201229167 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種黏著劑組成物，其係在將光學薄膜 黏貼在液晶單元等被著物時使用，言玄光學薄膜為偏光膜、 相位差膜等。更詳細而言，本發明係有關一種黏著劑組成 物，其即使在高溫高濕下亦顯示優異的耐久性，並且抑制 白斑產生之能力優異。 【先前技術】 液晶顯示裝置’通常係由液晶單元及光學薄膜所構 成，該液晶單元係將定向於預定方向之液晶成分夾持在玻 璃等2片支持基板之間而成，該光學薄膜為偏光膜或相位 差膜、亮度提高薄膜等。在將此等光學薄膜彼此積層、和 將光學薄膜黏貼在液晶單元時，經常使用黏著劑。 液晶顯示裝置，係作為個人電腦和電視、汽車導航等 顯示裝置而被廣泛使用。此等亦有時會在像高溫高濕下般 的嚴苛環境中使用。因此，要求開發一種黏著劑，其耐久 性優異，而即使長時間使用，亦不會發生剝離和氣泡產生 等此外例如.在像尚溫高濕下般的嚴苛環境中，光學 薄膜的收縮和膨脹的尺寸變化會變嚴重。習知的黏著劑層 無法減輕因這樣的尺寸變化而產生之應力，光學薄膜的殘 留應力會變得不均勾。結果，光從液晶顯示裝置的周邊部 漏出而變白之所謂「白斑」會成為問題。 3 201229167 為了改善樣的問題，而提案有一種黏著劑，其係在 黏著劑組成物中添加低分子量聚合物，而使其具有應力減 輕性。例如··專利文獻1(曰本特開平10-279907號公報）中 揭示一種偏光膜用黏著劑組成物，其係由高分子量丙烯酸 系共聚物、重量平均分子量$ 3萬以下之低分子量丙烯酸 系共聚物、以及多官能性化合物所構成。然而，專利文獻 1中所記載之黏著劑組成物，由於重量平均分子量為3萬 以下之低分子量丙烯酸系共聚物之添加量較多，故難以防 止在高溫高濕下起泡和剝離。 抑制白斑之方法有下述方法：如專利文獻丨中所記载 之黏著劑組成物，經由追隨偏光膜的尺寸變化，使應力集 中減輕，來防止白斑產生之方法；以及與此方法相反，使 用具有咼凝聚力之黏著劑組成物，將應力產生之區域抑制 在最小限度’而防止白斑產生之方法。 專利文獻2(曰本特開2〇〇7_1 12839號公報）中揭示—種 黏著劑組成物，其係為了改善黏著劑層之黏著性，而相對 於丙稀酸系共聚物100重量份，包含下述成分而成：過氧 化物0.02〜2重量份；異氰酸酯系交聯劑0 02〜2重量份； 以及軟化點為80。(：以上之黏著賦予樹脂1〜4〇重量份。然 而’專利文獻2中並無關於白斑之記載，且若僅具有上述 構成’則抑制白斑產生之能力會不充分。 [先前技術文獻] (專利文獻） 專利文獻1 :曰本特開平1〇_2799〇7號公報 201229167 專利文獻2 :日本特開2007-112839號公報 【發明内容】 [發明所欲解決之問題] 因此’本發明之目的在於提供一種黏著劑組成物，其 抑制白斑之能力及耐久性優異。 [解決問題之技術手段] 本發明為了達成上述目的，提供一種具備下述構成之 黏著劑組成物。 (1) 一種黏著劑組成物，其包含下述成分：包含羧基 之（曱基）丙烯酸系共聚物（A);包含羧基和羥基之（曱基）丙 烯酸系共聚物（B)，曱苯二異氰酸g旨（t〇iyiene diisocyanate) 系化合物（C) ’其係相對於前述（甲基）丙烯酸系共聚物（A) 和（B)之合計1〇〇重量份，為5〜20重量份；以及含環氧基 之矽烷耦合劑（D)。 (2) 如上述（1)所述之黏著劑組成物，其中，前述含環 氧基之石夕烧耦合劑（D) ’係在分子内至少具有曱氧基或乙氧 基之任一者。 (3) 如上述（1)或（2)所述之黏著劑組成物，其中，前述 含環氧基之石夕烧柄合劑（D)為募聚物。 (4) 如上述（1)至（3)中任一項所述之黏著劑組成物，其 中，復包含胺基改質矽氧（E)。 (5) 如上述（4)所述之黏著劑組成物，其中，相對於前 201229167 述（甲基）丙烯酸系共聚物（A)和（B)之合計loo重量份，包含 胺基改質矽氧（E)0.05〜1重量份。 (6) 如上述（1)至（5)中任一項所述之黏著劑組成物，其 中’復包含具有羥基和松香骨架之化合物（F)。 (7) 如上述（6)所述之黏著劑組成物，其中，前述具有 座基和松香骨架之化合物（F)，是在分子内具有下述式⑴ 所示之骨架之化合物：201229167 VI. Description of the Invention: [Technical Field] The present invention relates to an adhesive composition which is used when an optical film is adhered to a liquid crystal cell or the like, and the optical film is a polarizing film and has a phase difference. Membrane and the like. More specifically, the present invention relates to an adhesive composition which exhibits excellent durability even under high temperature and high humidity and which is excellent in suppressing generation of white spots. [Prior Art] A liquid crystal display device is generally composed of a liquid crystal cell in which a liquid crystal component oriented in a predetermined direction is sandwiched between two supporting substrates such as glass, and an optical film which is polarized. Film or retardation film, brightness enhancement film, and the like. When these optical films are laminated to each other and the optical film is adhered to the liquid crystal cell, an adhesive is often used. The liquid crystal display device is widely used as a display device such as a personal computer, a television, or a car navigation. These are also sometimes used in harsh environments like high temperatures and high humidity. Therefore, it is required to develop an adhesive which is excellent in durability, and even if it is used for a long period of time, peeling and bubble generation do not occur, etc. Further, for example, in a severe environment like high temperature and humidity, the shrinkage of the optical film and Dimensional changes in expansion can become severe. Conventional adhesive layers do not alleviate the stress caused by such dimensional changes, and the residual stress of the optical film becomes uneven. As a result, the so-called "white spot" in which light leaks from the peripheral portion of the liquid crystal display device and becomes white becomes a problem. 3 201229167 In order to improve the problem of the sample, there is proposed an adhesive which adds a low molecular weight polymer to the adhesive composition to impart stress reduction. An adhesive composition for a polarizing film comprising a high molecular weight acrylic copolymer and a low molecular weight acrylic having a weight average molecular weight of 30,000 or less is disclosed in Japanese Laid-Open Patent Publication No. Hei 10-279907. It is composed of a copolymer and a polyfunctional compound. However, in the adhesive composition described in Patent Document 1, since the amount of the low molecular weight acrylic copolymer having a weight average molecular weight of 30,000 or less is large, it is difficult to prevent foaming and peeling under high temperature and high humidity. The method for suppressing leukoplakia is a method of preventing leukoplakia by reducing the stress concentration by following the dimensional change of the polarizing film as in the adhesive composition described in the patent document; and in contrast to this method, An adhesive composition having a cohesive force, which suppresses the area where stress is generated to a minimum, and prevents the generation of white spots. An adhesive composition is disclosed in the patent document 2 (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. Hei. The following components are obtained: 0.02 to 2 parts by weight of a peroxide; 0 02 to 2 parts by weight of an isocyanate crosslinking agent; and a softening point of 80. (The above-mentioned adhesion imparting resin is 1 to 4 parts by weight. However, Patent Document 2 does not describe the white spot, and if it has only the above configuration, the ability to suppress the generation of white spots is insufficient. [Prior Art Document] ( [Patent Document 1] Patent Document 1: Japanese Patent Application Laid-Open No. Hei. No. Hei. No. 2007-112839 [Patent Document 2] [Problems to be Solved by the Invention] Therefore, the object of the present invention is In order to achieve the above object, the present invention provides an adhesive composition which is excellent in the ability to suppress white spots and has excellent durability. [Technical means for solving the problem] In order to achieve the above object, the present invention provides an adhesive composition having the following constitution: (1) An adhesive a composition comprising the following components: a (carboxyl)acrylic copolymer (A) comprising a carboxyl group; a (fluorenyl)acrylic copolymer (B) comprising a carboxyl group and a hydroxyl group; T〇iyiene diisocyanate) is a compound (C) which is 5 to 20 parts by weight based on 1 part by weight of the total of the (meth)acrylic copolymers (A) and (B); Base (2) The adhesive composition according to the above (1), wherein the epoxy group-containing ceramide coupling agent (D)' has at least a decyloxy group in the molecule. (3) The adhesive composition according to the above (1) or (2), wherein the epoxy group-containing stone stalk mixture (D) is a polymer. (4) The adhesive composition according to any one of (1) to (3) above which further comprises an amine-based modified oxime (E). (5) Adhesive as described in the above (4) The composition of the present invention contains 0.05 to 1 part by weight of the amine-modified oxime (E) based on the total loo parts by weight of the (meth)acrylic copolymers (A) and (B) of the above 201229167. The adhesive composition according to any one of the above (1), wherein the compound (F) having a hydroxyl group and a rosin skeleton is further contained. (7) The adhesive according to the above (6) In the composition, the compound (F) having a base group and a rosin skeleton is a compound having a skeleton represented by the following formula (1) in a molecule:
(8) 如上述（6)或（7)所述之黏著劑組成物，其中，相對 於前述丙烯酸系共聚物（A)和（B)之合計1〇〇重量份，包含 前述具有羥基和松香骨架之化合物（F)1〜2〇重量份。 (9) 如上述（1)至（8)中任一項所述之黏著劑組成物，其 中’相對於前述（甲基）丙烯酸系共聚物（A)和（B)之合計1〇〇 重量伤，包含刚述含環氧基之石夕烧耦合劑（D)〇 〜1重量 份。 [功效] 本發明之黏著劑組成物，即使在高溫高濕之環境中耐 久性亦優異，並且抑制白斑之能力優異。此外，使用本發 明之黏著劑組成物而得之光學㈣，由於抑制白斑之能力 優異’且即使在高溫、高濕之狀況下亦不會剝離和產生氣 泡，故能夠較佳地用於個人電腦、電視、汽車導航等顯示 201229167 裝置。 並且’本發明之黏著劑組成物’其黏著力之經時變化 少，而二次加工性優異。此處’所謂二次加工性，係指進 行下述作業之容易度：當在使用黏著劑將光學薄膜點貼在 被著物時發生異物嵌入等不良情形時，將光學薄膜從被著 物剝離去除，並重貼新的光學薄膜。 【實施方式】 [實施發明的較佳形態] 本發明人致力進行研究後，結果發現一種黏著劑組成 物，其耐久性及抑制白斑之能力優異，該黏著劑組成物， 包含下述成分：包含羧基之（曱基）丙烯酸系共聚物（A);包 含羧基和羥基之（甲基）丙烯酸系共聚物（B);曱苯二異氰酸 酯系化合物（c)’其係相對於前述（甲基）丙烯酸系共聚物（A) 和（B)之合計i〇0重量份，為5〜2〇重量份；以及含環氧基 之矽烷耦合劑（D)。 在本案中’所謂（曱基）丙烯酸系共聚物，係指下述共 聚物·以丙稀酸酯單體或曱基丙烯酸酯單體為主成分，至 >使丙稀酸醋單體或曱基丙烯酸酯單體與具有反應性官能 基之單體進行共聚而成。再者，在本案中，所謂「（甲基） 丙稀酸（（metha)acryl)」，係以表示「丙烯酸」及「曱基丙烯 酸」兩者之意義來使用。 (甲基）丙烯酸酯單體，只要為具有（曱基）丙烯酸酯構造 201229167 者’則無特別限定，能夠使用下述單體之1種或2種以上， 例如：（甲基）丙烯酸甲酉旨、（甲基）丙烯酸乙醋、（甲基）丙烯 酸正丁醋、（甲基）丙烯酸異丁酯、（曱基）丙烯酸三級丁酯、 (甲基）丙稀酸正辛酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸 2-乙基己醋 '(甲基）丙烯酸正壬酯、（曱基）丙烯酸異壬酯、 (甲基）丙烯酸正癸酯、（甲基）丙烯酸正十二烷酯、及（甲基） 丙稀酸硬脂酯等（曱基）丙烯酸之碳數1〜18之直鏈或分枝 烷基酯、以及此等之各種衍生物。 作為具有反應性官能基之單體，能夠使用下述單體之 1種或2種以上’例如：含羧基之單體；含羥基之單體； 含環氧丙基之單體；含醯胺基、N_取代醯胺基之單體；含 三級胺基之單體等。 作為含羧基之單體，能夠使用例如：丙烯酸、甲基丙 稀酸、馬來酸、馬來酸針、富馬酸、巴豆酸、伊康酸、棒 康酸、桂皮酸、號ϊό酸单經基乙醋（甲基）丙稀酸醋（succinate monohydroxyethyl (metha)acrylate) ' 馬來酸單羥基乙酯（甲 基）丙烯酸酯、富馬酸單羥基乙酯（甲基）丙烯酸酯、1，2_二 羧基環己烷單羥基乙酯（曱基）丙烯酸酯、（曱基）丙烯酸二聚 物、ω-羧基聚己内酯單（曱基）丙烯酸酯等，但並不受此等 所限定。 作為含羥基之單體，能夠使用例如：（曱基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯酸3-羥 基丙酯、（甲基）丙浠酸4 -經基丁酯、（曱基）丙稀酸3 -甲基- 3-羥基丁酯、（曱基）丙烯酸1,1-二甲基-3-丁酯、（甲基）丙烯酸 201229167 1，3-二曱基-3-羥基丁酯、（曱基）丙烯酸2,2,4_三曱基羥其 戊酯、（甲基）丙烯酸2-乙基_3_羥基己酯、甘油單（甲基）丙 烯酸酯、聚丙二醇單（甲基）丙烯酸酯、聚乙二醇單（甲基） 丙烯酸酯、聚（乙二醇-丙二醇）單（曱基）丙烯酸酯、N_羥甲 基丙烯醯胺、烯丙醇、甲基烯丙醇等，但並不受此等所限 定。 作為含環氧丙基之單體，能夠使用例如：（曱基）丙稀 酸環氧丙酯、（甲基）丙烯酸3，4-環氧環己基甲酯、環氧丙基 乙烯基醚、3,4 -環氧環己基乙烯基醚、環氧丙基（曱基）烯丙 基醚、3,4-環氧環己基（甲基）烯丙基醚等，但並不受此等所 限定。 作為含醯胺基、N-取代醯胺基之單體，能夠使用例如： 丙烯醯胺、甲基丙烯醯胺、N-曱基（甲基）丙烯醯胺、N—乙 基（曱基）丙烯醯胺、N-甲氧基甲基（甲基）丙烯醯胺、N_乙氧 基曱基（甲基）丙烯醯胺、N_丙氧基曱基（曱基）丙烯醯胺、 N-丁氧基曱基（甲基）丙烯醯胺、N-三級丁基丙烯醯胺、N_ 辛基丙烯醯胺、雙丙酮丙烯醯胺等，但並不受此等所限定。 作為含三級胺基之單體，能夠使用：（甲基）丙烯酸二 曱基胺基乙酯、（曱基）丙烯酸二乙基胺基乙酯、二甲基胺 基丙基（曱基）丙烯醢胺等，但並不受此等所限定。 本發明中所使用之（曱基）丙烯酸系共聚物（A)，包含（甲 基）丙烯酸酯單體和含羧基之單體，作為共聚物成分。在前 述（曱基）丙烯酸系共聚物（A)中，相對於（曱基）丙烯酸系共 聚物（A)，作為共聚物成分而包含之（曱基）丙烯酸酯單體之 9 201229167 比例，以80重量％以上為佳。 此外’在前述（甲基）丙烯酸系共聚物（A)中，相對於（甲 基）丙烯酸系共聚物（A) ’作為共聚物成分而包含之含窥基 之單體之比例’以〇. 5〜5重量％為佳，以1〜3重量％較 佳。若相對於（甲基）丙烯酸系共聚物（A)，含羧基之單體的 含量為0.5重量％以上，則能夠提高黏著劑組成物之凝聚 力、耐久性，故較佳β另一方面，若相對於（甲基）丙稀酸 糸共聚物（Α)’含叛基之早體之含量為5重量％以下，則一 次加工性優異，故較佳。 本發明中所使用之（曱基）丙烯酸系共聚物（Α)之重量平 均分子量（Mw)，以50萬〜250萬為佳，以1〇〇萬〜25〇萬 較佳。若（甲基）丙烯酸系共聚物（A)之重量平均分子量（Mw) 為50萬以上，則能夠獲得充分的凝聚力，且能夠抑制氣泡 產生，故較佳。此外，若（甲基）丙烯酸系共聚物（A)之重量 平均分子量（Mw)為250萬以下，則能夠容易地將黏著劑組 成物塗佈於光學薄膜等，故較佳。 本發明中所使用之（甲基）丙烯酸系共聚物（B)，包含（甲 基）丙烯酸酯單體、含羧基之單體及含羥基之單體，作為共 聚物成分。在前述（曱基）丙烯酸系共聚物（B)中，相對於（甲 基）丙烯酸系共聚物（B)，作為共聚物成分而包含之（甲基） 丙烯酸酯單體之比例，以80重量％以上為佳。 此外’在前述（曱基）丙烯酸系共聚物（B)中，相對於（曱 基）丙烯酸系共聚物（B)，作為共聚物成分而包含之含緩基 之單體的比例，以〇. 1〜5重量％為佳，以0.5〜3重量％較 10 201229167 佳。若相對於（甲基）丙烯酸系共聚物（B)，含羧基之單體的 含量為0· 1重量％以上’則能夠提高黏著劑組成物之耐久 性，故較佳。另一方面，若相對於（曱基）丙烯酸系共聚物 (B)，含羧基之單體的含量為5重量％以下，則二次加工性 優異，故較佳。 此外，在前述（甲基）丙稀酸系共聚物（B)中，相對於（甲 基）丙烯酸系共聚物（B)，作為共聚物成分而包含之含經基 之單體的比例’以〇. 〇 1〜2重量％為佳，以〇 · 1〜1重量％ 較佳。若相對於（甲基）丙烯酸系共聚物（B)，含羧基之單體 的含量為0.01重量％以上，則抑制白斑之能力較高，故較 佳。另一方面，若相對於（甲基）丙烯酸系共聚物（B)，含繞 基之單體的含量為2重量％以下，則能夠抑制黏著劑制 離，故較佳。 本發明中所使用之（甲基）丙烯酸系共聚物（B)之重量平 均分子量（Mw)，以50萬〜250萬為佳，以100萬〜25〇萬 較佳。若（甲基）丙烯酸系共聚物（B)之重量平均分子量（Mw) 為50萬以上，則能夠獲得充分的凝聚力，且能夠抑制氣泡 產生，故較佳。此外，若（曱基）丙烯酸系共聚物（B)之重量 平均分子量（Mw)為250萬以下，則能夠容易地將黏著劑級 成物塗佈於光學薄膜等，故較佳。 在本案中，（甲基）丙烯酸系共聚物之重量平均分子量 (Mw)，是藉由下述方法測得之值。 (重置平均分子量（Mw)之測定方法） 201229167 依照下述（1)〜（3)進行測定。 (1) 將丙稀酸系共聚物溶液塗佈於剝離紙，並在100°C 乾燥2分鐘’而獲得薄膜狀的丙烯酸系共聚物。 (2) 以使固形份成為〇 2 %之方式，以四氫呋喃使前述（i ) 中所得之薄膜狀的丙烯酸系共聚物溶解。 (3) 在下述條件下’使用凝膠滲透層析法（GPC)，測定丙 烯酸系共聚物之重量平均分子量（Mw)。 (條件） GPC:HLC-8220 GPC[Tosoh(股)製] 管柱：使用4支TSK-GEL GMHXL 移動相溶劑：四氫Π夫喃 標準樣品：標準聚苯乙稀 流速：〇.6mL/min、管柱溫度：40°C 本發明中所使用之（甲基）丙烯酸系共聚物（A)和（B)之 聚合方法’並無特別限制’能夠使用溶液聚合、乳化聚合、 懸浮聚合等方法。其中，因在從由進行聚合所得之共聚物 之混合物製造黏著劑組成物時，處理步驟較簡單且能夠在 短時間内進行，因此以藉由溶液聚合來進行聚合為佳。 溶液聚合，一般能夠使用下述方法：在聚合槽内饋入 預定的有機溶劑、單體、聚合起始劑、及因應需要而使用 之鏈轉移劑，並在氮氣氣流中或有機溶劑之回流下，一面 攪拌一面加熱反應數小時等。再者，本發明中所使用之（甲 基）丙烯酸系共聚物（A)和（B)之重量平均分子量（Mw)，能夠 經由調整反應溫度、時間、溶劑量、觸媒的種類和量，來 12 201229167 設定成所需之分子量。 本發明之黏著劑組成物，包含：甲苯二異氰酸酯系化 合物（c)。甲苯二異氰酸酯系化合物可舉例如：2,4_甲苯_ 異氰酸酯、2,6-甲苯二異氰酸醋；及此等之二聚物、三聚 以及三羥甲基丙烷加成物等。 相對於（甲基）丙烯酸系共聚物（A)和（B)之合計ι〇〇 量份，本發明之黏著劑組成物中之甲苯二異氰酸酯系化合 物⑹之含量’以5〜20重量份為佳。若相對於（甲基)丙: 酸系共聚物（A)和（B)之合計100重量份，甲苯二異氰酸酯 系化合物(C)之含量為5重量份以上，則抑制白斑之能二 異，故較佳。另-方面，若相對於（甲基）丙稀酸系#聚物㈧ 和(B)之合言"00重量份’甲苯二異氰酸醋系化合物⑹之 含量為20重量份以下，則能夠確保對（甲基）丙稀酸系共聚 物（A)和（B)之相溶性，且能夠獲得足以作為黏著劑的黏 性，故較佳。 此外，本發明之黏著劑組成物，亦能夠依期望而併用 上述甲苯二異氰酸酯系化合物（c)以外之交聯劑。 本發明之黏著劑組成物，包含：含環氧基之石夕院麵合 劑（D) 〇 本發明中能夠使用之含環麓 衣乳巷之石夕院耦合劑（D)之具 體例’可舉例如：3-環氧丙盏其兩盆一 孔内巩基丙基二甲氧基矽烷、3 -環 氧丙氧基丙基二乙氧基石夕按Μ Ο I® Λ»· τ >_ 孔丞7尻專3_%乳丙氧基丙基三烷氧基 矽烷等；3 -環氧丙氧基丙基甲 氧基丙基曱基二甲氧基矽烷等 基二乙氧基矽烷、3-環氧丙 3·環氧丙氧基丙基烷基二烷 13 201229167 氧基石夕院等；曱基三（環氧丙基）石夕烧；2-(3,4-環氡環己基） 乙基三曱氧基矽烷、2_(34_環氧環己基）乙基三乙氧基矽烷 等2-(3,4-環氧環己基）乙基三烷氧基矽烷等；3_環氧丙氧基 丙基三甲氧基矽烷與四乙氧基矽烷之共聚物、3_環氧丙氧 基丙基三甲氧基石夕院與甲基三曱氧基石夕烧之共聚物等！分 子中包含環氧基和水解性的烷氧基之矽氧烷氧基寡聚物 等’但並不受此等所限定。 若使用在分子内至少具有甲氧基或乙氧基之任一者之 化合物，作為本發明中之含環氧基之石夕烷柄合劑（d)，則能 夠容易調節黏著力及二次加工性，故較佳。 若併用2種以上者，作為本發明中之含環氧基之㈣ 耦合劑（D)，則能夠容易調節耐久性及二次加工性，故較佳。 並且，若使用寡聚物者，作為本發明中之含環氧基之 石夕㈣合劑（D)’騎發性低，因此能夠糾間安定地獲得 黏著力、耐久性、二次加工性等性能，故較佳。 本發明中能夠使用之含環氧基之矽烷耦合劑（d)，可舉 例如：信越化學卫業公司製之製品名ΚΒΜ·3〇3、kbm_4〇3、 Χ-41-1095Α ΚΒΕ-402 > ΚΒΕ-403 ^ Χ-41-1053 ^ Χ-41-1〇56 等’但並不受此等所限定。 相對於（f基）丙烯酸系共聚物（Α)和（Β)之合計ι〇〇重 量伤，本發明之黏著劑組成物中之含環氧基之矽烷耦合劑 ⑼之調配量，以Hi重量份為佳，以重量份 較佳。若含環氧基之石夕烧輕合劑（D)之調配量》〇〇2重量 份以上’貝能夠充分調節黏著力及二次加工性，故較佳。 14 201229167 此外’若含環氧基之矽烷耦合劑（D)之調配量為1重量份以 下’則黏著力不會過高、或二次加工性不會惡化，故較佳。 本發明之黏著劑組成物可包含胺基改質矽氧本發 明之黏著劑組成物’經由調整胺基改質矽氧（E)之含量，即 能夠容易控制黏著力及二次加工性。此外，經由使本發明 之黏著劑組成物中包含胺基改質矽氧，即能夠抑制黏著 力之經時變化。 前述胺基改質矽氧（E) ’以使用側鍵具有胺基者較佳。 本發明中能夠使用之胺基改質矽氧（E)，可舉例如：信 越化學工業公司製之製品名KF-868、KF-865、KF-864、 KF-859、KF-393、KF-860、KF-880、KF-8004、KF-8002、 KF-8005、KF-867、X-22-3820W、KF-869、KF-861、 X-22-3939A、KF-877 等。此外，Dow Corning Toray 公司 製之製品名 BY16-205、FZ-3760、SF8417、BY16-849、 BY16-892、FZ-3785、BY16-872、BY16-213、BY16203、 BY1 6-898、BY1 6-890、BY1 6-89卜 BY1 6-893、FZ-3789 等。 本發明中能夠使用之胺基改質矽氧（E)並不受上述例示任 何限定》 相對於（甲基）丙烯酸系共聚物（A)和（B)之合計100重 量份，本發明之黏著劑組成物中之胺基改質矽氧（E)之調配 量，以0.05〜1重量份為佳’以〇.1〜0.7重量份較佳。若 胺基改質矽氧（E)之調配量為〇·〇5重量份以上，則能夠容易 控制黏著力及二次加工性，且能夠抑制黏著力之經時變 化，故較佳。此外’若胺基改質矽氧（E)之調配量為1重量 201229167 份以下，則黏著力不會顯著降低，故較佳。 本發明之黏著劑組成物’能夠依期望而包含具有經基 和松香骨架之化合物（F)e純本發明中之黏著劑組成物包 含具有羥基和松香骨架之化合物(F)，則能夠更加抑制白 斑，故較佳。 本發明中能夠使用之具有羥基和松香骨架之化合物 (F) ’旎夠使用例如：松香與多元醇進行反應而得之反應 物、松香與環氧化合物進行反應而得之反應物、松香紛。 上述松香能夠使用例如：木松香、脂松香、氫化松香、歧 化松香（diSpr0portionated rosin)、松油松香（taU 〇ϋ r〇sin” 及木系聚合松香、膠系聚合松香、松油系聚合松香等聚合 松香；以及此等之混合物等。 作為上述多元醇，只要為一元以上者，則無特別限定。 可具體例示如：乙二醇、二乙二醇、丨，2_二羥基丙烷、丨，3· 二羥基丙烷、1，2-二羥基丁烷、丨，3_二羥基丁烷、2,3_二羥 基丁烷、新戊二醇、1，4-雙羥基甲基-環己烷、丨，6•己二醇、 辛烯二醇（octene glyc〇l)、聚乙二醇等二元醇；甘油（丙三 醇）、1，2,4-丁三醇、三乙二醇、三丙二醇、3_甲基戊 二醇等三元醇；二甘油、季戊四醇等四元醇，亦可使用五 元以上之醇類。 上述松香與多元醇之反應’並無特別限定，能夠利用 各種習知手段。具體而言，只要將松香與多元醇饋入反應 容器中（以在氮氣和鈍氣等惰性氣體氣流中為佳），通常只 要在大氣壓下將系統内加熱至150〜300。(：左右，一面將所 16 201229167 生成之水去除至系統外一面使其反應即可。此外，進行反 應時可使用醋化觸媒。具體而言可舉例如；乙酸；對甲苯 T酸等酸觸媒’·氫氧化鐘等驗金屬之氫氧化 等驗:金屬之氮氧化物;—氧化鎮等金屬氧= 彳為上述¥氧化合物，能夠使用各 合物。具體而言可舉例如：乙一"…的-環氧化 g—醉一％氧丙基_、二乙二 =二環氧丙基謎、三乙二醇二環氧丙基驗、聚乙二：二： … g 一醇一環氧丙基醚、二丙二醇二環氧丙基醚、 :丙-醇二環氧丙基醚、聚丙二醇二環氧丙基醚、新戊二 :環备氧丙基醚、A己二醇二環氧丙基醚等非環狀脂肪族 ::氧丙基趟類；2,2他基苯基)丙烧二環氧丙基醚、 雙（4·羥基苯基）甲烷 環氧丙基驗、U·雙（4_經基苯基）乙 …氧丙基趟、2,2_雙(心經基環己基)丙 ，，，5_四甲基·4,4，_二羥基聯苯二環氧丙基醚、22， =㈣基丙氧基）苯基）丙院二環氧丙基喊等芳香族或 衣？曰肪族二環氧丙基醚類；3,4_環氧環己基子基' 3冬環 基甲酸醋、乙烯基環己烯二氧化物等環狀脂肪族環 肽裱氧乙烷類。 农 上述松香與環氧化合物之反應，並無特別限定 利用各種習知手段。只要以下述方式進行反應即可，例如. =觸媒存在下’在12〇〜·。c使二環氧化合物i _與松 i mol持續進行開環加成反應，直到酸價成為$以下， 酸仏以成為3以下為佳。該觸媒能夠使用例如：三曱基胺、 乙基胺、二丁基胺、苯曱基二曱基胺、吡啶、2_甲基咪 17 201229167 唑等胺系觸媒；氯化苯甲基三甲基銨等四級銨鹽；路易斯 (Lewis)酸、硼酸酯、有機金屬化合物、有機金屬鹽等。由 該方法所獲得之反應物，為在分子中具有2個松香骨架與 2個羥基且分子量分布狹窄的二醇化合物。此外，同樣地 亦能夠使用以下述方式獲得之聚合物：以前述二醇化合物 作為起始劑，使環氧乙燒或環氧丙烧、或ε_己内酯進行開 環聚合。 作為松香酚，可舉例如：使酚類與松香進行加成反應 而得者；和使甲階酚醛（res〇1)型酚樹脂與松香進行反應而 得之所明松香改質酚等，該甲階酚醛型酚樹脂係在鹼觸媒 存在下使酚類及曱醛進行加成反應而得。酚類係只要為能 夠與松香進行加成者，則能夠使用任何物。具體而言可舉 例如：笨酚、曱酚、β_萘酚、對三級丁基苯酚、對辛基苯 龄、對壬基苯酚等。(8) The adhesive composition according to the above (6) or (7), wherein the hydroxy group and the rosin are contained in an amount of 1 part by weight based on the total of the acrylic copolymers (A) and (B) The compound (F) of the skeleton is 1 to 2 parts by weight. (9) The adhesive composition according to any one of the above (1) to (8), wherein 'the total weight of the (meth)acrylic copolymer (A) and (B) is 1 〇〇 The wound contains the epoxy group-containing coupling agent (D) 〇~1 part by weight. [Efficacy] The adhesive composition of the present invention is excellent in durability even in a high-temperature and high-humidity environment, and is excellent in the ability to suppress white spots. Further, the optical (four) obtained by using the adhesive composition of the present invention is excellent in the ability to suppress white spots and can be preferably used for a personal computer even if it does not peel off and generate bubbles even under high temperature and high humidity. , TV, car navigation, etc. display 201229167 device. Further, the "adhesive composition of the present invention" has less change in adhesion over time and is excellent in secondary workability. Here, the term "secondary workability" refers to the ease with which the optical film is peeled off from the object when a problem such as foreign matter insertion occurs when the optical film is attached to the object by using an adhesive. Remove and reattach the new optical film. [Embodiment] The present inventors have made an effort to carry out research, and as a result, have found that an adhesive composition is excellent in durability and ability to suppress white spots, and the adhesive composition comprises the following components: a carboxyl group (fluorenyl) acrylic copolymer (A); a (meth)acrylic copolymer (B) containing a carboxyl group and a hydroxyl group; and a terpene diisocyanate compound (c)' relative to the above (meth) The total weight of the acrylic copolymers (A) and (B) is 5 to 2 parts by weight, and the epoxy group-containing decane coupling agent (D). In the present case, 'the so-called (fluorenyl) acrylic copolymer means a copolymer having a acrylate monomer or a methacrylate monomer as a main component, to > an acrylic acid acrylate monomer or The mercapto acrylate monomer is copolymerized with a monomer having a reactive functional group. In the present case, "meth) acryl is used in the sense of both "acrylic" and "mercaptopropene". The (meth) acrylate monomer is not particularly limited as long as it has a (fluorenyl) acrylate structure 201229167, and one or two or more of the following monomers can be used, for example, (meth)acrylic acid methacrylate. Ethyl acetate (meth)acrylate, n-butyl methacrylate, isobutyl (meth)acrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl methacrylate, 2-ethylhexyl acrylate (ethyl) decyl (meth) acrylate, isodecyl (meth) acrylate, n- decyl (meth) acrylate, (methyl) a linear or branched alkyl ester having 1 to 18 carbon atoms of (decyl)acrylic acid such as n-dodecyl acrylate or stearyl methacrylate, and various derivatives thereof. As the monomer having a reactive functional group, one or two or more of the following monomers can be used, for example, a monomer having a carboxyl group; a monomer having a hydroxyl group; a monomer having a glycidyl group; and a mercaptoamine a monomer having a N-substituted amidino group; a monomer having a tertiary amino group; and the like. As the carboxyl group-containing monomer, for example, acrylic acid, methyl methic acid, maleic acid, maleic acid needle, fumaric acid, crotonic acid, itaconic acid, roconconic acid, cinnamic acid, and citric acid can be used. Succinate monohydroxyethyl (methaacrylate) succinic acid monohydroxyethyl (meth) acrylate, monohydroxyethyl fumarate (meth) acrylate, 1 , 2_dicarboxycyclohexane monohydroxyethyl (mercapto) acrylate, (mercapto) acrylic acid dimer, ω-carboxy polycaprolactone mono (indenyl) acrylate, etc., but not subject to such Limited. As the hydroxyl group-containing monomer, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) propyl hydrazine can be used. Acid 4-butyl butyl ketone, (meth)acrylic acid 3-methyl-3-hydroxybutyl ester, (mercapto)acrylic acid 1,1-dimethyl-3-butyl ester, (meth)acrylic acid 201229167 1,3-Dimercapto-3-hydroxybutyl ester, 2,2,4-trimethyl hydroxypentyl (meth)acrylate, 2-ethyl-3-hydroxyl (meth)acrylate, glycerol Mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(indenyl)acrylate, N-hydroxyl Acrylamide, allyl alcohol, methyl allyl alcohol, etc., but are not limited by these. As the monomer containing a glycidyl group, for example, (fluorenyl) propylene acrylate, (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester, epoxypropyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, epoxypropyl (decyl) allyl ether, 3,4-epoxycyclohexyl (methyl) allyl ether, etc., but not subject to such limited. As the monomer containing a guanamine group and an N-substituted guanamine group, for example, acrylamide, methacrylamide, N-fluorenyl (meth) acrylamide, N-ethyl (fluorenyl) can be used. Acrylamide, N-methoxymethyl (meth) acrylamide, N_ethoxymercapto (meth) acrylamide, N-propoxy fluorenyl (fluorenyl) acrylamide, N - butoxy-decyl (meth) acrylamide, N-tert-butyl butyl decylamine, N- octyl acrylamide, diacetone acrylamide, etc., but are not limited thereto. As the monomer having a tertiary amino group, it is possible to use: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (fluorenyl) Acrylamide or the like, but is not limited by these. The (fluorenyl)acrylic copolymer (A) used in the present invention contains a (meth) acrylate monomer and a carboxyl group-containing monomer as a copolymer component. In the (indenyl)acrylic copolymer (A), the ratio of the (nonyl) acrylate monomer contained in the (mercapto)acrylic copolymer (A) is 9 201229167 as the copolymer component. More preferably, it is 80% by weight or more. Further, 'in the above (meth)acrylic copolymer (A), the ratio of the fluorene-containing monomer contained in the (meth)acrylic copolymer (A) 'as a copolymer component' is 〇. 5 to 5 wt% is preferred, and 1 to 3 wt% is preferred. When the content of the carboxyl group-containing monomer is 0.5% by weight or more based on the (meth)acrylic copolymer (A), the cohesive force and durability of the adhesive composition can be improved, so that β is preferable. When the content of the (meth)acrylic acid ruthenium copolymer (Α) is less than or equal to 5% by weight, the primary workability is excellent, which is preferable. The weight average molecular weight (Mw) of the (fluorenyl) acrylic copolymer (Α) used in the present invention is preferably from 500,000 to 2,500, and preferably from 10,000 to 250,000. When the weight average molecular weight (Mw) of the (meth)acrylic copolymer (A) is 500,000 or more, sufficient cohesive force can be obtained, and generation of bubbles can be suppressed, which is preferable. In addition, when the weight average molecular weight (Mw) of the (meth)acrylic copolymer (A) is 2.5 million or less, the adhesive composition can be easily applied to an optical film or the like, which is preferable. The (meth)acrylic copolymer (B) used in the present invention contains a (meth) acrylate monomer, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer as a copolymer component. In the (meth)acrylic copolymer (B), the ratio of the (meth) acrylate monomer contained as a copolymer component to the (meth)acrylic copolymer (B) is 80% by weight. More than % is better. Further, in the above (fluorenyl) acrylic copolymer (B), the ratio of the monomer containing a slow-base group as a copolymer component to the (fluorenyl)acrylic copolymer (B) is 〇. 1 to 5 wt% is preferred, and 0.5 to 3 wt% is better than 10 201229167. When the content of the carboxyl group-containing monomer is 0.1% by weight or more based on the (meth)acrylic copolymer (B), the durability of the adhesive composition can be improved, which is preferable. On the other hand, when the content of the carboxyl group-containing monomer is 5% by weight or less based on the (fluorenyl) acrylic copolymer (B), the secondary workability is excellent, which is preferable. Further, in the (meth)acrylic acid-based copolymer (B), the ratio of the monomer having a radical group contained as a copolymer component to the (meth)acryl-based copolymer (B) is 〇. 〇1 to 2% by weight is preferably 〇·1 to 1% by weight. When the content of the carboxyl group-containing monomer is 0.01% by weight or more based on the (meth)acrylic copolymer (B), the ability to suppress white spots is high, which is preferable. On the other hand, when the content of the ring-containing monomer is 2% by weight or less based on the (meth)acryl-based copolymer (B), the adhesion of the adhesive can be suppressed, which is preferable. The (meth)acrylic copolymer (B) used in the present invention has a weight average molecular weight (Mw) of preferably 500,000 to 2,500, and preferably 1,000,000 to 250,000. When the weight average molecular weight (Mw) of the (meth)acrylic copolymer (B) is 500,000 or more, sufficient cohesive force can be obtained, and generation of bubbles can be suppressed, which is preferable. In addition, when the weight average molecular weight (Mw) of the (fluorenyl)acrylic copolymer (B) is 2.5 million or less, the adhesive composition can be easily applied to an optical film or the like, which is preferable. In the present invention, the weight average molecular weight (Mw) of the (meth)acrylic copolymer is a value measured by the following method. (Measurement Method of Reset Average Molecular Weight (Mw)) 201229167 The measurement was carried out in accordance with the following (1) to (3). (1) The acrylic copolymer solution was applied to a release paper and dried at 100 ° C for 2 minutes to obtain a film-form acrylic copolymer. (2) The film-form acrylic copolymer obtained in the above (i) was dissolved in tetrahydrofuran so that the solid content became 〇 2 %. (3) The weight average molecular weight (Mw) of the acrylic copolymer was measured by gel permeation chromatography (GPC) under the following conditions. (Condition) GPC: HLC-8220 GPC [Tosoh system] Column: 4 TSK-GEL GMHXL mobile phase solvent: tetrahydrofurfuran standard sample: standard polystyrene flow rate: 〇.6mL/min , column temperature: 40° C. The polymerization method of the (meth)acrylic copolymers (A) and (B) used in the present invention is not particularly limited, and methods such as solution polymerization, emulsion polymerization, and suspension polymerization can be used. . Among them, when the adhesive composition is produced from a mixture of copolymers obtained by polymerization, the treatment step is simple and can be carried out in a short time, and therefore it is preferred to carry out the polymerization by solution polymerization. For solution polymerization, it is generally possible to use a method in which a predetermined organic solvent, a monomer, a polymerization initiator, and a chain transfer agent used as needed are fed into a polymerization tank, and are refluxed in a nitrogen gas stream or an organic solvent. The reaction is heated for several hours while stirring. Further, the weight average molecular weight (Mw) of the (meth)acrylic copolymers (A) and (B) used in the present invention can be adjusted by adjusting the reaction temperature, time, amount of solvent, and type and amount of the catalyst. To 12 201229167 set to the desired molecular weight. The adhesive composition of the present invention comprises a toluene diisocyanate compound (c). Examples of the toluene diisocyanate-based compound include 2,4-toluene-isocyanate and 2,6-toluene diisocyanate; and such dimers, trimers, and trimethylolpropane adducts. The content of the toluene diisocyanate compound (6) in the adhesive composition of the present invention is 5 to 20 parts by weight based on the total amount of the (meth)acrylic copolymers (A) and (B). good. When the content of the toluene diisocyanate compound (C) is 5 parts by weight or more based on 100 parts by weight of the total of the (meth)acrylic acid copolymers (A) and (B), the white spot can be inhibited from being different. Therefore, it is better. On the other hand, when the content of the 'toluene diisocyanate-based compound (6) is 20 parts by weight or less based on the combination of the (meth)acrylic acid-based polymer (VIII) and (B), It is preferable to be able to secure compatibility with the (meth)acrylic acid-based copolymers (A) and (B) and to obtain a viscosity sufficient as an adhesive. Further, in the adhesive composition of the present invention, a crosslinking agent other than the toluene diisocyanate compound (c) can be used in combination as desired. The adhesive composition of the present invention comprises: an epoxy-containing stone cherished dough mixture (D) 具体 a specific example of a Shixiyuan coupling agent (D) containing a ring-shaped Latex Lane which can be used in the present invention For example: 3-epoxypropanone, two pots, one well, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one, one _ 丞 7丞 3_% lactopropyl propyl trialkoxy decane, etc.; 3-glycidoxypropyl methoxypropyl decyl dimethoxy decane and other base diethoxy decane, 3-epoxypropane 3·glycidoxypropylalkyldioxane 13 201229167 Oxygen Shi Xiyuan et al; mercapto tris(epoxypropyl) Shi Xizhuo; 2-(3,4-cyclononancyclohexyl Ethyl trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, etc., such as 2-(34-epoxycyclohexyl)ethyltriethoxydecane; Copolymer of oxypropoxypropyltrimethoxynonane and tetraethoxy decane, copolymer of 3-glycidoxypropyltrimethoxy sylvestre and methyltrimethoxy sulphide; The oxirane alkoxy oligomer of the epoxy group and the hydrolyzable alkoxy group is contained in the molecule, but is not limited thereto. When a compound having at least one of a methoxy group or an ethoxy group in the molecule is used, as the epoxy group-containing alkane handle compound (d) in the present invention, adhesion and secondary processing can be easily adjusted. Sex, so it is better. When two or more types are used in combination, the epoxy group-containing (four) coupling agent (D) in the present invention can be easily adjusted in durability and secondary workability, which is preferable. In addition, when the oligomer is used, the epoxy group-containing stone (four) mixture (D) of the present invention has low riding ability, and therefore, adhesion, durability, secondary workability, and the like can be obtained with stability. Performance is better. The epoxy group-containing decane coupling agent (d) which can be used in the present invention is, for example, a product name: 〇3〇3, kbm_4〇3, Χ-41-1095Α ΚΒΕ-402 > by Shin-Etsu Chemical Co., Ltd. ; ΚΒΕ-403 ^ Χ-41-1053 ^ Χ-41-1〇56 etc. 'But is not subject to these restrictions. The blending amount of the epoxy group-containing decane coupling agent (9) in the adhesive composition of the present invention is based on the weight of Hi relative to the total weight of the (f-based) acrylic copolymer (Α) and (Β). The portion is preferred and is preferably in parts by weight. It is preferred that the amount of the epoxy group-containing stone saponin (D) is 〇〇2 parts by weight or more, and the adhesiveness and secondary workability can be sufficiently adjusted. In addition, when the amount of the epoxy group-containing decane coupling agent (D) is 1 part by weight or less, the adhesion is not excessively high or the secondary workability is not deteriorated, which is preferable. The adhesive composition of the present invention may contain an amine-based modified oxime of the adhesive composition of the present invention. The content of the oxime (E) is adjusted by adjusting the amine group, that is, the adhesion and secondary workability can be easily controlled. Further, by including the amine group-modified oxime in the adhesive composition of the present invention, it is possible to suppress the change with time of the adhesive force. The above-mentioned amino group-modified oxime (E) ' is preferably one having an amine group using a side bond. The amine-based modified oxime (E) which can be used in the present invention may, for example, be a product name KF-868, KF-865, KF-864, KF-859, KF-393, KF- manufactured by Shin-Etsu Chemical Co., Ltd. 860, KF-880, KF-8004, KF-8002, KF-8005, KF-867, X-22-3820W, KF-869, KF-861, X-22-3939A, KF-877, etc. In addition, Dow Corning Toray's product names are BY16-205, FZ-3760, SF8417, BY16-849, BY16-892, FZ-3785, BY16-872, BY16-213, BY16203, BY1 6-898, BY1 6- 890, BY1 6-89, BY1 6-893, FZ-3789, etc. The amine-based modified oxime (E) which can be used in the present invention is not limited by the above-exemplified exemplification" with respect to 100 parts by weight of the total of the (meth)acrylic copolymers (A) and (B), and the adhesive of the present invention The amount of the amine-based modified oxime (E) in the composition of the composition is preferably from 0.05 to 1 part by weight, preferably from 0.1 to 0.7 part by weight. When the amount of the amine-based modified oxime (E) is 5 parts by weight or more, the adhesion and secondary workability can be easily controlled, and the change in the adhesive force with time can be suppressed, which is preferable. Further, if the amount of the amine-modified oxime (E) is 1 part by weight to 201229167 parts, the adhesion is not remarkably lowered, which is preferable. The adhesive composition of the present invention can contain a compound having a transuretic group and a rosin skeleton as desired. (F) e. The adhesive composition of the present invention contains a compound (F) having a hydroxyl group and a rosin skeleton, and can be further suppressed. White spots, so it is better. The compound (F) having a hydroxyl group and a rosin skeleton which can be used in the present invention can be used, for example, a reaction product obtained by reacting rosin with a polyhydric alcohol, a reaction product obtained by reacting rosin with an epoxy compound, and rosin. The rosin can be, for example, wood rosin, gum rosin, hydrogenated rosin, disSpr0portionated rosin, pine oil rosin (taU 〇ϋ r〇sin), woody polymerized rosin, gum polymerized rosin, pine oil polymerized rosin, etc. The above-mentioned polyol is not particularly limited as long as it is one or more. The specific examples are, for example, ethylene glycol, diethylene glycol, hydrazine, 2-dihydroxypropane, hydrazine, and the like. 3. Dihydroxypropane, 1,2-dihydroxybutane, hydrazine, 3-dihydroxybutane, 2,3-dihydroxybutane, neopentyl glycol, 1,4-bishydroxymethyl-cyclohexane , hydrazine, hexamethylene glycol, octene glycol, diol, etc.; glycerol (glycerol), 1,2,4-butanetriol, triethylene glycol And a trihydric alcohol such as tripropylene glycol or 3-methylpentanediol; a tetrahydric alcohol such as diglycerin or pentaerythritol; or an alcohol having five or more members. The reaction between the rosin and the polyhydric alcohol is not particularly limited and can be utilized. a variety of conventional means. Specifically, as long as the rosin and polyol are fed into the reaction vessel (for nitrogen It is preferable to use an inert gas flow such as gas or inert gas. Generally, the system is heated to 150 to 300 at atmospheric pressure. (: Left and right, the water generated by the 16201229167 is removed to the outside of the system for reaction. Further, a acetal catalyst may be used in the reaction, and specific examples thereof include acetic acid, an acid catalyst such as p-toluene T acid, a hydroxide such as a hydroxide clock, and the like: metal oxynitride; Metal Oxygen such as Oxidation Town = 彳 is the above-mentioned oxo compound, and each compound can be used. Specifically, for example, E- epoxidation g- drunk-% oxypropyl _, di- ethane = bicyclic ring Oxypropyl propyl mystery, triethylene glycol diepoxypropyl test, polyethylene two: two: g g-alcohol monoepoxypropyl ether, dipropylene glycol diepoxypropyl ether, : propanol diepoxypropyl Alkyl ether, polypropylene glycol diepoxypropyl ether, neopentyl: cyclopropyloxypropyl ether, A hexane diethylene oxide propyl ether and other acyclic aliphatic: oxypropyl hydrazine; 2, 2 Benzyl phenyl) propylene diethylene oxide ether, bis(4.hydroxyphenyl)methane epoxy propyl, U.bis(4-phenylphenyl)ethyl oxypropyl , 2,2_bis(neurocyclohexyl)propane,,,5-tetramethyl-4,4,-dihydroxybiphenyldiepoxypropyl ether, 22, =(tetra)propoxy)phenyl) Propylene compound di-epoxypropyl group and other aromatic or clothing? 曰 aliphatic diepoxypropyl ether; 3,4_epoxycyclohexyl ketone '3 winter ring carboxylic acid vinegar, vinyl cyclohexene dioxide The cyclic aliphatic cyclic peptide oxirane such as a compound. The reaction between the rosin and the epoxy compound is not particularly limited, and various conventional means can be used. The reaction can be carried out in the following manner, for example, in the presence of a catalyst. 'In 12〇~·.c, the diepoxy compound i _ and the pine i mol are continuously subjected to a ring-opening addition reaction until the acid value becomes $ or less, and the acid strontium is preferably 3 or less. The catalyst can use, for example, an amine-based catalyst such as tridecylamine, ethylamine, dibutylamine, benzoguanidinylamine, pyridine, 2-methylimyl 17 201229167 azole; benzyl chloride A quaternary ammonium salt such as trimethylammonium; a Lewis acid, a boric acid ester, an organometallic compound, an organic metal salt, or the like. The reactant obtained by this method is a diol compound having two rosin skeletons and two hydroxyl groups in the molecule and having a narrow molecular weight distribution. Further, it is also possible to use a polymer obtained by subjecting the above diol compound as a starter to ring-opening polymerization of ethylene bromide or propylene propylene or ε_caprolactone. Examples of the rosin phenol include those obtained by subjecting a phenol to a rosin to an addition reaction, and a rosin-modified phenol obtained by reacting a resole phenol resin with a rosin. The resol type phenol resin is obtained by subjecting a phenol and furfural to an addition reaction in the presence of a base catalyst. Any phenolic compound can be used as long as it can be added to rosin. Specific examples thereof include phenol, indophenol, β-naphthol, p-tert-butylphenol, p-octylbenzene, p-nonylphenol and the like.
作為上述具有羥基和松香骨架之化合物（F)，能夠較佳 使用例如以下述商品名於市面販售者：「PINEcrystaL D 6011」、r pinecrystal κε 615 3」、「piNECRYSTAL D-6240」、「PINECRYSTAL KE_359」[荒川化學工業（股） 製]、「NEOTALL 125P」、「NEOTALL 1 50P」[Harima 化成（股）] 等。 作為上述具有羥基和松香骨架之化合物（F)，以分子内 具有下述式（I)所示之骨架之化合物為佳。 201229167As the compound (F) having a hydroxyl group and a rosin skeleton, for example, a commercially available product such as "PINEcrysta L D 6011", "r pinecrystal κ ε 615 3", "piNECRYSTAL D-6240", "PINECRYSTAL" can be preferably used. KE_359" [Arakawa Chemical Industry Co., Ltd.], "NEOTALL 125P", "NEOTALL 1 50P" [Harima Chemical (share)], etc. The compound (F) having a hydroxyl group and a rosin skeleton is preferably a compound having a skeleton represented by the following formula (I) in the molecule. 201229167
作為具有羥基和松香骨架之化合物（F)，以下述式（π) 所示之骨架之化合物特佳。As the compound (F) having a hydroxyl group and a rosin skeleton, a compound having a skeleton represented by the following formula (π) is particularly preferable.
相對於（曱基）丙烯酸系共聚物⑷和⑻之合計⑽重 量份’本發明之黏著劑組成物中之具有經基和松香骨架之 化合物（F)之調配量，以U重量份為佳，以5〜15重量 純佳。若具㈣基和㈣骨架之化合物（F)之調配量為i 重讀以上’ m能夠抑制白斑’故較佳。此外，若具有羥 絲松香骨架之化合物（F)之調配量為2G t量份以下，則 黏者力不會過咼’而二次加工性亦不會降低，故較佳。 本發明之黏著劑組成物，能夠依期望而適當調配：各 種添加劑、溶劑、耐候性安^劑、塑化劑、軟化劑、染料、 顏料、無機填充劑等。 相對於（甲基）丙綿酸系共聚物⑷和⑻之合計ι〇〇重 201229167 染料、顏料、無 以下為佳，以20 經由使調配量成 劑組成物之黏著 量伤’耐候性安定劑、塑化劑、軟化劑、 機填充劑等之調配量之範圍以3 〇重量份 重塁份以下更佳’以i 〇重量份以下最佳。 為這樣的範圍内，即能夠適當保持黏著 力、濕潤性、耐熱性、糊劑轉黏性之平衡，而能夠獲得顯 示良好的各種物性之黏著劑組成物。 [實施例] 以下，依據實施例來詳細說明本發明，但本發明並不 受此等實施例任何限定。再者，實施例中所使用之試驗片 之製作、以及各種試驗方法及評估方法，係如下所述。 (1)試驗用光學薄膜之製作 使用作為光學薄膜的一例之偏光膜，製作具有黏著劑 層之偏光膜。於經矽氧系脫模，劑進行表面處理之剝離膜 上，以使乾燥後之塗佈量成為25 g/cm2之方式塗佈黏著劑 組成物。其次，在1 00t使用熱風循環式乾燥機乾燥9〇秒， 而形成黏著劑層。然後，將黏著劑層面貼合在偏光基底薄 膜（於以聚乙烯醇（PVA)膜為主體之偏光片之兩面積層三乙 酿纖維素（TAC)膜而成者；約1 9〇 pm)之背面，並使其通過 加壓夾輥來進行壓黏。壓黏後，在23t、65% RH熟成1〇 天，而獲得具有黏著劑層之偏光膜。 (2)耐久性之評估 以使長邊相對於光之吸收軸成為45。之方式切割「（〇 201229167 試驗用光學薄膜之製作」中所製得之偏光膜，而獲得140 mmx260 mm(長邊）之試驗片，使用該試驗片，使用積層機 黏貼在0.7 mm CORNING公司製無鹼玻璃板r # 1737」之 單面。其次，對此樣品實施高壓釜處理（5〇〇c , 5 kg/cm2， 20分鐘）後，在23 C、65% 之條件下放置24小時。然 後，在80 C乾燥環境中放置5〇〇小時，並在6〇。匸9〇% RH 之ί哀境中放置500小時後，以肉眼觀察來評估起泡、剝離 之狀態。評估基準係如下所述。 (耐久性評估基準） a)耐熱試驗（在⑽它乾燥環境中放置5〇〇小時後，評估有無 起泡） ◎:完全無起泡 〇：1角有起泡，但能夠實用 〇△· 2角有起泡，但能夠實用 △ . 2角以上有起泡，而無法實用 X .有顯著的起泡’而無法實用 )耐.........式驗（在60 C 90% RH環境中放置500小時後，評 估條紋、剝離） ◎:完全無條紋、剝離 〇.1角有條紋，但能夠實用 △ 2角有條紋或剝離，但能夠實用 △ : 2角以 μ女作， 有條紋或剝離’而無法實用 x:有顯著的條紋或剝離，而無法實用 21 201229167 (3)白斑現象之評估試驗With respect to the total (10) parts by weight of the (fluorenyl)acrylic copolymers (4) and (8), the compounding amount of the compound (F) having a warp group and a rosin skeleton in the adhesive composition of the present invention is preferably U by weight. It is pure by 5~15 weight. It is preferred that the compounding amount of the compound (F) having a (four) group and a (iv) skeleton is i. In addition, when the compounding amount of the compound (F) having a hydroxy silk rosin skeleton is 2 parts by weight or less, the viscosity is not excessively 咼, and the secondary workability is not lowered, which is preferable. The adhesive composition of the present invention can be appropriately formulated as desired: various additives, solvents, weathering agents, plasticizers, softeners, dyes, pigments, inorganic fillers and the like. With respect to the total of (meth)acrylic acid-based copolymers (4) and (8), ι 〇〇 201229167 dyes, pigments, and the like are not preferable, and the weather resistance stabilizer is damaged by the adhesion amount of the composition of the composition of 20 The blending amount of the plasticizer, the softener, the machine filler, and the like is preferably in the range of 3 parts by weight or less, more preferably in parts by weight. In such a range, it is possible to appropriately maintain the balance of adhesion, wettability, heat resistance, and paste transfer viscosity, and it is possible to obtain an adhesive composition which exhibits various physical properties. [Examples] Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited by the examples. Further, the production of the test piece used in the examples, various test methods and evaluation methods are as follows. (1) Preparation of optical film for test A polarizing film having an adhesive layer was produced by using a polarizing film as an example of an optical film. The adhesive composition was applied to a release film which was subjected to surface treatment by a deuterium-oxygen type release agent so that the coating amount after drying was 25 g/cm2. Next, it was dried at 100 00 using a hot air circulation dryer for 9 seconds to form an adhesive layer. Then, the adhesive layer is laminated on a polarizing base film (a two-layer layer of a trichlorocellulose (TAC) film of a polarizer having a polyvinyl alcohol (PVA) film as a main component; about 19 pm) The back side is pressed and pressed by a pressure nip roller. After pressure bonding, it was aged at 23 t and 65% RH for 1 day to obtain a polarizing film having an adhesive layer. (2) Evaluation of durability The length of the long side with respect to the absorption axis of light was 45. By cutting the polarizing film obtained in "(201222167 Production of Optical Film for Testing)", a test piece of 140 mm x 260 mm (long side) was obtained, and the test piece was adhered to a 0.7 mm CORNING company using a laminator. One side of the alkali-free glass plate r #1737. Next, the sample was subjected to autoclave treatment (5 〇〇c, 5 kg/cm2, 20 minutes), and then left at 23 C, 65% for 24 hours. Then, it was allowed to stand in an 80 C dry environment for 5 hours, and after standing for 500 hours in a 〇 〇 〇 〇 〇 R R R 哀 , , , , , , , , , 500 500 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 (Endurance evaluation criteria) a) Heat resistance test (evaluate the presence or absence of blistering after (5) placed in a dry environment for 5 hours) ◎: No foaming at all: 1 blistering, but practical 〇 △·2 corners have foaming, but they can be used △. There are blistering at 2 or more angles, but they are not practical. X. There is significant blistering 'and not practical'. After being placed in a 90% RH environment for 500 hours, the stripe and peeling were evaluated. ◎: No streaks, peeling 〇.1 Striped, but practical △ 2 angles have stripes or peeling, but can be practical △: 2 angles with μ female, striped or peeled 'can not be practical x: significant streaks or peeling, but not practical 21 201229167 (3 White spot phenomenon evaluation test
以使偏光轴相互垂直之方式，將具有與「（2)耐久性之 評估」同樣尺寸的黏著劑層之偏光膜黏貼在〇 7 mm之 CORNING公司製無鹼玻璃板「#1737」之兩面，而製作試 驗樣品。其次，對此樣品實施高壓釜處理（5〇t，5 kg/cm2， 20匀鐘）後，在2；rc、50% RH之條件下放置24小時。然 後，在80°C乾燥之條件下放置5〇〇小時。放置後，在23t、 0% RH之條件下使用均勻光源（股份有限公司I . SYSTEM 製）’並使用EyeScaie_3w(股份有限公司j . system製）， 以肉眼來確認白斑。將不均測定系統EyeScaie_3W2 CCD 相機設置於距離試驗片2〇〇 cm之位置後，評估白斑。 (白斑評估基準） ◎:完全無白斑 〇：有些許白斑 〇△:有白斑，但能夠實用 △:有白斑’而無法實用 X .有亮度高的白斑，而無法實用 (黏#力之評估） 單面經實施脫模處理之聚對酞酸乙二酷（ρΕτ)膜 == 脫模處理面’以使乾燥後之厚度成為約 ^方式流鑄塗佈下述各實施財所調製之㈣ 在⑽。C加熱乾W分鐘，而形成黏㈣層。液 P之外，另外準備單面經實施脫模處理之(輕剝離性之)聚 22 201229167 酞酸乙二酯（PET)臈q(厚声 予度.50 _) ’於PET膜P之黏著 材層之表面，以使PET膜〇之盼描南 、Q之脫模處理面接觸之方式人 PET膜Q，並使其通過加麼 主穴视果進仃壓黏而貼合。然後， 在溫度23 °C、相對濕度5〇% /0 <條件下進仃熟成7天，而獲 得在黏著劑層之兩面分別透過脫模處理而具有PET膜之兩 面黏著片。此兩面黏著片係藉由將透過脫模處理而設置之 2片PET膜剝離，而成為益其 驭马‘“、基材之由黏者材層本身所構成 之黏著片。 將設置於所得之兩面黏著片的一者之厚度38 _之 PET膜Q剝離後，以與所露出之黏著劑層之表面接觸之方 式疊合未經實施脫模處理之厚度1〇〇 0111之1>£丁膜]1[商品 名.A4 100，東洋紡績（股）製]，並使其通過加壓夾輥來進 行壓黏而貼合，而製作試驗用薄片。 [測定] 將上述之試驗用薄片切割成25 mmx 150 mm，而製作 成樣品片後，將所得之樣品片之厚度1〇〇 μπι的PET膜P 剝離’並使用桌上積層機，將所露出之黏著劑層的表面壓 黏在厚度2 mm的玻璃板上，而製作成試驗樣品。將所得 之試驗樣品在23°C、50% RH之條件下放置24小時後，使 用桌上型材料試驗機STA-1225((股）〇RIENTEC製），將PET 膜R的一端朝1 80。之方向拉扯，並測定1 80。剝離時之黏著 力（剝離速度：300mm/min)。評估係依照下述評估基準.來進 行。 23 201229167 <二次加工性評估基準> 〇：在23°C 1小時後、及在50°C 4小時後之任一者均在2 〜12N/2 5mm之範圍内 X :在23°C 1小時後、及在50°C 4小時後之任一者在2〜 12N/25mm之範圍外 ((曱基）丙浠酸系共聚物之製造） (製造例1) 在具備溫度計、攪拌機、氮氣導入管、及回流冷凝管 之反應器内’加入丙烯酸正丁酯（BA)99重量份、丙烯酸 (AA)1重量份、乙酸乙酯（eac)1〇〇重量份、及偶氮雙異丁 腈（AIBN)O.l重量份，並以氮氣來置換反應容器之空氣。然 後’在攪拌下，在氮氣環境中，使反應容器之内容物溫度 升溫至65°C ’並使其反應8小時。反應結束後，以乙酸乙 酯來稀釋反應混合物，而獲得固形份16.8重量％之丙烯酸 系共聚物溶液。丙烯酸系共聚物之重量平均分子量為167 萬。 (製造例2) 在具備溫度計、攪拌機、氮氣導入管、及回流冷凝管 之反應器内’加入丙烯酸正丁酯（BA)83.5重量份、丙烯酸 三級丁酯（t-BA)15重量份、丙烯酸2-羥基乙酯（2HEA)0_5 重量份、丙烯酸（ΑΑ)ι重量份、乙酸乙酯（EAc)lOO重量份、 及偶氮雙異丁腈（ΑΙΒΝ)〇.ι重量份，並以氮氣來置換反應容 24 201229167 器之空氣。然後’在攪拌下，在氮氣環境中’使反應容器 之内容物溫度升溫至651，並使其反應8小時°反應結束 後，以乙酸乙酯來稀釋反應混合物’而獲得固形份19.7重 量％之丙烯酸系共聚物溶液。丙烯酸系共聚物之重量平均 分子量為146萬。 (實施例1) 將下述成分充分攪拌混合而獲得黏著劑組成物：506 重量份之作為丙烯酸系共聚物（A)之製造例1中所合成之丙 烯酸系共聚物溶液（作為丙烯酸系共聚物（A)為85重量 份）、76重量份之作為丙烯酸系共聚物（B)之製造例2中所 合成之丙稀酸糸共聚物溶液（作為丙稀酸系共聚物（B)為Η 重量伤）、17重置份之作為甲苯二異氰酸酯系化合物（c)之 CORONATE L(日本P0LYURET_e公司製，有效成分為 I3重量份）、0·02重量份之作為環氧系交聯劑之 ΤΕΤ··Χ(三菱瓦斯化學公司製之環氧化合物，有效成分 為〇.〇2重量份）、5重量份之作為具有經基和松香骨架之化 合物（F)之D.6(m(荒川化學^公司製之含㈣的二醇， 有效成分為5重量份）、〇 2重量份之 姐_ 耦合劑（D)之X.41.1G53(信越化學八S *氧基之石夕烧 劑’有效成分為0.2重量份）、以及、么/製石夕炫耦合 改質石夕氧⑻《KF_859(信越化學工量份之作為胺基 氧，有效成分為（M重量份）。使用㈣二司製胺基改質石夕 藉由前述之試驗用光學薄膜 黏著劑組成物’ 製作^來製作試驗用光學 25 201229167 薄膜後，進行前述之各種測定。 結果’實施例1之光學薄膜係耐久性（8〇t乾燥環境、 l〇5°C乾燥環境、6(rc X90%RH)、白斑之項目之評估基準 顯示「©」。換言之，實施例丨之光學薄膜係顯示下述事^實： 即使在高溫高濕之環境巾耐久性亦優#，並讀 能力優異。 •曰斑& 除了將黏著劑組成物之微 配以外，其餘與實施们同樣^更為表1中所記載之調 及比較例Η之試驗用光學而製作實施们〜仏 ^ χ] /專骐，並評估其性能。 26 201229167 實施例11 OC κη *—< jrj "Η O 〇 ◎ 〇 〇 cs m 實施例10 ΙΛ 00 jn JO 0.05 1 o 〇 ◎ 〇 〇 r- On 實施例9 ΙΛ 00 52 jrj o o 〇 ◎ 〇 〇 〇\ 〇 雜例8 00 J£J o ◎ ◎ 〇 〇 CN Os 實施例7 00 JO W-J o ◎ ◎ 〇 〇 m 卜 實施例6 in 00 JO 0.02 o 〇 〇 〇 〇 o CN 實施例5 00 L〇 jn 0.01 o 〇 〇△ 〇 〇 實施例4 00 r—( *«< o ◎ ◎ ◎ 〇 v〇 卜 實施例3 \n oo wn o 〇 〇 〇 〇 00 On 實施例2 in 00 o 〇 〇 〇 〇 c\ 實施例1 \n oo in v〇 s ◎ ◎ ◎ 〇 卜 製造例i ! 製造例2 CORONATEL X-41-1053 X-41-1056 KBM-403 KBM-803 KF-859 KF-353 D-6011 (80〇CX500hr) ill P i its 80〇CX500hr 黏著力 300mm/min 23t>lhr 後 (N/25mm) 50〇〇4hr 後 (N/25mm) 丙烯酸系共聚物 甲苯^氣酸ai系 含環綠之梦烧! 胺基改質矽氧 fl ll Jqn 5 ^ 财久性 白斑 二办口工性 黏著力之經時變化 27 201229167 1 例 5 j vn 00 jn S in ◎ ◎ ◎ X CO 味例4 «ο 00 jn (N <N in < X ◎ X tmw 00 JO JO S t—Η X X ◎ 〇 ΙΓΐ 蛾例2 00 jn CN S »-Η κη <] X ◎ 〇 (S 00 tm例1 00 i2 寸 3 κη 〇 X <! 〇 vr> 卜 實施例17 00 jn S wo 〇 〇 ◎ 〇 00 〇 實施例16 oo <〇 S t-H ◎ ◎ ◎ 〇 oo 〇 實施例15 tr) ec 12 jo S ◎ ◎ 〇 〇 令 實施例14 纪 〇 CN S vn 〇△ 〇 ◎ 〇 CO 寸 實施例13 00 in S ◎ 〇 ◎ 〇 卜 〇\ 實施例Π oo <£J 1 1 〇 〇 〇 〇 〇 cs CO 製造例1 製造例2 CORONATEL X-41-1053 X-4M056 KBM-403 KBM-803 KF-859 KF-353 1X6011 财熱微 (80〇CX500hr) III ^ i S 80〇CX500hr 黏著力 300mm/min i 23。0】址後 (N/25mm) 50°〇4hr 後 (Ν/25ππη) $· 甲苯二氰酸酿系 化錄 含環 合劑 胺基改質矽氧 |! R1' 耐久性 白斑 二二城工性 黏著力之經時變化 28 201229167 CORONATE L :日本POLYURETHANE公司製，有致成八 為75% X-41-1053 :信越化學公司製，有效成分為ι〇〇%，為境氧 基寡聚物系且烷氧基為甲氧基/乙氧基 X-41-1056 :信越化學公司製，有效成分為1〇〇%，為燒氣 基寡聚物系且烷氧基為甲氧基 KBM-4〇3 :信越化學公司製 基單體系且烷氧基為曱氧基 三曱氧基矽烷 KBM-803 :信越化學公司製 基單體系且烷氧基為甲氧基 基矽烷 KF-859 :信越化學公司製， KF-353 :信越化學公司製， D-6011 :荒川化學公司製， 【圖式簡單說明】 無 【主要元件符號說明】 無 有效成分為100%，為院氧 化學名為3 -環氧丙氧基丙基 ’有效成分為1〇〇%，為院氧 ，化學名為3 -疏基丙基三曱氧 有效成分為100%，胺基改質 有效成分為100%，聚醚改質 有效成分為100% 29A polarizing film having an adhesive layer having the same size as "(2) Evaluation of durability" was adhered to both sides of an alkali-free glass plate "#1737" manufactured by CORNING Co., Ltd., 7 mm, so that the polarization axes were perpendicular to each other. And make test samples. Next, the sample was subjected to autoclave treatment (5 〇t, 5 kg/cm 2 , 20 tempering), and then placed under conditions of 2; rc, 50% RH for 24 hours. Then, it was allowed to stand under the conditions of drying at 80 ° C for 5 hours. After standing, a uniform light source (manufactured by Co., Ltd.) was used under the conditions of 23t and 0% RH, and EyeScaie_3w (manufactured by J. Co., Ltd.) was used to confirm white spots with the naked eye. The unevenness measurement system EyeScaie_3W2 CCD camera was placed at a position 2 cm away from the test piece, and white spots were evaluated. (White spot evaluation standard) ◎: There is no white spot plaque: Some white spot 〇 △: There are white spots, but it can be practical △: There are white spots 'can not be practical X. There are white spots with high brightness, but can not be practical (adhesive #力的评价) Polybutyric acid ruthenium ruthenium (ρΕτ) film with one side being subjected to mold release treatment == release treatment surface' so that the thickness after drying becomes about the same method, and the following implementations are prepared by coating (4) (10). C is heated to dry for W minutes to form a sticky (four) layer. In addition to the liquid P, another one is prepared by performing a mold release treatment (light peelability) of poly 22 201229167 ethylene phthalate (PET) 臈 q (thickness of the sound. 50 _) 'adhesion to the PET film P The surface of the material layer is such that the PET film is in contact with the surface of the release film of the Q film, and the human PET film Q is placed in contact with the surface of the film. Then, the mixture was aged for 7 days under the conditions of a temperature of 23 ° C and a relative humidity of 5 〇 % / 0 °, and a double-sided adhesive sheet having a PET film which was subjected to release treatment on both sides of the adhesive layer was obtained. The two-sided adhesive sheet is obtained by peeling off two PET films which are provided by the release treatment, and becomes an adhesive sheet composed of the adhesive layer itself of the substrate. After peeling off the PET film Q of one of the two-sided adhesive sheets, the thickness of the PET film Q is peeled off in contact with the surface of the exposed adhesive layer, and the thickness of the film is not subjected to the mold release treatment. [1] [product name: A4 100, manufactured by Toyobo Co., Ltd.], and pressed and pressed by a pressure nip roll to form a test sheet. [Measurement] The above test sheet was cut into 25 mm x 150 mm, and after the sample piece was formed, the obtained sample piece was peeled from the PET film P having a thickness of 1 μm and the surface of the exposed adhesive layer was pressure-bonded to the thickness 2 using a table laminator. A test sample was prepared on a glass plate of mm. The test sample was placed under conditions of 23 ° C and 50% RH for 24 hours, and then a desktop material testing machine STA-1225 (manufactured by RIENTEC) was used. ), pull one end of the PET film R toward 180°, and measure 1 80. When peeling off Adhesion (peeling speed: 300 mm/min). The evaluation was carried out in accordance with the following evaluation criteria. 23 201229167 <Secondary workability evaluation criteria> 〇: 1 hour after 23 ° C, and at 50 ° C 4 Any one of the hours after the hour is in the range of 2 to 12 N/2 5 mm X: after 1 hour at 23 ° C, and after 4 hours at 50 ° C, it is outside the range of 2 to 12 N / 25 mm (( (Production Example 1) In a reactor equipped with a thermometer, a stirrer, a nitrogen gas introduction tube, and a reflux condenser, 99 parts by weight of n-butyl acrylate (BA) was added, and acrylic acid ( AA) 1 part by weight, ethyl acetate (eac) 1 part by weight, and azobisisobutyronitrile (AIBN) Ol parts by weight, and the air of the reaction vessel is replaced with nitrogen. Then, under stirring, under nitrogen In the environment, the temperature of the contents of the reaction vessel was raised to 65 ° C and allowed to react for 8 hours. After the completion of the reaction, the reaction mixture was diluted with ethyl acetate to obtain a 16.8 wt% aqueous solution of the acrylic copolymer. The weight average molecular weight of the acrylic copolymer was 1.67 million. (Production Example 2) In the reactor of the meter, the agitator, the nitrogen inlet tube, and the reflux condenser, 83.5 parts by weight of n-butyl acrylate (BA), 15 parts by weight of butyl acrylate (t-BA), and 2-hydroxyethyl acrylate were added. (2HEA) 0_5 parts by weight, acrylic acid (ΑΑ) by weight parts, ethyl acetate (EAc) 100 parts by weight, and azobisisobutyronitrile (ΑΙΒΝ) 〇.1 parts by weight, and replacing the reaction volume with nitrogen 24 201229167 Air of the device. Then, the temperature of the contents of the reaction vessel was raised to 651 under stirring in a nitrogen atmosphere, and the reaction was allowed to proceed for 8 hours. After the reaction was completed, the reaction mixture was diluted with ethyl acetate to obtain a solid fraction of 19.7 wt%. Acrylic copolymer solution. The acrylic copolymer had a weight average molecular weight of 1.46 million. (Example 1) The following components were sufficiently stirred and mixed to obtain an adhesive composition: 506 parts by weight of an acrylic copolymer solution (as an acrylic copolymer) synthesized in Production Example 1 of the acrylic copolymer (A) (A) is 85 parts by weight), and 76 parts by weight of a bismuth acrylate copolymer solution synthesized in Production Example 2 as the acrylic copolymer (B) (as the acrylic acid copolymer (B) is Η weight In the case of the toluene diisocyanate compound (c), CORONATE L (manufactured by P0LYURET_e, Japan, the active ingredient is I3 parts by weight), and 0. 02 parts by weight of the epoxy-based crosslinking agent. Χ (epoxy compound made by Mitsubishi Gas Chemical Co., Ltd., active ingredient is 〇. 〇 2 parts by weight), and 5 parts by weight of D.6 (m) (Arakawa Chemical^ as a compound having a warp group and a rosin skeleton) The company's diol containing (4), the active ingredient is 5 parts by weight), 〇 2 parts by weight of the sister _ coupling agent (D) X.41.1G53 (Shin-Etsu Chemical VIII S * oxy-stone smelting agent' active ingredient 0.2 parts by weight), and, / / Shi Xixuan coupling modified Shi Xi oxygen (8) KF_859 (Shin-Etsu Chemicals Co., Ltd. as the amine-based oxygen, the active ingredient is (M parts by weight). Using (4) Acetone-based modified amine stone by the above-mentioned test optical film adhesive composition 'made ^ to make After the test optical 25 201229167 film, the above various measurements were performed. Results The optical film of Example 1 was durable (8 〇 dry environment, l 〇 5 ° C dry environment, 6 (rc X 90% RH), white spot The evaluation standard of the item shows "©". In other words, the optical film of the embodiment shows the following: Even in the case of high temperature and high humidity, the durability of the towel is excellent, and the reading ability is excellent. • Freckle & The micro-matching of the adhesive composition was carried out in the same manner as in the experiment, and the test opticals of the comparative examples described in Table 1 were used to produce the implements~仏^ χ]/specialized, and the performance was evaluated. 26 201229167 Example 11 OC κη *—< jrj "Η O 〇 ◎ 〇〇 c m Example 10 ΙΛ 00 jn JO 0.05 1 o 〇 ◎ 〇〇r- On Example 9 ΙΛ 00 52 jrj oo 〇 ◎ 〇〇〇\ 〇 8 8 00 J£J o ◎ ◎ 〇〇CN Os Example 7 00 JO WJ o ◎ ◎ 〇〇m 卜 Example 6 in 00 JO 0.02 o 〇〇〇〇o CN Example 5 00 L〇jn 0.01 o 〇〇 △ 〇〇 Example 4 00 r—(*«< o ◎ ◎ ◎ 〇v〇 Bu Example 3 \n oo wn o 〇〇〇〇00 On Example 2 in 00 o 〇〇〇〇c\ Example 1 \n oo in V〇s ◎ ◎ ◎ 制造 制造 manufacture example i ! Manufacturing example 2 CORONATEL X-41-1053 X-41-1056 KBM-403 KBM-803 KF-859 KF-353 D-6011 (80〇CX500hr) ill P i its 80〇CX500hr Adhesive force 300mm/min 23t> After 1hr (N/25mm) 50〇〇4hr (N/25mm) Acrylic copolymer toluene^Gas acid ai system containing ring green dream burning! Amine modified oxygen Fl ll Jqn 5 ^ Time-varying changes in the oral adhesion of the leukoplakia 27 201229167 1 Example 5 j vn 00 jn S in ◎ ◎ ◎ X CO Example 4 «ο 00 jn (N <N in < X ◎ X tmw 00 JO JO S t—Η XX ◎ 〇ΙΓΐ Moth example 2 00 jn CN S »-Η κη <] X ◎ 〇 (S 00 tm example 1 00 i2 inch 3 κη 〇X <! 〇vr> Example 17 00 jn S wo 〇〇 ◎ 〇 00 〇 Example 16 oo < 〇 S tH ◎ ◎ ◎ 〇 oo 〇 Example 15 tr) ec 12 jo S ◎ ◎实施 实施 实施 实施 〇 〇 〇 〇 〇 S 13 13 13 oo oo oo oo oo > £ J 1 1 〇〇〇〇〇 cs CO Manufacturing Example 1 Manufacturing Example 2 CORONATEL X-41-1053 X-4M056 KBM-403 KBM-803 KF-859 KF-353 1X6011 Finance Micro (80〇CX500hr) III ^ i S 80〇CX500hr Adhesion 300mm/min i 23.0 】After the address (N/25mm) 50°〇4hr (Ν/25ππη) $· Toluene dicyanate brewing system containing ring-containing agent amine-based modified 矽 oxygen|! R1' Durable white spot two-two industrial adhesive Time change of force 28 201229167 CORONATE L : Made by Japan POLYURETHANE company, it has 75% X-41-1053: manufactured by Shin-Etsu Chemical Co., Ltd., the active ingredient is ι〇〇%, which is an oxo oligomer and alkane. The oxy group is methoxy/ethoxy X-41-1056: manufactured by Shin-Etsu Chemical Co., Ltd., the active ingredient is 1%, which is a gas-burning base. Polymer and alkoxy group is methoxy KBM-4〇3: base system of Shin-Etsu Chemical Co., Ltd. and alkoxy group is decyloxy-decyloxydecane KBM-803: base system of Shin-Etsu Chemical Co., Ltd. Further, the alkoxy group is methoxy decane KF-859: manufactured by Shin-Etsu Chemical Co., Ltd., KF-353: manufactured by Shin-Etsu Chemical Co., Ltd., D-6011: manufactured by Arakawa Chemical Co., Ltd., [Simple description of the drawing] No [Main component symbol description] No active ingredient is 100%, the oxidation name of the hospital is 3 - glycidoxypropyl 'the active ingredient is 1〇〇%, it is the hospital oxygen, the chemical name is 3-isylpropyl trioxane active ingredient is 100%, the amino-based modified active ingredient is 100%, and the polyether modified active ingredient is 100%.