TWI586709B

TWI586709B - Polyamic acid and derivatives thereof, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device using the same

Info

Publication number: TWI586709B
Application number: TW102114738A
Authority: TW
Inventors: 大木洋一郎; 片野裕子; 松田智幸; 伊澤啓介
Original assignee: 捷恩智股份有限公司; 捷恩智石油化學股份有限公司
Priority date: 2012-04-25
Filing date: 2013-04-25
Publication date: 2017-06-11
Also published as: JP6057070B2; CN103374131A; KR101991969B1; KR20130120388A; JP2013241571A; TW201343724A

Description

聚醯胺酸或其衍生物、液晶配向劑、液晶配向膜及使用其的液晶顯示元件 Polylysine or its derivative, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same

本發明涉及一種液晶配向劑、使用該液晶配向劑的配向膜及具有該液晶配向膜的液晶顯示元件，所述液晶配向劑含有使特定的脂環式四羧酸二酐與二胺進行反應而獲得的聚醯胺酸或其衍生物。 The present invention relates to a liquid crystal alignment agent, an alignment film using the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film, wherein the liquid crystal alignment agent contains a reaction between a specific alicyclic tetracarboxylic dianhydride and a diamine. Polylysine obtained or a derivative thereof.

個人計算機的監視器、液晶電視機、攝像機的取景器、投影式顯示器等各種顯示裝置，進而光學打印頭、光學傅裏葉變換元件、光閥等光電子相關元件等如今已產品化且普遍流通的液晶顯示元件的主流是使用向列液晶的顯示元件。向列液晶顯示元件的顯示方式廣為人知的是扭轉向列(Twisted Nematic，TN)模式、超扭轉向列(Super Twisted Nematic，STN)模式。近年來，為了改善作為這些模式的問題之一的視角的狹小，提出有使用光學補償膜的TN型液晶顯示元件，並用垂直配向與突起構造物的技術的多區域垂直排列(Multi-domain Vertical Alignment，MVA)模式、或橫向電場方式的共面切換(In-Plane Switching，IPS)模式等，且已實用化。 Various display devices such as monitors for personal computers, viewfinders for liquid crystal televisions, camera viewfinders, and projection displays, and optical electronic components such as optical print heads, optical Fourier transform elements, and light valves are now commercially available and generally circulated. The mainstream of liquid crystal display elements is a display element using nematic liquid crystal. The display mode of the nematic liquid crystal display element is widely known as a twisted nematic (TN) mode or a super twisted nematic (STN) mode. In recent years, in order to improve the narrowness of the viewing angle which is one of the problems of these modes, a TN type liquid crystal display element using an optical compensation film and a technique of vertically aligning and protruding structures have been proposed. The Multi-domain Vertical Alignment (MVA) mode or the In-Plane Switching (IPS) mode of the transverse electric field method has been put into practical use.

為了使這些液晶顯示元件具有均一的顯示特性，必須均一地控制液晶的分子排列。具體而言，使基板上的液晶分子在一個方向上均一地配向、使液晶分子從基板面起具有固定的傾斜角(預傾角)等。承擔此種作用的是液晶配向膜。液晶配向膜是與液晶顯示元件的顯示品質相關的重要因素之一，隨著顯示元件的高品質化，液晶配向膜的作用一年年重要起來。 In order for these liquid crystal display elements to have uniform display characteristics, it is necessary to uniformly control the molecular arrangement of the liquid crystals. Specifically, the liquid crystal molecules on the substrate are uniformly aligned in one direction, and the liquid crystal molecules have a fixed tilt angle (pretilt angle) or the like from the substrate surface. It is the liquid crystal alignment film that bears this effect. The liquid crystal alignment film is one of the important factors related to the display quality of the liquid crystal display element, and the function of the liquid crystal alignment film is important year by year in accordance with the high quality of the display element.

液晶配向膜是使用液晶配向劑來形成。目前，主要使用的液晶配向劑是使聚醯胺酸或可溶性的聚醯亞胺溶解在有機溶劑中而成的溶液(清漆)。將該溶液塗布在基板上後，利用加熱等方法進行成膜，而形成聚醯亞胺系液晶配向膜。作為對該膜賦予使液晶分子進行配向的性質(配向處理)的方法，目前工業上使用的是摩擦法。摩擦法是使用植毛有尼龍、人造絲、聚酯等纖維的布在一個方向上摩擦液晶配向膜的表面的處理，由此可獲得液晶分子的一樣的配向。但是，摩擦法存在如下等問題：在步驟中發生的配向膜的削除、或由纖維塵等的附著所引起的顯示缺陷、或薄膜晶體管(Thin-Film-Transistor，TFT)元件因靜電的產生而毀壞所引起的顯示不良。 The liquid crystal alignment film is formed using a liquid crystal alignment agent. At present, a liquid crystal alignment agent mainly used is a solution (varnish) obtained by dissolving polylysine or soluble polyimine in an organic solvent. After the solution is applied onto a substrate, film formation is carried out by heating or the like to form a polyimine-based liquid crystal alignment film. As a method of imparting a property (alignment treatment) for aligning liquid crystal molecules to the film, a rubbing method is currently used industrially. The rubbing method is a process of rubbing the surface of the liquid crystal alignment film in one direction by using a cloth having fibers such as nylon, rayon, polyester or the like, whereby the same alignment of the liquid crystal molecules can be obtained. However, the rubbing method has problems such as removal of an alignment film which occurs in the step, display defects caused by adhesion of fiber dust or the like, or generation of a thin film transistor (TFT) element due to static electricity. Poor display caused by destruction.

為了解決所述問題，提出有對所形成的膜照射光來實施配向處理的光配向法，且迄今為止，已介紹有光分解法、光異構化法、光二聚化法、光交聯法等多種配向機制(例如，參照非專利文獻1及專利文獻1~專利文獻5)。與摩擦法與相比，光配向法具有如下等優點：配向的均一性高，且因其為非接觸的配向法，故膜不會受損，可減少揚塵或靜電等產生液晶顯示元件的顯示不良的原因。 In order to solve the above problem, a photo-alignment method in which an optical treatment is performed by irradiating light to a formed film has been proposed, and photodegradation and photo-isomerization have been described so far. Various alignment mechanisms such as a chemical method, a photodimerization method, and a photocrosslinking method (for example, refer to Non-Patent Document 1 and Patent Document 1 to Patent Document 5). Compared with the rubbing method, the photo-alignment method has the following advantages: the uniformity of the alignment is high, and since it is a non-contact alignment method, the film is not damaged, and the display of the liquid crystal display element such as dust or static electricity can be reduced. Bad cause.

用於利用光配向法的液晶配向膜(以下，有時略記為“光配向膜”)的材料的研究也已進行過多次，報告有使用將四羧酸二酐，特別是環丁烷四羧酸二酐用於原料的聚醯亞胺的光配向膜可使液晶分子均一且穩定地進行配向(例如，參照專利文獻1)。其為如下的方法：對形成在基板上的膜照射紫外線等，使聚醯亞胺產生化學變化，由此賦予使液晶在固定方向上進行配向的功能。但是，利用此種方式的光配向膜與利用摩擦法的配向膜相比，存在雜質離子的量增加且電壓保持率下降等電特性欠佳這一問題。為了解決該問題，對構成聚醯亞胺的分子結構進行了各種研究(例如，參照專利文獻2及專利文獻3)。 The study of a material for a liquid crystal alignment film (hereinafter sometimes abbreviated as "photoalignment film") by a photo-alignment method has been carried out many times, and it has been reported that tetracarboxylic dianhydride, particularly cyclobutane tetracarboxylate, is used. The acid dianhydride used for the photoalignment film of the polyimine of the raw material can align the liquid crystal molecules uniformly and stably (for example, refer to Patent Document 1). It is a method of irradiating a film formed on a substrate with ultraviolet rays or the like to cause a chemical change of the polyimide, thereby imparting a function of aligning the liquid crystal in a fixed direction. However, the optical alignment film of this type has a problem that the amount of impurity ions increases and the voltage retention rate decreases, and the electrical characteristics are not as good as those of the alignment film by the rubbing method. In order to solve this problem, various studies have been made on the molecular structure of the polyimine (see, for example, Patent Document 2 and Patent Document 3).

另一方面，光配向法與摩擦法相比，液晶分子的配向性欠佳，因此已被指出錨定能(anchoring energy)小、引起液晶顯示元件的響應速度的下降或殘像這一問題。 On the other hand, the photo-alignment method has a poor alignment property of the liquid crystal molecules as compared with the rubbing method. Therefore, it has been pointed out that the anchoring energy is small, causing a decrease in the response speed of the liquid crystal display element or an afterimage.

[先前技術文獻] [Previous Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平9-297313號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 9-297313

[專利文獻2]日本專利特開2004-206091號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-206091

[專利文獻3]國際公開第2005/83504號手冊 [Patent Document 3] International Publication No. 2005/83504

[專利文獻4]日本專利特開2005-275364號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-275364

[專利文獻5]日本專利特開2006-171304號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2006-171304

[非專利文獻] [Non-patent literature]

[非專利文獻1]液晶，第3卷，第4號，262頁，1999年 [Non-Patent Document 1] Liquid Crystal, Vol. 3, No. 4, 262 pages, 1999

本發明的課題在於提供一種液晶分子的配向性優異、且透過率高的液晶配向劑。進而，本發明的課題在於提供一種使用該液晶配向劑的配向膜，並提供一種使用該配向膜的液晶顯示元件。 An object of the present invention is to provide a liquid crystal alignment agent which is excellent in the alignment property of liquid crystal molecules and has high transmittance. Further, an object of the present invention is to provide an alignment film using the liquid crystal alignment agent and to provide a liquid crystal display element using the alignment film.

本發明者等人發現通過將以由式(1)所表示的四羧酸二酐與二胺為原料的聚醯胺酸或其衍生物用作液晶配向劑，可獲得配向性良好、且透過率高的液晶配向膜，從而完成了本發明。 The present inventors have found that by using a polyaminic acid or a derivative thereof using a tetracarboxylic dianhydride represented by the formula (1) as a raw material for a liquid crystal alignment agent, good alignment and permeation can be obtained. The liquid crystal alignment film having a high rate has completed the present invention.

本發明包含以下的構成。 The present invention includes the following constitutions.

[1]一種聚醯胺酸或其衍生物，其特徵在於：使至少含有由下述式(1)所表示的四羧酸二酐的四羧酸二酐與二胺進行反應而獲得。 [1] A poly-proline or a derivative thereof, which is obtained by reacting a tetracarboxylic dianhydride containing at least a tetracarboxylic dianhydride represented by the following formula (1) with a diamine.

[2]根據[1]所述的聚醯胺酸或其衍生物，其中：由式(1) 所表示的四羧酸二酐為由下述式(1-a)或式(1-b)所表示的四羧酸二酐的至少1種。 [2] Polylysine or a derivative thereof according to [1], wherein: (1) The tetracarboxylic dianhydride shown is at least one of tetracarboxylic dianhydride represented by the following formula (1-a) or formula (1-b).

[3]根據[1]或[2]所述的聚醯胺酸或其衍生物，其中：四羧酸二酐含有選自由下述式(AN-I)~式(AN-VII)所表示的四羧酸二酐的群組中的至少1種， [3] The poly-proline or a derivative thereof according to [1] or [2] wherein the tetracarboxylic dianhydride is selected from the group consisting of the following formula (AN-I) to formula (AN-VII) At least one of the group of tetracarboxylic dianhydrides,

[化3] [Chemical 3]

式(AN-I)、式(AN-IV)及式(AN-V)中，X獨立為單鍵或-CH₂-；式(AN-II)中，G為單鍵、碳數1~20的伸烷基、-CO-、-O-、-S-、-SO₂-、-C(CH₃)₂-、或-C(CF₃)₂-：式(AN-II)~式(AN-IV)中，Y獨立為選自下述的三價的基的群組中的1種； In the formula (AN-I), the formula (AN-IV) and the formula (AN-V), X is independently a single bond or -CH ₂ -; in the formula (AN-II), G is a single bond, and the carbon number is 1~ 20 alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -: (AN-II)~ In (AN-IV), Y is independently one selected from the group consisting of trivalent groups described below;

這些基的任意的氫可由甲基、乙基或苯基取代；式(AN-III)~式(AN-V)中，環A為碳數3~10的單環式烴的基或碳數6~30的縮合多環式烴的基，所述基的任意的氫可由甲基、乙基或苯基取代，連接在環上的結合鍵與構成環的任意的碳連結，2個結合鍵可與同一個碳連結；式(AN-VI)中，X¹⁰為碳數2~6的伸烷基；Me為甲基；Ph為苯基；式(AN-VII)中，G¹⁰獨立為-O-、-COO-或-OCO-；且r獨立為0或1。 Any hydrogen of these groups may be substituted by a methyl group, an ethyl group or a phenyl group; in the formula (AN-III) to the formula (AN-V), the ring A is a group or a carbon number of a monocyclic hydrocarbon having a carbon number of 3 to 10. a group of 6 to 30 condensed polycyclic hydrocarbons, wherein any hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, and a bond bonded to the ring may be bonded to any carbon constituting the ring, and 2 bond bonds may be used. It can be bonded to the same carbon; in the formula (AN-VI), X ¹⁰ is an alkylene group having 2 to 6 carbon atoms; Me is a methyl group; Ph is a phenyl group; and in the formula (AN-VII), G ^{10 is} independently -O-, -COO- or -OCO-; and r is independently 0 or 1.

[4]根據[1]至[3]中任一項所述的聚醯胺酸或其衍生物，其中：四羧酸二酐含有選自由下述式(AN-1-1)、式(AN-1-13)、式(AN-2-1)、式(AN-3-1)、式(AN-3-2)、式(AN-4-5)、式(AN-4-17)、式(AN-7-2)、式(AN-10)、及式(AN-11-3)所組成的群組中的至少1種，[化5] The poly-proline or a derivative thereof according to any one of [1] to [3] wherein the tetracarboxylic dianhydride is selected from the group consisting of the following formula (AN-1-1), AN-1-13), formula (AN-2-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17 At least one of the group consisting of formula (AN-7-2), formula (AN-10), and formula (AN-11-3), [Chem. 5]

式(AN-4-17)中，m為1~12的整數。 In the formula (AN-4-17), m is an integer of 1 to 12.

[5]根據[1]至[4]中任一項所述的聚醯胺酸或其衍生物，其中：二胺含有選自由下述式(DI-1)~式(DI-17)所組成的群組中的至少1種，[化6] [5] The poly-proline or a derivative thereof according to any one of [1] to [4] wherein the diamine is selected from the group consisting of the following formula (DI-1) to (DI-17) At least one of the group consisting of [Chemical 6]

式(DI-1)中，m為1~12的整數；(DI-3)及(DI-5)~(DI-7)中，G²¹獨立為單鍵、-NH-、-O-、-S-、-S-S-、-SO₂-、-CO-、-CONH-、-CONCH₃-、-NHCO-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m'-、-O-(CH₂)_m'-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、或-S-(CH₂)_m'-S-，m'獨立為1~12的整數，k為1~5的整數；(DI-6)及(DI-7)中，G²²獨立為單鍵、-O-、-S-、-CO-、-C(CH₃)₂-、-C(CF₃)₂-、或碳數1~10的伸烷基；式(DI-2)~式(DI-7)中的環己烷環及苯環的任意的-H可由-F、-CH₃、-OH、-CF₃、-CO₂H、-CONH₂、或苄基取代，此外，在式(DI-4)中，可由下述式(DI-4-a)~式(DI-4-c)取代，[化7] In the formula (DI-1), m is an integer of 1 to 12; in (DI-3) and (DI-5) to (DI-7), G ^{21 is} independently a single bond, -NH-, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -CONCH ₃ -, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -( CH ₂ ) _m' -, -O-(CH ₂ ) _m' -O-, -N(CH ₃ )-(CH ₂ ) _k -N(CH ₃ )-, or -S-(CH ₂ ) _m' -S-,m' is an integer from 1 to 12, and k is an integer from 1 to 5. In (DI-6) and (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or an alkylene group having a carbon number of 1 to 10; a ring in the formula (DI-2) to (DI-7) Any -H of the alkane ring and the benzene ring may be substituted by -F, -CH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ or a benzyl group, and further, in the formula (DI-4), It can be replaced by the following formula (DI-4-a)~ (DI-4-c), [Chemical 7]

式(DI-4-a)及式(DI-4-b)中，R²⁰獨立為-H或-CH₃；式(DI-2)~式(DI-7)中，結合位置未固定在構成環的任一個碳原子上的基表示在所述環上的結合位置任意；而且，-NH₂在環己烷環或苯環上的結合位置為除G²¹或G²²的結合位置以外的任意的位置。 In the formula (DI-4-a) and the formula (DI-4-b), R ^{20 is} independently -H or -CH ₃ ; in the formula (DI-2) to the formula (DI-7), the bonding position is not fixed at The group on any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; moreover, the bonding position of -NH ₂ on the cyclohexane ring or the benzene ring is other than the bonding position of G ²¹ or G ²² . Any position.

式(DI-8)中，R²¹及R²²獨立為碳數1~3的烷基或苯基；G²³獨立為碳數1~6的伸烷基、伸苯基或經烷基取代的伸苯基；n為1~10的整數；式(DI-9)中，R²³獨立為碳數1~5的烷基、碳數1~5的烷氧基或-Cl；p獨立為0~3的整數；q為0~4的整數；式(DI-10)中，R²⁴為-H、碳數1~4的烷基、苯基、或苄基；式(DI-11)中，G²⁴為-CH₂-或-NH-；式(DI-12)中，G²⁵為單鍵、碳數2~6的伸烷基或1,4-伸苯基；r為0或1；式(DI-12)中，結合位置未固定在構成環的任一個碳原子上的基表示在所述環上的結合位置任意；而且，式(DI-9)、式(DI-11)及式(DI-12)中，結合在苯環上的-NH₂的結合位置為任意的位置； In the formula (DI-8), R ²¹ and R ^{22 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group; and G ^{23 is} independently an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group. Phenyl is extended; n is an integer from 1 to 10; in the formula (DI-9), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl; and p is independently 0. An integer of ~3; q is an integer from 0 to 4; in the formula (DI-10), R ²⁴ is -H, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a benzyl group; in the formula (DI-11) , G ²⁴ is -CH ₂ - or -NH-; in the formula (DI-12), G ²⁵ is a single bond, an alkylene group having 2 to 6 carbon atoms or a 1,4-phenylene group; r is 0 or 1 In the formula (DI-12), the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; further, the formula (DI-9), the formula (DI-11) In the formula (DI-12), the binding position of -NH ₂ bonded to the benzene ring is an arbitrary position;

式(DI-13)中，G²⁶為單鍵、-O-、-COO-、-OCO-、-CO-、-CONH-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、或-(CH₂)_m'-，m'為1~12的整數；R²⁵為碳數3~20的烷基、苯基、具有類固醇骨架的基、或由下述的式(DI-13-a)所表示的基，所述烷基中，任意的-H可由-F取代，任意的-CH₂-可由-O-、-CH=CH-或-C≡C-取代，所述苯基的-H可由-F、-CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃、碳數3~20的烷基、或碳數3~20的烷氧基取代，所述環己基的-H可由碳數3~20的烷基或碳數3~20的烷氧基取代，結合在苯環上的-NH₂的結合位置表示在所述環中為任意的位置； In the formula (DI-13), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O- , -OCF ₂ -, or -(CH ₂ ) _m' -, m' is an integer from 1 to 12; R ²⁵ is an alkyl group having 3 to 20 carbon atoms, a phenyl group, a group having a steroid skeleton, or A group represented by the formula (DI-13-a) in which any -H may be substituted by -F, and any -CH ₂ - may be -O-, -CH=CH- or -C≡C Substituting -H of the phenyl group may be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 20 carbon atoms, or a carbon number of 3 to 20 Substituted by an alkoxy group, the -H of the cyclohexyl group may be substituted by an alkyl group having 3 to 20 carbon atoms or an alkoxy group having 3 to 20 carbon atoms, and the bonding position of -NH ₂ bonded to the benzene ring is represented by Any position in the ring;

式(DI-13-a)中，G²⁷、G²⁸及G²⁹表示結合基，這些獨立為單鍵、或碳數1~12的伸烷基，所述伸烷基的1個以上的-CH₂-可由-O-、-COO-、-OCO-、-CONH-、-CH=CH-取代；環B²¹、環B²²、環B²³、及環B²⁴獨立為1,4-伸苯基、1,4-伸環己基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、萘-1,4-二基、萘-1,5-二基、萘-2,6-二基、萘-2,7-二基、或蒽-9,10-二基；環B²¹、環B²²、環B²³、及環B²⁴中，任意的-H可由-F或-CH₃取代；s、t及u獨立為0~2的整數，這些的合計為1~5；當s、t或u為2時，各個括號內的2個結合基可相同，也可以不同，2個環可相同，也可以不同；R²⁶為-F、-OH、碳數1~30的烷基、碳數1~30的氟取代烷基、碳數1~30的烷氧基、-CN、-OCH₂F、-OCHF₂、或-OCF₃，所述碳數1~30的烷基的任意的-CH₂-可由以下述式(DI-13-b)所表示的二價的基取代； In the formula (DI-13-a), G ²⁷ , G ²⁸ and G ²⁹ represent a bonding group, and these are independently a single bond or an alkylene group having 1 to 12 carbon atoms, and one or more of the alkylene groups are - CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-; ring B ²¹ , ring B ²² , ring B ²³ , and ring B ^{24 are} independently 1,4-stretched Phenyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,4- Diyl, naphthalene-1,5-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or fluoren-9,10-diyl; ring B ²¹ , ring B ²² , ring B ²³ , and ring B ²⁴ , any -H may be substituted by -F or -CH ₃ ; s, t and u are independently integers of 0~2, the total of these is 1~5; when s, t or u is 2 When the two binding groups in each parenthesis may be the same or different, the two rings may be the same or different; R ²⁶ is -F, -OH, an alkyl group having 1 to 30 carbon atoms, and a carbon number of 1 to 30. Fluorine-substituted alkyl group, alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , any -CH ₂ - of the alkyl group having 1 to 30 carbon atoms Substituted by a divalent group represented by the following formula (DI-13-b);

式(DI-13-b)中，R²⁷及R²⁸獨立為碳數1~3的烷基；v為1~6的整數； In the formula (DI-13-b), R ²⁷ and R ^{28 are} independently an alkyl group having 1 to 3 carbon atoms; and v is an integer of 1 to 6;

式(DI-14)及式(DI-15)中，G³⁰獨立為單鍵、-CO-或-CH₂-；R²⁹獨立為-H或-CH₃；R³⁰為-H、碳數1~20的烷基、或碳數2~20的烯基；式(DI-15)中的苯環的1個-H可由碳數1~20的烷基或苯基取代；式(DI-14)及式(DI-15)中，結合位置未固定在構成環的任一個碳原子上的基表示在所述環上的結合位置任意；結合在苯環上的-NH₂表示在所述環上的結合位置任意； In formula (DI-14) and formula (DI-15), G ^{30 is} independently a single bond, -CO- or -CH ₂ -; R ^{29 is} independently -H or -CH ₃ ; R ³⁰ is -H, carbon number An alkyl group of 1 to 20 or an alkenyl group having 2 to 20 carbon atoms; one -H of the benzene ring in the formula (DI-15) may be substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group; 14) and in the formula (DI-15), the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; -NH ₂ bonded to the benzene ring means Any combination of positions on the ring;

式(DI-16)及式(DI-17)中，G³¹獨立為-O-或碳數1~6的伸烷基；G³²為單鍵或碳數1~3的伸烷基；R³¹為-H或碳數1~20的烷基，該烷基的任意的-CH₂-可由-O-、-CH=CH-或-C≡C-取代；R³²為碳數6~22的烷基；R³³為-H或碳數1~22的烷基；環B²⁵為1,4-伸苯基或1,4-伸環己基；r為0或1；且結合在苯環上的-NH₂表示在所述環上的結合位置任意。 In the formula (DI-16) and the formula (DI-17), G ^{31 is} independently -O- or an alkylene group having 1 to 6 carbon atoms; G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms; ³¹ is -H or an alkyl group having 1 to 20 carbon atoms, and any -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-; R ³² is a carbon number of 6-22 Alkyl; R ³³ is -H or an alkyl group having 1 to 22 carbon atoms; ring B ²⁵ is a 1,4-phenylene group or a 1,4-cyclohexylene group; r is 0 or 1; -NH ₂ on the above indicates that the bonding position on the ring is arbitrary.

[6]根據[1]至[5]中任一項所述的聚醯胺酸或其衍生物，其中：二胺含有選自下述式(2-a)~式(2-c)中的至少1種二醯肼， [6] The poly-proline or a derivative thereof according to any one of [1] to [5] wherein the diamine is selected from the group consisting of the following formula (2-a) to formula (2-c) At least one type of two,

式(2-a)中，G為單鍵、碳數1~20的伸烷基、-CO-、-O-、-S-、-SO₂-、-C(CH₃)₂-、或-C(CF₃)₂-；式(2-b)中，環B為環己烷環、苯環或萘環，所述基的任意的氫可由甲基、乙基、或苯基取代；式(2-c)中，環C分別獨立為環己烷環、或苯環，所述基的任意的氫可由甲基、乙基、或苯基取代；Y為單鍵、碳數1~20的伸烷基、-CO-、-O-、-S-、-SO₂-、-C(CH₃)₂-、或-C(CF₃)₂-。 In the formula (2-a), G is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; in the formula (2-b), the ring B is a cyclohexane ring, a benzene ring or a naphthalene ring, and any hydrogen of the group may be substituted by a methyl group, an ethyl group, or a phenyl group; In the formula (2-c), the ring C is independently a cyclohexane ring or a benzene ring, and any hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group; Y is a single bond, and the carbon number is 1~ 20 alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -.

[7]根據[6]所述的聚醯胺酸或其衍生物，其中：所述二醯肼為選自下述式(2-a-1)~式(2-a-2)、式(2-b-1)~式(2-b-3)或式(2-c-1)~式(2-c-6)中的至少1種二醯肼。 [7] The poly-proline or a derivative thereof according to [6], wherein the diterpene is selected from the group consisting of the following formula (2-a-1) to (2-a-2), (2-b-1)~ at least one of the formula (2-b-3) or the formula (2-c-1) to the formula (2-c-6).

[化15] [化15]

式(2-a-2)中，m為1~12的整數。 In the formula (2-a-2), m is an integer of 1 to 12.

[8]根據[1]至[7]中任一項所述的聚醯胺酸或其衍生物，其中：二胺含有選自下述式(DI-19-1)~式(DI-19-9)中的至少1種感光性二胺。 [A] The poly-proline or a derivative thereof according to any one of [1] to [7] wherein the diamine contains a compound selected from the following formula (DI-19-1) to (DI-19) At least one photosensitive diamine in -9).

[化16] [Chemistry 16]

[9]根據[1]至[8]中任一項所述的聚醯胺酸或其衍生物，其中：所述二胺含有選自由下述式(DI-1-3)、式(DI-1-4)、式(DI-4-1)、式(DI-5-1)、式(DI-5-5)、式(DI-5-9)、式(DI-5-12)、式(DI-5-21)、式(DI-5-28)、式(DI-5-30)、式(DI-5-31)、式(DI-7-3)、式(DI-9-1)、式(DI-13-4)、式(DI-13-5)、式(DI-13-47)、式(DI-16-1)、式(DI-16-2)、式(DI-16-4)、式(DI-19-1)、式(2-a-1)、式(2-a-2)、式(2-b-1)或式(2-b-2)所組成的群組中的至少1種。 [9] The polyaminic acid or derivative thereof according to any one of [1] to [8] wherein the diamine contains a compound selected from the following formula (DI-1-3), formula (DI) -1-4), formula (DI-4-1), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12) , formula (DI-5-21), formula (DI-5-28), formula (DI-5-30), formula (DI-5-31), formula (DI-7-3), formula (DI- 9-1), formula (DI-13-4), formula (DI-13-5), formula (DI-13-47), formula (DI-16-1), formula (DI-16-2), Formula (DI-16-4), formula (DI-19-1), formula (2-a-1), formula (2-a-2), formula (2-b-1) or formula (2-b) -2) At least one of the group consisting of.

[化17] [化17]

[化18] [化18]

式(DI-5-1)、式(DI-5-12)、式(DI-7-3)及式(2-a-2)中，m為1~12的整數；式(DI-5-30)中，k為1~5的整數；式(DI-7-3)中，n為1或2；式(DI-13-4)及式(DI-13-5)中，R³⁵為碳數1~30的烷基或碳數1~30的烷氧基；式(DI-16-1)及式(DI-16-2)中，R⁴⁰為-H或碳數1~20的烷基；式(DI-16-4)中，R⁴¹為-H或碳數1~12的烷基。 In the formula (DI-5-1), the formula (DI-5-12), the formula (DI-7-3), and the formula (2-a-2), m is an integer of 1 to 12; In -30), k is an integer of 1 to 5; in the formula (DI-7-3), n is 1 or 2; in the formula (DI-13-4) and the formula (DI-13-5), R ³⁵ It is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms; in the formula (DI-16-1) and the formula (DI-16-2), R ⁴⁰ is -H or a carbon number of 1 to 20 In the formula (DI-16-4), R ⁴¹ is -H or an alkyl group having 1 to 12 carbon atoms.

[10]一種液晶配向劑，其特徵在於：包括根據[1]至[9]中任一項所述的聚醯胺酸或其衍生物。 [10] A liquid crystal alignment agent comprising the poly-proline or a derivative thereof according to any one of [1] to [9].

[11]根據[10]所述的液晶配向劑，其中：更包括選自包含烯基取代納迪克醯亞胺化合物、具有自由基聚合性不飽和雙鍵的化合物、噁嗪化合物、噁唑啉化合物、及環氧化合物的化合物的群組中的至少1種。 [11] The liquid crystal alignment agent according to [10], which further comprises a compound selected from the group consisting of an alkenyl-substituted nadicilide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, and an oxazoline. At least one of the group of the compound and the compound of the epoxy compound.

[12]根據[11]所述的液晶配向劑，其中：烯基取代納迪克醯亞胺化合物為選自包含雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、N,N'-間苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、及N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)的化合物的群組中的至少1種。 [12] The liquid crystal alignment agent according to [11], wherein the alkenyl-substituted nadicilimine compound is selected from the group consisting of bis{4-(allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinoid imine)phenyl}methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene At least 1 in the group of compounds of the amine) and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine) Kind.

[13]根據[11]所述的液晶配向劑，其特徵在於：具有自由基聚合性不飽和雙鍵的化合物為選自包含N,N’-伸乙基雙丙烯醯胺、N,N’-(1,2-二羥基伸乙基)雙丙烯醯胺、伸乙基雙丙烯酸酯、及4,4’-亞甲基雙(N,N-二羥基伸乙基丙烯酸酯苯胺)的化合物的群組中的至少1種。 [13] The liquid crystal alignment agent according to [11], wherein the compound having a radical polymerizable unsaturated double bond is selected from the group consisting of N, N'-extended ethyl bis acrylamide, N, N' a compound of -(1,2-dihydroxyethylidene)bisacrylamide, ethylidene diacrylate, and 4,4'-methylenebis(N,N-dihydroxyethylidene anilide) At least one of the groups.

[14]根據[11]所述的液晶配向劑，其中：環氧化合物為選自包含N,N,N',N'-四縮水甘油基-間二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、2-[4-(2,3-環氧基丙氧基)苯基]-2-[4-[1,1-雙[4-([2,3-環氧基丙氧基]苯基)]乙基]苯基]丙烷、3,4-環氧基環己烯基甲基-3',4'-環氧基環己烯羧酸酯、N-苯基順丁烯二醯亞胺-甲基丙烯酸縮水甘油酯共聚物、及2-(3,4-環氧基環己基)乙基三甲氧基矽烷的化合物的群組中的至少1種。 [14] The liquid crystal alignment agent according to [11], wherein the epoxy compound is Selected from the group consisting of N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N , N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4 -[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane, 3,4-epoxycyclohexenylmethyl-3 ',4'-Epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2-(3,4-epoxycyclohexyl) At least one of the group of compounds of ethyltrimethoxydecane.

[15]一種液晶配向膜，其特徵在於：由根據[10]至[14]中任一項所述的液晶配向劑形成。 [15] A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of [10] to [14].

[16]一種光配向用液晶配向膜，其特徵在於：對由根據[10]至[14]中任一項所述的液晶配向劑形成的液晶配向膜照射偏光紫外線而獲得。 [16] A liquid crystal alignment film for photoalignment, which is obtained by irradiating a liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of [10] to [14] with a polarized ultraviolet ray.

[17]一種光配向用液晶配向膜，其特徵在於：經過如下的步驟而形成：將根據[10]至[14]中任一項所述的液晶配向劑塗布在基板上的步驟、對塗布有配向劑的基板進行加熱乾燥的步驟、以及對膜照射偏光紫外線的步驟。 [17] A liquid crystal alignment film for photoalignment, which is formed by the step of coating a liquid crystal alignment agent according to any one of [10] to [14] on a substrate, and coating the same. The step of heating and drying the substrate having the alignment agent and the step of irradiating the film with polarized ultraviolet rays.

[18]一種光配向用液晶配向膜，其特徵在於：經過如下的步驟而形成：將根據[10]至[14]中任一項所述的液晶配向劑塗布在基板上的步驟、對塗布有配向劑的基板進行加熱乾燥的步驟、對經乾燥的膜照射偏光紫外線的步驟、以及繼而對所述膜進行加熱煅燒的步驟。 [18] A liquid crystal alignment film for photoalignment, which is formed by the step of coating a liquid crystal alignment agent according to any one of [10] to [14] on a substrate, and coating the same. The step of heating and drying the substrate having the alignment agent, the step of irradiating the dried film with polarized ultraviolet rays, and the step of heating and calcining the film.

[19]一種光配向用液晶配向膜，其特徵在於：經過如下的步驟而形成：將根據[10]至[14]中任一項所述的液晶配向劑塗布在基板上的步驟、對塗布有配向劑的基板進行加熱乾燥的步驟、對經乾燥的膜進行加熱煅燒的步驟、以及繼而對所述膜照射偏光紫外線的步驟。 [19] A liquid crystal alignment film for photoalignment characterized by: The step of applying the liquid crystal alignment agent according to any one of [10] to [14] on a substrate, heating and drying the substrate coated with the alignment agent, and drying the dried film The step of heating the calcination, and then the step of irradiating the film with polarized ultraviolet light.

[20]一種液晶顯示元件，其特徵在於：包括根據[15]至[19]中任一項所述的液晶配向膜。 [20] A liquid crystal display element comprising the liquid crystal alignment film according to any one of [15] to [19].

若使用將本發明的酸二酐用作原料的配向劑，則可獲得由摩擦所產生的配向性、或由光照射所產生的化學變化的感光度良好，液晶分子的配向性優異的摩擦配向膜或光配向膜。而且，可獲得具有該配向膜的顯示特性優異的液晶顯示元件。 When an acid dianhydride of the present invention is used as an alignment agent for a raw material, the alignment which is caused by friction or the chemical change caused by light irradiation is excellent, and the alignment of the liquid crystal molecules is excellent. Film or photoalignment film. Further, a liquid crystal display element having excellent display characteristics of the alignment film can be obtained.

對本發明中所使用的用語進行說明。對化學結構式進行定義時所使用的“任意的”表示不僅位置任意，而且個數也任意。在化學結構式中，以六邊形包圍文字(例如A)的基是指環結構的基(環A)。 The terms used in the present invention will be described. The "arbitrary" used in defining the chemical structural formula means that the position is arbitrary and the number is arbitrary. In the chemical structural formula, a group enclosing a character (for example, A) in a hexagonal shape means a group (ring A) of a ring structure.

本發明的液晶配向劑含有作為四羧酸二酐與二胺的反應產物的聚醯胺酸或其衍生物。作為所述二胺，例如可列舉非側鏈型二胺、側鏈型二胺、感光性二胺、醯肼。所述聚醯胺酸的衍生物是指在製成含有溶劑的後述的液晶配向劑時溶解於溶劑中的成分，且是指當將該液晶配向劑製成後述的液晶配向膜時，可形成以聚醯亞胺為主成分的液晶配向膜的成分。作為此種聚醯胺酸的衍生物，例如可列舉可溶性聚醯亞胺、聚醯胺酸酯、聚醯肼酸、聚醯胺酸醯胺、及聚醯肼酸-醯胺酸等，更具體而言，可列舉：1)聚醯胺酸的所有胺基與羧基進行脫水閉環反應而成的聚醯亞胺、2)部分地進行脫水閉環反應而成的部分聚醯亞胺、3)將聚醯胺酸的羧基變換成酯而成的聚醯胺酸酯、4)將四羧酸二酐化合物中所含有的酸二酐的一部分取代成有機二羧酸並進行反應而獲得的聚醯胺酸-聚醯胺共聚物、以及5)使該聚醯胺酸-聚醯胺共聚物的一部分或全部進行脫水閉環反應而成的聚醯胺醯亞胺等。 The liquid crystal alignment agent of the present invention contains polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine. Examples of the diamine include a non-side chain type diamine, a side chain type diamine, a photosensitive diamine, and an anthracene. The derivative of polylysine refers to a solution which is dissolved in a solvent when it is prepared as a liquid crystal alignment agent to be described later containing a solvent. In the case where the liquid crystal alignment agent is formed into a liquid crystal alignment film to be described later, a component of a liquid crystal alignment film containing polyiminoimine as a main component can be formed. Examples of such a derivative of polyglycine include soluble polyimine, polyphthalate, polydecanoic acid, polyamidamine, and polydecanoic acid-proline, and the like. Specific examples include: 1) polyimine which is obtained by dehydration ring-closure reaction of all amine groups of poly-proline and carboxyl groups, 2) partial polyimine which is partially subjected to dehydration ring-closure reaction, and 3) A polyphthalate obtained by converting a carboxyl group of a poly-proline to an ester, and 4) a polycondensation obtained by substituting a part of an acid dianhydride contained in a tetracarboxylic dianhydride compound into an organic dicarboxylic acid A proline-polyamine copolymer and 5) a polyamidoximine obtained by subjecting a part or all of the polyamido-polyamine copolymer to a dehydration ring-closure reaction.

若有必要，則也可以通過摩擦處理或光照射來對由本發明的液晶配向劑所形成的配向膜賦予異向性。 If necessary, an anisotropic property may be imparted to the alignment film formed of the liquid crystal alignment agent of the present invention by rubbing treatment or light irradiation.

當通過光照射來賦予異向性時，若將本發明的液晶配向劑塗覆在基板上，通過預加熱來使其乾燥後，經由偏光板而照射紫外線的直線偏光，則與偏光方向大致平行的聚合物主鏈的源自感光性二胺的感光性基會產生光異構化。由於與偏光方向大致平行的聚合物的主鏈被選擇性地光異構化或光二聚化，因此形成膜的聚合物的主鏈的朝向相對於所照射的紫外線的偏光方向為大致直角方向的成分佔據支配地位。因此，對基板進行加熱而使聚醯胺酸進行脫水．閉環來製成聚醯亞胺膜後，使用該基板進行組裝而成的單元中所注入的液晶組合物的液晶分子使長軸與相對於所照射的紫外線的偏光方向為直角的方向一致來進行配向。對膜照射紫外線的直線偏光的步驟可在用於聚醯亞胺化的加熱步驟之前，也可以在進行加熱來進行聚醯亞胺化之後。 When the anisotropic property is imparted by light irradiation, the liquid crystal alignment agent of the present invention is applied onto a substrate, dried by preheating, and linearly polarized light that is irradiated with ultraviolet rays via a polarizing plate is substantially parallel to the polarizing direction. The photosensitive base derived from the photosensitive diamine of the polymer backbone generates photoisomerization. Since the main chain of the polymer substantially parallel to the polarizing direction is selectively photoisomerized or photodimerized, the orientation of the main chain of the polymer forming the film is substantially perpendicular to the direction of polarization of the irradiated ultraviolet light. The ingredients dominate. Therefore, the substrate is heated to dehydrate the polylysine. After the polyimine film is formed in a closed loop, the liquid crystal molecules of the liquid crystal composition injected in the unit assembled using the substrate are aligned with the direction perpendicular to the direction in which the polarized light of the ultraviolet light is irradiated. Orientation. Film irradiation The step of linearly polarizing the ultraviolet light may be performed before the heating step for polyimidization or after the polyimidization by heating.

對用於製造本發明的聚醯胺酸或其衍生物的四羧酸二酐進行說明。以下，“四羧酸二酐”這一記載不僅表示單獨使用四羧酸二酐的情況，也表示將多個四羧酸二酐用作混合物的情況。本發明使用由式(1)所表示的四羧酸二酐。在以下的說明中，有時以酸二酐(1)來表示由式(1)所表示的四羧酸二酐。 The tetracarboxylic dianhydride used to produce the poly-proline or its derivative of the present invention will be described. Hereinafter, the description of "tetracarboxylic dianhydride" means not only the case of using tetracarboxylic dianhydride alone, but also the case where a plurality of tetracarboxylic dianhydrides are used as a mixture. The present invention uses the tetracarboxylic dianhydride represented by the formula (1). In the following description, the tetracarboxylic dianhydride represented by the formula (1) may be represented by the acid dianhydride (1).

以下所示的式(1-a)及式(1-b)為將式(1)進一步具體化的例子。 The formula (1-a) and the formula (1-b) shown below are examples in which the formula (1) is further embodied.

酸二酐(1)可單獨使用1種化合物，也可以將2種以上混合使用。酸二酐(1)可與其他四羧酸二酐混合使用。此時的四羧酸二酐的混合物中的酸二酐(1)是以10 wt%(重量百分比)以上的比例來使用，優選30 wt%以上，若為50 wt%以上，則更優選。 The acid dianhydride (1) may be used alone or in combination of two or more. The acid dianhydride (1) can be used in combination with other tetracarboxylic dianhydrides. Four at this time The acid dianhydride (1) in the mixture of carboxylic acid dianhydride is used in a ratio of 10 wt% or more, preferably 30 wt% or more, and more preferably 50 wt% or more.

作為酸二酐(1)以外的其他四羧酸二酐，可無限制地從公知的四羧酸二酐中選擇。此種四羧酸二酐可為屬於二羧酸二酐直接結合在芳香環上的芳香族系(包含雜芳香環系)、及二羧酸二酐未直接結合在芳香環上的脂肪族系(包含雜環系)的任一群組中的四羧酸二酐。 Other tetracarboxylic dianhydrides other than the acid dianhydride (1) can be selected from known tetracarboxylic dianhydrides without limitation. The tetracarboxylic dianhydride may be an aromatic system (including a heteroaromatic ring system) in which a dicarboxylic dianhydride is directly bonded to an aromatic ring, and an aliphatic system in which a dicarboxylic dianhydride is not directly bonded to an aromatic ring. Tetracarboxylic dianhydride in any group (including a heterocyclic ring).

作為此種四羧酸二酐的適宜的例子，就原料獲得的容易性、或聚合物聚合時的容易性、膜的電特性的觀點而言，可列舉由式(AN-I)~式(AN-VII)所表示的四羧酸二酐。 A suitable example of such a tetracarboxylic dianhydride is a formula (AN-I) to a formula (E-I) to the viewpoint of easiness of obtaining a raw material, easiness in polymerization of a polymer, and electrical properties of a film. Tetracarboxylic dianhydride represented by AN-VII).

[化22] [化22]

式(AN-I)、式(AN-IV)及式(AN-V)中，X獨立為單鍵或-CH₂-，式(AN-II)中，G為單鍵、碳數1~20的伸烷基、-CO-、-O-、-S-、-SO₂-、-C(CH₃)₂-、或-C(CF₃)₂-，式(AN-II)~式(AN-IV)中，Y獨立為選自下述的三價的基的群組中的1種，結合鍵與任意的碳連結，該基的任意的氫可由甲基、乙基或苯基取代， In the formula (AN-I), the formula (AN-IV) and the formula (AN-V), X is independently a single bond or -CH ₂ -, in the formula (AN-II), G is a single bond, and the carbon number is 1~ 20 alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -, formula (AN-II)~ In (AN-IV), Y is independently one selected from the group consisting of trivalent groups described below, and a bond is bonded to an arbitrary carbon, and any hydrogen of the group may be a methyl group, an ethyl group or a phenyl group. Replace,

式(AN-III)~式(AN-V)中，環A為碳數3~10的單環式烴的基或碳數6~30的縮合多環式烴的基，該基的任意的氫可由甲基、乙基或苯基取代，連接在環上的結合鍵與構成環的任意的碳連結，2個結合鍵可與同一個碳連結，式(AN-VI)中，X¹⁰為碳數2~6的伸烷基，Me為甲基，且Ph為苯基，式(AN-VII)中，G¹⁰獨立為-O-、-COO-或-OCO-，r獨立為0或1。 In the formula (AN-III) to the formula (AN-V), the ring A is a group of a monocyclic hydrocarbon having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon having 6 to 30 carbon atoms, and any of the groups The hydrogen may be substituted by a methyl group, an ethyl group or a phenyl group, and the bonding bond attached to the ring may be bonded to any carbon constituting the ring, and the two bonding bonds may be bonded to the same carbon. In the formula (AN-VI), X ¹⁰ is a C 2~6 alkylene group, Me is a methyl group, and Ph is a phenyl group. In the formula (AN-VII), G ^{10 is} independently -O-, -COO- or -OCO-, and r is independently 0 or 1.

更詳細而言，可列舉由以下的式(AN-1)~式(AN-16-14)所表示的四羧酸二酐。 More specifically, tetracarboxylic dianhydride represented by the following formula (AN-1) to formula (AN-16-14) can be mentioned.

式(AN-1)中，G¹¹為單鍵、碳數1~12的伸烷基、1,4-伸苯基、或1,4-伸環己基。X¹¹獨立為單鍵或-CH₂-。G¹²獨立為CH或N。當G¹²為CH時，CH的氫可被-CH₃取代。當G¹²為N時，G¹¹不為單鍵及-CH₂-，X¹¹不為單鍵。而且，R¹¹為-H或-CH₃。作為由式(AN-1)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-1), G ¹¹ is a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group, or a 1,4-cyclohexylene group. X ^{11 is} independently a single bond or -CH ₂ -. G ^{12 is} independently CH or N. When G ¹² is CH, the hydrogen of CH may be substituted by -CH ₃ . When G ¹² is N, G ^{11 is} not a single bond and -CH ₂ -, and X ^{11 is} not a single bond. Moreover, R ¹¹ is -H or -CH ₃ . An example of the tetracarboxylic dianhydride represented by the formula (AN-1) is a compound represented by the following formula.

[化25] [化25]

式(AN-1-2)及式(AN-1-14)中，m為1~12的整數。 In the formula (AN-1-2) and the formula (AN-1-14), m is an integer of 1 to 12.

式(AN-2)中，R¹²獨立為-H、-CH₃、-CH₂CH₃、或苯基。作為由式(AN-2)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-2), R ^{12 is} independently -H, -CH ₃ , -CH ₂ CH ₃ or a phenyl group. An example of the tetracarboxylic dianhydride represented by the formula (AN-2) is a compound represented by the following formula.

[化27] [化27]

式(AN-3)中，環A¹¹為環己烷環或苯環。作為由式(AN-3)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-3), the ring A ¹¹ is a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formulas.

式(AN-4)中，G¹³為單鍵、-CH₂-、-CH₂CH₂-、-O-、-S-、-C(CH₃)₂-、-SO₂-、-CO-或-C(CF₃)₂-。環A¹¹分別獨立為環己烷環或苯環。G¹³可結合在環A¹¹的任意的位置上。作為由式(AN-4)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-4), G ¹³ is a single bond, -CH ₂ -, -CH ₂ CH ₂ -, -O-, -S-, -C(CH ₃ ) ₂ -, -SO ₂ -, -CO -or-C(CF ₃ ) ₂ -. Ring A ^{11 is} independently a cyclohexane ring or a benzene ring. G ¹³ can be bonded to any position of the ring A ¹¹ . Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulas.

[化32] [化32]

[化34] [化34]

式(AN-5)中，R¹¹為-H、或-CH₃。結合位置未固定在構成苯環的碳原子上的R¹¹表示在苯環中的結合位置任意。作為由式(AN-5)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-5), R ¹¹ is -H or -CH ₃ . R ¹¹ in which the bonding position is not fixed to the carbon atom constituting the benzene ring means that the bonding position in the benzene ring is arbitrary. An example of the tetracarboxylic dianhydride represented by the formula (AN-5) is a compound represented by the following formula.

式(AN-6)中，X¹¹獨立為單鍵或-CH₂-。X¹²為-CH₂-、-CH₂CH₂-或-CH=CH-。n為1或2。作為由式(AN-6)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-6), X ^{11 is} independently a single bond or -CH ₂ -. X ¹² is -CH ₂ -, -CH ₂ CH ₂ - or -CH=CH-. n is 1 or 2. An example of the tetracarboxylic dianhydride represented by the formula (AN-6) is a compound represented by the following formula.

[化37] [化37]

式(AN-7)中，X¹¹為單鍵或-CH₂-。作為由式(AN-7)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-7), X ¹¹ is a single bond or -CH ₂ -. An example of the tetracarboxylic dianhydride represented by the formula (AN-7) is a compound represented by the following formula.

[化40] [化40]

式(AN-8)中，X¹¹為單鍵或-CH₂-。R¹²為-H、-CH₃、-CH₂CH₃、或苯基，環A¹²為環己烷環或環己烯環。作為由式(AN-8)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-8), X ¹¹ is a single bond or -CH ₂ -. R ¹² is -H, -CH ₃ , -CH ₂ CH ₃ or a phenyl group, and ring A ¹² is a cyclohexane ring or a cyclohexene ring. An example of the tetracarboxylic dianhydride represented by the formula (AN-8) is a compound represented by the following formula.

式(AN-9)中，r分別獨立為0或1。作為由式(AN-9)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-9), r is independently 0 or 1. An example of the tetracarboxylic dianhydride represented by the formula (AN-9) is a compound represented by the following formula.

式(AN-10)為下述的四羧酸二酐。 The formula (AN-10) is the following tetracarboxylic dianhydride.

式(AN-11)中，環A¹¹獨立為環己烷環或苯環。作為由式(AN-11)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-11), the ring A ^{11 is} independently a cyclohexane ring or a benzene ring. An example of the tetracarboxylic dianhydride represented by the formula (AN-11) is a compound represented by the following formula.

式(AN-12)中，環A¹¹分別獨立為環己烷環或苯環。作為由式(AN-12)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-12), the ring A ^{11 is} independently a cyclohexane ring or a benzene ring. An example of the tetracarboxylic dianhydride represented by the formula (AN-12) is a compound represented by the following formula.

式(AN-13)中，X¹³為碳數2~6的伸烷基。作為由式(AN-13)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-13), X ¹³ is an alkylene group having 2 to 6 carbon atoms. An example of the tetracarboxylic dianhydride represented by the formula (AN-13) is a compound represented by the following formula.

[化51] [化51]

式(AN-14)中，G¹⁴獨立為-O-、-COO-或-OCO-，r獨立為0或1。作為由式(AN-14)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-14), G ^{14 is} independently -O-, -COO- or -OCO-, and r is independently 0 or 1. An example of the tetracarboxylic dianhydride represented by the formula (AN-14) is a compound represented by the following formula.

[化52] [化52]

式(AN-15)中，w為1~10的整數。作為由式(AN-15)所表示的四羧酸二酐的例子，可列舉由下述式所表示的化合物。 In the formula (AN-15), w is an integer of 1 to 10. Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formulas.

[化54] [54]

作為所述以外的四羧酸二酐，可列舉下述的化合物。 Examples of the tetracarboxylic dianhydride other than the above include the following compounds.

在重視提升液晶顯示元件的配向性的情況下，所述酸二酐之中，特優選由式(AN-1-1)、式(AN-2-1)、式(AN-3-1)、式(AN-3-2)、式(AN-4-5)、式(AN-4-17)、式(AN-4-21)、式 (AN-7-2)、式(AN-10)、及式(AN-11-3)所表示的化合物。 When it is important to improve the alignment of the liquid crystal display element, among the acid dianhydrides, the formula (AN-1-1), the formula (AN-2-1), and the formula (AN-3-1) are particularly preferable. , formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), (AN-7-2), a compound represented by the formula (AN-10), and the formula (AN-11-3).

在重視提升液晶顯示元件的透過率的情況下，所述酸二酐之中，特優選由式(AN-1-1)、式(AN-1-13)、式(AN-2-1)、式(AN-3-1)、式(AN-7-2)及式(AN-10)所表示的化合物。 When it is important to increase the transmittance of the liquid crystal display device, among the acid dianhydrides, the formula (AN-1-1), the formula (AN-1-13), and the formula (AN-2-1) are particularly preferable. A compound represented by the formula (AN-3-1), the formula (AN-7-2), and the formula (AN-10).

對用於製造本發明的聚醯胺酸或其衍生物的二胺進行說明。本發明的二胺成分可無限制地從用於製造聚醯胺酸或其衍生物的公知的二胺中選擇。另外，二胺可單獨使用，也可以將多種二胺用作混合物。 The diamine used to produce the polyaminic acid of the present invention or a derivative thereof will be described. The diamine component of the present invention can be selected from known diamines for producing polyglycine or a derivative thereof without limitation. Further, the diamine may be used singly or as a mixture of a plurality of diamines.

二胺化合物可根據其結構而分成2種。即，具有側鏈基的二胺與不具有側鏈基的二胺，該側鏈基是當將連結2個胺基的骨架看作主鏈時，從主鏈中分支的基。該側鏈基是具有增大預傾角的效果的基。具有此種效果的側鏈基必須是碳數3以上的基，作為具體例，可列舉：碳數3以上的烷基、碳數3以上的烷氧基、碳數3以上的烷氧基烷基、及具有類固醇骨架的基。具有1個以上的環，且其末端的環具有碳數1以上的烷基、碳數1以上的烷氧基及碳數2以上的烷氧基烷基的任一者作為取代基的基也具有作為側鏈基的效果。在以下的說明中，有時將具有此種側鏈基的二胺稱為側鏈型二胺。而且，有時將不具有此種側鏈基的二胺稱為非側鏈型二胺。 The diamine compound can be classified into two according to its structure. That is, a diamine having a side chain group and a diamine having no side chain group, the side chain group being a group branched from the main chain when the skeleton linking the two amine groups is regarded as a main chain. The side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect is required to have a carbon number of 3 or more. Specific examples thereof include an alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, and an alkoxyalkyl group having 3 or more carbon atoms. a base, and a group having a steroid skeleton. A group having one or more rings and having a ring having a carbon number of 1 or more, an alkoxy group having 1 or more carbon atoms, and an alkoxyalkyl group having 2 or more carbon atoms as a substituent It has an effect as a side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain type diamine. Further, a diamine having no such a side chain group is sometimes referred to as a non-side chain type diamine.

通過將非側鏈型二胺與側鏈型二胺適當地分開使用，可對應於各自所需要的預傾角。側鏈型二胺優選以無損本發明的特性的程度來並用。另外，關於側鏈型二胺及非側鏈型二胺，優選以提升對於液晶的垂直配向性、電壓保持率、殘像特性及配向性為目的進行取捨選擇來使用。 By suitably separating the non-side chain type diamine from the side chain type diamine, it is possible to correspond to the respective pretilt angles required. The side chain type diamine is preferably used in combination to the extent that the characteristics of the present invention are not impaired. Further, regarding the side chain type diamine and the non-side chain type diamine, preferably It is used for the purpose of improving the vertical alignment, the voltage holding ratio, the afterimage characteristics, and the alignment of the liquid crystal.

對非側鏈型二胺進行說明。作為已知的不具有側鏈的二胺，可列舉以下的式(DI-1)~式(DI-12)的二胺。 The non-side chain type diamine is described. Examples of the known diamine having no side chain include the following diamines of the formula (DI-1) to the formula (DI-12).

所述式(DI-1)中，m為1~12的整數，伸烷基的任意的氫可被-OH取代。(DI-3)及(DI-5)~(DI-7)中，G²¹獨立為單鍵、-NH-、-O-、-S-、-S-S-、-SO₂-、-CO-、-CONH-、-CONCH₃-、-NHCO-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m'-、-O-(CH₂)_m'-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、或-S-(CH₂)_m'-S-，m'獨立為1~12的整數，k為1~5的整數。(DI-6)及(DI-7)中，G²²獨立為單鍵、 -O-、-S-、-CO-、-C(CH₃)₂-、-C(CF₃)₂-、或碳數1~10的伸烷基。式(DI-2)~式(DI-7)中的環己烷環及苯環的任意的-H可由-F、-CH₃、-OH、-CF₃、-CO₂H、-CONH₂、或苄基取代，此外，在式(DI-4)中，可由下述式(DI-4-a)~式(DI-4-c)取代。結合位置未固定在構成環的碳原子上的基表示在該環中的結合位置任意。而且，-NH₂在環己烷環或苯環上的結合位置為除G²¹或G²²的結合位置以外的任意的位置。 In the formula (DI-1), m is an integer of 1 to 12, and any hydrogen of the alkyl group may be substituted by -OH. In (DI-3) and (DI-5)~(DI-7), G ^{21 is} independently a single bond, -NH-, -O-, -S-, -SS-, -SO ₂ -, -CO- , -CONH-, -CONCH ₃ -, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m' -, -O-(CH ₂ ) _m' -O-, -N(CH ₃ )-(CH ₂ ) _k -N(CH ₃ )-, or -S-(CH ₂ ) _m' -S-,m' is independently an integer from 1 to 12, and k is An integer from 1 to 5. In (DI-6) and (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, Or an alkyl group having a carbon number of 1 to 10. Any -H of the cyclohexane ring and the benzene ring of the formula (DI-2) to the formula (DI-7) may be -F, -CH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ Alternatively, or a benzyl group, in the formula (DI-4), it may be substituted by the following formula (DI-4-a) to formula (DI-4-c). The group in which the bonding position is not fixed to the carbon atom constituting the ring means that the bonding position in the ring is arbitrary. Further, the bonding position of -NH ₂ on the cyclohexane ring or the benzene ring is any position other than the bonding position of G ²¹ or G ²² .

式(DI-4-a)及式(DI-4-b)中，R²⁰獨立為-H或-CH₃。 In the formula (DI-4-a) and the formula (DI-4-b), R ^{20 is} independently -H or -CH ₃ .

[化58] [化58]

式(DI-8)中，R²¹及R²²獨立為碳數1~3的烷基或苯基，G²³獨立為碳數1~6的伸烷基、伸苯基或經烷基取代的伸苯基，w為1~10的整數。 In the formula (DI-8), R ²¹ and R ^{22 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and G ^{23 is} independently an alkylene group having 1 to 6 carbon atoms, a phenyl group or an alkyl group. Phenyl is extended, and w is an integer from 1 to 10.

式(DI-9)中，R²³獨立為碳數1~5的烷基、碳數1~5的烷氧基或-Cl，p獨立為0~3的整數，q為0~4的整數。 In the formula (DI-9), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4. .

式(DI-10)中，R²⁴為-H、碳數1~4的烷基、苯基、或苄基。 In the formula (DI-10), R ²⁴ is -H, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a benzyl group.

式(DI-11)中，G²⁴為-CH₂-或-NH-。 In the formula (DI-11), G ²⁴ is -CH ₂ - or -NH-.

式(DI-12)中，G²⁵為單鍵、碳數2~6的伸烷基或1,4-伸苯基，r為0或1。而且，結合位置未固定在構成環的碳原子上的基表示在該環中的結合位置任意。 In the formula (DI-12), G ²⁵ is a single bond, an alkylene group having 2 to 6 carbon atoms or a 1,4-phenylene group, and r is 0 or 1. Further, the group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary.

式(DI-9)、式(DI-11)及式(DI-12)中，結合在苯環上的-NH₂的結合位置為任意的位置。 In the formula (DI-9), the formula (DI-11) and the formula (DI-12), the bonding position of -NH ₂ bonded to the benzene ring is an arbitrary position.

作為所述式(DI-1)~式(DI-12)的不具有側鏈的二胺，可列舉以下的式(DI-1-1)~式(DI-12-1)的具體例。 Specific examples of the diamine having no side chain of the formula (DI-1) to the formula (DI-12) include the following formula (DI-1-1) to formula (DI-12-1).

以下表示由式(DI-1)~式(DI-3)所表示的二胺的例子。 Examples of the diamine represented by the formula (DI-1) to the formula (DI-3) are shown below.

以下表示由式(DI-4)所表示的二胺的例子。 An example of the diamine represented by the formula (DI-4) is shown below.

以下表示由式(DI-5)所表示的二胺的例子。 An example of the diamine represented by the formula (DI-5) is shown below.

[化63] [化63]

式(DI-5-1)中，m為1~12的整數。 In the formula (DI-5-1), m is an integer of 1 to 12.

式(DI-5-12)及式(DI-5-13)中，m為1~12的整數。 In the formula (DI-5-12) and the formula (DI-5-13), m is an integer of 1 to 12.

[化65] [化65]

式(DI-5-16)中，v為1~6的整數。 In the formula (DI-5-16), v is an integer of 1 to 6.

式(DI-5-30)中，k為1~5的整數。 In the formula (DI-5-30), k is an integer of 1 to 5.

以下表示由式(DI-6)所表示的二胺的例子。 An example of the diamine represented by the formula (DI-6) is shown below.

以下表示由式(DI-7)所表示的二胺的例子。 An example of the diamine represented by the formula (DI-7) is shown below.

式(DI-7-3)及式(DI-7-4)中，m為1~12的整數，n 獨立為1或2。 In the formula (DI-7-3) and the formula (DI-7-4), m is an integer from 1 to 12, n Independent is 1 or 2.

以下表示由式(DI-8)所表示的二胺的例子。 An example of the diamine represented by the formula (DI-8) is shown below.

以下表示由式(DI-9)所表示的二胺的例子。 An example of the diamine represented by the formula (DI-9) is shown below.

[化71] [71]

以下表示由式(DI-10)所表示的二胺的例子。 An example of the diamine represented by the formula (DI-10) is shown below.

[化74] [化74]

以下表示由式(DI-11)所表示的二胺的例子。 An example of the diamine represented by the formula (DI-11) is shown below.

以下表示由式(DI-12)所表示的二胺的例子。 An example of the diamine represented by the formula (DI-12) is shown below.

此種非側鏈型二胺具有降低液晶顯示元件的離子密度等改善電特性的效果。當使用非側鏈型二胺作為用於製造本發明的液晶配向劑中所使用的聚醯胺酸或聚醯亞胺的二胺時，優選將非側鏈型二胺在二胺總量中所占的比例設為0莫耳%~95莫耳%，更優選設為0莫耳%~90莫耳%。 Such a non-side chain type diamine has an effect of improving electrical characteristics such as ion density of a liquid crystal display element. When a non-side chain type diamine is used as the diamine of the polyphthalic acid or polyimine used in the production of the liquid crystal alignment agent of the present invention, it is preferred to use the non-side chain type diamine in the total amount of the diamine. The proportion is set to 0% by mole to 95% by mole, more It is preferably set to 0 mol% to 90 mol%.

對側鏈型二胺進行說明。作為側鏈型二胺的側鏈基，可列舉以下的基。 The side chain type diamine is described. Examples of the side chain group of the side chain type diamine include the following groups.

作為側鏈基，首先可列舉：烷基、烷氧基、烷氧基烷基、烷基羰基、烷基羰氧基、烷氧基羰基、烷基胺基羰基、烯基、烯氧基、烯基羰基、烯基羰氧基、烯氧基羰基、烯基胺基羰基、炔基、炔氧基、炔基羰基、炔基羰氧基、炔氧基羰基、炔基胺基羰基等。這些基中的烷基、烯基及炔基均是碳數3以上的基。但是，在烷氧基烷基中，只要整個基的碳數3以上即可。這些基可以是直鏈狀，也可以是支鏈狀。 The side chain group may, first, be an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkenyl group, an alkenyloxy group, or the like. Alkenylcarbonyl, alkenylcarbonyloxy, alkenoxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl, and the like. The alkyl group, the alkenyl group and the alkynyl group in these groups are each a group having 3 or more carbon atoms. However, in the alkoxyalkyl group, the carbon number of the entire group may be 3 or more. These groups may be linear or branched.

其次，以末端的環具有碳數1以上的烷基、碳數1以上的烷氧基或碳數2以上的烷氧基烷基作為取代基為條件，可列舉：苯基、苯基烷基、苯基烷氧基、苯氧基、苯基羰基、苯基羰氧基、苯氧基羰基、苯基胺基羰基、苯基環己氧基、碳數3以上的環烷基、環己基烷基、環己氧基、環己氧基羰基、環己基苯基、環己基苯基烷基、環己基苯氧基、雙(環己基)氧基、雙(環己基)烷基、雙(環己基)苯基、雙(環己基)苯基烷基、雙(環己基)氧基羰基、雙(環己基)苯氧基羰基、及環己基雙(苯基)氧基羰基等環結構的基。 Next, the terminal ring has an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms as a substituent, and examples thereof include a phenyl group and a phenylalkyl group. , phenylalkoxy, phenoxy, phenylcarbonyl, phenylcarbonyloxy, phenoxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexyl Alkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenoxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkyl, bis( Cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenoxycarbonyl, and cyclohexylbis(phenyl)oxycarbonyl base.

進而，可列舉如下的環集合基，其為具有2個以上的苯環的基、具有2個以上的環己烷環的基、或包含苯環及環己烷環的2個環以上的基，且結合基獨立為單鍵、-O-、-COO-、-OCO-、-CONH-或碳數1~3的伸烷基，末端的環具有碳數1以上的烷基、碳數1以上的氟取代烷基、碳數1以上的烷氧基、或碳數2以上的烷氧基烷基作為取代基。具有類固醇骨架的基作為側鏈基也有效。 Further, examples of the ring group include a group having two or more benzene rings, a group having two or more cyclohexane rings, or a group having two or more rings of a benzene ring and a cyclohexane ring. And the binding group is independently a single bond, -O-, -COO-, -OCO-, -CONH- or an alkylene group having 1 to 3 carbon atoms, and the terminal ring has an alkyl group having 1 or more carbon atoms, A fluorine-substituted alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms is used as a substituent. A group having a steroid skeleton is also effective as a side chain group.

作為具有側鏈的二胺，可列舉由以下的式(DI-13)~式(DI-17)所表示的化合物。 The diamine having a side chain includes a compound represented by the following formula (DI-13) to formula (DI-17).

式(DI-13)中，G²⁶為單鍵、-O-、-COO-、-OCO-、-CO-、-CONH-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、或-(CH₂)_m'-，m'為1~12的整數。G²⁶的優選的例子為單鍵、-O-、-COO-、-OCO-、-CH₂O-、及碳數1~3的伸烷基，特優選的例子為單鍵、-O-、-COO-、-OCO-、-CH₂O-、-CH₂-及-CH₂CH₂-。R²⁵為碳數3~30的烷基、苯基、具有類固醇骨架的基、或由下述的式(DI-13-a)所表示的基。該烷基中，任意的-H可由-F取代，且任意的-CH₂-可由-O-、-CH=CH-或-C≡C-取代。該苯基的-H可由-F、-CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃、碳數3~30的烷基或碳數3~30的烷氧基取代，該環己基的-H可由碳數3~30的烷基或碳數3~30的烷氧基取代，結合在苯環上的-NH₂的結合位置表示在該環中為任意的位置，但其結合位置優選間位或對位。即，當將基“R²⁵-G²⁶-”的結合位置設為1位時，2個結合位置優選3位與5位、或2位與5位。 In the formula (DI-13), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O- , -OCF ₂ -, or -(CH ₂ ) _m' -, m' is an integer from 1 to 12. Preferable examples of G ²⁶ are a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and an alkylene group having 1 to 3 carbon atoms, and a particularly preferred example is a single bond, -O- , -COO-, -OCO-, -CH ₂ O-, -CH ₂ -, and -CH ₂ CH ₂ -. R ²⁵ is an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (DI-13-a). In the alkyl group, any -H may be substituted by -F, and any -CH ₂ - may be substituted by -O-, -CH=CH- or -C≡C-. The -H of the phenyl group may be substituted by -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. The -H of the cyclohexyl group may be substituted by an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, and the bonding position of -NH ₂ bonded to the benzene ring means an arbitrary position in the ring. However, the binding position is preferably a meta or para position. That is, when the binding position of the group "R ²⁵ -G ²⁶ -" is set to 1 position, the two bonding positions are preferably 3 bits and 5 bits, or 2 bits and 5 bits.

式(DI-13-a)中，G²⁷、G²⁸及G²⁹為結合基，這些獨立為單鍵、或碳數1~12的伸烷基，該伸烷基的1個以上的-CH₂-可由-O-、-COO-、-OCO-、-CONH-、-CH=CH-取代。環B²¹、環B²²、環B²³、及環B²⁴獨立為1,4-伸苯基、1,4-伸環己基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、萘-1,5-二基、萘-2,7-二基或蒽-9,10-二基，環B²¹、環B²²、環B²³、及環B²⁴中，任意的-H可由-F或-CH₃取代，s、t及u獨立為0~2的整數，這些的合計為1~5，當s、t或u為2時，各個括號內的2個結合基可相同，也可以不同，且2個環可相同，也可以不同。R²⁶為-F、-OH、碳數1~30的烷基、碳數1~30的氟取代烷基、碳數1~30的烷氧基、-CN、-OCH₂F、-OCHF₂、或-OCF₃，該碳數1~30的烷基的任意的-CH₂-可由以下述式(DI-13-b)所表示的二價的基取代。 In the formula (DI-13-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, and these are independently a single bond or an alkylene group having 1 to 12 carbon atoms, and one or more -CH of the alkylene group. ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-. Ring B ²¹ , ring B ²² , ring B ²³ , and ring B ^{24 are} independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine -2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluoren-9,10-diyl, ring B ²¹ , ring B ²² , ring B ²³ , and ring B ²⁴ , any -H may be replaced by -F or -CH ₃ , and s, t, and u are independently integers of 0 to 2, and the total of these is 1 to 5, when s, t Or when u is 2, the two binding groups in each parenthesis may be the same or different, and the two rings may be the same or different. R ²⁶ is -F, -OH, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ Or -OCF ₃ , any -CH ₂ - of the alkyl group having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-13-b).

[化79] [化79]

式(DI-13-b)中，R²⁷及R²⁸獨立為碳數1~3的烷基，v為1~6的整數。R²⁶的優選的例子為碳數1~30的烷基及碳數1~30的烷氧基。 In the formula (DI-13-b), R ²⁷ and R ^{28 are} independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferable examples of R ²⁶ are an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.

式(DI-14)及式(DI-15)中，G³⁰獨立為單鍵、-CO-或-CH₂-，R²⁹獨立為-H或-CH₃，R³⁰為-H、碳數1~20的烷基、或碳數2~20的烯基。式(DI-15)中的苯環的1個-H可由碳數1~20的烷基或苯基取代。而且，結合位置未固定在構成環的任一個碳原子上的基表示在該環中的結合位置任意。優選式(DI-14)中的2個基“-伸苯基-G³⁰-O-”的一個結合在類固醇核的3位上，另一個結合在類固醇核的6位上。式(DI-15)中的2個基“-伸苯基 -G³⁰-O-”在苯環上的結合位置優選相對於類固醇核的結合位置，分別為間位或對位。式(DI-14)及式(DI-15)中，結合在苯環上的-NH₂表示在該環中的結合位置任意。 In formula (DI-14) and formula (DI-15), G ^{30 is} independently a single bond, -CO- or -CH ₂ -, R ^{29 is} independently -H or -CH ₃ , R ³⁰ is -H, carbon number An alkyl group of 1 to 20 or an alkenyl group having 2 to 20 carbon atoms. One-H of the benzene ring in the formula (DI-15) may be substituted with an alkyl group having 1 to 20 carbon atoms or a phenyl group. Further, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position in the ring is arbitrary. Preferably, one of the two base "-phenyl-G ³⁰ -O-" groups of formula (DI-14) is bonded at the 3-position of the steroid nucleus and the other is bound at the 6 position of the steroid nucleus. The binding position of the two base "-phenyl-G ³⁰ -O-" in the formula (DI-15) to the phenyl ring is preferably a meta position or a para position, respectively, with respect to the binding position of the steroid nucleus. In the formula (DI-14) and the formula (DI-15), -NH ₂ bonded to the benzene ring means that the bonding position in the ring is arbitrary.

式(DI-16)及式(DI-17)中，G³¹獨立為-O-或碳數1~6的伸烷基，G³²為單鍵或碳數1~3的伸烷基。R³¹為-H或碳數1~20的烷基，該烷基的任意的-CH₂-可由-O-、-CH=CH-或-C≡C-取代。R³²為碳數6~22的烷基，R³³為-H或碳數1~22的烷基。環B²⁵為1,4-伸苯基或1,4-伸環己基，r為0或1。而且，結合在苯環上的-NH₂表示在該環中的結合位置任意，但優選獨立且相對於G³¹的結合位置為間位或對位。 In the formula (DI-16) and the formula (DI-17), G ^{31 is} independently -O- or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms. R ³¹ is -H or an alkyl group having 1 to 20 carbon atoms, and any -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-. R ³² is an alkyl group having 6 to 22 carbon atoms, and R ³³ is -H or an alkyl group having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. Further, -NH ₂ bonded to the benzene ring means that the bonding position in the ring is arbitrary, but is preferably independent and the bonding position with respect to G ³¹ is meta or para.

以下例示側鏈型二胺的具體例。作為所述式(DI-13)~式(DI-17)的具有側鏈的二胺化合物，可列舉由下述的式(DI-13-1) ~式(DI-17-3)所表示的化合物。 Specific examples of the side chain type diamine are exemplified below. The diamine compound having a side chain of the formula (DI-13) to formula (DI-17) is exemplified by the following formula (DI-13-1) a compound represented by the formula (DI-17-3).

以下表示由式(DI-13)所表示的化合物的例子。 An example of the compound represented by the formula (DI-13) is shown below.

式(DI-13-1)~式(DI-13-11)中，R³⁴為碳數1~30的烷基或碳數1~30的烷氧基，優選碳數5~25的烷基或碳數5~25的烷氧基。R³⁵為碳數1~30的烷基或碳數1~30的烷氧基，優選碳數3~25的烷基或碳數3~25的烷氧基。 In the formula (DI-13-1) to the formula (DI-13-11), R ³⁴ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 5 to 25 carbon atoms. Or an alkoxy group having a carbon number of 5 to 25. R ³⁵ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, and preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

[化83] [化83]

式(DI-13-12)~式(DI-13-17)中，R³⁶為碳數4~30的烷基，優選碳數6~25的烷基。R³⁷為碳數6~30的烷基，優選碳數8~25的烷基。 In the formula (DI-13-12) to the formula (DI-13-17), R ³⁶ is an alkyl group having 4 to 30 carbon atoms, and preferably an alkyl group having 6 to 25 carbon atoms. R ³⁷ is an alkyl group having 6 to 30 carbon atoms, and preferably an alkyl group having 8 to 25 carbon atoms.

[化85] [化85]

式(DI-13-18)~式(DI-13-43)中，R³⁸為碳數1~20的烷基或碳數1~20的烷氧基，優選碳數3~20的烷基或碳數3~20的烷氧基。R³⁹為-H、-F、碳數1~30的烷基、碳數1~30的烷氧基、-CN、-OCH₂F、-OCHF₂或-OCF₃，優選碳數3~25的烷基、或碳數3~25的烷氧基。而且，G³³為碳數1~20的伸烷基。 In the formula (DI-13-18) to the formula (DI-13-43), R ³⁸ is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, preferably an alkyl group having 3 to 20 carbon atoms. Or an alkoxy group having a carbon number of 3 to 20. R ³⁹ is -H, -F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , preferably having a carbon number of 3 to 25 An alkyl group or an alkoxy group having a carbon number of 3 to 25. Further, G ³³ is an alkylene group having 1 to 20 carbon atoms.

[化89] [化89]

以下表示由式(DI-14)所表示的化合物的例子。 An example of the compound represented by the formula (DI-14) is shown below.

[化93] [化93]

以下表示由式(DI-15)所表示的化合物的例子。 An example of the compound represented by the formula (DI-15) is shown below.

以下表示由式(DI-16)所表示的化合物的例子。 An example of the compound represented by the formula (DI-16) is shown below.

[化99] [化99]

式(DI-16-1)~式(DI-16-12)中，R⁴⁰為-H或碳數1~20的烷基，優選-H或碳數1~10的烷基，而且，R⁴¹為-H或碳數1~12的烷基。 In the formula (DI-16-1) to the formula (DI-16-12), R ⁴⁰ is -H or an alkyl group having 1 to 20 carbon atoms, preferably -H or an alkyl group having 1 to 10 carbon atoms, and R ⁴¹ is -H or an alkyl group having 1 to 12 carbon atoms.

以下表示由式(DI-17)所表示的化合物的例子。 An example of the compound represented by the formula (DI-17) is shown below.

式(DI-17-1)~式(DI-17-3)中，R³⁷為碳數6~30的烷基，R⁴¹為-H或碳數1~12的烷基。 In the formula (DI-17-1) to the formula (DI-17-3), R ³⁷ is an alkyl group having 6 to 30 carbon atoms, and R ⁴¹ is -H or an alkyl group having 1 to 12 carbon atoms.

作為其他二胺，例如可使用由下述式(DI-18-1)~式(DI-18-13)所表示的化合物。 As the other diamine, for example, a compound represented by the following formula (DI-18-1) to formula (DI-18-13) can be used.

式(DI-18-1)~式(DI-18-8)中，R⁴²分別獨立地表示碳數3~30的烷基。 In the formula (DI-18-1) to the formula (DI-18-8), R ⁴² each independently represents an alkyl group having 3 to 30 carbon atoms.

[化102] [化102]

式(DI-18-9)~式(DI-18-11)中，e為2~10的整數，式(DI-18-12)中，R⁴³分別獨立為-H、-NHBoc或-N(Boc)₂，R⁴³的至少1個為-NHBoc或-N(Boc)₂，式(DI-18-13)中，R⁴⁴為-NHBoc或-N(Boc)₂，而且，m為1~12的整數。此處，Boc為第三丁氧基羰基。 In the formula (DI-18-9)~ (DI-18-11), e is an integer from 2 to 10. In the formula (DI-18-12), R ^{43 is} independently -H, -NHBoc or -N. (Boc) ₂ , at least one of R ⁴³ is -NHBoc or -N(Boc) ₂ , in the formula (DI-18-13), R ⁴⁴ is -NHBoc or -N(Boc) ₂ , and m is 1 An integer of ~12. Here, Boc is a third butoxycarbonyl group.

在使用本發明的液晶配向劑的液晶顯示元件需要大的預傾角的情況下，尤其當為了顯現2度以上的預傾角，而製造本發明的液晶配向劑中所使用的聚醯胺酸及其衍生物時，優選將側鏈型二胺在二胺總量中所占的比例設為5莫耳%~70莫耳%，更優選設為10莫耳%~50莫耳%。 In the case where a liquid crystal display element using the liquid crystal alignment agent of the present invention requires a large pretilt angle, particularly, in order to develop a pretilt angle of 2 degrees or more, the polylysine used in the liquid crystal alignment agent of the present invention and the like are produced. In the case of a derivative, the proportion of the side chain type diamine in the total amount of the diamine is preferably from 5 mol% to 70 mol%, more preferably from 10 mol% to 50 mol%.

可使用二醯肼作為用於製造本發明的聚醯胺酸或其衍生物的二胺。對所使用的二醯肼進行說明。本發明中所使用的二醯肼可無限制地從公知的二醯肼中選擇。 Dioxime can be used as the diamine for producing the poly-proline or its derivative of the present invention. Explain the two used. The diterpenes used in the present invention can be selected from known diterpenes without limitation.

作為此種二醯肼的適宜的例子，就原料獲得的容易性、或聚合物聚合時的容易性、膜的電特性的觀點而言，可列舉由式(2-a)~式(2-c)所表示的二醯肼。 As a suitable example of such a diterpene, from the viewpoints of easiness of obtaining a raw material, easiness in polymerization of a polymer, and electrical properties of a film, examples (2-a) to (2- c) the two indicated.

式(2-a)中，G為單鍵、碳數1~20的伸烷基、-CO-、-O-、-S-、-SO₂-、-C(CH₃)₂-、或-C(CF₃)₂-；式(2-b)中，環B為環己烷環、苯環或萘環，該基的任意的氫可由甲基、乙基、或苯基取代；式(2-c)中，環C分別獨立為環己烷環、或苯環，該基的任意的氫可由甲基、乙基、或苯基取代；Y為單鍵、碳數1~20的伸烷基、-CO-、-O-、-S-、-SO₂-、-C(CH₃)₂-、或-C(CF₃)₂-。 In the formula (2-a), G is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; in the formula (2-b), the ring B is a cyclohexane ring, a benzene ring or a naphthalene ring, and any hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group; In (2-c), ring C is independently a cyclohexane ring or a benzene ring, and any hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group; Y is a single bond and has a carbon number of 1 to 20 Alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -.

更詳細而言，可列舉由下述式(2-a-1)~式(2-a-2)、式(2-b-1)~式(2-b-3)或式(2-c-1)~式(2-c-6)所表示的二醯肼。 More specifically, the following formula (2-a-1) to formula (2-a-2), formula (2-b-1) to formula (2-b-3) or formula (2- C-1)~ The diterpene represented by the formula (2-c-6).

[化104] [化104]

當將本發明的液晶配向劑用作光配向用液晶配向劑時，在構成聚醯胺酸或其衍生物的二胺中，必須使用由下述式(DI-19-1)~式(DI-19-9)所表示的感光性二胺。 When the liquid crystal alignment agent of the present invention is used as a liquid crystal alignment agent for photoalignment, it is necessary to use the following formula (DI-19-1) to formula (DI) in the diamine constituting polyglycine or a derivative thereof. -19-9) The photosensitive diamine represented.

[化105] [化105]

所述二胺的具體例之中，在重視進一步提升液晶的配向性的情況下，二胺優選由以下的式(DI-4-1)、式(DI-4-12)~式(DI-4-14)、式(DI-5-1)、式(DI-5-5)、式(DI-5-9)、式(DI-5-12)、式(DI-5-13)、式(DI-5-22)、式(DI-5-28)、式(DI-5-30)、式(DI-7-3)、式(DI-9-1)、式(DI-13-4)、式(DI-13-5)、式(DI-13-47)、式(DI-16-1)、式(DI-16-2)或式(DI-16-4)所表示的二胺。或者，更優選由式(DI-4-1)、式(DI-5-1)、式(DI-5-5)、式(DI-5-9)、式(DI-5-12)、式(DI-5-13)、式(DI-5-22)、式(DI-7-3)及式(DI-9-1)所表示的二胺。 In the specific example of the diamine, when it is important to further improve the alignment of the liquid crystal, the diamine is preferably represented by the following formula (DI-4-1), formula (DI-4-12)-form (DI- 4-14), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), Formula (DI-5-22), formula (DI-5-28), formula (DI-5-30), formula (DI-7-3), formula (DI-9-1), formula (DI-13 -4), expressed by formula (DI-13-5), formula (DI-13-47), formula (DI-16-1), formula (DI-16-2) or formula (DI-16-4) Diamine. Alternatively, it is more preferable to have the formula (DI-4-1), the formula (DI-5-1), the formula (DI-5-5), the formula (DI-5-9), the formula (DI-5-12), A diamine represented by the formula (DI-5-13), the formula (DI-5-22), the formula (DI-7-3), and the formula (DI-9-1).

在重視提升液晶顯示元件的透過率的情況下，所述二胺之中，特優選由式(DI-1-1)~式(DI-1-4)、式(2-a-1)及式(2-a-2) 所表示的化合物。 When it is important to increase the transmittance of the liquid crystal display element, among the diamines, it is particularly preferable to use the formula (DI-1-1) to the formula (DI-1-4), the formula (2-a-1), and Formula (2-a-2) The compound represented.

在重視提升液晶顯示元件的感光性的情況下，所述感光性二胺之中，優選由式(DI-19-1)-式(DI-19-9)所表示的二胺。或者，更優選由式(DI-19-1)所表示的二胺。 When it is important to improve the photosensitivity of the liquid crystal display element, among the photosensitive diamines, a diamine represented by the formula (DI-19-1)-formula (DI-19-9) is preferable. Alternatively, the diamine represented by the formula (DI-19-1) is more preferable.

在各二胺中，二胺也可以在相對於二胺的單胺的比率為40莫耳%以下的範圍內，將二胺的一部分取代成單胺。此種取代可引起生成聚醯胺酸時的聚合反應的終止，可抑制聚合反應的進一步的進行。因此，通過此種取代，可容易地控制所獲得的聚合物(聚醯胺酸或其衍生物)的分子量，例如可無損本發明的效果而改善液晶配向劑的塗布特性。只要無損本發明的效果，則被取代成單胺的二胺可以是一種，也可以是兩種以上。作為所述單胺，例如可列舉：苯胺、4-羥基苯胺、環己胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、正十一胺、正十二胺、正十三胺、正十四胺、正十五胺、正十六胺、正十七胺、正十八胺、及正二十胺。 In the diamine, the diamine may be substituted with a part of the diamine in a range of 40 mol% or less with respect to the monoamine of the diamine. Such substitution can cause termination of the polymerization reaction when polyamic acid is formed, and further progress of the polymerization reaction can be suppressed. Therefore, by such substitution, the molecular weight of the obtained polymer (polyglycine or a derivative thereof) can be easily controlled, and for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. The diamine substituted with a monoamine may be one type or two or more types as long as the effects of the present invention are not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and positive ten Monoamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-dodecylamine.

本發明的液晶配向劑中所使用的聚醯胺酸可通過使至少含有所述酸二酐(1)的酸二酐與二胺成分在溶劑中進行反應而獲得。在該合成反應中，除原料的選擇以外，無需特別的條件，可直接應用通常的聚醯胺酸合成中的條件。所使用的溶劑將後述。 The polyphthalic acid used in the liquid crystal alignment agent of the present invention can be obtained by reacting an acid dianhydride containing at least the acid dianhydride (1) with a diamine component in a solvent. In the synthesis reaction, conditions other than the usual polyamine synthesis can be directly applied, except for the selection of the raw materials, without special conditions. The solvent to be used will be described later.

本發明的液晶配向劑可進而含有聚醯胺酸或其衍生物以外的其他成分。其他成分可以是1種，也可以是2種以上。 The liquid crystal alignment agent of the present invention may further contain other components than polyglycine or a derivative thereof. The other components may be one type or two or more types.

本發明的聚醯胺酸或其衍生物可在其單體中進而含有單異氰酸酯化合物。通過在單體中含有單異氰酸酯化合物，所獲得的聚醯胺酸或其衍生物的末端得到修飾，分子量得到調節。通過使用該末端修飾型的聚醯胺酸或其衍生物，例如可無損本發明的效果而改善液晶配向劑的塗布特性。就所述觀點而言，相對於單體中的二胺及四羧酸二酐的總量，單體中的單異氰酸酯化合物的含量優選1莫耳%~10莫耳%。作為所述單異氰酸酯化合物，例如可列舉：異氰酸苯酯、及異氰酸萘酯。 The polyaminic acid or derivative thereof of the present invention may further contain a single in its monomer Isocyanate compound. By containing a monoisocyanate compound in the monomer, the terminal of the obtained polyaminic acid or its derivative is modified, and the molecular weight is adjusted. By using the terminal-modified polyglycine or a derivative thereof, for example, the coating properties of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. From this point of view, the content of the monoisocyanate compound in the monomer is preferably from 1 mol% to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

本發明的聚醯胺酸或其衍生物可與用於聚醯亞胺的膜的形成的公知的聚醯胺酸或其衍生物同樣地製造。四羧酸二酐的總添加量優選設為與二胺的總莫耳數大致等莫耳(莫耳比為0.9~1.1左右)。 The polyaminic acid or a derivative thereof of the present invention can be produced in the same manner as the known polyaminic acid or a derivative thereof for forming a film of polyimine. The total addition amount of the tetracarboxylic dianhydride is preferably set to be approximately equal to the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1).

本發明的聚醯胺酸或其衍生物的分子量以聚苯乙烯換算的重量平均分子量(Mw)計，優選10,000~500,000，更優選20,000~200,000。所述聚醯胺酸或其衍生物的分子量可由利用凝膠滲透色譜法(Gel Permeation Chromatography，GPC)法的測定來求出。 The molecular weight of the poly-proline or the derivative thereof of the present invention is preferably 10,000 to 500,000, more preferably 20,000 to 200,000, in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the polyaminic acid or its derivative can be determined by measurement by a gel permeation chromatography (GPC) method.

本發明的聚醯胺酸或其衍生物可通過如下方式來確認它的存在：利用紅外線(Infrared，IR)、核磁共振(Nuclear Magnetic Resonance，NMR)對使本發明的聚醯胺酸或其衍生物在大量的不良溶劑中沉澱而獲得的固體成分進行分析。另外，可通過如下方式來確認所使用的單體：利用氣相色譜法(Gas Chromatography，GC)、高效液相色譜法(High Performance Liquid Chromatography，HPLC)或氣相色譜質譜法(Gas Chromatography-Mass Spectrometry，GC-MS)對使用KOH或NaOH等強鹼的水溶液將所述聚醯胺酸或其衍生物分解後，使用有機溶劑從其分解物中所萃取出的萃取物進行分析。 The poly-proline or a derivative thereof of the present invention can be confirmed by the following means: using poly Infrared (IR), Nuclear Magnetic Resonance (NMR) to make the polylysine of the present invention or its derivative The solid component obtained by precipitation in a large amount of poor solvent was analyzed. In addition, the monomer to be used can be confirmed by gas chromatography (GC), high performance liquid chromatography (HPLC) or gas chromatography mass spectrometry (Gas Chromatography-Mass). Spectrometry, GC-MS) Decomposes the poly-proline or a derivative thereof using an aqueous solution of a strong base such as KOH or NaOH, and then extracts the extract extracted from the decomposition product using an organic solvent.

<烯基取代納迪克醯亞胺化合物> <Alkenyl substituted nadic ylidene compound>

例如，就使液晶顯示元件的電特性長期穩定的目的而言，本發明的液晶配向劑可進而含有烯基取代納迪克醯亞胺化合物。烯基取代納迪克醯亞胺化合物可使用1種，也可以並用2種以上。就所述目的而言，相對於聚醯胺酸或其衍生物，烯基取代納迪克醯亞胺化合物的含量優選1 wt%~100 wt%，更優選1 wt%~70 wt%，進而更優選1 wt%~50 wt%。 For example, in order to stabilize the electrical characteristics of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the present invention may further contain an alkenyl group substituted nadic ylidene imine compound. The alkenyl substituted nadic ylidene imine compound may be used alone or in combination of two or more. For the purpose described, the content of the alkenyl-substituted nadic ylidene compound is preferably from 1 wt% to 100 wt%, more preferably from 1 wt% to 70 wt%, and furthermore, relative to the poly-proline or its derivative. It is preferably 1 wt% to 50 wt%.

以下對納迪克醯亞胺化合物進行具體說明。 The Nadik imine compound is specifically described below.

烯基取代納迪克醯亞胺化合物優選可溶解在溶解本發明中所使用的聚醯胺酸或其衍生物的溶劑中的化合物。此種烯基取代納迪克醯亞胺化合物的例子可列舉由下述的式(NA)所表示的化合物。 The alkenyl-substituted nadicylimine compound is preferably a compound which is soluble in a solvent which dissolves the poly-proline or a derivative thereof used in the present invention. Examples of such an alkenyl-substituted nadicylimine compound include compounds represented by the following formula (NA).

式(NA)中，L¹及L²獨立為-H、碳數1~12的烷基、碳數3~6的烯基、碳數5~8的環烷基、芳基或苄基，n為1或2。 In the formula (NA), L ¹ and L ^{2 are} independently -H, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group or a benzyl group. n is 1 or 2.

式(NA)中，當n=1時，W為碳數1~12的烷基、碳數2~6的烯基、碳數5~8的環烷基、碳數6~12的芳基、苄基、由-Z¹-(O)_r-(Z²O)_k-Z³-H(此處，Z¹、Z²及Z³獨立為碳數2~6的伸烷基，r為0或1，而且，k為1~30的整數)所表示的基、由-(Z⁴)_r-B-Z⁵-H(此處，Z⁴及Z⁵獨立為碳數1~4的伸烷基或碳數5~8的伸環烷基，B為伸苯基，而且，r為0或1)所表示的基、由-B-T-B-H(此處，B為伸苯基，而且，T為-CH₂-、-C(CH₃)₂-、-O-、-CO-、-S-、或-SO₂-)所表示的基、或這些基的1個~3個-H由-OH取代的基。 In the formula (NA), when n=1, W is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms. , benzyl, from -Z ¹ -(O) _r -(Z ² O) _k -Z ³ -H (here, Z ¹ , Z ² and Z ^{3 are} independently an alkylene group having 2 to 6 carbon atoms, r The base represented by 0 or 1, and k is an integer from 1 to 30, consists of -(Z ⁴ ) _r -BZ ⁵ -H (here, Z ⁴ and Z ⁵ independently represent a carbon number of 1 to 4). An alkyl group or a cycloalkyl group having 5 to 8 carbon atoms, B is a phenyl group, and r is a group represented by 0 or 1), and is represented by -BTBH (wherein B is a stretching phenyl group, and T is a group represented by -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, or -SO ₂ -), or 1 to 3 -H of these groups consisting of - OH substituted group.

此時，優選的W為碳數1~8的烷基、碳數3~4的烯基、環己基、苯基、苄基、碳數4~10的聚(乙烯氧基)乙基、苯氧基苯基、苯基甲基苯基、苯基異亞丙基苯基、及這些基的1個或2個-H由-OH取代的基。 In this case, preferred W is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, a poly(ethyleneoxy)ethyl group having 4 to 10 carbon atoms, and benzene. An oxyphenyl group, a phenylmethylphenyl group, a phenylisopropylidenephenyl group, and a group in which one or two -H of these groups are substituted by -OH.

式(NA)中，當n=2時，W為碳數2~20的伸烷基、碳數5~8的伸環烷基、碳數6~12的伸芳基、由-Z¹-O-(Z²O)_k-Z³-(此處，Z¹~Z³、及k的含義如上所述)所表示的基、由-Z⁴-B-Z⁵-(此處，Z⁴、Z⁵及B的含義如上所述)所表示的基、由-B-(O-B)_r-T-(B-O)_r-B-(此處，B為伸苯基，T為碳數1~3的伸烷基、-O-或-SO₂-，r的含義如上所述)所表示的基、或這些基的1個~3個-H由-OH取代的基。 In the formula (NA), when n=2, W is an alkylene group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, and -Z ¹ - a group represented by O-(Z ² O) _k -Z ³ - (here, Z ¹ -Z ³ , and k have the meanings as described above), consisting of -Z ⁴ -BZ ⁵ - (here, Z ⁴ , The meaning of Z ⁵ and B is as defined above. The group represented by -B-(OB) _r -T-(BO) _r -B- (here, B is a phenyl group and T is a carbon number of 1-3). The alkyl group, -O- or -SO ₂ -, r has the meaning indicated above, or a group of one to three -H of these groups substituted by -OH.

此時，優選的W為碳數2~12的伸烷基、伸環己基、伸苯基、伸甲苯基(tolylene)、苯二甲基、由-C₃H₆-O-(Z²-O)_n-O-C₃H₆- (此處，Z²為碳數2~6的伸烷基，n為1或2)所表示的基、由-B-T-B-(此處，B為伸苯基，而且，T為-CH₂-、-O-或-SO₂-)所表示的基、由-B-O-B-C₃H₆-B-O-B-(此處，B為伸苯基)所表示的基、及這些基的1個或2個-H由-OH取代的基。 In this case, preferred W is an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, a phenyl group, a tolylene group, a benzene dimethyl group, and a -C ₃ H ₆ -O-(Z ² - O) _n -OC ₃ H ₆ - (wherein Z ² is an alkylene group having 2 to 6 carbon atoms, and n is 1 or 2), represented by -BTB- (here, B is a phenylene group) Further, T is a group represented by -CH ₂ -, -O- or -SO ₂ -), a group represented by -BOBC ₃ H ₆ -BOB- (here, B is a stretching phenyl group), and these One or two -H groups substituted by -OH.

此種烯基取代納迪克醯亞胺化合物可使用例如如日本專利第2729565號公報中所記載般，通過將烯基取代納迪克酸酐衍生物與二胺在80℃~220℃的溫度下保持0.5小時~20小時來進行合成而獲得的化合物、或市售的化合物。作為烯基取代納迪克醯亞胺化合物的具體例，可列舉以下所示的化合物。 Such an alkenyl-substituted nadicylimine compound can be maintained at a temperature of from 80 ° C to 220 ° C by using an alkenyl-substituted nadic anhydride anhydride derivative and a diamine as described in, for example, Japanese Patent No. 2729565. A compound obtained by synthesis or a commercially available compound in an hour to 20 hours. Specific examples of the alkenyl-substituted nadicylimine compound include the compounds shown below.

N-甲基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-甲基-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-乙基己基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-乙基己基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-烯丙基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-異丙烯基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-異丙烯基-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-異丙烯基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-環己基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-環己基-烯丙基(甲基) 雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-環己基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苯基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苯基-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苄基-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苄基-烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-苄基-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-羥乙基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-羥乙基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2-羥乙基)-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2,2-二甲基-3-羥丙基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2,2-二甲基-3-羥丙基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2,3-二羥丙基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(2,3-二羥丙基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(3-羥基-1-丙烯基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-羥基環己基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-羥苯基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-羥苯基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-羥苯基)-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(4-羥苯基)-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(3-羥苯基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(3-羥苯基)-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(對羥基苄基)-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{2-(2-羥基乙氧基)乙基}-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{2-(2-羥基乙氧基)乙基}-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{2-(2-羥基乙氧基)乙基}-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{2-(2-羥基乙氧基)乙基}-甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-[2-{2-(2-羥基乙氧基)乙氧基}乙基]-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-[2-{2-(2-羥基乙氧基)乙氧基}乙基]-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-[2-{2-(2-羥基乙氧基)乙氧基}乙基]-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{4-(4-羥苯基異亞丙基)苯基}-烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{4-(4-羥苯基異亞丙基)苯基}-烯丙基(甲基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-{4-(4-羥苯基異亞丙基)苯基}-甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、及這些的寡聚物、N,N'-伸乙基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸乙基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸乙基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-三亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3- 二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸環己基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸環己基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、1,2-雙{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}乙烷、1,2-雙{3'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}乙烷、1,2-雙{3'-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}乙烷、雙[2'-{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}乙基]醚、雙[2'-{3'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}乙基]醚、1,4-雙{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}丁烷、1,4-雙{3'-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}丁烷、N,N'-對伸苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對伸苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間伸苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間伸苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-{(1-甲基)-2,4-伸苯基}-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙 (烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、2,2-雙[4-{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸、1,6-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-3-羥基-己烷、1,12-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-3,6-二羥基-十二烷、1,3-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-5-羥基-環己烷、1,5-雙{3'-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)丙氧基}-3-羥基-戊烷、1,4-雙(烯丙基雙環[2.2.1] 庚-5-烯-2,3-二羧基醯亞胺)-2-羥基-苯、1,4-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-2,5-二羥基-苯、N,N'-對(2-羥基)苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對(2-羥基)苯二甲基-雙(烯丙基甲基環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間(2-羥基)苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間(2-羥基)苯二甲基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對(2,3-二羥基)苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、2,2-雙[4-{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-2-羥基-苯氧基}苯基]丙烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-2-羥基-苯基}甲烷、雙{3-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-4-羥基-苯基}醚、雙{3-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)-5-羥基-苯基}碸、1,1,1-三{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)}苯氧基甲基丙烷、N,N',N"-三(乙烯甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)異三聚氰酸酯、及這些的寡聚物等。 N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-methyl-allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-methyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-methyl-A Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(2-ethylhexyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine, N-allyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-allyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N -Isopropenyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-isopropenyl-allyl (methyl)bicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine, N-isopropenyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N- Cyclohexyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allyl (methyl) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl Yttrium, N-phenyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-phenyl-allyl (methyl) bicyclo [2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N- Benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-benzyl-methylallylbicyclo[2.2.1]hept-5- Ace-2,3-dicarboxy quinone imine, N-(2-hydroxyethyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-( 2-hydroxyethyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-hydroxyethyl)-methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2,2-dimethyl-3-hydroxypropyl)-allylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-(2,2-dimethyl-3-hydroxypropyl)-allyl (methyl)bicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(2,3-dihydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine , N-(2,3-dihydroxypropyl)-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-(4-hydroxycyclohexyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine , N-(4-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(4-hydroxyphenyl)-allyl ( Methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-hydroxyphenyl)-methylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-(4-hydroxyphenyl)-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine , N-(3-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine, N-(3-hydroxyphenyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(p-hydroxybenzyl)- Allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-allyl bicyclo [2.2.1 Gh-5-ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-allyl (methyl)bicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-methylallylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-methylallylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, N-{4-(4-hydroxyphenyl isopropylidene)phenyl}-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine , N-{4-(4-hydroxyphenylisopropylene)phenyl}- Propyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-{4-(4-hydroxyphenylisopropylidene)phenyl}-methyl Allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, and oligomers thereof, N, N'-extended ethyl-bis (allyl bicyclo [2.2. 1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-extended ethyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3 -dicarboxy quinone imine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N '-Trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-bis(allyl bicyclol) [2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene -2,3- Dicarboxy quinone imine), N,N'-docamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N' - Dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-cyclohexylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine), 1,2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) propoxy Ethyl, 1,2-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethane, 1 ,2-double {3'-(methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)propoxy}ethane, bis[2'-{3 '-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, bis[2'-{3'-(allyl) Methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) propoxy} ethyl] ether, 1,4-double {3'-(allyl bicyclo [2.2. 1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}butane, 1,4-bis{3'-(allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine) propoxy}butane, N, N'- Phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide), N,N'-p-phenylene-bis(allylmethylbicyclic) [2.2.1]Hept-5-ene-2,3-dicarboxyindenine), N,N'-meta-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine), N, N'-meta-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-xylylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-m-xylylene-double (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindole Imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine Phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}methane, double {4-( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine) phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}ether, double {4-(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)phenyl}ether, bis{4-(methylallylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxyfluorene Amine) phenyl}ether, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}indole, double {4-(allyl Methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} fluorene, bis {4-(methylallyl bicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine) phenyl} fluorene, 1,6-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)-3- Hydroxy-hexane, 1,12-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)-3,6-dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)-5-hydroxy-cyclohexane, 1,5-bis{3'-( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) propoxy}-3-hydroxy-pentane, 1,4-bis(allyl bicyclo [2.2. 1] Hg-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-benzene, 1,4-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinoid imine)-2,5-dihydroxy-benzene, N,N'-p-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-p-(2-hydroxy)benzenedimethyl-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N' -p-(2,3-dihydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 2,2-bis[4 -{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-phenoxy}phenyl]propane, bis{4-(ene Propylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-phenyl}methane, bis{3-(allylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxyindolimine)-4-hydroxy-phenyl}ether, bis{3-(methylallylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine)-5-hydroxy-phenyl}indole, 1,1,1- {4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide)}phenoxymethylpropane, N,N',N"-tris(ethylene Methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinimine) isomeric cyanurate, oligomers of these, and the like.

進而，本發明中所使用的烯基取代納迪克醯亞胺化合物可為含有非對稱的伸烷基．伸苯基的由下述式所表示的化合物。 Further, the alkenyl-substituted nadicylimine compound used in the present invention may be an asymmetric alkyl group. A compound represented by the following formula which is a phenyl group.

[化107] [107]

以下表示烯基取代納迪克醯亞胺化合物中的優選的化合物。 Preferred compounds among the alkenyl substituted nadic quinone imine compounds are shown below.

N,N'-伸乙基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸乙基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸乙基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-三亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基雙環[2.2.1] 庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸環己基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸環己基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對伸苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對伸苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間伸苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間伸苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-{(1-甲基)-2,4-伸苯基}-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、2,2-雙[4-{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷。 N,N'-Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-extended ethyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindenine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxyindenine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine), N, N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-pair Phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide), N,N'-p-phenylene-bis(allylmethylbicyclo[ 2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N,N'-meta-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine), N,N'-meta-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N , N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N , N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-p-xylylene-double (allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-xylylene-bis(allylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine), 2,2-bis[4-{4-(allyl double [2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine) phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane.

雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}醚、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}碸。 Double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}methane, bis{4-(methylallylmethylbicyclo) [2.2.1]hept-5-ene-2,3-dicarboxyinimide)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy hydrazine Imine)phenyl}ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenimido)phenyl}ether, double {4-( Methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} ether, bis {4-(allylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine) phenyl} fluorene, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) benzene Base 碸, bis {4-(methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) phenyl} fluorene.

以下表示更優選的烯基取代納迪克醯亞胺化合物。 More preferred alkenyl substituted nadic quinone imine compounds are shown below.

N,N'-伸乙基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸乙基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸乙基-雙(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-三亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-六亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-十二亞甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸環己基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-伸環己基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)。 N,N'-Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-extended ethyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N '-Extended cyclohexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinylimine).

N,N'-對伸苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對伸苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間伸苯基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間伸苯基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯 -2,3-二羧基醯亞胺)、N,N'-{(1-甲基)-2,4-伸苯基}-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-對苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、N,N'-間苯二甲基-雙(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)。 N,N'-p-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene-bis( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-meta-phenyl-bis(allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine), N,N'-meta-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinoid imine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) , N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-m-phenylene Methyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-m-xylylene-bis(allylmethylbicyclo) [2.2.1] Hept-5-ene-2,3-dicarboxyinlimine).

2,2-雙[4-{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、2,2-雙[4-{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯氧基}苯基]丙烷、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、雙{4-(甲基烯丙基甲基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷。 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2- Bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-dual [ 4-{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, double {4-(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane , bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}methane.

而且，作為特優選的烯基取代納迪克醯亞胺化合物，可列舉：由下述式(NA-1)所表示的雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、由式(NA-2)所表示的N,N'-間苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、及由式(NA-3)所表示的N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)。 Further, as a particularly preferred alkenyl-substituted nadicylimine compound, a bis{4-(allylbicyclo[2.2.1]hept-5-ene represented by the following formula (NA-1) is exemplified. -2,3-dicarboxy quinhomine)phenyl}methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]heptane represented by formula (NA-2) 5-ene-2,3-dicarboxy quinimine), and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5 represented by formula (NA-3) -ene-2,3-dicarboxy quinone imine).

[化108] [化108]

<具有自由基聚合性不飽和雙鍵的化合物> <Compound having a radical polymerizable unsaturated double bond>

例如，就使液晶顯示元件的電特性長期穩定的目的而言，本發明的液晶配向劑可進而含有具有自由基聚合性不飽和雙鍵的化合物。具有自由基聚合性不飽和雙鍵的化合物可以是一種化合物，也可以是兩種以上的化合物。再者，在具有自由基聚合性不飽和雙鍵的化合物中不含烯基取代納迪克醯亞胺化合物。就所述目的而言，相對於聚醯胺酸或其衍生物，具有自由基聚合性不飽和雙鍵的化合物的含量優選1 wt%~100 wt%，更優選1 wt%~70 wt%，進而更優選1 wt%~50 wt%。 For example, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The compound having a radical polymerizable unsaturated double bond may be one kind of compound or two or more types of compounds. Further, an alkenyl-substituted nadic quinone imine compound is not contained in the compound having a radical polymerizable unsaturated double bond. For the purpose, the content of the compound having a radical polymerizable unsaturated double bond is preferably from 1% by weight to 100% by weight, more preferably from 1% by weight to 70% by weight, based on the polyphthalic acid or a derivative thereof. More preferably, it is 1 wt% to 50 wt%.

再者，關於相對於烯基取代納迪克醯亞胺化合物的具有自由基聚合性不飽和雙鍵的化合物的比率，為了降低液晶顯示元件的離子密度、抑制離子密度的經時的增加、進而抑制殘像的產生，具有自由基聚合性不飽和雙鍵的化合物/烯基取代納迪克醯亞胺化合物以重量比計優選0.1~10，更優選0.5~5。 In addition, the ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl substituted imidide compound is reduced in order to reduce the ion density of the liquid crystal display element, suppress the increase in the ion density over time, and further suppress Residual image generation, compound with a radical polymerizable unsaturated double bond/alkenyl substituted Nadik The amine compound is preferably from 0.1 to 10, more preferably from 0.5 to 5, by weight.

以下對具有自由基聚合性不飽和雙鍵的化合物進行具體說明。 The compound having a radical polymerizable unsaturated double bond will be specifically described below.

作為具有自由基聚合性不飽和雙鍵的化合物，可列舉：(甲基)丙烯酸酯、(甲基)丙烯醯胺等(甲基)丙烯酸衍生物、及雙順丁烯二醯亞胺。具有自由基聚合性不飽和雙鍵的化合物更優選具有2個以上的自由基聚合性不飽和雙鍵的(甲基)丙烯酸衍生物。 Examples of the compound having a radically polymerizable unsaturated double bond include a (meth)acrylic acid ester, a (meth)acrylic acid derivative such as (meth)acrylamide, and a bis-synylene diimide. The compound having a radical polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

作為(甲基)丙烯酸酯的具體例，例如可列舉：(甲基)丙烯酸環己酯、(甲基)丙烯酸-2-甲基環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸-2-羥基乙酯、及(甲基)丙烯酸-2-羥基丙酯。 Specific examples of the (meth) acrylate include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Dicyclopentyloxyethyl acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl methacrylate.

作為二官能(甲基)丙烯酸酯的具體例，例如可列舉：伸乙基雙丙烯酸酯，作為東亞合成化學工業(股份)的產品的Aronix M-210、Aronix M-240及Aronix M-6200，作為日本化藥(股份)的產品的KAYARAD HDDA、KAYARAD HX-220、KAYARAD R-604及KAYARAD R-684，作為大阪有機化學工業(股份)的產品的V260、V312及V335HP，以及作為共榮社油脂化學工業(股份)的產品的Light Acrylate BA-4EA、Light Acrylate BP-4PA及Light Acrylate BP-2PA。 Specific examples of the difunctional (meth) acrylate include, for example, exoethyl diacrylate, Aronix M-210, Aronix M-240, and Aronix M-6200, which are products of the East Asian synthetic chemical industry. KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604, and KAYARAD R-684, which are products of Nippon Kayaku (share), V260, V312, and V335HP, which are products of Osaka Organic Chemical Industry Co., Ltd., and Co., Ltd. Light Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA for the Grease Chemical Industry (shares) products.

作為三官能以上的多官能(甲基)丙烯酸酯的具體例，例如可列舉：4,4’-亞甲基雙(N,N-二羥基伸乙基丙烯酸酯苯胺)，作為東亞合成化學工業(股份)的產品的Aronix M-400、Aronix M-405、Aronix M-450、Aronix M-7100、Aronix M-8030、Aronix M-8060，作為日本化藥(股份)的產品的KAYARAD TMPTA、KAYARAD DPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60、KAYARAD DPCA-120，及作為大阪有機化學工業(股份)的產品的VGPT。 Specific examples of the trifunctional or higher polyfunctional (meth) acrylate include, for example, 4,4'-methylenebis(N,N-dihydroxyethylidene anilide). Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, products of the East Asian Synthetic Chemical Industry (share), as products of Nippon Chemical Co., Ltd. KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and VGPT as a product of Osaka Organic Chemical Industry Co., Ltd.

作為(甲基)丙烯醯胺衍生物的具體例，例如可列舉：N-異丙基丙烯醯胺、N-異丙基甲基丙烯醯胺、N-正丙基丙烯醯胺、N-正丙基甲基丙烯醯胺、N-環丙基丙烯醯胺、N-環丙基甲基丙烯醯胺、N-乙氧基乙基丙烯醯胺、N-乙氧基乙基甲基丙烯醯胺、N-四氫糠基丙烯醯胺、N-四氫糠基甲基丙烯醯胺、N-乙基丙烯醯胺、N-乙基-N-甲基丙烯醯胺、N,N-二乙基丙烯醯胺、N-甲基-N-正丙基丙烯醯胺、N-甲基-N-異丙基丙烯醯胺、N-丙烯醯基呱啶、N-丙烯醯基吡咯烷、N,N'-亞甲基雙丙烯醯胺、N,N,-伸乙基雙丙烯醯胺、N,N’-二羥基伸乙基雙丙烯醯胺、N-(4-羥苯基)甲基丙烯醯胺、N-苯基甲基丙烯醯胺、N-丁基甲基丙烯醯胺、N-(異丁氧基甲基)甲基丙烯醯胺、N-[2-(N,N-二甲胺基)乙基]甲基丙烯醯胺、N,N-二甲基甲基丙烯醯胺、N-[3-(二甲胺基)丙基]甲基丙烯醯胺、N-(甲氧基甲基)甲基丙烯醯胺、N-(羥甲基)-2-甲基丙烯醯胺、N-苄基-2-甲基丙烯醯胺，及N,N'-亞甲基雙甲基丙烯醯胺。 Specific examples of the (meth) acrylamide derivative include N-isopropyl acrylamide, N-isopropyl methacrylamide, N-n-propyl acrylamide, and N-positive Propyl methacrylamide, N-cyclopropyl acrylamide, N-cyclopropyl methacrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl methacrylate Amine, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N, N-di Ethyl acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-propenyl acridine, N-propenylpyrrolidine, N,N'-methylenebis propylene amide, N,N,-extended ethyl bis acrylamide, N,N'-dihydroxyethylidene bis decylamine, N-(4-hydroxyphenyl) Methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N-(isobutoxymethyl)methacrylamide, N-[2-(N,N- Dimethylamino)ethyl]methacrylamide, N,N-dimethylmethacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-( Methoxymethyl)methacrylamide, N-(hydroxyl Methyl)-2-methylpropenylamine, N-benzyl-2-methylpropenylamine, and N,N'-methylenebismethacrylamide.

所述(甲基)丙烯酸衍生物之中，特優選N,N'-亞甲基雙丙烯醯胺、N,N'-二羥基伸乙基-雙丙烯醯胺、伸乙基雙丙烯酸酯、及4,4’-亞甲基雙(N,N-二羥基伸乙基丙烯酸酯苯胺)。 Among the (meth)acrylic acid derivatives, N,N'-methylenebisacrylamide, N,N'-dihydroxyethylidene-bispropenylamine, ethylidene diacrylate, And 4,4'-methylenebis(N,N-dihydroxyethyl acrylate).

作為雙順丁烯二醯亞胺，例如可列舉：KI化成(KI Chemical Industry)(股份)製造的BMI-70及BMI-80，以及大和化成工業(股份)製造的BMI-1000、BMI-3000、BMI-4000、BMI-5000及BMI-7000。 Examples of the bis-s-butylene diimide include BMI-70 and BMI-80 manufactured by KI Chemical Industry Co., Ltd., and BMI-1000 and BMI-3000 manufactured by Daiwa Kasei Industrial Co., Ltd. , BMI-4000, BMI-5000 and BMI-7000.

<噁嗪化合物> <oxazine compound>

例如，就使液晶顯示元件的電特性長期穩定的目的而言，本發明的液晶配向劑可進而含有噁嗪化合物。噁嗪化合物可以是一種化合物，也可以是兩種以上的化合物。就所述目的而言，相對於聚醯胺酸或其衍生物，噁嗪化合物的含量優選0.1 wt%~50 wt%，更優選1 wt%~40 wt%，進而更優選1 wt%~20 wt%。 For example, the liquid crystal alignment agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The oxazine compound may be one compound or two or more compounds. For the purpose described, the content of the oxazine compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably from 1% by weight to 20%, based on the poly phthalic acid or a derivative thereof. Wt%.

以下對噁嗪化合物進行具體說明。 The oxazine compound will be specifically described below.

噁嗪化合物優選可溶於使聚醯胺酸或其衍生物溶解的溶劑中、且具有開環聚合性的噁嗪化合物。 The oxazine compound is preferably an oxazine compound which is soluble in a solvent which dissolves poly-proline or a derivative thereof and has ring-opening polymerizability.

另外，噁嗪化合物中的噁嗪結構的數量並無特別限定。 Further, the number of the oxazine structure in the oxazine compound is not particularly limited.

噁嗪的結構已知有各種結構。本發明中，噁嗪的結構並無特別限定，在噁嗪化合物中的噁嗪結構中，可列舉苯並噁嗪或萘並噁嗪等具有含有縮合多環芳香族基的芳香族基的噁嗪的結構。 The structure of the oxazine is known in various structures. In the present invention, the structure of the oxazine is not particularly limited, and examples of the oxazine structure in the oxazine compound include an aldehyde having a condensed polycyclic aromatic group such as benzoxazine or naphthoxazine. The structure of the azine.

作為噁嗪化合物，例如可列舉下述式(OX-1)~式(OX-6)所示的化合物。再者，在下述式中，朝向環的中心所表示的鍵表示結合在構成環且可結合取代基的任一個碳上。 Examples of the oxazine compound include compounds represented by the following formula (OX-1) to formula (OX-6). Further, in the following formula, the bond represented toward the center of the ring means that it is bonded to any of the carbons constituting the ring and capable of binding the substituent.

[化109] [化109]

式(OX-1)~式(OX-3)中，L³及L⁴為碳數1~30的有機基，式(OX-1)~式(OX-6)中，L⁵~L⁸為-H或碳數1~6的烴基，式(OX-3)、式(OX-4)及式(OX-6)中，Q¹為單鍵、-O-、-S-、-S-S-、-SO₂-、-CO-、-CONH-、-NHCO-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_v-、-O-(CH₂)_v-O-、-S-(CH₂)_v-S-，此處，v為1~6的整數，式(OX-5)及式(OX-6)中，Q²獨立為單鍵、-O-、-S-、-CO-、-C(CH₃)₂-、-C(CF₃)₂-或碳數1~3的伸烷基，Q²中的苯環、萘環上所結合的氫獨立且可由-F、-CH₃、-OH、-COOH、-SO₃H、-PO₃H₂取代。 In the formula (OX-1)~(OX-3), L ³ and L ⁴ are an organic group having 1 to 30 carbon atoms, and in the formula (OX-1) to (OX-6), L ⁵ to L ⁸ Is -H or a hydrocarbon group having 1 to 6 carbon atoms, and in the formula (OX-3), formula (OX-4) and formula (OX-6), Q ¹ is a single bond, -O-, -S-, -SS -, -SO ₂ -, -CO-, -CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _v -, -O-(CH ₂ ) _v -O-, -S-(CH ₂ ) _v -S-, where v is an integer from 1 to 6, in the formula (OX-5) and (OX-6), Q ^{2 is} independently a single a bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or an alkylene group having 1 to 3 carbon atoms, a benzene ring and naphthalene in Q ² bound hydrogen on the ring and may be independently _{-F, -CH 3, -OH, -COOH} , -SO 3 H, -PO 3 H 2 group.

另外，噁嗪化合物包括側鏈上具有噁嗪結構的寡聚物或聚合物、主鏈中具有噁嗪結構的寡聚物或聚合物。 Further, the oxazine compound includes an oligomer or polymer having an oxazine structure in a side chain, and an oligomer or polymer having an oxazine structure in the main chain.

作為由式(OX-1)所表示的噁嗪化合物，例如可列舉以下的噁嗪化合物。 As the oxazine compound represented by the formula (OX-1), for example, The underlying oxazine compound.

式(OX-1-2)中，L³優選碳數1~30的烷基，更優選碳數1~20的烷基。 In the formula (OX-1-2), L ³ is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

作為由式(OX-2)所表示的噁嗪化合物，例如可列舉以下的噁嗪化合物。 Examples of the oxazine compound represented by the formula (OX-2) include the following oxazine compounds.

式中，L³優選碳數1~30的烷基，更優選碳數1~20的烷基。 In the formula, L ³ is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms.

作為由式(OX-3)所表示的噁嗪化合物，可列舉由下述式(OX-3-I)所表示的噁嗪化合物。 The oxazine compound represented by the formula (OX-3) includes an oxazine compound represented by the following formula (OX-3-I).

式(OX-3-I)中，L³及L⁴為碳數1~30的有機基，L⁵~ L⁸為-H或碳數1~6的烴基，Q¹為單鍵、-CH₂-、-C(CH₃)₂-、-CO-、-O-、-SO₂-、-C(CH₃)₂-、或-C(CF₃)₂-。作為由式(OX-3-I)所表示的噁嗪化合物，例如可列舉以下的噁嗪化合物。 In the formula (OX-3-I), L ³ and L ⁴ are an organic group having 1 to 30 carbon atoms, L ⁵ to L ⁸ are -H or a hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ is a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -O-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -. Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

[化116] [116]

式中，L³及L⁴優選碳數1~30的烷基，更優選碳數1~20的烷基。 In the formula, L ³ and L ^{4 are} preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

作為由式(OX-4)所表示的噁嗪化合物，例如可列舉以下的噁嗪化合物。 Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.

作為由式(OX-5)所表示的噁嗪化合物，例如可列舉以下的噁嗪化合物。 Examples of the oxazine compound represented by the formula (OX-5) include the following oxazine compounds.

[化120] [化120]

作為由式(OX-6)所表示的噁嗪化合物，例如可列舉以下的噁嗪化合物。 Examples of the oxazine compound represented by the formula (OX-6) include the following oxazine compounds.

[化122] [化122]

這些噁嗪化合物之中，更優選可列舉由式(OX-2-1)、式(OX-3-1)、式(OX-3-3)、式(OX-3-5)、式(OX-3-7)、式(OX-3-9)、式(OX-4-1)~式(OX-4-6)、式(OX-5-3)、式(OX-5-4)、及式(OX-6-2)~式(OX-6-4)所表示的噁嗪化合物。 Among these oxazine compounds, more preferably, it is a formula (OX-2-1), a formula (OX-3-1), a formula (OX-3-3), a formula (OX-3-5), and a formula ((OX-3-5)) OX-3-7), formula (OX-3-9), formula (OX-4-1)~form (OX-4-6), formula (OX-5-3), formula (OX-5-4 And an oxazine compound represented by the formula (OX-6-2)~(OX-6-4).

噁嗪化合物可通過與國際公開2004/009708號手冊、日本專利特開平11-12258號公報、日本專利特開2004-352670號公報中所記載的方法相同的方法來製造。 Oxazine compounds can be used in the International Publication No. 2004/009708 manual, Japan It is produced by the same method as the method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2004-352670.

由式(OX-1)所表示的噁嗪化合物可通過使酚化合物與一級胺及醛進行反應而獲得(參照國際公開2004/009708號手冊)。 The oxazine compound represented by the formula (OX-1) can be obtained by reacting a phenol compound with a primary amine and an aldehyde (refer to International Publication No. 2004/009708).

由式(OX-2)所表示的噁嗪化合物可通過如下方式獲得：通過向甲醛中緩慢地添加一級胺的方法進行反應後，添加具有萘酚系羥基的化合物進行反應(參照國際公開2004/009708號手冊)。 The oxazine compound represented by the formula (OX-2) can be obtained by reacting a compound having a naphthol-based hydroxyl group by a method in which a primary amine is slowly added to formaldehyde, and reacting (refer to International Publication 2004/ Manual 009708).

由式(OX-3)所表示的噁嗪化合物可通過如下方式獲得：在二級脂肪族胺、三級脂肪族胺或鹼性含氮雜環化合物的存在下，使酚化合物1莫耳、相對於該酚化合物的1個酚性羥基至少為2莫耳以上的醛、以及1莫耳的一級胺在有機溶劑中進行反應(參照國際公開2004/009708號手冊及日本專利特開平11-12258號公報)。 The oxazine compound represented by the formula (OX-3) can be obtained by subjecting the phenol compound to 1 mol in the presence of a secondary aliphatic amine, a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound. An aldehyde having at least 2 mA or more of a phenolic hydroxyl group of the phenol compound and 1 mol of a primary amine are reacted in an organic solvent (refer to International Publication No. 2004/009708, and Japanese Patent Laid-Open No. 11-12258 Bulletin).

由式(OX-4)~式(OX-6)所表示的噁嗪化合物可通過如下方式獲得：在90℃以上的溫度下，使4,4'-二胺基二苯基甲烷等具有多個苯環及與這些苯環結合的有機基的二胺、甲醛等醛、以及苯酚在正丁醇中進行脫水縮合反應(參照日本專利特開2004-352670號公報)。 The oxazine compound represented by the formula (OX-4) to the formula (OX-6) can be obtained by having 4,4'-diaminodiphenylmethane or the like at a temperature of 90 ° C or higher. A benzene ring, an organic group-containing diamine bonded to the benzene ring, an aldehyde such as formaldehyde, and a phenol are subjected to a dehydration condensation reaction in n-butanol (refer to Japanese Laid-Open Patent Publication No. 2004-352670).

<噁唑啉化合物> <oxazoline compound>

例如，就使液晶顯示元件的電特性長期穩定的目的而言，本發明的液晶配向劑可進而含有噁唑啉化合物。噁唑啉化合物為具有噁唑啉結構的化合物。噁唑啉化合物可以是一種化合物，也可以是兩種以上的化合物。就所述目的而言，相對於聚醯胺酸或其衍生物，噁唑啉化合物的含量優選0.1 wt%~50 wt%，更優選1 wt%~40 wt%，進而優選1 wt%~20 wt%。或者，當將噁唑啉化合物中的噁唑啉結構換算成噁唑啉時，就所述目的而言，相對於聚醯胺酸或其衍生物，噁唑啉化合物的含量優選0.1 wt%~40 wt%。 For example, the liquid crystal alignment agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The oxazoline compound is a compound having an oxazoline structure. An oxazoline compound can be a compound The substance may also be two or more kinds of compounds. For the purpose described, the content of the oxazoline compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably from 1% by weight to 20%, based on the poly phthalic acid or a derivative thereof. Wt%. Alternatively, when the oxazoline structure in the oxazoline compound is converted to an oxazoline, the content of the oxazoline compound is preferably 0.1 wt% with respect to the polyamine or its derivative. 40 wt%.

以下對噁唑啉化合物進行具體說明。 The oxazoline compound will be specifically described below.

噁唑啉化合物可在1種化合物中僅具有1種噁唑啉結構，也可以具有2種以上。另外，噁唑啉化合物只要在1種化合物中具有1個噁唑啉結構即可，但優選具有2個以上。另外，噁唑啉化合物可以是側鏈上具有噁唑啉環結構的聚合物，也可以是共聚物。側鏈上具有噁唑啉結構的聚合物可以是側鏈上具有噁唑啉結構的單體的均聚物，也可以是側鏈上具有噁唑啉結構的單體與不具有噁唑啉結構的單體的共聚物。側鏈上具有噁唑啉結構的共聚物可以是側鏈上具有噁唑啉結構的2種以上的單體的共聚物，也可以是側鏈上具有噁唑啉結構的2種以上的單體與不具有噁唑啉結構的單體的共聚物。 The oxazoline compound may have only one oxazoline structure in one type of compound, or may have two or more types. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more. Further, the oxazoline compound may be a polymer having an oxazoline ring structure in a side chain, or may be a copolymer. The polymer having an oxazoline structure on the side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or a monomer having an oxazoline structure in a side chain and having no oxazoline structure. Copolymer of monomer. The copolymer having an oxazoline structure in a side chain may be a copolymer of two or more kinds of monomers having an oxazoline structure in a side chain, or two or more kinds of monomers having an oxazoline structure in a side chain. Copolymer with a monomer having no oxazoline structure.

噁唑啉結構優選以噁唑啉結構中的氧及氮的一者或兩者與聚醯胺酸的羰基可進行反應的方式存在於噁唑啉化合物中的結構。 The oxazoline structure is preferably a structure which exists in the oxazoline compound in such a manner that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polyphthalic acid.

作為噁唑啉化合物，例如可列舉：2,2'-雙(2-噁唑啉)、1,2,4-三-(2-噁唑啉基-2)-苯、4-呋喃-2-基亞甲基-2-苯基-4H-噁唑-5-酮、 1,4-雙(4,5-二氫-2-噁唑基)苯、1,3-雙(4,5-二氫-2-噁唑基)苯、2,3-雙(4-異丙烯基-2-噁唑啉-2-基)丁烷、2,2'-雙-4-苄基-2-噁唑啉、2,6-雙(異丙基-2-噁唑啉-2-基)吡啶、2,2'-亞異丙基雙(4-第三丁基-2-噁唑啉)、2,2'-異亞丙基雙(4-苯基-2-噁唑啉)、2,2'-亞甲基雙(4-第三丁基-2-噁唑啉)、及2,2'-亞甲基雙(4-苯基-2-噁唑啉)。除這些噁唑啉化合物以外，也可以列舉如Epocros(商品名，日本觸媒(股份)製造)般的具有噁唑基的聚合物或寡聚物。這些噁唑啉化合物之中，更優選可列舉1,3-雙(4,5-二氫-2-噁唑基)苯。 Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, and 4-furan-2. - benzylidene-2-phenyl-4H-oxazol-5-one, 1,4-Bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 2,3-bis(4- Isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6-bis(isopropyl-2-oxazoline -2-yl)pyridine, 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2- Oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), and 2,2'-methylenebis(4-phenyl-2-oxazoline) ). In addition to these oxazoline compounds, a polymer or oligomer having an oxazolyl group such as Epocros (trade name, manufactured by Nippon Shokubai Co., Ltd.) may be mentioned. Among these oxazoline compounds, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is more preferable.

<環氧化合物> <epoxy compound>

例如，就使液晶顯示元件的電特性長期穩定的目的而言，本發明的液晶配向劑可進而含有環氧化合物。環氧化合物可以是一種化合物，也可以是兩種以上的化合物。就所述目的而言，相對於聚醯胺酸或其衍生物，環氧化合物的含量優選0.1 wt%~50 wt%，更優選1 wt%~40 wt%，進而更優選1 wt%~20 wt%。 For example, the liquid crystal alignment agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The epoxy compound may be one compound or two or more compounds. For the purpose, the content of the epoxy compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably from 1% by weight to 20%, based on the polyaminic acid or a derivative thereof. Wt%.

以下對環氧化合物進行具體說明。 The epoxy compound will be specifically described below.

作為環氧化合物，可列舉分子內具有1個或2個以上的環氧環的各種化合物。作為分子內具有1個環氧環的化合物，例如可列舉：苯基縮水甘油醚、丁基縮水甘油醚、3,3,3-三氟甲基環氧丙烷、氧化苯乙烯、六氟環氧丙烷、環氧環己烷、3-縮水甘油氧基丙基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、N-縮水甘油基鄰苯二甲醯亞胺、(九氟-N-丁基)環氧化物、全氟乙基縮水甘油醚、表氯醇、表溴醇、N,N-二縮水甘油基苯胺、及3-[2-(全氟己基)乙氧基]-1,2-環氧基丙烷。 Examples of the epoxy compound include various compounds having one or two or more epoxy rings in the molecule. Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, and hexafluoroepoxy. Propane, epoxycyclohexane, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-glycidylphthalate Yttrium, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N,N-diglycidyl aniline, And 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane.

作為分子內具有2個環氧環的化合物，例如可列舉：乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油二縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、3,4-環氧基環己烯基甲基-3',4'-環氧基環己烯羧酸酯及3-(N,N-二縮水甘油基)胺基丙基三甲氧基矽烷。 Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol dihydrate. Glycerol ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-ring Oxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and 3-(N,N-diglycidyl)aminopropyltrimethoxydecane.

作為分子內具有3個環氧環的化合物，例如可列舉：2-[4-(2,3-環氧基丙氧基)苯基]-2-[4-[1,1-雙[4-([2,3-環氧基丙氧基]苯基)]乙基]苯基]丙烷(商品名“Techmore VG3101L”，(三井化學(股份)製造))。 Examples of the compound having three epoxy rings in the molecule include 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4] -([2,3-Epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name "Techmore VG3101L", manufactured by Mitsui Chemicals, Inc.).

作為分子內具有4個環氧環的化合物，例如可列舉：1,3,5,6-四縮水甘油基-2,4-己二醇、N,N,N',N'-四縮水甘油基-間二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、及3-(N-烯丙基-N-縮水甘油基)胺基丙基三甲氧基矽烷。 Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl. Base-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4' -Diaminodiphenylmethane, and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane.

除所述以外，也可以列舉具有環氧環的寡聚物或聚合物作為分子內具有環氧環的化合物的例子。作為具有環氧環的單體，例如可列舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧基環己酯、及(甲基)丙烯酸甲基縮水甘油酯。 In addition to the above, an oligomer having an epoxy ring or a polymer may be exemplified as a compound having an epoxy ring in the molecule. Examples of the monomer having an epoxy ring include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate.

作為與具有環氧環的單體進行共聚的其他單體，例如可列舉：(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、苯乙烯、甲基苯乙烯、氯甲基苯乙烯、(甲基)丙烯酸(3-乙基-3-氧雜環丁基)甲酯、N-環己基順丁烯二醯亞胺及N-苯基順丁烯二醯亞胺。 Examples of the other monomer copolymerized with the monomer having an epoxy ring include (meth)acrylic acid, methyl (meth)acrylate, and ethyl (meth)acrylate. Isopropyl acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (meth)acrylic acid (3-ethyl-3- Oxehydrobutyl butyl) methyl ester, N-cyclohexyl maleimide and N-phenyl maleimide.

作為具有環氧環的單體的聚合物的優選的具體例，可列舉聚甲基丙烯酸縮水甘油酯等。另外，作為具有環氧環的單體與其他單體的共聚物的優選的具體例，可列舉：N-苯基順丁烯二醯亞胺-甲基丙烯酸縮水甘油酯共聚物、N-環己基順丁烯二醯亞胺-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸苄酯-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸丁酯-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸2-羥基乙酯-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸(3-乙基-3-氧雜環丁基)甲酯-甲基丙烯酸縮水甘油酯共聚物、及苯乙烯-甲基丙烯酸縮水甘油酯共聚物。 Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Further, preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenyl maleimide-glycidyl methacrylate copolymer and N-ring. Hexyl maleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, methyl 2-hydroxyethyl acrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and styrene-A Glycidyl acrylate copolymer.

這些例之中，特優選N,N,N',N'-四縮水甘油基-間二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、商品名“Techmore VG3101L”、3,4-環氧基環己烯基甲基-3',4'-環氧基環己烯羧酸酯、N-苯基順丁烯二醯亞胺-甲基丙烯酸縮水甘油酯共聚物、及2-(3,4-環氧基環己基)乙基三甲氧基矽烷。 Among these, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane is particularly preferred. , N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Techmore VG3101L", 3,4-epoxycyclohexenylmethyl- 3',4'-epoxycyclohexene carboxylate, N-phenyl maleimide-glycidyl methacrylate copolymer, and 2-(3,4-epoxycyclohexyl) Ethyltrimethoxydecane.

更系統地說，作為環氧化合物，例如可列舉：縮水甘油醚、縮水甘油酯、縮水甘油胺、含有環氧基的丙烯酸系樹脂、縮水甘油基醯胺、異三聚氰酸縮水甘油酯、鏈狀脂肪族型環氧化合物、及環狀脂肪族型環氧化合物。再者，環氧化合物是指具有環氧基的化合物，環氧樹脂是指具有環氧基的樹脂。 More specifically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, and epoxy group-containing acrylic resin. Glycidylguanamine, glycidyl isocyanurate, a chain aliphatic epoxy compound, and a cyclic aliphatic epoxy compound. Further, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

作為環氧化合物，例如可列舉：縮水甘油醚、縮水甘油酯、縮水甘油胺、含有環氧基的丙烯酸系樹脂、縮水甘油基醯胺、異三聚氰酸縮水甘油酯、鏈狀脂肪族型環氧化合物、及環狀脂肪族型環氧化合物。 Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidyl decylamine, glycidyl isocyanurate, and chain aliphatic type. An epoxy compound and a cyclic aliphatic epoxy compound.

作為縮水甘油醚，例如可列舉：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚S型環氧化合物、雙酚型環氧化合物、氫化雙酚A型環氧化合物、氫化雙酚F型環氧化合物、氫化雙酚S型環氧化合物、氫化雙酚型環氧化合物、溴化雙酚A型環氧化合物、溴化雙酚F型環氧化合物、苯酚酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、溴化苯酚酚醛清漆型環氧化合物、溴化甲酚酚醛清漆型環氧化合物、雙酚A酚醛清漆型環氧化合物、含有萘骨架的環氧化合物、芳香族聚縮水甘油醚化合物、二環戊二烯苯酚型環氧化合物、脂環式二縮水甘油醚化合物、脂肪族聚縮水甘油醚化合物、多硫化物型二縮水甘油醚化合物、及聯苯酚型環氧化合物。 Examples of the glycidyl ether include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a bisphenol epoxy compound, a hydrogenated bisphenol A epoxy compound, and hydrogenation. Bisphenol F type epoxy compound, hydrogenated bisphenol S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol A type epoxy compound, brominated bisphenol F type epoxy compound, phenol novolak type ring Oxygen compound, cresol novolak type epoxy compound, brominated phenol novolak type epoxy compound, brominated cresol novolak type epoxy compound, bisphenol A novolac type epoxy compound, epoxy compound containing naphthalene skeleton , an aromatic polyglycidyl ether compound, a dicyclopentadiene phenol type epoxy compound, an alicyclic diglycidyl ether compound, an aliphatic polyglycidyl ether compound, a polysulfide type diglycidyl ether compound, and a biphenol Type epoxy compound.

作為縮水甘油酯，例如可列舉：二縮水甘油酯化合物及縮水甘油酯環氧化合物。 Examples of the glycidyl ester include a diglycidyl ester compound and a glycidyl ester epoxy compound.

作為縮水甘油胺，例如可列舉：聚縮水甘油胺化合物及縮水甘油胺型環氧樹脂。 Examples of the glycidylamine include a polyglycidylamine compound and a glycidylamine type epoxy resin.

作為含有環氧基的丙烯酸系化合物，例如可列舉：具有環氧乙烷基的單體的均聚物及共聚物。 Examples of the epoxy group-containing acrylic compound include a homopolymer and a copolymer of a monomer having an oxirane group.

作為縮水甘油基醯胺，例如可列舉：縮水甘油基醯胺型環氧化合物。 Examples of the glycidyl decylamine include a glycidyl guanamine type epoxy compound.

作為鏈狀脂肪族型環氧化合物，例如可列舉：將烯化合物的碳-碳雙鍵氧化而獲得的含有環氧基的化合物。 Examples of the chain aliphatic epoxy compound include an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of an olefin compound.

作為環狀脂肪族型環氧化合物，例如可列舉：將環烯化合物的碳-碳雙鍵氧化而獲得的含有環氧基的化合物。 Examples of the cyclic aliphatic epoxy compound include an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cycloolefin compound.

作為雙酚A型環氧化合物，例如可列舉：jER828、jER1001、jER1002、jER1003、jER1004、jER1007、jER1010(均為三菱化學(股份)製造)，Epotohto YD-128(東都化成(股份)製造)，DER-331、DER-332、DER-324(均為陶氏化學(The Dow Chemical Company)製造)，Epiclon840、Epiclon850、Epiclon1050(均為迪愛生(DIC)(股份)製造)，Epomik R-140、Epomik R-301、及Epomik R-304(均為三井化學(公司)製造)。 Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, and jER1010 (all manufactured by Mitsubishi Chemical Corporation), and Epotohto YD-128 (manufactured by Tohto Kasei Co., Ltd.). DER-331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epiclon 840, Epiclon 850, Epiclon 1050 (both manufactured by Di AI (DIC)), Epomik R-140, Epomik R-301 and Epomik R-304 (all manufactured by Mitsui Chemicals, Inc.).

作為雙酚F型環氧化合物，例如可列舉：jER806、jER807、jER4004P(均為三菱化學(股份)製造)，Epotohto YDF-170、Epotohto YDF-175S、Epotohto YDF-2001(均為東都化成(股份)製造)，DER-354(陶氏化學公司製造)，Epiclon830、及Epiclon835(均為迪愛生(股份)製造)。 Examples of the bisphenol F-type epoxy compound include jER806, jER807, and jER4004P (all manufactured by Mitsubishi Chemical Corporation), Epotohto YDF-170, Epotohto YDF-175S, and Epotohto YDF-2001 (all of which are Dongdu Huacheng (shares) ) Manufacturing), DER-354 (manufactured by The Dow Chemical Company), Epiclon 830, and Epiclon 835 (all manufactured by Di Ai Sheng (share)).

作為雙酚型環氧化合物，例如可列舉：2,2-雙(4-羥苯基)-1,1,1,3,3,3-六氟丙烷的環氧化物。 Examples of the bisphenol type epoxy compound include an epoxide of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

作為氫化雙酚A型環氧化合物，例如可列舉：Suntohto ST-3000(東都化成(股份)製造)、Rikaresin HBE-100(新日本理化(股份)製造)、及Denacol EX-252(長瀨化成(Nagase chemteX)(股份)製造)。 Examples of the hydrogenated bisphenol A type epoxy compound include: Suntohto ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Rikaresin HBE-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), and Denacol EX-252 (长濑化成成(Nagase chemteX) (share) manufacturing).

作為氫化雙酚型環氧化合物，例如可列舉：氫化2,2-雙(4-羥苯基)-1,1,1,3,3,3-六氟丙烷的環氧化物。 Examples of the hydrogenated bisphenol type epoxy compound include an epoxide of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

作為溴化雙酚A型環氧化合物，例如可列舉：jER5050、jER5051(均為三菱化學(股份)製造)，Epotohto YDB-360、Epotohto YDB-400(均為東都化成(股份)製造)，DER-530、DER-538(均為陶氏化學製造)，Epiclon152、及Epiclon153(均為迪愛生(股份)製造)。 Examples of the brominated bisphenol A type epoxy compound include jER5050 and jER5051 (all manufactured by Mitsubishi Chemical Corporation), Epotohto YDB-360, and Epotohto YDB-400 (all manufactured by Tohto Kasei Co., Ltd.), DER - 530, DER-538 (all manufactured by Dow Chemical), Epiclon 152, and Epiclon 153 (all manufactured by Di Ai Sheng (share)).

作為苯酚酚醛清漆型環氧化合物，例如可列舉：jER152、jER154(均為三菱化學(股份)製造)，YDPN-638(東都化成公司製造)，DEN431、DEN438(均為陶氏化學製造)，Epiclon N-770(迪愛生(股份)製造)，EPPN-201、及EPPN-202(均為日本化藥(股份)製造)。 Examples of the phenol novolac type epoxy compound include jER152 and jER154 (all manufactured by Mitsubishi Chemical Corporation), YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), DEN431 and DEN438 (all manufactured by Dow Chemical), and Epiclon. N-770 (made by Di Ai Sheng (share)), EPPN-201, and EPPN-202 (both manufactured by Nippon Kayaku Co., Ltd.).

作為甲酚酚醛清漆型環氧化合物，例如可列舉：jER180S75(三菱化學(股份)製造)，YDCN-701、YDCN-702(均為東都化成公司製造)，Epiclon N-665、Epiclon N-695(均為迪愛生(股份)製造)，EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1020、EOCN-1025、及EOCN-1027(均為日本化藥(股份)製造)。 Examples of the cresol novolac type epoxy compound include jER180S75 (manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all manufactured by Dongdu Chemical Co., Ltd.), Epiclon N-665, and Epiclon N-695 ( All are manufactured by Di Ai Sheng (share), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

作為雙酚A酚醛清漆型環氧化合物，例如可列舉：jER157S70(三菱化學(股份)製造)、及Epiclon N-880(迪愛生(股份)製造)。 Examples of the bisphenol A novolac type epoxy compound include jER157S70 (manufactured by Mitsubishi Chemical Corporation) and Epiclon N-880 (manufactured by Di Aisheng (stock)).

作為含有萘骨架的環氧化合物，例如可列舉：Epiclon HP-4032、Epiclon HP-4700、Epiclon HP-4770(均為迪愛生(股份)製造)，及NC-7000(日本化藥公司製造)。 Examples of the epoxy compound containing a naphthalene skeleton include Epiclon HP-4032, Epiclon HP-4700, and Epiclon HP-4770 (all manufactured by Di Aisin Co., Ltd.), and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.).

作為芳香族聚縮水甘油醚化合物，例如可列舉：對苯二酚二縮水甘油醚(下述式EP-1)，兒茶酚二縮水甘油醚(下述式EP-2)，間苯二酚二縮水甘油醚(下述式EP-3)，2-[4-(2,3-環氧基丙氧基)苯基]-2-[4-[1,1-雙[4-([2,3-環氧基丙氧基]苯基)]乙基]苯基]丙烷(下述式EP-4)，三(4-縮水甘油氧基苯基)甲烷(下述式EP-5)，jER1031S、jER1032H60(均為三菱化學(股份)製造)，TACTIX-742(陶氏化學製造)，Denacol EX-201(長瀨化成(股份)製造)，DPPN-503、DPPN-502H、DPPN-501H、NC6000(均為日本化藥(股份)製造)，Techmore VG3101L(三井化學(股份)製造)，由下述式EP-6所表示的化合物，及由下述式EP-7所表示的化合物。 Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (formula: EP-1), catechol diglycidyl ether (formula: EP-2), and resorcinol. Diglycidyl ether (formula EP-3), 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([ 2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (formula EP-4), tris(4-glycidoxyphenyl)methane (formula EP-5 below) ), jER1031S, jER1032H60 (all manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (manufactured by Dow Chemical), Denacol EX-201 (manufactured by Changchun Chemicals Co., Ltd.), DPPN-503, DPPN-502H, DPPN- 501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (manufactured by Mitsui Chemicals Co., Ltd.), a compound represented by the following formula EP-6, and a compound represented by the following formula EP-7 .

[化124] [化124]

作為二環戊二烯苯酚型環氧化合物，例如可列舉：TACTIX-556(陶氏化學製造)、及Epiclon HP-7200(迪愛生(股份)製造)。 Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by The Dow Chemical Co., Ltd.) and Epiclon HP-7200 (Di Aisheng (share) Manufacture)).

作為脂環式二縮水甘油醚化合物，例如可列舉：環己烷二甲醇二縮水甘油醚化合物、及Rikaresin DME-100(新日本理化(股份)製造)。 Examples of the alicyclic diglycidyl ether compound include a cyclohexane dimethanol diglycidyl ether compound and Rikaresin DME-100 (manufactured by Shin Nippon Chemical and Chemical Co., Ltd.).

作為脂肪族聚縮水甘油醚化合物，例如可列舉：乙二醇二縮水甘油醚(下述式EP-8)，二乙二醇二縮水甘油醚(下述式EP-9)，聚乙二醇二縮水甘油醚，丙二醇二縮水甘油醚(下述式EP-10)，三丙二醇二縮水甘油醚(下述式EP-11)，聚丙二醇二縮水甘油醚，新戊二醇二縮水甘油醚(下述式EP-12)，1,4-丁二醇二縮水甘油醚(下述式EP-13)，1,6-己二醇二縮水甘油醚(下述式EP-14)，二溴新戊二醇二縮水甘油醚(下述式EP-15)，Denacol EX-810、Denacol EX-851、Denacol EX-8301、Denacol EX-911、Denacol EX-920、Denacol EX-931、Denacol EX-211、Denacol EX-212、Denacol EX-313(均為長瀨化成(股份)製造)，DD-503(艾迪科(ADEKA)(股份)製造)，Rikaresin W-100(新日本理化(股份)製造)，1,3,5,6-四縮水甘油基-2,4-己二醇(下述式EP-16)，甘油聚縮水甘油醚，山梨醇聚縮水甘油醚，三羥甲基丙烷聚縮水甘油醚，季戊四醇聚縮水甘油醚，Denacol EX-313、Denacol EX-611、Denacol EX-321、及Denacol EX-411(均為長瀨化成(股份)製造)。 Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (hereinafter, EP-8), diethylene glycol diglycidyl ether (hereinafter, EP-9), and polyethylene glycol. Diglycidyl ether, propylene glycol diglycidyl ether (formula EP-10), tripropylene glycol diglycidyl ether (formula EP-11 below), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether ( Formula EP-12), 1,4-butanediol diglycidyl ether (formula EP-13 below), 1,6-hexanediol diglycidyl ether (formula EP-14 below), dibromo Neopentyl glycol diglycidyl ether (formula EP-15 below), Denacol EX-810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX- 211, Denacol EX-212, Denacol EX-313 (all manufactured by Changchun Huacheng (share)), DD-503 (made by ADEKA (share)), Rikaresin W-100 (New Japan Physical and Chemical (share)) Manufactured), 1,3,5,6-tetraglycidyl-2,4-hexanediol (formula EP-16), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane Polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-31 3. Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all manufactured by Changchun Huacheng (share)).

[化126] [化126]

作為多硫化物型二縮水甘油醚化合物，例如可列舉：FLDP-50、及FLDP-60(均為東麗巧固樂(Toray Thiokol)(股份)製造)。 Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (all manufactured by Toray Thiokol Co., Ltd.).

作為聯苯酚型環氧化合物，例如可列舉：YX-4000、YL-6121H(均為三菱化學(股份)製造)，NC-3000P、及NC-3000S(均為日本化藥(股份)製造)。 Examples of the biphenol-type epoxy compound include YX-4000 and YL-6121H (all manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all manufactured by Nippon Kayaku Co., Ltd.).

作為二縮水甘油酯化合物，例如可列舉：對苯二甲酸二縮水甘油酯(下述式EP-17)、鄰苯二甲酸二縮水甘油酯(下述式 EP-18)、鄰苯二甲酸雙(2-甲基環氧乙烷基甲基)酯(下述式EP-19)、六氫鄰苯二甲酸二縮水甘油酯(下述式EP-20)、由下述式EP-21所表示的化合物、由下述式EP-22所表示的化合物、及由下述式EP-23所表示的化合物。 Examples of the diglycidyl ester compound include diglycidyl terephthalate (formula: EP-17) and diglycidyl phthalate (the following formula) EP-18), bis(2-methyloxiranylmethyl) phthalate (formula EP-19), hexahydrophthalic acid diglycidyl ester (EP-20 below) And a compound represented by the following formula EP-21, a compound represented by the following formula EP-22, and a compound represented by the following formula EP-23.

作為縮水甘油酯環氧化合物，例如可列舉：jER871、jER872(均為三菱化學(股份)製造)，Epiclon200、Epiclon400(均為迪愛生(股份)製造)，Denacol EX-711、及Denacol EX-721(均為長瀨化成(股份)製造)。 Examples of the glycidyl ester epoxy compound include jER871 and jER872 (all manufactured by Mitsubishi Chemical Corporation), Epiclon 200 and Epiclon 400 (all manufactured by Di Aisin Co., Ltd.), Denacol EX-711, and Denacol EX-721. (All manufactured by Changchun Huacheng (share)).

作為聚縮水甘油胺化合物，例如可列舉：N,N-二縮水甘油基苯胺(下述式EP-24)、N,N-二縮水甘油基-鄰甲苯胺(下述式 EP-25)、N,N-二縮水甘油基-間甲苯胺(下述式EP-26)、N,N-二縮水甘油基-2,4,6-三溴苯胺(下述式EP-27)、3-(N,N-二縮水甘油基)胺基丙基三甲氧基矽烷(下述式EP-28)、N,N,O-三縮水甘油基-對胺基苯酚(下述式EP-29)、N,N,O-三縮水甘油基-間胺基苯酚(下述式EP-30)、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷(下述式EP-31)、N,N,N',N'-四縮水甘油基-間苯二甲胺(TETRAD-X(三菱瓦斯化學(股份)製造)、下述式EP-32)、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷(TETRAD-C(三菱瓦斯化學(股份)製造)、下述式EP-33)、1,4-雙(N,N-二縮水甘油基胺基甲基)環己烷(下述式EP-34)、1,3-雙(N,N-二縮水甘油基胺基)環己烷(下述式EP-35)、1,4-雙(N,N-二縮水甘油基胺基)環己烷(下述式EP-36)、1,3-雙(N,N-二縮水甘油基胺基)苯(下述式EP-37)、1,4-雙(N,N-二縮水甘油基胺基)苯(下述式EP-38)、2,6-雙(N,N-二縮水甘油基胺基甲基)雙環[2.2.1]庚烷(下述式EP-39)、N,N,N',N'-四縮水甘油基-4,4'-二胺基二環己基甲烷(下述式EP-40)、2,2'-二甲基-(N,N,N',N'-四縮水甘油基)-4,4'-二胺基聯苯(下述式EP-41)、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯醚(下述式EP-42)、1,3,5-三(4-(N,N-二縮水甘油基)胺基苯氧基)苯(下述式EP-43)、2,4,4'-三(N,N-二縮水甘油基胺基)二苯醚(下述式EP-44)、三(4-(N,N-二縮水甘油基)胺基苯基)甲烷(下述式EP-45)、3,4,3',4'-四(N,N-二縮水甘油基胺基)聯苯(下述式EP-46)、3,4,3',4'-四(N,N-二縮水甘油基胺基)二苯醚(下述式EP-47)、由下述式EP-48所表示的化合物、及由下述式EP-49所表示的化合物。 Examples of the polyglycidylamine compound include N,N-diglycidylaniline (hereinafter, EP-24) and N,N-diglycidyl-o-toluidine (the following formula) EP-25), N,N-diglycidyl-m-toluidine (formula EP-26), N,N-diglycidyl-2,4,6-tribromoaniline (formula EP- 27), 3-(N,N-diglycidyl)aminopropyltrimethoxydecane (formula EP-28), N,N,O-triglycidyl-p-aminophenol (described below) Formula EP-29), N,N,O-triglycidyl-m-aminophenol (formula EP-30), N,N,N',N'-tetraglycidyl-4,4'- Diaminodiphenylmethane (formula EP-31), N,N,N',N'-tetraglycidyl-m-xylylenediamine (TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), Formula EP-32), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-33 ), 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane (formula: EP-34), 1,3-bis(N,N-diglycidylamino) Cyclohexane (formula EP-35 below), 1,4-bis(N,N-diglycidylamino)cyclohexane (formula EP-36 below), 1,3-double (N, N) - diglycidylamino)benzene (formula EP-37 below), 1,4-bis(N,N-diglycidylamino)benzene (formula EP-38), 2,6-double (N,N-diglycidylaminomethyl)bicyclo[2.2.1]heptane ( Illustrative EP-39), N, N, N', N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (formula EP-40), 2,2'-dimethyl Base-(N,N,N',N'-tetraglycidyl)-4,4'-diaminobiphenyl (formula EP-41), N,N,N',N'-tetrahydration Glyceryl-4,4'-diaminodiphenyl ether (formula EP-42 below), 1,3,5-tris(4-(N,N-diglycidyl)aminophenoxy)benzene (Equation EP-43 below), 2,4,4'-tris(N,N-diglycidylamino)diphenyl ether (formula EP-44 below), tris(4-(N,N-) Diglycidyl)aminophenyl)methane (formula EP-45 below), 3,4,3',4'-tetrakis (N,N-diglycidylamino)biphenyl (formula EP below) -46), 3,4,3',4'-tetrakis(N,N-diglycidylamino)diphenyl ether (formula: EP-47), represented by the following formula EP-48 And a compound represented by the following formula EP-49.

[化132] [化132]

作為具有環氧乙烷基的單體的均聚物，例如可列舉聚甲基丙烯酸縮水甘油酯。作為具有環氧乙烷基的單體的共聚物，例如可列舉：N-苯基順丁烯二醯亞胺-甲基丙烯酸縮水甘油酯共聚物、N-環己基順丁烯二醯亞胺-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸苄酯-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸丁酯-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸2-羥基乙酯-甲基丙烯酸縮水甘油酯共聚物、甲基丙烯酸(3-乙基-3-氧雜環丁基)甲酯-甲基丙烯酸縮水甘油酯共聚物、及苯乙烯-甲基丙烯酸縮水甘油酯共聚物。 Examples of the homopolymer of the monomer having an oxiranyl group include polyglycidyl methacrylate. Examples of the copolymer of the monomer having an oxiranyl group include N-phenyl maleimide-glycidyl methacrylate copolymer and N-cyclohexylmethylene iodide. - glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-A A glycidyl acrylate copolymer, a (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer.

作為具有環氧乙烷基的單體，例如可列舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧基環己酯，及(甲基)丙烯酸甲基縮水甘油酯。 Examples of the monomer having an oxiranyl group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidol (meth)acrylate. ester.

作為具有環氧乙烷基的單體的共聚物中的具有環氧乙烷基的單體以外的其他單體，例如可列舉：(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、苯乙烯、甲基苯乙烯、氯甲基苯乙烯、(甲基)丙烯酸(3-乙基-3-氧雜環丁基)甲酯、N-環己基順丁烯二醯亞胺、及N-苯基順丁烯二醯亞胺。 Examples of the monomer other than the monomer having an oxiranyl group in the copolymer of the monomer having an oxiranyl group include (meth)acrylic acid, methyl (meth)acrylate, and (a) Ethyl acrylate, isopropyl (meth) acrylate, (meth) propylene Butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate , 2-hydroxypropyl (meth)acrylate, styrene, methyl styrene, chloromethylstyrene, (3-ethyl-3-oxetanyl)methyl (meth)acrylate, N- Cyclohexyl maleimide, and N-phenyl maleimide.

作為異三聚氰酸縮水甘油酯，例如可列舉：1,3,5-三縮水甘油基-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮(下述式EP-50)、1,3-二縮水甘油基-5-烯丙基-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮(下述式EP-51)、及異三聚氰酸縮水甘油酯型環氧樹脂。 As the glycidyl iso-glycidyl cyanide, for example, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (EP-50 of the following formula), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione ( The following formula EP-51) and an isomeric isocyanurate type epoxy resin.

作為鏈狀脂肪族型環氧化合物，例如可列舉：環氧化聚丁二烯、及Epolead PB3600(大賽璐(Daicel)(股份)製造)。 Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and Epolead PB3600 (manufactured by Daicel).

作為環狀脂肪族型環氧化合物，例如可列舉：3,4-環氧基環己烯基甲基-3',4'-環氧基環己烯羧酸酯(Celloxide2021(大賽璐(股份)製造)，下述式EP-52)，2-甲基-3,4-環氧基環己基甲基-2'-甲基-3',4'-環氧基環己基羧酸酯(下述式EP-53)，2,3-環氧基環戊烷-2',3'-環氧基環戊烷醚(下述式EP-54)，ε-己內酯改質3,4-環氧基環己基甲基-3',4'-環氧基環己烷羧酸酯，1,2：8,9-二環氧基檸檬烯(Celloxide3000(大賽璐(股份)製造)，下述式EP-55)，由下述式EP-56所表示的化合物，CY-175、CY-177、CY-179(均為汽巴嘉基化學公司(The Ciba-Geigy Chemical Corp.)製造(可從日本亨斯邁(Huntsman．Japan)(股份)獲得))，EHPD-3150(大賽璐(股份)製造)，及環狀脂肪族型環氧樹脂。 Examples of the cyclic aliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (Celloxide 2021 (Dai Sai (share) ))), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate (formula: EP-52) Formula EP-53), 2,3-epoxycyclopentane-2',3'-epoxycyclopentane ether (Equation EP-54), ε-caprolactone modified 3, 4-ring Oxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2:8,9-dicyclooxylimene (Celloxide 3000 (manufactured by Daicel), the following formula EP-55), a compound represented by the following formula EP-56, CY-175, CY-177, CY-179 (all manufactured by The Ciba-Geigy Chemical Corp.) Japan's Huntsman. Japan (shared)), EHPD-3150 (made by Daicel (share)), and cyclic aliphatic epoxy resin.

環氧化合物優選聚縮水甘油胺化合物、雙酚A酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、及環狀脂肪族型環氧化合物的一種以上，優選N,N,N',N'-四縮水甘油基-間二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、商品名“Techmore VG3101L”、3,4-環氧基環己烯基甲基-3',4'-環氧基環己烯羧酸酯、N-苯基順丁烯二醯亞胺-甲基丙烯酸縮水甘油酯共聚物、N,N,O-三縮水甘油基-對胺基苯酚、雙酚A酚醛清漆型環氧化合物、及甲酚酚醛清漆型環氧化合物的一種以上。 The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac type epoxy compound, a cresol novolak type epoxy compound, and a cyclic aliphatic type epoxy compound, and preferably N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl 4-,4'-diaminodiphenylmethane, trade name "Techmore VG3101L", 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylic acid Ester, N-phenyl maleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolac type epoxy compound, and Cresol novolak type More than one type of epoxy compound.

另外，例如本發明的液晶配向劑可進而含有各種添加劑。作為各種添加劑，例如可列舉聚醯胺酸及其衍生物以外的高分子化合物、及低分子化合物，可根據各個目的而選擇使用。 Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include a polymer compound other than polyglycine and a derivative thereof, and a low molecular compound, and can be selected and used according to each purpose.

例如，作為所述高分子化合物，可列舉可溶於有機溶劑的高分子化合物。就控制所形成的液晶配向膜的電特性或配向性的觀點而言，優選將此種高分子化合物添加至本發明的液晶配向劑中。作為該高分子化合物，例如可列舉：聚醯胺、聚胺酯、聚脲、聚酯、聚環氧化物、聚酯多元醇、矽酮改質聚胺酯、及矽酮改質聚酯。 For example, examples of the polymer compound include polymer compounds which are soluble in an organic solvent. From the viewpoint of controlling the electrical characteristics or the alignment property of the liquid crystal alignment film formed, it is preferred to add such a polymer compound to the liquid crystal alignment agent of the present invention. Examples of the polymer compound include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, anthrone modified polyamine, and anthrone modified polyester.

另外，作為所述低分子化合物，例如1)當期望提升塗布性時可列舉符合該目的之界面活性劑，2)當需要提升抗靜電時可列舉抗靜電劑，3)當期望提升與基板的密接性時可列舉矽烷偶聯劑或鈦系的偶聯劑，另外，4)當在低溫下進行醯亞胺化時可列舉醯亞胺化觸媒。 Further, as the low molecular compound, for example, 1) when it is desired to improve the coatability, a surfactant suitable for the purpose may be mentioned, 2) an antistatic agent may be cited when it is desired to raise the antistatic property, and 3) when it is desired to lift the substrate. In the case of adhesion, a decane coupling agent or a titanium-based coupling agent may be mentioned, and 4) when ruthenium imidization is carried out at a low temperature, a ruthenium-based catalyst may be mentioned.

作為矽烷偶聯劑，例如可列舉：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基三甲氧基矽烷、對胺基苯基三甲氧基矽烷、對胺基苯基三乙氧基矽烷、間胺基苯基三甲氧基矽烷、間胺基苯基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3- 氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、N-(1,3-二甲基亞丁基)-3-(三乙氧基甲矽烷基)-1-丙胺、及N,N'-雙[3-(三甲氧基甲矽烷基)丙基]乙二胺。優選的矽烷偶聯劑為3-胺基丙基三乙氧基矽烷。 Examples of the decane coupling agent include vinyltrimethoxydecane, vinyltriethoxydecane, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane. N-(2-Aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyl Trimethoxydecane, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Decane, 3-glycidoxypropylmethyldimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3- Chloropropyltrimethoxydecane, 3-methacryloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, N-(1,3-dimethylbutylidene)-3-( Triethoxymethane alkyl)-1-propanamine, and N,N'-bis[3-(trimethoxymethylalkyl)propyl]ethylenediamine. A preferred decane coupling agent is 3-aminopropyltriethoxydecane.

作為醯亞胺化觸媒，例如可列舉：三甲胺、三乙胺、三丙胺、三丁胺等脂肪族胺類；N,N-二甲基苯胺、N,N-二乙基苯胺、甲基取代苯胺、羥基取代苯胺等芳香族胺類；吡啶、甲基取代吡啶、羥基取代吡啶、喹啉、甲基取代喹啉、羥基取代喹啉、異喹啉、甲基取代異喹啉、羥基取代異喹啉、咪唑、甲基取代咪唑、羥基取代咪唑等環式胺類。所述醯亞胺化觸媒優選選自N,N-二甲基苯胺，鄰羥基苯胺、間羥基苯胺、對羥基苯胺，鄰羥基吡啶、間羥基吡啶、對羥基吡啶，及異喹啉中的一種或兩種以上。 Examples of the ruthenium imidization catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimethylaniline, N,N-diethylaniline, and A. Aromatic amines such as phenylamine and hydroxy-substituted aniline; pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxyl Substituted cyclic amines such as isoquinoline, imidazole, methyl substituted imidazole, and hydroxy substituted imidazole. The quinone imidization catalyst is preferably selected from the group consisting of N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, and isoquinoline. One or two or more.

矽烷偶聯劑的添加量通常為聚醯胺酸或其衍生物的總重量的0 wt%~20 wt%，優選0.1 wt%~10 wt%。 The amount of the decane coupling agent to be added is usually from 0% by weight to 20% by weight, preferably from 0.1% by weight to 10% by weight based on the total weight of the polyaminic acid or its derivative.

相對於聚醯胺酸或其衍生物的羰基，醯亞胺化觸媒的添加量通常為0.01當量~5當量，優選0.05當量~3當量。 The amount of the ruthenium-imidation catalyst added is usually from 0.01 equivalents to 5 equivalents, preferably from 0.05 equivalents to 3 equivalents, based on the carbonyl group of the poly-amic acid or a derivative thereof.

其他添加劑的添加量根據其用途而不同，但通常為聚醯胺酸或其衍生物的總重量的0 wt%~100 wt%，優選0.1 wt%~50 wt%。 The amount of the other additives to be added varies depending on the use thereof, but is usually 0% by weight to 100% by weight, preferably 0.1% by weight to 50% by weight based on the total weight of the polyaminic acid or its derivative.

另外，例如在無損本發明的效果的範圍(優選所述聚醯胺酸或其衍生物的20 wt%以內的量)內，本發明的液晶配向劑可進而含有丙烯酸聚合物、丙烯酸酯聚合物、及四羧酸二酐、作為二羧酸或其衍生物與二胺的反應產物的聚醯胺醯亞胺等其他聚合物成分。 Further, the liquid crystal alignment agent of the present invention may further contain an acrylic polymer or an acrylate polymer, for example, in a range not detracting from the effects of the present invention (preferably within 20% by weight of the polyaminic acid or a derivative thereof) And tetracarboxylic dianhydride, as Other polymer components such as polyamidoximine which is a reaction product of a dicarboxylic acid or a derivative thereof and a diamine.

另外，例如就液晶配向劑的塗布性或所述聚醯胺酸或其衍生物的濃度的調整的觀點而言，本發明的液晶配向劑可進而含有溶劑。所述溶劑只要是具有溶解高分子成分的能力的溶劑，則可無特別限制地應用。所述溶劑廣泛包含通常用於聚醯胺酸、可溶性聚醯亞胺等高分子成分的製造步驟或用途方面的溶劑，可根據使用目的而適宜選擇。所述溶劑可以是1種，也可以是2種以上的混合溶劑。 Further, for example, from the viewpoint of the coatability of the liquid crystal alignment agent or the adjustment of the concentration of the polyaminic acid or its derivative, the liquid crystal alignment agent of the present invention may further contain a solvent. The solvent is not particularly limited as long as it has a solvent having the ability to dissolve a polymer component. The solvent widely includes a solvent which is generally used for a production step or a use of a polymer component such as polyacrylic acid or a soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be one type or a mixture of two or more types.

作為溶劑，可列舉所述聚醯胺酸或其衍生物的親溶劑、或以改善塗布性為目的的其他溶劑。 The solvent may, for example, be a lyophilic solvent of the polyaminic acid or a derivative thereof or another solvent for the purpose of improving coatability.

作為相對於聚醯胺酸或其衍生物為親溶劑的非質子性極性有機溶劑，可列舉：N-甲基-2-吡咯烷酮、二甲基咪唑啶酮、N-甲基己內醯胺、N-甲基丙醯胺、N,N-二甲基乙醯胺、二甲基亞碸、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、二乙基乙醯胺、γ-丁內酯等內酯。 Examples of the aprotic polar organic solvent which is a solvophilic solvent with respect to polyglycine or a derivative thereof include N-methyl-2-pyrrolidone, dimethylimidazolidinone, and N-methyl caprolactam. N-methylpropionamide, N,N-dimethylacetamide, dimethyl hydrazine, N,N-dimethylformamide, N,N-diethylformamide, diethyl Lactam, γ-butyrolactone and the like.

作為以改善塗布性等為目的之其他溶劑的例子，可列舉：乳酸烷基酯、3-甲基-3-甲氧基丁醇、四氫萘、異佛爾酮、乙二醇單丁醚等乙二醇單烷基醚、二乙二醇單***等二乙二醇單烷基醚、乙二醇單烷基乙酸酯或乙二醇苯基乙酸酯、三乙二醇單烷基醚、丙二醇單甲醚、丙二醇單丁醚等丙二醇單烷基醚、丙二酸二乙酯等丙二酸二烷基酯、二丙二醇單甲醚等二丙二醇單烷基醚、這些的乙酸酯類等酯化合物。 Examples of other solvents for the purpose of improving coatability and the like include alkyl lactate, 3-methyl-3-methoxybutanol, tetrahydronaphthalene, isophorone, and ethylene glycol monobutyl ether. Diethylene glycol monoalkyl ether such as ethylene glycol monoalkyl ether or diethylene glycol monoethyl ether, ethylene glycol monoalkyl acetate or ethylene glycol phenyl acetate, triethylene glycol monoalkane Dipropylene glycol monoalkyl ether such as propylene glycol monoalkyl ether such as propylene glycol monomethyl ether or propylene glycol monobutyl ether; dialkyl malonate such as diethyl malonate; dipropylene glycol monomethyl ether; An ester compound such as an ether or an acetate.

這些溶劑之中，所述溶劑特優選N-甲基-2-吡咯烷酮、二甲基咪唑啶酮、γ-丁內酯、乙二醇單丁醚、二乙二醇單***、丙二醇單丁醚、丙二醇單甲醚、及二丙二醇單甲醚。 Among these solvents, the solvent is particularly preferably N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether. , propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.

本發明的配向劑中的聚醯胺酸的濃度優選0.1 wt%~40 wt%。當將該配向劑塗布在基板上時，為了調整膜厚，有時需要事先利用溶劑對所含有的聚醯胺酸進行稀釋的操作。 The concentration of the polylysine in the alignment agent of the present invention is preferably from 0.1% by weight to 40% by weight. When the alignment agent is applied onto a substrate, in order to adjust the film thickness, it is necessary to perform an operation of diluting the contained polyamic acid with a solvent in advance.

本發明的配向劑中的固體成分濃度並無特別限定，只要結合下述的各種塗布法而選擇最合適的值即可。通常，為了抑制塗布時的不均或針孔等，相對於清漆重量，優選0.1 wt%~30 wt%，更優選1 wt%~10 wt%。 The solid content concentration in the alignment agent of the present invention is not particularly limited, and may be selected in accordance with various coating methods described below. In general, in order to suppress unevenness at the time of coating, pinholes, and the like, it is preferably 0.1 wt% to 30 wt%, more preferably 1 wt% to 10 wt%, based on the weight of the varnish.

對本發明的液晶配向膜進行詳細說明。本發明的液晶配向膜是通過對所述本發明的液晶配向劑的塗膜進行加熱所形成的膜。本發明的液晶配向膜可通過從液晶配向劑製作液晶配向膜的通常的方法而獲得。例如，本發明的液晶配向膜可通過經過形成本發明的液晶配向劑的塗膜的步驟、進行加熱乾燥的步驟、及進行加熱煅燒的步驟而獲得。針對本發明的液晶配向膜，視需要，可如後述般對經過加熱乾燥步驟、加熱煅燒步驟所獲得的膜進行摩擦處理來賦予異向性。或者，視需要，可在塗膜步驟、加熱乾燥步驟後照射光，或在加熱煅燒步驟後照射光來賦予異向性。另外，也可以用作不進行摩擦處理的VA用液晶配向膜。 The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can be obtained by a step of forming a coating film of the liquid crystal alignment agent of the present invention, a step of performing heat drying, and a step of performing heating and calcination. In the liquid crystal alignment film of the present invention, if necessary, the film obtained by the heating and drying step and the heating and calcining step may be subjected to a rubbing treatment to impart anisotropy. Alternatively, if necessary, the light may be irradiated after the coating step, the heat drying step, or the light may be irradiated after the heating calcination step to impart anisotropy. Further, it can also be used as a liquid crystal alignment film for VA which is not subjected to rubbing treatment.

塗膜可與通常的液晶配向膜的製作同樣地，通過將本發明的液晶配向劑塗布在液晶顯示元件中的基板上來形成。基板可列舉可設置有氧化銦錫(Indium Tin Oxide，ITO)電極、氧化銦鋅(In₂O₃-ZnO，IZO)電極、氧化銦鎵鋅(In-Ga-ZnO₄，IGZO)電極等電極或彩色濾光片等的玻璃製的基板。 The coating film can be formed by applying the liquid crystal alignment agent of the present invention to a substrate in a liquid crystal display element, similarly to the production of a normal liquid crystal alignment film. The substrate may be an electrode such as an Indium Tin Oxide (ITO) electrode, an Indium Oxide (In ₂ O ₃ -ZnO, IZO) electrode, or an Indium Ga-Zn (In-Ga-ZnO ₄ , IGZO) electrode. Or a glass substrate such as a color filter.

作為將液晶配向劑塗布在基板上的方法，通常已知有旋轉器法、印刷法、浸漬法、滴加法、噴墨法等。這些方法也可以同樣地應用於本發明中。 As a method of applying a liquid crystal alignment agent onto a substrate, a rotator method, a printing method, a dipping method, a dropping method, an inkjet method, and the like are generally known. These methods can also be equally applied to the present invention.

所述加熱乾燥步驟通常已知有在烘箱或紅外爐中進行加熱處理的方法、在加熱板上進行加熱處理的方法等。加熱乾燥步驟優選在溶劑可蒸發的範圍內的溫度下實施，更優選在相對於加熱煅燒步驟中的溫度為比較低的溫度下實施。具體而言，加熱乾燥溫度優選30℃~150℃的範圍，更優選50℃~120℃的範圍。 The heating and drying step is generally known as a method of performing heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, and the like. The heat drying step is preferably carried out at a temperature within a range in which the solvent can be evaporated, more preferably at a relatively low temperature with respect to the temperature in the heating calcination step. Specifically, the heating and drying temperature is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C.

所述加熱煅燒步驟可在所述聚醯胺酸或其衍生物呈現脫水．閉環反應所需要的條件下進行。所述塗膜的煅燒通常已知有在烘箱或紅外爐中進行加熱處理的方法、在加熱板上進行加熱處理的方法等。這些方法也可以同樣地應用於本發明中。通常優選在100℃~300℃左右的溫度下進行1分鐘~3小時，更優選120℃~280℃，進而更優選150℃~250℃。 The heating calcination step may exhibit dehydration in the polyamic acid or a derivative thereof. The conditions required for the ring closure reaction are carried out. The calcination of the coating film is generally known as a method of heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, and the like. These methods can also be equally applied to the present invention. It is usually preferably carried out at a temperature of from about 100 ° C to about 300 ° C for from 1 minute to 3 hours, more preferably from 120 ° C to 280 ° C, still more preferably from 150 ° C to 250 ° C.

在本發明的液晶配向膜的形成方法中，為了使液晶相對於水平方向及/或垂直方向在一個方向上進行配向，可適宜地使用摩擦法或光配向法等公知的形成方法作為對配向膜賦予異向性的方法。可特別適宜地使用光配向法。 In the method for forming a liquid crystal alignment film of the present invention, in order to align the liquid crystal in one direction with respect to the horizontal direction and/or the vertical direction, a known formation method such as a rubbing method or a photo-alignment method can be suitably used as the alignment film. A method of imparting anisotropy. The photoalignment method can be used particularly suitably.

使用摩擦法的本發明的液晶配向膜可經過如下的步驟而形成：將本發明的液晶配向劑塗布在基板上的步驟、對塗布有配向劑的基板進行加熱乾燥的步驟、對該膜進行加熱煅燒的步驟、以及對膜進行摩擦處理的步驟。 The liquid crystal alignment film of the present invention using a rubbing method can be formed by the steps of applying the liquid crystal alignment agent of the present invention onto a substrate, heating and drying the substrate coated with the alignment agent, and heating the film. The step of calcining, and the step of subjecting the film to a rubbing treatment.

摩擦處理可與通常的用於液晶配向膜的配向處理的摩擦處理同樣地進行，只要是可在本發明的液晶配向膜中獲得充分的延遲的條件即可。優選的條件是毛壓入量為0.2 mm~0.8 mm，平臺移動速度為5 mm/sec~250 mm/sec，輥旋轉速度為500 rpm~2,000 rpm。 The rubbing treatment can be carried out in the same manner as the rubbing treatment for the alignment treatment of the liquid crystal alignment film, as long as it is a condition that a sufficient retardation can be obtained in the liquid crystal alignment film of the present invention. The preferred conditions are a hair indentation of 0.2 mm to 0.8 mm, a platform moving speed of 5 mm/sec to 250 mm/sec, and a roller rotation speed of 500 rpm to 2,000 rpm.

對利用光配向法的本發明的液晶配向膜的形成方法進行詳細說明。利用光配向法的本發明的液晶配向膜可通過如下方式形成：對塗膜進行加熱乾燥後，照射放射線的直線偏光或無偏光，由此對塗膜賦予異向性，然後對該膜進行加熱煅燒。或者，可通過在對塗膜進行加熱乾燥，並進行加熱煅燒後，照射放射線的直線偏光或無偏光來形成。就配向性的觀點而言，放射線的照射步驟優選在加熱煅燒步驟前進行。 A method of forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail. The liquid crystal alignment film of the present invention by the photo-alignment method can be formed by heating and drying the coating film, irradiating the linearly polarized light or the non-polarized light of the radiation, thereby imparting anisotropy to the coating film, and then heating the film. Calcination. Alternatively, it may be formed by subjecting the coating film to heat drying, heating and calcining, and then irradiating the linearly polarized light or the non-polarized light of the radiation. From the viewpoint of the alignment, the irradiation step of the radiation is preferably performed before the heating and calcining step.

進而，為了提高液晶配向膜的液晶配向性能，也可以一面對塗膜進行加熱一面照射放射線的直線偏光或無偏光。放射線的照射可在對塗膜進行加熱乾燥的步驟、或進行加熱煅燒的步驟中進行，也可以在加熱乾燥步驟與加熱煅燒步驟之間進行。該步驟中的加熱乾燥溫度優選30℃~150℃的範圍，更優選50℃~120℃的範圍。另外，該步驟中的加熱煅燒溫度優選30℃~300℃的範圍，更優選50℃~250℃的範圍。 Further, in order to improve the liquid crystal alignment performance of the liquid crystal alignment film, it is also possible to face the linearly polarized light or the non-polarized light which is irradiated with radiation while being heated by the coating film. The irradiation of the radiation may be carried out in the step of heating and drying the coating film or in the step of heating and calcining, or may be carried out between the heating and drying step and the heating and calcining step. The heating and drying temperature in this step is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C. In addition, the heating calcination temperature in this step is preferably in the range of 30 ° C to 300 ° C It is more preferably in the range of 50 ° C to 250 ° C.

作為放射線，例如可使用包含150 nm~800 nm的波長的光的紫外線或可見光，優選包含300 nm~400 nm的光的紫外線。另外，可使用直線偏光或無偏光。這些光只要是可對所述塗膜賦予液晶配向性能的光，則並無特別限定，但當欲對液晶顯現強的配向限制力時，優選直線偏光。 As the radiation, for example, ultraviolet light or visible light containing light having a wavelength of 150 nm to 800 nm, and ultraviolet light containing light of 300 nm to 400 nm can be used. In addition, linear or unpolarized light can be used. The light is not particularly limited as long as it imparts liquid crystal alignment performance to the coating film. However, when it is desired to exhibit a strong alignment regulating force to the liquid crystal, linear polarization is preferable.

即便是低能量的光照射，本發明的液晶配向膜也可以顯示高液晶配向性能。所述放射線照射步驟中的直線偏光的照射量優選0.05 J/cm²~20 J/cm²，更優選0.5 J/cm²~10 J/cm²。另外，直線偏光的波長優選200 nm~400 nm，更優選300 nm~400 nm。直線偏光對於膜表面的照射角度並無特別限定，當欲顯現出對於液晶的強的配向限制力時，就縮短配向處理時間的觀點而言，優選相對於膜表面盡可能垂直。另外，通過照射直線偏光，本發明的液晶配向膜可使液晶在相對於直線偏光的偏光方向垂直的方向上進行配向。 Even with low-energy light irradiation, the liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment properties. The irradiation amount of the linearly polarized light in the radiation irradiation step is preferably 0.05 J/cm ² to 20 J/cm ² , more preferably 0.5 J/cm ² to 10 J/cm ² . Further, the wavelength of the linearly polarized light is preferably 200 nm to 400 nm, more preferably 300 nm to 400 nm. The angle of irradiation of the film surface by the linearly polarized light is not particularly limited. When a strong alignment regulating force for the liquid crystal is to be exhibited, it is preferable to be as perpendicular as possible to the film surface from the viewpoint of shortening the alignment treatment time. Further, by irradiating the linearly polarized light, the liquid crystal alignment film of the present invention can align the liquid crystal in a direction perpendicular to the polarization direction of the linearly polarized light.

當欲使預傾角顯現時，對所述膜照射的光可以是與所述相同的直線偏光，也可以是無偏光。當欲使預傾角顯現時，對所述膜照射的光的照射量優選0.05 J/cm²~20 J/cm²，特優選0.5 J/cm²~10 J/cm²，其波長優選250 nm~400 nm，特優選300 nm~380 nm。當欲使預傾角顯現時，對所述膜照射的光對於所述膜表面的照射角度並無特別限定，但就縮短配向處理時間的觀點而言，優選30度~60度。 When the pretilt angle is to be made to appear, the light irradiated to the film may be the same linearly polarized light as described, or may be unpolarized. When the pretilt angle is to be exhibited, the irradiation amount of the light irradiated to the film is preferably 0.05 J/cm ² to 20 J/cm ² , particularly preferably 0.5 J/cm ² to 10 J/cm ² , and the wavelength thereof is preferably 250 nm. ~400 nm, particularly preferably 300 nm~380 nm. When the pretilt angle is to be expressed, the irradiation angle of the light irradiated to the film on the surface of the film is not particularly limited, but from the viewpoint of shortening the alignment treatment time, it is preferably 30 to 60 degrees.

照射放射線的直線偏光或無偏光的步驟中所使用的光源可無限制地使用超高壓水銀燈、高壓水銀燈、低壓水銀燈、深紫外線(Deep Ultraviolet，Deep UV)燈、鹵素燈、金屬鹵化物燈、高功率金屬鹵化物燈、氙燈、水銀氙燈、準分子燈、KrF準分子雷射、螢光燈、發光二極管(Light Emitting Diode，LED)燈、鈉燈、微波激發無電極燈等。 The light source used in the step of illuminating the linearly polarized or non-polarized light of the radiation can use an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a deep ultraviolet (Deep Ultraviolet, Deep UV) lamp, a halogen lamp, a metal halide lamp, and a high light source without limitation. Power metal halide lamps, xenon lamps, mercury xenon lamps, excimer lamps, KrF excimer lasers, fluorescent lamps, Light Emitting Diode (LED) lamps, sodium lamps, microwave-excited electrodeless lamps, and the like.

本發明的液晶配向膜可通過進而包含所述步驟以外的其他步驟的方法而適宜地獲得。例如，本發明的液晶配向膜雖然不將利用清洗液清洗煅燒或放射線照射後的膜的步驟作為必需步驟，但可根據其他步驟的情況而設置清洗步驟。 The liquid crystal alignment film of the present invention can be suitably obtained by a method including further steps other than the above steps. For example, although the liquid crystal alignment film of the present invention does not take a step of washing the film after firing or radiation irradiation with a cleaning liquid as an essential step, a cleaning step may be provided depending on other steps.

作為利用清洗液的清洗方法，可列舉：刷洗、噴霧、蒸氣清洗或超聲波清洗等。這些方法可以單獨進行，也可以並用。作為清洗液，可使用：純水，或甲醇、乙醇、異丙醇等各種醇類，苯、甲苯、二甲苯等芳香族烴類，二氯甲烷等鹵素系溶劑，丙酮、甲基乙基酮等酮類，但並不限定於這些清洗液。當然，這些清洗液可使用經充分精製的雜質少的清洗液。此種清洗方法也可以應用於形成本發明的液晶配向膜時的所述清洗步驟中。 Examples of the cleaning method using the cleaning liquid include brushing, spraying, steam cleaning, or ultrasonic cleaning. These methods can be performed separately or in combination. As the cleaning liquid, pure alcohol or various alcohols such as methanol, ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen solvents such as dichloromethane, acetone, and methyl ethyl ketone can be used. Ketones are not limited to these cleaning solutions. Of course, these cleaning liquids can use a cleaning liquid which is sufficiently refined and has less impurities. Such a cleaning method can also be applied to the cleaning step in forming the liquid crystal alignment film of the present invention.

為了提高本發明的液晶配向膜的液晶配向性能，可在加熱煅燒步驟的前後、摩擦步驟的前後、或者偏光或無偏光的放射線照射的前後應用利用熱或光的退火處理。在該退火處理中，退火溫度為30℃~180℃，優選50℃~150℃，時間優選1分鐘~2小時。另外，用於退火處理的退火光可列舉UV燈、螢光燈、LED 燈等。光的照射量優選0.3 J/cm²~10 J/cm²。 In order to improve the liquid crystal alignment property of the liquid crystal alignment film of the present invention, annealing treatment by heat or light may be applied before and after the heating calcination step, before and after the rubbing step, or before or after the polarized or unpolarized radiation irradiation. In the annealing treatment, the annealing temperature is 30 ° C to 180 ° C, preferably 50 ° C to 150 ° C, and the time is preferably 1 minute to 2 hours. Further, examples of the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, an LED lamp, and the like. The irradiation amount of light is preferably 0.3 J/cm ² to 10 J/cm ² .

本發明的液晶配向膜的膜厚並無特別限定，但優選10 nm~300 nm，更優選30 nm~150 nm。本發明的液晶配向膜的膜厚可使用輪廓儀或橢偏儀(ellipsometer)等公知的膜厚測定裝置來測定。 The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by using a known film thickness measuring device such as a profiler or an ellipsometer.

本發明的液晶配向膜的特徵在於具有特別大的配向的異向性。此種異向性的大小可通過日本專利特開2005-275364號公報等中所記載的使用偏光IR的方法來評價。另外，如以下的實施例所示，也可以通過使用橢圓偏振術(ellipsometry)的方法來評價。當將本發明的配向膜用作液晶組合物用配向膜時，可認為具有更大的膜的異向性的材料對於液晶組合物具有大的配向限制力。 The liquid crystal alignment film of the present invention is characterized by having an exceptionally oriented anisotropy. The size of the anisotropy can be evaluated by a method using polarized light described in JP-A-2005-275364. Further, as shown in the following examples, it can also be evaluated by a method using ellipsometry. When the alignment film of the present invention is used as an alignment film for a liquid crystal composition, it is considered that a material having a larger anisotropy of the film has a large alignment regulating force for the liquid crystal composition.

除液晶顯示器用的液晶組合物的配向用途以外，本發明的液晶配向膜可用於光學補償材料或其他所有液晶材料的配向控制。另外，本發明的配向膜由於具有大的異向性，因此可單獨用於光學補償材料用途。 In addition to the alignment use of the liquid crystal composition for liquid crystal displays, the liquid crystal alignment film of the present invention can be used for alignment control of optical compensation materials or all other liquid crystal materials. Further, the alignment film of the present invention can be used alone for optical compensation materials because of its large anisotropy.

本發明提供一種液晶顯示元件，其包括對向配置的一對基板、形成在所述一對基板各自的對向面的一者或兩者上的電極、形成在所述一對基板各自的對向面上的液晶配向膜、以及形成在所述一對基板間的液晶層，且所述液晶配向膜為本發明的配向膜。 The present invention provides a liquid crystal display element including a pair of substrates disposed oppositely, electrodes formed on one or both of opposite surfaces of the pair of substrates, and pairs formed on the pair of substrates a liquid crystal alignment film on the surface and a liquid crystal layer formed between the pair of substrates, and the liquid crystal alignment film is an alignment film of the present invention.

所述電極只要是形成在基板的一面上的電極，則並無特別限定。此種電極例如可列舉ITO或金屬的蒸鍍膜等。另外，電極可形成在基板的一個面的整個面上，也可以形成為例如經圖案化的所期望的形狀。電極的所述所期望的形狀例如可列舉梳型或鋸齒構造等。電極可形成在一對基板中的一個基板上，也可以形成在兩個基板上。電極的形成的形態根據液晶顯示元件的種類而不同，例如在IPS型液晶顯示元件的情況下，將電極配置在所述一對基板的一者上，在其他液晶顯示元件的情況下，將電極配置在所述一對基板兩者上。在所述基板或電極上形成所述液晶配向膜。 The electrode is not particularly limited as long as it is an electrode formed on one side of the substrate. Do not limit. Examples of such an electrode include a vapor deposited film of ITO or metal. Further, the electrode may be formed on the entire surface of one face of the substrate, or may be formed, for example, in a patterned desired shape. The desired shape of the electrode may be, for example, a comb type or a sawtooth structure. The electrodes may be formed on one of the pair of substrates or may be formed on the two substrates. The form in which the electrodes are formed differs depending on the type of the liquid crystal display element. For example, in the case of an IPS type liquid crystal display element, the electrodes are disposed on one of the pair of substrates, and in the case of other liquid crystal display elements, the electrodes are provided. Disposed on both of the pair of substrates. The liquid crystal alignment film is formed on the substrate or the electrode.

所述液晶層是以通過形成有液晶配向膜的面對向的所述一對基板來夾持液晶組合物的形式形成。在液晶層的形成過程中，視需要可使用微粒子或樹脂片等介於所述一對基板之間並形成適當的間隔的間隔片。 The liquid crystal layer is formed in a form of sandwiching a liquid crystal composition by the pair of substrates facing each other in which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a spacer such as a fine particle or a resin sheet interposed between the pair of substrates and forming an appropriate interval may be used as needed.

液晶組合物並無特別限制，可使用介電常數異向性為正或負的各種液晶組合物。介電常數異向性為正的優選的液晶組合物可列舉：日本專利第3086228號公報、日本專利第2635435號公報、日本專利特表平5-501735號公報、日本專利特開平8-157826號公報、日本專利特開平8-231960號公報、日本專利特開平9-241644號公報(EP885272A1說明書)、日本專利特開平9-302346號公報(EP806466A1說明書)、日本專利特開平8-199168號公報(EP722998A1說明書)、日本專利特開平9-235552號公報、日本專利特開平9-255956號公報、日本專利特開平9-241643號公報 (EP885271A1說明書)、日本專利特開平10-204016號公報(EP844229A1說明書)、日本專利特開平10-204436號公報、日本專利特開平10-231482號公報、日本專利特開2000-087040號公報、日本專利特開2001-48822號公報等中所揭示的液晶組合物。 The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. A preferred liquid crystal composition having positive dielectric anisotropy is exemplified by Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, and Japanese Patent Laid-Open No. Hei 8-157826 Japanese Patent Laid-Open No. Hei 8-231960, Japanese Patent Laid-Open No. Hei 9-241644 (A. pp. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, and Japanese Patent Laid-Open No. Hei 9-241643 Japanese Patent Laid-Open No. Hei 10-204016 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei. No. Hei. A liquid crystal composition disclosed in JP-A-2001-48822 or the like.

介電常數異向性為負的優選的液晶組合物可列舉：日本專利特開昭57-114532號公報、日本專利特開平2-4725號公報、日本專利特開平4-224885號公報、日本專利特開平8-40953號公報、日本專利特開平8-104869號公報、日本專利特開平10-168076號公報、日本專利特開平10-168453號公報、日本專利特開平10-236989號公報、日本專利特開平10-236990號公報、日本專利特開平10-236992號公報、日本專利特開平10-236993號公報、日本專利特開平10-236994號公報、日本專利特開平10-237000號公報、日本專利特開平10-237004號公報、日本專利特開平10-237024號公報、日本專利特開平10-237035號公報、日本專利特開平10-237075號公報、日本專利特開平10-237076號公報、日本專利特開平10-237448號公報(EP967261A1說明書)、日本專利特開平10-287874號公報、日本專利特開平10-287875號公報、日本專利特開平10-291945號公報、日本專利特開平11-029581號公報、日本專利特開平11-080049號公報、日本專利特開2000-256307號公報、日本專利特開2001-019965號公報、日本專利特開2001-072626號公報、日本專利特開2001-192657號公報等中所揭示的液晶組合物。即便向介電常數異向性為正或負的液晶組合物中添加一種以上的光學活化合物來使用，也無任何影響。 A preferred liquid crystal composition having a negative dielectric anisotropy is exemplified by Japanese Patent Laid-Open Publication No. SHO 57-114532, Japanese Patent Laid-Open No. Hei No. 2-4725, Japanese Patent Laid-Open No. Hei-4-224885, and Japanese Patent. Japanese Patent Publication No. Hei 8-104869, Japanese Patent Laid-Open No. Hei 8-104869, Japanese Patent Application Laid-Open No. Hei No. 10-168076, Japanese Patent Application Laid-Open No. Hei No. Hei 10- No. Japanese Laid-Open Patent Publication No. Hei 10-236990, Japanese Patent Laid-Open No. Hei 10-236992, Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236994, Japanese Patent Laid-Open No. Hei 10--237000, and Japanese Patent Japanese Patent Laid-Open No. Hei 10-237024, Japanese Patent Laid-Open No. Hei 10-237024, Japanese Patent Laid-Open No. Hei 10-237035, Japanese Patent Laid-Open No. Hei 10-237075, Japanese Patent Laid-Open No. Hei 10-237076, and Japanese Patent No. Japanese Patent Laid-Open No. Hei 10-287874, Japanese Patent Laid-Open No. Hei 10-287875, and Japanese Patent Laid-Open No. Hei 10-291945 Japanese Patent Laid-Open No. Hei 11-029581, Japanese Patent Laid-Open No. Hei 11-080049, Japanese Patent Laid-Open Publication No. 2000-256307, Japanese Patent Laid-Open Publication No. 2001-019965, and Japanese Patent Laid-Open No. 2001-072626 The liquid crystal composition disclosed in Japanese Laid-Open Patent Publication No. 2001-192657, and the like. Even if one or more optically active compounds are added to a liquid crystal composition having a positive or negative dielectric anisotropy, it has no effect.

[實施例] [Examples]

以下，通過實施例來說明本發明，但本發明並不限定於這些實施例。實施例中的液晶顯示元件的評價法如下。 Hereinafter, the present invention will be described by way of examples, but the invention is not limited to these examples. The evaluation method of the liquid crystal display element in the examples is as follows.

<重量平均分子量(Mw)> <weight average molecular weight (Mw)>

聚醯胺酸的重量平均分子量通過如下方式求出：使用2695分離模塊2414示差折射儀(沃特世(Waters)製造)並利用GPC法來測定，然後進行聚苯乙烯換算。利用磷酸-二甲基甲醯胺(Dimethylformamide，DMF)混合溶液(磷酸/DMF=0.6/100：重量比)，以聚醯胺酸濃度變成約2 wt%的方式對所獲得的聚醯胺酸進行稀釋。管柱使用HSPgel RT MB-M(沃特世製造)，將所述混合溶液作為展開劑，在管柱溫度為50℃、流速為0.40 mL/min的條件下進行測定。標準聚苯乙烯使用東曹(Tosoh)(股份)製造的TSK標準聚苯乙烯。 The weight average molecular weight of polylysine was determined by using a 2695 separation module 2414 differential refractometer (manufactured by Waters) and measuring by a GPC method, followed by polystyrene conversion. The obtained polylysine was obtained by using a mixed solution of phosphoric acid-dimethylformamide (DMF) (phosphoric acid/DMF=0.6/100: weight ratio) to a polyglycine concentration of about 2 wt%. Dilute. The column was measured using HSPgel RT MB-M (manufactured by Waters), and the mixed solution was used as a developing solvent under the conditions of a column temperature of 50 ° C and a flow rate of 0.40 mL / min. Standard polystyrene uses TSK standard polystyrene manufactured by Tosoh.

<配向膜的延遲及膜厚測定> <Measurement of retardation and film thickness of alignment film>

使用分光橢偏儀M-2000U(J.A.Woollam股份有限公司製造)來求出。在本實施例的情況下，膜的延遲值與聚合物主鏈的配向度成比例地增大。即，具有大的延遲值的膜具有大的配向度。 It was obtained using a spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Ltd.). In the case of the present embodiment, the retardation value of the film increases in proportion to the degree of alignment of the polymer main chain. That is, a film having a large retardation value has a large degree of alignment.

<配向膜的透過率測定> <Measurement of transmittance of alignment film>

使用UV-Vis光譜測定裝置(日本分光V-660)，測定配向膜的透過率。將未形成配向膜的玻璃基板作為參考。 The transmittance of the alignment film was measured using a UV-Vis spectrometer (Japan Spectroscopic V-660). A glass substrate on which an alignment film was not formed was used as a reference.

實施例中所使用的溶劑與添加劑如下。 The solvents and additives used in the examples are as follows.

<溶劑> <solvent>

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

丁基溶纖劑(乙二醇單丁醚)：BC Butyl cellosolve (ethylene glycol monobutyl ether): BC

<添加劑> <additive>

添加劑(Ad1)：雙[4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基]甲烷 Additive (Ad1): bis[4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)phenyl]methane

添加劑(Ad2)：N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷 Additive (Ad2): N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

添加劑(Ad3)：3-胺基丙基三乙氧基矽烷 Additive (Ad3): 3-aminopropyltriethoxydecane

添加劑(Ad4)：2-(3,4-環氧基環己基)乙基三甲氧基矽烷 Additive (Ad4): 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

添加劑(Ad5)：1,3-雙(4,5-二氫-2-噁唑基)苯 Additive (Ad5): 1,3-bis(4,5-dihydro-2-oxazolyl)benzene

<1.聚醯胺酸的合成> <1. Synthesis of polyaminic acid>

[合成例1] [Synthesis Example 1]

向具備溫度計、攪拌機、原料投入添加口及氮氣導入口的50 mL的褐色四口燒瓶中加入式(DI-5-1)中m為1的二胺0.446 g、及脫水NMP 13.5 g，在乾燥氮氣氣流下進行攪拌溶解。繼而，添加酸二酐(1-a)(日本精化(股份)製造)1.054 g及脫水NMP 5.0 g，並在室溫下持續攪拌24小時。向該反應溶液中添加BC 5.0 g，獲得聚合物固體成分濃度為6 wt%的聚醯胺酸溶液。將該聚醯胺酸溶液設為PA1。PA1中所含有的聚醯胺酸的重量平均分子量為74,000。 To a 50 mL brown four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet, 0.446 g of a diamine having a m of 1 in the formula (DI-5-1) and a dehydrated NMP 13.5 g were dried. The mixture was stirred and dissolved under a nitrogen stream. Then, 1.054 g of acid dianhydride (1-a) (manufactured by Nippon Seiki Co., Ltd.) and 5.0 g of dehydrated NMP were added, and stirring was continued for 24 hours at room temperature. To the reaction solution, 5.0 g of BC was added to obtain a polyglycine solution having a polymer solid concentration of 6 wt%. The polyaminic acid solution was set to PA1. The polyamine acid contained in PA1 has a weight average molecular weight of 74,000.

[合成例2~合成例37] [Synthesis Example 2 to Synthesis Example 37]

除如表1-1、表1-2所示般變更四羧酸二酐及二胺以外，依據合成例1製備聚合物固體成分濃度為6 wt%的聚醯胺酸溶液(PA2)~聚醯胺酸溶液(PA37)。包含合成例1的結果，將所獲得的聚醯胺酸的重量平均分子量的測定結果匯總於表1-1、表1-2中。 In addition to the tetracarboxylic dianhydride and the diamine as shown in Table 1-1 and Table 1-2, a polyamic acid solution (PA2) to a polymer having a solid concentration of 6 wt% was prepared according to Synthesis Example 1. Proline solution (PA37). The results of the synthesis example 1 were included, and the measurement results of the weight average molecular weight of the obtained polylysine were summarized in Table 1-1 and Table 1-2.

以相對於聚合物重量為5 wt%的比例，將添加劑(Ad1)添加至合成例1中所製備的聚合物固體成分濃度為6 wt%的聚醯胺酸溶液(PA1)中。將所獲得的聚醯胺酸溶液設為PA38。 The additive (Ad1) was added to a polyglycine solution (PA1) having a polymer solid content concentration of 6 wt% prepared in Synthesis Example 1 at a ratio of 5 wt% based on the weight of the polymer. The obtained polyaminic acid solution was designated as PA38.

如表2所示般，以表中所示的比例將添加劑(Ad2)~添加劑(Ad5)添加至聚醯胺酸溶液中，製備聚醯胺酸溶液(PA39)~聚醯胺酸溶液(PA43)。 As shown in Table 2, the additive (Ad2)~additive (Ad5) was added to the polyaminic acid solution at the ratio shown in the table to prepare a polylysine solution (PA39)~polyglycine solution (PA43). ).

<2.測定用基板的製作方法及透過率、延遲的測定方法> <2. Method for Producing Measurement Substrate, Method for Measuring Transmittance and Delay>

[實施例1] [Example 1]

向合成例1中所製備的聚合物固體成分濃度為1 wt%的聚醯胺酸溶液(PA1)中添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。利用旋轉器(米卡薩(Mikasa)股份有限公司製造，旋轉塗布機(1H-DX2))將液晶配向劑塗布在玻璃基板上。再者，也包括以後的實施例、比較例在內，對應於液晶配向劑的粘度調整旋轉器的旋轉速度，使配向膜變成下述的膜厚。塗膜後，在加熱板(亞速旺(ASONE)股份有限公司製造，EC加熱板(EC-1200N))上以70℃進行80秒加熱乾燥後，在潔淨烘箱(愛斯佩克(Espec)股份有限公司製造，潔淨烘箱(PVHC-231))中，以230℃進行15分鐘加熱處理，而形成膜厚為100±10 nm的配向膜。對所獲得的基板的透過率進行測定，結果波長300 nm下的透過率為79.9%。 A mixed solvent of NMP/BC=4/1 (weight ratio) was added to a polyglycine solution (PA1) having a polymer solid concentration of 1 wt% prepared in Synthesis Example 1, and diluted into a polymer solid component. A liquid crystal alignment agent was prepared at a concentration of 4 wt%. The liquid crystal alignment agent was coated on a glass substrate by a spinner (manufactured by Mikasa Co., Ltd., spin coater (1H-DX2)). In addition, in the following examples and comparative examples, the rotational speed of the rotator was adjusted in accordance with the viscosity of the liquid crystal alignment agent, and the alignment film was changed to the following film thickness. After coating, it was heated and dried at 70 ° C for 80 seconds on a hot plate (manufactured by ASONE Co., Ltd., EC heating plate (EC-1200N)) in a clean oven (Espec). In a manufacturing company, a clean oven (PVHC-231), heat treatment was performed at 230 ° C for 15 minutes to form an alignment film having a film thickness of 100 ± 10 nm. The transmittance of the obtained substrate was measured, and as a result, the transmittance at a wavelength of 300 nm was 79.9%.

繼而，使用飯沼計量器(Iinuma Gauge)製作所股份有限公司製造的摩擦處理裝置，在摩擦布(毛長1.8 mm：人造絲)的毛壓入量為0.20 mm、平臺移動速度為60 mm/sec，輥旋轉速度為 1,000 rpm的條件下，對所獲得的液晶配向膜進行摩擦處理。對所獲得的基板的延遲進行測定，結果為0.26 nm。 Then, using a friction treatment device manufactured by Iinuma Gauge Co., Ltd., the frictional cloth (hair length 1.8 mm: rayon) has a hair injection amount of 0.20 mm and a platform moving speed of 60 mm/sec. Roller rotation speed is The obtained liquid crystal alignment film was subjected to rubbing treatment at 1,000 rpm. The retardation of the obtained substrate was measured and found to be 0.26 nm.

[實施例2~實施例29] [Example 2 to Example 29]

向聚合物固體成分濃度為6 wt%的聚醯胺酸溶液PA2~聚醯胺酸溶液PA25、及聚醯胺酸溶液PA38~聚醯胺酸溶液PA41中分別添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。使用所獲得的液晶配向劑，利用依據實施例1的方法製作測定用基板，並測定透過率與延遲。對應於聚醯胺酸溶液PA2~聚醯胺酸溶液PA25及聚醯胺酸溶液PA38~聚醯胺酸溶液PA41而依次作為實施例2~實施例29。 NMP/BC=4/1 was added to the polyacrylic acid solution PA2~polyglycine solution PA25 and the polyglycine solution PA38~polyglycine solution PA41 with a polymer solid concentration of 6 wt%, respectively. The solvent mixture of the weight ratio was diluted to a solid concentration of the polymer of 4 wt% to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a substrate for measurement was produced by the method of Example 1, and the transmittance and retardation were measured. Corresponding to the polyacrylic acid solution PA2~polyglycine solution PA25 and the polyaminic acid solution PA38~polyglycine solution PA41, it was sequentially used as Example 2 to Example 29.

[比較例1] [Comparative Example 1]

向合成例36中所製備的聚合物固體成分濃度為6 wt%的聚醯胺酸溶液(PA36)中添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。使用所獲得的液晶配向劑，利用依據實施例1的方法製作測定用基板，並測定透過率與延遲。與實施例1~實施例29的結果一同匯總於表3中。 A mixed solvent of NMP/BC=4/1 (weight ratio) was added to a polyglycine solution (PA36) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 36, and diluted into a polymer solid component. A liquid crystal alignment agent was prepared at a concentration of 4 wt%. Using the obtained liquid crystal alignment agent, a substrate for measurement was produced by the method of Example 1, and the transmittance and retardation were measured. The results of Examples 1 to 29 are summarized in Table 3.

通過實施例1~實施例29與比較例1的比較，可知本發明的配向膜對於提升延遲，對液晶賦予高配向性非常有用，且透過率得到大幅改善。 From the comparison of Examples 1 to 29 and Comparative Example 1, it was found that the alignment film of the present invention is very useful for imparting high alignment to the liquid crystal for the lift delay, and the transmittance is greatly improved.

[實施例30] [Example 30]

向合成例26中所製備的聚合物固體成分濃度為1 wt%的聚醯胺酸溶液(PA26)中添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。利用旋轉器(米卡薩股份有限公司製造，旋轉塗布機(1H-DX2))將液晶配向劑塗布在玻璃基板上。再者，也包括以後的實施例、比較例在內，對應於液晶配向劑的粘度調整旋轉器的旋轉速度，使配向膜變成下述的膜厚。塗膜後，在加熱板(亞速旺股份有限公司製造，EC加熱板(EC-1200N))上以70℃進行80秒加熱乾燥。繼而，使用優志旺(Ushio)電機(股份)製造的Multi Light ML-501C/B，從鉛垂方向經由偏光板對基板照射紫外線的直線偏光。此時的曝光能量是使用優志旺電機(股份)製造的紫外線累計光量計UIT-150(光接收器UVD-S365)來測定光量，並以在波長365 nm下變成5.0±0.1 J/cm²的方式調整曝光時間。利用抗紫外線膜覆蓋整個裝置，並在室溫、空氣中進行紫外線的照射。繼而，在潔淨烘箱(愛斯佩克股份有限公司製造，潔淨烘箱(PVHC-231))中，以230℃進行15分鐘加熱處理，而形成膜厚為100±10 nm的配向膜。對所獲得的基板的透過率進行測定，結果波長300 nm下的透過率為63.0%。對所獲得的基板的延遲進行測定，結果為3.26 nm。 A mixed solvent of NMP/BC=4/1 (weight ratio) was added to a polyglycine solution (PA26) having a polymer solid concentration of 1 wt% prepared in Synthesis Example 26, and diluted into a polymer solid component. A liquid crystal alignment agent was prepared at a concentration of 4 wt%. The liquid crystal alignment agent was coated on a glass substrate by a spinner (manufactured by Micasa Co., Ltd., spin coater (1H-DX2)). In addition, in the following examples and comparative examples, the rotational speed of the rotator was adjusted in accordance with the viscosity of the liquid crystal alignment agent, and the alignment film was changed to the following film thickness. After coating, the film was heated and dried at 70 ° C for 80 seconds on a hot plate (manufactured by Azov Corporation, EC heating plate (EC-1200N)). Then, Multi Light ML-501C/B manufactured by Ushio Electric Co., Ltd. was used to irradiate the substrate with ultraviolet light linearly polarized from the vertical direction via a polarizing plate. The exposure energy at this time was measured by using an ultraviolet cumulative photometer UIT-150 (photoreceiver UVD-S365) manufactured by Uchihiro Electric Co., Ltd., and became 5.0±0.1 J/cm ² at a wavelength of 365 nm. The way to adjust the exposure time. The entire apparatus was covered with an ultraviolet-resistant film, and ultraviolet rays were irradiated at room temperature in the air. Then, in a clean oven (manufactured by ESPEC Co., Ltd., clean oven (PVHC-231)), heat treatment was performed at 230 ° C for 15 minutes to form an alignment film having a film thickness of 100 ± 10 nm. The transmittance of the obtained substrate was measured, and as a result, the transmittance at a wavelength of 300 nm was 63.0%. The retardation of the obtained substrate was measured and found to be 3.26 nm.

[實施例31~實施例41] [Example 31 to Example 41]

向聚合物固體成分濃度為6 wt%的聚醯胺酸溶液PA27~聚醯胺酸溶液PA35、及聚醯胺酸溶液PA42~聚醯胺酸溶液PA43 中分別添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。使用所獲得的液晶配向劑，利用依據實施例30的方法製作測定用基板，並測定透過率與延遲。對應於聚醯胺酸溶液PA27~聚醯胺酸溶液PA35及聚醯胺酸溶液PA42~聚醯胺酸溶液PA43而依次作為實施例31~實施例41。 Polyglycine solution PA27~polyglycine solution PA35 with polymer solid content concentration of 6 wt%, and polyglycine solution PA42~polyglycine solution PA43 A mixed solvent of NMP/BC = 4/1 (weight ratio) was added thereto, and diluted to a polymer solid content concentration of 4 wt% to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a substrate for measurement was produced by the method of Example 30, and the transmittance and retardation were measured. Corresponding to the polyphosphamic acid solution PA27~polyglycine solution PA35 and the polyaminic acid solution PA42~polyglycine solution PA43, they were sequentially used as Examples 31 to 41.

[比較例2] [Comparative Example 2]

向合成例37中所製備的聚合物固體成分濃度為6 wt%的聚醯胺酸溶液(PA37)中添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。使用所獲得的液晶配向劑，利用依據實施例30的方法製作測定用基板，並測定透過率與延遲。與實施例30~實施例41的結果一同匯總於表4-1中。 A mixed solvent of NMP/BC=4/1 (weight ratio) was added to a polyglycine solution (PA37) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 37, and diluted into a polymer solid component. A liquid crystal alignment agent was prepared at a concentration of 4 wt%. Using the obtained liquid crystal alignment agent, a substrate for measurement was produced by the method of Example 30, and the transmittance and retardation were measured. The results of Examples 30 to 41 are summarized in Table 4-1.

[實施例42] [Example 42]

向合成例26中所製備的聚合物固體成分濃度為1 wt%的聚醯胺酸溶液(PA26)中添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。利用旋轉器(米卡薩股份有限公司製造，旋轉塗布機(1H-DX2))將液晶配向劑塗布在玻璃基板上。再者，也包括以後的實施例、比較例在內，對應於液晶配向劑的粘度調整旋轉器的旋轉速度，使配向膜變成下述的膜厚。塗膜後，在加熱板(亞速旺股份有限公司製造，EC加熱板(EC-1200N))上以70℃進行80秒加熱乾燥。繼而，使用優志旺電機(股份)製造的UV燈(UVL-1500M2-N1)，從鉛垂方向經由偏光板對基板照射紫外線的直線偏光。此時的曝光能量是使用優志旺電機(股份)製造的紫外線累計光量計UIT-150(光接收器UVD-S365)來測定光量，並以在波長365 nm下變成5.0±0.1 J/cm²的方式調整曝光時間。利用抗紫外線膜覆蓋整個裝置，並在室溫、空氣中進行紫外線的照射。繼而，在潔淨烘箱(愛斯佩克股份有限公司製造，潔淨烘箱(PVHC-231))中，以230℃進行15分鐘加熱處理，而形成膜厚為100±10 nm的配向膜。最後，在潔淨烘箱中，以120℃對加熱後的基板進行30分鐘的加熱退火。對所獲得的基板的透過率進行測定，結果波長300 nm下的透過率為63.1%。對所獲得的基板的延遲進行測定，結果為3.62 nm。 A mixed solvent of NMP/BC=4/1 (weight ratio) was added to a polyglycine solution (PA26) having a polymer solid concentration of 1 wt% prepared in Synthesis Example 26, and diluted into a polymer solid component. A liquid crystal alignment agent was prepared at a concentration of 4 wt%. The liquid crystal alignment agent was coated on a glass substrate by a spinner (manufactured by Micasa Co., Ltd., spin coater (1H-DX2)). In addition, in the following examples and comparative examples, the rotational speed of the rotator was adjusted in accordance with the viscosity of the liquid crystal alignment agent, and the alignment film was changed to the following film thickness. After coating, the film was heated and dried at 70 ° C for 80 seconds on a hot plate (manufactured by Azov Corporation, EC heating plate (EC-1200N)). Then, a UV lamp (UVL-1500M2-N1) manufactured by Uchiwa Electric Co., Ltd. was used to irradiate the substrate with a linearly polarized light of ultraviolet rays from the vertical direction via a polarizing plate. The exposure energy at this time was measured by using an ultraviolet cumulative photometer UIT-150 (photoreceiver UVD-S365) manufactured by Uchihiro Electric Co., Ltd., and became 5.0±0.1 J/cm ² at a wavelength of 365 nm. The way to adjust the exposure time. The entire apparatus was covered with an ultraviolet-resistant film, and ultraviolet rays were irradiated at room temperature in the air. Then, in a clean oven (manufactured by ESPEC Co., Ltd., clean oven (PVHC-231)), heat treatment was performed at 230 ° C for 15 minutes to form an alignment film having a film thickness of 100 ± 10 nm. Finally, the heated substrate was subjected to heat annealing at 120 ° C for 30 minutes in a clean oven. The transmittance of the obtained substrate was measured, and as a result, the transmittance at a wavelength of 300 nm was 63.1%. The retardation of the obtained substrate was measured and found to be 3.62 nm.

[實施例43~實施例45] [Examples 43 to 45]

向聚合物固體成分濃度為6 wt%的聚醯胺酸溶液PA27、聚醯胺酸溶液PA33、及聚醯胺酸溶液PA34中分別添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。使用所獲得的液晶配向劑，利用依據實施例42的方法製作測定用基板，並測定透過率與延遲。對應於聚醯胺酸溶液PA27、聚醯胺酸溶液PA33、及聚醯胺酸溶液PA34而依次作為實施例43~實施例45。 A mixed solvent of NMP/BC=4/1 (weight ratio) is added to the polyamic acid solution PA27, the polyaminic acid solution PA33, and the polyaminic acid solution PA34 having a polymer solid concentration of 6 wt%, respectively. And diluted to a polymer solid content concentration of 4 wt% to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a substrate for measurement was produced by the method of Example 42, and the transmittance and retardation were measured. Corresponding to the polyamic acid solution PA27, the polyaminic acid solution PA33, and the polyaminic acid solution PA34, they were sequentially used as Examples 43 to 45.

[比較例3] [Comparative Example 3]

向合成例37中所製備的聚合物固體成分濃度為6 wt%的聚醯胺酸溶液(PA37)中添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。使用所獲得的液晶配向劑，利用依據實施例42的方法製作測定用基板，並測定透過率與延遲。與實施例42~實施例45的結果一同匯總於表4-2中。 A mixed solvent of NMP/BC=4/1 (weight ratio) was added to a polyglycine solution (PA37) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 37, and diluted into a polymer solid component. A liquid crystal alignment agent was prepared at a concentration of 4 wt%. Using the obtained liquid crystal alignment agent, a substrate for measurement was produced by the method of Example 42, and the transmittance and retardation were measured. The results of Examples 42 to 45 are summarized in Table 4-2.

[實施例46] [Example 46]

向合成例26中所製備的聚合物固體成分濃度為1 wt%的聚醯胺酸溶液(PA26)中添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。利用旋轉器(米卡薩股份有限公司製造，旋轉塗布機(1H-DX2))將液晶配向劑塗布在玻璃基板上。再者，也包括以後的實施例、比較例在內，對應於液晶配向劑的粘度調整旋轉器的旋轉速度，使配向膜變成下述的膜厚。塗膜後，在加熱板(亞速旺股份有限公司製造，EC加熱板(EC-1200N))上以70℃進行80秒加熱乾燥。繼而，使用優志旺電機(股份)製造的Multi Light ML-501C/B，從鉛垂方向經由偏光板對基板照射紫外線的直線偏光。此時的曝光能量是使用優志旺電機(股份)製造的紫外線累計光量計UIT-150(光接收器UVD-S365)來測定光量，並以在波長365 nm下變成5.0±0.1 J/cm²的方式調整曝光時間。在紫外線曝光中，將基板的溫度加熱至50℃。利用抗紫外線膜覆蓋整個裝置，並在室溫、空氣中進行紫外線的照射。繼而，在潔淨烘箱(愛斯佩克股份有限公司製造，潔淨烘箱(PVHC-231))中，以230℃進行15分鐘加熱處理，而形成膜厚為100±10 nm的配向膜。對所獲得的基板的透過率進行測定，結果波長300 nm下的透過率為63.0%。對所獲得的基板的延遲進行測定，結果為3.69 nm。 A mixed solvent of NMP/BC=4/1 (weight ratio) was added to a polyglycine solution (PA26) having a polymer solid concentration of 1 wt% prepared in Synthesis Example 26, and diluted into a polymer solid component. A liquid crystal alignment agent was prepared at a concentration of 4 wt%. The liquid crystal alignment agent was coated on a glass substrate by a spinner (manufactured by Micasa Co., Ltd., spin coater (1H-DX2)). In addition, in the following examples and comparative examples, the rotational speed of the rotator was adjusted in accordance with the viscosity of the liquid crystal alignment agent, and the alignment film was changed to the following film thickness. After coating, the film was heated and dried at 70 ° C for 80 seconds on a hot plate (manufactured by Azov Corporation, EC heating plate (EC-1200N)). Then, the Multi Light ML-501C/B manufactured by Uchiwa Electric Co., Ltd. was used to irradiate the substrate with ultraviolet light linearly polarized from the vertical direction via a polarizing plate. The exposure energy at this time was measured by using an ultraviolet cumulative photometer UIT-150 (photoreceiver UVD-S365) manufactured by Uchihiro Electric Co., Ltd., and became 5.0±0.1 J/cm ² at a wavelength of 365 nm. The way to adjust the exposure time. In the ultraviolet exposure, the temperature of the substrate was heated to 50 °C. The entire apparatus was covered with an ultraviolet-resistant film, and ultraviolet rays were irradiated at room temperature in the air. Then, in a clean oven (manufactured by ESPEC Co., Ltd., clean oven (PVHC-231)), heat treatment was performed at 230 ° C for 15 minutes to form an alignment film having a film thickness of 100 ± 10 nm. The transmittance of the obtained substrate was measured, and as a result, the transmittance at a wavelength of 300 nm was 63.0%. The retardation of the obtained substrate was measured and found to be 3.69 nm.

[實施例47~實施例49] [Examples 47 to 49]

向聚合物固體成分濃度為6 wt%的聚醯胺酸溶液PA27、聚醯胺酸溶液PA33、及聚醯胺酸溶液PA34中分別添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。使用所獲得的液晶配向劑，利用依據實施例46的方法製作測定用基板，並測定透過率與延遲。對應於聚醯胺酸溶液PA27、聚醯胺酸溶液PA33、及聚醯胺酸溶液PA34而依次作為實施例47~實施例49。 A mixed solvent of NMP/BC=4/1 (weight ratio) is added to the polyamic acid solution PA27, the polyaminic acid solution PA33, and the polyaminic acid solution PA34 having a polymer solid concentration of 6 wt%, respectively. And diluted into a solid polymer A liquid crystal alignment agent was prepared at a degree of 4 wt%. Using the obtained liquid crystal alignment agent, a substrate for measurement was produced by the method of Example 46, and the transmittance and retardation were measured. Corresponding to the polyamine acid solution PA27, the polyaminic acid solution PA33, and the polyaminic acid solution PA34, they were sequentially used as Examples 47 to 49.

[比較例4] [Comparative Example 4]

向合成例37中所製備的聚合物固體成分濃度為6 wt%的聚醯胺酸溶液(PA37)中添加NMP/BC=4/1(重量比)的混合溶劑，並稀釋成聚合物固體成分濃度為4 wt%而製成液晶配向劑。使用所獲得的液晶配向劑，利用依據實施例46的方法製作測定用基板，並測定透過率與延遲。與實施例46~實施例49的結果一同匯總於表4-3中。 A mixed solvent of NMP/BC=4/1 (weight ratio) was added to a polyglycine solution (PA37) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 37, and diluted into a polymer solid component. A liquid crystal alignment agent was prepared at a concentration of 4 wt%. Using the obtained liquid crystal alignment agent, a substrate for measurement was produced by the method of Example 46, and the transmittance and retardation were measured. The results of Examples 46 to 49 are summarized in Table 4-3.

通過實施例30~實施例49與比較例2~比較例4的比較，可知本發明的光配向膜對於提升延遲，對液晶賦予高配向性非常有用，且透過率得到大幅改善。 From the comparison of Examples 30 to 49 and Comparative Example 2 to Comparative Example 4, it is understood that the optical alignment film of the present invention is very useful for imparting high alignment to the liquid crystal for the lift delay, and the transmittance is greatly improved.

(產業上的可利用性) (industrial availability)

若將使用本發明的特定的脂環式四羧酸二酐作為原料的聚醯胺酸及其衍生物用作液晶配向劑，則可提供液晶分子的配向性優異、且透過率高的配向膜。而且，可提供具有該配向膜的顯示特性優異的液晶顯示元件。 If a polyglycine which uses a specific alicyclic tetracarboxylic dianhydride of the present invention as a raw material and a derivative thereof are used as a liquid crystal alignment agent, alignment of liquid crystal molecules can be provided. An alignment film excellent in properties and high in transmittance. Further, a liquid crystal display element having excellent display characteristics of the alignment film can be provided.

Claims

一種聚醯胺酸或其衍生物，其特徵在於：使至少含有由下述式(1)所表示的四羧酸二酐的四羧酸二酐與二胺進行反應而獲得，所述二胺含有選自下述式(2-a)~式(2-c)中的至少1種二醯肼，式(2-a)中，G為單鍵、碳數1~20的伸烷基、-CO-、-O-、-S-、-SO₂-、-C(CH₃)₂-、或-C(CF₃)₂-；式(2-b)中，環B為環己烷環、苯環或萘環，所述基的任意的氫可由甲基、乙基、或苯基取代；式(2-c)中，環C分別獨立為環己烷環、或苯環，所述基的任意的氫可由甲基、乙基、或苯基取代；Y為單鍵、碳數1~20的伸烷基、-CO-、-O-、-S-、-SO₂-、-C(CH₃)₂-、或-C(CF₃)₂-。 A poly-proline or a derivative thereof, which is obtained by reacting a tetracarboxylic dianhydride containing at least a tetracarboxylic dianhydride represented by the following formula (1) with a diamine, The diamine contains at least one diterpenoid selected from the following formula (2-a) to formula (2-c). In the formula (2-a), G is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; in the formula (2-b), the ring B is a cyclohexane ring, a benzene ring or a naphthalene ring, and any hydrogen of the group may be substituted by a methyl group, an ethyl group, or a phenyl group; In the formula (2-c), the ring C is independently a cyclohexane ring or a benzene ring, and any hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group; Y is a single bond, and the carbon number is 1~ 20 alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -.

如申請專利範圍第1項所述的聚醯胺酸或其衍生物，其中：由式(1)所表示的四羧酸二酐為由下述式(1-a)或式(1-b)所表示的四羧酸二酐的至少1種， The poly-proline or a derivative thereof according to the first aspect of the invention, wherein the tetracarboxylic dianhydride represented by the formula (1) is represented by the following formula (1-a) or (1-b) At least one of the tetracarboxylic dianhydrides represented by

如申請專利範圍第1項所述的聚醯胺酸或其衍生物，其中：所述四羧酸二酐含有選自由下述式(AN-I)~式(AN-VII)所表示的四羧酸二酐的群組中的至少1種，式(AN-I)、式(AN-IV)及式(AN-V)中，X獨立為單鍵或-CH₂-；式(AN-II)中，G為單鍵、碳數1~20的伸烷基、-CO-、-O-、-S-、-SO₂-、-C(CH₃)₂-、或-C(CF₃)₂-；式(AN-II)~式(AN-IV)中，Y獨立為選自下述的三價的基的群組中的1種；這些基的任意的氫可由甲基、乙基或苯基取代；式(AN-III)~式(AN-V)中，環A為碳數3~10的單環式烴的基或碳數6~30的縮合多環式烴的基，此基的任意的氫可由甲基、乙基或苯基取代，連接在環上的結合鍵與構成環的任意的碳連結，2個結合鍵可與同一個碳連結；式(AN-VI)中，X¹⁰為碳數2~6的伸烷基；Me為甲基；Ph為苯基；式(AN-VII)中，G¹⁰獨立為-O-、-COO-或-OCO-；且r獨立為0或1。 The poly-proline or a derivative thereof according to claim 1, wherein the tetracarboxylic dianhydride contains four selected from the group consisting of the following formula (AN-I) to formula (AN-VII) At least one of the group of carboxylic dianhydrides, In the formula (AN-I), the formula (AN-IV) and the formula (AN-V), X is independently a single bond or -CH ₂ -; in the formula (AN-II), G is a single bond, and the carbon number is 1~ 20 alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; (AN-II)~ In (AN-IV), Y is independently one selected from the group consisting of trivalent groups described below; Any hydrogen of these groups may be substituted by a methyl group, an ethyl group or a phenyl group; in the formula (AN-III) to the formula (AN-V), the ring A is a group or a carbon number of a monocyclic hydrocarbon having a carbon number of 3 to 10. a group of 6 to 30 condensed polycyclic hydrocarbons, wherein any hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, and a bond bonded to the ring may be bonded to any carbon constituting the ring, and two bond bonds may be used. Linked to the same carbon; in the formula (AN-VI), X ¹⁰ is an alkylene group having 2 to 6 carbon atoms; Me is a methyl group; Ph is a phenyl group; and in the formula (AN-VII), G ^{10 is} independently - O-, -COO- or -OCO-; and r is independently 0 or 1.

如申請專利範圍第1項所述的聚醯胺酸或其衍生物，其中：所述四羧酸二酐含有選自由下述式(AN-1-1)、式(AN-1-13)、式(AN-2-1)、式(AN-3-1)、式(AN-3-2)、式(AN-4-5)、式(AN-4-17)、式(AN-7-2)、式(AN-10)、及式(AN-11-3)所組成的群組中的至少1種，式(AN-4-17)中，m為1~12的整數。 The poly-proline or a derivative thereof according to claim 1, wherein the tetracarboxylic dianhydride is selected from the group consisting of the following formula (AN-1-1) and the formula (AN-1-13) , (AN-2-1), (AN-3-1), (AN-3-2), (AN-4-5), (AN-4-17), (AN- At least one of the group consisting of 7-2), (AN-10), and (AN-11-3), In the formula (AN-4-17), m is an integer of 1 to 12.

如申請專利範圍第1項所述的聚醯胺酸或其衍生物，其中：所述二胺含有選自由下述式(DI-1)~式(DI-17)所組成的群組中的至少1種，式(DI-1)中，m為1~12的整數；(DI-3)及(DI-5)~(DI-7)中，G²¹獨立為單鍵、-NH-、-O-、-S-、-S-S-、-SO₂-、-CO-、-CONH-、-CONCH₃-、-NHCO-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m'-、-O-(CH₂)_m'-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、或-S-(CH₂)_m'-S-，m'獨立為1~12的整數，k為1~5的整數；(DI-6)及(DI-7)中，G²²獨立為單鍵、-O-、-S-、-CO-、-C(CH₃)₂-、-C(CF₃)₂-、或碳數1~10的伸烷基；式(DI-2)~式(DI-7)中的環己烷環及苯環的任意的-H可由-F、-CH₃、-OH、-CF₃、-CO₂H、-CONH₂、或苄基取代，此外，在式(DI-4)中，可由下述式(DI-4-a)~式(DI-4-c)取代，式(DI-4-a)及式(DI-4-b)中，R²⁰獨立為-H或-CH₃；式(DI-2)~式(DI-7)中，結合位置未固定在構成環的任一個碳原子上的基表示在所述環上的結合位置任意；而且，-NH₂在環己烷環或苯環上的結合位置為除G²¹或G²²的結合位置以外的任意的位置；式(DI-8)中，R²¹及R²²獨立為碳數1~3的烷基或苯基；G²³獨立為碳數1~6的伸烷基、伸苯基或經烷基取代的伸苯基；n為1~10的整數；式(DI-9)中，R²³獨立為碳數1~5的烷基、碳數1~5的烷氧基或-Cl；p獨立為0~3的整數；q為0~4的整數；式(DI-10)中，R²⁴為-H、碳數1~4的烷基、苯基、或苄基；式(DI-11)中，G²⁴為-CH₂-或-NH-；式(DI-12)中，G²⁵為單鍵、碳數2~6的伸烷基或1,4-伸苯基；r為0或1；式(DI-12)中，結合位置未固定在構成環的任一個碳原子上的基表示在所述環上的結合位置任意；而且，式(DI-9)、式(DI-11)及式(DI-12)中，結合在苯環上的-NH₂的結合位置為任意的位置；式(DI-13)中，G²⁶為單鍵、-O-、-COO-、-OCO-、-CO-、 -CONH-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、或-(CH₂)_m'-，m'為1~12的整數；R²⁵為碳數3~20的烷基、苯基、具有類固醇骨架的基、或由下述的式(DI-13-a)所表示的基，所述烷基中，任意的-H可由-F取代，任意的-CH₂-可由-O-、-CH=CH-或-C≡C-取代，所述苯基的-H可由-F、-CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃、碳數3~20的烷基、或碳數3~20的烷氧基取代，所述環己基的-H可由碳數3~20的烷基或碳數3~20的烷氧基取代，結合在苯環上的-NH₂的結合位置表示在所述環中為任意的位置；式(DI-13-a)中，G²⁷、G²⁸及G²⁹表示結合基，這些獨立為單鍵、或碳數1~12的伸烷基，所述伸烷基的1個以上的-CH₂-可由-O-、-COO-、-OCO-、-CONH-、-CH=CH-取代；環B²¹、環B²²、環B²³、及環B²⁴獨立為1,4-伸苯基、1,4-伸環己基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、萘-1,4-二基、萘-1,5-二基、萘-2,6-二基、萘-2,7-二基、或蒽-9,10-二基；環B²¹、環B²²、環B²³、及環B²⁴中，任意的-H可由-F或-CH₃取代； s、t及u獨立為0~2的整數，這些的合計為1~5；當s、t或u為2時，各個括號內的2個結合基可相同，也可以不同，2個環可相同，也可以不同；R²⁶為-F、-OH、碳數1~30的烷基、碳數1~30的氟取代烷基、碳數1~30的烷氧基、-CN、-OCH₂F、-OCHF₂、或-OCF₃，所述碳數1~30的烷基的任意的-CH₂-可由以下述式(DI-13-b)所表示的二價的基取代；式(DI-13-b)中，R²⁷及R²⁸獨立為碳數1~3的烷基；v為1~6的整數；式(DI-14)及式(DI-15)中，G³⁰獨立為單鍵、-CO-或-CH₂-；R²⁹獨立為-H或-CH₃；R³⁰為-H、碳數1~20的烷基、或碳數2~20的烯基；式(DI-15)中的苯環的1個-H可由碳數1~20的烷基或苯基取代；式(DI-14)及式(DI-15)中，結合位置未固定在構成環的任一個碳原子上的基表示在所述環上的結合位置任意；結合在苯環上的-NH₂表示在所述環上的結合位置任意；式(DI-16)及式(DI-17)中，G³¹獨立為-O-或碳數1~6的伸烷基；G³²為單鍵或碳數1~3的伸烷基；R³¹為-H或碳數1~20的烷基，所述烷基的任意的-CH₂-可由-O-、-CH=CH-或-C≡C-取代；R³²為碳數6~22的烷基；R³³為-H或碳數1~22的烷基；環B²⁵為1,4-伸苯基或1,4-伸環己基；r為0或1；且結合在苯環上的-NH₂表示在所述環上的結合位置任意。 The poly-proline or a derivative thereof according to claim 1, wherein the diamine contains a group selected from the group consisting of the following formulas (DI-1) to (DI-17); At least one, In the formula (DI-1), m is an integer of 1 to 12; in (DI-3) and (DI-5) to (DI-7), G ^{21 is} independently a single bond, -NH-, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH-, -CONCH ₃ -, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -( CH ₂ ) _m' -, -O-(CH ₂ ) _m' -O-, -N(CH ₃ )-(CH ₂ ) _k -N(CH ₃ )-, or -S-(CH ₂ ) _m' -S-,m' is an integer from 1 to 12, and k is an integer from 1 to 5. In (DI-6) and (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or an alkylene group having a carbon number of 1 to 10; a ring in the formula (DI-2) to (DI-7) Any -H of the alkane ring and the benzene ring may be substituted by -F, -CH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ or a benzyl group, and further, in the formula (DI-4), It can be replaced by the following formula (DI-4-a)~ formula (DI-4-c). In the formula (DI-4-a) and the formula (DI-4-b), R ^{20 is} independently -H or -CH ₃ ; in the formula (DI-2) to the formula (DI-7), the bonding position is not fixed at The group on any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; moreover, the bonding position of -NH ₂ on the cyclohexane ring or the benzene ring is other than the bonding position of G ²¹ or G ²² . Arbitrary location; In the formula (DI-8), R ²¹ and R ^{22 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group; and G ^{23 is} independently an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group. Phenyl is extended; n is an integer from 1 to 10; in the formula (DI-9), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl; p is independently 0. An integer of ~3; q is an integer from 0 to 4; in the formula (DI-10), R ²⁴ is -H, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a benzyl group; in the formula (DI-11) , G ²⁴ is -CH ₂ - or -NH-; in the formula (DI-12), G ²⁵ is a single bond, an alkylene group having 2 to 6 carbon atoms or a 1,4-phenylene group; r is 0 or 1 In the formula (DI-12), the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; further, the formula (DI-9), the formula (DI-11) In the formula (DI-12), the binding position of -NH ₂ bonded to the benzene ring is an arbitrary position; In the formula (DI-13), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O- , -OCF ₂ -, or -(CH ₂ ) _m' -, m' is an integer from 1 to 12; R ²⁵ is an alkyl group having 3 to 20 carbon atoms, a phenyl group, a group having a steroid skeleton, or A group represented by the formula (DI-13-a) in which any -H may be substituted by -F, and any -CH ₂ - may be -O-, -CH=CH- or -C≡C Substituting -H of the phenyl group may be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 20 carbon atoms, or a carbon number of 3 to 20 Substituted by an alkoxy group, the -H of the cyclohexyl group may be substituted by an alkyl group having 3 to 20 carbon atoms or an alkoxy group having 3 to 20 carbon atoms, and the bonding position of -NH ₂ bonded to the benzene ring is represented by Any position in the ring; In the formula (DI-13-a), G ²⁷ , G ²⁸ and G ²⁹ represent a bonding group, and these are independently a single bond or an alkylene group having 1 to 12 carbon atoms, and one or more of the alkylene groups are - CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-; ring B ²¹ , ring B ²² , ring B ²³ , and ring B ^{24 are} independently 1,4-stretched Phenyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,4- Diyl, naphthalene-1,5-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or fluoren-9,10-diyl; ring B ²¹ , ring B ²² , ring B ²³ , and ring B ²⁴ , any -H may be substituted by -F or -CH ₃ ; s, t and u are independently integers of 0~2, the total of these is 1~5; when s, t or u is 2 When the two binding groups in each parenthesis may be the same or different, the two rings may be the same or different; R ²⁶ is -F, -OH, an alkyl group having 1 to 30 carbon atoms, and a carbon number of 1 to 30. Fluorine-substituted alkyl group, alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , any -CH ₂ - of the alkyl group having 1 to 30 carbon atoms Substituted by a divalent group represented by the following formula (DI-13-b); In the formula (DI-13-b), R ²⁷ and R ^{28 are} independently an alkyl group having 1 to 3 carbon atoms; and v is an integer of 1 to 6; In formula (DI-14) and formula (DI-15), G ^{30 is} independently a single bond, -CO- or -CH ₂ -; R ^{29 is} independently -H or -CH ₃ ; R ³⁰ is -H, carbon number An alkyl group of 1 to 20 or an alkenyl group having 2 to 20 carbon atoms; one -H of the benzene ring in the formula (DI-15) may be substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group; 14) and in the formula (DI-15), the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; -NH ₂ bonded to the benzene ring means Any combination of positions on the ring; In the formula (DI-16) and the formula (DI-17), G ^{31 is} independently -O- or an alkylene group having 1 to 6 carbon atoms; G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms; ³¹ is -H or an alkyl group having 1 to 20 carbon atoms, and any -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-; R ³² is a carbon number of 6~ An alkyl group of 22; R ³³ is -H or an alkyl group having 1 to 22 carbon atoms; ring B ²⁵ is a 1,4-phenylene group or a 1,4-cyclohexylene group; r is 0 or 1; and is bonded to benzene. -NH ₂ on the ring means that the bonding position on the ring is arbitrary.

如申請專利範圍第1項所述的聚醯胺酸或其衍生物，其中：所述二醯肼為選自下述式(2-a-1)~式(2-a-2)、式(2-b-1)~式(2-b-3)或式(2-c-1)~式(2-c-6)中的至少1種二醯肼，式(2-a-2)中，m為1~12的整數。 The poly-proline or a derivative thereof according to the first aspect of the invention, wherein the diterpene is selected from the group consisting of the following formula (2-a-1) to (2-a-2), (2-b-1)~ at least one of the formula (2-b-3) or the formula (2-c-1) to the formula (2-c-6), In the formula (2-a-2), m is an integer of 1 to 12.

如申請專利範圍第1項所述的聚醯胺酸或其衍生物，其中：所述二胺含有選自下述式(DI-19-1)~式(DI-19-9)中的至少1種感光性二胺， The poly-proline or a derivative thereof according to claim 1, wherein the diamine contains at least one selected from the group consisting of the following formula (DI-19-1) to (DI-19-9) 1 photosensitive diamine,

如申請專利範圍第1項至第7項中任一項所述的聚醯胺酸或其衍生物，其中：所述二胺含有選自由下述式(DI-1-3)、式(DI-1-4)、式(DI-4-1)、式(DI-5-1)、式(DI-5-5)、式(DI-5-9)、式(DI-5-12)、式(DI-5-21)、式(DI-5-28)、式(DI-5-30)、式(DI-5-31)、式(DI-7-3)、式(DI-9-1)、式(DI-13-4)、式(DI-13-5)、式(DI-13-47)、式(DI-16-1)、式(DI-16-2)、式(DI-16-4)、式(DI-19-1)、式(2-a-1)、式(2-a-2)、式(2-b-1)或式(2-b-2)所組成的群組中的至少1種，式(DI-5-1)、式(DI-5-12)、式(DI-7-3)及式(2-a-2)中，m為1~12的整數；式(DI-5-30)中，k為1~5的整數；式(DI-7-3)中，n為1或2；式(DI-13-4)及式(DI-13-5)中，R³⁵為碳數1~30的烷基或碳數1~30的烷氧基；式(DI-16-1)及式(DI-16-2)中，R⁴⁰為-H或碳數1~20的烷基；式(DI-16-4)中，R⁴¹為-H或碳數1~12的烷基。 The poly-proline or a derivative thereof according to any one of claims 1 to 7, wherein the diamine contains a compound selected from the following formula (DI-1-3), formula (DI) -1-4), formula (DI-4-1), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12) , formula (DI-5-21), formula (DI-5-28), formula (DI-5-30), formula (DI-5-31), formula (DI-7-3), formula (DI- 9-1), formula (DI-13-4), formula (DI-13-5), formula (DI-13-47), formula (DI-16-1), formula (DI-16-2), Formula (DI-16-4), formula (DI-19-1), formula (2-a-1), formula (2-a-2), formula (2-b-1) or formula (2-b) -2) at least one of the group consisting of In the formula (DI-5-1), the formula (DI-5-12), the formula (DI-7-3), and the formula (2-a-2), m is an integer of 1 to 12; In -30), k is an integer of 1 to 5; in the formula (DI-7-3), n is 1 or 2; in the formula (DI-13-4) and the formula (DI-13-5), R ³⁵ It is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms; in the formula (DI-16-1) and the formula (DI-16-2), R ⁴⁰ is -H or a carbon number of 1 to 20 In the formula (DI-16-4), R ⁴¹ is -H or an alkyl group having 1 to 12 carbon atoms.

一種液晶配向劑，其特徵在於：包括如申請專利範圍第1項至第8項中任一項所述的聚醯胺酸或其衍生物。 A liquid crystal alignment agent comprising the poly-proline or a derivative thereof according to any one of claims 1 to 8.

如申請專利範圍第9項所述的液晶配向劑，其中：更包括選自包含烯基取代納迪克醯亞胺化合物、具有自由基聚合性不飽和雙鍵的化合物、噁嗪化合物、噁唑啉化合物、及環氧化合物的化合物的群組中的至少1種。 The liquid crystal alignment agent according to claim 9, which further comprises a compound selected from the group consisting of an alkenyl-substituted nadic ylidene compound, a radical polymerizable unsaturated double bond, an oxazine compound, and an oxazoline. At least one of the group of the compound and the compound of the epoxy compound.

如申請專利範圍第10項所述的液晶配向劑，其中：所述烯基取代納迪克醯亞胺化合物為選自包含雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)苯基}甲烷、N,N'-間苯二甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)、及N,N'-六亞甲基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺)的化合物的群組中的至少1種。 The liquid crystal alignment agent according to claim 10, wherein the alkenyl-substituted nadicilide compound is selected from the group consisting of bis{4-(allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinhomine)phenyl}methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl In the group of compounds of quinone imine) and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine) At least one.

如申請專利範圍第10項所述的液晶配向劑，其中：所述具有自由基聚合性不飽和雙鍵的化合物為選自包含N,N’-伸乙基雙丙烯醯胺、N,N’-(1,2-二羥基伸乙基)雙丙烯醯胺、伸乙基雙丙烯酸酯、及4,4’-亞甲基雙(N,N-二羥基伸乙基丙烯酸酯苯胺)的化合物的群組中的至少1種。 The liquid crystal alignment agent according to claim 10, wherein the compound having a radical polymerizable unsaturated double bond is selected from the group consisting of N, N'-extended ethyl bis acrylamide, N, N' -(1,2-dihydroxyethylidene)bisacrylamide, ethylidene diacrylate, and 4,4'-methylenebis(N,N-dihydroxyethyl acrylate) At least one of the groups of the compounds.

如申請專利範圍第10項所述的液晶配向劑，其中：所述環氧化合物為選自包含N,N,N',N'-四縮水甘油基-間二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N',N'-四縮水甘油基-4,4'-二胺基二苯基甲烷、2-[4-(2,3-環氧基丙氧基)苯基]-2-[4-[1,1-雙[4-([2,3-環氧基丙氧基]苯基)]乙基]苯基]丙烷、3,4-環氧基環己烯基甲基-3',4'-環氧基環己烯羧酸酯、N-苯基順丁烯二醯亞胺-甲基丙烯酸縮水甘油酯共聚物、及2-(3,4-環氧基環己基)乙基三甲氧基矽烷的化合物的群組中的至少1種。 The liquid crystal alignment agent according to claim 10, wherein the epoxy compound is selected from the group consisting of N, N, N', N'-tetraglycidyl-m-xylene diamine, 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2-[ 4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]B Phenyl]propane, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, N-phenylbutyleneimine-A At least one of the group of the glycidyl acrylate copolymer and the compound of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

一種液晶配向膜，其特徵在於：由如申請專利範圍第9項至第13項中任一項所述的液晶配向劑形成。 A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 9 to 13.

一種光配向用液晶配向膜，其特徵在於：對由如申請專利範圍第9項至第13項中任一項所述的液晶配向劑形成的液晶配向膜照射偏光紫外線而獲得。 A liquid crystal alignment film for photoalignment, which is obtained by irradiating a liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of claims 9 to 13 to a polarized ultraviolet ray.

一種光配向用液晶配向膜，其特徵在於：經過如下的步驟而形成：將如申請專利範圍第9項至第13項中任一項所述的液晶配向劑塗布在基板上的步驟、對塗布有配向劑的基板進行加熱乾燥的步驟、以及對膜照射偏光紫外線的步驟。 A liquid crystal alignment film for photoalignment, which is formed by the step of coating a liquid crystal alignment agent according to any one of claims 9 to 13 on a substrate, and coating the same. The step of heating and drying the substrate having the alignment agent and the step of irradiating the film with polarized ultraviolet rays.

一種光配向用液晶配向膜，其特徵在於：經過如下的步驟而形成：將如申請專利範圍第9項至第13項中任一項所述的液晶配向劑塗布在基板上的步驟、對塗布有配向劑的基板進行加熱乾燥的步驟、對經乾燥的膜照射偏光紫外線的步驟、以及繼而對所述膜進行加熱煅燒的步驟。 A liquid crystal alignment film for photoalignment, which is formed by the step of coating a liquid crystal alignment agent according to any one of claims 9 to 13 on a substrate, and coating the same. a step of heating and drying the substrate with the alignment agent, a step of irradiating the dried film with polarized ultraviolet rays, and then The film is subjected to a step of heating and calcining.

一種光配向用液晶配向膜，其特徵在於：經過如下的步驟而形成：將如申請專利範圍第9項至第13項中任一項所述的液晶配向劑塗布在基板上的步驟、對塗布有配向劑的基板進行加熱乾燥的步驟、對經乾燥的膜進行加熱煅燒的步驟、以及繼而對所述膜照射偏光紫外線的步驟。 A liquid crystal alignment film for photoalignment, which is formed by the step of coating a liquid crystal alignment agent according to any one of claims 9 to 13 on a substrate, and coating the same. The step of heating and drying the substrate having the alignment agent, the step of heating and calcining the dried film, and the step of irradiating the film with polarized ultraviolet rays.

一種液晶顯示元件，其特徵在於：包括如申請專利範圍第14項至第18項中任一項所述的液晶配向膜。 A liquid crystal display element comprising the liquid crystal alignment film according to any one of claims 14 to 18.