TW201247600A - Diamine compound, method for preparing the same, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Diamine compound, method for preparing the same, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device Download PDF

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TW201247600A
TW201247600A TW101117898A TW101117898A TW201247600A TW 201247600 A TW201247600 A TW 201247600A TW 101117898 A TW101117898 A TW 101117898A TW 101117898 A TW101117898 A TW 101117898A TW 201247600 A TW201247600 A TW 201247600A
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liquid crystal
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diamino
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Seung-Kue Lee
Jin-Wook Choi
Yong-Ho Ahn
Sang-Wan So
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Dongjin Semichem Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
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  • Medicinal Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Polymers & Plastics (AREA)
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  • Optics & Photonics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to an amine compound, a method for preparing same, and a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device, having same. A liquid crystal alignment agent having polyamic acid or polyimide prepared using the amine compound of the present invention enables a liquid crystal alignment film and a liquid crystal display device having an excellent thermal stability even after forming the liquid crystal alignment film, and expressing high alignment and stability even after an ultraviolet ray irradiation.

Description

201247600 六、發明說明： 【相關申請案之交互參照】 本申請案對2011年5月18日提交至韓國特許廳之韓國特 許第10-2011-0047028號專利以及2011年5月18日提交至韓 國特許廳之韓國特許第10-2011-0047030號專利主張優先權及 享有其權益，該等申請案的全部内容併入本案以資參照。 【發明所屬之技術領域】 本發明涉及一種二胺類化合物、其製備方法、液晶配向 劑、液晶配向膜及液晶顯示裝置。更具體地涉及一種可使用於 光配向劑之新結構的二胺類化合物及其製備方法，以及應用該 二胺類化合物的液晶配向劑、液晶配向膜及液晶顯示裝置。 【先前技術】 在液晶顯示器之結構材料中，液晶配向膜與液晶分子接 觸’藉以使液晶分子均勻配向。液晶配向膜為液晶驅動之核心 材料’使液晶朝一側均勻配向，致使液晶能夠好好地執行作為 偏光之開關作用’且液晶配向膜之液晶配向特性及作為薄膜之 電特性會決定液晶顯示器的顯示品質。 形成液晶配向膜之代表性方法有無機物之傾斜沉積法、朗 穆爾-布拉傑特(Langmuir-Blodgett, LB)法、高分子延伸法、摩 擦法等’作為新的配向方法，被提出的有光配向法及離子束照 射法等。其中最普遍應用的方法係採用布摩擦基板表面之摩擦 (rubbing)法。摩擦法係指用紙沿規定的方向摩擦玻璃基板，使 液晶分子之長軸沿著其摩擦方向整齊排列並配向之方法。由於 此種摩擦法配向處理容易，適於大量生產 ，並具有配向穩定、 201247600 使用最多的配向 預傾(pretiIt)角控制容易之優點，因此為工業上 方法。 ' 作為配向膜材料使用最多的為介電常數低 =度優秀、以及製程性卓越之聚酿亞胺。但是二 胺作為配向膜材料存在如下問題或者缺點。第―，由於靜電可 能會破壞賴電晶體(TFT)裝置，因此生產機械—般都會針對 靜電問題有所對策，然而’摩擦法具有無法針對在配向過程中 所生成之靜電提供完整解決㈣的缺點。第二，透過摩捧法進 行配向的過程中可能會產生粉塵，因此f要進行後續的清潔製 程’使得製程過程巾可能會出現效率降低的問題。第三，具有 階梯部之排列層的平面部，與階梯部之摩擦條件不同，致使其 發生對準固定力和則科自的可紐高。第四，祕過程中 只沿一個方向摩擦，致使具有被分離之配向像素之排列層的生 產製程變得複雜。更且，為了能夠均勻摩擦大型基板，還需要 特殊设備。 因此’需要一種能夠解決現有光學圖案形成製程之經濟性 不佳、環境親和性不足、穩定性不佳以及所製備之光學圖案會 導致產品性能降低等問題的方案。 【發明内容】 為解決現有液晶配向方法中所存在之問題，本發明之目的 在於提供一種用於製備液晶配向劑的二胺類化合物，該液晶配 向劑採用在無摩擦狀態下使液晶分子排列的方法，亦即光配向 技術’在其形成配向膜之後仍具有優秀的熱穩定性，且在照射 兔外練之後還能實現高配向性和穩定性。 201247600 此外本t月之目的在於提供—種該二胺類化合物之 方法。 另卜本發月之目的在於提供—種液晶配向劑，該液晶配 向劑包括有透過使含有該二_化合物之二胺成分與四緩酸 二針反應哺得之雜纖或者㈣亞胺。 再者，本發明之目的在於提供一種由該液晶配向劑所形成 之液晶配向膜。 更且，本發明之目的在於提供一種具有該液晶配向膜之液 晶顯示裝置。 本發明提供-種由下列化學式1G表示之二胺類化合物。 [化學式10]201247600 VI. Description of invention: [Reciprocal reference of related application] This application was filed on May 18, 2011 with the Korean Patent No. 10-2011-0047028, which was submitted to the Korean Patent Office, and submitted to Korea on May 18, 2011. The Korean Patent No. 10-2011-0047030 of the Patent Office claims priority and enjoys its rights, and the entire contents of these applications are incorporated herein by reference. [Technical Field of the Invention] The present invention relates to a diamine compound, a process for producing the same, a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device. More specifically, it relates to a diamine compound which can be used for a novel structure of a photoalignment agent, a process for producing the same, a liquid crystal alignment agent using the diamine compound, a liquid crystal alignment film, and a liquid crystal display device. [Prior Art] In the structural material of a liquid crystal display, a liquid crystal alignment film is in contact with liquid crystal molecules to uniformly align liquid crystal molecules. The liquid crystal alignment film is the core material of the liquid crystal driving 'the liquid crystal is uniformly aligned toward one side, so that the liquid crystal can perform the switching function as a polarizing light well' and the liquid crystal alignment characteristics of the liquid crystal alignment film and the electrical characteristics of the film determine the display quality of the liquid crystal display. . Representative methods for forming a liquid crystal alignment film include a tilt deposition method of an inorganic substance, a Langmuir-Blodgett (LB) method, a polymer extension method, a rubbing method, etc. as a new alignment method. There are photo-alignment method and ion beam irradiation method. One of the most commonly used methods is the rubbing method of rubbing the surface of the substrate with a cloth. The rubbing method refers to a method in which a glass substrate is rubbed in a predetermined direction so that the long axes of the liquid crystal molecules are aligned and aligned along the rubbing direction thereof. This type of friction method is industrially suitable because it is easy to handle, suitable for mass production, and has the advantage of stable alignment and the most pre-tilt angle control of 201247600. 'As the aligning film material, it is the most widely used polyaniline which has a low dielectric constant = excellent degree of process and excellent processability. However, the diamine has the following problems or disadvantages as an alignment film material. First, because static electricity may damage the TFT device, production machinery generally has countermeasures against static electricity. However, the friction method has the disadvantage of not providing a complete solution to the static electricity generated during the alignment process. . Secondly, dust may be generated during the process of aligning by the method of buckling, so f is required to carry out the subsequent cleaning process, so that the process process towel may have a problem of reduced efficiency. Third, the flat portion having the alignment layer of the step portion is different from the friction condition of the step portion, so that the alignment fixing force and the self-alignment of the self are high. Fourth, the rubbing process in only one direction during the secret process complicates the production process of the alignment layer having the separated alignment pixels. Moreover, in order to be able to uniformly rub a large substrate, special equipment is also required. Therefore, there is a need for a solution that can solve the problems of poor economics of the existing optical pattern forming process, insufficient environmental affinity, poor stability, and reduced optical performance of the prepared optical pattern. SUMMARY OF THE INVENTION In order to solve the problems existing in the prior art liquid crystal alignment method, an object of the present invention is to provide a diamine compound for preparing a liquid crystal alignment agent which uses liquid crystal molecules to be aligned in a frictionless state. The method, that is, the photo-alignment technique, still has excellent thermal stability after it forms an alignment film, and can achieve high alignment and stability after irradiation of the rabbit. 201247600 In addition, the purpose of this month is to provide a method for the diamine compound. Further, the purpose of the present invention is to provide a liquid crystal alignment agent comprising a miscellaneous fiber or (iv) imine which is obtained by reacting a diamine component containing the di-compound with a tetra-acidic acid. Further, it is an object of the invention to provide a liquid crystal alignment film formed of the liquid crystal alignment agent. Furthermore, it is an object of the invention to provide a liquid crystal display device having the liquid crystal alignment film. The present invention provides a diamine compound represented by the following Chemical Formula 1G. [Chemical Formula 10]

而且本發明提供一種由下列化學式23表示之二胺類化合 物。 [化學式23] 201247600Further, the present invention provides a diamine compound represented by the following Chemical Formula 23. [Chemical Formula 23] 201247600

Re為相同或者相異’且分別獨立地表示Η、cn、N〇2、CF3、 i素、碳原子數為1至10之烷基、或者碳原子數為丨至1〇之 烷氧基。 而且’本發明提供一種包括聚醯胺酸或者聚醯亞胺之液晶 配向劑’所述聚醯亞胺或者聚醯胺酸係透過包括有由下列化學 式10表示之二胺類化合物或者由下列化學式23表示之二胺類 化合物的二胺成分，與四羧酸二酐反應而獲得者。 此外’本發明提供一種由該液晶配向劑形成之液晶配向 膜。 另外，本發明提供一種具有該液晶配向膜之液晶顯示裝 置。 另—方面，本發明提供一種由下列化學式10表示之二胺 類化合物的製備方法，包括以下步驟： 201247600 透過使下列化學式6表示之化合物與下列化學式8表示之 化合物反應，而製備以下列化學式9表示之化合物；以及 去除以下列化學式9表示之化合物中之保護基PG (protecting group 的縮寫）； [化學式6]Re is the same or different and independently represents Η, cn, N〇2, CF3, i, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having from 丨 to 1 碳. Further, the present invention provides a liquid crystal alignment agent comprising polylysine or polyimine, wherein the polyimine or polyamine is permeated by a diamine compound represented by the following Chemical Formula 10 or by the following chemical formula The diamine component of the diamine compound represented by 23 is obtained by reacting with a tetracarboxylic dianhydride. Further, the present invention provides a liquid crystal alignment film formed of the liquid crystal alignment agent. Further, the present invention provides a liquid crystal display device having the liquid crystal alignment film. In another aspect, the present invention provides a process for producing a diamine compound represented by the following Chemical Formula 10, which comprises the following steps: 201247600 By reacting a compound represented by the following Chemical Formula 6 with a compound represented by the following Chemical Formula 8, the following Chemical Formula 9 is prepared. a compound represented by the compound; and a protecting group PG (abbreviation of protecting group) in the compound represented by the following Chemical Formula 9; [Chemical Formula 6]

[化學式8][Chemical Formula 8]

NH-PGNH-PG

[化學式9][Chemical Formula 9]

[化學式10][Chemical Formula 10]

該化學式6、8、9及10中，η為1至20之整數；R,至 R8為相同或者相異，且分別獨立地表示Η、CN、Ν〇2、CF3、 201247600 鹵素、碳原子數為1至10之烷基、或者碳原子數為1至10之 烧氧基；PG為選自由苄氧幾基（carbobenzyloxy，縮寫cbz)、 對-甲氧基苄基幾基（p-Methoxybenzyl carbonyl，縮寫 Moz)、 叔丁氧幾基（tert-butyloxycarbonyl ’ 縮寫 BOC)、9-¾ 甲氧幾 基(9-fluorenylmethyloxycarbonyl， 縮寫FMOC )、乙醯基 (acetyl ’縮寫Ac)、苯曱醯基（benzoyl，縮寫Bz )、节基 (benzy卜縮寫Bn)、胺基甲酸鹽(Carbamate)、對-曱氧基苄基 (p-methoxybenzyl，縮寫 PMB )、3,4-二曱氧基苄基 (3,4-dimethoxybenzyl，縮寫 DMPM )、對-甲氧基笨美 (p_methoxyphenyl ’ 縮寫 PMP )、曱苯磺醯基（tosy卜縮寫 Ts )、 以及對硝基苯磺醯基（nosy卜縮寫Ns)構成之族群中的保護 基(Protecting group)。 另外，本發明提供一種由下列化學式23表示之二胺類化 合物的製備方法，包括以下步驟：In the chemical formulas 6, 8, 9 and 10, η is an integer of 1 to 20; R, R8 are the same or different, and each independently represents Η, CN, Ν〇2, CF3, 201247600 halogen, number of carbon atoms An alkyl group of 1 to 10 or an alkoxy group having 1 to 10 carbon atoms; PG is selected from the group consisting of carbobenzyloxy (abbreviated as cbz) and p-Methoxybenzyl carbonyl (p-Methoxybenzyl carbonyl) , abbreviation Moz), tert-butyloxycarbonyl 'abbreviation BOC', 9-3 fluorenylmethyloxycarbonyl (abbreviated FMOC), ethenyl (acetyl 'abbreviated Ac), phenyl fluorenyl ( Benzoyl, abbreviated as Bz), benzid (abbreviated as Bn), carbamate, p-methoxybenzyl (PMB), 3,4-dimethoxybenzyl (3,4-dimethoxybenzyl, abbreviated as DMPM), p-methoxyphenyl (pMP), phenyl sulfonyl (tosy), and p-nitrophenylsulfonyl (nosy) The Protecting group in the group that constitutes it. Further, the present invention provides a process for producing a diamine compound represented by the following Chemical Formula 23, comprising the steps of:

透過使下列化學式12表示之化合物與下列化學式21表八 之化合物反應，而製備以下列化學式22表示之化合物；以I 去除以下列化學< 22表示之化合物中之保護基pG (protecting group 的縮寫）： [化學式12]A compound represented by the following Chemical Formula 22 is prepared by reacting a compound represented by the following Chemical Formula 12 with a compound of the following Chemical Formula 21; and a protecting group pG (protecting group) in the compound represented by the following chemical < 22 is removed by I ): [Chemical Formula 12]

[化學式22][Chemical Formula 22]

201247600 [化學式21] [化學式23] 10 201247600201247600 [Chemical Formula 21] [Chemical Formula 23] 10 201247600

在該化學式12、21、22及23中，η為1至20之整數； R!至Rs為相同或者相異，且分別獨立地表示Η、Cn、Ν02、 CF3、鹵素、碳原子數為丨至1〇之烷基、或者碳原子數為1至 10之烧氧基，PG為選自由苄氧数基（carb〇benzyloxy，縮寫 Cbz)、對-甲氧基节基幾基（p_Methoxybenzyl carbonyl，縮寫 Moz)、叔丁氧幾基（tert-butyloxycarbonyl，縮寫 BOC)、9-芴 甲氧羰基（9-fluorenylmethyloxycarbony卜縮寫 FMOC)、乙醯 基（acetyl ’縮寫Ac)、苯甲酿基（benzoyl ’縮寫Bz)、节基 (benzyl ’縮寫Bn)、胺基甲酸鹽(Carbamate)、對-甲氧基苄基 (p-methoxybenzyl，縮寫 PMB )、3,4-二曱氧基苄夷 C 3,4-dimethoxybenzyl， 縮寫DMPM )、對·甲氧基笨基 (p-methoxypheny卜縮寫 PMP )、甲苯磺醯基（tosyl，縮寫 Ts )、 以及對硝基苯績醯基（nosy卜縮寫Ns)構成之族群中的保古蔓 基(Protecting group)。 201247600 本發明之包括有透過使用本發明之二胺類化合物所製備 之聚醯胺酸或者聚醯亞胺的液晶配向劑，能夠利用—種在無摩 擦狀態下使液晶分子排列之方法的光配向技術，確和 之安全性和經濟性，並具有環保性。 ' 另外，將本發明之二胺類化合物與其他用於製備液晶配向 膜之二胺類化合物混合之情況下，整體混合物也能夠進行光配 向。如此，本發明之二胺類化合物能使原先不能適用光配向之 其他化合物也能進行光配向，繼而能擴大光配向之範圍，且能 提高配向效果。 利用本發明之二胺類化合物製備之液晶配向劑，無需進行 摩擦處理，透過將偏光之紫外線(uv)照射於高分子臈之光配向 技術’就能夠製備液晶配向膜。 前揭光配向技術係利用如下所述之原理：透過引起光反 應，在膜上產生光學各向異性。因此，為利用液晶光配向控制 技術，需使用具有直線偏光方向性的光，並需要光致異構化、 光聚合或者光解等之高分子膜的光反應過程，且要求照射之光 的偏光方向能夠控制液晶分子的方向。 光致異構化反應具有受到逆反應影響之缺點，在光解反應 中存在有由於分解生成物使液晶層受到污染等缺點。對於光聚 合反應，最初雖然探討了聚（乙烯基肉桂酸）（p〇ly(vinyl cinnamate))類高分子，但由於所使用之紫外線波長短，因此具 有難以使用通用之大型曝光裝置等量產之問題。 因此，近來為了使所使用之紫外線波長長波化，正在探討 查耳酮(chalcone)類高分子，查耳酮類高分子與聚（乙烯基肉 201247600 紫 =)類高分子相比’其吸收波長為長波，且觀察到在 外線的照射下，也能㈣高效率地光聚合反應。本發明之1 ^ 類化合物作為财㈣於查耳嶋光聚合配向細單體胺 傾角、電壓轉率及配向性優秀，而且在與較難光配向之執= σ配向劑單體混合時，也驗行光配向，因此本發—胺^ 化合物為優秀的光聚合配向劑單體。 -知類 一般使用於光配向劑之聚醯亞胺樹脂係指，將芳香族四 酉夂或其仿生物和芳香族二胺或者芳香族二異氰_旨縮聚後 進行醯亞胺化所製得之高耐熱性樹脂。 聚醯亞胺樹脂依據所使用之單體種類，可具有多種分子結 構。-般來說，作為芳香族四缓酸成分係使用苯均四甲酸二酐 (PMDA)或者聯苯四羧酸二酐(BpDA);作為芳香族二胺成分係 使用對·笨二胺(p-PDA)、間-苯二胺(m-PDA)、4,4，-二胺基二苯 醚(〇DA)、4,4，_二胺基二苯曱烷(MDA)、2,2，-雙胺基苯六氟丙 烷(2,2’-bisamino phenyl hexafluoropropane，HFDA)、間-雙胺基 笨氧基二苯硪(m-BAPS)、對-雙胺基苯氧基二苯颯(p-BAPS)、 1，4-雙(4_胺基苯氧基）苯(TPE-Q)、1，3-雙(4-胺基苯氧基）苯 (TPE-R)、2，r-雙[4-(4-胺基苯氧基)苯基]丙烷(BAPp)、以及2,2’_ 雙[4-(4·胺基苯氧基)苯基]六氟丙烷(HFBAPP)等。 一般在垂直配向液晶模式（Vertical Alignment Liquid Crystal Mode)中，為了使由視角引起的亮度變化最小化，應形 成多區域(multi-domain)，是故需要多配向處理方式，但摩擦配 向方式無法以微米單位調整配向範圍，而必須利用在上下基板 上形成電極圖案或者形成突起之方式來解決。然而上述兩個方 201247600 式需要額外製程， 學特性問題等缺點 且存在有諸如響航度或者_漏光之電光 0 物二提供一種用於製備液晶配向膜之化合 物透過使用這種光配向技術，實現液晶顯示裝置中 子制，藉此在形絲向膜後，僅以uv曝光就 貫現預傾。 在本朗㈣之特定術語係為了向本領域技術人員詳細 二明本發_使用’並不是㈣限定含義或者限定在中請專利 範圍中所§己载之本發明之範圍。 【實施方式】 下面，參照實施例進一步詳細說明本發明之二胺類化合物 及其製備方法、液晶配向劑、液晶g&向膜及液晶顯示裝置。然 而，本發明之多個實關可變換為其他多種㈣，不應解釋為 本發明之範圍舰於下述實施例。本發明所提供的多個實施例 僅係為了向本領域中具有通常知識者更完整地說明本發明。 二胺類化合物及其製備方法 本發明之二胺類化合物能夠以下列化學式10或者化學式 23表示。 [化學式10]In the chemical formulas 12, 21, 22 and 23, η is an integer of 1 to 20; R! to Rs are the same or different, and each independently represents Η, Cn, Ν02, CF3, halogen, and the number of carbon atoms is 丨An alkyl group having 1 to 10 or an alkoxy group having 1 to 10 carbon atoms, and PG is selected from the group consisting of carb〇benzyloxy (abbreviated as Cbz) and p-Methoxybenzyl carbonyl (p_Methoxybenzyl carbonyl, The abbreviation Moz), tert-butyloxycarbonyl (abbreviated as BOC), 9-fluorenylmethyloxycarbony (abbreviated FMOC), ethenyl (acetyl 'abbreviated Ac), benzoyl ' Abbreviation Bz), benzyl 'abbreviation Bn', carbamate, p-methoxybenzyl (PMB), 3,4-dimethoxybenzyl C 3 , 4-dimethoxybenzyl, abbreviation DMPM), p-methoxypheny (pMP), tosyl (Ts), and p-nitrophenyl (nsy) The Protecting group in the group that constitutes it. 201247600 The liquid crystal alignment agent comprising polylysine or polyimine prepared by using the diamine compound of the present invention can utilize a light alignment method of arranging liquid crystal molecules in a frictionless state Technology, and it is safe and economical, and environmentally friendly. Further, in the case where the diamine compound of the present invention is mixed with another diamine compound for producing a liquid crystal alignment film, the entire mixture can also be optically aligned. Thus, the diamine compound of the present invention enables photo-alignment of other compounds which are not originally applicable to photo-alignment, thereby expanding the range of photo-alignment and improving the alignment effect. The liquid crystal alignment agent prepared by using the diamine compound of the present invention can prepare a liquid crystal alignment film by performing a rubbing treatment and irradiating a polarized ultraviolet ray (uv) onto a polymer ray light alignment technique. The pre-extrusion alignment technique utilizes the principle of producing optical anisotropy on the film by causing a light reaction. Therefore, in order to utilize the liquid crystal light alignment control technology, it is necessary to use light having a linear polarization directivity, and a photoreaction process of a polymer film such as photoisomerization, photopolymerization or photolysis is required, and polarized light of the irradiated light is required. The direction can control the direction of the liquid crystal molecules. The photoisomerization reaction has a drawback that it is affected by the reverse reaction, and there is a disadvantage that the liquid crystal layer is contaminated by the decomposition product in the photolysis reaction. In the photopolymerization reaction, a poly(vinyl cinnamate) polymer was first studied. However, since the ultraviolet wavelength used is short, it is difficult to mass-produce a large-scale exposure apparatus. The problem. Therefore, recently, in order to make the wavelength of ultraviolet rays used long, the chalcone-based polymer is being explored, and the absorption wavelength of the chalcone polymer is higher than that of the poly(vinyl meat 201247600 violet=) polymer. It is a long wave, and it is observed that under the irradiation of the external line, it is also possible to (4) photopolymerization reaction with high efficiency. The compound of the present invention is excellent in dip angle, voltage conversion and alignment of the fine monomeric amine in the photopolymerization of the chalcogen, and is also mixed with the π-aligning agent monomer which is more difficult to align with the light. The photo-alignment is carried out, so the present-amine compound is an excellent photopolymerization agent monomer. - Known as a polyimine resin generally used in a photo-aligning agent, which is obtained by polycondensation of an aromatic tetraterpene or a pseudo-organism thereof and an aromatic diamine or an aromatic diisocyanate. High heat resistant resin. Polyimine resins may have a variety of molecular structures depending on the type of monomer used. In general, pyromellitic dianhydride (PMDA) or biphenyltetracarboxylic dianhydride (BpDA) is used as the aromatic tetrazoic acid component, and p-diphenylamine is used as the aromatic diamine component. -PDA), m-phenylenediamine (m-PDA), 4,4,-diaminodiphenyl ether (〇DA), 4,4,-diaminodiphenyl decane (MDA), 2, 2 , 2,2'-bisamino phenyl hexafluoropropane (HFDA), m-bisamino phenoxy diphenyl hydrazine (m-BAPS), p-diaminophenoxy diphenyl hydrazine (p-BAPS), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 2, R-bis[4-(4-aminophenoxy)phenyl]propane (BAPp), and 2,2'-bis[4-(4.aminophenoxy)phenyl]hexafluoropropane (HFBAPP) )Wait. Generally, in the Vertical Alignment Liquid Crystal Mode, in order to minimize the change in luminance caused by the angle of view, a multi-domain should be formed, so that a multi-alignment processing method is required, but the friction alignment method cannot The micrometer unit adjusts the alignment range, and must be solved by forming an electrode pattern or forming a protrusion on the upper and lower substrates. However, the above two methods 201247600 require additional processes, problems such as learning characteristics, and there are electro-optical materials such as sounding or _light leakage. A compound for preparing a liquid crystal alignment film is provided by using such a light alignment technique. The liquid crystal display device is made in the neutron system, whereby the pretilt is formed by exposing only the uv after the filament is applied to the film. The specific terminology of the present invention is intended to be in the nature of the invention, and is not intended to limit the scope of the invention. [Embodiment] Hereinafter, a diamine compound of the present invention, a method for producing the same, a liquid crystal alignment agent, a liquid crystal g& film, and a liquid crystal display device will be described in further detail with reference to examples. However, the various aspects of the present invention can be converted into other various types (four), and should not be construed as the scope of the present invention in the following embodiments. The various embodiments of the present invention are intended to provide a more complete description of the invention. Diamine compound and preparation method thereof The diamine compound of the present invention can be represented by the following Chemical Formula 10 or Chemical Formula 23. [Chemical Formula 10]

⑧ 201247600 [化學式23]8 201247600 [Chemical Formula 23]

在該化學式10及化學式23中，η為1至20之整數；R, 至R8為相同或者相異，且分別獨立地表示Η、CN、N〇2、CF3、 鹵素、碳原子數為1至10之烷基、或者碳原子數為1至10之 烧氧基。 根據本發明之一實施例，在該化學式10及化學式23中， η為1至5之整數；比至R8為相同或者相異，且可分別獨立 地為Η或者碳原子數為1至10之烷基。例如，在該化學式10 及化學式23中，η為1，R!至R8可為Η。 以該化學式10表示之二胺類化合物之製備方法，包括以 下步驟： 透過使以下列化學式6表示之化合物與以下列化學式8表 示之化合物反應，而製備以下列化學式9表示之化合物；以及 去除以下列化學式9表示之化合物的保護基PG ; 201247600 [化學式6]In the chemical formula 10 and the chemical formula 23, η is an integer of 1 to 20; R, to R8 are the same or different, and each independently represents Η, CN, N〇2, CF3, halogen, and the number of carbon atoms is 1 to An alkyl group of 10 or an alkoxy group having 1 to 10 carbon atoms. According to an embodiment of the present invention, in the chemical formula 10 and the chemical formula 23, η is an integer of 1 to 5; the ratio to R8 is the same or different, and may be independently Η or a carbon number of 1 to 10, respectively. alkyl. For example, in the chemical formula 10 and the chemical formula 23, η is 1, and R! to R8 may be ruthenium. The method for producing a diamine compound represented by the chemical formula 10, comprising the steps of: preparing a compound represented by the following Chemical Formula 9 by reacting a compound represented by the following Chemical Formula 6 with a compound represented by the following Chemical Formula 8; The protecting group PG of the compound represented by the formula 9; 201247600 [Chemical Formula 6]

HOHO

cf3 [化學式8]Cf3 [Chemical Formula 8]

[化學式9][Chemical Formula 9]

[化學式10][Chemical Formula 10]

该化學式6、8、9及10中’η為1至20之整數；艮至 Rs為相同或者相異’且分別獨立地表示Η、CN、N〇2、CF3、 鹵素、碳原子數為1至10之烷基、或者碳原子數為丨至1〇之 炫•氧基，PG為選自由节氧幾基（carbobenzyloxy，縮寫Cbz)、 對-甲氧基苄基幾基（p-Methoxybenzyl carbonyl，縮寫 Moz)、 叔丁氧隸基（tert-butyloxycarbonyl，縮寫 BOC)、9-芴曱氧毅 201247600 基（9-fluorenylmethyloxycarbonyl，縮寫 FMOC )、乙醯基 (acetyl，縮寫Ac)、苯甲醯基（benzoyl，縮寫Bz )、节基 (benzyl，縮寫Bn)、胺基甲酸鹽(Carbamate)、對-甲氧基苄基 (p-methoxybenzyl ’ 縮寫卩]\0)、3,4-二曱氧基苄基 (3,4-dimethoxybenzyl，縮寫 DMPM )、對-甲氧基苯基 (p-methoxypheny卜縮寫PMP )、甲苯磺醯基（t〇Sy卜縮寫Ts ) 以及對硝基苯磺醯基（nosyl縮寫Ns)構成之族群中的保雙其 (Protecting group) ° 更具體地，例如當該PG為BOC時，以該化學式1〇表厂、 之二胺類化合物可透過逐步執行下列反應式I、η、ΠΙ、Iv及 V而製備。 [反應式I] f3q/>^ohIn the chemical formulas 6, 8, 9 and 10, 'η is an integer from 1 to 20; 艮 to Rs are the same or different' and independently represent Η, CN, N〇2, CF3, halogen, and the number of carbon atoms is 1. An alkyl group of 10 or a methoxy group having a carbon number of 丨 to 1 ,, PG is selected from the group consisting of carbobenzyloxy (abbreviated as Cbz) and p-Methoxybenzyl carbonyl (p-Methoxybenzyl carbonyl) , abbreviation Moz), tert-butyloxycarbonyl (abbreviated as BOC), 9-fluorenylmethyloxycarbonyl (abbreviated FMOC), acetyl group (acetyl, abbreviation Ac), benzamidine (benzoyl, abbreviated as Bz), benzyl (abbreviated as Bn), carbamate, p-methoxybenzyl (abbreviated 卩) \0), 3,4-di 3,4-dimethoxybenzyl (abbreviated as DMPM), p-methoxyphenyb (abbreviated as PMP), toluenesulfonyl (t〇Syb, abbreviated as Ts), and p-nitrophenylsulfonate Protecting group in the group formed by the base (nosyl abbreviation Ns). More specifically, for example, when the PG is BOC, the chemical formula 1 The diamine compound can be prepared by gradually performing the following reaction formulas I, η, ΠΙ, Iv and V. [Reaction formula I] f3q/>^oh

Msei, TEAMsei, TEA

——^ F3cnH^〇MS——^ F3cnH^〇MS

[反應式II][Reaction formula II]

17 201247600 [反應式IV]17 201247600 [Reaction formula IV]

NHNH

OHOH

Pd/C, H2(g) MeOH Η,ΝPd/C, H2(g) MeOH Η, Ν

B0C2O, NaHC〇3(aq) THFB0C2O, NaHC〇3(aq) THF

[反應式V][Reaction formula V]

cf3. 而且，以該化學式23表示之二胺類化合物，能夠透過下 述步驟製備。 透過使以下列化學式12表示之化合物與以下列化學式21 表示之化合物反應，而製備以下列化學式22表示之化合物； 以及 201247600 去除以下列化學式22表示之化合物的保護基PG : [化學式12]Cf3. Further, the diamine compound represented by the chemical formula 23 can be produced by the following procedure. The compound represented by the following Chemical Formula 22 is prepared by reacting a compound represented by the following Chemical Formula 12 with a compound represented by the following Chemical Formula 21; and 201247600 The protective group PG of the compound represented by the following Chemical Formula 22 is removed: [Chemical Formula 12]

[化學式22][Chemical Formula 22]

19 201247600 [化學式23]19 201247600 [Chemical Formula 23]

在該化學式12、21、22及23中，η為1至20之整數； R!至Rs為相同或者相異，且分別獨立表示H、CN、N02、CF3、 鹵素、碳原子數為1至10之烷基、或者碳原子數為丨至1〇之 烧氧基，PG為選自由苄氧獄基（carb〇benzyloxy，縮寫Cbz)、 對-甲氧基节基数基（p-Methoxybenzyl carbonyl，縮寫 Moz)、 叔丁氧幾基（tert-butyloxycarbonyl，縮寫 BOC)、9-芴甲氧幾 基（9-fluorenylmethyloxycarbonyl，縮寫 FMOC )、乙醯基 (acetyl ’縮寫Ac)、苯甲醯基（benzoyl，縮寫bz )、节芙 (benzy卜縮寫Bn)、胺基甲酸鹽(Carbamate)、對·甲氧基节夷 (p-methoxybenzyl，縮寫 PMB )、3,4-二甲氧美节美 (3,4-dimethoxybenzyl，縮寫 DMPM )、對甲备丑奸 T乳基本基 (p-methoxypheny卜縮寫ΡΜΡ )、曱笨磺醯基（t〇Syi，縮寫丁 以及對硝基笨磺醯基（nosyl縮寫Ns)構成之埃群 · 、f肀的保護基 201247600 (Protecting group)。 . 更具體地，例如當該PG為BOC時，以該化學式23表示In the chemical formulas 12, 21, 22 and 23, η is an integer of 1 to 20; R! to Rs are the same or different, and independently represent H, CN, N02, CF3, halogen, and the number of carbon atoms is 1 to An alkyl group of 10 or an alkoxy group having a carbon number of from 丨 to 1 ,, and PG is selected from the group consisting of carb〇benzyloxy (abbreviated as Cbz) and p-Methoxybenzyl carbonyl (p-Methoxybenzyl carbonyl, The abbreviation Moz), tert-butyloxycarbonyl (abbreviated as BOC), 9-fluorenylmethyloxycarbonyl (FMOC), acetyl-acetyl (abbreviated Ac), benzoyl (benzoyl) , abbreviated bz ), 芙 ( (benzy 卜 abbreviated Bn), carbamate, p-methoxybenzyl (abbreviated PMB), 3,4-dimethyloxime ( 3,4-dimethoxybenzyl, abbreviated as DMPM), 对 备 T T T ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The abbreviation Ns) constitutes the protective group of eugroup·, f肀 201247600 (Protecting group). More specifically, for example, when the PG is BOC, the chemistry 23 shows

_ 之二胺類化合物可透過逐步執行下列反應式VI、VII及VIII 而製備。 [反應式VI]The diamine compound can be prepared by gradually performing the following reaction formulas VI, VII and VIII. [Reaction formula VI]

_ MsCI, TEA -η— F3cnHT0Ms [反應式VII]_ MsCI, TEA -η- F3cnHT0Ms [Reaction formula VII]

201247600 [反應式VIII]201247600 [Reaction formula VIII]

類化合物的原料化合物、中間化合物以及生成化合物分別可以 化學式1至23表示。 [化學式1] [化學式2] F3C^M^〇Ms 22 201247600 [化學式3] Ο R| [化學式4]The starting compound, the intermediate compound, and the resulting compound of the compound can be represented by Chemical Formulas 1 to 23, respectively. [Chemical Formula 1] [Chemical Formula 2] F3C^M^〇Ms 22 201247600 [Chemical Formula 3] Ο R| [Chemical Formula 4]

r8 r3^Y^N)^>^cf3 0 R7 R4R8 r3^Y^N)^>^cf3 0 R7 R4

[化學式8][Chemical Formula 8]

NH-PGNH-PG

PG-HNPG-HN

.OH.OH

PG-HNPG-HN

23 201247600 [化學式ίο]23 201247600 [Chemical formula]

[化學式11][Chemical Formula 11]

[化學式12][Chemical Formula 12]

[化學式13][Chemical Formula 13]

[化學式16][Chemical Formula 16]

24 ⑧ 201247600 [化學式17] [化學式18] 〇2N 〇2Nh •co2h 心。H C02K Ρ^Η Θ2Ν 02Ν [化學式19] [化學式20] h2n OH PG-HN 0/〇h Λ. OH 3H h2n PG-HN [化學式21]24 8 201247600 [Chemical Formula 17] 〇2N 〇2Nh • co2h Heart. H C02K Ρ^Η Θ2Ν 02Ν [Chemical Formula 19] [Chemical Formula 20] h2n OH PG-HN 0/〇h Λ. OH 3H h2n PG-HN [Chemical Formula 21]

25 201247600 [化學式22]25 201247600 [Chemical Formula 22]

[化學式23][Chemical Formula 23]

201247600 PG為選自由苄氧Μ基（carbobenzyloxy，縮寫Cbz)、對甲氧 基苄基羰基（p-Methoxybenzyl carbony卜縮寫Moz)、叔丁氧 羰基（tert-butyloxycarbonyl，縮寫 BOC )、9-茴曱氧幾基 (9-fluorenylmethyloxycarbony卜縮寫 FMOC )、乙醯基（acetyi， 縮寫Ac )、苯甲醯基（benzoyl，縮寫Bz)、苄基（benZy卜縮 寫Bn)、胺基曱酸鹽（Carbamate)、對-甲氧基节基 (p-methoxybenzyl，縮寫 PMB )、3,4-二曱氧基苄基 (3,4-dimethoxybenzyl，縮寫 DMPM )、對-曱氧基笨基 (p-methoxypheny卜縮寫PMP)、甲苯磺醯基（tosy卜縮寫Ts) 以及對硝基苯磺醯基（nosy卜縮寫Ns)構成之族群中的保護 基(Protecting group) ° 以該化學式10表示之二胺類化合物或者以該化學式23表 示之二胺類化合物包含有查耳酮結構，且可用於與四羧酸二酐 進行反應而製備聚醯胺酸或者聚醯亞胺。 液晶配向劑 本發明提供一種液晶配向劑，其包括有透過二胺成分與四 羧酸二酐之反應而獲得的聚醯胺酸或者聚醯亞胺。該二胺成分 包括以下列化學式10表示之二胺類化合物。 而且，本發明提供一種液晶配向劑，其包括有透過二胺成 分與四羧酸二酐之反應而獲得的聚醯胺酸或者聚醯亞胺。該二 胺成分包括以下列化學式23表示之二胺類化合物。 27 201247600 [化學式ίο] h2n201247600 PG is selected from the group consisting of carbobenzyloxy (abbreviated as Cbz), p-Methoxybenzyl carbony (abbreviated as Moz), tert-butyloxycarbonyl (abbreviated as BOC), 9-anthracene 9-fluorenylmethyloxycarbony (FMOC), acetyi (Ac), benzoyl (Bz), benzyl (benZy), carbamate , p-methoxybenzyl (PMB), 3,4-dimethoxybenzyl (DMPM), p-methoxypheny Protecting group in the group consisting of the abbreviated PMP), the tosysulfonyl group (tosy) and the p-nitrophenylsulfonyl group (nsy). The diamine compound represented by the chemical formula 10 Alternatively, the diamine compound represented by the chemical formula 23 contains a chalcone structure, and can be used for reacting with a tetracarboxylic dianhydride to prepare a polyamic acid or a polyimine. Liquid Crystal Aligning Agent The present invention provides a liquid crystal aligning agent comprising a poly phthalic acid or a polyimine obtained by a reaction of a diamine component and a tetracarboxylic dianhydride. The diamine component includes a diamine compound represented by the following Chemical Formula 10. Moreover, the present invention provides a liquid crystal alignment agent comprising polylysine or polyimine obtained by a reaction of a diamine component with a tetracarboxylic dianhydride. The diamine component includes a diamine compound represented by the following Chemical Formula 23. 27 201247600 [chemical formula ίο] h2n

[化學式23][Chemical Formula 23]

在該化學式10及化學式23中，η為1至20之整數；R, 至R8為相同或者相異，且分別獨立地表示H、CN、N02、CF3、 鹵素、碳原子數為1至10之烷基、或者碳原子數為1至10之 烧氧基。 此時，「二胺成分」係指包括至少一種以該化學式10或者 化學式23表示之本發明的二胺類化合物，且選擇性地還包括 其他二胺類化合物。 尤其，本發明之以該化學式10或者化學式23表示之二胺 類化合物，可經由與無光學活性之其他二胺類化合物混合，形 28 ⑧ 201247600 成聚醯胺酸或者聚醯亞胺，從而 液晶之垂直配向穩定。 光配向性。因此’能夠使 能夠與以該化學式10或者化學 一起使用的二胺類化合物例如為由X〇表示之二胺類化合物 二氨基二苯曱烷、4,4，-二氨基: Ρ 、❿苯二胺、4,4’_ 醚、M，·二氨基二苯砜、3,3，_ _ 虱基一本硫 斤# 一甲基_4,4，-二氨基聯笨、44，- 二氣基苯醯替苯胺、4,4，_:氨基：麵、^:氨基萘、2:2，_ 甲基ΊΜ聯苯、5_A基小（4,氨基苯卜咖三甲基 茚滿、6_教基_1_ (4，-氨基笨）-似三甲基節滿、3,4，_二氨基 二苯醚、3,3’·二氨基二苯甲酮、3,4’_二氨基二苯甲酮、4,4，_二 氨基二苯甲酮、2,2-雙[4· (4-氨基笨氧基）苯基]丙院、2,2_雙 [4_ (4-氣基本氧基）本基]六氟丙烧、2,2_雙（4_氨基笨）六氟 丙烧、2,2-雙[4- (4-氨基苯氧基）笨基]颯、丨，4_雙（4_氨基笨 氧基）苯、1,3-雙（4-氨基苯氧基）苯、1,3-雙（3-氨基苯氧基） 苯、9,9-雙（4-氨基苯）_1〇_氫蒽、2,7-二氨基苟、9,9-雙（4-氨基苯）场、4,4，-亞曱基-雙（2-氯苯胺）、2,2，，5,5，-四氯-4,4，-二氨基聯苯、2,2’-二氯-4,4，-二氨基-5,5，-二甲氧基聯苯、3,3，-二甲氧基-4,4’-二氨基聯苯、K4’- (p-亞苯基異亞丙基）雙笨 胺、4,4’- (m·亞苯基異亞丙基）雙苯胺、2,2’·雙[4- (4·氨基-2-三氟甲基苯氧基）苯]六氟丙烷、4,4，-二氨基-2,2，-雙（三氟甲 基）聯苯、4,4’-雙[(4-氨基_2_三氟曱基）苯氧基]-八氟聯苯、 二（4-氨基苯）聯苯胺、】_ (4_氨基苯）-13,3-三甲基-1H-茚滿 -5-胺、1，1_間苯二曱胺、L3·丙二胺、四亞甲基二胺、戊二胺、 六亞曱基二胺、庚二胺、辛二胺、壬二胺、1，4-環己二胺 29 201247600 (l，4-diaminocyclohexane)、異佛爾酮二胺、四氫化二環戊亞二 稀基二胺、二ί哀[6.2.1.02’7]-十一碳稀二甲基二胺、4,4’·亞甲基 雙（環已胺）、1，3-雙（敦甲基）環己烧等脂肪族或脂環族二胺； 2,3-二氣基吼11定、2,6-二氨基比咬、3,4-二氨基°比。定、2,4-二氨 基嘧啶、5,6-二氨基-2,3-二氰吡嗪、5,6-二氨基-2,4-二羥基响 °定、2,4-一乱基-6-一曱基氣基-1，3,5-三嗓、1，4-雙（3-氨丙基） 0辰嗓、2,4-二氣基-6-異丙氧基-1，3,5-三唤、2,4-二氨基_6·〒氧 基-1，3,5-二嗓、2,4-一氣基_6_苯基-1，3,5-三嗪、2,4-二氨基-6-甲基-s-二嗪、2,4-二氨基-l，3,5-三嗪、4,6-二氨基-2-乙烯基-s_ 二β秦、2,4-二氨基-5-苯基。塞tf坐、2,6-二氨基嗓吟、5,6-二氨基-l，3-一甲基脲’。定、3,5-二氨基-1，2,4-三嗤、6,9-二氨基-2-乙氧基口丫 啶乳酸鹽(6,9-diamino_2_ethoxy-acridine Lactate)、3,8-二氨基-6- 苯基菲啶、l，4二氨基哌嗪、3,6·二氨基吖啶、雙（4-氨基苯基） 、1- (3,5-一氨基苯基）_3_癸基琥珀醯亞胺、ι_ (3,5_二氨 基本基）-3-辛基琥珀醯亞胺所構成之族群中之一種以上的二胺 類化合物。 用於合成本發明之液晶配向劑中之聚醯胺酸或者聚醯亞 胺的四羧酸二酐，可為脂環四羧酸二酐、脂肪族四羧酸二酐及 芳香族四羧酸二酐。 該脂環四㈣二gf之具體例可為⑶+環丁炫四叛酸二 肝1，2-一甲基_1，2,3,4-環丁烧四緩酸二針、1，3_二曱基_1，2,3,4_ 壤丁燒四舰二gf、以二氣-⑶+環丁烧四減二針、 酉夂一酐、1，2,4,5-環己院四幾酸二野、3,3，，4,4，_二環己基四缓酸 201247600 一酐順式3,7-一丁基環辛-1,5-二稀-1，2,5,6·四缓酸二針、2,3,5_ 二羧基裱戊烷基乙酸二酐、5· (2,5_二氧代四氫_3_呋喃基）_3_ 曱基-3-環乙婦-1，2-二紐二酐、3,5,6_三幾基_2_缓基降冰片烯 -2:3,5:6-二酐、2,3,4,5-四氫呋喃四羧酸二酐、六 氫-5 (四氫-2,5-二氧-3-呋喃基）_萘并[i，2_c]_吱喃_1，3_二_、 1，3,3&amp;，4,5,91)-六氫-5-甲基-5(四氫_2,5-二氧-3-0夫喃基）-萘并 [l，2-c]-呋喃 _1，3_ 二酮、1，3,3&amp;，4,5，％-六氫-5-乙基-5(四氫-2,5-二氧-3-呋喃基）-萘并[l，2-c]·呋喃_1,3_二酮、i，3,3a，4,5,9b-六氫 -7-甲基-5 (四氫-2,5-二氧-3-吱喃基）_蔡并[i，2-c]-a夫喃-1,3-二 酮、1，3,3&amp;,4,5，％-六氫-7-乙基-5(四氫-2,5-二氧-3-呋喃基）· 萘并[l，2-c]-呋喃-1，3-二酮、l，3,3a，4,5,9b-六氫-8-曱基_5 (四氫 -2,5-二氧-3-呋喃基）-萘并[l，2-c]-呋喃-1，3·二酮、l，3,3a,4,5,9b-六虱_8_乙基-5(四l-2,5-二氧-3-吱喃基）-萘并[l，2-c]-a夫喃-1,3· 二酮、1，3,3\4,5,91&gt;六氫-5,8-二甲基-5(四氫-2,5-二氧-3-呋喃 基）-萘并[l，2-c]·呋喃-1，3-二酮、5- (2,5-二氧四氫呋喃基）_3_ 曱基-3-環乙烯-1,2-二羧酸酐、二環[2,2,2]-辛-7-烯-2,3,5,6-四羧 酸二酐、3-氧雜二環[3,2，1]辛烷-2,4-二酮-6-螺-3’-(四氫呋喃 _2’，5’-二酮）等。該脂肪族四羧酸二酐之具體例可為丁烧四羧 酸二酐等。 該芳香族四羧酸二酐之具體例可為苯均四甲酸二酐、4,4’· 聯苯四缓酸二針(4,4’-Biphthalic dianhydride)、3,3’,4,4’-二笨曱 酮四羧酸二酐、3,3’，4,4’-雙苯磷四羧酸二酐、1,4,5,8-萘四羧酸 二酐、2,3,6,7-萘四羧酸二酐、3,3’,4,4’-二苯醚四羧酸二酐、 3,3，,4,4，-二甲基二苯矽烷四羧酸二酐、3,3，，4,4’_四苯矽烷四羧 31 201247600 酸二酐、1，2,3,4-呋喃四羧酸二酐、4,4，-雙（3,4-二羧基苯氧基） 二苯硫醚二酐、4,4’-雙（3,4-二羧基苯氧基）二苯礙二酐、4,4，-雙（3,4_二羧基苯氧基）二笨基丙烷二酐、3,3，，4,4，_全氟異亞 丙基二鄰苯二甲酸二酐、3,3’，4,4’-聯苯四羧酸二酐、雙（鄰苯 二甲酸）笨基氧化膦二酐(bis(phthalic acid)phenyl phosphine oxide)、ρ·亞笨基-雙（三笨基鄰苯二甲酸）二酐、m_亞笨基_ 雙（二苯基鄰苯二甲酸）二酐、雙（三苯基鄰苯二甲酸）_4,4，_ 二苯基醚二酐、雙（三苯基鄰苯二甲酸）-4,4，-二苯基曱烷二 酐、乙二醇·雙（脫水偏笨三酸酯）、丙二醇_雙（脫水偏苯三酸 S曰）、1，4-丁二醇-雙（脫水偏苯三酸酯）、丨，6_己二醇-雙（脫水 偏苯三酸醋）、1，8_辛二醇-雙（脫水偏苯三酸酯）、2,2·雙（4_ 經苯基）丙烷-雙（脫水偏苯三酸酯）等。 反應’可獲得聚醯胺酸。 經由包括有以該化學式10表示之二胺類化合物或者以該 化學式23表示之二胺類化合物的二胺成分與該四羧酸二酐之 用於該聚醯賊之合成反應的該四賴二肝和該二胺成 1當量胺基，該四 更優選約為0.7至 分之使用比例如下：相對於該二胺成分中的 綾酸二酐中之酸酐優選約為0.2至2當量， 1·2當量。 小時，更優選地可為3 下，反應時間優選可為約1小時至72 小時至48小時。 ’只要使用能夠溶解 此時，使用之有機溶劑沒有特別限制 201247600 所生成之聚醢胺酸者即可’例如可為N-甲基-2-»比洛燒酮、N，N-二曱基乙醯胺、N，N-二曱基曱醯胺、3_丁氧基_N，N_二曱基丙烷 醯胺、3-甲氧基-N，N-二曱基丙烷醯胺、3-己氧基_n，N_二曱基 丙烷醯胺等醯胺化合物、二曱基亞砜、γ_丁内酯、四甲基尿素、 六甲基磷醯二胺專非質子化合物；以及曱齡、二曱苯盼、 苯酚、苯酚鹵化物等笨酚化合物等。 另一方面’該有機溶劑在不析出所生成之聚醯胺酸之範圍 内，可以同時使用醇、酮、酯、醚、鹵化碳氫化合物、碳氫化 合物等聚醯胺酸之不良溶劑(poor solvent)。這種不良溶劑之具 體例可為曱醇、乙醇、異丙醇、環己醇、乙二醇、丙二醇、1，4· 丁二醇、三甘醇、乙二醇單曱醚、乳酸乙酯、乳酸丁酯、丙酮、 甲乙酮、甲基異丁基曱酮、環己酮、乙酸曱酯、乙酸乙酯、乙 酸丁醋、曱氧基丙酸曱酉旨(Methyl methoxy propanoate)、乙氧基 丙酸乙酯(ethyl ethoxy propanoate)、草酸二乙酯、丙二酸二乙 酯、二乙醚、乙二醇甲驗、乙二醇乙驗、乙二醇_n_丙醚、乙二 醇-i-丙醚、乙二醇-n-丁贼、乙二醇二曱趟、乙二醇乙驗乙酸酉旨、 二甘醇二甲基醚、二甘醇二乙醚、二甘醇單甲醚、二甘醇單乙 醚、二甘醇單曱趟乙酸酯、二甘醇單乙轉乙酸酯、四氫吱喃、 二氯甲烷、1，2-二氯乙烷、l，4-二氣丁烷、三氯乙烷、氣苯、鄰 二氯苯、己烷、庚烷、辛烷、笨、曱笨、二曱苯、丙酸異戊酯、 丁酸異戊醋、二異戊驗等。藉此獲得透過溶解聚醯胺酸而進行 反應的反應》谷液。之後，將此反應溶液加入大量不良溶劑中而 獲得析出物’並在減壓條件下，透過乾燥此析出物或者用蒸發 器減壓蒸餾並除去反應溶液而獲得聚醯胺酸。另外，可將此聚 33 201247600 酿胺酸重新溶解於有機溶劑中，接著透過執行一次或多次之將 用不良溶劑析出之製程或者用蒸發器減壓、蒸餾並除去之製程 而純化聚醯胺酸。 透過將所獲得之該聚醯胺酸脫水閉環，以進行醯亞胺化而 獲得聚醢亞胺。 進行該聚醯胺酸之脫水閉環的方式，優選地為⑴透過加熱 聚醯胺酸之方法，或者(π)將聚醯胺酸溶解於有機溶劑，並在 此溶液中添加脫水劑及脫水閉環用的催化劑後，根據需要加熱 之方法來進行。在該⑴加熱聚醯胺酸之方法中的反應溫度，優 選為約50C至約200。(：，更優選為約60°c至約170〇c。反應時 間優選為約1小時至約8小時，更優選為約3小時至約5小時。 右反應溫度低於50。(：，無法充分進行脫水閉環反應，若反應溫 度超過200C，有時會導致所獲得之聚醯亞胺的分子量變小。 另一方面，在該(u)在聚醯胺酸的溶液中中添加脫水劑及 脫水閉ί讀化劑之方法巾’脫水劑可使關如乙料、丙酸 酐、二氣乙酸畔酸酐。依據所要達成之酿亞胺化率，脫水劑 之使用量有所不同’然而相對於丨莫耳輯麟之醯胺酸結 構，優選為約〇.〇丨莫耳至約20莫耳。 而且，脫水閉環催化劑可以使用例如吡啶、三曱吡啶、二 甲比定—乙胺等二級胺，但是並不限於此。脫水閉環催化劑 之使用量’相對於所使用之1莫耳脫水劑，優選為約0.01莫 耳至Ί0莫耳。該脫水劑、脫水閉環劑之使用量越多，醯亞 胺化率就會越高。驗脫水_反應之有機溶劑，可使用已被 列舉可用於聚_酸之合成的有機溶劑。 201247600 脫水閉環反應之反應溫度優選為約至約180°c，更優 選為約10°c至約15〇。〇反應時間優選為約1小時至約8小時， 更優選為約3小時至約5小時。在該方法(i)中所獲得之聚醯亞 胺可直接用於製備液晶配向劑，或者可將所獲得之聚醯亞胺純 化後’才使用於液晶配向劑的製備中。 另一方面’在該方法(ii)中獲得之含聚醯亞胺的反應溶液 可直接用於製備液晶配向劑，也可從該反應溶液中除去脫水劑 以及脫水閉環催化劑後，才在液晶配向劑之製備中使用，也可 分離聚醯亞胺後，才在液晶配向劑之製備中使用，或者純化所 分離的聚醯亞胺後，才用於液晶配向劑之製備。從反應溶液中 除去脫水鼓脫水閉環催化_方法，可應關如㈣置換等 方法。聚醯亞胺之分離及純化，可透過與上述聚軸酸之分離 及純化方法相同的方式進行。 本發明之液晶配向含有該聚_酸或 =閉=得之聚亞醢胺，以根據需要而加入之二 選地，该聚合體及添加劑係溶解於有機溶劑。 傻 可使用於本發明之液晶配向劑中的有機溶劑例 甲基-2-鱗_、γ_丁内酉旨、γ_τ内酿胺、N N_ 了為N- N，N-二甲基乙醯胺、4_經基斗甲基_ ’ : ▲土甲醯胺、 酸丁酯、乙酸丁酯、甲氧基丙酸甲酯、 甲醚、乳 醇㈣、乙二醇乙鍵、乙二醇务丙轉乳二.酸乙醋、乙二 _.丨 &amp;两、中 ， ·η·丁醚（Butyl Cdl〇s〇lve ’ 或稱乙二醇單丁醚.二醇 喊、乙二醇乙喊乙酸酯、二甘醇二甲，、乙一醇一曱 甘醇單甲醚、二甘醇單乙酸、二甘t醚、一甘醇二乙醚、二 甘知早甲峻乙酸酉旨、二甘醇單 35 201247600 乙醚乙酸酯、3-丁氧基-N，N-二甲基丙烷醯胺、3_甲氧基_N,N_ -甲基丙院醯胺、3-己氧基-N，N-二甲基丙炫醯胺等。 在本發明之液晶配向劑中的固形物（係指除液晶配向劑之 /合劑以外之成分）濃度，考慮到黏性、揮發性等因素必須適當 地進行選擇，相對於液晶配向劑之總體重量，其固形物濃度可 優選為約1重量至約10重量％(wt%)之範圍。 當該固形物濃度低於1重量％(wt%)時，藉由塗覆液晶配 向劑而形成之膜的厚度過薄，無法獲得良好的液晶配向膜，另 一方面，當該固形物濃度超過10重量％(wt%)時，形成之膜的 厚度過厚，同樣無法獲得良好之液晶配向膜，並且，液晶配向 劑之黏性增大，會降低塗覆特性。 液晶配向膜 透過將本發明之液晶配向劑塗覆於基材上，並進行加熱而 形成液晶配向膜。 該液晶配向劑例如可透過輥塗法、旋轉法、印刷法、喷墨 法等方法進行塗覆，接著利用加熱塗覆表面而形成液晶配向 膜。 在塗覆液晶配向劑後，為了防止所塗覆之配向劑液體流 動，優選地可執行預熱（預烤）。預烤溫度，優選為約3〇。〇至 約300°C，更優選地為約40。(：至約20(TC，最優選為約50°C至 約 150。。。 此後’完全除去溶劑’並為了使聚醯胺酸熱醯亞胺化，可 以執行燒成（後烤）製程。該燒成（後烤）溫度，優選為約80 °C至約300°c，更優選為約12〇。(：至約250°c。如此，也可透過 36 ⑧ 201247600 塗覆包含聚醯亞胺之液晶配向劑，之後除去有機溶劑以形成即 將成為液晶配向膜之塗膜，並且利用加熱進行脫水閉環，從而 形成進一步被醯亞胺化的配向膜。所形成之液晶配向膜的厚 度，優選為約0.001 μηι至約1 μιη，更優選為約〇 005 μιη至約 0.5 μιη。 利用對乾燥後之塗膜表面照射波長範圍約15〇 nm至45〇 nm之紫外線來進行配向處理。此時，可以照射曝光強度約％ mJ/cm至約1 〇 j/cm之能量’優選為約5〇〇 mj/cm2至約5 j/cm2 之能量。 透過别述之光配向以及一系列過程之後，就能夠獲得具有 優秀之熱穩定性與高配向性之液晶配向膜。 液晶顯示裝置 本發明提供一種包括有上述液晶配向膜的液晶顯示裝置。 前述液晶顯示裝置可以利用本技術領域中常見的方法進 行製備。例如，將含有球狀間隔件之黏合劑塗覆於形成有本發 明之液晶配向膜之兩個基板令其中一個基板的端部後，將該基 板黏合於另一基板’從而完成單元(cell)的接合。之後將液晶注 入於所完成之單元中，並進行熱處理，從而完成液晶單元。 具有该液晶配向膜之本發明的液晶顯示裝置表現出優秀 的配向狀態，且在液晶配向狀態下的熱穩定性優秀。 以下，經由發明之具體實施例，更詳細地說明本發明之作 用及效果。惟，這些實施例只是為了作為本發明之示例而提 出，並不以此限定本發明之申請專利範圍。 &lt;實施例&gt; 37 201247600 二胺類化合物之製備實施例1 製備化學式10 (n=l，R广R8=H，PG=BOC時）之化合物 [反應式I ]In the chemical formula 10 and the chemical formula 23, η is an integer of 1 to 20; R, to R8 are the same or different, and each independently represents H, CN, N02, CF3, halogen, and the number of carbon atoms is 1 to 10. An alkyl group or an alkoxy group having 1 to 10 carbon atoms. In this case, the "diamine component" means a diamine compound of the present invention including at least one of the chemical formula 10 or the chemical formula 23, and optionally other diamine compounds. In particular, the diamine compound represented by the chemical formula 10 or the chemical formula 23 of the present invention can be mixed with other diamine-based compounds having no optical activity, and the form 28 8 201247600 is formed into a polyamine or a polyimine, thereby providing a liquid crystal. The vertical alignment is stable. Light alignment. Therefore, it is possible to enable a diamine compound which can be used together with the chemical formula 10 or a chemical, for example, a diamine compound represented by X〇, diaminodiphenyl decane, 4,4,-diamino: fluorene, anthracene Amine, 4,4'-ether, M, diaminodiphenyl sulfone, 3,3,_ _ 虱 一 本 硫 硫 #一 methyl _4,4,-diamino phenyl, 44,- two gas Benzoquinone, 4,4,_:amino: face, ^: aminonaphthalene, 2:2, _methyl fluorene biphenyl, 5_A base small (4, amino benzene, trimethyl sulphide, 6_教基_1_(4,-Amino stupid)-like trimethylmethane, 3,4,-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diamino Benzophenone, 4,4,-diaminobenzophenone, 2,2-bis[4·(4-aminophenyloxy)phenyl]propyl, 2,2_bis[4_ (4-gas basic Oxy)) hexafluoropropane, 2,2-bis (4-amino) hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl] hydrazine, hydrazine, 4_bis(4_aminophenyloxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis (4 -aminobenzene)_1〇_hydroquinone, 2,7-diaminopurine, 9,9-bis (4- Aminobenzene) field, 4,4,-decylene-bis(2-chloroaniline), 2,2,5,5,-tetrachloro-4,4,-diaminobiphenyl, 2,2'- Dichloro-4,4,-diamino-5,5,-dimethoxybiphenyl, 3,3,-dimethoxy-4,4'-diaminobiphenyl, K4'- (p-sub Phenylisopropylidene) bis-amine, 4,4'-(m.phenylene isopropylidene)diphenylamine, 2,2'.bis[4-(4.amino-2-trifluoromethyl) Phenoxy)benzene]hexafluoropropane, 4,4,-diamino-2,2,-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino_2_trifluoromethane) Phenoxy]-octafluorobiphenyl, bis(4-aminophenyl)benzidine, _(4-aminophenyl)-13,3-trimethyl-1H-indan-5-amine, 1, 1_m-phenylenediamine, L3·propylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 1,4-cyclohexane Diamine 29 201247600 (l,4-diaminocyclohexane), isophorone diamine, tetrahydrobicyclopentadienyl diamine, dioxime [6.2.1.02'7]-undecyl dimethicone An aliphatic or alicyclic diamine such as an amine, 4,4'. methylene bis(cyclohexylamine), 1,3-bis(d-methyl)cyclohexane; 2,3- Gas-based 吼11, 2,6-diamino ratio bite, 3,4-diamino ratio. Ding, 2,4-diaminopyrimidine, 5,6-diamino-2,3-cyanopyrazine, 5,6-diamino-2,4-dihydroxy oxime, 2,4-disorganyl-6-indolyl-based 1,3,5-triazine, 1,4-bis(3- Aminopropyl) 0 嗓, 2,4-dioxa-6-isopropoxy-1,3,5-tripa, 2,4-diamino-6-oxime-1,3,5 -bifluorene, 2,4-monomethyl-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-diazine, 2,4-diamino-l , 3,5-triazine, 4,6-diamino-2-vinyl-s-di-β-Qin, 2,4-diamino-5-phenyl. Tef sitting, 2,6-diaminopurine, 5,6-diamino-l,3-monomethylurea. 3,5-diamino-1,2,4-trimethyl, 6,9-diamino-2-ethoxy-acridine Lactate, 3,8- Diamino-6-phenylphenanthridine, 1,4 diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl), 1-(3,5-monoaminophenyl)_3_ One or more diamine compounds of the group consisting of mercapto amber imine and iota (3,5-diaminocarbyl)-3-octylsuccinimide. The tetracarboxylic dianhydride used for synthesizing the polyamic acid or polyimine in the liquid crystal alignment agent of the present invention may be an alicyclic tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride, and an aromatic tetracarboxylic acid. Diacid anhydride. A specific example of the alicyclic tetra(tetra)g gf may be (3)+cyclobutanthine tetrazoic acid di-hepatic 1,2-monomethyl-1,2,3,4-cyclobutane sulphonic acid two-needle, 1,3 _二曱基_1,2,3,4_ 地丁烧四船二gf, 二气-(3)+环丁烧四减二针, 酉夂一酐, 1,2,4,5-环己院Tetra-acidic acid, wild, 3,3,,4,4,_dicyclohexyltetrahydroacid 201247600 monoanhydride cis 3,7-monobutylcyclooctane-1,5-dilute-1,2,5, 6. Four-acidic acid two-needle, 2,3,5-dicarboxy-pivalyl acetic acid dianhydride, 5·(2,5-dioxotetrahydro- 3_furanyl)_3_ decyl-3-ring -1,2-di-n-dianhydride, 3,5,6-trisyl- 2_sulfanyl norbornene-2:3,5:6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylate Acid dianhydride, hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl)-naphtho[i,2_c]-pyranyl-1,3_di_, 1,3,3&amp; 4,5,91)-Hexahydro-5-methyl-5(tetrahydro-2,5-dioxo-3-0-folyl)-naphtho[l,2-c]-furan_1,3_ Diketone, 1,3,3&amp;,4,5,%-hexahydro-5-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c ]·furan_1,3_dione, i,3,3a,4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-indolyl)_ Cai and [i,2-c]-a --1,3-diketone, 1,3,3&amp;,4,5,%-hexahydro-7-ethyl-5(tetrahydro-2,5-dioxo-3-furanyl)·naphtho [l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-8-fluorenyl_5 (tetrahydro-2,5-dioxo-3 -furyl)-naphtho[l,2-c]-furan-1,3·dione, 1,3,3a,4,5,9b-hexa-6-ethyl-5 (four l-2 ,5-dioxo-3-indolyl)-naphtho[l,2-c]-a-propan-1,3·dione, 1,3,3\4,5,91&gt;hexahydro-5 , 8-dimethyl-5(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]·furan-1,3-dione, 5- (2,5 -dihydrotetrahydrofuranyl)_3_mercapto-3-cycloethene-1,2-dicarboxylic anhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic acid Dihydride, 3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), and the like. A specific example of the aliphatic tetracarboxylic dianhydride may be butadiene tetracarboxylic acid dianhydride or the like. Specific examples of the aromatic tetracarboxylic dianhydride may be pyromellitic dianhydride, 4,4'-biphenyltetrahydro acid (4,4'-Biphthalic dianhydride), 3,3', 4,4 '-Bistokerone tetracarboxylic dianhydride, 3,3',4,4'-bisphenylphosphine tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3, 6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3,4,4,-dimethyldiphenylnonane tetracarboxylic acid Anhydride, 3,3,,4,4'-tetraphenylnonane tetracarboxylate 31 201247600 Acid dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4,-bis (3,4-di Carboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4,-bis(3,4-dicarboxyphenoxy Di-p-propyl propane dianhydride, 3,3,,4,4,-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride Bis(phthalic acid) phenyl phosphine oxide, ρ·jumpy-bis(trimylphthalic acid) dianhydride, m_peptidyl _ Bis(diphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)_4,4,_ diphenyl Ether dianhydride, bis(triphenylphthalic acid)-4,4,-diphenylnonane dianhydride, ethylene glycol bis (dehydrated trimellitic acid ester), propylene glycol _ double (dehydrated benzene triacetate) Acid S曰), 1,4-butanediol-bis(hydrogen trimellitate), hydrazine, 6-hexanediol-bis(dehydrated trimellitic acid vinegar), 1,8-octanediol-double (dehydrated trimellitate), 2,2. bis(4-phenyl)propane-bis(hydrogen trimellitate), and the like. The reaction 'receives poly-proline. By the diamine component including the diamine compound represented by the chemical formula 10 or the diamine compound represented by the chemical formula 23, and the tetracarboxylic dianhydride for the synthesis reaction of the polyporphyrin The liver and the diamine are substituted with 1 equivalent of an amine group, and the fourth more preferably is used in an amount of about 0.7 to a fraction as follows: preferably about 0.2 to 2 equivalents based on the acid anhydride in the phthalic acid dianhydride in the diamine component. 2 equivalents. The hour, more preferably may be 3, and the reaction time may preferably be from about 1 hour to 72 hours to 48 hours. 'As long as it is capable of dissolving at this time, the organic solvent used is not particularly limited to the polyamine acid produced by 201247600. For example, it can be N-methyl-2-» pirone, N,N-didecyl. Acetamide, N,N-didecylguanamine, 3-butoxy-N,N-dimercaptopropane decylamine, 3-methoxy-N,N-dimercaptopropane decylamine, 3 a non-protic compound such as a decylamine compound such as hexyloxy_n,N-dimercaptopropane decylamine, dimercaptosulfoxide, γ-butyrolactone, tetramethylurea or hexamethylphosphonium diamine; A phenolic compound such as aging, diphenyl benzene, phenol, phenol halide, and the like. On the other hand, the organic solvent can simultaneously use a poor solvent of a poly-proline such as an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon or a hydrocarbon in the range of the polyamic acid formed without precipitation. Solvent). Specific examples of such a poor solvent may be decyl alcohol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monoterpene ether, ethyl lactate. , butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl fluorenone, cyclohexanone, decyl acetate, ethyl acetate, butyl acetate, Methyl methoxy propanoate, ethoxylate Ethyl propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol, ethylene glycol, ethylene glycol _n-propyl ether, ethylene glycol I-propyl ether, ethylene glycol-n-butyl thief, ethylene glycol dioxime, ethylene glycol ethyl acetate test, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol monoterpene acetate, diethylene glycol monoethyl acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, l,4-di Gas butane, trichloroethane, gas benzene, o-dichlorobenzene, hexane, heptane, octane, stupid, stupid, diphenyl, isoamyl propionate, isovaleric acid, diisoamyl Check and so on. Thereby, a reaction "solution" which is carried out by dissolving polylysine is obtained. Thereafter, the reaction solution is added to a large amount of a poor solvent to obtain a precipitate, and poly-proline is obtained by drying the precipitate under reduced pressure or by vacuum distillation under an evaporator and removing the reaction solution. Alternatively, the poly 33 201247600 tyrosine can be redissolved in an organic solvent, and then the polyamine can be purified by performing one or more processes of precipitating with a poor solvent or by evaporating, distilling and removing the evaporator. acid. The polyimine is obtained by dehydrating the obtained polylysine by ring closure to carry out oxime imidization. The method for performing the dehydration ring closure of the polyaminic acid is preferably (1) a method of permeating the poly-proline acid, or (π) dissolving the poly-proline in an organic solvent, and adding a dehydrating agent and a dehydration ring in the solution. After the catalyst is used, it is carried out according to the method of heating required. The reaction temperature in the method of (1) heating the polyamic acid is preferably from about 50C to about 200. (:, more preferably from about 60 ° C to about 170 ° C. The reaction time is preferably from about 1 hour to about 8 hours, more preferably from about 3 hours to about 5 hours. The right reaction temperature is lower than 50. (:, cannot The dehydration ring-closure reaction is sufficiently carried out, and if the reaction temperature exceeds 200 C, the molecular weight of the obtained polyimine may be decreased. On the other hand, the dehydrating agent is added to the solution of the (u) polylysine and The method of dehydrating the reading agent's dehydrating agent can be used as a kind of ethyl acetate, propionic anhydride, and di-acetic acid anhydride. The amount of dehydrating agent used varies according to the desired imidization rate. The structure of the proline of 丨莫耳麟麟, preferably from about 〇. 〇丨 耳 to about 20 摩尔. Moreover, the dehydration ring-closing catalyst can be used, for example, pyridine, triterpene pyridine, dimethylpyrazine-ethylamine, etc. The amine, but is not limited thereto. The amount of the dehydration ring-closing catalyst used is preferably from about 0.01 mol to about 0 mol with respect to the 1 mol dehydrating agent used. The more the dehydrating agent and the dehydration ring-closing agent are used, The higher the imidization rate of hydrazine. The organic solution of dehydration_reaction An organic solvent which has been enumerated for the synthesis of poly-acid can be used. The reaction temperature of the dehydration ring-closure reaction is preferably from about 10 to about 180 ° C, more preferably from about 10 ° C to about 15 Torr. The hydrazine reaction time is preferably From about 1 hour to about 8 hours, more preferably from about 3 hours to about 5 hours. The polyimine obtained in the method (i) can be used directly for preparing a liquid crystal alignment agent, or the obtained polyfluorene can be obtained. After the imine is purified, it is used in the preparation of the liquid crystal alignment agent. On the other hand, the polyimine-containing reaction solution obtained in the method (ii) can be directly used for preparing a liquid crystal alignment agent, and can also be used from the reaction. After the dehydrating agent and the dehydration ring-closing catalyst are removed from the solution, it is used in the preparation of the liquid crystal alignment agent, and after the polyimine is separated, it is used in the preparation of the liquid crystal alignment agent, or after the isolated polyimine is purified. It is only used for the preparation of liquid crystal alignment agent. The method of removing the dehydration drum dehydration ring-closing catalysis from the reaction solution can be carried out according to the method of (4) replacement, etc. The separation and purification of the polyimine can be separated from the above polyaluminate. And purified The liquid crystal alignment of the present invention contains the poly-acid or the poly-decylene obtained in the same manner as needed, and the polymer and the additive are dissolved in an organic solvent. The organic solvent used in the liquid crystal alignment agent of the present invention is, for example, methyl-2-scale, γ-butene, γ-τ internal amine, N N_ is N-N,N-dimethylacetamide, 4_ via base ketone methyl _ ' : ▲ carbamazepine, butyl acrylate, butyl acetate, methyl methoxypropionate, methyl ether, lactitol (tetra), ethylene glycol, ethylene glycol Milking two. Acid ethyl vinegar, ethylene bis. 丨 amp amp amp butyl ether Acetate, diethylene glycol dimethyl, ethylene glycol monoterpene glycol monomethyl ether, diethylene glycol monoacetic acid, diethylene t-ether, monoethylene glycol diethyl ether, digan Zhizaojia acetic acid, two Gan Alcohol mono 35 201247600 Ethyl acetate, 3-butoxy-N,N-dimethylpropane decylamine, 3-methoxy-N,N-methylpropanolamine, 3-hexyloxy-N , N-dimethylpropanamide, and the like. The concentration of the solid matter (the component other than the liquid crystal alignment agent/mixture) in the liquid crystal alignment agent of the present invention must be appropriately selected in consideration of the viscosity, the volatility, and the like, with respect to the total weight of the liquid crystal alignment agent. The solid concentration thereof may preferably range from about 1 weight to about 10% by weight (wt%). When the solid content concentration is less than 1% by weight (wt%), the thickness of the film formed by coating the liquid crystal alignment agent is too thin to obtain a good liquid crystal alignment film, and on the other hand, when the solid content exceeds When the content is 10% by weight (wt%), the thickness of the formed film is too thick, and a good liquid crystal alignment film is not obtained as well, and the viscosity of the liquid crystal alignment agent is increased to lower the coating characteristics. Liquid Crystal Alignment Film A liquid crystal alignment film is formed by applying the liquid crystal alignment agent of the present invention to a substrate and heating it. The liquid crystal alignment agent can be applied, for example, by a roll coating method, a spin method, a printing method, an inkjet method, or the like, and then the surface is coated by heating to form a liquid crystal alignment film. After the liquid crystal alignment agent is applied, in order to prevent the flow of the applied alignment agent liquid, it is preferable to perform preheating (prebaking). The pre-baking temperature is preferably about 3 Torr. It is about 300 ° C, more preferably about 40. (: to about 20 (TC, most preferably from about 50 ° C to about 150 ° . . . thereafter 'completely remove the solvent' and in order to thermally imidize the polyglycolic acid, a firing (post-baking) process can be performed. The firing (post-baking) temperature is preferably from about 80 ° C to about 300 ° C, more preferably about 12 〇. (: to about 250 ° C. Thus, it can also be coated through 36 8 201247600. An amine liquid crystal alignment agent, after which the organic solvent is removed to form a coating film which is to be a liquid crystal alignment film, and dehydration ring closure is performed by heating to form an alignment film which is further imidized. The thickness of the liquid crystal alignment film formed is preferably It is about 0.001 μηι to about 1 μηη, more preferably about 〇005 μηη to about 0.5 μηη. The alignment treatment is performed by irradiating the surface of the dried coating film with ultraviolet rays having a wavelength ranging from about 15 〇 nm to 45 〇 nm. It is possible to illuminate an energy having an exposure intensity of from about % mJ/cm to about 1 〇j/cm, preferably from about 5 〇〇mj/cm 2 to about 5 j/cm 2 . After passing through the optical alignment and a series of processes, Able to achieve excellent thermal stability and high alignment Liquid crystal alignment device The present invention provides a liquid crystal display device including the above liquid crystal alignment film. The foregoing liquid crystal display device can be prepared by a method common in the art, for example, a binder containing a spherical spacer. After bonding the two substrates on which the liquid crystal alignment film of the present invention is formed to the end of one of the substrates, the substrate is bonded to the other substrate' to complete the bonding of the cells. Then, the liquid crystal is injected into the completed The liquid crystal cell is completed by heat treatment in the cell. The liquid crystal display device of the present invention having the liquid crystal alignment film exhibits an excellent alignment state and is excellent in thermal stability in a liquid crystal alignment state. The effects and effects of the present invention are described in more detail. However, these examples are only intended to be illustrative of the present invention and are not intended to limit the scope of the invention. <Examples> 37 201247600 Diamines Preparation of a compound-like compound Example 1 Preparation of a chemical formula 10 (n=l, R broad R8=H, PG=BOC) [Reaction Scheme I]

MsCI, TEA ~~M0~~&quot; 將95.0g(〇.74mol)原料物質4,4,4-三氟丁烷-1-醇（化學 式 1)溶解於 135 mL (0.97 mol)三乙胺(triethylamine，TEA) 與1 L之二氣甲烷(Methylene Chloride，MC)，並將其冷卻至0 °C。於30分鐘内，在所生成的物質中緩慢地添加63.0mL(62.0 mol)甲續醯氯(methanesulfonyl chloride，MsCI)。在 0°C 下擾拌 該混合物10分鐘，並在室溫下使之反應2小時，以製備甲磺 酸 4,4,4-三 I 丁 基酉旨（4,4,4-trifluorobutyl methanesulfonate)(化 學式2)。 對化學式2之化合物進行NMR檢測，其結果如下。 ]H NMR (400 MHz, CDC13) δ 4.30 (t, 2Η), 3.04 (s, 3H), 2.28 (m, 2H), 2.05 (m, 2H) [反應式II]MsCI, TEA ~~M0~~&quot; Dissolve 95.0g (〇.74mol) of the starting material 4,4,4-trifluorobutan-1-ol (Formula 1) in 135 mL (0.97 mol) of triethylamine ( Triethylamine, TEA) and 1 L of Methane Chloride (MC) were cooled to 0 °C. 63.0 mL (62.0 mol) of methanesulfonyl chloride (MsCI) was slowly added to the resulting material over 30 minutes. The mixture was spoiled at 0 ° C for 10 minutes and allowed to react at room temperature for 2 hours to prepare 4,4,4-trifluorobutyl methanesulfonate (chemical formula). 2). The compound of Chemical Formula 2 was subjected to NMR measurement, and the results were as follows. ]H NMR (400 MHz, CDC13) δ 4.30 (t, 2Η), 3.04 (s, 3H), 2.28 (m, 2H), 2.05 (m, 2H) [Reaction formula II]

接著，將75.9 g ( 0.56 mol ) 4-經基苯乙酉同 (4-hydroxyacetophenone)(化學式 3 )、55.2 g ( 0.84 mol) KOH、 146 g (0.61 mol)化學式2之化合物曱磺酸4,4,4-三氟丁基醋 (4,4,4-trifluorobutyl methanesulfonate) ' 4.60 g (0.03 mol) ΚΙ 38 ⑧ 201247600 加至2 L乙醇中’並迴流(reflux)24小時，以製備4’- (4,4,4-三敦丁 氧基）笨乙酮（4’-(4,4,4-trifluorobutoxy)acetopherione)〇b 學式4)。 對化學式4之化合物進行NMR檢測，其結果如下。 JH NMR (400 MHz &gt; CDC13) δ 7.95 (d, 2Η), 6.91 (d, 2H), 4.10 (t, 2H), 2.56 (s, 3H), 2.32 (m, 2H), 2.09 (m, 2H) [反應式III]Next, 75.9 g (0.56 mol) 4-hydroxyacetophenone (chemical formula 3), 55.2 g (0.84 mol) KOH, 146 g (0.61 mol) of the compound of the formula 2 sulfonic acid 4, 4 , 4,4,4-trifluorobutyl methanesulfonate ' 4.60 g (0.03 mol) ΚΙ 38 8 201247600 Add to 2 L of ethanol 'recooled for 24 hours to prepare 4'- ( 4,4,4-Tridontoxy) acetophenone (4'-(4,4,4-trifluorobutoxy)acetopherione) 〇b. The compound of Chemical Formula 4 was subjected to NMR measurement, and the results were as follows. JH NMR (400 MHz &gt; CDC13) δ 7.95 (d, 2Η), 6.91 (d, 2H), 4.10 (t, 2H), 2.56 (s, 3H), 2.32 (m, 2H), 2.09 (m, 2H) [Reaction formula III]

將 51.6 g (0.34 mol) 4-甲醯苯曱酸(4-formylbenzoic acid) (化學式 5)、84.6 g (0.34 mol) 4，- (4,4,4-三氟丁氧基）苯乙 _l(4，-(4,4,4-trifluorobutoxy)acetophenone)(化學式 4)加至 2.2 L之80%乙醇中，並在此加入170 mL之25%的NaOH後，在 室溫使之反應24小時。其後添加1.5L之H20,並冷卻至0。(：。 恭加HC1直到pH值達到2為止，接著攪拌2小時，以製備化 學式6之化合物。 對化學式6之化合物進行NMR檢測，其結果如下。 ]H NMR (400 MHz, MeOD) δ 8.20 (d, 2H) ' 8.09 (d, 1H), 8-00 (s, 4H), 7.76 (d, 1H), 7.12 (d, 2H), 4.18 (t, 2H), 2.45 (m, 2H)、1.99 (m，2H) [反應式IV] 39 20124760051.6 g (0.34 mol) 4-formylbenzoic acid (chemical formula 5), 84.6 g (0.34 mol) 4,-(4,4,4-trifluorobutoxy)benzene _ l(4,-(4,4,4-trifluorobutoxy)acetophenone) (Chemical Formula 4) was added to 2.2 L of 80% ethanol, and 170 mL of 25% NaOH was added thereto, and then reacted at room temperature. hour. 1.5 L of H20 was then added and cooled to zero. (:. Add HC1 until the pH reaches 2, and then stir for 2 hours to prepare a compound of Chemical Formula 6. The NMR detection of the compound of Chemical Formula 6 is as follows. ]H NMR (400 MHz, MeOD) δ 8.20 ( d, 2H) ' 8.09 (d, 1H), 8-00 (s, 4H), 7.76 (d, 1H), 7.12 (d, 2H), 4.18 (t, 2H), 2.45 (m, 2H), 1.99 (m, 2H) [Reaction formula IV] 39 201247600

RzRz

OH Pd/C, Ha(g^ MeOHOH Pd/C, Ha(g^ MeOH

〇 Rt R4 EDCI, DMAP, DIPEA〇 Rt R4 EDCI, DMAP, DIPEA

將 70.0 g ( 0.30 mol ) 2,4-二硝基苯乙酸 (2,4-dinitrophenylacetic acid)(化學式 7)溶解於 700 mL 之 THF 後，慢慢加入39.0 mL (2.00 mol) BH3SMe3 ’並使其迴流3 小時。此後，將反應物質冷卻至室溫之後，加入100 mL之3N 的 HC1 ，以製備 2- ( 2,4-二硝基苯）乙醇 (2-(2,4-dinitrophenyl)ethanol)。在高壓蚤中放入 64.0 g (0.30 mol ) 2- ( 2,4-二硝基笨）乙醇(2-(2,4-dinitrophenyl)ethanol)、1.2 L曱醇、以及濕度為50%之10%Pd/C (64.0g，10%w/w)，並 在氫氣(3 atm)氣氛中使之反應12小時，以製備2-(2,4-二胺基 苯）乙醇(2-(2,4-diaminophenyl)ethanol)。將 54.0 g (0.30 mol) 2- (2,4-二胺基苯）乙醇(2-(2,4-diaminophenyl)ethanol)溶解於 600 mL之THF/500 mL之aq-NaHC03後，在〇°C下慢慢加入 165 g (〇·76 mol) Boc20。其後，在室溫下使之反應24小時而 製備化學式8之化合物。將60.0 g (0.17 mol)化學式8之化 201247600 合物溶解於1 L二氯甲燒(Methylene Chloride，MC)，並加入 83.6 g( 0.22 mol)化學式 3 之化合物、48.9 g( 0.26 mol)EDCI、 14.5g(0.12mol)DMAP、以及 ll9mL(0.68mol)DIPEA 後， 在室溫下使之反應12小時，以製備化學式9之化合物。 對化學式9之化合物進行NMR檢測，其結果如下。 lH NMR (400 MHz, CDC13) δ 8.05 (d, 4H) , 7.79 (m, 2H), 7.71 (d, 2H), 7.64 (d, 1H), 7.15 (d, 1H), 7.04 (b, 1H), 6.97 (d, 2H), 6.50 (b, 1H), 4.47 (t, 2H), 4.13 (t, 2H), 3.00 (t, 2H), 2.36 (m, 2H), 2.09 (m, 2H) [反應式V]After dissolving 70.0 g (0.30 mol) of 2,4-dinitrophenylacetic acid (chemical formula 7) in 700 mL of THF, slowly add 39.0 mL (2.00 mol) of BH3SMe3' and make it Reflux for 3 hours. Thereafter, after cooling the reaction mass to room temperature, 100 mL of 3N HCl was added to prepare 2-(2,4-dinitrophenyl)ethanol. 64.0 g (0.30 mol) of 2-(2,4-dinitrophenyl)ethanol, 1.2 L of sterol, and a humidity of 50% were placed in a high pressure crucible. %Pd/C (64.0 g, 10% w/w) and reacted in a hydrogen (3 atm) atmosphere for 12 hours to prepare 2-(2,4-diaminophenyl)ethanol (2-(2) , 4-diaminophenyl)ethanol). Dissolve 54.0 g (0.30 mol) of 2-(2,4-diaminophenyl)ethanol in 600 mL of THF/500 mL of aq-NaHC03 at 〇° Slowly add 165 g (〇·76 mol) of Boc20 under C. Thereafter, the compound of Chemical Formula 8 was prepared by allowing it to react at room temperature for 24 hours. 60.0 g (0.17 mol) of the chemical formula 201247600 was dissolved in 1 L of Methylene Chloride (MC), and 83.6 g (0.22 mol) of the compound of Chemical Formula 3, 48.9 g (0.26 mol) of EDCI, After 14.5 g (0.12 mol) of DMAP and ll9 mL (0.68 mol) of DIPEA, it was reacted at room temperature for 12 hours to prepare a compound of Chemical Formula 9. The compound of Chemical Formula 9 was subjected to NMR measurement, and the results were as follows. lH NMR (400 MHz, CDC13) δ 8.05 (d, 4H), 7.79 (m, 2H), 7.71 (d, 2H), 7.64 (d, 1H), 7.15 (d, 1H), 7.04 (b, 1H) , 6.97 (d, 2H), 6.50 (b, 1H), 4.47 (t, 2H), 4.13 (t, 2H), 3.00 (t, 2H), 2.36 (m, 2H), 2.09 (m, 2H) [ Reaction formula V]

將129g (0·18ιη〇1)化學式9之化合物溶解於^[二氯 曱烧(Methylene Chloride，MC) ’並在(TC下於1小時内緩慢加 入520 mL之TFA。其後，在室溫下進行4小時反應，透過減 壓除去溶劑’從而製備本發明之新型光配向劑單體(E)_2,4_二胺 基苯乙基-4- (3-氧代-3- (4- (4,4,4-三氟丁氧基）苯基）丙小 稀基）本曱酸醋（(E)-2,4-diaminophenethyl 4-(3-oxo-3-(4-(4,4,4-trifluorobutoxy)phenyl)pr〇p-i_enyl)benzoate) 201247600 (化學式10)。 對化學式10之化合物進行nmr檢測，其結果如下。 *H NMR (400 MHz, CDC13) δ 8.06 (m, 4Η), 7.82 (d, 1H), 7.71 (d，2H)，7.64 (d，1H)，6.97 (d，2H)，6.89 (d，1H)、6.10 (m， 2H)、4.47 (t，2H), 4.13 (t，2H), 3.89 (b，2H)，3.53 (b，2H)，2.89 (t， 2H)，2.33(m，2H)，2.11 (m，2H) 二胺類化合物之製備實施例2 化學式23 (n=l，RHRfH，PG=BOC時）化合物之製備 [反應式VI]129 g (0·18ιη〇1) of the compound of Chemical Formula 9 was dissolved in [Methylene Chloride (MC)' and slowly added 520 mL of TFA in 1 hour under TC. Thereafter, at room temperature The reaction was carried out for 4 hours, and the solvent was removed under reduced pressure to prepare a novel photo-aligning agent monomer (E) 2,4-diaminophenethyl-4-(3-oxo-3-(4-) of the present invention. (4,4,4-trifluorobutoxy)phenyl)propanyl) phthalic acid vinegar ((E)-2,4-diaminophenethyl 4-(3-oxo-3-(4-(4, 4,4-trifluorobutoxy)phenyl)pr〇p-i_enyl)benzoate) 201247600 (Chemical Formula 10). The compound of Chemical Formula 10 was subjected to nmr detection, and the results were as follows. *H NMR (400 MHz, CDC13) δ 8.06 (m, 4Η ), 7.82 (d, 1H), 7.71 (d, 2H), 7.64 (d, 1H), 6.97 (d, 2H), 6.89 (d, 1H), 6.10 (m, 2H), 4.47 (t, 2H) , 4.13 (t, 2H), 3.89 (b, 2H), 3.53 (b, 2H), 2.89 (t, 2H), 2.33 (m, 2H), 2.11 (m, 2H) Preparation Examples of Diamine Compounds 2 Preparation of the compound of the formula 23 (n=l, RHRfH, PG=BOC) [Reaction formula VI]

MsCI, TEA ~~MC OMs 將95.0 g (0.74 mol)原料物質4,4,4-三氟丁烷-1-醇（化學 式 1)溶解於 135 mL (0.97 mol)三乙胺(triethylamine，TEA) 與1 L之二氣曱烧(Methylene Chloride, MC)，並在30分鐘内於 〇 °C條件下慢慢加入63.0 mL ( 0.81 mol )甲磺醯氣 (methanesulfonyl chloride，MsCI)。在 0。〇 下攪拌該混合物 1〇 分 鐘，並在室溫下進行2小時反應而製備曱磺酸4,4,4-三氟丁基 酯(4,4,4-trifluorobutyl methanesulfonate)(化學式 2)。 對化學式2之化合物進行NMR檢測，其結果如下。 'H NMR (400 MHz, CDC13) δ 4.30 (t, 2H), 3.04 (s, 3H), 2.28 (m, 2H), 2.05 (m, 2H) [反應式VII] 201247600MsCI, TEA ~~MC OMs Dissolve 95.0 g (0.74 mol) of the starting material 4,4,4-trifluorobutan-1-ol (Formula 1) in 135 mL (0.97 mol) of triethylamine (TEA). With 1 L of Methylene Chloride (MC), 63.0 mL (0.81 mol) of methanesulfonyl chloride (MsCI) was slowly added under -30 °C for 30 minutes. At 0. The mixture was stirred for 1 Torr at room temperature, and reacted at room temperature for 2 hours to prepare 4,4,4-trifluorobutyl methanesulfonate (Chemical Formula 2). The compound of Chemical Formula 2 was subjected to NMR measurement, and the results were as follows. 'H NMR (400 MHz, CDC13) δ 4.30 (t, 2H), 3.04 (s, 3H), 2.28 (m, 2H), 2.05 (m, 2H) [Reaction formula VII] 201247600

將 72.5 g(0.53 111〇1)4-經基本乙酮(4_]^(11'〇\丫&amp;〇61:〇卩11611〇116) (化學式3)溶解於700 mL之DMF，並使之與由反應式VI 製備尤 152 g( 0.64 mol)甲石買酸 4,4,4-三氟丁基@旨(trifluorobutyl methanesulfonate)(化學式 2)以及 no g (0 80 m〇丨）k2C03 進行反應’以製備化學式4之化合物（98.0 g，75%)。將98.0 g(0.4 mol)化學式4之化合物溶解於1.2 L之MC/MeOH(2:l )， 並在10°C以下慢慢加入192 g (0.4 mol) Bu4NBr2。使其反應 12小時’以製備化學式11之化合物（12〇 g，93%)。將120 g (0.4 mol)化學式11之化合物加至丨93 mL ( 1.11 mol)亞磷 酸三乙酯(triethylphosphite)中，迴流(reflux)4小時，以製備化 學式12之化合物（60 g，43%)。 對化學式12之化合物進行NMR檢測，其結果如下。 'H NMR (400 MHz, CDC13) δ 8.01 (d, 2H), 6.93 (d, 2H), 4.12 (m，6H)，3.61 (s，1H)，3.53 (s，1H)，2.34 (m，2H), 2.08 (m， 43 201247600 2H), 1.33 (t, 6H) [反應式VIII]72.5 g (0.53 111〇1) 4- via basic ethyl ketone (4_]^(11'〇\丫&amp;〇61:〇卩11611〇116) (chemical formula 3) was dissolved in 700 mL of DMF and allowed to Reacts with tetrafluorobutyl methanesulfonate (chemical formula 2) and no g (0 80 m〇丨) k2C03 prepared from reaction formula VI, especially 152 g (0.64 mol) of formazan acid (4,4,4-trifluorobutyl) 'To prepare a compound of formula 4 (98.0 g, 75%). 98.0 g (0.4 mol) of the compound of formula 4 was dissolved in 1.2 L of MC/MeOH (2:1), and slowly added to 192 below 10 °C. g (0.4 mol) Bu4NBr2. It was reacted for 12 hours to prepare a compound of formula 11 (12 〇g, 93%). 120 g (0.4 mol) of the compound of formula 11 was added to 丨93 mL (1.11 mol) of phosphorous acid. In a triethylphosphite, refluxing for 4 hours to prepare a compound of Chemical Formula 12 (60 g, 43%). The compound of Chemical Formula 12 was subjected to NMR measurement, and the results were as follows. 'H NMR (400 MHz, CDC13) ) δ 8.01 (d, 2H), 6.93 (d, 2H), 4.12 (m, 6H), 3.61 (s, 1H), 3.53 (s, 1H), 2.34 (m, 2H), 2.08 (m, 43 201247600) 2H), 1.33 (t, 6H) [Reaction formula VIII]

KOH TcFTKOH TcFT

BuLi ACN THF %BuLi ACN THF %

H2S〇4H2S〇4

0&gt;N0&gt;N

將 100g(0.55mol)二苯甲酮(benzophenone)(化學式 13) 與 30·8 g (0.55 mol) KOH 加至 700 mL 乙腈(acetonitrile)中， 並迴流(reflux)2小時，以製備化學式14之化合物（98 0 g，100 g (0.55 mol) of benzophenone (Chemical Formula 13) and 30·8 g (0.55 mol) of KOH were added to 700 mL of acetonitrile, and refluxed for 2 hours to prepare Chemical Formula 14 Compound (98 0 g,

87% )。在-78 C的氮氣氣氛中，在88·0 mL ( 1.67 mol)乙腈 (acetonitrile)與900 mL之THF的混合溶液中慢慢加入480 mL 201247600 (1.19 mol)的 BuLi ( 2.5 M solution in hexane )，攪拌 3 小時， 再加入98.0 g( 0.48 mol)化學式14化合物和600 mL之THF， 並進行3小時反應’以製備化學式15化合物（l〇2 g，87%)。 將 460 mL 濃硫酸(concentrated sulfuric acid)和 69.1 mL 發煙硝 酸(fuming nitric acid)冷卻至 〇 至-5°C之間，並加至 91.5 g(0.37 mol)化學式15化合物中，在不到l〇°c的溫度下使之反應5 小時而製備化學式16化合物（103 g，83%)。 在 2 L 之 50%(v/v)的 H2S04 中加入 109 g (0.32 mol)化學 式16化合物，並在150°C下使之反應後降低溫度至室溫。之後 透過萃取反應物而製備化學式17化合物。將143 g (0.32 mol) 化學式17化合物溶解於1 L的THF，並在0°C慢慢添加90.5 mL (0.96mol) BH3SMe2，之後在50°C下使之反應5小時而製備 化學式18化合物。 在高壓釜中加入87 g(0.25 mol)化學式18化合物、1.2 L 甲醇、以及濕度為50%之10%Pd/C (18.0g，20%w/w)，並在 氫氣(3 atm)氣氛下使之反應24小時，以製備化學式19化合 物。將75.0 g (0.26 mol)化學式19化合物溶解於1.3 L之 THF/1.3 L 之 sat-NaHC03，並在 0°C 慢慢加入 172 g ( 0.79 mol) Boc20。其後，在室溫使之反應24小時而製備化學式20化合 物（98.4 g，77%)。 透過使用梦膠層析管柱（silica gel column chromatography)[EtOAc/MC (1:1 —3:1)]純化化學式 20 化合 物。將98.4 g (0.20 mol)化學式20化合物溶解於！·5 L乙腈 (acetonitrile)，之後於前述溶液中加入91.1 g (0.61 mol) 4-曱 45 201247600 醯苯曱酸(4-formylbenzoic acid)、167 g( 0.81 mol) EDCI、12.4 g (0.11 mol) DMAP 以及 87.0 mL (0.50 mol) DIPEA，並在 不到10°C溫度下使之進行反應，以製備化學式21化合物（80.0 g, 53% )〇 將利用反應式VII所製備之82.3 g (0.22 mol)化學式12 化合物溶解於650 mL之DMF，並加入將60%NaH (8.95 g， 0.23 mol)分散於DMF ( 520 mL )之溶液，進行24小時反應。 在此混合將64.5 g( 86.0 mmol)化學式21化合物溶解於650 mL 之DMF的溶液’並在室溫下使之反應14小時，以製備化學式 22之化合物（67.1 g ’ 65%)。將化學式22化合物使用管柱層 析法(column chromatography)[己烷(Hexane)/ 乙酸乙酯(EtOAc) (2:1)]進行純化。其後’將53.1 g (44.0 mmol)化學式22 化合物溶解於1.8 L乙腈(acetonitile)，並在0°C氮氣氣氛中加 入15.7mL ( 110 mmol) TMSI與260mL乙腈之混合溶液，而 後使之反應2小時。透過減壓除去溶劑，再使用管柱層析法 (column chromatography) (MC/EA=3:1)純化生成物，以製備 化學式23化合物（30_0g，68%)。 對化學式23之化合物進行NMR檢測，其結果如下。 'H NMR (400 MHz, CDC13) δ 8.00 (dd, 8H), 7.73 (d, 2H), 7.57 (d, 4H)，7.47(d, 2H)、7.06 (d，4H)，6.95 (d, 4H)，6.64 (d, 4H)， 4.21 (t, 4H), 4.09 (t, 4H), 3.61 (b, 4H), 2.63 (t, 4H), 2.35 (m, 4H), 2.11 (m，4H) 下面’記載使用本發明之二胺類化合物和羧酸二酐製備聚 醯胺酸、聚醯亞胺、液晶配向劑及液晶配向膜之實施例和與此 ⑧ 201247600 對比的比較例。而且透過比較及評價，使用本發明二胺類化合 物之配向膜的特性較優秀。 實施例1 將0.83 g之4,4·亞曱基二胺(MDA)、1.17 g對-苯二胺 (p-PDA)、1.57 g胆甾烧醇（3,5-二氨基苯曱酸酯）（CDB)以及 1.03 g之利用上述二胺類化合物製備實施例1製得之化學式1〇 (其中n=l ’ 所示的化合物’在氮氣氣氛下溶解於 49.0 g之N-甲基-2-吡咯烷酮(NMP)中，然後於維持20¾的同 時添加4.48 g之2,3,5-三羧基環戊烷基乙酸酐(2,3,5-tricarboxy cyclopentyl acetic anhydride，TCAAH)。其後’添加 32.7 g 之 γ- 丁内酯(GBL)，並使之反應24小時。反應後添加36.4 g之γ· 丁内酯(GBL)、2.73 g之Ν-曱基-2-吡咯烷酮(ΝΜΡ)以及51.8 g 乙二醇單丁醚(BC)，以獲得5 wt%的液晶配向劑a。（黏性13 cP，25〇C ) 實施例2 將0.75 g之4,4-亞曱基二胺(MDA)、〇.99 g對笨二胺 (p-PDA)、2.09 g胆留烷醇（3,5·二氨基苯曱酸醋）（CDB)以及 1.54 g之利用上述二胺類化合物製備實施例1製得之化學式 (其中n=l，R^RfH)所示的化合物，在氮氣氣氛下溶解於 53.2 g之N-曱基-2-吼咯烷酮(NMP)中，然後於維持2〇。(：的同 時添加4.48 g之2,3,5-三叛基環戊烧基乙酸酐(tcaaH)。其 後，添加35.5 g之γ-丁内酯(GBL)，並使之反應24小時。反應 後添加39.4 g之γ-丁内酯（GBL)、2·96 g之N-曱基_2_吡咯烷酮 (NMP)以及56.2 g乙二醇單了醚(BC)，以獲得5⑽的液晶配 201247600 向劑B。（黏性i〇 cP，25¾ ) 實施例3 將0.63 g之4,4_亞甲基二胺(MDA)、〇 84 g對-苯二胺 (p PDA) 2.61 g胆甾炫醇（3,5_二氣基苯甲酸酉旨）（cdb)以及 2.05 g之利用上述二胺類化合物製備實施例丨製得之化學式ι〇 (其中n=l ’ Ri〜r8=h)所示的化合物，在氮氣氣氛下溶解於 57.3 g之N-甲基_2·吡咯烷酮(NMp)中，然後於維持2〇它的同 時添加4.48 g之2,3,5-三竣基環戊烧基乙酸軒(tcaaH)。其 後，添加38.2 g之γ_丁内酯(GBL)，並使之反應24小時。反應 後添加42.4 g之γ_丁内酯（GBL)、3 19 g之N_曱基_2_吡咯烷酉同 (NMP)減6G.5 g乙二醇單丁_〇 ’以獲得5讓的液晶配 向劑C。（黏性7 cp，25°C ) 實施例4 將〇.83轻之4,4-亞甲基二胺(]^八）、1.17经對_笨二胺 (p-PDA)、1·57 g胆甾烷醇（3,5_二氨基苯曱酸乙醋）（CDB)以 及2.01 g之利用上述二胺類化合物製備實施例2製得之化學式 23 (其中n=l ’ RpRfH)所示的化合物，在氮氣氣氛下溶解 於54.3 g之N-甲基-2-。比嘻烷酮(NMP) ’然後於維持20°C的同 時添加4.48 g之2,3,5-三羧基環戊烷基乙酸酐(TCAAH)。其 後’添加32.2 g之7 -丁内酯(GBL)，並使之反應24小時。反 應後添加44.2 g之7-丁内酯（GBL)、3_02 g之N-甲基-2-吡咯 烷酮(NMP)以及57.3 g乙二醇單丁醚(BC)，以獲得5 wt%的液 晶配向劑D。（黏性1〇 cp，25¾ ) 實施例5 ⑧ 48 201247600 將〇.75 g之4,4·亞甲基二胺(MDA)、0.99 g對-笨二胺 (pPDA) 2· g胆甾燒醇（3,5_二氨基苯曱酸乙酉旨）(cdb)2.〇9 g以及3.02 g之利用上述二胺類化合物製備實施例2製得之化 學式23 (其中㈣，心〜R8=h)所示的化合物，在氮氣氣氛下 溶解於61.2 g之N-甲基-2-吡咯烷酮(NMP)中，然後於維持2〇 °C的同時添加4.48 g之2,3,5-三羧基環戊烷基乙酸酐 (TCAAH)。其後，添加4〇.8g之γ-丁内酯(GBL)，並使之反應 24小時。反應後添加45 3 g之γ·丁内醋(GBL)、3 4〇经之Ν_ 甲基-2-吡咯烷酮(ΝΜΡ)以及64.6 g乙二醇單丁醚(BC)，以獲得 5 wt%的液晶配向劑e。（黏性9 cp，25。(：） 實施例6 將〇.5〇 g之4,4-亞甲基二胺(MDA)、0.68 g對-苯二胺 (P ) 2.10 g胆甾烧醇（3,5-二氨基苯曱酸乙酉旨）（cdb)以 及3.23 g之利用上述二胺類化合物製備實施例2製得之化學 23 Γ Φ 、 ，R^RfH)所示的化合物，在氮氣氣氛下溶解 於54.6 g &lt; N_甲基心比咯烷酮(NMp)中然後於維持的 同時添加3·6〇 g之2,3,5-三叛基環戊烧基乙酸酐(tcaaH)。其 後，添加3M g之γ·丁内醋(GBL)，並使之反應24小時。反應 後添加4〇‘4 §之丁内醋(咖）、3.03 g之N-甲基_2_吼錢酉同 (NMP)J^ S7.6 g乙二醇單丁_(BC) ’以獲得5 wt%的液晶配 向劑F。（黏性7 cp，25〇c ) 比較例1 將0.75§之4,4-亞曱基二胺(觀八）、1〇2§對_苯二胺 (P )以及5.56 g之胆甾烷醇（3,5-二氨基笨甲酸乙酯） 49 201247600 (CDB) ’在氮氣氣氛下溶解於69.0 g之Ν·曱基κ洛&amp;嗣 (ΝΜΡ)中，然後於維持20°C的同時添加5.40g之2,35_三緩基 環戊院基乙酸Sf(TCAAH)。其後’添加46.0 g之γ 丁内醋 (GBL)，並使之反應24小時。反應後添加97_15容之7_丁内醋 (GBL)、72.9 g之Ν-甲基-2-吡咯烷酮(ΝΜΡ)以及72 9 g乙二醇 單丁醚(BC)，以獲得5 wt°/〇液晶配向劑G。（黏性12 ep，25〇c ) 液晶配向膜及液晶單元之製備 用孔徑為1 μπι之過濾裝置過濾以上述方法獲得之液晶配 向劑Α〜G。使用旋轉裝置，以500 rpm的旋轉速度和1〇秒之 旋轉時間以及1800 rpm旋轉速度和20秒之旋轉時間，在設置 於玻璃基板一表面之具有ITO膜的透明導電膜上，分兩步驟塗 覆上述液晶配向劑A〜G，並透過在180艺下預固化6〇秒以及 在210°C下固化20分鐘來除去溶劑，以形成塗膜。 之後利用曝光裝置’以300 mJ/cm2，10 mW之強度曝光 30秒，從而製備具有液晶配向膜之兩個基板。接著，在前述兩 個具有液晶配向膜之基板、具有液晶配向膜的各外緣部，塗覆 包含有直徑為4 μιη之氧化銘球的環氧樹脂黏合劑後，使前述 兩個基板之液晶配向膜相互面對而疊壓，並固化黏合劑。接著 透過液晶注入口，於基板之間填充向列相液晶156〇1，〜 1.4780)後，用丙烯酸類光固化黏合劑密封液晶注入口，以製 備液晶顯示褒置。 &lt;實驗例&gt; 液晶單元之物性評價 評價方法 201247600 1.黏度 在25°c下利用 cannon黏度計測定動黏度，用比重計測定 比重後’將兩個測定值相乘而計算黏度。 2·預傾角 根據記載於文獻（T.J. Schffer等人發表於1980年j.，Appl Phys.，期刊，第19卷，第2013頁）之方法，用He_Ne激光，’ 透過結晶旋轉法測定。 3液晶之配向性 當接通/斷開液晶顯示裝置之電壓時，用顯微鏡觀察在液 晶顯示裝置中有無異常液晶區域，當無異常液晶區域時，判斷 為良好。 4.電壓維持率 對液晶顯示裝置施加5 V電壓60微秒後，測定解除施加 電壓16.67毫秒後的電壓維持率。 經由本發明之實施例及比較例製備之液晶顯示裝置的物 性評價結果如下表1所示。參照表1，可知與比較例相比’實 施例1至6曝光後之配向性顯著優秀。 [表1]液晶單元之特性比較 分類 預傾角 電壓維持率 配向性 曝光前 曝光後 實施例1 89° 99% 不良 良好 實施例2 89° 99% 不良 良好 實施例3 89° 99% 不良 良好 實施例4 89° 99% 不良 良好 實施例5 89° 99% 不良 良好 實施例6 89° 99% 不良 良好 比較例1 89° 99% 不良 不良 51 201247600 本發明之實施例及比較例之液晶配向照片如下表2所示。 參照下表2，在實施例1至6曝光後之照片中看不到液晶 區域，然而比較例在曝光前後之液晶區域差異並不大，由此可 知比較例為不良品。 [表2]液晶配向照片 分類 配向性 曝光前 曝光後 實施例1 _ 實施例2 實施例3 圓 實施例4 實施例5 1 實施例6 wm 比較例1 m _ 52 ⑧87%). In a nitrogen atmosphere of -78 C, slowly add 480 mL of 201247600 (1.19 mol) of BuLi (2.5 M solution in hexane) in a mixed solution of 88.0 mL (1.67 mol) of acetonitrile and 900 mL of THF. After stirring for 3 hours, 98.0 g (0.48 mol) of the compound of the formula 14 and 600 mL of THF were added, and the reaction was carried out for 3 hours to prepare a compound of the formula 15 (10 g, 87%). 460 mL of concentrated sulfuric acid and 69.1 mL of fuming nitric acid were cooled to between -5 ° C and added to 91.5 g (0.37 mol) of the chemical formula 15 in less than l The compound of Chemical Formula 16 (103 g, 83%) was prepared by reacting at a temperature of 〇 °c for 5 hours. 109 g (0.32 mol) of the compound of the formula 16 was added to 2 L of 50% (v/v) H2S04, and the reaction was allowed to proceed at 150 ° C to lower the temperature to room temperature. The compound of the formula 17 is then prepared by extracting the reactants. 143 g (0.32 mol) of the compound of the formula 17 was dissolved in 1 L of THF, and 90.5 mL (0.96 mol) of BH3SMe2 was slowly added at 0 ° C, and then reacted at 50 ° C for 5 hours to prepare a compound of the formula 18. 87 g (0.25 mol) of the chemical formula 18 compound, 1.2 L of methanol, and 10% Pd/C (18.0 g, 20% w/w) having a humidity of 50% were added to the autoclave, and under a hydrogen (3 atm) atmosphere. This was allowed to react for 24 hours to prepare a compound of Chemical Formula 19. 75.0 g (0.26 mol) of the compound of formula 19 was dissolved in 1.3 L of THF / 1.3 L of sat-NaHC03, and 172 g (0.79 mol) of Boc20 was slowly added at 0 °C. Thereafter, the compound of Chemical Formula 20 (98.4 g, 77%) was prepared by allowing it to react at room temperature for 24 hours. The chemical formula 20 compound was purified by using silica gel column chromatography [EtOAc/MC (1:1 - 3:1)]. Dissolve 98.4 g (0.20 mol) of the chemical formula 20 in! · 5 L acetonitrile, then add 91.1 g (0.61 mol) 4-曱45 201247600 4-formylbenzoic acid, 167 g (0.81 mol) EDCI, 12.4 g (0.11 mol) to the above solution. DMAP and 87.0 mL (0.50 mol) DIPEA were reacted at less than 10 ° C to prepare the compound of formula 21 (80.0 g, 53%). 82.3 g (0.22 mol) prepared by using the reaction formula VII The compound of the formula 12 was dissolved in 650 mL of DMF, and a solution of 60% NaH (8.95 g, 0.23 mol) dispersed in DMF (520 mL) was added, and the reaction was carried out for 24 hours. Here, 64.5 g (86.0 mmol) of the compound of the formula 21 was dissolved in a solution of 650 mL of DMF and reacted at room temperature for 14 hours to prepare a compound of the formula 22 (67.1 g '65%). The compound of the formula 22 was purified using column chromatography [hexane (Hexane) / ethyl acetate (EtOAc) (2: 1)]. Thereafter, 53.1 g (44.0 mmol) of the compound of the formula 22 was dissolved in 1.8 L of acetonitile, and a mixed solution of 15.7 mL (110 mmol) of TMSI and 260 mL of acetonitrile was added under a nitrogen atmosphere at 0 ° C, and then reacted 2 hour. The solvent was removed under reduced pressure, and the product was purified by column chromatography (MC/EA = 3:1) to give the compound of formula 23 (30 - 0 g, 68%). The compound of Chemical Formula 23 was subjected to NMR measurement, and the results were as follows. 'H NMR (400 MHz, CDC13) δ 8.00 (dd, 8H), 7.73 (d, 2H), 7.57 (d, 4H), 7.47 (d, 2H), 7.06 (d, 4H), 6.95 (d, 4H) ), 6.64 (d, 4H), 4.21 (t, 4H), 4.09 (t, 4H), 3.61 (b, 4H), 2.63 (t, 4H), 2.35 (m, 4H), 2.11 (m, 4H) The following describes an example in which a polyamine acid, a polyimine, a liquid crystal alignment agent, and a liquid crystal alignment film are prepared using the diamine compound of the present invention and a carboxylic acid dianhydride, and a comparative example in comparison with this Patent No. 8 201247600. Further, by comparison and evaluation, the characteristics of the alignment film using the diamine compound of the present invention are excellent. Example 1 0.83 g of 4,4-decylenediamine (MDA), 1.17 g of p-phenylenediamine (p-PDA), and 1.57 g of cholesteryl alcohol (3,5-diaminobenzoate) (CDB) and 1.03 g of the compound of the formula 1 prepared by using the above diamine compound (wherein n = l ', dissolved in 49.0 g of N-methyl-2 under a nitrogen atmosphere) - Pyrrolidone (NMP), then add 4.48 g of 2,3,5-tricarboxycyclopentyl acetic anhydride (TCAAH) while maintaining 203⁄4. 32.7 g of γ-butyrolactone (GBL) was allowed to react for 24 hours. After the reaction, 36.4 g of γ·butyrolactone (GBL), 2.73 g of fluorenyl-mercapto-2-pyrrolidone (ΝΜΡ) and 51.8 were added. g ethylene glycol monobutyl ether (BC) to obtain 5 wt% of liquid crystal alignment agent a. (viscosity 13 cP, 25 〇C) Example 2 0.75 g of 4,4-decylenediamine (MDA) , 〇.99 g to stupid diamine (p-PDA), 2.09 g of cholestyl alcohol (3,5-diaminobenzoic acid vinegar) (CDB), and 1.54 g of the preparation example using the above diamine compound a compound of the formula (where n = l, R ^ RfH), obtained in nitrogen gas Dissolved in 53.2 g of N-mercapto-2-pyrrolidone (NMP), and then maintained at 2 〇. (:: add 4.48 g of 2,3,5-tri-resylcyclopentyl B Anhydride (tcaaH). Thereafter, 35.5 g of γ-butyrolactone (GBL) was added and allowed to react for 24 hours. After the reaction, 39.4 g of γ-butyrolactone (GBL) and 2.96 g of N- were added. Mercapto-2-pyrrolidone (NMP) and 56.2 g of ethylene glycol monoether (BC) to obtain 5 (10) liquid crystal with 201247600 agent B. (viscosity i〇cP, 253⁄4) Example 3 0.63 g of 4 , 4_methylenediamine (MDA), 〇84 g p-phenylenediamine (p PDA) 2.61 g cholesteryl alcohol (3,5-di-hydroxybenzoic acid) (cdb) and 2.05 g The compound of the formula 〇 (where n = 1 ' Ri~r8 = h) prepared in Example 制备 was prepared by using the above diamine compound, and dissolved in 57.3 g of N-methyl-2·pyrrolidone under a nitrogen atmosphere. (NMp), then add 4.48 g of 2,3,5-trimercaptocyclopentylacetate (tcaaH) while maintaining 2 。. Thereafter, add 38.2 g of γ-butyrolactone (GBL) ) and allowed to react for 24 hours. After the reaction, 42.4 g of γ-butyrolactone (GBL) and 3 19 g of N_mercapto-2_pyrene were added. The alkylene complex (C) is reduced by 6 G. 5 g of ethylene glycol monobutyl _ 〇 ' to obtain 5 liquid crystal alignment agent C. (viscosity 7 cp, 25 ° C) Example 4 〇.83 light 4,4-methylenediamine (]^8), 1.17-pair _stupidine (p-PDA), 1.57 G-cholestyl alcohol (3,5-diaminobenzoic acid ethyl vinegar) (CDB) and 2.01 g of the chemical formula 23 (where n = l 'RpRfH) obtained by the preparation of the above diamine compound The compound was dissolved in 54.3 g of N-methyl-2- under a nitrogen atmosphere. More than decyl ketone (NMP)' was then added to 4.48 g of 2,3,5-tricarboxycyclopentaneacetic anhydride (TCAAH) while maintaining 20 °C. Thereafter, 32.2 g of 7-butyrolactone (GBL) was added and allowed to react for 24 hours. After the reaction, 44.2 g of 7-butyrolactone (GBL), 3_02 g of N-methyl-2-pyrrolidone (NMP) and 57.3 g of ethylene glycol monobutyl ether (BC) were added to obtain a liquid crystal alignment of 5 wt%. Agent D. (viscosity 1 〇 cp, 253⁄4 ) Example 5 8 48 201247600 〇.75 g of 4,4·methylenediamine (MDA), 0.99 g of p-diphenylamine (pPDA) 2·g cholestasis Alcohol (3,5-diaminobenzoic acid ethyl ester) (cdb) 2. 〇 9 g and 3.02 g of the chemical formula 23 prepared by using the above diamine compound to prepare Example 2 (wherein (4), heart ~ R8 = h The compound shown was dissolved in 61.2 g of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere, and then 4.48 g of 2,3,5-tricarboxyl ring was added while maintaining 2 °C. Pentyl acetic anhydride (TCAAH). Thereafter, 4 〇.8 g of γ-butyrolactone (GBL) was added and allowed to react for 24 hours. After the reaction, 45 3 g of γ·butyrolactone (GBL), 3 4 hydrazine Νmethyl-2-pyrrolidone (ΝΜΡ), and 64.6 g of ethylene glycol monobutyl ether (BC) were added to obtain 5 wt%. Liquid crystal alignment agent e. (viscosity 9 cp, 25. (:) Example 6 4,4-methylenediamine (MDA), 0.68 g of p-phenylenediamine (P) 2.10 g of cholesteric alcohol (3,5-diaminobenzoic acid ethyl ester) (cdb) and 3.23 g of the compound represented by the preparation of the above chemical compound 23 Γ Φ, R^RfH) obtained by using the above diamine compound, in nitrogen Dissolved in 54.6 g of N_methyl heart pyrrolidone (NMp) under an atmosphere and then added 3·6〇g of 2,3,5-tritylcyclopentyl acetic anhydride (tcaaH) while maintaining ). Thereafter, 3 M g of γ·butyrolactone (GBL) was added and allowed to react for 24 hours. After the reaction, add 4〇'4 § of the vinegar (caffe), 3.03 g of N-methyl_2_吼钱酉同(NMP)J^S7.6 g ethylene glycol monobutyl _(BC) ' 5 wt% of the liquid crystal alignment agent F was obtained. (viscosity 7 cp, 25 〇 c ) Comparative Example 1 0.75 § 4,4-decylenediamine (Fig. 8), 1 〇 2 § p-phenylenediamine (P), and 5.56 g of cholestane Alcohol (3,5-diaminobenzoic acid ethyl ester) 49 201247600 (CDB) 'Dissolved in 69.0 g of hydrazine in a nitrogen atmosphere, and then maintained at 20 ° C while maintaining 20 ° C 5.40 g of 2,35-trisylcyclopentanyl acetic acid Sf (TCAAH) was added. Thereafter, 46.0 g of γ-butyl vinegar (GBL) was added and allowed to react for 24 hours. After the reaction, 97_15-7-7 vinegar (GBL), 72.9 g of hydrazine-methyl-2-pyrrolidone (ΝΜΡ) and 72 9 g of ethylene glycol monobutyl ether (BC) were added to obtain 5 wt ° / 〇 Liquid crystal alignment agent G. (viscosity 12 ep, 25 〇 c) Preparation of liquid crystal alignment film and liquid crystal cell The liquid crystal alignment agent Α to G obtained by the above method was filtered by a filter device having a pore size of 1 μm. Using a rotating device, a rotation speed of 500 rpm and a rotation time of 1 sec and a rotation speed of 1800 rpm and a rotation time of 20 seconds were applied in two steps on a transparent conductive film having an ITO film disposed on one surface of the glass substrate. The liquid crystal alignment agents A to G were applied, and the solvent was removed by pre-curing for 6 sec seconds at 180 ° C and curing at 210 ° C for 20 minutes to form a coating film. Thereafter, it was exposed to an intensity of 300 mJ/cm 2 and 10 mW for 30 seconds by means of an exposure apparatus ', thereby preparing two substrates having a liquid crystal alignment film. Next, after coating the outer edge portion of the two substrates having the liquid crystal alignment film and the liquid crystal alignment film, an epoxy resin adhesive containing an oxidation balloon having a diameter of 4 μm is applied, and then the liquid crystals of the two substrates are applied. The alignment films face each other and are laminated, and the adhesive is cured. Then, through the liquid crystal injection port, the nematic liquid crystals 156〇1 to 1.4780 are filled between the substrates, and then the liquid crystal injection port is sealed with an acrylic photocurable adhesive to prepare a liquid crystal display device. &lt;Experimental Example&gt; Evaluation of physical properties of liquid crystal cell Evaluation method 201247600 1. Viscosity The dynamic viscosity was measured at 25 ° C using a cannon viscometer, and the specific gravity was measured by a hydrometer. The two measured values were multiplied to calculate the viscosity. 2. Pretilt angle According to the method described in the literature (T.J. Schffer et al., 1980, J., Appl Phys., Journal, Vol. 19, p. 2013), a He_Ne laser was used, which was measured by a crystal rotation method. 3 Orientation of liquid crystal When the voltage of the liquid crystal display device was turned on/off, the presence or absence of an abnormal liquid crystal region in the liquid crystal display device was observed with a microscope, and it was judged to be good when there was no abnormal liquid crystal region. 4. Voltage holding ratio After a voltage of 5 V was applied to the liquid crystal display device for 60 μsec, the voltage holding ratio after the application of the voltage of 16.67 msec was released was measured. The physical property evaluation results of the liquid crystal display devices prepared according to the examples and comparative examples of the present invention are shown in Table 1 below. Referring to Table 1, it is understood that the alignment properties after the exposure of Examples 1 to 6 are remarkably excellent as compared with the comparative examples. [Table 1] Characteristics of Liquid Crystal Cell Comparison Classification Pretilt Voltage Maintenance Rate Orientation Exposure before Exposure Example 1 89° 99% Poor Good Example 2 89° 99% Poor Good Example 3 89° 99% Poor Good Example 4 89° 99% Poor good Example 5 89° 99% Poor good Example 6 89° 99% Poor good Comparative Example 1 89° 99% Unfavorable defect 51 201247600 The liquid crystal alignment photographs of the examples and comparative examples of the present invention are shown in the following table. 2 is shown. Referring to the following Table 2, the liquid crystal regions were not observed in the photographs after the exposure of Examples 1 to 6. However, in the comparative examples, the difference in the liquid crystal regions before and after the exposure was not large, and thus the comparative example was considered to be a defective product. [Table 2] Liquid crystal alignment photo classification Orientation before exposure Post exposure After Example 1 - Example 2 Example 3 Circle Example 4 Example 5 1 Example 6 wm Comparative Example 1 m _ 52 8

Claims (1)

201247600 七、申請專利範圍： . 1. 一種二胺類化合物，係以下列化學式10表示， [化學式10]201247600 VII. Patent application scope: 1. A diamine compound represented by the following chemical formula 10, [Chemical Formula 10] 該化學式10中， η為1至20之整數； R!至R8為相同或者相異，且分別獨立地表示H、CN、N02、 CF3、鹵素、碳原子數為1至10之烷基、或者碳原子數為1至 10之烷氧基。 2. 如申請專利範圍第1項所述之二胺類化合物，其中η 為1至5之整數；R!至118為相同或者相異，且分別獨立地表 示Η或者碳原子數為1至10之烷基。 3. —種二胺類化合物，係以下列化學式23表示， [化學式23] 53 201247600In the chemical formula 10, η is an integer of 1 to 20; R! to R8 are the same or different, and each independently represents H, CN, N02, CF3, halogen, an alkyl group having 1 to 10 carbon atoms, or An alkoxy group having 1 to 10 carbon atoms. 2. The diamine compound according to claim 1, wherein η is an integer of 1 to 5; R! to 118 are the same or different, and each independently represents hydrazine or has 1 to 10 carbon atoms; Alkyl group. 3. A diamine compound represented by the following chemical formula 23, [Chemical Formula 23] 53 201247600 該化學式23中， η為1至20之整數； R!至尺8為相同或者相異，且分別獨立地表示H、CN、N02、 CF3、_素、碳原子數為1至10之烷基、或者碳原子數為1至 10之烷氧基。 4. 如申請專利範圍第3項所述之二胺類化合物，其中η 為1至5之整數；R!至R8為相同或者相異，且分別獨立地表 示Η或者碳原子數為1至10之烷基。 5. —種液晶配向劑，包含有： 聚醯胺酸或者聚醯亞胺，該聚醯胺酸或者聚醯亞胺係透過 使一二胺成分與一四叛酸二酐反應而獲得，該二胺成分包含有 以下列化學式10所表示的二胺類化合物， [化學式10] ⑧ 201247600In the chemical formula 23, η is an integer of 1 to 20; R! to 8 are the same or different, and each independently represents H, CN, N02, CF3, _, and an alkyl group having 1 to 10 carbon atoms. Or an alkoxy group having 1 to 10 carbon atoms. 4. The diamine compound according to claim 3, wherein η is an integer of 1 to 5; R! to R8 are the same or different, and each independently represents hydrazine or has 1 to 10 carbon atoms; Alkyl group. 5. A liquid crystal alignment agent comprising: polylysine or polyimine, which is obtained by reacting a monoamine component with a tetracarboxylic acid dianhydride, The diamine component contains a diamine compound represented by the following Chemical Formula 10, [Chemical Formula 10] 8 201247600 〇^/vr-cF3 該化學式10中， η為1至20之整數； R!至R8為相同或者相異，且分別獨立地表示H、CN、N02、 CF3、鹵素、碳原子數為1至10之烷基、或者碳原子數為1至 10之烷氧基。 6. —種液晶配向劑，包含有： 聚醯胺酸或者聚醯亞胺，該聚醯胺酸或者聚醯亞胺係透過 使一二胺成分與一四叛酸二酐反應而獲得，該二胺成分包含有 以下列化學式23所表示的二胺類化合物， [化學式23]〇^/vr-cF3 In the chemical formula 10, η is an integer of 1 to 20; R! to R8 are the same or different, and each independently represents H, CN, N02, CF3, halogen, and the number of carbon atoms is 1 to An alkyl group of 10 or an alkoxy group having 1 to 10 carbon atoms. 6. A liquid crystal alignment agent comprising: polylysine or polyimine, which is obtained by reacting a monoamine component with a tetracarboxylic acid dianhydride, The diamine component contains a diamine compound represented by the following Chemical Formula 23, [Chemical Formula 23] 該化學式23中， 55 201247600 η為1至20之整數； Rl至R8為相同或者相異’且分別獨立地表示h、cn、no2、 CF3、函素、碳原子數為】至1〇之烷基、或者碳原子數為】至 10之烷氧基。 7.如申請專利範圍第5項或者第6項所述之液晶配向 劑，更包含有選自由p_苯二胺、m—苯二胺、4,4，_二氨基二苯甲 烷、4,4’-二氨基二苯乙烷、4,4，_二氨基二苯硫醚、4,4，_二氨基 一苯砜、3,3 -二曱基_4,4’_二氨基聯笨、4,4’_二氨基苯醯替苯 胺、4,4’-二氨基二笨醚、！,5_二氨基萘、2,2，_二甲基_4,4,二氨 基聯笨、5-氨基-1- (4’-氨基苯）]，3,3_三甲基節滿、6_氨基小 (4 -氨基苯）-1，3,3-三甲基茚滿、3,4，-二氨基二苯醚、3,3，-二 氨基二苯甲酮、3,4’-二氨基二苯甲酮、4,4，_二氨基二苯甲酮、 2,2-雙[4- (4-氨基笨氧基）苯基]丙烧、2,2_雙[4_ (4氨基苯氧 基）苯基]六IL丙烧、2,2·雙（4-氨基苯）六氟丙烧、2,2-雙[4-(4-氨基苯氧基）苯基]砜、14_雙（4_氨基苯氧基）苯、 雙（4-氨基笨氧基）苯、ι，3·雙（3·氨基笨氧基）苯、9 9_雙（4· 氨基笨）-10-氫蒽、2,7-二氨基芴、9,9-雙（4-氨基苯）芴、4,4，_ 亞甲基-雙（2-氣苯胺）、2,2’，5,5，-四氣-4,4，·二氨基聯苯、2,2’-二氯-4,4’-二氨基-5,5’-二甲氧基聯苯、3,3，_二甲氧基_4,4,二氨 基聯笨、1，4,4 - (p-亞苯基異亞丙基）雙苯胺、4,4，_ (m亞苯 基異亞丙基）雙苯胺、2,2’-雙[4- (4-氨基-2-三氟甲基苯氧基） ， 笨]六氟丙烷、4,4’-二氨基-2,2，-雙（三氟甲基）聯苯、4,4，_雙[(4- . 氨基-2-二氟甲基）笨氧基]-八氟聯苯、二（‘氨基苯）聯苯胺、 1- (4-氨基苯）-1，3,3-三甲基_1H•茚滿_5_胺、u•間苯二甲胺、 ⑧ 56 201247600 1，3-丙二胺、四亞甲基二胺、戊二胺、六亞甲基二胺、庚二胺、 辛一胺、壬二胺、1，4·環己二胺、異佛爾酮二胺、四氫化二枣 戊亞二縣二胺、三環㈤丄巧十—碳稀二，基二胺、^ 基雙（環已胺）、U·雙（氨甲基）環己财脂肪族或脂環 族二胺」2,3-二氨基吡啶、2,6·二氨基吡啶、3,4二氨基吡啶： 2,4-二氨基喷。定、5,6_二氨基_2,3_二氮料、5,6_二氨基·认二 羥基嘧啶、2,4-二氨基-6-二甲基氨基_丨，3,5_三嗪、丨，‘雙（Z 氨丙基）哌嗪、2,4_二氨基-6-異丙氧基-1，3,5-三嗪、2,4-二氨基 •6·甲氧基-1，3,5-三嗪、2,4-二氨基_6_苯基.13,5.三嗪、认二^ 基-6-甲基-s-三嗪' 2,4-二氨基_1，3,5_三嗪、4,6_二教基_2_乙烯 基-s-三嗪、2,4-二氨基_5_苯基噻唑、2,6-二氨基嘌呤、5,6_二氨 基-1，3-一甲基脲〇密咬、3,5-二氨基·ι，2,4-三唾、6,9-二氨基_2 乙氧基吖啶乳酸鹽、3,8_二氨基_6_苯基菲咬、Μ-二氨基派'^秦、 3,6-二氨基吖啶、雙（4_氨基苯基）苯胺、丨_ (3,5_二氨基笨基） -3-癸基琥拍醯亞胺以及1_ (3,5_二氨基苯）_3_辛基琥珀醯亞胺 所構成之族群中之一種以上的二胺類化合物。 8. —種液晶配向膜，係由申請專利範圍第5項至第7項 中之任一項所述之液晶配向劑所形成。 9. 一種液晶顯示裝置’具有如申請專利範圍第8項所述 之液晶配向膜。 10. —種二胺類化合物之製備方法’該二胺類化合物係由 下列化學式10表示，該製備方法包括以下步驟： 透過使下列化學式6表示之化合物與下列化學式8表示之 化合物反應，以製備下列化學式9表示之化合物；以及 57 201247600 去除以下列化學式9表示之化合物中之保護基PG (Protecting group)； [化學式6] R6 0 Ri | | H〇 IT Rs R3^^〇^M^cf3 0 R7 R4 [化學式8] NH-PGIn the chemical formula 23, 55 201247600 η is an integer of 1 to 20; R1 to R8 are the same or different 'and independently represent h, cn, no 2, CF 3 , a hydroxyl group, and a carbon number of 1 to 1 Å. A group or an alkoxy group having a carbon number of from 10 to 10. 7. The liquid crystal alignment agent according to claim 5 or 6, further comprising selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 4,4,diaminodiphenylmethane, 4, 4'-diaminodiphenylethane, 4,4,-diaminodiphenyl sulfide, 4,4,-diamino-phenylene sulfone, 3,3-dimercapto-4,4'-diamino , 4,4'-diaminobenzoquinone, 4,4'-diaminodiphenyl ether,! , 5_diaminonaphthalene, 2,2,-dimethyl-4,4,diaminobiphenyl, 5-amino-1-(4'-aminobenzene)], 3,3_trimethyl, 6_Amino small (4-aminophenyl)-1,3,3-trimethylindan, 3,4,-diaminodiphenyl ether, 3,3,-diaminobenzophenone, 3,4' -diaminobenzophenone, 4,4,-diaminobenzophenone, 2,2-bis[4-(4-aminophenyloxy)phenyl]propane, 2,2_bis[4_ ( 4aminophenoxy)phenyl]hexapropylpropene, 2,2·bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone , 14_bis(4-aminophenoxy)benzene, bis(4-aminophenyloxy)benzene, iota,3·bis(3·aminophenyloxy)benzene, 9 9_bis(4·amino stupid) -10-hydroquinone, 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4,_methylene-bis(2-aniline), 2,2',5 ,5,-tetraqi-4,4,diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3,_ Dimethoxy- 4,4,diamino-biphenyl, 1,4,4-(p-phenylene isopropylidene)diphenylamine, 4,4,_(m-phenyleneidene) double Aniline, 2,2'-bis[4-(4-amino-2-trifluoro) Methylphenoxy), stupid]hexafluoropropane, 4,4'-diamino-2,2,-bis(trifluoromethyl)biphenyl, 4,4,_bis[(4-.amino-2) -difluoromethyl) phenoxy]-octafluorobiphenyl, bis('aminophenyl)benzidine, 1-(4-aminophenyl)-1,3,3-trimethyl_1H•茚满_5 _amine, u•m-xylylenediamine, 8 56 201247600 1,3-propanediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine, heptanediamine, octylamine, bismuth Amine, 1,4, cyclohexanediamine, isophorone diamine, tetrahydrogenated jujube, pentylene diamine, tricyclic (five) 丄巧十-carbon dibasic, bisamine, ^ bis (cyclo Amine), U·bis(aminomethyl)cyclohexanyl aliphatic or alicyclic diamine” 2,3-diaminopyridine, 2,6·diaminopyridine, 3,4 diaminopyridine: 2,4- Diamino spray. Ding, 5,6-diamino-2,3-diaza, 5,6-diamino-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-oxime, 3,5_three Oxazine, hydrazine, 'bis(Z-aminopropyl)piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino•6·methoxy -1,3,5-triazine, 2,4-diamino-6-phenyl.13,5.triazine, bis-bis-6-methyl-s-triazine' 2,4-diamino _1,3,5_triazine, 4,6-dichoyl-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5 , 6-diamino-1,3-methylurea guanidine, 3,5-diamino·ι, 2,4-tris, 6,9-diamino 2 ethoxy acridine lactate, 3,8-diamino_6_phenylphenanthrene, anthracene-diamino-p-methyl, 3,6-diaminoacridine, bis(4-aminophenyl)aniline, 丨_ (3,5_2 One or more diamine compounds of the group consisting of -3-mercaptosyl sulfoximine and 1_(3,5-diaminophenyl)_3-octyl succinimide. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 5 to 7. A liquid crystal display device' having a liquid crystal alignment film according to item 8 of the patent application. 10. A method for producing a diamine compound, which is represented by the following Chemical Formula 10, which comprises the steps of: preparing a compound represented by the following Chemical Formula 6 by reacting a compound represented by the following Chemical Formula 8 with a compound represented by the following Chemical Formula 8 a compound represented by the following Chemical Formula 9; and 57 201247600 Removal of a protecting group PG (Protecting group) in the compound represented by the following Chemical Formula 9; [Chemical Formula 6] R6 0 Ri | | H〇IT Rs R3^^〇^M^cf3 0 R7 R4 [Chemical Formula 8] NH-PG [化學式9][Chemical Formula 9] PG-HN [化學式10]PG-HN [Chemical Formula 10] h2n 該化學式6、8、9及10中， η為1至20之整數； R,至尺8為相同或者相異，且分別獨立地表示H、CN、N02、 CF3、鹵素、碳原子數為1至10之烷基、或者碳原子數為1至 201247600 10之烷氧基； PG為選自由苄氧幾基（carbobenzyloxy，Cbz)、對-甲氧基 苄基幾基（p-Methoxybenzyl carbonyl，Moz )、叔丁氧 Μ 基 (tert-butyloxycarbonyl, BOC ) 、9-芴曱氧叛基 (9-fluorenylmethyloxycarbonyl，FMOC )、乙醯基（acetyl, Ac )、 苯曱醢基（benzoyl，Bz )、苄基（benzyl, Bn )、胺基曱酸鹽 (Carbamate)、對-曱氧基苄基（p-methoxybenzyl，PMB)、3,4-二曱氧基苄基（3,4-dimethoxybenzyl，DMPM)、對-甲氧基苯基 (p-methoxypheyl，PMP)、甲苯磺醯基（tosyi，Ts)、以及對硝 基苯磺醯基(nosyl, Ns)所構成之族群中的保護基(Pr〇tecting group) ° 11. 一種二胺類化合物之製備方法，該二胺類化合物係由 下列化學式23表示’該製備方法包括以下步驟： ,' 透過使下列化學式12表示之化合物與下列化學式2ι表、 之化合物反應，而製備下列化學式22表示之化合物；以及不 去除以下列化學式22表示之化合物中之保護義p (Protecting group)； [化學式12]H2n In the chemical formulas 6, 8, 9 and 10, η is an integer from 1 to 20; R, to the size 8 are the same or different, and each independently represents H, CN, N02, CF3, halogen, and the number of carbon atoms is An alkyl group of 1 to 10 or an alkoxy group having 1 to 201247600 10; PG is selected from the group consisting of carbobenzyloxy (Cbz) and p-Methoxybenzyl carbonyl (p-Methoxybenzyl carbonyl, Moz), tert-butyloxycarbonyl (BOC), 9-fluorenylmethyloxycarbonyl (FMOC), acetyl (Ac), benzoyl (Bz), Benzyl (benzyl, Bn), carbamate, p-methoxybenzyl (PMB), 3,4-dimethoxybenzyl (DMM) a protecting group in the group consisting of p-methoxypheyl (PMP), tosyi (Ts), and p-nitrophenylsulfonyl (Ns) (Pr) 〇tecting group) ° 11. A method for preparing a diamine compound, which is represented by the following chemical formula 23 'The preparation method comprises the following steps: , ' The compound represented by the following Chemical Formula 12 is reacted with a compound represented by the following Chemical Formula 2, to prepare a compound represented by the following Chemical Formula 22; and the protecting group p (Protecting group) in the compound represented by the following Chemical Formula 22 is not removed; [Chemical Formula 12] ] [化學式21] 59 201247600[Chemical Formula 21] 59 201247600 [化學式22][Chemical Formula 22] [化學式23] 60 201247600[Chemical Formula 23] 60 201247600 該化學式12、21、22及23中 η為1至20之整數； 至為相同或者相異，且分別獨立地表示h、CN、N02、 CF3、齒素、碳原子數為1至1〇之烷基、或者碳原子數為1至 10之烷氧基； PG為選自由苄氧幾基（carbobenzyloxy，Cbz)、對-甲氧基 苄基幾基（p-Methoxybenzyl carbonyl, Moz )、叔丁 氧幾基 (tert-butyloxycarbonyl, BOC ) 、 9-芴甲氧羰基 (9-fluorenylmethyloxycarbonyl，FMOC )、乙醯基（acetyl, Ac )、 苯曱醯基（benzoyl，Bz )、苄基（benzyl，Bn )、胺基曱酸鹽 (Carbamate)、對-曱氧基~ 基（p-methoxybenzyl，PMB)、3,4_ 二甲氧基苄基（3，4-dimethoxybenzyl，DMPM )、對-甲氧基苯基 (p-methoxyphenyl，PMP)、曱苯磺醯基（t〇syl，Ts)、以及對确 基苯磺醯基（nosyl，Ns)所構成之族群中的保護基(pr〇tecting 201247600 group)。 201247600 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： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： [化學式10]In the chemical formulas 12, 21, 22 and 23, η is an integer of 1 to 20; to be the same or different, and independently represent h, CN, N02, CF3, dentate, and the number of carbon atoms is 1 to 1 Å. An alkyl group or an alkoxy group having 1 to 10 carbon atoms; PG is selected from the group consisting of carbobenzyloxy (Cbz), p-Methoxybenzyl carbonyl (Moz), and tert-butyl Tert-butyloxycarbonyl (BOC), 9-fluorenylmethyloxycarbonyl (FMOC), acetyl (Ac), benzoyl (Bz), benzyl (benzyl, Bn) ), Carbamate, p-methoxybenzyl (PMB), 3,4-dimethoxybenzyl (DMPM), p-methoxy P-methoxyphenyl (PMP), terpene sulfonyl (t〇syl, Ts), and a protecting group in the group consisting of nosyl (Ns) (pr〇tecting 201247600 group ). 201247600 IV. Designation of representative drawings: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: [Chemical Formula 10] ] [化學式23] 201247600[Chemical Formula 23] 201247600 該化學式10及23中，η為1至20之整數；心至尺8為相 同或者相異，且分別獨立地表示Η、CN、N〇2、CF3、鹵素、 碳原子數為1至10的烷基或烷氧基。In the chemical formulas 10 and 23, η is an integer of 1 to 20; the core to the ruler 8 are the same or different, and each independently represents Η, CN, N〇2, CF3, halogen, and the number of carbon atoms is 1 to 10. Alkyl or alkoxy.
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