TW200940506A - Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same - Google Patents

Diamine compound, liquid crystal aligning agent, and liquid crystal display device using the same Download PDF

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TW200940506A
TW200940506A TW98103101A TW98103101A TW200940506A TW 200940506 A TW200940506 A TW 200940506A TW 98103101 A TW98103101 A TW 98103101A TW 98103101 A TW98103101 A TW 98103101A TW 200940506 A TW200940506 A TW 200940506A
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ring
group
liquid crystal
formula
crystal alignment
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TW98103101A
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TWI490207B (en
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Satoshi Minami
Kohei Goto
Takahiro Suga
Hiroshi Kita
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Nissan Chemical Ind Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/40—Acylated substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (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)
  • Pyridine Compounds (AREA)

Abstract

Disclosed is a liquid crystal aligning agent which enables formation of a liquid crystal alignment film having high voltage holding ratio, in which film relaxation of residual charges accumulated by a DC voltage is fast even after long-time exposure to high temperatures. Also disclosed are a polyamide acid and/or a polyimide (hereinafter also referred to as a polymer) contained in the liquid crystal aligning agent, a diamine compound which can be used as a raw material for the polyamide acid and/or the polyimide, and a highly reliable liquid crystal display device having the liquid crystal alignment film, which device can endure long-time use in severe environments. Specifically disclosed is a diamine compound represented by Formula [1]. [1] (In Formula [1], X1 represents at least one divalent organic group selected from the group consisting of -O-, -NQ1-, -CONQ1-, -NQ1CO-, -CH2O- and -OCO-; Q1 represents a hydrogen atom or an alkyl group having 1-3 carbon atoms; X2 represents a single bond or at least one divalent organic group selected from the group consisting of aliphatic hydrocarbon groups having 1-20 carbon atoms, non-aromatic cyclic hydrocarbon groups and aromatic cyclic hydrocarbon groups; X3 represents a single bond or at least one divalent organic group selected from the group consisting of -O-, -NQ2-, -CONQ2-, -NQ2CO-, -COO-, -OCO- and -O(CH2)m- (wherein m represents an integer of 1-5); Q2 represents a hydrogen atom or an alkyl group having 1-3 carbon atoms; X4 represents a nitrogen-containing aromatic heterocyclic ring; and n represents an integer of 1-4.)

Description

200940506 » 六、發明說明： 【發明所屬之技術領域】 本發明係關於液晶配向膜中使用之作爲聚合物原料用 之二胺化合物，使用該化合物獲得之聚醯胺酸及聚醯亞胺 ，以及液晶配向處理劑。另外，關於具有由上述液晶配向 處理劑獲得之液晶配向膜之液晶顯示元件。 0 【先前技術】 目前，液晶顯示元件之液晶配向膜主要係使用將以聚 醯胺酸等之聚醯亞胺前驅物或可溶性聚醯亞胺之溶液作爲 主要成分之液晶配向處理劑（亦稱爲液晶配向劑）塗佈於 玻璃基板上並經燒成而成之所謂的聚醯亞胺系液晶配向膜 〇 液晶配向膜係爲了控制液晶之配向狀態之目的而使用 者。然而，伴隨著液晶顯示元件之高精細化，由於液晶顯 Ο 示元件之對比降低之抑制或殘像顯像降低之要求，使得使 用之液晶配向膜中須提高電壓維持率、或施加直流電壓時 之殘留電荷減少、及/或提早緩和因直流電壓而累積之殘 留電荷之特性亦逐漸變得重要。 聚醯亞胺系液晶配向膜中，作爲使因直流電壓產生之 殘像消失之前之時間縮短者，已知有使用除聚醯胺酸或含 有醯亞胺之聚醯胺酸以外含有特定構造之三級胺之液晶配 向劑者（例如參照專利文獻1)，或使用於原料使用具有 吡啶骨架等之特定二胺之可溶性聚醯亞胺之液晶配向劑者 -5- 200940506 (例如參照專利文獻2)。另外，作爲使電壓維持率高且 因直流電壓產生之殘像消失之前之時間縮短者，已知有使 用除聚醯胺酸或其醯亞胺化聚合物等以外含有極少量之選 自分子內含有1個羧基之化合物、分子內含有1個羧酸酐 基之化合物及分子內含有1個三級胺基之化合物之化合物 之液晶配向劑者（例如參照專利文獻3 )。 然而，近年來大畫面且高精細之液晶電視已廣爲實用 化，該等用途之液晶顯示元件中，與迄今爲止主要顯示文 字或靜止畫面之顯示器用途相比較，相對於殘像之要求更 爲嚴苛，且要求有在過度嚴苛之使用環境下之耐長期使用 之特性。據此，所使用之液晶配向膜亦要求有比過去更高 之信賴性，且關於液晶配向膜之電特性不僅亦要求良好之 初期特性，亦要求有例如即使在高溫下長時間暴露後亦可 維持良好之特性。 〔專利文獻1〕特開平9-3 1 6200號公報 〔專利文獻2〕特開平10-104633號公報 〔專利文獻3〕特開平8-76 1 28號公報 【發明內容】 〔發明欲解決之課題〕 本發明之目的係提供下述液晶顯示元件用之液晶配向 膜、形成該液晶配向膜之液晶配向處理劑、該液晶配向處 理劑中含有之聚醯胺酸及/或聚醯亞胺（以下亦稱爲聚合 物）、可作爲該聚醯胺酸及聚醯亞胺之原料使用之二胺化 -6 - 200940506 合物。 再者，本發明之目的係提供一種可獲得電壓維持率高 、且即使在高溫下長時間暴露後亦可及早緩和因直流電壓 累積之殘留電荷之液晶配向膜之液晶配向處理劑、以及提 供具有該液晶配向膜且在過度嚴苛之使用環境下耐長期使 用之信賴性高之液晶顯示元件。 〇 〔用以解決課題之手段〕 本發明者爲達成上述目的而積極進行硏究，而發現達 成該目的之新穎二胺化合物。本發明依據該等見解而具有 下列要旨。 (1) 一種以下述式〔1〕表示之二胺化合物，[Technical Field] The present invention relates to a diamine compound used as a polymer raw material used in a liquid crystal alignment film, a polylysine obtained by using the compound, and a polyimine, and Liquid crystal alignment treatment agent. Further, the liquid crystal display element having the liquid crystal alignment film obtained from the above liquid crystal alignment treatment agent. [Prior Art] At present, a liquid crystal alignment film of a liquid crystal display element mainly uses a liquid crystal alignment treatment agent containing a solution of a polyamidene precursor such as polyacrylamide or a soluble polyimine as a main component (also referred to as a liquid crystal alignment treatment agent). A so-called polyimine-based liquid crystal alignment film which is applied to a glass substrate and fired by a liquid crystal alignment agent, and a liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, with the high refinement of the liquid crystal display element, the suppression of the contrast reduction of the liquid crystal display element or the reduction of the residual image development requires the voltage maintenance ratio to be increased or the DC voltage to be applied in the liquid crystal alignment film to be used. It is also becoming increasingly important to reduce the residual charge and/or to moderate the residual charge accumulated by the DC voltage. In the polyimine-based liquid crystal alignment film, it is known to use a specific structure other than polyacrylic acid or polyamido acid containing ruthenium, as the time until the residual image due to the DC voltage is lost. A liquid crystal alignment agent of a tertiary amine (for example, refer to Patent Document 1), or a liquid crystal alignment agent using a soluble polyimine of a specific diamine having a pyridine skeleton or the like as a raw material-5-200940506 (for example, refer to Patent Document 2) ). In addition, as a time period before the residual image due to a DC voltage is high and the time after the disappearance of the residual image due to the DC voltage is shortened, it is known to use a very small amount selected from the group other than polyacrylic acid or its ruthenium iodide polymer. A liquid crystal alignment agent containing a compound having one carboxyl group, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing one compound of a tertiary amino group in the molecule (for example, see Patent Document 3). However, in recent years, large-screen and high-definition liquid crystal televisions have been widely put into practical use, and liquid crystal display elements for such applications are more demanding than afterimages as compared with display applications that have mainly displayed characters or still pictures. It is demanding and requires long-term use in an environment of excessively harsh use. Accordingly, the liquid crystal alignment film used also requires higher reliability than in the past, and the electrical characteristics of the liquid crystal alignment film not only require good initial characteristics, but also require, for example, long-term exposure even at high temperatures. Maintain good characteristics. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 10-104633 (Patent Document 3) Japanese Patent Publication No. Hei 8-76 No. The object of the present invention is to provide a liquid crystal alignment film for a liquid crystal display element, a liquid crystal alignment treatment agent for forming the liquid crystal alignment film, and a polyamic acid and/or polyimine contained in the liquid crystal alignment treatment agent (hereinafter) Also known as a polymer), a diamined-6 - 200940506 compound which can be used as a raw material of the polyproline and polyimine. Further, an object of the present invention is to provide a liquid crystal alignment treatment agent which can obtain a liquid crystal alignment film which has a high voltage maintenance ratio and which can relax the residual electric charge accumulated by a DC voltage even after exposure for a long time at a high temperature, and provides The liquid crystal alignment film is resistant to long-term use and has a highly reliable liquid crystal display element in an excessively harsh use environment. 〔 [Means for Solving the Problem] The inventors of the present invention actively conducted research to achieve the above object, and found a novel diamine compound which achieves the object. The present invention has the following gist in the light of these findings. (1) A diamine compound represented by the following formula [1],

❹❹

[1] (式〔1〕中，Χι 爲選自由-0-、-NQ1-、-C0NQ1-、-NQkO-、-CH20-及-OCO-所組成組群之至少一種二價有機 基，Q1爲氫原子或碳數1至3之烷基’ X2爲單鍵或選自 由碳數1至20之脂肪族烴基、非芳香族環式烴基及芳香 族烴基所組成組群之至少一種二價有機基’ χ3爲單鍵或選 自由 _〇_、-NQ2-、-CONQ2-、-NQ2CO-、-COO-、-OCO-及-0 ( CH2) m- ( m爲1至5之整數）所組成組群之至少一種 二價有機基，Q2爲氫原子或碳數1至3之烷基，X4爲含 氮之芳香族雜環，η爲1至4之整數）。 200940506 (2)如上述（1)所述之二胺化合物，其中式〔1〕 之二胺化合物爲選自下述式〔la〕至式〔If〕表示之化合 物所組成組群之至少一種： 〔化〕 h2i[1] (In the formula [1], Χι is at least one divalent organic group selected from the group consisting of -0-, -NQ1-, -C0NQ1-, -NQkO-, -CH20-, and -OCO-, Q1 At least one divalent organic group consisting of a hydrogen atom or an alkyl group having a carbon number of 1 to 3 'X2 is a single bond or a group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group The base ' χ 3 is a single bond or selected from _〇_, -NQ2-, -CONQ2-, -NQ2CO-, -COO-, -OCO-, and -0 (CH2) m- (m is an integer from 1 to 5) At least one divalent organic group constituting the group, Q2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X4 is a nitrogen-containing aromatic heterocyclic ring, and η is an integer of 1 to 4. (2) The diamine compound according to the above (1), wherein the diamine compound of the formula [1] is at least one selected from the group consisting of the compounds represented by the following formula [la] to the formula [If]: H2i

νη2 nh2ο—X2-X3-X4) η [1 η2ν-|- χ2-Χ3-Χ*) η ΗΝη2 nh2ο—X2-X3-X4) η [1 η2ν-|- χ2-Χ3-Χ*) η Η

_ ρ-χ3-χ4)η[ι [lb]_ ρ-χ3-χ4)η[ι [lb]

ο (式中，Q1爲氫原子或碳數1至3之烷基，Χ2爲單 鍵或選自由碳數1至20之脂肪族烴基、非芳香族環式烴 基及芳香族烴基所組成組群之至少—種二價有機基’ Χ3爲 單鍵或選自由·〇·、_NQ2_、_c〇nQ2_、_NQ2co_、-coo-、-OCO -及- 〇(CH2) m-(m爲1至5之整數）所組成組群 之至少一種二價有機基，Q2爲氫原子或碳數1至3之烷基 〇 ，X4爲含氮之芳香族雜環’η爲1至4之整數）。 (3) 如上述（2)所述之二胺化合物’其中式〔la〕 至式〔If〕中之X2爲單鍵、碳數1至3之直鏈院基或苯 環。 (4) 如上述（2)或（3)所述之二胺化合物’其中 式〔la〕至式〔If〕中之X3爲單鍵、-〇C〇-或-〇CH2-。 (5 )如上述（2 )至（4 )中任一項所述之二胺化合 物，其中式〔la〕至式〔lf〕中之χ4爲咪唑環、吡啶環 -8- 200940506 或略陡環。 (6 )如上述（2 )至（5 )中任一項所述之二胺化合 物，其中式〔la〕至式〔If〕中之n爲1或2之整數。 (7) 如上述（1)或（2)所述之二胺化合物，其中 式〔la〕至式〔If〕中之Χ2爲選自由碳數1至10之直鏈 或分支伸烷基、環己烷環、苯環及萘環所組成組群之至少 —種，Χ3 爲選自由單鍵、·〇·、-CONH-、-NHCO·、-COO- Φ 、-OCO-及-0 ( CH2) m- ( m爲1至5之整數）所組成組群 之至少一種，X4爲選自由吡咯環、咪唑環、吡唑環、吡啶 環、嘧啶環、嗒嗪環、三嗪環、三唑環、哌啶環、苯咪唑 環及苯并咪唑環所組成組群之至少一種，η爲1或2之整 數。 (8) 如上述（1)或（2)所述之二胺化合物，其中 式〔la〕至式〔If〕中之Χ2爲選自由單鍵、碳數1至5 之直鏈或分支伸烷基及苯環所組成組群之至少一種，Χ3爲 〇 選自由單鍵、-〇-、-CONH-、-NHCO-、-COO-、-OCO-及-0 ( CH2 ) m_ ( m爲1至5之整數）所組成組群之至少一種 ，X4爲選自由吡咯環、咪唑環、吡唑環、吡啶環及嘧啶環 所組成組群之至少一種，η爲1或2之整數。 (9) 如上述（1)或（2)所述之二胺化合物，其中 式〔la〕至式〔If〕中之Χ2爲選自由單鍵、碳數1至3 之直鏈伸烷基及苯環所組成組群之至少一種，Χ3爲選自由 單鍵、-OCO-及-OCH2-所組成組群之至少一種，Χ4爲選自 由咪唑環、吡啶環及嘧啶環所組成組群之至少一種，η爲 -9- 200940506 1或2之整數。 (10) —種聚醯胺酸或聚醯亞胺，係由含有上述（1 )至（9)中任一項所述之二胺化合物之二胺成分與四羧 酸二酐反應所得之聚醯胺酸、或由該聚醯胺酸經脫水閉環 所得之聚醯亞胺。 (11) 如上述（10)所述之聚醯胺酸或聚醯亞胺，其 中以式〔1〕表示之二胺化合物佔二胺成分中之1至80莫 耳％ ° ❹ (12) —種液晶配向處理劑，其含有上述（10)或（ 11)所述之聚醯胺酸及聚醯亞胺中之至少任一者以及溶劑 〇 (13) 如上述（12)所述之液晶配向處理劑，其中該 液晶配向處理劑中所含之溶劑中之5至80質量％爲弱溶劑 〇 (14) 一種液晶配向膜，係使用上述（12)或（13) 所述之液晶配向處理劑所得。 ◎ (15) —種液晶顯示元件，係具有上述（14)所述之 液晶配向膜。 〔發明之效果〕 本發明之二胺化合物可以比較簡便之方法獲得，且使 用該二胺化合物作爲構成液晶配向膜之聚合物原料時，可 獲得電壓保持率高且即使於高溫下長時間暴露後亦可加速 緩和由直流電壓引起之累積殘留電荷之液晶配向膜。因此 -10- 200940506 ，具有由本發明之液晶配向處理劑獲得之液晶配向膜之液 晶顯示元件爲信賴性優異者，可適當利用於大畫面之高精 細液晶電視等。 【實施方式】 以下，就本發明加以詳細說明。 本發明爲以式〔1〕表示之二胺化合物、以式〔1〕表 〇 示之二胺化合物作爲原料獲得之聚合物、含有該聚合物之 液晶配向處理劑、使用該液晶配向處理劑獲得之液晶配向 膜，進而爲具有該液晶配向膜之液晶顯示元件。 本發明之二胺化合物爲側鏈上具有含氮之芳香族雜環 之二胺化合物（以下，有時亦稱爲特定二胺化合物）。該 含氮芳香族雜環由於藉由其共轭構造作爲電子之跳躍位置 (hopping site )之機能，故由含有自特定二胺化合物獲得 之聚合物之液晶配向處理劑製造之液晶配向膜，可促進液 〇 晶配向膜中之電荷移動。 藉由上述，本發明之液晶配向處理劑於成爲液晶配向 膜時，可獲得電壓保持率高且即使於高溫下長時間暴露後 亦可加速緩和由直流電壓引起之累積殘留電荷之液晶配向 膜。 <特定二胺化合物> 本發明之特定二胺化合物爲以下述式〔1〕表示之表 示之二胺化合物： -11 - [1] [1]200940506ο (wherein Q1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Χ2 is a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group; At least one of the divalent organic groups 'Χ3 is a single bond or is selected from the group consisting of 〇··, _NQ2_, _c〇nQ2_, _NQ2co_, -coo-, -OCO-, and -〇(CH2) m-(m is 1 to 5 Integer) at least one divalent organic group of the group consisting of Q2 being a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X4 being a nitrogen-containing aromatic heterocyclic ring 'n is an integer of 1 to 4). (3) The diamine compound as described in the above (2) wherein X2 in the formula [la] to the formula [If] is a single bond, a linear group having a carbon number of 1 to 3 or a benzene ring. (4) The diamine compound as described in the above (2) or (3) wherein X3 in the formula [la] to the formula [If] is a single bond, -〇C〇- or -〇CH2-. (5) The diamine compound according to any one of (2) to (4) above, wherein the oxime 4 in the formula [la] to the formula [lf] is an imidazole ring, a pyridine ring-8-200940506 or a slightly steep ring. . (6) The diamine compound according to any one of the above (2) to (5), wherein n in the formula [la] to the formula [If] is an integer of 1 or 2. (7) The diamine compound according to the above (1) or (2), wherein the oxime 2 in the formula [la] to the formula [If] is a linear or branched alkyl group selected from a carbon number of 1 to 10, and a ring At least one of the group consisting of a hexane ring, a benzene ring and a naphthalene ring, and Χ3 is selected from the group consisting of a single bond, 〇·, -CONH-, -NHCO·, -COO- Φ , -OCO- and -0 (CH2) M- (m is an integer from 1 to 5) at least one of the group consisting of, wherein X4 is selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, and a triazole At least one of a group consisting of a ring, a piperidine ring, a benzimidazole ring and a benzimidazole ring, and η is an integer of 1 or 2. (8) The diamine compound according to the above (1) or (2), wherein the oxime 2 in the formula [la] to the formula [If] is a linear or branched alkyl group selected from a single bond and having a carbon number of 1 to 5. At least one of the group consisting of a benzene ring and a benzene ring, Χ3 is selected from the group consisting of a single bond, -〇-, -CONH-, -NHCO-, -COO-, -OCO-, and -0 (CH2) m_ (m is 1 At least one of the group consisting of 5 integers, X4 is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring, and n is an integer of 1 or 2. (9) The diamine compound according to the above (1) or (2), wherein the oxime 2 in the formula [la] to the formula [If] is a linear alkyl group selected from a single bond, a carbon number of 1 to 3, and At least one group consisting of benzene rings, Χ3 is at least one selected from the group consisting of a single bond, -OCO-, and -OCH2-, and Χ4 is at least one selected from the group consisting of an imidazole ring, a pyridine ring, and a pyrimidine ring. One, η is an integer from -9 to 200940506 1 or 2. (10) A poly-proline or polyimine which is obtained by reacting a diamine component containing the diamine compound according to any one of the above (1) to (9) with a tetracarboxylic dianhydride. A proline, or a polyimine obtained by dehydration ring closure of the polyamic acid. (11) The polyaminic acid or polyimine according to the above (10), wherein the diamine compound represented by the formula [1] accounts for 1 to 80 mol% of the diamine component (12). A liquid crystal alignment treatment agent comprising at least one of the polyacrylic acid and the polyamidene according to the above (10) or (11), and a solvent hydrazine (13), wherein the liquid crystal alignment is as described in (12) above The treatment agent, wherein 5 to 80% by mass of the solvent contained in the liquid crystal alignment treatment agent is a weak solvent 〇 (14), a liquid crystal alignment film, which uses the liquid crystal alignment treatment agent according to (12) or (13) above Income. (15) A liquid crystal display element comprising the liquid crystal alignment film according to (14) above. [Effects of the Invention] The diamine compound of the present invention can be obtained by a relatively simple method, and when the diamine compound is used as a polymer raw material constituting the liquid crystal alignment film, a voltage holding ratio can be obtained and even after prolonged exposure at a high temperature It is also possible to accelerate the liquid crystal alignment film which alleviates the accumulated residual charge caused by the direct current voltage. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be suitably used for a high-definition liquid crystal television of a large screen. [Embodiment] Hereinafter, the present invention will be described in detail. The present invention is a polymer obtained by using a diamine compound represented by the formula [1], a diamine compound represented by the formula [1] as a raw material, a liquid crystal alignment treatment agent containing the polymer, and using the liquid crystal alignment treatment agent. The liquid crystal alignment film is further a liquid crystal display element having the liquid crystal alignment film. The diamine compound of the present invention is a diamine compound having a nitrogen-containing aromatic heterocyclic ring in the side chain (hereinafter sometimes referred to as a specific diamine compound). Since the nitrogen-containing aromatic heterocyclic ring functions as a hopping site of electrons by its conjugated structure, a liquid crystal alignment film produced from a liquid crystal alignment treatment agent containing a polymer obtained from a specific diamine compound can be used. Promotes the movement of charge in the liquid twinning alignment film. When the liquid crystal alignment treatment agent of the present invention is used as a liquid crystal alignment film, a liquid crystal alignment film having a high voltage holding ratio and accelerating the accumulation of residual electric charge due to a DC voltage even after exposure to a high temperature for a long period of time can be obtained. <Specific Diamine Compound> The specific diamine compound of the present invention is a diamine compound represented by the following formula [1]: -11 - [1] [1] 200940506

式〔1〕中，Χι 爲選自由-ο-、-NQ1-、-CONQ1-、· NQ'CO-、-CH20-及- OCO-所組成組群之至少一種二價有機 基，Q1爲氫原子或碳數1至3之烷基，X2爲單鍵或選自 由碳數1至20之脂肪族烴基、非芳香族環式烴基及芳香 族烴基所組成組群之至少一種二價有機基，Xs爲單鍵或選 自由-〇_、-NQ2-、-CONQ2-、-NQ2CO-、-CO〇-、-0C0-及-0 ( CH2) m- ( m爲1至5之整數）所組成組群之至少一種 二價有機基，Q2爲氫原子或碳數1至3之烷基，X4爲含 氮之芳香族雜環，η爲1至4之整數。 式〔1〕中之二個胺基（-ΝΗ2 )之鍵結位置並無限制 。具體而言，η爲1之整數時，舉例爲相對於側鏈之鍵結 基（Χι)，爲苯環上之2、3位置，2、4位置，2、5位置 ，2、6位置，3、4位置，3、5位置。η爲2之整數時， 舉例爲下列之位置。相對於側鏈之鍵結基（Χ2 )，苯環上 之2位置上具有側鏈鍵結基（X!)時，兩個胺基之鍵結位 置舉例爲3、4位置，3、5位置，3、6位置，4、5位置。 另外，相對於側鏈之鍵結基（Χι )，苯環上之3位置上具 有側鏈鍵結基（Χι)時，兩個胺基之鍵結位置舉例爲2、 4位置，2、5位置，4、5位置’ 4、6位置。另外，相對 於側鏈之鍵結基（Χί)，苯環上之4位置上具有側鏈之鍵 -12- 200940506 結基（χυ時，兩個胺基之鍵結位置舉例爲 、5位置，2、6位置，3、5位置。η爲3之 爲下列位置。相對於側鏈之鍵結基（X!)， 3位置上具有側鏈之鍵結基（Xt )時，兩個 置舉例爲4、5位置、4、6位置。另外，相 結基（X!)，苯環上之2、4位置上具有側 Xt)時，兩個胺基之鍵結位置舉例爲3、5 1 φ 置，5、6位置。另外，相對於側鏈鍵結基 上之3、5位置上具有側鏈之鍵結基（X!) 之鍵結位置舉例爲2、4位置。η爲4之整數 列位置。相對於側鏈之鍵結基（Xi )，苯環 位置上具有側鏈之鍵結基（Xi )時，兩個胺 舉例爲5、6位置。又，相對於側鏈之鍵結 環上之2、4、5位置上具有側鏈之鍵結基（ 胺基之鍵結位置舉例爲3、6位置。另外， 〇 鍵結基（Xi)，苯環上之2、4、6位置上具 基（Xi)時，兩個胺基之鍵結位置舉例爲3 等之中，就合成聚醯胺酸時之反應性之觀點 成二胺化合物時容易性而言，η爲1之整數 之鍵結位置最好爲2、4位置、2、5位置、： η爲2之整數時相對於側鏈之結合基（X!) 位置上具有側鏈鍵結基（X!)時，兩個胺基 好爲4、6位置。 式〔1〕中 X!爲選自由-〇-、-NQ1- 2、3位置，2 整數時，舉例 苯環上之2、 胺基之鍵結位 對於側鏈之鍵 鏈之鍵結基（ [立置、3、6位 (Χι )，苯環 時，兩個胺基 時，舉例爲下 上之 2、3、4 基之鍵結位置 基（Χι )，苯 Xi )時，兩個 相對於側鏈之 有側鏈之鍵結 、5位置。該 ，以及加上合 時，兩個胺基 ϊ、5位置，或 ，苯環上之3 之鍵結位置最 、-CONQ1-、- -13- 200940506 NQiCO-、-CH20-及-OCO-所組成組群之至少一種二價有機 基。其中，以-0-、-NQ1-、-C0NQ1-、-Ni^CO-較佳。而 且，Q1係與式〔1〕之定義相同。In the formula [1], Χι is at least one divalent organic group selected from the group consisting of -ο-, -NQ1-, -CONQ1-, ·NQ'CO-, -CH20-, and -OCO-, and Q1 is hydrogen. An atom or an alkyl group having 1 to 3 carbon atoms, X 2 being a single bond or at least one divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. Xs is a single bond or is selected from -〇_, -NQ2-, -CONQ2-, -NQ2CO-, -CO〇-, -0C0-, and -0 (CH2) m- (m is an integer from 1 to 5) At least one divalent organic group of the group, Q2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X4 is a nitrogen-containing aromatic heterocyclic ring, and η is an integer of 1 to 4. The bonding position of the two amine groups (-ΝΗ2) in the formula [1] is not limited. Specifically, when η is an integer of 1, an example is a bonding group (Χι) with respect to a side chain, and is a 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position on the benzene ring, 3, 4 position, 3, 5 position. When η is an integer of 2, the following positions are exemplified. With respect to the bonding group (Χ2) of the side chain, when the side of the benzene ring has a side chain bonding group (X!), the bonding positions of the two amine groups are exemplified by 3, 4 positions, 3, 5 positions. , 3, 6 position, 4, 5 position. Further, when the side chain linkage group (Χι) has a side chain bonding group (Χι) at the 3-position on the benzene ring, the bonding positions of the two amine groups are exemplified by 2, 4 positions, 2, 5 Position, 4, 5 position '4, 6 position. In addition, with respect to the bonding group of the side chain, the bond at the 4 position on the benzene ring has a side chain bond-12-200940506 (wherein, the bonding position of the two amine groups is, for example, 5 positions, 2, 6 position, 3, 5 position. η is 3 for the following position. Relative to the bonding group of the side chain (X!), when there are side chain bonding groups (Xt) at the 3 position, two examples are given. In the position of 4, 5, 4, 6. In addition, when the phase-bonding group (X!) has a side Xt at positions 2 and 4 on the benzene ring, the bonding positions of the two amine groups are exemplified as 3, 5 1 φ set, 5, 6 position. Further, the bonding position of the bonding group (X!) having a side chain at positions 3 and 5 on the side chain bonding group is exemplified by 2 and 4 positions. η is an integer number of 4 column positions. The two amines are exemplified by the bonding sites (Xi) of the side chain and the bonding group (Xi) of the side chain at the position of the benzene ring. Further, a bonding group having a side chain at positions 2, 4, and 5 on the bonding ring of the side chain (the bonding position of the amine group is exemplified by positions 3 and 6. Further, the fluorene bonding group (Xi), When the group (Xi) is present at the 2, 4, and 6 positions on the benzene ring, the bonding position of the two amine groups is exemplified as 3, and the viewpoint of the reactivity in synthesizing the polyamic acid is the diamine compound. In terms of easiness, the bonding position where η is an integer of 1 is preferably 2, 4 position, 2, 5 position, and: η is an integer of 2, and has a side chain at a position (X!) with respect to a side chain. When the bond group (X!) is bonded, the two amine groups are preferably at positions 4 and 6. In the formula [1], X! is selected from the group consisting of -〇-, -NQ1, 2, and 3, and 2 integers, for example, on the benzene ring. 2, the bond of the amine group to the bond group of the bond chain of the side chain ([立立, 3, 6 positions (Χι), benzene ring, when two amine groups, for example, the lower 2, 3 When the 4-base bond position group (Χι ), benzene Xi), the two side chains with respect to the side chain have a side bond, 5 positions, and when combined, the two amine groups 5, 5 positions , or, the bond position of the 3 on the benzene ring is the most, -CONQ1 -, - -13- 200940506 At least one divalent organic group consisting of NQiCO-, -CH20- and -OCO-, wherein -0-, -NQ1-, -C0NQ1-, -Ni^CO- Preferably, Q1 is the same as defined in formula [1].

Xi更具體之構造舉例爲下述式〔la〕至式〔If〕° 化 η2νΌ^°~ Χ2-Χ3-Χ4) n [la] H2丨 nh2气[id: wh2A more specific configuration of Xi is exemplified by the following formula [la] to the formula [If] ° η2νΌ^°~ Χ2-Χ3-Χ4) n [la] H2丨 nh2 gas [id: wh2

HzN- NH,HzN- NH,

IV〇-X2-X3-X4) [le]IV〇-X2-X3-X4) [le]

H2n^5t X2-X3-X4)H2n^5t X2-X3-X4)

Cl nCl n

o-c-x2-x3-x4) n [If] 其中，以式〔la〕、式〔lb〕、式〔1C〕及式〔Id〕 較佳。且，Q1係與式〔1〕之定義相同。 式〔1〕中，X2爲單鍵或選自由碳數1至20之脂肪族 烴基、非芳香族環式烴基及芳香族烴基所組成組群之至少 一種二價有機基。 ◎ 碳數1至20之脂肪族烴基可爲直鏈狀，亦可爲分支 。又，亦可具有不飽和鍵。較好爲碳數1至10之脂肪族 烴基。 非芳香族環狀烴基之具體例舉例爲環丙烷環、環丁烷 環、環戊烷環、環己烷環、環庚烷環、環辛烷環、環壬烷 環、環癸烷環、環^--烷環、環十二烷環、環十三烷環、 環十四垸環、環十五院環、環十六院環、環十七院環、環 十八烷環、環十九烷環、環二十烷環、三環二十烷環、三 -14- 200940506 環癸烷環、雙環丁烷環、十氫萘環、原冰片烯環、金剛院 環等。 芳香族烴基之具體例舉例爲苯環、萘環、四氫萘環、 葜環、茚環、芴環、蒽環、菲環、非那烯（Phenalene )環 等。 式〔1〕中，較佳之X2爲單鍵、碳數1至1〇之直鏈 或分支伸院基、碳數1至10之不飽和伸院基、環丙院環 〇 、環丁烷環、環戊烷環、環己烷環、環庚烷環、原冰片烯 環、金剛烷環、苯環、萘環、四氫萘環、芴環、蒽環，更 好爲單鍵、碳數1至10之直鏈或分支伸烷基、碳數丨至 1〇之不飽和伸烷基、環己烷環、原冰片烯環、金剛烷環、 苯環、萘環、芴環、蒽環，又更好爲單鍵、碳數1至10 之直鏈或分支伸烷基、環己烷環'苯環、萘環。特好爲單 鍵、碳數1至5之直鏈或分支伸烷基、苯環。最好爲單鍵 、碳數1至3之直鏈伸烷基或苯環。 ® 式〔1〕中，X3爲單鍵或選自由-O-'-NQ2-、- CONQ2-、_NQ2CO-、-COO-、-OCO-及-Ο ( CH2) m- ( m 爲 1至5之整數）所組成組群之至少一種二價有機基，較好 爲單鍵、-0-、-CONQ2-、-NQ2CO-、-COO-、-OCO-及-〇(〇112)1„-(111爲1至5之整數）。最好爲單鍵、-〇(：0-或- OCH2-。且，Q2係與式〔1〕之定義相同。 式〔1〕中，X4爲含氮之芳香族雜環’且爲含有選自 由下述式〔2a〕、式〔2b〕及式〔2c〕組成之組群之至少 一個構造之含氮芳香族雜環。 -15- 200940506O-c-x2-x3-x4) n [If] wherein, the formula [la], the formula [lb], the formula [1C] and the formula [Id] are preferred. Further, Q1 is the same as defined in the formula [1]. In the formula [1], X2 is a single bond or at least one divalent organic group selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon groups and aromatic hydrocarbon groups. ◎ The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Further, it may have an unsaturated bond. It is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Specific examples of the non-aromatic cyclic hydrocarbon group are a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, Ring---alkane ring, cyclododecane ring, cyclotridecane ring, ring fourteen ring, ring fifteen ring, ring sixteen ring, ring seventeen ring, cyclooctadecan ring, ring Pentadecane ring, cycloecosane ring, tricyclohexadecane ring, tri-14-200940506 cyclodecane ring, bicyclobutane ring, decahydronaphthalene ring, raw norbornene ring, diamond ring. Specific examples of the aromatic hydrocarbon group are a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, and a phenalene ring. In the formula [1], preferably, X2 is a single bond, a linear or branched stretching group having a carbon number of 1 to 1 Å, an unsaturated stretching group having a carbon number of 1 to 10, a ring of propylene ring, a cyclobutane ring. , cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring, anthracene ring, more preferably single bond, carbon number a linear or branched alkyl group of 1 to 10, an unsaturated alkyl group having a carbon number of 1 to 10, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring Further, it is preferably a single bond, a linear or branched alkyl group having a carbon number of 1 to 10, a cyclohexane ring 'benzene ring, and a naphthalene ring. Particularly preferred is a single bond, a straight or branched alkyl group having a carbon number of 1 to 5, and a benzene ring. It is preferably a single bond, a linear alkyl group having a carbon number of 1 to 3 or a benzene ring. ® In the formula [1], X3 is a single bond or is selected from -O-'-NQ2-, -CONQ2-, _NQ2CO-, -COO-, -OCO-, and -Ο(CH2) m- (m is 1 to 5) Integer) at least one divalent organic group of the group, preferably a single bond, -0-, -CONQ2-, -NQ2CO-, -COO-, -OCO-, and -〇(〇112)1„- (111 is an integer of 1 to 5). It is preferably a single bond, -〇(:0- or -OCH2-. Further, Q2 is the same as defined in the formula [1]. In the formula [1], X4 is nitrogen-containing. The aromatic heterocyclic ring ' is a nitrogen-containing aromatic heterocyclic ring containing at least one structure selected from the group consisting of the following formulas [2a], [2b], and [2c]. -15- 200940506

[2a] NH [2b] N—Y! [2 c] 式〔2c〕中’ Y!爲碳數1至5之直鏈或分支烷基。 式〔1〕中’較佳之X4爲卩比略環、咪哩環、嚼哩環、 噻唑環、吡唑環、吡啶環、嘧啶環、喹啉環、啦哩啉環、 異喹琳環、昨唑環、嘌玲環、噻二哩環、塔曉環、耻哩琳 環、三嗪環、吡唑啶環、三唑環、哌啶環、苯并咪哩環、 © 苯并咪哩環、嗟諾琳環、菲琳環、n引噪環、喹諾啉環、苯 并噻哩環、菲噻嗪環、噁二唑環、吖丁啶環，更好爲吡咯 環、咪哩環、卩比嗤環、卩比π定環、嚼陡環、耻哩啉環、味哩 環、嗒嗪環、吡唑琳環、三嗪環、吡唑啶環、三唑環、哌 啶環、苯并咪唑環、苯并咪唑環，又更好爲吡咯環、咪唑 環、吡唑環、吡啶環、嘧啶環、嗒嗪環、三嗪環、三唑環 、哌啶環、苯并咪唑環、苯并咪唑環，最好爲吡咯環、咪 ❹ 唑環、吡唑環、吡啶環、嘧啶環。又最好爲咪唑環、吡啶 環或嘧陡環。 又，Χ3較好與未與x4中所含之式〔2a〕、式〔2b〕 及式〔2c〕相鄰之取代基鍵結。 式〔1〕中，η爲1至4之整數，且就與四羧酸二酐之 反應性之觀點而言較好爲1至3之整數。最好，11爲丨或 2之整數。 式〔1〕中較佳之Χι、Χ2、Χ3、Χ4及η之組合爲Χι 爲選自由-ο-、-NQ1-、-CONQ1-、-NC^CO-、-CH20-及- -16- 200940506 OCO-所組成組群之至少一種，χ2爲選自由碳數1至1〇之 直鏈或分支伸烷基、碳數1至10之不飽和伸烷基、環丙 院環、環丁院環、環戊院環、環己院環、環庚院環、原冰 片烯環、金剛烷環、苯環、萘環、四氫萘環、芴環及蒽環 等組成之組群之至少一種，X3爲單鍵或選自由-O-'-NQ2-、-CONQ2-、-NQ2C0-、-COO-、-OCO-及-0(CH2)m- ( m 爲 1至5之整數）所組成組群之至少一種，χ4爲選自由吡略 ❹ 環、咪唑環、噁唑環、噻唑環、吡唑環、吡啶環、嘧啶環 、喹啉環、吡唑啉環、異喹啉環、咔唑環、嘌呤環、噻二 唑環、嗒嗪環、吡唑啉環、三嗪環、吡唑啶環、三唑環、 哌啶環、苯并咪唑環、苯并咪唑環、噻諾啉環、菲啉環、 吲哚環、喹諾啉環、苯并噻唑環、菲噻啶環、噁二唑環及 吖丁啶環所組成組群之至少一種，η爲1或2之整數。 更好式〔1〕中之X!、Χ2、Χ3、Χ4及η之組合爲Xl 爲選自由-Ο-、-NQ1-、-CONQ1-、-NC^CO-及-CH20-所組 O 成組群之至少一種，χ2爲選自由碳數1至ι〇之直鏈或分 支伸烷基、碳數1至10之不飽和伸烷基、環己烷環、原 冰片烯環、金剛烷環 '苯環、萘環、芴環及蒽環等組成之 組群之至少一種，Χ3爲選自由單鍵、-〇-、以(^2-、-CONQ2-、_NQ2C0-、-COO-、-0C0-及-0 ( CH2 ) m- ( m 爲 1至5之整數）所組成組群之至少一種，χ4爲選自由吡咯 環、咪唑環、吡唑環、吡啶環、嘧啶環、吡唑啉環、昨唑 環、嗒嗪環、吡唑啉環、三嗪環、吡唑啶環、三唑環、哌 啶環、苯并咪唑環及苯并咪唑環所組成組群之至少一種， -17- 200940506 η爲1或2之整數。 又更好式〔1〕中之Xl、x2、Χ3、Χ4及 Χι 爲選自由- 0-、-NQ1-、-CONQ1-、-NC^CO-0 CO-所組成組群之至少一種，X2爲選自由碳襲 直鏈或分支伸烷基、環己烷環、苯環及萘環組 至少一種，X3爲選自由單鍵、-Ο·、-C0NQ2 、-COO-、-OCO-及-0 ( CH2 ) m- ( m 爲 1 至 5 組成組群之至少一種，X4爲選自由吡咯環、咪 環、吡啶環、嘧啶環、嗒嗪環、三嗪環、三唑 、苯并咪唑環及苯并咪唑環所組成組群之至少 1或2之整數。 最好式〔1〕中之X丨、x2、X3、X4及H ; 爲選自由-〇-、-NQ1-、-CONQ1-、-NC^CO-及 成組群之至少一種，X2爲選自由單鍵、碳數1 或分支伸烷基及苯環所組成組群之至少一種， 單鍵、-〇-、-C0NQ2-、-NQ2C0- ' -COO-、 0(CH2)m- (m爲1至5之整數）所組成組群之 X4爲選自由吡咯環、咪唑環、吡唑環、吡啶環 組成組群之至少一種，η爲1或2之整數。 又最好式〔1〕中之Xi、Χ2、Χ3、Χ4及 X!爲選自由-0-、-NQ1-、-C0NQ1-及-NC^CO-之至少一種，X2爲選自由單鍵、碳數1至3之 及苯環所組成組群之至少一種，X3爲選自由骂 及-0CH2-所組成組群之至少一種，χ4爲選自 η之組合爲 、-C Η 2 〇 -及-t 1至10之 成之組群之 -、-nq2co- 之整數）所 唑環、吡唑 環、呱啶環 一種，η爲 之組合爲Xj -CH20-所組 至5之直鏈 X3爲選自由 -0C0-及 _ 至少一種， 及嘧啶環所 η之組合爲 所組成組群 直鏈伸烷基 【鍵、-0C0-由咪唑環、 200940506 [少一種，η爲1或2之整 Χ3、Χ4及η之組合爲下列 Q2係與式〔1〕之定義相同 吡啶環及嘧啶環所組成組群之兰 數。最好式〔1〕中之Χι、X2、 表1至表3中所示。且，Q1及 ❿ -19- 200940506 〔表1〕[2a] NH [2b] N—Y! [2 c] In the formula [2c], Y Y is a linear or branched alkyl group having 1 to 5 carbon atoms. In the formula [1], preferred X4 is an anthracene ring, a oxime ring, a chewable ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a porphyrin ring, an isoquine ring, Yesterday, azole ring, oxime ring, thiadiazine ring, taxiao ring, muscarin ring, triazine ring, pyrazolidine ring, triazole ring, piperidine ring, benzopyrene ring, © benzopyrene Ring, quinolone ring, phenanthrene ring, n noise ring, quinolino ring, benzothiazepine ring, phenothiazine ring, oxadiazole ring, azetidine ring, more preferably pyrrole ring, oxime ring,卩 嗤 嗤 ring, 卩 π ring, chewing steep ring, porphyrin ring, miso ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, piperidine ring, Benzimidazole ring, benzimidazole ring, more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, piperidine ring, benzimidazole ring The benzimidazole ring is preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring. Further preferably, it is an imidazole ring, a pyridine ring or a pyrimidine ring. Further, ruthenium 3 is preferably bonded to a substituent which is not adjacent to the formula [2a], formula [2b] and formula [2c] contained in x4. In the formula [1], η is an integer of 1 to 4, and is preferably an integer of 1 to 3 from the viewpoint of reactivity with tetracarboxylic dianhydride. Preferably, 11 is an integer of 丨 or 2. The preferred combination of Χι, Χ2, Χ3, Χ4 and η in the formula [1] is Χι is selected from -ο-, -NQ1-, -CONQ1-, -NC^CO-, -CH20-, and -16-200940506 OCO- at least one of the group consisting of χ2 is selected from a linear or branched alkyl group having a carbon number of 1 to 1 Å, an unsaturated alkyl group having 1 to 10 carbon atoms, a ring of propylene ring, and a ring of ring At least one of a group consisting of a ring of a ring, a ring of a ring, a ring of a ring, a ring of a ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, and an anthracene ring, X3 is a single bond or is selected from the group consisting of -O-'-NQ2-, -CONQ2-, -NQ2C0-, -COO-, -OCO-, and -0(CH2)m- (m is an integer from 1 to 5) At least one of the group, χ4 is selected from the group consisting of a pyridinium ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, and a carbazole. Ring, anthracene ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, piperidine ring, benzimidazole ring, benzimidazole ring, thienoline ring , phenanthroline ring, anthracene ring, quinololine ring, benzothiazole ring, phenothiazine ring, evil An oxazole ring and azetidine ring composed of at least one group, η is an integer of 1 or 2. More preferably, the combination of X!, Χ2, Χ3, Χ4 and η in the formula [1] is X1 selected from the group consisting of -Ο-, -NQ1-, -CONQ1-, -NC^CO- and -CH20- At least one of the group, χ2 is a linear or branched alkyl group selected from carbon number 1 to oxime, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, and an adamantane ring. At least one of a group consisting of a benzene ring, a naphthalene ring, an anthracene ring, and an anthracene ring, and Χ3 is selected from the group consisting of a single bond, -〇-, and (^2-, -CONQ2-, _NQ2C0-, -COO-, - 0C0- and -0 (CH2) m- (m is an integer from 1 to 5) at least one of the group consisting of pyrene ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline At least one of a ring, a azole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a piperidine ring, a benzimidazole ring, and a benzimidazole ring, - 17- 200940506 η is an integer of 1 or 2. Further, X1, x2, Χ3, Χ4 and Χι in the formula [1] are selected from - 0-, -NQ1-, -CONQ1-, -NC^CO-0 At least one of the group consisting of CO-, X2 is selected from a linear or branched alkyl group, a cyclohexane ring At least one of a benzene ring and a naphthalene ring group, and X3 is at least one selected from the group consisting of a single bond, -Ο·, -C0NQ2, -COO-, -OCO-, and -0 (CH2) m- (m is a group of 1 to 5) And X4 is an integer of at least 1 or 2 selected from the group consisting of a pyrrole ring, an amino ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole, a benzimidazole ring, and a benzimidazole ring. Preferably, X丨, x2, X3, X4 and H in the formula [1] are at least one selected from the group consisting of -〇-, -NQ1-, -CONQ1-, -NC^CO- and a group, and X2 is selected from the group consisting of At least one of a group consisting of a single bond, a carbon number of 1 or a branched alkyl group, and a benzene ring, a single bond, -〇-, -C0NQ2-, -NQ2C0- '-COO-, 0(CH2)m- (m is X4 of the group formed by the integer of 1 to 5 is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, and a pyridine ring, and η is an integer of 1 or 2. Further preferably in the formula [1] Xi, Χ2, Χ3, Χ4, and X! are at least one selected from the group consisting of -0-, -NQ1-, -C0NQ1-, and -NC^CO-, and X2 is selected from the group consisting of a single bond, a carbon number of 1 to 3, and benzene. At least one of the group consisting of a ring, X3 being at least one selected from the group consisting of 骂 and -CH 2 -. Χ4 is a group selected from the group consisting of η, -C Η 2 〇- and -t 1 to 10, and an integer of -nq2co-), an azole ring, a pyrazole ring, an acridine ring, η is The combination of Xj-CH20- to linear linear group X5 is selected from the group consisting of at least one of -0O0- and _, and the combination of y-pyrimidine ring η is a group of linear alkyl groups [key, -0C0- Imidazole ring, 200940506 [One less, η is 1 or 2, and the combination of Χ4 and η is the number of the following Q2 series and the group consisting of the same pyridine ring and pyrimidine ring as defined by formula [1]. Preferably, ι, X2, and Tables 1 to 3 in the formula [1] are shown. And, Q1 and ❿ -19- 200940506 [Table 1]

Xi X2 χ3 X4 A-l -0- 單鍵 單鍵 咪唑環 A-2 單鍵 單鍵 吡陡環 A-3 -0- 單鍵 單鍵 嘧啶環 A-4 -NQ1- 單鍵 單鍵 咪唑環 A-5 -NQ1- 單鍵 單鍵 耻陡環 A-6 -NQ1- 單鍵 單鍵 嘧啶環 A-7 -CONQ1- 單鍵 單鍵 咪唑環 A-8 -CONQ1- 單鍵 單鍵 吡陡環 A-9 -CONQ1- 單鍵 單鍵 嘧啶環 A-10 -nq'co- 單鍵 單鍵 咪唑環 A-ll -NQ1。。- 單鍵 單鍵 妣陡環 A-12 -NQ’CO- 單鍵 單鍵 嘧啶環 A-13 碳數1至3之直鏈伸烷基 單鍵 咪唑環 A-14 碳數1至3之直鏈伸烷基 單鍵 吡啶環 A-l 5 碳數1至3之直鏈伸烷基 單鍵 嘧啶環 A-16 碳數1至3之直鏈伸烷基 -OCO- 咪唑環 A-17 碳數1至3之直鏈伸烷基 -0C0- 吡啶環 A-18 碳數1至3之直鏈伸烷基 -0C0- 嘧啶環 A-19 -0- 碳數1至3之直鏈伸烷基 -och2- 咪唑環 A-20 -0- 碳數1至3之直鏈伸烷基 -och2- 口比陡環 A-21 -0- 碳數1至3之直鏈伸烷基 -och2- 嘧啶環 A-22 -NQ1- 碳數1至3之直鏈伸烷基 單鍵 咪唑環 A-23 -NQ1- 碳數1至3之直鏈伸烷基 單鍵 口比陡環 A-24 -NQ1- 碳數1至3之直鏈伸烷基 單鍵 嘧啶環 A-25 -NQ1- 碳數1至3之直鏈伸烷基 -0C0- 咪唑環 A-26 -NQ1- 碳數1至3之直鏈伸烷基 -OCO- 口比陡環 A-27 -NQ1- 碳數1至3之直鏈伸烷基 -0C0- 嘧啶環 A-28 -NQ1- 碳數1至3之直鏈伸烷基 -och2- 咪唑環 A-29 -NQ1- 碳數1至3之直鏈伸烷基 -och2- 口比u定環 A-30 -NQ1- 碳數1至3之直鏈伸烷基 -och2- 嘧啶環 A-31 -CONQ1- 碳數1至3之直鏈伸烷基 單鍵 咪唑環 200940506 〔表2〕Xi X2 χ3 X4 Al -0- single bond single bond imidazole ring A-2 single bond single bond pyridyl ring A-3 -0- single bond single bond pyrimidine ring A-4 -NQ1- single bond single bond imidazole ring A- 5 -NQ1- single bond single bond shame steep ring A-6 -NQ1- single bond single bond pyrimidine ring A-7 -CONQ1- single bond single bond imidazole ring A-8 -CONQ1- single bond single bond pyridyl ring A- 9 -CONQ1- single bond single bond pyrimidine ring A-10 -nq'co- single bond single bond imidazole ring A-ll-NQ1. . - One-button single bond 妣 steep ring A-12 -NQ'CO- Single bond single bond Pyrimidine ring A-13 Carbon number 1 to 3 Linear alkyl group Single bond Imidazole ring A-14 Carbon number 1 to 3 Chain alkyl group single bond pyridine ring Al 5 carbon chain number 1 to 3 linear alkyl group single bond pyrimidine ring A-16 carbon number 1 to 3 linear chain alkyl group - OCO - imidazole ring A-17 carbon number 1 Straight chain alkyl group to 3-C0-pyridine ring A-18 carbon chain 1 to 3 linear alkyl group -0C0-pyrimidine ring A-19 -0- straight chain alkyl group having 1 to 3 carbon atoms - Och2-imidazole ring A-20 -0- straight chain alkyl-ochoch with a carbon number of 1 to 3 - mouth ratio steep ring A-21 -0- linear alkyl-och2-pyrimidine ring having 1 to 3 carbon atoms A-22 -NQ1 - straight chain alkylene single bond imidazole ring of carbon number 1 to 3 A-23 -NQ1 - straight chain alkyl single bond ratio of carbon number 1 to 3 than steep ring A-24 -NQ1- Straight chain alkyl-terminated pyrimidine ring A-25 -NQ1- having a carbon number of 1 to 3, linear alkyl-C0-C0--imidazole ring A-26 -NQ1- having a carbon number of 1 to 3 Chain-alkyl-OCO-port ratio steep ring A-27 -NQ1- linear alkyl 1C-pyrimidine-A-C-pyrimidine ring A-28-NQ1- linear alkyl group having 1 to 3 carbon atoms -och2-imidazole ring A-29 -NQ1- carbon number 1 to 3 straight-chain alkyl-och2-mouth ratio u-ring A-30 -NQ1- straight-chain alkyl group having 1 to 3 carbon atoms -och2-pyrimidine ring A-31 -CONQ1- carbon number 1 to 3 Chain extended alkyl single bond imidazole ring 200940506 [Table 2]

Xi X2 x3 X4 A-32 -CONQ1- 碳數1至3之直鏈伸烷基 單鍵 耻陡環 A-33 -CONQ1- 碳數1至3之直鏈伸院基 單鍵 嘧幌 A-34 -CONQ1- 碳數1至3之直鏈伸院基 -OCO- 咪唑環 A-35 -CONQ1- 碳數1至3之直鏈伸烷基 -OCO- 口比陡環 A-36 -CONQ1- 碳數1至3之直鏈伸烷基 -OCO- 喃陡環 A-37 -CONQ1- 碳數1至3之直鏈伸烷基 -och2- 咪唑環 A-38 -CONQ1- 碳數1至3之直鏈伸烷基 -och2- 啦陡環 A-39 -CONQ1- 碳數1至3之直鏈伸烷基 -och2- 嘧啶環 A-40 -nq!co- 碳數1至3之直鏈伸烷基 單鍵 咪唑環 A-41 -NQ^O- 碳數1至3之直鏈伸烷基 單鍵 口比淀環 A-42 -NQ1。。- 碳數1至3之直鏈伸烷基 單鍵 嘧啶環 A-43 -NQ^O- 碳數1至3之直鏈伸烷基 -OCO- 咪唑環 A-44 -NQ^O- 碳數1至3之直鏈伸烷基 -OCO- 咖定環 A-45 -NQ1。。- 碳數1至3之直鏈伸烷基 -OCO- 嘧啶環 A-46 -NC^CO- 碳數1至3之直鏈伸烷基 -och2- 咪唑環 A-47 -nq!co- 碳數1至3之直鏈伸烷基 -och2- 咖定環 A-48 -NQ^O- 碳數1至3之直鏈伸烷基 -OCHr 嘧啶環 A-49 苯環 單鍵 咪唑環 A-50 -0- 苯環 單鍵 吡啶環 A-51 苯環 單鍵 嘧啶環 A-52 苯環 -OCO- 咪唑環 A-53 -0- 苯環 -OCO- 吡啶環 A-54 苯環 -OCO- 哺陡環 A-55 苯環 -och2- 咪唑環 A-56 苯環 -och2- 耻口定環 A-57 -0- 苯環 -och2- 嘧陡環 A-58 -NQ1- 苯環 單鍵 咪哩環 A-59 -NQ1- 苯環 單鍵 口比淀環 A-60 -NQ1- 苯環 單鍵 嘧啶環 A-61 -NQ1- 苯環 -OCO- 咪唑環 A-62 -NQ1- 苯環 -OCO- 口比口定環 -21 - 200940506 〔表3〕Xi X2 x3 X4 A-32 -CONQ1- Linear 1 to 3 straight chain alkyl single bond shaky steep ring A-33 -CONQ1- Carbon number 1 to 3 straight chain extension base single bond pyrimidine A-34 -CONQ1- linear chain of 1 to 3 carbon atoms -OCO-imidazole ring A-35 -CONQ1- linear alkyl-OCO- toluene ratio A-36 -CONQ1- carbon Linear 1 to 3 linear alkyl-OCO-pyramid A-37-CONQ1- linear alkyl 1 to 3 -och2-imidazole ring A-38 -CONQ1- carbon number 1 to 3 Linear alkyl-och2- 陡 steep ring A-39 -CONQ1- linear alkyl 1 to 3 alkyl-och2-pyrimidine ring A-40 -nq!co- linear extension of carbon number 1 to 3 Alkyl single bond imidazole ring A-41 -NQ^O- The linear one-link alkyl single bond of carbon number 1 to 3 is more than the precipitate ring A-42 -NQ1. . - a straight-chain alkyl-monomethylpyrimidine ring having a carbon number of 1 to 3, A-43 -NQ^O-, a linear alkyl group having 1 to 3 carbon atoms - OCO-imidazole ring A-44 - NQ^O- Straight chain alkyl-OCO-caco ring A-45-NQ1 of 1 to 3. . - Linear alkyl-OCO-pyrimidine ring A-46 -NC^CO- having a carbon number of 1 to 3, linear alkyl-och2-carbon number 1 to 3 -imidazole ring A-47 -nq!co- carbon直直 alkyl-och2- gading ring A-48 -NQ^O- straight chain alkyl group having 1 to 3 carbon atoms - OCHr pyrimidine ring A-49 benzene ring single bond imidazole ring A- 50 -0- phenyl ring single bond pyridine ring A-51 benzene ring single bond pyrimidine ring A-52 benzene ring-OCO- imidazole ring A-53 -0- benzene ring-OCO- pyridine ring A-54 benzene ring-OCO- Feeding ring A-55 benzene ring-och2-imidazole ring A-56 benzene ring-och2- shame ring A-57 -0- benzene ring-och2-pyrimidine ring A-58 -NQ1- benzene ring single bond Anthracycline A-59 -NQ1- benzene ring single bond port ratio ring A-60 -NQ1- benzene ring single bond pyrimidine ring A-61 -NQ1-benzene ring-OCO-imidazole ring A-62 -NQ1-benzene ring- OCO- mouth ratio ring - 21 - 200940506 [Table 3]

Xi x2 χ3 X4 A-63 -NQ1- 苯環 -OCO- 嘧啶環 A-64 -NQ1- 苯環 -och2- 咪唑環 A-65 -NQ1- 苯環 -OCH2- 吡啶環 A-66 -NQ1- 苯環 -OCH2- 嘧啶環 A-67 -CONQ1- 苯環 單鍵 咪哇環 A-68 -CONQ1- 苯環 單鍵 吡陡環 A-69 -CONQ1- 苯環 單鍵 嘧啶環 A-70 -CONQ1- 苯環 -OCO- 咪唑環 A-71 -CONQ1- 苯環 -OCO- 吡啶環 A-72 -CONQ1- 苯環 -OCO- 嘧幌 A-73 -CONQ1- 苯環 -och2- 咪唑環 A-74 -CONQ1- 苯環 -OCH2- 吡啶環 A-75 -CONQ1- 苯環 -OCH2- 嘧啶環 A-76 -NC^CO- 苯環 單鍵 咪唑環 A-77 -NQ^O- 苯環 單鍵 口比陡環 A-78 -NC^CO- 苯環 單鍵 嘧啶環 A-79 -NC^CO- 苯環 -OCO- 咪唑環 A-80 -NQ1。。- 苯環 -OCO- 口比陡環 A-81 -NQ^O- 苯環 -OCO- 嘧啶環 A-82 -nq'co- 苯環 -och2- 咪唑環 A-83 -NC^CO- 苯環 -OCH2- 耻陡環 A-84 -NQ1。。- 苯環 -OCH2- 嘧啶環 A-85 -CONQ1- 苯環 單鍵 咪唑環 A-86 -CONQ1- 苯環 單鍵 吡淀環 A-87 -CONQ1- 苯環 單鍵 嘧啶環 A-88 -CONQ1- 苯環 -OCO- 咪唑環 A-89 -CONQ1- 苯環 -OCO- 咖定環 A-90 -CONQ1- 苯環 -OCO- 嘧啶環 A-91 -CONQ1- 苯環 -och2- 咪唑環 A-92 -CONQ1- 苯環 -OCH2- 吡陡環 A-93 -CONQ1- 苯環 -OCH2- 嘧啶環 -22- 200940506 <特定二胺化合物之合成方法> 本發明之以式〔1〕表示之特定二胺化合物之製造方 法並無特別限制，但較佳之方法列舉於下。Xi x2 χ3 X4 A-63 -NQ1- benzene ring-OCO-pyrimidine ring A-64 -NQ1-benzene ring-och2-imidazole ring A-65 -NQ1-benzene ring-OCH2-pyridine ring A-66 -NQ1-benzene Cyclo-OCH2-pyrimidine ring A-67 -CONQ1- benzene ring single bond imiline ring A-68 -CONQ1- benzene ring single bond pyridyl ring A-69 -CONQ1- benzene ring single bond pyrimidine ring A-70 -CONQ1- Benzene ring-OCO-imidazole ring A-71-CONQ1-benzene ring-OCO-pyridine ring A-72-CONQ1-benzene ring-OCO-pyrimidine A-73 -CONQ1-benzene ring-och2-imidazole ring A-74 CONQ1-benzene ring-OCH2-pyridine ring A-75-CONQ1-benzene ring-OCH2-pyrimidine ring A-76 -NC^CO- benzene ring single bond imidazole ring A-77 -NQ^O- benzene ring single bond ratio Steep ring A-78 -NC^CO- benzene ring single bond pyrimidine ring A-79 -NC^CO- benzene ring-OCO- imidazole ring A-80 -NQ1. . - Benzene ring-OCO-port ratio steep ring A-81 -NQ^O- benzene ring-OCO-pyrimidine ring A-82 -nq'co- benzene ring-och2-imidazole ring A-83 -NC^CO- benzene ring -OCH2- shame steep ring A-84 - NQ1. . - Benzene ring-OCH2-pyrimidine ring A-85 -CONQ1- benzene ring single bond imidazole ring A-86 -CONQ1- benzene ring single bond pyridyl ring A-87 -CONQ1- benzene ring single bond pyrimidine ring A-88 -CONQ1 - Benzene ring-OCO-imidazole ring A-89 -CONQ1-benzene ring-OCO- gading ring A-90 -CONQ1- benzene ring-OCO-pyrimidine ring A-91 -CONQ1- benzene ring-och2-imidazole ring A- 92 -CONQ1 - phenyl ring-OCH2-pyrrole ring A-93 -CONQ1-benzene ring-OCH2-pyrimidine ring-22- 200940506 <Synthesis method of specific diamine compound> The present invention is represented by the formula [1] The method for producing the specific diamine compound is not particularly limited, and preferred methods are listed below.

0 本發明之特定二胺化合物係合成以式〔4〕表示之二 硝基體’接著使硝基還原轉化成胺基而獲得。使二硝基化 合物還原之方法並無特別限制，通常藉由使用鈀-碳、氧 化鈾、阮尼鎳、鉑黑、釕-氧化鋁、硫化鉑碳等觸媒，於 乙酸乙酯、甲苯、四氫呋喃、二噁烷、醇系等溶劑中，以 氫氣、聯胺、氯化氫等進行之方法。式〔4〕中之 、X3、X4及n與式〔1〕之定義相同。 式〔4〕之二硝基體可透過X3鍵結χ2及X4，隨後， 〇 透過χι鍵結二硝基部之方法，透過連結部Xi使二硝基部 與X2鍵結，隨後，透過χ3與χ4鍵結之方法等獲得。 X!爲選自由-Ο-(醚鍵）、-NQ1-(胺基鍵）、-CONQ1^ 醯胺鍵）'-NQicO-(反醯胺鍵）、-CH20-(亞 甲基醚鍵）及-OCO-(反酯鍵）所組成組群之至少一種鍵 結基’該等之鍵結基可以通常之有機合成方法形成。各鍵 結基之Q1係與式〔1〕之定義相同。 例如，於X1爲醚、亞甲基醚鍵之情況，舉例爲使對 應之含有二硝基之鹵素衍生物與含有x2、乂3及x4之羥基 -23- 200940506 衍生物在鹼存在下反應之方法，或使含有二硝基之羥基衍 生物與含有x2、x3及Χ4之鹵素取代之衍生物在鹼存在下 反應之方法。 於胺基鍵之情況，舉例爲使對應之含有二硝基之鹵素 衍生物與含有χ2、χ3及χ4之胺基衍生物在鹼存在下反應 之方法。 於反酯鍵之情況，舉例爲使對應之含有二硝基之羥基 衍生物與含有Χ2、Χ3及Χ4之醯氯體在鹼存在下反應之方 q 法。 於醯胺鍵之情況，舉例爲使對應之含有二硝基之醯氯 體與含有Χ2、χ3及χ4之胺基取代體在鹼存在下反應之方 法。 於反醯胺鍵之情況，舉例爲使對應之含有二硝基之胺 代體與含有Χ2、χ3及χ4之醯氯體在鹼存在下反應之 方法。 含有二硝基之鹵素衍生物及含有二硝基之衍生物之具 〇 體例舉例爲3,5-二硝基氯苯、2 4_二硝基氯苯、2,4_二硝 基氟苯、3,5-二硝基苯甲醯氯、3,5•二硝基苯甲酸、2,4_二 硝基苯甲醯氯、2，4-二硝基苯甲酸、3，5_二硝基苄基氯、 2.4- 二硝基节基氯、3,5_二硝基苄基醇、2,4_二硝基苄基醇 、2,4-二硝基苯胺、3,5_二硝基苯胺、2,6_二硝基苯胺、 2.4- 二硝基酌、2,5-二硝基酚、2,6_二硝基酚、2,4·二硝基 苯基乙酸等°考量原料之取得性、反應方面，可選擇一種 或複數種。 -24- 200940506 <聚合物> 本發明之聚合物係藉由含有特定二胺化合物之二胺成 分與四羧酸二酐之反應獲得之聚醯胺酸及使該聚醯胺酸脫 水閉環獲得之聚醯亞胺。該等聚醯胺酸及聚醯亞胺之任一 種均可使用作爲獲得液晶配向膜之聚合物。 使用本發明之聚合物獲得之液晶配向膜，若上述二胺 成分中之特定二胺化合物之含有比例越多，則電壓維持率 〇 高’且即使在高溫下長時間暴露後，亦可及早緩和因直流 電壓所累積之殘留電荷。 爲了提高上述特性之目的，以二胺成分之1莫耳％以 上爲特定二胺化合物較佳。另外，二胺成分之5莫耳％以 上爲特定二胺化合物較佳，更好爲10莫耳％以上。 亦可爲二胺成分之1 00莫耳％係特定二胺化合物，但 就塗佈液晶配向處理劑時之均勻塗佈性之觀點而言，特定 二胺化合物爲二胺成分之80莫耳％以下較佳，更好爲4〇 © 莫耳％以下。 本發明中亦可倂用特定二胺化合物以外之二胺（以下 亦稱爲其他二胺化合物），其他二胺化合物並無特別限制 。其具體例舉例於下。 對-苯二胺、2,3,5,6-四甲基-對-苯二胺、2,5-二甲基_ 對-苯二胺、間-苯二胺、2,4-二甲基-間-苯二胺、2,5·二胺 基甲苯、2,6-二胺基甲苯、2,5-二胺基酚、2,4-二胺基酣、 3.5- 二胺基酚、3,5-二胺基苄基醇、2,4-二胺基苄基醇、 4.6- 二胺基間苯二甲酚、4,4’-二胺基聯苯、3,3’-二甲基_ -25- 200940506 4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、3,3’-二羥基-4,4’-二胺基聯苯、3,3’-二氟-4,4’-聯苯、3,3’-三氟 甲基-4,4’-二胺基聯苯、3,4’-二胺基聯苯、3,3’-二胺基聯 苯、2,2’-二胺基聯苯、2,3’-二胺基聯苯、4,4’-二胺基二 苯基甲烷、3，3’-二胺基二苯基甲烷、3，4’-二胺基二苯基甲 烷、2,2’ -二胺基二苯基甲烷、2，3’ -二胺基二苯基甲烷、 4,4’ -二胺基二苯基醚、3,3’ -二胺基二苯基醚、3,4’ -二胺 基二苯基醚、2,2’-二胺基二苯基醚、2,3’-二胺基二苯基醚 、4,4’-磺醯基二苯胺、3,3’-磺醯基二苯胺、雙（4-胺基苯 基）矽烷、雙（3-胺基苯基）矽烷、二甲基-雙（4-胺基苯 基）矽烷、二甲基-雙（3-胺基苯基）矽烷、4，4’-硫二苯 胺、3,3’-硫二苯胺、4,4’-二胺基二苯基胺、3,3’-二胺基 二苯基胺、3,4’-二胺基二苯基胺、2,2’-二胺基二苯基胺、 2，3’-二胺基二苯基胺、N-甲基（4，4’-二胺基二苯基）胺、 N-甲基（3,3’_二胺基二苯基）胺、N-甲基（3,4’_二胺基二 苯基）胺、N-甲基（2,2’-二胺基二苯基）胺、N-甲基（ 2,3’ -二胺基二苯基）胺、4,4’ -二胺基二苯甲酮、3，3’ -二 胺基二苯甲酮、3,4’-二胺基二苯甲酮、1，4-二胺基萘、 2,2’-二胺基二苯甲酮、2,3’·二胺基二苯甲酮、1,5-二胺基 萘、1，6-二胺基萘、1，7-二胺基萘、1,8-二胺基萘、2,5-二 胺基萘、2,6-二胺基萘、2,7-二胺基萘、2,8-二胺基萘、 1.2- 雙（4-胺基苯基）乙烷、1,2-雙（3-胺基苯基）乙烷、 1.3- 雙（4-胺基苯基）丙烷、1,3-雙（3-胺基苯基）丙烷、 1.4- 雙（4-胺基苯基）丁烷、1,4-雙（3-胺基苯基）丁烷、 -26- 200940506 雙（3,5-二乙基-4-胺基苯基）甲烷、1,4-雙（4-胺基苯氧 基）苯、1，3-雙（4_胺基苯氧基）苯、I，4-雙（4_胺基苯基 )苯、1，3-雙（4-胺基苯基）苯、1，4-雙（4-胺基苄基）苯 、1,3-雙（4-胺基苯氧基）苯、4,4’-〔 1，4-伸苯基雙（亞 甲基）〕二苯胺、4,4’-〔1，3-伸苯基雙（亞甲基）〕二苯 胺、3,4’-〔 1,4-伸苯基雙（亞甲基）〕二苯胺、3,4’-〔 1,3-伸苯基雙（亞甲基）〕二苯胺、3,3’-〔 1，4-伸苯基雙 φ (亞甲基）〕二苯胺、3,3’-〔1,3-伸苯基雙（亞甲基）〕 二苯胺、1,4-伸苯基雙〔（4-胺基苯基）甲烷〕、1，4-伸 苯基雙〔（3-胺基苯基）甲烷〕、1，3-伸苯基雙〔（4-胺 基苯基）甲烷〕、1,3-伸苯基雙〔（3-胺基苯基）甲烷〕 、1，4-伸苯基雙（4-胺基苯甲酸酯）、1，4-伸苯基雙（3-胺 基苯甲酸酯）、1，3-伸苯基雙（4-胺基苯甲酸酯）、1，3-伸苯基雙（3-胺基苯甲酸酯）、雙（4-胺基苯基）對苯二 甲酸酯、雙（3-胺基苯基）對苯二甲酸酯、雙（4-胺基苯 φ 基）間苯二甲酸酯、雙（3 -胺基苯基）間苯二甲酸酯、 N，N’- ( 1，4-伸苯基）雙（4-胺基苄醯胺）、N，N’- ( 1，3-伸 苯基）雙（4-胺基苄醯胺）、N，N’- ( 1，4-伸苯基）雙（3-胺基苄醯胺）、N，N’- ( 1,3-伸苯基）雙（3-胺基苄醯胺） 、N,N’_ ( 4-胺基苯基）對苯二甲醯胺、N，N’- ( 3-胺基苯 基）對苯二甲醯胺、Ν,Ν’- ( 4-胺基苯基）間苯二甲醯胺 、Ν，Ν’- ( 3-胺基苯基）間苯二甲醯胺、9,10-雙（4-胺基 苯基）蒽、4,4’-雙（4-胺基苯氧基）二苯基颯、2,2’-雙〔 4-(4-胺基苯氧基）苯基〕丙烷、2,2’-雙〔4-(4-胺基苯 -27- 200940506 甲 氧基）苯基〕六氟丙烷、2，2’-雙（4-胺基苯基）六 、2,2’-雙（3-胺基苯基）六氟丙烷、2,2’-雙（3-脸^/ 基苯基）六氟丙烷、2，2，_雙胺基苯基）丙燒、 叹基、4 雙 丨-胺基苯基）丙烷、2,2’_雙（3_胺基-扣甲基苯赛） 、1,3-雙（4-胺基苯氧基）丙烷、ι，3-雙（ 丙院、1，4 -雙（4-胺基苯氧基）丁院、ι，4-雙（3-B* 基）丁烷、I，5-雙（4_胺基苯氧基）戊烷、1，5_雙 雙 苯氧基）戊烷、1，6-雙（4-胺基苯氧基）己烷、！ 1 5 Ο ，7 〇 胺基苯氧基）己烷、I，7 -雙（4_胺基苯氧基）庚棱 v 雙（3-胺基苯氧基）庚烷、ΐ，8·雙（4_胺基苯氧 1 、1,8-雙（3-胺基苯氧基）辛院、ι，9-雙（4-胺基萊 ^ 伞_荽、 壬院、1,9-雙（3-胺基苯氧基）壬焼、1，ίο -雙（ 、胺_勢 氧基）癸烷、1，10-雙（3-胺基苯氧基）癸烷、1 η 本 5 1 1 r 胺基苯氧基）Η—烷、i，li -雙（3 -胺基苯氧基）+ 4' 1，12·雙（4-胺基苯氧基）十二烷、^厂雙（3_胺 ' )十二烷、雙（4-胺基環己基）甲烷、雙（4-胺凝 赛 棊，3,甲敦 環己基）甲烷、1，3-二胺基丙烷、1,4-二胺基丁棱、 ^ 、1，s 〜 胺基戊烷、1，6-二胺基己烷、1，7-二胺基庚烷、1 s 辛烷、1，9-二胺基壬烷、1，10-二胺基癸烷、l，lK〜 ^ 一烷、1，12-二胺基十二烷等。 十 另外，可舉例爲二胺側鏈上具有烷基、含氟_ 、变： 香環、脂肪族環、雜環、以及由該等組成之大環狀# 代基 之二胺，具體而言可例示爲以下述式〔DA1〕至式〔DA26 〕表示之二胺化合物。 -28- 200940506The specific diamine compound of the present invention is synthesized by synthesizing a dinitro group represented by the formula [4], followed by reduction conversion of a nitro group to an amine group. The method for reducing the dinitro compound is not particularly limited, and is usually carried out by using a catalyst such as palladium-carbon, uranium oxide, ruthenium nickel, platinum black, ruthenium-alumina, or platinum sulfide carbon in ethyl acetate or toluene. Among the solvents such as tetrahydrofuran, dioxane, and alcohol, hydrogen, hydrazine, hydrogen chloride, and the like are used. In the formula [4], X3, X4 and n are the same as defined in the formula [1]. The dinitro group of the formula [4] can be bonded to the oxime 2 and X4 through the X3 bond, and then the ruthenium is bonded to the X 2 through the linking portion Xi by the χ 键 bond to the dinitro moiety, and then the χ 3 and χ 4 bonds are transmitted through the conjugate The method of the knot is obtained. X! is selected from the group consisting of -Ο-(ether bond), -NQ1-(amino bond), -CONQ1^ guanamine bond)'-NQicO-(reverse guanamine bond), -CH20- (methylene ether bond) And at least one bonding group of the group consisting of -OCO- (transesterification) - these bonding groups can be formed by a usual organic synthesis method. The Q1 system of each bonding group is the same as the definition of the formula [1]. For example, in the case where X1 is an ether or a methylene ether bond, for example, a corresponding halogen derivative containing a dinitro group and a hydroxy-23-200940506 derivative containing x2, oxime 3 and x4 are reacted in the presence of a base. Alternatively, or a method of reacting a dinitro group-containing hydroxy derivative with a halogen-substituted derivative containing x2, x3 and Χ4 in the presence of a base. In the case of an amino group bond, a method of reacting a corresponding halogen derivative containing a dinitro group with an amine derivative containing ruthenium, iridium 3 and ruthenium 4 in the presence of a base is exemplified. In the case of the reverse ester bond, for example, a method in which a corresponding dinitro group-containing hydroxy derivative is reacted with a ruthenium chloride containing ruthenium 2, iridium 3 and ruthenium 4 in the presence of a base is used. In the case of a guanamine bond, a method of reacting a corresponding dinitrogen-containing ruthenium chloride with an amine substituent containing ruthenium, iridium 3 and ruthenium 4 in the presence of a base is exemplified. In the case of the ruthenium amide bond, a method of reacting the corresponding dinitrogen-containing amine with a ruthenium chloride containing ruthenium, osmium 3 and ruthenium 4 in the presence of a base is exemplified. Examples of the halogen derivative containing a dinitro group and a derivative containing a dinitro group are 3,5-dinitrochlorobenzene, 24-dinitrochlorobenzene, 2,4-dinitrofluorobenzene. , 3,5-dinitrobenzimid chloride, 3,5•dinitrobenzoic acid, 2,4-dinitrobenzamide chloride, 2,4-dinitrobenzoic acid, 3,5_two Nitrobenzyl chloride, 2.4-dinitrohexyl chloride, 3,5-dinitrobenzyl alcohol, 2,4-dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5_ Dinitroaniline, 2,6-dinitroaniline, 2.4-dinitrobenzene, 2,5-dinitrophenol, 2,6-dinitrophenol, 2,4.dinitrophenylacetic acid, etc. ° One or more kinds may be selected in consideration of the availability and reaction of the raw materials. -24- 200940506 <Polymer> The polymer of the present invention is a polylysine obtained by reacting a diamine component containing a specific diamine compound with a tetracarboxylic dianhydride and dehydrating the polyglycine The obtained polyimine. Any of these polyamic acid and polyimine can be used as a polymer for obtaining a liquid crystal alignment film. When the liquid crystal alignment film obtained by using the polymer of the present invention has a higher ratio of a specific diamine compound in the above diamine component, the voltage maintenance ratio is high, and even after prolonged exposure at a high temperature, it can be relaxed early. The residual charge accumulated by the DC voltage. In order to enhance the above characteristics, it is preferred to use a specific diamine compound of 1 mol% or more of the diamine component. Further, more than 5 mol% of the diamine component is preferably a specific diamine compound, more preferably 10 mol% or more. Further, it may be a specific diamine compound of 100% by weight of the diamine component, but the specific diamine compound is 80% by mole of the diamine component from the viewpoint of uniform coatability when the liquid crystal alignment agent is applied. The following is preferred, and it is preferably 4% or less. In the present invention, a diamine other than a specific diamine compound (hereinafter also referred to as another diamine compound) may be used, and other diamine compounds are not particularly limited. Specific examples thereof are given below. p-Benzyldiamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl Base-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminopurine, 3.5-diaminophenol , 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4.6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'- Dimethyl _ -25- 200940506 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4, 4'-Diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4' -diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diamino Diphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-di Aminodiphenyl ether, 2,3'-diaminodiphenyl ether , 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-double (4-Aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diamine Diphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'- Diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl (3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2,3'-diaminodiphenyl) Amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene , 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-di Amino naphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1.2 - Double (4 -aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1.3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl) Propane, 1.4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, -26- 200940506 bis(3,5-diethyl-4-amine Phenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, I,4-bis(4-aminophenyl) Benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4 , 4'-[ 1,4-phenylphenylbis(methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'- [1,4-phenylphenylbis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[ 1,4 -Extended phenylbis(methylene)]diphenylamine, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylene bis[(4- Aminophenyl)methane], 1,4-phenylene bis[(3-aminophenyl)methane], 1,3-phenylene bis[(4-aminophenyl)methane], 1, 3 - phenyl bis[(3-aminophenyl)methane], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzene) Formate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminobenzene) Terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenylφ)isophthalate, bis(3-aminophenyl) ) isophthalate, N, N'-(1,4-phenylene) bis(4-aminobenzylamine), N,N'-(1,3-phenylene)bis (4) -aminobenzylamine, N,N'-(1,4-phenylene)bis(3-aminobenzylamine), N,N'-(1,3-phenylene)bis (3) -aminobenzylguanamine), N,N'_(4-aminophenyl)terephthalamide, N,N'-(3-aminophenyl)terephthalamide, hydrazine, Ν'-(4-Aminophenyl) m-xylylenediamine, hydrazine, Ν'-(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl) ), 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 '-Bis[4-(4-aminophenyl-27-200940506 methoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexa, 2,2'-bis ( 3-aminophenyl)hexafluoropropane, 2,2'-bis(3-faced^ylphenyl)hexafluoropropane, 2,2,-diaminophenyl)propane, singer, 4 pairs丨-Aminophenyl)propane, 2,2'-bis (3-amino-methyl ketone), 1,3-bis(4-aminophenoxy)propane, ι,3-double ( Propyl, 1,4-bis(4-aminophenoxy)butyl, i,4-bis(3-B*yl)butane, I,5-bis(4-aminophenoxy)pentane Alkane, 1,5-bis-bisphenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1 5 Ο , 7 〇 〇 苯 phenoxy) hexane, I, 7 - bis ( 4 -aminophenoxy) heptyl v bis (3-aminophenoxy) heptane, hydrazine, 8 · double (4_Aminophenoxy 1 , 1,8-bis(3-aminophenoxy) xinyuan, ι, 9-bis (4-aminola lan] umbrella 荽, brothel, 1,9-double (3-Aminophenoxy)anthracene, 1, ίο-bis(,amine-potentialoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1 η, 5 1 1 r aminophenoxy)anthracene, i,li-bis(3-aminophenoxy)+ 4' 1,12·bis(4-aminophenoxy)dodecane, ^factor double (3_amine') dodecane, bis(4-aminocyclohexyl)methane, bis(4-amine condensed oxime, 3, methylenedicyclohexyl)methane, 1,3-diaminopropane, 1, 4-diaminobutyl rib, ^, 1, s ~ aminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 s octane, 1,9-diamine Base decane, 1,10-diamino decane, 1,1K~^ monoalkane, 1,12-diaminododecane, etc. Further, it may be exemplified that the diamine has an alkyl group on its side chain, Fluorine _, change: fragrant ring, aliphatic ring, heterocyclic ring, and the large ring composed of these Specifically, the diamine compound is a diamine compound represented by the following formula [DA1] to formula [DA26]. -28- 200940506

[DAI] [DA2] [DA 3] [DA4] [DA5] (式〔DAI〕至式〔DA5〕中，Ri爲碳數1以上22 以下之院基或含氣院基）。[DAI] [DA2] [DA 3] [DA4] [DA5] (In the formula [DAI] to [DA5], Ri is a hospital base or a gas-containing yard base with a carbon number of 1 or more and 22 or less.

〔化6〕[6]

(式〔DA6〕至式〔DA9〕中，R2 表示-COO-'-OCO-、-CONH-、-NHCO-、-CH2-、-Ο-、-CO-或-NH-，R3 表示 碳數1以上22以下之烷基或含氟烷基）。 〔化7〕(In the formula [DA6] to formula [DA9], R2 represents -COO-'-OCO-, -CONH-, -NHCO-, -CH2-, -Ο-, -CO- or -NH-, and R3 represents a carbon number. 1 or more and 22 or less alkyl groups or fluorine-containing alkyl groups). [7]

(式〔DA10〕至式〔DA11〕中，R4 表示-0-、-OCH2-、-CH20-、-COOCH2-或-CH2OCO-，R5 表示碳數 1 以上22以下之烷基、烷氧基、含氟烷基或含氟烷氧基） -29- 200940506(In the formula [DA10] to the formula [DA11], R4 represents -0-, -OCH2-, -CH20-, -COOCH2- or -CH2OCO-, and R5 represents an alkyl group having 1 to 22 or less carbon atoms, an alkoxy group, Fluorinated alkyl or fluoroalkoxy) -29- 200940506

(式〔DA12〕至式〔DA14〕中，R6 表示-COO-、-(In the formula [DA12] to the formula [DA14], R6 represents -COO-, -

OCO-、 -CONH-、-NHCO-、 -COOCH2-、 -CH2OCO- > - CH2〇-、-OCH2-或- CH2-，R7表示碳數1以上22以下之烷 基、烷氧基、含氟烷基或含氟烷氧基）。OCO-, -CONH-, -NHCO-, -COOCH2-, -CH2OCO- > - CH2〇-, -OCH2- or -CH2-, and R7 represents an alkyl group having 1 to 22 or less carbon atoms, an alkoxy group, and the like Fluoroalkyl or fluoroalkoxy).

(式〔DA15〕至式〔DA16〕中，R8 表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2-、-CH2OCO-、-CH20-、-OCH2-、-CH2-、-Ο-或-NH-，R9 表示氟、氰基、 三氟甲基、硝基、偶氮基、甲醯基、乙醯基、乙醯氧基或 羥基）。 -30- 200940506(In the formula [DA15] to the formula [DA16], R8 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH2-, -CH2OCO-, -CH20-, -OCH2-, -CH2-, -Ο- or -NH-, R9 represents fluorine, cyano, trifluoromethyl, nitro, azo, formamyl, ethinyl, ethoxylated or hydroxy). -30- 200940506

〔化 1 〇〕〔化1 〇〕

〔化 1 1〕〔化1 1〕

-31 - 200940506 〔化12-31 - 200940506

[DA2 5] [DA2 6] 除此之外，亦可舉例爲以下述式〔DA27〕表示之二 胺基矽氧烷等。 〔化 1 3〕 h2n——(ch2>3[DA2 5] [DA2 6] In addition, a diamine oxirane represented by the following formula [DA27] can also be exemplified. [化1 3] h2n——(ch2>3

CH3CH3

Si—(CH2)3—NH2 [DA2 7] (式〔DA27〕中，m爲1至10之整數）。 其他二胺化合物可依據作爲液晶配向膜時之液晶配向 性、電壓維持特性、累積電荷等特性，以一種或混合兩種 以上使用。 與二胺成分反應以獲得本發明聚醯胺酸之四羧酸二酐 並無特別限制。其具體例舉例如下。 均苯四酸二酐、2,3,6,7-萘四羧酸二酐、1，2,5,6-萘四 羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-蒽四羧酸二酐 、1，2,5,6-蒽四羧酸二酐、3,3’，4,4’-聯苯四羧酸二酐、 2,3,3’，4-聯苯四羧酸二酐、雙（3,4-二羧基苯基）醚、 3,3’，4,4’-二苯甲酮四羧酸二酐、雙（3,4-二羧基苯基）碾 、雙（3,4-二羧基苯基）甲烷、2,2-雙（3,4-二羧基苯基） 丙烷、1,1 ,1,3,3,3-六氟-2,2-雙（3,4-二羧基苯基）丙烷、 200940506 雙（3,4-二狻基苯基）二甲基砂院、雙（3,4_二羧基苯基 )二苯基矽烷、2,3,4,5-耻啶四羧酸二酐、26雙（34_二 羧基苯基）吡陡、3,3’，4,4’-二苯基颯四竣酸二肝、 3,4,9，10-比四殘酸一肝、1，3-一本基-1，2,3,4_環丁烷四羧 Ο ❹ 酸二酐、氧基二苯四羧酸二酐、1，2,3,4_環丁院四竣酸二 酐、1，2,3,4-環戊院四羧酸二酐、1，2,4,5_環己院四竣酸二 酐、1，2,3,4-四甲基-1，2,3,4-環丁院四竣酸—肝、1 2 —甲 基-1，2,3,4-環丁院四殘酸二肝、U3-二甲基-1，2,3,4_環丁烷 四殘酸二軒、1，2,3,4-環庚院四竣酸二酐、2,3,4,5_四氫咲 喃四羧酸二酐、3,4-二羧基-1-環己基琥珀酸二酐、2,3,5_ 三殘基環戊基乙酸二肝、3,4-二殘基四氫-萘琥 拍酸一酐、雙環〔3,3,0〕辛院- 2,4,6,8-四幾酸二軒、雙環 〔4,3,0〕壬烷-2,4,7,9-四羧酸二酐、雙環〔4,4,〇〕癸院_ 2,4,7,9-四竣酸二肝、雙環〔4,4,0〕癸烷_2,4,8,ι〇·四羧酸 酐 9，11 -四羧酸二酐 環〔6.3.0.0&lt;2,6&gt;〕十一院-3,5 、12,3,4-丁院四竣酸二肝、4- (2,5-二氧代四氫呋喃_3_基 )·1，2,3,4-四氫萘-1，2-二羧酸二酐、雙環〔22,2〕辛_7_ 烯-2,3,5,6-四羧酸二酐、5-(2,5-二氧代四氫呋喃基）-3_ 甲基-3-環己烷·1，2-二羧酸二酐、四環癸_ 4,5，9,10-四羧酸二酐、3,5,6-三羧基原冰片烷_2: 3,5: 6-二羧酸二酐、1,2,4,5-環己烷四羧酸二酐等。 四羧酸二酐可依據成爲液晶配向膜時之液晶配向性、 電壓保持性、累積電荷等特性，以一種使用或兩種以上倂 用。 -33- 200940506 藉由四羧酸二酐與二胺成分之反應，以獲得本發明之 聚醯胺酸可使用習知之合成方法。通常爲使四羧酸二酐與 二胺在有機溶劑中反應之方法。四羧酸二酐與二胺之反應 在有機溶劑中比較容易進行，且不產生副產物而言較有利 0 四羧酸二酐與二胺之反應中使用之有機溶劑只要可使 產生之聚醯胺酸溶解則無特別限制。其具體例列舉於下。 舉例爲N，N-二甲基甲醯胺、Ν,Ν-二甲基乙醯胺、N-甲基-2-吡咯啶酮、Ν-甲基己內醯胺、二甲基亞碾、四甲 基尿素、吡啶、二甲基颯、六甲基亞碾、r-丁內酯、異 丙醇、甲氧基甲基戊醇、二戊烯、乙基戊基酮、甲基壬基 酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、甲基溶 纖素、乙基溶纖素、甲基溶纖素乙酸酯、乙基溶纖素乙酸 酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯 、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇 單乙酸酯、丙二醇單甲基醚、丙二醇第三丁基醚、二丙二 醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二 甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚 、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙 二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲 氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇 、二異丙基醚、乙基異丁基醚、二異丁烯、乙酸戊酯、丁 酸丁酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二 己基醚、二噁烷、正己烷、正戊烷、正辛烷、二乙基醚、 -34- 200940506 環己酮、碳酸乙烯酯、碳酸丙烯酯、乳酸甲酯、乳酸乙酯 、乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸丙二醇單乙基 醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙 氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、 3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、 二甘醇二甲醚、4-羥基-4-甲基-2-戊酮等。該等可單獨使 用，亦可混合使用。而且，即使無法使聚醯胺酸溶解之溶 ❹ 劑，在不使產生之聚醯胺酸析出之範圍內，亦可混合於上 述溶劑中使用。 另外，有機溶劑中之水分會妨礙聚合反應，進而成爲 使所生成之聚醯胺酸水解之原因，因此有機溶劑較好使用 儘可能經脫水乾燥者。 使四羧酸二酐與二胺成分在有機溶劑中反應時，舉例 爲攪拌使二胺成分分散或溶解於有機溶劑中而成之溶液， 且直接添加四羧酸二酐之方法，或使之分散或溶解於有機 〇 溶劑中而添加之方法；相反地使二胺成分添加於將四羧酸 二酐分散或溶解於有機溶劑中而成之溶液中之方法；交互 添加四羧酸二酐及二胺成分之方法等，亦可使用該等之任 一種方法。另外，四羧酸二酐或二胺成分爲由複數種化合 物構成之情況下，亦可在事先混合之狀態下反應，亦可個 別依序反應，進而亦可使個別反應成之低分子量體混合反 應成高分子量體。 此時之聚合溫度可選擇自-20°c至150°C之任意溫度， 但較好爲-5 °C至100 °C之範圍。另外，反應可在任意之濃 -35- 200940506 度下進行’但由於濃度太低時難以獲得高分子量之聚合物 ，濃度太高時反應液體之黏性過高使得均勻攪拌變得困難 ’因此四羧酸二酐與二胺成分之反應溶液中之合計濃度較 好爲1至50質量％，更好爲5至30質量％。反應初期可 在高濃度下進行，隨後，再追加有機溶劑。 聚醯胺酸之聚合反應中，四羧酸二酐之合計莫耳數， 與二胺成分之合計莫耳數之比，較好爲0.8至1.2。如一 般之聚縮合反應般’該莫耳比趨近於1.0所生成之聚醯胺 ^ 酸之分子量最大。 本發明之聚醯亞胺爲使上述之聚醯胺酸經脫水閉環獲 得之聚醯亞胺，可使用作爲用以獲得液晶配向膜之聚合物 〇 本發明之聚醯亞胺中，醯胺酸基之脫水閉環率（醯亞 胺化率）未必須爲100%，可依據用途或目的做任意調整 〇 使聚醯亞胺酸醯亞胺化之方法舉例爲將聚醯胺酸之溶 0 液直接加熱之熱醯亞胺化，將觸媒添加於聚醯胺酸之溶液 中之觸媒醯亞胺化。 使聚醯胺酸溶液中熱醯亞胺化時之溫度爲100 °c至 400°C，較好爲120°C至250°C，且較好同時將醯亞胺化反 應產生之水排除於系統外。 聚醯胺酸之觸媒醯亞胺化可在聚醯胺酸之溶液中添加 鹼性觸媒及酸酐，且在-20至250°C，較好在〇至180°C下 攪拌而進行。鹼性觸媒之量爲醯胺酸基之0.5至30莫耳 -36- 200940506 倍，較好爲2至20莫耳倍，酸酐之量爲酿胺酸基之1至 50莫耳倍’較好爲3至30莫耳倍。至於鹼性觸媒可列舉 爲吡啶、三乙胺、三甲基胺、三丁基胺、三辛基胺等，其 中吡陡由於可維持適度的鹼性以使反應進行而較佳。至於 酸酐可舉例爲乙酸酐、偏苯三酸酐、苯均四甲酸酐等，其 中若使用酸酐則反應結束後之純化變得容易而較佳。由觸 媒醯亞胺化之醯亞胺化率可藉由調節觸媒量及反應溫度、 ❹ 反應時間予以控制。 由聚醯胺酸或聚醯亞胺之反應溶液回收所產生之聚醯 胺酸或聚醯亞胺之情況，可將反應溶液倒入弱溶劑中形成 沉澱。沉澱所使用之弱溶劑可舉例爲甲醇、丙酮、己烷、 丁基溶纖素、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、 甲苯、苯、水等。倒入弱溶劑中而沉澱之聚合物經過濾回 收後，可在常壓或減壓下，於常溫或加熱乾燥。另外，使 沉澱回收之聚合物再溶解於有機溶劑中，重複再沉澱回收 © 操作2至1 〇次，可減少聚合物中之雜質。此時之弱溶劑 舉例爲例如醇類、酮類、烴等，若使用選自該等之內之三 種以上弱溶劑，由於可更進一步的提高純化效率而較佳。 本發明之液晶配向處理劑中所含聚醯胺酸及聚醯亞胺 之分子量，於考量自其獲得之塗膜強度及塗膜形成時之作 業性、塗膜之均勻性之情況下，以GPC (凝膠滲透層析） 法測定之重量平均分子量以5,000至1，000,000較佳，更 好爲 10,000 至 150,000。 -37- 200940506 &lt;液晶配向處理劑&gt; 本發明之液晶配向處理劑爲用以形成液晶配向膜之塗 佈液，爲將用以形成樹脂被膜之樹脂成分溶解於有機溶劑 中而成之溶液。其中，上述之樹脂成分爲含有選自上述本 發明之聚合物之至少一種聚合物之樹脂成分。此時，樹脂 成分之含量以1質量％至2 0質量％較佳，更好爲3質量％ 至1 5質量％，最好爲3至1 0質量％。 本發明中，上述之樹脂成分可全部爲本發明中使用之 q 共聚物，亦可混合本發明之聚合物以外之其他聚合物。此 時，樹脂成分中之本發明聚合物以外之其他聚合物之含量 爲0.5質量％至15質量％，較好爲1質量％至10質量％。 該等其他聚合物舉例爲例如使用特定二胺化合物以外 之二胺化合物作爲與四羧酸二酐成分反應之二胺成分所獲 得之聚醯胺酸或聚醯亞胺等。 本發明之液晶配向處理劑中使用之有機溶劑只要是可 使樹脂成分溶解之有機溶劑則無特別限制。其具體例列舉 Q 於下。 舉例爲N，N-二甲基甲醯胺、Ν,Ν-二甲基乙醯胺、N-甲基-2-吡咯啶酮、Ν-甲基己內醯胺、2-吡咯啶酮、Ν-乙基 吡咯啶酮、Ν-乙烯基吡咯啶酮、二甲基亞楓、四甲基尿素 、吡啶、二甲基砸、六甲基亞碾、丁內酯、1，3-二甲 基 戊 基 乙 ' 醇 啶 唑 咪 I 基 基、 丙醚 異甲 基二 甲醇 、 甘 酮二 基、 戊酯 異烯 基丙 甲酸 酮 基 壬 基 甲、 、 酮 嗣 嗣 己 環 酮 基 乙 基 甲 酯 烯 乙 酸 碳 等 酮 戊 I 2 I 基 甲 墨 4 基 羥 I 4 碳該 -38- 200940506 等可單獨使用，亦可混合使用。 本發明之液晶配向處理劑亦可含有上述以外之成分。 其例爲在塗佈液晶配向處理劑時可改善膜厚均勻性或表面 平滑性之溶劑或化合物，提高液晶配向膜與基板之密著性 之化合物等。 提高膜厚均勻性或表面平滑性之溶劑（弱溶劑）之具 體例舉例爲下列者。 ❹ 舉例爲例如異丙醇、甲氧基甲基戊醇、甲基溶纖素、 乙基溶纖素、丁基溶纖素、甲基溶纖素乙酸酯、乙基溶纖 素乙酸酯、丁基卡必醇、乙基卡必醇、乙基卡必醇乙酸酯 、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇 單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、 丙二醇第三丁基醚、二丙二醇單甲基醚、二乙二醇、二乙 二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單 甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二 ® 醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙 酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲 基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚 、二異丁烯、乙酸戊酯、丁酸丁酯、丁基醚、二異丁基酮 、甲基環己烯、丙基醚、二己基醚、1-己醇、正己烷、正 戊烷、正辛烷、二乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲 酯、乙酸乙酯、乙酸正丁酯、乙酸丙二醇單乙基醚、丙酮 酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸 甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基 -39- 200940506 丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單 甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二 醇、2-(2 -乙氧基丙氧基）丙醇、乳酸甲酯、乳酸乙酯、 乳酸正丙酯、乳酸正丁酯、乳酸異戊酯等具有低表面張力 之溶劑等。 該等弱溶劑可單一種使用，亦可混合複數種使用。使 用如上述之溶劑時，較好爲液晶配向處理劑中所含之全部 溶劑之5至80質量％，更好爲20至60質量％。 至於提高膜後均勻性或表面平滑性之化合物舉例爲氟 系界面活性劑、矽氧系界面活性劑、非離子系界面活性劑 等。 更具體而言舉例爲例如F TOP EF301、EF303、EF352 (TOKEMU PRODUCT 公司製造）、MEGAFAX F171、 F173、R-30 (大曰本油墨公司製造）、FLUORAD FC430 、FC431 (住友 3M 公司製造）、ASAHIGUARD AG710、 SURFLON S-382、SC101、SC102、SC103、SC104、SC105 、SC106(旭硝子公司製造）等。該等界面活性劑之使用 比例相對於液晶配向劑中所含樹脂成分1 00質量份較好爲 0.01至2質量份，更好爲0.01至1質量份。 提高液晶配向膜與基板之密著性之化合物之具體例舉 例爲以下所示之含有官能性矽烷之化合物或含有環氧基之 化合物等。 200940506 舉例爲例如3-胺基丙基三甲氧基矽烷、3-胺基丙基三 乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙 氧基矽烷、N- (2-胺基乙基）-3-胺基丙基三甲氧基矽烷、 N-( 2-胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、3-脲基 丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基 羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙 基三乙氧基矽烷、N-三乙氧基矽烷基丙基三伸乙基三胺、 φ N-三甲氧基矽烷基丙基三伸乙基三胺、10-三甲氧基矽烷 基-1，4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸 烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯' 9-三乙氧 基矽烷基-3,6-二氮雜壬基乙酸酯、N-苄基-3-胺基丙基三 甲氧基矽烷、N-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽 烷、N-雙（氧伸乙基）-3-胺基丙基三甲氧基矽烷、N-雙 (氧伸乙基）-3-胺基丙基三乙氧基矽烷、乙二醇二縮水甘 〇 油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三 丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇 二縮水甘油醚、1，6-己二醇二縮水甘油醚、丙三醇二縮水 甘油醚、2,2-二溴新戊二醇二縮水甘油醚、1，3,5,6-四縮水 甘油基-2,4-己二醇、Ν,Ν,Ν’，Ν’-四縮水甘油基-間-二甲苯 二胺、1,3-雙（N，N-二縮水甘油基胺基甲基）.環己烷、 Ν,Ν,Ν’，Ν’-四縮水甘油基- 4,4’-二胺基二苯基甲烷等。 使用提高與基板之密著性之化合物時，其使用量相對 於液晶配向處理劑中所含樹脂成份100質量份，較好爲 -41 - 200940506 0.1至30質量份，更好爲1至20質量份。使用量若低於 〇.1質量份，則無法期待密著性提高之效果，若多於30質 量份，則有液晶配向性變差之情況。 本發明之液晶配向處理劑中，除上述以外，在不損及 本發明效果之範圍內，於使液晶配向膜之介電率或導電性 等之電性特性改變之目的下，亦可添加介電體或導電物質 ，進而，亦可添加成爲液晶配向膜之際提高膜之硬度或致 密度之目的之交聯性化合物。 q &lt;液晶配向膜、液晶顯示元件&gt; 本發明之液晶配向處理劑塗佈於基板上並燒成之後， 以摩擦處理或光照射等予以配向處理，或於垂直配向用途 等未經配向處理，可作爲液晶配向膜使用。此時，作爲所 用之基板只要是透明性高的基板則無特別限制，而可使用 玻璃基板或丙烯酸基板或聚碳酸酯基板等之塑膠基板等。 又，由製程簡單化之觀點觀之，使用形成有用以驅動液晶 D 之ITO電極等之基板較佳。又，即使於反射型液晶顯示元 件之僅成爲單面基板之矽晶圓等之不透明物亦可使用，此 時之電極亦可使用鋁等之可反射光之材料。 液晶配向處理劑之塗佈方法並無特別限制，工業上， 一般爲以網版印刷、平版印刷、軟版印刷、噴墨印刷等進 行之方法。至於其他塗佈方法，有浸漬塗佈、輥塗佈、狹 縫塗佈、旋轉塗佈等，亦可依據目的使用該等。 將液晶配向處理劑塗佈於基板上後之燒成，可藉由加 -42- 200940506 熱板等之加熱機構，於50至3 00°C ’較好於80至25 0°C進 行，使溶劑蒸發並形成塗膜。燒成後所形成之塗膜厚度， 若過厚則對液晶顯示元件之消耗電力方面不利，若過薄則 有液晶顯示元件之信賴性降低之情況’因此較好爲5至 3 00nm，更好爲10至l〇〇nm。液晶於水平配向或傾斜配向 時，燒成後之塗膜以摩擦或偏光紫外線照射等予以處理。 本發明之液晶顯示元件爲藉由上述方法自本發明之液 φ 晶配向處理劑獲得貼附有液晶配向膜之基板後，以習知方 法製作液晶單元，並作爲液晶顯示元件者。 若舉出液晶元件製作之一例，可舉例有準備形成有液 晶配向膜之一對基板，於其中一基板之液晶配向膜上散佈 隔離材，使液晶配向膜面成爲內側之方式，貼合另一片基 板，減壓注入液晶並封裝之方法，或於散佈隔離材之液晶 配向膜面上滴下液晶後貼合基板並進行封裝之方法等。此 時之隔離材厚度較好爲1至30μιη，更好爲2至ΙΟμιη。 〇 如以上，使用本發明之液晶配向處理劑製作之液晶顯 示元件成爲信賴性優異者，可適當利用於大畫面且高精細 之液晶電視等。 〔實施例〕 以下列舉實施例及比較例以更詳細說明本發明，但本 發明之解釋並不受該等實施例之限制。 〔二胺化合物之合成〕 -43- 200940506 〈實施例ι&gt;Si—(CH 2 ) 3 —NH 2 [DA 2 7] (in the formula [DA27], m is an integer of 1 to 10). Other diamine compounds may be used singly or in combination of two or more kinds depending on the characteristics of liquid crystal alignment, voltage maintenance characteristics, and accumulated electric charge when used as a liquid crystal alignment film. The reaction with the diamine component to obtain the tetracarboxylic dianhydride of the polyglycolic acid of the present invention is not particularly limited. Specific examples thereof are as follows. Pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Anhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,5,6-fluorene tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, Bis(3,4-dicarboxyphenyl) milled, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3 , 3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, 200940506 bis(3,4-dimercaptophenyl)dimethyl sand, double (3,4_ Dicarboxyphenyl)diphenylnonane, 2,3,4,5-discylenetetracarboxylic dianhydride, 26 bis(34-dicarboxyphenyl)pyrrole, 3,3',4,4'-di Phenyltetradecanoic acid di-hepatic, 3,4,9,10-to-tetrahydrous-hepatic, 1,3-indolyl-1,2,3,4-cyclobutanetetracarboxyindole phthalic acid dianhydride , oxydiphenyltetracarboxylic dianhydride, 1,2,3,4-cyclobutanine tetraphthalic acid dianhydride, 1,2,3,4-cyclopentanine tetracarboxylic dianhydride, 1,2,4 , 5_Huanjiyuan tetradecanoic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutyl Teic acid-liver, 1 2 -methyl-1,2,3,4-cyclobutanine tetraresidic acid di-hepatic, U3-dimethyl-1,2,3,4-cyclobutane tetraresidic acid Xuan, 1,2,3,4-cycloheptene tetradecanoic acid dianhydride, 2,3,4,5-tetrahydrofurfuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic acid Di-anhydride, 2,3,5_ three-residue cyclopentyl acetic acid di-hepatic, 3,4-di residue tetrahydro-naphthoic acid mono-anhydride, bicyclo [3,3,0] xinyuan - 2,4, 6,8-tetraacid acid Erxuan, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,〇]癸院_ 2,4, 7,9-tetradecanoic acid di-hepatic, bicyclo[4,4,0]nonane-2,4,8, ι〇·tetracarboxylic anhydride 9,11-tetracarboxylic dianhydride ring [6.3.0.0 &lt; 2 ,6&gt;]Eleventh Hospital-3,5,12,3,4-Dingyuan tetradecanoic acid liver, 4-(2,5-dioxotetrahydrofuran_3_yl)·1,2,3,4 - tetrahydronaphthalene-1,2-dicarboxylic dianhydride, bicyclo[22,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxo Tetrahydrofuranyl-3-methyl-3-cyclohexane·1,2-dicarboxylic dianhydride, tetracyclic guanidine 4,5,9,10-tetracarboxylic dianhydride, 3,5,6-tricarboxyl Orbornane-2: 3,5:6-dicarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and the like. The tetracarboxylic dianhydride may be used alone or in combination of two or more depending on characteristics such as liquid crystal alignment property, voltage retention property, and accumulated electric charge when it is a liquid crystal alignment film. -33- 200940506 A conventional synthetic method can be used by reacting a tetracarboxylic dianhydride with a diamine component to obtain a poly-proline of the present invention. It is usually a method of reacting a tetracarboxylic dianhydride with a diamine in an organic solvent. The reaction of the tetracarboxylic dianhydride with the diamine is relatively easy to carry out in an organic solvent, and is advantageous in that no by-product is produced. The organic solvent used in the reaction of the tetracarboxylic dianhydride and the diamine is only required to be produced. There is no particular limitation on the dissolution of the amino acid. Specific examples thereof are listed below. For example, N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, N-methyl-2-pyrrolidone, hydrazine-methyl caprolactam, dimethyl arsenic, Tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl argon, r-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl fluorenyl Ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate Ester, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate , propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate Monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3- Methyl-3-methoxybutyl acetate, tripropyl Alcohol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, -34- 200940506 cyclohexanone, ethylene carbonate, carbonic acid Propylene ester, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate , 3-ethoxypropionic acid methyl ethyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3 - butyl methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used singly or in combination. Further, even if the lysine which is incapable of dissolving the polylysine is not contained in the range in which the produced polyaminic acid is precipitated, it may be used in the above solvent. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polylysine, the organic solvent is preferably used as long as it is dehydrated and dried. When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, a solution obtained by dispersing or dissolving a diamine component in an organic solvent by stirring, and directly adding a tetracarboxylic dianhydride, or making it a method of dispersing or dissolving in an organic hydrazine solvent; and conversely adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride in an organic solvent; and intercalating tetracarboxylic dianhydride and Any of these methods may be used as the method of the diamine component. Further, when the tetracarboxylic dianhydride or the diamine component is composed of a plurality of kinds of compounds, it may be reacted in a state of being mixed beforehand, or may be reacted individually or sequentially, or a mixture of individual molecules may be mixed. The reaction is carried out into a high molecular weight body. The polymerization temperature at this time may be selected from any of -20 ° C to 150 ° C, but preferably in the range of -5 ° C to 100 ° C. In addition, the reaction can be carried out at any concentration of -35-200940506 degrees. However, it is difficult to obtain a high molecular weight polymer because the concentration is too low. When the concentration is too high, the viscosity of the reaction liquid is too high to make uniform stirring difficult. The total concentration in the reaction solution of the carboxylic acid dianhydride and the diamine component is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent is added. In the polymerization reaction of polyamic acid, the ratio of the total number of moles of tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably from 0.8 to 1.2. As the general polycondensation reaction, the molecular weight of the polyamidamine formed by the molar ratio approaching 1.0 is the largest. The polyimine of the present invention is a polyimine obtained by subjecting the above polyamic acid to dehydration ring closure, and can be used as a polymer for obtaining a liquid crystal alignment film. In the polyimine of the present invention, proline is used. The dehydration ring closure ratio (the imidization ratio) of the base is not necessarily 100%, and can be arbitrarily adjusted according to the purpose or purpose. The method for imidating the polyphosphonium imide is exemplified by the solution of polylysine. The enthalpy of the direct heating is imidized, and the catalyst is added to the solution of the polyaminic acid to imidize. The temperature at which the hydrazide imidization reaction is carried out is carried out at a temperature of from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C. Outside the system. The ruthenium imidization of poly-proline may be carried out by adding a basic catalyst and an acid anhydride to a solution of poly-proline, and stirring at -20 to 250 ° C, preferably at 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles -36 to 200940506 times, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles of the alanine group. Good for 3 to 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridyl is preferred because it can maintain moderate alkalinity for the reaction to proceed. The acid anhydride may, for example, be acetic anhydride, trimellitic anhydride or benzene tetracarboxylic anhydride, and if an acid anhydride is used, purification after completion of the reaction becomes easy and preferable. The imidization rate of the imidization of the oxime by the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. In the case where the resulting polyamic acid or polyimine is recovered from a reaction solution of polyglycolic acid or polyimine, the reaction solution can be poured into a weak solvent to form a precipitate. The weak solvent used for the precipitation may, for example, be methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water or the like. The polymer precipitated by pouring into a weak solvent is filtered and recovered, and dried at normal temperature or under heat at normal pressure or reduced pressure. In addition, the polymer recovered from the precipitation is redissolved in an organic solvent, and the reprecipitation is repeated. © Operation 2 to 1 times, the impurities in the polymer can be reduced. The weak solvent at this time is exemplified by, for example, an alcohol, a ketone, a hydrocarbon, etc., and if three or more kinds of weak solvents selected from these are used, it is preferable to further improve the purification efficiency. The molecular weight of the poly-proline and the polyimine contained in the liquid crystal alignment treatment agent of the present invention is determined by considering the strength of the coating film obtained therefrom and the workability at the time of formation of the coating film, and the uniformity of the coating film. The weight average molecular weight measured by the GPC (gel permeation chromatography) method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000. -37-200940506 &lt;Liquid Crystal Alignment Treatment Agent&gt; The liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film, and is a solution obtained by dissolving a resin component for forming a resin film in an organic solvent. . The resin component is a resin component containing at least one polymer selected from the above polymers of the present invention. In this case, the content of the resin component is preferably from 1% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, most preferably from 3 to 10% by mass. In the present invention, all of the above resin components may be the q copolymer used in the present invention, and other polymers than the polymer of the present invention may be mixed. In this case, the content of the polymer other than the polymer of the present invention in the resin component is from 0.5% by mass to 15% by mass, preferably from 1% by mass to 10% by mass. These other polymers are exemplified by, for example, polyamine or polyimine obtained by using a diamine compound other than a specific diamine compound as a diamine component which reacts with a tetracarboxylic dianhydride component. The organic solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the resin component. Specific examples thereof are listed below. For example, N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, N-methyl-2-pyrrolidone, hydrazine-methyl caprolactam, 2-pyrrolidone, Ν-ethylpyrrolidone, fluorene-vinylpyrrolidone, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl yam, butyrolactone, 1,3-dimethyl Yl amyl b-aminopyridinium I-based, propyl ether isomethyl dimethanol, ketone diyl, amyl ester isoalkenyl ketone thioglycolyl, ketooxifenyl ethyl Ester alkanoic acid, such as ketone pentane I 2 I methyl ketone 4 hydroxy I 4 carbon The -38- 200940506 or the like may be used singly or in combination. The liquid crystal alignment agent of the present invention may contain components other than the above. Examples thereof include a solvent or a compound which can improve film thickness uniformity or surface smoothness when a liquid crystal alignment treatment agent is applied, and a compound which improves the adhesion between the liquid crystal alignment film and the substrate. Examples of the solvent (weak solvent) for improving film thickness uniformity or surface smoothness are as follows. ❹ For example, isopropanol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellulolytic, methyl cellosolve acetate, ethyl cellosolve acetate, Butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether , dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol single Acetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, B Isobutyl butyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, N-pentane Alkane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy-39- 200940506 propionic acid, 3-methyl Propyl oxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-B a solvent having a low surface tension such as an acid ester, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate Wait. These weak solvents may be used singly or in combination of plural kinds. When the solvent is as described above, it is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass, based on the total of the solvent contained in the liquid crystal alignment treatment agent. Examples of the compound which improves post-film uniformity or surface smoothness are fluorine-based surfactants, rhodium-based surfactants, nonionic surfactants, and the like. More specifically, for example, F TOP EF301, EF303, EF352 (manufactured by TOKEMU PRODUCT), MEGAFAX F171, F173, R-30 (manufactured by Otsuka Ink Co., Ltd.), FLUORAD FC430, FC431 (manufactured by Sumitomo 3M), ASAHIGUARD AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The proportion of the surfactant to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent. Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate are the functional decane-containing compound or the epoxy group-containing compound shown below. 200940506 is exemplified by, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxydecylpropyltriethylamine, φ N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1 ,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindole Acid ester '9-triethoxydecylalkyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amino Propyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethyl) 3-aminopropyl Methoxydecane, N-bis(oxyethyl)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl Ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-di Bromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-xylene Diamine, 1,3-bis(N,N-diglycidylaminomethyl).cyclohexane, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-4,4'-diamino Diphenylmethane and the like. When the compound which improves the adhesion to the substrate is used, the amount thereof is preferably from -41 to 200940506, from 0.1 to 30 parts by mass, more preferably from 1 to 20% by mass based on 100 parts by mass of the resin component contained in the liquid crystal alignment agent. Share. When the amount used is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it is more than 30 parts by mass, the liquid crystal alignment property may be deteriorated. In addition to the above, the liquid crystal alignment treatment agent of the present invention may be added for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film, without impairing the effects of the present invention. The electric or conductive material may further be a crosslinkable compound for the purpose of increasing the hardness or density of the film when it is a liquid crystal alignment film. q &lt;Liquid crystal alignment film, liquid crystal display element&gt; The liquid crystal alignment treatment agent of the present invention is applied onto a substrate and fired, and then subjected to alignment treatment by rubbing treatment or light irradiation, or unaligned treatment such as vertical alignment use. It can be used as a liquid crystal alignment film. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. Further, from the viewpoint of simplification of the process, it is preferable to use a substrate which forms an ITO electrode or the like which is useful for driving the liquid crystal D. Further, it is also possible to use an opaque material such as a tantalum wafer which is a single-sided substrate of the reflective liquid crystal display element, and a material such as aluminum which can reflect light can be used as the electrode. The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, it is generally a method of screen printing, lithography, flexographic printing, ink jet printing or the like. As for other coating methods, there are dip coating, roll coating, slit coating, spin coating, etc., and these may be used depending on the purpose. After the liquid crystal alignment agent is applied onto the substrate, the firing can be carried out by adding a heating mechanism such as a hot plate of -42 to 200940506 at 50 to 300 ° C ', preferably 80 to 25 ° C. The solvent evaporates and forms a coating film. When the thickness of the coating film formed after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element is lowered. Therefore, it is preferably 5 to 300 nm, more preferably. It is 10 to l〇〇nm. When the liquid crystal is aligned horizontally or obliquely, the film after firing is treated by rubbing or polarized ultraviolet rays. In the liquid crystal display device of the present invention, a substrate to which a liquid crystal alignment film is attached is obtained from the liquid φ crystal alignment treatment agent of the present invention, and a liquid crystal cell is produced by a conventional method as a liquid crystal display element. As an example of the production of the liquid crystal element, a pair of substrates on which a liquid crystal alignment film is formed may be prepared, and a spacer may be spread on the liquid crystal alignment film of one of the substrates, so that the liquid crystal alignment film surface is inside, and the other film is bonded. The substrate, a method of injecting a liquid crystal into a vacuum and encapsulating it, or a method of laminating a liquid crystal on a liquid crystal alignment film surface of a spacer material, bonding the substrate, and encapsulating the substrate. The thickness of the separator at this time is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμιη. As described above, the liquid crystal display device produced by using the liquid crystal alignment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like. [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the description of the invention is not limited by the examples. [Synthesis of Diamine Compound] -43- 200940506 <Example ι>

將含化合物（2) (29.92克，277毫莫耳）及三乙胺 ❹ (28.03克，277毫莫耳）之四氫呋喃（300克）溶液冷卻 至10 °C以下，且在一面注意發熱一面滴加含化合物（1) (60.76克，263毫莫耳）之四氫呋喃（150克）溶液。滴 加結束後，使反應溫度上升至23 °C，繼續進行反應。以 HPLC (高速液體層析）確認反應結束後，將反應液體倒 入蒸餾水（2升）中，過濾析出之固體，水洗後，以乙醇 (450克）分散洗淨，獲得化合物（3 )(產量：72.91克 ，產率：9 2 % )。 *H-NMR ( 400MHz &gt; DMSO-d6 &gt; &lt;5 ppm) ： 9.79 ( 1H, t) &gt; 9.10-9.09 ( 2H, m) - 9.00-8.96 ( 1 H, m) - 8.61 ( 1H,寬），8.50-8.48 ( 1 H，m) ，7.79-7.76 ( 1 H，m)， 7.40-7.3 6 ( 1 H, m ) ，4.57(2H，s)。 接著，在氫氣存在下，於60°C下攪拌化合物（3 )( 72.00克，238毫莫耳）、5%鈀/碳（含水型，7.2克， -44- 200940506 10wt% )及1,4-二噁烷（720克）之混合物。反應結束後 ，以矽藻土過濾觸媒後，以旋轉蒸發器餾除溶劑獲得粗製 產物。以乙醇（360克）使所得粗製產物分散洗淨，獲得 二胺化合物（4)(產量：43.62克，產率：76%)。 ^-NMR ( 400MHz &gt; DMSO-d6 ' δ ppm) ： 8.64 ( 1Η, t) ，8.50 ( 1H，d ) ，8.44 ( 1H，d) ，7.67 ( 1H，d ) ’ 7.34 ( 1H, q) ，6_23 ( 2H，d ) ，5.94 ( 1H，s ) &gt; 4.87 ( φ 4H，s ) ，4.39 ( 2H，d)。 &lt;實施例2&gt; 二胺化合物（7)之合成 〔化 1 5〕Cool a solution containing compound (2) (29.92 g, 277 mmol) and triethylamine oxime (28.03 g, 277 mmol) in tetrahydrofuran (300 g) to below 10 °C, and pay attention to the fever while A solution of compound (1) (60.76 g, 263 mmol) in tetrahydrofuran (150 g) was added. After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was continued. After confirming the completion of the reaction by HPLC (high-speed liquid chromatography), the reaction liquid was poured into distilled water (2 liters), and the precipitated solid was filtered, washed with water, and washed with ethanol (450 g) to obtain a compound (3). : 72.91 g, yield: 92%). *H-NMR (400 MHz &gt; DMSO-d6 &gt;&lt;5 ppm): 9.79 (1H, t) &gt; 9.10-9.09 ( 2H, m) - 9.00-8.96 ( 1 H, m) - 8.61 ( 1H, Width), 8.50-8.48 ( 1 H,m) , 7.79-7.76 ( 1 H,m), 7.40-7.3 6 ( 1 H, m ) , 4.57 (2H, s). Next, compound (3) (72.00 g, 238 mmol), 5% palladium/carbon (aqueous form, 7.2 g, -44-200940506 10 wt%) and 1,4 were stirred at 60 ° C in the presence of hydrogen. a mixture of dioxane (720 g). After completion of the reaction, the catalyst was filtered through diatomaceous earth, and then the solvent was distilled off on a rotary evaporator to obtain a crude product. The obtained crude product was dispersed and washed with ethanol (360 g) to obtain a diamine compound (4) (yield: 43.62 g, yield: 76%). ^-NMR (400MHz &gt; DMSO-d6 ' δ ppm) : 8.64 ( 1Η, t) , 8.50 ( 1H,d ) , 8.44 ( 1H,d ) , 7.67 ( 1H,d ) ' 7.34 ( 1H, q) , 6_23 ( 2H,d ) , 5.94 ( 1H,s ) &gt; 4.87 ( φ 4H,s ) , 4.39 ( 2H,d). &lt;Example 2&gt; Synthesis of diamine compound (7) [Chemical Formula 15]

將含化合物（5) (40.00克，328毫莫耳）及三乙胺 (33.18克’ 328毫莫耳）之四氫呋喃（400克）溶液冷卻 至10 °C以下’且—面注意發熱一面滴加含化合物（1)( 72.00克’ 312毫莫耳）之四氫呋喃（176克）溶液。滴加 結束後’使反應溫度上升至23 °C，繼續進行反應。以 HPLC確認反應結束後，將反應液體倒入蒸餾水（3.5升） -45- 200940506 中淨 ^ ) ΛΉ 6 固 C 之物 出合 析化 濾得 過獲 後 洗 水 產 洗 散。 分 )% 2 克 8 200率 ( 產 醇 Λ 甲 以 克 iH-NMR ( 400MHz，DMSO-d6，&lt;5 ppm ) ： 8.83-8.34 (5H, m) &gt; 7.83-7.66 ( 1H, m ) &gt; 7.39-7.33 ( 1 H, m ) ’ 4.69-4.49 ( 2H，m) ，2.91-2.85 ( 3H，m)。 接著’在氫氣存在下，於23 °C下攪拌化合物（6)( 80.00克，253毫莫耳）、氫氧化鈀/碳（含水型，8.0克， 10 wt%)及1，4-二噁烷（ 1200克）之混合物。反應結束後 ’以矽藻土過濾觸媒後，以旋轉蒸發器餾除溶劑獲得粗製 產物。以四氫呋喃（150克）使所得粗製產物均句溶解， 且在-2 0 °C下將溶液滴加於己烷（ 660克）中，析出固體。 隨後，過濾、以冷己烷洗淨，獲得二胺化合物（7)(產 量：74.98 克，產率：98%)。 lH-NMR ( 400MHz，DMSO-d6 &gt; δ ppm ) ： 8.46-8.34 (2Η, m) &gt; 7.63-7.54 ( 1 H,寬），7 · 3 6 - 7.3 3 ( 1 Η，m )， 5.86-5.76 ( 3 H，m) ，4.86 ( 4H，s) ，4.57-4.53 ( 2H，寬 )&gt; 2.80 ( 3H,寬）。 &lt;實施例3&gt; 二胺化合物（10)之合成 200940506 〔化 1 6〕Cool a solution containing compound (5) (40.00 g, 328 mmol) and triethylamine (33.18 g '328 mil) in tetrahydrofuran (400 g) to below 10 °C. A solution of compound (1) (72.00 g '312 mmol) in tetrahydrofuran (176 g). After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was continued. After confirming the completion of the reaction by HPLC, the reaction liquid was poured into distilled water (3.5 liters) -45-200940506 in the net ^) ΛΉ 6 solid C. The product was separated and filtered, and then washed and washed. Fraction) % 2 g 8 200 rate (produced alcohol 甲 Aike iH-NMR (400 MHz, DMSO-d6, &lt; 5 ppm ) : 8.83-8.34 (5H, m) &gt; 7.83-7.66 ( 1H, m ) &gt 7.39-7.33 ( 1 H, m ) ' 4.69-4.49 ( 2H,m) , 2.91-2.85 ( 3H,m). Then 'in the presence of hydrogen, stir the compound (6) at 8 ° C (80.00 g, a mixture of 253 mmol, palladium hydroxide/carbon (aqueous form, 8.0 g, 10 wt%) and 1,4-dioxane (1200 g). After the reaction, the filter was filtered with diatomaceous earth. The solvent was distilled off on a rotary evaporator to give a crude product. The obtained crude product was dissolved in tetrahydrofuran (150 g), and the solution was added dropwise to hexane (660 g) at -2 ° C to precipitate a solid. It was filtered and washed with cold hexane to obtain a diamine compound (7) (yield: 74.98 g, yield: 98%). lH-NMR (400 MHz, DMSO-d6 &gt; δ ppm ) : 8.46-8.34 (2Η , m) &gt; 7.63-7.54 ( 1 H, wide), 7 · 3 6 - 7.3 3 ( 1 Η, m ), 5.86-5.76 ( 3 H, m) , 4.86 ( 4H, s) , 4.57-4.53 ( 2H, width) &gt; 2.80 (3H, width) &lt;Example 3&gt; Diamine compound (10) Synthesis of [16] 200 940 506

(8) 將含化合物（8) (16.69克，137毫莫耳）及三乙胺 (13.82克’ 137毫莫耳）之四氫呋喃（2〇〇克）溶液冷卻 至10 °C以下’且一面注意發熱—面滴加含化合物（！）（ 30.00克，130毫莫耳）之四氫呋喃（150克）溶液。滴加 結束後，使反應溫度上升至23 °C，繼續進行反應。以 HPLC確認反應結束後，將反應液體倒入蒸餾水（2.8升） 中，過濾析出之固體’水洗後，以乙醇（ 2 00克）分散洗 淨’獲得化合物（9)(產量：34.53克，產率：84%)。 1 Η - N M R ( 4 0 0 Μ H z，D M S Ο - d 6，&lt;5 p p m ) : 9 · 3 0 ( 1 Η, t) ，9.01-9.00 ( 2H，m ) * 8.95-8.93 ( 1 H, m ) ，8.47 ( 1H，d) ，8.42 ( 1H, dd ) ，7.69 ( 2H，d) ，7.32 ( 1H，q) ’ 3.64-3.58 ( 2H，m) ，2.92 ( 2H，t)。 接著，在氫氣存在下，於60 °C下攪拌化合物（9)( 32.00克，1〇1毫莫耳）、5%鈀/碳（含水型，3.2克， l〇wt% )及I,4-二噁烷（320克）之混合物。反應結束後 ’以矽藻土過濾觸媒後，以旋轉蒸發器餾除溶劑獲得粗製 產物。以四氫呋喃（1 5 0克）分散洗淨所得粗製產物，獲 得二胺化合物（1〇)(產量：19.21克，產率：74%)。 -47- 200940506 ^-NMR ( 400MHz &gt; DMSO-d6 * δ ppm) ： 8.43-8.39 (2H, m) - 8.09 ( 1H, t) &gt; 7.63 ( 1H, d) &gt; 7.30 ( 1H, dd )，6.16 ( 2H, d ) ，5.92 ( 1H, d ) ，4.84 ( 4H, s)， 3.44-3.28 ( 3H，m) ，2.82 ( 3H，t)。 &lt;實施例4&gt; 二胺化合物（I4)之合成 〔化 1 7〕(8) Cool a solution containing compound (8) (16.69 g, 137 mmol) and triethylamine (13.82 g '137 mmol) in tetrahydrofuran (2 g) below 10 °C. A solution of the compound (!) (30.00 g, 130 mmol) in tetrahydrofuran (150 g) was added dropwise. After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was continued. After confirming the completion of the reaction by HPLC, the reaction liquid was poured into distilled water (2.8 liters), and the precipitated solid was filtered, washed with ethanol (200 g) to obtain a compound (9) (yield: 34.53 g. Rate: 84%). 1 Η - NMR ( 4 0 0 Μ H z, DMS Ο - d 6, &lt; 5 ppm ) : 9 · 3 0 ( 1 Η, t) , 9.01-9.00 ( 2H, m ) * 8.95-8.93 ( 1 H , m ) , 8.47 ( 1H, d) , 8.42 ( 1H, dd ) , 7.69 ( 2H,d) , 7.32 ( 1H,q) ' 3.64-3.58 ( 2H,m) , 2.92 ( 2H,t). Next, the compound (9) (32.00 g, 1 〇1 mmol), 5% palladium/carbon (aqueous form, 3.2 g, l〇wt%) and I, 4 were stirred at 60 ° C in the presence of hydrogen. a mixture of dioxane (320 g). After the completion of the reaction, the catalyst was filtered with diatomaceous earth, and the solvent was distilled off by a rotary evaporator to obtain a crude product. The obtained crude product was washed with tetrahydrofuran (150 g) to give a diamine compound (yield: 19.21 g, yield: 74%). -47- 200940506 ^-NMR (400MHz &gt; DMSO-d6 * δ ppm) : 8.43-8.39 (2H, m) - 8.09 ( 1H, t) &gt; 7.63 ( 1H, d) &gt; 7.30 ( 1H, dd ) , 6.16 ( 2H, d ) , 5.92 ( 1H, d ) , 4.84 ( 4H, s), 3.44-3.28 ( 3H, m) , 2.82 ( 3H, t). &lt;Example 4&gt; Synthesis of diamine compound (I4) [Chem. 1 7]

❹ 於含化合物（12) (35.00克，321毫莫耳）及三乙 胺（97.39克，962毫莫耳）之四氫呋喃（240克）溶液中 滴加含化合物（11) (29.84克，160毫莫耳）之四氫呋 喃（60克）溶液。滴加結束後，以HPLC追蹤反應，確認 反應結束後，添加二氯甲烷（1升）後，以蒸餾水（600 毫升）進行洗淨三次。以無水硫酸鎂使有機層乾燥後，過 濾、去除溶劑，獲得化合物（13)之粗製產物。以乙酸乙 酯（500克）/己烷（1升）使所得粗製產物再結晶，獲得 化合物（13)(產量：38.74克，產率：88%)。 *H-NMR ( 400MHz &gt; CDC13 &gt; δ ppm) : 8.79 ( 1H, d) ，8.7 1 ( 1H, d ) ，8.66 ( 1H，dd ) ，8.46 ( 1H, dd )， -48- 200940506 7.8 8-7.8 5 ( 1 H，m) ，7·40 ( 1H，q) ，7.30 ( 1H，d)， 5.38 ( 2H，s )。 接著，在氫氣存在下，於40 °C下攪拌化合物（13)( 20.00克，72.7毫莫耳）、氧化鉑（IV)(含水型，2.0克 ，10wt% )及乙酸乙酯 / 乙醇（200 克，1 00/50 ( v/v% )) 之混合物。反應結束後，以矽藻土過濾觸媒後，以旋轉蒸 發器餾除溶劑獲得化合物（1 4 )之粗製產物。所得粗製產 ❹㈣莖 矽膠管柱層析（溶離溶劑爲己烷/乙酸乙酯（ 1 0 0/5 0v/v% ))純化，獲得二胺化合物（14 )(產量： 15.27 克，產率：98%)。 1 Η - N M R ( 4 0 0 MH z，C D C 13， &lt;5 p p m ) : 8.66 ( 1H, d) &gt; 8.57 ( 1H, dd ) &gt; 7.77-7.73 ( 1 H, m ) * 7.33-7.29 ( 1 H, m ) ，6.67 ( 1H, d) ，5.00 ( 2H, s ) ，3.37( 4H, s )。 &lt;實施例5&gt; O 二胺化合物（16)之合成 〔化 1 8〕含 Compound (11) (29.84 g, 160 m) was added dropwise to a solution of compound (12) (35.00 g, 321 mmol) and triethylamine (97.39 g, 962 mmol) in tetrahydrofuran (240 g) Mohr) tetrahydrofuran (60 g) solution. After completion of the dropwise addition, the reaction was followed by HPLC. After confirming completion of the reaction, dichloromethane (1 L) was added, and then washed three times with distilled water (600 ml). After the organic layer was dried over anhydrous magnesium sulfate, the solvent was filtered and evaporated to give the crude product of compound (13). The obtained crude product was recrystallized from ethyl acetate (500 g) / hexane (1 liter) to give Compound (13) (yield: 38.74 g, yield: 88%). *H-NMR (400MHz &gt; CDC13 &gt; δ ppm) : 8.79 ( 1H, d) , 8.7 1 ( 1H, d ) , 8.66 ( 1H, dd ) , 8.46 ( 1H, dd ), -48- 200940506 7.8 8 -7.8 5 ( 1 H,m) , 7·40 ( 1H,q) , 7.30 ( 1H,d), 5.38 ( 2H,s ). Next, compound (13) (20.00 g, 72.7 mmol), platinum (IV) oxide (aqueous form, 2.0 g, 10 wt%) and ethyl acetate/ethanol (200) were stirred at 40 ° C in the presence of hydrogen. a mixture of grams, 1 00/50 (v/v%)). After completion of the reaction, the catalyst was filtered through diatomaceous earth, and then the solvent was distilled off by a rotary evaporator to obtain a crude product of compound (1 4 ). The obtained crude cockroach (4) was purified by stalk gum column chromatography (solvent solvent was hexane/ethyl acetate (1 0 0/5 0 v/v%)) to obtain a diamine compound (14) (yield: 15.27 g, yield: 98%). 1 Η - NMR ( 4 0 0 MH z, CDC 13, &lt; 5 ppm ) : 8.66 ( 1H, d) &gt; 8.57 ( 1H, dd ) &gt; 7.77-7.73 ( 1 H, m ) * 7.33-7.29 ( 1 H, m ) , 6.67 ( 1H, d) , 5.00 ( 2H, s ) , 3.37 ( 4H, s ). &lt;Example 5&gt; Synthesis of O diamine compound (16) [Chem. 1 8]

(2) 在23°C下於含化合物（2) (29.98克，277毫莫耳） 、碳酸氫鈉（29.12克，347毫莫耳）及蒸餾水（630克） -49- 200940506 之混合溶液中滴加含化合物（11) (43.0克，231毫莫耳 )之乙醇（830克）溶液。滴加結束後，以HPLC確認反 應結束後’添加二氯甲烷（2升）去除水層。隨後，有機 層以飽和食鹽水（500毫升）洗淨三次，以無水硫酸鎂使 有機層乾燥後，進行溶劑之餾除。以乙酸乙酯（500克）/ 己烷（1升）使所得粗製產物再結晶，獲得化合物（15) (產量：55.28克，產率：87%)。 'H-NMR ( 400MHz &gt; CDC13 » δ ppm) ： 9.18 ( 1H, d ) ’ 9.17 ( 1H，寬），8.66-8.62 ( 2H，m ) * 8.29-8.25 ( 1 H, m ) ’ 7.69-7.66 ( 1H，m ) · 7.37-7.33 ( 1 H, m ) &gt; 6.90 ( 1H，d ) ，4.68 ( 2H，m )。 接著，在氫氣存在下，於23 °C下攪拌化合物（15)( 3.0克’10.9毫莫耳）、氧化鉑（IV)(含水型，0.3克， l〇wt% )及1，4-二噁烷（30克）之混合物。反應結束後， 以矽藻土過濾觸媒後，以旋轉蒸發器餾除溶劑獲得二胺化 合物（16)(產量：2·30克，產率：98%)。 !H-NMR ( 400MHz &gt; CDC13 &gt; δ ppm ) : 8.63 ( 1H，d) '8.52 ( 1H, dd ) &gt; 7.71-7.66 ( 1H, m ) » 7.28-7.24 ( 1H, m ) ，6.53 (1H，d) ，6.18-6.11 (2H，m) ，4.22(2H，s )&gt; 3.70 ( 1H, s ) ，3.56-3.34 ( 4H，寬）。 &lt;實施例6&gt; 二胺化合物（19)之合成 -50- 200940506(2) At 23 ° C in a mixed solution containing compound (2) (29.98 g, 277 mmol), sodium bicarbonate (29.12 g, 347 mmol) and distilled water (630 g) -49- 200940506 A solution of the compound (11) (43.0 g, 231 mmol) in ethanol (830 g) was added dropwise. After completion of the dropwise addition, it was confirmed by HPLC that after completion of the reaction, dichloromethane (2 liters) was added to remove the aqueous layer. Subsequently, the organic layer was washed three times with saturated brine (500 ml), and the organic layer was dried over anhydrous magnesium sulfate and evaporated. The obtained crude product was recrystallized from ethyl acetate (500 g) / hexane (1 liter) to give Compound (15) (yield: 55.28 g, yield: 87%). 'H-NMR (400MHz &gt; CDC13 » δ ppm) : 9.18 ( 1H, d ) ' 9.17 ( 1H, Width), 8.66-8.62 ( 2H,m ) * 8.29-8.25 ( 1 H, m ) ' 7.69-7.66 (1H,m) · 7.37-7.33 ( 1 H, m ) &gt; 6.90 ( 1H,d ) , 4.68 ( 2H,m ). Next, the compound (15) (3.0 g '10.9 mmol), platinum (IV) oxide (aqueous form, 0.3 g, l〇wt%) and 1,4-two were stirred at 23 ° C in the presence of hydrogen. A mixture of oxane (30 g). After the completion of the reaction, the catalyst was filtered through celite, and then the solvent was evaporated on a rotary evaporator to obtain a diamine compound (16) (yield: 2·30 g, yield: 98%). !H-NMR (400MHz &gt; CDC13 &gt; δ ppm ) : 8.63 ( 1H,d) '8.52 ( 1H, dd ) &gt; 7.71-7.66 ( 1H, m ) » 7.28-7.24 ( 1H, m ) , 6.53 ( 1H, d), 6.18-6.11 (2H, m), 4.22 (2H, s) &gt; 3.70 (1H, s), 3.56-3.34 (4H, width). &lt;Example 6&gt; Synthesis of diamine compound (19) -50- 200940506

在40 °C下於含化合物（17) (50.00克，170毫莫耳 〇 )、碳酸鉀（47.01克，340毫莫耳）、碘化銅（I)( 6.48克，34_0毫莫耳）、N-甲基甘胺酸（6.06克，68.0 毫莫耳）及DMSO (二甲基亞颯）（1升）之混合溶液中 滴加化合物（2) (36.78克，340毫莫耳）。滴加結束後 ，以HPLC確認反應結束後，添加乙酸乙酯（4升）/蒸餾 水（5升），過濾去除不溶物。隨後，以乙酸乙酯（500 克）萃取自分液回收去除之水層兩次，且合倂有機層，並 φ 以無水硫酸鎂進行乾燥。以旋轉蒸發器餾除溶劑後，以乙 酸乙酯（700毫升）/己烷（2升）進行再結晶，獲得化合 物（18 )(產量：23.04克，產率：49% )。 h-NMR ( 400MHz，CDC13，&lt;5 ppm ) ： 8.63 ( 1H,寬 )，8.50-8.49 ( 1 H，寬），7.95 ( 1H，t) ，7.80-7.76 ( 3H，m ) ，7.67 ( 1H，t) ，7.39 ( 1H，q ) &gt; 4.52 ( 2H, d) 接著，在氫氣存在下，於23 °C下攪拌化合物（18)( 1.0克，3.65毫莫耳）、氧化鈷（IV)(含水型，0.1克， 10 wt% )及甲醇（1〇克）之混合物。反應結束後，以矽藻 -51 - 200940506 土過濾觸媒後，以旋轉蒸發器餾除溶劑獲得二胺化合物（ 19)(產量：0.97 克，產率：97%)。 h-NMR ( 400MHz，DMS 0-d6，δ ppm ) : 8.52 ( 1Η d) ，8.41 ( 1H，dd) ，7.69 ( 1H，d) - 7.32 ( 1H, q)， 5.60 (lH，t) ，5.17(2H，s) &gt; 4.37-4.14 ( 4H, m )。 &lt;實施例7&gt; 二胺化合物（23)之合成 〔化 20〕Containing compound (17) (50.00 g, 170 mmol), potassium carbonate (47.01 g, 340 mmol), copper iodide (I) (6.48 g, 34_0 mmol) at 40 °C, Compound (2) (36.78 g, 340 mmol) was added dropwise to a mixed solution of N-methylglycine (6.06 g, 68.0 mmol) and DMSO (dimethyl hydrazide) (1 liter). After completion of the dropwise addition, after confirming completion of the reaction by HPLC, ethyl acetate (4 L) / distilled water (5 L) was added, and the insoluble material was removed by filtration. Subsequently, the aqueous layer removed by liquid separation was extracted twice with ethyl acetate (500 g), and the organic layer was combined and dried over anhydrous magnesium sulfate. After distilling off the solvent by a rotary evaporator, ethyl acetate (yield: EtOAc) (yield: h-NMR (400MHz, CDC13, &lt;5 ppm): 8.63 (1H, Width), 8.50-8.49 (1H, Width), 7.95 (1H, t), 7.80-7.76 (3H,m), 7.67 ( 1H , t) , 7.39 ( 1H, q ) &gt; 4.52 ( 2H, d) Next, the compound (18) (1.0 g, 3.65 mmol) and cobalt (IV) are stirred at 23 ° C in the presence of hydrogen. (aqueous type, 0.1 g, 10 wt%) and a mixture of methanol (1 g). After the completion of the reaction, the catalyst was filtered with celite - 51 - 200940506, and then the solvent was distilled off on a rotary evaporator to obtain a diamine compound (19) (yield: 0.97 g, yield: 97%). h-NMR (400MHz, DMS 0-d6, δ ppm ) : 8.52 ( 1Η d) , 8.41 ( 1H, dd ) , 7.69 ( 1H, d) - 7.32 ( 1H, q), 5.60 (lH,t) , 5.17 (2H, s) &gt; 4.37-4.14 ( 4H, m ). &lt;Example 7&gt; Synthesis of diamine compound (23) [Chemical 20]

(21) 在氮氣氛圍下，使含化合物（21) (51·43克，281 毫莫耳）之四氫呋喃（300克）溶液維持於10°c以下，且 一面注意發熱一面滴加含化合物（20) ( 50.00克，281 毫莫耳）、三乙胺（170.5克，1.69毫莫耳）及DMAP ( 4-二甲胺基吡啶）（6.87克，56.2毫莫耳）之四氫呋喃（ 5 00克）溶液。滴加結束後，使反應溫度上升至231：，攪 拌1小時後，再進行加熱回流。以HPLC確認反應結束後 ，將反應液體倒入蒸餾水（6.4升）中，進行過濾、水洗 ，獲得粗製產物。以四氫呋喃（243克）/己烷（1 45 8克 200940506 )使粗製產物再結晶，獲得化合物（22 )(產量：72.58 克，產率·· 8 9%)。 ^-NMR ( 400MHz * DMSO-d6 5 δ ppm) ： 1 1 .25 ( 1 Η, s) ，9_18(lH，d) &gt; 9.09 ( 2H, dd) &gt; 8.82 ( 1H, dd )， 8.57 ( 1H, t) ，8.3 8-8.3 5 ( 1 H，m ) ，7.64 ( 1H，q )。 接著，在氫氣存在下，於90°C下攪拌化合物（22 )( 20.00克，69_4毫莫耳）、5%鈀-碳（含水型，2·0克， φ 10Wt% )及I，4-二噁烷（400克）之混合物。反應結束後 ，以矽藻土過濾觸媒後，以旋轉蒸發器餾除溶劑獲得粗製 產物。以乙醇（75克）分散洗淨所得粗製產物，獲得二胺 化合物（23)(產量：10.14克，產率：64%)。 *H-NMR ( 400MHz &gt; DMSO-d6 * δ ppm) ： 9.8 7 ( 1H, s ) &gt; 9.03-9.01 ( 1H, m) » 8.72-8.70 ( 1H, m) , 8.23- 8.19 ( 1H, m ) ，7.5 4-7.5 0 ( 1 H，m ) ，6.27-6.26 ( 2H, m )，5.63-5.61 ( 1H，m) ，4.75-4.73 ( 2H，m)。 ❹ &lt;實施例8&gt; 二胺化合物（26)之合成 -53- 200940506 〔化 2 1〕(21) The solution containing the compound (21) (51.43 g, 281 mmol) in tetrahydrofuran (300 g) was maintained at 10 ° C or less under nitrogen atmosphere, and the compound was added dropwise while paying attention to heat generation (20). (50.00 g, 281 mmol), triethylamine (170.5 g, 1.69 mmol) and DMAP (4-dimethylaminopyridine) (6.87 g, 56.2 mmol) of tetrahydrofuran (500 g) Solution. After completion of the dropwise addition, the reaction temperature was raised to 231:, and after stirring for 1 hour, it was heated to reflux. After confirming the completion of the reaction by HPLC, the reaction liquid was poured into distilled water (6.4 liter), filtered, and washed with water to obtain a crude product. The crude product was recrystallized from tetrahydrofuran (243 g) / hexane (1, 4 8 g, 200940506) to afford compound (22) (yield: 72.58 g, yield · 8 9%). ^-NMR (400MHz * DMSO-d6 5 δ ppm) : 1 1 .25 ( 1 Η, s) , 9_18(lH,d) &gt; 9.09 ( 2H, dd ) &gt; 8.82 ( 1H, dd ), 8.57 ( 1H, t) , 8.3 8-8.3 5 ( 1 H,m ) , 7.64 ( 1H,q ). Next, the compound (22) (20.00 g, 69_4 mmol), 5% palladium-carbon (aqueous form, 2.00 g, φ 10 Wt%) and I,4- were stirred at 90 ° C in the presence of hydrogen. A mixture of dioxane (400 g). After completion of the reaction, the catalyst was filtered through diatomaceous earth, and then the solvent was distilled off on a rotary evaporator to obtain a crude product. The obtained crude product was washed with ethanol (75 g) to give a diamine compound (23) (yield: 10.14 g, yield: 64%). *H-NMR (400MHz &gt; DMSO-d6 * δ ppm) : 9.8 7 ( 1H, s ) &gt; 9.03-9.01 ( 1H, m) » 8.72-8.70 ( 1H, m) , 8.23- 8.19 ( 1H, m ), 7.5 4-7.5 0 ( 1 H,m ) , 6.27-6.26 ( 2H, m ), 5.63-5.61 ( 1H,m) , 4.75-4.73 ( 2H,m). ❹ &lt;Example 8&gt; Synthesis of diamine compound (26) -53- 200940506 [Chem. 2 1]

(21) HCI 在氮氣氛圍下，使含化合物（21) (20.00克，112 毫莫耳）之四氫呋喃（120克）之溶液冷卻至l〇°C以下， 且一面注意發熱一面滴加含化合物（ 24 ) ( 20.57克，112 毫莫耳）、三乙胺（68.18克，674毫莫耳）及DMAP ( 2.74克，22.5毫莫耳）之四氫呋喃（200克）溶液。滴加 結束後，使反應溫度上升至23 °C，攪拌1小時後，再進行 加熱回流1 7小時。以HPLC確認反應結束後，將反應液 體倒入蒸餾水（2.6升）中，進行過濾、水洗，獲得粗製 產物。以乙醇（40克）將所得粗製產物分散洗淨後，進行 過濾、乾燥，獲得化合物（25)(產量：16.45克，產率 :5 1 % )。 *H-NMR ( 400MHz &gt; DMSO-d6 &gt; δ ppm ) ： 1 1.4 ( 1 Η, s ) ，9.15-9.14 ( 1Η，m ) ，8.86 ( 1H，d) ，8.77 ( 1H，d) ，8.64-8.60 ( 1H，m ) ，8.33 ( 1H，d ) ，8_06 ( 1H，d )， 7.66 ( 1H, q) ，2.92 ( 2H，t )。 接著，在氫氣存在下，於6(TC下攪拌化合物（25 )( 15.00克，52.0毫莫耳）、5 %鈀/碳（含水型，1.5克， -54-(21) HCI A solution containing the compound (21) (20.00 g, 112 mmol) in tetrahydrofuran (120 g) was cooled to below 10 ° C under a nitrogen atmosphere, and the compound was added dropwise while paying attention to heat generation ( 24) (20.57 g, 112 mmol), triethylamine (68.18 g, 674 mmol) and DMAP ( 2.74 g, 22.5 mmol) in tetrahydrofuran (200 g). After completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the mixture was stirred for 1 hour, and then heated under reflux for further 7 hours. After confirming the completion of the reaction by HPLC, the reaction liquid was poured into distilled water (2.6 liter), filtered, and washed with water to obtain a crude product. The obtained crude product was washed with ethanol (40 g), and then filtered and dried to give Compound (25) (yield: 16.45 g, yield: 51%). *H-NMR (400MHz &gt; DMSO-d6 &gt; δ ppm ) : 1 1.4 ( 1 Η, s ) , 9.15-9.14 ( 1Η,m ) , 8.86 ( 1H,d) , 8.77 ( 1H,d) ,8.64 -8.60 ( 1H,m ) , 8.33 ( 1H,d ) , 8_06 ( 1H,d ), 7.66 ( 1H, q) , 2.92 ( 2H,t ). Next, compound (25) (15.00 g, 52.0 mmol), 5% palladium/carbon (aqueous form, 1.5 g, -54-) was stirred at 6 (TC) in the presence of hydrogen.

(29) 200940506 10 wt % )及1，4-二噁烷（150克）之混合物。反應結 ，以矽藻土過濾觸媒後，以旋轉蒸發器餾除溶劑獲得 物（26 )之粗製產物。所得粗製產物經矽膠管柱層析 離溶劑爲己烷/乙酸乙酯（1 00/5 0WV% ))純化，接著 氫呋喃（400克）/己烷（600克）再結晶純化，獲得 化合物（26)(產量：6.11克，產率：51%)。 ^-NMR ( 400MHz - DMSO-d6 &gt; δ ppm ) ： 9.54 s ) ，9.10 ( 1H, d ) ，8.72 ( 1H，dd ) ，8.3 0-8.27 ( 1 )，7.90 ( 1H，s) ，7.52 ( 1H, q ) &gt; 6.75 ( 1H, d )， (1H，d) ，5.99 ( 1H，m) ，4.6 5 - 4.5 9 ( 4 H，m )。 &lt;實施例9&gt; 二胺化合物（29)之合成 ❹ 在氮氣氛圍下，於含化合物（27) (10.00克， 毫莫耳）及三乙胺（59.50克，588毫莫耳）之四氫 -55- 束後 化合 (溶 自四 二胺 ：1H, S, m 6.61 49.0 呋喃 200940506 (100克）溶液中緩慢滴加化合物（12) (21.39克，196 毫莫耳）。反應結束後，將反應液體倒入蒸餾水（1升） 中，進行過濾、洗淨，獲得化合物（28 )之粗製產物。以 乙腈（200克）/乙酸乙酯（300克）使所得粗製產物再結 晶，獲得化合物（2 8 )(產量·· 1 1 · 3 5克，產率：6 1 % ) 〇 ^-NMR ( 400MHz &gt; DMSO-d6 5 δ ppm) ： 8.74-8.73 (3H，m) ，8.61(2H，dd) &gt; 7.93 ( 2H, d ) » 7.50 ( 2H, q ) ，7.44 ( 1H, s ) ，5.56 ( 4H，s )。 接著，在氫氣存在下，於6(TC下攪拌化合物（28 )( 8.00克，20.1毫莫耳）、氧化鈾（IV)(含水型，0.8克 ，10 wt%)及1，4-二噁烷（80克）之混合物。反應結束後 ，以矽藻土過濾觸媒後，以旋轉蒸發器餾除溶劑獲得粗製 產物。以四氫呋喃（200克）/己烷（600克）使所得粗製 產物再結晶，獲得二胺化合物（29)(產量：4.66克，產 率：7 2 % ) 〇 ^-NMR ( 400MHz · DMSO-d6 * δ ppm) ： 8.65 ( 2Η, d) &gt; 8.52 ( 2H, dd ) &gt; 7.8 8 - 7 _ 8 5 ( 2 H, m ) ，7.4 0 ( 2 H，q )，6.68 ( 1H，s ) ，6.07 ( 1H, s ) ，4.96 ( 4H，s) ，4.25 (4H，s)。 &lt;實施例1 〇&gt; 二胺化合物（34)之合成 -56- 200940506 〔化 23〕(29) 200940506 10 wt % ) and a mixture of 1,4-dioxane (150 g). After the reaction mixture was filtered with celite, the solvent was distilled off on a rotary evaporator to obtain a crude product (26). The obtained crude product was purified by hexane/ethyl acetate (1 0 0 0 0 0%), and then purified by hexane (400 g) / hexane (600 g). 26) (yield: 6.11 g, yield: 51%). ^-NMR (400MHz - DMSO-d6 &gt; δ ppm ) : 9.54 s ) , 9.10 ( 1H, d ) , 8.72 ( 1H, dd ) , 8.3 0-8.27 ( 1 ), 7.90 ( 1H, s) , 7.52 ( 1H, q ) &gt; 6.75 ( 1H, d ), (1H, d) , 5.99 ( 1H, m) , 4.6 5 - 4.5 9 ( 4 H, m ). &lt;Example 9&gt; Synthesis of ruthenium compound (29) 四 Under a nitrogen atmosphere, tetrahydrogen containing compound (27) (10.00 g, millimolar) and triethylamine (59.50 g, 588 mmol) -55- After-beam combination (solvent from tetra-diamine: 1H, S, m 6.61 49.0 furan 200940506 (100 g) was slowly added dropwise to compound (12) (21.39 g, 196 mmol). The reaction liquid was poured into distilled water (1 liter), filtered, and washed to give the crude product of Compound (28). The obtained crude product was recrystallized from acetonitrile (200 g) / ethyl acetate (300 g). 2 8 ) (yield · · 1 1 · 3 5 g, yield: 6 1 %) 〇^-NMR (400 MHz &gt; DMSO-d6 5 δ ppm) : 8.74-8.73 (3H, m) , 8.61 (2H, Dd) &gt; 7.93 ( 2H, d ) » 7.50 ( 2H, q ) , 7.44 ( 1H, s ) , 5.56 ( 4H, s ). Next, stir the compound (28 ) at 6 (TC) in the presence of hydrogen ( a mixture of 8.00 g, 20.1 mmol, uranium oxide (IV) (aqueous form, 0.8 g, 10 wt%) and 1,4-dioxane (80 g). After the reaction, filter with diatomaceous earth After the media, The solvent was distilled off on a rotary evaporator to give a crude product. The obtained crude product was recrystallized from tetrahydrofuran (200 g) / hexane (600 g) to give the diamine compound (29) (yield: 4.66 g, yield: 7 2 %) 〇^-NMR (400MHz · DMSO-d6 * δ ppm) : 8.65 ( 2Η, d) &gt; 8.52 ( 2H, dd ) &gt; 7.8 8 - 7 _ 8 5 ( 2 H, m ) , 7.4 0 ( 2 H , q ), 6.68 ( 1H, s ) , 6.07 ( 1H, s ) , 4.96 ( 4H, s) , 4.25 (4H, s). &lt;Example 1 〇&gt; Synthesis of diamine compound (34)-56 - 200940506 [Chem. 23]

在氮氣氛圍下，將含化合物（31 ) ( 81.60克，74_1 毫莫耳）、氫氧化鉀（18.29克，24.7毫莫耳）及DMSO (3 75克）之混合物加熱至50°C後，滴加含化合物（30) (50.00克，24.7毫莫耳）之DMSO( 125克）溶液。滴加 結束後，以HPLC確認反應結束後，將反應液體注入5質 量％之鹽酸冰水（4升）中，過濾固體，經水洗，獲得化 合物（32 )之濕潤產物。隨後，以2-丙醇（20 5克）/己烷 (3 3 5克）進行再結晶，獲得化合物（32 )(產量：49.0 克，產率72% )。 ^-NMR ( 400MHz &gt; DMSO-d6 &gt; 5 ppm ) ： 9.73 ( 1Η, s ) ，8.86 ( 1H, d ) ，8.42 ( 1H, dd ) ，7.11-7.05 ( 3H, m )&gt; 6.90-6.87 ( 2H, m )。 接著，在氮氣氛圍下，使含化合物（21) (19.34克 ，109毫莫耳）之四氫呋喃（180克）溶液冷卻至1(TC以 下，且一面注意發熱一面滴加含化合物（31) ( 30.0克， -57- 200940506 109毫莫耳）、三乙胺（33.0克，324毫莫耳）及DMAP (2.65克，21·7毫莫耳）之DMSO(300克）溶液。滴加 結束後，使反應溫度上升至2 3 °C，攪拌1小時後，再進行 加熱回流1 9小時。以HPLC確認反應結束後，將反應液 體倒入蒸餾水（3.9升）中，經過濾、水洗、且進行甲醇 水洗，獲得粗製產物。使所得粗製產物溶解於氯仿中之後 ，過濾不溶物。隨後，濃縮濾液，且以矽膠管柱層析（溶 離溶劑爲1，2-二氯乙烷/乙酸乙酯（i〇〇/40v/v% ))純化， 獲得化合物（3 3 )(產量：3 5 · 8克，產率：8 6 % )。 ^-NMR ( 400MHz &gt; DMSO-d6，δ ppm ) : 9.29 ( 1Η, dd) ’ 8.92-8.9 1 ( 2H, m ) ，8.52-8.48 ( 2H, m ) &gt; 7.69-7.66 ( 1 H, m ) » 7.53-7.51 ( 2H, m ) ，7 · 4 4 - 7 · 4 0 ( 2 H，m )，7.24 ( 1H, d)。 接著，在氮氣氛圍下，使含化合物（33) ( 30.00克 ，78.7毫莫耳）及鐵粉（26.36克，472毫莫耳）之甲苯 (170克）溶液加熱至70°C後，滴加含10質量％氯化銨（ 12.63克，236毫莫耳）之水溶液。反應結束後，以矽藻 土過濾固體。隨後，自濾液去除水層後，以旋轉蒸發器濃 縮有機層，獲得粗製產物。接著，使所得粗製產物溶解於 乙酸乙酯（1升）中，以蒸餾水（500毫升）洗淨三次後 ，有機層以無水硫酸鎂乾燥，餾除溶劑，以甲醇（100克 )/2-丙醇（100克）使所得化合物（34 )之粗製產物再結 晶，獲得二胺化合物（3 4 )(產量：1 5.4克，產率：6 1 % -58- 200940506 !H-NMR ( 400MHz &gt; DMSO-d6，&lt;5 ppm ) : 9.20 ( 1H, dd) ’ 8.85 ( 1H, dd) &gt; 8.43-8.40 ( 1H, m) ，7.62-7.59 ( 1H，m) ，7.19-7.16 ( 2H，m ) ，6.88-6.84 ( 2H，m )， 6.53 ( 1H, d ) ，6.02 ( 1H，d) &gt; 5.81 ( 1H, dd ) ，4.69 ( 2H, s ) ，4.57 ( 2H, s )。 〈實施例1 1&gt;The mixture containing compound (31) (81.60 g, 74_1 mmol), potassium hydroxide (18.29 g, 24.7 mmol) and DMSO (3 75 g) was heated to 50 ° C under a nitrogen atmosphere. A solution of compound (30) (50.00 g, 24.7 mmol) in DMSO (125 g) was added. After completion of the dropwise addition, the reaction liquid was poured into 5 mass% hydrochloric acid ice water (4 L) after completion of the reaction, and the solid was filtered and washed with water to obtain a wet product of the compound (32). Subsequently, recrystallization was carried out with 2-propanol (20 5 g) / hexane (3 35 g) to obtain Compound (32) (yield: 49.0 g, yield: 72%). ^-NMR (400 MHz &gt; DMSO-d6 &gt; 5 ppm) : 9.73 (1 Η, s ) , 8.86 ( 1H, d ) , 8.42 ( 1H, dd ) , 7.11 - 7.05 ( 3H, m ) &gt; 6.90-6.87 ( 2H, m ). Next, a solution of the compound (21) (19.34 g, 109 mmol) in tetrahydrofuran (180 g) was cooled to 1 (TC or less) under a nitrogen atmosphere, and the compound (31) was added dropwise while paying attention to heat generation (30.0).克, -57- 200940506 109 millimolar), triethylamine (33.0 grams, 324 millimoles) and DMAP (2.65 grams, 21.7 millimoles) in DMSO (300 grams). After the addition, The reaction temperature was raised to 23 ° C, and the mixture was stirred for 1 hour, and then heated and refluxed for further 9 hours. After confirming the completion of the reaction by HPLC, the reaction liquid was poured into distilled water (3.9 liter), filtered, washed with water, and methanol was added. After washing with water, a crude product was obtained. After the obtained crude product was dissolved in chloroform, the insoluble material was filtered. Then, the filtrate was concentrated and chromatographed on a silica gel column (solvent solvent was 1,2-dichloroethane/ethyl acetate (i) Purification of 〇〇/40v/v%)) gave compound (3 3 ) (yield: 3 5 · 8 g, yield: 86 %). ^-NMR (400 MHz &gt; DMSO-d6, δ ppm ) : 9.29 ( 1Η, dd) ' 8.92-8.9 1 ( 2H, m ) , 8.52-8.48 ( 2H, m ) &gt; 7.69-7.66 ( 1 H, m ) » 7.53-7.51 ( 2H, m ), 7 · 4 4 - 7 · 4 0 ( 2 H, m ), 7.24 ( 1H, d). Next, the compound (33) (30.00 g, 78.7 mmol) and iron powder were added under a nitrogen atmosphere. A solution of (26.36 g, 472 mmol) of toluene (170 g) was heated to 70 ° C, and an aqueous solution containing 10% by mass of ammonium chloride ( 12.63 g, 236 mmol) was added dropwise. The celite was filtered to solids. Then, after the aqueous layer was removed from the filtrate, the organic layer was concentrated on a rotary evaporator to give a crude product. The crude product was then dissolved in ethyl acetate (1 liter) and washed with distilled water (500 ml). After three times, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated, and the crude product of the obtained compound (34) was recrystallized from methanol (100 g) / 2-propanol (100 g) to obtain a diamine compound (3 4 (yield: 1 5.4 g, yield: 6 1 % -58 - 200940506 !H-NMR (400 MHz &gt; DMSO-d6, &lt; 5 ppm ) : 9.20 ( 1H, dd ) ' 8.85 ( 1H, dd ) &gt 8.43-8.40 ( 1H, m) , 7.62 - 7.59 ( 1H, m) , 7.19 - 7.16 ( 2H, m ) , 6.88 - 6.84 ( 2H, m ), 6.53 ( 1H, d ) , 6.02 ( 1H, d) &gt; 5.81 ( 1H, Dd ) , 4.69 ( 2H, s ) , 4.57 ( 2H, s ). <Example 1 1>

二胺化合物（3 7 )之合成 〔化 24〕 ❹Synthesis of diamine compound (3 7 )

在氮氣氛圍下，以冰浴使含化合物（32) ( 17.00克 ，61.6毫莫耳）、化合物（35) (6.57毫升，67.7毫莫耳 )及三苯基膦（20.99克，80.0毫莫耳）之四氫呋喃（340 克）溶液冷卻，且緩慢滴加含DEAD (偶氮二羧酸二乙酯 )(40質量％甲苯溶液’ 34.84毫升’ 80.0毫莫耳）溶液 。滴加結束後，使反應溫度緩慢上升至2 3 °C進行反應。以 HPLC確認反應結束後，以蒸發器餾除溶劑’獲得粗製產 -59- 200940506 物。隨後，以2-丙醇（ 450克）進行再結晶兩次，獲得化 合物（36)(產量：17.77克，產率：79%)。 ^-NMR ( 400MHz &gt; CDC13 &gt; δ ppm) ： 8.84 ( 1Η, d ) ，8.71 ( 1H，寬）’ 8.63 ( 1H，dd) &gt; 8.30 ( 1H, dd )， 7.80 ( 1H, d ) ，7.36 ( 1H，q) ，7.1 2 - 7 · 0 8 ( 4 H，m )， 7.0 1 ( 1 H, d ) ，5.04 ( 2H，s )。 接著，在氮氣氛圍中，於氫氣存在下，於23 °C下攪拌 化合物（36) (15.00克，40_8毫莫耳）、氧化鉑（IV) q (含水型，1.5克，l〇wt%)及1，4-二噁烷（230克）之混 合物。反應結束後’以矽藻土過濾觸媒後，以旋轉蒸發器 餾除溶劑獲得粗製產物。所得粗製產物以2-丙醇（60克 )再結晶，獲得二胺化合物（37)(產量：9.66克’產率 ：7 7%) ° *H-NMR ( 400MHz &gt; CDC13 ' δ ppm) ： 8.66 ( 1Η, d ) ，8.57 ( 1H，dd) &gt; 7.77 ( 1H, m) ，7.34 ( 1H，q) &gt; 6.87 (4H，s) ，6.69(lH，d) ，6.16( lH，d) ，6.07(lH，dd ❹ )，5.02 ( 2H, s ) ，3.65 -3.48 ( 4H，寬）。 &lt;合成例1 &gt; -二胺化合物（40)之合成 -60- 200940506 〔化 25〕The compound (32) (1,700 g, 61.6 mmol), the compound (35) (6.57 ml, 67.7 mmol) and triphenylphosphine (20.99 g, 80.0 mmol) were placed in an ice bath under a nitrogen atmosphere. The tetrahydrofuran (340 g) solution was cooled, and a solution containing DEAD (diethyl azodicarboxylate) (40% by mass toluene solution '34.84 ml '80.0 mmol) was slowly added dropwise. After the completion of the dropwise addition, the reaction was slowly raised to 23 ° C to carry out a reaction. After confirming the completion of the reaction by HPLC, the solvent was distilled off by an evaporator to obtain a crude product -59-200940506. Subsequently, it was recrystallized twice with 2-propanol (450 g) to obtain Compound (36) (yield: 17.77 g, yield: 79%). ^-NMR (400 MHz &gt; CDC13 &gt; δ ppm) : 8.84 (1 Η, d ) , 8.71 ( 1H, Width) ' 8.63 ( 1H, dd) &gt; 8.30 ( 1H, dd ), 7.80 ( 1H, d ) , 7.36 ( 1H,q) , 7.1 2 - 7 · 0 8 ( 4 H,m ), 7.0 1 ( 1 H, d ) , 5.04 ( 2H, s ). Next, the compound (36) (15.00 g, 40_8 mmol), platinum (IV) oxide (aqueous form, 1.5 g, l〇wt%) was stirred at 23 ° C in the presence of hydrogen under a nitrogen atmosphere. And a mixture of 1,4-dioxane (230 g). After the completion of the reaction, the catalyst was filtered through diatomaceous earth, and the solvent was distilled off by a rotary evaporator to obtain a crude product. The obtained crude product was recrystallized from 2-propanol (60 g) to give the diamine compound (37) (yield: 9.66 g, yield: 7 7%). *H-NMR (400 MHz &gt; CDC13 ' δ ppm) : 8.66 ( 1Η, d ) , 8.57 ( 1H, dd) &gt; 7.77 ( 1H, m) , 7.34 ( 1H, q) &gt; 6.87 (4H, s) , 6.69 (lH, d) , 6.16 ( lH, d) , 6.07 (lH, dd ❹ ), 5.02 ( 2H, s ), 3.65 - 3.48 ( 4H, width). &lt;Synthesis Example 1 &gt; Synthesis of diamine compound (40) -60- 200940506 [Chem. 25]

(1) (39) (40)(1) (39) (40)

φ 使含化合物（3 8 ) ( 23.45克，190毫莫耳）及三乙 胺（19.23克，277毫莫耳）之四氫呋喃（230克）溶液冷 卻至1(TC以下，且一面注意發熱一面滴加含化合物（1) (41.68克，180毫莫耳）之四氫呋喃（110克）溶液。滴 加結束後，使反應溫度上升至23 °C，再進行反應。以 HPLC (高速液體層析）確認反應結束後，將反應液體倒 入蒸餾水（1.5升）中，過濾析出之固體，並經水洗。隨 後，以乙醇（3 80克）分散洗淨固體，獲得化合物（39 ) ❹ (產量：50.82克，產率：89% )。 ^-NMR ( 400MHz &gt; DMSO-d6 · δ ppm) ： 9.76 ( 1Η, t ) ，9.09-9.02 ( 2H, m ) ，8.99-8.93 ( 1 H，m ) ，8.50 ( 1H，寬），7.64-7.60 ( 1H，m ) ，7 · 3 6-7.3 2 ( 1 H, m ) ’ 7.20-7.14 ( 1H，m) ，4.57 ( 2H，s) ，3.35 ( 2H，s)。 接著，在氫氣存在下，於60 °C下攪拌化合物（39)( 48.00克，151毫莫耳）、5%鈀/碳（含水型，4.8克， 10 wt% )及1，4-二噁烷（4 90克）之混合物。反應結束後 ，以矽藻土過濾觸媒後，以旋轉蒸發器餾除溶劑獲得粗製 -61 - 200940506 產物。以乙醇（300克）分散洗淨所得粗製產物，獲得二 胺化合物（40)(產量：27.20克，產率：70%)。 *H-NMR ( 400MHz » DMSO-d6 &gt; δ ppm) ： 8.64 ( 1Η, t) ，8.50 ( 1H，d ) ，8.44 ( 1H，d) ，7.67 ( 1H，d )， 7.34 ( 1H, q ) 1 6.23 ( 2H, d ) ，5.94 ( 1H, s) &gt; 4.87 ( 4H, s ) ，4.39 ( 2H，d )。 &lt;合成例2&gt; 二胺化合物（43 )之合成 〔化 2 6〕φ Cool the solution containing the compound (3 8 ) ( 23.45 g, 190 mmol) and triethylamine (19.23 g, 277 mmol) in tetrahydrofuran (230 g) to 1 (TC or less, and pay attention to the heat while dripping A solution of the compound (1) (41.68 g, 180 mmol) in tetrahydrofuran (110 g) was added. After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further carried out, and confirmed by HPLC (high-speed liquid chromatography). After completion of the reaction, the reaction liquid was poured into distilled water (1.5 liters), and the precipitated solid was filtered and washed with water. Then, the solid was washed with ethanol (3 80 g) to obtain a compound (39) ❹ (yield: 50.82 g) , yield: 89%). ^-NMR (400MHz &gt; DMSO-d6 · δ ppm) : 9.76 ( 1Η, t ) , 9.09-9.02 ( 2H, m ) , 8.99-8.93 ( 1 H, m ) , 8.50 (1H, wide), 7.64-7.60 ( 1H,m ) , 7 · 3 6-7.3 2 ( 1 H, m ) ' 7.20-7.14 ( 1H,m) , 4.57 ( 2H,s) ,3.35 ( 2H,s Next, the compound (39) (48.00 g, 151 mmol), 5% palladium/carbon (aqueous form, 4.8 g, 10 wt%) and 1,4- are stirred at 60 ° C in the presence of hydrogen. Dioxane After the reaction was completed, the catalyst was filtered with celite, and then the solvent was distilled off on a rotary evaporator to obtain a crude product of -61 - 200940506. The crude product was obtained by dispersing with ethanol (300 g) to obtain two. Amine compound (40) (yield: 27.20 g, yield: 70%). *H-NMR (400 MHz » DMSO-d6 &gt; δ ppm) : 8.64 (1 Η, t) , 8.50 ( 1H, d ) , 8.44 ( 1H,d), 7.67 ( 1H,d ), 7.34 ( 1H, q ) 1 6.23 ( 2H, d ) , 5.94 ( 1H, s) &gt; 4.87 ( 4H, s ) , 4.39 ( 2H,d ). Synthesis Example 2 Synthesis of Diamine Compound (43) [Chem. 2 6]

(41) 使含化合物（41) (ΐ5·22克，142毫莫耳）及三乙 胺（15.09克’ 149毫莫耳）之四氫呋喃（150克）溶液冷 卻至10 °C以下’且—面注意發熱一面滴加含化合物（i) (31.1克，135毫莫耳）之四氫呋喃（50克）溶液。滴加 結束後，使反應溫度上升至2 3 °C，再進行反應。以HPLC 確認反應結束後’將反應液體倒入蒸餾水（1升）中，過 濾析出之固體’並經水洗。隨後，以乙醇（3〇〇克）分散 洗淨固體，獲得化合物（42)(產量：36.92克，產率： -62- 200940506 9 0%)。 !H-NMR ( 400MHz &gt; DMSO-de &gt; δ ppm) ： 9.75 ( 1H, 寬），9.10 ( 2H，s) ，8.97-8.92 ( 1H，m) ，7.40-7.22 ( 5H, m ) &gt; 4.59-4.52 ( 2H, m )。 接著，在氫氣存在下，於60°C下攪拌化合物（42 )( 36.00克，119毫莫耳）、5%鈀/碳（含水型，3.6克， 10 wt% )及I，4-二噁烷（3 00克）之混合物。反應結束後 〇 ，以矽藻土過濾觸媒後，以旋轉蒸發器餾除溶劑獲得粗製 產物。以甲醇（200克）使所得粗製產物再結晶，獲得^ 胺化合物（43 )(產量：21 ·5克，產率：72% )。 !H-NMR ( 400MHz &gt; DMSO-d^ &gt; δ ppm) ： 8.55 ( 1Η 寬），7.34-7.17 ( 5Η，m ) - 6.28 ( 2H, s ) - 6.98-6.94 ( 1H, m) &gt; 4.85-4.74 ( 4H，寬），4.42-4.35 ( 2H, m )。(41) Cooling a solution containing compound (41) (ΐ5·22 g, 142 mmol) and triethylamine (15.09 g '149 mmol) in tetrahydrofuran (150 g) to below 10 °C A solution of the compound (i) (31.1 g, 135 mmol) in tetrahydrofuran (50 g) was added dropwise while heating. After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction by HPLC, the reaction liquid was poured into distilled water (1 liter), and the precipitated solid was filtered off and washed with water. Subsequently, the solid was washed with ethanol (3 g) to obtain a compound (42) (yield: 36.92 g, yield: -62 - 200940506 90%). !H-NMR (400MHz &gt; DMSO-de &gt; δ ppm) : 9.75 ( 1H, Width), 9.10 ( 2H, s) , 8.97 - 8.92 ( 1H, m ) , 7.40 - 7.22 ( 5H, m ) &gt; 4.59-4.52 ( 2H, m ). Next, compound (42) (36.00 g, 119 mmol), 5% palladium/carbon (aqueous form, 3.6 g, 10 wt%) and I,4-dioxin were stirred at 60 ° C in the presence of hydrogen. a mixture of alkanes (300 g). After the completion of the reaction, 过滤, after filtering the catalyst with diatomaceous earth, the solvent was distilled off by a rotary evaporator to obtain a crude product. The obtained crude product was recrystallized from methanol (200 g) to give the amine compound (43) (yield: 21.5 g, yield: 72%). !H-NMR (400MHz &gt; DMSO-d^ &gt; δ ppm) : 8.55 ( 1Η wide), 7.34 - 7.17 ( 5Η,m ) - 6.28 ( 2H, s ) - 6.98-6.94 ( 1H, m) &gt; 4.85-4.74 (4H, wide), 4.42-4.35 (2H, m).

-63- 200940506 〔表4〕 二胺化合物 Χι x2 x3 X4 η 實施例1 4 -CONH- 亞甲基 單鍵 吡啶環 1 實施例2 7 -CON (CH3)- 亞甲基 單鍵 口比陡環 1 實施例3 10 -CONH- 伸乙基 單鍵 口比陡環 1 實施例4 14 -Ο- 亞甲基 單鍵 吡啶環 1 實施例5 16 -NH- 亞甲基 單鍵 口比陡環 1 實施例ό 19 -NH- 亞甲基 單鍵 咖定環 1 實施例7 23 -NHCO- 單鍵 單鍵 啦陡環 1 實施例8 26 -NHCO- 單鍵 單鍵 耻淀環 1 實施例9 29 亞甲基 單鍵 口比陡環 2 實施例10 34 -0 苯基 -OCO- 口比陡環 1 實施例11 37 苯基 -coh2- 口比π定環 1 合成例1 40 -COO- 伸乙基 單鍵 咖定環 1 合成例2 43 -CONH- 亞甲基 單鍵 苯環 1 〔聚醯胺酸及聚醯亞胺之合成〕 以下顯示所使用之四羧酸二酐等化合物之簡稱。 (四羧酸二酐） CBDA: 1,2,3,4-環丁烷四羧酸二酐 BODA:雙環〔3,3,0〕辛烷-2,4,6,8-四羧酸二酐 〔化 2 7〕-63- 200940506 [Table 4] Diamine compound Χι x2 x3 X4 η Example 1 4-CONH-methylene single bond pyridine ring 1 Example 2 7 -CON (CH3)-methylene single bond ratio steep ring 1 Example 3 10 -CONH-extension ethyl single bond port ratio steep ring 1 Example 4 14 -Ο-methylene single bond pyridine ring 1 Example 5 16 -NH-methylene single bond port ratio steep ring 1 EXAMPLES - 19 -NH-methylene single bond coffee ring 1 Example 7 23 -NHCO- single bond single bond steep ring 1 Example 8 26 -NHCO- single bond single bond mascara ring 1 Example 9 29 Methylene single bond port ratio steep ring 2 Example 10 34 -0 Phenyl-OCO-port ratio steep ring 1 Example 11 37 Phenyl-coh2-port ratio π-ring ring 1 Synthesis Example 1 40 -COO- stretching Basic single bond ring 1 Synthesis Example 2 43 -CONH-methylene single bond benzene ring 1 [Synthesis of polyamic acid and polyimine] The following is abbreviated as a compound such as tetracarboxylic dianhydride used. (tetracarboxylic dianhydride) CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid Anhydride (chemical 2 7)

200940506 AP18: 1，3-二胺基（4-正辛醯基）苯 PCH7DAB: 1,3-二胺基·4-〔4-(反式-4-正庚基環己 基）苯氧基〕苯 〔化 2 8〕200940506 AP18: 1,3-diamino(4-n-octyl)benzene PCH7DAB: 1,3-diamino-4-(4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene 2 8]

(有機溶劑） ΝΜΡ: Ν -甲基-2-吡咯啶酮 BCS : 丁基溶纖素 &lt;聚醯亞胺之分子量測定&gt; 合成例中之聚醯亞胺之分子量係使用昭和電工公司製 造之常溫凝膠滲透層析（GPC)裝置（GPC-101)， Shodex公司製造之管柱（KD-803，KD- 805 )，如下列般 測定。(Organic solvent) ΝΜΡ: Ν-methyl-2-pyrrolidone BCS: butyl cellulase &lt; molecular weight measurement of polyimine] The molecular weight of the polyimine in the synthesis example is the normal temperature manufactured by Showa Denko Co., Ltd. A gel permeation chromatography (GPC) apparatus (GPC-101), a column manufactured by Shodex Co., Ltd. (KD-803, KD-805), was measured as follows.

管柱溫度：50°C 溶離液：N，N’-二甲基甲醯胺（作爲添加劑，溴化鋰_ 水合物（LiBr · H20 )爲30毫莫耳/升，磷酸·無水結晶 (〇-磷酸）爲30毫莫耳/升’四氫呋喃（THF)爲10毫升 /升） 流速：1.0毫升/分鐘 校正線製作用標準樣品：東曹公司製造之TSK，標準 聚環氧乙烷（分子量 900,000，1 50,000，100,000，3〇,〇〇〇 -65- 200940506 )及聚合物實驗室公司製造之聚乙二醇（分子量約12,000 ，4,000，1,000 ) ° &lt;醯亞胺化率之測定&gt; 合成例中之聚醯亞胺之醯亞胺化率係如下列般測定。 將20毫克之聚醯亞胺粉末加入NMR樣品管（草野科 學公司製造之NMR樣品管標準，φ 5 )中，添加0.53毫 升之氘化二甲基亞楓（DMSO-d6，0.05%TMS混合物）， _ 且以超音波使之完全溶解。日本電子DATUM公司製造之 NMR測定器（JNW-ECA500 )，測定該溶液之500MHz之 質子NMR。醯亞胺化率係使用源自醯亞胺化前後未變化之 構造之質子作爲基準質子予以決定之該質子之峰估算値， 及自9.5至10. Oppm附近出現之來自醯胺酸之NH基之質 子峰之估算値，以下列之式求得。Column temperature: 50 ° C Dissolution: N, N'-dimethylformamide (as an additive, lithium bromide _ hydrate (LiBr · H20) is 30 mmol / liter, phosphoric acid · anhydrous crystals (〇-phosphoric acid ) 30 mmol / liter 'tetrahydrofuran (THF) 10 ml / liter) Flow rate: 1.0 ml / min Calibration line for the preparation of standard samples: TSK manufactured by Tosoh Corporation, standard polyethylene oxide (molecular weight 900,000, 1 50,000,100,000,3〇,〇〇〇-65- 200940506) and polyethylene glycol manufactured by Polymer Laboratories, Inc. (molecular weight: about 12,000, 4,000,1,000) ° &lt;Measurement of oxime imidization rate&gt; Synthesis example The imidization ratio of the polyimine in the medium is determined as follows. 20 mg of the polyimine powder was added to a NMR sample tube (NMR sample tube standard manufactured by Kusano Scientific Co., Ltd., φ 5 ), and 0.53 ml of dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture) was added. , _ and completely dissolve it by ultrasonic waves. A NMR analyzer (JNW-ECA500) manufactured by Japan Electronics DATUM Co., Ltd. was used to measure the proton NMR of the solution at 500 MHz. The ruthenium imidization ratio is a peak estimation of the proton determined by using a proton derived from an unaltered structure before and after the imidization as a reference proton, and an NH group derived from proline from 9.5 to 10. Oppm. The estimation of the proton peak is obtained by the following formula.

醯亞胺化率（％)=(l-a.x/y)xl〇〇 Q 上述式中，X爲源自醯胺酸之NH基之質子峰估算値 ，y爲基準質子峰估算値，0：爲聚醯胺酸（醯亞胺化率爲 0%)時相對於醯胺酸之NH基一個質子之基準質子之個數 比例。 &lt;實施例12&gt; 將 BODA(3.33 克，13.3 毫莫耳）、p_pDA(〇_67 克 -66- 200940506 ’ 6.21 毫莫耳）、PCH7DAB (3.38 克，8.87 毫莫耳）及 二胺化合物（4) ( 0.64克，2.66毫莫耳）於NMP ( 15.0 克）中混合’且於80°C下反應5小時後，添加CBDA ( 0.87克，4.44毫莫耳）及ΝΜΡ(13·1克），且在40。(：下 反應6小時’獲得樹脂成分之含量爲24質量％之聚醯胺酸 溶液（Α)。該聚醯胺酸之數平均分子量爲17,9〇〇，重量 平均分子量爲5 1，800。 ❹ &lt;實施例13&gt; 將ΝΜΡ添加於實施例12中獲得之聚醯胺酸溶液（a )(20.0克）中’稀釋成6質量％後，添加作爲醯亞胺化 觸媒之乙酸酐（2.63克）及吡啶（2.03克），且在80°C 下反應2小時。將該反應溶液倒入甲醇（250毫升）中， 過濾所得沉澱物。以甲醇洗淨該沉澱物，且於100 °C下減 壓乾燥，獲得聚醯亞胺粉末（B)。該聚醯亞胺之醯亞胺 G 化率爲40%，數平均分子量爲16,400，重量平均分子量爲 44,800 ° &lt;實施例14&gt; 將 BODA ( 2.33 克，9.33 毫莫耳）、p-PDA ( 0.94 克 ，8.71毫莫耳）、AP 18(0.47克，1.24毫莫耳）及二胺 化合物（7) (0.64克，2_63毫莫耳）於ΝΜΡ(8·10克） 中混合，且於80 °C下反應5小時後，添加CBDA (0.61克 ，3. 1 1毫莫耳）及NMP ( 6.51克），且在40°C下反應6 -67- 200940506 小時，獲得聚醯胺酸溶液。 將NMP添加於所得之聚醯胺酸溶液（10.0克）中， 稀釋成6質量％後，添加作爲醯亞胺化觸媒之乙酸酐（ 1.33克）及吡啶（1.04克），且在80°C下反應2小時。 將該反應溶液倒入甲醇（120毫升）中，過瀘所得沉澱物 。以甲醇洗淨該沉澱物，且於100 °C下減壓乾燥，獲得聚 醯亞胺粉末（C)。該聚醯亞胺之醯亞胺化率爲41%，數 平均分子量爲17,500，重量平均分子量爲46,400。 &lt;實施例15&gt;Ruthenium amination rate (%) = (la.x / y) xl 〇〇 Q In the above formula, X is the proton peak estimate derived from the NH group of the proline, y is the reference proton peak estimate 値, 0: It is the ratio of the number of reference protons of one proton relative to the NH group of valine by polyproline (0% imidization). &lt;Example 12&gt; BODA (3.33 g, 13.3 mmol), p_pDA (〇_67 g-66-200940506 ' 6.21 mmol), PCH7DAB (3.38 g, 8.87 mmol), and a diamine compound ( 4) (0.64 g, 2.66 mmol) mixed in NMP (15.0 g) and reacted at 80 ° C for 5 hours, then added CBDA (0.87 g, 4.44 mmol) and hydrazine (13·1 g) And at 40. (: 6 hours under the reaction to obtain a polyamic acid solution (Α) having a resin component content of 24% by mass. The polyamino acid has a number average molecular weight of 17,9 Å and a weight average molecular weight of 5 1,800. ❹ &lt;Example 13&gt; After adding hydrazine to the polyamic acid solution (a) (20.0 g) obtained in Example 12, 'diluted to 6 mass%, and then acetic anhydride was added as a ruthenium catalyzed catalyst. (2.63 g) and pyridine (2.03 g), and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (250 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and at 100 It was dried under reduced pressure at ° C to obtain a polyimine powder (B). The polyimine had a G of 40%, a number average molecular weight of 16,400, and a weight average molecular weight of 44,800 ° &lt;Example 14&gt;; BODA ( 2.33 g, 9.33 mmol), p-PDA (0.94 g, 8.71 mmol), AP 18 (0.47 g, 1.24 mmol) and diamine compound (7) (0.64 g, 2_63 m) Mole) was mixed in ΝΜΡ (8·10 g) and reacted at 80 ° C for 5 hours, then added CBDA (0.61 g, 3.11 mmol) And NMP (6.51 g), and reacted at 40 ° C for 6 -67 - 200940506 hours to obtain a poly-proline solution. NMP was added to the obtained poly-proline solution (10.0 g) and diluted to 6 masses. After the addition of acetic anhydride (1.33 g) and pyridine (1.04 g) as a ruthenium catalyst, the reaction was carried out at 80 ° C for 2 hours. The reaction solution was poured into methanol (120 ml) and passed through The obtained precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (C). The polyamidimide had a ruthenium imidation ratio of 41% and a number average molecular weight. It was 17,500 and the weight average molecular weight was 46,400. &lt;Example 15&gt;

將 BODA ( 3_25 克，13_0 毫莫耳）、p-PDA ( 0.66 克 ，6.07 毫莫耳）、PCH7DAB (3.30 克，8.67 毫莫耳）及 二胺化合物（10) (0.67克，2.60毫莫耳）混合於NMP (14.7克）中，且於80°C下反應5小時後，添加CBDA ( 0.85克，4.33毫莫耳）及NMP (12.0克），且在40°C下 反應6小時，獲得樹脂成分之含量爲25質量％之聚醯胺酸 溶液（D)。該聚醯胺酸之數平均分子量爲1 8,800，重量 平均分子量爲5 1,800。 &lt;實施例16&gt; 將NMP添加於實施例15中獲得之聚醯胺酸溶液（D )(20.0克）中，稀釋成6質量％後，添加作爲醯亞胺化 觸媒之乙酸酐（2_61克）及吡啶（2.07克），且在80°C 下反應2小時。將該反應溶液倒入甲醇（220毫升）中， -68- 200940506 過濾所得沉澱物。以甲醇洗淨該沉澱物，且於loot下減 壓乾燥，獲得聚醯亞胺粉末（E)。該聚醯亞胺之醯亞胺 化率爲42%，數平均分子量爲17,400，重量平均分子量爲 45,800 ° &lt;實施例17&gt; 將 BODA ( 2.22 克，8.87 毫莫耳）、p-PDA ( 0.58 克 φ ，5.32 毫莫耳）、PCH7DAB ( 1.35 克，3.55 毫莫耳）及 二胺化合物（14) (0.64克，2·96毫莫耳）於NMP ( 8.10 克）中混合，且於80°C下反應5小時後，添加CBDA ( 0.58克，2.96毫莫耳）及ΝΜΡ(6·30克），且在40°C下 反應6小時，獲得聚醯胺酸溶液。 將NMP添加於所得聚醯胺酸溶液（10.1克）中，稀 釋成6質量％後，添加作爲醯亞胺化觸媒之乙酸酐（1.34 克）及吡啶（1.04克），且在80 °C下反應2小時。將該 Ο 反應溶液倒入甲醇（140毫升）中，過濾所得沉澱物。以 甲醇洗淨該沉澱物，且於100 °C下減壓乾燥，獲得聚醯亞 胺粉末（F)。該聚醯亞胺之醯亞胺化率爲41%，數平均 分子量爲18,100’重量平均分子量爲47,300。 &lt;實施例18&gt; 將 BODA ( 2.18 克，8·72 毫莫耳）、p-PDA ( 0.69 克 ，6.39毫莫耳）、ΑΡ 18(0.66克，1.74毫莫耳）及二胺 化合物（16) (0.75克，3_49毫莫耳）於ΝΜΡ ( 10.0克 -69- 200940506 )中混合，且於80°C下反應5小時後，添加CBDA ( 0.57 克，2_91毫莫耳）及NMP(8.30克）’且在40 °C下反應 6小時，獲得聚醯胺酸溶液。 將NMP添加於所得聚醯胺酸溶液（10.1克）中，稀 釋成6質量％後，添加作爲醯亞胺化觸媒之乙酸酐（1.35 克）及吡啶（1.07克），且在80°C下反應2小時。將該 反應溶液倒入甲醇（140毫升）中，過濾所得沉澱物。以 甲醇洗淨該沉澱物，且於1〇〇 °C下減壓乾燥，獲得聚醯亞 胺粉末（G)。該聚醯亞胺之醯亞胺化率爲40%，數平均 分子量爲1 7,500，重量平均分子量爲46,000。 &lt;實施例19&gt;BODA (3_25 g, 13_0 mmol), p-PDA (0.66 g, 6.07 mmol), PCH7DAB (3.30 g, 8.67 mmol) and diamine compound (10) (0.67 g, 2.60 mmol) After mixing in NMP (14.7 g) and reacting at 80 ° C for 5 hours, CBDA (0.85 g, 4.33 mmol) and NMP (12.0 g) were added, and reacted at 40 ° C for 6 hours to obtain The polyaminic acid solution (D) having a resin component content of 25% by mass. The polyamine has a number average molecular weight of 1,800 and a weight average molecular weight of 1,1,800. &lt;Example 16&gt; NMP was added to the polyamic acid solution (D) (20.0 g) obtained in Example 15, and after diluting to 6 mass%, acetic anhydride (2_61) as a ruthenium catalyst was added. G) and pyridine (2.07 g) were reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (220 ml), and the obtained precipitate was filtered from -68-200940506. The precipitate was washed with methanol and dried under reduced pressure at a loot to obtain a polyimine powder (E). The polyamidimide had a ruthenium iodide ratio of 42%, a number average molecular weight of 17,400, and a weight average molecular weight of 45,800 ° &lt;Example 17&gt; BODA (2.22 g, 8.87 mmol), p-PDA (0.58克φ, 5.32 mmol, PCH7DAB (1.35 g, 3.55 mmol) and diamine compound (14) (0.64 g, 2.96 mmol) mixed in NMP (8.10 g) at 80° After reacting for 5 hours at C, CBDA (0.58 g, 2.96 mmol) and hydrazine (6·30 g) were added, and reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. NMP was added to the obtained polyamic acid solution (10.1 g), and after diluting to 6% by mass, acetic anhydride (1.34 g) and pyridine (1.04 g) as a ruthenium catalyst were added, and at 80 ° C. The reaction was carried out for 2 hours. The hydrazine reaction solution was poured into methanol (140 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (F). The polyimine had a ruthenium imidation ratio of 41%, a number average molecular weight of 18, and a weight average molecular weight of 47,300. &lt;Example 18&gt; BODA (2.18 g, 8.72 mmol), p-PDA (0.69 g, 6.39 mmol), ΑΡ18 (0.66 g, 1.74 mmol), and a diamine compound (16) (0.75 g, 3_49 mmol) mixed in ΝΜΡ (10.0 g-69-200940506) and reacted at 80 ° C for 5 hours, then added CBDA (0.57 g, 2_91 mmol) and NMP (8.30 g) ' and reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution. NMP was added to the obtained polyamic acid solution (10.1 g), and after diluting to 6% by mass, acetic anhydride (1.35 g) and pyridine (1.07 g) as a ruthenium catalyst were added, and at 80 ° C. The reaction was carried out for 2 hours. The reaction solution was poured into methanol (140 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimide powder (G). The polyimine had a hydrazine imidation ratio of 40%, a number average molecular weight of 17,500, and a weight average molecular weight of 46,000. &lt;Example 19&gt;

將 BODA ( 2.30 克，9.18 毫莫耳）、p-PDA ( 0.46 克 ，4.28 毫莫耳）、PCH7DAB (2.33 克，6.12 毫莫耳）及 二胺化合物（19) (0.39克，1.84毫莫耳）混合於NMP (10.5克）中，且於80°C下反應5小時後，添加CBDA ( 〇 0.57克，2.91毫莫耳）及NMP(8.00克），且在40°C下 反應6小時，獲得聚醯胺酸溶液。 將NMP添加於所得聚醯胺酸溶液（1〇.〇克）中，稀 釋成6質量％後，添加作爲醯亞胺化觸媒之乙酸酐（1.31 克）及吡啶（1.04克），且在80 °C下反應2小時。將該 反應溶液倒入甲醇（140毫升）中’過濾所得沉澱物。以 甲醇洗淨該沉澱物，且於100 °C下減壓乾燥，獲得聚醯亞 胺粉末（H)。該聚醯亞胺之醯亞胺化率爲40%，數平均 -70- 200940506 分子量爲18,900，重量平均分子量爲49,100。 &lt;實施例20&gt; 將 BODA ( 2.33 克，9.33 毫莫耳）、p-PDA ( 0_47 克 ’ 4.35 毫莫耳）、PCH7DAB(2.37 克，6.22 毫莫耳）及 二胺化合物（23 ) ( 0.43克，1.87毫莫耳）於NMP ( 10.50克）中混合，且於80°c下反應 5小時後，添加 〇 CBDA(0.61 克，3.11 毫莫耳）及 NMP ( 8.10 克），且在 4〇°C下反應6小時，獲得聚醯胺酸溶液。 將NMP添加於所得聚醯胺酸溶液（10.2克）中，稀 釋成6質量％後，添加作爲醯亞胺化觸媒之乙酸酐（1.37 克）及吡啶（1.04克），且在80°C下反應2小時。將該 反應溶液倒入甲醇（150毫升）中，過濾所得沉澱物。以 甲醇洗淨該沉澱物，且於1〇〇 °C下減壓乾燥，獲得聚醯亞 胺粉末（I)。該聚醯亞胺之醯亞胺化率爲42%，數平均 〇 分子量爲19,900，重量平均分子量爲52，100。 &lt;實施例21&gt; 將 BODA ( 2.26 克，9.03 毫莫耳）、p-PDA ( 0.72 克 ,6.62毫莫耳）、AP 18(0.45克，1.20毫莫耳）及二胺 化合物（26) (0.96克，4.21毫莫耳）混合於NMP (8.10 克）中，且於80°C下反應5小時後，添加CBDA(0.59克 ，3.01毫莫耳）及NMP(6.10克），且在40 °C下反應6 小時，獲得聚醯胺酸溶液。 -71 - 200940506 將NMP添加於所得聚醯胺酸溶液（10.0克）中，稀 釋成6質量％後，添加作爲醯亞胺化觸媒之乙酸酐（1.34 克）及吡啶（1.04克），且在80°C下反應2小時。將該 反應溶液倒入甲醇（150毫升）中，過濾所得沉澱物。以 甲醇洗淨該沉澱物，且於100°C下減壓乾燥，獲得聚醯亞 胺粉末（J)。該聚醯亞胺之醯亞胺化率爲40%，數平均 分子量爲17,900，重量平均分子量爲45,800。 &lt;實施例22&gt; 將 BODA ( 2.22 克，8.87 毫莫耳）、ρ-PDA ( 1.02 克 ，9_46毫莫耳）、ΑΡ18(0·44克，1.18毫莫耳）及二胺 化合物（29) (0.38克，1.18毫莫耳）於ΝΜΡ ( 7.00克 )中混合，且於80°C下反應5小時後，添加CBDA(0.58 克，2.96毫莫耳）及NMP (6.50克），且在40。(：下反應 6小時，獲得樹脂成分之含量爲26質量％之聚醯胺酸溶液 (K)。該聚醯胺酸之數平均分子量爲17,500，重量平均 分子量爲45,1 00。 &lt;實施例23&gt; 將 BODA ( 3.25 克，13.0 毫莫耳）、p-PDA ( 0.56 克 ，5·20 毫莫耳）、PCH7DAB(3_30 克，8_67 毫莫耳）及 二胺化合物（34) ( 1.11克，3.47毫莫耳）於NMP( 15.0 克）中混合，且於80°C下反應5小時後，添加CBDA( 0.85克，4.33毫莫耳）及NMP( 12.5克），且在4〇。〇下 -72- 200940506 反應6小時，獲得聚醯胺酸溶液。 將NMP添加於所得之聚醯胺酸溶液（20.0克）中， 稀釋成6質量％後，添加作爲醯亞胺化觸媒之乙酸酐（ 2.65克）及吡啶（2· 07克），且在80°C下反應2小時。 將該反應溶液倒入甲醇（310毫升）中，過濾所得沉澱物 。以甲醇洗淨該沉澱物，且於100 °C下減壓乾燥，獲得聚 醯亞胺粉末（L)。該聚醯亞胺之醯亞胺化率爲40%，數 Φ 平均分子量爲20,100，重量平均分子量爲53,400。 &lt;實施例24&gt; 將 BODA ( 3.25 克，13.0 毫莫耳）、p-PDA ( 0.66 克 ，6.07 毫莫耳）、PCH7DAB ( 3.30 克，8.67 毫莫耳）及 二胺化合物（37) (0.80克，2.60毫莫耳）於NMP (14.8 克）中混合，且於8(TC下反應5小時後，添加CBDA ( 0.85克，4_33毫莫耳）及ΝΜΡ(12·0克），且在40°C下 〇 反應6小時，獲得樹脂成分之含量爲25質量％之聚醯胺酸 溶液（M)。該聚醯胺酸之數平均分子量爲1 9,400，重量 平均分子量爲52,800。 &lt;實施例25&gt; 將NMP添加於實施例24中獲得之聚醯胺酸溶液（M )(20.2克）中，稀釋成6質量％後，添加作爲醯亞胺化 觸媒之乙酸酐（2.68克）及吡啶（2.07克），且在80°C 下反應2小時。將該反應溶液倒入甲醇（300毫升）中， -73- 200940506 過濾所得沉澱物。以甲醇洗淨該沉澱物’且於100°c下減 壓乾燥，獲得聚醯亞胺粉末（N)。該聚醯亞胺之醯亞胺 化率爲41%，數平均分子量爲18,100，重量平均分子量爲 48,100 ° &lt;合成例3&gt;BODA (2.30 g, 9.18 mmol), p-PDA (0.46 g, 4.28 mmol), PCH7DAB (2.33 g, 6.12 mmol) and diamine compound (19) (0.39 g, 1.84 mmol) After mixing in NMP (10.5 g) and reacting at 80 ° C for 5 hours, CBDA (〇0.57 g, 2.91 mmol) and NMP (8.00 g) were added, and reacted at 40 ° C for 6 hours. A polyaminic acid solution was obtained. NMP was added to the obtained poly-proline solution (1 gram.), and after diluting to 6 mass%, acetic anhydride (1.31 g) and pyridine (1.04 g) as a ruthenium catalyst were added, and The reaction was carried out at 80 ° C for 2 hours. The reaction solution was poured into methanol (140 ml) and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (H). The polyimine has a hydrazine imidization ratio of 40%, a number average of -70 to 200940506, a molecular weight of 18,900, and a weight average molecular weight of 49,100. &lt;Example 20&gt; BODA (2.33 g, 9.33 mmol), p-PDA (0_47 g ' 4.35 mmol), PCH7DAB (2.37 g, 6.22 mmol), and diamine compound (23 ) (0.43) Grams, 1.87 mmoles were mixed in NMP (10.50 g) and reacted at 80 ° C for 5 hours, then 〇CBDA (0.61 g, 3.11 mmol) and NMP (8.10 g) were added, and at 4 〇 The reaction was carried out at ° C for 6 hours to obtain a polyaminic acid solution. NMP was added to the obtained polyamic acid solution (10.2 g), and after diluting to 6 mass%, acetic anhydride (1.37 g) and pyridine (1.04 g) as a ruthenium catalyst were added, and at 80 ° C. The reaction was carried out for 2 hours. The reaction solution was poured into methanol (150 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a polyimine powder (I). The polyimine had a ruthenium iodide ratio of 42%, a number average 〇 molecular weight of 19,900, and a weight average molecular weight of 52,100. &lt;Example 21&gt; BODA (2.66 g, 9.03 mmol), p-PDA (0.72 g, 6.62 mmol), AP 18 (0.45 g, 1.20 mmol), and diamine compound (26) ( 0.96 g, 4.21 mmol) mixed in NMP (8.10 g) and reacted at 80 ° C for 5 hours, then added CBDA (0.59 g, 3.01 mmol) and NMP (6.10 g) at 40 ° The reaction was carried out for 6 hours at C to obtain a polyaminic acid solution. -71 - 200940506 NMP was added to the obtained polyaminic acid solution (10.0 g), and after diluting to 6 mass%, acetic anhydride (1.34 g) and pyridine (1.04 g) as a ruthenium catalyst were added, and The reaction was carried out at 80 ° C for 2 hours. The reaction solution was poured into methanol (150 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (J). The polyimine had a hydrazine imidation ratio of 40%, a number average molecular weight of 17,900, and a weight average molecular weight of 45,800. &lt;Example 22&gt; BODA (2.22 g, 8.87 mmol), ρ-PDA (1.02 g, 9-46 mmol), ΑΡ18 (0.44 g, 1.18 mmol), and a diamine compound (29) (0.38 g, 1.18 mmol) was mixed in ΝΜΡ (7.00 g), and after reacting at 80 ° C for 5 hours, CBDA (0.58 g, 2.96 mmol) and NMP (6.50 g) were added, and at 40 . (: The next reaction was carried out for 6 hours to obtain a polyaminic acid solution (K) having a resin component content of 26% by mass. The polyamino acid had a number average molecular weight of 17,500 and a weight average molecular weight of 45,100. Example 23&gt; BODA (3.25 g, 13.0 mmol), p-PDA (0.56 g, 5·20 mmol), PCH7DAB (3-30 g, 8_67 mmol) and diamine compound (34) (1.11 g) , 3.47 mmoles, mixed in NMP (15.0 g), and after reacting at 80 ° C for 5 hours, CBDA (0.85 g, 4.33 mmol) and NMP (12.5 g) were added, and at 4 Torr. -72- 200940506 Reaction for 6 hours to obtain a poly-proline solution. NMP was added to the obtained poly-proline solution (20.0 g), diluted to 6 mass%, and then added as a ruthenium-based catalyst. The acid anhydride (2.65 g) and pyridine (2.07 g) were reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (310 ml), and the resulting precipitate was filtered, and the precipitate was washed with methanol. And drying under reduced pressure at 100 ° C to obtain a polyimine powder (L). The ruthenium imidization ratio of the polyimine is 40%, the number Φ average The amount is 20,100 and the weight average molecular weight is 53,400. &lt;Example 24&gt; BODA (3.25 g, 13.0 mmol), p-PDA (0.66 g, 6.07 mmol), PCH7DAB (3.30 g, 8.67 mmol) The ear compound and the diamine compound (37) (0.80 g, 2.60 mmol) were mixed in NMP (14.8 g), and after 5 hours of reaction at TC, CBDA (0.85 g, 4_33 mmol) was added. ΝΜΡ (12.0 g), and hydrazine reaction at 40 ° C for 6 hours to obtain a polyaminic acid solution (M) having a resin component content of 25% by mass. The number average molecular weight of the poly-proline is 149,400. The weight average molecular weight was 52,800. <Example 25> NMP was added to the polyamic acid solution (M) (20.2 g) obtained in Example 24, and diluted to 6 mass%, and then added as a ruthenium. Catalyst (2.68 g) and pyridine (2.07 g) were reacted for 2 hours at 80 ° C. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was filtered from -73 to 200940506. The precipitate was washed 'and dried under reduced pressure at 100 ° C to obtain a polyimine powder (N). The oxime imide ratio was 41%, the number average molecular weight was 18,100, and the weight average molecular weight was 48,100 ° &lt;Synthesis Example 3&gt;

將 BODA ( 3_29 克，13.2 毫莫耳）、p-PDA ( 0.67 克 ，6.14 毫莫耳）、PCH7DAB(3.34 克，8.77 毫莫耳）及 二胺化合物（40) (0.68克，2.63毫莫耳）混合於NMP (15.0克）中，且於8(TC下反應5小時後，添加CBDA ( 0.86克，4.39毫莫耳）及NMP(11.5克），且在40°C下 反應6小時，獲得樹脂成分之含量爲25質量％之聚醯胺酸 溶液（〇)。該聚醯胺酸之數平均分子量爲22,600，重量 平均分子量爲54,900。 &lt;合成例4&gt; 將NMP添加於合成例3中獲得之聚醯胺酸溶液（Ο ) (20.0克）中，稀釋成6質量％後，添加作爲醯亞胺化觸 媒之乙酸酐（2.65克）及吡啶（2.08克），且在80 °C下 反應2小時。將該反應溶液倒入甲醇（3 2 0毫升）中，過 濾所得沉澱物。以甲醇洗淨該沉澱物，且於100 °C下減壓 乾燥’獲得聚醯亞胺粉末（P)。該聚醯亞胺之醯亞胺化 率爲40%，數平均分子量爲1 8,900，重量平均分子量爲 49,200 〇 -74- 200940506 &lt;合成例5&gt; 將 BODA ( 3.22 克，12.9 毫莫耳）、p-pDA ( 〇_65 克 ，6.00 毫莫耳）、PCH7DAB ( 3.26 克，8_57 毫莫耳）及 二胺化合物（43) (0.62克，2_57毫莫耳）於NMP ( 15_2 克）中混合，且於80°C下反應5小時後，添加CBDA( 0.84克，4_28毫莫耳）及NMP (11.1克），且在40°C下 φ 反應6小時，獲得樹脂成分之含量爲25質量％之聚醯胺酸 溶液（Q)。該聚醯胺酸之數平均分子量爲22,100，重量 平均分子量爲53,200 * &lt;合成例6&gt; 將NMP添加於合成例5中獲得之聚醯胺酸溶液（q) (20.1克）中’稀釋成6質量％後，添加作爲醯亞胺化觸 媒之乙酸酐（2.68克）及卩比陡（2.04克），且在80。(：下 Φ 反應2小時。將該反應溶液倒入甲醇（350毫升）中，過 濾所得沉殺物。以甲醇洗淨該沉澱物，且於l〇〇〇c下減壓 乾燥’獲得聚醯亞胺粉末（R)。該聚醯亞胺之醯亞胺化 率爲41%’數平均分子量爲18,400，重量平均分子量爲 49,100 ° -75- 200940506 〔表5〕 實施例 二胺成分(腿〇1) 四竣酸成分(mmol) 醯亞胺 化率(％) 特定二胺化雜 其1 也二胺 12 聚醯胺酸 ΓΑ1 化纖4) (2.66) p-PDA (6.21) PCH7DAB (8.87) CBDA (4.44) BODA (13.3) - 13 聚醯亞胺粉末[B] 化合物⑷ (2.66) p-PDA (6.21) PCH7DAB (8.87) CBDA (4.44) BODA (13.3) 40 14 聚醯亞胺粉末[C] 化合物⑺ (2.63) p-PDA (8.71) AP18 (1.24) CBDA (3.11) BODA (9.33) 41 15 聚醯胺酸[D] 化雜(10) (2.60) p-PDA (6.07) PCH7DAB (8.67) CBDA (4.33) BODA O3.0) - 16 聚醯亞胺粉末[E] 化合物⑽ (2.60) p-PDA (6.07) PCH7DAB (8.67) CBDA (4.33) BODA (13.0) 42 17 聚醯亞胺粉末[F] 化細14) (2.96) p-PDA (5.32) PCH7DAB (3.55) CBDA (2.96) BODA (8.87) 41 18 聚醯亞胺粉末[G] 化编16) (3-49) p-PDA (6.39) AP18 (1.74) CBDA (2.91) BODA (8.72) 40 19 聚醯亞胺粉末[H] 化合物(19) (1-84) p-PDA (4.28) PCH7DAB (6.12) CBDA (2.91) BODA (9.18) 40 20 聚醯亞胺粉末[I] 化合物(23) (1.87) p-PDA (4.35) PCH7DAB (6.22) CBDA (3.11) BODA (9.33) 42 21 聚醯亞胺粉末[J] 化编26) (4.21) p-PDA (6.62) AP18 (1.20) CBDA (3.01) BODA (9.03) 40 22 聚醯胺酸[K] 化合物(29) (1.18) p-PDA (9.46) API 8 Π.18) CBDA (2.96) BODA (8.87) - 23 聚醯亞胺粉末[L] 化编34) (3.47) p-PDA (5.20) PCH7DAB (8.67) CBDA (4.33) BODA (13.0) 40 24 聚醯胺酸[M] 化合物(37) (2.60) p-PDA (6.07) PCH7DAB (8.67) CBDA (4.33) BODA (13.0) - 25 聚醯亞胺粉末[N] 化合物(37) (2.60) p-PDA (6.07) PCH7DAB (8.67) CBDA (4.33) BODA (13.0) 41 -76- 200940506 〔表6〕 合成例 二胺成分(mmol) 四羧酸成分(mmol) 醯亞胺 化率(％) 3 聚醯胺酸[〇] 化编40) (2.63) p-PDA (6.14) PCH7DAB (8.77) CBDA (4.39) BODA (13.2) - 4 聚醯亞胺酸粉末[P] 化纖40) (2.63) p-PDA (6.14) PCH7DAB (8.77) CBDA (4.39) BODA (13.2) 40 5 聚醯胺酸[Q] 化雜(43) (2.57) p-PDA (6.00) PCH7DAB (8.57) CBDA (4.28) BODA (12.9) - 6 聚醯亞胺粉末[R] 化合物(43) (2-57) p-PDA (6.00) PCH7DAB (8.57) CBDA (4.28) BODA (12.9) 41 〔液晶配向處理劑之調配·評價〕 &lt;實施例26&gt; 將NMP (10.2克）、BCS(20.0克）添加於實施例 12中獲得之樹脂成分之含量爲24質量％之聚醯胺酸溶液 〔A〕 （ 10.0克）中，在25°C下攪拌2小時，獲得液晶配 向處理劑〔1〕。該液晶配向處理劑中未發現混濁或析出 等異常，確認樹脂成分均勻地溶解。 〔液晶元件之製作〕 將上述獲得之液晶配向處理劑〔1〕旋轉塗佈於貼附 3cmx4cm (長X寬）ITO電極之基板之ITO面上，在80°C 下5分鐘，且在2 1 0 °C之熱風循環式烘箱中進行燒成1小 時，製作膜厚l〇〇nm之聚醯亞胺塗膜。BODA (3_29 g, 13.2 mmol), p-PDA (0.67 g, 6.14 mmol), PCH7DAB (3.34 g, 8.77 mmol) and diamine compound (40) (0.68 g, 2.63 mmol) The mixture was mixed with NMP (15.0 g), and after reacting for 5 hours at 8 (TC), CBDA (0.86 g, 4.39 mmol) and NMP (11.5 g) were added, and reacted at 40 ° C for 6 hours to obtain The polyamic acid solution (〇) having a resin component content of 25% by mass. The polyamino acid had a number average molecular weight of 22,600 and a weight average molecular weight of 54,900. <Synthesis Example 4> NMP was added to Synthesis Example 3. The obtained polyamic acid solution (Ο) (20.0 g) was diluted to 6% by mass, and then acetic anhydride (2.65 g) and pyridine (2.08 g) as a ruthenium catalyst were added, and at 80 ° C. The reaction was carried out for 2 hours. The reaction solution was poured into methanol (30 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimine powder ( P). The polyimine has a ruthenium imidation ratio of 40%, a number average molecular weight of 1,800, and a weight average molecular weight of 49,200 〇-7. 4- 200940506 &lt;Synthesis Example 5&gt; BODA (3.22 g, 12.9 mmol), p-pDA (〇_65 g, 6.00 mmol), PCH7DAB (3.26 g, 8_57 mmol) and diamine compound (43) (0.62 g, 2_57 mmol) was mixed in NMP (15-2 g), and after reacting at 80 ° C for 5 hours, CBDA (0.84 g, 4-28 mmol) and NMP (11.1 g) were added. And φ was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (Q) having a resin component content of 25% by mass. The polyamino acid had a number average molecular weight of 22,100 and a weight average molecular weight of 53,200 * &lt; Synthesis Example 6 Addition of NMP to the polyamic acid solution (q) (20.1 g) obtained in Synthesis Example 5 was diluted to 6 mass%, and then acetic anhydride (2.68 g) as a ruthenium catalyst was added. And the ratio of 卩 is steep (2.04 g), and is at 80 ° (: Φ reaction for 2 hours. The reaction solution is poured into methanol (350 ml), and the resulting precipitate is filtered. The precipitate is washed with methanol, and l 〇〇〇c under reduced pressure drying to obtain a polyimine powder (R). The ruthenium imidization ratio of the polyimine is 41% 'number average molecular weight is 18,400, weight average molecular weight is 49,100 ° -75- 200940506 [Table 5] Example diamine component (leg 〇 1) tetradecanoic acid component (mmol) 醯 imidization rate (%) specific diamined heterogeneous 1 Amine 12 Polyphosphonium quinone 1 Chemical fiber 4) (2.66) p-PDA (6.21) PCH7DAB (8.87) CBDA (4.44) BODA (13.3) - 13 Polyimine powder [B] Compound (4) (2.66) p-PDA ( 6.21) PCH7DAB (8.87) CBDA (4.44) BODA (13.3) 40 14 Polyimine powder [C] Compound (7) (2.63) p-PDA (8.71) AP18 (1.24) CBDA (3.11) BODA (9.33) 41 15 Proline [D] complex (10) (2.60) p-PDA (6.07) PCH7DAB (8.67) CBDA (4.33) BODA O3.0) - 16 polyimine powder [E] Compound (10) (2.60) p- PDA (6.07) PCH7DAB (8.67) CBDA (4.33) BODA (13.0) 42 17 Polyimine powder [F] Thin 14) (2.96) p-PDA (5.32) PCH7DAB (3.55) CBDA (2.96) BODA (8.87 41 18 Polyimine powder [G] Chemical 16) (3-49) p-PDA (6.39) AP18 (1.74) CBDA (2.91) BODA (8.72) 40 19 Polyimine powder [H] Compound ( 19) (1-84) p-PDA (4.28) PCH7DAB (6.12) CBDA (2.91) BODA (9.18) 40 20 Polyimine powder [I] Compound (23) (1.87) p-PDA (4.35) PCH7DAB (6.22) CBDA (3.11) BODA (9.33) 42 21 Polyimine powder [J] ed. 26) (4.21) p-PDA (6.62) AP18 (1.20) CBDA ( 3.01) BODA (9.03) 40 22 Polyglycine [K] Compound (29) (1.18) p-PDA (9.46) API 8 Π.18) CBDA (2.96) BODA (8.87) - 23 Polyimine powder [ L] 编编34) (3.47) p-PDA (5.20) PCH7DAB (8.67) CBDA (4.33) BODA (13.0) 40 24 Polyglycine [M] Compound (37) (2.60) p-PDA (6.07) PCH7DAB (8.67) CBDA (4.33) BODA (13.0) - 25 Polyimine powder [N] Compound (37) (2.60) p-PDA (6.07) PCH7DAB (8.67) CBDA (4.33) BODA (13.0) 41 -76- 200940506 [Table 6] Synthesis Example Diamine Component (mmol) Tetracarboxylic Acid Component (mmol) Ruthenium Amination Rate (%) 3 Polyglycine [〇] 编编40) (2.63) p-PDA (6.14) PCH7DAB (8.77) CBDA (4.39) BODA (13.2) - 4 Polyimide powder [P] Chemical fiber 40) (2.63) p-PDA (6.14) PCH7DAB (8.77) CBDA (4.39) BODA (13.2) 40 5 Amino acid [Q] complex (43) (2.57) p-PDA (6.00) PCH7DAB (8.57) CBDA (4.28) BODA (12.9) - 6 Polyimine powder [R] Compound (43) (2-57) p-PDA (6.00) PCH7DAB (8.5 7) CBDA (4.28) BODA (12.9) 41 [Preparation and evaluation of liquid crystal alignment agent] &lt;Example 26&gt; NMP (10.2 g) and BCS (20.0 g) were added to the resin component obtained in Example 12. The polyamic acid solution [A] (10.0 g) having a content of 24% by mass was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [1]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. [Production of Liquid Crystal Element] The liquid crystal alignment treatment agent [1] obtained above was spin-coated on the ITO surface of a substrate to which a 3 cm x 4 cm (length X width) ITO electrode was attached, at 80 ° C for 5 minutes, and at 2 1 The film was fired in a hot air circulating oven at 0 ° C for 1 hour to prepare a polyimide film having a film thickness of 10 nm.

使該貼附液晶配向膜之基板在輥直徑1 20mm、嫘縈布 之摩擦裝置中，以旋轉數300rpm，輥進行速度20mm/SeC -77- 200940506 ，擠入量〇.3mm之條件下進行摩擦處理，獲得貼附液晶配 向膜之基板。 準備兩片該貼附液晶配向膜之基板’於其一片液晶配 向膜面上散佈之珠粒隔離材後，自其上印刷密封劑 。使另一片基板成爲液晶配向膜之內測，以摩擦方向成爲 反向之方式貼合後，使密封劑硬化製備空元件。藉由減壓 注入法於該空元件中注入液晶MLC-66 08 (日本默克公司 製造），獲得反向平行配向之向列型液晶元件。 〔電壓維持率之評價〕 在80°C之溫度下對上述獲得之液晶元件施加60 s之 4V電壓，且測定16.67ms及1 667ms後之電壓，計算可以 何種程度保持之電壓作爲電壓維持率。結果列於下表7。 〔殘留電荷之緩和評價〕 對測定電壓維持率後之液晶元件施加10V之直流電壓 Q 30分鐘，且經短路1秒後，測定1 800秒內於液晶元件內 產生之電位。且測定50秒後及1 000秒後之殘留電荷。另 外，測定係使用東陽技術公司製造之6254型液晶物性評 價裝置。結果列於下表8。 〔高溫放置後之評價〕 將測定殘留電荷後之液晶元件置於設定在1 〇〇 °C之高 溫槽中7天後，進行電壓維持率及殘留電荷之測定。結果 -78 - 200940506 列於下表7及表8。 &lt;實施例27&gt; 於實施例13中獲得之聚醯亞胺粉末〔B〕（ 5 · 1克） 中添加NMP ( 36.3克），且在70°C下攪拌40小時溶解。 於該溶液中添加NMP(18.1克）、BCS(25.6克），且在 25°C下攪拌2小時，獲得液晶配向處理劑〔2〕。該液晶 ❹ 配向處理劑中未發現渾濁或析出等異常，確認樹脂成分均 勻溶解。使用所得液晶配向處理劑〔2〕，如實施例2 6般 製備液晶元件，且進行電壓維持率之評價、殘留電荷緩和 之評價、高溫放置後之評價。結果列於下表7及表8。 &lt;實施例28&gt; 於實施例14中獲得之聚醯亞胺粉末〔C〕 （ 5.0克） 中添加NMP ( 32.8克），且在70°C下攪拌40小時溶解。 〇 於該溶液中添加NMP ( 16.4克）、BCS ( 29.2克），且在 2 5 °C下攪拌2小時，獲得液晶配向處理劑〔3〕。該液晶 配向處理劑中未發現渾濁或析出等異常，確認樹脂成分均 勻溶解。使用所得液晶配向處理劑〔3〕，如實施例26般 製備液晶元件，且進行電壓維持率之評價、殘留電荷緩和 之評價、高溫放置後之評價。結果列於下表7及表8。 &lt;實施例29&gt; 於實施例15中獲得之樹脂成分含量爲25質量％之聚 -79- 200940506 醯胺酸溶液〔D〕（10.5克）中添加NMP ( 8.9克）、BCS (23·6克），且在25°C下攪拌2小時，獲得液晶配向處 理劑〔4〕。該液晶配向處理劑中未發現渾濁或析出等異 常’確認樹脂成分均勻溶解。使用所得液晶配向處理劑〔 4〕，如實施例26般製備液晶元件，且進行電壓維持率之 評價、殘留電荷緩和之評價、高溫放置後之評價。結果列 於下表7及表8。 &lt;實施例30&gt; 於實施例16中獲得之聚醯亞胺粉末〔E〕（5.2克） 中添加NMP ( 34.1克），且在70°C下攪拌40小時溶解。 於該溶液中添加NMP ( 17.1克）、BCS ( 30.4克），且在 2 5 °C下攪拌2小時，藉此獲得液晶配向處理劑〔5〕。該 液晶配向處理劑中未發現渾濁或析出等異常，確認樹脂成 分均勻溶解。使用所得液晶配向處理劑〔5〕，如實施例 26般製備液晶元件，且進行電壓維持率之評價、殘留電荷 0 緩和之評價、高溫放置後之評價。結果列於下表7及表8 &lt;實施例3 1&gt; 於實施例17中獲得之聚醯亞胺粉末〔F〕（5.0克） 中添加NMP ( 35.6克），且在70°C下攪拌40小時溶解。 於該溶液中添加NMP ( 17.8克）、BCS ( 25.1克），且在 2 5 °C下攪拌2小時，藉此獲得液晶配向處理劑〔6〕。該 -80- 200940506 液晶配向處理劑中未發現渾濁或析出等異常，確認樹脂成 分均勻溶解。使用所得液晶配向處理劑〔6〕，如實施例 26般製備液晶元件，且進行電壓維持率之評價、殘留電荷 緩和之評價、高溫放置後之評價。結果列於下表7及表8 &lt;實施例32&gt; Q 於實施例18中獲得之聚醯亞胺粉末〔G〕（5.0克） 中添加NMP ( 30.1克），且在70°C下攪拌40小時溶解。 於該溶液中添加NMP (15.2克）、BCS(33.2克），且在 2 5 °C下攪拌2小時，藉此獲得液晶配向處理劑〔7〕。該 液晶配向處理劑中未發現渾濁或析出等異常，確認樹脂成 分均勻溶解。使用所得液晶配向處理劑〔7〕，如實施例 26般製備液晶元件，且進行電壓維持率之評價、殘留電荷 緩和之評價、高溫放置後之評價。結果列於下表7及表8 ❹ &lt;實施例33&gt; 於實施例19中獲得之聚醯亞胺粉末〔H〕（5.5克） 中添加NMP ( 42.2克），且在70°C下攪拌40小時溶解。 於該溶液中添加NMP ( 20.8克）、BCS ( 22.9克），且在 2 5 °C下攪拌2小時，藉此獲得液晶配向處理劑〔8〕。該 液晶配向處理劑中未發現渾濁或析出等異常，確認樹脂成 分均勻溶解。使用所得液晶配向處理劑〔8〕，如實施例 -81 - 200940506 26般製備液晶元件’且進行電壓維持率之評價 '殘留電荷 緩和之評價、高溫放置後之評價°結果列於下表7及表8 &lt;實施例34&gt; 於實施例20中獲得之聚醯亞胺粉末〔I〕 （ 5.0克） 中添加NMP (30.3克），且在70 °C下攪拌40小時溶解。 於該溶液中添加NMP ( 14.8克）、BCS ( 33.8克）’且在 2 51下攪拌2小時，藉此獲得液晶配向處理劑〔9〕。該 液晶配向處理劑中未發現渾濁或析出等異常，確認樹脂成 分均勻溶解。使用所得液晶配向處理劑〔9〕，如實施例 26般製備液晶元件，且進行電壓維持率之評價、殘留電荷 緩和之評價、高溫放置後之評價。結果列於下表7及表8The substrate to which the liquid crystal alignment film was attached was rubbed in a friction device having a roll diameter of 1 20 mm and a crepe cloth at a rotation speed of 300 rpm, a roll speed of 20 mm/SeC -77 to 200940506, and a squeeze amount of 33 mm. The substrate is obtained by attaching a liquid crystal alignment film. Two sheets of the substrate to which the liquid crystal alignment film was attached were prepared, and the sealant was printed thereon after the bead spacer which was spread on one of the liquid crystal alignment film faces. The other substrate was measured as a liquid crystal alignment film, and after the rubbing direction was reversed, the sealant was hardened to prepare an empty member. Liquid crystal MLC-66 08 (manufactured by Merck, Japan) was injected into the hollow member by a vacuum injection method to obtain an antiparallel alignment nematic liquid crystal cell. [Evaluation of Voltage Maintaining Rate] A voltage of 4 volts of 60 s was applied to the liquid crystal element obtained above at a temperature of 80 ° C, and voltages of 16.67 ms and 1 667 ms were measured, and the degree of voltage maintained as a voltage holding ratio was calculated. . The results are shown in Table 7 below. [Evaluation of relaxation of residual charge] A DC voltage of 10 V was applied to the liquid crystal element after the voltage holding ratio was measured for 30 minutes, and after a short circuit for 1 second, the potential generated in the liquid crystal element was measured for 1 800 seconds. The residual charge was measured after 50 seconds and after 1 000 seconds. Further, the measurement system used a 6254 type liquid crystal property evaluation device manufactured by Dongyang Technology Co., Ltd. The results are shown in Table 8 below. [Evaluation after high-temperature placement] The liquid crystal element after the measurement of the residual electric charge was placed in a high-temperature bath set at 1 〇〇 ° C for 7 days, and then the voltage maintenance ratio and the residual charge were measured. Results -78 - 200940506 are listed in Tables 7 and 8 below. &lt;Example 27&gt; NMP (36.3 g) was added to the polyimine powder [B] (5 · 1 g) obtained in Example 13, and stirred at 70 ° C for 40 hours to dissolve. NMP (18.1 g) and BCS (25.6 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [2]. No abnormality such as turbidity or precipitation was observed in the liquid crystal ❹ alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [2], a liquid crystal element was prepared as in Example 26, and evaluation of voltage maintenance ratio, evaluation of residual charge relaxation, and evaluation after high temperature standing were performed. The results are shown in Tables 7 and 8 below. &lt;Example 28&gt; NMP (32.8 g) was added to the polyimine powder [C] (5.0 g) obtained in Example 14, and the mixture was stirred at 70 ° C for 40 hours to dissolve. N NMP (16.4 g) and BCS (29. 2 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [3]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [3], a liquid crystal element was prepared as in Example 26, and evaluation of voltage maintenance ratio, evaluation of residual charge relaxation, and evaluation after high temperature standing were performed. The results are shown in Tables 7 and 8 below. &lt;Example 29&gt; NMP (8.9 g) and BCS (23·6) were added to the poly-79-200940506 proline solution [D] (10.5 g) obtained in Example 15 with a resin component content of 25% by mass. The mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [4]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent. It was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [4], a liquid crystal element was prepared as in Example 26, and evaluation of voltage holding ratio, evaluation of residual charge relaxation, and evaluation after high temperature standing were performed. The results are shown in Tables 7 and 8 below. &lt;Example 30&gt; NMP (34.1 g) was added to the polyimine powder [E] (5.2 g) obtained in Example 16 and stirred at 70 ° C for 40 hours to dissolve. To the solution, NMP (1.71 g) and BCS (30.4 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [5]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [5], a liquid crystal element was prepared as in Example 26, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge 0, and evaluation after high temperature standing were performed. The results are shown in Table 7 below and Table 8 &lt;Example 3 1&gt; NMP (35.6 g) was added to the polyimine powder [F] (5.0 g) obtained in Example 17, and stirred at 70 °C. Dissolved in 40 hours. NMP (17.8 g) and BCS (25.1 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [6]. In the -80-200940506, no abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [6], a liquid crystal element was prepared as in Example 26, and evaluation of voltage maintenance ratio, evaluation of residual charge relaxation, and evaluation after high-temperature standing were performed. The results are shown in Table 7 below and Table 8 &lt;Example 32&gt; Q NMP (30.1 g) was added to the polyimine powder [G] (5.0 g) obtained in Example 18, and stirred at 70 °C. Dissolved in 40 hours. NMP (15.2 g) and BCS (33.2 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [7]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [7], a liquid crystal element was prepared as in Example 26, and evaluation of voltage holding ratio, evaluation of residual charge relaxation, and evaluation after high temperature standing were performed. The results are shown in Table 7 below and Table 8 ❹ &lt;Example 33&gt; NMP (42.2 g) was added to the polyimine powder [H] (5.5 g) obtained in Example 19, and stirred at 70 °C. Dissolved in 40 hours. NMP (20.8 g) and BCS (22.9 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [8]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [8], the liquid crystal element was prepared as in Example-81 - 200940506 26 and the voltage maintenance rate was evaluated. Evaluation of residual charge relaxation and evaluation after high-temperature standing. The results are shown in Table 7 below. Table 8 &lt;Example 34&gt; NMP (30.3 g) was added to the polyimine powder [I] (5.0 g) obtained in Example 20, and the mixture was stirred at 70 ° C for 40 hours to dissolve. NMP (14.8 g) and BCS (33.8 g) were added to the solution, and the mixture was stirred at 2 51 for 2 hours to obtain a liquid crystal alignment treatment agent [9]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [9], a liquid crystal element was prepared as in Example 26, and evaluation of voltage maintenance ratio, evaluation of residual charge relaxation, and evaluation after high temperature standing were performed. The results are shown in Table 7 below and Table 8

&lt;實施例35&gt; Q 於實施例21中獲得之聚醯亞胺粉末〔J〕 （5.1克） 中添加NMP ( 33.0克），且在70 °C下攪拌40小時溶解。 於該溶液中添加NMP(17.1克）、BCS(29.8克），且在 2 5 °C下攪拌2小時，藉此獲得液晶配向處理劑〔1 〇〕。該 液晶配向處理劑中未發現渾濁或析出等異常，確認樹脂成 分均勻溶解。使用所得液晶配向處理劑〔1 0〕，如實施例 26般製備液晶元件，且進行電壓維持率之評價、殘留電荷 緩和之評價、高溫放置後之評價。結果列於下表7及表8 -82- 200940506 &lt;實施例36&gt; 於實施例22中獲得之樹脂成分含量爲26質量。/。之聚 醯胺酸溶液〔K〕 （10.0克）中添加NMP(15.6克）、 BCS ( 17.1克），且在25t：下攪拌2小時，藉此獲得液晶 配向處理劑〔1 1〕。該液晶配向處理劑中未發現渾濁或析 〇 出等異常，確認樹脂成分均句溶解。使用所得液晶配向處 理劑〔1 1〕，如實施例26般製備液晶元件，且進行電壓 維持率之評價、殘留電荷緩和之評價、高溫放置後之評價 。結果列於下表7及表8。 &lt;實施例37&gt; 於實施例23中獲得之聚醯亞胺粉末〔L〕（5.2克） 中添加NMP ( 34.5克），且在7(TC下攪拌40小時溶解° Φ 於該溶液中添加ΝΜΡ(16·5克）、BCS(30.3克）’且在 2 5°C下攪拌2小時，獲得液晶配向處理劑〔12〕°胃$ @ 配向處理劑中未發現渾濁或析出等異常，確認樹脂成分均 勻溶解。使用所得液晶配向處理劑〔12〕，如實施例26 般製備液晶元件，且進行電壓維持率之評價、殘留®胃緩 和之評價、高溫放置後之評價。結果列於下表7及表8° &lt;實施例38&gt; 於實施例24中獲得之樹脂成分含量爲25質羹％之聚 -83- 200940506 醯胺酸溶液〔Μ〕（8.5克）中添加NMP ( 9.5克）、BCS (17.3克），且在25 °C下攪拌2小時，獲得液晶配向處 理劑〔13〕。該液晶配向處理劑中未發現渾濁或析出等異 常，確認樹脂成分均勻溶解。使用所得液晶配向處理劑〔 13〕，如實施例26般製備液晶元件，且進行電壓維持率 之評價、殘留電荷緩和之評價、高溫放置後之評價。結果 列於下表7及表8。 ❹ &lt;實施例39&gt; 於實施例25中獲得之聚醯亞胺粉末〔N〕（5.0克） 中添加NMP (35.5克），且在70 °C下攪拌40小時溶解。 於該溶液中添加NMP (17·8克）、BCS(25.1克），且在 2 5 °C下攪拌2小時，藉此獲得液晶配向處理劑〔1 4〕。該 液晶配向處理劑中未發現渾濁或析出等異常，確認樹脂成 分均勻溶解。使用所得液晶配向處理劑〔14〕，如實施例 26般製備液晶元件，且進行電壓維持率之評價、殘留電荷 © 緩和之評價、高溫放置後之評價。結果列於下表7及表8 &lt;比較例1 &gt;&lt;Example 35&gt; Q NMP (33.0 g) was added to the polyimine powder [J] (5.1 g) obtained in Example 21, and the mixture was stirred at 70 ° C for 40 hours to dissolve. NMP (17.1 g) and BCS (29.8 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [1 〇]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [10], a liquid crystal element was prepared as in Example 26, and evaluation of voltage maintenance ratio, evaluation of residual charge relaxation, and evaluation after high-temperature standing were performed. The results are shown in Table 7 below and Tables 8-82-200940506 &lt;Example 36&gt; The resin component content obtained in Example 22 was 26 mass. /. NMP (15.6 g) and BCS (1. 1 g) were added to the lysine solution [K] (10.0 g), and the mixture was stirred at 25 t: for 2 hours to obtain a liquid crystal alignment treatment agent [1 1]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin components were all dissolved. Using the obtained liquid crystal alignment treatment agent [1 1], a liquid crystal element was prepared as in Example 26, and evaluation of voltage retention rate, evaluation of residual charge relaxation, and evaluation after high temperature standing were performed. The results are shown in Tables 7 and 8 below. &lt;Example 37&gt; NMP (34.5 g) was added to the polyimine powder [L] (5.2 g) obtained in Example 23, and dissolved at 7 (TC for 40 hours). Φ was added to the solution. ΝΜΡ (16.5 g) and BCS (30.3 g) were stirred at 2 5 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [12]° Stomach # @ No treatment such as turbidity or precipitation was observed in the treatment agent, and confirmation was confirmed. The resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [12], a liquid crystal element was prepared as in Example 26, and evaluation of voltage maintenance ratio, evaluation of residual® stomach relaxation, and evaluation after high temperature standing were carried out. The results are shown in the following table. 7 and Table 8° &lt;Example 38&gt; The NMP (9.5 g) was added to the poly-83-200940506 proline solution (8.5) (8.5 g) obtained in Example 24 with a resin component content of 25 % by mass. BCS (17.3 g) was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [13]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Treatment agent [13], liquid crystal was prepared as in Example 26. The components were evaluated for voltage maintenance ratio, evaluation of residual charge relaxation, and evaluation after high temperature deposition. The results are shown in Tables 7 and 8 below. ❹ &lt;Example 39&gt; Polyimine obtained in Example 25 NMP (35.5 g) was added to the powder [N] (5.0 g), and the mixture was stirred at 70 ° C for 40 hours to dissolve. NMP (17·8 g), BCS (25.1 g) was added to the solution, and at 25 The liquid crystal alignment treatment agent [14] was obtained by stirring at ° C for 2 hours. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. The obtained liquid crystal alignment treatment agent [14] was used. The liquid crystal element was prepared in the same manner as in Example 26. The evaluation of the voltage maintenance ratio, the evaluation of the residual charge © relaxation, and the evaluation after the high temperature standing were carried out. The results are shown in Table 7 below and Table 8 &lt; Comparative Example 1 &gt;

於合成例3中獲得之樹脂成分含量爲25質量％之聚醯 胺酸溶液〔〇〕 （10.4克）中添加NMP ( 17.5克）、BCS (15.3克），且在25 °C下攪拌2小時，藉此獲得液晶配 向處理劑〔15〕。該液晶配向處理劑中未發現渾濁或析出 -84- 200940506 等異常，確認樹脂成分均勻溶解。使用所得液晶配向處理 劑〔15〕，如實施例26般製備液晶元件，且進行電壓維 持率之評價、殘留電荷緩和之評價、高溫放置後之評價。 結果列於下表7及表8。 &lt;比較例2 &gt; 於合成例4中獲得之聚醯亞胺粉末〔P〕（4.5克）中 φ 添加NMP ( 34.5克），且在70°C下攪拌40小時溶解。於 該溶液中添加NMP (17.2克）、BCS(18.8克），且在 25 °C下攪拌2小時，藉此獲得液晶配向處理劑〔16〕。該 液晶配向處理劑中未發現渾濁或析出等異常，確認樹脂成 分均勻溶解。使用所得液晶配向處理劑〔16〕，如實施例 26般製備液晶元件，且進行電壓維持率之評價、殘留電荷 緩和之評價、高溫放置後之評價。結果列於下表7及表8 ❹ &lt;比較例3&gt;NMP (17.5 g) and BCS (15.3 g) were added to a polyglycine solution (10.4 g) having a resin component content of 25% by mass obtained in Synthesis Example 3, and stirred at 25 ° C for 2 hours. Thereby, a liquid crystal alignment treatment agent [15] is obtained. No abnormality such as turbidity or precipitation -84-200940506 was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [15], a liquid crystal element was prepared as in Example 26, and evaluation of voltage retention, evaluation of residual charge relaxation, and evaluation after high-temperature standing were performed. The results are shown in Tables 7 and 8 below. &lt;Comparative Example 2 &gt; In the polyimine powder [P] (4.5 g) obtained in Synthesis Example 4, NMP (34.5 g) was added as φ, and the mixture was stirred at 70 ° C for 40 hours to dissolve. NMP (17.2 g) and BCS (18.8 g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [16]. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [16], a liquid crystal element was prepared as in Example 26, and evaluation of voltage maintenance ratio, evaluation of residual charge relaxation, and evaluation after high-temperature standing were performed. The results are shown in Table 7 below and Table 8 ❹ &lt;Comparative Example 3&gt;

於合成例5中獲得之樹脂成分含量爲25質量％之聚醯 胺酸溶液〔Q〕 （10.0克）中添加NMP ( 18_8克）、BCS (12.2克），且在25°C下攪拌2小時，藉此獲得液晶配 向處理劑〔1 7〕。該液晶配向處理劑中未發現渾濁或析出 等異常，確認樹脂成分均勻溶解。使用所得液晶配向處理 劑〔1 7〕，如實施例2 6般製備液晶元件，且進行電壓維 持率之評價、殘留電荷緩和之評價、高溫放置後之評價。 -85- 200940506 結果列於下表7及表8。 &lt;比較例4&gt; 於合成例6中獲得之聚醯亞胺粉末〔r〕 （4.7克）中 添加NMP ( 3 8.6克），且在70。(：下攪拌40小時溶解。於 該溶液中添加ΝΜΡ(19·4克）、BCS(15.8克），且在 25 °C下攪拌2小時，藉此獲得液晶配向處理劑〔18〕。該 液晶配向處理劑中未發現渾濁或析出等異常，確認樹脂成 分均勻溶解。使用所得液晶配向處理劑〔18〕，如實施例 26般製備液晶元件，且進行電壓維持率之評價、殘留電荷 緩和之評價、高溫放置後之評價。結果列於下表7及表8 -86- 200940506 〔表7〕NMP (18_8 g) and BCS (12.2 g) were added to a polyamic acid solution [Q] (10.0 g) having a resin component content of 25% by mass obtained in Synthesis Example 5, and stirred at 25 ° C for 2 hours. Thereby, a liquid crystal alignment treatment agent [17] was obtained. No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [17], a liquid crystal element was prepared as in Example 26, and evaluation of voltage retention, evaluation of residual charge relaxation, and evaluation after high-temperature standing were performed. -85- 200940506 The results are shown in Tables 7 and 8 below. &lt;Comparative Example 4&gt; NMP (3 8.6 g) was added to the polyimine powder [r] (4.7 g) obtained in Synthesis Example 6, and was 70. (: Dissolved under stirring for 40 hours. To the solution, hydrazine (19.4 g) and BCS (15.8 g) were added, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent [18]. No abnormality such as turbidity or precipitation was observed in the alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal alignment treatment agent [18], a liquid crystal element was prepared as in Example 26, and evaluation of voltage maintenance ratio and evaluation of residual charge relaxation were performed. Evaluation after high temperature placement. The results are shown in Table 7 below and Table 8 -86- 200940506 [Table 7]

液晶配向 處理劑 電壓維持率（％) 液晶元1 [牛製作時 高溫放置後 16.67ms 1667ms 16.67ms 1667ms 聚醯胺酸 實施例26 〔1〕 93.3 58.9 93.2 57.2 實施例29 〔4〕 93.1 58.4 92.9 56.9 實施例36 〔11〕 93.2 59.1 93.0 56.1 實施例38 〔13〕 93.4 58.8 93.3 56.2 比較例1 〔15〕 92.3 56.5 91.5 51.4 比較例3 〔17〕 92.1 56.1 91.1 51.1 聚醯亞胺 實施例27 〔2〕 97.8 61.2 97.7 61.0 實施例28 〔3〕 97.7 61.1 97.6 60.8 實施例30 〔5〕 97.6 61.3 97.6 61.2 實施例31 〔6〕 97.3 61.0 97.2 60.8 實施例32 〔7〕 97.2 61.1 97.6 61.0 實施例33 〔8〕 97.1 60.8 97.0 60.7 實施例34 〔9〕 97.3 61.1 97.2 61.1 實施例35 〔10〕 97.4 61.1 97.3 61.0 實施例37 〔12〕 97.5 60,8 97.2 60.6 實施例39 〔14〕 97.7 61.2 97.5 61.1 比較例2 〔16〕 97.6 60.1 96.8 58.9 比較例4 〔18〕 97.3 59.8 96.3 57.8 87- 200940506 〔表8〕 液晶配向 處理劑 殘留電荷之緩和（V) 液晶元1 ί牛製作時 高灘置後 50秒後 1000秒後 50秒後 1000秒後 聚醯胺酸 實施例26 ⑴ 0.98 0.12 0.94 0.11 實施例29 〔4〕 1.01 0.11 1.02 0.13 實施例36 〔11〕 0.67 0.11 0.62 0.13 實施例38 〔13〕 0.99 0.13 0.97 0.15 比較例1 〔15〕 1.07 0.13 1.04 0.31 比較例3 〔17〕 1.05 0.15 1.08 0.43 聚輕胺 實施例27 〔2〕 1.19 0.17 1.16 0.18 實施例28 〔3〕 0.63 0.18 0.69 0.17 實施例30 〔5〕 1.21 0.18 1.24 0.21 實施例31 〔6〕 1.14 0.16 1.12 0.22 實施例32 〔7〕 0.81 0.16 0.89 0.18 實施例33 〔8〕 1.19 0.16 1.14 0.19 實施例34 〔9〕 1.15 0.17 U3 0.22 實施例35 〔10〕 0.67 0.14 0.70 0.19 實施例37 〔12〕 1.19 0.18 1.22 0.21 實施例39 〔14〕 1.15 0.17 1.15 0.20 比較例2 〔16〕 1.17 0.21 1.45 0.58 比較例4 [18] 1.16 0.23 1.51 0.63 〔產業上利用之可能性〕 本發明之液晶配向處理劑於成爲液晶配向膜時，可獲 得電壓保持率高且即使於高溫下長時間暴露後亦可加速緩 和由直流電壓引起之累積殘留電荷之液晶配向膜。另外可 提供可耐在過度嚴苛之使用環境下長期使用之信賴性高之 液晶顯示元件。其結果，可用於TN元件、STN元件、 200940506 TFT液晶元件，進而可用於垂直配向型或水平配 IPS)之液晶顯示元件等。 又，2008年1月25日申請之日本特願2008-號之說明書、申請專利範圍、及摘要之全部內容均 ，且倂入本發明之說明書之揭示中供參考。 〇 向型（ 014965 被引用Liquid crystal alignment agent voltage maintenance ratio (%) Liquid crystal cell 1 [16.67ms 1667ms 16.67ms 1667ms after high temperature placement in cattle production Polyuric acid example 26 [1] 93.3 58.9 93.2 57.2 Example 29 [4] 93.1 58.4 92.9 56.9 Example 36 [11] 93.2 59.1 93.0 56.1 Example 38 [13] 93.4 58.8 93.3 56.2 Comparative Example 1 [15] 92.3 56.5 91.5 51.4 Comparative Example 3 [17] 92.1 56.1 91.1 51.1 Polyimine Example 27 [2] 97.8 61.2 97.7 61.0 Example 28 [3] 97.7 61.1 97.6 60.8 Example 30 [5] 97.6 61.3 97.6 61.2 Example 31 [6] 97.3 61.0 97.2 60.8 Example 32 [7] 97.2 61.1 97.6 61.0 Example 33 [8] 97.1 60.8 97.0 60.7 Example 34 [9] 97.3 61.1 97.2 61.1 Example 35 [10] 97.4 61.1 97.3 61.0 Example 37 [12] 97.5 60,8 97.2 60.6 Example 39 [14] 97.7 61.2 97.5 61.1 Comparative Example 2 16] 97.6 60.1 96.8 58.9 Comparative Example 4 [18] 97.3 59.8 96.3 57.8 87- 200940506 [Table 8] Releasing the residual charge of the liquid crystal alignment agent (V) Liquid crystal cell 1 After 50 seconds, after 1000 seconds, after 50 seconds, and after 1000 seconds, the polyaminic acid Example 26 (1) 0.98 0.12 0.94 0.11 Example 29 [4] 1.01 0.11 1.02 0.13 Example 36 [11] 0.67 0.11 0.62 0.13 Example 38 [13 0.99 0.13 0.97 0.15 Comparative Example 1 [15] 1.07 0.13 1.04 0.31 Comparative Example 3 [17] 1.05 0.15 1.08 0.43 Polylamine Example 27 [2] 1.19 0.17 1.16 0.18 Example 28 [3] 0.63 0.18 0.69 0.17 Example 30 </ RTI> </ RTI> </ RTI> </ RTI> 35 [10] 0.67 0.14 0.70 0.19 Example 37 [12] 1.19 0.18 1.22 0.21 Example 39 [14] 1.15 0.17 1.15 0.20 Comparative Example 2 [16] 1.17 0.21 1.45 0.58 Comparative Example 4 [18] 1.16 0.23 1.51 0.63 [Industry The possibility of utilizing the liquid crystal alignment treatment agent of the present invention can obtain a high voltage holding ratio when the liquid crystal alignment film is used as a liquid crystal alignment film, and can accelerate the relaxation of the direct current even after exposure for a long time at a high temperature. Accumulation of residual charge causing the liquid crystal alignment film. In addition, it provides a highly reliable liquid crystal display element that can withstand long-term use in an extremely harsh environment. As a result, it can be used for a TN element, an STN element, a 200940506 TFT liquid crystal element, and can be used for a liquid crystal display element of a vertical alignment type or a horizontal alignment IPS). In addition, the entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2008-, filed on Jan. 25, 2008, are hereby incorporated by reference. 〇 type ( 014965 cited

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Claims (1)

200940506 七、申請專利範圍： 1·—種以下述式〔1〕表示之二胺化合物， 〔化1〕 乂2 ΗζΗΛ j(-Xl-X2-X3-X4) n [ 1 ] (式〔1〕中，Xi 爲選自由- 〇-、-NQ1-、-CONQ1-、-NQkO-、-CH20-及-OCO-所組成組群之至少一種二價有機❹ 基，Q1爲氫原子或碳數1至3之烷基，X2爲單鍵或選自 由碳數1至20之脂肪族烴基、非芳香族環式烴基及芳香 族烴基所組成組群之至少一種二價有機基，X3爲單鍵或選 自由-0-、-NQ2-、-CONQ2-、-NQ2CO-、-COO-、-OCO-及-〇 ( CH2) m- ( m爲1至5之整數）所組成組群之至少一種 二價有機基，Q2爲氫原子或碳數1至3之烷基，X4爲含 氮之芳香族雜環，η爲1至4之整數）。 2.如申請專利範圍第1項之二胺化合物，其中式〔1 〇 〕之二胺化合物爲選自下述式〔la〕至式〔If〕表示之化 合物所組成組群之至少一種： -90- 200940506200940506 VII. Patent application scope: 1. A diamine compound represented by the following formula [1], [Chemical Formula 1] 乂2 ΗζΗΛ j(-Xl-X2-X3-X4) n [ 1 ] (Formula [1] Wherein Xi is at least one divalent organic fluorenyl group selected from the group consisting of -〇-, -NQ1-, -CONQ1-, -NQkO-, -CH20-, and -OCO-, and Q1 is a hydrogen atom or a carbon number of 1 An alkyl group of 3, X2 is a single bond or at least one divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group, and X3 is a single bond or Select at least one of the groups consisting of -0-, -NQ2-, -CONQ2-, -NQ2CO-, -COO-, -OCO-, and -〇(CH2) m- (m is an integer from 1 to 5) The valence organic group, Q2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X4 is a nitrogen-containing aromatic heterocyclic ring, and η is an integer of 1 to 4. 2. The diamine compound according to claim 1, wherein the diamine compound of the formula [1] is at least one selected from the group consisting of the compounds represented by the following formula [la] to the formula [If]: 90- 200940506 (式中，Q1爲氫原子或碳數1至3之烷基，χ2爲單 鍵或選自由碳數〗至20之脂肪族烴基、非芳香族環式煙 基及芳香族烴基所組成組群之至少一種二價有機基’ Χ3爲 單鍵或選自由 _〇_、-NQ2-、-CONQ2-、_NQ2CO_、-COO-、-OCO-及-0(CH2) m-(m爲1至5之整數）所組成組群 之至少一種二價有機基’ Q2爲氫原子或碳數1至3之烷基 ，x4爲含氮之芳香族雜環，η爲1至4之整數）。 3. 如申請專利範圍第2項之二胺化合物’其中式〔 la〕至式〔If〕中之Χ2爲單鍵、碳數1至3之直鏈烷基 或苯瓌。 4. 如申請專利範圍第2或3項之二胺化合物，其中 式〔la〕至式〔if〕中之X3爲單鍵、-OCO-或-OCH2-。 5 ·如申請專利範圍第2至4項中任一項之二胺化合 物，其中式〔la〕至式〔If〕中之X4爲咪唑環' 吡啶環 或嗦Π定環。 6 ·如申請專利範圍第2至5項中任一項之二胺化合 物，其中式〔la〕至式〔If〕中之η爲1或2之整數。 -91 - 200940506 7. 如申請專利範圍第1或2項之二胺化合物，其中 式〔la〕至式〔If〕中之乂1爲選自由-0-、-&gt;^-、-(：01^-、-NHCO-、-CON ( CH3 ) -、_CH20·及-OCO-所組成組群 之至少一種，X2爲選自由碳數1至10之直鏈或分支伸 烷基、環己烷環、苯環及萘環所組成組群之至少一種，X3 爲選自由單鍵、-0-、-(：01^11-、-1^11(：0-、-(：00-、-0(：0-及-0 ( CH2) m- ( m爲1至5之整數）所組成組群之至少 一種，X4爲選自由吡咯環、咪唑環、吡唑環、吡啶環、嘧 啶環、嗒嗪環、三嗪環、三嗖環、哌啶環、苯咪唑環及苯 并咪唑環所組成組群之至少一種，η爲1或2之整數。 8. 如申請專利範圍第1或2項之二胺化合物，其中 式〔1〕中之 Χι 爲選自由-O-'-NH-'-CONH-'-NHCO-、-CON ( CH3 )-及-CH20-所組成組群之至少一種，X2爲 選自由單鍵、碳數1至5之直鏈或分支伸烷基及苯環所組 成組群之至少一種，X3爲選自由單鍵、-0-、-(：01^-、-NHC0-、-COO-、-0C0-及-0 ( CH2 ) m- ( m 爲 1 至 5 之整 數）所組成組群之至少一種，x4爲選自由吡咯環、咪唑環 、吡唑環、吡啶環及嘧啶環所組成組群之至少一種，η爲 1或2之整數。 9·如申請專利範圍第1或2項之二胺化合物，其中 式〔1〕中之 Χι 爲選自由-0-、-&gt;11^、-(：0!^11-、-1^11(：0-及-CON ( CH3 )-所組成組群之至少一種，X2爲選自由單 鍵、碳數1至3之直鏈伸烷基及苯環所組成組群之至少一 種，X3爲選自由單鍵、-0C0-及-0CH2-所組成組群之至少 -92- 200940506 一種，X4爲選自由咪唑環、吡啶環及嘧啶環所組成組群之 至少一種，η爲1或2之整數。 10. —種聚醯胺酸或聚醯亞胺，係由含有申請專利範 圍第1至9項中任一項之二胺化合物之二胺成分與四羧酸 二酐反應所得之聚醯胺酸、或由該聚醢胺酸經脫水閉環所 得之聚醯亞胺。 1 1.如申請專利範圍第1 0項之聚醯胺酸或聚醯亞胺 〇 ，其中以式〔1〕表示之二胺佔二胺成分中之1至80莫耳 %。 12. 一種液晶配向處理劑，其含有如申請專利範圍第 10或11項之聚醯胺酸及聚醯亞胺中之至少任一者以及溶 劑。 1 3 .如申請專利範圍第1 2項之液晶配向處理劑，其 中該液晶配向處理劑中所含之溶劑中之5至80質量％爲弱 溶劑。 © 1 4. 一種液晶配向膜，係使用如申請專利範圍第1 2 或1 3項之液晶配向處理劑所得。 1 5 . —種液晶顯示元件，係具有申請專利範圍第1 4 項之液晶配向膜。 -93- 200940506 四、指定代表圖： (一） 本案指定代表圖為：無 (二） 本代表圖之元件符號簡單說明：無(wherein Q1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and χ2 is a single bond or a group selected from an aliphatic hydrocarbon group having a carbon number of 20 to 20, a non-aromatic ring-type nicotine group, and an aromatic hydrocarbon group; At least one divalent organic group 'Χ3 is a single bond or selected from _〇_, -NQ2-, -CONQ2-, _NQ2CO_, -COO-, -OCO-, and -0(CH2) m-(m is 1 to 5 Integer) at least one divalent organic group 'Q2 of the group formed is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, x4 is a nitrogen-containing aromatic heterocyclic ring, and η is an integer of 1 to 4). 3. The diamine compound as claimed in claim 2 wherein the oxime 2 in the formula [la] to the formula [If] is a single bond, a linear alkyl group having 1 to 3 carbon atoms or benzoquinone. 4. The diamine compound according to claim 2 or 3, wherein X3 in the formula [la] to the formula [if] is a single bond, -OCO- or -OCH2-. The diamine compound according to any one of claims 2 to 4, wherein X4 in the formula [la] to the formula [If] is an imidazole ring 'pyridine ring or a hydrazine ring. The diamine compound according to any one of claims 2 to 5, wherein n in the formula [la] to the formula [If] is an integer of 1 or 2. -91 - 200940506 7. The diamine compound according to claim 1 or 2, wherein 乂1 in the formula [la] to the formula [If] is selected from -0-, -&gt;^-, -(: At least one of 01^-, -NHCO-, -CON(CH3)-, _CH20., and -OCO-, X2 is selected from a linear or branched alkyl group having a carbon number of 1 to 10, and cyclohexane. At least one of a group consisting of a ring, a benzene ring and a naphthalene ring, X3 being selected from the group consisting of a single bond, -0-, -(:01^11-, -1^11(:0-, -(:00-,- At least one of the group consisting of 0 (:0- and -0 (CH2) m- (m is an integer from 1 to 5), and X4 is selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, At least one of a group consisting of a pyridazine ring, a triazine ring, a trioxane ring, a piperidine ring, a benzimidazole ring, and a benzimidazole ring, and η is an integer of 1 or 2. 8. Patent Application No. 1 or 2 The diamine compound, wherein the oxime in the formula [1] is at least one selected from the group consisting of -O-'-NH-'-CONH-'-NHCO-, -CON(CH3)-, and -CH20- X2 is at least one selected from the group consisting of a single bond, a linear or branched alkyl group having a carbon number of 1 to 5, and a benzene ring, and X3 is At least one of a group consisting of a free single bond, -0-, -(:01^-, -NHC0-, -COO-, -0C0-, and -0 (CH2) m- (m is an integer from 1 to 5) And x4 is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring, and η is an integer of 1 or 2. 9. A diamine as described in claim 1 or 2 a compound wherein the oxime in the formula [1] is selected from the group consisting of -0-, -&gt;11^, -(:0!^11-, -1^11(:0- and -CON(CH3)- At least one of the group, X2 is at least one selected from the group consisting of a single bond, a linear alkyl group having 1 to 3 carbon atoms, and a benzene ring, and X3 is selected from the group consisting of a single bond, -0C0- and -CHCH2- At least -92- 200940506 of the group, X4 is at least one selected from the group consisting of an imidazole ring, a pyridine ring and a pyrimidine ring, and η is an integer of 1 or 2. 10. A poly-proline or poly The amine is obtained by reacting a polyamine derivative obtained by reacting a diamine component of a diamine compound according to any one of claims 1 to 9 with a tetracarboxylic dianhydride, or by dehydration ring closure of the polyamic acid. Polyimine. 1 1. If you apply for The polyamine or polyamidamine of the above item 10, wherein the diamine represented by the formula [1] accounts for 1 to 80 mol% of the diamine component. 12. A liquid crystal alignment treatment agent containing At least one of polyamic acid and polyimine and a solvent as claimed in claim 10 or 11. In the liquid crystal alignment treatment agent of the liquid crystal alignment treatment agent, 5 to 80% by mass of the solvent contained in the liquid crystal alignment treatment agent is a weak solvent. © 1 4. A liquid crystal alignment film obtained by using a liquid crystal alignment treatment agent of the first or third aspect of the patent application. A liquid crystal display element is a liquid crystal alignment film of claim 14 of the patent application. -93- 200940506 IV. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No -3- 200940506 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：-3- 200940506 V If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: [1] ❹ Ο -4-[1] ❹ Ο -4-
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