TWI343926B - Diamine - Google Patents

Diamine Download PDF

Info

Publication number
TWI343926B
TWI343926B TW093132516A TW93132516A TWI343926B TW I343926 B TWI343926 B TW I343926B TW 093132516 A TW093132516 A TW 093132516A TW 93132516 A TW93132516 A TW 93132516A TW I343926 B TWI343926 B TW I343926B
Authority
TW
Taiwan
Prior art keywords
group
formula
liquid crystal
atom
single bond
Prior art date
Application number
TW093132516A
Other languages
Chinese (zh)
Other versions
TW200516099A (en
Inventor
Norio Tamura
Original Assignee
Chisso Corp
Chisso Petrochemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chisso Corp, Chisso Petrochemical Corp filed Critical Chisso Corp
Publication of TW200516099A publication Critical patent/TW200516099A/en
Application granted granted Critical
Publication of TWI343926B publication Critical patent/TWI343926B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
    • C07C217/58—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal (AREA)

Description

15l90pif.doc 九、發明說明： 【發明所屬之技術領域】 本發明係關於二胺化合物、以此二胺製得的聚醯胺酸 或聚醯亞胺、使用此聚合物的液晶配向劑及具有使用此配 向劑之配向膜的液晶顯示元件。 【先前技術】 伴隨晝面大型化及彩色化、提高對比度及發光等顯示 質量及響應速度的要求，液晶顯示元件從扭轉向列型 (Twisted Nematic ’ TN)發展到超扭轉向列型(Super Twisted Nematic，STN) ’並進一步發展到晝素一個一個配置的彩 色薄膜型(Thin Filmed Transistor ’ TFT)顯示元件。近年來， TFT型顯示元件的驅動方式在不斷改良，例如為了進一步 擴大視角’開發了面内啟動開關(In Plane Switching，IPS) 方式及垂直配向（Vertical Alignment，VA)方式，另外正在 開發對於動晝可以保持響應速度的光學補償彎曲排列 (Optically Compensated Bend，OCB)方式。 配向膜達到使液晶顯示元件中的液晶分子按照一定 方向配向、以及相對於基板平面成傾斜狀態(形成預傾角） 二個效果。相對於基板平面液晶分子的傾斜稱為預傾角。 本s兒明書中以下也使用此名稱。配向膜中，為了將分子配 向的歷久、化學、及熱劣化抑制到最小限度，其材料主要 使用玻Μ轉移點(Tg)冋、耐樂品性及耐熱性優里的聚g筑亞 胺薄膜。通常將含有聚醯胺酸或可溶性聚酿亞胺的溶液(即 所謂的液晶配向劑）以旋轉塗膜法或印刷法塗佈於帶有電 15190pif.d〇c 極的基板上，加熱此基板，使聚醯胺酸脫水、閉環，或者 使可溶性聚醯亞胺溶液的溶劑蒸發，得到聚醯亞胺薄膜， 並進一步經過摩擦定向等配向處理步驟得到配向膜。 上述之配向膜被要求應為液晶顯示元件帶來如下效 果。 (1) 可使液晶分子形成合適的預傾角。此外，預傾角隨 摩擦定向的推力強度或者加熱的溫度差異變化幅度小。 (2) 可使液晶顯示元件可以進行無配向缺陷發生的配 向處理。 (3) 可以賦予液晶顯示元件合適的電壓保持率(v〇hage153. The invention relates to a diamine compound, a polyaminic acid or a polyimine prepared by using the same, a liquid crystal alignment agent using the polymer, and the like. A liquid crystal display element using an alignment film of the alignment agent. [Prior Art] The liquid crystal display element has evolved from a twisted nematic (TN) to a super twisted nematic type (Twisted Nematic 'TN) with the requirements for display quality and response speed such as enlargement and colorization of the facet, and improvement in contrast and light emission. Nematic, STN) 'and further developed into a single film of Thin Filmed Transistor 'TFT' display elements. In recent years, the driving method of TFT-type display elements has been continuously improved. For example, in order to further expand the viewing angle, an In Plane Switching (IPS) method and a Vertical Alignment (VA) method have been developed, and OOptically Compensated Bend (OCB) mode that maintains response speed. The alignment film achieves two effects of aligning the liquid crystal molecules in the liquid crystal display element in a certain direction and being inclined with respect to the plane of the substrate (forming a pretilt angle). The tilt of the liquid crystal molecules with respect to the substrate plane is referred to as a pretilt angle. This name is also used in the following book. In the alignment film, in order to minimize the long-term, chemical, and thermal deterioration of the molecular alignment, the material mainly uses a polyimide film having a glass transition point (Tg), a good resistance, and a heat resistance. A solution containing polylysine or soluble polyimine (so-called liquid crystal alignment agent) is usually applied to a substrate having an electric 15190 pif.d〇c electrode by a spin coating method or a printing method, and the substrate is heated. The polyphthalamide is dehydrated, closed, or the solvent of the soluble polyimine solution is evaporated to obtain a polyimide film, and further subjected to an alignment treatment step such as rubbing orientation to obtain an alignment film. The above alignment film is required to have the following effects for the liquid crystal display element. (1) The liquid crystal molecules can be formed into a suitable pretilt angle. In addition, the pretilt angle varies little with the thrust intensity or the temperature difference of the heating. (2) The liquid crystal display element can be subjected to alignment processing in which no alignment defect occurs. (3) It is possible to give the liquid crystal display element a suitable voltage holding ratio (v〇hage

Holding Ratio，VHR)。 ⑷不易發生所謂的“烙印(burn-in)”的現象’即液晶顯 示元件長時間顯示任意晝像後再變換為別的畫像時，前一 晝像殘留的現象》 烙印現象被5忍為是因施加電壓產生的雙極電層的延 遲現象引起的’或是液晶顯示元件中所含的離子等帶電離 子由於電壓施加發生局域化而產生的殘留電荷引起的，又 或是由於對液晶較低的配向控制力而引起的。特別是，相 對基板間液晶扭曲角大的STN方式或者使用杭型電極對 液晶施加的電場方向與基板界面基本平行的IPS方式的液 晶顯示元件中，對液晶配向控制力大的配向膜是眾望所歸 的0 特別是，IPS方式的顯示元件欲'尋求進行黑顯示時， 光洩漏少（黑平衡良好）。為了使得黑平衡良好，配向膜材 15190pif.doc 料不僅需要如上所述的對液晶配向控制力大，而且經摩擦 疋向可以良好貫現臈表面的配向方向。 進一步’近年伴隨著驅動電壓的低電壓化，誘電率異 方性大騎Bsa逐步被使用，顯示^面内發生顯示波動(輝度 波動）的問題不容忽視。特別是’為了去除摩擦定向處理配 向膜時產生的殘渣而進行水洗時，有發生因水洗痕跡造成 顯示波動殘留現象的情形，其成為一個大問題。 特，平11-322925號公報中記載了可以使用具有式(A) 之結構單位的聚合物作為液晶配向膜。然而，沒有關於使 用此聚合物作為液晶配向臈特性的記載。Holding Ratio, VHR). (4) It is not easy to cause a so-called "burn-in" phenomenon. That is, when the liquid crystal display element displays an arbitrary image for a long time and then converts it to another image, the phenomenon of the previous image remains. Caused by the delay phenomenon of the bipolar electric layer generated by the application of voltage, or the residual charge generated by the localization of the charged ions such as ions contained in the liquid crystal display element due to voltage application, or due to the liquid crystal Caused by low alignment control. In particular, in the STN method in which the liquid crystal twist angle between the substrates is large, or the IPS liquid crystal display element in which the electric field direction applied to the liquid crystal is substantially parallel to the substrate interface using the hanging electrode, the alignment film having a large liquid crystal alignment control force is highly desirable. 0 In particular, when the display element of the IPS method is intended to perform black display, the light leakage is small (the black balance is good). In order to make the black balance good, the alignment film 15190pif.doc material not only needs to have a large control force for the liquid crystal alignment as described above, but also can perfectly conform to the alignment direction of the surface of the crucible by the rubbing direction. Further, in recent years, with the low voltage of the driving voltage, the electric induction rate anisotropy is gradually used, and the problem of display fluctuation (luminance fluctuation) in the display surface cannot be ignored. In particular, when water is washed in order to remove the residue generated when the alignment film is treated by rubbing, there is a case where display fluctuations occur due to the washing marks, which becomes a big problem. JP-A-H11-322925 discloses that a polymer having a structural unit of the formula (A) can be used as a liquid crystal alignment film. However, there is no description about the use of this polymer as a property of liquid crystal alignment.

㈧ 特開平11-193346號公報中記載了藉由使用含有式(B) 之化合物的聚醯胺酸與其它聚醯胺酸溶液混合的配向劑所 製造之配向犋，可以改善其配向性、消耗電流、VHR及殘 留電荷的特性。 h2n (CH2)3—<^κ-νη2 (β) 專利第3169062號公報中記載了藉由使用含有式(c) 之化合物的聚醯胺酸與其它聚醯胺酸溶液混合的配向劑所 製造之配向膜，可以改善其配向性。(A) Japanese Patent Publication No. Hei 11-193346 discloses an alignment enthalpy produced by using an alignment agent in which a polyglycine containing a compound of the formula (B) and another polyaminic acid solution are mixed, whereby the alignment and consumption can be improved. Characteristics of current, VHR and residual charge. H2n (CH2)3 - <^κ-νη2 (β) Patent No. 3,169,062 describes an alignment agent which is prepared by mixing a polyaminic acid containing a compound of the formula (c) with another polyaminic acid solution. The alignment film produced can improve its alignment.

*0—(CH2)n—nh2 (c) 【發明内定】 15l90pif.doc 本發明提供一種聚醯胺酸或聚醯亞胺，此特料可1、β 供高水準以滿足上述液晶顯示元件所要求的各特性 ^ 配向膜 ^ — ’H B 日 本發明者們為解決上述課題而銳意研究結果發現，藉 由使用以下述結構的二胺為原料所合成而得到的聚臨胺酸 及/或聚酿亞爿女作為液晶顯不元件中所使用的液晶配向月莫 的材料，可以達到所期望的結果，並基於此發現完成本發 明。 本發明由以下而構成。 [1]具有式⑴所示之結構的二胺 R3 R1*0-(CH2)n-nh2 (c) [Invention of the invention] 15l90pif.doc The present invention provides a poly-proline or polyimine which can be used at a high level to satisfy the above liquid crystal display element. Each of the required characteristics ^ Alignment film ^ - 'HB Japanese inventors have made intensive research to solve the above problems, and found that poly- lysine and/or poly-broth obtained by synthesizing a diamine having the following structure as a raw material The present invention can be achieved by using the material of the liquid crystal alignment used in the liquid crystal display element to achieve the desired result. The present invention consists of the following. [1] Diamine having the structure represented by formula (1) R3 R1

式⑴中，Q 為_(CH2)n•或-((CH2)2〇)m(CH2)2·，n 為 3 至10的整數，m為1至3的整數；Α各自分別為單鍵或者 苯環上的任一氫原子被氟原子、碳原子數1〜4的烷基或碳 原子數1〜4的烷氧基所置換也可的丨，4_亞苯基；尺1及R2 各自分別為氫原子、氟原子、碳原子數1〜4的烷基或碳原 子數1〜4的烷氧基；R3及R4各自分別為氫原子、氟原子； X為單鍵、氧原子或硫原子；其中’ Q為_(CH2)n_，A為單 鍵、X為單鍵或硫原子時，R1或R2中任意的一個為氟原 子、破原子數1〜4的炫基或碳原子數1〜4的炫氧基；A 為單鍵、且X為氧原子時，R1〜R4中至少有一個為氟原子。 [2]式(1-A)〜（i_l)中任意的一個所示之如第1項所述 的二胺。 1343926 15190pif.docIn the formula (1), Q is _(CH2)n• or -((CH2)2〇)m(CH2)2·, n is an integer of 3 to 10, m is an integer of 1 to 3; Α each is a single bond Or any hydrogen atom on the benzene ring may be replaced by a fluorine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; 4, phenylene; 尺 1 and R 2 Each is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; each of R 3 and R 4 is a hydrogen atom or a fluorine atom; X is a single bond, an oxygen atom or a sulfur atom; wherein 'Q is _(CH2)n_, A is a single bond, and X is a single bond or a sulfur atom, and any one of R1 or R2 is a fluorine atom, a thio group having 1 to 4 atomic number or a carbon atom A oxy group having 1 to 4; when A is a single bond and X is an oxygen atom, at least one of R1 to R4 is a fluorine atom. [2] A diamine as described in any one of the formula (1-A) to (i-1). 1343926 15190pif.doc

(1-A) (1-B) R3 R1(1-A) (1-B) R3 R1

(1-C) (1-D)(1-C) (1-D)

(1-E) (1不)(1-E) (1 no)

NH2 (1-G) (1-H) (1-1)NH2 (1-G) (1-H) (1-1)

(1-J) (1-K) (1-L) 9 1343926 [3] 如第1項或第2項所述的二胺，其中式(1)中，R1 及R2各自分別為氟原子、氫原子或第三丁基；r3及R4為 氫原子；A為單鍵或ι，4_亞苯基。 [4] 如第3項所述的二胺，其中式（1)中X為單鍵。 [5] 如第3項所述的二胺，其中式（1)中X為氧原子。 [6] 如第3項戶斤述的二胺，其中式（1)中X為硫原子。 [7] 由10〜1〇〇莫耳百分比(M〇ie%)的式^…所示的結 構單位與9〇〜0莫耳百分比的式(2_2)所示的結構單位構成 的聚醯胺酸。(1-J) (1-K) (1-L) 9 1343926 [3] The diamine according to Item 1 or 2, wherein, in the formula (1), each of R1 and R2 is a fluorine atom, a hydrogen atom or a tributyl group; r3 and R4 are a hydrogen atom; and A is a single bond or ι, 4-phenylene. [4] The diamine according to item 3, wherein X in the formula (1) is a single bond. [5] The diamine according to item 3, wherein X in the formula (1) is an oxygen atom. [6] The diamine as described in Item 3, wherein X in the formula (1) is a sulfur atom. [7] Polyamine which is composed of a structural unit represented by the formula (2_2) of a structural unit represented by the formula (...) of 10 to 1 〇〇 mol% (M〇ie%) and a percentage of 9 〇 to 0 mol%. acid.

式（2-1)及式（2-2)中，Q 為-(CH2)n_ 或 -((CH2)2〇)m(CH2)2-，n 為 3 至 10 的整數，m 為 1 至 3 的 整數；A各自分別為單鍵或者苯環上的任意的一個氫原子 被氟原子、碳原子數1-4的烧基或礙原子數1〜4的烧氧基 所置換也可的1，4-亞苯基；R1及R2各自分別為氫原子、氣 原子、碳原子數1〜4的炫·基或碳原子數1〜4的烧氧基； R3及R4各自分別為氫原子、氟原芋；X為單鍵、氧原子 或硫原子；R5各自分別為碳原子數4〜30的4價有機基 10 1343926 15l90pif.doc 團；R6為碳原子數2〜60的2價有機基團；其中，Q為 -(CH2)n-，Λ為單鍵、X為單鍵或琉原子時，R1或R2中任 意的一個為氟原子、碳原子數1〜4的烷基或碳原子數1〜 4的烷氧基；Α為單鍵、且X為氧原子時，R1、R2、R3及 R4中至少有一個為氟原子。 [8]如第7項所述的聚醯胺酸，其中式(2-1)及(2-2)中 R5各自分別為選自式(3)〜（11)表示的基團中至少其中之一 的4價基團。In the formulae (2-1) and (2-2), Q is -(CH2)n_ or -((CH2)2〇)m(CH2)2-, n is an integer from 3 to 10, and m is 1 to An integer of 3; each of which is a single bond or an arbitrary hydrogen atom on the benzene ring may be replaced by a fluorine atom, a carbon atom having 1-4 carbon atoms or an alkoxy group having an atomic number of 1 to 4; , 4-phenylene; each of R1 and R2 is a hydrogen atom, a gas atom, a hexyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; each of R3 and R4 is a hydrogen atom; Fluorinogen; X is a single bond, an oxygen atom or a sulfur atom; R5 is each a tetravalent organic group having a carbon number of 4 to 30, 10 1343926 15l90 pif. doc; R6 is a divalent organic group having 2 to 60 carbon atoms; Wherein Q is -(CH2)n-, when Λ is a single bond, and X is a single bond or a ruthenium atom, any one of R1 or R2 is a fluorine atom, an alkyl group having 1 to 4 carbon atoms or a carbon atom. When the alkoxy group is 1 to 4; when Α is a single bond and X is an oxygen atom, at least one of R1, R2, R3 and R4 is a fluorine atom. [8] The polyaminic acid according to Item 7, wherein each of R5 in the formulae (2-1) and (2-2) is at least one selected from the group consisting of the formulas (3) to (11). One of the tetravalent groups.

式中，G1為單鍵、碳原子數1〜12的亞烷基、1,4-亞 苯基或1，4-亞環己基；G2為單鍵、-CH2-、-CH2CH2-、-0-、 -CO-、-S-、-C(CH3)-或-C(CF3)2- ; X1 為單鍵或 CH2- ; R32、 R33、R34及R35各自分別為氫原子、' 曱基、乙基或苯基； R36為氫原子或曱基；R37為氫原子、曱基、乙基或苯基； 11 1343926 15.U)〇pif^ a3為環己烷環或苯環；q為1或2 ;式（11)中所表示的基團 為2個結合鍵立為α-位的2組結合鍵。 [9]如第8項所述的聚醯胺，其中R5各自分別為下 述(I)〜(V)所表示的任意的一個基團。 (I) (II) (III) (IV) (V) [10]如第7項至第9項中任何一項所述的聚醯胺酸， 其中R6為下述的任意的一個基團。Wherein G1 is a single bond, an alkylene group having 1 to 12 carbon atoms, 1,4-phenylene group or 1,4-cyclohexylene group; G2 is a single bond, -CH2-, -CH2CH2-, -0 -, -CO-, -S-, -C(CH3)- or -C(CF3)2-; X1 is a single bond or CH2-; R32, R33, R34 and R35 are each a hydrogen atom, a thiol group, Ethyl or phenyl; R36 is a hydrogen atom or a fluorenyl group; R37 is a hydrogen atom, a fluorenyl group, an ethyl group or a phenyl group; 11 1343926 15. U) 〇pif^ a3 is a cyclohexane ring or a benzene ring; q is 1 Or 2; the group represented by the formula (11) is two sets of bond bonds in which the two bond bonds are α-position. [9] The polyamine according to Item 8, wherein each of R5 is an arbitrary one group represented by the following (I) to (V). The poly-polyglycolic acid according to any one of items 7 to 9, wherein R6 is any one of the following groups.

其中’ Βη表示苯曱基。 [11]如第7項至第9項中任何一項所述的聚醯胺酸， 其中R1及R2各自分別為氟原子、氫原子或第三丁基，R3 及R4為氫原-了、Α為單鍵或1，4-亞苯基。 12 1343926 15190pif.doc [12]如第7項至第9項中任何一項所述的聚醯胺酸， 其中如式(2-3)所示之構成式(2-1)其中一部分的基團為式 (1-A)〜（1-L)所示的二胺的作為二胺殘基的以及式（Ι-a)〜 (1-1)所示的基團的任意的一個。 R3 R1Where 'Βη denotes a phenylhydrazine group. [11] The polylysine according to any one of items 7 to 9, wherein each of R1 and R2 is a fluorine atom, a hydrogen atom or a third butyl group, and R3 and R4 are hydrogen atoms, respectively. Α is a single bond or 1,4-phenylene. The polylysine according to any one of items 7 to 9, wherein a part of the formula (2-1) represented by the formula (2-3) is a group The group is a diamine residue represented by the formula (1-A) to (1-L) and a group represented by the formula (Ι-a) to (1-1). R3 R1

13 1343926 15190pif.doc13 1343926 15190pif.doc

(1-a) (1-b) (1-c) (1-d) (1-e) d-f) (1-9) d-h)(1-a) (1-b) (1-c) (1-d) (1-e) d-f) (1-9) d-h)

(1-i) (1-j) (1-k) (1-1)(1-i) (1-j) (1-k) (1-1)

14 1343926 15190pi£doc [13] 如第12項中任何一項所述的聚醯胺酸，其中式 (2-1)中的X為單鍵。 [14] 如第12項中任何一項所述的聚醯胺酸，其中式 (2-1)中的X為氧原子。 [15] 如第12項中任何一項所述的聚醯胺酸，其中式' (2-1)中的X為硫原子。 [16] 如第7項至第15項中任何一項所述的聚醯胺酸， 其中重量平均分子量為5,〇〇〇〜5〇〇,〇〇〇。 [17] 如第7項至第16項中任何一項所述的聚酿胺酸經 脫水而得的聚亞醯胺。 [18] 含有如第7項至第16項中任何一項所述聚醯胺酸 的液晶配向劑。 [19] 含有如第17項所述聚亞醯胺的液晶配向劑。 [20] 自第18項或第19項所述液晶配向劑而得的液晶 配向膜。 [21] 使用第20項所述液晶配向膜的液晶顯示元件。 為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂，下文特舉較佳實施例，並配合所附圖式，作詳細說 明如下。 【實施方式】 以下說明中，聚醯胺酸及聚醯亞胺總稱為聚合物而表 述。本發明的特徵係關於使用具有式(1)所示之結構的二 、使用此二胺之具有式P-1)所示之結構單元、某些情形 15 15J9〇pifd :具有式（2 -2)所示之結構單元的聚醯胺酸及自此聚醯胺 S文毛f生的聚醢亞胺。以上述之聚合物中的其中至少1種組 ^作為液晶配向劑，則此液晶配向劑具有形成液晶配向膜 時可滿足上述要求的特性。 另外，本發明的聚合物係由聚醯胺酸與聚醯亞胺所構 成，其中聚醯亞胺為聚醯胺酸的醯胺酸部分或全部進行醯 亞胺化的聚合物。本發明也包含上述之聚合物的共混物， 例如含有部分醯亞胺化的聚合物的共混聚合物也稱為聚醯 亞胺。 式U)中的R1及R2可分別選自氫、氟、碳原子數】〜4 的烷基(alky丨)及碳原子數1〜4的烷氧基(alkoxy)中的其中 之一。 式（1)中的R3及R4可分別選自氫原子及氟中的其中之 ――〇 上述要求特性中’為減少殘留DC以防止因配向膜的 殘渣造成的顯示不良，較佳是在Ri、R2、尺3及R4中導入 甲基、乙基、曱氧基或氟等較小的取代基。特別是，為了 提咼配向膜的VHR ’較佳是在Ri、r2、R3及R4中導入丙 基、丁基、異丙基、第三丁基、乙氧基、丙氧基、丁氧基、 異丙氧基或第三丁氧基等價數高的取代基。 上述要求特性中，特別是希望降低殘留DC的情況 下，則A選擇1,4-亞苯基為佳。 一般式(2-1)中，χ表示單鍵、氧或硫。此時希望賦予 比液晶配向劑更高的VHR時，X為單鍵或氧為佳，X為單 16 1343926 15190pifdcx: 鍵:J佳。再者，例如2003年S1D國際研討會文摘中ιΐ66 . 頁等記載了 IPS用配向膜卜聚合物的體積電阻率小的液 晶配向膜有利於抑制烙印現象。因此，X為氧或硫為佳， X為硫最佳。 式⑴及(2-1)中 ’ q 為-(CH2)nK(CH2)2〇)m(CH2)2_， 為了保持本發明的配向膜具有良好的配向性及防止摩擦定 向時產生殘渣，η為3至10的整數或m為1至3的整數。 合適的例子如’ 1,3-亞丙基、1，4·亞丁基、i，5-亞戊基、1，6_ 亞己基、I，7-亞庚基、I，8·亞辛基、15&gt;_亞壬基與U0·亞癸 鲁 基。再者’例如由於增大預傾角等理由、希望減小本發明 液晶配向膜表面能的情況下，選擇_(CH2)n_作為q為佳。 再者’希望本發明的液晶配向膜的表面能大的情況下，選 擇_((CH2)20)m(CH2)2•作為 Q 為佳。 X限定於單鍵的式（1)所表示之二胺的合適實例示於 表1〜表5中。The polylysine according to any one of the items 12, wherein X in the formula (2-1) is a single bond. [14] The poly-proline as described in any one of item 12, wherein X in the formula (2-1) is an oxygen atom. [15] The polyaminic acid according to any one of the items 12, wherein X in the formula (2-1) is a sulfur atom. [16] The polylysine according to any one of items 7 to 15, wherein the weight average molecular weight is 5, 〇〇〇~5〇〇, 〇〇〇. [17] The polyamidamine obtained by dehydrating the poly-araminic acid according to any one of items 7 to 16. [18] A liquid crystal alignment agent containing the polyamic acid according to any one of items 7 to 16. [19] A liquid crystal alignment agent containing the polymethyleneamine according to item 17. [20] A liquid crystal alignment film obtained from the liquid crystal alignment agent according to item 18 or item 19. [21] A liquid crystal display element using the liquid crystal alignment film according to item 20. The above and other objects, features and advantages of the present invention will become more <RTIgt; [Embodiment] In the following description, polyglycine and polyimine are collectively referred to as a polymer and are described. The present invention is characterized by using a structure having the structure represented by the formula (1), using the structural unit represented by the formula P-1) using the diamine, and in some cases 15 15J9〇pifd: having the formula (2-2) The polyamic acid shown in the structural unit and the polyimine produced from the polyamine. When at least one of the above polymers is used as a liquid crystal alignment agent, the liquid crystal alignment agent has characteristics which satisfy the above requirements when forming a liquid crystal alignment film. Further, the polymer of the present invention is composed of polyamic acid and polyamidiamine, wherein the polyimine is a polymer which is partially or wholly ruminated by a proline of polylysine. The present invention also encompasses blends of the above polymers, such as blend polymers containing partially iridimized polymers, also known as polyimine. R1 and R2 in the formula U) may be selected from the group consisting of hydrogen, fluorine, an alkyl group (alky) having a carbon number of 〜4, and an alkoxy having 1 to 4 carbon atoms. R3 and R4 in the formula (1) may be selected from the group consisting of a hydrogen atom and fluorine, respectively, in the above-mentioned required characteristics, in order to reduce residual DC to prevent display defects caused by residues of the alignment film, preferably in Ri Further, a smaller substituent such as a methyl group, an ethyl group, a decyloxy group or a fluorine is introduced into R2, 尺3 and R4. In particular, in order to improve the VHR of the alignment film, it is preferred to introduce a propyl group, a butyl group, an isopropyl group, a third butyl group, an ethoxy group, a propoxy group, a butoxy group in Ri, r2, R3 and R4. An isovalent high substituent of isopropoxy or tert-butoxy. Among the above-mentioned required characteristics, in particular, when it is desired to reduce the residual DC, it is preferred that A is a 1,4-phenylene group. In the general formula (2-1), χ represents a single bond, oxygen or sulfur. At this time, when it is desired to impart a higher VHR than the liquid crystal alignment agent, X is preferably a single bond or oxygen, and X is a single 16 1343926 15190 pifdcx: bond: J is preferable. Further, for example, the liquid crystal alignment film having a small volume resistivity of the alignment film of the IPS for use in the abstract of the S1D International Symposium 2003 has been described to facilitate the suppression of the imprinting phenomenon. Therefore, X is preferably oxygen or sulfur, and X is sulfur most. In the formulas (1) and (2-1), 'q is -(CH2)nK(CH2)2〇)m(CH2)2_, in order to maintain the alignment of the alignment film of the present invention and to prevent residue during rubbing orientation, η An integer of 3 to 10 or m is an integer of 1 to 3. Suitable examples are '1,3-propylene, 1,4-butylene, i,5-pentylene, 1,6-hexylene, I,7-heptylene, I,8-octylene, 15&gt;_Aachen and U0·Aaruuki. Further, in the case where it is desired to reduce the surface energy of the liquid crystal alignment film of the present invention for reasons such as an increase in the pretilt angle, it is preferable to select _(CH2)n_ as q. Further, when it is desired that the surface energy of the liquid crystal alignment film of the present invention is large, it is preferable to select _((CH2)20)m(CH2)2• as Q. Suitable examples of the diamine represented by the formula (1) in which X is limited to a single bond are shown in Tables 1 to 5.

17 1343926 15190pif.doc 【表1】17 1343926 15190pif.doc [Table 1]

No. Q X R1 R2 R4 A 1-1 _(CH2)3- - Me H H H - 1-2 -(CH2)3_ - Me Me H H - 1-3 -(CH2)3- - Et H H H - 1-4 -(CH2)3- - Et Et H H - 1-5 -(CH2)3- Pr H H H - 1-6 -(CH2)3- - Pr Pr H H • 1-7 -(CH2)3- Bu H H H - 1-8 -(CH2)3- - Bu Bu H H - 1-9 -(CH2)3- - t-Bu H H H - 1-10 -(CH2)3_ - t-Bu t-Bu H H - 1-11 -(CH2)3- - OMe H H H - M2 -(CH2)3- - OMe OMe H H - 1-13 -(CH2)3- - OEt OEt H H - 1-14 -(CH2)3- OPr OPr H H - 1-15 -(CH2)3- - OBu OBu H H - 1-16 _(CH2)3_ F H H H - 1-17 -(CH2)3- - F F H H - 1-18 -(CH2)4- Me H H H - 1-19 -(CH2)4- - Me Me H H - 1-20 -(ch2)4- Et H H H - 1-21 _(CH2)4- - Et Et H H - 1-22 -(CH2)4- - Pr H H H 1-23 -(ch2)4- - Pr Pr H H - 1-24 -(CH2)4- Bu H H H - 1-25 -(CH2)4- - Bu Bu H H - 1-26 -(CH2)4- - t-Bu H H H • 1-27 -(CH2)4- - t-Bu t-Bu H H - 1-28 -(CH2)4- - OMe H H H - 1-29 -(CH2)4- - OMe OMe ，H H - 1-30 -(CH2)4_ - OEt OEt H H - 18 1343926 15190pif.doc 【表2】No. QX R1 R2 R4 A 1-1 _(CH2)3- - Me HHH - 1-2 -(CH2)3_ - Me Me HH - 1-3 -(CH2)3- - Et HHH - 1-4 - (CH2)3- - Et Et HH - 1-5 -(CH2)3- Pr HHH - 1-6 -(CH2)3- - Pr Pr HH • 1-7 -(CH2)3- Bu HHH - 1- 8 -(CH2)3- - Bu Bu HH - 1-9 -(CH2)3- - t-Bu HHH - 1-10 -(CH2)3_ - t-Bu t-Bu HH - 1-11 -(CH2 ) 3- - OMe HHH - M2 -(CH2)3- - OMe OMe HH - 1-13 -(CH2)3- - OEt OEt HH - 1-14 -(CH2)3- OPr OPr HH - 1-15 - (CH2)3- - OBu OBu HH - 1-16 _(CH2)3_ FHHH - 1-17 -(CH2)3- - FFHH - 1-18 -(CH2)4- Me HHH - 1-19 -(CH2 ) 4- - Me Me HH - 1-20 -(ch2)4- Et HHH - 1-21 _(CH2)4- - Et Et HH - 1-22 -(CH2)4- - Pr HHH 1-23 - (ch2)4- - Pr Pr HH - 1-24 -(CH2)4- Bu HHH - 1-25 -(CH2)4- - Bu Bu HH - 1-26 -(CH2)4- - t-Bu HHH • 1-27 -(CH2)4- - t-Bu t-Bu HH - 1-28 -(CH2)4- - OMe HHH - 1-29 -(CH2)4- - OMe OMe ,HH - 1-30 -(CH2)4_ - OEt OEt HH - 18 1343926 15190pif.doc [Table 2]

No. Q X R1 R2 RJ R4 A 1-31 -(CH2)4- - OPr OPr H H - 1-32 -(CH2)4- - OBu OBu H H - 1-33 -(CH2)4- - F H H H - 1-34 -(CH2)4- - F F H H - 1-35 -(CH2)5- Me H H H 1-36 -(CH2)5- - Me Me H H 1-37 -(CH2)5- - Et H H H - 1-38 -(CH2)5- - Et Et Me Me 1-39 -(ch2)5- - Pr H H H - 1-40 -(ch2)5- - Pr Pr H H 1-41 -(CH2)5- _ Bu H H H - 1-42 -(ch2)5- Bu Bu H H 1-43 -(CH2)5- t-Bu H H H - 1-44 -(CH2)5- - t-Bu t-Bu H H 1-45 -(CH2)5- - OMe H H H 1-46 -(ch2)5- - OMe OMe H H - 1-47 -(ch2)5- - OEt OEt H H _ 1-48 -(CH2)5_ - OPr OPr H H - 1-49 -(CH2)5- OBu OBu H H 1-50 -(CH2)5- - F H H H - 1-51 -(CH2)5- - F F H H - 1-52 -(CH2)6- - Me Me H H - 1-53 -(CH2)6- - Et Et H H - 1-54 -(CH2)6- Pr Pr H H 1-55 -(CH2)〇- - Bu Bu H H - 1-56 -(ch2)6- - t-Bu t-Bu H H - 1-57 -(CH2)6- - OMe H H H 1-58 -(ch2)6- - OEt OEt H H 1-59 -(CH2)6- - OPr OPr ,H H 1-60 -(CH2)6- - OBu OBu H H - 19 1343926 15l90pif.doc 【表3】No. QX R1 R2 RJ R4 A 1-31 -(CH2)4- - OPr OPr HH - 1-32 -(CH2)4- - OBu OBu HH - 1-33 -(CH2)4- - FHHH - 1- 34 -(CH2)4- - FFHH - 1-35 -(CH2)5- Me HHH 1-36 -(CH2)5- - Me Me HH 1-37 -(CH2)5- - Et HHH - 1-38 -(CH2)5- - Et Et Me Me 1-39 -(ch2)5- - Pr HHH - 1-40 -(ch2)5- - Pr Pr HH 1-41 -(CH2)5- _ Bu HHH - 1-42 -(ch2)5- Bu Bu HH 1-43 -(CH2)5- t-Bu HHH - 1-44 -(CH2)5- - t-Bu t-Bu HH 1-45 -(CH2) 5- - OMe HHH 1-46 -(ch2)5- - OMe OMe HH - 1-47 -(ch2)5- - OEt OEt HH _ 1-48 -(CH2)5_ - OPr OPr HH - 1-49 - (CH2)5- OBu OBu HH 1-50 -(CH2)5- - FHHH - 1-51 -(CH2)5- - FFHH - 1-52 -(CH2)6- - Me Me HH - 1-53 - (CH2)6- - Et Et HH - 1-54 -(CH2)6- Pr Pr HH 1-55 -(CH2)〇- - Bu Bu HH - 1-56 -(ch2)6- - t-Bu t -Bu HH - 1-57 -(CH2)6- - OMe HHH 1-58 -(ch2)6- - OEt OEt HH 1-59 -(CH2)6- - OPr OPr ,HH 1-60 -(CH2) 6- - OBu OBu HH - 19 1343926 15l90pif.doc [Table 3]

No. Q X R1 Rz RJ R4 A 1-61 -(CH2)6- - F F H H - 1-62 -(CH2)7- - Me H H H - 1-63 -(CH2)7_ - Et Et H H - 1-64 -(CH2)7- - Pr Pr H H - 1-65 -(CH2)7- - Bu H H H - 1-66 -(CH2)7- - t-Bu t-Bu H H 1-67 -(CH2)7- - OMe OMe H H - 1-68 -(CH2)7- - OEt OEt H H - 1-69 -(CH2)7- - OPr OPr H H - 1-70 -(CH2)7_ - OBu OBu H H - 1-71 -(CH2)7- - F F H H 1-72 -(CH2)8- - Me Me H H - 1-73 •(CH2)8· - Et H H H - 1-74 -(CH2)8- - Pr Pr H H - 1-75 -(CH2)jt - Bu Bu H H - 1-76 -(CH2)8- - t-Bu H H H - 1-77 -(CH2)8- - OMe OMe H H - 1-78 -(CH2)8- - OEt OEt H H - 1-79 -(CH2)8- - OPr OPr H H 1-80 -(CH2)8- OBu OBu H H - 1-81 -(CH2)g- 咖 F F H H - 1-82 -(CH2)9- - Me H H H 1-83 -(CH2)9- - Et Et H H 1-84 -(CH2)9- - Pr Pr Me Me - 1-85 -(CH2)9- - Bu Bu H H 1-86 -(CH2)9- - t-Bu t-Bu H H - 1-87 -(CH2)9- - OMe OMe H H - 1-88 -(CH2)9- - OEt OEt H H - 1-89 -(CH2)9- - OPr OPr ' H H - 1-90 -(CH2)9- - OBu OBu H H - 20 1343926 15190pif.doc 【表4】No. QX R1 Rz RJ R4 A 1-61 -(CH2)6- - FFHH - 1-62 -(CH2)7- - Me HHH - 1-63 -(CH2)7_ - Et Et HH - 1-64 - (CH2)7- - Pr Pr HH - 1-65 -(CH2)7- - Bu HHH - 1-66 -(CH2)7- - t-Bu t-Bu HH 1-67 -(CH2)7- - OMe OMe HH - 1-68 -(CH2)7- - OEt OEt HH - 1-69 -(CH2)7- - OPr OPr HH - 1-70 -(CH2)7_ - OBu OBu HH - 1-71 -( CH2)7- - FFHH 1-72 -(CH2)8- - Me Me HH - 1-73 •(CH2)8· - Et HHH - 1-74 -(CH2)8- - Pr Pr HH - 1-75 -(CH2)jt - Bu Bu HH - 1-76 -(CH2)8- - t-Bu HHH - 1-77 -(CH2)8- - OMe OMe HH - 1-78 -(CH2)8- - OEt OEt HH - 1-79 -(CH2)8- - OPr OPr HH 1-80 -(CH2)8- OBu OBu HH - 1-81 -(CH2)g- Coffee FFHH - 1-82 -(CH2)9- - Me HHH 1-83 -(CH2)9- - Et Et HH 1-84 -(CH2)9- - Pr Pr Me Me - 1-85 -(CH2)9- - Bu Bu HH 1-86 -(CH2 9- - t-Bu t-Bu HH - 1-87 -(CH2)9- - OMe OMe HH - 1-88 -(CH2)9- - OEt OEt HH - 1-89 -(CH2)9- - OPr OPr ' HH - 1-90 -(CH2)9- - OBu OBu HH - 20 1343926 15190pif.doc [Table 4]

No. Q X R1 R&quot; RJ R4 A 1-91 -(CH2)9_ - F H H H - 1-92 -(CH2)i〇- Me Me H H - 1-93 -(CH2),〇- Et Et H H - 1-94 -(CH2)l〇- - Pr Pr H H 1-95 -(CH2)10_ - Bu Bu H H 1-96 -(CH2)9- t-Bu t-Bu H H 1-97 -(CH2)i〇- - OMe OMe H H - 1-98 -(CH2)l〇- OEt OEt H H 1-99 _(CH2)l〇- - F F H H - 1-100 -(CH2)3- H H H H Ph 1-101 -(CH2)3- - Me H H H Ph 1-102 -(CH2)3- - Me Me H H Ph 1-103 -(CH2)3_ Me Me Me Me Ph 1-104 -(CH2)3- H H H H Ph(2-Me) 1-105 -(CH2)3- H H H H Ph(3-Me) 1-106 -(CH2)3- - t-Bu t-Bu H H Ph 1-107 -(CH2)3- - OMe OMe H H Ph 1-108 -(CH2)3- - F F H H Ph 1-109 -(CH2)4- - Me H H H Ph 1-110 -(CH2)4- _ Me Me H H Ph 1-111 -(CH2)4- - Me Me Me Me Ph 1-112 -(ch2)4- - H H H H Ph(2-Me) 1-113 -(CH2)4- - H H H H Ph(3-Me) 1-114 -(ch2)4- t-Bu t-Bu H H Ph 1-115 -(CH2)4- OMe OMe H H Ph 1-116 -(CH2)4- - F F H H Ph 1-117 -(CH2)5- - Me H H H Ph 1-118 -(CH2)5- - Me Me H H Ph 1-119 -(CH2)5- - Me Me Me Me Ph 1-120 -(CH2)5- t-Bu t-Bu H H Ph 21 1343926 15190pif.doc 【表5】No. QX R1 R&quot; RJ R4 A 1-91 -(CH2)9_ - FHHH - 1-92 -(CH2)i〇- Me Me HH - 1-93 -(CH2),〇- Et Et HH - 1- 94 -(CH2)l〇- - Pr Pr HH 1-95 -(CH2)10_ - Bu Bu HH 1-96 -(CH2)9- t-Bu t-Bu HH 1-97 -(CH2)i〇- - OMe OMe HH - 1-98 -(CH2)l〇- OEt OEt HH 1-99 _(CH2)l〇- - FFHH - 1-100 -(CH2)3- HHHH Ph 1-101 -(CH2)3 - - Me HHH Ph 1-102 -(CH2)3- - Me Me HH Ph 1-103 -(CH2)3_ Me Me Me Me Ph 1-104 -(CH2)3- HHHH Ph(2-Me) 1- 105 -(CH2)3-HHHH Ph(3-Me) 1-106 -(CH2)3- - t-Bu t-Bu HH Ph 1-107 -(CH2)3- - OMe OMe HH Ph 1-108 - (CH2)3- - FFHH Ph 1-109 -(CH2)4- - Me HHH Ph 1-110 -(CH2)4- _ Me Me HH Ph 1-111 -(CH2)4- - Me Me Me Me Ph 1-112 -(ch2)4- - HHHH Ph(2-Me) 1-113 -(CH2)4- - HHHH Ph(3-Me) 1-114 -(ch2)4- t-Bu t-Bu HH Ph 1-115 -(CH2)4- OMe OMe HH Ph 1-116 -(CH2)4- - FFHH Ph 1-117 -(CH2)5- - Me HHH Ph 1-118 -(CH2)5- - Me Me HH Ph 1-119 -(CH2)5- - Me Me Me Me Ph 1-120 -(CH2)5- t-Bu t-Bu HH Ph 21 1343926 15190pif.doc 【table 5】

No. Q X R1 Rz Rj R4 A 1-121 -(CH2)5- OMe OMe H H Ph 1-122 -(ch2)5- - F F H H Ph 1-123 -(CH2)6- - Me H H H Ph 1-124 -(CH2)6- Me Me H H Ph 1-125 -(CH2)6- - Me Me Me Me Ph 1-126 -(CH2)6- - t-Bu t-Bu H H Ph 1-127 -(CH2)6- - OMe OMe H H Ph 1-128 -(CH2)6- - F F H H Ph 1-129 -(CH2)7- - Me H H H Ph 1-130 -(CH2)7_ - Me Me H H Ph 1-131 -(CH2)7_ - Me Me Me Me Ph 1-132 -(CH2)7- t-Bu t-Bu H H Ph 1-133 -(CH2)7- - OMe OMe H H Ph 1-134 -(CH2)7- - F F Ph 1-135 -(CH2)8- Me H H H Ph 1-136 -(CH2)8- - Me Me H H Ph 1-137 -(CH2)8- - Me Me Me Me Ph 1-138 -(CH2)JT t-Bu t-Bu H H Ph 1-139 -(CH2)ir - OMe OMe H H Ph 1-140 -(CH2)8- - F F - - Ph 1-141 -(CH2)9- - Me H H H Ph 1-142 -(CH2)9- - Me Me H H Ph 1-143 _(CH2)9· - Me Me Me Me Ph 1-144 -(CH2)9， - t-Bu t-Bu H H Ph 1-145 -(CH2)9- * OMe OMe H H Ph 1-146 -(CH2)9- F F Ph 1-147 -(CH2)i〇- - Me H H H Ph 1-148 -(CH2)i〇- - Me Me H H Ph 1-149 -(CH2)i〇- - Me Me , Me Me Ph 1-150 -(CH2)i〇- - t-Bu t-Bu H H Ph 1-151 -(CH2)i〇- - OMe OMe H H Ph 1-152 -(CH2)i〇- - F F Ph 22 1343926 15190pif.doc 表1〜表5中，Ph表示1,4-亞苯基；取代位置表示胺 基的對位；Me表示曱基；Et表示乙基；Pr表示丙基；Bu 表示丁基；t-Bu表示第三丁基。 X限定於氧的式（1)所表示之二胺的合適實例示於表6 及表7中。 1343926 15190pif.doc 【表6】No. QX R1 Rz Rj R4 A 1-121 -(CH2)5- OMe OMe HH Ph 1-122 -(ch2)5- - FFHH Ph 1-123 -(CH2)6- - Me HHH Ph 1-124 - (CH2)6- Me Me HH Ph 1-125 -(CH2)6- - Me Me Me Me Ph 1-126 -(CH2)6- - t-Bu t-Bu HH Ph 1-127 -(CH2)6 - - OMe OMe HH Ph 1-128 -(CH2)6- - FFHH Ph 1-129 -(CH2)7- - Me HHH Ph 1-130 -(CH2)7_ - Me Me HH Ph 1-131 -(CH2 7_ - Me Me Me Me Ph 1-132 -(CH2)7- t-Bu t-Bu HH Ph 1-133 -(CH2)7- - OMe OMe HH Ph 1-134 -(CH2)7- - FF Ph 1-135 -(CH2)8- Me HHH Ph 1-136 -(CH2)8- - Me Me HH Ph 1-137 -(CH2)8- - Me Me Me Me Ph 1-138 -(CH2)JT t-Bu t-Bu HH Ph 1-139 -(CH2)ir - OMe OMe HH Ph 1-140 -(CH2)8- - FF - - Ph 1-141 -(CH2)9- - Me HHH Ph 1- 142 -(CH2)9- - Me Me HH Ph 1-143 _(CH2)9· - Me Me Me Me Ph 1-144 -(CH2)9, - t-Bu t-Bu HH Ph 1-145 -( CH2)9- * OMe OMe HH Ph 1-146 -(CH2)9- FF Ph 1-147 -(CH2)i〇- - Me HHH Ph 1-148 -(CH2)i〇- - Me Me HH Ph 1 -149 -(CH2)i〇- - Me Me , Me Me Ph 1-150 -(CH2)i〇- - t-Bu t-Bu HH Ph 1-151 -(CH2)i - - OMe OMe HH Ph 1-152 -(CH2)i〇- - FF Ph 22 1343926 15190pif.doc In Tables 1 to 5, Ph represents 1,4-phenylene; the substitution position represents the alignment of the amine group; Me represents a thiol group; Et represents an ethyl group; Pr represents a propyl group; Bu represents a butyl group; and t-Bu represents a tertiary butyl group. Suitable examples of the diamine represented by the formula (1) in which X is limited to oxygen are shown in Table 6 and Table 7. 1343926 15190pif.doc [Table 6]

No. Q X RJ R' RJ R4 A 2-1 -(CH2)3- o F H H H 2-2 -(CH2)3- 〇 F F H H - 2-3 -(CH2)3- 0 H H F F - 2-4 -(CH2)4- 0 F F H H 2-5 -(CH2)4- 0 H H F F 2-6 -(CH2)5- 0 F F H H - 2-7 -(ch2)5- 〇 H H F F 2-8 -(CH2)6- 0 F F H H - 2-9 -(ch2)6- 〇 H H F F - 2-10 -(ch2)7- 0 F F H H - 2-11 -(CH2)7_ 0 H H F F - 2-12 -(CH2)8- o F F H H 2-13 -(CH2)8- 〇 H H F F 2-14 -(CH2)9_ 0 F F H H 2-15 -(CH2)9- o H H F F 2-16 -(CH2)i〇- 0 F F H H - 2-17 -(CH2)i〇- 0 H H F F - 2-18 -(ch2)3- 〇 H H H H Ph 2-19 -(CH2)3- 〇 Me H H H Ph 2-20 -(CH2)3- 0 Me Me H H Ph 2-20 -(CH2)3- 0 Me Me Me Me Ph 2-21 -(CH2)4- 0 H H H H Ph 2-22 -(ch2)4- 〇 Me H H H Ph 2-23 -(ch2)4- 〇 Me Me H H Ph 2-24 -(ch2)4- 〇 Me Me Me Me Ph 2-25 -(ch2)5- 0 H H H H Ph 2-26 -(CH2)5- 0 Me H H H Ph 2-27 -(ch2)5- 〇 Me Me H H Ph 2-28 -(ch2)5- 〇 Me Me , Me Me Ph 2-29 -(ch2)6- 0 H H H H Ph 2-30 -(ch2)6- 〇 Me H H H Ph 24 1343926 15190piCdoc 【表7】No. QX RJ R' RJ R4 A 2-1 -(CH2)3- o FHHH 2-2 -(CH2)3- 〇FFHH - 2-3 -(CH2)3- 0 HHFF - 2-4 -(CH2 ) 4- 0 FFHH 2-5 -(CH2)4- 0 HHFF 2-6 -(CH2)5- 0 FFHH - 2-7 -(ch2)5- 〇HHFF 2-8 -(CH2)6- 0 FFHH - 2-9 -(ch2)6- 〇HHFF - 2-10 -(ch2)7- 0 FFHH - 2-11 -(CH2)7_ 0 HHFF - 2-12 -(CH2)8- o FFHH 2-13 -(CH2)8- 〇HHFF 2-14 -(CH2)9_ 0 FFHH 2-15 -(CH2)9- o HHFF 2-16 -(CH2)i〇- 0 FFHH - 2-17 -(CH2)i 〇- 0 HHFF - 2-18 -(ch2)3- 〇HHHH Ph 2-19 -(CH2)3- 〇Me HHH Ph 2-20 -(CH2)3- 0 Me Me HH Ph 2-20 -(CH2 ) 3- 0 Me Me Me Me Ph 2-21 -(CH2)4- 0 HHHH Ph 2-22 -(ch2)4- 〇Me HHH Ph 2-23 -(ch2)4- 〇Me Me HH Ph 2- 24 -(ch2)4- 〇Me Me Me Me Ph 2-25 -(ch2)5- 0 HHHH Ph 2-26 -(CH2)5- 0 Me HHH Ph 2-27 -(ch2)5- 〇Me Me HH Ph 2-28 -(ch2)5- 〇Me Me , Me Me Ph 2-29 -(ch2)6- 0 HHHH Ph 2-30 -(ch2)6- 〇Me HHH Ph 24 1343926 15190piCdoc [Table 7]

No. Q X R1 R2 R3 R4 A 2-31 -(CH2)6- 0 Me Me H H Ph 2-32 -(CH2)6- 0 Me Me Me Me Ph 2-33 -(CH2)7- 0 H H H H Ph 2-34 -(CH2)7_ o Me H H H Ph 2-35 -(CH2)7_ o Me Me H H Ph 2-36 -(CH2)7- 0 Me Me Me Me Ph 2-37 -(CH2)8_ 0 H H H H Ph 2-38 -(CH2)8- 0 Me H H H Ph 2-39 (CH2)8- 0 Me Me H H Ph 2-40 -(CH2)8- 0 Me Me Me Me Ph 2-41 -(CH2)9_ o H H H H Ph 2-42 _(CH2)9· 0 Me H H H Ph 2-43 _(CH2)9_ 0 Me Me H H Ph 2-44 -(CH2)9_ 0 Me Me Me Me Ph 2-45 -(CH2)i〇_ 〇 H H H H Ph 2-46 -(CH2)i〇· 0 Me H H H Ph 2-47 -(CH2)i〇- 0 Me Me H H Ph 2-48 -(CH2)i〇- 〇 Me Me Me Me Ph 表6及表7中，Ph表示1，4-亞苯基；取代位置表示胺 基的對位；Me表示甲基；Et表示乙基；Pr表示丙基；Bu 表示丁基；t-Bu表示第三丁基。 X限定於硫的式（1)所表示之二胺的合適實例示於表8 25 1343926 15190pif.doc 〜表10中。 【表8】No. QX R1 R2 R3 R4 A 2-31 -(CH2)6- 0 Me Me HH Ph 2-32 -(CH2)6- 0 Me Me Me Me Ph 2-33 -(CH2)7- 0 HHHH Ph 2 -34 -(CH2)7_ o Me HHH Ph 2-35 -(CH2)7_ o Me Me HH Ph 2-36 -(CH2)7- 0 Me Me Me Me Ph 2-37 -(CH2)8_ 0 HHHH Ph 2-38 -(CH2)8- 0 Me HHH Ph 2-39 (CH2)8- 0 Me Me HH Ph 2-40 -(CH2)8- 0 Me Me Me Me Ph 2-41 -(CH2)9_ o HHHH Ph 2-42 _(CH2)9· 0 Me HHH Ph 2-43 _(CH2)9_ 0 Me Me HH Ph 2-44 -(CH2)9_ 0 Me Me Me Me Ph 2-45 -(CH2)i 〇_ 〇HHHH Ph 2-46 -(CH2)i〇· 0 Me HHH Ph 2-47 -(CH2)i〇- 0 Me Me HH Ph 2-48 -(CH2)i〇- 〇Me Me Me Me Ph In Tables 6 and 7, Ph represents 1,4-phenylene; the substitution position represents the para position of the amine group; Me represents a methyl group; Et represents an ethyl group; Pr represents a propyl group; Bu represents a butyl group; t-Bu represents Third butyl. Suitable examples of the diamine represented by the formula (1) in which X is limited to sulfur are shown in Table 8 25 1343926 15190 pif.doc to Table 10. [Table 8]

No. 0 X Ri V RJ A 3-1 -(CH2)3- s Me Me H H - 3-2 -(CH2)3- s Et H H H - 3-3 -(CH2)3- s Et Et H H - 3-4 -(CH2)3- s Pr H H H - 3-5 -(CH2)3- s Pr Pr H H - 3-6 -(CH2)3- s Bu H H H - 3-7 -(CH2)3- s Bu Bu H H - 3-8 -(CH2)3- s t-Bu H H H - 3-9 -(CH2)3- s t-Bu t-Bu H H - 3-10 -(CH2)3- s F H H H - 3-11 -(CH2)3- s F F H H - 3-12 -(CH2)4- s Me H H H - 3-13 -(CH2)4- s Et Et H H - 3-14 -(ch2)4- s Pr Pr H H - 3-15 -(CH2)4- s Bu Bu H H - 3-16 -(CH2)4- s t-Bu H H H - 3-17 -(CH2)4- s t-Bu t-Bu H H - 3-18 -(CH2)4- s F H H H - 3-19 -(CH2)4- s F F H H - 3-20 -(CH2)5- s Me Me H II - 3-21 -(CH2)5- s Et Et H H - 3-22 -(CH2)5- s Pr Pr H H - 3-23 -(ch2)5- s Bu Bu H H - 3-24 -(CH2)5- s t-Bu H H H - 3-25 -(CH2)5- s t-Bu t-Bu H H - 3-26 -(CH2)5- s F F H H - 3-27 -(CH2)6- s Me Me H H - 3-28 -(CH2)6- s Et Et H H - 3-29 -(ch2)6- s OMe OMe H H - 3-30 -(CH2)6- s t-Bu t-Bu H H - 3-31 -(CH2)6- s F F H H - 3-32 -(CH2)7- s Me Me H H - 3-33 -(ch2)7- s Et Et H H - 3-34 -(ch2)7- s OMe OMe H H - 3-35 -(CH2)7- s t-Bu t-Bu H H - 3-36 -(CH2)7- s F F H H - 3-37 -(ch2)8- s Me Me H H - 3-38 -(CH2)8- s Et Et H H - 3-39 -(CH2)8- s OMe OMe， H H - 26 1343926 15190pif.doc 【表9】No. 0 X Ri V RJ A 3-1 -(CH2)3- s Me Me HH - 3-2 -(CH2)3- s Et HHH - 3-3 -(CH2)3- s Et Et HH - 3 -4 -(CH2)3- s Pr HHH - 3-5 -(CH2)3- s Pr Pr HH - 3-6 -(CH2)3- s Bu HHH - 3-7 -(CH2)3- s Bu Bu HH - 3-8 -(CH2)3- s t-Bu HHH - 3-9 -(CH2)3- s t-Bu t-Bu HH - 3-10 -(CH2)3- s FHHH - 3- 11 -(CH2)3- s FFHH - 3-12 -(CH2)4- s Me HHH - 3-13 -(CH2)4- s Et Et HH - 3-14 -(ch2)4- s Pr Pr HH - 3-15 -(CH2)4- s Bu Bu HH - 3-16 -(CH2)4- s t-Bu HHH - 3-17 -(CH2)4- s t-Bu t-Bu HH - 3- 18 -(CH2)4- s FHHH - 3-19 -(CH2)4- s FFHH - 3-20 -(CH2)5- s Me Me H II - 3-21 -(CH2)5- s Et Et HH - 3-22 -(CH2)5- s Pr Pr HH - 3-23 -(ch2)5- s Bu Bu HH - 3-24 -(CH2)5- s t-Bu HHH - 3-25 -(CH2 ) 5-s t-Bu t-Bu HH - 3-26 -(CH2)5- s FFHH - 3-27 -(CH2)6- s Me Me HH - 3-28 -(CH2)6- s Et Et HH - 3-29 -(ch2)6- s OMe OMe HH - 3-30 -(CH2)6- s t-Bu t-Bu HH - 3-31 -(CH2)6- s FFHH - 3-32 - (CH2)7- s Me Me HH - 3-33 -(ch2)7- s Et Et HH - 3-34 -(ch2)7- s OMe OMe H H - 3-35 -(CH2)7- s t-Bu t-Bu HH - 3-36 -(CH2)7- s FFHH - 3-37 -(ch2)8- s Me Me HH - 3-38 - (CH2)8- s Et Et HH - 3-39 -(CH2)8- s OMe OMe, HH - 26 1343926 15190pif.doc [Table 9]

No. 0 X Ri R&quot; RJ R4 A 3-40 -(ch2)8- s t-Bu t-Bu H H - 3-41 -(ch2)8- s F F H H - 3-42 -(CH2)9- s Me Me H H - 3-43 -(ch2)9- s Et Et H H - 3-44 -(CH2V s OMe OMe H H - 3-45 -(CH2)9- s t-Bu t-Bu H H - 3-46 -(CH2),〇- s F F H H - 3-47 -(CH2),〇- s Me Me H H - 3-48 -(CH2),〇- s Et Et H H - 3-49 -(CH2),〇- s OMe OMe H H - 3-50 -(CH2),〇- s t-Bu t-Bu H H - 3-51 -(CH2),〇- s F F H H - 3-52 -(CH2)3- s H H H H Ph 3-53 -(CH2)3- s Me H H H Ph 3-54 -(CH2)3- s Me Me H H Ph 3-55 -(ch2)3- s Me Me Me Me Ph 3-56 -(CH2)4- s H H H H Ph 3-57 -(CH2)4- s Me H H H Ph 3-58 -(CH2)4- s Me Me H H Ph 3-59 -(CH2)4- s Me Me Me Me Ph 3-60 -(CH2)5- s H H H H Ph 3-61 -(CH2)5- s Me H H H Ph 3-62 -(CH2)5- s Me Me H H Ph 3-63 -(CH2)s- s Me Me Me Me Ph 3-64 -(CH2)6- s H H H H Ph 3-65 -(ch2)6- s Me H H H Ph 3-66 -(ch2)6- s Me Me H H Ph 3-67 -(ch2)6- s Me Me Me Me Ph 3-68 -(CH2)7- s H H H H Ph 3-69 -(CH2)7- s Me H H H Ph 3-70 -(CH2)7- s Me Me H H Ph 3-71 -(CH2)7- s Me Me Me Me Ph 3-72 -(CH2)g- s H H H H Ph 3-73 -(CH2)g- s Me H H H Ph 3-74 -(CH2)8- s Me Me H H Ph 3-75 -(ch2)8- s Me Me Me Me Ph 3-76 -(CH2)9- s H H H H Ph 3-77 -(CH2)9- s Me H H H Ph 3-78 -(CH2)9- s Me Me H H Ph 27 1343926 15190pif.doc 【表10】No. 0 X Ri R&quot; RJ R4 A 3-40 -(ch2)8- s t-Bu t-Bu HH - 3-41 -(ch2)8- s FFHH - 3-42 -(CH2)9- s Me Me HH - 3-43 -(ch2)9- s Et Et HH - 3-44 -(CH2V s OMe OMe HH - 3-45 -(CH2)9- s t-Bu t-Bu HH - 3-46 -(CH2), 〇- s FFHH - 3-47 -(CH2), 〇- s Me Me HH - 3-48 -(CH2), 〇- s Et Et HH - 3-49 -(CH2), 〇- s OMe OMe HH - 3-50 -(CH2),〇- s t-Bu t-Bu HH - 3-51 -(CH2),〇- s FFHH - 3-52 -(CH2)3- s HHHH Ph 3 -53 -(CH2)3- s Me HHH Ph 3-54 -(CH2)3- s Me Me HH Ph 3-55 -(ch2)3- s Me Me Me Me Ph 3-56 -(CH2)4- s HHHH Ph 3-57 -(CH2)4- s Me HHH Ph 3-58 -(CH2)4- s Me Me HH Ph 3-59 -(CH2)4- s Me Me Me Me Ph 3-60 -( CH2)5-s HHHH Ph 3-61 -(CH2)5- s Me HHH Ph 3-62 -(CH2)5- s Me Me HH Ph 3-63 -(CH2)s- s Me Me Me Me Ph 3 -64 -(CH2)6- s HHHH Ph 3-65 -(ch2)6- s Me HHH Ph 3-66 -(ch2)6- s Me Me HH Ph 3-67 -(ch2)6- s Me Me Me Me Ph 3-68 -(CH2)7- s HHHH Ph 3-69 -(CH2)7- s Me HHH Ph 3-70 -(CH2)7- s Me Me HH Ph 3-71 -(CH2)7 - s Me Me Me Me Ph 3-7 2 -(CH2)g- s HHHH Ph 3-73 -(CH2)g- s Me HHH Ph 3-74 -(CH2)8- s Me Me HH Ph 3-75 -(ch2)8- s Me Me Me Me Ph 3-76 -(CH2)9- s HHHH Ph 3-77 -(CH2)9- s Me HHH Ph 3-78 -(CH2)9- s Me Me HH Ph 27 1343926 15190pif.doc [Table 10]

No. Q X R1 R2 R3 R4 A 3-79 -(CH2)9- s Me Me Me Me Ph 3-80 -(CH2)i〇- s H H H H Ph 3-81 -(CH2)i〇- s Me H H H Ph 3-82 -(CH2)i〇- s Me Me H H Ph 3-83 -(CH2)10- s Me Me Me Me Ph 表8〜表10中，Ph表示1，4-亞苯基；取代位置表示 胺基的對位；Me表示甲基；Et表示乙基；Pr表示丙基； Bu表示丁基；t-Bu表示第三丁基。 Q為-((CH2)20)m(CH2)2-的式⑴所表示之二胺的合適 實例示於表11中。 28 1343926 15190pif.doc 【表11】No. QX R1 R2 R3 R4 A 3-79 -(CH2)9- s Me Me Me Me Ph 3-80 -(CH2)i〇- s HHHH Ph 3-81 -(CH2)i〇- s Me HHH Ph 3-82 -(CH2)i〇- s Me Me HH Ph 3-83 -(CH2)10- s Me Me Me Me Ph In Table 8 to Table 10, Ph represents 1,4-phenylene; The para position of the amine group; Me represents a methyl group; Et represents an ethyl group; Pr represents a propyl group; Bu represents a butyl group; and t-Bu represents a third butyl group. Suitable examples of the diamine represented by the formula (1) wherein Q is -((CH2)20)m(CH2)2- are shown in Table 11. 28 1343926 15190pif.doc [Table 11]

No. Q X R1 R2 R3 R4 A 3-4-1 -(CH2)20(CH2)2- 0 Me H H H - 3-4-2 -(CH2)20(CH2)2- 0 H Me H H - 3-4-3 -(CH2)20(CH2)2- 0 H H Me H - 3-4-4 -(CH2)20(CH2)2- 0 Me Me H H 3-4-5 -(CH2)20(CH2)2- o Me Me Me Me - 3-4-6 -(ch2)2o(ch2)2- s H H H H - 3-4-7 -(CH2)20(CH2)2- s Me H H H - 3-4-8 -(CH2)20(CH2)2- s H Me H H - 3-4-9 -(CH2)20(CH2)2- s Me Me H H - 3-4-10 -(CH2)20(CH2)2- s Me Me Me Me - 3-4-11 -(CH2)20(CH2)2- s H H H H - 3-4-12 -(ch2)20 (ch2)2o(ch2)2- s H H H H - 3-4-13 -(ch2)20 (ch2)20 (ch2)2o(ch2)2- s H H H H 作為生成本發明的式(2-1)及(2-2)中R5所表示的4價 有機基團之四缓酸二針(tetracarboxylie acid anhydride)， 可以使用公知的全部四竣酸二酐。特別合適的例子示於表 12〜表14中。 29 1343926 15190pif.doc 【表12】No. QX R1 R2 R3 R4 A 3-4-1 -(CH2)20(CH2)2- 0 Me HHH - 3-4-2 -(CH2)20(CH2)2- 0 H Me HH - 3-4 -3 -(CH2)20(CH2)2- 0 HH Me H - 3-4-4 -(CH2)20(CH2)2- 0 Me Me HH 3-4-5 -(CH2)20(CH2)2 - o Me Me Me Me - 3-4-6 -(ch2)2o(ch2)2- s HHHH - 3-4-7 -(CH2)20(CH2)2- s Me HHH - 3-4-8 - (CH2)20(CH2)2- s H Me HH - 3-4-9 -(CH2)20(CH2)2- s Me Me HH - 3-4-10 -(CH2)20(CH2)2- s Me Me Me Me - 3-4-11 -(CH2)20(CH2)2- s HHHH - 3-4-12 -(ch2)20 (ch2)2o(ch2)2- s HHHH - 3-4-13 -(ch2)20 (ch2)20 (ch2)2o(ch2)2- s HHHH as a tetravalent organic group represented by R5 in the formulae (2-1) and (2-2) of the present invention As the tetracarboxylie acid anhydride, all known tetradecanoic dianhydrides can be used. Particularly suitable examples are shown in Tables 12 to 14. 29 1343926 15190pif.doc [Table 12]

30 1343926 15190pif.doc 【表13】30 1343926 15190pif.doc [Table 13]

31 1343926 15190pif.doc 【表14】 4-27 1x^4 Ο 〇 4-28 Ο I 0 。处。 ο ο 4-29 0 4-30 ο 4-31 4-32 。綠 4-33 ο ο X。 Υ 'Λ ο ο 4-34 ο ο 。滅。 ο ο 4-35 4-36 4-37 y 0 Ο 4-38 4-39 ㈣ Ο ο 4-4031 1343926 15190pif.doc [Table 14] 4-27 1x^4 Ο 〇 4-28 Ο I 0 . At the office. ο ο 4-29 0 4-30 ο 4-31 4-32 . Green 4-33 ο ο X. Υ 'Λ ο ο 4-34 ο ο. Off. ο ο 4-35 4-36 4-37 y 0 Ο 4-38 4-39 (4) Ο ο 4-40

上述化合物中有含有異構體者，異構體混合物也可。 32 1343926 15l9〇pitdc 再者，本發明所使用的四羧酸二酐也可以是上述化合物以 外者。 口 由合適例的四羧酸二酐構成的、式(2)表示的聚醯胺酸 或聚醯亞胺所組成的液晶配向膜，任一都滿足作為配向膜 所必需的上述特性。因此，特別適宜作為含有臨界值電壓 低的，晶組合物、低電壓驅動的TFT型顯示元件用配向膜。 希望賦予液晶顯示元件高VHR時，藉由自N〇4_2、 4-12、4·13、4_14、4-15、4-16、4·Π、4-18、4_19、4-20、 4-2 卜 4·22、、似、4_28、4·29、㈣、仰、4·32、 4-38等具有脂環基H的化合物巾選出至少—種你 現。另外’特別是希望防止烙印現象時，藉由 4-4、4-5、4-6、4-7、4_8、4_9、4]〇、411419等化合 物與其它化合物適宜組合，可以實現。 口 生成式(2-2)中R6所表示的有機 用公知的全部二胺。特別合適的例 妝J 乂便 &lt; ^卞’不於表15〜表π。 33 1343926 15100pif.doc 【表15】Among the above compounds, those containing isomers may also be used. 32 1343926 15l9〇pitdc Further, the tetracarboxylic dianhydride used in the present invention may be any of the above compounds. The liquid crystal alignment film composed of the polyamic acid or the polyimine represented by the formula (2), which is composed of a tetracarboxylic dianhydride of a suitable example, satisfies the above-mentioned characteristics necessary as an alignment film. Therefore, it is particularly suitable as an alignment film for a TFT-type display element which contains a crystal composition having a low threshold voltage and a low voltage drive. It is desirable to give the liquid crystal display element a high VHR by using N〇4_2, 4-12, 4·13, 4_14, 4-15, 4-16, 4·Π, 4-18, 4_19, 4-20, 4- 2 Bu 4·22, like, 4_28, 4·29, (4), Yang, 4.32, 4-38 and other compound towels with alicyclic group H are selected at least one kind of you. Further, in particular, when it is desired to prevent the imprinting phenomenon, a compound such as 4-4, 4-5, 4-6, 4-7, 4_8, 4_9, 4] 〇, 411419 or the like can be suitably combined with other compounds. The organic compound represented by R6 in the formula (2-2) is all known as a diamine. A particularly suitable example of makeup J 乂 &lt; ^卞' is not in Table 15 to Table π. 33 1343926 15100pif.doc [Table 15]

No. 二胺 No. 二胺 5-1 h2n(ch2)3nh2 5-2 h2n(ch2)4nh2 5-3 h2n(ch2)6nh2 5-4 h2n(ch2)12nh2 5-5 H2N—^ y~NH2 5-6 H2N—^ y~NH2 5-7 5-8 H2N—nh2 5-9 HzN—jj^pNHa 5-10 户Hfl H2N—^ nh2 5-11 0^12^25 «2Ν—^ \-m2 5-12 h2n^O/〇nO_nhz 5-13 Η2ν_0/χ0_νη2 5-14 HzN NH2 5-15 h2n_^/n&lt;^_nh2 5-16 5-17 HaN^D)/N^_NH2 5-18 ^O^yNH2 5-19 5-20 5-21 o h2nH0/Sn0~nh2 5-22 h2n^O/Sn^^nhz 5-23 h2n-&lt;^^S'^NQ-nh2 5-24 5-25 o HzN—〇^〇~叫 5-26 34 1343926 15190pif.doc 【表16】 5-27 NH, 0 NHj 5-28 HzN^0^0~NH2 5-29 C^i/ NH2 5-30 F3C cf3 ^N~C!y&gt;^C^_NH2 5-31 5-32 h2n~^〇'^~^〇'^~nh2 5-33 h^-©^〇nS^^〇v©-nh* 5-34 c4h9 h/i^〇^X^〇^)-nh2 5-35 5-36 c4h9 5-37 η,ν-Ο^ΑΛ^Α^-νη, 5-38 C7H15 5-39 5-40No. Diamine No. Diamine 5-1 h2n(ch2)3nh2 5-2 h2n(ch2)4nh2 5-3 h2n(ch2)6nh2 5-4 h2n(ch2)12nh2 5-5 H2N—^ y~NH2 5 -6 H2N—^ y~NH2 5-7 5-8 H2N—nh2 5-9 HzN—jj^pNHa 5-10 Household Hfl H2N—^ nh2 5-11 0^12^25 «2Ν—^ \-m2 5 -12 h2n^O/〇nO_nhz 5-13 Η2ν_0/χ0_νη2 5-14 HzN NH2 5-15 h2n_^/n&lt;^_nh2 5-16 5-17 HaN^D)/N^_NH2 5-18 ^O^yNH2 5-19 5-20 5-21 o h2nH0/Sn0~nh2 5-22 h2n^O/Sn^^nhz 5-23 h2n-&lt;^^S'^NQ-nh2 5-24 5-25 o HzN— 〇^〇~叫5-26 34 1343926 15190pif.doc [Table 16] 5-27 NH, 0 NHj 5-28 HzN^0^0~NH2 5-29 C^i/ NH2 5-30 F3C cf3 ^N~ C!y&gt;^C^_NH2 5-31 5-32 h2n~^〇'^~^〇'^~nh2 5-33 h^-©^〇nS^^〇v©-nh* 5-34 c4h9 h /i^〇^X^〇^)-nh2 5-35 5-36 c4h9 5-37 η,ν-Ο^ΑΛ^Α^-νη, 5-38 C7H15 5-39 5-40

35 1343926 15190pif.doc 【表17】35 1343926 15190pif.doc [Table 17]

一般而言，液晶的預傾角係藉'由改變聚醯胺酸或聚醯 亞胺的側鏈大小而進行調節，但在大多數的情形下，係藉 36 1343926 I5190pif.doc 由改變-胺殘基的大小而進行。若使用表5的合 Να5-1 〜5-33、5-35、5-37、及 5_43〜5_52 所表示的二胺 作為式(2-2)的V，職別適合於作為要求比較大預傾角的 Ty、OCB及VA則己向膜。综合考慮上述觀點，較佳的 R 為 No.5-8、5-12、5-13、5-18、5-22、5-36、5-37、w、 5-41 ' 5-42'5-44 ' 5-46 ° 為進一步有效地表現配向臈所要求的特性，混合2 種以上薄膜化時表面能不同的聚合物溶解於溶劑所得清漆 6勺方法（以下柄為聚合物共混物)被多次使用。例如，特開 平8 43831 f虎A報中公開了纟2個組成以上的聚合物混合 液形成樹脂塗膜時，利用表面張力小的組成自發地易於在 ，表面偏析的特性，並藉由使表現良好之液晶配向特性的 樹脂塗臈的表面張力比表現良好電學特性的樹脂塗膜的表 面張力逛小2dyne/cm以上，於配向膜表面形成表現良好液 晶配向性的樹脂或於配向膜内部形成表現良好電學特性的 樹脂，從而得到配向臈的方法。 本發明聚醯胺酸及由其衍生的聚醯亞胺也可以提高 配向膜所要求的特性，為了達到上述目的，相異的本發明 聚合物之間或本發明聚合物及其它聚合物也可以進行共 混。 具有—般式(2-1)所示之結構單元的聚合物具有特別 優異的液晶配向性。因此，本發明的聚合物與其它聚合物 進行聚合物共混時，若使用本發明故合物作為表面張力小 的組成’則可以得到穩定的有效表現液昱配向特性的配向 37 1343926 15190pif.doc 膜。為此，一般式(2-2)所示的結構單元的R6，以使用上述 的具有大側鏈的取代基為佳。 聚合物共混物藉由將相異的本發明聚合物溶液或本 發明水合物，谷液與其匕聚合物溶液混合作為混合物，並自 此混合物中去除溶劑而得到。自混合物溶液製造配向膜‘ 中，使用其以適當溶劑稀釋所得的溶液(清漆）。若混合物 溶液的各聚合物組成的濃度為所期望值，則不作稀釋:直 接用於製造配向膜也可。 為了進-步改善本發明液晶配向膜的特性、進行配向鲁 膜於玻璃基板的密著性及硬度的調節，可於本發明的液晶 配向劑中添加有機矽化合物。 Ba 為了進行配向膜於破璃基板的密著性及硬度的調節， 於液晶配向财所添加的有機狐合物例如是魏偶聯劑 (silane coupling agent)或矽油（siHc〇ne 〇i丨）。其中矽烷偶俨 劑例如是胺丙基三曱氡基矽烷、胺丙基三乙氧基矽^ 烯基三甲氧基矽烷、Ν·(2-胺乙基)3_胺丙基曱基二曱氧基矽 烷、Ν-(2-胺乙基)3-胺丙基三曱氧基矽烷、乙烯基三乙&amp;基 石夕烧、3-曱基丙稀氧丙基三曱氧基石夕烷、3·去水甘油氧二· 基三曱氧基魏、3-去水甘油氧丙基甲基二曱氧基魏或 2·(3,4:環氧環己基）乙基三曱氧基石夕坑。矽油例如是二甲基 聚石夕氧烧、聚二曱基魏@絲二苯基錢^Λ 合物於配向細添加量，相對於含有配㈣的反應生成物 固形物為0.01〜5重量百分比(wt%)，較佳為〇丨〜〕重 38 1343926 I5l90pif.doc 為配製本發明的各種液晶配向劑而使用的溶劑例如 是N-曱基-2-吡咯鲖(NMp)、二曱基曱醯胺(DMF)、二曱基 乙醯胺(DMAc)、二曱基亞砜(DMSO)、乙二醇單丁喊(BC)、 乙二醇單***或γ-丁内酯，且也可使用上述之2種以上的 溶劑混合。再者，若反應生成物可溶的上述溶劑以外者， 並不限定於此。 為了使得向玻璃基板的塗佈容易進行並且摩擦定向 時防止殘渣’本發明的聚醯胺酸的重量平均分子量，以 5,000〜500,000為佳，較佳為10 000〜100 000。再者以最 新的噴墨法印刷進行塗佈時，本發明的聚醯胺酸的重量分 子量以5,000〜1〇〇,000為佳，較佳為1〇〇〇〇〜5〇〇〇〇。自 上述分子量的聚醯胺酸衍生而來的聚醯亞胺作為本發明的 聚醯亞胺為佳。 &gt;谷劑中’以總重量0.1〜3〇重量百分比，較佳為1〜 10重里百分比的濃度溶解本發明聚合物中的至少一種及 其它組分而配製液晶配向劑，此配向劑經毛刷塗佈法、浸 潤法、旋轉塗膜法、噴濺法或印刷法等塗佈於基板上。其 後，於50〜150°C，較佳為80〜12(TC下蒸發溶劑後，加熱 至150〜40(TC，較佳為180〜28(rc，以進行成膜。塗佈前 以矽烷偶聯劑處理基板表面，若在其上成膜可以改善膜與 •板的接著性。其後，以布等物品按一個方向摩擦膜表面 即可以得到配向臈。 由上述構成的含有本發明聚合杨的液晶配向劑，可以 作為配向膜、保護膜或絕緣膜使用，特別是最適於作為液 39 15l9〇pird〇c晶 顯 示元件用的配向膜。另外，配向劑也可以與聚酿胺亞 月女或聚酿胺等其它高分子化合物混合 再者’本發明的聚合物除液晶配向膜之外，也可以應 用於各種聚醯亞胺塗膜劑或聚醯亞胺樹脂成型品、薄膜、 或纖維等。 / ' 本發明的式（1)表示的化合物可以藉由下述方法合成。 (1)A為單鍵的情形In general, the pretilt angle of the liquid crystal is adjusted by changing the size of the side chain of the poly-proline or polyimine, but in most cases, it is changed by the amine residue by 36 1343926 I5190pif.doc The size of the base is carried out. If the diamines represented by the combinations α5-1 to 5-33, 5-35, 5-37, and 5_43 to 5_52 in Table 5 are used as the V of the formula (2-2), the job is suitable as a relatively large requirement. The angles of Ty, OCB and VA are already directed to the film. Taking the above viewpoint into consideration, preferred R is No. 5-8, 5-12, 5-13, 5-18, 5-22, 5-36, 5-37, w, 5-41 ' 5-42' 5-44 ' 5-46 ° In order to further effectively characterize the properties required for the alignment, a mixture of two or more types of films with different surface energies can be dissolved in a solvent to obtain a 6-spoon varnish (the following handle is a polymer blend) ) was used multiple times. For example, in the case of forming a resin coating film of a polymer mixture of two or more components, a composition having a small surface tension is spontaneously easy to be segregated and surface segregation is exhibited by the technique disclosed in Japanese Laid-Open Patent Publication No. Hei. The surface tension of the resin coated with good liquid crystal alignment characteristics is smaller than the surface tension of the resin coating film exhibiting good electrical properties by 2 dyne/cm or more, forming a resin exhibiting good liquid crystal alignment on the surface of the alignment film or forming an inner surface of the alignment film. A resin having good electrical properties, thereby obtaining a method of aligning enthalpy. The polylysine of the present invention and the polyimine derived therefrom can also improve the properties required for the alignment film. To achieve the above object, the polymers of the present invention or the polymers of the present invention and other polymers can also be used. Blend. The polymer having the structural unit represented by the general formula (2-1) has particularly excellent liquid crystal alignment. Therefore, when the polymer of the present invention is polymer-blended with other polymers, if the composition of the present invention is used as a composition having a small surface tension, a stable and effective expression of the alignment property of the liquid enthalpy can be obtained. 37 1343926 15190pif.doc membrane. For this reason, R6 of the structural unit represented by the general formula (2-2) is preferably a substituent having a large side chain as described above. The polymer blend is obtained by mixing a different polymer solution of the present invention or the hydrate of the present invention, a gluten solution with a ruthenium polymer solution as a mixture, and removing the solvent from the mixture. The resulting solution (varnish) is diluted with a suitable solvent from the mixture solution to produce an alignment film. If the concentration of each polymer composition of the mixture solution is a desired value, it is not diluted: it may be used directly for the production of an alignment film. In order to further improve the characteristics of the liquid crystal alignment film of the present invention, adjust the adhesion of the alignment film to the glass substrate, and adjust the hardness, an organic ruthenium compound can be added to the liquid crystal alignment agent of the present invention. Ba In order to adjust the adhesion and hardness of the alignment film on the glass substrate, the organic fox compound added to the liquid crystal alignment is, for example, a silane coupling agent or an eucalyptus oil (siHc〇ne 〇i丨). Among them, the decane oxime agent is, for example, aminopropyltridecyl decane, amine propyl triethoxy oxime alkenyl trimethoxy decane, ruthenium (2-aminoethyl) 3 -aminopropyl decyl ruthenium Oxydecane, Ν-(2-aminoethyl) 3-aminopropyltrimethoxy decane, vinyl triethyl amp; gems, 3-mercaptopropyloxypropyltrimethoxy oxetane, 3. Dehydroglyceryloxydiyltrimethoxy-Wei, 3-dehydroglyceryloxypropylmethyldimethoxy-Wei or 2·(3,4:epoxycyclohexyl)ethyltrimethoxylate pit. The eucalyptus oil is, for example, a dimethyl agglomerated gas, a polydifluorenyl-Wei-Si diphenylene ruthenium compound, and is added in an amount of 0.01 to 5 by weight based on the solid content of the reaction product containing the compound (IV). (wt%), preferably 〇丨~〕 weight 38 1343926 I5l90pif.doc The solvent used for formulating the various liquid crystal alignment agents of the present invention is, for example, N-mercapto-2-pyrroleium (NMp), dimercaptopurine Indamine (DMF), dimercaptoacetamide (DMAc), dimercaptosulfoxide (DMSO), ethylene glycol monobutyl (BC), ethylene glycol monoethyl ether or γ-butyrolactone, and may also The two or more solvents described above are mixed. In addition, the solvent other than the solvent in which the reaction product is soluble is not limited thereto. The weight average molecular weight of the polyglycolic acid of the present invention is preferably from 5,000 to 500,000, preferably from 10,000 to 100,000, in order to facilitate the application to the glass substrate and to prevent the residue from being rubbed. Further, when the coating is carried out by the latest ink jet printing, the molecular weight of the polyglycolic acid of the present invention is preferably 5,000 to 1 Å,000, preferably 1 Å to 5 Å. The polyimine derived from the above molecular weight polyamine is preferred as the polyimine of the present invention. &gt; In the granules, a liquid crystal alignment agent is prepared by dissolving at least one of the polymers of the present invention and other components at a concentration of 0.1 to 3 weight percent, preferably 1 to 10 weight percent, based on the total weight. A brush coating method, a wetting method, a spin coating method, a sputtering method, a printing method, or the like is applied onto a substrate. Thereafter, at 50 to 150 ° C, preferably 80 to 12 (after evaporating the solvent under TC, heating to 150 to 40 (TC, preferably 180 to 28 (rc, for film formation). The coupling agent treats the surface of the substrate, and if the film is formed thereon, the adhesion between the film and the plate can be improved. Thereafter, the surface of the film is rubbed in one direction with an article such as cloth to obtain a alignment enthalpy. Yang's liquid crystal alignment agent can be used as an alignment film, a protective film or an insulating film, and is particularly suitable as an alignment film for liquid 39 15l9 〇pird 〇c crystal display elements. In addition, the alignment agent can also be used with polyamine In addition to the liquid crystal alignment film, the polymer of the present invention can be applied to various polyimine coating agents or polyimine resin molded articles, films, or Fiber or the like. / ' The compound represented by the formula (1) of the present invention can be synthesized by the following method: (1) A is a single bond

(式中’ Q、R1、R2、R3及R4如前述，prt.為保護基團， T表示碳原子數1至8的直鏈或支鏈炫基。） 第1階段：式（卜1)所不的市售苯酚衍生物按照Bull. Chem.Soc. Jpn.，60,4187 (l987)或 Syn丨eU，1241(1997)等方 法進行溴化，以得到式（1-2)所示化合物。 第2階段：按照常法以甲基或装曱基等保護基保護式 (1-2)所示之化合物。 40 1343926 15190pif.doc 第 3 階段：按照 Organic Reaction, 22, 253 (1975)等， 將式（1-3)所示之化合物製成格林納試劑，與式（μ)所示之 醯氣化物發生偶聯反應’接著經酸水解，即可以得到式（丨_5) 所示之化合物。 第4階段：將式（1-5)所示之化合物經吩烧還原或 Wolff-Kishner還原變換為式（1-7)所示之化合物。 第5階段.按照常法’將式（1_7)所示之化合物以亞石黃 醯氣等化合物進行氯化’以得到式（1-8)所示之化合物，與 前述相同，藉由與式（1_9)所示之化合物反應得到式（ι_1〇) 所示之化合物。 第6階段：將式（1-10)所示之化合物經脫保護，可以 得到式(1 -11)所示化合物。化合物按照常法與無水三氟乙酸 等反應，得到式（1-12)所示化合物。 第 7 階段：藉由按照 Tetrahedron Lett.，38, 6367(1997) 等將三氟曱基磺酸酯基變換為胺基，可以得到式（1)所示之 化合物。 R1=R2及R3=R4的化合物，可以藉由上述反應中使用 2倍當量於式（1-4)所示化合物的式（1-3)所示化合物而更容 易合成。(wherein Q, R1, R2, R3 and R4 are as defined above, prt. is a protecting group, and T represents a linear or branched leuco having 1 to 8 carbon atoms.) Stage 1: Formula (Bu 1) The commercially available phenol derivative is brominated according to the method of Bull. Chem. Soc. Jpn., 60, 4187 (l987) or Syn丨eU, 1241 (1997) to obtain a compound of the formula (1-2). . Stage 2: The compound of the formula (1-2) is protected by a protecting group such as a methyl group or a fluorenyl group according to a conventional method. 40 1343926 15190pif.doc Stage 3: According to Organic Reaction, 22, 253 (1975), etc., the compound of formula (1-3) is made into a Grignard reagent, and the helium gas formed by formula (μ) occurs. The coupling reaction is followed by acid hydrolysis to give a compound of the formula (丨_5). Stage 4: The compound of the formula (1-5) is converted to the compound of the formula (1-7) by phenanthrene reduction or Wolff-Kishner reduction. In the fifth stage, the compound represented by the formula (1-7) is chlorinated with a compound such as sulphate or the like according to the usual method to obtain a compound represented by the formula (1-8), which is the same as defined above. The compound shown by (1_9) is reacted to obtain a compound represented by the formula (ι_1). Stage 6: The compound represented by the formula (1-10) is deprotected to give a compound of the formula (1-11). The compound is reacted with anhydrous trifluoroacetic acid or the like according to a usual method to give a compound of the formula (1-12). Stage 7: A compound represented by the formula (1) can be obtained by converting a trifluoromethyl sulfonate group to an amine group according to Tetrahedron Lett., 38, 6367 (1997) or the like. The compound of R1 = R2 and R3 = R4 can be more easily synthesized by using the compound of the formula (1-3) in which the compound represented by the formula (1-4) is used twice in the above reaction.

(2)A為1，4·亞苯基的情形 ， (式中，R5、R6、R7、R8表示氫、碳原子數1〜4的 烷基、烷氧基或氟。） 41 1343926 15l90pir.doc 式（1-12)所示之化合物可以按照J. Org. Chem.，58, 2201 (1993)及 Synthesis，735 (1993)的方法與式（ι_ΐ3)所示 之化合物表達的硼酸衍生物反應得到。此時，式（M3)所 示之化合物可以按照 J. Am. Chem. Soc., 80, 3609 (1958) 及 US4462819 得到。 本發明的式（1)所示化合物也可以藉由以下實施例所 示方法合成。 以下藉由實施例詳細說明利用本發明聚合物得到的 製品，即聚酿亞胺樹脂液晶配向劑。實施例中，全部反應 在氮氣氛圍中進行，利用GpC法測定分子量，使用聚苯乙 烯標準溶液，使用DMF作為溶出液進行測定。然而，本 發明並非限定於該等實施例。 液晶顯示元件的評價法 以下記載實施例中所用液晶顯示元件的評價法。 1.預傾角 、 利用晶體旋轉法進行。 2. 烙印(殘留 ,，^“三宅他信學技報EID9MU, P19，，中記載的方 诚二留1。使液晶盒上重疊50mV，1kHz的交流及 頻率0,0〇36Hz的吉、、ώ从-么山 直机的二角波而進行測定。殘留DC作為 各。總之，殘留DC越多越容易烙印。 3. 電壓保持率 載的他’第14回液晶討*會予稿集P78”中記 行。測定條件為振幅69/zs、頻率60H7、波高 42 1343926 15190piCdoc ±4.5V。 4. 液晶配向性與黑平衡 利用偏光顯微鏡目測進行。特別是黑平衡，在直交偏 光狀怨下與入射光與盒的摩擦方向相同的狀態下觀察。 5. 殘渣 ” 利用顯微鏡目測進行。 實施例1 (1，3-一(4-胺基-2-甲基苯基）丙烷；化合物N〇u的合 成） 首先’將4-溴-2-曱基苯曱醛(按照Chem Ber, 1〇2, 2493 (1969)合成)(1〇,〇8’5〇_〇1)、曱基（曱基硫）曱基亞石風 (12.4g ’ l〇〇mm〇l)與三曱基苯曱基氫氧化胺4〇%曱醇溶液 (10ml)的混合物回流5小時。 冷卻後’加入曱苯(5〇ml)及純水(5〇ml)進行抽提操 作。以0.5M硫酸水(5〇mi)及純水(5〇mix2)洗淨有機層，然 後以無水硫酸鎂乾燥有機層，之後，過濾及減壓蒸去溶劑 以得到粗結晶的化合物。於此化合物中加入乙醇(2〇ml)及 6MHC1(20ml)，回流5小時。然後，減壓蒸去溶劑後’將 所得到的殘潰以乙酸乙醋（5〇ml)及純水(50m丨)進行與上述 同樣的抽提操作，以得到粗產物，並以乙醇對粗產物進行 再結晶’即可得到產物4-溴-2-曱基苯基乙酸，其產率為 7.4g(64〇/〇)。 ' 接著’将上述之化合物(7.4g ’ 32mmol)及鐵粉(1.8g， 43 1343926 15190pitdoc 32mmol)於250°C下加熱30分鐘。冷卻後，加入甲苯 (100ml) ’並濾去不溶物。減壓蒸去曱苯後，將所得到的殘 渣以管柱層析法(column chromatography)(石夕耀/曱苯)精製， 即可得到產物1,3-二（4-溴-2-曱基苯基）-2-丙酮，其產率 為 3_8g(60%)。 然後’將化合物(3.8g，9.6mmol)、聯胺(hydrazine)l 水和物（l_9m卜 39mmol)及 KOH(0.77g，19mmol)的乙二醇 (l〇ml)溶液於140°C下攪拌1小時，然後於200°C下攪拌2 小時。冷卻後，以曱苯(5〇ml)及純水(50ml)進行抽提操作。 然後進行與上述相同的操作，以管枉層析法（矽膠/戊烷） 精製殘渣，即可得到產物1,3-二(4-溴-2-曱基苯基)丙烷， 其產率為3.4g(92%)。 之後，將上述之化合物(3.4g，8.9mmol)、二苯曱g同亞 胺(benzophenone imine)(3.9g，2lmmol)、乙酸把(palladium acetate)(40mg，0.18mmol)、2,2’ -二(二笨基膦)-l，l-二萘基 (BINAP)(166mg ，0.27mmo])及碳酸铯（cesium carbonate)(4.0g，12mmol)的混合物在曱苯(20ml)中回流7 小時。冷卻後，加入甲苯(40ml)及純水(5〇ml)進行抽提。然 後進行與上述相同的操作，以管柱層析法（矽膠/曱苯）精 製殘渣。化合物使用5%Pd/C、曱苯-乙醇(1:1，i〇〇mi)中 按照常法發生氫化分解反應。濾去催化劑後，減壓蒸去溶 劑，並將所得到的殘渣於乙醇中進行再結晶，即可得到產 物1，3-二（4-胺基-2-甲基苯基）丙烷/其產率為l.4g(61%)。 44 15l90pif.doc 實施例2 兩燒；化合物No.1-17的 (1，3-二（4-胺基-2-氟苯基） 合成。） 首无 _氟本基乙醆(8 〇g，34mm〇卜以特 開昭62-252774號公報中記栽的方法合成)及鐵粉， 34_丨μχ與實闕1囉的柯餘反應。並將所 的殘潰以管柱層析法(石夕膠/甲笨)精製，即可得到產物a 二(4-漠-2-氣苯基)-2-丙院，其產率為4 〇g(58%)。， ，’將^述之化合物經上述同樣變換得到產物^ 二(4-胺基-2-氟苯基)丙炫&gt;。 各階段的收率及精製條件如下所示。 W〇1ff-Kishner還原；精製：管柱層析_/戊 9Ω% ° -苯曱酮亞胺化m管柱層析(⑦膠/戍烧）。 氫化分解；精製：再結晶（乙醇）。產率：64%。 實施例3 (1，5_二（4-胺基-2-曱基苯基）丙烷；化合物No.1-35 的合成。） 首先’由4-&gt;臭-3-曱基苯曱醚(25g，ι24πιηι〇ι)及鎂 (3_3g ’ 135mmol)按照常法配製格林納試劑(溶劑THF)中於 0C以下加入碘化銅(24g，i26mm〇i)的THF(200ml)溶液。 進一步於（TC以下加入戊二醯政（1〇 5g，67mmoi)的 THF(50ml)溶液。在室溫下攪拌3〇分鐘後，於反應物中滴 45 1343926 15190pif.doc 入3N的HCl(lOOml)，並以曱笨進行與上述同樣的抽提操 ‘ 作。之後，將所得到的粗產物經管柱層析(矽膠/曱笨)精製， 即可得到產產物1，5-二（4-曱氧基-2-甲基苯基)_ι，5·戊二 酮，其產率為9.1g(43%)。 接著，在上述之化合物(9.0g，26mmol)、四氣曱燒 (19.4g，104mmol)及80ml二氣甲烧的混合物_，於室溫下 加入18_6ml(114mmol)的三曱基矽烷，室溫下攪拌2小時。 反應後’將反應混合物投入冰水中，接著與上述同樣進行 抽提操作。減壓蒸德去除反應生成的六乙基石夕氧炫後，即 可得到產物1，5-二(4-曱氧基-2-曱基苯基)戊烧。此化合物 沒有經過精製而用於以下的反應。 之後，在溶有化合物(8_3g，26mmol)的二氣曱烧(8〇ml) &gt;谷液中-，於50°C以下加入三漠化删（13g，52mmol)。室温 下攪拌1夜後，於反應物t加入純水(80ml)。然後與上述 同樣進行抽提操作後，經再結晶(環己烧），即可得到產物 1，5-二(4-羥基-2-曱基苯基)戊烷，其產率為6.3g(86%)。 接著’在溶有化合物(6.3g，22mmol)的。比咬(20ml)溶 液中’於0-5。(：下加入三氟曱基磺酸酐（13.7g，49mmol)。 室溫下攪拌1夜後，減壓蒸去吡啶，以曱苯-純水進行抽提 操作，然後將所得到的粗產物經管柱層析（矽膠/曱苯)精 製’即可得到產物1，5-二(4·三氟曱基su丨fonyloxy-2-曱基苯 基)戊烷，其產率為10.7g(89%)。 之後’將化合物(lO.Og，18mmol)'、二苯曱酮亞胺(7.3g， 4〇mmol)、乙酸鈀(81mg，〇,36mmol)、BINAP(332mg， 46 1343926 15190pir.doc 0.54mmol)及石发酸飽（16.8g，54mmol)的混合物在 THF(lOOml)中回流20小時。冷卻後，減壓蒸去溶劑後， 加入曱苯(200ml)及純水(200ml)以進行抽提。然後進行與上 述相同的操作，以管柱層析法(矽膠/曱苯)精製殘逢。上述 之化合物使用5%Pd/C、甲苯·乙醇(1:1 ’ 2〇〇ml)中按照常法 發生氫化分解反應。濾去催化劑後，減壓蒸去溶劑，將所 得到之殘渣於乙醇中進行再結晶，即可得到產物丨，5_二(4_ 胺基-2-甲基苯基)戊烧，其產率為2.3g(45%)。 實施例4 (1，5-二(4-(4·胺苯基）-2·曱基苯基）戊烷；化合物 No.1-118 的合成。） 實施例3中合成的〖，5-二(4-三氟曱基suif〇nyl〇xy-2_ 甲基苯基)戊烷(4.0g，7.3mmol)、按照 J‘Am. Chem. Soc.，80, 3609 (1958)合成的4-胺苯基硼酸(2.0g，15mm〇i)、四(三苯 基膦)鈀(0)(210mg，〇.i8mmol)與碳酸鈉(5.7g，54mmol)的 混合物於曱苯/乙醇/純水=1/1/1(v/v/v，6〇ml)中回流8小 時。冷卻後，以甲苯-純水系進行抽提操作。進行與上述同 樣的操作所得到的袓產物經管柱層析（矽膠/甲苯：甲醇 -20. 1)精製，即可得到產物以二……胺苯基甲基苯 基)戊烷，其產率為l.8g(57%)。 實施例4-2 ' (1,3 一(4 (4-胺苯基)苯基)丙烧；化合物n〇 moo的 47 1343926 15l90pif.doc 合成） 知:照WO8803134說明書合成的1，3-二（4·漠苯基）丙 烧(10.0g，28_〇l)、按照 j· Am Chem s〇c，8〇, 36〇9 (1958) 合成的4-胺苯基棚酸(7.7g，56mmol)、四（三苯基膦）把 (〇)(7=mg ’ 〇.67mmo丨）、碳酸鈉(21g，2〇〇mm〇丨）的混合物 於曱苯/乙醇/純水=l/1/1(v/v/v，3〇〇ml)中回流8小時。冷 卻^ ’以甲笨-純水系進行抽提操作。然後進行與上述同^ 的操作，並將所得到的粗產物經管柱層析(石夕膠/曱苯：曱 醇-20. 1)精製，即可得到產物13_二(4♦胺苯基)苯基） 丙烷’其產率為18g(54%)。 實施例5 (1，4-二(4-胺基_2_第三丁基苯氧基）丁烷；化合物 No.2-19的合成。） 使用按照J_ 0rg Chem，％，必，（1%8)記載方法合成 的4_硝基·2_第三丁基苯酚(4.8g，25mmol)及1,4-二溴丁烷 (2.6g，12mm〇1)，按照 J. Polym. Sci., Part A, Polym. Chem., 31, 1423(1993)同樣的方法合成。 實施例5-2 (((月女本基確胺）乙基)謎的合成；化合物Νο.4·6 的合成。） 首先’將4·硝基苯硫酚(20.0g，'129mmol)、2-氣*** (9.2g 64mm〇l)^ K2C03(21g » 150mmol)^ DMF(lOOml) 48 1343926 15lD0pif.doc 80J：反應4小時。冷卻後’反應液中加入純水(1〇〇ml) 及二氣曱烧(200ml) ’以進行抽提操作。接著，將有機層以 ，水(100ml)分2次洗淨’以無水硫酸鎂乾燥。過渡及減壓 ^去溶劑後，殘渣經管柱層析(矽膠/二氣曱烷)及再結晶（曱 笨）’即可得到產產物(2- (4-胺苯基續胺）乙基)趟，其產率 為 22g(910/〇)。 ' 接著將化合物(22g ’ 58mmol)及鐵粉(i9g，340mmol) 溶解於50°/〇乙醇水溶液(4〇mi)中，氮氣流下回流，並緩慢 滴下1N鹽酸的50%乙醇水溶液(2〇ml)。滴下後，進一步 回流3小時。冷卻後加入3〇%NaOH，調至pH12。於反應 液中加入二氣曱烷(l〇〇ml)，以鐵鋁酸四鈣(Cdite)過遽。之 後’將有機層以純水(100ml)分2次洗淨，以無水硫酸鎂乾 燥。過濾及減壓蒸去溶劑後’經管柱層析(秒膠/二氯甲院： 曱醇=1 : 1)及再結晶（乙醇)精製，即可得到產物，其產率 為 14g (74%)。 實施例5-3 (1，4-二(4’-胺基二苯基-4-續胺）丁烧的合成；化合物 No.3-64的合成） 除以 J. Am. Chem. Soc.，200, 122 (3688)中所記載的 4-(4-硝基苯基)苯硫盼替代4-琐基苯硫盼以及用ι,4-二漠 丁烷替代2·氯***之外，與實施例5-2同樣方法進行合 成，總產率54%。 ’ 49 1343926 15190pif.doc 實施例6 (聚醯胺酸6及含有此聚醯胺酸6的液晶配向劑6的配 * 製） . 首先，於配有攪拌器、氮氣導入口、溫度計及原料導 入口的100ml之四口燒瓶中，投入i MSgGJOOmmol)之溶 解於10g的NMP中的實施例1中合成的1,3_二(4_胺基-2-曱基苯基）丙烷。然後，於此溶液中加入〇 4908g(2.250mmol) 的苯均四酸二酐（以下稱為 Pyromellitic dianhydride，PMDA) 及0.4412g(2.250mmol)的ι，2,3,4-環丁烷四羧酸二針(以下 鲁 稱為CBTA)，攪拌6小時。其後，以29g的NMP稀釋前 述之溶液’即可得到聚醯胺酸濃度約為5重量百分比的透 明溶液。上述之聚合物的重量平均分子量為5 6萬，溶液 的粘度為35mPa.s(25°C)。其中’此溶液作為液晶配向劑6。 實施例7 (聚醯胺酸7及含有此聚醯胺酸7的液晶配向劑7的配 製） 離 除以1.1803g(4.500mmol)之實施例2中合成的1,3-二 (4-胺基-2-氟苯基）丙烷替代ι,3·二(4·胺基_2_曱基苯基）丙 , 烷以外，按照實施例5的合成方法得到清漆(vamish)。上 述之聚合物的重量平均分子量為55萬，溶液的粘度為 32mPa.s(25C)。其中，此溶液以下作為液晶配向劑7。 實施例8 50 1343926 15190pif.doc (聚醒亞胺及含有此聚醯亞胺的液晶配向劑8的配製） 以實施例6的方法配製的清漆1中加入4_6g(45mmol) 無水乙酸，100°C反應1小時。冷卻後，反應液加入i〇0ml 純水，過濾得到生成的沉淀。沉淀以純水(25ml)及甲醇 (25ml)洗淨、真空乾燥，得到聚醯亞胺。物性評價中使用 聚合物溶解於NMP所得的濃度5%溶液。此溶液於下述中 作為液晶配向劑8。如圖1所示，其是實施例6中合成的 聚醯胺酸於曱醇中再沉澱、過濾、真空加熱乾燥所得樣品 的紅外吸收光譜。 以實施例6及實施例7中的方法，配製表a中所示 的液晶配向劑。 實施例 (液晶液晶 配向劑） •胺 a) δ交酐b&gt; 枯度（mPa-s)/ 分子量(ΧΙΟ·3)(2) In the case where A is a 1,4-phenylene group, (wherein R5, R6, R7, and R8 represent hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or fluorine). 41 1343926 15l90pir. Doc The compound of the formula (1-12) can be reacted with a boronic acid derivative expressed by a compound represented by the formula (ι_ΐ3) according to the method of J. Org. Chem., 58, 2201 (1993) and Synthesis, 735 (1993). get. In this case, the compound of the formula (M3) can be obtained in accordance with J. Am. Chem. Soc., 80, 3609 (1958) and US4462819. The compound of the formula (1) of the present invention can also be synthesized by the methods shown in the following examples. Hereinafter, an article obtained by using the polymer of the present invention, i.e., a polyimide resin liquid crystal alignment agent, will be described in detail by way of examples. In the examples, all the reactions were carried out in a nitrogen atmosphere, and the molecular weight was measured by a GpC method, and the measurement was carried out using DMF as a solution using a polystyrene standard solution. However, the invention is not limited to the embodiments. Evaluation Method of Liquid Crystal Display Element The evaluation method of the liquid crystal display element used in the examples is described below. 1. Pretilt angle, using the crystal rotation method. 2. Branding (residual, ^^" Miyake Thaksin's technical report EID9MU, P19, the Fang Cheng 2 left in the record 1. Make the LCD box overlap 50mV, 1kHz AC and frequency 0,0〇36Hz Ji,, ώThe measurement is carried out from the two-angle wave of the Moshan straight machine. The residual DC is used as the each. In short, the more the residual DC is, the easier it is to imprint. 3. The voltage retention rate of the '14th LCD will be submitted to the P78. Zhong Kexing. The measurement conditions are amplitude 69/zs, frequency 60H7, wave height 42 1343926 15190piCdoc ±4.5V. 4. Liquid crystal alignment and black balance are measured by polarized light microscopy. Especially black balance, under orthogonal polarized resentment and incident The light was observed in the same state as the rubbing direction of the cell. 5. Residues were visually observed by a microscope. Example 1 (1,3-A(4-Amino-2-methylphenyl)propane; Compound N〇u Synthesis) First, '4-bromo-2-mercaptophenylfurfural (synthesized according to Chem Ber, 1〇2, 2493 (1969)) (1〇, 〇8'5〇_〇1), fluorenyl (fluorenyl) A mixture of sulfur) sulfhydryl wind (12.4 g 'l〇〇mm〇l) and trimethylphenyl hydrazinamide 4 〇% decyl alcohol solution (10 ml) was refluxed for 5 hours. After the 'addition of toluene (5 〇 ml) and pure water (5 〇 ml) for extraction. Wash the organic layer with 0.5M sulphuric acid water (5 〇mi) and pure water (5 〇 mix2), then anhydrous sulfuric acid The organic layer was dried over magnesium sulfate, and the solvent was evaporated to give crystals of crystals of crystals of crystals to give crystals of crude crystals, and ethyl alcohol (2 mM) and 6 MHCI (20 ml), and refluxed for 5 hours. 'The obtained residue was subjected to the same extraction operation as above in ethyl acetate (5 ml) and pure water (50 m) to obtain a crude product, which was recrystallized from ethanol. The product 4-bromo-2-indolylphenylacetic acid was obtained in a yield of 7.4 g (64 〇/〇). 'Next' the above compound (7.4g '32mmol) and iron powder (1.8g, 43 1343926 15190pitdoc 32mmol) After heating at 250 ° C for 30 minutes, after cooling, toluene (100 ml) was added and the insoluble matter was filtered off. After the distillation of the benzene was carried out under reduced pressure, the obtained residue was subjected to column chromatography. The product is purified by trituration to obtain the product 1,3-bis(4-bromo-2-indolylphenyl)-2-propanone in a yield of 3-8 g (60%). (3.8 g, 9.6 mmol), hydrazine 1 water and (1-9 m, 39 mmol) and KOH (0.77 g, 19 mmol) in ethylene glycol (10 ml) were stirred at 140 ° C for 1 hour, then Stir at 200 ° C for 2 hours. After cooling, extraction was carried out with terpene (5 〇 ml) and pure water (50 ml). Then, the same operation as above was carried out, and the residue was purified by column chromatography (gelatin/pentane) to obtain the product 1,3-bis(4-bromo-2-indolylphenyl)propane in the yield. 3.4 g (92%). Thereafter, the above compound (3.4 g, 8.9 mmol), benzophenone imine (3.9 g, 2 l mmol), palladium acetate (40 mg, 0.18 mmol), 2, 2' - A mixture of bis(diphenylphosphine)-1,1-diphthyl (BINAP) (166 mg, 0.27 mmol) and cesium carbonate (4.0 g, 12 mmol) was refluxed in toluene (20 ml) for 7 hours. . After cooling, toluene (40 ml) and pure water (5 〇 ml) were added for extraction. Then, the same operation as above was carried out, and the residue was purified by column chromatography (tank/benzene). The compound was subjected to a hydrogenation decomposition reaction in a usual manner using 5% Pd/C, toluene-ethanol (1:1, i〇〇mi). After filtering off the catalyst, the solvent is evaporated under reduced pressure, and the obtained residue is recrystallized from ethanol to give the product 1,3-bis(4-amino-2-methylphenyl)propane / The rate was 1.4 g (61%). 44 15l90pif.doc Example 2 Two-burning; (1,3-di(4-amino-2-fluorophenyl)) of compound No. 1-17.) No _fluorobenzidine (8 〇g) 34mm 合成 以 合成 62 62 62 62-252774 合成 的 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 62 。 。 The residue was purified by column chromatography (Shishijiao/Jia), and the product a bis(4-dihydro-2-phenyl)-2-propanol was obtained in a yield of 4 〇g (58%). The compound described above was converted in the same manner as above to give the product bis(4-amino-2-fluorophenyl)propane&gt;. The yield and purification conditions at each stage are as follows. W〇1ff-Kishner reduction; refining: column chromatography _ / pent 9 Ω% ° - benzophenone imidization m column chromatography (7 gel / smoldering). Hydrogenation decomposition; refining: recrystallization (ethanol). Yield: 64%. Example 3 (1,5-bis(4-Amino-2-mercaptophenyl)propane; Synthesis of Compound No. 1-35.) First 'from 4-&gt; odor-3-mercaptophenyl oxime ether (25g, ι24πιηι〇ι) and magnesium (3_3g '135mmol) A solution of copper iodide (24g, i26mm〇i) in THF (200ml) was added to the Grignard reagent (solvent THF) according to the usual procedure below 0C. Further, a solution of pentane oxime (1〇5g, 67mmoi) in THF (50ml) was added below (TC). After stirring at room temperature for 3 minutes, 45 1343926 15190 pif.doc was added to the reaction solution to 3N HCl (100 ml). And the same extraction operation as above is carried out in a sturdy manner. After that, the obtained crude product is purified by column chromatography (silicone/small) to obtain the product 1,5-di (4-曱oxy-2-methylphenyl)_ι,5·pentanedione, the yield was 9.1 g (43%). Next, the above compound (9.0 g, 26 mmol), tetrakisole (19.4 g) , 104 mmol) and 80 ml of a mixture of methane, _, and added 18_6 ml (114 mmol) of tridecyl decane at room temperature, and stirred at room temperature for 2 hours. After the reaction, the reaction mixture was poured into ice water, followed by the same procedure as above. The extraction operation is carried out by vacuum distillation to remove the hexaethyl oxaxanide produced by the reaction, thereby obtaining the product 1,5-bis(4-decyloxy-2-mercaptophenyl) pentane. It is purified and used in the following reaction. After that, in the solution of the compound (8_3g, 26mmol) in dioxane (8〇ml) &gt; trough liquid, add three desertification below 50 °C. (13 g, 52 mmol). After stirring at room temperature for 1 night, pure water (80 ml) was added to the reactant t. Then, after the extraction operation was carried out in the same manner as above, the product was obtained by recrystallization (cyclohexane). - bis(4-hydroxy-2-mercaptophenyl)pentane in a yield of 6.3 g (86%) followed by 'in solution of compound (6.3 g, 22 mmol) in a bite (20 ml) solution' 0-5. (: Trifluoromethanesulfonic anhydride (13.7 g, 49 mmol) was added. After stirring at room temperature for 1 night, pyridine was evaporated under reduced pressure, and extracted with benzene-pure water. The obtained crude product is purified by column chromatography (tank / benzene) to give the product 1,5-bis(4.trifluoromethyl]su丨fonyloxy-2-mercaptophenyl)pentane in the yield. 10.7 g (89%). Then 'Compound (lO.Og, 18 mmol)', benzophenone imine (7.3 g, 4 mmol), palladium acetate (81 mg, hydrazine, 36 mmol), BINAP (332 mg, 46) A mixture of 1343926 15190 pir.doc (0.54 mmol) and sulphuric acid (16.8 g, 54 mmol) was refluxed in THF (100 ml) for 20 hr. After cooling, the solvent was evaporated under reduced pressure, and then toluene (200 ml) and purified water (200 ml) ) for extraction. Then proceed as above Operation, by column chromatography (silica gel / benzene Yue) every residue was purified compound of the above 5% Pd / C, toluene-ethanol: hydrogenation decomposition reaction (11 '2〇〇ml) occurs by a known method. After filtering off the catalyst, the solvent was evaporated under reduced pressure, and the obtained residue was recrystallized from ethanol to give the product hydrazine, 5-di(4-amino-2-methylphenyl)pentane. It is 2.3 g (45%). Example 4 (1,5-bis(4-(4-aminophenyl)-2.nonylphenyl)pentane; Synthesis of Compound No. 1-118.) Synthesis of Example 3, 5- Bis(4-trifluorodecyl suif〇nyl〇xy-2_methylphenyl)pentane (4.0 g, 7.3 mmol), 4- synthesized according to J'Am. Chem. Soc., 80, 3609 (1958) a mixture of aminophenylboronic acid (2.0 g, 15 mm 〇i), tetrakis(triphenylphosphine)palladium(0) (210 mg, 〇.i8 mmol) and sodium carbonate (5.7 g, 54 mmol) in toluene/ethanol/pure water Reflux for 8 hours in =1/1/1 (v/v/v, 6 〇ml). After cooling, the extraction operation was carried out in a toluene-pure water system. The hydrazine product obtained by the same operation as above is purified by column chromatography (gelatin/toluene:methanol -0.1) to obtain the product as bis-aminophenylmethylphenylpentane. It is l.8g (57%). Example 4-2 '(1,3-(4 (4-Aminophenyl)phenyl)propane; Compound n〇moo 47 1343926 15l90pif.doc Synthesis) Know: 1,3-two synthesized according to the specification of WO8803134 (4. Desert phenyl) Propylene (10.0g, 28_〇l), 4-amine phenyl arsenic acid (7.7g, synthesized according to j· Am Chem s〇c, 8〇, 36〇9 (1958) 56mmol), tetrakis(triphenylphosphine) a mixture of (〇) (7=mg '〇.67mmo丨), sodium carbonate (21g, 2〇〇mm〇丨) in toluene/ethanol/pure water=l/ Reflux was carried out for 8 hours in 1/1 (v/v/v, 3 〇〇 ml). The cold is ^', and the extraction operation is carried out in a stupid-pure water system. Then, the same operation as above is carried out, and the obtained crude product is purified by column chromatography (Shixijiao/Phenylbenzene:nonanol-20.1) to obtain the product 13_2 (4♦ amine phenyl group). The yield of phenyl)propane was 18 g (54%). Example 5 (1,4-Di(4-amino-2-t-butylphenoxy)butane; Synthesis of Compound No. 2-19.) Use according to J_0rg Chem, %, mandatory, (1 %8) 4-_nitro-2_t-butylphenol (4.8 g, 25 mmol) synthesized by the method and 1,4-dibromobutane (2.6 g, 12 mm 〇1), according to J. Polym. Sci. , Part A, Polym. Chem., 31, 1423 (1993) synthesized by the same method. Example 5-2 (((Journal of Erythramine)ethyl) mystery synthesis; synthesis of compound Νο.4·6.) First '4 nitrothiophenol (20.0 g, '129 mmol), 2-air diethyl ether (9.2 g 64 mm 〇l) ^ K2C03 (21 g » 150 mmol) ^ DMF (lOOml) 48 1343926 15lD0pif.doc 80J: reaction for 4 hours. After cooling, pure water (1 ml) and dioxane (200 ml) were added to the reaction mixture to carry out an extraction operation. Next, the organic layer was washed with water (100 ml) twice and dried over anhydrous magnesium sulfate. After the transition and depressurization, the solvent is removed, and the residue is subjected to column chromatography (ruthenium / dioxane) and recrystallization (曱 )) to obtain the product (2-(4-aminophenyl)-ethyl) The yield was 22 g (910/〇). Then, the compound (22 g '58 mmol) and iron powder (i9g, 340 mmol) were dissolved in a 50 ° / 〇 aqueous ethanol solution (4 〇mi), refluxed under a nitrogen stream, and a 1 N hydrochloric acid in 50% aqueous ethanol solution (2 〇 ml) was slowly dropped. ). After the dropwise addition, it was further refluxed for 3 hours. After cooling, 3% NaOH was added and adjusted to pH 12. Dioxane (10 ml) was added to the reaction solution, and the mixture was ferric with tetracalcium iron aluminate (Cdite). Thereafter, the organic layer was washed twice with pure water (100 ml) and dried over anhydrous magnesium sulfate. After filtration and evaporation of the solvent under reduced pressure, the product was obtained by column chromatography (second gel/dichlorocarbazide: decyl alcohol = 1 : 1) and recrystallization (ethanol), and the yield was 14 g (74%). ). Example 5-3 (Synthesis of 1,4-bis(4'-aminodiphenyl-4-transamine) butylate; Synthesis of Compound No. 3-64) Divided by J. Am. Chem. Soc. , 4-(4-nitrophenyl)benzenethione as described in 200, 122 (3688), in place of 4-zinophenylthiophene, and in place of 2,chloroethyl ether with ι,4-dihydrobutane, The synthesis was carried out in the same manner as in Example 5-2, with a total yield of 54%. '49 1343926 15190pif.doc Example 6 (Polymeric acid 6 and liquid crystal alignment agent 6 containing the poly-proline 6) First, with a stirrer, a nitrogen inlet, a thermometer, and a raw material introduction The 1,3_bis(4-amino-2-mercaptophenyl)propane synthesized in Example 1 dissolved in 10 g of NMP was placed in a 100 ml four-necked flask of the mouth. Then, 4908 g (2.250 mmol) of pyromellitic dianhydride (hereinafter referred to as Pyromellitic dianhydride, PMDA) and 0.4412 g (2.250 mmol) of iota, 2,3,4-cyclobutane tetracarboxylate were added to the solution. The acid two needles (hereinafter referred to as CBTA) were stirred for 6 hours. Thereafter, the above solution was diluted with 29 g of NMP to obtain a transparent solution having a polyglycine concentration of about 5 wt%. The above polymer had a weight average molecular weight of 56,000 and a solution viscosity of 35 mPa.s (25 ° C). Wherein this solution serves as the liquid crystal alignment agent 6. Example 7 (Preparation of polyproline 7 and liquid crystal alignment agent 7 containing the polyamic acid 7) The 1,3-bis(4-amine synthesized in Example 2 was separated by 1.1803 g (4.500 mmol). A varnish was obtained according to the synthesis method of Example 5, except that i.sub.2-fluorophenyl)propane was replaced by i.sub.3, bis(4.amino-2-indolylphenyl)propane. The above polymer had a weight average molecular weight of 550,000 and a solution viscosity of 32 mPa.s (25C). Among them, this solution is hereinafter referred to as a liquid crystal alignment agent 7. Example 8 50 1343926 15190 pif.doc (Preparation of polyamidimide and liquid crystal alignment agent 8 containing the polyimine) To the varnish 1 prepared by the method of Example 6, 4-6 g (45 mmol) of anhydrous acetic acid was added, 100 ° C Reaction for 1 hour. After cooling, the reaction solution was added with 0 ml of pure water, and filtered to give a formed precipitate. The precipitate was washed with pure water (25 ml) and methanol (25 ml) and dried in vacuo to give a polyimine. For the physical property evaluation, a 5% solution obtained by dissolving the polymer in NMP was used. This solution was used as the liquid crystal alignment agent 8 in the following. As shown in Fig. 1, it is an infrared absorption spectrum of a sample obtained by reprecipitation, filtration, and vacuum heating of the polylysine synthesized in Example 6 in decyl alcohol. The liquid crystal alignment agents shown in Table a were prepared in the same manner as in Example 6 and Example 7. EXAMPLES (Liquid crystal liquid crystal alignment agent) • Amine a) δ-hydroxy anhydride b&gt; Dryness (mPa-s) / molecular weight (ΧΙΟ·3)

{表18】配製的液晶配向，丨(括號内為分比） 51 1343926 15l9〇pifd〇c 實施例22 ‘ 將l〇g的實施例6方法配製的液晶配向劑6與6 7g的. BC加入。到螺旋口小瓶中，得到濃度約3重量百分比的溶 液。在單面設製有ΙΤΟ電極的透明玻璃基板上，滴入上述 之/谷液，經旋轉塗膜法塗佈(25〇〇rpm，15秒）。塗佈後， 在80 C下加熱5分鐘，热發溶劑後，再於烤箱中以25〇。〇 進行加熱處理30分鐘，即可得到約6〇nm的聚醯亞胺樹脂 薄膜。接著，摩擦處理此形成有樹脂薄膜的玻璃基板，並 ，與摩擦方向逆平行方向以使2片玻璃基板貼合，並組成· 盒厚為2〇Um的液晶盒。由下述化合物組成的液晶組合物 A ’主入„亥孟中，於n〇c進行3〇分鐘的各向同性處理，然 後々卻至至溫即可得到液晶顯示元件。液晶顯示元件的殘 留 DC25°C 為 0.25V，20、60 及 9(TC 時，其 VHR 分別為 99.6、98.9、96.7%。再者’使用顯示元件測定預傾角的結 果為1.2度。另外，進一步以顯微鏡觀察，其結果沒有觀 察到液晶的配向缺陷，而黑平衡也良好’且也沒有觀察到 殘渣（以下，以上述之測定值作為初值）。 將此盒於1UTC下靜置20小時，冷卻至室溫後，再測 · 定上述之值。其結果是殘留DC為〇.26V(25°C)，VHR為 9^5(20)、98.5(60)、96.3%(90。〇，預傾角為 u 度。再者 . 沒有觀察到液晶的配向缺陷，而黑平衡也良好，且進—步 也’又有觀察到殘渣（以下，以上述之測定值作為加熱後值）。 52 1343926 15100pif.doc{Table 18] Formulated liquid crystal alignment, 丨 (in parentheses) 51 1343926 15l9〇pifd〇c Example 22 'The liquid crystal alignment agent 6 prepared by the method of Example 6 was added to 6.7 g of BC. . Into the screw-bottom vial, a solution having a concentration of about 3 weight percent was obtained. On the transparent glass substrate provided with the ruthenium electrode on one side, the above-mentioned / gluten solution was dropped, and it was applied by a spin coating method (25 rpm, 15 seconds). After coating, it was heated at 80 C for 5 minutes, and after hot solvent, it was again 25 Torr in an oven.进行 Heat treatment for 30 minutes gives a polyimide film of about 6 〇 nm. Then, the glass substrate on which the resin film was formed was rubbed, and two glass substrates were bonded in a direction parallel to the rubbing direction to form a liquid crystal cell having a cell thickness of 2 〇Um. The liquid crystal composition A' consisting of the following compound is mainly introduced into the haimen, and is subjected to isotropic treatment for 3 minutes at n〇c, and then the liquid crystal display element is obtained by enthalpy until the temperature is reached. Residue of the liquid crystal display element DC25°C is 0.25V, 20, 60, and 9 (when TC, the VHR is 99.6, 98.9, and 96.7%, respectively. The result of measuring the pretilt angle using the display element is 1.2 degrees. In addition, it is further observed by a microscope. As a result, no alignment defect of the liquid crystal was observed, and the black balance was also good, and no residue was observed (hereinafter, the above-mentioned measured value was used as the initial value). The cartridge was allowed to stand at 1 UTC for 20 hours, and cooled to room temperature. Then, the above values are determined. The result is that the residual DC is 〇.26V (25°C), VHR is 9^5(20), 98.5(60), 96.3% (90.〇, pretilt angle is u degree Furthermore, no alignment defect of the liquid crystal was observed, and the black balance was also good, and the residue was observed again (hereinafter, the above measured value was used as the heating value). 52 1343926 15100pif.doc

液晶組合物A· FLiquid crystal composition A·F

17 wt% 17wt% 16wt%17 wt% 17wt% 16wt%

10 wt% 5wt°/〇 10 wt%10 wt% 5wt°/〇 10 wt%

FF

6wt% 6wt% 13 wt%6wt% 6wt% 13 wt%

實施例23 除使用液晶配向劑7替代液晶配向劑6之外，以實施 例22的方法製作液晶顯示元件，並測定其特性。 初值：殘留 DC : 0.29V，VHR : 99.1(20)、96.3(60)、 94.9%(90°C)，預傾角：1.3度，無紇向缺陷及殘渣，黑平 衡良好。 53 1343926 15190pif.doc 加熱後值··殘留 DC : 0.30V，VHR : 99.0(20)、96.2(60)、 94.7%(90°C)，預傾角：1.2度，無配向缺陷及殘渣，黑平 衡良好。 以實施例22及實施例23為基準製作以下液晶顯示元 件，並測定其特性。 【表19】 實施例 配向劑 條件 殘留 VHR(%) 預傾角 δ己向 黑平 殘渣 DC(V) 2〇°c 60°C 90 °C (度） 缺陷 衝 24 8 初期 0.24 99.3 98.1 96.7 1.1 無 良 無 加熱後 0.25 99.1 98.0 96.8 1.2 無 良 無 26 14 初期 0.46 98.8 96.5 95.0 1.5 無 良 無 加熱後 0.58 98.7 96.4 94.7 1.6 無 良 無 28 18 初期 0.19 99.0 98.0 96.7 1.0 無 良 無 加熱後 0.24 99.1 97.9 96.5 1.2 無 良 無 28-2 21-2 初期 0.09 96.4 95.7 93.4 0.8 無 良 無 加熱後 0.10 96.4 94.4 92.5 0.9 無 良 無 28-3 21-3 初期 0.08 96.0 95.0 92.7 1.3 無 良 無 加熱後 0.08 96.1 94.9 92.6 1.3 無 良 無 實施例28 除使用液晶配向劑6與液晶配向劑21的混合物(液晶 配向劑6 :液晶配向劑21 = 10 : 1(重量比))替代液晶配向劑 6之外，以實施例22的方法製作液晶顯示元件，並測定特 性。 初值：殘留 DC : 0.48V，VHR ; 98.4(20)、97.4(60)、 95.2%(90°C)，預傾角：7.5度。無配向缺陷。黑平衡良好。 加熱後值：殘留 DC : 0.53V，VHR: 98.3(20)、97.5(60)、 54 1343926 15190pif.doc 94.5%(90°C)，預傾角·· 7.6度，無配向缺陷，黑平衡良好。 比較例1 按照專利第1587418號，使用化合物No.4-2及化合物 No.5-13 ’並以實施例6的方法配製液晶配向劑A。除使用 液晶配向劑A替代液晶配向劑6之外，以實施例22的方 法製作液晶顯示元件’測定特性。其結果示於表20中。 【表20】配向膜特性 條件 殘留 VHR(%) 預傾角 S己向 黑平 殘渣 DC(V) 20°C 60 °C 90°C (度） 缺陷 衡 初期 0.75 98.6 97.3 95,5 1.5 有 不良 無 加熱後 0.84 98.4 96.6 95.5 1.4 有 不良 無 由實施例22至實施例27與比較例1的比較可知，使 用本發明的液晶配向劑，可以製作無殘留DC及等特 性惡化現象、配向性及黑平衡良好的顯示元件。 比較例2 按照特開平5-43687號公報，按照實施例6的方法以 下列組分配製液晶配向劑B。除使用液晶配向劑B替代液 晶配向劑6之外，以實施例22的方法製作液晶顯示元件， 測定特性。其結果示於表21中。 55 1343926 15190pif.doc 酸肝化合物：化合物No. 4-1 100莫耳百分比 二胺： 化合物No. 5-8 80莫耳百分比 化合物No. 5-11 20莫耳百分比 【参21】配向膜特性 殘留DC (V) VHR(%) 預傾角 (度） 配向 缺陷 黑平衡 殘渣 20 eC 60°C 90°C 初期 1.25 97.4 96.1 93.5 5.3 有 不良 無 1.09 97.1 95.4 93.1 5.0 有 不良 無 由實施例29與比較例2的比較可知，即使是具有相 同大小預傾角的配向膜，本發明的液晶配向膜的殘留 E)C(V)少、VHR高。再者，由比較結果可知液晶的配向性 良好。 比較例3 按照專利第3169062號，以實施例6的方法以下列組 分配製液晶配向劑C。除使用液晶配向劑C替代液晶配向 劍6之外，以實施例22的方法製作液晶顯示元件，測定特 性。其結果示於表22中。 酸酐化合物：化合物Νο·4-1(表1) 1〇〇莫耳百分比 ； 刚莫耳百分比 56 1343926 15l90pif.doc 【表22】配向膜特性 條件 殘留DC (V) VHR(% 預傾角 (度） 配向 缺陷 黑平衡 殘渣 20 °C 60°C 90°C 初期 0.42 95.2 94.2 91.8 1.3 無 良 無 加熱後 0.48 95.0 94.4 91.1 1.2 無 良 無 由實施例26與比較例3的比較可知，本發明的液晶 配向劑的VHR高。 產業上利用可行性 本發明的液晶配向劑，表現穩定的預傾角、具有高的 電壓保持率(VHR)、殘留DC少、不易發生顯示波動等、 南水準滿足液晶顯示元件所要求的諸特性，特別是表現優 異配向性的液晶配向劑。 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 =範圍内，當可作些許之更動與潤飾，因此本發明之保譚 範圍當視後附之申請專利範圍所界定者為準。 ，、又 【圖式簡單說明】 圖1是實施例6中合成的聚醯胺酸於甲醇中 過濾、真空加熱乾燥所得樣品的紅外吸收光譜。儿&quot;、又 【主要元件符號說明】 益 57Example 23 A liquid crystal display device was produced in the same manner as in Example 22 except that the liquid crystal alignment agent 7 was used instead of the liquid crystal alignment agent 6, and the properties were measured. Initial value: Residual DC: 0.29V, VHR: 99.1 (20), 96.3 (60), 94.9% (90 ° C), pretilt angle: 1.3 degrees, no defects and residue, black balance is good. 53 1343926 15190pif.doc Value after heating · Residual DC : 0.30V, VHR : 99.0 (20), 96.2 (60), 94.7% (90 ° C), pretilt angle: 1.2 degrees, no alignment defects and residue, black balance good. The following liquid crystal display elements were produced on the basis of Example 22 and Example 23, and their characteristics were measured. [Table 19] Example Reagent Condition Residual VHR (%) Pretilt angle δ has been black residue DC (V) 2 〇 ° c 60 ° C 90 ° C (degrees) Defect rush 24 8 Initial 0.24 99.3 98.1 96.7 1.1 None Good without heating 0.25 99.1 98.0 96.8 1.2 No good 26 14 Initial 0.46 98.8 96.5 95.0 1.5 No good without heating 0.58 98.7 96.4 94.7 1.6 No good 28 18 Initial 0.19 99.0 98.0 96.7 1.0 No good after heating 0.24 99.1 97.9 96.5 1.2 无良无28-2 21-2 Initial 0.09 96.4 95.7 93.4 0.8 No good after heating 0.10 96.4 94.4 92.5 0.9 No good 28-3 21-3 Initial 0.08 96.0 95.0 92.7 1.3 No good after heating 0.08 96.1 94.9 92.6 1.3 Nothing Example 28 In addition to the use of a mixture of the liquid crystal alignment agent 6 and the liquid crystal alignment agent 21 (liquid crystal alignment agent 6: liquid crystal alignment agent 21 = 10:1 (weight ratio)) instead of the liquid crystal alignment agent 6, by way of example The method of 22 was to produce a liquid crystal display element, and the characteristics were measured. Initial value: residual DC: 0.48V, VHR; 98.4 (20), 97.4 (60), 95.2% (90 ° C), pretilt angle: 7.5 degrees. No alignment defects. The black balance is good. After heating: residual DC: 0.53V, VHR: 98.3 (20), 97.5 (60), 54 1343926 15190 pif.doc 94.5% (90 ° C), pretilt angle · 7.6 degrees, no alignment defects, good black balance. Comparative Example 1 Liquid crystal alignment agent A was prepared in the same manner as in Example 6 according to Patent No. 1587418, using Compound No. 4-2 and Compound No. 5-13'. The measurement characteristics of the liquid crystal display element were produced by the method of Example 22 except that the liquid crystal alignment agent A was used instead of the liquid crystal alignment agent 6. The results are shown in Table 20. [Table 20] Alignment film characteristic condition residual VHR (%) Pretilt angle S to black flat residue DC (V) 20 ° C 60 ° C 90 ° C (degrees) Defective balance initial 0.75 98.6 97.3 95,5 1.5 After heating, 0.84 98.4 96.6 95.5 1.4 There is no defect. From the comparison of Example 22 to Example 27 with Comparative Example 1, it is understood that the use of the liquid crystal alignment agent of the present invention can produce no residual DC and other characteristics deterioration, alignment and black balance. Good display elements. Comparative Example 2 A liquid crystal alignment agent B was prepared in accordance with the method of Example 6 in accordance with the method of Example 6 in accordance with JP-A-H05-43687. A liquid crystal display element was produced by the method of Example 22 except that the liquid crystal alignment agent B was used instead of the liquid crystal alignment agent 6, and the characteristics were measured. The results are shown in Table 21. 55 1343926 15190pif.doc Acid liver compound: Compound No. 4-1 100 mole percent diamine: Compound No. 5-8 80 mole percentage compound No. 5-11 20 mole percentage [Ref 21] alignment film characteristic residue DC (V) VHR (%) Pretilt angle (degrees) Alignment defect black balance residue 20 eC 60 ° C 90 ° C Initial 1.25 97.4 96.1 93.5 5.3 There is no defect 1.09 97.1 95.4 93.1 5.0 There is no defect No. 29 and comparative example As is clear from 2, even in the alignment film having the pretilt angle of the same size, the liquid crystal alignment film of the present invention has a small E) C (V) and a high VHR. Further, from the comparison results, it was found that the alignment of the liquid crystal was good. Comparative Example 3 Liquid crystal alignment agent C was formulated in the following manner in the same manner as in Example 6 in accordance with Patent No. 3,169,062. A liquid crystal display element was produced by the method of Example 22 except that the liquid crystal alignment agent C was used instead of the liquid crystal alignment sword 6, and the characteristics were measured. The results are shown in Table 22. Anhydride compound: compound Νο·4-1 (Table 1) 1% molar percentage; percentage of just Molar 56 1343926 15l90pif.doc [Table 22] Alignment film characteristic condition residual DC (V) VHR (% pretilt angle (degrees) Alignment defect black balance residue 20 ° C 60 ° C 90 ° C initial 0.42 95.2 94.2 91.8 1.3 no good after no heating 0.48 95.0 94.4 91.1 1.2 no good by comparison of example 26 and comparative example 3, the liquid crystal alignment of the present invention The liquid crystal alignment agent of the present invention exhibits a stable pretilt angle, has a high voltage holding ratio (VHR), has a small residual DC, and is less likely to cause display fluctuations, etc., and the south level satisfies the liquid crystal display element. The required characteristics, particularly the liquid crystal alignment agent which exhibits excellent alignment. Although the invention has been disclosed in the preferred embodiments as above, it is not intended to limit the invention, and any person skilled in the art without departing from the spirit of the invention Within the scope of the invention, the scope of the protection of the present invention is subject to the definition of the patent application scope. FIG 1 is a polyamide acid synthesized in Example 6 in methanol embodiment filtered, dried under vacuum resulting sample was heated infrared absorption spectrum of children &quot;, and reference numerals DESCRIPTION Main benefits 57

Claims (1)

1343926 15190pif.doc 爲第93132516號中文專利範圍無劃線修 十、申請專利範圍： 修正日期:100年3月24日 ^ ...... · ·. —V · · L h一種二胺’具有式（1)所示的結構：1343926 15190pif.doc For the Chinese patent scope of No. 93132516, there is no underline repair, the scope of application for patent: Revision date: March 24, 100 ^ ...... · ·. -V · · L h a diamine The structure shown in formula (1): 式⑴令 ’ Q 為-(CH2)n•或_((CH2)2〇)m(CH2)2-，η 為 3 至10的整數’m為1至3的整數；a各自分別為單鍵、14_ 亞苯基或苯環上的任意的—個氫原子被㈣、子、碳原子數 1〜4，烷基或碳原子數丨〜4的烷氧基所取代的14亞苯 基，R及R2各自分別為氫原子、氟原子、碳原子數卜4 的烧基或碳料數1〜4攸氧基；r3及r4各自分別為氣 肩子或氟原子；X為單鍵、氧料或縣子； 1、其2中Κ€Η2)η·’Α為單鍵，χ為單鍵或硫原子時， R或R中任意的-個者為氟原子、碳原子數丨〜4的燒基 或;炭原:子數1〜4的烷氧基;Α為單鍵，且X為氧原子時， R〜R中至少其中之一為氟原子。 2.如申請專利範圍第1項所述之二胺，其中該二胺包 括式(1-A)〜（1-L)中任意的一個所示。 58 1343926 15190pif.doc爲第93132516號中文專利範圍無劃線修正本 修正日期:100年3月24曰Formula (1) Let 'Q be -(CH2)n• or _((CH2)2〇)m(CH2)2-, η is an integer from 3 to 10, 'm is an integer from 1 to 3; a is each a single bond Any 14-phenylene group on the 14-phenylene or benzene ring, which is substituted by (four), a sub, a carbon atom number of 1 to 4, an alkyl group or an alkoxy group having a carbon number of 丨~4, R And R2 are each a hydrogen atom, a fluorine atom, a carbon atom number of 4 or a carbon number of 1 to 4 methoxy groups; r3 and r4 are each a gas shoulder or a fluorine atom; X is a single bond, an oxygen material Or county; 1. In 2, Κ€Η2) η·'Α is a single bond, when χ is a single bond or a sulfur atom, any one of R or R is a fluorine atom, and the number of carbon atoms is 丨4. An alkyl group; a carbon atom: an alkoxy group having a number of 1 to 4; when hydrazine is a single bond, and X is an oxygen atom, at least one of R to R is a fluorine atom. 2. The diamine according to claim 1, wherein the diamine comprises any one of the formulae (1-A) to (1-L). 58 1343926 15190pif.doc is the Chinese patent scope of No. 93132516 without a slash correction. Amendment date: March 24, 100 (1-A) (1-B) (1-C) (1-D) (1-E) (1-F) (1-G) (1-H) (1-1) (1-J) (1-K) (1-L)(1-A) (1-B) (1-C) (1-D) (1-E) (1-F) (1-G) (1-H) (1-1) (1-J) (1-K) (1-L) 59 1343926 15190pif.doc 爲第93132516號中文專利範圍無劃線修正本 修正日期:100年3月24日 3·如申請專利範圍第μ 式⑴中，R1及R2各自分Υ斤边 其中 R3及R4為氫原子；Α為單鍵'、、氫原子或第三丁基； 马早鍵或1，4-亞笨基。 4·如申請專利範圍第3頊 為單鍵。 第3項所述之二胺’其中式⑴中χ 為氧=中請專利範圍第3項所述之二胺，其中式⑴中χ 為二申請專利範圍第3項所述之二胺，其中式⑴中χ 7·-種聚醯胺酸’該聚酿胺酸是由ι〇〜而莫耳百分 比的式(2·1)所tf之結構單位與9()〜 的 表示之結構單位所構成， 、耳百刀比的式(2-2) 〇 〇 n3-η/Λ„- ho2c/co2h R3 R159 1343926 15190pif.doc For the Chinese patent scope of No. 93132516, there is no slash correction. The date of this amendment is: March 24, 100. 3. If the scope of application is in the formula μ (1), R1 and R2 are each divided into R3 and R4. It is a hydrogen atom; hydrazine is a single bond ', a hydrogen atom or a tert-butyl group; a horse early bond or a 1,4-phenylene group. 4. If the scope of patent application is 3rd, it is a single bond. The diamine of the third aspect, wherein χ in the formula (1) is oxygen; the diamine described in the third paragraph of the patent scope, wherein the oxime in the formula (1) is the diamine described in item 3 of the patent application scope, wherein In the formula (1), χ7·-poly-proline sulphate is a structural unit represented by the formula (2·1) tf and the structural unit represented by 9()~ Composition, (2-2) 耳n3-η/Λ„- ho2c/co2h R3 R1 Q-Q- R2 (2-1) 〇 OΛ儿 -HN r5 nh-r6 ho2c/ 'co2h (2-2) 式（2·1)及式（2-2)中，Q 為-(CH2)n-或 -((CH2)2〇)m(CH2)2- ’n為 3 至 l〇 的整數，m為 1 至3 的整數；A各自分別為單鍵、ι，4-亞苯基或苯環上的任意的 一個氫原子被氟原子、碳原子數1-4的烷基或碳原子數i 〜4的烷氧基所取代的1,4-亞笨基；Ri及R2各自分別為氫 60 1343926 15190pif.doc 修正曰期:1〇〇年3月24曰 爲第93132516號中文專利範圍無劃線修丨# 原·^、氟1子、峡原子數！〜4的院基或碳原子數Η的 ，氧基；R3及Μ各自分別為氫原子或氟原子；又為單鍵、 氧原子或^原子，R5各自分別為碳原子數 4〜30的4價有 機基團；R6為碳原子數2〜6㈣2價有機基團； 其2中’ Q為-(CH2)n· ’ A為單鍵，χ為單鍵或硫原子時， 山或R中任意的—個為氟原子、碳原子數1〜4的院基或 =原子數1〜4的院氧基；A為單鍵，且χ為氧原子時， R、R、R、R4中至少其中之-為氟原子。 8·如申請專利翻第7項所述之聚醯胺gt，其中式(2-1) 及(2·2)中，R5各自分別為選自式(3)〜(11)所示之基團中至 少其中之一的4價基團，R2 (2-1) 〇OΛ-HN r5 nh-r6 ho2c/ 'co2h (2-2) In the formula (2·1) and (2-2), Q is -(CH2)n- or -( (CH2)2〇)m(CH2)2- 'n is an integer from 3 to l〇, m is an integer from 1 to 3; A is each a single bond, an iota, a 4-phenylene group or an benzene ring a hydrogen atom is substituted by a fluorine atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having a carbon number of i to 4; and Ri and R2 are each hydrogen 60 1343926 15190 pif. Doc Amendment of the flood season: 1 March, March 24, the number of Chinese patents No. 93132516, no underline repair #原·^, fluorine 1 child, the number of gorges! 〜4的院基 or carbon atom Η, oxy; R3 and Μ each are a hydrogen atom or a fluorine atom; respectively, a single bond, an oxygen atom or a ^ atom, R5 are each a carbon atom number 4~30 4 a valence organic group; R6 is a 2 to 6 (tetra) 2 -valent organic group having a carbon number; wherein 2 'Q is -(CH 2 ) n · ' A is a single bond, when χ is a single bond or a sulfur atom, any of mountains or R One is a fluorine atom, a hospital group having a carbon number of 1 to 4, or a hospitaloxy group having an atomic number of 1 to 4; A is a single bond, and when χ is an oxygen atom, at least R, R, R, and R4 are - is a fluorine atom. 8. The polyamine gt as described in claim 7, wherein in the formulae (2-1) and (2. 2), each of R5 is a group selected from the group consisting of the formulas (3) to (11). a tetravalent group of at least one of the group, 式(3)〜(11)中，G1為單鍵、碳原子數1〜12的亞烷基、 认亞笨基或1，4-亞環己基；&amp;為單鍵、媽…CH2CHr、 -〇-、-Co·、·δ· _C(CH3)_或-C(CF3)2-; X1 為單鍵或 CHr ; 61 1343926 15190pif.doc 爲第93132516號中文專利範圍無劃線修正# 修正日期:1〇〇年3月24日 β、^、β及妙各自分別為氫原子、甲基 基；R為氫原子或曱基；1137為氯原子 ，或本 基；Α3為環己烧環或苯環；q為】或2 ^ 基或苯 團為2個結合鍵互為α_位的2故結合鍵: 不的基 “9：如申請專利範圍第8項所述之聚醯胺酸，㈠r5 义別g(i)〜3所表示的任意的 、 » X Κ »χ (1)(丨丨）（川） CV) (v) 10.如申請專利範圍第7項至第9項中任何— 聚=酸’其巾r6為下述的任意的-個基團，In the formulae (3) to (11), G1 is a single bond, an alkylene group having 1 to 12 carbon atoms, a phenylene group or a 1,4-cyclohexylene group; &amp; is a single bond, a mother...CH2CHr, - 〇-, -Co·,·δ· _C(CH3)_ or -C(CF3)2-; X1 is a single bond or CHr; 61 1343926 15190pif.doc is the Chinese patent scope of No. 93132516 without a slash correction # :1, March 24, β, ^, β and Miao are each a hydrogen atom, a methyl group; R is a hydrogen atom or a sulfhydryl group; 1137 is a chlorine atom, or a radical; Α3 is a cyclohexane ring or Benzene ring; q is or 2 ^ group or benzene group is 2 binding bonds are α_ position of each other 2 bonding bond: non-based "9: as described in the scope of claim 8 of the poly-proline, (1) r5 Anything represented by g(i)~3, » X Κ »χ (1)(丨丨)(川) CV) (v) 10.If any of items 7 to 9 of the patent application scope — poly = acid', the towel r6 is any of the following groups, ?7H15?7H15 Bn Bn ]Bn Bn ] 其中’Bn表示苯甲基。 U.如申請專利範圍第7項至第9項中任何— 聚^酸’其中式㈤)中，RjR2各自分別為之 虱，、子或第三丁基；R3及R4為氫原子；A為單鍵或14_ 62 1343926 15190pif.doc 修正日期:1〇〇年3月24日 爲第93132516號中文專利範圍無劃線修正本 亞苯基。 12.如申請專利範圍第7項至第9項中任何一項所述之 聚醯胺酸，其中如式(2-3)所示之構成式(2-1)其中一部分的 基團為式（1-A)〜（1-L)所示的二胺作為二胺殘基以及如式 (Ι-a)〜（1-1)所示的基團的任意的一個。 R3 R1Wherein 'Bn represents a benzyl group. U. As in any of items 7 to 9 of the patent application - in the formula (5), RjR2 is each a ruthenium, a sub or a butyl group; R3 and R4 are a hydrogen atom; Single-key or 14_ 62 1343926 15190pif.doc Date of revision: 1 March of the year of March 24, the Chinese patent scope of No. 93132516 is not underlined to modify the present phenylene group. 12. The polyaminic acid according to any one of claims 7 to 9, wherein the group of the formula (2-1) represented by the formula (2-3) is a formula The diamine represented by (1-A) to (1-L) is a diamine residue and a group represented by the formula (Ι-a) to (1-1). R3 R1 63 1343926 15190pif.doc爲第93132516號中文專利範圍無劃線修正本 修正日期:1〇〇年3月24日63 1343926 15190pif.doc is the Chinese patent scope of No. 93132516 without a slash correction. Amendment date: March 24, 1 (1-a) (1-b) (1-c) (1-d)(1-a) (1-b) (1-c) (1-d) (1-e) (1-f) (i-g) (1-h)(1-e) (1-f) (i-g) (1-h) (1-i) (1-j) (1-k) (1-1) 64 1343926 15190pif.doc 爲第93132516號中文專利範圍無劃線修正本 修正日期:100年3月24日 13.如申請專利範圍第12項所述之聚醯胺酸，其中式 (2-1)中的X為單鍵。 '、 14_如申請專利範圍第12項所述之聚醯胺酸，其中式 (2-1)中的X為氧原子。 、 15. 如申請專利範圍第12項所述之聚醯胺酸，其中式 (2-1)中的X為硫原子。 16. 如申請專利範圍第7項至第9項中任何一項所述之(1-i) (1-j) (1-k) (1-1) 64 1343926 15190pif.doc The Chinese patent scope of No. 93132516 is not underlined. Amendment date: March 24, 100. 13. If applying The polyaminic acid according to the 12th aspect of the invention, wherein X in the formula (2-1) is a single bond. The polyamino acid of claim 12, wherein X in the formula (2-1) is an oxygen atom. 15. The polyamic acid according to claim 12, wherein X in the formula (2-1) is a sulfur atom. 16. As stated in any of items 7 to 9 of the patent application scope 聚醯胺酸’其中該聚醯胺酸之重量平均分子量為5,〇〇〇〜 500,000。 17. 如申請專利範圍第11項所述之聚醯胺酸，其中該 聚醯胺酸之重量平均分子量為5 〇〇〇〜5〇〇,〇〇〇。 18. 如申請專利範圍第13項所述之聚醯胺酸，其中該 聚醯胺酸之重量平均分子量為5,〇〇〇〜5〇〇,〇〇〇。 19_如申請專利範圍第14項所述之聚醯胺酸，其中該 聚醯胺酸之重量平均分子量為5,000〜5〇〇,〇〇〇。Polylysine wherein the polyamic acid has a weight average molecular weight of 5, 〇〇〇 〜 500,000. 17. The polylysine according to claim 11, wherein the polyamic acid has a weight average molecular weight of 5 〇〇〇 5 〇〇, 〇〇〇. 18. The polyaminic acid according to claim 13, wherein the polyglycine has a weight average molecular weight of 5, 〇〇〇 5 〇〇, 〇〇〇. The polyamic acid according to claim 14, wherein the polyglycine has a weight average molecular weight of 5,000 to 5 Å, 〇〇〇. 2〇.如申請專利範圍第15項所述之聚醯胺酸，其中該 聚醯胺酸之重量平均分子量為5,〇〇〇〜5〇〇 〇〇〇。 21. —種聚亞醯胺，該聚亞醯胺為如申請專利範圍第7 項至第16項令任何一項所述之聚醯胺酸經脫水而得到。 22. 種液晶配向劑，該液晶配向劑含有如申請專利範 圍第7項至第16項中任何一項所述之聚醯胺酸。 23. 種液晶配向劑，該液晶配向劑含有如申請專利範 圍第21項所述之聚亞醯胺。 24. —種液晶配向膜’該液晶配向膜是由如申請專利範 65 1343926 15190pif.doc 修正日期:1〇〇年3月24日 爲第93132516號中文專利範圍無劃線修正本 圍第22項或第23項所述之液晶配向劑而得到。 2 5. —種液晶顯示元件，該液晶顯示元件使用如申請專 利範圍第24項所述之液晶配向膜。The polyamic acid according to claim 15, wherein the polyglycine has a weight average molecular weight of 5, 〇〇〇 5 5 〇〇. A polyammoniumamine obtained by dehydrating a polyaminic acid according to any one of claims 7 to 16. A liquid crystal alignment agent containing the polyamic acid as described in any one of items 7 to 16 of the patent application. A liquid crystal alignment agent containing the polymethyleneamine as described in claim 21 of the patent application. 24. A liquid crystal alignment film 'The liquid crystal alignment film is as claimed in the patent No. 65 1343926 15190pif.doc Date of revision: March 24, 2014 is the Chinese patent scope No. 93132516 No line correction No. 22 Or obtained by the liquid crystal alignment agent of item 23. A liquid crystal display element using the liquid crystal alignment film of claim 24 of the patent application. 6666
TW093132516A 2003-11-05 2004-10-27 Diamine TWI343926B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2003375856 2003-11-05

Publications (2)

Publication Number Publication Date
TW200516099A TW200516099A (en) 2005-05-16
TWI343926B true TWI343926B (en) 2011-06-21

Family

ID=37244331

Family Applications (1)

Application Number Title Priority Date Filing Date
TW093132516A TWI343926B (en) 2003-11-05 2004-10-27 Diamine

Country Status (2)

Country Link
KR (1) KR20050043707A (en)
TW (1) TWI343926B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107615145B (en) * 2015-03-24 2021-05-07 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Also Published As

Publication number Publication date
TW200516099A (en) 2005-05-16
KR20050043707A (en) 2005-05-11

Similar Documents

Publication Publication Date Title
TWI375095B (en)
Yin et al. Synthesis and characterization of novel polyimides derived from 1, 1-bis [4-(4′-aminophenoxy) phenyl]-1-[3 ″, 5 ″-bis (trifluoromethyl) phenyl]-2, 2, 2-trifluoroethane
TWI293078B (en)
CN101117319B (en) Diamine, liquid crystal tropism agent, liquid crystal tropism film and liquid crystal display device
WO2010092989A1 (en) Tetracarboxylic acid derivatives, processes for producing same, and liquid-crystal alignment material
JP4894120B2 (en) Phenylenediamine derivative, liquid crystal alignment film, and liquid crystal display element
KR100510760B1 (en) Acid anhydride, liquid crystal alignment layer and liquid crystal display device
TW200940506A (en) Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same
TW200906768A (en) Diamine compound, polyamic acid, polyimide and liquid crystal aligning agent
WO2004052962A1 (en) Novel diaminobenzene derivative, polyimide precursor and polyimide obtained therefrom, and aligning agent for liquid crystal
CN101824327A (en) Alignment agent and liquid crystalline polyimide used therein
TWI452398B (en) Alignment material for liquid crystal display device and a preparing method of the same
JP4665487B2 (en) New diamine and polymer made from it
JP4779339B2 (en) Liquid crystal aligning agent and liquid crystal display element using the same
Han et al. Synthesis, characterization, and properties of thermosets based on the cocuring of an acetylene‐terminated liquid‐crystal and silicon‐containing arylacetylene oligomer
TWI281908B (en) Polyimide resin for non-rubbing vertical alignment materials and preparation method thereof
TWI275630B (en) Composition of containing polyamic acid blends and liquid crystal alignment layer and cell using them
JP4140252B2 (en) Phenylenediamine having a siloxane moiety, a liquid crystal alignment material including a polymer using the same, and a liquid crystal display element including the liquid crystal alignment material
TW200813158A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device
TWI343926B (en) Diamine
TW201221554A (en) The liquid crystal orientation agent, the liquid crystal orientation membrane, the liquid crystal display device, compounds and polymers
TW201012801A (en) Diamine, liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display device
TW200426193A (en) Varnish for forming liquid crystal oriented film, liquid crystal oriented film, and liquid crystal display device
TW201811864A (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device
JP5092382B2 (en) Diamine with liquid crystal-like structure

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees