TW200811488A

TW200811488A - Optical film with adhesive

Info

Publication number: TW200811488A
Application number: TW096118560A
Authority: TW
Inventors: Ryu Takeko; Kook-Seung Shin
Original assignee: Sumitomo Chemical Co
Priority date: 2006-05-26
Filing date: 2007-05-24
Publication date: 2008-03-01
Also published as: JP2007316377A; WO2007139173A1

Abstract

Disclosed is an optical film with adhesive which is obtained by forming an adhesive layer on at least one side of an optical film. The adhesive layer is composed of a composition containing an acrylic resin, an ionic compound containing cations, and a crosslinking agent.

Description

200811488 九、發明說明【發明所屬之技術領域】本發明係關於附黏著劑之光學薄膜。本發明中作爲對象的光學薄膜，可列舉例如，偏光薄膜和相位差薄膜。本發明亦關於使用此附黏著劑之光學薄膜之液晶顯示用的光學層合體。【先前技術】偏光薄膜爲被裝配至液晶顯示裝置，廣泛被使用，且以偏光子之兩面層合透明保護薄膜，並於至少一者之保護薄膜表面形成黏著劑層，且於此黏著劑層上貼黏以剝離薄膜之狀態下流通。又，亦有於偏光子之兩面貼合保護薄膜之狀態的偏光薄膜上，層合以相位差薄膜作成橢圓偏光薄膜，並且於此相位差薄膜側貼黏以黏著劑層/剝離薄膜。更且，亦可於相位差薄膜之表面貼黏以黏著劑層/剝離薄膜。貼合至液晶元件前，由此等之偏光薄膜、橢圓偏光薄膜、相位差薄膜等將剝離薄膜剝出，並透過露出的黏著劑層貼合至液晶元件。此類偏光薄膜、橢圓偏光薄膜或相位差薄膜因在將剝離薄膜予以剝離且貼合至液晶元件時，發生靜電，故期望開發出防止之對策。其對策之一，於專利第3 0 1 2860號公報（專利文獻1) 中，提案於偏光子薄膜表面層合以保護薄膜，並且於保護薄膜表面設置黏著劑層的偏光薄膜中，使用電解質鹽和有機基聚矽氧烷所構成的離子導電性組成物及含有丙烯酸系 -4- 200811488 共聚物的組成物作爲黏著劑。經由使用此類黏著劑，可表現防止帶電性，但其性能不能稱爲一定充分，且黏著耐久性亦不能稱爲充分之性能。另一方面，於特表2004-536940號公報（專利文獻2) 中’揭示於感壓接黏劑（黏著劑）中配合有機鹽系之抗靜電劑，對此黏著劑賦予防止帶電性。更且，於特開2004-1 14665號公報（專利文獻3)中，記載令接黏劑等中含有總碳數爲4-20個之四級銨陽離子與含氟原子之陰離子所構成之鹽，賦予抗靜電性。更且，如上述之附黏著劑之光學薄膜，以.其黏著劑層側貼合至液晶元件作成液晶顯示裝置，但以此狀態放置於高溫或高溫高濕條件，並且重複加熱和冷卻時，隨著光學薄膜的尺寸變化，於黏著劑層發生氣泡，並且於光學薄膜與黏著劑層之間，或黏著劑層與液晶元件玻璃之間發生浮起和剝離等，故亦要求不會產生此類不適、耐久性優良。又，於暴露在高溫之情形中，作用於光學薄膜之殘留應力分佈變得不均勻，並且引起應力集中於光學薄膜的外周部，結果發生黑色顯示時外周部變成發白之所謂飛白的現象，並產生色斑，故亦要求抑制此類飛白和色斑。更且，將附黏著劑之光學薄膜貼合至液晶元件時，於不完全之情形中，暫時剝離其光學薄膜後，再度重貼，但亦要求於其剝離時黏著劑層爲伴隨光學薄膜被拉剝，於元件玻璃上未殘留黏著劑，則亦不會產生朦朧等之所謂的再次加工性。本發明之課題爲在於提供將提高抗靜電性，耐久性亦 -5- 200811488 優良之黏著劑層設置於光學薄膜表面之附黏著劑之光學薄膜。本發明者等人爲了解決此類課題進行致力硏究之結果 ’發現對於含有特定之丙烯酸樹脂的黏著劑，配合特定之離子性化合物，並將此組成物以黏著劑層型式設置於光學薄膜之表面，則可取得防止帶電性及耐久性優良之附黏著劑之光學薄膜，並且達到本發明。【發明內容】即，若根據本發明，則爲提供於光學薄膜之至少單面形成黏著劑層而成，其黏著劑層爲由含有下列成分（A)、 (B)及（C)之組成物所形成之附黏著劑之光學薄膜。 (A)以來自下式（I)200811488 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to an optical film with an adhesive. The optical film to be used in the present invention may, for example, be a polarizing film or a retardation film. The present invention also relates to an optical laminate for liquid crystal display using the optical film with the adhesive. [Prior Art] A polarizing film is widely used in a liquid crystal display device, and a transparent protective film is laminated on both sides of a polarizer, and an adhesive layer is formed on at least one of the protective film surfaces, and the adhesive layer is formed thereon. The adhesive is affixed to the film to be detached. Further, on the polarizing film in which the protective film is bonded to both surfaces of the polarizer, the retardation film is laminated to form an elliptically polarizing film, and the retardation film side is adhered to the adhesive layer/release film. Further, an adhesive layer/peeling film may be adhered to the surface of the retardation film. Before being bonded to the liquid crystal element, the release film is peeled off by a polarizing film, an elliptically polarizing film, a retardation film or the like, and is adhered to the liquid crystal element through the exposed adhesive layer. When such a polarizing film, an elliptically polarizing film, or a retardation film is peeled off and bonded to a liquid crystal element, static electricity is generated. Therefore, it is desired to develop measures for prevention. One of the countermeasures is disclosed in Japanese Patent Publication No. 3 0 1 2860 (Patent Document 1), in which a polarizing film is laminated on a surface of a polarizing film, and an electrolyte salt is used in a polarizing film provided with an adhesive layer on the surface of the protective film. An ion conductive composition composed of an organic polyoxyalkylene oxide and a composition containing an acrylic-4-200811488 copolymer are used as an adhesive. By using such an adhesive, it is possible to prevent the chargeability, but the performance cannot be said to be sufficient, and the adhesion durability cannot be called sufficient performance. On the other hand, JP-A-2004-536940 (Patent Document 2) discloses that an organic salt-based antistatic agent is blended in a pressure-sensitive adhesive (adhesive) to impart charge-preventing properties to the adhesive. Further, Japanese Patent Publication No. 2004-1 14665 (Patent Document 3) discloses a salt comprising an anion having a total carbon number of 4 to 20 and a fluorinated atom. , giving antistatic properties. Further, as described above, the optical film with an adhesive is attached to the liquid crystal cell as a liquid crystal display device, but is placed in a high temperature or high temperature and high humidity condition in this state, and when heating and cooling are repeated, As the size of the optical film changes, bubbles are formed in the adhesive layer, and floating and peeling occur between the optical film and the adhesive layer, or between the adhesive layer and the liquid crystal cell glass, so that it is not required to occur. Class discomfort and excellent durability. Further, in the case of exposure to a high temperature, the residual stress distribution acting on the optical film becomes uneven, and stress is concentrated on the outer peripheral portion of the optical film, and as a result, the phenomenon that the outer peripheral portion becomes whitish when the black display occurs is caused. It also produces stains, so it is also required to suppress such whitening and staining. Further, when the optical film with an adhesive is attached to the liquid crystal element, in the case of incompleteness, the optical film is temporarily peeled off and then reattached, but it is also required that the adhesive layer is accompanied by the optical film when it is peeled off. When the peeling is performed and no adhesive remains on the glass of the element, so-called reworkability such as ruthenium is not generated. An object of the present invention is to provide an optical film of an adhesive which is provided with an adhesive layer which is excellent in antistatic property and has excellent durability and is provided on the surface of an optical film. The inventors of the present invention have made efforts to solve such problems and have found that for an adhesive containing a specific acrylic resin, a specific ionic compound is blended, and the composition is placed on the optical film in an adhesive layer form. On the surface, an optical film with an adhesive which is excellent in chargeability and durability can be obtained, and the present invention can be achieved. SUMMARY OF THE INVENTION According to the present invention, an adhesive layer is formed on at least one side of an optical film, and the adhesive layer is composed of the following components (A), (B), and (C). An optical film of an adhesive formed by the object. (A) from the following formula (I)

ch2=c-c-〇-r2 (I) (式中，R!爲表示氫原子或甲基，R2爲分別表示亦可經碳數1〜10個之烷氧基所取代之碳數1〜14個之烷基或芳烷基 )所示之（甲基）丙烯酸酯之構造單位作爲主成分，更且，於分子內含有一個烯烴性雙鍵和來自具有至少一個羧基之不飽和羧酸的構造單位，且含有重量平均分子量爲 800,0〇〇〜2,000,000之第一丙烯酸樹脂，且來自前述不飽和羧酸之構造單位的含量，相對於樹脂全體1 00重量份，爲0.5〜10重量份之丙烯酸樹脂、 -6 - 200811488 (B)下式（II)Ch2=cc-〇-r2 (I) (wherein R! represents a hydrogen atom or a methyl group, and R2 represents a carbon number of 1 to 14 which may be substituted by an alkoxy group having 1 to 10 carbon atoms, respectively. The structural unit of the (meth) acrylate represented by the alkyl group or the aralkyl group as a main component, and further contains an olefinic double bond in the molecule and a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group. And containing the first acrylic resin having a weight average molecular weight of 800,0 〇〇 2,000,000, and the content of the structural unit derived from the unsaturated carboxylic acid is 0.5 to 10 parts by weight based on 100 parts by weight of the entire resin. Resin, -6 - 200811488 (B) Formula (II)

(Π) (式中，R3爲表示碳數1〜12個之烷基，R4、R5及R6爲分別獨立表示碳數6〜12個之院基）所示之含有陽離子之離子性化合物、及 (C)交聯劑。上述之丙烯酸樹脂（A)亦可僅由上述規定之第一丙烯酸樹脂所構成，且亦可除第一丙烯酸樹脂，加上與以不同於其之丙烯酸樹脂（視爲第二丙烯酸樹脂）的混合物所構成。第二丙烯酸樹脂可列舉例如，以來自前述式（I)所示之（甲基）丙烯酸酯之構造單位作爲主成分，且重量平均分子量爲 50,000〜500,000 者。又，若根據本發明，亦提供此附黏著劑之光學薄膜爲以其黏著劑層側層合至玻璃基板所成的光學層合體。【實施方式】以下，詳細說明本發明。於本發明中，作爲構成黏著劑之樹脂成分的丙烯酸樹脂（A)，以來自前述式（I)所示之（甲基）丙烯酸酯之構造單位作爲主成分，更且，於分子內含有一個烯烴性雙鍵和來自具有至少一個羧基之不飽和殘酸的構造單位，且含有重量平均分子量爲800,000〜2,〇〇〇,〇〇〇 200811488 之第一丙烯酸樹脂。丙烯酸樹脂（A)亦可僅由此處所規定之第一丙烯酸樹脂所構成，且亦可爲第一丙烯酸樹脂，與以不同於其之丙烯酸樹脂（視爲第二丙烯酸樹脂）的混合物所構成。來自上述不飽和羧酸之構造單位，以丙烯酸樹脂 (A)全體視爲100重量份，以0.5〜10重量份之比例於第一丙烯酸樹脂中含有。另外，所謂（甲基）丙烯酸，係意指丙烯酸或甲基丙烯酸之任一者，另外，以（甲基）丙烯酸酯等稱謂時之「（甲基）」亦爲相同主旨。於作爲第一丙烯酸樹脂之主要構造單位的前述式（I) 中，Ri爲氫原子或甲基，R2爲碳數1〜14個之烷基或芳烷基，較佳爲烷基。R2所示之烷基或芳烷基爲各個基中之氫原子亦可經碳數1〜1 〇個之烷氧基所取代。式（I)所示之（甲基）丙烯酸酯，具體而言，可例示丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸正辛酯、丙烯酸月桂酯般之直鏈狀丙烯酸烷酯；丙烯酸異丁酯、丙烯酸2-乙基己酯 '丙烯酸異辛酯般之分支狀丙烯酸烷酯；甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸正辛酯、甲基丙烯酸月桂酯般之直鏈狀甲基丙烯酸烷酯、甲基丙烯酸異丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸異辛酯般之分支狀甲基丙烯酸烷酯等。 R2爲經烷氧基所取代之烷基時，即，R2爲烷氧烷基時之式（I)所示之（甲基）丙烯酸酯’具體而言，可例示丙烯酸2-甲氧乙酯、丙烯酸乙氧甲酯、甲基丙烯酸2-甲氧乙 -8 - 200811488 酯、甲基丙烯酸乙氧甲酯等。R2爲芳烷基時之式（I)所示之（甲基）丙烯酸酯，具體而言，可例示丙烯酸苄酯和甲基丙烯酸苄酯等。於製造弟一丙細酸樹脂時，式（I)所不之（甲基）丙燦酸酯可使用某一種之化合物，且亦可使用二種以上之化合物。其中，使用丙烯酸丁酯作爲至少一個單體爲佳。於是，來自構成第一丙烯酸樹脂之（甲基）丙烯酸酯的構造單位，含有來自丙烯酸丁酯之單位爲較佳的形態。作爲第一丙烯酸樹脂之又一個構造單位的不飽和羧酸，爲分子內具有一個烯烴性雙鍵和至少一個羧基的化合物，具體例可列舉丙烯酸、甲基丙烯酸、順丁烯二酸、衣康酸等。其中，亦以丙烯酸或甲基丙烯酸爲適當。又，第一丙烯酸樹脂亦可含有來自具有羧基以外之極性官能基之單體的構造單位。羧基以外之極性官能基可列舉例如，羥基、醯胺基、環氧基、氧環丁烷基、胺基、異氰醯基、醛基等。極性官能基爲羥基之單體，可列舉例如，（甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸4-羥丁酯等。極性官能基爲醯胺基之單體，可列舉例如，丙烯醯胺、甲基丙烯醯胺、N，N-二甲胺丙基丙烯醯胺、N，N-二甲基丙烯醯胺、N，N-二乙基丙烯醯胺、N-羥甲基丙烯醯胺等。極性官能基爲環氧基之單體，可列舉例如，丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、丙烯酸3,4·環氧環己基甲酯、甲基丙烯酸3,4-環氧環己基甲酯等。極性官能基 -9- 200811488 爲氧環丁烷基之單體’可列舉例如’（甲基）丙烯酸氧環丁院酯、（甲基）丙嫌酸3 -氧環丁院基甲酯、（甲基）丙烯酸（3-甲基-3-氧環丁院基）甲酯、(甲基）丙燒酸（3_乙基-3-氧環丁院基）甲酯等、極性官能基爲胺基之單體，可列舉例如’ 丙燒酸N，N -二甲胺基乙酯、丨希丙胺等。極性官能基爲異氰酸基之單體，可列舉例如，異氰酸2 -甲基丙烯醯氧乙酯等。又，極性官能基爲醛基之單體，可列舉例如，丙烯醛等。於第一丙烯酸樹脂中，以此不揮發成分之全體之重量爲基準，來自式（I)所示之（甲基）丙烯酸酯之構造單位通常含有60〜99.5重量％，較佳爲80〜99·5重量％。又，來自不飽和羧酸之構造單位通常爲含有0·5〜10重量％左右、較佳爲1〜6重量％。來自不飽和羧酸之構造單位相對於丙烯酸樹脂（A)全體1〇〇重量份，即，於丙烯酸樹脂（A)僅由第一丙烯酸樹脂所構成時’相對於其1 〇0重量份，又’於第一丙烯酸樹脂及與其不同之第二丙烯酸樹脂所構成時，相對於彼等合計100重量份，含有0.5〜10重量份之比例。相對於丙烯酸樹脂（A)全體100重量份，來自不飽和羧酸之構造單位的比例較佳爲0.5〜6重量份。相對於丙烯酸樹脂（A) 100重量份，若來自不飽和羧酸之構造單位的份量爲0.5重量％以上，則將含有其之黏著劑層貼合至玻璃基板時，具有可抑制玻璃基板與黏著劑層之間之浮起和剝離的傾向，故爲佳。又，其份量若爲10重量份以下，則即使經由溫度變化等令光學薄膜的尺寸變化，亦可令黏著劑 -10- 200811488 層追隨此尺寸變化而變動，故液晶元件周緣部的明亮度與中心部的明亮度之間並無差異，具有可抑制飛白和色斑的傾向，故爲佳。更且，相對於丙烯酸樹脂（A) 1 00重量份，若來自不飽和羧酸之構造單位的份量爲0.5〜10重量份之範圍，則由與後述離子性化合物（B)之相溶性的觀點而言亦爲佳。第一丙烯酸樹脂亦可含有前述式（I)所示之（甲基）丙烯酸酯及來自前述之不飽和羧酸以外之單體的構造單位。此類可任意使用的單體可列舉例如，於分子內具有一個烯烴性雙鍵和至少一個五員環以上之雜環基的雜環系單體。此處，所謂五員環以上之雜環基，爲意指於碳數5個以上、較佳爲碳數5〜7個之脂環式烴基中，其中之至少一個亞甲基爲經氮原子、氧原子、硫原子等之雜原子所取代之基。雜環系單體之具體例可列舉丙烯醯嗎啉、乙烯基己內醯胺、N-乙烯基-2-吡咯烷酮、丙烯酸四氫糠酯、甲基丙烯酸四氫糠酯、己內酯改性丙烯酸四氫糠酯等。又，丙烯酸3，4-環氧環己基甲酯、甲基丙烯酸3，4-環氧環己基甲酯等之雜原子爲構成三員環及七員環之單體爲具有七員環的雜環基，故可以雜環系單體型式操作。更且，如2,5-二氫呋喃般，亦可於雜環基中含有烯烴性雙鍵。雜環系單體亦可使用不同之二種以上的單體。雜環系單體其中亦以N-乙烯基吡咯烷酮、乙烯基己內醯胺、丙烯醯嗎啉或其混合物爲適當。令第一丙烯酸樹脂中含有來自雜環系單體之構造單位 -11 - 200811488 時，其份量爲以第一丙烯酸樹脂作爲基準，通常爲30重量％左右，較佳爲20重量％以下。另外，若第一丙烯酸樹脂中含有0.1重量％以上來自雜環系單體之構造單位，則即使光學薄膜之尺寸變化，此尺寸變化亦追隨黏著劑層變動，故液晶元件之周緣部的明亮度與中心部的明亮度之間變成無差異，有抑制發白和色斑之傾向。又，可任意使用之其他的單體，可列舉於分子內具有一個烯烴性雙鍵和至少一個脂環式構造的脂環式單體。脂環式構造通常爲碳數5個以上、較佳爲碳數5〜7個左右之環烷構造或環烯烴構造，於環烯烴構造中，於脂環式構造中具有烯烴性雙鍵。具體而言，具有脂環式構造之丙烯酸酯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、丙烯酸第三丁基環.己酯、α -乙氧基丙烯酸環己酯、丙烯酸環己基苯酯等，具有脂環式構造之甲基丙烯酸酯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酯、甲基丙烯酸第三丁基環己酯、甲基丙烯酸環己基苯酯等。又，於分子內具有數個脂環式構造之丙烯酸酯，可列舉衣康酸雙環己基甲酯、衣康酸二環辛酯、琥珀酸二環十二烷基甲酯等。更且，具有乙烯基之醋酸乙烯基環己酯等亦可作爲脂環式單體。其中，亦以丙烯酸異冰片酯、丙烯酸環己酯、甲基丙烯酸異冰片酯、甲基丙烯酸環己酯、丙烯酸二環戊酯由於易 -12- 200811488 於取得，故爲佳。脂環式單體亦可組合使用不同之二種以上的化合物。令第一丙烯酸樹脂中含有來自脂環式單體之構造單位時，其份量爲以第一丙烯酸樹脂作爲基準，通常爲30重量％左右，較佳爲15重量％以下。另外，若第一丙烯酸樹脂中含有0.1重量％以上，更且爲1重量％以上來自脂環式單體之構造單位，則具有抑制玻璃基板與黏著劑層之間之浮起和剝落的傾向。更且，作爲其他單體之式（I)所示之（甲基）丙烯酸酯、雜環系單體及脂環式單體之任一者均可使用不同的乙烯基系單體。此類乙烯基系單體可列舉例如，脂肪酸乙烯酯' 鹵素化乙烯基、鹵素化亞乙烯基、（甲基）丙烯腈、共軛二烯化合物、芳香族乙烯基等。此處，脂肪酸乙烯酯可例示例如，醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯基、月桂酸乙烯酯等。鹵素化乙烯基可例示氯乙烯、溴乙烯等。且鹵素化亞乙烯基可例示偏氯乙烯，（甲基）丙烯腈可例示丙烯腈及甲基丙烯腈。共軛二烯化合物爲於分子內具有共軛雙鍵的烯烴，具體例可列舉異戊二烯、丁二烯、氯丁烯等。芳香族乙烯基爲具有芳香族環和乙烯基的化合物，具體例可列舉苯乙烯、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、庚基苯乙烯、辛基苯乙烯、氟苯乙烯、氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯、 -13- 200811488 硝基苯乙烯、乙醯苯乙烯、甲氧基苯乙烯般之苯乙烯系單體、乙烯基吡啶和乙烯基咔唑般之含氮芳香族乙烯基等。此些乙烯基系單體亦可組合使用不同之二種以上的化合物〇令第一丙烯酸樹脂中含有來自如上述乙烯基系單體之構造單位時，其份量爲以第一丙烯酸樹脂作爲基準，通常爲5重量％以下，較佳爲0.05重量％以下，但以實質上不含有爲更佳。將來自雜環系單體之構造單位、來自脂環式單體之構造單位及來自乙烯基系單體之構造單位中導入數個時，彼等之合計量爲以第一丙烯酸樹脂作爲基準，爲30重量％以下，更且以20重量％以下爲佳。以上說明之第一丙烯酸樹脂的製造方法可列舉例如，溶液聚合法、乳化聚合法、塊狀聚合法、懸浮聚合法等，其中亦以溶液聚合法爲佳。溶液聚合法之具體例可列舉將所欲之單體及有機溶劑混合，調製成單體濃度爲5 0重量 %以上，較佳爲5 0〜6 0重量％之混合液後，於氮氛圍氣下，單體合計每100重量份添加0.00 1〜5重量份左右之聚合引發劑，並於40〜90°C左右、較佳爲50〜70°C左右攪拌8 小時以上、較佳爲8〜1 2小時左右之方法等。聚合引發劑可使用熱聚合引發劑和光聚合引發劑等。光聚合引發劑可列舉例如，4-(2·羥乙氧基）苯基（2-羥基-2-丙基）酮等。熱聚合引發劑可列舉例如，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-:^腈） -14- 200811488 、2,2’-偶氮雙（2,4-二甲基戊腈）、2,2’-偶氮雙（2,4-二甲基-4-甲氧基戊腈）、二甲基-2,2’-偶氮雙（2-丙酸甲酯）、 2,2’-偶氮雙（2-羥甲基丙腈）般之偶氮系化合物；過氧化月桂醯、氫過氧化第三丁基、過氧化苯甲醯、第三丁基過氧基苯甲酸酯、氫過氧化枯烯、二異丙基過氧基二碳酸酯、二正丙基過氧基二碳酸酯、第三丁基過氧基新癸酸酯、第三丁基過氧基特戊酸酯、（3,5，5-三甲基己醯基）過氧化物般之有機過氧化物，過硫酸鉀、過硫酸銨、過硫酸氫般之無機過氧化物等。又，倂用過氧化物和還原劑的氧化還原系引發劑等亦可使用作爲聚合引發劑。聚合反應中所用之有機溶劑可列舉例如，甲苯、二甲苯般之芳香族烴類，醋酸乙酯、醋酸丁酯般之酯類；正丙醇、異丙醇般之脂肪族醇類；丙酮、甲基乙基酮、甲基異丁基酮般之酮類等。第一丙烯酸樹脂之分子量以膠滲透層析（GPC)換算成聚苯乙烯之重量平均分子量（Mw)爲800,000〜2,000,000之範圍。若重量平均分子量爲8 00,000以上，則可提高於高溫高濕下的接黏性，且令玻璃基板與黏著劑層之間發生浮起和剝落的可能性有變低的傾向，並且有提高再次加工性的傾向，故爲佳。又，若重量平均分子量爲2,000,000以下，則即使此黏著劑層所貼合之光學薄膜的尺寸隨著溫度變化等而變化，黏著劑層爲追隨此尺寸變化而變動，故液晶元件之周緣部的明亮度與中心部的明亮度之間變成無差異，具有抑制飛白和色斑之傾向，故爲佳。以重量平均分 -15- 200811488 子量（Mw)與數平均分子量（Μη)之比（Mw/Mn)表示的分子量分佈，通常爲2〜10左右之範圍。本發明所用之黏著劑亦可含有與上述第一丙烯酸樹脂不同之第二丙烯酸樹脂作爲丙烯酸樹脂（A)。可另外含有之第二丙烯酸樹脂，可列舉例如，以來自前述式（I)所示之（甲基）丙烯酸酯之構造單位作爲主成分，且根據GPC之換算成標準聚苯乙烯的重量平均分子量（Mw)爲 50,000〜500,000左右之範圍之低分子量物質。使用低分子量之第二丙烯酸樹脂時，其份量，相對於丙烯酸樹脂（A)之不揮發成分合計100重量份，通常爲 10〜50重量份，較佳爲20〜4 0重量份左右。第二丙烯酸樹脂之份量相對於全丙烯酸樹脂之不揮發成分1 00重量份若爲1 〇重量份以上，則即使光學薄膜之尺寸變化，黏著層亦追隨此尺寸變化而變動，故液晶元件之周緣部的明亮度與中心部的明亮度之間變成無差異，具有抑制飛白和色斑之傾向，故爲佳，若第二丙烯酸樹脂之份量爲50重量份以下，則可提高於高溫高濕下的接黏性，且令玻璃基板與黏著劑層之間發生浮起和剝落的可能性有變低的傾向，並且有提高再次加工性的傾向，故爲佳。黏著劑中所用之丙烯酸樹脂（A)僅將丙烯酸樹脂（僅使用第一丙烯酸樹脂時爲其丙烯酸樹脂，又混合使用第一丙烯酸樹脂和第二丙烯酸樹脂時爲其混合物）溶解於醋酸乙酯並且調整至不揮發成分濃度20重量％的溶液，於溫度25 °C中顯示l〇Pa· s以下，更且爲0.1〜7Pa*s之黏度爲佳。此 -16- 200811488 黏度若爲1 0 P a · S以下，則可提高於高溫高濕下的接黏性 ’且令玻璃基板與黏著劑層之間發生浮.起和剝落的可能性有變低的傾向，並且有提高再次加工性的傾向，故爲佳。黏度可以布魯克菲爾德黏度計予以測定。本發明中，如上述之丙烯酸樹脂（A)，可加上使用離子性化合物（B)。此離子性化合物（B)爲含有前述式（II)所示之陽離子，於此式（II)中，R3爲表示碳數1〜12個之烷基’ R4、R5及R6爲分別獨立表示碳數6〜12個之烷基。因此’式（II)所示之陽離子爲四烷基銨陽離子。此離子性化合物（B)有利於常溫（23 °C附近）中爲液體。式（II)所示之四烷基銨陽離子爲總碳數爲15個以上，更佳爲20個以上、尤佳爲22個以上，由與丙烯酸樹脂（A)之相溶性的觀點而言爲佳。又，其總碳數爲3 6個以下，再佳爲3 0個以下。式（Π)所示之四烷基銨陽離子的具體例可列舉下列物質。四己基銨陽離子，四辛基銨陽離子，三己基甲基銨陽離子，三辛基甲基銨陽離子，三癸基甲基銨陽離子，三己基乙基銨陽離子，三辛基乙基銨陽離子等。另一方面，構成離子性化合物（B)之陰離子成分爲以 -17- 200811488 滿足成爲離子性液體者爲佳，且其他無特別限定，可列舉例如下列物質。氯陰離子[cr]、溴陰離子[ΒΓ]、碘陰離子[Γ]、 ^ 四氯鋁酸鹽陰離子[A1C14·]、七氯鋁酸鹽陰離子[A12C17_]、四氟硼酸鹽陰離子[BF4·]、六氟磷酸鹽陰離子[PF6·]、過氯酸鹽陰離子[C104·]、硝酸鹽陰離子[N03_]、醋酸鹽陰離子[CH3COCn、三氟醋酸鹽陰離子[CF3COO·]、甲烷磺酸鹽陰離子[CH3S03·]、三氟甲烷磺酸鹽陰離子[CF3S〇r]、雙（三氟甲烷磺醯基）醯亞胺陰離子[(cf3s〇2)2n-]、三（三氟甲烷磺醯基）碳陰離子[(CFsSo^hcrj、六氟砷酸鹽陰離子[AsF6-]、六氟銻酸鹽陰離子[SbF6-]、六氟鈮酸鹽陰離子[NbF6_]、六氟鉅酸鹽陰離子[TaF6·]、 (聚）氫化氟氟化物陰離子[Ρ(ΗΡ)η·](η爲1〜3 > 工右）、二氰醯胺陰離子[(CN)2N_]、全氟丁烷磺酸鹽陰離子[C4F9S〇3-]、 200811488 雙（五氟乙烷磺醯基）醯亞胺陰離子[(c2F5so2)2N·]、全氟丁酸鹽陰離子[c3f7coct]、 (三氟甲烷磺醯基）（三氟甲烷羰基）醯亞胺陰離子 [(cf3so2)(cf3co)n·]等。其中特別以含有氟原子之陰離子成分，因可取得低熔點之離子性化合物故爲較佳使用，尤其以雙（三氟甲烷磺醯基）醯亞胺陰離子爲佳。本發明所用之離子性化合物的具體例可由上述陽離子成分與陰離子成分之組合中適當選擇。具體的陽離子成分與陰離子成分之組合的化合物可列舉下列物質。四己基銨雙（三氟甲烷磺醯基）醯亞胺、三己基甲基銨雙（三氟甲烷磺醯基）醯亞胺、三辛基甲基銨、雙（三氟甲烷磺醯基）醯亞胺、四己基銨六氟磷酸酯、三己基甲基銨六氟磷酸酯、三辛基甲基銨六氟磷酸酯、四己基銨全氯酸酯、三己基甲基銨全氯酸酯、三辛基甲基銨全氯酸酯等。離子性化合物（B)爲相對於前述之丙烯酸樹脂（A)之不揮發成分100重量份，含有0.5〜10重量份左右之比例爲佳，更且，以1〜6重量份之比例爲更佳。相對於丙烯酸樹脂（A)之不揮發成分1〇〇重量份，若離子性化合物（B)含有〇·5重量份以上，則可提高防止帶電性能故爲佳，若爲j 〇重量份以下，則離子性化合物（B)難滲出故爲佳。於如上述之丙烯酸樹脂（A)及離子性化合物（B)中，再配合交聯劑（C)，作成黏著劑組成物。交聯劑（C)爲於丙烯酸樹脂（A)中，特別於分子內具有至少二個可與來自第一 -19- 200811488 丙烯酸樹脂中之不飽和羧酸之構造單位交聯之官能基的化合物，具體而言，可例示異氰酸酯系化合物、環氧系化合物、金屬嵌合系化合物、氮丙啶系化合物等。異氰酸酯系化合物爲於分子內具有至少二個異氰醯基 (-NCO)的化合物，可列舉例如，甲苯二異氰酸酯、己二異氰酸酯、異佛爾酮二異氰酸酯、二異氰酸二甲苯酯、氫化二異氰酸二甲苯酯、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。又，於此等異氰酸酯化合物中，以甘油和三羥甲基丙烯等之多元醇反應的加成物、和將異氰酸酯化合物作成二聚物、三聚物等，亦作爲黏著劑中所用的交聯劑。亦可混合使用二種以上之異氰酸酯系化合物。環氧系化合物爲於分子內具有至少二個以上環氧基的化合物，可列舉例如，雙酚 A型之環氧樹脂、乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、甘油二縮水甘油醚、甘油三縮水甘油醚、1,6-己二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、N，N-二縮水甘油基苯胺、 N，N，N’，N’ -四縮水甘油基-m-二甲苯二胺、l，3-雙（N，N’ - 一縮水甘油胺甲基）環己院等。亦可混合使用二種以上之環氧系化合物。金屬嵌合化合物可列舉例如，於鋁、鐵、銅、鋅、錫、鈦、鎳、銻、鎂、釩、鉻及鉻等之多價金屬中，配位乙醯丙酮和乙醯醋酸乙酯的化合物等。，氮丙啶系化合物爲於分子內具有至少二個亦被稱爲伸 -20- 200811488 乙基亞胺之一個氮原子與二個碳原子所構成之三員環骨架的化合物，可列舉例如，二苯基甲烷-4,4’ -雙（1-氮丙啶羧醯胺）、甲苯-2,4-雙（1-氮丙啶羧醯胺）、三伸乙基蜜胺、異酞醯雙-1-(2-甲基氮丙啶）、三-1-氮丙啶氧化膦、伸己基-1，6-雙（1-氮丙啶羧醯胺）、三羥甲基丙烷-三-氮丙啶基丙酸酯、四羥甲基甲烷-三-/3 -氮丙啶基丙酸酯等。此些交聯劑中，含異氰酸酯系化合物，尤其以苯二甲撐二異氰酸酯或甲苯撐二異氰酸酯、或其異氰酸酯，以甘油和三羥甲基丙烷等多元醇反應的加成物，和令異氰酸酯化合物作成二聚物、三聚物等之混合物，將彼等異氰酸醋系化合物混合者等爲較佳使用。適當的異氰酸酯系化合物可列舉，甲苯撐二異氰酸酯、令甲苯撐二異氰酸酯以多元醇反應的加成體、甲苯撐二異氰酸酯的二聚物、及甲苯撐二異氰酸酯的三聚物。交聯劑（C)爲相對於丙烯酸樹脂（A) 100重量份，通常配合0.01〜10重量份左右、較佳爲0.1〜7重量份左右的比例。相對於丙烯酸樹脂（A) 100重量份若交聯劑（C)的份量爲〇·〇 1重量份以上，則具有提高黏著劑層之耐久性的傾向故爲佳，又，若爲1 〇重量份以下，則將附黏著劑之光學薄膜應用於液晶顯示裝置時的飛白並不明顯，故爲佳。於形成本發明之黏著劑層的黏著劑中，爲了提高黏著劑層與玻璃基板的密黏性，含有矽烷系化合物爲佳，尤其，令配合交聯劑前之丙烯酸樹脂中含有矽烷系化合物爲佳 -21 - 200811488 矽烷系化合物可列舉例如，乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三（2-甲氧乙氧基）矽烷、N-(2-胺乙基）-3-胺丙基甲基二甲氧基矽烷、N-(2-胺乙基）_3·胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-縮水甘油氧丙基三甲氧基矽烷、3 -縮水甘油氧丙基甲基二甲氧基矽烷、2-(3,4·環氧環己基）乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3_甲基丙烯醯氧丙基三甲氧基矽烷、3-氫硫丙基三甲氧基矽烷、3-縮水甘油氧丙基三甲氧基矽烷、3 -縮水甘油氧丙基三乙氧基矽烷、3-縮水甘油氧丙基二甲氧基甲基矽烷、3-縮水甘油氧丙基乙氧基二甲基矽烷等。亦可使用二種以上之矽烷系化合物。矽烷系化合物可爲聚矽氧低聚物型之物質。聚矽氧低聚物若以（單體）低聚物之形式表示，則可列舉例如下列物質。 3 -氫硫丙基三甲氧基矽烷-四甲氧基矽烷共聚物、 3-氫硫丙基三甲氧基矽烷-四乙氧基矽烷共聚物、 3-氫硫丙基三乙氧基矽烷-四甲氧基矽烷共聚物、 3 -氫硫丙基三乙氧基矽烷-四乙氧基矽烷共聚物般之含有氫硫丙基的共聚物；氫硫甲基三甲氧基矽烷-四甲氧基矽烷共聚物、氫硫甲基三甲氧基矽烷四乙氧基矽烷共聚物、氫硫甲基三乙氧基矽烷-四甲氧基矽烷共聚物、氫硫甲基三乙氧基矽烷-四乙氧基矽烷共聚物般之含 22、 200811488 有氫硫甲基的共聚物； 3 -甲基丙烯醯氧丙基三甲氧基矽烷-四甲氧基矽烷共聚物、 3 -甲基丙烯醯氧丙基三甲氧基矽烷-四乙氧基矽烷共聚物、 3-甲基丙烯醯氧丙基三乙氧基矽烷-四甲氧基矽烷共聚物、 3 -甲基丙烯醯氧丙基三乙氧基矽烷·四乙氧基矽烷共聚物、 3-甲基丙烯醯氧丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、 3_甲基丙烯醯氧丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、 3 -甲基丙烯醯氧丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、 3-甲基丙烯醯氧丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物般之含有甲基丙烯醯氧丙基的共聚物； 3-丙烯醯氧丙基三甲氧基矽烷-四甲氧基矽烷共聚物， 3_丙烯醯氧丙基三甲氧基矽烷-四乙氧基矽烷共聚物， 3-丙烯醯氧丙基三乙氧基矽烷-四甲氧基矽烷共聚物， 3-丙烯醯氧丙基三乙氧基矽烷-四乙氧基矽烷共聚物， 3-丙烯醯氧丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物， 3-丙烯醯氧丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚 -23- 200811488 物， 3 -丙烯醯氧丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物， 3 -丙烯醯氧丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物般之含有丙烯醯氧丙基的共聚物；乙烯基三甲氧基矽烷-四甲氧基矽烷共聚物，乙烯基三甲氧基矽烷-四乙氧基矽烷共聚物，乙烯基三乙氧基矽烷-四甲氧基矽烷共聚物，乙烯基三乙氧基矽烷-四乙氧基矽烷共聚物，乙烯基甲基二甲氧基矽烷-四甲氧基矽烷共聚物，乙烯基甲基二甲氧基矽烷-四乙氧基矽烷共聚物，乙烯基甲基二乙氧基矽烷-四甲氧基矽烷共聚物，乙烯基甲基二乙氧基矽烷-四乙氧基矽烷共聚物般之含有乙烯基的共聚物； 3 -胺丙基三甲氧基矽烷-四甲氧基矽烷共聚物， 3 -胺丙基三甲氧基矽烷-四乙氧基矽烷共聚物， 3-胺丙基三乙氧基矽烷-四甲氧基矽烷共聚物， 3-胺丙基三乙氧基矽烷-四乙氧基矽烷共聚物， 3-胺丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物， 3-胺丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物， 3-胺丙基甲基二乙氧基矽烷·四甲氧基矽烷共聚物， 3 ·胺丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物般之含有胺基的共聚物等。此等矽烷系化合物於許多情況爲液體。黏著劑中矽烷 -24- 200811488 系化合物的配合量’相對於丙烯酸樹脂（A)之不揮發成分 100重量份（使用二種以上之情況爲其合計重量）通常爲 0.0001〜10重量份左右，較佳爲使用0.01〜5重量份之比例。相對於丙烯酸樹脂之不揮發成分100重量份’若矽烷系化合物之份量爲0.0001重量份以上，則可提高黏著劑層與玻璃基板的密黏性故爲佳。又，其量若爲1 〇重量份以下，則具有抑制矽烷系化合物由黏著劑層中滲出之傾向，故爲佳。於上述說明之黏著劑中，亦可再配合交聯觸媒、耐氣候安定劑、增黏劑、可塑劑、軟化劑、染料、顏料、無機充塡劑等。其中，若於黏著劑中配合交聯劑及交聯觸媒，則可在短時間的熟化下調製黏著劑層。且於所得之附黏著劑之光學薄膜中，可抑制光學薄膜與黏著劑層之間發生浮起和剝落，且可抑制於黏著劑層內產生發泡，並且再次加工性亦更加良好。交聯觸媒可列舉例如，己二胺、乙二胺、聚伸乙基亞胺 '伸己基四胺、二伸乙基三胺、三伸乙基四胺、異佛爾酮二胺、三亞甲基二胺、聚胺基樹脂、蜜胺樹脂般之胺系化合物等。於黏著劑中配合胺系化合物作爲交聯劑觸媒時，交聯劑之異氰酸酯系化合物爲適當。本發明之附黏著劑之光學薄膜中所用的光學薄膜爲具有光學特性的薄膜，可列舉例如，偏光薄膜、相位差薄膜等。所謂偏光薄膜，係對於自然光等之入射光，具有射出偏光之機能的光學薄膜。於偏光薄膜，具有將某方向具振 -25- 200811488 動面之直線偏光予以吸收，且令具有垂直其之振動面的直線偏光予以穿透之性質的直線偏光薄膜’及具有將某方向具振動面之直線偏光予以反射，且令具有垂直其之振動面的直線偏光予以穿透之性質的偏光分離薄膜，令偏光薄膜與後述之相位差薄膜予以層合的橢圓偏光薄膜等。偏光薄膜、特別爲直線偏光薄膜（亦稱爲偏光子、或偏光子薄膜）的適當具體例可列舉於單軸延拉之聚乙烯醇系樹脂薄膜，將碘和二色性染料等之二色性色素予以吸黏配向者。所謂相位差薄膜，係爲顯示光學異向性的光學薄膜，可列舉例如，令聚乙烯醇、聚碳酸酯、聚酯、多芳基化合物、聚醯亞胺、聚烯烴、環狀聚烯烴、聚苯乙烯、聚颯、聚醚礪、聚偏氟乙烯/聚甲基丙烯酸甲酯、液晶聚酯、乙醯纖維素、乙烯-醋酸乙烯酯共聚物鹼化物、聚氯乙烯等所構成的高分子薄膜延拉1. 〇 1〜6倍左右所得的延拉薄膜等。其中，以聚碳酸酯薄膜和環狀聚烯烴系薄膜予以單軸延拉或雙軸延拉的高分子薄膜爲佳。亦稱爲單軸性相位差薄膜、廣視野角相位差薄膜、低光彈性率相位差薄膜等，對於任一者均可應用。又，經由液晶性化合物之塗佈，配向令光學異向性表現的薄膜、和經由無機層狀化合物之塗佈令光學異向性表現的薄膜，亦可使用作爲相位差薄膜。此類相位差薄膜有稱爲溫度補償型相位差薄膜者，和、由新日本石油（股）以 '' LC Film〃之商品名販售之棒狀液晶爲以扭轉配向的薄膜、由相同之新日本石油（股）以& NH Film〃之商品名販 -26- 200811488 售之棒狀液晶爲以傾斜配向的薄膜、由富士照相軟片（股）以、WV Film〃之商品名販售之圓盤狀液晶爲以傾斜配向的薄膜、由住友化學（股）以★ VAC Film〃之商品名販售之完全雙軸配向型的薄膜，由相同之住友化學（股）以、、new V A C F i 1 m 〃之商品名販售之雙軸配向型的薄膜等。更且，於此等光學薄膜貼黏保護薄膜者，亦可使用作爲光學薄膜。保護薄膜爲使用透明的樹脂薄膜，且此透明樹脂可列舉例如，以三乙醯纖維素和二乙醯纖維素所代表之乙醯纖維素系樹脂、以聚甲基丙烯酸甲酯所代表之甲基丙烯酸系樹脂、聚酯樹脂、聚烯烴系樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚楓樹脂等。於構成保護薄膜之樹脂中，亦可配合水楊酸酯系化合物、二苯酮系化合物、苯并三唑系化合物、三哄系化合物、氰基丙烯酸酯系化合物、鎳錯鹽系化合物等之紫外線吸收劑。保護薄膜可適當使用三乙醯纖維素薄膜等之乙醯纖維素系樹脂薄膜。上述說明之光學薄膜中，直線偏光薄膜爲多於構成其之偏光子，例如，於聚乙烯醇系樹脂所構成之偏光子薄膜的單面或兩面，貼黏保護薄膜的狀態下供使用。又，前述之橢圓偏光薄膜爲將直線偏光薄膜與相位差薄膜予以層合者，此偏光薄膜亦多於偏光子薄膜的單面或兩面，貼黏保護薄膜的狀態。於此類橢圓偏光薄膜，形成本發明之黏著劑層時，通常，於其相位差薄膜側形成黏著劑層。本發明之附黏著劑之光學薄膜，可以其黏著劑層層合至玻璃基板，作成光學層合體。此處，玻璃基板可列舉例 -27- 200811488 如，液晶元件之玻璃基板、防眩用玻璃、太陽眼鏡用玻璃等。其中，於液晶元件前面側（辨視側）之玻璃基板層合附黏著劑之光學薄膜（上偏光薄膜），並於液晶元件背面側之玻璃基板層合另外之附黏著劑之光學薄膜（下偏光薄膜）而成的光學層合體，可使用作爲液晶顯示裝置故爲佳。玻璃基板之材料可列舉例如鹼石灰玻璃、低鹼玻璃、無鹼玻璃等。附黏著劑之光學薄膜爲例如根據，於剝離薄膜上層合黏著劑，並對所得之黏著劑層再層合光學薄膜的方法，於光學薄膜上層合黏著劑，並於其黏著劑層貼合剝離薄膜將其保護，作成附黏著劑之光學薄膜的方法等，則可製造。此處，剝離薄膜可列舉例如，以聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碳酸酯、多芳基化合物等之各種樹脂所構成的薄膜作爲基材，並且於此基材之黏著劑層的接合面，施以如聚矽氧處理般之脫模處理等。將附黏著劑之光學薄膜層合至玻璃基板作成光學層合體上，例如，由如上處理所得之附黏著劑之光學薄膜中，將剝離薄膜予以剝離，並將露出的黏著劑層貼合至玻璃基板之表面即可。本發明之附黏著劑之光學薄膜貼黏至玻璃基板作成光學層合體後，於任何不適造成此光學薄膜由玻璃基板剝離時，黏著劑層爲伴隨光學薄膜而剝離，且於黏著劑層所連接之玻璃基板表面，由於幾乎完全未發生朦矓和糊殘留等，故對剝離後之玻璃基板，可輕易貼回附黏著劑之光學薄膜。即，所謂之再次加工性優良。 -28- 200811488 由本發明之光學層合體所形成的液晶顯示裝置，例如，可使用於包含筆記型、盤頂型、PDA(Personal Digital Assistance，個人數碼助理）等之個人電腦用液晶顯示器、電視、車輛用顯示器、電子辭典、數碼相機、數碼攝錄機、電子桌上計算機、時鐘等。以下，列舉實施例進一步具體說明本發明，但本發明不被此些例所限定。例如，表示使用量或含量之「份」及「％」只要無特別指明則爲重量基準。不揮發成分爲以JIS K5 4 07爲基準之方法測定之値。具體而言，於玻璃皿中以任意重量採取黏著劑溶液，於防爆烤爐中以1 1 5 °C乾燥2小時後之殘留不揮發成分重量，以相對於最初測定之溶液重量的比例表示。重量平均分子量的測定爲於GPC裝置中，依序直列接連配置東梭（股）製之、、TSK gel G6000HXL"二根與、、TSL gel G5000HXL" 二根圓柱，且使用四氫呋喃作爲溶出液，並以試料濃度5 毫克/毫升、試料導入量100微升、溫度40 °c、流速1毫升/分鐘之條件，以換算成聚苯乙烯則可進行測定。首先，示出製造本發明所規定之高分子量第一丙烯酸樹脂例。 [聚合例1] 於具備冷卻管、導氮管、溫度計及攪拌機之反應器中，裝入醋酸乙酯81 ·8份、丙烯酸丁酯77·0份、丙烯酸甲酯2 0· 0份及丙烯酸3.0份之混合溶液，以氮氣取代裝置 -29- 200811488 內之空氣作成不含氧氣，且一邊將內溫升至55 °C。其後，將偶氮雙異丁腈（聚合引發劑）0.14份溶解於醋酸乙酯10 份之溶液予以全量添加。引發劑添加1小時後，一邊於反應器中以添加速度1 7.3份/hr將醋酸乙酯以除去單體之丙烯酸系樹脂濃度爲35%般連續添加，一邊以內溫54〜56°C 保溫1 2小時，最後添加醋酸乙酯，將丙烯酸樹脂之濃度調整爲20%。所得之丙烯酸樹脂以GPC換算成聚苯乙烯之重量平均分子量Mw爲1，560,000、Mw/Mn爲4.7。將其視爲丙烯酸樹脂A1。 [聚合例2] 除了將單體組成變更爲丙烯酸丁酯98.9份及丙烯酸 1 .1份以外，同聚合例1處理取得丙烯酸樹脂溶液。所得之丙烯酸樹脂以GPC換算成聚苯乙烯之重量平均分子量 Mw爲 1，200,000、Mw/Mn爲3.9。將其視爲丙烯酸樹脂 A 2 〇其次，示出製造低分子量之第二丙烯酸樹脂例。 [聚合例3] 於聚合例1所用之相同反應器中，裝入醋酸乙酯222 份、丙烯酸丁酯35份、甲基丙烯酸丁酯44份、丙烯酸甲酯20份及丙烯酸2-羥乙酯1份，以氮氣取代反應器內之空氣後，將內溫上升至7 5 t：。將偶氮雙異丁腈（聚合引發劑）0·55份溶解於醋酸乙酯12.5份之溶液予以全量添加後 -30- 200811488 ，一邊將內溫保持於69〜71 °C且一邊保溫8小時，令反應完成。所得之丙烯酸樹脂以GPC換算成聚苯乙烯之重量平均分子量Mw爲90000。將其視爲丙烯酸樹脂A3。其次，示出使用上述製造之丙烯酸樹脂製造黏著劑，應用於光學薄膜的實施例及比較例。下列例中，使用下列物質作爲離子性化合物。各化合物之記號爲加以供後述參照。以雙（三氟甲烷磺醯）醯亞胺作爲陰離子的化合物1、化合物4、化合物5及化合物6於常溫中爲液體。化合物1 :三辛基甲基銨雙（三氟甲烷磺醯）醯亞胺（具有下式之構造） (cf3so2)2n (?h2)7ch3 ch3 —N —(CH 2)7〇H 3 (CH2)7CH3(Π) (wherein R3 is an alkyl group having 1 to 12 carbon atoms, and R4, R5 and R6 are each independently representing a carbon number of 6 to 12), and a cation-containing ionic compound, and (C) Crosslinker. The above acrylic resin (A) may be composed only of the first acrylic resin specified above, and may be added in addition to the first acrylic resin, and a mixture of acrylic resin (which is regarded as the second acrylic resin) different from the above. Composition. The second acrylic resin may, for example, be a structural unit derived from the (meth) acrylate represented by the above formula (I) as a main component, and having a weight average molecular weight of 50,000 to 500,000. Further, according to the present invention, the optical film with the adhesive is also provided as an optical laminate formed by laminating the adhesive layer side to the glass substrate. [Embodiment] Hereinafter, the present invention will be described in detail. In the present invention, the acrylic resin (A) which is a resin component constituting the adhesive contains a structural unit derived from the (meth) acrylate represented by the above formula (I) as a main component, and further contains one in the molecule. An olefinic double bond and a structural unit derived from an unsaturated residual acid having at least one carboxyl group, and a first acrylic resin having a weight average molecular weight of 800,000 to 2, 〇〇〇, 〇〇〇 200811488. The acrylic resin (A) may be composed only of the first acrylic resin specified herein, and may be composed of a first acrylic resin and a mixture of acrylic resin (which is regarded as a second acrylic resin) different from the acrylic resin. The structural unit derived from the above unsaturated carboxylic acid is regarded as 100 parts by weight based on the entire acrylic resin (A), and is 0. The ratio of 5 to 10 parts by weight is contained in the first acrylic resin. In addition, the term "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid", and "(meth)" when it is called (meth)acrylate or the like is also the same. In the above formula (I) which is a main structural unit of the first acrylic resin, Ri is a hydrogen atom or a methyl group, and R2 is an alkyl group or an aralkyl group having 1 to 14 carbon atoms, preferably an alkyl group. The alkyl group or the aralkyl group represented by R2 may be substituted by alkoxy group having 1 to 1 carbon atoms in each group. The (meth) acrylate represented by the formula (I) may, for example, be a linear chain of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate or lauryl acrylate. Alkyl acrylate; isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, branched alkyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid n-Butyl ester, n-octyl methacrylate, linear linear alkyl methacrylate like lauryl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate Branches such as alkyl methacrylate and the like. When R 2 is an alkyl group substituted by an alkoxy group, that is, a (meth) acrylate represented by the formula (I) when R 2 is an alkoxyalkyl group, specifically, 2-methoxyethyl acrylate can be exemplified. , ethoxy acrylate, 2-methoxyethyl -8 - 200811488 methacrylate, ethoxymethyl methacrylate and the like. When the R2 is an aralkyl group, the (meth) acrylate represented by the formula (I) is specifically exemplified by benzyl acrylate and benzyl methacrylate. In the case of producing a propylene-acrylic acid resin, a compound of any one type may be used as the (meth) propyl laurate of the formula (I), and two or more kinds of compounds may be used. Among them, it is preferred to use butyl acrylate as at least one monomer. Therefore, the structural unit derived from the (meth) acrylate constituting the first acrylic resin preferably contains a unit derived from butyl acrylate. The unsaturated carboxylic acid which is another structural unit of the first acrylic resin is a compound having an olefinic double bond and at least one carboxyl group in the molecule, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, and itaconic acid. Acid, etc. Among them, acrylic acid or methacrylic acid is also suitable. Further, the first acrylic resin may contain a structural unit derived from a monomer having a polar functional group other than a carboxyl group. The polar functional group other than the carboxyl group may, for example, be a hydroxyl group, a decylamino group, an epoxy group, an oxocyclobutane group, an amine group, an isocyanoguanidinyl group, an aldehyde group or the like. The monomer having a polar functional group of a hydroxyl group may, for example, be 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate. The polar functional group is a guanamine-based monomer, and examples thereof include acrylamide, methacrylamide, N,N-dimethylaminopropyl acrylamide, N,N-dimethyl decylamine, and N. , N-diethyl acrylamide, N-methylol acrylamide, and the like. The monomer having a polar functional group is an epoxy group, and examples thereof include glycidyl acrylate, glycidyl methacrylate, 3,4·epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexyl methacrylate. Methyl ester, etc. The polar functional group-9-200811488 is a monomer of the oxycyclobutane group, and examples thereof include 'oxycarbonylcyclobutane ester (meth)acrylate, (meth)acrylic acid 3-oxocyclobutanylmethyl ester, Methyl)acrylic acid (3-methyl-3-oxocyclobutanyl) methyl ester, (meth)propionic acid (3_ethyl-3-oxocyclobutanyl) methyl ester, etc., polar functional group The monomer of the amine group may, for example, be N,N-dimethylaminoethyl acetonate or oxime. The monomer having a polar functional group is an isocyanate group, and examples thereof include 2-methacryloyloxyethyl isocyanate. Further, the monomer having a polar functional group is an aldehyde group, and examples thereof include acrylaldehyde and the like. In the first acrylic resin, the structural unit derived from the (meth) acrylate represented by the formula (I) usually contains 60 to 99 based on the total weight of the nonvolatile components. 5% by weight, preferably 80 to 99.5% by weight. Further, the structural unit derived from the unsaturated carboxylic acid is usually from about 0.5 to 10% by weight, preferably from 1 to 6% by weight. The structural unit derived from the unsaturated carboxylic acid is 1 part by weight with respect to the entire acrylic resin (A), that is, when the acrylic resin (A) is composed only of the first acrylic resin, 'relative to 1 〇 0 parts by weight, When it is composed of the first acrylic resin and the second acrylic resin different therefrom, it contains 0 parts by weight with respect to 100 parts by weight of the total. A ratio of 5 to 10 parts by weight. The ratio of the structural unit derived from the unsaturated carboxylic acid is preferably 0% by weight based on 100 parts by weight of the entire acrylic resin (A). 5 to 6 parts by weight. With respect to 100 parts by weight of the acrylic resin (A), if the amount of the structural unit derived from the unsaturated carboxylic acid is 0. When the adhesive layer containing the adhesive layer is bonded to the glass substrate in an amount of 5% by weight or more, the floating and peeling between the glass substrate and the adhesive layer tend to be suppressed, which is preferable. In addition, when the amount is 10 parts by weight or less, even if the size of the optical film changes due to a temperature change or the like, the layer of the adhesive-10-200811488 can be changed in accordance with the dimensional change, so that the brightness of the peripheral portion of the liquid crystal element is There is no difference in the brightness of the center portion, and it is preferable to have a tendency to suppress whitening and staining. Further, with respect to 100 parts by weight of the acrylic resin (A), if the amount of the structural unit derived from the unsaturated carboxylic acid is 0. The range of 5 to 10 parts by weight is also preferable from the viewpoint of compatibility with the ionic compound (B) described later. The first acrylic resin may also contain a structural unit of the (meth) acrylate represented by the above formula (I) and a monomer other than the above unsaturated carboxylic acid. The monomer which can be used arbitrarily is, for example, a heterocyclic monomer having one olefinic double bond and at least one heterocyclic group of five or more members in the molecule. Here, the heterocyclic group of the above five-membered ring means an alicyclic hydrocarbon group having 5 or more carbon atoms, preferably 5 to 7 carbon atoms, wherein at least one methylene group is a nitrogen atom. a group substituted with a hetero atom such as an oxygen atom or a sulfur atom. Specific examples of the heterocyclic monomer include propylene morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, and caprolactone modification. Tetrahydrofurfuryl acrylate and the like. Further, the hetero atom such as 3,4-epoxycyclohexylmethyl acrylate or 3,4-epoxycyclohexylmethyl methacrylate is a monomer having a three-membered ring and a seven-membered ring. The ring group can be operated in a heterocyclic monomer type. Further, as in the case of 2,5-dihydrofuran, an olefinic double bond may be contained in the heterocyclic group. The heterocyclic monomer may also use two or more different monomers. The heterocyclic monomer is also preferably N-vinylpyrrolidone, vinyl caprolactam, propylene morpholine or a mixture thereof. When the first acrylic resin contains a structural unit derived from a heterocyclic monomer, -11 - 200811488, the amount thereof is usually about 30% by weight, preferably 20% by weight or less, based on the first acrylic resin. In addition, if the first acrylic resin contains 0. When 1% by weight or more is derived from the structural unit of the heterocyclic monomer, even if the size of the optical film changes, the dimensional change follows the change of the adhesive layer, so that the brightness of the peripheral portion of the liquid crystal element and the brightness of the central portion become No difference, there is a tendency to inhibit blushing and staining. Further, other monomers which can be optionally used include alicyclic monomers having one olefinic double bond and at least one alicyclic structure in the molecule. The alicyclic structure is usually a naphthene structure or a cycloolefin structure having 5 or more carbon atoms, preferably 5 to 7 carbon atoms, and has an olefinic double bond in the alicyclic structure in the cycloolefin structure. Specifically, examples of the acrylate having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methylcyclohexyl acrylate, and trimethylcyclohexyl acrylate. Ester, tert-butyl ring of acrylic acid. Hexyl ester, cyclohexyl α-ethoxy acrylate, cyclohexyl phenyl acrylate, etc., and methacrylates having an alicyclic structure include isobornyl methacrylate, cyclohexyl methacrylate, and methacrylic acid. Cyclopentyl ester, cyclododecyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, t-butylcyclohexyl methacrylate, cyclohexyl phenyl methacrylate Wait. Further, examples of the acrylate having a plurality of alicyclic structures in the molecule include dicyclohexyl methyl itaconate, dicyclooctyl itaconate, and dicyclododecyl succinate. Further, vinyl vinyl cyclohexyl acetate having a vinyl group or the like can also be used as the alicyclic monomer. Among them, isobornyl acrylate, cyclohexyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, and dicyclopentanyl acrylate are preferred because of -12-200811488. The alicyclic monomer may also be used in combination of two or more kinds of compounds. When the first acrylic resin contains a structural unit derived from an alicyclic monomer, the amount thereof is usually about 30% by weight, preferably 15% by weight or less, based on the first acrylic resin. In addition, if the first acrylic resin contains 0. 1% by weight or more, and more preferably 1% by weight or more, from the structural unit of the alicyclic monomer, tends to suppress floating and peeling between the glass substrate and the adhesive layer. Further, as the other monomer, any of the (meth) acrylate, the heterocyclic monomer, and the alicyclic monomer represented by the formula (I) may be a different vinyl monomer. Examples of such a vinyl monomer include a fatty acid vinyl ester 'halogenated vinyl group, a halogenated vinylene group, a (meth)acrylonitrile, a conjugated diene compound, an aromatic vinyl group, and the like. Here, the fatty acid vinyl ester may, for example, be vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate or the like. The halogenated vinyl group may, for example, be vinyl chloride or vinyl bromide. Further, the halogenated vinylene group is exemplified by vinylidene chloride, and the (meth)acrylonitrile is exemplified by acrylonitrile and methyl acrylonitrile. The conjugated diene compound is an olefin having a conjugated double bond in the molecule, and specific examples thereof include isoprene, butadiene, and chlorobutene. The aromatic vinyl group is a compound having an aromatic ring and a vinyl group, and specific examples thereof include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, and diethyl styrene. Triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodine styrene , -13- 200811488 Nitrostyrene, styrene styrene, styrene-like styrene monomer, vinyl pyridine and vinyl carbazole-containing nitrogen-containing aromatic vinyl. These vinyl monomers may be used in combination with two or more different compounds. When the first acrylic resin contains a structural unit derived from the vinyl monomer as described above, the amount thereof is based on the first acrylic resin. Usually 5% by weight or less, preferably 0. It is 05% by weight or less, but it is more preferably contained substantially. When a structural unit derived from a heterocyclic monomer, a structural unit derived from an alicyclic monomer, and a structural unit derived from a vinyl monomer are introduced into a plurality of units, the total amount thereof is based on the first acrylic resin. It is preferably 30% by weight or less, more preferably 20% by weight or less. The method for producing the first acrylic resin described above may, for example, be a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method or the like, and a solution polymerization method is also preferred. Specific examples of the solution polymerization method include a mixture of a desired monomer and an organic solvent to prepare a mixed solution having a monomer concentration of 50% by weight or more, preferably 50 to 60% by weight, and then a nitrogen atmosphere. Next, the total of the monomers is added every 100 parts by weight. 00 1 to 5 parts by weight of a polymerization initiator, and a method of stirring at about 40 to 90 ° C, preferably about 50 to 70 ° C for 8 hours or longer, preferably 8 to 12 hours or so. As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like can be used. The photopolymerization initiator may, for example, be 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone or the like. The thermal polymerization initiator may, for example, be 2,2,-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1,-azobis(cyclohexane- :^carbonitrile) -14- 200811488, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxy An azo compound such as valeronitrile; dimethyl-2,2'-azobis(2-propionic acid methyl ester) or 2,2'-azobis(2-hydroxymethylpropionitrile); Peroxidic lauryl hydrazine, tert-butyl hydroperoxide, benzammonium peroxide, tert-butylperoxybenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, di-negative Propylperoxydicarbonate, tert-butylperoxy neodecanoate, tert-butylperoxy pivalate, (3,5,5-trimethylhexyl) peroxide Common organic peroxides, potassium persulfate, ammonium persulfate, inorganic peroxide like hydrogen peroxide. Further, a redox initiator such as a peroxide or a reducing agent may be used as a polymerization initiator. The organic solvent used in the polymerization reaction may, for example, be an aromatic hydrocarbon such as toluene or xylene, an ester of ethyl acetate or butyl acetate; an aliphatic alcohol such as n-propanol or isopropanol; acetone; Methyl ethyl ketone, methyl isobutyl ketone like ketones, and the like. The molecular weight of the first acrylic resin is converted into a polystyrene weight average molecular weight (Mw) in the range of 800,000 to 2,000,000 by gel permeation chromatography (GPC). When the weight average molecular weight is 800,000 or more, the adhesion at high temperature and high humidity can be improved, and the possibility of floating and peeling between the glass substrate and the adhesive layer tends to be low, and there is a tendency to improve again. The tendency to workability is good. In addition, when the weight average molecular weight is 2,000,000 or less, the size of the optical film to which the pressure-sensitive adhesive layer is bonded changes with temperature or the like, and the adhesive layer changes in accordance with the dimensional change, so that the peripheral portion of the liquid crystal element There is no difference between the brightness and the brightness of the center portion, and it is preferable to suppress the tendency of whitening and color spots. The molecular weight distribution expressed by the ratio (Mw/Mn) of the weight average fraction -15 - 200811488 sub-quantity (Mw) to the number average molecular weight (?n) is usually in the range of about 2 to 10. The adhesive used in the present invention may further contain, as the acrylic resin (A), a second acrylic resin different from the above first acrylic resin. The second acrylic resin which may be further contained may, for example, be a structural unit derived from the (meth) acrylate represented by the above formula (I) as a main component, and converted into a weight average molecular weight of a standard polystyrene according to GPC. (Mw) is a low molecular weight substance in the range of about 50,000 to 500,000. When the second acrylic resin having a low molecular weight is used, the amount thereof is usually 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the total of the nonvolatile components of the acrylic resin (A). When the amount of the second acrylic resin is 1 part by weight or more based on 100 parts by weight of the non-volatile component of the all-acrylic resin, even if the size of the optical film changes, the adhesive layer changes in accordance with the dimensional change, so the periphery of the liquid crystal element It is preferable that there is no difference between the brightness of the portion and the brightness of the center portion, and it is preferable to suppress the whitening and the color unevenness. When the amount of the second acrylic resin is 50 parts by weight or less, the temperature can be improved under high temperature and high humidity. The adhesion is increased, and the possibility of floating and peeling between the glass substrate and the adhesive layer tends to be low, and the reworkability tends to be improved. The acrylic resin (A) used in the adhesive dissolves only the ethyl acetate (only a mixture of the acrylic resin and the first acrylic resin and the second acrylic resin when the first acrylic resin is used) and is dissolved in ethyl acetate. The solution adjusted to a concentration of 20% by weight of the non-volatile component showed a temperature below 25 ° C and a value of 0 〇Pa· s or less. The viscosity of 1~7Pa*s is better. This -16- 200811488 viscosity is 10 P a · S or less, which can improve the adhesion under high temperature and high humidity ‘ and float between the glass substrate and the adhesive layer. The possibility of lifting and peeling tends to be low, and there is a tendency to improve reworkability, so it is preferable. Viscosity can be measured by a Brookfield viscometer. In the present invention, the ionic compound (B) may be added as the above-mentioned acrylic resin (A). The ionic compound (B) is a cation represented by the above formula (II), and in the formula (II), R3 is an alkyl group having 1 to 12 carbon atoms, and R4, R5 and R6 each independently represent carbon. A number of 6 to 12 alkyl groups. Therefore, the cation represented by the formula (II) is a tetraalkylammonium cation. This ionic compound (B) is advantageous for liquid at normal temperature (near 23 ° C). The tetraalkylammonium cation represented by the formula (II) has a total carbon number of 15 or more, more preferably 20 or more, and particularly preferably 22 or more, and is compatible with the acrylic resin (A). good. Further, the total carbon number is 36 or less, and preferably more than 30. Specific examples of the tetraalkylammonium cation represented by the formula (Π) include the following. Tetrahexylammonium cation, tetraoctyl ammonium cation, trihexylmethylammonium cation, trioctylmethylammonium cation, trimethylmethylammonium cation, trihexylethylammonium cation, trioctylethylammonium cation, and the like. On the other hand, the anion component constituting the ionic compound (B) is preferably an ionic liquid in the range of -17 to 200811488, and the others are not particularly limited, and examples thereof include the following. Chloride anion [cr], bromine anion [ΒΓ], iodine anion [Γ], ^ tetrachloroaluminate anion [A1C14·], heptachloroaluminate anion [A12C17_], tetrafluoroborate anion [BF4·], Hexafluorophosphate anion [PF6·], perchlorate anion [C104·], nitrate anion [N03_], acetate anion [CH3COCn, trifluoroacetate anion [CF3COO·], methanesulfonate anion [CH3S03 ·], trifluoromethanesulfonate anion [CF3S〇r], bis(trifluoromethanesulfonyl) quinone imine [(cf3s〇2)2n-], tris(trifluoromethanesulfonyl)carbon anion [(CFsSo^hcrj, hexafluoroarsenate anion [AsF6-], hexafluoroantimonate anion [SbF6-], hexafluoroantimonate anion [NbF6_], hexafluorophosphate anion [TaF6·], ( Poly)hydrogenated fluorofluoride anion [Ρ(ΗΡ)η·] (η is 1~3 > Gongyou), dicyandiamide anion [(CN)2N_], perfluorobutanesulfonate anion [C4F9S〇 3-], 200811488 bis(pentafluoroethanesulfonyl) quinone imine [(c2F5so2)2N·], perfluorobutyrate anion [c3f7coct], (trifluoromethanesulfonyl) (trifluoromethane a quinone imine anion [(cf3so2)(cf3co)n·], etc. Among them, an anion component containing a fluorine atom is particularly preferably used because it can obtain an ionic compound having a low melting point, especially bis(trifluoromethane) The sulfonyl) quinone imine anion is preferred. Specific examples of the ionic compound used in the present invention can be appropriately selected from the combination of the above cationic component and anionic component. Specific examples of the compound of the cationic component and the anionic component include the following. Tetrahexylammonium bis(trifluoromethanesulfonyl) quinone imine, trihexylmethylammonium bis(trifluoromethanesulfonyl) quinone imine, trioctylmethylammonium, bis(trifluoromethanesulfonyl) Yttrium, tetrahexylammonium hexafluorophosphate, trihexylmethylammonium hexafluorophosphate, trioctylmethylammonium hexafluorophosphate, tetrahexylammonium perchlorate, trihexylmethylammonium perchlorate , octylmethylammonium perchlorate, etc. The ionic compound (B) is contained in an amount of 0.1 part by weight based on 100 parts by weight of the nonvolatile component of the acrylic resin (A). A ratio of about 5 to 10 parts by weight is more preferable, and a ratio of 1 to 6 parts by weight is more preferable. When the ionic compound (B) is contained in an amount of 5% by weight or more based on 1 part by weight of the non-volatile component of the acrylic resin (A), it is preferable to improve the charging performance, and if it is not more than j 〇 by weight, It is preferred that the ionic compound (B) is difficult to bleed out. In the acrylic resin (A) and the ionic compound (B) as described above, a crosslinking agent (C) is further blended to prepare an adhesive composition. The crosslinking agent (C) is a compound having an at least two functional groups in the molecule which are crosslinkable with a structural unit derived from an unsaturated carboxylic acid in the first -19-200811488 acrylic resin in the acrylic resin (A). Specifically, an isocyanate compound, an epoxy compound, a metal chimeric compound, an aziridine compound, or the like can be exemplified. The isocyanate compound is a compound having at least two isocyanato groups (-NCO) in the molecule, and examples thereof include toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, ditolyl diisocyanate, and hydrogenation. Xylyl diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like. Further, among the isocyanate compounds, an adduct obtained by reacting a polyhydric alcohol such as glycerin and trimethylol propylene, and an isocyanate compound as a dimer or a trimer are also used as crosslinks for use in an adhesive. Agent. Two or more kinds of isocyanate compounds may be used in combination. The epoxy compound is a compound having at least two epoxy groups in the molecule, and examples thereof include a bisphenol A type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and glycerin. Diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N,N-diglycidylaniline, N,N,N', N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N'-glycidylaminemethyl)cyclohexanthes and the like. Two or more epoxy compounds may be used in combination. The metal chiral compound may, for example, be a complex of a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, ruthenium, magnesium, vanadium, chromium or chromium, and is coordinated with ethyl acetonide and ethyl acetate. Compounds, etc. The aziridine-based compound is a compound having at least two three-membered ring skeletons, which are also referred to as a nitrogen atom and two carbon atoms of an ethylimine of -20-200811488, in the molecule, for example, Diphenylmethane-4,4'-bis(1-aziridinecarboxamide), toluene-2,4-bis(1-aziridinecarboxamide), tri-ethyl melamine, isoindole Bis-1-(2-methylaziridine), tri-1-aziridine phosphine oxide, exohexyl-1,6-bis(1-aziridine carboxamide), trimethylolpropane-three - aziridine propionate, tetramethylol methane-tri-/3-aziridine propionate, and the like. Among these crosslinking agents, isocyanate-containing compounds, especially xylylene diisocyanate or tolylene diisocyanate, or isocyanates thereof, adducts which are reacted with a polyol such as glycerin and trimethylolpropane, and isocyanate The compound is preferably used as a mixture of a dimer, a trimer or the like, and a mixture of such isocyanate-based compounds. Suitable isocyanate-based compounds include tolylene diisocyanate, an adduct of toluene diisocyanate which is reacted with a polyhydric alcohol, a dimer of tolylene diisocyanate, and a terpolymer of tolylene diisocyanate. The crosslinking agent (C) is 100 parts by weight relative to the acrylic resin (A), usually 0. 01~10 parts by weight, preferably 0. A ratio of about 1 to 7 parts by weight. When the amount of the crosslinking agent (C) is not more than 1 part by weight based on 100 parts by weight of the acrylic resin (A), the durability of the pressure-sensitive adhesive layer is improved, and the weight is preferably 1 〇. In the following, it is preferable that the optical film with an adhesive is applied to a liquid crystal display device without being noticeable. In the adhesive for forming the adhesive layer of the present invention, in order to improve the adhesion between the adhesive layer and the glass substrate, a decane-based compound is preferable, and in particular, the decane-based compound is contained in the acrylic resin before the crosslinking agent is added.佳-21 - 200811488 The decane-based compound may, for example, be vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)_3.aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropane Trimethoxy decane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4·epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy Basear, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropyldimethoxymethylnonane, 3-glycidoxypropylethoxydi Methyl decane, etc. Two or more decane-based compounds may also be used. The decane compound may be a polyoxo oligomer type. The polyoxymethylene oligomer is, for example, in the form of a (monomer) oligomer, and examples thereof include the following. 3-Hydroxythiopropyltrimethoxydecane-tetramethoxydecane copolymer, 3-hydrothiopropyltrimethoxydecane-tetraethoxydecane copolymer, 3-hydrothiopropyltriethoxydecane- a tetramethoxy decane copolymer, a copolymer containing a hydrogen thiopropyl group as a copolymer of 3-hydrothiopropyltriethoxydecane-tetraethoxydecane; hydrogen thiomethyltrimethoxy decane-tetramethoxy Base argon copolymer, hydrogen thiomethyltrimethoxy decane tetraethoxy decane copolymer, hydrogen thiomethyl triethoxy decane-tetramethoxy decane copolymer, hydrogen thiomethyl triethoxy decane - four Ethoxy decane copolymer containing 22, 200811488 copolymer with hydrogen thiomethyl group; 3-methyl propylene oxypropyl trimethoxy decane-tetramethoxy decane copolymer, 3-methyl propylene oxime Propyltrimethoxydecane-tetraethoxydecane copolymer, 3-methacryloxypropyltriethoxydecane-tetramethoxydecane copolymer, 3-methylpropenyloxypropyltriethoxylate Base decane-tetraethoxy decane copolymer, 3-methylpropenyl propyl propyl dimethoxy decane-tetramethoxy decane copolymer, 3-methyl Iridium oxypropylmethyldimethoxydecane-tetraethoxydecane copolymer, 3-methacryloxypropylmethyldiethoxydecane-tetramethoxydecane copolymer, 3-methyl Copolymer containing methacryloxypropyl propyl as a copolymer of propylene oxypropylmethyldiethoxy decane-tetraethoxy decane; 3-propenyloxypropyltrimethoxydecane-tetramethoxy Decane copolymer, 3_propylene oxypropyl trimethoxy decane-tetraethoxy decane copolymer, 3-propenyl methoxypropyl triethoxy decane-tetramethoxy decane copolymer, 3-propene oxime Propylene triethoxy decane-tetraethoxy decane copolymer, 3-propenyl methoxypropyl methyl dimethoxy decane-tetramethoxy decane copolymer, 3-propenyl methoxypropyl methyl dimethyl Oxydecane-tetraethoxydecane copolymerization-23- 200811488, 3-propenylmethoxypropylmethyldiethoxydecane-tetramethoxydecane copolymer, 3-propenyloxypropylmethyldiethyl a copolymer containing a propylene oxypropyl group as a oxy decane-tetraethoxy decane copolymer; a vinyl trimethoxy decane-tetramethoxy decane copolymer, ethylene Trimethoxy decane-tetraethoxy decane copolymer, vinyl triethoxy decane-tetramethoxy decane copolymer, vinyl triethoxy decane-tetraethoxy decane copolymer, vinyl methyl a dimethoxy decane-tetramethoxy decane copolymer, a vinyl methyl dimethoxy decane-tetraethoxy decane copolymer, a vinyl methyl diethoxy decane-tetramethoxy decane copolymer, Copolymer containing vinyl group like vinyl methyl diethoxy decane-tetraethoxy decane copolymer; 3-aminopropyl trimethoxy decane-tetramethoxy decane copolymer, 3-aminopropyl trimethyl a oxydecane-tetraethoxydecane copolymer, a copolymer of 3-aminopropyltriethoxydecane-tetramethoxydecane, a copolymer of 3-aminopropyltriethoxydecane-tetraethoxydecane, 3-aminopropylmethyldimethoxydecane-tetramethoxydecane copolymer, 3-aminopropylmethyldimethoxydecane-tetraethoxydecane copolymer, 3-aminopropylmethyldi Ethoxy decane tetramethoxy decane copolymer, 3 · aminopropyl methyl diethoxy decane - tetraethoxy decane copolymer Copolymers, etc. These decane-based compounds are liquid in many cases. The amount of the decane-24-200811488 compound to be added in the adhesive is 100% by weight relative to the non-volatile component of the acrylic resin (A) (the total weight is used in the case of using two or more kinds). 0001~10 parts by weight, preferably 0. The ratio of 01 to 5 parts by weight. The amount of the monomer component of the non-volatile component relative to the non-volatile component of the acrylic resin is 0. When the amount is 0001 parts by weight or more, the adhesion between the pressure-sensitive adhesive layer and the glass substrate can be improved. Further, when the amount is less than 1 part by weight, it is preferable because the decane-based compound is prevented from oozing out of the adhesive layer. In the above-mentioned adhesive, a cross-linking catalyst, a weather-resistant stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, and the like may be further blended. Among them, when a crosslinking agent and a crosslinking catalyst are blended in the adhesive, the adhesive layer can be prepared in a short time of aging. Further, in the obtained optical film with an adhesive, occurrence of floating and peeling between the optical film and the adhesive layer can be suppressed, and foaming in the adhesive layer can be suppressed, and the reworkability is further improved. The cross-linking catalyst may, for example, be hexamethylenediamine, ethylenediamine, polyethyleneimine, exohexyltetramine, diethylidenetriamine, triethylidenetetraamine, isophoronediamine, Sanya. A methyl diamine, a polyamine resin, an amine compound such as a melamine resin, or the like. When an amine compound is blended as a crosslinking agent catalyst in the adhesive, an isocyanate compound of a crosslinking agent is suitable. The optical film used in the optical film with an adhesive of the present invention is a film having optical characteristics, and examples thereof include a polarizing film and a retardation film. The polarizing film is an optical film that emits polarized light for incident light such as natural light. In the polarizing film, there is a linear polarizing film which absorbs linear polarized light having a moving surface of -25-200811488 in a certain direction, and a linear polarized light having a vertical vibration surface thereof is penetrated and has a vibration in a certain direction A polarized light-separating film in which a linear polarized light of a surface is reflected and a linearly polarized light having a vibration surface perpendicular thereto is penetrated, and an elliptically polarizing film in which a polarizing film and a retardation film to be described later are laminated is used. A specific example of a polarizing film, particularly a linear polarizing film (also referred to as a polarizing film or a polarizing film) is a uniaxially stretched polyvinyl alcohol resin film, and two colors of iodine and a dichroic dye are used. Sex pigments are used to attract adhesives. The retardation film is an optical film which exhibits optical anisotropy, and examples thereof include polyvinyl alcohol, polycarbonate, polyester, polyarylate, polyimine, polyolefin, and cyclic polyolefin. High in polystyrene, polyfluorene, polyether oxime, polyvinylidene fluoride/polymethyl methacrylate, liquid crystal polyester, acetyl cellulose, ethylene-vinyl acetate copolymer alkalinium, polyvinyl chloride, etc. Molecular film stretching 1. 延 1 to 6 times the obtained stretched film and the like. Among them, a polymer film in which a polycarbonate film and a cyclic polyolefin film are uniaxially stretched or biaxially stretched is preferred. Also known as a uniaxial retardation film, a wide viewing angle retardation film, or a low photoelasticity retardation film, it can be applied to any of them. Further, a film which exhibits an optical anisotropy by a coating of a liquid crystal compound and a film which exhibits optical anisotropy by coating with an inorganic layered compound can also be used as a retardation film. Such a retardation film is a film called a temperature-compensated retardation film, and a bar-shaped liquid crystal sold by Nippon Oil Co., Ltd. under the trade name "LC Film" is a film which is twisted and aligned, and is the same. Nippon Oil Co., Ltd. is sold under the trade name of Fujifilm Photo Film Co., Ltd., under the trade name of Fujifilm Photo Film Co., Ltd., under the trade name of Panasonic -26-200811488. The discotic liquid crystal is a film that is obliquely aligned, and a completely biaxially oriented film sold by Sumitomo Chemical Co., Ltd. under the trade name of ★ VAC Film〃, by the same Sumitomo Chemical Co., Ltd., new VACF i A biaxial alignment type film sold under the trade name of 1 m 〃. Furthermore, these optical film adhesive protective films can also be used as optical films. The protective film is a transparent resin film, and the transparent resin may, for example, be an acetaminocellulose resin represented by triethyl fluorene cellulose and diethyl fluorene cellulose, and a group represented by polymethyl methacrylate. Acrylic resin, polyester resin, polyolefin resin, polycarbonate resin, polyether ether ketone resin, poly maple resin, and the like. In the resin constituting the protective film, a salicylate-based compound, a benzophenone-based compound, a benzotriazole-based compound, a triterpenoid compound, a cyanoacrylate-based compound, a nickel-salted salt-based compound, or the like may be blended. UV absorber. As the protective film, an acetaminocellulose-based resin film such as a triacetone cellulose film can be suitably used. In the optical film described above, the linear polarizing film is more than a polarizer constituting the optical film, and is used in a state in which a protective film is adhered to one surface or both surfaces of a polarizing film composed of a polyvinyl alcohol resin. Further, the elliptically polarizing film is formed by laminating a linear polarizing film and a retardation film, and the polarizing film is also more than one side or both sides of the polarizing film, and the protective film is adhered. When such an elliptically polarizing film is formed into the adhesive layer of the present invention, an adhesive layer is usually formed on the side of the retardation film. The optical film with an adhesive of the present invention can be laminated to a glass substrate with an adhesive layer to form an optical laminate. Here, examples of the glass substrate include, for example, a glass substrate for a liquid crystal element, an antiglare glass, and a glass for sunglasses. Wherein, an optical film (upper polarizing film) to which an adhesive is attached is laminated on a glass substrate on the front side (viewing side) of the liquid crystal element, and an additional optical film with an adhesive is laminated on the glass substrate on the back side of the liquid crystal element (under The optical laminate formed of the polarizing film can be preferably 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, for example, a method in which an adhesive is laminated on a release film, and an optical film is laminated on the obtained adhesive layer, an adhesive is laminated on the optical film, and the adhesive layer is laminated and peeled off. The film can be produced by protecting it as a method of forming an optical film with an adhesive. Here, as the release film, for example, a film composed of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate is used as a substrate, and The bonding surface of the adhesive layer of the substrate is subjected to a release treatment such as polyfluorination treatment. The optical film with an adhesive is laminated to the glass substrate to form an optical laminate. For example, in the optical film with the adhesive obtained as described above, the release film is peeled off, and the exposed adhesive layer is bonded to the glass. The surface of the substrate can be used. After the optical film with the adhesive of the present invention is adhered to the glass substrate to form an optical laminate, when the optical film is peeled off from the glass substrate by any discomfort, the adhesive layer is peeled off accompanying the optical film and is bonded to the adhesive layer. Since the surface of the glass substrate is almost completely free from flaws and paste, the optical film to which the adhesive is attached can be easily attached to the glass substrate after peeling. That is, the so-called reworkability is excellent. -28- 200811488 The liquid crystal display device formed by the optical laminate of the present invention can be used, for example, for a liquid crystal display for personal computers including a notebook type, a disk top type, a PDA (Personal Digital Assistance), and the like. Vehicle display, electronic dictionary, digital camera, digital camcorder, electronic desktop computer, clock, etc. Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples. For example, "parts" and "%" indicating the amount or content of use are based on weight unless otherwise specified. The nonvolatile matter is measured by a method based on JIS K5 4 07. Specifically, the adhesive solution was taken in an arbitrary weight in a glass dish, and the weight of the residual non-volatile component after drying at 1 15 ° C for 2 hours in an explosion-proof oven was expressed as a ratio with respect to the weight of the solution initially measured. The weight average molecular weight is determined by sequentially arranging, in series, TSK gel G6000HXL" two and, TSL gel G5000HXL" two cylinders in the GPC apparatus, and using tetrahydrofuran as the eluate, and The measurement was carried out by converting to polystyrene at a sample concentration of 5 mg/ml, a sample introduction amount of 100 μl, a temperature of 40 ° C, and a flow rate of 1 ml/min. First, an example of producing a high molecular weight first acrylic resin prescribed by the present invention is shown. [Polymerization Example 1] In a reactor equipped with a cooling pipe, a nitrogen conduit, a thermometer, and a stirrer, 81. 8 parts of ethyl acetate, 77.0 parts of butyl acrylate, 20.0 parts of methyl acrylate, and acrylic acid were charged. 3. Mixing solution of 0 parts, replacing the air in the device -29- 200811488 with oxygen to form oxygen-free, and raising the internal temperature to 55 °C. Thereafter, azobisisobutyronitrile (polymerization initiator) is 0. 14 parts of the solution dissolved in 10 parts of ethyl acetate were added in full. After the initiator was added for 1 hour, the addition speed was 1 in the reactor. 3 parts/hr of ethyl acetate was continuously added at a concentration of 35% of the acrylic resin to remove the monomer, and the temperature was kept at an internal temperature of 54 to 56 ° C for 12 hours. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20%. The weight average molecular weight Mw of the obtained acrylic resin in terms of GPC to polystyrene was 1,560,000, and Mw/Mn was 4. 7. Think of it as acrylic resin A1. [Polymerization Example 2] except that the monomer composition was changed to butyl acrylate 98. 9 parts and acrylic 1 . The acrylic resin solution was obtained by the same treatment as in Polymerization Example 1 except for one part. The obtained acrylic resin had a weight average molecular weight Mw of 1,200,000 and a Mw/Mn of 3. 9. This is regarded as an acrylic resin A 2 〇 Next, an example of producing a second acrylic resin having a low molecular weight is shown. [Polymerization Example 3] In the same reactor as used in Polymerization Example 1, 222 parts of ethyl acetate, 35 parts of butyl acrylate, 44 parts of butyl methacrylate, 20 parts of methyl acrylate, and 2-hydroxyethyl acrylate were charged. After replacing the air in the reactor with nitrogen, the internal temperature was raised to 7 5 t:. 0. 55 parts of azobisisobutyronitrile (polymerization initiator) was dissolved in ethyl acetate. After 5 parts of the solution was added in its entirety, -30-200811488, while maintaining the internal temperature at 69 to 71 °C for 8 hours, the reaction was completed. The obtained acrylic resin was converted into polystyrene by GPC, and the average molecular weight Mw was 90,000. This was regarded as acrylic resin A3. Next, examples and comparative examples in which an adhesive is produced using the acrylic resin produced above and applied to an optical film are shown. In the following examples, the following materials were used as the ionic compound. The symbols of the respective compounds are referred to for later reference. Compound 1, Compound 4, Compound 5 and Compound 6 which are bis(trifluoromethanesulfonyl) sulfoximine as an anion are liquid at normal temperature. Compound 1: trioctylmethylammonium bis(trifluoromethanesulfonate) quinone imine (having the structure of the following formula) (cf3so2) 2n (?h2)7ch3 ch3 —N —(CH 2)7〇H 3 (CH2 )7CH3

化合物2:三辛基甲基錢過氯酸酯（具有下式之構造） (CH2)7CH3 _ CH3—N—(〇Η2)7〇Η3 (CI〇4) (CH2)7CH3 化合物3 : N -己基-4 -甲基啦B定鏠過氯酸酯（具有下式之構造） -31 - 200811488 ch3Compound 2: trioctylmethyl-peracetate (having the structure of the following formula) (CH2)7CH3 _ CH3—N—(〇Η2)7〇Η3 (CI〇4) (CH2)7CH3 Compound 3: N - Hexyl-4-methyl-B-deuterated perchlorate (having the structure of the following formula) -31 - 200811488 ch3

n-(ch2)5ch3 (CI04) 化合物4 : N-己基-4-甲基吡啶鏺雙（三氟甲烷磺醯）醯亞胺（具有下式之構造）N-(ch2)5ch3 (CI04) Compound 4: N-hexyl-4-methylpyridinium bis(trifluoromethanesulfonate) fluorene Imine (structure having the following formula)

一 (ch2)5ch3One (ch2)5ch3

(CF3S〇2)2N(CF3S〇2) 2N

化合物5 :己基三甲基銨雙（三氟甲烷磺醯）醯亞胺 (具有下式之構造）Compound 5: Hexyltrimethylammonium bis(trifluoromethanesulfonate) quinone imine (having the structure of the following formula)

ch3 ch2)5〇h3Ch3 ch2)5〇h3

(CF3S〇2)2N 化合物6 : N-丁基-N-甲基吡咯烷鎗雙（三氟甲烷磺醯）醯亞胺（具有下式之構造） (cf3so2)2n r\-CH3 W、(ch2)3ch3 又，分別使用下列物質作爲交聯劑及矽烷化合物（均爲商品名）。 •32- 200811488 交聯劑(CF3S〇2) 2N Compound 6: N-butyl-N-methylpyrrolidine gun bis(trifluoromethanesulfonate) quinone imine (having the structure of the following formula) (cf3so2)2n r\-CH3 W, ( Ch2) 3ch3 Further, the following materials were used as a crosslinking agent and a decane compound (both trade names). •32- 200811488 Crosslinker

Colonate L:甲苯撐二異氰酸酯之三羥甲基丙烷加成體的醋酸乙酯溶液（固形成分濃度75%)，由日本Polyurethane 工業（股）所取得。矽烷化合物 X - 4 1 - 1 8 0 5 :具有氫硫基之矽烷低聚物（液體），由信越化學工業（股）所取得。 [實施例1〜4、比較例1〜8] (a)黏著劑之製造將聚合例1所得之丙細酸樹脂A1以單獨、或將聚合例2所得之丙烯酸樹脂A2與聚合例3所得之丙烯酸樹脂 A3以表1所示之重量比率混合，作成醋酸乙酯溶液。相對於所得溶液之不揮發成分1 〇〇份，將上述所示之離子性化合物1〜化合物6、交聯劑1 '' Colonate L"、及矽烷化合物、X-41-1 8 05 〃分別以表1所示之比例混合，調製黏著劑組成物。但表1中’交聯劑'' Colonate L〃的配合量（份）爲固形成分之份量。單獨使用丙烯酸樹脂A1之例中，來自其中不飽和羧酸之構造單位的份量，相對於丙烯酸樹脂1 〇〇份爲以3份’將丙烯酸樹脂A2與丙烯酸樹脂A3 以7 0/30之重量比予以混合之例中，來自其中不飽和羧酸之構造單位的份量，相對於丙烯酸樹脂1 〇〇份爲0.77份。 -33- 200811488 表1 高分子量低分子量離子性交聯劑矽烷化合物丙烯酸樹脂丙烯酸樹脂化合物 Colonate L Χ-41-1805 實施例1 A1/100 份化合物1/4.5份 5.0份 0.1份實施例2 A1/100 份 - 化合物2/6.0份 5.0份 0.1份實施例3 A2/70 份 A3/30 份化合物1/4.5份 3.0份 0.1份實施例4 A2/70 份 A3/30 份化合物1/3.0份 3.0份 0.1份比較例1 A1/100 份 - - 5.0份〇·ΐ份比較例2 A1/100 份 - 化合物3/4.5份 5.0份 0.1份比較例3 A2/70 份 A3/30 份 - 2.3份〇·ΐ份比較例4 A2/70 份 A3/30 份化合物5/5.0份 3.0份 0.1份比較例5 A2/70 份 A3/30 份化合物4/3.0份 3.0份 0·1份比較例6 A2/70 份 A3/30 份化合物5/3.0份 2.3份〇·ΐ份比較例7 A2/70 份 A3/30 份化合物6/3.0份 2.3份〇·ΐ份比較例8 A2/70 份 A3/3 0 份化合物4/3.0份 2.3份 0.1份Colonate L: Ethyl acetate solution of trimethylolpropane addition toluene diisocyanate (solid content concentration: 75%), obtained from Polyurethane Industries, Ltd., Japan. Decane compound X - 4 1 - 1 8 0 5 : decane oligomer (liquid) having a thiol group, obtained by Shine Chemical Industry Co., Ltd. [Examples 1 to 4 and Comparative Examples 1 to 8] (a) Production of Adhesive Agent The acrylic acid resin A1 obtained in Polymerization Example 1 was obtained by using the acrylic resin A2 obtained in Polymerization Example 2 alone or in Polymerization Example 3. Acrylic resin A3 was mixed at a weight ratio shown in Table 1 to prepare an ethyl acetate solution. The above-mentioned ionic compound 1 to compound 6, cross-linking agent 1 '' Colonate L", and decane compound, X-41-1 8 05 〃 were respectively obtained with respect to 1 part by weight of the non-volatile component of the obtained solution. The ratios shown in Table 1 were mixed to prepare an adhesive composition. However, the compounding amount (part) of the 'crosslinking agent'' Colonate L〃 in Table 1 is the amount of the solid component. In the example in which the acrylic resin A1 is used alone, the amount of the structural unit derived from the unsaturated carboxylic acid is 7/30 by weight of the acrylic resin A2 and the acrylic resin A3 with respect to 1 part of the acrylic resin. In the case of mixing, the amount of the structural unit derived from the unsaturated carboxylic acid was 0.77 parts based on 1 part by weight of the acrylic resin. -33- 200811488 Table 1 High molecular weight low molecular weight ionic crosslinker decane compound Acrylic resin Acrylic resin compound Colonate L Χ-41-1805 Example 1 A1/100 parts of compound 1/4.5 part 5.0 part 0.1 part Example 2 A1/100 Parts - Compound 2 / 6.0 parts 5.0 parts 0.1 parts Example 3 A2 / 70 parts A3 / 30 parts of compound 1 / 4.5 parts 3.0 parts 0.1 parts Example 4 A2 / 70 parts A3 / 30 parts of compound 1 / 3.0 parts 3.0 parts 0.1 Comparative Example 1 A1/100 parts - - 5.0 parts ΐ · 比较 Parts Comparative Example 2 A1/100 parts - Compound 3 / 4.5 parts 5.0 parts 0.1 parts Comparative Example 3 A2 / 70 parts A3 / 30 parts - 2.3 parts 〇 · ΐ Comparative Example 4 A2/70 parts A3/30 parts of compound 5/5.0 parts 3.0 parts 0.1 parts Comparative Example 5 A2/70 parts A3/30 parts of compound 4/3.0 parts 3.0 parts 0·1 parts Comparative Example 6 A2/70 parts A3/30 parts of compound 5/3.0 parts 2.3 parts 〇·ΐ parts Comparative Example 7 A2/70 parts A3/30 parts of compound 6/3.0 parts 2.3 parts 〇·ΐ Parts Comparative Example 8 A2/70 parts A3/3 0 parts of compound 4/3.0 parts 2.3 parts 0.1 parts

(b)附黏著劑之光學薄膜的製作將上述之黏著劑組成物，於經脫模處理之聚對苯二甲酸乙二酯薄膜（商品名''PET 3811〃，由Lintech(股）所取得；稱爲間隔件）的脫模處理面，使用塗佈器以乾燥後之厚度爲25 μιη般塗佈，並於90 °C下乾燥1分鐘，取得薄片狀之黏著劑。其次，將吸黏配向碘之聚乙烯醇偏光子的兩面，以三乙醯纖維素所構成之保護薄膜夾住之三層構造的偏光薄膜的單面，將上述所得之薄片狀黏著劑的間隔件反側面（黏著劑面）以層合器予以貼合後，於溫度231、相對濕度65%之條件下熟成10日，取得附黏著劑之偏光薄膜 -34- 200811488 (〇附黏著劑之光學薄膜的防止帶電性評價將所得之附黏著劑之偏光薄膜的間隔件剝離時，以表面固有電阻測定裝置[三菱化學（股）製之Miirest-up MCP-HT 450 〃（商品名）]測定黏著劑的表面電阻値，並且評價防止帶電性。表面電阻値若爲1 0 12 Ω /□以下，則取得相應的防止帶電性，若爲1011 Ω /□以下則爲更佳。 (d)光學層合體之製作及評價將上述（b)所製作之附黏著劑之偏光薄膜對於液晶元件用玻璃基板[Coning公司製之'' 1 737〃（商品名）]的兩面，以正交尼科耳稜鏡般貼黏，製作光學層合體。將此光學層合體於溫度80°C之乾燥條件下保管96小時之情形（耐熱試驗），以目視觀察飛白的表現狀態。將進行上述耐熱試驗之情形、與溫度60 °C、相對濕度90%下保管96小時之情形（耐濕熱試驗），由60 °C中加熱之狀態，降溫至-20 °C，其次升溫至60°C之過程視爲一個循環（1小時），將其重複1 〇〇個循環之情形（耐熱衝擊試驗）分別以目視觀察試驗後的光學層合體。結果以下列之基準予以分類，並且整理於表2。 <飛白之表現狀態> 由偏光薄膜之一側入射光時之飛白的表現狀態’以下列之四個階段予以評價。 ◎:完全未察見飛白。 -35- 200811488 〇：飛白幾乎不明顯。 △:飛白稍微明顯。 X :顯著察見飛白。 <耐熱性、耐濕熱性及耐熱衝擊性（表2中以「耐HS性」表示）> 此些評價爲以下列四個階段進行。 ◎:完全未察見浮起、剝落、發泡等之外觀變化。〇：幾乎未察見浮起、剝落、發泡等之外觀變化。 △=浮起、剝落、發泡等之外觀變化稍微明顯。 X :顯著察見浮起、剝落、發泡等之外觀變化。 (e)附黏著劑之光學薄膜的再次加工性評價再次加工性的評價爲如下進行。首先，將前述之附黏著劑之偏光薄膜裁斷成25mmxl50mm大小之試驗片。其次，將此試驗片以其黏著劑側，使用貼附裝置[富士塑膠機械（股）製之"Lampaker 〃（商品名）]貼附至液晶元件用玻璃基板，並於50t：、5kg/cm2(490.3 kPa)進行20分鐘壓熱處理。其次於70 T：下加熱處理2小時，接著於50°C之烤爐中保管48小時後，於溫度231，相對濕度50%之氛圍氣中，由此貼黏試驗片將偏光薄膜以3 00mm/分鐘之速度於1 80°方向上剝離，並觀察玻璃板表面之狀態，以下列基準予以分類。結果合倂示於表2。 ◎:於玻璃板表面完全未察見朦朧等。 -36- 200811488 〇：於玻璃板表面幾乎未察見矇朧等。 △:於玻璃板表面察見矇朧等。 X :於玻璃板表面察見黏著劑之殘留。(b) Preparation of an optical film with an adhesive The above-mentioned adhesive composition was obtained from a release-treated polyethylene terephthalate film (trade name ''PET 3811〃, obtained by Lintech) The release-treated surface, which is called a spacer, was coated with a thickness of 25 μm after drying using an applicator, and dried at 90 ° C for 1 minute to obtain a sheet-like adhesive. Next, the adhesive sheet is bonded to the both sides of the polyvinyl alcohol polarizer of the iodine, and the one side of the polarizing film of the three-layer structure sandwiched by the protective film made of triacetyl cellulose is used to separate the above-mentioned flaky adhesive. The opposite side (adhesive surface) is laminated with a laminator, and then aging at a temperature of 231 and a relative humidity of 65% for 10 days to obtain a polarizing film with an adhesive-34-200811488 (optical with an adhesive) Evaluation of the antistatic property of the film When the separator of the obtained polarizing film with an adhesive was peeled off, the adhesion was measured by a surface specific resistance measuring device [Miirest-up MCP-HT 450® (trade name) manufactured by Mitsubishi Chemical Corporation). The surface resistance of the agent is 値, and the charge resistance is evaluated. When the surface resistance 値 is 1 0 12 Ω /□ or less, the corresponding charge-preventing property is obtained, and if it is 1011 Ω /□ or less, it is more preferable. (d) Optical layer Production and evaluation of the polarizing film with the adhesive prepared in the above (b) on both sides of the glass substrate for liquid crystal elements ["1 737" (trade name) manufactured by Coning Co., Ltd.) Sticky like a mirror, The optical laminate was stored in a dry condition at a temperature of 80 ° C for 96 hours (heat resistance test), and the performance state of the whitening was visually observed. The heat resistance test was carried out at a temperature of 60 ° C. Stored at a relative humidity of 90% for 96 hours (damp heat resistance test), heated from 60 °C to -20 °C, and then heated to 60 °C as a cycle (1 hour). The optical laminates after the test were visually observed by repeating one cycle (heat shock test). The results were classified according to the following criteria, and are summarized in Table 2. <Expression state of flying white> by polarized light The performance state of whitening when one side of the film is incident on the light is evaluated in the following four stages. ◎: No whitening is observed at all. -35- 200811488 〇: Flying white is almost inconspicuous. △: Flying white is slightly noticeable. X: Significantly It is observed that it is white. <Heat resistance, heat and humidity resistance and thermal shock resistance (indicated by "HS resistance" in Table 2)> These evaluations were carried out in the following four stages: ◎: No floating, peel The appearance of the falling, foaming, etc. changes. 〇: The appearance change of floating, peeling, foaming, etc. is hardly observed. △=The appearance change of floating, peeling, foaming, etc. is slightly obvious. X: Significantly observed floating (e) Reworkability evaluation of optical film with adhesive The evaluation of reworkability was carried out as follows. First, the above-mentioned polarizing film with an adhesive was cut into a test of 25 mm x 150 mm. Then, the test piece was attached to the glass substrate for liquid crystal elements by the attachment device [Lampaker 〃 (trade name) manufactured by Fuji Plastic Machinery Co., Ltd.) on the adhesive side, and at 50 t: 5 kg/cm 2 (490.3 kPa) was subjected to autoclave for 20 minutes. Next, it was heat-treated at 70 T: for 2 hours, then stored in an oven at 50 ° C for 48 hours, and then at a temperature of 231 and a relative humidity of 50%, thereby adhering the test piece to a polarizing film of 300 mm. The speed of /min was peeled off in the direction of 180°, and the state of the surface of the glass plate was observed, and classified according to the following criteria. The results are shown in Table 2. ◎: No defects were observed on the surface of the glass plate. -36- 200811488 〇: There are almost no obscurities on the surface of the glass plate. △: The surface of the glass plate was observed to be obscured. X: The residue of the adhesive was observed on the surface of the glass plate.

表2 離子性化合物表面電阻値飛白耐熱性耐濕熱性耐HS性再次加工性實施例1化合物1 1.3χ10ηΩ/口〇 ◎ ◎ ◎ ◎ 實施例2化合物2 6.4χ10ηΩ/Π 〇 ◎ ◎ 〇 ◎ 實施例3化合物1 5.1χ1010Ω/口 ◎ ◎ 〇 ◎ 〇實施例4化合物1 9.7χ1010Ω/Π ◎ ◎ ◎ ◎ 〇比較例1 - >1014Ω/口〇 ◎ 〇 ◎ ◎ 比較例2化合物3 6.0χ1012Ω/口 ◎ X △ X ◎ 比較例3 - 2.7x1013 Ω/Π ◎ ◎ ◎ ◎ 〇比較例4化合物5 2.0x1010 Ω/Q ◎ ◎ Δ ◎ 〇比較例5化合物4 7.4χ1010Ω/Π ◎ 〇 X ◎ 〇比較例6化合物5 7·5χ1010Ω/口 ◎ ◎ X ◎ ◎ 比較例7化合物6 1.1χ10ηΩ/Π ◎ X X ◎ 〇比較例8化合物4 6.1χ1010Ω/Π ◎ ◎ X ◎ Δ 如表1及表2所得知般，配合本發明所規定之離子性化合物的實施例1〜4爲表面電阻値變低，故防止帶電性優良’並且難引起飛白，又，耐熱性、耐濕熱性、耐熱衝擊性及再次加工性任一者均取得大約滿足之結果。相對地，未配.合離子性化合物之比較例1及3爲面電阻値高，故無法期望防止帶電性，另一方面，雖具有離子性，但配合不滿足本發明規定之化合物3的比較例2，表面電阻値的降低亦小。雖具離子性，但配合不滿足本發明規定之化合物 -37- 200811488 4、化合物5或化合物6的比較例4〜8，雖察見防止帶電效果，但耐熱性、耐濕熱性、耐熱衝擊性及再次加工性任一者未取得充分之結果。本發明之附黏著劑之光學薄膜爲賦予高的防止帶電性，且即使大型化亦難引起飛白，耐久性亦優良，故適合使用於液晶顯示裝置。例如，適於TN液晶元件等，可一邊賦予防止帶電性，一邊抑制飛白，且可提高耐久性。又，若將此附黏著劑之光學薄膜使用於S T N液晶元件，則可抑制色斑的發生。本發明之附黏著劑之光學薄膜可有效抑制光學構材的 w電。此附黏著劑之光學薄膜爲例如，層合至液晶元件的玻璃基板下，提供液晶顯示用之光學層合體。此光學層合體爲於濕熱條件下，令起因於光學薄膜及玻璃基板之尺寸變化的應力被黏著劑層所吸收、緩和，故減輕局部的應力集中，抑制黏著劑層對於玻璃基板的浮起和剝落等。又，由於防止起因於不均勻應力分佈的光學性缺陷，故可抑制飛白。更且，將附黏著劑之光學薄膜暫時層合至玻璃基板，即使於具有任何不適之情形中，令此光學薄膜由黏著劑及玻璃基板剝離，亦於剝離後之玻璃基板表面少發生糊殘留和朦矓，且可再度使用作爲玻璃基板，再次加工性優良。 -38-Table 2 Ionic Compound Surface Resistance 値 Flying White Heat Resistance Humidity Resistance HS Resistance Reworkability Example 1 Compound 1 1.3 χ 10 η Ω / 〇 ◎ ◎ ◎ ◎ Example 2 Compound 2 6.4 χ 10 η Ω / Π 〇 ◎ ◎ 〇 ◎ Example 3 Compound 1 5.1 χ 1010 Ω / □ ◎ 〇〇〇 Example 4 Compound 1 9.7 χ 1010 Ω / Π ◎ ◎ ◎ ◎ 〇 Comparative Example 1 - > 1014 Ω / 〇〇 ◎ ◎ ◎ Comparative Example 2 Compound 3 6.0 χ 1012 Ω / mouth ◎ X △ X ◎ Comparative Example 3 - 2.7x1013 Ω/Π ◎ ◎ ◎ ◎ 〇Comparative Example 4 Compound 5 2.0x1010 Ω/Q ◎ ◎ Δ ◎ 〇Comparative Example 5 Compound 4 7.4χ1010 Ω/Π ◎ 〇X ◎ 〇Comparative Example 6 Compound 5 7·5χ1010 Ω/□ ◎ ◎ X ◎ ◎ Comparative Example 7 Compound 6 1.1χ10ηΩ/Π ◎ XX ◎ 〇Comparative Example 8 Compound 4 6.1χ1010Ω/Π ◎ ◎ X ◎ Δ As shown in Table 1 and Table 2, match In Examples 1 to 4 of the ionic compound defined by the present invention, the surface resistance enthalpy is low, so that the chargeability is excellent, and it is difficult to cause whitening, and heat resistance, moist heat resistance, thermal shock resistance, and reworkability are either By About the outcome of the meet. On the other hand, in Comparative Examples 1 and 3 in which the ionic compound was not added, the surface resistance was high, and therefore it was not possible to prevent the chargeability. On the other hand, although it had ionic properties, it was compared with the compound 3 which did not satisfy the requirements of the present invention. In Example 2, the reduction in surface resistance 値 is also small. Although it is ionic, it is compatible with Comparative Examples 4 to 8 which do not satisfy the requirements of the present invention -37-200811488 4, Compound 5 or Compound 6, although heat-proof, heat-resistant, and thermal shock resistance are observed. And either of the reworkability did not achieve sufficient results. The optical film with an adhesive according to the present invention is suitable for use in a liquid crystal display device because it imparts high charge-preventing property and is difficult to cause whitening even if it is large in size and excellent in durability. For example, it is suitable for a TN liquid crystal element or the like, and it is possible to suppress whitening while imparting antistatic property, and to improve durability. Further, when the optical film with an adhesive is used for the S T N liquid crystal element, the occurrence of color unevenness can be suppressed. The optical film with an adhesive of the present invention can effectively suppress the electric power of the optical member. The optical film with an adhesive is, for example, laminated under a glass substrate of a liquid crystal element to provide an optical laminate for liquid crystal display. The optical laminate is such that the stress caused by the dimensional change of the optical film and the glass substrate is absorbed and relaxed by the adhesive layer under moist heat conditions, thereby alleviating local stress concentration and suppressing the floating of the adhesive layer on the glass substrate and Peeling and so on. Further, since optical defects caused by uneven stress distribution are prevented, whitening can be suppressed. Moreover, the optical film with an adhesive is temporarily laminated to the glass substrate, and even if there is any discomfort, the optical film is peeled off from the adhesive and the glass substrate, and the paste residue on the surface of the glass substrate after peeling is less likely to occur. And 朦胧, and can be reused as a glass substrate, and is excellent in reworkability. -38-

Claims

200811488 十、申請專利範園 1. 一種附黏著劑之光學薄膜，其爲於光學薄單面上形成黏著劑層而成的附黏著劑之光學薄膜爲該黏著劑層爲由含有 (1)以來自下式（I) 膜之至少，其特徵200811488 X. Patent application garden 1. An optical film with an adhesive, which is an adhesive film formed by forming an adhesive layer on an optical thin single surface, wherein the adhesive layer is composed of (1) At least from the film of the following formula (I), its characteristics

CH2=c-C-〇一R2 II 〇CH2=c-C-〇一R2 II 〇

(式中，Ri爲表示氫原子或甲基，R2爲分別表示數1〜1 〇個之烷氧基所取代之碳數1〜1 4個之烷基 )所示之（甲基）丙烯酸酯之構造單位作爲主成分於分子內含有一個烯烴性雙鍵和來自具有至少一不飽和羧酸的構造單位，且含有重量平均ί 800,000— 2,000,000之第一丙烯酸樹脂，且來自和羧酸之構造單位的含量，相對於樹脂全體100 0.5〜10重量份之丙烯酸樹脂、 (Β)下式（II) 亦可經碳或方院基，更且，個羧基之子子量爲前述不飽重量份爲 R3-N—r5 (Π)(wherein, Ri is a hydrogen atom or a methyl group, and R2 is an alkyl group having 1 to 14 carbon atoms substituted by an alkoxy group each of a number of 1 to 1 each) The structural unit as a main component contains an olefinic double bond in the molecule and a structural unit derived from at least one unsaturated carboxylic acid, and contains a first acrylic resin having a weight average of 8,000,000 to 2,000,000, and a structural unit derived from the carboxylic acid The content is 0.5 to 10 parts by weight of the acrylic resin with respect to 100% by weight of the entire resin, and the following formula (II) may be passed through a carbon or a square base, and the amount of the carboxyl group is the aforementioned unsaturated portion. -N-r5 (Π)

(式中，R3爲表示碳數1〜12個之烷基，R4、R5 R6爲分 -39- 200811488 別獨立表示碳數6〜12個之烷基）所示之含有陽離子之離子性化合物、及 (C)交聯劑之組成物所形成。 2 ·如申請專利範圍第1項之附黏著劑之光學薄膜，其中，來自構成第一丙烯酸樹脂之（甲基）丙烯酸酯的構造單位爲含有來自丙烯酸丁酯的單位。 3 .如申請專利範圍第1項或第2項之附黏著劑之光學薄膜，其中，丙烯酸樹脂（A)爲於前述第一丙烯酸樹脂，加上含有以來自前述式（I)所示之（甲基）丙烯酸酯的構造單位作爲主成分，且重量平均分子量爲50,000〜500,000之第二丙烯酸樹脂。 4.如申請專利範圍第1項〜第3項中任一項之附黏著劑之光學薄膜，其中，離子性化合物（B)爲其陰離子爲含有氟原子。 5·如申請專利範圍第4項之附黏著劑之光學薄膜，其中，陰離子爲雙（三氟甲烷磺醯）醯亞胺。 6 ·如申請專利範圍第1項〜第5項中任一項之附黏著劑之光學薄膜’其中，離子性化合物（B)爲相對於丙烯酸樹脂（A)100重量份，存在〇·5〜10重量份。 7 ·如申請專利範圍第1項〜第6項中任一項之附黏著劑之光學薄膜’其中，交聯劑（C)爲異氰酸酯系化合物。 8.如申請專利範圍第7項之附黏著劑之光學薄膜，其中，交聯劑（C)爲由甲苯撐二異氰酸酯、令甲苯撐二異氰 -40- 200811488 酸酯與多元醇反應的加成物、甲苯撐二異氰酸酯之二聚物、及甲苯撐二異氰酸酯之三聚物所組成群中選出。 9 ·如申請專利範圍第1項〜第8項中任一項之附黏著劑之光學薄膜，其中，形成黏著劑層之組成物爲再含有矽烷系化合物。 10·如申請專利範圍第1項〜第9項中任一項之附黏著劑之光學薄膜，其中，光學薄膜爲由偏光薄膜及相位差薄膜中選出。 11. 一種光學層合體，其特徵爲令如申請專利範圍第1 項〜第1 〇項之附黏著劑之光學薄膜，以其黏著劑層側層合至玻璃基板而成。(wherein R3 is an alkyl group having a carbon number of 1 to 12, R4 and R5 R6 are a group of -39-200811488 and independently represents an alkyl group having 6 to 12 carbon atoms), and a cation-containing ionic compound is used. And (C) a composition of a crosslinking agent. An optical film with an adhesive according to the first aspect of the invention, wherein the structural unit derived from the (meth) acrylate constituting the first acrylic resin contains a unit derived from butyl acrylate. 3. The optical film with an adhesive according to claim 1 or 2, wherein the acrylic resin (A) is added to the first acrylic resin as shown in the above formula (I) ( The structural unit of the methyl acrylate is a main component, and the second acrylic resin having a weight average molecular weight of 50,000 to 500,000. 4. The optical film of the adhesive according to any one of claims 1 to 3, wherein the ionic compound (B) has an anion containing a fluorine atom. 5. An optical film with an adhesive according to item 4 of the patent application, wherein the anion is bis(trifluoromethanesulfonate) quinone imine. [6] The optical film of the adhesive according to any one of the above-mentioned claims, wherein the ionic compound (B) is present in an amount of 重量·5~ relative to 100 parts by weight of the acrylic resin (A). 10 parts by weight. The optical film of the adhesive according to any one of the above-mentioned claims, wherein the crosslinking agent (C) is an isocyanate compound. 8. The optical film with an adhesive according to claim 7, wherein the crosslinking agent (C) is a reaction of toluene diisocyanate, toluene diisocyanate-40-200811488 acid ester and polyol. The composition of the product, the dimer of tolylene diisocyanate, and the terpolymer of tolylene diisocyanate are selected. The optical film with an adhesive according to any one of claims 1 to 8, wherein the composition forming the adhesive layer further contains a decane-based compound. The optical film of the adhesive according to any one of the items 1 to 9, wherein the optical film is selected from the group consisting of a polarizing film and a retardation film. An optical laminate characterized in that the optical film of the adhesive according to the first to the first aspects of the invention is laminated on the side of the adhesive layer to the glass substrate.

-41- 200811488 七明說單無簡為符圖件表元代之定圖 :指表圖案代表本本代定一二匕曰八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：無 -3--41- 200811488 七明说单单单为图图表元代定图: Refers to the table pattern representing the book, one for the second, and if the case has a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: none -3-