TW200904930A - Adhesive composition and optical film having adhesive agent - Google Patents

Adhesive composition and optical film having adhesive agent Download PDF

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Publication number
TW200904930A
TW200904930A TW097102019A TW97102019A TW200904930A TW 200904930 A TW200904930 A TW 200904930A TW 097102019 A TW097102019 A TW 097102019A TW 97102019 A TW97102019 A TW 97102019A TW 200904930 A TW200904930 A TW 200904930A
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adhesive
optical film
film
organopolyoxane
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TW097102019A
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Chinese (zh)
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TWI437066B (en
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Akinari Itagaki
Ryu Takeko
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Shinetsu Chemical Co
Sumitomo Chemical Co
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    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)
  • Paints Or Removers (AREA)

Abstract

Disclosed is an adhesive composition comprising: (A) an acrylic resin; (B) a crosslinking agent; (C) a first organopolysiloxane having a functional group and a methoxy group and/or an ethoxy group in the molecule, and (D) a second organopolysiloxane having a functional group and a methoxy group and/or an ethoxy group and also having an alkoxy group having 3 carbon atoms and/or an alkoxy group having 4 carbon atoms (e.g., a propoxy group, a butoxy group) in the molecule. When the composition is adhered to an optical film to produce an optical film having an adhesive agent, the resulting optical film exhibits steady properties over a long period, and can exhibit good rework property and excellent durability even when upsized. Therefore, the optical film having the adhesive agent can be suitably used in a liquid crystal display device.

Description

200904930 九、發明說明 【發明所屬之技術領域】 本發明係關於黏著劑組成物，以及特別是被使用於貼 合於液晶顯示用玻璃室（glass cell)之附黏著劑之光學薄膜 【先前技術】 一般 TN(Twisted Nematic，扭轉向列型）、STN(Super Twisted Nematic，超扭轉向列型）等之液晶顯示裝置所使 用的液晶室（liquid crystal cell)，係具有液晶成分挾持於 二片的玻璃基板間之結構，而且，各玻璃基板的表面上介 由以丙烯酸樹脂爲主成分之黏著劑，層合偏光薄膜、相位 差薄膜等之光學薄膜，此處之光學薄膜通常以至少單面上 形成黏著劑層之附黏著劑之光學薄膜的形態流通，在組立 液晶室之階段，將此黏著劑側貼合於玻璃基板之形態，爲 一般採取的形態。 如此的附黏著劑之光學薄膜，在熱或濕熱條件下因爲 伸縮而造成尺寸變化大，故貼合於玻璃基板之光學層合物 的狀態，會有黏著劑層內發泡，黏著劑層與玻璃基板之間 發生浮起或剝離等之問題。而且最近，亦使用液晶顯示裝 置作爲汽車導航系統等之車輛用，但在車輛用途，則更需 要具有在即使高溫•高濕條件下亦不會發生發泡或浮起、 剝離等之持久性。 此外，將附黏著劑之光學薄膜貼合於液晶顯示用玻璃 -5- 200904930 室時，有不週全的地方時，剝離此光學薄膜再重貼，亦要 求進行此剝離時，黏著劑層隨著光學薄膜剝離，在玻璃上 不會殘留黏著劑層、不會產生霧點等之所謂的再加工性。 最近隨著電視用途等的大型化，光學薄膜的面積亦在變大 中，故要求具有比先前技術更優異的再加工性。 爲了解決該相關的問題，提出許多關於以丙烯酸樹脂 爲主成分之黏著劑之各種提案，例如日本特許第3022993 號公報（專利文獻1)中，記載著將含有具有環氧基的矽烷 化合物之丙烯酸樹脂黏著劑層設置於偏光薄膜的表面。又 日本特許第3487940號公報（專利文獻2)中，亦記載著在丙 烯酸樹脂中摻合硬化劑與特定的矽酸鹽寡聚物之黏著劑組 成物，將此黏著劑組成物使用於偏光薄膜等之光學薄膜。 專利文獻1 :日本特許第3022993號公報（特開平4-223403號公報） 專利文獻2 :日本特許第3 4 8 7 9 4 0號公報（特開平8 -1 99 1 3 0號公報） 【發明內容】 [發明所欲解決之課題] 惟’本發明者等人經過精心硏究的結果，已知先前技 術習知之設置了黏著劑之光學薄膜，雖然在黏著劑塗佈後 3個月左右’介由此黏著劑層貼合於玻璃基板後的再加工 性或黏著持久性較優異，但塗佈後經過半年或1年的長時 間’會有介由此黏著劑層貼合於玻璃基板後的黏著持久性 -6- 200904930 或再加工性降低的情形。 在此，本發明的目的在於提供再加工性優良，同時貼 合於玻璃基時，可抑制玻璃基板與黏著劑層之間的浮起或 剝離，以及黏著劑層內的發泡，黏著劑塗佈後，即使經過 半年或1年的長時間後，不易發生上述的浮起或剝離、發 泡、霧點，且持久性及再加工性優異，因而適合作爲光學 薄膜的黏著劑之黏著劑組成物，以及使用其之附黏著劑之 光學薄膜。 [用以解決課題之手段] 本發明者等人，爲了該相關的課題而經過精心硏究的 結果，發現於黏著劑成分中摻合一分子內含有锍基等之官 能基與甲氧基及/或乙氧基之有機聚矽氧烷、與一分子內 含有同樣的锍基等之官能基與甲氧基及/或乙氧基之外， 再含有丙氧基或丁氧基等之碳原子數3及/或4的烷氧基之 有機聚矽氧烷，爲有效的作法。 亦即，自先前技術起即被使用於黏著劑領域之矽烷化 合物至有機聚矽氧烷，以分子內具有甲氧基及/或乙氧基 者較多，在此情況下，其水解性無法充分地控制，保存安 定性亦有問題，特別是因爲丙烯酸系黏著劑中含有水分， 故很難使含有矽烷化合物之黏著劑，長時間安定其作爲黏 著劑的性質。因此，發現可藉由倂用含有水解反應性高的 甲氧基或乙氧基之有機聚矽氧烷、與含有水解反應性低的 丙氧基或丁氧基等之碳原子數3及/或4的烷氧基之有機聚 200904930 矽氧烷’任意地變化矽烷化合物的水解反應性。所以，將 該2種的有機聚矽氧烷與丙烯酸樹脂及交聯劑一起摻合之 黏著劑組成物，水解之烷氧基的量因爲經過長時間亦保持 一定，故性能安定。 此外，於黏著劑中，依此層所設置的光學薄膜的種類 、使用條件等，摻合於其中的矽烷化合物的水解反應性會 有不同，但依各自的目的提共改變烷氧基的種類及含量的 單一製品這一點有限度，因此，藉由準備水解反應性不同 的至少2種的有機聚矽氧烷，使其成爲依所要求的階級而 改變此等的混合比率之組成物，擴大可應對的範圍。 而且，發現上述的有機聚矽氧烷，因爲具有作爲矽偶 合劑的效果，玻璃與丙烯酸樹脂的親和性高，故設置了由 摻合此成分的黏著劑組成物所形成的黏著劑層之附黏著劑 之光學薄膜，以此黏著劑層側貼合於玻璃基板時，黏著劑 層與玻璃基板之間的浮起或剝離等受到抑制；而且此有機 聚矽氧烷，因爲亦表現出作爲聚矽氧系剝離劑的效果，故 設置了由摻合此成分的黏著劑組成物所形成的黏著劑層之 附黏著劑之光學薄膜，成爲再加工性亦優異者，而完成本 發明。 所以，本發明係提供下述黏著劑組成物及附黏著劑之 光學薄膜。 (1)一種黏著劑組成物，其特徵係含有 (A)丙烯酸樹脂、 (B )交聯劑、 200904930 (C) 下述平均組成式（I)所表示的第一有機聚矽氧烷、 YaR1bSi(OCH3)c(〇C2H5)d(〇H)e〇(4-a-b-c-d-e)/2 …（I) (式中，γ表示具有至少1種選自锍基、環氧基、（甲 基）丙烯醯氧基、烯基、鹵化烷基及胺基之有機基；R1表 示至少1種之不具有脂肪族不飽和鍵的碳原子數1 ~8的非取 代的一價烴基；a、b、c'd及 e符合0.01SaSl、0$b < 2 ' 0 ^ c ^ 2 ' 各 2、OSegl，且 〇.1 刍 c + d^2.5 及 2 S a + b + c + d + e S 3 之數。） (D) 下述平均組成式（II)所表示的第二有機聚矽氧烷、 YfR1gSi(OCH3)h(〇C2H5)i(OR2)J(OH)kO(4-f.g.h-i-j-k)/2-·· (II) (式中，Y及R1表示與上述相同的意義；R2爲碳原子 數3及/或4的烷基或甲氧基丙基；f、g、h、i、j及k係符 合 O.OISfgl、〇Sg<2、0ShS2、〇Si$2、0<jS2、0 SkSl，而h與i不同時爲0’且0.1$h + i+jS2.5及2$ f+g + h + i+j + k S 3 之數》) (2)如（1)所記載之黏著劑組成物，其中丙烯酸樹脂（A) 係包含以（甲基）丙烯酸烷基酯所衍生的結構單元爲主成分 ，含有具有極性官能基之（甲基）丙烯酸系化合物所衍生的 結構單元之丙烯酸樹脂。 (3 )如（2 )所記載之黏著劑組成物，其中極性官能基爲 200904930 選自游離羧基、羥基、胺基及環氧環。 (4) 如（1)〜（3)中任—項所記載之黏著劑組成物，其中 交聯劑（B)含有異氰酸酯系化合物。 (5) 如（1)〜（4)中任一項所記載之黏著劑組成物，其中 表示第一有機聚矽氧烷（C)之上述平均組成式⑴及表示第 二有機聚矽氧烷（D)之上述平均組成式（II)中，γ爲具有锍 基或環氧基之有機基。 (6) 如（1)〜（5)中任一項所記載之黏著劑組成物，其中 表示第一有機聚矽氧烷（C)之上述平均組成式（I)及表示第 二有機聚矽氧烷（D)之上述平均組成式（II)中，b及g爲正 數，R1爲甲基，R2爲丙基或異丙基。 (7) 如（1)〜（6)中任一項所記載之黏著劑組成物，其中 表示第一有機聚矽氧烷（C)之上述平均組成式（I)中，c及d 皆爲正數，表示第二有機聚矽氧烷（D)之上述平均組成式 (II)中，h及i皆爲正數。 (8) 如（1)〜（7)中任一項所記載之黏著劑組成物，其中 第一有機聚矽氧烷（C)及第二有機聚矽氧烷（D)，各自的平 均聚合度爲3〜1 00。 (9) 一種附黏著劑之光學薄膜，其特徵係於光學薄膜 的至少一側的面上’設置由（〗）〜（8 )中任一項所記載的黏著 劑組成物所形成的黏著劑層。 (1 〇)如（9)所記載之附黏著劑之光學薄膜，其中光學薄 膜選自偏光薄膜及相位差薄膜。 (1 1)如（1 〇)所記載之附黏著劑之光學薄膜，其中光學 -10- 200904930 薄膜包含偏光子的至少一側的面上黏黏由乙醯纖維素系樹 脂或非晶性環狀聚烯烴系樹脂所成的保護膜之偏光薄膜。 [發明之效果] 本發明的黏著劑組成物，黏著於光學薄膜，成爲附黏 著劑之光學薄膜的狀態下，長時間性能安定，又即使大型 化，再加工性亦優良，同時持久性亦優異。所以此附黏著 劑之光學薄膜，適合使用於液晶顯示裝置。 [實施發明之最佳形態] 以下，詳細地說明本發明的實施形態，本發明的黏著 劑組成物，爲必須含有（A)丙烯酸樹脂、（B)交聯劑、（C) 上述平均組成式（I)所表示之一分子內含有疏基等的官能 基與甲氧基及/或乙氧基之第一有機聚矽氧烷、以及（D)上 述平均組成式（Π)所表示之一分子內含有锍基等的官能基 與甲氧基及/或乙氧基與碳原子數3及/或4的烷氧基之第二 有機聚矽氧烷者，首先，說明關於此等的成分。 [丙烯酸樹脂] 本發明所使用的丙烯酸樹脂，具體而言，以（甲基）丙 烯酸烷基酯所衍生的結構單作爲主成分，含有具有以游離 羧基、羥基、胺基、環氧環爲首之雜環基等極性官能基之 單體，較佳爲具有極性官能基之（甲基）丙烯酸系化合物所 衍生的結構單元之丙烯酸樹脂（A-1)較佳。其中，（甲基）丙 -11 - 200904930 烯酸之意，係指丙烯酸或甲基丙烯酸之任一個，另外，（ 甲基）丙烯酸酯等的「（甲基）」亦爲相同的意義，此外， 其中的烷基不包括具有脂環式結構之烷基（環烷基）。 作爲（甲基）丙烯酸酯，可列舉如丙烯酸甲酯、丙烯酸 乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸異丁酯、丙烯酸 2-乙基己酯、丙烯酸辛酯、丙烯酸異辛酯、丙烯酸月桂酯 、丙烯酸硬脂醯酯、丙烯酸苄酯、丙烯酸甲氧基乙酯、丙 烯酸乙氧基甲酯之丙烯酸烷基酯，或者如甲基丙烯酸甲酯 、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、 甲基丙烯酸異丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸 辛酯、甲基丙烯酸異辛酯、甲基丙烯酸月桂酯、甲基丙烯 酸硬脂醯酯、甲基丙烯酸苄酯、甲基丙烯酸甲氧基乙酯、 甲基丙烯酸乙氧基甲酯之甲基丙烯酸烷基酯。此等的（甲 基）丙烯酸烷基酯，可各自單獨使用之外，亦可使用不同 的複數者使其共聚合。 作爲具有極性官能基之單體之例子，可列舉如丙烯酸 、甲基丙烯酸、/3-羧基乙基丙烯酸酯之具有游離羧基的 單體；如（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2_羥基 丙酯、（甲基）丙烯酸2-或3-氯-2-羥基丙酯、二乙二醇單（ 甲基）丙烯酸酯之具有羥基的單體；如丙烯醯基嗎啉、乙 烯基己內醯胺、N -乙烯基-2 -吡咯烷酮、四氫糠基（甲基）丙 烯酸酯、己內酯改性四氫糠基丙烯酸酯、3,4-環氧基環己 基甲基（甲基）丙烯酸酯、環氧丙基（甲基）丙烯酸酯、2,5-二氫呋喃之具有雜環基的單體；N，N-二甲基胺基乙基（甲 -12- 200904930 基）丙烯酸酯之具有與雜環不同的胺基的單體等°此等$ 具有極性官能基的單體，可各自單獨使用之外’亦司彳吏$ 不同的複數者。 黏著劑組成物中之丙烯酸樹脂（A-1)，此100質量份中 ，通常以60〜99.9質量份，較佳爲80〜99.6質量份的比例含 有（甲基）丙烯酸烷基酯所衍生的結構單元’此外’通常以 0 .卜2 0質量份，較佳爲0.4〜1 0質量份的比例含有具有極性 官能基的單體所衍生的結構單元。 本發明所使用的丙烯酸樹脂（A-1 )，亦可含有上述所 說明的（甲基）丙烯酸烷基酯及具有極性官能基的單體以外 的單體所衍生的結構單元，作爲此等的例子’可列舉分子 內具有脂環式結構之（甲基）丙烯酸酯所衍生的結構單元' 苯乙烯系單體所衍生的結構單元、乙烯系單體所衍生的結 構單元、分子內具有複數的（甲基）丙烯醯基的單體所衍生 的結構單元等。 脂環式結構，通常爲碳數5以上’較佳爲碳數5〜7左右 的環烷烴結構。作爲具有脂環式結構之丙烯酸酯的具體例 子，可列舉丙烯酸異冰片酯、丙烯酸環己酯、丙烯酸二環 戊酯、丙烯酸環十二烷酯、丙烯酸甲基環己酯、丙烯酸三 甲基環己酯、丙烯酸tert-丁基環己酯、α-乙氧基丙烯酸 環己酯、丙烯酸環己基苯酯等’作爲具有脂環式結構之甲 基丙烯酸酯的具體例子，可列舉甲基丙烯酸異冰片酯、甲 基丙烯酸環己酯、甲基丙烯酸二環戊酯、甲基丙烯酸環十 二烷酯、甲基丙烯酸甲基環己酯、甲基丙烯酸三甲基環己 -13- 200904930 酯、甲基丙烯酸tert-丁基環己酯、甲基丙烯酸環己基苯 酯等。 作爲苯乙烯系單體的例子，苯乙烯之外，可列舉如甲 基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、 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、戊基苯乙烯、辛基苯乙烯之烷基苯乙烯； 如氟苯乙烯、氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙 烯之鹵化苯乙烯；更可列舉硝基苯乙烯、乙醯基苯乙烯、 甲氧基苯乙烯、二乙烯基苯等。 作爲乙烯系單體之例子，可列舉如乙酸乙烯酯、丙酸 乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯 之脂肪酸乙烯酯；如氯乙烯或溴乙烯之鹵乙烯；如偏氯乙 烯之偏鹵乙烯；如乙烯吡啶、乙烯吡咯烷酮、乙烯基咔唑 之含氮芳香族乙烯基；丁二烯、異戊二烯、氯丁二烯之共 軛二烯單體；更可列舉丙烯腈、甲基丙烯腈等。 作爲分子內具有複數的（甲基）丙烯醯基之單體的例子 ，可列舉如1,4 - 丁二醇二（甲基）丙烯酸酯、1，6 -己二醇二（ 甲基）丙烯酸酯、1，9 -壬二醇二（甲基）丙烯酸酯、乙二醇二 (甲基）丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、四乙二醇 二（甲基）丙烯酸酯、三丙二醇二（甲基）丙烯酸酯之分子內 具有2個的（甲基）丙烯醯基之單體；如三羥甲基丙烷三（甲 基）丙烯酸酯之分子內具有3個的（甲基）丙烯醯基之單體等 〇 (甲基）丙烯酸酯及具有極性官能基之單體以外的單體 -14- 200904930 ，可各自單獨使用，或可組合2種以上使用。構成黏著劑 組成物之丙烯酸樹脂（A-1)中，具有（甲基）丙烯酸酯及極性 官能基之單體以外的單體所衍生的結構單元，係在丙烯酸 樹脂（A-l)lOO質量份中，通常以0〜20質量份，較佳爲0〜10 質量份的比例含有。 黏著劑組成物的有效成分，亦可含有2種以上如上述 之以（甲基）丙烯酸烷基酯所衍生的結構單元作爲主成分， 含有具有極性官能基的單體所衍生的結構單元之丙烯酸樹 脂（A-1)。而且，上述丙烯酸樹脂（A-1)中，具有與此不同 之丙烯酸樹脂（A-2)，具體而言，例如亦可爲具有丙烯酸 烷基酯所衍生的結構單元，混合了不含有極性官能基之丙 烯酸樹脂等，但以（甲基）丙烯酸烷基酯所衍生的結構單元 作爲主成分，含有具有極性官能基的單體所衍生的結構單 元之丙烯酸樹脂（A-1)，爲總丙烯酸樹脂的60〜100質量％， 特別佳爲80〜100質量％。 以（甲基）丙烯酸烷基酯所衍生的結構單元作爲主成分 ，含有具有極性官能基的單體所衍生的結構單元之丙烯酸 樹脂（A-1)，藉由凝膠滲透層析法（GPC)之標準聚苯乙烯換 算的重量平均分子量（Mw)爲1,000,000〜2，〇〇〇,〇〇〇的範圍較 佳，標準苯乙烯換算的重量平均分子量爲〗，〇〇〇,〇〇〇以上 ，因爲會有高溫高濕下的黏著性提高，玻璃基板與黏著劑 層之間發生浮起或剝離的可能性變低之傾向，而且亦有再 加工性提高的傾向，故較佳。此外此重量平均分子量爲 2,000,000以下，因爲即使黏著於此黏著劑層的光學薄膜 -15- 200904930 的尺寸變化，黏著劑層隨著此尺寸變化而改變，而會有液 晶室的周緣部的明亮度與中心部的明亮度之間的差距消失 ，泛白（w h i t e V 〇 i d)或顏色不均受到抑制的傾向，故較佳 。重量平均分子量（Mw)與數平均分子量（Μη)之比（Mw/Μη) 所表示的分子量分佈，通常爲2~ 10程度的範圍。 丙烯酸樹脂（組合2種類以上時爲兩者的混合物），將 其溶於乙酸乙酯中後調整爲不揮發份濃度2 0質量％之溶液 ，於25°C顯示出20Pa· s以下，而且顯示出0.1〜7Pa. s的 黏度較佳，此時的黏著爲20Pa · s以下，因爲會有高溫高 濕下的黏著性提高，玻璃基板與黏著劑層之間發生浮起或 剝離的可能性變低之傾向，而且亦有再加工性提高的傾向 ，故較佳。黏度例如可藉由Brookfield黏度計測量。 構成黏著劑組成物之丙烯酸樹脂（A - 1 )，例如可藉由 溶液聚合性、乳化聚合法、塊狀聚合法、懸濁聚合法等習 知的各種方法製造，此丙烯酸樹脂的製造，通常使用聚合 起始劑，聚合起始劑係相對於丙烯酸樹脂的製造所使用的 全部的單體的合計100質量份，使用0.001〜5質量份左右。 作爲聚合起始劑，可使用熱聚合起始劑或光聚合起始 劑等；作爲光聚合起始劑’可列舉例如4-2(-羥基乙氧基） 苯基（2-羥基-2-丙基）酮等；作爲熱聚合起始劑，可列舉例 如2,2’-偶氮雙異丁腈、2,2’-偶氮雙（2-甲基丁腈）、1,1’-偶 氮雙（環己烷-卜腈）、2,2’-偶氮（2,4-二甲基戊腈）、2,2’-偶 氮（2,4-二甲基-4 -甲氧基戊腈）、二甲基-2,2’-偶氮（2 -甲基 丙酸酯）、2,2’-偶氮（2-羥基甲基丙腈）之偶氮系化合物； -16- 200904930 如過氧化月桂醯、tert-丁基過氧化氫、過 tert-丁基過氧化苯甲酸酯、枯烯過氧化氫、 化二碳酸酯、二丙基過氧化二碳酸酯、tert-癸酸酯、tert -丁基過氧化三甲基乙酸酯、（3 醯基）過氧化物之有機過氧化物；過硫酸鉀 過氧化氫之無機過氧化物。此外，倂用過氧 之氧化還原系起始劑等，亦可作爲聚合起始 作爲丙烯酸樹脂（A-1)的製造方法，上 法中，又以溶液聚合法較佳，列舉溶液聚合 說明，可列舉混合所望的單體及有機溶劑， 環境下，添加熱聚合起始劑，以4 0〜9 0。(：程 6〇~8(TC程度攪拌3~10小時程度之方法等。 制反應，於聚合中連續地或間歇地添加單體 劑，或於溶解於有機溶劑狀態下添加亦可， 機溶劑，可使用例如甲苯、二甲苯之芳香族 乙酯、乙酸丁酯之酯類；如丙醇、異丙醇之 甲基乙基酮、甲基異丁基酮之酮類等。 [交聯劑] 本發明的黏著劑組成物中，再於以上所 脂中，摻合交聯劑。交聯劑爲分子內具有3 極性官能基交聯的官能基之化合物，具體而 異氰酸酯系化合物、環氧系化合物、金屬螯 氮雜環丙烷系化合物等。 氧化苯甲醯、 一異丙基過氧 •丁基過氧化新 ,5,5·三甲基己 、過硫酸綾、 化物與還原劑 劑使用。 述所表示的方 法的具體例子 在氮氣的氣體 度，較佳爲以 此外，爲了控 或熱聚合起始 其中，作爲有 烴類；如乙酸 脂肪族醇類； 述的丙烯酸樹 i少2個之可與 言可列舉例如 合劑化合物、 -17- 200904930 異氰酸酯系化合物’爲分子內具有至少2個的異氰酸 基（-NCO)之化合物，可列舉例如甲苯撐二異氰酸酯、六甲 撐二異氰酸酯、異氟爾酮二異氰酸酯、二甲苯撐二異氰酸 酯、氫化二甲苯撐二異氰酸酯、二苯基甲烷二異氰酸酯、 氫化二苯基甲烷二異氰酸酯 '萘二異氰酸酯、三苯基甲烷 三異氰酸酯等。此外，使此等的異氰酸酯化合物，與丙三 醇或三羥甲基丙烷等之多元醇進行反應之加成物，或使異 氰酸酯成爲2聚物、3聚物等者，可成爲被使用於黏著劑組 成物之交聯劑。而且，亦可混合2種以上的異氰酸酯系化 合物使用。 環氧系化合物，爲分子內具有至少2個的環氧基之化 合物，可列舉例如雙酚A型的環氧樹脂、乙二醇二縮水 甘油醚、聚乙二醇二縮水甘油醚、丙三醇二縮水甘油醚、 丙三醇縮水甘油醚、1，6-己二醇二縮水甘油醚、三羥甲基 丙烷三縮水甘油醚、Ν,Ν-二縮水甘油苯胺、N,N，N’，N’-四 縮水甘油基-m-二甲苯二胺、1,3-雙（N，N’_二縮水甘油基胺 基甲基）環己烷等。亦可混合2種以上的環氧系化合物使用 〇 作爲金屬螯合劑化合物’可列舉例如錫、鐵、銅、鉢 、錫、鈦、鎳、銻、鎂、釩、鉻及鍩等之多價金屬上’配 位乙醯丙酮或乙醯乙酸乙酯之化合物等。 氮雜環丙烷系化合物’爲分子內具有至少2個被稱爲 乙抱亞胺之由1個氮原子與2個碳原子所成的3員環的骨架 之化合物，可列舉例如二苯基甲烷·4,4，-雙（1_氮雜環丙烷 -18- 200904930 甲醯胺）、甲苯-2,4-雙（1-氮雜環丙烷甲醯胺）、三乙撐三 聚氰胺、異鄰苯二甲醯雙-1-(2-甲基氮雜環丙烷）、參-1- 氮雜環丙基膦氧化物、六甲撐-1，6 -雙（1-氮雜環丙烷甲醯 胺）、三羥甲基丙烷-三氮雜環丙烷丙酸酯、四羥甲基 甲烷-三-0-氮雜環丙烷丙酸酯等。 此等交聯劑中，又以使用異氰酸酯系化合物較佳，此 外，倂用異氰酸酯系化合物與氮雜環丙烷系化合物亦具有 效果。 [有機聚矽氧烷] 本發明再摻合一分子內含有有機官能基與甲氧基及/ 或乙氧基，下述平均組成式（I)所表示的第一有機聚矽氧 烷，以及一分子內同時含有有機官能基、與甲氧基及/或 乙氧基、丙氧基或丁氧基等之碳原子數3及/或4的烷氧基 之下述平均組成式（II)所表示的第二有機聚矽氧烷。200904930 IX. Description of the Invention [Technical Field] The present invention relates to an adhesive composition, and in particular to an optical film for adhering to an adhesive for a glass cell for liquid crystal display [Prior Art] A liquid crystal cell used in a liquid crystal display device such as TN (Twisted Nematic) or STN (Super Twisted Nematic), which has a liquid crystal component held in two sheets of glass. The optical film of a polarizing film or a retardation film is laminated on the surface of each glass substrate via an adhesive mainly composed of an acrylic resin, and the optical film is usually formed on at least one surface. In the form of an optical film with an adhesive attached to the adhesive layer, the adhesive side is bonded to the glass substrate at the stage of assembling the liquid crystal cell, and is generally adopted. Such an optical film with an adhesive has a large dimensional change due to expansion and contraction under heat or humid heat conditions, so that it adheres to the optical laminate of the glass substrate, and foams in the adhesive layer, and the adhesive layer and the adhesive layer Problems such as floating or peeling occur between the glass substrates. Further, recently, a liquid crystal display device has been used as a vehicle for a car navigation system or the like. However, in a vehicle use, it is more desirable to have a durability such as foaming, floating, peeling, and the like even under high temperature and high humidity conditions. In addition, when the optical film with an adhesive is attached to the glass for liquid crystal display-5-200904930, when the film is incomplete, the optical film is peeled off and re-attached, and when the peeling is required, the adhesive layer is used. The optical film is peeled off, and the adhesive layer is not left on the glass, and so-called reworkability such as fogging does not occur. Recently, as the size of televisions and the like has increased, the area of optical films has also become larger, and it is required to have more excellent reworkability than the prior art. In order to solve the problem, various proposals have been made for an adhesive containing an acrylic resin as a main component. For example, Japanese Patent No. 3022993 (Patent Document 1) discloses an acrylic acid containing a decane compound having an epoxy group. The resin adhesive layer is provided on the surface of the polarizing film. Japanese Patent No. 3487940 (Patent Document 2) also discloses an adhesive composition in which an acrylic resin is blended with a curing agent and a specific niobate oligomer, and the adhesive composition is used for a polarizing film. Optical film. Patent Document 1: Japanese Patent No. 3022993 (JP-A-No. 4-223403) Patent Document 2: Japanese Patent No. 3 4 7 7 9 0 Contents [Problems to be Solved by the Invention] Only the results of the inventors of the present invention have been carefully studied, and an optical film provided with an adhesive is known in the prior art, although about 3 months after the application of the adhesive. Since the adhesive layer is bonded to the glass substrate, the reworkability or adhesion durability is excellent, but after a half year or a year after the application, the adhesive layer is bonded to the glass substrate. Adhesion persistence-6-200904930 or reduced reworkability. Here, an object of the present invention is to provide an excellent reworkability, and at the same time, when it is bonded to a glass base, it can suppress floating or peeling between the glass substrate and the adhesive layer, and foaming in the adhesive layer, and adhesion of the adhesive. After the cloth is applied, even after a long period of six months or one year, the above-mentioned floating or peeling, foaming, and fogging are less likely to occur, and the durability and reworkability are excellent, so that it is suitable as an adhesive for an optical film. And an optical film using the adhesive attached thereto. [Means for Solving the Problem] The inventors of the present invention have found that a functional group having a mercapto group or the like in a molecule is blended with a methoxy group and a result of careful investigation of the related subject. Or an ethoxylated organic polyoxyalkylene, a functional group having the same thiol group in one molecule and a methoxy group and/or an ethoxy group, and further containing a carbon such as a propoxy group or a butoxy group An organopolyoxane having an alkoxy group of 3 and/or 4 is effective. That is, since the prior art, the decane compound to the organopolyoxane used in the field of the adhesive has a large amount of methoxy group and/or ethoxy group in the molecule, and in this case, the hydrolyzability cannot be obtained. There is a problem in that the stability of the storage is sufficiently controlled, and in particular, since the acrylic pressure-sensitive adhesive contains water, it is difficult to stabilize the adhesive containing the decane compound for a long period of time as an adhesive. Therefore, it has been found that by using an organic polyoxyalkylene having a methoxy group or an ethoxy group having a high hydrolysis reactivity, and a carbon atom having a hydrolysis-reactive reactivity of a propoxy group or a butoxy group, etc. 3 and/or Or the organopoly 200904930 decane of the alkoxy group of 4 'arablely changes the hydrolysis reactivity of the decane compound. Therefore, the adhesive composition of the two kinds of organic polyoxyalkylenes blended with the acrylic resin and the crosslinking agent, the amount of the alkoxy group hydrolyzed is kept constant for a long period of time, so that the performance is stable. Further, in the adhesive, depending on the type of the optical film provided in the layer, the use conditions, and the like, the hydrolysis reactivity of the decane compound blended therein may be different, but the type of the alkoxy group is changed in accordance with the respective purposes. There is a limit to the content of the single product. Therefore, by preparing at least two kinds of organic polyoxoxanes having different hydrolysis reactivity, the composition of the mixing ratio is changed according to the required class, and the composition is expanded. The range that can be handled. Further, it has been found that the above-mentioned organopolyoxane has a high affinity for the glass and the acrylic resin because of its effect as a ruthenium coupling agent, so that an adhesive layer formed of an adhesive composition blended with the component is provided. When the adhesive film layer is attached to the glass substrate, the floating or peeling between the adhesive layer and the glass substrate is suppressed; and the organic polysiloxane is also used as a poly Since the effect of the oxime-based release agent is to provide an optical film with an adhesive attached to the pressure-sensitive adhesive layer formed by the adhesive composition of the component, the reworkability is also excellent, and the present invention has been completed. Therefore, the present invention provides the following adhesive composition and optical film with an adhesive attached thereto. (1) An adhesive composition comprising (A) an acrylic resin, (B) a crosslinking agent, 200904930 (C) a first organopolyoxane represented by the following average composition formula (I), YaR1bSi (OCH3)c(〇C2H5)d(〇H)e〇(4-abcde)/2 (I) wherein γ represents at least one selected from the group consisting of fluorenyl, epoxy, (meth) propylene An organic group of a decyloxy group, an alkenyl group, a halogenated alkyl group and an amine group; and R1 represents at least one unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have an aliphatic unsaturated bond; a, b, c 'd and e meet 0.01SaSl, 0$b < 2 ' 0 ^ c ^ 2 ' each 2, OSegl, and 〇.1 刍c + d^2.5 and 2 S a + b + c + d + e S 3 (D) The second organopolyoxane represented by the following average composition formula (II), YfR1gSi(OCH3)h(〇C2H5)i(OR2)J(OH)kO(4-fgh-ijk (2) (II) (wherein Y and R1 represent the same meanings as above; R2 is an alkyl or methoxypropyl group having 3 and/or 4 carbon atoms; f, g, h, i , j and k are in accordance with O.OISfgl, 〇Sg<2, 0ShS2, 〇Si$2, 0<jS2, 0 SkSl, and h and i are different at 0' and 0.1$h + i+jS2.5 and 2$ f+g + h + (2) The adhesive composition according to (1), wherein the acrylic resin (A) comprises a structural unit derived from an alkyl (meth)acrylate. The component is an acrylic resin containing a structural unit derived from a (meth)acrylic compound having a polar functional group. (3) The adhesive composition according to (2), wherein the polar functional group is 200904930 selected from the group consisting of a free carboxyl group, a hydroxyl group, an amine group, and an epoxy ring. (4) The adhesive composition according to any one of (1) to (3) wherein the crosslinking agent (B) contains an isocyanate compound. (5) The adhesive composition according to any one of (1) to (4), wherein the first organopolyoxane (C) has the above average composition formula (1) and represents a second organopolyoxane In the above average composition formula (II) of (D), γ is an organic group having a mercapto group or an epoxy group. (6) The adhesive composition according to any one of (1) to (5), wherein the first organic polyoxane (C) has the above average composition formula (I) and represents a second organic polyfluorene In the above average composition formula (II) of the oxyalkylene (D), b and g are positive numbers, R1 is a methyl group, and R2 is a propyl group or an isopropyl group. (7) The adhesive composition according to any one of (1) to (6) wherein, in the above average composition formula (I) of the first organopolyoxane (C), c and d are A positive number indicates that in the above average composition formula (II) of the second organopolyoxane (D), both h and i are positive numbers. (8) The adhesive composition according to any one of (1) to (7) wherein the first organopolyoxane (C) and the second organopolyoxane (D) are each polymerized in an average manner. The degree is 3~1 00. (9) An optical film with an adhesive characterized in that an adhesive formed of the adhesive composition according to any one of (1) to (8) is provided on at least one side of the optical film. Floor. (1) The optical film of the adhesive according to (9), wherein the optical film is selected from the group consisting of a polarizing film and a retardation film. (1) The optical film of the adhesive according to (1), wherein the optical-10-200904930 film comprises at least one side of the polarizer bonded to the acetaminocellulose resin or the amorphous ring. A polarizing film of a protective film made of a polyolefin resin. [Effects of the Invention] The adhesive composition of the present invention adheres to an optical film and becomes an optical film with an adhesive. The long-term performance is stable, and even if it is large, the reworkability is excellent, and the durability is excellent. . Therefore, the optical film with an adhesive is suitable for use in a liquid crystal display device. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an embodiment of the present invention will be described in detail. The adhesive composition of the present invention must contain (A) an acrylic resin, (B) a crosslinking agent, and (C) the above average composition formula. (I) one of the first organopolyoxane having a functional group having a thiol group or the like and a methoxy group and/or an ethoxy group, and (D) one of the above average composition formulas (Π) A second organopolyoxyalkylene having a functional group such as a fluorenyl group and a methoxy group and/or an ethoxy group and an alkoxy group having 3 and/or 4 carbon atoms in the molecule, first, a description of the components . [Acrylic Resin] The acrylic resin used in the present invention, specifically, a structural unit derived from an alkyl (meth)acrylate as a main component, and having a free carboxyl group, a hydroxyl group, an amine group, and an epoxy ring The monomer having a polar functional group such as a heterocyclic group is preferably an acrylic resin (A-1) which is preferably a structural unit derived from a (meth)acrylic compound having a polar functional group. In the meantime, (meth) propyl-11 - 200904930 olefinic acid means any one of acrylic acid and methacrylic acid, and "(meth)" such as (meth) acrylate has the same meaning. Wherein the alkyl group does not include an alkyl group (cycloalkyl group) having an alicyclic structure. Examples of the (meth) acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, and acrylic acid. Lauryl ester, stearyl acrylate, benzyl acrylate, methoxyethyl acrylate, alkyl acrylate of ethoxymethyl acrylate, or such as methyl methacrylate, ethyl methacrylate, propyl methacrylate Ester, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, stearin methacrylate Esters, benzyl methacrylate, methoxyethyl methacrylate, alkyl methacrylate of ethoxymethyl methacrylate. These (meth)acrylic acid alkyl esters may be used singly or in combination with a plurality of different monomers. Examples of the monomer having a polar functional group include a monomer having a free carboxyl group such as acrylic acid, methacrylic acid, or 3-carboxyethyl acrylate; such as 2-hydroxyethyl (meth)acrylate, (A) a monomer having a hydroxyl group; 2-hydroxypropyl acrylate, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate; Porphyrin, vinyl caprolactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexyl Methyl (meth) acrylate, epoxy propyl (meth) acrylate, 2,5-dihydrofuran having a heterocyclic group; N,N-dimethylaminoethyl (A- 12-200904930 A acrylate monomer having an amine group different from a hetero ring, etc. Such a monomer having a polar functional group may be used alone or in addition to a different plural. The acrylic resin (A-1) in the adhesive composition is usually derived from (meth)acrylic acid alkyl ester in a ratio of 60 to 99.9 parts by mass, preferably 80 to 99.6 parts by mass, per 100 parts by mass. The structural unit 'further' generally contains a structural unit derived from a monomer having a polar functional group in a ratio of 0.2 parts by mass, preferably 0.4 to 10 parts by mass. The acrylic resin (A-1) used in the present invention may contain a structural unit derived from a monomer other than the above-described (meth)acrylic acid alkyl ester and a monomer having a polar functional group, and the like. The example 'may be exemplified by a structural unit derived from a (meth) acrylate having an alicyclic structure in a molecule, a structural unit derived from a styrene monomer, a structural unit derived from a vinyl monomer, and a plurality of molecules in a molecule. A structural unit derived from a monomer of (meth)acrylonyl group. The alicyclic structure is usually a cycloalkane structure having a carbon number of 5 or more and preferably a carbon number of 5 to 7. Specific examples of the acrylate having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methylcyclohexyl acrylate, and trimethyl acrylate. Hexyl ester, tert-butylcyclohexyl acrylate, cyclohexyl α-ethoxy acrylate, cyclohexyl phenyl acrylate, etc. As a specific example of the methacrylate having an alicyclic structure, methacrylic acid is exemplified. Borneol ester, cyclohexyl methacrylate, dicyclopentanyl methacrylate, cyclododecyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate-13-200904930, Tert-butylcyclohexyl methacrylate, cyclohexyl phenyl methacrylate, and the like. Examples of the styrene-based monomer include, in addition to styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, and triethyl styrene. Alkyl styrene of propyl styrene, butyl styrene, hexyl styrene, amyl styrene, octyl styrene; such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodobenzene The halogenated styrene of ethylene; more specifically, nitrostyrene, ethyl styrene styrene, methoxy styrene, divinyl benzene, and the like. Examples of the vinyl monomer include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl acetate of lauric acid; such as vinyl chloride or vinyl bromide. a vinyl halide; a vinylidene halide such as vinylidene chloride; a nitrogen-containing aromatic vinyl such as vinylpyridine, vinylpyrrolidone or vinylcarbazole; a conjugated diene of butadiene, isoprene, chloroprene Examples of the compound include acrylonitrile and methacrylonitrile. Examples of the monomer having a complex (meth) acrylonitrile group in the molecule include, for example, 1,4-butanediol di(meth)acrylate and 1,6-hexanediol di(meth)acrylic acid. Ester, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylic acid a monomer having two (meth)acrylonitrile groups in the molecule of an ester or tripropylene glycol di(meth)acrylate; for example, three molecules of trimethylolpropane tri(meth)acrylate have The fluorene (meth) acrylate such as a monomer of a methyl methacrylate group and the monomer-14-200904930 other than the monomer having a polar functional group may be used alone or in combination of two or more. In the acrylic resin (A-1) constituting the adhesive composition, a structural unit derived from a monomer other than the monomer having a (meth) acrylate and a polar functional group is contained in 100 parts by mass of the acrylic resin (Al). It is usually contained in a proportion of 0 to 20 parts by mass, preferably 0 to 10 parts by mass. The active ingredient of the adhesive composition may further contain two or more kinds of structural units derived from a monomer having a polar functional group as a main component, such as the above-mentioned structural unit derived from an alkyl (meth)acrylate. Resin (A-1). Further, the acrylic resin (A-1) has an acrylic resin (A-2) different from the above, and specifically, for example, may be a structural unit derived from an alkyl acrylate, which is mixed with no polar functional groups. An acrylic resin (A-1) having a structural unit derived from a monomer having a polar functional group as a main component, and a structural unit derived from an alkyl (meth)acrylate, is a total acrylic acid The resin is 60 to 100% by mass, particularly preferably 80 to 100% by mass. An acrylic resin (A-1) containing a structural unit derived from a monomer having a polar functional group as a main component, a structural unit derived from an alkyl (meth)acrylate, by gel permeation chromatography (GPC) The standard polystyrene-equivalent weight average molecular weight (Mw) is 1,000,000 to 2, and the range of ruthenium and osmium is preferred, and the weight average molecular weight in terms of standard styrene is 〗 〖, 〇〇〇, 〇〇〇 Since the adhesiveness under high temperature and high humidity is improved, the possibility of floating or peeling between the glass substrate and the adhesive layer tends to be low, and the reworkability tends to be improved, which is preferable. Further, the weight average molecular weight is 2,000,000 or less, because even if the size of the optical film -15-200904930 adhered to the adhesive layer changes, the adhesive layer changes with the change of the size, and the brightness of the peripheral portion of the liquid crystal chamber is present. The difference between the brightness and the brightness of the center portion disappears, and white V 〇 id or color unevenness tends to be suppressed, which is preferable. The molecular weight distribution represented by the ratio (Mw/Μη) of the weight average molecular weight (Mw) to the number average molecular weight (?η) is usually in the range of about 2 to 10. Acrylic resin (a mixture of two types when two or more types are combined), which is dissolved in ethyl acetate, and adjusted to a non-volatile content of 20% by mass, and exhibits 20 Pa·s or less at 25 ° C, and is displayed. The viscosity of 0.1 to 7 Pa.s is better, and the adhesion at this time is 20 Pa·s or less. Since the adhesion under high temperature and high humidity is improved, the possibility of floating or peeling between the glass substrate and the adhesive layer becomes variable. It tends to be low, and there is also a tendency to improve reworkability. Viscosity can be measured, for example, by a Brookfield viscometer. The acrylic resin (A-1) constituting the adhesive composition can be produced, for example, by various methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc., and the production of the acrylic resin is usually In the polymerization initiator, the polymerization initiator is used in an amount of about 0.001 to 5 parts by mass based on 100 parts by mass of the total of all the monomers used in the production of the acrylic resin. As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator or the like can be used; as the photopolymerization initiator, for example, 4-2 (-hydroxyethoxy)phenyl (2-hydroxy-2-) can be cited. A propyl) ketone or the like; as a thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'- Azobis(cyclohexane-b-carbonitrile), 2,2'-azo (2,4-dimethylvaleronitrile), 2,2'-azo (2,4-dimethyl-4-methyl) An azo compound of oxyvaleronitrile), dimethyl-2,2'-azo (2-methylpropionate), 2,2'-azo (2-hydroxymethylpropionitrile); 16- 200904930 Such as oxidized bay laurel, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, cumene hydroperoxide, dicarbonate, dipropyl peroxydicarbonate, tert - an organic peroxide of phthalic acid ester, tert-butyl peroxytrimethyl acetate, (3 fluorenyl) peroxide; inorganic peroxide of potassium persulfate hydrogen peroxide. Further, a peroxidic redox initiator or the like may be used as a polymerization starting method as a method for producing the acrylic resin (A-1), and in the above method, a solution polymerization method is preferred, and a solution polymerization description is given. The monomer and the organic solvent which are expected to be mixed may be mentioned, and a thermal polymerization initiator is added in an environment of 40 to 90. (:6〇~8 (the method of stirring at a level of TC for 3 to 10 hours, etc. The reaction is carried out by adding a monomer agent continuously or intermittently in the polymerization, or adding it in an organic solvent state, the solvent For example, an ester of aromatic ethyl ester of toluene, xylene, or butyl acetate; a methyl ethyl ketone of propanol, isopropanol, a ketone of methyl isobutyl ketone, or the like can be used. In the adhesive composition of the present invention, a crosslinking agent is blended in the above lipid. The crosslinking agent is a compound having a functional group crosslinked by a 3 polar functional group in the molecule, specifically an isocyanate compound, epoxy a compound, a metal chelate azepine compound, etc. Benzene oxide, monoisopropyl peroxy-2-butyl peroxide, 5,5·trimethylhexyl, bismuth persulfate, a compound and a reducing agent A specific example of the method represented by the method is a gas degree of nitrogen gas, preferably further, for the purpose of controlling or thermal polymerization, as a hydrocarbon; for example, an aliphatic alcohol of acetic acid; It can be exemplified by a mixture of compounds, -17- 2009 04930 The isocyanate compound 'is a compound having at least two isocyanato groups (-NCO) in the molecule, and examples thereof include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate. Hydrogenated xylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate 'naphthalene diisocyanate, triphenylmethane triisocyanate, etc. Further, such isocyanate compounds are made with glycerol or trishydroxyl An adduct which reacts with a polyol such as methyl propane, or an isocyanate which is a dimer or a trimer, may be used as a crosslinking agent for the adhesive composition. Further, two or more kinds may be mixed. The epoxy compound is a compound having at least two epoxy groups in the molecule, and examples thereof include an epoxy resin of a bisphenol A type, an ethylene glycol diglycidyl ether, and a polyethylene glycol II. Glycidyl ether, glycerol diglycidyl ether, glycerol glycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane tricondensate Ether, hydrazine, hydrazine-diglycidylaniline, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N'-diglycidylamine Methyl)cyclohexane or the like. Two or more epoxy compounds may be mixed, and ruthenium is used as the metal chelating agent compound, and examples thereof include tin, iron, copper, ruthenium, tin, titanium, nickel, ruthenium, magnesium, and vanadium. , a compound such as ruthenium acetonate or ethyl acetoacetate on a polyvalent metal such as chromium or ruthenium. The aziridine compound 'is a molecule having at least two molecules called ethaneimine. The compound of the skeleton of the 3-membered ring formed by a nitrogen atom and two carbon atoms may, for example, be diphenylmethane·4,4,-bis(1-azacyclopropane-18-200904930 formamidine), toluene -2,4-bis(1-azabiidinecarbamamine), triethylene melamine, isophthalic bis-(2-methylaziridine), gin-1-aza Cyclopropylphosphine oxide, hexamethylene-1,6-bis(1-azetidincarbamide), trimethylolpropane-triazapropane propionate, tetramethylolethane-tri- 0-azepine propionate and the like. Among these crosslinking agents, an isocyanate-based compound is preferably used, and in addition, an isocyanate-based compound and an aziridine-based compound are also effective. [Organic Polyoxane] The present invention further comprises a first organopolyoxane represented by the formula (I), wherein the organic compound is contained in a molecule together with a methoxy group and/or an ethoxy group, and The following average composition formula (II) of an alkoxy group having an organic functional group, a methoxy group, and/or an ethoxy group, a propoxy group or a butoxy group, and having 3 or more carbon atoms; The second organopolyoxane is represented.

YaR1bSi(OCH3)c(〇C2H5)d(〇H)eO(4-a.b-cd-e)/2 …U)YaR1bSi(OCH3)c(〇C2H5)d(〇H)eO(4-a.b-cd-e)/2 ...U)

YfR1gSi(OCH3)h(〇C2H5)i(〇R2)j(〇H)kO(4.f.g-h-1-j.k)/2 …（Π) 上述式（I)及（Π)中，Y爲具有選自锍基、環氧基、（甲 基）丙烯醯氧基、烯基、鹵化烷基及胺基的官能基之有機 基。此等官能基中，锍基、環氧基、（甲基）丙烯醯氧基及 胺基，通常介由連結基而鍵結於矽原子，該相關的連結基 ，可列舉可夾雜醚鍵（-0-)、亞胺基（-NH-)等之碳數的 -19- 200904930 伸烷基、伸烷基-伸芳基-伸烷基等之2價的烴基，可列舉 例如包括伸甲基、伸乙基、伸丙基、伸己基、伸癸基等之 伸烷基、包括甲基苯基乙基等之中間具有芳香族環之2價 的烴基、包括甲氧基甲基、甲氧基乙基、甲氧基丙基等之 中間具有氧原子之2價的脂肪族基。烯基或鹵化烷基，亦 可介由上述連結基而鍵結於矽原子，亦可直接鍵結於矽原 子。 列舉Y所表示之具有官能基之有機基（以下，亦將γ 所表示的基稱爲「有機官能基」）的具體例子，作爲具有 锍基之有機基，可列舉锍基甲基、3-酼基丙基、6-锍基己 基、10-锍基十二烷基、2-(4-锍基甲基苯基）乙基等；作爲 具有環氧基之有機基，可列舉環氧丙氧基甲基' 3-環氧丙 氧基丙基、5，6-環氧己基、9,10 -環氧癸基、2-(3,4-環氧環 己基）乙基、2-(3,4-環氧-4-甲基環己基）丙基等；作爲具有 (甲基）丙烯醯氧基之有機基’可列舉丙烯醯氧基甲基、3-丙烯醯氧基丙基、6 -丙烯醯氧基己基' 10 -丙烯醯氧基癸 基、甲基丙烯醯氧基甲基、3-甲基丙烯醯氧基丙基、6-甲 基丙烯醯氧基己基、10-甲基丙烯醯氧基癸基等；作爲具 有烯基之有機基’可列舉乙烯基、烯丙基、5-己烯基、9-己烯基、3 -乙烯基氧基丙基、P·苯乙烯基、環己烯基乙基 等；作爲具有鹵化烷基之有機基，可列舉氯甲基、3 -氯丙 基、6-氯己基、10-氯癸基、溴甲基、3-溴丙基等；作爲 具有胺基之有機基’可列舉胺基甲基、3·胺基丙基、6-胺 基己基、N -甲基-3-胺基丙基、Ν，Ν·二甲基_3_胺基丙基、 -20- 200904930 N-苯基-3-胺基丙基、N-(2-胺基乙基）_3-胺基丙基 胺基己基）-3 -胺基丙基、N-(乙嫌基节基）_2_胺基乙 基丙基等。 作爲上述平均組成式（I)所表示的第一有機聚 及平均組成式（II)所表示的第二有機聚矽氧烷，可 有不同的Y者’但具有同一系統的官能基者較佳 在此狀況下，爲連接末端官能基與矽原子之伸烷基 個有機基中的官能基取代數不同者亦可。 平均組成式（I)及（II)的有機聚矽氧烷中，上述 官能基中’爲具有锍基、環氧基或（甲基）丙烯醯氧 機基時’因爲此高的反應性而爲較佳者，特別是具 或環氧基之有機基’因爲提高玻璃與光學薄膜的黏 效果高而更佳。 又上述式（I)及（II)中，R1爲至少1種之不具有 不飽和鍵的碳原子數1〜8的非取代的一價烴基，具 可列舉甲基、乙基、丙基、異丙基、1-甲基丙基、 異丁基、tert-丁基、己基、辛基、苯基 '甲苯基、 苯基乙基等之烷基、芳基、芳烷基，若有需要，亦 複數的基作爲R1。其中，由相對於有機官能基的 之立體障礙的影響或成本面而言，R1爲甲基特別佳 上述式（Π)中’ R2爲碳原子數3及/或4的烷基， 言，可爲丙基、異丙基、1-甲基丙基、丁基、異丁 tert-丁基。此外，甲氧基丙基亦以可得到同等的效 包含於R2。若有需要，亦可導入複數的基作爲R2 、Ν·(6-基-3-胺 矽氧烷 使用具 ，即使 等或一 的有機 基之有 有锍基 著力的 脂肪族 體而言 丁基、 苄基、 可導入 反應性 〇 具體而 基、或 果者而 。其中 -21 - 200904930 ，由使水解反應性適度地降低之觀點，或 於上述的有機官能基的含量（當量）造成影 R2特別佳爲丙基或異丙基。 而且於上述式（I)中，a、b、c、d及< ' 〇^b<2' 0^c^2> 0^d^2' 2-5 及 2$a + b + c + d + eS3 之數。此外，上 5 、h、i、j 及 k 符合 0.01 $ 1、0$ g< 2 S2、0<j$2、OSkSl，而 h 與 i 不會辰 h + i+j S 2.5及 2$ f+g + h + i+j+kg 3之數 其中，係數a及f，表示相對於矽原 的取代度之數値，此數値太小，則使用有 原本應具有之藉由有機官能基的反應性所 被發揮，必須爲至少一分子中具有一個的 另一方面，有機官能基的取代度大於1， 或成本面上而言會有困難，故使其爲0.01 S1的範圍，較佳爲O.lSaSl及O.ISfS] 〇.lSaS〇.8及 0_lSfg0.8的範圍。 係數b及g，表示相對於矽原子之不 和鍵的碳原子數1〜8的非取代的一價烴基 ，此數値爲〇或接近〇時，烷氧基的含量相 解反應或矽烷化反應的貢獻率提高，依情 砂氧烷相對於水的親和性提高。另一方面 依一價烴基的種類的不同，具有對有機聚 性（烷基等）、使與丙烯酸樹脂的相溶性提 :院基的容積高對 響之觀點而言， 2符合〇.〇1各ag 1 1，且 0.1 s c + dg 式（II)中，f、g 、0 g h g 2、0 s i ϋ時爲〇，且〇. i g :子之有機官能基 機聚矽氧烷時， 產生的特性無法 有機官能基者。 因爲由合成法上 $ as 1 及 〇_(H $ f ί的範圍，更佳爲 具有脂肪族不飽 的取代度之數値 對地增加，對水 況不同，有機聚 ’此數値大時， 矽氧烷賦予疏水 :高（苯基等）、對 -22- 200904930 黏著劑的硬化物賦予柔軟性或離型性（甲基）等的效果’ b 或g變大則因爲烷氧基的含量相對地減少’變得不適合活 用烷氧基矽烷基的反應性之黏者劑用途°因此’依使用目 的而使其爲〇Sb<2及〇$g<2的範圍’較佳爲0SbS1及〇 ^§$1的範圍，更佳爲〇‘^>$〇.8及〇‘§‘〇.8的範圍° 式（I)中之係數c及d ’以及式（11)中之係數h、1及j ，表示相對於矽原子之碳原子數爲不同的複數種的丨完氧基 的取代度之値，c及h表示甲氧基的取代度’ d及i表示 乙氧基的取代度，j表示上述平均組成式（Π)所表示的有 機聚矽氧烷中之碳原子3及/或4的烷氧基的取代度。 上述平均組成式（I)所表示的第一有機聚矽氧烷’爲 含有水解反應性高的甲氧基及乙氧基的至少一方者’依使 用目的，可任意地設定取代度’但使表示各自的含有率之 c及d爲0ScS2、0SdS2的範圍’且使表示甲氧基與乙 氧基的合計取代度之c + d爲0.1 S c + d$ 2.5的範圍’較佳 舄0$〇$1.8、0$£1$1.8的範圍，且0.2$〇 + (1$2.35的範 圔。式（I)中之c及d皆爲超過0的數字’含有甲氧基與乙 氧基兩者之有機聚矽氧烷，在水解反應性中其範圍廣，同 時倂用上述平均組成式（Π)所表示的第二有機聚矽氧烷時 ’可期待有助於階段的水解反應之所謂的等級效果，其中 c 及 d，更佳爲 O.lgcSl.8、0.1SdS1.8，且 〇.5Sc + dS 2 · 3 5的範圍。 上述平均組成式（II)所表示的第二有機聚矽氧烷中， 袠示水解反應性高的甲氧基及乙氧基的含有率之h及i， -23- 200904930 表示水解反應性低的丙氧基或丁氧基等之碳原子數3及/或 4的烷氧基的含有率之j，依各自的使用目的及所望的水解 反應性的情況而適當地設定’但由使水解反應性降低而控 制與平均組成式（I)所表示的第一有機聚矽氧烷倂用時的 水解反應性，且如上述，在倂用時的水解反應中，在不會 僅留下第二有機聚矽氧烷下，表現出有助於階段的水解反 應之所謂的等級效果之本發的目的而言，使其爲0 S h S 2 、〇SiS2的範圍，而h與i不會同時爲〇，〇<j$2的範圍 ，而且表示烷氧基的合計取代度之h + i+j爲0.1Sh + i+jS 2.5的範圍，較佳爲0ShS1.8、OSigl.8，h與i至少一 方爲 0.1以上，〇.2Sh + i+jS2_35的範圍，更 佳爲 O.lShS 1.8、0.1S iS 1.8、O.lgjS 1.8、0.5Sh + i+j S2.35的範圍。式（II)中之h及i皆爲超過0的數字，含有 甲氧基與乙氧基兩者較佳。 此外，式（I)中之係數e及式（11)中之係數k ’表示相 對於矽原子之羥基的取代度’亦即表示矽烷醇基的含有率 之數値，此矽烷醇基可參與矽烷基化反應或縮合反應’具 有對有機聚矽氧烷賦予親水性效果’但由有機聚矽氧烷的 保存安定性確保的觀點而言’僅可能降低用量較佳。因此 ，使其爲O^eSl及的範圍，較佳爲〇SeS〇.5及0 S 0.5的範圍，更佳爲〇_2及〇‘ kS 0.2的範圍。 式（I)中之各係數的合計（a + b + c + d + e)、及式（11)中之各 係數的合計（f+g + h + i+j+k) ’爲決定表不上述平均組成式 (I)及（II)所表示的有機聚矽氧院的縮合度[4_ -24- 200904930 (a + b + c + d + e)]/2 及[4-(f+g + h + i+j+k)]/2之數値，使其爲 a + b + c + d + e$3及2$f+g + h + i+ j + k$3的範圍’此有機聚砂 氧烷的聚合度，可爲從矽原子2個的二聚物至矽原子數百 個程度的聚合物爲止的範圍。但平均聚合度爲2時’所製 造的有機聚矽氧烷中的單體含量變多’而聚砂氧垸垸氧基 寡聚物的原本的使用目的被破壞，平均聚合度太大’因爲 成爲高黏度品或膏狀或固體狀而操作困難’故使平均聚合 度爲3〜1 0 0的範圍較佳，更佳爲3 ~ 5 0的範圍。由此觀點而 言，關於上述的（a + b + c + d + e)及（f+g + h + i+j+k)’較佳爲2$ & + 匕 + 〇 + (1 + 6$2.67及2$£+8 + 11 + 丨+』+ 1^€2.67的範圍，更佳爲 2< a + b + c + d + e^ 2.67S.2< f+g + h + i+ j+ k^ 2.67^ |bH|。 一分子內含有有機官能基與甲氧基及/或乙氧基之第 一有機聚矽氧烷、及、一分子內含有有機官能基與甲氧基 及/或乙氧基與碳數3及/或4的烷氧基之第二有機聚矽氧烷 ，各自以上述平均組成式⑴及（II)表示，係數a〜e及係數 f~k各自爲滿足上述範圍之數即可，具有直鏈狀、支鏈狀 、環狀、及組合此等之結構亦可。 [有機聚矽氧烷的製造方法] 接著，說明關於有機聚矽氧烷的製造方法。上述平均 組成式（I)所表示之一分子內含有有機官能基與甲氧基及/ 或乙氧基之第一有機聚矽氧烷’可藉由先前技術習知的各 種處方製造。例如以上述的含有有機官能基與甲氧基及/ 或乙氧基之矽烷偶合劑作爲原料’單獨進行部份水解.聚 -25- 200904930 縮口之方法；或者使其他的烷氧基矽烷類及/或其部份水 解物及/或其縮合物’進行部份共水解•聚縮合之方法。 因此所得到的第一有機聚矽氧烷大部份的情況爲液體。 下述平均組成式（π)所表示之一分子內含有有機官能 基與甲氧基及/或乙氧基與碳原子數3及/或4的院氧基之第 一有機聚砂氧烷’亦可藉由先前技術習知的各種處方製造 ’作爲一般的手段，可列舉例如如下述方法。 (1) 使上述之含有有機官能基與碳原子數不同的複數 種的院氧基之烷氧基矽烷，單獨進行部份水解.聚縮合之 方法。 (2) 使含有有機官能基之烷氧基矽烷，及含有與其碳 原子數不同之烷氧基且不含有機官能基之烷氧基矽烷，進 行部份共水解•聚縮合之方法。 (3) 於藉由同樣的部份水解.聚縮合操作所得到的含 有有機官能基與甲氧基及/或乙氧基之有機聚矽氧烷中， 藉由與碳原子數3及/或4的醇之酯交換反應，導入碳原子 數3及/或4的烷氧基之方法。 本發明中’由上述平均組成式（II)所表示的有機聚矽 氧烷的結構設計的自由度、原料取得的容易度之觀點而言 ，基於上述（2)的處方’將至少一種的下述一般式（III)所 表示之含有有機官能基的烷氧基矽烷及/或其部份水解物 、與至少一種的下述一般式（IV)所表示之含有院氧基的砂 烷化合物及/或其部份水解物及/或其縮合物的混合物，進 行部份共水解及聚縮合’而成爲有機聚矽氧烷較佳。 • 26 - 200904930 YR1mSi(〇CH3)n(〇C2H5)3-m-n …（III) R1pSi(0CH3)q(0C2H5)r(0R2)4.p.q,r …（iv) 其中’ γ、R1及R2各自與上述式（II)中所表示的意義 相同，m爲0〜2的整數’ n爲〇〜3的整數，但m + n爲3以下 ’ p爲0~2的整數’ q爲〇〜4的整數，r爲0〜4的整數， P + q + r爲4以下’但’作爲—般式（IV)的含有烷氧基之矽烷 化合物，使用至少一種具有OR2基之成分。 此外作爲變形法，藉由下述方法可成爲有機聚矽氧烷 ’亦即，首先’使上述一般式（III)所表示之含有有機官能 基之烷氧基矽烷、與上述一般式（IV)所表示之含有至少一 種的烷氧基之矽烷化合物，預先進行部份共水解，接著將 此部份共水解生成物’混合上述一般式（IV)所表示之與先 使用於部份共水解者不同之含有烷氧基之矽烷化合物及/ 或其部份水解物及/或其縮合物，使其進行部份水解及聚 縮合後’得到有機聚矽氧烷。此方法亦使用至少一種具有 基之成分’作爲上述一般式（IV)所表示的含烷氧基之 矽烷化合物。 列舉上述一般式（III)所表示之含有有機官能基之烷氧 基矽烷的具體例子，作爲有機官能基，可列舉具有毓基甲 基、3-锍基丙基、6-锍基己基、1 0-锍基十二烷基、2-(4_ 疏基甲基本基）乙基、環氧丙氧基甲基、3 -環氧丙氧基丙 基、5,6-環氧己基、9,10-環氧癸基、2-(3,4-環氧環己基） 乙基、2_(3,4_環氧-4-甲基環己基）丙基、丙烯醯氧基甲基 -27- 200904930 备基丙基、6-丙嫌酿氧基己基、10-丙嫌醒氧 、3 -丙烯醯剩班 ^ ^ 由篡丙烯醯氧基甲基'3 -甲基丙烯醯氧基丙基、 基癸基、中费 6_甲其丙嫌酿氧基己基、10-甲基丙烯醯氧基癸基、乙烯 # β ^甘、5-己烯基、9-癸烯基、3-乙烯基氧基丙基、 基、烯丙基 —7 α甘、環己烯基乙基、氯甲基、3_氯丙基、6_氯己 Ρ -本乙猫巷 ^ 其、溴甲基、3 -溴丙基、胺基甲基、3 -胺基 基、1 0-氯笑费 …其丙基、Ν-甲基_3_胺基丙基、Ν，Ν_二甲基-3-丙基、6 -胺基η $ ^ ^苯基·3_胺基丙基、Ν-(2-胺基乙基）-3-胺基YfR1gSi(OCH3)h(〇C2H5)i(〇R2)j(〇H)kO(4.fg-h-1-jk)/2 (() In the above formula (I) and (Π), Y is An organic group having a functional group selected from the group consisting of a mercapto group, an epoxy group, a (meth)acryloxy group, an alkenyl group, a halogenated alkyl group, and an amine group. Among these functional groups, a mercapto group, an epoxy group, a (meth) propylene oxime group, and an amine group are usually bonded to a ruthenium atom via a linking group, and the related linking group may be an entrapped ether bond ( -0-), a carbon number of the imido group (-NH-), etc., -19-200904930, a divalent hydrocarbon group such as an alkyl group, an alkylene group, an exoaryl group or an alkylene group, and examples thereof include, for example, a formazan. a dialkyl group having an aromatic ring in the middle, including an ethyl group, a propyl group, a hexyl group, a hydrazine group, a methyl group, and the like, including a methoxymethyl group. A divalent aliphatic group having an oxygen atom in the middle of an oxyethyl group, a methoxypropyl group or the like. The alkenyl group or the halogenated alkyl group may be bonded to the ruthenium atom via the above-mentioned linking group or may be directly bonded to the oxime atom. Specific examples of the organic group having a functional group represented by Y (hereinafter, a group represented by γ is also referred to as "organic functional group"), and examples of the organic group having a mercapto group include mercaptomethyl group and 3- Mercaptopropyl, 6-fluorenylhexyl, 10-decyldodecyl, 2-(4-mercaptomethylphenyl)ethyl, etc.; as an organic group having an epoxy group, a propylene-propylene group is mentioned. Oxymethylmethyl 3-epoxypropoxypropyl, 5,6-epoxyhexyl, 9,10-epoxyindenyl, 2-(3,4-epoxycyclohexyl)ethyl, 2-( 3,4-epoxy-4-methylcyclohexyl)propyl and the like; as the organic group having a (meth)acryloxy group, 'acrylomethoxymethyl group, 3-propenyloxypropyl group, 6-Allyloxyhexyl '10-propenyloxycarbonyl, methacryloxymethyl, 3-methylpropenyloxypropyl, 6-methylpropenyloxyhexyl, 10-methyl a propylene fluorenyl fluorenyl group or the like; as an organic group having an alkenyl group, a vinyl group, an allyl group, a 5-hexenyl group, a 9-hexenyl group, a 3-vinyloxypropyl group, a P·benzene group Vinyl, cyclohexenylethyl, etc.; as an organic having a halogenated alkyl group Examples of the group include a chloromethyl group, a 3-chloropropyl group, a 6-chlorohexyl group, a 10-chloroindenyl group, a bromomethyl group, a 3-bromopropyl group and the like; and an organic group having an amine group is exemplified as an aminomethyl group. , 3-aminopropyl, 6-aminohexyl, N-methyl-3-aminopropyl, hydrazine, hydrazine dimethyl 3-aminopropyl, -20- 200904930 N-phenyl- 3-aminopropyl, N-(2-aminoethyl)-3-ylaminopropylaminohexyl)-3-aminopropyl, N-(ethyl phenyl)-2-aminoethyl Propyl and the like. The second organopolyoxane represented by the first organic poly-and the average composition formula (II) represented by the above average composition formula (I) may have different Y-members, but those having the same system are preferred. In this case, the number of substitutions of the functional groups in the alkyl group in which the terminal functional group and the fluorene atom are bonded may be different. In the organopolysiloxane having the average composition formula (I) and (II), when the functional group is 'having a mercapto group, an epoxy group or a (meth) propylene oxime group, 'because of such high reactivity Preferably, especially the organic group having an epoxy group is more preferred because it enhances the adhesion of the glass to the optical film. Further, in the above formulae (I) and (II), R1 is at least one unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have an unsaturated bond, and examples thereof include a methyl group, an ethyl group, and a propyl group. Isopropyl, 1-methylpropyl, isobutyl, tert-butyl, hexyl, octyl, phenyl 'tolyl, phenylethyl, etc. alkyl, aryl, aralkyl, if necessary , also the base of the plural as R1. Wherein R1 is a methyl group particularly preferably in the above formula (Π), wherein R 2 is an alkyl group having 3 and/or 4 carbon atoms, or a cost aspect, relative to the steric hindrance of the organic functional group. It is propyl, isopropyl, 1-methylpropyl, butyl, isobutyl tert-butyl. Further, methoxypropyl group is also included in R2 in an equivalent effect. If necessary, a plurality of groups can also be introduced as R2, Ν·(6-yl-3-amine oxane used, even if the organic group has a thiol-based aliphatic butyl group , benzyl, can be introduced into the reactive oxime, specific, or fruit. Among them - 21 - 200904930, from the viewpoint of moderately reducing the hydrolysis reactivity, or the content of the above organic functional group (equivalent) caused R2 Particularly preferred is propyl or isopropyl. Further, in the above formula (I), a, b, c, d, and < ' 〇^b<2' 0^c^2> 0^d^2' 2- 5 and 2$a + b + c + d + eS3. In addition, the upper 5, h, i, j and k are in accordance with 0.01 $ 1, 0 $ g < 2 S2, 0 < j $ 2 , OSkSl, and h and i does not h + i + j S 2.5 and 2 $ f + g + h + i + j + kg 3 where the coefficients a and f represent the number of degrees of substitution relative to the 矽, this number 値Too small, the use of an organic functional group that is supposed to have its reactivity, must be at least one molecule, on the other hand, the degree of substitution of the organic functional group is greater than 1, or in terms of cost. There will be difficulties, so The range of 0.01 S1 is preferably the range of O.lSaSl and O.ISfS] 〇.lSaS〇.8 and 0_lSfg0.8. The coefficients b and g represent the number of carbon atoms 1~8 relative to the bond of the deuterium atom. The unsubstituted monovalent hydrocarbon group, when the number 値 is 〇 or close to 〇, the content of the alkoxy group is increased, or the contribution rate of the decaneization reaction is increased, and the affinity of the oxalate relative to water is increased. Depending on the type of monovalent hydrocarbon group, it has the advantage of organic poly (alkyl group, etc.) and compatibility with acrylic resin: the volume of the hospital base is high, and 2 is consistent with 〇.〇1ag 1 1, and 0.1 sc + dg In the formula (II), when f, g, 0 ghg 2, 0 si ϋ is 〇, and 〇. ig : sub-organic functional group polyoxyalkylene, the characteristics produced cannot Organic functional group. Because of the range of $ as 1 and 〇 _ (H $ f ί in the synthesis method, it is better to increase the degree of substitution with aliphatic and unsaturated, to the ground, and to the different water conditions, organic poly' When the number is large, the oxane imparts hydrophobicity: high (phenyl, etc.), and imparts softness or release to the cured product of -22-200904930 adhesive. When the effect of (methyl) or the like is increased, b or g is increased because the content of the alkoxy group is relatively decreased, and it becomes unsuitable for the use of a reactive alkoxy group in which alkoxyalkylene group is used. Therefore, it is used depending on the purpose of use. The range of 〇Sb<2 and 〇$g<2 is preferably in the range of 0SbS1 and 〇^§$1, more preferably 〇'^>$〇.8 and 〇'§'〇.8 range ° The coefficients c and d ' in (I) and the coefficients h, 1 and j in the formula (11) indicate the degree of substitution of a plurality of kinds of oxime oxy groups different from the number of carbon atoms of the ruthenium atom, c And h represents the degree of substitution of the methoxy group 'd and i represents the degree of substitution of the ethoxy group, and j represents the alkoxy group of the carbon atom 3 and/or 4 in the organopolyoxane represented by the above average composition formula (Π). The degree of substitution of the base. The first organopolyoxane represented by the above average composition formula (I) is at least one of a methoxy group and an ethoxy group having high hydrolysis reactivity, and the degree of substitution can be arbitrarily set depending on the purpose of use. The ratios c and d of the respective contents are 0ScS2, the range of 0SdS2', and the range of c + d indicating the total substitution degree of the methoxy group and the ethoxy group is 0.1 S c + d$ 2.5 'better 舄0$ 〇 $1.8, 0$£1$1.8 range, and 0.2$〇+ (1$2.35. The c and d in formula (I) are all numbers greater than 0' containing both methoxy and ethoxy groups. The organic polyoxane has a wide range in hydrolysis reactivity, and at the same time, when the second organopolyoxane represented by the above average composition formula (Π) is used, a so-called grade which can be expected to contribute to the stage of hydrolysis reaction can be expected. The effect, wherein c and d are more preferably O.lgcSl.8, 0.1SdS1.8, and the range of 〇.5Sc + dS 2 · 3 5 . The second organic polyfluorene represented by the above average composition formula (II) In the alkane, the content of the methoxy group and the ethoxy group having high hydrolysis reactivity is h and i, and -23-200904930 is a propoxy group having a low hydrolysis reactivity. The content ratio of the alkoxy group having 3 or more carbon atoms, etc., is appropriately set depending on the purpose of use and the desired hydrolysis reactivity, but the control and the average composition are lowered by lowering the hydrolysis reactivity. The hydrolysis reactivity of the first organopolyoxane represented by the formula (I), and as described above, in the hydrolysis reaction at the time of use, not leaving only the second organopolyoxane For the purpose of the so-called grade effect which contributes to the hydrolysis reaction of the stage, it is made to be in the range of 0 S h S 2 and 〇SiS2, and h and i are not simultaneously 〇, 〇 <j The range of $2, and the total substitution degree of the alkoxy group is h + i + j is 0.1Sh + i + jS 2.5, preferably 0ShS1.8, OSigl.8, and at least one of h and i is 0.1 or more. The range of 〇.2Sh + i+jS2_35 is more preferably the range of O.lShS 1.8, 0.1S iS 1.8, O.lgjS 1.8, 0.5Sh + i+j S2.35. Both h and i in formula (II) For the number exceeding 0, both a methoxy group and an ethoxy group are preferred. Further, the coefficient e in the formula (I) and the coefficient k ' in the formula (11) indicate a substitution with respect to the hydroxyl group of the ruthenium atom. 'That means the number of decyl alcohol groups, this stanol group can participate in the oximation reaction or condensation reaction 'has a hydrophilic effect on the organic polyoxane' but is stabilized by the preservation of the organopolysiloxane From the viewpoint of ensuring the property, it is only possible to reduce the amount of use. Therefore, it is in the range of O^eSl and is preferably in the range of 〇SeS〇.5 and 0 S 0.5, more preferably 〇_2 and 〇' The range of kS 0.2. The sum of the coefficients in the formula (I) (a + b + c + d + e), and the sum of the coefficients in the formula (11) (f + g + h + i + j + k) ' is a decision table The condensation degree of the organic polyoxo hospital represented by the above average composition formulas (I) and (II) [4_ -24- 200904930 (a + b + c + d + e)]/2 and [4-(f+ g + h + i+j+k)] /2 the number 値, making it a range of a + b + c + d + e$3 and 2$f+g + h + i+ j + k$3 'this organic poly The degree of polymerization of the siloxane may range from two dimers of ruthenium atoms to hundreds of polymers of ruthenium atoms. However, when the average degree of polymerization is 2, the content of the monomer in the produced organopolysiloxane is increased, and the original purpose of the polyoxynoxy oligo is destroyed, and the average degree of polymerization is too large because It is difficult to operate as a high-viscosity product or a paste or a solid. Therefore, the average polymerization degree is preferably from 3 to 100, and more preferably from 3 to 50. From this point of view, the above (a + b + c + d + e) and (f + g + h + i + j + k) ' are preferably 2$ & + 匕 + 〇 + (1 + 6$2.67 and 2$£+8 + 11 + 丨+』+ 1^€2.67 range, more preferably 2< a + b + c + d + e^ 2.67S.2< f+g + h + i+ j+ K^ 2.67^ |bH|. The first organopolyoxane having an organic functional group and a methoxy group and/or an ethoxy group in one molecule, and an organic functional group and a methoxy group in one molecule and/or The second organopolyoxane having an ethoxy group and a carbon number of 3 and/or 4 alkoxy groups, each represented by the above average composition formulas (1) and (II), each of the coefficients a to e and the coefficient f to k satisfying the above The number of the ranges may be linear, branched, cyclic, or a combination thereof. [Method for Producing Organic Polyoxane] Next, a method for producing an organic polyoxane will be described. The first organopolyoxane of the above-mentioned average composition formula (I) having an organic functional group and a methoxy group and/or an ethoxy group in the molecule can be produced by various prescriptions known in the prior art. The above contains an organic functional group and a methoxy group and/or Ethoxy decane coupling agent as a raw material 'partially hydrolyzed separately. Poly-25-200904930 condensed method; or other alkoxy decane and/or its partial hydrolyzate and/or its condensate' Partial cohydrolysis/polycondensation is carried out. Therefore, most of the obtained first organopolyoxane is a liquid. The following average composition formula (π) represents one of the molecules containing an organic functional group and a The first organic polyoxaxane having an oxy group and/or an ethoxy group and a tertiary alkyl group having 3 and/or 4 carbon atoms can also be produced by various prescriptions known in the prior art as a general means. For example, the method described below is as follows: (1) A method of partially hydrolyzing and polycondensing a plurality of alkoxy decane having a plurality of organofunctional groups and a plurality of carbon atoms having a different number of carbon atoms. a method of partial co-hydrolysis/polycondensation of a functional alkoxydecane, and an alkoxydecane having an alkoxy group different from the number of carbon atoms thereof and having no organic functional group. (3) By the same Partial hydrolysis. The polycondensation operation results in In an organopolyoxane having a functional group and a methoxy group and/or an ethoxy group, an alkoxy group having 3 and/or 4 carbon atoms is introduced by transesterification with an alcohol having 3 and/or 4 carbon atoms. In the present invention, 'the prescription based on the above (2) from the viewpoint of the degree of freedom in the structural design of the organopolysiloxane represented by the above average composition formula (II) and the ease of obtaining the raw material At least one of the organofunctional group-containing alkoxydecane represented by the following general formula (III) and/or a partial hydrolyzate thereof, and at least one of the following general formula (IV) It is preferred that the mixture of the sandane compound and/or its partial hydrolyzate and/or its condensate undergo partial co-hydrolysis and polycondensation to form an organopolyoxane. • 26 - 200904930 YR1mSi(〇CH3)n(〇C2H5)3-mn (III) R1pSi(0CH3)q(0C2H5)r(0R2)4.pq,r ((iv) where 'γ, R1 and R2 are each The same as the meaning expressed in the above formula (II), m is an integer of 0 to 2 'n is an integer of 〇~3, but m + n is 3 or less 'p is an integer of 0 to 2' q is 〇~4 An integer of r is an integer of 0 to 4, and P + q + r is 4 or less 'but' is an alkoxy group-containing decane compound of the general formula (IV), and at least one component having an OR2 group is used. Further, as a modification method, an organopolyoxane can be obtained by the following method, that is, first, the alkoxysilane having an organic functional group represented by the above general formula (III), and the above general formula (IV) The decane compound containing at least one alkoxy group is partially pre-hydrolyzed, and then the partially hydrolyzed product is mixed with the above-mentioned general formula (IV) and previously used for partial co-hydrolysis. Different alkoxy-containing decane compounds and/or partial hydrolyzates thereof and/or condensates thereof are subjected to partial hydrolysis and polycondensation to obtain an organic polyoxyalkylene. This method also employs at least one component having a group as the alkoxy group-containing decane compound represented by the above general formula (IV). Specific examples of the organofunctional group-containing alkoxydecane represented by the above general formula (III) include, as the organic functional group, a mercaptomethyl group, a 3-mercaptopropyl group, a 6-fluorenylhexyl group, and 1 0-decyldodecyl, 2-(4-disylmethylphenyl)ethyl, glycidoxymethyl, 3-glycidoxypropyl, 5,6-epoxyhexyl, 9, 10-epoxymethyl, 2-(3,4-epoxycyclohexyl)ethyl, 2-(3,4-epoxy-4-methylcyclohexyl)propyl, acryloxymethyl-27- 200904930 Prepared propyl, 6-propanol, oxyhexyl, 10-propanol, 3, propylene, 醯 ^ ^ ^ ^ 篡 醯 醯 醯 methoxymethyl '3 - methacryloxypropyl propyl,癸基基,中费6_甲甲丙含氧基基基, 10-methylpropenyloxy fluorenyl, ethylene #β^甘, 5-hexenyl, 9-nonenyl, 3-vinyl Oxypropyl, yl, allyl-7α-glycyl, cyclohexenylethyl, chloromethyl, 3-chloropropyl, 6-chlorohexanyl - Benyi Cat Lane, bromomethyl, 3 -Bromopropyl, aminomethyl, 3-amino, 10-chlorolamine, its propyl, hydrazine-methyl-3-aminopropyl, hydrazine, hydrazine-dimethyl-3 -propyl, 6-amino η $ ^ ^phenyl·3_aminopropyl, Ν-(2-aminoethyl)-3-amino

胺基丙基、P 胺基己基）-3 -胺基丙基、N-(乙稀基卞基）-2 -胺 丙基、N - (6 -职土 基乙基_3 •胺基丙基等之三甲氧基矽烷化合物、三乙氧基 石夕Γ {匕a物、甲基二甲氧基砂院化合物、甲基二乙氧基砂 ^ Λ ^ 7基二甲氧基矽院化合物、乙基二乙氧基较！：完 烷化合物、：$ 其二甲氧基矽烷化合物、丙基二乙氧基矽烷化 化合物、丙晷 合 物 物、乙 一甲棊甲氧基砂丨完化合物 '二甲基乙氧基完化€ —甲氧基矽烷化合物、甲氧基二乙氧基矽烷化 氧基一 ^ 合物等。 忙〜，列舉上述一般式（IV)所表示之含有烷氧基的石夕 接者 院化合物的具體例子，作爲p = 〇的烷氧基矽烷，可列舉四 甲氧基砍嫁、四乙氧基矽烷、四丙氧基矽烷、四異芮氧基 砂院、四丁氧基政院、四異丁氧基砂院等；作爲的嫁 氧基矽烷’可列舉具有甲基、乙基、丙基、異丙基、卜甲 基丙基、丁基、異丁基、tert-丁基、己基、辛基、苯基、 甲苯其、罕基、苯基乙基等之三甲氧基矽烷、三乙氧基石夕 院、三丙氧基矽烷、三異丙氧基矽烷、三丁氧基矽烷、二 -28- 200904930 異丁氧基矽烷等；作爲p = 2的烷氧基矽烷，可列舉二甲基 二甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二丙氧基矽 烷、二甲基二丁氧基矽烷、甲基乙基二甲氧基矽烷、二苯 基二甲氧基矽烷、二苯基二乙氧基矽烷等。 再者，由原料的取得容易度或成本面而言，上述一般 式（III)中之m爲0，且n爲3或〇者，亦即，使用含有有機 官能基之三甲氧基矽烷、三乙氧基矽烷及/或其部份水解 物、與上述一般式（IV)中之R1爲甲基，且ρ爲1及/或0者 ，亦即，甲基三烷氧基矽烷、四烷氧基矽烷及/或其部份 水解物及/或其縮合物較佳。而且，以上述一般式（IV)中 之q及r皆爲0之含有烷氧基的矽烷化合物及/或其部份水 解物及/或其縮合物作爲必須成分更佳。 特別是，作爲上述一般式（III)所表示的含有有機官能 基的烷氧基矽烷，可使用至少一種選自3 -锍基丙基三甲氧 基矽烷、3 -锍基丙基三乙氧基矽烷、3 -環氧丙氧基丙基三 甲氧基矽烷、3 -環氧丙氧基丙基三乙氧基矽烷、2-(3,4 -乙 氧基環己基）乙基三甲氧基矽烷、2-(3,4 -乙氧基環己基）乙 基三乙氧基矽烷；作爲上述一般式（IV)所表示之含有烷氧 基的矽烷化合物，使用至少一種選自甲基三甲氧基矽烷、 甲基三乙氧基矽烷、甲基三丙氧基矽烷、甲基三異丙氧基 矽烷、甲基三丁氧基矽烷、甲基三異丁氧基矽烷、四甲氧 基矽烷、四乙氧基矽烷、四丙氧基矽烷、四異丙氧基矽烷 、四丁氧基矽烷、四異丁氧基矽烷（惟，以具有丙氧基、 異丙氧基、丁氧基或異丁氧基之至少一種的矽烷化合物作 -29- 200904930 爲必須成分），特別佳。 此等之含有有機官能基的烷氧基矽烷及/或其部份水 解物、與含有烷氧基的矽烷化合物及/或其部份水解物及/ 或其縮合物，可倂用各複數種，但上述一般式（III)所表示 之含有有機官能基的烷氧基矽烷及/或其部份水解物使用 二種以上時，具有相同的有機官能基者較佳，此外，爲了 任意地設計有機聚矽氧烷中的甲氧基、乙氧基、碳原子數 3及或4的烷氧基的比率，作爲上述一般式（IV)所表示之含 有烷氧基的矽烷化合物及/或其部份水解物及/或其縮合物 ，倂用烷氧基的種類不同的二種以上較佳。 上述一般式（III)所表示之含有有機官能基的烷氧基矽 烷及/或其部份水解物、與上述一般式（IV)所表示之含有 烷氧基的矽烷化合物及/或其部份水解物及/或其縮合物之 摻合比率並沒有特別的限制，但前者的摻合比率太少，因 爲所得到的有機聚矽氧烷於使用時，原本應具有之基於有 機官能基的反應性的特性無法充分地被發揮，必須爲一分 子中至少具有一個的有機官能基者，故兩成分的Si原子 換算莫耳比爲1: 99〜99: 1的範圍較佳，更佳爲10: 90〜80 :2 0的範圍。 此外，此等各種原料的摻合順序或混合方法、及進行 部份共水解、聚縮合之方法並沒有特別的限制，基於先前 技術習知的方法，例如可藉由於上述含有有機官能基的烷 氧基矽烷及/或其部份水解物、與含有烷氧基的矽烷化合 物及/或其部份水解物及/或其縮合物的混合物中’在水分 -30- 200904930 解•縮合反應觸媒的存在下，加入水後進行部份共水解及 聚縮合而得到，此時，必要時可使用適當的有機溶劑。 作爲此反應中之水分解·縮合反應觸媒，可使用各種 先前技術以來既已習知者，作爲具體例子，可列舉乙酸、 三氟乙酸、丁酸、草酸、馬來酸、枸櫞酸、甲烷磺酸、P-甲苯磺酸、三氟甲烷磺酸等之有機酸類、鹽酸、硝酸、磷 酸、硫酸等之無機酸類，氫氧化鈉、氫氧化鉀、碳酸氫鈉 、碳酸鈉、乙酸鈉、乙酸鉀、氨、氫氧化銨、三甲基胺等 之鹼性化合物類，氟化鉀、氟化銨等之含氟化合物類，四 異丙基鈦酸酯、四丁基鈦酸酯、二辛基二月桂酸錫、鋁螯 合劑類等之有機金屬化合物類等。上述觸媒可單獨使用， 或亦可倂用複數，但觸媒的使用量，相對於原料總整中所 存在的 Si原子莫耳數，爲0.0001〜10莫耳％的範圍，更佳 爲0 · 0 0 1〜3莫耳％的範圍。 如上述，有機聚矽氧烷的聚合度只要是從矽原子2個 的二聚物至矽原子數百個程度的聚合物爲止即可，但藉由 部份水解、聚縮合所使用的水的量決定平均聚合度，添加 過量的水’則此部份的烷氧基被水解而成爲支鏈結構多的 樹脂體’而無法得到目的之聚矽氧烷烷氧基寡聚物，故水 解所使用的量須要嚴格決定。例如，所使用的烷氧基矽烷 原料皆爲矽原子丨個的單體時，爲了調製平均聚合度Z的 有機聚矽氧烷，可相對於Z莫耳的烷氧基矽烷原料使用 (Z- 1 )莫耳的水進行部份水解、聚縮合。 此時’必要時亦可使用醇類、醚類、酯類、酮類等之 -31 - 200904930 有機溶劑，作爲此等的有機溶劑的具體例子，可列舉甲醇 、乙醇、η-丙醇、異丙醇、丙二醇單甲基醚等之醇類，二 乙基醚、二丙基醚等之醚類，乙酸甲酯、乙酸乙酯、乙醯 乙酸乙酯等之酯類，丙酮、甲基乙基酮、甲基異丁酮等之 酮類等。此外，可與如上述的極性溶劑，同時倂用己烷、 甲苯、二甲苯等之非極性溶劑，特別是使用甲醇、乙醇、 異丙醇等之醇類較佳。 有機溶劑的使用量，相對於原料之烷氧基矽烷及/或 其部份水解及/或縮合物之合計100質量份而言，可使其爲 0〜1 0 0 0質量份的範圍，但使用量太少，會有水解開始時的 反應系無法均勻的情況，太多則因爲不但看不到更好的添 加效果’且Ρ 01 y i e 1 d降低而在經濟面較不利，故以1 0〜5 0 0 質量份的範圍較佳，更佳爲2 0〜2 0 0質量份的範圍。 部份（共）水解及聚縮合反應中之實際的操作，係在由 烷氧基矽烷原料、觸媒及有機溶劑所成的混合系中，滴入 所定量的水或水/有機溶劑的混合液，或者於由烷氧基矽 烷原料及有機溶劑所成的混合系中，滴入所定量的水/觸 媒的混合溶劑或水/觸媒/有機溶劑的混合溶液較佳。此時 ’亦可將具有水解反應性高的甲氧基或乙氧基之烷氧基矽 烷原料、與具有水解反應性低的丙氧基或丁氧基等之碳原 子數3及/或4的烷氧基之烷氧基矽烷原料，預先分別進行 部份水解後，混合兩成分’依情況再進行部份共水解後， 再進行縮合反應。各反應可在〇~15〇°c的溫度範圍實施， 但一般而言，低於室溫的溫度，因爲反應的進行變慢而不 -32- 200904930 實用，此外太高溫時’亦因爲巯基、環氧基等之熱分解或 丙烯醯氧基的熱聚合等對有機官能基產生壞影響，故使其 爲2 0 ~ 1 3 0 C的溫度範圍較佳。反應後’所使用的觸媒藉由 中和、吸附、過濾等去除之操作，或藉由所使用的有機溶 劑與副產生的醇、低沸點物的蒸餾去除等而進行純化，可 得到目的之有機聚矽氧烷，因此所得到的有機聚矽氧烷大 部份的情況爲液體。 [黏著劑組成物] 本發明中，如上述說明的丙烯酸樹脂中，摻合同上述 說明的交聯劑、第一有機聚矽氧烷與第二有機聚矽氧烷， 成爲黏著劑組成物。交聯劑係相對於構成黏著劑組成物之 丙烯酸樹脂100質量份（使用2種以上時爲其合計量），通常 以0 . 1〜1 0質量份程度，較佳爲0 . 1〜7質量份程度，更佳爲 0.2〜3質量份程度的比例摻合。相對於丙烯酸樹脂100質量 份之交聯劑的量爲0. 1質量份以上，因爲會有黏著劑層的 持久性提高的傾向而較佳，此外，此量爲1 〇質量份以下， 因爲將附黏著劑之光學薄膜用於液晶顯示裝置時之所謂的 泛白變不明顯而較佳。 第一有機聚矽氧烷與第二有機聚矽氧烷，相對於構成 黏著劑組成物之丙烯酸樹脂100質量份（使用2種以上時爲 其合計量），通常以0.0001〜10質量份程度’較佳爲0.01〜5 質量份程度，更佳爲0.1~1質量份程度的比例使用。相對 於丙烯酸樹脂100質量份之有機聚矽氧烷的量爲0.0001質 -33- 200904930 量份以上，因爲會有黏著劑層與玻璃基板的密著 傾向而較佳，此外’此量爲1 0質量份以下，因爲 從黏著劑層溢出有機聚矽氧烷的傾向而較佳。 關於弟一有機聚砂氧院及第一有機聚砂氧院 率’並沒有特別的限制’可依使用目的而適當的 由兩者混合的狀態下控制水解反應性的觀點而1 後者的混合比率以質量而言爲10/90〜90/10的範 而且以質量比而言爲20/80〜80/20的範圍更佳。 機聚矽氧烷及第二有機聚矽氧烷，可預先混合後 烯酸樹脂及交聯劑，亦可各別準備後摻合丙烯酸 聯劑’預先混合時’或是於黏著劑組成物調製時 只要單純混合必要成分即可，對於其混合方法或 溫度條件％並沒有特別的限制。 以上說明的黏著劑組成物，亦可再摻合交聯 候安定劑、增黏劑、可塑劑、軟化劑、染料、顏 塡充劑等’其中，又以於黏著劑中與交聯劑同時 觸媒，則可以短時間的熟成調製黏著劑層，所得 著劑之光學薄膜貼合於液晶室玻璃時，可抑制黏 光學薄膜之間發生浮起或剝離，或者黏著劑層內 ’而且再加工性亦更加優異。作爲交聯觸媒，可 甲撐二胺、乙撐二胺、聚乙抱亞胺、六甲撐四胺 三胺、三乙撐四胺、異氟爾酮二胺、三甲撐二胺 樹脂、三聚氰胺樹脂之胺系化合物等。於黏著劑 系化合物作爲交聯觸媒時，以異氰酸酯系化合物 性提高的 會有抑制 的混合比 選擇，但 Ϊ，前者/ 圍較佳， 由第一有 再摻合丙 樹脂及交 摻合時， 混合時的 觸媒、耐 料、無機 摻合交聯 到的附黏 著劑層與 引起發泡 列舉如六 、二乙撐 、聚胺基 中摻合胺 作爲交聯 -34- 200904930 劑較適合。 黏著劑組成物通常被調製成上述的各成分溶解於有機 溶劑的狀態，因此所使用的有機溶劑’只要是可溶解上述 的各成分即可，例如可使用如甲苯或二甲苯之芳香族烴類 ，如乙酸乙酯或乙酸丁酯之酯類，如丙酮或甲基乙基酮、 甲基異丁基酮之酮類等。 [附黏著劑之光學薄膜] 本發明之附黏著劑之光學薄膜’係光學薄膜的至少一 側的面上，設置如上述之由黏著劑組成物所成的黏著劑層 者。其中所使用的光學薄膜，係指具有光學特性之薄膜， 可列舉例如偏光薄膜、相位差薄膜等。 偏光薄膜，爲相對於自然光等的入射光’具有射出偏 光的機能之光學薄膜。偏光薄膜中，包括具有吸收具有某 方向的振動面之直線偏光，而穿透具有與其正交的振動面 之直線偏光的性質之直線偏光薄膜；具有反射具有某方向 的振動面之直線偏光，而穿透具有與其正交的振動面之直 線偏光的性質之偏光分離薄膜；層合偏光薄膜與後述的相 位差薄膜之楕圓偏光薄膜等。作爲偏光薄膜’特別是作爲 直線偏光薄膜（亦被稱爲偏光子、或偏光子薄膜）的適合具 體例子，可列舉經一軸延伸的聚乙烯醇系樹脂薄膜上吸附 配向碘或二色性染料等之二色性色素者。 相位差薄膜，爲顯示出光學各向異性之光學薄膜’可 列舉例如藉由將由聚乙烯醇、聚碳酸酯、聚酯、聚芳香酯 -35- 200904930 、聚醯亞胺、聚稀烴、環狀聚燦烴、聚苯乙燦、聚颯、聚 醚颯、聚偏氟乙嫌/聚甲基甲基丙烧酸酯、液晶聚酯、乙 醯纖維素、乙烯-乙酸乙烯酯共聚物皂化物、聚氯乙it等 所成的高分子薄膜，延伸1.01〜6倍程度而得到的延伸薄膜 等。其中，又以將碳酸酯薄膜或環狀聚烯烴系薄膜經一軸 延伸或二軸延伸的高分子薄膜較佳’亦有被稱爲一軸性相 位差薄膜、廣視野角相位差薄膜、低光彈性率相位差薄膜 等者，任一種皆可適用。 此外，藉由液晶性化合物的塗佈•配向而使其表現出 光學各向異性之薄膜、或藉由無機層狀化合物的塗佈而使 其表現出光學各向異性之薄膜’皆可作爲相位差薄膜使用 ，如此的相位差薄膜中，被稱爲溫度補償型相位差薄膜者 ，此外，由新日本石油（股）以”LC薄膜”的商品名販賣之 棒狀液晶經扭轉配向的薄膜、同樣是由新日本石油（股）以 ”NH薄膜”的商品名販賣之棒狀液晶經傾斜配向的薄膜、 由富士薄膜（股）以” WV薄膜”的商品名販賣之圓盤狀液晶 經傾斜配向的薄膜、由住友化學（股）以” VAC薄膜”的商品 名販賣之完全二軸配向型的薄膜、同樣是由住友化學（股） 以” n e w V A C薄膜”的商品名販賣之二軸配向型的薄膜等。 而且，此等光學薄膜黏著保護薄膜者，亦可作爲光學 薄膜使用。作爲保護薄膜，使用透明的樹脂薄膜，作爲此 透明樹脂，可列舉例如以三乙醯纖維素或二乙醯纖維素爲 代表的乙醯纖維素系樹脂、以降冰片烯系樹脂爲代表的非 晶性環狀聚稀煙系樹脂、以聚甲基甲基丙稀酸酯爲代表的 -36- 200904930 甲基丙烯酸樹脂、聚酯樹脂、聚烯 脂、聚醚醚酮樹脂、聚颯樹脂等。 ，亦可摻合水楊酸酯系化合物、二 三唑系化合物、三曉系化合物、氰 鎳錯鹽系化合物等之紫外線吸收劑 乙醯纖維素薄膜等之乙醯纖維素系 系樹脂薄膜等之非晶性環狀聚烯烴 。非晶性環狀聚烯烴系樹脂薄膜 JSR(股）所販賣的“ARTON薄膜”、 “ ZEONOR”等（皆爲商品名），此外 差薄膜作爲直接保護薄膜。 上述所說明的光學薄膜中，直 以構成其之偏光子，例如由聚乙烯 薄膜的單面或兩面上黏貼保護薄膜 述的楕圓偏光薄膜，爲層合直線偏 ，但此直線偏光薄膜，亦大部份爲 上黏貼保護薄膜的狀態。在如此的 本發明的黏著劑層時，通常在此相 層，設置本發明之黏著劑層之光學 可列舉包括偏光子的至少一方的面 樹脂或非晶性環狀聚烯烴系樹脂所 膜者。 附黏著劑之光學薄膜，例如， ，塗佈上述所說明的黏著劑組成物 烴系樹脂、聚碳酸酯樹 構成保護薄膜之樹脂中 苯甲酮系化合物、苯並 基丙烯酸酯系化合物、 。作爲保護薄膜，以三 樹脂薄膜、或降冰片烯 系樹脂薄膜較適合使用 的市售品，有例如由 由（股）OPTES所販賣的 ，亦可使用上述的相位 線偏光薄膜，大部份是 醇系樹脂所成的偏光子 的狀態使用。此外，上 光薄膜與相位差薄膜者 偏光薄膜的單面或兩面 楕圓偏光薄膜上’形成 位差薄膜側形成黏著劑 薄膜的較適合的例子， 上黏貼由乙醯纖維素系 成的保護薄膜之偏光薄 可藉由在剝離薄膜之上 後形成黏著劑層’於所 -37- 200904930 得到的黏著劑層上再層合光學薄膜之方法，於光學薄膜之 上塗佈黏著劑組成物後形成黏著劑層，於此黏著劑面貼合 剝離薄膜進行保護，成爲附黏著劑之光學薄膜之方法等而 製造。其中，作爲剝離薄膜，可列舉例如將由聚對苯二甲 酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚碳酸酯、聚芳基 酯等之各種樹脂所成的薄膜作爲基材，在此基材與黏著劑 層的黏合面上^施加如聚砂氧院處理之脫模處理者等。黏 著劑層，可藉由將成爲如上述的有機溶劑溶液之黏著劑組 成物，於上述的剝離薄膜或光學薄膜上進行塗佈、乾燥之 方法而製造。塗佈可使用習知的各種塗佈機，塗佈後通常 以0〜50 °C程度的溫度及20〜80%程度的相對濕度，使其進 行3〜1 4天程度熟成，熟成的較佳條件，係溫度爲2 0〜3 0 °C 程度、相對濕度爲5 5〜7 5 %程度、期間爲5〜7天程度。藉由 此熟成，黏著劑的交聯反應進行，在剝離薄膜之上設置黏 著劑層時，熟成可在於此剝離薄膜上形成黏著劑層的狀態 下進行，於光學薄膜上層合剝離薄膜上的黏著劑層後進行 亦可。 黏著劑層的厚度並沒有特別的限制，但通常爲3 0 // m 以下者較佳’又以1 0 # m以上者較佳。黏著劑層的厚度爲 3 0 // m以下’會有高溫高濕下的黏著性提高，玻璃基板與 黏著劑層之間發生浮起或剝離的可能性變低的傾向，而且 會有再加工性提高的傾向而較佳，此外，厚度爲1 〇 # m以 上，會有因爲即使與其貼合的光學薄膜的尺寸變化，其尺 寸變化隨者黏著劑層變動，故液晶室的周緣部的明亮度與 -38- 200904930 中心部的明亮度之間的差距消失，泛白或顏色不均受到抑 制的傾向而較佳。 本發明的附黏著劑之光學薄膜，以其黏著劑層進行層 合於玻璃基板，可成爲光學層合物。其中，作爲玻璃基板 ’可列舉例如液晶室的玻璃基板、防眩用玻璃、太陽眼鏡 用玻璃等。其中’又以液晶室的前面側（觀看側）的玻璃基 板上層合附黏著劑之光學薄膜（上偏光薄膜），液晶室的背 面側的玻璃基板上層合其他的附黏著劑之光學薄膜（下偏 光薄膜）而成的光學層合物，可作爲液晶顯示裝置使用。 作爲玻璃基板的材料，可列舉例如鹼石灰玻璃、低鹼玻璃 、無鹼玻璃等。將附黏著劑之光學薄膜層合於玻璃基板後 成爲光學層合物’例如可將剝離薄膜從如上述作法所得到 的附黏著劑之光學薄膜剝離，將露出的黏著劑層貼合於玻 璃基板的表面即可。 本發明的附黏著劑之光學薄膜，黏著於玻璃基板後成 爲光學層合物後，因爲某些不佳的狀況，將此光學薄膜自 玻璃基板剝離時，黏著劑層跟著光學薄膜剝離，與黏著劑 層接觸的玻璃基板的表面上，幾乎未發生霧點或漿糊殘留 等，故很容易於剝離後的玻璃基板上再重新貼合附黏著劑 之光學薄膜。亦即，所謂的再加工性優異。 將本發明的附黏著劑之光學薄膜，貼合於液晶室玻璃 的至少一方的面上後所形成的液晶顯示裝置，例如可使用 於包括卓記型、桌上型、PDA(Personal Digital Assistance)等 之個人電腦用液晶顯示器、電視、車用顯示器、電子字典 -39- 200904930 、數位相機、數位攝影機、電子計算機、手錶等。 【實施方式】 實施例 以下，列舉實施例更具體地說明本發明，但本發明並 非限定於此等之例子’實施例中’表示使用量及含量之份 及％，在沒有特別的理由下爲質量基準。 以下的例子中，丙烯酸樹脂的不揮發份’爲使用依據 JIS K 5 407之方法所測量的値，具體而言，係以黏著劑溶 液用任意的質量放於盤中’用防爆烘箱以1 1 5 °C使其乾燥2 小時後的殘留不揮發份質量’相對於最初所測得的溶液的 質量之比例表示。丙烯酸樹脂的重量平均分子量’係於 GPC裝置中，將作爲管柱之東曹（股）製的“ TSK gel G Μ H H R - Η ( S) ” 2支直列地串聯進行配置，使用四氫呋喃作 爲溶離液，以試料濃度5mg/ml、試料導入量ΙΟΟμ1、溫度 4 〇 °C、流速1 m 1/分鐘的條件，藉由標準聚苯乙換算所測 量的値。 此外，各實施例所得到有機聚矽氧烷的分析’用以下 所表示的方法進行。 (1)有機聚矽氧烷的平均分子量及平均聚合度 藉由凝膠滲透層析法（GPC)分析，以由聚苯乙烯標準 試料所製作的檢量線爲基準，計算出重量平均分子量，而 且由此等算出平均聚合度。 -40- 200904930 (2)有機聚矽氧烷中的烷氧基含量 藉由鹼裂解·氣相層析法（GC)分析法[參考聚矽氧烷手 冊’ 7 9 2 - 7 9 3 ( 1 9 9 0年，日刊工業新聞公司發行）]，測量烷 氧基含量，決定上述平均組成式（I)中之係數c、d及，以 及上述平均組成式（Π)中之係數h、i及j。 (3 )有機聚矽氧烷的結構解析 藉由進行矽核磁共振光譜（29Si-NMR)分析及質子核磁 共振光譜CH-NMR)分析，由測量結果決定上述平均組成 式（1)中之係數a、b及e，以及上述平均組成式（II)中之係 數f、g及k。 (4)有機聚矽氧烷的锍基當量 依據乙酸/碘化鉀/碘酸鉀添加-硫代硫酸鈉溶液滴定法 [參考分析化學便覧，改訂二版，432-433頁（1976年’九 善股份有限公司發行）]而測量。 (5 )有機聚矽氧烷的黏度 依據JIS K 8 8 0 3之方法，測量於2 5 °C的黏度。 首先，列出製造本發明所使用的丙烯酸樹脂之例。 [聚合例1 ] 具備冷卻管、氮氣導入管、溫度計及攪拌機之反應器 中，裝入乙酸乙酯81.8份、丙烯酸丁醋98.9份及丙稀酸1.1 -41 - 200904930 份的混合溶液，一邊用氮氣置換裝置內的空氣後成爲不含 氧，一邊將內溫提高至55°C。然後，將於乙酸乙酯10份中 溶解偶氮雙異丁腈（聚合起始劑）〇.1 4份的溶液全量添加， 起始劑添加1小時後，以添加速度1 7 · 3份/ h r連續地添加乙 酸乙酯於反應器中’使除了單體之外的丙稀酸樹脂的濃度 成爲3 5 %，於內溫5 4〜5 6 °C保溫1 2小時，最後添加乙酸乙 酯，調節至丙烯酸樹脂的濃度成爲2 0 %，所得到的丙嫌酸 樹脂A，藉由GPC之聚苯乙烯換算的重量平均分子量Mw 爲 1,670,000，Mw/Mn 爲 4.4。 接著’列出合成本發明所使用的有機聚矽氧烷之例。 [有機聚矽氧烷合成例1](第一有機聚矽氧烷） 於裝有攪拌裝置、冷卻電容器、溫度計及滴入漏斗之 容量1L的燒瓶中，裝入3 -锍基丙基三甲氧基砂院39.3g (〇_2莫耳）、甲基三甲氧基砂院40.9g(0·3莫耳）、四乙氧基 石夕院104.2g(0_5莫耳）、甲醇80.2g及乙醇i〇4.2g，一邊於 內溫20〜30C下攪拌燒瓶內’ 一邊用30分鐘滴入o.in鹽酸 水溶液16.2g(水：0_9莫耳’氯化氫：1.62χ1(Γ3莫耳）與乙 醇16.2g之混合溶液，更於昇溫後而還流下進行2小時熟成 〇 接著，添加氟化鉀的1%乙醇溶液9.4g(KF: 1.62xl〇-3 莫耳）’更在還流下進行2小時熟成後，進行部份共水解及 聚縮合反應。接著’在常壓下一邊使內溫昇溫至8 〇 t爲止 ’ 一邊蒸餾去除醇成分，更於30Torr(約4kPa)的減壓條件 -42- 200904930 下，使內溫昇溫至100°c後蒸餾去除殘留醇成分與低沸點 成分後，進行過濾而得到無色透明液狀的有機聚矽氧烷 C(產量：117.0g’ 產率：90%)。 此有機聚矽氧垸C’於上述平均組成式（I)中，Y爲3-锍基丙基，R1爲甲基，由所使用的各原料（有機溶劑以外） 的莫耳比、上述的分析結果所計算得到的重量平均分子量 、平均聚合度、相當於上述式（I)之平均組成式、锍基當 量、及黏度’如下述。 “有機聚矽氧烷c ”的原料莫耳比、平均組成式及物性 値 原料莫耳比： HS(CH2)3Si(〇CH3)3/CH3Si(〇CH3)3/Si(OC2H5 )4 = 0_2/0.3/0.5 觸媒：HC1/KF/水=0.00 1 62/0.00 1 62/0.9 重量平均分子量：1，380 平均聚合度：10.6 平均組成式： [HS(CH2)3]0.2(CH3)03Si(〇CH3)061(〇C2H5)108〇0905 锍基當量：測量値63 8g/莫耳，理論値65 1 g/莫耳 黏度：20.5mm2/s [有機聚矽氧烷合成例2](第二有機聚矽氧烷） 於裝有攪拌裝置、冷卻電容器、溫度計及滴入漏斗之 容量1L的燒瓶中，裝入四丙氧基矽烷1 32 2g(〇5莫耳）及 異丙醇1 32.2g ’ 一邊攪拌混合一邊於油浴中加熱而使內溫 -43 - 200904930 昇溫至50。(：爲止。一邊攪拌燒瓶內’ 一邊用10分鐘滴入 1N鹽酸水溶液7.2g(水：0·4莫耳’氯化氫：7_2xl0_3莫耳） 與異丙醇7 · 2 g之混合溶液’更於昇溫後進行2小時熟成後 得到預備水解反應液D1 ° 上述之外，另外於3_锍基丙基三乙氧基矽烷47.7g(0_2 莫耳）、甲基三乙氧基矽烷17_8g(0.1莫耳）、甲基三異丙氧 基矽烷44.1g(0.2莫耳）、乙醇65.5g及異丙醇44.1g的混合 溶液中，於內溫20~30°C下用10分鐘滴入1N鹽酸水溶液 7.2g(水：0.4莫耳，氯化氫：7.2X10·3莫耳）與異丙醇7.2g 之混合溶液，更於內溫2〇〜3 0°C下進行30分鐘熟成後’得 到預備水解反應液D2 ° 於上述的預備水解反應液D 1中添加預備水解反應液 D2後，攪拌混合後，一邊於內溫20〜3 0°C下添加1N鹽酸水 溶液1.8§(水：〇_1莫耳，氯化氫：1.8/1〇-3莫耳）與異丙醇 1 . 8 g之混合溶液，一邊於油浴中加熱而於還流下進行2小 時熟成。接著，添加氟化鉀〇.94§(〖？：1.62\10_2莫耳）， 更在還流下進行2小時熟成後，進行部份共水解及聚縮合 反應。 接著，在常壓下一邊使內溫昇溫至8 0 °C爲止，一邊蒸 餾去除醇成分’更於30Torr(約4kPa)的減壓條件下，使內 溫昇溫至1 〇〇 後蒸餾去除殘留醇成分與低沸點成分後’ 進行過濾而得到無色透明液狀的有機聚矽氧烷D(產量： 140_8g，產率：90%)。 此有機聚矽氧烷D，於上述平均組成式（II)中，Y爲 -44 - 200904930 3-锍基丙基，R1爲甲基，R2爲丙基及異丙基，由所使用的 各原料（有機溶劑以外）的莫耳比、上述的分析結果所計算 得到的重量平均分子量、平均聚合度、相當於上述式（II) 之平均組成式、锍基當量、及黏度，如下述。 “有機聚矽氧烷D”的原料莫耳比、平均組成式及物性 値 原料莫耳比： HS(CH2)3Si(OC2H5)3/CH3Si(〇C2H5)3/CH3Si(OC3H7)3/Si(〇C3H7)4=0.2/0.1/0.2/0.5 觸媒：HC1/KF/水=〇_〇162/0_0162/0.9 重量平均分子量：1，620 平均聚合度：1 0.3 平均組成式： [HS(CH2)3]0.2(CH3)0,3Si(OC2H5)0.39(〇C3H7)l.3 1〇0.9 S荒基當量：測量値803 g/莫耳，理論値785g/莫耳 黏度：33.6mm2/s 接著，使用上述所製作的丙烯酸樹脂及有機聚矽氧烷 ，調製黏著劑’列示出適用於光學薄膜的實施例及比較例 ，其中，使用下述者作爲交聯劑。 “CORONATE L” ：甲苯撐二異氰酸醋的三經甲基丙垸 加成物之乙酸乙酯溶液（固形分濃度7 5 % )，日本聚胺基甲 酸乙酯工業（股）製商品名 “TAZM” ：三羥甲基丙院三-氧雜環丙基丙酸酯（ 液體）、相互藥工（股）製商品名 此外’各自使用下述者，作爲比較例的矽烷化合物。 -45- 200904930 “ ΚΒΜ- 803 ” ： 3-锍基丙基三甲氧基矽烷（液體），信越 化學工業（股）製商品名 “KBM-303 ”： 2-(3,4-環氧環己基）乙基三甲氧基矽烷 (液體），信越化學工業（股）製商品名 [貫施例1〜3及比較例1~4] (a)黏著劑的製造 聚合例1所得到的丙烯酸樹脂A的乙酸乙酯溶液，此 處依表1所表示的量摻合CORONATE L”與”TAZM”作爲交 聯劑，以及依表1所表示的量各自摻合表1所示之聚有機聚 矽氧烷（或矽烷化合物），調製黏著劑組成物，惟，表1中 ，交聯劑”CORONATE L”的摻合量（份），爲固形分的量。 [表1] 例 黏著劑組成 丙烯酸樹 脂(量） 交聯劑(量） 第一有機聚矽氧烷 第二有機聚矽氧烷 CORONATE L ΤΑΖΜ 種類 量 種類 量 實施例1 1〇〇份 2_〇份 0.02 份 C 〇_1〇份 D 0.05 份 實施例2 1〇〇份 2·0份 0.02 份 C 〇_20 份 D 0.10份 比較例1 100份 2.0份 0.02 份 C 0.15份 _ _ 比較例2 100份 2.0份 0.02 份 _ _ D 〇.1〇 份 比較例3 100份 2_0份 0.02 份 ΚΒΜ-803 0.15份 一 _ 比較例4 1〇〇份 2_〇份 0.02 份 ΚΒΜ-303 0_15份 • _ (b)附黏著劑之光學薄膜的製作 -46 - 200904930 將上述的各黏著劑組成物，使用塗佈機塗佈於經脫模 處理的聚對苯二甲酸乙二醇酯薄膜（“PET 381 1”，Lintec( 股）製商品名，稱爲分隔板）之脫膜處理面上而使乾燥後的 厚度成爲1 5 μηι，使其以9 0 °C乾燥1分鐘，得到薄片狀的黏 著劑。接著，將碘吸附配向的聚乙烯醇偏光子的兩面，以 由三乙醯纖維素所成的保護薄膜挾住之3層結構的偏光薄 膜的單面上，藉由層合而貼合上述所得到的薄片狀黏著劑 之與分隔板相反側的面（黏著劑面）後，以溫度23它、相對 濕度6 5 %的條件使其進行7天熟成，得到附黏著劑之偏光 薄膜。此外，將此等的附黏著劑之偏光薄膜用附鋁箔的包 裝行密封，於溫度6CTC下再進行6天熟成，促進因爲熱所 產生的經時變化。 (c) 光學層合物（偏光薄膜的玻璃黏貼品）的製作 將上述（b)所製作的附黏著劑之偏光薄膜（經23 °C X 6 5%RHx7天熟成者，及後續再經60°C x6天熟成者），各自 以黏著劑層側進行黏貼而使液晶室用玻璃基板（“ 1 73 7”， CORING公司製商品名）的兩面成爲直接偏光下（cross-nicol)，製作光學層合物。 (d) 光學層合物的耐熱性及耐濕熱性的評估 關於上述（〇所得到的光學層合物，進行在溫度80 °C 的乾燥條件下保時3 0 0小時之耐熱試驗，此外進行在溫度 60°C、相對濕度90%下保管3 00小時之耐濕熱試驗，以目 -47- 200904930 視觀察各自試驗後的光學層合物，以下述4階段評估，結 果統一列示於表2。 (耐熱性及耐濕熱性的評估基準） ◎:完全沒有浮起、剝離、發泡等之外觀變化。 〇：幾乎看不到浮起、剝離、發泡等之外觀變化。 △:浮起、剝離、發泡等之外觀變化稍微明顯。 X:浮起、剝離、發泡等之外觀變化明顯。 (e)附黏著劑之光學薄膜的再加工性評估 再加工性的評估如下述進行，首先，將（b)所製作的 附黏著劑之偏光薄膜（經2 3 °C X 6 5 % RH X 7天熟成者，及後續 再經60°C x6天熟成者）各自裁切成25mmxl50mm大小的試 驗片，接著，將此試驗片以其黏著劑層側使用黏著裝置 (“LAMIPACKER”，FIJIPLA(股）製商品名）黏著於液晶室用 玻璃基板，以50°C、5kgf/cm2(490.3kPa)進行20分鐘高壓 鍋處理，接著，製作在溫度2 3 °C、相對濕度5 〇%的氣體環 境中保管24小時之試樣，與在5(TC的烘箱中保管48小時的 試樣之2種，以溫度2 3 °C、相對濕度5 0 %的氣體環境中， 從此黏著試驗片以3 00mm/分鐘的速度在1 80 °方向剝離， 觀察各自的玻璃基板表面的狀態，依以下的基準評估，結 果一起列示於表2。 〈再加工性評估基準〉 -48 - 200904930 ◎:玻璃板表面上完全沒有霧點等。 〇：玻璃板表面上幾乎沒有霧點等。 △:玻璃板表面上確認有霧點等。 X .玻璃板表面上確認有黏著劑殘留。 [表2]Aminopropyl, P-aminohexyl)-3-aminopropyl, N-(ethenyl)-2-aminopropyl, N-(6-protecternylethyl-3)-aminopropyl Trimethoxy decane compound, triethoxy oxime {匕a substance, methyl dimethoxy sand compound, methyl diethoxy sand Λ ^ 7 -dimethoxy oxime compound, Ethyl diethoxy compared to :: a complete alkyl compound,: $ dimethoxy decane compound, propyl diethoxy decyl compound, propylene conjugate, ethyl methacrylate methoxy quinone compound Dimethylethoxy completes the methoxy methoxy compound, methoxy diethoxy decyloxy compound, etc. Busy ~, exemplifies the alkoxy group represented by the above general formula (IV) Specific examples of the compounds of the Shishiji Institute, as the alkoxydecane of p = oxime, a tetramethoxy cyanide, a tetraethoxy decane, a tetrapropoxy decane, a tetraisodecyl oxylate, The tetrabutoxy government, the tetraisobutoxy sand courtyard, etc.; as the grafted oxydecane' may be exemplified by having a methyl group, an ethyl group, a propyl group, an isopropyl group, a methyl propyl group, a butyl group, Isobutyl, tert-butyl, hexyl, octyl, phenyl, toluene, thiol, phenylethyl, etc. trimethoxy decane, triethoxy sylvestre, tripropoxy decane, triisopropyl Oxy decane, tributoxy decane, di-28-200904930 isobutoxy decane, etc.; as the alkoxydecane of p = 2, dimethyl dimethoxy decane, dimethyl diethoxy group Decane, dimethyldipropoxydecane, dimethyldibutoxydecane, methylethyldimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, etc. In view of the ease of obtaining raw materials or the cost, the m in the above general formula (III) is 0, and n is 3 or less, that is, using trimethoxydecane having an organic functional group, triethyl Oxydecane and/or a partial hydrolyzate thereof, and R1 in the above general formula (IV) is a methyl group, and ρ is 1 and/or 0, that is, methyltrialkoxydecane, tetraalkoxy The decane and/or a partial hydrolyzate thereof and/or a condensate thereof are preferred. Further, the alkoxy group-containing decane compound having the q and r in the above general formula (IV) is 0 and/or The partial hydrolyzate and/or its condensate is more preferably an essential component. In particular, as the organofunctional group-containing alkoxydecane represented by the above general formula (III), at least one member selected from the group consisting of 3 -fluorenyl groups can be used. Propyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2- (3,4-ethoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-ethoxycyclohexyl)ethyltriethoxydecane; as the above-mentioned general formula (IV) The alkoxy decane compound is at least one selected from the group consisting of methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, methyltriisopropoxydecane, and methyltributyloxy. Decane, methyl triisobutoxy decane, tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetraisopropoxy decane, tetrabutoxy decane, tetraisobutoxy decane It is necessary to use decane compound having at least one of propoxy, isopropoxy, butoxy or isobutoxy as -29-200904930 Ingredients), especially good. These organofunctional alkoxydecanes and/or partial hydrolyzates thereof, and alkoxy-containing decane compounds and/or partial hydrolyzates thereof and/or condensates thereof may be used in various plural However, when two or more kinds of alkoxysilanes containing an organic functional group represented by the above general formula (III) and/or a partial hydrolyzate thereof are used, those having the same organic functional group are preferable, and further, for arbitrarily designed a ratio of a methoxy group, an ethoxy group, an alkoxy group having 3 or 4 carbon atoms in the organopolyoxane, as the alkoxy group-containing decane compound represented by the above general formula (IV) and/or The partial hydrolyzate and/or its condensate is preferably two or more different types of alkoxy groups. The organofunctional group-containing alkoxydecane represented by the above formula (III) and/or a partial hydrolyzate thereof, and the alkoxy group-containing decane compound represented by the above general formula (IV) and/or a part thereof The blending ratio of the hydrolyzate and/or its condensate is not particularly limited, but the blending ratio of the former is too small because the obtained organopolyoxane should have an organic functional group-based reaction when it is used. The property of the property cannot be sufficiently exerted, and it must be one having at least one organic functional group in one molecule. Therefore, the range of the Si atom of the two components is preferably 1:99 to 99:1, more preferably 10 : 90~80: 2 0 range. Further, the order of mixing or mixing of the various raw materials, and the method of performing partial co-hydrolysis and polycondensation are not particularly limited, and may be, for example, by the above-mentioned organic functional group-containing alkane, based on a conventionally known method. a mixture of oxydecane and/or a partial hydrolyzate thereof, an alkoxy group-containing decane compound and/or a partial hydrolyzate thereof and/or a condensate thereof, in a moisture--30-200904930 solution/condensation catalyst In the presence of water, partial co-hydrolysis and polycondensation are carried out after adding water, and in this case, an appropriate organic solvent may be used as necessary. As the catalyst for the hydrolysis and condensation reaction in this reaction, various prior art techniques have been known, and specific examples thereof include acetic acid, trifluoroacetic acid, butyric acid, oxalic acid, maleic acid, and citric acid. Organic acids such as methanesulfonic acid, P-toluenesulfonic acid, trifluoromethanesulfonic acid, inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, etc., sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, sodium acetate, Basic compounds such as potassium acetate, ammonia, ammonium hydroxide, trimethylamine, fluorine-containing compounds such as potassium fluoride and ammonium fluoride, tetraisopropyl titanate, tetrabutyl titanate, and An organometallic compound such as an octyl dilaurate or an aluminum chelating agent. The above catalyst may be used alone or in combination, but the amount of the catalyst used is 0 relative to the number of moles of Si atoms present in the total amount of the raw material. 0001~10% of the range of Mo, more preferably 0. 0 0 1~3% of the range of Mo. As described above, the degree of polymerization of the organopolyoxane may be from a dimer of two deuterium atoms to a polymer of several hundred atoms of a deuterium atom, but water used for partial hydrolysis or polycondensation The amount determines the average degree of polymerization, and the excess amount of water is added, so that the alkoxy group in this portion is hydrolyzed to become a resin body having a large branched structure, and the desired polyoxyalkylene alkoxy oligomer is not obtained, so the hydrolysis station The amount used must be determined strictly. For example, when the alkoxydecane raw materials used are all monomers having a fluorene atom, in order to prepare an organopolyoxane having an average degree of polymerization Z, it can be used with respect to the Z-alked alkoxy decane raw material (Z- 1) Moer water is partially hydrolyzed and polycondensed. In this case, an organic solvent such as an alcohol, an ether, an ester or a ketone may be used as necessary. Specific examples of such an organic solvent include methanol, ethanol, η-propanol, and the like. An alcohol such as propanol or propylene glycol monomethyl ether; an ether such as diethyl ether or dipropyl ether; an ester of methyl acetate, ethyl acetate or ethyl acetate; acetone, methyl ethyl Ketones such as ketones and methyl isobutyl ketones. Further, a polar solvent such as the above may be used together with a nonpolar solvent such as hexane, toluene or xylene, and particularly an alcohol such as methanol, ethanol or isopropanol. The amount of the organic solvent to be used may be in the range of 0 to 100 parts by mass based on 100 parts by mass of the total alkoxysilane of the starting material and/or its partial hydrolysis and/or condensate, but When the amount used is too small, there is a case where the reaction system at the start of hydrolysis is not uniform, and too much is because not only a better addition effect is not seen, and Ρ 01 yie 1 d is lowered and economically disadvantageous, so 10 0 The range of the mass parts of 〜500 is preferably more preferably in the range of 2 0 to 2 0 parts by mass. The actual operation in the partial (co)hydrolysis and polycondensation reactions is carried out by mixing a predetermined amount of water or a mixture of water/organic solvent in a mixed system of alkoxydecane starting materials, catalysts and organic solvents. The liquid or a mixed solution of a water/catalyst mixed solvent or a water/catalyst/organic solvent is preferably added dropwise to the mixed system of the alkoxydecane raw material and the organic solvent. In this case, a raw material having a methoxy or ethoxy alkoxydecane having a high hydrolysis reactivity and a carbon atom having a hydrolysis reactivity of a propoxy group or a butoxy group may have a carbon number of 3 and/or 4 The alkoxy alkoxydecane starting material is partially hydrolyzed in advance, and the two components are mixed, and then partially hydrolyzed, and then subjected to a condensation reaction. Each reaction can be carried out at a temperature range of 〇~15〇°c, but in general, the temperature is lower than room temperature, because the progress of the reaction is slower than -32-200904930, and when it is too high, it is also because of sulfhydryl groups. The thermal decomposition of an epoxy group or the like, or thermal polymerization of an acryloxy group has a bad influence on an organic functional group, so that a temperature range of from 20 to 130 ° C is preferred. After the reaction, the catalyst used is removed by neutralization, adsorption, filtration, or the like, or purified by distillation of the organic solvent and the by-produced alcohol or low-boiling substance, and the like. The organic polyoxane is such that most of the obtained organopolyoxyalkylene is a liquid. [Adhesive Composition] In the present invention, the acrylic resin described above is blended with the above-described crosslinking agent, the first organopolyoxane and the second organopolyoxane to form an adhesive composition. The crosslinking agent is usually used in an amount of 0 parts by mass based on 100 parts by mass of the acrylic resin constituting the pressure-sensitive adhesive composition.  1 to 10 parts by mass, preferably 0.  1 to 7 parts by mass, more preferably 0. A ratio of 2 to 3 parts by mass is blended. The amount of the crosslinking agent relative to 100 parts by mass of the acrylic resin is 0.  1 part by mass or more is preferable because the durability of the adhesive layer is increased. Further, the amount is 1 part by mass or less, because the so-called pan-pan of the optical film with an adhesive is used for a liquid crystal display device. Whitening is not obvious and is preferred. The first organopolysiloxane and the second organopolyoxane are usually used in an amount of 0 parts by mass based on 100 parts by mass of the acrylic resin constituting the adhesive composition. 0001 to 10 parts by mass ' is preferably 0. 01 to 5 parts by mass, more preferably 0. Use in a ratio of 1 to 1 part by mass. The amount of the organopolyoxane relative to 100 parts by mass of the acrylic resin is 0. 0001-33-200904930 or more, because there is a tendency to adhere the adhesive layer to the glass substrate, and in addition, this amount is 10 parts by mass or less because of overflow of the organic polyoxane from the adhesive layer. It is preferred and preferred. There is no particular limitation on the rate of the organic polyxide and the first organic polyoxo hospital. The mixing ratio can be controlled by mixing the two depending on the purpose of use. The range of 10/90 to 90/10 in terms of mass and the range of 20/80 to 80/20 in terms of mass ratio is more preferable. The polyoxyalkylene oxide and the second organic polyoxyalkylene can be pre-mixed with the olefinic acid resin and the crosslinking agent, or can be prepared by blending the acrylic acid agent 'premixed' or preparing the adhesive composition. In the case where the necessary components are simply mixed, there is no particular limitation on the mixing method or the temperature condition %. The adhesive composition described above may be further blended with a cross-linking stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, and the like, and simultaneously with the crosslinking agent in the adhesive. The catalyst can be used to prepare the adhesive layer in a short time. When the optical film of the obtained agent is applied to the liquid crystal glass, the floating or peeling between the adhesive optical films can be suppressed, or the adhesive layer can be reprocessed. Sex is also more excellent. As cross-linking catalyst, methylene diamine, ethylene diamine, polyethylenimine, hexamethylenetetramine triamine, triethylenetetramine, isophorone diamine, trimethyl diamine resin, melamine An amine compound such as a resin. When the adhesive-based compound is used as a crosslinking catalyst, the mixing ratio is improved by the improvement of the isocyanate-based compound property, but the former is preferably the same, and the first is re-blended with the propylene resin and blended. The binder, the inorganic binder, the inorganic binder, and the adhesive layer which are crosslinked to the foaming agent are suitable for the foaming enumeration, such as the hexamethylenediamine or the polyamine group, as the cross-linking agent-34-200904930 . The adhesive composition is usually prepared in a state in which the above-described respective components are dissolved in an organic solvent. Therefore, the organic solvent used may be any component which can dissolve the above-mentioned components, and for example, an aromatic hydrocarbon such as toluene or xylene may be used. For example, esters of ethyl acetate or butyl acetate, such as acetone or methyl ethyl ketone, ketones of methyl isobutyl ketone, and the like. [Optical film to which an adhesive is attached] The surface of at least one side of the optical film of the adhesive-attached optical film of the present invention is provided with an adhesive layer formed of the above-described adhesive composition. The optical film used herein refers to a film having optical properties, and examples thereof include a polarizing film and a retardation film. The polarizing film is an optical film having a function of emitting polarization with respect to incident light of natural light or the like. The polarizing film includes a linear polarizing film having a linear polarized light that absorbs a vibrating surface having a certain direction and a linear polarized light having a vibrating surface orthogonal thereto; and a linear polarized light that reflects a vibrating surface having a certain direction, and A polarized light separation film that penetrates a property of linearly polarized light having a vibration plane orthogonal thereto; a laminated polarizing film and a circularly polarizing film of a retardation film to be described later. As a specific example of a polarizing film, in particular, a linear polarizing film (also referred to as a polarizing film or a polarizing film), adsorption-aligned iodine or a dichroic dye on a polyvinyl alcohol-based resin film which is stretched by one axis is exemplified. The dichroic pigment. The retardation film, which is an optical film exhibiting optical anisotropy, can be exemplified by, for example, polyvinyl alcohol, polycarbonate, polyester, polyarylate-35-200904930, polythenimine, polysulfide, and ring. Polyglycol, polystyrene, polyfluorene, polyether oxime, polyvinylidene fluoride/polymethylmethylpropionate, liquid crystal polyester, acetyl cellulose, ethylene-vinyl acetate copolymer saponification a polymer film made of a substance, a polychloroethylene or the like, extending 1. An extended film obtained in an amount of 01 to 6 times or the like. Among them, a polymer film in which a carbonate film or a cyclic polyolefin film is extended by one axis or two axes is preferably referred to as a one-axis phase difference film, a wide viewing angle retardation film, and low photoelasticity. Any one of the rate retardation film and the like can be applied. In addition, a film which exhibits optical anisotropy by application or alignment of a liquid crystalline compound or a film which exhibits optical anisotropy by application of an inorganic layered compound can be used as a phase In the case of the retardation film, it is called a temperature-compensated retardation film, and the film of the twisted alignment of the rod-shaped liquid crystal which is sold under the trade name "LC film" by Nippon Oil Co., Ltd. In the same way, a thin film of a rod-shaped liquid crystal sold by Nippon Oil Co., Ltd. under the trade name "NH film" is tilted, and a disc-shaped liquid crystal sold by Fujifilm Co., Ltd. under the trade name "WV film" is tilted. The aligning film, the full two-axis alignment film sold by Sumitomo Chemical Co., Ltd. under the trade name "VAC film", and the two-axis alignment sold by Sumitomo Chemical Co., Ltd. under the trade name "new VAC film" Type of film, etc. Moreover, these optical film adhesive protective films can also be used as optical films. As the protective film, a transparent resin film is used, and examples of the transparent resin include an acetonitrile cellulose resin typified by triethylene fluorene cellulose or diethyl fluorene cellulose, and an amorphous resin represented by a norbornene resin. A ring-shaped poly-smoke resin, which is represented by polymethylmethyl acrylate, -36-200904930 methacrylic resin, polyester resin, polyolefin, polyether ether ketone resin, polyfluorene resin, and the like. In addition, an acetaminophen-based resin film such as a UV absorber acetam cellulose film such as a salicylate-based compound, a ditriazole-based compound, a tri-cyan compound or a cyanide-salt-based compound may be blended. Amorphous cyclic polyolefin. Amorphous cyclic polyolefin-based resin film "ARTON film", "ZEONOR", etc. (all trade names) sold by JSR (shares), and a poor film as a direct protective film. In the above-mentioned optical film, the polarizing film is formed directly, for example, a circular polarizing film which is adhered to the protective film on one side or both sides of the polyethylene film, which is a linear deviation of the lamination, but the linear polarizing film is also Most of them are in a state of adhering a protective film. In the case of the pressure-sensitive adhesive layer of the present invention, the optical layer of the adhesive layer of the present invention is usually provided in the phase layer, and the surface resin including at least one of the polarizers or the amorphous cyclic polyolefin resin is included. . The optical film to which the adhesive is applied is, for example, a benzophenone-based compound or a benzo acrylate-based compound which is coated with the above-described adhesive composition hydrocarbon resin or polycarbonate resin. As a protective film, a commercially available product in which a three-resin film or a norbornene-based resin film is suitably used is, for example, sold by OPTES, and the above-mentioned phase-line polarizing film may be used, and most of them are The state of the polarizer formed by the alcohol resin is used. In addition, on the one-side or two-sided round polarizing film of the polarizing film and the retardation film, a suitable example of forming an adhesive film on the side of the retardation film is attached, and a protective film made of acetonitrile is attached thereto. The polarizing thin can be formed by laminating an optical film on the adhesive layer obtained by forming an adhesive layer on the release film, and applying an adhesive composition on the optical film. The adhesive layer is produced by adhering a release film to the adhesive surface to protect it, and to form an optical film with an adhesive. In addition, as the release film, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate is used as a substrate. On the bonding surface of the substrate and the adhesive layer, a mold release treatment agent such as polyoxan treatment is applied. The adhesive layer can be produced by applying and drying the above-mentioned release film or optical film by using an adhesive composition which is an organic solvent solution as described above. The coating can be carried out by using various conventional coating machines. After coating, it is usually aged at a temperature of about 0 to 50 ° C and a relative humidity of about 20 to 80%, and is preferably aged for 3 to 14 days. The conditions are such that the temperature is 20 to 30 ° C, the relative humidity is 5 5 to 7 5 %, and the period is 5 to 7 days. By the aging, the crosslinking reaction of the adhesive is carried out, and when the adhesive layer is provided on the release film, the aging can be carried out in the state where the adhesive layer is formed on the release film, and the adhesion on the release film is laminated on the optical film. It can also be carried out after the agent layer. The thickness of the adhesive layer is not particularly limited, but it is usually preferably 30 Å or less, and preferably 10 Å or more. When the thickness of the adhesive layer is less than 30 // m, the adhesiveness under high temperature and high humidity is improved, and the possibility of floating or peeling between the glass substrate and the adhesive layer tends to be low, and there is a possibility of reprocessing. It is preferable that the thickness is 1 〇# m or more, and even if the size of the optical film to be bonded thereto changes, the dimensional change varies depending on the adhesive layer, so that the peripheral portion of the liquid crystal chamber is bright. The difference between the degree and the brightness of the center portion of -38-200904930 disappears, and whitening or color unevenness tends to be suppressed. The optical film with an adhesive of the present invention can be laminated on a glass substrate with an adhesive layer to form an optical laminate. In addition, examples of the glass substrate ′ include a glass substrate of a liquid crystal cell, a glass for antiglare, and a glass for sunglasses. Wherein, an optical film (upper polarizing film) with an adhesive is laminated on the glass substrate on the front side (viewing side) of the liquid crystal cell, and another optical film with an adhesive is laminated on the glass substrate on the back side of the liquid crystal cell (below An optical laminate formed of a polarizing film can be used as a liquid crystal display device. Examples of the material of the glass substrate include soda lime glass, low alkali glass, and alkali-free glass. The optical film with an adhesive is laminated on a glass substrate to form an optical laminate. For example, the release film can be peeled off from the optical film of the adhesive obtained as described above, and the exposed adhesive layer can be attached to the glass substrate. The surface is fine. After the optical film with an adhesive of the present invention is adhered to the glass substrate and becomes an optical laminate, the adhesive film is peeled off from the optical film when the optical film is peeled off from the glass substrate due to some poor conditions, and the adhesive film is adhered to the optical film. On the surface of the glass substrate that is in contact with the agent layer, almost no fogging or residue remains, so that it is easy to reattach the optical film with the adhesive to the peeled glass substrate. That is, the so-called reworkability is excellent. The liquid crystal display device formed by bonding the optical film with an adhesive of the present invention to at least one surface of a liquid crystal cell glass can be used, for example, for a notebook, a desktop, or a PDA (Personal Digital Assistance). Such as LCD monitors for personal computers, TVs, car monitors, electronic dictionaries -39- 200904930, digital cameras, digital cameras, electronic computers, 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, and the 'in the examples' indicates the amount and % of the amount and content used, and for no particular reason, Quality benchmark. In the following examples, the non-volatile portion of the acrylic resin is a crucible measured by a method according to JIS K 5 407, specifically, an adhesive solution is placed in a pan with an arbitrary mass. The ratio of the residual non-volatile mass 'after drying for 2 hours at 5 ° C is expressed relative to the mass of the initially measured solution. The weight average molecular weight of the acrylic resin is set in a GPC apparatus, and two sets of "TSK gel G Μ HHR - Η (S)" manufactured by Tosoh Corporation as a column are arranged in series, and tetrahydrofuran is used as a dissolving solution. The enthalpy measured by standard polystyrene conversion was measured at a sample concentration of 5 mg/ml, a sample introduction amount ΙΟΟμ1, a temperature of 4 〇 ° C, and a flow rate of 1 m 1 /min. Further, the analysis of the organopolyoxane obtained in each of the examples was carried out by the method shown below. (1) The average molecular weight and average degree of polymerization of the organopolysiloxane are determined by gel permeation chromatography (GPC), and the weight average molecular weight is calculated based on a calibration curve prepared from a polystyrene standard sample. Then, the average degree of polymerization is calculated from this. -40- 200904930 (2) Alkoxy group content in organic polyoxane by alkali cracking gas chromatography (GC) analysis [Ref. Polyoxane Handbook ' 7 9 2 - 7 9 3 ( 1 In 1990, issued by Nikkan Kogyo Shimbun Co., Ltd.), measuring the alkoxy group content, determining the coefficients c, d and the coefficients in the above average composition formula (I), and the coefficients h, i in the above average composition formula (Π) j. (3) The structural analysis of the organopolyoxane is carried out by performing 矽 nuclear magnetic resonance spectroscopy (29Si-NMR) analysis and proton nuclear magnetic resonance spectroscopy (CH-NMR) analysis, and the coefficient a in the average composition formula (1) is determined by the measurement result. , b and e, and the coefficients f, g and k in the above average composition formula (II). (4) The thiol equivalent of organic polyoxane is based on the addition of acetic acid/potassium iodide/potassium iodate-sodium thiosulfate solution [Ref. Analytical Chemistry Notes, Rev. 2, pp. 432-433 (June's shares, 1976) Ltd. issued)] and measured. (5) Viscosity of organopolyoxane The viscosity at 25 ° C was measured according to the method of JIS K 8 8 0 3 . First, an example of producing an acrylic resin used in the present invention is listed. [Polymerization Example 1] A reactor equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer was charged with ethyl acetate 81. 8 parts, acrylic acid butyl vinegar 98. 9 parts and acrylic acid 1. 1 -41 - 200904930 parts of the mixed solution, while replacing the air in the apparatus with nitrogen, the internal temperature was raised to 55 °C without oxygen. Then, azobisisobutyronitrile (polymerization initiator) will be dissolved in 10 parts of ethyl acetate. 1 4 parts of the solution was added in total, and after adding the initiator for 1 hour, ethyl acetate was continuously added to the reactor at an addition rate of 1 7 · 3 parts / hr to make the concentration of the acrylic resin other than the monomer. It is 35%, and is kept at an internal temperature of 5 4 to 5 6 ° C for 12 hours. Finally, ethyl acetate is added to adjust the concentration of the acrylic resin to 20%, and the obtained acrylic acid A is obtained by GPC. The polystyrene-equivalent weight average molecular weight Mw was 1,670,000, and Mw/Mn was 4. 4. Next, an example of synthesizing the organopolyoxane used in the present invention will be listed. [Organic Polyoxane Synthesis Example 1] (First Organic Polyoxane) In a flask equipped with a stirrer, a cooling capacitor, a thermometer, and a dropping funnel, a volume of 1 L was charged with 3-mercaptopropyltrimethoxy Base sand court 39. 3g (〇_2 mol), methyl trimethoxy sand court 40. 9g (0·3 mole), tetraethoxy Shi Xiyuan 104. 2g (0_5 mol), methanol 80. 2g and ethanol i〇4. 2 g, while stirring the inside of the flask at an internal temperature of 20 to 30 C, while dropping into the o. for 30 minutes. In hydrochloric acid aqueous solution 16. 2g (water: 0_9 moles) hydrogen chloride: 1. 62χ1 (Γ3mol) and ethanol 16. 2g of the mixed solution, after further heating, but also flow down for 2 hours of ripening 〇 Next, adding potassium fluoride in 1% ethanol solution 9. 4g (KF: 1. 62xl〇-3 Moer) was subjected to partial cohydrolysis and polycondensation after 2 hours of aging. Then, 'the internal temperature was raised to 8 〇t under normal pressure', the alcohol component was distilled off, and the internal temperature was raised to 100 ° C and then distilled under a reduced pressure of -42 to 200904930 of 30 Torr (about 4 kPa). After removing the residual alcohol component and the low boiling component, the mixture was filtered to obtain a colorless transparent liquid organopolyoxane C (yield: 117. 0g' yield: 90%). The organopolyfluorene oxime C' is in the above average composition formula (I), Y is 3-mercaptopropyl group, R1 is a methyl group, and the molar ratio of each raw material (other than the organic solvent) used, the above The weight average molecular weight, the average degree of polymerization calculated by the analysis results, the average composition formula corresponding to the above formula (I), the fluorenyl equivalent, and the viscosity ' are as follows. Raw material molar ratio, average composition and physical properties of "organic polyoxyalkylene c": molar ratio: HS(CH2)3Si(〇CH3)3/CH3Si(〇CH3)3/Si(OC2H5)4 = 0_2 /0. 3/0. 5 Catalyst: HC1/KF/water=0. 00 1 62/0. 00 1 62/0. 9 Weight average molecular weight: 1,380 Average polymerization degree: 10. 6 Average composition: [HS(CH2)3]0. 2(CH3)03Si(〇CH3)061(〇C2H5)108〇0905 锍 base equivalent: measured 値63 8g/mole, theoretical 値65 1 g/mole Viscosity: 20. 5mm2/s [Organic Polyoxane Synthesis Example 2] (Second Organic Polyoxane) In a flask equipped with a stirring device, a cooling capacitor, a thermometer, and a dropping funnel in a volume of 1 L, tetrapropoxydecane was charged. 1 32 2g (〇5 moles) and isopropanol 1 32. 2g ' while heating and heating in an oil bath, the internal temperature -43 - 200904930 is raised to 50. (: until the inside of the flask was stirred), a 1N aqueous hydrochloric acid solution was added dropwise over 10 minutes. 2g (water: 0. 4 mole 'hydrogen chloride: 7_2xl0_3 moles) and isopropyl alcohol 7 · 2 g mixed solution 'more than 2 hours after the temperature rise, the preliminary hydrolysis reaction solution D1 ° is obtained. 3_mercaptopropyltriethoxydecane 47. 7g (0_2 mole), methyltriethoxydecane 17_8g (0. 1 mole), methyl triisopropoxy decane 44. 1g (0. 2 mol), ethanol 65. 5g and isopropanol 44. In a mixed solution of 1 g, an aqueous solution of 1 N hydrochloric acid was added dropwise at an internal temperature of 20 to 30 ° C for 10 minutes. 2g (water: 0. 4 moles, hydrogen chloride: 7. 2X10·3 mol) and isopropanol 7. 2 g of the mixed solution is further aged at an internal temperature of 2 〇 to 3 0 ° C for 30 minutes, and then a preliminary hydrolysis reaction liquid D2 is obtained. After the preliminary hydrolysis reaction liquid D2 is added to the above preliminary hydrolysis reaction liquid D 1 , the mixture is stirred and mixed. After that, 1N hydrochloric acid aqueous solution was added at an internal temperature of 20 to 30 ° C. 8§ (water: 〇_1 mol, hydrogen chloride: 1. 8/1〇-3 mol) and isopropanol 1 .  The mixed solution of 8 g was incubated in an oil bath for 2 hours while still flowing. Next, add potassium fluoride. 94§(〖?:1. 62\10_2 mol), after further aging for 2 hours, partial co-hydrolysis and polycondensation reactions were carried out. Next, while the internal temperature is raised to 80 ° C under normal pressure, the alcohol component is distilled off to a temperature of more than 30 Torr (about 4 kPa), and the internal temperature is raised to 1 Torr, and then the residual alcohol is distilled off. The component and the low-boiling component were filtered to obtain a colorless transparent liquid organopolyoxane D (yield: 140_8 g, yield: 90%). The organopolyoxane D, in the above average composition formula (II), Y is -44 - 200904930 3-mercaptopropyl, R1 is methyl, R2 is propyl and isopropyl, and each is used. The molar ratio of the raw material (other than the organic solvent), the weight average molecular weight calculated by the above analysis results, the average degree of polymerization, the average composition formula corresponding to the above formula (II), the fluorenyl equivalent, and the viscosity are as follows. Raw material molar ratio, average composition and physical properties of "organic polyoxane D": Mo (r2) 〇C3H7)4=0. 2/0. 1/0. 2/0. 5 Catalyst: HC1/KF/water=〇_〇162/0_0162/0. 9 Weight average molecular weight: 1,620 Average polymerization degree: 1 0. 3 Average composition: [HS(CH2)3]0. 2(CH3)0,3Si(OC2H5)0. 39(〇C3H7)l. 3 1〇0. 9 S waste base equivalent: measured 値803 g/mole, theoretical 値785g/mole Viscosity: 33. 6 mm 2 / s Next, using the acrylic resin and the organic polydecane which were produced as described above, the adhesive was prepared and the examples and comparative examples suitable for the optical film were shown. The following were used as the crosslinking agent. "CORONATE L": Ethyl acetate solution of trimethyl methacrylate adduct of toluene diisocyanate (solid content concentration: 7 5 %), trade name of Japan Polyurethane Industrial Co., Ltd. "TAZM": a trimethylol propyl tri-oxopropyl propionate (liquid), a trade name of a mutual pharmaceutical product, and a decane compound as a comparative example. -45- 200904930 " ΚΒΜ- 803 " : 3-mercaptopropyltrimethoxydecane (liquid), trade name "KBM-303" manufactured by Shin-Etsu Chemical Co., Ltd.: 2-(3,4-epoxycyclohexyl Ethyltrimethoxydecane (liquid), trade name of Shin-Etsu Chemical Co., Ltd. [Comprehensive Examples 1 to 3 and Comparative Examples 1 to 4] (a) Production of Adhesive Acryl Resin A obtained in Polymerization Example 1 Ethyl acetate solution, where CORONATE L" and "TAZM" were blended as crosslinking agents in the amounts indicated in Table 1, and the polyorganopolyoxane shown in Table 1 was blended according to the amounts shown in Table 1. An alkane (or a decane compound) to prepare an adhesive composition. However, in Table 1, the blending amount (parts) of the crosslinking agent "CORONATE L" is the amount of the solid component. [Table 1] Example Adhesive Composition Acrylic Resin (Quantity) Crosslinking agent (amount) First organopolyoxane second organic polyoxane CORONATE L 种类 kind and kind of amount Example 1 1 part 2_〇0. 02 copies C 〇_1 backup D 0. 05 parts Example 2 1 part 2 parts 0 parts 0. 02 copies C 〇 _ 20 copies D 0. 10 parts Comparative example 1 100 parts 2. 0 copies 0. 02 copies C 0. 15 copies _ _ Comparative example 2 100 parts 2. 0 copies 0. 02 copies _ _ D 〇. 1〇 Parts Comparative Example 3 100 parts 2_0 parts 0. 02 copies ΚΒΜ-803 0. 15 parts a _ comparison example 4 1 part 2 〇 part 0. 02 parts 303-303 0_15 parts • _ (b) Preparation of optical film with adhesive-46 - 200904930 The above-mentioned adhesive compositions were applied to the release-treated poly(terephthalic acid) using a coater. The thickness of the ethylene glycol ester film ("PET 381 1", the trade name of Lintec (called a separator), which is called a separator), and the thickness after drying is 15 μm, so that it is 90 °C. After drying for 1 minute, a sheet-like adhesive was obtained. Next, the both sides of the polarized film of the three-layer structure in which the protective film formed of the triacetyl cellulose is adhered to the both sides of the polarized film of the three-layered structure in which the iodine is adsorbed are bonded to each other by lamination. The surface of the obtained sheet-like adhesive on the opposite side to the separator (adhesive surface) was aged for 7 days under the conditions of a temperature of 23 and a relative humidity of 65% to obtain a polarizing film with an adhesive. Further, these polarizing films with an adhesive were sealed with a packaging line with an aluminum foil, and further aged at 6 CTC for 6 days to promote the change with time due to heat. (c) Preparation of optical laminate (glass paste for polarizing film) The polarizing film of the adhesive prepared in (b) above (cooked at 23 ° C X 6 5% RHx for 7 days, and subsequently passed 60 °) (C x 6 days matured), each of which is adhered to the side of the adhesive layer, and the two sides of the liquid crystal cell glass substrate ("1 73 7", trade name of CORING Co., Ltd.) are directly polarized (cross-nicol) to form an optical layer. Compound. (d) Evaluation of heat resistance and heat and humidity resistance of the optical laminate. With respect to the above-mentioned optical laminate, a heat resistance test was carried out for 30 hours under a drying condition at a temperature of 80 ° C, and further, The damp heat test was carried out for 300 hours at a temperature of 60 ° C and a relative humidity of 90%, and the optical laminates after the respective tests were observed by the method of -47-200904930, and evaluated in the following four stages, and the results are collectively shown in Table 2. (Evaluation criteria for heat resistance and heat and humidity resistance) ◎: There is no change in appearance such as lifting, peeling, foaming, etc. 〇: The appearance change such as floating, peeling, foaming, etc. is hardly observed. The appearance change of the peeling, foaming, etc. is slightly obvious. X: The appearance of the float, peeling, foaming, etc. changes significantly. (e) Reworkability evaluation of the optical film with an adhesive The evaluation of the reworkability is performed as follows. First, the polarizing film with adhesive prepared in (b) (manufactured by 23 ° C X 6 5 % RH X for 7 days, and subsequently matured at 60 ° C for 6 days) is cut into 25 mm x 150 mm. a test piece, and then the test piece was made with its adhesive layer side Adhesive device ("LAMIPACKER", trade name manufactured by FIJIPLA) was attached to a glass substrate for a liquid crystal cell at 50 ° C, 5 kgf / cm 2 (490. 3 kPa) The autoclave treatment was carried out for 20 minutes, and then a sample stored in a gas atmosphere at a temperature of 23 ° C and a relative humidity of 5 〇% for 24 hours was prepared, and a sample of the sample stored in a 5 (TC oven for 48 hours) was prepared. In the gas atmosphere at a temperature of 2 3 ° C and a relative humidity of 50%, the adhesive test piece was peeled off at a speed of 300 mm/min in the direction of 180°, and the state of the surface of each glass substrate was observed, according to the following criteria. The results are shown in Table 2. <Reworkability Evaluation Criteria> -48 - 200904930 ◎: There is no fog at the surface of the glass plate, etc. 〇: There is almost no fog on the surface of the glass plate. △: Surface of the glass plate Confirm that there is fog, etc. X. Adhesive residue was confirmed on the surface of the glass plate. [Table 2]

例 通常熟成品 ’ 通常熟成後,60°c x6天熟成 耐熱性 耐濕 熱性 再加 工性 耐熱性 耐濕 熱性 再加 工性 23°C X 24小時 50°C X 48小時 23 °C X 24小時 50°C X 48小時 實施例1 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ 實施例2 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 比較例1 〇 ◎ ◎ ◎ ◎ ◎ ◎ Δ 比較例2 △ X 〇 ◎ ◎ ◎ ◎ ◎ 比較例3 Δ X 〇 X X X 〇 X 比較例4 X ◎ Δ X X Δ ◎ X 由表1及表2可得知，丙烯酸樹脂及交聯劑中，摻合本 發明規定的有機聚矽氧烷之實施例i及2，耐熱性、耐濕熱 性及再加工性的任一項皆顯示出優良的性質，此外，將此 等附黏著劑之光學薄膜，以60。(：進行6天熟成後，在耐熱 性、耐濕熱性及再加工性，亦得到約令人滿意的結果。 相對於此’摻合僅摻合第一有機聚矽氧烷之比較例1 、僅摻合第二有機聚矽氧烷之比較例2、以及摻合單體型 的矽烷化合物之比較例3及4，於耐熱性、耐濕熱性及再加 工性的任一項，皆爲不足的結果。 -49-For example, the cooked product is usually cooked at 60°c x 6 days. Heat resistance, heat and humidity resistance, reworkability, heat resistance, heat and humidity resistance, reworkability, 23°CX, 24 hours, 50°CX, 48 hours, 23°CX, 24 hours, 50°CX 48. ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Comparative Example 2 △ X 〇 ◎ ◎ ◎ ◎ ◎ Comparative Example 3 Δ X 〇XXX 〇X Comparative Example 4 X ◎ Δ XX Δ ◎ X It can be seen from Tables 1 and 2 that Examples 1 and 2 of the acrylic resin and the crosslinking agent are blended with the organopolyoxane specified in the present invention, Any of heat resistance, moist heat resistance, and reworkability exhibits excellent properties, and in addition, the optical film of these adhesives is 60. (: After 6 days of aging, about satisfactory results were obtained in heat resistance, heat and humidity resistance, and reworkability. In contrast to Comparative Example 1 in which only the first organopolyoxane was blended, Comparative Examples 2 and 2 in which only the second organopolyoxyalkylene was blended, and Comparative Examples 3 and 4 in which the monomeric decane compound was blended were insufficient in any of heat resistance, moist heat resistance, and reworkability. The result. -49-

Claims (1)

200904930 十、申請專利範圍 1 . 一種黏著劑組成物，其特徵係含有 (A) 丙烯酸樹脂、 (B) 交聯劑、 (C) 下述平均組成式（I)所表示的第一有機聚矽氧烷、 YaR'SUOCHOaOC^HsWOHhOM —a-b_c.d-e)/2 …⑴ (式中’ Y表示具有至少1種選自锍基、環氧基、（甲基 )丙烯醯氧基、烯基、鹵化烷基及胺基之有機基；R1表承 至少1種之不具有脂肪族不飽和鍵的碳原子數1〜8的非取代 的一價烴基；a、b、c、d 及 e 符合 o.oigaSl、0^b&lt;2 、0ScS2、0Sd$2、〇Se$i，且 〇」Sc + dS2.5 及 2S a + b + c + d + e$ 3 之數） (D) 下述平均組成式（II)所表示的第二有機聚矽氧烷、 YfR1gSi(OCH3)h(〇C2H5)1(〇R2)J(OH)kO(4.f-g.h-1.J-k)/2 …（II) (式中，Y及R1表示與上述相同的意義；R2爲碳原子 數3及/或4的院基或甲氧基丙基；f、g、h、i、j及k係符 合 O.OlgfSl、〇Sg&lt;2、Ogh各 2、0SiS2、0&lt;jg2、0 SkSl，而h與i不同時爲0，且〇_l$h + i+ jg2.5及 f+g + h + i+j+k S 3 之數）。 2 ·如申請專利範圍第1項之黏著劑組成物，其中丙稀 -50- 200904930 酸樹脂（A)係包含以（甲基）丙烯酸烷基酯所衍生的結構單元 爲主成分’含有具有極性官能基之（甲基）丙烯酸系化合物 所衍生的結構單元之丙烯酸樹脂。 3 ·如申請專利範圍第2項之黏著劑組成物，其中極性 官能基爲選自游離羧基、羥基、胺基及環氧環。 4.如申請專利範圍第1〜3項中任一項之黏著劑組成物 ，其中交聯劑（B)含有異氰酸酯系化合物。 5 ·如申請專利範圍第1〜4項中任一項之黏著劑組成物 ，其中表示第一有機聚矽氧烷（C)之上述平均組成式（I)及 表示第二有機聚矽氧烷（D)之上述平均組成式（II)中，γ爲 具有锍基或環氧基之有機基。 6.如申請專利範圍第1〜5項中任一項之黏著劑組成物 ，其中表示第一有機聚矽氧烷（C)之上述平均組成式（I)及 表示第二有機聚矽氧烷（D)之上述平均組成式（II)中，b及 g爲正數，R1爲甲基，R2爲丙基或異丙基。 7 ·如申請專利範圍第1〜6項中任一項之黏著劑組成物 ，其中表示第一有機聚矽氧烷（C)之上述平均組成式（I)中 ，〇及d皆爲正數，表示第二有機聚矽氧烷（D)之上述平均 組成式（Π)中，h及i皆爲正數。 8 .如申請專利範圍第1〜7項中任一項之黏著劑組成物 ，其中第一有機聚矽氧烷（C)及第二有機聚矽氧烷（D)，各 自的平均聚合度爲3〜100。 9 · 一種附黏著劑之光學薄膜，其特徵係於光學薄膜的 至少一側的面上，設置由申請專利範圍第1〜8項中任一項 -51 - 200904930 所記載的黏著劑組成物所形成的黏著劑層。 1 0.如申請專利範圍第9項之附黏著劑之光學薄膜’其 中光學薄膜選自偏光薄膜及相位差薄膜。 1 1 ·如申請專利範圍第丨〇項之附黏著劑之光學薄膜， 其中光學薄膜包含偏光子的至少一側的面上黏貼由乙醯纖 維素系樹脂或非晶性環狀聚烯烴系樹脂所成的保護膜之偏 光薄膜。 -52- 200904930 明 說 單 無簡 為符 圖件 表元 代之 定圖 :指表 圖案代 表本本 無 代 \ 定一二 t日 Vw/ 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無200904930 X. Patent application scope 1. An adhesive composition comprising (A) an acrylic resin, (B) a crosslinking agent, (C) a first organic polyfluorene represented by the following average composition formula (I) Oxane, YaR'SUOCHOaOC^HsWOHhOM —a-b_c.de)/2 (1) (wherein Y represents at least one selected from the group consisting of an anthracenyl group, an epoxy group, a (meth)acryloxy group, an alkenyl group, An alkyl group having an alkyl group and an amine group; R1 represents at least one unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have an aliphatic unsaturated bond; a, b, c, d and e correspond to o .oigaSl, 0^b&lt;2, 0ScS2, 0Sd$2, 〇Se$i, and 〇"Sc + dS2.5 and 2S a + b + c + d + e$ 3) (D) Average composition as follows A second organopolyoxane represented by the formula (II), YfR1gSi(OCH3)h(〇C2H5)1(〇R2)J(OH)kO(4.fg.h-1.Jk)/2 (II (wherein, Y and R1 represent the same meanings as above; R2 is a hospital or methoxypropyl group having 3 and/or 4 carbon atoms; and f, g, h, i, j and k are in accordance with O. OlgfSl, 〇Sg&lt;2, Ogh 2, 0SiS2, 00&2; 0g2, 0 SkSl, and h and i are not 0, and 〇_l$h + i+ Jg2.5 and f+g + h + i+j+k S 3). 2) The adhesive composition of claim 1 wherein propylene-50-200904930 acid resin (A) comprises a structural unit derived from an alkyl (meth) acrylate as a main component 'containing polarities An acrylic resin of a structural unit derived from a functional (meth)acrylic compound. 3. The adhesive composition of claim 2, wherein the polar functional group is selected from the group consisting of a free carboxyl group, a hydroxyl group, an amine group, and an epoxy ring. 4. The adhesive composition according to any one of claims 1 to 3, wherein the crosslinking agent (B) contains an isocyanate compound. The adhesive composition according to any one of claims 1 to 4, wherein the above average composition formula (I) of the first organopolyoxane (C) and the second organopolyoxane are represented. In the above average composition formula (II) of (D), γ is an organic group having a mercapto group or an epoxy group. 6. The adhesive composition according to any one of claims 1 to 5, wherein the above average composition formula (I) of the first organopolyoxane (C) and the second organopolyoxane are represented. In the above average composition formula (II) of (D), b and g are positive numbers, R1 is a methyl group, and R2 is a propyl group or an isopropyl group. The adhesive composition according to any one of claims 1 to 6, wherein in the above average composition formula (I) of the first organopolyoxane (C), both 〇 and d are positive numbers, In the above average composition formula (Π) representing the second organopolyoxane (D), both h and i are positive numbers. 8. The adhesive composition according to any one of claims 1 to 7, wherein the first organopolyoxyalkylene (C) and the second organopolyoxane (D) each have an average degree of polymerization of 3 to 100. An optical film with an adhesive attached to at least one side of the optical film, and an adhesive composition according to any one of the first to eighth aspects of the invention, which is described in the above-mentioned. The layer of adhesive formed. An optical film with an adhesive as disclosed in claim 9 wherein the optical film is selected from the group consisting of a polarizing film and a retardation film. The optical film with an adhesive according to the invention of claim 3, wherein the optical film comprises at least one side of the polarizer bonded with an acetonitrile cellulose resin or an amorphous cyclic polyolefin resin. A polarizing film of the resulting protective film. -52- 200904930 The statement is not a simple figure. It means that the table pattern represents the book without a generation. It is fixed for one or two days. Vw/ VIII. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: none
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