TW201229183A - Adhesive resin composition for image display device, adhesive sheet for image display device, image display device and fabricating method thereof - Google Patents
Adhesive resin composition for image display device, adhesive sheet for image display device, image display device and fabricating method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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Abstract
Description
201229183 六、發明說明： 【發明所屬之技術領域】 本發明是有關於影像顯示裝置用黏著性樹脂組成物、 影像顯示裝置用黏著片及影像顯示裝置。 【先前技術】 嚴酷之條件下，產4 層6之黏著力降低， 代表性的影像顯示裝置之例子可例示液晶顯示裝置 (液晶顯示器（Liquid Crystal Display，LCD ))。於液晶顯 示裝置之液晶顯示單元等光學部件中通常貼附有偏光板或 偏光板與相位差板之積層體等，但近年來内置有觸控面板 之液晶顯示裝置之需要不斷增長。將該結構之略圖例示於 圖1中。内置有觸控面板之液晶顯示裝置包含透明保護板 (玻璃或塑膠基材）1、觸控面板2、偏光板3、液晶顯示 單元4，於最近之液晶顯示裝置中，為了防止液晶顯示裝 置之破裂、緩和應力及衝擊、以及提高視認性，設有用以 貼附透明保護板與觸控面板之黏著層5，另外設有用以貼 合觸控面板與偏光板之黏著層6。此種液晶顯示裝置開始 用於車載用、室外計量儀器、行動電話、個人電腦等多種 用途中’因此隨之帶來使用環境亦變得非常嚴酷。於此種 產生對各部件進行貼合之黏著層5及黏著201229183 6. EMBODIMENT OF THE INVENTION: TECHNICAL FIELD The present invention relates to an adhesive resin composition for an image display device, an adhesive sheet for an image display device, and an image display device. [Prior Art] Under severe conditions, the adhesion of the four layers 6 is lowered. An example of a representative image display device can be a liquid crystal display (LCD). In the optical components such as the liquid crystal display unit of the liquid crystal display device, a polarizing plate, a laminate of a polarizing plate and a phase difference plate, and the like are usually attached. However, in recent years, there has been an increasing demand for a liquid crystal display device incorporating a touch panel. A schematic diagram of the structure is shown in Fig. 1. The liquid crystal display device with the touch panel includes a transparent protection plate (glass or plastic substrate), a touch panel 2, a polarizing plate 3, and a liquid crystal display unit 4. In the recent liquid crystal display device, in order to prevent the liquid crystal display device The adhesive layer 5 is attached to the transparent protective plate and the touch panel, and the adhesive layer 6 for attaching the touch panel and the polarizing plate is provided for rupturing, mitigating stress and impact, and improving visibility. Such a liquid crystal display device has been used in various applications such as in-vehicle use, outdoor measuring instruments, mobile phones, and personal computers. As a result, the use environment has become very severe. In this way, the adhesive layer 5 and the adhesive layer for bonding the respective components are produced.
4 201229183 _ v〆〆'扈f 且成:於日本專利特開2007-238853號公報中有所例示。 而，作為日本專利特開2007-238853號公報中所記 載材料為了使控接性提高而含有具有叛基之成分，存 在酸成分雜觸控面板之ΙΤΟ透明電極之虞 。而且，日本 ^利特開2G07-238853號公報中所記載之材料之玻璃轉移 溫度低，因此預測其使用性差。 【發明内容】 士發明之目的在於提供對於防止破裂、缓和應力及衝 擊而言有用，透明性優異，改善顯示影像之模糊、閃燦等， 且抑制特別是於高溫條件下（例如贼以上）及高濕條件 了（例如85t/85%RH以上）所產生之氣泡、隆起、剝落 等的，用性優異之影像顯示裝置用黏著性樹脂組成物、使 用。^像顯7F裝置轉著性樹驗成物之影像顯示裝置用 黏著片及影像顯示裝置。 本發明者等人為了解決上述課題而進行了銳意研究， 結果發現藉由於（曱基）丙烯酸系衍生物聚合物、於分子内 具有1個（甲基)丙烯醯基之（曱基)丙烯酸系衍生物單體中 έ有特疋之具有2官能之（甲基）丙烯醯基之交聯劑、及光 聚合起始劑的樹脂組成物，可解決上述課題。基於該 而完成本發明。 亦即，本發明提供： (1) 一種影像顯示裝置用黏著性樹脂組成物，含有 (Α)(甲基）丙烯酸系衍生物聚合物、（Β)於分子内具有工 個（甲基)丙稀醯基之（曱基)丙烯酸系衍生物單體、（c)具 54 201229183 _ v〆〆'扈f and exemplified in Japanese Patent Laid-Open No. 2007-238853. Further, the material recorded in Japanese Laid-Open Patent Publication No. 2007-238853 contains a component having a rebel basis in order to improve the controllability, and a transparent electrode of an acid component miscellaneous touch panel. Further, since the material described in Japanese Patent Publication No. 2G07-238853 has a low glass transition temperature, it is predicted to have poor usability. SUMMARY OF THE INVENTION The object of the invention is to provide a function for preventing cracking, mitigating stress and impact, and having excellent transparency, improving blurring of a display image, flashing, etc., and suppressing particularly high temperature conditions (for example, thieves or more) and In the case of a high-humidity condition (for example, 85t/85% RH or more), an adhesive resin composition for an image display device excellent in usability, such as a bubble, a bulge, or a peeling, is used. ^The image display device for the image display device of the 7F device is used for the adhesive display and image display device. The present inventors have conducted intensive studies to solve the above problems, and as a result, it has been found that a (mercapto)acrylic derivative polymer having a (meth)acrylonium group in the molecule The above-mentioned problem can be solved by a resin composition having a bifunctional (meth)acryloyl group-containing crosslinking agent and a photopolymerization initiator in the derivative monomer. The present invention has been completed based on this. That is, the present invention provides: (1) An adhesive resin composition for an image display device comprising (Α) (meth)acrylic derivative polymer, (Β) having a (meth) propyl group in the molecule Dilute-based (fluorenyl) acrylic derivative monomer, (c) with 5
L 201229183 有Wb，之(甲基)内烯酿基之交聯劑及⑼光聚合起始 劑I戶^八T具有2官能之(甲基)丙烯醯基之交聯劑包含 重^刀「I量為2.〇Xl〇4〜4.〇XU)4之交聯劑（以下，有 ί ί樹r相3劑Y」）’該交聯劑Y之調配量相對於該黏 者性樹成物總量而言為4質量％〜8質量％ ; (2j 一種影像顯示裝置_料，其是將如上述⑴ =之2顯示裝置用黏著性樹脂組成物硬化為㈣^ 獲得，以及 “，影像顯示裝置，其於視認側具有由如上述⑴ 所述貝不裳置用黏著性樹脂組成_形 帛發ϋ ’可提供具有耐衝擊性，視認性優異之影 ^2^°=別是可提供視認側之透明保護板（例如玻 璃。）與黏者性樹脂組成物之密接力高，即使暴露於如 8氣5=5%f這樣的高溫高濕下，亦不產生剝落'、隆起、 著性榭月匕组顯不器之視認性降低之影像顯示裝置用黏 者树月曰，，且成物及影像顯示裝置用黏著片。 1即’藉由本發明可提供能夠將例如液晶顯示單元與 保i板不單元與透明保護板、觸控面板與透明 部件、單元與其他影像顯示裝置中所必需的 或者位於較影像顯示裝置之影像顯示單元更靠視辦 /之部件彼此貼合的影像顯示裝^ 【實施方式】 i 6 201229183 物單體、特定之f 目‘ s 具有2官能之（甲基）丙烯醯基之交聯 ^ 合起始劑，本發明之影像顯示裝置用黏著片 二脂組成物加工為片材狀後進行硬化而成 V裝置是使用該黏著性樹脂組成物或該黏著片 ^ '以下，對本發明之實施形態加以詳細說明。 〈影像顯示裝置雌著性樹脂組成物〉 、本發明之影像顯示裝置用黏著性樹脂組成物 (以下有時_稱為「黏著性樹脂組成物」）巾所含有之成分 逐一加以說明。 [(Α)(甲基)丙烯酸系衍生物聚合物] 本發明中之（Α)(甲基)丙烯酸系衍生物聚合物是指使 1種於分子内具有1個（甲基)丙稀醯基之單«合或者將2 種以上之於分子内具有1個（曱基)丙_基之單體組合而 ”聚而成者3外’若為不損及本發明之效果之範圍内， 則亦可共聚於分子内具有2個以上（曱基)丙_基之化合 物或不具（甲基)丙烯醯基之聚合性化合物（例如丙婦猜、 笨乙烯、乙酸乙稀醋、乙烯、丙稀等於分子内具有i個聚 合性不飽和鍵之化合物或者二乙烯基笨等於分子内具有\ 個以上聚合性不飽和鍵之化合物）。 形成（A)(曱基)丙烯酸系衍生物聚合物之單體例如可 列舉：（曱基)丙烯酸、（甲基)丙稀醯胺、（曱基)丙缚酸甲醋、 (曱基)丙烯酸乙醋、（曱基)丙烯酸正丁酯、（曱基)丙稀酸異 丁酯、（曱基)丙烯酸第二丁酯、（曱基)丙稀酸_2_乙基己酯、 (曱基)丙烯酸異癸酷、（曱基)丙烯酸正月桂基醋、（甲基j丙 201229183 ^酸硬脂基㈣碳數為1〜18之(甲細烯酸絲醋；（甲 基)丙烯鮮基醋、（甲基)丙烯酸苯氧基 (甲基)丙稀義；丁氧基乙二醇(甲基)丙稀酸醋、 =酵(曱基)丙烯酸m基三乙二醇(甲基)丙稀酸醋等 八有院氧基之(甲基)丙嫦酸醋；（甲基)丙婦酸環己基 基)丙烯酸異冰片基醋、（甲基)丙稀酸二環戊基醋等具有脂 核族基之（甲基)丙烯酸0旨；（甲基)丙稀酸·2錄乙醋 基)丙稀酸-3_經基丙醋、（甲基)丙烯酸_4經基丁醋等具有經 基^(。甲基)丙烯酸酯；（甲基）丙稀酸四氫咬σ南甲基酯；四乙 二醇單曱趟（甲基)丙烯酸g旨、六乙二醇單甲喊（甲基)丙稀酸 酯、八乙二醇單甲醚（曱基）丙烯酸酯、九乙二醇甲醚（甲美） 丙烯酸酯等聚乙二醇單甲醚（曱基）丙烯酸酯；七丙二醇^ 甲驗（甲基)丙稀酸醋等聚丙二醇單甲峻（甲基)丙締酸醋；四 乙二醇乙醚（甲基）丙烯酸酯等聚乙二醇乙醚（甲基）丙烯酸 酯；四乙二醇（曱基）丙烯酸酯、六乙二醇（曱基）丙烯酸酯、 八乙二醇（甲基)丙烯酸酯等。 於上述化合物中，較佳的是含有具有碳數為4〜18之 烷基的（甲基)丙烯酸酯，於將共聚之丨分子之聚合物設為 100質量％之情形時，具有碳數為4〜18之烷基的（曱基） 丙烯酸酯之比例較佳的是5質量％〜95質-量％，更佳的是 10質量％〜90質量％。若為5質量。/〇〜95質量％，則存在 於形成黏著片後之加工性中，玻璃或塑膠等之透明基材之 密接性提高之傾向。 此種共聚比例之聚合物通常可藉由以與上述共聚比例 8 201229183 ^— r 相同之比例而調配各單體，使其共聚而獲得，較佳 聚合率實質上接近100質量％。 作為與具有碳數為4〜18之烷基的（甲基)丙烯酸酯共 聚之單體’並不限定於上述所記載之化合物，較佳的是^ 有羥基、嗎啉基'胺基、羧基、氰基、羰基、硝基等極^ 基之單體，亦即，較佳的是具有該些極性基之（甲基）丙烯 酸醋具有使與塑膠等透明基材之黏著性提高之傾向。 (Α)(曱基)丙烯酸系衍生物聚合物之重量平均分子量 是藉由凝膠滲透色譜法，使用標準聚苯乙烯之校準曲線而 換算$之值，較佳的是lxl〇5〜1χ1〇6，更佳的是1χΐ〇5〜 5χΐ05。。藉由使重量平均分子量為1χ1〇5以上，可於高溫（例 如80 C以上）、咼溫高濕（例如85°c/85%RH)之環境下獲 得相對於，明基材等而言並不產生剝落之黏著力；藉由& 其為1X106以下，則影像顯示裝置用黏著性樹脂組成物之 黏度並不過於變高，製成黏著片時之加工性變良好。 而且’（甲基）丙烯酸衍生物聚合物之聚合方法可使用 溶液聚合、乳化聚合、懸浮聚合、本體聚合等已知之 方法。 聚合起始劑可使用由於熱而產生自由基之化合物，具 ，而言可列舉：如過氧化苯甲酿、過氧苯甲酸第三丁醋、 氣過氧化異丙苯、過氧化二碳酸二異丙醋、過氧化二碳酸 丙酯、過氧化二碳酸二(2-乙氧基乙基)酯、過氧化新 癸酸第二丁酯、過氧化特戊酸第三丁酯、過氧化(3,5,5-三 甲基己醯基）、過氧化二丙醯基、過氧化二乙醯基、過氧化 201229183 一(十二烧基)這樣的有機過氧化物，或者如2,2，_偶氣雙異 丁腈、2,2-偶氮雙(2-曱基丁腈）、ι，ι’_偶氮雙(環己炫_丨_羰 基）、2.2’-偶氮雙(2,4-二曱基戊腈）、2,2，_偶氮雙(2,4_二曱基 4曱氧基戊猜）、2,2 -偶氮雙(2_曱基丙酸)二曱醋、4,4，-偶 氮雙(4-氰基戍酸）、2,2|-偶氮雙(2-羥基曱基丙腈）、2,2，_偶 氮雙[2-(咪唑啉·2-基)丙烷]這樣的偶氬系化合物等。 (曱基）丙烯酸系衍生物聚合物之調配量相對於黏著性 樹脂組成物之總量而言較佳的是1〇質量％〜7〇質量％，更 佳的是質量％〜60質量％。若（Α)(甲基)丙烯酸系衍 生物聚合物之調配量為1G質量％〜7G f量％，則影像顯示 裝置用黏著性_組成物之減進人製作黏著片時之適當 的黏度範财，加讀良好。而且，所得之崎4對於玻 璃或塑膠等透明基材之黏著性良好。 [(B)(甲基)丙稀酸系衍生物單體] 本發明之影像顯示裝置用黏著性樹脂組成物中之⑻ (曱基)丙触系衍生物單體若為於分子内具有丨個（甲 丙稀醯基之賴則並無特觀定，可使用公知之材料，t亦 m種以上組合使用。其具體例可列舉（甲基)丙烯酸、（甲 予丙稀醯胺、(甲基)丙烯酸甲醋、(甲基)丙烯酸乙甲 丁丙：酸么丁醋、(甲基)丙稀酸異丁醋、(甲基)丙烯酸第 二:二二·2-乙基己醋、(曱基)丙稀酸異癸酯、 1〜18之桂基§1、（？基)丙触魏基碳數為 之(甲基)丙稀酸炫基醋；（ 丙稀酸苯減乙料具有料環之（U)㈣^，(甲丁基氧） 201229183, 基乙二醇（甲基）丙烯義、了氧基二乙二醇（甲基）丙稀酸 酯、曱氧基三乙二醇（曱基)丙烯酸酯等（曱基)丙烯酸酯K甲 基）丙烯酸環己基酯、（曱基）丙烯酸異冰片基酯、（曱基)丙 烯酸二環戊基醋等具有脂環族基之(曱基)丙稀酸§旨；（$基) 丙稀I 2-起基乙醋、（曱基)丙烯酸-3-經基丙g旨、（曱基)丙 烯酸-4-羥基丁酯等具有羥基之（甲基）丙烯酸酯；（甲丙 烯酸四氫呋喃曱基酯；（曱基）丙烯酸-N，N-二甲基胺基乙 S曰、N，N-二甲基胺基丙基丙烯醢胺、N，N_二甲基丙浠醯 胺、（曱基）丙烯醯嗎啉、N-異丙基丙烯醯胺、N，N_二乙基 丙烯醯胺、N-羥基乙基丙烯醯胺等具有醯胺基之（曱基)二 烯酸酯；2-(2-曱基丙烯醯氧基乙基氧基）乙基異氰酸、 2-(曱基)丙烯醯氧基乙基異氰酸酯等具有異氰酸酯基之（曱 基)丙烯酸酯；四乙二醇單甲醚（曱基)丙烯酸酯、六乙二醇 單曱醚（甲基)丙烯酸酯、八乙二醇單甲醚（甲基)丙烯酸酯、 九乙二醇曱醚（甲基）丙烯酸酯等聚乙二醇單甲喊（曱基）丙 烯酸酯；七丙二醇單曱醚（曱基)丙烯酸酯等聚丙二醇"單甲 喊（曱基)丙細酸S旨，四乙二醇乙驗（甲基）丙稀酸酷等聚乙-醇乙醚（曱基)丙烯酸酯；四乙二醇（甲基)丙烯酸醋、六乙二 醇（甲基)丙烯酸酯、八乙二醇（曱基)丙烯酸酯等。 特別是將烷基之碳數為4〜18之（曱基)丙烯酸烧基醋 與下述通式（b)所表示之含有羥基之丙烯酸酯併用之方法 較佳 CH2 = CXCOO(CmH2mO)nH..· (b) (於式中，X為Η或CH3，m表示2〜4之整數，n表 201229183 示1〜10之整數。） 之㈣㈣酸絲料列舉（甲 曰、(甲基)丙稀酸正戊醋、(甲基)丙稀酸正 己S曰、（曱基)丙_正辛醋、（甲基)丙烯酸異辛s旨、 丙__2_乙基已§旨、（甲基)丙稀酸十二炫基醋、（^) 稀酸硬脂基㈣’較麵是（甲基)丙烯酸正丁自旨、（$ 丙烯酉夂異辛醋、（甲基)丙稀酸_2_乙基己醋、（甲基)^ 正辛醋等，特佳的是（甲基)丙稀酸乙基己醋。私 而且丙埽®^· s旨較甲基丙烯酸酯更佳。該些（甲其^ 烯酸酯亦可將2種以上組合使用。 —土）丙 通式⑻所表示之含有經基之(甲基)丙烯酸酿可 (甲基)丙稀酸-2-經基乙醋、（甲基)丙烯酸]•經基乙醋 基)丙稀酸-2-經基丙醋、（甲基)丙烯酸·3_羥基丙酯、（甲 丙烯酸小經基丙酉旨、（曱基)丙烯酸-4-經基丁酉旨、（τ基)^ 烯酸-3-經基丁醋、（甲基)丙烯酸·2•經基丁酯、（甲基)土 酸-1-經基丁醋等含有經基之(甲基)丙稀酸醋；二乙二 (如甲基)丙烯酸醋或三乙二醇單（甲基)丙稀酸醋等聚乙二醇 f (甲基)丙烯酸g旨；二丙二醇單(甲基)丙烯酸酯或三丙二醇 甲基)丙烯酸酯等聚丙二醇單（甲基)丙烯酸醋；二丁二醇 甲基）丙烯酸酯或三丁二醇單（甲基）丙烯酸酯等聚丁二 醇單（F基)丙烯酸酯等。該些化合物中較佳的是（甲基)丙 酸-2-經基乙酯、（甲基)丙稀酸」·歸乙酿、（甲基)丙稀酸 丨羥基丙醋、（甲基)丙稀酸_3_經基丙醋、（甲基)丙婦酸小 羥基丙酯、（甲基)丙烯酸_4_羥基丁酯、（甲基）丙烯酸_3羥 12 201229183, 基丁醋、（甲基）丙細酸-2-經基丁fi旨、（曱基）丙稀酸_ι_經基 丁酯等，特佳的是（曱基）丙烯酸-2-羥基乙酯及（甲基）丙稀 酸-4-羥基丁酯’極佳的是（曱基）丙烯酸_4_羥基丁醋。而 且，該些（甲基)丙烯酸酯亦可將2種以上組合使用。 而且’自可使本發明之效果進一步提高之觀點考慮， 較佳的是（B)(曱基)丙烯酸系衍生物單體含有（曱基)丙婦 醯嗎琳。 使用（曱基)丙細酿嗎琳之情形時之含量相對於黏著性 樹脂組成物之總量而言較佳的是5質量％〜4〇質量％，更 佳的是10質量％〜30質量％，特佳的是15質量％〜25質 量％ 〇 本發明中之（B)(甲基)丙烯酸系衍生物單體之含量對 於黏著性樹脂組成物之總量而言較佳的是15質量％〜8〇 質量％。若（B)(曱基)丙烯酸衍生物單體之含量為15質 量％〜80質量％之範圍’則將所得之黏著片貼合於玻璃基 板與玻璃基板之間後，抑制實施高溫下（8〇。〇以上）及高 溫高濕下（85°C/85%RH)之可紐試驗後之氣泡的產生°、 剝落。自以上觀點考慮，⑻（甲基)丙烯酸衍生物單體之 含量更佳的是30質量％〜80質量％，特佳的是4〇質量％ 〜80質量％。 [(C)具有2官能之(甲基)丙烯醯基之交聯劑] 本發明中之（C)具有2官能之（曱基)丙烯醯基之交聯 =疋於分子内具有j個（曱基)丙烯轉之單體。於本發明 ’必須包含特^量之重量平均分子量為2•帽4〜以上 13 201229183. 4.0 χ 104之交聯劑γ。藉此可抑制高溫條件下及高濕條件 之氣泡、隆起、剝落等之產生。 製造具有此種重量平均分子量之具有2官能之（曱美 丙烯醯基之交聯劑γ之方法可使用公知之方法，例如可^ 由使如異佛爾酮二異氰酸酯、曱苯二異氰酸酯、二苯基^ 烧一異氰酸酯、六亞曱基二異氰酸醋等各種二異氰酸酯， 與烧二醇、聚烧二醇、聚酯多元醇等各種二醇，與（甲基) 丙烯酸羥基烷基酯、内酯改質（曱基）丙烯酸羥烷基酯、^ 氰酸酯（曱基）丙烯酸烷基酯等各種（曱基）丙烯酸酯以兩末 端成為（曱基)丙烯醯基之方式進行反應而合成。 其中，若為具有起因於異佛爾g同二異氰酸酯之骨架、 亦即下述通式（a)所表示之骨架的二（甲基）丙烯酸胺基曱 酸酉S，則本發明之氣泡、隆起、剝落等之產生抑制效果優 異而較佳。 [化1]L 201229183 has a crosslinker of (b), a (meth) internal olefinic group, and (9) a photopolymerization initiator I, a tetracene having a bifunctional (meth) acrylonitrile group containing a heavy knife The amount of I is 2. 〇Xl 〇 4~4. 〇XU) 4 cross-linking agent (hereinafter, there is ί ί r phase 3 agent Y)) 'The amount of the cross-linking agent Y is relative to the viscous tree The total amount of the product is 4% by mass to 8% by mass; (2j is an image display device which is obtained by hardening the adhesive resin composition of the display device as described above (1) = 2 to (4), and ", The image display device is provided with an adhesive resin made of the adhesive resin as described in the above (1), and has an impact resistance and an excellent visibility. 2^^°= Providing a transparent protective plate (such as glass) on the viewing side with high adhesion to the adhesive resin composition, even if exposed to high temperature and high humidity such as 8 gas 5 = 5% f, no peeling, bulging, The image display device with the reduced visibility of the sexual sputum is not used for the image display device, and the adhesive for the object and the image display device is used. It can provide an image display unit capable of, for example, a liquid crystal display unit and a transparent protection board, a touch panel and a transparent member, a unit and other image display devices, or located in a video display device. Image display device in which the components are attached to each other. [Embodiment] i 6 201229183 A monomer, a specific cross-linking initiator having a bifunctional (meth) acrylonitrile group, the present invention The image display device is processed into a sheet shape by the adhesive sheet diester composition and then cured. The V device is described in detail using the adhesive resin composition or the adhesive sheet. The embodiment of the present invention will be described in detail. The display device is a female resin composition. The components of the adhesive resin composition (hereinafter sometimes referred to as "adhesive resin composition") of the image display device of the present invention are described one by one. [(Α) (Meth)acrylic derivative polymer] The (meth)acrylic derivative polymer in the present invention means a single one having one (meth) acrylonitrile group in the molecule. Or a combination of two or more monomers having one (indenyl)propyl group in the molecule and "merging into three" may be copolymerized if it does not impair the effects of the present invention. a compound having two or more (fluorenyl) propyl groups in the molecule or a polymerizable compound having no (meth) acryl fluorenyl group (for example, propylene, stupid ethylene, ethyl acetate, ethylene, propylene is equal to intramolecular A compound having i polymerizable unsaturated bonds or a divinyl group is equivalent to a compound having more than one polymerizable unsaturated bond in the molecule). The monomer forming the (A) (fluorenyl) acrylic derivative polymer may be, for example, Listed: (mercapto) acrylic acid, (meth) acrylamide, (mercapto) methyl acetonate, (mercapto) acrylate, n-butyl (meth) acrylate, (mercapto) propylene Isobutyl acrylate, second butyl (meth) acrylate, (2-mercapto) acrylic acid 2-ethylhexyl acrylate, (mercapto) acrylic acid, fluorene (mercapto) acrylic lauryl vinegar, Methyl j-propyl 201229183 ^ acid stearyl (four) carbon number is 1 to 18 (methyl methacrylate vinegar; (methyl) propylene fresh vinegar, (methyl) Phenyloxy(methyl)propene olefinic acid; butoxyethylene glycol (meth) acrylate vinegar, = leaven (mercapto) acrylate m-based triethylene glycol (meth) acrylate vinegar, etc. Octaoloxy (meth) propionate vinegar; (methyl) propyl cyclohexyl acrylate) isobornyl vinegar, (meth) acrylate dicyclopentyl vinegar, etc. (Meth)acrylic acid 0; (methyl) acrylic acid · 2 recorded ethyl acrylate) acrylic acid - 3 - propyl acetonate, (meth) acrylic acid _ 4 via butyl vinegar, etc. (. Methyl) acrylate; (methyl) acrylic acid tetrahydronose sigma methyl ester; tetraethylene glycol monoterpene (meth) acrylate g, hexaethylene glycol monomethyl (meth) propylene Ethylene glycol monomethyl ether (mercapto) acrylate such as acid ester, octaethylene glycol monomethyl ether (mercapto) acrylate, nonaethylene glycol methyl ether (methyl methacrylate) acrylate; heptapropanediol ^ Polypropylene glycol monomethyl (meth) propionate vinegar such as methyl acrylate vinegar; polyethylene glycol (meth) acrylate such as tetraethylene glycol diethyl ether (meth) acrylate; tetraethylene glycol (fluorenyl) acrylate, hexaethylene glycol (decyl) acrylate, octaethylene glycol (meth) acrylate, and the like. Among the above compounds, a (meth) acrylate having an alkyl group having a carbon number of 4 to 18 is preferred, and when the polymer of the copolymerized ruthenium molecule is 100% by mass, the carbon number is The proportion of the (mercapto) acrylate of 4 to 18 alkyl groups is preferably from 5% by mass to 95% by mass, more preferably from 10% by mass to 90% by mass. If it is 5 mass. In the processability after the formation of the pressure-sensitive adhesive sheet, the adhesion of the transparent substrate such as glass or plastic tends to be improved. The polymer of such a copolymerization ratio can be usually obtained by copolymerizing each monomer in the same ratio as the above copolymerization ratio 8 201229183 - r, and the polymerization ratio is preferably substantially 100% by mass. The monomer which is copolymerized with the (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is not limited to the above-described compound, and preferably has a hydroxyl group, a morpholinyl 'amine group, and a carboxyl group. A monomer such as a cyano group, a carbonyl group or a nitro group, that is, a (meth)acrylic acid vinegar having such a polar group tends to have an improved adhesion to a transparent substrate such as a plastic. The weight average molecular weight of the (fluorene) (meth)acrylic derivative polymer is converted to a value of $ by gel permeation chromatography using a calibration curve of standard polystyrene, preferably lxl 〇 5 〜 1 χ 1 〇 6, better is 1χΐ〇5~5χΐ05. . By setting the weight average molecular weight to 1 χ 1 〇 5 or more, it is possible to obtain a relatively high temperature (for example, 80 C or more), enthalpy temperature and high humidity (for example, 85 ° C / 85% RH) relative to the bright substrate, etc. The adhesiveness of the peeling is generated. When it is 1×10 or less, the viscosity of the adhesive resin composition for the image display device is not too high, and the workability when the adhesive sheet is formed becomes good. Further, a known method of polymerization of the (meth)acrylic acid derivative polymer can be carried out by solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization or the like. As the polymerization initiator, a compound which generates a radical due to heat can be used, and examples thereof include, for example, benzoic acid benzoate, peroxybenzoic acid, third butyl vinegar, cumene peroxide, and diperoxydicarbonate. Isopropyl vinegar, propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, dibutyl peroxy neodecanoate, tert-butyl peroxypivalate, peroxidation 3,5,5-trimethylhexyl), dipropenyl peroxide, diethylperoxy peroxide, peroxidized organic peroxide such as 201229183 (didecyl), or as 2, 2 , _ Oxygen double isobutyronitrile, 2,2-azobis(2-mercaptobutyronitrile), ι, ι'_ azobis(cyclohexyl 丨-carbonyl), 2.2'-azobis ( 2,4-dimercapto valeronitrile), 2,2,-azobis(2,4-diindolyl 4 decyloxypenta), 2,2-azobis(2-mercaptopropionic acid) Diterpenoid vinegar, 4,4,-azobis(4-cyanodecanoic acid), 2,2|-azobis(2-hydroxydecylpropionitrile), 2,2,_azobis[2- (Imidazoline-2-yl)propane] such an argon-based compound or the like. The blending amount of the (fluorenyl) acrylic derivative polymer is preferably from 1% by mass to 7% by mass, and more preferably from 3% by mass to 60% by mass based on the total amount of the adhesive resin composition. When the blending amount of the (meth)acrylic derivative polymer is from 1% by mass to 7% by weight, the adhesiveness of the image display device is reduced by the appropriate viscosity when the adhesive sheet is produced. Finance, plus good reading. Moreover, the obtained Nasaki 4 has good adhesion to a transparent substrate such as glass or plastic. [(B) (Methyl) acrylic acid derivative monomer] The (8) (fluorenyl) propylene contact derivative monomer in the adhesive resin composition for image display device of the present invention has ruthenium in the molecule. There is no particular preference for the use of a propylene group, and a known material may be used, and t may be used in combination of more than m. Specific examples thereof include (meth)acrylic acid, (methyl acrylamide, ( Methyl)methacrylate, ethyl (meth)acrylate: acid butyl vinegar, (meth) acrylic acid isobutyl vinegar, (meth)acrylic acid second: di-2-ethylhexanoic vinegar , (mercapto) isononyl acrylate, 1 to 18, ke, § 1, (?), propionate, ketone, methic acid (meth) acetonate; (acrylic acid benzene reduction) The material has a ring of (U) (tetra), (methylbutyloxy) 201229183, ethylene glycol (meth) propylene, oxy diethylene glycol (meth) acrylate, decyloxy Triethylene glycol (mercapto) acrylate (mercapto) acrylate (methyl) methacrylate, cyclohexyl acrylate, (fluorenyl) isobornyl acrylate, (nonyl) acrylic acid, dicyclopentyl vinegar, etc. Family-based (曱基)acrylic acid § (meth) acrylate (meth) acrylate having a hydroxyl group such as propylene I 2-ethyl acetoacetate, (fluorenyl) acrylate -3- propyl propyl ketone; (tetrahydrofuranyl methacrylate; (mercapto)acrylic acid-N,N-dimethylaminoethyl sulfonium, N,N-dimethylaminopropyl acrylamide, N,N-dimethyl propyl Amidoxime, (mercapto) propylene morpholine, N-isopropyl acrylamide, N, N-diethyl acrylamide, N-hydroxyethyl acrylamide, etc. a dibasic acid ester having a isocyanate group such as 2-(2-mercaptopropenyloxyethyloxy)ethyl isocyanate or 2-(indenyl)propenyloxyethyl isocyanate Acrylate; tetraethylene glycol monomethyl ether (mercapto) acrylate, hexaethylene glycol monoterpene ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, octaethylene glycol hydrazine Polyethylene glycol monomethyl sulfonate such as ether (meth) acrylate; polypropylene glycol such as heptapropanediol monoterpene ether (mercapto) acrylate "monomethyl sulfonate , tetraethylene glycol test (methyl) Diethyl ethoxylate (mercapto) acrylate; tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, octaethylene glycol (decyl) acrylate, and the like. In particular, a method of using a hydroxy group-containing acrylate having a carbon number of 4 to 18 in an alkyl group and a hydroxy group-containing acrylate represented by the following formula (b) is preferably CH2 = CXCOO(CmH2mO)nH. (b) (In the formula, X is Η or CH3, m represents an integer of 2 to 4, and n table 201229183 shows an integer of 1 to 10.) (4) (4) Acid filaments are listed (methyl hydrazine, (meth) propyl Dilute acid n-pentyl vinegar, (meth) acrylic acid, hexanyl sulfonate, (fluorenyl) propyl hydrazine vinegar, (meth) acrylate octyl sulfate, propylene __2_ethyl §, (methyl ) benzoic acid decyl vinegar, (^) dilute stearyl sulphate (four) 'face is (meth) acrylate n-butyl, ($ propylene bismuth vinegar, (meth) acrylic acid _ 2_ethylhexyl vinegar, (methyl)^-n-octyl vinegar, etc., particularly preferred is (meth)acrylic acid ethyl hexanoic acid. Private and Benedict® ^· s is better than methacrylate. These (methicone) may be used in combination of two or more kinds. The soil contains a (meth)acrylic acid (meth)acrylic acid-2-carboxylate represented by the formula (8). Ethyl vinegar, (meth)acrylic acid] • ethyl acetoacetate) acrylic acid 2- propyl propyl vinegar, (meth) acrylate · 3 hydroxypropyl ester, (methacrylic acid small carbaryl) (fluorenyl)acrylic acid-4-pyridyl, (τ)) enoic acid-3-butyl butyl vinegar, (meth)acrylic acid · 2 • butyl butyl ester, (methyl) oxalate-1- Polyethylene glycol f (such as butyl vinegar or the like containing a base of (meth) acrylate vinegar; diethyl bis (such as methyl) acrylate vinegar or triethylene glycol mono (meth) acrylate vinegar Acrylic acid; dipropylene glycol mono(meth)acrylate or tripropylene glycol methyl) acrylate such as polypropylene glycol mono(meth)acrylate vinegar; dibutyl diol methyl) acrylate or tributyl diol mono Polybutylene glycol mono(F-based) acrylate such as methyl acrylate. Preferred among these compounds are 2-(ethyl)propionic acid 2-ethylidene ethyl ester, (meth)acrylic acid, "branched", (meth)acrylic acid, hydroxypropyl vinegar, (methyl) Acetic acid _3_ propyl propyl vinegar, (meth) propyl acetophenone hydroxypropyl ester, (meth) acrylate _4 hydroxybutyl ester, (meth) acrylate _ 3 hydroxy 12 201229183, butyl vinegar , (meth)propionic acid-2-transformyl, (mercapto)acrylic acid, butyl butyl acrylate, etc., particularly preferably 2-hydroxyethyl (meth) acrylate and ( Methyl) acrylate 4-hydroxybutyl acrylate is excellent (mercapto)acrylic acid _4-hydroxybutyrate. Further, these (meth) acrylates may be used in combination of two or more kinds. Further, from the viewpoint of further improving the effects of the present invention, it is preferred that the (B) (fluorenyl) acrylic derivative monomer contains (indenyl) propylene. The content in the case of using (mercapto) propylene fine lining is preferably 5% by mass to 4% by mass, more preferably 10% by mass to 30% by mass based on the total amount of the adhesive resin composition. %, particularly preferably 15% by mass to 25% by mass. The content of the (B) (meth)acrylic derivative monomer in the present invention is preferably 15 by mass for the total amount of the adhesive resin composition. %~8〇% by mass. When the content of the (B) (fluorenyl) acrylic acid derivative monomer is in the range of 15% by mass to 80% by mass, the obtained adhesive sheet is bonded between the glass substrate and the glass substrate, and then the high temperature is suppressed (8). 〇.〇)) and under high temperature and high humidity (85 °C / 85% RH), the generation of bubbles after the test can be peeled off. From the above viewpoints, the content of the (8) (meth)acrylic acid derivative monomer is more preferably from 30% by mass to 80% by mass, particularly preferably from 4% by mass to 80% by mass. [(C) Crosslinking agent having a bifunctional (meth) acrylonitrile group] (C) Crosslinking of a bifunctional (fluorenyl) acrylonitrile group in the present invention = 疋 has j in the molecule (曱 base) propylene to monomer. In the present invention, it is necessary to include a specific weight average molecular weight of 2 • cap 4 to above 13 201229183. 4.0 χ 104 crosslinker γ. Thereby, generation of bubbles, bulging, peeling, and the like under high temperature conditions and high humidity conditions can be suppressed. A method of producing a bifunctional (comparable propylene fluorene-based cross-linking agent γ) having such a weight average molecular weight can be carried out by a known method, for example, such as isophorone diisocyanate, toluene diisocyanate, or Phenyl group - various diisocyanates such as monoisocyanate, hexamethylene diisocyanate, and various diols such as diol, polyglycol diol, polyester polyol, and hydroxyalkyl (meth) acrylate Various (mercapto) acrylates such as lactone-modified (mercapto) hydroxyalkyl acrylate and cyanate (alkyl) acrylate are reacted in such a manner that they become (fluorenyl) acrylonitrile at both ends. Further, the present invention is a bis(meth)acrylic acid ruthenium bismuth ruthenate S having a skeleton derived from isophor and a diisocyanate, that is, a skeleton represented by the following formula (a). It is preferable that the bubble, the bulging, the peeling, and the like are excellent in suppressing effects.
而且’所述交聯劑Y相對於黏著性樹脂組成物總量而 言必須為4質量％〜8質量％，較佳的是5質量％〜7質量 %。於不足4質量％之情形時，交聯密度低，黏著片於高 溫下之尺寸穩定性差；於超過8質量％之情形時，交聯密 201229183 ，，觸控面H日日單元等貼合對象部件之間後，於= 鉍南溫下⑽。(：以上）及高濕T (85t:/85% ^ 試驗後產生氣泡或產生剝落。 之了#性 另外，於本發明中，作為（C)成分， 劑Y以外，亦可於不損及本發明之圍用= ，劑，亦即偏離所述重量平均分子量之分 B月b之（甲基)丙稀醯基之交聯劑或具有3官能以上 丙烯醯基之交聯劑等。 丞） [(D)光聚合起始劑] 本發明巾所使狀（D)找合起㈣是藉由活性 促進硬化反應之化合物’此處所謂活性能量 線疋“紫外線、電子束、α射線、Ρ射線、γ射線等。 .光聚合起始劑之選定並無特別限定’可使用二苯甲酮 =、蒽酿系、笨曱醯系、疏鹽、重氮鹽、鏽鹽等公知之材 具體而言可列舉：二苯曱酮' Ν，Ν，_四曱基_4,4，·二胺基 -苯曱酮（米其勒_)、Ν，Ν_四乙基_4,4，·二胺基二苯甲^ 4甲氧基-4,4-一甲.基胺基二苯曱酮、α_羥基異丁基苯酮' 2_乙基蒽醌、第三丁基蒽醌、丨，4_二甲基蒽醌、丨-氣蒽醌' 2,3-二氯蒽鲲、3_氯_2_曱基蒽醌、u_笨并蒽醌、基蒽 醌、1,4-萘輥、9，1〇_菲醌、噻噸酮、2_氯噻噸酮、丨_經基^ 己基苯基酮、2,2-二曱氧基-1，2-二苯基乙烷4•酮、2_羥^_2: 甲基-1-苯基丙烷-i·酮、2,2-二乙氧基苯乙酮等芳香族酮化 201229183 =’安息香、甲基安息香、乙基安息香等安息香化合物； 香甲ϋ、安息香乙Μ、安息香異丁_、安息香苯趟等 香ϋ化合物；苯偶醯、苯偶醯二？基_等笨偶醯化 a物，Ρ-(吖啶_9_基)（曱基）丙烯酸之酯化合物；9_苯基吖 啶、一比咬基啊、以二。丫咬基庚烧等十定化合物、二鄰 氯本基)_4,5-二笨基㈣二聚體、2•(鄰氣苯基)_4,5二(間甲 氧基苯基)咪唑二聚體、2_(鄰氟苯基)_4,5_二苯基咪唑二聚 體三2_(鄰曱氧基苯基)-4,5-二苯基咪唑二聚體、2_(對曱氧 ^基)·4,5·二笨基咪嗤二聚體、2,4_二(對曱氧基苯基)^ 本°米°坐二聚體、2_(2,4_二甲氧基苯基)·4,5·二苯基味唾二聚 體2 (對曱基疏基苯基)-4,5-二苯基味β坐二聚體等245二 :編二聚體、2_节基_2_二甲基胺基小(傳嗎琳基； 基)-1_丁酮、2_甲基小[4_(曱硫基）笨基]_2Ν_嗎啉基]丙 烧雙(2’4,6-二甲基苯甲醯基)-笨基氧化膦、寡(2_經基_2_ 甲基-1-(4-(1-甲基乙烯基)苯基)丙酮)等。 而且，特別是不使黏著性樹脂組成物著色之聚合起始 劑較佳的是丨_羥基環己基苯基酮、2_羥基_2甲基小苯基\ 丙則肩、1_[4-(2-羥乙氧基)_苯基]-2-經基-2-曱基小丙^ 小_f α•經基燒基苯酮系化合物；雙(2,4,6-三甲基苯甲^ 基)·苯基氧化膦、雙(2,6-二曱氧基苯甲醯基)_2,4,4-三甲基 戊基氧化膦、2,4,6-三甲基苯甲醯基_二苯基氧化膦^酿^ 氧化膦系化合物；寡(2-羥基-2-曱基-1-(4-(1-甲基乙烯 苯基)丙酮)及該些化合物組合而成者。 土 而且，特別是為了製作厚的片材，較佳的是包含雙 201229183 ! 减膦、2,4,6-三甲基苯甲醯A - 本基氧化鱗醯基氧化膦㈣合物的光聚合起土 - 為了減少片材之臭氣，較佳的 酮)。該些光聚合_ 樹月=2中之⑼綠合起㈣之含量相對於黏著性 白Γ所得之黏著片之透射率高，且色調 「甘1"、自以上觀點考慮’更佳的是3質量％以下。 [其他添加劑】 本發明之影像顯示用黏著性樹脂組成物中，除了Further, the crosslinking agent Y must be 4% by mass to 8% by mass, preferably 5% by mass to 7% by mass based on the total amount of the adhesive resin composition. When the amount is less than 4% by mass, the crosslinking density is low, and the dimensional stability of the adhesive sheet at a high temperature is poor; when it exceeds 8% by mass, the cross-linked dense 201229183, the touch surface H, the day unit, and the like After the parts, after = 铋南温(10). (: above) and high-humidity T (85t: /85% ^ After the test, bubbles are generated or peeled off. In addition, in the present invention, as the component (C), the agent Y may not be damaged. The agent for use in the present invention, that is, a crosslinking agent which deviates from the weight average molecular weight of (b) b (meth) propyl fluorenyl group or a crosslinking agent which has a trifunctional or higher acryl fluorenyl group, etc. [(D) Photopolymerization initiator] The film of the invention (D) is a compound (4) which is a compound which promotes a hardening reaction by an activity. Here, the active energy ray "UV, electron beam, α-ray, X-ray, gamma ray, etc. The selection of the photopolymerization initiator is not particularly limited, and a known material such as a benzophenone = a brewing system, a clumping system, a salty salt, a diazonium salt, or a rust salt can be used. Specific examples thereof include: diphenyl fluorenone ' hydrazine, hydrazine, _tetradecyl _ 4, 4, diamino benzophenone (Michele _), hydrazine, hydrazine _ tetraethyl _ 4, 4 , · Diaminodibenzoic acid 4 methoxy-4,4-methylamino benzophenone, α-hydroxyisobutyl benzophenone ' 2 - ethyl hydrazine, tert-butyl hydrazine醌, 丨, 4_ dimethyl hydrazine, 丨-gas 蒽醌 ' 2,3- Dichloropurine, 3-chloro-2-indenyl hydrazine, u_stupidinium, hydrazine, 1,4-naphthalene roll, 9,1 〇 phenanthrenequinone, thioxanthone, 2-chlorothiazide Tons of ketone, oxime-based hexyl phenyl ketone, 2,2-dimethoxyoxy-1,2-diphenylethane 4 ketone, 2-hydroxyx-2:methyl-1-phenylpropane- Aromatic ketones such as ketone and 2,2-diethoxyacetophenone 201229183 = benzoin compounds such as benzoin, methylbenzoin, ethyl benzoin, etc.; fragrant armor, benzoin, benzoin, benzoin, benzoin Aromatic compound such as benzoquinone; benzophenone, benzophenanthrene yl group, etc., an ester compound of fluorene-(acridine-9-yl)(fluorenyl)acrylic acid; 9-phenylhydrazine Acridine, one bite base, two. Bite base Geng Shao et al., di-o-chloro-based) _4,5-di-phenyl (tetra) dimer, 2 • (o-phenyl)_4,5 Di(m-methoxyphenyl)imidazole dimer, 2_(o-fluorophenyl)-4,5-diphenylimidazole dimer tris(2-o-oxyphenyl)-4,5-diphenyl Imidazole dimer, 2_(p-oxooxy)- 4,5·di-phenylidene dimer, 2,4_bis(p-methoxyphenyl)^ this is a dimer, 2_(2,4-dimethoxyphenyl)·4,5 Diphenyl-saliva dimer 2 (p-mercapto-phenyl)-4,5-diphenyl-flavored β-six dimer, etc. 245 II: Dimer, 2_nod 2_dimethyl Amino group small (trans-mercapto; base)-1_butanone, 2_methyl small [4_(decylthio) stupyl]_2Ν_morpholinyl]propane double (2'4,6-two Methyl benzhydrazinyl)-phenylphosphine oxide, oligo(2_carbyl-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone), etc. The polymerization initiator for coloring the adhesive resin composition is preferably hydrazine-hydroxycyclohexyl phenyl ketone, 2-hydroxyl-2-methylphenyl group, propyl shoulder, and 1_[4-(2-hydroxyethoxy group). _Phenyl]-2-yl-2-yl phenylpropanol^ small _f α• mercaptobenzophenone-based compound; bis(2,4,6-trimethylbenzylidene)·benzene Phosphine oxide, bis(2,6-dimethoxybenzylphenanthryl) 2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzylidene-diphenyl A phosphine oxide compound, a phosphine oxide compound, an oligo(2-hydroxy-2-mercapto-1-(4-(1-methylvinylphenyl)acetone), and a combination of these compounds. Soil and, especially for the production of thick sheets, it is preferred to contain light of 201229183! Phosphine-reducing, 2,4,6-trimethylbenzhydrazide A-based oxidized fluorenylphosphine oxide (tetra) Polymerized soil - in order to reduce the odor of the sheet, a preferred ketone). The photopolymerization _ tree month = 2 (9) green combination (4) content is higher than that of the adhesive sheet obtained by the adhesive white enamel, and the color tone is "give", from the above viewpoints, it is better that 3 % by mass or less. [Other Additives] In addition to the adhesive resin composition for image display of the present invention,
Ji/Bi、（c)及⑼以外，亦可視需要而調配各種 1' 發明中可調配之各種添加劑例如可列舉：以提 =配=、⑻、⑻及（D)而所得之黏著性樹脂組 =之保存，定性為目的而添加之對甲氧基苯酴等聚合抑 二劑，以提高藉由光使黏著性樹脂組成物硬化而所得之黏 =片的财熱性為目的而添加之三苯基膦等 ，對於紫外線等光之耐受性為目的而添加的耻^ =mderedAmine Light Stabilizer，受阻胺光穩定劑）等光 =定劑’用以提高對玻璃等之密接細添加㈣烧偶合劑 寻。 而且，於使用本發明之影像顯示用黏著性樹脂組成物 而獲得黏著片時’成為以聚對苯二甲酸乙二醋膜等失持的 17 201229183 =:『二，酸乙二醋膜等基材之剝 枯《·、ι—甲基魏炫系、氣系等界面活性劑。 麻I 加财單獨使用，且亦可組合舰多種添加 ?卜，該些其他添加劑之含量通常情況下小於上述 於及⑼之合計含量，—般情況下相對 ;霉者性枒脂組成物之總量而言為0.01質量％〜5質量％ 左右。 <黏著片> 其次，於以下說明對影像顯示用黏著性樹脂組成物昭 射活性能量，使其硬化而所得之黏著片。本發明之影像顯 不用黏著輯脂組成物可直接崎狀之狀態而作為黏著劑 使用，較佳的製成片材狀之黏著片而使用。 於以下例示本發明中之黏著片之製作方法。 本發明中之黏著片可藉由於基材上，將黏著性樹脂組 成物塗佈為片材狀，對其照射活性能量線使其硬化而猝 得。活性能量線之光源較佳的是於波長為4〇〇 nm以下^ 有發光分布者，例如可使用低壓水銀燈、中壓水銀燈、/高 壓水銀燈、超高壓水銀燈、化學燈、黑光燈、金屬_素燈 及微波激發水銀燈。而且，照射能量並無特別限定，通常 為 500 mJ/cm2〜5000 mJ/cm2左右。 本發明之影像顯示裝置用黏著片（以下有時簡稱為「黏 著片」）兼具適度之黏著力與二次加工性，且對於所期望之 厚度而言不含氣泡等，而且可設為能夠發揮優異之衝擊緩 和性的厚度。本發明之黏著片之厚度並不由於使用用途及 201229183 方法而特別限定，較佳的是〇 〇5 mm〜2 mm左右之 於該範圍内使用之情形時，作為用以將光學部件貼合“ 不器上的透明黏著片而發揮出特別優異之效果。 而且，黏著片之玻璃轉移溫度較佳的是l(TC〜3(n：。 <影像顯示裝置> 其次，對使用本發明之黏著性樹脂組成物或黏著片之 影像顯示裝置加以說明。 本發明之黏著性樹脂組成物及黏著片可適用於各種影 像顯示裝置中。作為影像顯示裝置，可列舉電漿顯示器 (PDP)、液晶顯示器（LCD)、陰極射線管（CRT)、場發 射顯示器（FED)、有機電激發光顯示器（OELD)、3D顯 示器、電子紙（EP)等。本發明之黏著性樹脂組成物及黏 著片例如可用以將所述影像顯示裝置之抗反射層、防污 層色素層、硬塗層荨具有功能性之功能層，或將該層成 膜或積層於聚乙烯膜、聚酯膜等基材膜等之光學濾光片基 材上而成之多層物，玻璃、壓克力、聚碳酸酯等之透明保 s蒦板或於其上成膜或積層有具有各種功能之功能層而成的 多層物等加以組合而貼合。而且，亦可製成與此種多層物 組合之光學濾光片而使用。另外’本發明之黏著性樹脂組 成物亦可於該些多層物上塗佈、填充等之後而加以硬化。 所述抗反射層若為具有可見光反射率成為5%以下之 抗反射性之層即可，可使用藉由已知之抗反射方法對透明 之塑膠膜等之透明基材進行了處理之層。 所述防污層是用以使表面上難以附著污垢之層，可使 201229183 用為了使表面張力降低而由I㈣脂切酮系樹脂所構成 之已知之層。 _所述色素層疋用以提高色純度之層，用以於自液 示單元等影像齡單元所發k光的色純度叙情形時減 低所不需要之光。可藉由如下方式而獲得：使吸收不需要 之部分之光的色素溶解於樹脂中，於聚乙稀膜、聚酯膜等 基材膜上進行成膜或積層。 ' 所述硬塗層用以提高表面硬度。硬塗層可使用將丙婦 酸胺基甲酸酯或環氧丙烯酸酯等丙烯酸樹脂或環氧樹脂等 成膜或積層於聚乙浠膜等基材膜上而成者。同樣地，為了 提高表面硬度，亦可使用玻璃、壓克力、聚碳酸酯等透明 保5蒦基板或者於该些板上成膜或積層有硬塗層者。 本發明之黏著性樹脂組成物及黏著片可積層於偏光板 上而使用。於此情形時，可積層於偏光板之視認面側，亦 可積層於其相反側。 於偏光板之視認面側使用之情形時，可於黏著片之視 認面侧進一步積層抗反射層、防污層、硬塗層；且於偏光 板與液晶單元之間使用之情形時，可於偏光板之視認面侧 積層具有功能性之層。 於製成此種積層物之情形時’黏著片可使用輥層壓機 或真空貼合機、及單片貼合機而進行積層。 較佳的是黏著片配置於影像顯示裝置之影像顯示單元 與視認側最前面之透明保護板（前面板）之間，視認側之 適宜位置。具體而言’較佳的是應用（use)於影像顯示單 201229183 元與透明保護板之間。 而且，於將觸控面板組合於影像顯示單元中而成的影 像，示裝置中’較佳的是應用（use)於觸控面板與影像 不單70之間及/或觸控面板與所述透明保護板（前面板）之 間，如果在影像顯示裝置之構成上可適用本發明之黏著 片，則並不限於上述所記載之位置。 另外，於透明保護板、觸控面板、或影像顯示單元中 具有10 μιη〜80 μιη之階差之情形時，於藉由黏著片而將 透明保s蔓板與觸控面板之間、觸控面板與影像顯示單元之 間、或透明保護板與影像顯示單元之間貼合之步驟後自 能夠進一步除去階差附近之氣泡的觀點考慮，較佳的是於 40°C 〜8(TC (較佳的是 50°C 〜70。〇、0.3 MPa〜〇.8 MPa (較佳的是0.4 MPa〜0.7 MPa)、5分鐘〜60分鐘（較佳 的是10分鐘〜50分鐘）之條件下進行加熱加壓處理（言 壓釜處理）。 ^ 影像顯示裝置之透明保護板（前面板）可使用一般的 光學用透明基板《具體而言可列舉：玻璃板、石英等=機 物之板，壓克力板、聚碳酸酯板、聚對苯二曱酸乙二酯板 等塑膠（有機物）板’厚的聚酯片材等樹脂片材等。 於所述影像顯示裳置為液晶顯示裝置之情形時，液曰 顯示單元可使用一般的液晶顯示單元。液晶顯示單元根據 液晶材料之控制方法而分類為TN(Twisted Nematic，扭轉 向列）方式、STN ( Super-twisted nematic，超扭轉向列） 方式、VA ( Virtical Alignment，垂直配向）方式、Ips 21 201229183In addition to Ji/Bi, (c) and (9), various additives which can be blended in various 1' inventions can be exemplified, for example, an adhesive resin group obtained by adding =, = (8), (8) and (D) The addition of triphenylbenzene, such as p-methoxybenzoquinone, which is added for the purpose of the purpose of the purpose of improving the heat retention of the adhesive sheet obtained by hardening the adhesive resin composition by light. For the purpose of improving the resistance to light such as ultraviolet rays, such as shame = mdered Amine Light Stabilizer, hindered amine light stabilizer, etc., light-fixing agent is used to improve adhesion to glass and the like (4) smouldering agent Searching. Further, when the adhesive sheet is obtained by using the adhesive resin composition for image display of the present invention, it becomes "a polyethylene terephthalate film or the like". 201229183 =: "Second, acid acetonitrile film and the like The stripping of the material "··, ι-methyl Wei Xuan, gas system and other surfactants. Ma I can be used alone, and can also be combined with a variety of additions. The content of these other additives is usually less than the total content of the above and (9), in general, relative; the total of the moldy rouge composition The amount is about 0.01% by mass to about 5% by mass. <Adhesive sheet> Next, an adhesive sheet obtained by curing the active resin energy for image display adhesive composition and curing it will be described below. The image of the present invention is preferably used as an adhesive in a state where the adhesive composition is directly smear-like, and is preferably used as a sheet-like adhesive sheet. The method of producing the adhesive sheet of the present invention is exemplified below. The adhesive sheet of the present invention can be obtained by coating an adhesive resin composition into a sheet form on a substrate, irradiating it with an active energy ray to harden it. The light source of the active energy ray is preferably at a wavelength of 4 〇〇 nm or less. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black lamp, or a metal element can be used. Lights and microwaves activate the mercury lamp. Further, the irradiation energy is not particularly limited, but is usually about 500 mJ/cm 2 to 5000 mJ/cm 2 . The adhesive sheet for an image display device of the present invention (hereinafter sometimes simply referred to as "adhesive sheet") has both an appropriate adhesive force and secondary workability, and does not contain bubbles or the like for a desired thickness, and can be made capable of The thickness that exerts excellent impact relaxation. The thickness of the adhesive sheet of the present invention is not particularly limited by the use and the method of 201229183, and it is preferably used for attaching optical components when 〇〇5 mm to 2 mm is used in the range. The transparent adhesive sheet on the device has a particularly excellent effect. Further, the glass transition temperature of the adhesive sheet is preferably 1 (TC to 3 (n: < image display device>, secondly, the use of the present invention The image display device of the adhesive resin composition or the adhesive sheet is described. The adhesive resin composition and the adhesive sheet of the present invention can be applied to various image display devices. As the image display device, a plasma display (PDP) or a liquid crystal can be cited. Display (LCD), cathode ray tube (CRT), field emission display (FED), organic electroluminescent display (OELD), 3D display, electronic paper (EP), etc. Adhesive resin composition and adhesive sheet of the present invention, for example The anti-reflective layer, the antifouling layer pigment layer, the hard coat layer of the image display device may have a functional functional layer, or the layer may be formed into a film or laminated on a polyethylene film or a polyester film. a multilayer formed on an optical filter substrate such as a substrate film, a transparent slab of glass, acryl, polycarbonate, or the like, or a film or laminate thereon having functional layers having various functions The multilayered product or the like may be combined and bonded, and may be used as an optical filter in combination with such a multilayer. Further, the adhesive resin composition of the present invention may be applied to the multilayered material. The antireflection layer may be a layer having an antireflection property in which the visible light reflectance is 5% or less, and a transparent plastic film or the like may be used by a known antireflection method. A layer treated with a transparent substrate. The antifouling layer is a layer for making it difficult to adhere to dirt on the surface, and 201229183 can be used as a known layer composed of I(tetra)-denidone-based resin for lowering the surface tension. The layer of the pigment layer used to increase the color purity is used to reduce the unnecessary light in the case of the color purity of the light emitted by the image-age unit such as the liquid display unit, which can be obtained by: To absorb unwanted parts The light pigment is dissolved in the resin, and is formed into a film or laminated on a base film such as a polyethylene film or a polyester film. The hard coat layer is used to increase the surface hardness. The hard coat layer may be used. An acrylic resin such as a carbamic acid ester or an epoxy acrylate, or an epoxy resin is formed into a film or laminated on a base film such as a polyethylene film. Similarly, in order to increase the surface hardness, glass or acrylic may be used. A transparent resin substrate such as a force or a polycarbonate may be used to form a film or laminate a hard coat layer on the plates. The adhesive resin composition and the adhesive sheet of the present invention may be laminated on a polarizing plate and used. When it is used on the side of the viewing surface of the polarizing plate, it may be laminated on the opposite side of the polarizing plate. When used on the viewing side of the polarizing plate, an anti-reflection layer, an anti-fouling layer, and an anti-reflection layer may be further laminated on the viewing side of the adhesive sheet. A hard coat layer; and when used between a polarizing plate and a liquid crystal cell, a functional layer may be laminated on the viewing side of the polarizing plate. In the case of producing such a laminate, the adhesive sheet can be laminated using a roll laminator, a vacuum laminator, and a single sheet bonding machine. Preferably, the adhesive sheet is disposed between the image display unit of the image display device and the transparent protective plate (front panel) at the forefront of the viewing side, and the position of the viewing side is appropriate. Specifically, it is preferred to use between the image display sheet 201229183 and the transparent protection board. Moreover, in the image obtained by combining the touch panel in the image display unit, the display device is preferably used between the touch panel and the image not only 70 and/or the touch panel and the transparent The adhesive sheet of the present invention can be applied to the configuration of the image display device between the protective sheets (front panel), and is not limited to the position described above. In addition, when the transparent protection board, the touch panel, or the image display unit has a step of 10 μm to 80 μm, the transparent protection panel and the touch panel are connected by the adhesive sheet. The viewpoint of bonding between the panel and the image display unit or between the transparent protective plate and the image display unit is preferably from 40 ° C to 8 (TC) from the viewpoint of further removing bubbles near the step. Preferably, it is carried out under conditions of 50 ° C to 70 ° 〇, 0.3 MPa to 〇.8 MPa (preferably 0.4 MPa to 0.7 MPa), and 5 minutes to 60 minutes (preferably 10 minutes to 50 minutes). Heat and pressure treatment (pressure tank treatment) ^ The transparent protective plate (front panel) of the image display device can use a general optical transparent substrate. "Specifically, glass plate, quartz, etc. = machine plate, pressure a resin sheet such as a plastic sheet (such as a polyester sheet) such as a slab, a polycarbonate sheet or a polyethylene terephthalate sheet, or the like, and a liquid crystal display device. In case, the liquid helium display unit can use a general liquid crystal display The liquid crystal display unit is classified into a TN (Twisted Nematic) method, an STN (Super-twisted nematic) method, a VA (virtical Alignment) method, and an Ips 21 according to a control method of the liquid crystal material. 201229183
L (In-Place-Switching，橫向電場切換）方式等，於本發明 中，可為使用任意控制方法之液晶顯示單元。 [實例] 以下，藉由實例對本發明加以說明。另外，本發明並 不限制於該些實例。 <評價> 關於各實例及比較例中所得之各黏著片，藉由以下之 試驗方法進行評價。 1. 玻璃轉移溫度 製作厚度為0·5 mm、寬度為1〇 mm、長度為1〇 mm 之黏著片，使用廣域動態黏彈性測定裝置（phe〇metricThe L (In-Place-Switching) mode or the like may be a liquid crystal display unit using any control method in the present invention. [Examples] Hereinafter, the present invention will be described by way of examples. Further, the invention is not limited to the examples. <Evaluation> Each of the adhesive sheets obtained in each of the examples and the comparative examples was evaluated by the following test method. 1. Glass transfer temperature Make an adhesive sheet with a thickness of 0·5 mm, a width of 1〇 mm, and a length of 1〇 mm, using a wide-area dynamic viscoelasticity measuring device (phe〇metric
Scientific 公司製造、Solids Analyzer RSA-II )，於剪切三明 治模式（shear sandwich mode )、頻率為i .〇 Hz、測定溫度 範圍為-40°C〜80°C、升溫速度為5°C/min下測定玻璃轉移 溫度。 玻璃轉移溫度（Tg)是於上述測定溫度範圍中，tan5 顯示為峰值之溫度。於該溫度範圍中觀測到2個以上tan§ 峰值時’將tan5之值顯示為最大值的溫度作為玻璃轉移溫 度。 2. 外觀評價 將所製作之黏者片切出為寬50 mm、長100 mm之尺 寸，使用輥而貼附於50 mmxlOO mmxt0.7 mm之尺寸的玻 璃基板上。其次，使用輥而於其上貼合同樣之玻璃基板， 製作於玻璃基板與玻璃基板之間夾持有黏著片之結構。其 22 201229183 (6(TC、0.5 MPa)而製成 後’進行30分鐘之高壓釜處理 樣品。 J所完成之樣品於以下之環境條件下放置設定之時 進仃取出後之外_價（氣泡、>評價基準是藉 ==ΓΒ氣泡及剝落之情形記為A ’產生氣泡及 •高溫高濕試驗（以下記载為「85/85」）； 將樣品於85。。、85%RH之條件下放置24小時。 •高溫試驗（以下記載為「100」） 將樣品於100¾之條件下放置24小時。 熱循環试驗（以下記載為「tct」） 實施100次之將樣品於_4(rc之環境下放置3〇分鐘， 於100C之環境下放置3〇分鐘之熱循環。 3·剪力評價 將所製作之黏著片切出為寬25 mmx長25 mm之尺 寸。將忒黏著片貼於25 mmx 1〇〇 mm之不鏽鋼板上，自其 上貼合切為25 mmxlOO mm之PET膜，於PET膜之端附 上1〇〇§之鉛垂。其後，於80〇C之恆溫乾燥機内，以100g 之鉛垂吊垂之方式固定不鏽鋼板，測定24小時後之黏著片 之尺寸變化量。若該尺寸變化量為0.5 mm以下，則記為 OK。 製造例1 < (A)(甲基)丙烯酸系衍生物聚合物之合 成> 於附有冷凝管、溫度計、攪拌裝置、滴液漏斗及氮氣 23 201229183 導入管之反應容器中稱取丙烯酸-2-乙基己酯84 〇 g、丙烯 酸-2-羥基乙酯36.0 g及丁酮150.0 g作為初始單體，一面 藉由100 ml/min之風量進行氮氣置換，一面以15分鐘自 常溫（25°C)加熱至70°C。 其後，面保持為该溫度，一面使用丙稀酸_2_乙基己 酯21.0 g及丙稀酸_2•經基乙醋9 〇 g作為追加單體，準備 於該些化合物中溶解有過氧化月桂醯1〇 g之溶液，以6〇 分鐘滴加該溶液，於滴加結束後進一步反應2小時。 繼而，藉由館去丁酮而獲得丙稀酸_2_乙基己酿與丙稀 酸-2-經基乙S旨之共聚物（重量平均分子量為⑼，議）（以 下將該共聚物稱為「丙烯㈣触物聚合物」）。 另外重量平均分子量之測定是使用以thf為溶劑之 法而進行，使用下述裝置及測定條件而使用 軚準聚本乙烯之杈準曲線而決定。 裝置：日立製作所股份有限公司 RI偵測器：L-3350Made by Scientific, Solids Analyzer RSA-II), in shear sandwich mode, frequency is i.〇Hz, measuring temperature range is -40 °C ~ 80 °C, heating rate is 5 °C / min The glass transition temperature was measured. The glass transition temperature (Tg) is the temperature at which the tan5 shows a peak value in the above-described measurement temperature range. When two or more tan§ peaks were observed in this temperature range, the temperature at which the value of tan5 was shown as the maximum value was taken as the glass transition temperature. 2. Appearance evaluation The prepared adhesive sheet was cut into a size of 50 mm in width and 100 mm in length, and attached to a glass substrate of a size of 50 mm x 100 mm x 0.7 mm using a roller. Next, the same glass substrate was bonded thereto by using a roll, and a structure in which an adhesive sheet was sandwiched between the glass substrate and the glass substrate was produced. After 22 201229183 (6 (TC, 0.5 MPa) was made, the sample was processed in autoclave for 30 minutes. The sample completed by J was placed under the following environmental conditions and was taken out after the extraction. , > The evaluation criteria are as follows: = bubble and peeling are described as A 'bubble and high temperature and high humidity test (hereinafter referred to as "85/85"); sample is 85., 85% RH It is left for 24 hours under conditions. • High temperature test (hereinafter referred to as "100") The sample is allowed to stand under conditions of 1003⁄4 for 24 hours. Thermal cycle test (hereinafter referred to as "tct") 100 times of the sample is placed at _4 ( Place in rc environment for 3 minutes, and place heat cycle for 3 minutes in 100C environment. 3.·Shear evaluation: Cut the prepared adhesive sheet into a width of 25 mmx and a length of 25 mm. On a 25 mm x 1 mm stainless steel plate, a PET film cut to 25 mm x 100 mm is attached thereto, and a 1 § plumb is attached to the end of the PET film. Thereafter, the temperature is 80 ° C. In the dryer, the stainless steel plate was fixed with a hanging gage of 100 g, and the adhesive sheet was measured 24 hours later. The change amount of the inch is marked as OK if the dimensional change amount is 0.5 mm or less. Production Example 1 <(A) Synthesis of (meth)acrylic derivative polymer> With a condenser tube, a thermometer, and a stirring Apparatus, dropping funnel and nitrogen gas 23 201229183 Into the reaction vessel of the introduction tube, weighed 84 〇g of 2-ethylhexyl acrylate, 36.0 g of 2-hydroxyethyl acrylate and 150.0 g of methyl ethyl ketone as initial monomers. Nitrogen replacement was carried out by air volume of 100 ml/min, and heated from room temperature (25 ° C) to 70 ° C for 15 minutes. Thereafter, the surface was maintained at this temperature while using 2-ethylhexyl acrylate 2-1.0. g and acrylic acid _2. 基 基 经 9 9 9 作为 作为 作为 作为 作为 作为 作为 作为 作为 9 9 9 9 9 9 9 9 9 9 9 9 9 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过 过After the completion of the reaction, the reaction was further carried out for 2 hours. Then, by using the butanone to obtain a copolymer of acrylic acid and ethyl acrylate, the weight average molecular weight was (9). (The copolymer is hereinafter referred to as "propylene (tetra) contact polymer"). The measurement of the weight average molecular weight is The thf solvent used for the method is performed, it is determined using the following apparatus and measurement conditions using quasi-hand drive prongs polyethylene calibration curve of ethylene present apparatus: manufactured by Hitachi, Ltd. The RI detector: L-3350
使用溶劑：THF 管柱：曰立化成工業 GL-R420 + R430 + R440 管柱溫度：40°C 流量.2.0ml/min 比較製造例1 股份有限公司製造之Gelpac 1> < (C)具有2 g此之(甲基)丙烯醯基之交聯劑之 合成 24 201229183 於附有冷凝管、溫度計、授拌裝置、滴液漏斗及空氣 >主入管之反應容器中稱取聚丙二醇（分子量為2,〇〇〇) 223.12g、内醋改質丙烯酸羥基乙酿7,、丙烯酸々·乙 旨99.68 g、作為聚合抑制劑之對曱氧基苯㈣i2 g及 心觸，之二丁基二月桂酸錫G 5 g，—面流通空氣一面升 ^佛後’於^ Ύ —面縣—面以2小時均勾地滴加 ”佛爾酮二異氰酸酯49.35 g，進行反應。 ，滴加結束後，使其反應5小時Γ紐進—步追加丙 ^果g ’使其反應1小時。進行IR測定 。確1、鼠酸酯消失而結束反應，獲得具 聚二異佛_二異氰_旨作為重複單元，錄兩末端直^ ^性不飽和鍵之聚丙烯酸胺基甲酸自旨（重量平均八&旦 峻=3該聚丙稀酸胺基甲酸醋稱為 ^聚二丙烯 製造例2 b <(C)具有2官能之(甲基)丙_基之交聯劑之合成 注入tit凝官、溫度計、攪拌裝置、滴液漏斗及空氣 :㈣.74g、作為聚合：二8=苯:=_2-乙基 Ϊ^™Γ"0·58'-^ 小時均勻地滴加異 25 201229183 於滴加結束後’使其反應5小時，然後進一步追加 烯酸-2·羥基乙酯44.88 g，使其反應1小時。進行= 之結果，確認異氰酸醋消失而結束反應，獲得具有聚丙一 醇與異佛爾酮二異氰酸酯作為重複單元，且於兩末端4 聚合性不飽和鍵之聚丙烯酸胺基曱酸酯（重量平均分子旦 為20,〇〇〇)(以下將該聚丙烯酸胺基曱酸酯稱為「聚二里 烯酸胺基甲酸酯2」）。 — 製造例3 < (C)具有2官能之（甲基)丙稀酿基之交聯劑之合成 3> ° 於附有冷凝管、溫度計、授拌裝置、滴液漏斗及空氣 /主入g•之反應谷器中稱取聚丙二醇（分子量為2,〇〇〇 )285.3 g、丙烯酸-2-乙基己酯100. g、作為聚合抑制劑之對曱氧基 苯酚0.13 g及作為觸媒之二丁基二月桂酸錫〇 5g，一面流 通空氣一面升溫至75。(：後，一面於75。(：下攪拌一面以2 小時均勻地滴加異佛爾酮二異氰酸酯39.6 g，進行反應。 於滴加結束後，使其反應4小時後，投入内酯改^丙 烯酸羥基乙酯24.5 g，然後進一步於丨小時後追加丙烯酸 -2-羥基乙酯45.0 g，使其反應i小時。進行IR測定之結果， 確認異氰酸酯消失而結束反應，獲得具有聚丙二醇與異佛 爾酮二異氰酸酯作為重複單元，且於兩末端具有聚合性不 飽和鍵之聚丙烯酸胺基甲酸酯（重量平均分子量為3g，〇〇〇) (以下將該聚丙烯酸胺基甲酸s旨稱為「聚二丙烯酸胺基甲 酸酯3」）。 26 201229183a 比較製造例2 < (C)具有2官能之(曱基)丙_基之交聯劑之合成 4> 於附有冷凝管、溫度計、攪拌裝置、滴液漏斗及空氣 注入管之反應容器中稱取聚丙二醇（分子量為3 g、丙烯酸-2-乙基己酯100. g、作為聚合抑制劑之對甲氧基 苯酚0.13 g及作為觸媒之二丁基二月桂酸錫〇 5 g，—面二 通空氣一面升溫至75°C後，一面於75°C下擾拌一面以2 小時均勻地滴加異佛爾酮二異氰酸酯39.6 g，進行反應。 於滴加結束後，使其反應5小時後，投入内酯改質丙 烯酸羥基乙酯24.5 g，然後進一步於丨小時後追加丙烯酸 -2-羥基乙酯45.0 g，使其反應1小時。進行IR測定之結果， 確認異氰酸酯消失而結束反應，獲得具有聚丙二醇與異佛 爾酮二異氰酸酯作為重複單元，且於兩末端具有聚合性不 飽和鍵之聚丙烯酸胺基甲酸酯（重量平均分子量為56,〇〇〇) (以下將該聚丙烯酸胺基甲酸酯稱為「聚二丙烯酸胺基甲 酸酯4」）。 實例1 <樣品調配及黏著片製作> 稱量製造例1中所得之丙烯酸系衍生物聚合物3〇 8 g、丙稀酸-2-乙基己酯（EHA ) 38.7 g、丙婦酿基嗎琳 (ACMO) 18.5 g、丙烯酸-4-羥基丁酯（4-HBA) 5·〇 g、 製造例2中所得之聚二丙烯酸胺基甲酸酯2 6.5 g、經基 環己基苯基酮（1-184) 0.5 g，進行攪拌混合而獲得黏著性 27 201229183 樹脂組成物。 其後，於聚對笨二 著片用黏著性樹脂組成物， =醋’藉由梃而將黏著性樹脂組成物甲 使1外線照射裝置’照射2，_mJ/cm2之紫外線而獲得 透明黏著片。 實例2、實例3及比較例1〜比較例4 以表1及表2中所記载之調配成分及調配量，藉由與 實例1同樣之方法而製作黏著性樹脂組成物及黏著片。 [表Solvent: THF Column: 曰立化成工业 GL-R420 + R430 + R440 Column temperature: 40 ° C Flow rate 2.0 ml/min Comparative Manufacturing Example 1 Gelpac 1 manufactured by Co., Ltd. < (C) 2 g Synthesis of the (meth)acrylonitrile-based cross-linking agent 24 201229183 Weigh polypropylene glycol in a reaction vessel with a condenser, a thermometer, a mixing device, a dropping funnel, and an air inlet tube (molecular weight is 2, 〇〇〇) 223.12g, internal vinegar modified acrylic hydroxyethyl 7 , yttrium acrylate · 99.68 g, as a polymerization inhibitor of p-nonyl benzene (tetra) i2 g and heart contact, dibutyl lauric Acid tin G 5 g, the surface is ventilated on the side of the air, and the reaction is carried out by adding "Folketone diisocyanate 49.35 g" to the surface of the buddha. The reaction was allowed to proceed for 5 hours, and the reaction was carried out for 1 hour. The IR measurement was carried out. It was confirmed that the steric acid ester disappeared and the reaction was terminated to obtain a polydextrose-diisocyanide. Repeat unit, recording polyacrylamide formic acid at both ends of the direct ^ ^ unsaturated bond (weight average eight & am p;Danjun=3 The polyacrylic acid carboxylic acid vinegar is called [polydipropylene] Production Example 2 b < (C) Synthetic injection of a bifunctional (meth) propyl-based cross-linking agent , thermometer, stirring device, dropping funnel and air: (4). 74g, as polymerization: 2 8 = benzene: = 2 - ethyl Ϊ ^ TM Γ " 0 · 58 '- ^ hourly evenly add different 25 201229183 After the completion of the addition, the reaction was allowed to proceed for 5 hours, and then 44.88 g of the enoic acid-2·hydroxyethyl ester was further added thereto, and the mixture was allowed to react for 1 hour. As a result of the determination, it was confirmed that the isocyanic acid disappeared and the reaction was terminated to obtain a polypropanol. Polyacrylamide decanoate (weight average molecular denier 20, 〇〇〇) with isophorone diisocyanate as a repeating unit and 4 polymerizable unsaturated bonds at both ends (hereinafter the polyacrylamide hydrazide) The acid ester is referred to as "polydimonic acid urethane 2"). - Production Example 3 < (C) Synthesis of a crosslinking agent having a bifunctional (meth) propylene monomer 3 > ° Weighing polypropylene glycol (molecular weight 2, 〇〇) in a reaction vessel with a condenser, a thermometer, a mixing device, a dropping funnel, and an air/main g• 285.3 g, 2-ethylhexyl acrylate 100 g, 0.13 g of p-nonyloxyphenol as a polymerization inhibitor, and 5 g of dibutyltin laurate as a catalyst, heated to 75 while flowing air (: Afterwards, one side was 75. (: 39.6 g of isophorone diisocyanate was uniformly added dropwise over 2 hours while stirring, and the reaction was carried out. After the completion of the dropwise addition, the reaction was carried out for 4 hours, and then the lactone was changed. ^ 24.5 g of hydroxyethyl acrylate, and further, 45.0 g of 2-hydroxyethyl acrylate was added after 丨 hours, and allowed to react for 1 hour. As a result of the IR measurement, it was confirmed that the isocyanate disappeared and the reaction was terminated, and a polyacrylamide having a polyacrylic acid and isophorone diisocyanate as a repeating unit and having a polymerizable unsaturated bond at both terminals (weight average molecular weight) was obtained. It is 3g, 〇〇〇) (hereinafter, this polyacrylic acid carboxylic acid s is called "polydiacrylate urethane 3"). 26 201229183a Comparative Production Example 2 < (C) Synthesis of a bifunctional (fluorenyl)propyl-based crosslinking agent 4> Reaction with a condenser, a thermometer, a stirring device, a dropping funnel, and an air injection tube In the container, polypropylene glycol (molecular weight: 3 g, 2-ethylhexyl acrylate 100. g, p-methoxyphenol as a polymerization inhibitor, 0.13 g, and dibutyltin dilaurate as a catalyst) were weighed. g, the surface of the two-pass air was raised to 75 ° C, and then, while stirring at 75 ° C, 39.6 g of isophorone diisocyanate was uniformly added dropwise over 2 hours to carry out the reaction. After reacting for 5 hours, the lactone was changed to 24.5 g of hydroxyethyl acrylate, and further, 45.0 g of 2-hydroxyethyl acrylate was added thereto for 1 hour, and the reaction was carried out for 1 hour. The result of IR measurement confirmed that the isocyanate disappeared. The reaction was terminated to obtain a polyacrylic acid urethane having a polypropylene glycol and isophorone diisocyanate as a repeating unit and having a polymerizable unsaturated bond at both terminals (weight average molecular weight: 56, 〇〇〇) (hereinafter) Polyacrylamide The acid ester is referred to as "polyacrylic acid urethane 4"). Example 1 <Sample preparation and adhesive sheet preparation> The acrylic derivative polymer obtained in Production Example 1 was weighed 3 〇 8 g, propylene Acid-2-ethylhexyl ester (EHA) 38.7 g, propylene-glycoline (ACMO) 18.5 g, 4-hydroxybutyl acrylate (4-HBA) 5·〇g, the polymerization obtained in Production Example 2 26.5 g of bisacrylic acid urethane and 0.5 g of cyclohexyl phenyl ketone (1-184) were stirred and mixed to obtain an adhesive composition of 2012 201283183. Thereafter, it was used for the use of polypyrene Adhesive resin composition, = vinegar's adhesive resin composition was made by 梃, and the external light irradiation device was irradiated with ultraviolet rays of 2, _mJ/cm2 to obtain a transparent adhesive sheet. Example 2, Example 3, and Comparative Example 1 Comparative Example 4 An adhesive resin composition and an adhesive sheet were produced in the same manner as in Example 1 by using the blending components and the blending amounts described in Tables 1 and 2.
Cgr碰減甲㈣2 (於製造例2中 两嫌酸胺基甲酸醋3 (於製造例Cgr hits A (4) 2 (in Production Example 2, two succinic acid carboxylic acid vinegar 3 (in the manufacturing example)
剪力評價 28 201229183 -· · Α· ϊ [表2]Shear evaluation 28 201229183 -· · Α· ϊ [Table 2]
if a 比較例1 比較例2 比較例3 比較例4 調配條件 (A) 丙烯酸系衍生物聚合物 r於匍造例1中調製） 30.8 30.8 30.8 30.8 (B) RHA 37.2 35.2 38.7 38.7 ACMO 18.5 18.5 18.5 18.5 4-HBA 10.0 5.0 5.0 5.0 (C) 聚二丙烯酸胺基甲酸酯1(於比較製 造例1中調製） - - 6.5 - 聚二丙烯酸胺基甲酸酯3(於製造例 3中調製） 3.0 10.0 - - 聚二丙烯酸知基甲酸酯4(於比較製 造例2中調製） - - - 6.5 (D) 1-184 0.5 0.5 0.5 0.5 ____玻璃轉移溫度（°c) 9 16 10 B 外觀評價 85/85 A B B 100 A B B TCT A B A _ 剪力評價 B A AIf a Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Preparation conditions (A) Acrylic derivative polymer r was prepared in Preparation Example 1) 30.8 30.8 30.8 30.8 (B) RHA 37.2 35.2 38.7 38.7 ACMO 18.5 18.5 18.5 18.5 4-HBA 10.0 5.0 5.0 5.0 (C) Polydiacrylate urethane 1 (prepared in Comparative Production Example 1) - - 6.5 - Polydiacrylate urethane 3 (modulated in Production Example 3) 3.0 10.0 - - Polydimethacrylate 4 (modulated in Comparative Production Example 2) - - - 6.5 (D) 1-184 0.5 0.5 0.5 0.5 ____ Glass transition temperature (°c) 9 16 10 B Appearance Evaluation 85/85 ABB 100 ABB TCT ABA _ Shear evaluation BAA
[產業上之可利用性] 藉由使用本發明之影像顯示裝置用黏著性樹脂組成 物，了提供具有耐衝擊性、視認性優異之影像顯示裝置。 特別疋視涊側之透明保護板（例如玻璃）與黏著性樹脂組 ^物之密接力高，即使暴露於如85〇c/85%RH這樣的高溫 產生剝落、隆起、氣泡等，不使顯示器之視認 之邻件貼二即’可將影像顯示單元與影像顯示裝置所必需 ί可將較影像顯示裝置之影像顯示單元更靠 明保護板等崎讀透龍護板、難面板與透 【圖式簡單說明】 29 201229183 圖1是表示本發明之影像顯示裝置之剖面結構的概略 圖。 【主要元件符號說明】 1 :透明保護板（玻璃或塑膠基材） 2 :觸控面板 3 :偏光板 4.液晶顯不夺元 5:用以貼合透明保護板與觸控面板之黏著層 6:用以貼合觸控面板與偏光板之黏著層[Industrial Applicability] By using the adhesive resin composition for an image display device of the present invention, an image display device having excellent impact resistance and visibility is provided. In particular, the transparent protective plate (for example, glass) on the side of the crucible has a high adhesion to the adhesive resin group, and does not cause the display to be peeled off, swelled, bubbled, or the like even when exposed to a high temperature such as 85 〇c/85% RH. It can be seen that the image display unit and the image display device can be used to display the image display unit of the image display device, and the image protection unit of the image display device can be read by the stencil, the hard cover panel and the transparent image. BRIEF DESCRIPTION OF THE DRAWINGS 29 201229183 FIG. 1 is a schematic view showing a cross-sectional structure of a video display device of the present invention. [Main component symbol description] 1 : Transparent protection board (glass or plastic substrate) 2 : Touch panel 3 : Polarizer 4. Liquid crystal display does not take element 5: used to adhere the transparent protection board and the touch panel adhesive layer 6: used to adhere the adhesive layer of the touch panel and the polarizing plate
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| Application Number | Priority Date | Filing Date | Title |
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| JP2010276330 | 2010-12-10 |
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| TW201229183A true TW201229183A (en) | 2012-07-16 |
| TWI535813B TWI535813B (en) | 2016-06-01 |
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| TW100145741A TWI535813B (en) | 2010-12-10 | 2011-12-12 | Adhesive resin composition for image display device, adhesive sheet for image display device, image display device and fabricating method thereof |
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| Country | Link |
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| JP (1) | JP5790663B2 (en) |
| TW (1) | TWI535813B (en) |
| WO (1) | WO2012077809A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108473830A (en) * | 2015-05-18 | 2018-08-31 | 藤森工业株式会社 | Adhesive resin layer and adhesive resin film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104755517B (en) * | 2012-10-31 | 2017-12-08 | 昭和电工株式会社 | Polymerizable composition, polymerizable composition, polymer, optical-use pressure-sensitive adhesive sheet, image display device and its manufacture method |
| JP6038660B2 (en) * | 2013-01-10 | 2016-12-07 | 日立マクセル株式会社 | Curable adhesive composition, adhesive and adhesive sheet |
| JP6163824B2 (en) * | 2013-03-28 | 2017-07-19 | 日立化成株式会社 | Adhesive resin composition for image display device, adhesive sheet for image display device, method for producing image display device, and image display device |
| JP6155778B2 (en) * | 2013-04-08 | 2017-07-05 | 日立化成株式会社 | Adhesive composition |
| JP6610256B2 (en) * | 2014-07-22 | 2019-11-27 | 三菱ケミカル株式会社 | Active energy ray-curable pressure-sensitive adhesive composition, pressure-sensitive adhesive using the same, and pressure-sensitive adhesive sheet |
| JP5997405B1 (en) * | 2016-04-06 | 2016-09-28 | 大日精化工業株式会社 | Adhesive composition and laminate |
| JP7160838B2 (en) * | 2017-12-18 | 2022-10-25 | 株式会社クラレ | Method for manufacturing liquid crystal display protection plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61207476A (en) * | 1985-03-12 | 1986-09-13 | Hitachi Chem Co Ltd | Radiation-curable self-adhesive for surface protective film used for drawing process |
| JP3660462B2 (en) * | 1997-03-26 | 2005-06-15 | トッパン・フォームズ株式会社 | Pressure-sensitive adhesive printing sheet |
| CN101998982A (en) * | 2008-04-11 | 2011-03-30 | 3M创新有限公司 | Transparent adhesive sheet and image display device including the same |
| JP2010189545A (en) * | 2009-02-18 | 2010-09-02 | Nitto Denko Corp | Double-sided self-adhesive sheet and self-adhesive optical member |
-
2011
- 2011-12-09 WO PCT/JP2011/078619 patent/WO2012077809A1/en active Application Filing
- 2011-12-09 JP JP2012547936A patent/JP5790663B2/en not_active Expired - Fee Related
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|---|---|---|---|---|
| CN108473830A (en) * | 2015-05-18 | 2018-08-31 | 藤森工业株式会社 | Adhesive resin layer and adhesive resin film |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI535813B (en) | 2016-06-01 |
| JPWO2012077809A1 (en) | 2014-05-22 |
| JP5790663B2 (en) | 2015-10-07 |
| WO2012077809A1 (en) | 2012-06-14 |
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