TW201235436A - Pressure sensitive adhesive sheet, optical film with pressure sensitive adhesive and optical laminate - Google Patents

Pressure sensitive adhesive sheet, optical film with pressure sensitive adhesive and optical laminate Download PDF

Info

Publication number
TW201235436A
TW201235436A TW101102631A TW101102631A TW201235436A TW 201235436 A TW201235436 A TW 201235436A TW 101102631 A TW101102631 A TW 101102631A TW 101102631 A TW101102631 A TW 101102631A TW 201235436 A TW201235436 A TW 201235436A
Authority
TW
Taiwan
Prior art keywords
film
adhesive
group
weight
acrylate
Prior art date
Application number
TW101102631A
Other languages
Chinese (zh)
Other versions
TWI553085B (en
Inventor
Yosuke Ota
Ryu Takeko
Satoshi Nagayasu
Original Assignee
Sumitomo Chemical Co
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
Application filed by Sumitomo Chemical Co filed Critical Sumitomo Chemical Co
Publication of TW201235436A publication Critical patent/TW201235436A/en
Application granted granted Critical
Publication of TWI553085B publication Critical patent/TWI553085B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/005—Diaphragms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A pressure sensitive adhesive sheet can be obtained by forming in a sheet shape from a pressure sensitive adhesive composition comprising 100 parts by weight of copolymer (A) and from 0.01 to 5 parts by weight of a crosslinker (B); wherein the copolymer (A) is obtained from monomer mixture comprising the following monomers (A-1), (A-2) and (A-3), and has weight average molecular weigh of from 1000000 to 2000000; (A-1) from 94.8 to 99.89 % by weight of (meth)acrylic ester of formula (I), wherein R1 represents a hydrogen atom or a methyl group and R2 represents an alkyl group having 14 carbon atoms or less or an aralkyl group having 14 carbon atoms or less, an hydrogen atom constituting R2 may be substituted by -O-(C2H4)-R3 group, n shows 0 or an integer of from 1 to 4, R3 represents an alkyl group having 12 carbon atoms or less or an aryl group having 12 carbon atoms or less, (A-2) from 0.1 to 5 % by weight of (meth)acrylic monomer having a hydroxyl group, (A-3) from 0.01 to 0.2 % by weight of (meth)acrylic ester containing carboxyl group of the formula (II), wherein R4 represents a hydrogen atom or a methyl group and A represents a bivalent organic group having 2 to 4 carbon atoms.

Description

201235436 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種黏著劑片材及使用其之附有黏著劑之 光學膜》 於本發明中作為對象之光學膜例如包含偏光板或相位差 膜。本發明亦關於一種使用該附有黏著劑之光學膜且較佳 地用於液晶顯示之光學積層體。 【先前技術】 偏光板係安裝於液晶顯示裝置中而得以廣泛使用。偏光 板通常係以於偏光膜之兩面積層透明保護膜，於至少一面 之保護膜之表面形成黏著劑層，且於該黏著劑層上貼合剝 離膜之狀態而廣泛通用。 又’有時亦於偏光膜之兩面貼合有保護膜之狀態的偏光 板上積層相位差膜而製成橢圓偏光板，並於該相位差.膜側 依序貼合黏著劑層/剝離膜。進而，有時亦於相位差膜之 表面依序貼合黏著劑層/剝離膜。於本說明書中，將如此 設置黏著劑層之偏光板、橢圓偏光板、相位差膜等一併稱 為光學膜。於向液晶單元之貼合前，將該等設置有黏著劑 層之光學膜裁剪為規定之大小後，使剝離膜剝離，經由露 出之黏著劑層而貼合於液晶單元上。此種設置有黏著劑層 之光學膜存在於裁剪時黏著劑層容易缺損之加工性問題。 因此，通常於形成黏著劑層後，花費充分之時間使其固化 (所謂固化，係指於形成黏著劑層後，花費一定時間進行 交聯反應而提高凝膠分率）而供於使用，就生產性之方面 161767.doc 201235436 而言，仍有改良之餘地。 就透明性或對候性之觀點而言，於光學膜所使用之黏著 劑中大量使用以丙烯酸酯作為主成分且藉由使具有如羥基 或羧基之極性官能基之單體共聚合而製造之丙烯酸系樹 脂。於該丙稀酸系樹脂中調配交聯劑而賦予必要之凝聚 力。此處，所謂交聯劑，係指於分子内至少具有2個可與 構成丙烯酸系樹脂之極性官能基進行反應而形成交聯結構 之官能基的化合物，具體而言，有異氰酸酯系化合物、環 氧系化合物、金屬螯合物系化合物、胺系化合物等。其 中’異氰酸酯系化合物可廣泛用作交聯劑。 即’於具有極性官能基之丙烯酸系樹脂中調配於分子内 至少具有2個異氰酸基（_NC0)之異氰酸酯系交聯劑，藉此 丙稀酸系樹脂中之官能基與交聯劑中之異氰酸基隨著時間 經過而進行反應並形成交聯結構，表現凝聚力並且加工性 亦k尚。因此，只要提高其交聯反應之速度，則可縮短直 至顯示充分之加工性為止所需要之時間。作為提高交聯反 應之速度之方法，例如於JP2004-190012-A中記載有將胺 系化合物作為交聯觸媒而進行調配之方法，於該情形時， ， 作為交聯劑’較佳為異氰酸酯系化合物。 又’於2009-173772-A十，提出有於具有羥基之丙烯酸 系樹月曰中調配具有胺基之石夕烧化合物及異氰酸醋系交聯劑 而製成顯示良好之加工性的光學構件用黏著劑組合物之方 法。進而’於JP2009-215528-A中，提出於具有芳香環及 少里胺基並且具有叛基及/或經基之丙稀酸系樹脂中調配 161767.doc 201235436 異氰酸醋系交聯劑及矽烷偶合劑而製成同樣顯示良好之加 工性的光學膜用黏著劑組合物之方法。 如此’若將具有胺基之化合物或具有胺基之丙烯酸系樹 脂作為黏著劑組合物之一種成分，則可促進黏著劑之交聯 反應’但於構成成分中具有胺基之黏著劑組合物與某種剝 離膜接觸之情形時，存在剝離膜中之脫模劑與該胺基進行 反應而牢固地接著於剝離膜，有時使該剝離膜無法剝離之 問題。 另一方面，雖然附有黏著劑之光學膜係以其黏著劑層側 貼合於液晶單元上而製成液晶面板，但於以該狀態放置於 南溫或高溫高濕條件下、或反覆進行加熱與冷卻之情形 時，有時會隨著光學膜之尺寸變化，於黏著劑層中產生發 泡，或於光學膜與黏著劑層之間、或黏著劑層與液晶單元 玻璃之間產生浮起或剝離等，故而要求不產生上述不良情 形且耐久性優異。又，於暴露於高溫下之情形時，作用於 光學膜上之殘留應力之分佈變得不均，於光學膜之外周部 產生應力集中’結果有時於黑色顯示時產生外周部泛白之 現象、所謂發白（light leakage)，或產生顏色不均，故而亦 要求抑制該發白或顏色不均。進而，亦要求有二次加工 性’所謂二次加工性，係指將附有黏著劑之光學膜貼合於 液晶單70時，於存在不完善之情形時，將該光學膜暫時剝 離後再次重貼新的膜，於該剝離時黏著劑層隨著光學膜而 剝離，於單元玻璃上不殘留黏著劑，亦不產生污點等。 本發明之課題在於提供一種耐久性及二次加工性優異， 161767.doc 201235436 且形成黏著劑層後直至使裁剪等加工無問題地進行為止所 需要之固化時間較短，加工性優異之黏著劑片材及附有黏 著劑之光學膜；進而將該附有黏著劑之光學膜貼合於以液 晶單元作為代表例之玻璃基板上而提供一種光學積層體。 本發明者等人為了解決上述問題而進行了努力研究，結果 發現：若將如下黏著劑組合物形成為片狀，則可獲得於較 短之固化時間内顯示高凝膠分率且加工性優異之黏著劑片 材，該黏著劑組合物係於藉由以（甲基）丙烯酸酯作為主成 分且含有具有羥基之（甲基）丙烯酸系單體、及於自藉由聚 合而成為主鏈之部位分離規定原子數之位置具有羧基之 (甲基）丙烯酸酯單體的單體混合物之共聚合所獲得之丙烯 酸系樹脂中調配交聯劑而成。又，發現：若將該黏著劑片 材設置於光學膜之表面作為黏著劑層，則可獲得耐久性、 二次加工性及加工性優異之附有黏著劑之光學膜。 【發明内容】 即，本發明包含下述者。 [1] 一種黏著劑片材，其係將含有丙烯酸系樹脂（A) 1〇〇重 量份、以及交聯劑（B) 〇.〇1〜5重量份之黏著劑組合物形成 為片狀而獲得，該丙烯酸系樹脂（A)係由含有下式⑴所八 之（甲基）丙烯酸酯（A-1) 94.8〜99.89重量％、具有經基之（甲 基）丙烯酸系單體（A-2) 0.1〜5重量。/。、及下式（π)所示 I 羧基之（甲基）丙烯酸酯（A-3) 0.004〜0.2重量％的單體混合^ 所獲得之共聚物，且重量平均分子量為1〇〇萬〜2〇〇萬；0勿 16I767.doc 201235436 CH2==i"~^,—〇*™R2 (I) (式中’ Ri表示氫原子或甲基，R2表示碳數14以下之烧基 或碳數14以下之芳烷基’構成R2之氫原子可經基_〇_ (C2H4〇)n-R3取代’ η表示〇或1〜4之整數，r3表示碳數12以 下之烷基或碳數12以下之芳基） CH2=i-C-0—A-COOH (Π) Ο (式中’ R4表示氫原子或甲基，A表示碳數2〜4之2價有機 基）。 [2] 如上述[1 ]之黏著劑片材，其中將黏著劑組合物塗佈成 片狀2天後之凝膠分率相對於塗佈成片狀7天後之凝膠分率 的比為0.8以上。 [3] 如上述[1]或[2]之黏著劑片材，其中含羧基之（甲基）丙 烯酸酯（A-3)為丙烯酸2-羧基乙酯。 [4] 如上述⑴至[3]中任一項之黏著劑片材，其中交聯劑 (B)含有異氛酸醋系化合物。 [5] 如上述[1]至[4]中任—項之黏著劑片材，其中黏著劑组 合物進而含有矽烷系化合物（c)〇 〇3〜2重量份。 ⑷如上述⑴至附任-項之黏著劑片材，其係形成於塑 膠膜上。 m如上述[6]之黏著劑片材，其中塑膠臈為實施脫模處理 之剝離膜。 161767.doc 201235436 m -種附有黏著劑之光學膜，其係由光學膜及貼合於光 學膜上之如上述⑴至[5]中任―項之黏著劑片材所構成。 [9] 如上述[8]之附有黏著劑之光學膜其中光學膜係選自 偏光板及相位差膜者。 [10] 一種光學積層體，其係由玻璃基板、及以其黏著劑 片材側積層於玻璃基板上之如上述[8]或[9]之附有黏著劑 之光學膜所構成。 形成本發明之黏著劑片材之黏著劑組合物係將以於自藉 由聚合而成為主鏈之部位分離規定原子數之位置具有羧基 之（甲基）丙烯酸酯（A-3)作為構成成分的丙烯酸系樹脂（A) -又為主成分，並於其中調配交聯劑（B)，藉此可快速進行 交聯反應並可縮短將該黏著劑組合物塗佈成片狀後直至達 到規定之凝膠分率為止的固化時間，從而提高加工性。因 此，可縮短直至實施裁剪等加工為止所需要之固化時間。 又，將本發明之附有黏著劑之光學膜一旦積層於玻璃基 板上後，於存在稍微之異常之情形時，即便自玻璃基板上 與黏著劑一起剝離，亦較少於剝離後之玻璃基板之表面產 生糨糊殘餘或污點，可再次用作玻璃基板’成為二次加工 性優異者。 該附有黏著劑之光學膜例如藉由積層於液晶單元之玻璃 基板上而提供液晶顯示用光學積層體。該光學積層體於高 溫條件下或濕熱條件下且於反覆進行加熱與冷卻之環境 下，黏著劑片材吸收並緩和因光學膜及玻璃基板之尺寸變 化所產生之應力’故而減輕局部之應力集中，抑制黏著劑 161767.doc 201235436 層於玻璃基板中之浮起戋釗離望 ^ ^ a別離專。又，亦可防止暴露於高 溫下之情形之應力集中，永也 Ύ抑制發白或顏色不均之產生。 【實施方式】 以下，對本發明進行詳細說明。本發明之黏著劑片材係 將含有丙稀酸系樹脂(Α)及交聯劑W之黏著劑組合物形成 為片狀而成者。首先，對構成黏著劑組合物之各成分進行 [丙烯酸系樹脂（Α)] 於形成黏著劑片材之黏著劑組合物中，丙烯酸系樹脂 ⑷係將來自上述式⑴所示之（甲基）丙烯酸醋⑹）之結構 單位作為主成分’進而含有來自具有經基之（甲基）丙稀酸 系單體（Α·2)之結構單位、及來自上述式⑼所示之含幾基 之（甲基）丙稀酸醋（Α·3)之結構單位者。此處，所謂（f基） 丙稀酸，係、指可為丙稀酸或甲基丙烯酸之任—者，除此以 :卜’稱為(甲基)丙烯酸酯等時之「(甲基)」亦為相同之主 曰於本說明書中’有時分別將上述式⑴所示之(甲基)丙 婦酸MA-1)僅稱為「單體（A1)」，將具有經基之（甲基） 丙_系單體稱為「單體（Α·2)」，且將上述式（11) 所不之3羧基之（甲基）丙烯酸酯（Α-3)僅稱為「單體（Α_ 3)」。 於丙烯酸系樹脂（Α)成為主要之結構單位之上述式⑴ 中’Rl為氫原子或甲基，R2為碳數14以下（碳數卜⑷之烷 f或碳數14以下（碳數7〜14)之芳烷基。&所表示之烷基或 方烷基之各自之氫原子亦可經基_〇_(C2H4〇)n_R3取代。此 161767.doc 201235436 處，η表示0或1〜4之整數’ &表示碳數12以下（礙數1〜12) 之烷基或碳數12以下（碳數6〜12)之芳基。 單體（A-1)中，作為上述式（I)中之R2為非取代烷基者， 具體而言’可例示：如丙烯酸甲酯、丙烯酸乙酯、丙烯酸 丙酯、丙烯酸正丁酯、丙烯酸正辛酯、及丙烯酸十二烷酯 之類的直鏈狀丙烯酸（碳數1〜14)烷酯；如丙烯酸異丁酯、 丙烯酸2-乙基己酯、及丙烯酸異辛酯之類的分支狀丙烯酸 (碳數3〜14)烧酯；如曱基丙烯酸甲酯、甲基丙烯酸乙酯、 曱基丙烯酸丙酯、曱基丙烯酸正丁酯、曱基丙烯酸正辛 酯、及曱基丙烯酸十二烷酯之類的直鏈狀曱基丙烯酸（碳 數1~14)烷酯；以及如甲基丙烯酸異丁酯、.曱基丙烯酸2· 乙基己酯、及曱基丙稀酸異辛酯之類的分支狀甲基丙稀酸 (碳數3〜14)烷酯》 該等中’較佳為丙烯酸正丁酯，具體而言，較佳為以構 成丙烯酸系樹脂（A)之全部單體中之丙烯酸正丁酯為5〇重 量0/❶以上且滿足關於上述單體（A_丨）之規定之方式使用。 又’單體（A-1)中，作為式⑴中之尺2為（碳數7〜14)芳烷基 者，具體而言，可例示丙烯酸苄酯或曱基丙烯酸苄酯等。 繼而，單體（A-1)中，對於構成式⑴中之R2之烷基或芳 烧基之氫原子經基-〇_(C2H4〇)n_R3取代者進行說明。於該 基-0-(C2H4〇)n-R3中，n如先前定義般，為〇或卜4之整數， 尤佳為〇、1或2。又，Rs亦如先前定義般，為碳數12以下 (¼數1〜12)之烷基或碳數12以下（碳數6〜12)之芳基，於烷 基之碳數為3以上之情形時，可為直鏈，亦可分支。若列 161767.doc 201235436 舉構成之芳基之例，則除苯基或萘基以外，亦存在包含 甲苯基、二甲苯基、乙基苯基等之經核烷基取代之苯基、 聯本基（或本基苯基）等。R3尤佳為該等芳基。 單體（A-ι)中，式⑴中之I為烷基，作為其氫原子經 基·0-((：2Η4〇)η·Ιΐ3取代者，具體而言，可例示：如丙烯酸 2-甲氧基乙酯、丙烯酸乙氧基甲酯、丙烯酸2_苯氧基乙 酯、丙烯酸2-(2-苯氧基乙氧基）乙酯、及丙烯酸2_(鄰苯基 苯氧基）乙酯之類的丙烯酸之烷氧基烷酯、丙烯酸之芳氧 基烷酯或丙烯酸之芳氧基乙氧基烷酯；如甲基丙烯酸2_甲 氧基乙酯、甲基丙烯酸乙氧基甲酯、甲基丙烯酸2苯氧基 乙酯、甲基丙烯酸2-(2-苯氧基乙氧基）乙酯、及甲基丙烯 酸2-(鄰苯基苯氧基）乙酯之類的甲基丙烯酸之烷氧基烷 酯、曱基丙烯酸之芳氧基烷酯或曱基丙烯酸之芳氧基乙氧 基烷酯等。 該4單體（A-1)可分別單獨使用以外，除此以外亦可與 另1種以上混合使用。如上述般，單體（A—丨）尤佳為將丙烯 酸正丁酯作為主成分，除此以外，較有效為使相當於式（1) 之其他（甲基）丙烯酸酯共聚合。作為單體之較佳之組 成之一，可列舉如下者：以使於構成丙烯酸系樹脂（A)之 全部單體中丙烯酸正丁酯為50重量％以上，另外，以3〜15 重量°/❶之比例調配上述式⑴所示之式中之r2為氩原子經 基-0-(C2H4〇)n-R3(此處n及&表示與上述相同之意思）取代 之院基的（甲基）丙稀酸醋而成。 單體（A-2)為具有羥基之（甲基）丙烯酸系單體，作為其例 161767.doc 201235436 子，可列舉：（甲基）丙烯酸2_羥基乙酯、（甲基）丙烯酸3_羥 基丙酯、（曱基）丙烯酸4_羥基丁酯、（甲基）丙烯酸2_(2_羥 基乙氧基）乙酯等（曱基）丙烯酸（碳數丨〜6)羥基烷酯。該等 中，較佳為將丙烯酸2-羥基乙酯用作構成丙烯酸系樹脂 (A)之單體（A-2)之一。 單體（A-3)由上述式（11)表示。於該式（11)中，心為氫原子 或甲基，A為碳數2〜4之2價有機基。a所表示之2價有機基 典型為伸烷基’其亦較佳為直鍵之伸烷基，以連接（甲基） 丙烯酸部位CH2=C(R4)COO-與末端之羧基-coon之碳鍵串 聯且至少成為2個為前提’若碳數為3以上，則亦可分支。 式（II)中，較佳為丙烯酸酯’具體而言，可例示丙稀酸2· 叛基乙酯、丙浠酸3-叛基丙酯、丙稀酸4-叛基丁酯等丙稀 酸羧基（碳數1〜6)烷酯。當然，將該等丙烯酸酯變更為甲 基丙婦酸酯之化合物亦可成為單體（A- 3 )。 丙烯酸2-叛基乙酯通常係藉由丙稀酸之二聚化而生產， 於該情形時’除作為主成分之丙稀酸2 -叛基乙酯以外，大 多情況下作為丙烯酸本身、或與丙烯酸之三聚物以上之低 聚物的混合物而獲得並以混合物之形式直接販賣。當然， 亦可將含有該式（II)所示之含羧基之（甲基）丙烯酸酯（A_ 2)、與除此以外之含羧基之（甲基）丙烯酸系單體的混合物 用於共聚合。 於本發明所規定之丙烯酸系樹脂（A)中，來自上述式⑴ 所示之（甲基）.丙烯酸酯、即單體（A-1)之結構單位之含量為 94.8〜99.89重量％，來自具有羥基之（曱基）丙烯酸系單體 161767.doc 201235436 (A-2)之結構單位之含量為m〜5重量％，並且來自上述式 (jl)所不之3羧基之（甲基）丙烯酸酯、即單體（A·])之結構 :位之含量為0.01〜0.2重量％。藉由以如此限定之比例使 單體（A 1)、（Α·2)及（Α·3)#Μ，可製成顯示優異之加工 性，並且偏光板化，防止作為光學積層體而承受受熱歷程 時之發白’各種耐久性或二次加工性亦優異之黏著劑片 材。來自單體⑹）之結構單位之含量較佳為95重量％以 上，尤其是96重量％以上，且較佳為99 5重量％以下。來 自單體(Α-2)之結構單位之含量較佳為〇5重量％以上，且 較佳為4重量％以下，尤其是3重量％以下。進而，來自單 體（Α-3)之結構單位之含量較佳為〇 12重量。以下，尤其是 〇.1重量％以下。當然’分別來自單體(A1)、(A 2)及(a_” 之結構單位之合計量不超過100重量％。 本發明所使用之丙烯酸系樹脂亦可包含來自除以上 說明之單體（A-丨）、（A_2)及（A_3)以外之單體之結構單位。 若列舉除單體（A_1}、（A_2)及（A_3)以外之單體之例則有 具有除羥基以外之極性官能基之除式（1〗）以外之不飽和單 體、於分子内具有脂環式結構之（甲基）丙烯酸酯、苯乙烯 系單體、乙烯系單體、（甲基）丙烯醯胺衍生物、於分子内 具有複數個（曱基）丙烯醯基之單體等。 對於具有除羥基以外之極性官能基之除式（11)以外之不 飽和單體進行說明。此處，所謂除羥基以外之極性官能基 可為游離羧基、或以環氧環為首之雜環基等。先前單體 (3)之°卩分說明之丙稀酸本身或丙稀酸之三聚物以上之 161767.doc -14· 201235436 低聚物符合具有游離羧基之除式（π)以外之不飽和單體。 又’若列舉具有雜環基之不飽和單體之例，則有丙烯醯基 咪啉、乙烯基己内醯胺、Ν-乙烯基-2-吡咯烷酮、（曱基）丙 烯酸四氫糠酯 '己内酯改質丙烯酸四氫糠酯、（曱基）丙烯 ^ 3，4-%氧環己基甲酯、（曱基）丙稀酸縮水甘油酯等。 於使具有除羥基以外之極性官能基之不飽和單體共聚合 之情形時，將包含必需成分之具有羥基之（甲基）丙烯酸系 早體（Α·2)及上述式（11)所示之含羧基之（甲基）丙烯酸酯 3)的構成丙烯酸系樹脂（A)之全部單體作為基準，較佳為 使具有極性官能基之不飽和單體之合計量成為5重量％以 下’進而較佳為成為4重量％以下，尤佳為成為3重量。乂以 下。 繼而，對於於分子内具有脂,裒式結構之（甲基）丙稀酸醋 進行說明。所謂脂環式結構，係指碳數通常為5以上、較 佳為5〜7左右之環院結構彳舉具有脂環式結構之丙稀 酸醋之具體例’則有丙烯酸異冰片醋、丙烯酸環己醋、丙 稀酸雙環戊醋、丙烯酸環十n丙烯酸甲基環己酷、 丙烯酸三甲基環己酯、丙烯酸第三丁基環己酯、&乙氧基 二烯酸環己醋、丙烯酸環己基苯酿等。又，若列舉具有脂 %式結構之甲基㈣酸S旨之具體例，則有甲基丙烯酸里冰 片醋、甲基丙稀酸環己醋、甲基丙稀酸雙環戊醋、甲基丙 稀酸環十二朗、甲基丙稀酸甲基環㈣、甲基丙烯酸三 甲基5衣己西旨、曱基丙檢酿笛— τ丞丙烯酸第二丁基環己酯'甲基丙烯酸環 己基苯酯等。 161767.doc •15· 201235436 若列舉苯乙烯系單體之例，則除笨乙烯以外，有如曱基 本乙稀、一甲基本乙稀、二甲基苯乙稀、乙基苯乙稀、二 乙基苯乙烯、三乙基苯乙烯、丙基苯乙烯、丁基苯乙烯、 己基苯乙烯、庚基苯乙烯、及辛基苯乙烯之類的烷基苯乙 烯；如氟苯乙烯、氣苯乙烯、溴苯乙婦、二溴苯乙稀、及 碘苯乙烯之類的_化苯乙烯；進而，硝基苯乙烯、乙醯笨 乙烯、甲氧基苯乙烯、二乙烯基苯等。 若列舉乙烯系單體之例，則有如乙酸乙烯酯、丙酸乙稀 醋、丁酸乙稀醋、2 -乙基己酸乙稀g旨、及十二炫酸乙稀g旨 之類的脂肪酸乙稀酯；如氣化乙烯或溴化乙稀之類的鹵化 乙烯；如偏二氯乙烯之類的偏二南乙烯；如乙稀基吡咬、 乙稀基°比。各院酮、及乙浠基°卡0坐之類的含氮芳香族乙稀 基；如丁二烯、異戊二豨、及氣丁二稀之類的共輛二稀單 體；進而丙烯腈、甲基丙烯腈等。 若列舉（甲基）丙稀酿胺衍生物之例，則有N-經曱基（曱 基）丙稀醯胺、N-(2-羥基乙基）（甲基）丙烯醯胺、N-(3-羥基 丙基）（曱基）丙烯酿胺、N-(4-羥基丁基）（曱基）丙烯醯胺、 N-(5-羥基戊基）（曱基）丙烯醯胺、N-(6-羥基己基）（曱基）丙 稀酿胺、N-(曱氧基甲基）（曱基）丙婦酿胺、N-(乙氧基曱 基）（曱基）丙烯醯胺、N-(丙氧基甲基）（曱基）丙稀醯胺、N-(丁氧基甲基）（甲基）丙烯醯胺、N，N-二甲基（甲基）丙烯醯 胺、N，N-二乙基（曱基）丙烯醯胺、N-異丙基（甲基）丙烯醯 胺、N-(3-二甲基胺基丙基）（甲基）丙烯醯胺、N-(l，l-二甲 基-3-氧代丁基）（甲基）丙烯醯胺、N-[2-(2-側氧基-1-咪唑啶 161767.doc -16 · 201235436 基）乙基](曱基）丙烯醯胺、2-丙烯醯基胺基-2-曱基-1-丙項 酸等。 若列舉於分子内具有複數個（曱基）丙烯醯基之單體之 例’則有如1,4-丁二醇二（曱基）丙烯酸酯、丨，6_己二醇二 (甲基）丙烯酸酯、1，9-壬二醇二（曱基）丙烯酸酯、乙二醇二 (甲基）丙稀酸醋、一乙一醇二（曱基）丙稀酸醋、四乙二醇 二（甲基）丙烯酸酯、及三丙二醇二（曱基）丙烯酸酯之類的 於分子内具有2個（曱基）丙稀酿基之單體；如三經甲基丙院 三（曱基）丙烯酸酯之類的於分子内具有3個（甲基）丙稀醯基 之單體等。 於使成為丙烯酸系樹脂（A)之必需成分之除單體（A_丨）、 (A-2)及（A-3)以外且不具有極性官能基之單體共聚合之情 形時’其量係以構成丙烯酸系樹脂（A)之全部單體作為基 準’通常較佳成為5重量％以下，進而較佳為成為3重量0/〇 以下’尤佳為成為1重量。/。以下。 構成黏著劑組合物之樹脂成分亦可為混合2種以上之以 上說明之具有分別來自式（I)所示之（甲基）丙烯酸酯即單體 (A-1)、具有羥基之（甲基）丙烯酸系單體（a_2)，及式（π)所 示之含缓基之（甲基）丙烯酸酯即單體（Α_3)之結構單位的丙 稀酸系樹脂（Α)者。又’亦可於以規定之比例具有來自單 體（A-1)、（Α-2)及（Α-3)之結構單位之丙烯酸系樹脂中混 合與其不同之丙烯酸系樹脂。於該情形時，所混合之不同 之丙烯酸系樹脂例如可列舉具有來自上述式（I)之（甲基）丙 稀酸醋之結構單位且不具有極性官能基者等。以規定比例 161767.doc •17- 201235436 具有來自單體（A-l)、（A-2)及（A-3)之結構單位之丙烯酸系 樹脂（A)於丙烯酸系樹脂整體中，較佳為成為8〇重量0/〇以 上’進而較佳為成為90重量％以上。 藉由含有單體（A-l)、（A-2)及（A-3)之單體混合物之共聚 合而獲得之丙烯酸系樹脂（A)係採用藉由凝膠滲透層析儀 (GPC，gel-permeati〇n chromatography)所求出之標準聚苯 乙稀換算之重量平均分子量Mw於100萬〜200萬之範圍者。 若標準聚苯乙烯換算之重量平均分子量為1〇〇萬以上，則 有高溫高濕下之接著性提高’於玻璃基板與黏著劑片材之 間產生浮起或剝離之可能性變低的傾向，並且有二次加工 性亦提高之傾向，故較佳。又，若該重量平均分子量為 200萬以下’則即便貼合於該黏著劑片材上之光學膜之尺 寸發生變化，黏著劑層亦隨著該尺寸變化而變動，故於液 晶單元之周緣部的亮度與中心部的亮度之間亦不存在差 異’有抑制發白或顏色不均之傾向，故較佳。重量平均分 子量Mw與數平均分子量Μη之比Mw/Mn所表示之分子量分 佈並無特別限定，例如較佳為處於3〜7左右之範圍。 又’該丙烯酸系樹脂（A)為了表現黏著性，其玻璃轉移 概度較佳為處於_ 1 〇〜_60°C之範圍。樹脂之玻璃轉移溫度 可藉由示差掃描熱卡計進行測定。 構成黏著劑片材之丙烯酸系樹脂（A)例如可藉由溶液聚 合法、乳化聚合法、塊狀聚合法、懸浮聚合法等公知之各 種方法進行製造。於該丙烯酸系樹脂之製造時，通常使用 聚合起始劑。聚合起始劑相對於丙烯酸系樹脂之製造所使 161767.doc 201235436 用之全部單體之合計100重量份’使用〇 〇〇ι〜5重量份左 右。 ★作為聚合起始劑，使用熱聚合起始劑或光聚合起始劑 等。作為光量合起始劑’例如可列舉4_(2_經基乙氧基）苯 基羥基-2-丙基）酮等。作為熱聚合起始劑，例如可列 舉.如2,2'-偶氮二異丁腈、2,2,_偶氮二（2_甲基丁腈）、 丄，1-偶氮二（環己烷-1-腈）、2,2，_偶氮二（24_二曱基戊腈）、 2,2 -偶氮二（2,4·二甲基_4_甲氧基戊腈）、二曱基偶氮 一（2-丙酸甲酯）、及2,2·-偶氮二羥基甲基丙腈）之類的偶 氮系化合物；如十二烷基過氧化物、第三丁基過氧化氫、 過氡化苯曱醯基、第三丁基過氧化笨曱酸酯、過氧化氫異 丙笨、過氧化二碳酸二異丙酯、過氧化二碳酸二丙酯、過 氧化新癸酸第三丁酯、過氧化特戊酸第三丁酯、及（3,5,5_ 二甲基己醯基）過氧化物之類的有機過氧化物；如過硫酸 鉀、過硫酸銨、及過氧化氫之類的無機過氧化物等❶又 併用過氧化物與還原劑之氧化還原系起始劑等亦可用作聚 合起始劑。 作為丙烯酸系樹脂之製造方法，於以上所示之方法中， 較佳為溶液聚合法。 若列舉溶液聚合法之具體例進行說明，則可列舉如下方 法：將所需之單體及有機溶劑混合，於氮氣環境下添加熱 聚合起始劑，於40〜90°C左右、較佳為於60〜80。(：左右下授 拌3〜10小時左右。又，為了控制反應，可於聚合中連續或 間歇性地添加單體或熱聚合起始劑，或亦可以溶解於有機 161767.doc -19- 201235436 溶劑中之狀態添加。此處，作為有機溶劑，例如可使用： 如甲笨或一曱笨之類的芳香族烴類；如乙酸乙酯或乙酸丁 酯之類的酯類；如丙醇或異丙醇之類的脂肪族醇類；如丙 酮、甲基乙基酮、及甲基異丁基酮之類的酮類等。 [交聯劑（B)] 於如以上之丙烯酸系樹脂（A)中調配交聯劑（B)而製成黏 著劑組合物。交聯劑（B)為與丙烯酸系樹脂（A)中之作為極 性官能基之羥基或羧基反應，於分子内至少具有2個可使 丙烯酸系樹脂交聯之官能基的化合物，具體而言，可例示 異氰酸酯系化合物、環氧系化合物、金屬螯合物系化合 物、氮丙啶系化合物等。 異氰酸酯系化合物為於分子内至少具有2個異氰酸基 (-NCO)之化合物，例如可列舉：.甲苯二異氰酸酯、六亞甲 基二異氰酸酯、異佛爾酮二異氰酸酯、苯二亞甲基二異氰 、氫化笨二亞曱基二異氰酸酯、二苯基甲烷二異氰酸 酉曰氫化一苯基曱燒二異氰酸醋、冑二異氮酸醋、三苯基 甲烷三異氰酸酿等。又’使該等異氰酸醋化合物與如丙： 醇或三經甲基丙烧之類的多元醇反應之加合物、或使異氛 I s曰化合物成為二量體、三量體等者亦可成為黏著劑所使 用之交聯劑。亦可混合2種以上之異氰酸酯系化合物而使 用。 衣氧系化合物為於分子内至少具有2個環氧基之化合 物’例如可列舉：雙酚八型環氧樹脂、乙二醇二縮水甘油 鍵聚乙一醇二縮水甘油趟、甘油二縮水甘油喊、甘油三 161767.doc 201235436 縮水甘油醚、1，6-己二醇二縮水甘油醚、三羥甲基丙烷三 縮水甘油喊、N，N-二縮水甘油基苯胺、N，N，N，,N,_四縮水 甘油-間笨二甲胺等。亦可混合2種以上之環氧系化合物而 使用。 作為金屬螯合物’例如可列舉於如鋁、鐵、銅、鋅、 錫、鈦、鎳、銻、鎂、釩、鉻及锆之類的多價金屬中配位 乙醯丙酮或乙醯乙酸乙酯之化合物等。 氮丙咬系化合物為於分子内至少具有2個亦稱為乙稀亞 胺之含有1個氮原子與2個碳原子的3員環之骨架之化合 物，例如可列舉··二苯基曱烷_4,4，_雙（1_氮丙啶曱醯胺）、 曱苯-2,4-雙（1-氮丙啶曱醯胺）、三伸乙基三聚氰胺、間苯 二曱醯雙-1-(2-甲基氮丙啶）、三-1-氮丙啶基氧化膦、六亞 曱基-1，6-雙（1_氮丙啶甲醯胺）、三羥曱基丙烷三_p_氮丙啶 基丙酸酯、四羥曱基曱烷三-β-氮丙啶基丙酸酯等。 該等交聯劑中’較佳為使用異氰酸酯系化合物，尤其是 苯二亞曱基二異氰酸酯、甲苯二異氰酸酯或者六亞甲基二 異氰酸S旨；或使該等異氛酸g旨化合物與如丙三醇或三經曱 基丙烷之類的多元醇反應之加合物；或使異氰酸酯化合物 成為一 ·5:體、二置體等者；該等異氰酸醋系化合物之混合 物等。 作為尤佳之異氰酸酯系化合物，可列舉：使甲苯二異氣 酸酯、曱苯二異氰酸酯與多元醇反應之加合物、曱苯二異 氰酸酯之二量體、及甲笨二異氰酸酯之三量體。 交聯劑（Β)係以相對於丙烯酸系樹脂（Α)100重量份為 161767.doc -21- 201235436 0 · 01〜5重量伤之比例調配。交聯劑（b)之調配量較佳為相對 於丙烯酸系樹脂（A)100重量份為0.^重量份左右，進而較 佳為0.1〜1重量份左右。若交聯劑（B)相對於丙烯酸系樹脂 (A) 1〇〇重量份之量為〇 〇1重量份以上、尤其是〇1重量份以 上，則有黏著劑片材之耐久性提高之傾向，故較佳，又， 若為5重量份以下’則將附有黏著劑之光學膜用於液晶顯 不裝置時之發白變得不顯眼，故較佳。 [構成黏著劑組合物之其他成分] 於用以形成本發明之黏著劑片材之黏著劑組合物中，為 了提向該黏著劑片材與玻璃基板之密著性，較佳為含有矽 烷系化合物（C) ’尤佳為預先於調配交聯劑前之丙烯酸系 樹脂中含有矽烷系化合物（C)。 作為矽烷系化合物（c)，例如可列舉：乙烯三甲氧基矽 烷、乙烯三乙氧基矽烷、乙烯三（2·甲氧基乙氧基）矽烷、 3'缩水甘油氧基丙基三甲氧基矽烷、3'缩水甘油氧基丙基 甲基二甲氧基石夕燒、2-(3,4·環氧環己基）乙基三甲氧基石夕 烷、3-氣丙基甲基二曱氧基矽烷、3_氣丙基三甲氧基矽 烷3曱基丙烯醯氧基丙基三甲氧基矽烷、3_酼基丙基三 甲氧基矽烷、3'缩水甘油氧基丙基三甲氧基矽烷、3'缩水 甘油氧基丙基三乙氧基$院、3_縮水甘油氧基丙基二甲氧 基甲基㈣、3·縮水甘油氧基丙基乙氧基二甲基㈣等。 亦可使用2種以上之矽烷系化合物（c)。 矽烷系化合物（C)亦可為聚矽氧低聚物型者。若以（單 體Η單體)共聚物之形式表示聚矽氧低聚物，則例如可列 161767.doc -22- 201235436 舉如下者： 如3 -酼基丙基三曱氧基矽炫_四甲氧基矽炫共聚物、3 -巯 基丙基三曱氧基矽烷-四乙氧基矽烷共聚物、3-巯基丙基三 乙氧基矽烷-四甲氧基矽烷共聚物、及3-酼基丙基三乙氧基 矽烷-四乙氧基矽烷共聚物之類的含酼基丙基之共聚物； 如巯基甲基三甲氧基矽烷-四曱氧基矽烷共聚物、巯基 甲基三甲氧基矽烷-四乙氧基矽烷共聚物、酼基曱基三乙 氧基矽烷-四曱氧基矽烷共聚物、及巯基甲基三乙氧基矽 烧-四乙氧基矽烷共聚物之類的含酼基曱基之共聚物； 如3-甲基丙烯醯氧基丙基三甲氧基矽烷_四甲氧基矽烷 共聚物、3-甲基丙烯醯氧基丙基三曱氧基矽烷_四乙氧基矽 烧共聚物、3 -曱基丙烯醯氧基丙基三乙氧基矽烷_四甲氧基 石夕烧共聚物、3-曱基丙烯醯氧基丙基三乙氧基矽烷_四乙氧 基矽烷共聚物、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷_ 四曱氧基石夕院共聚物、3 -曱基丙婦酿氧基丙基甲基二曱氧 基矽烷-四乙氧基矽烷共聚物、3_甲基丙烯醯氧基丙基甲基 二乙氧基矽烷-四甲氧基矽烷共聚物、及3_甲基丙烯醯氧基 丙基曱基二乙氧基矽烷_四乙氧基矽烷共聚物之類的含甲 基丙烯酿氧基丙基之共聚物； 如3-丙烯醯氧基丙基三甲氧基矽烷_四甲氧基矽烷共聚 物、3-丙烯醯氧基丙基三曱氧基矽烷_四乙氧基矽烷共聚 物、3-丙烯醯氧基丙基三乙氧基矽烷·四甲氧基矽烷共聚 物3丙烯醯氧基丙基二乙氧基矽烷-四乙氧基矽烷共聚 物3丙烯醯氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷共 161767.doc -23· 201235436 聚物、3-丙烯醯氧基丙基甲基二甲氧基矽烷_四乙氧基矽烷 共聚物、3-丙烯醯氧基丙基曱基二乙氧基矽烷_四甲氧基矽 烷共聚物、及3-丙烯醯氧基丙基曱基二乙氧基矽烷_四乙氧 基石夕燒共聚物之類的含丙烯醯氧基丙基之共聚物； 如乙烯三曱氧基矽烷·四曱氧基矽烷共聚物、乙烯三甲 氧基石夕燒-四乙氧基矽烷共聚物、乙烯三乙氧基矽烷-四甲 氧基矽烷共聚物、乙烯三乙氧基矽烷_四乙氧基矽烷共聚 物、乙烯甲基二甲氧基矽烷-四甲氧基矽烷共聚物、乙烯 曱基二曱氧基矽烷-四乙氧基矽烷共聚物、乙烯甲基二乙 氧基石夕烧-四曱氧基矽烷共聚物、及乙烯曱基二乙氧基石夕 烧-四乙氧基矽烷共聚物之類的含乙烯基之共聚物等。 該等矽烷系化合物於較多之情形時為液體。黏著劑組合 物中之矽烷系化合物（C)之調配量以相對於丙烯酸系樹脂 (A)之固形分1〇〇重量份，通常為〇〇1〜1〇重量份左右，較佳 為0·03〜2重量份，進而較佳為〇 034重量份之比例使用。 若矽烷系化合物相對於丙烯酸系樹脂（Α)之固形分1〇〇重量 伤之量為0.01重量份以上、尤其是〇.〇3重量份以上，則黏 著劑片材與玻璃基板之密著性提高，故較佳。又，若該量 為10重量份以下、尤其是2重量份以下或i重量份以下，則 有抑制矽烷系化合物自黏著劑片材溢出之傾向，故較佳。 以上說明之黏著劑組合物為顯示良好之性能者，於與既 定之剝離膜接觸之情形時，為了避免牢固地接著，較佳為 不含有胺基。尤佳為不具有三級胺基。 於黏著劑組合物中，亦可進而調配交聯觸媒、抗靜電 161767.doc •24· 201235436 劑、耐候穩定劑、膠黏劑、可塑劑、軟化劑、染料、顏 料、無機填料、除丙烯酸系樹脂（A)以外之樹脂等。又， 於黏著劑組合物中調配紫外線硬化性化合物，形成黏著劑 片材後照射紫外線而使其硬化，製成更硬之黏著劑層亦有 用。其中，若於黏著劑組合物中調配交聯劑及交聯觸媒， 則可藉由短時間之固化而製備黏著劑片材，於所獲得之附 有黏著劑之光學膜中，可抑制於光學膜與黏著劑片材之間 產生浮起或剝離或於黏著劑片材内產生發泡，且二次加工 性亦有時變得更加良好。 構成黏著劑組合物之該等各成分係於溶解於溶劑中之狀 態下混合，塗佈於適當之基材上，使其乾燥而製成黏著劑 片材。此處’所用之基材通常為塑膠膜，作為其典型之 例’可列舉實施脫模處理之剝離膜。剝離膜例如可為於包 含聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碳酸 酯、聚芳酯等各種樹脂之膜之形成黏著劑片材之面實施如 聚石夕氧處理之類的脫模處理者等。 [黏著劑片材之凝膠分率] 藉由使用以上所說明之黏著劑組合物形成本發明之黏著 劑片材’可將使其塗佈成片狀後於室溫下放置2天後之凝 膠分率相對於使其塗佈成片狀後於室溫下放置7天後之凝 膠分率的比設為0.8以上。該比為〇·8以上，係指塗佈成片 狀後快速進行交聯反應，於2天時黏著劑之硬化大致結 束。即’該比成為加工性之大致目標。此處，凝膠分率係 按照以下（1)〜(4)而測定之值。 161767.doc -25- 201235436 (1) 將面積約為8 cmx約8 cm之黏著劑片材、與包含約 10 cmx約1〇 cm之SljS304之金屬網（將其重量設為Wm)貼 合0 (2) 稱量上述（1)所獲得之貼合物，將其重量設為ws， 繼而以包裹黏著劑片材之方式摺疊4次並用鐵絲訂書機（訂 書機）固定後進行稱量，將其重量設為Wb。 (3) 將上述（2)中訂書機固定之網放入玻璃容器，加入乙 酸乙醋60 mL浸潰後’將該玻璃容器於室溫下保管3天。 (4) 自玻璃容器取出網’於i2〇〇c下乾燥24小時後進行 稱量’將其重量設為Wa，根據以下式計算凝膠分率。 凝膠分率（重量 ％)=[{Wa-(Wb-Ws)-Wm}/(Ws-Wm)]xl00 黏著劑片材如上所述大多情況下於製造後花費一定時間 進行固化而使其進行交聯反應，使其成為顯示某種程度之 凝膠分率之狀態而使用。於如此進行交聯反應之狀態、即 固化終止之狀態下之凝膠分率例如可根據形成其之黏著劑 組合物之有效成分的丙烯酸系樹脂（A)之種類或交聯劑之 量而進行調整。具體而言，若增加丙烯酸系樹脂（A)中之 包含單體（A_2)及單體（A-3)之具有極性官能基的單體之 量，或增加黏著劑組合物中之交聯劑（B)之量，則凝膠分 率變同，故只要藉由調節該等之量而調整凝膠分率即可。 [附有黏著劑之光學膜] 本發明之附有黏著劑之光學膜為於光學膜之至少一面貼 〇由如以上之黏著劑組合物所形成之黏著劑片材而成者。 於如此黏㈣片#貼合於光學膜之狀態之附有黏著劑之光 161767.doc -26- 201235436 學膜、或其進而積層於玻璃基板之狀態之光學積層體中， 於本說明書中有時將該黏著劑片材之層僅稱為「黏著劑 層」。所謂附有黏著劑之光學膜所使用之光學膜，係指具 有光學特性之膜’例如可列舉偏光板、相位差膜等。 所謂偏光板，係指對於自然光等入射光具有射出偏光之 功能之光學膜。於偏光板中，有具有吸收包含某方向之振 動面之直線偏光且穿透包含與其正交之振動面之直線偏光 之丨生質的直線偏光板；具有反射包含某方向之振動面之直 線偏光且穿透包含與其正交之振動面之直線偏光之性質的 偏光分離板；積層偏光板與後述之相位差膜之橢圓偏光板 等。作為偏光板、尤其是表現直線偏光板之功能之偏光膜 (有時稱為偏光子）的較佳之具體例’可列舉於單轴延伸之 聚乙烯醇系樹脂膜中吸附配向碘或二色性染料等二色性色 素者。 所謂相位差膜，係指顯示光學異向性之光學膜，例如可 列舉藉由將包含聚乙烯醇、聚碳酸酯、聚酯、聚芳酯、聚 醢亞胺、聚烯烴、環狀聚烯烴、聚苯乙烯、聚砜、聚醚 颯、聚偏二氟乙烯/聚甲基丙烯酸曱酯、液晶聚酯、乙醯 纖維素、乙烯_乙酸乙烯酯共聚物皂化物、聚氯化乙烯等 之同分子膜延伸至1.01〜6倍左右而獲得之延伸膜等。其 中’較佳為將聚碳酸酯膜或環狀聚烯烴系膜單軸延伸或雙 轴延伸而成之高分子膜。有被稱為單軸性位相差膜、廣視 野角相位差膜、低光彈性模數相位差膜等者，對於任一者 均可使用。 161767.doc •27- 201235436 又’藉由液晶性化合物之塗佈、配向而表現光學異向性 之膜、或藉由無機層狀化合物之塗佈而表現光學異向性之 膜亦可用作相位差膜。於該相位差膜中，有稱為温度補償 型相位差膜者、及自新曰本石油（股份有限公司）以「LC 膜j之商品名販賣且棒狀液晶扭轉而配向之膜、同樣地自 新口本石油（股份有限公司）以「NH膜」之商品名販賣且棒 狀液晶傾斜配向之膜、自Fuji Film(股份有限公司）以「WV 膜」之商品名販賣且圓盤狀液晶傾斜配向之膜、自住友化 學（股份有限公司）以「VAC膜」之商品名販賣且完全雙軸 配向型之膜、同樣地自住友化學（股份有限公司）以「nevv VAC膜」之商品名販賣且雙軸配向型之膜等。 進而’於該等光學膜中黏著保護膜者亦可用作光學膜。 作為保護膜，使用透明之樹脂膜，作為該透明樹脂，例如 可列舉：三乙醯纖維素或二乙醯纖維素所代表之乙醯纖維 素系樹脂’聚甲基丙烯酸甲酯所代表之曱基丙烯酸樹脂、 聚醋樹脂、聚烯烴系樹脂、聚碳酸酯樹脂 '聚醚醚酮樹 脂、聚硬樹脂等。於構成保護膜之樹脂中，亦可調配水楊 酸酯系化合物、二苯曱酮系化合物、苯并三唑系化合物、 三唯系化合物、氰基丙烯酸酯系化合物、鎳絡鹽系化合物 等紫外線吸收劑》作為保護膜，可較佳地使用三乙醯纖維 素膜等乙醯纖維素系樹脂膜。 於以上所說明之光學膜中，直線偏光板大多情況下以構 成其之偏光膜、例如於包含聚乙烯醇系樹脂之偏光膜之單 面或兩面黏著保護膜的狀態使用。又，上述橢圓偏光板為 161767.doc -28 - 201235436 積層直線偏光板與相位差膜者，該直線偏光板大多為於偏 光膜之單面或兩面黏著保護膜之狀態。於該橢圓偏光板中 貼合本發明之黏著劑片材之情形時，通常貼合於該相位差 膜側。 附有黏著劑之光學膜較佳為於其黏著劑層之表面黏著如 上述之實施脫模處理之剝離膜而保護黏著劑層表面直至使 用時為止。如此設置剝離膜之附有黏著劑之光學膜例如可 藉由如下方法等進行製造：於剝離膜之脫模處理面塗佈上 述黏著劑組合物並形成黏著劑片材，將所獲得之黏著劑片 材積層於光學膜之方法；於光學膜之上塗佈黏著劑組合物 並形成黏著劑片材，於其黏著劑面貼合剝離膜而加以保 護’從而製成附有黏著劑之光學膜之方法等。 形成於光學膜上之黏著劑層之厚度並無特別限定，通常 較佳為3 0 μιη以下’且較佳為1 〇 以上，進而較佳為 15〜25 μπι。若黏著劑層之厚度為3〇 μηι以下，則有高溫高 濕下之接著性提高，於玻璃基板與黏著劑層之間產生浮起 或剝離之可能性變低之傾向’並且有二次加工性提高之傾 向，故較佳，又，若其厚度為1 〇 μιη以上，則即便其所貼 合之光學膜之尺寸發生變化，黏著層亦隨著該尺寸變化而 變動’故於液晶單元之周緣部的亮度與中心部的亮度之間 亦不存在差異，有抑制發白或顏色不均之傾向，故較佳。 本發明之附有黏著劑之光學膜於黏著於玻璃基板製成光 學積層體後’有稍微之不妥而自玻璃基板上剝離該光學膜 之情形時’黏著劑層隨著光學膜而剝離，於與黏著劑層鄰 161767.doc •29· 201235436 接之玻璃基板之表面幾乎未產生污點或槐糊殘餘等，故容 易於剝離後之玻璃基板再次重貼附有黏著劑之光學膜。 即，所謂二次加工性優異。 [光學積層體] 本發明之附有黏著劑之光學膜可將其黏著劑層侧積層於 玻璃基板上而製成光學積層體。於將附有黏著劑之光學膜 積層於玻璃基板而製成光學積層體時，例如只要自如上述 般而獲得之附有黏著劑之光學膜剝離剝離膜，將露出之黏 著劑層面貼合於玻璃基板之表面即可。作為玻璃基板，例 如可列舉液晶單元之玻璃基板、防眩用玻璃、太陽眼鏡用 玻璃等。其中，於液晶單元之前面側（視認側）之玻璃基板 積層附有黏著劑之光學膜（上偏光板）且於液晶單元之背面 側之玻璃基板積層另一個附有黏著劑之光學膜（下偏光板） 而成之光學積層體由於可用作用於液晶顯示裝置之面板 (液晶面板），故較佳。作為玻璃基板之材料，例如有鈉鈣 玻璃、低鹼玻璃、無鹼玻璃等，液晶單元可較佳地使用無 鹼玻璃。 關於本發明之光學積層體，將若干個較佳之層構成之例 以剖面模式圖示於圖1。於圖1(A)所示之例中，於偏光膜J 之單面上將具有表面處理層2之保護膜3黏著於與該表面處 理層2為相反側之面而構成偏光板5。 於該例中，偏光板5亦同時成為本發明中之所謂光學膜 1 〇。於偏光膜1之與保護膜3為相反側之面設置黏著劑層2〇 而構成附有黏著劑之光學膜25 ^並且將該黏著劑層2〇之與 161767.doc •30· 201235436 偏光板5為相反側之面貼合於玻璃基板之液晶單元3 〇上而 構成光學積層體40。 於圖1(B)所示之例中’於偏光膜1之單面上將具有表面 處理層2之第一保護膜3黏著於與該表面處理層2為相反側 之面，於偏光膜1之其他面黏著第二保護膜4而構成偏光板 5。於該例中，偏光板5同時亦成為本發明中之所謂光學膜 1〇。於構成偏光板5之第二保膜4之外側設置黏著劑層2〇而 構成附有黏著劑之光學膜25。並且將該黏著劑層2〇之與偏 光板5為相反側之面貼合於玻璃基板之液晶單元3 〇上而構 成光學積層體40。 於圖1(C)所示之例中，於偏光膜i之單面上將具有表面 處理層2之保護膜3黏著於與該表面處理層2為相反側之面 而構成偏光板5。於偏光膜丨之與保護膜3為相反側之面， 經由層間黏著劑8黏著相位差膜7而構成光學膜1〇。於構成 光學膜10之相位差膜7之外側設置黏著劑層2〇而構成附有 黏著劑之光學膜25。 並且將該黏著劑層20之與光學膜1〇為相反側之面貼合於 玻璃基板之液晶單元3〇,從而製成光學積層體4〇。 又，於圖1(D)所示之例中，於偏光膜丨之單面上將具有 表面處理層2之第一保護膜3黏著於與該表面處理層2:相 反側之面’於偏光膜！之其他面黏著第二保護膜*而構成偏 光板5。於構成偏光板5之第二保護膜4之外側，經由層間 黏著劑8黏著相位差膜7而構成光學膜10。於構成光學膜10 之相位差臈7之外側設置黏著劑㈣而構成附有黏著劑之 I61767.doc •31· 201235436 光學膜25 ^並且將該黏著劑層2〇之與光學膜1〇為相反側之 面貼合於玻璃基板之液晶單元3〇上而構成光學積層體4〇。 於該等之例中，第一保護膜3及第二保護膜4通常由三乙 醢纖維素膜構成，除此以外，亦可由先前敍述之各種透明 樹脂膜構成。又，形成於第一保護膜3之表面之表面處理 層可為硬塗層、防眩層、抗反射層、抗靜電層等。 於該等中，亦可設置複數個層β 如圖1之（C)及（D)所示之例般，於偏光板5積層相位差膜 7之清形時，若為中小型液晶顯示裝置，則作為該相位差 膜7之較佳之例，可列舉1/4波長板。於該情形時，通常以 使偏光板5之吸收軸與1/4波長板的相位差膜7之遲相轴大 致以45度交差之方式進行配置，有時亦根據液晶單元3〇之 特性，將該角度自45度偏移某程度。另一方面，若為電視 等大型液晶顯示裝置，則為了液晶單元3〇之相位差補償或 視野角補償，使用符合該液晶單元3〇之特性且具有各種相 位差值之相位差膜。 於該晴形時，通常以使偏光板5之吸收軸與相位差膜7之 遲相軸成為大致正交或大致平行之關係之方式進行配置。 於由1 /4波長板構成相位差膜7之情形時，可較佳地使用單 軸或雙軸之延伸膜。又，於為了液晶單元3〇之相位差補償 或視野角補償而設置相位差膜7之情形時，除單轴或雙軸 延伸膜以外，亦可將除單軸或雙軸延伸以外亦於厚度方向 配向之膜、於支持膜上塗佈液晶等相位差表現物質並配向 固定之膜等被稱為光學補償膜者用作相位差膜7 ^ I6I767.doc •32· 201235436 同樣’如圖1之（C)及（D)所示之例般，於經由層間黏著 劑8而貼合偏光板5與相位差膜7之情形時，該層間黏著劑8 通常之例為使用通常之丙稀酸系黏著劑，此處當然亦可使 用本發明所規定之黏著劑月材。如先前所述之大型液晶顯 示裝置般，於以使偏光板5之吸收軸與相位差膜7之遲相軸 成為大致正交或大致平行之關係之方式進行配置之情形 時，於可將偏光板5與相位差膜7進行報對輥（r〇ii t〇 r〇u)貼 合而不要求兩者間之再剝離性之用途中，亦可使用一旦接 著後便牢固地接合而無法剝離之接著劑代替圖丨之（c)及 (D)所示之層間黏著劑8。作為該接著劑，例如可列舉由水 溶液或水分散液構成且藉由使溶劑之水蒸發而表現接著力 之水系接著劑、藉由紫外線照射而硬化並表現接著力之紫 外線硬化型接著劑等》 再者，圖1之（C)及（D)所示之於相位差膜7上形成黏著劑 層20者本身亦可以其本身之形式而廣泛通用，可成為本發 明中之所謂附有黏著劑之光學膜。於相位差膜上形成黏著 劑層之附有黏著劑之光學膜除可將該黏著劑層貼合於玻璃 基板之液晶單元並製成光學積層體以外，亦可於該相位差 膜側貼合偏光板而製成其他附有黏著劑之光學膜。 圖1係表示設想將附有黏著劑之光學膜25配置於液晶單 元30之視認側之情形的例子，本發明之附有黏著劑之光學 膜亦可配置於液晶單元之背面側、即背光側。於將本發明 之附有黏著劑之光學膜配置於液晶單元之背面側之情形 時，採用不具有表面處理層之保護膜代替圖丨所示之具有 161767.doc -33- 201235436 表面處理層2之保護膜3，其他可以與圖1之（A)〜(D)相同之 方式構成。又，於該情形時’亦可於構成偏光板之保護膜 之外側設置亮度提高膜、集光膜、擴散膜等已知配置於液 晶單元之背面側之各種光學膜。 如以上所說明般’本發明之光學積層體可較佳地用於液 晶顯不裝置。由本發明之光學積層體所形成之液晶顯示裝 置例如可用於包含筆記型、桌上型、PDA(Pers〇nal Dighal201235436 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to an adhesive sheet and an optical film with an adhesive attached thereto. The optical film to which the present invention is applied includes, for example, a polarizing plate or a phase difference. membrane. The present invention also relates to an optical laminate using the optical film with an adhesive and preferably for liquid crystal display. [Prior Art] The polarizing plate is widely used because it is mounted in a liquid crystal display device. The polarizing plate is generally used for a two-layer transparent protective film of a polarizing film, and an adhesive layer is formed on the surface of at least one of the protective films, and a state in which the peeling film is bonded to the adhesive layer is widely used. Further, a retardation film is laminated on a polarizing plate in which a protective film is bonded to both surfaces of the polarizing film to form an elliptically polarizing plate, and the phase difference is obtained. The adhesive layer/release film was sequentially attached to the film side. Further, the adhesive layer/release film may be attached to the surface of the retardation film in order. In the present specification, the polarizing plate, the elliptically polarizing plate, the retardation film, and the like in which the adhesive layer is provided are collectively referred to as an optical film. Before the bonding to the liquid crystal cell, the optical film provided with the pressure-sensitive adhesive layer is cut to a predetermined size, and then the release film is peeled off and bonded to the liquid crystal cell via the exposed adhesive layer. Such an optical film provided with an adhesive layer has a problem of workability in which the adhesive layer is easily broken at the time of cutting. Therefore, usually, after the formation of the adhesive layer, it takes a sufficient time to cure (so-called curing, which takes a certain period of time after the formation of the adhesive layer to increase the gel fraction) and is used for use. Productive aspect 161767. As for doc 201235436, there is still room for improvement. From the viewpoint of transparency or adhesion, a large amount of an acrylate is used as a main component in an adhesive used for an optical film, and is produced by copolymerizing a monomer having a polar functional group such as a hydroxyl group or a carboxyl group. Acrylic resin. A crosslinking agent is blended in the acrylic resin to impart the necessary cohesive force. Here, the term "crosslinking agent" means a compound having at least two functional groups capable of reacting with a polar functional group constituting the acrylic resin to form a crosslinked structure, and specifically, an isocyanate compound and a ring. An oxygen compound, a metal chelate compound, an amine compound, or the like. Among them, the 'isocyanate compound can be widely used as a crosslinking agent. That is, an 'isocyanate-based crosslinking agent having at least two isocyanato groups (_NC0) in the molecule is blended in an acrylic resin having a polar functional group, whereby the functional group and the crosslinking agent in the acrylic resin are The isocyanate groups react with time and form a crosslinked structure, exhibiting cohesive force and workability. Therefore, as long as the speed of the crosslinking reaction is increased, the time required until sufficient processing property is displayed can be shortened. As a method of increasing the rate of the crosslinking reaction, for example, JP 2004-190012-A describes a method of formulating an amine compound as a crosslinking catalyst. In this case, it is preferably an isocyanate as a crosslinking agent. a compound. Further, in Japanese Patent Publication No. 2009-173772-A, it is proposed to prepare an optical film exhibiting good processability by blending an amine-based compound with an amine group and an isocyanate-based cross-linking agent in an acrylic resin having a hydroxyl group. A method of using an adhesive composition for a member. Further, in JP2009-215528-A, it is proposed to be formulated in an acrylic resin having an aromatic ring and a oligoamine group and having a thiol and/or a trans group. Doc 201235436 Isocyanate-based cross-linking agent and decane coupling agent are used to produce a pressure-sensitive adhesive composition for an optical film which also exhibits good workability. When the compound having an amine group or the acrylic resin having an amine group is used as a component of the adhesive composition, the crosslinking reaction of the adhesive can be promoted, but the adhesive composition having an amine group in the constituent component is When a certain release film is in contact with each other, there is a problem in that the release agent in the release film reacts with the amine group to firmly adhere to the release film, and the release film may not be peeled off. On the other hand, although the optical film with an adhesive is attached to the liquid crystal cell with the adhesive layer side to form a liquid crystal panel, it is placed in this state under conditions of south temperature or high temperature and high humidity, or repeated. In the case of heating and cooling, foaming may occur in the adhesive layer depending on the size of the optical film, or between the optical film and the adhesive layer, or between the adhesive layer and the liquid crystal cell glass. Since it is peeling off or peeling, etc., it is required that the above-mentioned malfunction is not produced and it is excellent in durability. Further, when exposed to a high temperature, the distribution of the residual stress acting on the optical film becomes uneven, and stress concentration occurs at the outer periphery of the optical film. As a result, the outer peripheral portion is whitened in the case of black display. The so-called light leakage or color unevenness is also required to suppress the blush or color unevenness. Further, it is required to have secondary workability. The so-called secondary workability means that when the optical film with the adhesive is bonded to the liquid crystal cell 70, when the film is imperfect, the optical film is temporarily peeled off and then again. A new film is reattached, and the adhesive layer is peeled off along with the optical film at the time of peeling, and no adhesive remains on the unit glass, and no stain or the like is generated. An object of the present invention is to provide an excellent durability and secondary workability, 161767. Doc 201235436 After the formation of the adhesive layer, the curing time required for the processing such as cutting is not problematic, and the adhesive sheet having excellent workability and the optical film with the adhesive are attached; further, the adhesive is attached thereto. The optical film is bonded to a glass substrate having a liquid crystal cell as a representative example to provide an optical laminate. In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that when the following adhesive composition is formed into a sheet form, it is possible to exhibit a high gel fraction and excellent processability in a short curing time. An adhesive sheet which is obtained by using (meth) acrylate as a main component and containing a (meth)acrylic monomer having a hydroxyl group, and being polymerized as a main chain The acrylic resin obtained by copolymerization of a monomer mixture having a carboxyl group (meth) acrylate monomer at a position where the number of atoms is defined is determined by disposing a crosslinking agent. Further, it has been found that when the pressure-sensitive adhesive sheet is placed on the surface of the optical film as an adhesive layer, an optical film with an adhesive having excellent durability, secondary workability, and workability can be obtained. SUMMARY OF THE INVENTION That is, the present invention includes the following. [1] An adhesive sheet comprising 1 part by weight of an acrylic resin (A) and a crosslinking agent (B). The adhesive composition of 〇1 to 5 parts by weight is obtained in the form of a sheet, and the acrylic resin (A) is obtained by containing (meth) acrylate (A-1) of the following formula (1). 8~99. 89% by weight of a (meth)acrylic monomer (A-2) having a mercapto group. 1 to 5 weight. /. And the following formula (π) shows the carboxyl group (meth) acrylate (A-3). 004~0. 2% by weight of the monomer is mixed with the obtained copolymer, and the weight average molecular weight is 1 million to 2 million; 0 does not 16I767. Doc 201235436 CH2==i"~^,—〇*TMR2 (I) (wherein Ri represents a hydrogen atom or a methyl group, and R2 represents a burnt group having a carbon number of 14 or less or an aralkyl group having a carbon number of 14 or less] The hydrogen atom of R2 may be substituted by the group _〇_(C2H4〇)n-R3, 'η represents 〇 or an integer of 1 to 4, and r3 represents an alkyl group having 12 or less carbon atoms or an aryl group having 12 or less carbon atoms) CH2=iC -0-A-COOH (Π) Ο (wherein R4 represents a hydrogen atom or a methyl group, and A represents a divalent organic group having 2 to 4 carbon atoms). [2] The adhesive sheet according to the above [1], wherein the ratio of the gel fraction after the adhesive composition is applied to the sheet form for 2 days with respect to the gel fraction after 7 days of application to the sheet form Is 0. 8 or more. [3] The adhesive sheet according to the above [1] or [2] wherein the carboxyl group-containing (meth) acrylate (A-3) is 2-carboxyethyl acrylate. [4] The adhesive sheet according to any one of the above (1) to (3) wherein the crosslinking agent (B) contains an oleic acid-based compound. [5] The adhesive sheet according to any one of the above [1] to [4] wherein the adhesive composition further contains 3 to 2 parts by weight of the decane-based compound (c). (4) An adhesive sheet according to the above (1) to the appended item, which is formed on a plastic film. The adhesive sheet according to the above [6], wherein the plastic enamel is a release film subjected to a release treatment. 161767. Doc 201235436 m - An optical film with an adhesive comprising an optical film and an adhesive sheet as described in any one of the above (1) to [5] attached to an optical film. [9] The optical film with an adhesive as described in [8] above, wherein the optical film is selected from the group consisting of a polarizing plate and a retardation film. [10] An optical layered body comprising a glass substrate and an optical film with an adhesive as described in [8] or [9] above, which is laminated on the glass substrate side of the adhesive sheet. The adhesive composition for forming the adhesive sheet of the present invention is a component which has a carboxyl group (meth) acrylate (A-3) at a position where a predetermined number of atoms is separated from a portion which is polymerized as a main chain. Acrylic resin (A) - as a main component, and a crosslinking agent (B) is blended therein, whereby the crosslinking reaction can be quickly carried out and the adhesive composition can be shortened until it reaches the specification. The curing time until the gel fraction is increased, thereby improving the workability. Therefore, the curing time required until the processing such as cutting is performed can be shortened. Moreover, when the optical film with the adhesive of the present invention is laminated on the glass substrate, even if it is slightly abnormal, even if it is peeled off from the glass substrate together with the adhesive, it is less than the glass substrate after peeling. The surface of the surface is stained or stained, and can be used again as a glass substrate to become excellent in secondary workability. The optical film with an adhesive is provided, for example, by laminating on a glass substrate of a liquid crystal cell to provide an optical laminate for liquid crystal display. The optical layered body absorbs and relaxes the stress caused by the dimensional change of the optical film and the glass substrate under high temperature conditions or under humid heat and under repeated heating and cooling conditions, thereby alleviating local stress concentration. , inhibiting adhesive 161767. Doc 201235436 Layers floating in the glass substrate 戋钊 戋钊 ^ ^ a separate from the special. Moreover, it is possible to prevent stress concentration in the case of exposure to high temperatures, and to suppress blushing or color unevenness. [Embodiment] Hereinafter, the present invention will be described in detail. The adhesive sheet of the present invention is obtained by forming an adhesive composition containing an acrylic resin and a crosslinking agent W into a sheet form. First, the [acrylic resin (Α)] is applied to each of the components constituting the adhesive composition in the adhesive composition for forming the adhesive sheet, and the acrylic resin (4) is derived from the (meth) group represented by the above formula (1). The structural unit of acryl vinegar (6)) as a main component 'further contains a structural unit derived from a (meth)acrylic acid monomer (Α·2) having a trans group, and a certain group derived from the above formula (9) The structural unit of methyl acrylate vinegar (Α·3). Here, the "f-based" acrylic acid, which means that it can be either acrylic acid or methacrylic acid, is referred to as "(methyl) acrylate, etc." The same is true in the present specification. 'The (meth) acetoacetate MA-1 shown in the above formula (1) is sometimes referred to as "monomer (A1), respectively), and will have a base. The (methyl)-propyl-based monomer is referred to as "monomer (Α·2)", and the 3-carboxyl (meth)acrylate (Α-3) of the above formula (11) is simply referred to as "single". Body (Α_ 3)". In the above formula (1) in which the acrylic resin (Α) is the main structural unit, 'R1 is a hydrogen atom or a methyl group, and R2 is a carbon number of 14 or less (carbon number (4) of an alkane f or a carbon number of 14 or less (carbon number of 7~) 14) The aralkyl group and the hydrogen atom of the alkyl group or the aryl group represented by the group may also be substituted by the group _〇_(C2H4〇)n_R3. This 161767. Doc 201235436, η represents an integer of 0 or 1 to 4' & represents an alkyl group having a carbon number of 12 or less (in hinder 1 to 12) or an aryl group having a carbon number of 12 or less (carbon number: 6 to 12). In the monomer (A-1), as the unsubstituted alkyl group in the above formula (I), R2 is specifically exemplified by methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, Linear acrylic acid (carbon number 1 to 14) alkyl esters such as n-octyl acrylate and dodecyl acrylate; such as isobutyl acrylate, 2-ethylhexyl acrylate, and isooctyl acrylate Branched acrylic acid (carbon number 3 to 14) alkyl ester; such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, and methacrylic acid a linear thioglycolic acid (C14-1) alkyl ester such as dodecyl ester; and isobutyl methacrylate, Branched methacrylic acid (carbon number 3 to 14) alkyl ester such as 2, ethylhexyl methacrylate and isooctyl decyl acrylate, etc. Specifically, it is preferably used in such a manner that the n-butyl acrylate in all the monomers constituting the acrylic resin (A) has a weight of 5 Å or more and satisfies the requirements for the above monomer (A_丨). . Further, in the monomer (A-1), the rule 2 in the formula (1) is a (carbon number: 7 to 14) aralkyl group, and specific examples thereof include benzyl acrylate or benzyl methacrylate. Then, in the monomer (A-1), the hydrogen atom constituting the alkyl group or the aryl group of R2 in the formula (1) is replaced by the group -〇_(C2H4〇)n_R3. In the group -0-(C2H4〇)n-R3, n is an integer of 〇 or 卜, as defined above, and is preferably 〇, 1 or 2. Further, Rs is also an alkyl group having a carbon number of 12 or less (1⁄4 1 to 12) or an aryl group having a carbon number of 12 or less (carbon number: 6 to 12) as defined above, and the carbon number of the alkyl group is 3 or more. In the case of a straight chain, it can also be branched. If column 161767. Doc 201235436 In the case of the aryl group, in addition to the phenyl or naphthyl group, a phenyl group, a phenyl group, or a phenyl group substituted with a tolyl group, a xylyl group, an ethylphenyl group or the like may be present. Phenylphenyl) and the like. R3 is especially preferred for these aryl groups. In the monomer (A-I), I in the formula (1) is an alkyl group, and as its hydrogen atom is substituted by a group -0-((:2Η4〇)η·Ιΐ3, specifically, it is exemplified as: 2-ethyl acrylate Methoxyethyl ester, ethoxymethyl acrylate, 2-phenoxyethyl acrylate, 2-(2-phenoxyethoxy)ethyl acrylate, and 2-(o-phenylphenoxy)ethyl acrylate An alkoxyalkyl acrylate such as an ester, an aryloxyalkyl acrylate or an aryloxy ethoxyalkyl acrylate; such as 2-methoxyethyl methacrylate or ethoxy methacrylate Ester, 2-phenoxyethyl methacrylate, 2-(2-phenoxyethoxy)ethyl methacrylate, and 2-(o-phenylphenoxy)ethyl methacrylate An alkoxyalkyl ester of acrylic acid, an aryloxyalkyl ester of methacrylic acid or an aryloxy ethoxyalkyl ester of methacrylic acid, etc. The four monomers (A-1) can be used alone or separately. In addition to the above, the monomer (A-丨) is preferably made of n-butyl acrylate as a main component, and is effective to make the equivalent of the formula (1) ( Acrylate copolymerization. One of the preferable compositions of the monomer is, for example, 50% by weight or more of n-butyl acrylate in all the monomers constituting the acrylic resin (A), and 3 to 15 parts by weight / ❶ ratio of r2 in the formula of the above formula (1) is replaced by an argon atom via a group -0-(C2H4〇)n-R3 (where n and & represents the same meaning as above) The monomer (A) is a (meth)acrylic monomer having a hydroxyl group, as an example thereof 161767. Doc 201235436, which can be exemplified by 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-(2-hydroxyl)(meth)acrylate. (Hydroxy)ethyl ester or the like (mercapto)acrylic acid (carbon number 6~6) hydroxyalkyl ester. Among these, 2-hydroxyethyl acrylate is preferably used as one of the monomers (A-2) constituting the acrylic resin (A). The monomer (A-3) is represented by the above formula (11). In the formula (11), the core is a hydrogen atom or a methyl group, and A is a divalent organic group having 2 to 4 carbon atoms. The divalent organic group represented by a is typically an alkylene group which is also preferably a linear alkyl group for linking a (meth)acrylic acid moiety CH2=C(R4)COO- with a terminal carboxyl group-coon carbon. It is premised that the keys are connected in series and at least two. If the number of carbon atoms is 3 or more, it is also possible to branch. In the formula (II), preferred is an acrylate. Specifically, acrylic acid such as acrylic acid 2, thioglycolic acid, 3- cytosyl propionate, or benzoic acid benzoate may be exemplified. Acid carboxyl group (carbon number 1 to 6) alkyl ester. Of course, the compound in which the acrylate is changed to methyl propionate may also be a monomer (A-3). 2-Ret made ethyl acrylate is usually produced by dimerization of acrylic acid, in which case 'except as the main component of acrylic acid 2- ridicyl ethyl ester, in most cases as acrylic acid itself, or It is obtained from a mixture of oligomers of acrylic acid terpolymer and sold directly as a mixture. Of course, a mixture containing a carboxyl group-containing (meth) acrylate (A-2) represented by the formula (II) and a carboxyl group-containing (meth)acrylic monomer may also be used for copolymerization. . In the acrylic resin (A) specified in the present invention, it is derived from the (meth) group represented by the above formula (1). The content of the structural unit of the acrylate, that is, the monomer (A-1) is 94. 8~99. 89% by weight, derived from a (hydroxyl) acrylic monomer having a hydroxyl group 161767. The content of the structural unit of doc 201235436 (A-2) is m 5% by weight, and the structure of the (meth) acrylate which is not the carboxyl group of the above formula (jl), that is, the monomer (A·): The content of the bit is 0. 01~0. 2% by weight. By making the monomers (A 1), (Α·2), and (Α·3)#Μ in such a limited ratio, it is possible to produce excellent workability and to polarize the sheet to prevent it from being an optical laminate. Adhesive sheet which is excellent in various durability or secondary workability when it is heated. The content of the structural unit derived from the monomer (6) is preferably 95% by weight or more, particularly 96% by weight or more, and preferably 99% by weight or less. The content of the structural unit derived from the monomer (Α-2) is preferably 5% by weight or more, and preferably 4% by weight or less, especially 3% by weight or less. Further, the content of the structural unit derived from the monomer (Α-3) is preferably 〇 12 by weight. Below, especially 〇. 1% by weight or less. Of course, the total amount of structural units derived from the monomers (A1), (A 2), and (a_) is not more than 100% by weight. The acrylic resin used in the present invention may also contain monomers derived from the above (A). Structural units of monomers other than -()), (A_2), and (A_3). Examples of monomers other than the monomers (A_1}, (A_2), and (A_3) have polar functions other than hydroxyl groups. An unsaturated monomer other than the formula (1), a (meth) acrylate having an alicyclic structure in a molecule, a styrene monomer, a vinyl monomer, and a (meth) acrylamide derivative a monomer having a plurality of (fluorenyl) acrylonitrile groups in the molecule, etc. An unsaturated monomer other than the formula (11) having a polar functional group other than a hydroxyl group is described. The polar functional group other than the above may be a free carboxyl group, or a heterocyclic group headed by an epoxy ring, etc. The previous monomer (3) is described as the acrylic acid itself or the terpolymer of the acrylic acid. Doc -14· 201235436 The oligomer conforms to an unsaturated monomer other than the formula (π) having a free carboxyl group. Further, if an example of an unsaturated monomer having a heterocyclic group is exemplified, there are acryloyl morpholine, vinyl caprolactam, fluorene-vinyl-2-pyrrolidone, and (indenyl) ethinyl acrylate. Caprolactone is modified with tetrahydrofurfuryl acrylate, (mercapto) propylene, 3,4-% oxycyclohexylmethyl ester, (mercapto) propylene glycol glycidyl ester, and the like. In the case of copolymerizing an unsaturated monomer having a polar functional group other than a hydroxyl group, a (meth)acrylic precursor (Α·2) having a hydroxyl group containing an essential component and the above formula (11) In the case of all the monomers constituting the acrylic resin (A) of the carboxyl group-containing (meth) acrylate 3), the total amount of the unsaturated monomers having a polar functional group is preferably 5% by weight or less. It is preferably 4% by weight or less, and particularly preferably 3 parts by weight. Below you. Next, the (meth)acrylic acid vinegar having a lipid and a quinoid structure in the molecule will be described. The alicyclic structure refers to a ring-shaped structure having a carbon number of usually 5 or more, preferably about 5 to 7, and a specific example of an acrylic acid vinegar having an alicyclic structure, and an acrylic isobornic vinegar or acrylic acid. Cyclohexanoic vinegar, propylene dicyclopentanacetate, acrylic acid cyclomethicone methylcyclohexyl acrylate, trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate, & ethoxydiene hexanoic acid , cyclohexyl acrylate brewing, etc. Further, specific examples of the methyl (tetra) acid S having a structure of a lipid % are methacrylic acid borneol vinegar, methyl propylene glycol hexanoacetic acid, methacrylic acid dicyclopentan vinegar, methyl propyl acrylate. Dilute acid ring 12 mil, methyl methacrylate methyl ring (4), methacrylic acid trimethyl 5 hexidine, thiol-propionate flute - τ 丞 acrylic acid dibutyl cyclohexyl ester 'methacrylic acid Cyclohexyl phenyl ester and the like. 161767. Doc •15· 201235436 If the example of styrene monomer is listed, it is similar to stupid ethylene, such as 曱 basic ethylene, methyl methoxide, dimethyl styrene, ethyl styrene, diethyl benzene. Alkyl styrenes such as ethylene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, and octyl styrene; such as fluorostyrene, gas styrene, bromine Benzene, dibromostyrene, and iodine styrene, and the like; further, nitrostyrene, ethylene styrene, methoxy styrene, divinyl benzene, and the like. Examples of the vinyl monomer include vinyl acetate, ethyl acetonate, ethyl butyrate, ethyl 2-ethylhexanoate, and tetradecyl gluconate. Ethyl fatty acid ester; such as halogenated ethylene such as vaporized ethylene or ethylene bromide; partial diamethylene ethylene such as vinylidene chloride; such as ethylene-based bite, ethylene ratio. Nitrogen-containing aromatic vinyl groups such as ketones and ketone groups, such as butadiene, isoprene, and dibutyl sulphide; Nitrile, methacrylonitrile, and the like. When an example of a (meth) acrylamide derivative is exemplified, there are N-fluorenyl (mercapto) acrylamide, N-(2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl)(fluorenyl)propenylamine, N-(4-hydroxybutyl)(fluorenyl)propenylamine, N-(5-hydroxypentyl)(fluorenyl)propenylamine, N -(6-hydroxyhexyl)(indenyl)propanolamine, N-(decyloxymethyl)(indenyl)propanol, N-(ethoxymethyl)(fluorenyl)propenylamine , N-(propoxymethyl)(fluorenyl) acrylamide, N-(butoxymethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide , N,N-diethyl(fluorenyl) acrylamide, N-isopropyl (meth) acrylamide, N-(3-dimethylaminopropyl) (meth) acrylamide, N-(l,l-dimethyl-3-oxobutyl)(meth)propenylamine, N-[2-(2-o-oxy-1-imidazolium 161767. Doc -16 · 201235436 yl)ethyl](fluorenyl) acrylamide, 2-propenylamino-2-mercapto-1-propionic acid, and the like. If it is exemplified as a monomer having a plurality of (fluorenyl) acrylonitrile groups in the molecule, it is, for example, 1,4-butanediol bis(indenyl) acrylate, hydrazine, 6-hexanediol di(methyl). Acrylate, 1,9-nonanediol bis(indenyl) acrylate, ethylene glycol di(meth)acrylic acid vinegar, monoethylol bis(indenyl) acrylate vinegar, tetraethylene glycol bis ( a monomer having two (indenyl) acrylonitrile groups in the molecule such as methyl acrylate and tripropylene glycol bis(indenyl) acrylate; for example, trimethyl ketone tris(fluorenyl) acrylate A monomer having three (meth) acrylonitrile groups in the molecule, such as an ester. When a monomer other than the monomer (A_丨), (A-2), and (A-3) which is an essential component of the acrylic resin (A) and which does not have a polar functional group is copolymerized, The amount is preferably 5% by weight or less, more preferably 3% by weight or less, based on all monomers constituting the acrylic resin (A), and particularly preferably 1 part by weight. /. the following. The resin component constituting the adhesive composition may be a mixture of two or more kinds of (meth) acrylates represented by the formula (I), that is, a monomer (A-1) having a hydroxyl group. An acrylic monomer (a_2) and an acrylic resin (Α) having a structural unit of a monomer (Α_3) which is a (meth)acrylate represented by the formula (π). Further, an acrylic resin having a structural unit derived from the monomer (A-1), (Α-2), and (Α-3) in a predetermined ratio may be mixed with an acrylic resin different therefrom. In this case, the acrylic resin to be mixed may, for example, be a structural unit having a (meth)acrylic acid vinegar of the above formula (I) and having no polar functional group. In the prescribed ratio 161767. Doc •17- 201235436 The acrylic resin (A) having structural units derived from the monomers (Al), (A-2) and (A-3) is preferably a weight of 8 Å in the entire acrylic resin. Further, it is more preferably 90% by weight or more. The acrylic resin (A) obtained by copolymerization of a monomer mixture containing monomers (Al), (A-2) and (A-3) is used by a gel permeation chromatography (GPC, gel) -permeati〇n chromatography) The standard weight average molecular weight Mw of the standard polystyrene conversion is from 1 million to 2 million. When the weight average molecular weight in terms of standard polystyrene is 10,000 or more, the adhesion at high temperature and high humidity is improved, and the possibility of floating or peeling between the glass substrate and the adhesive sheet tends to be low. It is preferred because it has a tendency to improve secondary workability. Further, when the weight average molecular weight is 2,000,000 or less, even if the size of the optical film bonded to the adhesive sheet changes, the adhesive layer changes in accordance with the dimensional change, so that it is on the peripheral portion of the liquid crystal cell. There is also no difference between the brightness of the center portion and the brightness of the center portion, which is preferable because it tends to suppress blushing or color unevenness. The molecular weight distribution represented by the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Μη is not particularly limited, and is preferably, for example, in the range of about 3 to 7. Further, the acrylic resin (A) preferably has a glass transition property in the range of _ 1 〇 to _60 ° C in order to exhibit adhesiveness. The glass transition temperature of the resin can be measured by a differential scanning calorimeter. The acrylic resin (A) constituting the adhesive sheet can be produced, for example, by various known methods such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. At the time of production of the acrylic resin, a polymerization initiator is usually used. The polymerization initiator is made relative to the manufacture of the acrylic resin. Doc 201235436 Total 100 parts by weight of all monomers used 〇 〜 〜 〜 5 parts by weight. ★ As a polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator or the like is used. The photo-quantitative initiator "e.g., 4-(2-carbyloxy)phenylhydroxy-2-propyl) ketone or the like can be mentioned. As a thermal polymerization initiator, for example, it can be listed. Such as 2,2'-azobisisobutyronitrile, 2,2,-azobis(2-methylbutyronitrile), hydrazine, 1-azobis(cyclohexane-1-carbonitrile), 2,2 , _ azobis(24-dioxyl valeronitrile), 2,2-azobis(2,4.dimethyl-4-ylmethoxyvaleronitrile), dimercaptoazo-(2-propane) An azo compound such as methyl ester) and 2,2·-azodihydroxymethylpropionitrile; such as dodecyl peroxide, tert-butyl hydroperoxide, and fluorene benzoquinone Sulfhydryl, tert-butyl peroxyformate, hydrogen peroxide isopropyl, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, perbutyl neodecanoate, peroxidation Organic peroxides such as tert-butyl pivalate and (3,5,5-dimethylhexyl) peroxide; inorganics such as potassium persulfate, ammonium persulfate, and hydrogen peroxide A peroxide such as a peroxide and a redox initiator of a reducing agent and a reducing agent can also be used as a polymerization initiator. As a method of producing an acrylic resin, in the method described above, a solution polymerization method is preferred. Specific examples of the solution polymerization method include a method in which a desired monomer and an organic solvent are mixed, and a thermal polymerization initiator is added under a nitrogen atmosphere at a temperature of about 40 to 90 ° C, preferably At 60~80. (: about 3 to 10 hours of mixing is applied to the left and right. Further, in order to control the reaction, a monomer or a thermal polymerization initiator may be continuously or intermittently added in the polymerization, or may be dissolved in the organic 161767. Doc -19- 201235436 Adding the state in the solvent. Here, as the organic solvent, for example, an aromatic hydrocarbon such as a stupid or a silly compound; an ester such as ethyl acetate or butyl acetate; an alcohol such as propanol or isopropanol; Aliphatic alcohols; such as acetone, methyl ethyl ketone, and ketones such as methyl isobutyl ketone. [Crosslinking agent (B)] The crosslinking agent (B) is blended in the above acrylic resin (A) to prepare an adhesive composition. The crosslinking agent (B) is a compound which reacts with a hydroxyl group or a carboxyl group which is a polar functional group in the acrylic resin (A), and has at least two functional groups which can crosslink the acrylic resin in the molecule. Specifically, An isocyanate type compound, an epoxy type compound, a metal chelate type compound, an aziridine type compound, etc. are illustrated. The isocyanate compound is a compound having at least two isocyanato groups (-NCO) in the molecule, and examples thereof include: Toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate, hydrogenated stumylene diisocyanate, diphenylmethane diisocyanate hydrogenated monophenyl Simmered diisocyanate, guanidine diisocyanate, triphenylmethane triisocyanate, etc. Further, 'the adduct of reacting the isocyanate compound with a polyol such as a C: alcohol or a tri-methylpropane or a dimeric, tris, etc. It can also be used as a crosslinking agent for adhesives. Two or more kinds of isocyanate compounds may be mixed and used. The oxygenated compound is a compound having at least two epoxy groups in the molecule, and examples thereof include bisphenol eight type epoxy resin, ethylene glycol diglycidyl bond polyethylene glycol diglycidyl hydrazine, and glycerol diglycidyl , glycerin three 161767. Doc 201235436 glycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl shunt, N,N-diglycidylaniline, N,N,N,,N,_four shrinkage Glycerol-m-dimethylamine and the like. Two or more epoxy compounds may be mixed and used. As the metal chelate compound, for example, it can be exemplified by coordination of acetamidineacetone or acetamidineacetic acid in a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, ruthenium, magnesium, vanadium, chromium, and zirconium. Ethyl ester compounds and the like. The aziridine compound is a compound having at least two skeletons of a 3-membered ring containing one nitrogen atom and two carbon atoms, which are also called ethyleneimine in the molecule, and examples thereof include diphenyl decane. _4,4,_bis(1_aziridine), toluene-2,4-bis(1-aziridine), tri-ethyl melamine, m-benzoquinone- 1-(2-methylaziridine), tri-1-aziridine phosphine oxide, hexamethylene-1,6-bis(1-aziridinecarboxamide), trishydroxypropylpropane _p_ aziridine propionate, tetrahydrocarbyl decane tri-β-aziridine propionate, and the like. Among these crosslinking agents, it is preferred to use an isocyanate compound, especially phenyldiamidino diisocyanate, toluene diisocyanate or hexamethylene diisocyanate; or to make the quaternary acid An adduct which is reacted with a polyol such as glycerol or tris-propyl propane; or an isocyanate compound which is a one-to-one, two-pot, etc.; a mixture of such isocyanate-based compounds, etc. . Examples of the particularly preferable isocyanate-based compound include an adduct of toluene diisophthalate, a reaction of toluene diisocyanate with a polyhydric alcohol, a dimer of indole diisocyanate, and a trimeric body of methyl diisocyanate. . The crosslinking agent (Β) is 161767 with respect to 100 parts by weight of the acrylic resin (Α). Doc -21- 201235436 0 · 01~5 The proportion of weight injury is adjusted. The amount of the crosslinking agent (b) is preferably 0. by weight relative to 100 parts by weight of the acrylic resin (A). ^% by weight, and more preferably 0. 1 to 1 part by weight or so. When the amount of the crosslinking agent (B) based on 1 part by weight of the acrylic resin (A) is 〇〇1 part by weight or more, particularly 〇1 part by weight or more, the durability of the adhesive sheet tends to be improved. Therefore, it is preferable that if it is 5 parts by weight or less, the whitening of the optical film with an adhesive for the liquid crystal display device becomes inconspicuous, which is preferable. [Other components constituting the adhesive composition] In the adhesive composition for forming the adhesive sheet of the present invention, in order to improve the adhesion between the adhesive sheet and the glass substrate, it is preferred to contain a decane system. The compound (C) is preferably a decane-based compound (C) which is contained in the acrylic resin before the crosslinking agent is prepared. Examples of the decane-based compound (c) include ethylene trimethoxy decane, ethylene triethoxy decane, ethylene tris(2·methoxyethoxy) decane, and 3' glycidoxypropyl trimethoxy group. Decane, 3' glycidoxypropylmethyldimethoxycarbazide, 2-(3,4.epoxycyclohexyl)ethyltrimethoxy aspartate, 3-cyclopropylmethyldimethoxyl Decane, 3-propyltrimethoxydecane, 3,mercaptopropoxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3'glycidoxypropyltrimethoxydecane, 3 'Glycidoxypropyl triethoxy", 3 - glycidoxypropyl dimethoxymethyl (tetra), 3 · glycidoxypropyl ethoxy dimethyl (tetra), and the like. Two or more kinds of decane-based compounds (c) can also be used. The decane-based compound (C) may also be a polyoxyphthalocene oligomer type. If the polyfluorene oxide oligomer is represented by a (monomeric monomer) copolymer, for example, it can be listed as 161767. Doc -22- 201235436 Take the following: such as 3-mercaptopropyltrimethoxy oxime _tetramethoxy fluorene copolymer, 3-mercaptopropyltrimethoxy decane-tetraethoxy decane copolymer , mercaptopropyl-containing copolymers such as 3-mercaptopropyltriethoxydecane-tetramethoxydecane copolymer and 3-mercaptopropyltriethoxydecane-tetraethoxydecane copolymer Such as mercaptomethyltrimethoxydecane-tetradecyloxydecane copolymer, mercaptomethyltrimethoxydecane-tetraethoxydecane copolymer, mercaptodecyltriethoxydecane-tetradecyloxydecane a copolymer, and a mercapto-based mercapto group-containing copolymer such as a mercaptomethyltriethoxysulfonium-tetraethoxydecane copolymer; such as 3-methylpropenyloxypropyltrimethoxydecane-four Methoxy decane copolymer, 3-methacryloxypropyltrimethoxy decane _ tetraethoxy oxime copolymer, 3-mercapto propylene methoxy propyl triethoxy decane _ four Oxyzepine copolymer, 3-mercaptopropenyloxypropyltriethoxydecane-tetraethoxydecane copolymer, 3-methylpropenyloxypropylmethyldimethoxyindole _ tetradecyl oxalate copolymer, 3-mercaptopropene oxypropylmethyldimethoxy decane-tetraethoxy decane copolymer, 3-methacryloxypropylmethyl Ethoxy decane-tetramethoxydecane copolymer, and 3-methacryloxypropyl decyl diethoxy decane-tetraethoxy decane copolymer a copolymer such as 3-propenyloxypropyltrimethoxydecane-tetramethoxydecane copolymer, 3-propenyloxypropyltrimethoxydecane-tetraethoxydecane copolymer, 3 - propylene methoxy propyl triethoxy decane - tetramethoxy decane copolymer 3 propylene methoxy propyl diethoxy decane - tetraethoxy decane copolymer 3 propylene methoxy propyl methyl 2 Methoxy decane-tetramethoxy decane total 161767. Doc -23· 201235436 Polymer, 3-propenylmethoxypropylmethyldimethoxydecane_tetraethoxydecane copolymer, 3-propenyloxypropylmercaptodiethoxydecane_four a oxydecane copolymer, and a copolymer containing a propylene methoxy propyl group such as 3-propenyl methoxypropyl decyl diethoxy decane _ tetraethoxy sulphuric acid copolymer; such as ethylene trioxane Pyridinium tetradecyloxydecane copolymer, ethylene trimethoxycarbazide-tetraethoxydecane copolymer, ethylene triethoxydecane-tetramethoxydecane copolymer, ethylene triethoxydecane_tetraethyl Oxy decane copolymer, ethylene methyl dimethoxy decane-tetramethoxy decane copolymer, ethylene decyl decyl decane-tetraethoxy decane copolymer, ethylene methyl diethoxy sulphur - a tetradecyloxydecane copolymer, and a vinyl group-containing copolymer such as a vinyl fluorenyl diethoxy sulphur-tetraethoxy decane copolymer. These decane-based compounds are liquid in many cases. The amount of the decane-based compound (C) in the adhesive composition is from 1 part by weight to the solid part of the acrylic resin (A), and is usually about 1 to 1 part by weight, preferably 0. It is used in a ratio of 03 to 2 parts by weight, more preferably 〇 034 parts by weight. If the amount of the decane compound relative to the acrylic resin (Α) is 1 〇〇, the amount of damage is 0. 01 parts by weight or more, especially 〇. When the amount of the ruthenium is 3 parts by weight or more, the adhesion between the adhesive sheet and the glass substrate is improved, which is preferable. In addition, when the amount is 10 parts by weight or less, particularly 2 parts by weight or less or i part by weight or less, the decane-based compound tends to be prevented from overflowing from the adhesive sheet, which is preferable. The above-described adhesive composition exhibits good performance, and in the case of contact with a predetermined release film, it is preferred to contain no amine group in order to avoid strong adhesion. It is especially preferred that it does not have a tertiary amine group. In the adhesive composition, it is also possible to formulate a cross-linking catalyst and antistatic 161767. Doc •24· 201235436 Agent, weathering stabilizer, adhesive, plasticizer, softener, dye, pigment, inorganic filler, resin other than acrylic resin (A). Further, it is also useful to prepare an ultraviolet curable compound in an adhesive composition, form an adhesive sheet, and then cure it by irradiating ultraviolet rays to form a harder adhesive layer. Wherein, if a crosslinking agent and a crosslinking catalyst are formulated in the adhesive composition, the adhesive sheet can be prepared by curing for a short period of time, and can be suppressed in the obtained optical film with an adhesive attached thereto. Float or peeling occurs between the optical film and the adhesive sheet or foaming occurs in the adhesive sheet, and secondary workability sometimes becomes better. These components constituting the adhesive composition are mixed in a state of being dissolved in a solvent, applied to a suitable substrate, and dried to prepare an adhesive sheet. The substrate used herein is usually a plastic film, and a typical example thereof is a release film which is subjected to a release treatment. The release film may be, for example, a surface of an adhesive sheet comprising a film of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate. A mold release processor such as an oxygen treatment. [Gel Fraction of Adhesive Sheet] The adhesive sheet of the present invention can be formed by using the above-described adhesive composition, which can be applied in a sheet form and left at room temperature for 2 days. The ratio of the gel fraction to the gel fraction after leaving it at room temperature for 7 days after being coated into a sheet was set to 0. 8 or more. When the ratio is 〇·8 or more, it means that the crosslinking reaction is rapidly carried out after being applied in a sheet form, and the curing of the adhesive is substantially completed at 2 days. That is, the ratio is an approximate target of workability. Here, the gel fraction is a value measured in accordance with the following (1) to (4). 161767. Doc -25- 201235436 (1) Adhesive sheet with an area of about 8 cmx and about 8 cm, and a metal mesh of SljS304 containing about 10 cmx and about 1 〇cm (when the weight is set to Wm) is 0 (2) The weight of the composition obtained in the above (1) is weighed, and the weight is set to ws, and then folded four times by wrapping the adhesive sheet and fixed by a wire stapler (stapler), and then weighed. Its weight is set to Wb. (3) The net fixed in the stapler of the above (2) was placed in a glass container, and 60 mL of ethyl acetate was added to be immersed, and the glass container was stored at room temperature for 3 days. (4) The net was taken out from the glass container, and dried under i2〇〇c for 24 hours, and then weighed. The weight was made into Wa, and the gel fraction was calculated according to the following formula. Gel fraction (% by weight) = [{Wa - (Wb - Ws) - Wm} / (Ws - Wm)] xl00 As described above, in many cases, the adhesive sheet is cured after a certain period of time after production. The crosslinking reaction is carried out to be used in a state in which a certain degree of gel fraction is exhibited. The gel fraction in the state in which the crosslinking reaction is carried out in such a manner that the curing is terminated can be carried out, for example, according to the kind of the acrylic resin (A) or the amount of the crosslinking agent of the active component of the adhesive composition forming the adhesive composition. Adjustment. Specifically, if the amount of the monomer having a polar functional group including the monomer (A_2) and the monomer (A-3) in the acrylic resin (A) is increased, or the crosslinking agent in the adhesive composition is increased In the amount of (B), the gel fraction is changed, so that the gel fraction can be adjusted by adjusting the amounts. [Optical film to which an adhesive is attached] The optical film with an adhesive of the present invention is obtained by attaching an adhesive sheet formed of an adhesive composition such as the above to at least one side of the optical film. Such a sticky (four) sheet # attached to the state of the optical film with the adhesive light 161767. Doc -26-201235436 In the optical layered body in which the film is laminated or laminated on the glass substrate, the layer of the adhesive sheet may be simply referred to as "adhesive layer" in the present specification. The optical film used for the optical film with an adhesive is a film having optical characteristics, and examples thereof include a polarizing plate and a retardation film. The polarizing plate refers to an optical film that has a function of emitting polarized light for incident light such as natural light. In the polarizing plate, there is a linear polarizing plate having a linear polarized light that absorbs a vibrating surface including a certain direction and penetrates a linear polarized light including a vibrating surface orthogonal thereto; and a linear polarized light that reflects a vibrating surface including a certain direction Further, a polarizing plate that penetrates the property of linearly polarized light having a vibration plane orthogonal thereto; a polarizing plate that laminates a polarizing plate and a retardation film to be described later, and the like. A preferred example of a polarizing film (particularly referred to as a polarizer) which functions as a polarizing plate, in particular, a linear polarizing plate is exemplified by adsorption-aligned iodine or dichroism in a uniaxially stretched polyvinyl alcohol-based resin film. A dichroic dye such as a dye. The retardation film refers to an optical film exhibiting optical anisotropy, and for example, by including polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimide, polyolefin, cyclic polyolefin , polystyrene, polysulfone, polyether oxime, polyvinylidene fluoride / polymethyl methacrylate, liquid crystal polyester, acetyl cellulose, ethylene - vinyl acetate copolymer saponified, polyvinyl chloride, etc. The same molecular film extends to 1. A stretch film obtained by about 01 to 6 times. Among them, a polymer film in which a polycarbonate film or a cyclic polyolefin film is uniaxially stretched or biaxially stretched is preferable. There is a uniaxial phase difference film, a wide field retardation film, and a low photoelastic modulus retardation film, and any of them can be used. 161767. Doc •27-201235436 Further, a film which exhibits optical anisotropy by coating or alignment of a liquid crystal compound or a film exhibiting optical anisotropy by application of an inorganic layered compound can also be used as a phase difference. membrane. In the retardation film, a film called a temperature-compensated retardation film, and a film which is sold under the trade name of LC film j and twisted by a rod-shaped liquid crystal, is similarly used. A film sold under the trade name of "NH film" and a rod-shaped liquid crystal tilting distribution from Shin-Koumoto Oil Co., Ltd., sold under the trade name "WV film" by Fuji Film Co., Ltd. and disc-shaped liquid crystal The film of the "nevv VAC film" is sold by Sumitomo Chemical Co., Ltd. under the trade name "VAC film" and is sold under the trade name "VAC film". A film that is sold and biaxially aligned. Further, an adhesive film can be used as an optical film in the optical films. As the protective film, a transparent resin film is used, and as the transparent resin, for example, an ethylene glycol-based resin represented by triethyl fluorene cellulose or diethyl phthalocyanine, which is represented by polymethyl methacrylate, is used. A base acrylic resin, a polyester resin, a polyolefin resin, a polycarbonate resin 'polyether ether ketone resin, a polyhard resin, and the like. In the resin constituting the protective film, a salicylate-based compound, a benzophenone-based compound, a benzotriazole-based compound, a tri-systemic compound, a cyanoacrylate-based compound, a nickel complex-based compound, or the like may be blended. Ultraviolet Absorber As the protective film, an acetaminocellulose-based resin film such as a triethylene fluorene cellulose film can be preferably used. In the optical film described above, the linear polarizing plate is often used in a state in which a polarizing film is formed, for example, a single surface or a double-sided adhesive film containing a polyvinyl alcohol-based resin. Moreover, the above elliptically polarizing plate is 161767. Doc -28 - 201235436 For laminated linear polarizers and retarders, the linear polarizers are mostly bonded to the protective film on one or both sides of the polarizing film. When the adhesive sheet of the present invention is bonded to the elliptically polarizing plate, it is usually bonded to the retardation film side. The optical film to which the adhesive is attached is preferably adhered to the surface of the adhesive layer as described above to release the release film of the release treatment to protect the surface of the adhesive layer until it is used. The optical film with an adhesive attached to the release film in this manner can be produced, for example, by applying the above-mentioned adhesive composition to the release-treated surface of the release film and forming an adhesive sheet, and the obtained adhesive is obtained. a method of laminating a sheet on an optical film; applying an adhesive composition on the optical film to form an adhesive sheet, and adhering the release film to the adhesive surface to protect it to form an optical film with an adhesive Method and so on. The thickness of the adhesive layer formed on the optical film is not particularly limited, and is usually preferably 30 μm or less and preferably 1 Å or more, and more preferably 15 to 25 μm. When the thickness of the adhesive layer is 3 〇μηι or less, the adhesion under high temperature and high humidity is improved, and the possibility of floating or peeling between the glass substrate and the adhesive layer becomes low, and there is secondary processing. It is preferable that the thickness is 1 〇μιη or more, and even if the size of the optical film to which it is attached changes, the adhesive layer fluctuates with the change of the size. There is also no difference between the brightness of the peripheral portion and the brightness of the central portion, and there is a tendency to suppress blushing or color unevenness, which is preferable. When the optical film with the adhesive of the present invention is adhered to the glass substrate to form an optical laminate, 'the adhesive layer is peeled off with the optical film when there is a slight defect in peeling off the optical film from the glass substrate. With the adhesive layer adjacent to 161767. Doc •29· 201235436 The surface of the glass substrate is almost free of stains or residue, so that the glass substrate which is easily peeled off is reattached to the optical film with the adhesive. That is, the secondary workability is excellent. [Optical Laminate] The optical film with an adhesive of the present invention can be laminated on a glass substrate to form an optical laminate. When an optical film having an adhesive is laminated on a glass substrate to form an optical layered body, for example, an optical film with an adhesive obtained as described above is peeled off from the release film, and the exposed adhesive layer is bonded to the glass. The surface of the substrate can be used. Examples of the glass substrate include a glass substrate of a liquid crystal cell, a glass for antiglare, and a glass for sunglasses. Wherein, the glass substrate on the front side (viewing side) of the liquid crystal cell is laminated with an optical film (upper polarizing plate) of an adhesive, and the glass substrate on the back side of the liquid crystal cell is laminated with another optical film with an adhesive (lower) The optical laminate formed of the polarizing plate is preferable because it can be used as a panel (liquid crystal panel) for a liquid crystal display device. As the material of the glass substrate, for example, soda lime glass, low alkali glass, alkali-free glass, or the like, and the liquid crystal cell can preferably use alkali-free glass. Regarding the optical laminate of the present invention, an example of a plurality of preferred layer constitutions is shown in Fig. 1 in a cross-sectional mode. In the example shown in Fig. 1(A), the protective film 3 having the surface treated layer 2 is adhered to the surface opposite to the surface treatment layer 2 on one surface of the polarizing film J to constitute the polarizing plate 5. In this example, the polarizing plate 5 also serves as the so-called optical film 1 in the present invention. An adhesive layer 2 is disposed on the opposite side of the polarizing film 1 from the protective film 3 to form an optical film 25 with an adhesive, and the adhesive layer 2 is bonded to 161767. Doc • 30· 201235436 The polarizing plate 5 is bonded to the liquid crystal cell 3 of the glass substrate on the opposite side to constitute the optical layered body 40. In the example shown in FIG. 1(B), the first protective film 3 having the surface treatment layer 2 is adhered to the surface opposite to the surface treatment layer 2 on one side of the polarizing film 1, on the polarizing film 1. The other protective surface 4 is adhered to the other surface to constitute the polarizing plate 5. In this example, the polarizing plate 5 also becomes the so-called optical film 1 in the present invention. An adhesive layer 2 is provided on the outer side of the second protective film 4 constituting the polarizing plate 5 to constitute an optical film 25 with an adhesive. Further, the surface of the adhesive layer 2 opposite to the polarizing plate 5 is bonded to the liquid crystal cell 3 of the glass substrate to form the optical layered body 40. In the example shown in Fig. 1(C), the protective film 3 having the surface treated layer 2 is adhered to the surface opposite to the surface treated layer 2 on one surface of the polarizing film i to constitute the polarizing plate 5. The optical film 1 is formed by adhering the retardation film 7 to the surface of the polarizing film 与 opposite to the protective film 3 via the interlayer adhesive 8. An adhesive layer 2 is provided on the outer side of the retardation film 7 constituting the optical film 10 to constitute an optical film 25 with an adhesive. Further, the surface of the adhesive layer 20 on the opposite side to the optical film 1 is bonded to the liquid crystal cell 3 of the glass substrate to form an optical layered body 4'. Further, in the example shown in FIG. 1(D), the first protective film 3 having the surface treatment layer 2 is adhered to the surface opposite to the surface treatment layer 2 on one side of the polarizing film '. membrane! The other surface is adhered to the second protective film* to constitute the polarizing plate 5. The optical film 10 is formed by adhering the retardation film 7 to the outside of the second protective film 4 constituting the polarizing plate 5 via the interlayer adhesive 8. An adhesive (4) is disposed on the outer side of the phase difference 臈7 constituting the optical film 10 to constitute an I61767 with an adhesive. Doc • 31·201235436 The optical film 25 is bonded to the liquid crystal cell 3 of the glass substrate by bonding the surface of the adhesive layer 2 to the opposite side of the optical film 1〇 to form an optical layered body 4〇. In these examples, the first protective film 3 and the second protective film 4 are usually composed of a trimethyl cellulose film, and may be composed of various transparent resin films described above. Further, the surface treatment layer formed on the surface of the first protective film 3 may be a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer or the like. In the above, a plurality of layers β may be provided, as in the case of (C) and (D) of FIG. 1 , when the polarizing plate 5 is laminated to form a retardation film 7 , if it is a small-sized liquid crystal display device A preferred example of the retardation film 7 is a quarter-wave plate. In this case, the absorption axis of the polarizing plate 5 and the retardation axis of the retardation film 7 of the quarter-wavelength plate are usually arranged at substantially 45 degrees, and depending on the characteristics of the liquid crystal cell 3, The angle is offset from 45 degrees to some extent. On the other hand, in the case of a large-sized liquid crystal display device such as a television, a phase difference film having various phase difference values in accordance with the characteristics of the liquid crystal cell 3 is used for phase difference compensation or viewing angle compensation of the liquid crystal cell 3 . In the case of the clear shape, the absorption axis of the polarizing plate 5 and the slow axis of the retardation film 7 are usually arranged in a substantially orthogonal or substantially parallel relationship. In the case where the retardation film 7 is composed of a 1/4 wavelength plate, a uniaxial or biaxial stretching film can be preferably used. Further, in the case where the retardation film 7 is provided for the phase difference compensation or the viewing angle compensation of the liquid crystal cell 3, in addition to the uniaxial or biaxially stretched film, the thickness may be increased in addition to the uniaxial or biaxial stretching. A film that is oriented in the direction, a film that is coated with a phase difference in a liquid crystal, and a film that is aligned and fixed, etc., is called an optical compensation film and is used as a retardation film 7 ^ I6I767. Doc •32· 201235436 Similarly, when the polarizing plate 5 and the retardation film 7 are bonded via the interlayer adhesive 8 as in the example shown in FIGS. 1(C) and (D), the interlayer adhesive 8 A usual example is the use of a conventional acrylic adhesive, and it is of course also possible to use the adhesive monthly material specified in the present invention. As in the case of the large-sized liquid crystal display device described above, when the absorption axis of the polarizing plate 5 and the slow axis of the retardation film 7 are arranged in a substantially orthogonal or substantially parallel relationship, the polarized light can be polarized. In the use in which the plate 5 and the retardation film 7 are bonded to each other without requiring re-peelability between the two, the plate 5 and the retardation film 7 may be used to be firmly bonded after being bonded. The adhesive is substituted for the interlayer adhesive 8 shown in (c) and (D) of the figure. Examples of the adhesive agent include a water-based adhesive which is composed of an aqueous solution or an aqueous dispersion and which exhibits an adhesive force by evaporating water of a solvent, and an ultraviolet-curable adhesive which is cured by ultraviolet irradiation and exhibits an adhesive force. Further, the adhesive layer 20 formed on the retardation film 7 shown in (C) and (D) of FIG. 1 can be widely used in its own form, and can be referred to as an adhesive in the present invention. Optical film. The optical film with an adhesive formed on the retardation film may be attached to the liquid crystal cell of the glass substrate and formed into an optical laminate, or may be attached to the retardation film side. The plate is made into other optical films with an adhesive. 1 is a view showing an example in which an optical film 25 with an adhesive is disposed on the viewing side of the liquid crystal cell 30. The optical film with an adhesive of the present invention may be disposed on the back side of the liquid crystal cell, that is, on the backlight side. . When the optical film with an adhesive of the present invention is disposed on the back side of the liquid crystal cell, a protective film having no surface treatment layer is used instead of the one shown in Fig. 161767. Doc -33- 201235436 The protective film 3 of the surface treatment layer 2 can be configured in the same manner as (A) to (D) of Fig. 1 . In this case, various optical films which are known to be disposed on the back side of the liquid crystal cell, such as a brightness enhancement film, a light-concentrating film, and a diffusion film, may be provided outside the protective film constituting the polarizing plate. As described above, the optical laminate of the present invention can be preferably used for a liquid crystal display device. The liquid crystal display device formed by the optical laminate of the present invention can be used, for example, for a notebook type, a desktop type, or a PDA (Pers〇nal Dighal).

Assistant，個人數碼助理）等之個人電腦用液晶顯示器、電 視、車輛用顯示器、電子辭典、數位相機、數位攝影機、 電子桌上計算器、手錶等。 實施例 以下列舉實施例，對本發明進行更具體地說明，但本發 明並不限定於該等例子。例中，表示使用量或含量之％及 份只要無特別說明，則為重量基準。 於以下例子中，重量平均分子量為如下值：串聯連接東 曹（股份有限公司）製造之「TSKgel XL」4根、與昭和電工 (版伤有限公司）製造且昭光通商（股份有限公司）販賣之 「Shodex GPC KF-802」1根之共計5根作為管柱而配置於 GPC裝置中’使用四氫。夫喊作為溶出《，於試樣濃度為$ mg/mL、試樣導入量為100从、溫度為4〇<5(： 分鐘之條件下’藉由標準聚苯乙稀換算進行測定而獲得。 首先，表示製造成為黏著劑組合物之主成分之本發明所 規定之丙烯酸系樹脂（A)、及與其類似但偏離本發明之規 定之丙烯酸系、樹脂的聚合例。於以下之聚合例中，使用如 161767.doc •34· 201235436 下者作為羧基含有單體。 PCEA為自Daicel-Cytec股份有限公司以「β-CEA」之商 品名販賣之β-丙烯酸羧基乙酯。其化學組成表示為 CH2=CH(COOCH2CH2)nCOOH(n=平均 1)，具體而言為丙稀 酸2-羧基乙酯（丙烯酸之二聚物）40%、丙烯酸之三聚物以 上之低聚物40%、丙稀酸20%。以下，仿效其商品名表示 為「PCEA」。其中，於表中將「」省略（以下相同）。 AA:丙烯酸CH2=CHCOOH。 M-5300為自東亞合成股份有限公司以「M-5300」之商 品名販賣且具有CH2=CHCOO(C5H1()COO)nH之化學組成之 ω-羧基聚己内酯（n与2)單丙烯酸酯》以下，仿效其商品名 表示為「Μ-5300」。 A-SA為自新中村化學工業股份有限公司以「A-SA」之 商品名販賣、 具有 CH2=CHCOOCH2CH2OCOCH2CH2COOH之化學組成 之丁二酸2-丙烯醯氧基乙酯。以下，仿效其商品名表示為 「A-SA」。 [聚合例1] 於具備冷卻管、氮氣導入管、溫度計及攪拌機之反應容 器中’加入作為溶劑之乙酸乙酯818份、作為單體之 丙烯酸丁酯70.8份、丙烯酸曱酯2〇.〇份及丙烯酸2-(2-苯氧 基乙氧基）乙S旨8.0份、作為單體（Α·2)之丙烯酸2_羥基乙酯 1.0份、以及作為單體（Α_3)之「pcEA」〇 2份，由氮氣置 換裝置内之空氣而使裝置内不含氧，並且使内溫上升至 161767.doc •35· 201235436 55°C。其後’添加足夠量之使偶氮二異丁腈（聚合起始 劑）〇·Μ份溶解於乙酸乙酯1〇份中而成之溶液。添加起始劑 後’於該溫度下保持1小時’繼而使内溫保持於5 4〜5 6。(3， 並且以添加速度1 7·3份/hr將乙酸乙醋連續地加入反應容器 内’於丙稀酸系樹脂之濃度成為35%時停止添加乙酸乙 醋’進而自開始添加乙酸乙酯開始直至經過12小時為止， 於該溫度下保溫。最後加入乙酸乙酯，以使丙稀酸系樹脂 之濃度成為20%之方式進行調節而製備丙烯酸系樹脂之乙 酸乙酯溶液。所獲得之丙烯酸系樹脂係藉由GPC而求出之 聚苯乙稀換算之重量平均分子量Mw為166萬，Mw/Mn為 4 · 0。將其设為丙稀酸系樹脂A。該丙稀酸系樹脂含有來自 相當於單體（A-3)之丙烯酸2-羧基乙酯之結構單位〇 〇8%， 除此以外含有來自丙烯酸之三聚物之結構單位〇 〇8%及來 自丙烯酸之結構單位0.04%» [聚合例2] 於單體組成中，分別將丙烯酸丁酯之量變更為70.9份、 將「PCEA」之量變更為0.1份，除此以外以與聚合例i相同 之方式製備丙烯酸系樹脂之乙酸乙酯溶液》所獲得之丙婦 酸系樹脂藉由GPC而求出之聚苯乙烯換算之重量平均分子 量Mw為164萬，Mw/Mn為4.0。將其設為丙烯酸系樹脂b。 該丙稀酸系樹脂含有來自相當於單體（A-3)之丙烯酸2-繞基 乙酯之結構單位0.04%，除此以外含有來自丙烯酸之三聚 物之結構單位0.04%及來自丙烯酸之結構單位〇_〇2%。 [聚合例3] 161767.doc -36- 201235436 於單體組成中，分別將丙烯酸丁酯之量變更為7〇 92 份’將「PCEA」之量變更為〇.08份，除此以外以與聚合例 1相同之方式製備丙烯酸系樹脂之乙酸乙酯溶液。所獲得 之丙烯酸系樹脂係藉由GPC而求出之聚苯乙烯換算之重量 平均分子量Mw為151萬，Mw/Mn為4.7。將其設為丙稀酸 系樹脂C。該丙烯酸系樹脂含有來自相當於單體（a_3)之丙 烯酸2-羧基乙酯之結構單位0.032%，除此以外，含有來自 丙烯酸之三聚物之結構單位0.032%及來自丙烯酸之結構單 位 0.016%。 [聚合例4] 於單體組成中，分別將丙烯酸丁酯之量變更為70.95 份，將「PCEA」之量變更為〇.〇5份，除此以外以與聚合例 1相同之方式製備丙烯酸系樹脂之乙酸乙酯溶液。所獲得 之丙烯酸系樹脂係藉由GPC而求出之經聚苯乙烯換算之重 量平均分子量Mw為166萬，Mw/Mn為4.8。將其設為丙稀 酸系樹脂D。該丙烯酸系樹脂含有來自相當於單體（A_3)之 丙烯酸2-羧基乙酯之結構單位〇.〇2°/〇，除此以外含有來自 丙烯酸之三聚物之結構單位0.02%及來自丙烯酸之結構單 位 0.01%。 [聚合例5] 於單體組成中，分別將丙烯酸丁酯之量變更為70.9份， 將「PCEA」之量變更為0.1份，使用相同量（1.0份）之丙缔 酸4-羥基丁酯代替丙烯酸2-羥基乙酯，除此以外以與聚合 例1相同之方式製備丙烯酸系樹脂之乙酸乙酯溶液。所獲 161767.doc •37- 201235436 得之丙烯酸系樹脂係藉由GPC而求出之聚笨乙稀換算之重 量平均分子量Mw為166萬，Mw/Mn為4.0»將其气為丙稀 酸樹脂E。該丙稀酸系樹脂含有來自相當於單體（A—])之丙 烯酸2-羧基乙酯之結構單位0.04%，除此以外含有來自丙 烯酸之三聚物之結構單位0.04%及來自丙烯酸之結構單位 0·02〇/〇。 [聚合例6](比較用） 於單體組成中，分別將丙烯酸丁酯之量變更為7〇 4份， 將「0CEA」之量變更為〇·6份，使用相同量（8 〇份）之丙烯 酸2-苯氧基乙酯代替丙烯酸2_(2·苯氧基乙氧基）乙酯，除 此以外以與聚合例1相同之方式製備丙烯酸系樹脂之乙酸 乙醋溶液。所獲得之丙烯酸系樹脂係藉由GPC而求出之聚 苯乙烯換算之重量平均分子量Mw為丨69萬，Mw/Mn為 4.2。將其設為丙烯酸系樹脂v ^該丙烯酸樹脂含有來自相 當於單體（A-3)之丙烯酸2-羧基乙酯之結構單位0.24%，除 此以外含有來自丙烯酸之三聚物之結構單位〇 24%及來自 丙烯酸之結構單位〇.12〇/。。 [聚合例7](比較用） 於單體組成中，使用相同量（0.6份）之丙烯酸代替 「0CEA」’除此以外以與聚合例6相同之方式製備丙烯酸 系樹脂之乙酸乙酯溶液。所獲得之丙烯酸系樹脂係藉由 GPC而求出之聚苯乙烯換算之重量平均分子量Mw為142 萬’ Mw/Mn為5.2 ^將其設為丙烯酸系樹脂w。該丙烯酸 樹脂不含有相當於單體（A_3)之結構單位，取而代之含有 161767.doc • 38 - 201235436 來自丙烯酸之結構單位0.6%。 [聚合例8](比較用） 於單體組成中，使用相同量（〇·6份）r M_53〇〇」代替 「PCEA」，除此以外以與聚合例6相同之方式製備丙烯酸 系樹脂之乙酸乙醋溶液。所獲得之丙烯酸系樹脂係藉由 GPC而求出之聚苯乙烯換算之重量平均分子量Mw為15 8 萬’ Mw/Mn為4.5。將其設為丙烯酸系樹脂X。該丙烯酸系 樹脂亦不含有相當於單體（A-3)之結構單位，取而代之含有 來自ω-羧基聚己内酯單丙烯酸酯cH2=CHCOO(；C5HI()COO)nH (η f 2)之結構單位〇 · 6 % » [聚合例9](比較用） 於單體組成中，將丙稀酸丁 g旨之量變更為6 9.3份，將 「M-5300」之量變更為1 _7份’除此以外以與聚合例8相同 之方式製備丙烯酸系樹脂之乙酸乙酯溶液。 所獲得之丙烯酸系樹脂係藉由GPC而求出之聚苯乙烯換 真之重量平均分子量Mw為174萬，Mw/Mn為3.9。將其設 為丙烯酸系樹脂Y。該丙烯酸系樹脂亦不含有相當於單體 (A-3)之結構單位，取而代之含有來自‘羧基聚己内醋單 丙烯酸酯CH2=CHCOO(C5H丨〇COO)nH(n与2)之結構單位 1.7%。 [聚合例10](比較用） 於單體組成中，使用相同量（0.1份）之r A-SA」代替 「pCEA」’除此以外以與聚合例2相同之方式製備丙稀酸 系樹脂之乙酸乙酯溶液。所獲得之丙烯酸系樹脂係藉由Gpc 161767.doc -39- 201235436Assistants, personal digital assistants, etc. LCD monitors for personal computers, televisions, vehicle displays, electronic dictionaries, digital cameras, digital cameras, electronic desk calculators, watches, etc. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In the examples, the % and the parts used and the content are based on weight unless otherwise specified. In the following examples, the weight average molecular weight is as follows: 4 pieces of "TSKgel XL" manufactured by Tosoh Corporation, and manufactured by Showa Denko (Version Co., Ltd.) and sold by Zhaoguang Trading Co., Ltd. A total of five "Shodex GPC KF-802" was placed in a GPC apparatus as a column, and "tetrahydrogen was used. The husband shouted as a dissolution, obtained by measuring the sample concentration of $ mg/mL, the sample introduction amount of 100, and the temperature of 4 〇 < 5 (: minutes) by standard polystyrene conversion First, an acrylic resin (A) specified in the present invention which is a main component of the adhesive composition, and a polymerization example similar to the acrylic resin or resin which is different from the present invention are produced. In the following polymerization examples, For example, 161767.doc •34·201235436 is used as a carboxyl group-containing monomer. PCEA is a β-acrylic acid carboxyethyl ester sold under the trade name “β-CEA” by Daicel-Cytec Co., Ltd. Its chemical composition is expressed as CH2=CH(COOCH2CH2)nCOOH (n=average 1), specifically, 2-carboxyethyl acrylate (dimer of acrylic acid) 40%, oligomer of acrylic acid terpolymer 40%, C The dilute acid is 20%. Hereinafter, the trade name is expressed as "PCEA". In the table, "" is omitted (the same applies hereinafter). AA: Acrylic acid CH2=CHCOOH. M-5300 is from East Asia Synthetic Co., Ltd. The trade name of M-5300" is sold and has CH2=CHCOO(C5H1()C Ω) ω-carboxypolycaprolactone (n and 2) monoacrylate having the chemical composition of nH is hereinafter referred to as "Μ-5300" by the trade name. A-SA is a self-made Zhongcun Chemical Industry Co., Ltd. "A-SA" is sold under the trade name of 2-acrylic acid succinic acid having a chemical composition of CH2=CHCOOCH2CH2OCOCH2CH2COOH. Hereinafter, the product name is expressed as "A-SA". [Polymer Example 1] In a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirrer, '818 of ethyl acetate as a solvent, 70.8 parts of butyl acrylate as a monomer, 2 parts of decyl acrylate, and 2 - 2 of acrylic acid were added. - phenoxyethoxy) B, 8.0 parts, 1.0 part of 2-hydroxyethyl acrylate as a monomer (Α·2), and 2 parts of "pcEA" as a monomer (Α_3), replaced by nitrogen The air in the device does not contain oxygen in the device, and the internal temperature is raised to 161767.doc •35· 201235436 55°C. Then add a sufficient amount of azobisisobutyronitrile (polymerization initiator)〇 · A solution prepared by dissolving 1 part of ethyl acetate. After adding the initiator, 'at this temperature The temperature was maintained for 1 hour, and then the internal temperature was maintained at 5 4 to 5 6 (3, and ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts/hr. When the concentration was 35%, the addition of ethyl acetate vinegar was stopped, and the temperature was kept at this temperature from the start of the addition of ethyl acetate until 12 hours passed. Finally, ethyl acetate was added to make the concentration of the acrylic resin 20%. The method was adjusted to prepare an ethyl acetate solution of an acrylic resin. The obtained acrylic resin was obtained by GPC, and the weight average molecular weight Mw in terms of polystyrene was 1.66 million, and Mw/Mn was 4·0. This was made into the acrylic resin A. The acrylic resin contains 8% of the structural unit derived from 2-carboxyethyl acrylate of the monomer (A-3), and contains 8% of the structural unit derived from the terpolymer of acrylic acid. Structural unit derived from acrylic acid 0.04%» [Polymerization Example 2] In the monomer composition, the amount of butyl acrylate was changed to 70.9 parts, the amount of "PCEA" was changed to 0.1 part, and the polymerization example i was used. The polystyrene-equivalent weight average molecular weight Mw obtained by GPC obtained from the ethyl acetate solution obtained by preparing the ethyl acetate solution of the acrylic resin in the same manner was 1.64 million, and Mw/Mn was 4.0. This was made into the acrylic resin b. The acrylic resin contains 0.04% of a structural unit derived from 2-cycloethyl acrylate of the monomer (A-3), and contains 0.04% of a structural unit derived from a terpolymer of acrylic acid and derived from acrylic acid. The structural unit 〇 _ 〇 2%. [Polymerization Example 3] 161767.doc -36- 201235436 In the monomer composition, the amount of butyl acrylate was changed to 7〇92 parts, and the amount of "PCEA" was changed to 〇.08 parts, and In the same manner as in Polymerization Example 1, an ethyl acetate solution of an acrylic resin was prepared. The obtained acrylic resin was obtained by GPC and had a weight average molecular weight Mw of 1.15 million and Mw/Mn of 4.7. This was made into an acrylic resin C. The acrylic resin contains 0.032% of a structural unit derived from 2-carboxyethyl acrylate corresponding to the monomer (a-3), and contains 0.032% of a structural unit derived from an acrylic acid terpolymer and 0.016% of a structural unit derived from acrylic acid. . [Polymerization Example 4] Acrylic acid was prepared in the same manner as in Polymerization Example 1, except that the amount of the butyl acrylate was changed to 70.95 parts and the amount of "PCEA" was changed to 5 parts by weight. An ethyl acetate solution of a resin. The obtained acrylic resin was obtained by GPC and had a polystyrene-equivalent weight average molecular weight Mw of 1.66 million and Mw/Mn of 4.8. This was made into an acrylic resin D. The acrylic resin contains a structural unit of 2-carboxyethyl acrylate corresponding to the monomer (A-3) 〇.〇2°/〇, and other than the structural unit of the terpolymer derived from acrylic acid, 0.02% and derived from acrylic acid. The structural unit is 0.01%. [Polymerization Example 5] In the monomer composition, the amount of butyl acrylate was changed to 70.9 parts, the amount of "PCEA" was changed to 0.1 part, and the same amount (1.0 part) of 4-hydroxybutyl propionate was used. An ethyl acetate solution of an acrylic resin was prepared in the same manner as in Polymerization Example 1, except that 2-hydroxyethyl acrylate was used. The obtained 161767.doc •37-201235436 acrylic resin obtained by GPC has a weight average molecular weight Mw of 1.66 million, Mw/Mn of 4.0», and its gas is an acrylic resin. E. The acrylic resin contains 0.04% of a structural unit derived from 2-carboxyethyl acrylate corresponding to the monomer (A-), and contains 0.04% of a structural unit derived from a terpolymer of acrylic acid and a structure derived from acrylic acid. Unit 0·02〇/〇. [Polymerization Example 6] (Comparative) In the monomer composition, the amount of butyl acrylate was changed to 7〇4 parts, and the amount of “0CEA” was changed to 〇·6 parts, and the same amount (8 parts) was used. An acrylic acid ethyl acetate solution of an acrylic resin was prepared in the same manner as in Polymerization Example 1, except that 2-phenoxyethyl acrylate was used instead of 2-(2-phenoxyethoxy)ethyl acrylate. The obtained acrylic resin was obtained by GPC, and the weight average molecular weight Mw in terms of polystyrene was 690,000, and Mw/Mn was 4.2. This is made into an acrylic resin v. This acrylic resin contains 0.24% of structural units derived from the 2-carboxyethyl acrylate of the monomer (A-3), and contains the structural unit of the terpolymer derived from acrylic acid. 24% and structural units from acrylic acid 〇.12〇/. . [Polymerization Example 7] (Comparative) An ethyl acetate solution of an acrylic resin was prepared in the same manner as in Polymerization Example 6, except that the same amount (0.6 part) of acrylic acid was used instead of "0CEA". The obtained acrylic resin was obtained by GPC, and the weight average molecular weight Mw in terms of polystyrene was 1.42 million 'Mw/Mn was 5.2 ^, and this was made into an acrylic resin w. The acrylic resin does not contain a structural unit equivalent to the monomer (A_3), but instead contains 161767.doc • 38 - 201235436 0.6% of the structural unit derived from acrylic acid. [Polymerization Example 8] (Comparative) Acrylic resin was prepared in the same manner as in Polymerization Example 6, except that the same amount (〇·6 parts) r M_53〇〇 was used instead of "PCEA" in the monomer composition. Ethyl acetate solution. The obtained acrylic resin was obtained by GPC and had a polystyrene-equivalent weight average molecular weight Mw of 1,580,000 Mw/Mn of 4.5. This was made into the acrylic resin X. The acrylic resin also does not contain a structural unit corresponding to the monomer (A-3), and instead contains ω-carboxypolycaprolactone monoacrylate cH2=CHCOO (; C5HI()COO)nH (η f 2) Structural unit 〇·6 % » [Polymerization Example 9] (for comparison) In the monomer composition, the amount of acrylic acid butyl gram was changed to 6 9.3 parts, and the amount of "M-5300" was changed to 1 _7 parts. An ethyl acetate solution of an acrylic resin was prepared in the same manner as in Polymerization Example 8 except for the above. The obtained acrylic resin was obtained by GPC and had a weight average molecular weight Mw of 1.74 million and Mw/Mn of 3.9. This was made into an acrylic resin Y. The acrylic resin also does not contain a structural unit corresponding to the monomer (A-3), and instead contains a structural unit derived from 'carboxypolycaprolactone monoacrylate CH2=CHCOO(C5H丨〇COO)nH(n and 2). 1.7%. [Polymerization Example 10] (Comparative) An acrylic resin was prepared in the same manner as in Polymerization Example 2 except that the same amount (0.1 part) of r A-SA" was used instead of "pCEA" in the monomer composition. Ethyl acetate solution. The obtained acrylic resin is obtained by Gpc 161767.doc -39- 201235436

而求出之聚苯乙稀換算之重量平均分子量Mw為173萬’ Mw/Mn為3.9。將其設為丙稀酸系樹脂Z °該丙稀酸系樹脂亦 不含有相當於單體（A_3)之結構單位’取而代之含有來自丁 二酸 2-丙烯醯氧基乙酯 CH2=CHCOOCH2CH2OCOCH2CH2COOH 之結構單位0.1%。 將以上聚合例1~10中之單體之加入組成、以及所獲得之 丙烯酸系樹脂之重量平均分子量及Mw/Mn之一覽匯總於表 [表1] 聚合例 1 2 3 4 5 6 7 8 9 10 單體之加入組成 (丙烯酸酯） BA 70.8% 70.9% 70.92% 70.95% 70.9% 70.4% 70.4% 70.4% 69.3% 70.9% MA 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% PEA2 8.0% 8.0% 8.0% 8.0% 8.0% - - - 8.0% PEA - - - - - 8.0% 8.0% 8.0% 8.0% - (含羥基之單體） 2HEA 1.0% 1.0% 1.0% 1.0% - 1.0% 1.0% 1.0% 1.0% 1.0% 4HBA - - - - 1.0% - - - - - (含羧基之單體） PCEA 0.2% 0.1% 0.08% 0.05% 0.1% 0.6% - - - AA - - - 0.6% - - - M-5300 - - - - - - 0.6% 1.7% - A-SA - - - - - - - - 0.1% 所獲得之丙烯酸系樹脂 分子量 166萬 164萬 151萬 166萬 166萬 169萬142萬 158萬 174萬 173萬 Mw/Mn 4.0 4.0 4.7 4.8 4.0 4.2 5.2 4.5 3.9 4.1 符號 A B C D E V W X Y Z (備考） 比 較 用 (表1之腳註係表示單體之符號之意思） BA :丙烯酸丁酯 MA :丙烯酸甲酯 161767.doc -40- 201235436 PEA2 :丙烯酸2-(2-苯氧基乙氧基）乙酯 PEA :丙烯酸2-苯氧基乙酯 2HEA :丙烯酸2-羥基乙酯 4HBA :丙烯酸4-羥基丁酯 PCEA : β-丙烯酸羧基乙酯 CH2=CH(COOCH2CH2)nCOOH(n=平均 1) [含有丙烯酸2-羧基乙酯（上式中n= 1)40%] AA :丙烯酸 M-5300 : ω-羧基聚己内酯（n与2)單丙烯酸酯 A-SA : 丁二酸2-丙烯醯氧基乙酯 繼而’表示使用以上所製造之丙烯酸系樹脂製備黏著 劑’並應用於光學膜之實施例及比較例。於以下例子中， 分別使用以下者（均為商品名）作為交聯劑及矽烷系化合 物。 <交聯劑>The weight average molecular weight Mw of the obtained polystyrene conversion was 1.73 million 'Mw/Mn was 3.9. This is made into an acrylic resin Z °. The acrylic resin does not contain a structural unit corresponding to the monomer (A_3) and instead contains a structure derived from 2-acryloxyethyl succinate CH2=CHCOOCH2CH2OCOCH2CH2COOH. Unit is 0.1%. A summary of the composition of the monomers in the above Polymerization Examples 1 to 10 and the weight average molecular weight and Mw/Mn of the obtained acrylic resin are summarized in the table [Table 1] Polymerization Example 1 2 3 4 5 6 7 8 9 10 monomer addition composition (acrylate) BA 70.8% 70.9% 70.92% 70.95% 70.9% 70.4% 70.4% 70.4% 69.3% 70.9% MA 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% PEA2 8.0% 8.0% 8.0% 8.0% 8.0% - - - 8.0% PEA - - - - - 8.0% 8.0% 8.0% 8.0% - (hydroxyl-containing monomer) 2HEA 1.0% 1.0% 1.0% 1.0% - 1.0% 1.0% 1.0% 1.0% 1.0% 4HBA - - - - 1.0% - - - - - (Carboxyl group-containing monomer) PCEA 0.2% 0.1% 0.08% 0.05% 0.1% 0.6% - - - AA - - - 0.6 % - - - M-5300 - - - - - - 0.6% 1.7% - A-SA - - - - - - - - 0.1% The acrylic resin obtained has a molecular weight of 1.66.14 million 1.511.16 million. 1.42 million 1.78 million 1.73 million Mw / Mn 4.0 4.0 4.7 4.8 4.0 4.2 5.2 4.5 3.9 4.1 Symbol ABCDEVWXYZ (Remarks) Comparison (the footnote of Table 1 indicates the meaning of the symbol of the single element) BA: butyl acrylate MA: methyl acrylate 161767.doc -40- 201235436 PEA2: 2-(2-phenoxyethoxy)ethyl acrylate PEA: 2-phenoxyethyl acrylate 2HEA: acrylic acid 2- Hydroxyethyl ester 4HBA: 4-hydroxybutyl acrylate PCEA: β-Acrylic carboxyethyl ester CH2=CH(COOCH2CH2)nCOOH (n=average 1) [Contains 2-carboxyethyl acrylate (n=1 in the above formula) 40%) ] AA : Acrylic acid M-5300 : ω-carboxypolycaprolactone (n and 2) monoacrylate A-SA : 2-propenyl methoxy succinate and then 'represents the preparation of the acrylic resin produced above The adhesive was applied to the examples and comparative examples of the optical film. In the following examples, the following (all trade names) were used as a crosslinking agent and a decane-based compound. <Crosslinking agent>

Coronate L:甲苯二異氰酸酯之三羥甲基丙烷加合物之 乙酸乙酯溶液（固形分濃度為75%)、自日本聚胺酯（股份有 限公司）獲得。 <矽烷系化合物> KBM-403 : 3-縮水甘油氧基丙基三甲氧基矽烷、液體、 自仏越化學工業（股份有限公司）獲得。 [實施例1〜5及比較例1〜6] (a)黏著劑之製造 使用聚合例1〜10中所獲得之丙烯酸系樹脂之2〇0/〇乙酸乙 161767.doc •41 · 201235436 δ旨溶液，相對於各自之固形分100份，混合表2所示之各自 之量之上述交聯劑（Coronate L)、及0.5份之上述矽烷系化 合物（KBM-403)，進而以使固形分濃度成為13%之方式添 加乙酸乙酯而製成黏著劑組合物。再者，交聯劑（c〇r〇nate L)如上述般為固形分濃度為75%之乙酸乙酯溶液，表2所示 之添加量為其固形分量。 (b) 黏著劑片材之製作 使用敷料器’以使乾燥後之厚度成為2 〇 pm之方式將上 述（a)所製備之各黏著劑組合物塗佈於實施脫模處理之聚對 本一甲酸乙二酯膜[商品名「PLR-382050」、自LINTEC(股 份有限公司）獲得，稱為隔板]之脫模處理面，於l〇〇〇c下乾 燥1分鐘而製作黏著劑片材。 (c) 黏著劑片材之凝膠分率測定 於將上述（b)所製作之黏著劑片材於室溫下放置2天後、 及於室溫下放置7天後’分別藉由先前敍述之方法測定凝 膠分率。分別將放置2天後之值示於表2之「第2天」之 攔，將放置7天後之值示於表2之「第7天」之攔，並且將 放置2天後之凝膠分率相對於放置7天後之凝膠分率的比示 於表2之「第2天/第7天」之攔。 (d) 附有黏著劑之偏光板之製作 於藉由包含三乙醯纖維素之保護膜夾持碘吸附配向於聚 乙稀醇中之偏光膜之兩面的3層結構之偏光板之單面，藉 由貼合機使上述（b)所製作之黏著劑片材之與隔板為相反側 之面（黏著劑面）貼合後’於溫度為23〇c、相對濕度為65〇/〇 161767.doc •42- 201235436 之條件下固化7天而製作附有黏著劑之偏光板。 (e)光學積層體之製作及評價 自上述⑷所製作之附有黏著劑之偏光板剝離隔板後， 以成為正交偏光鏡之方式將其黏著劑面黏著於液晶單元用 玻璃基板[商品名「EAGLE XG」、自康寧公司獲得]之兩 面而製作光學積層體。對該光學積層體進行於溫度為8(rc 之乾燥條件下保管96小時之耐熱試驗。其後，卩目視觀察 自一偏光板側射人光時之發白之表現狀態。將結果按照以 下基準分類並示於表2之「發白」之攔。 (發白之表現狀態） ◎.完全未發現發白。 〇：發白幾乎不顯眼。 △:發白稍微顯眼。 χ :明顯確認有發白。 又，於進行於溫度80。(：之乾燥條件下保管3〇〇小時之耐 熱試驗之情形（表2中表示為「耐熱」）；進行於溫度為 60 C、相對濕度為90¾下保管300小時之耐濕熱試驗之情 形（於表2中表示為「耐濕熱」）；及進行將自加熱至川艽之 狀態降溫至-30eC，繼而升溫至70°C之過程作為1個週期 小時），對其反覆進行100個週期之耐熱震試驗之情形（表2 中表示為「耐HS」）時，以目視觀察試驗後之光學積層 體。將結果按照以下基準進行分類並匯總於表2。 <耐熱試驗、财濕熱試驗及财熱震試驗之評價基準> ◎:完全未發現浮起、剝離、發泡等外觀變化。 161767.doc •43· 201235436 〇：幾乎未發現浮起、剝離、發泡等外觀變化。 △:浮起、剝離、發泡等外觀變化稍微顯眼。 X :明顯確認有浮起、剝離、發泡等外觀變化。 (f)附有黏著劑之光學膜之二次加工性評價 二次加工性之評價係以如下方式進行。首先，將上述(c〕 所製作之附有黏著劑之偏光板裁剪成25匪仙腿大小 之式片繼而n式片於其黏著劑側，使用黏附裝置 [FUJIPLA(股份有限公司）製造之「Lamipackerj (商品名）] 而黏附於液晶單元用玻螭基板上，於50t、5 kg/cm2 (490.3 kPa)之加壓下進行2G分鐘高壓爸處理。繼而於賊 下進行2小時加熱處理’繼而於抓之烘箱中保管48小時 後，於溫度為23。。、相對濕度為50%之環境下，進行以 麗/分鐘之速度將偏光板自該黏著試片沿剛。方向（折 回而沿著玻璃基板面之方向）剝離之剝離試驗，觀察剝離 後之玻璃基板表面之狀態，按照以下基準進行分類。將結 果一併示於表2之「二次加工性」之欄。 <二次加工性之評價基準> ◎.於玻璃基板表面完全未確認有污點等。 〇.於玻璃基板表面幾乎未確認有污點等。 △.於玻璃基板表面確認有污點等。 X:於玻璃基板表面確認有黏著劑之殘留。 16l767.doc -44· 201235436 [表2] 凝膠分率 第2天(％) 第7天(％) 第2天/ 第7天 發白 耐久性 耐熱 耐濕熱 耐HS 二次加工性 8 5 15 7 2 14 762 743 4 5 5 7 ο ο 8 8 9 4 6 7 9 3 5 7 2 9 7 7 4 7 7 7 2 4 7 7 0· 91 0· 96 0. 97 0. 3 9 0· 0· 6 0· 72 0· •° 0· 40 0· ο 〇 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ 〇◎〇© 〇◎〇〇 〇◎〇〇 ◎ ◎ ◎ ◎ ◎〇〇X ◎ ◎〇〇 ◎ ◎ ◎ ◎ 〇〇◎〇 ◎ ◎ ◎〇 〇〇◎〇 實施例 ___比較例 1 2 3 4 5 1 2 3 4 5 6 丙稀酸樹脂 A B C D E V W X X Y Z (含OH之成分） 2HEA(%) 1.0 1.0 1.0 1.0 - 1.0 1.0 1.0 1.0 1.0 1.0 4HBA(°/〇) - - - - 1.0 - - - - - (含COOH之成分） 2CEA(°/〇) 0.08 0.04 0.032 0.02 0.04 0.24 - - - AA-3(%) 0.08 0.04 0.032 0.02 0.04 0.24 _ - - - AA(°/〇) 0.04 0.02 0.016 0.01 0.02 0.12 0.6 - - - M-5300(%) 0.6 0.6 1.7 - A-SA(%) 0.1 交聯劑 添加量(份） 0.2 0.3 0.27 0.375 0.2 0.3 0.5 0.2 0.4 0.2 0.4 (表2之腳註係表示丙烯酸系樹脂之單體之符號之意思） 2HEA :丙歸酸2-經基乙酯Coronate L: Ethyl acetate solution of toluene diisocyanate trimethylolpropane adduct (solids concentration: 75%), obtained from Japan Polyurethane (Stock Co., Ltd.). <decane compound> KBM-403: 3-glycidoxypropyltrimethoxydecane, liquid, obtained from Toyo Chemical Industry Co., Ltd. [Examples 1 to 5 and Comparative Examples 1 to 6] (a) Production of an adhesive The use of an acrylic resin obtained in Polymerization Examples 1 to 10 was carried out using 2〇0/〇 acetic acid B 161767.doc •41 · 201235436 δ The solution was mixed with the above-mentioned crosslinking agent (Coronate L) and 0.5 part of the above decane-based compound (KBM-403) in the respective amounts shown in Table 2 with respect to 100 parts of the respective solid content, thereby further adjusting the solid concentration. Ethyl acetate was added in a manner of 13% to prepare an adhesive composition. Further, the crosslinking agent (c〇r〇nate L) was an ethyl acetate solution having a solid concentration of 75% as described above, and the addition amount shown in Table 2 was a solid content. (b) Preparation of the adhesive sheet The adhesive composition prepared in the above (a) was applied to the poly(p-formic acid) subjected to the release treatment by using the applicator 'to make the thickness after drying to 2 〇pm. The release film of the ethylene glycol film [trade name "PLR-382050", obtained from LINTEC Co., Ltd., called a separator] was dried at 1 ° C for 1 minute to prepare an adhesive sheet. (c) The gel fraction of the adhesive sheet was measured after the adhesive sheet prepared in the above (b) was allowed to stand at room temperature for 2 days and left at room temperature for 7 days, respectively. The method was used to determine the gel fraction. The values after 2 days of placement are shown in the "Day 2" of Table 2, and the values after 7 days are shown in the "7th day" of Table 2, and the gel will be placed after 2 days. The ratio of the fraction to the gel fraction after 7 days of placement is shown in Table 2, "Day 2 / Day 7". (d) A polarizing plate with an adhesive is formed on one side of a polarizing plate having a three-layer structure in which iodine is adsorbed to both sides of a polarizing film in polyethylene glycol by a protective film containing triacetyl cellulose. After bonding the adhesive sheet prepared in the above (b) to the opposite side of the separator (adhesive surface) by a laminating machine, the temperature is 23 〇c and the relative humidity is 65 〇/〇. 161767.doc • 42-201235436 cured for 7 days to make a polarizer with adhesive. (e) Production and evaluation of the optical layered body After peeling off the separator from the polarizing plate with an adhesive prepared in the above (4), the adhesive surface is adhered to the glass substrate for liquid crystal cell so as to be a crossed polarizer. An optical laminate was produced on both sides of the name "EAGLE XG" and obtained from Corning. The optical laminate was subjected to a heat resistance test under a drying condition of a temperature of 8 (r) for 96 hours. Thereafter, the state of blushing when the human light was emitted from a polarizing plate side was visually observed. The results were based on the following criteria. The classification is shown in Table 2, "Whitening". (Whitening performance status) ◎. No blushing at all. 〇: Whitening is almost inconspicuous. △: Whitening is slightly conspicuous. χ: Obviously confirmed In addition, it is carried out at a temperature of 80. (In the case of a heat-resistant test for 3 hours under dry conditions (in Table 2, "heat-resistant"); it is stored at a temperature of 60 C and a relative humidity of 902⁄4. 300 hours of heat and humidity resistance test (shown as "moisture resistance" in Table 2); and the process of cooling from the state of heating to Chuanxiong to -30eC, and then heating to 70 °C as one cycle hour) When the thermal shock test of 100 cycles was repeated (indicated as "HS resistance" in Table 2), the optical laminate after the test was visually observed. The results were classified according to the following criteria and summarized in Table 2. <Heat resistance test, heat and humidity Evaluation criteria for the test and the thermal shock test> ◎: No change in appearance such as lifting, peeling, foaming, etc. was observed. 161767.doc •43· 201235436 〇: Appearance changes such as floating, peeling, and foaming were hardly observed. △: Appearance changes such as floatation, peeling, and foaming were noticeable. X: Appearance changes such as floatation, peeling, and foaming were clearly confirmed. (f) Secondary processing evaluation of optical film with adhesive agent Secondary processing The evaluation of the nature is carried out in the following manner. First, the polarizing plate with the adhesive prepared in the above (c) is cut into a sheet of 25 匪 腿 leg size, and then the n-type sheet is on the adhesive side, using an adhesive device [ "Lamipackerj (trade name)" manufactured by FUJIPLA Co., Ltd., adhered to a glass substrate for liquid crystal cells, and subjected to 2G minutes of high pressure dad treatment under a pressure of 50t, 5 kg/cm2 (490.3 kPa). The thief under the heat treatment for 2 hours', and then stored in the oven for 48 hours, at a temperature of 23%, and a relative humidity of 50%, the polarizing plate was applied at a speed of ML/minute from the adhesive test piece. Along the direction The peeling test of the peeling of the glass substrate surface was performed, and the state of the surface of the glass substrate after peeling was observed, and the classification was performed according to the following criteria. The results are shown together in the column of "secondary workability" in Table 2. <Secondary processing [Evaluation criteria] ◎. No stains were observed on the surface of the glass substrate. 污. No stains were observed on the surface of the glass substrate. △. Stain was observed on the surface of the glass substrate. X: Adhesion was confirmed on the surface of the glass substrate. Residue of the agent. 16l767.doc -44· 201235436 [Table 2] Gel fraction rate 2nd day (%) Day 7 (%) Day 2 / Day 7 Whitening Durability Heat and moisture resistance Heat resistant HS Secondary processing Sex 8 5 15 7 2 14 762 743 4 5 5 7 ο ο 8 8 9 4 6 7 9 3 5 7 2 9 7 7 4 7 7 7 2 4 7 7 0· 91 0· 96 0. 97 0. 3 9 0· 0· 6 0· 72 0· • ° 0· 40 0· ο 〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 〇 〇〇〇 〇〇〇 〇〇 〇〇 ◎ ◎ ◎ ◎ ◎ 〇〇 X ◎ ◎ 〇〇 ◎ ◎ ◎ ◎ 〇〇 〇 〇 ◎ ◎ ◎ 〇〇〇 ◎ 〇 Example ___ Comparative Example 1 2 3 4 5 1 2 3 4 5 6 Acrylic resin ABCDEVWXXYZ (Components containing OH) 2HEA(%) 1.0 1.0 1.0 1.0 - 1.0 1.0 1.0 1.0 1.0 1.0 4HBA(°/〇) - - - - 1.0 - - - - - (Components containing COOH) 2CEA(°/〇) 0.08 0.04 0.032 0.02 0.04 0.24 - - - AA-3(%) 0.08 0.04 0.032 0.02 0.04 0.24 _ - - - AA(°/〇) 0.04 0.02 0.016 0.01 0.02 0.12 0.6 - - - M-5300(%) 0.6 0.6 1.7 - A-SA (%) 0.1 Crosslinking amount (parts) 0.2 0.3 0.27 0.375 0.2 0.3 0.5 0.2 0.4 0.2 0.4 (The footnote of Table 2 indicates the symbol of the monomer of the acrylic resin) 2HEA: Acrylate 2 - thioethyl ester

4ΗΒΑ 2CEA ΑΑ-3 ΑΑ Μ-5300 A-SA 丙烯酸4-羥基丁酯 丙稀酸2-緩基乙醋（丙稀酸之二聚物） 丙烯酸之三聚物以上之低聚物 丙稀酸 ω-缓基聚己内I旨（η与2)單丙稀酸醋 丁二酸2-丙烯醯氧基乙酯 I61767.doc •45- 201235436 如表1及表2所示般，於使相當於上述式（II)之丙烯酸2-叛基乙醋於本發明所規定之範圍内以規定量共聚合之丙烯 酸系樹脂A〜E中調配規定量之交聯劑而構成黏著劑組合物 之實施例1〜5 ’提供自塗佈成片狀後第2天之凝膠分率相對 於第7天之凝膠分率的比較高之黏著劑片材。因此，可縮 短塗佈成片狀後直至裁剪等加工可無問題地進行為止之固 化時間’成為加工性優異者。該等實施例之黏著劑片材供 給有效地防止發白之光學積層體，二次加工性亦良好。 又’獲得於耐熱性、耐濕熱性及耐熱震性方面亦可大致滿 足之結果。尤其是實施例4具有於加工性、防止發白、耐 熱性、耐濕熱性、耐熱震性及二次加工性之所有方面均優 異之性能。 相對於此，使用存在超過0.2%之來自相當於上述式（^) 之丙烯酸2-羧基乙酯之結構單位的丙烯酸系樹脂v之比較 例1 ’雖然將黏著劑組合物塗佈成片狀後第2天顯示可與第 7天匹敵之凝膠分率，但二次加工性不足。又，使用使丙 烯酸共聚合之丙烯酸系樹脂W而並非上述式（II)所示之含 羧基之（曱基）丙烯酸酯（A-3)的比較例2、及使用使雖然與 上述式（II)類似但藉由聚合而成為主鏈之部位與羧基之間 的原子數多於式（II)之含羧基之丙烯酸酯單體共聚合之丙 烯酸系樹脂X、Y或Z的比較例3〜6，塗佈成片狀後第2天之 凝膠分率相對於第7天之凝膠分率的比低於0.8，加工性不 可謂充分。又，總而言之，顯示容易因加熱而稍微發白之 傾向。 161767.doc •46- 201235436 本發明之黏著劑片材係耐久性及二次力。工性優異，且可 縮短形成片材後直至可進行加工為止所需要之固化時間， 加工性優異。設置有該黏著㈣材之光學膜可較佳地用於 液晶顯示裝置。 【圖式簡單說明】 圖 1(A)- -(D)係表示本發明之光學積層體之較佳之層構成 的例子之剖面模式圖。 【主要元件符號說明】 1 偏光膜 2 表面處理層 3 (第一）保護膜 4 第二保護膜 5 偏光板 7 相位差膜 8 層間黏著劑 10 光學膜 20 貼合於液晶單元（玻璃基板）上之黏著劑層（黏著 劑片材） 25 附有黏著劑之光學膜 30 液晶單元（玻璃基板） 40 光學積層體 161767.doc -47-4ΗΒΑ 2CEA ΑΑ-3 ΑΑ Μ-5300 A-SA 4-hydroxybutyl acrylate acrylic acid 2-fustoethyl acetonate (dimer of acrylic acid) oligomer of acrylic acid terpolymer acrylic acid ω - 缓基聚己内I (η and 2) monoacrylic acid succinic acid 2-propenyl methoxyethyl ester I61767.doc •45- 201235436 As shown in Table 1 and Table 2, Example of the adhesive composition of the acrylic acid resin A to E of the above formula (II) in which a predetermined amount of the crosslinking agent is blended in a predetermined amount of the acrylic resin A to E. 1 to 5 'provided an adhesive sheet having a relatively high gel fraction on the second day after coating into a sheet shape with respect to the gel fraction on the seventh day. Therefore, the curing time which can be shortened after being applied in a sheet form until the processing such as cutting can be carried out without problems is excellent in workability. The adhesive sheet of the examples was supplied to an optical laminate which effectively prevented blushing, and the secondary workability was also good. Further, the results obtained in terms of heat resistance, moist heat resistance, and thermal shock resistance can be substantially satisfied. In particular, Example 4 has excellent properties in all aspects of workability, prevention of blushing, heat resistance, heat and humidity resistance, thermal shock resistance and secondary workability. On the other hand, Comparative Example 1 in which more than 0.2% of the acrylic resin v derived from the structural unit of 2-carboxyethyl acrylate of the above formula (^) was used was used, and the adhesive composition was applied in a sheet form. The second day showed a gel fraction which was comparable to the seventh day, but the secondary workability was insufficient. Further, Comparative Example 2 using the acrylic resin W copolymerizing acrylic acid and not containing the carboxyl group-containing (fluorenyl) acrylate (A-3) represented by the above formula (II), and the use of the above formula (II) Comparative Examples 3 to 6 of acrylic resin X, Y or Z similar in that the number of atoms between the main chain and the carboxyl group is more than the carboxyl group-containing acrylate monomer of the formula (II) The ratio of the gel fraction on the second day after application to the sheet form to the gel fraction on the seventh day was less than 0.8, and the workability was not sufficient. Further, in summary, it tends to be slightly whitened by heating. 161767.doc •46- 201235436 The adhesive sheet of the present invention is durability and secondary force. The workability is excellent, and the curing time required until the sheet can be formed can be shortened, and the workability is excellent. The optical film provided with the adhesive (four) material can be preferably used for a liquid crystal display device. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (A) - (D) are schematic cross-sectional views showing an example of a preferred layer constitution of an optical layered body of the present invention. [Description of main components] 1 polarizing film 2 surface treatment layer 3 (first) protective film 4 second protective film 5 polarizing plate 7 retardation film 8 interlayer adhesive 10 optical film 20 bonded to liquid crystal cell (glass substrate) Adhesive layer (adhesive sheet) 25 Optical film with adhesive 30 Liquid crystal cell (glass substrate) 40 Optical laminate 161767.doc -47-

Claims (1)

201235436 七、申請專利範圍： 1 · 一種黏著劑片材，其係將含有（A)丙烯酸系樹脂1 00重量 份、以及 (B)交聯劑〇.〇 1〜5重量份之黏著劑組合物形成為片狀而 製成，該（A)丙烯酸系樹脂係由含有以下（A-1)〜(a_3)之 單體混合物所獲得之共聚物，且重量平均分子量為1〇〇 萬〜200萬： (A-1)下式（I)所示之（曱基）丙烯酸酯94.8〜99.89重量 %、201235436 VII. Patent application scope: 1 . An adhesive sheet comprising (A) acrylic resin 100 parts by weight, and (B) crosslinking agent 〇. 〇 1 to 5 parts by weight of the adhesive composition The (A) acrylic resin is a copolymer obtained from a monomer mixture containing the following (A-1) to (a-3), and has a weight average molecular weight of 10,000 to 2,000,000. : (A-1) (meth) acrylate represented by the following formula (I): 94.8 to 99.89 wt%, (式中’ Ri表示氫原子或曱基，表示碳數14以下之烧基 或碳數14以下之芳烧基’構成I之氫原子可由基 (C2H4〇)n-R3取代’ n表示〇或1〜4之整數，R_3表示碳數12 以下之燒基或碳數12以下之芳基） (A-2)具有羥基之（甲基）丙烯酸系單體〇丨〜5重量％、及 (A-3)下式（π)所示之含羧基之（甲基）丙烯酸酯〇 〇1〜〇 2 重量％ CH2=c-C-0—A-COOH (H) Ο (式中，R·4表示氫原子或曱基，A表示碳數2〜4之2價有機 基）。 2.如請求項丨之黏著劑片材，其中將黏著劑組合物塗佈成 161767.doc 201235436 片狀2天後之凝膠分率相對於塗佈成片狀7天後之凝膠分 率之比為0.8以上。 3·如凊求項1或2之黏著劑片材，其中含羧基之（曱基）丙烯 酸酯（A-3)為丙烯酸2-羧基乙酯。 4. 如請求項1至3中任一項之黏著劑片材，其中交聯劑（B)含 有異氰酸酯系化合物。 5. 如請求項1至4中任-項之黏著劑片材，其中黏著劑組合 物進而含有（C)矽烷系化合物〇.〇3〜2重量份。 6. 如請求項!至5中任一項之黏著劑片材，其係形成於塑膠 膜上。 如請求項6之黏著劑片材，其中塑膠膜為實施脫模處理 之剝離膜。 8· -種附有黏著劑之光學膜，其係由光學膜及貼合於光學 膜之如請求項1至5中任一項之黏著劑片材所構成。 9.如請求項8之附有黏著劑之光學膜，其中光學膜係選自 偏光板及相位差膜者。 10. 一種光學積層體，其係、由玻璃基板、及以絲著劑片 側積層於玻璃基板上之如請求項8或9之附 學膜所構成。 < 161767.doc(wherein 'R represents a hydrogen atom or a fluorenyl group, and a aryl group having a carbon number of 14 or less or an aryl group having a carbon number of 14 or less'. The hydrogen atom constituting I may be replaced by a group (C2H4〇)n-R3, and 'n" represents hydrazine or An integer of 1 to 4, R_3 represents an alkyl group having a carbon number of 12 or less or an aryl group having a carbon number of 12 or less. (A-2) A (meth)acrylic monomer having a hydroxyl group 〇丨 5% by weight, and (A) -3) a carboxyl group-containing (meth) acrylate represented by the following formula (π) 〇〇1 to 〇2% by weight CH2=cC-0-A-COOH (H) Ο (wherein R·4 represents hydrogen Atom or a fluorenyl group, A represents a divalent organic group having a carbon number of 2 to 4. 2. The adhesive sheet according to claim 1, wherein the adhesive composition is coated into a 161767.doc 201235436 sheet form after 2 days, the gel fraction is relative to the gel fraction after 7 days of application in a sheet form. The ratio is 0.8 or more. 3. The adhesive sheet according to claim 1 or 2, wherein the carboxyl group-containing (mercapto) acrylate (A-3) is 2-carboxyethyl acrylate. 4. The adhesive sheet according to any one of claims 1 to 3, wherein the crosslinking agent (B) contains an isocyanate compound. 5. The adhesive sheet according to any one of claims 1 to 4, wherein the adhesive composition further contains (C) a decane-based compound 〇. 〇 3 to 2 parts by weight. 6. The adhesive sheet according to any one of claims 5 to 5, which is formed on a plastic film. The adhesive sheet of claim 6, wherein the plastic film is a release film which is subjected to a release treatment. An optical film to which an adhesive is attached, which is composed of an optical film and an adhesive sheet according to any one of claims 1 to 5 attached to the optical film. 9. The optical film of claim 8, wherein the optical film is selected from the group consisting of a polarizing plate and a retardation film. An optical laminate comprising a glass substrate and an appendage film of claim 8 or 9 laminated on the glass substrate with a side of the filament. < 161767.doc
TW101102631A 2011-01-25 2012-01-20 Pressure sensitive adhesive sheet, optical film with pressure sensitive adhesive and optical laminate TWI553085B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2011012641A JP5648494B2 (en) 2011-01-25 2011-01-25 Adhesive sheet, optical film with adhesive, and optical laminate

Publications (2)

Publication Number Publication Date
TW201235436A true TW201235436A (en) 2012-09-01
TWI553085B TWI553085B (en) 2016-10-11

Family

ID=46558402

Family Applications (1)

Application Number Title Priority Date Filing Date
TW101102631A TWI553085B (en) 2011-01-25 2012-01-20 Pressure sensitive adhesive sheet, optical film with pressure sensitive adhesive and optical laminate

Country Status (4)

Country Link
JP (1) JP5648494B2 (en)
KR (1) KR101887693B1 (en)
CN (1) CN102618183B (en)
TW (1) TWI553085B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9419067B2 (en) 2014-08-06 2016-08-16 Everdisplay Optronics (Shanghai) Limited Display panel and manufacturing method thereof

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6302410B2 (en) * 2012-10-19 2018-03-28 リンテック株式会社 Adhesive composition and adhesive sheet
JPWO2014069542A1 (en) * 2012-10-30 2016-09-08 旭硝子株式会社 Laminated body and display device
JP6058390B2 (en) * 2012-12-27 2017-01-11 日本カーバイド工業株式会社 Adhesive composition and optical member surface protective film
JP2014206684A (en) * 2013-04-15 2014-10-30 大日本印刷株式会社 Optical film, optical film transfer body, and image display device
JP6236848B2 (en) * 2013-04-18 2017-11-29 大日本印刷株式会社 Optical film, optical film transfer body, image display device, optical film manufacturing method, and optical film transfer body manufacturing method
JP6111836B2 (en) * 2013-05-10 2017-04-12 Dic株式会社 Adhesive tape
JP6602201B2 (en) * 2013-08-29 2019-11-06 日本カーバイド工業株式会社 Adhesive composition for polarizing plate, polarizing plate with adhesive, and display device
TWI645010B (en) * 2014-03-17 2018-12-21 日商住友化學股份有限公司 Resin film with adhesive and optical laminate using the same
KR20160134681A (en) * 2014-03-18 2016-11-23 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 Adhesive composition for polarizing plate, adhesive sheet and polarizing plate with adhesive layer
JP6804843B2 (en) * 2015-01-30 2020-12-23 日東電工株式会社 Optical surface protective film with separator
JP6613818B2 (en) * 2015-10-30 2019-12-04 東洋インキＳｃホールディングス株式会社 Pressure sensitive adhesive and pressure sensitive adhesive film
JP2017090700A (en) * 2015-11-11 2017-05-25 住友化学株式会社 Polarizing plate and IPS mode liquid crystal display device
JP6700032B2 (en) * 2015-12-15 2020-05-27 住友化学株式会社 Optical film with pressure-sensitive adhesive layer and optical laminate
TWI668285B (en) * 2015-12-31 2019-08-11 長興材料工業股份有限公司 Thermally polymerizable composition, combonied solution formed therefrom and use thereof
KR102137345B1 (en) * 2016-10-12 2020-07-23 코니카 미놀타 가부시키가이샤 Manufacturing method of optical film
WO2019004047A1 (en) * 2017-06-27 2019-01-03 住友化学株式会社 Adhesive composition and film with adhesive layer
JP7327740B2 (en) * 2017-08-09 2023-08-16 日本カーバイド工業株式会社 Adhesive composition for polarizing plate and polarizing plate with adhesive layer
JP6431162B2 (en) * 2017-11-17 2018-11-28 藤森工業株式会社 Adhesive composition and surface protective film
JP7275650B2 (en) * 2018-03-02 2023-05-18 三菱ケミカル株式会社 Adhesive composition for difficult-to-adhere adherends, adhesive for difficult-to-adhere adherends, and adhesive tape for difficult-to-adhere adherends
JP2022061624A (en) * 2020-10-07 2022-04-19 日東電工株式会社 Adhesive sheet, optical film with adhesive sheet, and image display unit
CN114517041B (en) * 2020-11-18 2023-06-13 深圳市万普拉斯科技有限公司 Film forming composition, preparation method and application thereof
CN113917577B (en) * 2021-12-13 2022-05-31 恒美光电股份有限公司 High-water-resistance and bending-resistance optical protective film, polarizer and liquid crystal display device

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004005067A (en) * 2002-05-30 2004-01-08 Nifty Corp Method and program for mediating individual proxy contract
JP3997270B2 (en) * 2005-11-21 2007-10-24 綜研化学株式会社 Optical film pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet, and optical member using the same
JP2007169329A (en) * 2005-12-19 2007-07-05 Saiden Chemical Industry Co Ltd Adhesive composition for optical use and adhesive sheet
JP2008045067A (en) * 2006-08-18 2008-02-28 Nitto Denko Corp Pressure-sensitive adhesive composition, adhesive layer, method for producing the same, and optical member with adhesive
JP5204612B2 (en) * 2007-12-20 2013-06-05 日東電工株式会社 Adhesive composition for optical film, adhesive optical film, and image display device
JP5379409B2 (en) * 2008-02-15 2013-12-25 日東電工株式会社 Adhesive composition for optical film, adhesive optical film, and image display device
JP5379410B2 (en) * 2008-03-14 2013-12-25 日東電工株式会社 Adhesive composition for optical film, adhesive optical film, and image display device
JP5281318B2 (en) * 2008-05-23 2013-09-04 日東電工株式会社 Adhesive composition and adhesive sheet for metal surface sticking
JP5507858B2 (en) * 2008-05-29 2014-05-28 日東電工株式会社 Adhesive composition for optical member, adhesive optical member, and image display device
KR101635234B1 (en) * 2008-08-11 2016-06-30 스미또모 가가꾸 가부시키가이샤 Optical film with adhesive and optical laminate using same
JP5187973B2 (en) * 2009-04-30 2013-04-24 日東電工株式会社 Optical film adhesive composition, optical film adhesive layer, adhesive optical film, and image display device
CN103168083B (en) * 2010-10-12 2015-11-25 日本合成化学工业株式会社 The optical component of Adhesive composition for optical component, optical component tackiness agent, band binder layer and image display device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9419067B2 (en) 2014-08-06 2016-08-16 Everdisplay Optronics (Shanghai) Limited Display panel and manufacturing method thereof

Also Published As

Publication number Publication date
TWI553085B (en) 2016-10-11
JP5648494B2 (en) 2015-01-07
KR20120086265A (en) 2012-08-02
JP2012153772A (en) 2012-08-16
CN102618183A (en) 2012-08-01
CN102618183B (en) 2016-05-04
KR101887693B1 (en) 2018-08-10

Similar Documents

Publication Publication Date Title
TW201235436A (en) Pressure sensitive adhesive sheet, optical film with pressure sensitive adhesive and optical laminate
CN104927691B (en) Adhesive-attached resin film and optical laminate using same
KR101900982B1 (en) Optical film having adhesive agent, and optical laminated body in which same is used
JP5354674B2 (en) Optical film with adhesive and optical laminate using the same
JP6721322B2 (en) Adhesive composition, adhesive sheet and optical film with adhesive
JP6605914B2 (en) Adhesive composition, adhesive layer, and optical member with adhesive layer
TWI837777B (en) Adhesive composition, adhesive layer and optical member attached with the same
TWI701306B (en) Adhesive composition, adhesive sheet, optical film with adhesive and optical laminate
JP2010066755A (en) Optical film with adhesive and optical laminate using it
KR20140120937A (en) Adhesive sheet, optical film with adhesive, optical laminate, and method for producing adhesive sheet
JP4839744B2 (en) Optical laminate and method for producing the same
JP2022125327A (en) Resin film with pressure-sensitive adhesive and optical laminate including the same
TWI579355B (en) An adhesive composition, an adhesive sheet, an optical film with an adhesive, and an optical laminate
TWI727008B (en) Optical member having adhesive layer
JP6024125B2 (en) Adhesive composition
JP6441018B2 (en) Adhesive composition and adhesive sheet
JP6518422B2 (en) Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and optical member with pressure-sensitive adhesive layer
JP5949013B2 (en) Adhesive sheet, optical film with adhesive, and optical laminate
JP6160743B2 (en) Adhesive sheet, optical film with adhesive, and optical laminate
JP6197919B2 (en) Adhesive sheet, optical film with adhesive, and optical laminate
JP2018124578A (en) Optical member with adhesive layer
JP2019044190A (en) Adhesive composition, adhesive layer, and adhesive layer-attached optical member