TW201943845A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, polymer, and compound - Google Patents

Abstract

A polymer (P) having structural units U1 derived from a compound represented by formula (1), and structural units U2 different from the structural units U1, the structural units U2 being derived from a compound having a partial structure represented by formula (2), formula (3), formula (4), or formula (5), is contained in a liquid crystal alignment agent. G1 is a group having a crosslinkable cyclic structure, a group having an aromatic condensed polycyclic structure, or a group having a nitrogen-containing heterocyclic structure. E1 is a group having a polymerizable carbon-carbon unsaturated bond, a carbon atom of the polymerizable carbon-carbon unsaturated bond being bonded via a single bond or -COO- or the like to a ring of the crosslinkable cyclic structure, aromatic condensed polycyclic structure, or nitrogen-containing heterocyclic structure of G1. (1): (E1)i-(G1)j.

Description

液晶配向劑、液晶配向膜、液晶元件、聚合體及化合物Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, polymer and compound

本揭示是有關於一種液晶配向劑、液晶配向膜、液晶元件、聚合體及化合物。
[相關申請的交叉參考]The present disclosure relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, a polymer, and a compound.
[Cross Reference to Related Applications]

本申請案基於2018年4月19日提出申請的日本專利申請編號2018-80881號，並將其記載內容引用於本申請案中。This application is based on Japanese Patent Application No. 2018-80881 filed on April 19, 2018, and the content thereof is incorporated in this application.

液晶元件用於以電視機或個人電腦、智慧型電話等顯示裝置為代表的各種用途中。該些液晶元件包括具有使液晶分子於一定方向上配向的功能的液晶配向膜。通常，液晶配向膜是藉由將使聚合體成分溶解於有機溶媒中而成的液晶配向劑塗佈於基板上，較佳為進行加熱而形成於基板上。作為液晶配向劑的聚合體成分，就機械強度或液晶配向性、與液晶的親和性優異的方面而言，廣泛使用聚醯胺酸或可溶性聚醯亞胺（例如，參照專利文獻1或專利文獻2）。
[現有技術文獻]
[專利文獻]Liquid crystal elements are used in various applications including display devices such as televisions, personal computers, and smart phones. These liquid crystal elements include a liquid crystal alignment film having a function of aligning liquid crystal molecules in a certain direction. Generally, a liquid crystal alignment film is formed by applying a liquid crystal alignment agent obtained by dissolving a polymer component in an organic solvent on a substrate, and preferably by heating it. As the polymer component of the liquid crystal alignment agent, polyamic acid or soluble polyimide is widely used in terms of excellent mechanical strength, liquid crystal alignment, and affinity with liquid crystal (for example, refer to Patent Document 1 or Patent Document) 2).
[Prior Art Literature]
[Patent Literature]

[專利文獻1]國際公開第2012/176822號
[專利文獻2]日本專利特開2017-138575號公報[Patent Document 1] International Publication No. 2012/176822
[Patent Document 2] Japanese Patent Laid-Open No. 2017-138575

[發明所欲解決之課題][Problems to be Solved by the Invention]

若液晶配向膜帶來的液晶分子的配向限制力弱，則於使液晶元件長時間動作的情況下，初始配向的方向會偏離液晶元件製造最初的方向，有時會產生被稱為交流（alternating current，AC）殘像的燒印。尤其是，於藉由光配向處理而獲得液晶配向膜的情況下，與摩擦處理相比，液晶分子的配向限制力並不充分，存在容易產生AC殘像的傾向。作為液晶元件，為了滿足近年來的進一步的高性能化的要求，除了充分減少AC殘像以外，還期望作為液晶元件的基本特性的電特性優異（電壓保持率高）。If the alignment restriction force of the liquid crystal molecules brought by the liquid crystal alignment film is weak, when the liquid crystal element is operated for a long time, the direction of the initial alignment will deviate from the original direction of the liquid crystal element manufacturing, and sometimes called alternating current (alternating). current, AC) Burning of afterimages. In particular, when a liquid crystal alignment film is obtained by a photo-alignment process, compared with the rubbing process, the alignment restraining force of liquid crystal molecules is insufficient, and an AC afterimage tends to be easily generated. As a liquid crystal element, in order to meet the demand for further higher performance in recent years, in addition to sufficiently reducing AC afterimages, it is also desired that the basic characteristics of the liquid crystal element be excellent in electrical characteristics (high voltage retention rate).

本揭示是鑒於所述情況而成，其目的之一在於提供一種可獲得顯示出高的電壓保持率且AC殘像經減少的液晶元件的液晶配向劑。
[解決課題之手段]This disclosure is made in view of the said situation, and one of the objective is to provide the liquid crystal aligning agent which can obtain the liquid crystal element which shows a high voltage holding ratio and reduced AC afterimage.
[Means for solving problems]

根據本揭示而提供以下的方法。
[1] 一種液晶配向劑，其含有聚合體（P），所述聚合體（P）具有：結構單元U1，源自下述式（1）所表示的化合物；以及結構單元U2，為源自具有下述式（2）、式（3）、式（4）或式（5）所表示的部分結構的化合物的結構單元，且與所述結構單元U1不同：

(E¹ )_i -(G¹ )_j …（1）

（式（1）中，G¹ 為具有顯示出交聯性的環狀結構的基、具有芳香族縮合多環結構的基、或具有含氮雜環結構的基；E¹ 為具有聚合性碳-碳不飽和鍵的基，形成聚合性碳-碳不飽和鍵的至少一個碳原子與G¹ 所具有的顯示出交聯性的環狀結構、芳香族縮合多環結構或含氮雜環結構的環藉由單鍵而鍵結，或經由**-COO-、**-CONR⁵⁰ -、**-CH₂ -CONR⁵⁰ -、-O-或伸苯基（其中，「**」表示與形成聚合性碳-碳不飽和鍵的碳原子鍵結的鍵結鍵）而鍵結；R⁵⁰ 為氫原子，或表示R⁵⁰ 與其他基鍵結而構成的環結構；i及j中，其中一者為1且另一者為2，或i=j=1）
[化1]



（式（2）中，R¹ 為碳數1以上的一價有機基，R² 及R³ 分別獨立地為氫原子或甲基；式（3）中，R⁴ 為碳數1以上的一價有機基，R⁵ 為氫原子或碳數1以上的一價有機基，R⁶ 及R⁷ 分別獨立地為氫原子或甲基；式（4）中，R⁸ 為碳數1以上的一價有機基，R¹¹ 為氫原子或碳數1以上的一價有機基，R⁹ 及R¹⁰ 分別獨立地為氫原子或甲基；X¹⁰ 及X¹¹ 中的一者為單鍵，另一者為亞甲基；式（5）中，R¹² 為碳數1以上的一價有機基，R¹³ 及R¹⁴ 分別獨立地為氫原子或甲基）。
[2] 一種液晶配向膜，其是使用所述[1]的液晶配向劑而形成。
[3] 一種液晶元件，其包括所述[2]的液晶配向膜。
[4] 一種聚合體，其具有：結構單元U1，源自所述式（1）所表示的化合物；以及結構單元U2，為源自具有所述式（2）、式（3）、式（4）或式（5）所表示的部分結構的化合物的結構單元，且與所述結構單元U1不同。
[5] 一種化合物，其由下述式（6）表示，
[化2]



（式（6）中，B¹ 為下述式（7）、式（8）、式（9）或式（10）所表示的一價基，D¹ 為下述式（11）所表示的二價基，X¹ 及X² 分別獨立地為單鍵、-CO-O-、-O-CO-、-CS-O-、-O-CS-、-CO-S-、-S-CO-、-O-CH₂ -、-CH₂ -O-或碳數1～3的烷二基，A¹ 及A² 分別獨立地為經取代或未經取代的伸苯基、伸環己基或伸萘基，R¹⁸ 為碳數2～20的烷基、烷氧基、氟烷基、氟烷氧基或-R¹⁹ -Y¹ （其中，R¹⁹ 為碳數2～20的烷二基，Y¹ 為三烷基矽烷基）；m為0～2的整數，n為1～3的整數；於m為2的情況下，多個A¹ 、X¹ 分別獨立地具有所述定義；於n為2或3的情況下，多個R¹⁸ 分別獨立地具有所述定義）
[化3]



（式（7）中，R² 及R³ 分別與所述式（2）為相同含義；式（8）中，R⁵ 、R⁶ 及R⁷ 分別與所述式（3）為相同含義；式（9）中，R⁹ 、R¹⁰ 、R¹¹ 、X¹⁰ 及X¹¹ 分別與所述式（4）為相同含義；式（10）中，R¹³ 及R¹⁴ 分別與所述式（5）為相同含義；「*」表示鍵結鍵）
[化4]



（式（11）中，A³ 、A⁴ 及A⁵ 分別獨立地為經取代或未經取代的伸苯基或伸環己基，L¹ 及L² 分別獨立地為單鍵、碳數1～5的烷二基、或所述烷二基的至少一個亞甲基經「-O-」取代的基（其中，氧原子並不連續），X³ 及X⁴ 分別獨立地為-CO-O-、-O-CO-、-CS-O-、-O-CS-、-CO-S-、-S-CO-或-O-，R¹⁶ 及R¹⁷ 分別獨立地為氫原子、甲基、鹵素原子或氰基；k及r分別獨立地為0或1；「*¹ 」及「*² 」表示鍵結鍵；其中，包含「*¹ 」與B¹ 鍵結的情況、以及「*² 」與B¹ 鍵結的情況）。
[發明的效果]The following methods are provided according to the present disclosure.
[1] A liquid crystal alignment agent comprising a polymer (P), the polymer (P) having: a structural unit U1 derived from a compound represented by the following formula (1); and a structural unit U2 derived from A structural unit of a compound having a partial structure represented by the following formula (2), formula (3), formula (4) or formula (5), and is different from the structural unit U1:

(E ¹ ) _i- (G ¹ ) _j … (1)

(In formula (1), G ¹ is a group having a cyclic structure exhibiting crosslinkability, a group having an aromatic condensation polycyclic structure, or a group having a nitrogen-containing heterocyclic structure; E ¹ is a polymerizable carbon. -A carbon unsaturated bond group, at least one carbon atom forming a polymerizable carbon-carbon unsaturated bond, and a cyclic structure, an aromatic polycondensation ring structure, or a nitrogen-containing heterocyclic structure having crosslinkability with G ¹ Is bonded by a single bond, or via **-COO-, **-CONR ^50- , **-CH ₂ -CONR ^50- , -O- or phenylene (where "**" forming the polymerizable carbon - carbon atoms bonded to carbon unsaturated bond bond bond) and the bond; R & lt ⁵⁰ is a hydrogen atom, or represents a ⁵⁰ ring structure with other groups bonded constituted R; i and j, the One of them is 1 and the other is 2, or i = j = 1)
[Chemical 1]



(In formula (2), R ¹ is a monovalent organic group having a carbon number of 1 or more, and R ² and R ³ are each independently a hydrogen atom or a methyl group; in formula (3), R ⁴ is a one having a carbon number of 1 or more Valent organic group, R ⁵ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group; in the formula (4), R ⁸ is a group having a carbon number of 1 or more Valent organic group, R ¹¹ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group; one of X ¹⁰ and X ¹¹ is a single bond, and the other Is methylene; in formula (5), R ¹² is a monovalent organic group having 1 or more carbon atoms, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group).
[2] A liquid crystal alignment film formed using the liquid crystal alignment agent of [1].
[3] A liquid crystal element including the liquid crystal alignment film of [2].
[4] A polymer having: a structural unit U1 derived from the compound represented by the formula (1); and a structural unit U2 derived from the formula (2), the formula (3), and the formula ( 4) or a structural unit of a partial structure compound represented by formula (5), which is different from the structural unit U1.
[5] a compound represented by the following formula (6),
[Chemical 2]



(In formula (6), B ¹ is a monovalent group represented by the following formula (7), (8), (9), or (10), and D ¹ is represented by the following formula (11) Divalent base, X ¹ and X ² are each independently a single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO -, -O-CH _2- , -CH ₂ -O- or an alkanediyl group having 1 to 3 carbon atoms, and A ¹ and A ² are each independently substituted or unsubstituted phenylene, cyclohexyl or Naphthyl, R ¹⁸ is an alkyl group, alkoxy group, fluoroalkyl group, fluoroalkoxy group, or -R ¹⁹ -Y ¹ (wherein R ¹⁹ is an alkanediyl group having 2 to 20 carbon atoms) , Y ¹ is a trialkylsilyl group); m is an integer of 0 to 2 and n is an integer of 1 to 3; when m is 2, a plurality of A ¹ and X ¹ each independently have the definition; In the case where n is 2 or 3, a plurality of R ¹⁸ each independently have the definition)
[Chemical 3]



(In formula (7), R ² and R ³ have the same meanings as the formula (2); in formula (8), R ⁵ , R ^6, and R ⁷ have the same meanings as the formula (3); In the formula (9), R ⁹ , R ¹⁰ , R ¹¹ , X ¹⁰ and X ¹¹ have the same meanings as the formula (4); in the formula (10), R ¹³ and R ¹⁴ are respectively the same as the formula (5) ) Have the same meaning; "*" means bond key)
[Chemical 4]



(In formula (11), A ³ , A ^4, and A ⁵ are each independently substituted or unsubstituted phenylene or cyclohexyl, and L ¹ and L ² are each independently a single bond and a carbon number of 1 to 5 alkanediyl, or at least one methylene group of said alkanediyl substituted with "-O-" (wherein the oxygen atom is not continuous), X ³ and X ⁴ are each independently -CO-O -, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO- or -O-, R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a methyl group , a halogen atom or a cyano group; K and r are independently 0 or 1; ^"1 *" and "* ^2" represents a bond bond; wherein, includes "* ^1" in the case of B ¹ bond, and "* ² ”with B ¹ ).
[Effect of the invention]

根據含有聚合體[P]的液晶配向劑，可獲得顯示出高的電壓保持率且AC殘像經減少的液晶元件。According to a liquid crystal alignment agent containing a polymer [P], a liquid crystal element can be obtained which exhibits a high voltage holding ratio and has reduced AC afterimages.

《液晶配向劑》
本揭示的液晶配向劑含有聚合體（P），所述聚合體（P）具有：結構單元U1，源自所述式（1）所表示的化合物；以及結構單元U2，為源自具有所述式（2）、式（3）、式（4）或式（5）所表示的部分結構的化合物的結構單元且與所述結構單元U1不同。以下，對本揭示的液晶配向劑中所含的成分、以及視需要而任意調配的其他成分進行說明。《Liquid crystal alignment agent》
The liquid crystal alignment agent of the present disclosure contains a polymer (P) having: a structural unit U1 derived from the compound represented by the formula (1); and a structural unit U2 derived from having the The structural unit of the compound having a partial structure represented by formula (2), formula (3), formula (4), or formula (5) is different from the structural unit U1. Hereinafter, the components contained in the liquid crystal alignment agent of the present disclosure, and other components arbitrarily blended as necessary will be described.

再者，於本說明書中，所謂「烴基」，為包含鏈狀烴基、脂環式烴基及芳香族烴基的含義。所謂「鏈狀烴基」，是指於主鏈不含環狀結構而僅由鏈狀結構構成的直鏈狀烴基及分支狀烴基。其中，可飽和亦可不飽和。所謂「脂環式烴基」，是指僅包含脂環式烴的結構作為環結構，而不包含芳香環結構的烴基。其中，無需僅由脂環式烴的結構構成，亦包含於其一部分中具有鏈狀結構者。所謂「芳香族烴基」，是指包含芳香環結構作為環結構的烴基。其中，無需僅由芳香環結構構成，亦可於其一部分中包含鏈狀結構或脂環式烴的結構。In addition, in this specification, a "hydrocarbon group" means the meaning which includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that have only a chain structure without a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it does not need to be comprised only of the structure of an alicyclic hydrocarbon, and it is also included in the part which has a chain structure. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be included in a part thereof.

＜聚合體（P）＞
·關於結構單元U1
所述式（1）中，於G¹ 為具有顯示出交聯性的環狀結構的基的情況下，該環狀結構較佳為可藉由熱或光而於相同或不同的分子間形成共價鍵的基。作為G¹ 為具有顯示出交聯性的環狀結構的基時的具體例，可列舉具有環狀醚結構、環狀(硫代)碳酸酯結構、內酯結構、內醯胺結構或噁唑啉結構的基等。環狀醚結構較佳為氧雜環丙基（1,2-環氧乙烷結構）或氧雜環丁基（1,3-環氧丙烷結構），就藉由熱或光的反應性高的方面而言，更佳為氧雜環丙基。<Polymer (P)>
· About the structural unit U1
In the formula (1), when G ¹ is a group having a cyclic structure exhibiting crosslinkability, the cyclic structure is preferably formed between the same or different molecules by heat or light. The base of a covalent bond. Specific examples when G ¹ is a group having a cyclic structure exhibiting crosslinkability include a cyclic ether structure, a cyclic (thio) carbonate structure, a lactone structure, a lactam structure, or an oxazole The base of the phospholine structure. The cyclic ether structure is preferably oxetanyl (1,2-oxirane structure) or oxetanyl (1,3-epoxypropane structure), and is highly reactive by heat or light. In this respect, oxetanyl is more preferred.

作為G¹ 為具有顯示出交聯性的環狀結構的基時的較佳的具體例，可列舉下述式（2-A-1）～式（2-A-6）分別所表示的結構。
[化5]



（式（2-A-1）～式（2-A-6）中，R⁵¹ ～R⁵⁶ 分別獨立地為一價取代基；r1、r3、r5、r7、r9及r11分別獨立地為0～2的整數，r2、r4、r6、r8及r10分別獨立地為1～5的整數；「*」表示與E¹ 中的形成聚合性碳-碳不飽和鍵的碳原子鍵結的鍵結鍵）As a preferable specific example when G ¹ is a group having a cyclic structure exhibiting crosslinkability, the structures represented by the following formulae (2-A-1) to (2-A-6) can be listed. .
[Chemical 5]



(In formulas (2-A-1) to (2-A-6), R ⁵¹ to R ⁵⁶ are each independently a monovalent substituent; r1, r3, r5, r7, r9, and r11 are each independently 0. An integer of ～ 2, r2, r4, r6, r8, and r10 are each independently an integer of 1-5; “*” represents a bond with a carbon atom forming a polymerizable carbon-carbon unsaturated bond in E ¹ key)

所述式（2-A-1）～式（2-A-6）中，作為R⁵¹ ～R⁵⁶ 的具體例，可列舉：甲基、乙基、鹵素原子（例如，氟原子、氯原子、溴原子、碘原子等）等。r1、r3、r5、r7、r9及r11較佳為0或1，更佳為0。Specific examples of R ⁵¹ to R ⁵⁶ in the formulae (2-A-1) to (2-A-6) include a methyl group, an ethyl group, and a halogen atom (for example, a fluorine atom and a chlorine atom). , Bromine atom, iodine atom, etc.). r1, r3, r5, r7, r9, and r11 are preferably 0 or 1, and more preferably 0.

作為芳香族縮合多環結構，例如可列舉：萘環、蒽環、芴環等芳香族烴環；萘醌環、蒽醌環、喹啉環、喹唑啉環、苯并咪唑環、吲哚環等芳香族雜環、或於該些環的環部分導入有取代基的結構等。作為取代基，例如可列舉：甲基、乙基、鹵素原子、羧基、經保護的羧基、胺基、經保護的胺基等。該些中，芳香族縮合多環結構較佳為具有萘環、芴環、蒽環、萘醌環或蒽醌環的結構，更佳為具有萘環或蒽環的結構。Examples of the aromatic condensed polycyclic structure include aromatic hydrocarbon rings such as naphthalene ring, anthracene ring, and fluorene ring; naphthoquinone ring, anthraquinone ring, quinoline ring, quinazoline ring, benzimidazole ring, and indole An aromatic heterocyclic ring such as a ring, or a structure in which a substituent is introduced into a ring portion of these rings. Examples of the substituent include a methyl group, an ethyl group, a halogen atom, a carboxyl group, a protected carboxyl group, an amine group, and a protected amine group. Among these, the aromatic condensed polycyclic structure is preferably a structure having a naphthalene ring, a fluorene ring, an anthracene ring, a naphthoquinone ring, or an anthraquinone ring, and more preferably a structure having a naphthalene ring or an anthracene ring.

作為含氮雜環結構，可為單環亦可為縮合環，例如可列舉：吡咯、咪唑、吡唑、***、吡啶、嘧啶、噠嗪、吡嗪、吲哚、苯并咪唑、1H-吡咯并[2,3-b]吡啶、嘌呤、喹啉、異喹啉、萘啶、吩嗪、喹噁啉、酞嗪、三嗪、咔唑、吖啶、哌啶、哌嗪、吡咯啶、嗎啉、六亞甲基亞胺、噁唑、異噁唑、4,5-二氫噁唑、4,5-二氫苯并噁唑、二氫馬來醯亞胺、苯并馬來醯亞胺等含氮雜環、以及於該含氮雜環中導入有取代基的結構等。作為該取代基，例如可列舉：碳數1～5的烷基、烷氧基等。
於G¹ 為具有含氮雜環結構的一價基的情況下，作為G¹ 的較佳的具體例，可列舉：將與吡咯、咪唑、咔唑、嘌呤、吲哚、嗎啉、苯并咪唑、二氫馬來醯亞胺或苯并馬來醯亞胺的氮原子鍵結的氫原子除去而得的基；將與吡啶、嘧啶、吡嗪、吖啶、吩嗪、喹啉、異喹啉、萘啶、異噁唑、4,5-二氫噁唑或苯并噁唑的碳原子鍵結的至少一個氫原子除去而得的基等。The nitrogen-containing heterocyclic structure may be a monocyclic ring or a condensed ring, and examples thereof include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, 1H- Pyrrolo [2,3-b] pyridine, purine, quinoline, isoquinoline, naphthyridine, phenazine, quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine , Morpholine, hexamethyleneimine, oxazole, isoxazole, 4,5-dihydrooxazole, 4,5-dihydrobenzoxazole, dihydromaleimide, benzomalay Nitrogen-containing heterocycles such as hydrazone, and structures in which a substituent is introduced into the nitrogen-containing heterocycle. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and the like.
Under a G ¹ is a monovalent group having a nitrogen-containing heterocyclic structure of the case, as preferred specific examples of G ¹ include: a pyrrole, imidazole, carbazole, purine, indole, morpholine, benzo A group obtained by removing a hydrogen atom bonded to a nitrogen atom of imidazole, dihydromaleimide or benzomaleimide; it is a group obtained by removing pyridine, pyrimidine, pyrazine, acridine, phenazine, quinoline, isopropyl A group obtained by removing at least one hydrogen atom bonded to a carbon atom of quinoline, naphthyridine, isoxazole, 4,5-dihydrooxazole, or benzoxazole, and the like.

所述式（1）中，關於E¹ 所具有的聚合性碳-碳不飽和鍵，形成該聚合性碳-碳不飽和鍵的至少一個碳原子與顯示出交聯性的環狀結構、芳香族縮合多環結構或含氮雜環結構中的環經由單鍵、**-COO-、**-CONR⁵⁰ -、**-CH₂ -CONR⁵⁰ -、-O-或伸苯基而鍵結。具體而言，E¹ 較佳為下述式（e-1）～式（e-11）分別所表示的基的任一者。
[化6]



（式（e-1）～式（e-11）中，R²⁰ ～R³⁴ 、R³⁶ ～R⁴⁰ 、R⁴² 、R⁴³ 及R⁴⁵ ～R⁴⁹ 分別獨立地為氫原子或甲基；R³⁵ 、R⁴¹ 及R⁴⁴ 分別獨立地為氫原子或碳數1以上的一價有機基；「*3」表示與G¹ 所具有的環的鍵結鍵，「*4」表示與R⁵⁰ 的鍵結鍵）In the formula (1), regarding the polymerizable carbon-carbon unsaturated bond of E ¹ , at least one carbon atom forming the polymerizable carbon-carbon unsaturated bond, and a cyclic structure and aromaticity exhibiting crosslinkability. The rings in the group condensed polycyclic structure or nitrogen-containing heterocyclic structure are bonded via a single bond, **-COO-, **-CONR ^50- , **-CH ₂ -CONR ^50- , -O-, or phenylene Knot. Specifically, E ^{1 is} preferably any one of the groups represented by the following formulae (e-1) to (e-11).
[Chemical 6]



(In formulae (e-1) to (e-11), R ²⁰ to R ³⁴ , R ³⁶ to R ⁴⁰ , R ⁴² , R ⁴³ and R ⁴⁵ to R ⁴⁹ are each independently a hydrogen atom or a methyl group; R ³⁵ , R ⁴¹ and R ⁴⁴ are each independently a hydrogen atom or a monovalent organic group having a carbon number of 1 or more; "* 3" represents a bond with a ring of G ¹ and "* 4" represents a bond with R ⁵⁰ Knot key)

作為R³⁵ 、R⁴¹ 、R⁴⁴ 為一價有機基時的具體例，可列舉：碳數1～30的一價烴基，該烴基的至少一個亞甲基經-O-、-CO-、-COO-或-NR⁶⁰ -（其中，R⁶⁰ 為氫原子或一價烴基。以下相同）取代的基（以下，亦稱為「基α」），碳數1～30的一價烴基或基α的至少一個氫原子經鹵素原子取代的基等。R³⁶ 、R⁴² 較佳為氫原子或碳數1～10的烷基，更佳為氫原子或碳數1～3的烷基。
就可進一步提高所獲得的液晶元件的電壓保持率的方面、可進一步減少AC殘像的方面、及單體的選擇自由度高的方面而言，所述中，E¹ 較佳為所述式（e-1）～式（e-4）分別所表示的基的任一者，更佳為所述式（e-1）～式（e-3）分別所表示的基的任一者。
i及j較佳為均為1。Specific examples when R ³⁵ , R ⁴¹ , and R ⁴⁴ are monovalent organic groups include a monovalent hydrocarbon group having 1 to 30 carbon atoms, and at least one methylene group of the hydrocarbon group is -O-, -CO-,- COO- or -NR ^60- (wherein R ⁶⁰ is a hydrogen atom or a monovalent hydrocarbon group. The same applies hereinafter), a substituted group (hereinafter, also referred to as "group α"), a monovalent hydrocarbon group or group α having 1 to 30 carbon atoms At least one hydrogen atom is substituted with a halogen atom and the like. R ³⁶ and R ^{42 are} preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
Among the aspects in which the voltage retention of the obtained liquid crystal element can be further improved, the AC residual image can be further reduced, and the degree of freedom in selecting the monomer is high, among the above, E ^{1 is} preferably the formula Any one of the groups represented by (e-1) to formula (e-4) is more preferably any one of the groups represented by the formula (e-1) to (e-3).
Both i and j are preferably 1.

關於所述式（1）所表示的化合物的具體例，作為G¹ 為具有顯示出交聯性的環狀結構的基的化合物（以下，亦稱為「化合物（G-1）」），例如可列舉下述式（1-1-1）～式（1-1-18）分別所表示的化合物、下述式（1-3-11）所表示的化合物等；作為G¹ 為具有芳香族縮合多環結構的基的化合物（以下，亦稱為「化合物（G-2）」），例如可列舉下述式（1-2-1）～式（1-2-19）分別所表示的化合物等；作為G¹ 為具有含氮雜環結構的基的化合物（以下，亦稱為「化合物（G-3）」），例如可列舉下述式（1-3-1）～式（1-3-18）、式（1-1-10）、式（1-1-11）、式（1-2-8）及式（1-2-9）分別所表示的化合物等。再者，聚合體（P）可具有源自該些中的一種化合物的結構單元，亦可具有源自兩種以上的化合物的結構單元。
[化7]



[化8]



[化9]



（式中，R為氫原子或甲基）As a specific example of the compound represented by the formula (1), as a compound in which G ¹ is a group having a cyclic structure exhibiting crosslinkability (hereinafter, also referred to as “compound (G-1)”), for example, Examples thereof include compounds represented by the following formulae (1-1-1) to (1-1-18), compounds represented by the following formula (1-3-11), and the like; G ¹ is an aromatic compound. A compound (hereinafter, also referred to as a "compound (G-2)") having a condensed polycyclic structure group includes, for example, those represented by the following formulae (1-2-1) to (1-2-19) Compounds and the like; as compounds in which G ¹ is a group having a nitrogen-containing heterocyclic structure (hereinafter, also referred to as "compound (G-3)"), for example, the following formulae (1-3-1) to (1) -3-18), compounds represented by formula (1-1-10), formula (1-1-11), formula (1-2-8), and formula (1-2-9), and the like. The polymer (P) may have a structural unit derived from one kind of these compounds, or may have a structural unit derived from two or more kinds of compounds.
[Chemical 7]



[Chemical 8]



[Chemical 9]



(Where R is a hydrogen atom or a methyl group)

聚合體（P）可具有源自化合物（G-1）的結構單元、源自化合物（G-2）的結構單元、以及源自化合物（G-3）的結構單元中的僅一種作為結構單元U1，亦可具有該些中的兩種以上作為結構單元U1。另外，聚合體（P）亦可具有源自化合物（G-1）的結構單元與源自化合物（G-2）的結構單元以及源自化合物（G-3）的結構單元。
就充分獲得電壓保持率的提高效果及AC殘像的減少效果的觀點而言，相對於聚合體（P）所具有的源自單體的結構單元的總量，聚合體（P）中的結構單元U1的含有比例較佳為設為1莫耳%以上，更佳為設為3莫耳%～60莫耳%，進而佳為設為4莫耳%～50莫耳%。The polymer (P) may have only one of the structural unit derived from the compound (G-1), the structural unit derived from the compound (G-2), and the structural unit derived from the compound (G-3) as the structural unit. U1 may have two or more of these as the structural unit U1. The polymer (P) may have a structural unit derived from the compound (G-1), a structural unit derived from the compound (G-2), and a structural unit derived from the compound (G-3).
From the viewpoint of sufficiently obtaining the effect of improving the voltage holding ratio and the effect of reducing the afterimage of AC, the structure in the polymer (P) is larger than the total amount of the structural units derived from the monomer that the polymer (P) has. The content ratio of the unit U1 is preferably 1 mol% or more, more preferably 3 mol% to 60 mol%, and even more preferably 4 mol% to 50 mol%.

·關於結構單元U2
所述式（2）～式（5）中，關於R⁵ 及R¹¹ 的一價有機基的具體例，可應用所述式（e-6）的R³⁵ 及式（e-8）的R⁴¹ 的一價有機基的說明。
作為R¹ 、R⁴ 、R⁸ 及R¹² 的一價有機基，例如可列舉：碳數1～30的一價烴基、該烴基的至少一個亞甲基經-O-、-CO-、-COO-或-NR⁶⁰ -取代的基α、碳數1～30的一價烴基或基α的至少一個氫原子經鹵素原子取代的基、具有光配向性基的一價基、具有交聯性基的基等。
藉由對使用聚合體（P）形成的有機膜照射偏光或非偏光的放射線而對膜賦予各向異性，藉此可控制液晶的配向，就該方面而言，聚合體（P）所具有的結構單元U2的至少一部分較佳為具有光配向性基。所述情況下，聚合體（P）具有R¹ 、R⁴ 或R⁸ 為具有光配向性基的一價基的結構單元作為結構單元U2。· About the structural unit U2
In the formulae (2) to (5), as specific examples of the monovalent organic group of R ⁵ and R ¹¹ , R ^{35 of} the formula (e-6) and R of the formula (e-8) can be applied. Explanation of the monovalent organic group of ⁴¹ .
Examples of the monovalent organic group of R ¹ , R ⁴ , R ⁸ and R ¹² include a monovalent hydrocarbon group having 1 to 30 carbon atoms, and at least one methylene group of the hydrocarbon group is -O-, -CO-,- COO- or -NR ⁶⁰ -substituted group α, a monovalent hydrocarbon group having 1 to 30 carbon atoms or a group in which at least one hydrogen atom of a group α is substituted with a halogen atom, a monovalent group having a photo-alignment group, and a crosslinkability Base, etc.
An organic film formed using a polymer (P) is irradiated with polarized or unpolarized radiation to impart anisotropy to the film, thereby controlling the alignment of the liquid crystal. In this respect, the polymer (P) has At least a part of the structural unit U2 preferably has a photo-alignment group. In this case, the polymer (P) has a structural unit in which R ¹ , R ^4, or R ⁸ is a monovalent group having a photo-alignment group as the structural unit U 2.

光配向性基較佳為藉由利用光照射的光異構化反應、光二聚化反應、光致弗里斯重排（photo Fries rearrangement）反應或光分解反應而可對膜賦予各向異性的官能基。作為光配向性基的具體例，可列舉：包含偶氮苯或其衍生物作為基本骨架的含偶氮苯的基、包含肉桂酸或其衍生物（肉桂酸結構）作為基本骨架的含肉桂酸結構的基、包含查耳酮或其衍生物作為基本骨架的含查耳酮的基、包含二苯甲酮或其衍生物作為基本骨架的含二苯甲酮的基、包含香豆素或其衍生物作為基本骨架的含香豆素的基、包含環丁烷或其衍生物作為基本骨架的含環丁烷的結構等。就對光的感度高的方面、或者容易導入至聚合體側鏈的方面而言，該些中，光配向性基較佳為含肉桂酸結構的基。The photo-alignment group is preferably a photo-isomerization reaction, photo-dimerization reaction, photo-Fries rearrangement reaction, or photo-decomposition reaction using light irradiation to impart anisotropic functions to the film. base. Specific examples of the photo-alignment group include an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, and a cinnamic acid containing cinnamic acid or a derivative thereof (cinnamic acid structure) as a basic skeleton. Structural group, chalcone-containing group containing chalcone or its derivative as a basic skeleton, benzophenone-containing group containing benzophenone or its derivative as a basic skeleton, coumarin or its A coumarin-containing group having a basic skeleton as a derivative, a cyclobutane-containing structure including cyclobutane or a derivative thereof as a basic skeleton, and the like. In terms of high sensitivity to light or easy introduction into a polymer side chain, among these, the photo-alignment group is preferably a group containing a cinnamic acid structure.

聚合體（P）較佳為具有源自下述式（6）所表示的化合物（以下，亦稱為「特定單體」）的結構單元作為結構單元U2。
[化10]



（式（6）中，B¹ 為下述式（7）、式（8）、式（9）或式（10）所表示的一價基，D¹ 為下述式（11）所表示的二價基，X¹ 及X² 分別獨立地為單鍵、-CO-O-、-O-CO-、-CS-O-、-O-CS-、-CO-S-、-S-CO-、-O-CH₂ -、-CH₂ -O-或碳數1～3的烷二基，A¹ 及A² 分別獨立地為經取代或未經取代的伸苯基、伸環己基或伸萘基，R¹⁸ 為碳數2～20的烷基、烷氧基、氟烷基、氟烷氧基或-R¹⁹ -Y¹ （其中，R¹⁹ 為碳數2～20的烷二基，Y¹ 為三烷基矽烷基）；m為0～2的整數，n為1～3的整數；於m為2的情況下，多個A¹ 、X¹ 分別獨立地具有所述定義；於n為2或3的情況下，多個R¹⁸ 分別獨立地具有所述定義）
[化11]



（式（7）中，R² 及R³ 分別與所述式（2）為相同含義；式（8）中，R⁵ 、R⁶ 及R⁷ 分別與所述式（3）為相同含義；式（9）中，R⁹ 、R¹⁰ 、R¹¹ 、X¹⁰ 及X¹¹ 分別與所述式（4）為相同含義；式（10）中，R¹³ 及R¹⁴ 分別與所述式（5）為相同含義；「*」表示鍵結鍵）
[化12]



（式（11）中，A³ 、A⁴ 及A⁵ 分別獨立地為經取代或未經取代的伸苯基或伸環己基，L¹ 及L² 分別獨立地為單鍵、碳數1～5的烷二基、或該烷二基的至少一個亞甲基經「-O-」取代的基（其中，氧原子並不連續），X³ 及X⁴ 分別獨立地為-CO-O-、-O-CO-、-CS-O-、-O-CS-、-CO-S-、-S-CO-或-O-，R¹⁶ 及R¹⁷ 分別獨立地為氫原子、甲基、鹵素原子或氰基；k及r分別獨立地為0或1；「*¹ 」及「*² 」表示鍵結鍵；其中，包含「*¹ 」與B¹ 鍵結的情況、以及「*² 」與B¹ 鍵結的情況）。The polymer (P) preferably has a structural unit derived from a compound represented by the following formula (6) (hereinafter, also referred to as a “specific monomer”) as the structural unit U2.
[Chemical 10]



(In formula (6), B ¹ is a monovalent group represented by the following formula (7), (8), (9), or (10), and D ¹ is represented by the following formula (11) Divalent base, X ¹ and X ² are each independently a single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO -, -O-CH _2- , -CH ₂ -O- or an alkanediyl group having 1 to 3 carbon atoms, and A ¹ and A ² are each independently substituted or unsubstituted phenylene, cyclohexyl or Naphthyl, R ¹⁸ is an alkyl group, alkoxy group, fluoroalkyl group, fluoroalkoxy group, or -R ¹⁹ -Y ¹ (wherein R ¹⁹ is an alkanediyl group having 2 to 20 carbon atoms) , Y ¹ is a trialkylsilyl group); m is an integer of 0 to 2 and n is an integer of 1 to 3; when m is 2, a plurality of A ¹ and X ¹ each independently have the definition; In the case where n is 2 or 3, a plurality of R ¹⁸ each independently have the definition)
[Chemical 11]



(In formula (7), R ² and R ³ have the same meanings as the formula (2); in formula (8), R ⁵ , R ^6, and R ⁷ have the same meanings as the formula (3); In the formula (9), R ⁹ , R ¹⁰ , R ¹¹ , X ¹⁰ and X ¹¹ have the same meanings as the formula (4); in the formula (10), R ¹³ and R ¹⁴ are respectively the same as the formula (5) ) Have the same meaning; "*" means bond key)
[Chemical 12]



(In formula (11), A ³ , A ^4, and A ⁵ are each independently substituted or unsubstituted phenylene or cyclohexyl, and L ¹ and L ² are each independently a single bond and a carbon number of 1 to 5, and at least one methylene group of the alkanediyl group is substituted with "-O-" (wherein the oxygen atom is not continuous), and X ³ and X ⁴ are each independently -CO-O- , -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO- or -O-, R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a methyl group, a halogen atom or a cyano group; K and r are independently 0 or 1; ^"1 *" and "* ^2" represents a bond bond; wherein the case comprises a "* ^1" and B ¹ is bonded, and "* ² ”To B ¹ ).

所述式（6）中，就容易進行聚合反應且獲得分子量充分大的聚合體的觀點而言，B¹ 較佳為所述式（7）、式（8）或式（9）所表示的基，特佳為所述式（7）或式（8）所表示的基。所述式（9）中，包含下述式（9-1）及式（9-2）。
[化13]



（式（9-1）及式（9-2）中，R⁹ 、R¹⁰ 、R¹¹ 、X¹⁰ 及X¹¹ 分別與所述式（4）為相同含義；「*」表示鍵結鍵）
就可進一步提高所獲得的液晶元件的電壓保持率的改善效果的方面而言，X¹ 及X² 較佳為單鍵、-CO-O-、-O-CO-、-O-或碳數1～3的烷二基，更佳為單鍵、-CO-O-或-O-CO-。於A¹ 及A² 具有取代基的情況下，作為該取代基，例如可列舉：甲基、乙基、鹵素原子（例如，氟原子、氯原子、溴原子、碘原子等）。作為R¹⁶ 及R¹⁷ 為鹵素原子時的具體例，可列舉：氟原子、氯原子、溴原子及碘原子。R¹⁶ 及R¹⁷ 較佳為氫原子。In the formula (6), B ^{1 is} preferably represented by the formula (7), the formula (8), or the formula (9) from the viewpoint that a polymerization reaction is easily performed and a polymer having a sufficiently large molecular weight is obtained. The base is particularly preferably a base represented by the formula (7) or (8). The formula (9) includes the following formulas (9-1) and (9-2).
[Chemical 13]



(In formulas (9-1) and (9-2), R ⁹ , R ¹⁰ , R ¹¹ , X ¹⁰ and X ¹¹ have the same meaning as the formula (4), respectively; “*” represents a bond bond)
In terms of further improving the effect of improving the voltage retention of the obtained liquid crystal element, X ¹ and X ^{2 are} preferably a single bond, -CO-O-, -O-CO-, -O-, or carbon number. The alkanediyl group of 1 to 3 is more preferably a single bond, -CO-O- or -O-CO-. When A ¹ and A ² have a substituent, examples of the substituent include a methyl group, an ethyl group, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). Specific examples when R ¹⁶ and R ¹⁷ are halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R ¹⁶ and R ^{17 are} preferably a hydrogen atom.

就可進一步減少所獲得的液晶元件的AC殘像的方面而言，m較佳為1或2。該情況下，就可進一步提高液晶元件的電特性及AC殘像特性的改善效果的方面而言，式（6）中的「-A² -X² -(A¹ -X¹ )m-」較佳為下述式（a-1）～式（a-9）分別所表示的基的任一者。該些中，更佳為下述式（a-1）～式（a-3）、及式（a-6）～式（a-8）分別所表示的基，進而佳為下述式（a-1）、式（a-7）及式（a-8）分別所表示的基，特佳為下述式（a-1）及式（a-8）分別所表示的基。
[化14]



（式中，「*⁵ 」表示與R¹⁸ 鍵結的鍵結鍵，「*⁶ 」表示與B¹ 鍵結的鍵結鍵）From the viewpoint that the AC afterimage of the obtained liquid crystal element can be further reduced, m is preferably 1 or 2. In this case, in terms of improving the electric characteristics of the liquid crystal element and the improvement effect of the AC afterimage characteristics, "-A ² -X ^2- (A ¹ -X ¹ ) m-" in the formula (6) Any of the groups represented by the following formulae (a-1) to (a-9) is preferable. Among these, the groups represented by the following formulae (a-1) to (a-3) and (a-6) to (a-8) are more preferable, and the following formulas (a The groups represented by a-1), formula (a-7), and formula (a-8) are each particularly preferably the groups represented by the following formula (a-1) and formula (a-8).
[Chemical 14]



(In the formula, “* ⁵ ” represents a bond bond with R ¹⁸ , and “* ⁶ ” represents a bond bond with B ¹ )

R¹⁸ 的烷基、烷氧基、氟烷基、氟烷氧基及-R¹⁹ -Y¹ 可為直鏈狀亦可為分支狀，較佳為直鏈狀。就可進一步提高液晶元件的電壓保持率的提高及AC殘像的減少的效果的方面而言，R¹⁸ 較佳為氟烷基、氟烷氧基或-R¹⁹ -Y¹ ，更佳為氟烷基或氟烷氧基，特佳為「-R⁶¹ -Y² 」所表示的基（其中，R⁶¹ 為烷二基，Y² 為全氟烷基，R⁶¹ 與Y² 的合計碳數為2以上）。n較佳為1或2。於R¹⁸ 為烷基、烷氧基、氟烷基或氟烷氧基的情況下，R¹⁸ 的碳數較佳為3以上，更佳為4以上。R ^{18 is} alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, and -R ¹⁹ -Y ¹ may be straight chain may also be branched, preferably linear. From the viewpoint of further improving the effect of improving the voltage holding ratio of the liquid crystal element and reducing the afterimage of AC, R ^{18 is} preferably a fluoroalkyl group, a fluoroalkoxy group, or -R ¹⁹ -Y ¹ , and more preferably a fluorine group. Alkyl or fluoroalkoxy, particularly preferably the group represented by "-R ⁶¹ -Y ² " (wherein R ⁶¹ is an alkyldiyl group, Y ² is a perfluoroalkyl group, and the total carbon number of R ⁶¹ and Y ² Is 2 or more). n is preferably 1 or 2. When R ¹⁸ is an alkyl group, an alkoxy group, a fluoroalkyl group or a fluoroalkoxy group, the carbon number of R ¹⁸ is preferably 3 or more, and more preferably 4 or more.

就可進一步提高所獲得的液晶元件的電特性及AC殘像減少的改善效果的方面而言，所述式（6）所表示的化合物較佳為具有下述式（b-1）所表示的基。再者，式（b-1）中的「R⁸⁰ -(CF₂ )_a1 -(CH₂ )_a2 -X⁵ -」對應於式（6）的R¹⁸ 。
[化15]



（式（b-1）中，A⁶ 、A⁷ 及A⁸ 分別獨立地為經取代或未經取代1,4-伸環己基或1,4-伸苯基，X⁵ 為單鍵或氧原子，R⁸⁰ 為氟甲基或甲基，a1為0～2的整數，a2為1～20的整數，a3為0或1；其中，於R⁸⁰ 為甲基的情況下，a1=0；「*」表示鍵結鍵）The compound represented by the formula (6) is preferably one having the following formula (b-1) in terms of further improving the electrical characteristics of the obtained liquid crystal element and the effect of improving the reduction of AC afterimages. base. Furthermore, "R ^80- (CF ₂ ) _a1- (CH ₂ ) _a2 -X ^5- " in formula (b-1) corresponds to R ¹⁸ in formula (6).
[Chemical 15]



(In formula (b-1), A ⁶ , A ⁷ and A ⁸ are each independently substituted or unsubstituted 1,4-cyclohexyl or 1,4-phenylene, and X ⁵ is a single bond or oxygen Atom, R ⁸⁰ is fluoromethyl or methyl, a1 is an integer of 0 to 2, a2 is an integer of 1 to 20, and a3 is 0 or 1; where R ⁸⁰ is a methyl group, a1 = 0; "*" Means bond key)

所述式（b-1）中，就可進一步提高AC殘像的減少效果及電壓保持率的方面而言，A⁶ 較佳為經取代或未經取代的1,4-伸環己基，特佳為1,4-伸環己基。
於a3為0的情況下，A⁸ 較佳為1,4-伸環己基，於a3為1的情況下，A⁸ 較佳為1,4-伸苯基，更佳為A⁷ 為1,4-伸環己基，A⁸ 為1,4-伸苯基。
作為A⁶ ～A⁸ 可具有的取代基，例如可列舉：甲基、乙基、鹵素原子（氟原子、氯原子、溴原子、碘原子等）。a1較佳為0或1。a2較佳為2以上。就合成或獲得的容易性的方面而言，a3較佳為1；就殘像特性的改善效果高的方面而言，a3較佳為2。就可進一步提高液晶元件的電特性及AC殘像減少的改善效果的方面而言，R⁸⁰ 較佳為三氟甲基。In the formula (b-1), A ^{6 is} preferably a substituted or unsubstituted 1,4-cyclohexyl group, in terms of further improving the reduction effect of the AC afterimage and the voltage retention rate. It is preferably 1,4-cyclohexyl.
When a3 is 0, A ^{8 is} preferably 1,4-cyclohexyl, and when a3 is 1, A ^{8 is} preferably 1,4-phenylene, and more preferably A ⁷ is 1, 4-hexylcyclohexyl, A ⁸ is 1,4-phenylene.
Examples of the substituent that A ⁶ to A ⁸ may have include a methyl group, an ethyl group, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). a1 is preferably 0 or 1. a2 is preferably 2 or more. In terms of ease of synthesis or acquisition, a3 is preferably 1; in terms of high effect of improving afterimage characteristics, a3 is preferably 2. R ^{80 is} preferably a trifluoromethyl group in terms of further improving the electrical characteristics of the liquid crystal element and the effect of improving the reduction of AC afterimages.

關於所述式（11），A³ 、A⁴ 及A⁵ 可具有的取代基可應用所述A¹ 及A² 的取代基的說明。
就所獲得的液晶元件的電壓保持率的提高效果更高的方面而言，X³ 及X⁴ 較佳為-CO-O-、-O-CO-、-O-或碳數1～3的烷二基，更佳為-CO-O-或-O-CO-。
於「*² 」與B¹ 鍵結的情況下，就可進一步提高AC殘像的減少效果的方面而言，L¹ 較佳為單鍵，特佳為L¹ 為單鍵且k=0，或L¹ 為單鍵且X³ 為-CO-O-或-O-CO-。就相同的理由而言，於「*¹ 」與B¹ 鍵結的情況下，在r=1時，較佳為L² 為單鍵，特佳為L² 為單鍵且X⁴ 為-CO-O-或-O-CO-。Regarding the formula (11), the substituents that A ³ , A ^4, and A ⁵ may have are the descriptions of the substituents of A ¹ and A ² .
It is preferable that X ³ and X ⁴ are -CO-O-, -O-CO-, -O-, or a carbon number of 1 to 3 in terms of the effect of improving the voltage retention of the obtained liquid crystal element. Alkyl diyl is more preferably -CO-O- or -O-CO-.
In the case of “* ² ” and B ¹ bonding, in terms of further improving the reduction effect of the AC afterimage, L ^{1 is} preferably a single bond, particularly preferably L ¹ is a single bond and k = 0, Or L ¹ is a single bond and X ³ is -CO-O- or -O-CO-. For the same reason it is, in the case where the "* ^1" and B ¹ is bonded, at r = 1, L ² is preferably a single bond, particularly preferably L ² is a single bond and X ⁴ is -CO -O- or -O-CO-.

作為特定單體的具體例，例如可列舉下述式（6-1）～式（6-41）分別所表示的化合物等。該些中，特定單體可較佳地使用式（11）中的「*² 」與B¹ 鍵結的化合物。再者，聚合體（P）可具有僅一種源自特定單體的結構單元作為結構單元U1，亦可具有兩種以上的源自特定單體的結構單元作為結構單元U1。
[化16]



[化17]



[化18]



[化19]



（式（6-1）～式（6-41）中，B¹ 與所述式（6）為相同含義；R⁶⁴ 為碳數2～20的伸烷基或氧伸烷基，b1為2～20的整數，b2為1或2）Specific examples of the specific monomer include compounds represented by the following formulae (6-1) to (6-41). Among these, as the specific monomer, a compound in which “* ² ” in Formula (11) is bonded to B ¹ can be preferably used. The polymer (P) may have only one type of structural unit derived from a specific monomer as the structural unit U1, or may have two or more types of structural units derived from a specific monomer as the structural unit U1.
[Chemical 16]



[Chemical 17]



[Chemical 18]



[Chemical 19]



(In the formulae (6-1) to (6-41), B ¹ has the same meaning as the formula (6); R ⁶⁴ is an alkylene or oxyalkylene group having 2 to 20 carbon atoms, and b1 is 2 An integer of -20, b2 is 1 or 2)

合成特定單體的方法並無特別限定，可藉由根據所需的化合物的分子結構將有機化學的常規方法適宜組合來合成。例如，B¹ 為所述式（7）所表示的基的化合物可藉由如下方法獲得：使含羥基的馬來醯亞胺（4-羥基苯基馬來醯亞胺、4-羥基環己基馬來醯亞胺、3-羥基苯基馬來醯亞胺、4-羥基-2-甲基苯基馬來醯亞胺、4-羥基-3-甲基苯基馬來醯亞胺等）、與具有對應的基「R¹⁸ -A² -X² -(A¹ -X¹ )m-」的肉桂酸衍生物反應。另外，B¹ 為所述式（8）所表示的基的化合物例如可藉由如下方法獲得：使「R¹⁸ -A² -X² -(A¹ -X¹ )m-D¹ -NH₂ 」所表示的胺化合物、與馬來酸酐反應。B¹ 為所述式（9）所表示的基的化合物例如可藉由如下方法獲得：使「R¹⁸ -A² -X² -(A¹ -X¹ )m-D¹ -NH₂ 」所表示的胺化合物、與衣康酸酐反應，B¹ 為所述式（10）所表示的基的化合物例如可藉由使B¹ 為所述式（9）所表示的基的化合物B¹ 中的酮部分還原而獲得。其中，特定單體的合成方法並不限定於所述方法。The method of synthesizing a specific monomer is not particularly limited, and it can be synthesized by appropriately combining conventional methods of organic chemistry according to the molecular structure of a desired compound. For example, a compound in which B ¹ is a group represented by the formula (7) can be obtained by the following method: a hydroxyl-containing maleimide (4-hydroxyphenylmaleimide, 4-hydroxycyclohexyl group) Maleimide, 3-hydroxyphenylmaleimide, 4-hydroxy-2-methylphenylmaleimide, 4-hydroxy-3-methylphenylmaleimide, etc.) And react with a cinnamic acid derivative having a corresponding group "R ¹⁸ -A ² -X ^2- (A ¹ -X ¹ ) m-". In addition, a compound in which B ¹ is a group represented by the formula (8) can be obtained, for example, by the method of "R ¹⁸ -A ² -X ^2- (A ¹ -X ¹ ) mD ¹ -NH ₂ " The amine compound shown reacts with maleic anhydride. A compound in which B ¹ is a group represented by the formula (9) can be obtained, for example, by the method represented by "R ¹⁸ -A ² -X ^2- (A ¹ -X ¹ ) mD ¹ -NH ₂ " An amine compound and a compound reacting with itaconic anhydride, in which B ¹ is a group represented by the formula (10), can be achieved by, for example, making B ¹ a ketone moiety in the compound B ¹ of the group represented by the formula (9). Obtained by reduction. However, the method for synthesizing a specific monomer is not limited to the method described above.

聚合體（P）可僅包含具有光配向性基的結構單元（以下，亦稱為「結構單元U2A」）作為結構單元U2，但亦可於包含結構單元U2A的同時包含不具有光配向性基的結構單元（以下，亦稱為「結構單元U2B」）。結構單元U2B並無特別限定，例如可列舉：N-甲基馬來醯亞胺、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、N-(4-縮水甘油基氧基苯基)馬來醯亞胺、N-縮水甘油基馬來醯亞胺、3-(2,5-二氧代-3-吡咯啉-1-基)苯甲酸、4-(2,5-二氧代-3-吡咯啉-1-基)苯甲酸、4-(2,5-二氧代-3-吡咯啉-1-基)苯甲酸甲酯、N-甲基衣康醯亞胺、N-(間甲氧基苯基)衣康醯亞胺、及該些的開環體等。The polymer (P) may include only a structural unit having a photo-alignment group (hereinafter, also referred to as a “structural unit U2A”) as the structural unit U2, but may also include a structural unit U2A without a photo-alignment group Structural unit (hereinafter also referred to as "structural unit U2B"). The structural unit U2B is not particularly limited, and examples thereof include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N- (4-glycidyl Oxyphenyl) maleimide, N-glycidylmaleimide, 3- (2,5-dioxo-3-pyrrolinolin-1-yl) benzoic acid, 4- (2, 5-Dioxo-3-pyrrolidin-1-yl) benzoic acid, 4- (2,5-dioxo-3-pyrrolidin-1-yl) benzoic acid methyl ester, N-methylitaconine Imines, N- (m-methoxyphenyl) itacantimines, and ring-openings thereof.

相對於聚合體（P）所具有的源自單體的結構單元的總量，聚合體（P）中的結構單元U2的含有比例（於具有結構單元U2A及結構單元U2B的情況下為其合計量）較佳為設為1莫耳%以上，更佳為設為3莫耳%～60莫耳%，進而佳為設為4莫耳%～40莫耳%。
就可充分獲得AC殘像的減少效果的方面而言，相對於聚合體（P）所具有的源自單體的結構單元的總量，結構單元U2A的含有比例較佳為設為1莫耳%以上，更佳為設為3莫耳%～50莫耳%，進而佳為設為4莫耳%～30莫耳%。The content ratio of the structural unit U2 in the polymer (P) with respect to the total amount of the structural units derived from the monomer (the total of the structural unit U2A and the structural unit U2B) The amount is preferably 1 mol% or more, more preferably 3 mol% to 60 mol%, and even more preferably 4 mol% to 40 mol%.
From the standpoint that the reduction effect of the AC afterimage can be sufficiently obtained, the content ratio of the structural unit U2A is preferably set to 1 mol relative to the total amount of the structural units derived from the monomer that the polymer (P) has. % Or more, more preferably 3 mol% to 50 mol%, and even more preferably 4 mol% to 30 mol%.

本揭示的液晶配向劑藉由含有具有結構單元U1及結構單元U2的聚合體而可改善電特性及AC殘像特性，為了進一步提高該特性的改善效果，聚合體（P）亦可具有結構單元U1及結構單元U2以外的其他結構單元。關於聚合體（P），作為其他結構單元，較佳為於側鏈具有下述（x1）及（x2）中的至少任一者，特佳為於側鏈具有（x1）及（x2）兩者。
（x1）氧雜環丁基及氧雜環丙基（其中，將結構單元U1所具有的氧雜環丁基及氧雜環丙基除外）的至少一者的官能基（以下，亦稱為「官能基（x1）」）
（x2）藉由加熱而與氧雜環丁基及氧雜環丙基的至少一者反應的官能基（以下，亦稱為「官能基（x2）」）The liquid crystal alignment agent of the present disclosure can improve electrical characteristics and AC afterimage characteristics by including a polymer having a structural unit U1 and a structural unit U2. In order to further improve the improvement effect of this characteristic, the polymer (P) may also have a structural unit U1 and structural units other than U2. Regarding the polymer (P), as another structural unit, it is preferable to have at least one of the following (x1) and (x2) in the side chain, and it is particularly preferable to have both (x1) and (x2) in the side chain. By.
(X1) a functional group of at least one of an oxetanyl group and an oxetanyl group (excluding the oxetanyl group and the oxetanyl group included in the structural unit U1) (hereinafter, also referred to as "Functional group (x1)")
(X2) a functional group that reacts with at least one of an oxetanyl group and an oxetanyl group by heating (hereinafter, also referred to as a "functional group (x2)")

（關於官能基（x1））
聚合體（P）具有官能基（x1）的情況就即便於降低配向膜形成時的煅燒溫度的情況下亦可獲得顯現出高的液晶配向性的液晶配向膜的方面而言較佳。作為官能基（x1），於氧雜環丁基及氧雜環丙基（以下，亦簡稱為「環氧基」）中，就反應性高的方面而言，較佳為氧雜環丙基。(About functional group (x1))
The case where the polymer (P) has a functional group (x1) is preferable in that a liquid crystal alignment film exhibiting high liquid crystal alignment can be obtained even when the firing temperature at the time of formation of the alignment film is reduced. As the functional group (x1), among oxetanyl and oxetanyl (hereinafter also simply referred to as "epoxy"), oxetanyl is preferred in terms of high reactivity. .

（關於官能基（x2））
就可更充分地發揮AC殘像的減少及高的電壓保持率的方面而言，聚合體（P）較佳為具有官能基（x2）。作為官能基（x2），例如可列舉：羧基、羥基、異氰酸酯基及胺基、以及該些各基經保護基保護而成的基、烷氧基甲基等。就可使所獲得的液晶配向劑的保存穩定性更良好、且藉由加熱而與氧雜環丁烷環及氧雜環丙烷環的反應性高的方面而言，其中，官能基（x2）較佳為選自由羧基、經保護的羧基（以下，亦稱為「保護羧基」）、胺基、以及經保護的胺基（以下，亦稱為「保護胺基」）所組成的群組中的至少一種。再者，胺基包含一級胺基、二級胺基及三級胺基。(About functional group (x2))
The polymer (P) preferably has a functional group (x2) from the viewpoint that the reduction of the AC afterimage and the high voltage holding ratio can be more fully utilized. Examples of the functional group (x2) include a carboxyl group, a hydroxyl group, an isocyanate group and an amine group, a group in which each of these groups is protected by a protecting group, an alkoxymethyl group, and the like. The functional group (x2) is one in which the storage stability of the obtained liquid crystal alignment agent can be made more favorable and the reactivity with the oxetane ring and the oxetane ring is high by heating. Preferably, it is selected from the group consisting of a carboxyl group, a protected carboxyl group (hereinafter, also referred to as a "protected carboxyl group"), an amine group, and a protected amine group (hereinafter, also referred to as a "protected amine group"). At least one. Furthermore, the amine group includes a primary amine group, a secondary amine group, and a tertiary amine group.

保護羧基只要為藉由熱而脫離並生成羧基者則並無特別限定。作為保護羧基的較佳的具體例，可列舉下述式（12）所表示的結構、羧酸的縮醛酯結構、羧酸的縮酮酯結構等。
[化20]



（式（12）中，R³¹ 、R³² 及R³³ 分別獨立地為碳數1～10的烷基或碳數3～20的一價脂環式烴基，或者R³¹ 與R³² 相互鍵結並與R³¹ 及R³² 所鍵結的碳原子一起形成碳數4～20的二價脂環式烴基或環狀醚基，且R³³ 為碳數1～10的烷基、碳數2～10的烯基或碳數6～20的芳基；「*」表示鍵結鍵）The protected carboxyl group is not particularly limited as long as it is detached by heat and generates a carboxyl group. Preferred specific examples of protecting the carboxyl group include a structure represented by the following formula (12), an acetal structure of a carboxylic acid, and a ketal structure of a carboxylic acid.
[Chemical 20]



(In formula (12), R ³¹ , R ^32, and R ³³ are each independently an alkyl group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ³¹ and R ³² are bonded to each other And together with the carbon atoms bonded by R ³¹ and R ³² to form a divalent alicyclic hydrocarbon group or cyclic ether group having 4 to 20 carbon atoms, and R ³³ is an alkyl group having 1 to 10 carbon atoms and 2 to 3 carbon atoms Alkenyl group of 10 or aryl group having 6 to 20 carbon atoms; "*" indicates a bonding bond)

保護胺基只要為藉由熱而脫離並生成一級胺基者則並無特別限定。作為保護基，例如可列舉：胺甲酸酯系保護基、醯胺系保護基、醯亞胺系保護基、磺醯胺系保護基等。該些中，就藉由熱的脫離性高的方面、及可儘可能減少源自脫離的保護基的化合物於膜中的殘存量的方面而言，特佳為第三丁氧基羰基（BOC基）。The protective amine group is not particularly limited as long as it is detached by heat to form a primary amine group. Examples of the protective group include a urethane-based protective group, a fluorenyl-based protective group, a fluorenimine-based protective group, and a sulfonamide-based protective group. Among these, a third butoxycarbonyl group (BOC) is particularly preferred in terms of its high releasability by heat, and in terms of reducing the remaining amount of the compound derived from the protecting group in the film as much as possible. base).

就可使所獲得的液晶元件的電特性更良好的方面、以及單體的選擇自由度高的方面而言，官能基（x1）及官能基（x2）較佳為藉由選自由苯乙烯系化合物及(甲基)丙烯酸系化合物所組成的群組中的至少一種來導入至聚合體（P）中。再者，於本說明書中，「(甲基)丙烯酸系化合物」是指於一分子內具有僅一個(甲基)丙烯酸基的化合物，從而與馬來醯亞胺系化合物及衣康醯亞胺系化合物加以區別。The functional group (x1) and the functional group (x2) are preferably selected from a styrene-based system in terms of making the obtained liquid crystal element more excellent in electrical characteristics and in terms of high degree of freedom in selecting monomers. At least one of the group consisting of the compound and the (meth) acrylic compound is introduced into the polymer (P). In addition, in this specification, a "(meth) acrylic compound" means a compound which has only one (meth) acrylic group in one molecule, and is compatible with a maleimide-based compound and an itaconimine System compounds are distinguished.

作為其他結構單元，於具有源自具有官能基（x1）的化合物（以下，亦稱為「化合物E1」）的結構單元的情況下，化合物E1較佳為具有下述式（13）所表示的部分結構作為具有環氧基的基。下述式（13）中的R⁷⁰ 較佳為碳數2以上。

*-R⁷⁰ -G² …（13）

（式（13）中，R⁷⁰ 為碳數1～20的烷二基或於該烷二基的碳-碳鍵間具有-O-、-COO-或-OCO-的基，G² 為氧雜環丁基、氧雜環丙基或3,4-環氧環己基；「*」表示鍵結鍵）As another structural unit, when it has the structural unit derived from the compound which has a functional group (x1) (henceforth a "compound E1"), it is preferable that the compound E1 has the following formula (13) Part of the structure serves as a group having an epoxy group. R ⁷⁰ in the following formula (13) is preferably 2 or more carbon atoms.

* -R ⁷⁰ -G ² … (13)

(In formula (13), R ⁷⁰ is an alkanediyl group having 1 to 20 carbon atoms or a group having -O-, -COO- or -OCO- between carbon-carbon bonds of the alkanediyl group, and G ² is oxygen Heterobutyl, oxepropyl, or 3,4-epoxycyclohexyl; "*" means a bond)

化合物E1、以及具有官能基（x2）的化合物（以下，亦稱為「化合物E2」）若可與形成結構單元U1的單體及形成結構單元U2的單體聚合，則並無特別限定，就容易進行聚合反應的方面及單體的選擇自由度高的方面而言，較佳為選自由所述式（e-1）、式（e-3）～式（e-7）及式（e-10）所組成的群組中的至少一種，更佳為選自由所述式（e-3）及式（e-5）～式（e-7）所組成的群組中的至少一種。The compound E1 and the compound having a functional group (x2) (hereinafter, also referred to as "compound E2") are not particularly limited as long as they can be polymerized with the monomer forming the structural unit U1 and the monomer forming the structural unit U2. It is preferable to select from the formula (e-1), the formula (e-3) to the formula (e-7), and the formula (e) in terms of easy polymerization reaction and high degree of freedom in selecting monomers. -10) is at least one selected from the group consisting of the formula (e-3) and the formula (e-5) to the formula (e-7).

作為化合物E1的具體例，苯乙烯系化合物例如可列舉：3-(縮水甘油基氧基甲基)苯乙烯、4-(縮水甘油基氧基甲基)苯乙烯、4-縮水甘油基-α-甲基苯乙烯等，
(甲基)丙烯酸系化合物例如可列舉：(甲基)丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧丁酯、α-乙基丙烯酸3,4-環氧丁酯、(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸6,7-環氧庚酯、α-乙基丙烯酸6,7-環氧庚酯、丙烯酸4-羥基丁基縮水甘油醚、(甲基)丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯等。再者，化合物E1可單獨使用該些的一種，亦可將兩種以上組合使用。Specific examples of the compound E1 include styrene-based compounds: 3- (glycidyloxymethyl) styrene, 4- (glycidyloxymethyl) styrene, 4-glycidyl-α -Methylstyrene, etc.
Examples of the (meth) acrylic compound include glycidyl (meth) acrylate, glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, glycidyl α-n-butylacrylate, ( 3,4-epoxybutyl methacrylate, 3,4-epoxybutyl α-ethyl acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 6, (meth) acrylic acid 6, 7-epoxyheptyl, α-ethylacrylic 6,7-epoxyheptyl, 4-hydroxybutyl glycidyl acrylate, (3-ethyloxetane-3-yl (meth) acrylate ) Methyl esters, etc. The compound E1 may be used alone or in combination of two or more.

作為化合物E2的具體例，苯乙烯系化合物例如可列舉：3-乙烯基苯甲酸、4-乙烯基苯甲酸、下述式（m1-1）～式（m1-4）分別所表示的化合物等，
(甲基)丙烯酸化合物例如可列舉：(甲基)丙烯酸、α-乙基丙烯酸酯、馬來酸、富馬酸、乙烯基苯甲酸、丁烯酸、檸康酸、中康酸、衣康酸、3-馬來醯亞胺苯甲酸、3-馬來醯亞胺丙酸等含羧基的化合物；下述式（m2-1）～式（m2-12）分別所表示的含保護羰基的化合物；下述式（m1-5）～式（m1-7）分別所表示的含胺基的化合物；下述式（m1-8）及式（m1-9）分別所表示的含保護胺基的化合物等。再者，於合成聚合體（P）時，化合物E2可單獨使用該些的一種或將兩種以上組合使用。
[化21]



[化22]



（式中，R¹⁵ 為氫原子或甲基）Specific examples of the compound E2 include styrene-based compounds such as 3-vinylbenzoic acid, 4-vinylbenzoic acid, compounds represented by the following formulae (m1-1) to (m1-4), and the like. ,
Examples of the (meth) acrylic compound include (meth) acrylic acid, α-ethyl acrylate, maleic acid, fumaric acid, vinylbenzoic acid, butenoic acid, citraconic acid, mesaconic acid, and itaconic acid. Carboxylic acid-containing compounds such as acids, 3-maleimide benzoic acid, and 3-maleimide iminopropionic acid; protected carbonyl-containing compounds represented by the following formulae (m2-1) to (m2-12) Compounds; amine group-containing compounds represented by the following formulae (m1-5) to (m1-7); protected amine group-containing compounds represented by the following formulas (m1-8) and (m1-9) Compounds. When synthesizing the polymer (P), the compound E2 may be used alone or in combination of two or more.
[Chemical 21]



[Chemical 22]



(Wherein R ¹⁵ is a hydrogen atom or a methyl group)

聚合體（P）中，相對於聚合體（P）所具有的源自單體的結構單元的總量，源自化合物E1的結構單元的含有比例較佳為設為2莫耳%以上，更佳為設為5莫耳%～70莫耳%，進而佳為設為10莫耳%～60莫耳%。
相對於聚合體（P）所具有的源自單體的結構單元的總量，源自化合物E2的結構單元的含有比例較佳為設為2莫耳%以上，更佳為設為3莫耳%～60莫耳%，進而佳為設為5莫耳%～50莫耳%。In the polymer (P), the content ratio of the structural unit derived from the compound E1 is preferably 2 mol% or more with respect to the total amount of the structural unit derived from the monomer which the polymer (P) has. It is preferably set to 5 mol% to 70 mol%, and further preferably set to 10 mol% to 60 mol%.
The content ratio of the structural unit derived from the compound E2 to the total amount of the structural unit derived from the monomer contained in the polymer (P) is preferably 2 mol% or more, and more preferably 3 mol. % To 60 mol%, more preferably 5 to 50 mol%.

聚合體（P）亦可具有源自不具有官能基（x1）及官能基（x2）的任一者的單體的結構單元作為其他結構單元。作為該單體，例如可列舉：(甲基)丙烯酸烷基酯、(甲基)丙烯酸環烷基酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸-2-乙基己酯等(甲基)丙烯酸系化合物；苯乙烯、甲基苯乙烯、二乙烯基苯等芳香族乙烯基化合物；1,3-丁二烯、2-甲基-1,3-丁二烯等共軛二烯化合物；馬來酸酐等。相對於聚合體（P）所具有的源自單體的結構單元的總量，源自該單體的結構單元的含有比例較佳為設為20莫耳%以下，更佳為設為10莫耳%以下，進而佳為設為3莫耳%以下。The polymer (P) may have a structural unit derived from a monomer which does not have any of the functional group (x1) and the functional group (x2) as another structural unit. Examples of the monomer include alkyl (meth) acrylate, cycloalkyl (meth) acrylate, benzyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. (Meth) acrylic compounds; aromatic vinyl compounds such as styrene, methylstyrene, and divinylbenzene; conjugates such as 1,3-butadiene and 2-methyl-1,3-butadiene Diene compounds; maleic anhydride, etc. The content ratio of the structural unit derived from the monomer to the total amount of the structural unit derived from the monomer contained in the polymer (P) is preferably 20 mol% or less, and more preferably 10 mol. The ear% is preferably 3% or less.

（聚合體（P）的合成）
合成聚合體（P）的方法並無特別限定，例如可藉由在聚合起始劑的存在下、在有機溶媒中使所述單體進行自由基聚合而獲得。作為使用的聚合起始劑，例如較佳為2,2'-偶氮雙(異丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)等偶氮化合物。相對於反應中使用的所有單體100質量份，聚合起始劑的使用比例較佳為設為0.01質量份～30質量份。作為使用的有機溶媒，例如可列舉：醇、醚、酮、醯胺、酯、烴化合物等。
所述聚合反應中，反應溫度較佳為設為30℃～120℃，反應時間較佳為設為1小時～36小時。有機溶媒的使用量（a）較佳為設為反應中使用的單體的合計量（b）相對於反應溶液的總體量（a+b）而成為0.1質量%～60質量%的量。溶解聚合體而成的反應溶液例如可使用如下公知的分離方法將反應溶液中所含的聚合體（P）分離後供於液晶配向劑的製備，所述分離方法為對將反應溶液注入大量的不良溶媒中所獲得的析出物於減壓下進行乾燥的方法、利用蒸發器將反應溶液減壓餾去的方法等。聚合體（P）的合成例如可藉由使用RAFT試劑的活性自由基聚合等來進行。(Synthesis of Polymer (P))
The method for synthesizing the polymer (P) is not particularly limited, and can be obtained, for example, by subjecting the monomer to radical polymerization in an organic solvent in the presence of a polymerization initiator. As the polymerization initiator used, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2 'are preferred. -Azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile). The use ratio of the polymerization initiator is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of all the monomers used in the reaction. Examples of the organic solvent used include alcohols, ethers, ketones, amidines, esters, and hydrocarbon compounds.
In the polymerization reaction, the reaction temperature is preferably 30 ° C. to 120 ° C., and the reaction time is preferably 1 hour to 36 hours. The amount (a) of the organic solvent used is preferably a total amount (b) of the monomers used in the reaction in an amount of 0.1 to 60% by mass based on the total amount (a + b) of the reaction solution. The reaction solution obtained by dissolving the polymer can be used for the preparation of a liquid crystal alignment agent after the polymer (P) contained in the reaction solution is separated using a known separation method, for example. A method of drying a precipitate obtained in a poor solvent under reduced pressure, a method of distilling off a reaction solution under reduced pressure using an evaporator, and the like. The polymer (P) can be synthesized, for example, by living radical polymerization using a RAFT reagent.

聚合體（P）的藉由凝膠滲透層析法（gel permeation chromatography，GPC）測定的聚苯乙烯換算的重量平均分子量（Mw）較佳為1,000～300,000，更佳為2,000～100,000。Mw與藉由GPC測定的聚苯乙烯換算的數量平均分子量（Mn）的比所表示的分子量分佈（Mw/Mn）較佳為7以下，更佳為5以下。再者，液晶配向劑的製備中使用的聚合體（P）可僅為一種，亦可組合兩種以上。The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (P) measured by gel permeation chromatography (GPC) is preferably 1,000 to 300,000, and more preferably 2,000 to 100,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 7 or less, and more preferably 5 or less. The polymer (P) used in the preparation of the liquid crystal alignment agent may be only one type, or two or more types may be combined.

就可充分獲得液晶元件的電特性及低殘像特性的改善效果的方面而言，相對於液晶配向劑中所含的聚合體成分的總量，液晶配向劑中的聚合體（P）的含有比例較佳為設為1質量%以上，更佳為設為2質量%以上，進而佳為設為3質量%以上。聚合體（P）的含有比例的上限值並無特別限制，為了充分獲得併用與聚合體（P）不同的聚合體所帶來的各種特性（例如，液晶配向性或電特性等）的改善效果、及為了實現低成本化，相對於液晶配向劑中所含的所有聚合體，較佳為將聚合體（P）的含有比例的上限值設為90質量%以下，更佳為設為60質量%以下，進而佳為設為40質量%以下。The content of the polymer (P) in the liquid crystal alignment agent is sufficient to obtain the effect of improving the electrical characteristics and low afterimage characteristics of the liquid crystal element with respect to the total amount of the polymer components contained in the liquid crystal alignment agent. The proportion is preferably 1 mass% or more, more preferably 2 mass% or more, and even more preferably 3 mass% or more. The upper limit of the content ratio of the polymer (P) is not particularly limited. In order to fully obtain the improvement of various characteristics (for example, liquid crystal alignment or electrical characteristics) brought about by using a polymer different from the polymer (P) in combination. For the effect and cost reduction, the upper limit of the content ratio of the polymer (P) is preferably set to 90% by mass or less, and more preferably to all polymers contained in the liquid crystal alignment agent. It is preferably 60% by mass or less, and more preferably 40% by mass or less.

＜其他成分＞
本揭示的液晶配向劑視需要亦可含有聚合體（P）以外的其他成分。作為其他成分，只要無損本揭示的效果，則並無特別限定，例如可列舉以下成分＜ Other ingredients ＞
The liquid crystal alignment agent of this disclosure may contain other components other than a polymer (P) as needed. The other components are not particularly limited as long as the effects of the present disclosure are not impaired, and examples thereof include the following components

（聚合體（Q））
本揭示的液晶配向劑較佳為於含有聚合體（P）的同時含有選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種聚合體（以下，亦稱為「聚合體（Q）」）。該情況下，使聚合體（P）偏向存在於上層，藉此，可藉由儘可能少量的聚合體（P）來實現聚合體（P）帶來的電特性及AC殘像特性的改善效果，就該方面而言適宜。藉由設為聚合體（P）為具有鹵素原子或矽原子的聚合體且聚合體（Q）為不具有鹵素原子及矽原子的聚合體的組合，而可容易產生相分離，就該方面而言較佳。(Aggregate (Q))
The liquid crystal alignment agent of the present disclosure preferably contains a polymer (P) and at least one polymer selected from the group consisting of polyamic acid, polyamidate, and polyimide (hereinafter, Also known as "aggregate (Q)"). In this case, the polymer (P) is biased to exist in the upper layer, whereby the effect of improving the electrical characteristics and AC afterimage characteristics brought about by the polymer (P) can be achieved with as few polymers (P) as possible. Is appropriate in this respect. When the polymer (P) is a combination of a polymer having a halogen atom or a silicon atom and the polymer (Q) is a combination of a polymer having no halogen atom and a silicon atom, phase separation can easily occur. In this respect, Speak better.

聚合體（Q）可依照現有公知的方法來合成。例如，聚醯胺酸可藉由使四羧酸二酐與二胺反應而獲得。再者，於本說明書中，「四羧酸衍生物」為包含四羧酸二酐、四羧酸二酯及四羧酸二酯二鹵化物的含義。The polymer (Q) can be synthesized according to a conventionally known method. For example, polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine. In addition, in this specification, "tetracarboxylic acid derivative" has the meaning which includes tetracarboxylic dianhydride, a tetracarboxylic-acid diester, and a tetracarboxylic-acid diester dihalide.

聚合中使用的四羧酸二酐並無特別限定，可使用各種四羧酸二酐。作為該些的具體例，可列舉：丁烷四羧酸二酐、乙二胺四乙酸二酐等脂肪族四羧酸二酐；1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、5-(2,5-二氧代四氫呋喃-3-基)-3a,4,5,9b-四氫萘并[1,2-c]呋喃-1,3-二酮、5-(2,5-二氧代四氫呋喃-3-基)-8-甲基-3a,4,5,9b-四氫萘并[1,2-c]呋喃-1,3-二酮、2,4,6,8-四羧基雙環[3.3.0]辛烷-2:4,6:8-二酐、環戊烷四羧酸二酐、環己烷四羧酸二酐等脂環式四羧酸二酐；均苯四甲酸二酐、4,4'-(六氟亞異丙基)二鄰苯二甲酸酐、對伸苯基雙(偏苯三甲酸單酯酐)、乙二醇雙(偏苯三甲酸酐酯)、1,3-丙二醇雙(偏苯三甲酸酐酯)等芳香族四羧酸二酐等，除此以外，亦可使用日本專利特開2010-97188號公報中記載的四羧酸二酐。再者，四羧酸二酐可單獨使用一種，亦可將兩種以上組合使用。The tetracarboxylic dianhydride used in the polymerization is not particularly limited, and various tetracarboxylic dianhydrides can be used. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and ethylenediaminetetraacetic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxo Tetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran-3- ) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo [3.3. 0] Cyclic dianhydride such as octane-2: 4,6: 8-dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride; pyromellitic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, p-phenylene bis (trimellitic acid monoester anhydride), ethylene glycol bis (trimellitic anhydride), 1,3 -In addition to aromatic tetracarboxylic dianhydrides such as propylene glycol bis (trimellitic anhydride), tetracarboxylic dianhydrides described in Japanese Patent Laid-Open No. 2010-97188 can also be used. In addition, tetracarboxylic dianhydride may be used individually by 1 type, and may be used in combination of 2 or more type.

作為所述聚合中使用的二胺，例如可列舉：乙二胺、四亞甲基二胺等脂肪族二胺；對環己烷二胺、4,4'-亞甲基雙(環己基胺)等脂環式二胺；十六烷氧基二胺基苯、膽甾烷基氧基二胺基苯、二胺基苯甲酸膽甾烷基酯、二胺基苯甲酸膽甾烯基酯、二胺基苯甲酸羊毛甾烷基酯、3,6-雙(4-胺基苯甲醯基氧基)膽甾烷、3,6-雙(4-胺基苯氧基)膽甾烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-丁基環己烷、2,5-二胺基-N,N-二烯丙基苯胺、下述式（2-1）～式（2-3）分別所表示的化合物等側鏈型的芳香族二胺；
[化23]

Examples of the diamine used in the polymerization include aliphatic diamines such as ethylenediamine and tetramethylenediamine; p-cyclohexanediamine and 4,4'-methylenebis (cyclohexylamine). ) And other alicyclic diamines; hexadecyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholesteryl diaminobenzoate, cholesteryl diaminobenzoate Lanosteryl diaminobenzoate, 3,6-bis (4-aminobenzyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane , 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 2,5-diamino-N, N-diallylaniline, lower The side chain-type aromatic diamines such as the compounds represented by formulae (2-1) to (2-3);
[Chemical 23]

對苯二胺、4,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基胺、4-胺基苯基-4'-胺基苯甲酸酯、4,4'-二胺基偶氮苯、3,5-二胺基苯甲酸、2,4-二胺基苯甲酸、2,5-二胺基苯甲酸、4,4'-二胺基聯苯基-3-羧酸、1,5-雙(4-胺基苯氧基)戊烷、雙[2-(4-胺基苯基)乙基]己二酸、雙(4-胺基苯基)胺、N,N-雙(4-胺基苯基)甲基胺、N,N'-雙(4-胺基苯基)-聯苯胺、2,2'-二甲基-4,4'-二胺基聯苯、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、4,4'-二胺基二苯基醚、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、4,4'-(伸苯基二亞異丙基)雙苯胺、1,4-雙(4-胺基苯氧基)苯、4-(4-胺基苯氧基羰基)-1-(4-胺基苯基)哌啶、4,4'-[4,4'-丙烷-1,3-二基雙(哌啶-1,4-二基)]二苯胺等非側鏈型的芳香族二胺；1,3-雙(3-胺基丙基)-四甲基二矽氧烷等二胺基有機矽氧烷等，除此以外，亦可使用日本專利特開2010-97188號公報中記載的二胺。再者，二胺可單獨使用一種，亦可將兩種以上組合使用。P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4-aminophenyl-4'-aminobenzoate, 4, 4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 4,4'-diaminobiphenyl 3-carboxylic acid, 1,5-bis (4-aminophenoxy) pentane, bis [2- (4-aminophenyl) ethyl] adipic acid, bis (4-aminobenzene ) Amine, N, N-bis (4-aminophenyl) methylamine, N, N'-bis (4-aminophenyl) -benzidine, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 4,4 '-(phenylene diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) Benzene, 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine, 4,4 '-[4,4'-propane-1,3-diylbis (piperidine) Pyridine-1,4-diyl)] diphenylamine and other non-side chain aromatic diamines; 1,3-bis (3-aminopropyl) -tetramethyldisilazane In addition to oxane and the like, diamines described in Japanese Patent Laid-Open No. 2010-97188 can also be used. Moreover, a diamine may be used individually by 1 type, and may be used in combination of 2 or more type.

聚醯胺酸的合成反應較佳為於有機溶媒中進行。此時的反應溫度較佳為-20℃～150℃，反應時間較佳為0.1小時～24小時。作為反應中使用的有機溶媒，例如可列舉：非質子性極性溶媒、酚系溶媒、醇、酮、酯、醚、鹵化烴、烴等。有機溶媒的使用量較佳為設為四羧酸二酐及二胺化合物的合計量相對於反應溶液的總量而成為0.1質量%～50質量%的量。The synthesis reaction of the polyamic acid is preferably performed in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and the reaction time is preferably 0.1 hour to 24 hours. Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The used amount of the organic solvent is preferably an amount of 0.1 to 50% by mass based on the total amount of the tetracarboxylic dianhydride and the diamine compound with respect to the total amount of the reaction solution.

於聚合體（Q）為聚醯胺酸酯的情況下，該聚醯胺酸酯例如可藉由如下方法等而獲得：使所述獲得的聚醯胺酸與酯化劑（例如，甲醇或乙醇、N,N-二甲基甲醯胺二乙基縮醛等）反應的方法、使四羧酸二酯與二胺化合物於適當的脫水觸媒的存在下反應的方法、使四羧酸二酯二鹵化物與二胺於適當的鹼的存在下反應的方法。In the case where the polymer (Q) is a polyamidate, the polyamidate can be obtained, for example, by a method or the like in which the polyamidoacid obtained and an esterifying agent (for example, methanol or Ethanol, N, N-dimethylformamide diethyl acetal, etc.), a method for reacting a tetracarboxylic acid diester with a diamine compound in the presence of a suitable dehydration catalyst, and a tetracarboxylic acid A method in which a diester dihalide is reacted with a diamine in the presence of a suitable base.

於聚合體（Q）為聚醯亞胺的情況下，該聚醯亞胺例如可藉由將所述獲得的聚醯胺酸脫水閉環並加以醯亞胺化而獲得。聚醯亞胺的醯亞胺化率較佳為20%～95%，更佳為30%～90%。該醯亞胺化率是以百分率來表示聚醯亞胺的醯亞胺環結構的數量相對於醯胺酸結構的數量與醯亞胺環結構的數量的合計所佔的比例。In the case where the polymer (Q) is polyimide, the polyimide can be obtained, for example, by dehydrating and closing the obtained polyamidic acid and then performing imidization. The fluorene imidization rate of the polyfluorene imine is preferably 20% to 95%, and more preferably 30% to 90%. The fluorene imidization ratio is a percentage representing the ratio of the number of fluorene imine ring structures of the polyfluorene imine to the total number of fluorene acid structures and the number of fluorene imine ring structures.

關於聚合體（Q），藉由GPC測定的聚苯乙烯換算的重量平均分子量（Mw）較佳為1,000～500,000，更佳為2,000～300,000。分子量分佈（Mw/Mn）較佳為7以下，更佳為5以下。再者，液晶配向劑中含有的聚合體（Q）可僅為一種，或者亦可組合兩種以上。Regarding the polymer (Q), the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn) is preferably 7 or less, and more preferably 5 or less. The polymer (Q) contained in the liquid crystal alignment agent may be only one kind, or two or more kinds may be combined.

於使用聚合體（P）與聚合體（Q）作為液晶配向劑的聚合體成分的情況下，就充分獲得AC殘像特性及電特性的改善效果的觀點而言，相對於液晶配向劑的製備中使用的聚合體（Q）的100質量份，聚合體（P）的調配比例較佳為設為1質量份以上。更佳為2質量份～50質量份，進而佳為5質量份～30質量份。再者，聚合體（P）及聚合體（Q）分別可單獨使用一種，亦可將兩種以上組合使用。In the case where the polymer (P) and the polymer (Q) are used as the polymer component of the liquid crystal alignment agent, from the viewpoint of sufficiently obtaining the effects of improving the afterimage characteristics and electrical characteristics, compared to the preparation of the liquid crystal alignment agent 100 parts by mass of the polymer (Q) used in the polymer, and the blending ratio of the polymer (P) is preferably 1 part by mass or more. It is more preferably 2 to 50 parts by mass, and even more preferably 5 to 30 parts by mass. The polymer (P) and the polymer (Q) may be used singly or in combination of two or more kinds.

（溶劑）
本揭示的液晶配向劑是以溶液狀組成物的形式而製備，所述溶液狀組成物是將聚合體成分及視需要而任意調配的成分較佳為溶解於有機溶媒中而成。該有機溶媒例如可列舉：非質子性極性溶媒、酚系溶媒、醇、酮、酯、醚、鹵化烴、烴等。溶劑成分可為該些的一種，亦可為兩種以上的混合溶媒。(Solvent)
The liquid crystal alignment agent of the present disclosure is prepared in the form of a solution-like composition, which is preferably obtained by dissolving a polymer component and a component arbitrarily blended as necessary in an organic solvent. Examples of the organic solvent include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The solvent component may be one of these or a mixed solvent of two or more.

作為液晶配向劑的溶劑成分，可列舉聚合體的溶解性及調平性高的溶劑（以下，亦稱為「第1溶劑）、潤濕擴展性良好的溶劑（以下，亦稱為「第2溶劑）、以及該些的混合溶劑。
作為溶劑的具體例，第1溶劑例如可列舉：N-甲基-2-吡咯啶酮、γ-丁內酯、γ-丁內醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、4-羥基-4-甲基-2-戊酮、二異丁基酮、碳酸伸乙酯、碳酸伸丙酯、N-乙基-2-吡咯啶酮、N-(正戊基)-2-吡咯啶酮、N-(第三丁基)-2-吡咯啶酮、N-甲氧基丙基-2-吡咯啶酮、1,3-二甲基-2-咪唑啶酮、3-丁氧基-N,N-二甲基丙烷醯胺、3-甲氧基-N,N-二甲基丙烷醯胺等；
第2溶劑例如可列舉：乙二醇單丁醚（丁基溶纖劑）、乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、二丙酮醇、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基***、丙二醇單甲醚、丙二醇單甲醚乙酸酯、3-甲氧基-1-丁醇、環戊酮、乳酸丁酯、乙酸丁酯、甲基甲氧基丙酸酯、乙基乙氧基丙酸酯、異戊基丙酸酯、異戊基異丁酸酯、丙二醇二乙酸酯、二丙二醇單甲基醚、丙二醇單丁醚、二異戊基醚等。再者，溶劑可單獨使用該些的一種，亦可將兩種以上混合使用。Examples of the solvent component of the liquid crystal alignment agent include solvents having high polymer solubility and leveling properties (hereinafter, also referred to as "first solvents") and solvents having good wetting and spreading properties (hereinafter, also referred to as "second Solvents), and mixed solvents.
Specific examples of the solvent include, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamidamine, 4-hydroxy-4-methyl-2-pentanone, diisobutyl ketone, ethylene carbonate, propylene carbonate, N-ethyl-2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N- (third butyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, 1,3-dimethyl -2-imidazolidinone, 3-butoxy-N, N-dimethylpropanehydrazone, 3-methoxy-N, N-dimethylpropanehydrazone, etc .;
Examples of the second solvent include ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diacetone alcohol, and diethylene glycol dimethyl ether. , Diethylene glycol diethyl ether, diethylene glycol methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, cyclopentanone, butyl lactate, butyl acetate Ester, methylmethoxypropionate, ethylethoxypropionate, isoamylpropionate, isoamylisobutyrate, propylene glycol diacetate, dipropylene glycol monomethyl ether, propylene glycol monoester Butyl ether, diisoamyl ether, etc. The solvents may be used singly or in combination of two or more kinds.

於將液晶配向劑的溶劑成分設為第1溶劑與第2溶劑的混合溶劑的情況下，相對於溶劑成分的總量，第1溶劑的含有比例較佳為設為10質量%以上，更佳為設為15質量%～85質量%。When the solvent component of the liquid crystal alignment agent is a mixed solvent of the first solvent and the second solvent, the content ratio of the first solvent relative to the total amount of the solvent component is preferably 10% by mass or more, and more preferably It is set to 15% by mass to 85% by mass.

作為液晶配向劑中所含的其他成分，除了所述以外，例如還可列舉：與聚合體（P）及聚合體（Q）不同的聚合體、於分子內具有至少一個環氧基的分子量1000以下的低分子化合物（例如，乙二醇二縮水甘油醚、N,N,N',N'-四縮水甘油基-間二甲苯二胺、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷等）、官能性矽烷化合物、多官能(甲基)丙烯酸酯、抗氧化劑、金屬螫合化合物、硬化促進劑、界面活性劑、填充劑、分散劑、光增感劑等。其他成分的調配比例可於無損本揭示的效果的範圍內，根據各化合物而適宜選擇。Examples of the other components contained in the liquid crystal alignment agent include a polymer different from the polymer (P) and the polymer (Q), and a molecular weight of at least one epoxy group in the molecule of 1,000, for example. The following low-molecular compounds (for example, ethylene glycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, N, N, N', N'-tetraglycidyl -4,4'-diaminodiphenylmethane, etc.), functional silane compounds, polyfunctional (meth) acrylates, antioxidants, metal bonding compounds, hardening accelerators, surfactants, fillers, Dispersant, light sensitizer, etc. The blending ratio of other components may be appropriately selected depending on each compound within a range that does not impair the effects of the present disclosure.

液晶配向劑中的固體成分濃度（液晶配向劑的溶媒以外的成分的合計質量於液晶配向劑的總質量中所佔的比例）可考慮黏性、揮發性等適宜選擇，較佳為1質量%～10質量%的範圍。於固體成分濃度小於1質量%的情況下，塗膜的膜厚過小而難以獲得良好的液晶配向膜。另一方面，於固體成分濃度超過10質量%的情況下，塗膜的膜厚過大而難以獲得良好的液晶配向膜，另外液晶配向劑的黏性增大而存在塗佈性降低的傾向。The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) may be appropriately selected in consideration of viscosity and volatility, and is preferably 1% by mass. A range of -10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small, and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film is too large, and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent tends to increase and the coatability tends to decrease.

《液晶配向膜及液晶元件》
本揭示的液晶配向膜是由如所述般製備的液晶配向劑形成。另外，本揭示的液晶元件包括使用所述說明的液晶配向劑而形成的液晶配向膜。液晶元件中的液晶的動作模式並無特別限定，例如可應用於扭轉向列（Twisted Nematic，TN）型、超扭轉向列（Super Twisted Nematic，STN）型、垂直配向（Vertical Alignment，VA）型（包括垂直配向-多域垂直配向（Vertical Alignment - Multi-domain Vertical Alignment，VA-MVA）型、垂直配向-圖案垂直配向（Vertical Alignment-Patterned Vertical Alignment，VA-PVA）型等）、共面切換（In-Plane Switching，IPS）型、邊緣場切換（Fringe Field Switching，FFS）型、光學補償彎曲（Optically Compensated Bend，OCB）型、聚合物穩定配向（Polymer Sustained Alignment，PSA）型等多種模式。液晶元件例如可藉由包括以下的步驟1～步驟3的方法來製造。步驟1中，使用基板視所需的動作模式而不同。步驟2及步驟3於各動作模式下共通。"Liquid crystal alignment film and liquid crystal element"
The liquid crystal alignment film of the present disclosure is formed of a liquid crystal alignment agent prepared as described above. The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited. For example, it can be applied to a Twisted Nematic (TN) type, a Super Twisted Nematic (STN) type, or a Vertical Alignment (VA) type. (Including Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), coplanar switching (In-Plane Switching, IPS) type, Fringe Field Switching (FFS) type, Optically Compensated Bend (OCB) type, Polymer Sustained Alignment (PSA) type and other modes. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the substrate to be used differs depending on the required operation mode. Steps 2 and 3 are common in each operation mode.

＜步驟1：塗膜的形成＞
首先，於基板上塗佈液晶配向劑，較佳為對塗佈面進行加熱，藉此於基板上形成塗膜。作為基板，例如可使用包含以下材料的透明基板：浮法玻璃、鈉玻璃等玻璃；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯、聚(脂環式烯烴)等塑膠。設置於基板的一個面上的透明導電膜可使用：包含氧化錫（SnO₂ ）的奈塞（NESA）膜（美國PPG公司註冊商標）、包含氧化銦-氧化錫（In₂ O₃ -SnO₂ ）的氧化銦錫（Indium Tin Oxide，ITO）膜等。於製造TN型、STN型或VA型液晶元件的情況下，使用設置有經圖案化的透明導電膜的兩塊基板。另一方面，於製造IPS型或FFS型液晶元件的情況下，使用設置有經圖案化為梳齒型的電極的基板、與並未設置電極的相向基板。對基板的液晶配向劑的塗佈是於電極形成面上較佳為藉由平板印刷法、柔版印刷法、旋轉塗佈法、輥塗佈機法或噴墨印刷法進行。<Step 1: Formation of a coating film>
First, a liquid crystal alignment agent is coated on a substrate, and it is preferable to heat a coating surface to form a coating film on the substrate. As the substrate, for example, a transparent substrate including glass such as float glass and soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, polycarbonate, poly ( Alicyclic olefins) and other plastics. The transparent conductive film provided on one surface of the substrate can be used: a NESA film (registered trademark of the United States PPG) containing tin oxide (SnO ₂ ), and an indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Indium Tin Oxide (ITO) film. In the case of manufacturing a TN type, STN type, or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, in the case of manufacturing an IPS-type or FFS-type liquid crystal element, a substrate provided with an electrode patterned into a comb-tooth type and an opposing substrate provided with no electrode are used. The application of the liquid crystal alignment agent to the substrate is preferably performed on the electrode formation surface by a lithographic printing method, a flexographic printing method, a spin coating method, a roll coater method, or an inkjet printing method.

塗佈液晶配向劑後，出於防止所塗佈的液晶配向劑的滴液等目的，較佳為實施預加熱（預烘烤）。預烘烤溫度較佳為30℃～200℃，預烘烤時間較佳為0.25分鐘～10分鐘。其後，出於將溶劑完全去除、視需要將聚合體中存在的醯胺酸結構加以熱醯亞胺化的目的，而實施煅燒（後烘烤）步驟。此時的煅燒溫度（後烘烤溫度）較佳為80℃～250℃，更佳為80℃～200℃。後烘烤時間較佳為5分鐘～200分鐘。如此形成的膜的膜厚較佳為0.001 μm～1 μm。After the liquid crystal alignment agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing dripping of the applied liquid crystal alignment agent. The pre-baking temperature is preferably 30 ° C to 200 ° C, and the prebaking time is preferably 0.25 minutes to 10 minutes. Thereafter, a calcining (post-baking) step is performed for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amido acid structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 250 ° C, and more preferably 80 ° C to 200 ° C. The post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the thus formed film is preferably 0.001 μm to 1 μm.

＜步驟2：配向處理＞
於製造TN型、STN型、IPS型或FFS型的液晶元件的情況下，實施對所述步驟1中形成的塗膜賦予液晶配向能力的處理（配向處理）。藉此，對塗膜賦予液晶分子的配向能力而成為液晶配向膜。作為配向處理，可列舉：利用捲繞著包含例如尼龍（nylon）、人造絲（rayon）、棉（cotton）等纖維的布的輥對塗膜朝一定方向進行擦拭而對塗膜賦予液晶配向能力的摩擦處理、對基板上所形成的塗膜進行光照射而對塗膜賦予液晶配向能力的光配向處理等。該些中較佳為光配向處理。於製造垂直配向型液晶元件的情況下，可將所述步驟1中形成的塗膜直接用作液晶配向膜，但為了進一步提高液晶配向能力，亦可對該塗膜實施配向處理。<Step 2: Alignment Processing>
When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, a process (alignment process) of imparting liquid crystal alignment ability to the coating film formed in the step 1 is performed. Thereby, the alignment ability of liquid crystal molecules is given to a coating film, and it becomes a liquid crystal alignment film. Examples of the alignment treatment include applying a liquid crystal alignment ability to the coating film by wiping the coating film in a certain direction with a roller wound with a cloth including fibers such as nylon, rayon, and cotton. A rubbing treatment, a light alignment treatment that irradiates a coating film formed on a substrate with light to give a liquid crystal alignment ability to the coating film, and the like. Among these, photo-alignment processing is preferred. In the case of manufacturing a vertical alignment type liquid crystal element, the coating film formed in the step 1 may be directly used as a liquid crystal alignment film, but in order to further improve the liquid crystal alignment capability, an alignment treatment may be performed on the coating film.

用於光配向的光照射可藉由如下方法等進行：對後烘烤步驟後的塗膜進行照射的方法、對預烘烤步驟後且後烘烤步驟前的塗膜進行照射的方法、於預烘烤步驟及後烘烤步驟的至少任一步驟中於塗膜的加熱中對塗膜進行照射的方法。作為照射至塗膜的放射線，例如可使用包含150 nm～800 nm的波長的光的紫外線及可見光線。較佳為包含200 nm～400 nm的波長的光的紫外線。於放射線為偏光的情況下，可為直線偏光亦可為部分偏光。於使用的放射線為直線偏光或部分偏光的情況下，照射可從垂直於基板面的方向進行，亦可從傾斜方向進行，或者亦可將該些方向組合來進行。非偏光的放射線時的照射方向設為傾斜方向。The light irradiation for light alignment can be performed by a method such as a method of irradiating a coating film after the post-baking step, a method of irradiating a coating film after the pre-baking step and before the post-baking step, and A method of irradiating a coating film while heating the coating film in at least one of the pre-baking step and the post-baking step. As radiation to be applied to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. Ultraviolet light including light having a wavelength of 200 nm to 400 nm is preferred. When the radiation is polarized, linearly polarized light or partially polarized light may be used. When the radiation used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction, or a combination of these directions may be used. The irradiation direction at the time of non-polarized radiation is an oblique direction.

作為使用的光源，例如可列舉低壓水銀燈、高壓水銀燈、氘燈、金屬鹵化物燈、氬共振燈、氙燈、準分子雷射等。放射線的照射量較佳為400 J/m² ～50,000 J/m² ，更佳為1,000 J/m² ～20,000 J/m² 。於用於賦予配向能力的光照射後，亦可進行對基板表面使用例如水、有機溶媒（例如，甲醇、異丙醇、1-甲氧基-2-丙醇乙酸酯、丁基溶纖劑、乳酸乙酯等）或該些的混合物進行清洗的處理、或對基板進行加熱的處理。Examples of the light source used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and the like. The radiation dose is preferably 400 J / m ² to 50,000 J / m ² , and more preferably 1,000 J / m ² to 20,000 J / m ² . After the light irradiation for imparting the alignment ability, the substrate surface may be subjected to, for example, water, an organic solvent (for example, methanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cellosolve, Ethyl lactate, etc.) or a mixture of these is subjected to a cleaning process or a substrate heating process.

＜步驟3：液晶單元的構築＞
準備兩塊以所述方式形成有液晶配向膜的基板，並將液晶配置於相向配置的兩塊基板之間，藉此製造液晶單元。於製造液晶單元時，例如可列舉如下方法等：以液晶配向膜相向的方式隔著間隙將兩塊基板相向配置，使用密封劑將兩塊基板的周邊部貼合，於由基板表面與密封劑所包圍的單元間隙內注入/填充液晶並將注入孔密封的方法；利用液晶滴注（One Drop Fill，ODF）方式的方法。密封劑例如可使用含有硬化劑及作為間隔件（spacer）的氧化鋁球的環氧樹脂等。液晶可列舉向列液晶及層列液晶，其中較佳為向列液晶。PSA模式中，於構築液晶單元後，對一對基板所具有的導電膜間施加電壓，在該狀態下對液晶單元進行光照射處理。<Step 3: Construction of liquid crystal cell>
Two substrates having a liquid crystal alignment film formed in the manner described above were prepared, and liquid crystals were arranged between the two substrates arranged opposite to each other, thereby manufacturing a liquid crystal cell. When manufacturing a liquid crystal cell, for example, the following methods can be cited: the two substrates are arranged opposite to each other with a gap between the liquid crystal alignment films, the peripheral portions of the two substrates are bonded with a sealant, and the substrate surface and the sealant are bonded together. A method of injecting / filling liquid crystal in the enclosed cell gap and sealing the injection hole; a method using a liquid crystal drip (ODF) method. As the sealant, for example, an epoxy resin containing a hardener and alumina balls as a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferred. In the PSA mode, after the liquid crystal cell is constructed, a voltage is applied between the conductive films included in a pair of substrates, and the liquid crystal cell is subjected to light irradiation treatment in this state.

繼而，視需要於液晶單元的外側表面上貼合偏光板，製成液晶元件。偏光板可列舉：以乙酸纖維素保護膜夾持被稱為「H膜」的偏光膜而得的偏光板、或包含H膜其自身的偏光板，所述「H膜」是一邊使聚乙烯基醇延伸配向一邊使其吸收碘而成。Then, if necessary, a polarizing plate is laminated on the outer surface of the liquid crystal cell to form a liquid crystal element. Examples of the polarizing plate include a polarizing plate obtained by sandwiching a polarizing film called an "H film" with a protective cellulose acetate film, or a polarizing plate including the H film itself. Alcohol is extended by one side so that it absorbs iodine.

本揭示的液晶元件可有效地應用於各種用途，例如可應用於鐘錶、可攜式遊戲、文字處理器、筆記型個人電腦、汽車導航系統、攝錄像機、個人數位助理（Personal Digital Assistant，PDA）、數位相機、行動電話、智慧型電話、各種監視器、液晶電視機、資訊顯示器等各種顯示裝置、或調光膜、相位差膜等中。
[實施例]The liquid crystal element disclosed herein can be effectively used in various applications, such as clocks, portable games, word processors, notebook personal computers, car navigation systems, camcorders, and personal digital assistants (PDAs). , Digital cameras, mobile phones, smart phones, various monitors, LCD televisions, information displays, and other display devices, or dimming films, retardation films, etc.
[Example]

以下，藉由實施例進行具體說明，但本揭示內容並不限定於以下實施例。
於以下的例子中，聚合體的重量平均分子量（Mw）、數量平均分子量（Mn）及分子量分佈（Mw/Mn）是藉由以下方法測定。
＜重量平均分子量、數量平均分子量及分子量分佈＞
藉由凝膠滲透層析法（GPC）於下述條件下測定Mw及Mn。另外，分子量分佈（Mw/Mn）是藉由所獲得的Mw及Mn算出。
裝置：昭和電工（股）的「GPC-101」
GPC管柱：將島津GLC（SHIMADZU GLC）（股）製造的「GPC-KF-801」、「GPC-KF-802」、「GPC-KF-803」及「GPC-KF-804」結合
移動相：四氫呋喃（tetrahydrofuran，THF）、或含溴化鋰及磷酸的N,N-二甲基甲醯胺溶液
管柱溫度：40℃
流速：1.0 mL/分鐘
試樣濃度：1.0質量%
試樣注入量：100 μL
檢測器：示差折射計
標準物質：單分散聚苯乙烯
以下示出下述例中使用的化合物的結構式。In the following, specific examples are used to explain, but the present disclosure is not limited to the following examples.
In the following examples, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymer were measured by the following methods.
<Weight average molecular weight, number average molecular weight, and molecular weight distribution>
Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution (Mw / Mn) is calculated from the obtained Mw and Mn.
Installation: "GPC-101" by Showa Denko Corporation
GPC column: "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804" manufactured by Shimadzu GLC (SHIMADZU GLC) : Tetrahydrofuran (THF), or N, N-dimethylformamide solution containing lithium bromide and phosphoric acid. Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Reference material: Monodisperse polystyrene The structural formula of the compound used in the following examples is shown below.

[表1]



[表2]



[表3]



[表4]



[表5]



[表6]

[Table 1]



[Table 2]



[table 3]



[Table 4]



[table 5]



[TABLE 6]

[化24]



[化25]

[Chemical 24]



[Chemical 25]

＜單體的合成＞
[合成例1：化合物（MI-01）的合成]
按照下述流程1來合成化合物（MI-01）。
[化26]

＜ Synthesis of monomer ＞
[Synthesis Example 1: Synthesis of Compound (MI-01)]
Compound (MI-01) was synthesized according to the following scheme 1.
[Chemical 26]

·化合物（MI-01）的合成
於裝有攪拌器的100 mL茄形燒瓶中添加14.0 g的(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸、20 g的亞硫醯氯、以及0.01 g的N,N-二甲基甲醯胺，並80℃下攪拌1小時。其後，利用膜片泵將過剩的亞硫醯氯去除，並添加100 g的四氫呋喃而製成溶液A。
重新於裝有攪拌器的500 mL三口燒瓶中添加5.67 g的4-羥基苯基馬來醯亞胺、200 g的四氫呋喃、以及12.1 g的三乙基胺，並進行冰浴。向其中滴加溶液A並於室溫下攪拌3小時。利用800 mL的水對反應液進行再沈澱，對所獲得的白色固體進行真空乾燥，藉此獲得14.3 g的化合物（MI-01）。· Synthesis of compound (MI-01) In a 100 mL eggplant-shaped flask equipped with a stirrer, 14.0 g of (E) -3- (4-((4 '-(4,4,4-trifluorobutyl) )-[1,1'-bi (cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid, 20 g of thionyl chloride, and 0.01 g of N, N-dimethylformamide And stirred at 80 ° C for 1 hour. Thereafter, the excess thionyl chloride was removed by a diaphragm pump, and 100 g of tetrahydrofuran was added to prepare a solution A.
In a 500 mL three-necked flask equipped with a stirrer, 5.67 g of 4-hydroxyphenylmaleimide, 200 g of tetrahydrofuran, and 12.1 g of triethylamine were added again, and an ice bath was performed. Solution A was added dropwise thereto and stirred at room temperature for 3 hours. The reaction solution was reprecipitated with 800 mL of water, and the obtained white solid was vacuum-dried to obtain 14.3 g of a compound (MI-01).

[合成例2：化合物（MI-02）的合成]
按照下述流程2來合成化合物（MI-02）。
[化27]

[Synthesis Example 2: Synthesis of Compound (MI-02)]
The compound (MI-02) was synthesized according to the following scheme 2.
[Chemical 27]

·化合物（M-2-1）的合成
於裝有攪拌器的1000 mL三口燒瓶中取11.5 g的4-胺基-環己醇，添加150 g的四氫呋喃並進行冰浴。向其中滴加包含9.81 g的馬來酸酐與150 g的四氫呋喃的溶液，並於室溫下攪拌3小時。其後，藉由過濾回收所析出的白色固體。對該白色固體進行真空乾燥，藉此獲得20.2 g的化合物（M-2-1）。
·化合物（M-2-2）（4-羥基環己基馬來醯亞胺）的合成
於裝有攪拌器的500 mL三口燒瓶中添加17.1 g的化合物（M-2-1）、10.9 g的氯化鋅(II)、以及250 g的甲苯，並於80℃下加熱攪拌。向其中滴加包含23.2 g的雙(三甲基矽烷基)胺與100 g的甲苯的溶液，並於80℃下攪拌5小時。其後，向反應液中添加300 g的乙酸乙酯，並進行2次利用1 mol/L鹽酸的分液清洗、1次利用碳酸氫鈉水溶液的分液清洗、3次利用水的分液清洗。其後，利用旋轉蒸發器（rotary evaporator）對有機層進行濃縮。將所獲得的白色固體放入至THF/乙醇/水的混合溶媒中，並藉由過濾回收中途所析出的白色固體。對該白色固體進行真空乾燥，藉此獲得7.99 g的化合物（M-2-2）。
·化合物（MI-02）的合成
於合成例1中，代替4-羥基苯基馬來醯亞胺而使用4-羥基環己基馬來醯亞胺，除此以外，藉由與合成例1相同的方法而獲得14.0 g的化合物（MI-02）。· Synthesis of compound (M-2-1) In a 1000 mL three-necked flask equipped with a stirrer, 11.5 g of 4-amino-cyclohexanol was taken, 150 g of tetrahydrofuran was added, and an ice bath was performed. A solution containing 9.81 g of maleic anhydride and 150 g of tetrahydrofuran was added dropwise thereto, and stirred at room temperature for 3 hours. Thereafter, the precipitated white solid was recovered by filtration. This white solid was vacuum-dried, whereby 20.2 g of a compound (M-2-1) was obtained.
· Synthesis of compound (M-2-2) (4-hydroxycyclohexylmaleimide) In a 500 mL three-necked flask equipped with a stirrer, 17.1 g of compound (M-2-1) and 10.9 g of Zinc (II) chloride and 250 g of toluene were heated and stirred at 80 ° C. A solution containing 23.2 g of bis (trimethylsilyl) amine and 100 g of toluene was added dropwise thereto, and stirred at 80 ° C. for 5 hours. Thereafter, 300 g of ethyl acetate was added to the reaction solution, and the liquid was washed twice with 1 mol / L hydrochloric acid, the liquid was washed once with a sodium bicarbonate aqueous solution, and the liquid was washed three times with water. . Thereafter, the organic layer was concentrated using a rotary evaporator. The obtained white solid was put into a mixed solvent of THF / ethanol / water, and the white solid precipitated in the middle was recovered by filtration. This white solid was vacuum-dried to obtain 7.99 g of a compound (M-2-2).
Compound (MI-02) was synthesized in the same manner as in Synthesis Example 1 except that 4-hydroxycyclohexylmaleimide was used instead of 4-hydroxyphenylmaleimide. Method to obtain 14.0 g of the compound (MI-02).

[合成例3：化合物（MI-03）的合成]
按照下述流程3來合成化合物（MI-03）。
[化28]

[Synthesis Example 3: Synthesis of Compound (MI-03)]
The compound (MI-03) was synthesized according to the following scheme 3.
[Chemical 28]

·化合物（M-3-1）的合成
於裝有攪拌器的2000 mL三口燒瓶中取11.5 g的N-Boc-4-羥基苯胺（N-BOC-4- hydroxyaniline）、23.3 g的(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸，添加1000 g的二氯甲烷並進行冰浴。向其中依次添加1.21 g的N,N-二甲基胺基吡啶、11.5 g的1-乙基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽，於室溫下攪拌8小時後，利用500 g的蒸餾水進行4次分液清洗。其後，利用旋轉蒸發器對有機層進行緩慢濃縮直至內容量為100 g為止，並藉由過濾回收中途所析出的白色固體。對該白色固體進行真空乾燥，藉此獲得31.6 g的化合物（M-3-1）。
·化合物（M-3-2）的合成
於裝有攪拌器的300 mL茄形燒瓶中取30.3 g的化合物（M-3-1）、33.8 g的三氟乙酸，添加50 g的二氯甲烷，於室溫下攪拌1小時。其後，利用飽和碳酸氫鈉水溶液進行中和後，利用50 g的蒸餾水進行4次分液清洗。其後，利用旋轉蒸發器對有機層進行緩慢濃縮直至內容量為50 g為止，並藉由過濾回收中途所析出的白色固體。對該白色固體進行真空乾燥，藉此獲得24.8 g的化合物（M-3-2）。
·化合物（MI-03）的合成
於裝有攪拌器的2000 mL三口燒瓶中取24.7 g的化合物（M-3-2），添加200 g的四氫呋喃並進行冰浴。向其中滴加包含4.34 g的馬來酸酐與200 g的四氫呋喃的溶液，並於室溫下攪拌3小時。其後，藉由過濾回收所析出的固體。對該黃色固體進行真空乾燥，藉此獲得28.9 g的化合物（MI-03）。· Synthesis of compound (M-3-1) In a 2000 mL three-neck flask equipped with a stirrer, 11.5 g of N-Boc-4-hydroxyaniline and 23.3 g of (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid, Add 1000 g of dichloromethane and perform an ice bath. To this, 1.21 g of N, N-dimethylaminopyridine and 11.5 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride were sequentially added. After stirring at room temperature for 8 hours, the solution was washed with 500 g of distilled water 4 times. Thereafter, the organic layer was concentrated slowly by a rotary evaporator until the content was 100 g, and a white solid precipitated in the middle was recovered by filtration. This white solid was vacuum-dried to obtain 31.6 g of a compound (M-3-1).
· Synthesis of compound (M-3-2) In a 300 mL eggplant-shaped flask equipped with a stirrer, 30.3 g of compound (M-3-1) and 33.8 g of trifluoroacetic acid were added, and 50 g of dichloromethane was added. , And stirred at room temperature for 1 hour. Thereafter, neutralization was performed with a saturated sodium bicarbonate aqueous solution, and then liquid separation and washing were performed four times with 50 g of distilled water. Thereafter, the organic layer was slowly concentrated with a rotary evaporator until the content was 50 g, and a white solid precipitated in the middle was recovered by filtration. This white solid was vacuum-dried, whereby 24.8 g of a compound (M-3-2) was obtained.
· Synthesis of compound (MI-03) In a 2000 mL three-necked flask equipped with a stirrer, 24.7 g of compound (M-3-2) was taken, 200 g of tetrahydrofuran was added, and the mixture was ice-baked. A solution containing 4.34 g of maleic anhydride and 200 g of tetrahydrofuran was added dropwise thereto, and stirred at room temperature for 3 hours. Thereafter, the precipitated solid was recovered by filtration. This yellow solid was vacuum-dried to obtain 28.9 g of a compound (MI-03).

[合成例4：化合物（MI-04）的合成]
按照下述流程4來合成化合物（MI-04）。
[化29]

[Synthesis Example 4: Synthesis of Compound (MI-04)]
The compound (MI-04) was synthesized according to the following scheme 4.
[Chemical 29]

·化合物（MI-04）的合成
於裝有攪拌器的500 mL茄形燒瓶中添加6.53 g的馬來酸單甲酯、25 g的亞硫醯氯、以及0.01 g的N,N-二甲基甲醯胺，並於60℃下攪拌2小時。其後，利用膜片泵將過剩的亞硫醯氯去除，並添加50 g的四氫呋喃而製成溶液A。
重新於裝有攪拌器的1000 mL三口燒瓶中添加26.8 g的化合物（M-3-2）、500 g的四氫呋喃、以及13.2 g的三乙基胺，並進行冰浴。向其中滴加溶液A並於室溫下攪拌8小時。利用1200 mL的水對反應液進行再沈澱，對所獲得的白色固體進行真空乾燥，藉此獲得25.4 g的化合物（MI-04）。· Synthesis of compound (MI-04) In a 500 mL eggplant-shaped flask equipped with a stirrer, 6.53 g of monomethyl maleate, 25 g of thionyl chloride, and 0.01 g of N, N-dimethylformate were added. Formamidine and stirred at 60 ° C for 2 hours. Thereafter, the excess thionyl chloride was removed by a diaphragm pump, and 50 g of tetrahydrofuran was added to prepare a solution A.
In a 1000 mL three-necked flask equipped with a stirrer, 26.8 g of the compound (M-3-2), 500 g of tetrahydrofuran, and 13.2 g of triethylamine were added again, and an ice bath was performed. Solution A was added dropwise thereto and stirred at room temperature for 8 hours. The reaction solution was reprecipitated with 1200 mL of water, and the obtained white solid was vacuum-dried to obtain 25.4 g of a compound (MI-04).

[合成例5：化合物（MI-05）的合成]
於合成例3中，作為原料而使用化合物（M-3-2）、以及代替馬來酸酐而使用衣康酸酐，除此以外，藉由與合成例1-3相同的方法而獲得19.1 g的化合物（MI-05）。
[合成例6：化合物（MI-06）的合成]
於合成例1中，代替4-羥基苯基馬來醯亞胺而使用4-羥基-2-甲基苯基馬來醯亞胺，除此以外，藉由與合成例1相同的方法而獲得14.4 g的化合物（MI-06）。再者，於合成例2的M-2-1的合成中，代替4-羥基環己基胺而使用2-甲基-4-羥基苯胺來合成4-羥基-2-甲基苯基馬來醯亞胺。
[合成例7：化合物（MI-07）的合成]
於合成例1中，代替4-羥基苯基馬來醯亞胺而使用4-羥基-3-甲基苯基馬來醯亞胺，除此以外，藉由與合成例1相同的方法而獲得14.5 g的化合物（MI-07）。再者，於合成例2的化合物（M-2-1）的合成中，代替4-羥基環己基胺而使用3-甲基-4-羥基苯胺來合成4-羥基-3-甲基苯基馬來醯亞胺。[Synthesis Example 5: Synthesis of Compound (MI-05)]
Except for using Compound (M-3-2) as a raw material and using itaconic anhydride instead of maleic anhydride in Synthesis Example 3, 19.1 g was obtained by the same method as in Synthesis Example 1-3. Compound (MI-05).
[Synthesis Example 6: Synthesis of Compound (MI-06)]
In Synthesis Example 1, the same method as in Synthesis Example 1 was used, except that 4-hydroxy-2-methylphenylmaleimide was used instead of 4-hydroxyphenylmaleimide. 14.4 g of compound (MI-06). Furthermore, in the synthesis of M-2-1 in Synthesis Example 2, 4-hydroxy-2-methylphenylmaleamidine was synthesized using 2-methyl-4-hydroxyaniline instead of 4-hydroxycyclohexylamine. Imine.
[Synthesis Example 7: Synthesis of Compound (MI-07)]
In Synthesis Example 1, the same method as in Synthesis Example 1 was used, except that 4-hydroxy-3-methylphenylmaleimide was used instead of 4-hydroxyphenylmaleimide. 14.5 g of compound (MI-07). Furthermore, in the synthesis of the compound (M-2-1) of Synthesis Example 2, 4-hydroxy-3-methylphenyl was synthesized using 3-methyl-4-hydroxyaniline instead of 4-hydroxycyclohexylamine. Maleimidine.

[合成例8：化合物（MI-08）的合成]
按照下述流程8來合成化合物（MI-08）。
[化30]

[Synthesis Example 8: Synthesis of Compound (MI-08)]
Compound (MI-08) was synthesized according to the following scheme 8.
[Chemical 30]

·4-羥基-α-甲基肉桂酸（化合物（M-8-1））的合成
於裝有攪拌器的200 mL三口燒瓶中混合9.74 g的4-羥基苯甲醛、25 g的丙酸酐、以及15.2 g的丙酸鈉，於氮氣環境下、145℃下攪拌16小時。反應後，利用冰浴進行冷卻，添加100 ml的水並攪拌3小時，使固體析出並進行過濾。將所獲得的固體添加至10%氫氧化鈉水溶液中，於0℃下攪拌30分鐘。對不溶物進行過濾後，於濾液中添加鹽酸並製成酸性，過濾所生成的固體。使固體溶解於乙酸乙酯200 ml中，利用水清洗3次。利用無水硫酸鈉對有機層進行乾燥後，將溶媒減壓餾去，獲得8.73 g的4-羥基-α-甲基肉桂酸（將其設為化合物（M-8-1））。
·化合物（M-8-2）的合成
藉由與合成例1相同的方法使4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羧酸與4-羥基-α-甲基肉桂酸反應，從而獲得15.0 g的化合物（M-8-2）。
·化合物（MI-08）的合成
於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（M-8-2），除此以外，藉由與合成例1相同的方法而獲得14.6 g的化合物（MI-08）。· Synthesis of 4-hydroxy-α-methylcinnamic acid (compound (M-8-1)) In a 200 mL three-necked flask equipped with a stirrer, 9.74 g of 4-hydroxybenzaldehyde, 25 g of propionic anhydride, And 15.2 g of sodium propionate were stirred under a nitrogen atmosphere at 145 ° C for 16 hours. After the reaction, the mixture was cooled in an ice bath, and 100 ml of water was added and stirred for 3 hours to precipitate a solid and then filtered. The obtained solid was added to a 10% aqueous sodium hydroxide solution, and stirred at 0 ° C for 30 minutes. After filtering insoluble matter, hydrochloric acid was added to the filtrate to make it acidic, and the produced solid was filtered. The solid was dissolved in 200 ml of ethyl acetate and washed three times with water. After the organic layer was dried with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 8.73 g of 4-hydroxy-α-methylcinnamic acid (this compound was designated as compound (M-8-1)).
· Synthesis of compound (M-8-2): 4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)] was synthesized by the same method as in Synthesis Example 1. The 4-carboxylic acid was reacted with 4-hydroxy-α-methylcinnamic acid to obtain 15.0 g of a compound (M-8-2).
· Compound (MI-08) was synthesized in Synthesis Example 1 instead of (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-linked (Cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid was used in the same manner as in Synthesis Example 1 except that compound (M-8-2) was used to obtain 14.6 g of compound (MI -08).

[合成例9：化合物（MI-09）的合成]
按照下述流程9來合成化合物（MI-09）。
[化31]

[Synthesis Example 9: Synthesis of Compound (MI-09)]
The compound (MI-09) was synthesized according to the following scheme 9.
[Chemical 31]

於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（M-9-1），除此以外，藉由與合成例1相同的方法而獲得14.5 g的化合物（MI-09）。再者，於合成例8中，代替4-羥基-α-甲基肉桂酸而使用2-甲基-4-羥基肉桂酸，除此以外，藉由相同的方法來合成化合物（M-9-1）。In Synthesis Example 1, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4- Except for using carbonyl) oxy) phenyl) acrylic acid and using compound (M-9-1), 14.5 g of compound (MI-09) was obtained in the same manner as in Synthesis Example 1. In Synthesis Example 8, a compound (M-9-) was synthesized by the same method except that 2-methyl-4-hydroxycinnamic acid was used instead of 4-hydroxy-α-methylcinnamic acid. 1).

[合成例10：化合物（MI-10）的合成]
按照下述流程10來合成化合物（MI-10）。
[化32]

[Synthesis Example 10: Synthesis of Compound (MI-10)]
Compound (MI-10) was synthesized according to the following scheme 10.
[Chemical 32]

於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（M-10-1），除此以外，藉由與合成例1相同的方法而獲得14.5 g的化合物（MI-10）。再者，於合成例8中，代替4-羥基-α-甲基肉桂酸而使用3-甲基-4-羥基肉桂酸，除此以外，藉由相同的方法來合成化合物（M-10-1）。In Synthesis Example 1, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4- Except for using carbonyl) oxy) phenyl) acrylic acid as the compound (M-10-1), 14.5 g of the compound (MI-10) was obtained in the same manner as in Synthesis Example 1. In addition, in Synthesis Example 8, a compound (M-10-) was synthesized by the same method except that 3-methyl-4-hydroxycinnamic acid was used instead of 4-hydroxy-α-methylcinnamic acid. 1).

[合成例11：化合物（MI-11）的合成]
按照下述流程11來合成化合物（MI-11）。
[化33]

[Synthesis Example 11: Synthesis of Compound (MI-11)]
Compound (MI-11) was synthesized according to the following scheme 11.
[Chemical 33]

於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)硫基)苯基)丙烯酸酯，除此以外，藉由與合成例1相同的方法而獲得14.4 g的化合物（MI-11）。
再者，(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)硫基)苯基)丙烯酸是使用4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羧酸與4-巰基肉桂酸並藉由與所述流程8相同的方法來合成。4-巰基肉桂酸可藉由日本專利第2646314號公報中記載的方法來合成。In Synthesis Example 1, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4- (Carbonyl) oxy) phenyl) acrylic acid and (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane) 14.4 g of compound (MI-11) was obtained by the same method as in Synthesis Example 1 except for] -4-carbonyl) thio) phenyl) acrylate.
Furthermore, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4-carbonyl) thio ) Phenyl) acrylic acid is obtained by using 4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4-carboxylic acid and 4-mercaptocinnamic acid It is synthesized by the same method as the above-mentioned scheme 8. 4-Mercaptocinnamic acid can be synthesized by the method described in Japanese Patent No. 2646314.

[合成例12：化合物（MI-12）的合成]
於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用(E)-3-(4-((4'-戊基-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸，除此以外，藉由與合成例1相同的方法而獲得13.4 g的化合物（MI-12）。[Synthesis Example 12: Synthesis of Compound (MI-12)]
In Synthesis Example 1, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4- (Carbonyl) oxy) phenyl) acrylic acid and (E) -3- (4-((4'-pentyl- [1,1'-bi (cyclohexane)]-4-carbonyl) oxy) benzene Except for acrylic acid, 13.4 g of a compound (MI-12) was obtained in the same manner as in Synthesis Example 1.

[合成例13：化合物（MI-13）的合成]
按照下述流程13來合成化合物（MI-13）。
[化34]

[Synthesis Example 13: Synthesis of Compound (MI-13)]
Compound (MI-13) was synthesized according to the following scheme 13.
[Chem 34]

於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用(E)-3-(4-((4-(4-(4,4,4-三氟丁基)環己基)苯甲醯基)氧基)苯基)丙烯酸，除此以外，藉由與合成例1相同的方法而獲得12.3 g的化合物（MI-13）。再者，(E)-3-(4-((4-(4-(4,4,4-三氟丁基)環己基)苯甲醯基)氧基)苯基)丙烯酸酯是使用4-(4-(4,4,4-三氟丁基)環己基)苯甲酸與香豆酸並藉由與所述流程8相同的方法來合成。In Synthesis Example 1, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4- (Carbonyl) oxy) phenyl) acrylic acid and (E) -3- (4-((4- (4- (4- (4,4,4-trifluorobutyl) cyclohexyl) benzyl) oxy)) Except for phenyl) acrylic acid, 12.3 g of a compound (MI-13) was obtained in the same manner as in Synthesis Example 1. In addition, (E) -3- (4-((4- (4- (4- (4,4,4-trifluorobutyl) cyclohexyl) benzyl) oxy) phenyl) acrylate is used 4 -(4- (4,4,4-trifluorobutyl) cyclohexyl) benzoic acid and coumaric acid were synthesized by the same method as in Scheme 8.

[合成例14：化合物（MI-14）的合成]
於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用(E)-3-(4-((4-(4-(3-(三甲基矽烷基)丙氧基)環己基)苯甲醯基)氧基)苯基)丙烯酸，除此以外，藉由與合成例1相同的方法而獲得15.7 g的化合物（MI-14）。[Synthesis Example 14: Synthesis of Compound (MI-14)]
In Synthesis Example 1, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4- (Carbonyl) oxy) phenyl) acrylic acid and (E) -3- (4-((4- (4- (4- (3- (trimethylsilyl) propoxy) cyclohexyl) benzyl) oxy) 15.7 g of a compound (MI-14) was obtained in the same manner as in Synthesis Example 1 except that the group was phenyl) acrylic acid.

[合成例15：化合物（MI-15）的合成]
按照下述流程15來合成化合物（MI-15）。
[化35]

[Synthesis Example 15: Synthesis of Compound (MI-15)]
Compound (MI-15) was synthesized according to the following scheme 15.
[Chemical 35]

·化合物（M-15-1）的合成
於300 mL三口燒瓶中放入6.36 g的第三丁醇鉀，並進行氮氣置換。繼而，滴加溶解於四氫呋喃180 ml中的碘化4,4,4-三氟丁基三苯基鏻28.3 g，於室溫下反應1小時。其後，添加4-(1,4-二氧雜螺環[4.5]癸-8-基)環己酮10.4 g，於室溫下反應72小時。利用旋轉蒸發器將溶媒餾去後，利用二乙基醚進行提取，並將己烷/乙酸乙酯作為展開溶媒利用矽膠管柱進行精製。利用旋轉蒸發器將溶劑去除而獲得8.1 g的化合物（M-15-1）。
·化合物（M-15-2）的合成
於500 mL三口燒瓶中放入7.7 g的化合物（M-15-1），並進行氮氣置換。繼而，添加225 ml的甲醇與1.23 g的鈀-活性炭（Pd10%），利用氫氣對燒瓶內進行置換，安裝充滿氫氣的氣球（balloon）。於室溫下劇烈攪拌12小時後，利用矽藻土進行過濾，並利用二氯甲烷清洗殘留物。利用水對濾液進行3次分液清洗，並利用旋轉蒸發器將溶劑去除，從而獲得7.5 g的化合物（M-15-2）。
·化合物（M-15-3）的合成
於200 mL三口燒瓶中放入7.5 g的化合物（M-15-2），並進行氮氣置換。繼而，添加30 ml的丙酮與15 ml的水後，滴加23.4 ml的三氟乙酸，並於室溫下反應16小時。利用旋轉蒸發器將溶劑去除，並利用矽膠管柱（己烷/乙酸乙酯）對乙酸乙酯提取液進行精製。利用旋轉蒸發器將溶劑去除後，進行真空乾燥，藉此獲得4.6 g的化合物（M-15-3）。
·化合物（M-15-4）的合成
於100 mL三口燒瓶中放入0.44 g的鎂，並進行氮氣置換。繼而，添加脫水四氫呋喃10 ml，並利用冰浴進行冷卻。緩慢滴加溶解於脫水四氫呋喃4 ml中的碘化苯0.15 ml，於室溫下反應30分鐘，且於70℃下反應30分鐘。恢復至室溫並利用冰浴進行冷卻，緩慢滴加4.6 g的溶解於脫水四氫呋喃20 ml中的化合物（M-15-3）。恢復至室溫並將反應了5小時的溶液投入至氯化銨飽和水溶液中。回收有機層，並利用氯化銨飽和水溶液進行2次分液清洗，之後將己烷/乙酸乙酯作為展開溶媒並利用矽膠管柱進行精製。利用旋轉蒸發器將溶劑去除而獲得4.1 g的化合物（M-15-4）。
·化合物（M-15-5）的合成
於100 mL三口燒瓶中放入4.1 g的化合物（M-15-4），並進行氮氣置換。繼而，添加2.5 ml的乙酸與0.25 g的鈀-活性炭（Pd10%）、20 ml的四氫呋喃，置換為氫氣環境，並於室溫下攪拌6小時。利用矽藻土對反應液進行過濾，並利用四氫呋喃進行清洗。利用旋轉蒸發器對濾液進行濃縮，並添加乙酸乙酯，於0℃下攪拌1小時。對所析出的固體進行過濾並進行真空乾燥，藉此獲得3.4 g的化合物（M-15-5）。
·化合物（M-15-6）的合成
於100 mL三口燒瓶中放入3.4 g的化合物（M-15-5）與氯化鐵(III)0.03 g，並進行氮氣置換。繼而，添加5.5 g的15%溴氫酸水溶液，之後滴加7.4 g的10%次氯酸鈉水溶液，並於室溫下攪拌2小時。回收有機層，並依次利用5%碳酸氫鈉水溶液、蒸餾水進行分液清洗。利用旋轉蒸發器將溶劑去除後，進行真空乾燥，藉此獲得2.5 g的化合物（M-15-6）。
·化合物（M-15-7）的合成
於100 mL三口燒瓶中放入0.43 g的丙烯酸、2.02 g的第三丁醇鉀，並進行氮氣置換。繼而，添加12 ml的水並於室溫下攪拌10分鐘，之後添加1.35 g的乙酸鈀與2.5 g的化合物（M-15-6），於100℃下攪拌24小時。恢復至室溫後，滴加鹽酸水溶液直至pH值為1為止。其後，利用二氯甲烷進行提取，並依次利用鹽水（brine）、硫酸鈉水溶液、水進行分液清洗。利用快速管柱層析法（flash column chromatography）進行精製，並利用旋轉蒸發器將溶劑去除且進行真空乾燥，藉此獲得2.1 g的化合物（M-15-7）。
·化合物（MI-15）的合成
於合成例1-1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（M-15-7），除此以外，藉由與合成例1-1相同的方法而獲得1.7 g的化合物（MI-15）。· Synthesis of compound (M-15-1) In a 300 mL three-necked flask, 6.36 g of potassium tert-butoxide was placed and replaced with nitrogen. Then, 28.3 g of 4,4,4-trifluorobutyltriphenylphosphonium iodide dissolved in 180 ml of tetrahydrofuran was added dropwise, and the mixture was reacted at room temperature for 1 hour. Thereafter, 10.4 g of 4- (1,4-dioxaspiro [4.5] dec-8-yl) cyclohexanone was added, and the mixture was reacted at room temperature for 72 hours. After the solvent was distilled off with a rotary evaporator, extraction was performed with diethyl ether, and hexane / ethyl acetate was used as a developing solvent for purification with a silica gel column. The solvent was removed using a rotary evaporator to obtain 8.1 g of a compound (M-15-1).
· Synthesis of compound (M-15-2) In a 500 mL three-necked flask, 7.7 g of compound (M-15-1) was placed and replaced with nitrogen. Next, 225 ml of methanol and 1.23 g of palladium-activated carbon (Pd10%) were added, the inside of the flask was replaced with hydrogen, and a balloon filled with hydrogen was installed. After vigorously stirring at room temperature for 12 hours, it was filtered through celite, and the residue was washed with dichloromethane. The filtrate was separated and washed three times with water, and the solvent was removed with a rotary evaporator to obtain 7.5 g of a compound (M-15-2).
• Synthesis of compound (M-15-3) In a 200 mL three-necked flask, 7.5 g of compound (M-15-2) was placed and replaced with nitrogen. Then, after adding 30 ml of acetone and 15 ml of water, 23.4 ml of trifluoroacetic acid was added dropwise, and the reaction was carried out at room temperature for 16 hours. The solvent was removed using a rotary evaporator, and the ethyl acetate extract was purified using a silica gel column (hexane / ethyl acetate). After removing the solvent with a rotary evaporator, vacuum drying was performed to obtain 4.6 g of a compound (M-15-3).
· Synthesis of compound (M-15-4) In a 100 mL three-necked flask, 0.44 g of magnesium was placed and replaced with nitrogen. Then, 10 ml of dehydrated tetrahydrofuran was added, and it cooled with the ice bath. 0.15 ml of benzene iodide dissolved in 4 ml of dehydrated tetrahydrofuran was slowly added dropwise, reacted at room temperature for 30 minutes, and reacted at 70 ° C for 30 minutes. After returning to room temperature and cooling with an ice bath, 4.6 g of the compound (M-15-3) dissolved in 20 ml of dehydrated tetrahydrofuran was slowly added dropwise. The temperature was returned to room temperature, and the solution reacted for 5 hours was poured into a saturated aqueous solution of ammonium chloride. The organic layer was recovered and separated and washed twice with a saturated aqueous solution of ammonium chloride. Thereafter, hexane / ethyl acetate was used as a developing solvent, and purification was performed using a silica gel column. The solvent was removed using a rotary evaporator to obtain 4.1 g of a compound (M-15-4).
· Synthesis of compound (M-15-5) In a 100 mL three-necked flask, 4.1 g of compound (M-15-4) was placed and replaced with nitrogen. Then, 2.5 ml of acetic acid, 0.25 g of palladium-activated carbon (Pd10%), and 20 ml of tetrahydrofuran were added, replaced with a hydrogen atmosphere, and stirred at room temperature for 6 hours. The reaction solution was filtered with diatomaceous earth and washed with tetrahydrofuran. The filtrate was concentrated on a rotary evaporator, ethyl acetate was added, and the mixture was stirred at 0 ° C for 1 hour. The precipitated solid was filtered and vacuum-dried to obtain 3.4 g of a compound (M-15-5).
· Synthesis of compound (M-15-6) In a 100 mL three-necked flask, 3.4 g of compound (M-15-5) and 0.03 g of iron (III) chloride were placed, and nitrogen substitution was performed. Then, 5.5 g of a 15% aqueous solution of hydrobromic acid was added, and then 7.4 g of a 10% aqueous solution of sodium hypochlorite was added dropwise, followed by stirring at room temperature for 2 hours. The organic layer was recovered and separated and washed with a 5% sodium bicarbonate aqueous solution and distilled water in this order. After removing the solvent with a rotary evaporator, vacuum drying was performed to obtain 2.5 g of a compound (M-15-6).
· Synthesis of compound (M-15-7) In a 100 mL three-necked flask, 0.43 g of acrylic acid and 2.02 g of potassium tert-butoxide were placed, and nitrogen substitution was performed. Next, 12 ml of water was added and stirred at room temperature for 10 minutes, and then 1.35 g of palladium acetate and 2.5 g of the compound (M-15-6) were added, followed by stirring at 100 ° C for 24 hours. After returning to room temperature, an aqueous hydrochloric acid solution was added dropwise until the pH was 1. After that, extraction was performed with dichloromethane, and then liquid separation and washing were sequentially performed using brine, an aqueous sodium sulfate solution, and water. Purification was performed by flash column chromatography, and the solvent was removed using a rotary evaporator and vacuum dried to obtain 2.1 g of a compound (M-15-7).
· Synthesis of compound (MI-15) In Synthesis Example 1-1, instead of (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1' -Bis (cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid, except that compound (M-15-7) was used, 1.7 g was obtained in the same manner as in Synthesis Example 1-1. Compound (MI-15).

[合成例16：化合物（MI-16）的合成]
按照下述流程16來合成化合物（MI-16）。
[化36]

[Synthesis Example 16: Synthesis of Compound (MI-16)]
Compound (MI-16) was synthesized according to the following scheme 16.
[Chemical 36]

·化合物（M-16-1）的合成
於500 mL三口燒瓶中放入22.4 g的4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羧酸，並進行氮氣置換。繼而，添加200 mL的THF，並於0℃下進行攪拌。向其中添加3.3 g的硼氫化鈉後，緩慢滴加12.1 g的三氟化硼二乙基醚，並反應18小時。反應結束後，將反應液轉移至2 L的燒杯中，利用鹽酸進行中和，向其中添加1.5 L的水。對所析出的固體進行過濾後，進行真空乾燥，藉此獲得20.6 g的化合物（M-16-1）。
·化合物（M-16-2）的合成
於1 L三口燒瓶中添加20.6 g的化合物（M-16-1）、0.819 g的N,N-二甲基-4-胺基吡啶、200 mL的二氯甲烷、13.6 g的三乙基胺，並冷卻至0℃。向其中緩慢滴加使14.1 g的對甲苯磺醯氯溶解於100 mL的二氯甲烷中而成的溶液，其後，反應20小時。反應結束後，添加100 mL的二氯甲烷，並利用500 mL的水對反應液進行3次分液，利用硫酸鎂對有機層進行乾燥，之後，利用過濾將硫酸鎂去除。繼而，利用旋轉蒸發器將濾液的溶媒餾去並對所生成的固體進行真空乾燥，藉此獲得29.3 g的化合物（M-16-2）。
·化合物（M-16-3）的合成
向1 L三口燒瓶中添加29.3 g的化合物（M-16-2）、7.82 g的4-羥基苯甲醛、13.3 g的碳酸鉀、200 mL的N,N-二甲基甲醯胺，並於100℃下反應5小時。反應結束後，添加500 mL的乙酸乙酯，並利用500 mL的水進行3次分液，之後利用硫酸鎂對有機層進行乾燥。繼而，利用過濾將硫酸鎂去除。繼而，利用過濾對硫酸鎂進行過濾，並利用旋轉蒸發器將濾液的溶媒餾去且對所生成的固體進行真空乾燥，藉此獲得23.4 g的化合物（M-16-3）。
·化合物（M-16-4）的合成
於1 L茄形燒瓶中添加23.4 g的化合物（M-16-3）、11.9 g的丙二酸、300 mL的吡啶、7.29 g的哌啶，並於回流條件下反應8小時。其後，將反應液冷卻至室溫後，添加300 mL的乙醇，濾取固體。利用乙醇對所獲得的固體進行清洗後，進行真空乾燥，藉此獲得18.1 g的化合物（M-16-4）。
·化合物（MI-16）的合成
於合成例1-1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（M-16-4），除此以外，藉由與合成例1-1相同的方法而獲得17.8 g的化合物（MI-16）。· Synthesis of compound (M-16-1) In a 500 mL three-necked flask, 22.4 g of 4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane) ] -4-carboxylic acid and nitrogen substitution. Then, 200 mL of THF was added and stirred at 0 ° C. After 3.3 g of sodium borohydride was added thereto, 12.1 g of boron trifluoride diethyl ether was slowly added dropwise and reacted for 18 hours. After the reaction, the reaction solution was transferred to a 2 L beaker, neutralized with hydrochloric acid, and 1.5 L of water was added thereto. The precipitated solid was filtered and then vacuum-dried to obtain 20.6 g of a compound (M-16-1).
· Synthesis of compound (M-16-2) In a 1 L three-necked flask, 20.6 g of compound (M-16-1), 0.819 g of N, N-dimethyl-4-aminopyridine, and 200 mL of Dichloromethane, 13.6 g of triethylamine, and cooled to 0 ° C. A solution prepared by dissolving 14.1 g of p-toluenesulfonyl chloride in 100 mL of dichloromethane was slowly added dropwise thereto, and then reacted for 20 hours. After the reaction, 100 mL of dichloromethane was added, and the reaction solution was separated three times with 500 mL of water. The organic layer was dried with magnesium sulfate, and then magnesium sulfate was removed by filtration. Then, the solvent of the filtrate was distilled off using a rotary evaporator, and the generated solid was vacuum-dried, thereby obtaining 29.3 g of a compound (M-16-2).
· Synthesis of compound (M-16-3) To a 1 L three-necked flask were added 29.3 g of compound (M-16-2), 7.82 g of 4-hydroxybenzaldehyde, 13.3 g of potassium carbonate, 200 mL of N, N-dimethylformamide, and reacted at 100 ° C for 5 hours. After the reaction was completed, 500 mL of ethyl acetate was added, and the mixture was separated three times with 500 mL of water, and then the organic layer was dried with magnesium sulfate. Then, magnesium sulfate was removed by filtration. Then, magnesium sulfate was filtered by filtration, and the solvent of the filtrate was distilled off using a rotary evaporator, and the resulting solid was vacuum-dried, thereby obtaining 23.4 g of a compound (M-16-3).
· Synthesis of compound (M-16-4) In a 1 L eggplant-shaped flask, 23.4 g of compound (M-16-3), 11.9 g of malonic acid, 300 mL of pyridine, 7.29 g of piperidine, and The reaction was carried out under reflux conditions for 8 hours. Thereafter, the reaction solution was cooled to room temperature, 300 mL of ethanol was added, and the solid was collected by filtration. The obtained solid was washed with ethanol, and then vacuum-dried to obtain 18.1 g of a compound (M-16-4).
· Synthesis of compound (MI-16) In Synthesis Example 1-1, instead of (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1' -Bis (cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid, except using compound (M-16-4), 17.8 g was obtained in the same manner as in Synthesis Example 1-1. Compound (MI-16).

[合成例17：化合物（MI-17）的合成]
按照下述流程17來合成化合物（MI-17）。
[化37]

[Synthesis Example 17: Synthesis of Compound (MI-17)]
Compound (MI-17) was synthesized according to the following scheme 17.
[Chemical 37]

於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用(E)-3-(4-((4-(4,4,4-三氟丁氧基)苯甲醯基)氧基)苯基)丙烯酸酯，除此以外，藉由與合成例1相同的方法而獲得12.6 g的化合物（MI-17）。In Synthesis Example 1, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4- Carbonyl) oxy) phenyl) acrylic acid and (E) -3- (4-((4- (4,4,4-trifluorobutoxy) benzyl) oxy) phenyl) acrylate Other than that, 12.6 g of a compound (MI-17) was obtained by the same method as in Synthesis Example 1.

[合成例18：化合物（MI-18）的合成]
按照下述流程18來合成化合物（MI-18）。
[化38]

[Synthesis Example 18: Synthesis of Compound (MI-18)]
Compound (MI-18) was synthesized according to the following scheme 18.
[Chemical 38]

·化合物（M-18-1）的合成
於1 L茄形燒瓶中投入82 g的4-羥基苯甲酸甲酯、166 g的碳酸鉀、以及400 mL的N,N-二甲基乙醯胺，並於室溫下進行1小時攪拌後，添加95 g的4,4,4-三氟-1-碘丁烷，並於室溫下、5小時攪拌下進行反應。反應結束後，利用水進行再沈澱。其次，向該沈澱中添加32 g的氫氧化鈉及400 mL的水，並回流4小時，進行水解反應。反應結束後，利用鹽酸進行中和，並利用乙醇對所生成的沈澱進行再結晶，藉此獲得80 g的化合物（M-18-1）。
·化合物（MI-18-2）的合成
於反應容器中取46.4 g的化合物（M-18-1），向其中添加200 mL的亞硫醯氯及0.2 mL的N,N-二甲基甲醯胺，並於80℃下攪拌1小時。其次，於減壓下將亞硫醯氯餾去後，添加四氫呋喃並製成溶液A。其次，於與所述不同的2 L三口燒瓶中投入30 g的4-羥基苯甲酸、55 g的碳酸鉀、2.4 g的四丁基銨、200 mL的四氫呋喃、以及400 mL的水。對該水溶液進行冰浴冷卻，並緩慢滴加溶液A，進而於2小時攪拌下進行反應。反應結束後，向反應混合物中添加鹽酸並進行中和，利用乙酸乙酯進行提取後，利用硫酸鎂對提取液進行乾燥，並進行濃縮，之後利用乙醇進行再結晶，藉此獲得39 g的化合物（M-18-2）的白色結晶。
·化合物（M-18-3）的合成
作為原料，代替化合物（M-18-1）而使用化合物（M-18-2），並代替4-羥基苯甲酸而使用4-羥基肉桂酸，除此以外，藉由與化合物（M-18-2）相同的方法獲得33 g的化合物（M-18-3）。
·化合物（MI-18）的合成
於合成例1-1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（MI-18-3），除此以外，藉由與合成例1-1相同的方法而獲得15.4 g的化合物（MI-18）。· Synthesis of compound (M-18-1) In a 1 L eggplant-shaped flask, 82 g of methyl 4-hydroxybenzoate, 166 g of potassium carbonate, and 400 mL of N, N-dimethylacetamidamine were charged. After stirring at room temperature for 1 hour, 95 g of 4,4,4-trifluoro-1-iodobutane was added, and the reaction was performed at room temperature with stirring for 5 hours. After completion of the reaction, reprecipitation was performed with water. Next, 32 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 4 hours to perform a hydrolysis reaction. After completion of the reaction, 80 g of a compound (M-18-1) was obtained by neutralizing with hydrochloric acid and recrystallizing the resulting precipitate with ethanol.
· Synthesis of compound (MI-18-2) Take 46.4 g of compound (M-18-1) in a reaction vessel, and add 200 mL of thionyl chloride and 0.2 mL of N, N-dimethylformamide Phenamine was stirred at 80 ° C for 1 hour. Next, the thionyl chloride was distilled off under reduced pressure, and then tetrahydrofuran was added to prepare solution A. Next, into a 2 L three-necked flask different from the above, 30 g of 4-hydroxybenzoic acid, 55 g of potassium carbonate, 2.4 g of tetrabutylammonium, 200 mL of tetrahydrofuran, and 400 mL of water were charged. This aqueous solution was cooled in an ice bath, solution A was slowly added dropwise, and the reaction was further performed under stirring for 2 hours. After the reaction was completed, hydrochloric acid was added to the reaction mixture for neutralization, and after extraction with ethyl acetate, the extract was dried with magnesium sulfate, concentrated, and then recrystallized with ethanol to obtain 39 g of a compound. (M-18-2) white crystals.
· Synthesis of compound (M-18-3) As a raw material, compound (M-18-2) is used instead of compound (M-18-1), and 4-hydroxycinnamic acid is used instead of 4-hydroxybenzoic acid. Other than that, 33 g of a compound (M-18-3) was obtained by the same method as the compound (M-18-2).
· Synthesis of compound (MI-18) In Synthesis Example 1-1, instead of (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1' -((Cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid, except that compound (MI-18-3) was used. 15.4 g was obtained in the same manner as in Synthesis Example 1-1. Compound (MI-18).

[合成例19：化合物（MI-19）的合成]
按照下述流程19來合成化合物（MI-19）。
[化39]

[Synthesis Example 19: Synthesis of Compound (MI-19)]
Compound (MI-19) was synthesized according to the following scheme 19.
[Chemical 39]

於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（M-19-3），除此以外，藉由與合成例1相同的方法而獲得16.1 g的化合物（MI-19）。再者，於合成例18中，代替4,4,4-三氟-1-碘丁烷而使用1,1,1,2,2-五氟-4-碘丁烷來合成化合物（M-19-1）～化合物（MI-19-3）。In Synthesis Example 1, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4- Carbonyl) oxy) phenyl) acrylic acid was used in the same manner as in Synthesis Example 1 except that compound (M-19-3) was used to obtain 16.1 g of compound (MI-19). Furthermore, in Synthesis Example 18, instead of 4,4,4-trifluoro-1-iodobutane, 1,1,1,2,2-pentafluoro-4-iodobutane was used to synthesize the compound (M- 19-1) ~ Compound (MI-19-3).

[合成例20：化合物（MI-20）的合成]
於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用(E)-4-((3-(4-((4-(4,4,4-三氟丁氧基)苯甲醯基)氧基)苯基)丙烯醯基)氧基)苯甲酸，除此以外，藉由與合成例1相同的方法而獲得16.1 g的化合物（MI-20）。[Synthesis Example 20: Synthesis of Compound (MI-20)]
In Synthesis Example 1, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4- Carbonyl) oxy) phenyl) acrylic acid and (E) -4-((3- (4-((4- (4,4,4-trifluorobutoxy) benzyl) oxy) benzene 16.1 g of a compound (MI-20) was obtained in the same manner as in Synthesis Example 1 except that the group was acryl) acryl) oxy) benzoic acid.

[合成例21：化合物（MI-21）的合成]
按照下述流程21來合成化合物（MI-21）。
[化40]

[Synthesis Example 21: Synthesis of Compound (MI-21)]
Compound (MI-21) was synthesized according to the following scheme 21.
[Chemical 40]

於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（MI-21-3），除此以外，藉由與合成例1相同的方法而獲得15.8 g的化合物（MI-21）。再者，於合成例22中，將起始物質自4-羥基-2,3,5,6-四氟苯基苯甲酸代替為3-氟-4-羥基苯甲酸，除此以外，藉由相同的方法來合成化合物（M-21-1）～化合物（M-21-3）。In Synthesis Example 1, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)]-4- 15.8 g of a compound (MI-21) was obtained by the same method as in Synthesis Example 1 except that carbonyl) oxy) phenyl) acrylic acid was used as the compound (MI-21-3). In addition, in Synthesis Example 22, 4-hydroxy-2,3,5,6-tetrafluorophenylbenzoic acid was replaced with 3-fluoro-4-hydroxybenzoic acid as the starting material. Compound (M-21-1) to compound (M-21-3) were synthesized by the same method.

[合成例22：化合物（MI-22）的合成]
按照下述流程22來合成化合物（MI-22）。
[化41]

[Synthesis Example 22: Synthesis of Compound (MI-22)]
Compound (MI-22) was synthesized according to the following scheme 22.
[Chemical 41]

·化合物（M-22-1）的合成
於裝有攪拌器的1000 mL三口燒瓶中添加21.0 g的4-羥基-2,3,5,6-四氟苯基苯甲酸、53.0 g的4,4,4-三氟-1-碘丁烷、83.2 g的碳酸鉀、以及500 mL的二甲基乙醯胺，並於氮氣環境下、90℃下加熱10小時。反應後，注入至500 mL的水中，並利用300 mL乙酸乙酯進行3次提取。利用無水硫酸鈉對有機層進行乾燥後，將溶媒減壓餾去。向所獲得的粗產物中添加100 mL的THF、100 mL的乙醇、以及50 mL的水，進而添加9.2 g的氫氧化鋰一水合物，並於室溫下攪拌5小時。反應後，利用1規定鹽酸而製成酸性，之後利用100 mL的乙酸乙酯進行3次提取。向有機層中添加無水硫酸鈉並進行乾燥，之後將溶媒減壓餾去，並利用乙酸乙酯/己烷進行再結晶，獲得25.0 g的化合物（M-22-1）。
·化合物（M-22-2）的合成
於合成例18中，代替化合物（M-18-2）而使用化合物（M-22-1），除此以外，藉由相同的方法來合成，從而獲得22.1 g的化合物（M-22-2）。
·化合物（M-21-3）的合成
於合成例18中，代替化合物（M-18-1）而使用化合物（M-22-2），除此以外，藉由相同的方法來合成，從而獲得17.1 g的化合物（M-22-3）。
·化合物（MI-22）的合成
於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（M-22-3），除此以外，藉由與合成例1相同的方法而獲得17.2 g的化合物（MI-22）。· Synthesis of compound (M-22-1) In a 1000 mL three-necked flask equipped with a stirrer, 21.0 g of 4-hydroxy-2,3,5,6-tetrafluorophenylbenzoic acid and 53.0 g of 4, 4,4-trifluoro-1-iodobutane, 83.2 g of potassium carbonate, and 500 mL of dimethylacetamide, and heated under a nitrogen atmosphere at 90 ° C. for 10 hours. After the reaction, it was poured into 500 mL of water and extracted three times with 300 mL of ethyl acetate. After the organic layer was dried with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. To the obtained crude product, 100 mL of THF, 100 mL of ethanol, and 50 mL of water were added, and 9.2 g of lithium hydroxide monohydrate was further added, followed by stirring at room temperature for 5 hours. After the reaction, it was made acidic with a predetermined amount of hydrochloric acid, and then extracted three times with 100 mL of ethyl acetate. Anhydrous sodium sulfate was added to the organic layer and dried, and then the solvent was distilled off under reduced pressure and recrystallized with ethyl acetate / hexane to obtain 25.0 g of a compound (M-22-1).
-Synthesis of Compound (M-22-2) In Synthesis Example 18, a compound (M-22-1) was used in place of the compound (M-18-2). 22.1 g of a compound (M-22-2) was obtained.
-Synthesis of Compound (M-21-3) In Synthesis Example 18, compound (M-22-2) was used in place of compound (M-18-1). 17.1 g of the compound (M-22-3) was obtained.
· Compound (MI-22) was synthesized in Synthesis Example 1 instead of (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-linked (Cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid was used in the same manner as in Synthesis Example 1 except that compound (M-22-3) was used to obtain 17.2 g of compound (MI -twenty two).

[合成例23：化合物（MI-23）的合成]
按照下述流程23來合成化合物（MI-23）。
[化42]

[Synthesis Example 23: Synthesis of Compound (MI-23)]
Compound (MI-23) was synthesized according to the following scheme 23.
[Chemical 42]

·化合物（M-23-1）的合成
於裝有攪拌器的500 mL三口燒瓶中添加16.8 g的3,4-二羥基苯甲酸甲酯、53.0 g的4,4,4-三氟-1-碘丁烷、83.2 g的碳酸鉀、以及500 mL的二甲基乙醯胺，並於氮氣環境下、90℃下加熱10小時。反應後，注入至500 mL的水中，並對沈澱進行過濾。將經過濾的固體添加至10%氫氧化鈉水溶液中，並於室溫下攪拌5小時。反應後，利用1規定鹽酸製成酸性，並對所生成的沈澱進行過濾，之後，利用真空乾燥機進行乾燥，從而獲得28.0 g的化合物（M-23-1）。
·化合物（M-23-2）的合成
於合成例18中，代替化合物（M-18-2）而使用化合物（M-23-1），除此以外，藉由相同的方法來合成，從而獲得23.4 g的化合物（M-23-2）。
·化合物（M-23-3）的合成
於合成例18中，代替化合物（M-18-1）而使用化合物（M-23-2），除此以外，藉由相同的方法來合成，從而獲得17.3 g的化合物（M-23-2）。
·化合物（MI-23）的合成
於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（MI-23-3），除此以外，藉由與合成例1相同的方法而獲得17.2 g的化合物（MI-23）。· Synthesis of compound (M-23-1) In a 500 mL three-necked flask equipped with a stirrer, 16.8 g of methyl 3,4-dihydroxybenzoate and 53.0 g of 4,4,4-trifluoro-1 were added. -Iodobutane, 83.2 g of potassium carbonate, and 500 mL of dimethylacetamide, and heated under a nitrogen atmosphere at 90 ° C for 10 hours. After the reaction, it was poured into 500 mL of water, and the Shendian was filtered. The filtered solid was added to a 10% aqueous sodium hydroxide solution and stirred at room temperature for 5 hours. After the reaction, a predetermined amount of hydrochloric acid was used to make the acidic, and the resulting precipitate was filtered, and then dried with a vacuum dryer to obtain 28.0 g of a compound (M-23-1).
-Synthesis of Compound (M-23-2) In Synthesis Example 18, a compound (M-23-1) was used in place of the compound (M-18-2). 23.4 g of a compound (M-23-2) was obtained.
-Synthesis of Compound (M-23-3) In Synthesis Example 18, a compound (M-23-2) was used in place of the compound (M-18-1). 17.3 g of the compound (M-23-2) was obtained.
· Synthesis of compound (MI-23) In Synthesis Example 1, instead of (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-linked (Cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid was used in the same manner as in Synthesis Example 1 except that compound (MI-23-3) was used to obtain 17.2 g of compound (MI -twenty three).

[合成例24：化合物（MI-24）的合成]
按照下述流程24來合成化合物（MI-24）。
[化43]

[Synthesis Example 24: Synthesis of Compound (MI-24)]
Compound (MI-24) was synthesized by following Scheme 24.
[Chemical 43]

·化合物（M-24-1）的合成
於裝有攪拌器的500 mL茄形燒瓶中添加10.0 g的4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羧酸、37 g的亞硫醯氯、以及0.02 g的N,N-二甲基甲醯胺，於60℃下攪拌2小時。其後，利用膜片泵將過剩的亞硫醯氯去除，並添加250 g的四氫呋喃而製成溶液A。
重新於裝有攪拌器的1000 mL三口燒瓶中添加6.8 g的對苯二酚、140 g的四氫呋喃、以及4.9 g的吡啶，並進行冰浴。向其中滴加溶液A並於室溫下攪拌8小時。利用2500 mL的水對反應液進行再沈澱，對所獲得的白色固體進行真空乾燥。利用乙酸乙酯進行提取，並將己烷/乙酸乙酯作為展開溶媒且利用矽膠管柱進行精製。利用旋轉蒸發器將溶劑去除後，進行真空乾燥，藉此獲得3.8 g的化合物（M-24-1）。
·化合物（MI-24）的合成
添加1.77 g的(E)-3-(4-(2,5-二氧代-2,5-二氫-1H-吡咯-1-基)苯基)丙烯酸、8.7 g的亞硫醯氯、以及0.01 g的N,N-二甲基甲醯胺，於60℃下攪拌2小時。其後，利用膜片泵將過剩的亞硫醯氯去除，並添加50 g的四氫呋喃而製成溶液B。
重新於裝有攪拌器的100 mL三口燒瓶中添加3.0 g的化合物（M-24-1）、25 g的四氫呋喃、以及1.2 g的吡啶，並進行冰浴。向其中滴加溶液B並於室溫下攪拌8小時。利用1000 mL的水對反應液進行再沈澱，對所獲得的白色固體進行真空乾燥，藉此獲得3.7 g的化合物（MI-24）。· Synthesis of compound (M-24-1) In a 500 mL eggplant-shaped flask equipped with a stirrer, 10.0 g of 4 '-(4,4,4-trifluorobutyl)-[1,1'-linked (Cyclohexane)]-4-carboxylic acid, 37 g of thionyl chloride, and 0.02 g of N, N-dimethylformamide, and stirred at 60 ° C for 2 hours. Thereafter, the excess thionyl chloride was removed by a diaphragm pump, and 250 g of tetrahydrofuran was added to prepare a solution A.
In a 1000 mL three-necked flask equipped with a stirrer, 6.8 g of hydroquinone, 140 g of tetrahydrofuran, and 4.9 g of pyridine were added again, and an ice bath was performed. Solution A was added dropwise thereto and stirred at room temperature for 8 hours. The reaction solution was reprecipitated with 2500 mL of water, and the obtained white solid was dried under vacuum. Extraction was performed with ethyl acetate, and hexane / ethyl acetate was used as a developing solvent, and purification was performed using a silica gel column. After removing the solvent by using a rotary evaporator, vacuum drying was performed to obtain 3.8 g of a compound (M-24-1).
· Synthesis of compound (MI-24) Added 1.77 g of (E) -3- (4- (2,5-dioxo-2,5-dihydro-1H-pyrrole-1-yl) phenyl) acrylic acid , 8.7 g of thionyl chloride, and 0.01 g of N, N-dimethylformamide, and stirred at 60 ° C for 2 hours. Thereafter, the excess thionyl chloride was removed by a diaphragm pump, and 50 g of tetrahydrofuran was added to prepare a solution B.
In a 100 mL three-necked flask equipped with a stirrer, 3.0 g of the compound (M-24-1), 25 g of tetrahydrofuran, and 1.2 g of pyridine were added, and the mixture was ice-baked. Solution B was added dropwise thereto and stirred at room temperature for 8 hours. The reaction solution was reprecipitated with 1000 mL of water, and the obtained white solid was vacuum-dried to obtain 3.7 g of a compound (MI-24).

[合成例25]
按照下述流程25來合成化合物（MI-25）。
[化44]

[Synthesis example 25]
Compound (MI-25) was synthesized by following Scheme 25.
[Chemical 44]

·化合物（M-25-1）的合成
於合成例18中，代替4-羥基苯甲酸甲酯而使用6-羥基-2-萘甲酸甲酯，除此以外，藉由相同的方法來合成，從而獲得30.1 g的化合物（M-25-1）。
·化合物（M-25-2）的合成
於合成例18中，代替化合物（M-18-2）而使用化合物（M-25-1），除此以外，藉由相同的方法來合成，從而獲得15.0 g的化合物（M-25-2）。
·化合物（MI-25）的合成
於合成例1中，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用化合物（M-25-2），除此以外，藉由與合成例1相同的方法而獲得13.5 g的化合物（MI-25）。-Synthesis of Compound (M-25-1) In Synthesis Example 18, methyl 6-hydroxy-2-naphthoate was used instead of methyl 4-hydroxybenzoate, and was synthesized by the same method. Thus, 30.1 g of a compound (M-25-1) was obtained.
-Synthesis of Compound (M-25-2) In Synthesis Example 18, compound (M-25-1) was used instead of compound (M-18-2). 15.0 g of a compound (M-25-2) was obtained.
· Synthesis of compound (MI-25) In Synthesis Example 1, instead of (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-linked (Cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid was used in the same manner as in Synthesis Example 1 except that compound (M-25-2) was used to obtain 13.5 g of compound (MI -25).

[合成例26：化合物（MI-26）的合成]
於合成例1中，代替4-羥基苯基馬來醯亞胺而使用3-羥基苯基馬來醯亞胺，除此以外，藉由與合成例1相同的方法而獲得14.2 g的化合物（MI-26）。[Synthesis Example 26: Synthesis of Compound (MI-26)]
In Synthesis Example 1, except that 3-hydroxyphenylmaleimide was used instead of 4-hydroxyphenylmaleimide, 14.2 g of a compound was obtained in the same manner as in Synthesis Example 1 ( MI-26).

[合成例27：化合物（MI-27）的合成]
按照下述流程27來合成化合物（MI-27）。
[化45]

[Synthesis Example 27: Synthesis of Compound (MI-27)]
Compound (MI-27) was synthesized by following Scheme 27.
[Chemical 45]

·化合物（M-27-1）的合成
於裝有攪拌器的2000 mL三口燒瓶中取6.90 g的(4-胺基苯基)乙醇，添加200 g的四氫呋喃並進行冰浴。向其中滴加包含5.11 g的馬來酸酐與200 g的四氫呋喃的溶液，並於室溫下攪拌3小時。其後，藉由過濾回收所析出的固體。對該固體進行真空乾燥，藉此獲得11.5 g的化合物（M-27-1）。
·化合物（M-27-2）的合成
於裝有攪拌器的500 mL三口燒瓶中添加10.9 g的化合物（M-27-1）、9.38 g的氯化鋅(II)、250 g的甲苯，並於80℃下加熱攪拌。向其中滴加包含14.8 g的雙(三甲基矽烷基)胺與100 g的甲苯的溶液，並於80℃下攪拌5小時。其後，向反應液中添加300 g的乙酸乙酯，並進行2次利用1 mol/L鹽酸的分液清洗、1次利用碳酸氫鈉水溶液的分液清洗、1次利用飽和食鹽水的分液清洗。其後，利用旋轉蒸發器對有機層進行緩慢濃縮直至內容量為50 g為止，並藉由過濾回收中途所析出的白色固體。對該白色固體進行真空乾燥，藉此獲得5.86 g的化合物（M-27-2）。
·化合物（MI-27）的合成
於裝有攪拌器的100 mL茄形燒瓶中添加9.37 g的(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸、25 g的亞硫醯氯、0.02 g的N,N-二甲基甲醯胺，並於80℃下攪拌1小時。其後，利用膜片泵將過剩的亞硫醯氯去除，從而獲得化合物（M-27-3）。向其中添加100 g的四氫呋喃而製成溶液A。
重新於裝有攪拌器的500 mL三口燒瓶中添加4.34 g的化合物（M-27-2）、200 g的四氫呋喃、以及2.58 g的三乙基胺，並進行冰浴。向其中滴加溶液A並於室溫下攪拌3小時。利用800 mL的水對反應液進行再沈澱，對所獲得的白色固體進行真空乾燥，藉此獲得8.78 g的化合物（MI-27）。· Synthesis of compound (M-27-1) In a 2000 mL three-necked flask equipped with a stirrer, 6.90 g of (4-aminophenyl) ethanol was taken, 200 g of tetrahydrofuran was added, and an ice bath was performed. A solution containing 5.11 g of maleic anhydride and 200 g of tetrahydrofuran was added dropwise thereto, and stirred at room temperature for 3 hours. Thereafter, the precipitated solid was recovered by filtration. This solid was vacuum-dried, whereby 11.5 g of a compound (M-27-1) was obtained.
· Synthesis of compound (M-27-2) In a 500 mL three-necked flask equipped with a stirrer, add 10.9 g of compound (M-27-1), 9.38 g of zinc (II) chloride, and 250 g of toluene. And heated and stirred at 80 ° C. A solution containing 14.8 g of bis (trimethylsilyl) amine and 100 g of toluene was added dropwise thereto, and stirred at 80 ° C. for 5 hours. Thereafter, 300 g of ethyl acetate was added to the reaction solution, and the liquid was washed twice with 1 mol / L hydrochloric acid, the liquid was washed once with a sodium bicarbonate aqueous solution, and the liquid was washed once with saturated saline. Fluid cleaning. Thereafter, the organic layer was slowly concentrated with a rotary evaporator until the content was 50 g, and a white solid precipitated in the middle was recovered by filtration. This white solid was vacuum-dried to obtain 5.86 g of a compound (M-27-2).
· Synthesis of compound (MI-27) In a 100 mL eggplant-shaped flask equipped with a stirrer, 9.37 g of (E) -3- (4-((4 '-(4,4,4-trifluorobutyl) )-[1,1'-bi (cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid, 25 g of thionyl chloride, 0.02 g of N, N-dimethylformamide, And stirred at 80 ° C for 1 hour. Thereafter, the excess thionyl chloride was removed by a diaphragm pump to obtain a compound (M-27-3). 100 g of tetrahydrofuran was added thereto to prepare a solution A.
In a 500 mL three-necked flask equipped with a stirrer, 4.34 g of the compound (M-27-2), 200 g of tetrahydrofuran, and 2.58 g of triethylamine were added again, and an ice bath was performed. Solution A was added dropwise thereto and stirred at room temperature for 3 hours. The reaction solution was reprecipitated with 800 mL of water, and the obtained white solid was vacuum-dried to obtain 8.78 g of a compound (MI-27).

[合成例28：化合物（MI-28）的合成]
按照下述流程28來合成化合物（MI-28）。
[化46]

[Synthesis Example 28: Synthesis of Compound (MI-28)]
Compound (MI-28) was synthesized according to the following scheme 28.
[Chemical 46]

於合成例27的化合物（MI-27）的合成中，作為原料，代替化合物（M-27-3）及化合物（M-27-2）而使用1-[4-(羥基甲基)苯基]吡咯-2,5-二酮，除此以外，藉由與合成例27的化合物（MI-27）的合成相同的方法來獲得24.1 g的化合物（MI-28）。In the synthesis of the compound (MI-27) of Synthesis Example 27, 1- [4- (hydroxymethyl) phenyl was used instead of the compound (M-27-3) and the compound (M-27-2) as a raw material. Except for pyrrole-2,5-dione, 24.1 g of a compound (MI-28) was obtained by the same method as the synthesis of the compound (MI-27) of Synthesis Example 27.

[合成例29：化合物（MI-29）的合成]
按照下述流程29來合成化合物（MI-29）。
[化47]

[Synthesis Example 29: Synthesis of Compound (MI-29)]
Compound (MI-29) was synthesized according to the following scheme 29.
[Chemical 47]

·化合物（M-29-1）的合成
於裝有攪拌器的2000 mL三口燒瓶中取15.1 g的4-(4-胺基苯基)丙烷-1-醇、1000 g的四氫呋喃，添加15.2 g的三乙基胺並進行冰浴。向其中滴加包含26.1 g的二碳酸第三丁酯與100 g的四氫呋喃的溶液，並於室溫下攪拌10小時，之後向反應液中添加300 g的乙酸乙酯，並利用200 g的蒸餾水進行4次分液清洗。其後，利用旋轉蒸發器對有機層進行緩慢濃縮直至內容量為100 g為止，並藉由過濾回收中途所析出的白色固體。對該白色固體進行真空乾燥，藉此獲得23.6 g的化合物（M-29-1）。
·化合物（M-29-2）～化合物（M-29-4）的合成
於合成例3中，作為原料，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸及N-Boc-4-羥基苯胺而使用化合物（M-29-1），除此以外，藉由與合成例3相同的方法而獲得30.0 g的化合物（M-29-4）。
·化合物（MI-29）的合成
於裝有攪拌器的2000 mL三口燒瓶中添加30.0 g的化合物（M-29-4）、8.79 g的氯化鋅(II)、以及250 g的甲苯，並於80℃下加熱攪拌。向其中滴加包含13.8 g的雙(三甲基矽烷基)胺與100 g的甲苯的溶液，並於80℃下攪拌5小時。其後，向反應液中添加300 g的乙酸乙酯，並進行2次利用1 mol/L鹽酸的分液清洗、1次利用碳酸氫鈉水溶液的分液清洗、1次利用飽和食鹽水的分液清洗。其後，利用旋轉蒸發器對有機層進行緩慢濃縮直至內容量為50 g為止，並藉由過濾回收中途所析出的白色固體。對該白色固體進行真空乾燥，藉此獲得9.18 g的化合物（MI-29）。· Synthesis of compound (M-29-1) In a 2000 mL three-necked flask equipped with a stirrer, 15.1 g of 4- (4-aminophenyl) propane-1-ol and 1000 g of tetrahydrofuran were added, and 15.2 g was added. Triethylamine and ice bath. A solution containing 26.1 g of third butyl dicarbonate and 100 g of tetrahydrofuran was added dropwise thereto, followed by stirring at room temperature for 10 hours, and then 300 g of ethyl acetate was added to the reaction solution, and 200 g of distilled water was used. Perform 4 liquid separation washings. Thereafter, the organic layer was concentrated slowly by a rotary evaporator until the content was 100 g, and a white solid precipitated in the middle was recovered by filtration. This white solid was vacuum-dried, whereby 23.6 g of a compound (M-29-1) was obtained.
· Synthesis of compound (M-29-2) to compound (M-29-4) In Synthesis Example 3, as a raw material, (E) -3- (4-((4 '-(4,4,4) -Trifluorobutyl)-[1,1'-bi (cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid and N-Boc-4-hydroxyaniline using compound (M-29-1 ), 30.0 g of a compound (M-29-4) was obtained by the same method as in Synthesis Example 3.
· Synthesis of compound (MI-29) In a 2000 mL three-necked flask equipped with a stirrer, 30.0 g of compound (M-29-4), 8.79 g of zinc (II) chloride, and 250 g of toluene were added, and Heat and stir at 80 ° C. A solution containing 13.8 g of bis (trimethylsilyl) amine and 100 g of toluene was added dropwise thereto, and stirred at 80 ° C. for 5 hours. Thereafter, 300 g of ethyl acetate was added to the reaction solution, and the liquid was washed twice with 1 mol / L hydrochloric acid, the liquid was washed once with a sodium bicarbonate aqueous solution, and the liquid was washed once with saturated saline. Fluid cleaning. Thereafter, the organic layer was slowly concentrated with a rotary evaporator until the content was 50 g, and a white solid precipitated in the middle was recovered by filtration. This white solid was vacuum-dried to obtain 9.18 g of a compound (MI-29).

[合成例30：化合物（MI-30）的合成]
按照下述流程30來合成化合物（MI-30）。
[化48]

[Synthesis Example 30: Synthesis of Compound (MI-30)]
Compound (MI-30) was synthesized according to the following scheme 30.
[Chemical 48]

·化合物（M-30-1）的合成
於裝有攪拌器的500 mL三口燒瓶中添加20.9 g的N-Boc-4-羥基苯胺、15.0 g的2-溴乙醇、20.7 g的碳酸鉀、250 mL的N,N-二甲基甲醯胺，並於60℃下反應4小時。反應後，將反應液注入至1500 mL的蒸餾水中，並濾取所析出的固體。其後，對固體進行真空乾燥，藉此獲得24.8 g的化合物（M-30-1）。
·化合物（MI-30）的合成
於合成例29的化合物（M-29-1）～化合物（M-29-4）及化合物（MI-29）的合成中，作為原料，代替化合物（M-29-1）而使用化合物（M-30-1），除此以外，藉由與合成例29相同的方法而獲得32.0 g的化合物（MI-30）。· Synthesis of compound (M-30-1) In a 500 mL three-necked flask equipped with a stirrer, 20.9 g of N-Boc-4-hydroxyaniline, 15.0 g of 2-bromoethanol, 20.7 g of potassium carbonate, 250 mL of N, N-dimethylformamide, and reacted at 60 ° C for 4 hours. After the reaction, the reaction solution was poured into 1500 mL of distilled water, and the precipitated solid was collected by filtration. Thereafter, the solid was vacuum-dried, thereby obtaining 24.8 g of a compound (M-30-1).
· Synthesis of Compound (MI-30) In the synthesis of Compound (M-29-1) to Compound (M-29-4) and Compound (MI-29) in Synthesis Example 29, it was used as a raw material in place of Compound (M- 29-1) Except for using compound (M-30-1), 32.0 g of compound (MI-30) was obtained in the same manner as in Synthesis Example 29.

[合成例31：化合物（MI-31）的合成]
於合成例27中，作為原料，代替(E)-3-(4-((4'-(4,4,4-三氟丁基)-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸而使用(E)-3-(4-((4'-戊基-[1,1'-聯(環己烷)]-4-羰基)氧基)苯基)丙烯酸，除此以外，藉由與合成例27相同的方法而獲得14.4 g的化合物（MI-31）。[Synthesis Example 31: Synthesis of Compound (MI-31)]
In Synthesis Example 27, as a raw material, (E) -3- (4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bi (cyclohexane)] was used instead. -4-carbonyl) oxy) phenyl) acrylic acid and (E) -3- (4-((4'-pentyl- [1,1'-bi (cyclohexane))-4-carbonyl) oxy Except for the group) phenyl) acrylic acid, 14.4 g of a compound (MI-31) was obtained in the same manner as in Synthesis Example 27.

[比較例合成例1及比較合成例2]
化合物（MI-32）是依照日本專利第4296821號公報的記載方法來合成，化合物（MI-33）是依照日本專利第3055062號公報的記載方法來合成。[Comparative Example Synthesis Example 1 and Comparative Synthesis Example 2]
Compound (MI-32) was synthesized in accordance with the method described in Japanese Patent No. 4296621, and compound (MI-33) was synthesized in accordance with the method described in Japanese Patent No. 3055062.

[合成例32：化合物（MI-34）的合成]
於合成例15中，代替丙烯酸而使用甲基丙烯酸，除此以外，藉由與化合物（MI-15）相同的方法來獲得化合物（MI-34）（參照下述流程32）。
[化49]

[Synthesis Example 32: Synthesis of Compound (MI-34)]
In Synthesis Example 15, a compound (MI-34) was obtained by the same method as the compound (MI-15), except that methacrylic acid was used instead of acrylic acid (see Scheme 32 below).
[Chemical 49]

[合成例33：化合物（MI-35）的合成]
於合成例15中，代替4-羥基苯基馬來醯亞胺而使用4-羥基-3-甲基苯基馬來醯亞胺，除此以外，藉由與化合物（MI-15）相同的方法而獲得化合物（MI-35）（參照下述流程33）。
[化50]

[Synthesis Example 33: Synthesis of Compound (MI-35)]
In Synthesis Example 15, the same compound as the compound (MI-15) was used except that 4-hydroxy-3-methylphenylmaleimide was used instead of 4-hydroxyphenylmaleimide. The compound (MI-35) was obtained by the method (refer to the following scheme 33).
[Chemical 50]

[合成例34：化合物（MI-36）的合成]
於合成例15中，代替丙烯酸而使用甲基丙烯酸，且代替4-羥基苯基馬來醯亞胺而使用4-羥基-3-甲基苯基馬來醯亞胺，除此以外，藉由與化合物（MI-15）相同的方法而獲得化合物（MI-36）。[Synthesis Example 34: Synthesis of Compound (MI-36)]
In Synthesis Example 15, methacrylic acid was used instead of acrylic acid, and 4-hydroxy-3-methylphenylmaleimide was used instead of 4-hydroxyphenylmaleimide. The compound (MI-36) was obtained by the same method as the compound (MI-15).

[合成例35：化合物（MI-37）的合成]
於化合物（MI-34）的合成中，代替碘化4,4,4-三氟丁基三苯基鏻而使用碘化戊基三苯基鏻，除此以外，藉由與化合物（MI-34）相同的方法而獲得化合物（MI-37）（參照下述流程35）。
[化51]

[Synthesis Example 35: Synthesis of Compound (MI-37)]
In the synthesis of compound (MI-34), instead of 4,4,4-trifluorobutyltriphenylsulfonium iodide, pentyltriphenylsulfonium iodide was used. 34) Compound (MI-37) was obtained in the same manner (see Scheme 35 below).
[Chemical 51]

[合成例36：化合物（MI-38）的合成]
於化合物（MI-35）的合成中，代替碘化4,4,4-三氟丁基三苯基鏻而使用碘化戊基三苯基鏻，除此以外，藉由與化合物（MI-35）相同的方法而獲得化合物（MI-38）。
[合成例37：化合物（MI-39）的合成]
於化合物（MI-36）的合成中，代替碘化4,4,4-三氟丁基三苯基鏻而使用碘化戊基三苯基鏻，除此以外，藉由與化合物（MI-36）相同的方法而獲得化合物（MI-39）。
[合成例38：化合物（MI-40）的合成]
於化合物（MI-37）的合成中，代替甲基丙烯酸而使用2-(三氟甲基)丙烯酸，除此以外，藉由與化合物（MI-37）相同的方法而獲得化合物（MI-40）。[Synthesis Example 36: Synthesis of Compound (MI-38)]
In the synthesis of compound (MI-35), instead of 4,4,4-trifluorobutyltriphenylphosphonium iodide, pentyltriphenylphosphonium iodide was used. 35) Compound (MI-38) was obtained in the same manner.
[Synthesis Example 37: Synthesis of Compound (MI-39)]
In the synthesis of compound (MI-36), instead of 4,4,4-trifluorobutyltriphenylphosphonium iodide, pentyltriphenylphosphonium iodide was used. 36) Compound (MI-39) was obtained in the same manner.
[Synthesis Example 38: Synthesis of Compound (MI-40)]
In the synthesis of compound (MI-37), except that 2- (trifluorometh) acrylic acid was used instead of methacrylic acid, compound (MI-40) was obtained by the same method as compound (MI-37). ).

[合成例39：化合物（MI-41）的合成]
於合成例15中，代替4-羥基苯基馬來醯亞胺而使用4-羥基-3-甲氧基苯基馬來醯亞胺，除此以外，藉由與化合物（MI-15）相同的方法而獲得化合物（MI-41）。再者，關於4-羥基-3-甲氧基苯基馬來醯亞胺，是藉由在合成例2的化合物（M-2-1）的合成中代替4-羥基環己基胺而使用4-羥基-3-甲氧基苯胺來合成。
[合成例40：化合物（MI-42）的合成]
於化合物（M-37）的合成中，代替4-羥基苯基馬來醯亞胺而使用4-羥基-3-氟苯基馬來醯亞胺，除此以外，藉由與化合物（MI-37）相同的方法而獲得化合物（MI-42）。再者，關於4-羥基-3-氟苯基馬來醯亞胺，是藉由在合成例2的化合物（M-2-1）的合成中代替4-羥基環己基胺而使用3-氟-4-羥基苯胺來合成。
[合成例41：化合物（MI-43）的合成]
於化合物（M-36）的合成中，代替甲基丙烯酸而使用2-氟丙烯酸，除此以外，藉由與化合物（MI-36）相同的方法來獲得化合物（MI-43）。[Synthesis Example 39: Synthesis of Compound (MI-41)]
In Synthesis Example 15, it was the same as compound (MI-15) except that 4-hydroxy-3-methoxyphenylmaleimide was used instead of 4-hydroxyphenylmaleimide. To obtain compound (MI-41). The 4-hydroxy-3-methoxyphenylmaleimide is used in place of 4-hydroxycyclohexylamine in the synthesis of the compound (M-2-1) of Synthesis Example 2 -Hydroxy-3-methoxyaniline.
[Synthesis Example 40: Synthesis of Compound (MI-42)]
In the synthesis of the compound (M-37), 4-hydroxy-3-fluorophenylmaleimide was used instead of 4-hydroxyphenylmaleimide. In addition, the compound (MI- 37) Compound (MI-42) was obtained in the same manner. In addition, regarding 4-hydroxy-3-fluorophenylmaleimide, 3-fluorocyclohexylamine was used instead of 4-hydroxycyclohexylamine in the synthesis of the compound (M-2-1) of Synthesis Example 2. -4-Hydroxyaniline.
[Synthesis Example 41: Synthesis of Compound (MI-43)]
In the synthesis of compound (M-36), compound (MI-43) was obtained by the same method as compound (MI-36), except that 2-fluoroacrylic acid was used instead of methacrylic acid.

＜聚合體的合成＞
[實施例1-1：聚合體（P-1）的合成]
於氮氣下，於100 mL二口燒瓶中添加作為聚合單體的5.00 g（7.5 mmol）的所述合成例27中所獲得的化合物（MI-27）、1.05 g（7.5 mmol）的化合物（A-3）、4.80 g（33.8 mmol）的化合物（D-1）、以及2.26 g（26.3 mmol）的化合物（D-4）、作為自由基聚合起始劑的0.39 g（1.6 mmol）的2,2'-偶氮雙(2,4-二甲基戊腈)、作為鏈轉移劑的0.39 g（1.7 mmol）的2,4-二苯基-4-甲基-1-戊烯、以及作為溶媒的52.5 ml的N-甲基-2-吡咯啶酮（NMP），並於70℃下聚合6小時。於甲醇中進行再沈澱後，對沈澱物進行過濾，並於室溫下進行8小時真空乾燥，藉此獲得目標聚合體（P-1）。藉由利用GPC的聚苯乙烯換算而測定的重量平均分子量Mw為30000，分子量分佈Mw/Mn為2。<Synthesis of Polymer>
[Example 1-1: Synthesis of Polymer (P-1)]
In a 100 mL two-necked flask under nitrogen, 5.00 g (7.5 mmol) of the compound (MI-27) obtained in Synthesis Example 27 and 1.05 g (7.5 mmol) of the compound (A) were added as polymerized monomers. -3), 4.80 g (33.8 mmol) of compound (D-1), 2.26 g (26.3 mmol) of compound (D-4), 0.39 g (1.6 mmol) of 2, as a radical polymerization initiator, 2'-azobis (2,4-dimethylvaleronitrile), 0.39 g (1.7 mmol) of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and as A solvent of 52.5 ml of N-methyl-2-pyrrolidone (NMP) was polymerized at 70 ° C for 6 hours. After reprecipitation in methanol, the precipitate was filtered and vacuum-dried at room temperature for 8 hours to obtain the target polymer (P-1). The weight average molecular weight Mw measured by polystyrene conversion by GPC was 30,000, and the molecular weight distribution Mw / Mn was 2.

[實施例1-2～實施例1-45及比較聚合例1-1～比較聚合例1-8]
將聚合單體設為下述表7及表8所示的種類及莫耳比，除此以外，與實施例1-1同樣地進行聚合，獲得與聚合體（P-1）為同等的重量平均分子量及分子量分佈的聚合體（P-2）～聚合體（P-45）及聚合體（R-1）～聚合體（R-8）的各聚合體。再者，聚合單體的總莫耳數與實施例1-1同樣地設為75.1 mmol。表7及表8中的數值表示相對於聚合體的合成中使用的所有單體的、各單體的投入量[莫耳%]。[Example 1-2 to Example 1-45 and Comparative Polymerization Example 1-1 to Comparative Polymerization Example 1-8]
The polymerization monomers were polymerized in the same manner as in Example 1-1 except that the types and mole ratios of the polymerized monomers shown in Tables 7 and 8 below were obtained, and the weight equivalent to that of the polymer (P-1) was obtained. Polymers (P-2) to Polymer (P-45) and polymers (R-1) to Polymer (R-8) each having an average molecular weight and molecular weight distribution. The total mole number of the polymerized monomer was 75.1 mmol in the same manner as in Example 1-1. The numerical values in Tables 7 and 8 indicate the input amount [mole%] of each monomer with respect to all the monomers used in the synthesis of the polymer.

[表7]



[表8]

[TABLE 7]



[TABLE 8]

[合成例42：聚醯胺酸的合成]
使作為四羧酸二酐的11.0 g（49.0 mmol）的2,3,5-三羧基環戊基乙酸二酐、作為二胺的10.0 g（50.0 mmol）的4,4'-亞甲基二苯胺溶解於84 g的NMP中，並於60℃下進行24小時反應，藉此獲得含有20質量%的聚醯胺酸的溶液。繼而，將該聚醯胺酸溶液注入至大量過剩的甲醇中並使反應產物沈澱。利用甲醇對該沈澱物進行清洗，並於減壓下以40℃乾燥15小時，藉此獲得聚醯胺酸（PAA）。[Synthesis Example 42: Synthesis of Polyamic Acid]
11.0 g (49.0 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, and 10.0 g (50.0 mmol) of 4,4'-methylene diamine as diamine Aniline was dissolved in 84 g of NMP and reacted at 60 ° C. for 24 hours to obtain a solution containing 20% by mass of polyamic acid. Then, the polyphosphonic acid solution was poured into a large amount of excess methanol and the reaction product was precipitated. The precipitate was washed with methanol, and dried at 40 ° C. for 15 hours under reduced pressure, thereby obtaining polyamic acid (PAA).

＜光垂直型液晶顯示元件的製造及評價＞
[實施例2-1]
1. 液晶配向劑（AL-1）的製備
向放入有10質量份的實施例1-1中獲得的聚合體（P-1）、及100質量份的聚醯胺酸（PAA）的容器中添加作為溶劑的NMP及丁基溶纖劑（BC），製成溶媒組成為NMP/BC=50/50（質量比）、固體成分濃度為3.5質量%的溶液。利用孔徑為1 μm的過濾器對該溶液進行過濾，藉此製備液晶配向劑（AL-1）。
2. 光垂直型液晶顯示元件的製造
於帶包含ITO膜的透明電極的玻璃基板的透明電極面上使用旋轉器塗佈所述製備的液晶配向劑（AL-1），並以80℃的加熱板進行1分鐘預烘烤。其後，於對庫內進行了氮氣置換的烘箱中，以230℃加熱1小時，形成膜厚0.1 μm的塗膜。繼而，對該塗膜表面使用Hg-Xe燈及格蘭-泰勒稜鏡（glan-taylor prism），從自基板法線傾斜40°的方向照射包含313 nm的明線的1,000 J/m² 的偏光紫外線而賦予液晶配向能力。重覆進行相同的操作，製成一對（兩塊）具有液晶配向膜的基板。
於所述基板中的一塊基板的具有液晶配向膜的面的外周，利用網版印刷來塗佈加入有直徑3.5 μm的氧化鋁球的環氧樹脂接著劑後，使一對基板的液晶配向膜面相向，以各基板的紫外線的光軸於基板面的投影方向成為逆平行的方式進行壓接，於150℃下歷時1小時使接著劑熱硬化。繼而，從液晶注入口於基板間的間隙中填充負型液晶（默克（Merck）公司製造、MLC-6608）後，以環氧系接著劑將液晶注入口密封。進而，為了去除液晶注入時的流動配向，將其以130℃加熱後緩緩冷卻到室溫。其次，於基板的外側兩面，以偏光板的偏光方向彼此正交且與液晶配向膜的紫外線的光軸於基板面的射影方向成45°角度的方式貼合偏光板，藉此製造液晶顯示元件。<Manufacturing and Evaluation of Optical Vertical Liquid Crystal Display Elements>
[Example 2-1]
1. Preparation of Liquid Crystal Alignment Agent (AL-1) To a container containing 10 parts by mass of the polymer (P-1) obtained in Example 1-1 and 100 parts by mass of polyamic acid (PAA) NMP and butyl cellosolve (BC) were added as solvents to make a solution with a solvent composition of NMP / BC = 50/50 (mass ratio) and a solid content concentration of 3.5% by mass. This solution was filtered through a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (AL-1).
2. Manufacture of light vertical liquid crystal display element On the transparent electrode surface of a glass substrate with a transparent electrode containing an ITO film, the prepared liquid crystal alignment agent (AL-1) was applied using a spinner, and heated at 80 ° C. The plate was pre-baked for 1 minute. Then, it heated at 230 degreeC for 1 hour in the oven which replaced the inside of the chamber with nitrogen, and formed the coating film with a film thickness of 0.1 micrometer. Next, a Hg-Xe lamp and a glan-taylor prism were applied to the surface of the coating film, and a polarized light of 1,000 J / m ² including a bright line of 313 nm was irradiated from a direction inclined by 40 ° from the substrate normal. Ultraviolet rays give liquid crystal alignment ability. The same operation was repeated to make a pair (two pieces) of substrates having a liquid crystal alignment film.
A liquid crystal alignment film of a pair of substrates was coated on an outer periphery of a surface of the substrate having a liquid crystal alignment film by screen printing to apply an epoxy resin adhesive with alumina balls having a diameter of 3.5 μm. The surfaces face each other, and the pressure bonding is performed so that the projection direction of the optical axis of the ultraviolet rays of each substrate on the substrate surface becomes antiparallel, and the adhesive is thermally cured at 150 ° C for 1 hour. Next, a negative liquid crystal (Merck, MLC-6608) was filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it was gradually cooled to room temperature after being heated at 130 ° C. Next, the polarizing plates are laminated on the two outer surfaces of the substrate such that the polarizing directions of the polarizing plates are orthogonal to each other and at an angle of 45 ° to the projection direction of the ultraviolet axis of the liquid crystal alignment film on the substrate surface, thereby manufacturing a liquid crystal display element .

3. 電壓保持率（VHR）的評價
對於所述2.中製造的液晶顯示元件，以60微秒的施加時間、167毫秒的跨距（span）施加5 V的電壓後，測定從施加解除起167毫秒後的電壓保持率。測定裝置是使用東陽特克尼卡（TOYO Technica）（股）製造的VHR-1。此時，於電壓保持率為90%以上的情況下設為「優良（A）」，於70%以上且小於90%的情況下設為「良好（B）」，於小於70%的情況下設為「不良（C）」。結果，該實施例中的電壓保持率為「優良（A）」的評價。3. Evaluation of the voltage holding ratio (VHR) For the liquid crystal display device manufactured in 2. described above, a voltage of 5 V was applied at an application time of 60 microseconds and a span of 167 milliseconds, and the measurement was performed after the release was applied. Voltage retention after 167 ms. As the measuring device, VHR-1 manufactured by TOYO Technica (KK) was used. At this time, it is set to "excellent (A)" when the voltage retention is 90% or more, and set to "good (B)" when it is 70% or more and less than 90%, and when it is less than 70% Set it to "defective (C)". As a result, the voltage holding ratio in this example was evaluated as "excellent (A)".

4. 預傾角的評價
關於所述2.中製造的液晶顯示元件，依據非專利文獻（T.J.謝弗等人.應用物理期刊.第19卷，p.2013（1980）（T.J.Scheffer et.al.J.Appl.Phys.vo.19,p.2013（1980）））中所記載的方法，藉由使用He-Ne雷射光的結晶旋轉法來測定液晶分子相對於基板面的傾斜角的值，並將該值設為預傾角。此時，於預傾角為85.0°以上且小於88.0°的情況下設為「優良（A）」，於88.0°以上且小於89.0°的情況下設為「良好（B）」，於89.0°以上或小於85.0°的情況下設為「不良（C）」。結果，該實施例中，預傾角為「良好（B）」的評價。4. Evaluation of the pretilt angle Regarding the liquid crystal display element manufactured in 2. described above, it is based on non-patent literature (TJ Schaeffer et al. Journal of Applied Physics. Volume 19, p. 2013 (1980) (TJScheffer et.al. J .Appl.Phys.vo.19, p.2013 (1980))), the value of the tilt angle of the liquid crystal molecules with respect to the substrate surface is measured by a crystal rotation method using He-Ne laser light, and This value is set as the pretilt angle. At this time, when the pretilt angle is 85.0 ° or more and less than 88.0 °, it is set to "Excellent (A)", and when it is 88.0 ° or more and less than 89.0 °, it is set to "Good (B)" and is 89.0 ° or more When it is less than 85.0 °, it is set to "defective (C)". As a result, in this example, the pretilt angle was evaluated as "good (B)".

5. AC殘像特性的評價
關於所述2.中製造的液晶顯示元件，以交流電壓15 V驅動20小時後，測定預傾角，並藉由下述數式（1）來求出傾斜差Δθ。

Δθ=θ1-θ2 …（1）

（數式（1）中，θ1為驅動前的預傾角，θ2為驅動後的預傾角）
於Δθ為0.05°以下的情況下設為「優良（A）」，於大於0.05°且小於0.10°的情況下設為「良好（B）」，於0.10°以上的情況下設為「不良（C）」。結果，該實施例中為「優良（A）」的評價。5. Evaluation of AC residual image characteristics Regarding the liquid crystal display element manufactured in 2. described above, after driving at an AC voltage of 15 V for 20 hours, the pretilt angle was measured, and the tilt difference Δθ was determined by the following formula (1) .

Δθ = θ1-θ2… (1)

(In Equation (1), θ1 is the pretilt angle before driving, and θ2 is the pretilt angle after driving)
When Δθ is less than or equal to 0.05 °, it is set to "excellent (A)", when it is greater than 0.05 ° and less than 0.10 °, it is set to "good (B)", and when it is 0.10 or more, it is set to "poor ( C) ". As a result, this example was evaluated as "excellent (A)".

[實施例2-2～實施例2-49、及比較例2-1～比較例2-8]
將調配組成如下述表9～表11所示般加以變更，除此以外，以與實施例1相同的固體成分濃度進行製備，分別獲得液晶配向劑。另外，使用各液晶配向劑與實施例2-1同樣地製造光垂直型液晶顯示元件並進行各種評價。將該些結果示於下述表9～表11中。再者，實施例2-8及實施例2-24中，作為添加劑而將化合物（ad-1）、化合物（ad-2）分別調配至液晶配向劑中。[Example 2-2 to Example 2-49, and Comparative Example 2-1 to Comparative Example 2-8]
The prepared composition was changed as shown in the following Tables 9 to 11, and was prepared at the same solid content concentration as in Example 1 to obtain liquid crystal alignment agents. Moreover, using each liquid crystal aligning agent, it carried out similarly to Example 2-1, and manufactured the light vertical liquid crystal display element, and performed various evaluation. These results are shown in Tables 9 to 11 below. In addition, in Example 2-8 and Example 2-24, the compound (ad-1) and the compound (ad-2) were each formulated as a liquid crystal alignment agent as an additive.

[表9]



[表10]


[表11]

[TABLE 9]



[TABLE 10]


[TABLE 11]

如表9～表11所示般，於使用含有聚合體（P）的液晶配向劑的實施例2-1～實施例2-49中，電壓保持率為「A」或「B」。另外，預傾角特性及AC殘像特性亦為「A」或「B」，且至少一者為「A」的評價，電特性、預傾角特性及AC殘像特性經平衡良好地改善。相對於此，使用並不含有聚合體（P）的液晶配向劑的比較例2-1～比較例2-8中，為比實施例2-1～實施例2-49差的結果。再者，比較例2-2及比較例2-4中，預傾角的評價為「C」，但該些的預傾角均為89°以上而為高的值。As shown in Tables 9 to 11, in Examples 2-1 to 2-49 in which a liquid crystal alignment agent containing a polymer (P) was used, the voltage holding ratio was "A" or "B". In addition, the evaluations of the pretilt angle characteristics and the AC afterimage characteristics were also "A" or "B", and at least one of them was "A", and the electrical characteristics, the pretilt angle characteristics, and the AC afterimage characteristics were well balanced. On the other hand, in Comparative Examples 2-1 to 2-8 using a liquid crystal alignment agent not containing a polymer (P), the results were inferior to those of Examples 2-1 to 2-49. In addition, in Comparative Example 2-2 and Comparative Example 2-4, the pretilt angle was evaluated as "C", but these pretilt angles were all 89 ° or more and a high value.

無no

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Claims (12)

一種液晶配向劑，其含有聚合體（P），所述聚合體（P）具有： 結構單元U1，源自下述式（1）所表示的化合物；以及 結構單元U2，為源自具有下述式（2）、式（3）、式（4）或式（5）所表示的部分結構的化合物的結構單元，且與所述結構單元U1不同： (E¹ )_i -(G¹ )_j …（1） （式（1）中，G¹ 為具有顯示出交聯性的環狀結構的基、具有芳香族縮合多環結構的基、或具有含氮雜環結構的基；E¹ 為具有聚合性碳-碳不飽和鍵的基，形成聚合性碳-碳不飽和鍵的至少一個碳原子與G¹ 所具有的顯示出交聯性的環狀結構、芳香族縮合多環結構或含氮雜環結構的環藉由單鍵而鍵結，或經由**-COO-、**-CONR⁵⁰ -、**-CH₂ -CONR⁵⁰ -、-O-或伸苯基（其中，「**」表示與形成聚合性碳-碳不飽和鍵的碳原子鍵結的鍵結鍵）而鍵結；R⁵⁰ 為氫原子，或表示R⁵⁰ 與其他基鍵結而構成的環結構；i及j中，其中一者為1且另一者為2，或i=j=1） （式（2）中，R¹ 為碳數1以上的一價有機基，R² 及R³ 分別獨立地為氫原子或甲基；式（3）中，R⁴ 為碳數1以上的一價有機基，R⁵ 為氫原子或碳數1以上的一價有機基，R⁶ 及R⁷ 分別獨立地為氫原子或甲基；式（4）中，R⁸ 為碳數1以上的一價有機基，R¹¹ 為氫原子或碳數1以上的一價有機基，R⁹ 及R¹⁰ 分別獨立地為氫原子或甲基；X¹⁰ 及X¹¹ 中的一者為單鍵，另一者為亞甲基；式（5）中，R¹² 為碳數1以上的一價有機基，R¹³ 及R¹⁴ 分別獨立地為氫原子或甲基）。A liquid crystal alignment agent comprising a polymer (P) having: a structural unit U1 derived from a compound represented by the following formula (1); and a structural unit U2 derived from a compound having the following The structural unit of the partial structure compound represented by formula (2), formula (3), formula (4), or formula (5), and is different from the structural unit U1: (E ¹ ) _i- (G ¹ ) _j (1) (In formula (1), G ¹ is a group having a cyclic structure exhibiting crosslinkability, a group having an aromatic condensed polycyclic structure, or a group having a nitrogen-containing heterocyclic structure; E ¹ is having a polymerizable carbon - carbon unsaturated bond to form polymerizable carbon - carbon unsaturated bond is at least one carbon atom and G ¹ has exhibited crosslinkable cyclic structure or an aromatic condensed polycyclic structure containing The rings of the nitrogen heterocyclic structure are bonded by a single bond, or via **-COO-, **-CONR ^50- , **-CH ₂ -CONR ^50- , -O- or phenylene (wherein " ** "indicates formed polymerizable carbon - carbon atoms bonded bonded bonded carbon unsaturated bond) and the bond; R ⁵⁰ is a hydrogen atom, or represent a ring structure ⁵⁰ and bonded to other groups constituted R i and j, where one is 1 and the other is 2, or i = j = 1) (In formula (2), R ¹ is a monovalent organic group having a carbon number of 1 or more, and R ² and R ³ are each independently a hydrogen atom or a methyl group; in formula (3), R ⁴ is a one having a carbon number of 1 or more Valent organic group, R ⁵ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group; in the formula (4), R ⁸ is a group having a carbon number of 1 or more Valent organic group, R ¹¹ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group; one of X ¹⁰ and X ¹¹ is a single bond, and the other Is methylene; in formula (5), R ¹² is a monovalent organic group having 1 or more carbon atoms, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group). 如申請專利範圍第1項所述的液晶配向劑，其中所述聚合體（P）具有氧雜環丁基及氧雜環丙基（其中，將所述結構單元U1所具有的氧雜環丁基及氧雜環丙基除外）的至少一者。The liquid crystal alignment agent according to item 1 of the scope of the patent application, wherein the polymer (P) has an oxetanyl group and an oxetanyl group (wherein the oxetan group of the structural unit U1 At least one of oxo and oxepropyl). 如申請專利範圍第2項所述的液晶配向劑，其中所述聚合體（P）具有藉由加熱而與氧雜環丁基及氧雜環丙基的至少一者反應的官能基。The liquid crystal alignment agent according to item 2 of the patent application scope, wherein the polymer (P) has a functional group that reacts with at least one of an oxetanyl group and an oxetanyl group by heating. 如申請專利範圍第1項至第3項中任一項所述的液晶配向劑，其中所述聚合體[P]具有選自由羧基、經保護的羧基、胺基及經保護的胺基所組成的群組中的至少一種。The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the polymer [P] has a member selected from the group consisting of a carboxyl group, a protected carboxyl group, an amine group, and a protected amine group. At least one of the group. 如申請專利範圍第1項至第4項中任一項所述的液晶配向劑，其進而含有選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種聚合體。The liquid crystal alignment agent according to any one of claims 1 to 4, further comprising at least one selected from the group consisting of polyamic acid, polyamidate, and polyimide. An aggregate. 如申請專利範圍第1項至第5項中任一項所述的液晶配向劑，其中所述聚合體（P）為具有光配向性基的聚合體。The liquid crystal alignment agent according to any one of claims 1 to 5, in which the polymer (P) is a polymer having a photo-alignment group. 如申請專利範圍第1項至第5項中任一項所述的液晶配向劑，其中所述結構單元U2為源自下述式（6）所表示的化合物的結構單元： （式（6）中，B¹ 為下述式（7）、式（8）、式（9）或式（10）所表示的一價基，D¹ 為下述式（11）所表示的二價基，X¹ 及X² 分別獨立地為單鍵、-CO-O-、-O-CO-、-CS-O-、-O-CS-、-CO-S-、-S-CO-、-O-CH₂ -、-CH₂ -O-或碳數1～3的烷二基，A¹ 及A² 分別獨立地為經取代或未經取代的伸苯基、伸環己基或伸萘基，R¹⁸ 為碳數2～20的烷基、烷氧基、氟烷基、氟烷氧基或-R¹⁹ -Y¹ （其中，R¹⁹ 為碳數2～20的烷二基，Y¹ 為三烷基矽烷基）；m為0～2的整數，n為1～3的整數；於m為2的情況下，多個A¹ 、X¹ 分別獨立地具有所述定義；於n為2或3的情況下，多個R¹⁸ 分別獨立地具有所述定義） （式（7）中，R² 及R³ 分別與所述式（2）為相同含義；式（8）中，R⁵ 、R⁶ 及R⁷ 分別與所述式（3）為相同含義；式（9）中，R⁹ 、R¹⁰ 、R¹¹ 、X¹⁰ 及X¹¹ 分別與所述式（4）為相同含義；式（10）中，R¹³ 及R¹⁴ 分別與所述式（5）為相同含義；「*」表示鍵結鍵） （式（11）中，A³ 、A⁴ 及A⁵ 分別獨立地為經取代或未經取代的伸苯基或伸環己基，L¹ 及L² 分別獨立地為單鍵、碳數1～5的烷二基、或所述烷二基的至少一個亞甲基經「-O-」取代的基（其中，氧原子並不連續），X³ 及X⁴ 分別獨立地為-CO-O-、-O-CO-、-CS-O-、-O-CS-、-CO-S-、-S-CO-或-O-，R¹⁶ 及R¹⁷ 分別獨立地為氫原子、甲基、鹵素原子或氰基；k及r分別獨立地為0或1；「*¹ 」及「*² 」表示鍵結鍵；其中，包含「*¹ 」與B¹ 鍵結的情況、以及「*² 」與B¹ 鍵結的情況）。The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the structural unit U2 is a structural unit derived from a compound represented by the following formula (6): (In formula (6), B ¹ is a monovalent group represented by the following formula (7), (8), (9), or (10), and D ¹ is represented by the following formula (11) Divalent base, X ¹ and X ² are each independently a single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO -, -O-CH _2- , -CH ₂ -O- or an alkanediyl group having 1 to 3 carbon atoms, and A ¹ and A ² are each independently substituted or unsubstituted phenylene, cyclohexyl or Naphthyl, R ¹⁸ is an alkyl group, alkoxy group, fluoroalkyl group, fluoroalkoxy group, or -R ¹⁹ -Y ¹ (wherein R ¹⁹ is an alkanediyl group having 2 to 20 carbon atoms) , Y ¹ is a trialkylsilyl group); m is an integer of 0 to 2 and n is an integer of 1 to 3; when m is 2, a plurality of A ¹ and X ¹ each independently have the definition; In the case where n is 2 or 3, a plurality of R ¹⁸ each independently have the definition) (In formula (7), R ² and R ³ have the same meanings as the formula (2); in formula (8), R ⁵ , R ^6, and R ⁷ have the same meanings as the formula (3); In the formula (9), R ⁹ , R ¹⁰ , R ¹¹ , X ¹⁰ and X ¹¹ have the same meanings as the formula (4); in the formula (10), R ¹³ and R ¹⁴ are respectively the same as the formula (5) ) Have the same meaning; "*" means bond key) (In formula (11), A ³ , A ^4, and A ⁵ are each independently substituted or unsubstituted phenylene or cyclohexyl, and L ¹ and L ² are each independently a single bond and a carbon number of 1 to 5 alkanediyl, or at least one methylene group of said alkanediyl substituted with "-O-" (wherein the oxygen atom is not continuous), X ³ and X ⁴ are each independently -CO-O -, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO- or -O-, R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a methyl group , a halogen atom or a cyano group; K and r are independently 0 or 1; ^"1 *" and "* ^2" represents a bond bond; wherein, includes "* ^1" in the case of B ¹ bond, and "* ² ”with B ¹ ). 如申請專利範圍第1項至第7項中任一項所述的液晶配向劑，其中所述結構單元U2具有下述式（b-1）所表示的部分結構： （式（b-1）中，A⁶ 、A⁷ 及A⁸ 分別獨立地為經取代或未經取代1,4-伸環己基或1,4-伸苯基，X⁵ 為單鍵或氧原子，R⁸⁰ 為氟甲基或甲基，a1為0～2的整數，a2為1～20的整數，a3為0或1；其中，於R⁸⁰ 為甲基的情況下，a1=0；「*」表示鍵結鍵）。The liquid crystal alignment agent according to any one of claims 1 to 7, wherein the structural unit U2 has a partial structure represented by the following formula (b-1): (In formula (b-1), A ⁶ , A ⁷ and A ⁸ are each independently substituted or unsubstituted 1,4-cyclohexyl or 1,4-phenylene, and X ⁵ is a single bond or oxygen Atom, R ⁸⁰ is fluoromethyl or methyl, a1 is an integer of 0 to 2, a2 is an integer of 1 to 20, and a3 is 0 or 1; where R ⁸⁰ is a methyl group, a1 = 0; "*" Means bond key). 一種液晶配向膜，其是使用如申請專利範圍第1項至第8項中任一項所述的液晶配向劑而形成。A liquid crystal alignment film is formed by using the liquid crystal alignment agent according to any one of claims 1 to 8 of a patent application scope. 一種液晶元件，其包括如申請專利範圍第9項所述的液晶配向膜。A liquid crystal element includes the liquid crystal alignment film according to item 9 of the scope of patent application. 一種聚合體，其具有： 結構單元U1，源自下述式（1）所表示的化合物；以及 結構單元U2，為源自具有下述式（2）、式（3）、式（4）或式（5）所表示的部分結構的化合物的結構單元，且與所述結構單元U1不同： (E¹ )_i -(G¹ )_j …（1） （式（1）中，G¹ 為具有顯示出交聯性的環狀結構的基、具有芳香族縮合多環結構的基、或具有含氮雜環結構的基；E¹ 為具有聚合性碳-碳不飽和鍵的基，形成聚合性碳-碳不飽和鍵的至少一個碳原子與G¹ 所具有的顯示出交聯性的環狀結構、芳香族縮合多環結構或含氮雜環結構的環藉由單鍵而鍵結，或經由**-COO-、**-CONR⁵⁰ -、**-CH₂ -CONR⁵⁰ -、-O-或伸苯基（其中，「**」表示與形成聚合性碳-碳不飽和鍵的碳原子鍵結的鍵結鍵）而鍵結；R⁵⁰ 為氫原子，或表示R⁵⁰ 與其他基鍵結而構成的環結構；i及j中，其中一者為1且另一者為2，或i=j=1） （式（2）中，R¹ 為碳數1以上的一價有機基，R² 及R³ 分別獨立地為氫原子或甲基；式（3）中，R⁴ 為碳數1以上的一價有機基，R⁵ 為氫原子或碳數1以上的一價有機基，R⁶ 及R⁷ 分別獨立地為氫原子或甲基；式（4）中，R⁸ 為碳數1以上的一價有機基，R¹¹ 為氫原子或碳數1以上的一價有機基，R⁹ 及R¹⁰ 分別獨立地為氫原子或甲基；X¹⁰ 及X¹¹ 中的一者為單鍵，另一者為亞甲基；式（5）中，R¹² 為碳數1以上的一價有機基，R¹³ 及R¹⁴ 分別獨立地為氫原子或甲基）。A polymer having: a structural unit U1 derived from a compound represented by the following formula (1); and a structural unit U2 derived from a compound having the following formula (2), formula (3), formula (4), or The structural unit of the partially structured compound represented by formula (5) is different from the structural unit U1: (E ¹ ) _i- (G ¹ ) _j … (1) (In formula (1), G ¹ has A group having a cross-linking cyclic structure, a group having an aromatic condensed polycyclic structure, or a group having a nitrogen-containing heterocyclic structure; E ¹ is a group having a polymerizable carbon-carbon unsaturated bond and forms a polymerizability At least one carbon atom of a carbon-carbon unsaturated bond is bonded to a ring structure having a crosslinkability, an aromatic condensed polycyclic structure or a nitrogen-containing heterocyclic structure possessed by G ¹ through a single bond, or Via **-COO-, **-CONR ^50- , **-CH ₂ -CONR ^50- , -O- or phenylene (where "**" means a polymer that forms a polymerizable carbon-carbon unsaturated bond Carbon atom bonding bond) and bonding; R ⁵⁰ is a hydrogen atom, or a ring structure formed by R ⁵⁰ bonding to other groups; one of i and j is 1 and the other is 2 , Or i = j = 1) (In formula (2), R ¹ is a monovalent organic group having a carbon number of 1 or more, and R ² and R ³ are each independently a hydrogen atom or a methyl group; in formula (3), R ⁴ is a one having a carbon number of 1 or more Valent organic group, R ⁵ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group; in the formula (4), R ⁸ is a group having a carbon number of 1 or more Valent organic group, R ¹¹ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group; one of X ¹⁰ and X ¹¹ is a single bond, and the other Is methylene; in formula (5), R ¹² is a monovalent organic group having 1 or more carbon atoms, and R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group). 一種化合物，其由下述式（6）表示： （式（6）中，B¹ 為下述式（7）、式（8）、式（9）或式（10）所表示的一價基，D¹ 為下述式（11）所表示的二價基，X¹ 及X² 分別獨立地為單鍵、-CO-O-、-O-CO-、-CS-O-、-O-CS-、-CO-S-、-S-CO-、-O-CH₂ -、-CH₂ -O-或碳數1～3的烷二基，A¹ 及A² 分別獨立地為經取代或未經取代的伸苯基、伸環己基或伸萘基，R¹⁸ 為碳數2～20的烷基、烷氧基、氟烷基、氟烷氧基或-R¹⁹ -Y¹ （其中，R¹⁹ 為碳數2～20的烷二基，Y¹ 為三烷基矽烷基）；m為0～2的整數，n為1～3的整數；於m為2的情況下，多個A¹ 、X¹ 分別獨立地具有所述定義；於n為2或3的情況下，多個R¹⁸ 分別獨立地具有所述定義） （式（7）中，R² 及R³ 分別獨立地為氫原子或甲基；式（8）中，R⁵ 為氫原子或碳數1以上的一價有機基，R⁶ 及R⁷ 分別獨立地為氫原子或甲基；式（9）中，R¹¹ 為氫原子或碳數1以上的一價有機基，R⁹ 及R¹⁰ 分別獨立地為氫原子或甲基；X¹⁰ 及X¹¹ 中的一者為單鍵，另一者為亞甲基；式（10）中，R¹³ 及R¹⁴ 分別獨立地為氫原子或甲基；「*」表示鍵結鍵） （式（11）中，A³ 、A⁴ 及A⁵ 分別獨立地為經取代或未經取代的伸苯基或伸環己基，L¹ 及L² 分別獨立地為單鍵、碳數1～5的烷二基、或所述烷二基的至少一個亞甲基經「-O-」取代的基（其中，氧原子並不連續），X³ 及X⁴ 分別獨立地為-CO-O-、-O-CO-、-CS-O-、-O-CS-、-CO-S-、-S-CO-或-O-，R¹⁶ 及R¹⁷ 分別獨立地為氫原子、甲基、鹵素原子或氰基；k及r分別獨立地為0或1；「*¹ 」及「*² 」表示鍵結鍵；其中，包含「*¹ 」與B¹ 鍵結的情況、以及「*² 」與B¹ 鍵結的情況）。A compound represented by the following formula (6): (In formula (6), B ¹ is a monovalent group represented by the following formula (7), (8), (9), or (10), and D ¹ is represented by the following formula (11) Divalent base, X ¹ and X ² are each independently a single bond, -CO-O-, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO -, -O-CH _2- , -CH ₂ -O- or an alkanediyl group having 1 to 3 carbon atoms, and A ¹ and A ² are each independently substituted or unsubstituted phenylene, cyclohexyl or Naphthyl, R ¹⁸ is an alkyl group, alkoxy group, fluoroalkyl group, fluoroalkoxy group, or -R ¹⁹ -Y ¹ (wherein R ¹⁹ is an alkanediyl group having 2 to 20 carbon atoms) , Y ¹ is a trialkylsilyl group); m is an integer of 0 to 2 and n is an integer of 1 to 3; when m is 2, a plurality of A ¹ and X ¹ each independently have the definition; In the case where n is 2 or 3, a plurality of R ¹⁸ each independently have the definition) (In formula (7), R ² and R ³ are each independently a hydrogen atom or a methyl group; in formula (8), R ⁵ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, and R ⁶ and R ⁷ are respectively Independently a hydrogen atom or a methyl group; in formula (9), R ¹¹ is a hydrogen atom or a monovalent organic group having a carbon number of 1 or more, and R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group; X ¹⁰ and X ^{One of 11} is a single bond and the other is a methylene group; in formula (10), R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group; “*” represents a bonding bond) (In formula (11), A ³ , A ^4, and A ⁵ are each independently substituted or unsubstituted phenylene or cyclohexyl, and L ¹ and L ² are each independently a single bond and a carbon number of 1 to 5 alkanediyl, or at least one methylene group of said alkanediyl substituted with "-O-" (wherein the oxygen atom is not continuous), X ³ and X ⁴ are each independently -CO-O -, -O-CO-, -CS-O-, -O-CS-, -CO-S-, -S-CO- or -O-, R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a methyl group , a halogen atom or a cyano group; K and r are independently 0 or 1; ^"1 *" and "* ^2" represents a bond bond; wherein, includes "* ^1" in the case of B ¹ bond, and "* ² ”with B ¹ ).