581920 Μ _ Β7_ 五、發明説明（,） 技術領域 (請先閲讀背面之注意事項再填寫本頁) 本發明係有關利用可具有扭曲配向之彎曲配向狀態， 改變光透過率而進行顯示之液晶顯示元件、該液晶顯示元 件用配向膜及形成該配向膜用之液晶配向劑漆。 技術背景 經濟部智慧財產局員工消費合作社印製 以往之液晶顯示元件係以使用向列液晶之顯示元件爲 主流，9 0 °扭轉之T N型液晶顯示元件、一般1 8 0 °以 上扭轉之S T N型液晶顯示元件、使用薄膜電晶體之所謂 T F T型液晶顯示元件正邁向實用化。然而，此類液晶顯 示元件有回應速度緩慢之缺點。又可適當辨識影像之視角 狹窄，自斜方向觀看時，發生亮度或對比度降低，以及中 間色調亮度反轉之缺點。其中，有關後者之視角問題，現 今正藉由橫電場方式之平面開關（In Plane Switching,下文 簡稱I P S )型液晶顯示元件、垂直配向與突起構造物之 技術倂用之多域垂直配向（Multi_domain Vertical Alignment ，下文簡稱Μ V A )型，或使用光學補償薄膜之液晶顯示 元件等技術加以改良並實用化。然而，有關前述回應速度 之問題仍未解決，目前正積極開發高速動畫之顯示與自斜 方向觀看時均能獲得良好辨識之液晶顯示元件。 例如，日本特開平7 - 8 4 2 5 4號公報揭示利用可 具有扭曲配向之準安定之彎曲配向狀態，改變光透過率而 顯不之光學補償雙折射 （Optically Compensate d Birefringence，下文簡稱〇C B )型液晶顯示元件。該 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -4- 581920 A7 B7 五、發明説明（2 ) 〇C B型液晶顯示元件有回應速度極爲迅速且視角亦較廣 之特徵，正殷切期望作爲下一世代之液晶顯示元件。 (請先閲讀背面之注意事項再填寫本頁) 該〇C B型液晶顯示元件之一例示於第1圖。與以往 之液晶顯示元件相同，具有形成透明電極2之玻璃基版1 、形成透明電極7之玻璃基版8、配置於玻璃基版1，8 間之液晶層4。此外於透明電極2，7上形成配向膜3 , 6，於該配向膜上可將液晶分子平行且同一方向配向而進 行配向處理。前述透明電極2與透明電極7之間隔係藉由 間隔板9維持一定。又，基板1 , 8之外側相互配置偏光 板1 0、1 2，而該偏光板1 0、1 2與基版1，8間存 在有將透過光進行光學補償之位相補償板1 1，1 3。 上述構造之液晶顯示元件其特徵爲，藉由施加電壓而 引發可具有扭曲配向之準安定之彎曲配向狀態，以及配置 低電壓驅動與視角擴大用之位相補償板1 1， 1 3。其性 能係具有於中間色調顯示領域亦可高速回應且視角亦寬廣 之特性。 經濟部智慧財產局員工消費合作社印製 ◦ C B型液晶顯示元件係於影像顯示開始前，由輻射 配向狀態4轉移至準安定之彎曲配向狀態5之初期化處理 係必須者。該初期化處理例如可施加1 0至3 Ο V之高電 壓而以較短時間進行。但是，不能負荷過大之驅動I C而 以低電壓驅動時，不能轉移至彎曲配向狀態，或即使轉移 其初期化處理亦有必須以分爲單位時間之問題。 爲解決上述問題，提案各種方法。例如日本特開平 9 一 9 6 7 9 0號公報揭示組合T N型液晶顯示元件與同 本紙張尺度適用中國®家標準（CNS ) A4規格（210X297公釐) 一 -5- 581920 A7 B7 五、發明説明（3 ) (請先閲讀背面之注意事項再填寫本頁) 樣扭曲之配向狀態與〇C B型液晶顯示元件類似之基板之 法線方向建立之配向狀態之技術。該技術無須形成彎曲配 向狀態而可迴避上述問題，同時形成與彎曲配向狀態類似 之配向狀態時亦爲回應速度較T N型液晶顯示元件更高速 者。然而，實際上，即使形成類似上述般之彎曲配向之配 向狀態亦未必能獲得高速之回應速度。 又，特開平1 1 一 7 0 1 8號公報揭示於配向膜表面 形成賦予較周圍更大之傾斜角之高度傾斜角領域，再將液 晶中含有手徵劑（chiral agent )之液晶分子之扭曲角設定 爲1 6 0至2 0 0度之技術。該技術係於配向膜表面形成 賦予較周圍更大之傾斜角之高度傾斜角領域，並使其成爲 向彎曲配向狀態之轉移核者。然而，實際上如此構成之配 向膜容易受到製造過程之影響，並不容易安定的形成高度 傾斜角領域。此外，傾斜角若大到一定程度時，信賴性試 驗等之傾斜角之變動有變大之傾向，亦成爲問題之一。 經濟部智慧財產局員工消費合作社印製 又，亦揭示與Μ V A型液晶顯示元件同樣的藉由在電 極上設置小突起構造物而短時間轉移至彎曲配向狀態之技 術。但此種情況因增加設置突起之步驟而使製造步驟複雜 化，突起構造物部分亦容易引起配向缺陷等問題。 此外，迄今亦有多數提案揭示於配向膜中含有固體微 粒子之技術。然而，此等技術係適用於一般液晶顯示元件 或強介電性型液晶顯示元件，而與適用於特殊驅動模式之 〇C B型液晶顯示元件之後述本發明之技術爲本質上不同 者。此外，此等先前技術中，並未觸及有關0 C B型液晶 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -6 - 581920 A7 B7 五、發明説明（4 ) 採頁不兀件，亦非可推知者。例如，於一般液晶顯示元件中 含有固體微粒子之技術，係如下揭示者。日本特開平 7 - 1 8 1 4 9 9號公報揭示以於配向膜中分散電場調製 粒子爲特徵之液晶顯示元件，其效果係部分改變對液晶施 加電壓之強度而改善視角者。該技術特別是對視角成爲問 題之T N型液晶顯示元件或S T N型液晶顯示元件有效者 ，但與本發明之〇C B型液晶顯示元件將彎曲配向狀態安 定化之技術爲本質上不同者。又，特開平 7-3018104號公報、特開平8-54629號公 幸艮、特開平8 — 5 4 6 3 1號公報、特開平 8 - 1 1 4 8 0 3號公報等亦揭示相同之技術，但均爲改 善視角、防止顯示不良或熔接、防止磨損者，爲與本發明 之〇C B型液晶顯示元件將彎曲配向狀態安定化之技術本 質上不同者。 另一方面，特開平6 - 9 5 1 2 2號公報揭示作爲強 介電性型液晶顯示中含有固體粒子之技術，係將平均粒徑 3 0至3 0 0 A之超微粒子分散於配向控制層之液晶光學 元件，其效果爲中間色調或諧調特性經改善者，又電極基 體表面自然發生之凹凸偏差依微粒子徑之微小凹凸埋藏而 改善其配向性。該技術特別是對配向安定性成爲問題之強 介電性型液晶顯示元件有效者，但與本發明之◦ C B型液 晶顯示元件將彎曲配向狀態安定化之技術爲本質上不同者 。其他如特開平3 - 5 5 5 1 8號公報、特開平 3 - 9 2 8 2 4號公報、特開平3 — 2 3 9 2 2 1號公報 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I.-------衣-- (請先閱讀背面之注意事項再填寫本頁) -訂 經濟部智慧財產局員工消費合作社印製 581920 A7 B7 五、發明説明（5 ) ~^ (請先閲讀背面之注意事項再填寫本頁) 、特開平4 一 2 9 6 8 2 1號公報、特開平 δ - 1 8 0 4 5 5號公報等揭示者均爲提昇強介電性型液 晶顯示元件特有之雙安定性、改善諧調特性及改善V - Τ 滯後現象者，與本發明之〇 C Β型液晶顯示元件將彎曲配 向狀態安定化之技術爲本質上不同者。如此，以往之技術 係於Τ Ν型、S Τ Ν型或強介電性型液晶顯示元件用配向 膜中含有固體微粒子之技術，係與本發明之◦ C Β型液晶 顯示元件將彎曲配向狀態安定化之技術爲本質上不同者。 本發明之目的係提供於上述〇 C Β型液晶顯示元件中 ，以低電壓即可迅速且確實的自輻射配向狀態轉移至彎曲 配向狀態之液晶顯示元件、該液晶顯示元件用配向膜及形 成該配向膜用之液晶配向劑漆。 發明之揭示 經濟部智慧財產局員工消費合作社印製 爲解決上述問題銳意進行檢討，結果發現藉由於 〇C Β型液晶顯示元件中使用由含有固體微粒子之液晶配 向劑漆所形成之配向膜或固體微粒子分散於表面之配向膜 即可解決上述問題，基於此而完成本發明。 本發明係由以下構成。 本發明之第1種液晶配向劑漆，其特徵爲於形成利用 可具有扭配向之彎曲配向狀態，改變光透過率而進行顯示 之液晶顯示元件用配向膜用之液晶配向劑漆中，該劑漆係 至少含有一種固體微粒子者。 其較佳樣式爲該固體微粒子爲無機固體微粒子之液晶 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -8 - 581920 A7 B7 五、發明説明（6 ) 配向劑漆。 (請先閲讀背面之注意事項再填寫本頁) 其它之較佳樣式爲該固體微粒子爲金屬微粒子或金屬 氧化物微粒子之液晶配向劑漆。 更佳樣式爲該固體微粒子爲含有至少一種選自C、 Μ g A 1 ' S i 、 C a 、T i 、V、 F e 、 C c )、 N i C u Ζ η 、As Z r 、 R u、R h 、P d ’ ‘A g、 C d I η 、 S η、 S b 、C e 、W、 〇 s 、 I i P t A u 之 元素 的無機固體微粒子之液晶配 丨向 劑漆 o 其 它 較佳 樣式爲 該 固 體微 粒 子爲有 機 固體 微粒子 之液 晶 配 向 劑 漆。 其它之較佳樣式爲該固體微粒子之平均粒徑爲1至 5 0 0 n m之液晶配向劑漆。 本發明之第2項係由上述液晶配向劑漆所得之液晶配 向膜。 本發明之第3項係固體微粒子分散於表面之液晶配向 經濟部智慧財產局員工消費合作社印製 本發明之第4項係使用上述之液晶配向膜利用可具有 扭配向之彎曲配向狀態改變光透過率而進行顯示之液晶顯 示元件。 其較佳樣式爲該固體微粒子之一次粒子徑或二次粒子 徑爲配向膜膜厚之0 . 1至5 0 0倍之液晶顯示元件。 其它較佳樣式之液晶顯示元件其特徵爲，不施加電壓 時於固體微粒子之週邊並無配向缺陷。 另外之較佳樣式之液晶顯示元件其特徵爲，施加電壓 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) -9 - 581920 A7 B7 五、發明説明（7 ) 時固體微粒子係成爲自輻射配向狀態轉移至彎曲配向狀態 之核。 (請先閱讀背面之注意事項再填寫本頁) 亦即，藉由採用上述構造而當施加電壓於透明電極之 間時，配向膜表面之固體微粒子其分散部位係成爲自輻射 配向狀態至準安定之彎曲配向狀態之轉移核，以此爲契機 ，爲使轉移領域擴大成長，所有領域之上述轉移必須短時 間內確實的進行。而且由於該轉移所需之電能小，不會造 成驅動電路之負擔。因此，可降低欲持續保持彎曲配向狀 態所需之最低電壓，換言之亦即可降低輻射配向狀態與彎 曲配向狀態之境界電壓（V c r )。 推測由於配向膜表面之固體微粒子分散之部位，雖無 明確理由但由於其週邊附近液晶分子之電樞連結強度較弱 ，因而具有作爲自輻射配向狀態至彎曲配向狀態之轉移核 的物理作用。又，不施加電壓時於固體微粒子之週邊並未 發生配向缺陷，由於電流刺激而開始具有作爲往彎曲配向 狀態之轉移核的作用。 經濟部智慧財產局員工消費合作社印製 圖示之簡單說明 第1圖係示以往之〇C B型液晶顯示元件構造之縱咅ij 視圖。 符號之說明 1，8 ......玻璃基版 2 , 7 ......透明電極 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -10- 581920 A7 _ B7 五、發明説明（8 ) 3，6……配向膜 4 ............不施加電壓時之液晶配向（輻射配向狀態） (請先閲讀背面之注意事項再填寫本頁) 5 ............施加電壓時之液晶配向（彎曲配向狀態） 9 ..................間隔板 10，12……偏光板 11，13……位相補償板 14 ...............液晶電池 實施發明之最佳型態 本發明之較佳型態係於〇C B型之液晶顯示元件中， 使用含有固體微粒子之液晶配向劑漆所形成之配向膜或固 體微粒子分散於表面之配向膜，而更好該固體微粒子爲金 屬微粒子或金屬氧化物微粒子等無機固體微粒子或有機固 體微粒子。 經濟部智慧財產局員工消費合作社印製 本發明所使用之固體微粒子，由於不施加電壓時其週 邊不產生配向缺陷之範圍甚大，因此於電極間不施加電壓 之部位亦不產生配向缺陷。另一方面，施加電壓時電極部 分之固體微粒子係作爲自輻射配向狀態向彎曲配向狀態轉 移核之作用。 有關本發明之固體微粒子，可例舉如無機固體微粒子 或有機固體微粒子，只要能達到本發明目的之任何固體微 粒子均可。本發明可使用之無機固體微粒子，可例舉如含 有選自Li 、Be、Na、Mg、Al 、Si 、K、Ca 、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X；297公釐) " -11 - 581920 A7 B7 五、發明説明（10) (請先閲讀背面之注意事項再填寫本頁) 膜之膜厚而言過大時則在配向膜表面欲安定的保持固體微 粒子相當困難，而於揉擦等步驟時該固體微粒子會飛散， 而極端之情況下，有時亦成爲液晶顯示元件之光利用效率 惡化之原因。 本發明所使用之固體微粒子之含有量對配向劑漆溶劑 乾燥後之固形成分量（聚合物成分量）爲0 _ 1至 90.0重量％，較好爲0.1至70·0重量％，更好 爲1 0 . 0至5 0 . 0重量％，若固體微粒子之含有量過 少時則作爲向彎曲配向狀態之轉移核心的效果小，反之若 過多則會引起配向膜機能故障。 經濟部智慧財產局員工消費合作社印製 本發明所使用之固體微粒子，較好係含於形成配向膜 用之液晶配向劑漆中使用，只要不損及本發明目的之任何 型態均可使用。以配向劑漆中固體微粒子之一次粒子或二 次粒子凝集形成之二次粒子之型態均勻分散者爲佳，即使 係部分凝集、沉降之各種情況若於配向劑漆使用前以過濾 等步驟可去除時即無問題。又，以提高液晶配向劑漆中之 固體微粒子之分散性爲目的，亦可添加各種分散劑、表面 處理劑、其他添加劑，只要不妨礙本發明之目的即可。 有關本發明之液晶配向劑漆係指將聚合物成分溶解於 溶劑中呈溶解狀態之漆組成物，塗佈於基板後將溶劑乾燥 則形成配向膜。該聚合物成分可爲無規共聚、嵌段共聚等 共聚物，亦可倂用多種聚合物成分。 本發明之液晶配向劑漆中之聚合物成分較好使用四羧 酸二酐與二胺反應而得之聚醯胺酸，該醯胺酸經脫水反應 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） 一 -13- 581920 A7 _B7 五、發明説明（11 ) 等而得 之可溶 性聚醯亞胺，及二 羧 酸 或 二 羧 酸 鹵 與 二 胺 反 應而得 之聚醯 胺等。又該聚醯胺 之 醯 胺 鍵 結 ( C 〇 N Η ) 的氫原 子爲經 其他基取代者亦可。 作 爲提供 本發明之聚醯胺酸 可 溶 性 聚 醯 亞 胺 之 四 羧 酸二酐 之具體· 例可例舉如下。 均 苯四甲 酸二酐、3， 3 ’ j 4 4 ， — 二 苯 基 四 羧 酸二 二酐 、3， 3 ，4，4 ’ — 二 苯 甲 酮 四 羧 酸 二 酐 Λ 萘 酸二 二酐 (2 , 3，6，7 -萘酸酉: F ) > 3 ， 3 ， 4 y 4， — 聯苯基 磺四羧酸二酐、3 y 3 9 ， 4 4 ， — 聯 苯 (請先閲讀背面之注意事項再填寫本頁) 基醚四羧酸二酐、3， 3’ ， 4， 4’ 一二甲基二苯基矽 烷四羧酸二酐、4， 4’ 一雙（3, 4-二羧基苯氧基） 二苯基硫二酐、4，4’ —雙（3，4 —二羧基苯氧基） 二苯基磺酸二酐、4，4’ 一雙（3，4 一二羧基苯氧基 )二苯基丙烷二酐、3， 3’ ， 4， 4’ 一全氟吡啶二苯 甲酸二酐、3， 3’ ，4，4’ —聯苯基四羧酸二酐、雙 經濟部智慧財產局員工消費合作社印製 (苯二甲酸）苯基亞硫醯氧化物二酐、對-苯撐-雙（三 苯基苯二甲酸）二酐、間一苯撐一雙（三苯基苯二甲酸） 二酐、雙（三苯基苯二甲酸）一 4，4’ 一二苯基醚二酐 、雙（三苯基苯二甲酸）一4， 4’ 一二苯基甲烷二酐等 〇 環丁烷四羧酸二酐、環戊烷四羧酸二酐、環〔2.2 • 2〕—辛—7 -烯—2，3，5，6 -四羧酸二酐、環 己烷—1，2， 5，6 -四羧酸二酐、3，3’ —雙環己 基一 1， 1’ ， 2，2’ —四羧酸二酐、2， 3， 5 -三 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -14- 581920 A7 _____Β7_ 五、發明説明（12 ) (請先閲讀背面之注意事項再填寫本頁) 羧基環戊基乙酸二酐、5 -（2，5 -二氧代四氫呋喃基 )—3 -甲基—3 —環己烯—1，2 —二羧酸二酐、1， 3， 3 a , 4， 5， 9b —六氫—5 —四氫一2， 5 —二 氧代三呋喃基）萘并〔1，2，— c〕呋喃一 1 , 3 —二 酮、3， 5 , 6 -三羧基降冰片烷一 2 -乙酸二酐、或此 等化合物之一部分氫原子被甲基、乙基等低級烷基取代之 四羧酸二酐。 乙烯四羧酸二酐、丁烷四羧酸二酐、戊烷四羧酸二酐 、己烷四羧酸二酐、庚烷四羧酸二酐等。 有關本發明之四羧酸二酐並非限定於此，只要能達成 本發明目的之範圍內不言可喻亦可以其他各種型態存在。 又，此等四羧酸二酐可單獨亦可兩種以上組合使用。 可提供本發明聚醯胺之二羧酸或二羧酸鹵之具體例可 例舉如下。 二羧酸之型態爲丙二酸、草酸、二甲基丙二酸、琥珀 酸、富馬酸、麩胺酸、己二酸、己二烯二酸、2 —甲基己 二酸、三甲基己二酸、庚二酸、2， 2-二甲基麩胺酸、 經濟部智慧財產局員工消費合作社印製 3， 3二乙基琥珀酸、壬二酸、癸二酸及辛二酸等。 1，1 一環丙烷二羧酸、 1，2 -環丙烷二羧酸、 1，1 一環丁烷二羧酸、 1， 2-環丁烷二羧酸、 1,3-環丁烷二羧酸、 3，4 —二苯基—1，2 -環丁烷二羧酸、 本紙張尺度適用中國國家標準（CNS) A4規格（210x297公釐) ~~" -15- 581920 A7 B7 五、發明説明（13) 2，4 一-^苯基一 1，3 -環丁院一竣酸、 3，4 一雙（2 -羥基苯基）一 1，2 -環丁烷二竣 (請先閲讀背面之注意事項再填寫本頁) 酸、 2，4 一雙（2 -羥基苯基）一 1，3 —環丁烷二翔 酸、 1 一環丁烯一 1，2 -二羧酸、 1一環丁烯一3， 4一二羧酸、 1，1 一環戊烷二羧酸、 1， 2-環戊烷二羧酸、 1， 3-環戊烷二羧酸、 1，1 一環己烷二羧酸、 1， 2-環己烷二羧酸、 1， 3-環己烷二羧酸、 1， 4一環己烷二羧酸、 1，4 一（降冰片烯）二羧酸、 降冰片烯一 2，3 -二羧酸、 雙環〔2 · 2 . 2〕一辛烷一 1，4 —二羧酸、 經濟部智慧財產局員工消費合作社印製 雙環〔2.2.2〕一辛烷一2， 3-二羧酸、 2， 5- 二氧代—1，4 —雙環〔2. 2 .2〕—辛 烷二羧酸、 1，3 -金剛烷二羧酸、 4，8 -二氧代一 1，3 -金剛烷二羧酸、 2，6 -螺〔3. 3〕一庚烷二羧酸、 1，3 -金剛烷二乙酸、 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -16- 581920 A7 B7 五、發明説明（14 ) 樟腦酸等。 鄰一苯二甲酸、 (請先閱讀背面之注意事項再填寫本頁) 間一苯二曱酸、 對一苯二甲酸、 5—甲基間一苯二甲酸、 5 -第三丁基間一苯二甲酸、 5 -胺基間一苯二甲酸、 5 -羥基間一苯二甲酸、 2， 5—二甲基對一苯二甲酸、 四甲基對一苯二甲酸、 1，4 一萘二羧酸、 2，5 -萘二羧酸、 2，6 -萘二羧酸、 2，7 -萘二羧酸、 1，4蒽二羧酸、 1，4蒽醌二羧酸、 2，5 -聯苯基二羧酸、 經濟部智慧財產局員工消費合作社印製 4，4 ’ 一聯苯基二羧酸、 1，5 -聯苯基二殘酸、 4，4 ’’ 一聯三苯基二羧酸、 4， 4’ 一二苯基甲烷二羧酸、 4， 4’ 一二苯基乙烷二羧酸、 4，4 ’ 一二苯基丙烷二羧酸、 4， 4’ 一二苯基六氟丙烷二羧酸、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -17- 581920 A7 B7 五、發明説明（15 ) 4， 4’ 一二苯基醚二羧酸、 4，4 ’ 一聯苯甲基二羧酸、 (請先閲讀背面之注意事項再填寫本頁) 4，4 ’ 一苯乙烯二羧酸、 4，4 ’ —二苯乙炔二羧酸、 4， 4’ 一羰基二苯甲酸、 4， 4’ 一磺醯基二苯甲酸、 4，4 ’ 一二硫代二苯甲酸、 對苯撐二乙酸、 3， 3-對苯撐二丙酸、 4 一羧基肉桂酸、 對苯撐二丙烯酸、 3， 3’ — 〔4，4’ 一 （甲撐二對苯撐）〕二丙酸 4，4’ —〔4，4’ 一（氧基一二對苯撐）〕二丙 酸、 4，4’ —〔4，4’ —（氧基一二對苯撐）〕二丁 酸、 經濟部智慧財產局員工消費合作社印製 (亞異丙烯基一二對苯撐二氧基）二丁酸、 雙（對-羧基苯基）二甲基矽烷、 1，5 -（9 一氧代芴）二羧酸、 3，4 一呋喃二羧酸、 4，5 -噻唑二羧酸、 2 -苯基一 4，5 -噻唑二羧酸、 1，2，5 —噻二唑一 3，4 一二羧酸、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18- 581920 A7 B7 五、發明説明（16 ) 2， 3 一吡啶二 二羧酸、 2， 4 一 D比口定— 二羧酸、 2， 5 一 H比D定二 二羧酸、 2， 6 一啦D定- 二羧酸、 3， 4 一吡啶二羧酸、 3， 5 一吡啶二 二羧酸、 (請先閱讀背面之注意事項再填寫本頁) 3，6 -吡啶二羧酸等，此等二羧酸亦可爲二羧酸鹵 之型態者。 有關本發明之二羧酸或二羧酸鹵並非限定於此等，只 要能達成本發明目的之範圍內不言可喻亦可以其他各種型 態存在。又，此等二羧酸或二羧酸鹵可單獨亦可兩種以上 組合使用。 可提供本發明之聚醯胺酸、可溶性聚醯亞胺之二胺之 具體例可例舉如下。 對一苯撐二胺、 間一苯撐二胺、 鄰一苯撐二胺、 經濟部智慧財產局員工消費合作社印製 對一甲苯撐二胺、 間一甲苯撐二胺、 對一二甲苯撐二胺、 間一二甲苯撐二胺、 2， 4一二胺基甲苯、 ，6 -二胺基甲苯、 2，3, 5，6 —四甲基一對—苯撐二胺、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -19- 581920 A7 B7 五、發明説明（17 ) 2， 5—二甲基一對一苯撐二胺、 3，3 — —*胺基—^苯基甲院、 4， 4’ 一二胺基二苯基甲烷、 3， 3’ 一二胺基二苯基乙烷、 4， 4 ， 二 胺基二苯基乙烷 1， 3 一雙 ( 4 一胺基苯基） 丙烷、 2， 2 一雙 ( 4 一胺基苯基） 丙烷、 2 , 2 一雙 ( 3 -胺基苯基） 丙烷、 2 , 2 一雙 ( 4 -胺基苯基） 全氟丙烷、 2 , 2 -雙 ( 3 -胺基苯基） 全氟丙烷、 (請先閱讀背面之注意事項再填寫本頁) 雙（4 一胺基一 3 -甲基苯基）甲烷、 雙（4一胺基一2-甲基苯基）甲烷、 1，2 -雙（4 一胺基—3 -甲基苯基）乙烷、 1，3 -雙（4 一胺基一 3 -甲基苯基）丙烷、 1，2 -雙（4 一胺基一 2 -甲基苯基）乙烷、 1，3 -雙（4 —胺基一 2 -甲基苯基）丙烷、 1， 4一雙〔（4一胺基苯基）甲基〕苯、 經濟部智慧財產局員工消費合作社印製 1，4 —雙〔（3 -胺基苯基）甲基〕苯、 1， 4一雙〔（4一胺基苯基）乙基〕苯、 1， 4一雙〔（3-胺基苯基）乙基〕苯、 1， 4一雙〔（4一胺基一3-甲基苯基）甲基〕苯 1， 4 一雙〔（4 一胺基一 3 -甲基苯基）乙基〕本 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -20- 581920 Α7 Β7 五、發明説明（18 ) 雙〔4 一（4 一胺基苯基甲基）苯基〕甲烷、 雙〔4 一（4 一胺基苯基甲基）苯基〕乙烷、 (請先閲讀背面之注意事項再填寫本頁) 雙〔4 一（3 -胺基苯基甲基）苯基〕甲烷、 雙〔4 一（ 3 -胺基苯基甲基）苯基〕乙烷、 2， 2’ 一雙〔4一（4一胺基苯基甲基）苯基〕丙 院、 2， 2’ 一雙〔4一（3-胺基苯基甲基）苯基〕丙 院、 2， 2 一雙〔4 一（3 —胺基苯基甲基）苯基〕全 氟丙院、 1，4 一雙（4 一胺基苯氧基）苯、 1，3 -雙（4 一胺基苯氧基）苯、 2，2’ 一雙（4 一胺基苯氧基）丙烷、 雙〔4 一（4 一胺基苯氧基）苯基〕曱院 2，2’ 一雙〔4 一（4 一胺基苯氧基）苯基〕乙烷 1，1 一雙〔4 一（4 一胺基苯氧基）苯基〕丙烷、 經濟部智慧財產局員工消費合作社印製 2，2’ 一雙〔4 一（4 一胺基苯氧基）苯基〕丙烷 Λ 1，2 -雙〔4 一（4 一胺基苯氧基）苯基〕丙院、 2， 2 -雙〔4 一（2 -胺基苯氧基）苯基〕全氟丙 烷、 2，2 -雙〔4 一（3 -胺基苯氧基）苯基〕全氟丙 院、 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -21 - 581920 A7 B7 五、發明説明（19 ) 2，2 -雙〔4 一（4 —胺基苯氧基）苯基〕全氟丙 院、 (請先閱讀背面之注意事項再填寫本頁) 2，2 -雙〔4 一（4 一胺基苯氧基）苯基〕丁烷、 4，4 ’ 一二胺基聯苯、 3，3 ’ 一二甲基聯苯胺、 3，3 ’ 一二甲氧基聯苯胺、 1，4 一雙（4 一胺基苯基）苯、 4，4 ’ 一雙（4 —胺基苯基）聯苯、 4，4 ’ 一二胺基聯三苯、 3，3’ —二甲基—4，4’ —二胺基聯苯、 1，3 -雙〔4 一（4 一胺基苯氧基）苯基〕苯、 1，4 一雙〔4 一（4 一胺基苯氧基）苯基〕苯、 4，4 一雙〔4 一（ 4 一胺基苯氧基）苯基〕聯苯、 1，2 -雙〔4 一（4 —胺基苯氧基）苯基〕環己院 1， 3 -雙〔4 一（4 一胺基苯氧基）苯基〕環己院 經濟部智慧財產局員工消費合作社印製 1，4 一雙〔4 一（4 一胺基苯氧基）苯基〕環己院 1，5二胺基萘、 2，6二胺基萘、 2，7二胺基芴、 9，9 一雙（4 一胺基苯基）芴、 9，9 —雙（4 一胺基苯基）—10 -蒽、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -22- 581920 A7 B7 五、發明説明（20 ) 4，4’ 一（對一苯撐二亞異丙基）雙苯胺、 4，4’ 一（間一苯撐二亞異丙基）雙苯胺、 (請先閱讀背面之注意事項再填寫本頁) 4， 4’ 一二胺基苯醯苯胺、 3， 3’ 一二胺基二苯甲酮、 3， 4’ 一二胺基二苯甲酮、 4， 4’ 一二胺基二苯甲酮、 3，3’ — —^胺基—^苯基_^^苯基嗣、 4，4’ 一雙（4-胺基苯氧基）二苯基酮、 3， 3’ 一二胺基二苯基硫、 4， 4’ 一二胺基二苯基硫、 雙〔4 一（4 一胺基苯氧基）苯基〕硫、 3，3 - —^^胺基—~^苯基碼、 4，4 ’ 一 —~•胺基—~*苯基碼、 雙〔4 一（4 一胺基苯氧基）苯基〕碼、 3，3’ —>胺基—^苯基S迷、 4，4’ 一 —^胺基—^苯基醚、 3，4 一 —*胺基—^^苯基醚、 經濟部智慧財產局員工消費合作社印製 雙一（4 一胺基苯基）二乙基矽烷、 雙一（4 一胺基苯基）二苯基矽烷、 雙-（4 一胺基苯基）乙基膦氧化物、 2， 2 —雙〔4 一（3 -胺基甲醯基—4 一胺基苯氧 基）苯基〕全氟丙烷、 2，2 -雙一（3 -胺磋釀基一 4 一胺基苯基）全赢 丙烷、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23- 581920 A7 B7 五、發明説明（21 ) 2，2 -雙一（3 -羧基一 4 一胺基苯基）全氟丙院 Λ (請先閲讀背面之注意事項再填寫本頁) 2， 2-雙〔4一（3-胺磺醯基一4一胺基苯氧基 )苯基〕全氟丙烷、 2，2 -雙〔4 一（ 3 -竣基一 4 —胺基苯氧基）苯 基〕全氟丙烷、 1，3 -雙〔2 -丨4 一（4 —胺基苯氧基）苯基} 全氟異丙基〕苯、 2，4 一雙一（/5 -胺基一第三丁基）甲苯、 雙一（對一 /3 -甲基—r 一胺基戊基）苯、 雙一對一（1，1 一二甲基一 5 -胺基戊基）苯、 雙一（對一 Θ -胺基第三丁基苯基）醚、 雙一（對一 4 一胺基苯醯氧基）甲烷、 雙一（對一 4 一胺基苯醯氧基）乙烷、 雙一（對一 4 一胺基苯醯氧基）丙烷、 雙一（對一 4 一胺基苯醯氧基）環己烷、 2，3 - —*胺基啦π定、 經濟部智慧財產局員工消費合作社印製 2，6 - —*胺基啦D定、 3，4 一—胺基卩比D定、 2，4 一二胺基吡啶、 二胺基嘧啶、 二胺基六氫_嗪、 雙一（4 一胺基苯基）一 N -丁胺、 N，N -雙一（4 —胺基苯基）一 N -甲胺、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -24- 581920 Α7 Β7 五、發明説明（22 ) N -（ 3 -胺基苯基）一 4 一胺基苯醯胺等。 1， 4一二胺基環己烷、 (請先閱讀背面之注意事項再填寫本頁) 1，3 -雙一（胺基甲基）環己烷、 1，4 一雙一（胺基甲基）環己烷、 . 異佛爾酮二胺、 降冰片烷二胺、 4， 4’ 一二胺基二環己基甲烷、 雙（2 -甲基一 4 一胺基環己基）甲烷、 四氫二環戊二烯二胺、 六氫一 4，7 —曱伸茚滿基二曱撐二胺、‘ 三環〔6 . 2 . 1 . 02、7〕—十一碳烯撐二甲二胺 Λ 4，4’ 一甲撐雙（環己胺）、 2，5 -雙（胺基甲基）一雙環庚院、 2， 6-雙胺基甲基一雙環庚烷、 2， 3-二胺基雙環〔2， 2， 1〕庚烷、 2， 5-二胺基雙環〔2， 2， 1〕庚烷、 經濟部智慧財產局員工消費合作社印製 2， 6-二胺基雙環〔2， 2， 1〕庚烷、 2， 7-二胺基雙環〔2， 2， 1〕庚烷、 2， 3-二胺基一7-氮雜雙環〔2， 2， 1〕庚烷 2， 5-二胺基一7-氮雜雙環〔2， 2， 1〕庚烷 2， 6-二胺基一7-氮雜雙環〔2， 2， 1〕庚烷 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -25- 581920 A7 B7 五、發明説明（23 ) 2， 3 - —>胺基一 7 -硫雑雙環〔2，2， 1〕庚院 (請先閱讀背面之注意事項再填寫本頁) Λ 2， 5-二胺基一7-硫雜雙環〔2， 2， 1〕庚烷 2， 6-二胺基一7-硫雜雙環〔2， 2， 1〕庚烷 2， 3 一二胺基雙環〔 2 ，2 , 2 ) 辛烷 2， 5 一二胺基雙環〔 2 ，2 , 2 ] 辛烷 > 2 , 6 一二胺基雙環〔 2 ,2 , 2 ] 辛烷 Λ 2 , 5 一二胺基雙環〔 2 ,2 , 2 ) 辛一 7 - 烯、 2 , 5 —二胺基一 7 - -氮雜雙環 C 2 , 2 , 2〕辛烷 2， 5-二胺基一7-氧雜雙環〔2， 2， 2〕辛烷 2， 5-二胺基一7-硫雜雙環〔2， 2， 2〕辛烷 經濟部智慧財產局員工消費合作社印製 2， 6-二胺基雙環〔3， 2， 1〕辛烷、 2， 6-二胺基氮雜雙環〔3， 2， 1〕辛烷、 2， 6-二胺基氧雜雙環〔3， 2， 1〕辛烷、 2， 6-二胺基硫雜雙環〔3， 2， 1〕辛烷、 2， 6-二胺基雙環〔3， 2， 2〕壬烷、 2，6 —二胺基雙環〔3，2，2〕壬-8 —烯、 2， 6-二胺基一8-氮雜雙環〔3， 2， 2〕壬院 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐) -26- 581920 A7 B7 五、發明説明（24 ) 2，6 -二胺基一 8 —氧雜雙環〔3，2，2〕壬院 (請先閲讀背面之注意事項再填寫本頁) 2，6 -二胺基一 8 —硫雜雙環〔3，2，2〕壬院 乙二胺、三甲二胺、丙二胺、丁二胺、戊二胺、己二 胺、庚二胺、辛二胺、壬二胺、4，4 一二胺基庚二胺等 脂族二胺化合物及烷撐中具有氧原子之烷撐二胺等。 1， 1 一雙〔4 一（4 —胺基苯氧基）苯基〕環己院 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4— 甲基環己烷、 1， 1 一雙〔4— (4 —胺基苯氧基）苯基〕一 4 一 乙基環己烷、 1， 1 一雙〔4 一（4 —胺基苯氧基）苯基〕一 4 一 正丙基環己烷、 1， 1 一雙〔4— (4 —胺基苯氧基）苯基〕一 4 一 經濟部智慧財產局員工消費合作社印製 正丁基環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 正戊基環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 正己基環己烷、 1， 1 一雙〔4 一（4 一胺基苯氧基）苯基〕一 4 一 正庚基環己烷、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -27- 581920 Α7 Β7 五、發明説明（25 ) 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 正辛基環己烷、 (請先閱讀背面之注意事項再填寫本頁) 1， 1 一雙〔4 一（4 —胺基苯氧基）苯基〕一 4 一 正壬基環己烷、 1， 1 一雙〔4 一（4 一胺基苯氧基）苯基〕一 4 一 正癸基環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 正十一烷基環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 正十二烷基環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 正十三烷基環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 正十四烷基環己烷、 1， 1 一雙〔4 一（4 一胺基苯氧基）苯基〕一 4 一 正十五院基環己院、 1，1 一雙4 一（4 一胺基苯基）環己烷、 經濟部智慧財產局員工消費合作社印製 1， 1 一雙4 一（4 一胺基苯基）一 4 —甲基環己烷 Λ 1， 1 一雙4 一（4 一胺基苯基）—4 一乙基環己烷 1， 1 一雙4 一（4 一胺基苯基）一 4 一正丙基環己 烷、 1， 1 一雙4 一（4 一胺基苯基）一 4 一正丁基環己 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） -28- 581920 A7 B7 五、發明説明（26 ) 烷、 1， 1一雙4一（4一胺基苯基）一4一正丁基環己 (請先閱讀背面之注意事項再填寫本頁) 烷、 1， 1一雙4一（4一胺基苯基）一4一正戊基環己 院、 1， 1一雙4一（4一胺基苯基）一4一正己基環己 院、 1， 1 一雙4 一（4 一胺基苯基）—4 —正庚基環己 院、 1， 1 一雙4 一（4 一胺基苯基）—4 一正辛基環己 院、 1， 1 一雙4 一（4 一胺基苯基）一 4 —正壬基環己 院、 1， 1—雙4 一（4 一胺基苯基）一 4 —正癸基環己 烷、 1， 1一雙4一（4一胺基苯基）一4一正十一烷基 環己烷、 經濟部智慧財產局員工消費合作社印製 1， 1一雙4一（4一胺基苯基）一4一正十二烷基 環己烷、 1， 1 一雙4 一（4 一胺基苯基）一 4 一正十三烷基 環己烷、 1， 1 一雙4 一（4 一胺基苯基）一 4 一正十四烷基 環己烷、 1， 1 一雙4 一（4 一胺基苯基）—4 一正十五烷基 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -29- 581920 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（27 ) 環己院、 1， 1—雙4 一（4 —胺基苯基）一 4 一環己基環己 烷、 1， 1—雙4 — (4 —胺基苯基）—4 — (4 —甲基 -反式-環己基）環己烷、 1， 1—雙4 — (4 —胺基苯基）—4 — (4 —乙基 -反式一環己基）環己烷、 1， 1一雙4一（4—胺基苯基）一4—(4一正丙 基-反式-環己基）環己烷、 1， 1 一雙4 一（4 一胺基苯基）一 4 一（4 —正丁 基-反式-環己基）環己烷、 1， 1 一雙4— (4 —胺基苯基）—4 一（4 —正戊 基-反式-環己基）環己烷、 1， 1—雙4 一（4 —胺基苯基）一 4 一（4 —正己 基-反式-環己基）環己烷、 1， 1 一雙4 一（4 —胺基苯基）一 4 一（4 一正庚 基-反式-環己基）環己烷、 1， 1 一雙4 一（4 —胺基苯基）一 4 一（4 —正辛 基-反式-環己基）環己烷、 1， 1—雙4 — (4 —胺基苯基）—4 — (4 —正壬 基-反式-環己基）環己烷、 1， 1—雙4 一（4 —胺基苯基）—4 一（4 —正癸 基-反式-環己基）環己烷、 1， 1—雙4 一（4 —胺基苯基）—4 — (4 —正十 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -30- 581920 A7 B7 五、發明説明（28 ) 一烷基一反式一環己基）環己烷、 (請先閲讀背面之注意事項再填寫本頁) 1， 1 一雙4— (4 一胺基苯基）—4 — (4 一正十 二烷基一反式一環己基）環己烷、 1, 1 一雙4 一（4 一胺基苯基）一 4 — (4 一正十 三烷基-反式-環己基）環己烷、 1， 1 一雙4 — (4 —胺基苯基）—4 — (4 —正十 四烷基-反式-環己基）環己烷、 1， 1—雙4— (4 —胺基苯基）一4一（4 —正十 五烷基-反式-環己基）環己烷、 1， 1 一雙〔4— (4 一胺基苯氧基）苯基〕—4 一 (環己基）環己烷、 1， 1 一雙〔4一（4 一胺基苯氧基）苯基〕一 4 一 (4 一甲基環己基）環己烷、 1， 1 一雙〔4 一（4 —胺基苯氧基）苯基〕一 4 一 (4 一乙基環己基）環己烷、 1， 1 一雙〔4 一（4 一胺基苯氧基）苯基〕一 4 一 (4 一丙基環己基）環己烷、 經濟部智慧財產局員工消費合作社印製 1， 1 一雙〔4 一（4 一胺基苯氧基）苯基〕一 4 一 (4一丁基環己基）環己烷、 1， 1 一雙〔4 一（4 一胺基苯氧基）苯基〕一 4 一 (4一戊基環己基）環己烷、 1， 1 一雙〔4 一（4 —胺基苯氧基）苯基〕一 4 一 (4 一己基環己基）環己烷、 1 , 1 一雙〔4 — ( 4 一胺基苯氧基）苯基〕—4 — 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -31- 581920 A7 B7 五、發明説明（29 ) (4 一庚基環己基）環己烷、 1， 1 一雙〔4 一（4 一胺基苯氧基）苯基〕—4 一 (請先閱讀背面之注意事項再填寫本頁) (4 一辛基環己基）環己烷、 1， 1—雙一（4 一胺基苯基）—4 一（環己基甲基 ).環己烷、 1， 1 一雙—（4 一胺基苯基）一 4 一〔 （4 —甲基 環己基）曱基〕環己烷、 1， 1 一雙一（4 —胺基苯基）—4 一〔 （4 一乙基 環己基）甲基〕環己烷、 1, 1 一雙一（4 一胺基苯基）一 4 一〔 （4 —丙基 環己基）甲基〕環己烷、 1， 1 一雙—（4 —胺基苯基）—4 一〔 （4 一丁基 環己基）甲基〕環己烷、 1， 1 一雙一（4 一胺基苯基）一 4 一〔 （4 —戊基 環己基）甲基〕環己烷、 1， 1 一雙一（4 一胺基苯基）一 4 —〔 （4 一己基 環己基）甲基〕環己烷、 經濟部智慧財產局員工消費合作社印製 1， 1 一雙一（4 一胺基苯基）一 4 一〔 （4 一庚基 環己基）甲基〕環己烷、 1， 1 一雙一（4 一胺基苯基）一 4 一〔 （4 一辛基 環己基）甲基〕環己烷、 1， 1 一雙一〔4 一（4 一胺基苯氧基）苯基〕一 4 一（苯基甲基）環己烷、 1， 1 一雙一〔4 一（4 一胺基苯氧基）苯基〕—4 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -32- 581920 A7 B7 五、發明説明（30 ) 一〔（4 一甲基苯基）甲基〕環己烷、 1， 1一雙一〔4一（4一胺基苯氧基）苯基〕一4 (請先閲讀背面之注意事項再填寫本頁) 一〔（4 一乙基苯基）甲基〕環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 〔（4 一丙基苯基）甲基〕環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 〔（4 一丁基苯基）甲基〕環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 〔（4 一戊基苯基）甲基〕環己烷、 1， 1 一雙〔4 一（4 —胺基苯氧基）苯基〕一 4 — 〔（4 一戊基苯基）甲基〕環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 〔（4 一己基苯基）甲基〕環己烷、 1， 1一雙〔4一（4一胺基苯氧基）苯基〕一4一 〔（4 一庚基苯基）甲基〕環己烷、 1， 1一雙〔4—(4一胺基苯氧基）苯基〕一4一 〔（4一辛基苯基）甲基〕環己院、 經濟部智慧財產局員工消費合作社印製 1， 1 一雙一（4 一胺基苯基）—4 一（苯基甲基） 環己烷、 1， 1—雙一（4 —胺基苯基）一 4 —〔 （4 一甲基 苯基）甲基〕環己烷、 1， 1—雙一（4 —胺基苯基）—4 —〔 （4 一乙基 苯基）甲基〕環己烷、 1， 1—雙—（4 一胺基苯基）—4 一〔 （4 一丙基 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -33- 581920 A7 B7 五、發明説明（31 ) 苯基）甲基〕環己烷、 1， 1 一雙一（4 —胺基苯基）—4 一〔 （4 — 丁基 (請先閱讀背面之注意事項再填寫本頁) 苯基）甲基〕環己烷、 1， 1 一雙一（4 —胺基苯基）一4 一〔 （4 一戊基 苯基）甲基〕環己烷、 1， 1—雙—（4 —胺基苯基）—4 一〔 （4 —己基 苯基）甲基〕環己烷、 1， 1 一雙—（4 —胺基苯基）—4 一〔 （4 —庚基 苯基）甲基〕環己烷、 1， 1 一雙—（4 —胺基苯基）一4 一〔 （4 —辛基 苯基）甲基〕環己烷、 1， 1 一雙一丨4 一（4 一胺基苯基）甲基〕苯基} 一 4 一（苯基甲基）環己烷、 1， 1—雙一丨4 一（4 一胺基苯基）甲基〕苯基} 一 4 一〔 （4 一甲基苯基）甲基〕環己烷、 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 一 4 一〔 （4 一乙基苯基）甲基〕環己烷、 經濟部智慧財產局員工消費合作社印製 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 一 4 一〔 （4 一丙基苯基）甲基〕環己烷、 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 一 4 一〔 （4 一丁基苯基）甲基〕環己烷、 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 一 4 一〔（4 一戊基苯基）甲基〕環己烷、 1， 1 一雙一 ( 4 一（4 一胺基苯基）甲基〕苯基} 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -34- 581920 A7 B7 五、發明説明（32 ) 一 4 一〔 （4 一己基苯基）甲基〕環己烷、 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} (請先閲讀背面之注意事項再填寫本頁) 一 4 一〔 （4 一庚基苯基）曱基〕環己烷、 1， 1 一雙一 { 4 一（4 一胺基苯基）甲基〕苯基} 一 4 一〔 （4 一辛基苯基）甲基〕環己烷、 1， 1 一雙一 {4 一〔（4 —胺基苯基）甲基〕苯基 }環己烷、 1， 1 一雙一丨4 一（4 一胺基苯基）甲基〕苯基} 一4一曱基環己烷、 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 一 4 —乙基環己烷、 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 一4一丙基環己院、 1， 1 一雙一 { 4 一（4 一胺基苯基）甲基〕苯基} 一4一丁基環己院、 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 一4一戊基環己院、 經濟部智慧財產局員工消費合作社印製 1， 1 一雙一丨4 一（4 一胺基苯基）甲基〕苯基} 一 4 一己環己烷、 1， 1 一雙一丨4 一（4 一胺基苯基）甲基〕苯基} 一4一庚基環己烷、 1， 1 一雙一丨4 一（4 一胺基苯基）甲基〕苯基} 一 4 一辛基環己院、 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -35- 581920 A7 B7 五、發明説明（33 ) 一 4 —〔 2—(環己基）乙基〕環己烷、 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} (請先閲讀背面之注意事項再填寫本頁) 一 4 一〔 2 -（4 一甲基一反式一環己基）乙基〕環己院 1， 1 一雙一丨4 一（4 一胺基苯基）甲基〕苯基} —4 一〔 2 -（4 一乙基一反式一環己基）乙基〕環己烷 1， 1一雙一丨4一（4一胺基苯基）曱基〕苯基} 一 4 一〔2 -（4 一丙基一反式一環己基）乙基〕環己烷 1 , 1 一雙一丨4 一（4 一胺基苯基）甲基〕苯基} 一 4 一〔 2 -（4 一丁基一反式一環己基）乙基〕環己烷 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 一 4 一〔 2 -（4 一戊基一反式一環己基）乙基〕環己烷 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 經濟部智慧財產局員工消費合作社印製 一 4 一〔2 -（4 一正戊基一反式一環己基）乙基〕環己 院、 1， 1 一雙一 { 4— (4 一胺基苯基）甲基〕苯基} 一 4一〔 2— (4 —己基一反式—環己基）乙基〕環己院 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 一 4 一〔 2— (4 -庚基一反式一環己基）乙基〕環己院 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -36- 581920 A7 B7 五、發明説明（34 ) 1， 1 一雙一丨4 一（4 一胺基苯基）甲基〕苯基} (請先閱讀背面之注意事項再填寫本頁) —4 —〔2— (4 —辛基—反式—環己基）乙基〕環己烷 1， 1 一雙一 {4 一（4 一胺基苯基）甲基〕苯基} 一 4 一〔2 -（4 —壬基一反式—環己基）乙基〕環己烷 Λ 1， 1 一雙一丨4 — (4 一胺基苯基）甲基〕苯基} 一 4 一〔2 -（4 一十二烷基一反式一環己基）乙基〕環 己烷、 1， 1 一雙一〔4 一（4 一胺基苯氧基）苯基〕戊烷 2，2 -雙一〔4 一（4 —胺基苯氧基）苯基〕戊烷 3， 3 -雙一〔4 一（4 一胺基苯氧基）苯基〕戊烷 、 1， 1 一雙一〔4 一（4 一胺基苯氧基）苯基〕己烷 經濟部智慧財產局員工消費合作社印製 % 2， 2 -雙一〔4 一（4 一胺基苯氧基）苯基〕己烷 3， 3 -雙一〔4 一（4 一胺基苯氧基）苯基〕己院 1， 1 一雙一〔4 一（4 一胺基苯氧基）苯基〕庚院 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） -37 - 581920 A7 B7 五、發明説明（35 ) 2 , 2 -雙一〔4 一（4 一胺基苯氧基）苯基〕庚烷 4 3 4 2 3 4 2 雙 雙 雙 4581920 Μ _ Β7_ V. Description of the invention (,) Technical field (please read the precautions on the back before filling this page) The present invention relates to a liquid crystal display for displaying by using a bending alignment state that can have a twisted alignment to change the light transmittance Element, the alignment film for a liquid crystal display element, and a liquid crystal alignment agent paint for forming the alignment film. Technical background Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The previous liquid crystal display elements were mainly TN liquid crystal display elements with 90 ° twist, and STN types with 180 ° twist or more. Liquid crystal display elements and so-called TFT-type liquid crystal display elements using thin film transistors are being put into practical use. However, such liquid crystal display devices have the disadvantage of slow response speed. It can also properly identify the narrow viewing angle of the image. When viewed from an oblique direction, the shortcomings of brightness or contrast reduction and the inversion of the intermediate tonal brightness occur. Among them, regarding the latter's perspective, multi-domain vertical alignment (Multi_domain Vertical), which is currently used by the technology of horizontal electric field (In Plane Switching, hereinafter referred to as IPS) type liquid crystal display elements, vertical alignment and protruding structures Alignment (hereinafter abbreviated as M VA) type, or a liquid crystal display element using an optical compensation film, is improved and put into practical use. However, the problem of the aforementioned response speed has not been solved. Currently, active development is being made of liquid crystal display elements that can obtain good identification when displaying high-speed animations and viewing from oblique directions. For example, Japanese Patent Application Laid-Open No. 7-8 4 2 5 4 discloses optically compensated birefringence (hereinafter referred to as "OCB") which uses a quasi-stable curved alignment state that can have a twisted alignment to change the transmittance of the light without being noticeable. ) Type liquid crystal display element. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) -4- 581920 A7 B7 V. Description of the invention (2) 〇CB type liquid crystal display element has extremely fast response speed and wide viewing angle. Features, are eagerly expected as the next generation of liquid crystal display elements. (Please read the precautions on the back before filling out this page) An example of this 〇C B-type liquid crystal display element is shown in Figure 1. Similar to the conventional liquid crystal display element, it has a glass substrate 1 forming a transparent electrode 2, a glass substrate 8 forming a transparent electrode 7, and a liquid crystal layer 4 arranged between the glass substrates 1, 8. In addition, alignment films 3, 6 are formed on the transparent electrodes 2, 7, and liquid crystal molecules can be aligned in parallel and in the same direction on the alignment film to perform alignment processing. The distance between the transparent electrode 2 and the transparent electrode 7 is maintained constant by the spacer 9. Further, polarizing plates 10 and 12 are arranged on the outer sides of the substrates 1 and 8 and a phase compensation plate 1 1 and 1 for optically compensating transmitted light are present between the polarizing plates 10 and 12 and the base plates 1 and 8. 3. The liquid crystal display element having the above-mentioned structure is characterized in that a quasi-stable curved alignment state which can have a twisted alignment is induced by applying a voltage, and a phase compensation plate 1 1, 1 3 for low-voltage driving and viewing angle expansion is arranged. Its performance is that it can respond quickly in the halftone display field and has a wide viewing angle. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ◦ Type C B liquid crystal display elements are required for the initial processing of transition from radiation alignment state 4 to quasi-stable curved alignment state 5 before image display starts. This initializing process can be performed in a short time, for example, by applying a high voltage of 10 to 30 V. However, when the drive IC with an excessive load cannot be driven and driven at a low voltage, it cannot be shifted to the bending alignment state, or even if the initializing process is shifted, there is a problem that it must be divided into unit time. In order to solve the above problems, various methods have been proposed. For example, Japanese Unexamined Patent Publication No. 9-1 9 6 9 0 discloses that the combination of a TN-type liquid crystal display element and the same paper size applies the China® Standard (CNS) A4 specification (210X297 mm) -5- 581920 A7 B7 V. Invention Explanation (3) (Please read the precautions on the back before filling in this page) The technology of the alignment state created by the normal direction of the substrate similar to that of the OCB liquid crystal display element. This technology does not need to form a curved alignment state to avoid the above problems. At the same time, when forming an alignment state similar to the curved alignment state, the response speed is higher than that of a TN type liquid crystal display element. However, in fact, even if the alignment state of the curved alignment like the above is formed, a high response speed may not be obtained. In addition, Japanese Patent Application Laid-Open No. 1 1 7 0 1 8 discloses that a high tilt angle region is formed on the surface of the alignment film to give a larger tilt angle than the surroundings, and the liquid crystal molecules containing a chiral agent in the liquid crystal are distorted. The angle is set to a technique of 160 to 200 degrees. This technology is to form an area of a high inclination angle on the surface of the alignment film, which gives a larger inclination angle than the surroundings, and make it a transition core to a curved alignment state. However, the alignment film thus constituted is susceptible to the influence of the manufacturing process, and it is not easy to form a highly inclined region in a stable manner. In addition, if the inclination angle is large to a certain degree, the variation in the inclination angle of the reliability test and the like tends to become larger, which also becomes one of the problems. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. It also revealed the same technology as the MV A liquid crystal display element, which can be transferred to a curved alignment state in a short time by providing a small protruding structure on the electrode. However, in this case, the steps of providing the protrusions complicate the manufacturing steps, and the protrusion structure portion easily causes problems such as alignment defects. In addition, there have been many proposals to date that disclose technologies for containing solid particles in an alignment film. However, these technologies are applicable to general liquid crystal display elements or ferroelectric liquid crystal display elements, and the technology of the present invention described later is essentially different from the OC B-type liquid crystal display element suitable for special driving modes. In addition, in these prior technologies, the relevant 0 CB-type liquid crystals are not covered by the Chinese National Standard (CNS) A4 specification (210X 297 mm) -6-581920 A7 B7. 5. Description of the invention (4) The pieces are not inferable. For example, a technique for including solid fine particles in a general liquid crystal display device is disclosed below. Japanese Patent Application Laid-Open No. 7-1 8 1 4 9 9 discloses a liquid crystal display element characterized by dispersing electric field-modulated particles in an alignment film. The effect is to partially change the intensity of the voltage applied to the liquid crystal to improve the viewing angle. This technology is particularly effective for a T N type liquid crystal display element or an S T N type liquid crystal display element whose viewing angle becomes a problem, but it is fundamentally different from the technology of stabilizing the bending alignment state of the OC B type liquid crystal display element of the present invention. In addition, Japanese Patent Application Laid-Open No. 7-3018104, Japanese Patent Application Laid-Open No. 8-54629, Japanese Patent Application Laid-Open No. 8-5 4 6 31, Japanese Patent Application Laid-Open No. 8-114 1 403, etc. also disclose the same technology, However, all of them are those that improve the viewing angle, prevent poor display or welding, and prevent abrasion. They are essentially different from the technology of stabilizing the bending alignment state of the 0CB liquid crystal display element of the present invention. On the other hand, Japanese Patent Application Laid-Open No. 6-9 5 1 2 2 discloses a technique for containing solid particles in a ferroelectric liquid crystal display, in which ultrafine particles having an average particle diameter of 30 to 300 A are dispersed in alignment control. The liquid crystal optical element of the layer has the effect of improving the halftone or harmonic characteristics, and the unevenness of the unevenness naturally occurring on the surface of the electrode substrate is buried according to the minute unevenness of the particle diameter to improve its alignment. This technology is particularly effective for strong dielectric liquid crystal display elements where alignment stability is a problem, but it is fundamentally different from the technique of stabilizing the bending alignment state of the C B type liquid crystal display element of the present invention. Others such as JP-A-3-5 5 5 1 8, JP-A-3-9 2 8 2 4, JP-A-3-2 3 9 2 2 1 This paper is applicable to Chinese National Standard (CNS) A4 specifications. (210X297 mm) I. ------- Clothing-(Please read the notes on the back before filling out this page)-Order printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economy 581920 A7 B7 V. Description of Invention (5) ~ ^ (Please first Read the precautions on the back and fill in this page), JP-A-Hei 4-2 9 6 8 2 No. 1, JP-A Hei-δ 8 1 0 4 5 5 and other disclosures all enhance the ferroelectric liquid crystal display element The characteristic of dual stability, improved harmonic characteristics, and improved V-T hysteresis is fundamentally different from the technique of stabilizing the bending alignment state of the OC type B liquid crystal display element of the present invention. In this way, the conventional technology is based on the technology of containing solid particles in the alignment film for TN type, S TN type, or ferroelectric liquid crystal display element, which is in a state of bending alignment with the CB type liquid crystal display element of the present invention. The stabilization technology is essentially different. An object of the present invention is to provide a liquid crystal display element in the above-mentioned OC type B liquid crystal display element, which can quickly and reliably transition from a self-radiation alignment state to a curved alignment state at a low voltage, an alignment film for the liquid crystal display element, and forming the liquid crystal display element. Liquid crystal alignment agent paint for alignment film. Disclosure of the Invention Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to conduct an intensive review in order to solve the above problems, it was found that due to the use of alignment films or solids formed by the liquid crystal alignment agent paint containing solid particles in the 0C B type LCD display An alignment film with fine particles dispersed on the surface can solve the above problems, and the present invention has been completed based on this. The present invention is constituted as follows. The first liquid crystal alignment agent paint of the present invention is characterized in that it forms a liquid crystal alignment agent paint for an alignment film for a liquid crystal display element that uses a bending alignment state that can have twist alignment to change the light transmittance to display. Lacquers contain at least one solid particle. Its preferred style is that the solid particles are liquid crystals of inorganic solid particles. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -8-581920 A7 B7 5. Description of the invention (6) Aligner paint. (Please read the precautions on the back before filling this page.) Other preferred styles are liquid crystal alignment paints where the solid particles are metal particles or metal oxide particles. A more preferred form is that the solid particles contain at least one selected from the group consisting of C, MG g A 1 'S i, C a, T i, V, F e, C c), N i C u Z η, As Z r, R Liquid crystal alignment of inorganic solid particles of u, Rh, P d '' A g, C d I η, S η, S b, C e, W, 〇s, I i P t A u o Other preferred styles are liquid crystal alignment paints in which the solid particles are organic solid particles. The other preferred style is a liquid crystal alignment agent paint with an average particle diameter of the solid fine particles of 1 to 500 nm. The second aspect of the present invention is a liquid crystal alignment film obtained from the above-mentioned liquid crystal alignment agent paint. The third aspect of the present invention is printed by liquid crystal alignment with solid particles dispersed on the surface. The fourth aspect of the present invention is the use of the above-mentioned liquid crystal alignment film to change the light transmission using the curved alignment state with twist alignment. Liquid crystal display element that performs display at a high rate. Its preferred style is that the primary particle diameter or secondary particle diameter of the solid microparticles is 0% of the film thickness of the alignment film. 1 to 5000 times the liquid crystal display element. Other preferred liquid crystal display elements are characterized in that there are no alignment defects around the solid particles when no voltage is applied. In addition, the liquid crystal display element of a better style is characterized in that the applied paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -9-581920 A7 B7 V. Description of the invention (7) The nucleus shifts from the radiation alignment state to the bending alignment state. (Please read the precautions on the back before filling this page) That is, by applying the above-mentioned structure, when a voltage is applied between the transparent electrodes, the solid particles on the surface of the alignment film are dispersed from a self-radiating alignment state to a quasi-stable state. The transition core of the bending alignment state is used as an opportunity. In order to expand and grow the field of transfer, the above-mentioned transfers in all areas must be carried out in a short period of time. And because the power required for this transfer is small, it will not cause a burden on the drive circuit. Therefore, the minimum voltage required to continuously maintain the bending alignment state can be reduced, in other words, the boundary voltage (V c r) of the radiation alignment state and the bending alignment state can be reduced. It is presumed that the solid particles dispersed on the surface of the alignment film, although there is no clear reason, because the armature connection strength of the liquid crystal molecules in the vicinity of the periphery is weak, it has a physical role as a transition nucleus from the radiation alignment state to the bending alignment state. In addition, no alignment defect occurred around the solid particles when no voltage was applied, and it started to function as a transition nucleus to the bending alignment state due to current stimulation. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics. Brief description of the diagram. Figure 1 is a longitudinal ij view showing the structure of a conventional OC B-type liquid crystal display element. Explanation of symbols 1, 8. . . . . . Glass base plate 2, 7. . . . . . Transparent electrode The size of this paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) -10- 581920 A7 _ B7 V. Description of the invention (8) 3, 6 ... Alignment film 4. . . . . . . . . . . . Liquid crystal alignment (radiation alignment state) when no voltage is applied (Please read the precautions on the back before filling this page) 5. . . . . . . . . . . . Liquid crystal alignment (bent alignment state) when voltage is applied 9. . . . . . . . . . . . . . . . . . Spacer plates 10, 12 ... Polarizing plates 11, 13 ... Phase compensation plates 14. . . . . . . . . . . . . . . The best form of implementing the invention of a liquid crystal cell The preferred form of the present invention is in an OCB type liquid crystal display element, an alignment film formed using a liquid crystal alignment agent paint containing solid particles or an alignment film in which solid particles are dispersed on the surface Preferably, the solid fine particles are inorganic solid fine particles or organic solid fine particles such as metal fine particles or metal oxide fine particles. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The solid particles used in the present invention have a large range of no alignment defects around the voltage when no voltage is applied, so no alignment defects occur at the locations where no voltage is applied between the electrodes. On the other hand, when the voltage is applied, the solid particles in the electrode part act as a core for transferring the self-radiating alignment state to the bending alignment state. The solid fine particles of the present invention include, for example, inorganic solid fine particles or organic solid fine particles, as long as any solid fine particles can achieve the object of the present invention. The inorganic solid fine particles that can be used in the present invention include, for example, papers containing Li, Be, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and this paper. Standards are applicable to China National Standard (CNS) A4 specifications (210X; 297 mm) " -11-581920 A7 B7 V. Description of the invention (10) (Please read the precautions on the back before filling this page) The film thickness of the film is When it is too large, it is very difficult to stabilize the solid particles on the surface of the alignment film, and the solid particles are scattered during the rubbing and other steps. In extreme cases, it may sometimes cause the light utilization efficiency of the liquid crystal display element to deteriorate. . The content of the solid fine particles used in the present invention is 0 to 1 to 90. 0% by weight, preferably 0. 1 to 70 · 0% by weight, more preferably 10. 0 to 5 0. 0% by weight. If the content of the solid fine particles is too small, the effect as a core for transferring to a curved alignment state is small. On the contrary, if the content is too large, the alignment membrane may malfunction. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the solid particles used in the present invention are preferably contained in a liquid crystal alignment agent paint for forming an alignment film, and can be used as long as it does not impair the purpose of the present invention. It is better to uniformly disperse the primary particles or secondary particles formed by the aggregation of solid particles in the alignment agent paint, even if it is partially agglomerated and settled. If the alignment agent paint is used, it can be filtered and other steps. No problem when removing. Moreover, for the purpose of improving the dispersibility of the solid fine particles in the liquid crystal alignment agent paint, various dispersants, surface treatment agents, and other additives may be added as long as they do not hinder the object of the present invention. The liquid crystal alignment agent varnish of the present invention refers to a varnish composition in which a polymer component is dissolved in a solvent, and after being applied to a substrate, the solvent is dried to form an alignment film. The polymer component may be a copolymer such as random copolymerization or block copolymerization, or a plurality of polymer components may be used. The polymer component in the liquid crystal alignment agent paint of the present invention is preferably a polyamidic acid obtained by reacting a tetracarboxylic dianhydride with a diamine. The amino acid is subjected to dehydration reaction. The paper standard is applicable to Chinese National Standard (CNS) A4. Specification (210 X297 mm) -13- 581920 A7 _B7 V. soluble polyfluorene imine obtained from the description of the invention (11), etc., and polyfluorene obtained from the reaction of dicarboxylic acid or dicarboxylic acid halogen with diamine Wait. The hydrogen atom of the amidine bond (C0NΗ) of the polyamine may be substituted by another group. The specific examples of the tetracarboxylic acid dianhydride which provides the polyamidine-soluble polyimide of the present invention are as follows. Pyromellitic dianhydride, 3, 3 'j 4 4, —diphenyltetracarboxylic dianhydride, 3, 3, 4, 4' — benzophenone tetracarboxylic dianhydride Λ naphthoic dianhydride (2,3,6,7-naphthalene naphthalate: F) > 3, 3, 4 y 4, — biphenylsulfonic tetracarboxylic dianhydride, 3 y 3 9, 4 4 — — biphenyl (please first Read the notes on the back and fill in this page again.) Ethertetracarboxylic dianhydride, 3, 3 ', 4, 4' dimethyldiphenylsilane tetracarboxylic dianhydride, 4, 4 'bis (3, 4-dicarboxyphenoxy) diphenylthiodianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfonic acid dianhydride, 4,4 'bis (3,4 Monodicarboxyphenoxy) diphenylpropane dianhydride, 3, 3 ', 4, 4' monoperfluoropyridine dibenzoic dianhydride, 3, 3 ', 4, 4'-biphenyltetracarboxylic acid di Anhydride, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Phthalic acid) phenylsulfinyl oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-1 Bis (triphenylphthalic acid) dianhydride, bis (triphenylbenzene) Formic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, etc. Cyclobutanetetracarboxylic dianhydride, cyclopentane Tetracarboxylic dianhydride, ring [2. 2 • 2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclohexane-1,2,5,6-tetracarboxylic dianhydride, 3,3'-dicyclohexyl -1, 1 ', 2, 2'-Tetracarboxylic dianhydride, 2, 3, 5-Three paper sizes apply Chinese National Standard (CNS) A4 specifications (210X297 mm) -14- 581920 A7 _____ Β7_ V. Invention Explanation (12) (Please read the notes on the back before filling this page) Carboxycyclopentylacetic dianhydride, 5-(2,5 -dioxotetrahydrofuranyl) -3 -methyl -3 -cyclohexene- 1,2 —dicarboxylic dianhydride, 1, 3, 3 a, 4, 5, 9b —hexahydro-5 —tetrahydro —2, 5-dioxotrifuranyl) naphtho [1,2, — c) Furan 1,3-dione, 3,5,6-tricarboxynorbornane-2, acetic dianhydride, or a part of these compounds in which a part of hydrogen atoms are replaced by lower alkyl such as methyl, ethyl, etc. Carboxylic dianhydride. Ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, pentane tetracarboxylic dianhydride, hexane tetracarboxylic dianhydride, heptane tetracarboxylic dianhydride, and the like. The tetracarboxylic dianhydride of the present invention is not limited to this, as long as it can achieve the object of the present invention, it can be understood that it may exist in various other forms. These tetracarboxylic dianhydrides may be used alone or in combination of two or more. Specific examples of the dicarboxylic acid or dicarboxylic acid halide which can provide the polyamidoamine of the present invention are as follows. Types of dicarboxylic acids are malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutamic acid, adipic acid, adipic acid, 2-methyladipic acid, and Methyl adipic acid, pimelic acid, 2, 2-dimethylglutamic acid, printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs, 3, 3 diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid Acid etc. 1,1 monocyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1 cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid , 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, this paper size applies Chinese National Standard (CNS) A4 specification (210x297 mm) ~~ " -15- 581920 A7 B7 V. Invention Explanation (13) 2,4-mono-phenyl-1,3-cyclobutane-one dicarboxylic acid, 3,4-bis (2-hydroxyphenyl) -1,2-cyclobutane di-dicarboxylic acid (please read first Note on the back page, please fill in this page again) Acid, 2,4-bis (2-hydroxyphenyl) -1,3-cyclobutane dixiang acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-ring Butene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1 cyclohexanedi Carboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-mono (norbornene) dicarboxylic acid, norbornane Ene-2,3-dicarboxylic acid, bicyclic [2 · 2. 2] Octane-1,4-dicarboxylic acid, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Shuanghuan [2. 2. 2] monooctane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo [2. 2 . 2] -octane dicarboxylic acid, 1,3-adamantane dicarboxylic acid, 4,8-dioxo- 1,3-adamantane dicarboxylic acid, 2,6-spiroline [3. 3] monoheptane dicarboxylic acid, 1,3-adamantane diacetic acid, this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -16- 581920 A7 B7 V. Description of the invention (14) Camphor acid and so on. Phthalic acid, (Please read the precautions on the back before filling out this page) m-phthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid Phthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalene Dicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4 anthracene dicarboxylic acid, 1,4 anthraquinone dicarboxylic acid, 2, 5-Biphenyldicarboxylic acid, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 4,4 'monobiphenyldicarboxylic acid, 1,5-biphenyldicarboxylic acid, 4,4' 'triphenylene Phenyldicarboxylic acid, 4, 4'-diphenylmethanedicarboxylic acid, 4, 4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4, 4 ' Diphenyl hexafluoropropane dicarboxylic acid. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm) -17- 581920 A7 B7 5. Description of the invention (15) 4, 4 'diphenyl Ether dicarboxylic acid, 4,4'-biphenylmethyl Carboxylic acid, (Please read the notes on the back before filling this page) 4,4 'Monostyrenedicarboxylic acid, 4,4'-Diphenylacetylene dicarboxylic acid, 4, 4' Monocarbonyldibenzoic acid, 4 , 4 'monosulfofluorenyl dibenzoic acid, 4,4' monodithiodibenzoic acid, p-phenylene diacetic acid, 3, 3-p-phenylene dipropionic acid, 4-monocarboxycinnamic acid, p-phenylene diene Acrylic acid, 3, 3 '— [4,4' mono (methylene di-p-phenylene)] dipropionic acid 4,4 '— [4,4' mono (oxyl-p-phenylene)] dipropionic acid, 4,4 '— [4,4' — (oxy-1,2-p-phenylene)] dibutyric acid, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Butyric acid, bis (p-carboxyphenyl) dimethylsilane, 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-monofurandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2 -Phenyl-4,5-thiathiazole dicarboxylic acid, 1,2,5 —thiadiazole-3,4-dicarboxylic acid, this paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -18 -581920 A7 B7 V. Description of the invention (16) 2,3-pyridinedicarboxylic acid, 2,4-D-Dipidine-dicarboxylic acid, 2,5-H-D Dipidine-dicarboxylic acid, 2,6-La-Dipidine-dicarboxylic acid , 3, 4-pyridinedicarboxylic acid, 3, 5-pyridinedicarboxylic acid, (Please read the notes on the back before filling out this page) 3,6-pyridinedicarboxylic acid, etc. These dicarboxylic acids are also available Those who are dicarboxylic acid halides. The dicarboxylic acid or dicarboxylic acid halogen of the present invention is not limited to these, as long as it can achieve the purpose of the present invention, it goes without saying that it may exist in various other forms. These dicarboxylic acids or dicarboxylic acid halides may be used alone or in combination of two or more. Specific examples of the diamine capable of providing the polyamidic acid and soluble polyamidoimine of the present invention are as follows. P-Phenylenediamine, m-Phenylenediamine, o-Phenylenediamine, printed by p-toluylenediamine, m-toluylenediamine, p-xylenephenyl Diamine, m-xylylenediamine, 2,4-diaminotoluene, 6-diaminotoluene, 2,3,5,6-tetramethyl-p-phenylene diamine, paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) -19- 581920 A7 B7 V. Description of the invention (17) 2, 5-dimethyl one-to-one phenylene diamine, 3, 3 — — * amino group — ^ Phenylformin, 4, 4'-diaminodiphenylmethane, 3, 3'-diaminodiphenylethane, 4, 4, diaminodiphenylethane 1, 3- Bis (4-monoaminophenyl) propane, 2,2-bis (4-monoaminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-amine Phenyl) perfluoropropane, 2, 2-bis (3-aminophenyl) perfluoropropane, (please read the precautions on the back before filling this page) bis (4-amine-3-methylbenzene Base) methane, double (4 Amine mono-2-methylphenyl) methane, 1,2-bis (4-monoamino-3-methylphenyl) ethane, 1,3-bis (4-monoamino-3-methylphenyl) ) Propane, 1,2-bis (4-amino-2-methylphenyl) ethane, 1,3-bis (4-amino-2-methylphenyl) propane, 1,4-bis [ (4-Aminophenyl) methyl] benzene, 1,4-bis [(3-aminophenyl) methyl] benzene, 1,4-bis [(4 Monoaminophenyl) ethyl] benzene, 1,4-bis [(3-aminophenyl) ethyl] benzene, 1,4-bis [(4-aminoamino3-methylphenyl) methyl Phenyl] benzene 1,4 bis [(4-aminoamino-3 -methylphenyl) ethyl] The size of this paper applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -20- 581920 Α7 Β7 5 Explanation of the invention (18) Bis [4-mono (4-aminoaminophenylmethyl) phenyl] methane, Bis [4-mono (4-aminoaminophenylmethyl) phenyl] ethane, (Please read the back first For the matters needing attention, please fill in this page again) bis [4-mono (3-aminophenylmethyl) phenyl] methane, bis 4 mono (3-aminophenylmethyl) phenyl] ethane, 2, 2 'monobis [4-mono (4-aminoaminophenylmethyl) phenyl] propane, 2, 2' monobis [ 4-((3-aminophenylmethyl) phenyl] propanone, 2, 2-bis [4-((3-aminophenylmethyl) phenyl] perfluoropropane, 1,4-bis ( 4-monoaminophenoxy) benzene, 1,3-bis (4-monoaminophenoxy) benzene, 2,2'-bis (4-monoaminophenoxy) propane, bis [4 one (4 one Aminophenoxy) phenyl] Houyuan 2,2'-bis [4 mono (4-monoaminophenoxy) phenyl] ethane 1,1 bis [4 mono (4-aminophenoxy ) Phenyl] propane, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 2,2 'one pair [4 one (4-aminoaminophenoxy) phenyl] propane Λ 1,2-bis [4 one (4 one Aminophenoxy) phenyl] propanone, 2, 2-bis [4-mono (2-aminophenoxy) phenyl] perfluoropropane, 2,2-bis [4-mono (3-aminobenzene (Oxy) phenyl] Perfluoropropanein, this paper is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -21-58192 0 A7 B7 V. Description of the invention (19) 2,2-bis [4-mono (4-aminophenoxy) phenyl] perfluoropropane, (Please read the precautions on the back before filling this page) 2, 2-bis [4-mono (4-monoaminophenoxy) phenyl] butane, 4,4'-diaminobiphenyl, 3,3'-dimethylbenzidine, 3,3'-dimethylformamide Oxybenzidine, 1,4-bis (4-aminophenyl) benzene, 4,4'-bis (4-aminophenyl) biphenyl, 4,4'-diaminobitriphenyl, 3 , 3'-dimethyl-4,4'-diaminobiphenyl, 1,3-bis [4-mono (4-monoaminophenoxy) phenyl] benzene, 1,4-bis [4-a ( 4-monoaminophenoxy) phenyl] benzene, 4,4-bis [4-mono (4-monoaminophenoxy) phenyl] biphenyl, 1,2-bis [4-mono (4-aminobenzene (Oxy) phenyl] cyclohexyl 1,3-bis [4-((4-aminoaminophenoxy) phenyl] cyclohexyl printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1,4 [double] (4 monoaminophenoxy) phenyl] cyclohexyl 1,5 diaminonaphthalene, 2,6 diaminonaphthalene, 2,7 diaminofluorene, 9 , 9-bis (4-aminoaminophenyl) fluorene, 9,9-bis (4-aminoaminophenyl) -10-anthracene, This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -22- 581920 A7 B7 V. Description of the invention (20) 4,4 'mono (p-phenylene diisopropylidene) bisaniline, 4,4' mono (m-phenylene diisopropylidene) bisaniline (Please read the precautions on the back before filling out this page) 4, 4 'Monodiaminobenzidine, 3, 3' Monodiaminobenzophenone, 3, 4 'Monodiaminobenzophenone Ketone, 4, 4 'monodiaminobenzophenone, 3,3' — ^ amino — ^ phenyl — ^ phenylphenyl, 4,4 'monobis (4-aminophenoxy) dione Phenyl ketone, 3, 3'-diaminodiphenylsulfide, 4, 4'-diaminodiphenylsulfide, bis [4-((4-aminoaminophenoxy) phenyl] sulfur, 3, 3-— ^^ amino — ~ ^ phenyl code, 4,4 'mono — ~ • amino — ~ * phenyl code, bis [4-mono (4-aminophenoxy) phenyl] code, 3 , 3 '— > Amino- ^ phenyl S, 4,4'-Amine- ^ phenyl ether, 3,4-A- * amino- ^^ Phenyl ether, printed by Bis (4 monoaminophenyl) diethylsilane, Bis (4 monoaminophenyl) diphenylsilane, Bi- (4 Monoaminophenyl) ethylphosphine oxide, 2,2-bis [4-mono (3-aminomethylamido-4monoaminophenoxy) phenyl] perfluoropropane, 2,2-bisone (3-Amine base-4 Aminophenyl) All-propane, this paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -23- 581920 A7 B7 V. Description of the invention (21) 2 2,2-bis (3-carboxy-1, 4-aminoaminophenyl) perfluoropropane Λ (Please read the precautions on the back before filling out this page) 2, 2-bis [4- (3-aminesulfonyl -4-monoaminophenoxy) phenyl] perfluoropropane, 2,2-bis [4-mono (3- (3-alkylamino-4-phenylphenoxy) phenyl] perfluoropropane, 1,3-bis [2-丨 4 Mono (4-aminophenoxy) phenyl] Perfluoroisopropyl] benzene, 2,4-Bis (/ 5-amino-third butyl) toluene, Bis (p- One / 3 -methyl-r monoaminopentyl) benzene, two one to one (1,1 one Dimethyl-5-aminopentyl) benzene, bis (p-Θ-amino third butylphenyl) ether, bis- (p-4-aminophenylphenoxy) methane, bis ( P-4-monoaminophenylfluorenyloxy) ethane, bis (p-4-monoaminophenylfluorenyloxy) propane, bis (p-4-monoaminophenylfluorenyloxy) cyclohexane, 2, 3-—Aminopyridine, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 2,6--* Aminopyridine D, 3,4-Aminopyridine D, 2,4-Diamine Pyridine, diaminopyrimidine, diaminohexahydro_azine, bis (4-monoaminophenyl) -N-butylamine, N, N-bis (4-aminophenyl) -N-formyl Amine, this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -24- 581920 A7 B7 V. Description of the invention (22) N-(3-aminophenyl) -4 monoaminobenzidine Wait. 1,4-diaminocyclohexane, (Please read the precautions on the back before filling out this page) 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (monoamino) Group) cyclohexane,. Isophoronediamine, norbornanediamine, 4, 4 'monodiaminodicyclohexylmethane, bis (2-methyl-4 monoaminocyclohexyl) methane, tetrahydrodicyclopentadiene di Amine, hexahydro-4,7-fluorene indanyl difluorene diamine, 'tricyclic [6. 2 . 1 . 02, 7] —Undecenyldimethylenediamine Λ 4,4 'monomethylenebis (cyclohexylamine), 2,5-bis (aminomethyl) -bicycloheptyl, 2, 6-bis Aminomethyl-bicycloheptane, 2,3-diaminobicyclo [2, 2, 1] heptane, 2,5-diaminobicyclo [2, 2, 1] heptane, Intellectual Property Bureau of the Ministry of Economic Affairs Employee Consumer Cooperative printed 2, 6-diaminobicyclo [2, 2, 1] heptane, 2, 7-diaminobicyclo [2, 2, 1] heptane, 2, 3-diamine-7 -Azabicyclo [2, 2, 1] heptane 2,5-diamino-7-azabicyclo [2, 2, 1] heptane 2,6-diamino-7-azabicyclo [2 2, 1, 1] heptane This paper is in accordance with Chinese National Standards (CNS) A4 specifications (210X 297 mm) -25- 581920 A7 B7 V. Description of the invention (23) 2, 3--> Amine 7- Thiobicyclo [2, 2, 1] Geng Yuan (Please read the precautions on the back before filling out this page) Λ 2,5-diamino-7-thiabicyclo [2, 2, 1] heptane 2, 6-diamino-7-thiabicyclo [2, 2, 1] heptane 2, 3 diaminobicyclo [2, 2, 2) octane 2, 5 monodiaminobicyclo [2,2,2] octane > 2,6monodiaminobicyclo [2,2,2] octane Λ2,5diaminobicyclo [2,2,2) Octyl 7-ene, 2, 5-diamino- 7-aza-bicyclo C 2, 2, 2] octane 2, 5-diamino- 7-oxabicyclo [2, 2, 2] octane Alkyl 2,5-diamino-7-thiabicyclo [2, 2, 2] Octane Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 2, 6-diaminobicyclo [3, 2, 1] octane , 2, 6-diaminoazabicyclo [3, 2, 1] octane, 2, 6-diaminooxabicyclo [3, 2, 1] octane, 2, 6-diaminothio Bicyclic [3, 2, 1] octane, 2, 6-diaminobicyclo [3, 2, 2] nonane, 2,6-diaminobicyclo [3, 2, 2] non-8-ene, 2, 6-diamino-8-azabicyclo [3, 2, 2] The size of this paper applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -26- 581920 A7 B7 V. Description of the invention (24) 2,6-Diamino-8-oxabicyclo [3,2,2] Renyuan (Please read the precautions on the back before filling this page) 2,6 -Diamino-8-thiabicyclo [3,2,2] Renyuan ethylenediamine, trimethyldiamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine Aliphatic diamine compounds such as nonanediamine, 4,4-diaminoheptanediamine, and alkylene diamines having an oxygen atom in alkylene, and the like. 1, 1-bis [4-((4-aminoaminophenoxy) phenyl] cyclohexane) 1,1-bis (4-((4-aminoaminophenoxy) phenyl)] 4-methylcyclohexyl Alkane, 1, 1-bis [4- (4-aminophenoxy) phenyl] -4-ethylcyclohexane, 1,1-bis [4-amino (4-aminophenoxy) phenyl ] 4-n-propylcyclohexane, 1, 1-[4- (4-aminophenoxy) phenyl]-4-n-butylcyclohexane printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs , 1, 1-bis [4-((4-aminoaminophenoxy) phenyl]] 4- 4-n-pentylcyclohexane, 1, 1-bis [4-((4-aminoaminophenoxy) phenyl) ] 4-n-hexylcyclohexane, 1, 1-bis [4-(4-aminophenoxy) phenyl]-4-n-heptylcyclohexane, this paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) -27- 581920 A7 B7 V. Description of the invention (25) 1, 1-bis [4-((4-aminoaminophenoxy) phenyl]] 4- 4-n-octylcyclohexane, (Please read the notes on the back before filling out this page) 1, 1, one pair [4 one (4-amino Phenoxy) phenyl]-4 -n-nonylcyclohexane, 1, 1-bis [4-(4-aminoaminophenoxy) phenyl]-4-n-decyl cyclohexane, 1, 1 Bis [4-((4-aminoaminophenoxy) phenyl]] 4- (n-undecylcyclohexane), 1, 1-bis [4-((4-aminoaminophenoxy) phenyl]] 4-n-dodecylcyclohexane, 1, 1-bis [4-((4-aminoaminophenoxy) phenyl]-4-n-tridecyl cyclohexane, 1, 1-bis [4 Mono (4-monoaminophenoxy) phenyl] 4- 4-n-tetradecylcyclohexane, 1, 1-bis [4- mono (4-aminophenoxy) phenyl] 4- 4-n-deca Wuyuanji Cyclone House, 1,1 one pair 4 one (4-aminoaminophenyl) cyclohexane, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1,1 one pair 4 one (4-aminoaminophenyl) ) 4-methylcyclohexane Λ 1, 1 bis 4 mono (4 monoaminophenyl)-4 monoethylcyclohexane 1, 1 bis 4 mono (4 monoaminophenyl)-4 1-n-propylcyclohexane, 1, 1-bis-4 4- (4-aminoaminophenyl) -4 4-n-butylcyclohexyl paper standard applicable to China Standard (CNS) A4 specification (210 × 297 mm) -28- 581920 A7 B7 V. Description of the invention (26) alkanes, 1, 1-bis-4-1 (4-aminoaminophenyl) -4-n-butylcyclohexyl (Please read the notes on the back before filling out this page) Alkanes, 1, 1-double 4-1 (4-aminoaminophenyl)-4-n-pentylcyclohexane, 1, 1-double-4 1 (4-1 Aminophenyl)-4-n-hexylcyclohexane, 1, 1-double 4-(4-monoaminophenyl)-4-n-heptylcyclohexane, 1, 1-double 4-(4-monoamine Phenyl) -4 4-n-octylcyclohexane, 1, 1-bis-4 4- (4-aminoaminophenyl) -4-n-nonylcyclohexan, 1, 1-bis-4 mono (4-monoamine Phenyl)-4-n-decyl cyclohexane, 1, 1-bis 4-(4-aminophenyl)-4-n-undecyl cyclohexane, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation of 1, 1, bis 4-(4-aminoaminophenyl)-4-n-dodecylcyclohexane, 1, 1-bis 4-(4-aminoaminophenyl)-4-n-tridecane Cyclohexane, 1, 1 double 4 4 (4 aminoaminophenyl) 4 4 n-tetradecyl cyclohexane, 1, 1 double 4 1 (4 monoaminophenyl)-4 n-pentadecyl This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) -29- 581920 A7 B7 Intellectual Property Bureau, Ministry of Economic Affairs Printed by the employee consumer cooperative V. Description of the invention (27) Cyclone House, 1, 1-bis 4 1 (4-aminophenyl) 4 4-cyclohexylcyclohexane, 1, 1-bis 4 — (4-amine Phenyl) -4— (4-methyl-trans-cyclohexyl) cyclohexane, 1,1-bis-4— (4-aminophenyl) -4— (4-ethyl-trans-monocyclic Hexyl) cyclohexane, 1, 1-bis 4-a (4-aminophenyl)-4- (4-n-propyl-trans-cyclohexyl) cyclohexane, 1, 1-double 4-(4 Monoaminophenyl) -4 4- (4-n-butyl-trans-cyclohexyl) cyclohexane, 1, 1-bis 4- (4-aminophenyl) -4 4- (4-n-pentyl -Trans-cyclohexyl) cyclohexane, 1, 1-bis 4-mono (4-aminophenyl)-4- 4- (n-hexyl-trans-cyclohexyl) cyclohexane, 1, 1-bis 4-a (4-aminophenyl) -a 4- (n-heptyl-trans-cyclohexyl) cyclohexyl , 1, 1-bis-4 4- (4-aminophenyl) -1, 4- (4-n-octyl-trans-cyclohexyl) cyclohexane, 1, 1-bis-4 — (4-aminophenyl) ) —4— (4—n-nonyl-trans-cyclohexyl) cyclohexane, 1, 1-bis-4 mono (4-aminophenyl) -4— (4-n-decyl-trans-cyclo Hexyl) cyclohexane, 1, 1-bis-4 one (4-aminophenyl)-4-(4-normal ten (please read the precautions on the back before filling this page) This paper size applies Chinese national standards ( CNS) A4 specification (210X 297 mm) -30- 581920 A7 B7 V. Description of the invention (28) Monoalkyl-trans-cyclohexyl) cyclohexane, (Please read the precautions on the back before filling this page) 1 , 1-bis 4- (4-aminoaminophenyl) -4— (4-n-dodecyl-trans-cyclohexyl) cyclohexane, 1, 1-bis 4-4- (4-aminoaminophenyl) 4- (4-n-tridecyl-trans-cyclohexyl) cyclohexane, 1, 1-bis 4- (4-aminophenyl) -4 — (4-n-tetradecyl-trans Formula-cyclohexyl) cyclohexane, 1, 1-bis 4- (4-aminophenyl)-4-(4 N-pentadecyl-trans-cyclohexyl) cyclohexane, 1, 1 bis [4- (4-aminoaminophenoxy) phenyl] -4 mono (cyclohexyl) cyclohexane, 1, 1 Bis [4-((4-aminoaminophenoxy) phenyl]] 4-((4-methylcyclohexyl) cyclohexane, 1, 1-bis [4-mono (4-aminophenoxy) benzene Group]-4-(4-ethylcyclohexyl) cyclohexane, 1, 1 -bis [4-(4-aminoaminophenoxy) phenyl] -4-(4-propylcyclohexyl) cyclohexyl Alcohol, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1, 1 double [4-mono (4-aminoaminophenoxy) phenyl] 4- 4- (4-butylcyclohexyl) cyclohexane, 1, 1 One bis [4-((4-aminoaminophenoxy) phenyl]] 4- (4- (pentylylcyclohexyl) cyclohexane, 1, 1, bis [4-((aminoaminophenoxy) benzene) [4] (4-hexylcyclohexyl) cyclohexane, 1, 1-1 [4 — (4-monoaminophenoxy) phenyl] — 4 — This paper size applies to Chinese National Standard (CNS) A4 Specifications (210X297 mm) -31- 581920 A7 B7 V. Description of the invention (29) (4 1 g Cyclohexyl) cyclohexane, 1, 1 bis [4 1 (4 monoaminophenoxy) phenyl]-4 1 (Please read the notes on the back before filling this page) (4 1 octyl ring Hexyl) cyclohexane, 1, 1-bis- (4-aminoaminophenyl) -4 4- (cyclohexylmethyl). Cyclohexane, 1, 1-bis- (4-aminoaminophenyl) -4-[(4-methylcyclohexyl) fluorenyl] cyclohexane, 1, 1-bis- (4-aminophenyl) ) —4-[(4-ethylcyclohexyl) methyl] cyclohexane, 1, 1-bis (4-aminoaminophenyl) -4 — [(4-propylcyclohexyl) methyl] ring Hexane, 1, 1-bis- (4-aminophenyl) -4-[(4-butylcyclohexyl) methyl] cyclohexane, 1,1-bis- (4-aminoaminophenyl) One 4 one [(4-pentylcyclohexyl) methyl] cyclohexane, 1, 1, one bis one (4-aminoaminophenyl) one 4- 4-((4-hexylcyclohexyl) methyl] cyclohexane 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1, 1-bis (4-aminoaminophenyl), 4-([(4-heptylcyclohexyl) methyl] cyclohexane, 1, 1-1,2 (4-monoaminophenyl)-4-[(4-octylcyclohexyl) methyl] cyclohexane, 1, 1-bis- [4-(4-aminoaminophenoxy) phenyl]-4 Mono (phenylmethyl) cyclohexane, 1, 1, one double one [4 one (4 one Aminophenoxy) phenyl] -4 This paper is in accordance with Chinese National Standard (CNS) A4 (210X297mm) -32- 581920 A7 B7 V. Description of the invention (30)-[(4-methylphenyl ) Methyl] cyclohexane, 1, 1-bis- [4-a (4-aminoaminophenoxy) phenyl] -4 (Please read the precautions on the back before filling out this page) One [(4 1-B Phenyl) methyl] cyclohexane, 1,1-bis [4-((4-aminoaminophenoxy) phenyl] -4-[(4-propylphenyl) methyl] cyclohexane, 1, 1-bis [4-((4-aminoaminophenoxy) phenyl]] 4- 4-((4-butylphenyl) methyl] cyclohexane, 1, 1-bis [4- (4- Aminophenoxy) phenyl] -4 4-[(4-pentylphenyl) methyl] cyclohexane, 1, 1-bis [4-mono (4-aminophenoxy) phenyl] -4 — [[4-pentylphenyl) methyl] cyclohexane, 1, 1-bis [4-((4-aminoaminophenoxy) phenyl]] 4-([(4-hexylphenyl) methyl ] Cyclohexane, 1, 1-bis [4-((4-aminoaminophenoxy) phenyl]] 4-([4-heptylphenyl ) Methyl] cyclohexane, 1, 1-bis [4- (4-aminoaminophenoxy) phenyl] 4- 4-[(4-octylphenyl) methyl] cyclohexane, Ministry of Economic Affairs, wisdom Printed by the Consumer Affairs Cooperative of the Property Bureau, 1, 1-bis (4-aminoaminophenyl) -4, 4- (phenylmethyl) cyclohexane, 1,1-bis (4-aminophenyl) -1 — [(4-methylphenyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4 — [(4-ethylphenyl) methyl] cyclohexane, 1, 1—bis— (4-aminoaminophenyl) —4 — [(4-propyl) The size of this paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -33- 581920 A7 B7 V. Description of the invention (31) Phenyl) methyl] cyclohexane, 1, 1-bis (4-aminophenyl) -4-[(4-butyl (please read the precautions on the back before filling this page) benzene (Methyl) methyl] cyclohexane, 1, 1-bis (4-aminophenyl) -4 ([4-pentylphenyl) methyl] cyclohexane, 1, 1-bis- (4 —Aminophenyl) -4 — [(4-hexylphenyl) methyl Cyclohexane, 1, 1-bis- (4-aminophenyl) -4-[(4-heptylphenyl) methyl] cyclohexane, 1,1-bis- (4-aminophenyl) ) 4- 4-[(4-octylphenyl) methyl] cyclohexane, 1, 1-bis-4- 4- (4-aminoaminophenyl) methyl] phenyl} 4- 4- (phenylmethyl Group) cyclohexane, 1, 1-bis-1, 4-mono (4-aminoaminophenyl) methyl] phenyl}, 4-4-[(4-methylphenyl) methyl] cyclohexane, 1, 1 one pair one {4 one (4 monoaminophenyl) methyl] phenyl} one 4 one [(4-ethylphenyl) methyl] cyclohexane, printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 1, 1, bis- {4-mono (4-aminoaminophenyl) methyl] phenyl} 4- 4-[(4-propylphenyl) methyl] cyclohexane, 1, 1, 2-bis {4 Mono (4-monoaminophenyl) methyl] phenyl} 4- 4-[(4-butylphenyl) methyl] cyclohexane, 1, 1-bis- {4-mono (4-aminoaminophenyl) ) Methyl] phenyl} -4-[(4-pentylphenyl) methyl] cyclohexane, 1, 1-one double one (4 one (4 one Aminophenyl) methyl] phenyl} This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -34- 581920 A7 B7 V. Description of the invention (32) One 4 One [(4 Hexylbenzene (Methyl) methyl] cyclohexane, 1, 1-bis ({4-mono (4-aminoaminophenyl) methyl] phenyl} (Please read the notes on the back before filling out this page)-4 1 [( 4 1-heptylphenyl) fluorenyl] cyclohexane, 1, 1-bis-1 {4 1- (4-aminoaminophenyl) methyl] phenyl} 4 4-[(4-octylphenyl) methyl Group] cyclohexane, 1, 1-bis ({4-[[4-aminophenyl) methyl] phenyl} cyclohexane, 1, 1-bis-1 丨 4-((4-aminoaminophenyl) ) Methyl] phenyl} 4-4-fluorenylcyclohexane, 1, 1-bis- {4-mono (4-aminoaminophenyl) methyl] phenyl} 4-ethylcyclohexane, 1, 1 bis- {4 mono (4-aminoaminophenyl) methyl] phenyl} 4-bipropylcyclohexane, 1, 1-bis ({4-mono (4-aminophenyl) methyl] Phenyl} 4-4-butylcyclohexane, 1, 1-bis- {4-mono (4-aminoaminophenyl) methyl] } 1 4-pentylcyclohexane, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1, 1 double 1 丨 4 1 (4-aminoaminophenyl) methyl] phenyl} 4 4-hexanecyclohexane , 1, 1 bis-1 丨 4 ((4-aminoaminophenyl) methyl] phenyl} -1 4-heptylcyclohexane, 1, 1-bis-1 丨 4-mono (4-aminophenyl) Methyl] phenyl} 4- 4-octylcyclohexane, 1, 1-bis-1 {4-mono (4-aminoaminophenyl) methyl] phenyl} This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) -35- 581920 A7 B7 V. Description of the invention (33)-4-[2- (cyclohexyl) ethyl] cyclohexane, 1, 1-double one {4-(4-aminoaminobenzene) (Methyl) phenyl] (Please read the notes on the back before filling out this page)-4-[2-(4-methyl-trans-cyclohexyl) ethyl] cyclohexane丨 4 mono (4-aminoaminophenyl) methyl] phenyl} —4-mono [2-(4-monoethyl-trans-cyclohexyl) ethyl] cyclohexane 1, 1-double one 丨 4-one ( 4-monoaminophenyl) fluorenyl] phenyl} 4- 4- [2- -Trans-cyclohexyl) ethyl] cyclohexane1, 1-bis-1 丨 4 ((4-aminoaminophenyl) methyl] phenyl} -4-4 [2- (4-butyl-trans Monocyclohexyl) ethyl] cyclohexane 1, 1 bis one {4 mono (4 monoaminophenyl) methyl] phenyl} 4 4- [2-(4-pentyl-trans-cyclohexyl) ethyl Group] cyclohexane 1, 1, one pair one {4 one (4-aminoaminophenyl) methyl] phenyl} Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy One 4 one [2-(4-n-pentyl One trans one cyclohexyl) ethyl] cyclohexyl, 1, 1, one bis one {4 -— (4-aminoaminophenyl) methyl] phenyl} 4— [2— (4-hexyl-trans— Cyclohexyl) ethyl] cyclohexyl 1,1 bis one {4 one (4 monoaminophenyl) methyl] phenyl} 4 4- [2- (4-heptyl-trans-cyclohexyl) ethyl Base] The scale of this paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -36- 581920 A7 B7 V. Description of the invention (34) 1, 1 double 1 丨 4 1 (4 monoaminobenzene (Methyl) phenyl] (Please read the notes on the back first (Fill in this page) —4 — [2— (4-octyl-trans-cyclohexyl) ethyl] cyclohexane1, 1-bis-1 {4 ((4-aminoaminophenyl) methyl] phenyl }-4-[2-(4-nonyl-trans-cyclohexyl) ethyl] cyclohexane Λ 1, 1-bis-4-(4-aminoaminophenyl) methyl] phenyl}- 4- [2- (4-dodecyl-trans-cyclohexyl) ethyl] cyclohexane, 1, 1-bis- [4-((4-aminoaminophenoxy) phenyl] pentane 2, 2-Bis [4-mono (4-aminophenoxy) phenyl] pentane 3,3-Bis [4-mono (4-aminophenoxy) phenyl] pentane, 1, 1 double Mono- [4- mono (4-aminophenoxy) phenyl] hexane Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, employee consumer cooperatives% 2, 2-bis- [4-mono (4-monoaminophenoxy) phenyl] Hexane 3, 3-bis (4-mono (4-aminophenoxy) phenyl] hexamethylene 1, 1, 2-bis [4-mono (4-aminophenoxy) phenyl] heptane paper Standards are applicable to Chinese National Standard (CNS) Α4 specifications (210 × 297 mm) -37-581920 A7 B7 V. Description of the invention (3 5) 2, 2 -Bis [4 mono (4 monoaminophenoxy) phenyl] heptane 4 3 4 2 3 4 2 Bis Bi Bis 4
4 /IV 4 Γν 雙 雙 雙 雙 雙 4 4 4 Γν 4 基 氧 苯 基 胺 基 苯 烷 庚 基 氧 苯 基 胺 基 氧 苯 基 胺 基 氧 苯 基 胺 基 氧 苯 基 胺 基 氧 苯 基 胺 基 氧 苯 基 胺 基 氧 苯 基 胺 基 苯 基 苯 基 苯 基 苯 基 苯 基 苯 基 苯 烷 庚 烷 辛 烷 辛 烷 辛 烷 辛 烷 壬 烷 壬 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 3 4 5 雙 雙 雙 4 基 氧 苯 基 胺 基 氧 苯 基 胺 基 氧 苯 基 胺 基 苯 基 苯 基 苯 烷 壬 烷 壬 烷 壬 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -38- 581920 A7 B7 五、發明説明（36 ) 1， 1 一雙一〔4 一（4 一胺基苯氧基）苯基〕癸院 2 雙 基 苯 基 氧 苯 基 胺 烷 癸 3 雙 基 苯 \1/ 基 氧 苯 基 胺 烷 癸 4 雙 44 / IV 4 Γν Bishuang Bishuang Bi 4 4 4 Γν 4 Glyoxyphenylaminobenzylheptyloxyphenylaminophenylphenyloxyphenylaminooxyphenylaminophenyloxyphenylaminophenyloxyphenylamine Aminoaminooxyphenylaminophenylphenylphenylphenylphenylphenylphenyl phenyl heptane octane octane octane nonane nonane (Please read the notes on the back before filling this page) Ministry of Economy Printed by the Intellectual Property Bureau's Employee Cooperatives 3 4 5 Bishuangbi 4 based oxyphenylamino amine phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl phenyl nonane nonane nonane nonyl This paper size applies to Chinese national standards (CNS ) A4 specification (210 × 297 mm) -38- 581920 A7 B7 V. Description of the invention (36) 1, 1 one pair one [4 one (4 monoaminophenoxy) phenyl] decyl 2 bisylphenyloxy Phenylamine decane 3 Bisylbenzene \ 1 / yloxyphenylamine decane 4 Double 4
4 /IV 基 苯 \1/ 基 氧 苯 基 胺 烷 癸 5 雙 基 苯 NM/ 基 氧 苯 基 胺 烷 癸 (請先閲讀背面之注意事項再填寫本頁) 2 雙 基 苯 \ly 基 氧 苯 基 胺 烷 2 雙 基 苯 基 氧 苯 基 胺 烷 2 雙4 / IV based benzene \ 1 / based oxyphenylamine decane 5 based benzene NM / based oxyphenylamine decane (please read the notes on the back before filling this page) 2 based on benzene \ ly based oxybenzene Amine 2 Diphenylphenyloxyphenylamine 2 bis
4 /IV 基 苯 基 氧 苯 基 胺 三 烷 2 雙 基 苯 基 氧 苯 基 胺 四 經濟部智慧財產局員工消費合作社印製 烷 烷 烷 烷 2 2 2 雙 雙 雙 基 苯 基 氧 苯 基 胺 五 4 4 基 苯 基 氧 苯 基 胺 基 苯 基 氧 苯 基 胺 六 七 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -39- 581920 A7 B7 五、發明説明（37 ) 2，2 -雙一〔4 一（4 一胺基苯氧基）苯基〕十八 烷、 (請先閱讀背面之注意事項再填寫本頁) 2，2 -雙一〔4 一（4 一胺基苯氧基）苯基〕十九 烷、 1， 1 一雙一 {4 一〔 （4 一胺基苯基）曱基〕苯基 }戊院、 2，2 -雙一 {4 一〔 （4 一胺基苯基）甲基〕苯基 }戊院、 3， 3 -雙一 {4 一〔 （4 一胺基苯基）甲基〕苯基 }戊院、 1， 1一雙一{4一〔（4一胺基苯基）甲基〕苯基 }己院、 2，2 -雙一 {4 一〔 （4 一胺基苯基）曱基〕本基 }己烷、 3， 3 -雙一 {4 一〔 （4 —胺基苯基）甲基〕苯基 }己院、 1， 1 一雙一 {4 一〔 （4 一胺基苯基）曱基〕苯基 經濟部智慧財產局員工消費合作社印製 }庚烷、 2，2 -雙一丨4 一〔 （4 一胺基苯基）甲基〕苯基 }庚烷、 3， 3 -雙一丨4 一〔 （4 一胺基苯基）甲基〕苯基 }庚烷、 4，4 一雙一丨4 一〔 （4 —胺基苯基）甲基〕苯基 }庚烷、 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐） -40- 581920 A7 B7 五、發明説明（38 雙 基 苯 基 胺 基 甲 基 苯 烷 辛 2 雙 基 苯 基 胺 基 甲 基 苯 烷 辛 3 雙 4 基 苯 基 胺 基 甲 基 苯 辛 辛 烷 4 烷 4 雙 4 基 苯 基 胺 基 甲 基 苯 雙 4 基 苯 基 胺 基 曱 基 苯 (請先閲讀背面之注意事項再填寫本頁) 烷 壬 2 雙 4 基 苯 基 胺 基 甲 基 苯 烷 壬 3 雙 基 苯 基 胺 基 甲 基 苯 烷 壬 4 雙 基 苯 基 胺 基 甲 基 苯 烷 壬 5 雙 基 苯 基 胺 基 甲 基 苯 經濟部智慧財產局員工消費合作社印製 烷 壬 烷 癸 烷 癸 烷 癸 雙 基 苯 基 胺 基 曱 基 苯 2 3 雙 雙 4 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 基 苯 基 胺 基 ，苯 基 胺 基 甲 基 曱 基 苯 基 苯 -41 - 581920 A7 B7 經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 五、發明説明（39 ) 4，4 —雙—{ 4 —〔 }癸烷、 5，5 -雙-{ 4 -〔 }癸烷、 2，2 -雙-{ 4 -〔 }十一烷、 2，2 -雙-{ 4 -〔 }十二烷、 2，2 -雙-{ 4 -〔 }十三烷、 2，2 -雙-{ 4 -〔 }十四烷、 2，2 -雙-{ 4 -〔 }十五烷、 2，2 -雙-{ 4 -〔 }十六烷、 2，2 -雙-{ 4 -〔 }十七院、 2，2 -雙-{ 4 -〔 }十八院、 2，2 -雙-{ 4 -〔 }十九院、 1，1 -雙-{ 4 -〔 }全氟戊烷、 (4一胺基苯基）甲基〕苯基 (4一胺基苯基）甲基〕苯基 (4 一胺基苯基）甲基〕本基 (4一胺基苯基）甲基〕苯基 (4一胺基苯基）甲基〕苯基 (4一胺基苯基）甲基〕苯基 (4一胺基苯基）甲基〕苯基 (4一胺基苯基）甲基〕苯基 (4一胺基苯基）甲基〕苯基 (4一胺基苯基）甲基〕苯基 (4一胺基苯基）甲基〕苯基 (4一胺基苯基）甲基〕苯基 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -42- 581920 A7 B7 五、發明説明（40 ) 2 雙 基 苯 基 胺 基 甲 基 苯 烷 戊 氟 全 雙 4 4 基 苯 基 胺 基 甲 基 苯 全 全 烷1 烷 戊，己 S1 氟 雙 基 苯 基 胺 基 甲 基 苯 雙 4 基 苯 基 胺 基 甲 基 苯 全 全 全 烷.CO 烷 1 烷 己 ，己 ，庚 氟 3 氟 1 氟 雙 雙 雙 4 基 苯 基 胺 基 苯 基 胺 基 苯 基 胺 基 甲 基 甲 基 甲 基 苯 基 苯 基 苯 (請先閲讀背面之注意事項再填寫本頁) 全 全 烷 3 烷 庚，庚 氟 3 氟 雙 基 苯 基 胺 基 甲 基 苯 雙 4 基 苯 基 胺 基 甲 基 苯 經濟部智慧財產局員工消費合作社印製 全 全 全 全 烷 1烷 庚，辛 戴1 氟 烷3 烷 辛，辛 氟 3 氟 雙 雙 雙 基 苯 基 胺 基 甲 基 苯 4 4 4 本紙張尺度適用中國國家標準（CNS ) A4規格{ 210 X297公釐） 基 苯 基 胺 基 苯 基 胺 基 甲 基 曱 基 苯 基 苯 -43- 581920 A7 B7 五、發明説明（41 ) 4， 4 一雙一丨4 一〔 （4 一胺基苯基）甲基〕苯基 }全氟辛院、 (請先閲讀背面之注意事項再填寫本頁) 1， 1 一雙一 {4 一〔 （4 一胺基苯基）甲基〕苯基 }全氟壬院、 2， 2-雙一{4一〔 （4一胺基苯基）甲基〕苯基 }全氟壬院、 3， 3-雙一丨4一〔（4一胺基苯基）甲基〕苯基 }全氟壬院、 4，4 一雙一丨4 一〔 （4 一胺基苯基）甲基〕苯基 }全氟壬院、 5， 5 -雙一 {4 一〔 （4 一胺基苯基）甲基〕苯基 }全氟壬院、 1， 1一雙一{4一〔（4一胺基苯基）甲基〕苯基 }全氟癸院、 2， 2-雙一{4一〔 （4一胺基苯基）甲基〕苯基 }全氟癸院、 3， 3 -雙一 {4 一〔 （4 —胺基苯基）甲基〕苯基 經濟部智慧財產局員工消費合作社印製 }全氟癸烷、 4，4 一雙一 {4 一〔 （4 一胺基苯基）甲基〕苯基 }全氟癸烷、 5， 5 -雙一 {4 一〔 （4 一胺基苯基）曱基〕苯基 }全贏癸院、 2.， 2 -雙一丨4 一〔 （4 —胺基苯基）甲基〕苯基 }全赢i *院、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -44- 581920 A7 B7 五、發明説明（42 ) 2， 2 -雙一丨4 一〔 （4 一胺基苯基）甲基〕苯基 }全氟十二院、 (請先閱讀背面之注意事項再填寫本頁) 2， 2 -雙一 {4 一〔 （4 一胺基苯基）甲基〕本基 }全氟十三院、 2， 2 -雙一丨4 一〔 （4 一胺基苯基）甲基〕苯基 }全氟十四烷、 2， 2 —雙一 {4 一〔 （4 一胺基苯基）甲基〕苯基 }全赢十五院、 2，2 -雙一 {4 一〔 （4 一胺基苯基）甲基〕苯基 }全氟十六院、 2， 2 -雙一丨4 一〔 （4 —胺基苯基）甲基〕苯基 }全氟十七院、 2，2 -雙一 {4 一〔 （4 一胺基苯基）甲基〕苯基 }全氟十八院、 2， 2 -雙一丨4 一〔 （4 一胺基苯基）甲基〕苯基 }全氟/十九院等。 經濟部智慧財產局員工消費合作社印製 4 一〔3 -（4 一聯苯氧基）丙氧基〕一 1， 3 -二 胺基苯、 4 一〔8 -（4 一聯苯氧基）辛氧基〕一 1， 3 -二 胺基苯、 4 一〔3 -（4 一氰基聯苯基一 4’ 一氧基）丙氧基 〕一1， 3-一胺基苯、 4 一〔 1 2 -（4 一氯基聯苯基一 4 一氧基）十—^ 院氧基〕一 1，3 - 一胺基苯、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -45- 581920 A7 B7 五、發明説明（43 ) 4 —〔6 -（4 —甲氧基聯苯基一 4’ —氧基）己氧 基〕一 1，3 -一胺基苯、 (請先閲讀背面之注意事項再填寫本頁) 4 一〔 3 -（4 一氟聯苯基一 4’ 一氧基）丙氧基〕 —1，3 -一胺基苯、 2， 4一二胺基苯甲酸十二烷酯、 2，4 一二胺基苯甲酸辛酯、 1，5 - 一胺基一 2 -辛氧基幾基胺基苯、 1，4 —二胺基—3 —〔4— (4 —院基環己基）環 己氧基〕苯、 1，4 一二胺基一 3 -〔4 一（4 —院基苯基）環己 氧基〕苯、 1，4 一二胺基一 3 -（（4 一烷基聯三苯基）氧基 )苯、 1，4 一二胺基—（2 -院基）苯、 1，4 一二胺基一（2，5 -二烷基）苯、 2-烷氧基一1， 4一二胺基苯等。 1 一環己基一 4 一（4 一胺基苯甲基—2 -胺基苯基 經濟部智慧財產局員工消費合作社印製 院 己 環 4 基 己 環 基 甲 4 4 基 甲 苯 基 胺 基 苯 基 胺- 2 環 4 丙 基 苯 基 胺 I 2 環 基 、 己 、 烷環烷 己基己 44 / IV-based phenyloxyphenylamine trioxane 2 bisphenylphenyloxyphenylamine tetraane printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives printed alkanealkane 2 2 2 bisbisbisoxyphenylamine five 5 4-based phenyloxyphenylamine phenyloxyphenylamine sixty-seven paper size applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) -39- 581920 A7 B7 V. Description of the invention (37) 2, 2 -Bis [4-mono (4-aminoaminophenoxy) phenyl] octadecane, (Please read the precautions on the back before filling out this page) 2,2-Bis [4-mono (4-monoaminobenzene (Oxy) phenyl] 19-decane, 1, 1-bis- {4 1 [(4-monoaminophenyl) fluorenyl] phenyl} pentanyl, 2,2-bis- {4 1 [(4 1 Aminophenyl) methyl] phenyl} pentanyl, 3,3-bis- {4-a [(4-aminoaminophenyl) methyl] phenyl} pentanyl, 1, 1-bis-1 {4-1 [(4-Aminophenyl) methyl] phenyl} Hexane, 2,2-bis- {4-([(4-Aminophenyl) fluorenyl] benzyl] hexane}, 3,3-bis One {4 one [(4-aminophenyl) methyl Base] phenyl} Hexane, 1, 1, one double one {4 one [(4-Aminophenyl) fluorenyl] phenyl printed by the Intellectual Property Bureau Employees ’Cooperative of the Ministry of Economic Affairs} heptane, 2, 2-bis Mono- (4- (aminoaminophenyl) methyl] phenyl} heptane, 3,3-bis- (4- (aminoaminophenyl) methyl] phenyl} heptane, 4 , 4 one pair one 丨 4 one [(4-aminophenyl) methyl] phenyl} heptane, this paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -40- 581920 A7 B7 five Description of the invention (38 Diphenylphenylaminomethylbenzyloctane 2 Diphenylphenylaminomethylbenzyloctane 3 Bis 4-phenylphenylaminomethylphenoctane 4 Alkane 4 Bis 4-phenylphenyl Aminomethylbenzene bis 4-ylphenylaminofluorenylbenzene (Please read the precautions on the back before filling this page) Alkanon 2 Bis 4-phenylphenylaminomethylbenzylnon 3 Bisylphenylamino Methylbenzyl nonyl 4 Diphenylphenylaminomethylbenzyl nonyl 5 Diphenylphenylaminomethylbenzene Intellectual property bureau employee consumption Printed by Sakusha Co., Ltd. Alkanonane decane decane decyl bis phenyl amine fluorenyl benzene 2 3 bis bis 4 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) phenyl phenyl amine, phenyl Aminomethylfluorenylphenylbenzene-41-581920 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) V. Description of the invention (39) 4, 4 — Double — {4 — [} decane, 5,5-bis- {4-[} decane, 2,2-bis- {4-[} undecane, 2,2-bis- {4-[} ten Dioxane, 2,2-bis- {4-[} tridecane, 2,2-bis- {4-[} tetradecane, 2,2-bis- {4-[} pentadecane, 2, 2 -bis- {4-[} hexadecane, 2, 2 -bis- {4-[} Seventeen Houses, 2, 2 -bis- {4-[} 18 Houses, 2, 2 -Double- { 4-[} Nineteen Yuan, 1,1-bis- {4-[} Perfluoropentane, (4-monoaminophenyl) methyl] phenyl (4-monoaminophenyl) methyl] phenyl (4-monoaminophenyl) methyl] benzyl (4-monoaminophenyl) methyl] phenyl (4-monoaminophenyl) methyl] phenyl (4-monoaminophenyl Methyl] phenyl (4-aminoaminophenyl) methyl] phenyl (4-aminoaminophenyl) methyl] phenyl (4-aminoaminophenyl) methyl] phenyl (4-monoaminobenzene Methyl) phenyl] phenyl (4-aminoaminophenyl) methyl] phenyl (4-aminoaminophenyl) methyl] phenyl This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm)- 42- 581920 A7 B7 V. Description of the invention (40) 2 Diphenylphenylaminomethylbenzylpentafluoroperbis 4 4ylphenylaminomethylbenzeneperperane 1 alkanyl, hexafluorodiylbenzene Methylaminomethylbenzenebis 4-ylphenylaminomethylbenzene all peroxane.CO alkane 1 hexane hexane, hexane, heptane 3 fluoro 1 fluorobis bisbis 4-based phenylamino phenylamino phenylamine Methylmethylmethylmethylphenylphenylbenzene (please read the precautions on the back before filling out this page) all-per-alkane 3 alkane heptane, heptafluoro 3 fluorobisylphenylamino methylbenzene bis 4-ylphenyl Aminomethylbenzene Intellectual Property Bureau of the Ministry of Economic Affairs Employee Co-operative Cooperative Printed full allane 1 heptane, octane 1 halothane 3 Octafluoro 3 Fluorobisbisbisphenylphenylaminomethylbenzene 4 4 4 This paper size applies to Chinese National Standard (CNS) A4 specifications {210 X297 mm) phenylphenylaminophenylaminomethylfluorenylphenyl Benzene-43- 581920 A7 B7 V. Description of the invention (41) 4, 4 one pair one 丨 4 one [(4-aminoaminophenyl) methyl] phenyl} perfluorooctane, (Please read the note on the back first Please fill in this page again for the matters) 1, 1, one double one {4 one [(4 one aminophenyl) methyl] phenyl} perfluorononan, 2, 2-bis one {4 one [(4 one amino group Phenyl) methyl] phenyl} perfluorononin, 3,3-bis-4- 4-[(4-aminoaminophenyl) methyl] phenyl} perfluoronon-in, 4,4-bis-1 4 mono [(4-aminoaminophenyl) methyl] phenyl} perfluorononane, 5, 5-bis- {4-mono [(4-aminoaminophenyl) methyl] phenyl} perfluorononane , 1, 1-bis- {4-([4-aminoaminophenyl) methyl] phenyl} perfluorodecane, 2,2-bis- {4-([4-aminoaminophenyl) methyl ] Phenyl} perfluorodecane, 3,3-bis- {4-mono [(4-aminophenyl) methyl] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs} Perfluorodecane, 4,4 one pair one {4 one [(4-aminoaminophenyl) methyl] phenyl} perfluorodecane, 5, 5- Bis ({4-([4-aminoaminophenyl) fluorenyl] phenyl}}, 2, 2-Bis 4-([4-aminophenyl) methyl] phenyl}} All wins i * Institute, this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -44- 581920 A7 B7 V. Description of the invention (42) 2, 2-double one 丨 4 one [(4 monoamine Phenyl) methyl] phenyl} Perfluorododecane, (Please read the precautions on the back before filling out this page) 2, 2-Bis {4-a [(4-Aminophenyl) methyl] The base} Perfluorothirteen, 2, 2-Bis 4- 4- [[(4-Aminophenyl) methyl] phenyl} perfluorotetradecane, 2, 2-Bis {4 one [( 4 monoaminophenyl) methyl] phenyl} 15 wins, 2,2-bis- {4-mono [(4-monoaminophenyl) methyl] phenyl} perfluorohexadecane, 2 , 2 -bis-1 丨 4-[[4-aminophenyl) methyl] phenyl} perfluoroseventeen, 2,2-bis- {4-mono [(4-monoaminophenyl) methyl] phenyl} perfluorodecane, 2,2-bis- 丨 4-mono [(4-monoaminophenyl) methyl ] Phenyl} Perfluoro / Nineteen Houses, etc. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4-[3-(4-biphenyloxy) propoxy]-1, 3-diaminobenzene, 4-[8-(4-biphenyloxy) Octyloxy] -1,3-diaminobenzene, 4-a [3- (4-Cyanobiphenyl-4'-oxy) propoxy] -1,3-monoaminobenzene, 4-a [1 2-(4 -Chlorobiphenyl- 4 -oxyl) deca- ^ co-oxyl] -1,3 -monoaminobenzene, this paper size applies Chinese National Standard (CNS) A4 (210X 297 (Mm) -45- 581920 A7 B7 V. Description of the invention (43) 4- [6- (4-methoxybiphenyl-4'-oxy) hexyloxy] -1,3-monoaminobenzene (Please read the precautions on the back before filling this page) 4-[3-(4 -fluorobiphenyl-4 '-oxy) propoxy] -1,3 -monoaminobenzene, 2, 4 Dodecyl monoaminobenzoate, octyl 2,4-diaminobenzoate, 1,5-monoamino-2-octyloxypolyaminobenzene, 1,4-diamino- 3- [4- (4-Cyclocyclohexyl) cyclohexyloxy] benzene, 1,4-diamino- 3- 4-mono (4-Cyclophenyl) cyclohexyloxy] benzene, 1,4-diamino-3-((4-alkylbitriphenyl) oxy) benzene, 1,4-diamino — (2-Cyclosyl) benzene, 1,4-diaminomono (2,5-dialkyl) benzene, 2-alkoxy-1,4-diaminobenzene, etc. 1 monocyclohexyl-1 4-mono (4-aminophenylbenzyl-2-aminophenylphenyl) Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives Printing Institute, Hexacycline 4 Hexylcyclomethyl 4 4 Tolylaminophenylphenylamine -2 ring 4 propylphenylamine I 2 ring, hex, alkanecyclohexyl hexane 4
4 /IV 基 甲 苯 基 胺 r—Η 4 基 己 環 基 戊 44 / IV methylmethylphenylamine r-fluorene 4yl hexyl pentyl 4
4 /(V 基 甲 苯 基 胺 基 苯 基 胺- 2 烷 己 環 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -46- 581920 A7 ---^________ 五、發明説明（44 ) 1— (4 一辛基環己基）一 4 一（4 一胺基苯甲基一 2〜胺基苯基）環己烷、 1 一（4 一癸基環己基）一 4 一（4 —胺基苯甲基一 2〜胺基苯基）環己烷、 1 一（4 —十二烷基環己基）—4 一（4 一胺基苯甲 基一2-胺基苯基）環己烷、 1一環己基一4—(3-胺基苯甲基一2-胺基苯基 )環己院、 1— (4 一甲基環己基）一 4 一（3 —胺基苯甲基一 2-胺基苯基）環己烷、 1 一（4 —丙基環己基）—4 一（3 -胺基苯甲基一 2-胺基苯基）環己烷、 1— (4 —戊基環己基）—4 一（3 -胺基苯甲基— 2 -胺基苯基）環己院、 1 一（4 一辛基環己基）一 4 一（3 -胺基苯甲基一 2-胺基苯基）環己烷、 1_ (4 —癸基環己基）一 4 一（3 -胺基苯甲基一 2-胺基苯基）環己烷、 1 一（4 —十一院基環己基）一 4 一（3 -胺基苯甲 基一2-胺基苯基）環己烷等。 此外，膽固醇、雄留酮、Θ -膽固醇、表雄留酮、麥 角固醇、雌激素、1 Ια —羥甲基固醇、1 ία 一黃體素 、羊毛甾醇、哌苯甲醇、甲基睪九素、降睪九素、孕留稀 醇酮、Α -谷甾醇、豆甾醇、睪九素、乙酸膽固醇g旨等具 I -- (請先閲讀背面之注意事項再填寫本頁)4 / (V-based tolylaminophenyl phenylamine-2 alkanecyclohexylcyclohexyl chloride This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) -46- 581920 A7 --- ^ ________ V. Description of the invention (44 ) 1— (4-octylcyclohexyl) —4— (4-aminoaminobenzyl—2 ~ aminophenyl) cyclohexane, 1— (4-decylcyclohexyl) —4— (4 — Aminobenzyl- 2 ~ aminophenyl) cyclohexane, 1- (4-dodecylcyclohexyl) -4 (4-aminoaminobenzyl-2-aminophenyl) cyclohexyl Alkanes, 1-cyclohexyl-4- (3-aminobenzyl-2-aminophenyl) cyclohexane, 1- (4-methylcyclohexyl) -4- (3-aminobenzyl- 2-aminophenyl) cyclohexane, 1- (4-propylcyclohexyl) -4- (3-aminophenylmethyl 2-aminophenyl) cyclohexane, 1- (4-pentyl Cyclohexyl) -4 4- (3-aminobenzyl-2-aminophenyl) cyclohexyl, 1- (4-octylcyclohexyl) -4 4- (3-aminobenzyl-2 -Aminophenyl) cyclohexane, 1- (4-decylcyclohexyl) -4 (3-aminophenylmethyl 2-amine Phenyl) cyclohexane, 1- (4-undecylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane, etc. In addition, cholesterol, androstyl Ketones, Θ-cholesterol, epiandrostenone, ergosterol, estrogen, 1 Ια-hydroxymethyl sterol, 1 ία-lutein, lanosterol, piperhydrol, methylpentanosin, norbinoxine Vegetarians, sterols, A-sitosterol, stigmasterol, lindensin, cholesterol acetate, etc.-(Please read the precautions on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作社印製Printed by 1T Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs
-47- 581920 A7 B7__ 五、發明説明（45 ) 有類固醇骨架側鏈之二胺。 (請先閲讀背面之注意事項再填寫本頁) 有關本發明之二胺並非限定於上述者，能達成本發明 目的之範圍內可有各種其他型態存在乃母庸贅言。又，此 等二胺可單獨亦可2種以上組合使用。 此外，此等二羧酸、二羧酸鹵、四羧酸二酐及二胺以 外欲形成聚醯胺酸之反應末端，亦可倂用單胺化合物或/ 及單羧酸酐。爲使對基板之黏著性良好，亦可導入胺基矽 化合物或二胺基砂化合物。 胺基矽化合物可例舉如對-胺基苯基三甲氧基矽烷、 對-胺基苯基三乙氧基矽烷、間-胺基苯基三曱氧基矽烷 、間-胺基苯基三乙氧基矽烷、胺基丙基三甲氧基矽烷、 胺基丙基三乙氧基矽烷等。 此外，二胺基矽化合物亦可例舉如1 , 3 -雙（3 - 胺基丙基）—1, 1，3，3 -四苯基二矽氧烷、1，3 一雙（3 -胺基丙基）一 1， 1，3， 3 -四甲基二矽氧 烷、1， 3 —雙（4一 胺基丁基）—1， 1， 3， 3 —四 甲基二矽氧烷等。 經濟部智慧財產局員工消費合作社印製 本發明之液晶配向劑漆中聚合物成分之濃度以0 · 4 重量％爲佳。雖然將液晶配向劑漆塗布於基板之際，有時 必需先以溶劑將所含之聚合物成分稀釋以調整膜厚，但若 聚合物成分之濃度超過4 0重量％則液晶配向劑漆之黏度 過高，即使添加溶劑與液晶配向劑漆之混合亦不佳，而發 生難以獲得均勻溶液等缺點而不宜。若爲旋鍍法或印刷法 之情況，爲了良好保持膜厚，通常大多爲1 0重量％以下 本紙張尺度適用中國國家標準（CNS ) A4規格（210'〆297公釐） -48- 581920 A7 B7 五、發明説明（46 ) (請先閱讀背面之注意事項再填寫本頁) 。其他塗佈方法例如浸漬法亦可爲低於1 0重量％之濃度 。另一方面，若聚合物成分之濃度低於0 · 1重量％則易 產生所得配向膜膜厚過薄之問題。因此一般旋鍍法或印刷 法等情況，聚合物成分之濃度爲0 . 1重量％以上，較好 爲0 . 5至1 0重量％左右。然而，依據液晶配向劑漆之 塗布方法亦可使用更稀薄之濃度。 經濟部智慧財產局員工消費合作社印製 本發明之液晶配向劑漆中與前述聚合物成分共同使用 之溶劑，可使用任何可溶解聚合物成分之溶劑並無特殊限 定。該溶劑廣泛包括聚醯胺酸、可溶性聚醯亞胺、聚醯胺 之製造步驟或用途方面常使用之溶劑，可視使用目的選擇 適當之較佳溶劑。此等溶劑可使用例如對聚醯胺酸、可溶 性聚醯亞胺、聚醯胺爲優良溶劑之非質子性極性有機溶劑 ，例如N -甲基一 2 -吡咯烷酮、二甲基咪唑烷酮、N -甲基己內醯胺、N —甲基二乙基甲酮醯胺、N，N —二甲 基乙醯乙醯胺、二甲基咪唑二酮、N，N —二甲基甲醯胺 、N， N—二乙基甲醯胺、二乙基乙醯乙醯胺或r一丁內 酯等，爲改善塗佈性等目的亦可使用其他溶劑，例如乳酸 烷酯、3 -甲基一 3 -甲氧基丁醇、四氫化萘、異佛爾酮 、乙二醇單丁基醚等乙二醇單烷基醚，二乙二醇單乙基醚 等二乙二醇單烷基醚，乙二醇單烷基酯或苯基乙酸酯、三 乙二醇單烷基醚、丙二醇單丁基醚等丙二醇單烷基醚，丙 二酸二乙酯等丙二酸二烷酯，二丙二醇單甲基醚等二丙二 醇單烷基醚，或此等之乙酸酯化合物等酯系化合物。 欲形成配向膜時，將液晶配向劑漆塗布於基板之步驟 本紙張尺度適用中國國家標準（CNS ) A4規格（2⑴X297公釐） -49 - 581920 A7 ___B7 五、發明説明（47 ) 、後續之乾燥步驟及脫水•閉環反應可藉施與必要之加熱 處理步驟而進行。進行此種步驟之塗佈方法爲旋鍍法、印 (請先閲讀背面之注意事項再填寫本頁) 刷法、浸漬法或滴下法等一般習知方法，此等亦同樣適用 於本發明中使用。又，加熱方法爲烘箱或紅外線爐中加熱 處理之方法或於熱板上進行加熱處理之方法等習知方法， 此等亦同樣適用於本發明中使用。 乾燥方法以於溶劑可蒸發範圍內之較低溫度下進行爲 佳，又加熱處理之溫度一般以1 5 0至3 0 0 t範圍爲佳 0 本發明之液晶配向劑漆視需要亦可含有各種添加劑。 例如，欲提昇塗佈性時可配合達成該目的之介面活性劑， 必需提昇帶電防止性時可配合帶電防止劑，或欲提高與基 板之黏著性時可配合矽烷偶合劑或鈦系偶合劑。 經濟部智慧財產局員工消費合作社印製 使微粒子分散於上述配向劑漆中而作成配向膜並非必 要之條件，亦可分別調製配向劑漆及微粒子，於塗佈配向 劑漆後再使微粒子分散於其表面。例如，將不含固體微粒 子之液晶配向劑漆以旋塗法塗布於基板後，使溶劑乾燥而 作成薄膜，再將以分散劑分散之微粒子分散於其表面後， 經加熱處理而作成配向膜。又，固體微粒子可使用與液晶 配向劑漆中所添加者相同之物。當然，亦可於塗布含有固 體微粒子之本發明液晶配向劑漆後，另外再將固體微粒子 分散於薄膜上。 本發明所用配向膜之前置傾斜角較好爲3至2 0度， 更好爲4至1 5度。由於〇C B型液晶顯示元件中，若液 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -50- 581920 A7 B7 五、發明説明（48 ) 晶之傾斜角變大則彎曲配向狀態安定，因而以傾斜角大者 爲佳，但若過大則受製造過程等影響而傾斜角之變動變大 (請先閲讀背面之注意事項再填寫本頁) 〇 實施例 下文說明自輻射配向狀態快速轉移至彎曲配向狀態之 〇C B型液晶顯示元件之例。 實施例1 1)液晶配向劑漆之合成 於備有溫度計、攪拌機、原料投入口及氮氣導入口之 200ml四頸燒瓶中置入〇.8118g 4， 4’ — 二胺基二苯基乙烷、2 . 5200g 1， 1—雙{4 — 經濟部智慧財產局員工消費合作社印製 4 〔 （4 — fee基本氧基）苯基丨丨—4 一〔2 -（4 一庚 基—反式—環己基）乙基〕環己烷、30 · 00g脫水N 一甲基一 2 -啦咯院酮（NMP),於乾燥氮氣流下攪拌 溶解之。將反應系之溫度保持於5 °C並一邊添加 1 . 6 6 8 2 g均苯四甲酸二酐，反應3 0小時後，添加 35.00g 丁基溶纖劑（BC) 、35.00g γ -丁內酯而合成聚合物成分之濃度爲6重量％之聚醯胺酸液 晶配向劑漆。原料之反應中若反應溫度上升時，將反應溫 度控制在約7 0 °C以下進行反應。又，本發明之實施例， 係於反應進行中一邊檢測黏度，以添加丁基溶纖劑後液晶 配向劑漆之黏度成爲5 5至6 5mP a · s (使用E型黏 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -51- 581920 A7 經濟部智慧財產局員工消費合作社印製 _ B7五、發明説明（49 ) 度劑，2 5 °C )時作爲反應終點，於低溫下保存。 於如上所得之液晶配向劑漆中，混合對聚合物成分量 爲1 0重量％之平均粒徑2 0 nm之銦錫氧化物（下文稱 爲1丁〇），再將該混合系以NMP與BC爲1 : 1之混 合溶劑稀釋，調整成全部聚合物成分之濃度爲3重量％作 爲塗布用液晶配向劑漆並以旋轉式塗布於透明基板上，於 8 0 °C進行約5分鐘之預備焙烤。繼之於2 1 0 °C進行加 熱處理3 0分鐘而形成膜厚6 0 nm之配向膜，於其表面 全面藉由揉擦進行配向處理。此處，以掃描式電子顯微鏡 (S E Μ )進行觀察，可確認於該配向膜表面上二次粒徑 6 0 0 nm至1 8 0 0 nm之I Τ〇微粒子係呈均勻分散 狀態。 2 )電氣特性評估用電池之製作 將如上所得之配向膜於乙醇中以超音波洗滌5分鐘後 ，以流水洗淨表面，再於烘箱中1 2 0 °C乾燥3 0分鐘。 於上述基板上散佈5 // m之塡縫材，以形成配向膜之面爲 內側並以環氧硬化劑密封，作成間隙5 // m之平行電池。 於上述電池中注入液晶材料，以光硬化劑封閉注入口。繼 之於1 1 0 °C加熱處理3 〇分鐘，作成電氣特性評估用電 池。作爲液晶材料使用之液晶組成物其組成如下示。（％ 係表示重量％ )。 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇χ297公釐） -52- 581920 A7 _B7-47- 581920 A7 B7__ 5. Description of the invention (45) Diamine with side chain of steroid skeleton. (Please read the notes on the back before filling this page.) The diamine of the present invention is not limited to the above, and there can be various other forms within the scope of the purpose of the invention. These diamines may be used alone or in combination of two or more. In addition, in addition to these dicarboxylic acids, dicarboxylic acid halides, tetracarboxylic dianhydrides, and diamines, it is also possible to use a monoamine compound or / and a monocarboxylic acid anhydride in order to form a reaction terminal of polyamic acid. In order to improve the adhesion to the substrate, an amine silicon compound or a diamine sand compound may be introduced. Examples of the amino silicon compound include p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenyltrisiloxane. Ethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, etc. In addition, the diamino silicon compound can also be exemplified by 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetraphenyldisilaxane, 1, 3-bis (3- Aminopropyl) -1,1,3,3-tetramethyldisilaxane, 1,3-bis (4-aminoaminobutyl) -1,1,3,3-tetramethyldisilaxane Alkanes, etc. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The concentration of the polymer component in the liquid crystal alignment agent paint of the present invention is preferably 0.4% by weight. Although the liquid crystal alignment agent paint is applied to the substrate, it may be necessary to first dilute the polymer component contained in the solvent to adjust the film thickness. If the concentration of the polymer component exceeds 40% by weight, the viscosity of the liquid crystal alignment agent paint If it is too high, even if the solvent is mixed with the liquid crystal alignment agent paint, the disadvantages such as difficulty in obtaining a uniform solution and the like are not suitable. In the case of spin plating or printing, in order to maintain the film thickness, it is usually mostly less than 10% by weight. This paper size applies the Chinese National Standard (CNS) A4 specification (210'〆297 mm) -48- 581920 A7 B7 V. Description of Invention (46) (Please read the notes on the back before filling this page). Other coating methods, such as the dipping method, may also have a concentration of less than 10% by weight. On the other hand, if the concentration of the polymer component is less than 0.1% by weight, there is a problem that the thickness of the obtained alignment film is too thin. Therefore, the concentration of the polymer component is generally 0.1% by weight or more, and preferably about 0.5 to 10% by weight in the case of spin coating or printing. However, a thinner concentration may be used according to the coating method of the liquid crystal alignment agent paint. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The solvent used in the liquid crystal alignment agent paint of the present invention with the aforementioned polymer components may be any solvent that can dissolve the polymer components and is not particularly limited. The solvent widely includes solvents commonly used in the production steps or applications of polyamidonic acid, soluble polyamidoimide, and polyamidoamine. An appropriate and suitable solvent can be selected according to the purpose of use. As these solvents, aprotic polar organic solvents, such as polyamidomic acid, soluble polyamidoimide, polyamidomine, can be used, such as N-methyl-2-pyrrolidone, dimethylimidazolidone, N -Methylcaprolactam, N-methyldiethylketamine, N, N-dimethylacetamidine, dimethylimidazolidine, N, N-dimethylformamide , N, N-diethylformamidine, diethylacetamidine or r-butyrolactone, etc. Other solvents can also be used for the purpose of improving coating properties, such as alkyl lactate, 3-methyl Monoethylene glycol monoalkyl ethers such as 3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, and diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether Ethers, propylene glycol monoalkyl ethers such as ethylene glycol monoalkyl esters or phenyl acetates, triethylene glycol monoalkyl ethers, propylene glycol monobutyl ethers, and dialkyl malonates such as diethyl malonate , Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, or ester compounds such as acetate compounds. Steps for applying the liquid crystal alignment agent paint to the substrate when an alignment film is to be formed The steps and dehydration-closed loop reactions can be performed by applying necessary heat treatment steps. The coating method for performing this step is spin plating, printing (please read the precautions on the back before filling this page), brushing, dipping or dripping, and other conventional methods, which are also applicable to the present invention. use. In addition, the heating method is a conventional method such as a method of heating in an oven or an infrared oven or a method of heating on a hot plate. These methods are also applicable to the present invention. The drying method is preferably carried out at a lower temperature within the solvent's evaporable range, and the temperature of the heat treatment is generally in the range of 150 to 300 t. The liquid crystal alignment agent paint of the present invention can also contain various kinds as required. additive. For example, a surfactant can be used to improve the coating property, a charging preventive agent can be used to improve the antistatic property, or a silane coupling agent or a titanium coupling agent can be used to improve the adhesion to the substrate. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints that it is not necessary to disperse the particles in the above-mentioned alignment agent paint to make an alignment film. It is also possible to separately prepare the alignment agent paint and the particles, and then disperse the particles in the alignment agent paint. Its surface. For example, a liquid crystal alignment agent lacquer containing no solid particles is spin-coated on a substrate, and then the solvent is dried to form a thin film. The particles dispersed with a dispersant are dispersed on the surface, and then subjected to heat treatment to form an alignment film. As the solid fine particles, the same as those added to the liquid crystal alignment agent paint can be used. Of course, after coating the liquid crystal alignment agent paint of the present invention containing solid fine particles, the solid fine particles may be further dispersed on the film. The inclination angle of the alignment film used in the present invention is preferably 3 to 20 degrees, more preferably 4 to 15 degrees. As for the 〇CB type liquid crystal display element, if the size of the liquid paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -50- 581920 A7 B7 V. Description of the invention (48) The orientation of the crystal becomes larger, the bending alignment The state is stable, so the larger tilt angle is better, but if it is too large, the variation of the tilt angle will be affected by the manufacturing process and so on (please read the precautions on the back before filling this page) 〇 The examples below explain the self-radiation alignment state An example of a 0CB liquid crystal display element that quickly transitions to a curved alignment state. Example 1 1) Synthesis of liquid crystal alignment agent paint In a 200 ml four-necked flask equipped with a thermometer, a stirrer, a raw material input port and a nitrogen inlet port, 0.8118 g of 4, 4'-diaminodiphenylethane, 2. 5200g 1, 1-bis {4 — Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 [(4 — fee basic oxygen) phenyl 丨 丨 4 — [2-(4 heptyl — trans — Cyclohexyl) ethyl] cyclohexane, 30. 00 g of dehydrated N-methyl-2- 2-pyrrolidinone (NMP), which was dissolved by stirring under a stream of dry nitrogen. While maintaining the temperature of the reaction system at 5 ° C, 1. 6 8 2 g of pyromellitic dianhydride was added. After 30 hours of reaction, 35.00 g of butyl cellosolve (BC) and 35.00 g of γ-butyrolactone were added. The synthetic polymer liquid crystal alignment agent paint has a concentration of 6 wt%. When the reaction temperature rises during the reaction of the raw materials, the reaction temperature is controlled to be below 70 ° C. In addition, in the embodiment of the present invention, the viscosity is measured while the reaction is in progress, and the viscosity of the liquid crystal alignment agent paint becomes 5 5 to 6 5 mP a · s after the butyl cellosolve is added. (CNS) A4 specification (210X297 mm) -51- 581920 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs _ B7 V. Description of the invention (49) Degree agent, 25 ° C) as the reaction endpoint, at low temperature save. In the liquid crystal alignment agent paint obtained above, an indium tin oxide (hereinafter referred to as 1butyl) having an average particle size of 20 nm and an average particle size of 10% by weight of a polymer component was mixed, and then the mixture was mixed with NMP and BC is diluted with a mixed solvent of 1: 1, and the concentration of all polymer components is adjusted to be 3% by weight. As a coating liquid crystal alignment agent paint, it is spin-coated on a transparent substrate and prepared at 80 ° C for about 5 minutes. Bake. Then, heat treatment was performed at 210 ° C for 30 minutes to form an alignment film with a thickness of 60 nm, and the entire surface was subjected to alignment treatment by rubbing. Here, when observed with a scanning electron microscope (SEM), it was confirmed that the I TO fine particles having a secondary particle diameter of 600 nm to 1800 nm on the surface of the alignment film were uniformly dispersed. 2) Production of battery for evaluation of electrical characteristics After the alignment film obtained above was washed with ethanol for 5 minutes in ultrasonic, the surface was washed with running water, and then dried in an oven at 120 ° C for 30 minutes. A 5 // m quilting material was spread on the above substrate, with the surface forming the alignment film as the inner side and sealed with an epoxy hardener to form a parallel battery with a gap of 5 // m. A liquid crystal material is injected into the battery, and the injection port is closed with a light hardener. Then, it was heat-treated at 110 ° C for 30 minutes to prepare a battery for evaluating electrical characteristics. The composition of a liquid crystal composition used as a liquid crystal material is shown below. (% Means% by weight). (Please read the precautions on the back before filling this page) The paper size is applicable to Chinese National Standard (CNS) A4 (21〇297297 mm) -52- 581920 A7 _B7
五、發明説明（50 )V. Description of the invention (50)
(請先閲讀背面之注意事項再填寫本頁) 對所得之液晶電池施加周波數3 0 H z、7 V之矩形 波電壓，觀察每個電極全面（1 · 0 c m 2 )自輻射配向狀 態至彎曲配向狀態之轉移核產生之數目，可確認電極大約 全面均有無數之轉移核產生，約5秒鐘電極全面即自輻射 配向狀態確實轉移至彎曲配向狀態。 對上述液晶顯示元件施加周波數3 0 Η z、〇至5 V 之矩形波電壓，測定彎曲轉移核之產生電壓爲3 · 0 2 V 。又，輻射配向及彎曲配向狀態之境界電壓（V c r )爲 1 . 7 3 V。又，液晶之配向性亦良好。 經濟部智慧財產局員工消費合作社印製 3 )前置傾斜角測定用電極之製作 除了使用2 0 // m之塡縫材作成且爲反平行之外，依 據電池電氣特性評估用電池之相同方法製作前置傾斜角測 定用電池。又，前置傾斜角測定所用之液晶材料亦使用電 池電氣特性測定時所用者相同物。使用該電池以晶體旋轉 法測定液晶之前置傾斜角爲9 . 6度。 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -53 - 581920 A7 B7 五、發明説明（51 ) 實施例2 (請先閲讀背面之注意事項再填寫本頁) 除了於液晶配向劑漆中混合3 0重量％之I T ◦以外 ，依據實施例1之方法製作電池，觀察每個電極全面（ 1 . 0 c m 2 )自輻射配向狀態至彎曲配向狀態之轉移核產 生之數目，而確認電極大約全面均有無數之轉移核產生， 約4秒鐘電極全面即自輻射配向狀態確實轉移至彎曲配向 狀態。 對上述液晶顯示元件施加周波數3 0 Η z、〇至5 V 之矩形波電壓，測定彎曲轉移核之產生電壓爲2 · 8 0 V 。輻射配向及彎曲配向狀態之境界電壓（V c r )爲 1 . 7 0 V。又，液晶之配向性亦良好。 又，依據實施例1製作前置傾斜角測定用電池，以晶 體旋轉法測定液晶之前置傾斜角爲9 . 2度。 實施例3 除了液晶配向劑漆中係混合5 0重量％之I T〇以外 依據實施例1之方法製作電池，觀察每個電極全面（ 經濟部智慧財產局員工消費合作社印製 1 . 0 c m 2 )自輻射配向狀態至彎曲配向狀態之轉移核產 生之數目，而確認電極大約全面均有無數之轉移核產生， 約1秒鐘電極全面即自輻射配向狀態確實轉移至彎曲配向 狀態。 對上述液晶顯示元件施加周波數3 0 Η z、〇至5 V 之矩形波電壓，測定彎曲轉移核之產生電壓爲2 . 5 0 V 。輻射配向及彎曲配向狀態之境界電壓（V c r )爲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 -54 - 581920 A7 B7 五、發明説明（52 ) 1 · 6 5 V。又，液晶之配向性亦良好。 (請先閲讀背面之注意事項再填寫本頁) 又，依據實施例1製作前置傾斜角測定用電池，以晶 體旋轉法測定液晶之前置傾斜角爲8 . 8度。 實施例4 除了於實施例1之液晶配向劑漆中係混合1 0重量％ 之2 0 n m氧化銻以外，依據實施例1之方法製作電池， 觀察每個電極全面（1 . 0 c m 2 )自輻射配向狀態至彎曲 配向狀態之轉移核產生之數目，而確認電極大約全面均有 無數之轉移核產生，約8秒鐘電極全面即自輻射配向狀態 確實轉移至彎曲配向狀態。 對上述液晶顯示元件施加周波數3 Ο Η z、0至5 V 之矩形波電壓，測定彎曲轉移核之產生電壓爲3 . 1 Ο V 。輻射配向及彎曲配向狀態之境界電壓（V c I* )爲 1 . 7 4 V。又，液晶之配向性亦良好。 又，依據實施例1製作前置傾斜角測定用電池，以晶 體旋轉法測定液晶之前置傾斜角爲9 . 8度。 經濟部智慧財產局員工消費合作社印製 實施例5 除了實施例1之液晶配向劑漆中係混合3 0重量％之 2 0 n m氧化銻以外，依據實施例1之方法製作電池，觀 察每個電極全面（1 · 0 c m 2 )自輻射配向狀態至彎曲配 向狀態之轉移核產生之數目，而確認電極大約全面均有無 數之轉移核產生，約6秒鐘電極全面即自輻射配向狀態確 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -55- 581920 A7 B7 五、發明説明（53 ) 實轉移至彎曲配向狀態。 (請先閲讀背面之注意事項再填寫本頁) 對上述液晶顯示元件施加周波數3 0 Η z、〇至5 V 之矩形波電壓，而測定彎曲轉移核之產生電壓時爲 2 · 9 0 V。又，輻射配向及彎曲配向狀態之境界電壓（ v c r )爲1 . 7 1 V。又，液晶之配向性亦良好。 又，依據實施例1製作前置傾斜角測定用電池，以晶 體旋轉法測定液晶之前置傾斜角爲9 . 4度。 實施例6 除了實施例1之液晶配向劑漆中係混合1 0重量％之 氧化矽以外，依據實施例1之方法製作電池，觀察每個電 極全面（1 · 0 c m 2 )自輻射配向狀態至彎曲配向狀態之 轉移核產生之數目，而確認電極大約全面均有無數之轉移 核產生，約7秒鐘電極全面即自輻射配向狀態確實轉移至 彎曲配向狀態。 經濟部智慧財產局員工消費合作社印製 對上述液晶顯示元件施加周波數3 0 Η z、〇至5 V 之矩形波電壓，測定彎曲轉移核之產生電壓爲3 . 0 5 V 。輻射配向及彎曲配向狀態之境界電壓（V c r )爲 1 . 7 3 V。又，液晶之配向性亦良好。 又，依據實施例1製作前置傾斜角測定用電池，以晶 體旋轉法測定液晶之前置傾斜角爲9 . 7度。 實施例7 除了於實施例1之液晶配向劑漆中係混合3 0重量％ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -56- 581920 Α7 Β7 五、發明説明（54 ) 之氧化矽以外，依據實施例1之方法製作電池，觀察每個 電極全面（1 · 0 c m 2 )自輻射配向狀態至彎曲配向狀態 (請先閲讀背面之注意事項再填寫本頁) 之轉移核產生之數目，而確認電極大約全面均有無數之轉 移核產生，約5秒鐘電極全面即自輻射配向狀態確實轉移 至彎曲配向狀態。 對上述液晶顯示元件施加周波數3 Ο Η z 、0至5 V 之矩形波電壓，測定彎曲轉移核之產生電壓爲2 . 8 5 V 。又，輻射配向及彎曲配向狀態之境界電壓（V c I* )爲 1 · 7 1 V。又，液晶之配向性亦良好。 又，依據實施例1製作前置傾斜角測定用電池，以晶 體旋轉法測定液晶之前置傾斜角爲9 . 3度。 比較例1 經濟部智慧財產局員工消費合作社印製 除了於實施例1之液晶配向劑漆中不添加固體微粒子 以外，依據實施例1之方法製作電池，觀察每個電極全面 (1 . 0 c m 2 )自輻射配向狀態至彎曲配向狀態之轉移核 產生之數目，確認約有2 0個轉移核產生，約1 5秒鐘電 極全面自輻射配向狀態轉移至彎曲配向狀態。 對上述液晶顯示元件施加周波數3 Ο Η z、〇至5 V 之矩形波電壓，而測定彎曲轉移核之產生電壓時爲 3 · 7 4 V。又，輻射配向及彎曲配向狀態之境界電壓（ V c r )爲1 · 7 8 V。又，液晶之配向性亦良好。 又，依據實施例1製作前置傾斜角測定用電池，以晶 體旋轉法測定液晶之前置傾斜角爲1 〇 . 7度。 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ297公釐） -57- 581920 A7 B7 五、發明説明（55 ) 實施例1至7、比較例1之結果示於表1。 表1 固體 微粒子 對聚合物成分 量之固體微粒 子之雷量％ 彎曲轉移 核產生數 (個/cm2) 自輻射配向轉移 至彎曲配向之轉 移時間(秒） 產生彎曲 轉移核之 電壓(V) Vcr(V) 前置傾 斜角(° ) 實 1 ITO 10 00 5 3.02 1.73 9.6 施 2 ITO 30 00 4 2.80 1.70 9.2 例 3 ITO 50 〇〇 1 2.50 1.65 8.8 4 氧化銻 10 〇〇 8 3.10 1.74 9.8 5 氧化銻 30 00 6 2.90 1.71 9.4 6 氧化石夕 10 00 7 3.05 1.73 9.7 7 氧化石夕 30 〇〇 5 2.85 1.71 9.3 比 較 例 1 不添加 — 20 15 3.74 1.78 10.7 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 如上述，添加固體微粒子之液晶顯示元件順利的局部 產生自輻射配向狀態至彎曲配向狀態之轉移核，而於短時 間內進行轉移，此外V c r亦降低，亦即配向膜中固體微 粒子附近之電壓局部變高，推測該結果造成產生自輻射配 向狀態轉移至彎曲配向狀態之轉移核之機會。 一般而言，已知液晶之前置傾斜角變低時其轉移電壓 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -58 - 581920 A7 __B7 五、發明説明（56 ) 有增大之傾向，而添加固體微粒子之液晶顯示元件相反的 彎曲轉移核之發生電壓降低。確認添加固體微粒子之配向 劑漆之液晶之前置傾斜角爲較未添加固體微粒子時之前置 傾斜角，1 0 . 7度爲更低之値。 產業上利用之可能性 本發明係藉由使用由含有固體微粒子之液晶配向劑漆 所形成之配向膜或固體微粒子分散於表面之配向膜，而提 供於低電壓即可迅速且確實的進行自輻射配向狀態至彎曲 配向狀態之轉移之0 C B型液晶顯示元件。 !,1II (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） •59-(Please read the precautions on the back before filling this page) Apply a rectangular wave voltage of 3 0 H z, 7 V to the obtained liquid crystal cell, and observe the full (1 · 0 cm 2) self-radiation alignment state of each electrode to The number of transition nuclei generated in the bending alignment state can be confirmed that there are countless transition nuclei generated in the electrode in an approximately comprehensive manner. In about 5 seconds, the electrode is fully transferred from the radiation alignment state to the curved alignment state. A rectangular wave voltage with a cycle number of 30 Η z and 0 to 5 V was applied to the above-mentioned liquid crystal display element, and the generated voltage of the bending transition nucleus was measured to be 3.02 V. The boundary voltage (V c r) of the radiation alignment and bending alignment states is 1. 7 3 V. In addition, the alignment of the liquid crystal is also good. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3) The same method used to evaluate the electrical properties of batteries based on the electrical characteristics of the batteries, except that the electrodes for measuring the front tilt angle are made using a quilted material of 20 // m A battery for measuring front tilt angle was produced. The liquid crystal material used for the measurement of the front tilt angle is the same as that used for the measurement of the electrical characteristics of the battery. Using this battery, the inclination angle of the liquid crystal measured by the crystal rotation method was 9.6 degrees. This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) -53-581920 A7 B7 V. Description of the invention (51) Example 2 (Please read the precautions on the back before filling this page) Except for In addition to mixing 30% by weight of IT in the liquid crystal alignment agent paint, a battery was fabricated according to the method of Example 1, and the number of transition nuclei generated from the radiation alignment state to the bending alignment state of each electrode in its entirety (1.0 cm 2) was observed. And it is confirmed that there are countless transition nuclei generated in the electrode in about the entirety. In about 4 seconds, the electrode is completely transferred from the radiation alignment state to the curved alignment state. A rectangular wave voltage with a cycle number of 30 Η z and 0 to 5 V was applied to the above-mentioned liquid crystal display element, and the voltage generated by measuring the bending transition nucleus was 2.80 V. The boundary voltage (V c r) of the radiation alignment and bending alignment states is 1.70 V. In addition, the alignment of the liquid crystal is also good. In addition, a battery for measuring the front tilt angle was produced according to Example 1, and the front tilt angle of the liquid crystal was measured by the crystal rotation method to be 9.2 degrees. Example 3 A battery was produced according to the method of Example 1 except that 50% by weight of IT was mixed in the liquid crystal alignment agent paint, and each electrode was observed in its entirety (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1.0 cm 2). The number of transition nuclei generated from the radiation alignment state to the curved alignment state, and it is confirmed that there are countless transition nuclei generated about the entire electrode. About 1 second, the electrode is completely transferred from the radiation alignment state to the curved alignment state. A rectangular wave voltage with a cycle number of 30 Η z, 0 to 5 V was applied to the above-mentioned liquid crystal display element, and the voltage generated by measuring the bending transition nucleus was 2.50 V. The boundary voltage (V cr) of the radiation alignment and bending alignment is based on the Chinese paper standard (CNS) A4 specification (210X297 mm) for paper size. -54-581920 A7 B7 V. Description of the invention (52) 1 · 6 5 V . In addition, the alignment of the liquid crystal is also good. (Please read the precautions on the back before filling in this page.) In addition, a battery for front tilt angle measurement was produced according to Example 1, and the tilt angle before the liquid crystal was measured by the crystal rotation method was 8.8 degrees. Example 4 A battery was fabricated according to the method of Example 1 except that 10% by weight of 20 nm antimony oxide was mixed in the liquid crystal alignment agent paint of Example 1. Observe that each electrode is fully (1.0 cm 2) from The number of transition nuclei generated from the radiation alignment state to the curved alignment state, and it is confirmed that there are countless transition nuclei generated about the entire electrode. About 8 seconds, the electrode is completely transferred from the radiation alignment state to the curved alignment state. A rectangular wave voltage with a cycle number of 3 Η Η z and 0 to 5 V was applied to the above-mentioned liquid crystal display element, and the voltage generated by measuring the bending transition nucleus was 3.1 0 V. The boundary voltage (V c I *) of the radiation alignment and bending alignment states is 1. 7 4 V. In addition, the alignment of the liquid crystal is also good. Furthermore, a battery for front tilt angle measurement was produced according to Example 1, and the front tilt angle of the liquid crystal was measured by the crystal rotation method to be 9.8 degrees. Printed in Example 5 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Except that the liquid crystal alignment agent paint of Example 1 was mixed with 30% by weight of 20 nm antimony oxide, a battery was produced according to the method of Example 1, and each electrode was observed. The number of transition nucleuses generated from the full-scale (1.0 cm 2) alignment state to the bend alignment state, and it was confirmed that there were countless transition nucleuses generated from about the entire electrode. About 6 seconds, the electrode was fully aligned from the radiation-aligned state to confirm the paper. The dimensions are applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -55- 581920 A7 B7 5. Description of the invention (53) Actually transferred to the bending alignment state. (Please read the precautions on the back before filling in this page) Apply a rectangular wave voltage of 3 0 Η z, 0 to 5 V to the above-mentioned liquid crystal display element, and measure 2 · 9 0 V when the voltage generated by the bending transition core . In addition, the boundary voltage (v c r) of the radiation alignment and bending alignment states is 1.7 1 V. In addition, the alignment of the liquid crystal is also good. Furthermore, a battery for measuring the front tilt angle was produced according to Example 1, and the front tilt angle of the liquid crystal was measured by the crystal rotation method to be 9.4 degrees. Example 6 A battery was fabricated according to the method of Example 1 except that 10% by weight of silicon oxide was mixed in the liquid crystal alignment agent paint of Example 1. Observe that the overall (1.0 cm 2) state of each electrode from the radiation alignment state to The number of transition nuclei generated in the bending alignment state, and it is confirmed that there are countless transition nuclei generated in about the entire electrode. About 7 seconds, the electrode is completely transferred from the radiation alignment state to the curved alignment state. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. A square wave voltage of 30 Η z, 0 to 5 V was applied to the above-mentioned liquid crystal display element, and the voltage generated by measuring the bending transfer core was 3.05 V. The boundary voltage (V c r) of the radiation alignment and bending alignment states is 1. 7 3 V. In addition, the alignment of the liquid crystal is also good. Further, a battery for measuring the front tilt angle was produced according to Example 1, and the front tilt angle of the liquid crystal was measured by the crystal rotation method to be 9.7 degrees. Example 7 Except for 30% by weight of the liquid crystal alignment agent paint in Example 1, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -56- 581920 Α7 Β7 V. Description of the invention (54) In addition to silicon oxide, a battery was fabricated according to the method of Example 1. Observe the full transition (1.0 cm 2) of each electrode from the state of radiation alignment to the state of bending alignment (please read the precautions on the back before filling this page). The number of generated electrodes was confirmed, and countless transition nuclei were generated around the electrode. About 5 seconds, the electrode was completely transferred from the radiation alignment state to the curved alignment state. A rectangular wave voltage with a cycle number of 3 Η Η z and 0 to 5 V was applied to the above-mentioned liquid crystal display element, and the voltage generated by measuring the bending transition core was 2.8 5 V. The boundary voltage (V c I *) of the radiation alignment and bending alignment states is 1 · 7 1 V. In addition, the alignment of the liquid crystal is also good. In addition, a battery for front tilt angle measurement was produced in accordance with Example 1, and the front tilt angle of the liquid crystal measured by the crystal rotation method was 9.3 degrees. Comparative Example 1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, except that no solid particles were added to the liquid crystal alignment agent paint of Example 1, a battery was produced in accordance with the method of Example 1, and each electrode was fully observed (1.0 cm 2 ) The number of transition nuclei generated from the radiation alignment state to the bending alignment state. It was confirmed that about 20 transition nuclei were generated. About 15 seconds, the electrode was completely transferred from the radiation alignment state to the bending alignment state. A rectangular wave voltage with a cycle number of 3 0 Η z, 0 to 5 V was applied to the above-mentioned liquid crystal display element, and when the voltage generated by the bending transition nucleus was measured, it was 3 · 7 4 V. The boundary voltage (V c r) of the radiation alignment and bending alignment states is 1 · 7 8 V. In addition, the alignment of the liquid crystal is also good. In addition, a battery for measuring the front tilt angle was produced according to Example 1, and the front tilt angle of the liquid crystal was measured by the crystal rotation method to be 1.0 degree. This paper size applies Chinese National Standard (CNS) A4 specification (21 × 297 mm) -57- 581920 A7 B7 V. Description of the invention (55) The results of Examples 1 to 7 and Comparative Example 1 are shown in Table 1. Table 1 Lightning amount of solid microparticles to the amount of polymer particles of solid particles% Number of bending transition nuclei generated (number / cm2) Transfer time (seconds) from radiation alignment to bending alignment Voltage (V) Vcr ( V) Front tilt angle (°) Real 1 ITO 10 00 5 3.02 1.73 9.6 Application 2 ITO 30 00 4 2.80 1.70 9.2 Example 3 ITO 50 〇〇1 2.50 1.65 8.8 4 Antimony oxide 10 〇08 3.10 1.74 9.8 5 Antimony oxide 30 00 6 2.90 1.71 9.4 6 oxidized stone 10 00 7 3.05 1.73 9.7 7 oxidized stone 30 〇 05 2.85 1.71 9.3 Comparative Example 1 Not added — 20 15 3.74 1.78 10.7 (Please read the precautions on the back before filling this page ) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as described above, the liquid crystal display element with solid particles added successfully locally generates a transition nucleus from the radiation alignment state to the curved alignment state, and the transfer is performed in a short time, and V cr is also reduced. That is, the voltage near the solid particles in the alignment film becomes locally high, and it is speculated that this result causes a transition nucleus that is generated from the radiation alignment state to the curved alignment state. Opportunities. Generally speaking, it is known that the liquid crystal's transfer voltage when the front tilt angle becomes low. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -58-581920 A7 __B7 V. Description of the invention (56) Yes It tends to increase, and the voltage of the liquid crystal display element to which the solid fine particles are added is opposite to that of the bending transition core. It is confirmed that the tilt angle of the liquid crystal of the alignment agent paint with solid particles added is lower than the tilt angle of the liquid crystal before the addition of solid particles, and 10.7 degrees is lower. Possibility of industrial utilization The present invention uses an alignment film formed of a liquid crystal alignment agent paint containing solid particles or an alignment film in which solid particles are dispersed on the surface, and can provide self-radiation quickly and reliably at a low voltage. 0 CB type liquid crystal display element with transition from alignment state to curved alignment state. !, 1II (Please read the notes on the back before filling out this page) Order Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Printed by the Consumer Cooperatives of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 (210 X 297 mm) • 59-