TWI520948B - A liquid crystal alignment device, a liquid crystal alignment device, a liquid crystal display device, and a liquid crystal display device, and a polymerizable compound - Google Patents

A liquid crystal alignment device, a liquid crystal alignment device, a liquid crystal display device, and a liquid crystal display device, and a polymerizable compound Download PDF

Info

Publication number
TWI520948B
TWI520948B TW100123258A TW100123258A TWI520948B TW I520948 B TWI520948 B TW I520948B TW 100123258 A TW100123258 A TW 100123258A TW 100123258 A TW100123258 A TW 100123258A TW I520948 B TWI520948 B TW I520948B
Authority
TW
Taiwan
Prior art keywords
liquid crystal
crystal alignment
group
alignment agent
polymerizable compound
Prior art date
Application number
TW100123258A
Other languages
Chinese (zh)
Other versions
TW201217352A (en
Inventor
Ryoichi Ashizawa
Daniel Antonio Sahade
Kinya Matsumoto
Hirokazu Yamanouchi
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 TW201217352A publication Critical patent/TW201217352A/en
Application granted granted Critical
Publication of TWI520948B publication Critical patent/TWI520948B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F24/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/58—One oxygen atom, e.g. butenolide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Liquid Crystal (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Furan Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Description

液晶配向劑、液晶配向膜、液晶顯示元件及液晶顯示元件之製造方法，以及聚合性化合物Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, and method for producing liquid crystal display element, and polymerizable compound

本發明係關於可使用於藉由在於液晶分子外加電壓的狀態下，照射紫外線而製作之液晶顯示元件的製造上之液晶配向劑、液晶配向膜、液晶顯示元件及液晶顯示元件之製造方法以及聚合性化合物。The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, and a liquid crystal display element manufacturing method and polymerization which can be used for manufacturing a liquid crystal display element produced by irradiating ultraviolet rays in a state where a voltage is applied to liquid crystal molecules. Sex compounds.

將對於基板配向呈垂直的液晶分子藉由電場使其應答之方式(亦稱為垂直配向(VA)方式)的液晶顯示元件中，對於該製造過程，含有於液晶分子一邊外加電壓一邊照射紫外線之步驟者。In a liquid crystal display device in which a liquid crystal molecule having a vertical alignment with respect to a substrate is responsive to an electric field (also referred to as a vertical alignment (VA) method), in the manufacturing process, ultraviolet rays are applied while applying a voltage to the liquid crystal molecules. Stepper.

在如此垂直配向方式之液晶顯示元件中，預先於液晶組成物中添加光聚合性化合物，與聚醯亞胺等垂直配向膜同時使用，藉由於液晶胞一邊外加電壓，一邊照射紫外線，加速液晶之應答速度的技術(例如參照專利文獻1及非專利文獻1)(PSA(Polymer sustained Alignment)型液晶顯示器)。一般對電場應答之液晶分子的傾斜方向，雖藉由設置於基板上的突起或設置於顯示用電極的縫隙等來控制，但藉由於液晶組成物中添加光聚合性化合物，於液晶胞一邊外加電壓，一邊照射紫外線，液晶分子的傾斜方向被記憶的聚合物結構物形成於液晶配向膜上，故與僅由突起或縫隙來控制液晶分子的傾斜方向之方法相比較，可加速液晶顯示元件的應答速度。In the liquid crystal display device of such a vertical alignment type, a photopolymerizable compound is added to the liquid crystal composition in advance, and a vertical alignment film such as polyimide or the like is used at the same time, and ultraviolet rays are applied to the liquid crystal cell to accelerate the liquid crystal. A technique for responding to a speed (for example, refer to Patent Document 1 and Non-Patent Document 1) (PSA (Polymer sustained Alignment) type liquid crystal display). Generally, the tilt direction of the liquid crystal molecules responsive to the electric field is controlled by a protrusion provided on the substrate or a slit provided in the display electrode, but a photopolymerizable compound is added to the liquid crystal composition, and is added to the liquid crystal cell. The voltage is irradiated with ultraviolet rays, and the polymer structure in which the liquid crystal molecules are tilted is formed on the liquid crystal alignment film, so that the liquid crystal display element can be accelerated compared with the method of controlling the tilt direction of the liquid crystal molecules only by the protrusions or slits. Response speed.

又，已有報告指出即使將光聚合性化合物非添加於液晶組成物中，而添加於液晶配向膜中，亦可加速液晶顯示元件的應答速度(SC-PVA型液晶顯示器)(例如參照非專利文獻2)。In addition, it has been reported that even if a photopolymerizable compound is added to a liquid crystal alignment film without being added to a liquid crystal alignment film, the response speed of the liquid crystal display element can be accelerated (SC-PVA liquid crystal display) (for example, refer to the non-patent) Literature 2).

[先行技術文獻][Advanced technical literature]

[專利文獻][Patent Literature]

[專利文獻1]特開2003-307720號公報[Patent Document 1] JP-A-2003-307720

[非專利文獻][Non-patent literature]

[非專利文獻1]K.Hanaoka,SID 04 DIGEST、P.1200-1202[Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, P.1200-1202

[非專利文獻2]K.H Y.-J.Lee,SID 09 DIGEST、P.666-668[Non-Patent Document 2] K.H Y.-J.Lee, SID 09 DIGEST, P.666-668

然而，可望進一步加速液晶顯示元件之應答速度。其中，雖考慮到藉由增多光聚合性化合物之添加量，可加速液晶顯示元件之應答速度，若該光聚合性化合物於液晶中未反應下直接殘留時會成為雜質(污染)，成為降低液晶顯示元件的信賴性之原因。此時考慮到使用對液晶之少量添加下可加速應答速度的聚合性化合物之方法，但此亦有著極限。在上述背景中，期待一種即使於液晶中未含有聚合性化合物，亦可加速應答速度的液晶配向劑。However, it is expected that the response speed of the liquid crystal display element can be further accelerated. In addition, it is considered that the increase in the amount of addition of the photopolymerizable compound can accelerate the response speed of the liquid crystal display device, and if the photopolymerizable compound remains directly in the liquid crystal without being reacted, it becomes an impurity (contamination) and becomes a liquid crystal. The reason for the reliability of the display component. At this time, it is considered to use a method of adding a polymerizable compound which accelerates the response speed to a small amount of liquid crystal, but this also has a limit. In the above background, a liquid crystal alignment agent which accelerates the response speed even when the liquid crystal does not contain a polymerizable compound is desired.

然而液晶配向劑在完全去除溶劑時必須要進行高溫之燒成，故期待即使在如此高溫下燒成，亦可加速應答速度。 However, since the liquid crystal alignment agent must be fired at a high temperature when the solvent is completely removed, it is expected that the reaction speed can be accelerated even if it is fired at such a high temperature.

且，加速如此應答速度之要求並未限定於垂直配向方式之液晶顯示元件，對於超扭轉向列(Twisted Nematic TN)方式等其他方式亦同樣存在。 Further, the requirement for accelerating the response speed is not limited to the liquid crystal display element of the vertical alignment type, and the like also exists for other methods such as the Twisted Nematic TN method.

本發明的課題係為解決上述過去技術之問題點，提供一種將液晶顯示元件的應答速度，即使在液晶中未含有聚合性化合物且在高溫下進行燒成的情況下亦可提高的液晶配向劑、液晶配向膜、液晶顯示元件及液晶顯示元件之製造方法、以及聚合性化合物。 In order to solve the problems of the prior art, the present invention provides a liquid crystal alignment agent which can improve the response speed of a liquid crystal display element even when the liquid crystal does not contain a polymerizable compound and is fired at a high temperature. A liquid crystal alignment film, a liquid crystal display element, a method for producing a liquid crystal display element, and a polymerizable compound.

解決上述課題之本發明的液晶配向劑係以含有聚合性化合物、聚合物及溶劑為特徵，其中聚合性化合物為持有具有α-亞甲基-γ-丁內酯基之末端與具有進行光聚合或光交聯之基的末端之聚合性化合物，其中聚合物為形成能使液晶配向之液晶配向膜的聚合物。 The liquid crystal alignment agent of the present invention which solves the above problems is characterized by containing a polymerizable compound, a polymer, and a solvent, wherein the polymerizable compound has a terminal having an α-methylene-γ-butyrolactone group and has light. A polymerizable compound at the end of a polymerized or photocrosslinkable group, wherein the polymer is a polymer which forms a liquid crystal alignment film capable of aligning liquid crystals.

前述聚合性化合物可為選自下述式[I-1]~[I-4]之至少一種。 The polymerizable compound may be at least one selected from the group consisting of the following formulas [I-1] to [I-4].

(式[I-1]~[I-4]中，V表示單鍵或-R31O-，R31為直鏈或分支之碳數1~10的伸烷基，例如V為-(CH2)n1-O-，W表示單鍵或-OR32-，R32為直鏈或分支之碳數1~10的伸烷基，例如W為-O-(CH2)n1-，n1為1~10的整數，較佳為2~10，x及y各獨立為1或2，R1為氫或甲基，A21為單鍵或選自下述之基) (In the formula [I-1] to [I-4], V represents a single bond or -R 31 O-, and R 31 is a linear or branched alkyl group having 1 to 10 carbon atoms, for example, V is -(CH) 2 ) n1 -O-, W represents a single bond or -OR 32 -, R 32 is a linear or branched alkyl group having 1 to 10 carbon atoms, for example, W is -O-(CH 2 ) n1 -, n1 is An integer of 1 to 10, preferably 2 to 10, x and y are each independently 1 or 2, R 1 is hydrogen or methyl, and A 21 is a single bond or a group selected from the group consisting of

(式中，p1為2~10之整數，q1為0~2之整數，z為1或2) (where p1 is an integer from 2 to 10, q1 is an integer from 0 to 2, and z is 1 or 2)

又，前述聚合性化合物可為選自下述式[II-1]~[II-3]的至少一種。Further, the polymerizable compound may be at least one selected from the group consisting of the following formulas [II-1] to [II-3].

[化3][Chemical 3]

(式[II-1]～[II-3]中，n2為2～11的整數，m1為0～11的整數，x為1或2，R2為氫、-OCH3或鹵素原子，R3為氫、-CN、-O(CH2)m1CH3或鹵素原子，R4為-(CH2)m1CH3(m1為0～11的整數)，A22為單鍵、-O-C6H4-或-O-C6H4-C6H4-)(In the formula [II-1] to [II-3], n2 is an integer of 2 to 11, m1 is an integer of 0 to 11, x is 1 or 2, and R 2 is hydrogen, -OCH 3 or a halogen atom, R 3 is hydrogen, -CN, -O(CH 2 ) m1 CH 3 or a halogen atom, R 4 is -(CH 2 ) m1 CH 3 (m1 is an integer of 0 to 11), and A 22 is a single bond, -OC 6 H 4 - or -OC 6 H 4 -C 6 H 4 -)

又，前述聚合性化合物可為下述式[III-1]。Further, the polymerizable compound may be the following formula [III-1].

[化4][Chemical 4]

(式[III-1]中，11為2～9的整數，X1為選自下述式[iii-1]～[iii-3]的基)(In the formula [III-1], 11 is an integer of 2 to 9, and X 1 is a group selected from the following formulas [iii-1] to [iii-3])

[化5][Chemical 5]

(式[iii-2]中，m2為4～8之整數，式[iii-3]中，R5為選自下述式的基)(In the formula [iii-2], m2 is an integer of 4 to 8, and in the formula [iii-3], R 5 is a group selected from the following formula)

[化6][Chemical 6]

(式中，X2為氫、鹵素原子、氰基或烷氧基，R1為氫或甲基，n3為2～10之整數，p2為3～10的整數，o1為0～6之整數)(wherein, X 2 is hydrogen, a halogen atom, a cyano group or an alkoxy group, R 1 is hydrogen or a methyl group, n3 is an integer of 2 to 10, p2 is an integer of 3 to 10, and o1 is an integer of 0 to 6 )

而前述聚合性化合物可為下述式[IV]。The polymerizable compound may be the following formula [IV].

[化7][Chemistry 7]

(式中，X3、X4、X5及X6各獨立為氫或氟原子，R6為氫、鹵素原子、氰基、烷基、烷氧基、或烷氧基羰基，G為-C(=O)O-或-OC(=O)-基，n4為4～10之整數)(wherein, X 3 , X 4 , X 5 and X 6 are each independently hydrogen or a fluorine atom, and R 6 is hydrogen, a halogen atom, a cyano group, an alkyl group, an alkoxy group or an alkoxycarbonyl group, and G is - C(=O)O- or -OC(=O)-group, n4 is an integer from 4 to 10)

又，形成配向前述液晶所得之液晶配向膜的聚合物，具有將液晶配向呈垂直之側鏈為佳。Further, it is preferred that the polymer which forms the liquid crystal alignment film obtained by aligning the liquid crystal has a side chain in which the liquid crystal is aligned perpendicularly.

本發明的液晶配向膜係以將上述液晶配向劑塗佈於基板後經燒成而得者為佳。The liquid crystal alignment film of the present invention is preferably obtained by applying the liquid crystal alignment agent to a substrate and firing it.

而本發明的液晶顯示元件係以具備將上述液晶配向劑塗佈於基板上並燒成所得之液晶配向膜上設置液晶層並與其接觸，於該液晶層一邊外加電壓一邊照射紫外線所製作之液晶胞為特徵。 In the liquid crystal display device of the present invention, a liquid crystal layer is provided on a liquid crystal alignment film obtained by applying the liquid crystal alignment agent onto a substrate and fired thereon, and a liquid crystal layer is irradiated with ultraviolet rays while applying a voltage to the liquid crystal layer. The cell is characterized.

又，本發明的液晶顯示元件之製造方法係以將上述液晶配向劑塗佈於基板上，並燒成後所得之液晶配向膜上設置液晶層並與其接觸，於該液晶層一邊外加電壓一邊照射紫外線而製作液晶胞為特徵。 Further, in the method for producing a liquid crystal display device of the present invention, the liquid crystal alignment agent is applied onto a substrate, and a liquid crystal layer is provided on the liquid crystal alignment film obtained by firing, and is brought into contact with the liquid crystal layer, and a voltage is applied while the liquid crystal layer is applied thereto. It is characterized by the production of liquid crystal cells by ultraviolet rays.

又，本發明的聚合性化合物係以下述式中任一所示者為特徵。 Further, the polymerizable compound of the present invention is characterized by any one of the following formulae.

本發明係為可提供一種將液晶顯示元件的應答速度， 即使於液晶中未含有聚合性化合物，且在高溫下進行燒成的情況中亦可提高的液晶配向劑。而亦可提供藉由使用該液晶配向劑，應答速度快的垂直配向方式之液晶顯示元件。 The present invention is to provide a response speed of a liquid crystal display element, A liquid crystal alignment agent which can be improved even when the liquid crystal does not contain a polymerizable compound and is fired at a high temperature. Further, a liquid crystal display element of a vertical alignment type having a fast response speed by using the liquid crystal alignment agent can be provided.

實施發明的型態 Type of implementation of the invention

以下對於本發明做詳細說明。 The invention will be described in detail below.

本發明的液晶配向劑為含有聚合性化合物、聚合物及溶劑，其中聚合性化合物為持有具有α-亞甲基-γ-丁內酯基之末端與具有進行光聚合或光交聯之基的末端之聚合性化合物，聚合物為形成能使液晶配向之液晶配向膜的聚合物。且，所謂液晶配向劑為作成液晶配向膜時的溶液，所謂液晶配向膜為使液晶配向為所定方向，例如配向為垂直方向之膜。以下對於本發明之液晶配向劑所含之各成分做詳細說明。 The liquid crystal alignment agent of the present invention contains a polymerizable compound, a polymer, and a solvent, wherein the polymerizable compound has a terminal having an α-methylene-γ-butyrolactone group and a group having photopolymerization or photocrosslinking. The polymerizable compound at the end, the polymer is a polymer which forms a liquid crystal alignment film capable of aligning the liquid crystal. Further, the liquid crystal alignment agent is a solution when a liquid crystal alignment film is formed, and the liquid crystal alignment film is a film in which the liquid crystal is aligned in a predetermined direction, for example, in a vertical direction. Hereinafter, each component contained in the liquid crystal alignment agent of the present invention will be described in detail.

<聚合性化合物> <Polymerizable compound>

含有本發明之液晶配向劑的聚合性化合物係為持有具有α-亞甲基-γ-丁內酯基之末端、與具有進行光聚合或光交聯之基的末端者。如此本發明的液晶配向劑所含有之聚合性化合物為持有具有α-亞甲基-γ-丁內酯基之末端、及具有進行光聚合或光交聯之基的末端。即於二個末端(兩末端)因具有α-亞甲基-γ-丁內酯基及進行光聚合或光交聯之基，藉由照射光，與形成配向液晶所得之液晶配向膜 的聚合物，或聚合性化合物的聚合物進行反應，可與彼等進行交聯。當然因持有具有α-亞甲基-γ-丁內酯基之末端、及具有進行光聚合或光交聯之基的末端，故聚合性化合物彼此間亦可進行反應而形成聚合物。且，所謂進行光聚合之基為，藉由照射光可產生聚合的官能基，所謂進行光交聯之基為藉由照射光，與形成配向液晶所得之液晶配向膜的聚合物或聚合性化合物的聚合物進行反應，可將彼等進行交聯之官能基。 The polymerizable compound containing the liquid crystal alignment agent of the present invention is a terminal having a terminal having an α-methylene-γ-butyrolactone group and a terminal having a photopolymerization or photocrosslinking. The polymerizable compound contained in the liquid crystal alignment agent of the present invention is a terminal having a terminal having an α-methylene-γ-butyrolactone group and a group having photopolymerization or photocrosslinking. That is, at the two ends (both ends), by having an α-methylene-γ-butyrolactone group and performing photopolymerization or photocrosslinking, by irradiating light, a liquid crystal alignment film obtained by forming an alignment liquid crystal The polymer, or the polymer of the polymerizable compound, reacts and can be crosslinked with them. Of course, since the terminal having an α-methylene-γ-butyrolactone group and a terminal having a photopolymerization or photocrosslinking group are held, the polymerizable compounds can react with each other to form a polymer. Further, the photopolymerization base is a polymerizable functional group by irradiation of light, and the photocrosslinking group is a polymer or a polymerizable compound which forms a liquid crystal alignment film obtained by aligning liquid crystal by irradiation with light. The polymers are reacted to pass the functional groups to which they are crosslinked.

而因具有兩末端之官能基中，至少1個為α-亞甲基-γ-丁內酯基，故所得之聚合物為硬性結構，具有優良的液晶之配向固定化能力，故如後述之實施例所示，藉由使用於PSA型液晶顯示器或SC-PVA型液晶顯示器等垂直配向方式等液晶顯示元件的製造上，即使在高溫下燒成亦可大幅度增加應答速度。此推測為本發明的液晶配向劑所含有之聚合性化合物係為缺乏熱聚合性的結構，故例如於200℃以上的燒成溫度下可充分耐住。當然即使於液晶中未含有聚合性化合物，要可大幅度增加應答速度。對於使用於本發明的液晶配向劑之聚合性化合物，於兩末端所具有官能基中至少1個必須為α-亞甲基-γ-丁內酯基，例如僅具有專利文獻1所記載之丙烯酸酯基、甲基丙烯酸酯基、乙烯基、乙烯氧基、環氧基等官能的化合物中，缺乏熱安定性，難耐住在高溫之燒成，故少量添加且高溫下進行燒成時，無法大幅度增加垂直配向方式等液晶顯示元件的應答速度。 Further, since at least one of the functional groups having both terminals is an α-methylene-γ-butyrolactone group, the obtained polymer has a rigid structure and has excellent alignment ability of liquid crystal alignment, and thus will be described later. In the production of a liquid crystal display element such as a vertical alignment method such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, the response speed can be greatly increased even at a high temperature. This is presumed to be a structure in which the polymerizable compound contained in the liquid crystal alignment agent of the present invention lacks thermal polymerization properties, and therefore, it can be sufficiently resistant to, for example, a firing temperature of 200 ° C or higher. Of course, even if the liquid crystal does not contain a polymerizable compound, the response speed can be greatly increased. In the polymerizable compound to be used in the liquid crystal alignment agent of the present invention, at least one of the functional groups at both terminals must be an α-methylene-γ-butyrolactone group, and for example, only the acrylic acid described in Patent Document 1 is used. A compound having a functional group such as an ester group, a methacrylate group, a vinyl group, a vinyloxy group, or an epoxy group lacks thermal stability and is difficult to withstand firing at a high temperature. Therefore, when it is added in a small amount and is fired at a high temperature, it cannot be baked. The response speed of the liquid crystal display element such as the vertical alignment mode is greatly increased.

作為進行光聚合或光交聯之基，例如可舉出下述式所 示一價基。將進行光聚合基或光交聯之基作為α-亞甲基-γ-丁內酯基時，因聚合性化合物於兩末端所具有的官能基因僅為α-亞甲基-γ-丁內酯基，故可耐住較高燒成溫度。 Examples of the group to carry out photopolymerization or photocrosslinking include the following formula. Show a price base. When the photopolymerizable group or the photocrosslinking group is used as the α-methylene-γ-butyrolactone group, the functional gene having the polymerizable compound at both ends is only α-methylene-γ-butane Ester group, so it can withstand higher firing temperature.

(式中，R15為氫或碳數1~4的烷基，Z1為可藉由碳數1~12的烷基或碳數1~12的烷氧基所取代之二價芳香環或雜環，Z2為可由碳數1~12的烷基或碳數1~12的烷氧基所取代之一價芳香環或雜環) (wherein R 15 is hydrogen or an alkyl group having 1 to 4 carbon atoms; and Z 1 is a divalent aromatic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms or a heterocyclic ring, Z 2 is a monovalent aromatic ring or a heterocyclic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms)

又，聯繫α-亞甲基-γ-丁內酯基與進行光聚合或光交聯之基的連結基係為二價有機基，作為該二價有機基，可舉出可由鹵素原子、氰基、碳數1~12的烷基、碳數1~12的烷氧基或碳數1~12的烷氧基羰所取代之具有二價芳香環、雜環或雜環之二價有機基。 Further, the linking group which is bonded to the α-methylene-γ-butyrolactone group and the photopolymerization or photocrosslinking group is a divalent organic group, and examples of the divalent organic group include a halogen atom and a cyanogen. a divalent organic group having a divalent aromatic ring, a heterocyclic ring or a heterocyclic ring substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or an alkoxycarbonyl group having 1 to 12 carbon atoms .

作為如此聚合性化合物的結構例，可舉出選自下述式之至少一種。且，式中，R15為氫或碳數1~4的烷基，Z1為可由碳數1~12的烷基或碳數1~12的烷氧基所取代之二價芳香環或雜環，Z2為可由碳數1~12的烷基或碳數1~12的烷氧基所取代之一價芳香環或雜環，Q1為二價有機基。Q1為具有伸苯基(-C6H4-)、聯伸苯基(-C6H4-C6H4-)或環伸己基(-C6H10-)等環結構者為佳。因與液晶之相互 作用容易變大之故。 The structural example of such a polymerizable compound is at least one selected from the following formulae. Further, in the formula, R 15 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and Z 1 is a divalent aromatic ring or a hetero group which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. The ring, Z 2 , is a monovalent aromatic ring or a heterocyclic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and Q 1 is a divalent organic group. Q 1 is a ring structure having a stretching phenyl group (-C 6 H 4 -), a stretching phenyl group (-C 6 H 4 -C 6 H 4 -) or a cyclohexyl group (-C 6 H 10 -) good. The interaction with the liquid crystal tends to become large.

作為聚合性化合物之具體例，可舉出上述式[I-1]~[I-4]、[II-1]~[II-3]、[III-1]、[IV]。作為上述式[I-1]之具體例，可舉出下述式[I-1-a]所示聚合性化合物，對於該聚合性化合物，因另外申請，故可由本發明除去。 Specific examples of the polymerizable compound include the above formulas [I-1] to [I-4], [II-1] to [II-3], [III-1], and [IV]. Specific examples of the above formula [I-1] include a polymerizable compound represented by the following formula [I-1-a], and the polymerizable compound can be removed from the present invention by another application.

(式中，V表示單鍵或-R31O-，R31為直鏈或分支之碳數1~10的伸烷基，W表示單鍵或-OR32-，R32為直鏈或分支之碳數1~10的伸烷基) (wherein, V represents a single bond or -R 31 O-, R 31 is a linear or branched alkyl group having 1 to 10 carbon atoms, W represents a single bond or -OR 32 -, and R 32 is a straight chain or a branch Carbon number of 1 to 10 alkyl groups)

使用於本發明的液晶配向劑之聚合性化合物可藉由組合有機合成化學中之手法而合成，該合成法並無特別限定。例如可依據後述實施例而製造。例如藉由下述反應式所示Talaga等在P.Talaga,M.Schaeffer,C.Benezra and J.L.Stampf,Synthesis,530(1990)所提案之方法，可使用SnCl2將2-(溴甲基)丙烯酸(2-(bromomethyl) propenoic acid)與醛或酮進行反應而合成。且，Amberlyst 15為Rohm and Haas Company製之強酸性離子交換樹脂。 The polymerizable compound used in the liquid crystal alignment agent of the present invention can be synthesized by a combination of methods in organic synthetic chemistry, and the synthesis method is not particularly limited. For example, it can be manufactured according to the embodiment described later. For example, 2-(bromomethyl)acrylic acid can be used with SnCl 2 by the method proposed by Talaga et al., P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990), as shown in the following reaction formula. (2-(bromomethyl) propenoic acid) is synthesized by reaction with an aldehyde or a ketone. Further, Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas Company.

(式中，R’表示一價有機基) (wherein R' represents a monovalent organic group)

又，2-(溴甲基)丙烯酸可由下述反應式所示Ramarajan等在K.Ramarajan,K.Kamalingam,D.J.O’Donnell and K.D.Berlin,Organic Synthesis,vol.61,56-59(1983)所提案之方法合成。 Further, 2-(bromomethyl)acrylic acid can be represented by the following reaction formula by Ramarajan et al., K. Ramarajan, K. Kamalingam, DJO'Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983). The method of the proposal is synthesized.

又，在使用SnCl2的2-(溴甲基)丙烯酸之反應中，取代醛或酮藉由與所對應之縮醛或縮酮之反應，可得到α-亞甲基-γ-丁內酯結構。作為縮醛或縮酮可舉出二甲基縮醛基、二乙基縮醛基、1,3-二噁烷基、1,3-二噁戊烷基等。以下表示該合成法及保護基。Further, in the reaction using 2-(bromomethyl)acrylic acid of SnCl 2 , the substituted aldehyde or ketone can be obtained by reacting with the corresponding acetal or ketal to obtain α-methylene-γ-butyrolactone. structure. Examples of the acetal or ketal include a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxanyl group, and a 1,3-dipentopentyl group. The synthesis method and protecting group are shown below.

[化14][Chemistry 14]

(式中，R’表示一價有機基)(wherein R' represents a monovalent organic group)

具體的合成例如說明如下。且對於下述反應式，M為選自以下之基，R1為與上述式[I-1]～[I-4]中之R1相同。The specific synthesis is explained, for example, as follows. And for the following reaction formula, M being selected from the group, R 1 is the same as in the above formula [I-1] ~ [I -4] in the R 1.

[化15][化15]

(上述式[I-1]～[I-4]所示聚合性化合物之合成例)(Synthesis Example of Polymerizable Compounds of the above Formulas [I-1] to [I-4])

A21=單鍵且W=-O-(CH2)n1-(n1為1～10之整數)時，可由下述式的反應進行合成。When A 21 = a single bond and W = -O-(CH 2 ) n1 - (n1 is an integer of from 1 to 10), it can be synthesized by a reaction of the following formula.

[化16][Chemistry 16]

A21=單鍵且W=單鍵時，可由下述式的反應進行合成。When A 21 = a single bond and W = a single bond, the synthesis can be carried out by a reaction of the following formula.

[化17][化17]

A21=單鍵且W=單鍵時，可由下述式的反應進行合成。When A 21 = a single bond and W = a single bond, the synthesis can be carried out by a reaction of the following formula.

[化18][化18]

A21=-(CH2)q1-O-(C=O)-時，可由下述式的反應進行合成。When A 21 = -(CH 2 ) q1 -O-(C=O)-, the synthesis can be carried out by a reaction of the following formula.

[化19][Chemistry 19]

A21=-(C=O)-O-(CH2)p1-O-(C=O)-時，可由下述式的反應進行合成。 A 21 = - (C = O ) -O- (CH 2) p1 -O- (C = O) - , the reaction can be synthesized by the following formula.

[化20][Chemistry 20]

A21=-(C=O)-O-(CH2)q1-(C6H4)z-(CH2)q1-O-(C=O)-時，可由下述式的反應進行合成。When A 21 =-(C=O)-O-(CH 2 ) q1 -(C 6 H 4 ) z -(CH 2 ) q1 -O-(C=O)-, it can be synthesized by the reaction of the following formula .

[化21][Chem. 21]

A21=-(C=O)-O-(C6H4COC6H4)-O-(C=O)-時，可由下述式的反應進行合成。When A 21 = -(C=O)-O-(C 6 H 4 COC 6 H 4 )-O-(C=O)-, the synthesis can be carried out by a reaction of the following formula.

[化22][化22]

A21=-(C=O)-O-(CH2)p1-O-(C6H4)z-O-(CH2)p1-O-(C=O)-時，可由下述式的反應進行合成。A 21 =-(C=O)-O-(CH 2 ) p1 -O-(C 6 H 4 ) z -O-(CH 2 ) p1 -O-(C=O)-, which may be represented by the following formula The reaction is carried out.

[化23][化23]

A21=-O-(C=O)-(C6H4)z-(C=O)-O-時，可由下述式的反應進行合成。When A 21 = -O-(C=O)-(C 6 H 4 ) z -(C=O)-O-, the synthesis can be carried out by a reaction of the following formula.

[化24][Chem. 24]

A21=-O-(C=O)-(C6H10)-(C=O)-O-時，可由下述式的反應進行合成。When A 21 = -O-(C=O)-(C 6 H 10 )-(C=O)-O-, the synthesis can be carried out by a reaction of the following formula.

[化25][化25]

A21=-(C=O)-O-(CH2)q1-(C6H10)-(CH2)q1-O-(C=O)-時，可由下述式的反應進行合成。 A 21 = - (C = O ) -O- (CH 2) q1 - (C 6 H 10) - (CH 2) q1 -O- (C = O) - , the reaction can be synthesized by the following formula.

[化26][Chem. 26]

又，上述式[I-3]及[I-4]所示聚合性化合物，可由下述式的反應進行合成。Further, the polymerizable compounds represented by the above formulas [I-3] and [I-4] can be synthesized by a reaction of the following formula.

[化27][化27]

(上述式[II-1]～[II-3]所示聚合性化合物之合成例)(Synthesis example of the polymerizable compound represented by the above formula [II-1] to [II-3])

上述式[II-1]所示聚合性化合物，可由下述式的反應進行合成。The polymerizable compound represented by the above formula [II-1] can be synthesized by a reaction of the following formula.

[化28][化28]

對於上述式[II-2]所示聚合性化合物，A22=單鍵時，可由下述式的反應進行合成。When the polymerizable compound represented by the above formula [II-2], A 22 = a single bond, it can be synthesized by a reaction of the following formula.

[化29][化29]

對於上述式[II-2]所示聚合性化合物，A22=-O-(C6H4)-、-O-(C6H4)-(C6H4)-時，可由下述式的反應進行合成。For the polymerizable compound represented by the above formula [II-2], when A 22 = -O-(C 6 H 4 )-, -O-(C 6 H 4 )-(C 6 H 4 )-, the following may be used. The reaction of the formula is carried out.

[化30][化30]

上述式[II-3]所示聚合性化合物，可由下述式的反應進行合成。The polymerizable compound represented by the above formula [II-3] can be synthesized by a reaction of the following formula.

[化31][化31]

且，上述反應中之原料，例如可由下述反應進行合成。Further, the raw material in the above reaction can be synthesized, for example, by the following reaction.

[化32][化32]

(式中，THP表示四氫吡喃)(where THP stands for tetrahydropyran)

[化34][化34]

[化35][化35]

而上述式[III-1]所示聚合性化合物可由國際公開第2006/115112號手冊、國際公開第2008/072652號手冊、國際公開第2010/044384號手冊所記載之方法，或下述反應所合成。Further, the polymerizable compound of the above formula [III-1] may be a method described in International Publication No. 2006/115112, International Publication No. 2008/072652, International Publication No. 2010/044384, or the following reaction. synthesis.

[化36][化36]

又，上述式[IV]所示聚合性化合物可由下述反應所合成。Further, the polymerizable compound represented by the above formula [IV] can be synthesized by the following reaction.

[化37][化37]

<形成配向液晶所得之液晶配向膜的聚合物><Polymer for forming a liquid crystal alignment film obtained by aligning liquid crystals>

本發明的液晶配向劑所含有之形成配向液晶所得之液晶配向膜的聚合物僅能配向於基板上所形成之液晶配向膜上的液晶者即可，並無特別限定，例如可舉出可將形成於基板上之液晶配向膜上的液晶配向呈對基板之垂直方向的聚合物。作為如此可形成於基板上之液晶配向膜上的液晶配向呈對基板之垂直方向的聚合物，以具有將液晶配向呈垂直之側鏈的聚合物為佳，可舉出具有將液晶配向呈垂直之側鏈的聚醯胺酸或聚醯胺酸酯等聚醯亞胺前驅物、該聚醯胺酸或聚醯胺酸酯等經醯亞胺化等所得之聚醯亞胺。The polymer for forming the liquid crystal alignment film obtained by aligning the liquid crystal contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can be aligned to the liquid crystal on the liquid crystal alignment film formed on the substrate, and for example, The liquid crystal on the liquid crystal alignment film formed on the substrate is aligned to form a polymer in a direction perpendicular to the substrate. The liquid crystal alignment on the liquid crystal alignment film which can be formed on the substrate in this manner is a polymer in a direction perpendicular to the substrate, and a polymer having a side chain in which the liquid crystal is aligned perpendicularly is preferable, and the liquid crystal alignment is vertical. A polyimine precursor such as polyamine or polyperurate in a side chain, or a polyimine obtained by hydrazine imidization or the like, such as polylysine or polylysine.

將液晶配向呈垂直之側鏈若為可將液晶配向呈對基板為垂直方向的結構即可並無特別限定，例如可舉出長鏈的烷基、長鏈烷基途中具有環結構或分支之結構的基、類固醇基等烴基或這些基的氫之一部份或全部由氟原子取代的基等。當然亦可具有二種類以上之將液晶配向呈垂直的側鏈。將液晶配向呈垂直之側鏈可直接結合於聚醯胺酸或聚醯胺酸酯等聚醯亞胺前驅物或聚醯亞胺等聚合物之主鏈，即聚醯胺酸骨架或聚醯亞胺骨架等，又亦可介著適當鍵結基而結合。作為將液晶配向呈垂直之側鏈，例如可舉出氫可由氟取代之碳數為8～30，較佳為8～22之烴基，具體可舉出烷基、氟烷基、烯基、苯乙基、苯乙烯烷基、萘基、氟苯基烷基等。其他作為將液晶配向呈垂直之側鏈，例如可舉出下述式(a)所示者。The side chain in which the liquid crystal is aligned in the vertical direction is not particularly limited as long as it can align the liquid crystal in a direction perpendicular to the substrate. For example, a long-chain alkyl group or a long-chain alkyl group has a ring structure or a branch. A hydrocarbon group such as a structural group or a steroid group or a group in which a part or all of hydrogen of these groups is substituted by a fluorine atom or the like. Of course, there may be two or more types of side chains in which the liquid crystals are aligned vertically. The vertical side chain of the liquid crystal alignment can be directly bonded to the main chain of a polymer such as a polyimide or a polyamidomate or a polymer such as a polyimide, that is, a polyamine skeleton or a polyfluorene. The imine skeleton or the like may be bonded via a suitable bonding group. Examples of the side chain in which the liquid crystal is aligned vertically may, for example, be a hydrocarbon group having a carbon number of 8 to 30, preferably 8 to 22, which may be substituted by fluorine, and specific examples thereof include an alkyl group, a fluoroalkyl group, an alkenyl group and a benzene group. Ethyl, styrenealkyl, naphthyl, fluorophenylalkyl, and the like. Other examples of the side chain in which the liquid crystal is aligned vertically are, for example, those represented by the following formula (a).

[化38][化38]

(式(a)中l、m及n各獨立表示0或1之整數，R7表示碳數2～6的伸烷基、-O-、-COO-、-OCO-、-NHCO-、-CONH-或碳數1～3的伸烷基-醚基，R8、R9及R10各獨立表示伸苯基或環伸烷基，R11表示氫、碳數2～24的烷基或含有氟之烷基、一價芳香環、一價脂肪族環、一價雜環或這些所成之一價大環狀取代體)(In the formula (a), l, m and n each independently represent an integer of 0 or 1, and R 7 represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, - CONH- or an alkylene-ether group having 1 to 3 carbon atoms, R 8 , R 9 and R 10 each independently represent a phenyl or cycloalkyl group, and R 11 represents hydrogen, an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent hetero ring or a monovalent large cyclic substituent

且，上述式(a)中之R7由合成容易性的觀點來看，以-O-、-COO-、-CONH-、碳數1～3的伸烷基-醚基為佳。Further, R 7 in the above formula (a) is preferably an alkyl-ether group having -O-, -COO-, -CONH- or a carbon number of 1-3 from the viewpoint of easiness of synthesis.

又，式(a)中之R8、R9及R10由合成容易性及將液晶配向呈垂直之能力的觀點來看，下述表1所示l、m、n、R8、R9及R10的組合為佳。Further, R 8 , R 9 and R 10 in the formula (a) are represented by the following Table 1, from the viewpoints of easiness of synthesis and ability to align the liquid crystal to be perpendicular, and l, m, n, R 8 and R 9 shown in Table 1 below. The combination of R 10 is preferred.

而l、m、n的至少一個為1時，式(a)中之R11較佳為氫或碳數2～14的烷基或含有氟之烷基，更佳為氫或碳數2～12的烷基或含有氟之烷基。又，l、m、n皆為0時，R11較佳為碳數12～22的烷基或含有氟之烷基、一價芳香環、一價脂肪族環、一價雜環、彼等所成之一價大環狀取代體，較佳為碳數12～20的烷基或含有氟之烷基。When at least one of l, m and n is 1, R 11 in the formula (a) is preferably hydrogen or an alkyl group having 2 to 14 carbon atoms or an alkyl group containing fluorine, more preferably hydrogen or a carbon number of 2 to ～. An alkyl group of 12 or an alkyl group containing fluorine. Further, when l, m, and n are all 0, R 11 is preferably an alkyl group having 12 to 22 carbon atoms or an alkyl group containing fluorine, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, and the like. The monovalent large cyclic substituent is preferably an alkyl group having 12 to 20 carbon atoms or an alkyl group containing fluorine.

將液晶配向呈垂直之側鏈的存在量，僅液晶配向膜可將液晶配向呈垂直的範圍即可並無特別限定。但，對於具備前述液晶配向膜之液晶顯示元件，在不損害電壓保持率或殘留DC電壓之蓄積等元件的顯示特性之範圍內，將液晶配向呈垂直之側鏈的存在量盡可能較少為佳。The amount by which the liquid crystal is aligned in the vertical side chain is not particularly limited as long as the liquid crystal alignment film can align the liquid crystal in a vertical range. However, in the liquid crystal display element including the liquid crystal alignment film, the amount of the side chain in which the liquid crystal alignment is perpendicular is as small as possible within a range that does not impair the display characteristics of the element such as the voltage holding ratio or the accumulation of the residual DC voltage. good.

且，具有將液晶配向呈垂直之側鏈的聚合物將液晶配向呈垂直之能力，依將液晶配向呈垂直之側鏈的結構而相異，一般而言，將液晶配向呈垂直之側鏈的量越多時，將液晶配向呈垂直之能力會提高，若少則會下降。又，若具有環狀結構時，與不具有環狀結構之情況比較，有著將液晶配向呈垂直之能力較高的傾向。Moreover, the polymer having the side chain of the liquid crystal alignment perpendicularly has the ability to align the liquid crystal in a vertical direction, and is different according to the structure in which the liquid crystal is aligned in a vertical side chain. Generally, the liquid crystal is aligned in a vertical side chain. The greater the amount, the higher the ability to align the liquid crystal alignment, and the lower the capacity. Moreover, when it has a cyclic structure, compared with the case where it does not have a cyclic structure, it has the tendency for the liquid-crystal alignment to become perpendicular.

又，形成將液晶配向呈垂直的液晶配向膜之聚合物以具有光反應性側鏈者為佳。若具有光反應性側鏈時，可進一步提高應答速度。當然亦可使用形成將不具有光反應性側鏈的液晶配向呈垂直之液晶配向膜的聚合物。其中，所謂光反應性側鏈為，藉由紫外線(UV)等光的照射進行反應，具有形成共價鍵之官能基(以下亦稱為光反應性基)的側鏈，若具有該能力者即可該結構並未被限定。作為光反應性側鏈，例如作為光反應性基，可舉出具有乙烯基、丙烯基、甲基丙烯基、烯丙基、苯乙烯基、桂皮醯基、chalconyl、香豆素基、馬來亞醯胺、環氧基、乙烯氧基、丙烯氧基等等側鏈，例如可舉出這些光反應性基自體，或由這些光反應性基取代氫之烷基等。經取代的氫為1個以上，較佳為1個。氫由光反應性基所取代之烷基碳數，由應答速度與垂直配向性之觀點來看以1～30為佳，較佳為1～10，更佳為1～5。當然亦可具有二種類以上的光反應性側鏈。光反應性側鏈亦可直接結合聚醯亞胺前驅物或聚醯亞胺等聚合物的主鏈，又可介著適當鍵結基結合。作為光反應性側鏈，例如可舉出下述式(b)所示者。Further, it is preferred to form a polymer having a liquid crystal alignment film in which the liquid crystal is aligned to have a photoreactive side chain. If the photoreactive side chain is present, the response speed can be further increased. It is of course also possible to use a polymer which forms a liquid crystal alignment film which is oriented perpendicular to the liquid crystal having no photoreactive side chain. In the above, the photoreactive side chain is a side chain which has a functional group (hereinafter also referred to as a photoreactive group) which forms a covalent bond by irradiation with light such as ultraviolet rays (UV), and has such a capability. That is, the structure is not limited. Examples of the photoreactive side chain include a vinyl group, a propylene group, a methacryl group, an allyl group, a styryl group, a cinnamyl group, a chalcone group, a coumarin group, and a Malay. Examples of the side chain such as a methylene chloride, an epoxy group, a vinyloxy group, and a propyleneoxy group include these photoreactive groups, or an alkyl group in which hydrogen is replaced by these photoreactive groups. The number of substituted hydrogens is one or more, preferably one. The number of alkyl carbon atoms in which hydrogen is replaced by a photoreactive group is preferably from 1 to 30, more preferably from 1 to 10, still more preferably from 1 to 5, from the viewpoint of response speed and vertical alignment. Of course, it is also possible to have two or more kinds of photoreactive side chains. The photoreactive side chain may also directly bind to the main chain of a polymer such as a polyimine precursor or a polyimine, or may be bonded via a suitable bonding group. Examples of the photoreactive side chain include those represented by the following formula (b).

[化39][39]

-R12-R13-R14　(b)-R 12 -R 13 -R 14 (b)

(式(b)中，R12表示單鍵或-CH2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、-CON(CH3)-、-N(CH3)CO-中任一，R13表示單鍵或非取代或由氟原子所取代之碳數1～20的伸烷基，伸烷基的-CH2-可由-CF2-或-CH=CH-做任意取代，對於以下所舉的任一基未彼此鄰接時可取代為這些基；-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、二價碳環、二價雜環。R14表示乙烯基、丙烯基、甲基丙烯基、烯丙基、苯乙烯基、-N(CH2CH=CH2)2或下述式所示結構)(In the formula (b), R 12 represents a single bond or -CH 2 -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O-, -N Any of (CH 3 )-, -CON(CH 3 )-, -N(CH 3 )CO-, R 13 represents a single bond or an alkyl group having 1 to 20 carbon atoms which are unsubstituted or substituted by a fluorine atom. , the alkyl-CH 2 - may be optionally substituted by -CF 2 - or -CH=CH-, and may be substituted for any of the following groups which are not adjacent to each other; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, a divalent heterocyclic ring. R 14 represents a vinyl group, a propenyl group, a methacryl group, an allyl group, a styryl group, -N (CH 2 CH=CH 2 ) 2 or the structure shown by the following formula)

[化40][化40]

且，上述式(b)中之R12可由一般有機合成的手法所形成，但由合成之容易性的觀點來看以-CH2-、-O-、-COO-、-NHCO-、-NH-、-CH2O-為佳。Further, R 12 in the above formula (b) can be formed by a general organic synthesis method, but from the viewpoint of easiness of synthesis, -CH 2 -, -O-, -COO-, -NHCO-, -NH -, -CH 2 O- is preferred.

又，作為取代R13的任意-CH2-的二價碳環或二價雜環之碳環或雜環，具體可舉出如以下之結構，但並未限定於此。Further, as the carbon ring or hetero ring of the divalent carbocyclic ring or the divalent heterocyclic ring of any -CH 2 - substituted for R 13 , specifically, the following structures are given, but the invention is not limited thereto.

[化41][化41]

R14由光反應性之觀點來看，以乙烯基、丙烯基、甲基丙烯基、烯丙基、苯乙烯基、-N(CH2CHCH2)2或下述式所示結構為佳。R 14 is preferably a vinyl group, a propylene group, a methacryl group, an allyl group, a styryl group, -N(CH 2 CHCH 2 ) 2 or a structure represented by the following formula from the viewpoint of photoreactivity.

[化42][化42]

又，上述式(b)之較佳為下述結構。Further, the above formula (b) is preferably the following structure.

[化43][化43]

光反應性側鏈的存在量，藉由紫外線之照射進行反應而形成共價鍵時可加速液晶的應答速度的範圍為佳，欲進一步加速液晶的應答速度，以不影響其他特性的範圍下，儘可能多為佳。When the amount of the photoreactive side chain is reacted by irradiation with ultraviolet rays to form a covalent bond, the range of the response speed of the liquid crystal can be accelerated, and the response speed of the liquid crystal is further accelerated, so as not to affect other characteristics. As much as possible.

製造形成將如此液晶配向呈垂直的液晶配向膜之聚合物的方法並無特別限定，例如製造具有將液晶配向呈垂直之側鏈的聚醯胺酸時，藉由二胺與四羧酸二酐之反應，得到聚醯胺酸之方法中，使具有將液晶配向呈垂直之側鏈之二胺或具有將液晶配向呈垂直之側鏈的四羧酸二酐進行共聚合的方法為簡便。又，使於形成將液晶配向呈垂直之液晶配向膜的聚合物含有光反應性側鏈時，僅共聚合具有光反應性側鏈的二胺或具有光反應性側鏈的四羧酸二酐即可。The method for producing a polymer which forms a liquid crystal alignment film having such a liquid crystal alignment is not particularly limited. For example, when a polyglycine having a side chain in which a liquid crystal is aligned is formed, a diamine and a tetracarboxylic dianhydride are used. In the method of obtaining poly-proline, it is convenient to carry out a method of copolymerizing a diamine having a side chain which is perpendicular to the liquid crystal or a tetracarboxylic dianhydride having a side chain in which the liquid crystal is aligned vertically. Further, when the polymer forming the liquid crystal alignment film in which the liquid crystal is aligned perpendicularly contains a photoreactive side chain, only the diamine having a photoreactive side chain or the tetracarboxylic dianhydride having a photoreactive side chain is copolymerized. Just fine.

作為具有將液晶配向呈垂直之側鏈的二胺，可舉出具有長鏈的烷基、長鏈烷基的途中具有環結構或分支之結構的基、類固醇基等烴基，或這些基的氫之一部份或全部取代為氟原子的基作為側鏈之二胺，例如可舉出具有上述式(a)所示側鏈之二胺。更具體而言，例如可舉出具有氫可由氟取代的碳數為8～30之烴基等之二胺或下述式(2)、(3)、(4)、(5)所示二胺，但不限定於此等。Examples of the diamine having a side chain in which the liquid crystal is aligned in a vertical direction include a long-chain alkyl group, a long-chain alkyl group, a group having a ring structure or a branched structure, a hydrocarbon group such as a steroid group, or a hydrogen group of these groups. A diamine in which a part of the fluorine atom is partially or wholly substituted with a side chain, and examples thereof include a diamine having a side chain represented by the above formula (a). More specifically, for example, a diamine having a hydrocarbon group having 8 to 30 carbon atoms in which hydrogen can be substituted by fluorine or a diamine represented by the following formulas (2), (3), (4), and (5) However, it is not limited to this.

[化44][化44]

(式(2)中的l、m、n、R7～R11之定義與上述式(a)相同)(The definitions of l, m, n, R 7 to R 11 in the formula (2) are the same as those in the above formula (a))

[化45][化45]

(式(3)及式(4)中，A10表示-COO-、-OCO-、-CONH-、-NHCO-、-CH2-、-O-、-CO-或-NH-，A11表示單鍵或者伸苯基，a表示與上述式(a)所示將液晶配向呈垂直之側鏈的相同結構，a’表示由與上述式(a)所示將液晶配向呈垂直之側鏈的相同結構取出1個氫等元素之結構的二價基)(In the formulae (3) and (4), A 10 represents -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, -CO- or -NH-, A 11 Represents a single bond or a phenyl group, a represents the same structure as the side chain perpendicular to the liquid crystal alignment shown in the above formula (a), and a' represents a side chain perpendicular to the liquid crystal alignment shown in the above formula (a) The same structure takes out a divalent group of the structure of an element such as hydrogen)

[化46][Chem. 46]

(式(5)中，A14為可由氟原子取代的碳數3～20的烷基，A15為1,4-環伸己基或1,4-伸苯基，A16為氧原子或-COO-*(但附有「*」之結合鍵與A3結合)，A17為氧原子或-COO-*(但附有「*」之結合鍵與(CH2)a2結合)。又，a1為0或1的整數，a2為2～10的整數，a3為0或1的整數)(In the formula (5), A 14 is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A 15 is a 1,4-cyclohexyl group or a 1,4-phenylene group, and A 16 is an oxygen atom or - COO - * (but with "*" of the bond binding to A 3), A 17 is an oxygen atom or -COO - * (but with "*" bond with (CH 2) binding of a 2) in turn. , a 1 is an integer of 0 or 1, a 2 is an integer of 2 to 10, and a 3 is an integer of 0 or 1.

式(2)中之二個胺基(-NH2)之鍵結位置並被限定。具體而言對於側鏈的鍵結基而言，可舉出苯環上之2,3的位置、2,4的位置、2,5的位置、2,6的位置、3,4的位置、3,5的位置。其中亦由合成聚醯胺酸時的反應性觀點來看，以2,4的位置、2,5的位置或3,5的位置為佳。加上合成二胺時的容易性時，以2,4的位置或3,5的位置為較佳。Bonding position of formula (2) in the two group (-NH 2) of and defined. Specifically, the bonding group of the side chain may be a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, a position of 3, 4, 3,5 position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, it is preferred to have a position of 2, 4, a position of 2, 5, or a position of 3, 5. When the ease of synthesizing a diamine is added, it is preferable to use a position of 2, 4 or a position of 3, 5.

作為式(2)的具體結構，可舉出下述式[A-1]～式[A-24]所示二胺，但並未限定於此。Specific examples of the formula (2) include diamines represented by the following formulas [A-1] to [A-24], but are not limited thereto.

[化47][化47]

(式[A-1]～式[A-5]中，A1為碳數2～24的烷基或含有氟之烷基)(In the formula [A-1] to the formula [A-5], A 1 is an alkyl group having 2 to 24 carbon atoms or an alkyl group containing fluorine)

[化48][48]

(式[A-6]及式[A-7]中，A2表示-O-、-OCH2-、-CH2O-、-COOCH2-或-CH2OCO-，A3為碳數1～22的烷基、烷氧基、含有氟之烷基或含有氟之烷氧基)(In the formula [A-6] and the formula [A-7], A 2 represents -O-, -OCH 2 -, -CH 2 O-, -COOCH 2- or -CH 2 OCO-, and A 3 is a carbon number. 1 to 22 alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups)

[化49][化49]

(式[A-8]～式[A-10]中，A4表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-或-CH2-，A5表示碳數1～22的烷基、烷氧基、含有氟之烷基或含有氟之烷氧基)(In the formula [A-8] to the formula [A-10], A 4 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O -, -OCH 2 - or -CH 2 -, A 5 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)

[化50][化50]

(式[A-11]及式[A-12]中，A6表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH2-、-CH2OCO-、-CH2O-、-OCH2-、-CH2-、-O-或-NH-，A7為氟基、氰基、三氟甲烷基、硝基、偶氮基、甲醯基、乙醯基、乙醯氧基或羥基)(In the formula [A-11] and the formula [A-12], A 6 represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O -, -OCH 2 -, -CH 2 -, -O- or -NH-, A 7 is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, a Alkoxy or hydroxy)

[化51][化51]

(式[A-13]及式[A-14]中，A8為碳數3～12的烷基，1,4-環伸己基的順-反異性各為反式異構物)(In the formula [A-13] and the formula [A-14], A 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of the 1,4-cyclohexyl group is a trans isomer)

[化52][化52]

(式[A-15]及式[A-16]中，A9為碳數3～12的烷基，1,4-環伸己基的順-反異性各為反式異構物)(In the formula [A-15] and the formula [A-16], A 9 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of the 1,4-cyclohexyl group is a trans isomer)

[化53][化53]

作為式(3)所示二胺的具體例，可舉出下述式[A-25]～式[A-30]所示二胺，但並未限定於此。Specific examples of the diamine represented by the formula (3) include the diamines represented by the following formulas [A-25] to [A-30], but are not limited thereto.

[化54][54]

(式[A-25]～式[A-30]中，A12表示-COO-、-OCO-、-CONH-、-NHCO-、-CH2-、-O-、-CO-或-NH-，A13表示碳數1～22的烷基或含有氟之烷基。)(In the formula [A-25] to the formula [A-30], A 12 represents -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, -CO- or -NH -, A 13 represents an alkyl group having 1 to 22 carbon atoms or an alkyl group containing fluorine.

作為式(4)所示二胺的具體例，可舉出下述式[A-31]～式[A-32]所示二胺，但並未限定於此。Specific examples of the diamine represented by the formula (4) include a diamine represented by the following formula [A-31] to the formula [A-32], but are not limited thereto.

[化55][化55]

其中由將液晶配向呈垂直之能力、液晶的應答速度之觀點來看，以[A-1]、[A-2]、[A-3]、[A-4]、[A-5]、[A-25]、[A-26]、[A-27]、[A-28]、[A-29]、[A-30]的二胺為佳。Among them, [A-1], [A-2], [A-3], [A-4], [A-5], from the viewpoint of the ability to align the liquid crystal in the vertical direction and the response speed of the liquid crystal. The diamines of [A-25], [A-26], [A-27], [A-28], [A-29], and [A-30] are preferred.

上述二胺對應作為液晶配向膜時的液晶配向性、傾斜角、電壓保持特性、存儲電荷等特性，可使用1種類或混合2種類以上使用。The diamine may be used in one type or in a mixture of two or more types depending on characteristics such as liquid crystal alignment property, tilt angle, voltage holding property, and storage charge when it is used as a liquid crystal alignment film.

具有如此將液晶配向呈垂直之側鏈的二胺，其使用量為使用於聚醯胺酸合成的二胺成分之5～50莫耳%為佳，較佳為二胺成分的10～40莫耳%為具有將液晶配向呈垂直之側鏈的二胺，特佳為15～30莫耳%。將如此具有將液晶配向呈垂直之側鏈的二胺，使用聚醯胺酸之合成上所使用的二胺成分之5～50莫耳%的量時，應答速度的提高或液晶配向固定化能力的觀點來看為特佳。The diamine having such a side chain in which the liquid crystal is aligned in a vertical direction is preferably used in an amount of 5 to 50 mol%, preferably 10 to 40 mol%, of the diamine component used for the synthesis of the polyamic acid. The ear % is a diamine having a side chain in which the liquid crystal is aligned vertically, and particularly preferably 15 to 30 mol%. When the diamine having a side chain in which the liquid crystal is aligned vertically is used in an amount of 5 to 50 mol% of the diamine component used in the synthesis of polylysine, the response speed is improved or the liquid crystal alignment is immobilized. The point of view is particularly good.

作為具有光反應性側鏈的二胺，可舉出具有將乙烯基、丙烯基、甲基丙烯基、烯丙基、苯乙烯基、桂皮醯基、chalconyl、香豆素基、馬來亞醯胺、環氧基、乙烯氧基、丙烯氧基等光反應性基作為側鏈之二胺，例如可舉出具有上述式(b)所示側鏈之二胺。更具體為例如可舉出下述一般式(6)所示二胺，但並未限定於此。Examples of the diamine having a photoreactive side chain include a vinyl group, a propenyl group, a methacryl group, an allyl group, a styryl group, a cinnamyl group, a chalcone group, a coumarin group, and a malayanide. Examples of the diamine which is a side chain of a photoreactive group such as an amine, an epoxy group, a vinyloxy group or a propyleneoxy group include a diamine having a side chain represented by the above formula (b). More specifically, for example, the diamine represented by the following general formula (6) can be mentioned, but it is not limited thereto.

[化56][化56]

(式(6)中之R12、R13及R14的定義與上述式(b)相同)(The definitions of R 12 , R 13 and R 14 in the formula (6) are the same as those in the above formula (b))

式(6)中之二個胺基(-NH2)之鍵結位置並未限定。具體對於側鏈的鍵結基而言，可舉出苯環上的2,3的位置、2,4的位置、2,5的位置、2,6的位置、3,4的位置、3,5的位置。其中由合成聚醯胺酸時的反應性觀點來看，以2,4的位置、2,5的位置或3,5的位置為佳。加上合成二胺時的容易性，以2,4的位置或3,5的位置為較佳。The bonding position of the two amine groups (-NH 2 ) in the formula (6) is not limited. Specific examples of the bonding group of the side chain include a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, a position of 3, 4, and 3, 5 location. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, it is preferred to have a position of 2, 4, a position of 2, 5, or a position of 3, 5. In addition to the ease of synthesizing the diamine, it is preferred to have a position of 2, 4 or a position of 3, 5.

作為具有光反應性側鏈的二胺，具體可舉出如以下之化合物，但並未限定於此。Specific examples of the diamine having a photoreactive side chain include the following compounds, but are not limited thereto.

[化57][化57]

(式中，X表示單鍵或選自-O-、-COO-、-NHCO-、-NH-的鍵結基，Y表示單鍵或非取代或由氟原子所取代之碳數1～20的伸烷基)(wherein, X represents a single bond or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, and Y represents a single bond or an unsubstituted or substituted carbon number of 1 to 20 by a fluorine atom. Alkyl

具有上述光反應性側鏈的二胺，對應作為液晶配向膜時的液晶配向性、傾斜角、電壓保持特性、存儲電荷等特性、作為液晶顯示元件時的液晶之應答速度等，可使用1種類或混合2種類以上使用。The diamine having the photoreactive side chain can be used in a liquid crystal alignment, a tilt angle, a voltage holding property, a charge storage property, and the like, and a response speed of a liquid crystal when used as a liquid crystal display element. Or use 2 or more types.

又，具有如此光反應性側鏈的二胺，其使用量為使用於聚醯胺酸之合成的二胺成分之10～70莫耳%為佳，較佳為20～60莫耳%，特佳為30～50莫耳%。Further, the diamine having such a photoreactive side chain is preferably used in an amount of 10 to 70 mol%, preferably 20 to 60 mol%, based on the diamine component of the synthesis of polyamic acid. Good for 30 to 50 moles.

且，聚醯胺酸僅不損害本發明的效果下，可與除具有上述將液晶配向呈垂直之側鏈之二胺，或具有光反應性側鏈的二胺以外之其他二胺作為二胺成分並用。具體而言，例如可舉出p-伸苯基二胺、2,3,5,6-四甲基-p-伸苯基二胺、2,5-二甲基-p-伸苯基二胺、m-伸苯基二胺、2,4-二甲基-m-伸苯基二胺、2,5-二胺基甲苯、2,6-二胺基甲苯、2,5-二胺基酚、2,4-二胺基酚、3,5-二胺基酚、3,5-二胺基苯甲基醇、2,4-二胺基苯甲基醇、4,6-二胺基間苯二酚、4,4’-二胺基聯苯基、3,3’-二甲基-4,4’-二胺基聯苯基、3,3’-二甲氧基-4,4’-二胺基聯苯基、3,3’-二羥基-4,4’-二胺基聯苯基、3,3’-二羧基-4,4’-二胺基聯苯基、3,3’-二氟-4,4’-聯苯基、3,3’-三氟甲基-4,4’-二胺基聯苯基、3,4’-二胺基聯苯基、3,3’-二胺基聯苯基、2,2’-二胺基聯苯基、2,3’-二胺基聯苯基、4,4’-二胺基二苯基甲烷、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、2,2’-二胺基二苯基甲烷、2,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、2,2’-二胺基二苯基醚、2,3’-二胺基二苯基醚、4,4’-磺醯基二苯胺、3,3’-磺醯基二苯胺、雙(4-胺基苯基)矽烷、雙(3-胺基苯基)矽烷、二甲基-雙(4-胺基苯基)矽烷、二甲基-雙(3-胺基苯基)矽烷、4,4’-硫二苯胺、3,3’-硫二苯胺、4,4’-二胺基二苯基胺、3,3’-二胺基二苯基胺、3,4’-二胺基二苯基胺、2,2’-二胺基二苯基胺、2,3’-二胺基二苯基胺、N-甲基(4,4’-二胺基二苯基)胺、N-甲基(3,3’-二胺基二苯基)胺、N-甲基(3,4’-二胺基二苯基)胺、N-甲基(2,2’-二胺基二苯基)胺、N-甲基(2,3’-二胺基二苯基)胺、4,4’-二胺基二苯甲酮、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、1,4-二胺基萘基、2,2’-二胺基二苯甲酮、2,3’-二胺基二苯甲酮、1,5-二胺基萘基、1,6-二胺基萘基、1,7-二胺基萘基、1,8-二胺基萘基、 2,5-二胺基萘基、2,6二胺基萘基、2,7-二胺基萘基、2,8-二胺基萘基、1,2-雙(4-胺基苯基)乙烷、1,2-雙(3-胺基苯基)乙烷、1,3-雙(4-胺基苯基)丙烷、1,3-雙(3-胺基苯基)丙烷、1,4-雙(4胺基苯基)丁烷、1,4-雙(3-胺基苯基)丁烷、雙(3,5-二乙基-4-胺基苯基)甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、1,4-雙(4-胺基苯甲基)苯、1,3-雙(4-胺基苯氧基)苯、4,4’-[1,4-伸苯基雙(亞甲基)]二苯胺、4,4’-[1,3-伸苯基雙(亞甲基)]二苯胺、3,4’-[1,4-伸苯基雙(亞甲基)]二苯胺、3,4’-[1,3-伸苯基雙(亞甲基)]二苯胺、3,3’-[1,4-伸苯基雙(亞甲基)]二苯胺、3,3’-[1,3-伸苯基雙(亞甲基)]二苯胺、1,4-伸苯基雙[(4-胺基苯基)甲酮]、1,4-伸苯基雙[(3-胺基苯基)甲酮]、1,3-伸苯基雙[(4-胺基苯基)甲酮]、1,3-伸苯基雙[(3-胺基苯基)甲酮]、1,4-伸苯基雙(4-胺基苯甲酸酯)、1,4-伸苯基雙(3-胺基苯甲酸酯)、1,3-伸苯基雙(4-胺基苯甲酸酯)、1,3-伸苯基雙(3-胺基苯甲酸酯)、雙(4-胺基苯基)對苯二甲酸酯、雙(3-胺基苯基)對苯二甲酸酯、雙(4-胺基苯基)異苯二甲酸酯、雙(3-胺基苯基)異苯二甲酸酯、N,N’-(1,4-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(4-胺基苯甲醯胺)、N,N’-(1,4-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-(1,3-伸苯基)雙(3-胺基苯甲醯胺)、N,N’-雙(4-胺基苯基)對苯二甲醯胺、 N,N’-雙(3-胺基苯基)對苯二甲醯胺、N,N’-雙(4-胺基苯基)異苯二甲醯胺、N,N’-雙(3-胺基苯基)異苯二甲醯胺、9,10-雙(4-胺基苯基)蒽、4,4’-雙(4-胺基苯氧基)二苯基碸、2,2’-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2’-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2’-雙(4-胺基苯基)六氟丙烷、2,2’-雙(3-胺基苯基)六氟丙烷、2,2’-雙(3-胺基-4-甲基苯基)六氟丙烷、2,2’-雙(4-胺基苯基)丙烷、2,2’-雙(3-胺基苯基)丙烷、2,2’-雙(3-胺基-4-甲基苯基)丙烷、3,5-二胺基安息香酸、2,5-二胺基安息香酸、1,3-雙(4-胺基苯氧基)丙烷、1,3-雙(3-胺基苯氧基)丙烷、1,4-雙(4-胺基苯氧基)丁烷、1,4-雙(3-胺基苯氧基)丁烷、1,5-雙(4-胺基苯氧基)戊烷、1,5-雙(3-胺基苯氧基)戊烷、1,6-雙(4-胺基苯氧基)己烷、1,6-雙(3-胺基苯氧基)己烷、1,7-雙(4-胺基苯氧基)庚烷、1,7-(3-胺基苯氧基)庚烷、1,8-雙(4-胺基苯氧基)辛烷、1,8-雙(3-胺基苯氧基)辛烷、1,9-雙(4-胺基苯氧基)壬烷、1,9-雙(3-胺基苯氧基)壬烷、1,10-(4-胺基苯氧基)癸烷、1,10-(3-胺基苯氧基)癸烷、1,11-(4-胺基苯氧基)十一烷、1,11-(3-胺基苯氧基)十一烷、1,12-(4-胺基苯氧基)十二烷、1,12-(3-胺基苯氧基)十二烷等芳香族二胺、雙(4-胺基環己基)甲烷、雙(4-胺基-3-甲基環己基)甲烷等脂環式二胺、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9- 二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷等脂肪族二胺。 Further, the polyamine can be used as a diamine other than the diamine having the side chain perpendicular to the alignment of the liquid crystal or the diamine having a photoreactive side chain, without impairing the effects of the present invention. Use the ingredients together. Specific examples thereof include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, and 2,5-dimethyl-p-phenylene Amine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diamine Phenolic, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-di Amino resorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy- 4,4'-Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl , 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diamine linkage Phenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodi Phenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3 '-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-double (3-Aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiyl Phenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4, 4'-Diaminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone , 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthyl, 2,2'-diaminobenzophenone, 2,3'-Diaminobenzophenone, 1,5-diaminonaphthyl, 1,6-diaminonaphthyl, 1,7-diaminonaphthyl, 1,8-diamino Naphthyl, 2,5-Diaminonaphthyl, 2,6-diaminonaphthyl, 2,7-diaminonaphthyl, 2,8-diaminonaphthyl, 1,2-bis(4-aminobenzene Ethylene, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane , 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane , 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1, 3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'- [1,4-phenylphenylbis(methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4 -phenylphenylbis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-phenylene Bis(methylene)]diphenylamine, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylene bis[(4-aminophenyl) Methyl ketone], 1,4-phenylene bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3- Phenyl bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoic acid) Ester), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis ( 3-amino benzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl) ) isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide) , N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-double (3 -aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2, 2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2' - bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl) Hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4) -methylphenyl)propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4-aminophenoxy)propane, 1,3-double ( 3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis ( 4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-double (3-Aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-double (4-aminophenoxy)octane 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane 1,10-(4-Aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-Aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane An alicyclic diamine such as an aromatic diamine, bis(4-aminocyclohexyl)methane or bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1, 4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, 9- An aliphatic diamine such as diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane.

上述其他二胺，對應作為液晶配向膜時的液晶配向性、傾斜角、電壓保持特性、存儲電荷等特性，可使用1種類或混合2種類以上使用。 The other diamines can be used in one type or in a mixture of two or more types in accordance with characteristics such as liquid crystal alignment property, tilt angle, voltage holding property, and storage charge when used as a liquid crystal alignment film.

在聚醯胺酸之合成上與上述二胺成分進行反應的四羧酸二酐並無特別限定。具體可舉出均苯四酸、2,3,6,7-萘基四羧酸、1,2,5,6-萘基四羧酸、1,4,5,8-萘基四羧酸、2,3,6,7-蒽四羧酸、1,2,5,6-蒽四羧酸、3,3’,4,4’-聯苯基四羧酸、2,3,3’,4-聯苯基四羧酸、雙(3,4-二羧基苯基)醚、3,3’,4,4’-二苯甲酮四羧酸、雙(3,4-二羧基苯基)碸、雙(3,4-二羧基苯基)甲烷、2,2-雙(3,4-二羧基苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3,4-二羧基苯基)丙烷、雙(3,4-二羧基苯基)二甲基矽烷、雙(3,4-二羧基苯基)二苯基矽烷、2,3,4,5-吡啶四羧酸、2,6-雙(3,4-二羧基苯基)吡啶、3,3’,4,4’-二苯基碸四羧酸、3,4,9,10-苝四羧酸、1,3-二苯基-1,2,3,4-環丁烷四羧酸、氧二鄰苯二甲基四羧酸、1,2,3,4-環丁烷四羧酸、1,2,3,4-環戊烷四羧酸、1,2,4,5-環己烷四羧酸、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸、1,2-二甲基-1,2,3,4-環丁烷四羧酸、1,3-二甲基-1,2,3,4-環丁烷四羧酸、1,2,3,4-環庚烷四羧酸、2,3,4,5-四氫呋喃四羧酸、3,4-二羧基-1-環己基琥珀酸、2,3,5-三羧基環戊基乙酸、3,4-二羧基-1,2,3,4-四氫-1-萘基琥珀酸、雙環[3,3,0]辛烷-2,4,6,8-四羧酸、雙環[4,3,0]壬烷- 2,4,7,9-四羧酸、雙環[4,4,0]癸烷-2,4,7,9-四羧酸、雙環[4,4,0]癸烷-2,4,8,10-四羧酸、三環[6.3.0.0<2,6>]十一烷-3,5,9,11-四羧酸、1,2,3,4-丁烷四羧酸、4-(2,5-二側氧四氫呋喃-3-基)-1,2,3,4-四氫萘基-1,2-二羧酸、雙環[2,2,2]辛-7-烯-2,3,5,6-四羧酸、5-(2,5-二側氧四氫呋喃)-3-甲基-3-環己烷-1,2-二羧酸、四環[6,2,1,1,0,2,7]十二烷-4,5,9,10-四羧酸、3,5,6-三羧基降冰片烷-2：3,5：6二羧酸、1,2,4,5-環己烷四羧酸等。當然四羧酸二酐亦對應作為液晶配向膜時的液晶配向性、電壓保持特性、存儲電荷等特性，使用1種類或亦可並用2種類以上。 The tetracarboxylic dianhydride which reacts with the above-mentioned diamine component in the synthesis of poly-proline is not specifically limited. Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthyltetracarboxylic acid, 1,2,5,6-naphthyltetracarboxylic acid, and 1,4,5,8-naphthyltetracarboxylic acid. , 2,3,6,7-decanetetracarboxylic acid, 1,2,5,6-nonanedicarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3' , 4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxybenzene Base, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2 , 2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2, 3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4, 9,10-decanetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydi-phthalic acid, 1,2,3,4 - cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofuran Carboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1- Naphthyl succinic acid, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]decane- 2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2,4, 8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-di-side oxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthyl-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7- Alkene-2,3,5,6-tetracarboxylic acid, 5-(2,5-di-oxo-tetrahydrofuran)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6 , 2,1,1,0,2,7]dodecane-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5:6 dicarboxyl Acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and the like. Of course, the tetracarboxylic dianhydride also has one type or two or more types in combination with the liquid crystal alignment property, the voltage retention property, and the storage charge when the liquid crystal alignment film is used.

藉由二胺成分與四羧酸二酐之反應，得到聚醯胺酸時，可使用公知合成手法。一般為將二胺成分與四羧酸二酐在有機溶劑中進行反應之方法。二胺成分與四羧酸二酐之反應在有機溶劑中比較容易進行，且不會產生副產物故較有利。 When a polyamine acid is obtained by the reaction of a diamine component and a tetracarboxylic dianhydride, a well-known synthetic method can be used. A method of reacting a diamine component with a tetracarboxylic dianhydride in an organic solvent is generally employed. The reaction of the diamine component with the tetracarboxylic dianhydride is relatively easy to carry out in an organic solvent, and it is advantageous in that no by-product is produced.

作為使用於上述反應之有機溶劑，若為溶解所生成之聚醯胺酸者即可，並無特別限定。且，即使為不溶解聚醯胺酸的有機溶劑，在不析出所生成之聚醯胺酸的範圍下，可混合於上述溶劑後使用。且有機溶劑中之水分為不阻礙聚合反應，且會成為水解所生成之聚醯胺酸的原因，故有機溶劑使用先脫水乾燥者為佳。作為使用於反應之有機溶劑，例如可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基甲醯胺、N-甲基甲醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、2-吡咯烷酮、1,3-二甲基-2-咪唑 烷酮、3-甲氧基-N,N-二甲基丙烷醯胺、N-甲基己內醯胺、二甲基亞碸、四甲基脲、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙醇、甲氧基甲基戊醇、二戊烯、乙基戊基酮、甲基壬基酮、甲基乙酮、甲基異戊基酮、甲基異丙酮、甲基賽路蘇、乙基賽路蘇、甲基賽路蘇乙酸酯、乙二醇二丁醚乙酸酯、乙二醇二***乙酸酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇單丁基醚、丙二醇-第三丁基醚、二丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二乙二醇二乙基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酸酯、丁基醚、二異丁酮、甲基環己烯、丙基醚、己基醚、二噁烷、n-己烷、n-戊烷、n-辛烷、二乙基醚、環己酮、碳酸乙二酯、碳酸丙二酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二甘醇二甲醚、4-羥基-4-甲基-2-戊酮、2-乙基-1-己醇等。這 些有機溶劑可單獨使用或亦可混合後使用。 The organic solvent to be used in the above reaction is not particularly limited as long as it is a polylysine which is produced by dissolution. Further, even if it is an organic solvent which does not dissolve polyamic acid, it can be used after being mixed with the above solvent in the range in which the produced polyamic acid is not precipitated. Further, since the water in the organic solvent does not inhibit the polymerization reaction and becomes a polylysine which is formed by hydrolysis, it is preferred that the organic solvent be dried by dehydration. Examples of the organic solvent used in the reaction include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, and N-methylmethyl. Indoleamine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-di Methylpropane decylamine, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropanol, A Oxymethylpentanol, dipentene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, methyl sarsulu, ethyl 赛路Sue, methyl sarbuta acetate, ethylene glycol dibutyl ether acetate, ethylene glycol diethyl ether acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol Acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol - tert-butyl ether, two Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate single Ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3 - methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, Propyl ether, Hexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, acetic acid Methyl ester, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate , 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, diethylene glycol Dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, and the like. These organic solvents may be used singly or in combination.

將二胺成分與四羧酸二酐成分在有機溶劑中進行反應時，攪拌將二胺成分分散或溶解於有機溶劑的溶液，將四羧酸二酐直接或分散或溶解於有機溶劑後添加之方法、相反地於將四羧酸二酐分散或溶解於有機溶劑之溶液中添加二胺成分之方法、交互添加四羧酸二酐與二胺成分之方法等可舉出，使用這些任一方法皆可。又，四羧酸二酐或二胺成分係由複數種化合物所成時，可預先混合之狀態下進行反應，或亦可各別順序進行反應，且各別反應之低分子量體可經混合反應後作為高分子量體。 When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride is directly or dispersed or dissolved in an organic solvent, and then added. In the method, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method of mutually adding a tetracarboxylic dianhydride and a diamine component, and the like may be mentioned, and any of these methods may be used. Can be. Further, when the tetracarboxylic dianhydride or the diamine component is formed of a plurality of compounds, the reaction may be carried out in a state of being mixed in advance, or the reaction may be carried out in a separate order, and the low molecular weight bodies of the respective reactions may be subjected to a mixing reaction. After that, it is a high molecular weight body.

使二胺成分與四羧酸二酐成分進行反應時的溫度為，可選擇任意溫度，例如-20℃~150℃，較佳為-5℃~100℃的範圍。又，反應可在任意濃度下進行，例如對於反應液之二胺成分與四羧酸二酐成分的合計量以1~50質量%為佳，較佳為5~30質量%。 The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted may be any temperature, for example, -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration. For example, the total amount of the diamine component and the tetracarboxylic dianhydride component of the reaction liquid is preferably from 1 to 50% by mass, preferably from 5 to 30% by mass.

上述聚合反應中，對於二胺成分之合計莫耳數而言，四羧酸二酐成分的合計莫耳數比率為，對應所得之聚醯胺酸的分子量可選擇任意值。與一般聚縮合反應同樣地，越接近該莫耳比1.0，所生成之聚醯胺酸的分子量變的越大。較佳範圍為0.8~1.2。 In the above polymerization reaction, the total molar ratio of the tetracarboxylic dianhydride component to the total number of moles of the diamine component is an arbitrary value depending on the molecular weight of the obtained polyamic acid. As in the case of the general polycondensation reaction, the closer to the molar ratio of 1.0, the larger the molecular weight of the produced polyamine. The preferred range is from 0.8 to 1.2.

合成本發明所使用的聚醯胺酸之方法並未限定於上述手法，與一般聚醯胺酸之合成方法同樣地，取代上述四羧酸二酐，使用對應結構的四羧酸或四羧酸二鹵化物等四羧酸衍生物，即使以公知方法進行反應亦可得到對應之聚醯 胺酸。 The method for synthesizing the polyaminic acid used in the present invention is not limited to the above method, and similarly to the general method for synthesizing poly-proline, a tetracarboxylic or tetracarboxylic acid having a corresponding structure is used instead of the above tetracarboxylic dianhydride. A tetracarboxylic acid derivative such as a dihalide can be obtained by a known method even if it is reacted by a known method. Amino acid.

作為將上述聚醯胺酸進行醯亞胺化的聚醯亞胺之方法，可舉出將聚醯胺酸的溶液直接加熱的熱醯亞胺化、於聚醯胺酸的溶液添加觸媒的觸媒醯亞胺化。且，由聚醯胺酸對聚醯亞胺之醯亞胺化率非必須為100%。 The method of the polyimine which bismuthizes the said poly lysine is the heat-imidation of the solution of the poly phthalic acid, and the catalyst of the solution of the poly phthalic acid. The catalyst is imidized. Moreover, the ruthenium imidization ratio of the polyamidene to the polyimine is not necessarily 100%.

將聚醯胺酸在溶液中使其熱醯亞胺化時的溫度為100℃~400℃，較佳為120℃~250℃，一邊將藉由醯亞胺化反應所生成之水排除於系統外一邊進行為佳。 The temperature at which the polyaminic acid is thermally imidated in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the hydrazine imidization reaction is excluded from the system. It is better to carry out the outside.

聚醯胺酸的觸媒醯亞胺化為於聚醯胺酸的溶液中，添加鹼性觸媒與酸酐，可在-20~250℃，較佳為在0~180℃下攪拌而進行。鹼性觸媒的量為醯胺酸基之0.5~30莫耳倍，較佳為2~20莫耳倍，酸酐的量為醯胺酸基之1~50莫耳倍，較佳為3~30莫耳倍。作為鹼性觸媒，可舉出吡啶、三乙胺、三甲胺、三丁胺、三辛胺等，其中亦以吡啶具有對於進行反應為適度之鹼性故較佳。作為酸酐，可舉出乙酸酐、偏苯三甲酸酐、均苯四甲酸二酐等，其中亦以使用乙酸酐時，反應終了後的純化變的容易故較佳。藉由觸媒醯亞胺化之醯亞胺化率可藉由調節觸媒量與反應溫度、反應時間而控制。 The ruthenium ruthenium of the polyptanic acid is added to a solution of polyglycine, and a basic catalyst and an acid anhydride are added, and the mixture can be stirred at -20 to 250 ° C, preferably at 0 to 180 ° C. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the prolyl group. 30 moles. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has a moderate alkalinity for the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride. Among them, when acetic anhydride is used, purification after completion of the reaction is preferred, which is preferable. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

又，聚醯胺酸酯為，四羧酸二酯二氯化物與與上述聚醯胺酸之合成同樣的二胺之反應，或四羧酸二酯與與上述聚醯胺酸之合成同樣的二胺在適當縮合劑或鹼存在下等使其反應而可製造。或以上述方法預先合成聚醯胺酸，利用高分子反應將醯胺酸中之羧酸進行酯化而可得。具體而言 ，例如可將四羧酸二酯二氯化物與二胺在鹼與有機溶劑之存在下，於-20℃~150℃，較佳為於0℃~50℃中，進行30分鐘~24小時，較佳為進行1小時~4小時反應後合成聚醯胺酸酯。而將聚醯胺酸酯在高溫下加熱，即使藉由促進脫醇而使其閉環，亦可得到聚醯亞胺。 Further, the polyphthalate is a reaction of a tetracarboxylic acid diester dichloride with a diamine similar to the synthesis of the above polyamic acid, or a tetracarboxylic acid diester having the same composition as that of the above polyamic acid. The diamine can be produced by reacting it in the presence of a suitable condensing agent or a base. Alternatively, polylysine may be synthesized in advance by the above method, and a carboxylic acid in valeric acid may be esterified by a polymer reaction to obtain a carboxylic acid. in particular For example, the tetracarboxylic acid diester dichloride and the diamine can be carried out in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably at 0 ° C to 50 ° C for 30 minutes to 24 hours. Preferably, the polyphthalate is synthesized after a reaction of from 1 hour to 4 hours. On the other hand, when the polyglycolate is heated at a high temperature, even if it is closed by promoting the dealcoholization, a polyimine can be obtained.

由聚醯胺酸、聚醯胺酸酯等聚醯亞胺前驅物或聚醯亞胺的反應溶液中回收所生成之聚醯胺酸、聚醯胺酸酯等聚醯亞胺前驅物或聚醯亞胺時，將反應溶液投入於弱溶劑中使其沈澱即可。作為使用於沈澱之弱溶劑，可舉出甲醇、丙酮、己烷、乙二醇二丁醚、庚烷、甲基乙酮、甲基異丁酮、乙醇、甲苯、苯、水等。投入於弱溶劑使其沈澱的聚合物經過濾回收後，在常壓或減壓下，可在常溫或加熱下乾燥。又，將沈澱回收之聚合物再溶解於有機溶劑，再沈澱回收的操作重複2~10次後，可減少聚合物中之雜質。作為此時的弱溶劑，例如可舉出醇類、酮類、烴等，使用彼等中所選出的3種類以上弱溶劑時，可進一步提高純化效率故較佳。 The polyimine precursor or the like which is formed from a polyimine precursor such as polyglycolic acid or a polyamidomate or a polyimine is recovered from a polyimine precursor or a polyphthalamide precursor. In the case of quinone imine, the reaction solution may be placed in a weak solvent to precipitate. Examples of the weak solvent used for precipitation include methanol, acetone, hexane, ethylene glycol dibutyl ether, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer precipitated by the weak solvent is recovered by filtration, and then dried under normal pressure or under reduced pressure at normal temperature or under reduced pressure. Further, the precipitate-recovered polymer is redissolved in an organic solvent, and the reprecipitation recovery operation is repeated 2 to 10 times to reduce impurities in the polymer. Examples of the weak solvent at this time include alcohols, ketones, hydrocarbons, and the like. When three or more kinds of weak solvents selected from the above are used, the purification efficiency can be further improved, which is preferable.

本發明的液晶配向劑為具有以下聚合性化合物、聚合物及溶劑即可，該聚合性化合物為持有具有如上述之α-亞甲基-γ-丁內酯基的末端與具有進行光聚合或光交聯之基的末端的聚合性化合物，該聚合物為形成配向液晶所得之液晶配向膜的聚合物，該配合比率雖無特別限定，持有具有α-亞甲基-γ-丁內酯基之末端與具有進行光聚合或光交聯之基的末端之聚合性化合物含有量，對於形成配向液 晶所得之液晶配向膜的聚合物100質量份而言，以1~50質量份為佳，更佳為5~30質量份。又，於液晶配向劑所含有之形成配向液晶所得之液晶配向膜的聚合物之含有量以1質量%~20質量%為佳，較佳為3質量%~15質量%，特佳為3~10質量%。 The liquid crystal alignment agent of the present invention may be a polymerizable compound having a terminal having an α-methylene-γ-butyrolactone group as described above and having a photopolymerization, and a solvent. Or a polymerizable compound at the terminal of the photocrosslinking group, which is a polymer which forms a liquid crystal alignment film obtained by aligning a liquid crystal, and the compounding ratio is not particularly limited, and it has an α-methylene-γ-butyl group. The content of the polymerizable compound at the end of the ester group and the terminal having a photopolymerization or photocrosslinking group, for forming an alignment liquid 100 parts by mass of the polymer of the liquid crystal alignment film obtained by the crystal is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass. Further, the content of the polymer of the liquid crystal alignment film obtained by forming the alignment liquid crystal contained in the liquid crystal alignment agent is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, particularly preferably 3% by mass. 10% by mass.

又，本發明的液晶配向劑亦可含有除形成配向液晶所得之液晶配向膜的聚合物以外之其他聚合物。此時，聚合物全成分中之該其他聚合物之含有量以0.5質量%~15質量%為佳，較佳為1質量%~10質量%。 Further, the liquid crystal alignment agent of the present invention may contain a polymer other than the polymer which forms the liquid crystal alignment film obtained by aligning the liquid crystal. In this case, the content of the other polymer in the entire polymer component is preferably 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.

具有液晶配向劑之聚合物的分子量，若考慮到塗佈液晶配向劑所得之液晶配向膜的強度及塗膜形成時的作業性、塗膜的均勻性時，以GPC(Gel Permeation Chromatography)法測定之重量平均分子量以5,000~1,000,000為佳，較佳為10,000~150,000。 The molecular weight of the polymer having a liquid crystal alignment agent is determined by GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained by coating the liquid crystal alignment agent, the workability at the time of coating film formation, and the uniformity of the coating film. The weight average molecular weight is preferably 5,000 to 1,000,000, preferably 10,000 to 150,000.

<溶劑> <solvent>

本發明的液晶配向劑所含有之溶劑並無特別限定，若可溶解或分散持有具有α-亞甲基-γ-丁內酯基之末端與具有進行光聚合或光交聯之基的末端的聚合性化合物、或形成配向液晶所得之液晶配向膜的聚合物等含有成分者即可。例如可舉出如上述聚醯胺酸之合成所例示之有機溶劑。其中亦以N-甲基-2-吡咯烷酮、γ-丁內酯、N-乙基-2-吡咯烷酮、1,3-二甲基-2-咪唑烷酮、3-甲氧基-N,N-二甲基丙烷醯胺由溶解性之觀點來看為佳。當然可使用2種類以上 之混合溶劑。 The solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited, and if it is soluble or dispersible, it has an end having an α-methylene-γ-butyrolactone group and an end having a group which undergoes photopolymerization or photocrosslinking. The polymerizable compound or a polymer which forms a liquid crystal alignment film obtained by aligning the liquid crystal may contain a component. For example, an organic solvent exemplified as the synthesis of the above polyamic acid can be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N - Dimethylpropane decylamine is preferred from the viewpoint of solubility. Of course, more than 2 types can be used. a mixed solvent.

又，可將提高塗膜均勻性或平滑性之溶劑混合於液晶配向劑之含有成分的溶解性高之溶劑中使用為佳。作為提高塗膜之均勻性或平滑性之溶劑，例如可舉出異丙醇、甲氧基甲基戊醇、甲基賽路蘇、乙二醇二***、乙二醇二丁醚、甲基賽路蘇乙酸酯、乙二醇二丁醚乙酸酯、乙二醇二***乙酸酯、丁基卡必醇、乙基卡必醇、乙基卡必醇乙酸酯、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇單丁基醚、丙二醇-第三丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二乙二醇二乙基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酸酯、丁基醚、二異丁酮、甲基環己烯、丙基醚、二己基醚、n-己烷、n-戊烷、n-辛烷、二乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、 1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯酯、乳酸乙酯酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊酯、2-乙基-1-己醇等。這些溶劑可混合複數種類。使用這些溶劑時，液晶配向劑中所含之溶劑全體的5~80質量%為佳，較佳為20~60質量%。 Further, it is preferred to use a solvent which improves the uniformity or smoothness of the coating film in a solvent having a high solubility in the component contained in the liquid crystal alignment agent. Examples of the solvent for improving the uniformity or smoothness of the coating film include isopropyl alcohol, methoxymethylpentanol, methyl sarbuta, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and methyl group.赛路苏acetate, ethylene glycol dibutyl ether acetate, ethylene glycol diethyl ether acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol , ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol - third Butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate Methyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetic acid Ester monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Butyl ether, Isobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octyl Alkane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid Propyl ester, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-B Acid ester, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-Ethyl-1-hexanol and the like. These solvents can be mixed in a plurality of types. When these solvents are used, the total amount of the solvent contained in the liquid crystal alignment agent is preferably from 5 to 80% by mass, preferably from 20 to 60% by mass.

於液晶配向劑可含有除上述以外之成分。作為該例子，可舉出提高塗佈液晶配向劑時的膜厚均勻性或表面平滑性之化合物、提高液晶配向膜與基板之密著性的化合物等。 The liquid crystal alignment agent may contain components other than the above. As such an example, a compound which improves the film thickness uniformity or surface smoothness when a liquid crystal alignment agent is applied, and a compound which improves the adhesion between the liquid crystal alignment film and the substrate can be mentioned.

作為提高膜厚均勻性或表面平滑性之化合物，可舉出氟系界面活性劑、聚矽氧系界面活性劑、非離子系界面活性劑等。更具體例如可舉出Eftop EF301、EF303、EF352(TOHKEM PRODUCTS CORP製)、Megafac F171、F173、R-30(大日本油墨公司製)、Fluorad FC430、FC431(住友3M公司製)、Asahiguard AG710、SurflonS-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子公司製)等。使用這些界面活性劑時，該使用比率對於含於液晶配向劑之聚合物總量100質量份而言，較佳為0.01~2質量份，更佳為0.01~1質量份。 Examples of the compound for improving film thickness uniformity or surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. More specifically, for example, Eftop EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS CORP), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahiguard AG710, and Surflon S -382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). When the surfactant is used, the use ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent.

作為提高液晶配向膜與基板之密著性的化合物之具體例，可舉出含有官能性矽烷之化合物或含有環氧基之化合物等。例如可舉出3-胺基丙基三甲氧基矽烷、3-胺基丙基 三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-醯脲丙基三甲氧基矽烷、3-醯脲丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽基丙基三伸乙基三胺、N-三甲氧基矽基丙基三伸乙基三胺、10-三甲氧基矽基-1,4,7-三氮雜癸烷、10-三乙氧基矽基-1,4,7-三氮雜癸烷、9-三甲氧基矽基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽基-3,6-二氮雜壬基乙酸酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧基伸乙基)-3-胺基丙基三甲氧基矽烷、N-雙(氧基伸乙基)-3-胺基丙基三乙氧基矽烷、乙二醇二氧化丙烯醚、聚乙二醇二氧化丙烯醚、丙二醇二氧化丙烯醚、三丙二醇二氧化丙烯醚、聚丙二醇二氧化丙烯醚、新戊二醇二氧化丙烯醚、1,6-己二醇二氧化丙烯醚、甘油二氧化丙烯醚、2,2-二溴新戊二醇二氧化丙烯醚、1,3,5,6-四氧化丙烯基-2,4-己二醇、N,N,N’,N’,-四氧化丙烯基-間二甲苯二胺、1,3-雙(N,N-二氧化丙烯基胺基甲基)環己烷、N,N,N’,N’,-四氧化丙烯基-4、4’-二胺基二苯基甲烷、3-(N-烯丙基-N-氧化丙烯基)胺基丙基三甲氧基矽烷、3-(N,N-二氧化丙烯基)胺基丙基三甲氧基矽烷等。又欲進一步提高液晶配向膜之膜強度，可添加2,2’-雙(4-羥 基-3,5-二羥基甲基苯基)丙烷、四(甲氧基甲基)雙酚等酚化合物。使用這些化合物時，對於液晶配向劑中所含有之聚合物總量100質量份而言以0.1~30質量份為佳，較佳為1~20質量份之含有環氧基之化合物等可舉出。 Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a compound containing a functional decane or a compound containing an epoxy group. For example, 3-aminopropyltrimethoxydecane and 3-aminopropyl are mentioned. Triethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane , N-(2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N -ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylidene Triamine, N-trimethoxydecylpropyltrisethyltriamine, 10-trimethoxyindolyl-1,4,7-triazadecane, 10-triethoxyindolyl-1, 4,7-triazadecane, 9-trimethoxyindolyl-3,6-diazaindolyl acetate, 9-triethoxyindolyl-3,6-diazaindoleyl Acid ester, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethyl Oxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylidene)-3-aminopropyltrimethoxydecane, N-bis(oxyethyl) )-3-aminopropyltriethoxydecane, ethylene glycol propylene oxide, Ethylene glycol propylene oxide ether, propylene glycol propylene oxide ether, tripropylene glycol propylene oxide ether, polypropylene glycol propylene oxide ether, neopentyl glycol propylene oxide ether, 1,6-hexanediol propylene oxide ether, glycerin Dipropylene oxide, 2,2-dibromoneopentyl glycol propylene oxide, 1,3,5,6-tetrapropenyl-2,4-hexanediol, N,N,N',N' ,-Tetrapropenyl-m-xylenediamine, 1,3-bis(N,N-propylene oxide aminomethyl)cyclohexane, N,N,N',N',-Tetrapropylene oxide 4-, 4'-diaminodiphenylmethane, 3-(N-allyl-N-oxypropylene)aminopropyltrimethoxydecane, 3-(N,N-propylene oxide Aminopropyltrimethoxydecane, and the like. In order to further increase the film strength of the liquid crystal alignment film, 2,2'-bis(4-hydroxyl can be added. A phenolic compound such as benzyl-3,5-dihydroxymethylphenyl)propane or tetrakis(methoxymethyl)bisphenol. When these compounds are used, the amount of the epoxy group-containing compound is preferably from 0.1 to 30 parts by mass, preferably from 1 to 20 parts by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent. .

且於液晶配向劑中以不損害本發明的效果之範圍內，可添加以變化液晶配向膜的介電率或導電性等電氣特性為目的的介電體或導電物質之上述其他成分。 Further, in the liquid crystal alignment agent, the above-mentioned other components of the dielectric material or the conductive material for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film may be added to the extent that the effects of the present invention are not impaired.

藉由將該液晶配向劑塗佈於基板上後燒成，可形成將液晶配向呈垂直的液晶配向膜等配向液晶所得之液晶配向膜。本發明的液晶配向劑因具有持有具有α-亞甲基-γ-丁內酯基的末端與具有進行光聚合或光交聯之基的末端之聚合性化合物，故即使在液晶中未含有聚合性化合物且在高溫進行燒成時，亦可使使用所得之液晶配向膜的液晶顯示元件的應答速度成為快速者。當然，於液晶中含有聚合性化合物時、或在低溫(例如140℃以下)進行燒成時，亦可使其成為液晶顯示元件的應答速度快速者。 By applying the liquid crystal alignment agent to the substrate and baking it, a liquid crystal alignment film obtained by aligning liquid crystals such as a liquid crystal alignment film having a vertical liquid crystal alignment can be formed. Since the liquid crystal alignment agent of the present invention has a polymerizable compound having a terminal having an α-methylene-γ-butyrolactone group and a terminal having a photopolymerization or photocrosslinking group, it is not contained in the liquid crystal. When the polymerizable compound is fired at a high temperature, the response speed of the liquid crystal display element using the obtained liquid crystal alignment film can be made fast. Needless to say, when the liquid crystal contains a polymerizable compound or when it is fired at a low temperature (for example, 140 ° C or lower), the response speed of the liquid crystal display element can be made fast.

例如將本發明的液晶定向劑塗佈於基板後，視必要經乾燥並進行燒成後所得之硬化膜，可直接作為液晶定向膜使用。又，可摩擦該硬化膜，或照射偏光或特定波長之光等，或進行離子束等處理，亦可作為PSA用定向膜於液晶填充後的液晶顯示元件外加電壓的狀態下照射UV。特別可作為PSA用定向膜使用。 For example, after the liquid crystal aligning agent of the present invention is applied onto a substrate, the cured film obtained by drying and drying after necessary may be used as a liquid crystal alignment film as it is. Further, the cured film may be rubbed, or irradiated with polarized light or light of a specific wavelength, or subjected to an ion beam or the like, or may be irradiated with UV as a PSA oriented film in a state where a voltage is applied to the liquid crystal display element after liquid crystal filling. It is especially useful as an oriented film for PSA.

此時，作為所使用的基板，若為透明性高的基板即可，並無特別限定，可使用玻璃板、聚碳酸酯、聚(甲基) 丙烯酸酯、聚醚碸、聚芳酯、聚胺酯、聚碸、聚醚、聚醚酮、三甲基戊烯、聚烯烴、聚乙烯對苯二甲酸酯、(甲基)丙烯腈、三乙酸纖維素、二乙酸纖維素、乙酸酯丁酸酯纖維素等塑質基板等。又，使用形成欲使其液晶驅動的ITO電極等的基板時，由製程的簡單化之觀點來看為佳。又，若在反射型液晶顯示元件中僅為單側基板，亦可使用矽晶圓等不透明物，此時的電極可使用反射鋁等光之材料素、二乙酸纖維素、乙酸酯丁酸酯纖維素等塑質基板等。 In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass plate, polycarbonate, or poly(methyl) can be used. Acrylate, polyether oxime, polyarylate, polyurethane, polyfluorene, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetic acid A plastic substrate such as cellulose, cellulose diacetate or acetate butyrate cellulose. Further, when a substrate on which an ITO electrode or the like to be driven by liquid crystal is formed is used, it is preferable from the viewpoint of simplification of the process. Further, in the case of the reflective liquid crystal display device, only a single-sided substrate can be used, and an opaque material such as a germanium wafer can also be used. In this case, an optical material such as aluminum or the like, cellulose diacetate or acetic acid butyric acid can be used as the electrode. A plastic substrate such as ester cellulose.

液晶配向劑的塗佈方法並為特別限定，可舉出網版印刷、柯式印刷、揉版印刷等印刷法、噴射法、噴射法、輥塗佈法或浸漬、輥塗佈、縫隙塗佈、旋轉塗佈器等。由生產性的層面來看，於工業上廣泛被採用的轉印印刷法亦適用於本發明。 The method of applying the liquid crystal alignment agent is particularly limited, and examples thereof include a printing method such as screen printing, offset printing, or stencil printing, a spraying method, a spraying method, a roll coating method, or dipping, roll coating, and slit coating. , spin coater, etc. From the viewpoint of productivity, a transfer printing method widely used in the industry is also applicable to the present invention.

塗佈液晶定向劑後之乾燥步驟，雖非必要，但塗佈後至燒成的時間對於每基板而言並非一定之情況或塗佈後未馬上燒成時，進行乾燥步驟為佳。該乾燥為基板的搬送等不會使塗膜形狀變形的程度下除去溶劑即可，對於該乾燥手段並無特別限定。例如可舉出在溫度40℃~150℃，較佳為60℃~100℃的加熱板上，進行0.5分鐘~30分鐘，較佳為1分鐘~5分鐘乾燥之方法。 Although the drying step after the application of the liquid crystal aligning agent is not necessary, the drying step is preferably performed when the time from the application to the baking is not constant for each substrate or when the film is not immediately baked after coating. This drying is not particularly limited as long as the drying means is such that the solvent is removed without deforming the shape of the coating film. For example, a method of drying at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C, for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes, may be mentioned.

在上述方法塗佈液晶配向劑所形成之塗膜可經燒成而成為硬化膜。藉由塗佈液晶定向劑所形成的塗膜之燒成溫度並無限定，例如可在100~350℃之任意溫度下進行，較佳為120℃~300℃，更佳為150℃~250℃。可在燒成時間 為5分鐘~240分鐘的任意時間下進行燒成。較佳為10分鐘~90分鐘，更佳為20分鐘~90分鐘。加熱可使用一般公知方法，例如可使用加熱板、熱風循環爐、紅外線爐等進行。 The coating film formed by applying the liquid crystal alignment agent in the above method can be fired to form a cured film. The baking temperature of the coating film formed by coating the liquid crystal aligning agent is not limited, and can be carried out, for example, at any temperature of 100 to 350 ° C, preferably 120 ° C to 300 ° C, more preferably 150 ° C to 250 ° C. . Can be burned It is baked at any time from 5 minutes to 240 minutes. It is preferably from 10 minutes to 90 minutes, more preferably from 20 minutes to 90 minutes. The heating can be carried out by a generally known method, and can be carried out, for example, using a hot plate, a hot air circulating furnace, an infrared furnace or the like.

又，燒成所得之液晶配向膜的厚度並無特別限定，較佳為5~300nm，更佳為10~100nm。 Further, the thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 100 nm.

而本發明的液晶顯示元件可藉由上述方法，於基板形成液晶配向膜後，以公知方法製作液晶胞。作為液晶顯示元件的具體例，係為具備具有配置成相對方向向的2片基板、設置於基板間之液晶層、基板與液晶層之間所設置的藉由本發明的液晶配向劑所形成之上述液晶配向膜的液晶胞之液晶顯示元件。具體而言，將本發明的液晶配向劑塗佈於2片基板上並燒成後形成液晶配向膜，將2片基板配置成液晶配向膜為相對方向，於該2片基板之間挾持以液晶構成之液晶層，即，具備使其於液晶配向膜接觸後設置液晶層，於液晶配向膜及液晶層一邊外加電壓下一邊照射紫外線所製作之液晶胞的垂直配向方式等液晶顯示元件。使用藉由如此本發明的液晶配向劑所形成之液晶配向膜，於液晶配向膜及液晶層一邊外加電壓一邊照射紫外線，使持有具有α-亞甲基-γ-丁內酯基之末端與具有進行光聚合或光交聯之基的末端之聚合性化合物進行聚合的同時，形成配向液晶所得之液晶配向膜的聚合物或聚合性化合物之聚合物與聚合性化合物進行反應，藉由彼等進行交聯而成為應答速度優良的液晶顯示元件。 On the other hand, in the liquid crystal display device of the present invention, after the liquid crystal alignment film is formed on the substrate by the above method, the liquid crystal cell is produced by a known method. Specific examples of the liquid crystal display device include the above-described liquid crystal alignment agent having the two substrates arranged in the opposite direction, the liquid crystal layer provided between the substrates, and the liquid crystal layer provided by the liquid crystal alignment agent of the present invention. A liquid crystal display element of a liquid crystal cell of a liquid crystal alignment film. Specifically, the liquid crystal alignment agent of the present invention is applied onto two substrates and fired to form a liquid crystal alignment film, and the two substrates are arranged such that the liquid crystal alignment film is in a relative direction, and the liquid crystal alignment film is held between the two substrates. A liquid crystal display element such as a vertical alignment method in which a liquid crystal layer is formed by bringing a liquid crystal layer into contact with a liquid crystal alignment film and a liquid crystal cell is irradiated with ultraviolet light while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. By using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, ultraviolet rays are applied to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, and the end having the α-methylene-γ-butyrolactone group is held. The polymerizable compound having a terminal for photopolymerization or photocrosslinking is polymerized, and a polymer of a polymer or a polymerizable compound which forms a liquid crystal alignment film obtained by aligning with a liquid crystal is reacted with a polymerizable compound, by which they are reacted. Crosslinking is performed to obtain a liquid crystal display element having excellent response speed.

作為使用本發明的液晶顯示元件之基板，若為透明性高之基板即可並無特別限定，一般為於基板上形成欲使液晶驅動的透明電極之基板。作為具體例，可舉出與在上述液晶配向膜所記載之相同基板。雖可使用過去設有電極圖型或突起圖型之基板，對於本發明之液晶顯示元件，作為形成液晶配向膜之液晶配向劑，使用具有以下聚合性化合物之本發明的液晶配向劑，該聚合性化合物為持有具有α-亞甲基-γ-丁內酯基之末端與具有進行光聚合或光交聯之基的末端之聚合性化合物；於單側基板上形成例如1至10μm的線/縫隙電極圖型，對於相對方向基板上未形成縫隙圖型或突起圖型之結構亦可作用，藉由該結構之液晶顯示元件，可簡略化製造時的製程而得到高透過率。 The substrate using the liquid crystal display element of the present invention is not particularly limited as long as it is a substrate having high transparency, and is generally a substrate on which a transparent electrode to be driven by a liquid crystal is formed on a substrate. As a specific example, the same substrate as described in the above liquid crystal alignment film can be mentioned. In the liquid crystal display device of the present invention, a liquid crystal alignment agent for forming a liquid crystal alignment film is used as the liquid crystal alignment agent of the present invention, and a liquid crystal alignment agent of the present invention having the following polymerizable compound is used. The compound is a polymerizable compound having a terminal having an α-methylene-γ-butyrolactone group and a terminal having a photopolymerization or photocrosslinking group; and a line of, for example, 1 to 10 μm is formed on the one-sided substrate. The pattern of the slit electrode can also function for a structure in which a slit pattern or a protrusion pattern is not formed on the opposite direction substrate, and the liquid crystal display element of the structure can simplify the manufacturing process to obtain a high transmittance.

又，對於如TFT型之元件的高功能元件，使用於欲液晶驅動的電極與基板之間形成如晶體管之元件者。 Further, for a high-function element such as a TFT type element, an element such as a transistor is formed between an electrode to be driven by a liquid crystal and a substrate.

透過型液晶顯示元件之情況為，一般使用如上述之基板，在反射型液晶顯示元件中，若僅為單側基板亦可使用矽晶圓等不透明基板。此時，形成於基板之電極中，可使用可反射光之如鋁的材料。 In the case of a transmissive liquid crystal display device, a substrate as described above is generally used. In the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the single-sided substrate. At this time, a material such as aluminum which can reflect light can be used in the electrode of the substrate.

液晶配向膜係由於該基板上塗佈本發明的液晶配向劑後經燒成而形成者，詳細內容如上述。 The liquid crystal alignment film is formed by applying the liquid crystal alignment agent of the present invention to the substrate and firing it, and the details are as described above.

構成本發明之液晶顯示元件的液晶層之液晶材料並無特別限定，可使用過去垂直配向方式等所使用之液晶材料，例如莫克公司製之MLC-6608或MLC-6609等負型液晶。 The liquid crystal material constituting the liquid crystal layer of the liquid crystal display device of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method or the like, for example, a negative liquid crystal such as MLC-6608 or MLC-6609 manufactured by Moker Corporation can be used.

作為將該液晶層挾持於2片基板之間的方法，可舉出 公知方法。例如準備形成液晶配向膜之1對基板，於一方基板的液晶配向膜上散佈珠子等間隔物，貼合另一方基板使液晶配向膜所形成之面成為內側，將液晶經減壓注入後封止的方法可舉出。又，準備液晶配向膜所形成之1對基板，於一方基板的液晶配向膜上散佈珠子等間隔物後滴入液晶，其後貼合另一方基板使液晶配向膜所形成之面成為內側後進行封止之方法亦可製作液晶胞。此時的間隔物厚度較佳為1~30μm，更佳為2~10μm。 As a method of holding the liquid crystal layer between two substrates, a method can be mentioned A known method. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are spread on the liquid crystal alignment film of one substrate, and the other substrate is bonded to the inside of the surface formed by the liquid crystal alignment film, and the liquid crystal is injected under reduced pressure and then sealed. The method can be mentioned. In addition, a pair of substrates formed by the liquid crystal alignment film are prepared, and a spacer such as a bead is spread on the liquid crystal alignment film of one of the substrates, and then the liquid crystal is dropped, and then the other substrate is bonded to the inside of the liquid crystal alignment film. The method of sealing can also produce a liquid crystal cell. The spacer thickness at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

於液晶配向膜及液晶層一邊外加電壓一邊照射紫外線而製造液晶胞的步驟為，例如可舉出於基板上所設置之電極間輸入電壓後於液晶配向膜及液晶層外加電場，保持該電場下照射紫外線之方法。其中，於電極間輸入的電壓例如為5~30Vp-p，較佳為5~20Vp-p。紫外線的照射量例如為1~60J，較佳為40J以下，紫外線照射量越少構成液晶顯示元件之構件的破壊所產生的信頼性低下會受到抑制，且藉由減少紫外線照射時間可提高製造效率故較佳。 The step of producing a liquid crystal cell by applying a voltage to the liquid crystal alignment film and the liquid crystal layer while applying a voltage is, for example, an electric field applied to the liquid crystal alignment film and the liquid crystal layer after the input voltage between the electrodes provided on the substrate is applied, and the electric field is maintained. A method of irradiating ultraviolet rays. The voltage input between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the lower the amount of ultraviolet irradiation, the lower the letter reliability caused by the breakage of the members constituting the liquid crystal display element, and the manufacturing efficiency can be improved by reducing the ultraviolet irradiation time. Therefore, it is better.

如此，於液晶配向膜及液晶層一邊外加電壓一邊照射紫外線時，持有具有α-亞甲基-γ-丁內酯基之末端與具有進行光聚合或光交聯之基的末端之聚合性化合物會反應而形成聚合物，藉由該聚合物，液晶分子的傾斜方向被記憶，可加速所得之液晶顯示元件的應答速度。 When the ultraviolet ray is applied to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, the terminal having the α-methylene-γ-butyrolactone group and the terminal having the photopolymerization or photocrosslinking group are polymerizable. The compound reacts to form a polymer, and by the polymer, the tilt direction of the liquid crystal molecules is memorized, and the response speed of the obtained liquid crystal display element can be accelerated.

上述中，雖對於使於形成液晶配向膜之液晶配向劑中含有以下聚合性化合物所製作的液晶顯示元件做說明，其中該聚合性化合物為持有具有α-亞甲基-γ-丁內酯基的末 端與具有進行光聚合或光交聯之基的末端之聚合性化合物，本發明的液晶顯示元件亦可為使液晶中含有以下聚合性化合物而製造者，其中聚合性化合物為持有具有α-亞甲基-γ-丁內酯基之末端與具有進行光聚合或光交聯之基的末端之聚合性化合物。 In the above, the liquid crystal display element produced by including the following polymerizable compound in the liquid crystal alignment agent for forming a liquid crystal alignment film in which the polymerizable compound is held has α-methylene-γ-butyrolactone is described. End of the base In the liquid crystal display device of the present invention, the liquid crystal display device of the present invention may be produced by including the following polymerizable compound in a liquid crystal, wherein the polymerizable compound is held with α- The terminal of the methylene-γ-butyrolactone group and the polymerizable compound having a terminal group for photopolymerization or photocrosslinking.

又，上述液晶配向劑不僅可作為製造PSA型液晶顯示器或SC-PVA型液晶顯示器等垂直配向方式等液晶顯示元件時的液晶配向劑為有用，亦適用於藉由摩擦處理或光配向處理所製作之液晶配向膜的用途上。 Further, the liquid crystal alignment agent is useful not only as a liquid crystal alignment agent for producing a liquid crystal display element such as a vertical alignment method such as a PSA liquid crystal display or an SC-PVA liquid crystal display, but also for use in rubbing treatment or photoalignment processing. The use of the liquid crystal alignment film.

[實施例] [Examples]

以下舉出實施例及比較例，更詳細說明本發明，但本發明內容並未限定於此等實施例。 Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. However, the present invention is not limited thereto.

實施例所使用之簡稱如以下所示。 The abbreviations used in the examples are as follows.

(四羧酸二酐) (tetracarboxylic dianhydride)

BODA：雙環[3,3,0]辛烷-2,4,6,8-四羧酸二酐CBDA：1,2,3,4-環丁烷四羧酸二酐 BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

TCA：下述式所示2,3,5-三羧基環戊基乙酸-1,4：2,3-二酐 TCA: 2,3,5-tricarboxycyclopentyl acetic acid-1,4:2,3-dianhydride shown by the following formula

(二胺) (diamine)

m-PDA：m-伸苯基二胺 m-PDA: m-phenylene diamine

p-PDA：p-伸苯基二胺 p-PDA: p-phenylenediamine

PCH：1,3-二胺基-4-[4-(4-庚基環己基)苯氧基]苯 PCH: 1,3-diamino-4-[4-(4-heptylcyclohexyl)phenoxy]benzene

DBA：3,5-二胺基安息香酸 DBA: 3,5-diamino benzoic acid

3AMPDA：3,5-二胺基-N-(吡啶-3-基甲基)-苯甲醯胺 3AMPDA: 3,5-Diamino-N-(pyridin-3-ylmethyl)-benzamide

DA-1：下述式所示2-(甲基丙烯醯氧基)乙基3,5-二胺基苯甲酸酯 DA-1: 2-(methacryloxy)ethyl 3,5-diaminobenzoate represented by the following formula

DA-2：下述式所示N1,N1-二稀丙基苯-1,2,4-三胺 DA-2: N 1 ,N 1 -dipropyl phenyl-1,2,4-triamine represented by the following formula

DA-3：下述式所示3,5-二胺基安息香酸膽巢烷酯DA-3: 3,5-diamino benzoic acid cholestyl ester shown by the following formula

[化59][化59]

(胺化合物)(amine compound)

3-AMP：3-胺基甲基吡啶3-AMP: 3-aminomethylpyridine

(有機溶劑)(Organic solvents)

NMP：N-甲基-2-吡咯烷酮NMP: N-methyl-2-pyrrolidone

BCS：乙二醇二丁醚BCS: ethylene glycol dibutyl ether

<聚合性化合物><Polymerizable compound>

(聚合性化合物(RM1)之合成)(Synthesis of polymerizable compound (RM1))

於附有冷卻管之300ml茄形燒瓶中加入4、4’-雙酚6.7g(35.9mmol)、2-(4-溴丁基)-1,3-二噁戊烷15.0g(71.7mmol)、碳酸鉀19.8g(143mmol)、及丙酮150ml作為混合物，在60℃一邊進行48小時攪拌一邊使其進行反應。反應終了後，在減壓下將溶劑餾去，得到黃色濕潤固體。其後該固體與水200ml混合，加入氯仿80ml並萃取。萃取進行3次。4,4'-bisphenol 6.7 g (35.9 mmol) and 2-(4-bromobutyl)-1,3-dioxolane 15.0 g (71.7 mmol) were placed in a 300 ml eggplant-shaped flask with a cooling tube. Further, 19.8 g (143 mmol) of potassium carbonate and 150 ml of acetone were used as a mixture, and the mixture was stirred at 60 ° C for 48 hours to carry out a reaction. After the completion of the reaction, the solvent was distilled off under reduced pressure to give a yellow, dry solid. Thereafter, the solid was mixed with 200 ml of water, and 80 ml of chloroform was added thereto and extracted. The extraction was carried out 3 times.

於經分液的有機層加入無水硫酸鎂並乾燥，過濾後在減壓下使溶劑餾去，得到黃色固體。將該固體以再結晶(己烷/氯仿=4/1(體積比))進行純化後得到白色固體14.6g。將所得之白色固體以NMR進行測定之結果如以下所示。且所得之固體溶解於氘-氯仿(CDCl3)，使用核磁共振裝置(Diol公司製)以300MHz進行測定。由該結果確認，該白色固體為下述反應式所示化合物(RM1-A)。產率為92%。Anhydrous magnesium sulfate was added to the organic layer which was separated and dried, filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was purified by recrystallization (hexane / chloroform = 4 / 1 (volume ratio)) to yield 14.6 g of white solid. The results of measurement of the obtained white solid by NMR are shown below. The obtained solid was dissolved in cesium-chloroform (CDCl 3 ), and measured at 300 MHz using a nuclear magnetic resonance apparatus (manufactured by Diol Co., Ltd.). From the results, it was confirmed that the white solid was a compound (RM1-A) represented by the following reaction formula. The yield was 92%.

1H-NMR(CDCl3)δ：1.65(m,4H),1.74(m,4H),1.87(m,4H),3.86(m,4H),3.97(m,8H),4.89(t,2H),6.92(m,4H),7.44(m,4H)。 1 H-NMR (CDCl 3 ) δ: 1.65 (m, 4H), 1.74 (m, 4H), 1.87 (m, 4H), 3.86 (m, 4H), 3.97 (m, 8H), 4.89 (t, 2H) ), 6.92 (m, 4H), 7.44 (m, 4H).

[化60][60]

其次，於附有冷卻管之500ml茄形燒瓶中加入上述所得之化合物(RM1-A)13.3g(30mmol)、2-(溴甲基)丙烯酸11.6g(70mmol)、10%鹽酸(aq)50ml、四氫呋喃(THF)160ml、氯化錫(II)13.2g(70mmol)作為混合物，在70℃進行20小時攪拌使其反應。反應終了後，將反應液經減壓過濾後與純水200ml混合，於此加入二氯仿100ml並萃取。萃取進行3次。Next, the above-obtained compound (RM1-A) 13.3 g (30 mmol), 2-(bromomethyl)acrylic acid 11.6 g (70 mmol), 10% hydrochloric acid (aq) 50 ml were placed in a 500 ml eggplant-shaped flask equipped with a cooling tube. 160 ml of tetrahydrofuran (THF) and 13.2 g (70 mmol) of tin (II) chloride were mixed as a mixture at 70 ° C for 20 hours. After the completion of the reaction, the reaction mixture was filtered under reduced pressure and mixed with 200 ml of purified water, and then 100 ml of dichloroform was added and extracted. The extraction was carried out 3 times.

於經分液的有機層加入無水硫酸鎂並乾燥，由減壓過濾後的溶液將溶劑餾去後得到白色固體。將該固體以再結晶(己烷/氯仿=2/1)進行純化後，得到白色固體9.4g。將所得之白色固體與上述同樣地以NMR進行測定結果，確認該白色固體為目的之下述反應式所示聚合性化合物(RM1)。產率為64%。Anhydrous magnesium sulfate was added to the organic layer to be separated and dried, and the solvent was filtered off under reduced pressure to give a white solid. The solid was purified by recrystallization (hexane / chloroform = 2 / 1) to yield 9.4 g of white solid. The obtained white solid was measured by NMR in the same manner as above, and the polymerizable compound (RM1) represented by the following reaction formula for the purpose of the white solid was confirmed. The yield was 64%.

1H-NMR(CDCl3)δ：1.69(m,12H),2.61(m,2H),3.09(m,2H),4.00(t,4H),4.57(m,2H),5.64(m,2H),6.24(m,2H),6.92(d,4H),7.45(m,4H)。 1 H-NMR (CDCl 3 ) δ: 1.69 (m, 12H), 2.61 (m, 2H), 3.09 (m, 2H), 4.40 (t, 4H), 4.57 (m, 2H), 5.64 (m, 2H) ), 6.24 (m, 2H), 6.92 (d, 4H), 7.45 (m, 4H).

[化61][化61]

(聚合性化合物(RM2)之合成)(Synthesis of Polymerizable Compound (RM2))

於附有冷卻管之300ml茄形燒瓶中加入4,4’-聯苯基二羧基醛5.0g(23.8mmol)、2-(溴甲基)丙烯酸7.9g(47.6mmol)、10%鹽酸(aq)33ml、四氫呋喃(THF)100ml、氯化錫(II)9.5g(50mmol)作為混合物，在70℃進行20小時攪拌使其反應。反應終了後，將反應液注入於純水300ml，得到白色固體。分離所得之固體，以再結晶(己烷/氯仿=2/1)進行純化後，得到白色固體3.5g。該固體以NMR進行測定結果，確認該白色固體為目的之下述反應式所示聚合性化合物(RM2)。產率為72%。Add 4,4'-biphenyldicarboxyaldehyde 5.0g (23.8mmol), 2-(bromomethyl)acrylic acid 7.9g (47.6mmol), 10% hydrochloric acid (aq) to a 300ml eggplant-shaped flask with a cooling tube. 33 ml, 100 ml of tetrahydrofuran (THF), and 9.5 g (50 mmol) of tin (II) chloride were used as a mixture, and the mixture was stirred at 70 ° C for 20 hours to cause a reaction. After the completion of the reaction, the reaction solution was poured into 300 ml of pure water to obtain a white solid. The obtained solid was separated and purified by recrystallization (hexane / chloroform = 2 / 1) to afford 3.5 g of white solid. The solid was measured by NMR, and it was confirmed that the white solid was the polymerizable compound (RM2) represented by the following reaction formula. The yield was 72%.

1H-NMR(CDCl3)δ：2.99(m,2H),3.42(m,2H),5.60(m,2H),5.74(m,2H),6.36(m,2H),7.42(m,4H),7.60(m,4H)。 1 H-NMR (CDCl 3 ) δ: 2.99 (m, 2H), 3.42 (m, 2H), 5.60 (m, 2H), 5.74 (m, 2H), 6.36 (m, 2H), 7.42 (m, 4H) ), 7.60 (m, 4H).

[化62][化62]

(聚合性化合物(RM3)之合成)(Synthesis of Polymerizable Compound (RM3))

於附有冷卻管之500ml茄形燒瓶中加入4、4’-雙酚11.2g(60mmol)、2-(2-溴乙基)-1,3-二噁戊烷25.0g(138mmol)、碳酸鉀35.9g(260mmol)、及丙酮200ml作為混合物，在60℃一邊進行48小時攪拌一邊使其進行反應。反應終了後，在減壓下將溶劑餾去，得到黃色濕潤固體。其後該固體與水200ml混合，加入氯仿100ml並萃取。萃取進行3次。4,4'-bisphenol 11.2g (60mmol), 2-(2-bromoethyl)-1,3-dioxolane 25.0g (138mmol), carbonic acid were added to a 500ml eggplant-shaped flask with a cooling tube. 35.9 g (260 mmol) of potassium and 200 ml of acetone were used as a mixture, and the reaction was carried out while stirring at 60 ° C for 48 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure to give a yellow, dry solid. Thereafter, the solid was mixed with 200 ml of water, and 100 ml of chloroform was added thereto and extracted. The extraction was carried out 3 times.

經分液的有機層，加入無水硫酸鎂使其乾燥，過濾後在減壓下使溶劑餾去，得到黃色固體。將該固體溶解於氯仿，使用己烷以(己烷/氯仿=2/1)沈澱後，得到白色固體17.6g。將該固體以NMR進行測定之結果如以下所示。由結果確認該白色固體為下述反應式所示化合物(RM3-A)。產率為76%。The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. This solid was dissolved in chloroform, and precipitated with hexane (hexane/chloroform = 2/1) to afford 17.6 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a compound (RM3-A) represented by the following reaction formula. The yield was 76%.

1H-NMR(CDCl3)δ：2.19(m,4H),3.89(m,4H),4.01(m,4H),4.16(m,4H),5.11(m,2H),6.95(m,4H),7.45(m,4H)。 1 H-NMR (CDCl 3 ) δ: 2.19 (m, 4H), 3.89 (m, 4H), 4.01 (m, 4H), 4.16 (m, 4H), 5.11 (m, 2H), 6.95 (m, 4H) ), 7.45 (m, 4H).

[化63][化63]

其次，於附有冷卻管之500ml茄形燒瓶中加入上述所得之化合物(RM3-A)10.0g(26mmol)、2-(溴甲基)丙烯酸10.0g(60.6mmol)、10%HCl(aq)32ml、四氫呋喃(THF)140ml、氯化錫(II)11.4g(60.6mmol)、作為混合物，在70℃進行20小時攪拌使其反應。反應終了後，將反應液經減壓過濾後與純水200ml混合，於此加入氯仿100ml並萃取。萃取進行3次。Next, 10.0 g (26 mmol) of the above-obtained compound (RM3-A), 10.0 g (60.6 mmol) of 2-(bromomethyl)acrylic acid, and 10% HCl (aq) were added to a 500 ml eggplant-shaped flask equipped with a cooling tube. 32 ml, 140 ml of tetrahydrofuran (THF), and 11.4 g (60.6 mmol) of tin (II) chloride were mixed as a mixture at 70 ° C for 20 hours to cause a reaction. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and then mixed with 200 ml of purified water, and then 100 ml of chloroform was added and extracted. The extraction was carried out 3 times.

於萃取後的有機層中加入無水硫酸鎂使其乾燥，由減壓過濾後的溶液將溶劑餾去後得到白色固體。將該固體溶解於氯仿，使用己烷以(己烷/氯仿=2/1)沈澱後得到白色固體。將該固體以甲醇洗淨後，得到白色固體4.7g。將該固體以NMR進行測定之結果如以下所示。由該結果確認該白色固體為目的之下述反應式所示聚合性化合物(RM3)。產率42%。Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was filtered off under reduced pressure to give a white solid. This solid was dissolved in chloroform and precipitated with hexane (hexane/chloroform = 2/1) to give a white solid. The solid was washed with methanol to give 4.7 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a polymerizable compound (RM3) represented by the following reaction formula. The yield was 42%.

1H-NMR(CDCl3)δ：2.18(m,4H),2.76(m,2H),3.16(m,2H),4.18(m,4H),4.84(m,2H),5.67(m,2H),6.27(m,2H),6.95(d,4H),7.46(m,4H)。 1 H-NMR (CDCl 3 ) δ: 2.18 (m, 4H), 2.76 (m, 2H), 3.16 (m, 2H), 4.18 (m, 4H), 4.84 (m, 2H), 5.67 (m, 2H) ), 6.27 (m, 2H), 6.95 (d, 4H), 7.46 (m, 4H).

[化64][化64]

(聚合性化合物(RM4))(Polymerizable compound (RM4))

將公知下述式所示聚合性化合物作為聚合性化合物(RM4)。A polymerizable compound represented by the following formula is known as a polymerizable compound (RM4).

[化65][化65]

(聚合性化合物(RM5)之合成)(Synthesis of Polymerizable Compound (RM5))

於附有冷卻管之200ml茄形燒瓶中加入4-羥基安息香酸甲基7.61g(50.0mmol)、6-溴-1-己醇9.1g(50.0mmol)、碳酸鉀13.8g(100mmol)、及丙酮70ml作為混合物，在64℃一邊進行24小時攪拌一邊使其反應。反應終了後，將反應液經減壓過濾，在減壓下餾去溶劑，得到黃色濕潤固體。將該固體藉由矽膠管柱層析法(管柱：矽膠60,0.063-0.200mm,Merck製，溶離液：己烷/乙酸乙酯=1/1(v/v))進行純化。由所得之溶液餾去溶劑，得到白色固體11.3g。將該固體的NMR測定結果如以下所示。由結果確認該白色固體為下述反應式所示化合物(RM5-A)。產率為90%。To a 200 ml eggplant-shaped flask equipped with a cooling tube, 7.61 g (50.0 mmol) of 4-hydroxybenzoic acid methyl group, 9.1 g (50.0 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate, and 70 ml of acetone was used as a mixture, and the mixture was reacted while stirring at 64 ° C for 24 hours. After the completion of the reaction, the reaction mixture was filtered under reduced pressure. The solid was purified by ruthenium column chromatography (column: oxime 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate = 1/1 (v/v)). The solvent was evaporated to give a white solid (11.3 g). The NMR measurement results of this solid are shown below. From the results, it was confirmed that the white solid was a compound (RM5-A) represented by the following reaction formula. The yield was 90%.

1H-NMR(CDCl3)δ：1.3-1.7(m,8H),3.67(m,2H),3.88(s,3H),4.03(t,2H),6.91(d,2H),7.99(d,2H)。 1 H-NMR (CDCl 3 ) δ: 1.3-1.7 (m, 8H), 3.67 (m, 2H), 3.88 (s, 3H), 4.03 (t, 2H), 6.91 (d, 2H), 7.99 (d) , 2H).

[化66][化66]

其次，於附冷卻管之100ml三口燒瓶中放入氯鉻酸吡啶鹽(PCC)2.2g(10.0mmol)、及CH2Cl215.0ml並在攪拌混合狀態下，滴入溶解上述所得之化合物(RM5-A)2.5g(10.0mmol)於CH2Cl215.0ml的溶液，在室溫再攪拌6小時。其後，於除去附著於燒瓶壁上的油狀物之溶液中，加入二乙基醚90ml並使其減壓過濾後，在減壓下將溶劑餾去，得到濃綠色之濕潤固體。將該固體藉由矽膠管柱層析法(管柱：矽膠60,0.063-0.200mm,Merck製，溶離液：己烷/乙酸乙酯=2/1(v/v))進行純化。餾去所得之溶液的溶劑，得到無色固體1.3g。將該固體以NMR進行測定之結果如以下所示。由該結果確認該無色固體為下述反應式所示化合物(RM5-B)。產率為50%。Next, 2.2 g (10.0 mmol) of chlorochromate pyridinium salt (PCC) and 15.0 ml of CH 2 Cl 2 were placed in a 100 ml three-necked flask equipped with a cooling tube, and the compound obtained above was dissolved in a stirred state. RM5-a) 2.5g (10.0mmol) to a solution of 2 Cl 2 15.0ml CH, stirred for additional 6 hours at room temperature. Thereafter, 90 ml of diethyl ether was added to the solution of the oily substance adhering to the wall of the flask, and the mixture was filtered under reduced pressure, and the solvent was evaporated under reduced pressure to give a concentrated green solid. The solid was purified by ruthenium column chromatography (column: oxime 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane/ethyl acetate = 2/1 (v/v)). The solvent of the obtained solution was evaporated to give 1.3 g of a colorless solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the colorless solid was a compound (RM5-B) represented by the following reaction formula. The yield was 50%.

1H-NMR(CDCl3)δ：1.3-1.8(m,6H),2.49(t,2H),3.88(s,3H),3.99(t,2H),6.87(d,2H),7.99(d,2H),9.78(s,1H)。 1 H-NMR (CDCl 3 ) δ: 1.3-1.8 (m, 6H), 2.49 (t, 2H), 3.88 (s, 3H), 3.99 (t, 2H), 6.87 (d, 2H), 7.99 (d) , 2H), 9.78 (s, 1H).

[化67][67]

其次於附有冷卻管之50ml茄形燒瓶中加入上述所得之化合物(RM5-B)1.25g(5.0mmol)、2-(溴甲基)丙烯酸0.83g(5.0mmol)、Amberlyst(註冊商標)15(Rohm and Haas Company商品名)0.8g、THF8.0ml、氯化錫(II)0.95g(5.0mmol)、及純水2.0ml作為混合物，在70℃進行5小時攪拌並使其反應。反應終了後，將反應液經減壓過濾後與純水40ml混合，於此加入二乙基醚50ml並進行萃取。萃取進行3次。Next, 1.25 g (5.0 mmol) of the compound (RM5-B) obtained above, 0.83 g (5.0 mmol) of 2-(bromomethyl)acrylic acid, and Amberlyst (registered trademark) 15 were added to a 50 ml eggplant-shaped flask equipped with a cooling tube. (Rohm and Haas Company trade name) 0.8 g, THF 8.0 ml, tin (II) chloride 0.95 g (5.0 mmol), and pure water 2.0 ml were used as a mixture, and the mixture was stirred at 70 ° C for 5 hours to cause a reaction. After the completion of the reaction, the reaction solution was filtered under reduced pressure, and then mixed with 40 ml of purified water, and 50 ml of diethyl ether was added thereto and extracted. The extraction was carried out 3 times.

於萃取後的有機層中加入無水硫酸鎂使其乾燥，由減壓過濾後的溶液餾去溶劑，得到無色固體1.5g。將該固體的NMR測定結果如以下所示。由該結果確認，該無色固體為下述反應式所示化合物(RM5-C)。產率為94%。Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was evaporated under reduced pressure to give 1.5 g of a colorless solid. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the colorless solid was a compound (RM5-C) represented by the following reaction formula. The yield was 94%.

1H-NMR(DMSO-d6)δ：1.3-1.8(m,8H),2.62(m,1H),3.04(s,1H),3.81(s,3H),4.05(t,2H),4.54(m,1H),5.70(s,1H),6.01(s,1H),7.03(d,2H),7.89(d,2H)。 1 H-NMR (DMSO-d6) δ: 1.3-1.8 (m, 8H), 2.62 (m, 1H), 3.04 (s, 1H), 3.81 (s, 3H), 4.05 (t, 2H), 4.54 ( m, 1H), 5.70 (s, 1H), 6.01 (s, 1H), 7.03 (d, 2H), 7.89 (d, 2H).

[化68][化68]

於附有冷卻管之100ml茄形燒瓶中加入乙醇35ml、上述所得之化合物(RM5-C)1.5g(4.7mmol)、及10%氫氧化水溶液5ml作為混合物，在85℃一邊進行3小時攪拌一邊使其反應。反應終了後，於500ml的燒杯中加入水300ml與反應液，30分鐘在室溫進行攪拌後，滴入10%HCl水溶液5ml後，過濾後得到白色固體1.3g。To a 100 ml eggplant-shaped flask equipped with a cooling tube, 35 ml of ethanol, 1.5 g (4.7 mmol) of the compound (RM5-C) obtained above, and 5 ml of a 10% aqueous hydrogen hydroxide solution were added as a mixture, and the mixture was stirred at 85 ° C for 3 hours. Make it react. After the completion of the reaction, 300 ml of water and a reaction liquid were added to a 500 ml beaker, and the mixture was stirred at room temperature for 30 minutes, and then 5 ml of a 10% aqueous HCl solution was added dropwise thereto, followed by filtration to obtain a white solid (1.3 g).

其次於附有冷卻管之50ml茄形燒瓶中加入所得之白色固體1.1g、Amberlyst(註冊商標)15(Rohm and Haas Company商品名)1.0g、及THF20.0ml作為混合物，在70℃進行5小時攪拌並使其反應。反應終了後，將反應液經減壓過濾後由溶液餾去溶劑，得到黃色固體。將該黃色固體經再結晶(己烷/乙酸乙酯=1/1(v/v))進行純化後，得到白色固體0.9g。將該固體的NMR測定結果如以下所示。由結果確認該白色固體為下述反應式所示化合物(RM5-D)。產率為71%。Next, 1.1 g of the obtained white solid, 1.0 g of Amberlyst (registered trademark) 15 (trade name of Rohm and Haas Company), and 20.0 ml of THF were added as a mixture to a 50 ml eggplant-shaped flask equipped with a cooling tube, and 5 hours at 70 ° C. Stir and react. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and then the solvent was evaporated. The yellow solid was purified by recrystallization (hexane / ethyl acetate = 1 / 1 (v / v)) The NMR measurement results of this solid are shown below. From the results, it was confirmed that the white solid was a compound (RM5-D) represented by the following reaction formula. The yield was 71%.

1H-NMR(DMSO-d6)δ：1.2-1.8(m,8H),2.60(m,1H),3.09(m,1H),4.04(m,2H),4.55(m,1H),5.69(s,1H),6.02(s,1H),6.99(d,2H),7.88(d,2H),12.5(s,broad,1H)。 1 H-NMR (DMSO-d6) δ: 1.2-1.8 (m, 8H), 2.60 (m, 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5.69 ( s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1H).

[化69][化69]

上述所得之化合物(RM5-D)21.1g(69.3mmol)、1,4-環己烷二甲醇5.0g(34.7mmol)、N,N-二甲基-4-胺基吡啶(DMAP)0.35g及少量2,6-二-第三丁基-p-甲酚(BHT)在室溫進行攪拌下，懸浮於二氯甲烷100ml，於此加入溶解於二氯甲烷50ml之二環己基碳二亞胺(DCC)15.5g(75.0mmol)，進行48小時攪拌使其反應。反應終了後，過濾分離經析出之DCC脲，將該濾液依順序，以各60ml的0.5N-HCl與飽和碳酸氫鈉水溶液與飽和食鹽水進行2次洗淨，以硫酸鎂乾燥後，餾去溶劑後以乙醇進行再結晶操作，得到下述反應式所示聚合性化合物(RM5)20.1g。以NMR進行測定之結果如以下所示。又，產率為81%。The above-obtained compound (RM5-D) 21.1 g (69.3 mmol), 1,4-cyclohexanedimethanol 5.0 g (34.7 mmol), N,N-dimethyl-4-aminopyridine (DMAP) 0.35 g And a small amount of 2,6-di-t-butyl-p-cresol (BHT) was stirred at room temperature, and suspended in 100 ml of dichloromethane, and dicyclohexylcarbodiene dissolved in 50 ml of dichloromethane was added thereto. An amine (DCC) of 15.5 g (75.0 mmol) was stirred for 48 hours to cause a reaction. After the completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 60 ml of 0.5 N-HCl and a saturated aqueous sodium hydrogencarbonate solution and brine, and dried over magnesium sulfate. After the solvent was recrystallized from ethanol, 20.1 g of a polymerizable compound (RM5) represented by the following reaction formula was obtained. The results of measurement by NMR are shown below. Also, the yield was 81%.

1H-NMR(CDCl3)δ：1.15(m,4H),1.50(m,8H),1.66(m,2H),1.79(m,8H),1.92(m,4H),2.60(m,2H),3.08(m,2H),4.01(m,4H),4.12(m,4H),4.53(m,2H),5.63(d,2H),6.24(d,2H),6.89(d,4H),7.97(d,4H)。 1 H-NMR (CDCl 3 ) δ: 1.15 (m, 4H), 1.50 (m, 8H), 1.66 (m, 2H), 1.79 (m, 8H), 1.92 (m, 4H), 2.60 (m, 2H) , 3.08 (m, 2H), 4.01 (m, 4H), 4.12 (m, 4H), 4.53 (m, 2H), 5.63 (d, 2H), 6.24 (d, 2H), 6.89 (d, 4H), 7.97 (d, 4H).

[化70][化70]

(聚合性化合物(RM6)之合成)(Synthesis of polymerizable compound (RM6))

將上述方法所得之化合物(RM5-D)6.1g(20.0mmol)、4-[(6-丙烯氧基)己基氧基]酚(SYNTHON Chemicals公司)5.3g(20.0mmol)、N,N-二甲基-4-胺基吡啶(DMAP)0.1g、及少量BHT在室溫進行攪拌下，懸浮於二氯甲烷100ml，於此加入溶解二環己基碳二亞胺(DCC)5.1g(25.0mmol)的溶液並進行一晚攪拌。將析出之DCC脲經過濾分離，將該濾液以0.5N-HCl 100ml、飽和碳酸氫鈉水溶液100ml、飽和食鹽水150ml之順序進行2次洗淨，以硫酸鎂乾燥後，在減壓下使溶劑餾去，得到黃色固體。將該固體藉由二氧化矽管柱層析(管柱：矽膠600.063-0.200mm莫克公司製之溶離液：己烷/乙酸乙酯=1/1)進行純化。餾去於此所得之溶液的溶劑，得到下述反應式所示聚合性化合物(RM6)4.3g。以NMR進行測定之結果如以下所示。又，產率為39%。The compound obtained by the above method (RM5-D) 6.1 g (20.0 mmol), 4-[(6-propenyloxy)hexyloxy]phenol (SYNTHON Chemicals) 5.3 g (20.0 mmol), N, N-di 0.1 g of methyl-4-aminopyridine (DMAP) and a small amount of BHT were stirred at room temperature, and suspended in 100 ml of dichloromethane, and dissolved in cyclohexylcarbodiimide (DCC) 5.1 g (25.0 mmol) was added thereto. The solution was stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 0.5 N of HCl, 100 ml of a saturated aqueous sodium hydrogencarbonate solution and 150 ml of a saturated aqueous sodium chloride solution, and dried over magnesium sulfate. It was distilled off to give a yellow solid. The solid was purified by column chromatography on silica gel column (column: colloidal solution of 600.063-0.200 mm Mocco: hexane/ethyl acetate = 1/1). The solvent of the solution obtained above was distilled off to obtain 4.3 g of a polymerizable compound (RM6) represented by the following reaction formula. The results of measurement by NMR are shown below. Also, the yield was 39%.

1H NMR(CDCl3)δ：1.53(m,10H),1.72(m,2H),1.79(m,4H),2.58(m,1H),3.07(m,1H),3.96(t,2H),4.05(t,2H),4.18(t,2H),4.54(m,1H),5.64(d,1H),5.81(d,1H),6.14(m,1H),6.24(d,1H),6.40(d,1H),6.97(m,4H),7.09(d,2H),8.14(d,2H)。1H NMR (CDCl3) δ: 1.53 (m, 10H), 1.72 (m, 2H), 1.79 (m, 4H), 2.58 (m, 1H), 3.07 (m, 1H), 3.96 (t, 2H), 4.05 (t, 2H), 4.18 (t, 2H), 4.54 (m, 1H), 5.64 (d, 1H), 5.81 (d, 1H), 6.14 (m, 1H), 6.24 (d, 1H), 6.40 ( d, 1H), 6.97 (m, 4H), 7.09 (d, 2H), 8.14 (d, 2H).

[化71][71]

(聚合性化合物(RM7)之合成)(Synthesis of Polymeric Compound (RM7))

將下述反應式所示化合物(RM7-A)2.1g(7.3mmol)、化合物(RM7-B)2.5g(7.3mmol)、DMAP 0.015g及少量BHT在室溫進行攪拌下，懸浮於二氯甲烷30ml，於此加入溶解於二氯甲烷5ml之DCC 1.8g(9.0mmol)並進行一晚攪拌後，過濾分離經析出之DCC脲，將該濾液依順序以各50ml的0.5N-HCl與飽和碳酸氫鈉水溶液與飽和食鹽水進行2次洗淨，以硫酸鎂乾燥後，餾去溶劑後以乙醇進行再結晶操作，得到下述反應式所示聚合性化合物(RM7)1.3g。以NMR進行測定之結果如以下所示。又，產率為30%。2.1 g (7.3 mmol) of the compound of the following reaction formula (RM7-A), 2.5 g (7.3 mmol) of the compound (RM7-B), 0.015 g of DMAP and a small amount of BHT were stirred at room temperature, and suspended in dichloro 30 ml of methane was added thereto, and 1.8 g (9.0 mmol) of DCC dissolved in 5 ml of dichloromethane was added thereto, and after stirring overnight, the precipitated DCC urea was separated by filtration, and the filtrate was sequentially saturated with 50 ml of 0.5 N-HCl. The sodium hydrogencarbonate aqueous solution and the saturated aqueous sodium chloride solution were washed twice, dried over magnesium sulfate, and the solvent was distilled off, followed by recrystallization from ethanol to obtain 1.3 g of a polymerizable compound (RM7) represented by the following reaction formula. The results of measurement by NMR are shown below. Also, the yield was 30%.

1H NMR(CDCl3))：δ1.40-1.90(m,14H),2.64(m,1H),3.07(m,1H),4.00(t,2H),4.05(t,2H),4.18(t,2H),4.54(m,1H),5.83(d,1H),6.14(m,1H),6.25(d,1H),6.37(d,1H),6.97(d,2H),7.26(d,2H),7.50(d,2H),7.57(d,2H),8.17(d,2H)。 1 H NMR (CDCl 3 )): δ 1.40-1.90 (m, 14H), 2.64 (m, 1H), 3.07 (m, 1H), 4.00 (t, 2H), 4.05 (t, 2H), 4.18 ( t, 2H), 4.54 (m, 1H), 5.83 (d, 1H), 6.14 (m, 1H), 6.25 (d, 1H), 6.37 (d, 1H), 6.97 (d, 2H), 7.26 (d) , 2H), 7.50 (d, 2H), 7.57 (d, 2H), 8.17 (d, 2H).

[化72][化72]

(聚合性化合物(RM8)之合成)(Synthesis of polymerizable compound (RM8))

於附有冷卻管之100ml茄形燒瓶中加入4-羥基苯甲醛6.1g(50mmol)、6-溴-1-己醇9.1g(50mmol)、碳酸鉀13.8g(100mmol)、及丙酮100ml作為混合物，在64℃一邊進行24小時攪拌一邊使其反應。反應終了後，在減壓下將溶劑餾去後得到黃色濕潤固體。其後混合該固體與水70ml，加入二乙基醚50ml並萃取。萃取進行3次。To a 100 ml eggplant-shaped flask equipped with a cooling tube, 6.1 g (50 mmol) of 4-hydroxybenzaldehyde, 9.1 g (50 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate, and 100 ml of acetone were added as a mixture. The reaction was carried out while stirring at 64 ° C for 24 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure to give a yellow, wet solid. Thereafter, 70 ml of the solid and water were mixed, and 50 ml of diethyl ether was added and extracted. The extraction was carried out 3 times.

經分液的有機層，加入無水硫酸鎂使其乾燥，過濾後在減壓下使溶劑餾去，得到黃色固體。將該固體溶解於乙酸乙酯5ml，以管柱層析(管柱：矽膠600.063-0.200mm Merck製之溶離液：己烷/乙酸乙酯=2/1)進行純化。於此由所得之溶液餾去溶劑，得到白色固體7.4g。將該固體以NMR進行測定之結果如以下所示。由結果確認該白色固體為下述反應式所示化合物(RM8-A)。產率為67%。The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was dissolved in 5 ml of ethyl acetate, and purified by column chromatography (column: hexane: 600.063-0.200 mm Merck, hexane/ethyl acetate = 2/1). The solvent was distilled off from the obtained solution to obtain 7.4 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a compound (RM8-A) represented by the following reaction formula. The yield was 67%.

1H NMR(DMSO-d6)δ：1.55(m,4H),1.62(m,2H),1.84(m,2H),3.67(t,2H),4.05(t,2H),4.20(t,2H),7.00(d,2H),7.84(d,2H),9.88(s,1H)。1H NMR (DMSO-d6) δ: 1.55 (m, 4H), 1.62 (m, 2H), 1.84 (m, 2H), 3.67 (t, 2H), 4.05 (t, 2H), 4.20 (t, 2H) , 7.00 (d, 2H), 7.84 (d, 2H), 9.88 (s, 1H).

[化73][化73]

於50ml三口燒瓶混合化合物(RM8-A)2.2g、三乙胺1.7ml、BHT0.2mg及THF10ml並溶解。該溶液之攪拌下，將丙烯酸氯化物(acryloyl chloride)0.8ml溶解於THF10ml的溶液經15分鐘滴入。此時，將三口燒瓶以水浴(水溫20℃)冷卻。滴入後，在該狀態下直接進行30分鐘攪拌後，將燒瓶由水浴取出，由氮氣取代並在室溫下再進行3小時攪拌使其反應。過濾該反應液，將濾液減壓濃縮至3/4的容量後加入二氯甲烷100ml。將該溶液以飽和碳酸鈉溶液100ml、0.5N之鹽酸100ml、飽和食鹽水100ml的順序進行洗淨，以硫酸鎂乾燥後，餾去溶劑後得到黃色固體。將該固體溶解於乙酸乙酯3ml，以管柱層析(管柱：矽膠600.063-0.200mm Merck製之溶離液：己烷/乙酸乙酯=2/1)進行純化。於此由所得之溶液餾去溶劑，得到白色固體2.0g。將該固體以NMR進行測定之結果如以下所示。由結果確認該白色固體為下述反應式所示化合物(RM8-B)。產率為72%。In a 50 ml three-necked flask, 2.2 g of a compound (RM8-A), 1.7 ml of triethylamine, 0.2 mg of BHT and 10 ml of THF were mixed and dissolved. Under stirring of the solution, a solution of 0.8 ml of acryloyl chloride dissolved in 10 ml of THF was added dropwise over 15 minutes. At this time, the three-necked flask was cooled in a water bath (water temperature: 20 ° C). After the dropwise addition, the mixture was directly stirred for 30 minutes in this state, and the flask was taken out from a water bath, replaced with nitrogen, and stirred at room temperature for further 3 hours to cause a reaction. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure to a volume of 3/4. This solution was washed with 100 ml of a saturated sodium carbonate solution, 100 ml of 0.5 N hydrochloric acid, and 100 ml of a saturated aqueous sodium chloride solution, and dried over magnesium sulfate, and the solvent was evaporated to give a yellow solid. The solid was dissolved in 3 ml of ethyl acetate, and purified by column chromatography (column: hexane: 600.063-0.200mm Merck, hexane/ethyl acetate = 2/1). The solvent was distilled off from the obtained solution to obtain 2.0 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a compound (RM8-B) represented by the following reaction formula. The yield was 72%.

1H NMR(CDCl3)δ：1.48(m,4H),1.75(m,2H),1.85(m,2H),4.05(t,2H),4.18(t,2H),5.81(d,1H),6.14(m,1H),6.37(d,1H),6.99(m,2H),7.82(m,2H),9.88(s,1H)。1H NMR (CDCl3) δ: 1.48 (m, 4H), 1.75 (m, 2H), 1.85 (m, 2H), 4.05 (t, 2H), 4.18 (t, 2H), 5.81 (d, 1H), 6.14 (m, 1H), 6.37 (d, 1H), 6.99 (m, 2H), 7.82 (m, 2H), 9.88 (s, 1H).

[化74][化74]

其次於附有冷卻管之50ml的茄形燒瓶中，加入與上述同樣下得到之中間體化合物(RM8-B)2.0g(7mmol)、2-(溴甲基)丙烯酸1.2g(7.0mmol)、Amberlyst(註冊商標)15(Rohm and Haas商品名)1.2g、THF8.0ml、氯化錫(II)1.4g(7mmol)、純水2.0ml作為混合物，在溫度70℃進行24小時攪拌並使其反應。反應終了後，將反應液經減壓過濾後與純水60ml混合，於此加入二乙基醚50ml並進行萃取。萃取進行3次。於萃取後的有機層中加入無水硫酸鎂使其乾燥，由經減壓過濾後的溶液餾去溶劑後得到淡褐色之固體。Next, in an eggplant-shaped flask containing 50 ml of a cooling tube, 2.0 g (7 mmol) of the intermediate compound (RM8-B) obtained in the same manner as above, and 1.2 g (7.0 mmol) of 2-(bromomethyl)acrylic acid were added. 1.2 g of Amberlyst (registered trademark) 15 (Rohm and Haas trade name), 8.0 ml of THF, 1.4 g (7 mmol) of tin (II) chloride, and 2.0 ml of pure water were mixed as a mixture at a temperature of 70 ° C for 24 hours. reaction. After the completion of the reaction, the reaction solution was filtered under reduced pressure, and then mixed with 60 ml of purified water, and 50 ml of diethyl ether was added thereto and extracted. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was evaporated under reduced pressure to give a pale brown solid.

將該固體溶解於乙酸乙酯3ml，以矽膠管柱層析(管柱：矽膠600.063-0.200mm Merck製之溶離液：己烷/乙酸乙酯=2/1)進行純化。由於此所得之溶液餾去溶劑，得到白色固體1.0g。該固體以NMR進行測定結果，確認該白色固體為下述反應式所示聚合性化合物(RM8)。產率為40%。The solid was dissolved in 3 ml of ethyl acetate, and purified by silica gel column chromatography (column: silica gel, 600.063-0.200 mm Merck, hexane/ethyl acetate = 2/1). The solvent thus obtained was distilled off to give a white solid (1.0 g). The solid was measured by NMR, and it was confirmed that the white solid was a polymerizable compound (RM8) represented by the following reaction formula. The yield was 40%.

1H NMR(CDCl3) δ：1.48(m,4H),1.75(m,4H),2.94(m,1H),3.39(m,1H),3.95(t,2H),4.17(t,2H),5.45(t,1H),5.68(m,1H),5.83(m,1H),6.13(m,1H),6.30(m,1H),6.40(d,1H),6.88(d,2H),7.26(m,2H)。1H NMR (CDCl3) δ: 1.48 (m, 4H), 1.75 (m, 4H), 2.94 (m, 1H), 3.39 (m, 1H), 3.95 (t, 2H), 4.17 (t, 2H), 5.45 (t, 1H), 5.68 (m, 1H), 5.83 (m, 1H), 6.13 (m, 1H), 6.30 (m, 1H), 6.40 (d, 1H), 6.88 (d, 2H), 7.26 ( m, 2H).

[化75][化75]

(聚合性化合物(RM9)之合成)(Synthesis of Polymeric Compound (RM9))

與上述同樣方法所得之化合物(RM5-D)22.0g(72.4mmol)、1,4-苯基二甲醇5.0g(36.2mmo1)、N,N-二甲基-4-胺基吡啶(DMAP)0.35g及少量BHT在室溫進行攪拌下，懸浮於二氯甲烷100ml，於此加入溶解於二氯甲烷50ml之二環己基碳二亞胺(DCC)17.0g(80.0mmol)並進行48小時攪拌使其反應。反應終了後，過濾分離經析出之DCC脲，將該濾液依順序，以各60ml的0.5N-HCl與飽和碳酸氫鈉水溶液與飽和食鹽水進行2次洗淨，以硫酸鎂乾燥後，餾去溶劑後以乙醇進行再結晶操作，得到下述反應式所示聚合性化合物(RM9)16.6g。以NMR進行測定之結果如以下所示。又，產率為65%。Compound (RM5-D) obtained in the same manner as above, 22.0 g (72.4 mmol), 1,4-phenyldimethanol 5.0 g (36.2 mmol), N,N-dimethyl-4-aminopyridine (DMAP) 0.35 g and a small amount of BHT were suspended in 100 ml of dichloromethane under stirring at room temperature, and 17.0 g (80.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 50 ml of dichloromethane was added thereto and stirred for 48 hours. Make it react. After the completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 60 ml of 0.5 N-HCl and a saturated aqueous sodium hydrogencarbonate solution and brine, and dried over magnesium sulfate. After the solvent was recrystallized from ethanol, 16.6 g of a polymerizable compound (RM9) represented by the following reaction formula was obtained. The results of measurement by NMR are shown below. Also, the yield was 65%.

1H-NMR(CDCl3) δ：1.46(m,12H),1.80(m,4H),2.60(m,2H),3.08(m,2H),4.01(m,4H),4.56(m,2H),5.34(s,4H),5.63(d,2H),6.23(d,2H),6.90(d,4H),7.46(s,4H),8.00(d,4H)。 1 H-NMR (CDCl 3 ) δ: 1.46 (m, 12H), 1.80 (m, 4H), 2.60 (m, 2H), 3.08 (m, 2H), 4.01 (m, 4H), 4.56 (m, 2H) , 5.34 (s, 4H), 5.63 (d, 2H), 6.23 (d, 2H), 6.90 (d, 4H), 7.46 (s, 4H), 8.00 (d, 4H).

[化76][化76]

(聚合性化合物(RM10)之合成)(Synthesis of Polymerizable Compound (RM10))

將與上述同樣方法所得之化合物(RM5-D)6.1g(20.0mmol)、4,4’-聯苯基二甲醇2.1g(10.0mmol)、N,N-二甲基-4-胺基吡啶(DMAP)0.15g及少量BHT在室溫進行攪拌下，懸浮於二氯甲烷50ml，於此加入溶解於二氯甲烷25ml的二環己基碳二亞胺(DCC)5.3g(25.0mmol)並進行48小時攪拌使其反應。反應終了後，過濾分離經析出之DCC脲，將該濾液依順序，以各60ml的0.5N-HCl與飽和碳酸氫鈉水溶液與飽和食鹽水進行2次洗淨，以硫酸鎂乾燥後，餾去溶劑後以乙醇進行再結晶操作，得到下述反應式所示聚合性化合物(RM10)6.4g。以NMR進行測定之結果如以下所示。又，產率為81%。Compound (RM5-D) obtained in the same manner as above, 6.1 g (20.0 mmol), 4,4'-biphenyldimethanol 2.1 g (10.0 mmol), N,N-dimethyl-4-aminopyridine (DMAP) 0.15 g and a small amount of BHT were suspended in 50 ml of dichloromethane under stirring at room temperature, and 5.3 g (25.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 25 ml of dichloromethane was added thereto. The reaction was carried out by stirring for 48 hours. After the completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 60 ml of 0.5 N-HCl and a saturated aqueous sodium hydrogencarbonate solution and brine, and dried over magnesium sulfate. After the solvent was recrystallized from ethanol, 6.4 g of a polymerizable compound (RM10) represented by the following reaction formula was obtained. The results of measurement by NMR are shown below. Also, the yield was 81%.

1H-NMR(CDCl3) δ：1.48(m,12H),1.75(m,4H),2.60(m,2H),3.08(m,2H),4.01(m,4H),4.55(m,2H),5.38(s,4H),5.63(d,2H),6.23(d,2H),6.89(d,4H),7.51(d,4H),7.62(d,4H),8.05(d,4H)。 1 H-NMR (CDCl 3 ) δ: 1.48 (m, 12H), 1.75 (m, 4H), 2.60 (m, 2H), 3.08 (m, 2H), 4.01 (m, 4H), 4.55 (m, 2H) , 5.38 (s, 4H), 5.63 (d, 2H), 6.23 (d, 2H), 6.89 (d, 4H), 7.51 (d, 4H), 7.62 (d, 4H), 8.05 (d, 4H).

[化77][化77]

(聚合性化合物(RM11)之合成)(Synthesis of polymerizable compound (RM11))

將與上述同樣方法所得之化合物(RM5-D)6.1g(20.0mmol)、4,4’-二羥基二苯甲酮2.1g(10.0mmol)、N,N-二甲基-4-胺基吡啶(DMAP)0.1g、及少量BHT在室溫進行攪拌下，懸浮於二氯甲烷80ml，於加入溶解二環己基碳二亞胺(DCC)5.2g(24.0mmol)之溶液並進行一晚攪拌。將析出之DCC脲經過濾分離，將該濾液以0.5N-HCl 50ml、飽和碳酸氫鈉水溶液50ml、飽和食鹽水100ml之順序進行2次洗淨，以硫酸鎂乾燥後，在減壓下使溶劑餾去，得到黃色固體。將該固體使用乙醇進行再結晶而純化，得到白色固體6.2g。將該固體以NMR進行測定之結果如以下所示。由該結果確認，該白色固體為下述反應式所示聚合性化合物(RM11)。產率為79%。Compound (RM5-D) obtained in the same manner as above, 6.1 g (20.0 mmol), 4,4'-dihydroxybenzophenone 2.1 g (10.0 mmol), N,N-dimethyl-4-amino group 0.1 g of pyridine (DMAP) and a small amount of BHT were stirred at room temperature, and suspended in 80 ml of dichloromethane, and a solution of 5.2 g (24.0 mmol) of dissolved dicyclohexylcarbodiimide (DCC) was added thereto and stirred overnight. . The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 ml of 0.5 N-HCl, 50 ml of a saturated aqueous sodium hydrogen carbonate solution and 100 ml of a saturated aqueous sodium chloride solution, and dried over magnesium sulfate. It was distilled off to give a yellow solid. The solid was purified by recrystallization using ethanol to give 6.2 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a polymerizable compound (RM11) represented by the following reaction formula. The yield was 79%.

1H NMR(CDCl3) δ：1.45-1.95(m,16H),2.58(m,2H),3.07(m,2H),4.05(t,4H),4.54(m,2H),5.64(s,2H),6.24(s,2H),6.98(d,4H),7.32(d,4H),7.91(d,4H),8.18(d,4H)。1H NMR (CDCl3) δ: 1.45-1.95 (m, 16H), 2.58 (m, 2H), 3.07 (m, 2H), 4.05 (t, 4H), 4.54 (m, 2H), 5.64 (s, 2H) , 6.24 (s, 2H), 6.98 (d, 4H), 7.32 (d, 4H), 7.91 (d, 4H), 8.18 (d, 4H).

[化78][化78]

(聚合性化合物(RM12)之合成)(Synthesis of polymerizable compound (RM12))

於附有冷卻管之500ml的茄形燒瓶中加入4-羥基苯甲醛12.2g(100mmol)、1、6-二溴己烷12.2g(50mmol)、碳酸鉀16.0g(116mmol)、丙酮150ml作為混合物，在溫度64℃一邊進行48小時攪拌一邊使其反應。將反應溶液經過濾後在減壓下使溶劑餾去，得到淡褐色濕潤固體15.4g。將該固體以NMR進行測定之結果如以下所示。由該結果確認，該固體為下述反應式所示化合物(RM12-A)。產率為94%。To a 500 ml eggplant-shaped flask equipped with a cooling tube, 12.2 g (100 mmol) of 4-hydroxybenzaldehyde, 12.2 g (50 mmol) of 1,6-dibromohexane, 16.0 g (116 mmol) of potassium carbonate, and 150 ml of acetone were added as a mixture. The mixture was reacted while stirring at a temperature of 64 ° C for 48 hours. The reaction solution was filtered, and the solvent was evaporated under reduced pressure to yield 15.4 g of pale brown wet solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the solid was a compound (RM12-A) represented by the following reaction formula. The yield was 94%.

1H-NMR(CDCl3)δ：1.49(m,4H),1.77(m,4H),4.12(t,4H),7.10(d,2H),7.86(d,2H),9.87(s,2H)。 1 H-NMR (CDCl 3 ) δ: 1.49 (m, 4H), 1.77 (m, 4H), 4.12 (t, 4H), 7.10 (d, 2H), 7.86 (d, 2H), 9.87 (s, 2H) ).

[化79][化79]

其次，於附有冷卻管之100ml的茄形燒瓶中加入與上述同樣所得之化合物(RM12-A)3.3g(10.0mmol)、2-(溴甲基)丙烯酸3.3g(20.0mmol)、Amberlyst(註冊商標)15(Rohm and Haas商品名)3.0g、THF32.0ml、氯化錫(II)3.8g(20.0mmol)、純水8.0ml作為混合物，在溫度70℃進行24小時攪拌並使其反應。反應終了後，將反應液經減壓過濾後與純水60ml混合，於此加入二乙基醚70ml並萃取。萃取進行3次。於萃取後的有機層中加入無水硫酸鎂使其乾燥，由經減壓過濾後的溶液餾去溶劑後得到淡褐色之固體。Next, 3.3 g (10.0 mmol) of the compound (RM12-A) obtained in the same manner as above, 3.3 g (20.0 mmol) of 2-(bromomethyl)acrylic acid, and Amberlyst (Amberlyst) were added to a 100 ml eggplant-shaped flask equipped with a cooling tube. Registered trademark) 15 (Rohm and Haas trade name) 3.0g, THF 32.0ml, tin (II) chloride 3.8g (20.0mmol), pure water 8.0ml as a mixture, stirred at a temperature of 70 ° C for 24 hours and reacted . After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and then mixed with 60 ml of purified water. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was evaporated under reduced pressure to give a pale brown solid.

將該固體溶解於乙酸乙酯10ml，矽膠管柱層析(管柱：矽膠600.063-0.200mm Merck製之溶離液：己烷/乙酸乙酯=1/1)進行純化。由於此所得之溶液餾去溶劑，得到白色固體2.6g。將該固體以NMR進行測定之結果如以下所示。由該結果確認，該白色固體為下述反應式所示聚合性化合物(RM12)。產率為55%。The solid was dissolved in 10 ml of ethyl acetate, and purified by column chromatography (column: silica gel, 600.063-0.200 mm Merck, hexane/ethyl acetate = 1/1). The solvent thus obtained was evaporated to give a white solid (2.6 g). The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a polymerizable compound (RM12) represented by the following reaction formula. The yield was 55%.

1H-NMR(CDCl3) δ：1.54(m,4H),1.80(m,4H),2.94(m,2H),3.35(m,2H),3.97(t,4H),5.47(m,2H),5.68(m,2H),6.30(m,2H),6.88(d,4H),7.26(d,4H)。 1 H-NMR (CDCl 3 ) δ: 1.54 (m, 4H), 1.80 (m, 4H), 2.94 (m, 2H), 3.35 (m, 2H), 3.97 (t, 4H), 5.47 (m, 2H) ), 5.68 (m, 2H), 6.30 (m, 2H), 6.88 (d, 4H), 7.26 (d, 4H).

[化80][化80]

(聚合性化合物(RM13)之合成)(Synthesis of Polymerizable Compound (RM13))

於附有冷卻管之300ml茄形燒瓶中加入對甲醛苯甲酸7.5g(50.0mmol)、2-(溴甲基)丙烯酸9.1g(55.0mmol)、THF80.0ml、氯化錫(II)10.5g(110.0mmol)、及鹽酸水溶液(10%)35.0ml作為混合物，在70℃進行24小時攪拌並使其反應。反應終了後，與純水200ml混合，於此加入二乙基醚100ml並萃取。萃取進行3次。7.5 g (50.0 mmol) of p-formaldehyde benzoic acid, 9.1 g (55.0 mmol) of 2-(bromomethyl)acrylic acid, 80.0 ml of THF, and 10.5 g of tin chloride (II) were added to a 300 ml eggplant-shaped flask equipped with a cooling tube. (110.0 mmol) and 35.0 ml of an aqueous hydrochloric acid solution (10%) were mixed as a mixture at 70 ° C for 24 hours. After the completion of the reaction, it was mixed with 200 ml of pure water, and 100 ml of diethyl ether was added thereto and extracted. The extraction was carried out 3 times.

於萃取後的有機層中加入無水硫酸鎂使其乾燥，由減壓過濾後的溶液餾去溶劑，得到無色固體8.3g。將該固體的NMR測定結果如以下所示。由該結果確認，該無色固體為下述反應式所示化合物(RM13-A)。產率為76%。Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was filtered off under reduced pressure to give 8.3 g of a colorless solid. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the colorless solid was a compound (RM13-A) represented by the following reaction formula. The yield was 76%.

1H-NMR(DMSO-d6) δ：2.85(m,1H),3.50(m,1H),5.75(m,1H),5.80(s,1H),6.18(s,1H),7.45(d,2H),7.98(d,2H),13.08(s,1H)。 1 H-NMR (DMSO-d6) δ: 2.85 (m, 1H), 3.50 (m, 1H), 5.75 (m, 1H), 5.80 (s, 1H), 6.18 (s, 1H), 7.45 (d, 2H), 7.98 (d, 2H), 13.08 (s, 1H).

[化81][化81]

將上述所得之化合物(RM13-A)2.4g(11.0mmol)、1,6-己二醇0.6g(5.0mmol)、N,N-二甲基-4-胺基吡啶(DMAP)0.05g及少量BHT在室溫進行攪拌下，懸浮於二氯甲烷10ml，於此阿入溶解於二氯甲烷5ml的二環己基碳二亞胺(DCC)2.5g(12.0mmol)並進行48小時攪拌使其反應。反應終了後，過濾分離經析出之DCC脲，將該濾液依順序，以各60ml的0.5N-HCl與飽和碳酸氫鈉水溶液與飽和食鹽水進行2次洗淨，以硫酸鎂乾燥後，餾去溶劑後以乙醇進行再結晶操作，得到下述反應式所示聚合性化合物(RM13)1.3g。以NMR進行測定之結果如以下所示。又，產率為50%。2.4 g (11.0 mmol) of the compound (RM13-A) obtained above, 0.6 g (5.0 mmol) of 1,6-hexanediol, 0.05 g of N,N-dimethyl-4-aminopyridine (DMAP) and A small amount of BHT was suspended in 10 ml of dichloromethane at room temperature, and 2.5 g (12.0 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 5 ml of dichloromethane was added thereto and stirred for 48 hours. reaction. After the completion of the reaction, the precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 60 ml of 0.5 N-HCl and a saturated aqueous sodium hydrogencarbonate solution and brine, and dried over magnesium sulfate. The solvent was then subjected to recrystallization operation in ethanol to obtain 1.3 g of a polymerizable compound (RM13) represented by the following reaction formula. The results of measurement by NMR are shown below. Also, the yield was 50%.

1H-NMR(CDCl3) δ：1.53(m,4H),1.80(m,4H),2.85(m,2H),3.45(m,2H),4.36(m,4H),5.60(t,2H),6.72(d,2H),6.34(d,2H),7.40(d,4H),8.06(d,4H)。 1 H-NMR (CDCl 3 ) δ: 1.53 (m, 4H), 1.80 (m, 4H), 2.85 (m, 2H), 3.45 (m, 2H), 4.36 (m, 4H), 5.60 (t, 2H) , 6.72 (d, 2H), 6.34 (d, 2H), 7.40 (d, 4H), 8.06 (d, 4H).

[化82][化82]

(聚合性化合物(RM14)之合成)(Synthesis of polymerizable compound (RM14))

於附有冷卻管之300ml三口燒瓶中加入PCC 6.2g(28.7mmol)、及CH2Cl2 100.0ml並在攪拌混合狀態下，滴入將下述反應式所示化合物(RM14-A)8.0g(28.7mmol)溶解於CH2Cl2(30.0ml)的溶液，在室溫下再進行2小時攪拌。其後，於除去附著於燒瓶壁上的油狀物之溶液中，加入二乙基醚150ml並減壓過濾後，在減壓下使溶劑餾去，得到濃綠色濕潤固體。6.2 g (28.7 mmol) of PCC and 100.0 ml of CH 2 Cl 2 were added to a 300 ml three-necked flask equipped with a cooling tube, and 8.0 g of a compound (RM14-A) represented by the following reaction formula was added dropwise with stirring. (28.7 mmol) A solution dissolved in CH 2 Cl 2 (30.0 ml) was stirred at room temperature for additional 2 hours. Thereafter, 150 ml of diethyl ether was added to the solution of the oily substance adhering to the wall of the flask, and the mixture was filtered under reduced pressure, and the solvent was evaporated under reduced pressure to give a concentrated green solid.

將該固體藉由矽膠管柱層析法(管柱：矽膠60,0.063-0.200mm,莫克公司製，溶離液：己烷/乙酸乙酯=1/1)進行純化。餾去所得之溶液的溶劑，得到無色固體5.7g。將該固體以NMR進行測定之結果如以下所示。由該結果確認該無色固體為下述反應式所示化合物(RM14-B)。產率為72%。The solid was purified by ruthenium column chromatography (column: oxime 60, 0.063-0.200 mm, manufactured by Mock Corporation, eluent: hexane/ethyl acetate = 1/1). The solvent of the obtained solution was evaporated to give 5.7 g of a colorless solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the colorless solid was a compound (RM14-B) represented by the following reaction formula. The yield was 72%.

1H NMR(CDCl3) δ：1.50(m,2H),1.70(m,2H),1.85(m,2H),2.45(m,2H),3.80(s,3H),4.00(t,2H),6.25(d,1H),6.83(d,2H),7.45(d,2H),7.84(d,1H),9.80(s,1H)。1H NMR (CDCl3) δ: 1.50 (m, 2H), 1.70 (m, 2H), 1.85 (m, 2H), 2.45 (m, 2H), 3.80 (s, 3H), 4.00 (t, 2H), 6.25 (d, 1H), 6.83 (d, 2H), 7.45 (d, 2H), 7.84 (d, 1H), 9.80 (s, 1H).

[化83][化83]

其次，於附有冷卻管之100ml茄形燒瓶中加入上述所得之化合物(RM14-B)5.7g(20.6mmol)、2-(溴甲基)丙烯酸3.4g(20.6mmol)、10%鹽酸水溶液16ml、THF50ml、及氯化錫(II)3.9g(20.6mmol)作為混合物，溫度在70℃進行20小時攪拌使其反應。反應終了後，將反應液經減壓過濾後與純水100ml混合，於此加入二乙基醚150ml並萃取。萃取進行3次。Next, 5.7 g (20.6 mmol) of the compound (RM14-B) obtained above, 3.4 g (20.6 mmol) of 2-(bromomethyl)acrylic acid, and 16 ml of 10% hydrochloric acid aqueous solution were added to a 100 ml eggplant-shaped flask equipped with a cooling tube. Further, THF (50 ml) and tin (II) chloride (3.9 g) (20.6 mmol) were used as a mixture, and the mixture was stirred at 70 ° C for 20 hours to cause a reaction. After the completion of the reaction, the reaction solution was filtered under reduced pressure, and then mixed with 100 ml of purified water, and 150 ml of diethyl ether was added thereto and extracted. The extraction was carried out 3 times.

於萃取後的有機層中加入無水硫酸鎂使其乾燥，由減壓過濾後的溶液餾去溶劑，進行再結晶(己烷/乙酸乙酯、1/1)，得到無色固體4.6g。將該固體以NMR進行測定之結果如以下所示。由該結果確認，該無色固體為下述反應式所示聚合性化合物(RM14)。產率為65%。Anhydrous magnesium sulfate was added to the organic layer after the extraction to dryness, and the solvent was evaporated under reduced pressure to give crystals (hexane/ethyl acetate, 1/1) to afford 4.6 g of colorless solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the colorless solid is a polymerizable compound (RM14) represented by the following reaction formula. The yield was 65%.

1H NMR(CDCl3)δ：1.40-1.90(m,8H),2.60(m,1H),3.05(m,1H),3.80(s,3H),4.02(t,2H),4.55(m,1H),5.63(s,1H),6.25(s,1H),6.33(d,1H),6.90(d,2H),7.45(d,2H),7.65(d,1H)。1H NMR (CDCl3) δ: 1.40-1.90 (m, 8H), 2.60 (m, 1H), 3.05 (m, 1H), 3.80 (s, 3H), 4.02 (t, 2H), 4.55 (m, 1H) , 5.63 (s, 1H), 6.25 (s, 1H), 6.33 (d, 1H), 6.90 (d, 2H), 7.45 (d, 2H), 7.65 (d, 1H).

[化84][化84]

(聚合性化合物(RM15)之合成)(Synthesis of polymerizable compound (RM15))

於附有冷卻管之200ml茄形燒瓶中加入4-溴丁基-1,3-二噁戊烷5.0g(24.0mmol)、2-(溴甲基)丙烯酸4.5g(27.0mmol)、10%鹽酸水溶液19ml、THF60ml、及氯化錫(II)4.7g(27.0mmol)作為混合物，溫度在70℃進行20小時攪拌使其反應。反應終了後，將反應液經減壓過濾後與純水100ml混合，於此加入二乙基醚100ml並萃取。萃取進行3次。4-bromobutyl-1,3-dioxolane 5.0 g (24.0 mmol) and 2-(bromomethyl)acrylic acid 4.5 g (27.0 mmol), 10% were added to a 200 ml eggplant-shaped flask equipped with a cooling tube. 19 ml of an aqueous hydrochloric acid solution, 60 ml of THF, and 4.7 g (27.0 mmol) of tin (II) chloride were mixed as a mixture, and the mixture was stirred at 70 ° C for 20 hours to cause a reaction. After the completion of the reaction, the reaction solution was filtered under reduced pressure, and then mixed with 100 ml of purified water, and diethyl ether (100 ml) was added and extracted. The extraction was carried out 3 times.

於萃取後的有機層中加入無水硫酸鎂使其乾燥，由減壓過濾後的溶液餾去溶劑，得到無色液體5.2g。將該液體以NMR進行測定之結果如以下所示。由該結果確認，該無色液體為下述反應式所示化合物(RM15-A)。產率為93%。Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was filtered off under reduced pressure to give 5.2 g of a colorless liquid. The results of measurement of this liquid by NMR are shown below. From the results, it was confirmed that the colorless liquid was a compound (RM15-A) represented by the following reaction formula. The yield was 93%.

1H NMR(CDCl3) δ：1.64(m,4H),1.96(m,2H),2.06(m,1H),3.07(m,1H),3.44(t,2H),4.55(m,1H),5.65(s,1H),6.25(s,1H)。1H NMR (CDCl3) δ: 1.64 (m, 4H), 1.96 (m, 2H), 2.06 (m, 1H), 3.07 (m, 1H), 3.44 (t, 2H), 4.55 (m, 1H), 5.65 (s, 1H), 6.25 (s, 1H).

[化85][化85]

於附有冷卻管之100ml茄形燒瓶中加入上述所得之化合物(RM15-A)4.7g(20.0mmol)、4-甲氧基肉桂酸3.6g(20.0mmol)、碳酸鉀5.1g(40.0mmol)、及N,N-二甲基甲醯胺(DMF)50ml作為混合物，在110℃一邊進行48小時攪拌一邊使其反應。反應終了後，與純水200ml混合，於此加入乙酸乙酯50ml並萃取。萃取進行3次。於萃取後的有機層中加入無水硫酸鎂使其乾燥，由減壓過濾後的溶液餾去溶劑，得到固體。將該固體溶解於乙酸乙酯10ml，矽膠管柱層析(管柱：矽膠60 0.063-0.200mm Merck製之溶離液：己烷/乙酸乙酯=1/1)進行純化。由於此所得之溶液餾去溶劑，得到白色固體2.8g。將該固體的NMR測定結果如以下所示。由該結果確認，該固體為下述反應式所示聚合性化合物(RM15)。產率為43%。4.7 g (20.0 mmol) of the compound (RM15-A) obtained above, 3.6 g (20.0 mmol) of 4-methoxycinnamic acid, and 5.1 g (40.0 mmol) of potassium carbonate were added to a 100 ml eggplant-shaped flask equipped with a cooling tube. 50 ml of N,N-dimethylformamide (DMF) was used as a mixture, and the mixture was reacted at 110 ° C for 48 hours while stirring. After the completion of the reaction, it was mixed with 200 ml of pure water, and 50 ml of ethyl acetate was added thereto and extracted. The extraction was carried out 3 times. Anhydrous magnesium sulfate was added to the organic layer after extraction to dryness, and the solvent was filtered off under reduced pressure to give a solid. The solid was dissolved in 10 ml of ethyl acetate, and purified by column chromatography (column: silica gel 60 0.063-0.200 mm Merck solvent: hexane / ethyl acetate = 1 / 1). The solvent thus obtained was distilled off to give a white solid (2.8 g). The NMR measurement results of this solid are shown below. From the results, it was confirmed that the solid was a polymerizable compound (RM15) represented by the following reaction formula. The yield was 43%.

1H NMR(CDCl3)δ：1.50(m,2H),1.75(m,4H),2.63(m,1H),3.05(m,1H),3.85(s,3H),4.20(t,2H),4.55(m,1H),5.65(s,1H),6.23(s,1H),6.50(d,1H),6.90(d,2H),7.45(d,2H),7.66(d,1H)。1H NMR (CDCl3) δ: 1.50 (m, 2H), 1.75 (m, 4H), 2.63 (m, 1H), 3.05 (m, 1H), 3.85 (s, 3H), 4.20 (t, 2H), 4.55 (m, 1H), 5.65 (s, 1H), 6.23 (s, 1H), 6.50 (d, 1H), 6.90 (d, 2H), 7.45 (d, 2H), 7.66 (d, 1H).

[化86][化86]

(聚合性化合物(RM16)之合成)(Synthesis of polymerizable compound (RM16))

於附有冷卻管之200ml茄形燒瓶中加入4-溴丁基-1,3-二噁戊烷9.4g(45.0mmol)、反-4-苯基肉桂酸10.0g(45.0mmol)、碳酸鉀12.0g(90.0mmol)、及DMF100ml作為混合物，在110℃一邊進行48小時攪拌一邊使其反應。反應終了後，與純水100ml混合，得到固體。過濾該固體，加入乙醇50ml作為混合物並過濾。由減壓過濾後的溶液餾去溶劑，得到固體6.2g。將該固體的NMR測定結果如以下所示。由該結果確認，該固體為下述反應式所示化合物(RM16-A)。產率為40%。Add 4-bromobutyl-1,3-dioxolane 9.4g (45.0mmol), trans-4-phenylcinnamic acid 10.0g (45.0mmol), potassium carbonate to a 200ml eggplant-shaped flask with a cooling tube. 12.0 g (90.0 mmol) and 100 ml of DMF were used as a mixture, and the reaction was carried out while stirring at 110 ° C for 48 hours. After the completion of the reaction, it was mixed with 100 ml of pure water to obtain a solid. The solid was filtered, and 50 ml of ethanol was added as a mixture and filtered. The solvent was distilled off from the solution after filtration under reduced pressure to give 6.2 g of a solid. The NMR measurement results of this solid are shown below. From the results, it was confirmed that the solid was a compound (RM16-A) represented by the following reaction formula. The yield was 40%.

1H NMR(CDCl3) δ：1.55(m,2H),1.75(m,4H),3.83(m,2H),3.98(m,2H),4.24(t,2H),4.85(m,1H),6.45(d,1H),7.36(m,1H),7.46(m,2H),7.60(m,6H),7.75(d,1H)。1H NMR (CDCl3) δ: 1.55 (m, 2H), 1.75 (m, 4H), 3.83 (m, 2H), 3.98 (m, 2H), 4.24 (t, 2H), 4.85 (m, 1H), 6.45 (d, 1H), 7.36 (m, 1H), 7.46 (m, 2H), 7.60 (m, 6H), 7.75 (d, 1H).

[化87][化87]

其次，於附有冷卻管之100ml茄形燒瓶中加入上述所得之化合物(RM16-A)6.2g(18.0mmol)、2-(溴甲基)丙烯酸3.3g(20.0mmol)、10%鹽酸水溶液16ml、THF32ml、及氯化錫(II)3.8g(20.0mmol)作為混合物，溫度在70℃進行20小時攪拌使其反應。反應終了後，將反應液與純水100ml混合，於此加入二乙基醚50ml並進行萃取。萃取進行3次。Next, 6.2 g (18.0 mmol) of the compound (RM16-A) obtained above, 3.3 g (20.0 mmol) of 2-(bromomethyl)acrylic acid, and 16 ml of 10% hydrochloric acid aqueous solution were added to a 100 ml eggplant-shaped flask equipped with a cooling tube. THF (32 ml) and 3.8 g (20.0 mmol) of tin (II) chloride were mixed as a mixture, and the mixture was stirred at 70 ° C for 20 hours to cause a reaction. After the completion of the reaction, the reaction mixture was mixed with 100 ml of pure water, and 50 ml of diethyl ether was added thereto and extracted. The extraction was carried out 3 times.

於萃取後的有機層中加入無水硫酸鎂使其乾燥，由減壓過濾後的溶液餾去溶劑，進行再結晶(己烷/乙酸乙酯、2/1)得到固體3.6g。將該固體以NMR進行測定之結果如以下所示。由該結果確認，該固體為下述反應式所示聚合性化合物(RM16)。產率為53%。Anhydrous magnesium sulfate was added to the organic layer after the extraction to dryness, and the solvent was filtered off under reduced pressure, and then recrystallized (hexane/ethyl acetate, 2/1) to give 3.6 g of solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the solid was a polymerizable compound (RM16) represented by the following reaction formula. The yield was 53%.

1H NMR(CDCl3) δ：1.68(m,6H),2.63(m,1H),3.07(m,1H),4.24(t,2H),4.55(m,1H),5.64(s,1H),6.25(s,1H),6.50(d,1H),7.36(m,1H),7.46(m,2H),7.65(m,6H),7.75(d,1H)。1H NMR (CDCl3) δ: 1.68 (m, 6H), 2.63 (m, 1H), 3.07 (m, 1H), 4.24 (t, 2H), 4.55 (m, 1H), 5.64 (s, 1H), 6.25 (s, 1H), 6.50 (d, 1H), 7.36 (m, 1H), 7.46 (m, 2H), 7.65 (m, 6H), 7.75 (d, 1H).

[化88][化88]

(聚合性化合物(RM17)之合成)(Synthesis of Polymerizable Compound (RM17))

將上述方法所得之化合物(RM5-D)7.6g(25.0mmol)、乙基4-羥基肉桂酸酯4.8g(25.0mmol)、N,N-二甲基-4-胺基吡啶(DMAP)0.1g、及少量BHT在室溫進行攪拌下，懸浮於二氯甲烷100ml，於此加入溶解二環己基碳二亞胺(DCC)6.7g(32mmol)的溶液後進行一晚攪拌。將析出之DCC脲經過濾分離，將該濾液以0.5N-HCl 50ml、飽和碳酸氫鈉水溶液50ml、飽和食鹽水100ml之順序進行2次洗淨，以硫酸鎂乾燥後，在減壓下使溶劑餾去，得到黃色固體。將該固體使用乙醇進行再結晶而純化，得到白色固體7.1g。將該固體以NMR進行測定之結果如以下所示。由該結果確認，該白色固體為下述反應式所示聚合性化合物(RM17)。產率為59%。The compound obtained by the above method (RM5-D) 7.6 g (25.0 mmol), ethyl 4-hydroxycinnamate 4.8 g (25.0 mmol), N,N-dimethyl-4-aminopyridine (DMAP) 0.1 g, and a small amount of BHT were suspended in 100 ml of dichloromethane under stirring at room temperature, and a solution of 6.7 g (32 mmol) of dicyclohexylcarbodiimide (DCC) was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 ml of 0.5 N-HCl, 50 ml of a saturated aqueous sodium hydrogen carbonate solution and 100 ml of a saturated aqueous sodium chloride solution, and dried over magnesium sulfate. It was distilled off to give a yellow solid. The solid was purified by recrystallization using ethanol to give 7.1 g of a white solid. The results of measurement of the solid by NMR are shown below. From the results, it was confirmed that the white solid was a polymerizable compound (RM17) represented by the following reaction formula. The yield was 59%.

1H NMR(CDCl3) δ：1.35(t,3H),1.40-1.90(m,8H),2.60(m,1H),3.08(m,1H),4.05(t,2H),4.25(m,2H),4.55(m,1H),5.64(s,1H),6.22(s,1H),6.40(d,1H),6.97(d,2H),7.22(d,2H),7.60(d,2H),7.70(d,1H),8.15(d,2H)。1H NMR (CDCl3) δ: 1.35 (t, 3H), 1.40-1.90 (m, 8H), 2.60 (m, 1H), 3.08 (m, 1H), 4.05 (t, 2H), 4.25 (m, 2H) , 4.55 (m, 1H), 5.64 (s, 1H), 6.22 (s, 1H), 6.40 (d, 1H), 6.97 (d, 2H), 7.22 (d, 2H), 7.60 (d, 2H), 7.70 (d, 1H), 8.15 (d, 2H).

[化89][化89]

(聚合性化合物(RM18)之合成)(Synthesis of polymerizable compound (RM18))

將上述方法所得之化合物(RM5-D)7.3g(24.0mmol)、甲基4-羥基-3-甲氧基肉桂酸酯5.0g(24.0mmol)、N,N-二甲基-4-胺基吡啶(DMAP)0.1g、及少量BHT在室溫進行攪拌下，懸浮於二氯甲烷100ml，於此加入溶解二環己基碳二亞胺(DCC)6.4g(31.0mmol)之溶液並進行一晚攪拌。將析出之DCC脲經過濾分離，將該濾液以0.5N-HCl 100ml、飽和碳酸氫鈉水溶液100ml、飽和食鹽水150ml之順序進行2次洗淨，以硫酸鎂乾燥後，在減壓下使溶劑餾去，得到黃色固體。將該固體藉由再結晶(乙醇)進行純化，得到下述反應式所示聚合性化合物(RM18)6.1g。以NMR進行測定之結果如以下所示。又，產率為51%。The compound obtained by the above method (RM5-D) 7.3 g (24.0 mmol), methyl 4-hydroxy-3-methoxycinnamate 5.0 g (24.0 mmol), N,N-dimethyl-4-amine 0.1 g of pyridine (DMAP) and a small amount of BHT were suspended in 100 ml of dichloromethane at room temperature, and a solution of 6.4 g (31.0 mmol) of dicyclohexylcarbodiimide (DCC) was added thereto and a solution was added thereto. Stir at night. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 0.5 N of HCl, 100 ml of a saturated aqueous sodium hydrogencarbonate solution and 150 ml of a saturated aqueous sodium chloride solution, and dried over magnesium sulfate. It was distilled off to give a yellow solid. This solid was purified by recrystallization (ethanol) to obtain 6.1 g of a polymerizable compound (RM18) represented by the following reaction formula. The results of measurement by NMR are shown below. Also, the yield was 51%.

1H NMR(CDCl3)δ：1.40-1.90(m,8H),2.58(m,1H),3.08(m,1H),3.80(m,6H),4.05(t,2H),4.55(m,1H),5.62(s,1H),6.22(s,1H),6.42(d,1H),6.97(d,2H),7.18(m,3H),7.65(d,1H),8.18(d,2H)。1H NMR (CDCl3) δ: 1.40-1.90 (m, 8H), 2.58 (m, 1H), 3.08 (m, 1H), 3.80 (m, 6H), 4.05 (t, 2H), 4.55 (m, 1H) , 5.62 (s, 1H), 6.22 (s, 1H), 6.42 (d, 1H), 6.97 (d, 2H), 7.18 (m, 3H), 7.65 (d, 1H), 8.18 (d, 2H).

[化90][化90]

<聚醯亞胺分子量測定><Polymerimide molecular weight determination>

聚醯亞胺之分子量使用Senshu科學公司製　常溫凝膠滲透層析法(GPC)裝置(SSC-7200)、Shodex公司製管柱(KD-803、KD-805)並如以下進行測定。The molecular weight of the polyimine was measured using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd., and a column (KD-803, KD-805) manufactured by Shodex Co., Ltd., and the following.

管柱溫度：50℃Column temperature: 50 ° C

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

流速：1.0ml/分Flow rate: 1.0ml/min

檢量線作成用標準樣品：Tosho公司製TSK標準聚環氧乙烷(分子量約900,000、150,000、100,000、30,000)、及Polymer Laboratories Ltd.製　聚乙二醇(分子量約12,000、4,000、1,000)。A standard sample for the calibration curve was prepared: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosho Co., Ltd., and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories Ltd.

<醯亞胺化率的測定><Measurement of yttrium imidation rate>

聚醯亞胺的醯亞胺化率如以下進行測定。將聚醯亞胺粉末20mg放入NMR樣品管(草野科學公司製　NMR標準取樣管)，添加氘化二甲基亞碸(DMSO-d6、0.05%TMS混合品)0.53mL，在超音波中使其完全溶解。將該溶液之500MHz的質子NMR以日本電子DATUM公司製的NMR測定器(JNW-ECA500)進行測定。醯亞胺化率係由來自在醯亞胺化前後無變化的結構之質子作為基準質子而決定，使用該質子的波峰積分值、與來自於9.5～10.0ppm附近出現的醯胺酸之NH基的質子波峰積分值，依以下式子求得。The oxime imidization ratio of polyimine was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube (NMR standard sampling tube manufactured by Kusano Scientific Co., Ltd.), and 0.53 mL of deuterated dimethyl hydrazine (DMSO-d6, 0.05% TMS mixture) was added to make it in ultrasonic waves. It is completely dissolved. The proton NMR at 500 MHz of this solution was measured by an NMR measuring instrument (JNW-ECA500) manufactured by JEOL DATUM. The ruthenium imidization ratio is determined by a proton derived from a structure which does not change before and after the imidization, and the peak integral value of the proton and the NH group derived from proline which is present in the vicinity of 9.5 to 10.0 ppm are used. The proton peak integral value is obtained by the following equation.

醯亞胺化率(%)=(1-α‧x/y)×100醯 imidization rate (%) = (1-α‧x/y) × 100

對於下述式，x表示來自醯胺酸之NH基的質子波峰積分值，y表示基準質子的波峰積分值，α表示聚醯胺酸(醯亞胺化率為0%)時的醯胺酸之1個NH基質子所對應的基準質子個數比率。For the following formula, x represents the integral value of the proton peak derived from the NH group of proline, y represents the peak integral value of the reference proton, and α represents the proline acid when the polyproline (0% imidization ratio is 0%) The ratio of the number of reference protons corresponding to one NH matrix.

(實施例1)(Example 1)

將BODA(28.15g、112.5mmol)、m-PDA(4.86g、45mmol)、PCH(11.42g、30mmol)、DBA(11.41g、75mmol)在NMP(187.8g)中混合，在80℃進行5小時反應後，加入CBDA(6.77g、36mmol)與NMP(62.6g)，在40℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(313g)中加入NMP，稀釋至6質量%後，作為醯亞胺化觸媒加入乙酸酐(79.1g)、及吡啶(30.7g)，在100℃進行3小時反應。將反應溶液投入於甲醇(4000ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，以100℃進行減壓乾燥後得到聚醯亞胺粉末(A)。該聚醯亞胺的醯亞胺化率為70%，數平均分子量為18000，重量平均分子量為59000。BODA (28.15 g, 112.5 mmol), m-PDA (4.86 g, 45 mmol), PCH (11.42 g, 30 mmol), DBA (11.41 g, 75 mmol) were mixed in NMP (187.8 g), and carried out at 80 ° C for 5 hours. After the reaction, CBDA (6.77 g, 36 mmol) and NMP (62.6 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (313 g) and diluting to 6 mass%, acetic anhydride (79.1 g) and pyridine (30.7 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 100 ° C for 3 hours. . The reaction solution was poured into methanol (4000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A). The polyimine had a hydrazine imidation ratio of 70%, a number average molecular weight of 18,000, and a weight average molecular weight of 59,000.

於所得之聚醯亞胺粉末(A)(6.0g)加入NMP(40.2g)，在50℃進行12小時攪拌並使其溶解。於該溶液中加入3-AMP的5.0重量%NMP溶液(6.0g)(3-AMP為0.3g)、NMP(27.9g)、及BCS(20.0g)，在50℃進行5小時攪拌後得到液晶配向劑(A1)。To the obtained polyimine powder (A) (6.0 g), NMP (40.2 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. 3-AMP 5.0 wt% NMP solution (6.0 g) (3-AMP 0.3 g), NMP (27.9 g), and BCS (20.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal. Orienting agent (A1).

又，對於上述液晶配向劑(A1)10.0g添加0.06g(對於固體成分為10wt%)之RM1，在室溫進行3小時攪拌並使其溶解，調製出液晶配向劑(A2)。同樣地，液晶配向劑(A1)10.0g添加0.18g(對於固體成分為30wt%)之RM1，在室溫進行3小時攪拌並使其溶解，調製出液晶配向劑(A3)。In addition, 0.06 g (10 wt% of the solid content) of RM1 was added to 10.0 g of the liquid crystal alignment agent (A1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (A2). In the same manner, 0.18 g (30 wt% of the solid content) of RM1 was added to 10.0 g of the liquid crystal alignment agent (A1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (A3).

(實施例2)(Example 2)

將BODA(8.76g、35.0mmol)、p-PDA(3.78g、35.0mmol)、PCH(5.33g、14.0mmol)、DA-1(5.55g、21.0mmol)在NMP(90.0g)中混合，在80℃進行5小時反應後，加入CBDA(6.59g、33.6mmol)與NMP(30.0g)，在40℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(140.0g)加入NMP稀釋至6質量%後，作為醯亞胺化觸媒添加乙酸酐(20.0g)、及吡啶(25.8g)，在50℃進行3小時反應。將該反應溶液投入於甲醇(1800ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(B)。該聚醯亞胺的醯亞胺化率為50%，數平均分子量為22000，重量平均分子量為77000。BODA (8.76 g, 35.0 mmol), p-PDA (3.78 g, 35.0 mmol), PCH (5.33 g, 14.0 mmol), DA-1 (5.55 g, 21.0 mmol) were mixed in NMP (90.0 g). After reacting at 80 ° C for 5 hours, CBDA (6.59 g, 33.6 mmol) and NMP (30.0 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After the NMP was diluted to 6 mass% with the polyamidic acid solution (140.0 g), acetic anhydride (20.0 g) and pyridine (25.8 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. The reaction solution was poured into methanol (1800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (B). The polyamidimide had a ruthenium iodide ratio of 50%, a number average molecular weight of 22,000, and a weight average molecular weight of 77,000.

於所得之聚醯亞胺粉末(B)(6.0g)加入NMP(74.0g)，在50℃進行12小時攪拌並使其溶解。於溶液加入BCS(20.0g)，在50℃進行5小時攪拌後得到液晶配向劑(B1)。To the obtained polyimine powder (B) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (B1).

又，對於上述液晶配向劑(B1)10.0g添加0.06g(對於固體成分為10wt%)之RM1，在室溫進行3小時攪拌並使其溶解，調製出液晶配向劑(B2)。In addition, 0.06 g (10 wt% of the solid content) of RM1 was added to 10.0 g of the liquid crystal alignment agent (B1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (B2).

(實施例3)(Example 3)

將BODA(3.13g、12.5mmol)、p-PDA(1.08g、10mmol)、PCH(1.90g、5mmol)、DA-1(2.64g、10mmol)在NMP(33.3g)中混合，在80℃進行5小時反應後，加入CBDA(2.35g、12mmol)與NMP(11.1g)，在40℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(55.5g)中加入NMP並稀釋至6質量%後，作為醯亞胺化觸媒添加乙酸酐(7.7g)、及吡啶(9.9g)，在50℃進行3小時反應。將該反應溶液投入於甲醇(710ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(C)。該聚醯亞胺的醯亞胺化率為48%，數平均分子量為26000，重量平均分子量為102000。BODA (3.13 g, 12.5 mmol), p-PDA (1.08 g, 10 mmol), PCH (1.90 g, 5 mmol), DA-1 (2.64 g, 10 mmol) were mixed in NMP (33.3 g) at 80 ° C After 5 hours of reaction, CBDA (2.35 g, 12 mmol) and NMP (11.1 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (55.5 g) and diluting it to 6 mass%, acetic anhydride (7.7 g) and pyridine (9.9 g) were added as a ruthenium-imiding catalyst, and it was carried out at 50 ° C for 3 hours. reaction. The reaction solution was poured into methanol (710 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (C). The polyimine had a ruthenium iodide ratio of 48%, a number average molecular weight of 26,000, and a weight average molecular weight of 102,000.

於所得之聚醯亞胺粉末(C)(6.0g)中，加入NMP(74.0g)，在50℃進行12小時攪拌並使其溶解。於溶液加入BCS(20.0g)，在50℃進行5小時攪拌後得到液晶配向劑(C1)。NMP (74.0 g) was added to the obtained polyimine powder (C) (6.0 g), and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (C1).

又，對於上述液晶配向劑(C1)10.0g添加0.06g(對於固體成分為10wt%)之RM1，在室溫進行3小時攪拌並使其溶解，調製出液晶配向劑(C2)。In addition, 0.06 g (10 wt% of the solid content) of RM1 was added to 10.0 g of the liquid crystal alignment agent (C1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (C2).

(實施例4)(Example 4)

將BODA(3.13g、12.5mmol)、p-PDA(0.81g、7.5mmol)、PCH(1.90g、5mmol)、DA-1(3.30g、12.5mmol)在NMP(34.5g)中混合，在80℃進行5小時反應後，加入CBDA(2.35g、12mmol)與NMP(11.5g)，在40℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(57.5g)中加入NMP並稀釋至6質量%後，作為醯亞胺化觸媒添加乙酸酐(7.7g)、及吡啶(9.9g)，在50℃進行3小時反應。將該反應溶液投入於甲醇(730ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(D)。該聚醯亞胺的醯亞胺化率為50%，數平均分子量為23000，重量平均分子量為63000。BODA (3.13 g, 12.5 mmol), p-PDA (0.81 g, 7.5 mmol), PCH (1.90 g, 5 mmol), DA-1 (3.30 g, 12.5 mmol) were mixed in NMP (34.5 g) at 80 After reacting for 5 hours at ° C, CBDA (2.35 g, 12 mmol) and NMP (11.5 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (57.5 g) and diluting it to 6 mass%, acetic anhydride (7.7 g) and pyridine (9.9 g) were added as a ruthenium-imiding catalyst, and the mixture was carried out at 50 ° C for 3 hours. reaction. The reaction solution was poured into methanol (730 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (D). The polyimine had a hydrazide conversion ratio of 50%, a number average molecular weight of 23,000, and a weight average molecular weight of 63,000.

於所得之聚醯亞胺粉末(D)(6.0g)加入NMP(74.0g)，在50℃進行12小時攪拌並使其溶解。於溶液加入BCS(20.0g)，在50℃進行5小時攪拌後得到液晶配向劑(D1)。To the obtained polyimine powder (D) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (D1).

又，對於上述液晶配向劑(D1)10.0g添加0.06g(對於固體成分為10wt%)之RM1，在室溫進行3小時攪拌並使其溶解，調製出液晶配向劑(D2)。In addition, 0.06 g (10 wt% of the solid content) of RM1 was added to 10.0 g of the liquid crystal alignment agent (D1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (D2).

(實施例5)(Example 5)

將BODA(5.00g、20mmol)、p-PDA(0.87g、8mmol)、PCH(3.05g、8mmol)、DA-1(6.34g、24mmol)在NMP(57.1g)中混合，在80℃進行5小時反應後，加入CBDA(3.77g、19.2mmol)與NMP(19.0g)，在40℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(95.5g)加入NMP稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(12.3g)、及吡啶(15.9g)，在50℃進行3小時反應。將該反應溶液投入於甲醇(1200ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(E)。該聚醯亞胺的醯亞胺化率為51%，數平均分子量為31000，重量平均分子量為111000。BODA (5.00 g, 20 mmol), p-PDA (0.87 g, 8 mmol), PCH (3.05 g, 8 mmol), DA-1 (6.34 g, 24 mmol) were mixed in NMP (57.1 g) at 80 ° C After an hour of reaction, CBDA (3.77 g, 19.2 mmol) and NMP (19.0 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After the polyacrylic acid solution (95.5 g) was diluted with NMP to 6 mass%, acetic anhydride (12.3 g) and pyridine (15.9 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (1200 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (E). The polyamidimide had a ruthenium iodide ratio of 51%, a number average molecular weight of 31,000, and a weight average molecular weight of 111,000.

於所得之聚醯亞胺粉末(E)(6.0g)加入NMP(74.0g)，在50℃進行12小時攪拌並使其溶解。於溶液加入BCS(20.0g)，在50℃進行5小時攪拌後得到液晶配向劑(E1)。To the obtained polyimine powder (E) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (E1).

又，對於上述液晶配向劑(E1)10.0g添加0.06g(對於固體成分為10wt%)之RM1，在室溫進行3小時攪拌並使其溶解，調製出液晶配向劑(E2)。In addition, 0.06 g (10 wt% of the solid content) of RM1 was added to 10.0 g of the liquid crystal alignment agent (E1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (E2).

(實施例6)(Example 6)

將BODA(5.00g、20.0mmol)、p-PDA(2.16g、20.0mmol)、PCH(3.04g、8.0mmol)、DA-2(2.44g、12.0mmol)在NMP(49.2g)中混合，在80℃進行5小時反應後，加入CBDA(3.77g、19.2mmol)與NMP(16.4g)，在40℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(75.0g)加入NMP稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(9.33g)、及吡啶(14.6g)，在50℃進行3小時反應。將該反應溶液投入於甲醇(950ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(F)。該聚醯亞胺的醯亞胺化率為47%，數平均分子量為20100，重量平均分子量為106000。BODA (5.00 g, 20.0 mmol), p-PDA (2.16 g, 20.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (2.44 g, 12.0 mmol) were mixed in NMP (49.2 g). After reacting at 80 ° C for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (16.4 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After the polyacrylic acid solution (75.0 g) was diluted with NMP to 6 mass%, acetic anhydride (9.33 g) and pyridine (14.6 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (950 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (F). The polyamidimide had a ruthenium iodide ratio of 47%, a number average molecular weight of 20,100, and a weight average molecular weight of 106,000.

於所得之聚醯亞胺粉末(F)(6.0g)加入NMP(74.0g)，在50℃進行12小時攪拌並使其溶解。於溶液加入BCS(20.0g)，在50℃進行5小時攪拌後得到液晶配向劑(F1)。To the obtained polyimine powder (F) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (F1).

又，對於上述液晶配向劑(F1)10.0g添加0.06g(對於固體成分為10wt%)RM1，在室溫進行3小時攪拌並使其溶解，調製出液晶配向劑(F2)。In addition, 0.06 g (10 wt% of solid content) RM1 was added to 10.0 g of the liquid crystal alignment agent (F1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (F2).

(實施例7)(Example 7)

將BODA(5.00g、20.0mmol)、p-PDA(0.87g、8.0mmol)、PCH(3.04g、8.0mmol)、DA-2(4.88g、24.0mmol)在NMP(52.7g)中混合，在80℃進行5小時反應後，加入CBDA(3.77g、19.2mmol)與NMP(17.56g)，在40℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(75g)加入NMP並稀釋至6質量%後，作為醯亞胺化觸媒加入乙酸酐(8.7g)、及吡啶(13.5g)，在50℃進行3小時反應。將該反應溶液投入於甲醇(950ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(G)。該聚醯亞胺的醯亞胺化率為50%，數平均分子量為20000，重量平均分子量為86000。BODA (5.00 g, 20.0 mmol), p-PDA (0.87 g, 8.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (4.88 g, 24.0 mmol) were mixed in NMP (52.7 g). After reacting at 80 ° C for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (17.56 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (75 g) and diluting it to 6 mass%, acetic anhydride (8.7 g) and pyridine (13.5 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. The reaction solution was poured into methanol (950 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (G). The polyimine has a hydrazine imidation ratio of 50%, a number average molecular weight of 20,000, and a weight average molecular weight of 86,000.

於所得之聚醯亞胺粉末(G)(6.0g)加入NMP(74.0g)，在50℃進行12小時攪拌並使其溶解。於溶液加入BCS(20.0g)，在50℃進行5小時攪拌後得到液晶配向劑(G1)。To the obtained polyimine powder (G) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (G1).

又，對於上述液晶配向劑(G1)10.0g添加0.06g(對於固體成分為10wt%)之RM1，在室溫進行3小時攪拌並使其溶解，調製出液晶配向劑(G2)。In addition, 0.06 g (10 wt% of the solid content) of RM1 was added to 10.0 g of the liquid crystal alignment agent (G1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (G2).

(實施例8)(Example 8)

將BODA(6.01g、24.0mmol)、p-PDA(2.60g、24.0mmol)、PCH(6.85g、18.0mmol)、DA-1(4.76g、18.0mmol)溶解於NMP(81.5g)中，在80℃進行5小時反應後，加入CBDA(6.94g，35.4mmol)與NMP(27.2g)，在40℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(135g)中加入NMP並稀釋至6質量%後，作為醯亞胺化觸媒加入乙酸酐(18.3g)、及吡啶(23.6g)，在50℃進行3小時反應。將反應溶液投入於甲醇(1700ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(H)。該聚醯亞胺的醯亞胺化率為60%，數平均分子量為12000，重量平均分子量為39000BODA (6.01 g, 24.0 mmol), p-PDA (2.60 g, 24.0 mmol), PCH (6.85 g, 18.0 mmol), DA-1 (4.76 g, 18.0 mmol) were dissolved in NMP (81.5 g), After reacting at 80 ° C for 5 hours, CBDA (6.94 g, 35.4 mmol) and NMP (27.2 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (135 g) and diluting it to 6 mass%, acetic anhydride (18.3 g) and pyridine (23.6 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (1700 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (H). The polyimine has a hydrazide conversion ratio of 60%, a number average molecular weight of 12,000, and a weight average molecular weight of 39,000.

於所得之聚醯亞胺粉末(H)(6.0g)加入NMP(74.0g)，在50℃進行12小時攪拌並使其溶解。於溶液加入BCS(20.0g)，在50℃進行5小時攪拌後得到液晶配向劑(H1)。To the obtained polyimine powder (H) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (H1).

又，對於上述液晶配向劑(H1)10.0g添加聚合性化合物RM10.06g(對於固體成分為10質量%)，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H2)。In addition, 10.0 g of the liquid crystal alignment agent (H1) was added to the polymerizable compound RM10.06 g (10% by mass for the solid content), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (H2).

(實施例9)(Example 9)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM2，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H3)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM2 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H3).

(實施例10)(Embodiment 10)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM3，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H4)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM3 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H4).

(比較例1)(Comparative Example 1)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM4，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H5)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM4 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H5).

(實施例11)(Example 11)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM5，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H6)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM5 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H6).

(實施例12)(Embodiment 12)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM6，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H7)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM6 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H7).

(實施例13)(Example 13)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM7，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H8)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM7 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H8).

(實施例14)(Example 14)

對於液晶配向劑(H1)10.0g添加聚合性化合物RM80.06g(對於固體成分為10質量%)，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H9)。The polymerizable compound RM80.06 g (10% by mass of the solid content) was added to 10.0 g of the liquid crystal alignment agent (H1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (H9).

(實施例15)(Example 15)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM9，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H10)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM9 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H10).

(實施例16)(Embodiment 16)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM10，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H11)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM10 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H11).

(實施例17)(Example 17)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM11，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H12)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM11 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H12).

(實施例18)(Embodiment 18)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM12，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H13)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM12 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H13).

(實施例19)(Embodiment 19)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM13，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H14)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM13 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H14).

(實施例20)(Embodiment 20)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM14，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H15)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM14 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H15).

(實施例21)(Example 21)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM15，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H16)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM15 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H16).

(實施例22)(Example 22)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM16，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H17)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM16 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H17).

(實施例23)(Example 23)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM17，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H18)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM17 was added and stirred at room temperature for 3 hours to dissolve the liquid crystal alignment agent (H18).

(實施例24)(Example 24)

對於液晶配向劑(H1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM18，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(H19)。To the 10.0 g of the liquid crystal alignment agent (H1), 0.06 g (10% by mass of the solid content) of the polymerizable compound RM18 was added, and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (H19).

(實施例25)(Embodiment 25)

將BODA(4.38g、17.5mmol)、m-PDA(2.65g、24.5mmol)、PCH(4.00g、10.5mmol)溶解於NMP(42.8g)中，在80℃進行5小時反應後，加入CBDA(3.22g、16.5mmol)與NMP(14.2g)，在40℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(70.0g)加入NMP並稀釋至6質量%後，作為醯亞胺化觸媒加入乙酸酐(17.6g)、及吡啶(5.44g)，在100℃進行3小時反應。將該反應溶液投入於甲醇(900ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(I)。該聚醯亞胺的醯亞胺化率為73%，數平均分子量為15000，重量平均分子量為47000。BODA (4.38 g, 17.5 mmol), m-PDA (2.65 g, 24.5 mmol), PCH (4.00 g, 10.5 mmol) were dissolved in NMP (42.8 g), and after reacting at 80 ° C for 5 hours, CBDA was added ( 3.22 g, 16.5 mmol) and NMP (14.2 g) were reacted at 40 ° C for 10 hours to obtain a polyaminic acid solution. After the NMP was added to the polyamic acid solution (70.0 g) and diluted to 6% by mass, acetic anhydride (17.6 g) and pyridine (5.44 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 100 ° C for 3 hours. . The reaction solution was poured into methanol (900 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (I). The polyimine had a ruthenium iodide ratio of 73%, a number average molecular weight of 15,000, and a weight average molecular weight of 47,000.

於所得之聚醯亞胺粉末(I)(6.0g)加入NMP(74.0g)，在50℃進行12小時攪拌並使其溶解。於溶液加入BCS(20.0g)，在50℃進行5小時攪拌後得到聚醯亞胺溶液(I1)。To the obtained polyimine powder (I) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a polyimine solution (I1).

又對於聚醯亞胺溶液(I1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM1，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(I2)。Further, 0.06 g (10% by mass of the solid content) of the polymerizable compound RM1 was added to 10.0 g of the polyimine solution (I1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (I2). .

(實施例26)(Example 26)

將3AMPDA(2.54g、10.5mmol)、PCH(4.00g、10.5mmol)、DA-1(3.70g、1.4mmol)溶解於NMP(34.1g)中，在水浴中加入CBDA(6.79g、35.0mmol)與NMP(34.1g)，在23℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(84.0g)加入NMP稀釋至6質量%後，作為醯亞胺化觸媒，加入乙酸酐(10.6g)、及吡啶(4.51g)，在40℃進行3小時反應。將該反應溶液投入於甲醇(1000ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(J)。該聚醯亞胺的醯亞胺化率為41%，數平均分子量為13000，重量平均分子量為47000。3AMPDA (2.54g, 10.5mmol), PCH (4.00g, 10.5mmol), DA-1 (3.70g, 1.4mmol) were dissolved in NMP (34.1g), and CBDA (6.79g, 35.0mmol) was added to a water bath. A polyglycine solution was obtained by reacting with NMP (34.1 g) at 23 ° C for 10 hours. After the polyacrylic acid solution (84.0 g) was diluted with NMP to 6 mass%, acetic anhydride (10.6 g) and pyridine (4.51 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 40 ° C for 3 hours. . The reaction solution was poured into methanol (1000 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (J). The polyimine had a ruthenium iodide ratio of 41%, a number average molecular weight of 13,000, and a weight average molecular weight of 47,000.

於所得之聚醯亞胺粉末(J)(6.0g)加入NMP(54.0g)，於40℃進行12小時攪拌使其溶解。於溶液加入BCS(40.0g)，於40℃進行5小時攪拌後得到聚醯亞胺溶液(J1)。To the obtained polyimine powder (J) (6.0 g), NMP (54.0 g) was added, and the mixture was stirred at 40 ° C for 12 hours to be dissolved. BCS (40.0 g) was added to the solution, and the mixture was stirred at 40 ° C for 5 hours to obtain a polyimine solution (J1).

又，對於聚醯亞胺溶液(J1)10.0g添加0.06g(對於固體成分為10質量%)之聚合性化合物RM1，在室溫下進行3小時攪拌使其溶解，調製出液晶配向劑(J2)。In addition, 0.06 g (10% by mass of the solid content) of the polymerizable compound RM1 was added to 10.0 g of the polyimine solution (J1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal alignment agent (J2). ).

(實施例27)(Example 27)

將TCA(3.36g、15.0mmol)、p-PDA(1.30g、12.0mmol)、DA-3(3.14g、6.0mmol)、DA-1(3.17g、12.0mmol)在NMP(41.6g)中混合，在60℃進行5小時反應後，加入CBDA(2.88g、14.7mmol)與NMP(13.9g)，在40℃進行10小時反應後得到聚醯胺酸溶液。於該聚醯胺酸溶液(68g)中加入NMP並稀釋至6質量%後，作為醯亞胺化觸媒添加乙酸酐(6.0g)、及吡啶(11.7g)，在50℃進行3小時反應。將該反應溶液投入於甲醇(850ml)，過濾出所得之沈澱物。將該沈澱物以甲醇洗淨，在100℃進行減壓乾燥後得到聚醯亞胺粉末(K)。該聚醯亞胺的醯亞胺化率為50%，數平均分子量為18000，重量平均分子量為58000。TCA (3.36 g, 15.0 mmol), p-PDA (1.30 g, 12.0 mmol), DA-3 (3.14 g, 6.0 mmol), DA-1 (3.17 g, 12.0 mmol) were mixed in NMP (41.6 g). After reacting at 60 ° C for 5 hours, CBDA (2.88 g, 14.7 mmol) and NMP (13.9 g) were added, and the reaction was carried out at 40 ° C for 10 hours to obtain a polyaminic acid solution. After adding NMP to the polyamic acid solution (68 g) and diluting it to 6 mass%, acetic anhydride (6.0 g) and pyridine (11.7 g) were added as a ruthenium amide catalyst, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (850 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (K). The polyamidimide had a ruthenium iodide ratio of 50%, a number average molecular weight of 18,000, and a weight average molecular weight of 58,000.

於所得之聚醯亞胺粉末(K)(6.0g)加入NMP(74.0g)，在50℃進行12小時攪拌並使其溶解。於溶液加入BCS(20.0g)，在50℃進行5小時攪拌後得到液晶配向劑(K1)。To the obtained polyimine powder (K) (6.0 g), NMP (74.0 g) was added, and the mixture was stirred at 50 ° C for 12 hours and dissolved. BCS (20.0 g) was added to the solution, and the mixture was stirred at 50 ° C for 5 hours to obtain a liquid crystal alignment agent (K1).

又，對於上述液晶配向劑(K1)10.0g添加0.06g(對於固體成分為10wt%)之RM1，在室溫進行3小時攪拌並使其溶解，調出液晶配向劑(K2)。In addition, 0.06 g (10 wt% of the solid content) of RM1 was added to 10.0 g of the liquid crystal alignment agent (K1), and the mixture was stirred and dissolved at room temperature for 3 hours to adjust the liquid crystal alignment agent (K2).

(實施例28)(Embodiment 28)

使用實施例1所得之液晶配向劑(A2)進行如下述所示順序進行液晶胞的製作。Using the liquid crystal alignment agent (A2) obtained in Example 1, the production of liquid crystal cells was carried out in the order shown below.

[液晶胞的製作][Production of liquid crystal cell]

液晶配向劑(A2)旋轉塗佈於形成畫素尺寸為100μm×300μm且線/間距各5μm的ITO電極圖型之ITO電極基板的ITO面上，在80℃的加熱板進行90秒乾燥後，在200℃的熱風循環式烤箱中進行30分鐘燒成，形成膜厚100nm的液晶配向膜。The liquid crystal alignment agent (A2) was spin-coated on an ITO surface of an ITO electrode substrate having an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line/pitch of 5 μm, and dried on a hot plate at 80 ° C for 90 seconds. The film was fired in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.

又，將液晶配向劑(A2)旋轉塗佈於未形成電極圖型之ITO面上，在80℃的加熱板上進行90秒乾燥後，在200℃的熱風循環式烤箱中進行30分鐘燒成，形成膜厚100nm的液晶配向膜。Further, the liquid crystal alignment agent (A2) was spin-coated on the ITO surface on which the electrode pattern was not formed, dried on a hot plate at 80 ° C for 90 seconds, and then fired in a hot air circulating oven at 200 ° C for 30 minutes. A liquid crystal alignment film having a film thickness of 100 nm was formed.

對於上述2片基板，於一方基板的液晶配向膜上散佈6μm的珠子間隔物後，由該上面塗佈密封劑(溶劑型熱硬化型環氧樹脂)。其次，將形成另一基板的液晶配向膜之面作為內側，與先前的基板貼合後，使密封劑硬化後製作出空胞。於該空胞將MLC-6608藉由減壓注入法注入，在120℃的烤箱中進行Isotropic處理(藉由加熱之液晶的再配向處理)製作出液晶胞。On the two substrates, a 6 μm bead spacer was spread on the liquid crystal alignment film of one of the substrates, and then a sealant (solvent-type thermosetting epoxy resin) was applied from the upper surface. Next, the surface of the liquid crystal alignment film forming the other substrate was set to the inside, and after bonding to the previous substrate, the sealant was cured to prepare a hollow cell. MLC-6608 was injected into the cell by a reduced pressure injection method, and Isotropic treatment (re-alignment treatment by heated liquid crystal) was performed in an oven at 120 ° C to prepare a liquid crystal cell.

將所得之液晶胞的製作後應答速度藉由下述方法進行測定。其後，在於該液晶胞外加20Vp-p的電壓之狀態下，由液晶胞外側照射通過313nm的帶通濾波器(Band-pass filter)之UV20J。其後，再次測定應答速度，比較在UV照射前後之應答速度。液晶胞的製作直後(初期)、及照射UV之20J後(UV20J後)之應答速度的結果如表2～4所示。The post-production response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, in a state where a voltage of 20 Vp-p was applied to the liquid crystal cell, UV20J which passed through a 313 nm band-pass filter was irradiated from the outside of the liquid crystal cell. Thereafter, the response speed was measured again, and the response speed before and after the UV irradiation was compared. Tables 2 to 4 show the results of the response speeds of the liquid crystal cells immediately after (initial) and after irradiation with UV 20J (after UV20J).

(實施例29)(Example 29)

將液晶配向劑(A2)變更為液晶配向劑(A3)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (A3), and the response speed before and after the UV irradiation was compared.

(比較例2)(Comparative Example 2)

將液晶配向劑(A2)變更為液晶配向劑(A1)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (A1), and the response speed before and after the UV irradiation was compared.

(實施例30)(Embodiment 30)

將液晶配向劑(A2)變更為液晶配向劑(B2)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (B2), and the response speed before and after the UV irradiation was compared.

(比較例3)(Comparative Example 3)

將液晶配向劑(A2)變更為液晶配向劑(B1)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (B1), and the response speed before and after the UV irradiation was compared.

(實施例31)(Example 31)

將液晶配向劑(A2)變更為液晶配向劑(C2)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (C2), and the response speed before and after the UV irradiation was compared.

(比較例4)(Comparative Example 4)

將液晶配向劑(A2)變更為液晶配向劑(C1)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (C1), and the response speed before and after the UV irradiation was compared.

(實施例32)(Example 32)

將液晶配向劑(A2)變更為液晶配向劑(D2)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (D2), and the response speed before and after the UV irradiation was compared.

(比較例5)(Comparative Example 5)

將液晶配向劑(A2)變更為液晶配向劑(D1)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (D1), and the response speed before and after the UV irradiation was compared.

(實施例33)(Example 33)

將液晶配向劑(A2)變更為液晶配向劑(E2)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (E2), and the response speed before and after the UV irradiation was compared.

(比較例6)(Comparative Example 6)

將液晶配向劑(A2)變更為液晶配向劑(E1)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (E1), and the response speed before and after the UV irradiation was compared.

(實施例34)(Example 34)

將液晶配向劑(A2)變更為液晶配向劑(F2)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (F2), and the response speed before and after the UV irradiation was compared.

(比較例7)(Comparative Example 7)

將液晶配向劑(A2)變更為液晶配向劑(F1)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (F1), and the response speed before and after the UV irradiation was compared.

(實施例35)(Example 35)

將液晶配向劑(A2)變更為液晶配向劑(G2)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (G2), and the response speed before and after the UV irradiation was compared.

(比較例8)(Comparative Example 8)

將液晶配向劑(A2)變更為液晶配向劑(G1)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (G1), and the response speed before and after the UV irradiation was compared.

(實施例36)(Example 36)

將液晶配向劑(A2)變更為液晶配向劑(H2)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H2), and the response speed before and after the UV irradiation was compared.

(實施例37)(Example 37)

將液晶配向劑(A2)變更為液晶配向劑(H2)，將燒成溫度變更為140℃以外，與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H2), and the firing rate was changed to 140 ° C. The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared.

(實施例38)(Example 38)

將液晶配向劑(A2)變更為液晶配向劑(H3)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H3), and the response speed before and after the UV irradiation was compared.

(實施例39)(Example 39)

將液晶配向劑(A2)變更為液晶配向劑(H3)，將燒成溫度變更為140℃以外，與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H3), and the firing rate was changed to 140 ° C. The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared.

(實施例40)(Embodiment 40)

將液晶配向劑(A2)變更為液晶配向劑(H4)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H4), and the response speed before and after the UV irradiation was compared.

(實施例41)(Example 41)

將液晶配向劑(A2)變更為液晶配向劑(H4)，將燒成溫度變更為140℃以外，與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H4), and the firing rate was changed to 140 ° C. The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared.

(比較例9)(Comparative Example 9)

將液晶配向劑(A2)變更為液晶配向劑(H5)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H5), and the response speed before and after the UV irradiation was compared.

(比較例10)(Comparative Example 10)

將液晶配向劑(A2)變更為液晶配向劑(H5)，將燒成溫度變更為140℃以外，與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal alignment agent (A2) was changed to a liquid crystal alignment agent (H5), and the firing rate was changed to 140 ° C. The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared.

(比較例11)(Comparative Example 11)

將液晶配向劑(A2)變更為液晶配向劑(H1)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H1), and the response speed before and after the UV irradiation was compared.

(比較例12)(Comparative Example 12)

將液晶配向劑(A2)變更為液晶配向劑(H1)，將燒成溫度變更為140℃以外，與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H1), and the firing rate was changed to 140 ° C. The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared.

(實施例42)(Example 42)

將液晶配向劑(A2)變更為液晶配向劑(I2)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (I2), and the response speed before and after the UV irradiation was compared.

(實施例43)(Example 43)

將液晶配向劑(A2)變更為液晶配向劑(I2)，將燒成溫度變更為140℃以外，與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (I2), and the firing rate was changed to 140 ° C. The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared.

(比較例13)(Comparative Example 13)

液晶配向劑(A2)變更為聚醯亞胺溶液(I1)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。When the liquid crystal alignment agent (A2) was changed to the polyimine solution (I1), the liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared.

(比較例14)(Comparative Example 14)

液晶配向劑(A2)變更為聚醯亞胺溶液(I1)，將燒成溫度變更為140℃以外，與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal alignment agent (A2) was changed to a polyimine solution (I1), and the firing rate was changed to 140 ° C. The liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared.

(實施例44)(Example 44)

將液晶配向劑(A2)變更為液晶配向劑(H6)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H6), and the response speed before and after the UV irradiation was compared.

(實施例45)(Example 45)

將液晶配向劑(A2)變更為液晶配向劑(H7)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H7), and the response speed before and after the UV irradiation was compared.

(實施例46)(Example 46)

將液晶配向劑(A2)變更為液晶配向劑(H8)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H8), and the response speed before and after the UV irradiation was compared.

(實施例47)(Example 47)

將液晶配向劑(A2)變更為液晶配向劑(H9)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H9), and the response speed before and after the UV irradiation was compared.

(實施例48)(Example 48)

將液晶配向劑(A2)變更為液晶配向劑(H10)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H10), and the response speed before and after the UV irradiation was compared.

(實施例49)(Example 49)

將液晶配向劑(A2)變更為液晶配向劑(H11)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H11), and the response speed before and after the UV irradiation was compared.

(實施例50)(Example 50)

將液晶配向劑(A2)變更為液晶配向劑(H12)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H12), and the response speed before and after the UV irradiation was compared.

(實施例51)(Example 51)

將液晶配向劑(A2)變更為液晶配向劑(H13)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H13), and the response speed before and after the UV irradiation was compared.

(實施例52)(Example 52)

將液晶配向劑(A2)變更為液晶配向劑(H14)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H14), and the response speed before and after the UV irradiation was compared.

(實施例53)(Example 53)

將液晶配向劑(A2)變更為液晶配向劑(H15)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H15), and the response speed before and after the UV irradiation was compared.

(實施例54)(Example 54)

將液晶配向劑(A2)變更為液晶配向劑(H16)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H16), and the response speed before and after the UV irradiation was compared.

(實施例55)(Example 55)

將液晶配向劑(A2)變更為液晶配向劑(H17)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H17), and the response speed before and after the UV irradiation was compared.

(實施例56)(Example 56)

將液晶配向劑(A2)變更為液晶配向劑(H18)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H18), and the response speed before and after the UV irradiation was compared.

(實施例57)(Example 57)

將液晶配向劑(A2)變更為液晶配向劑(H19)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (H19), and the response speed before and after the UV irradiation was compared.

(實施例58)(Example 58)

將液晶配向劑(A2)變更為液晶配向劑(J2)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was prepared in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (J2), and the response speed before and after the UV irradiation was compared.

(實施例59)(Example 59)

將液晶配向劑(A2)變更為液晶配向劑(K2)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。The liquid crystal cell was produced in the same manner as in Example 28 except that the liquid crystal alignment agent (A2) was changed to the liquid crystal alignment agent (K2), and the response speed before and after the UV irradiation was compared.

(比較例15)(Comparative Example 15)

液晶配向劑(A2)變更為聚醯亞胺溶液(J1)以外與實施例28同樣地製作液晶胞後比較在UV照射前後之應答速度。When the liquid crystal alignment agent (A2) was changed to the polyimine solution (J1), the liquid crystal cell was produced in the same manner as in Example 28, and the response speed before and after the UV irradiation was compared.

「應答速度的測定方法」"Method for measuring response speed"

設定為背光、正交偏光狀態的一組以偏光板、光量檢測器的順序所構成之測定裝置，於一組偏光板之間配置液晶胞。A measuring device comprising a polarizing plate and a light amount detector in a state of a backlight and a quadrature polarization state is disposed, and a liquid crystal cell is disposed between a group of polarizing plates.

此時線/間距所形成之ITO電極的圖型對於正交偏光而言，使其成為45°之角度。此時線/間距所形成之ITO電極的圖型對於正交偏光而言，使其成為45°之角度。而於上述液晶胞外加電壓±4V、周波數1kHz之矩形波，藉由光量檢測器所觀測的亮度到達飽和之變化由示波器(oscilloscope)讀取，未外加電壓時的亮度為0%，外加±4V的電壓，且飽和亮度之值作為100%，將亮度自10%變化至90%的時間作為應答速度。結果如表2~4所示。 At this time, the pattern of the ITO electrode formed by the line/pitch is made to be an angle of 45° for the orthogonal polarized light. At this time, the pattern of the ITO electrode formed by the line/pitch is made to be an angle of 45° for the orthogonal polarized light. In the above-mentioned liquid crystal cell, a rectangular wave with a voltage of ±4 V and a frequency of 1 kHz is applied, and the change in brightness observed by the light amount detector is read by an oscilloscope, and the brightness when the voltage is not applied is 0%, plus ± The voltage of 4V, and the value of the saturation brightness is taken as 100%, and the time when the brightness is changed from 10% to 90% is taken as the response speed. The results are shown in Tables 2 to 4.

由表2的結果確認添加於末端具有α-亞甲基-γ-丁基內酯基的聚合性化合物RM1後，UV照射後之應答速度會顯著提高。又，確認增加聚合性化合物的添加量時顯示應答速度提高率增高之傾向，但使用持有光反應性側鏈的聚合物時，即使聚合性化合物之添加量較少，亦維持應答速度的提高率。 From the results of Table 2, it was confirmed that the polymerization rate after the UV irradiation was remarkably improved after the addition of the polymerizable compound RM1 having an α-methylene-γ-butyl lactone group at the terminal. In addition, when the addition amount of the polymerizable compound is increased, the rate of improvement of the response rate tends to increase. However, when a polymer having a photoreactive side chain is used, the reaction rate is improved even when the amount of the polymerizable compound added is small. rate.

由表3的結果顯示在如200℃的高溫下進行燒成時，使用含有於末端具有α-亞甲基-γ-丁基內酯基的RM1~RM3之聚合性化合物的液晶配向劑時，比於末端不具有α-亞甲基-γ-丁基內酯基而具有甲基丙烯基結構的RM4顯示顯著更高應答速度的提高率之傾向。此表示α-亞甲基-γ-丁基內酯結構即使在高溫亦安定，反應基係為比甲基丙烯基更不容易引起熱聚合之結構之故。 When the liquid crystal alignment agent containing the polymerizable compound of RM1 to RM3 having an α-methylene-γ-butyl lactone group at the terminal is used, when the baking is performed at a high temperature of 200 ° C, the results are shown in Table 3 RM4 having a methacryl structure rather than an α-methylene-γ-butyl lactone group at the end showed a tendency to significantly increase the rate of response. This indicates that the α-methylene-γ-butyl lactone structure is stable even at a high temperature, and the reaction group is a structure which is less likely to cause thermal polymerization than the methacryl group.

由表4的結果確認，作為聚合性化合物即使使用於種種末端上具有α-亞甲基-γ-丁基內酯基的聚合性化合物時，其應答速度亦顯著提高。又，作為欲提高應答速度之具有α-亞甲基-γ-丁基內酯基之聚合性化合物，僅含有1個該結構即可期待相同效果，作為其他結構即使含有丙烯基等聚合性基或桂皮醯基等藉由光二量化之光交聯性基等亦可提高應答速度。From the results of Table 4, it was confirmed that the polymerizable compound was used in a polymerizable compound having an α-methylene-γ-butyl lactone group at various terminals, and the response rate was remarkably improved. In addition, as the polymerizable compound having an α-methylene-γ-butyl lactone group to increase the response speed, the same effect can be obtained by including only one such structure, and a polymerizable group such as a propylene group is contained as another structure. The light-crosslinking group or the like which is quantified by the light bismuth or the like may also increase the response speed.

Claims (8)

一種液晶配向劑，其特徵為含有以下聚合性化合物、聚合物及溶劑者；其中該聚合性化合物為持有具有α-亞甲基-γ-丁內酯基之末端與具有進行光聚合或光交聯之基的末端的聚合性化合物；該聚合物為形成能使液晶配向之液晶配向膜的聚合物。 A liquid crystal alignment agent characterized by containing a polymerizable compound, a polymer, and a solvent; wherein the polymerizable compound has a terminal having an α-methylene-γ-butyrolactone group and has photopolymerization or light A polymerizable compound at the end of the crosslinked group; the polymer is a polymer which forms a liquid crystal alignment film capable of aligning liquid crystals. 如申請專利範圍第1項之液晶配向劑，其中前述聚合性化合物為選自下述式[I-1]~[I-4]的至少一種； (式[I-1]~[I-4]中，V表示單鍵或-R31O-，R31為直鏈或分支之碳數1~10的伸烷基，W表示單鍵或-OR32-，R32為直鏈或分支之碳數1~10的伸烷基，n1為1~10的整數，x及y各獨立為1或2，R1為氫或甲基，A21為單鍵或選自下述的基) (式中，p1為2~10的整數，q1為0~1的整數，z為1或2)。 The liquid crystal alignment agent of claim 1, wherein the polymerizable compound is at least one selected from the group consisting of the following formulas [I-1] to [I-4]; (In the formula [I-1] to [I-4], V represents a single bond or -R 31 O-, and R 31 is a linear or branched alkyl group having 1 to 10 carbon atoms, and W represents a single bond or - OR 32 -, R 32 is a linear or branched alkyl group having 1 to 10 carbon atoms, n1 is an integer of 1 to 10, x and y are each independently 1 or 2, and R 1 is hydrogen or methyl, A 21 Is a single bond or a base selected from the group consisting of (In the formula, p1 is an integer of 2 to 10, q1 is an integer of 0 to 1, and z is 1 or 2). 如申請專利範圍第1項之液晶配向劑，其中前述聚合性化合物為選自下述式[II-1]~[II-3]的至少一種； (式[II-1]~[II-3]中，n2為2~11的整數，m1為0~11的整數，x為1或2，R2為氫、-OCH3或鹵素原子，R3為氫、-CN、-O(CH2)m1CH3或鹵素原子，R4為-(CH2) m1CH3(m1為0~11之整數)，A22為單鍵、-O-C6H4-或-O-C6H4-C6H4-)。 The liquid crystal alignment agent of claim 1, wherein the polymerizable compound is at least one selected from the group consisting of the following formulas [II-1] to [II-3]; (In the formula [II-1] to [II-3], n2 is an integer of 2 to 11, m1 is an integer of 0 to 11, x is 1 or 2, and R 2 is hydrogen, -OCH 3 or a halogen atom, R 3 is hydrogen, -CN, -O(CH 2 ) m1 CH 3 or a halogen atom, R 4 is -(CH 2 ) m1 CH 3 (m1 is an integer of 0 to 11), and A 22 is a single bond, -OC 6 H 4 - or -OC 6 H 4 -C 6 H 4 -). 如申請專利範圍第1項之液晶配向劑，其中前述聚合性化合物為下述式[III-1]； (式[III-1]中，11為2~9的整數，X1為下述式[iii-3]的基) (式[iii-3]中，R5為選自下述式之基) (式中，R1為氫或甲基，n3為2~10之整數，p2為3~10之整數)。 The liquid crystal alignment agent of claim 1, wherein the polymerizable compound is the following formula [III-1]; (In the formula [III-1], 11 is an integer of 2 to 9, and X 1 is a group of the following formula [iii-3]) (In the formula [iii-3], R 5 is a group selected from the following formula) (wherein R 1 is hydrogen or methyl, n 3 is an integer of 2 to 10, and p 2 is an integer of 3 to 10). 如申請專利範圍第1項之液晶配向劑，其中前述形成能使液晶配向之液晶配向膜的聚合物，為具有將液晶配 向呈垂直之側鏈。 The liquid crystal alignment agent of claim 1, wherein the polymer forming the liquid crystal alignment film capable of aligning the liquid crystal has a liquid crystal matching The side chain is vertical. 一種液晶配向膜，其特徵為將如申請專利範圍第1項至第5項中任一項之液晶配向劑塗佈於基板上，經燒成後所得者。 A liquid crystal alignment film which is obtained by applying a liquid crystal alignment agent according to any one of claims 1 to 5 to a substrate and firing it. 一種液晶顯示元件，其特徵為具有以下液晶胞者，該液晶胞係由將如申請專利範圍第1項至第5項中任一項之液晶配向劑塗佈於基板上，經燒成所得之液晶配向膜上設置液晶層並與其接觸，於該液晶層一邊外加電壓一邊照射紫外線而製作。 A liquid crystal display device characterized by having a liquid crystal cell coated on a substrate by a liquid crystal alignment agent according to any one of claims 1 to 5, which is obtained by firing. A liquid crystal layer is provided on the liquid crystal alignment film and brought into contact therewith, and the liquid crystal layer is irradiated with ultraviolet rays while applying a voltage. 一種液晶顯示元件的製造方法，其特徵為將如申請專利範圍第1項至第5項中任一項之液晶配向劑塗佈於基板上，經燒成所得之液晶配向膜上設置液晶層並與其接觸，於該液晶層一邊外加電壓一邊照射紫外線而製作液晶胞。 A method for producing a liquid crystal display device, characterized in that a liquid crystal alignment agent according to any one of claims 1 to 5 is applied onto a substrate, and a liquid crystal layer is provided on the liquid crystal alignment film obtained by firing In contact with this, a liquid crystal cell is produced by applying a voltage to the liquid crystal layer while irradiating ultraviolet rays.
TW100123258A 2010-06-30 2011-06-30 A liquid crystal alignment device, a liquid crystal alignment device, a liquid crystal display device, and a liquid crystal display device, and a polymerizable compound TWI520948B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010150126 2010-06-30
JP2011080764 2011-03-31

Publications (2)

Publication Number Publication Date
TW201217352A TW201217352A (en) 2012-05-01
TWI520948B true TWI520948B (en) 2016-02-11

Family

ID=45402215

Family Applications (2)

Application Number Title Priority Date Filing Date
TW104118756A TW201534594A (en) 2010-06-30 2011-06-30 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, manufacturing method for liquid crystal display element, and polymerisable compound
TW100123258A TWI520948B (en) 2010-06-30 2011-06-30 A liquid crystal alignment device, a liquid crystal alignment device, a liquid crystal display device, and a liquid crystal display device, and a polymerizable compound

Family Applications Before (1)

Application Number Title Priority Date Filing Date
TW104118756A TW201534594A (en) 2010-06-30 2011-06-30 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, manufacturing method for liquid crystal display element, and polymerisable compound

Country Status (5)

Country Link
JP (2) JP5943203B2 (en)
KR (1) KR101896727B1 (en)
CN (2) CN104910106B (en)
TW (2) TW201534594A (en)
WO (1) WO2012002512A1 (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101912955B1 (en) * 2010-06-30 2018-10-29 닛산 가가쿠 가부시키가이샤 Polymerizable compound, liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and method for producing liquid crystal display device
JP6048398B2 (en) * 2011-02-25 2016-12-21 日産化学工業株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and alignment film
KR102113892B1 (en) * 2012-10-05 2020-05-21 닛산 가가쿠 가부시키가이샤 Manufacturing method for substrate having liquid crystal alignment film for in-plane switching-type liquid crystal display element
JP2014112192A (en) * 2012-10-31 2014-06-19 Jsr Corp Liquid crystal orienting agent for psa mode liquid crystal display element, liquid crystal orientation film for psa mode liquid crystal display element, psa mode liquid crystal display element, and method for producing the same
JP6017407B2 (en) * 2013-05-13 2016-11-02 国立大学法人 東京大学 POLYMER AND METHOD FOR PRODUCING POLYMER
CN105705497B (en) * 2013-10-04 2018-02-16 日产化学工业株式会社 Polymerizable liquid crystal compound, liquid-crystalline polymer, liquid crystalline composition and single coating type horizontal alignment film
TWI647226B (en) * 2014-01-30 2019-01-11 日商日產化學工業股份有限公司 Polymeric compound squeeze by halogen atom
TWI657297B (en) * 2014-01-30 2019-04-21 日商日產化學工業股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
KR102224841B1 (en) * 2014-06-11 2021-03-10 삼성디스플레이 주식회사 Liquid crystal display device and method for manufacturing the same
CN104049413A (en) * 2014-06-28 2014-09-17 中能柔性光电（滁州）有限公司 Liquid crystal optical orientation method
JP6414226B2 (en) * 2014-09-25 2018-10-31 日産化学株式会社 Liquid crystal display element
KR102508578B1 (en) * 2014-11-04 2023-03-09 닛산 가가쿠 가부시키가이샤 Butyrolactone compound, and production method
KR20160090451A (en) * 2015-01-21 2016-08-01 삼성디스플레이 주식회사 Liquid crystal display and manufacturing method thereof
KR102352286B1 (en) 2015-02-05 2022-01-18 삼성디스플레이 주식회사 Alignment layer, liquid crystal display comprising the same and method for manufacturing liquid crystal display
CN107250902B (en) * 2015-02-06 2021-01-26 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
TWI665522B (en) * 2015-12-07 2019-07-11 奇美實業股份有限公司 Photosensitive resin composition and applications thereof
TWI639890B (en) * 2015-12-17 2018-11-01 奇美實業股份有限公司 Photosensitive resin composition and applications thereof
JP7001602B2 (en) * 2016-08-25 2022-01-19 テルモ株式会社 Hydrophilic copolymers and medical devices
TW202225227A (en) * 2020-09-25 2022-07-01 日商富士軟片股份有限公司 Resin composition, cured product, laminate, cured product production method, and semiconductor device

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1124515C (en) * 1997-12-02 2003-10-15 日产化学工业株式会社 Liquid crystal aligning agent
JP3849138B2 (en) * 2002-02-18 2006-11-22 Ｊｓｒ株式会社 Liquid crystal aligning agent, method for forming liquid crystal aligning film, and liquid crystal display element
JP4039281B2 (en) * 2002-03-18 2008-01-30 チッソ株式会社 Cyclopropane compound and polymer thereof
JP4175826B2 (en) 2002-04-16 2008-11-05 シャープ株式会社 Liquid crystal display
AU2003218476A1 (en) * 2002-05-31 2003-12-19 Elsicon, Inc. Hybrid polymer materials for liquid crystal alignment layers
US7157124B2 (en) * 2003-01-06 2007-01-02 Chisso Petrochemical Corporation Polymerizable compounds and their polymers
JP4522662B2 (en) * 2003-03-31 2010-08-11 香港科技大学 Composition for liquid crystal alignment film, liquid crystal alignment film, method for producing liquid crystal alignment film, and maleimide compound
KR101261463B1 (en) 2005-04-20 2013-05-10 닛산 가가쿠 고교 가부시키 가이샤 Polymerizable liquid crystal compound, polymerizable liquid crystal composition comprising the same, and polymer produced using them
JP2007297606A (en) * 2006-03-31 2007-11-15 Dainippon Printing Co Ltd Ultraviolet-curable composition, retardation film and method for producing retardation film
JP5428336B2 (en) * 2006-07-18 2014-02-26 日産化学工業株式会社 Coating liquid, liquid crystal alignment film and liquid crystal display element using the same
JP2008050440A (en) * 2006-08-23 2008-03-06 Fujifilm Corp Polymerizable monomer, macromolecular compound, optically anisotropic film, optical compensation sheet, polarizing plate, liquid crystal display, and method for producing optical compensation sheet
US7862867B2 (en) * 2006-10-05 2011-01-04 Nissan Chemical Industries, Ltd. Bifunctional polymerizable compound, polymerizable liquid crystal composition, and oriented film
JP5212643B2 (en) * 2006-12-15 2013-06-19 日産化学工業株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal composition and alignment film
JP2009102245A (en) * 2007-10-22 2009-05-14 Adeka Corp Polymerizable compound and polymerizable composition
JP5578079B2 (en) * 2008-10-14 2014-08-27 日産化学工業株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal composition and alignment film
RU2011126148A (en) * 2008-11-27 2013-01-10 Шарп Кабусики Кайся LIQUID CRYSTAL DISPLAY DEVICE AND METHOD FOR ITS MANUFACTURE
JP5419474B2 (en) * 2009-01-14 2014-02-19 富士フイルム株式会社 Polymerizable liquid crystal composition, optically anisotropic film, optical member, and liquid crystal display element
EP2479170B1 (en) * 2009-09-16 2018-01-03 Nissan Chemical Industries, Ltd. Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and oriented film
TWI525085B (en) 2010-06-30 2016-03-11 Nissan Chemical Ind Ltd Liquid crystal alignment device, liquid crystal alignment film, liquid crystal display device, and liquid crystal display device manufacturing method

Also Published As

Publication number Publication date
CN104910106A (en) 2015-09-16
WO2012002512A1 (en) 2012-01-05
JPWO2012002512A1 (en) 2013-08-29
CN104910106B (en) 2017-08-11
JP2015222445A (en) 2015-12-10
TW201217352A (en) 2012-05-01
CN103080823B (en) 2015-09-30
TW201534594A (en) 2015-09-16
JP6108126B2 (en) 2017-04-05
KR20130038339A (en) 2013-04-17
KR101896727B1 (en) 2018-09-07
CN103080823A (en) 2013-05-01
JP5943203B2 (en) 2016-06-29

Similar Documents

Publication Publication Date Title
TWI520948B (en) A liquid crystal alignment device, a liquid crystal alignment device, a liquid crystal display device, and a liquid crystal display device, and a polymerizable compound
JP6725885B2 (en) Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device
TWI525085B (en) Liquid crystal alignment device, liquid crystal alignment film, liquid crystal display device, and liquid crystal display device manufacturing method
TWI495665B (en) Liquid crystal alignment device, liquid crystal alignment film, liquid crystal display device, and liquid crystal display device manufacturing method
KR101688687B1 (en) Liquid crystal aligning agent
TWI564339B (en) A polymerizable compound, a liquid crystal alignment device, a liquid crystal alignment film, and a liquid crystal display device, and a method of manufacturing the liquid crystal display device
TWI499615B (en) The liquid crystal alignment agent, the liquid crystal display with the film, the liquid crystal element and a method of manufacturing the liquid crystal display element
TWI464196B (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device and liquid crystal display device, and polymerizable compound
TWI476241B (en) Liquid crystal alignment device, liquid crystal display device, manufacturing method of liquid crystal display device, and polymerizable compound
TWI607265B (en) Liquid crystal alignment agent containing a crosslinkable compound having a photoreactive group
JP6666598B2 (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device
KR20160114645A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
TWI485201B (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
KR102600209B1 (en) Polyimide precursor, and liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element having precursor
TWI683857B (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element