TW201130937A - Photo-mask protection film - Google Patents

Photo-mask protection film Download PDF

Info

Publication number
TW201130937A
TW201130937A TW099139404A TW99139404A TW201130937A TW 201130937 A TW201130937 A TW 201130937A TW 099139404 A TW099139404 A TW 099139404A TW 99139404 A TW99139404 A TW 99139404A TW 201130937 A TW201130937 A TW 201130937A
Authority
TW
Taiwan
Prior art keywords
adhesive
weight
film
reticle
meth
Prior art date
Application number
TW099139404A
Other languages
Chinese (zh)
Other versions
TWI579354B (en
Inventor
Kouhei Yano
Daiki Yamashita
Original Assignee
Asahi Kasei E Materials Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009263118A external-priority patent/JP5319500B2/en
Priority claimed from JP2009263119A external-priority patent/JP5319501B2/en
Application filed by Asahi Kasei E Materials Corp filed Critical Asahi Kasei E Materials Corp
Publication of TW201130937A publication Critical patent/TW201130937A/en
Application granted granted Critical
Publication of TWI579354B publication Critical patent/TWI579354B/en

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/66—Containers specially adapted for masks, mask blanks or pellicles; Preparation thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

An objective of the invention is to provide a photo-mask protection film having an adhesive agent excellent in organic gas absorption performance. The photo-mask protection film is characterized by having a photo-mask protection film frame. An end surface of the photo-mask protection film frame has a photo-mask protection thin film, while another end surface has the adhesive agent. The weight degree of swelling for the adhesive agent to toluene is above five times.

Description

201130937 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種製造LSI (large scale integration，大型 積體電路）、超LSI等半導體裝置或液晶顯示板等時，為了 防止異物附著於光罩而使用的微影用光罩護膜。尤其是關 於一種使用需要南解像度之曝光所使用之準分子雷射的微 影用光罩護膜。尤佳為關於一種2〇〇 nm以下之紫外光曝光 所使用之微影用光罩護膜。 【先前技術】 於半導體製造之光微影步驟中，為了於晶圓上形成與積 體電路對應之光阻圖案，目前係使用步進機（縮小投影曝 光裝置）等半導體製造裝置。光罩護膜係於具有框形狀之 光罩護膜框之一端面鋪設有透明薄膜者，可防止因形成電 路圖案而導致異物直接附著於光罩上的情況。因此，即便 假设光微影步驟中有異物附著於光罩護膜上由於該等異 物於塗佈有光阻之晶圓上不會成像，因而可防止由異物之 像引起的半導體積體電路之短路或斷線等，可提高光微影 步驟之製造良率。 近年來，隨著半導體裝置之高積體化，光微影步驟中所 使用之曝光光趨於短波長化。即，要求於晶圓上描繪積體 電路圖案時可以更窄之線寬描緣微細電路圖案之技術。為 了應對該要求，例如作為光微影用步進機之曝光光，自先 前之g射線（波長436 nm)、i射線（波長365 nm)發展到使用 KrF準刀子雷射（波長248 nm)、ArF準分子雷射（波長I” 15J745.doc 201130937 nm)進而F2準分子雷射（波長157 nm)等更短波長之光。 」乍為將光罩護膜固定於光罩上之方法，通常採用利用黏 f劑以可剝離之方式進行固定的方法，作為用於固定之黏 著劑，已知有丙稀酸系、橡膠系、聚丁稀系、聚胺基甲酸 醋系、聚石夕氧系等黏著劑（參照專利文獻…黏著劑層係形 成在一端面鋪設有光罩護膜薄膜之光罩護膜框的另一端 面因此於光罩護膜薄膜或光罩被污染時，必需自光罩暫 時剝離光罩護膜並除去污垢而再將光罩護膜重新貼在光罩 上。又，為了消除曝光步驟中光罩護膜會自光罩脫落等問 題，對上述黏著劑亦要求即使施加一定負重亦不會剝離之 财負重性。 另一方面，隨著上述曝光光之短波長化、高能量化，光 罩護膜；！膜或光罩隨著曝光而產生污垢（稱為「霧化」）之 頻率增高。 現，為曝光過程中自黏著賴產生之有機氣體成分係導 致隨著上述曝光光之短波長化、高能量化而發生霧化的原 因之一。至今所使用之聚石夕氧系黏著劑或橡膠系黏著劑在 曝f過程中會產生較多氣體成分。作為降低自黏著劑產生 之氣體成分的方法，眾所周知的是專利文獻2〜4所揭示之 技術’但尚未完全解決問題。 又，隨著上述曝光光之短波長化、高能量化，光罩護膜 薄膜或光罩隨著曝光產生污垢之頻率增高，因此光罩護膜 或光罩之替換之頻率亦增強。於上述狀況下，較理想的是 穩定具有適當之黏著力並且替換時光罩上不產生殘膠之光 I5i745.doc 201130937 罩護膜用黏著劑。尤其是使用波長短於2GG nm之光的光微 影步驟中，更易於發生上述#化，因此更加要求將W護 膜自光罩剝離時光罩上不殘留黏著劑殘膠之特質。另一方 面田引使用KrF準分子雷射（波長248 nm)之光微影步驟 中’用作光罩護膜用霉占著劑之聚石夕氧系黏著劑存在光罩上 易殘留黏著劑殘膠，及耐負重性不充分之問題。 作為改善剝離光罩護膜後殘留殘膠之方法，於專利文獻 5中揭示有具有凝聚斷裂強度為2〇 g/mm2以上之黏著層的 光罩護膜。^，黏著劑之殘膠與耐負重性問題通常為取 捨關係，會產生殘膠較少之黏著劑的耐負重性差，曝光過 程中黏著劑會發生剝離的問題。 又’隨著近年來曝光光之短波長化、高能量化，圖案趨 於微細化，因此認為若光罩之平坦性差則會產生如下問 通於曝光時產生焦點偏移，燒接而成之圖案的精度變 差。因此，對光罩之平坦性要求會比先前更加嚴格。 現s忍為光罩護膜係使光罩之平坦性改變的因素之一，尤 其是利用光罩黏著材料改變平坦性的方法，於專利文獻 6、7中有揭示。 [先前技術文獻] [專利文獻] [專利文獻1 ]曰本專利特開平〇5_28丨7丨丨號公報 [專利文獻2]曰本專利特開平1 〇_丨7丨丨〇3號公報 [專利文獻3]曰本專利特開2〇〇1_147518號公報 [專利文獻4]國際公開第2〇〇4 〇46827號手冊 151745.doc 201130937 [專利文獻5]日本專利特開2006-146085號公報 [專利文獻6]曰本專利特開2009-276504號公報 [專利文獻7]日本專利特開2009-025560號公報 【發明内容】 [發明所欲解決之問題] 本發明者4人經研究得知：自黏著劑產生之有機氣體成 分中，以甲苯、乙酸乙酯為代表之有機溶劑成分係光罩上 所產生之霧化的主要原因。 有機溶劑主要於溶液聚合時使用，尤其是甲苯、乙酸乙 酯對黏著劑之溶解性較高，具有適度之沸點，因此為2業 上非常易於使用之溶劑。然而，使用上述有機溶劑所製造 之黏著劑中殘留有-定量之有機溶劑成分，其於曝光過程 中會以氣體形式釋放。為了減少自黏著劑層所產生之氣 體，通常採用將所使用之溶劑等低彿點成分於高溫下長時 間乾燥，儘量減少黏著劑層所殘留之溶劑的方法。然而， 長時間乾燥有損生產性，又，即便實施除去點著劑中之有 :溶劑成分之方法，亦必定會殘留一定量之有機溶劑成 刀，忒有機溶劑成分揮發會導致霧化。 因^，本發明者等人經過努力研究，結果發現：藉由使 先罩護膜所使用之黏著劑本身具有有機氣體吸附性能，可 防止會導致霧化之有機氣體吸附在以上’從而完成本申 清發明。 本發明之目的在於提供一 之黏著劑的光罩護膜。 種具有有機氣體 吸附性能優異 151745.doc 201130937 [解決問題之技術手段] 本發明者等人經過努力研究，結果得知藉由以下發明可 解決上述課題。 即，本發明如下： 1 ·種光罩濩膜，其係具有光罩護膜框，於該光罩護膜框 之端面具有光罩護膜薄膜且於另一端面具有黏著劑者， 並且該黏著劑對甲笨之重量膨潤度為5倍以上。 2. 如上述1之光罩護膜，其中該黏著劑含有（甲基）丙烯酸烷 基酯共聚物與硬化材料之反應生成物，並且該（甲基）丙烯 酸烷基酯共聚物係具有碳數4〜14之烷基之（甲基）丙烯酸烷 基酯與含有與硬化材料具有反應性之官能基之單體的共聚 物。 3. 如上述1或2之光罩護膜，其中該黏著劑藉由拉伸速度為 30 mm/min之拉伸試驗所獲得之23t下的3〇〇%模數值為 50〜350 mN/mm2。 4. 如上述1或2之光罩護膜，其中該硬化材料係選自由多官 能性環氧化合物及異氰酸酯系化合物所組成之群中之至少 一種硬化材料。 5. 如上述1或2之光罩護膜，其中該黏著劑係包含含有具備 聚合起始末端之聚合物及聚合起始劑之黏著劑組合物者， 該黏著劑中之聚合起始劑之總重量相對於黏著劑總重量為 8 ppm以下。 6. 如上述1或2之光罩護膜，其中該黏著劑係含有（甲基）丙 烯酸烷基酯共聚物重量份與硬化材料(K〇5〜3重量份之 151745.doc 201130937 反應生成物者。 如上述4之光罩6蒦膜’其中該多官能性環氧化合物係具 有2〜4個環氧基之含氮環氧化合物。 ’、 8. 如上述3之光罩護膜，盆各古工此私^ 、” 3有丙烯酸作為含有與該硬化 材料具有反應性之官能基的單體，該丙稀酸之量相對於構 成-亥(曱基)丙烯酸烷基酯共聚物之全部單體為〇 .卜 %。 9. 如上述3之光罩護膜’其中該(甲基)丙烯酸烷基酯共聚物 之重量平均分子量為7〇萬〜25〇萬。 1〇·-種光罩護膜’其係具有光罩護膜框於該光罩護膜 框之「端面具有光罩護膜薄膜且於另-端面具有黏著劑 者，並且該黏著劑係包含含有具備聚合起始末端之聚合物 及聚合起始劑之黏著劑組合物者，該黏著劑中之聚合^始 劑之總重量相對於黏著劑總重量為8 p p m以下。 11. 如上述10之光罩護膜，其中該聚合起始劑為過氧化物 系聚合起始劑或偶氮系聚合起始劑、或者烷基苯酮系聚合 起始劑或醯基氧化膦系聚合起始劑。 12. 如上述1〇或11之光罩護膜，其中該黏著劑含有（甲基）丙 烯酸烷基酯共聚物與硬化材料之反應生成物，該（甲基）丙 烯酸烷基酯共聚物係具有碳數4〜14之烷基之（甲基）丙烯酸 烷基酯與含有與硬化材料具有反應性之官能基之單體的共 聚物。 13.如上述10或1〗之光罩護膜’其中該黏著劑藉由拉伸速 度為30 mm/min之拉伸試驗所獲得之23t下的300%模數值 15J745.doc 201130937 為 50〜350 mN/mm2。 Η.如上述之光罩護膜，其中該硬化材料係選自由 多官能性環氧化合物及異氰酸酯系化合物所組成之群中之 至少一種硬化材料。 15. 如上述i〇4U之光罩護膜，其中該黏著劑對甲苯之重 量膨潤度為5倍以上。 16. 如上述12之光罩護膜，其中該黏著劑係含有（曱基）丙稀 酸烷基酯共聚物1〇〇重量份與硬化材料〇 〇5〜3重量份之反 應生成物者。 17_如上述14之光罩護膜，其中該多官能性環氧化合物係 具有2〜4個環氧基之含氮環氧化合物。 18. 如上述12之光罩護膜，其含有丙烯酸作為含有與該硬 化材料具有反應性之官能基的單體，該丙稀酸之量相對於 構成該（曱基）丙烯酸烷基酯共聚物之全部單體為〇丨〜5重量 % Ο 19. 如上述12之光罩護膜，其中該（甲基）丙烯酸烷基酯共聚 物之重量平均分子量為70萬〜250萬。 2〇·—種黏著劑，其係含有（甲基）丙烯酸烷基酯共聚物1〇〇 重量份與多官能性環氧化合物〇 〇5〜3重量份之反應生成物 者，该（甲基）丙烯酸烷基酯共聚物係具有碳數4~14之烷基 之（甲基）丙烯酸烷基酯與含有與環氧基具有反應性之官能 基的單體的共聚物，並且該黏著劑對甲苯之重量膨潤度為 5倍以上。 [發明之效果] I51745.doc 201130937 本發明之光罩護膜係有機氣體吸附性能優異之光罩護 膜，因此可有效地抑制光罩上所產生之霧化。 【實施方式】 以下’詳細說明用以實施本發明之形態（以下僅稱為 「本實施形態」）。以下之本實施形態僅為用以說明本發 明之例示，並非意在將本發明限定為以下内容。本發明可 於其主旨之範圍内適當變形而實施。 本發明之光罩護膜所使 —«V- π⑴β I今、〜王里Λ夕》同度 為5倍以上。此處所謂膨濶，係指彈性凝膠吸收液體（溶劑） 而使體積、重量增加的現象’重量膨潤度表示彈性凝膠吸 收液體（溶劑）而使重量增加時之增加比例。 若黏著劑之重量膨潤度較Α，則可利用黏著劑吸附由光 罩護膜與光罩所圍成之封閉空間中存在的以甲苯、乙酸乙 醋為代表的有機氣體，可大幅度降低有機氣體與光罩接觸 之頻率。結果可大幅度抑制霧化之產生。 藉由增大重Ϊ膨潤度’不僅可吸附有機氣體，亦可 降低所產生之氣體之量。 具體5，判明藉由控制製作黏 者劑時所使用之溶劑及作Α 哲 ρ你 作為4質之聚合物的重量膨潤度， 即便溶劑殘留於聚合物中 ^ -V Μ ⑷j个a自聚合物中以氣體 形式釋放，而保留在聚合物令。 ^ ^ ^ ^ 藉由控制重量膨潤度可減 劑之親Μ，… ^㈣為藉由提高聚合物與溶 溶劑渗入聚合物中。 I。構’而使殘留之 則推測聚合物 進而’若甲苯之重量膨潤度為5倍以上 I51745.doc 201130937 之交聯網狀結構之大小達到最適合吸附由光罩護膜與光罩 所圍成之封閉空間中存在的以甲$、乙酸乙酯為代表之有 機氣體的大小，大幅度抑制霧化之產生。 基於以上原因，較佳為光罩護膜所使用之黏著劑對甲笨 之重量膨潤度為5倍以上，較佳為7倍以上，更佳為9倍以 上’尤佳為10倍以上。 若本申請發明之光罩護膜所使用之黏著劑的重量膨潤度 為5倍以上則無限定，尤其就與光罩之接著力充分且剝離 後之殘膠較少之方面而言，較佳為包含含有（甲基）丙烯酸 烷基酯共聚物與硬化材料之反應生成物而成之組合物的黏 著劑，並且該（曱基）丙烯酸烷基酯共聚物係藉由使具有碳 數4〜14之烷基之（甲基）丙烯酸烷基酯（以下稱為「a成 分」）、與含有與硬化材料具有反應性之官能基之單體（以 下稱為「B成分」）中的至少兩種單體成分共聚合而獲得之 共聚物。 烧基醋共聚物為A成分99〜80重量％、B成分1〜20重量〇/0 之單體昆合物的共聚物時可表現出適度的與光罩之接著 力，故而更佳。 此處’將A成分之單體分為碳數4〜14之烷基為直鏈狀者 (以下稱為「A1成分」）與碳數4〜14之烷基為支鏈狀者（以 下稱為「A2成分」）之情形時，若上述（甲基）丙烯酸烷基 酯共聚物係A2成分9〜59%之單體混合物的共聚物，則黏著 力優異’因而更佳。若為A1成分4〇〜90重量％、A2成分 9〜59重量％、B成分1〜2〇重量％之單體混合物之共聚物，則 151745.doc 201130937 剝離後之殘膠減少，因而更佳。 A1成分之丙烯酸酯系單體係烷基碳數為4〜14之（曱基）丙 烯酸烷基酯，具體可列舉：（甲基）丙烯酸丁酯、（甲基）丙 烯酸己酯、（甲基）丙烯酸辛酯、（甲基）丙烯酸癸酯、（曱基） 丙烯酸十二烷基酯、（甲基）丙烯酸月桂酯等直鏈脂肪族醇 之（甲基）丙烯酸酯。該等可單獨使用亦可併用2種以上。其 中，（甲基）丙烯酸丁酯、（曱基）丙烯酸辛酯等具有碳數4〜8 之烧基之（曱基）丙稀酸烧基酯表現出適度之與光罩之接著 性’因此可較好地使用。 A2成分之丙烯酸酯系單體為具有支鏈狀烷基鏈者，具體 可列舉：（甲基）丙烯酸異丁酯、（甲基）丙烯酸異戊酯、（甲 基）丙烯酸2-乙基己酯、（甲基）丙烯酸異辛酯、（曱基）丙烯 酸異壬酯。該等可單獨使用亦可併用2種以上。其中，就 共聚性方面而言，較佳為使用（甲基）丙烯酸異丁酯（例如丙 烯酸異丁酯）或（甲基）丙烯酸2_乙基己酯（例如丙烯酸2_乙基 B成分之單體係可與上述八成分之單體共聚合的單體， 且為與環氧基具有&應性的單冑。例如為（甲基）丙稀酸、 衣康酸、順丁烯二酸、 烯酸2-羥基乙酯、（甲j 西文、丁烯酸等含羧基單體，或（甲基）丙 (甲基）丙烯酸3_羥基丙酯、（甲基）丙烯酸 羥基丙S曰（甲基）丙烯酸4-羥基丁酯等含羥基單體。該 等可單獨使用亦可併用2種以上^其巾，就共聚性、通用[Technical Field] The present invention relates to a semiconductor device such as an LSI (large scale integration circuit) or a super LSI, or a liquid crystal display panel, etc., in order to prevent foreign matter from adhering to the reticle. The lithography used is a reticle film. In particular, it is a reticle mask for lithography that uses excimer lasers for exposures that require south resolution. Optima is a lithographic mask for lithography used for exposure to ultraviolet light below 2 〇〇 nm. [Prior Art] In the photolithography step of semiconductor manufacturing, in order to form a photoresist pattern corresponding to an integrated circuit on a wafer, a semiconductor manufacturing apparatus such as a stepping machine (reduced projection exposure apparatus) is currently used. The mask film is provided with a transparent film on one end surface of the mask film frame having a frame shape, and it is possible to prevent foreign matter from directly adhering to the mask due to the formation of the circuit pattern. Therefore, even if foreign matter adheres to the mask film in the photolithography step, since the foreign matter is not imaged on the wafer coated with the photoresist, the semiconductor integrated circuit caused by the image of the foreign matter can be prevented. Short circuit or disconnection, etc., can improve the manufacturing yield of the photolithography step. In recent years, with the high integration of semiconductor devices, the exposure light used in the photolithography step tends to be short-wavelength. That is, it is required to draw a fine circuit pattern with a narrower line width when an integrated circuit pattern is drawn on a wafer. In order to cope with this requirement, for example, exposure light as a stepper for photolithography has been developed from the previous g-ray (wavelength 436 nm), i-ray (wavelength 365 nm) to the use of KrF quasi-knife laser (wavelength 248 nm), ArF excimer laser (wavelength I) 15J745.doc 201130937 nm) and then F2 excimer laser (wavelength 157 nm) and other shorter wavelengths of light. "The method of fixing the mask film to the mask is usually A method of fixing by means of a viscous agent in a peelable manner is used. As an adhesive for fixing, an acrylic acid type, a rubber type, a polybutylene type, a polyamino carboxylic acid vinegar type, and a polychlorinated oxygen are known. Adhesives (refer to the patent document... the adhesive layer is formed on the other end surface of the reticle film frame on which the reticle film is coated on one end surface, so when the reticle film or the reticle is contaminated, it is necessary to The mask temporarily peels off the mask film and removes the dirt, and then reattaches the mask film to the mask. In addition, in order to eliminate the problem that the mask film will fall off the mask during the exposure step, the above adhesive is also required. Even if a certain load is applied, the financial burden will not be stripped. On the other hand, as the exposure light is shortened in wavelength and energy is increased, the frequency of the photomask protective film; the film or the mask is contaminated by exposure (referred to as "atomization"). In the process, the organic gas component generated by the adhesion is one of the causes of atomization due to the short-wavelength and high energy of the exposure light. The polyoxo-based adhesive or the rubber-based adhesive used so far. In the process of exposure f, a large amount of gas components are generated. As a method of reducing the gas component generated by the self-adhesive agent, the techniques disclosed in Patent Documents 2 to 4 are known 'but the problem has not been completely solved. The short-wavelength and high-energy, the frequency of the mask film or the mask is increased with exposure, so the frequency of replacement of the mask or the mask is also enhanced. Under the above circumstances, it is desirable. Stabilizes the light with the proper adhesion and does not produce residual glue on the mask. I5i745.doc 201130937 Adhesive for the cover film, especially in the photolithography step using light shorter than 2GG nm, It is easy to occur in the above-mentioned #化, so it is more required to leave the W film on the reticle without leaving the adhesive residue. On the other hand, the field uses the KrF excimer laser (wavelength 248 nm) in the light lithography step. 'The use of a polysulfide-based adhesive for the use of a mold-preserving agent for a mask film has a problem of residual adhesive residue on the mask, and insufficient load-bearing resistance. In the method of gluing, Patent Document 5 discloses a photomask film having an adhesive layer having a cohesive breaking strength of 2 〇g/mm 2 or more. ^, the adhesive residue and the load-bearing property of the adhesive are usually trade-off relations, and are generated. Adhesives with less residual adhesive have poor load-bearing properties, and the adhesive may be peeled off during exposure. In addition, with the short-wavelength and high energy of exposure light in recent years, the pattern tends to be finer. When the flatness of the cover is poor, the focus shift occurs when exposed, and the accuracy of the pattern formed by burning is deteriorated. Therefore, the flatness requirements for the reticle are more stringent than before. One of the factors for changing the flatness of the mask, such as a method of changing the flatness by using a mask adhesive material, is disclosed in Patent Documents 6 and 7. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 5_28丨7丨丨 [Patent Document 2] 曰本专利特开平1 〇_丨7丨丨〇3号 [Patent [Patent Document 3] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2006-146085 [Patent Document 5] Japanese Patent Laid-Open No. Hei. No. 2006-146085 [Patent Document 6] Japanese Laid-Open Patent Publication No. 2009-276504 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2009-025560 (Summary of the Invention) [Inventors of the Invention] Among the organic gas components produced by the adhesive, the organic solvent component represented by toluene or ethyl acetate is the main cause of atomization generated on the reticle. The organic solvent is mainly used in solution polymerization, and in particular, toluene and ethyl acetate have high solubility to the adhesive and have a moderate boiling point, so it is a solvent which is very easy to use in the industry. However, the amount of the organic solvent component remaining in the adhesive produced by using the above organic solvent is released as a gas during the exposure. In order to reduce the gas generated from the adhesive layer, a method in which a low-foam component such as a solvent to be used is dried at a high temperature for a long period of time and the solvent remaining in the adhesive layer is minimized is usually employed. However, long-term drying impairs productivity, and even if a solvent component is removed from the dispensing agent, a certain amount of the organic solvent is surely left to form a knife, and the organic solvent component volatilizes to cause atomization. As a result of the diligent study, the inventors of the present invention found that the organic gas adsorbing property of the adhesive film itself can prevent the organic gas which is atomized from being adsorbed on the above. Shen Qing invention. It is an object of the present invention to provide a mask film for an adhesive. The organic gas has excellent adsorption performance. 151745.doc 201130937 [Technical means for solving the problem] As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by the following invention. That is, the present invention is as follows: 1. A reticle enamel film having a reticle film frame, having a reticle film on the end surface of the reticle film frame and having an adhesive on the other end surface, and The adhesion of the adhesive to the weight of the nail is more than 5 times. 2. The photomask film according to the above 1, wherein the adhesive contains a reaction product of an alkyl (meth) acrylate copolymer and a hardening material, and the alkyl (meth) acrylate copolymer has a carbon number A copolymer of an alkyl (meth) acrylate having 4 to 14 alkyl groups and a monomer having a functional group reactive with a hardening material. 3. The photomask film according to the above 1 or 2, wherein the adhesive has a value of 3〇〇% at 23t obtained by a tensile test at a tensile speed of 30 mm/min of 50 to 350 mN/mm2. . 4. The photomask film according to the above 1 or 2, wherein the hardening material is at least one selected from the group consisting of a polyfunctional epoxy compound and an isocyanate compound. 5. The photomask film according to the above 1 or 2, wherein the adhesive comprises an adhesive composition containing a polymer having a polymerization starting end and a polymerization initiator, and a polymerization initiator in the adhesive The total weight is 8 ppm or less relative to the total weight of the adhesive. 6. The photomask film according to the above 1 or 2, wherein the adhesive contains a (meth)acrylic acid alkyl ester copolymer in parts by weight and a hardening material (K〇5 to 3 parts by weight of 151745.doc 201130937 reaction product) The photomask 6 蒦 film of the above 4, wherein the polyfunctional epoxy compound has a nitrogen-containing epoxy compound having 2 to 4 epoxy groups. ', 8. The photomask film of the above 3, the basin Each of the ancient workers has an acrylic acid as a monomer having a functional group reactive with the hardening material, and the amount of the acrylic acid is relative to the entire composition of the alkyl acrylate copolymer. The monomer is 〇.b%. 9. The photomask film of the above 3, wherein the (meth)acrylic acid alkyl ester copolymer has a weight average molecular weight of 70,000 to 250,000. 1〇·-species light The cover film has a reticle cover frame on the end face of the reticle cover film having a reticle film and having an adhesive on the other end face, and the adhesive contains a polymerization start end The adhesive composition of the polymer and the polymerization initiator, the total weight phase of the polymerization initiator in the adhesive The total weight of the adhesive is 8 ppm or less. 11. The photomask according to 10 above, wherein the polymerization initiator is a peroxide polymerization initiator or an azo polymerization initiator, or an alkyl benzophenone A polymerization initiator or a fluorenylphosphine oxide-based polymerization initiator. 12. The photomask according to the above 1 or 11 wherein the adhesive contains a reaction of an alkyl (meth)acrylate copolymer with a hardening material. The product, the (meth)acrylic acid alkyl ester copolymer is a copolymer of an alkyl (meth)acrylate having an alkyl group having 4 to 14 carbon atoms and a monomer having a functional group reactive with a hardening material. 13. The photomask film of the above 10 or 1] wherein the adhesive is obtained by a tensile test at a tensile speed of 30 mm/min, and the 300% modulus value obtained at 23 t is 15 J745.doc 201130937 is 50~ The photomask film according to the above, wherein the hardening material is at least one selected from the group consisting of a polyfunctional epoxy compound and an isocyanate compound. 15. As described above, i〇4U Photomask cover film, wherein the adhesive has a swelling degree to the weight of toluene More than 5 times. 16. The photomask film according to the above 12, wherein the adhesive comprises a reaction of 1 part by weight of a (mercapto)alkyl acrylate copolymer and 5 to 3 parts by weight of the hardening material The photomask according to the above 14, wherein the polyfunctional epoxy compound is a nitrogen-containing epoxy compound having 2 to 4 epoxy groups. 18. The photomask film of the above 12, It contains acrylic acid as a monomer having a functional group reactive with the hardening material, and the amount of the acrylic acid is 〇丨5 wt% with respect to all monomers constituting the (alkyl) alkyl acrylate copolymer. Ο 19. The photomask film of the above 12, wherein the (meth)acrylic acid alkyl ester copolymer has a weight average molecular weight of 700,000 to 2.5 million. 2〇-- an adhesive comprising a reaction product of 1 part by weight of a (meth)acrylic acid alkyl ester copolymer and 5 to 3 parts by weight of a polyfunctional epoxy compound, (methyl An alkyl acrylate copolymer is a copolymer of an alkyl (meth) acrylate having an alkyl group having 4 to 14 carbon atoms and a monomer having a functional group reactive with an epoxy group, and the adhesive pair The weight of toluene is 5 times or more. [Effect of the Invention] I51745.doc 201130937 The photomask film of the present invention is a photomask film having excellent organic gas adsorption performance, so that atomization generated on the photomask can be effectively suppressed. [Embodiment] Hereinafter, the mode for carrying out the invention (hereinafter simply referred to as "this embodiment") will be described in detail. The following examples are merely illustrative of the invention and are not intended to limit the invention to the following. The present invention can be carried out with appropriate modifications within the scope of the gist of the invention. The photomask film of the present invention has a degree of equality of -{V-π(1)β I, ~王里Λ夕. The term "expansion" as used herein refers to a phenomenon in which the elastic gel absorbs a liquid (solvent) to increase the volume and weight. The weight swelling degree indicates an increase ratio when the weight of the elastic gel absorbs the liquid (solvent). If the viscosity of the adhesive is relatively low, the adhesive can adsorb the organic gas represented by toluene and ethyl acetate in the enclosed space surrounded by the reticle film and the reticle, which can greatly reduce the organic The frequency at which the gas contacts the reticle. As a result, the generation of atomization can be greatly suppressed. By increasing the degree of swelling, it is possible to adsorb not only the organic gas but also the amount of gas generated. Specifically, it is determined by controlling the weight of the solvent used in the preparation of the adhesive and the weight of the polymer as a 4-type polymer, even if the solvent remains in the polymer ^ -V Μ (4) j a self-polymer It is released as a gas and remains in the polymer order. ^ ^ ^ ^ By controlling the relatives of the weight-swelling depressibility, ... (4) is by infiltrating the polymer with the solvent into the polymer. I. The structure of the residue is estimated to be the same as the weight of the toluene is 5 times or more. I51745.doc 201130937 The size of the network structure of the intersection is the most suitable for the adsorption by the reticle and the reticle. The size of the organic gas represented by A$ and ethyl acetate present in the space greatly suppresses the generation of atomization. For the above reasons, it is preferred that the adhesive used for the reticle film has a weight swelling degree of 5 times or more, preferably 7 times or more, more preferably 9 times or more, and more preferably 10 times or more. The adhesive used in the photomask coating of the present invention has a weight swelling degree of not less than 5 times, and is particularly preferably in terms of sufficient adhesion to the photomask and less residual adhesive after peeling. An adhesive comprising a composition comprising a reaction product of a (meth)acrylic acid alkyl ester copolymer and a hardening material, and the (alkyl)alkyl acrylate copolymer is obtained by having a carbon number of 4~ At least two of an alkyl (meth)acrylate (hereinafter referred to as "a component") having 14 alkyl groups and a monomer having a functional group reactive with a hardening material (hereinafter referred to as "component B") A copolymer obtained by copolymerizing a monomer component. The calcined vinegar copolymer is preferably a copolymer of a monomeric composition of 99 to 80% by weight of the A component and 1 to 20 parts by weight of the B component, and a binder of the monomer, which exhibits an appropriate adhesion to the mask. Here, 'the monomer of the A component is divided into a linear one having a carbon number of 4 to 14 (hereinafter referred to as "A1 component") and an alkyl group having 4 to 14 carbon atoms as a branch (hereinafter referred to as In the case of the "A2 component", when the (meth)acrylic acid alkyl ester copolymer is a copolymer of a monomer mixture of 9 to 59% of the A2 component, the adhesion is excellent, and thus it is more preferable. If it is a copolymer of a monomer mixture of 4 to 90% by weight of the A1 component, 9 to 59% by weight of the A2 component, and 1 to 2% by weight of the component B, the residual rubber after the 151745.doc 201130937 peeling is reduced, so that it is better. . The acrylate-based single-system alkyl group having a carbon number of 4 to 14 is a (meth)acrylic acid alkyl ester, and specific examples thereof include butyl (meth)acrylate, hexyl (meth)acrylate, and (methyl). A (meth) acrylate of a linear aliphatic alcohol such as octyl acrylate, decyl (meth) acrylate, lauryl (meth) acrylate or lauryl (meth) acrylate. These may be used alone or in combination of two or more. Among them, a (mercapto) propyl acrylate having a carbon number of 4 to 8 such as butyl (meth)acrylate or octyl methacrylate exhibits a moderate adhesion to the reticle. Can be used well. The acrylate monomer of the component A2 is a branched alkyl chain, and specific examples thereof include isobutyl (meth)acrylate, isoamyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Ester, isooctyl (meth)acrylate, isodecyl (mercapto) acrylate. These may be used alone or in combination of two or more. Among them, in terms of copolymerizability, it is preferred to use isobutyl (meth)acrylate (for example, isobutyl acrylate) or 2-ethylhexyl (meth)acrylate (for example, 2-ethyl ethyl acrylate) a monomer which can be copolymerized with a monomer of the above eight components, and which is a mono-peptate having an <RTIgt;</RTI> Acid, 2-hydroxyethyl enoate, carboxyl group-containing monomer such as methyl methacrylate or crotonic acid, or 3-hydroxypropyl (meth) acrylate (meth) acrylate, hydroxy propyl acrylate (meth) acrylate a hydroxyl group-containing monomer such as 4-hydroxybutyl (meth)acrylate, which may be used alone or in combination of two or more kinds thereof, in terms of copolymerizability and general use.

151745.doc 201130937 (甲基）丙烯酸酯，（甲基）丙烯酸等含羧基單體。尤其就殘 膠方面而言，較佳為（曱基）丙烯酸，（曱基）丙烯酸之含量 相對於構成（甲基）丙稀酸烧基醋共聚物之全部單體為〇 1〜5 重量％，更佳為0.5〜4重量❶/。，更佳為〇 8〜3重量0/〇。 上述（甲基）丙烯酸烷基酯共聚物中，上述A1成分之丙烯 酸酯系單體之用量於單體混合物中為4〇〜9〇重量％、較佳 為45〜80重量％。又，A2成分宜為9〜59重量％ ,較佳為 15〜50重量％，B成分宜為卜20重量％，較佳為2〜1〇重量 〇/〇。 若（曱基）丙烯酸烷基酯共聚物之重量平均分子量為70萬 以上' 250萬以下，則黏著劑層之凝聚力、接著力達到適 度之大小，成為不易殘留殘膠且具有充分之接著力、耐負 重性的黏著劑，故而較佳。重量平均分子量較佳為9〇萬以 上' 230萬以下’更佳為1〇〇萬以上、2〇〇萬以下。關於重 量平均分子量之控制方法，可藉由眾所周知之方法進行控 制。具體而言，通常有如下傾向：聚合反應時之單體濃度 越高則重量平均分子量越大，聚合起始劑量之量越少，且 聚合溫度越低則重量平均分子量越大。 上述（曱基）丙烯酸烷基酯共聚物之製造可適當選用溶液 聚合、塊狀聚合、乳化聚合、各種自由基聚合等眾所周知 之製造方法。又，所獲得之（甲基）丙烯酸烷基酯共聚物可 為無規共聚物、嵌段共聚物、接枝共聚物等中任一種。再 者，溶液聚合中，聚合溶劑例如可使用乙酸乙酯、曱苯 等。 151745.doc 201130937 作為具體之溶液聚合例’於氮氣等惰性氣體氣流下，例 如相對於單體總量1 〇〇重量份添加偶氮雙異丁腈〇 〇 U 0重 量份作為聚合起始劑，通常於50〜70。(：左右下反應8〜3 0小 時左右。自由基聚合所使用之聚合起始劑、鏈轉移劑、乳 化劑等並無特別限定，可適當選擇使用。 作為較佳之聚合起始劑，例如可列舉：偶氮系之2,2,_偶 氮雙異丁腈、2,2’-偶氮雙-2-曱基丁腈、2,2，-偶氮雙（2-曱 基丙酸甲酯）、4,4，_偶氮雙-4-氰基纈草酸等，或過氧化物 系之過氧化苯甲醯等。 本申請發明之光罩護膜所使用之黏著劑尤佳為包含含有 (曱基）丙烯酸烷基醋共聚物與硬化材料之反應生成物而成 之組合物的黏著劑。 作為該硬化材料，可列舉：金屬鹽、金屬烷氧化物、醛 系化合物、非胺基樹脂系胺基化合物、脲系化合物、異氰 酸I系化合物、金屬螯合物系化合物、三聚氰胺系化合 物、氮丙咬系化合物等通常黏著劑所使用之硬化材料，就 與（甲基）丙稀酸院基酷共聚物所具有之官能基成分之反應 性方面而[較佳為選自由異氰酸醋系化合物及多官能性 環氧化合物所組成之群中之至少—種硬化材料，更佳為多 官能性環氧化合物。 具體而言’作為異氛酸酿系化合物，可列舉甲苯二異氰 酸醋，作為多官能性環氧化合物，可列舉：新戊二醇二缩 水甘油"乙二醇二縮水甘油_、雙紛A二縮水甘油 趟、雙紛F二縮水甘油越、對苯二甲酸二縮水甘油酿、二 151745.doc 201130937 聚酸二縮水甘油酯、異氰尿酸三縮水甘油酯、二甘油基三 縮水甘油峻、山梨糖醇四縮水甘油醚、n，n,n'，n'-四縮水 甘油基間二甲苯二胺、^-雙（N，N_二縮水甘油基胺基甲 基）環己烧、N，N，N，，N，-四縮水甘油基二胺基二苯基甲烷 等。 該等中’較佳為具有2〜4個環氧基之含氮環氧化合物， 就反應性方面而言’宜使用具有4個環氧基之含氮環氧化 合物。若反應性良好，則於塗佈黏著劑後，交聯反應迅速 結束’因此特性於短時間内穩定’於生產性方面優異。 又’藉由調整硬化材料之含量，可控制重量膨潤度。所 謂膨潤係指溶劑分子進入聚合物分子間，使擴大分子間距 之力與交聯網狀結構之彈性取得平衡的狀態。膨潤的大小 丈/谷劑與聚合物之親和性及聚合物之交聯度的影響，可藉 由控制該等而控制甲苯之重量膨潤度。溶劑與聚合物之親 和性較高者通常重量膨潤度會提高。作為親和性之標準， 通常使用SP值（Solubility parameter，溶解度參數），提出 sp值較近者彼此親和性較高之「p〇lymerhandb〇〇k (4th edition) WILEY-INTER SCIENCE P689-711」中有各 種SP值之記載，甲苯為18 2(Mpaw2)，乙酸乙醉為18 6 (MPa〗/2)，為大致相同之值。因此，構成聚合物之單體成 分的SP值接近於甲苯、乙酸乙酯使重量膨潤度提高。例 如，作為丙烯酸系黏著劑之單體成分之丙烯酸丁酯 〇 (MPa1")，丙烯酸異丁酯為 17 4(Mpa]/2), 劑之單體成分的丁二烯為14 5(MPaw2) 1/2λ t f办田- ~ * 作為橡膠系黏著 ’異丁烯為15.0 151745.doc 201130937 (Mh )，乙婦為 15·76(ΜΡ,)，丁稀為 i3 7(Mpa，，作 為聚^氧黏著劑之單體成分之二甲基石夕氧燒為则〜⑴ 二V。…就聚合物與溶劑之親和性之觀點而言， 較佳為丙烯酸系黏著劑。 又’重量膨潤度亦取決於聚合物 切疋父聯度。若交聯度過 低’則冷劑分子不會滲人聚合物交聯網狀結構中，重量膨 潤度降低。又1交聯度過高，則不會進人聚合物交聯網 ㈣構’ί量膨潤度減小。因此，可藉由適當控制聚合物 之交聯度而控制重量膨潤度。 若硬化材料之含量相對於上述（甲基）丙稀酸烧基醋共聚 物100重量份為0·05〜3重量份’貝”苯或乙酸乙酯之重量 膨潤度為5倍以上，成為較佳的光罩護膜用黏著劑。其 中，若硬化材料之含量為〇 〇5重量份〜〇 2〇重量份，則甲苯 或乙酸乙酯之重量膨潤度進一步增大，成為更加的光罩護 膜用黏著劑，抑制霧化之產生，變得不易殘留殘膠。進 而，達到適度之交聯密度，因此成為不易對光罩之平坦性 造成特別影響（尤其可抑制光罩之變形）的光罩黏著劑。認 為其原因在於’若硬化材料之含量在〇2〇重量份以下，則 交聯密度不會變得過大，因此黏著劑吸收對光罩施加之應 力，緩和對光罩之平坦性的影響。另一方面，認為若為 0.05重量份以上’則交聯密度不會變得過小，因此維持製 造步驟中之操作性’不會產生自光罩剝離光罩護膜時殘留 殘膠的問題。 於含有上述（曱基）丙烯酸烷基酯共聚物及多官能性環氧 151745.doc 201130937 化合物之組合物之情形時，可藉由將聚合物之交聯度控制 為適度，而將重量膨潤度最大調整至15倍左右。尤其是若 甲苯之重量膨潤度為8倍〜14倍左右，則所吸附之甲苯或乙 酸乙酯等有機氣體保留在黏著劑中之效果較大，故而較 佳。認為其原因在於，若甲苯之重量膨潤度為8倍〜M倍左 右，則聚合物間之交聯網狀結構間隔達到適合捕獲曱苯及 乙酸乙酯的大小。 用以獲得（曱基）丙烯酸烷基酯共聚物與多官能性環氧化 合物之反應生成物的反應係藉由如下方式進行：稱量（甲 基）丙烯酸烷基醋共聚物溶液與多官能性環氧化合物溶 液’進行混合、㈣以達到均句混合，將溶劑加熱乾燥除 去後，再進行加溫。 若調節（曱基）丙烯酸烷基酯共聚物之平均分子量與硬化 材料之含量，以使黏著劑藉由拉伸速度為3〇 之拉 伸試驗所獲得的23t下的300%模數值達到5〇〜35〇 mN/mm2,則黏著劑之耐負重性優異，成為不易殘留殘膠 之黏著劑，因此較佳。此處，所謂3〇〇%模數值係指於 23°C、65%RH氣體環境下，使用自動立體測圖儀，將黏著 層之厚度為0.2 mm且寬度為。mm之黏著劑樣品以炎盤間 距為10 mm、拉伸速度為3〇 mm/min之條件下進行拉伸時 300%應變的每單位剖面積之應力。3〇〇%模數值主要藉由 (甲基）丙烯酸烷基酯共聚物之重量平均分子量與硬化材料 之含量控制。（甲基）丙烯酸烷基酯共聚物之重量平均分子 量越大則300%模數值亦越大，多官能性環氧化合物之含 151745.doc 201130937 量越多則300%模數值亦越大。 (甲基）丙烯酸烷基酯共聚物之重量平均分子量在可使 300%模數值達到50~350 mN/mm2之範圍内即可，尤其是重 量平均分子量為70萬以上、250萬以下時，黏著劑層之凝 聚力、接著力達到適度之大小，成為不易殘留殘膠且具有 充分之接著力、耐負重性之黏著劑，故而較佳。重量平均 分子量較佳為90萬以上、230萬以下，更佳為ι〇〇萬以上、 200萬以下。 關於重量平均分子量之控制方法’可藉由眾所周知之方 法控制。具體而言’通常有如下傾向：聚合反應時之單體 濃度越高則重量平均分子量越大，聚合起始劑量之量越 少’另外聚合溫度越低則重量平均分子量越大。 硬化材料之含量在可使300%模數值達到5〇〜35〇 mN/mm2 之範圍内即可，尤其是相對於上述（甲基）丙烯酸烷基酯共 聚物100重量份，較佳為〇.〇5〜3重量份，更佳為〇1〜2 5重 量份。更佳為0.1 5〜2.0重量份。若硬化材料之含量在上述 範圍内’則交聯密度達到適度之密度，成為不易殘留殘膠 且具有充分之接著力、耐負重性之黏著劑。 上述（曱基）丙烯酸炫基酯共聚物之重量平均分子量與硬 化材料之含量的範圍中，尤佳為黏著劑藉由拉伸速度為3〇 mm/min之拉伸試驗所獲得之23。(：下之300%模數值為 5〇〜350 mN/mm2之範圍的值，更佳為8〇〜3〇〇 mN/mm2,更 佳為 100〜280 mN/mm2。若 300%模數為 5〇〜35〇 mN/mm2， 則具有充分之接著性、耐負重性，且剝離時之殘膠亦減 151745.doc 201130937 少，故而較佳。 關於黏著劑中殘留之聚合起始劑，較佳為相對於黏著劑 重量為8 PPm以下。若黏著劑中殘留之聚合起始劑相對於 黏著劑總重量為8 PPm以下，則可大幅度抑制霧化之產 生。關於藉由降低黏著劑層中殘留之聚合起始劑之量會改 善光罩之霧化的原因尚不明確，現考慮如下 產生霧化之原因有多種，現認為其主要原因為：曝光氣 體環境下存在之有機氣體成分藉由曝光光m引起化 學反應，其反應生成物會附著於光罩上而導致產生霧化。 推測若黏著劑層存在某-定量以上之聚合起始劑，則該聚 合起始劑會藉由曝光光之能量而開裂，引發有機氣體之化 學反應，結果導致霧化之反應生成物之生成量大幅度增 加。 基於以上原因 聚合起始劑的用 更佳為7 ppm以下 ，關於光罩護膜所使用之黏著劑中殘留的 量相對於黏著劑重量較佳為8 ppm以下， ’更佳為6 ppm以下。 關於降低、控制黏著劑層中殘留之聚合起始劑的方法， 有如下方法等··降低黏著劑聚合物聚合時之聚合起始劑 量，或使用易於熱分解之聚合起始劑；又，藉由黏著劑之 ㈣ '乾無步驟’ &時間施加高溫’藉由乾燥步驟使聚合 起始劑分解。 σ 表示聚合起始劑 度。所謂半衰期， 的時間，1 0小時半 之熱分解速度的指標有1 〇小時半衰期溫 係指聚合起始劑分解直至原來量之一半 衰期溫度表示半衰期為10小時之溫度。 151745.doc •19· 201130937 10小時半衰期溫度較低之聚合起始劑易熱分解，因此不易 殘留在黏著劑層上。尤佳為使用10小時半衰期溫度為8代 以下' 較佳為75。(：以下之聚合起始劑。 若上述聚合起始劑為偶氮系聚合起始劑，則可列舉： 2,2’-偶氮雙（4-曱氧基-2,4-二甲基戊腈）（1〇小時半衰期溫度 30°C)、2,2'-偶氮雙異丁腈（10小時半衰期溫度6〇。〇、2,2，_ 偶氮雙（2,4-二曱基戊腈）（1〇小時半衰期溫度51。匚）、2〗，-偶 氮雙（2-甲基丙酸曱酯）（i 〇小時半衰期溫度66它）、2,广偶氮 雙（2-甲基丁猜）（1〇小時半衰期溫度67。〇,若為過氧化物 系聚合起始劑，則可列舉：過氧化二苯甲醯（1〇小時半衰 期溫度74C)、過氧化二月桂醯（10小時半衰期溫度6yc) 等，但並不限於此。 又，光聚合起始劑亦會導致產生霧化。作為降低、控制 黏著劑層中殘留之光聚合起始劑之方法，可考慮如下方 法：藉由加熱使之熱分解或乾燥、蒸發之方法，或照射紫 外線而使光聚合起始劑分解之方法，使用藉由上述方法而 易於分解之光聚合起始劑之方法等^作為藉由上述方法而 易於分解之光聚合起始劑，可列舉：院基苯酉同系聚合起始 劑或酿基氧化鱗系聚合起始劑等。作為烷基苯酮系聚合起 始劑’具體可列舉：2,2-二甲氧基·丨，2_二苯基乙烧、 1-經基環己基-苯基酬、2-經基_2_甲基_丨_笨基丙烷酮、 1-[4-(2-羥基乙氧基）苯基]-2-羥基-2-甲基丙烷_丨_酮、2羥 基-1_{4-[4-(2-羥基-2-曱基-丙醯基）_苄基]苯基}·2_甲基丙 烧-Η同、2-甲基-Η4-甲基硫笨基）·2·嗎啉基丙烧小^同、 151745.doc •20· 201130937 2-节基-2-二曱胺基-丨气‘嗎啉基苯基）·丁酮、2_(二曱胺 基）-2-[(4-曱基苯基）曱基]嗎啉基）苯基丁 _ 等。作為醯基氧化膦系聚合起始劑，可列舉：2,4,6-三甲 基苯曱醯基-二苯基-氧化膦、雙（2,4,6_三曱基苯甲醯基）笨 基氧化膦等。 為使黏著劑中殘留之聚合起始劑之總重量相對於黏著劑 總重量為8 ppm以下，較佳為使用包含含有（甲基）丙烯釀 烷基酯共聚物與硬化材料之反應生成物而成之組合物的黏 著劑’該（甲基）丙烯酸烷基酯共聚物係藉由使具有碳數 4〜14之烷基之（曱基）丙烯酸烷基酯與含有與硬化材料具有 反應性之官能基之單體中之至少兩種單體成分共聚合而獲 得的共聚物。 又’黏著劑組合物中除上述反應生成物以外亦可視需要 含有填充劑、顏料、稀釋劑、抗老化劑、紫外線穩定劑等 先刖眾所周知之添加劑。該等添加劑可使用丨種或2種以 上。然而，較佳為適時設定添加量，以獲得所需物性。 本發明之光罩護膜例如可藉由以下方法適宜地製造。 首先，將上述（甲基）丙烯酸烷基酯共聚物溶液與多官能 性環氧化合物溶液加以混合，獲得黏著劑前驅物組合物。 於該情形時’ & 了塗佈特^厚度、寬度之光罩黏著劑層， 進而利用溶劑將黏著劑前驅物組合物稀釋’調整溶液濃度 (黏度）。基於溶解性、蒸發速度等觀點選擇用以稀釋之溶 劑。作為溶劑之較佳具體例，可列舉：丙酮、乙酸乙酿： 甲苯，但並不限定於該等。 151745.doc 201130937 其次’將該黏著劑前驅物植a私备> ^ 初，，且口物塗佈至一端面具有光罩 護膜薄膜之光罩護膜框之另一娃； 为知面。塗佈方法並蛊特別限 定，較佳為使用分注器進行參佑 ^ 塗佈。上述黏著劑前驅物組合 物中之丙烯酸共聚物溶液（稱為含有溶劑與（甲基）丙稀酸烧 基醋共聚物之溶液）㈣度並無特職定，較佳為5〇ρ以 下，更佳為10〜40 Ρ，更佳在 文佳為20〜30 ρ左右⑺型黏度計， 25°C )。利用分注器進行涂佑主 仃土佈時，利用溶劑進行稀釋，此 時塗佈液之黏絲較少，容易詷软 谷勿兩整為穩定之寬度、厚度。 再人可藉由將所塗佈之點著劑層加熱乾燥，而除去溶 劑及/或殘留單體。進❿，若（甲基）丙稀酸院基醋共聚物所 具有之官能基與硬化材料發生加熱反應而形成交聯結構， 則光罩護膜框黏著劑組合物形成—體，而密著於光革護膜 框表面。 又考慮到溶劑及殘留單體之沸點、（甲基）丙稀酸院基醋共 聚物之分解溫度，該乾燥溫度較佳為50〜200t，較佳為 、，190 C。X ’較佳為將黏著劑於充分乾燥之狀態下用於 光罩以使黏著劑中所含溶劑於下述逸氣試驗中達到 5〇 ppb以下。 亦可於乾燥、交聯後’貼附用以保護黏著面之脫模片。 脫模？通常使用聚酿等之厚度為3〇〜2〇〇 -左右之膜。 又二若自黏著_下脫模片時之剝離力較大，則有剝下時 著劑發i變形之虞’因此可於與黏著劑接觸之膜表面進 行聚矽氧或氟等之脫模處理而形成適當之剝離力。 可於貼附用以保護黏著面之脫模片後，施加負重，將黏 151745.doc •22· 201130937 著劑表面成型為大致平坦之表面。 [實施例] 以下，藉由實施例及比較例進而具體說明本發明，佴本 發明並不受該等之任何限定。 <實施例1> (黏著劑前驅物組合物之製備） (甲基）丙烯酸烷基酯共聚物1係藉由眾所周知之方法製 備。具體而言’於具備攪拌機、溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙酯（30重量 份），以30/66/1.5/2.5/1.0之重量比加入丙烯酸異丁酯/兩烯 酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2，-偶氮雙異丁腈之混 合物（32重量份），於氮氣環境下，使該反應溶液於6(TC下 反應8小時。反應結束後’添加甲苯（38重量份），獲得不揮 發成分濃度為32重量％之丙烯酸共聚物溶液（重量平均分子 量130萬）。於所獲得之丙烯酸共聚物溶液1〇〇重量份中添 加0.3重量份多官能性環氧化合物（1，3_雙（队小二縮水甘油 基胺基甲基）環己烷，不揮發成分濃度為5%，甲苯溶液）， 並進行攪拌混合，獲得黏著劑前驅物組合物。 (附帶黏著劑之光罩護膜之製作） 其後， 塗佈至一 (外徑11 3 利用分注器將所調配之上述黏著劑前驅物組合物 端面接著有光罩護膜薄膜之鋁合金製光罩護祺框 mm)之另-端面上。以2個階段對其進行加熱乾燥、 (第1階段.100。。，8分鐘；第2階段：18(Γ(：，8分鐘) 固化151745.doc 201130937 (meth) acrylate, carboxyl group-containing monomer such as (meth)acrylic acid. In particular, in terms of residual glue, it is preferably (mercapto)acrylic acid, and the content of (mercapto)acrylic acid is 〇1 to 5 wt% with respect to all monomers constituting the (meth)acrylic acid-based vinegar copolymer. More preferably 0.5 to 4 weight ❶ /. More preferably 〇 8~3 weight 0/〇. In the above (meth)acrylic acid alkyl ester copolymer, the amount of the above-mentioned A1 component acrylate monomer is 4 Torr to 9 9% by weight, preferably 45 to 80% by weight, based on the monomer mixture. Further, the component A2 is preferably 9 to 59% by weight, preferably 15 to 50% by weight, and the component B is preferably 20% by weight, preferably 2 to 1% by weight. When the weight average molecular weight of the (meth)acrylic acid alkyl ester copolymer is 700,000 or more and 2.5 million or less, the cohesive force and the adhesion force of the adhesive layer are appropriately increased, and it is difficult to leave residual glue and have sufficient adhesion. A load-resistant adhesive is preferred. The weight average molecular weight is preferably 190,000 or more and more than 10,000 and 2,000 or less. The control method for the weight average molecular weight can be controlled by a well-known method. Specifically, there is usually a tendency that the higher the monomer concentration at the time of polymerization, the larger the weight average molecular weight, the smaller the amount of the polymerization starting dose, and the lower the polymerization temperature, the larger the weight average molecular weight. As the production of the above (mercapto)acrylic acid alkyl ester copolymer, a known production method such as solution polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization can be suitably employed. Further, the obtained alkyl (meth)acrylate copolymer may be any of a random copolymer, a block copolymer, a graft copolymer and the like. Further, in the solution polymerization, for example, ethyl acetate, terpene or the like can be used as the polymerization solvent. 151745.doc 201130937 As a specific solution polymerization example, under an inert gas flow such as nitrogen, for example, adding azobisisobutyronitrile 〇〇U 0 parts by weight as a polymerization initiator relative to 1 part by weight of the total amount of monomers, Usually 50~70. (The reaction is carried out for about 8 to 30 hours in the left and right. The polymerization initiator, the chain transfer agent, the emulsifier, and the like used in the radical polymerization are not particularly limited, and can be appropriately selected and used. As a preferred polymerization initiator, for example, Listed: azo system 2,2,_azobisisobutyronitrile, 2,2'-azobis-2-mercaptobutyronitrile, 2,2,-azobis(2-mercaptopropionate A Ester), 4,4, azobis-4-cyanophthalic acid, etc., or peroxide-based benzamidine peroxide, etc. The adhesive used for the photomask film of the present invention is particularly preferably contained. An adhesive containing a composition obtained by reacting a (mercapto)acrylic alkyl vinegar copolymer with a hardening material. Examples of the hardening material include a metal salt, a metal alkoxide, an aldehyde compound, and a non-amino group. A hardening material used for a general adhesive such as a resin-based amine compound, a urea-based compound, an isocyanate-based compound, a metal chelate-based compound, a melamine-based compound, or an amide-based compound, and (meth) propyl The reactivity of the functional group component of the dilute acid base copolymer is preferably [selected from The at least one type of hardening material in the group consisting of the isocyanate type compound and the polyfunctional epoxy compound is more preferably a polyfunctional epoxy compound. Specifically, 'as an isocyanic acid-based compound, toluene is exemplified Diisocyanate, as a polyfunctional epoxy compound, may be exemplified by neopentyl glycol diglycidyl "ethylene glycol diglycidyl _, double alicyclic diglycidyl hydrazine, double fused diglycidyl glycerin, Diglycidyl terephthalate brewing, two 151745.doc 201130937 polyglycidyl polyacrylate, triglycidyl isocyanurate, diglyceryl triglycidyl sulphate, sorbitol tetraglycidyl ether, n, n, n ',n'-tetraglycidyl-m-xylenediamine, ^-bis(N,N-diglycidylaminomethyl)cyclohexene, N,N,N,,N,-tetraglycidyl Diaminodiphenylmethane, etc. These are preferably nitrogen-containing epoxy compounds having 2 to 4 epoxy groups, and in terms of reactivity, it is preferred to use a nitrogen-containing ring having 4 epoxy groups. Oxygen compound. If the reactivity is good, the crosslinking reaction will end quickly after the application of the adhesive. This property is stable in a short period of time. It is excellent in productivity. It also controls the weight swelling degree by adjusting the content of the hardened material. The so-called swelling refers to the interaction of solvent molecules into the polymer molecules, so that the force of the molecular spacing is increased. The elasticity of the networked structure is balanced. The influence of the size of the swelling on the affinity of the polymer and the polymer and the degree of crosslinking of the polymer can be controlled by controlling the weight of the toluene. Solvent and polymerization The higher the affinity of the substance, the higher the degree of swelling of the weight is. As a standard of affinity, the SP value (solubility parameter) is usually used, and the "p〇lymerhandb" with higher affinity for the sp value is proposed. There are various SP values in k (4th edition) WILEY-INTER SCIENCE P689-711, the toluene is 18 2 (Mpaw2), and the acetic acid is drunk is 18 6 (MPa)/2, which is approximately the same value. Therefore, the SP value of the monomer component constituting the polymer is close to that of toluene or ethyl acetate to increase the weight swelling degree. For example, as a monomer component of an acrylic adhesive, butyl acrylate (MPa1"), isobutyl acrylate is 17 4 (Mpa]/2), and the monomer component of the agent is 14 5 (MPaw2). 1/2λ tf Domino - ~ * As a rubber-based adhesive 'isobutylene is 15.0 151745.doc 201130937 (Mh), B-woman is 15.76 (ΜΡ,), Ding is i3 7 (Mpa, as a poly-oxygen adhesive The dimethyl sulphur oxide of the monomer component of the agent is ~(1) bis.... In terms of the affinity of the polymer to the solvent, an acrylic adhesive is preferred. The 'weight swelling degree also depends on If the cross-linking degree is too low, the refrigerant molecules will not infiltrate into the polymer network, and the weight swelling degree will decrease. If the cross-linking degree is too high, it will not enter the polymerization. The physical cross-linking (four) structure 'the amount of swelling is reduced. Therefore, the degree of cross-linking can be controlled by appropriately controlling the degree of cross-linking of the polymer. If the content of the hardened material is relative to the above (meth) acrylic acid-based vinegar 100 parts by weight of the copolymer is 0. 05 to 3 parts by weight, and the weight of the benzene or ethyl acetate is 5 times or more. A preferred adhesive for a photomask film, wherein if the content of the hardening material is 重量5 parts by weight to 2 parts by weight, the degree of swelling of toluene or ethyl acetate is further increased to become a more reticle. The adhesive for the film prevents the generation of the atomization, and it is difficult to leave the residual glue. Further, since the crosslink density is moderately formed, it is difficult to particularly affect the flatness of the mask (especially, the deformation of the mask can be suppressed). The mask adhesive is considered to be because if the content of the hardened material is less than 2 parts by weight, the crosslinking density does not become too large, so the adhesive absorbs the stress applied to the mask, and the flatness of the mask is alleviated. On the other hand, it is considered that if it is 0.05 parts by weight or more, the crosslinking density does not become too small, so that the operability in the manufacturing step is maintained, and no residual glue remains when the mask is peeled off from the mask. In the case of a composition containing the above (meth)acrylic acid alkyl ester copolymer and the polyfunctional epoxy 151745.doc 201130937 compound, the degree of crosslinking of the polymer can be controlled to Degree, and the weight swelling degree is adjusted to a maximum of about 15 times. Especially if the weight swelling degree of toluene is about 8 times to 14 times, the effect of the adsorbed organic gas such as toluene or ethyl acetate remaining in the adhesive is better. It is preferred, and is considered to be because if the weight of the toluene is from about 8 times to about M times, the inter-polymer structure spacing between the polymers is suitable for capturing the size of benzene and ethyl acetate. The reaction of the reaction product of the (alkyl)acrylic acid alkyl ester copolymer with the polyfunctional epoxy compound is carried out by weighing a (meth)acrylic acid alkyl vinegar copolymer solution and a polyfunctional epoxy compound. The solution is mixed, (4) to achieve uniform mixing, and the solvent is heated and dried to remove, and then heated. If the average molecular weight of the (meth)acrylic acid alkyl ester copolymer and the content of the hardening material are adjusted, the 300% modulus value at 23t obtained by the tensile test of the adhesive by a tensile test speed of 3 达到 is 5〇. When it is ~35 〇mN/mm2, the adhesive is excellent in load-bearing property, and it is preferable because it is an adhesive which does not easily retain residual glue. Here, the 3 〇〇% modulus value means that the thickness of the adhesive layer is 0.2 mm and the width is 23 ° C in a 65% RH gas atmosphere using an autostereograph. The adhesive sample of mm was subjected to tensile stress per unit sectional area of 300% strain at a stretching distance of 10 mm and a tensile speed of 3 mm mm/min. The 3〇〇% modulus value is mainly controlled by the weight average molecular weight of the (meth)acrylic acid alkyl ester copolymer and the content of the hardening material. The larger the weight average molecular weight of the (meth)acrylic acid alkyl ester copolymer, the larger the 300% modulus value, and the more the polyfunctional epoxy compound contains 151745.doc 201130937, the larger the 300% modulus value. The weight average molecular weight of the (meth)acrylic acid alkyl ester copolymer can be in the range of 300% modulus value of 50 to 350 mN/mm2, especially when the weight average molecular weight is 700,000 or more and 2.5 million or less. It is preferable that the cohesive force and the adhesion force of the agent layer are appropriately large, and it is an adhesive which does not easily retain residual glue and has sufficient adhesion and load resistance. The weight average molecular weight is preferably 900,000 or more and 2.3 million or less, more preferably 10,000 million or more and 2,000,000 or less. The method of controlling the weight average molecular weight ' can be controlled by a well-known method. Specifically, 'there is usually a tendency that the higher the monomer concentration in the polymerization reaction, the larger the weight average molecular weight and the smaller the amount of the polymerization starting dose. The lower the polymerization temperature, the larger the weight average molecular weight. The content of the hardening material may be in the range of 300% modulus to 5 〇 35 〇 mN/mm 2 , especially 100 parts by weight of the above alkyl (meth) acrylate copolymer, preferably 〇. 〇 5 to 3 parts by weight, more preferably 〇 1 to 2 5 parts by weight. More preferably, it is 0.1 5 to 2.0 parts by weight. When the content of the hardened material is within the above range, the crosslink density reaches a moderate density, and the adhesive is less likely to remain in the residual rubber and has sufficient adhesion and load resistance. In the range of the weight average molecular weight of the above (fluorenyl) methacrylate copolymer and the content of the hardened material, it is particularly preferable that the adhesive is obtained by a tensile test at a tensile speed of 3 mm / min. (The lower 300% modulus value is in the range of 5 〇 to 350 mN/mm 2 , more preferably 8 〇 to 3 〇〇 mN/mm 2 , more preferably 100 to 280 mN/mm 2 . If 300% modulus is 5〇~35〇mN/mm2, it has sufficient adhesion and load-bearing property, and the residual glue at the time of peeling is also reduced by 151,745.doc 201130937, so it is preferable. Regarding the polymerization initiator remaining in the adhesive, Preferably, the weight of the adhesive is 8 ppm or less with respect to the weight of the adhesive. If the total amount of the polymerization initiator remaining in the adhesive is 8 ppm or less with respect to the total weight of the adhesive, the generation of atomization can be greatly suppressed. The reason why the amount of the polymerization initiator remaining in the film improves the atomization of the mask is not clear, and there are various reasons for the atomization as follows. It is considered that the main reason is that the organic gas component existing in the exposed gas environment is borrowed. A chemical reaction is caused by the exposure light m, and the reaction product adheres to the photomask to cause fogging. It is presumed that if a certain amount of the polymerization initiator is present in the adhesive layer, the polymerization initiator will be exposed by exposure. Cracking of the energy of light, triggering the chemical reaction of organic gases As a result, the amount of formation of the atomized reaction product is greatly increased. For the above reasons, the polymerization initiator is preferably used in an amount of 7 ppm or less, and the amount of the adhesive used in the mask film is relative to the binder. The weight is preferably 8 ppm or less, and more preferably 6 ppm or less. The method for lowering and controlling the polymerization initiator remaining in the adhesive layer is as follows: · Reduction of polymerization initiation in polymerization of the adhesive polymer Dosage, or use a polymerization initiator which is easy to thermally decompose; in addition, by the (4) 'dry no step' & time application of high temperature by the adhesive, the polymerization initiator is decomposed by a drying step. σ represents a polymerization initiator The so-called half-life, the time, the index of the thermal decomposition rate of 10 hours and a half is 1 〇 hour half-life temperature refers to the decomposition of the polymerization initiator until one half of the original amount represents a half-life of 10 hours. 151745.doc •19 · 201130937 The polymerization initiator with a low 10-hour half-life temperature is easily decomposed and therefore does not easily remain on the adhesive layer. It is especially preferred to use a 10-hour half-life temperature of 8 generations or less. Preferably, it is 75. (The following polymerization initiator. If the polymerization initiator is an azo polymerization initiator, 2,2'-azobis(4-decyloxy-2, 4-dimethylvaleronitrile) (1 〇 hour half-life temperature 30 ° C), 2,2'-azobisisobutyronitrile (10 hour half-life temperature 6 〇. 〇, 2, 2, _ azo double (2 , 4-dimercapto valeronitrile) (1 〇 half-life temperature 51. 匚), 2 〗, - azobis(2-methylpropionate) (i 〇 hour half-life temperature 66 it), 2, wide Azobis(2-methylbutyl) (1 hr half-life temperature 67). 〇, in the case of a peroxide-based polymerization initiator, there may be mentioned, but not limited to, diphenylguanidine peroxide (1 〇 half-life temperature 74 C), dilaurin peroxide (10-hour half-life temperature 6 yc), and the like. this. Also, the photopolymerization initiator also causes fogging. As a method for lowering and controlling the photopolymerization initiator remaining in the adhesive layer, a method of decomposing the photopolymerization initiator by thermal decomposition or drying, evaporation, or irradiation with ultraviolet rays may be considered. A photopolymerization initiator which is easily decomposed by the above method, etc., as a photopolymerization initiator which is easily decomposed by the above method, may be exemplified by a phenyl fluorene homopolymerization initiator or a oxidized base. A scaly polymerization initiator or the like. Specific examples of the alkyl ketone-based polymerization initiator include 2,2-dimethoxy-anthracene, 2-diphenylethene, 1-cyclohexyl-phenyl-, 2-perylene-based 2_methyl_丨_styl propane ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropane 丨-ketone, 2-hydroxy-1_{4- [4-(2-Hydroxy-2-indolyl-propenyl)-benzyl]phenyl}·2-methylpropanone-oxime, 2-methyl-indole 4-methylthiophenyl)·2 · morpholinylpropanone Xiaotong, 151745.doc •20· 201130937 2-pyryl-2-diamine-helium 'morpholinylphenyl)·butanone, 2_(diguanylamino)- 2-[(4-Mercaptophenyl)indenyl]morpholinyl)phenylbutene_ and the like. Examples of the thiol phosphine oxide-based polymerization initiator include 2,4,6-trimethylphenylnonyl-diphenyl-phosphine oxide and bis(2,4,6-trimethyl benzhydryl group). ) Stupid phosphine oxide and the like. In order to make the total weight of the polymerization initiator remaining in the adhesive 8 ppm or less based on the total weight of the adhesive, it is preferred to use a reaction product containing a (meth)acrylic alkyl ester copolymer and a hardening material. The adhesive of the composition of the alkyl (meth) acrylate copolymer is obtained by reacting an alkyl (meth) acrylate having an alkyl group having 4 to 14 carbon atoms with a hardening material. A copolymer obtained by copolymerizing at least two monomer components of a functional group monomer. Further, the adhesive composition may contain, in addition to the above reaction product, a filler, a pigment, a diluent, an anti-aging agent, a UV stabilizer, and the like as well as known additives. These additives may be used alone or in combination of two or more. However, it is preferred to set the addition amount at a proper time to obtain desired physical properties. The photomask film of the present invention can be suitably produced, for example, by the following method. First, the above (meth)acrylic acid alkyl ester copolymer solution and a polyfunctional epoxy compound solution are mixed to obtain an adhesive precursor composition. In this case, the mask adhesive layer having a thickness and a width is applied, and the adhesive precursor composition is diluted with a solvent to adjust the solution concentration (viscosity). The solvent to be diluted is selected from the viewpoints of solubility, evaporation rate, and the like. Preferable specific examples of the solvent include acetone and acetic acid: toluene, but are not limited thereto. 151745.doc 201130937 Next, 'the adhesive precursor is planted in a private preparation> ^ Initially, and the mouth is coated to another end of the reticle film frame with a reticle film; . The coating method is particularly limited, and it is preferred to use a dispenser for coating. The acrylic copolymer solution (referred to as a solution containing a solvent and a (meth)acrylic acid-based vinegar copolymer) in the above adhesive precursor composition has no special duty, preferably 5 〇ρ or less. More preferably 10 to 40 Ρ, more preferably in Wenjia 20~30 ρ (7) type viscometer, 25 ° C). When using the dispenser to apply the main clay cloth, it is diluted with a solvent. At this time, the coating liquid has less adhesive filaments, and it is easy to soften the valley to a stable width and thickness. Further, the solvent and/or residual monomers can be removed by heating and drying the applied dot layer. In the case where the functional group of the (meth)acrylic acid-based vinegar copolymer is heated and reacted with the hardening material to form a crosslinked structure, the photomask cover adhesive composition is formed into a body, and is adhered to On the surface of the light-protecting film frame. Further, considering the boiling point of the solvent and the residual monomer and the decomposition temperature of the (meth)acrylic acid-based vinegar copolymer, the drying temperature is preferably 50 to 200 t, preferably 190 C. X ' is preferably used for the photomask in a state where the adhesive is sufficiently dried so that the solvent contained in the adhesive reaches 5 ppb or less in the following outgassing test. It is also possible to attach a release sheet for protecting the adhesive surface after drying and crosslinking. Demoulding? Usually, a film having a thickness of about 3 〇 2 〇〇 - is used. On the other hand, if the peeling force is large when the self-adhesive_lower release sheet is used, the agent may be deformed when it is peeled off. Therefore, the surface of the film which is in contact with the adhesive may be demolded by polyoxygen or fluorine. Treatment to form a suitable peel force. After attaching the release sheet for protecting the adhesive surface, a load is applied to form the surface of the adhesive 151745.doc •22· 201130937 into a substantially flat surface. [Examples] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, and the present invention is not limited thereto. <Example 1> (Preparation of Adhesive Precursor Composition) The (meth)acrylic acid alkyl ester copolymer 1 was prepared by a well-known method. Specifically, 'in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube, ethyl acetate (30 parts by weight) was added, and the weight ratio was 30/66/1.5/2.5/1.0. a mixture of isobutyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2,-azobisisobutyronitrile (32 parts by weight), the reaction solution was allowed to react under nitrogen atmosphere (Reaction at TC for 8 hours. After completion of the reaction, 'toluene (38 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 1.3 million) having a nonvolatile content of 32% by weight. The obtained acrylic copolymer solution 1 was obtained. 0.3 parts by weight of a polyfunctional epoxy compound (1,3_bis(team small diglycidylaminomethyl)cyclohexane, a nonvolatile content of 5%, a toluene solution) is added to the 〇〇 part by weight, and The mixture is stirred and mixed to obtain an adhesive precursor composition. (Preparation of a mask film with an adhesive) Thereafter, it is applied to an outer diameter of 11 3 using a dispenser to combine the above-mentioned adhesive precursors. The end face of the object is followed by a mask film Aluminum alloy reticle guard frame mm) on the other end face. It is heated and dried in two stages (first stage. 100., 8 minutes; second stage: 18 (Γ (:, 8 minutes) Curing

151745.doc -23- 201130937 得形成有3有上述黏著劑前驅物組合物之黏著劑層（厚度 〇·2 nun)的實施例丨之光罩護膜。繼而，貼附經聚矽氧脫^ 處理之厚度為100 4„!之聚酯製保護膜，於室溫（2〇±3<t)下 熟化3天，使黏著力穩定化，製作附帶黏著劑之光罩護 膜。藉由以下方法對所獲得之附帶黏著劑之光罩護膜進行 評價。 (逸氣試驗） 自光罩護膜產生之逸氣可利用吸附材料進行捕獲而進行 分析。於50 mL/min之氦氣流下，將實施例中獲得之光罩 濩膜於5 0 C下加熱處理3 0分鐘，並利用吸附劑進行捕獲。 及附劑係使用TENAX TA(GL Science製造）》樣品對GC裝 置之導入係使用頂空進樣器，使吸附管於25〇。〇下處理1 〇 刀4里，並進行熱脫附’藉由GC/MS(gas chromatography/mass spectroscope ’氣相層析/質譜儀）對所產生之逸氣進行分 析。GC/MS分析條件如下。 GC裝置：Agilent Technologies 7890A GC System 管柱：Agilent Technologies 19091J-413 HP-5(30 mx〇.320 mmx〇.25 μιη) 温度條件：30°C 〜280°C(10°C/min) MS裝置·· je〇L Jms-QIOOOGC K9 離子化：70 eV 掃摇範圍：m/z=l〇〜500 曱笨之定量係用根據絕對校準曲線求出之重量除以1片 光罩護獏之重量而算出，並按照以下基準進行評價。 15l745.doc • 24- 201130937 1 0 ppb以下…◎ 5 0 ppb以下…Ο 5 1 ppb以上…x (霧化測試） 將實施例中所獲得之附帶黏著劑之光罩護膜剝下保護 膜，利用簡易型貼合機（mounter)，於負重（30 Kgf，60秒） 下將其貼附至6025石英空白基材上，獲得貼附有光罩護膜 之基材。 以 0.7 mJ/cm2/pulse、頻率 250 Hz，且以 8 小時、5000 J/cm2之照射量對所獲得之基材照射ArF準分子雷射。對照 射後之基材及光罩護膜，目測有無產生霧化，按照以下基 準進行評價。 0…基材及光罩護膜未產生霧化 x··.基材及光罩護膜產生霧化 (剝離性評價）151745.doc -23-201130937 A photomask film of an embodiment having an adhesive layer (thickness 〇·2 nun) having the above adhesive precursor composition was formed. Then, a polyester protective film having a thickness of 100 4 „!, which was treated by polyfluorene deoxidation, was attached and aged at room temperature (2 〇 ± 3 < t) for 3 days to stabilize the adhesion and make adhesive adhesion. The reticle film of the agent is evaluated by the following method. (The gas escaping test) The outgas generated from the reticle film can be captured by the absorbing material for analysis. The reticle film obtained in the example was heat-treated at 50 C for 30 minutes under a helium flow of 50 mL/min, and was captured by an adsorbent. The attached agent was TENAX TA (manufactured by GL Science). The introduction of the sample to the GC device uses a headspace sampler to make the adsorption tube at 25 Torr. The underarm is treated with 1 boring tool 4 and thermally desorbed by GC/MS (gas chromatography/mass spectroscope) The resulting outgases were analyzed by phase chromatography/mass spectrometer. The GC/MS analysis conditions were as follows: GC unit: Agilent Technologies 7890A GC System Column: Agilent Technologies 19091J-413 HP-5 (30 mx〇.320 mmx〇 .25 μιη) Temperature conditions: 30 ° C ~ 280 ° C (10 ° C / min) MS device · je〇L Jms-QIOOOGC K9 Ionization: 70 eV sweep range: m/z=l〇~500 The basis weight is calculated by dividing the weight calculated from the absolute calibration curve by the weight of one mask protector. And evaluated according to the following criteria. 15l745.doc • 24- 201130937 1 0 ppb or less... ◎ 5 0 ppb or less...Ο 5 1 ppb or more...x (atomization test) The light with the adhesive obtained in the examples The protective film was peeled off from the cover film, and attached to a 6025 quartz blank substrate under a load (30 Kgf, 60 seconds) using a simple type of mounter to obtain a base to which the mask film was attached. The obtained substrate was irradiated with an ArF excimer laser at an irradiation dose of 0.7 mJ/cm 2 /pulse at a frequency of 250 Hz and an exposure of 8 hours and 5000 J/cm 2 to the substrate and the mask film after the irradiation. The presence or absence of atomization was visually observed and evaluated according to the following criteria: 0: The substrate and the mask film were not atomized. x. The substrate and the mask film were atomized (evaluation evaluation)

狀恐，牧脒以下基準進行評價。 ◎ ··殘膠面積為整體貼附面積 之〇〜50/〇 15I745.doc •25· 201130937 〇.殘膠面積為整體貼附面積之6〜2〇% X .殘膠面積為整體貼附面積之21〜 (耐負重試驗） 將實施例中所獲得之附帶黏著劑之光罩護膜剝下保護 膜，利用簡易型貼合機，於負重（3〇 Kgf，6〇咖）下將其貼 附至6025石英空白基材及6〇25附帶鉻之空白基材上，獲得 貼附有光罩護膜之基材。於貼附有光罩護膜之基材上設置 1 Kg之重物，並於室溫下放置。按照以下基準對光罩護膜 自基材剝離為止之時間進行評價。 ◎:經過3天亦無氣道 〇·經過1天後光罩護膜自基材脫落 x :經過3小時後光罩護膜自基材脫落 (分子量測定） 將黏著劑試料真空乾燥，除去溶劑。於試料中添加溶離 液，調整為1.0 mg/rnL。利用0.5微米過濾器進行過濾，將 滤液作為GPC試料。GPC之測定條件如下。Terrorism, the pastoral evaluation of the following criteria. ◎ ·· The area of the residual glue is the total attached area~50/〇15I745.doc •25· 201130937 〇. The area of the residual glue is 6~2〇% of the total attached area. X. The area of the residual glue is the overall attached area. 21~ (load-bearing test) The protective film of the mask film with the adhesive obtained in the examples was peeled off, and the film was attached under a load (3〇Kgf, 6〇) using a simple type bonding machine. Attached to the 6025 quartz blank substrate and 6〇25 blank substrate with chrome, the substrate with the reticle film attached is obtained. A 1 Kg weight was placed on the substrate to which the reticle film was attached, and placed at room temperature. The time until the mask film was peeled off from the substrate was evaluated according to the following criteria. ◎: No airway after 3 days 〇· After 1 day, the mask film was peeled off from the substrate. x: After 3 hours, the mask film was peeled off from the substrate (molecular weight measurement) The adhesive sample was vacuum dried to remove the solvent. The solution was added to the sample and adjusted to 1.0 mg/rnL. Filtration was carried out using a 0.5 μm filter, and the filtrate was used as a GPC sample. The measurement conditions of GPC are as follows.

GPC 資料處理：Tosoh GPC-8020 裝置：Tosoh HLC-8220GPCGPC Data Processing: Tosoh GPC-8020 Device: Tosoh HLC-8220GPC

管柱：TSKgel SuperHZN-M(4.6 mmI.D.xl5 根 + TSKgel SuperHZ2000(4.6 mmI.D.xl5 ⑽口根 烘箱·· 40°C 溶離液：0.35 mL/min CHC13 試料量：50 μ1(1.0 mg/mL)Column: TSKgel SuperHZN-M (4.6 mmI.D.xl5 + TSKgel SuperHZ2000 (4.6 mmI.D.xl5 (10) Bottom oven · 40 °C Solubility: 0.35 mL/min CHC13 Sample volume: 50 μl (1.0 mg /mL)

檢測器：RI 151745.doc -26- 201130937 校準曲線：聚苯乙烯 (利用甲苯或乙酸乙酯之膨潤度測定） 利用到刀自實施例中所獲得之黏著劑層刮取約ι〇〇 mg(重里A)之黏著劑，包在由尼龍網（網眼2〇〇 p⑷中，於 ^&gt;°c之條件下於甲苯溶液或乙酸乙醋溶液中浸潰1周。其 後自/合液取出包裹體，測定剛自溶液中取出後之黏著劑 未溶解部分的重量（重量B )。此時將以B/A算出之值作為 甲苯或乙酸乙酯之重量膨潤度。 〈實施例2&gt; 除了將多官能性環氧化合物（1，3_雙（N，N_二縮水甘油基 胺基甲基）環己烷，不揮發成分濃度為5%，曱苯溶液）變成 〇 · 2重1伤以外，藉由與實施例丨相同之方法製作光罩護膜 樣品，並進行評價。 &lt;實施例3&gt; (曱基）丙婦酸烧基酯共聚物2係藉由眾所周知之方法製 備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙酯（3〇重量 份）’以98/2/1之重量比加入丙烯酸丁酯/丙烯酸/2,2,·偶氮 雙異丁腈之混合物（32重量份）’於氮氣環境下，使該反應 溶液於60 C下反應8小時。反應結束後，添加甲苯（3 8重量 份）’獲得不揮發成分濃度為32重量％之丙烯酸共聚物溶液 (重量平均分子量170萬）。於所獲得之丙烯酸共聚物溶液 100重量份中添加0 _2重量份多官能性環氧化合物（丨，3 _雙 (N，N-二縮水甘油基胺基曱基）環己烷，不揮發成分濃度為 I51745.doc •27· 201130937 5%’甲笨溶液），並進行攪拌混合，獲得黏著劑前驅物組 合物。其後藉由與實施Μ !相同之方式製作&amp;罩護膜樣 品，並進行評價。 &lt;實施例4&gt; 除了將多官能性環氧化合物（1,3_雙（N，N_二縮水甘油基 胺基甲基)環己烷變成曱苯二異氰酸酯之三羥甲基丙烷加 成物0.45份以外，藉由與實施例1相同之方法製作光罩護 膜樣品，並進行評價。 &lt;實施例5&gt; (甲基）丙烯酸烷基酯共聚物3係藉由眾所周知之方法製 備。具體而言，於具備授掉機、溫度計、回流冷卻器、滴 加裝置 '氮氣導入管之反應容器中放入乙酸乙醋⑼重量 Μ以98/2/1之重量比加入丙烯酸丁酷/丙稀酸偶氮 =猜。之混合物(32重量份)，於氣氣環境下，使該反應 65C下反應8小時。反應結束後，添加甲苯（18重量 ㈣成分濃度為32重量％之丙稀酸共聚物溶液 重:份:二子:=)。於所獲得之丙婦酸共聚物溶液10。 1水甘=官能性環氧化合物(1，3，N，N-二=基胺基甲基)環己院，不揮發成分濃度為⑽， 甲本冷液），並進行攪拌混合，獲得㈣料 人 物。其後藉由與實施例丨相同方 、，且σ 並進行評價。 ^之方式製作光罩護膜樣品， &lt;實施例6&gt; 除了將多官能性環氧化合物（1，3•雙（Ν算二縮水甘油基 15J745.doc •28· 201130937 胺基甲基）環己烷’不揮發成分濃度為5%，甲苯溶液）變成 2.0份以外，藉由與實施例1相同之方法製作光罩護膜樣 品，並進行評價 &lt;實施例7&gt; (曱基）丙烯酸烷基酯共聚物4係藉由眾所周知之方法製 備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙酯（5〇重量 份）’以30/66/1.5/2.5/1.0之重量比加入丙稀酸異丁酿/丙稀 酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2·-偶氮雙異丁腈之混 合物（50重量份），於氮氣環境下，使該反應溶液於55〇c下 反應8小時。反應結束後，添加曱苯（20重量份），獲得丙稀 酸共聚物溶液（重量平均分子量為280萬）。於所獲得之丙稀 酸共聚物溶液1 〇 〇重量份中添加〇 · 3重量份多官能性環氧化 合物（1，3-雙（N，N-二縮水甘油基胺基甲基）環己烷，不揮發 成分濃度為5 °/〇 ’甲苯溶液），並進行擾拌混合，獲得黏著 劑前驅物組合物。 &lt;比較例1 &gt; 除了將多官能性環氧化合物（1,3-雙（N，N-二縮水甘油基 胺基甲基）環己烷變成〇〇2份以外，藉由與實施例1相同之 方法製作光罩護膜，並進行評價。 &lt;比較例2&gt; 相對於聚矽氧黏著劑（Dowcorning(股）製造，SD4580(商 品名）不揮發成分濃度為40%，曱苯/二曱苯溶液）丨00重量 伤添加〇.9重量份硬化劑（Dowcorning(股）製造’ SRX212)， 151745.doc -29- 201130937 獲得黏著劑前驅物 式製作先罩護膜樣 &lt;比較例3&gt; 乡且合物°其後藉由與實施例1相同之方 品，並進行評價。 將苯乙稀-乙稀/ 丁稀_苯乙稀之橡膠系熱炼黏著劑塗佈於 女而面接著有光罩護膜薄膜之鋁合金製的光罩護膜框（外 控 113 mmxl49 mm，内徑 1〇9 mm，高度4.8 mm) 之另一端面。其後藉由與實施例1相同之方式製作光罩護 膜樣品，並進行評價 151745.doc 30- 201130937 職 Μ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎Detector: RI 151745.doc -26- 201130937 Calibration curve: Polystyrene (determined by the degree of swelling of toluene or ethyl acetate) Using an adhesive layer obtained from the knives in the examples, scraping about 1 〇〇 mg (heavy The adhesive of A) is encapsulated in a nylon mesh (mesh 2〇〇p(4), under the condition of ^&gt;°c, in a toluene solution or an ethyl acetate solution for 1 week. Thereafter, it is taken out from the liquid/liquid mixture. The inclusions were measured for the weight (weight B) of the undissolved portion of the adhesive immediately after removal from the solution. At this time, the value calculated by B/A was used as the weight swelling degree of toluene or ethyl acetate. <Example 2> The polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, non-volatile content of 5%, benzene solution) becomes 〇·2 weight 1 injury A sample of the photomask film was prepared and evaluated in the same manner as in Example &. <Example 3> (Mercapto) propylene glycolate copolymer 2 was prepared by a known method. In terms of a mixer, a thermometer, a reflux cooler, a dropping device, and a nitrogen gas introduction Ethyl acetate (3 parts by weight) was placed in the reaction vessel. A mixture of butyl acrylate/acrylic acid/2,2,-azobisisobutyronitrile was added in a weight ratio of 98/2/1 (32 parts by weight). 'The reaction solution was allowed to react at 60 C for 8 hours under a nitrogen atmosphere. After the completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic copolymer solution having a nonvolatile content of 32% by weight (weight average molecular weight 170). Adding 0 _2 parts by weight of a polyfunctional epoxy compound (丨, 3 bis(N,N-diglycidylamino) fluorene) to 100 parts by weight of the obtained acrylic copolymer solution, The concentration of the non-volatile component was I51745.doc •27·201130937 5% 'A solution of stupid solution), and the mixture was stirred and mixed to obtain an adhesive precursor composition. Thereafter, a film was prepared in the same manner as in the implementation of the film. The sample was evaluated and evaluated. <Example 4> In addition to the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane was changed to indole diisocyanate In addition to 0.45 parts of hydroxymethylpropane adduct, by the same as Example 1 The reticle film sample was produced and evaluated. <Example 5> The (meth)acrylic acid alkyl ester copolymer 3 was prepared by a known method. Specifically, it was provided with a transfer machine, a thermometer, and the like. In the reaction vessel of the reflux cooler and the dropping device 'nitrogen inlet tube, the weight of acetic acid (9) is added to the reaction vessel, and the mixture of butyl acrylate/acrylic acid azo = guess is added in a weight ratio of 98/2/1 (32 weight). The reaction was allowed to react for 8 hours at 65 C in an air atmosphere. After the completion of the reaction, toluene (18 parts by weight of the component of the acrylic acid copolymer having a concentration of 32% by weight) was added: part: two: =). The obtained bupropion acid copolymer solution 10 was obtained. 1 water Gan = functional epoxy compound (1,3,N,N-di-ylaminomethyl) cyclohexanin, non-volatile content concentration (10), a cold liquid), and stirred and mixed to obtain (4) Material characters. Thereafter, it was evaluated in the same manner as in Example 且 and σ. A method of making a photomask film, &lt;Example 6&gt; except for a polyfunctional epoxy compound (1,3•bis (Ν 二 diglycidyl 15J745.doc •28·201130937 aminomethyl) ring A sample of the photomask film was prepared and evaluated in the same manner as in Example 1 except that the hexane 'nonvolatile content was 5% and the toluene solution was changed to 2.0 parts. <Example 7> (fluorenyl) acrylate The base ester copolymer 4 is prepared by a well-known method. Specifically, in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, ethyl acetate (5 parts by weight) is placed in a weight ratio of 30/66/1.5/2.5/1.0. A mixture of butyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2·-azobisisobutyronitrile (50 parts by weight) was added, and the reaction was carried out under a nitrogen atmosphere. The solution was reacted at 55 ° C for 8 hours. After completion of the reaction, toluene (20 parts by weight) was added to obtain an acrylic acid copolymer solution (weight average molecular weight: 2.8 million). Adding 〇·3 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane to 1 part by weight of the obtained acrylic acid copolymer solution The alkane, the concentration of the non-volatile component was 5 ° / 〇 'toluene solution, and was mixed by scramble to obtain an adhesive precursor composition. &lt;Comparative Example 1 &gt; Except that the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane was changed to 2 parts) The mask film was produced and evaluated in the same manner. <Comparative Example 2> The concentration of the non-volatile component of the SD4580 (trade name) was 40% with respect to the polyoxyxide adhesive (manufactured by Dow Corning Co., Ltd.). Diphenylbenzene solution) 丨00 weight injury added 9. 9 parts by weight of hardener (Dowcorning (manufactured by the company) 'SRX212), 151745.doc -29- 201130937 Obtained adhesive precursor precursor film sample &lt;Comparative Example 3&gt; The mixture was evaluated by the same method as in Example 1. The styrene-ethylene/butyl styrene-based rubber-based heat-adhesive was applied to the woman. The other end face of the reticle film frame (external control 113 mm×l49 mm, inner diameter 1〇9 mm, height 4.8 mm) of the aluminum alloy mask film is followed by the same as in the first embodiment. The method of making a mask film and evaluating it 151745.doc 30- 201130937 Μ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎

X Μ ◎ ◎ ◎ 〇 〇 ◎ Ο ◎X Μ ◎ ◎ ◎ 〇 〇 ◎ Ο ◎

XX

X 〇 〇 〇 〇 0 〇 〇X 〇 〇 〇 〇 0 〇 〇

X ◎ ◎ ◎ ◎ ◎ ◎ ◎X ◎ ◎ ◎ ◎ ◎ ◎ ◎

X &gt;Νν®&lt;0絰(0¾ 01 S1 ^§0 發峒*&gt;蚪6-寂 6 llX &gt;Νν®&lt;0绖(03⁄4 01 S1 ^§0 hair峒*&gt;蚪6-静 6 ll

II 01 01 οι S-1 _屮令 won i€on ip 摊§ 埏09 摊oa «:08(ν 摊 0&lt;Νι (φ&gt;Η*^^¥ί 骚總 2 Γ0 s i 2 2 S.0 60 嘁碱ϊί 嘁碱fi 嘁碱fi 浓忒ϊί 嗛碱fiII 01 01 οι S-1 _屮令won i€on ip § 埏09 摊 oa «:08(ν 摊0&lt;Νι (φ&gt;Η*^^¥ί 骚 total 2 Γ0 si 2 2 S.0 60嘁 base ϊί 嘁 base fi 嘁 base fi thick 忒ϊ 嗛 base fi

313X&quot;HS S(N/S· l/99/0f=v3H/vv/va/vm_ S.(N/S_ l/99/0〔=v3H/vv/vD3/vCQ-!313X&quot;HS S(N/S· l/99/0f=v3H/vv/va/vm_ S.(N/S_ l/99/0[=v3H/vv/vD3/vCQ-!

i=vv/vCQ 3「10e=v3H/vv/va/va-! i=vvi ςΓ4/ς· 1/99/0TVUJH/VV/V9/VCQ-! s.N/5 l/99/0t:=v3H/vv/vQa/vm-! soi/5 l/99/0c=VWH/vv/va/vDQ-! ssf sf 一苳銻^ s-杏錨^ £一#銻玉 溜»0硪墩^盔爱¢: V3H 键装¢: vv 溫卜盔爱叱：VH shwlc键装《 : va-!:餱坊瞀缓 151745.doc -31 - 201130937 〈實施例8&gt; (黏著劑前驅物組合物之製備） (曱基）丙晞酸烧基酯共聚物5係藉由眾所周知之方法製 備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙酯（30重量 份），以48/48/1.5/2.5/1.0之重量比加入丙烯酸異丁酯/丙稀 酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2·-偶氮雙異丁腈之混 合物（32重量份），於氮氣環境下，使該反應溶液於6〇〇c下 反應8小時。反應結束後，添加甲苯（3 8重量份），獲得不揮 發成分濃度為32重量％之丙烯酸共聚物溶液（重量平均分子 量為120萬）。於所獲得之丙烯酸共聚物溶液1 00重量份中 添加0.25重量份多官能性環氧化合物（1，3-雙（N，N-二縮水甘 油基胺基甲基）環己烷，不揮發成分濃度為5〇/〇，曱苯溶 液）’並進行攪拌混合，獲得黏著劑前驅物組合物。 (附帶黏著劑之光罩護膜之製作） 其後，利用分注器將所調配之上述黏著劑組合物塗佈至 一端面接著有光罩護膜薄膜之鋁合金製的光罩護膜框（外 徑113 mmx 149 mm，内徑1〇9 mmx 145 mm ’ 高度4.8 mm) 之另一端面。以2個階段將其加熱乾燥、固化（第丨階段： 100°C，8分鐘；第2階段：180t，8分鐘），獲得形成有含 有上述黏著劑前驅物組合物之黏著劑層（厚度〇 2 mm)的實 施例8之光罩護膜。繼而，貼附經聚矽氧脫模處理之厚度 為100 μιη之聚酯製保護膜，於室溫（2〇±3〇c)下熟化3天， 使黏著力穩定化，製作附帶黏著劑之光罩護膜。對所獲得 151745.doc -32· 201130937 之附帶黏著劑之光罩 述評價。 、仃’〔坪價，除此以外實施下 (模數測定） 使用自動立體測圖儀，將黏著層之 1.5 mm之黏著劑 厪0.2 mm、寬度 則樣以夾盤間1〇 m—抑下進行拉伸’測定此時之力/伸速度扣 用3’/。拉伸時之力除以試料之剖面 300%模數值。 字所仔值設為 〈實施例9&gt; —除了將多官能性環氧化合物(1,3_雙(__二縮水甘油基 胺基曱基）環己院’不揮發成分濃度為5%，甲苯溶液）變成 〇·15重量份以外，藉由與實施例8相同之方法製作光罩護 膜樣品’並進行評價。 &lt;實施例10&gt; 除了將多官能性環氧化合物（1，3_雙（]^小_二縮水甘油基 胺基曱基）環己烷，不揮發成分濃度為5%，曱笨溶液）變成 1 · 8重量份以外’藉由與實施例8相同之方法製作光罩護膜 樣品’並進行評價。 &lt;實施例11&gt; (曱基）丙稀酸烧基酯共聚物6係藉由眾所周知之方法製 備。具體而言’於具備攪拌機、溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙酯（30重量 份），以99/1/1.0之重量比加入丙烯酸丁酯/丙烯酸/2,2、偶 氮雙異丁腈之混合物（32重量份），於氮氣環境下，使該反 151745.doc -33· 201130937 應溶液於60°C下反應8小時。反應結束後，添加甲苯（38重 量份），獲得不揮發成分濃度為32重量％之丙烯酸共聚物溶 液（重量平均分子量為18〇萬）。於所獲得之丙烯酸共聚物溶 液100重量份中添加0.15重量份多官能性環氧化合物（1，3_ 雙（Ν，Ν-一縮水甘油基胺基曱基）環己烷，不揮發成分濃度 為5%，曱苯溶液）’並進行攪拌混合，獲得黏著劑前驅物 組合物。其後藉由與實施例8相同之方式製作光罩護膜樣 品，並進行評價。 &lt;實施例12&gt; (曱基）丙烯酸烷基酯共聚物7係藉由眾所周知之方法製 備具體而5，於具備攪拌機、溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙酯（5〇重量 份）’以99/1/1.0之重量比加入丙烯酸丁酯/丙烯酸/2,2，·偶 氮雙異丁腈之混合物（32重量份），於氮氣環境下，使該反 應溶液於65 C下反應8小時。反應結束後，添加甲苯（丨8重 量份）’獲得不揮發成分濃度為32重量％之丙烯酸共聚物溶 液（重量平均分子量為60萬）。於所獲得之丙烯酸共聚物溶 液1〇〇重量份中添加0 25重量份多官能性環氧化合物（1，3_ 雙（Ν，Ν-一縮水甘油基胺基甲基）環己烷，不揮發成分濃度 為5%，甲笨溶液），並進行攪拌混合，獲得黏著劑前驅物 組σ物。其後藉由與實施例8相同之方式製作光罩護膜樣 品’並進行評價。 &lt;比較例4&gt; 除了將多官能性環氧化合物（1，3_雙&quot;卞_二縮水甘油基 151745.doc •34· 201130937 胺基尹基）環己烧變成3.2份以外，藉由與實施制目同之方 法裏作光罩護膜樣品，並進行評價。 &lt;比較例5&gt; 除了將多官能性環氧化合物(1，3，n算二縮水甘油基 胺基甲基）環己院變成〇.〇3份以外，藉由與實施例8相同之 方法製作光罩護膜，並進行評價。 &lt;比較例6&gt; 相對於聚石夕氧黏著齊!（D〇wc〇ming(股）製造，叩4谓（商 °°名）不揮發成分濃度為40%，甲苯/二甲苯溶液）1〇〇重量 二、〇.9重畺伤硬化劑（Dowcorning(股）製造，SRX2 12)， 獲传黏著劑前驅物組合物。其後藉由與實施例8相同之方 式製作光罩護臈樣品，並進行評價。 &lt;比較例7&gt; 將苯乙烯·乙烯/丁烯_苯乙烯之橡膠系熱熔黏著劑塗佈於 端面接著有光罩護膜薄膜之鋁合金製的光罩護膜框（外 徑 113 職&quot;149 _，内徑1〇9 mmxl45 mm，高度 4_8 mm) 之另端面。其後藉由與實施例8相同之方式製作光罩護 膜樣品’並進行評價。 151745.doc -35- 201130937 【(Νί 耐負重試驗 ◎ ◎ 〇 ◎ 〇 X X X X 剝離性 ◎ ◎ 〇 ◎ 〇 ◎ X X X B 1 | m 〇 »—Η 290 140 450 00 270 220 重量平均分子量 120萬 120萬 120萬 180萬 60萬 120萬 120萬 30萬 1 硬化材料(份） 份數 ! 0.25 0.15 〇〇 0.15 0.25 CN rn -1 0.03 〇&gt; 〇 1 種類 環氧系 環氧系 環氧系 環氧系 環氧系 環氧系 環氧系 SRX212 1 主劑 組成 i-BA/BA/AA/HEA-48/48/l .5/2.5 i-BA/BA/AA/HEA=48/48/l .5/2.5 i-BA/BA/AA/HEA=48/48/l .5/2.5 BA/AA=99/1 BA/AA=99/1 i-BA/BA/AA/HEA=48/48/l .5/2.5 i-BA/BA/AA/HEA=48/48/l .5/2.5 聚矽氧系黏著材料 橡膠系黏著材料 實施例8 實施例9 實施例10 實施例11 實施例12 比較例4 比較例5 比較例6 比較例7 溫(0蝴朝-3铛装VHH 韹笈肊：W 溫h邮毽爱¢: VOQ-I:龋街瞀塄 151745.doc •36· 201130937 &lt;實施例13&gt; (黏著劑前驅物組合物之製備） (甲基）丙烯酸烷基酯共聚物8係藉由眾所周知之方法製 備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙酯（3〇重量 份）’以48/48/1.5/2.5/1.0之重量比加入丙烯酸異丁酿/兩歸 酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2，2'-偶氮雙異丁产 (ΑΙΒΝ)(1〇小時半衰期溫度60〇c)之混合物（32重量份），於 氮氣環境下，使該反應溶液於6〇°C下反應8小時。反應於 束後，添加甲苯（38重量份），獲得不揮發成分濃度為32重 量％之丙烯酸共聚物溶液（重量平均分子量為12〇萬）。於所 獲得之丙烯酸共聚物溶液100重量份中添加〇 25重量份多 官能性環氧化合物（1，3-雙（N，N_二縮水甘油基胺基甲基）環 己烧不揮發成分〉辰度為5 %，甲苯溶液），並進行攪拌、、θ 合’獲得黏著劑前驅物組合物。 (附帶黏著劑之光罩護膜之製作） 其後，利用分注器將所調配之上述黏著劑前驅物組合物 塗佈至一端面接著有光罩護膜薄膜之鋁合金製的光罩護膜 框（外徑 113 mmx149 mm，内徑 1〇9 mmxM5 _，高度u _)之另一端面。以2個階段將其加熱乾燥、固化（第^階 段：崎，8分鐘；第2階段：峨，8分鐘)，獲得形成 有：有上述光罩護膜用黏著劑前驅物組合物之黏著劑層 (厚度為G·2 _)的光罩護膜。其後，將光罩護膜於靴 下加熱處理60分鐘’調整黏著劑層中殘留之偶氮雙異 151745.doc -37- 201130937 丁腈（聚合起始劑）的量。繼而，貼附經聚矽氧脫模處理之 厚度為100 μηι之聚酯製保護膜，於室溫（2〇±3&lt;Jc)下熟化3 天，使黏著力穩定化，製作附帶黏著劑之光罩護膜。對所 獲得之附帶黏著劑之光罩護膜’進行上述評價，除此以外 實施下述評價。 (聚合起始劑之殘留量測定） 使用高效液相層析法（HPLC，high Perf0rmance liquid chromatography)對黏著劑中殘留之聚合起始劑之殘留量進 行分析。取黏著劑0·2 g置於20 mL螺旋管中，添加乙猜1〇 mL。利用浸透器，以120 r.p.m. ’於25°C下攪拌8小時，以 萃取定量成分。分析裝置、萃取條件設定如下。i=vv/vCQ 3"10e=v3H/vv/va/va-! i=vvi ςΓ4/ς· 1/99/0TVUJH/VV/V9/VCQ-! sN/5 l/99/0t:=v3H/ Vv/vQa/vm-! soi/5 l/99/0c=VWH/vv/va/vDQ-! ssf sf 一苳锑^ s-杏锚^ £一#锑玉溜»0硪墩^helter love¢ : V3H key mounting: vv Wenbo helmet love 叱: VH shwlc key loaded " : va-!: Weifang relief 151745.doc -31 - 201130937 <Example 8&gt; (Preparation of adhesive precursor composition) ( The mercaptopropionate copolymer 5 is prepared by a well-known method. Specifically, ethyl acetate is placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. (30 parts by weight), isobutyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2·-azobisisobutyl acrylate in a weight ratio of 48/48/1.5/2.5/1.0 A mixture of nitrile (32 parts by weight) was reacted under nitrogen for 8 hours at 6 ° C. After the reaction was completed, toluene (38 parts by weight) was added to obtain a nonvolatile content concentration of 32% by weight. Acrylic copolymer solution (weight average molecular weight of 1.2 million). To 100 parts by weight of the olefinic acid copolymer solution, 0.25 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) having a nonvolatile content of 5 is added. 〇/〇, 曱 溶液 solution)' and stirring and mixing to obtain an adhesive precursor composition. (Preparation of a mask film with an adhesive) Thereafter, the above-mentioned adhesive composition formulated by a dispenser is used The other end face of the reticle cover film (outer diameter 113 mmx 149 mm, inner diameter 1〇9 mmx 145 mm 'height 4.8 mm) coated to the end face and then with the reticle film film. In one stage, it was dried by heating and solidified (third stage: 100 ° C, 8 minutes; second stage: 180 t, 8 minutes) to obtain an adhesive layer (thickness 〇 2 mm) formed with the above-mentioned adhesive precursor composition. The reticle cover film of Example 8. Then, a polyester protective film having a thickness of 100 μm which was subjected to polysilicon oxidizing release treatment was attached, and aged at room temperature (2 〇 ± 3 〇 c) for 3 days. Stabilize the adhesion and make a reticle film with an adhesive. 151745.doc -32· 201130937 The evaluation of the light cover with the adhesive. 仃'[Plating price, other than this (modulus measurement) Using an autostereograph, the adhesive of 1.5 mm of the adhesive layer is 0.2 mm, and the width is the same. Stretching is performed with 1 〇m between the chucks. The force/extension speed at this time is measured by 3'/. The force at the time of stretching is divided by the profile of the sample, 300% of the modulus value. The value of the word is set to <Example 9> - except that the concentration of the polyfunctional epoxy compound (1,3_bis(__diglycidylamino)-cyclohexanol' non-volatile component is 5%, A sample of the photomask film was prepared and evaluated in the same manner as in Example 8 except that the toluene solution was changed to 15 parts by weight. &lt;Example 10&gt; In addition to a polyfunctional epoxy compound (1,3-bis(?) small-diglycidylamino)cyclohexane, a nonvolatile content of 5%, a solution of a solution A sample of the photomask film was produced by the same method as in Example 8 except that it was changed to 1·8 parts by weight. &lt;Example 11&gt; (Mercapto) acrylate acid ester copolymer 6 was prepared by a well-known method. Specifically, in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, ethyl acetate (30 parts by weight) was placed, and butyl acrylate was added in a weight ratio of 99/1/1.0. A mixture of acrylic acid/2,2, azobisisobutyronitrile (32 parts by weight) was reacted at 60 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, toluene (38 parts by weight) was added to obtain a solution of an acrylic copolymer having a nonvolatile content of 32% by weight (weight average molecular weight: 180,000). To 100 parts by weight of the obtained acrylic copolymer solution, 0.15 parts by weight of a polyfunctional epoxy compound (1,3 bis(indole, fluorenyl-glycidylamino fluorenyl) cyclohexane was added, and the concentration of the nonvolatile component was 5%, benzene solution)' and stirring and mixing to obtain an adhesive precursor composition. Thereafter, a mask film sample was produced and evaluated in the same manner as in Example 8. &lt;Example 12&gt; (Alkyl) alkyl acrylate copolymer 7 was prepared by a well-known method, and was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. Ethyl acetate (5 parts by weight) was added in a weight ratio of 99/1/1.0 to a mixture of butyl acrylate/acrylic acid/2,2,-azobisisobutyronitrile (32 parts by weight) under a nitrogen atmosphere. The reaction solution was allowed to react at 65 C for 8 hours. After completion of the reaction, toluene (8 parts by weight of ruthenium) was added to obtain an acrylic copolymer solution (weight average molecular weight: 600,000) having a nonvolatile content of 32% by weight. Adding 0 25 parts by weight of a polyfunctional epoxy compound (1,3 bis(indole, fluorenyl-glycidylaminomethyl)cyclohexane to 1 part by weight of the obtained acrylic copolymer solution, non-volatile The concentration of the component was 5%, and the solution was stirred and mixed to obtain the σ substance of the adhesive precursor group. Thereafter, a photomask film sample was produced and evaluated in the same manner as in Example 8. &lt;Comparative Example 4&gt; In addition to changing the polyfunctional epoxy compound (1,3_double &quot;卞_diglycidyl 151745.doc •34·201130937 amino-based) to 3.2 parts, A sample of the mask film was prepared and evaluated in the same manner as in the practice of the method. &lt;Comparative Example 5&gt; The same procedure as in Example 8 except that the polyfunctional epoxy compound (1,3, n-diglycidylaminomethyl) cyclohexan was changed to 3 parts of ruthenium A reticle film was produced and evaluated. &lt;Comparative Example 6&gt; Adhesively bonded to the poly-stone; (D〇wc〇ming (manufactured by the company), 叩4 (commercial name) non-volatile component concentration: 40%, toluene/xylene solution) 1 〇〇 Weight II, 〇.9 heavy sclerosing hardener (manufactured by Dow Corning, SRX2 12), the adhesive precursor composition was obtained. Thereafter, a mask ankle sample was prepared and evaluated in the same manner as in Example 8. &lt;Comparative Example 7&gt; A rubber-based hot-melt adhesive of styrene-ethylene/butylene-styrene was applied to a mask film frame of an aluminum alloy film having an end face and a mask film (outer diameter 113) &quot;149 _, inner diameter 1〇9 mmxl45 mm, height 4_8 mm) The other end face. Thereafter, a photomask film sample was produced and evaluated in the same manner as in Example 8. 151745.doc -35- 201130937 [(Νί Load-bearing test ◎ ◎ 〇 ◎ 〇XXXX Peelability ◎ ◎ 〇 ◎ 〇 ◎ XXXB 1 | m 〇»-Η 290 140 450 00 270 220 Weight average molecular weight 1200.12 million 1.86 million 1,200,200,300,000 1 hardened material (parts) Copies! 0.25 0.15 〇〇0.15 0.25 CN rn -1 0.03 〇&gt; 〇1 Type epoxy epoxy epoxy epoxy Epoxy-based epoxy-based SRX212 1 main component composition i-BA/BA/AA/HEA-48/48/l .5/2.5 i-BA/BA/AA/HEA=48/48/l .5/2.5 i-BA/BA/AA/HEA=48/48/l .5/2.5 BA/AA=99/1 BA/AA=99/1 i-BA/BA/AA/HEA=48/48/l .5 /2.5 i-BA/BA/AA/HEA=48/48/l.5/2.5 Polyoxygenated Adhesive Material Rubber Adhesive Material Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 4 Comparison Example 5 Comparative Example 6 Comparative Example 7 Temperature (0 butterfly toward -3 armored VHH 韹笈肊: W temperature h 毽 毽 毽: VOQ-I: 龋街瞀塄 151745.doc • 36· 201130937 &lt;Example 13&gt; (Preparation of Adhesive Precursor Composition) The (meth)acrylic acid alkyl ester copolymer 8 is prepared by a well-known method. In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube, ethyl acetate (3 parts by weight) was placed in a weight ratio of 48/48/1.5/2.5/1.0. Adding a mixture of butyl acrylate/butyl phthalate/acrylic acid/2-hydroxyethyl acrylate/2,2'-azobisisobutyrate (ΑΙΒΝ) (1 〇 half-life temperature 60 〇c) (32 weight) The reaction solution was reacted at 6 ° C for 8 hours under a nitrogen atmosphere. After the reaction, the toluene (38 parts by weight) was added to obtain an acrylic copolymer solution having a nonvolatile content of 32% by weight. The weight average molecular weight is 120,000.) To the 100 parts by weight of the obtained acrylic copolymer solution, 25 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylamino) is added. Base) a non-volatile component of cyclohexene, a 5% molarity, a toluene solution, and agitation, and a mixture of θ, to obtain an adhesive precursor composition. (Preparation of a photomask film with an adhesive) Applying the formulated adhesive precursor composition described above by means of a dispenser Next one end to the other end face with a mask made of an aluminum alloy pellicle film of the photomask pellicle frame (outer diameter of 113 mmx149 mm, an inner diameter 1〇9 mmxM5 _, _ U height) of. It is dried and solidified in two stages (the second stage: Saki, 8 minutes; the second stage: 峨, 8 minutes), and an adhesive having the adhesive precursor composition for the above-mentioned photomask film is obtained. A mask film with a thickness of G·2 _. Thereafter, the mask film was heat-treated under the boot for 60 minutes to adjust the amount of azobis(151745.doc -37-201130937) butyronitrile (polymerization initiator) remaining in the adhesive layer. Then, a polyester protective film having a thickness of 100 μm was subjected to polysilicon deoxidation treatment, and aged at room temperature (2 〇 ± 3 &lt; Jc) for 3 days to stabilize the adhesion, and an adhesive was prepared. Photomask film. The evaluation was carried out by performing the above evaluation on the obtained photomask film with an adhesive attached thereto. (Measurement of Residual Amount of Polymerization Starter) The residual amount of the polymerization initiator remaining in the adhesive was analyzed by high-performance liquid chromatography (HPLC). Take 0. 2 g of the adhesive in a 20 mL spiral tube and add B guess 1 mL. The components were extracted by a penetrator at 120 r.p.m.' at 25 ° C for 8 hours. The analysis device and extraction conditions were set as follows.

分析裝置：Tosoh製造，HPL CCPM 管柱：NuCLEOSLL 7C18(4.8 mm 沴 χ250 mm)Analytical unit: manufactured by Tosoh, HPL CCPM Column: NuCLEOSLL 7C18 (4.8 mm 沴 χ 250 mm)

管柱壓力：41 Kg/cm2 管柱溫度：40°C 注入量：10 pL 聚合起始劑之定量係用根據絕對校準曲線求出之重量除 以1片光罩護膜之黏著劑重量而算出。 &lt;實施例14&gt; (甲基）丙稀酸燒基酯共聚物9係藉由眾所周知之方法製 備。具體而言’於具備攪拌機、溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙酯（30重量 份），以99/1/1.0之重量比加入丙烯酸丁酯/丙稀酸/2,2，-偶 氮雙異丁腈之混合物（32重量份），於氮氣環境下，使該反 I51745.doc -38· 201130937 應溶液於60 C下反應8小時。反應結束後，添加甲苯（3 §重 量份），獲得不揮發成分濃度為32重量％之丙烯酸共聚物溶 液（重1平均分子量為180萬）。於所獲得之丙烯酸共聚物溶 液100重量份中添加0.15重量份多官能性環氧化合物（1，3_ 雙（N，N-二縮水甘油基胺基甲基）環己烷，不揮發成分濃度 為5%，曱苯溶液），並進行攪拌混合，獲得黏著劑前驅物 組合物。其後藉由與實施例1 3相同之方式製作光罩護膜樣 品，並進行評價。 &lt;實施例15&gt; (甲基）丙烯酸烷基酯共聚物10係藉由眾所周知之方法製 備。具體而言，於具備攪拌機' 溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙酯（5〇重量 份）’以99/1/2.0之重量比加入丙烯酸丁酯/丙烯酸/2,2|_偶 氮雙異丁腈之混合物（32重量份），於氮氣環境下，使該反 應溶液於65t下反應8小時。反應結束後，添加甲苯（㈣ 里伤）獲彳于不揮發成分濃度為32重量％之丙烯酸共聚物溶 液（重量平均分子量為6G萬）。於所獲得之㈣酸共聚物溶 液⑽重量份中添加〇.25重量份多官能性環氧化合物（1，3_ 雙（N，N•二縮水甘油基胺基曱基）環己炫，不揮發成分濃度 為5 /〇 f苯冷液）’並進行授拌現合，獲得黏著劑前驅物 組合物。其後藉由與實施例1G相同之方式製作光罩護膜樣 品，並進行評價。 &lt;實施例16&gt; 除了將實施例13中獲得之附帶黏著材料層之光罩護膜的 151745.doc •39- 201130937 加熱處理條件自13(TC下60分鐘變更成l〇〇tT6〇分鐘以 外，藉由與實施例13相同之方式製作光罩護膜樣品，並進 行評價。 &lt;比較例8&gt; 除了使實施例13中獲得之附帶黏著材料層之光罩護膜不 進行UOt下⑽鐘之加熱處理，而製作光罩護膜樣品以 外’藉由與實施例13相同之方式，進行評價。 〈比較例9&gt; 相對於聚石夕氧黏著^j(D〇wc〇rning(股）製造，sd4則（商 品名）不揮發成分漠度為4 G %，甲苯/ :甲苯溶液）⑽重量 伤添加0.9重莖份硬化劑（D〇wc〇rning(股）製造，srx⑴）， 獲得黏著劑前驅物組合物。其後藉由與實施例⑽同之方 式製作光罩護膜樣品，並進行評價。 &lt;比較例10&gt; 將苯乙烯-乙稀/丁稀·苯乙烯之橡膠系熱溶黏著劑塗佈於 一端面接著有光罩護膜薄膜之鋁合金製的光罩護膜框（外 位113 mmxl49 mm，内徑109匪乂⑷mm，高度4 8叫 之另一端面。其後藉由與實施例13相同之方式製作光罩護 膜樣品，並進行評價。 151745.doc 201130937 【e&lt;】 耐負重試 Μ ◎ ◎ 〇 ◎ ◎ X X 剝離性 ◎ ◎ 〇 ◎ ◎ X X 霧化 試驗 〇 〇 〇 〇 X X X 聚合起始 劑殘留量 2 ppm 1 2 ppm 4 ppm 7 ppm 9 ppm 1 1 聚合起 始劑 AIBN AIBN AIBN AIBN AIBN 1 1 重量平均 分子量 120萬 180萬 60萬 1 120萬 120萬 4*5* 沄 1 硬化材料(份） 份數 0.25 0.15 0.25 0.25 0.25 1 〇 1 種類 ! 環氧系 環氧系 環氧系 環氧系 環氧系 SRX212 1 主劑 組成 i-BA/BA/AA/HEA=48/48/l .5/2.5 BA/AA=99/1 BA/AA=99/1 i-BA/BA/AA/HEA=48/48/l .5/2.5 i-BA/BA/AA/HEA=48/48/l .5/2.5 聚矽氧系黏著材料 橡膠系黏著材料 實施例13 ! 實施例14 實施例15 實施例16 比較例8 比較例9 比較例10 llso4¥5Κ^裳¢: V3H 餒装¢: VV ilmlh毽装叱：VPQ 遛h邮毽爱¢: va-i:餚珠瞀塄 41 151745.doc 201130937 〈實施例17&gt; (黏著材料組合物之製備） (甲基）丙烯酸院基醋共聚物11係藉由眾所周知之方法製 備。具體而言’於具備授拌機、溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙酯（3〇重量 份）’以48/48/1.5/2.5/0.5之重量比加入丙稀酸異丁醋/丙稀 酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2，-偶氮雙異丁腈之混 合物（32重量份），於氮氣環境下，使該反應溶液於回流溫 度下反應8小時。反應結束後，添加甲苯（3 8重量份），獲得 不揮發成分濃度為32重量％之丙稀酸共聚物溶液（重量平均 分子量為120萬）。於所獲得之丙稀酸共聚物溶液1〇〇重量 份中添加0.05重量份多官能性環氧化合物（丨^雙^^-二縮 水甘油基胺基甲基）環己院’不揮發成分濃度為5%，甲苯 溶液）’並進行攪拌混合，獲得黏著材料組合物。 (附帶黏著材料之光罩護膜之製作） 其後’利用分注器將所調配之上述黏著材料組合物塗佈 至一端面接著有光罩護膜薄膜之紹合金製的光罩護膜框 (外徑 113 mmxl49 mm，内徑 109 mmxl45 mm，高度4.8 mm)之另一端面。以2個階段將其加熱乾燥、固化（第1階 段：100°C ’ 8分鐘；第2階段：18(TC，8分鐘），獲得形成 有含有實施例17之光罩護膜用黏著材料組合物之黏著材料 層（厚度0.2 mm)的實施例17之光罩護膜。繼而，貼附經聚 矽氧脫模處理之厚度為100 μιη之聚酯製保護膜，於室溫 (20±3°C )下熟化3天’使黏著力穩定化，製作附帶黏著材 151745.doc .42- 201130937 料之光罩護膜。對所獲得之附帶黏著材料之光罩護膜進行 上述評價，除此以外實施下述評價。 (光罩變形之評價） 光罩變形之評價係使用Trope丨公司製造之FlatMaster 200 進行測定。於貼附光罩護膜前測定光罩（6〇25石英）之平坦 度’其後貼附光罩護膜’測定貼附光罩護膜後之平坦度 (測定範圍：135 mmxllO mm)。將貼附前後之平坦度相 減，算出因貼附光罩護膜導致6025石英發生何種程度之變 形。 利用簡易型貼合機，將光罩護膜貼附在石英（負重：3〇 Kgf，60 sec)上。 ◎:由貼附光罩護膜引起之光罩之變形量為1〇〇nm以下 〇:由貼附光罩護膜引起之光罩之變形量為2〇〇nm以下 X :由貼附光罩護膜引起之光罩之變形量為2〇〇 nm以上 &lt;實施例18&gt; 除了將多官能性環氧化合物（1，3_雙（N，N_二縮水甘油基 胺基曱基)環己烷’不揮發成分濃度為5%，甲苯溶液)變成 (M份以外，藉由與實施例17相同之方法製作光罩護膜樣 品，並進行評價。 〈實施例19&gt; 除了將多官能性 胺基甲基）環己烧， 0.2份以外，藉由與 品，並進行評價。 環氧化合物（1，3-雙（N，N_二縮水甘油基 不揮發成分漢度為5% ’甲苯溶液）變成 實施例17相同之方法製作光罩護膜樣 151745.doc -43· 201130937 &lt;比較例11 &gt; 除了將多官能性環氧化合物二縮水甘油基 胺基甲基）環己烧’不揮發成分濃度為5%，甲苯溶液）變成 0.24份以外，ϋ由與實施例17相同之方法製作光罩護膜樣 品，並進行評價。 &lt;比較例12&gt; 除了將乡官能性環氧化合物(1，3_雙(Ν，Ν_二縮水甘油基 胺基曱基）環己院，不揮發成分濃度為5%，甲苯溶液）變成 〇广份以外’#由與實施例17相同之方法製作光罩護膜樣 品，並進行評價。 15l745.doc 201130937 【寸&lt;】 霧化試驗 〇 〇 〇 〇 〇 光罩之變形 ◎ 〇 〇 X ◎ 剝離性 〇 ◎ ◎ ◎ X 重量平均分子量 130萬 130萬 130萬 130萬 1- 130萬 硬化材料(份） 份數 0.05 (N 〇 0.24 1 0.01 種類 環氧系 環氧系 環氧系 環氧系 環氧系 主劑 組成 i-BA/BA/AA/HEA=30/66/l .5/2.5 i-BA/BA/AA/HEA=30/66/l .5/2.5 i-BA/BA/AA/HEA=30/66/l .5/2.5 i-BA/BA/AA/HEA=30/66/l .5/2.5 i-BA/BA/AA/HEA=30/66/l .5/2.5 實施例17 實施例18 實施例19 比較例11 比較例12 煎§0砩墩-^韹装肊：VHH 翹跋^: VV IS卜怒爱¢: VCQ 遛h畹毽爱¢: va-·.:餒街替塄 -45 - 151745.doc 201130937 &lt;實施例20&gt; 除了將多官能性環氧化合物（1，3-雙（N，N-二縮水甘油美 胺基曱基）環己烷’不揮發成分濃度為5%，甲笨溶液）變成 曱本二異氰酸醋之二經甲基丙烧加成物0_15份以外，获由 與實施例17相同之方法製作光罩護膜樣品，並進行評價。 〈實施例21&gt; (黏著材料組合物之製備） (甲基）丙烯酸院基酯共聚物12係藉由眾所周知之方法製 備。具體而言’於具備攪拌機、溫度計、回流冷卻器、滴 加裝置、氮氣導入管之反應容器中放入乙酸乙醋（3〇重量 份），以69/30/1/0.5之重量比加入丙烯酸2_乙基己酯/丙烯 酸丁酯/丙烯酸/2,2，-偶氮雙異丁腈之混合物（32重量份）， 於氮氣環丨兄下’使該反應溶液於回流溫度下反應8小時。 反應結束後’添加甲苯（3 8重量份），獲得不揮發成分濃度 為32重量％之丙烯酸共聚物溶液（重量平均分子量為15〇 萬）。於所獲得之丙烯酸共聚物溶液1〇〇重量份中添加〇15 重置伤多S旎性環氧化合物（1,3_雙（N，N_二縮水甘油基胺 基曱基）環己烷，不揮發成分濃度為5%，甲苯溶液），並進 行攪拌混合，獲得黏著材料組合物。其後藉由與實施例工7 相同之方式製作光罩護膜樣品，並進行評價。 15l745.doc -46· 201130937 【5 &lt;】 耐負重 試驗 〇 〇 1 剝離 〇 ◎ 1 霧化 試驗 〇 〇 1 逸氣 試驗 ◎ ◎ 對乙酸乙酯之重 量膨潤度(倍） 00 〇〇 1 對甲苯之重量| 膨潤度(倍） OS OS 1 重量平均 分子量 130萬 1 150萬 硬化材料(份） 份數 0.15 0.15 種類 異氰酸酯系 1 環氧系 主劑 组成 i-B A/B A/AA/HEA=48/48/l .5/2.5 Γ 2ΗΕΑ/ΒΑ/ΑΑ=69/30/1 實施例20 實施例21 Isro砩ιο·(Ν窗发¢: VH3(N 溫|0^澈-3盔教《 : V3H 窗|€: VV 溫-一絰装肊：V8 IShBlc盔裝¢: VCQ-!:艏街皆塄 151745.doc -47- 201130937 [產業上之可利用性] 本發明之光罩護膜為逸氣產生量較少且有機氣體吸附性 月t&gt;優異之光罩5蒦膜，因此可適宜地用於ic(integrated circuit ’積體電路）、LSI(大規模積體電路）、TFT型 LCD(thin-film transistor liquid crystal displayer，薄膜電 晶體型液晶顯示器）等之微影步驟。 151745.doc -48-Column pressure: 41 Kg/cm2 Column temperature: 40 °C Injection amount: 10 pL The amount of polymerization initiator is calculated by dividing the weight determined from the absolute calibration curve by the weight of the adhesive of one mask. . &lt;Example 14&gt; (Methyl) acrylate acrylate copolymer 9 was prepared by a well-known method. Specifically, in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, ethyl acetate (30 parts by weight) was placed, and butyl acrylate was added in a weight ratio of 99/1/1.0. A mixture of acrylic acid/2,2,-azobisisobutyronitrile (32 parts by weight) was reacted under a nitrogen atmosphere for 8 hours at 60 C under the reaction of N51745.doc -38·201130937. After the completion of the reaction, toluene (3 § by weight) was added to obtain a solution of an acrylic copolymer having a nonvolatile content of 32% by weight (weight 1 average molecular weight: 1.8 million). To 100 parts by weight of the obtained acrylic copolymer solution, 0.15 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane was added, and the concentration of the nonvolatile matter was 5%, benzene solution), and stirred and mixed to obtain an adhesive precursor composition. Thereafter, a mask film sample was produced and evaluated in the same manner as in Example 13. &lt;Example 15&gt; The alkyl (meth)acrylate copolymer 10 was prepared by a well-known method. Specifically, ethyl acetate (5 parts by weight) was placed in a reaction vessel equipped with a stirrer 'thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube' to add butyl acrylate in a weight ratio of 99/1/2.0. /Acrylic/2,2|_ a mixture of azobisisobutyronitrile (32 parts by weight), and the reaction solution was allowed to react at 65 t for 8 hours under a nitrogen atmosphere. After the completion of the reaction, toluene ((4) was added) to obtain a solution of an acrylic copolymer having a nonvolatile content of 32% by weight (weight average molecular weight: 6 Gb). Adding 〇.25 parts by weight of the polyfunctional epoxy compound (1,3_bis(N,N• diglycidylamino) cycline) to the (4) parts by weight of the obtained (tetra) acid copolymer solution, non-volatile The concentration of the component is 5 / 〇f benzene cold liquid) and is mixed and obtained to obtain an adhesive precursor composition. Thereafter, a mask film sample was produced and evaluated in the same manner as in Example 1G. &lt;Example 16&gt; The heat treatment conditions of 151745.doc •39-201130937 of the mask film with the adhesive material layer obtained in Example 13 were changed from 13 (60 minutes under TC to l〇〇tT6 minutes) A sample of the photomask film was prepared and evaluated in the same manner as in Example 13. <Comparative Example 8> The photomask film with the adhesive material layer obtained in Example 13 was not subjected to UOt (10) clock. The heat treatment was carried out to prepare a sample of the mask film, and the evaluation was carried out in the same manner as in Example 13. <Comparative Example 9> Manufactured in accordance with the polyglycol oxide (j) , sd4 (trade name) non-volatile component indifference 4 G %, toluene / : toluene solution) (10) weight injury added 0.9 heavy stem hardener (D〇wc〇rning (stock), srx (1)), to obtain adhesive Precursor composition. A sample of the photomask film was prepared and evaluated in the same manner as in Example (10). &lt;Comparative Example 10&gt; The styrene-ethylene/butylene-styrene rubber was thermally dissolved. The adhesive is applied to one end surface and then the aluminum film of the photomask film The reticle cover frame (outer position 113 mm x l49 mm, inner diameter 109 匪乂 (4) mm, height 4 8 is called the other end face. Thereafter, a reticle film sample was prepared and carried out in the same manner as in Example 13 Evaluation 151745.doc 201130937 [e&lt;] Resistance test ◎ ◎ 〇 ◎ ◎ XX peelability ◎ ◎ 〇 ◎ ◎ XX atomization test 〇〇〇〇 XXX polymerization initiator residue 2 ppm 1 2 ppm 4 ppm 7 Ppm 9 ppm 1 1 Polymerization initiator AIBN AIBN AIBN AIBN AIBN 1 1 Weight average molecular weight 1.2 million 1.86 million 1 1200 1200 million 4*5* 沄1 Hardened material (parts) Parts 0.25 0.15 0.25 0.25 0.25 1 〇 1 type! Epoxy epoxy-based epoxy epoxy-based SRX212 1 Main component composition i-BA/BA/AA/HEA=48/48/l .5/2.5 BA/AA=99/1 BA /AA=99/1 i-BA/BA/AA/HEA=48/48/l .5/2.5 i-BA/BA/AA/HEA=48/48/l .5/2.5 Polyoxygenated Adhesive Rubber-based adhesive material Example 13 ! Example 14 Example 15 Example 16 Comparative Example 8 Comparative Example 9 Comparative Example 10 llso4 ¥5Κ^¢¢: V3H 馁 ¢: VV ilmlh毽 叱: VPQ 遛h postal love ¢: va-i: 瞀塄珠瞀塄 4 1 151745.doc 201130937 <Example 17> (Preparation of adhesive material composition) The (meth)acrylic acid-based vinegar copolymer 11 was prepared by a well-known method. Specifically, 'in a reaction vessel equipped with a mixer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube, ethyl acetate (3 parts by weight) was placed in an amount of 48/48/1.5/2.5/0.5. a mixture of butyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2,-azobisisobutyronitrile (32 parts by weight) was added in a weight ratio under nitrogen atmosphere. The reaction solution was reacted at reflux temperature for 8 hours. After completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic acid copolymer solution (weight average molecular weight: 1.2 million) having a nonvolatile content of 32% by weight. Adding 0.05 parts by weight of a polyfunctional epoxy compound (丨^ bis-^- diglycidylaminomethyl) cyclohexine' non-volatile component concentration to 1 part by weight of the obtained acrylic acid copolymer solution It is 5%, toluene solution)' and stirred and mixed to obtain an adhesive material composition. (Preparation of photomask film with adhesive material) Thereafter, the above-mentioned adhesive material composition prepared by applying the dispenser to a single end surface and then a mask film of the mask film is used. The other end face (outer diameter 113 mm x l49 mm, inner diameter 109 mm x l45 mm, height 4.8 mm). It was heat-dried and solidified in two stages (first stage: 100 ° C '8 minutes; second stage: 18 (TC, 8 minutes), and an adhesive material combination formed with the mask film of Example 17 was obtained. a visor film of the coating material of Example 17 having a thickness of 0.2 mm. Then, a protective film of polyester having a thickness of 100 μm which was subjected to polysilicon oxidizing treatment was attached at room temperature (20±3). °C) under aging for 3 days' to stabilize the adhesion, and make a reticle film with 151745.doc.42- 201130937 material. The above-mentioned evaluation of the obtained visor film with adhesive material is performed. The following evaluations were carried out. (Evaluation of mask deformation) The evaluation of the mask deformation was performed using a FlatMaster 200 manufactured by Trope Co., Ltd. The flatness of the mask (6 〇 25 quartz) was measured before attaching the mask film. 'After attaching the mask to protect the film', the flatness of the mask is measured (measurement range: 135 mmxllO mm). The flatness before and after the attachment is subtracted, and the result is 6025 due to the attached mask. What is the degree of deformation of quartz? Using a simple laminator, the mask The film is attached to quartz (load: 3 〇 Kgf, 60 sec). ◎: The amount of deformation of the reticle caused by attaching the reticle film is 1 〇〇 nm or less 〇: caused by attaching the reticle film The amount of deformation of the mask is 2 〇〇 nm or less. X: The amount of deformation of the reticle caused by attaching the reticle film is 2 〇〇 nm or more. &lt;Example 18&gt; In addition to the polyfunctional epoxy compound (1, 3_ bis (N,N- diglycidylamino fluorenyl) cyclohexane 'nonvolatile content concentration 5%, toluene solution) was changed to (M part, the same method as in Example 17 was used to prepare a photomask The film sample was evaluated and evaluated. <Example 19> In addition to 0.2 part of the polyfunctional aminomethyl group, it was evaluated by the product and the mixture. N, N_ diglycidyl non-volatile content of 5% 'toluene solution> was changed to the same method as in Example 17 to prepare a mask film 151745.doc -43·201130937 &lt;Comparative Example 11 &gt; Functional epoxy compound diglycidylaminomethyl) cyclohexanol [nonvolatile content of 5%, toluene solution) became 0.24 parts Further, a mask film sample was produced and evaluated in the same manner as in Example 17. &lt;Comparative Example 12&gt; In addition to the cyclization of the oxime compound (1,3 bis(indole, Ν_ diglycidyl fluorenyl fluorenyl), the concentration of the nonvolatile component was 5%, the toluene solution) was changed. A reticle film sample was prepared and evaluated in the same manner as in Example 17 except for 〇广份. 15l745.doc 201130937 [Inch&lt;] Deformation of the enamel mask of the atomization test ◎ 〇〇X ◎ Peeling 〇 ◎ ◎ ◎ X Weight average molecular weight 1,300,130,130,130,130,000-1, 1.3 million hardened material (Parts) Parts 0.05 (N 〇0.24 1 0.01 Type epoxy-based epoxy epoxy-based epoxy base agent composition i-BA/BA/AA/HEA=30/66/l .5/2.5 i-BA/BA/AA/HEA=30/66/l .5/2.5 i-BA/BA/AA/HEA=30/66/l .5/2.5 i-BA/BA/AA/HEA=30/ 66/l .5/2.5 i-BA/BA/AA/HEA=30/66/l.5/2.5 Example 17 Example 18 Example 19 Comparative Example 11 Comparative Example 12 Fried §0砩墩-^韹肊: VHH 跋 跋 ^: VV IS 怒 ¢ ¢: VCQ 遛h畹毽 love ¢: va-·.: 馁 塄 塄 -45 - 151745.doc 201130937 &lt;Example 20&gt; In addition to the polyfunctional ring Oxygen compound (1,3-bis(N,N-diglycidylmercapto)-cyclohexane' non-volatile content of 5%, a solution of sputum) becomes bismuth diisocyanate A sample of the mask film was prepared and evaluated in the same manner as in Example 17 except that the base-acrylic acid addition product was 0 to 15 parts. <Example 21> ( Preparation of Adhesive Material Composition) The (meth)acrylic acid ester copolymer 12 is prepared by a well-known method. Specifically, it is a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube. Ethyl acetate (3 parts by weight) was added, and 2-ethylhexyl acrylate/butyl acrylate/acrylic acid/2,2,-azobisisobutyronitrile was added in a weight ratio of 69/30/1/0.5. The mixture (32 parts by weight) was reacted under reflux with nitrogen gas for 8 hours. After completion of the reaction, 'toluene (38 parts by weight) was added to obtain a nonvolatile content of 32% by weight. Acrylic copolymer solution (weight average molecular weight is 150,000). Add 〇15 to 1 part by weight of the obtained acrylic copolymer solution to replace the multi-S epoxide (1,3_double (N, N_ diglycidylamino fluorenyl) cyclohexane, a nonvolatile content of 5%, a toluene solution, and stirred and mixed to obtain an adhesive material composition. Thereafter, in the same manner as in Example 7 Make a mask film sample and perform Evaluation 15l745.doc -46· 201130937 [5 &lt;] load-bearing test 〇〇 1 peeling 〇 ◎ 1 atomization test 〇〇 1 outgassing test ◎ ◎ weight of ethyl acetate swelling (times) 00 〇〇 1 Weight of toluene | Degree of swelling (times) OS OS 1 Weight average molecular weight 1.3 million 1 1.5 million hardened materials (parts) Parts 0.15 0.15 Type isocyanate system 1 Epoxy based agent composition iB A/BA/AA/HEA=48 /48/l .5/2.5 Γ 2ΗΕΑ/ΒΑ/ΑΑ=69/30/1 Example 20 Example 21 Isro砩ιο·(Ν窗¢: VH3(N温|0^澈-3Helmets: V3H window|€: VV temperature-one armor: V8 IShBlc helmet mount: VCQ-!: 艏街塄塄151745.doc -47- 201130937 [Industrial Applicability] The photomask cover of the present invention is Since the amount of outgas generation is small and the organic gas adsorption property is excellent, the mask 5 is excellent in the film, so it can be suitably used for ic (integrated circuit 'integrated circuit), LSI (large-scale integrated circuit), and TFT type LCD. A lithography step such as a thin-film transistor liquid crystal display. 151745.doc -48-

Claims (1)

201130937 七、申請專利範圍： 1. 一種光罩護膜，其特徵係具有光罩護膜框，於該光罩護 膜框之一端面具有光罩護膜薄膜且於另一端面具有黏著 劑者’並且該點著劑對甲苯之重量膨潤度為5倍以上。 2. 如請求項1之光罩護膜，其中該黏著劑含有（曱基）丙烯酸 ，烷基酯共聚物與硬化材料之反應生成物，並且該（甲基） 丙烯酸烷基酯共聚物係具有碳數4〜14之烷基之（曱基）丙 烯酸烷基酯與含有與硬化材料具有反應性之官能基之單 體的共聚物。 3 ·如明求項1或2之光罩護膜，其中該黏著劑藉由拉伸速度 為30 mm/min之拉伸試驗所獲得之2yc下的3〇〇%模數值 為 50〜350 mN/mm2。 4.如請求項2之光罩護膜，其中該硬化材料係選自由多官 能性裱氧化合物及異氰酸酯系化合物所組成之群中之至 少一種硬化材料。 5·如請求項1或2之光罩護膜，其中該黏著劑係包含含有具 備聚合起始末端之聚合物及聚合起始劑之黏著劑組合物 者，該黏著劑中之聚合起始劑之總重量相對於黏著劑總 重量為8 ppm以下。 6. 如請求項丨或2之光罩護膜，其中該黏著劑係含有（甲基） 丙烯酸烷基酯共聚物100重量份與硬化材料〇〇5〜3重量^分 之反應生成物者。 7. 如請求項4之光罩護膜，其中該多官能性環氧化合物係 具有2〜4個環氧基之含氮環氧化合物。 151745.doc 201130937 月求項2之光罩濩膜，其含有丙烯酸作為含有與該硬 化材料具有反應性之官能基的單體，並且㈣烯酸之量 相對於構成該（甲基）丙烯酸烷基酯共聚物之全部單體為 〇·1〜5重量％。 9·如請求項2之光罩護膜，其中該（甲基）丙稀酸炫基醋共聚 物之重量平均分子量為70萬〜250萬。 種光罩4膜，其特徵係具有光罩護膜框，於該光罩護 膜框之一端面具有光罩護膜薄膜且於另一端面具有黏著 劑者，並且該黏著劑係包含含有具備聚合起始末端之聚 合物及聚合起始劑之黏著劑組合物者，該黏著劑中之聚 合起始劑之總重量相對於黏著劑總重量為8 ppm以下。 11.如凊求項10之光罩護膜，其中該聚合起始劑為過氧化物 系聚合起始劑或偶氮系聚合起始劑、或者烷基苯酮系聚 合起始劑或醯基氧化膦系聚合起始劑。 12_如請求項1〇或u之光罩護膜，其中該黏著劑含有（甲基） 丙烯酸烷基酯共聚物與硬化材料之反應生成物，該（甲 基）丙烯酸烷基酯共聚物係具有碳數4〜丨4之烷基之（甲基） 丙烯酸烷基酯與含有與硬化材料具有反應性之官能基之 單體的共聚物。 13. 如請求項1〇或11之光罩護膜，其中該黏著劑藉由拉伸速 度為30 mm/min之拉伸試驗所獲得之23°c下的3〇〇%模數 值為 50〜350 mN/mm2。 14. 如請求項11或12之光罩護膜’其中該硬化材料係選自由 多官能性環氧化合物及異氰酸醋系化合物所組成之群中 151745.doc 201130937 之至少一種硬化材料。 15. 如請求項！OSU之光罩護膜，其中該黏著劑對甲苯之重 量膨潤度為5倍以上。 16. 如請求項12之光罩護膜，其中該黏著劑係含有（甲基）丙 • 烯酸烷基酯共聚物1〇0重量份與硬化材料〇·〇5〜3重量份之 . 反應生成物者。 17. 如請求項14之光罩護膜，其中該多官能性環氧化合物係 具有2〜4個環氧基之含氮環氧化合物。 18_如請求項12之光罩護膜，其含有丙烯酸作為含有與該硬 化材料具有反應性之官能基的單體，並且該丙稀酸之量 相對於構成該（甲基）丙烯酸烷基酯共聚物之全部單體為 0 · 1〜5重量％。 19. 如請求項12之光罩護膜，其中該（曱基）丙烯酸烷基酯共 聚物之重量平均分子量為7〇萬〜250萬。 20. —種黏著劑，其特徵為其係含有（甲基）丙烯酸烷基酯共 聚物100重量份與多官能性環氧化合物〇〇5〜3重量份之反 應生成物者，該（曱基）丙烯酸烷基酯共聚物係具有碳數 4〜14之烷基之（曱基）丙烯酸烷基酯與含有與環氧基具有 . 反應性之官能基之單體的共聚物，並且該黏著劑對甲苯 之重量膨潤度為5倍以上。 151745.doc 201130937 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明·· 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 151745.doc • 2 ·201130937 VII. Patent application scope: 1. A reticle protective film, which is characterized in that it has a reticle protective film frame, and has a reticle film on one end surface of the reticle protective film frame and an adhesive on the other end face. 'And the point agent has a degree of swelling of toluene of 5 times or more. 2. The reticle film of claim 1, wherein the adhesive contains (mercapto)acrylic acid, a reaction product of an alkyl ester copolymer and a hardening material, and the (meth)acrylic acid alkyl ester copolymer has A copolymer of an alkyl (indenyl) acrylate having a carbon number of 4 to 14 and a monomer having a functional group reactive with a hardening material. 3. The reticle film of claim 1 or 2, wherein the adhesive has a value of 3 〇〇% at 2 yc obtained by a tensile test at a tensile speed of 30 mm/min of 50 to 350 mN /mm2. 4. The reticle film of claim 2, wherein the hardening material is selected from the group consisting of at least one hardening material consisting of a plurality of functional oxygen compounds and isocyanate compounds. 5. The photomask film of claim 1 or 2, wherein the adhesive comprises an adhesive composition comprising a polymer having a polymerization starting end and a polymerization initiator, and a polymerization initiator in the adhesive The total weight is 8 ppm or less relative to the total weight of the adhesive. 6. The reticle film of claim 2 or 2, wherein the adhesive contains 100 parts by weight of an alkyl (meth) acrylate copolymer and 5 to 3 parts by weight of the hardened material. 7. The photomask film of claim 4, wherein the polyfunctional epoxy compound is a nitrogen-containing epoxy compound having 2 to 4 epoxy groups. 151745.doc 201130937 The mask enamel film of claim 2, which contains acrylic acid as a monomer having a functional group reactive with the hardening material, and (iv) an amount of the olefinic acid relative to the alkyl group constituting the (meth) acrylate The total monomer of the ester copolymer is 〇·1 to 5% by weight. 9. The photomask film of claim 2, wherein the (meth)acrylic acid sulfonic acid vinegar copolymer has a weight average molecular weight of from 700,000 to 2.5 million. The reticle 4 film is characterized in that the reticle film frame has a reticle film on one end surface of the reticle film frame and has an adhesive on the other end surface, and the adhesive agent includes In the adhesive composition of the polymer of the polymerization starting end and the polymerization initiator, the total weight of the polymerization initiator in the adhesive is 8 ppm or less based on the total weight of the adhesive. 11. The photomask film according to claim 10, wherein the polymerization initiator is a peroxide polymerization initiator or an azo polymerization initiator, or an alkylphenone polymerization initiator or a mercapto group. A phosphine oxide-based polymerization initiator. 12_ The photomask film of claim 1 or u, wherein the adhesive comprises a reaction product of a (meth)acrylic acid alkyl ester copolymer and a hardening material, the (meth)acrylic acid alkyl ester copolymer system A copolymer of an alkyl (meth) acrylate having an alkyl group having 4 to 4 carbon atoms and a monomer having a functional group reactive with a hardening material. 13. The reticle film of claim 1 or 11, wherein the adhesive has a value of 3 〇〇% at 23 ° C obtained by a tensile test at a tensile speed of 30 mm/min of 50 〜 350 mN/mm2. 14. The reticle film of claim 11 or 12 wherein the hardening material is selected from the group consisting of a polyfunctional epoxy compound and an isocyanate compound 151745.doc 201130937 of at least one hardening material. 15. As requested! The mask of the OSU mask, wherein the adhesive has a degree of swelling of toluene of 5 times or more. 16. The reticle film of claim 12, wherein the adhesive comprises 1 〇 0 parts by weight of a (meth) acrylate alkyl ester copolymer and 5 to 3 parts by weight of the hardening material 〇·〇. Producer. 17. The reticle film of claim 14, wherein the polyfunctional epoxy compound is a nitrogen-containing epoxy compound having 2 to 4 epoxy groups. The photomask film of claim 12, which contains acrylic acid as a monomer having a functional group reactive with the hardening material, and the amount of the acrylic acid is relative to the alkyl (meth)acrylate The total monomer of the copolymer is from 0 to 1 to 5% by weight. 19. The reticle film of claim 12, wherein the (mercapto)alkyl acrylate copolymer has a weight average molecular weight of from 70,000 to 2.5 million. An adhesive comprising a reaction product of 100 parts by weight of an alkyl (meth) acrylate copolymer and 5 to 3 parts by weight of a polyfunctional epoxy compound, An alkyl acrylate copolymer is a copolymer of an alkyl (meth) acrylate having an alkyl group having 4 to 14 carbon atoms and a monomer having a functional group reactive with an epoxy group, and the adhesive The degree of swelling of the toluene is 5 times or more. 151745.doc 201130937 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple. · 5. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: (none) 151745.doc • 2 ·
TW099139404A 2009-11-18 2010-11-16 Mask mask TWI579354B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2009263118A JP5319500B2 (en) 2009-11-18 2009-11-18 Pellicle
JP2009263117 2009-11-18
JP2009263119A JP5319501B2 (en) 2009-11-18 2009-11-18 Pellicle

Publications (2)

Publication Number Publication Date
TW201130937A true TW201130937A (en) 2011-09-16
TWI579354B TWI579354B (en) 2017-04-21

Family

ID=44031809

Family Applications (1)

Application Number Title Priority Date Filing Date
TW099139404A TWI579354B (en) 2009-11-18 2010-11-16 Mask mask

Country Status (3)

Country Link
KR (1) KR101371949B1 (en)
CN (1) CN102073213B (en)
TW (1) TWI579354B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6326059B2 (en) * 2013-10-15 2018-05-16 旭化成株式会社 Pellicle, photomask with pellicle, and method for manufacturing semiconductor device
US10353283B2 (en) * 2016-07-11 2019-07-16 Shin-Etsu Chemical Co., Ltd. Adhesive for pellicle, pellicle, and method of selecting adhesive for pellicle

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2714450B2 (en) * 1989-08-10 1998-02-16 ダイセル化学工業株式会社 Dustproof film
JP4363725B2 (en) * 1999-11-19 2009-11-11 旭化成イーマテリアルズ株式会社 Pellicle
JP4707320B2 (en) * 2003-12-22 2011-06-22 電気化学工業株式会社 Two-component acrylic adhesive composition and joined body using the same
KR20060116152A (en) * 2005-05-09 2006-11-14 미쓰이 가가쿠 가부시키가이샤 Pellicles having low adhesive residue
CN101243153B (en) * 2005-09-05 2010-10-06 日东电工株式会社 Adhesive composition, adhesive sheet and surface-protecting film
JP5863157B2 (en) * 2006-12-18 2016-02-16 日東電工株式会社 Adhesive sheet
JP2009025559A (en) * 2007-07-19 2009-02-05 Shin Etsu Chem Co Ltd Pellicle frame

Also Published As

Publication number Publication date
CN102073213B (en) 2014-03-12
KR101371949B1 (en) 2014-03-07
CN102073213A (en) 2011-05-25
TWI579354B (en) 2017-04-21
KR20110055430A (en) 2011-05-25

Similar Documents

Publication Publication Date Title
TWI525385B (en) A protective film for an adhesive film, a mask for a protective film, and a method for manufacturing a semiconductor element
JP4318743B1 (en) Ultraviolet curable removable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the same
JP6156443B2 (en) LAMINATE AND SUBSTRATE PROCESSING METHOD
JP2016167070A (en) Pellicle
TW201038701A (en) Radiation-cure adhesive composition for optical member and adhesive optical member
JP2011241377A (en) Adhesive composition for optical member, adhesive layer, optical member having adhesive layer, image display with optical member, and method of manufacturing image display device
JP5785489B2 (en) Pellicle
JP6316686B2 (en) Pellicle, photomask with pellicle, and method for manufacturing semiconductor device
JP2010002895A (en) Adhesive material composition for pellicle
JP5622427B2 (en) Optical member pressure-sensitive adhesive composition, optical member pressure-sensitive adhesive layer, pressure-sensitive adhesive optical member, and image display device
CN105683834B (en) Pellicle, photomask with pellicle, and method for manufacturing semiconductor element
JP2003049128A (en) Method for producing acrylic adhesive sheet for optical member and acrylic adhesive sheet for optical member
JP5319501B2 (en) Pellicle
JP6062806B2 (en) Active ray curable adhesive composition for re-peeling protective tape for glass etching, re-peeling protective tape for glass etching
TW201130937A (en) Photo-mask protection film
KR20180031330A (en) Optically Clear Adhesive Composition, and Optically Clear Adhesive Film comprising the Same, and Flat Panel Display
TW200535207A (en) Hot melt adhesive composition
JP5002777B2 (en) Acrylic adhesive tape manufacturing method and acrylic adhesive tape
TW201720891A (en) Pellicle which contains a pellicle frame, a pellicle film disposed on one end rface of the pellicle frame, and an adhesive layer adhered to the other end face of the pellicle frame
JP5756744B2 (en) Pellicle pressure-sensitive adhesive composition
KR101750589B1 (en) Solvent-type adhesive composition by photopolymerisation
TW201829700A (en) Optically clear adhesive composition, optically clear adhesive film comprising the same, and flat panel display device
WO2023149347A1 (en) Pellicle, exposure original plate, exposure apparatus, method for producing pellicle, and method for testing adhesive layer for mask