TW553932B - Material for light-oriented film, light-oriented film and process for producing the same - Google Patents
Material for light-oriented film, light-oriented film and process for producing the same Download PDFInfo
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- TW553932B TW553932B TW90121017A TW90121017A TW553932B TW 553932 B TW553932 B TW 553932B TW 90121017 A TW90121017 A TW 90121017A TW 90121017 A TW90121017 A TW 90121017A TW 553932 B TW553932 B TW 553932B
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- Taiwan
- Prior art keywords
- photo
- alignment
- group
- polymerizable
- maleimide
- Prior art date
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- 239000000463 material Substances 0.000 title claims description 34
- 238000000034 method Methods 0.000 title description 34
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000011907 photodimerization Methods 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- -1 fluorene imine Chemical class 0.000 claims description 37
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- 125000002947 alkylene group Chemical group 0.000 claims description 17
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- 238000006116 polymerization reaction Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
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- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
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- SZKKRCSOSQAJDE-UHFFFAOYSA-N Schradan Chemical group CN(C)P(=O)(N(C)C)OP(=O)(N(C)C)N(C)C SZKKRCSOSQAJDE-UHFFFAOYSA-N 0.000 description 2
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- ISSDFLKUSQAECW-UHFFFAOYSA-N acetic acid;pyrrole-2,5-dione Chemical compound CC(O)=O.O=C1NC(=O)C=C1 ISSDFLKUSQAECW-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
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- 210000002858 crystal cell Anatomy 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical group C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- PTOUKUHRSZKAQU-UHFFFAOYSA-N 2-phenoxy-3-phenylprop-2-enoic acid Chemical compound C=1C=CC=CC=1C=C(C(=O)O)OC1=CC=CC=C1 PTOUKUHRSZKAQU-UHFFFAOYSA-N 0.000 description 1
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- SUYVCIVJBLTQPZ-UHFFFAOYSA-N bis[4-(2-hydroxyethoxy)phenyl]methanone Chemical compound C1=CC(OCCO)=CC=C1C(=O)C1=CC=C(OCCO)C=C1 SUYVCIVJBLTQPZ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- Liquid Crystal (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
553932 五、 發明說明 ( 1 ) [ 技 術 領 域 ] 本 發 明 係有 關 一 種液 晶 顯示元 件所使用 的 光配 向 膜 ， 更 詳 言 之 係有 關 一 種藉 由 光照射 、不 會進 行 積層 、 可使 液 晶 分 子 配 向 之 光 配 向膜 的 形成材料、 由該 材 料所 成 的 光 配 向 膜 、 其 製 法 及使 用該 光 配向膜 之液 晶顯 示 元件 〇 [ 先前技 術 1 於 液 晶 顯 示 裝 置 中， 利 用使液 晶之 分子 配 列狀 態 藉 由 電 場 等 作 用 變 化 > 伴 隨該 變 化顯示 光學 特性 變 化。 多 數 時 候 ， 液 晶 使用 夾 在二張 基板 之間 隙 的狀 態 5 惟 此 處 爲 使 液 晶 分 子 朝 特定 方 向配列 ，在 基板 內 側須 進 行 配 向 處 理 〇 通 常 ， 配 向 處 理 係使 用 在玻璃 等基 板上 設 有聚 醯 亞 胺 等 局 分 子 膜 以布 等 朝一 方 向擦拭 該物 、予 以 積層 的 方 法 Ο 藉 此 接 於 基 板 之 液 晶分 子 的長軸 直接 平行 配 列於 積 層 方 向 〇 例 如 扭 轉 配 列（TN)晶 胞 係在二 張直 交的 偏 光板 間 使 二 張 塗 覆 有 配 向 膜 之 基 板對 向 ，使其 積層 方向 相 互直 交 配 置 且 可 藉 由 光 透 過 率 變化 予 以顯示 〇 然 而 積 層 法 雖 具有 製 造裝置 簡單 的優 點 ，惟 於 製 造 工 程 中 會 有 靜 電 與 塵 埃產 生 的情形 ，故 於配 向 處理 後 必 須 進 行洗 淨 工 程 ， 特別 是近年來大多‘ 使用 TFT 方 式的 液 晶 晶 胞 由 於 靜 電 會 破 壞 基板 上 所設置| 的TFT元 件 ，係 爲 降 低 製 時 之 處 理 性 的 原 因。 另 外，爲 使液 晶顯 示 元件 所 構 成 的 液 晶 分 子 具 有 方 向 性， 因 液晶兀 -3- 件之 方向 會 有顯 示 色 與 對 553932 五、發明說明（2 ) 比變化等視野角之相關性的問題。 改善此點方法之一係分割畫面、在範圍內改變液晶分子 之預傾角（日本特開昭62 - 1 59 1 1 9號）或配向方向（特開昭 63 - 1 06624號公報）的配向分割法。該分割範圍之配向因習 知方法的工程煩雜，不適合實用化。 爲解決該方法時，近年來著重於進行積層之液晶配向控 制技術。該積層之配向技術係進行檢討斜方蒸熔法、lb( 蘭米爾-普羅傑特）膜法、微影術法、光配向法等。換言之 ’使偏光照射於基板上所設置的塗膜上、產生液晶配向性 的光配向法極爲簡便、於配向處理後不須洗淨工程，且藉 由使用微影術等可容易地進行上述配向分割，故盛行硏究 。該光配向法提案有藉由有機分子中具有光配向功能之光 配向基、例如藉由偶氮基等光異性化者、肉桂醯基、香豆 素基、苯丙烯醯苯基等光二聚合法者、藉由二苯甲酮基等 之光交聯或聚醯亞胺樹脂等之光分解者等。 此等利用光異性化、光二聚合或光交聯的光配向膜材料 大多使用塗覆於玻璃等基板上時可得均勻膜之高分子材料 ，上述之光配向性基大多導入該高分子材料之側鏈或主鏈 上。而且，以具有光配向性之主分子，且分散於由高分子 化合物所成的主要化合物。 然而，爲光異性化時由於利用偏光紫外線照射使分子正 反（c 1 s - t r an s )異性化，故於光配向處理後會有光安定性 的問題。另外，爲光分解型時由於進行光配向處理時產生 553932 五、 發明說明 ( 3) - 的 分 解 生 成 物 使液晶受 到 污染，故於處理 後 必 須 洗 淨 基 板 \ 會 失 去 不 須 洗淨光配 向 膜之特徵。此外 大 多 數 使 用 局 分 子 材料 之 光 配向材料 對 溶劑而言溶解性低 會 有 塗 覆 於 基 板 時 可 使 用 溶劑的種 類 有限之問題。 例 如於 W09637807號公報（美國專利第 6001277 號 說 明 書 特 開 平 8 -328005 □ pfe Μ 公報）中揭示，使 用 具 有可光 異 性 化 之 二 色 向 性 的構造單 位 及具有反應性官 能 基 之 樹 脂 的 液 晶 配 向 膜 惟 該材料爲 高 分子化合物，塗 覆 於 基 板 時 可使 用 的 溶 劑 種 類 有限，一 般 而言可使用Ν , Ν - 二 甲 基 乙 醯 胺 或 N- 甲 基 -2 -吡D 各烷酮等· 高 沸點極性溶劑。 此 時 該 材 料 由 於 樹 脂 中 之 反 應性官能 基 的比例低，故交 聯 密 度 低 結 果 由 該 材料所成 的配向膜 之 耐熱性不充分。 爲 解 決 此 等 問題、且 可 製得光配向膜之 液 晶 配 向 能 長 期 間 安 定 性 的 方 法，例如 藉 由偏光照射使加 成 有 具 配 向 性 之 光 配 向 性 基 的 聚合性單 聚 物以熱或光聚合 且 藉 由 偏 光 照 射 予 以 光 配 向 的方法。 然 而多數時候於使 單 聚 物 以 熱 或 光 聚 合 時 必 須 添 加聚合起 始 劑。由於該聚合 起 始 劑 爲 低分 子 化 合 物 即 使 於 光配向膜 硬 化後，經過長時 間 後 在 晶 胞 內 液 晶 層 擴 散 於 聚 合起始劑 且恐怕會使作爲 液 晶 顯 示 元 件 之 特性 例如 電 壓保持率 惡 化的問題。 聚 合 起 始 劑 不需的光 聚 合性基爲聚合性 馬 來 醯 亞 胺 基 〇 該 使 用 具 有 聚 合性馬來 醯 亞胺基之化合物 的 光 配 向 膜 係如 特 開 2000 - 5 3 766號公; 報 (美國專利第62 1 85〇1 -5- 號說明書） 553932 五、發明說明（4) 或專利296 247 3號公報（特開平11-2815號公報、美國專 利第6048928號說明書）揭示。此等光配向膜係爲在聚醯 亞胺之主鏈上加成有具有光配向之官能基作爲側鏈者，惟 此等光配向膜對耐熱性或液晶配向能之長期安定性不充分 〇 【發明之揭示】 本發明所解決的課題係提供一種具有良好液晶顯示元件 特性、例如電壓保持率、且具有良好的配向安定性與對光 或熱而言充分耐久性之液晶顯示元件用光配向膜。 本發明爲解決上述課題提供一種光配向膜用材料，其特 徵爲由在一分子中具有至少1個藉由光二聚合反應而顯現 光配向功能之光配向性基（Photo-alignment moiety)與具 有至少2個聚合性馬來醯亞胺基之聚合性單體所形成。 而且，本發明爲解決上述課題提供一種光配向膜，其係 由在一分子中具有至少1個藉由光二聚合反應而顯現光配 向功能之光配向性基與具有至少2個聚合性馬來醯亞胺基 之聚合性單體所形成，且具有藉由光配向基之光二聚合而 顯現光配向功能與藉由聚合性馬來醯亞胺基聚合產生的交 聯構造。 另外，本發明爲解決上述課題提供一種光配向膜之製法 ，其特徵爲將一分子中具有至少1個藉由光二聚合反應而 顯現光配向功能之光配向性基與具有至少2個聚合性馬來 醯亞胺基之聚合性單體塗覆於基板上，該塗膜上藉由光照 553932 五、 發明說明 ( 5 ) 射 產 生 構 造 單 位 之 光 二 聚 合 反 應 與 聚 合性 馬來 醯 亞 胺 基 之 光 聚 合 反 應 形 成 交 聯 的 局 分 子 膜 且該 高分 子 膜 具 有 光 配 向 功能 〇 此 外 本 發 明 爲 解 決 上 述 三田 題 提 供 一種 光配 向 膜 之 製 法 其特 徵 爲 將 一 分 子 中 具 有 至 少 1 個 藉由 光二 聚 合 反 應 而 顯 現 光 配 向 功 能 之 光 配 向性 基 與 具 有至少 2個 聚 合性 馬 來 醯 亞 胺 基 之 聚 合性 單 體 塗 覆 於 基 板 上 ，該 塗膜 上 藉 由 加 熱 產 生 聚 合 性 馬 來 醯 亞 胺 基 之 熱 聚 合 反 應、 形成 交 聯 的 局 分 子 膜 且 該 筒 分 子 膜 藉 由 光 照 射 產 生 構造 單位 之 光 二 聚 合 反 應 該 高 分 子 膜 具 有光 配 向 功 能 0 而 且 5 本 發 明 爲 解 決 上 述 課 題 提 供 一種 液晶 顯 示 元 件 其 係 於 具 有在 內 側 具 配 向 膜 之 二 張 基 板間 夾住 液 晶 構 造 的 液 晶 顯 示 元 件 中 5 其特 徵 爲 一 分 子 中: 具有至少 1 個 藉 由 光 二 聚 合 反 應 而 顯 現光 配 向 功 能 之 光 配 向性 基與 具 有 至 少 2 個 聚 合性 馬 來 醯 亞 胺 基 之 聚 合 性 單 體 所成 ，具 有 藉 由 光 配 向 基 之 光 二 聚 合所 具 的光 配 向 功 能 與 藉由 聚合性 馬 來 醯 亞 胺 基 聚 合 產 生 的 交 聯 構 造 0 藉 由 使 用 本 發 明 由 馬 來 醯 亞 胺 衍 生 物所成的 光 配 向 膜 用 材料 可 製 得 具 有 良 好 液 晶 顯 示 元 件 特性 、例 如 電 壓 保持 率 、 且 具 有 良 好 的 配 向 安 定 性 與 對 光 或熱 而言 充分 耐 久 性 之 光 配 向 膜 〇 本 發 明 之 光 配 向 膜 用 材料所使 用 的 在一 分子 中 具 有 至 少 1 個 藉 由 光 二 聚 合 反 /vULiN 而 顯 現 -7. 光 配 向 功能 之光 配 向 性 基 與 553932 五、發明說明（6) 具有至少2個聚合性馬來醯亞胺基之聚合性單體中，藉由 光二聚合反應而顯現光配向功能之光配向性基係爲藉由照 射偏光、可得二聚合配向性之產生光反應的官能基即可， 沒有特別限制，惟其中以使用具有至少一個C = C、C = 0所 示雙鍵（惟除形成芳香環之雙鍵外）之構造單位較佳。 藉由此等二聚合反應而顯現光配向性功能之光配向性基 的基本構造例如下述者。 藉由具有C = C鍵之二聚合反應而顯現光配向性功能之光 配向性基例如具有聚烯基、二苯乙烯基、二苯乙烯唑基、 苯乙基哌錠基、肉桂醯基、半硫靛藍基、苯丙烯醯苯基等 構造之基。藉由具有C = 0鍵之二聚合反應而顯現光配向性 功能之光配向性基例如具有二苯甲酮基、香豆素基等構造 之基。 具體而言，例如具有下述構造之基。當然，在此等構造 中亦可具有烷基、烷氧基、芳基、芳氧基、醯基、烷氧基 羰基、羥基、磺酸基、鹵化烷基等之取代基。553932 V. Description of the Invention (1) [Technical Field] The present invention relates to a light alignment film used in a liquid crystal display element, and more specifically to a light alignment film that can align liquid crystal molecules by light irradiation without lamination. Material for forming photo-alignment film, photo-alignment film made of the material, manufacturing method thereof, and liquid crystal display element using the photo-alignment film 0 [Prior art 1 In a liquid crystal display device, the state of alignment of molecules of liquid crystals is passed through an electric field Equal effect change> A change in the optical characteristics is shown in accordance with the change. In most cases, liquid crystals are sandwiched between two substrates. 5 However, in order to align the liquid crystal molecules in a specific direction, alignment processing must be performed on the inside of the substrate. Generally, alignment processing is performed on a substrate such as glass. A method for laminating a molecular film such as imine with cloth or the like in one direction and laminating it. 0 The long axis of the liquid crystal molecules connected to the substrate is aligned directly in parallel with the lamination direction. For example, the twisted alignment (TN) cell system is in two sheets. Between two orthogonal polarizing plates, two substrates coated with an alignment film are opposed to each other, so that their lamination directions are arranged perpendicular to each other and can be displayed by the change in light transmittance. However, although the lamination method has the advantages of simple manufacturing equipment, it is only for manufacturing. There may be static electricity and dust in the process, so after the alignment process, a cleaning process must be performed, especially in recent years. Jingjing cell set by the static electricity would destroy the substrate | a TFT element, due to processing of the original based upon the system is reduced. In addition, in order to make the liquid crystal display element composed of the liquid crystal display element has a directional, because the direction of the liquid crystal may have a display color and the angle of view and other aspects of the 553932 V. invention description (2) ratio changes. One of the methods to improve this point is to divide the screen, change the pretilt angle of the liquid crystal molecules within the range (Japanese Patent Application Laid-Open No. 62-1 59 1 1 9) or the alignment direction (Japanese Patent Application Laid-Open No. 63-1 06624). law. The orientation of this divided range is not suitable for practical use due to the complicated engineering of the conventional method. In order to solve this method, in recent years, emphasis has been placed on a liquid crystal alignment control technology for lamination. The layered alignment technology is reviewed by the orthorhombic evaporation method, the lb (Ramir-Progett) film method, the lithography method, and the photo-alignment method. In other words, 'the light alignment method that makes polarized light irradiate a coating film provided on a substrate to generate liquid crystal alignment is extremely simple, does not require a cleaning process after alignment processing, and can easily perform the above-mentioned alignment by using lithography etc. Divide, so popular research. This photo-alignment method proposal includes a photo-dimerization method using a photo-alignment group having a photo-alignment function in an organic molecule, for example, a photo-anisolator such as an azo group, a cinnamyl group, a coumarin group, and a phenylpropenyl phenyl group. , Photocrosslinking by benzophenone group, etc., or photodecomposition by polyimide resin, etc. These photo-alignment film materials using photo-anisotropy, photo-dimerization, or photo-crosslinking are mostly polymer materials that can obtain a uniform film when coated on a substrate such as glass. Most of the above-mentioned photo-alignment groups are introduced into the polymer material. Side chain or main chain. In addition, a main molecule having photo-alignment is dispersed in a main compound made of a polymer compound. However, in the case of photo-anisotropy, because the molecules are anisotropy (c 1 s-t r an s) with polarized ultraviolet radiation, there is a problem of light stability after the photo-alignment treatment. In addition, in the case of photodecomposition type, 553932 is generated when performing photo-alignment treatment. 5. Description of the invention (3)-The liquid crystal is contaminated by the decomposition product, so the substrate must be cleaned after processing. The photo-alignment film will be lost without cleaning. Characteristics. In addition, most of the photo-alignment materials that use local molecular materials have low solubility in solvents, which may have limited problems in the types of solvents that can be used when coating substrates. For example, disclosed in W09637807 (U.S. Patent No. 6001277, Japanese Unexamined Patent Application Publication No. Hei 8-328005 □ pfe M), liquid crystal alignment using a structural unit having photoisotropic dichroism and a resin having a reactive functional group is disclosed. Membrane, but this material is a polymer compound, and the types of solvents that can be used when coating on the substrate are limited. Generally speaking, N, N-dimethylacetamide or N-methyl-2 -pyridine, etc. · High boiling point polar solvents. At this time, the material has a low proportion of the reactive functional groups in the resin, so the crosslink density is low. As a result, the alignment film made of the material has insufficient heat resistance. In order to solve these problems, and a method for preparing liquid crystal alignment energy of a photo-alignment film for a long period of time, for example, by polarizing light, a polymerizable monopolymer added with a photo-alignment group having alignment properties can be thermally or A method of photopolymerization and photoalignment by polarized light irradiation. However, in most cases, a polymerization initiator must be added when the monomer is polymerized by heat or light. Since the polymerization initiator is a low-molecular compound, even after the photo-alignment film is hardened, the liquid crystal layer diffuses into the polymerization initiator in the unit cell after a long period of time, and the characteristics such as the voltage retention of the liquid crystal display element may be deteriorated. problem. The photopolymerizable group not required for the polymerization initiator is a polymerizable maleimide group. The photo-alignment film system using a compound having a polymerizable maleimide group is, for example, JP 2000-5 3 766; (U.S. Patent No. 62 1 85〇1 -5-) 553932 V. Description of Invention (4) or Patent Publication No. 296 247 3 (Japanese Patent Application Laid-Open No. 11-2815, US Patent No. 6048928). These photo-alignment films are those in which a functional group having photo-alignment is added to the main chain of polyimide as a side chain, but these photo-alignment films have insufficient long-term stability to heat resistance or liquid crystal alignment. [Disclosure of the Invention] The problem to be solved by the present invention is to provide a light alignment for a liquid crystal display element which has good liquid crystal display element characteristics, such as voltage retention, and has good alignment stability and sufficient durability against light or heat. membrane. The present invention provides a photo-alignment film material for solving the above-mentioned problems, which is characterized by having at least one photo-alignment moiety (Photo-alignment moiety) in a molecule that exhibits a photo-alignment function through photo-dimerization reaction and at least one photo-alignment moiety. Two polymerizable maleimide imide-based polymerizable monomers. In addition, the present invention provides a photo-alignment film for solving the above-mentioned problems. The photo-alignment film comprises at least one photo-alignment group in a molecule that exhibits a photo-alignment function through a photo-dimerization reaction and at least two polymerizable malays. It is formed by a polymerizable monomer of an imine group, and has a photo-alignment function by photo-dimerization of a photo-alignment group and a cross-linked structure generated by polymerization of a polymerizable maleimide imide group. In addition, the present invention provides a method for manufacturing a photo-alignment film for solving the above-mentioned problems, which is characterized in that at least one photo-alignment group in a molecule exhibiting a photo-alignment function through photo-dimerization reaction and at least two polymerizable horses are provided. The polymerizable monomer of lyme imine is coated on the substrate, and the coating film is illuminated by light 553932. V. Description of the invention (5) The photodimerization reaction that generates structural units and the light of polymerizable maleimide The polymerization reaction forms a cross-linked local molecular film and the polymer film has a photo-alignment function. In addition, the present invention provides a method for manufacturing a photo-alignment film to solve the above-mentioned Mita problem, which is characterized in that at least one of A photo-alignment group exhibiting a photo-alignment function and a polymerizable monomer having at least two polymerizable maleimide imide groups are coated on a substrate, and the coating film generates a polymerizable maleimide imide group by heating. Thermal polymerization reaction, forming a crosslinked local molecular film, and the tube molecular film generating photodimerization reaction of structural units by light irradiation. The polymer film has a photo-alignment function. 0 and 5 The present invention provides a liquid crystal display element for solving the above-mentioned problems. It is in a liquid crystal display element having a liquid crystal structure sandwiched between two substrates with an alignment film on the inside. 5 It is characterized in one molecule: it has at least one photo-alignment group that exhibits a photo-alignment function through photo-dimerization reaction. It is formed with a polymerizable monomer having at least two polymerizable maleimide imine groups, has a photo-alignment function by photodimerization of a photo-alignment group, and is produced by polymerizable maleimide imide group polymerization. Crosslinked structure 0 By using the material for a photo-alignment film formed from a maleimide imide derivative of the present invention, a good liquid crystal display element can be obtained. Photo-alignment film with characteristics such as voltage retention, good alignment stability, and sufficient durability against light or heat. The material used for the photo-alignment film of the present invention has at least one borrow in one molecule. Revealed by photodimerization inverse / vULiN-7. Photoalignment group with photoalignment function and 553932 V. Description of the invention (6) Among photopolymerizable monomers having at least two polymerizable maleimide imide groups, photodimer The photo-alignment group that exhibits the function of photo-alignment by polymerization reaction may be a functional group that generates a photo-reaction with dimerization alignment by irradiating polarized light, and is not particularly limited, but among them, at least one C = C, The structural unit of the double bond shown by C = 0 (except for the double bond forming the aromatic ring) is better. The basic structure of a photo-alignment group that exhibits a photo-alignment function by such a dimerization reaction is, for example, the following. A photo-alignment group exhibiting a photo-alignment function by a dimerization reaction having a C = C bond, for example, has a polyalkenyl group, a distyryl group, a stilbazole group, a phenethylpiperidinyl group, a cinnamonyl group, Semi-thioindigo group, phenylpropenyl phenyl and other structural bases. A photo-alignment group exhibiting a photo-alignment function by a dimerization reaction having a C = 0 bond, for example, a group having a structure such as a benzophenone group or a coumarin group. Specifically, for example, it has the following structure. Of course, these structures may have substituents such as an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a fluorenyl group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, a halogenated alkyl group, and the like.
553932553932
553932 五、發明說明（8) 於通式（1 )及（2 )中，R!係表示至少一種選自於碳數1〜 30之直鏈狀或支鏈狀伸烷基、碳數3〜1 2之伸環烷基、芳 基伸烷基及環烷基伸烷基之基。 h所示之有機基的具體例如伸甲基、伸乙基、三伸甲基 、四伸甲基、五伸甲基、六伸甲基、七伸甲基、八伸甲基 、九伸甲基、十伸甲基、--伸甲基、十二伸甲基之直鏈 狀伸烷基；1-甲基伸乙基、1-甲基-三甲基、2 -甲基-三甲 基、1-甲基-四伸甲基、2 -甲基-四伸甲基、1-甲基-五伸 甲基、2 -甲基-五伸甲基、3 -甲基-五伸甲基、新戊基之具 支鏈烷基的伸烷基； 環伸戊基、環伸己基之伸環烷基；伸苯基、2，2 -二苯基 -三伸甲基、1-苯基-伸乙基、1-苯基-四伸乙基之在主鏈 或側鏈上具有芳基之芳基伸烷基；環己基伸甲基、1 -環己 基-伸乙基、1 -環己基-四伸乙基之在主鏈或側鏈上具有環 烷基之環烷基-伸烷基等。於此等之中以碳數1〜3 0之伸 烷基或碳數3〜1 2之伸環烷基較佳。 另外，h亦可以爲2〜5個此等上述例舉之基以單鍵、 酯鍵、醚鍵或胺基甲酸酯鍵連結的基。 該鍵結的基例如有至少2個伸烷基以醚鍵連結的（聚）醚 構成之基、至少2個伸烷基以酯鍵連結的（聚）酯構成之基 、至少2個伸烷基以胺基甲酸酯鍵連結的（聚）胺基甲酸酯 構成的基、至少2個伸烷基以醚鍵連結的（聚）醚（聚）醇與 (聚）羧酸酯化所得的（聚）羧酸丨（聚）醚（聚）醇丨酯構成的基 -10- 553932 五、發明說明（9) 等。 上述通式（1)及（2)中，]^2係表示藉由上述光二聚合反應 而顯現光配向功能之上述光配向性基。 於上述藉由光二聚合反應而顯現光配向功能之光配向性 基中，使用具有二苯甲酮構造而具有光配性功能的光配向 性基之馬來醯亞胺衍生物的光配向材料，由於具有光配向 功能之必要偏光照射量很少、且所得的光配向膜之熱安定 性、經時安定性優異故更佳 於通式（1)及（2)所示化合物中，此等^所示藉由二聚合 反應而顯現光配向功能之光配向性基係經由單鍵、酯鍵或 胺基甲酸酯鍵.與h所示之基鍵結。藉由光二聚合反應而顯 現光配向功能之光配向性基的鍵結數爲與一分子中具有的 聚合性馬來醯亞胺數相同，惟本發明所使用的馬來醯亞胺 衍生物由於具有數個聚合性馬來醯亞胺基，故該數以2〜4 較佳。其中，由於容易進行聚合性馬來醯亞胺基之聚合、 且形成安定的馬來醯亞胺聚合物、使具有光配向功能之光 配向基的光配向所需必要的能量較少，故藉由光二聚合反 應而顯現光配向功能之光配向性基的鍵結數以2個較佳。 於上述通式（1 )及（2)中，R3及R4各自獨立地表示氫原 子、碳數1〜8之烷基、苯基或鹵素原子。 於上述通式（1 )中，η係表示2〜4之整數。其中，由於 容易進行聚合性馬來醯亞胺基之聚合、且形成安定的馬來 醯亞胺聚合物、使具有光配向功能之光配向基的光配向所 -11- 553932 五、發明說明（1 o) 需必要的能量較少，故以η爲2之通式（2 )所示化合物更 佳。 於本發明之光配向材料中，以調整藉由光二聚合反應而 顯現光配向功能之光配向性基的導入密度、且提高液晶之 配向狀態爲目的時，或以改善對溶劑之溶解度、且提高對 基板之塗覆性爲目的時，亦可適當地混合下述通式（3 )所 示馬來醯亞胺化合物。而且，爲得到爲光配向時對照射光 之良好感度時，亦可使通式（2)所示含有藉由光二聚合反 應而顯現光配向功能之光配向性基的馬來醯亞胺衍生物、 與通式（3 )所示不含藉由光二聚合反應而顯現光配向功能 之光配向性基的馬來醯亞胺衍生物共聚合。553932 V. Description of the invention (8) In the general formulae (1) and (2), R! Represents at least one kind of linear or branched alkylene group having a carbon number of 1 to 30, and a carbon number of 3 to 1 2 cycloalkylene, arylalkylene and cycloalkylalkylene. Specific examples of the organic group represented by h are methyl, ethyl, trimethyl, tetramethyl, pentamethyl, hexamethyl, hexamethyl, octamethyl, nonmethyl Straight-chain alkylene groups of methyl, decamethyl, --methylene, dodecamethyl; 1-methylalkyl, 1-methyl-trimethyl, 2-methyl-trimethyl Methyl, 1-methyl-tetramethyl, 2-methyl-tetramethyl, 1-methyl-pentamethyl, 2-methyl-pentamethyl, 3-methyl-pentamethyl Alkylene, neopentyl, branched alkyl; cycloalkylene, cyclohexyl cycloalkylene; phenylene, 2,2-diphenyl-trimethylidene, 1-benzene Aryl-alkylene, 1-phenyl-tetra-ethylethyl having an aryl group on the main or side chain; cyclohexylmethyl, 1-cyclohexyl-ethyl, 1-cyclo Hexyl-tetraalkyl has a cycloalkyl-alkylene group having a cycloalkyl group in the main chain or a side chain, and the like. Among these, an alkylene group having 1 to 30 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms is preferable. In addition, h may be 2 to 5 groups in which the above-exemplified groups are connected by a single bond, an ester bond, an ether bond, or a urethane bond. The bonded group includes, for example, a group composed of (poly) ethers having at least two alkylene groups connected by ether bonds, a group composed of (poly) ethers having at least two alkylene groups connected by ester bonds, and at least two alkylene groups. A (poly) urethane group having a urethane bond and a (poly) ether (poly) alcohol having at least two alkylene groups connected by an ether bond with a (poly) carboxylic acid (Poly) carboxylic acid 丨 (Poly) ether (poly) alcohol → Ester group -10- 553932 V. Description of the invention (9) and so on. In the general formulae (1) and (2), [^ 2] represents the photo-alignment group that exhibits a photo-alignment function by the photo-dimerization reaction. In the above-mentioned photo-alignment group that exhibits a photo-alignment function by photo-dimerization reaction, a photo-alignment material using a maleimide derivative of a photo-alignment group having a benzophenone structure and a photo-alignment function, Due to the small amount of polarized light irradiation required for the photo-alignment function, and the obtained photo-alignment film has excellent thermal stability and stability over time, it is better than the compounds represented by the general formulae (1) and (2). The photo-alignment group shown to exhibit the photo-alignment function by dimerization is via a single bond, an ester bond, or a urethane bond. The photo-alignment group is bonded to the group shown by h. The number of bonds of the photo-alignment group that exhibits the photo-alignment function by photo-dimerization reaction is the same as the number of polymerizable maleimide in a molecule, but the maleimide derivative used in the present invention is Since it has several polymerizable maleimide imide groups, the number is preferably 2 to 4. Among them, since it is easy to polymerize the polymerizable maleimide group and form a stable maleimide imine polymer, the energy required for photo-alignment of the photo-alignment group having a photo-alignment function is small, so it is borrowed The number of bonds of the photo-alignment group which exhibits a photo-alignment function by a photodimerization reaction is preferably two. In the general formulae (1) and (2), R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a halogen atom. In the general formula (1), η represents an integer of 2 to 4. Among them, since it is easy to polymerize the polymerizable maleimide group and form a stable maleimide imine polymer, the photo-alignment center of a photo-alignment group having a photo-alignment function-11-553932 V. Description of the invention ( 1 o) Less energy is required, so compounds of general formula (2) with η as 2 are more preferred. In the photo-alignment material of the present invention, the purpose is to adjust the introduction density of the photo-alignment group that exhibits the photo-alignment function by photo-dimerization reaction, and to improve the alignment state of the liquid crystal, or to improve the solubility of the solvent and improve When the substrate is coated, the maleimide compound represented by the following general formula (3) may be appropriately mixed. In addition, in order to obtain a good sensitivity to irradiated light during photo-alignment, a maleimide derivative represented by the general formula (2) containing a photo-alignment group that exhibits a photo-alignment function by photo-dimerization reaction, It is copolymerized with a maleimide derivative represented by the general formula (3) which does not contain a photo-alignment group that exhibits a photo-alignment function by a photo-dimerization reaction.
該不含藉由光二聚合反應而顯現光配向功能之光配向性 基的馬來醯·亞胺衍生物對全部而言以〇〜8 0重量％較佳、 更佳者爲0〜50重量％。 於上述通式（3 )中，R 7係表示至少一個選自於（1 )碳數1 〜3 0之直鏈狀伸院基、（2 )碳數1〜3 0之支鏈狀伸院基、 (3 )碳數3〜1 2之伸環烷基、（4 )芳基伸烷基及（5 )環烷基 伸烷基之基。R5及1各自獨立地表示氫原子、碳數1〜8 -12- 553932 五、發明說明（11) 之院基、苯基或鹵素原子。 通式（3 )之R 7的具體例如伸甲基、伸乙基、三伸甲基、 四伸甲基、五伸甲基、六伸甲基、七伸甲基、八伸甲基、 九伸甲基 '十伸甲基、十一伸甲基、十二伸甲基之直鏈狀 伸烷基；1-甲基伸乙基、1-甲基-三甲基、2 -甲基-三甲基 、卜甲基-四伸甲.基、2 -甲基-四伸甲基、1-甲基-五伸甲 基、2 -甲基-五伸甲基、3 -甲基-五伸甲基、新戊基之具支 鍵院基的伸院基； 環伸戊基、環伸己基之伸環烷基；伸苯基、2，2 -二苯基 •三伸甲基、1-苯基-伸乙基、1-苯基-四伸乙基之在主鏈 或側鏈上具有芳基之芳基伸烷基；環己基伸甲基、丨-環己 基-伸乙基、1 -環己基-四伸乙基之在主鏈或側鏈上具有環 烷基之環烷基-伸烷基等。 另外，通式（3 )之R7亦可爲數個此等上述例舉之基以單 鍵、酯鍵、醚鍵或胺基甲酸酯鍵連結的基。 該鍵結的基例如有至少2個伸烷基以醚鍵連結的（聚）醚 構成之基、至少2個伸烷基乙酯鍵連結的（聚）酯構成之基 、至少2個伸烷基以胺基甲酸酯鍵連結的（聚）胺基甲酸酯 構成的基、至少2個伸烷基以醚鍵連結的（聚）醚（聚）醇與 (聚）羧酸酯化所得的（聚）羧酸{(聚）醚（聚）醇）酯構成的基 等。 其次，說明使用本發明之光配向膜用材料、製造光配向 膜與具該物之液晶顯示元件的方法例。 553932 五、發明說明（12) 首先，將本發明之光配向材料溶解於適當的溶劑中。此 時，溶劑沒有特別的限制，惟一般使用N -甲基吡咯院酮、 二甲基甲醯胺、丁基溶纖劑、r - 丁內酯、氯苯、二甲基 亞楓、二甲基乙醯胺、四氫呋喃等。其中，丁基溶纖劑、 τ - 丁內酯由於塗覆性佳、可得均勻的膜、故更佳。此等 溶劑就考慮塗覆性、或塗覆後在短時間內使溶劑揮發而言 ，可混合2種以上使用。 使上述光配向材料之溶液藉由旋轉塗覆法、印刷法等方 法塗覆、乾燥後，進行聚合性馬來醯亞胺基之聚合及光配 向操作。 . 本發明所使用的基板係爲一般光配向膜所使用的基板， 爲具有可耐熱硬化之耐熱性者。該基板例如有玻璃基板。 藉由光或熱之聚合性馬來醯亞胺基的聚合操作，由於會 因光二聚合反應而使光配合的構造單位受到影響，故以預 先進行配合操作更佳。 聚合性馬來醯亞胺基之聚合係藉由紫外線等光照射或加 熱進行。以光照射進行時，以光配向性基不具光配向功能 之波長光較佳。另外，以加熱聚合時進行光配向操作前於 塗覆於基板時可同時乾燥溶劑，故更佳。而且，爲使聚合 性馬來醯亞胺基完全聚合，亦可以先以光照射或加熱進行 聚合，再藉由光照射進行具有光配向的操作後，進行加熱 或適合聚合性馬來醯亞胺基光聚合之無偏光光照射。 另外，使聚合性馬來醯亞胺基聚合的光波長與具有光配 -14- 553932 五、發明說明（13) 向功能之光波長相近時，可同時以一次光照射聚合性馬來 醯亞胺基之聚合與具有光配向功能之操作。該聚合性馬來 醯亞胺基光聚合所使用的照射光沒有特別的限制，惟以使 用紫外線較佳。有關照射方法亦沒有特別限制，可使用無 偏光或直線偏光、橢圓偏光等之偏光。 藉由二聚合反應而顯現光配向之操作係藉由照射偏光進 行。偏光之波長可選自光配向性基之效率佳的二聚合波長 ，例如有可視光、紫外線等，其中以紫外線較佳。而且， 偏光大多使用直線偏光或橢圓偏光。此時，爲得到液晶分 子之預傾角時，亦可使用使偏光自對基板而言之斜向方向 照射的方法、或於偏光照射後自斜向方向照射無偏光之光 的方法。 本發明係將含有在一分子中具藉由光二聚合反應而顯現 光配向功能之光配向性基、與數種具聚合性馬來醯亞胺基 的聚合性單體之聚合性單體的光配向膜用材料塗覆於基板 後，使聚合性馬來醯亞胺基聚合，再藉由產生聚光配性功 能之光配向基的光二聚合反應以製得光配向膜。本發明所 使用的馬來醯亞胺化合物由於爲低分子，故具有溶劑溶解 性高、容易塗覆的特徵。而且，本發明由於藉由聚合性馬 來醯亞胺基聚合形成交聯構造、且可藉由上述光配向性基 之光二聚合反應實現光配向，故可製得對光或熱而言安定 性高的光配向膜。 另外，藉由馬來醯亞胺基聚合時由於不須聚合起始劑， -15- 553932 五、發明說明（14) 故可除去降低電壓保持率等、液晶顯示元件之性能惡化的 原因。 【實施例】 於下述中使用合成例、實施例及比較例等更詳細地說明 本發明。本發明不受此等實施例之範圍所限制。 合成例1 具有二苯甲酮構造之馬來醯亞胺系光配向膜用材料之合 成 a .馬來醯亞胺醋酸之合成 在具備有攪拌機、溫度計、滴下漏斗、申史塔克（譯音） 分餾器及冷卻管之容量500m 1的四口燒瓶中，順序加入 140g甲苯、5.2g對-甲苯磺酸一水合物及2.8g三乙胺， 攪拌且加入30g馬來酸酐後，昇溫至30°C且予以溶解。另 外，加入23g甘氨酸後，攪拌且在7〇°C下反應3小時。加 入50g甲苯、60g三乙胺，使溶劑加熱回流、除去生成的 水且反應1小時。自反應混合物餾去溶劑所得的殘留物中 加入4莫耳/ dm3之鹽酸使pH値調整爲2後，予以加熱-再 結晶、製得7 . 3 g馬來醯亞胺醋酸之淡黃色固體。 b. 4,4、雙（2 -經基乙氧基）二苯甲酮之合成 在具備有攪拌機、溫度計、滴下漏斗及冷卻管之容量 3 00m 1四口燒瓶中加入6 2 . 5 g2 -溴化乙醇，在冰浴中冷卻 下、攪拌且加入l〇〇gN-甲基吡咯烷酮。於其中加入lOmg 對-甲苯磺酸一水合物。在約1 0分鐘內滴入42 . 1 g二氫吡 -16- 553932 五、發明說明（15) 喃。在冰冷下攪拌2小時，且在室溫下攪拌2小時後’加 入42.8g4, 4，-二羥基二苯甲酮及69.lg碳酸鈣’在120 °C 下反應3小時。冷卻後，在400m 1水中加入反應混合物’ 以4 00m 1甲苯萃取2次、且使所得的甲苯層以無水硫酸鈉 乾燥、以蒸餾餾去溶劑。 在所得的殘渣中加入450g甲醇、70g水、1 · 〇g濃鹽酸 ，在室溫下攪拌1晚、過濾所生成的沉澱、且以甲醇充分 洗靜後予以乾燥，製得52g4,4，-雙（2-羥基乙氧基）二苯甲 酮。 c ·馬來醯亞胺系光配向膜用材料之合成 在具備有攪拌機、溫度計、申史塔克分餾器及冷卻管之 容量500ml的三口燒瓶中，順序加入8. 8g合成例1之a 所得的馬來醯亞胺醋酸、6 . 1 g以合成例1之b所得的 4,4’-雙（2-羥基乙氧基）二苯甲酮、〇.4g對-甲苯磺酸一水 合物、20mg氫醌及150ml甲苯，在減壓下加熱至90°C、 使溶劑加熱回流、除去生成的水且反應1 5小時。反應終 了後’熱時過濾反應混合物、以甲醇充分洗淨所得的固體 、予以乾燥，製得8.6g以式（4)所示2官能基馬來醯亞胺 系光配向膜用材料。The maleimidine-imine derivative which does not contain a photo-alignment group that exhibits a photo-alignment function by photodimerization is preferably 0 to 80% by weight, and more preferably 0 to 50% by weight. . In the above general formula (3), R 7 represents at least one selected from the group consisting of (1) a straight chain base having a carbon number of 1 to 30, and (2) a branched chain base having a carbon number of 1 to 30. (3) a cycloalkylene group having 3 to 12 carbon atoms, (4) an arylalkylene group, and (5) a cycloalkylenealkylene group. R5 and 1 each independently represent a hydrogen atom, a carbon number of 1 to 8 -12 to 553932. 5. The description of the invention (11) is a radical, a phenyl group, or a halogen atom. Specific examples of R 7 in the general formula (3) include methyl, ethyl, trimethyl, tetramethyl, pentamethyl, hexamethyl, hexamethyl, octamethyl, and nonyl Straight-chain alkylene groups of methylene, decamethyl, undecymethyl, and dodecamethyl; 1-methylethyl, 1-methyl-trimethyl, 2-methyl- Trimethyl, p-methyl-tetramethyl. 2-methyl-tetramethyl, 1-methyl-pentamethyl, 2-methyl-pentamethyl, 3-methyl-pentamethyl Base, neopentyl, branched base; cyclopentyl, cyclohexyl, cycloalkyl; phenyl, 2,2-diphenyl, trimethyl, 1-benzene Aryl-alkylene having 1-phenyl-tetraethenyl having an aryl group on the main chain or side chain; cyclohexylmethyl, 丨 -cyclohexyl-ethyl, 1-cyclo Hexyl-tetraalkyl has a cycloalkyl-alkylene group having a cycloalkyl group in the main chain or a side chain, and the like. In addition, R7 of the general formula (3) may be a group in which several of the above-exemplified groups are connected by a single bond, an ester bond, an ether bond, or a urethane bond. The bonded group includes, for example, a group consisting of (poly) ethers having at least two alkylene groups connected by ether bonds, a group consisting of (poly) esters having at least two alkylene groups bonded to ethyl esters, and at least two alkylene groups. A (poly) urethane group having a urethane bond and a (poly) ether (poly) alcohol having at least two alkylene groups connected by an ether bond with a (poly) carboxylic acid (Poly) carboxylic acid {(poly) ether (poly) alcohol) ester and the like. Next, an example of a method for manufacturing a photo-alignment film and a liquid crystal display element having the same using the material for a photo-alignment film of the present invention will be described. 553932 V. Description of the invention (12) First, the photo-alignment material of the present invention is dissolved in an appropriate solvent. At this time, the solvent is not particularly limited, but N-methylpyrrolidone, dimethylformamidine, butyl cellosolve, r-butyrolactone, chlorobenzene, dimethylmethylene maple, and dimethylethyl are generally used. Lamine, tetrahydrofuran, etc. Among them, butyl cellosolve and τ-butyrolactone are more preferable because they have good coating properties and a uniform film can be obtained. These solvents can be used as a mixture of two or more kinds in consideration of coating properties or volatilization of the solvent in a short time after coating. After the solution of the photo-alignment material is applied by a spin coating method, a printing method or the like, and dried, polymerizable maleimide group polymerization and photo-alignment operations are performed. The substrate used in the present invention is a substrate used in a general photo-alignment film, and has a heat resistance which is heat-resistant and hardenable. The substrate is, for example, a glass substrate. In light or heat polymerization of a polymerizable maleimide group, it is better to perform the compounding operation in advance because the photo-combination structural unit is affected by the photo-dimerization reaction. The polymerization of the polymerizable maleimide group is performed by irradiation or heating with light such as ultraviolet rays. When light irradiation is performed, wavelength light having a photo-alignment group without a photo-alignment function is preferred. In addition, it is preferable to dry the solvent at the same time as coating the substrate before performing the photo-alignment operation during thermal polymerization. In addition, in order to completely polymerize the polymerizable maleimide imide group, it may be polymerized by light irradiation or heating, and then subjected to light alignment operation by light irradiation, and then heated or suitable for polymerizable maleimide imine. Irradiation of polarized light without photopolymerization. In addition, when the wavelength of light for polymerizing the polymerizable maleimide group is similar to the wavelength of the light having a light distribution of -14-553932. 5. Description of the invention (13) When the wavelength of the light function is similar, the polymerizable maleimide can be irradiated with a single light at the same time. Polymerization of amine group and operation with photo-alignment function. The irradiation light used for this polymerizable maleimide imine-based photopolymerization is not particularly limited, but it is preferable to use ultraviolet rays. There is no particular limitation on the irradiation method, and unpolarized light, linearly polarized light, or elliptically polarized light can be used. The operation of developing light alignment by a dimerization reaction is performed by irradiating polarized light. The wavelength of polarized light can be selected from the dimerization wavelengths with good efficiency of photo-alignment groups, such as visible light and ultraviolet rays, among which ultraviolet rays are preferred. Furthermore, linearly polarized light or elliptically polarized light is often used as the polarized light. In this case, in order to obtain the pretilt angle of the liquid crystal molecules, a method of irradiating polarized light from an oblique direction to the substrate or a method of irradiating unpolarized light from an oblique direction after the polarized light irradiation may be used. The present invention is a light-polymerizing monomer containing a photo-alignment group that exhibits a photo-alignment function through photo-dimerization reaction in one molecule, and a plurality of polymerizable monomers having polymerizable maleimide imide groups. After the material for the alignment film is coated on the substrate, the polymerizable maleimide group is polymerized, and then a photo-dimerization reaction of a photo-alignment group that generates a photo-alignment function is used to obtain a photo-alignment film. Since the maleimide compound used in the present invention is low in molecular weight, it has the characteristics of high solvent solubility and easy application. In addition, in the present invention, since a crosslinked structure is formed by polymerizing a maleimidine imine group, and photo-alignment can be achieved by the photo-dimerization reaction of the photo-alignment group, stability to light or heat can be obtained. High light alignment film. In addition, since a polymerization initiator is not required during the polymerization of maleimidine imide, -15-553932 V. Description of the invention (14) Therefore, the cause of deterioration of the performance of the liquid crystal display element, such as lowering the voltage retention rate, can be removed. [Examples] The present invention will be described in more detail using Synthesis Examples, Examples, Comparative Examples and the like below. The invention is not limited by the scope of these embodiments. Synthesis Example 1 Synthesis of maleimide-based photo-alignment film material with benzophenone structure a. Synthesis of maleimide imine and acetic acid is provided with a stirrer, thermometer, dropping funnel, and Shinstek. A 500-milliliter four-necked flask with a fractionator and a cooling tube was charged with 140 g of toluene, 5.2 g of p-toluenesulfonic acid monohydrate, and 2.8 g of triethylamine in order. After stirring and adding 30 g of maleic anhydride, the temperature was raised to 30 ° C and dissolved. In addition, after adding 23 g of glycine, it was stirred and reacted at 70 ° C for 3 hours. 50 g of toluene and 60 g of triethylamine were added, and the solvent was heated under reflux to remove the generated water and reacted for 1 hour. To the residue obtained by distilling off the solvent from the reaction mixture, 4 mol / dm3 hydrochloric acid was added to adjust the pH to 2 and then heating-recrystallization was performed to obtain 7.3 g of maleimide imine acetate as a pale yellow solid. b. Synthesis of 4, 4, and bis (2-ethoxyethoxy) benzophenone In a 300 m 1 four-necked flask equipped with a stirrer, thermometer, dropping funnel and cooling tube, 6 2. 5 g2- Ethanol bromide was stirred in a ice bath with cooling and 100 g of N-methylpyrrolidone was added. 10 mg of p-toluenesulfonic acid monohydrate was added thereto. 42.1 g of dihydropyridine -16-553932 was added dropwise in about 10 minutes. 5. Description of the invention (15). After stirring under ice-cooling for 2 hours, and stirring at room temperature for 2 hours, 42.8 g of 4,4, -dihydroxybenzophenone and 69.lg of calcium carbonate were added and reacted at 120 ° C for 3 hours. After cooling, the reaction mixture was added to 400 m 1 of water and extracted twice with 400 m 1 of toluene. The obtained toluene layer was dried over anhydrous sodium sulfate, and the solvent was distilled off. 450 g of methanol, 70 g of water, and 1.0 g of concentrated hydrochloric acid were added to the obtained residue, and the mixture was stirred at room temperature for one night, the generated precipitate was filtered, and the precipitate was sufficiently washed with methanol and then dried to obtain 52 g of 4,4,- Bis (2-hydroxyethoxy) benzophenone. c · Synthesis of materials for maleimide-based photo-alignment films In a 500-ml three-necked flask equipped with a stirrer, a thermometer, a Shine Stark fractionator, and a cooling tube, 8. 8 g of Synthesis Example 1a was obtained in order Maleimide acetic acid, 6.1 g of 4,4'-bis (2-hydroxyethoxy) benzophenone obtained in b of Synthesis Example 1, and 0.4 g of p-toluenesulfonic acid monohydrate 20 mg of hydroquinone and 150 ml of toluene were heated to 90 ° C. under reduced pressure, and the solvent was heated under reflux to remove the generated water and reacted for 15 hours. After completion of the reaction, the reaction mixture was filtered while hot, and the obtained solid was sufficiently washed with methanol and dried to obtain 8.6 g of a bifunctional maleimide-based photo-alignment film material represented by the formula (4).
-17- 553932 五、發明說明（16) 合成例2 不具二苯甲酮構造之馬來醯亞胺衍生物的合成 在具備有攪拌機、溫度計、申史塔克分餾器及冷卻管之 容量500ml的三口燒瓶中，順序加入8 . 8g合成例1之a 所得的馬來醯亞胺醋酸、5 · 0g數平均分子量400之聚丙二 醇、〇 · 4g對-甲苯磺酸一水合物、2〇mg氫醌及150ml甲苯 ’在減壓下加熱至90t、使溶劑加熱回流、除去生成的水 且反應1 5小時。反應終了後，使反應混合物以稀氫氧化 鈉溶液洗淨2次、再以純水洗淨3次，餾去甲苯、製得 7 · 7 g以式（5 )所示2官能基馬來醯亞胺衍生物。-17- 553932 V. Description of the invention (16) Synthesis example 2 The synthesis of maleimide derivative without benzophenone structure was carried out in a 500ml volume equipped with a stirrer, thermometer, Shinstock fractionator and cooling tube. In a three-necked flask, 8.8 g of maleimide iminoacetic acid obtained in Synthesis Example 1 a, 5.0 g of polypropylene glycol having a number average molecular weight of 400, 0.4 g of p-toluenesulfonic acid monohydrate, and 20 mg of hydrogen were sequentially added. Quinone and 150 ml of toluene 'were heated to 90 t under reduced pressure, the solvent was heated to reflux, the generated water was removed, and reacted for 15 hours. After the reaction was completed, the reaction mixture was washed twice with a dilute sodium hydroxide solution and then three times with pure water, and toluene was distilled off to obtain 7. 7 g of a bifunctional maleic acid represented by the formula (5). Imine derivative.
合成例3 a· 4-(2 -羥基乙氧基）-肉桂酸-2-羥基乙酯之合成 在容量500ml之壓熱鍋中加入40. 0g( 1.0莫耳）氫氧化 鈉之80ml乙醇、l〇〇ml水之混合溶液，加入82.1g( 0.5莫 耳）4-羥基肉桂酸予以溶解、冰冷且加入l32.2g(3.0莫耳） 環氧乙烷、密閉，且在80°C下反應6小時。加入200ιώ1水 予以稀釋、以10 0ml醋酸乙酯萃取2次。以矽膠色層分析 法精製萃取液後，使醋酸乙酯在減壓下餾去、乾固、且以 丁醇再結晶，製得90.8g(72%)4-(2-羥基乙氧基）肉桂酸- •18- 553932 五、發明說明（17) 2 -羥基乙酯。 b .具有肉桂醯基之馬來醯亞胺衍生物之合成 在具備有攪拌機、溫度計、申史塔克分餾器及冷卻管之 容量500ml的三口燒瓶中，順序加入8 . 8g成例1之a所 得的馬來醯亞胺醋酸、5 · 1 g以合成例3之a所得的4 - ( 2 -羥基乙氧基）肉桂酸-2 -羥基乙酯、〇 . 4g對-甲苯磺酸一水 合物、20mg氫醌及150ml甲苯，在減壓下加熱至90°C、 使溶劑加熱回流、除去生成的水且反應1 5小時。反應終 了後，熱時過濾反應混合物、以甲醇充分洗淨所得的固體 、予以乾燥’製得7 · 8g以式（6 )所示2官能基馬來醯亞胺 衍生物。Synthesis Example 3 Synthesis of a · 4- (2-hydroxyethoxy) -cinnamic acid-2-hydroxyethyl ester In a 500 ml autoclave, 40.0 g (1.0 mole) of sodium hydroxide in 80 ml of ethanol, 100 ml of a mixed solution of water, added 82.1 g (0.5 mol) of 4-hydroxycinnamic acid to dissolve, ice-cooled and added 132.2 g (3.0 mol) of ethylene oxide, sealed, and reacted at 80 ° C 6 hours. Add 200ml of 1 water to dilute and extract twice with 100ml ethyl acetate. After the extract was purified by silica gel chromatography, ethyl acetate was distilled off under reduced pressure, dried and recrystallized with butanol to obtain 90.8 g (72%) of 4- (2-hydroxyethoxy). Cinnamic acid-18-553932 V. Description of the invention (17) 2-hydroxyethyl ester. b. Synthesis of Cinnamonyl-based maleimidine imine derivative In a 500-ml three-necked flask equipped with a stirrer, thermometer, Shinstock fractionator, and cooling tube, 8.8 g of Example 1a was added sequentially. The obtained maleimine imine acetic acid, 5.1 g of 4- (2-hydroxyethoxy) cinnamate-2-hydroxyethyl ester obtained in Synthesis Example 3a, 0.4 g of p-toluenesulfonic acid monohydrate The substance, 20 mg of hydroquinone and 150 ml of toluene were heated to 90 ° C. under reduced pressure, the solvent was heated to reflux, the generated water was removed, and the reaction was performed for 15 hours. After the completion of the reaction, the reaction mixture was filtered under heat, the solid obtained was sufficiently washed with methanol, and dried 'to obtain 7.8 g of a bifunctional maleimidine imide derivative represented by formula (6).
^-NMRC 300MHz ' (CD3)2SO) 5 =3.75〜4.47(m ， 12H) 、 6.84〜7.15(m ， 8H) 、 7.63〜 8 · 18(m，6H) 比較合成例1 具有二苯甲酮構造之2官能基丙烯酸酯的合成 於合成例1之c·馬來醯亞胺衍生物之合成中，使用丙 _酸取代馬來醯亞胺醋酸以製得式（7 )所示2官能基丙烯 酸酯。 -19- 553932 五、發明說明（ι〇^ -NMRC 300MHz '(CD3) 2SO) 5 = 3.75 ~ 4.47 (m, 12H), 6.84 ~ 7.15 (m, 8H), 7.63 ~ 8 · 18 (m, 6H) Comparative Synthesis Example 1 Has a benzophenone structure Synthesis of Bifunctional Acrylate In Synthesis of c. Maleimide imine derivative in Synthesis Example 1, propionic acid was used in place of maleimide acetic acid to obtain bifunctional acrylic acid represented by formula (7) ester. -19- 553932 V. Description of the invention (ι〇
比較合成例2 在主鏈上具有聚馬來醯亞胺、且在側鏈上具有對氟苯甲 醯基肉桂醯基之光配向膜用材料的合成 a.聚羥基苯基馬來醯亞胺之合成 在塡充有氮氣之三口燒瓶中加入5g美國聚科學公司 (Polyscience co.，U.S.A.)之馬來酸酐聚合物與3g胺基 苯酚加入100ml二甲苯中，在常溫下攬拌30分鐘、且加 入2 . 9g異喹啉、徐徐地昇溫至150°C後，繼續除去反應中 生成的水且繼續反應3小時。確認完全沒有水生成時使反 應終了，使溫度降爲常溫後注入50ml甲醇以使生成物沉 澱，減壓過濾後在10(TC下真空乾燥、製得聚羥基苯基馬 來醯亞胺。 b .對氟苯甲醯基肉桂醯基氯化物之合成 在 100ml水與 1 00m 1二甲基亞碼l ( DMS0 )中溶解 16.42g(0. 1莫耳）對羥基肉桂酸與8g氫氧化鈉，在（TC下 激烈攬拌且慢慢地滴入15.86g(0.1莫耳）對氟苯甲醯基氯 化物。在常溫下反應約2小時後，以稀鹽酸中和至PH = 6〜 7。使所得的固體中間物過濾、以水完全洗淨。在真空下 完全乾燥後’在乙醇中再結晶、製得收率90%之對氟苯甲 -20- 553932 五、發明說明（19) 醯氧基肉桂酸。於其中添加1 . 2當量氯化亞硫醯與50ml 氯化伸甲基，在常溫下反應製得透明溶液。於反應後，在 真空下除去溶劑與氯化亞硫醯，完全乾燥、製得對氟苯甲 醯基肉桂醯基氯化物。 c ·在主鏈上具有聚馬來醯亞胺、且在側鏈上具有對氟苯甲 醯基肉桂醯基之光配向膜用材料的合成 使1 . 7 g比較合成例2之a .所得的聚羥基苯基馬來醯亞 胺溶解於50ιώ1Ν-甲基吡咯烷酮（NMP)中，加入1 .0g三乙胺 、攪拌30分鐘。使反應溫度降低5°C、激烈攪拌且慢慢地 滴入2 . 1 3g上述比較合成例2之b .所得的對氟苯甲醯基肉 桂醯基氯化物。完全滴入對氟苯甲醯基肉桂醯基氯化物後 ，持續攪拌1小時使反應終了。使反應液注入混合有各 2ΟΟιώ 1水與甲醇之燒杯中使生成物沉澱，再以過量的水與 甲醇徹底洗淨後，減壓過濾、真空乾燥、最終製得在主鏈 上具有聚馬來醯亞胺、且在側鏈上具有對氟苯甲醯基肉桂 醯基之光配向膜用材料。 使用藉由上述合成例及比較合成例所得的光配向膜用材 料，作成光配向膜進行物性評估。光配向膜之作成方法及 物性評估方法係如下述方法進行。 光配向膜之作成方法 a .光配向材料溶液之調製 使以合成例所得的馬來醯亞胺衍生物溶解於N -甲基吡咯 院酮/ 丁基溶纖劑=1 / 1之混合溶劑中，不揮發成分濃度5 % -21 - 553932 五、發明說明（2〇) 溶液、且使其以0 . 1 // m之過濾器過濾成光配向膜用材料 溶劑。 b - 1 .光配向膜作成（熱硬化方法） 使上述a .之方法所得的光配向膜用材料溶液藉由旋轉塗 覆器均勻地塗覆於附有ITO電極之玻璃基板上，在190°C 下進行乾燥及硬化1小時。然後，在所得的塗膜表面上藉 由超高壓水銀燈、以積算光量30 J / cm2之3 65nm附近直線 偏光的紫外光照射，且作成光配向膜。 b - 2 .光配向膜作成（光硬化方法） 使上述a .之方法所得的光配向膜用材料溶液藉由旋轉塗 覆器均勻地塗覆於附有ITO電極之玻璃基板上，在l〇〇°C 下進行乾燥1 5分鐘後，在塗膜表面上藉由超高壓水銀燈 、以積算光量2〗/cm2之波長31 3nm附近的紫外光照射。然 後，在所得的塗膜表面上藉由超高壓水銀燈、以積算光量 30 J/cm2之3 65nm附近之直線偏光的紫外光照射，且作成 光配向膜。 c.液晶晶胞之作成 在上述b - 1或2所得的光配向膜基板之周圍上塗覆含有 直徑8 // m之苯乙烯珠的環氧系黏合劑、殘留液晶注入口 ，且使配向面相對、偏光方向直交下重疊壓熔，且使黏合 劑在150°C下硬化90分鐘。 然後，自液晶注入口以同位素相真空注入扭轉液晶（5CB) 予以塡充後，以環氧系黏合劑將液晶注入口密封。 -22- 553932 五、發明說明（22) 熱性皆佳。 實施例2 自合成例1所得的馬來醯亞胺衍生物（4 )以上述光配向 膜用材料溶液之調製方法調製光配向膜用材料溶液，再以 b - 2 .之光配向膜的熱硬化作成方法作成光配向膜。使用 所得的光配向膜作成液晶晶胞，且以上述評估方法進行物 性評估。 結果’電壓保持率爲9 9 %、且液晶配向性、耐久性、耐 熱性皆佳。 實施例3 除使用合成例1所得的馬來醯亞胺衍生物（4 )及合成例2 所得的馬來醯亞胺衍生物（5 )之重量比爲1 : 1的混合物取 代合成例1所得的馬來醯亞胺衍生物（4 )外，與實施例1 相同地進行評估。 結果，電壓保持率爲99%、且液晶配向性、耐久性、耐 熱性皆佳。 實施例4 除使用合成例3所得的馬來醯亞胺衍生物（6 )取代合成 例1所得的馬來醯亞胺衍生物（4 )外，與實施例1相同地 進行評估。 結果，電壓保持率爲99%、且液晶配向性、耐久性、耐 熱性皆佳。 比較例1 -24- 553932 五、發明說明（23) 除使用比較合成例1所合成的丙規酸衍生物（7 )及對此 而言加入0 . 1 % 2，2 ’ -偶氮雙異丁腈者取代合成例1所得的 馬來釀亞胺衍生物（4 )外’與貫施例1相同地進行評估。 結果，液晶配向性、耐久性、耐熱性雖佳、惟電壓保持 率爲89%。 比較例2 除使用比較合成例2所合成的在主鏈上具有聚馬來醯亞 胺、且在側鏈上具有對氟苯甲醯基肉桂醯基之光配向膜用 材料取代合成例1所得的馬來醯亞胺衍生物（4 )外，與實 施例1相同地進行評估。 結果，電壓保持率爲98%、且液晶配向性佳，惟耐久性 或耐熱性試驗後明暗之切換不淸楚、配向性降低。 -25-Comparative Synthesis Example 2 Synthesis of a material for a photo-alignment film having polymaleimide on the main chain and p-fluorobenzyl cinnamyl on the side chain a. Polyhydroxyphenylmaleimide Synthesis In a three-neck flask filled with nitrogen, 5 g of maleic anhydride polymer from Polyscience Co., USA and 3 g of aminophenol were added to 100 ml of xylene, and stirred at room temperature for 30 minutes, and After 2.9 g of isoquinoline was added and the temperature was gradually raised to 150 ° C., water generated during the reaction was continuously removed and the reaction was continued for 3 hours. When it was confirmed that no water was generated at all, the reaction was completed. After reducing the temperature to normal temperature, 50 ml of methanol was injected to precipitate the product, and the product was filtered under reduced pressure and dried under vacuum at 10 ° C to obtain polyhydroxyphenylmaleimide. B . Synthesis of p-fluorobenzyl cinnamyl fluorenyl chloride dissolved in 100 ml of water and 100 m 1 dimethyl methylene l (DMSO) 16.42 g (0.1 mol) p-hydroxycinnamic acid and 8 g sodium hydroxide Intensively stir at (TC) and slowly add 15.86g (0.1 mole) of p-fluorobenzyl chloride. After reacting at room temperature for about 2 hours, neutralize with dilute hydrochloric acid to pH = 6 ~ 7 The solid intermediate obtained was filtered and completely washed with water. After being completely dried under vacuum, 'recrystallized in ethanol to obtain p-fluorobenzo-20-553932 in a yield of 90% V. Description of the invention (19) Phenoxycinnamic acid. 1.2 equivalents of thionyl chloride and 50 ml of methyl chloride were added to the reaction to prepare a transparent solution at room temperature. After the reaction, the solvent and thionyl chloride were removed under vacuum. , Completely dry to produce p-fluorobenzyl cinnamyl fluorenyl chloride. C. Have polymaleimide on the main chain And the synthesis of a material for a photo-alignment film having a p-fluorobenzylfluorenyl cinnamonyl group on the side chain dissolves 1.7 g of the obtained polyhydroxyphenylmaleimide imide in 50 g of 1N- To methylpyrrolidone (NMP), 1.0 g of triethylamine was added and stirred for 30 minutes. The reaction temperature was lowered by 5 ° C, vigorously stirred and slowly dripped into 2.1 3 g of the above Comparative Synthesis Example 2 b. P-fluorobenzyl cinnamyl fluorenyl chloride. After completely dripping p-fluorobenzyl cinnamyl fluorenyl chloride, continue to stir for 1 hour to complete the reaction. The reaction solution was poured into a beaker mixed with 200 liters of water and methanol. After the product is precipitated, thoroughly washed with excess water and methanol, filtered under reduced pressure, and dried under vacuum to finally obtain polymaleimide on the main chain and p-fluorobenzyl on the side chain. Material for fluorene-based cinnamon fluorene-based photo-alignment film. Use the material for photo-alignment film obtained in the above Synthesis Example and Comparative Synthesis Example to make a photo-alignment film for physical property evaluation. The method for making the photo-alignment film and the physical property evaluation method are as follows The method described above is carried out. Method a. Preparation of the solution of the photo-alignment material so that the maleimidine imide derivative obtained in the synthesis example is dissolved in a mixed solvent of N-methylpyrrolidinone / butyl cellosolvant = 1/1, and the concentration of the non-volatile component is 5 % -21-553932 V. Description of the invention (20) Solution and filter it into a material solvent for photo-alignment film with a filter of 0.1 / 1 m. B-1. Preparation of photo-alignment film (thermal curing method) The photo-alignment film material solution obtained by the method of a. Was uniformly coated on a glass substrate with an ITO electrode by a spin coater, and dried and hardened at 190 ° C for 1 hour. Then, the obtained coating film surface was irradiated with ultraviolet light with linearly polarized light in the vicinity of 3 65 nm with a cumulative light amount of 30 J / cm2 by an ultra-high pressure mercury lamp, and a photo-alignment film was formed. b-2 Preparation of photo-alignment film (light-hardening method) The material solution for photo-alignment film obtained by the method of a. above was uniformly coated on a glass substrate with an ITO electrode by a spin coater, at l0. After drying at 0 ° C for 15 minutes, the surface of the coating film was irradiated with ultra-high pressure mercury lamp with ultraviolet light in the vicinity of a wavelength of 31 3 nm with a cumulative light quantity of 2 / cm2. Then, an ultrahigh-pressure mercury lamp was used to irradiate the surface of the obtained coating film with ultraviolet light with a linearly polarized light in the vicinity of 3 65 nm at a cumulative light amount of 30 J / cm2, and a photo-alignment film was formed. c. Preparation of liquid crystal cell Coat the periphery of the photo-alignment film substrate obtained in b-1 or 2 above with an epoxy-based adhesive containing styrene beads with a diameter of 8 // m, and the remaining liquid crystal injection port, and make the alignment surface The relative and polarized light directions are overlapped and pressed under orthogonal directions, and the adhesive is hardened at 150 ° C for 90 minutes. After that, the twisted liquid crystal (5CB) is vacuum-injected from the liquid crystal injection port and filled with an isotope phase vacuum, and then the liquid crystal injection port is sealed with an epoxy-based adhesive. -22- 553932 V. Description of the invention (22) All thermal properties are good. Example 2 The maleimidine imine derivative (4) obtained from Synthesis Example 1 was prepared by the method for preparing a material solution for a photo-alignment film described above, and then the heat of the photo-alignment film of b-2 was used. The hardening method produces a photo-alignment film. A liquid crystal cell was formed using the obtained photo-alignment film, and physical properties were evaluated by the above-mentioned evaluation method. As a result, the voltage holding ratio was 99%, and the liquid crystal alignment, durability, and heat resistance were all good. Example 3 A mixture of maleimide imine derivative (4) obtained in Synthesis Example 1 and maleimide imine derivative (5) obtained in Synthesis Example 2 at a weight ratio of 1: 1 was used instead of the mixture obtained in Synthesis Example 1. The evaluation was performed in the same manner as in Example 1 except for the maleimidine derivative (4). As a result, the voltage retention was 99%, and the liquid crystal alignment, durability, and heat resistance were all good. Example 4 Evaluation was performed in the same manner as in Example 1 except that the maleimide derivative (6) obtained in Synthesis Example 3 was used in place of the maleimide derivative (4) obtained in Synthesis Example 1. As a result, the voltage retention was 99%, and the liquid crystal alignment, durability, and heat resistance were all good. Comparative Example 1 -24- 553932 V. Description of the invention (23) Except using the malonate derivative (7) synthesized in Comparative Synthesis Example 1 and adding 0.1% 2,2'-azobisiso The butyronitrile was evaluated in the same manner as in Example 1 except that the maleimide derivative (4) obtained in Synthesis Example 1 was replaced. As a result, although the liquid crystal alignment, durability, and heat resistance were good, the voltage retention was 89%. Comparative Example 2 Except that the material used in the photo-alignment film synthesized in Comparative Synthesis Example 2 with polymaleimide in the main chain and p-fluorobenzyl cinnamyl fluorenyl in the side chain was substituted for Synthesis Example 1 The evaluation was performed in the same manner as in Example 1 except for the maleimidine derivative (4). As a result, the voltage retention was 98%, and the liquid crystal had good alignment. However, after the durability or heat resistance test, the switching between light and dark was not good, and the alignment was reduced. -25-
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| JP2001229471A JP4900632B2 (en) | 2000-08-30 | 2001-07-30 | Photo-alignment film material, photo-alignment film and method for producing the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8174653B2 (en) | 2005-05-13 | 2012-05-08 | Sharp Kabushiki Kaisha | Liquid crystal display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8174653B2 (en) | 2005-05-13 | 2012-05-08 | Sharp Kabushiki Kaisha | Liquid crystal display device |
| US8184250B2 (en) | 2005-05-13 | 2012-05-22 | Sharp Kabushiki Kaisha | Liquid crystal display device |
| US8189151B2 (en) | 2005-05-13 | 2012-05-29 | Sharp Kabushiki Kaisha | Liquid crystal display device |
| US8497962B2 (en) | 2005-05-13 | 2013-07-30 | Sharp Kabushiki Kaisha | Liquid crystal display device |
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