TW201718709A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDF

Info

Publication number
TW201718709A
TW201718709A TW105124225A TW105124225A TW201718709A TW 201718709 A TW201718709 A TW 201718709A TW 105124225 A TW105124225 A TW 105124225A TW 105124225 A TW105124225 A TW 105124225A TW 201718709 A TW201718709 A TW 201718709A
Authority
TW
Taiwan
Prior art keywords
liquid crystal
crystal alignment
alignment agent
component
polyphthalate
Prior art date
Application number
TW105124225A
Other languages
Chinese (zh)
Other versions
TWI781910B (en
Inventor
Hiroki Yamagiwa
Takao Hori
Original Assignee
Nissan Chemical Ind Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Ind Ltd filed Critical Nissan Chemical Ind Ltd
Publication of TW201718709A publication Critical patent/TW201718709A/en
Application granted granted Critical
Publication of TWI781910B publication Critical patent/TWI781910B/en

Links

Classifications

    • 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
    • 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

Landscapes

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

Abstract

Provided are a polyamic acid ester capable of exhibiting various types of characteristics at high levels even when being blended with various polyamic acids, and a polyamic acid ester/polyamic acid blend-based liquid crystal alignment agent. This liquid crystal alignment agent contains: a polyamic acid ester (A) having a repeating unit represented by formula (1) and a repeating unit represented by formula (2); and a polyamic acid (B) (the definitions of the signs in the formulae are as described in the specification).

Description

液晶配向劑、液晶配向膜及液晶顯示元件 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

本發明係關於含有聚醯胺酸酯的液晶配向劑、以及由前述液晶配向劑所得到的液晶配向膜及液晶顯示元件。 The present invention relates to a liquid crystal alignment agent containing a polyphthalate, and a liquid crystal alignment film and a liquid crystal display element obtained from the liquid crystal alignment agent.

液晶顯示元件現在被廣泛使用作為數位相機、筆記型電腦、移動攜帶終端等的顯示元件。液晶顯示元件係一般由液晶、液晶配向膜、電極、基板等的構成構件所構築，又因應其用途等而採用各種的驅動方式。例如為了實現液晶顯示元件的廣視野角化，故採用使用橫向電場的IPS(In Plane Switching)驅動方式、或進而其改良型的FFS(Fringe-Field Switching)驅動方式等。 Liquid crystal display elements are now widely used as display elements of digital cameras, notebook computers, mobile portable terminals, and the like. The liquid crystal display element is generally constructed of constituent members such as a liquid crystal, a liquid crystal alignment film, an electrode, and a substrate, and various driving methods are employed depending on the application and the like. For example, in order to achieve a wide viewing angle of the liquid crystal display device, an IPS (In Plane Switching) driving method using a lateral electric field or a modified FFS (Fringe-Field Switching) driving method or the like is used.

作為上述驅動方式所使用的液晶配向膜，係廣泛地使用利用聚醯胺酸的液晶配向膜，但為了進而滿足提升液晶配向性之要求，故使用利用聚醯胺酸酯的液晶配向劑。 A liquid crystal alignment film using polyacrylic acid is widely used as the liquid crystal alignment film used in the above-described driving method. However, in order to further satisfy the requirement of improving liquid crystal alignment, a liquid crystal alignment agent using polyphthalate is used.

使用聚醯胺酸酯(以下亦稱為PAE)的液晶配向劑，為了滿足液晶顯示元件所需要的各種特性，大多與聚醯胺酸 (以下亦稱為PAA)以摻合之形式來使用(以下將如此般的液晶配向劑亦稱為PAE/PAA摻合系液晶配向劑)。 A liquid crystal alignment agent using a polyphthalate (hereinafter also referred to as PAE) is often used with polylysine in order to satisfy various characteristics required for a liquid crystal display element. (hereinafter also referred to as PAA) is used in the form of blending (hereinafter, such a liquid crystal alignment agent is also referred to as a PAE/PAA blending liquid crystal alignment agent).

但，從塗布PAE/PAA摻合系液晶配向劑時之PAE、PAA及溶劑之舉動，卻屢屢產生所得到的液晶配向膜並無法滿足液晶顯示元件所需要的各種特性之情形。為了解決此問題，報告著一種摻合特定構造的PAA、與PAE的液晶配向劑(專利文獻1)。 However, the behavior of PAE, PAA, and solvent in the case of coating a PAE/PAA blended liquid crystal alignment agent repeatedly produces the liquid crystal alignment film which does not satisfy various characteristics required for the liquid crystal display element. In order to solve this problem, a liquid crystal alignment agent which blends PAA of a specific structure and PAE is reported (Patent Document 1).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]國際公報WO2014-157143號說明書 [Patent Document 1] International Publication WO2014-157143

但，隨著近年液晶顯示元件的高精細化，液晶配向劑亦被要求著以高等級來兼具各種特性。其中，可用於與PAE做摻合的PAA之材料被限定於特定構造，將難以對聚醯胺酸、進而是使用此者的PAE/PAA摻合系液晶配向劑賦予各種特性。 However, with the recent high definition of liquid crystal display elements, liquid crystal alignment agents are required to have various characteristics at a high level. Among them, the material of the PAA which can be used for blending with PAE is limited to a specific structure, and it is difficult to impart various properties to poly-proline, and further to PAE/PAA blending liquid crystal alignment agent using the same.

因此，本發明的課題係開發一種PAE，其係即使是與不論何種的PAA做摻合亦可以高等級來兼具各種特性，以及開發使用如此般的PAE的PAE/PAA摻合系液晶配向劑。 Therefore, the subject of the present invention is to develop a PAE which can have various characteristics at a high level even if blended with any PAA, and develops a PAE/PAA blending liquid crystal alignment using such a PAE. Agent.

本發明人經重複檢討之結果發現一種使用特定構造的二胺作為原料而成的PAE，藉由該PAE可不依附於所摻合的PAA之構造，並賦予具有優異的液晶配向性或電氣特性等的液晶配向膜的PAE/PAA摻合系液晶配向劑，進而完成本發明。 As a result of repeated review, the inventors have found a PAE using a specific structure of a diamine as a raw material, by which the PAE can be attached to the structure of the blended PAA, and imparts excellent liquid crystal alignment or electrical properties. The PAE/PAA blending liquid crystal alignment agent of the liquid crystal alignment film further completes the present invention.

即，本發明係如同下述。 That is, the present invention is as follows.

1.一種液晶配向劑，其特徵係含有聚醯胺酸酯(A)、與聚醯胺酸(B)，該聚醯胺酸酯(A)具有下述式(1)所表示的重複單位及式(2)所表示的重複單位， (式中，R1為碳數1~6之烷基，R2~R5相互獨立為氫原子或碳數1~6之烷基，Y1為下述式(Y1-2)所表示的2價有機基，Y2為選自由下述式(Y2-1)及(Y2-2)所成之群之至少1種的2價有機基， (式中，A1及A5分別獨立為單鍵、或碳數1~5之伸烷基，A2及A4分別獨立為碳數1~5之伸烷基，A3為碳數1~6之伸烷基、或伸環烷基，B1及B2分別獨立為單鍵、-O-、-NH-、-NMe-、-C(=O)-、-C(=O)O-、-C(=O)NH-、-C(=O)NMe-、-OC(=O)-、-NHC(=O)-、或-N(Me)C(=O)-，D1為tert-丁氧基羰基、或9-茀基甲氧基羰基，a為0或1，n為2~6之整數)。 A liquid crystal alignment agent characterized by comprising a polyphthalate (A) and a poly (trans) acid (B) having a repeating unit represented by the following formula (1) And the repeating unit represented by the formula (2), (wherein R 1 is an alkyl group having 1 to 6 carbon atoms, and R 2 to R 5 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y 1 is represented by the following formula (Y 1 - 2) The divalent organic group, Y 2 is a divalent organic group selected from at least one of the group consisting of the following formulas (Y 2 -1) and (Y 2 -2), (wherein, A 1 and A 5 are each independently a single bond or an alkylene group having a carbon number of 1 to 5, and A 2 and A 4 are each independently an alkylene group having 1 to 5 carbon atoms, and A 3 is a carbon number of 1 ~6 alkylene, or cycloalkyl, B 1 and B 2 are independently a single bond, -O-, -NH-, -NMe-, -C(=O)-, -C(=O) O-, -C(=O)NH-, -C(=O)NMe-, -OC(=O)-, -NHC(=O)-, or -N(Me)C(=O)-, D 1 is tert-butoxycarbonyl or 9-fluorenylmethoxycarbonyl, a is 0 or 1, and n is an integer of 2 to 6).

本發明的PAE/PAA摻合系液晶配向劑可不依附於所摻合的PAA之構造，並使所得到的液晶配向膜展現出高度的液晶配向性。因此，可得到一種液晶配向劑，其係能選擇各種的PAA並以高等級來滿足液晶顯示元件所需要的各種特性。 The PAE/PAA blending liquid crystal alignment agent of the present invention may not adhere to the structure of the blended PAA, and the resulting liquid crystal alignment film exhibits a high degree of liquid crystal alignment. Therefore, a liquid crystal alignment agent which can select various PAAs and which satisfies various characteristics required for the liquid crystal display element at a high level can be obtained.

[實施發明之最佳形態] [Best Mode for Carrying Out the Invention] <聚醯胺酸酯(A)> <Polyurethane (A)>

本發明的液晶配向劑中所使用的聚醯胺酸酯，係含有上述式(1)的重複單位及式(2)的重複單位。式(1)及式(2)中的記號之定義係如同上述般。 The polyphthalate used in the liquid crystal alignment agent of the present invention contains the repeating unit of the above formula (1) and the repeating unit of the formula (2). The definitions of the symbols in the formulas (1) and (2) are as described above.

尚，式(1)及式(2)中的碳數1~6之烷基可任意為直鏈狀或支鏈狀，以碳數1~4者為較佳。作為較佳具體例，可舉出甲基、乙基、丙基、異丙基、n-丁基、異丁基、s-丁基、t-丁基、戊基、己基等。 Further, the alkyl group having 1 to 6 carbon atoms in the formula (1) and the formula (2) may be optionally linear or branched, and preferably having 1 to 4 carbon atoms. Preferable examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, and a hexyl group.

於式(1)及式(2)中，就液晶配向性之觀點而言，R2~R5較佳為：R2與R4為氫，R3與R5為碳數1~6之烷基，特別是甲基或乙基；或是，R2與R4為碳數1~6之烷基，特別是甲基或乙基，R3與R5為氫。 In the formulae (1) and (2), from the viewpoint of liquid crystal alignment, R 2 to R 5 are preferably: R 2 and R 4 are hydrogen, and R 3 and R 5 are carbon numbers 1 to 6. An alkyl group, especially a methyl group or an ethyl group; or, R 2 and R 4 are an alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, and R 3 and R 5 are hydrogen.

式(1)中的Y1為下述式(Y1-2)所表示的2價有機基，該2價有機基係由式：H2N-Y1-NH2所表示的二胺化合物所衍生。 Y 1 in the formula ( 1 ) is a divalent organic group represented by the following formula (Y 1 -2), which is derived from a diamine compound represented by the formula: H 2 NY 1 -NH 2 .

於(Y1-2)中的A1、A5、A2及A4的定義係如同上述般，但其中就與密封劑中的官能基之反應性之觀點而言，A1、A5係以單鍵或亞甲基為較佳。又，A2、A4係以亞甲 基、或伸乙基為較佳。 The definitions of A 1 , A 5 , A 2 and A 4 in (Y 1 -2) are as described above, but in view of the reactivity with the functional groups in the sealant, A 1 , A 5 It is preferred to use a single bond or a methylene group. Further, it is preferred that A 2 and A 4 are a methylene group or an ethyl group.

就與密封劑中的官能基之反應性之觀點而言，A3以亞甲基或伸乙基為較佳。就液晶配向性之觀點而言，B1、B2以單鍵或-O-為較佳。就進行脫保護的溫度之觀點而言，D1以tert-丁氧基羰基為較佳。a係以0~3為較佳。 From the viewpoint of reactivity with a functional group in the sealant, A 3 is preferably a methylene group or an ethylidene group. From the viewpoint of liquid crystal alignment, B 1 and B 2 are preferably a single bond or -O-. From the viewpoint of the temperature at which deprotection is carried out, D 1 is preferably a tert-butoxycarbonyl group. a is preferably 0 to 3.

作為式(Y1-2)的較佳具體例，可舉出下述式(1-1)~式(1-21)。 Preferred examples of the formula (Y 1 -2) include the following formulas (1-1) to (1-21).

於式(1-1)~(1-21)中，Me係表示甲基，D2係 表示tert-丁氧基羰基。 In the formulae (1-1) to (1-21), Me represents a methyl group, and D 2 represents a tert-butoxycarbonyl group.

聚醯胺酸酯(A)中的式(1)所表示的重複單位之含有比例，相對於全重複單位以5~60莫耳%為較佳，10~20莫耳%為又較佳。 The content ratio of the repeating unit represented by the formula (1) in the polyphthalate (A) is preferably from 5 to 60 mol%, more preferably from 10 to 20 mol%, based on the total repeat unit.

式(2)所表示的重複單位中的Y2為選自由下述式(Y2-1)與(Y2-2)之至少1種所表示的2價有機基。該2價有機基係由式：H2N-Y2-NH2所表示的二胺化合物所衍生。 Y 2 in the repeating unit represented by the formula (2) is a divalent organic group selected from at least one of the following formulae (Y 2 -1) and (Y 2 -2). The divalent organic group is derived from a diamine compound represented by the formula: H 2 NY 2 -NH 2 .

於式(Y2-1)及式(Y2-2)中的n，其中以2~5之整數為較佳，2之整數為更佳。 In the formula (Y 2 -1) and the formula (Y 2 -2), n is preferably an integer of 2 to 5, and an integer of 2 is more preferable.

聚醯胺酸酯(A)中的式(2)所表示的重複單位之含有比例，相對於全重複單位以10~70莫耳%為較佳，20~40莫耳%為又較佳。 The content ratio of the repeating unit represented by the formula (2) in the polyphthalate (A) is preferably from 10 to 70 mol%, more preferably from 20 to 40 mol%, based on the total repeat unit.

本發明的液晶配向劑中所使用的聚醯胺酸酯，在能發揮本發明之效果之範圍內，除了上述式(1)、式(2)的重複單位以外，亦可具有下述式(3)的重複單位。 The polyphthalate used in the liquid crystal alignment agent of the present invention may have the following formula in addition to the repeating units of the above formulas (1) and (2) within the range in which the effects of the present invention can be exerted ( 3) The repeating unit.

於式(3)中，R1~R5係與式(1)、式(2)之情形為相同定義。又，Y3係由式：H2N-Y3-NH2所表示的二胺化合物所衍生的2價有機基，該構造係由除了Y1、Y2以外的2價有機基中予以適當選擇。可舉出Y3之具體例如下述。 In the formula (3), R 1 to R 5 are the same as defined in the case of the formulas (1) and (2). Further, Y 3 is a divalent organic group derived from a diamine compound represented by the formula: H 2 NY 3 —NH 2 , and the structure is appropriately selected from divalent organic groups other than Y 1 and Y 2 . Specific examples of Y 3 include the following.

其中就液晶配向性之觀點而言，作為Y3以上述(Y-7)所表示的構造為較佳。 Among them, from the viewpoint of liquid crystal alignment, Y 3 is preferably a structure represented by the above (Y-7).

若含有聚醯胺酸酯(A)中的式(3)所表示的重複單位時，其含有比例相對於全重複單位以10~50莫耳%為較 佳，30~50莫耳%為又較佳。 When the repeating unit represented by the formula (3) in the polyphthalate (A) is contained, the content ratio thereof is 10 to 50 mol% with respect to the total repeating unit. Good, 30~50% is better.

<聚醯胺酸(B)> <Polyamic acid (B)>

本發明的液晶配向劑中所使用的聚醯胺酸，係使四羧酸二酐成分和二胺成分(聚縮合)反應而得到者，該構造並未特別限定。 The polyphthalic acid used in the liquid crystal alignment agent of the present invention is obtained by reacting a tetracarboxylic dianhydride component and a diamine component (polycondensation), and the structure is not particularly limited.

<四羧酸二酐成分> <tetracarboxylic dianhydride component>

本發明中所使用的聚醯胺酸的原料之四羧酸二酐成分，較佳如下述式所表示。 The tetracarboxylic dianhydride component of the raw material of the polylysine used in the present invention is preferably represented by the following formula.

若表示X之具體例，可舉出下述式(X-1)~(X-43)。就取得性之觀點而言，以(X-1)~(X-14)為又較佳，以(X-1)(但，R7~R10全部為氫原子)、(X-2)、(X-3)、(X-5)、(X-6)、(X-7)、(X-8)、(X-10)、(X-11)、或(X-14)為特佳。 Specific examples of X include the following formulas (X-1) to (X-43). From the viewpoint of availability, (X-1) to (X-14) are preferable, and (X-1) (however, all of R 7 to R 10 are hydrogen atoms), (X-2) , (X-3), (X-5), (X-6), (X-7), (X-8), (X-10), (X-11), or (X-14) Very good.

<二胺成分> <Diamine component>

本發明中所使用的聚醯胺酸的原料之二胺，該具體例係與上述聚醯胺酸酯(A)的原料的H2N-Y1-NH2、H2N-Y2-NH2、或NH2-Y3-NH2(Y1、Y2及Y3的定義係如同上述般)為相同。 The diamine of the raw material of polylysine used in the present invention, which is H 2 NY 1 -NH 2 , H 2 NY 2 -NH 2 , or the raw material of the above polyglycolate (A), or NH 2 -Y 3 -NH 2 (the definitions of Y 1 , Y 2 and Y 3 are as described above) are the same.

<聚醯胺酸酯(A)之製造方法> <Method for Producing Polyurethane (A)> <聚醯胺酸酯之製造方法> <Method for producing polyamidomate>

上述式(1)所表示的聚醯胺酸酯，係藉由下述式(1a)或式(1a’)所表示的四羧酸二酐或其衍生物之任一，與H2N-Y1-NH2、H2N-Y2-NH2、或NH2-Y3-NH2(Y1、Y2及Y3的定義係如同上述般)式：H2N-Y1-NH2、H2N-Y2-NH2、或NH2- Y3-NH2(Y1、Y2及Y3的定義係如同上述般)之反應而可得到。 The polyphthalate represented by the above formula (1) is any one of tetracarboxylic dianhydride or a derivative thereof represented by the following formula (1a) or formula (1a'), and H 2 NY 1 -NH 2 , H 2 NY 2 -NH 2 , or NH 2 -Y 3 -NH 2 (Y 1 , Y 2 and Y 3 are as defined above) Formula: H 2 NY 1 -NH 2 , H 2 NY A reaction of 2 -NH 2 or NH 2 -Y 3 -NH 2 (the definitions of Y 1 , Y 2 and Y 3 are as described above) can be obtained.

於式(1a)及式(1a’)中，R1~R5與上述為相同定義，R為羥基或氯原子。 In the formula (1a) and the formula (1a'), R 1 to R 5 are the same as defined above, and R is a hydroxyl group or a chlorine atom.

上述式(1)所表示的聚醯胺酸酯係可使用上述單體並採用例如下述所表示的(i)~(iii)之方法來合成。 The polyperurethane ester represented by the above formula (1) can be synthesized by using the above monomers, for example, by the methods (i) to (iii) shown below.

(i)聚醯胺酸之製造方法 (i) Method for producing polylysine

聚醯胺酸酯係可藉由將由式(1a)所表示的四羧酸二酐與式：H2N-Y1-NH2所表示的二胺化合物所得到的聚醯胺酸進行酯化來製造。 Polyurethane ester can be produced by esterifying a polyamic acid obtained from a tetracarboxylic dianhydride represented by the formula (1a) with a diamine compound represented by the formula: H 2 NY 1 -NH 2 . .

具體而言，在有機溶劑的存在下，可藉由將聚醯胺酸與酯化劑於-20℃~150℃、較佳為0℃~50℃、以30分鐘~24小時、較佳為1~4小時進行反應來製造。 Specifically, in the presence of an organic solvent, the polyamic acid and the esterifying agent can be used at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably It is produced by reacting for 1 to 4 hours.

作為前述酯化劑，以藉由純化而可容易除去者為較佳，可舉出N,N-二甲基甲醯胺二甲基縮醛、N,N-二甲基甲醯胺二乙基縮醛、N,N-二甲基甲醯胺二丙基縮醛、N,N-二甲基甲醯胺二新戊基丁基縮醛、N,N-二甲基甲醯胺二-t-丁基縮醛、1-甲基-3-p-甲苯基三氮烯、1-乙基-3-p-甲苯基三氮烯、1-丙基-3-p-甲苯基三氮烯、4-(4,6-二甲氧基- 1,3,5-三嗪-2-基)-4-甲基嗎啉氯化物等。酯化劑之使用量，相對於聚醯胺酸的重複單位1莫耳以2~6莫耳當量為較佳。 The esterification agent is preferably one which can be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide II. Acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dinepentyl butyl acetal, N,N-dimethylformamide -t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyl III Nitroene, 4-(4,6-dimethoxy- 1,3,5-triazin-2-yl)-4-methylmorpholine chloride, and the like. The amount of the esterifying agent to be used is preferably 2 to 6 mole equivalents per 1 mole of the repeating unit of the polyamic acid.

就聚合物之溶解性之觀點而言，前述有機溶劑以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、γ-丁內酯為較佳，該等可使用1種或亦可混合2種以上來使用。於反應系中的聚合物的濃度，就不易引起聚合物的析出、且易於得到高分子量體之觀點而言，以1~30質量%為較佳，5~20質量%為又較佳。 From the viewpoint of solubility of the polymer, the above organic solvent is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone, and these can be used. One type or two or more types may be used in combination. The concentration of the polymer in the reaction system is preferably from 1 to 30% by mass, and preferably from 5 to 20% by mass, from the viewpoint of not easily causing precipitation of the polymer and easily obtaining a high molecular weight body.

(ii)四羧酸二烷基酯二氯化物與二胺化合物之製造方法 (ii) Method for producing dialkyl tetracarboxylate dichloride and diamine compound

聚醯胺酸酯係可藉由將式(1a’)所表示的四羧酸二烷基酯二氯化物(R為氯原子時)，與式(1b)所表示的二胺化合物進行聚縮合來製造。 Polyurethane ester can be polycondensed with a diamine compound represented by the formula (1b) by using a dialkyl tetracarboxylate dichloride represented by the formula (1a') (when R is a chlorine atom) To manufacture.

具體而言，在鹼及有機溶劑的存在下，可藉由將四羧酸二烷基酯二氯化物與二胺化合物於-20℃~150℃、較佳為0℃~50℃、以30分鐘~24小時、較佳為1~4小時進行反應來製造。 Specifically, in the presence of a base and an organic solvent, the dicarboxylic acid dialkyl ester dichloride and the diamine compound can be used at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, to 30 It is produced by reacting in minutes to 24 hours, preferably 1 to 4 hours.

前述鹼係可使用吡啶、三乙基胺、4-二甲基胺基吡啶等，但為了使反應穩定地進行以吡啶為較佳。鹼之添加量，以容易除去之量、且易於得到高分子量體之觀點而言，相對於四羧酸二烷基酯二氯化物以2~4倍莫耳為較佳。 Although pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used as the base, pyridine is preferably used in order to stably carry out the reaction. The amount of the base to be added is preferably 2 to 4 moles per mole of the dicarboxylic acid dialkyl ester dichloride from the viewpoint of easy removal and easy availability of a high molecular weight body.

就單體及聚合物之溶解性之觀點而言，前述有機溶劑 以N-甲基-2-吡咯啶酮、γ-丁內酯為較佳，該等係可使用1種或亦可混合2種以上來使用。於反應系中的聚合物的濃度，就不易引起聚合物的析出、且易於得到高分子量聚合物之觀點而言，以1~30質量%為較佳，5~20質量%為又較佳。又，為了防止四羧酸二烷基酯二氯化物的水解，聚醯胺酸酯之製造中使用的溶劑以盡可能地脫水為較佳，以在氮氣氛中進行從而防止外來氣體的混入為較佳。 The aforementioned organic solvent from the viewpoint of the solubility of the monomer and the polymer N-methyl-2-pyrrolidone and γ-butyrolactone are preferred, and these may be used alone or in combination of two or more. The concentration of the polymer in the reaction system is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint of not easily causing precipitation of the polymer and easily obtaining a high molecular weight polymer. Further, in order to prevent hydrolysis of the dicarboxylic acid dialkyl ester dichloride, the solvent used in the production of the polyphthalate is preferably dehydrated as much as possible, and is carried out in a nitrogen atmosphere to prevent the intrusion of foreign gases. Preferably.

(iii)四羧酸二烷基酯與二胺化合物之製造方法 (iii) Method for producing dialkyl tetracarboxylate and diamine compound

聚醯胺酸酯係可藉由將式(1a’)所表示的四羧酸二烷基酯(R為羥基時)，與式：H2N-Y1-NH2所表示的二胺化合物進行聚縮合來製造。 The polyphthalamide can be polymerized with a diamine compound represented by the formula: H 2 NY 1 —NH 2 by using a dialkyl tetracarboxylate represented by the formula (1a′) (when R is a hydroxyl group). Condensation to make.

具體而言，在縮合劑、鹼及有機溶劑的存在下，可藉由將四羧酸二烷基酯與二胺化合物於0℃~150℃、較佳為0℃~100℃、以30分鐘~24小時、較佳為3~15小時進行反應來製造。 Specifically, in the presence of a condensing agent, a base and an organic solvent, the dialkyl tetracarboxylate and the diamine compound can be used at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C for 30 minutes. It is produced by reacting for ~24 hours, preferably 3 to 15 hours.

前述縮合劑係可使用三苯基亞磷酸酯、二環己基碳二亞胺、1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽、N,N’-羰基二咪唑、二甲氧基-1,3,5-三嗪甲基嗎啉、O-(苯并***-1-基)-N,N,N’,N’-四甲基脲四氟硼酸鹽、O-(苯并***-1-基)-N,N,N’,N’-四甲基脲六氟磷酸鹽、(2,3-二氫-2-硫基-3-苯并唑基)膦酸二苯酯等。縮合劑之使用量，相對於四羧酸二烷基酯以2~3倍莫耳為較佳。 As the condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N, N can be used. '-Carbonyldiimidazole, dimethoxy-1,3,5-triazinemethylmorpholine, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyl Urea tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thio -3-Benzene Diphenyl zoledophosphonate and the like. The amount of the condensing agent used is preferably 2 to 3 moles per mole of the tetracarboxylic acid dialkyl ester.

前述鹼係可使用吡啶、三乙基胺等的3級 胺。鹼之添加量，就容易除去的量、且易於得到高分子量體之觀點而言，相對於二胺成分以2~4倍莫耳為較佳。 As the base, a grade 3 such as pyridine or triethylamine can be used. amine. The amount of the base to be added is preferably 2 to 4 moles per mole of the diamine component from the viewpoint of easy removal amount and easy availability of a high molecular weight body.

作為前述有機溶劑，就對於四羧酸二烷基酯與二胺之溶解性之觀點而言，以N-甲基-2-吡咯啶酮、γ-丁內酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基己內醯胺、二甲基亞碸、二甲基碸、六甲基亞碸為較佳。該等係可使用1種或2種以上。 As the organic solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, and N,N-dimethyl group are used for the viewpoint of solubility of a dialkyl tetracarboxylate and a diamine. Formamide, N,N-dimethylacetamide, N-methylcaprolactam, dimethyl hydrazine, dimethyl hydrazine, hexamethylarylene is preferred. These systems can be used alone or in combination of two or more.

又，於上述製造方法中，藉由加入路易斯酸作為添加劑可使反應有效率地進行。作為路易斯酸以氯化鋰、溴化鋰等的鹵化鋰為較佳。路易斯酸之添加量，相對於二胺成分以0~1.0倍莫耳為較佳。 Further, in the above production method, the reaction can be efficiently carried out by adding a Lewis acid as an additive. As the Lewis acid, lithium halide such as lithium chloride or lithium bromide is preferred. The addition amount of the Lewis acid is preferably 0 to 1.0 times the molar amount of the diamine component.

上述3種類的聚醯胺酸酯之製造方法中，為了得到高分子量的聚醯胺酸酯，以上述(i)或上述(ii)之製造法為特佳。 In the method for producing the above-mentioned three types of polyphthalate, in order to obtain a high molecular weight polyphthalate, the production method of the above (i) or (ii) is particularly preferable.

以如上述般之方式所得到的聚醯胺酸酯的溶液，可藉由一邊充分的攪拌一邊注入至不良溶劑中來使聚合物析出。進行數次析出並以不良溶劑洗淨後，經常溫或加熱乾燥而可得到純化的聚醯胺酸酯的粉末。不良溶劑並未特別限定，可舉出水、甲醇、乙醇、己烷、丁基溶纖劑、丙酮、甲苯等。 The solution of the polyglycolate obtained as described above can be precipitated by injecting into a poor solvent while stirring sufficiently. After several times of precipitation and washing with a poor solvent, the powder of the purified polyphthalate is obtained by heating at room temperature or by heating. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

<末端經修飾的聚醯胺酸酯之製造方法> <Method for producing terminal modified polyphthalate>

末端經修飾的聚醯胺酸酯，可將下述式(1c’)所表示的氯羰基化合物與如上述般之方式所得的在末端具有胺基 的聚醯胺酸酯進行反應而得到， The terminal modified polyphthalate may have a chlorocarbonyl compound represented by the following formula (1c') and an amine group at the terminal obtained as described above. Polyacetate is obtained by reaction,

(式中，A5及R8係與上述為相同定義)。 (wherein A 5 and R 8 are the same as defined above).

作為上述氯羰基化合物，碳數越少的構造則末端之間的相互作用越小，可抑制聚醯胺酸酯之凝集。因此，作為氯羰基化合物以丙烯醯氯、甲基丙烯醯氯、巴豆醯氯、2-呋喃甲醯氯、2-噻吩甲醯氯、氯甲酸乙酯、氯甲酸乙烯酯、氯甲酸環戊基酯、氯硫甲酸S-苯酯、或C-29為又較佳。以丙烯醯氯、甲基丙烯醯氯、巴豆醯氯、2-呋喃甲醯氯或2-噻吩甲醯氯為更佳。 As the chlorocarbonyl compound, the structure in which the carbon number is smaller has a smaller interaction between the terminals, and aggregation of the polyphthalate can be suppressed. Therefore, as a chlorocarbonyl compound, it is acryloyl chloride, methacryloyl chloride, crotonyl chloride, 2-furoylguanidinium chloride, 2-thienylguanidinium chloride, ethyl chloroformate, vinyl chloroformate, cyclopentyl chloroformate. Ester, S-phenyl chlorosulfate, or C-29 is further preferred. More preferably, it is propylene chloride, methacrylium chloride, croton chloride, 2-furoylguanidinium chloride or 2-thienylguanidinium chloride.

末端經修飾的聚醯胺酸酯，具體而言可舉出：將在末端具有胺基的聚醯胺酸酯的粉末溶解於有機溶劑中後，在鹼的存在下添加氯羰基化合物來使其反應之方法；或將式：H2N-Y1-NH2所表示的二胺化合物與式(1a’)所表示的四羧酸二烷基酯衍生物，在有機溶劑中使其反應而得到在末端具有胺基的聚醯胺酸酯之情形下，不離析該聚醯胺酸酯，對該反應系中添加氯羰基化合物，並使其與存在於反應系中的在末端具有胺基的聚醯胺酸酯反應之方法等。其中，後者的對反應系中添加氯羰基化合物之方法，由於藉由再沈澱之聚醯胺酸酯之純化以1次即可，可縮短製造步驟，故為更佳。 Specific examples of the terminal modified polyphthalate include a method in which a powder of a polyphthalate having an amine group at the terminal is dissolved in an organic solvent, and then a chlorocarbonyl compound is added in the presence of a base to make it a method of reacting; or a diamine compound represented by the formula: H 2 NY 1 -NH 2 and a dialkyl tetracarboxylate derivative represented by the formula (1a'), which are reacted in an organic solvent to obtain In the case of a polyglycolate having an amine group at the end, the polyphthalate is not isolated, a chlorocarbonyl compound is added to the reaction system, and the polyamine group having an amine group present at the terminal is present in the reaction system. A method of reacting a phthalate or the like. Among them, the latter method of adding a chlorocarbonyl compound to the reaction system is preferably carried out by purification of the re-precipitated polyglycolate once, and the production step can be shortened, which is more preferable.

為了得到本發明的末端經修飾的聚醯胺酸酯，需要製造在主鏈末端存在有胺基的聚醯胺酸酯。因此，式(1b)所表示的二胺化合物與式(1a’)所表示的四羧酸二烷基酯衍生物之莫耳比率係以1：0.7~1：1為較佳，1：0.8~1：1為又較佳。 In order to obtain the terminal modified polyphthalate of the present invention, it is necessary to produce a polyphthalate having an amine group at the end of the main chain. Therefore, the molar ratio of the diamine compound represented by the formula (1b) to the dialkyl tetracarboxylate derivative represented by the formula (1a') is preferably from 1:0.7 to 1:1, and 1:0.8. ~1:1 is better.

作為上述對反應系中添加氯羰基化合物之方法如下述：與四羧酸二烷基酯衍生物同時添加並使其與二胺反應之方法；使四羧酸二烷基酯衍生物與二胺充分反應來製造末端為胺基的聚醯胺酸酯，之後再添加氯羰基化合物之方法。就易於控制聚合物之分子量之觀點而言，以後者的方法為更佳。 As a method of adding a chlorocarbonyl compound to the reaction system as described above, a method of simultaneously adding a dicarboxylic acid tetraalkyl ester derivative and reacting it with a diamine; and a dicarboxylic acid tetraalkyl ester derivative and a diamine The reaction is sufficiently carried out to produce a polyamine phthalate having an amine group at the end, followed by a method of adding a chlorocarbonyl compound. The latter method is more preferable from the viewpoint of easy control of the molecular weight of the polymer.

於得到末端經修飾的聚醯胺酸酯時，在鹼及有機溶劑的存在下，末端為胺基的聚醯胺酸酯與氯羰基化合物之反應以於-20~150℃、較佳為0~50℃，以30分鐘~24小時、較佳為30分鐘~4小時來進行為較佳。 When the terminal modified polyphthalate is obtained, the amine group-containing polyphthalate is reacted with the chlorocarbonyl compound in the presence of a base and an organic solvent at -20 to 150 ° C, preferably 0. It is preferably carried out at from -50 ° C for 30 minutes to 24 hours, preferably from 30 minutes to 4 hours.

氯羰基化合物之添加量，相對於末端為胺基的聚醯胺酸酯的一個重複單位以0.5~60mol%為較佳，1~40mol%為又較佳。若添加量過多時，由於殘留未反應的氯羰基化合物而難以除去，故以1~20mol%為更佳。 The amount of the chlorocarbonyl compound to be added is preferably 0.5 to 60 mol%, more preferably 1 to 40 mol%, per one repeating unit of the amine group-containing polyphthalate. When the amount is too large, it is difficult to remove the unreacted chlorocarbonyl compound, and it is more preferably 1 to 20 mol%.

前述鹼較佳為可使用吡啶、三乙基胺、或二甲基胺基吡啶，但為了使反應穩定地進行故以吡啶為較佳。鹼之添加量若過多時則難以除去，若過少時則因分子量變小，故相對於氯羰基化合物以2~4倍莫耳為較佳。 The base is preferably pyridine, triethylamine or dimethylaminopyridine. However, in order to allow the reaction to proceed stably, pyridine is preferred. When the amount of the base added is too large, it is difficult to remove. When the amount is too small, the molecular weight is small, so that it is preferably 2 to 4 moles per mole of the chlorocarbonyl compound.

經修飾末端的聚醯胺酸酯之製造中所使用的有機溶 劑，就單體及聚合物之溶解性而言以N-甲基-2-吡咯啶酮、γ-丁內酯為較佳，該等係可使用1種或亦可混合2種以上來使用。製造時的濃度若過高時則易引起聚合物的析出，若過低時則分子量無法提高，因此以1~30質量%為較佳，5~20質量%為又較佳。又，為了防止氯羰基化合物的水解，以經修飾末端的聚醯胺酸酯之製造中所使用的有機溶劑盡可能地脫水、又保存於氮氣氛中來防止外來氣體的混入為較佳。 Organic solvent used in the manufacture of modified terminal polyphthalate In the case of the solubility of the monomer and the polymer, N-methyl-2-pyrrolidone or γ-butyrolactone is preferred. These may be used alone or in combination of two or more. . When the concentration at the time of production is too high, precipitation of the polymer is liable to occur. If the molecular weight is too low, the molecular weight cannot be increased. Therefore, it is preferably 1 to 30% by mass, more preferably 5 to 20% by mass. Further, in order to prevent hydrolysis of the chlorocarbonyl compound, it is preferred that the organic solvent used in the production of the modified polyamic acid ester is dehydrated as much as possible and stored in a nitrogen atmosphere to prevent the incorporation of foreign gas.

<聚醯胺酸(B)之製造方法> <Method for Producing Polylysine (B)>

本發明的聚醯胺酸(B)係可藉由將四羧酸二酐成分與二胺成分進行反應而得到。具體而言，在有機溶劑的存在下，可藉由將四羧酸二酐成分與二胺成分於-20℃~150℃、較佳為0℃~50℃，以30分鐘~24小時、較佳為1~12小時使其反應來製造。 The polyproline (B) of the present invention can be obtained by reacting a tetracarboxylic dianhydride component with a diamine component. Specifically, in the presence of an organic solvent, the tetracarboxylic dianhydride component and the diamine component can be used in the range of -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours. It is made for 1 to 12 hours to make it react.

就單體及聚合物之溶解性之觀點而言，前述有機溶劑以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、或γ-丁內酯為較佳，該等係可使用1種或亦可混合2種以上來使用。於反應系中的聚合物的濃度，就不易引起聚合物的析出、且易於得到高分子量體之觀點而言，以1~30質量%為較佳，5~20質量%為又較佳。 The organic solvent is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the monomer and the polymer. These may be used alone or in combination of two or more. The concentration of the polymer in the reaction system is preferably from 1 to 30% by mass, and preferably from 5 to 20% by mass, from the viewpoint of not easily causing precipitation of the polymer and easily obtaining a high molecular weight body.

以如上述般之方式所得到的聚醯胺酸，係可藉由一邊充分的攪拌反應溶液一邊注入至不良溶劑中來使聚合物析出並回收。又，進行數次析出並以不良溶劑洗淨 後，經常溫或加熱乾燥可得到純化的聚醯胺酸的粉末。不良溶劑並無特別限定，可舉出水、甲醇、乙醇、己烷、丁基溶纖劑、丙酮、甲苯等。 The polyamic acid obtained as described above can be precipitated and recovered by injecting into a poor solvent while sufficiently stirring the reaction solution. Also, it is precipitated several times and washed with a poor solvent. Thereafter, the powder of the purified polyaminic acid is obtained by heating at room temperature or by heating. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

<液晶配向劑> <Liquid alignment agent>

本發明的液晶配向劑較佳為具有聚醯胺酸酯(A)與聚醯胺酸(B)溶解於有機溶劑中而得到的溶液形態。聚醯胺酸酯(A)之分子量，以其重量平均分子量，較佳為2,000~500,000，又較佳為5,000~300,000，更佳為10,000~100,000。又，數平均分子量，較佳為1,000~250,000，又較佳為2,500~150,000，更佳為5,000~50,000。 The liquid crystal alignment agent of the present invention is preferably in the form of a solution obtained by dissolving polyphthalate (A) and polyphthalic acid (B) in an organic solvent. The molecular weight of the polyglycolate (A) is preferably from 2,000 to 500,000, more preferably from 5,000 to 300,000, still more preferably from 10,000 to 100,000, based on the weight average molecular weight thereof. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, still more preferably from 5,000 to 50,000.

另一方面，聚醯胺酸(B)的重量平均分子量，較佳以2,000~500,000為宜，又較佳為5,000~300,000，更佳為10,000~100,000。又，數平均分子量，較佳為1,000~250,000，又較佳為2,500~150,000，更佳為5,000~50,000。 On the other hand, the weight average molecular weight of the polyamic acid (B) is preferably from 2,000 to 500,000, more preferably from 5,000 to 300,000, still more preferably from 10,000 to 100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, still more preferably from 5,000 to 50,000.

藉由使聚醯胺酸酯(A)的分子量小於聚醯胺酸(B)的分子量，可進而減低因相分離所致的微小凹凸。聚醯胺酸酯(A)與聚醯胺酸(B)之平均分子量的差，作為重量平均分子量較佳以1,000~1200,000為宜，3,000~80,000為又較佳，5,000~60,000為特佳。 By making the molecular weight of the polyphthalate (A) smaller than the molecular weight of the poly-proline (B), minute irregularities due to phase separation can be further reduced. The difference in average molecular weight between the polyamidomate (A) and the polyamic acid (B) is preferably from 1,000 to 1,200,000 as the weight average molecular weight, preferably from 3,000 to 80,000, and preferably from 5,000 to 60,000. good.

本發明的液晶配向劑中所含有的聚醯胺酸酯(A)與聚醯胺酸(B)之質量比率(聚醯胺酸酯/聚醯胺酸)係以 1/9~9/1為較佳。上述比率又較佳為2/8~8/2，特佳為3/7~7/3。藉由將上述比率設為此範圍內，可提供液晶配向性與電氣特性皆為良好的液晶配向劑。 The mass ratio of the polyamidomate (A) to the polyaminic acid (B) contained in the liquid crystal alignment agent of the present invention (polyperurethane/polyglycine) is 1/9~9/1 is preferred. The above ratio is preferably 2/8 to 8/2, and particularly preferably 3/7 to 7/3. By setting the above ratio within this range, it is possible to provide a liquid crystal alignment agent which is excellent in liquid crystal alignment and electrical properties.

本發明的液晶配向劑較佳為具有聚醯胺酸酯(A)及聚醯胺酸(B)溶解於有機溶劑中的溶液形態。該製造方法並無特別限定，例如有：將聚醯胺酸酯及聚醯胺酸的兩種粉末混合後溶解於有機溶劑中之方法；將聚醯胺酸酯的粉末與聚醯胺酸的溶液混合之方法；將聚醯胺酸酯的溶液與聚醯胺酸的粉末混合之方法；將聚醯胺酸酯的溶液與聚醯胺酸的溶液混合之方法。即使是溶解聚醯胺酸酯及聚醯胺酸的良溶劑各自為不同之情形，亦由於可得到均勻的聚醯胺酸酯-聚醯胺酸混合溶液，故以將聚醯胺酸酯溶液與聚醯胺酸溶液混合之方法為又較佳。 The liquid crystal alignment agent of the present invention is preferably in the form of a solution in which a polyphthalate (A) and a poly (trans) acid (B) are dissolved in an organic solvent. The production method is not particularly limited, and examples thereof include a method in which two powders of a polyphthalate and a poly-proline are mixed and dissolved in an organic solvent; and a powder of a polyphthalate and a poly-proline a method of mixing a solution; a method of mixing a solution of a polyphthalate with a powder of poly-proline; a method of mixing a solution of a polyphthalate with a solution of poly-proline. Even if the good solvents for dissolving the polyamidomate and the poly-proline are different, and because the uniform polyphthalate-polyamide mixture solution can be obtained, the polyphthalate solution is used. The method of mixing with the polyaminic acid solution is further preferred.

又，在有機溶劑中製造聚醯胺酸酯或聚醯胺酸之情形時，聚醯胺酸酯的溶液及聚醯胺酸的溶液可以是分別所得到的反應溶液之本身，又亦可以是利用適當的溶劑將該反應溶液稀釋而得到的溶液。又，以粉末形式得到的聚醯胺酸酯或聚醯胺酸之情形時，亦可將此者溶解於有機溶劑中來製成溶液。此時，有機溶劑中之總聚合物濃度係以10~30質量%為較佳，10~15質量%為特佳。又，於溶解聚醯胺酸酯及/或聚醯胺酸的粉末時亦可進行加熱。加熱溫度係以20~150℃為較佳，20~80℃為特佳。 Further, in the case of producing a polyphthalate or a poly-proline in an organic solvent, the solution of the polyphthalate and the solution of the poly-proline may be the respective reaction solutions obtained, or may be The solution obtained by diluting the reaction solution with a suitable solvent. Further, in the case of a polyglycolate or polylysine obtained in the form of a powder, the solution may be dissolved in an organic solvent to prepare a solution. In this case, the total polymer concentration in the organic solvent is preferably 10 to 30% by mass, and particularly preferably 10 to 15% by mass. Further, heating may be carried out when the powder of the polyphthalate and/or polyphthalic acid is dissolved. The heating temperature is preferably 20 to 150 ° C, and particularly preferably 20 to 80 ° C.

本發明的液晶配向劑中，聚醯胺酸酯(A)及聚醯胺酸(B)之總含有量(固體成分濃度)係可依所欲形成的 液晶配向膜的厚度之設定來做適當變更。其中，就為了形成均勻且沒有缺陷的塗膜之觀點而言，相對於有機溶劑以0.5質量%以上為較佳，就溶液的保存穩定性之觀點而言，以15質量%以下為較佳。以0.5~10質量%為又較佳，1~10質量%為特佳。 In the liquid crystal alignment agent of the present invention, the total content (solid content concentration) of the polyglycolate (A) and the poly-proline (B) can be formed as desired. The thickness of the liquid crystal alignment film is set to be appropriately changed. In view of the fact that the coating film is uniform and has no defects, it is preferably 0.5% by mass or more based on the organic solvent, and preferably 15% by mass or less from the viewpoint of storage stability of the solution. It is preferably 0.5 to 10% by mass, and more preferably 1 to 10% by mass.

於本發明的液晶配向劑中，除了聚醯胺酸酯(A)及聚醯胺酸(B)之外，亦可含有具有液晶配向性的其他的聚合物。作為該等其他的聚合物，可舉出除了聚醯胺酸酯(A)以外的聚醯胺酸酯、可溶性聚醯亞胺、及/或除了聚醯胺酸(B)以外的聚醯胺酸等。 The liquid crystal alignment agent of the present invention may contain other polymers having liquid crystal alignment properties in addition to the polyphthalate (A) and the polyamic acid (B). Examples of such other polymers include polyglycolate other than polyphthalate (A), soluble polyimine, and/or polyamine other than polyglycolic acid (B). Acid, etc.

本發明的液晶配向劑可含有的有機溶劑，只要是聚醯胺酸酯(A)及聚醯胺酸(B)的聚合物成分呈均勻地溶解者即可並無特別限定。若舉出其具體例，可舉出N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-甲基己內醯胺、2-吡咯啶酮、N-乙烯基-2-吡咯啶酮、二甲基亞碸、二甲基碸、γ-丁內酯、1,3-二甲基-2-咪唑啉酮、3-甲氧基-N,N-二甲基丙醯胺等。該等係可使用1種或亦可混合2種以上來使用。尚，就本發明的液晶配向劑中所含有的PAE與PAA之相溶性等的觀點而言，N-甲基-2-吡咯啶酮之含有比率，相對於液晶配向劑之全重量以30~50質量%為較佳。又，即使是無法單獨均勻地溶解聚合物成分的溶劑，只要是在不析出聚合物的範圍內，亦可混合至上述有機溶劑中。 The organic solvent which can be contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is uniformly dissolved in the polymer component of the polyphthalate (A) and polyphthalic acid (B). Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2- Pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl azine, dimethyl Anthracene, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, and the like. These may be used alone or in combination of two or more. In view of the compatibility between PAE and PAA contained in the liquid crystal alignment agent of the present invention, the content ratio of N-methyl-2-pyrrolidone is 30% with respect to the total weight of the liquid crystal alignment agent. 50% by mass is preferred. Moreover, even if it is a solvent which cannot melt|dissolve a polymer component uniformly, it can mix with the said organic solvent in the range which does not isolate a polymer.

本發明的液晶配向劑，除了含有用於溶解聚合物成分的有機溶劑以外，亦可含有用於提高將液晶配向劑塗布至基板上時的塗膜均勻性的溶劑。如此般之溶劑，一般而言係採用表面張力較上述有機溶劑為低之溶劑。若舉出其具體例時，可舉出乙基溶纖劑、丁基溶纖劑、乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲醚-2-乙酸酯、丙二醇-1-單***-2-乙酸酯、丁基溶纖劑乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯等。該等的溶劑係可併用2種以上。 The liquid crystal alignment agent of the present invention may contain a solvent for improving the uniformity of the coating film when the liquid crystal alignment agent is applied onto the substrate, in addition to the organic solvent for dissolving the polymer component. Such a solvent is generally a solvent having a lower surface tension than the above organic solvent. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and 1-methoxyl. 2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate Ester, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, dipropylene glycol, 2-(2-ethoxypropoxy group ) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents may be used in combination of two or more kinds.

本發明的液晶配向劑係亦可含有矽烷偶合劑或交聯劑等的各種添加劑。若添加矽烷偶合劑或交聯劑時，為了防止聚合物的析出，對液晶配向劑加入不良溶劑之情形時，以在這之前來做添加為較佳。又，為了於燒成塗膜時使聚醯胺酸酯(A)及聚醯胺酸(B)的醯亞胺化有效率地進行，亦可添加醯亞胺化促進劑。 The liquid crystal alignment agent of the present invention may contain various additives such as a decane coupling agent or a crosslinking agent. When a decane coupling agent or a crosslinking agent is added, in order to prevent precipitation of a polymer, when a poor solvent is added to a liquid crystal alignment agent, it is preferable to add it beforehand. Further, in order to efficiently carry out the hydrazine imidization of the polyperurethane (A) and the poly-proline (B) in the case of firing the coating film, a ruthenium promoter may be added.

若於本發明的液晶配向劑中添加矽烷偶合劑之情形時，可在將聚醯胺酸酯溶液與聚醯胺酸溶液混合之前，添加於聚醯胺酸酯溶液、聚醯胺酸溶液、或聚醯胺酸酯溶液與聚醯胺酸溶液之兩者中。又，矽烷偶合劑係可添加於聚醯胺酸酯-聚醯胺酸混合溶液中。矽烷偶合劑由於是為了使聚合物與基板之密合性提升之目的下來做添加， 故作為矽烷偶合劑之添加方法係以添加可不均勻分布於膜內部及基板界面的聚醯胺酸溶液，並使聚合物與矽烷偶合劑充分地反應後，再與聚醯胺酸酯溶液混合之方法為又較佳。矽烷偶合劑之添加量若過多時，則未反應者將對液晶配向性造成不良影響，若過少時由於無法展現出對於密合性之效果，故相對於聚合物之固體成分以0.01~5.0質量%為較佳，0.1~1.0質量%為又較佳。 When the decane coupling agent is added to the liquid crystal alignment agent of the present invention, it may be added to the polyphthalate solution or the polyaminic acid solution before mixing the polyphthalate solution with the polyaminic acid solution. Or both of the polyamidate solution and the poly-proline solution. Further, a decane coupling agent may be added to the polyphthalate-polyaminic acid mixed solution. The decane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate. Therefore, as a method for adding a decane coupling agent, a polyamic acid solution which is unevenly distributed in the inside of the film and at the interface of the substrate is added, and the polymer is sufficiently reacted with the decane coupling agent, and then mixed with the polyphthalate solution. The method is further preferred. When the amount of the decane coupling agent added is too large, the unreacted person will adversely affect the liquid crystal alignment property, and if it is too small, since the effect on the adhesion cannot be exhibited, the solid content of the polymer is 0.01 to 5.0 mass. % is preferably, and 0.1 to 1.0% by mass is more preferable.

以下可舉出矽烷偶合劑之具體例，但可使用於本發明的液晶配向劑的矽烷偶合劑並不限定於此等之中。如3-胺基丙基三乙氧基矽烷、3-(2-胺基乙基)胺基丙基三甲氧基矽烷、3-(2-胺基乙基)胺基丙基甲基二甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、3-胺基丙基二乙氧基甲基矽烷等的胺系矽烷偶合劑；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、乙烯甲基二甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三異丙氧基矽烷、烯丙基三甲氧基矽烷、p-苯乙烯基三甲氧基矽烷等的乙烯系矽烷偶合劑；3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等的環氧系矽烷偶合劑；3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙 烯醯氧基丙基三乙氧基矽烷等的甲基丙烯基系矽烷偶合劑；3-丙烯醯氧基丙基三甲氧基矽烷等的丙烯系矽烷偶合劑；3-脲丙基三乙氧基矽烷等的脲系矽烷偶合劑；雙(3-(三乙氧基矽烷基)丙基)二硫基、雙(3-(三乙氧基矽烷基)丙基)四硫基等的硫基系矽烷偶合劑；3-巰丙基甲基二甲氧基矽烷、3-巰丙基三甲氧基矽烷、3-辛醯基硫代-1-丙基三乙氧基矽烷等的巰基系矽烷偶合劑；3-異氰酸酯基丙基三乙氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷等的異氰酸酯系矽烷偶合劑；三乙氧基矽烷基丁醛等的醛系矽烷偶合劑；三乙氧基矽烷基丙基甲基胺甲酸酯、(3-三乙氧基矽烷基丙基)-t-丁基胺甲酸酯等的胺甲酸酯系矽烷偶合劑。 Specific examples of the decane coupling agent are exemplified below, but the decane coupling agent to be used in the liquid crystal alignment agent of the present invention is not limited thereto. Such as 3-aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-(2-aminoethyl)aminopropylmethyl dimethyl Oxydecane, 3-aminopropyltrimethoxydecane, 3-anilinopropyltrimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propane An amine decane coupling agent such as a base amine or 3-aminopropyldiethoxymethyl decane; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxy ethoxylate) Base) decane, ethylene methyl dimethoxy decane, vinyl triethoxy decane, vinyl triisopropoxy decane, allyl trimethoxy decane, p-styryl trimethoxy decane, etc. Ethylene decane coupling agent; 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxy An epoxy decane coupling agent such as decane, 3-glycidoxypropylmethyldimethoxydecane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-methyl Propylene methoxy propyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl Trimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropane a methacrylic decane coupling agent such as an enemethoxypropyltriethoxy decane; a propylene decane coupling agent such as 3-propenyloxypropyltrimethoxydecane; and 3-ureidopropyltriethoxy Urea-based decane coupling agent such as decane or the like; sulfur such as bis(3-(triethoxydecyl)propyl)dithio or bis(3-(triethoxydecyl)propyl)tetrathio Base decane coupling agent; fluorenyl decane couple such as 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-octylthio-l-propyltriethoxydecane Mixture; isocyanate-based decane coupling agent such as 3-isocyanate propyl triethoxy decane or 3-isocyanate propyl trimethoxy decane; aldehyde decane coupling agent such as triethoxy decyl butyl aldehyde; An urethane-based decane coupling agent such as oxonium propylmethylamine formate or (3-triethoxydecylpropyl)-t-butylamine formate.

以下可舉出聚醯胺酸酯(A)及聚醯胺酸(B)的醯亞胺化促進劑之具體例，但並非被限定於此等之中。 Specific examples of the ruthenium imidization accelerator of the polyglycolate (A) and the polyglycolic acid (B) are exemplified below, but are not limited thereto.

於上述式(I-1)~(I-17)中的D分別獨立為t-丁氧基羰基、或9-茀基甲氧基羰基、苄氧甲醯基。尚，於(I-14)~(I-17)中，一個式中存在複數的D，該等係可相互相同，亦可不同。 D in the above formulas (I-1) to (I-17) are each independently a t-butoxycarbonyl group, a 9-fluorenylmethoxycarbonyl group or a benzoxycarbonyl group. Further, in (I-14) to (I-17), a plural D exists in one formula, and the lines may be identical to each other or different.

只要是在可得到促進聚醯胺酸酯(A)及聚醯胺酸(B)的熱醯亞胺化之效果之範圍內即可，醯亞胺化促進劑之含有量並無特別限制。若要表示其下限時，可舉出相對於聚醯胺酸酯中所含的醯胺酸或其酯部位1莫耳，較佳為0.01莫耳以上，又較佳為0.05莫耳以上，更佳為0.1莫耳以上。又，就將燒成後的膜中所殘留的醯亞胺化促進劑本身 對液晶配向膜的各特性造成不良影響控制在最低限度之觀點而言，若要表示其上限時，可舉出相對於本發明的聚醯胺酸酯及聚醯胺酸(B)中所含的醯胺酸或其酯部位1莫耳，較佳為醯亞胺化促進劑為2莫耳以下，又較佳為1莫耳以下，更佳為0.5莫耳以下。 The content of the ruthenium imidization accelerator is not particularly limited as long as it can provide an effect of promoting the heat imidization of the polyphthalate (A) and the poly (resource). When the lower limit is shown, it is preferably 1 mol or more, more preferably 0.05 mol or more, or more preferably 0.05 mol or more, based on the valeric acid or its ester moiety contained in the polyphthalate. Good for 0.1 moles or more. Moreover, the ruthenium amide promoter itself remaining in the film after firing From the viewpoint of minimizing the control of the respective characteristics of the liquid crystal alignment film, the upper limit of the liquid crystal alignment film is included in the polyphthalate and the polyamine (B) of the present invention. The proline or its ester moiety is 1 mol, preferably the quinone imidization promoter is 2 mol or less, more preferably 1 mol or less, still more preferably 0.5 mol or less.

若添加醯亞胺化促進劑時，因會有藉由加熱而進行醯亞胺化之可能性，故以用良溶劑及不良溶劑做稀釋後加入為較佳。 When a ruthenium iodide promoter is added, there is a possibility that ruthenium imidization by heating may be carried out by diluting with a good solvent and a poor solvent.

<液晶配向膜> <Liquid alignment film>

本發明的液晶配向膜係將上述液晶配向劑塗布至基板上，並乾燥、燒成，接著進行配向處理而成的膜。 In the liquid crystal alignment film of the present invention, the liquid crystal alignment agent is applied onto a substrate, dried, fired, and then subjected to alignment treatment.

作為塗布本發明的液晶配向劑的基板，只要是透明性高的基板即可並無特別限定，可使用玻璃基板、氮化矽基板、丙烯酸基板或聚碳酸酯基板等的塑膠基板等。就製程的簡單化之觀點而言，以使用形成有用於液晶驅動的ITO電極等的基板為較佳。又，反射型的液晶顯示元件中，若僅為單側之基板時，亦可使用矽晶圓等之不透明物，此情形之電極亦可使用鋁等將光反射之材料。 The substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate or a polycarbonate substrate can be used. From the viewpoint of simplification of the process, it is preferred to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. Further, in the reflective liquid crystal display device, when it is only a single-sided substrate, an opaque material such as a germanium wafer may be used. In this case, a material such as aluminum or the like may be used.

作為本發明的液晶配向劑之塗布方法，可舉出旋轉塗布法、印刷法、噴墨法等。塗布液晶配向劑後的乾燥、燒成步驟係可選擇任意的溫度與時間。通常，為了充分地除去所含有的有機溶劑，以50~120℃使其乾燥1分鐘至10分鐘，其後以150~300℃進行5~120分鐘的燒 成。燒成後的塗膜的厚度並未特別限定，但若過薄時，則因液晶顯示元件的可靠性有降低之情形，所以為5~300nm，較佳為10~200nm。 The coating method of the liquid crystal alignment agent of the present invention may, for example, be a spin coating method, a printing method, an inkjet method or the like. The drying and baking steps after the application of the liquid crystal alignment agent can be selected to any temperature and time. Usually, in order to sufficiently remove the organic solvent contained, it is dried at 50 to 120 ° C for 1 minute to 10 minutes, and then burned at 150 to 300 ° C for 5 to 120 minutes. to make. The thickness of the coating film after firing is not particularly limited. However, when it is too thin, the reliability of the liquid crystal display element is lowered, so that it is 5 to 300 nm, preferably 10 to 200 nm.

作為將此塗膜進行配向處理之方法，可舉出摩擦法、光配向處理法等，但本發明的液晶配向劑係對於採用光配向處理法來使用時為特別有用。 The method of performing the alignment treatment on the coating film may be a rubbing method or a photo-alignment treatment method. However, the liquid crystal alignment agent of the present invention is particularly useful when used by a photo-alignment treatment method.

作為光配向處理法之具體例可舉出：對前述塗膜表面照射一定方向偏光的放射線，並依情形進而以150~250℃的溫度來進行加熱處理來賦予液晶配向能之方法。作為放射線，可使用具有100~800nm的波長的紫外線及可見光線。其中，以具有100~400nm的波長的紫外線為較佳，具有200~400nm的波長的紫外線為特佳。又，為了改善液晶配向性，亦可以50~250℃加熱塗膜基板並同時照射放射線。前述放射線之照射量以在1~10,000mJ/cm2的範圍內為較佳，100~5,000mJ/cm2的範圍內為特佳。所製作的液晶配向膜可穩定使液晶分子向一定的方向來配向。 Specific examples of the photo-alignment treatment method include a method of irradiating the surface of the coating film with radiation polarized in a certain direction, and further heating the film at a temperature of 150 to 250 ° C to impart alignment energy to the liquid crystal. As the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and ultraviolet rays having a wavelength of 200 to 400 nm are particularly preferable. Further, in order to improve the liquid crystal alignment property, the coated substrate may be heated at 50 to 250 ° C while irradiating the radiation. In the irradiation amount of radiation is preferably in the range of 1 ~ 10,000mJ / cm 2, and in the range of 100 ~ 5,000mJ / cm 2 is particularly preferred. The liquid crystal alignment film produced can stably align liquid crystal molecules in a certain direction.

<液晶顯示元件> <Liquid crystal display element>

本發明的液晶顯示元件係由上述液晶配向劑得到附有液晶配向膜的基板後，以周知之方法來製作液晶晶胞從而成為液晶顯示元件。 In the liquid crystal display device of the present invention, after the substrate having the liquid crystal alignment film is obtained from the liquid crystal alignment agent, a liquid crystal cell is produced by a known method to form a liquid crystal display element.

若舉出液晶晶胞之製作之一例子時，係如同下述般。首先，準備形成有液晶配向膜的一對基板。接 著，於一片的基板的液晶配向膜上散布間隔物，以液晶配向膜面作為內側之方式來貼合另一片的基板後，減壓注入液晶並密封。又，對於散布間隔物的液晶配向膜面滴入液晶後，再貼合基板來進行密封亦可。此時的間隔物的厚度係較佳為1~30μm，又較佳為2~10μm。 An example of the production of a liquid crystal cell is as follows. First, a pair of substrates on which a liquid crystal alignment film is formed are prepared. Connect The spacer is spread on the liquid crystal alignment film of one of the substrates, and the other substrate is bonded so that the liquid crystal alignment film surface is inside. Then, the liquid crystal is injected under reduced pressure and sealed. Further, after the liquid crystal is dropped onto the liquid crystal alignment film surface on which the spacer is dispersed, the substrate may be bonded and sealed. The thickness of the spacer at this time is preferably from 1 to 30 μm, and more preferably from 2 to 10 μm.

[實施例] [Examples]

以下可舉出實施例來更具體地說明本發明。但，本發明係不受該等的實施例限定來做解釋。 The invention will be more specifically described below by way of examples. However, the invention is not to be construed as limited by the embodiments.

於下述所使用的化合物的縮寫、及各特性之測定方法係如同以下般。 The abbreviations of the compounds used below and the methods for measuring the respective properties are as follows.

<單體> <monomer>

1,3DMCBDE-Cl：二甲基1,3-雙(氯羰基)-1,3-二甲基環丁烷-2,4-二羧酸酯 1,3DMCBDE-Cl: dimethyl 1,3-bis(chlorocarbonyl)-1,3-dimethylcyclobutane-2,4-dicarboxylate

CBDA：1,2,3,4-環丁烷四羧酸二酐 CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

BDA：1,2,3,4-丁烷四羧酸二酐 BDA: 1,2,3,4-butane tetracarboxylic dianhydride

PMDA：焦蜜石酸二酐 PMDA: pyrethic acid dianhydride

BPDA：3,3’,4,4’-聯苯四羧酸二酐 BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

BAPU：1,3-雙(4-胺基苯乙基)尿素 BAPU: 1,3-bis(4-aminophenethyl)urea

DADPA：4,4’-二胺基二苯基胺 DADPA: 4,4'-diaminodiphenylamine

Me-DADPA：N,N-雙(胺基苯基)-甲基胺 Me-DADPA: N,N-bis(aminophenyl)-methylamine

DBA：3,5-二胺基苯甲酸 DBA: 3,5-diaminobenzoic acid

p-PDA：p-苯二胺 p-PDA: p-phenylenediamine

TDA：4-(2,5-二氧代四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二羧酸酐 TDA: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride

DDM：4,4’-二胺基二苯基甲烷 DDM: 4,4'-diaminodiphenylmethane

<溶劑> <solvent>

NMP：N-甲基-2-吡咯啶酮、BCS：丁基溶纖劑、 NMP: N-methyl-2-pyrrolidone, BCS: butyl cellosolve,

BCA：丁基溶纖劑乙酸酯、GBL：γ-丁內酯 BCA: butyl cellosolve acetate, GBL: γ-butyrolactone

PB：丙二醇單丁基醚、 PB: propylene glycol monobutyl ether,

DME：1,2-二甲氧基乙烷 DIBC：二異丁基甲醇、 DME: 1,2-dimethoxyethane DIBC: diisobutylmethanol,

DAA：雙丙酮醇 DAA: diacetone alcohol

<黏度> <viscosity>

於合成例中，聚合物溶液的黏度係使用E型黏度計TVE-22H(東機產業公司製)，以樣品量1.1mL、錐形轉子TE-1(1°34’、R24)、溫度25℃來進行測定。 In the synthesis example, the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL, a conical rotor TE-1 (1° 34', R24), and a temperature of 25 The measurement was carried out at °C.

<分子量> <molecular weight>

於合成例中，聚合物的分子量係藉由GPC(常溫凝膠 滲透色譜法)裝置來測定，以聚乙二醇、聚環氧乙烷換算值來計算出數平均分子量(以下亦稱為Mn)與重量平均分子量(以下亦稱為Mw)。 In the synthesis example, the molecular weight of the polymer is by GPC (normal temperature gel) The number average molecular weight (hereinafter also referred to as Mn) and the weight average molecular weight (hereinafter also referred to as Mw) were calculated in terms of polyethylene glycol and polyethylene oxide by a permeation chromatography apparatus.

GPC裝置：Shodex公司製(GPC-101) GPC device: manufactured by Shodex (GPC-101)

管柱：Shodex公司製(KD803、KD805的串聯)、管柱溫度：50℃ Pipe column: made by Shodex (series of KD803, KD805), column temperature: 50 ° C

溶離液：N,N-二甲基甲醯胺(作為添加劑之溴化鋰-水合物(LiBr‧H2O)為30mmol/L、磷酸‧脫水結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml/L) Dissolution: N,N-dimethylformamide (lithium bromide-hydrate (LiBr‧H 2 O) as an additive is 30 mmol/L, ‧ dehydrated crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) ) is 10ml/L)

流速：1.0ml/分鐘 Flow rate: 1.0ml/min

檢量線製作用標準樣品：Tosoh公司製TSK標準聚環氧乙烷(重量平均分子量(Mw)約900,000、150,000、100,000、30,000)、及POLYMER LABORATORIES公司製聚乙二醇(波峰頂分子量(Mp)約12,000、4,000、1,000)。測定係為了避免波峰重疊，分別測定了900,000、100,000、12,000、1,000之4種類混合而成的樣品、及150,000、30,000、4,000之3種類混合而成的樣品之2種樣品。 Standard sample for the production of calibration lines: TSK standard polyethylene oxide manufactured by Tosoh Co., Ltd. (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by POLYMER LABORATORIES (peak peak molecular weight (Mp) ) about 12,000, 4,000, 1,000). In order to avoid peak overlap, two types of samples of a mixture of four types of 900,000, 100,000, 12,000, and 1,000 and two types of samples of 150,000, 30,000, and 4,000 were measured.

<表面粗糙度之測定> <Measurement of Surface Roughness>

將藉由旋轉塗布所得到的液晶配向劑的塗膜，在溫度80℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成後，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板，對燒成膜照射# # # mJ/cm2 的254nm的紫外線從而可得到附有液晶配向膜的基板。利用原子力顯微鏡(AFM)來觀察該塗膜的膜表面，並測定膜表面的中心線平均粗糙度(Ra)來評估膜表面之平坦性。測定裝置：L-trace探針顯微鏡(SII‧Technology公司製) The coating film of the liquid crystal alignment agent obtained by spin coating was dried on a hot plate at a temperature of 80 ° C for 5 minutes, and fired in a hot air circulating oven at a temperature of 230 ° C for 10 minutes to obtain a film thickness of 100 nm. A ruthenium-imided film. Irradiation of the fired film through the polarizing plate ## # mJ/cm2 The ultraviolet light of 254 nm can thereby obtain a substrate with a liquid crystal alignment film. The film surface of the coating film was observed by an atomic force microscope (AFM), and the center line average roughness (Ra) of the film surface was measured to evaluate the flatness of the film surface. Measuring device: L-trace probe microscope (manufactured by SII‧Technology Co., Ltd.)

(合成例1) (Synthesis Example 1)

於附有攪拌裝置及氮導入管的2L分液瓶中，量取p-PDA 10.00g(92.4mmol)、DA-B 13.60g(55.5mmol)、及DA-C 12.60g(37.0mmol)，並加入NMP 379.00g與GBL 1023.00g及吡啶34.60g(0.43mol)後使其溶解。接著，一邊攪拌該溶液一邊添加58.30g(179.4mmol)的1,3DMCBDE-Cl，在水冷下使其反應14小時。於所得到的聚醯胺酸溶液中，添加2.40g(26.6mmol)的丙烯醯氯並進而反應4小時後，一邊攪拌一邊將該溶液投入至8653ml的異丙醇中，從而過濾取得析出的白色沈澱，接著，使用21635ml的異丙醇分5次來做洗淨，藉由進行乾燥可得到白色的聚醯胺酸酯樹脂粉末(PWD-1)。該聚醯胺酸酯之分子量為Mn=24,366、Mw=54,808。 10.00 g (92.4 mmol) of p-PDA, 13.60 g (55.5 mmol) of DA-B, and 12.60 g (37.0 mmol) of DA-C were weighed in a 2 L liquid separation bottle equipped with a stirring device and a nitrogen introduction tube, and NMP 379.00 g and GBL 1023.00 g and pyridine 34.60 g (0.43 mol) were added and dissolved. Next, while stirring the solution, 58.30 g (179.4 mmol) of 1,3DMCBDE-Cl was added, and the mixture was reacted under water cooling for 14 hours. After 2.40 g (26.6 mmol) of acrylonitrile chloride was added to the obtained polyamic acid solution and further reacted for 4 hours, the solution was poured into 8653 ml of isopropyl alcohol while stirring, and the precipitated white was obtained by filtration. Precipitation, followed by washing with 21635 ml of isopropyl alcohol 5 times, and drying was carried out to obtain a white polyphthalate resin powder (PWD-1). The molecular weight of the polyglycolate was Mn = 24,366 and Mw = 54,808.

將上述所得到的聚醯胺酸酯樹脂粉末(PWD-1)溶解於GBL中，而得到固體成分濃度12質量%的聚醯胺酸酯溶液(PAE-1)。 The polyphthalate resin powder (PWD-1) obtained above was dissolved in GBL to obtain a polyamidate solution (PAE-1) having a solid concentration of 12% by mass.

(合成例2) (Synthesis Example 2)

於附有攪拌裝置及氮導入管的2L分液瓶中，量取p- PDA 10.00g(92.4mmol)、DA-B 11.30g(46.24mmol)、及DA-C 5.26g(15.41mmol)，加入以NMP與GBL之質量比成為25：75之方式所調整的混合溶液1230.9g與吡啶28.38g(358.79mmol)並使其溶解。接著，一邊攪拌該溶液一邊添加48.60g(358.79mmol)的1,3DMCBDE-Cl，在水冷下使其反應14小時。於所得到的聚醯胺酸溶液中，添加2.008g(22.19mmol)的丙烯醯氯並進而反應4小時後，一邊攪拌一邊將該溶液投入至5132ml的異丙醇中，從而過濾取得析出的白色沈澱，接著，使用1711ml的異丙醇分5次來做洗淨，藉由進行乾燥可得到白色的聚醯胺酸酯樹脂粉末(PWD-2)。該聚醯胺酸酯之分子量為Mn=25,386、Mw=58,908。 In a 2L liquid dispensing bottle with a stirring device and a nitrogen inlet tube, measure p- PDA 10.00 g (92.4 mmol), DA-B 11.30 g (46.24 mmol), and DA-C 5.26 g (15.41 mmol), and a mixed solution adjusted to have a mass ratio of NMP to GBL of 25:75 was added to 1230.9 g. It was dissolved in 28.38 g (358.79 mmol) of pyridine. Next, while stirring the solution, 48.60 g (358.79 mmol) of 1,3DMCBDE-Cl was added, and the mixture was reacted under water cooling for 14 hours. After adding 2.008 g (22.19 mmol) of acrylonitrile chloride to the obtained polyamic acid solution and further reacting for 4 hours, the solution was poured into 5132 ml of isopropyl alcohol while stirring, and the precipitated white was obtained by filtration. Precipitation, followed by washing with 1711 ml of isopropyl alcohol 5 times, and drying was carried out to obtain a white polyphthalate resin powder (PWD-2). The molecular weight of the polyglycolate was Mn = 25,386 and Mw = 58,908.

將上述所得到的聚醯胺酸酯樹脂粉末(PWD-2)溶解於GBL中，而得到固體成分濃度12質量%的聚醯胺酸酯溶液(PAE-2)。 The polyphthalate resin powder (PWD-2) obtained above was dissolved in GBL to obtain a polyamine solution (PAE-2) having a solid concentration of 12% by mass.

(合成例3) (Synthesis Example 3)

於附有攪拌裝置及氮導入管的100mL四頸燒瓶中，量取DADPA 4.80g(24.0mmol)及DDM 1.20g(6.00mmol)，加入NMP 85.50g，一邊送入氮一邊攪拌並使其溶解。一邊攪拌該二胺溶液一邊添加CBDA 1.40g(6.90mmol)、DH-A 5.60g(22.5mmol)，進而以固體成分濃度成為12重量%之方式來加入NMP，並在室溫下攪拌24小時而得到聚醯胺酸溶液(PAA-1)。該聚醯胺酸溶液的溫度25℃時的黏度 係1918mPa‧s。又，該聚醯胺酸之分子量為Mn=13,384、Mw=32,796。 4.80 g (24.0 mmol) of DADPA and 1.20 g (6.00 mmol) of DDM were weighed in a 100 mL four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, and 85.50 g of NMP was added thereto, and the mixture was stirred and dissolved while supplying nitrogen. While stirring the diamine solution, 1.40 g (6.90 mmol) of CBDA and 5.60 g (22.5 mmol) of DH-A were added, and NMP was added so that the solid content concentration became 12 weight%, and it stirred at room temperature for 24 hours. A polylysine solution (PAA-1) was obtained. Viscosity of the polyamic acid solution at a temperature of 25 ° C It is 1918mPa‧s. Further, the molecular weight of the polyamic acid was Mn = 13,384 and Mw = 32,796.

進而，於該溶液中加入以NMP/GBL質量比為2/8的混合溶液來稀釋成為0.3質量%的3-環氧丙氧基丙基甲基二乙氧基矽烷溶液13.00g，而得到聚醯胺酸溶液(PAA-1)。 Further, a mixed solution of NMP/GBL in a mass ratio of 2/8 was added to the solution to dilute it to a 0.3% by mass solution of 3-glycidoxypropylmethyldiethoxydecane (13.00 g) to obtain a poly Proline solution (PAA-1).

(合成例4) (Synthesis Example 4)

於附有攪拌裝置及氮導入管的100mL四頸燒瓶中，量取BAPU 2.09g(7.00mmol)及DDM 5.55g(27.99mol)量取，加入NMP 10.00g、GBL 10.00g，一邊送入氮一邊攪拌並使其溶解。一邊攪拌該二胺溶液一邊添加CBDA 3.91g(19.93mmol)、BDA 2.77g(13.98mmol)，進而以固體成分濃度成為15重量%、又以NMP：GBL的質量比成為2：8之方式來加入兩溶劑，並在室溫下攪拌24小時而得到聚醯胺酸溶液(PAA-2)。該聚醯胺酸溶液的溫度25℃時的黏度係752mPa‧s。又，該聚醯胺酸之分子量為Mn=12,385、Mw=30,896。 In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, the amount of BAPU 2.09 g (7.00 mmol) and DDM 5.55 g (27.99 mol) was measured, and NMP 10.00 g and GBL 10.00 g were added, and nitrogen was fed. Stir and dissolve. While stirring the diamine solution, 3.81 g (19.93 mmol) of CBDA and 2.77 g (13.98 mmol) of BDA were added, and the solid content concentration was 15% by weight, and the mass ratio of NMP:GBL was 2:8. The two solvents were stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-2). The viscosity of the polyamic acid solution at a temperature of 25 ° C was 752 mPa ‧ s. Further, the molecular weight of the polyamic acid was Mn = 12,385 and Mw = 30,896.

(合成例5) (Synthesis Example 5)

於附有攪拌裝置及氮導入管的100mL四頸燒瓶中，量取Me-4APhA 2.103g(13.99mmol)及DDE 4.20g(20.97mmol)，加入NMP 10.00g、GBL 10.00g，一邊送入氮一邊攪拌並使其溶解。一邊攪拌該二胺溶液一邊添 加CBDA 2.40g(12.24mmol)、DH-A 5.25g(20.98mmol)，進而以固體成分濃度成為15重量%、又以NMP：GBL的質量比成為2：8之方式來追加兩溶劑，並在室溫下攪拌24小時而得到聚醯胺酸溶液(PAA-3)。該聚醯胺酸溶液的溫度25℃時的黏度係652mPa‧s。又，該聚醯胺酸之分子量為Mn=11,385、Mw=29,896。 In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, Me-4APhA 2.103 g (13.99 mmol) and DDE 4.20 g (20.97 mmol) were weighed, and NMP 10.00 g and GBL 10.00 g were added, and nitrogen was fed. Stir and dissolve. Adding while stirring the diamine solution CBDA 2.40g (12.24mmol) and DH-A 5.25g (20.98mmol) were further added, and the solid content concentration was 15% by weight, and the mass ratio of NMP:GBL was 2:8, and the two solvents were added. The mixture was stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-3). The viscosity of the polyamic acid solution at a temperature of 25 ° C was 652 mPa ‧ s. Further, the molecular weight of the polylysine was Mn = 11,385 and Mw = 29,896.

(合成例6) (Synthesis Example 6)

於附有攪拌裝置及氮導入管的100mL四頸燒瓶中，量取DBA 2.103g(6.99mmol)及DDE 4.90g(24.47mmol)，加入NMP 10.00g、GBL 10.00g，一邊送入氮一邊攪拌並使其溶解。一邊攪拌該二胺溶液一邊添加CBDA 1.23g(6.27mmol)、BDA 5.54g(27.96mmol)，進而以固體成分濃度成為15重量%、又以NMP：GBL的質量比成為2：8之方式來追加兩溶劑，並在室溫下攪拌24小時而得到聚醯胺酸溶液(PAA-4)。該聚醯胺酸溶液的溫度25℃時的黏度係682mPa‧s。又，該聚醯胺酸之分子量為Mn=11,225、Mw=30,196。 In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, DBA 2.103 g (6.99 mmol) and DDE 4.90 g (24.47 mmol) were weighed, and NMP 10.00 g and GBL 10.00 g were added, and while stirring, nitrogen was added thereto. Let it dissolve. While stirring the diamine solution, 1.23 g (6.27 mmol) of CBDA and 5.54 g (27.96 mmol) of BDA were added, and the solid content concentration was 15% by weight, and the mass ratio of NMP:GBL was 2:8. The two solvents were stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-4). The viscosity of the polyamic acid solution at a temperature of 25 ° C was 682 mPa ‧ s. Further, the molecular weight of the polyamic acid was Mn = 11,225 and Mw = 30,196.

(合成例7) (Synthesis Example 7)

於附有攪拌裝置及氮導入管的100mL四頸燒瓶中，量取Me-4APhA 1.052g(7.00mmol)、DDE 4.20g(20.97mmol)、及DADPA 1.395g(7.00mmol)，加入NMP 10.00g、GBL 10.00g，一邊送入氮一邊攪拌並使其溶 解。一邊攪拌該二胺溶液一邊添加CBDA 1.24g(6.32mmol)、BDA 5.54g(27.96mmol)，進而以固體成分濃度成為15重量%、又以NMP：GBL的質量比成為2：8之方式來追加兩溶劑，並在室溫下攪拌24小時而得到聚醯胺酸溶液(PAA-5)。該聚醯胺酸溶液的溫度25℃時的黏度係672mPa‧s。又，該聚醯胺酸之分子量為Mn=12,385、Mw=30,226。 In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.04 g (7.00 mmol) of Me-4APhA, 4.20 g (20.97 mmol) of DDE, and 1.395 g (7.00 mmol) of DADPA were weighed, and 10.00 g of NMP was added thereto. GBL 10.00g, stir and dissolve it while feeding nitrogen solution. While stirring the diamine solution, 1.24 g (6.32 mmol) of CBDA and 5.54 g (27.96 mmol) of BDA were added, and the solid content concentration was 15% by weight, and the mass ratio of NMP:GBL was 2:8. The two solvents were stirred at room temperature for 24 hours to obtain a polyaminic acid solution (PAA-5). The viscosity of the polyaminic acid solution at a temperature of 25 ° C was 672 mPa ‧ s. Further, the molecular weight of the polyamic acid was Mn = 12,385 and Mw = 30,226.

<比較合成例1> <Comparative Synthesis Example 1>

將附有攪拌裝置的500mL的四頸燒瓶設定為氮氣氛，加入p-pD 4.58g(42.4mmol)、DA-A 1.79g(4.71mmol)、NMP 84.70g、GBL 254.00g、及作為鹼的吡啶8.40g(106mmol)，並攪拌後使其溶解。接著，一邊攪拌該二胺溶液一邊添加1,3DMCBDE-Cl 14.4g(44.2mmol)，並以15℃使其反應一晚。攪拌一晚後，加入丙烯醯氯1.23g(13.6mmol)，並以15℃使其反應4小時。將所得到的聚醯胺酸酯的溶液一邊攪拌一邊投入至1477.00g的IPA中，從而過濾取得析出的白色沈澱，接著，使用738g的IPA來洗淨5次，藉由進行乾燥可得到白色的聚醯胺酸酯樹脂粉末17.30g。收率為96.9%。又，該聚醯胺酸酯之分子量為Mn=14,288、Mw=29,956。 A 500 mL four-necked flask equipped with a stirring device was set to a nitrogen atmosphere, and p-pD 4.58 g (42.4 mmol), DA-A 1.79 g (4.71 mmol), NMP 84.70 g, GBL 254.00 g, and pyridine as a base were added. 8.40 g (106 mmol) was stirred and dissolved. Next, 14.3 g (44.2 mmol) of 1,3DMCBDE-Cl was added while stirring the diamine solution, and the reaction was carried out overnight at 15 °C. After stirring for one night, 1.23 g (13.6 mmol) of propylene chloride was added, and the reaction was allowed to proceed at 15 ° C for 4 hours. The solution of the obtained polyphthalate was added to 1477.00 g of IPA while stirring, and a precipitated white precipitate was obtained by filtration, and then washed with 738 g of IPA for 5 times, and dried to obtain white color. Polyurethane resin powder 17.30 g. The yield was 96.9%. Further, the molecular weight of the polyphthalate was Mn = 14,288 and Mw = 29,956.

將所得到的聚醯胺酸酯樹脂粉末3.69g取入至100mL三角燒瓶中並加入GBL 33.2g，在室溫下攪拌24小時並使其溶解，而得到10%濃度的聚醯胺酸酯溶液(PAE-3)。 3.69 g of the obtained polyphthalate resin powder was taken into a 100 mL Erlenmeyer flask and 33.2 g of GBL was added thereto, and stirred at room temperature for 24 hours and dissolved to obtain a 10% concentration polyglycolate solution. (PAE-3).

<比較合成例2> <Comparative Synthesis Example 2>

於附有攪拌裝置及氮導入管的300mL四頸燒瓶中，量取DBA 1.20g(8.00mmol)並加入NMP 7.30g，一邊送入氮一邊攪拌並使其溶解。接著，加入Me-DADPA 6.80g(32.0mmol)、GBL 18.30g，並一邊送入氮一邊攪拌並使其溶解。一邊攪拌該二胺溶液一邊加入BDA 7.19g(36.0mmol)、GBL 18.30g，利用GBL以固體成分濃度成為25%之方式來做稀釋，並在水冷下攪拌2小時。接著加入PMDA 0.90g(4.00mmol)，以系中的固體成分濃度成為18%之方式來加入GBL，並在水冷下攪拌24小時。於所得到的聚醯胺酸溶液的溫度25.0℃中之黏度係780mPa‧s。又，該聚醯胺酸之分子量為Mn=11700、Mw=24780。 In a 300 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.20 g (8.00 mmol) of DBA was weighed and 7.30 g of NMP was added thereto, and the mixture was stirred and dissolved while supplying nitrogen. Next, 6.80 g (32.0 mmol) of Me-DADPA and 18.30 g of GBL were added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring the diamine solution, BDA 7.19 g (36.0 mmol) and GBL 18.30 g were added, and the mixture was diluted with GBL to have a solid concentration of 25%, and stirred under water cooling for 2 hours. Next, PMDA 0.90 g (4.00 mmol) was added, and GBL was added so that the solid content concentration in the system became 18%, and the mixture was stirred under water cooling for 24 hours. The viscosity of the obtained polyaminic acid solution at a temperature of 25.0 ° C was 780 mPa ‧ s. Further, the molecular weight of the polyamic acid was Mn = 11700 and Mw = 24,780.

進而，於該溶液中加入以NMP/GBL質量比為2/8的混合溶液來稀釋成為0.3質量%的3-環氧丙氧基丙基甲基二乙氧基矽烷溶液16.0g，而得到聚醯胺酸溶液(PAA-6)。 Further, 16.0 g of a 3-glycidoxypropylmethyldiethoxydecane solution diluted to 0.3% by mass in a mixed solution of NMP/GBL by mass ratio of 2/8 was added to the solution to obtain a poly Proline solution (PAA-6).

(實施例1) (Example 1)

於放入攪拌子的20ml樣品管中，取入合成例1所得到的聚醯胺酸酯溶液(PAE-1)1.80g、合成例3所得到的聚醯胺酸溶液(PAA-1)2.80g，加入NMP 4.90g、GBL 6.70g、BCA 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-1)。將液晶配向劑A-1以-20℃保管1週時，未發現固 形物的析出而呈現為均勻的溶液。 Into a 20 ml sample tube in which a stir bar was placed, 1.80 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and the polyaminic acid solution (PAA-1) 2.80 obtained in Synthesis Example 3 were taken. g, N90 4.90 g, GBL 6.70 g, BCA 1.80 g were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-1). When the liquid crystal alignment agent A-1 was stored at -20 ° C for 1 week, no solid was found. The precipitation of the shape appears as a homogeneous solution.

(實施例2) (Example 2)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)1.80g、合成例3所得到的聚醯胺酸溶液(PAA-1)2.80g，加入NMP 3.10g、GBL 8.50g、BCA 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-2)。將液晶配向劑A-2以-20℃保管1週時，未發現固形物的析出而呈現為均勻的溶液。 1.80 g of the polyphthalate solution (PAE-1) obtained in Synthesis Example 1 and the polyamidic acid solution (PAA-1) 2.80 obtained in Synthesis Example 3 were placed in a 20 ml sample tube in which a stir bar was placed. g, NMP 3.10 g, GBL 8.50 g, BCA 1.80 g were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-2). When the liquid crystal alignment agent A-2 was stored at -20 ° C for one week, no precipitation of solid matter was observed and a uniform solution was observed.

(實施例3) (Example 3)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)1.80g、合成例2所得到的聚醯胺酸溶液(PAA-1)2.80g，加入NMP 1.30g、GBL 10.30g、BCA 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-3)。將液晶配向劑A-3以-20℃保管1週時，未發現固形物的析出而呈現為均勻的溶液。 The polyphthalate solution (PAE-1) obtained in Synthesis Example 1 was weighed in a 20 ml sample tube in which a stir bar was placed, and the polyaminic acid solution (PAA-1) 2.80 obtained in Synthesis Example 2 was weighed. g, 1.30 g of NMP, 10.30 g of GBL, and 1.80 g of BCA were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-3). When the liquid crystal alignment agent A-3 was stored at -20 ° C for one week, no precipitation of the solid matter was observed and a uniform solution was observed.

(實施例4) (Example 4)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)2.40g、合成例2所得到的聚醯胺酸溶液(PAA-1)2.40g，加入NMP 5.30g、GBL 6.20g、BCA 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-4)。將液晶配向劑A-4以-20℃保管1週時，未發現固 形物的析出而呈現為均勻的溶液。 2.40 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and the polyaminic acid solution (PAA-1) 2.40 obtained in Synthesis Example 2 were placed in a 20 ml sample tube placed in a stir bar. g, NMP 5.30 g, GBL 6.20 g, BCA 1.80 g were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-4). When the liquid crystal alignment agent A-4 was stored at -20 ° C for 1 week, no solid was found. The precipitation of the shape appears as a homogeneous solution.

(實施例5) (Example 5)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)2.40g、合成例2所得到的聚醯胺酸溶液(PAA-1)2.40g，加入NMP 3.50g、GBL 8.00g、BCA 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-5)。將液晶配向劑A-5以-20℃保管1週時，未發現固形物的析出而呈現為均勻的溶液。 2.40 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and the polyaminic acid solution (PAA-1) 2.40 obtained in Synthesis Example 2 were placed in a 20 ml sample tube placed in a stir bar. g, NMP 3.50 g, GBL 8.00 g, BCA 1.80 g were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-5). When the liquid crystal alignment agent A-5 was stored at -20 ° C for one week, no precipitation of the solid matter was observed and a uniform solution was observed.

(實施例6) (Example 6)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)2.40g、合成例2所得到的聚醯胺酸溶液(PAA-1)2.40g，加入NMP 1.70g、GBL 9.80g、BCA 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-6)。將液晶配向劑A-6以-20℃保管1週時，未發現固形物的析出而呈現為均勻的溶液。 2.40 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and the polyaminic acid solution (PAA-1) 2.40 obtained in Synthesis Example 2 were placed in a 20 ml sample tube placed in a stir bar. g, 1.70 g of NMP, 9.80 g of GBL, and 1.80 g of BCA were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-6). When the liquid crystal alignment agent A-6 was stored at -20 ° C for one week, no precipitation of solid matter was observed and it appeared as a uniform solution.

(實施例7) (Example 7)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)3.00g、合成例2所得到的聚醯胺酸溶液(PAA-1)2.00g，加入NMP 5.60g、GBL 6.60g、BCA 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-7)。將液晶配向劑A-7以-20℃保管1週時，未發現固 形物的析出而呈現為均勻的溶液。 3.00 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and the polyaminic acid solution (PAA-1) 2.00 obtained in Synthesis Example 2 were weighed in a 20 ml sample tube in which a stir bar was placed. g, N60 5.60 g, GBL 6.60 g, BCA 1.80 g were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-7). When the liquid crystal alignment agent A-7 was stored at -20 ° C for 1 week, no solid was found. The precipitation of the shape appears as a homogeneous solution.

(實施例8) (Example 8)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)3.00g、合成例2所得到的聚醯胺酸溶液(PAA-1)2.00g，加入NMP 3.80g、GBL 7.40g、BCA 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-8)。將液晶配向劑A-8以-20℃保管1週時，未發現固形物的析出而呈現為均勻的溶液。 3.00 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and the polyaminic acid solution (PAA-1) 2.00 obtained in Synthesis Example 2 were weighed in a 20 ml sample tube in which a stir bar was placed. g, N80 3.80 g, GBL 7.40 g, BCA 1.80 g were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-8). When the liquid crystal alignment agent A-8 was stored at -20 ° C for one week, no precipitation of the solid matter was observed and a uniform solution was observed.

(實施例9) (Example 9)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)3.00g、合成例2所得到的聚醯胺酸溶液(PAA-1)2.00g，加入NMP 3.80g、GBL 7.40g、BCA 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-9)。將液晶配向劑A-9以-20℃保管1週時，未發現固形物的析出而呈現為均勻的溶液。 3.00 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and the polyaminic acid solution (PAA-1) 2.00 obtained in Synthesis Example 2 were weighed in a 20 ml sample tube in which a stir bar was placed. g, N80 3.80 g, GBL 7.40 g, BCA 1.80 g were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-9). When the liquid crystal alignment agent A-9 was stored at -20 ° C for one week, no precipitation of solid matter was observed and a uniform solution was observed.

(實施例10) (Embodiment 10)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)2.40g、合成例5所得到的聚醯胺酸溶液(PAA-3)2.40g，加入NMP 1.70g、GBL 9.80g、PB 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-10)。將液晶配向劑A-6以-20℃保管1週時，未發現固形 物的析出而呈現為均勻的溶液。 2.40 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and the polyaminic acid solution (PAA-3) 2.40 obtained in Synthesis Example 5 were weighed in a 20 ml sample tube in which a stir bar was placed. g, 1.70 g of NMP, 9.80 g of GBL, and 1.80 g of PB were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-10). When the liquid crystal alignment agent A-6 was stored at -20 ° C for 1 week, no solid form was observed. The precipitation of the material appears as a homogeneous solution.

(實施例11) (Example 11)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)2.40g、合成例6所得到的聚醯胺酸溶液(PAA-4)2.40g，加入NMP 1.70g、GBL 9.80g、DME 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-11)。將液晶配向劑A-6以-20℃保管1週時，未發現固形物的析出而呈現為均勻的溶液。 2.40 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and the polyaminic acid solution (PAA-4) 2.40 obtained in Synthesis Example 6 were weighed in a 20 ml sample tube in which a stir bar was placed. g, 1.70 g of NMP, 9.80 g of GBL, and 1.80 g of DME were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-11). When the liquid crystal alignment agent A-6 was stored at -20 ° C for one week, no precipitation of solid matter was observed and it appeared as a uniform solution.

(實施例12) (Embodiment 12)

於放入攪拌子的20ml樣品管中，量取合成例1所得到的聚醯胺酸酯溶液(PAE-1)2.40g、合成例7所得到的聚醯胺酸溶液(PAA-5)2.40g，加入NMP 1.70g、GBL 9.80g、DPM 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-12)。將液晶配向劑A-6以-20℃保管1週時，未發現固形物的析出而呈現為均勻的溶液。 2.40 g of the polyamidomate solution (PAE-1) obtained in Synthesis Example 1 and the polyaminic acid solution (PAA-5) 2.40 obtained in Synthesis Example 7 were placed in a 20 ml sample tube in which a stir bar was placed. g, 1.70 g of NMP, 9.80 g of GBL, and 1.80 g of DPM were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-12). When the liquid crystal alignment agent A-6 was stored at -20 ° C for one week, no precipitation of solid matter was observed and it appeared as a uniform solution.

(實施例13) (Example 13)

於放入攪拌子的20ml樣品管中，量取合成例2所得到的聚醯胺酸酯溶液(PAE-2)2.40g、合成例5所得到的聚醯胺酸溶液(PAA-3)2.40g，加入NMP 1.70g、GBL 9.80g、DAA 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-13)。將液晶配向劑A-6以-20℃保管1週時，未發現固 形物的析出而呈現為均勻的溶液。 The polyphthalate solution (PAE-2) obtained in Synthesis Example 2 (2.40 g) and the polyaminic acid solution (PAA-3) obtained in Synthesis Example 5 were weighed in a 20 ml sample tube in which a stir bar was placed. g, 1.70 g of NMP, 9.80 g of GBL, and 1.80 g of DAA were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-13). When the liquid crystal alignment agent A-6 was stored at -20 ° C for 1 week, no solid was found. The precipitation of the shape appears as a homogeneous solution.

(實施例14) (Example 14)

於放入攪拌子的20ml樣品管中，量取合成例2所得到的聚醯胺酸酯溶液(PAE-1)2.40g、合成例6所得到的聚醯胺酸溶液(PAA-4)2.40g，加入NMP 1.70g、GBL 9.80g、DIBC 1.80g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(A-14)。將液晶配向劑A-6以-20℃保管1週時，未發現固形物的析出而呈現為均勻的溶液。 The polyphthalate solution (PAE-1) obtained in Synthesis Example 2 (2.40 g) and the polyaminic acid solution (PAA-4) obtained in Synthesis Example 6.40 were weighed in a 20 ml sample tube in which a stir bar was placed. g, 1.70 g of NMP, 9.80 g of GBL, and 1.80 g of DIBC were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (A-14). When the liquid crystal alignment agent A-6 was stored at -20 ° C for one week, no precipitation of solid matter was observed and it appeared as a uniform solution.

(比較例1) (Comparative Example 1)

於放入攪拌子的20ml樣品管中，量取比較合成例1所得到的聚醯胺酸酯溶液(PAE-2)8.0g、比較合成例2所得到的聚醯胺酸溶液(PAA-2)7.50g，加入NMP 3.70g、GBL 25.80g、BCA 5.00g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(B-1)。將液晶配向劑B-1以-20℃保管1週時，未發現固形物的析出而呈現為均勻的溶液。 Into a 20 ml sample tube in which a stir bar was placed, 8.0 g of the polyamidomate solution (PAE-2) obtained in Comparative Synthesis Example 1 was compared, and the polyaminic acid solution (PAA-2 obtained in Comparative Synthesis Example 2) was compared. 7.50 g, N70 3.70 g, GBL 25.80 g, BCA 5.00 g were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (B-1). When the liquid crystal alignment agent B-1 was stored at -20 ° C for one week, no solid matter was precipitated and a uniform solution was observed.

(比較例2) (Comparative Example 2)

於放入攪拌子的20ml樣品管中，量取比較合成例1所得到的聚醯胺酸酯溶液(PAE-2)8.00g、比較合成例2所得到的聚醯胺酸溶液(PAA-2)7.50g，加入NMP 13.7g、GBL 15.8g、BCA 5.0g並用磁攪拌器攪拌30分鐘而得到液晶配向劑(B-2)。將液晶配向劑A1以-20℃保管1週 時，可發現固形物的析出。 The polyamine solvent solution (PAE-2) obtained in Comparative Synthesis Example 1 was weighed to 8.00 g in a 20 ml sample tube placed in a stirrer, and the polyaminic acid solution (PAA-2 obtained in Comparative Synthesis Example 2) was compared. 7.50 g, NMP 13.7 g, GBL 15.8 g, BCA 5.0 g were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (B-2). Store the liquid crystal alignment agent A1 at -20 ° C for 1 week. When the solid matter is precipitated, it can be found.

(實施例15) (Example 15)

用1.0μm的過濾器將實施例1所得到的液晶配向劑(A-1)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射250mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(C-1)。對於該液晶配向膜來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent (A-1) obtained in Example 1 was filtered with a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 60 ° C for 5 minutes, and used. The hot air circulating oven having a temperature of 230 ° C was fired for 10 minutes to obtain a ruthenium film having a thickness of 100 nm. The fired film was irradiated with ultraviolet rays of 254 nm of 250 mJ/cm 2 through a polarizing plate to obtain a substrate (C-1) with a liquid crystal alignment film. The average surface roughness (Ra) of this liquid crystal alignment film was measured and shown in Table 1.

(實施例16) (Embodiment 16)

用1.0μm的過濾器將實施例2所得到的液晶配向劑(A-2)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射250mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(C-2)。對於該液晶配向膜來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent (A-2) obtained in Example 2 was filtered with a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 60 ° C for 5 minutes, and used. The hot air circulating oven having a temperature of 230 ° C was fired for 10 minutes to obtain a ruthenium film having a thickness of 100 nm. The fired film was irradiated with ultraviolet rays of 254 nm of 250 mJ/cm 2 through a polarizing plate to obtain a substrate (C-2) with a liquid crystal alignment film. The average surface roughness (Ra) of this liquid crystal alignment film was measured and shown in Table 1.

(實施例17) (Example 17)

用1.0μm的過濾器將實施例3所得到的液晶配向劑 (A-3)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射250mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(C-3)。對於該液晶配向膜來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent obtained in Example 3 was treated with a 1.0 μm filter. (A-3) After filtration, it was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 60 ° C for 5 minutes, and fired in a hot air circulating oven at a temperature of 230 ° C for 10 minutes. A ruthenium-imided film having a film thickness of 100 nm was obtained. The fired film was irradiated with ultraviolet rays of 254 nm of 250 mJ/cm 2 through a polarizing plate to obtain a substrate (C-3) with a liquid crystal alignment film. The average surface roughness (Ra) of this liquid crystal alignment film was measured and shown in Table 1.

(實施例18) (Embodiment 18)

用1.0μm的過濾器將實施例4所得到的液晶配向劑(A-4)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射250mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(C-4)。對於該液晶配向膜來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent (A-4) obtained in Example 4 was filtered with a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 60 ° C for 5 minutes, and used. The hot air circulating oven having a temperature of 230 ° C was fired for 10 minutes to obtain a ruthenium film having a thickness of 100 nm. The fired film was irradiated with ultraviolet rays of 254 nm of 250 mJ/cm 2 through a polarizing plate to obtain a substrate (C-4) with a liquid crystal alignment film. The average surface roughness (Ra) of this liquid crystal alignment film was measured and shown in Table 1.

(實施例19) (Embodiment 19)

用1.0μm的過濾器將實施例5所得到的液晶配向劑(A-5)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射 250mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(C-5)。對於該膜液晶配向來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent (A-5) obtained in Example 5 was filtered with a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 60 ° C for 5 minutes, and used. The hot air circulating oven having a temperature of 230 ° C was fired for 10 minutes to obtain a ruthenium film having a thickness of 100 nm. Irradiation of the fired film through a polarizing plate A 254 nm ultraviolet ray of 250 mJ/cm 2 was obtained to obtain a substrate (C-5) with a liquid crystal alignment film. The average surface roughness (Ra) was measured for the liquid crystal alignment of the film and is shown in Table 1.

(實施例20) (Embodiment 20)

用1.0μm的過濾器將實施例6所得到的液晶配向劑(A-6)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射250mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(C-6)。對於該液晶配向膜來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent (A-6) obtained in Example 6 was filtered with a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 60 ° C for 5 minutes, and used. The hot air circulating oven having a temperature of 230 ° C was fired for 10 minutes to obtain a ruthenium film having a thickness of 100 nm. The fired film was irradiated with ultraviolet rays of 254 nm of 250 mJ/cm 2 through a polarizing plate to obtain a substrate (C-6) with a liquid crystal alignment film. The average surface roughness (Ra) of this liquid crystal alignment film was measured and shown in Table 1.

(實施例21) (Example 21)

用1.0μm的過濾器將實施例7所得到的液晶配向劑(A-7)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射250mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(C-7)。對於該液晶配向膜來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent (A-7) obtained in Example 7 was filtered with a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 60 ° C for 5 minutes, and used. The hot air circulating oven having a temperature of 230 ° C was fired for 10 minutes to obtain a ruthenium film having a thickness of 100 nm. The fired film was irradiated with ultraviolet rays of 254 nm of 250 mJ/cm 2 through a polarizing plate to obtain a substrate (C-7) with a liquid crystal alignment film. The average surface roughness (Ra) of this liquid crystal alignment film was measured and shown in Table 1.

(實施例22) (Example 22)

用1.0μm的過濾器將實施例8所得到的液晶配向劑(A-8)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射250mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(C-8)。對於該液晶配向膜來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent (A-8) obtained in Example 8 was filtered with a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 60 ° C for 5 minutes, and used. The hot air circulating oven having a temperature of 230 ° C was fired for 10 minutes to obtain a ruthenium film having a thickness of 100 nm. The fired film was irradiated with ultraviolet rays of 254 nm of 250 mJ/cm 2 through a polarizing plate to obtain a substrate (C-8) with a liquid crystal alignment film. The average surface roughness (Ra) of this liquid crystal alignment film was measured and shown in Table 1.

(實施例23) (Example 23)

用1.0μm的過濾器將實施例9所得到的液晶配向劑(A-9)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射250mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(C-9)。對於該液晶配向膜來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent (A-9) obtained in Example 9 was filtered with a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 60 ° C for 5 minutes, and used. The hot air circulating oven having a temperature of 230 ° C was fired for 10 minutes to obtain a ruthenium film having a thickness of 100 nm. The fired film was irradiated with ultraviolet rays of 254 nm of 250 mJ/cm 2 through a polarizing plate to obtain a substrate (C-9) with a liquid crystal alignment film. The average surface roughness (Ra) of this liquid crystal alignment film was measured and shown in Table 1.

(比較例3) (Comparative Example 3)

用1.0μm的過濾器將比較例1所得到的液晶配向劑(B-1)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃ 的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射500mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(D-1)。對於該液晶配向膜來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent (B-1) obtained in Comparative Example 1 was filtered with a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 60 ° C for 5 minutes, and used. Temperature 230 ° C The hot air circulating oven was fired for 10 minutes to obtain a ruthenium film having a film thickness of 100 nm. The 245 nm ultraviolet rays of 500 mJ/cm 2 were irradiated to the fired film through a polarizing plate to obtain a substrate (D-1) with a liquid crystal alignment film. The average surface roughness (Ra) of this liquid crystal alignment film was measured and shown in Table 1.

(比較例4) (Comparative Example 4)

用1.0μm的過濾器將比較例2所得到的液晶配向劑(B-2)做過濾後，旋轉塗布至附有透明電極的玻璃基板上，在溫度60℃的加熱板上乾燥5分鐘，並用溫度230℃的熱風循環式烘箱經過10分鐘的燒成，而得到膜厚100nm的醯亞胺化的膜。介隔著偏光板對燒成膜照射500mJ/cm2的254nm的紫外線，而得到附有液晶配向膜的基板(D-2)。對於該液晶配向膜來測定平均面粗糙度(Ra)並表示於表1中。 The liquid crystal alignment agent (B-2) obtained in Comparative Example 2 was filtered with a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 60 ° C for 5 minutes, and used. The hot air circulating oven having a temperature of 230 ° C was fired for 10 minutes to obtain a ruthenium film having a thickness of 100 nm. The fired film was irradiated with ultraviolet rays of 254 nm of 500 mJ/cm 2 through a polarizing plate to obtain a substrate (D-2) with a liquid crystal alignment film. The average surface roughness (Ra) of this liquid crystal alignment film was measured and shown in Table 1.

(實施例24) (Example 24)

用離子化位能測定裝置AC-2(理研計器)，將實施例15所得到的基板(C-1)之膜表面進行測定膜表面之光電子數。若測定膜由2種類以上的材料所構成時，分別測定於材料中單獨的光電子數，並從該光電子比率來計算出混合時的層分離比率。例如若A材料單膜之光電子數為X，B材料單膜之光電子數Y，由AB兩材料所構成的混合膜之光電子數為Z時，該表層比例C係可以下式來表示。將 基於本式所算出的結果表示於表1。 The surface of the film of the substrate (C-1) obtained in Example 15 was measured for the number of photoelectrons on the surface of the film by an ionization potential energy measuring device AC-2 (Researcher). When the measurement film is composed of two or more types of materials, the number of individual photoelectrons in the material is measured, and the layer separation ratio at the time of mixing is calculated from the photoelectron ratio. For example, when the number of photoelectrons of the single film of the A material is X, the number of photoelectrons Y of the single film of the B material, and the number of photoelectrons of the mixed film composed of the two materials of AB are Z, the surface layer ratio C can be expressed by the following formula. will The results calculated based on this formula are shown in Table 1.

C=(Y-Z)/(Y-X)＊ 100 C=(Y-Z)/(Y-X)* 100

(實施例25~32、比較例5、6) (Examples 25 to 32, Comparative Examples 5 and 6)

即使是對於實施例15以後所得到的基板(C-2)~(C-9)、(D-1)、(D-2)，亦進行與實施例24相同之操作來測定膜表面的光電子數並表示於表1。 Even in the substrates (C-2) to (C-9), (D-1), and (D-2) obtained in Example 15, the same operation as in Example 24 was carried out to measure photoelectrons on the surface of the film. The numbers are shown in Table 1.

<配向性評估晶胞之製作方法> <Method for producing alignment evaluation unit cell> ‧評估晶胞之製作方法 ‧Evaluation method of making cell

首先準備附有電極的基板。基板係使用大小30mm×50mm、厚度0.7mm的玻璃基板。於基板上，形成作為第 1層之構成對向電極之具備整面圖型的ITO電極。於第1層的對向電極之上，形成作為第2層之藉由CVD法而成膜的SiN(氮化矽)膜。第2層的SiN膜的膜厚為500nm，作為層間絕緣膜之機能。於第2層的SiN膜之上，形成作為第3層之配置有ITO膜經圖型化而形成的梳齒狀像素電極之第1像素及第2像素的2種像素。各像素的尺寸係以長10mm寬約5mm。此時，第1層的對向電極與第3層的像素電極係因第2層的SiN膜的作用而電絕緣。 First, a substrate with electrodes is prepared. A glass substrate having a size of 30 mm × 50 mm and a thickness of 0.7 mm was used as the substrate. On the substrate, formed as the first One layer of the ITO electrode having the entire surface pattern of the counter electrode. On the counter electrode of the first layer, a SiN (tantalum nitride) film formed as a second layer by a CVD method is formed. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. On the SiN film of the second layer, two types of pixels of the first pixel and the second pixel of the comb-shaped pixel electrode formed by patterning the ITO film are formed. The size of each pixel is about 5 mm in length and 10 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

第3層的像素電極係具有多個中央部分為彎曲的“ㄑ”字形狀的電極元件排列所構成的梳齒狀之形狀。各電極元件的短邊方向的寬為3μm，電極元件間的間隔為6μm。形成各像素的像素電極由多個中央部分彎曲的“ㄑ”字形狀的電極元件排列所構成，故各像素的形狀不是長方形狀，而是具備有與電極元件相同地在中央部分彎曲的類似粗體字的“ㄑ”字的形狀。又，各像素係將其中央的彎曲部分為界線被分割成上下，具有彎曲部分上側的第1區域與下側的第2區域。 The pixel electrode of the third layer has a comb-like shape in which a plurality of central electrode portions are arranged in a curved "ㄑ"-shaped electrode element. The width of each electrode element in the short-side direction was 3 μm, and the interval between the electrode elements was 6 μm. The pixel electrode forming each pixel is composed of a plurality of "ㄑ"-shaped electrode elements in which the central portion is curved. Therefore, the shape of each pixel is not rectangular, but is similar to the electrode element, and is curved in the central portion. The shape of the word "ㄑ". Further, each pixel is divided into upper and lower sides by a curved portion at the center thereof, and has a first region on the upper side of the curved portion and a second region on the lower side.

若比較各像素的第1區域與第2區域時，則構成該等的像素電極的電極元件之形成方向為不同的。即，若將後述的液晶配向膜之配向方向作為基準時，像素的第1區域中像素電極的電極元件以呈+10°的角度(順時針)之方式來形成，而像素的第2區域中像素電極的電極元件以呈-10°的角度(順時針)之方式來形成。即，各像素的第1區域與第2區域中，以藉由像素電極與對向電極之 間的外加電壓而被激起的液晶在基板面內的旋轉動作(平面內切換)之方向為彼此相反方向之方式來構成。 When the first region and the second region of each pixel are compared, the direction in which the electrode elements constituting the pixel electrodes are formed is different. In other words, when the alignment direction of the liquid crystal alignment film to be described later is used as a reference, the electrode elements of the pixel electrodes in the first region of the pixel are formed at an angle of +10° (clockwise), and in the second region of the pixel. The electrode elements of the pixel electrode are formed at an angle of -10° (clockwise). That is, in the first region and the second region of each pixel, the pixel electrode and the opposite electrode are used. The direction in which the liquid crystal excited by the applied voltage is excited in the plane of the substrate (in-plane switching) is configured to be opposite to each other.

依據上述之方法，用1.0μm的過濾器將所得到的液晶配向劑做過濾後，分別旋轉塗布至已準備的上述附有電極的基板、與作為對向基板的內面成膜有ITO膜且具有高4μm的柱狀間隔物的玻璃基板上，藉由在80℃的加熱板上乾燥5分鐘後，以230℃燒成30分鐘，可於各基板上得到膜厚為70nm以上的塗膜的聚醯亞胺膜。以指定的配向方向對該聚醯亞胺膜照射波長200~300nm的紫外線0.01J~1J/cm2，之後以230℃乾燥30分鐘。 According to the method described above, the obtained liquid crystal alignment agent was filtered with a 1.0 μm filter, and then spin-coated, respectively, onto the prepared electrode-attached substrate, and an ITO film was formed on the inner surface of the counter substrate. The glass substrate having a columnar spacer having a height of 4 μm was dried on a hot plate at 80° C. for 5 minutes and then baked at 230° C. for 30 minutes to obtain a coating film having a film thickness of 70 nm or more on each substrate. Polyimine film. The polyimide film was irradiated with ultraviolet rays having a wavelength of 200 to 300 nm at a range of 0.01 J to 1 J/cm 2 in a predetermined alignment direction, and then dried at 230 ° C for 30 minutes.

使用附有上述液晶配向膜的2種類基板，以分別的配向方向呈反向平行之方式來組合，留下液晶注入口並密封周圍，製作晶胞間隙為3.6μm的空晶胞。在常溫下向該空晶胞中真空注入液晶(MLC-2041、Merck公司製)後，密封注入口而製作反向平行配向的液晶晶胞。所得到的液晶晶胞係構成IPS模式液晶顯示元件。之後，以110℃將所得到的液晶晶胞加熱1小時並放置一晚可得到液晶配向晶胞。 Two types of substrates with the above-described liquid crystal alignment film were used, and the respective alignment directions were combined in antiparallel to leave a liquid crystal injection port and sealed around to form an empty cell having a cell gap of 3.6 μm. Liquid crystal (MLC-2041, manufactured by Merck) was vacuum-injected into the empty cell at normal temperature, and then the injection port was sealed to produce a liquid crystal cell in which the antiparallel alignment was performed. The obtained liquid crystal cell system constitutes an IPS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heated at 110 ° C for 1 hour and left overnight to obtain a liquid crystal alignment unit cell.

(實施例33) (Example 33)

對於實施例1所得到的液晶配向劑(A-1)，依據上述之方法製作液晶評估晶胞(E-1)。 With respect to the liquid crystal alignment agent (A-1) obtained in Example 1, a liquid crystal evaluation unit cell (E-1) was produced in accordance with the above method.

(實施例34~46、比較例7、8) (Examples 34 to 46, Comparative Examples 7, 8)

對於實施例2之後所得到的液晶配向劑(A-2)~(A-14)、(B-1)、(B-2)，亦進行與實施例33相同之操作來製作評估用晶胞(E-2)~(E-14)、(F-1)、(F-2)。 The liquid crystal alignment agents (A-2) to (A-14), (B-1), and (B-2) obtained after the second embodiment were also subjected to the same operation as in Example 33 to prepare a cell for evaluation. (E-2)~(E-14), (F-1), (F-2).

(實施例47) (Example 47)

對於實施例33所得到的液晶評估晶胞(E-1)，實施藉由長期驅動之殘影評估。藉由長期交流驅動之殘影評估方法係如同以下般。 With respect to the liquid crystal evaluation unit cell (E-1) obtained in Example 33, the residual image evaluation by long-term driving was carried out. The residual image evaluation method driven by long-term communication is as follows.

(藉由長期驅動之殘影評估) (assessed by long-term driving residuals)

在60℃的恆溫環境下，以頻率30Hz外加8VPP的交流電壓100小時。之後，使液晶晶胞的像素電極與對向電極之間呈短路狀態，直接在室溫下放置一日。 An AC voltage of 8 VPP was applied at a frequency of 30 Hz for 100 hours at a constant temperature of 60 °C. Thereafter, the pixel electrode of the liquid crystal cell and the counter electrode were short-circuited, and were allowed to stand at room temperature for one day.

放置後，將液晶晶胞設置在以偏光軸呈垂直之方式所配置的2片偏光板之間，在無外加電壓的狀態下點亮背光源，並以透過光的輝度達到最小之方式來調整液晶晶胞之配置角度。又，將液晶晶胞從第1像素的第2區域最暗的角度，旋轉至第1區域最暗的角度時的旋轉角度作為角度△並算出該值。第2像素也相同地，將第2區域與第1區域進行比較，並相同地算出角度△。又，將第1像素與第2像素的角度△值之平均值作為液晶晶胞的角度△並算出該值。若該液晶晶胞的角度△之值超過0.2度時，定義並評估為「不良」。若該液晶晶胞的角度△之值未超過0.2度時，則定義並評估為「良好」。將評估結果表示於表 2。 After being placed, the liquid crystal cell is placed between two polarizing plates arranged in a manner perpendicular to the polarizing axis, and the backlight is lit without an applied voltage, and is adjusted in such a manner that the luminance of the transmitted light is minimized. The arrangement angle of the liquid crystal cell. Further, the liquid crystal cell is rotated from the darkest angle of the second region of the first pixel to the angle of the darkest angle of the first region as the angle Δ, and the value is calculated. Similarly to the second pixel, the second region is compared with the first region, and the angle Δ is calculated in the same manner. Moreover, the average value of the angle Δ values of the first pixel and the second pixel is defined as the angle Δ of the liquid crystal cell, and this value is calculated. If the value of the angle Δ of the liquid crystal cell exceeds 0.2 degrees, it is defined and evaluated as "poor". If the value of the angle Δ of the liquid crystal cell does not exceed 0.2 degrees, it is defined and evaluated as "good". Express the results of the assessment on the table 2.

(實施例48~60、比較例7、8) (Examples 48 to 60, Comparative Examples 7, 8)

對於實施例34~實施例46、比較例7~8所得到的液晶評估晶胞(E-2)~(E-14)、(F-1)、(F-2)，亦進行與實施例47相同之操作，實施長時間交流驅動時之殘影評估。對於測定結果係表示於表2。 The liquid crystal evaluation unit cells (E-2) to (E-14), (F-1), and (F-2) obtained in Examples 34 to 46 and Comparative Examples 7 to 8 were also subjected to the examples. 47 The same operation, the residual image evaluation when implementing long-term AC drive. The measurement results are shown in Table 2.

(實施例61) (Example 61)

對於實施例33所得到的液晶評估晶胞(E-1)，實施藉由交流驅動+直流驅動之殘影評估。殘影評估方法係如同以下般。 For the liquid crystal evaluation cell (E-1) obtained in Example 33, the afterimage evaluation by AC drive + DC drive was performed. The residual image evaluation method is as follows.

(殘影評估) (afterimage evaluation)

使用以下的光學體系等來進行殘影之評估。 The evaluation of the afterimage was performed using the following optical system or the like.

將所製作的液晶晶胞設置在以偏光軸呈垂直之方式所配置的2片偏光板之間，在無外加電壓的狀態下點亮LED背光源，並以透過光的輝度呈最小之方式來調整液晶晶胞之配置角度。 The liquid crystal cell to be fabricated is placed between two polarizing plates arranged in a manner perpendicular to the polarization axis, and the LED backlight is lit without an applied voltage, and the luminance of the transmitted light is minimized. Adjust the arrangement angle of the liquid crystal cell.

接著，一邊對該液晶晶胞外加頻率30Hz的交流電壓，一邊測定V-T曲線(電壓-透過率曲線)，將相對透過率達到23%的交流電壓作為驅動電壓並算出該值。 Next, a V-T curve (voltage-transmittance curve) was measured while applying an AC voltage having a frequency of 30 Hz to the liquid crystal cell, and an AC voltage having a transmittance of 23% was used as a driving voltage to calculate the value.

殘影評估中，外加相對透過率達到23%、且頻率30Hz的交流電壓來使液晶晶胞驅動，同時外加1V 的直流電壓使其驅動60分鐘。之後，使外加直流電壓值為0V而僅停止直流電壓的外加，在該狀態下進而驅動30分鐘。 In the afterimage evaluation, an AC voltage with a relative transmittance of 23% and a frequency of 30 Hz is applied to drive the liquid crystal cell, and 1 V is applied. The DC voltage is driven for 60 minutes. Thereafter, the applied DC voltage value was 0 V, and only the addition of the DC voltage was stopped, and in this state, the drive was further driven for 30 minutes.

殘影評估係從停止外加直流電壓的時間點起至經過60分鐘為止，若相對透過率回復至25%以下時，定義且評估為「良好」。相對透過率回復至25%以下為止若需要30分鐘以上時，則定義且評估為「不良」。 The image sticking evaluation was defined and evaluated as "good" when the relative transmittance was returned to 25% or less from the time when the DC voltage was applied to the time when the DC voltage was stopped. If it takes more than 30 minutes for the relative transmittance to return to 25% or less, it is defined and evaluated as "poor".

又，依據上述方法之殘影評估係液晶晶胞的溫度在23℃的狀態之溫度條件下來進行。將所得到的結果表示於表2。 Further, the residual image evaluation based on the above method was carried out under the temperature condition of the state of the liquid crystal cell at 23 °C. The results obtained are shown in Table 2.

(實施例62~74、比較例9、10)) (Examples 62 to 74, Comparative Examples 9, 10))

對於實施例34~46、比較例7、8所得到的液晶評估晶胞(E-2)~(E-14)、(F-1)、(F-2)，亦進行與實施例47相同之操作，實施交流+直流驅動時之殘影評估。對於測定結果係表示於表2。 The liquid crystal evaluation cells (E-2) to (E-14), (F-1), and (F-2) obtained in Examples 34 to 46 and Comparative Examples 7 and 8 were also the same as in Example 47. Operation, implementation of AC + DC drive residual image evaluation. The measurement results are shown in Table 2.

[產業利用性] [Industry Utilization]

使用本發明的液晶配向劑所製作的液晶顯示元件，係顯示品質為優異之同時可靠性亦為優異，可廣泛地使用於大畫面且高精細的液晶電視或智慧手機等。 The liquid crystal display element produced by using the liquid crystal alignment agent of the present invention is excellent in display quality and excellent in reliability, and can be widely used for a large-screen and high-definition liquid crystal television or smart phone.

尚，在此引用2015年7月31日提出專利申請的日本特願2015-152600號的說明書、申請專利範圍、圖式、及摘要的全部內容來做為本發明說明書之揭示。 The entire disclosure of the specification, the claims, the drawings, and the abstract of the Japanese Patent Application No. 2015-152600, filed on Jul. 31, 2015, the entire disclosure of which is hereby incorporated by reference.

Claims (13)

一種液晶配向劑，其特徵係含有聚醯胺酸酯成分(A)、與聚醯胺酸成分(B)，該聚醯胺酸酯成分(A)具有下述式(1)所表示的重複單位及式(2)所表示的重複單位， (式中，R1為碳數1~6之烷基，R2~R5相互獨立為氫原子或碳數1~6之烷基，Y1為下述式(Y1-2)所表示的2價有機基，Y2為選自由下述式(Y2-1)及(Y2-2)所成之群之至少1種的2價有機基) (式中，A1及A5分別獨立為單鍵、或碳數1~5之伸烷基，A2及A4分別獨立為碳數1~5之伸烷基，A3為碳數1~6之 伸烷基、或伸環烷基，B1及B2分別獨立為單鍵、-O-、-NH-、-NMe-、-C(=O)-、-C(=O)O-、-C(=O)NH-、-C(=O)NMe-、-OC(=O)-、-NHC(=O)-、或-N(Me)C(=O)-，D1為tert-丁氧基羰基、或9-茀基甲氧基羰基，a為0或1，n為2~6之整數)。 A liquid crystal alignment agent comprising a polyphthalate component (A) and a polyaminic acid component (B) having a repeat represented by the following formula (1) Unit and the repeating unit represented by formula (2), (wherein R 1 is an alkyl group having 1 to 6 carbon atoms, and R 2 to R 5 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y 1 is represented by the following formula (Y 1 - 2) The divalent organic group, Y 2 is a divalent organic group selected from at least one of the group consisting of the following formulas (Y 2 -1) and (Y 2 -2) (wherein, A 1 and A 5 are each independently a single bond or an alkylene group having a carbon number of 1 to 5, and A 2 and A 4 are each independently an alkylene group having 1 to 5 carbon atoms, and A 3 is a carbon number of 1 ~6 alkylene, or cycloalkyl, B 1 and B 2 are independently a single bond, -O-, -NH-, -NMe-, -C(=O)-, -C(=O) O-, -C(=O)NH-, -C(=O)NMe-, -OC(=O)-, -NHC(=O)-, or -N(Me)C(=O)-, D 1 is tert-butoxycarbonyl or 9-fluorenylmethoxycarbonyl, a is 0 or 1, and n is an integer of 2 to 6). 如請求項1之液晶配向劑，其中，聚醯胺酸酯(A)成分與聚醯胺酸(B)成分之含有比率以質量比(A/B)為1/9~9/1，前述(A)成分與(B)成分之固體成分濃度之合計為0.5~10質量%。 The liquid crystal alignment agent of claim 1, wherein the content ratio of the polyphthalate (A) component to the polyamic acid (B) component is 1/9 to 9/1 by mass ratio (A/B), The total solid content concentration of the component (A) and the component (B) is 0.5 to 10% by mass. 如請求項1或2之液晶配向劑，其中，聚醯胺酸酯(A)成分中的式(1)的重複單位，相對於全重複單位為5~60莫耳%。 The liquid crystal alignment agent of claim 1 or 2, wherein the repeating unit of the formula (1) in the polyphthalate (A) component is 5 to 60 mol% with respect to the total repeating unit. 如請求項1~3中任一項之液晶配向劑，其中，聚醯胺酸酯(A)成分中的式(2)的重複單位，相對於全重複單位為10~70莫耳%。 The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the repeating unit of the formula (2) in the polyphthalate (A) component is 10 to 70 mol% with respect to the total repeating unit. 如請求項1之液晶配向劑，其中，除了前述重複單位以外，聚醯胺酸酯(A)成分進而具有下述式(3)所表示的重複單位， (式中，R1~R5與前述式(1)、(2)為相同，Y3為下述式(Y-7)所表示的2價有機基) The liquid crystal alignment agent of claim 1, wherein the polyphthalate (A) component further has a repeating unit represented by the following formula (3), in addition to the above repeating unit; (wherein R 1 to R 5 are the same as the above formulae (1) and (2), and Y 3 is a divalent organic group represented by the following formula (Y-7)) 如請求項5之液晶配向劑，其中，聚醯胺酸酯(A)成分中的式(3)的重複單位，相對於前述聚醯胺酸酯(A)成分的全重複單位為30~50莫耳%。 The liquid crystal alignment agent of claim 5, wherein the repeating unit of the formula (3) in the polyphthalate (A) component is 30 to 50 with respect to the total repeating unit of the polyamidomate (A) component. Moer%. 如請求項1或5之液晶配向劑，其中，前述式(1)~(3)所表示的重複單位中的R2、R4為甲基。 The liquid crystal alignment agent of claim 1 or 5, wherein R 2 and R 4 in the repeating unit represented by the above formulas (1) to (3) are a methyl group. 如請求項1或7之液晶配向劑，其中，聚醯胺酸(B)成分為下述式(4)所表示的四羧酸二酐成分與二胺成分反應而得到者， (式中，X為選自下述至少1種所表示的4價有機基) The liquid crystal alignment agent of claim 1 or 7, wherein the poly (protonic acid) (B) component is obtained by reacting a tetracarboxylic dianhydride component represented by the following formula (4) with a diamine component, (wherein X is a tetravalent organic group selected from at least one of the following) 如請求項1~8中任一項之液晶配向劑，其中，含有有機溶劑，該有機溶劑的N-甲基-2-吡咯啶酮之含有比率，相對於液晶配向劑之全重量為30~50質量%。 The liquid crystal alignment agent according to any one of claims 1 to 8, which contains an organic solvent, and the content ratio of the N-methyl-2-pyrrolidone of the organic solvent is 30% with respect to the total weight of the liquid crystal alignment agent. 50% by mass. 如請求項1~9中任一項之液晶配向劑，其係光配向處理液晶配向膜用。 The liquid crystal alignment agent according to any one of claims 1 to 9, which is used for photoalignment treatment of a liquid crystal alignment film. 一種液晶配向膜，其係由請求項1~10中任一項之液晶配向劑而得到。 A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of claims 1 to 10. 一種液晶顯示元件，其係具有請求項11之液晶配向膜。 A liquid crystal display element having the liquid crystal alignment film of claim 11. 一種液晶配向膜之製造方法，其係將請求項1~10中任一項之液晶配向劑塗布至附有電極的基板上，進行光配向處理。 A method for producing a liquid crystal alignment film by applying the liquid crystal alignment agent according to any one of claims 1 to 10 to a substrate with an electrode and performing photoalignment treatment.
TW105124225A 2015-07-31 2016-07-29 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element TWI781910B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-152600 2015-07-31
JP2015152600 2015-07-31

Publications (2)

Publication Number Publication Date
TW201718709A true TW201718709A (en) 2017-06-01
TWI781910B TWI781910B (en) 2022-11-01

Family

ID=57943062

Family Applications (1)

Application Number Title Priority Date Filing Date
TW105124225A TWI781910B (en) 2015-07-31 2016-07-29 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

Country Status (5)

Country Link
JP (1) JP6791143B2 (en)
KR (1) KR102672865B1 (en)
CN (1) CN108139633B (en)
TW (1) TWI781910B (en)
WO (1) WO2017022636A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7243628B2 (en) * 2017-09-26 2023-03-22 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using the same
KR101905112B1 (en) 2018-07-02 2018-10-08 (주)오알켐 Coating composition for printed circuit boards and manufacturing method of thereof
WO2020255890A1 (en) * 2019-06-20 2020-12-24 Ｊｆｅケミカル株式会社 Polyimide solution and polyimide
CN114479077B (en) * 2022-01-19 2024-03-29 波米科技有限公司 Polyamic acid ester and application thereof in liquid crystal aligning agent, liquid crystal aligning film and liquid crystal unit

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008176304A (en) * 2006-12-22 2008-07-31 Jsr Corp Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display element, and optical member
JP5355970B2 (en) * 2008-09-16 2013-11-27 株式会社ジャパンディスプレイ Liquid crystal display
JPWO2011115079A1 (en) * 2010-03-15 2013-06-27 日産化学工業株式会社 Liquid crystal aligning agent for photo-alignment treatment method, and liquid crystal alignment film using the same
TWI501998B (en) * 2010-03-15 2015-10-01 Nissan Chemical Ind Ltd A liquid crystal aligning agent containing a polyamic acid ester, and a liquid crystal alignment film
EP2705808B1 (en) * 2010-07-30 2024-05-01 Alcon Inc. Silicone hydrogel lenses with water-rich surfaces
WO2013081067A1 (en) * 2011-11-30 2013-06-06 日産化学工業株式会社 Liquid crystal alignment film, method for producing liquid crystal alignment film, and liquid crystal display element
CN105283801B (en) 2013-03-25 2019-07-09 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
CN105659156B (en) * 2013-10-23 2019-02-01 日产化学工业株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element
KR102391044B1 (en) * 2013-11-15 2022-04-26 닛산 가가쿠 가부시키가이샤 Liquid crystal aligning agent, and liquid crystal display element using same

Also Published As

Publication number Publication date
JPWO2017022636A1 (en) 2018-05-24
JP6791143B2 (en) 2020-11-25
CN108139633B (en) 2021-04-23
TWI781910B (en) 2022-11-01
KR102672865B1 (en) 2024-06-05
KR20180037013A (en) 2018-04-10
WO2017022636A1 (en) 2017-02-09
CN108139633A (en) 2018-06-08

Similar Documents

Publication Publication Date Title
TWI656173B (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP6627772B2 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device using the same
TWI622621B (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP6314827B2 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
US11352564B2 (en) Liquid crystal alignment agent composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, liquid crystal display using the same
TWI596137B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
TW201518408A (en) Liquid crystal aligning agent and liquid crystal aligning film using same
TWI781910B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
TW201529727A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
TW201736440A (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2012176822A1 (en) Liquid crystal orientation agent for photo-orientation treatment method and liquid crystal orientation film using same
TW201700538A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
KR102572922B1 (en) Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using the same
TWI670293B (en) Liquid crystal alignment agent and liquid crystal display element using same
TW201825658A (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
TWI657099B (en) Liquid crystal alignment agent and liquid crystal display element using the same
TW201502202A (en) Liquid crystal orientation agent, liquid crystal orientation membrane, and liquid crystal display element using same
TWI596201B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
TW201609968A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
TWI668247B (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal alignment element using the same
TW201734088A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
KR20220076312A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal device, and polymer
JP2023109149A (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer, and compound
CN115997162A (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
JP2021521487A (en) Liquid crystal alignment agent composition, manufacturing method of liquid crystal alignment film using this, liquid crystal alignment film and liquid crystal display element using this