200521578 九、發明說明： 【發明所屬之技術領域】 本發明係關於藉由積層體所構成之液晶配向膜及其製 法。更詳細而言，係關於一種於液晶顯示元件中藉由液晶配 向膜輔助配向控制，然後電壓保持率高且殘留DC電壓低之 可進行液晶顯示元件面板生產之液晶配向膜及其製法。 【先前技術】 現今，液晶顯示元件方面，已知具有在設置有透明導電 膜之官能基板的該表面上形成由聚醯胺酸、聚亞醯胺等所構 成之液晶配向膜而成爲液晶顯示元件用基板，並相向配置該 兩片基板而形成在該間隙內具有正介電異方性之向列型液 晶層而成爲三明治構造之元件，該液晶分子之長軸從一側之 官能基板朝向另一側之官能基板來連續地進行成爲90度扭 轉，即TN型（扭曲向歹丨J (Twisted Nematic))液晶元件之 TN型液晶顯示元件。又，最近正開發一種比較於TN型液晶 顯示元件對比高、其視角依賴性少之STN (超扭曲向列 (Super Twisted Nematic))型液晶顯示元件。該STN型液 晶顯示元件係使用於向列型液晶中植入其爲光學活性物質 之凱伊拉耳劑者作爲液晶，其係利用藉由該液晶分子之長軸 在基板間扭曲成1 80度以上來成爲連續扭曲之狀態所生成的 複折射效果者。在該TN型液晶顯示元件及STN型液晶顯示 元件中之液晶的配向，通常，係藉由已實施摩擦處理之液晶 配向膜所發現者。 相對於此，提案有如記載於非專利文獻1及專利文獻 200521578 1，於ITO上形成突起來控制液晶之配向方向之MVA方式， 或如揭示記載於非專利文獻2之鑽硏電極構造來控制配向方 向之EVA方式、如揭示記載於非專利文獻3之藉由光照射 來改質配向膜而來控制配向方向方式等之垂直配向型液晶 顯示元件。該等垂直配向型液晶顯示元件係視角、對比優 異，於液晶配向膜之形成中未進行摩擦處理而佳等，在製造 步驟方面亦優異。然而比較於前述TN型、STN型之液晶顯 示元件則性能尙不充足，特別是正尋求關於垂直配向性及液 晶顯示元件之殘像消去時間之性能提昇。 Φ 另外，在液晶之配向控制中，特別是相對於基板面垂直 配向之合順向配向，已知以在液晶中混合具有卵磷脂或十六 烷基三甲基溴化銨等之具有疏水性基之化合物或僅以浸漬 基板於該等溶液中而未採取摩擦處理等手段而可簡便地達 成配向控制。 【專利文獻1】特開平1 1 -25 8605號公報 【非專利文獻1】”液晶” vol. 3 No· 2 1 1 7 ( 1 999年） 【非專利文獻2】”液晶” vol· 3 No. 4 272 ( 1 999年） _ 【非專利文獻 3】，，Jpn. Appl. Phys.” Vol 36 428( 1997 年） 【發明內容】 發明所欲解決之課題 該等垂直配向型液晶顯示元件係希望特別規定初期配 向、並賦予朝向極角方向之強的配向限制力。 又，在以固定之幀週期驅動之情況下，在得到對比良好 之顯示方面，係希望在該液晶顯示元件中之電壓保持率（在 200521578 ,. 幀週期間之電壓保持率）爲高。 再者，從起因於殘像之對比的降低及防止畫像之燒鍍現 象的觀點來看，希望在解除施加電壓後所殘留之直流電壓 (以下，稱爲「殘留DC電壓」）立即變低。 然而，僅以習知之垂直液晶配向膜，則有在該液晶顯示 元件中，不能提供充分滿足高對比、高電壓保持率、低殘留 DC電壓之液晶顯示元件的現況。 本發明係基於如上述課題所構成者，本發明之目的係在 於提供可製作對比高、電壓保持率高、而且殘留DC電壓低 之液晶顯示元件的液晶配向膜。 本發明之其他目的係在於提供上述液晶配向膜之製法。 本發明之再其他目的及優點係從以下說明而變得明瞭。 用於解決課顆之丰段 根據本發明，本發明之上述目的及優點，第1方面，藉 由其爲積層體之液晶配向膜而達成。 根據本發明，本發明之上述目的及優點，第2方面，藉 由以於在與基板之液晶接觸面上存在聚醯胺酸及聚亞醯胺 之膜之2片被夾住之官能基板間，與液晶一起密封裝入具有 含有乙烯性不飽和鍵之官能基與疏水性基之化合物，其次進 行放射線照射或加熱而於上述聚醯胺酸或聚亞醯胺膜上聚 合該化合物爲特徵之液晶配向膜的製造方法來達成。 發明之效罢 根據本發明，可提供一種輔助垂直配向性、賦予高電壓 保持率、低殘像型之液晶顯示元件之液晶配向膜。 200521578 本發明之液晶配向膜係爲了構成MVA型液晶顯示元件 及PVA型液晶顯示元件而可適宜地使用。又，具備該液晶 配向膜之液晶顯示元件係液晶之配向性及信賴性均優異，而 可有效地使用於各種裝置，例如可適宜地使用作爲桌上型計 算機、手錶、座鐘、計數顯示板、文字處理機、個人電腦、 液晶電視等之顯不裝置。 【實施方式】 用於實施發明之最佳样能 以下詳細地說明本發明。 •一 [藉由積層體所構成之液晶配向膜] 藉由積層體所構成之液晶配向膜係藉由以選自聚醯胺 酸及聚亞醯胺（以下，稱爲「聚醯胺酸等」）至少一種所構 成之第一膜以及以具有含有乙烯性不飽和鍵之官能基與疏 水性基之化合物（以下，稱爲「特定化合物」）之聚合體所 構成之第二膜所構成。 其爲第1層之第一膜係可藉由使用通常之液晶配向膜形 成用液晶配向劑而形成。該膜厚係以1〇〇〜5，000人爲佳，以 ® 200〜1，000A爲較佳。 聚醯胺酸等係可由藉由使用四羧酸二酐及二胺而以通 常之方法來合成（參照特開2001-311080號公報）。 其爲第2層之第二膜係可藉由在液晶顯示元件之面板內 在液晶之存在下聚合特定化合物而形成。該膜厚係以i 〇〜 2,000人爲佳’以50〜1，〇〇〇人爲較佳，以50〜700A爲更佳。 特性化合物係如上述具有含有乙烯性不飽和鍵之官能 200521578 . 基與疏水性基。具有乙烯性不飽和鍵之官能基方面’舉例以 (甲基）丙烯醯氧基爲佳。疏水性基方面，舉出有6〜40碳 數之直鏈狀或支鏈狀烷基、或如環狀脂肪族基之1價基及如 環己烯基、聯環己烯基、伸苯基、伸聯苯基、伸聯三苯基、 伸萘基之2價基。該等官能基係亦可具有烷基、烷氧基、鹵 素基、苯基等之取代基。 特定化合物之具體範例方面，可舉出有以下述通式（1) 所表示之化合物。 R-Y1- ( A-Y2 ) n-Z ( 1 ) (通式中，R係1〜40碳數之直鏈狀或支鏈狀烷基、或 環狀脂肪族基；A係選自1〜10碳數之伸烷基、環己烯基、 聯環己基、伸苯基、伸聯苯基、伸聯三苯基及伸萘基、以及 選自下述通式之2價有機基；Y1及Y2係互相獨立，爲選自 單鍵、醚鍵、酯鍵及醯胺鍵之鍵結基；Z係包含乙烯性不飽 和鍵之聚合性官能基，然後η係0〜3之整數。但是，R之 上述烷基係亦可由1〜10碳數之烷氧基、羥基、鹵素原子或 苯基取代，R之上述環狀脂肪族基及Α之2價有機基係亦可 由1〜10碳數之烷基、1〜10碳數之烷氧基、羥基、鹵素原 子或苯基取代。） 200521578200521578 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a liquid crystal alignment film composed of a laminated body and a method for manufacturing the same. More specifically, it relates to a liquid crystal alignment film capable of performing liquid crystal display element panel production in a liquid crystal display element by assisting alignment control with a liquid crystal alignment film, and then having a high voltage retention and low residual DC voltage. [Prior Art] Nowadays, in the aspect of liquid crystal display elements, it is known to have a liquid crystal alignment film made of polyamic acid, polyimide, or the like formed on the surface of a functional substrate provided with a transparent conductive film to become a liquid crystal display element. A substrate is used to arrange the two substrates facing each other to form a nematic liquid crystal layer with positive dielectric anisotropy in the gap to form a sandwich structure element. The long axis of the liquid crystal molecules faces from the functional substrate on one side toward the other. The functional substrate on one side is continuously turned into a 90-degree twist, that is, a TN-type (TN-type (Twisted Nematic)) liquid crystal element. Recently, a STN (Super Twisted Nematic) type liquid crystal display element which has a high contrast and has a small viewing angle dependency as compared with a TN type liquid crystal display element is recently being developed. The STN-type liquid crystal display element is used as a liquid crystal in which nematic liquid crystals are implanted as an optically active substance. It uses a long axis of the liquid crystal molecules to be twisted to 180 degrees between substrates. The above is the effect of the birefringence produced by the continuously twisted state. The alignment of the liquid crystal in the TN-type liquid crystal display element and the STN-type liquid crystal display element is usually found by a liquid crystal alignment film that has been subjected to a rubbing treatment. On the other hand, the proposal is as described in Non-Patent Document 1 and Patent Document 200521578 1, an MVA method in which protrusions are formed on ITO to control the alignment direction of liquid crystals, or the drill collar electrode structure described in Non-Patent Document 2 is disclosed to control the alignment The EVA method of the direction is disclosed in Non-Patent Document 3, which is a vertical alignment type liquid crystal display element in which the alignment film is modified by light irradiation to control the alignment direction method. These vertical alignment type liquid crystal display elements are excellent in viewing angle and contrast, are excellent in the formation of a liquid crystal alignment film without rubbing treatment, and are excellent in terms of manufacturing steps. However, in comparison with the aforementioned TN-type and STN-type liquid crystal display elements, the performance is not sufficient, and in particular, performance improvements regarding vertical alignment and the afterimage erasure time of liquid crystal display elements are being sought. Φ In addition, in the control of liquid crystal alignment, in particular, the forward alignment with respect to the vertical alignment of the substrate surface, it is known that liquid crystals having a mixture of lecithin, cetyltrimethylammonium bromide, and the like are mixed in the liquid crystal. The compound based on the base can be simply controlled by immersing the substrate in these solutions without using a rubbing treatment or the like. [Patent Document 1] JP-A No. 1 1-25-25605 [Non-Patent Document 1] "Liquid Crystal" vol. 3 No. 2 1 1 7 (1999) [Non-Patent Document 2] "Liquid Crystal" vol · 3 No 4 272 (1999) _ [Non-Patent Document 3], Jpn. Appl. Phys. ”Vol 36 428 (1997) [Contents of the Invention] Problems to be Solved by the Invention The vertical alignment type liquid crystal display element system It is desirable to specify the initial alignment and to provide a strong alignment restraining force in the direction of the polar angle. In addition, in the case of driving at a fixed frame period, in order to obtain a comparatively good display, the voltage in the liquid crystal display element is desired. The retention rate (voltage retention rate during the period of 200521578, frame period) is high. Furthermore, from the viewpoint of reducing the contrast caused by the afterimage and preventing the phenomenon of burn-in of the image, it is desirable to remain after the voltage is released. The DC voltage (hereinafter referred to as "residual DC voltage") immediately becomes low. However, the conventional vertical liquid crystal alignment film alone cannot provide a liquid crystal display element that satisfies high contrast, high voltage retention, and low residual DC voltage in the liquid crystal display element. The present invention is based on the problems described above, and an object of the present invention is to provide a liquid crystal alignment film capable of producing a liquid crystal display element with high contrast, high voltage holding ratio, and low residual DC voltage. Another object of the present invention is to provide a method for manufacturing the liquid crystal alignment film. Still other objects and advantages of the present invention will become apparent from the following description. According to the present invention, the above-mentioned object and advantages of the present invention, the first aspect, is achieved by a liquid crystal alignment film which is a laminated body. According to the present invention, in the above-mentioned object and advantages of the present invention, in a second aspect, between two functional substrates sandwiched between a polyamic acid and a polyimide film on a liquid crystal contact surface of the substrate It is characterized in that a compound having a functional group containing an ethylenically unsaturated bond and a hydrophobic group is sealed and filled with the liquid crystal, followed by radiation irradiation or heating to polymerize the compound on the polyamic acid or polyimide film. A method for manufacturing a liquid crystal alignment film is achieved. Effect of the Invention According to the present invention, it is possible to provide a liquid crystal alignment film for a liquid crystal display element that assists vertical alignment, provides a high voltage retention, and has a low afterimage type. 200521578 The liquid crystal alignment film of the present invention is suitably used for constituting an MVA type liquid crystal display element and a PVA type liquid crystal display element. In addition, the liquid crystal display element system liquid crystal provided with the liquid crystal alignment film has excellent alignment and reliability, and can be effectively used in various devices. For example, it can be suitably used as a desktop computer, a watch, a table clock, a counting display board, Word processor, personal computer, LCD TV and other display devices. [Embodiment] Best Modes for Implementing the Invention The present invention will be described in detail below. • [Liquid crystal alignment film composed of laminated body] The liquid crystal alignment film composed of laminated body is selected from polyamic acid and polyimide (hereinafter referred to as "polyamic acid, etc." ") At least one kind of first film and a second film made of a polymer having a compound containing a functional group containing an ethylenically unsaturated bond and a hydrophobic group (hereinafter referred to as" specific compound "). The first film, which is the first layer, can be formed by using a general liquid crystal alignment film forming liquid crystal alignment agent. The film thickness is preferably 100 to 5,000 people, and more preferably 200 to 1,000 A. Polyamic acid and the like can be synthesized by a usual method by using tetracarboxylic dianhydride and diamine (see Japanese Patent Application Laid-Open No. 2001-311080). The second film, which is the second layer, can be formed by polymerizing a specific compound in the presence of liquid crystal in a panel of a liquid crystal display element. The thickness of the film is preferably from 〇 to 2,000 people, more preferably from 50 to 10,000 people, and even more preferably from 50 to 700 A. The characteristic compound is a functional group containing an ethylenically unsaturated bond as described above. 200521578. The functional group having an ethylenically unsaturated bond is preferably exemplified by (meth) acrylfluorenyloxy. In terms of hydrophobic groups, linear or branched alkyl groups having 6 to 40 carbon atoms, or monovalent groups such as cyclic aliphatic groups, and cyclohexenyl, bicyclohexenyl, and benzene are listed. Divalent radicals of phenylene, diphenylene, triphenylene, and naphthyl. These functional groups may have a substituent such as an alkyl group, an alkoxy group, a halogen group, or a phenyl group. Specific examples of the specific compound include a compound represented by the following general formula (1). R-Y1- (A-Y2) nZ (1) (In the general formula, R is a linear or branched alkyl group having 1 to 40 carbon atoms, or a cyclic aliphatic group; A is selected from 1 to 10 Carbon number of alkylene, cyclohexenyl, bicyclohexyl, phenylene, phenylene, phenylene, triphenyl, and naphthyl, and divalent organic groups selected from the following general formula; Y1 and Y2 is independent of each other and is a bonding group selected from a single bond, an ether bond, an ester bond, and a amide bond; Z is a polymerizable functional group containing an ethylenically unsaturated bond, and η is an integer of 0 to 3. However, The alkyl group of R may be substituted by an alkoxy group, a hydroxyl group, a halogen atom, or a phenyl group of 1 to 10 carbon atoms, and the cyclic aliphatic group of R and the divalent organic group of A may also be 1 to 10 carbon atoms. Substituted with alkyl, alkoxy with 1 to 10 carbons, hydroxyl, halogen atom or phenyl.) 200521578
R方面係以4〜40碳數之直鏈狀或支鏈狀烷基爲佳；a 方面係以環己烯基、聯環己烯基、伸苯基、伸聯苯基或上述 通式爲佳。 又，Y1方面係以單鍵或醚鍵或酯鍵爲佳；Y2方面係以 酯鍵爲較佳。再者，Z方面係以乙烯基、1-甲基乙烯基爲佳。 以Z-Y2表示之官能基方面係以丙烯醯基及甲基丙烯醯基爲 特佳。 以上述通式（1)表示之特定化合物方面，可舉例有丙 烯酸-2-丁基苯酯、丙烯酸-2-戊基苯酯、丙烯酸-2-己基苯 酯、丙烯酸-2-庚基苯酯、丙烯酸-2-辛基苯酯、丙烯酸-2-壬 基苯酯、丙烯酸-2-癸基苯酯、丙烯酸十二烷基苯酯、丙 烯酸-2-十六烷基苯酯、丙烯酸-2-十八烷基苯酯、甲基丙烯 酸-2-丁基苯酯、甲基丙烯酸-2-戊基苯酯、甲基丙烯酸-2-己 -10- 200521578 基苯酯、甲基丙烯酸-2-庚基苯酯、甲基丙烯酸-2-辛基苯酯、 甲基丙烯酸-2-壬基苯酯、甲基丙烯酸-2-癸基苯酯、甲基丙 烯酸-2-十二烷基苯酯、甲基丙烯酸-2-十六烷基苯酯、甲基 丙烯酸-2-十八烷基苯酯、丙烯酸-2-丁氧基苯酯、丙烯酸- 2-戊氧基苯酯、丙烯酸-2-己氧基苯酯、丙烯酸-2-庚氧基苯酯、 丙烯酸-2-辛氧基苯酯、丙烯酸-2-壬氧基苯酯、丙烯酸-2-癸 氧基苯酯、丙烯酸-2-十二烷氧基苯酯、丙烯酸-2-十六烷氧 基苯酯、丙烯酸-2-十八烷氧基苯酯、甲基丙烯酸-2-丁氧基 苯酯、甲基丙烯酸-2-戊氧基苯酯、甲基丙烯酸-2-己氧基苯 酯、甲基丙烯酸-2-庚氧基苯酯、甲基丙烯酸-2-辛氧基苯酯、 甲基丙烯酸-2-壬氧基苯酯、甲基丙烯酸-2-癸氧基苯酯、甲 基丙烯酸-2-十二烷氧基苯酯、甲基丙烯酸-2-十六烷氧基苯 酯、甲基丙烯酸-2-十八烷氧基苯酯、丙烯酸-2-丁基環己酯、 丙烯酸-2-戊基環己酯、丙烯酸-2-己基環己酯、丙烯酸-2-庚 基環己酯、丙烯酸-2-辛基環己酯、丙烯酸-2-壬基環己酯、 丙烯酸-2-癸基環己酯、丙烯酸-2-十二烷基環己酯、丙烯酸 -2-十六烷基環己酯、丙烯酸-2-十八烷基環己酯、甲基丙烯 酸-2-丁基環己酯、甲基丙烯酸-2-戊基環己酯、甲基丙烯酸 -2-己基環己酯、甲基丙烯酸-2_庚基環己酯、甲基丙烯酸-2-辛基環己酯、甲基丙烯酸-2-壬基環己酯、甲基丙烯酸-2-癸 基環己酯、甲基丙烯酸-2-十二烷基環己酯、甲基丙烯酸-2-十六烷基環己酯、甲基丙烯酸-2-十八烷基環己酯、丙烯酸-2-丁氧基環己酯、丙烯酸-2-戊氧基環己酯、丙烯酸-2·己氧基 環己酯、丙烯酸-2-庚氧基環己酯、丙烯酸-2-辛氧基環己酯、 -11- 200521578 丙烯酸-2-壬氧基環己酯、丙烯酸-2-癸氧基環己酯、丙烯酸 -2-十二烷氧基環己酯、丙烯酸-2-十六烷氧基環己酯、Θ丙烯 酸-2-十八烷氧基環己酯、甲基丙烯酸-2-丁氧基環己酯、甲 基丙烯酸-2-戊氧基環己酯、甲基丙烯酸-2-己氧基環己酯、 甲基丙烯酸-2-庚氧基環己酯、甲基丙烯酸-2-辛氧基環己 酯、甲基丙烯酸-2-壬氧環己酯、甲基丙烯酸-2-癸氧基環 己酯、甲基丙烯酸-2-十二烷氧基環己酯、甲基丙烯酸-2-十 六烷氧基環己酯、甲基丙烯酸-2-十八烷氧基環己酯、丙烯 酸-3-丁基苯酯、丙烯酸-3-戊基苯酯、丙烯酸-3-己基苯酯、 丙烯酸-3-庚基苯酯、丙烯酸-3-辛基苯酯、丙烯酸-3-壬基苯 酯、丙烯酸-3-癸基苯酯、丙烯酸-3-十二烷基苯酯、丙烯酸 -3-十六烷基苯酯、丙烯酸-3-十八烷基苯酯、甲基丙烯酸-3-丁基苯酯、甲基丙烯酸-3-戊基苯酯、甲基丙烯酸-3-己基苯 酯、甲基丙烯酸-3-庚基苯酯、甲基丙烯酸-3-辛基苯酯、甲 基丙烯酸-3-壬基苯酯、甲基丙烯酸-3-癸基苯酯、甲基丙烯 酸-3-十二烷基苯酯、曱基丙烯酸-3-十六烷基苯酯、甲基丙 烯酸-3-十八烷基苯酯、丙烯酸-3-丁氧基苯酯、丙烯酸-3-戊 氧基苯酯、丙烯酸-3-己氧基苯酯、丙烯酸-3-庚氧基苯酯、 丙烯酸-3-辛氧基苯酯、丙烯酸-3-壬氧基苯酯、丙烯酸-3-癸 氧基苯酯、丙烯酸-3-十二烷氧基苯酯、丙烯酸-3-十六烷氧 基苯酯、丙烯酸-3-十八氧基苯酯、甲基丙烯酸-3-丁氧基苯 酯、甲基丙烯酸-3 _戊氧基苯酯、甲基丙烯酸-3-己氧基苯酯、 甲基丙烯酸-3-庚氧基苯酯、甲基丙烯酸-3-辛氧基苯酯、甲 基丙烯酸-3-壬氧基苯酯、甲基丙烯酸-3-癸氧基苯酯、甲基 -12- 200521578 . 丙烯酸-3-十二烷氧基苯酯、甲基丙烯酸-3-十六烷氧基苯 酯、甲基丙烯酸-3-十八烷氧基苯酯、丙烯酸-3-丁基環己酯、 丙烯酸-3-戊基環己酯、丙烯酸-3-己基環己酯、丙烯酸-3-庚 基環己酯、丙烯酸-3-辛基環己酯、丙烯酸-3-壬基環己酯、 丙烯酸-3-癸基環己酯、丙烯酸-3-十二烷基環己酯、丙烯酸 -3-十六烷基環己酯、丙烯酸-3-十八烷基環己酯、甲基丙烯 酸-3-丁基環己酯、甲基丙烯酸-3-戊基環己酯、甲基丙烯酸 -3-己基環己酯、甲基丙烯酸-3-庚基環己酯、甲基丙烯酸-3-辛基環己酯、甲基丙烯酸-3-壬基環己酯、甲基丙烯酸-3-癸 基環己酯、甲基丙烯酸-3-十二烷基環己酯、甲基丙烯酸- 3-十六烷基環己酯、甲基丙烯酸-3-十八烷基環己酯、丙烯酸-3-丁氧基環己酯、丙烯酸-3-戊氧基環己酯、丙烯酸-3-己氧基 環己酯、丙烯酸-3-庚氧基環己酯、丙烯酸-3,辛氧基環己酯、 丙烯酸-3-壬氧基環己酯、丙烯酸-3-癸氧基環己酯、丙烯酸 -3-十二烷氧荸環己酯、丙烯酸-3-十六烷氧基環己酯、丙烯 酸-3-十八烷氧基環己酯、甲基丙烯酸-3-丁氧基環己酯、甲 基丙烯酸-3-戊氧基環己酯、甲基丙烯酸-3-己氧基環己酯、 甲基丙烯酸-3-庚氧基環己酯、甲基丙烯酸-3-辛氧基環己 酯、甲基丙烯酸-3-壬氧基環己酯、甲基丙烯酸-3-癸氧基環 己酯、甲基丙烯酸-3-十二烷氧基環己酯、曱基丙烯酸-3-十 六烷氧基環己酯、甲基丙烯酸-3-十八烷氧基環己酯、丙烯 酸-4-· 丁基苯酯、丙烯酸-4-戊基苯酯、丙烯酸-4-己基苯酯、 丙烯酸-4-庚基苯酯、丙烯酸-4-辛基苯酯、丙烯酸-4-壬基苯 酯、丙烯酸-4-癸基苯酯、丙烯酸-4-十二烷基苯酯、丙烯酸 -13- 200521578 -4-十六烷基苯酯、丙烯酸-4-十八烷基苯酯、甲基丙烯酸-4-丁基苯酯、甲基丙烯酸-4-戊基苯酯、甲基丙烯酸-4-己基苯 酯、甲基丙烯酸-4-庚基苯酯、甲基丙烯酸-4-辛基苯酯、甲 基丙烯酸-4-壬基苯酯、甲基丙烯酸-4-癸基苯酯、甲基丙烯 酸-4-十二烷基苯酯、甲基丙烯酸-4-十六烷基苯酯、甲基丙 烯酸-4-十八烷基苯酯、丙烯酸-4-丁氧基苯酯、丙烯酸-4-戊 氧基苯酯、丙烯酸-4-己氧基苯酯、丙烯酸-4-庚氧基苯酯、 丙烯酸-4-辛氧基苯酯、丙烯酸-4-壬氧基苯酯、丙烯酸-4-癸 氧基苯酯、丙烯酸-4-十二烷氧基苯酯、丙烯酸-4-十六烷氧 基苯酯、丙烯酸-4-十八氧基苯酯、甲基丙烯酸-4-丁氣基苯 酯、甲基丙烯酸-4-戊氧基苯酯、甲基丙烯酸-4-己氧基苯酯、 甲基丙烯酸-4-庚氧基苯酯、甲基丙烯酸-4-辛氧基苯酯、甲 基丙烯酸-4-壬氧基苯酯、甲基丙烯酸-4-癸氧基苯酯、甲基 丙烯酸-4-十二烷氧基苯酯、甲基丙烯酸-4-十六烷氧基苯 酯、甲基丙烯酸-4-十八烷氧基苯酯、丙烯酸-4-丁基環己酯、 丙烯酸-4-戊基環己酯、丙烯酸-4-己基環己酯、丙烯酸-4-庚 基環己酯、丙烯酸-4-辛基環己酯、丙烯酸-4-壬基環己酯、 丙烯酸-4-癸基環己酯、丙烯酸-4-十二烷基環己酯、丙烯酸 -4-十六烷基環己酯、丙烯酸十八烷基環己酯、甲基丙烯 酸-4-丁基環己酯、甲基p烯酸-4-戊基環己酯、甲基丙烯酸 -4-己基環己酯、甲基丙烯酸-4-庚基環己酯、甲基丙烯酸- 4-辛基環己酯、甲基丙烯酸-心壬基環己酯、甲基丙烯酸-4-癸 基環己酯、甲基丙烯酸-4-十二烷基環己酯、甲基丙烯酸- 4-十六烷基環己酯、甲基丙烯酸-4-十八烷基環己酯、丙烯酸-4-\ -14- 200521578 丁氧基環己酯、丙烯酸-4-戊氧基環己酯、丙烯酸-4-己氧基 環己酯、丙烯酸-4-庚氧基環己酯、丙烯酸-4-辛氧基環己酯、 丙烯酸-4-壬氧基環己酯、丙烯酸-4-癸氧基環己酯、丙烯酸 -4-十二烷氧基環己酯、丙烯酸-4-十六烷氧基環己酯、丙烯 酸-4-十八烷氧基環己酯、甲基丙烯酸-4-丁氧基環己酯、甲 基丙烯酸-4-戊氧基環己酯、甲基丙烯酸-4-己氧基環己酯、 甲基丙烯酸-4-庚氧基環己酯、甲基丙烯酸-4-辛氧基環己 酯、甲基丙烯酸-4-壬氧基環己酯、甲基丙烯酸-4-癸氧基環 己酯、甲基丙烯酸-4-十二烷氧基環己酯、甲基丙烯酸-4-十 六烷氧基環己酯、甲基丙烯酸-4-十八烷氧基環己酯、丙烯 酸-4- (4-丁基環己基）苯酯、丙烯酸_ 4- (4-戊基環己基） 苯酯、丙烯酸-4_(4-己基環己基）苯酯、丙烯酸-4- (4-辛 基環己基）苯酯、丙烯酸-4- (4-癸基環己基）苯酯、丙烯酸 -4- (4-十二烷基環己基）苯酯、丙烯酸-4- (4-十六烷基環 己基）苯酯、丙烯酸-4- ( 4-十八烷基環己基）苯酯、甲基丙 烯酸_4_( 4-丁基環己基）苯酯、甲基丙烯酸-4-(4-戊基環 己基）苯酯、甲基丙烯酸-4-(4-己基環己基）苯酯、甲基丙 烯酸-4- (4-辛基環己基）苯酯、甲基丙烯酸-4- (4-癸基環 己基）苯酯、甲基丙烯酸-4- (4-十二烷基環己基）苯酯、甲 基丙烯酸-4-(4-十六烷基環己基）苯酯、甲基丙烯酸-4-( 4-十八烷基環己基）苯酯、丙烯酸-4_(4_ 丁基環己基）環己酯、 丙烯酸-4- (4-戊基環己基）環己酯、丙烯酸-4- (4-己基環 己基）環己酯、丙烯酸- 4-(4-辛基環己基）環己酯、丙烯酸 -4- (4-癸基環己基）環己酯、丙烯酸-4-(4-十二烷基環己 -15- 200521578 . 基）環己酯、丙烯酸- 4-(4-十六烷基環己基）環己酯、丙烯 酸- 4-(4-十八烷基環己基）環己酯、甲基丙烯酸-4-(4-丁 基環己基）環己酯、甲基丙烯酸-4-(4-戊基環己基）環己酯、 甲基丙烯酸- 4-(4-己基環己基）環己酯、甲基丙烯酸- 4-(4-辛基環己基）環己酯、甲基丙烯酸-4- (4-癸基環己基）環己 酯、甲基丙烯酸- 4-(4-十二烷基環己基）環己酯、甲基丙烯 酸-4-(4-十六烷基環己基）環己酯、甲基丙烯酸-4-( 4-十 八烷基環己基）環己酯、丙烯酸膽固醇酯、甲基丙烯酸膽固 醇酯、丙烯酸膽甾烷酯、甲基丙烯酸膽甾烷酯、丙烯酸-3-脫氫松香氧基-羥丙酯、甲基丙烯酸-3-脫氫松香氧基-羥丙酯 作爲較佳之化合物。 於該等化合物中，以丙烯酸-4-丁基苯酯、丙烯酸-4·戊 基苯酯、丙烯酸-4-己基苯酯、丙烯酸-4-庚基苯酯、丙烯酸 -4-辛基苯酯、丙烯酸-4-壬基苯酯、丙烯酸-4-癸基苯酯、丙 烯酸-4-十二烷基苯酯、丙烯酸-4-十六烷基苯酯、丙烯酸- 4-十八烷基苯酯、甲基丙烯酸-4-丁基苯酯、甲基丙烯酸-4-戊 基苯酯、甲基丙烯酸-4-己基苯酯、甲基丙烯酸-4-庚基苯酯、 甲基丙烯酸-4-辛基苯酯、甲基丙烯酸-4-壬基苯酯、甲基丙 烯酸-4-癸基苯酯、甲基丙烯酸-4-十二烷基苯酯、甲基丙烯 酸-心十六烷基苯酯、甲基丙烯酸-4-十八烷基苯酯、丙烯酸 -4-丁氧基苯酯、丙烯酸-4-戊氧基苯酯、丙烯酸-4-己氧基苯 酯、丙烯酸-4 _庚氧基苯酯、丙烯酸-4-辛氧基苯酯、丙烯酸 -4-壬氧基苯酯、丙烯酸-4-癸氧基苯酯、丙烯酸-4-十二烷氧 基苯酯、丙烯酸-4-十六烷氧基苯酯、丙烯酸-4-十八烷氧基 -16- 200521578 苯酯、甲基丙烯酸-4-丁氧基苯酯、甲基丙烯酸-4-戊氧基苯 酯、甲基丙烯酸-4-己氧基苯酯、甲基丙烯酸-4-庚氧基苯酯、 甲基丙烯酸-4-辛氧基苯酯、甲基丙烯酸-4-壬氧基苯酯、甲 基丙烯酸-4-癸氧基苯酯、甲基丙烯酸-4-十二烷氧基苯酯、 甲基丙烯酸-4-十六烷氧基苯酯、甲基丙烯酸-4-十八烷氧基 苯酯、丙烯酸-4-丁基環己酯、丙烯酸-4-戊基環己酯、丙烯 酸-4-己基環己酯、丙烯酸-4-庚基環己酯、丙烯酸-4-辛基環 己酯、丙烯酸-4-壬基環己酯、丙烯酸-4-癸基環己酯、丙烯 酸-4-十二烷基環己酯、丙烯酸-4-十六烷基環己酯、丙烯酸 -4-十八烷基環己酯、甲基丙烯酸-4-丁基環己酯、甲基丙烯 酸-4-戊基環己酯、甲基丙烯酸-4-己基環己酯、甲基丙烯酸 -4-庚基環己酯、甲基丙烯酸-4-辛基環己酯、甲基丙烯酸-4-壬基環己酯、甲基丙烯酸-4-癸基環己酯、甲基丙烯酸-4-十 二烷基環己酯、甲基丙烯酸-4-十六烷基環己酯、甲基丙烯 酸-4-十八烷基環己酯、丙烯酸-4-丁氧基環己酯、丙烯酸-4-戊氧基環己酯、丙烯酸-4-己氧基環己酯、丙烯酸-4-庚氧基 環己酯、丙烯酸-4-辛氧基環己酯、丙烯酸-4-壬氧基環己酯、 丙烯酸-4-癸氧基環己酯、丙烯酸-4-十二烷氧基環己酯、丙 烯酸-4-十六烷氧基環己酯、丙烯酸-4-十八烷氧基環己酯、 甲基丙烯酸-4-丁氧基環己酯、甲基丙烯酸-4-戊氧基環己 酯、甲基丙烯酸-4-己氧基環己酯、甲基丙烯酸-4-庚氧基環 己酯、甲基丙烯酸-4-辛氧基環己酯、甲基丙烯酸-4-壬氧基 環己酯、甲基丙烯酸-4-癸氧基環己酯、甲基丙烯酸-4-十二 烷氧基環己酯、甲基丙烯酸-4-十六院氧基環己酯、甲基丙 -17- 200521578 烯酸-4-十八烷氧基環己酯、丙烯酸-4- ( 4-丁基環己基）苯 酯、丙烯酸-4-(4-戊基環己基）苯酯、丙烯酸-4-( 4-己基 環己基）苯酯、丙烯酸-4-( 4-辛基環己基）苯酯、丙烯酸-4-(4-癸基環己基）苯酯、丙烯酸-4- (4-十二烷基環己基）苯 酯、丙烯酸-4-(4-十六烷基環己基）苯酯、丙烯酸_4_ (4-十八烷基環己基）苯酯、甲基丙烯酸-4-( 4-丁基環己基）苯 酯、甲基丙烯酸-4- (4-戊基環己基）苯酯、甲基丙烯酸-4-(4-己基環己基）苯酯、甲基丙烯酸-4-( 4-辛基環己基）苯 酯、甲基丙烯酸-4- (4-癸基環己基）苯酯、甲基丙烯酸-4-(4-十二烷基環己基）苯酯、甲基丙烯酸-4-(4-十六烷基環 己基）苯酯、甲基丙烯酸-4- (4-十八烷基環己基）苯酯、丙 烯酸-4- ( 4-丁基環己基）環己酯、丙烯酸-4- ( 4-戊基環己 基）環己酯、丙烯酸-4- (4-己基環己基）環己酯、丙烯酸-4-(4-辛基環己基）環己酯、丙烯酸-4- (4-癸基環己基）環己 酯、丙烯酸-4-(4-十二烷基環己基）環己酯、丙烯酸-4_( 4-十六烷基環己基）環己酯、丙烯酸-4-( 4-十八烷基環己基） 環己酯、甲基丙烯酸-4-(4-丁基環己基）環己酯、甲基丙烯 酸-4- (4-戊基環己基）環己酯、甲基丙烯酸-4- (4-己基環 己基）環己酯、甲基丙烯酸-4-(4-辛基環己基）環己酯、甲 基丙烯酸-4- (4-癸基環己基）環己酯、甲基丙烯酸-4-(4-十二烷基環己基）環己酯、甲基丙烯酸- 4-(4-十六烷基環己 基）環己酯、甲基丙烯酸-4- ( 4-十八烷基環己基）環己酯、 丙烯酸膽固醇酯、甲基丙烯酸膽固醇酯、丙烯酸膽甾烷酯、 甲基丙烯酸膽甾烷酯爲更佳。 -18- 200521578 特定化合物、例如於上述通式（1)中Y2爲酯鍵之化合 物係藉由使具有疏水基之醇或鹵化物，與（甲基）丙烯酸或 其衍生物反應而得。 [醇] 具有疏水基之醇方面，可舉例有烷基醇、環狀脂肪族 醇、芳香族醇等。該等化合物之烷基、環狀脂肪族基及芳香 族基係亦可由例如烷基（除了上述烷基之情況以外）、苯基、 烷氧基、鹵素基、烷氧羧基代換。相關之醇方面，可舉例有 以己醇、庚醇、辛醇、壬醇、癸醇、十二烷醇、十六烷醇、 十八烷醇、環己醇、甲基環己醇、乙基環己醇、己基己醇、 聯環己醇、十氫-2-萘酚、膽固醇、膽窜烷醇、酚、甲酚、 乙酚、丁酚、己酚、辛酚、壬酚環己酚、（乙基環己基）酚、 (丙基環己基）酚、（丁基環己基）酚、（戊基環己基）酚、 (己基環己基）酚、（辛基環己基）酚、聯環己酚、（乙基 環己基）環己醇、（丙基環己基）環己醇、（丁基環己基） 環己醇、（戊基環己基）環己醇、（己基環己基）環己醇、 (辛基環己基）環己醇、4-正己醇、4-正庚醇、4-正辛醇、 4-正己氧醇、4-正庚氧醇、4-正辛氧醇、4-第三丁基酚、三 氟甲酚、4-氟酚、2,5-二氟酚、羥基聯酚、萘酚爲佳者。 [鹵化烷基] 鹵化物係以鹵素原子取代上述醇之羥基的化合物’其範 例方面，舉出有氯化物、溴化物、碘化物。在鹵化物爲例如 鹵化烷基之情況的烷基方面，舉例有己基、庚基、辛基、壬 基、癸基、十二院基、十六院基、十八院基。該等院基爲直 -19- 200521578 . 鏈或分枝均可，亦可由烷氧基取代。 [(甲基）丙烯酸酯之合成] 提供於（甲基）丙烯酸之合成反應之（甲基）丙烯酸或 其衍生物、與醇之使用比例係以相對於1當量包含於醇之羥 基，（甲基）丙烯酸或其衍生物爲1〜2當量之比例爲佳， 以1 · 1〜1 · 5當量之比例爲更佳。（甲基）丙烯酸衍生物方面， 舉例有（甲基）丙烯酸、（甲基）丙烯酸之鹼金屬鹽、鹵化 (甲基）丙烯醯等。 在（甲基）丙烯酸酯之合成中，可使用通常之酯化反應， 可利用例如使用酸觸媒或鹼觸媒來脫水縮合羧酸與醇的方 法、羧酸鹵化物與醇之反應、羧酸鹼金屬鹽與鹵化烷基之反 應。反應係於-20〜150°C下、而以0〜100°C爲佳之溫度條件 下進行。反應溶劑方面，如果爲醇或1，2級胺以外、可溶解 所合成之（甲基）丙烯酸酯及起始原料者，則無特別之限制， 可舉例有乙醚、四氫呋喃、二氯甲烷、12 -二氯乙烷、1，4_ 二氯丁烷、三氯乙烷、氯苯、鄰二氯苯、己烷、庚烷、辛烷、 苯、甲苯、二甲苯、丙酮、甲基乙基酮、甲基異丁基酮、環 己酮、乙酸甲酯、乙酸乙酯、乙酸丁酯、乳酸乙酯、乳酸丁 酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、N-甲基-2-四氫吡 咯酮、N，N-二甲基乙醯胺、N，N-二甲基甲醯胺、二甲基礪、 7 -丁內酯。 又，有機溶劑之使用量係以例如其爲起始原料之醇相對 於反應溶液全量（有機溶劑與醇之合計使用量）成爲0 · 1〜 20重量％之量爲佳。 -20- 200521578 其中，爲了防止反應中之聚合，亦可於反應系統中，在 無妨害反應之範圍中添加聚合抑制劑。 聚合抑制劑之具體範例方面，舉出有氫醌、氫醌單甲基 醚、N-硝苯基氫胺鋁鹽、對第三丁基兒茶酚、2,4-二硝基酚 等。 如以上而來，得到（甲基）丙烯酸酯之粗生成物。然後， 可藉由再結晶、蒸餾、層析術等來精製該反應生成物。 [具有複數個（甲基）丙烯酸基之（甲基）丙烯酸酯] 於本發明中，與特定化合物一起，在未妨害該配向性之 範圍內，與特定化合物共聚合。亦可一起使用具有複數個（甲 基）丙烯酸基之（甲基）丙烯酸酯。相關之（甲基）丙烯酸 酯方面，可舉例有如乙二醇、丙二醇之烷基二醇的二丙烯酸 酯或二甲基丙烯酸酯；如多乙二醇、多丙二醇之多烷基二醇 的二丙烯酸酯或二甲基丙烯酸酯；如三羥甲基丙基二丙烯酸 酯、三羥甲基丙基二甲基丙烯酸酯之單羥基二丙烯酸酯或單 羥基寡聚甲基丙烯酸酯，與如丙二酸、丁二酸、戊二酸之二 羧酸的含有游離羧基單酯化物；如丙-1，2,3-三羧酸（三羧基 酸）、丁 -1，2,4-三羧酸、苯-1，2,3-三羧酸、苯-1，3,4-三羧酸、 苯-1,3,5-三羧酸之三羧酸，與如丙烯酸-2-羥基乙酯、甲基丙 烯酸-2-羥基乙酯、丙烯酸-2-羥基丙酯、甲基丙烯酸-2-羥基 丙酯之單羥基單丙烯酸酯或單羥基單甲基丙烯酸酯之含有 游離羧基之寡聚酯化物；如聚酯、環氧樹脂、胺甲酸酯樹脂、 醇酸樹脂、聚矽氧樹脂、螺烷樹脂之寡聚丙烯酸酯或寡聚甲 基丙烯酸酯；如兩終端羥基聚1 ,3-丁二烯、兩終端羥基聚異 -21- 200521578 丁烯、兩終端羥基聚己內酯之兩終端羥基化聚合物的二丙烯 酸酯或二甲基丙烯酸酯、及三（2_丙烯醯氧基乙基）磷酸鹽、 三（2 -甲基腈氧基乙基）磷酸鹽等。 [其他聚合性化合物] (甲基）丙烯酸化合物以外之具有乙烯性不飽和雙鍵的 化合物，係可在無損於本發明之效果程度中來倂用。可使用 之化合物方面，可舉例有順式丁烯亞醯胺系化合物、苯乙烯 系化合物。 [積層配向膜、該配向膜之製造方法、及使用其之液晶顯示 元件] 本發明之積層配向膜及使用該配向膜而得之液晶顯示 元件係可藉由例如以下之方法來製造。 在設置有已形成圖案之透明導電膜的基板單面、或雙面 上，形成藉由有機材料所形成之突起狀構造物。在僅於基板 單面上形成突起狀構造物的情況下，基板另一面之導電性膜 則必須有細縫狀之圖案。又，未形成突起狀構造物之情況 下，亦可使基板雙面上之透明導電膜形成細縫狀之圖形。構 成突起狀構造物之有機材料方面，以可形成圖案爲佳，從該 觀點來看則以光阻劑材料爲佳。再者，如使用正型光阻劑 時，則容易控制突起狀構造物之形狀，從配向控制之觀點來 看亦佳。所使用之正型光阻劑範例方面，可舉出有酚醛樹 脂、丙烯酸酯樹脂。基板方面，可使用例如由漂浮玻璃’鈉 玻璃等之玻璃；聚對苯二甲酸二乙酯、聚對苯二甲酸二丁 酯、聚醚颯、聚碳酸酯等之塑膠所構成之透明基板。設置於 -22- 200521578 基板之單面上的透明導電膜方面，可使用例如由氧化錫 (Sn02)所構成之NESA膜（美國PPG公司登錄商標）、由 氧化銦-氧化錫（In203-Sn02 )所構成之ITO膜等。在該等 透明導電膜之圖案形成中，係使用例如光蝕刻法或預先使用 遮罩之方法。於形成突起之官能基板上，藉由輥塗法、旋轉 塗布機法、印刷法等之方法來塗布通常之液晶配向膜形成用 液晶配向劑，其次，藉由加熱塗布面而形成塗膜。在該液晶 配向劑之塗布時，爲了使基板表面及透明導電膜與塗膜之接 著性變得更好，亦可於基板之該表面上預先塗布含有官能性 矽烷之化合物、含有官能性鈦之化合物等。該液晶配向劑塗 布後之加熱溫度係以80〜3 00°C爲佳，以120〜250°C爲較 佳。還有，含有聚醯胺酸之液晶配向劑係於塗布後藉由除去 有機溶劑而形成作爲配向膜之塗膜，亦可藉由進一步加熱來 進行脫水閉環，而成爲亞醯胺化之塗膜。其爲所形成之第一 層的第一膜膜厚係如上述。 如上述來製作2片已形成第一層之官能基板，並經由間 隙（元件夾具）來相向配置，使用密封劑來貼合2片基板之 周邊部分。 密封劑方面，可使用例如含有熱硬化劑或感光性硬化 劑、及作爲間隔物之氧化鋁球的環氧樹脂等。 在基板及以密封劑劃分之元件夾具內，注入充塡液晶與 特定化合物、因情況進一步注入充塡具有複數個（甲基）丙 烯酸基之（甲基）丙烯酸酯，封住注入孔而構成液晶元件。 可使用之液晶方面，可舉例有向列型液晶及蝶型液晶。 -23- 200521578 其中以向列型液晶爲特佳，可使用例如希夫鹼系液晶、氧化 偶氮系液晶、聯苯系液晶、苯基環己院系液晶、酯系液晶、 聯三苯系液晶、聯苯基環己烷系液晶、嘧啶系液晶、二噚烷 系液晶、聯環辛烷系液晶、Q龐系液晶等。又，於該等液晶 中，亦可添加例如氯化膽固醇、壬酸膽固醇酯、碳酸膽固醇 酯等之膽固醇型液晶或如以商品名「C-15」 「CB-15」（美 耳克公司製）販售之凱伊拉耳劑等來使用。再者，亦可使用 桂皮酸對癸氧基亞苄基-對胺基-2-甲基丁酯等之強介電性液 晶。 _ 混合特定化合物與液晶，並在注入於液晶顯示元件內之 後’藉由照射放射線於液晶顯示元件，於第一層上形成其爲 第二層之第二膜。 液晶中之具有不飽和雙鍵基之化合物的濃度爲例如1 〇 重量％以下，以5重量％以下爲佳，以3重量％以下爲更佳。 濃度超過1 0重量％時，則由於引起透過光之散射而難以得 到良好之畫面。 聚合特定化合物之放射線方面，可使用例如可見光線、 · 紫外線 '遠紫外線、電子射線、X射線等。以波長在i 5 0nm 〜8〇Onm之範圍的放射線爲佳，其中以具有240nm〜 500nm 之波長的放射線爲特佳。 前述光源方面，可使用例如低壓水銀燈、高壓水銀燈、 重氫燈、鹵化金屬燈、氬氣共振燈、氙氣燈、激光雷射等。 曝光量方面係以0·01〜50J/CH12爲佳，以0.1〜20J/cm2 爲更佳。又’以所使用之液晶顯示液晶相之溫度來曝光爲佳。 -24- 200521578 然後，在液晶元件之外表面，即，構成液晶元件之各個 基板之另一側面上，藉由貼合偏光板成爲該偏光方向互相垂 直，而得到液晶顯示元件。 貼合於液晶元件之外表面的偏光板方面，可舉出有延伸 配向聚乙烯醇、同時以乙酸纖維素保護膜夾著被稱爲已吸收 碘之Η膜之偏光膜的偏光板或由Η膜本身所構成之偏光板。 以下，雖藉由實例來更具體地說明本發明，但本發明係 不受該等實例所限制者。還有，針對藉由以下實例及比較例 所製作之液晶顯示元件的測定方法及評估方法係如以下所 述。 [積層配向膜之第二層的膜厚] 分解液晶顯示元件，並在以丙酮除去液晶之後，以刮刀 刮傷配向膜而露出基板表面，藉由以接觸式膜厚測定計測定 所產生之階層差距來測定積層型配向膜之膜厚（第一層膜厚 爲 800Α )。 從特定化合物而來之第二層膜厚（Α)係由下式算出。 (第二層膜厚）=(積層型配向膜之膜厚）-8 00 [液晶之配向性] 以偏光顯微鏡觀察開•關電壓於液晶顯示元件時之異 常磁疇之有無，來判定無異常磁疇之情況爲「良好」。 [電壓保持率] 以於室溫下5 V之電壓、6 0微秒之施加時間、1 6,7毫秒 之間隔施加於液晶顯示元件時，使用東陽技術股份有限公司 製VHR-1測定從5V施加解除至16.7毫秒後之保持電壓， 200521578 求得電壓保持率。 [殘留DC] 於 25 °C之環境溫度下施加已重疊1.0V直流電壓之 3 0Hz、3.0V之矩形波於液晶顯示元件2小時，藉由閃光消 去法求得殘留於切斷直流電壓後之液晶元件內的電壓而求 得殘留DC電壓。 【合成例1】 在附加矽膠乾燥管之5 0 OmL容量之三口燒瓶中加入10g 冷-膽甾烷醇、200mL脫水四氫呋喃並攪拌之後，加入35mg 2-甲氧基二氫醌及6g三乙胺，於室溫下攪拌並溶解。於其 中滴下6g氯化丙烯醯於反應溶液，於室溫攪拌2小時。 以10% K2C03水溶液、飽和食鹽水、水之順序洗淨反應 液，以硫酸鎂乾燥後，蒸餾除去溶劑。 藉由以乙醇再結晶所得之固體而得到純度良好（92%產 率）之l〇.5g丙烯酸膽甾烷基酯（以下，稱爲「丙烯酸酯化 合物（I )」）。 【合成例2】 於合成例1中，除了使用氯化甲基丙烯醯來取代氯化丙 烯醯以外，藉由同樣之方法，以93%產率得到目的之甲基丙 烯酸膽甾烷基酯（以下，稱爲「甲基丙烯酸酯化合物（II)」）。 【合成例3】 於合成例1中，除了使用膽固醇來取代膽甾烷醇以 外，藉由同樣之方法，以93%產率得到目的之丙烯酸膽固醇 酯（以下，稱爲「丙烯酸酯化合物（ΠΙ )」）。 200521578 . ' 【合成例4】 於合成例1中，除了使用膽固醇與氯化甲基丙儲醯來取 代/3 -膽甾烷醇與氯化丙烯醯以外，藉由同樣之方法，以95 %產率得到目的之甲基丙烯酸膽固醇酯（以下，稱胃「巾^ 丙烯酸酯化合物（IV)」）。 【合成例5】 於合成例1中，除了使用4-己氧基酚來取代$ _膽<畜文完 醇以外，藉由同樣之方法，藉由層析術來精製，以9 3 %產$ 得到目的之丙烯酸-4己氧基酚酯（以下，稱爲「丙燏酸醋化； 合物（V)」）。 【合成例6】 於合成例5中，除了使用4_辛氧基酚來取代4-己氧基 酷以外’藉由R樣之方法’以93%產率得到目的之丙嫌酸 辛氧基酚酯（以下，稱爲「丙烯酸酯化合物（VI)」）。 【合成例7】 於合成例5中’除了使用4_ ( 4-己苯基）酚來取代4_ 己氧基酚以外，藉由同樣之方法，以94%產率得到目的之丙 稀酸-4- (4-己苯基）酌醋（以下’稱爲「丙烯酸酯化合物 (VII )」）。 【合成例8】 於合成例5中’除了使用4-(4-己基環己基）酚來取代 己氧基酚以外，藉由同樣之方法，以92%產率得到目的之 丙嫌酸-4- (4-己基環己基）酌醋（以下，稱爲「丙稀酸醋化 合物（VIII )」）。 -27- 200521578 【實例1】 (1 )液晶混合物之調製 溶解10mg於合成例1中所得之丙烯酸酯與lOmg二羥 甲基-三環癸烷二丙烯酸酯於lg負型液晶MLC-6608 (美耳 克公司製）而成爲混合物。 (2)第一層形成用液晶配向劑之製造 溶解 9.7g ( 90mmol)對苯二胺與 5.2g ( lOmmol) 3,5-二胺基苯甲酸膽固醇酯於20 0ml 1-甲基-2-四氫吡咯酮，於 其中加入6.78(3〇1!1111〇1)2,3,5-三羧基環戊基乙酸二酐、15§ (70mmol)苯四甲酸二酐，於60°C進行6小時反應。然後， 注入反應溶液於5,000ml而得到白色沉澱物。藉由將其在減 壓下於室溫乾燥，得到l.〇dl/g固有黏度（1-甲基-2-四氫吡 咯酮中、25 °C )之白色聚醯胺酸粉末。溶解該聚醯胺酸粉末 於1-甲基-2-四氫吡咯酮中而得到3%固體成分濃度之液晶 配向劑。 (3 )液晶顯示元件之製作： [1] 在由設置於1mm厚度之玻璃基板單面之ITO膜所構成 之透明導電性膜上，藉由旋轉塗布法塗布於（2 )所製作之 液晶配向劑，藉由於180°C下燒成1小時而形成800A乾燥 膜厚的塗膜。 [2] 如上述來製作2片已形成其爲第一層之第一膜的基 板，於個別基板之外緣部分，藉由絹網印刷法塗布含有5 // m 直徑之氧化鋁球之環氧樹脂系接著劑後，經由間隙相向配置 2片基板’連接外緣部分等並壓著來硬化接著劑。 -28- 200521578 [3 ] 在藉由基板表面及外緣部分之接著劑所劃分之元件夾 具內，注入充塡如上述所調製之向列型液晶「MLC-6608」 (美耳克公司製）之混合物，其次，以環氧系接著劑密封注 入孔而構成液晶元件。於該液晶顯示元件中，經由光罩，照 射l〇J/cm2包含365nm、405nm、436nm波長之光線的紫外 線，於液晶中聚合特定化合物。然後，於液晶元件之外表面， 藉由貼合偏光板來製作液晶顯示元件。 [4] 針對如上述所製作之液晶顯示元件，測定第二層膜厚、 垂直配向性、電壓保持率及殘留DC電壓。結果示於表1。 【實例2〜8】 依照示於下述表1之處理方法，使用於合成例2〜8中 所得之（甲基）丙烯酸酯（II〜VIII)來與實例1同樣地調 製液晶混合物。其次，使用各個如此所調製之液晶顯示混合 物，與實例1同樣地製作液晶顯示元件。針對各個所製作之 液晶顯示元件，與實例1同樣地進行評估。結果合倂示於表 【比較例1〜2】 依照示於下述表1之處理方法，藉由未包含本發明中之 特定化合物的液晶，與實例1同樣地製作液晶顯示元件。針 對各個所製作之液晶顯示元件，與實例1同樣地進行評估。 【比較例3】 除了於液晶顯示元件外，藉由光照射來聚合特定化合物 與液晶之混合物，並將其注入於液晶顯示元件之外，與實例 1同樣地進行評估。結果合倂示於表1。 -29- 200521578 表1 (甲基） 丙烯酸酯 二(甲基） 丙烯酸酯 第二層膜厚 (A) 液晶之 配向性 電壓保持率 (% ) 殘留DC電壓 (mV) 實例 1 合成例1 有 300 良好 99 10 2 合成例2 有 100 良好 99 10 3 合成例3 有 300 良好 99 20 4 合成例4 有 200 良好 99 30 5 合成例5 有 100 良好 99 20 6 合成例6 有 200 良好 99 40 7 合成例7 有 300 良好 99 20 8 合成例8 有 300 良好 99 20 比較例 1 /γγΓ 無 有 300 不良 98 70 2 4τττ TTTF y» \ν ΛτΤ ΙΙΠ J\\\ 0 不良 93 320 3 有 有 0 不良 93 500The R side is preferably a linear or branched alkyl group having 4 to 40 carbons; the a side is cyclohexenyl, bicyclohexenyl, phenylene, phenylene, or the general formula above. good. Further, Y1 is more preferably a single bond, an ether bond, or an ester bond; Y2 is more preferably an ester bond. The Z side is preferably vinyl or 1-methylvinyl. The functional groups represented by Z-Y2 are particularly preferably acrylfluorenyl and methacrylfluorenyl. As the specific compound represented by the above general formula (1), examples include 2-butylphenyl acrylate, 2-pentylphenyl acrylate, 2-hexylphenyl acrylate, and 2-heptylphenyl acrylate , 2-octylphenyl acrylate, 2-nonylphenyl acrylate, 2-decylphenyl acrylate, dodecylphenyl acrylate, 2-hexadecylphenyl acrylate, acrylic acid-2 -Octadecyl phenyl ester, 2-butyl phenyl methacrylate, 2-pentyl phenyl methacrylate, 2-hexyl-10-methacrylate 2005 2005578, methacrylic acid-2 -Heptylphenyl ester, 2-octylphenyl methacrylate, 2-nonylphenyl methacrylate, 2-decylphenyl methacrylate, 2-dodecylbenzene methacrylate Ester, 2-hexadecylphenyl methacrylate, 2-octadecylphenyl methacrylate, 2-butoxyphenyl acrylate, 2-pentyloxyphenyl acrylate, acrylic acid- 2-hexyloxyphenyl ester, 2-heptyloxyphenyl acrylate, 2-octyloxyphenyl acrylate, 2-nonyloxyphenyl acrylate, 2-decyloxyphenyl acrylate, acrylic acid- 2-dodecyloxyphenyl ester, acrylic acid 2-hexadecyloxy Ester, 2-octadecyloxyphenyl acrylate, 2-butoxyphenyl methacrylate, 2-pentyloxyphenyl methacrylate, 2-hexyloxyphenyl methacrylate, 2-heptyloxyphenyl methacrylate, 2-octyloxyphenyl methacrylate, 2-nonyloxyphenyl methacrylate, 2-decyloxyphenyl methacrylate, methyl 2-dodecyloxyphenyl acrylate, 2-hexadecyloxyphenyl methacrylate, 2-octadecyloxyphenyl methacrylate, 2-butylcyclohexyl acrylate, 2-pentylcyclohexyl acrylate, 2-hexylcyclohexyl acrylate, 2-heptylcyclohexyl acrylate, 2-octylcyclohexyl acrylate, 2-nonylcyclohexyl acrylate, acrylic acid 2-Decylcyclohexyl, 2-dodecylcyclohexyl acrylate, 2-hexadecylcyclohexyl acrylate, 2-octadecylcyclohexyl acrylate, methacrylic acid-2 -Butyl cyclohexyl, 2-pentylcyclohexyl methacrylate, 2-hexyl cyclohexyl methacrylate, 2-heptyl cyclohexyl methacrylate, 2-octyl methacrylate Cyclohexyl, 2-nonylcyclohexyl methacrylate, 2-decylcyclohexyl methacrylate , 2-dodecyl cyclohexyl methacrylate, 2-hexadecyl cyclohexyl methacrylate, 2-octadecyl cyclohexyl methacrylate, 2-butoxy acrylate Cyclohexyl, 2-pentyloxycyclohexyl acrylate, 2-hexyloxycyclohexyl acrylate, 2-heptyloxycyclohexyl acrylate, 2-octyloxycyclohexyl acrylate, -11 -200521578 2-nonyloxycyclohexyl acrylate, 2-decyloxycyclohexyl acrylate, 2-dodecyloxycyclohexyl acrylate, 2-hexadecyloxycyclohexyl acrylate, Θ-2-octadecylcyclohexyl acrylate, 2-butoxycyclohexyl methacrylate, 2-pentyloxycyclohexyl methacrylate, 2-hexyloxy methacrylate Hexyl ester, 2-heptyloxycyclohexyl methacrylate, 2-octyloxycyclohexyl methacrylate, 2-nonylcyclohexyl methacrylate, 2-decyloxy methacrylate Cyclohexyl, 2-dodecyloxycyclohexyl methacrylate, 2-hexadecyloxycyclohexyl methacrylate, 2-octadecyloxycyclohexyl methacrylate, acrylic acid 3-butylphenyl ester, 3-pentylphenyl acrylate, 3-hexylphenyl acrylate, propylene 3-heptylphenyl ester, 3-octylphenyl acrylate, 3-nonylphenyl acrylate, 3-decylphenyl acrylate, 3-dodecylphenyl acrylate, 3-acrylate Cetylphenyl ester, 3-octadecylphenyl acrylate, 3-butylphenyl methacrylate, 3-pentylphenyl methacrylate, 3-hexylphenyl methacrylate, 3-heptylphenyl methacrylate, 3-octylphenyl methacrylate, 3-nonylphenyl methacrylate, 3-decylphenyl methacrylate, 3-decylphenyl methacrylate Dodecylphenyl ester, 3-hexadecylphenyl methacrylate, 3-octadecylphenyl methacrylate, 3-butoxyphenyl acrylate, 3-pentyloxy acrylate Phenyl ester, 3-hexyloxyphenyl acrylate, 3-heptyloxyphenyl acrylate, 3-octyloxyphenyl acrylate, 3-nonyloxyphenyl acrylate, 3-decyloxy acrylate Phenyl ester, 3-dodecyloxyphenyl acrylate, 3-hexadecyloxyphenyl acrylate, 3-octadecyloxy acrylate, 3-butoxyphenyl methacrylate, Methacrylic acid 3 _pentyloxyphenyl ester, methacrylic acid 3-hexyloxyphenyl ester, methacrylic acid- 3-heptyloxyphenyl ester, 3-octyloxyphenyl methacrylate, 3-nonyloxyphenyl methacrylate, 3-decyloxyphenyl methacrylate, methyl-12-200521578 . 3-Dodecyloxyphenyl acrylate, 3-hexadecyloxyphenyl methacrylate, 3-octadecyloxyphenyl methacrylate, 3-butylcyclohexyl acrylate , 3-pentylcyclohexyl acrylate, 3-hexylcyclohexyl acrylate, 3-heptylcyclohexyl acrylate, 3-octylcyclohexyl acrylate, 3-nonylcyclohexyl acrylate, 3-decylcyclohexyl acrylate, 3-dodecylcyclohexyl acrylate, 3-hexadecylcyclohexyl acrylate, 3-octadecylcyclohexyl acrylate, methacrylic acid- 3-butylcyclohexyl, 3-pentylcyclohexyl methacrylate, 3-hexylcyclohexyl methacrylate, 3-heptylcyclohexyl methacrylate, 3-octyl methacrylate Cyclohexyl, 3-nonylcyclohexyl methacrylate, 3-decylcyclohexyl methacrylate, 3-dodecylcyclohexyl methacrylate, 3-methacrylic acid Hexylcyclohexyl, 3-octadecylcyclohexyl methacrylate, 3-butoxyacrylic acid Hexyl ester, 3-pentyloxycyclohexyl acrylate, 3-hexyloxycyclohexyl acrylate, 3-heptyloxycyclohexyl acrylate, acrylic acid-3, octyloxycyclohexyl acrylate, acrylic acid-3 -Nonoxycyclohexyl, 3-decoxycyclohexyl acrylate, 3-dodecyloxycyclohexyl acrylate, 3-hexadecyloxycyclohexyl acrylate, 3-decayl acrylate Octadecylcyclohexyl methacrylate, 3-butoxycyclohexyl methacrylate, 3-pentyloxycyclohexyl methacrylate, 3-hexyloxycyclohexyl methacrylate, methacrylic acid -3-heptyloxycyclohexyl methacrylate, -3-octyloxycyclohexyl methacrylate, -3-nonyloxycyclohexyl methacrylate, -3-decyloxycyclohexyl methacrylate, methyl 3-dodecyloxycyclohexyl acrylate, 3-hexadecyloxycyclohexyl acrylate, 3-octadecylcyclohexyl methacrylate, 4- · butyl acrylate Phenyl phenate, 4-pentyl phenyl acrylate, 4-hexyl phenyl acrylate, 4-heptyl phenyl acrylate, 4-octyl phenyl acrylate, 4-nonyl phenyl acrylate, acrylic acid- 4-decylphenyl ester, 4-dodecylphenyl acrylate, acrylic acid-13- 200521578 -4- Hexaalkylphenyl ester, 4-octadecylphenyl acrylate, 4-butylphenyl methacrylate, 4-pentylphenyl methacrylate, 4-hexylphenyl methacrylate, methyl 4-heptylphenyl methacrylate, 4-octylphenyl methacrylate, 4-nonylphenyl methacrylate, 4-decylphenyl methacrylate, 4-decyl methacrylate Dialkyl phenyl ester, 4-hexadecyl phenyl methacrylate, 4-octadecyl phenyl methacrylate, 4-butoxyphenyl acrylate, 4-pentyloxy acrylate Ester, 4-hexyloxyphenyl acrylate, 4-heptyloxyphenyl acrylate, 4-octyloxyphenyl acrylate, 4-nonyloxyphenyl acrylate, 4-decyloxybenzene acrylate Ester, 4-dodecyloxyphenyl acrylate, 4-hexadecyloxyphenyl acrylate, 4-octadecyloxy acrylate, 4-butanylphenyl methacrylate, methyl 4-pentyloxyphenyl methacrylate, 4-hexyloxyphenyl methacrylate, 4-heptyloxyphenyl methacrylate, 4-octyloxyphenyl methacrylate, methacrylic acid -4-nonyloxyphenyl ester, methacrylic acid 4-decyloxyphenyl ester, methacrylic acid-4- Dialkoxyphenyl ester, 4-hexadecyloxyphenyl methacrylate, 4-octadecyloxyphenyl methacrylate, 4-butylcyclohexyl acrylate, 4-pentyl acrylate Cyclohexyl acrylate, 4-hexyl cyclohexyl acrylate, 4-heptyl cyclohexyl acrylate, 4-octyl cyclohexyl acrylate, 4-nonyl cyclohexyl acrylate, 4-decyl acrylate Cyclohexyl, 4-dodecylcyclohexyl acrylate, 4-hexadecylcyclohexyl acrylate, stearylcyclohexyl acrylate, 4-butylcyclohexyl methacrylate, methyl P-enoic acid-4-pentylcyclohexyl, 4-hexylcyclohexyl methacrylate, 4-heptylcyclohexyl methacrylate, 4-octylcyclohexyl methacrylate, methyl Acrylic-nonyl cyclohexyl acrylate, 4-decyl cyclohexyl methacrylate, 4-dodecyl cyclohexyl methacrylate, 4-hexadecyl cyclohexyl methacrylate, methyl 4-octadecylcyclohexyl acrylate, 4- \ -14- 200521578 butoxycyclohexyl acrylate, 4-pentyloxy cyclohexyl acrylate, 4-hexyloxy cyclohexyl acrylate , 4-heptyloxycyclohexyl acrylate, 4-octyloxycyclohexyl acrylate, propylene -4-nonyloxycyclohexyl, 4-decyloxycyclohexyl acrylate, 4-dodecyloxycyclohexyl acrylate, 4-hexadecyloxycyclohexyl acrylate, -4 -Octadecylcyclohexyl ester, 4-butoxycyclohexyl methacrylate, 4-pentyloxycyclohexyl methacrylate, 4-hexyloxycyclohexyl methacrylate, methyl 4-heptyloxycyclohexyl methacrylate, 4-octyloxycyclohexyl methacrylate, 4-nonyloxycyclohexyl methacrylate, 4-decylcyclohexyl methacrylate , 4-dodecyloxycyclohexyl methacrylate, 4-hexadecyloxycyclohexyl methacrylate, 4-octadecyloxycyclohexyl methacrylate, acrylic acid-4- (4-butylcyclohexyl) phenyl ester, 4- (4-pentylcyclohexyl) acrylate, 4- (4-hexylcyclohexyl) phenyl acrylate, 4- (4-octylcyclohexyl) acrylate ) Phenyl ester, 4- (4-decylcyclohexyl) phenyl acrylate, 4- (4-dodecylcyclohexyl) phenyl acrylate, 4- (4-hexadecylcyclohexyl) acrylate Phenyl ester, 4- (4-octadecylcyclohexyl) phenyl acrylate, _4_ (4-butylcyclohexyl) methacrylate Ester, 4- (4-pentylcyclohexyl) phenyl methacrylate, 4- (4-hexylcyclohexyl) phenyl methacrylate, 4- (4-octylcyclohexyl) benzene methacrylate Ester, 4- (4-decylcyclohexyl) phenyl methacrylate, 4- (4-dodecylcyclohexyl) phenyl methacrylate, 4- (4-hexadecane) methacrylate Cyclohexyl) phenyl ester, 4- (4-octadecylcyclohexyl) phenyl methacrylate, 4- (4-butylcyclohexyl) cyclohexyl acrylate, 4- (4-pentyl ring acrylate Hexyl) cyclohexyl, 4- (4-hexylcyclohexyl) cyclohexyl acrylate, 4- (4-octylcyclohexyl) cyclohexyl acrylate, 4- (4-decylcyclohexyl) acrylate Hexyl ester, 4- (4-dodecylcyclohexyl-15-200521578. Acrylic) cyclohexyl acrylate, 4- (4-hexadecylcyclohexyl) cyclohexyl acrylate, 4- ( 4-octadecylcyclohexyl) cyclohexyl, 4- (4-butylcyclohexyl) cyclohexyl methacrylate, 4- (4-pentylcyclohexyl) cyclohexyl methacrylate, methyl Acrylic acid-4- (4-hexylcyclohexyl) cyclohexyl, methacrylic acid-4- (4-octylcyclohexyl) cyclohexyl, methacrylic acid -4- (4-decylcyclohexyl) cyclohexyl, methacrylic acid 4- (4-dodecylcyclohexyl) cyclohexyl, methacrylic acid 4- (4-hexadecylcyclohexyl) ) Cyclohexyl, 4- (4-octadecylcyclohexyl) cyclohexyl methacrylate, cholesterol acrylate, cholesterol methacrylate, cholesteryl acrylate, cholesteryl methacrylate, acrylic acid 3-dehydrorosinoxy-hydroxypropyl ester and 3-dehydrorosinoxy-hydroxypropyl methacrylate are preferred compounds. Among these compounds, 4-butylphenyl acrylate, 4-pentylphenyl acrylate, 4-hexylphenyl acrylate, 4-heptylphenyl acrylate, and 4-octylphenyl acrylate , 4-nonylphenyl acrylate, 4-decylphenyl acrylate, 4-dodecylphenyl acrylate, 4-hexadecylphenyl acrylate, 4-octadecylbenzene acrylate Ester, 4-butylphenyl methacrylate, 4-pentylphenyl methacrylate, 4-hexylphenyl methacrylate, 4-heptylphenyl methacrylate, 4-methacrylic acid-4 -Octylphenyl ester, 4-nonylphenyl methacrylate, 4-decylphenyl methacrylate, 4-dodecylphenyl methacrylate, hexadecyl methacrylate Phenyl ester, 4-octadecylphenyl methacrylate, 4-butoxyphenyl acrylate, 4-pentyloxyphenyl acrylate, 4-hexyloxyphenyl acrylate, 4_ Heptyloxyphenyl ester, 4-octyloxyphenyl acrylate, 4-nonyloxyphenyl acrylate, 4-decyloxyphenyl acrylate, 4-dodecyloxyphenyl acrylate, acrylic acid- 4-hexadecyloxyphenyl ester, 4-octadecyloxy-16-2005215 78 Phenyl ester, 4-butoxyphenyl methacrylate, 4-pentoxyphenyl methacrylate, 4-hexyloxyphenyl methacrylate, 4-heptyloxy methacrylate Ester, 4-octyloxyphenyl methacrylate, 4-nonyloxyphenyl methacrylate, 4-decyloxyphenyl methacrylate, 4-dodecyloxybenzene methacrylate Ester, 4-hexadecyloxyphenyl methacrylate, 4-octadecyloxyphenyl methacrylate, 4-butylcyclohexyl acrylate, 4-pentylcyclohexyl acrylate, 4-hexylcyclohexyl acrylate, 4-heptylcyclohexyl acrylate, 4-octylcyclohexyl acrylate, 4-nonylcyclohexyl acrylate, 4-decylcyclohexyl acrylate, acrylic acid 4-dodecylcyclohexyl, 4-hexadecylcyclohexyl acrylate, 4-octadecylcyclohexyl acrylate, 4-butylcyclohexyl methacrylate, methacrylic acid 4-pentylcyclohexyl, 4-hexylcyclohexyl methacrylate, 4-heptylcyclohexyl methacrylate, 4-octylcyclohexyl methacrylate, methacrylic acid-4- Nonylcyclohexyl, 4-decylcyclohexyl methacrylate, 4-dodecane methacrylate Cyclohexyl, 4-hexadecylcyclohexyl methacrylate, 4-octadecylcyclohexyl methacrylate, 4-butoxycyclohexyl acrylate, 4-pentyloxy acrylate Cyclohexyl, 4-hexyloxycyclohexyl acrylate, 4-heptyloxycyclohexyl acrylate, 4-octyloxycyclohexyl acrylate, 4-nonyloxycyclohexyl acrylate, acrylic acid- 4-decyloxycyclohexyl, 4-dodecyloxycyclohexyl acrylate, 4-hexadecyloxycyclohexyl acrylate, 4-octadecyloxycyclohexyl acrylate, methyl 4-butoxycyclohexyl acrylate, 4-pentyloxycyclohexyl methacrylate, 4-hexyloxycyclohexyl methacrylate, 4-heptyloxycyclohexyl methacrylate, 4-octyloxycyclohexyl methacrylate, 4-nonyloxycyclohexyl methacrylate, 4-decylcyclohexyl methacrylate, 4-dodecyl methacrylate Cyclohexyl, 4-Hexadecyloxycyclohexyl methacrylate, Methyl Prop-17-200521578 enoic acid 4-octadecylcyclohexyl ester, 4- (4-butyl ring acrylic acid) Hexyl) phenyl ester, 4- (4-pentylcyclohexyl) phenyl acrylate, 4- (4-hexylcyclohexyl) acrylate Phenyl ester, 4- (4-octylcyclohexyl) phenyl acrylate, 4- (4-decylcyclohexyl) phenyl acrylate, 4- (4-dodecylcyclohexyl) phenyl acrylate, 4- (4-hexadecylcyclohexyl) phenyl acrylate, 4- (4-octadecylcyclohexyl) phenyl acrylate, 4- (4-butylcyclohexyl) phenyl methacrylate, 4- (4-pentylcyclohexyl) phenyl methacrylate, 4- (4-hexylcyclohexyl) phenyl methacrylate, 4- (4-octylcyclohexyl) phenyl methacrylate, 4- (4-Decylcyclohexyl) phenyl methacrylate, 4- (4-dodecylcyclohexyl) phenyl methacrylate, 4- (4-hexadecyl ring methacrylate) Hexyl) phenyl ester, 4- (4-octadecylcyclohexyl) phenyl methacrylate, 4- (4-butylcyclohexyl) cyclohexyl acrylate, 4- (4-pentyl ring acrylate) Hexyl) cyclohexyl, 4- (4-hexylcyclohexyl) cyclohexyl acrylate, 4- (4-octylcyclohexyl) cyclohexyl acrylate, 4- (4-decylcyclohexyl) ring acrylic Hexyl ester, 4- (4-dodecylcyclohexyl) cyclohexyl acrylate, 4- (4-hexadecylcyclohexyl) cyclohexyl acrylate, -4 -(4-octadecylcyclohexyl) cyclohexyl, 4- (4-butylcyclohexyl) cyclohexyl methacrylate, 4- (4-pentylcyclohexyl) cyclohexyl methacrylate , 4- (4-hexylcyclohexyl) cyclohexyl methacrylate, 4- (4-octylcyclohexyl) cyclohexyl methacrylate, 4- (4-decylcyclohexyl) methacrylate Cyclohexyl, 4- (4-dodecylcyclohexyl) cyclohexyl methacrylate, 4- (4-hexadecylcyclohexyl) cyclohexyl methacrylate, 4-methacrylic acid-4- (4-octadecylcyclohexyl) cyclohexyl, cholesterol acrylate, cholesterol methacrylate, cholesterol acrylate, and cholesterol methacrylate are more preferred. -18- 200521578 A specific compound, for example, a compound in which Y2 is an ester bond in the general formula (1), is obtained by reacting an alcohol or a halide having a hydrophobic group with (meth) acrylic acid or a derivative thereof. [Alcohol] Examples of the alcohol having a hydrophobic group include alkyl alcohols, cyclic aliphatic alcohols, and aromatic alcohols. The alkyl group, cyclic aliphatic group, and aromatic group of these compounds may be replaced by, for example, an alkyl group (other than the above-mentioned alkyl group), a phenyl group, an alkoxy group, a halogen group, and an alkoxycarboxyl group. Related alcohols include, for example, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, cetyl alcohol, stearyl alcohol, cyclohexanol, methylcyclohexanol, and ethyl alcohol. Cyclohexanol, hexylhexanol, bicyclohexanol, decahydro-2-naphthol, cholesterol, cholanganol, phenol, cresol, ethylphenol, butylphenol, hexylphenol, octylphenol, nonanylcyclohexyl Phenol, (ethylcyclohexyl) phenol, (propylcyclohexyl) phenol, (butylcyclohexyl) phenol, (pentylcyclohexyl) phenol, (hexylcyclohexyl) phenol, (octylcyclohexyl) phenol, biphenyl Cyclohexylphenol, (ethylcyclohexyl) cyclohexanol, (propylcyclohexyl) cyclohexanol, (butylcyclohexyl) cyclohexanol, (pentylcyclohexyl) cyclohexanol, (hexylcyclohexyl) ring Hexanol, (octylcyclohexyl) cyclohexanol, 4-n-hexanol, 4-n-heptanol, 4-n-octanol, 4-n-hexyl alcohol, 4-n-heptyl alcohol, 4-n-octyl alcohol, 4-Third-butylphenol, trifluorocresol, 4-fluorophenol, 2,5-difluorophenol, hydroxybiphenol and naphthol are preferred. [Halogenated alkyl] Halides are compounds in which a hydroxyl atom of the above-mentioned alcohol is substituted by a halogen '. Examples of the halogen compounds include chloride, bromide, and iodide. Examples of the alkyl group in the case where the halide is a halogenated alkyl group include hexyl, heptyl, octyl, nonyl, decyl, dodecanyl, hexadecyl, and octadecyl. The bases are straight -19- 200521578. The chain or branch can be substituted by alkoxy. [Synthesis of (meth) acrylic acid ester] (meth) acrylic acid or a derivative thereof provided in a synthetic reaction of (meth) acrylic acid, and the use ratio of the (meth) acrylic acid or its derivative with the alcohol is based on 1 equivalent of the hydroxyl group contained in the alcohol. The ratio of 1 to 2 equivalents of acrylic acid or its derivative is more preferred, and the ratio of 1 to 1 to 5 equivalents is more preferred. Examples of (meth) acrylic acid derivatives include (meth) acrylic acid, alkali metal salts of (meth) acrylic acid, and halogenated (meth) acrylic acid. In the synthesis of (meth) acrylic acid esters, ordinary esterification reactions can be used. For example, a method of dehydrating and condensing a carboxylic acid with an alcohol using an acid catalyst or an alkali catalyst, a reaction of a carboxylic acid halide with an alcohol, and a carboxylic acid can be used. Reaction of acid and alkali metal salt with alkyl halide. The reaction is carried out at a temperature of -20 to 150 ° C, and preferably at a temperature of 0 to 100 ° C. The reaction solvent is not particularly limited as long as it can dissolve the synthesized (meth) acrylates and starting materials other than alcohols or 1,2-amines. Examples include diethyl ether, tetrahydrofuran, dichloromethane, and 12 -Dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, acetone, methyl ethyl ketone , Methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N- Methyl-2-tetrahydropyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylamidine, 7-butyrolactone. The amount of the organic solvent to be used is preferably such that the alcohol as a starting material is from 0.1 to 20% by weight based on the total amount of the reaction solution (the total amount of the organic solvent and the alcohol used). -20- 200521578 Among them, in order to prevent polymerization during the reaction, a polymerization inhibitor may be added to the reaction system in a range that does not hinder the reaction. Specific examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, aluminum N-nitrophenylhydrogenamine salt, p-tert-butylcatechol, 2,4-dinitrophenol, and the like. As described above, a crude product of (meth) acrylate was obtained. Then, the reaction product can be purified by recrystallization, distillation, chromatography, or the like. [Meth) acrylate having a plurality of (meth) acrylic groups] In the present invention, the specific compound is copolymerized with the specific compound so long as the alignment is not impaired. It is also possible to use (meth) acrylates having a plurality of (meth) acrylic groups together. Related (meth) acrylates include, for example, diacrylates or dimethacrylates of alkyl glycols such as ethylene glycol and propylene glycol; and dialkyl diols of polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Acrylate or dimethacrylate; such as trimethylolpropyldiacrylate, monohydroxydiacrylate or monohydroxyoligomeric methacrylate of trimethylolpropyldimethacrylate, and Dicarboxylic acid, succinic acid, glutaric acid dicarboxylic acid containing free carboxy monoesters; such as propane-1,2,3-tricarboxylic acid (tricarboxylic acid), butan-1,2,4-tricarboxylic acid Acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid tricarboxylic acid, and acrylic acid such as 2-hydroxyethyl Oligomers containing free carboxyl esters, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, or monohydroxy monomethacrylate Esters; such as polyester, epoxy resin, urethane resin, alkyd resin, polysiloxane resin, oligopolyacrylate or oligomethacrylate; Di- or dimethacrylate of two-terminal hydroxylated polymer of terminal hydroxyl poly 1,3-butadiene, two-terminal hydroxyl polyiso-21-200521578 butene, two-terminal hydroxyl polycaprolactone, and three (2-propenyloxyethyl) phosphate, tris (2-methylnitroxyethyl) phosphate, and the like. [Other polymerizable compounds] Compounds having ethylenically unsaturated double bonds other than (meth) acrylic compounds can be used to the extent that the effects of the present invention are not impaired. Examples of usable compounds include cis-butenimide-based compounds and styrene-based compounds. [Laminated Alignment Film, Method for Manufacturing the Alignment Film, and Liquid Crystal Display Element Using the Same] The laminated alignment film of the present invention and a liquid crystal display element obtained by using the alignment film can be manufactured by, for example, the following method. On one or both sides of the substrate provided with the patterned transparent conductive film, a protrusion-like structure formed of an organic material is formed. When a protruding structure is formed only on one side of the substrate, the conductive film on the other side of the substrate must have a slit-like pattern. When no protruding structure is formed, the transparent conductive film on both sides of the substrate may be formed into a slit-like pattern. The organic material constituting the protruding structure is preferably a pattern-formable material, and from this viewpoint, a photoresist material is more preferable. Furthermore, when a positive photoresist is used, it is easy to control the shape of the protruding structure, and it is also preferable from the viewpoint of alignment control. Examples of the positive photoresist to be used include phenol resins and acrylic resins. As the substrate, for example, a transparent substrate composed of glass such as float glass' soda glass, and plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, and polycarbonate can be used. As for the transparent conductive film provided on one side of the -22-200521578 substrate, for example, a NESA film (registered trademark of PPG, USA) made of tin oxide (Sn02), and indium oxide-tin oxide (In203-Sn02) can be used. The structure of the ITO film. In the patterning of these transparent conductive films, a method such as photolithography or a mask is used in advance. A liquid crystal alignment agent for forming a normal liquid crystal alignment film is applied to a functional substrate on which protrusions are formed by a method such as a roll coating method, a spin coater method, or a printing method. Next, a coating film is formed by heating a coating surface. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a compound containing a functional silane and a compound containing a functional titanium may be coated on the surface of the substrate in advance. Compounds etc. The heating temperature after the liquid crystal alignment agent is applied is preferably 80 to 300 ° C, and more preferably 120 to 250 ° C. In addition, the liquid crystal alignment agent containing polyamic acid is a coating film formed as an alignment film by removing an organic solvent after coating, and may be dehydrated and closed by further heating to form an imidized aminated coating film. . The first film thickness of the first layer formed is as described above. As described above, two functional substrates on which the first layer has been formed are made, and they are arranged to face each other through a gap (element jig), and a peripheral portion of the two substrates is bonded with a sealant. As the sealant, for example, an epoxy resin containing a thermosetting agent or a photosensitive curing agent and an alumina ball as a spacer can be used. Liquid crystal and specific compounds are injected into the substrate and the component jig divided by the sealant, and (meth) acrylate having a plurality of (meth) acrylic groups is further injected and filled according to the situation, and the injection hole is sealed to form a liquid crystal element. Examples of usable liquid crystals include nematic liquid crystals and butterfly liquid crystals. -23- 200521578 Among them, nematic liquid crystals are particularly preferred. For example, Schiff base liquid crystals, azo oxide liquid crystals, biphenyl liquid crystals, phenylcyclohexyl liquid crystals, ester liquid crystals, and terphenylene liquid crystals can be used. Liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, Q-pane liquid crystals, and the like. In addition, to these liquid crystals, for example, cholesterol-type liquid crystals such as cholesterol chloride, cholesterol nonanoate, and cholesterol carbonate may be added, or, for example, under the trade names "C-15" and "CB-15" (manufactured by Merkel Corporation). ) For sale, use Keilal ear preparations. Furthermore, strong dielectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamic acid can also be used. _ After mixing a specific compound and liquid crystal, and injecting into a liquid crystal display element, a liquid crystal display element is irradiated with radiation to form a second film which is a second layer on the first layer. The concentration of the compound having an unsaturated double bond group in the liquid crystal is, for example, 10% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less. When the concentration exceeds 10% by weight, it is difficult to obtain a good picture due to scattering of transmitted light. For the polymerization of a specific compound, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron rays, and X-rays can be used. Radiation having a wavelength in the range of i 50 nm to 800 nm is preferable, and radiation having a wavelength of 240 nm to 500 nm is particularly preferable. As the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a heavy hydrogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, a laser laser, and the like can be used. The exposure amount is preferably from 0.01 to 50 J / CH12, and more preferably from 0.1 to 20 J / cm2. In addition, it is preferable to perform exposure at the temperature of the liquid crystal phase of the liquid crystal display used. -24- 200521578 Then, on the outer surface of the liquid crystal element, that is, on the other side of each substrate constituting the liquid crystal element, a polarizing plate is bonded so that the polarization directions are perpendicular to each other to obtain a liquid crystal display element. Examples of the polarizing plate attached to the outer surface of the liquid crystal element include a polarizing plate having stretched alignment polyvinyl alcohol and a protective film of cellulose acetate sandwiched with a so-called iodine-absorbing film, or a polarizing film. The polarizing plate formed by the film itself. Hereinafter, the present invention will be described more specifically by examples, but the present invention is not limited by these examples. The measurement methods and evaluation methods for the liquid crystal display elements produced by the following examples and comparative examples are as follows. [Film thickness of the second layer of the laminated alignment film] After disassembling the liquid crystal display element and removing the liquid crystal with acetone, the alignment film was scratched with a doctor blade to expose the surface of the substrate, and the resulting layer was measured by a contact-type film thickness meter. The gap is used to measure the film thickness of the laminated alignment film (the film thickness of the first layer is 800A). The film thickness (A) of the second layer from the specific compound is calculated by the following formula. (Second layer film thickness) = (film thickness of laminated alignment film) -8 00 [Liquid crystal alignment] Observe the presence or absence of abnormal magnetic domains when the on / off voltage is applied to the liquid crystal display element with a polarizing microscope to determine that there is no abnormality The condition of the magnetic domain was "good". [Voltage holding ratio] When applied to a liquid crystal display device at a voltage of 5 V at room temperature, an application time of 60 microseconds, and an interval of 16, 7 milliseconds, the voltage was measured from 5 V using VHR-1 manufactured by Toyo Technology Co., Ltd. After the application is released to the holding voltage of 16.7 milliseconds, 200521578 obtains the voltage holding rate. [Residual DC] A rectangular wave of 30Hz and 3.0V with 1.0V DC voltage superimposed was applied to the liquid crystal display element at an ambient temperature of 25 ° C for 2 hours, and the residual after cutting off the DC voltage was obtained by the flash elimination method. The voltage in the liquid crystal element is used to determine the residual DC voltage. [Synthesis Example 1] After adding 10 g of cold-cholestanol and 200 mL of dehydrated tetrahydrofuran to a three-necked flask with a 50-mL capacity with a silicone drying tube and stirring, add 35 mg of 2-methoxydihydroquinone and 6 g of triethylamine. , Stir and dissolve at room temperature. 6 g of propylene chloride chloride was dropped into the reaction solution, and the mixture was stirred at room temperature for 2 hours. The reaction solution was washed with a 10% K2C03 aqueous solution, saturated saline, and water in that order, and dried over magnesium sulfate, and then the solvent was distilled off. By recrystallizing the solid obtained with ethanol, 10.5 g of cholesteryl acrylate (hereinafter referred to as "acrylate compound (I)") was obtained in good purity (92% yield). [Synthesis Example 2] In Synthesis Example 1, except that chlorinated methacrylic acid was used instead of chlorinated propylene fluorene, by the same method, the intended cholesteryl methacrylate was obtained in a yield of 93% ( Hereinafter, it is referred to as "methacrylate compound (II)"). [Synthesis Example 3] In Synthesis Example 1, except that cholesterol was used instead of cholestanol, the desired cholesterol acrylate (hereinafter, referred to as "acrylate compound (II)" was obtained by a similar method in 93% yield. ) "). 200521578. '[Synthesis Example 4] In Synthesis Example 1, except using cholesterol and methylpropanyl chloride instead of / 3-cholestanol and propylene chloride, using the same method, at 95% Yields the desired cholesterol methacrylate (hereinafter, referred to as "stomach ^ acrylate compound (IV)"). [Synthesis Example 5] In Synthesis Example 1, except for using 4-hexyloxyphenol instead of $ _biliary < Except for glutamate, by the same method and purification by chromatography, the desired acrylic acid-4hexyloxyphenolate (hereinafter referred to as "propionate" was obtained at 93% yield). ; Compound (V) "). [Synthesis Example 6] In Synthesis Example 5, except that 4-hexyloxyphenol was used instead of 4-hexyloxyphenol, the desired propanoic acid octyloxyphenol was obtained in a yield of 93% by the "R-like method". Ester (hereinafter referred to as "acrylate compound (VI)"). [Synthesis Example 7] In Synthesis Example 5, except that 4- (4-hexylphenyl) phenol was used instead of 4-hexyloxyphenol, the desired acrylic acid-4 was obtained in the same manner in 94% yield. -(4-hexylphenyl) acetic acid (hereinafter referred to as "acrylate compound (VII)"). [Synthesis Example 8] In Synthesis Example 5, except that 4- (4-hexylcyclohexyl) phenol was used instead of hexyloxyphenol, the intended propionic acid-4 was obtained in the same manner in 92% yield. -(4-hexylcyclohexyl) (hereinafter referred to as "acrylic acid compound (VIII)"). -27- 200521578 [Example 1] (1) Preparation of liquid crystal mixture Dissolve 10 mg of acrylate obtained in Synthesis Example 1 and 10 mg of dimethylol-tricyclodecane diacrylate in lg negative liquid crystal MLC-6608 (US (Made by Erke) and become a mixture. (2) Manufacture of liquid crystal alignment agent for first layer formation Dissolve 9.7 g (90 mmol) of p-phenylenediamine and 5.2 g (10 mmol) of 3,5-diamino benzoic acid cholesterol in 200 ml of 1-methyl-2- Tetrahydropyrrolidone, to which 6.78 (3〇1! 1111〇1) 2,3,5-tricarboxycyclopentylacetic dianhydride, 15§ (70mmol) pyromellitic dianhydride were added, and carried out at 60 ° C for 6 Hour response. Then, the reaction solution was poured into 5,000 ml to obtain a white precipitate. By drying it under reduced pressure at room temperature, a white polyamic acid powder having an inherent viscosity (1-methyl-2-tetrahydropyrrolidone, 25 ° C) of 1.0 dl / g was obtained. The polyamic acid powder was dissolved in 1-methyl-2-tetrahydropyrrolidone to obtain a liquid crystal alignment agent having a solid content concentration of 3%. (3) Production of liquid crystal display element: [1] On a transparent conductive film composed of an ITO film provided on one side of a glass substrate with a thickness of 1 mm, apply the liquid crystal alignment produced by (2) by a spin coating method. Agent, and a 800 A dry film thickness coating film was formed by firing at 180 ° C for 1 hour. [2] As described above, two substrates having the first film of the first layer formed thereon, and the outer edge of each substrate was coated with a ring containing alumina balls with a diameter of 5 // m by a silk screen printing method. After the oxyresin-based adhesive, the two substrates are disposed to face each other via a gap to connect the outer edges and the like and are pressed to harden the adhesive. -28- 200521578 [3] Into the component fixture divided by the adhesive on the substrate surface and the outer edge part, inject and fill the nematic liquid crystal "MLC-6608" (Merck) manufactured as above. The mixture is followed by sealing the injection hole with an epoxy-based adhesive to form a liquid crystal element. In this liquid crystal display element, ultraviolet rays including light having a wavelength of 365 nm, 405 nm, and 436 nm were irradiated through a photomask to polymerize a specific compound in the liquid crystal. Then, a polarizing plate is bonded to the outer surface of the liquid crystal element to produce a liquid crystal display element. [4] With respect to the liquid crystal display element produced as described above, the second layer film thickness, vertical alignment, voltage holding ratio, and residual DC voltage were measured. The results are shown in Table 1. [Examples 2 to 8] The liquid crystal mixture was prepared in the same manner as in Example 1 by using the (meth) acrylates (II to VIII) obtained in Synthesis Examples 2 to 8 in accordance with the treatment methods shown in Table 1 below. Next, a liquid crystal display element was produced in the same manner as in Example 1 using each of the liquid crystal display mixtures thus prepared. Each of the produced liquid crystal display elements was evaluated in the same manner as in Example 1. The results are shown in the table. [Comparative Examples 1 to 2] A liquid crystal display device was produced in the same manner as in Example 1 using a liquid crystal that does not include the specific compound in the present invention in accordance with the processing method shown in Table 1 below. For each produced liquid crystal display element, evaluation was performed in the same manner as in Example 1. [Comparative Example 3] Except for a liquid crystal display element, a mixture of a specific compound and liquid crystal was polymerized by light irradiation and injected into the liquid crystal display element. Evaluation was performed in the same manner as in Example 1. The combined results are shown in Table 1. -29- 200521578 Table 1 (Meth) acrylate di (meth) acrylate second film thickness (A) Alignment voltage retention of liquid crystal (%) Residual DC voltage (mV) Example 1 Synthesis example 1 300 Good 99 10 2 Synthesis example 2 Yes 100 Good 99 10 3 Synthesis example 3 Yes 300 Good 99 20 4 Synthesis example 4 Yes 200 Good 99 30 5 Synthesis example 5 Yes 100 Good 99 20 6 Synthesis example 6 Yes 200 Good 99 40 7 Synthesis Example 7 Yes 300 Good 99 20 8 Synthesis Example 8 Yes 300 Good 99 20 Comparative Example 1 / γγΓ No Yes 300 Bad 98 70 2 4τττ TTTF y »\ ν ΛτΤ ΙΙΠ J \\\ 0 Bad 93 320 3 Yes Yes 0 Bad 93 500
【圖式簡單說明】 無0 -30-[Schematic description] None 0 -30-