200914953 九、發明說明： 【發明所屬·=δ^技領域3 本發明係有關於一種液晶顯示元件用配向材料及其製 造方法，特別是有關於液晶配向性及耐磨擦性優異’電壓 5 維持率及對比率高，且可降低電荷蓄積之以下述化學式1所 示之二胺基苯衍生物、其製造方法及利用該衍生物之液晶 配向膜。 【先前技術□ 一般，現有的陰極線管（CRT/cathode ray tube)方式之顯 10 示器元件具有優異特性，卻仍因為隨著晝面變大而其體積 及重量急速增加之缺點，因此，不適於使用在最近須要高 畫質、大晝面及平板型之多媒體系統，為改善此情況，而 開發出液晶顯示器態樣(Liquid Crystal Device(LCD);液晶 元件）。200914953 IX. Description of the Invention: [Technical Field] The present invention relates to an alignment material for a liquid crystal display element and a method for producing the same, and particularly relates to an excellent liquid crystal alignment property and abrasion resistance. A diaminobenzene derivative represented by the following Chemical Formula 1 having a high rate and a high contrast ratio and a low charge accumulation, a method for producing the same, and a liquid crystal alignment film using the derivative. [Prior Art] In general, the conventional CRT/cathode ray tube type display device has excellent characteristics, but it is still disadvantageous in that its volume and weight increase rapidly as the kneading surface becomes larger. In order to improve the situation, a liquid crystal display (LCD) (liquid crystal element) has been developed for use in a multimedia system that requires a high-definition, large-faced, and flat-panel type.
15 C 液晶顯示裝置之製造過程中，配向膜之配向效果是決 定LCD品質良好與否之重要因素。液晶顯示元件所使用之 配向膜，基本上疋須使液晶分子配向，以於基板面與液晶 分子之間具有依驅動方法而定之適當的預傾角，形成穩定 且均勻之配向膜，不僅如此，更須於液晶分子與配向膜之 間形成具有諸如W>1G-4〗/em2這般強之翻能量。這是因 為配向膜是決定液晶顯示元件的可靠性 '顯示均勻性、爹 像殘留及電壓維持率等之重要的因素的關係。 目前’當做為液晶配向騎使用者，已知有各種的聚 合物化合物。其中最常被利用之代表性高分子化合物係諸 20 200914953 如有將聚醯胺酸進行醯亞胺化而使用之聚胺酸系及可冷 性《亞成物。其f組成物係以優^ 财熱性及耐化學性而被當做為使液晶配向之配向劑，廣 在工業上。此外’其等高分子化合物係藉使二胺與四綾: 二酐聚合而形成’以使單體構造顯示高分子化合物之物· 特性者。 液晶配向膜之基本要求條件係於預傾角的控制。已知 液晶分子之預傾角係依配向膜表面之形狀、側鍵之長户 受很大的影響。尤其對於IPS模式之液晶顯示元件而 10 求低的預傾角，約1至2度左右。 液晶顯示元件之驅動方式乃可區分為：在透明電極上 塗佈配向膜之兩枚透明基板之間配置向列液晶分子之扭轉 向歹彳（Twist nematic ··以下稱為“TN”）模式、超扭轉向列 (Super twist nematic ;以下稱為“STN”）模式、平面轉換 15 (In-Plane Switching ;以下稱為“IPS”）模式、垂直配向 (Vertical alignment ;以下稱為“VA”)模式、及使用薄膜電晶 體（Thin film transistor:以下稱為“TFT”）之 TFT 型。 可改善視角之IPS模式之液晶顯示裝置中，在相互平行 之2基板中任一個基板上全部形成有相互平行且呈線狀之2 20電極。充滿在兩基板之間之液晶層的液晶分子之長軸係與 兩基板平行、或與電極平行，而排列於形成一定角度之方 向上。對兩電極施加電場時，藉與基板平行之電場，使液 晶分子之長軸與電場平行排列。惟，現有的IPS模式液晶顯 示裝置有如下問題衍生，即，在黑暗狀態下有漏光現象發 200914953 生，使對比率降低，使液晶分子的響應速度變慢者。 IPS模式係使用液晶分子在同一平面内驅動之橫向電 場方式，可得到左右對稱之視角特性。已知僅於基板一側 形成電極，施加與基板平行方向之電場之橫向電場方式， 5 係與習知之形成在上下基板之電極施加電壓而使液晶驅動 . 之縱向電場相比，有較廣大的視角特性，又可作為進行高 • 品質顯示之液晶顯示元件。利用如此之橫向電場方式之液 晶顯示元件係如下列專利文獻1所揭示者。 如前述’橫向電場方式之液晶細胞5雖具有優異之視 10 角特性，但形成在基板内之電極部分少，因此容易在液晶 _ 細胞内蓄積靜電，又藉由驅動所產生之非對稱電壓之施 - 加，亦使電荷蓄積於液晶細胞内，而衍生下列問題，即， 其等所蓄積之電荷混亂了液晶的配向，或以殘留影像、殘 留影像持續性而對顯示造成影響，顯著地降低液晶元件之 15 顯示品質。因此，尤其是以橫向電場驅動用液晶顯示元件 而言，被要求顯示低預傾角（1〜2度），且為減少殘留影像， I 而須改善液晶配向膜之特性。 [專利文獻1 ]日本發明專利申請案公開公報第H05 — 505247號 【發明内容】 20 為解決如此習知技術之問題點，本發明之目的係於提 供一種使液晶穩定配向，具優異的耐磨擦性，不僅電壓維 持率及對比率高，具有低預傾角，尤其是減少液晶之殘留 影像之二胺基苯衍生物、其製造方法及利用該衍生物之液 晶配向膜。 7 200914953 為達成前述目的，本發明乃提供一種以下述化學式1所 示之二胺基苯衍生物。 〔化學式1〕In the manufacturing process of the 15 C liquid crystal display device, the alignment effect of the alignment film is an important factor in determining whether the LCD quality is good or not. The alignment film used for the liquid crystal display element basically does not need to align the liquid crystal molecules, so as to have a proper pretilt angle between the substrate surface and the liquid crystal molecules according to the driving method to form a stable and uniform alignment film, not only that, but also A strong turning energy such as W > 1G-4 〗 / em2 must be formed between the liquid crystal molecules and the alignment film. This is because the alignment film is a factor that determines the reliability of the liquid crystal display element, such as display uniformity, image retention, and voltage maintenance ratio. At present, various polymer compounds are known as liquid crystal alignment users. The most widely used representative polymer compounds are 20 200914953. For example, there are polyamine acids and cold-formable sub-forms which are used for the imidization of poly-proline. The composition of the f is widely used in the industry as an alignment agent for alignment of liquid crystals with excellent heat and chemical resistance. Further, the polymer compound is formed by polymerizing a diamine and a tetrahydrogen: dianhydride to form a monomer structure to exhibit the properties and characteristics of the polymer compound. The basic requirement for the liquid crystal alignment film is the control of the pretilt angle. It is known that the pretilt angle of liquid crystal molecules is greatly affected by the shape of the surface of the alignment film and the length of the side bonds. In particular, for a liquid crystal display element of the IPS mode, a low pretilt angle is obtained, which is about 1 to 2 degrees. The driving method of the liquid crystal display element can be divided into a twisting direction (Twist nematic · hereinafter referred to as "TN") mode in which nematic liquid crystal molecules are disposed between two transparent substrates on which an alignment film is coated on a transparent electrode. Super twist nematic (hereinafter referred to as "STN") mode, plane conversion 15 (In-Plane Switching; hereinafter referred to as "IPS") mode, vertical alignment (hereinafter referred to as "VA") mode And a TFT type using a thin film transistor (hereinafter referred to as "TFT"). In the liquid crystal display device of the IPS mode in which the viewing angle is improved, all of the two parallel electrodes which are linear in shape are formed on any of the two substrates which are parallel to each other. The long axis of the liquid crystal molecules filled in the liquid crystal layer between the two substrates is parallel to the two substrates or parallel to the electrodes, and arranged in a direction forming an angle. When an electric field is applied to the two electrodes, the long axis of the liquid crystal molecules is arranged in parallel with the electric field by an electric field parallel to the substrate. However, the existing IPS mode liquid crystal display device has the following problems: that is, a light leakage phenomenon occurs in a dark state, which lowers the contrast ratio and slows the response speed of liquid crystal molecules. The IPS mode uses a lateral electric field mode in which liquid crystal molecules are driven in the same plane, and a viewing angle characteristic of left and right symmetry can be obtained. It is known that an electrode is formed only on one side of the substrate, and a transverse electric field of an electric field in a direction parallel to the substrate is applied. The conventional method forms a relatively large electric field by applying a voltage to the electrodes of the upper and lower substrates to drive the liquid crystal. The viewing angle characteristics are also used as liquid crystal display elements for high quality display. A liquid crystal display element using such a transverse electric field method is as disclosed in Patent Document 1 below. As described above, the liquid crystal cell 5 of the transverse electric field type has excellent viewing angle characteristics, but the number of electrode portions formed in the substrate is small, so that it is easy to accumulate static electricity in the liquid crystal cell, and the asymmetric voltage generated by the driving is generated. The application of the charge also accumulates in the liquid crystal cells, and the problem is that the accumulated charge confuses the alignment of the liquid crystal, or the residual image and the residual image persistence affect the display, and the display is significantly reduced. 15 display quality of the liquid crystal element. Therefore, in particular, in the case of a liquid crystal display element for driving a transverse electric field, it is required to display a low pretilt angle (1 to 2 degrees), and in order to reduce residual images, I must improve the characteristics of the liquid crystal alignment film. [Patent Document 1] Japanese Patent Application Publication No. H05-505247 [Description of the Invention] In order to solve the problems of the prior art, the object of the present invention is to provide a liquid crystal stable alignment with excellent wear resistance. The rubbing property is not only a voltage holding ratio and a high contrast ratio, but also a low pretilt angle, particularly a diaminobenzene derivative which reduces residual image of liquid crystal, a method for producing the same, and a liquid crystal alignment film using the derivative. 7 200914953 In order to achieve the above object, the present invention provides a diaminobenzene derivative represented by the following Chemical Formula 1. [Chemical Formula 1]
5 在前述化學式1中，八1至八5各獨立地為一Η、一F、一 CF3、一 OCF3、碳數為1至7之烷基、碳數為1至7之烷氧基、 下述化學式2a、2b、2c或2d，且八1至入5中之至少一個不為 一Η。5 In the above Chemical Formula 1, each of VIII to VIII is independently a fluorene, an F, a CF3, an OCF3, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and The chemical formula 2a, 2b, 2c or 2d is described, and at least one of VIII to 5 is not monoterpene.
〔化學式2a〕 〔化學式2b〕 〔化學式2c〕 〔化學式2d〕 10 在前述化學式2a、2b、2c、2d中，R各獨立地為碳數1 至7之烷基或碳數1至7之烷氧基。 又，本發明係提供一種二胺化合物之製造方法，該二 胺化合物係以前述化學式1所示者，前述製造方法包含有下 列階段，即：（a)使下述化學式3之化合物與4,4一二氣二苯 15 曱酮反應，製造化學式4之化合物者；（b)使p—曱苯磺酸 200914953 (p-toluenesulfonic acid)及甲苯使前述化學式4之化合物脫 水，製造化學式5之化合物；（c)使前述化學式5之化合物與 雙（三甲基矽烷基）醯胺鋰、（二苯亞甲基丙酮）鈀、三環己基 膦一同反應，製造下述化學式6之化合物；及，（d)於Pd/C 5 觸媒下，使前述化學式6之化合物進行氫還原，且使化合物 再結晶分離。[Chemical Formula 2a] [Chemical Formula 2b] [Chemical Formula 2c] [Chemical Formula 2d] 10 In the above Chemical Formulas 2a, 2b, 2c, and 2d, R is each independently an alkyl group having 1 to 7 carbon atoms or an alkyl group having 1 to 7 carbon atoms. Oxygen. Furthermore, the present invention provides a method for producing a diamine compound according to the above Chemical Formula 1, wherein the production method comprises the following steps: (a) bringing a compound of the following Chemical Formula 3 to 4, 4-2 diphenylene 15 fluorenone reaction to produce a compound of formula 4; (b) p-toluenesulfonic acid 200914953 (p-toluenesulfonic acid) and toluene to dehydrate the compound of the above formula 4 to produce a compound of formula 5 (c) reacting a compound of the above Chemical Formula 5 with lithium bis(trimethyldecyl)guanamine, palladium (diphenylmethyleneacetone), or tricyclohexylphosphine to produce a compound of the following Chemical Formula 6; (d) Hydrogen reduction of the compound of the above Chemical Formula 6 under a Pd/C 5 catalyst, and recrystallization of the compound.
〔化學式3 〔化學式4 〔化學式5 〔化學式6〕 前述化學式3至6中，入1至八5係如前述所揭露者。 200914953 又，本發明係提供一種液晶顯示裝置之配向劑用聚醯 亞胺樹脂之製造方法，前述聚醯亞胺樹脂係下述化學式10 所示者，前述製造方法包含有下列階段，即：（a)在溶劑下 使前述化學式1之二胺化合物、下述化學式7之四羧酸酐、 5 及化學式8之無側鏈基團之二胺化合物反應，製造下述化學 式9之聚醯胺酸系嵌段共聚物；及，（b)將前述聚醯胺酸系嵌 段共聚物熱處理，以脫水閉環反應轉換成聚醯亞胺。 〔化學式7〕 λ Λ[Chemical Formula 3 [Chemical Formula 4] [Chemical Formula 6] In the above Chemical Formulas 3 to 6, the incorporation of 1 to 8 is as disclosed above. Further, the present invention provides a method for producing a polyimide resin for an alignment agent of a liquid crystal display device, wherein the polyimine resin is represented by the following Chemical Formula 10, and the production method includes the following stages: a) The diamine compound of the above Chemical Formula 1, the tetracarboxylic acid anhydride of the following Chemical Formula 7, and the diamine compound having no side chain group of Chemical Formula 8 are reacted under a solvent to produce a polyamine acid of the following Chemical Formula 9 a block copolymer; and, (b) heat-treating the poly-polyamine-based block copolymer, and converting it into a polyimine by a dehydration ring-closure reaction. [Chemical Formula 7] λ Λ
Vx\/° ο ό 〔化學式8〕 — Ζ—HHg 〔化學式9〕Vx\/° ο ό [Chemical Formula 8] — Ζ—HHg [Chemical Formula 9]
〔化學式10〕[Chemical Formula 10]
"ί 0 0 Ο Ο N Jxf Ν'Ύ-τ 〇 0 Η. JX: ν-ζ4 ν'+’ 'ί 0 ο - J 10 前述化學式7至10中，X為4價有機基，Y為源自前述化 學式1之側鏈型2價有機基，Z為無側鏈基之2價有機基，在 此，m為1，η為1以上之整數。 10 200914953 又，本發明係提供一種液晶顯示裝置之配向劑用聚醯 亞胺樹脂，其係藉前述方法所製造，且重量平均分子量為 1，000至200,000者。 又，本發明係提供一種液晶配向膜，其利用前述液晶 5 顯示裝置之配向劑用聚醯亞胺樹脂而製造者。 又，本發明係提供一種液晶顯示元件，其包含有前述 液晶配向膜。 [發明之效果] 本發明之化學式1之側鏈型二胺化合物係可運用為橫 10 向電場驅動用液晶配向劑，又，使用前述二胺化合物而製 造之聚醯亞胺樹脂之液晶配向性穩定，且耐磨擦性佳，可 實現1.5±0.2度之低預傾角，進而依本發明之聚醯亞胺樹脂 在對比率及減少殘留影像觀點上有顯著改善，可作為液晶 顯示元件之配向劑之用。 15 [圖式簡單說明] 益 4 *»> 【實施方式3 以下詳細說明本發明。 本發明之液晶配向材料不僅可使液晶穩定配向，耐磨 20 擦性佳，電壓維持率及對比率高，又具有低預傾角，尤其 可減少液晶之殘留影像之狀態下設計側鏈，而使用化學式1 般之二胺化合物，為本發明之特徵所在。 前述化學式1之二胺化合物乃可透過反應式1般之方法 製造者。該方法包含有以下階段，即： 11 200914953 第1階段 在氮氛圍下，將前述化學式3之化合物與鎂溶解在醚 (ether)之溶液冷卻到常溫之後，將四氫吱喃（THF)中溶解有 4,4一二氯二苯曱酮之溶液緩慢地滴落其中，可得到前述化 5 學式4之化合物。 第2階段 將前述化學式4之化合物在p —甲苯續酸（p-toluene sulfonic acid ; PTSA) · —水合物下進行脫水，可得到化學 式5之化合物。 10 第3階段 將前述化學式5之化合物與雙（三甲基矽烷基）醯胺鋰、 雙（二苯亞甲基丙酮）鈀、三環己基膦一同反應，可得到下述 化學式6之二胺化合物。 第4階段 15 將前述化學式6之化合物在Pd/C觸媒下進行氫還原，使 異構體分離，可得到化學式1之最終二胺化合物。 12 200914953"ί 0 0 Ο Ο N Jxf Ν'Ύ-τ 〇0 Η. JX: ν-ζ4 ν'+' 'ί 0 ο - J 10 In the above Chemical Formulas 7 to 10, X is a tetravalent organic group, and Y is The divalent organic group derived from the side chain of the above Chemical Formula 1, Z is a divalent organic group having no side chain group, and m is 1, and n is an integer of 1 or more. Further, the present invention provides a polyimine resin for an alignment agent for a liquid crystal display device which is produced by the aforementioned method and which has a weight average molecular weight of 1,000 to 200,000. Further, the present invention provides a liquid crystal alignment film which is produced by using a polyimide resin of an alignment agent of the liquid crystal display device. Further, the present invention provides a liquid crystal display element comprising the above liquid crystal alignment film. [Effects of the Invention] The side chain type diamine compound of Chemical Formula 1 of the present invention can be used as a liquid crystal alignment agent for a horizontally 10 direction electric field drive, and a liquid crystal alignment property of a polyimide resin produced by using the above diamine compound. Stable, and good abrasion resistance, can achieve a low pretilt angle of 1.5 ± 0.2 degrees, and further improve the contrast ratio of the polyimine resin according to the present invention in terms of contrast ratio and reduction of residual image, and can be used as an alignment of liquid crystal display elements For the use of agents. 15 [Simple Description of the Drawings] Benefits 4 *»> [Embodiment 3] Hereinafter, the present invention will be described in detail. The liquid crystal alignment material of the invention not only can stably align the liquid crystal, has good wear resistance, good rubbing performance, high voltage maintenance ratio and high contrast ratio, and low pre-tilt angle, and particularly reduces the design of the side chain under the residual image of the liquid crystal, and uses The diamine compound of the formula 1 is a feature of the present invention. The bisamine compound of the above Chemical Formula 1 can be produced by a method similar to that of the reaction formula 1. The method comprises the following steps, namely: 11 200914953 Stage 1 Dissolving tetrahydrofuran (THF) in a solution of the compound of the above formula 3 and magnesium dissolved in ether under a nitrogen atmosphere after cooling to room temperature A solution of 4,4-dichlorobenzophenone is slowly dropped thereinto to obtain the compound of the above formula 5. Second stage The compound of the above Chemical Formula 4 is dehydrated under p-toluene sulfonic acid (PTSA) hydrate to obtain the compound of Chemical Formula 5. 10 In the third stage, the compound of the above chemical formula 5 is reacted with lithium bis(trimethyldecyl) decylamine, bis(dibenzylideneacetone)palladium or tricyclohexylphosphine to obtain a diamine of the following chemical formula 6 Compound. In the fourth stage, the compound of the above Chemical Formula 6 is subjected to hydrogen reduction under a Pd/C catalyst to separate the isomer, whereby the final diamine compound of Chemical Formula 1 can be obtained. 12 200914953
在前述反應式1中，八1至八5係如前述所定義者。 又，本發明係提供一種使用前述化學式1之二胺化合物 5 之聚醯亞胺樹脂之製造方法及聚醯亞胺樹脂，前述方法之 特徵係於包含有以下階段，即：（a)在溶劑下將前述化學式1 之二胺化合物、下述化學式7之四羧酸酐、及化學式8之無 側鏈基團之二胺化合物反應，製造下述化學式9之聚醯胺酸 系嵌段共聚物；及，（b)將前述聚醯胺酸系嵌段共聚物熱處 10 理，以脫水閉環反應轉換成聚醯亞胺。 以一具體例為例，一邊維持5°C，一邊將前述化學式7 之四羧酸二酐在氮氛圍慢慢滴落於使前述化學式1之側鏈 13 200914953 型二胺化合物與前述化學式8之二胺溶解在n—曱基—2 — t各烧酮而得狀反應毅後，_6小時，製造聚酿胺酸 系嵌段共聚物。此時，黏度則可利用諸如二甘醇單甲謎、 一甘醇單乙_、乙二醇單丁料之溶纖劑(^―)系溶 5 劑調整者。 之後，本發明係使聚醯胺酸系嵌段共聚物在则。C至 25(TC之間進行熱處襲分鐘至2小時，以脫水閉環反應轉 換成聚醯亞胺。 又’在驗性觸媒與酸酐之存在下，以〇〜i8(rc授掉聚酿 10 15 20 胺酸1至小時，透過化學性亞胺化反應，可轉變成聚醯 亞胺士此所得到之聚醯亞胺溶液係如前述聚醯胺酸合成 所言，以進行沈澱回收者為佳。 在製述聚酿胺酸所使用之溶劑只要是使所產生之 聚^胺酸☆解者’即無特別限^，而以具體例而言，諸如N 一甲基一2—吡咯烷酮（NMp)、n，n一二甲基甲醯胺 (DMF) Ν,Ν —甲基乙酸胺、N—甲基己内醯胺、二甲基 亞風(DMSO) 7 丁内g旨、六甲基碟酸醯胺、四氫。塞吩石風、 Ρ—氣紛、Ρ-溴齡、2一氯—4一經基甲苯、二魏、四氯 吱喃(THF)、環己轉等。又，即使不使聚_酸溶解之溶 劑’在不析出所產生之聚_酸之範圍内，亦可混合在前 述溶劑中使用。進而，有機溶劑中的水份成為阻礙聚合反 應而使所產生之聚ϋ胺酸加水分解之原因，因此有機溶 劑，可以的話，以使用使其脫水乾燥者為佳。 在於聚醯胺酸之製造階段上之四羧酸二酐的X為4價之 14 200914953 有機基。以具體例而言，3,3'，4,4’一二苯甲酮四羧酸二酐 (BTDA)、4,4’一氧二鄰苯二甲酸酐（ODPA)、3,3'，4,4'—雙笨 基四羧酸二酐(BPDA)、1,2,4,5-苯四羧酸二酐(PMDA)、環 丁烷四羧酸二酐（CBDA)及4一（2,5 —二氧四氢呋喃一3 —基) 5 — 1，2,3,4—四氫萘一1,2—二羧酸二酐(TDA)等。 又，前述化學式9或10之用以構成具有氮原子之Y之二 • 胺係源自前述化學式1之二胺。與位於該二胺之側鏈末端之 曱撐基相連結之苯甲基衍生物可顯示水平配向性，含有很 多芳香族之主鏈及側鏈二胺，又，四羧酸二酐可將表面極 10 性加大，同時提高配向膜之表面張力，顯示很小之預傾角。 又，連結胺之苯曱基係於鏈之間形成可使有機溶劑滲入之 空間，可增加溶解性。 又，前述化學式9或10之用以構成具有氮原子之Z之前 述二胺化合物可使用不具側方取代基之二胺化合物。具體 15 而言，4,4’一二胺基二苯醚(ODA)、4,4’一甲撐基雙環己胺 (PACM)、4,4'—曱撐基 _2—甲基環己胺(ANCAMINE)、4,4’ ^ 一甲撐基二苯胺、二胺基二苯甲酮、4,4’一曱撐基二苯基二 胺（MDA)、4,4'—六氟異丙基二苯基二胺（6FDA)、p—苯撐 基二胺(P_PDA)等。 為得到聚醯胺酸’而將四羧酸二酐成分及二胺成分在 2〇 . 有機溶劑中反應時’通常以5至l〇(TC為佳。溫度高時，具 合玎快速結束，高分子之分子量變得過高，因此不得不注 意。又，反應濃度做成5至3〇重量％，進行均勻的攪拌，可 将·到所需之分子量。所得到之聚醯胺酸亦可將反應溶液稀 15 200914953 釋而予以使用，透過沈;殿回收，再溶解後加以使用。使用 在沈;殿回收之弱溶劑並無特別限定，但可舉甲醇、乙醇、 己烷、丙酮、丁基溶纖劑、甲基乙基甲酮、甲苯、苯、二 乙起等為例。藉投入弱溶劑而所得到之聚醯胺酸沈殿物係 ’·里過濾、&錢再回收’且在常壓或_下進行常溫或加 熱乾燥，可得到固態部分。 10 15 對於前述聚酿亞胺，側鏈型2價有機基(γ)係用以於附 =諸如液晶配向性、溶解性及膜透過性般之聚醯亞胺之機 月b I·生者；f具侧鏈之2價有機基⑺係用以於調節側鍵間之 間隔而決定側鏈基之分布度者。在前述化學式7巾，m為卜 n為1至10之整數，更以2至4為佳。 前述側鏈型2價有機基⑺之側鏈長度係宜調節液晶分 子長軸之平時長度的比成狀Η 5倍，又，宜決定不具侧 鏈基之2½有機基(ζ)之賴及使用量，俾使側鏈基間之長 度比液晶好長歡長度紅5〜3.5倍者。則σ此方法，可 製作具特&構奴㈣亞胺樹脂，其以聚醯亞胺顯示優 異的配向性’具有溶解性、膜穿雜、化學敎性優異之 特性。較佳的是，前述聚醯亞胺樹脂之重量平均分子量以 1，000至200,000為佳。 又，本發明係提供-種利用前述聚醯亞胺樹脂之液晶 配:膜’前述液晶配向膜可在業經圖案化之基板上塗佈含 «述聚醯亞胺化合物之配向液後燒成而得到者。使用在 前述配向液之溶劑只要是通常是使用在液晶配向液，可將 前述聚醯亞胺化合物溶解者’即無特別限定，又配向液係 16 200914953 以3有前述聚醯亞胺化合物1至30重量％者為佳。 本發明之液晶配向膜係於液晶配向性及耐磨擦性優 〃、電壓維持率及對比率高，不僅減少電荷蓄積，更可做 成才對於向列液晶具有丨至2度之預傾角，沒有殘留影像者。 乂下’根據下列貫施例詳細記述本發明，而本發明範 ' 圍並不受限於下列實施例者。 [實施例1] f 藉反應式1合成化學式1之二胺化合物。依各階段，如 下說明合成方法。 10 在氬氣圍下’將蛾片及鎂3.5g放入&|(ether)100ml，緩 慢地進行還流後，再將曱基苯甲基溴22.1g慢慢地加入醚 卜還流2小時，製造格利雅(Grignard)反應物。將此物 冷卻到常溫後，再將4,4—二氯二苯甲酮20g溶解到四氫呋 15 喃〇^?)15〇111卜慢慢滴加，花1小時30分鐘進行還流。將反 應物冷卻後，添加飽和氣化銨l〇m卜以C鹽過濾後，再以氯 > 仿及氯化鈉擷取，又以無水硫酸鎂使其乾燥，減壓蒸顧， 付到1，1 一雙一（4 —氯一苯基）一 2 —曱基本基乙醇之淡黃色 液體。（25g、90%) 20 4 NMR(CDC13、ppm):7_20(d、4H)、7.13(d、4H)、7.09(d、 1H)、6.93(d、1H)、6.92(s、1H)、6.88(d、1H)、3.32(d、2H)、 2_35(d、3H)、2.00(s、1H) 放入1,1 —雙一（4一氣一苯基）一2 -甲基笨基乙醇35g 17 200914953 及p-曱苯石黃酸•一水和物（p-toluene sulfonic acid · l-hydrate)2.7g，並放入曱苯200ml。將該溶液還流12小時並 使其反應，俟以TLC板(TLC plate)確認反應的結束之後，以 飽和氣化鈉及醚沖洗後擷取之。以無水硫酸鎂乾燥減壓， 5 蒸餾所剩餘的水份，得到茶色的1，1 一雙一（4—氯一苯基) 一2—甲基笨基乙烯液體。（3ig、95%) NMR(CDC13、ppm):7.36(d、4H)、7.27(d ' 4H)、7.23(d ' 1H)、7.22(s、1H)、7.14(d、1H)、6.92(s、1H)、6.91(d、1H)、 2.35(d > 3H) 10 第3階段 放入1，1_雙一（4 一氣一苯基）—2 —甲基苯基乙烯 2〇g、雙(三甲基矽烷基)醯胺鋰43.2g、三環己膦2.6g、雙(二 苯亞曱基丙酮）!巴5.3g後，再置入i5〇ml之曱苯(Toliene)。在 氮氛圍下，將反應容器内維持90°c，在使其反應12小時。 15以GC/Mass確認反應的進行。放入2〇〇mi的醚，將反應混合 物稀釋，放入1N鹽酸(HCl)300ml，結束反應。對有機層及 水層利用1N氫氧化鈉及醚沖洗而所得到之有機層係放入無 水硫酸鎮’經乾燥後再過濾。對溶劑減壓蒸餾再除去而得 到之混合物以二氯甲烧進行再結晶，得到白色的U—雙— 20 (4一胺基一苯基）一2—甲基苯基乙烯固體。（9g、5〇%) !H NMR(CDC13、ppm):7.23(d、1H)、7.22(s、1H)、7.14(d、 1H)、7.17(d、4H)、6_91(d、1H)、6_92(s、1H)、6.46(d、4H)、 3.74(s、broad、4H)、2.35(d、3H) 第4階段 18 200914953 將1，1 —雙一（4 —胺基一苯基）一2—曱基苯基乙稀i〇g 溶解在苯（benzene)及乙醇（ethanol)後，放I巴（l〇wt% 〇n activated carbon)lg ’在4kg/cm2的壓力下’撲拌5小時。確 認反應之結束之後，利用C鹽進行過濾後，將溶液減壓蒸 5 餾，得到白色固體。對該固體以乙二醇二乙酸酯及乙醇進 行再結晶，得到白色的1，1_雙一（4—胺基一苯基）—2 —甲 基苯基乙烷(ethane)固體。（5g、50%) iH NMR(CDC13、ppm):7_09(t、1H)、6.93(d、1H)、6_92(s、 1H)、6.88(d、1H)、6.87(d、4H)、6.41(d、4H)、4.44(t、1H)、 10 3.74(s、broad ' 4H)、3.17(d、2H)、2_35(d、3H) [實施例2] 除使用氟苯曱基溴以取代實施例1之第1階段的曱基苯 甲基溴之外，其餘以與實施例1同一之方法，合成1,1 —雙 —(4 —胺基一苯基）一2—氟苯基乙烧(ethane)。（5g、20%) 15 iH NMR(CDC13、ppm):7.19(t、1H)、6_89(d、1H)、6.87(s、 1H)、6.79(d、1H)、6_87(d、4H)、6.41(d、4H)、4.44(t、1H)、 3.75(s、broad、4H)、3_17(d、2H) [實施例3] 在氮氛圍下將1，1 —雙一（4一胺基一苯基）一 2—甲基苯 2〇 基乙烷(ethane)6.3g及4,4，一二胺基二苯醚(〇DA)8.3g溶解在 N—甲基一2—吡咯烷酮122g後，一邊維持在5°C，一邊添加 3,3'，4,4'一二笨甲酮四羧酸二酐(BTDA)20g。花2小時慢慢地 滴下所剩下之N—曱基一2—吡咯烷酮132g，反應10小時。 將該反應溶液放入過量的超純水，過濾所析出之沈澱物。 19 200914953 該過濾物係以甲醇洗淨，以50°C之真空烤箱減壓乾燥，收 得聚醯胺酸。（重量平均分子量二60,000) [實施例4] 除了以3,3',4,4'—雙苯基四羧酸二酐（BPDA)代替前述 5 實施例3所使用之3,3',4,4’一二苯曱酮四羧酸二酐（BTDA)之 外，其餘以與實施例3同一之方法，取得聚醯胺酸固態部 分。（重量平均分子量=70,000) [實施例5] 除使用1,1 —雙一（4 一胺基一苯基）一2— I苯基乙炫 10 (ethane)以代替前述實施例3所使用之1,1 一雙一（4—胺基一 苯基）一2—甲基苯基乙烷(ethane)，其餘以與實施例3同一之 方法，取得聚醯胺酸固態部分。（重量平均分子量= 60,000) [實施例6] 除使用1,1 —雙一（4_胺基一苯基）一 2—氣苯基乙烧 15 (ethane)以代替前述實施例3所使用之1,1 一雙一（4一胺基一 苯基）一2—曱基苯基乙烷(ethane)，且以3,3',4,4'—雙苯基四 羧酸二酐（BPDA)代替3,3',4,4'—二苯曱酮四羧酸二酐 (BTDA)之外，其餘以與實施例3同一之方法，取得聚醯胺 酸固態部分。（重量平均分子量=70,000) 20 [比較例1] 除了以1，1 一雙一（4 —胺基一苯基）一 2—苯基乙烧 (ethane)代替前述實施例3所使用之1,1 一雙一（4—胺基一苯 基）一2—曱基苯基乙烷之外，其餘以與實施例3同一之方 法，取得聚醯胺酸固態部分。（重量平均分子量=60,000) 20 200914953 物性評價方法係使用了如下方法。 (1)聚合物之重量平均分子量 為算出聚合物之重量平均分子量，測定凝膠滲透色譜 (GPC)。以 60°C 測定將二甲基乙醯胺(Dimethyl acetamide、 5 D M A c)作為移動相且充填有高分子物質之柱的滯留時間.， ， 由業已補正苯乙烯高分子之平均分子量及滞留時間之結 ' 果，計算聚醯胺酸固態部分之平均分子量。構成液晶配向 劑之聚合物係具有1，000〜200,000g/mol程度之重量平均分 ( 子量之值。 10 (2)液晶顯示元件之預傾角 藉文獻（T.J.Schffer、et.al.、J.、Appl.、Phys.、vol.19、 2013 (1980))所揭露之方法，使用He-Ne雷射光線，藉晶體 旋轉法測定者。 (3) 液晶之配向性 15 以顯微鏡觀察對液晶顯示元件施加及不施加電壓時液 晶細胞中之異常領域(domain)之有無，將沒有異常領域之型 " 態判斷為‘良好’。 (4) 液晶顯示元件之電壓維持率 對液晶顯示元件施加5V電壓達6〇微秒後，測定解除施 20加狀態後經過16.67毫秒後之電壓維持率。 (5) 對比率（Contrast ratio) 對液晶顯示元件測定無施加電壓狀態（黑暗狀態）下之 光透射率及光透射率成為最大之電壓下（明亮狀態）之光透 射率，進行計算。 21 200914953 (6)殘留影像評價 在具有電極寬度5 # m、電極間間隔1 〇 # m之鑛齒狀電 極(super-IPS)之基板上印刷液晶配向劑，且使其乾燥、烘烤 後，製作了膜厚200nm之薄膜（基板1)。同樣，在無電極之 5 玻璃基板上印刷液晶配向劑，且使其乾燥、烘烤後，製作 了膜厚200nm之薄膜（基板2)。對基板1進行磨擦處理，使液 晶配向劑朝電極方向具有2〇度的角度者。又，對基板2進行 磨擦處理，使基板1與磨擦方向平行者，在該基板上散佈間 隔件後貼合，製作間隙4/zm之細胞，將液晶MJ991735(外 10商M e rc k公司製造）注入該細胞，製作了液晶細胞。在0至1 〇 V 之間以0· lV/s速率、頻率（frequency) 1 kHz，施加在液晶細 胞，測定該液晶細胞之電壓一透射率（V — τ)特性之後，再 細加直流電壓1〇V達30分鐘。關閉直流電壓後馬上再測定v —T特性，由施加直流電壓前後之電壓—透射率特性之變 15化，評價殘留影像。即，藉使V—T特性引起變化，而使施 加一定電壓時之透射率變化時，在該領域内可觀測其變 化，當作為殘留影像。 又，將前述實施例3至6及比較例1所製造之聚醯胺酸固 態部分放到NMP與2—丁氧基乙醇以3:〖重量比混合而成之 〇 /合劑中，製得濃度4重量％之溶液。以〇.1 之過濾器過濾 該溶液，在已使透明導電膜圖案化之玻璃基板上，以旋塗 法塗佈600A之厚度。經塗佈後，以9〇它進行前烘烤3分鐘 後，再以21〇。(：烘烤1小時，得到形成有聚醯亞胺配向膜之 基板。 22 200914953 又，將利用附有IPS用梳齒形電極之玻璃基板及沒有電 極之玻璃基板等2枚玻璃基板所得到之配向膜，在乙醇中進 行超音波洗淨3分鐘後，再以超純水洗淨表面，隨後用烤爐 乾燥，散佈4//m之間隔材料，將其等黏合後，再注入液晶， 5 以環氧固化劑密封，製作液晶細胞。如此製作之液晶細胞 之特性示於下列表1。 〔表1〕液晶細胞之特性 項目 預傾角 (度） 電壓維持率 (%) 對比率 配向性 殘留影像 實施例3 1.5(±0.2) 99 100 良好 無 實施例4 1.5(±0.2) 98 100 良好 益 實施例5 1.5(±0.2) 99 100 良好 無 實施例6 1.5(±0.2) 98 100 良好 益 比較例1 1.5(+0.2) 97 98 良好 有 如前述表1所示，對於本發明之實施例3至6與比較例 10 1，可以確認全部做為橫向電場驅動用液晶配向劑時具有優 異特性，同時電壓維持率及配向性亦佳者。尤其可以確認 前述實施例3至6，與比較例1相比，殘留影像顯著地減少者。 L圖式簡單說明3 無 15 【主要元件符號說明】 無 23In the aforementioned Reaction Formula 1, eight to eight are as defined above. Further, the present invention provides a method for producing a polyimine resin using the diamine compound 5 of the above Chemical Formula 1, and a polyimine resin, which is characterized by comprising the following steps: (a) in a solvent The diamine compound of the above Chemical Formula 1, the tetracarboxylic acid anhydride of the following Chemical Formula 7, and the diamine compound having no side chain group of Chemical Formula 8 are reacted to produce a polyamic acid-based block copolymer of the following Chemical Formula 9; And (b) heat-treating the polyamic acid-based block copolymer to form a polyimine by a dehydration ring-closure reaction. In a specific example, while maintaining the temperature of 5 ° C, the tetracarboxylic dianhydride of the above Chemical Formula 7 is gradually dropped in a nitrogen atmosphere to the side chain 13 of the above Chemical Formula 1 and the 2009-14953 type diamine compound and the aforementioned Chemical Formula 8 The diamine was dissolved in the n-fluorenyl- 2 - t ketone and the reaction was carried out for -6 hours to prepare a poly-branched acid-based block copolymer. At this time, the viscosity can be adjusted by using a solvent such as diethylene glycol monomethyl mystery, monoglycol monoethyl amide, and ethylene glycol monobutylate (^-). Thereafter, in the present invention, the polyamic acid-based block copolymer is used. C to 25 (thermal attack between TC for 2 hours, converted to polyimine by dehydration ring-closing reaction. Also in the presence of an organic catalyst and an acid anhydride, 〇~i8 10 15 20 Amino acid for 1 hour, through chemical imidization reaction, can be converted into polyimine. The polyimine solution obtained by this method is as described above for the synthesis of polylysine for precipitation recovery. Preferably, the solvent used in the preparation of the polyamic acid is not particularly limited as long as it is used to produce the poly-amic acid, and in specific examples, such as N-methyl-2-pyrrolidone (NMp), n, n-dimethylformamide (DMF) Ν, Ν-methylacetic acid amine, N-methyl caprolactam, dimethyl nitrous oxide (DMSO) 7 Methyl decanoate, tetrahydrogen, phenotype, Ρ-gas, Ρ-bromine, 2-chloro-4-yl-toluene, di-wei, tetrachloropyran (THF), cyclohexene, and the like. Further, even if the solvent which does not dissolve the poly-acid is in the range of the poly-acid which is not precipitated, it can be used in the solvent. Further, the water in the organic solvent becomes a polymerization inhibitor. Further, the polylysine produced is hydrolyzed by decomposition, so that the organic solvent is preferably used for dehydration or drying. The X of the tetracarboxylic dianhydride at the production stage of the polyproline is 4 14 141414953 organic base. For specific examples, 3,3',4,4'-dibenzophenone tetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (ODPA) ), 3,3',4,4'-bis-phenyltetracarboxylic dianhydride (BPDA), 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), cyclobutane tetracarboxylic dianhydride (CBDA) and 4-(2,5-dihydrotetrahydrofuran-3-yl)-5-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (TDA), etc. The amine of the formula 9 or 10 which is a Y atom having a nitrogen atom is derived from the diamine of the above Chemical Formula 1. The benzyl derivative linked to the oxime group at the terminal of the side chain of the diamine can be displayed. It is horizontally oriented and contains many aromatic main chains and side chain diamines. Moreover, tetracarboxylic dianhydride can increase the surface polarity and increase the surface tension of the alignment film, showing a small pretilt angle. The benzoquinone group of the linked amine forms between the chains Further, in the space in which the organic solvent can be infiltrated, the solubility can be increased. Further, the above-described diamine compound of the above Chemical Formula 9 or 10 which constitutes Z having a nitrogen atom can be used as the diamine compound having no side substituent. ,4,4'-diaminodiphenyl ether (ODA), 4,4'-methylene-based dicyclohexylamine (PACM), 4,4'-nonylphenyl-2-methylcyclohexylamine (ANCAMINE) , 4,4' ^ monomethylenediphenylamine, diaminobenzophenone, 4,4'-indolyl diphenyldiamine (MDA), 4,4'-hexafluoroisopropyldiphenyl Diamine (6FDA), p-phenylene diamine (P_PDA), and the like. In order to obtain poly-proline acid, the tetracarboxylic dianhydride component and the diamine component are reacted in an organic solvent, which is usually 5 to 10 Torr (TC is preferred. When the temperature is high, the enthalpy is quickly ended, high. Since the molecular weight of the molecule becomes too high, it has to be noted. Further, the reaction concentration is made 5 to 3 % by weight, and uniform stirring can be carried out to obtain the desired molecular weight. The obtained polylysine can also be obtained. The reaction solution is diluted and used in 2009, and it is used in the process of recovery and re-dissolution. The weak solvent used in the recovery of the temple is not particularly limited, but may be methanol, ethanol, hexane, acetone or butyl cellosolve. For example, a reagent such as methyl ethyl ketone, toluene, benzene or diethylbenzene, which is obtained by a weak solvent, is used in the filtration process, & money recovery, and at atmospheric pressure. Or, under normal temperature or heat drying, a solid portion can be obtained. 10 15 For the above-mentioned polyimine, a side chain type divalent organic group (γ) is used for attachment = such as liquid crystal alignment, solubility, and membrane permeability. The same kind of polyimine machine month b I·sheng; f with side chain 2 price The machine base (7) is used to adjust the distribution of the side chain groups by adjusting the interval between the side keys. In the above chemical formula 7, m is an integer of 1 to 10, more preferably 2 to 4. The side chain length of the chain-type divalent organic group (7) is preferably adjusted to be 5 times the ratio of the usual length of the long axis of the liquid crystal molecule, and it is preferable to determine the amount of the organic group (ζ) which does not have a side chain group.俾The length between the side chain bases is 5 to 3.5 times longer than that of the liquid crystal. The σ method can be used to produce a special & nuclear (iv) imine resin, which exhibits excellent alignment with polyimine. 'There are characteristics of solubility, film penetration, and chemical enthalpy. Preferably, the weight average molecular weight of the polyimine resin is preferably from 1,000 to 200,000. Further, the present invention provides Liquid crystal matching of polyimide resin: film 'The liquid crystal alignment film can be obtained by coating an alignment liquid containing the above-mentioned polyimine compound on a patterned substrate, and then firing it. Using the solvent in the above alignment liquid As long as it is usually used in a liquid crystal alignment liquid, the aforementioned polyimine compound can be dissolved. The present invention is not particularly limited, and the alignment liquid system 16 200914953 preferably has 1 to 30% by weight of the above polyamidiamine compound. The liquid crystal alignment film of the present invention is excellent in liquid crystal alignment and abrasion resistance. The voltage maintenance ratio and the contrast ratio are high, and not only the charge accumulation but also the pretilt angle of the nematic liquid crystal to 2 degrees, and no residual image is obtained. The present invention is described in detail based on the following examples. The present invention is not limited to the following examples. [Example 1] f The bisamine compound of Chemical Formula 1 is synthesized by the reaction formula 1. According to each stage, the synthesis method will be explained as follows. Moth flakes and magnesium 3.5g were placed in &|(ether) 100ml, and slowly refluxed, and then 22.1 g of mercaptobenzyl bromide was slowly added to the ether bromide for 2 hours to produce a Grignard reactant. . After cooling the mixture to room temperature, 20 g of 4,4-dichlorobenzophenone was dissolved in tetrahydrofuran, and 155% of the mixture was slowly added dropwise, and the mixture was refluxed for 1 hour and 30 minutes. After cooling the reaction mixture, the saturated ammonium sulfate l〇m b was added and filtered with C salt, and then extracted with chlorine > and sodium chloride, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. 1,1 a double yellow (4-chlorophenyl)-2-pyrene basic pale yellow liquid. (25g, 90%) 20 4 NMR (CDC13, ppm): 7_20 (d, 4H), 7.13 (d, 4H), 7.09 (d, 1H), 6.93 (d, 1H), 6.92 (s, 1H), 6.88 (d, 1H), 3.32 (d, 2H), 2_35 (d, 3H), 2.00 (s, 1H) are placed in 1,1 -bis(4-mono-phenyl)-2-methylphenylethanol 35g 17 200914953 and 2.7 g of p-toluene sulfonic acid · l-hydrate, and placed in 200 ml of toluene. The solution was further flowed for 12 hours and allowed to react. After confirming the end of the reaction with a TLC plate, the mixture was washed with saturated sodium carbonate and ether and then taken. The pressure was dried under anhydrous magnesium sulfate, and the remaining water was distilled to give a brownish-yellow 1,1-di-(4-chlorophenyl)-2-methylphenylethylene liquid. (3ig, 95%) NMR (CDC13, ppm): 7.36 (d, 4H), 7.27 (d ' 4H), 7.23 (d ' 1H), 7.22 (s, 1H), 7.14 (d, 1H), 6.92 ( s, 1H), 6.91 (d, 1H), 2.35 (d > 3H) 10 In the third stage, 1,1_bis(4-monophenyl)-2-methylphenylethylene 2〇g, After 43.2 g of lithium bis(trimethyldecyl) guanamine, 2.6 g of tricyclohexylphosphine, and 5.3 g of bis(diphenylarhenylidene)! bar, i5 〇ml of toluene was placed. The inside of the reaction vessel was maintained at 90 ° C under a nitrogen atmosphere, and allowed to react for 12 hours. 15 Confirm the progress of the reaction by GC/Mass. 2 〇〇mi of ether was placed, the reaction mixture was diluted, and 300 ml of 1N hydrochloric acid (HCl) was added to complete the reaction. The organic layer obtained by rinsing the organic layer and the aqueous layer with 1N sodium hydroxide and ether was placed in a water-free sulfuric acid town. After drying, it was filtered. The mixture obtained by subjecting the solvent to distillation under reduced pressure was recrystallized from methylene chloride to give a white solid of U-bis(4-aminophenyl-phenyl)-2-methylphenylethylene. (9g, 5〇%) !H NMR (CDC13, ppm): 7.23 (d, 1H), 7.22 (s, 1H), 7.14 (d, 1H), 7.17 (d, 4H), 6_91 (d, 1H) , 6_92 (s, 1H), 6.46 (d, 4H), 3.74 (s, broad, 4H), 2.35 (d, 3H), stage 4 18 200914953 1,1 - double one (4-amino-phenyl) After dissolving in benzene and ethanol, put 1 bar (l〇wt% 〇n activated carbon) lg 'under 4kg/cm2 under pressure Mix for 5 hours. After confirming the completion of the reaction, the mixture was filtered through Celite, and the solution was evaporated under reduced pressure to give a white solid. The solid was recrystallized from ethylene glycol diacetate and ethanol to give a white 1,1-bis-(4-aminophenyl)-2-methylphenylethane (ethane) solid. (5g, 50%) iH NMR (CDC13, ppm): 7_09 (t, 1H), 6.93 (d, 1H), 6_92 (s, 1H), 6.88 (d, 1H), 6.87 (d, 4H), 6.41 (d, 4H), 4.44 (t, 1H), 10 3.74 (s, broad ' 4H), 3.17 (d, 2H), 2_35 (d, 3H) [Example 2] In addition to the use of fluorophenyl fluorenyl bromide In the same manner as in Example 1, except that the mercaptobenzyl bromide of the first stage of Example 1 was synthesized, 1,1 -bis-(4-aminophenyl)-2-fluorophenyl Ethylene. (5g, 20%) 15 iH NMR (CDC13, ppm): 7.19 (t, 1H), 6_89 (d, 1H), 6.87 (s, 1H), 6.79 (d, 1H), 6_87 (d, 4H), 6.41 (d, 4H), 4.44 (t, 1H), 3.75 (s, broad, 4H), 3_17 (d, 2H) [Example 3] 1,1 -di-(4-amino group) under nitrogen atmosphere 6.3 g of monophenyl)-2-methylbenzene-2-decylethane (ethane) and 8.3 g of 4,4,diaminodiphenyl ether (〇DA) were dissolved in N-methyl-2-pyrrolidone 122 g While maintaining the temperature at 5 ° C, 20 g of 3,3',4,4'-dibenzoiconetetracarboxylic dianhydride (BTDA) was added. The remaining N-mercapto-2-pyrrolidone 132 g was slowly dropped over 2 hours, and reacted for 10 hours. The reaction solution was placed in an excess of ultrapure water, and the deposited precipitate was filtered. 19 200914953 The filtrate was washed with methanol and dried under reduced pressure in a vacuum oven at 50 ° C to obtain polylysine. (weight average molecular weight: 260,000) [Example 4] In place of 3,3',4 used in the above 5th embodiment, 3,3',4,4'-bisphenyltetracarboxylic dianhydride (BPDA) In the same manner as in Example 3, except for 4'-dibenzophenone tetracarboxylic dianhydride (BTDA), a solid portion of polyamic acid was obtained. (weight average molecular weight = 70,000) [Example 5] In place of the above-mentioned Example 3, except that 1,1 -di-(4-amino-phenyl)-2-phenylene ethane was used. 1,1 mono-(4-aminophenyl)-2-methylphenylethane (ethane), and the same procedure as in Example 3 was carried out to obtain a solid portion of polylysine. (weight average molecular weight = 60,000) [Example 6] In place of the above-mentioned Example 3, except that 1,1 -di-(4-aminophenyl)-2-ethanephthalene 15 (ethane) was used. 1,1 mono-(4-aminophenyl)-2-nonylphenylethane (ethane), and 3,3',4,4'-bisphenyltetracarboxylic dianhydride (BPDA) The polyamic acid solid portion was obtained in the same manner as in Example 3 except that 3,3',4,4'-dibenzophenonetetracarboxylic dianhydride (BTDA) was used. (weight average molecular weight = 70,000) 20 [Comparative Example 1] In place of 1,1 mono-(4-aminophenyl)-2-phenylene ethane, the first used in the above Example 3 was replaced. In the same manner as in Example 3, a solid portion of polyglycolic acid was obtained except for mono-(4-aminophenyl)-2-nonylphenylethane. (weight average molecular weight = 60,000) 20 200914953 The physical property evaluation method used the following method. (1) Weight average molecular weight of polymer To calculate the weight average molecular weight of the polymer, gel permeation chromatography (GPC) was measured. The retention time of the column of dimethyl acetamide (5 DMA c) as a mobile phase and filled with a polymer substance was measured at 60 ° C. The average molecular weight and residence time of the styrene polymer were corrected. The result is calculated by calculating the average molecular weight of the solid portion of the polyamic acid. The polymer constituting the liquid crystal alignment agent has a weight average value of about 1,000 to 200,000 g/mol (the value of the sub-quantity. 10 (2) Pretilt angle of the liquid crystal display element by the literature (TJ Schffer, et. al., J , Appl., Phys., vol. 19, 2013 (1980)), using He-Ne laser light, measured by crystal rotation method. (3) Orientation of liquid crystal 15 Observation of liquid crystal by microscope The presence or absence of an abnormal domain in the liquid crystal cell when the display element is applied and not applied, and the type of the non-abnormal field is judged as 'good'. (4) The voltage holding ratio of the liquid crystal display element is applied to the liquid crystal display element. After the voltage of 5 V was 6 〇 microseconds, the voltage maintenance rate after 16.67 milliseconds after the application of the 20-plus state was measured. (5) Contrast ratio The light of the liquid crystal display element was measured without the applied voltage state (dark state). The transmittance and the light transmittance are calculated as the light transmittance at the maximum voltage (bright state). 21 200914953 (6) The residual image is evaluated in a mineral tooth shape having an electrode width of 5 # m and an interelectrode spacing of 1 〇# m Electrode (super-IP The liquid crystal alignment agent was printed on the substrate of S), dried, and baked to prepare a film having a film thickness of 200 nm (substrate 1). Similarly, a liquid crystal alignment agent was printed on the electrodeless 5 glass substrate and dried. After baking, a film having a thickness of 200 nm (substrate 2) was produced, and the substrate 1 was subjected to a rubbing treatment so that the liquid crystal alignment agent had an angle of 2 degrees in the direction of the electrode. Further, the substrate 2 was subjected to a rubbing treatment to form a substrate. (1) Parallel to the direction of the rubbing, the spacers were spread on the substrate, and the cells were bonded to each other to prepare cells having a gap of 4/zm, and liquid crystal MJ991735 (manufactured by Meishi Co., Ltd.) was injected into the cells to prepare liquid crystal cells. 0 to 1 〇V is applied to the liquid crystal cells at a rate of 0·lV/s and a frequency of 1 kHz. After measuring the voltage-transmittance (V τ) characteristic of the liquid crystal cell, the DC voltage is further applied. 〇V for 30 minutes. Immediately after the DC voltage is turned off, the v-T characteristic is measured, and the residual-image is evaluated by the voltage-transmittance characteristic before and after the application of the DC voltage. That is, the V-T characteristic causes a change, and When a certain voltage is applied When the luminosity is changed, the change can be observed in the field as a residual image. Further, the solid portions of the polyamic acid produced in the above Examples 3 to 6 and Comparative Example 1 were placed in NMP and 2-butoxy group. A solution having a concentration of 4% by weight was prepared by mixing ethanol in a mixture of 3: by weight ratio. The solution was filtered by a filter of 〇.1 on a glass substrate on which a transparent conductive film was patterned, The thickness of 600 A was applied by spin coating. After coating, it was pre-baked for 9 minutes at 9 Torr and then at 21 Torr. (: Baking for 1 hour, a substrate on which a polyimide film is formed. 22 200914953 Further, two glass substrates, such as a glass substrate with a comb-shaped electrode for IPS and a glass substrate without an electrode, are used. The alignment film is ultrasonically washed in ethanol for 3 minutes, and then the surface is washed with ultrapure water, then dried in an oven, spread with a spacer of 4/m, bonded, and then injected into the liquid crystal. The liquid crystal cells were prepared by sealing with an epoxy curing agent. The characteristics of the liquid crystal cells thus produced are shown in the following Table 1. [Table 1] Characteristics of liquid crystal cells Pretilt angle (degrees) Voltage maintenance ratio (%) Comparative ratio directional residual image Example 3 1.5 (±0.2) 99 100 Good No Example 4 1.5 (±0.2) 98 100 Good Example 5 1.5 (±0.2) 99 100 Good No Example 6 1.5 (±0.2) 98 100 Good Comparative Example 1 1.5 (+0.2) 97 98 is as good as the above-mentioned Table 1, and it is confirmed that all of the examples 3 to 6 and the comparative example 10 of the present invention have excellent characteristics as a liquid crystal alignment agent for driving a transverse electric field, and voltage Maintenance rate and alignment Those particular it was confirmed that the Example 3-6, as compared with Comparative Example 1, the residual image are significantly reduced. Brief Description of the drawings L 3 Main reference numerals 15 None None DESCRIPTION 23