201245380 六、發明說明： 【發明所屬之技術領域】 本發明係關於藉由電子束或紫外料之活性能 '' 可接著各種基材之活性能量線硬化型接著 成物。 本發明之組成物係適用於作為光學零件使用之 薄膜:戈塑膠片（以下將「薄膜或片」統一稱為「薄! 荨之薄層被接著體的積層接著，進—步適用於使用 晶顯示元件、EL(電致發光）顯示元件投影顯示元 電漿顯示元件等之各種光學薄膜或片之製造，在此 術領域t獲得讚賞而被使用。 【先前技術】 以往’在貼合塑膠薄膜等之薄層被接著體彼此 、或塑膠薄膜等之薄層被接著體和由此外的素材所 之薄層被接著體之積層法中，主要施行在第1薄層 著體上塗布含有乙烯-乙酸乙烯共聚物或聚胺基甲 系聚合物之溶劑型接著劑組成物並乾燥後，於其上 軋輥荨將第2薄層被接著體加壓接著之乾式積層法 於此方法所使用之接著劑組成物，一般係為了 成物之塗布量均勻而含有許多溶劑者，為此在乾燥 揮發大量的溶劑蒸氣，造成毒性、作業安全性以及 污染性之問題。 作為解決此等問題之接著劑組成物，探討無溶 之接著劑組成物。 量線 劑組 塑膠 莫j ) 在液 件、 等技 之間 構成 被接 酸酯 藉由 〇 使組 時會 環境 劑系 -4 - 201245380 作為無溶劑系接著劑組成物，廣泛使用2液型接著 劑組成物以及藉由紫外線或電子束等之活性能量線硬化 之接著劑組成物。 作為2液型接著劑組成物’主要使用末端具有羥基 之聚合物作為主劑、末端具有異氰酸酯基之聚異氰酸酯 化合物作為硬化劑’即所謂的聚胺基甲酸酯系接著劑組 成物。然而該組成物有耗費過多硬化時間之缺點。 相對於此，活性能量線硬化型接著劑組成物因為硬 化速度快而生産性優異，最近受到注目。 另一方面’以液晶顯示裝置作為代表之薄型顯示裝 置，在電子時鐘或各種電子製品中之簡單的顯示裝置自 不用提，還廣泛使用為電視、筆記型電腦、手機及文字 處理機等之顯示元件。近年來，在貼合使用於該液晶顯 不7L件之各種光學薄膜時，亦使用活性能量線硬化型 著劑。 對於使用於該光學薄膜之接著劑組成物，要求在高 溫及咼濕條件下之嚴苛條件中，可維持其接著力之性能 Ο 作為高溫及高濕度下接著性優異之活性能量線硬化 型接著劑組成物’本案申請人至今已提出含有胺基曱酸 酯（曱基）丙烯酸酯與玻璃轉移溫度為4〇ec以上之聚合物 的組成物（專利文獻1)、以及含有胺基甲酸酯（曱基）丙烯 酸酯與具有環狀亞胺基之（甲基）丙烯酸酯的組成物（專利 文獻2)。 -5- 專利文獻1 專利文獻2 專利文獻3 專利文獻4 專利文獻5 專利文獻6 201245380 又’作為接著劑’本案申請人提出一種活性能量 硬化型接著劑組成物（專利文獻3 )，其係包含特定結構 胺基甲酸S旨（曱基）丙烯酸酯與具有環狀結構之特定單 能（曱基）丙稀酸酯的組成物，在其中以特定比例含有 基丙烯酸酯。 又’除了上述接著劑組成物以外，已知併用胺基 酸醋（甲基）丙稀酸酯與（甲基）丙烯醯胺系化合物之活 能量線硬化型接著劑缒成物（專利文獻4〜6)。 先前技術文獻 專利文獻 曰本特開2000-072833號公報 曰本特開2001-064594號公報 國際公開第2006/1 1 8078號小冊子 曰本特開平9-157317號公報 曰本特開平7-3 10067號公報 曰本特開2007-177169號公報 【發明内容】 [發明所欲解決之課題] 然而’將以往之活性能量線接著劑組成物使用於 勝薄膜之接著時’有時會因硬化收縮而使所得之積層 發生麵曲（捲曲）。 再加上近年來由於顯示裝置的薄型化、小型化， 種驅動裝置或光源等所產生的熱不被擴散而集中於薄 積層體之一部分，再者，當在會被陽光照射之戶外使 汽車導航裝置等製品時，不是製品整體而會有僅一部 線 之 官 甲 甲 性 塑 體 各 膜 用 分 -6- 201245380 過度地溫度升高。當薄膜積層體使用以往提出之接著劑 組成物時，若熱集中於薄膜積層體之一部分 '則會產生 撓曲，其結果造成所得之圖像的可見性降低或歪斜 題。 此外，本發明者等探討之結果，在專利文獻4〜6所 記載之組成物中，當所得之積層體很少翹曲或撓曲時， 接著強度有時不充分；當所得之積層體沒有翹曲、接著 力優異時’有時撓曲會變多；而無所得之積層體不但沒 有翹曲或撓曲、接著力亦優異者。 又 於是本發明者等為了找出接著力優異、所得之積層 體很少勉曲、即使在部分地被加熱之狀況下薄膜積層二 亦很少撓曲之活性能量線硬化型接著劑組成物而專心致 力進行了探討。 [用以解決課題之手段] 本發明者等經過各種研究的結果，發現—種活性能 量線硬化型接著劑組成物，其係包含胺基甲酸酯（甲基&) 丙烯酸酯與（曱基）丙烯醯胺化合物之組成物，在其中'"以 特定比例含有具有曱基丙烯醯基之彳匕合物的組成物接= 力優異、即使在高溫下使用亦可抑制薄膜之撓曲、並已 達到實用性等級，而完成了以下所示之本發明。 本發明係關於一種活性能量線硬化型接著劑組成物 (以下亦僅稱為「本發明之接著劑組成物」或「本發明之 組成物」），其含有 (Α)成分.胺基甲酸酯（甲基）丙烯酸酯（以下稱為「 成分」）， 201245380 (B) 成分.含有以後述式（1)所表示之化么_私/ 〜。物（以下稱 為「（甲基）丙烯醯胺（1)」）及以後述式（2)所表Γ 不之化合物 (以下稱為「（甲基）丙烯醯胺（2)」），相對於^ Μ、 丁 ％ (甲基）丙烯醯 胺（1)及（2)之合計量100重量份，包含* ° 5重量份的（ 曱基）丙烯醯胺（1)與5〜95重量份的（甲甚、 丞）丙烯醯胺（1) 之（曱基）丙烯醯胺化合物（以下稱為「（B)成分」），以 (C) 成分：上述（A)及（B)成分以外之具有^稀性 和基之化合物（以下稱為「（C)成分」）， 相對於（Α)〜（C)成分之合計量，以下述比例含有 〜（C)成分及具有曱基丙烯醯基之化合物。 (Α)成分：5〜50重量％ (Β)成分：30〜93重量％ (C)成分：2〜65重量％ 具有曱基丙烯醯基之化合物：2〜3〇重量％ 作為（Α)成允，較佳為非芳香族系之胺基甲酸酯（曱 基）丙烯酸酯。又，作為（Α)成分，較佳為具有聚碳酸酯 月架之胺基甲酸酯（甲基）丙烯酸酯。又，作為（Α)成分， 較佳為重量平均分子量500〜5萬之化合物。 作為（Β)成分’較佳為（甲基）丙烯醯胺（1)在後述式（1) 中’ R及R3為氫原子或碳原子數1〜3之烷基的化合物 作為本發明之組成物，較佳為進一步含有（D)光聚合 起始劑者’較佳為相對於組成物丨〇 〇重量份以〇丨〜丄〇 重$份之比例含有上述（D)成分者。 -8- 201245380 作為本發明之組成物，較佳為硬化物之玻璃轉移溫 度為60〜180 °C者。 又，本發明之組成物可較佳使用於薄層積層體之製 造，較佳為由基材、本發明之組成物的硬化物以及其它 基材所構成之積層體，作為該基材，較佳為至少一方的 基材為塑膠基材者。 本發明之組成物，可較佳使用作為塑膠基材之接著 劑組成物’又，可較佳使用作為光學材料用之接著劑組 成物，又，可較佳使用作為光學薄膜積層用接著劑組成 又，本發明係一種積層體之製造方法，其包含 在第1基材上塗布上述任一組成物之步驟， 在上述組成物貼合第2基材之步驟， 自上述第1基材或第2基材側照射活性能量線之步 作為第1基材或第2基材，較佳為至少—方為㈣ 土材，較佳為光學構件，較佳為光學薄膜。 再者，本發明亦關於一種由第i基材、上述組成物 及第2基材所構成之積層體。作為第1基材或 弟2基材，較佳為至少一方為塑膠基材。 [發明效果] 據本發明之組成物’可提供對基材之接著性優 特別對塑膠基材之接著性優異，所得之積層體的經 翹曲少，進一步在加熱試驗後的撓曲少之活性 化型接著劑組成物 -9 - 201245380 因此，本發明之組成物係活用此等特性，有效於作 為各種光學構件所使用的塑膠薄膜等之薄層被接著體的 接著，特別可適用於製造用於液晶顯示裝置等之光學薄 膜。 【實施方式】 以下詳細說明本發明。 此外，在本說明書中，將丙烯酸酯及/或甲基丙婦酸 醋表示為（曱基）丙稀酸酯、將丙稀醯基及/或甲基丙烯酿 基表示為（甲基）丙烯醯基、以及將丙烯酸及/或曱基丙稀 酸表示為（甲基）丙烯酸。 本發明之活性能量線硬化型接著劑組成物係作為必 要成分含有上述（A)、（B)成分及（C)成分者。 以下針對各成分作說明。 此外’作為（A)〜（C)成分，可單獨使用後述各自之 化合物’亦可併用2種以上使用。 1 · (A)成分 (A)成分係胺基曱酸酯（曱基）丙烯酸酯。 作為（A)成分’可使用各種胺基甲酸酯（曱基）丙稀酸 醋’具體而言’可列舉具有聚酯骨架、聚醚骨架或聚碳 酸醋骨架之胺基曱酸酯（曱基）丙烯酸酯。 此等之中’在所得之硬化物在高溫及高濕條件下之 接著力優異的觀點，較佳為具有聚酯骨架或聚碳酸酯骨 架之胺基曱酸酿（甲基）丙烯酸酯，更佳為具有聚碳酸酯 骨架之胺基甲酸酯（曱基）丙烯酸酯。 -10- 201245380 作為（A)成分，低聚物及聚合物之任一者都可使用， 較佳為重量平均分子量500〜5萬者，更佳為3,000〜5 萬者’特佳為1萬〜4萬者。 此外，在本發明中，重量平均分子量係將藉由凝膠 滲透層析法測定之分子量換算為聚苯乙烯之値。 作為（A)成分，更具體而言，可列舉多元醇、有機聚 異氰酸酯及含有羥基之（甲基）丙烯酸酯的反應物等，較 佳為使έ有經基之（曱基）丙稀酸醋對多元醇與有機聚異 氰酸酯反應物反應之化合物。 又’作為（Α)成分，較佳為具有2個（曱基）丙烯醯基 之胺基甲酸酯（甲基）丙烯酸酯（以下亦稱為2官能胺基甲 酸醋（曱基）丙烯酸酯），更佳為使含有羥基之（甲基）丙烯 酸酯對具有聚酯、聚醚或聚碳酸酯骨架之二醇與有機二 異氰酸酯之反應物反應而成之2官能胺基曱酸酯（甲基） 丙浠酸酯。 作為多元醇，較佳為具有聚酯骨架之二醇、具有聚 醚骨架之二醇及具有聚碳酸酯骨架之二醇。 作為具有聚酯骨架之多元醇，可列舉低分子量二醇 或聚己内酯二醇等之二醇成分，與二元酸或其酐等之酸 成分的酯化反應物等。 作為低分子量二醇，可列舉乙二醇、丙二醇、環己 二甲醇、3-甲基-1，5-戊二醇及1，6-己二醇等。 作為二元酸或其酐，可列舉己二酸、丁二酸、酞酸 、四氫酞酸、六氫酞酸及對苯二曱酸等、以及此等之酐 等。 -11- 201245380 作為聚醚多元醇，可列舉聚乙二醇、聚丙二醇、聚 四曱二醇等。 作為聚碳酸酯多元醇，可列舉上述低分子量二醇或/ 及雙酚A等之雙酚，與碳酸乙二酯及碳酸二丁酯等之碳 酸二烷基酯的反應物等。 作為有機聚異氰酸酯，可列舉甲苯二異氰酸酯、1，6 -己二異氰酸酯、二苯甲烷-4，4·-二異氰酸酯、聚亞曱基聚 苯基異氰酸酯、1，6 -己二異氰酸酯三聚物、氫化曱苯二 異氰酸酯、氫化-4，4L二苯甲烷二異氰酸酯、苯二曱基二 異氰酸酯、氫化苯二甲基二異氰酸酯、對苯二異氰酸酯 、甲苯二異氰酸酯二聚物、1，5_萘二異氰酸酯、六亞甲 二異氰酸酯相互加成物' 4,4 ’ -二環己基曱院二異氰酸酯 、三羥曱丙烷參（甲苯二異氰酸酯）加成物及異佛酮二異 氰酸酯等。 又，有機聚異氰酸酯較佳為有機二異氰酸酯。 作為含有經基之（甲基）丙稀酸酯，可列舉（甲基）丙稀 酸2 -經乙酯、（甲基）丙稀酸2 -經丙酯、（甲基）丙烯酸經 丁酿、（甲基）丙浠酸經戊g旨、（甲基）丙稀酸經己醋及（甲 基）丙烯酸羥辛酯等之（甲基）丙烯酸羥烷基酯；新戊四醇 二、二或單（甲基）丙稀酸酯’及三經甲丙燒二或單（甲基） 丙烯酸酯等之含有羥基之多元醇聚（曱基）丙烯酸酯等。 作為含有羥基之（甲基）丙烯酸酯，較佳為（甲基）丙稀 酸羥烷酯。 作為（A)成分之製造方法，遵循常用方法即可，可列 舉： -12- 201245380 1) 胺基甲酸酯化觸媒的存在下，加熱攪拌多元醇與 有機聚異氰酸酯使其加成反應而製造具有異氰醆酯之預 水物於其中添加（甲基）丙烯酸羥烷基酯，加熱攪拌使 其加成反應之製造方法，及 2) 胺基甲酸酷化觸媒的存在下，加熱攪拌多元醇、 有機聚異氰酸酯及（甲基）丙烯酸羥烷基酯之製造方法等 〇 作為（A)成分’較佳為藉由上述丨）之製造方法所得者 〇 作為胺基曱酸酯化觸媒，可列舉二丁錫二月桂酸酯 等之錫系觸媒、參（乙醯丙酮）鐵等之鐵系觸媒、雙（乙醯 丙酮）鋅等之鋅系觸媒。 作為（A)成分’在高濕度下的接著強度特別優異、硬 化後之接著劑的經時性著色少之觀點，較佳為非芳香族 系之胺基甲酸酯（曱基）丙烯酸酯。 非^'香族系之胺基曱酸f旨（甲基）丙烯酸g旨，具體而 言’可列舉由非芳香族系之多元醇及非芳香族系之聚異 氰酸5旨所製造的胺基甲酸酯（甲基）丙烯酸酯。 作為非芳香族系之多元醇’可列舉非芳香族系之聚 S曰多元醇、聚碳酸酯多元醇，較佳為非芳香族系之聚碳 酸S旨多元醇。 2·(Β)成分 (Β)成分係含有（甲基）丙烯醯胺（1)及（甲基）丙烯醯胺 (2)，且相對於（曱基）丙烯醯胺（1)及（2)之合計量1〇〇重量 份’包含5〜95重量份的（曱基）丙烯醯胺（丨）與95〜5重 量份的（甲基）丙烯醯胺（2)之（甲基）丙烯醯胺化合物。 -13- 201245380 本發明藉由含有（B)成分’可提升對基材之附著性， 並且提高組成物硬化物之玻璃轉移溫度，因此可防止所 得之積層體在加熱試驗後之撓曲。 (甲基）丙烯醯胺（1)係以下述式（1)所表示之化合物。201245380 VI. Description of the Invention: [Technical Field] The present invention relates to an active energy ray-curable splicing of various substrates by the active energy of an electron beam or a UV material. The composition of the present invention is suitable for use as a film for optical parts: Go plastic sheet (hereinafter, "film or sheet" is collectively referred to as "thin! The thin layer of tantalum is laminated by a bonding layer, and the step is applied to the use of crystal The manufacture of various optical films or sheets of display elements, EL (electroluminescence) display elements, projection display meta-plasma display elements, etc., has been appreciated in this field of art. [Prior Art] Conventional 'In-Plastic Plastic Films In the lamination method in which the thin layer is bonded to each other, or a thin layer of the plastic film or the like, and the thin layer of the material to be bonded thereto, the coating is mainly applied to the first thin layer. After the solvent-based adhesive composition of the vinyl acetate copolymer or the polyaminomethyl polymer is dried and then rolled, the second thin layer is pressed by the adherend and then the dry laminate method is used for the method. The composition of the agent generally contains a large amount of solvent in order to uniformly coat the amount of the product, and for this reason, a large amount of solvent vapor is volatilized and dried, causing problems of toxicity, work safety, and pollution. To determine the composition of the adhesives of these problems, to discuss the composition of the insoluble binder. The amount of the agent of the amount of the agent is a mixture of liquids and other techniques. -4 - 201245380 As a solventless adhesive composition, a two-component adhesive composition and an adhesive composition which is cured by active energy rays such as ultraviolet rays or electron beams are widely used. As a two-liquid type adhesive composition' A polyisocyanate compound having a hydroxyl group-terminated polymer as a main component and an isocyanate group at the end is mainly used as a hardener, that is, a so-called polyurethane-based adhesive composition. However, the composition has a disadvantage of excessive hardening time. On the other hand, the active energy ray-curable adhesive composition has recently been attracting attention because of its high curing speed and excellent productivity. On the other hand, a thin display device represented by a liquid crystal display device is used in an electronic clock or various electronic products. The simple display device is not used, and is widely used as a television, a notebook computer, a mobile phone, a word processor, and the like. In recent years, an active energy ray-curing type agent has been used in combination with various optical films used for the liquid crystal display. The adhesive composition used for the optical film is required to be at a high temperature and enthalpy. In the severe conditions under wet conditions, the performance of the adhesion can be maintained. 活性 An active energy ray-curable adhesive composition excellent in high-temperature and high-humidity adhesion. The applicant has so far proposed to contain an amino phthalate ( a composition of a fluorenyl acrylate and a polymer having a glass transition temperature of 4 〇 ec or more (Patent Document 1), and a urethane (fluorenyl) acrylate and a cyclic imine group (methyl group) Acetate composition (Patent Document 2). -5- Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 201245380 Further, as an adhesive, the applicant proposed an active energy hardening type. Composition (Patent Document 3), which comprises a specific structure of amino carboxylic acid S (meth) acrylate and a specific monoenergetic (fluorenyl) acrylate having a cyclic structure A composition in which a specific proportion of an acrylate-containing group. Further, in addition to the above-mentioned adhesive composition, an active energy ray-curable adhesive composition of an amino acid vinegar (meth) acrylate and a (meth) acrylamide compound is known (Patent Document 4) ~6). CITATION LIST Patent Literature Patent Publication No. 2000-072833, JP-A-2001-064594, International Publication No. 2006/1 1 8078, pp. Ben-Kei Kai 9-157317, 曰本特开平 7-3 10067 SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] However, the use of the conventional active energy ray-bonding agent composition in the case of the film is sometimes caused by hardening shrinkage. The resulting laminate was subjected to surface curling (curling). In addition, in recent years, due to the thinning and miniaturization of the display device, the heat generated by the driving device or the light source is not diffused and concentrated on one part of the thin laminated body, and further, when the automobile is exposed to the sun. When a product such as a navigation device is used, it is not a product as a whole, and there is only one line of the official nail-shaped plastic body. The film is excessively heated by the -6-201245380. When the film laminate is a conventionally proposed adhesive composition, if heat is concentrated on a portion of the film laminate, deflection occurs, and as a result, the visibility of the resulting image is lowered or skewed. Further, as a result of the investigation by the inventors of the present invention, in the compositions described in Patent Documents 4 to 6, when the obtained laminate is less warped or bent, the strength is sometimes insufficient; when the obtained laminate is not When the warpage and the adhesion are excellent, the deflection sometimes increases; and the laminate which is not obtained has no warpage or deflection, and the adhesion is excellent. In addition, the present inventors have found an active energy ray-curable adhesive composition which is excellent in adhesion, and the obtained laminated body is less distorted, and the film laminate 2 is rarely deflected even when partially heated. Dedicated to the discussion. [Means for Solving the Problem] The present inventors have found, as a result of various studies, an active energy ray-curable adhesive composition comprising a urethane (methyl & acrylate) and (曱A composition of a acrylamide compound in which a composition containing a mercaptopropenyl group-containing chelate in a specific ratio is excellent in strength, and can suppress film deflection even when used at a high temperature. The practicality level has been reached, and the present invention shown below has been completed. The present invention relates to an active energy ray-curable adhesive composition (hereinafter also referred to simply as "the adhesive composition of the present invention" or "the composition of the present invention"), which contains a (Α) component. Aminocarboxylic acid Ester (meth) acrylate (hereinafter referred to as "component"), 201245380 (B) Component. Contains the formula (1) described later. The compound (hereinafter referred to as "(meth)acrylamide (1)") and the compound represented by the following formula (2) (hereinafter referred to as "(meth)acrylamide (2)"), 100 parts by weight of the total amount of (meth) decylamine (1) and (2), containing 5 parts by weight of (mercapto) acrylamide (1) and 5 to 95 parts by weight (A, E, 丞) acrylamide (1) (mercapto) acrylamide compound (hereinafter referred to as "(B) component"), (C) component: other than the above components (A) and (B) The compound having a thinness and a base (hereinafter referred to as "(C) component") contains a component (~) and a mercaptopropene oxime in a ratio of (Α) to (C). Base compound. (Α) Component: 5 to 50% by weight (Β) Component: 30 to 93% by weight (C) Component: 2 to 65% by weight Compound having a mercaptopropenyl group: 2 to 3 % by weight as (Α) Preferably, it is a non-aromatic urethane (mercapto) acrylate. Further, as the (Α) component, a urethane (meth) acrylate having a polycarbonate shelf is preferable. Further, as the (Α) component, a compound having a weight average molecular weight of 500 to 50,000 is preferable. The (Β) component is preferably a (meth) acrylamide (1) compound in which R and R3 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms in the following formula (1). Preferably, the material further containing (D) a photopolymerization initiator is preferably one containing the component (D) in a proportion of 〇丨 to $ by weight of the composition 丨〇〇 by weight. -8- 201245380 As the composition of the present invention, it is preferred that the glass transition temperature of the cured product is 60 to 180 °C. Further, the composition of the present invention can be preferably used for the production of a thin layered laminate, preferably a laminate composed of a substrate, a cured product of the composition of the present invention, and other substrates, as the substrate. Preferably, at least one of the substrates is a plastic substrate. The composition of the present invention can be preferably used as an adhesive composition of a plastic substrate. Further, it can be preferably used as an adhesive composition for an optical material, and can be preferably used as an adhesive for an optical film laminate. Moreover, the present invention provides a method for producing a laminate comprising the step of applying the above-mentioned one of the above-described components on the first substrate, and bonding the second substrate to the composition, from the first substrate or the first substrate. 2 The step of irradiating the active energy ray on the substrate side is preferably the first substrate or the second substrate, and at least the material is (4), preferably an optical member, preferably an optical film. Furthermore, the present invention also relates to a laminate comprising an i-th substrate, the above composition, and a second substrate. As the first substrate or the second substrate, at least one of them is preferably a plastic substrate. [Effect of the Invention] The composition of the present invention can provide excellent adhesion to a substrate, and is particularly excellent in adhesion to a plastic substrate, and the obtained laminate has less warpage, and further has less deflection after a heating test. Activated adhesive composition -9 - 201245380 Therefore, the composition of the present invention utilizes these characteristics and is effective for the subsequent adhesion of a thin layer of a plastic film or the like used as various optical members, and is particularly suitable for use in manufacturing. An optical film used for a liquid crystal display device or the like. [Embodiment] Hereinafter, the present invention will be described in detail. Further, in the present specification, acrylate and/or methyl acetoacetate is represented as (mercapto) acrylate, and acrylonitrile and/or methacrylate is represented as (meth) propylene. The fluorenyl group, and the acrylic acid and/or mercaptoacrylic acid are represented as (meth)acrylic acid. The active energy ray-curable adhesive composition of the present invention contains the above components (A), (B) and (C) as essential components. The components are described below. Further, as the components (A) to (C), the respective compounds described below may be used singly or in combination of two or more kinds. 1 (A) Component The component (A) is an amino phthalate (mercapto) acrylate. As the component (A), various urethane (mercapto) acrylate vinegars can be used, and 'specifically' can be exemplified by an amino phthalic acid ester having a polyester skeleton, a polyether skeleton or a polycarbonate skeleton. Base) acrylate. Among these, 'the viewpoint of excellent adhesion of the obtained cured product under high temperature and high humidity conditions is preferably an amine phthalic acid (meth) acrylate having a polyester skeleton or a polycarbonate skeleton, and more A urethane (mercapto) acrylate having a polycarbonate skeleton is preferred. -10- 201245380 As the component (A), any of the oligomer and the polymer can be used, preferably a weight average molecular weight of 500 to 50,000, more preferably 3,000 to 50,000. ~40,000 people. Further, in the present invention, the weight average molecular weight is obtained by converting the molecular weight measured by gel permeation chromatography into polystyrene. Specific examples of the component (A) include a polyol, an organic polyisocyanate, and a reactant of a hydroxyl group-containing (meth) acrylate, and the like, and preferably a sulfhydryl group. A compound of vinegar that reacts a polyol with an organic polyisocyanate reactant. Further, as the (Α) component, a urethane (meth) acrylate having two (indenyl) acrylonitrile groups (hereinafter also referred to as a bifunctional amino carboxylic acid (mercapto) acrylate is preferable. More preferably, a bifunctional amine phthalate ester obtained by reacting a hydroxyl group-containing (meth) acrylate with a reaction of a diol having a polyester, a polyether or a polycarbonate skeleton with an organic diisocyanate (A) Base) propionate. The polyhydric alcohol is preferably a diol having a polyester skeleton, a diol having a polyether skeleton, and a diol having a polycarbonate skeleton. Examples of the polyol having a polyester skeleton include a diol component such as a low molecular weight diol or a polycaprolactone diol, and an esterification reaction product with an acid component such as a dibasic acid or an anhydride thereof. Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. Examples of the dibasic acid or its anhydride include adipic acid, succinic acid, citric acid, tetrahydrofurfuric acid, hexahydrononanoic acid, terephthalic acid, and the like, and the like. -11- 201245380 Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. The polycarbonate polyol may, for example, be a reaction product of a low molecular weight diol or a bisphenol such as bisphenol A or a dialkyl carbonate such as ethylene carbonate or dibutyl carbonate. Examples of the organic polyisocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane-4,4·-diisocyanate, polyfluorene polyphenyl isocyanate, and 1,6-hexamethylene diisocyanate terpolymer. , hydrogenated phthalic acid diisocyanate, hydrogenated-4,4L diphenylmethane diisocyanate, benzodiazepine diisocyanate, hydrogenated dimethyl diisocyanate, p-phenylene diisocyanate, toluene diisocyanate dimer, 1,5-naphthalene Diisocyanate, hexamethylene diisocyanate inter-addition product '4,4 '-dicyclohexyl sulfonium diisocyanate, trihydrogen propylene propane (toluene diisocyanate) adduct and isophorone diisocyanate. Further, the organic polyisocyanate is preferably an organic diisocyanate. Examples of the (meth) acrylate containing a trans group include (meth)acrylic acid 2-ethyl ester, (meth)acrylic acid 2-propyl ester, and (meth)acrylic acid. And (meth)propionic acid by glutinous, (meth)acrylic acid by hexyl vinegar and hydroxyoctyl (meth) acrylate, such as hydroxyalkyl (meth) acrylate; neopentyl alcohol A hydroxy group-containing polyol poly(mercapto) acrylate such as di- or mono-(meth) acrylate- and tri- or propylene-di- or mono-(meth) acrylate. As the hydroxyl group-containing (meth) acrylate, hydroxyalkyl (meth) acrylate is preferred. The method for producing the component (A) may be a conventional method, and may be exemplified by the following: -12- 201245380 1) In the presence of a urethane catalyst, the polyol and the organic polyisocyanate are heated and stirred to cause an addition reaction. A method for producing a pre-hydrated product having isocyanuric acid ester by adding a hydroxyalkyl (meth) acrylate thereto, heating and stirring to form an addition reaction, and 2) heating and stirring in the presence of an aminocarboxylic acid-cooling catalyst The method for producing a polyhydric alcohol, an organic polyisocyanate, and a hydroxyalkyl (meth) acrylate, etc., as the component (A) is preferably obtained by the production method of the above-mentioned ruthenium) as an amino phthalate catalyst. Examples thereof include tin-based catalysts such as dibutyltin dilaurate, iron-based catalysts such as acetylacetate, and zinc-based catalysts such as bis(acetonitrile)zinc. The non-aromatic urethane (mercapto) acrylate is preferred because the (A) component ' is particularly excellent in adhesion strength under high humidity and less time-dependent coloring of the adhesive after hardening. The non-aromatic amino acid is a (meth)acrylic acid, and specific examples thereof include a non-aromatic polyol and a non-aromatic polyisocyanate 5; Urethane (meth) acrylate. Examples of the non-aromatic polyol include a non-aromatic poly-S-polyhydric alcohol and a polycarbonate polyol, and a non-aromatic poly-carbonic acid S-based polyol. 2. (Β) component (Β) component contains (meth) acrylamide (1) and (meth) acrylamide (2), and relative to (mercapto) acrylamide (1) and (2) a total of 1 part by weight 'containing 5 to 95 parts by weight of (mercapto) acrylamide (hydrazine) and 95 to 5 parts by weight of (meth) acrylamide (2) of (meth) propylene Amidoxime compound. -13- 201245380 The present invention can improve the adhesion to the substrate by containing the component (B), and increase the glass transition temperature of the cured product of the composition, thereby preventing the resulting laminate from being flexed after the heating test. (Methyl) acrylamide (1) is a compound represented by the following formula (1).
(式（1)中，R1表示氫原子或甲基，R2及R3表示氩原 子或碳原子數1〜20之烴基，1分子中之R2及R3可為相 同之基，亦可為不同之基）。 作為碳原子數1〜20之烴基，較佳為烷基，可為直 鏈狀、亦可具有分支。作為烷基，亦可為進一步具有羥 基、芳香族基及二胺基烷基之烷基。 作為烷基之具體例，可列舉曱基、丙基、丁基、丁 基及己基等。 作為具有經基之炫基，可列舉羥曱基及羥乙基等。 作為具有芳香族基之烷基，可列舉苄基等。 作為具有經基之烧基，可列舉羥甲基、經乙基及經 丙基等。 作為二烧基胺基烧基’可列舉N，N-二甲基胺基乙基 及n，n-二曱基胺基丙基等。 此等之中又以烷基為較佳，更佳為碳原子數1〜3之 院基。 作為（曱基）丙烯醯胺（1)之具體例，可列舉N-甲基（ 曱基）丙烯醯胺、N-正丙基（甲基）丙烯醯胺、N-異丙基（ -14- 201245380 曱基）丙烯醯胺、N-正丁基（曱基）丙烯醯胺、N-二級丁基 (甲基）丙烯醯胺、N-三級丁基（曱基）丙烯醢胺、N-正己基 (甲基）丙烯醯胺、N-苄基（曱基）丙烯醯胺、N-羥基乙基（ 曱基）丙烯醯胺、N，N-二曱基胺基乙基（曱基）丙烯醯胺、 N，N-二曱基胺基丙基（曱基）丙烯醯胺、N，N-二甲基（曱基 )丙烯醯胺、N，N-二乙基（曱基）丙烯醯胺、N，N-二正丙基 (甲基）丙烯醯胺、N，N-二異丙基（甲基）丙烯醯胺、N，N-二正丁基（曱基）丙烯醯胺、Ν,Ν-二己基（曱基）丙烯醯胺、 二苄基（曱基）丙烯醯胺等之（甲基）丙烯醯胺衍生物。 此等之中又以對基材之浸蝕性高的Ν，Ν-二甲基（曱 基）丙烯醯胺、Ν，Ν-二乙基（曱基）丙烯醯胺為較佳。 (Β)成分藉由將（曱基）丙烯醯胺（1)與以下述式（2)所 表示之（甲基）丙烯醯胺（2)併用而使用，可不阻礙對基材 之浸蝕性’而可減少所得到之積層體在加熱狀況下的撓 曲。(In the formula (1), R1 represents a hydrogen atom or a methyl group, and R2 and R3 represent an argon atom or a hydrocarbon group having 1 to 20 carbon atoms, and R2 and R3 in one molecule may be the same group or may be different groups. ). The hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group, and may be linear or branched. The alkyl group may be an alkyl group further having a hydroxyl group, an aromatic group and a diaminoalkyl group. Specific examples of the alkyl group include a mercapto group, a propyl group, a butyl group, a butyl group, a hexyl group and the like. Examples of the thiol group having a thiol group include a hydroxy group and a hydroxyethyl group. Examples of the alkyl group having an aromatic group include a benzyl group and the like. Examples of the alkyl group having a mercapto group include a methylol group, an ethyl group, a propyl group and the like. Examples of the dialkylaminoalkyl group include N,N-dimethylaminoethyl and n,n-didecylaminopropyl. Among these, an alkyl group is preferred, and a hospital base having 1 to 3 carbon atoms is more preferred. Specific examples of the (fluorenyl) acrylamide (1) include N-methyl(fluorenyl) acrylamide, N-n-propyl (meth) acrylamide, and N-isopropyl (-14). - 201245380 曱 ) 醯 醯 、, N-n-butyl (decyl) acrylamide, N-butyl butyl (meth) acrylamide, N-tertiary butyl (fluorenyl) acrylamide, N-n-hexyl (meth) acrylamide, N-benzyl (fluorenyl) acrylamide, N-hydroxyethyl (decyl) acrylamide, N,N-didecylaminoethyl (曱) Acrylamide, N,N-didecylaminopropyl (decyl) acrylamide, N,N-dimethyl(decyl)propenylamine, N,N-diethyl (fluorenyl) ) acrylamide, N,N-di-n-propyl (meth) acrylamide, N,N-diisopropyl (meth) acrylamide, N,N-di-n-butyl (decyl) propylene A (meth) acrylamide derivative such as decylamine, hydrazine, hydrazine-dihexyl (fluorenyl) acrylamide or dibenzyl (fluorenyl) acrylamide. Among these, ruthenium-dimethyl(fluorenyl) acrylamide, ruthenium, osmium-diethyl(decyl) acrylamide, which is highly etchable to the substrate, is preferred. The (Β) component is used by using (mercapto) acrylamide (1) in combination with (meth) acrylamide (2) represented by the following formula (2), and does not inhibit the etchability to the substrate. The deflection of the obtained laminate under heating conditions can be reduced.
(式（2)中，R4表示氫原子或甲基）。 作為（曱基）丙烯醯胺（2)之具體例，可列舉丙稀酿基 味啉、甲基丙烯醯基咮啉。 (Β)成分中（甲基）丙烯醯胺（1)及（2)之比例為相對於（ 曱基）丙烯醯胺（1)及（2)之合計量1〇〇重量份，包含5〜％ 重量％的（曱基）丙烯醯胺（1)及95〜5重量。/0的（甲基）丙稀 醯胺（2)，較佳為10〜90重量％的（甲基）丙烯醯二（^及 201245380 90〜10重量％的（曱基）丙烯醯胺（2)。若（甲基）丙烯醯胺 (1)之比例小於5重量％、或（甲基）丙稀醯胺（2)之比例大 於95重量％，則接著強度下降。另一方面，若（曱基）丙 烯酿胺（1)之比例大於95重量％、或（曱基）丙烯醯胺（2) 之比例小於5重量％，則在加熱狀況下所得到之積層體 的挽曲會變大。 3.(C)成分 (C)成分係上述（A)及（B)成分以外之具有乙烯性不 飽和基的化合物。 作為（C)成分’只要是（A)及（B)成分以外的化合物， 可使用各種的化合物。作為（C)成分，有單體、低聚物及 聚合物^ 3-1.單體 作為單體，可列舉具有1個（甲基）丙烯醯基之化合 物。 作為該化合物，可列舉（甲基）丙烯酸乙酯、（曱基） 丙烯酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸戊酯、（ 甲基）丙烯酸己酯、（曱基）丙烯酸庚酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸苄酯及（曱基）丙烯酸異莰酯、（ 曱基）丙烯酸二環戊烯酯、（甲基）丙烯酸二環戊烷酯等。 又，（甲基）丙烯酸酯以外，亦可列舉N-乙稀吡咯啶 酮及N-乙烯己内醯胺等之N-乙烯化合物等。 作為具有2個以上（甲基）丙烯醯基之化合物，可列 舉乙二醇二（甲基）丙烯酸酯、四乙二醇二（甲基）丙烯酸酯 、及丙二醇二（甲基）丙烯酸酯及三丙二醇二（甲基）丙烯酸 -16- 201245380 酯等之烯烴基二醇二（曱基）丙烯酸酯；1，6 -己烷二醇二（ 曱基）丙稀酸酯及新戊二醇二（甲基）丙稀酸酯等之二醇二 (曱基）丙烯酸酯；雙酚A二（曱基）丙烯酸酯或其鹵素核 置換物及雙酚F二（曱基）丙烯酸酯或其函素核置換物等 之雙酚型二（曱基）丙烯酸酯；二羥曱基三環癸烷二（甲基） 丙烯酸酯、三羥甲丙烷三（甲基）丙烯酸酯、二三羥甲丙 烷四（曱基）丙烯酸酯、新戊四醇三（曱基）丙烯酸酯、新戊 四醇四（曱基）丙烯酸酯及二新戊四醇六（甲基）丙烯酸酯 等之多元醇聚（甲基）丙烯酸酯；上述多元醇之環氧烷加 成物的聚（曱基）丙烯酸酯；異三聚氰酸環氧烷之二或三（ 曱基）丙烯酸酯等；此等以外亦可列舉如文獻「最新UV 硬化技術」（（股）印刷情報協會，1991年發行）之53〜56 頁所記載之化合物等。 3-2.低聚物 作為低聚物，可列舉聚酯（甲基）丙烯酸酯、環氧（曱 基）丙烯酸酯及聚醚（曱基）丙烯酸酯等。 3 -2-1.聚酯（曱基）丙烯酸酯低聚物 作為聚酯（甲基）丙烯酸酯低聚物，可列舉聚酯多元 醇與（甲基）丙烯酸之脫水縮合物等。 在此，作為聚酯多元醇，可列舉與多元醇之與羧酸 或與其酐的反應物等。 作為多元醇，可列舉乙二醇、二乙二醇、三乙二醇 、四乙二醇、聚乙二醇、丙二醇、二丙二醇、三丙二醇 、聚丙二醇、丁二醇、聚丁二醇、伸丁二醇、六亞曱二 醇、新戊二醇、環己烷二甲醇、3-甲基-1,5-戊二醇、丨，6- -17- 201245380 己烧二醇、三羥曱丙烧、丙三醇、新戊四醇及 醇等之低分子量多元醇，以及此等之環氧烷加 作為羧酸或其酐’可列舉鄰酞酸、異酞酸 、己二酸、丁二酸、反丁烯二酸、順丁烯二酸 酸、四氫酞酸及偏苯三酸等之二元酸或其酐等 作為此等以外的聚酯聚（甲基）丙烯酸酯， 上述文獻「UV . EB硬化材料」之74〜76頁所 合物等。 3-2-2·環氧（甲基）丙烯酸酯低聚物 J衣氧（甲基）丙烯酸酯係使（甲基）丙烯酸對 加成反應之化合物，可列舉如上述文獻「uv · 材料」之74〜75頁所記載之化合物等。 作為環氧樹脂，可列舉芳香族環氧樹脂及 氧樹脂等。 ^作為芳香族環氧樹脂，具體而言，可列舉 裒氧丙基醚；雙酚A、雙酚f、雙酚s、雙酚 氧烧加成物的-+ & & 匕 的—或艰王展氧丙基醚；酚酚醛清漆 月曰及甲酚紛駿杳 .js2 月漆型嶮氧樹脂等之酚醛清漆型 氧丙基笨二甲醯亞胺；鄰酞酸二環氧丙基 处3列舉如文獻「環氧名 (昭晃堂，19.90玍欢， % 90年發行）2章、及文獻 40 ^ 卷增刊號環氧樹脂（高分 48年發行）之4〜6 0貝、9〜16頁所記載： 乍為脂肪族王夢$ 而一 p '衣氧祕脂，具體而言， 内一醇、1 4 ~r - ’ 丁 一醇及1，6-己二醇等之烯 二新戊四 成物等。 、對酞酸 、六氫酞 〇 可列舉如 記載之化 環氧樹脂 EB硬化 脂肪族環 間苯二齡 薙或其環 型環氧樹 %氧樹脂 酉旨等。 近的進步 子加工」 會，昭和 物。 乙二醇、 醇的二環 201245380 氧丙基越’聚乙二醇及聚丙二醇的二環氧丙基醚等之聚 烯烴基二醇的二環氧丙基醚；新戊二醇、二溴新戊二醇 及其環氧烷加成物的二環氧丙基醚；三羥甲乙烷、三羥 甲丙烷、丙三醇及其環氧烷加成物的二或三環氧丙基醚 ，以及新戊四醇及其環氧烷加成物的二、三或四環氧丙 基鍵等之多元醇的聚環氧丙基醚；加氫雙酚A及其環氧 烷加成物的二或聚環氧丙基醚；四氫酞酸二環氧丙基醚 :氫醌二環氧丙基醚等。 此等以外，亦可列舉如上述文獻「高分子加工」別 冊袁氧樹月曰之3〜6頁所記載的化合物。此等芳香族環氧 樹脂及脂肪族環氧樹脂以外，亦可列舉在骨架中具有三 啩核之環氧化合物，例如TEPIC(日產化學（股））、Denacol EX_3 1〇(長瀨化成（股））等’又，可列舉如上述文獻「高分 子加工」別冊環氧樹脂之289〜296頁所記載的化合物等 〇 在上述中’作為環氧烷加成物之環氧烷，較佳為環 氧乙烷及環氧丙烷等。 3-2-3·聚醚（甲基）丙烯酸酯低聚物 作為聚喊（甲基）丙烯酸酯低聚物，可列舉為聚烯烴 基一醇（甲基）二丙烯酸酯的聚乙二醇二（曱基）丙烯酸酯 聚丙二醇二（曱基）丙烯酸酯及聚四甲二醇二（曱基）丙烯 酸酯等。 3 - 3.聚合物 作為聚合物，可列舉在具有（曱基）丙烯醯基氧基的（ 甲基）丙烯酸系聚合物、具有官能基的（甲基）丙烯酸系聚 -19- 201245380 …勿，於側鍵導入(甲基)丙婦醯基者，以及 二，硬化材料……所記載之化合=獻 作為（c)成分之化合物，較佳為以使後述組成物^。 化物的玻璃轉移溫度成為較佳範圍而選定。 石更 作為（C)成分，以在上述化合物之中附著性良 點，較佳為具有丨個（甲基）丙烯醯基的單體。 觀 再者，作為（C)成分，較佳為具有同元聚合物之破 轉移溫度（以下稱為「Tg」）為〇〜200〇c者，更佳為具有 60〜1 80°C之化合物。作為該化合物之例，可列舉二環戊 烧基丙烯酸酯（同元聚合物之Tg : 1 20。(：。以下括孤為相 同意義）、二環戊烷基甲基丙烯酸酯（175»c)、異茨基丙歸 酸酯（94°C )及異莰基甲基丙烯酸酯（180X：)等。 此外，在本發明中，Tg意味著在1Hz下所測定之硬 化物的黏彈性比之損失正切（tan <5 )的主要波峰為最大之 溫度。 4.摻合比例 在本發明中，作為（A)、（B)及（C)成分之比例，相對 於（A)〜（C)成分之合計量為（A)成分5〜50重量％、（B)成 分30〜93重量％及（C)成分2〜65重量％ ’較佳為（A)成 分15〜40重量％、（B)成分30〜85重量°/〇及（C)成分2〜 55重量％。 當（A)成分之比例小於5重量％時’接著力下降’而 另一方面當大於50重量％時’所得之積層體之在加熱狀 況下的撓曲變大。當（B)成分小於30重量。/()時或（B)成分 大於93重量％時，任一方之情形都會使接著力下降。當 -20- 201245380 (C)成分大於65重量％時，接著力下降。藉由使（c)成分 為2重量％以上’而可使其成為接著力優異者。 又，本發明之組成物係相對於（A)〜（c)成分之合計 量，必須含有2〜30重量％的具有曱基丙烯醯基之化合 物，較佳為5〜30重量％ ,更佳為5〜25重量％。當小於 2重量％時’貼合時會出現翹曲；當大於3 〇重量％時則 會延遲硬化性’而生產性降低。 該具有曱基丙烯醯基之化合物，自上述（A)、（B)及 (C)成分之中適宜選擇即可。作為具有曱基丙烯醯基之化 合物，由（C)成分選擇具有甲基丙烯醯基之化合物係簡便 而較佳。 5.其他成分 當本發明之組成物藉由紫外線硬化時，亦可因應需 要摻合光聚合起始劑（以下亦稱為（D)成分）。 作為（D)成分，可列舉安息香、安息香曱基醚、安息 香乙基醚及安息香異丙基醚等之安息香與其烷基醚；苯 乙酮、2,2-二曱氧基-2-苯基苯乙酮、2,2_二乙氧基苯 基苯乙酮、1，1-一氣笨乙酮、1_經基苯乙酮、卜羥基環己 基苯基酮及2-曱基-1-[4-(甲基硫）苯基]_2，味啉-丙烷 酮等之苯乙2-曱基蒽醌、2·乙基蒽醌、2_三級丁基筑 醌、1 -氣蒽醌及2-戍蒽醌等之蒽醌；2 4--甲A a , —T I嗔嘲酮 、2,4-二乙基噻噸酮、2-氯噻噸酮及2,4•二異丙基噻噸_ 等之噻嘲酮；苯乙酮二甲基縮_及节基二甲基縮酮等之 縮_ ’ 2,4,6 -二曱基苯曱酿基二苯基氧化膦等之單酿 膦或雙酿氧化膦；二苯基酮等之二苯基 化 w，Μ及咄綱 -21 - 201245380 類等。此等之光聚合起始劑可單獨使用，亦可與安息香 酸系、胺系等之光聚合起始促進劑組合使用。 (D)成分之較佳摻合比例，係相對於組成物〖〇〇重量 份為〇·1重量份以上10重量份以下，更佳為〇 5重量份 以上5重量份以下。 此等之中，由於硬化物之經時性著色少，較佳為以 羥基苯乙酮類及氧化膦類。 又，在本發明之組成物，（Α)〜（c)成分之合計每1〇〇 重量份，可添加至5重量份為止之量的氧化劑、紫外線 吸收劑、HALS(受阻胺系光安定劑)等之耐久性提升劑， 或者使塗布之膜厚均等的調平劑、抑制發泡的消泡劑。 6.製造及使用方法 本發明之組成物的製造方法並未特別限定，可藉由 以一般施行之方法’攪拌或混合本發明之必要成分、曰或 必要成分及因應需要的其他成分而得到。 "" 此時’亦可因應需要而加溫或加熱。 本發明之組成物’可較佳使用於作為不含有機溶劑 的無溶劑型之組成物。藉此’不會有在有機溶劑乾燥時 的大量溶劑蒸氣揮發，可避免毒性、作業安全性及環境 污染性之問題，並進_ 4=- X Φ* Φ m 進步不㊉要使用於乾燥的熱能，可 低成本地製造目標製品。 作為本發明之組成物，較佳為具有硬化物之Tg為 60〜180°C 者。若 Te A , g為60 C以上，則耐熱試驗時之接著 強度優異，若Tg為]π g马180CU下’則可充分獲得初期之剝 離強度。 -22- 201245380 本發明之組成物可使用於各種基材之接著。 作為基材，可列舉塑膠 '金屬及紙等，可適用於塑 膠之接著。 作為本發明之組成物的使用方法’遵循常用方法即 可’可列舉塗布於基材後照射活性能量線之方法等。 作為活性能量線，可列舉可見光、紫外線、χ光及 電子束等，然而由於可使用廉價的裝置，而以紫外線為 較佳。 作為藉由紫外線硬化時之光源’可使用各種光源， 例如可列舉加壓或高壓水銀燈，金屬_素燈、氙燈、無 電極放電燈、碳弧燈及led等。 當藉由電子束硬化時’作為可使用之電子束（EB)照 射裝置，可使用各種裝置，例如可列舉柯克勞夫沃爾頓 型、范德格拉夫型及調諧變壓器型之裝置等，作為電子 束，較佳為具有之能量者，更佳為1〇〇〜 300eV。 本發明之組成物可較佳使用於積層體之製造，遵德 一般製造積層時所施行之方法即可。例如可列舉在第^ 基材塗布組成物，於此貼合第2基材後，自任一之基材 之表面照射活性能量線之方法。 如此所製造之積層體，係由基材、本發明之組成物 的硬化物及其他基材所構成者。此時，作為基材，較佳 為至少其中一方為塑膠基材。 本發明之組成物， 著劑組成物，又，可 著劑組成物。 物，可較佳使用於作為光學材料 可#父佳使用於作為光學薄膜積層 用接 用接 -23- 201245380 用 係 因 度 脂 苯 、 乙 使 的 輥 方 層 於 裝 膜 此時’作為上述之基材，可使用作為光學構件所使 之薄層被接著體’遵循與上述相同之方法製造積層體 在此’作為光學構件所使用之薄層被接著體，主要 使用塑膠薄膜’必須是可使活性能量線穿透者，膜厚 應能使用的薄層被接著體及用途選擇即可，較佳為厚 為 1 m m以下。 在塑膠薄膜中’作為塑膠’例如可列舉聚氯乙烯樹 聚氣亞乙稀、纖維素系樹脂、聚乙烯、聚丙烯、聚 乙烯丙烯腈-丁二烯-苯乙烯樹脂（ABS樹脂）、聚醯胺 聚日聚奴曰、聚胺基曱酸酯、聚乙稀醇、乙稀_ 酸乙烯共聚物及氣化聚丙烯等。0應使用用途，亦可 用在表面經過金屬蒸鍍等之處理者。 作為對於薄層被接著體之塗布方法，遵循以往周知 方法即可，可列舉天然塗布機、^刀帶塗布機、浮刀 親】刀毯上刮刀、嘴塗、浸潰、接觸上膠輥、壓 反向輥IL刀、@幕流程塗布機及凹板塗布機等之 法。 又’本發明之組成物的 被接著體及用途選擇即可 更佳為1〜5〇"m。 自本發明之接著劑組成 在高溫條件下接著力優異 置等的偏光薄膜、相位差 、導光板、擴散板等之光 塗布厚度，因應所使用的薄 ’然而較佳為0.1〜l,〇〇〇/zm 物所得之積層薄膜或片，由 ’可適宜的使用於液晶顯示 薄犋、稜鏡片、亮度提升薄 學薄膜或片。 '24* 201245380 [實施例] 以下列舉實施例及比較例，更具體地說明本發明。 其中，以下的各例子中之「份」係意味著重量份。 〇實施例1〜6及比較例1〜5 將下述表1及表2所示（A)、（B)、（C)及（D)成分，於 6 0°C加熱攪拌1小時而使其溶解，製造活性能量線硬化 型接著劑組成物。 遵循下述之試驗方法評價所得之組成物。 表1(In the formula (2), R4 represents a hydrogen atom or a methyl group). Specific examples of the (mercapto) acrylamide (2) include acryloyl porphyrin and methacryl fluorenyl porphyrin. The ratio of (meth)acrylamide (1) and (2) in the (Β) component is 1 part by weight based on the total amount of (nonyl) acrylamide (1) and (2), and contains 5 to 5 parts by weight. % by weight of (mercapto) acrylamide (1) and 95 to 5 by weight. (0) (meth) acrylamide (2), preferably 10 to 90% by weight of (meth) propylene bismuth (^ and 201245380 90 to 10% by weight of (mercapto) acrylamide (2 If the ratio of (meth)acrylamide (1) is less than 5% by weight or the ratio of (meth) acrylamide (2) is more than 95% by weight, the strength is lowered. On the other hand, if When the proportion of the fluorenylamine (1) is more than 95% by weight or the ratio of the (fluorenyl) acrylamide (2) is less than 5% by weight, the laminate of the laminate obtained under heating becomes large. 3. The component (C) is a compound having an ethylenically unsaturated group other than the components (A) and (B). The component (C) is not limited to the components (A) and (B). As the compound, various compounds can be used. Examples of the component (C) include a monomer, an oligomer, and a polymer. 3-1. A monomer as a monomer includes a compound having one (meth) acryloyl group. Examples of the compound include ethyl (meth)acrylate, propyl (mercapto)acrylate, butyl (meth)acrylate, and amyl (meth)acrylate. (meth) hexyl acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate and isodecyl (mercapto) acrylate, (decyl) acrylate Dicyclopentenyl ester, dicyclopentanyl (meth) acrylate, etc. Further, other than (meth) acrylate, N-ethylpyrrolidone and N-vinyl caprolactam may be mentioned. Examples of the compound having two or more (meth)acryl fluorenyl groups include ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di(methyl). Alkenyl diol bis(indenyl) acrylate such as acrylate and tripropylene glycol di(meth)acrylic acid-16-201245380 ester; 1,6-hexanediol bis(indenyl) acrylate and new Glycol bis(indenyl) acrylate such as pentanediol di(meth) acrylate; bisphenol A bis(indenyl) acrylate or its halogen core replacement and bisphenol F bis(indenyl) acrylate a bisphenol type bis(indenyl) acrylate such as an ester or a nucleus replacement thereof; a dihydroxyindenyl tricyclodecane II Acrylate, trimethylolpropane tri(meth)acrylate, ditrihydroxymethylpropane tetra(indenyl)acrylate, pentaerythritol tris(decyl)acrylate, neopentyl alcohol tetrakis(yl) Polyol poly(meth) acrylate such as acrylate and dipentaerythritol hexa(meth) acrylate; poly(indenyl) acrylate of alkylene oxide adduct of the above polyol; heterotrimerization Cyanate alkylene oxide or di(trimyl) acrylate, etc.; other than these, as described in the document "Latest UV Hardening Technology" (issued by the Printing Information Association, issued in 1991), pages 53-56. 3-2. Oligomers Examples of the oligomers include polyester (meth) acrylate, epoxy (fluorenyl) acrylate, and polyether (fluorenyl) acrylate. 3 - 2-1. Polyester (mercapto) acrylate oligomer The polyester (meth) acrylate oligomer may, for example, be a dehydrated condensate of a polyester polyol and (meth)acrylic acid. Here, examples of the polyester polyol include a reaction product with a carboxylic acid or an anhydride thereof. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, and polybutylene glycol. Butanediol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, hydrazine, 6--17- 201245380 hexane diol, trihydroxyl Low-molecular-weight polyols such as propylene-acrylic acid, glycerin, neopentyl alcohol, and alcohol, and the alkylene oxides added thereto as carboxylic acids or anhydrides thereof may be exemplified by ortho-decanoic acid, isophthalic acid, adipic acid, As a polyester poly(meth)acrylate other than these, a dibasic acid such as succinic acid, fumaric acid, maleic acid, tetrahydrononanoic acid or trimellitic acid or an anhydride thereof, The above-mentioned document "UV. EB hardening material", 74 to 76 pages, and the like. 3-2-2. Epoxy (meth) acrylate oligomer J. Oxygen (meth) acrylate is a compound which reacts (meth)acrylic acid to the addition reaction, and the above-mentioned document "uv · material" is mentioned. The compounds described in pages 74 to 75, etc. Examples of the epoxy resin include an aromatic epoxy resin and an oxygen resin. ^As an aromatic epoxy resin, specifically, oxime propyl ether; bisphenol A, bisphenol f, bisphenol s, bisphenol oxy-fired adduct-+ && Oxygen propyl ether; phenol novolac varnish and cresol 杳 杳.js2 month lacquer type enamel resin and other novolac type oxypropyl phenyl dimethyl sulfoxide; o-nonanoic acid epoxide Section 3 lists 4 to 60 shells of the epoxy resin (Zhao Shengtang, 19.90 Yu Huan, % 90 years of issue), and the literature 40 ^ Volume Supplement Epoxy (high score 48 years) Recorded on pages 9 to 16: 乍 is an aliphatic king dream $ and a p 'coating oxygen secret, specifically, lactone, 14 4 -r - 'butanol and 1,6-hexanediol, etc. Ethylene pentane tetrachloride or the like. For citric acid or hexahydroanthracene, the epoxy resin EB-hardened aliphatic epoxide benzoate or its cyclic epoxy resin Nearly progressive sub-processing", Showa. Ethylene glycol, alcohol, bicyclol 201245380 oxypropyl group, polyethylene glycol diol, such as polyethylene glycol and polypropylene glycol diglycidyl ether, diepoxypropyl ether; neopentyl glycol, dibromo Di-epoxypropyl ether of neopentyl glycol and its alkylene oxide adduct; di- or tri-epoxypropyl group of trimethylolethane, trimethylolpropane, glycerol and its alkylene oxide adduct Ether, and polyepoxypropyl ether of polyhydric alcohol such as di-, tri- or tetra-glycidyl bond of pentaerythritol and its alkylene oxide adduct; hydrogenated bisphenol A and its alkylene oxide addition Di- or polyepoxypropyl ether; tetrahydroabietic acid diepoxypropyl ether: hydroquinone diepoxypropyl ether and the like. In addition to these, the compounds described in the above-mentioned document "Polymer Processing", No. 3 to 6 of Yuan Ou Shu Yue. Other than the aromatic epoxy resin and the aliphatic epoxy resin, an epoxy compound having a triterpene core in the skeleton, for example, TEPIC (Nissan Chemical Co., Ltd.) and Denacol EX_3 1〇 (Chang Yuhua Cheng (share) Further, the compound described in the above-mentioned "Polymer Processing", the epoxy resin, 289 to 296, etc., in the above-mentioned "alkylene oxide as an alkylene oxide adduct, preferably Ethylene oxide and propylene oxide. 3-2-3·Polyether (meth)acrylate oligomer As the poly(meth)acrylate oligomer, polyethylene glycol monoalcohol (meth) diacrylate polyethylene glycol is exemplified Di(indenyl) acrylate polypropylene glycol bis(indenyl) acrylate and polytetramethylene glycol bis(indenyl) acrylate. 3 - 3. Polymer as a polymer, which may be exemplified by a (meth)acrylic polymer having a (fluorenyl)acrylenyloxy group and a (meth)acrylic polyfunctional group having a functional group. The compound which is introduced into the (meth) propyl group and the second side, and the hardened material ...... the compound described as the component (c) is preferably a composition which will be described later. The glass transition temperature of the compound is selected to be a preferred range. As the component (C), the stone has a good adhesion among the above compounds, and preferably a monomer having a fluorene (meth) acryl fluorenyl group. Further, as the component (C), it is preferred that the breaking temperature (hereinafter referred to as "Tg") of the homopolymer is 〇~200〇c, more preferably a compound having 60 to 180 °C. . Examples of the compound include dicyclopentanyl acrylate (Tg of a homopolymer: 1 20 (:: the following meanings are the same), dicyclopentyl methacrylate (175»c) , isodecylpropionic acid ester (94 ° C) and isodecyl methacrylate (180X:), etc. Further, in the present invention, Tg means the viscoelasticity ratio of the cured product measured at 1 Hz. The main peak of the loss tangent (tan <5) is the maximum temperature. 4. Blending ratio In the present invention, as the ratio of the components (A), (B) and (C), relative to (A) ~ ( The total amount of the component C) is 5 to 50% by weight of the component (A), 30 to 93% by weight of the component (B), and 2 to 65% by weight of the component (C). Preferably, the component (A) is 15 to 40% by weight. (B) Component 30 to 85 weight % / 〇 and (C) component 2 to 55 % by weight. When the ratio of the component (A) is less than 5% by weight, 'the adhesive force decreases' and on the other hand when it exceeds 50% by weight' The deflection of the obtained laminate under heating conditions becomes large. When the component (B) is less than 30% by weight/() or the component (B) is more than 93% by weight, either case is brought into contact. When the component of -20-201245380 (C) is more than 65% by weight, the force is lowered. By making the component (c) 2% by weight or more', it is excellent in the adhesion. The composition must contain 2 to 30% by weight of a compound having a mercaptopropenyl group with respect to the total amount of the components (A) to (c), preferably 5 to 30% by weight, more preferably 5 to 25 parts by weight. %. When it is less than 2% by weight, warpage occurs when it is bonded; when it is more than 3% by weight, the hardenability is delayed and the productivity is lowered. The compound having a mercapto acrylonitrile group, from the above (A) The components (B) and (C) may be appropriately selected. As the compound having a mercaptopropenyl group, the compound having a methacrylinyl group selected from the component (C) is simple and preferable. When the composition of the present invention is cured by ultraviolet rays, a photopolymerization initiator (hereinafter also referred to as a component (D)) may be blended as needed. As the component (D), benzoin, benzoin oxime, benzoin may be mentioned. Benzoin and its alkyl ethers such as ethyl ether and benzoin isopropyl ether Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyphenylacetophenone, 1,1-one acetophenone, 1_p-phenylene Ketone, hydroxycyclohexyl phenyl ketone and 2-mercapto-1-[4-(methylthio)phenyl]_2, morpholine-propane ketone, etc.蒽醌, 2_ tertiary butyl ruthenium, 1 - gas 蒽醌 and 2-戍蒽醌 戍蒽醌; 2 4--A A a, - TI 嗔 酮 ketone, 2,4-diethyl thiophene a small amount of ketone, such as ketone, 2-chlorothioxanthone and 2,4•diisopropylthioxan; acetophenone dimethyl condensed _ and benzyl ketal 4,6-dimercaptobenzoquinone-based diphenylphosphine oxide, such as mono-phosphorus or double-brewed phosphine oxide; diphenyl ketone and the like, diphenylation w, hydrazine and hydrazine-21 - 201245380, and the like. These photopolymerization initiators may be used singly or in combination with a photopolymerization initiation accelerator such as a benzoic acid or an amine. The blending ratio of the component (D) is preferably from 1 part by weight to 10 parts by weight, more preferably from 5 parts by weight to 5 parts by weight, based on the total weight of the composition. Among these, hydroxyacetophenones and phosphine oxides are preferred because of the less time-dependent coloration of the cured product. Further, in the composition of the present invention, the oxidizing agent, the ultraviolet absorbing agent, and the HALS (hindered amine light stabilizer) may be added in an amount of up to 5 parts by weight per 1 part by weight of the total of the components (Α) to (c). A durability enhancer such as a leveling agent that equalizes the thickness of the applied film, and an antifoaming agent that suppresses foaming. 6. Manufacture and use method The method for producing the composition of the present invention is not particularly limited, and it can be obtained by stirring or mixing the essential components, hydrazine or essential components of the present invention and other components as necessary in a usual manner. "" At this time, it can be heated or heated as needed. The composition of the present invention' can be preferably used as a solventless type composition which does not contain an organic solvent. Therefore, there is no need to volatilize a large amount of solvent vapor when the organic solvent is dried, and the problems of toxicity, work safety and environmental pollution can be avoided, and _ 4=- X Φ* Φ m is not used for dry heat. The target product can be manufactured at low cost. As the composition of the present invention, it is preferred that the cured product has a Tg of 60 to 180 °C. When Te A and g are 60 C or more, the adhesion strength at the time of the heat resistance test is excellent, and if the Tg is π g at 180 CU, the initial peel strength can be sufficiently obtained. -22- 201245380 The compositions of the present invention can be used in the subsequent steps of various substrates. Examples of the substrate include plastics such as metal and paper, and can be applied to plastics. The method of using the composition of the present invention 'follow the usual method' may be a method of applying an active energy ray to a substrate and then irradiating it. Examples of the active energy ray include visible light, ultraviolet ray, calendering, and electron beam. However, since an inexpensive device can be used, ultraviolet rays are preferred. Various light sources can be used as the light source in the case of curing by ultraviolet rays, and examples thereof include pressurized or high-pressure mercury lamps, metal-based lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, and led electrodes. When it is used as an electron beam (EB) irradiation device that can be used by electron beam hardening, various devices can be used, and examples thereof include a Kirklaw Walton type, a Van de Graaff type, and a tuning transformer type device. As the electron beam, it is preferably one having an energy, more preferably from 1 〇〇 to 300 eV. The composition of the present invention can be preferably used for the production of a laminate, and it is generally possible to carry out the method which is carried out when the laminate is produced. For example, a method in which the composition is coated on the second substrate and the second substrate is bonded thereto is irradiated with an active energy ray from the surface of any of the substrates. The laminate produced in this manner is composed of a substrate, a cured product of the composition of the present invention, and other substrates. In this case, it is preferred that at least one of the substrates is a plastic substrate. The composition of the present invention, the composition of the composition, and the composition of the composition. The material can be preferably used as an optical material. The parent can be used as an optical film laminate. -23-201245380. For the substrate, a thin layer can be used as an optical member. The laminate is manufactured in the same manner as described above. Here, the thin layer is used as the optical member. The main plastic film is used. For the active energy ray penetrator, the thin layer to be used for the film thickness may be selected by the adherend and the use, and preferably has a thickness of 1 mm or less. In the plastic film, 'as a plastic', for example, a polyvinyl chloride tree, a cellulose resin, a polyethylene, a polypropylene, a polyethylene acrylonitrile-butadiene-styrene resin (ABS resin), and a poly Amidoxime polyglycol, polyamino phthalate, polyethylene glycol, ethylene-ethylene copolymer and gasified polypropylene. 0 should be used for the purpose, or it can be used for the treatment of metal vapor deposition on the surface. As a coating method for a thin-layered adherend, a conventionally known method can be used, and examples thereof include a natural coater, a knife coater, a float knife, a knife blade, a mouth coating, a dipping, and a contact rubber roller. Pressure reverse roller IL knife, @ curtain process coating machine and gravure coating machine. Further, the composition of the composition of the present invention and the use thereof can be more preferably 1 to 5 Å " m. The coating thickness of the polarizing film, the phase difference, the light guide plate, the diffusion plate, and the like which are excellent in adhesion strength under high temperature conditions in the adhesive composition of the present invention, and the thinness used in response to the thinner one, however, preferably 0.1 to 1, 〇〇 The laminated film or sheet obtained from the 〇/zm material can be suitably used for liquid crystal display, enamel film, brightness enhancement thin film or sheet. '24* 201245380 [Examples] Hereinafter, the present invention will be described more specifically by way of examples and comparative examples. Here, the "parts" in the following examples mean parts by weight. Examples 1 to 6 and Comparative Examples 1 to 5 The components (A), (B), (C) and (D) shown in Tables 1 and 2 below were heated and stirred at 60 ° C for 1 hour. This dissolves to produce an active energy ray-curable adhesive composition. The obtained composition was evaluated in accordance with the test method described below. Table 1
實施例 1 2 3 4 5 6 UN9200A u 20 20 30 30 ㈧ OT-1001 2) 20 KY-303 3) 30 丙烯醯胺(1) dmaa4) 20 10 10 20 30 (B) DEAA5) 35 丙烯醯胺(2) ACMO 6) 50 40 40 35 20 35 組 成 IBX7) 20 20 10 5 BzMA8) 10 物 (C) ibxa9> M-lll |0) 10 FA-513M11) 10 FA-513AS 12) 10 (D) Irgl84 13) 3 3 TPO 14) 1 1 1 1 MA之比例|5) (%) 10 20 20 10 10 5 硬化物之Tg(°C) 130 121 127 140 110 120 剝離強度(N/25mm) 材破 8 10 材破 材破 材破 貼合時之起曲(mm) <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 評 判定 A A A A A A 價 加熱試驗(80°C，mm) <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 判定 A A A A A A 加熱試驗(120°C，mm) <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 判定 A A A A A A -25- 201245380 表2Example 1 2 3 4 5 6 UN9200A u 20 20 30 30 (8) OT-1001 2) 20 KY-303 3) 30 acrylamide (1) dmaa4) 20 10 10 20 30 (B) DEAA5) 35 acrylamide ( 2) ACMO 6) 50 40 40 35 20 35 Composition IBX7) 20 20 10 5 BzMA8) 10 (C) ibxa9> M-lll |0) 10 FA-513M11) 10 FA-513AS 12) 10 (D) Irgl84 13 3 3 TPO 14) 1 1 1 1 ratio of MA|5) (%) 10 20 20 10 10 5 Tg of the hardened material (°C) 130 121 127 140 110 120 Peel strength (N/25mm) Material break 8 10 The starting material of the broken material of the broken material (mm) <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Evaluation of the AAAAAA price heating test (80 ° C, mm) <0.5 <;0.5<0.5<0.5<0.5<0.5 AAAAAA heating test (120 ° C, mm) < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 AAAAAA -25 - 201245380 2
比較例 1 2 3 4 5 UN9200A1) 30 20 20 ㈧ OT-1001 2) 20 20 KY-303 3) 丙烯醯胺(1) DMAA4) 30 50 40 (B) DEAA5) 丙烯醯胺(2) ACMO6) 20 50 組 成 rox7) 20 20 20 BzMAS) 20 10 物 (C) IBXA9) 30 10 M-111 10) 10 10 M-120 16) 20 OPPA17) 30 (D) Irgl84 13) 3 3 3 TPO |4) 1 1 MA之比例(%) 20 20 0 10 20 硬化物之Tg(°C) 22 127 145 95 98 剝離強度(N/25mm) 16 1 材破 材破 15 貼合時之組曲(mm) <0.5 <0.5 2.0 <0.5 <0.5 評 判定 A A D A A 價 加熱試驗(80°C，mm) 1.5 <0.5 <0.5 0.5 0.5 判定 D A A B B 加熱試驗(120°C，mm) 2.0 <0.5 <0.5 1.0 1.0 判定 D A A c C 在表1及表2中，（A)〜（D)成分中之各數字意味著 份數，各簡稱則表示以下之意義。 1) UN9200A :非芳香族系之具有聚碳酸酯骨架的聚 碳酸酯系胺基甲酸酯丙烯酸酯，重量平均分子量約2萬（ 根上工業（股）製Artrejin UN9200A) 2) OT-1001 :非芳香族系之具有聚酯骨架的聚酯系胺 基甲酸酯丙烯酸酯，重量平均分子量約4萬（東亞合成（ 股）製 Aronix ΟΤ-1001) -26- 201245380 3) ΚΥ-303 :聚醚系胺基甲酸酯丙烯酸酯，重量平均 分子量約1萬5千（根上工業（股）製ΚΥ-303) 4) DMAA : Ν，Ν-二曱基丙烯醯胺（（股）興人製DMAA) 5) DEAA: Ν，Ν-二乙基丙烯酿胺（（股）興人製DEAA) 6) ACMO:丙烯醯基咮啉（（股）興人製ACMO) 7) IBX:曱基丙烯酸異莰基酯（共榮社化學（股）製 Light Acrylate IB-X) 8) BzMA :曱基丙烯酸苄基酯 9) IBXA :丙烯酸異莰基酯（共榮社化學（股）製Light Acrylate IB-XA) 10) M-111 :壬酚環氧乙烷變性丙烯酸酯（東亞合成（ 股）製 AronixM-111) 11) FA-5 13M :(甲基）丙烯酸二環戊烷基酯（日立化成 工業（股）製 Fancryl FA-513M) 12) FA-513AS :(甲基）丙烯酸二環戊烷基酯（日立化 成工業（股）製 Fancryl FA-513AS) 13) Irgl84 : 1-羥基環己基苯酮（BASF社製Comparative Example 1 2 3 4 5 UN9200A1) 30 20 20 (8) OT-1001 2) 20 20 KY-303 3) Acrylamide (1) DMAA4) 30 50 40 (B) DEAA5) Acrylamide (2) ACMO6) 20 50 Composition rox7) 20 20 20 BzMAS) 20 10 (C) IBXA9) 30 10 M-111 10) 10 10 M-120 16) 20 OPPA17) 30 (D) Irgl84 13) 3 3 3 TPO |4) 1 1 Ratio of MA (%) 20 20 0 10 20 Tg of hardened material (°C) 22 127 145 95 98 Peel strength (N/25mm) 16 1 Broken material broken 15 Set of stitches (mm) <0.5 <;0.5 2.0 <0.5 <0.5 Evaluation AADAA Price Heating Test (80 ° C, mm) 1.5 < 0.5 < 0.5 0.5 0.5 Determination DAABB Heating Test (120 ° C, mm) 2.0 < 0.5 < 0.5 1.0 1.0 Judging DAA c C In Tables 1 and 2, each of the numbers (A) to (D) means the number of copies, and each abbreviation means the following meaning. 1) UN9200A: a non-aromatic polycarbonate urethane acrylate having a polycarbonate skeleton, and a weight average molecular weight of about 20,000 (Artrejin UN9200A manufactured by Kokusai Industrial Co., Ltd.) 2) OT-1001: Non Aromatic polyester urethane acrylate having a polyester skeleton, weight average molecular weight of about 40,000 (Aronix ΟΤ-1001 manufactured by Toagosei Co., Ltd.) -26- 201245380 3) ΚΥ-303 : Polyether A urethane acrylate having a weight average molecular weight of about 15,000 (manufactured by Kosei Co., Ltd. - 303) 4) DMAA: Ν, Ν-dimercaptopropene amide (() 5) DEAA: Ν, Ν-diethyl acrylamide (DEAA) 6) ACMO: acryloyl porphyrin (ACMO) (7) IBX: thiol acrylate Mercaptoester (Light Acrylate IB-X, manufactured by Kyoeisha Chemical Co., Ltd.) 8) BzMA: benzyl methacrylate 9) IBXA: isodecyl acrylate (Light Acrylate IB-made by Kyoeisha Chemical Co., Ltd.) XA) 10) M-111 : Indophenol oxirane modified acrylate (Aronix M-111 manufactured by East Asia Synthetic Co., Ltd.) 11) FA-5 13M : Dicyclopentane (meth)acrylate Base ester (Fancryl FA-513M manufactured by Hitachi Chemical Co., Ltd.) 12) FA-513AS: Dicyclopentyl (meth)acrylate (Fancryl FA-513AS manufactured by Hitachi Chemical Co., Ltd.) 13) Irgl84 : 1 -hydroxycyclohexyl phenyl ketone (made by BASF)
Irgacure184) 14) TPO : 2,4,6-三甲基苯甲醯基二苯氧化膦（BASF 社製 Lucirin TPO) 15) MA之比例：相對於（A)〜（C)成分合計量之具有 曱基丙烯醯基的化合物之比例（單位：重量％) 16) M-120 : 2-乙基己基環氧乙烷變性丙烯酸醋（東亞 合成（股）製 AronixM-120) -27- 201245380 17)OPPA:鄰苯酚丙烯酸酯（東亞合成（股）製Aronix TO-2344) 〇試驗方法 1) Tg 在聚對酞酸乙二酯（PET)薄膜上厚度imm之橡膠型 模中注入所得之組成物’以PET薄膜積層於其上之後， 於1 20W/cm、集光型之金屬鹵素燈之下方起3〇cm的位 置，以運送速度l〇m/min之條件，反覆通過燈下1〇次而 得到硬化物。 藉由動態黏彈性測定裝置（SII Nano Technology(股） 製EXSTAR DMS6 1 00)測定所得之硬化物的黏彈性比，由 在1 Hz下測定之硬化物的黏彈性比之損失正切（tan占）的 主要波峰為最大之溫度，測定T g。 2) 試驗體之製造 在厚度50 μ m之聚碳酸酯（以下省略為pc)薄膜 (Iupilon FE-2000 : MITSUBISHI Engineering-Plastics(^ )製）上’藉由棒塗布機塗布1〇ym厚度的所得之組成物 〇 於其上藉由軋輕貼合厚度5〇ym之pc薄膜後，將 其置於120W/cm、集光型之金屬函素燈之下方起3〇cm 的位置，以運送速度10m/min之條件，反覆通過燈下3 次’使薄膜彼此接著，製造積層薄膜。 將所得之試驗體於恆溫恆濕（23^ 5〇%RH)室放置一 天一夜後’評價剝離強度及貼合時之翹曲。 -28- 201245380 3 )剝離強度 • 在怪溫恆濕下，藉由拉伸試驗機以下述之條件測定 試驗體之剝離強度。 • 5式驗片：25mmx100mm •剝離角度：180度 •剝離速度：200mm/min 此外’當接著強度非常強’在測定剝離強度時基材 破裂之情形，記為母材破壞（材破）。 又，剝離強度之測定單位：克重/英吋（gf/inch)為 l(gf/inch)= 3.86xl0'3(N/cm) 〇 4) 貼合時之翹曲 將4驗體切出1 〇 c m x丨〇 c m之大小，在恆溫恆濕下放 置一天一夜後，測定四角的翹曲高度。表中之數值表示 四角高度之平均値。數值越高表示翹曲越大。基於測定 結果，依以下的4種水準判定。 Α:小於〇.5mm(無翹曲而良好）、Β : 〇 5mm以上小 於l.〇mm(有輕微翹曲）、C : 1.0mm以上小於15mm(有 翹曲）、D : 1.5mm以上（翹曲大） 5) 加熱試驗 將忒驗體切出1 〇cmx 1 〇cm之大小，以使試驗體之一 部分（5x10cm)接觸加熱板上之狀態，加熱8〇。〇 1〇分鐘或 1 20 C 10分鐘。評價此時之試驗體的撓曲（浮起的最大高 度-最小南度）。數值越高表示撓曲越大。基於測定結果 ，依以下的4種水準作判定。 -29- 201245380Irgacure 184) 14) TPO: 2,4,6-trimethylbenzimidyl diphenylphosphine oxide (Lucirin TPO manufactured by BASF Corporation) 15) Proportion of MA: relative to the total amount of (A) to (C) components Ratio of compound of mercapto acrylonitrile group (unit: % by weight) 16) M-120 : 2-ethylhexyl oxirane modified acryl vinegar (Aronix M-120 manufactured by Toagosei Co., Ltd.) -27- 201245380 17) OPPA: o-phenol acrylate (Aronix TO-2344 manufactured by Toagosei Co., Ltd.) 〇 test method 1) Tg Injected into the rubber mold of thickness imm on polyethylene terephthalate (PET) film' After the PET film is laminated thereon, it is placed at a position of 3 〇cm below the 1 20 W/cm, concentrating metal halide lamp, and the condition of the transport speed l〇m/min is repeated one by one. A hardened product is obtained. The viscoelasticity ratio of the obtained cured product was measured by a dynamic viscoelasticity measuring device (EXSTAR DMS6 1 00 manufactured by SII Nano Technology Co., Ltd.), and the tangent to the viscoelasticity ratio of the cured product measured at 1 Hz (tan accounted for) The main peak is the maximum temperature and the T g is determined. 2) Production of test piece A polycarbonate (hereinafter abbreviated as pc) film having a thickness of 50 μm (Iupilon FE-2000: manufactured by MITSUBISHI Engineering-Plastics (^)) was coated with a thickness of 1 μm by a bar coater. The obtained composition was placed on a pc film having a thickness of 5 μm by rolling, and placed at a position of 3 〇cm below the 120 W/cm, concentrating metal element lamp for transport. At a speed of 10 m/min, the film was repeatedly passed through the lamp three times to form a laminated film. The obtained test body was allowed to stand in a constant temperature and humidity (23 ^ 5 % RH) chamber for one day and one night, and the peel strength and the warpage at the time of bonding were evaluated. -28- 201245380 3) Peel strength • The peel strength of the test body was measured by a tensile tester under the following conditions under the constant temperature and humidity. • Type 5 test piece: 25 mm x 100 mm • Peeling angle: 180 degrees • Peeling speed: 200 mm/min Further, 'When the bonding strength is very strong', the substrate is broken when the peel strength is measured, and it is recorded as the base material destruction (material breaking). In addition, the unit of measurement of the peel strength is: gram weight / inch (gf / inch) is l (gf / inch) = 3.86xl0'3 (N / cm) 〇 4) warping when fitting 4 cut out 1 〇cmx丨〇cm size, placed under constant temperature and humidity for one day and one night, the height of the four corners of the warp. The values in the table indicate the average 値 of the height of the four corners. Higher values indicate greater warpage. Based on the measurement results, the following four levels were determined. Α: less than 〇5mm (good without warping), Β: 〇5mm or more and less than l.〇mm (with slight warpage), C: 1.0mm or more and less than 15mm (with warpage), D: 1.5mm or more ( Large warpage) 5) Heat test The cut body is cut to a size of 1 〇cmx 1 〇cm so that one part of the test body (5x10cm) is in contact with the hot plate and heated for 8 〇. 〇 1 minute or 1 20 C 10 minutes. The deflection of the test body at this time (maximum height of floating - minimum south degree) was evaluated. Higher values indicate greater deflection. Based on the measurement results, the following four levels are used for judgment. -29- 201245380
A 、’ mm(無撓曲而良好）、B: 0_5mm以上小 於[0_(有輕微撓曲）、c: 1 〇_以上小於i 5職（有 撓曲）、D : 1.5mm以上（撓曲大） 實施例1〜6之組成物均為剝離強度優異、無貼合時 之翹曲、無加熱試驗後之撓曲者。 另方面，不含（B)成分之比較例1的組成物雖然剝 離強度優異、無貼合時之翹曲，在加熱試驗後卻產生大 幅度撓曲。又，不含本發明（B)成分之必要成分的丙烯酿 胺（1)之比較例2的組成物，雖然無貼合時之翹曲或加熱 試驗後之撓曲，剝離強度卻大幅度下降。又，雖然含有 (A)〜（C)成分，卻完全不含具有曱基丙烯醯基之化合物 的比較例3之組成物’ $然剝離強度優異、無加熱試驗 後之撓曲，在貼合時卻產生大幅度翹曲。在（B)成分中不 含丙稀酿胺（2)之比較例4 & 5的組成物，雖然剝離強度 優異、無貼合時之翹曲’在較嚴苛的12〇。。之加熱試驗 後所得之積層體卻產生大幅度撓曲。 [産業上之可利用性] 根據本發明之接著劑組成物，可在高溫下亦維持優 異的接著力，亦少經時性著色’有效於作為各種光學構 件所使用的塑膠薄膜等之薄層被接著體彼此的積層接著 ，特別可適宜的使用在液晶顯示裝置等、光學薄膜之製 造。 ' 明 U 說 明 號 說 符 單 件 簡。元。 式無要無 圖 主 ί Γ -30-A, 'mm (no deflection is good), B: 0_5mm or more is less than [0_ (slightly deflected), c: 1 〇_ is less than i 5 (with deflection), D: 1.5mm or more (flexible) Large) The compositions of Examples 1 to 6 were excellent in peel strength, warpage when there was no bonding, and deflection after no heating test. On the other hand, the composition of Comparative Example 1 which does not contain the component (B) has excellent peeling strength and warpage when it is not bonded, and causes a large deflection after the heating test. Further, in the composition of Comparative Example 2 of the acrylamide (1) which does not contain the essential component of the component (B) of the present invention, the peel strength was greatly lowered although there was no warpage at the time of bonding or deflection after the heating test. . Further, the composition of Comparative Example 3 containing no (A) to (C) component but completely containing no compound having a mercaptopropenyl group had excellent peel strength and no deflection after the heating test, and was bonded. At the time, there was a large warpage. The composition of Comparative Example 4 & 5 which does not contain acrylamide (2) in the component (B) has excellent peel strength and warpage at the time of no bonding is less severe. . The laminate obtained after the heating test produced a large deflection. [Industrial Applicability] According to the adhesive composition of the present invention, it is possible to maintain excellent adhesion at high temperatures and to reduce coloration with less time. It is effective for thin layers such as plastic films used as various optical members. The laminate of the adherends is preferably used in the production of an optical film such as a liquid crystal display device. ' Ming U said the number is a simple one. yuan. Nothing, no picture, main ί Γ -30-