201022742 六、發明說明： 【發明所屬之技術領域】 本發明關於液晶顯示裝置等所使用的偏光板及其製法。 【先前技術】 偏光板係使用作爲液晶顯示裝置中的偏光之供給元件 ，而且使用作爲偏光的檢測元件。以往，作爲偏光板，使 用由在摻雜有碘等、經拉伸的聚乙烯醇（PVA)薄膜所成的偏 光鏡之至少一面上，黏著有三乙醯纖維素（TAC)所成的保護 〇 膜者。於此情況下，若在保護膜本身中有雙折射的存在， 則作爲偏光板的機能會大幅降低，爲了防止此，使用以溶 劑流延法所製作的沒有光學各向異性之TAC薄膜。 於如此的以往之偏光板中，由於PVA薄膜被高倍率拉 '伸，而在緩和方向發生大的應力。保護膜必須有耐得住此 應力的剛性，但是當使用TAC當作保護膜時，於液晶TV 等的大畫面用途中，薄膜周邊部的偏光鏡之收縮應力勝過 TAC的剛性而發生變形，由於伴隨其所發生的TAC保護膜 ® 之雙折射，故會發生脫色。 特開200 5-92 1 1 2號公報中，提案以活性能量線硬化性 樹脂組成物的硬化物代替TAC保護膜。若依照此技術，則 可得到雙折射小、耐濕熱性優異的偏光板。然而，僅雙折 射小，在如上述偏光鏡之收縮應力大的地方，雙折射會變 化，而損害作爲偏光板的機能。 先前技術文獻 專利文獻 -4- 201022742 [專利文獻1]特開2005-92 1 1 2號公報 【發明內容】 發明所欲解決的問題 本發明之目的在於提供保護膜爲透明，雙折射小，而且 即使受到應力，雙折射也不易變化的偏光板及其製法。 解決問題的手段 本發明者們爲了達成上述目的，進行專心致力的檢討， 結果發現在對偏光鏡的至少一面，以由含有特定量的特定 © 2種硬化性化合物之活性能量線硬化性樹脂組成物的硬化 物所成的保護膜所直接保護的偏光板中，保護膜的雙折射 少，而且即使受到應力，雙折射也不易變化，而完成本發 明》 即，本發明提供一種偏光板，其係具有偏光鏡的至少一 面不透過其它層而經由樹脂所成的保護膜所直接保護的構 造之偏光板，其特徵爲：前述樹脂係含有具有2個以上不 飽和羧酸醯基且具有橋聯脂環式骨架之化合物（A)與具有2 ® 個以上不飽和羧酸醯基且具有鏈狀飽和脂肪族烴骨架之化 合物（B)的活性能量線硬化性樹脂組成物之硬化物，前述具 有2個以上不飽和羧酸醯基且具有橋聯脂環式骨架之化合 物（A)及前述具有2個以上不飽和羧酸醯基且具有鏈狀飽和 脂肪族烴骨架之化合物（B)在活性能量線硬化性樹脂組成 物中的含量，相對於該活性能量線硬化性樹脂組成物中的 活性能量線硬化性化合物全體而言，分別爲30〜98重量％ 及1〜4 0重量％。 201022742 作爲前述具有2個以上不飽和羧酸醯基且具有橋聯脂 環式骨架之化合物（A)，較佳爲下述式（1)所示的化合物，201022742 VI. Description of the Invention: [Technical Field] The present invention relates to a polarizing plate used in a liquid crystal display device or the like and a method of manufacturing the same. [Prior Art] A polarizing plate is used as a supply element for polarized light in a liquid crystal display device, and a detecting element as a polarized light is used. Conventionally, as a polarizing plate, a protective layer made of triethylenesulfonate (TAC) adhered to at least one surface of a polarizing mirror made of a stretched polyvinyl alcohol (PVA) film doped with iodine or the like is used. Membrane. In this case, if birefringence exists in the protective film itself, the function as a polarizing plate is greatly reduced. To prevent this, a TAC film having no optical anisotropy produced by a solvent casting method is used. In such a conventional polarizing plate, since the PVA film is stretched at a high magnification, a large stress is generated in the relaxation direction. The protective film must have rigidity to withstand this stress. However, when TAC is used as the protective film, in a large-screen use such as a liquid crystal TV, the contraction stress of the polarizer at the peripheral portion of the film is more than the rigidity of the TAC and is deformed. Decoloration occurs due to the birefringence of the TAC protective film® that occurs with it. In JP-A-200 5-92 1 1 2, it is proposed to replace the TAC protective film with a cured product of the active energy ray-curable resin composition. According to this technique, a polarizing plate having a small birefringence and excellent moist heat resistance can be obtained. However, only the double-folding is small, and in the case where the contraction stress of the polarizer is large as described above, the birefringence changes, and the function as a polarizing plate is impaired. [Problem to be Solved by the Invention] [Problem to be Solved by the Invention] An object of the present invention is to provide a protective film which is transparent and has low birefringence, and A polarizing plate that is not easily changed by birefringence even under stress, and a method of manufacturing the same. Means for Solving the Problems In order to achieve the above object, the inventors of the present invention conducted an intensive review and found that at least one side of the polarizer is composed of an active energy ray-curable resin containing a specific amount of two specific curable compounds. In the polarizing plate directly protected by the protective film formed by the cured product of the object, the birefringence of the protective film is small, and the birefringence is not easily changed even if subjected to stress, and the present invention provides a polarizing plate. A polarizing plate having a structure in which at least one surface of a polarizer does not transmit through another layer and is directly protected by a protective film made of a resin, wherein the resin contains two or more unsaturated carboxylic acid sulfhydryl groups and has a bridge a cured product of an active energy ray-curable resin composition of the alicyclic skeleton compound (A) and the compound (B) having 2 + or more unsaturated carboxylic acid sulfhydryl groups and having a chain saturated aliphatic hydrocarbon skeleton, a compound (A) having two or more unsaturated carboxylic acid sulfhydryl groups and having a bridged alicyclic skeleton, and the aforementioned thiol group having two or more unsaturated carboxylic acids and having The content of the compound (B) of the chain-like saturated aliphatic hydrocarbon skeleton in the active energy ray-curable resin composition is the same as the total amount of the active energy ray-curable compound in the active energy ray-curable resin composition. 30 to 98% by weight and 1 to 40% by weight. 201022742 The compound (A) having two or more unsaturated carboxylic acid fluorenyl groups and having a bridged alicyclic skeleton is preferably a compound represented by the following formula (1).
⑴ (式中，R1、R2係相同或不同，表示氫原子或碳數1〜4的 烷基，X1、X2係相同或不同，表示單鍵、碳數1〜8的伸 烷基、或1或2個以上碳數1〜8的伸烷基與1或2個以上 氧原子或硫原子所鍵結的2價基；m、η各自表示0或1) 又，作爲前述具有2個以上不飽和羧酸醯基且具有鏈狀 飽和脂肪族烴骨架之化合物（Β)，較佳爲下述式（2)所示的化 合物， R3 R4 0 0 (式中，R3、R4係相同或不同，表示氫原子或碳數1〜4的 烷基，Α表示碳數2〜15的直鏈狀或支鏈狀的伸烷基，X3 、X4係相同或不同，表示單鍵或連結基）。 又，本發明提供一種偏光板之製法，其特徵爲在偏光鏡 的至少一面上，不透過其它層而直接塗佈活性能量線硬化 性樹脂組成物後，使該活性能量線硬化性樹脂組成物硬化 201022742 而形成保護膜，其中該活性能量線硬化性樹脂組成物含有 具有2個以上不飽和羧酸醯基且具有橋聯脂環式骨架之化 合物（A)與具有2個以上不飽和羧酸醯基且具有鏈狀飽和脂 肪族烴骨架之化合物（B)，同時前述具有2個以上不飽和羧 酸醯基且具有橋聯脂環式骨架之化合物（A)及前述具有2個 以上不飽和羧酸醯基且具有鏈狀飽和脂肪族烴骨架之化合 物（B)的含量，相對於該活性能量線硬化性樹脂組成物中的 活性能量線硬化性化合物全體而言，分別爲3 0〜9 8重量％ © 及1〜4 0重量％ » 再者，於前述具有2個以上不飽和羧酸醯基且具有鏈狀 飽和脂肪族烴骨架之化合物（B)中，不包含具有2個以上不 飽和羧酸醯基且具有橋聯脂環式骨架之化合物。 發明的效果 依照本發明的偏光板，由於使用含有特定量的特定2 種硬化性化合物之活性能量線硬化性樹脂組成物的硬化物 當作偏光鏡的保護膜，故保護膜爲透明，不僅雙折射小， ® 而且即使受到應力，雙折射也不易變化。又，亦具有韌性 高、不易破裂的特性。依照本發明的製造方法，可簡易地 製造具有如此優異特性的偏光板。 【實施方式】 實施發明的最佳形態 本發明的偏光板係具有偏光鏡的至少一面由樹脂所成 的保護膜所保護的構造。作爲偏光鏡，並沒有特別的限定 ，可使用在聚乙烯醇（PVA)、其縮醛化物、乙烯-醋酸乙烯 201022742 酯共聚物、其皂化物等的基材中摻雜有碘、二色性染料而 經拉伸的薄膜，或彼等經交聯處理的薄膜等。於此等之中 ，特佳爲在聚乙烯醇中摻雜有碘而經拉伸之含碘的聚乙烯 醇薄膜，或以硼酸等交聯其者。 於本發明中，作爲構成保護膜的樹脂，使用含有具有2 個以上不飽和羧酸醯基且具有橋聯脂環式骨架之化合物（A) 與具有2個以上不飽和羧酸醯基且具有鏈狀飽和脂肪族烴 骨架之化合物(B)的活性能量線硬化性樹脂組成物之硬化 ® 物。再者，於本說明書中，活性能量線硬化性樹脂組成物 係意味可形成藉由活性能量線的照射而硬化之樹脂的組成 物。 [具有2個以上不飽和羧酸醯基且具有橋聯脂環式骨架之化 合物（A)] 作爲具有2個以上不飽和羧酸醯基且具有橋聯脂環式 骨架之化合物（A)，只要是分子內具有橋聯脂環式骨架及2 個以上不飽和羧酸醯基之自由基硬化性化合物即可，並沒 ® 有特別的限定。作爲不飽和羧酸醯基，可舉出丙烯醯基、 甲基丙烯醯基、α-乙基丙烯醯基、ct-丙基丙烯醯基、心丁 基丙烯醯基、巴豆酸醯基等之碳數3〜10左右的不飽和羧 酸醯基等。 作爲橋聯脂環式骨架，例如可舉出三環[5.2.1. 〇2,6]癸烷 環、三環[4.4.0.12,5]十一烷環、五環[6·5.1_13,6.〇2,7.〇9，ΐ3] 十五烷環、五環[6.6.1.13’6.02’7.09’14]十六烷環、原冰片烷 環、莰烷環、異冰片烷環、四環[4·4·0·12’5.17>1()]十二烷環 201022742 、金剛烷環、萘烷環、全氫茚環等。於此等之中，較佳爲 三環[5.2.1.〇2,6]癸烷環、三環[4.4_〇.12’5]十—烷環、五環 [6.5.1.13,6.〇2,7 〇9，13]十五烷環、五環[6 6 丨 l3,6 〇2 7 〇9 14] 十六烷環，特佳爲三環[5.2.1.02,6]癸烷環。 橋聯脂環式骨架可具有取代基。作爲該取代基，例如可 舉出氟原子、氣原子等的鹵素原子；甲基、乙基、丙基等 的院基（碳數1〜6的院基等）；甲氧基、乙氧基、丙氧基等 的烷氧基；乙醯基等的醯基；甲氧羰基、乙氧羰基等的烷 © 氧羰基；羥基；羧基等。 不飽和羧酸醯基與橋聯脂環式骨架可直接鍵結，亦可經 由連結基來鍵結。 作爲連結基，可舉出可有取代基的多價（例如2價）烴基 、氧原子（-0-)、硫原子（-S-)、-NR-(R表示氫原子或碳數1 〜6的烷基）、羰基（_c〇-)、或此等以2個以上所鍵結的基 。作爲2價烴基，例如可舉出亞甲基、伸乙基、甲基亞甲 基、二甲基亞甲基、伸丙基、三亞甲基、四亞甲基、五亞 ® 甲基、六亞甲基、七亞甲基、八亞甲基等的伸烷基（碳數1 〜8的伸烷基等）；伸環戊基、伸環己基、亞環戊基、亞環 己基等的伸環烷基等之2價脂環式烴基；伸苯基、伸芳基 等的伸芳基（ary lene)基；此等鍵以2個以上所鍵結的基。 作爲前述連結基，較佳爲下述式（3)所示的基， -X5-0- (3) (式中，X5表示單鍵、碳數1〜8的伸烷基、或1或2個以 上碳數1〜8的伸烷基與1或2個以上氧原子（-0-)或硫原 201022742 子（-S-)所鍵結的2價基。X5的左側係鍵結於橋聯脂環式骨 架，〇的右側係鍵結於不飽和羧酸醯基）。 作爲碳數1〜8的伸烷基，例如可舉出亞甲基、伸乙基 、甲基亞甲基、二甲基亞甲基、伸丙基、三亞甲基、四亞 甲基、五亞甲基、六亞甲基、七亞甲基、八亞甲基等。 作爲1或2個以上碳數1〜8的伸烷基與1或2個以上 氧原子或硫原子所鍵結的2價基，例如可舉出碳數1〜8的 氧基伸烷基、碳數2〜8的伸烷氧基伸烷基、碳數1〜8的 〇 硫伸烷基、碳數2〜8的伸烷基硫伸烷基、碳數2〜8的聚（ 氧基伸烷基）基、碳數3〜8的伸烷基聚（氧基伸烷基）基等。 作爲X5,特佳爲單鍵或碳數1〜8的伸烷基，極佳爲亞 甲基。 作爲具有2個以上不飽和羧酸醯基且具有橋聯脂環式 骨架之化合物（A)之代表例，可舉出前述式（1)所示的化合 物。式（1)中，R1、R2係相同或不同，表示氫原子或碳數1 〜4的烷基，X1、X2係相同或不同，表示單鍵、碳數1〜8 ® 的伸烷基、或1或2個以上碳數1〜8的伸烷基與1或2個 以上氧原子或硫原子所鍵結的2價基。m、η各自表示〇或 1 ° 作爲R1、R2中的碳數1〜4的烷基，例如可舉出甲基、 乙基、丙基、異丙基、丁基、異丁基、第三丁酯。作爲R1 、R2，特佳爲氫原子或甲基。 作爲X1、X2中的碳數1〜8的伸烷基、1或2個以上碳 數1〜8的伸烷基與1或2個以上氧原子或硫原子所鍵結的 -10- 201022742 2價基，係與上述X5同樣。作爲Χ^Χ2,各自特佳爲單鍵 或碳數1〜8的伸烷基，極佳爲亞甲基。 m、η各自特佳爲0。 作爲式（1)所示的化合物之具體例，可舉出三環 [5.2.1.02’6]癸烷二甲醇二（甲基）丙烯酸酯、三環[5.2.1.02,6] 癸二醇二（甲基）丙烯酸酯、三環[4.4.0.1 2,5]十一烷二甲醇二 (甲基）丙烯酸酯、三環[4.4.0.1 2’5]十一烷二醇二（甲基）丙烯 酸酯、五環[6.5.1.I3’6.Ο2’7.09’13]十五烷二甲醇二（甲基）丙 〇 烯酸酯、五環[6.5.1.13’6.02’7.09’13]十五烷二醇二（甲基）丙 烯酸酯、五環[6.6.1.13’6.Ο2’7.09’14]十六烷二甲醇二（甲基） 丙烯酸酯、五環[6.6.1.13’6.02’7.09’14]十六烷二醇二（甲基） 丙烯酸酯等》 [具有2個以上不飽和羧酸醯基且具有鏈狀飽和脂肪族烴骨 架之化合物（Β)] 作爲具有2個以上不飽和羧酸醯基且具有鏈狀飽和脂 肪族烴骨架之化合物（Β)，只要分子內具有鏈狀飽和脂肪族 ® 烴骨架與2以上不飽和羧酸醯基之自由基硬化性化合物即 可，並沒有特別的限定。作爲不飽和羧酸醯基，可舉出丙 烯醯基、甲基丙烯醯基、α-乙基丙烯醯基、α-丙基丙烯醯 基、α-丁基丙烯醯基、巴豆酸醯基等的碳數3〜10左右之 不飽和羧酸醯基等。 鏈狀飽和脂肪族烴骨架的碳數，例如爲1〜20,較佳爲 2〜20，更佳爲3〜15(尤其3〜10)。 於鏈狀飽和脂肪族烴骨架中，含有2價以上鏈狀飽和脂 -11- 201022742 肪族烴基。作爲2價以上鏈狀飽和脂肪族烴基， 價鏈狀飽和脂肪族烴基之直鏈狀或支鏈狀的伸烷 應於此的3價〜4價鏈狀飽和脂肪族烴基等。作 或支鏈狀的伸烷基，例如可舉出亞甲基、伸乙基 甲基、二甲基亞甲基、伸丙基、三亞甲基、四亞 亞甲基、六亞甲基、七亞甲基、八亞甲基、三甲 基、十亞甲基、十二亞甲基、十四亞甲基等的碳 之直鏈狀或支鏈狀的伸烷基。於此等之中，較佳 Ο 〜20的直鏈狀或支鏈狀的伸烷基，特佳爲碳數3 3〜10)之直鏈狀或支鏈狀的伸烷基。 鏈狀飽和脂肪族烴骨架可具有取代基。作爲髮 例如可舉出氟原子、氯原子等的鹵素原子；甲氧 基、丙氧基等的烷氧基；乙醯基等的醯基；甲氧 氧羰基等的烷氧羰基；羥基；羧基等。 不飽和羧酸醯基與鏈狀飽和脂肪族烴骨架可 ，也可經由連結基來鍵結。 ® 作爲連結基，可舉出可有取代基的多價（例如 環式或芳香族烴基、氧原子（-〇-)、硫原子（-S-)、 示氫原子或碳數1〜6的烷基）、羰基（-CO-)、或 個以上所鍵結的基、或此等的1個以上與可有取 價（例如2價）之脂肪族烴基的1個以上所鍵結的 爲多價的脂環式或芳香族烴基，可舉出伸環戊基 基、伸苯基等。作爲多價的脂肪族烴基，例如可 基、伸乙基、甲基亞甲基、二甲基亞甲基、伸丙 可舉出2 基、及對 爲直鏈狀 、甲基亞 甲基、五 基六亞甲 數 1〜20 爲碳數2 〜1 5(例如 t取代基， 基、乙氧 羰基、乙 直接結合 2價）之脂 -N R - (R 表 此等以2 代基的多 基等。作 、伸環己 舉出亞甲 基、三亞 -12- 201022742 甲基、四亞甲基、五亞甲基、六亞甲基、七亞甲基、八亞 甲基等的伸院基（碳數1〜8的伸院基等）等。 作爲具有2個以上不飽和羧酸醯基且具有鏈狀飽和脂 肪族烴骨架之化合物（B)的代表例，可舉出前述式（2)所示的 化合物。式（2)中’ R3、R4係相同或不同，表示氫原子或碳 數1〜4的烷基’ A表示碳數2〜15的直鏈狀或支鏈狀之伸 烷基，X3、X4係相同或不同，表示單鍵或連結基。 作爲R3、R4中的碳數1〜4的烷基，例如可舉出甲基、 ® 乙基、丙基、異丙基、丁基、異丁基、第三丁酯。作爲R3 、R4，特佳爲氫原子或甲基。 作爲A中的碳數2〜15的直鏈狀或支鏈狀之伸烷基， 例如可舉出伸乙基、伸丙基、三亞甲基、四亞甲基、五亞 甲基、六亞甲基、七亞甲基、八亞甲基、三甲基六亞甲基 、十亞甲基、十二亞甲基、十四亞甲基等。於此等之中， 較佳爲碳數3〜12的直鏈狀或支鏈狀之伸烷基，特佳爲六 亞甲基、三甲基六亞甲基。 ® 作爲X3、X4中的前述連結基，可舉出1或2個以上碳 數1〜8之伸烷基與由氧原子（-〇-)、硫原子（-S-)、-NR-(R 表示氫原子或碳數1〜6的烷基）及羰基（-CO-)所選出的1 或2個以上基所鍵結之2價基等。 作爲X3、X4中的前述連結基之代表例，例如可舉出 -NH-C0-0-CH2CH2- 、 -NH-CO-O-CH2CH2CH2- 、 -NH-CO-0-CH2CH2CH2CH2- 、 -nh-co-o-ch2ch2ch2ch2ch2ch2-(皆左側鍵結於 A，右側 -13- 201022742 鍵結於不飽和羧酸醢氧基的氧原子）等。 作爲式（2)所示的化合物之具體例，可舉出六亞甲基二 異氰酸酯與（甲基）丙烯酸羥乙酯的反應生成物、三甲基六 亞甲基二異氰酸酯與（甲基）丙烯酸羥乙酯的反應生成物等 之飽和脂肪族聚異氰酸酯與（甲基）丙烯酸羥烷基酯的反應 生成物等之具有2以上不飽和羧酸醯基且具有鏈狀飽和脂 肪族烴骨架的胺甲酸酯化合物等。 於前述式（2)所示的化合物之中，較佳爲下述式（2 a)所示 © 的化合物，(1) (wherein R1 and R2 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and X1 and X2 are the same or different and each represents a single bond, an alkylene group having 1 to 8 carbon atoms, or 1 Or a divalent group of two or more alkylene groups having 1 to 8 carbon atoms and one or more oxygen atoms or sulfur atoms; m and η each represent 0 or 1), and 2 or more a compound having a saturated carboxylic acid sulfhydryl group and having a chain-like saturated aliphatic hydrocarbon skeleton, preferably a compound represented by the following formula (2), R3 R4 0 0 (wherein R3 and R4 are the same or different, The hydrogen atom or the alkyl group having 1 to 4 carbon atoms, Α represents a linear or branched alkyl group having 2 to 15 carbon atoms, and X3 and X4 are the same or different and each represents a single bond or a linking group. Moreover, the present invention provides a method for producing a polarizing plate, characterized in that the active energy ray-curable resin composition is directly applied to at least one surface of a polarizing mirror without applying another layer, and then the active energy ray-curable resin composition is applied. Hardening 201022742 to form a protective film, wherein the active energy ray-curable resin composition contains a compound (A) having two or more unsaturated carboxylic acid sulfonium groups and having a bridged alicyclic skeleton and having two or more unsaturated carboxylic acids a compound (B) having a fluorenyl group and having a chain-like saturated aliphatic hydrocarbon skeleton, and the above compound (A) having two or more unsaturated carboxylic acid fluorenyl groups and having a bridged alicyclic skeleton, and the above having two or more unsaturated groups The content of the compound (B) having a carboxylic acid sulfhydryl group and having a chain-like saturated aliphatic hydrocarbon skeleton is 30 to 9 for the entire active energy ray-curable compound in the active energy ray-curable resin composition, respectively. 8 wt% © and 1 to 40% by weight » In addition, the compound (B) having two or more unsaturated carboxylic acid sulfhydryl groups and having a chain-like saturated aliphatic hydrocarbon skeleton does not contain Two or more unsaturated carboxylic acid compounds and acyl bridged alicyclic skeleton having the. Advantageous Effects of Invention According to the polarizing plate of the present invention, since a cured product of an active energy ray-curable resin composition containing a specific amount of a specific two kinds of curable compounds is used as a protective film for a polarizer, the protective film is transparent, not only double The refraction is small, ® and the birefringence does not change easily even under stress. In addition, it also has high toughness and is not easily broken. According to the manufacturing method of the present invention, a polarizing plate having such excellent characteristics can be easily produced. [Embodiment] The best mode for carrying out the invention The polarizing plate of the present invention has a structure in which at least one surface of the polarizer is protected by a protective film made of a resin. The polarizer is not particularly limited, and a substrate such as polyvinyl alcohol (PVA), an acetal, an ethylene-vinyl acetate 201022742 ester copolymer, or a saponified product thereof may be doped with iodine or dichroism. Films which are stretched by dyes, or films which have been crosslinked, and the like. Among them, a polyvinyl alcohol film containing iodine which is stretched with iodine in polyvinyl alcohol is preferably used, or it is crosslinked by boric acid or the like. In the present invention, as the resin constituting the protective film, a compound (A) having a fluorenyl group having two or more unsaturated carboxylic acids and having a bridged alicyclic skeleton and a fluorenyl group having two or more unsaturated carboxylic acids are used. A hardening agent of an active energy ray-curable resin composition of a compound (B) of a chain-like saturated aliphatic hydrocarbon skeleton. Further, in the present specification, the active energy ray-curable resin composition means a composition of a resin which can be cured by irradiation with an active energy ray. [Compound (A) having two or more unsaturated carboxylic acid fluorenyl groups and having a bridged alicyclic skeleton] As the compound (A) having two or more unsaturated carboxylic acid fluorenyl groups and having a bridged alicyclic skeleton, Any radical curable compound having a bridged alicyclic skeleton and two or more unsaturated carboxylic acid sulfhydryl groups in the molecule may be used, and it is not particularly limited. Examples of the unsaturated carboxylic acid thiol group include an acryl fluorenyl group, a methacryl fluorenyl group, an α-ethyl acryl fluorenyl group, a ct-propyl acryl fluorenyl group, a cardibutyl acryl fluorenyl group, a crotonic acid decyl group, and the like. An unsaturated carboxylic acid sulfhydryl group having a carbon number of from 3 to 10 or the like. Examples of the bridged alicyclic skeleton include a tricyclo[5.2.1. 〇2,6]decane ring, a tricyclo[4.4.0.12,5]undecane ring, and a penta ring [6·5.1_13, 6.〇2,7.〇9,ΐ3] pentadecane ring, pentacyclic ring [6.6.1.13'6.02'7.09'14] hexadecane ring, norbornane ring, decane ring, isobornane ring, four Ring [4·4·0·12'5.17>1()] dodecane ring 201022742, adamantane ring, decalin ring, perhydroanthracene ring, and the like. Among these, a tricyclo[5.2.1.〇2,6]decane ring, a tricyclo[4.4_〇.12'5]decane ring, and a pentacyclic ring [6.5.1.13, 6. 〇2,7 〇9,13]pentadecane ring, pentacyclo[6 6 丨l3,6 〇2 7 〇9 14] hexadecane ring, especially preferably tricyclo[5.2.1.02,6]decane ring . The bridged alicyclic skeleton may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom or a gas atom; a hospital group such as a methyl group, an ethyl group, and a propyl group (such as a hospital having a carbon number of 1 to 6); a methoxy group and an ethoxy group; An alkoxy group such as a propoxy group; a mercapto group such as an ethenyl group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; a hydroxyl group; a carboxyl group; The unsaturated carboxylic acid thiol group may be directly bonded to the bridged alicyclic skeleton or may be bonded via a linking group. Examples of the linking group include a polyvalent (for example, divalent) hydrocarbon group which may have a substituent, an oxygen atom (-0-), a sulfur atom (-S-), and -NR- (R represents a hydrogen atom or a carbon number of 1 to 6 alkyl), carbonyl (_c〇-), or these two or more bonded groups. Examples of the divalent hydrocarbon group include a methylene group, an ethylidene group, a methylmethylene group, a dimethylmethylene group, a propylidene group, a trimethylene group, a tetramethylene group, a pentylene group, a methyl group, and a hexamethyl group. An alkylene group such as a methylene group, a heptamethylene group or an octamethylene group (such as an alkylene group having 1 to 8 carbon atoms); a cyclopentyl group, a cyclohexylene group, a cyclopentylene group, a cyclohexylene group or the like; a divalent alicyclic hydrocarbon group such as a cycloalkyl group; an ary lene group such as a phenyl group or an aryl group; and these bonds are bonded to two or more groups. The linking group is preferably a group represented by the following formula (3), -X5-0- (3) (wherein, X5 represents a single bond, an alkylene group having 1 to 8 carbon atoms, or 1 or 2) More than one alkyl group having 1 to 8 carbon atoms and a divalent group bonded to one or more oxygen atoms (-0-) or sulfogen 201022742 (-S-). The left side of X5 is bonded to the bridge. A bicyclic ring skeleton in which the right side of the oxime is bonded to an unsaturated carboxylic acid sulfhydryl group. Examples of the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylidene group, a methylmethylene group, a dimethylmethylene group, a propyl group, a trimethylene group, a tetramethylene group, and a penta Methylene, hexamethylene, heptamethylene, octamethylene and the like. Examples of the divalent group in which one or two or more alkylene groups having 1 to 8 carbon atoms are bonded to one or more oxygen atoms or sulfur atoms include, for example, an alkylene group having 1 to 8 carbon atoms and carbon. a 2 to 8 alkylene oxide alkyl group, a carbon number 1 to 8 sulfonium alkylene group, a carbon number 2 to 8 alkylthioalkylene group, and a carbon number 2 to 8 poly(oxyalkylene alkyl group) a group, an alkylene poly(oxyalkylene) group having 3 to 8 carbon atoms, and the like. As X5, a single bond or an alkylene group having a carbon number of 1 to 8 is particularly preferable, and it is preferably a methylene group. A representative example of the compound (A) having two or more unsaturated carboxylic acid fluorenyl groups and having a bridged alicyclic skeleton is exemplified by the compound represented by the above formula (1). In the formula (1), R1 and R2 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X1 and X2 are the same or different and each represents a single bond, an alkylene group having 1 to 8 carbon atoms, Or a divalent group in which one or two or more alkyl groups having 1 to 8 carbon atoms are bonded to one or more oxygen atoms or sulfur atoms. Each of m and η represents 〇 or 1 ° as an alkyl group having 1 to 4 carbon atoms in R1 and R2, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a third group. Butyl ester. As R1 and R2, a hydrogen atom or a methyl group is particularly preferred. Examples of the alkylene group having 1 to 8 carbon atoms in X1 and X2, and the alkylene group having 1 or 2 carbon atoms and 1 to 8 carbon atoms bonded to one or more oxygen atoms or sulfur atoms -10- 201022742 2 The price base is the same as X5 above. As Χ^Χ2, each is preferably a single bond or an alkylene group having 1 to 8 carbon atoms, and is preferably a methylene group. Each of m and η is particularly preferably 0. Specific examples of the compound represented by the formula (1) include tricyclo[5.2.1.02'6]decane dimethanol di(meth)acrylate, tricyclo[5.2.1.02,6]nonanediol II. (Meth) acrylate, tricyclo[4.4.0.1 2,5]undecane dimethanol di(meth) acrylate, tricyclo[4.4.0.1 2'5]undecanediol di(methyl) Acrylate, pentacyclic [6.5.1.I3'6.Ο2'7.09'13] pentadecane dimethanol di(methyl)propionate, pentacyclic [6.5.1.13'6.02'7.09'13] Pentalinediol di(meth)acrylate, pentacyclo[6.6.1.13'6.Ο2'7.09'14]hexadecanedimethylethanol di(meth)acrylate, pentacyclic [6.6.1.13'6.02'7.09 '14]hexadecanediol di(meth)acrylate or the like [compound having two or more unsaturated carboxylic acid sulfhydryl groups and having a chain saturated aliphatic hydrocarbon skeleton (Β)] as having two or more unsaturated groups a compound having a carboxylic acid sulfhydryl group and having a chain-like saturated aliphatic hydrocarbon skeleton, as long as it has a chain-like saturated aliphatic hydrocarbon skeleton and a radically curable compound having two or more unsaturated carboxylic acid sulfhydryl groups in the molecule, and nothing special Set. Examples of the unsaturated carboxylic acid thiol group include an acrylonitrile group, a methacryl fluorenyl group, an α-ethyl propylene fluorenyl group, an α-propyl acryl fluorenyl group, an α-butyl acryl fluorenyl group, a crotonic acid decyl group, and the like. The unsaturated carboxylic acid thiol group having a carbon number of about 3 to 10 or the like. The carbon number of the chain-like saturated aliphatic hydrocarbon skeleton is, for example, 1 to 20, preferably 2 to 20, more preferably 3 to 15 (particularly 3 to 10). The chain saturated aliphatic hydrocarbon skeleton contains a divalent or higher chain saturated aliphatic -11-201022742 aliphatic hydrocarbon group. The linear or branched alkylene having a linear or branched chain-like saturated aliphatic hydrocarbon group as a divalent or higher chain saturated aliphatic hydrocarbon group is preferably a trivalent to tetravalent chain saturated aliphatic hydrocarbon group. Examples of the alkylene group which may be a branched or branched chain include a methylene group, an ethylidene group, a dimethylmethylene group, a propylidene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. a linear or branched alkylene group of carbon such as heptamethylene, octamethyl, trimethyl, decamethylene, dodecamethylene or tetradecyl. Among these, a linear or branched alkyl group of ～20 is preferable, and a linear or branched alkyl group having a carbon number of 3 3 to 10) is particularly preferable. The chain saturated aliphatic hydrocarbon skeleton may have a substituent. Examples of the hair source include a halogen atom such as a fluorine atom or a chlorine atom; an alkoxy group such as a methoxy group or a propoxy group; a mercapto group such as an ethenyl group; an alkoxycarbonyl group such as a methoxyoxycarbonyl group; a hydroxyl group; and a carboxyl group. Wait. The unsaturated carboxylic acid sulfhydryl group and the chain saturated aliphatic hydrocarbon skeleton may be bonded via a linking group. As the linking group, a polyvalent group having a substituent (for example, a cyclic or aromatic hydrocarbon group, an oxygen atom (-〇-), a sulfur atom (-S-), a hydrogen atom or a carbon number of 1 to 6 may be mentioned. The alkyl group, the carbonyl group (-CO-), or more than one of the bonded groups, or one or more of these, and one or more of the aliphatic hydrocarbon groups which may have a value (for example, a divalent) are bonded. The polyvalent alicyclic or aromatic hydrocarbon group may, for example, be a cyclopentyl group or a phenyl group. Examples of the polyvalent aliphatic hydrocarbon group include a ketone group, an ethylidene group, a methylmethylene group, a dimethylmethylene group, a propenyl group, and a linear group, a methylmethylene group. Pentayl hexamethylene 1 to 20 is a carbon number of 2 to 1 5 (for example, t substituent, ethoxycarbonyl group, and B is directly bonded to the valence of 2 valence) of lipid-NR - (R is such that the number of bases is 2 Base, etc., the extension, the extension of the methylene, Sanya-12- 201022742 methyl, tetramethylene, pentamethylene, hexamethylene, heptamethyl, octamethyl, etc. A representative example of the compound (B) having two or more unsaturated carboxylic acid sulfhydryl groups and having a chain-like saturated aliphatic hydrocarbon skeleton, and the above formula ( 2) The compound shown. In the formula (2), R3 and R4 are the same or different and each represents a hydrogen atom or an alkyl group having a carbon number of 1 to 4, and A represents a linear or branched carbon number of 2 to 15. The alkyl group, X3 and X4 are the same or different and each represents a single bond or a linking group. Examples of the alkyl group having 1 to 4 carbon atoms in R3 and R4 include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Base, butyl, different Butyl or tert-butyl ester. R3 and R4 are particularly preferably a hydrogen atom or a methyl group. As a linear or branched alkyl group having 2 to 15 carbon atoms in A, for example, Base, propyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, trimethylhexamethylene, decamethylene, twelve Methylene group, tetradecyl group, etc. Among them, a linear or branched alkyl group having a carbon number of 3 to 12 is preferred, and a hexamethylene group or a trimethyl group is particularly preferred. Methylene group. As the above-mentioned linking group in X3 and X4, one or two or more alkylene groups having a carbon number of 1 to 8 and an oxygen atom (-〇-), a sulfur atom (-S-), -NR- (R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and a divalent group to which one or more substituents selected by a carbonyl group (-CO-) are bonded, etc. As described above in X3 and X4 Representative examples of the linking group include, for example, -NH-C0-0-CH2CH2-, -NH-CO-O-CH2CH2CH2-, -NH-CO-0-CH2CH2CH2CH2-, -nh-co-o-ch2ch2ch2ch2ch2ch2-( Both the left side is bonded to A, the right side is -13-201022742 is bonded to the oxygen atom of the unsaturated carboxylic acid oxime). Specific examples of the compound represented by the formula (2) include a reaction product of hexamethylene diisocyanate and hydroxyethyl (meth)acrylate, trimethylhexamethylene diisocyanate and (meth)acrylic acid. An amine having 2 or more unsaturated carboxylic acid sulfhydryl groups and having a chain saturated aliphatic hydrocarbon skeleton, such as a reaction product of a saturated aliphatic polyisocyanate such as a reaction product of hydroxyethyl ester and a hydroxyalkyl (meth) acrylate The compound represented by the above formula (2) is preferably a compound represented by the following formula (2 a),
(式中，R3、R4係與前述相同。R5、R6、R7係相同或不同 ，表示氫原子或碳數1〜4的烷基）。 作爲R5、R6、R7中的碳數1〜4的烷基，例如可舉出甲 基、乙基、丙基、異丙基、丁基、異丁基、第三丁酯。作 ® 爲r3、r4，特佳爲氫原子或甲基。 作爲具有2個以上不飽和羧酸醯基且具有鏈狀飽和脂 肪族烴骨架之化合物（B)的其它例，例如可舉出1，4_丁二醇 二（甲基）丙烯酸酯、1，6·己二醇二（甲基）丙烯酸酯、新戊二 醇二（甲基）丙烯酸酯、乙二醇二（甲基）丙烯酸酯等的伸烷二 醇二（甲基）丙烯酸酯[C^5伸烷二醇二（甲基）丙烯酸酯等] 、聚乙二醇二（甲基）丙烯酸酯、聚丙二醇二（甲基）丙烯酸酯 等的聚伸烷二醇二（甲基）丙烯酸酯、雙酚A-二縮水甘油醚 -14- 201022742 二（甲基）丙烯酸酯、環氧乙烷改性雙酚A-二（甲基）丙烯酸 酯等的2官能性（甲基）丙烯酸酯；三羥甲基丙烷三（甲基） 丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、季戊四醇五（甲基） 丙烯酸酯 '季戊四醇六（甲基）丙烯酸酯、附加有環氧乙烷 的三羥甲基丙烷的三（甲基）丙烯酸酯、二季戊四醇五（甲基） 丙烯酸酯等的3官能以上之多官能性單體。於此等之中， 較佳爲1,6-己二醇二（甲基）丙烯酸酯等的C2-15伸烷二醇二 (甲基）丙烯酸酯（尤其C4_12伸烷二醇二（甲基）丙烯酸酯）。 ❹ 於本發明的活性能量線硬化性樹脂組成物中，作爲活性 能量線硬化性化合物，可僅包含上述具有2個以上不飽和 羧酸醯基且具有橋聯脂環式骨架之化合物（A)及具有2個以 上不飽和羧酸醯基且具有鏈狀飽和脂肪族烴骨架之化合物 (B)，也可更含有其它活性能量線硬化性化合物。作爲如此 的其它活性能量線硬化性化合物，可舉出自由基硬化性化 合物、陽離子硬化性化合物。 作爲自由基硬化性化合物，可舉出分子內具有至少1 ® 個乙烯性雙鍵，在聚合引發劑的存在下藉由活性能量線（例 如紫外線、可見光、電子線、X射線等）的照射可聚合的化 合物。作爲如此的化合物，例如可舉出（甲基）丙烯酸；（甲 基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（ 甲基）丙烯酸丁酯、（甲基）丙烯酸第三丁酯、（甲基）丙烯酸 2-乙基己酯、（甲基）丙烯酸壬酯、（甲基）丙烯酸苄酯、（甲 基）丙烯酸環己酯、（甲基）丙烯酸二環戊烯酯、（甲基）丙烯 酸縮水甘油酯、（甲基）丙烯酸甲氧基乙酯、（甲基）丙烯酸乙 -15- 201022742 氧基乙酯、（甲基）丙烯酸四氫糠酯、（甲基）丙烯酸2-羥乙醋 、（甲基）丙烯酸2·羥丙酯、（甲基）丙烯酸苯氧基乙酯、（甲 基）丙烯酸原冰片酯、（甲基）丙烯酸異冰片酯、（甲基）丙烯 醯基嗎啉、γ-(甲基）丙烯醯氧基丙基三甲氧基矽烷等的單官 能（甲基）丙烯酸酯系單體；苯乙烯、α-甲基苯乙烯、乙烯基 甲苯、醋酸乙烯酯、醋酸烯丙酯、丙酸乙烯酯、苯甲酸乙 烯酯、Ν-乙烯基吡咯啶酮、Ν-乙烯基咪唑、Ν-乙烯基己內 醯胺等的乙烯基系單體；氰尿酸三烯丙酯、異氰尿酸三烯 〇 丙酯、1，3,5-三丙烯醯基六氫-S·肼等。於此等之中，較佳 爲2官能以上多官能性單體。此等的自由基硬化性化合物 可爲單獨或組合2種以上來使用。 又，作爲自由基硬化性化合物，亦可使用酯（甲基）丙烯 酸酯、胺甲酸酯（甲基）丙烯酸酯、環氧（甲基）丙烯酸酯、丙 烯醯基（甲基）丙烯酸酯等的（甲基）丙烯酸酯寡聚物。 作爲陽離子硬化性化合物，例如可舉出乙烯基醚系化合 物、環氧系化合物、氧雜環丁烷系化合物等》 ® 作爲乙烯基醚系化合物，例如可舉出環氧乙烷改性雙酣 Α-二乙烯基醚、環氧乙烷改性氫醌二乙烯基醚等。 作爲環氧系化合物，例如可舉出1，2-環氧基環己烷、檸 檬烯二環氧化物、3,4-環氧基環己基甲基-3’，4’-環氧基環己 烷羧酸酯、1，4·丁二醇二縮水甘油醚、三羥甲基丙烷二縮 水甘油醚、雙（3,4-環氧基-6-甲基環己基甲基）己二酸酯、 雙酚Α-二縮水甘油醚、雙酚F-二縮水甘油醚、雙酚S-二縮 水甘油醚、氫化雙酚Α-二縮水甘油醚等。 -16- 201022742 作爲氧雜環丁烷系化合物，可舉出3-乙基-3-羥基甲基 氧雜環丁烷、3 -乙基- 3-(苯氧基甲基）氧雜環丁烷、二[(3-乙基-3-氧雜環丁烷基）甲基]醚等。 於本發明的活性能量線硬化性樹脂組成物中，除了活性 能量線硬化性化合物，亦可含有熱硬化性化合物。 活性能量線硬化性樹脂組成物中的全部硬化性化合物 中所佔有的上述具有2個以上不飽和羧酸醯基且具有橋聯 脂環式骨架之化合物（A)的比例爲3 0〜9 8重量％，較佳爲 Ο 50〜98重量％，更佳爲70〜98重量％。藉由以此範圍含有 具有2個以上不飽和羧酸醯基且具有橋聯脂環式骨架之化 合物（A)，可得到雙折射小且即使受到應力，雙折射也不易 變化的保護膜。 活性能量線硬化性樹脂組成物中的全部硬化性化合物 中所佔有的上述具有2個以上不飽和羧酸醯基且具有鏈狀 飽和脂肪族烴骨架之化合物（B)的比例爲1〜40重量％，較 佳爲1.5〜30重量％，更佳爲1.5〜20重量％。具有2個以 ® 上不飽和羧酸醢基且具有鏈狀飽和脂肪族烴骨架之化合物 (B)的含量若過少，則硬化物脆弱，作爲偏光板的保護膜使 用時，容易發生破裂等的問題。另一方面，當具有2個以 上不飽和羧酸醯基且具有鏈狀飽和脂肪族烴骨架之化合物 (B)的含量過多時，保護膜的玻璃轉移溫度（Tg)變過低，而 難以得到即使受到應力，雙折射也不易變化的特性。 活性能量線硬化性樹脂組成物中的全部硬化性化合物 中所佔有的上述具有2個以上不飽和羧酸醯基且具有橋聯 -17- 201022742 脂環式骨架之化合物（A)與具有2個以上不飽和羧酸醯基且 具有鏈狀飽和脂肪族烴骨架之化合物（B)之合計比例，例如 爲30重量％以上，較佳爲50重量％以上，更佳爲70重量％ 以上，特佳90重量％以上。 於活性能量線硬化性樹脂組成物中，除了上述硬化性化 合物，亦可配合光聚合引發劑、及視需要的光增感劑、光 陽離子聚合引發劑、熱陽離子聚合引發劑、熱自由基聚合 引發劑、光促進劑、光安定劑、紫外線吸收劑、均平劑、 〇 消泡劑等。 作爲光聚合引發劑，可按照硬化手段的活性能量線之種 類來適宜選擇。作爲光聚合引發劑之例，可舉出苯乙酮、 3-甲基苯乙酮、二苯甲酮、4-氯二苯甲酮、4,4-二胺基二苯 甲酮、1·羥基-環己基-苯基-酮、2,2-二甲氧基-2-苯基丙酮 、黃弗酮、苯甲醛、蒽醌、苯偶姻乙基醚、苯偶姻丙基醚 、苄基二甲基縮酮、1-(4-異丙基苯基）-2-羥基-2-甲基丙烷 -1-酮、4-蒽酚酮、樟腦醌、2-甲基-1-[4-(甲硫基）苯基]-2-® 嗎啉基丙烷-1-酮等。 上述具有2個以上不飽和羧酸醯基且具有橋聯脂環式 骨架之化合物（A)與具有2個以上不飽和羧酸醯基且具有鏈 狀飽和脂肪族烴骨架之化合物（B)的合計在活性能量線硬 化性樹脂組成物中的含量，相對於活性能量線硬化性樹脂 組成物中的固體成分全體（包含經由硬化而固形化的成分） 而言，例如爲3 0〜9 9.9重量％，較佳爲5 0〜9 9.5重量％， 更佳爲70〜99重量％，特佳爲90〜99重量％。 -18- 201022742 光聚合引發劑在活性能量線硬化性樹脂組成物中的含 量，相對於活性能量線硬化性樹脂組成物中的固體成分全 體（包含經由硬化而固形化的成分）而言，例如爲0.1〜10 重量％，較佳爲1〜8重量％左右。 本發明的偏光板係藉由在偏光鏡的至少一面上，不透過 其它層而直接塗佈上述活性能量線硬化性樹脂組成物後， 使該活性能量線硬化性樹脂組成物硬化以形成保護膜而製 造。 © 作爲活性能量線硬化性樹脂組成物的塗佈方法，並沒有 特別的限定，可利用刮刀、線桿、口模式塗佈機、凹槽輥 塗佈機等各種塗佈方式。於塗佈之際，可使用溶劑來調整 硬化性樹脂組成物的黏度。 活性能量線硬化性樹脂組成物所成的塗膜係經由照射 活性能量線而硬化，形成保護膜。作爲活性能量線，可舉 出紫外線、可見光線、電子線、X射線等。於此等之中， 較佳爲使用紫外線。作爲紫外線的發生源，可舉出低壓水 ® 銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈 、氙燈、黑光燈、金屬鹵化物燈等》 從薄型輕量性、保護性、操作性等的觀點來看，保護膜 的厚度例如爲10〜200 μιη，較佳爲30〜100 μιη。 本發明的偏光板由於使用含有各自特定量之具有2個 以上不飽和竣酸醯基且具有橋聯脂環式骨架之化合物（Α) 與具有2個以上不飽和羧酸醯基且具有鏈狀飽和脂肪族烴 骨架之化合物（Β)的活性能量線硬化性樹脂組成物之硬化 •19- 201022742 物當作偏光鏡的保護膜，故具有保護膜爲透明，不僅雙折 射小，而且即使受到應力，雙折射也不易變化的大優點。 [實施例] 以下以實施例爲基礎來更詳細說明本發明，惟本發明不 受此等實施例所限定。再者，硬化膜（硬化薄膜）的光彈性 係數及相位差之測定、玻璃轉移溫度之測定係藉由以下的 方法來進行。 [光彈性係數及相位差的測定] ® 製作厚度ΙΟΟμιη的硬化薄膜，使用王子計測機器股份 有限公司製的3次元雙折射計（「KOBRA-WR」）來測定。 [玻璃轉移溫度的測定] 於冷軋鋼板（厚度0.3mmx寬度20mmx長度50mm)上，塗 佈活性能量線硬化性樹脂組成物（厚度40μιη)，用小型UV 照射機（Eyegraphics股份有限公司製，「ECS-401GX」，額 定電壓200V，高壓水銀燈），在離llcm的距離，照射累計 光量3 50mJ/Cm2的紫外線，而得到活性能量線硬化性樹脂 ® 組成物的硬化薄膜。對此，使用剛體擺錘型黏彈性測定裝 置（A&D股份有限公司製，「rpt-3000W」），從25°C升溫 到200°C爲止’測定玻璃轉移溫度（Tg)。 合成例1(具有2個以上不飽和羧酸醯基且具有鏈狀飽和脂 肪族烴骨架之化合物的合成） 於具備攪拌機、溫度計及的冷凝器的1升之燒瓶中，投 入52.5重量份（2莫耳）的丙烯酸2-羥乙酯、0.02重量份 (200ppm ’相對於所得化合物的添加量）月桂酸二丁錫及 -20- 201022742 0.08重量份（800ppm，相對於所得化合物的添加量）氫醌單 甲基魅’邊攪拌邊使內溫成爲701後，費3小時滴下475 重量份（1莫耳）的三甲基己烷二異氰酸酯，然後進行反應直 到殘留的異氰酸酯基成爲0.1 %以下爲止，而得到具有2個 以上不飽和羧酸醯基且具有鏈狀飽和脂肪族烴骨架之化合 物。 實施例1 於95重量份的下述式（ia)所示的三環[5 2.1 02’”癸烷 ® 二甲醇二丙烯酸酯（大賽璐氰特股份有限公司製，商品名「 IRR-2 1 4 K」）中，添加混合5重量份的合成例1所得之化合 物及5重量份的1-羥基-環己基-苯基-酮，而得到活性能量 線硬化性樹脂組成物1。於玻璃板上，使用塗佈機來塗佈 1 20μιη的膜厚之活性能量線硬化性樹脂組成物i，用小型 UV照射機（Eyegraphics股份有限公司製，「ECS-401GX」 ，額定電壓200V，高壓水銀燈），在離iicm的距離，照射 2次累計光量3 5 0mJ/cm2的紫外線，而得到活性能量線硬化 ® 性樹脂組成物1的單獨硬化薄膜。目視觀察所得到的硬化 薄膜之外觀，同時測定光彈性係數及相位差。(In the formula, R3 and R4 are the same as defined above. R5, R6 and R7 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Examples of the alkyl group having 1 to 4 carbon atoms in R5, R6 and R7 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tert-butyl ester. ® is r3, r4, particularly preferably a hydrogen atom or a methyl group. Other examples of the compound (B) having two or more unsaturated carboxylic acid sulfhydryl groups and having a chain-like saturated aliphatic hydrocarbon skeleton include, for example, 1,4-butanediol di(meth)acrylate and 1, 6. Alkanediol di(meth)acrylate such as hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate or ethylene glycol di(meth)acrylate [C ^5-alkylene glycol di(meth)acrylate, etc., polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc., polyalkylene glycol di(meth)acrylic acid Ester, bisphenol A-diglycidyl ether-14- 201022742 Bifunctional (meth) acrylate such as di(meth) acrylate or ethylene oxide modified bisphenol A-di(meth) acrylate ; trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate 'pentaerythritol hexa (meth) acrylate, ethylene oxide added tris Trimethyl (meth) acrylate of methyl propane, dipentaerythritol penta (meth) acrylate, etc. A trifunctional or higher polyfunctional monomer. Among them, C2-15 alkylene glycol di(meth)acrylate such as 1,6-hexanediol di(meth)acrylate (especially C4_12 alkylene glycol di(methyl) is preferred. )Acrylate). In the active energy ray-curable resin composition of the present invention, the active energy ray-curable compound may contain only the above compound (A) having two or more unsaturated carboxylic acid sulfhydryl groups and having a bridged alicyclic skeleton. Further, the compound (B) having two or more unsaturated carboxylic acid sulfhydryl groups and having a chain-like saturated aliphatic hydrocarbon skeleton may further contain other active energy ray-curable compounds. Examples of such other active energy ray-curable compound include a radical curable compound and a cationic curable compound. The radical curable compound may have at least 1 ethyl double bond in the molecule, and may be irradiated with an active energy ray (for example, ultraviolet light, visible light, electron beam, X-ray, or the like) in the presence of a polymerization initiator. Polymerized compound. Examples of such a compound include (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate; ) tert-butyl acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate Cyclopentenyl ester, glycidyl (meth)acrylate, methoxyethyl (meth)acrylate, ethyl b-15-201022742 oxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl ketone (meth)acrylate, 2-hydroxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, borneol (meth)acrylate, isobornyl (meth)acrylate a monofunctional (meth) acrylate monomer such as (meth) propylene decylmorpholine or γ-(meth) propylene methoxy propyl trimethoxy decane; styrene, α-methyl styrene , vinyl toluene, vinyl acetate, allyl acetate, vinyl propionate, benzo a vinyl monomer such as vinyl acetate, fluorene-vinyl pyrrolidone, fluorene-vinylimidazole or hydrazine-vinyl caprolactam; triallyl cyanurate or triallyl isocyanurate; 1,3,5-tripropylene decyl hexahydro-S·肼 and the like. Among these, a bifunctional or higher polyfunctional monomer is preferred. These radical curable compounds may be used singly or in combination of two or more. Further, as the radical curable compound, ester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, acryl methacrylate (meth) acrylate, etc. may be used. (meth) acrylate oligomer. Examples of the cation-curable compound include a vinyl ether-based compound, an epoxy-based compound, and an oxetane-based compound, such as a vinyl ether-based compound, and examples thereof include an ethylene oxide-modified biguanide. Α-divinyl ether, ethylene oxide-modified hydroquinone divinyl ether, and the like. Examples of the epoxy compound include 1,2-epoxycyclohexane, limonene diepoxide, and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane. Alkyl carboxylate, 1,4-butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate , bisphenol hydrazine-diglycidyl ether, bisphenol F-diglycidyl ether, bisphenol S-diglycidyl ether, hydrogenated bisphenol quinone-diglycidyl ether, and the like. -16- 201022742 Examples of the oxetane-based compound include 3-ethyl-3-hydroxymethyloxetane and 3-ethyl-3-(phenoxymethyl)oxetane Alkane, bis[(3-ethyl-3-oxetanyl)methyl]ether, and the like. The active energy ray-curable resin composition of the present invention may contain a thermosetting compound in addition to the active energy ray-curable compound. The ratio of the compound (A) having two or more unsaturated carboxylic acid sulfhydryl groups and having a bridged alicyclic skeleton, which is contained in all the curable compounds in the active energy ray-curable resin composition, is from 30 to 9 8 The weight % is preferably 〜 50 to 98% by weight, more preferably 70 to 98% by weight. By containing the compound (A) having two or more unsaturated carboxylic acid sulfhydryl groups and having a bridged alicyclic skeleton in this range, a protective film having a small birefringence and being hard to change birefringence even under stress can be obtained. The ratio of the compound (B) having two or more unsaturated carboxylic acid sulfhydryl groups and having a chain saturated aliphatic hydrocarbon skeleton, which is contained in all the curable compounds in the active energy ray-curable resin composition, is from 1 to 40% by weight. % is preferably 1.5 to 30% by weight, more preferably 1.5 to 20% by weight. When the content of the compound (B) having two saturated carboxylic acid groups and having a chain-like saturated aliphatic hydrocarbon skeleton is too small, the cured product is weak, and when used as a protective film for a polarizing plate, cracking or the like is likely to occur. problem. On the other hand, when the content of the compound (B) having two or more unsaturated carboxylic acid sulfhydryl groups and having a chain-like saturated aliphatic hydrocarbon skeleton is too large, the glass transition temperature (Tg) of the protective film becomes too low, and it is difficult to obtain Even if subjected to stress, birefringence does not easily change. The compound (A) having two or more unsaturated carboxylic acid sulfhydryl groups and having a bridged-17-201022742 alicyclic skeleton, which is occupied by all the curable compounds in the active energy ray-curable resin composition, has two The total proportion of the compound (B) having a saturated aliphatic carboxylic acid group and a chain-like saturated aliphatic hydrocarbon skeleton is, for example, 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more, particularly preferably 90% by weight or more. In the active energy ray-curable resin composition, in addition to the curable compound, a photopolymerization initiator, an optional photo sensitizer, a photocationic polymerization initiator, a thermal cationic polymerization initiator, or a thermal radical polymerization may be blended. Initiator, light accelerator, light stabilizer, ultraviolet absorber, leveling agent, antifoaming agent, and the like. The photopolymerization initiator can be appropriately selected in accordance with the type of the active energy ray of the curing means. Examples of the photopolymerization initiator include acetophenone, 3-methylacetophenone, benzophenone, 4-chlorobenzophenone, 4,4-diaminobenzophenone, and 1·. Hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-2-phenylacetone, yellow ketone, benzaldehyde, hydrazine, benzoin ethyl ether, benzoin propyl ether, benzyl Dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-indolyl ketone, camphorquinone, 2-methyl-1-[ 4-(Methylthio)phenyl]-2-carboxymorpholinan-1-one. The above compound (A) having two or more unsaturated carboxylic acid fluorenyl groups and having a bridged alicyclic skeleton and a compound (B) having two or more unsaturated carboxylic acid sulfhydryl groups and having a chain saturated aliphatic hydrocarbon skeleton The total content of the active energy ray-curable resin composition is, for example, 30 to 9 9.9 by weight based on the total solid content (including a component solidified by curing) in the active energy ray-curable resin composition. %, preferably from 5 0 to 9 9.5 wt%, more preferably from 70 to 99 wt%, particularly preferably from 90 to 99 wt%. -18-201022742 The content of the photopolymerization initiator in the active energy ray-curable resin composition is, for example, the total solid content (including a component solidified by curing) in the active energy ray-curable resin composition. It is 0.1 to 10% by weight, preferably about 1 to 8% by weight. In the polarizing plate of the present invention, the active energy ray-curable resin composition is directly applied to at least one surface of the polarizer without passing through other layers, and then the active energy ray-curable resin composition is cured to form a protective film. And manufacturing. The coating method of the active energy ray-curable resin composition is not particularly limited, and various coating methods such as a doctor blade, a wire rod, a die coater, and a gravure coater can be used. At the time of coating, a solvent can be used to adjust the viscosity of the curable resin composition. The coating film formed of the active energy ray-curable resin composition is cured by irradiation with an active energy ray to form a protective film. Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, and X-rays. Among these, it is preferred to use ultraviolet rays. Examples of sources of ultraviolet rays include low-pressure water® silver lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, chemical lamps, xenon lamps, black lamps, metal halide lamps, etc., from thin, lightweight, protective, and operable. The thickness of the protective film is, for example, 10 to 200 μm, preferably 30 to 100 μm, from the viewpoint of properties and the like. The polarizing plate of the present invention has a chain structure by using a compound having a specific amount of two or more unsaturated ceric acid sulfonium groups and having a bridged alicyclic skeleton (Α) and having two or more unsaturated carboxylic acid sulfhydryl groups. Hardening of active energy ray-curable resin composition of a compound of saturated aliphatic hydrocarbon skeleton (Β) 19- 201022742 The object is used as a protective film for a polarizer, so that the protective film is transparent, not only has small birefringence, but also is subjected to stress. The double refraction is also not easy to change. [Examples] Hereinafter, the present invention will be described in more detail based on the examples, but the present invention is not limited by the examples. Further, the measurement of the photoelastic coefficient and the phase difference of the cured film (hardened film) and the measurement of the glass transition temperature were carried out by the following methods. [Measurement of Photoelastic Coefficient and Phase Difference] ® A cured film of thickness ΙΟΟμηη was produced and measured using a three-dimensional birefringence meter ("KOBRA-WR") manufactured by Oji Scientific Instruments Co., Ltd. [Measurement of glass transition temperature] An active energy ray-curable resin composition (thickness: 40 μm) was applied to a cold-rolled steel sheet (thickness: 0.3 mm x width: 20 mm x length: 50 mm), and a small UV irradiation machine (manufactured by Eyegraphics Co., Ltd., ECS-401GX", rated voltage 200V, high-pressure mercury lamp), irradiated with ultraviolet light having a cumulative light amount of 3 50 mJ/cm 2 at a distance of llcm to obtain a cured film of an active energy ray-curable resin® composition. On the other hand, a glass transition temperature (Tg) was measured using a rigid body pendulum type viscoelasticity measuring apparatus ("rpt-3000W" manufactured by A&D Co., Ltd.) and raised from 25 °C to 200 °C. Synthesis Example 1 (Synthesis of a compound having two or more unsaturated carboxylic acid sulfhydryl groups and having a chain-like saturated aliphatic hydrocarbon skeleton) In a 1-liter flask equipped with a stirrer, a thermometer, and a condenser, 52.5 parts by weight (2) was charged. 2-hydroxyethyl acrylate, 0.02 parts by weight (200 ppm 'relative to the amount of the compound obtained) dibutyltin laurate and -20-201022742 0.08 parts by weight (800 ppm, relative to the amount of the compound obtained) hydrogen After the internal temperature was 701, the 醌 monomethyl charm was added, and 475 parts by weight (1 mol) of trimethyl hexane diisocyanate was added dropwise over 3 hours, and then the reaction was carried out until the residual isocyanate group became 0.1% or less. Thus, a compound having two or more unsaturated carboxylic acid fluorenyl groups and having a chain-like saturated aliphatic hydrocarbon skeleton is obtained. Example 1 95 parts by weight of tricyclo[52.1 02'"decane® dimethanol diacrylate represented by the following formula (ia) (manufactured by Daicel Co., Ltd., trade name "IRR-2 1" In 4 K"), 5 parts by weight of the compound obtained in Synthesis Example 1 and 5 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone were added to obtain an active energy ray-curable resin composition 1. On the glass plate, a film thickness of the active energy ray-curable resin composition i of 1 20 μm was applied using a coater, and a small UV irradiation machine ("ECS-401GX" manufactured by Eyegraphics Co., Ltd., rated voltage of 200 V, was used). The high-pressure mercury lamp) was irradiated with ultraviolet light having a cumulative light amount of 305 mJ/cm 2 twice at a distance of iicm to obtain a single hardened film of the active energy ray-hardening resin composition 1. The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and phase difference were measured.
實施例2 於90重量份的三環[5.2.1· 02,6]癸烷二甲醇二丙烯酸酯（ 大賽璐氰特股份有限公司製，商品名「IRR-2 14K」）中，添 201022742 加混合10重量份的合成例1所得之化合物及5重量份的 1-羥基-環己基-苯基-酮，而得到活性能量線硬化性樹脂組 成物2。於玻璃板上，使用塗佈機來塗佈I20fim的膜厚之 活性能量線硬化性樹脂組成物2，與實施例1同樣地照射 紫外線，而得到活性能量線硬化性樹脂組成物2的單獨硬 化薄膜。目視觀察所得到的硬化薄膜之外觀，同時測定光 彈性係數及相位差》 實施例3 ❹ 於90重量份的三環[5.2.1_02’6]癸烷二甲醇二丙烯酸酯（ 大賽璐氟特股份有限公司製，商品名「IRR-2 14K」），添加 混合 1〇重量份 1，6·己二醇二丙烯酸酯（Cytec Surface Specialties公司製，商品名「HDDAj )及5重量份的1-羥 基-環己基-苯基·酮，而得到活性能量線硬化性樹脂組成物 3。於玻璃板上，使用塗佈機來塗佈120 μιη的膜厚之活性 能量線硬化性樹脂組成物3，與實施例1同樣地照射紫外 線，而得到活性能量線硬化性樹脂組成物3的單獨硬化薄 © 膜。目視觀察所得到的硬化薄膜之外觀，同時測定光彈性 係數及相位差。 比較例1 於雙酚Α縮水甘油醚與2莫耳的丙烯酸所反應成的1〇〇 重量份之環氧丙烯酸酯中，添加混合5重量份的1-羥基_ 環己基-苯基-酮，而得到活性能量線硬化性樹脂組成物4 。於玻璃板上，使用塗佈機來塗佈120 μιη的膜厚之活性能 量線硬化性樹脂組成物4，與實施例1同樣地照射紫外線 -22- 201022742 ’而得到活性能量線硬化性樹脂組成物4的單獨硬化薄膜 。測定所得到的硬化薄膜之光彈性係數及相位差。 比較例2 於100重量份的合成例1所得之化合物中，添加混合5 重量份的1-羥基-環己基-苯基-酮，而得到活性能量線硬化 性樹脂組成物5。於玻璃板上，使用塗佈機來塗佈120μιη 的膜厚之活性能量線硬化性樹脂組成物5，與實施例1同 樣地照射紫外線，而得到活性能量線硬化性樹脂組成物5 ® 的單獨硬化薄膜。目視觀察所得到的硬化薄膜之外觀，同 時測定光彈性係數及相位差。 比較例3 混合50重量份的季戊四醇三丙烯酸酯、50重量份的合 成例1所得之化合物、5重量份的1-羥基-環己基-苯基-酮 ，而得到活性能量線硬化性樹脂組成物6。於玻璃板上， 使用塗佈機來塗佈12〇μιη的膜厚之活性能量線硬化性樹脂 組成物6，與實施例1同樣地照射紫外線，而得到活性能 ® 量線硬化性樹脂組成物6的單獨硬化薄膜。目視觀察所得 到的硬化薄膜之外觀，同時測定光彈性係數及相位差。 比較例4 混合50重量份的三羥甲基丙烷之2莫耳環氧乙烷加成 物的三丙烯酸酯、50重量份的合成例1所得之化合物、5 重量份的1-羥基-環己基-苯基·酮’而得到活性能量線硬化 性樹脂組成物7。於玻璃板上，使用塗佈機來塗佈120μιη 的膜厚之活性能量線硬化性樹脂組成物7，與實施例1同 -23- 201022742 樣地照射紫外線，而得到活性能量線硬化性樹脂組成物7 的單獨硬化薄膜。目視觀察所得到的硬化薄膜之外觀，同 時測定光彈性係數及相位差。 比較例5 • 混合50重量份的貳三羥甲基丙烷四丙烯酸酯、50重量 份的合成例1所得之化合物、5重量份的1 _羥基-環己基-苯基-酮，而得到活性能量線硬化性樹脂組成物8。於玻璃 板上’使用塗佈機來塗佈12 0 μιη的膜厚之活性能量線硬化 © 性樹脂組成物8，與實施例1同樣地照射紫外線，而得到 .活性能量線硬化性樹脂組成物8的單獨硬化薄膜。目視觀 察所得到的硬化薄膜之外觀，同時測定光彈性係數及相位 差。 比較例6 於100重量份的三環[5.2.1.02’6]癸烷二甲醇二丙烯酸酯 (大赛璐氰特股份有限公司製，商品名「IRR-214K」）中， 添加混合5重量份的1_羥基-環己基-苯基-酮，而得到活性 ® 能量線硬化性樹脂組成物9。於玻璃板上，使用塗佈機來 塗佈120μηι的膜厚之活性能量線硬化性樹脂組成物9,與 實施例1同樣地照射紫外線，而得到活性能量線硬化性樹 脂組成物9的單獨硬化薄膜》目視觀察所得到的硬化薄膜 之外觀，同時測定光彈性係數及相位差。再者，所得之硬 化薄膜係非常脆弱，以手來彎曲時容易破裂。相對於此， 上述實施例1〜3、比較例1〜5所得之硬化薄膜，即使以 手來彎曲也不會破裂。 -24- 201022742 比較例7 於100重量份的1,6-己二醇二丙嫌酸醋（Cytec Surface Specialties公司製，商品名「HDDAj )中，混合5重量份 的1-羥基-環己基-苯基-酮，而得到活性能量線硬化性樹脂 組成物10。於玻璃板上，使用塗佈機來塗佈120 μιη的膜厚 之活性能量線硬化性樹脂組成物1 0，與實施例1同樣地照 射紫外線。結果，塗膜在UV硬化時發生破裂，無法得到 硬化薄膜。 ® 表1中顯示實施例及比較例所得之硬化薄膜的外観、性 質狀態、玻璃轉移溫度、光彈性係數及相位差的測定結果 。表中，「-」表示無法測定。比較例1的硬化薄膜，在 測定光彈性係數及相位差之際，由於在測定荷重範圍發生 塑性變形，故無法測定光彈性係數及相位差。由表1可知 ，實施例所得之硬化薄膜係透明，且相位差及光彈性係數 皆顯示小的値，不僅雙折射小，而且即使受到應力，雙折 射也不易變化。 ❹ -25- 201022742Example 2 In 90 parts by weight of tricyclo[5.2.1·02,6]decane dimethanol diacrylate (manufactured by Daicel Co., Ltd., trade name "IRR-2 14K"), add 201022742 plus 10 parts by weight of the compound obtained in Synthesis Example 1 and 5 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone were mixed to obtain an active energy ray-curable resin composition 2. On the glass plate, the active energy ray-curable resin composition 2 having a film thickness of I20fim was applied by using a coater, and ultraviolet rays were irradiated in the same manner as in Example 1 to obtain individual hardening of the active energy ray-curable resin composition 2. film. The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and phase difference were measured. Example 3 90 90 parts by weight of tricyclo [5.2.1_02'6] decane dimethanol diacrylate (Daily 璐 璐 特 股份Co., Ltd., trade name "IRR-2 14K"), adding 1 part by weight of 1,6·hexanediol diacrylate (trade name "HDDAj" manufactured by Cytec Surface Specialties Co., Ltd.) and 5 parts by weight of 1-hydroxyl - a cyclohexyl-phenyl ketone to obtain an active energy ray-curable resin composition 3. On a glass plate, a 120 μm thick active energy ray-curable resin composition 3 was applied using a coater, and In the same manner as in Example 1, ultraviolet rays were irradiated to obtain a single-cured thin film of the active energy ray-curable resin composition 3. The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and phase difference were measured. Comparative Example 1 1 part by weight of epoxy acrylate obtained by reacting phenolphthalein glycidyl ether with 2 moles of acrylic acid, and adding 5 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone to obtain an active energy ray Sclerosing tree Composition 4: An active energy ray-curable resin composition 4 having a film thickness of 120 μm was applied onto a glass plate by a coater, and ultraviolet ray-22-201022742' was irradiated in the same manner as in Example 1 to obtain an active energy ray. A single cured film of the curable resin composition 4. The photoelastic coefficient and the phase difference of the obtained cured film were measured. Comparative Example 2 In 100 parts by weight of the compound obtained in Synthesis Example 1, 5 parts by weight of 1-hydroxy group was added and mixed. -cyclohexyl-phenyl-ketone to obtain an active energy ray-curable resin composition 5. On the glass plate, a 120 μm thick active energy ray-curable resin composition 5 was applied using a coater, and was carried out. In the same manner, Example 1 was irradiated with ultraviolet rays to obtain a single cured film of the active energy ray-curable resin composition 5 ® . The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and phase difference were measured. Comparative Example 3 50 parts by weight The pentaerythritol triacrylate, 50 parts by weight of the compound obtained in Synthesis Example 1, and 5 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, thereby obtaining an active energy ray-curable resin Composition 6. On the glass plate, an active energy ray-curable resin composition 6 having a film thickness of 12 μm was applied by using a coater, and ultraviolet rays were irradiated in the same manner as in Example 1 to obtain active energy® wire-hardening. A single cured film of the resin composition 6. The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and the phase difference were measured. Comparative Example 4 50 parts by weight of 2 mol of ethylene oxide of trimethylolpropane was added. The active tris acrylate, 50 parts by weight of the compound obtained in Synthesis Example 1, and 5 parts by weight of 1-hydroxy-cyclohexyl-phenyl ketone' were used to obtain an active energy ray-curable resin composition 7. On a glass plate. The active energy ray-curable resin composition 7 having a film thickness of 120 μm was applied by a coater, and ultraviolet rays were irradiated as in Example 1 to -23-201022742 to obtain a separate active energy ray-curable resin composition 7. Hardened film. The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and the phase difference were measured at the same time. Comparative Example 5 • 50 parts by weight of hydrazine trimethylolpropane tetraacrylate, 50 parts by weight of the compound obtained in Synthesis Example 1, and 5 parts by weight of 1-hydroxy-cyclohexyl-phenyl-one were mixed to obtain active energy. Linear curable resin composition 8. The active energy ray-curable resin composition 8 having a film thickness of 120 μm was applied to a glass plate by a coating machine, and ultraviolet rays were irradiated in the same manner as in Example 1 to obtain an active energy ray-curable resin composition. A separate hardened film of 8. The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and the phase difference were measured. Comparative Example 6 In 100 parts by weight of tricyclo [5.2.1.0''6] decane dimethanol diacrylate (manufactured by Daicel Co., Ltd., trade name "IRR-214K"), 5 parts by weight of a mixture was added. 1 - hydroxy-cyclohexyl-phenyl-ketone to give an active® energy ray-curable resin composition 9. On the glass plate, the active energy ray-curable resin composition 9 having a film thickness of 120 μm was applied by using a coater, and ultraviolet rays were irradiated in the same manner as in Example 1 to obtain individual hardening of the active energy ray-curable resin composition 9. Film" The appearance of the obtained cured film was visually observed, and the photoelastic coefficient and phase difference were measured. Furthermore, the resulting hardened film is very fragile and is easily broken when bent by hand. On the other hand, the cured films obtained in the above Examples 1 to 3 and Comparative Examples 1 to 5 were not broken even if they were bent by hand. -24- 201022742 Comparative Example 7 5 parts by weight of 1-hydroxy-cyclohexyl group was mixed with 100 parts by weight of 1,6-hexanediol dipropylene vinegar (manufactured by Cytec Surface Specialties, trade name "HDDAj"). The active energy ray-curable resin composition 10 was obtained as a phenyl-ketone. The active energy ray-curable resin composition 10 of a film thickness of 120 μm was applied on a glass plate using a coater, and Example 1 As a result, the coating film was broken at the time of UV curing, and a cured film could not be obtained. ® Table 1 shows the outer diameter, property state, glass transition temperature, photoelastic coefficient, and phase of the cured film obtained in the examples and the comparative examples. The measurement result of the difference. In the table, "-" indicates that measurement is impossible. In the cured film of Comparative Example 1, when the photoelastic coefficient and the phase difference were measured, plastic deformation occurred in the measurement load range, and thus the photoelastic coefficient and the phase difference could not be measured. As is clear from Table 1, the cured film obtained in the examples was transparent, and the phase difference and the photoelastic coefficient all showed small enthalpy, and the birefringence was small, and the birefringence was not easily changed even under stress. ❹ -25- 201022742
比較例 卜 1 1 1 1 VO «酿 m每 ά 5 盤祖 赃ii 155 j 12.5 1—Η 透明 115 22.4 1 1 (N d 寸 透明 102 25.4 1 m 透明 133 23.2 o <N 透明 20.4 <N Τ"Η 透明 v〇 1 1 實施例 cn 透明 145 12.4 1_______ 寸 透明 114 12.5 ro d i-H 透明 156 12.8 寸 d 外觀、性質狀態 Tg(°C ) 光彈性係數 (xlQ-^Pa'1) 相位差(nm) 駆。旧’ 牯摧摧 醒 州Comparative example 1 1 1 1 VO « Brewing m per ά 5 Pan Zu 赃 ii 155 j 12.5 1 - 透明 Transparent 115 22.4 1 1 (N d inch transparent 102 25.4 1 m transparent 133 23.2 o < N transparent 20.4 < N Τ"Ηtransparent v〇1 1 embodiment cn transparent 145 12.4 1_______ inch transparent 114 12.5 ro d iH transparent 156 12.8 inch d appearance, property state Tg (°C) photoelastic coefficient (xlQ-^Pa'1) phase difference ( Nm) 駆. Old' 牯 摧 摧 州