TWI306529B

TWI306529B - Composition for liquid crystal alignment film, liquid crystal alignment film, liquid crystal holding substrate and liquid crystal display device

Info

Publication number: TWI306529B
Application number: TW094104802A
Authority: TW
Inventors: Takahiro Mori; Makoto Arase; Yuuichi Suga
Original assignee: Chisso Corp; Chisso Petrochemical Corp
Priority date: 2004-03-01
Filing date: 2005-02-18
Publication date: 2009-02-21
Also published as: KR101038691B1; JP4645213B2; TW200530712A; JP2006220676A; KR20060043247A

Description

I30652SU 九、發明說明：【發明所屬之技術領域】本發明係關於藉由主導性平行於基板表面的電場的形成而進行顯示的橫向電場方式，意即Ips (InPlane Switching，橫向電場驅動）型液晶顯示元件用聚醯亞胺配向、膜用組成物，使用此組成物所形成的配向膜以及含有此配、向膜的液晶保持基板及含有此液晶保持基板的橫電場方式液晶顯示元件（以下，稱為IPS型液晶顯示元件）。 Φ 【先前技術】液晶顯示元件最初被用於筆記型電腦或桌上型電腦的.4示盗、可攜式攝錄影機的觀景器(viewfinder)及投影型顯不器等各種液晶顯示裝置，最近亦被用作電視用顯示元件。此外，還用於光列印系統喷頭、光傅立葉變換元件及《栅料光電子元件。過去的液晶顯示元件以使用向列型液晶的顯示元件為主流，現在扭轉9〇度的TN(Twisted Nematic扭轉向列）型液晶顯示元件、通常扭轉i8〇度以上 • 的STN(SuperTwistedNematic超扭轉向列）型〉夜晶顯示元件、使用薄膜電晶體被稱為TFT (Thin_fUm transist〇r薄膜電晶體)型液晶顯示元件正在逐步實用化。然而，此種液晶顯示元件可正確辨識圖像的可視角度、狹窄’從斜方向觀看時，存在著亮度或對比度下降及半色、。周(half tone)發纟冗度反轉等缺點。近年來，此可視角度問題正在藉由使用光學補償義的TN魏晶顯示^件、併用垂直配向及突起構造物技術的MVA(Multi d〇main I306S2@ifd〇c =ca副gnment，多象限垂直配向法)型元件顯示元件或 ^向電場方式的IPS型液晶顯示元件等技術被進行改良而貫用化例如，可參照日本專利早期公開第特公昭— 21907號公報、日本專利早期公㈣特開平—1.8號公報及日本專利早期公開第特開平卜丨测號公報。其中’於過去的TN型液晶顯示元件中併用光學補償膜的方法’雖雜備投㈣的負擔少容易實現，但是半色調(halft_)顯示巾可視角度的改善效果不佳。方面’以MVA型液晶顯示元件為代表的垂直配向方式液晶顯不το件，是將具有負介電率異向性❹形向列液晶相對於基板面法線方向排列，施加電場使液晶傾斜而進行顯㈣。由於沒魏加電場時液晶趋配向、完全不產生雙折射，故人射光的偏光面幾乎無變化的通過液晶:因此，正交偏光—sed Nic〇1她)下可以容易實現黑顯示，故此液晶顯示元件可獲得高對比度。此種MVA舰晶顯示元件是於對^度方面非常有利的垂直配向方式液晶顯示元件。但是，MVA型液晶顯示元件與上述料補伽併时法同樣，_是半色調_ tone)顯不中液晶相對於基板面呈傾斜狀態，且可視性惡化。MVA魏晶_元件是藉由於基板上形成突^構造物及控舰晶的傾斜方向㈣少可視肖度依存或缺陷發生’關於此可視角度特性還有進—步改善的餘地。 IPS型液晶顯示元件是使液晶基本平行於基板面配向，同時藉由基板上所形成的杭狀電極產生的基本平行於 ⑧ I3〇6529Pifd〇c 基板面的電場，使液晶於基板面内轉動而進行顯示的。此 ips型液晶顯示元件本身即使施加電場，液晶也不會相對於基板面發生傾斜。因而’隨可視角度變化雙折射基本上不發生大的變化’故IPS型液晶顯示元件可獲得包含半色调(halftone)調顯示在内，非常理想的可視角度特性。I30652SU IX. Description of the Invention: [Technical Field] The present invention relates to a transverse electric field method for displaying by an electric field which is dominant parallel to a surface of a substrate, that is, an Ips (InPlane Switching) type liquid crystal An alignment film formed using the composition, an alignment film formed using the composition, a liquid crystal holding substrate containing the alignment film, and a lateral electric field type liquid crystal display element including the liquid crystal holding substrate (hereinafter, It is called IPS type liquid crystal display element). Φ [Prior Art] The liquid crystal display element was originally used for various liquid crystal displays such as a .4 thief of a notebook computer or a desktop computer, a viewfinder of a portable video recorder, and a projection type display device. The device has recently also been used as a display element for televisions. In addition, it is also used in optical printing system nozzles, optical Fourier transform elements and "grating optoelectronic components. In the past, liquid crystal display elements were mainly used as display elements using nematic liquid crystals, and now TN (Twisted Nematic) liquid crystal display elements with a twist of 9 degrees, and STNs that are usually twisted by i8 or more • SuperTwisted Nematic The column type> night crystal display element, and a thin film transistor called a TFT (Thin_fUm transist〇r thin film transistor) type liquid crystal display element are being gradually put into practical use. However, such a liquid crystal display element can correctly recognize the viewing angle of an image, and when viewed from an oblique direction, there is a decrease in brightness or contrast and a half color. Half tone has a shortcoming such as redundancy reversal. In recent years, this viewing angle problem is being achieved by using optically compensated TN Weijing display components and MVA (Multi d〇main I306S2@ifd〇c = ca subgnment, multi-quadrant vertical) using vertical alignment and protrusion structure technology. For example, the technique of the eigen-type device display device or the IPS-type liquid crystal display device of the electric field type is improved and can be used. For example, refer to Japanese Patent Laid-Open Publication No. SHO-121907, Japanese Patent No. (4) - Bulletin No. 1.8 and Japanese Patent Early Disclosure. Among them, the method of using an optical compensation film in the conventional TN type liquid crystal display device is easy to realize because the burden of the miscellaneous projection (4) is small, but the improvement effect of the half angle hue (halft_) display towel viewing angle is not good. The aspect of the vertical alignment mode liquid crystal display device represented by an MVA type liquid crystal display device is such that a negative dielectric constant anisotropic nematic nematic liquid crystal is aligned with respect to a normal direction of a substrate surface, and an electric field is applied to tilt the liquid crystal. Perform the display (four). Since there is no Weijia electric field, the liquid crystal tends to match, and no birefringence is generated at all. Therefore, the polarized surface of the human light is almost unchanged through the liquid crystal: therefore, the orthogonal display is sed Nic〇1, and the black display can be easily realized, so the liquid crystal display The component achieves high contrast. Such an MVA ship crystal display element is a vertical alignment type liquid crystal display element which is very advantageous in terms of degree. However, the MVA type liquid crystal display element is the same as the above-described material additive merging method, and _ is a halftone_tone), the liquid crystal is inclined with respect to the substrate surface, and the visibility is deteriorated. The MVA Weijing_ component is due to the formation of the protrusion structure on the substrate and the tilt direction of the control ship crystal. (4) Less visual dependence or defect occurrence. There is room for improvement in the viewing angle characteristics. The IPS type liquid crystal display element is such that the liquid crystal is aligned substantially parallel to the substrate surface, and the electric field substantially parallel to the surface of the 8 I3 〇 6529 Pifd 〇 c substrate is generated by the hanging electrode formed on the substrate, so that the liquid crystal rotates in the surface of the substrate. Displayed. Even if an electric field is applied to the ips type liquid crystal display element itself, the liquid crystal does not tilt with respect to the substrate surface. Therefore, the birefringence does not substantially change greatly depending on the viewing angle. Therefore, the IPS type liquid crystal display element can obtain a very desirable viewing angle characteristic including a halftone tone display.

/旦是，IPS型液晶顯示元件，由於是在正交偏光消光位獲得黑顯示，因而對液晶的配向狀態很敏感，會因發生光茂露而造成對比度下降。特別是與利用垂直配向完全不產生雙折射的MVA型顯示元件相比較，此對比度問題是很嚴重的。、如上所述，IPS液晶顯示元件在可視角度方面與其他方式相比品質優異，但在對比度方面劣於以廣可視角度型液晶顯示元件著稱的MVA型液晶顯示元件，例如，可參照曰經微器件（日経Y彳夕口于，〆彳乂），，，2〇〇3年5月號， p71。白顯示亮度與黑顯示亮度比率的對比度被用作表述液μ顯示元件性能的指標之一。一般而言，白顯示亮度沒有大的變化，因此對比度很大程度上取決於作為分母的署顯示亮度。因而，為了提高對比度，降低黑顯示亮度很重要0 * IPS型液晶顯示元件，一般藉由正交偏光下使單片偏光板的方向與液晶的配向方向一致，作為無施加電場時進行黑顯示的無電暗(normally black)顯示。構成此種元件時，若配向膜的單軸配向性不充分，則發生以分子排列秩 I306529pif.doc 序性表不的液晶配向方向分佈為起因的光茂露示特性惡化及對比度下降。進一步，^ 成…、頁中亦可藉由摩擦處理賦予配向膜單 ^液：4不疋件有梳狀電極的臺階旁區域難於L ;理。二而二配置單軸配向性不完全。由於此區域里，故配向膜的露及導致_度惡化。[料秩序性配向而產生光茂如上所述’為提高IPS型液曰制配向膜的單軸配向性很重要。曰曰‘”、不兀牛的對比度’控進一步，作為IPS型液晶顯示元件中共有的問題可列舉長時間顯示同一書面後：時前一畫像作為殘像殘留的被稱為殘存的：像是非常2獲仔向品質液晶顯示元件’改善此殘存現 ί:;:;要的問題。殘存的原因被認為是配向膜表面的 :::2純離子等電荷積累，或因殘留Dc液晶分于上所加的電壓不能被消除而引起的。 _ 方式與IPS方式的電場方向不同，液晶層中In the case of the IPS type liquid crystal display element, since the black display is obtained at the orthogonal polarization extinction position, the alignment state of the liquid crystal is sensitive, and the contrast is lowered due to the occurrence of the light exposure. This contrast problem is particularly serious in comparison with MVA type display elements which do not produce birefringence at all by vertical alignment. As described above, the IPS liquid crystal display element is superior in quality to other methods in terms of viewing angle, but is inferior to the MVA type liquid crystal display element known as a wide viewing angle type liquid crystal display element in contrast, for example, Device (Japanese Y経夕口, 〆彳乂),,, 2, 3, May, p71. The contrast ratio of the white display luminance to the black display luminance ratio is used as one of the indexes for expressing the performance of the liquid μ display element. In general, the white display brightness does not change much, so the contrast is largely determined by the brightness of the display as the denominator. Therefore, in order to improve the contrast, it is important to reduce the black display brightness. 0 * IPS type liquid crystal display element, generally, the direction of the single polarizing plate is aligned with the alignment direction of the liquid crystal by orthogonal polarization, and black display is performed when no electric field is applied. Normally black display. In the case of constituting such an element, if the uniaxial alignment property of the alignment film is insufficient, deterioration of the photoluminescence characteristic and deterioration of contrast due to the liquid crystal alignment direction distribution indicated by the molecular arrangement rank I306529pif.doc sequence occur. Further, it is also possible to impart an alignment film to the alignment film by rubbing treatment: 4, and the step side region having the comb electrode is difficult to be treated. Two-two configuration Single-axis alignment is not complete. Due to this area, the appearance of the alignment film deteriorates. [Organization of ordered alignment to produce photo-optical as described above] It is important to improve the uniaxial alignment of the IPS-type liquid helium alignment film.曰曰'", the contrast of the yak is not further controlled. As a problem common to IPS-type liquid crystal display elements, it can be cited that the same image is displayed for a long time: When the previous image is left as an afterimage remains, it is called: Very 2 get the quality of the liquid crystal display element 'improve this residual 现:;;; the problem. The remaining reason is considered to be the surface of the alignment film::: 2 pure ions and other charge accumulation, or due to residual Dc liquid crystal The voltage applied above cannot be eliminated. _ The mode is different from the electric field direction of the IPS method, in the liquid crystal layer

累的電壓消除過程亦不同。總而言之TN 膜m電㈣直於基板方向’躲晶層與配向膜或絕緣膜或絕緣:接二:r)fIPS方式中液晶水平方向扩力基ί成刀王並列相接，這可由電場沿基板的、因而，由於液晶層與其他組立(cell)構成部件之間的電 ’ lps方式與TN方式產生不同的電性動作，故欣晶顯示元件必須採取獨有的減少積累電荷對策。 130652ft if.doc 例如，可參照非專利文獻，，液晶”，1998 目前’已有提案公開TN方式液晶顯示元件卷中=1用 :有硫鍵的聚醯亞胺’可較少形成累積二使用件的液晶配向劑’但是未說明液日日日層與 ^^ 式液晶顯示元件中減少累積;•的並 =如’可參照日本專利早期公開第特開平5 — 2_^公The tired voltage elimination process is also different. In summary, TN film m electricity (four) straight to the substrate direction 'hiding layer and alignment film or insulating film or insulation: connect two: r) fIPS mode liquid crystal horizontal direction expansion force ί into the knife king juxtaposed, which can be electric field along the substrate Therefore, since the electric 'lps mode between the liquid crystal layer and the other cell components is different from the TN mode, the X-Crystal display element must take a unique measure to reduce the accumulated charge. 130652ft if.doc For example, refer to the non-patent literature, Liquid Crystal", 1998. At present, there is a proposal to disclose a TN-type liquid crystal display element in a volume = 1: a sulfur-bonded polyimine can be used to form less than two. The liquid crystal alignment agent of the piece 'but does not explain the reduction of the accumulation in the liquid day and the liquid crystal display element; and the sum == can refer to the Japanese Patent Early Publication No. 5 - 2_^

IPS 仁未β及IPS方式中硫鍵對對比度果，例如’可參照曰本專利早期公開第=電r f公報及日本專利早期公開第特開平1G〜1G535號公報。7In the case of the IPS, the sulphur bond and the IPS method are in the form of a contrast ratio, for example, the Japanese Patent Laid-Open Publication No. Hei. 7

【非專利文獻2】液晶，1998年第2表ρΉ ;UA 。【發明内容】牛弟2卷P3H 課勒純可形成料高單做向性成的配向模以及含有此配向膜二==形晶保持基板、具有優異對比度、不少的IPS型液晶顯示元件。、電何减本發％人為解決±麟題❿專心研冑絲發現醢：四鲮酸一酐的反應生成物聚醯胺酸或可溶性令 =胺的聚㈣㈣液日日日配向職域物、由此組成t :::液晶配向膜、含有此配向膜的液晶保持基板以及2 t液晶保持基板的液晶顯示元件，對於解決課題非常：效’從而完成本發明。 ^ I30653Qif.doc 本發明之構成如下所述。 (1) 一種適用於橫電場方式液晶顯示元件的聚醯亞胺系液晶配向膜用組成物，含有四羧酸二酐與二胺的反應生成物聚醯胺酸或聚醯亞胺，其特徵在於二胺含有式[1]化合物作為必需成分，進一步含有式[2]及式[3]化合物中的至少 1種。 [1] [2] Η2Ν — Xj — NH2 H2N —X — X2 — X — NH2[Non-Patent Document 2] Liquid crystal, 1998, Table 2, Ή; UA. SUMMARY OF THE INVENTION Niu Di 2 volumes P3H can be formed into a directional alignment mold and an IPS type liquid crystal display element having the alignment film and the shape retention substrate, which has excellent contrast and is excellent. , how to reduce the power of the hair%% of the solution to solve the problem of the 麟麟 ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ 醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢醢The liquid crystal display element having the composition t:: liquid crystal alignment film, the liquid crystal holding substrate containing the alignment film, and the 2 t liquid crystal holding substrate is very effective in solving the problem. ^ I30653Qif.doc The constitution of the present invention is as follows. (1) A composition for a polyfluorene-based liquid crystal alignment film which is suitable for a liquid crystal display device of a transverse electric field type, and contains a reaction product of a tetracarboxylic dianhydride and a diamine, a polyamine or a polyimine. The diamine contains the compound of the formula [1] as an essential component, and further contains at least one of the compounds of the formula [2] and the formula [3]. [1] [2] Η2Ν — Xj — NH2 H2N —X — X2 — X — NH2

[3] 式中，X1為含有-s-的2價有機基團，每一 χ分別為苯環或環己烷，X2為含有-(CH2)n-或的2價有機基團。 η為2〜7的整數，R!及R2各自分別為氫原子、氫氧基、或碳數為1〜5的烷基或碳數為1~5的烷氧基。[3] wherein X1 is a divalent organic group containing -s-, each of which is a benzene ring or a cyclohexane, and X2 is a divalent organic group containing -(CH2)n- or. η is an integer of 2 to 7, and each of R and R2 is a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

(2)如第1項所述之液晶配向祺用組成物，其中式中，Xi為式[4]所示的2價基團。 [4] 式中，A分別為^ ，一或-(CH2)r-，Y分别為單鍵、-S·或-0，u為0或:I’U為0時q為〇，uJg q為0、1或2，r為2〜10的整數。 ‘、、' f (3)如第2項所述之液晶配向犋用組成物，其中式[4] 所示的2價基團為式[5]或式[6]所示的基團。(2) The liquid crystal alignment composition according to Item 1, wherein Xi is a divalent group represented by the formula [4]. [4] where A is ^, or -(CH2)r-, Y is a single bond, -S· or -0, u is 0 or: when I'U is 0, q is 〇, uJg q Is 0, 1 or 2, and r is an integer of 2 to 10. The liquid crystal alignment composition according to the item 2, wherein the divalent group represented by the formula [4] is a group represented by the formula [5] or the formula [6].

I30652ftfdoc (8) 如第5項所述之液晶配向膜用組成物，在式[8]中， Y為式[10]所示的2價基團。 (9) 如第1〜8中任一項所述之液晶配向膜組成物，在式 [3]中’ 1^及R2各自分別為氫原子或碳數1〜3的烷基或燒氧基。 (10) 如第1〜9中任一項所述之液晶配向膜組成物，在式[3]中二個胺基的位置為對位。 (11) 如第1〜10中任一項所述之液晶配向膜組成物，在二胺中，使式[1]與式[2]化合物、式[1]與式化合物、或式[1]與式[2]與式[3]化合物的組合中’式[η化合物的含量為30〜99莫爾％，式[2]及式[3]所示化合物的含量合計為 (12) 如第1〜11中任-項所述之液晶配向膜組成物，盆中四羧酸二酐由20〜80莫爾％苯均四酸二酐與8〇〜2〇莫爾 %環丁烷四酸二酐所構成。、 (13) 由第1〜12中任-項所述之液晶配向膜組成物所形成的液晶配向膜。 (14) 3有如第π項所述之液晶配向朗液晶保持基板。 (15)朝向液晶面設置有電極的液晶保持基板上，含有如第13項所述之液晶配向膜的液晶顯示元件。 ⑽-種適用於橫電場方式液晶顯示元件的液晶配向 ”物’含有四羧酸二酐與二胺的反應生成物聚醯胺 H«亞胺’其特徵在於該液晶配向則纟歧物至少含 13 I3065S9iw〇c 有下述反應生成物A及反應生成物B。反應生成物A :四羧酸二酐與含有式[1]化合物作為必需成分的二胺的反應生成物聚醯胺酸或聚醯亞胺。反應生成物B :四羧酸二酐與含有式[2]化合物作為必需成分的二胺的反應生成物聚醯胺酸或聚醯亞胺。 H2N — X — X2 一 X 一 NH2 [2](10) The composition for liquid crystal alignment film according to Item 5, wherein Y is a divalent group represented by the formula [10]. (9) The liquid crystal alignment film composition according to any one of the first to eighth aspects, wherein in the formula [3], each of '1^ and R2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or an alkoxy group. . (10) The liquid crystal alignment film composition according to any one of the preceding claims, wherein the position of the two amine groups in the formula [3] is para. (11) The liquid crystal alignment film composition according to any one of 1 to 10, wherein a compound of the formula [1] and the formula [2], a formula [1], a compound of the formula, or a formula [1] is used in the diamine. In combination with the compound of the formula [2] and the compound of the formula [3], the content of the formula [η is 30 to 99 mol%, and the total content of the compound represented by the formula [2] and the formula [3] is (12) The liquid crystal alignment film composition according to any one of the items 1 to 11, wherein the tetracarboxylic dianhydride in the pot is composed of 20 to 80 mol% of pyromellitic dianhydride and 8 Å to 2 Torr of Mohr% cyclobutane IV. It is composed of acid dianhydride. (13) A liquid crystal alignment film formed from the liquid crystal alignment film composition according to any one of items 1 to 12. (14) 3 The liquid crystal alignment liquid crystal holding substrate as described in the item π. (15) A liquid crystal display element comprising the liquid crystal alignment film according to item 13 on the liquid crystal holding substrate provided with the electrode on the liquid crystal surface. (10) A liquid crystal alignment "object" suitable for a horizontal electric field type liquid crystal display element contains a reaction product of a tetracarboxylic dianhydride and a diamine, polyamine H«imine, which is characterized in that the liquid crystal alignment is at least 13 I3065S9iw〇c has the following reaction product A and reaction product B. Reaction product A: a reaction product of tetracarboxylic dianhydride and a diamine containing a compound of the formula [1] as an essential component, polyglycine or poly醯imine. Reaction product B: a reaction product of a tetracarboxylic dianhydride with a diamine containing a compound of the formula [2] as an essential component, a polyamine or a polyimine. H2N — X — X 2 — X — NH 2 [2]

式中，X,為含有-S-的2價有機基團，X分別為笨環或環己烧，X2為含有-(CH2)n-或-0-的2價有機基團 2〜7的整數。 (17) 如第16項所述之液晶配向膜用組成物，其中式中，X!為式[4]所示的2價基團。丫[4] 式中’ A分別為或-(CH2)r-，γ分別為單鍵、-S-或-0_，u為0或1，U為0時q為0，u為1時 q為0、1或2，r為2〜10的整數。、 (18) 如第17項所述之液晶配向膜用組成物’其中式[4] 所示的2價基團為式[5]或式[6]所示的2價基團。 fO~设 [5] ^^-S-(CH2)-S-^y [6] 式中，t為1，2或3，rl為2〜7的整數。 (19)如第Π項所述之液晶配向膜用組成物，其中式[4] ⑧ 14 I30653ftf.doc 其中反應生成物A中所用的四羧酸二酐是由20〜80莫爾〇/〇苯均四酸二酐與80〜20莫爾％環丁烷四酸二酐所構成。 (26) 如第16〜25中任一項所述之液晶配向膜組成物，其中反應生成物B中所用的四羧酸二酐是由20〜80莫爾％苯均四酸二酐與80〜20莫爾％環丁烷四酸二酐所構成。 (27) 由第16〜26中任一項所述之液晶配向膜組成物所形成的液晶配向膜。 (28) 含有如第27項所述之液晶配向膜的液晶保持基板。 (29) 朝向液晶面設置有電極的液晶保持基板上，含有如第27項所述之液晶配向膜的液晶顯示元件。本發明可提供具有特別優異對比度、減少殘留DC不引起殘存的累積電荷減少的IPS型液晶顯示元件，可實現此目的的配向膜以及可形成該配向膜的液晶配向膜用組成物。 *為讓本發明之上述和其他目的、特徵和優點能更明顯Wherein X is a divalent organic group containing -S-, X is a stupid ring or a cyclohexene, and X2 is a divalent organic group having a -(CH2)n- or -0- 2~7 Integer. (17) A composition for a liquid crystal alignment film according to the above formula, wherein X! is a divalent group represented by the formula [4].丫[4] where 'A is or -(CH2)r-, γ is a single bond, -S- or -0_, u is 0 or 1, when U is 0, q is 0, and u is 1 when q Is 0, 1 or 2, and r is an integer of 2 to 10. (18) The composition for liquid crystal alignment film according to Item 17, wherein the divalent group represented by the formula [4] is a divalent group represented by the formula [5] or the formula [6]. fO~ is set to [5] ^^-S-(CH2)-S-^y [6] where t is 1, 2 or 3, and rl is an integer of 2 to 7. (19) A composition for a liquid crystal alignment film according to the above item, wherein the tetracarboxylic dianhydride used in the reaction product A is from 20 to 80 mol?/? It is composed of pyromellitic dianhydride and 80 to 20 mol% cyclobutane tetracarboxylic dianhydride. The liquid crystal alignment film composition according to any one of the items 16 to 25, wherein the tetracarboxylic dianhydride used in the reaction product B is 20 to 80 mol% of pyromellitic dianhydride and 80 ～20 mol% cyclobutane tetraacid dianhydride. (27) A liquid crystal alignment film formed from the liquid crystal alignment film composition according to any one of the items 16 to 26. (28) A liquid crystal holding substrate comprising the liquid crystal alignment film according to item 27. (29) A liquid crystal display element comprising the liquid crystal alignment film according to item 27, which is provided on the liquid crystal holding substrate provided with the electrode toward the liquid crystal surface. The present invention can provide an IPS type liquid crystal display element which has particularly excellent contrast ratio and which reduces residual charge reduction which does not cause residual DC, and an alignment film which can achieve the object and a composition for a liquid crystal alignment film which can form the alignment film. * To make the above and other objects, features and advantages of the present invention more apparent

易懂，下文特舉較佳實施例，並配合所附圖<，作詳細說明如下。【實施方式】本發明的液晶配向膜用組成物的—種較佳的形態為胺的反應生成物聚_酸或聚醯亞胺配向膜用組成物，其中該聚醯胺酸或聚主夕1種的二胺與四羧酸二酐的共聚反應 ⑧ 16 I30652Sfd 生成物為特徵的，且適用於橫電場方式液晶顯示元件的聚醯亞胺系液晶配向膜用組成物。本發明中，式[1]所示的二胺可列舉以下化合物。It is to be understood that the preferred embodiments are described below and are described in detail with reference to the accompanying drawings. [Embodiment] A preferred embodiment of the composition for a liquid crystal alignment film of the present invention is a composition for a reaction product of an amine, a poly-acid or a polyimine-imparting film, wherein the poly-proline or poly-primary A composition of a polyimine-based liquid crystal alignment film which is characterized by a copolymerization reaction of a diamine and a tetracarboxylic dianhydride, which is characterized by a composition of 8 16 I30652 Sfd, and which is suitable for a horizontal electric field type liquid crystal display device. In the present invention, the diamine represented by the formula [1] includes the following compounds.

R,R-H,CH3,C2H5,C3H7,C4H9,C5Hl 1 OCH3,OC2H5,OC3H7,Cl,Br,I,〇HR, R-H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, 〇H

R,R'=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 OCH3,OC2H5,OC3H7,Cl,Br,I,〇HR, R'=H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, 〇H

⑧ 11I30652Skd〇 9 10 h2n8 11I30652Skd〇 9 10 h2n

1212

16 1716 17

ζ,/S-R -NH 2ζ, /S-R -NH 2

H2N R=CH3,C2H5,C3H7,C4H9, C5Hll,C6Hl3,C7Hl5H2N R=CH3, C2H5, C3H7, C4H9, C5Hll, C6Hl3, C7Hl5

R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 0CH3,0C2H5,0C3H7,Cl,Br,I,0H 18R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 0CH3,0C2H5,0C3H7,Cl,Br,I,0H 18

H2NH2N

R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 0CH3,0C2H5,0C3H7,Cl,Br,I,0HR=H, CH3, C2H5, C3H7, C4H9, C5Hl 1 0CH3, 0C2H5, 0C3H7, Cl, Br, I, 0H

R=H,CH3，C2H5,C3H7，C4H9，C5Hl 1 OCH3,OC2H5,OC3H7，Cl，Br，I，OH 20R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 OCH3,OC2H5,OC3H7,Cl,Br,I,OH 20

RR

R二 H，CH3，C2H5，C3H7，C4H9，C5Hll 0CH3,0C2H5,0C3H7,Cl,Br,I,0HR 2 H, CH3, C2H5, C3H7, C4H9, C5Hll 0CH3, 0C2H5, 0C3H7, Cl, Br, I, 0H

R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 OCH3,OC2H5,OC3H7,Cl,Br,I,〇H 18 23 23R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 OCH3,OC2H5,OC3H7,Cl,Br,I,〇H 18 23 23

13 065!29?>? d〇c 22 H2 h213 065!29?>? d〇c 22 H2 h2

R=H，CH3，C2H5，C3H7，C4H9，C5Hl 1 OCH3,OC2H5,OC3H7,Cl，Br,I,OHR=H, CH3, C2H5, C3H7, C4H9, C5Hl 1 OCH3, OC2H5, OC3H7, Cl, Br, I, OH

R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 ◦CH3,OC2H5,OC3H7，Cl，Br,I，OH 26 27R=H,CH3,C2H5,C3H7,C4H9,C5Hl 1 ◦CH3,OC2H5,OC3H7,Cl,Br,I,OH 26 27

⑧ 130652^>fd〇c 28 298 130652^>fd〇c 28 29

⑧ I30652ftifd〇c8 I30652ftifd〇c

40 (CH2)-S-p40 (CH2)-S-p

n=2〜10n=2~10

4444

H2N〇_S_(CH2irS^0)~S_(CH2n"'SH2N〇_S_(CH2irS^0)~S_(CH2n"'S

22

45 h2n〇~s_(CH2!t° 46 O—(CH2)—S n45 h2n〇~s_(CH2!t° 46 O—(CH2)—S n

H2N〇^S_(CH2iTS n=2〜10H2N〇^S_(CH2iTS n=2~10

n=2〜10 S—(CH2)—s nn=2~10 S—(CH2)—s n

21 2 I306527Qif.doc 4721 2 I306527Qif.doc 47

4848

4949

5050

51 ~^—^NH251 ~^—^NH2

s-s h2n 式[1]所示較佳的二胺，可列舉以下化合物。 22 52 13 Ο652® if d〇cS-s h2n The preferred diamine represented by the formula [1] includes the following compounds. 22 52 13 Ο652® if d〇c

H2NH2N

NH 2NH 2

54 53 ΧΧχχχΓ2 H2N~^ ^~S—(CH2)2-S—^ ^—1 —^ ^-s—(CH2)3-S—^ ^-nh2 56 H2N~^ ^~s—(ch2)4-s—^ ^-1 —^ ^-s—(ch2)5-s—^ ^-nh2 58 H2N~^ ^~s—(ch2)6-s—^ ^—1 —^ ^-S—(CH2)7'S—^ ^—nh2 60 H2N~^ ^~S-S~^ ^-NH2 NH 2 NH 2 NH 254 53 ΧΧχχχΓ2 H2N~^ ^~S—(CH2)2-S—^ ^—1 —^ ^-s—(CH2)3-S—^ ^-nh2 56 H2N~^ ^~s—(ch2)4 -s-^ ^-1 —^ ^-s—(ch2)5-s—^ ^-nh2 58 H2N~^ ^~s—(ch2)6-s—^ ^—1 —^ ^-S—( CH2)7'S—^ ^—nh2 60 H2N~^ ^~SS~^ ^-NH2 NH 2 NH 2 NH 2

H2N 55H2N 55

H2N 57 h2n 59 式[1]所示更佳的二胺，可列舉以下化合物 h2nQ-S^NH2 式[1]所示特佳的二胺 1-1 可列舉以下化合物。 1-2H2N 57 h2n 59 The more preferable diamine represented by the formula [1], the following compounds h2nQ-S^NH2 The particularly preferred diamine 1-1 represented by the formula [1] can be exemplified by the following compounds. 1-2

H2N 0S{^NH2 η2ν νη2 可以使用一種式[1]所示的二胺，亦可二種以上混合使用 23 1306SQi 9p*f d〇c 式[2]所示的二胺可列舉以下化合物。H2N 0S{^NH2 η2ν νη2 The diamine represented by the formula [1] may be used, or two or more kinds may be used in combination. 23 1306SQi 9p*f d〇c The diamine represented by the formula [2] may be exemplified by the following compounds.

69 7069 70

71 .〇-(CH2)71 .〇-(CH2)

H?N- n=2 〜7H?N- n=2 ～7

(D 24 13065妙ifdoc 72 h2n ο-°-α (ch2) r :2 〜*7(D 24 13065 妙 ifdoc 72 h2n ο-°-α (ch2) r : 2 ~*7

NH 2 73NH 2 73

(CH2) α nh2(CH2) α nh2

74 H〇N74 H〇N

7676

H2NH2N

nh2 h2n n=2~7 n=2〜7, P=1 〜2Nh2 h2n n=2~7 n=2~7, P=1 ～2

25 ③ 130652ft if.doc 式[2]所示較佳的二胺，可列舉以下化合物 84 h2n—nh2 85 H2N87 H2N89 H2N91 h2n -a- (ch2)4 ~Qr J^r (ch2)6 <y%25 3 130652ft if.doc The preferred diamines of the formula [2] include the following compounds 84 h2n-nh2 85 H2N87 H2N89 H2N91 h2n -a- (ch2)4 ~Qr J^r (ch2)6 <y %

86 H2N88 H2N90 H2N -o- (ch2)3 <y (CH2)5 Or JOr (ch2)7 92 —<~(CH2)2-〇—^~>—NH2 H2N—~o—(CH2)3-Q-^~^)-nh2 93 94 H2N—〇一(CH2)4-〇—NH2 H2N—^~^-〇-(CH2)5-〇—nh2 95 96 o—(ch2)6-o 乂]^nh2 h2n-^^- o-(ch2)7-o ^Q^nh2 97 98 26 10013065妙 if.doc 99 101 102 h2N—〇Ή^^>—(CH2)6-^^)—NH2 H2N^~^^〇一(CH2)7H^^h-NH2 103 h2n104 h2n105 h2n <y (ch2)2 <y (ch2)2^D^0^O^(ch2)2HO^°^j^ 106 H2N107 h2n108 h2n109 h2n \ I0^〇_O^(ch2)7{^〇_<0^ no h2nh〇cH2{^· (CH2)3 {^ch2{^nh2 27 I3065i29pifd〇c 111 h2n (ch2)2 JOr (CH2)6 (ch2)2 112 h2n (CH2)2 JOr (ch2)7 o (ch2)2 113 h2n114 (CH2)3 (ch2)2 (CH2)386 H2N88 H2N90 H2N -o- (ch2)3 <y (CH2)5 Or JOr (ch2)7 92 —<~(CH2)2-〇—^~>—NH2 H2N—~o—(CH2) 3-Q-^~^)-nh2 93 94 H2N—〇一(CH2)4-〇—NH2 H2N—^~^-〇-(CH2)5-〇—nh2 95 96 o—(ch2)6-o乂]^nh2 h2n-^^- o-(ch2)7-o ^Q^nh2 97 98 26 10013065妙 if.doc 99 101 102 h2N—〇Ή^^>—(CH2)6-^^)— NH2 H2N^~^^〇一(CH2)7H^^h-NH2 103 h2n104 h2n105 h2n <y (ch2)2 <y (ch2)2^D^0^O^(ch2)2HO^°^j ^ 106 H2N107 h2n108 h2n109 h2n \ I0^〇_O^(ch2)7{^〇_<0^ no h2nh〇cH2{^· (CH2)3 {^ch2{^nh2 27 I3065i29pifd〇c 111 h2n (ch2 ) 2 JOr (CH2)6 (ch2)2 112 h2n (CH2)2 JOr (ch2)7 o (ch2)2 113 h2n114 (CH2)3 (ch2)2 (CH2)3

NH 丨2NH 丨2

h2n115 H2N (CH2)3 (CH2)3 JOr (CH2)3 JOr Ό- (CH2)3 <y (CH2)4 <y (CH2)3H2n115 H2N (CH2)3 (CH2)3 JOr (CH2)3 JOr Ό- (CH2)3 <y (CH2)4 <y (CH2)3

NH '2NH '2

116 H2N ) _ _ _ _ <y (CH2)3 (CH2)5 JOr (CH2)3 發H2 117 h2n JOr (CH2)3 (ch2)6 (ch2)3 118 h2n (CH2)3 <y (ch2)7 (CH2)3 〇~nh2 式[2]所示更佳的二胺，可列舉以下化合物 ⑧ 28 120 Ι3065®9ρ_ 119 η2ν 122 Η2Ν 121 η2ν <y (CH2)3 η2ν <y (ch2)4 123 124 h2N—^~^-(ch2)5-<^^>—nh2 h2n—(ch2)2-^^>—(Ch2)2-^^>—116 H2N ) _ _ _ _ <y (CH2)3 (CH2)5 JOr (CH2)3 Hair H2 117 h2n JOr (CH2)3 (ch2)6 (ch2)3 118 h2n (CH2)3 <y ( Ch2)7 (CH2)3 〇~nh2 The more preferable diamine represented by the formula [2], the following compounds 8 28 120 Ι3065®9ρ_ 119 η2ν 122 Η2Ν 121 η2ν <y (CH2)3 η2ν <y ( Ch2)4 123 124 h2N—^~^-(ch2)5-<^^>-nh2 h2n—(ch2)2-^^>—(Ch2)2-^^>—

NH 2 2NH 2 2

125 H2N—0——(CH2)2-(^ ^—0—ζ^ NH125 H2N—0——(CH2)2-(^^—0—ζ^ NH

126 H2N126 H2N

NH 2 2 2 129 H2N ch2 (ch2)3 <y ch2 <y nh2 可以使用一種式[2]所示的二胺，亦可二種以上混合使用。式[3]所示的二胺可列舉以下化合物。 ⑧ Ι306539ρϋ 130 131NH 2 2 2 129 H2N ch2 (ch2) 3 <y ch2 <y nh2 The diamine represented by the formula [2] may be used, or two or more kinds may be used in combination. The following compounds are exemplified as the diamine represented by the formula [3]. 8 Ι306539ρϋ 130 131

132132

R=CH3,C2H5,C3H7,C4H9,C5Hl 1 133R=CH3, C2H5, C3H7, C4H9, C5Hl 1 133

134134

R=CH3,C2H5,C3H7,C4H9,C5Hl 1 R'=CH3,C2H5,C3H7,C4H9,C5Hl 1 R=CH3,C2H5,C3H7,C4H9,C5Hl 1 R'=CH3，C2H5，C3H7，C4H9，C5Hl 1 式[3]所示較佳的二胺，可列舉以下化合物。 135 136 !η3 137 H2N Η2Ν h2n 1 1R=CH3, C2H5, C3H7, C4H9, C5Hl 1 R'=CH3, C2H5, C3H7, C4H9, C5Hl 1 R=CH3, C2H5, C3H7, C4H9, C5Hl 1 R'=CH3, C2H5, C3H7, C4H9, C5Hl 1 Preferred examples of the diamine represented by the formula [3] include the following compounds. 135 136 !η3 137 H2N Η2Ν h2n 1 1

138 139 C2H5 H2N H2fS I V^NH2^^CH3 ^ CQu138 139 C2H5 H2N H2fS I V^NH2^^CH3 ^ CQu

c2h5 141 142 93H7 143 h2n JL ) 1 T 1 JL 2、 h2n l '^^NH2kv/kc2Hs 1 ecuC2h5 141 142 93H7 143 h2n JL ) 1 T 1 JL 2, h2n l '^^NH2kv/kc2Hs 1 ecu

C3H7C3H7

C3H7 ⑧ 147I30652ftifd〇c 145C3H7 8 147I30652ftifd〇c 145

146146

H2NH2N

och3 148 OC2H5 149 H2N H2N rvT"YOC2H5 I nh2 I u. U nh2 150Och3 148 OC2H5 149 H2N H2N rvT"YOC2H5 I nh2 I u. U nh2 150

H2NH2N

〇c2h5 153〇c2h5 153

151151

152152

H2NH2N

OC3H7 154 155OC3H7 154 155

159 160159 160

OH H2NOH H2N

H2NH2N

OH OH 31 130652ft if.docOH OH 31 130652ft if.doc

OCH-, 166OCH-, 166

式[3]所示更佳的二胺，可列舉以下化合物Preferred diamines of the formula [3] include the following compounds

171171

9CH,9CH,

0CH, 1720CH, 172

可以使用一種式[3]所示的二胺，亦可二種以上混人使示的二再者，為提高無電壓施加時的黑顯示特性，式所示的二胺中二個胺基的位置為對位者較鄰位或間位者為佳: 本發明中’式[1]所示的二胺與式[2]或式[3]所胺併用，或與式[2]及式[3]所示的二胺皆併用。此時，式Π]與式[2]、式⑴與式[习或式⑴與式[2] :]々所不的胺組合中，式⑴的二胺含量為3。莫爾％〜99莫广圍内為佳。若其含量為3G莫爾％以上，則使用所得聚醯亞胺系液晶配向膜用組成物的液晶顯示元件明顯表^ I30652^ifd〇c 積電荷或稱為殘留DC降低的顯著效果。式[1]所示的二胺中併用式p]及/或式[3]所示的二胺’ 使用所得聚醯亞胺系液晶配向膜用組成物的液晶顯示元件，無施加電壓時黑顯示特性被提高的效果明顯。式[2] 及/或式[3]的二胺含量多可以使得此黑顯示特性提高，同時考慮減少殘留DC效果，此含量的合計較佳為i莫爾％〜7〇莫爾％的範圍内。再者，本發明中亦可進一步包括上述式[1]、式P]及式 • [3]以外的二胺（以下稱為“其他二胺”），此情形的其他二胺的比例較佳為為二胺總量的30%以下，超過3〇%則使用所得聚醯亞胺系液晶配向膜用組成物的液晶顯示元件中，並無殘留DC降低或對比度提高的效果。可作為上述式[1]、式[2]及式[3]以外的其他二胺使用的化合物示例如下。4,4’-二胺基二苯基曱烷、3,3，-二胺基二苯基曱烷、3,3’-二曱基-4,4，-二胺基二苯基曱烷、2,2-二 [4-(4-胺基苯氧基)苯基]丙烧、2,2-二[4-(4·胺基苯氧基)苯基] • 六氟丙烷、間·苯基二胺、對-笨基二胺、間-二曱苯基二胺、對-二甲苯基二胺、2,2’-二胺基二苯基丙烷、對二胺基聯苯、1,1-二[4-(4-胺基苯氧基)苯基]環己烷、U二[4-(4-胺基苯氧基)苯基]-4-曱基環己烷、二[4-(4-胺基苯曱基)苯基] 曱烷、1，1-二[4·(4-胺基苯甲基）苯基]環己烷、1，1_二[4-(4- .胺基笨曱基)苯基]-4-曱基環己烷、1,1-二[4-(4·胺基苯曱基）苯基]環己烷、1,1-二[4-(4-胺基苯曱基）苯基]-4-曱基環己烧、1，1-二[4-(4-胺基苯曱基)苯基]甲烷。 33 13 Ο 6 5 2^pif.d〇c 可以使用一種上述的其他二胺，亦可將上述的二種以上其他二胺混合使用。此外’只要能達成本發明的目的，本發明並不限定於上述二胺。 ’ 作為讀酸二酐’較佳為佔所使用的四敌酸二軒的20莫爾％以上的比例使用苯均四酸二酕，、’心置尺1土為20〜Sn 莫爾〇/〇的比例使用笨均四酸二酐。作為笨均四酸二四酸二四氫萘基二酸的四羧酸二酐為環丁烷四酸二酐、1 24 <…—针以外，，Ή展己貌酐、4-(2,5-二氧四氫呋喃-3-基)-1，2,3,4_ 酐、5-(2,5-二氧四曱喃醇)_3-曱基-3-環己基:和佳。苯均四酸二酐的使用量為80莫爾％二醪酐等為 2提高;2〇莫爾%以上，使用所得的=亞= 向犋用組成物的液晶顯示元件中，容易蘇妝糸液晶配謂殘留DC的降低。只現累積電荷及所在不損害本發明特性的限度内四羧酸二酐、脂環族四羧酸二針、炉&二用/、他冷香族系丄心細肪族四羧酸〜& 本發明中可使用的苯均四酸二〜酐。舉如下。〜乂外的二酐示例列 ⑧ 34 130652蘇 if.doc -ίτο r\ η Λ7ΛA diamine represented by the formula [3] may be used, or two or more of the two may be used in combination to enhance the black display property when no voltage is applied, and the two amine groups in the diamine represented by the formula may be used. It is preferred that the position is more ortho or meta-positioned to the aligner: in the present invention, the diamine represented by the formula [1] is used in combination with the amine of the formula [2] or the formula [3], or with the formula [2] and The diamines shown in [3] are used in combination. In this case, the diamine content of the formula (1) is 3 in combination with the amine of the formula [2], the formula (1), and the formula [1 or the formula [2]:]. Moore%~99 Mo is better inside Guangwei. When the content is 3 Gmol% or more, the liquid crystal display element using the obtained composition for a polyimine-based liquid crystal alignment film clearly exhibits a remarkable effect of a charge accumulation or a residual DC reduction. In the diamine represented by the formula [1], the liquid crystal display element of the composition of the obtained polyimine-based liquid crystal alignment film is used in combination with the diamine represented by the formula [3] and/or the formula [3], and black is not applied. The effect of the display characteristics being improved is obvious. The content of the diamine of the formula [2] and/or the formula [3] can increase the black display property while considering the reduction of the residual DC effect, and the total of the content is preferably in the range of i mole% to 7 〇mol%. Inside. Further, in the present invention, a diamine other than the above formula [1], formula P] and formula [3] (hereinafter referred to as "other diamine") may be further included, and the ratio of other diamines in this case is preferably When it is 30% or less of the total amount of the diamine, and more than 3% by weight, the liquid crystal display element using the composition for the obtained polyimine-based liquid crystal alignment film does not have an effect of reducing DC reduction or contrast. Examples of the compound which can be used as the other diamines other than the above formula [1], formula [2] and formula [3] are as follows. 4,4'-diaminodiphenyl decane, 3,3,-diaminodiphenyl decane, 3,3'-dimercapto-4,4,-diaminodiphenyl decane , 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4.aminophenoxy)phenyl] • hexafluoropropane, Phenyldiamine, p-styldiamine, m-diphenylphenyldiamine, p-xylyldiamine, 2,2'-diaminodiphenylpropane, p-diaminobiphenyl, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, U bis[4-(4-aminophenoxy)phenyl]-4-mercaptocyclohexane, Bis[4-(4-aminophenylhydrazino)phenyl]decane, 1,1-bis[4.(4-aminophenylmethyl)phenyl]cyclohexane, 1,1_2[4 -(4-.Amino-Alkyl)phenyl]-4-indolylcyclohexane, 1,1-bis[4-(4.aminophenylphenyl)phenyl]cyclohexane, 1,1 - bis[4-(4-aminophenylhydrazino)phenyl]-4-mercaptocyclohexene, 1,1-bis[4-(4-aminophenylhydrazino)phenyl]methane. 33 13 Ο 6 5 2^pif.d〇c One of the above other diamines may be used, or two or more of the above other diamines may be used in combination. Further, the present invention is not limited to the above diamine as long as the object of the present invention can be attained. 'As a reading acid dianhydride', it is preferable to use a pyromellitic acid dioxime in a ratio of 20 mol% or more of the four dicarboxylic acid dixan used, and 'heart set 1 soil is 20~Sn moir/ The proportion of bismuth is stupid tetracarboxylic dianhydride. The tetracarboxylic dianhydride which is stupid tetrasuccinate ditetrahydronaphthyl diacid is cyclobutane tetracarboxylic dianhydride, 1 24 <...-needle, and the anhydride is formed, 4-(2) , 5-dihydrotetrahydrofuran-3-yl)-1,2,3,4-acetic anhydride, 5-(2,5-dioxotetradecanoyl)-3-mercapto-3-cyclohexyl: and preferably. The amount of use of pyromellitic dianhydride is 80% by mole of phthalic anhydride or the like; 2 is more than 2% by mole, and it is easy to use the obtained liquid crystal display element of the composition of y = yttrium. The liquid crystal is referred to as a reduction in residual DC. Only the accumulated charge and the limit of the characteristics of the present invention do not impair the characteristics of the present invention, tetracarboxylic dianhydride, alicyclic tetracarboxylic acid two needles, furnace & dual use /, his cold fragrant family of 丄 heart fine aliphatic tetracarboxylic acid ~ &amp The pyromellitic dianhydride which can be used in the present invention. As follows. ~ 乂 dianhydride example column 8 34 130652 苏 if.doc -ίτο r\ η Λ7Λ

35 130652ft if.doc 185 18635 130652ft if.doc 185 186

188 187188 187

190 189190 189

193193

194 195194 195

⑧ 36 130652ft if.doc8 36 130652ft if.doc

200 202200 202

203 204203 204

37 213 212 I3065i29pif.doc 21137 213 212 I3065i29pif.doc 211

214214

217217

使用。；羧馱一酐可一種單獨使用，亦可二種以上混合use. Carboxylic acid anhydride may be used alone or in combination of two or more kinds.

所示的二^併明中使用的可與式[1]、式[2]及式[3] 烷系二胺。此舉含有矽氧烷基的矽氧者可適宜使用於本胺非特·定者，如式[11]所示 h2n fR5^Si--〇)_S|^R5t_NH2 R4 R4 [11] 3的烷基或苯基，亞苯基。X分別為式[11]中，R3及R4分別為碳數1〜 R5分別為亞甲基、亞苯基或烷基取代的 1~6的整數，y為1〜1〇的整數。 ⑧ 38 I3065i29pif.doc 本發明液晶配向膜用組成物的其他適宜形態，為含有四羧酸二酐與二胺的反應生成物聚醯胺酸或聚醯亞胺的聚醯亞胺系液晶配向膜用組成物，此液晶配向膜用組成物至少含有下述反應生成物A及反應生成物B為特徵的適用於橫電場方式液晶顯示元件的液晶配向膜組成物。反應生成物A :作為四羧酸二酐與含有式[1]化合物為必需成分的二胺的反應生成物聚醯胺酸或聚醯亞胺。 H2N — Xj — NH2 [1] 鲁反應生成物B :作為四羧酸二酐與含有式p]化合物為必需成分的二胺的反應生成物聚醯胺酸或聚醯亞胺。 H2N — X — X2 — X — NH2 [2] 式[1 ]及式[2]中’ Χι為含有-S-的2價有機基團，X分別為苯環或環己烷’ X2為含有-(CH2)n-或-0-的2價有機基團’ η為2〜7的整數。另外，此液晶配向膜用組成物可以僅僅含有反應生成物Α及反應生成物Β，亦可因應必要並且在不損害本發明 φ 效果的範圍内，進一步含有反應生成物A及反應生成物B 以外的聚醯胺酸或聚醯亞胺。反應生成物A中所使用的二胺，以式[丨]化合物作為必需成分，進一步可併用式[2]、式[3]、上述“其他二胺,，、或如式[11]所示的二胺。並且，可併用的各種二胺可以使用1種類，亦可2種類以上混合使用。此時，上述二胺的組合中式π]的二胺含量隨液晶配向膜用組合物中反應生成物Α及反應生成物Β的含量不同， 39 I3065i39pifd〇c 較佳為30莫爾°/〇〜100莫爾％，更佳為51莫爾％〜i〇〇莫爾 %範圍内。式[1]的二胺含量越大，則累積電荷、所謂殘留 DC的降低效果更顯著，故適宜。若其含量為30莫爾％以上，則可適宜作為本發明的聚醯亞胺系液晶配向膜用組成物使用。反應生成物A中所使用的四羧酸二酐，可列舉與上述四羧酸二酐的說明中所述的四羧酸二酐同樣的示例。即，四羧酸二酐中將苯均四酸二酐較佳為使用四羧酸二酐總量瞻的20莫爾％以上的比例，更佳為以20〜80莫爾％的比例使用苯均四酸二酐。苯均四酸二酐以外的四羧酸二酐為環丁烷四酸二酐、1,2,4,5-環己烷四酸二酐、4-(2,5-二氧四氫呋喃-3-基)-1，2,3,4-四氫萘基-1,2-二酸酐、5-(2,5-二氧四曱口南醇)-3·曱基-3-ί哀己基-1，2-二酸酐等為宜。較佳的是反應生成物A中所使用的四羧酸二酐為由20〜80%苯均四酸二酐與80〜20%環丁四羧酸二酐組成。反應生成物B中所使用的二胺，以式[2]化合物作為必 Φ 需成分’進一步可併用式[1]、式[3]、上述‘‘其他二胺，，、或如式[11]所示的二胺。並且’可併用的各種二胺可以使用一種類，亦可二種類以上混合使用。此時’上述二胺的組合中式P]的二胺含量隨液晶配向膜用組合物中反應生成物A及反應生成物B的含量不同，為30莫爾％〜1〇〇莫爾％為佳’較佳為51莫爾％〜1〇〇莫爾 °/〇範圍内。式[2]的二胺含量越大’則液晶顯示元件的黑顯示特性提昇，故適宜。右其含1為30莫爾％以上，則可適 I306529pif.doc 宜作為本發明的聚醢亞胺系液晶配向顧組成物使用。The alkylene diamines of the formula [1], the formula [2] and the formula [3] which are used in the above-mentioned two compounds can be used. The oxygen-containing alkyloxy group can be suitably used in the present amine, such as the formula [11], h2n fR5^Si--〇)_S|^R5t_NH2 R4 R4 [11] 3 alkyl group Or phenyl, phenylene. X is a formula [11], and R3 and R4 are each an integer of 1 to 6 in which a carbon number of 1 to R5 is a methylene group, a phenylene group or an alkyl group, and y is an integer of 1 to 1 Å. 8 38 I3065i29pif.doc Another suitable form of the composition for a liquid crystal alignment film of the present invention is a polyimine-based liquid crystal alignment film containing a reaction product of a tetracarboxylic dianhydride and a diamine, a polyamine or a polyimine. In the composition for liquid crystal alignment film, the composition for liquid crystal alignment film contains at least the following reaction product A and reaction product B, and is suitable for a liquid crystal alignment film composition of a horizontal electric field type liquid crystal display element. Reaction product A: Polyamine or polyimine which is a reaction product of tetracarboxylic dianhydride and a diamine containing an essential component of the compound of the formula [1]. H2N - Xj - NH2 [1] Lu reaction product B: a polyamine or polyimine which is a reaction product of a tetracarboxylic dianhydride and a diamine containing an essential component of the compound of the formula p]. H2N — X — X2 — X — NH2 [2] In the formula [1 ] and in the formula [2], Χι is a divalent organic group containing -S-, and X is a benzene ring or a cyclohexane respectively. X2 is contained - The (CH2)n- or -0-divalent organic group 'n is an integer of 2 to 7. In addition, the composition for a liquid crystal alignment film may contain only the reaction product Α and the reaction product Β, and may further contain the reaction product A and the reaction product B, if necessary, and without impairing the φ effect of the present invention. Polylysine or polyimine. The diamine used in the reaction product A may have a compound of the formula [丨] as an essential component, and may further be used in combination with the formula [2], the formula [3], the above-mentioned "other diamine, or, as shown in the formula [11]. Further, the diamines which can be used in combination may be used in combination of two or more kinds. In this case, the diamine content of the formula π] in the combination of the above diamines is formed by reaction in the composition for liquid crystal alignment film. The content of the substance and the reaction product is different, and 39 I3065i39pifd〇c is preferably 30 mol/〇~100 mol%, more preferably 51 mol% to i〇〇mol%. The larger the diamine content, the more the effect of reducing the accumulated charge and the residual DC is more remarkable, and it is suitable. When the content is 30 mol% or more, it can be suitably used as the polyimide-based liquid crystal alignment film of the present invention. The composition of the tetracarboxylic dianhydride used in the reaction product A is the same as the tetracarboxylic dianhydride described in the above description of the tetracarboxylic dianhydride. Preferably, the pyromellitic dianhydride is a ratio of 20 mole% or more of the total amount of the tetracarboxylic dianhydride used. More preferably, pyromellitic dianhydride is used in a ratio of 20 to 80 mol%, and tetracarboxylic dianhydride other than pyromellitic dianhydride is cyclobutane tetracarboxylic dianhydride, 1, 2, 4, 5- Cyclohexanetetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthyl-1,2-dianhydride, 5-(2,5 - dioxetanyl alcohol) - 3 - mercapto-3- lysyl-1,2-dianhydride, etc. Preferably, the tetracarboxylic dianhydride used in the reaction product A is preferred. 20 to 80% of pyromellitic dianhydride and 80 to 20% of cyclobutanetetracarboxylic dianhydride. The diamine used in the reaction product B is compounded with the compound of the formula [2] as a necessary component. a formula [1], a formula [3], the above-mentioned 'other diamine, or a diamine as shown in the formula [11]. And the various diamines which can be used in combination may be used in one type or in a mixture of two or more types. In this case, the content of the diamine of the formula P] in the combination of the above diamines is different from the content of the reaction product A and the reaction product B in the liquid crystal alignment film composition, and is 30 mol% to 1 mol%. Preferably, the amount of diamine in the formula [2] is greater than the range of 51% Mohr% to 1 〇〇 Mohr °/〇. The black display characteristic of the liquid crystal display element is improved, and it is suitable. When the content of 1 is 30 mol% or more, the I306529 pif.doc is preferably used as the polyimine-based liquid crystal alignment composition of the present invention.

反應生成物B中所使用的四竣酸二針，可列舉與上述四羧酸二酐的說明中所述的四魏二㈣樣的示例。音即’四紐二时將苯均讀二野較㈣使用赠酸二^ 總量的20莫爾％以上的比例，更佳為以2〇〜8〇莫爾％的比例使用笨均四酸二if。苯均四酸二_外的吨酸二針為環丁烷四酸二酐、1,2,4,5-環己烷四酸二酐、4_(2 5二氧四氫咬喃各幻^-四氫萘基-❻二騎^^二氧四甲喊醇)_3-曱基-3-環己基-1，2-二酸酐等為宜。較佳的是反應生成物A中所使用的四羧酸二酐為由2〇〜8〇%笨均四酸一針與80〜20%環丁四緩酸二酐組成的。再者’反應生成物B與上述反應生成物a的原料組成不同。反應生成物A及反應生成物B的反應原料四羧酸二酐與二胺可以為完全相同的原料組成，但此時的反應生物必然成為上述共聚合反應生成物。含有反應生成物A及反應生成物B的液晶配向膜用組成物’是藉由將反應生成物A、反應生成物B及因應必要所添加的反應生成物A及反應生成物B以外的聚II胺^^ < 聚醯亞胺混合而配製。一所混合的反應生成物A的含量較佳為全部聚酿胺@ 或聚醯亞胺中的50〜95莫爾％。其含量若為5〇莫爾0/ = 上，則使用所得到的聚醯亞胺系液晶配向膜用絚成物夜晶顯示元件中，明顯表現累積電荷、殘留DC顯著降、效果。 _The tetrakisperic acid di-needle used in the reaction product B may be exemplified by the tetra-wei (four)-like example described in the above description of the tetracarboxylic dianhydride. The sound is 'four new two when the benzene is read in the second field (four) using the acid 2 ^ total amount of 20% Moore% or more, more preferably 2 〇 ~ 8 〇 Moll% ratio using stupid tetracarboxylic acid Two if. The two needles of benzene tetracarboxylic acid are the cyclobutane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and 4_(2 5 dioxane tetrahydronethane) - tetrahydronaphthyl-anthracene ^^dioxytetramethylene alcohol)_3-mercapto-3-cyclohexyl-1,2-dianhydride or the like is suitable. It is preferred that the tetracarboxylic dianhydride used in the reaction product A is composed of 2 Torr to 8 〇% of stearidonic acid, a needle and 80 to 20% of cyclobutane sulphuric acid dianhydride. Further, the reaction product B is different from the raw material composition of the above reaction product a. The reaction raw material of the reaction product A and the reaction product B may be the same raw material composition as the tetracarboxylic dianhydride and the diamine. However, the reaction product at this time necessarily becomes the above-mentioned copolymerization product. The composition for liquid crystal alignment film containing the reaction product A and the reaction product B is a polymerization II, a reaction product B, and a reaction product A and a reaction product B added as necessary. Amines ^^ < Polyimine mixed to prepare. The content of a mixed reaction product A is preferably from 50 to 95 mol% of the total polyamine@ or polyamidomine. When the content is 5 〇 Mohr 0/ =, the obtained polyimine-based liquid crystal alignment film for the obtained yttrium crystal display element clearly exhibits an accumulated charge and a significant decrease in residual DC. _

(D 130652§pifdoc 所混合的反應生成物B的含量較佳為全部聚醯胺酸或聚醯亞胺中的5〜50莫爾％。其含量若為5莫爾％以上，則使用所得到的聚醯亞胺系液晶配向膜用組成物的液晶顯示元件的黑顯示特性提高。〔amino silicon) 再者，為改善本發明的液晶配向膜材料與基板的密著性，液晶配向膜用組成物中可添加胺基矽烷(£ 化合物。作為胺基矽烷化合物，可列舉對胺基苯基三甲氧基矽烷、對胺基苯基三乙氧基矽烷、間胺基苯基三甲氧基石夕^、間胺基苯基三乙氧基矽烷、胺丙基三甲氧基矽烷、胺丙基三乙氧基矽烷等。曰本發明所用的聚醯胺酸或可溶性聚醯亞胺的分子置:藉由例如凝膠滲透層析法(Gpc)，以聚苯乙烯換算的重Ή：平均分子量(Mw)為1〇,〇〇〇〜5〇〇,〇〇〇，更佳為2〇〇〇〇〜 200,〇〇〇〇 ’ 本毛明中聚醯亞胺系液晶配向膜用組成物中高分子 •成分聚酿胺酸或可溶性聚醯亞胺等的濃度無特別限定，較曰為0.1 40重量％。將此組成物塗佈於基板時，為調整膜，有必要進行縣以溶嶋釋所含高分子成分的操作。高刀子的浪度為4〇重量％以下時，液晶配向膜用組成物的可传取適的勒度，並且為調整膜厚有必要稀釋液晶配向，用組^物時’溶劑容易與液日Β日配向顧組成物混合，故 ^為適，、。為了在旋轉塗膜法或印刷法時保持良好的膜旱’通常為10重量％以下。其他塗佈方法，例如浸潤法或 ⑧ I306S3Qif.doc ^墨^!/要更低的濃度m高分子成分的濃度為 0.1重望%以卜，、工各易得到最適宜的配向膜膜厚。因此，通吊的，ϋ或印刷法等其濃度為（U重量％以上，較佳為 0.5~10重量％。扯、稀薄繼，而，藉由此清漆塗佈方法，亦可使用更言八本4 ^的聚酿亞胺系液晶配向膜用組成物中，與上述 =二，j二一起所用的溶劑，若為具有溶解高分子能力的分Ξ別限制。此溶劑涵蓋聚義酸、可溶性聚酿對鹿使=沾ΐ分的製程或用途方面通常使用的溶劑’可胺酸或可溶性擇。此等溶劑的示例如下所示。聚酿劑，其示_ 的可雜溶縣料子性有機溶 f基己内醯肱 ' 比咯烷酮、二曱基咪唑烷酮、N- 基二二=丙酸胺、N，N-二甲基乙酿胺、二甲基乙醯胺，丁：：ir罐、N算二乙基甲酿胺、二甲内酉日專内g旨。為改盖+ 溶劑的示例有燒基乳酸醋、3=;=，目的的其他萘、異佛樂綱、乙二醇單丁基“V, 丁醇、四氫化二醇單乙基喊等二乙二醇單I乙—醇單烷基醚、二乙乙酸醋、三乙二醇單烧基鍵、二醇單·或苯基燒基醚、丙二酸二乙醋等丙二基喊等丙二醇單基鍵等二丙二醇單烧基趟，這此2基二二丙二醇單甲中，較佳的為Ν_甲基〜比“二 ‘醇單乙基趟、丙二醇單丁内酯、乙二醇單丁基醚、二乙土米坐烷酮、γ· 丁基醚及二丙二醇單甲基醚等。 43 13 〇652^ifdoc 本聚酿亞胺系液晶配向臈用組成物，因應必要町包含各種添加劑。例如，希望提高塗佈性時可混人現此目的的介面活性劑，有必要提高防止靜電性時^合靜電防希望提高與基板的密著性時混合魏偶合劍或银系偶合劑。本發明相關的IPS型液晶顯示元件中，薄膜由所形成的第-透縣板，與其相二透縣板二及此等基板間所夾持的液晶所組成。第—透明基板具有如交互狀梳齒延伸卿成的晝素電極及共通電極板具有遮蔽晝素區域以外光的黑矩陣、濾色片、平ί化ΐ 等=狀電極’破璃等透明基板上利用_法等堆積鉻等形狀！光阻圖案為光罩進行刻蝕而形成。膜用组i物所得到的二枚透明基板上塗佈液晶配向膜用，，且成物H然後是乾燥餘，環必要的加熱處理製程。了及脫κ閉去方物的塗佈製程中的塗佈方法中，習知方法為方疋轉塗膜法、印刷法、浸潤法水及閉核反應必要的加熱處理製程的方法中，習力或紅外爐中加熱處理的方法、於加熱臺上，、、、=的方法。此等方法也同樣適用於本發明。的基許的範圍崎低的溫度下實施溶劑的溫^進行程—般較佳為在i5Q〜左右 d) 44 I3〇652«kdoc 曰其後’實施所得液晶配向膜的配向處理製程、所得液曰曰 =持基板藉由間隔材相向組合的製程、封入液晶材料的制心及黏貼偏光臈的製程以製造液晶顯示元件。配向處理氣程中的配向處理方法中，f知方法有摩擦法、光配兩法 t轉寫㈣。在實現本發明目_範圍，此等方法同樣可適用於本發明。杏 ^明中特別適宜使用的配向處理方法為摩擦法，在 Γι月目的的範圍内’任何摩擦處理條件都可以。特 5 的條件為纖維推人量G.2〜G.8mm，試樣台移動速度咖―、輥軸旋轉速度500〜2,000rpm。清洗液進型液晶顯7^①件於配向處理前後可以以清洗或超聲波清洗等。此等方、^^舉财、_、祕苯、二甲裳_乙®予、異兩醇等各種醇類、苯、甲本等方g私類、氣代甲々所使清洗妓當然，本發明的IP S型液晶顯示元田二的沒有特別_，可以使时f 晶組成物，成物。適宜的液晶組成物示例日^為正的各種液晶組報、曰本專利第2635435號公報專利第3〇86228號公 5-501735㉟公報、日本專利 ^本專利公告第特表平號公報、日本專利早期公開第開平8- 157828 曰本專利早期公開第特開^〜231960號公報、十9 — 241644號公報 Φ 45 if.doc 130652¾ (EP885272A1說明書）、曰本專利早期公開第特開平 3〇2346號公報(EP806466A1說明書）、日本專利早期公開第特開平8—199168號公報(EP722998A1說明書）、日本專利早期公開第特開平9 —235552號公報、曰本專利早期公開第特開平9-255956號公報、日本專利早期公開第特開平9-241643號公報(EP885271A1說明書）、日本專利早^ 公開第特開平10 — 204016號公報(EP844229A1說明書卜曰本專利早期公開第特開平1〇 —204436號公報、曰本曰專利早期公開第特開平10 —2難2號公報、日本專利第特開雇-〇87_號公報、日本專利早期公開第= 2001 —48822號公報所公開的。，碣 f可=介電率異向性為貞的各魏晶 =夜晶組成物’例如參考日本專利早期公開第特開^ 報532ίί報、日本專利早期公開第特開平2 —4725 h 報、曰本專利早期公開第特開平4 —22牝就公專利早期公開第·平8—姻 =報、日本開第特開平I_9號公報、日本專利早期公平H_76號公報、日本專利早期公開第特開 1_號公報、曰本專利早特開平曰本專利早期公開、=:2369%號公報、早期公開料開平1G —236993G^6/92號公報、第特開平ΙΟ-2%994號公報、日^ =本專利早期公開 ―號公親'曰本專利早特開平號公報、曰本專利早期公開第特開平^特0〜23_ 本專利早期厶〇s23699〇號公刼、曰本專利開 46 10 丄 *3〇652ftifdoc 號公報號公報、日本專利日早^^#_第制平237〇24 ^ 1〇~237〇35E^ , 早期公開第特開平^ = 〇~ 237075號公報、日本專利第特開平H)s237448 pf6號公報、日本專利早期公開專利早期公開βΓΓ (EP967261A1說明書）、日本開平10 —2919 #u么報、曰本專利早期公開第特 -029581號八鉬〜么報、日本專利早期公開第特開平11 號公報、日m 特開平n—〇_ 日本專刹It專利早期公開第特開2_ —256307號公報、早期八門^公開第特開2GG1 — G19965號公報、日本專利 J仏二制_ —_6號公報、日本專利早期弟特開繼―192奶號公報等中所公開的。 j介電率異向性為正或負的液日日日組成物中添加— 種乂上光學活性化合物使用$無任何差異。，步’本發明的聚驢亞胺系液晶配向膜用組成物 :’在不損害本發明特性的範圍(較佳為2〇莫爾％以内）， =以混合使用含有其他組成的聚_酸、可溶性聚酿亞丙烯酸聚合物、丙_§旨聚合物等聚合物成分。再者’本發明的聚酿亞胺系液晶配向膜用組成物中，在不損害本發明目的的範圍内添加液晶配向顧組成物所用的t合物成分’如—羧酸或其衍生物與二胺的反應生成物聚醯胺或四賊讀、二羧1¾其触物與三胺的反應生成物聚醯胺醯亞胺等聚合物成分。此時的二胺，除本發 47 13 Ο652ft if doi 明的式[1]，式[2]以及式[3]所示的二胺之外，可列舉可與此二胺併用的上述二胺以及此等二胺的混合物。【實施例】以下，藉由實施例及比較例說明本發明，然而本發明並非限定於此等實施例。實施例以及比較例中所用的四羧酸二酐、二胺以及溶劑的名稱以縮寫表示。以下的描述中可能使用此縮寫。四羧酸二酐(D 130652 § pifdoc The content of the reaction product B to be mixed is preferably 5 to 50 mol% of the total polyamine or polyimine. If the content is 5 mol% or more, the obtained is obtained by using The black display property of the liquid crystal display device of the composition for a polyimine-based liquid crystal alignment film is improved. [amino silicon] Further, in order to improve the adhesion between the liquid crystal alignment film material of the present invention and the substrate, the composition of the liquid crystal alignment film Amino decane (£ compound may be added to the compound. Examples of the amino decane compound include amino phenyl trimethoxy decane, p-aminophenyl triethoxy decane, and m-aminophenyl trimethoxy sulphate. , m-aminophenyl triethoxy decane, amine propyl trimethoxy decane, amine propyl triethoxy decane, etc. 分子 molecular grouping of poly-proline or soluble polyimine used in the present invention: For example, gel permeation chromatography (Gpc), polystyrene-equivalent weight: average molecular weight (Mw) is 1 〇, 〇〇〇~5 〇〇, 〇〇〇, more preferably 2 〇〇〇〇 ~ 200, 〇〇〇〇' Benmao's high score in the composition of polyimine liquid crystal alignment film The concentration of the component polyamic acid or soluble polyimine is not particularly limited, and is 0.140% by weight. When the composition is applied to a substrate, it is necessary to carry out the dissolution of the county. When the wave height of the high knife is 4% by weight or less, the composition for the liquid crystal alignment film can be appropriately transferred, and it is necessary to dilute the liquid crystal alignment to adjust the film thickness, and the composition is used. When the solvent is easily mixed with the liquid composition, it is suitable for use in order to maintain a good film drought during the spin coating method or the printing method, and is usually 10% by weight or less. Other coating methods, For example, infiltration method or 8 I306S3Qif.doc ^ ink ^! / to lower concentration m polymer concentration of 0.1% of the weight of the cloth, the work is easy to get the most appropriate alignment film thickness. Therefore, through the hanging The concentration of the ruthenium or the printing method is (U% by weight or more, preferably 0.5% to 10% by weight. Pulling, thinning, and by this varnish coating method, it is also possible to use a more uniform In the composition for the brewing imine liquid crystal alignment film, together with the above = two, j two The solvent used is limited by the ability to dissolve the polymer. This solvent covers the solvent used in the process or use of poly-acid, soluble polymer, deer, or dilute. An example of such a solvent is shown below. A polystyrene, which is a miscible material, an organically soluble f-caprolactone, a pyrrolidone, a dinonyl imidazolidinone, and an N-based di- = propionate amine, N,N-dimethyletheneamine, dimethylacetamide, butyl::ir can, N count diethyl amide, dimethyl sulphate, special purpose. Examples of cap + solvent are calcined lactic acid vinegar, 3 =; =, other naphthalenes of the purpose, isophora, ethylene glycol monobutyl "V, butanol, tetrahydroethylene glycol, single ethyl shunt, etc. Alcohol mono I ethyl alcohol monoalkyl ether, diacetic acid vinegar, triethylene glycol monoalkyl bond, diol mono or phenyl alkyl ether, malonic acid diethyl vinegar, etc. a dipropylene glycol monoalkyl group such as a base bond, and among the 2 groups of dipropylene glycol monomethyl, preferably Ν_methyl~ than "di" alcohol monoethyl hydrazine, propylene glycol monobutyrolactone, ethylene glycol single Butyl , Diethyl meters soil sit pyrrolidone, γ · butyl ether and dipropylene glycol monomethyl ether and the like. 43 13 〇652^ifdoc This is a composition of a poly-imine-based liquid crystal alignment compound. It is necessary to contain various additives. For example, it is desirable to increase the applicability of the surfactant which can be mixed for the purpose, and it is necessary to improve the antistatic property. When the static electricity is prevented from being mixed with the adhesion of the substrate, the Wei coupling sword or the silver coupling agent is mixed. In the IPS type liquid crystal display device according to the present invention, the film is composed of the formed first-period plate, and the liquid crystal sandwiched between the two plates and the substrates. The first transparent substrate has a halogen electrode such as an alternating comb-shaped electrode and a common electrode plate having a black matrix for shielding light outside the halogen region, a color filter, a flat-shaped electrode, a transparent electrode such as a glass electrode, and the like. Use _ method to stack chrome and other shapes! The photoresist pattern is formed by etching the mask. The liquid crystal alignment film is coated on the two transparent substrates obtained for the film group, and the product H is then dried and the ring is subjected to a heat treatment process. In the coating method in the coating process of the de-kneading and de-blocking, the conventional method is a method of a heat treatment process necessary for a square-turn coating method, a printing method, a wetting method water, and a closed-nuclear reaction, Or a method of heat treatment in an infrared furnace, a method of heating on a table, and, =. These methods are equally applicable to the present invention. The temperature of the solvent is carried out at a sublime temperature, preferably in the range of i5Q~d, d) 44 I3〇652«kdoc 曰 subsequent implementation of the alignment treatment process of the obtained liquid crystal alignment film, the obtained liquid曰曰=The substrate is manufactured by a process in which the spacers are opposed to each other, a process of sealing the liquid crystal material, and a process of attaching the polarizing film to manufacture a liquid crystal display element. In the alignment processing method in the gas processing, the f-method is a friction method or a photo-matching method (t). These methods are equally applicable to the present invention in achieving the scope of the present invention. The alignment treatment method particularly suitable for use in apricot is a rubbing method, and any rubbing treatment condition can be used within the range of the purpose of the ruby. The condition of the special 5 is that the fiber pushing amount G.2 to G.8 mm, the moving speed of the sample stage, the rotation speed of the roller shaft, 500 to 2,000 rpm. The cleaning liquid inlet type liquid crystal display 7^1 pieces can be cleaned or ultrasonically cleaned before and after the alignment treatment. These parties, ^^, _, _, benzene, dimethyl _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The IP S-type liquid crystal display of the present invention has no special _, and can be made into a f-crystal composition. Examples of suitable liquid crystal compositions are various liquid crystal group reports, and Japanese Patent No. 2635435, Japanese Patent No. 3, 862, 862, and Japanese Patent No. 5-50173535, Japanese Patent No. 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 Japanese Laid-Open Patent Publication No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-235552, Japanese Laid-Open Patent Publication No. Hei 9-255956, Japanese Patent Laid-Open Publication No. Hei 9-241643 (Patent No. EP 885 271 A1), Japanese Patent Laid-Open Publication No. Hei No. Hei 10-204016 (Embodiment No. EP 844 229 A1) The patent of the earlier publication of the Japanese Patent Laid-Open No. 10-2, No. 2 Bulletin, Japanese Patent Special Employment - 〇87_, Japanese Patent Early Disclosure Japanese Laid-Open Patent Publication No. 2001-48822, 碣f can be used for each of the Weijing = night crystal compositions having a dielectric anisotropy of 贞, for example, refer to Japanese Patent Laid-Open Publication No. 532 ίί, Japanese Patent Early publication of the special opening of the Kaiping 2 - 4725 h report, 曰专利专利专利早期早期 4 4 4 4 4 4 4 4 4 4 4 4 公公公公公公公公公公公公公公公公、、、、、、、、、、、、、、 H_76, Japanese Patent Laid-Open No. 1_, Japanese Patent Laid-Open Patent Publication No. 2369%, Early Publication Kaiping 1G-236993G^6/92, No. Special Kaikai -2%994 bulletin, day ^ = early publication of this patent - No. of the public pro- 曰专利专利早早早早早曰曰曰曰 699 699 699 699 699 699 699 699 699 699 699 699 699 699 699 699 699 699 〇刼刼刼曰 46 46 46 10 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 日本日本日本日本日本日本日本 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 〇〇〇〇〇〇〇〇〇 = 〇~ 237075, Japanese Patent No. H. s237448 pf6 Japanese Patent Early Disclosure Patent Early Publication βΓΓ (EP967261A1 Specification), Japan Kaiping 10-2919 #u么报, 曰本专利早公开第特-029581号八钼〜么报, Japanese Patent Early Disclosure Special Kaiping 11 , 日 m 特开平n-〇_ Japanese special patent It patent early open special opening 2_-256307 bulletin, early eight-door public open special 2GG1 - G19965 bulletin, Japanese patent J仏 two system ___6 bulletin The Japanese patent was first published in the "192 Milk Bulletin" and the like. j The dielectric anisotropy is positive or negative in the liquid day and day composition. There is no difference in the use of the optically active compound on the substrate. , the step of the polyimine-based liquid crystal alignment film of the present invention: 'in the range which does not impair the characteristics of the present invention (preferably within 2% Mohr%), = mixed use of poly-acids containing other compositions A polymer component such as a soluble polyacrylic acid polymer or a polymer. In the composition for a polyacrylonitrile-based liquid crystal alignment film of the present invention, a t-component of a liquid crystal alignment composition such as a carboxylic acid or a derivative thereof is added to the range which does not impair the object of the present invention. The reaction product of the diamine is a polymer component such as polyamine or a thief, a dicarboxylic acid, a reaction product of a touch with a triamine, and a polyamidoximine. The diamine at this time includes, in addition to the diamine represented by the formula [1], the formula [2] and the formula [3] of the present invention, the above-mentioned diamine which can be used in combination with the diamine. And a mixture of such diamines. [Examples] Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited to the Examples. The names of the tetracarboxylic dianhydride, the diamine and the solvent used in the examples and the comparative examples are represented by abbreviations. This abbreviation may be used in the following description. Tetracarboxylic dianhydride

1，2,3,4-環丁烷四酸二酐：CBDA1,2,3,4-cyclobutanetetracarboxylic dianhydride :CBDA

苯均四酸二酐：PMDAPyromellitic dianhydride: PMDA

1,2,3,4-丁四酸二酐：BBDA 二胺1,2,3,4-butyric acid dianhydride: BBDA diamine

4,4’-二胺基二苯基曱烷：DDM4,4'-diaminodiphenyl decane : DDM

4,4’-二胺基二笨基硫化物：ASD4,4'-Diaminodiphenyl sulfide: ASD

4,4’-二胺基-1，2-二苯基乙烷：DDET4,4'-Diamino-1,2-diphenylethane: DDET

2-笨曱基-1,4-二苯基二胺：P1PDA 1，3-二(4-(4-胺基苯曱基)苯基)丙烷：BZ32-Azainyl-1,4-diphenyldiamine: P1PDA 1,3-bis(4-(4-aminophenylphenyl)phenyl)propane: BZ3

4,4’-二胺基-1,3-二苯基丙烷：DDPP4,4'-Diamino-1,3-diphenylpropane: DDPP

4,4’-二胺基-1，4-二苯基丁烷：DDPB4,4'-diamino-1,4-diphenylbutane: DDPB

1，4-二(4-胺基苯基硫基)丁烷：DDSB1,4-bis(4-aminophenylthio)butane: DDSB

1,3-二(4-胺基苯基硫基）丙烷：DDSP1,3-bis(4-aminophenylthio)propane: DDSP

1.2- 二(4-胺基苯基硫基）乙烷：DDSE1.2- bis(4-aminophenylthio)ethane : DDSE

4-二(4-胺基苯基氧基)丁烷：DDOB4-bis(4-aminophenyloxy)butane :DDOB

1.3- 二(4-胺基苯基氧基）丙烷：DDOP 48 130652分 if.doc1.3- bis(4-aminophenyloxy)propane: DDOP 48 130652 points if.doc

:DD0E :ΑΡΕ :APDS :ΝΜΡ ：GBL :BC 1，2-二(4-胺基笨基氧基）乙烷 4,4’-二胺基二苯基醚 1，3’-二(3-胺丙基）四曱基二石夕烧溶劑成分 N-曱基-2-°比略院酮 γ-丁内酯丁基纖維素溶劑實施例1:DD0E :ΑΡΕ :APDS :ΝΜΡ :GBL :BC 1,2-bis(4-aminophenyloxy)ethane 4,4'-diaminodiphenyl ether 1,3'-di(3- Amine propyl) tetradecyl bismuth sulphate solvent component N-mercapto-2-° ratio ketone γ-butyrolactone butyl cellulose solvent Example 1

1)聚= 胺系液晶配向膜用組成物A1(清漆Α⑽配製備有溫度計、攪拌機、原料投 20-四π燒瓶中加人i.28g 、1 入二 ==氣流下授掉溶解。反應體系的溫二; 入2鄭c,GBL'，m^3G分鐘後，加酿胺酸的清漆》原料的反財讀為5重量％的聚制反應溫度為7。。。以;==使=上昇時’控二在=㈣查二：添==1) Poly=Amine-based liquid crystal alignment film composition A1 (varnish Α(10) is prepared with a thermometer, a stirrer, a raw material, a 20-tetra π flask, and a solution of i.28g, 1 and 2 == gas flow, and the solution is dissolved. The temperature of the second; into 2 Zheng c, GBL ', m ^ 3G minutes, add tyrosine of tyrosine lacquer" raw material read the reaction temperature of 5% by weight of the polymerization reaction rate of 7 to; = = make = When rising, 'control two in = (four) check two: add ==

^月= 35η^ (使用MM計，MO 時反應、止，於低溫下保存。所得到均分子量為。其中，重量平均分子量· 所(公司名）製GPC測定襄置（Chr〇mat〇Pack c_r7a，產品名）層析柱溫度50°C下測定。如胃上所述得到的清漆Μ以nmp/BC/GBL(=60/25/ 15 ’重里比）的混合溶劑稀釋調整至全部高分子成分的濃度 49 I3065i29pifd〇c 為3重量％，作為塗佈用清漆。 2)對比度及殘留DC測定用組立(cd]l)的製作使用如圖i所示的IPS用帶有梳狀電極的玻璃基板及無電極的玻璃基板等二片玻璃基板。將得到的塗佈用清漆以旋轉塗膜塗佈於上述們有梳狀電極的玻璃基板上，塗佈條件為23〇〇_，。 :膜嫌結後’於啊進行3〇分鐘加熱處㈣約8〇麵的液晶配向膜。所得到的聚醯亞胺 =標準尺製作所股份有限公司製的摩擦處理裝乂在摩擦布(纖維長19mm :醋酸纖維)的纖維推樣台移動速度60_/sec，輕軸旋轉速度 lOOOrpm條件下，進行摩擦處理。 Γ到的液晶保持基板於乙醇中超聲波清洗5分鐘，用清洗薄膜後烘箱中12(rc乾燥分鐘。上述IPS 成有配^電極的玻璃基板上散佈4_大小的間隔物，形以的—面作為内側與無電極的玻璃基板相對後，钽H、主化劑松封’製作間隔4μΠ1的平行組立(cell)。上述進杆液晶材料，注人口以細化封。其後，⑽。C 偏^，I理3G分賴，相向的朗基板的外側貼付二片的奶用H比度及殘留DC測定用組立。另外，相向雜;電極的玻璃基板及無電極的破璃基板的 2向為同—方向。一側偏光臈的偏光透過軸與摩另一側與此垂直配置。作為液晶材料使用曰曰、、成物Α的組成如下所示。此組成物的ΝΙ點為 50 ③ I306539piM〇〇^月= 35η^ (Use MM, react with MO, stop, and store at low temperature. The average molecular weight obtained is obtained. Among them, the weight average molecular weight and the (company name) GPC measurement device (Chr〇mat〇Pack c_r7a) , product name) The column temperature is measured at 50 ° C. The varnish obtained as described in the stomach is diluted with a mixed solvent of nmp / BC / GBL (= 60 / 25 / 15 ' weight ratio) to adjust the total polymer composition The concentration of 49 I3065i29pifd〇c was 3% by weight, and it was used as a varnish for coating. 2) Preparation of contrast and residual DC measurement group (cd) 1 Using a glass substrate with a comb electrode as shown in Fig. i And two glass substrates such as a glass substrate without electrodes. The obtained coating varnish was applied onto the glass substrate having the comb electrodes described above by a spin coating film under the conditions of 23 Å. : After the film is suspected, it is heated for 3 minutes. (4) A liquid crystal alignment film of about 8 inches. The obtained polyimine = the friction treatment device manufactured by Standard Scale Co., Ltd. in a friction cloth (fiber length: 19 mm: acetate), the speed of the fiber push table is 60 Å/sec, and the speed of the light shaft is 1000 rpm. Perform rubbing treatment. The obtained liquid crystal holding substrate was ultrasonically cleaned in ethanol for 5 minutes, and after cleaning the film, 12 (rc drying minutes) in the oven. The above IPS was placed on the glass substrate with the electrode to spread a spacer of 4 mm size. After the inner side is opposed to the electrodeless glass substrate, 钽H and the main agent are loosely sealed to form a parallel cell having a spacing of 4 μΠ1. The above-mentioned liquid crystal material is filled with a fine seal, and then (10). ^, I, 3G, and the two sides of the opposite side of the Lang substrate are attached with two pieces of milk for H-degree and residual DC measurement. In addition, the phase is mismatched; the electrode glass substrate and the electrodeless glass substrate are oriented in two directions. In the same direction, the polarized light transmission axis of one side is perpendicular to the other side of the motor. The composition of the liquid crystal material is as follows: The composition of the composition is as follows: The defect of this composition is 50 3 I306539piM〇〇

100.0°C，雙折射為 0.093。液晶組成物AAt 100.0 ° C, the birefringence is 0.093. Liquid crystal composition A

!7wt.% 17wt.%!7wt.% 17wt.%

c2h5 ο c2h4. 16wt.%C2h5 ο c2h4. 16wt.%

10wt.°/〇10wt.°/〇

C3H7C3H7

5wt.% 10wt.% C5H115wt.% 10wt.% C5H11

6wt.% 6wt.% 13wt.% (1)對比度的測定其後，使用如上所述製作的對比度測定用組立以大塚電子股份有限公司製的液晶面板評價裝置(LCD-5100，產品名）求得透過率-施加電壓曲線，由白顯示的輝度與黑顯示的輝度之比算出對比度為195。再者，摩擦痕跡等配向斑或配向缺陷完全未發現，得到非常均勻的顯示。其中，對比度測定時的條件為驅動電壓〇〜l〇Vp_p，驅動頻率 70Hz，矩形波。 ⑧ 130653¾ if.doc (2)殘留DC的測定 30Hz、3V的矩形波上疊加lv的直流電壓3()分鐘後立即測㈣爍消除電壓，此值的％留DC越小殘存越少，被認為良好。使用如上所述製作的測定殘留Dc用組立以上述所述方法測定時，殘留DC為45mV。實施例2〜36，比較例1〜6 分別以如下表1中所示的原料組成配製清漆A2〜a36 及清漆B1〜B6，替代實施例i中的清漆A卜與實施例i 同樣進行對比度及殘留DC電壓的評價。比較例5中所示的TN組立的製作一對帶有IT0(銦錫氧化物)透明電極的玻璃基板，使用4μ!η用間隔材作成，按照摩擦方向成9〇。組合，使用添加有光學活性化合物的液晶組成物A，除成為正常黑 (normal black)模式貼付偏光膜之外，藉由與對比度及殘留 DC電壓測疋用盒同樣的方法製作TN組立，與實施例1 同樣進行殘留DC電壓的評價。各種清漆的配製，清漆A2〜A36及清漆B1〜B6以與清漆A1同樣的方法配製。反應中由於反應熱引起溫度上升時，控制反應溫度約7〇 C以下使其反應。另外，配製聚醯胺酸的清漆時，在反應的進行中檢查反應物的黏度，添加BC與GBL後清漆的黏度達到30〜35mPa.s(使用E型黏度計，25。〇時反應終止’於低溫下保存。 ④ I306529pifd。。意即’最初的聚醯胺酸僅在NMP中合成，其後加入 BC及GBL ’最終調整清漆的聚醯胺酸濃度為5重量％。各實施例及比較例的原料莫爾比及重量平均分子量示於表1〜4中。【表1】6wt.% 6wt.% 13wt.% (1) Measurement of Contrast After the use of the liquid crystal panel evaluation device (LCD-5100, product name) manufactured by Otsuka Electronics Co., Ltd., the composition for contrast measurement prepared as described above was used. The transmittance-applied voltage curve calculates a contrast ratio of 195 from the ratio of the luminance displayed in white to the luminance displayed in black. Furthermore, alignment spots or alignment defects such as rubbing marks are not found at all, and a very uniform display is obtained. Among them, the conditions for contrast measurement are drive voltage 〇~l〇Vp_p, drive frequency 70 Hz, and rectangular wave. 8 1306533⁄4 if.doc (2) Determination of residual DC 30Hz, 3V rectangular wave superimposed lv DC voltage 3 () minutes immediately after the test (four) Shuo elimination voltage, the value of this value left DC the smaller the residual, is considered good. When the measurement residual Dc prepared as described above was measured by the above-described method, the residual DC was 45 mV. Examples 2 to 36, Comparative Examples 1 to 6 The varnishes A2 to a36 and the varnishes B1 to B6 were prepared by the raw material compositions shown in the following Table 1, respectively, and the varnish A in Example i was subjected to the same contrast as in Example i. Evaluation of residual DC voltage. Production of TN assembly shown in Comparative Example 5 A pair of glass substrates with an IT0 (indium tin oxide) transparent electrode were formed using a spacer of 4 μm; and were formed in a rubbing direction of 9 Å. In combination with the liquid crystal composition A to which the optically active compound is added, in addition to the normal black mode-attached polarizing film, the TN assembly is produced by the same method as the contrast and residual DC voltage measurement cassette. Example 1 The evaluation of the residual DC voltage was also performed. Preparation of various varnishes, varnishes A2 to A36 and varnishes B1 to B6 were prepared in the same manner as varnish A1. When the temperature rises due to the heat of reaction during the reaction, the reaction temperature is controlled to be about 7 〇 C or less to cause a reaction. In addition, when preparing a varnish of poly-proline, the viscosity of the reactant is checked during the progress of the reaction, and the viscosity of the varnish after adding BC and GBL reaches 30 to 35 mPa.s (using an E-type viscometer, 25. When the reaction is terminated) Stored at low temperature. 4 I306529pifd. This means that the initial poly-proline is synthesized only in NMP, followed by the addition of BC and GBL. The final adjustment of the varnish has a polyamine concentration of 5% by weight. The raw material molar ratio and weight average molecular weight of the examples are shown in Tables 1 to 4. [Table 1]

清漆酸二酐^ 二胺分子量^ 組立 PMDA CBDA ASD DDET P1PDA ΒΖ3 ΑΡΕ DDM 實施例Ϊ Α1 25 25 25 25 63,000 IPS 實施例2 Α2 25 25 25 25 54,000 IPS 實施例3 A3 25 25 25 25 65,000 IPS 實施例4 Α4 25 25 25 15 10 58,000 IPS 資施例5 Α5 25 25 25 25 68,000 IPS 實施例6 Α6 25 25 25 !5 10 65,000 IPS 比較例1 Β1 25 25 25 25 55,000 IPS 比較例2 Β2 25 25 50 57,000 IPS 比較例3 Β3 25 25 50 70,000 IPS 比較例4 Β4 25 25 50 51,000 IPS 比較例5 Β5 25 25 25 25 48,000 IPS 比較例ό Β6 25 25 25 25 63,000 TN 注·· 1)四羧酸二酐 2)重量平均分子量【表2】Lacquer acid dianhydride ^ Diamine molecular weight ^ Formation PMDA CBDA ASD DDET P1PDA ΒΖ 3 ΑΡΕ DDM Example Α 1 25 25 25 25 63,000 IPS Example 2 Α 2 25 25 25 25 54,000 IPS Example 3 A3 25 25 25 25 65,000 IPS Example 4 Α4 25 25 25 15 10 58,000 IPS Example 5 Α5 25 25 25 25 68,000 IPS Example 6 Α6 25 25 25 !5 10 65,000 IPS Comparative Example 1 Β1 25 25 25 25 55,000 IPS Comparative Example 2 Β2 25 25 50 57,000 IPS Comparative Example 3 Β3 25 25 50 70,000 IPS Comparative Example 4 Β4 25 25 50 51,000 IPS Comparative Example 5 Β5 25 25 25 25 48,000 IPS Comparative Example Β6 25 25 25 25 63,000 TN Note·· 1) Tetracarboxylic dianhydride 2 ) Weight average molecular weight [Table 2]

清漆酸二酐11 —_胺分子量組立 PMDA CBD A ASD DDSB DDSP DDSE DDET DDPB 實施例7 A7 25 25 10 15 25 65,000 IPS 實施例8 A8 25 25 10 15 25 61,000 IPS 實施例9 A9 25 25 10 15 25 60,000 IPS 實施例10 A10 25 25 25 25 63,000 IPS 實施例11 All 25 25 25 25 58,000 IPS 實施例12 A12 25 25 25 25 57,000 IPS 實施例13 A13 25 25 10 15 25 63,000 IPS 實施例14 A14 25 25 10 15 25 58,000 IPS 實施例15 A15 25 25 10 15 25 57,000 IPS 實施例16 A16 25 25 30 20 70,000 IPS 實施例Π A17 25 25 30 20 68,000 IPS 實施例18 A18 25 25 30 20 67,000 IPSLacquer acid dianhydride 11 - amine weight molecular composition PMDA CBD A ASD DDSB DDSP DDSE DDET DDPB Example 7 A7 25 25 10 15 25 65,000 IPS Example 8 A8 25 25 10 15 25 61,000 IPS Example 9 A9 25 25 10 15 25 60,000 IPS Example 10 A10 25 25 25 25 63,000 IPS Example 11 All 25 25 25 25 58,000 IPS Example 12 A12 25 25 25 25 57,000 IPS Example 13 A13 25 25 10 15 25 63,000 IPS Example 14 A14 25 25 10 15 25 58,000 IPS Example 15 A15 25 25 10 15 25 57,000 IPS Example 16 A16 25 25 30 20 70,000 IPS Example Π A17 25 25 30 20 68,000 IPS Example 18 A18 25 25 30 20 67,000 IPS

注：1)四羧酸二酐 2)重量平均分子量【表3】Note: 1) tetracarboxylic dianhydride 2) weight average molecular weight [Table 3]

清漆酸二酐" 二胺分子量2) 組立 PMDA CBDA ASD DDOB DDOP DDOE DDET DDPB 實施例 19 A19 25 25 20 10 20 71,000 IPS 實施例 20 A20 25 25 20 10 20 68,000 IPS 實施例 21 A21 25 25 20 10 20 69,000 IPS 實施例 22 A22 25 25 20 10 20 68,000 IPS 實施例 23 A23 25 25 20 10 20 64,000 IPS 實施例 24 A24 25 25 20 10 20 65,000 IPS 53 I30652i9)pif.d〇c 注：1)四羧酸二酐 2)重量平均分子量【表4】Varnish acid dianhydride "Diamine molecular weight 2) Formation PMDA CBDA ASD DDOB DDOP DDOE DDET DDPB Example 19 A19 25 25 20 10 20 71,000 IPS Example 20 A20 25 25 20 10 20 68,000 IPS Example 21 A21 25 25 20 10 20 69,000 IPS Example 22 A22 25 25 20 10 20 68,000 IPS Example 23 A23 25 25 20 10 20 64,000 IPS Example 24 A24 25 25 20 10 20 65,000 IPS 53 I30652i9) pif.d〇c Note: 1) Tetracarboxylate Acid dianhydride 2) Weight average molecular weight [Table 4]

清漆二針卜二胺分子董 2> 组立 PMDA BBD A ASD DDSB DDSP DDSE DDET DDPB 貧施例25 A25 25 25 10 15 25 58,000 IPS 實施例26 A26 25 25 10 15 25 56,000 IPS 實施例27 A27 25 25 10 15 25 55,000 IPS 實施例28 A28 25 25 25 25 65,000 IPS 實施例29 A29 25 25 25 25 63,000 IPS 貧施例30 A30 25 25 25 25 000 IPS 實施例31 A31 25 25 Ϊ0 15 25 55 000 IPS 賞施例32 A32 25 25 10 15 25 54,000 IPS _施例34 賞施例35 實施例36 A33 25 25 10 15 25 51 000 IPS A34 A35 A36 25 25 25 25 25 25 30 30 30 20 20 20 65.000 62.000 61,000 IPS IPS IPS 注：1)四羧酸二酐 2)重量平均分子量清漆A1〜A36及清漆B1〜B5的對比度及殘留DC的評價結果、B6的殘留DC評價結果示於表5。、其中，本發明的實施例的試驗方法中，較佳的對比度值為150以上，較佳的殘留Dc為7〇mV以下。Lacquer bis-diamine molecule 2> PMDA BBD A ASD DDSB DDSP DDSE DDET DDPB Lean application 25 A25 25 25 10 15 25 58,000 IPS Example 26 A26 25 25 10 15 25 56,000 IPS Example 27 A27 25 25 10 15 25 55,000 IPS Example 28 A28 25 25 25 25 65,000 IPS Example 29 A29 25 25 25 25 63,000 IPS Lean Example 30 A30 25 25 25 25 000 IPS Example 31 A31 25 25 Ϊ0 15 25 55 000 IPS Appreciation Example 32 A32 25 25 10 15 25 54,000 IPS _ Example 34 Reward Example 35 Example 36 A33 25 25 10 15 25 51 000 IPS A34 A35 A36 25 25 25 25 25 25 30 30 30 20 20 20 65.000 62.000 61,000 IPS IPS IPS Note: 1) tetracarboxylic dianhydride 2) weight average molecular weight varnishes A1 to A36 and varnishes B1 to B5, the results of evaluation of residual DC and residual DC evaluation results of B6 are shown in Table 5. Among them, in the test method of the examples of the present invention, a preferable contrast value is 150 or more, and a preferable residual Dc is 7 〇 mV or less.

54 I3065i29pifd〇【表5】54 I3065i29pifd〇 [Table 5]

清漆對比度殘留 DC/mV 實施例1 A1 195 45 實施例2 A2 175 62 實施例3 A3 205 58 實施例4 A4 185 60 實施例5 A5 175 65 實施例6 A6 202 55 實施例7 A7 230 55 實施例8 A8 205 57 實施例9 A9 220 57 實施例10 A10 250 60 實施例11 A12 210 63 實施例12 A13 235 64 實施例13 A13 240 55 實施例14 A14 220 57 實施例15 A15 235 57 實施例16 A16 250 50 實施例17 A17 210 52 實施例18 A18 230 52 實施例19 A19 190 60 實施例20 A20 185 60 實施例21 A21 200 60 實施例22 A22 195 63 實施例23 A23 180 63 實施例24 A24 200 63 實施例25 A25 230 55 實施例26 A26 205 57 實施例27 A27 215 58 實施例28 A28 250 61 實施例29 A29 205 63 實施例30 A30 230 63 實施例31 A31 240 57 實施例32 A32 220 59 實施例33 A33 230 59 實施例34 A34 250 53 實施例35 A35 210 55 實施例36 A36 225 55 比較例1 B1 110 85 比較例2 B2 115 35 比較例3 B3 210 110 比較例4 B4 180 120 比較例5 B5 106 100 比較例6 B6 - 130 55 ⑧ Ι3065ι29ρ if.doc 各種清漆的配製 ,清漆A37〜A41及清漆B7以與清漆A1同樣的方法配製。。反應中由於反應熱引起溫度上升時，控制反應溫度約 70 C以下使其反應。另外，配製聚醯胺酸的清漆時，在反應的進行中檢查反應物的黏度，添加BC與GBL後清漆的黏度達到30〜35mPa.s (使用E型黏度計，25。〇時反應終止’於低溫下保存。意即’最初的聚醯胺酸僅在NMP中合成，其後加入鲁 BC及GBL，最終調整清漆的聚醯胺酸濃度為5重量％。各實施例及比較例的原料莫爾比及重量平均分子量示於表6中。【表6】Varnish Contrast Residual DC/mV Example 1 A1 195 45 Example 2 A2 175 62 Example 3 A3 205 58 Example 4 A4 185 60 Example 5 A5 175 65 Example 6 A6 202 55 Example 7 A7 230 55 Example 8 A8 205 57 Example 9 A9 220 57 Example 10 A10 250 60 Example 11 A12 210 63 Example 12 A13 235 64 Example 13 A13 240 55 Example 14 A14 220 57 Example 15 A15 235 57 Example 16 A16 250 50 Example 17 A17 210 52 Example 18 A18 230 52 Example 19 A19 190 60 Example 20 A20 185 60 Example 21 A21 200 60 Example 22 A22 195 63 Example 23 A23 180 63 Example 24 A24 200 63 Example 25 A25 230 55 Example 26 A26 205 57 Example 27 A27 215 58 Example 28 A28 250 61 Example 29 A29 205 63 Example 30 A30 230 63 Example 31 A31 240 57 Example 32 A32 220 59 Example 33 A33 230 59 Example 34 A34 250 53 Example 35 A35 210 55 Example 36 A36 225 55 Comparative Example 1 B1 110 85 Comparative Example 2 B2 115 35 Comparative Example 3 B3 210 110 Comparative Example 4 B4 180 120 Comparative Example 5 B5 106 100 Comparative Example 6 B6 - 130 55 8 Ι3065ι29ρ if.doc Preparation of various varnishes, varnishes A37 to A41 and varnish B7 were prepared in the same manner as varnish A1. . When the temperature rises due to the heat of reaction during the reaction, the reaction temperature is controlled to be about 70 C or less to cause a reaction. In addition, when the varnish of poly-proline is prepared, the viscosity of the reactant is checked during the progress of the reaction, and the viscosity of the varnish after adding BC and GBL reaches 30 to 35 mPa.s (using an E-type viscometer, 25. When the reaction is terminated) It is stored at low temperature. That is, the original poly-proline is synthesized only in NMP, and then Lu BC and GBL are added, and finally the lysine concentration of the varnish is adjusted to 5% by weight. The raw materials of the respective examples and comparative examples The molar ratio and weight average molecular weight are shown in Table 6. [Table 6]

合成例1 清漆 A37 酸二i 计" 二胺分子量 2 ) 盒 PMDA 25 CBD A 〇5 APDS 10 DDM B23 DDET DDPB ddbu 合成例2 A38 25 25 10 40 ---— 46,000 IPS 45 〇〇〇合成例J 25 25 10 40 40,000 IPS 合成例4 A40 25 25 10 40^ _ 43,000 IPS 合成例5 A41 25 25 15 35 ----- 38,000 IPS 合成例6 B7 25 25 to 40 ''·— .J 40,000 IPS 注：1)四羧酸二酐 2)重量平均分子量實施例37〜42、比較例7 清漆A37〜42及清漆B7分別與清漆B2以下述表7中所示的聚合物組成配製，使用此與實施例同樣進行對比度及殘留DC電壓的評價。其中，本發明的實施例的試驗方法中，較佳的對比度為150以上的值，較佳的殘留DC為70mV以下的值。 56 13 Ο652ft if doc 【表7】反應生成物A 反應生成物B 混合比對比度殘留DC/mV 實施例37 B2 A37 A37/B2=l/9 200 50 實施例38 B2 A38 A38/B2=l/9 190 55 實施例39 B2 A39 A39/B2=l/9 210 58 實施例40 B2 A40 A40/B2-1/9 220 60 實施例41 B2 A41 A41/B2=l/9 210 60 實施例42 B2 A37 A37/B2=2/8 220 60 比較例7 B2 B7 B7/B2=l/9 120 40 實施例1〜42及比較例1〜7的結果顯示，藉由使用對比度150以上且殘留DC70mV以下的清漆可得到良好的 IPS型顯示元件。再者，實施例1與比較例6的結果示明，含有硫基的ASD的累積電荷降低效果在TN型液晶顯示元 _ 件中並不明顯，為IPS型液晶顯示元件所特有。雖然本發明已以較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍内，當可作些許之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。【圖式簡單說明】圖1繪示IPS用梳狀電極構造。【主要元件符號說明】嫌無。 ⑧Synthesis Example 1 Varnish A37 Acid II "Diamine Molecular Weight 2) Box PMDA 25 CBD A 〇5 APDS 10 DDM B23 DDET DDPB ddbu Synthesis Example 2 A38 25 25 10 40 --- 46,000 IPS 45 〇〇〇 Synthesis Example J 25 25 10 40 40,000 IPS Synthesis Example 4 A40 25 25 10 40^ _ 43,000 IPS Synthesis Example 5 A41 25 25 15 35 ----- 38,000 IPS Synthesis Example 6 B7 25 25 to 40 ''··.J 40,000 IPS Note: 1) tetracarboxylic dianhydride 2) weight average molecular weight Examples 37 to 42 and Comparative Example 7 Varnishes A37 to 42 and varnish B7 were respectively prepared with varnish B2 in the polymer composition shown in Table 7 below, using this and In the examples, the contrast and the residual DC voltage were evaluated in the same manner. Among the test methods of the examples of the present invention, a preferred contrast ratio is 150 or more, and a preferred residual DC is 70 mV or less. 56 13 Ο652ft if doc [Table 7] Reaction product A Reaction product B Mix ratio contrast residual DC/mV Example 37 B2 A37 A37/B2=l/9 200 50 Example 38 B2 A38 A38/B2=l/9 190 55 Example 39 B2 A39 A39/B2=l/9 210 58 Example 40 B2 A40 A40/B2-1/9 220 60 Example 41 B2 A41 A41/B2=l/9 210 60 Example 42 B2 A37 A37 /B2=2/8 220 60 Comparative Example 7 B2 B7 B7/B2=l/9 120 40 The results of Examples 1 to 42 and Comparative Examples 1 to 7 show that a varnish having a contrast ratio of 150 or more and having a DC of 70 mV or less can be used. A good IPS type display element is obtained. Further, the results of Example 1 and Comparative Example 6 show that the cumulative charge lowering effect of the sulfur-containing ASD is not remarkable in the TN type liquid crystal display element, and is unique to the IPS type liquid crystal display element. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a comb electrode structure for IPS. [Main component symbol description] No. 8

Claims

1306529 修正曰期:97年1!月26日爲第94104802號中文專利範圍無劃線修正本 16170pif.doc 十、申請專利範圍： 1.一種液晶配向膜用組成物，為聚醯亞胺系，適用於橫電，方式液晶顯示元件，含有一四叛酸二軒與一二鞍的反應生成物一聚醯胺酸或一聚醯亞胺的聚醯亞胺系液晶配向膜用組成物，其特徵在於該二胺中包括式[i]的化合物作為必需成分，更包括式[2]及式[3]的化合物中至少一種， H2N—X!—NH2 [l] ^ H2N-X-X2-x_NH2 [2]1306529 Revision period: 97 years 1! Month 26th is the Chinese patent scope of No. 94104802. No slash correction 16170pif.doc X. Patent application scope: 1. A composition for liquid crystal alignment film, which is a polyimine system. The utility model relates to a cross-electricity, a liquid crystal display element, and a composition for a polyimine-based liquid crystal alignment film containing a reaction product of a retinoic acid and a two-saddle, a polyamine or a poly-imine. It is characterized in that the diamine includes a compound of the formula [i] as an essential component, and further includes at least one of the compounds of the formula [2] and the formula [3], H2N-X!-NH2 [l] ^ H2N-X-X2- x_NH2 [2]

h2n 1 [3] 式中’ Xi為含有-S-的2價有機基團，每一 X分別為本環或％己院’ X2為含有_(CH2)n-或_0·的2價有機基，n 為2〜7的整數，心及I分別為氫原子、氫氧基、碳數為 1〜5的烷基或碳數為^5的烷氧基。 2.如申請專利範圍第1項所述之液晶配向膜用組成 φ 物，在式[1]中\為式[4]所示的2價基團， -YV^A-s)r〇" [4] 式中，A分別為或_(CH2)r-，γ為單鍵、-S-或’ u為〇或i’u為〇時q為〇，u為1時9為〇、1或2 ’ r為2〜1〇的整數。 3,如申請專利範圍第2項所述之液晶配向膜用組成物’其中式[4]所示的2價基團為式[5]或式[6]所示的基團， 58 [5] 1306529 16170pif.docH2n 1 [3] where 'X is a divalent organic group containing -S-, each X is a ring or a % singular 'X2 is a divalent organic containing _(CH2)n- or _0· The group n is an integer of 2 to 7, and the core and I are each a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 5 carbon atoms. 2. The composition φ of the liquid crystal alignment film according to the first aspect of the patent application, in the formula [1], is a divalent group represented by the formula [4], -YV^As)r〇" 4) where A is either _(CH2)r-, γ is a single bond, -S- or 'u is 〇 or i'u is 〇, q is 〇, u is 1 when 9 is 〇, 1 or 2 ' r is an integer of 2 to 1 。. 3. The liquid crystal alignment film composition according to the second aspect of the invention, wherein the divalent group represented by the formula [4] is a group represented by the formula [5] or the formula [6], 58 [5] ] 1306529 16170pif.doc

[6] 式中’t為1，2或3，rl為2〜7的整數。 4.如申請專利範圍第2項所述之液晶配向膜用組成物’其中式[4]所示的基團為式[7]所示的2價基團。[6] where 't is 1, 2 or 3, and rl is an integer of 2 to 7. 4. The composition for liquid crystal alignment film according to the second aspect of the invention, wherein the group represented by the formula [4] is a divalent group represented by the formula [7].

5.如申請專利範圍第1〜4中任一項所述之液晶配向膜用組成物’在式Ρ]中Χ2為式[8]所示的2價基團， ——Y)m— Γ815. The composition for liquid crystal alignment film according to any one of claims 1 to 4, wherein Χ2 is a divalent group represented by the formula [8], - Y) m - Γ 81

[10][10]

Y分別為-0-、苯環、環己烷環、單鍵、式[9]或式[10] 所示的2價基團，乙分別為碳數2〜7的亞烷基，m為〇或 1’卩為1或2，其中，111為〇時，丫為_〇_、式[9]或式[1〇] 所不的基團。 6. 如申請專利範圍第5項所述之液晶配向骐用組成物，在[8]中，Y為單鍵。 7. 如申請專利範圍第5項所述之液晶配向膜用組成物’在式[8]中，Y為式[9]所示的2價基團。 8. 如申請專利範圍第5項所述之液晶配向膜用組成 59 1306529 16170pif.doc 物，在式[8]中，Y為式[l〇]所示的2價基團。 9. 如申請專利範圍第1項所述之液晶配向膜用組成物，在式[3]中，Ri及R2分別為氫原子、碳數1〜3的烧基或烧氧基。 10. 如申請專利範圍第1項所述之液晶配向膜用組成物，在式[3]中二個胺基的位置為對位。 11. 如申請專利範圍第1項所述之液晶配向膜用組成物，在該二胺中’使式[1]與式[2]的化合物、式[1]與式[3] ® 的化合物、或式[1]與式[2]與式[3]的化合物的組合中，式[1] 的化合物的含量為30〜99莫爾％，式[2]及式[3]所示的化合物的含量合計為1〜70莫爾％。 12. 如申請專利範圍第1項所述之液晶配向膜用組成物，其中該四羧酸二酐由20~80莫爾％苯均四酸二酐與 80〜20莫爾°/〇環丁院四酸二肝所構成。 13. —種液晶配向膜，其為由申請專利範圍第1項所述之液晶配向膜組成物經預燒結、加熱所形成。 # Μ·一種液晶保持基板，其特徵在於，在基板上設置有申請專利範圍第13項所述之液晶配向膜。 15.—種液晶顯示元件，包括：無電極基板；設置有電極的液晶保持基板；以及液晶材料’設置於上述無電極基板與上述設置有電極的液晶保持基板之間，其特徵在於朝向液晶面設置有電極的液晶保持基板上’設置有申請專利範圍第13項所述之液 1306529 16170pif.doc 晶配向膜。 16. —種液晶配向膜用組成物，適用於橫電場方式液晶顯示元件，其為含有一四羧酸二酐與一二胺的反應生成物一聚醯胺酸或一聚醯亞胺的聚醯亞胺系液晶配向膜用組成物，其特徵在於該液晶配向膜用組成物至少含有下述一反應生成物A及一反應生成物B，該反應生成物A :該四叛酸二針與含有式[1]的化合物 φ 作為必需成分的該二胺的反應生成物該聚醯胺酸或該聚醯亞胺； H2N-X厂 ΝΗ2 [η 該反應生成物B :該四羧酸二酐與含有式[2]的化合物作為必需成分的該二胺的反應生成物該聚醯胺酸或該聚醯亞胺； Η2Ν-Χ-Χ2-χ-ΝΗ2 [2] 式中，Χι為含有-S-的2價有機基團，X分別為苯環或環己烷，X2為含有_(CH2)n-或-〇-的2價有機基團，n為鲁 2〜7的整數。 17. 如申請專利範圍第16項所述之液晶配向膜用組成物’在式[1]中’ X】為式所示的2價基團；〇-“A_YV~(A-s)^^ [4] j中，A分別為""或_(CH2)r-，γ分別為單鍵、-S-或-0·，u為〇或i’u為0時q為〇，u為1時q為 0、1或2，r為2〜1〇的整數。 1306529 16170pif.doc 18.如申請專利範圍第17項所述之液晶配向膜用組成物，其中式[4]所示的2價基團為式[5]或式[6]所示的2價基團；Y is a -O-, benzene ring, cyclohexane ring, single bond, a divalent group represented by the formula [9] or the formula [10], and each is an alkylene group having 2 to 7 carbon atoms, and m is 〇 or 1'卩 is 1 or 2, wherein, when 111 is 〇, 丫 is a group which is not represented by _〇_, formula [9] or formula [1〇]. 6. In the liquid crystal alignment composition according to item 5 of the patent application, in [8], Y is a single bond. 7. The composition for liquid crystal alignment film according to claim 5, wherein Y is a divalent group represented by the formula [9]. 8. The composition for liquid crystal alignment film according to claim 5, wherein the Y is a divalent group represented by the formula [10〇], in the formula [8]. 9. The composition for a liquid crystal alignment film according to claim 1, wherein in the formula [3], Ri and R2 each independently represent a hydrogen atom or a carbon group having 1 to 3 carbon atoms or an alkoxy group. 10. The composition for a liquid crystal alignment film according to claim 1, wherein the position of the two amine groups in the formula [3] is para. 11. The composition for liquid crystal alignment film according to claim 1, wherein the compound of the formula [1] and the formula [2], the compound of the formula [1] and the formula [3] ® are made in the diamine. Or a combination of the formula [1] and the compound of the formula [2] and the formula [3], the content of the compound of the formula [1] is 30 to 99 mol%, represented by the formula [2] and the formula [3]. The total content of the compound is from 1 to 70 mol%. 12. The liquid crystal alignment film composition according to claim 1, wherein the tetracarboxylic dianhydride is composed of 20 to 80 mol% of pyromellitic dianhydride and 80 to 20 mol/〇 The hospital consists of four acids and two livers. A liquid crystal alignment film formed by pre-sintering and heating a liquid crystal alignment film composition according to claim 1 of the patent application. A liquid crystal holding substrate characterized in that the liquid crystal alignment film according to claim 13 is provided on the substrate. A liquid crystal display device comprising: an electrodeless substrate; a liquid crystal holding substrate provided with an electrode; and a liquid crystal material disposed between the electrodeless substrate and the liquid crystal holding substrate provided with the electrode, wherein the liquid crystal surface is oriented The liquid crystal holding substrate provided with the electrode is provided with a liquid 1306529 16170pif.doc crystal alignment film as described in claim 13 of the patent application. 16. A liquid crystal alignment film composition suitable for a horizontal electric field type liquid crystal display element, which is a polymerization product containing a tetracarboxylic dianhydride and a diamine, a polyamine or a polyamidene And a composition for a liquid crystal alignment film containing at least one reaction product A and a reaction product B, the reaction product A: the four-reagent a reaction product of the diamine containing the compound φ of the formula [1] as an essential component of the polyamine or the polyimine; H2N-X plant ΝΗ 2 [η The reaction product B: the tetracarboxylic dianhydride a reaction product of the diamine containing the compound of the formula [2] as an essential component of the polyamine or the polyimine; Η2Ν-Χ-Χ2-χ-ΝΗ2 [2] wherein Χι is contained - The divalent organic group of S-, X is a benzene ring or a cyclohexane, and X2 is a divalent organic group containing _(CH2)n- or -〇-, and n is an integer of 2 to 7. 17. The composition for a liquid crystal alignment film according to claim 16 of the invention, wherein the 'X' in the formula [1] is a divalent group represented by the formula; 〇-"A_YV~(As)^^ [4 ] j, A is respectively "" or _(CH2)r-, γ is a single bond, -S- or -0·, u is 〇 or i'u is 0, q is 〇, u is 1 When q is 0, 1 or 2, r is an integer of 2 to 1 。. 1306529 16170pif.doc 18. The liquid crystal alignment film composition according to claim 17, wherein 2 is represented by the formula [4] The valence group is a divalent group represented by the formula [5] or the formula [6];

S-(CH2)prSS-(CH2)prS

[6] 式中，t為1，2或3，rl為2〜7的整數。 19.如申請專利範圍第17項所述之液晶配向膜用組成物，其中式[4]所示的基團為式[7]所示的2價基團。[6] wherein t is 1, 2 or 3, and rl is an integer of 2 to 7. The composition for a liquid crystal alignment film according to claim 17, wherein the group represented by the formula [4] is a divalent group represented by the formula [7].

[7] 20.如申請專利範圍第16項所述之液晶配向膜用組成物，在式[2]中X2為式[8]所示的2價基團； -Y-(Z-Y)m— [8] [9] [10] Y分別為-〇-、苯環、環己烷環、單鍵、式[9]或式[10] 所示的2價基團，Ζ分別為碳數2〜7的亞烧基，m為0或 l，p為1或2,其中，m為0時，Y為-0-、式[9]或式[10] 所示的基團。[7] 20. The liquid crystal alignment film composition according to claim 16, wherein in the formula [2], X2 is a divalent group represented by the formula [8]; -Y-(ZY)m- [8] [9] [10] Y is a 2-valent group represented by -〇-, benzene ring, cyclohexane ring, single bond, formula [9] or formula [10], respectively, carbon number 2 a sub-alkyl group of -7, m is 0 or 1, and p is 1 or 2, wherein, when m is 0, Y is a group represented by -0-, formula [9] or formula [10].

o^o^

(C%- 62 1306529 16170pif.doc 21.如申請專利範圍第20項所述之液晶配向膜用組成物，在式[8]中，Y為單鍵。 22·如申請專利範圍第20項所述之液晶配向膜用組成物，在式[8]中，γ為式[9]所示的2價基團。 23·如申請專利範圍第20項所述之液晶配向膜用組成物，在式[8]中，Y為式[10]所示的2價基團。 24. 如申請專利範圍第16項所述之液晶配向膜用組成物’在該聚酿亞胺系液晶配向膜用組成物中，該反應生成物A的含量為50〜95莫爾％，該反應生成物B的含量為5 莫爾％〜50莫爾％。 25. 如申請專利範圍第16項所述之液晶配向膜用組成物，其中該反應生成物A中所用的該四羧酸二酐是由 20〜80莫爾％苯均四酸二酐與80〜20莫爾％環丁烷四酸二酐所構成。 26·如申請專利範圍第16項所述之液晶配向膜用組成物，其中該反應生成物B中所用的該四護酸二酐是由 • 20〜莫爾％苯均四酸二酐與80〜20莫爾％環丁烷四酸二酐所構成。 27. —種液晶配向膜，其為由申請專利範圍第16項所述之液晶配向膜組成物經預燒結、加熱所形成的。 28. —種液晶保持基板，其特徵在於，在基板上設置有辛請專利範園第27項所述之液晶配向膜。 29·—種液晶顯示元件，包括：無電極基板； 63 1306529 16170pif.doc 設置有電極的液晶保持基板;以及液晶材料，設置於上述無電極基板與上述設置有電極的液晶保持基板之間，其特徵在於朝向液晶面設置有電極的液晶保持基板上’設置有申請專利範圍第項所述之液晶配向膜。(C%-62 1306529. The method of the liquid crystal alignment film according to claim 20, wherein Y is a single bond in the formula [8]. In the formula [8], γ is a divalent group represented by the formula [9], and the composition for a liquid crystal alignment film according to claim 20, In the formula [8], Y is a divalent group represented by the formula [10]. 24. The composition for liquid crystal alignment film according to claim 16 of the invention is used in the polyaniline liquid crystal alignment film. In the composition, the content of the reaction product A is 50 to 95 mol%, and the content of the reaction product B is 5 mol% to 50 mol%. 25. The liquid crystal according to claim 16 of the patent application. The composition for an alignment film, wherein the tetracarboxylic dianhydride used in the reaction product A is composed of 20 to 80 mol% of pyromellitic dianhydride and 80 to 20 mol% of cyclobutane tetracarboxylic dianhydride. The liquid crystal alignment film composition according to claim 16, wherein the tetracarboxylic acid dianhydride used in the reaction product B is • 20 to Mohr% benzene. And the composition of the liquid crystal alignment film is pre-sintered by the liquid crystal alignment film composition described in claim 16 of the patent application scope. 28. A liquid crystal holding substrate, characterized in that a liquid crystal alignment film according to item 27 of the patent application No. 27 is provided on the substrate. 29. A liquid crystal display element comprising: no electrode a liquid crystal holding substrate provided with an electrode; and a liquid crystal material disposed between the electrodeless substrate and the liquid crystal holding substrate provided with the electrode, wherein the liquid crystal holding substrate is provided with an electrode facing the liquid crystal surface The liquid crystal alignment film described in the above patent application is provided.

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