TW201239069A

TW201239069A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

Info

Publication number: TW201239069A
Application number: TW101108996A
Authority: TW
Inventors: Yoshikazu Miyamoto; Kouji Kashishita; Toshiyuki Akiike; Hiroaki Tokuhisa
Original assignee: Jsr Corp
Priority date: 2011-03-17
Filing date: 2012-03-16
Publication date: 2012-10-01
Also published as: CN102676179A; JP6102997B2; CN104560061A; JP2012208471A; KR20170117926A; TWI600750B; TWI529240B; JP2016001328A; KR20120106588A; KR101873248B1; TW201544581A; JP5994257B2; CN102676179B; KR101861185B1; CN104560061B

Abstract

The present invention is providing a liquid crystal alignment agent, which could prepare a liquid crystal display element capable of fast response with superior voltage retention rate, afterimage characteristics and light resistance, and excellent in coating uniformity. The liquid crystal alignment agent contains polymer [A], which is at least one selected from a group including polyamic acid, polyimide, methacrylic polymer, polysiloxane and polyamic acid ester. Furthermore, the polymer is having a group represented by the following formula (1), wherein R3 is preferred a group represented by the following formula (2).

Description

201239069 六、發明說明：【發明所屬之技術領域】液晶配向膜以及液晶顯本發明係關於液晶配向劑示元件。【先前技術】近年，液晶顯示元杜心# 几件由於具有消耗電力小、容易於小型化以及平坦化等優、便^，因此適用於從移動電話等的小型液晶顯示裝置到液a番曰日電視等的大螢幕液晶顯示裝置的廣泛用途。根據液晶分子的gp h fr丨、一 ° (排列）狀態的變化，作為液晶顯示裝置的驅動模式已知有TN(扭曲向列)、STN(超扭曲向列）、IPS(面内切換型）、VA(垂直配向）等。另外，在 VA模式中為了藉由配向分割使能見角提高，而採用 MVA(多域垂直配向）方式、pvA(圖型化垂直配向）方式，為了進-步使高速回應性、面板開口率提高，並且賦予液晶預傾肖’正在研討採用光垂直配向方式、psA(聚合物穩定配向)方式等。在此等中的任一個驅動模式中，液晶分子的配向狀態都被液晶配向膜直接控制，液晶配向膜在液晶顯示元件的功能特性的表現和控制方面擔負著相當大的份量。 ' 由於期待此般液晶顯示裝置作為移動電話或液晶電視等的動態晝面顯示用裝置’因此作為液晶顯示元件所被要求的特性，應該既流暢地顯示動態晝面又儘量抑制殘影’要求電光學效果之回應時間的更進一步的高速化。對於此要求，有報告對液晶配向膜所使用的聚合物 -4- 201239069 側鏈賦予提供介電各向導性的結構而圖謀改善之技術 (參照曰本特表2007_52 1361號公報以及曰本特表 2 0 0 7 - 5 2 1 5 0 6號公報）。然而，該專利文獻中除了電光學回應時間的高速化以外，關於在實用方面上重要的電壓保持率、殘影特性等電特性完全沒有記載。考慮到這樣的狀況，期望開發出一種液晶配向劑，其一方面實現液晶元件的高速回應，並可製作電壓保持率等諸性能優異的液晶顯示元件。先前技術文獻專利文獻專利文獻1曰本特表2007-52 1 36 1號公報專利文獻2 日本特表2007-521 506號公報【發明内容】發明要解決的課題本發明係基於如以上的情形而進行，其目的在於提供可製作可高速回應且電壓保持率、殘影特性以及耐光性優異的液晶顯不元件，並且均勻塗布性亦優異之液晶配向劑。用於解決問題的方案為了解決上述課題而進行之發明為一種液晶配向劑，其含有[A]選自包含聚醯胺酸、聚醯亞胺、（甲基）丙烯酸聚合物、聚矽氧烷以及聚醯胺酸酯之群組中的至少 1種聚合物（以下也稱為“[A]聚合物”），且上述聚合物具有以下述式（1)表示的基團。 201239069 R3-(R2^R1_ (1) (式（1)中，R丨為亞曱基、碳數為2 3 U的伸烷基、 -(CbH2bO)c-、伸苯基或伸環己基。b為〇 ^ 馬0〜20的整數。c 為0〜10的整數。並且這些基團的氫原子可被取代。 “子的-部分或全部 R2為包含碳-碳雙鍵、碳-碳三鍵、胺鍵的連結基。 #鍵、酿鍵或醢 R3為至少具有兩個單環結構的基團。 a為0或1的整數。）由於該液晶配向劑含有具有以上 _ 定結構之基團的[A]聚合物，而 X (1)表示的特由於ili各的撰摆母ώ a 員兄阿迷回應。另外’ 由於適田的選擇選自包含聚合物主鏈姓酸、聚醯亞胺、（？基)丙稀酸聚合物:。毒不同的聚酿胺醯胺酸酯之群組中的至少丨種聚八物A矽氧烷以及聚示元件所希望的特性（電壓保持賦予液晶顯性、耐光性）。汊〜特性、均勻塗布上述R3較佳為以下述式⑺所表示之基團。 (十»〜（2) (式⑺中HR6各自獨立地萘基、伸環己基、雙伸環己A "伸聯本基、且此等基團的氫原子的w環己基伸苯基或雜環。二風原子的一部分或全部可被取代。為已亞甲基、碳數A ) 鍵、舻# 1 為2〜10的伸烷基、碳-碳雙連結基的氯原子的部的連結基。並且上述 1刀一飞王部可被取代。 -6 * 201239069 R為氫原子、氰基、氟原子、三氟曱基、烷氧基羰基、烧基、烷氧基、三氟甲氧基或烷基羰氧基。 b為0或卜<:為1〜9的整數。其中，R7為複數的情形’複數個R7可以相同也可不同。）透過導入以上述式（2)表示的結構作為[A]聚合物的側鏈，可更加提高所獲得之液晶配向元件的回應速度。本發明適合包括由該液晶配向劑形成的液晶配向膜及具備該液晶配向膜的液晶顯示元件《如上述’根據該液晶配向劑’由於可製作出：可高速回應且電壓保持率、殘影特性、均勻塗布性、耐光性等諸性能優異的液晶顯示元件，因此該液晶顯示元件也町適合用於TN、STN ' IPS、FFS、Ht-VA(VA-IPS)、VA(包括 MVA、PVA、光垂直配向、PSA等方式）等驅動模式。發明的效果根據本發明可提供一種液晶配向劑，其可製作出可高速響應且電壓保持率、殘影特性、耐光性等諸性能優異的液晶顯示元件’且均勻塗布性也優異。因此，該液晶顯示元件可適宜適用於 TN、STN、IPS、FFS、 Ht-VA(VA-IPS)、VA(包括 MVA、PVA、光垂直配向、PSA 等方式）等驅動模式。【實施方式】 <液晶配向劑> 本發明的液晶配向劑含有[A]聚合物。另外，該液晶配向劑可在不損害本發明的效果的範圍含有其他任意成分。以下詳述各成分。 201239069 < [A]聚合物> [A]聚合物含有選自勺人基）丙烯酸聚合物、聚矽匕3聚醯胺酸、聚醯亞胺、（甲至少1種聚合物，且h貌以及聚酿胺酸酿之群組中的上述聚合物且右w u 基團。該液晶配向劑透過人 /、述式（1)表示的定結構之基團的[A〗聚八有具有以上述式（1)表示的特透過適宜選擇選自包八頁兄阿逮回應。另外， 3眾·合物主鐘έ士播了 η 酸、聚醯亞胺、（^发、域、，°構不同的聚醯胺 ^暴）丙烯酸聚合物、醯胺酸酯之群組中的m 聚石夕氧烷以及聚 J主y 1種帶示元件所希望的特性 σ ，可賦予液晶顯性、耐光性）。以下 2保料、殘影特性 '均句塗布各聚合物。 W34 mu⑴表示的基團、 [以式（1)表示的基團] -(CbH2b.、伸苯 '數：2〜3。的伸烧基、〜IT衣〇暴。b為〇〜20沾敕杳々。。為〇〜1〇的整數。並且這些巧20的H c 可被取代。〜含碳:碳雙：=:的鍵部鍵或醒胺鍵的連結基。建、鍵鍵、酉旨團。a為〇或】的整數。 ^有兩個早環結構的基作為由上述R2表示的連沾其 ^ ^ 酿胺基。的連、，。基，权佳為喊基、醋基、 =上述R、表示的碳數為2〜則伸烧基，例如可列舉出：伸乙基、伸丙基 L . w T 丁基、伸戊基、伸己基、伸辛基、伸壬基丞狎十一烷基、伸十二烷基、伸十四烷基、伸十六桉美、抽卞、坑基伸十八烷基、伸十九烷基、 -8 - 基 201239069 伸一十烧基、伸二十一烧基、伸二十二烧基、伸二十四烧基、伸二十五烧基、伸二伸一十七燒基、伸二十八烧基、伸二十九姨烷基等。，作為上述R3所表示的至少具有兩個單團’較佳為以上述式（2)表示的基團。透過導 (2)表示的結構作為[A]聚合物的側鏈，可更得之液晶配向元件的回應速度。上述式（2)中，R4及R6各自獨立地為伸苯基、萘基、伸環己基、雙伸環己基、伸環或雜環。並且這些基團的氫原子的一部分或代。R5為包含亞曱基、碳數為2〜1〇的伸烷鍵、奴-¾二鍵、醚鍵、酯鍵或雜環的連結基連結基的氫原子的一部分或全部可被取^ :亂基a原子、三氟甲基、烷氧基羰基氧基、三氟甲氧基或烷基羰氧的整數。其令，R7 馬υ a R為複數的情形，複數個f 可不同。又，在本說明書中中。工述奈基等稠環作為上述R4及R6所裊+ ^ —π 4 所表不的雜環，例如啶ί哀、嗒听環、衣例戈201239069 VI. Description of the Invention: [Technical Field of the Invention] Liquid crystal alignment film and liquid crystal display The present invention relates to a liquid crystal alignment agent. [Prior Art] In recent years, liquid crystal display elements have been used for small liquid crystal display devices such as mobile phones, etc., because they have low power consumption, are easy to be miniaturized, and are flattened. A wide range of uses for large-screen liquid crystal display devices such as Japanese TV. TN (twisted nematic), STN (super twisted nematic), and IPS (in-plane switching type) are known as driving modes of liquid crystal display devices according to changes in gp h fr丨 and one-degree (arrangement) state of liquid crystal molecules. , VA (vertical alignment), etc. In addition, in the VA mode, the MVA (Multi-Domain Vertical Alignment) method and the pvA (Picture Vertical Alignment) method are used to improve the high-speed response and the panel aperture ratio in order to improve the viewing angle by the alignment division. In addition, the liquid crystal pre-shaping method is being studied, and the optical vertical alignment method, the psA (polymer stable alignment) method, and the like are being studied. In any of these driving modes, the alignment state of the liquid crystal molecules is directly controlled by the liquid crystal alignment film, and the liquid crystal alignment film plays a considerable role in the performance and control of the functional characteristics of the liquid crystal display element. Since the liquid crystal display device is expected to be a dynamic kneading display device such as a mobile phone or a liquid crystal television, it is required to be a liquid crystal display element, and it is necessary to smoothly display the dynamic surface and suppress the residual image as much as possible. The response time of the optical effect is further increased. In response to this request, there is a report on the technique of providing a dielectric-instructive structure to the polymer -4-201239069 side chain used for the liquid crystal alignment film (see 曰本特表2007_52 1361号 and 曰本特表) 2 0 0 7 - 5 2 1 5 0 6). However, in this patent document, in addition to the increase in the electro-optical response time, electrical characteristics such as voltage holding ratio and afterimage characteristics which are important in practical use are not described at all. In view of such a situation, it has been desired to develop a liquid crystal alignment agent which realizes high-speed response of a liquid crystal element and can produce liquid crystal display elements excellent in performance such as voltage holding ratio. PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PRIOR ART In order to provide a liquid crystal alignment agent which can produce a liquid crystal display element which is excellent in voltage retention, image retention, and light resistance with high speed response and excellent uniform coating property. Solution to Problem The invention for solving the above problems is a liquid crystal alignment agent containing [A] selected from the group consisting of polyamic acid, polyimine, (meth)acrylic acid polymer, polyoxyalkylene oxide. And at least one polymer (hereinafter also referred to as "[A] polymer") in the group of polyphthalamides, and the above polymer has a group represented by the following formula (1). 201239069 R3-(R2^R1_ (1) (In the formula (1), R丨 is an anthracene group, an alkylene group having a carbon number of 2 3 U, -(CbH2bO)c-, a phenylene group or a cyclohexyl group. b is an integer of 0^ horse 0 to 20. c is an integer of 0 to 10. And the hydrogen atom of these groups may be substituted. "Part-part or all of R2 is a carbon-carbon double bond, carbon-carbon three A bond of a bond or an amine bond. The # bond, the tie bond or the oxime R3 is a group having at least two single ring structures. a is an integer of 0 or 1.) Since the liquid crystal alignment agent contains a group having the above structure The [A] polymer of the group, and the X (1) expressed by the ili each of the singer's mother ώ a member of the brother A fans responded. In addition, because the choice of the field is selected from the polymer main chain name acid, poly Imine, (?) acrylic acid polymer: at least bismuth polyoxane A oxane in groups of toxic different polyamine amine phthalate and desired properties of the concentrating element (voltage retention) It is preferable to apply the above-mentioned R3 to the group represented by the following formula (7). (10) to (2) (in the formula (7), each of the HR6 groups independently has a naphthyl group and a ring-extension ring. already And a double-stranded ring A " a phenyl group or a heterocyclic ring of a hydrogen atom of such a group, and a part or all of a dipole atom may be substituted. The number A) bond and 舻#1 are a linking group of a part of a chlorine atom of an alkylene group or a carbon-carbon double linking group of 2 to 10, and the above-mentioned one-knife-one-flying part can be substituted. -6 * 201239069 R is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, a alkyl group, an alkoxy group, a trifluoromethoxy group or an alkylcarbonyloxy group. b is 0 or a <: 1 to 9 In the case where R7 is a complex number, the plural R7s may be the same or different.) By introducing the structure represented by the above formula (2) as the side chain of the [A] polymer, the obtained liquid crystal alignment can be further improved. The response speed of the component is suitable for the liquid crystal alignment film formed of the liquid crystal alignment agent and the liquid crystal display element having the liquid crystal alignment film, as described above, according to the liquid crystal alignment agent, which can be manufactured: high-speed response and voltage retention Liquid crystal display with excellent properties such as rate, afterimage characteristics, uniform coating properties, and light resistance Therefore, the liquid crystal display element is suitable for driving modes such as TN, STN 'IPS, FFS, Ht-VA (VA-IPS), VA (including MVA, PVA, optical vertical alignment, PSA, etc.). According to the present invention, it is possible to provide a liquid crystal display element which is excellent in various properties such as high-speed response, voltage holding ratio, image sticking property, and light resistance, and is excellent in uniform coating property. Therefore, the liquid crystal display is excellent. The components can be suitably applied to driving modes such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), VA (including MVA, PVA, optical vertical alignment, PSA, etc.). [Embodiment] <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains [A] a polymer. Further, the liquid crystal alignment agent may contain other optional components insofar as the effects of the present invention are not impaired. Each component is detailed below. 201239069 < [A] polymer> [A] polymer containing acrylic acid polymer selected from the group consisting of scoop, poly(poly) phthalic acid, polyimine, (at least 1 polymer, and h And the above-mentioned polymer and the right wu group in the group of the polyamic acid-brewed group. The liquid crystal alignment agent is passed through the group of the structure of the formula (1) represented by the formula (1) The special transmissive expression expressed by the above formula (1) is selected from the package of the eight-page brother A-catch. In addition, the three common singer Zhong Yushi broadcasts η acid, polyimine, (^ hair, domain, ° Different properties of polyacrylamide, acrylic polymer, m-polyoxane in the group of phthalate groups, and the desired characteristic σ of the poly-J main y 1 type of display element can impart liquid crystal dominantness, Light fastness). The following 2 materials and image retention characteristics are applied to each polymer. W34 mu (1) represents a group, [group represented by formula (1)] - (CbH2b., benzene) number: 2 to 3. The extension base, ~IT clothing 。。. b is 〇 ~ 20 敕杳々〇整数〇〇〇〇。。。。。。。。〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇。。。 The group is a whole number of 〇 or ]. ^The group having two early ring structures is the hydrazine group, which is represented by the above R2. =, the above R, the carbon number is 2 to extend the alkyl group, for example, exoethyl, propyl L. w T butyl, pentyl, hexyl, octyl, thiol丞狎11-decyl, extended dodecyl, tetradecyl, hexadecane, convulsion, pit-based octadecyl, hexadecyl, -8-yl 201239069 Base, stretch twenty-one base, stretch twenty-two base, stretch twenty-four base, stretch twenty-five base, stretch two stretch seventeen base, stretch twenty-eight base, stretch twenty-nine Alkyl group, etc., as represented by the above R3, having at least two orders The group ' is preferably a group represented by the above formula (2). The structure represented by the conduction (2) serves as a side chain of the [A] polymer, and the response speed of the liquid crystal alignment element can be obtained. Wherein R 4 and R 6 are each independently a phenylene group, a naphthyl group, a cyclohexylene group, a dicyclohexyl group, a stretched ring or a heterocyclic ring, and a part or a plurality of hydrogen atoms of these groups. R 5 is an anthracene group. A part or all of a hydrogen atom having a carbon number of 2 to 1 Å of an alkylene bond, a sulphate - a double bond, an ether bond, an ester bond or a heterocyclic linker may be taken. An integer of a methyl group, an alkoxycarbonyloxy group, a trifluoromethoxy group or an alkylcarbonyloxy group. In the case where R7 is a plural, a plurality of f may be different. Further, in the present specification. A fused ring such as a naphthyl group as a heterocyclic ring represented by the above R4 and R6 袅 + ^ - π 4 , such as a pyridine, a hearing ring, a clothing case

S啶衣專。作為包含卜沭R 5 數為2〜1〇的伸ρ 3上述R …m 中的碳數為2〜10 例如可列舉出伸？ w 山丨r乙基、伸丙基、基、伸辛其楚彳申丁基、伸丞伸辛基專。作為上述r5 出吡啶環、。又啤不的雜J衣，。呀環、嘧啶環耸^ A 1 1 衣寺。作為R7戶/t表、伸二十三十六烧基、基、伸三十環結構的基入以上述式加提高所獲苯基、伸聯己基伸苯基全部可被取 I、碳-碳雙。並且上述 1 R7為氣原、烧基、烧 1 〇 c為1〜9 可以相同也包含於單環可列舉出吡所表示的碳的伸烧基，戊基、伸己例如可列舉示的烧氧基 201239069 幾基’例如可列舉出曱氧基羰基、乙氧基羰基、丙氧基幾基等。作為R7所表示的烷基，例如可列舉出甲基、乙基、丙基、正丁基、異丁基等碳數為1〜2〇的直鏈或支鏈狀的炫基等。作為R7所表示的烷氧基，例如可列舉出曱氧基乙氧基、丙氧基等。作為R7所表示的烷基羰氧基，例如列舉出甲氧基羰氧基、乙氧基羰氧基、丙氧基羰氧攸使用該液晶配向劑的液晶顯示元件之言觀點來看，作為上述R7，較、回應的】Μ ^ 住馮烷基，更較佳A炉 1〜20之直鏈狀的烷基。另外，上述R、R6 為娀個基團較佳為具有氟原子。、至少作為以上述式（2)表㈣基L可列式表示的基團等。出以下述 201239069S 衣 clothing special. The number of carbons in the above R ... m is 2 to 10, and the number of carbon atoms in the above R × m is 2 to 10, for example, w Hawthorn r ethyl, propyl, ketone, extension of Xinqi Chu 彳丁基 butyl, stretch 丞辛基专. As the above r5, a pyridine ring is obtained. Also, the beer is not mixed with J clothes. Ah ring, pyrimidine ring tower ^ A 1 1 Yi Temple. As the R7 household / t table, the extension of the twenty-six-six-six-burning, base, and extension of the 30-ring structure, the above formula can be used to increase the obtained phenyl group, and the extended phenyl group can be taken as I, carbon- Carbon double. Further, the above-mentioned 1 R7 is a gas atom, a burnt group, and a burnt 1 〇c is 1 to 9. The same may be included in the monocyclic ring, and examples thereof include a carbon-based stretching group represented by pyridyl, and examples of the pentyl group and the exogenous group may be calcined. Examples of the oxy group 201239069 aryl group include a decyloxycarbonyl group, an ethoxycarbonyl group, a propoxy group, and the like. The alkyl group represented by R7 may, for example, be a linear or branched thio group having a carbon number of 1 to 2 Å such as a methyl group, an ethyl group, a propyl group, an n-butyl group or an isobutyl group. Examples of the alkoxy group represented by R7 include a decyloxyethoxy group and a propoxy group. The alkylcarbonyloxy group represented by R7 is, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group or a propoxycarbonyloxindole, which is a liquid crystal display device using the liquid crystal alignment agent. The above R7, relatively responsive to Μ ^ live von alkyl, more preferably a linear alkyl group of 1 to 20 in the furnace A. Further, it is preferred that the above R and R6 have a fluorine atom. At least, it is a group which can be represented by the formula (4) of the above formula (2). With the following 201239069

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(2-31) (2 - 32 ) (2-33) (2-34) (2-35)(2-31) (2 - 32 ) (2-33) (2-34) (2-35)

(2 - 30) -12- 201239069(2 - 30) -12- 201239069

-13- 201239069-13- 201239069

-14- 201239069-14- 201239069

(2-73)(2-73)

(2-74) F(2-74) F

-15- 201239069-15- 201239069

2-86) (2 -87) (2 · 88 )2-86) (2 -87) (2 · 88 )

(2 > 99 ) (2-100) (2-101) (2-102) (2-103)(2 > 99 ) (2-100) (2-101) (2-102) (2-103)

(2*104) (2-105) (2-107} (2106 )(2*104) (2-105) (2-107} (2106 )

106) 109) 110) 111 ) 118) 201239069106) 109) 110) 111 ) 118) 201239069

p铥# 认两咴数為院氧基。X各自獨立地P铥# recognizes two turns as the hospitaloxy. X independently

)中’ R8為碳數為U0 8也為虱原子或氟原子。作為上述R8，較枯％山為妷數為1〜20的烷基，更較佳為奴數為1〜10的烷基。作為以上述式（2)表甘 )衣不的基團，從使用了該液晶配向劑的液晶顯示元件之高速回應的觀點來看，較佳為以上述式（2-1)、式（2_4)、式（2-6)、式（2-41)、式（2-5 0)〜(2-6 0)、式（2-64)、式（2-65)〜（2-123)表示的基團，更較佳為如式 (2_41)、式（2-50)〜（2-58)、式（2-65)〜（2-123)之具有氟原子並且在末端具有烷基的基團、以式（2_72)表示的基及以式（2_90)表示的基團。 [^^酿胺酸] 作為[A]聚合物的聚醯胺酸’係藉由使四羧酸二酐與一 ^化合物進行反應而獲得。需要使上述二胺化合物的一部分為包含以上述式（1)表示之基團的二胺化合物。 201239069 作為四羧酸二酐，例如可列舉出脂肪族四羧酸二酐、脂環式四羧酸二酐、芳香族四羧酸二酐等。這些四羧酸二酐可單獨使用或組合兩種以上而使用。作為脂肪族四羧酸二酐，例如可列舉出丁烷四羧酸二針等。作為脂環式四羧酸二酐，例如可列舉出1，2,3,4-環丁烷四酸二酐、2,3,5-三羧基環戊基乙酸二酐、 1，3,3&，4,5,91)-六風-5-(四鼠-2,5-二氧-3-咬喃基）-奈并 [l，2-c]呋喃-1，3-二酮、l,3,3a,4,5,9b-六氫-8-曱基-5-(四氫-2,5-二氧-3-呋喃基）-萘并[l，2-c]呋喃-1,3-二酮、3-氧雜雙環[3.2.1]辛烷- 2,4-二酮-6-螺-3’-(四氫呋喃-2，，5’-二嗣）、5-(2,5-二氧四風-3 -0夫喃基）-3 -甲基-3 -環己稀-1,2-二羧酸酐、3,5,6-三羧基-2-羧甲基降莰烷-2:3,5:6-二酐、 2,4,6,8-四羧基雙環[3.3.0]辛烷-2:4,6:8-二酐、4,9-二氧雜三環[5.3· 1.02’6]十一烷- 3,5,8,10-四酮等。作為芳香族四羧酸二酐，例如可列舉出均苯四酸二酐等之外，還可列舉出曰本特願20 10-97 1 88號中記載的四缓酸二酐。這些四羧酸二酐之中，較佳為脂環式四羧酸二酐，更較佳為2,3,5-三羧基環戊基乙酸二酐、1,2,3,4-環丁烷四酸二酐。作為二胺化合物，例如可列舉出脂肪族二胺、脂環式二胺、二胺基有機矽氧烷、芳香族二胺等。這些二胺化合物可單獨使用或組合兩種以上而使用。 -18- 201239069 作為脂肪族二胺，例如可列舉出間二曱苯二胺' 1，3 -丙二胺、四亞甲基二胺、五亞甲基二胺、六亞甲基二胺等。作為脂環式二胺，例如可列舉出1，4 -二胺基環己烧、4,4’-亞甲基雙（環己胺）、丨，3_雙（胺基甲基）環己烷等。作為二胺基有機矽氧烷，除了可列舉出例如1,3 _雙 (3 -胺基丙基）_四甲基二石夕氧烧等之外，還可列舉出曰本特願2009-97 188號中記載的二胺。作為芳香族二胺，例如可列舉出：對苯二胺、4,4 ’ -二胺基二苯基甲烷、4，4，-二胺基二苯硫醚、1,5-二胺基萘、2,2，-二甲基- 4,4’-二胺基聯苯、4,4，-二胺基-2,2，-雙 (三氟曱基）聯苯、2,7-二胺基芴、4,4，-二胺基二苯基醚、 2,2-雙[4-(4-胺基苯氧基）苯基]丙烷、9,9-雙（4-胺基苯基）苟、2,2-雙[4-(4-胺基苯氧基）苯基]六氟丙烷、2,2-雙（4-胺基笨基）六氟丙烷、4,4，-(對苯基二亞異丙基）雙（苯胺）、4,4，-(間苯基二亞異丙基）雙（苯胺）、ι，4-雙（4-胺基苯氧基）苯、4,4，-雙（4-胺基苯氧基）聯苯、2,6-二胺基吼。定、3,4-二胺基吡啶、2,4-二胺基嘧啶、3,6-二胺基吖啶、 3，6_二胺基咔唑、N-曱基-3,6-二胺基咔唑、N-乙基- 3,6-二胺基咔唑、N-苯基-3,6-二胺基咔唑、N，N，-雙（4-胺基苯基）-聯苯胺、N，N，-雙（4-胺基苯基）-Ν,Ν，-二曱基聯笨胺、1，4·雙-(4-胺基苯基）-哌啡、3,5-二胺基苯甲酸、十 —烧氧基-2,4 -二胺基苯、十四烧氧基_2,4 -二胺基苯、十五烧氧基-2,4 -二胺基苯、十六院氧基-2,4 -二胺基苯、十八烷氧基-2,4-二胺基苯、十二烷氧基-2,5-二胺基苯、十 -19- 201239069 四烷氧基-2,5-二胺基苯、十五烷氧基-2,5-二胺基苯、十六烷氧基-2，5-二胺基苯、十八烷氧基-2,5-二胺基苯、膽甾烷氧基-3,5-二胺基苯、膽崔烯氧基-3，5-二胺基苯、膽 U烧氧基-2,4 -二胺基笨、膽留稀氧基-2,4-· —胺基本、3,5-二胺基苯甲酸膽留烧酯、3,5 -二胺基苯曱酸膽留烯酯、 3,5 -二胺基苯曱酸羊毛甾烧酯、3,6 -雙（4 -胺基苯甲醯氧基）膽甾烷、3,6-雙（4-胺基苯氧基）膽留烷、4-(4’-三氟甲氧基苯曱醯氡基）環己基-3,5_二胺基苯甲酸酯、4-(4，-三氟曱基苯曱酿氧基）環己基-3,5-二胺基苯甲酸酯、1,1-雙 (4-((胺基苯基）曱基）苯基）_4 丁基環己烷、151_雙（4_((胺基苯基）曱基）笨基）_4_庚基環己烷、込卜雙（4_((胺基苯氧基）甲基）苯基）-4_庚基環己烷、1，1-雙（4-((胺基苯基）甲基）苯基）-4-(4-庚基環己基）環己烷、2,扣二胺基_N，N_二烯丙基本胺、4-胺基苄胺、3_胺基苄胺、以下述式（3)表示的下述式（4)表示的化合物等。Wherein 'R8 is a carbon number of U0 8 which is also a halogen atom or a fluorine atom. As the above R8, an alkyl group having a number of turns of 1 to 20 is more preferred, and an alkyl group having a number of slaves of 1 to 10 is more preferable. As a group which is not coated with the above formula (2), from the viewpoint of high-speed response of the liquid crystal display element using the liquid crystal alignment agent, it is preferred to use the above formula (2-1) and formula (2_4). ), formula (2-6), formula (2-41), formula (2-5 0)~(2-6 0), formula (2-64), formula (2-65)~(2-123) The group represented by the formula (2_41), the formula (2-50) to (2-58), and the formula (2-65) to (2-123) have a fluorine atom and have an alkyl group at the terminal. a group represented by the formula (2-72) and a group represented by the formula (2-90). [^^Taolinic acid] The polylysine as the [A] polymer is obtained by reacting a tetracarboxylic dianhydride with a compound. It is necessary to make a part of the above diamine compound into a diamine compound containing a group represented by the above formula (1). 201239069 Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. These tetracarboxylic dianhydrides can be used singly or in combination of two or more. Examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic acid, two needles, and the like. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3&;,4,5,91)-Liufeng-5-(four-rat-2,5-dioxy-3-chitosan)-naphtho[l,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-mercapto-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[l,2-c]furan- 1,3-diketone, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2,,5'-dioxin), 5-( 2,5-Dioxytetrazol-3 -0-furanyl)-3-methyl-3-cyclohexan-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethyl Decalin-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-di Oxatricyclo[5.3.1.02'6]undecane-3,5,8,10-tetraketone, and the like. Examples of the aromatic tetracarboxylic dianhydride include, for example, pyromellitic dianhydride, and the tetrazoic acid dianhydride described in Japanese Patent Application No. 20 10-97 1 88. Among these tetracarboxylic dianhydrides, preferred are alicyclic tetracarboxylic dianhydrides, more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,3,4-cyclobutylene. Alkanetetracarboxylic dianhydride. The diamine compound may, for example, be an aliphatic diamine, an alicyclic diamine, a diamine organosiloxane or an aromatic diamine. These diamine compounds may be used singly or in combination of two or more. -18- 201239069 Examples of the aliphatic diamine include m-diphenylene diamine, 1,3 -propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like. . Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), anthracene, and 3-bis(aminomethyl)cyclohexane. Alkane, etc. Examples of the diamine-based organooxane include, for example, 1,3 -bis(3-aminopropyl)-tetramethyldiazepine, and the like. The diamine described in 97,188. Examples of the aromatic diamine include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4,-diaminodiphenyl sulfide, and 1,5-diaminonaphthalene. , 2,2,-dimethyl-4,4'-diaminobiphenyl, 4,4,-diamino-2,2,-bis(trifluoromethyl)biphenyl, 2,7-di Aminoguanidine, 4,4,-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminobenzene) Base, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4,- (p-phenyldiisopropylidene) bis(aniline), 4,4,-(m-phenyldiisopropylidene)bis(aniline), iota,bis(4-aminophenoxy)benzene 4,4,-bis(4-aminophenoxy)biphenyl, 2,6-diaminoguanidine. D,3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-mercapto-3,6-di Aminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N,-bis(4-aminophenyl)- Benzidine, N,N,-bis(4-aminophenyl)-indole, indole,-dimercaptophenylamine, 1,4·bis-(4-aminophenyl)-piperone, 3, 5-diaminobenzoic acid, deca-oxyalkyl-2,4-diaminobenzene, tetradecyloxy 2,4-diaminobenzene, fifteen alkoxy-2,4-diamine Benzobenzene, hexadecanthoxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, ten- 19- 201239069 Tetraalkoxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecane Oxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholesteneoxy-3,5-diaminobenzene, biliary U alkoxy-2, 4-diamino stupid, cholestyloxy-2,4-·-amine basic, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid cholesteryl ester , 3,5-diaminobenzoic acid wool sizzling , 3,6-bis(4-aminobenzyloxy) cholestane, 3,6-bis(4-aminophenoxy)cholane, 4-(4'-trifluoromethoxy Benzoyl)cyclohexyl-3,5-diaminobenzoate, 4-(4,-trifluoromethylphenylphosphonium oxy)cyclohexyl-3,5-diaminobenzoic acid Ester, 1,1-bis(4-((aminophenyl)indenyl)phenyl)-4 butylcyclohexane, 151_bis(4-((aminophenyl)indolyl))) Heptylcyclohexane, bismuth (4_((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl))) Phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2, dimethylamino-N,N-diallylamine, 4-aminobenzylamine, 3-aminobenzylamine A compound represented by the following formula (4) represented by the following formula (3).

R10 (3) 化合物、以R10 (3) compound,

、R9及R9’’’各自獨立地為單鍵、 -。其中’ R9的氺為與二胺基苯基及R9的*為結合於伸苯基侧的 3的烧二基。d為〇或l°e為〇〜2 R1Q為直鏈狀、支鏈狀或環狀的烷 2個胺基較佳結合於2,4位或3,5 -20- 201239069R9 and R9'' are each independently a single bond, -. Wherein ’ of R9 is a dialkyl group bonded to the diaminophenyl group and R9 is bonded to the phenyl group side. d is 〇 or l°e is 〇~2 R1Q is a linear, branched or cyclic alkane. 2 amine groups are preferably bonded to 2, 4 or 3,5 -20- 201239069

上述式（4)中，R9、d以及e與上述式（3)同樣定義。 R1〜R3以及a與上述式（1)同樣定義。二胺基苯基中的2 個胺基較佳結合於2,4位或3,5位。g為1〜5的整數。關於上述R1〜R3,可直接適用上述[以式（1)表示的基團]中各個基團之定義的說明以及較佳之基團的說明。作為上述g，由使用了該液晶配向劑的液晶顯示元件之高速回應的觀點來看，較佳為1〜3，更較佳為2或3。作為以上述式（4)表示的二胺，例如可列舉出以下述式表示的二胺等。 -2 1- 201239069In the above formula (4), R9, d and e are as defined in the above formula (3). R1 to R3 and a are defined in the same manner as in the above formula (1). The two amine groups in the diaminophenyl group are preferably bonded to the 2, 4 or 3, 5 position. g is an integer of 1 to 5. With respect to the above R1 to R3, the description of the definition of each group in the above [group represented by the formula (1)] and the description of the preferred group can be directly applied. The above g is preferably from 1 to 3, more preferably 2 or 3 from the viewpoint of high-speed response of the liquid crystal display element using the liquid crystal alignment agent. The diamine represented by the above formula (4) is, for example, a diamine represented by the following formula. -2 1- 201239069

-22- 201239069 c3h7 C3H7 c3h7 C3H7-22- 201239069 c3h7 C3H7 c3h7 C3H7

oc2h4-oc2h4-OC2H4 O - C1 〇H 20 _ CO O - C2H 4 — O —|p 〇Oc2h4-oc2h4-OC2H4 O - C1 〇H 20 _ CO O - C2H 4 — O —|p 〇

NH 丨2NH 丨2

NH '2 〇_c10h20-coo-c2h4-o—、/)—nh5 h2n nh9 OC2H4-〇C2H4-〇C2H4-〇—ΙοNH '2 〇_c10h20-coo-c2h4-o-, /)-nh5 h2n nh9 OC2H4-〇C2H4-〇C2H4-〇-Ιο

NH 2 c7h15NH 2 c7h15

O-^0^)20-COO-〇2Η4~0O-^0^)20-COO-〇2Η4~0

nh2 C7H15Nh2 C7H15

〇 —Ci〇H2〇*COO~C2H4—O〇—Ci〇H2〇*COO~C2H4-O

nh2 h2nNh2 h2n

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h2nH2n

°'C1〇H2〇-〇—Nh2°'C1〇H2〇-〇-Nh2

、言此一八 H2N 況下"由二=擇酸作為[a]聚合物的情來看，至少需要使以式⑴表示之基團的；1式(4)表不的化合物等的具有為併用其他-胺的产，作為二胺中的1個。又，作化合物。—私的情況’較佳為使用以上述式⑺表示的胺化合物的使用九5成反應的四綾酸二酐與二 1當量，四鲮酸-’相對於二胺化合物中所含的胺基更較佳為0”：的酸野基較佳為0.2當量〜2當量， •田里〜1 ·2當量。 &成反應較估尤、較佳為-2〇。(：〜15()。溶劑中進行。作為反應溫度，間，較佳為〇,5 & B±更較佳為G°C ~10()°C。作為反應時、卞〜24小時’更較佳為2小時〜丨2小時。 -24- 201239069 作為有機溶劑，σ 有機溶劑則沒有特別;；在要疋可溶解所合成之聚醯胺酸的 …(ΝΜΡ)、Νν _ : ’例如可列舉出：Ν-甲基·2·°比 Ν Μ β ^ ,，—甲基乙醯胺、Ν，Ν-二甲基甲醯胺、 Ρ主 —甲基亞石風、γ -丁内醋、四甲基尿素、六甲基磷醯=脸、几〜一胺間甲酚、二甲苯酚、苯酚、鹵化本紛…二醇乙基甲基_等。作為有機办劑的用量’相對於四羧酸二酐以及二胺、合物的總量100質量份，較佳為0.1質量份〜50質量伤，更較佳為5質量份〜4〇質量份。 <反應後得到的聚醯胺酸溶液可直接供給於液晶配向齊J的製備’也可預先單離出反應溶液中所含的聚醯胺酸再供給於液晶配向劑的製備’也可先精製單離出的聚醢胺酸，再供給於液晶配向劑的製備。作為聚醯胺酸的單離方法’例如可列舉出：在減壓下乾燥透過將反應溶液注入大量的不良溶劑中而獲得的析出物之方法，利用蒸發器將反應溶液減壓蒸餾去除的方法等。作為聚醯胺酸的精製方法，可列舉出：再次將單離出的聚醯胺酸溶解於有機溶劑，並利用不良溶劑使其析出的方法，利用蒸發器進行1次或多次將有機溶劑等減壓蒸餾去除之步驟的方法。 [聚醯亞胺] 聚醯亞胺可藉由使上述聚醯胺酸所具有的醯胺酸結構脫水閉環’酿亞胺化而製造<»聚醯亞胺係可為使其前體的聚醯胺酸所具有之全部的醯胺酸結構脫水閉環的完全醯亞胺化物，亦可為僅使醯胺酸結構的一部分脫水閉環、醯胺酸結構和醯亞胺環結構並存的部分醯亞胺化物。 -25- 201239069 a众作為聚醯亞胺的合成方法，例如可列舉出：聚蟪 :馱的加熱方法(以下也稱為“方法⑴，，)，(⑴將聚醯胺峻冷解於有機溶劑，在此溶液中添加脫水劑以及脫水閉環催化J，根據需要進行加熱的方法（以下也稱為“方法 (11))等藉由聚醯胺酸的脫水閉環反應之方法。作為方法⑴中的反應溫度，較佳為50。(：〜200°C，更較佳為6(TC 〜17(rc。若反應溫度未滿5〇<>c，則無法充分 =行脫水閉環反應，而若反應溫度超過2〇(rc則獲得I 聚醯亞胺的分子量有時會降低。作為反應時間，較佳為 0.5小時〜48小時’更較佳為2小時〜2〇小時。在方法（i)中獲得的聚醯亞胺可直接供給於液晶配向劑的製備，也可預先單離出聚醯亞胺再供給於液晶配向劑的製備，或者預先精製單離出的聚醯亞胺或預先精製所獲彳于的聚醯亞胺再供給於液晶配向劑的製備。作為方法（U)中的脫水劑，例如可列舉出乙酸肝、丙西文if、二氟乙酸肝等酸酐。作為脫水劑的用量’根據所希望的醯亞胺化率來適虽地選擇’但是相對於聚醯胺酸的醯胺酸結構1莫耳，較佳為〇.〇1莫耳〜2〇莫耳。作為方法（ii)中的脫水閉環催化劑，例如可列舉出吼啶、柯林鹼、二甲吡啶、三乙胺等。作為脫水閉環催化劑的用量，相對於含有的脫水劑 1莫耳，較佳為0.01莫耳〜10莫耳。又，上述脫水劑以及脫水閉環劑的含量越多則可使醯亞胺化率越高。 -26- 201239069 作為方法（ii)中使用的有機溶劑，例 J例如可列舉出：與作為用於聚醯胺酸的合成者所例示之右心有機溶劑同樣的有機溶劑等。作為方法（11)中的反應溫度，較佳為〇。匚〜1 8 〇。匸，更較佳為HTC〜丨50。〇。作為反應時間，較佳為〇 5小時’〜2〇小時，更較…小時〜8小時。透過使反應條件為上述範圍，可使脫水閉環反應充分進行，另外可使所獲得的聚酿亞胺的分子量為恰當的分子量。在方法（Π)中可獲得含有聚醯亞胺的反應溶液。可直接將此反應溶液供給於液晶配向劑的製備，也可在從反應溶液中預先去除了脫水劑以及脫水閉環催化劑再供給於液晶配向劑的製備，也可預先單離出聚醯亞胺再供給於液晶配向劑的製備，或者預先精製了單離出的聚醯亞胺再供給於液晶配向劑的製備。作為從反應溶液去除脫水劑以及脫水閉環催化劑的方法，例如可列舉出溶劑置換的方法等。作為聚醯亞胺的單離方法以及精製方法，例如可列舉出：與作為聚醯胺酸的單離方法以及精製方法而例示者相同的方法等。 [(甲基）丙烯酸聚合物] 作為[A]聚合物的（甲基）丙烯酸聚合物，只要是包含以上述式（1)表示之基團的（曱基）丙烯酸聚合物則無特別限定，可藉由利用公知方法將習知的乙烯性不飽和化合物聚合而獲得。例如透過使（a)含環氧基的乙烯性不飽和化合物（以下也稱為“（a)不飽和化合物，，）和（bl)乙烯性不飽和羧酸和/或聚合性不飽和多元羧酸酐（以下也稱為 -27- 201239069 “（bl)不飽和化合物”）和除了不飽和化合物及（bl)不飽和化合物以外的聚合性不飽和化合物（以下也稱為“（b2) 不飽和化合物”）的共聚物進行聚合而獲得。作為（a)不飽和化合物’例如可列舉出：（甲基）丙烯酸縮水甘油酯、α-乙基丙稀酸縮水甘油酯、α_正丙基丙烯酸縮水甘油酯、α -正丁基丙烯酸縮水甘油酯、（甲基）丙烯酸3,4-環氧丁酯、α-乙基丙烯酸3，4-環氧丁酯、（甲基）丙烯酸6,7-環氧庚酯、α-乙基丙烯酸6,7-環氧庚酯等。作為（b 1)不飽和化合物，例如可列舉出：（曱基）丙烯酸、巴豆酸、α -乙基丙烯酸、α -正丙基丙稀酸、α -正丁基丙稀酸、馬來酸、富馬酸、檸康酸、中康酸、衣康酸等不飽和叛酸類；馬來酸酐、衣康酸針、檸康酸酐、川員式-1，2,3,4-四氫鄰笨二甲酸酐等不飽和多元羧酸酐類等。作為（b 2)不飽和化合物，例如可列舉出：具有以上述式（1)表示之基團的（曱基）丙烯酸酯，（曱基）丙烯酸2_ 鉍乙酯、（曱基）丙烯酸2-羥丙酯等具有（曱基）丙烯酸羥基的酯類；知(甲基）丙稀酸曱酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙酯、（曱基）丙烯酸正丁酯、 β基）丙稀酸異丁 §旨、（曱基）丙烯酸二級丁醋、（甲基）丙烯馱一級丁酿等（甲基）丙烯酸烷酯類；而祕（甲土）丙稀酉文&戊醋、（曱基）丙烯酸環己酯、（甲基）、酸2_甲基環己酿 ' (曱基）丙烯酸三環[S 2丄〇2,6]癸土酉曰（曱基）丙烯冑2·二環戊烧氧基乙S旨、（曱基）内 -28- 201239069 稀酸異冰片酯、（甲基）丙烯酸膽留烷酯等（甲基）丙烯酸脂環式酯類； (曱基）丙烯酸苯酯、（甲基）丙烯酸苄酯等（甲基）丙烯酸芳基酯類；馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等不飽和二羧酸二酯類； N-苯基馬來醯亞胺、N_节基馬來醯亞胺、N_環己基馬來醯亞胺、N-琥珀醯亞胺基-3 _馬來醯亞胺基苯甲酸 S曰、N-號轴酿亞胺基_4_馬來醯亞胺基丁酸酯、N_琥珀醯亞胺基-6-馬來醯亞胺基已酸酯、N_琥珀醯亞胺基·3_馬來醯亞胺基丙酸酯、Ν_(9_吖啶基）馬來醯亞胺等不飽和二羰基醯亞胺衍生物； (甲基）丙烯腈、α-氣丙烯腈、偏二氰乙烯等氰化乙烯基化合物； (甲基）丙烯醯胺、Ν，Ν-二曱基（甲基）丙烯醯胺等不飽和醯胺化合物；苯乙烯、ct-甲基笨乙烯、間甲基苯乙烯、對曱基苯乙烯、乙烯基曱苯、對甲氧基苯乙烯等芳香族乙烯基化合物；茚、1 -曱基茚等茚衍生物類； 1，3-丁二稀、異戊二烯、2,3•二甲基·υ•丁二燦等共軛二烯系化合物以外，氣乙烯、偏二氣乙烯、乙酸酯等。作為（a)不飽和化合物，軔祛盔罕乂佳為（甲基）丙烯酸縮水甘油酯，作為（b 1)不飽和化合物，鲂佔 m孕乂佳為（甲基）丙烯酸，作 -29- 201239069 為(b2)不飽和化合物，較佳為（甲基)丙烯酸膽崔烷醋。夢由自由基聚合而合成作為[A]聚合物的（甲基)丙稀心合物的情況下’由將以上述式⑴表示之基團導入聚合物中的觀點來看，至少需要使用具有以上述式⑴表示之團的不飽和化合物作為不飽和化合物中的丨 : 面，例如也可利用不具有以上述式物中的環氧基，藉由以往習知的二)=基團的聚合述式⑴表示的基團。的…反應而導入以上劑以酸聚合物的合成方法，…的溶來-成劑的存在下，例如藉由自由基聚合 =係為歧。作為有機溶劑，例如可列舉出：為用於聚醯胺酸的合成者而例 /、溶劑等。之有機洛劑相同的有機作為聚合反應起始劑，例如可列舉出： 2,2’-偶氮雙異丁腈、2,2，腈）、2,2，m(4_f Α _二甲基戊物，過氧化二甲基戊猜）等偶氮化合丁賴Λ t 過氧化月桂酿、過氧化新戊酸三級物，過氧m級丁基過氧化)環己烧等有機過氧化型起始劑等。這此令人…2和還原劑的氧化還原種以上而使用。反應起始劑可單獨使用或混合兩 [聚矽氧烷] 表示㈣彻’只要是包含以上述式⑴ 如下述：人：矽氧烷則無特別限定’但是例如可藉由而合成：將至少1種選自包含絲基錢化合物 -30-In the case of H2N under the condition of H2N, it is necessary to have at least a group represented by the formula (1), and a compound represented by the formula (4), etc. For the production of other -amines in combination, one of the diamines. Also, as a compound. In the case of a private one, it is preferred to use a tetradecanoic acid dianhydride having a reaction of the above-mentioned formula (7) and a tetradecanoic acid dianhydride having two equivalents, and a tetradecanoic acid-' relative to the amine group contained in the diamine compound. More preferably, the acid field group of 0": is preferably 0.2 equivalents to 2 equivalents, and the field is preferably ~1 · 2 equivalents. The reaction is more preferably, preferably -2 Torr. (: ~15 () The reaction temperature is preferably 〇, 5 & B ± is more preferably G ° C ~ 10 () ° C. As the reaction time, 卞 24 hours 'more preferably 2 hours ~ - 2 hours. -24- 201239069 As an organic solvent, σ organic solvent is not special; in order to dissolve the synthesized polyamine acid (...), Νν _ : ' For example, Ν- ············ , hexamethylphosphonium = face, a few ~ an amine m-cresol, xylenol, phenol, halogenated diol ... diol ethyl methyl _, etc. as an organic agent in the amount 'relative to tetracarboxylic dianhydride And a diamine, The total amount of the substance is 100 parts by mass, preferably 0.1 part by mass to 50 parts by mass, more preferably 5 parts by mass to 4 parts by mass. <The polyphthalic acid solution obtained after the reaction can be directly supplied to the liquid crystal alignment unit. The preparation of J can also be carried out before the single release of the polylysine contained in the reaction solution and then supplied to the preparation of the liquid crystal alignment agent. It is also possible to first refine the isolated polylysine and then supply it to the preparation of the liquid crystal alignment agent. As a method of separating the poly-proline, for example, a method of drying a precipitate obtained by injecting a reaction solution into a large amount of a poor solvent under reduced pressure is used, and the reaction solution is distilled off under reduced pressure by an evaporator. In the method for purifying polylysine, a method in which the separated polylysine is dissolved in an organic solvent and precipitated by a poor solvent is used, and the method is carried out one or more times by an evaporator. A method of removing a step of distilling off an organic solvent or the like under reduced pressure. [Polyimide] Polyimine can be produced by dehydrating ring-opening of a proline structure of the above polyamic acid. »Polyimine system can make The precursor of the poly-proline has all of the glycosidic structure dehydration ring-closed fully ruthenium imide, or it can be only a part of the proline structure, dehydration ring closure, proline structure and quinone ring structure A part of the coexisting quinone imide. -25- 201239069 a. As a method of synthesizing the polyimine, for example, a heating method of polyfluorene: hydrazine (hereinafter also referred to as "method (1),)), ((1) The polydecylamine is cooled in an organic solvent, and a dehydrating agent and a dehydration ring-closing catalyst J are added to the solution, and a method of heating as needed (hereinafter also referred to as "method (11)) is used to dehydrate the closed loop by polyglycine. The reaction temperature in the method (1) is preferably 50. (: ~200 ° C, more preferably 6 (TC ~ 17 (rc. If the reaction temperature is less than 5 〇 <> c, it is not sufficient = dehydration ring closure reaction, and if the reaction temperature exceeds 2 〇 (rc The molecular weight of the I polyimine is sometimes lowered. The reaction time is preferably from 0.5 to 48 hours, more preferably from 2 to 2 hours. The polyimine obtained in the method (i) It can be directly supplied to the preparation of the liquid crystal alignment agent, or can be separately supplied from the polyimide and then supplied to the preparation of the liquid crystal alignment agent, or pre-refined the separated polyimine or the previously obtained polyfluorene. The imine is further supplied to the preparation of the liquid crystal alignment agent. Examples of the dehydrating agent in the method (U) include acid anhydrides such as acetic acid liver, propylifif, and difluoroacetic acid. The amount of the dehydrating agent is 'according to the desired The ruthenium imidization rate is suitably selected 'but the valeric acid structure of the polyglycolic acid is 1 mole, preferably 〇.〇1 mole to 2 〇mol. Dehydration in the method (ii) Examples of the ring closure catalyst include acridine, Colin base, dimethylpyridine, triethylamine, and the like. The amount of the catalyst used is preferably from 0.01 mol to 10 mol based on 1 mol of the dehydrating agent contained. Further, the higher the content of the above dehydrating agent and the dehydration ring-closure agent, the higher the niobium amination rate. 26-201239069 The organic solvent used in the method (ii), for example, is an organic solvent similar to the right-hearted organic solvent exemplified as a synthon for polyglycolic acid. The reaction temperature in the reaction is preferably 〇.1~8 8 〇.匸, more preferably HTC~丨50. 〇. As the reaction time, preferably 〇5 hours '~2〇 hours, more than... hours~ 8 hours. By allowing the reaction conditions to be in the above range, the dehydration ring-closure reaction can be sufficiently carried out, and the molecular weight of the obtained polystyrene can be made into an appropriate molecular weight. In the method (Π), a polyimine containing polyimine can be obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the dehydration agent and the dehydration ring closure catalyst can be removed from the reaction solution before being supplied to the preparation of the liquid crystal alignment agent, or the polymerization can be preliminarily separated. Asian Further, it is supplied to the preparation of the liquid crystal alignment agent, or the monomerized polyimide is preliminarily purified and supplied to the liquid crystal alignment agent. As a method for removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, solvent replacement is mentioned. The method of the separation and the purification method of the polyimine, for example, the same method as that exemplified as the separation method and the purification method of the poly-proline. [(Meth)acrylic acid polymerization The (meth)acrylic polymer as the [A] polymer is not particularly limited as long as it is a (fluorenyl)acrylic polymer containing a group represented by the above formula (1), and can be used by a known method. It is obtained by polymerizing a conventional ethylenically unsaturated compound, for example, by passing (a) an epoxy group-containing ethylenically unsaturated compound (hereinafter also referred to as "(a) unsaturated compound,) and (bl) ethylenicity. Saturated carboxylic acid and/or polymerizable unsaturated polycarboxylic acid anhydride (hereinafter also referred to as -27-201239069 "(bl) unsaturated compound") and in addition to unsaturated compounds and (bl) unsaturated compounds Outer polymerizable unsaturated compound (hereinafter, also referred to as "(B2) an unsaturated compound") is a copolymer obtained by polymerizing. Examples of the (a) unsaturated compound' include, for example, glycidyl (meth)acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and α-n-butyl acrylate. Glyceryl ester, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl (meth)acrylate, α-ethyl acrylate 6,7-epoxyheptyl ester and the like. Examples of the (b 1) unsaturated compound include (mercapto)acrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, and maleic acid. , fumaric acid, citraconic acid, mesaconic acid, itaconic acid and other unsaturated treason; maleic anhydride, itaconic acid needle, citraconic anhydride, Chuanyou-1,2,3,4-tetrahydroortene An unsaturated polycarboxylic acid anhydride such as a dibasic acid anhydride or the like. Examples of the (b 2 ) unsaturated compound include (fluorenyl) acrylate having a group represented by the above formula (1), 2-mercaptoethyl (meth) acrylate, and 2-(fluorenyl) acrylate. An ester having a (hydroxy) acrylic acid hydroxy group such as hydroxypropyl acrylate; decyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate Ester, (n-butyl) butyl acrylate, β-based propylene acrylate, (meth) acrylic acid secondary vinegar, (meth) propylene hydrazine, etc. And secret (a soil) acrylic hydrazine & pentane vinegar, (fluorenyl) hexyl hexyl acrylate, (methyl), acid 2 - methylcyclohexene '(mercapto) acrylic tricyclic [S 2 丄〇2,6] 癸酉曰曱曱曱曱 · · · · · · · · · · · · 曱曱曱曱 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 (meth) acrylate cyclic esters such as esters; phenyl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; maleic acid II Unsaturated dicarboxylic acid diesters such as ethyl ester, diethyl fumarate and diethyl itaconate; N-phenyl maleimide, N-based maleimide, N_cyclohexyl Maleate, N-succinimide-3, maleic acid, benzoic acid, hydrazine, N-axis, imino group, _4_maleimide butyrate, N_ Amber quinone imine-6-maleimido hexanoate, N-succinimide, 3_maleimido propionate, Ν_(9_acridinyl), Malayan An unsaturated dicarbonyl ruthenium derivative such as an amine; a vinyl cyanide compound such as (meth)acrylonitrile, α-gas acrylonitrile or divinyl cyanoethylene; (meth) acrylamide, hydrazine, hydrazine-dioxin An unsaturated decylamine compound such as benzyl (meth) acrylamide; styrene, ct-methyl stupid ethylene, m-methyl styrene, p-nonyl styrene, vinyl fluorene, p-methoxy styrene, etc. Group vinyl compounds; anthracene derivatives such as fluorene, 1 -fluorenyl hydrazine; conjugated diene such as 1,3-butadiene, isoprene, 2,3 dimethyl hydrazine In addition to the compound, ethylene, vinylidene, acetate, and the like. As (a) unsaturated compound, 轫祛乂乂 is preferably (glycidyl) methacrylate, as (b 1) unsaturated compound, 鲂 m 乂乂乂乂乂 ( ( ( ( ( ( 201239069 is a (b2) unsaturated compound, preferably (meth)acrylic acid. In the case where a dream is synthesized by radical polymerization to form a (meth)acrylic acid complex of the [A] polymer, 'at least from the viewpoint of introducing a group represented by the above formula (1) into the polymer, at least The unsaturated compound of the group represented by the above formula (1) can be used as a ruthenium surface in the unsaturated compound, for example, by polymerization of a conventionally known b)= group which does not have an epoxy group in the above formula. The group represented by the formula (1). The reaction of introducing the above agent into the acid polymer is carried out in the presence of a solvent-forming agent, for example, by radical polymerization. The organic solvent may, for example, be a compound used for the synthesis of polyglycolic acid, a solvent or the like. The same organic compound as the polymerization initiator can be exemplified by: 2,2'-azobisisobutyronitrile, 2,2, nitrile), 2,2,m (4_f Α _ dimethyl Amyl, dimethyl pentoxide, etc., butyl nitride, butyl lanthanide, peroxidized laurel, peroxidic pivalic acid tertiary, peroxy m-butyl peroxidation, cyclohexene, etc. Starter and the like. This is useful for both the redox species of 2 and the reducing agent. The reaction initiator may be used singly or in combination of two [polyoxyalkylene] to indicate (four) 'as long as it is contained in the above formula (1) as follows: human: oxane is not particularly limited 'but can be synthesized, for example, by: at least 1 kind is selected from the group consisting of silk-based compounds -30-

S 201239069 以及ii化矽烷化合物之群 A ^ ^ A 吁，且〒的矽烷化合物（以下也稱為原料石夕烧化合物”），較 )1又佳為在適當的有機溶劑中，在水及催化劑的存在下水解或水解·縮合。作為原料石夕貌化合物，例如可列舉出：四甲氧基石夕烷、四乙氧基石夕烧、四正丙氧基石夕烷、四異丙减矽烷、四正丁氧基矽烷、四(二級丁氧基)矽烷四（二級丁氧基）矽烷、四氯矽烷等；曱基三甲氧基矽烷、甲基三乙氧基矽烷、十八烷基二乙氧基矽烷、甲基三正丙氧基矽烷、甲基三異丙氧基 =、甲基三正丁氧基石夕燒、甲基三（二級丁氧基）石夕烧、二（二級丁氧基）矽烷、甲基三苯氧基矽烷、曱基三氣石夕烧、乙基三甲氧基石夕院、乙基三乙氧基石夕院、乙基二正丙氧基矽烷、乙基三異丙氧基矽烷、乙基三正丁氧基矽烷、乙基三（二級丁氧基）矽烷、乙基三（三級丁氧基）矽烷、乙基三氣矽&、苯基三曱氧基矽&、苯基三乙氧基石夕烷、苯基三氣矽烷等； —曱基二甲氧基矽烷、二甲基二乙氧基矽烷、二曱基二氯矽烷等；三甲基曱氧基矽烷、^甲基乙氧基矽烷、三曱基氯矽烷等；具有以上述式（1)表示之基團的矽烷等。這些原料矽烷化合物之中，較佳為四曱氧基矽烷、四乙氧基石夕m三甲氧基錢、甲基三乙氧基石夕炫、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、三甲基曱氧基矽烷、三 -3 1- 201239069 甲基乙氧基矽烷、十乂式⑴表示之基：的二燒基二乙氧基石夕烧、具有以上迷的情況下，由將以上氧烧作為⑷聚h 觀點來看，至少需要使用且有之基團導入聚合物中的爾為原料以化合物；2…⑴表示之基圏的在合成聚石夕氧烧時1個。例如可列舉出乍為可任意使用的有機溶劑， ^ ^ σ 、_化合物、醯胺化合物、st 口物次其他的非質蜎化合兩種以上來使用。匕物。它們可單獨使用也、 σ成聚矽氧烷時的反應溫度，較佳為〇。 °c，更較佳為15t 又杈佳為〇c〜1〇〇〇.5 平乂佳為1小時〜8小時。 [聚醯胺酸酯] 聚醯胺酸g旨儀士 μ L 1 、精由使上述的聚醯胺酸與物、醇類或盼類反應而獲得的聚合物。有機南化又，[A]聚合物為至少i種選自包含聚醯胺亞胺"甲基)丙稀酸聚合物、聚石夕氧烧以及聚酿胺：:: 之群組中的聚合物時，在[A]聚合物係選擇多種聚合物：情況下’只要至少i種聚合物具有以上述式⑴表示的：團，則可實現本案所期望之效果的高速回應性。之 [A]聚合物藉由凝膠滲透層析法以苯乙烯換算的均分子量（Mw)沒有特別限定，但是若為聚醯 4 亞胺或聚醯胺酸酯時，較佳為1，〇〇〇〜5〇〇,〇〇〇，更較佳為 2,000〜300,000。（甲基）丙烯酸聚合物的情況下較佳^ 1，000〜！，000,000’更較佳為2,000〜500,〇〇〇。若為聚石夕氧 -32- 201239069 元夺較佳為1,000〜200,000，更較佳為2,000〜l〇〇,〇〇〇〇透過在這樣的分子量範圍，可確保液晶顯示元件之良好的配向性及穩定性。 <其他任意成分〉〇要不損害本發明的效果，該液晶配向劑可含有例如硬化劑、硬化催化劑、硬化促進劑、環氧化合物、表面活〖生劑等其他的任意成分。又，肚單：使用各成分也可混合兩種以上而；用。另:卜成= 任成刀的配合量可根據其目的而適當地決定。以下詳述各成分。 [硬化劑、硬化催化劑以及硬化促進劑] 以使[Α]聚合物的交聯反應更強固的目的而可在該液晶配向劑中含有硬化劑以及硬化催化劑。以促進硬化劑所擔任之硬化反應的目的，而可在該液晶配向劑中含有硬化促進劑。作為硬化劑’可使用具有環氧基的硬化性化合物或含有具有環氧基之化合物的硬化性組合物之硬化中通常使用的硬化劑。作為這樣的硬化劑，例如可列舉出多元胺、多元羧酸酐等。作為多元緩酸肝，例如可列舉出環己烷三羧酸的酸酐以及其他的多元羧酸酐。作為環己烷三羧酸酐，例如可列舉出環己烷-1，3,4-三曱酸_3,4_酐、環己烷-^、三甲酸-3,5-酐、環己烷-1，2,3-三曱酸_2,3_酐等。作為其他的多元叛酸酐’例如可列舉出4-甲基四氫鄰苯二甲酸酐、甲基納迪克酸酐、十二烯基琥珀酸酐、琥珀酸酐、馬來酸酐、鄰苯二甲酸酐、偏苯三酸酐等。 -33- 201239069 作為硬化催化劑，例如可列舉出六氟化銻化合物、六氣化碟化合物、三乙醯丙鲷鋁等。這些催化劑可藉由加熱催化環氧基的陽離子聚合。作為硬化促進劑’例如可列舉出咪唑化合物；四級填化合物；四級胺化合物；丨，8_二氮雜雙環[5 4 〇]十—碳 -7-烯或其有機酸鹽等的二氮雜雙環烯烴；辛酸鋅、辛酸錫、乙醢丙酮鋁複合體化合物等的有機金屬化合物；三氟化硼、硼酸三苯酯等的硼化合物；氯化辞、氣化錫等的金屬齒化合物；二氰二胺、胺與環氧樹脂之加成物等的胺加成型促進劑等的高熔點分散型潛在性硬化促進劑，以聚合物被覆四級鱗鹽等的表面之微膠囊型潛在性硬化促進劑；胺鹽型潛在性硬化促進劑；路易士酸鹽、布忍斯特酸鹽等的高溫解離型之熱陽離子聚合型潛在性硬化促進劑等。 [環氧化合物] 從提高所形成的液晶配向膜對於基板表面的接著性的觀點來看’可在該液晶取向劑中含有環氧化合物。作為環氧化合物，較佳為乙二醇二縮水甘油基趟、聚乙二醇一縮水甘油基峻、丙二醇二縮水甘油基喊、三丙一醇一細水甘油基醚、聚丙二醇二縮水甘油基喊、新戊一醇一 lig水甘油基醚、1，6 -己二醇二縮水甘油基驗' 甘油二縮水甘油基醚、2,2-二溴化新戊二醇二縮水甘油基醚、1，3,5,6-四縮水甘油基-2,4-己二醇、N，N，N，，N，-ra 縮水甘油基間二曱苯二胺、1，3-雙（N，N-二縮水甘油基胺基曱基）環己烧、N，N，N’，N’-四縮水甘油基-4,4’-二胺基二 -34- 201239069 :基二縮水甘油基彳胺、n，n-二縮水甘油基 -月女基甲基環己烷。 [表面活性劑] 作為表面活性劑，例如可列舉出非離子表劑、陰離子表面活性劑、陽離子表面活性劑、兩活,劑、聚矽氧烷表面活性劑、聚環氧烷表面活性劑、含氟表面活性劑等。月 <液晶配向劑的製備方法〉如上述般該液晶配向劑含有[A]聚合物作於分，可根據雪要人古计為必品成 ^根據力要3有其他任意成分，但是各成為溶解於有機溶劑之溶液狀的組合物而製備。佳作乍為可使用於為了製備該液晶配向劑的有〜較佳為溶解[A]聚合物以及其他任意成分且不：洛劑’ 應者。作為有機溶劑，例如可列舉出作為用於：此等反胺酸的合成者而在上述例示的有機溶劑等。另：述聚酿併用作為用於聚酿胺酸的合成者而例示的卜，也可又’這些有機溶劑可單獨使用也可使用兩種^洛劑。作為可用於製備該液晶配向劑的較佳溶劑為：述的較佳固體成分湲度下，不使該液晶配向^ ·在後各成分析出、且使液晶配向劑的表斤含的 25mN/m〜40mN/m的範圍者。 ^力為作為該液晶配向劑的固體成分濃度，即劑中溶劑以外之全部成分的重量占液晶配向劑的:配向之比例，考慮純、揮發性等來選擇，較佳為。重量質量0/❶的範圍。該液晶配向劑塗布於基板表= 〜U) 取成作 -35- 201239069 為液晶配向膜的塗膜，在固體成分濃度為丨質量％以時，可使S亥塗膜的膜厚不易變得過小而且獲得S 201239069 and group ii decane compound A ^ ^ A ,, and 〒矽化合物化合物 ( ( 以下以下以下以下以下以下以下以下 , , , , 又在在在在在在在在在在在在在在Hydrolysis or hydrolysis/condensation in the presence of the compound. Examples of the raw material compound include tetramethoxy oxacyclohexane, tetraethoxy cerium, tetra-n-propoxy oxacyclohexane, tetraisopropyl decane, and tetra. n-Butoxydecane, tetrakis(2-butoxy)decanetetrakis(2-butoxy)decane, tetrachlorodecane, etc.; mercaptotrimethoxydecane, methyltriethoxydecane, octadecyl Ethoxy decane, methyl tri-n-propoxy decane, methyl triisopropoxy=, methyl tri-n-butoxy oxysulfonate, methyl tri(2-butoxy) zebra, two (two Butoxy) decane, methyltriphenoxydecane, decyl triphosite, ethyltrimethoxy sylvestre, ethyltriethoxy sylvestre, ethyldi-n-propoxy decane, B Triisopropoxy decane, ethyl tri-n-butoxy decane, ethyl tri(2-butoxy) decane, ethyl three Tertiary butoxy) decane, ethyl trigas oxime & phenyl trimethoxy oxime & phenyl triethoxy oxane, phenyl trioxane, etc.; - decyl dimethoxy decane , dimethyldiethoxydecane, dimercaptodichlorodecane, etc.; trimethyl decyloxydecane, methyl ethoxy decane, tridecyl chlorodecane, etc.; having the formula (1) a decane or the like of a group. Among these decane compounds, tetradecyloxydecane, tetraethoxy oxam trimethoxy hydroxy, methyltriethoxy sulphur, phenyltrimethoxydecane, benzene are preferred. Triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, trimethyl decyl decane, tri-3 1- 201239069 methyl ethoxy decane, decimidine (1) In the case of the above-mentioned group: the dialkyl-based diethoxy group, in the case of the above, from the viewpoint of the above oxygen burning as (4) polyh, at least the group needs to be used and the group is introduced into the polymer. The starting material is one of the bases represented by the compound; 2...(1) in the case of synthesizing polysulfide. For example, the hydrazine is optional. The organic solvent used, ^ ^ σ , _ compound, guanamine compound, st-block, other non-quality oxime compounds are used in combination. They can be used alone or in the case of σ-forming polyoxyalkylene. The temperature is preferably 〇. °c, more preferably 15t, and preferably 〇c~1〇〇〇.5 乂乂 is preferably from 1 hour to 8 hours. [Polyurethane] Polyglycine g The instrument is obtained by reacting the above polylysine with a substance, an alcohol or a desired one. The organically modified, [A] polymer is at least one selected from the group consisting of polyfluorene. In the case of a polymer of a group of amine imine "methyl)acrylic acid polymers, polyoxo oxyhydrogen and polystyrene:::, a plurality of polymers are selected in the [A] polymer system: in the case of ' As long as at least one of the polymers has a group represented by the above formula (1), high-speed responsiveness of the effect desired in the present invention can be achieved. The average molecular weight (Mw) in terms of styrene by gel permeation chromatography of the [A] polymer is not particularly limited, but is preferably 1, if it is a polyfluorene 4 imine or a polyphthalate, 〇〇〇~5〇〇, 〇〇〇, more preferably 2,000~300,000. In the case of (meth)acrylic polymer, it is preferable to ^1,000~! ,000,000' is more preferably 2,000 to 500, 〇〇〇. It is preferably from 1,000 to 200,000, more preferably from 2,000 to 1 Torr, in the case of polysulfide-oxygen-32-201239069, and the good alignment of the liquid crystal display element is ensured in such a molecular weight range. And stability. <Other optional components> The liquid crystal alignment agent may contain other optional components such as a curing agent, a curing catalyst, a curing accelerator, an epoxy compound, and a surface active agent, without impairing the effects of the present invention. Further, the belly list can be mixed with two or more types using the respective components. Another: Bu Cheng = The amount of the Ren Cheng knife can be appropriately determined according to its purpose. The ingredients are detailed below. [Hardener, hardening catalyst, and hardening accelerator] The liquid crystal alignment agent may contain a curing agent and a curing catalyst for the purpose of making the crosslinking reaction of the [Α] polymer stronger. The liquid crystal alignment agent may contain a hardening accelerator for the purpose of promoting the hardening reaction by the hardener. As the curing agent, a curing agent which is usually used for curing of a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used. Examples of such a curing agent include a polyamine, a polycarboxylic acid anhydride, and the like. Examples of the polybasic acid-reducing liver include an acid anhydride of cyclohexanetricarboxylic acid and other polycarboxylic acid anhydrides. Examples of the cyclohexane tricarboxylic anhydride include cyclohexane-1,3,4-tridecanoic acid-3,4-anhydride, cyclohexane-, tricarboxylic acid-3,5-anhydride, and cyclohexane. -1,2,3-tridecanoic acid, 2, 3-anhydride, and the like. Examples of the other polyoxoic anhydride include 4-methyltetrahydrophthalic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and trimellitic anhydride. Wait. -33- 201239069 Examples of the curing catalyst include a ruthenium hexafluoride compound, a six gasified disk compound, and triethylenesulfonium aluminum. These catalysts can be cationically polymerized by heating to catalyze an epoxy group. Examples of the curing accelerator include, for example, an imidazole compound; a quaternary compound; a quaternary amine compound; ruthenium, 8-diazabicyclo [5 4 fluorene] deca- 7-ene or an organic acid salt thereof; Azabicycloalkene; organometallic compound such as zinc octoate, tin octoate, acetonitrile aluminum complex compound; boron compound such as boron trifluoride or triphenyl borate; metal tooth compound such as chlorinated or vaporized tin a high-melting-point-dispersion latent curing accelerator such as an amine addition accelerator such as dicyandiamide, an amine or an epoxy resin addition product, or a microcapsule type surface coated with a polymer such as a quaternary phosphonium salt or the like Sex hardening accelerator; amine salt type latent hardening accelerator; thermal cationic polymerization type latent hardening accelerator of high temperature dissociation type such as Lewis acid or Buchner's salt. [Epoxy compound] From the viewpoint of improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate, an epoxy compound may be contained in the liquid crystal aligning agent. As the epoxy compound, ethylene glycol diglycidyl hydrazine, polyethylene glycol monoglycidyl sulphate, propylene glycol diglycidyl sulphate, tripropanol mono glyceryl ether, polypropylene glycol diglycidyl Base shouting, neopentyl alcohol-ligglycidyl ether, 1,6-hexanediol diglycidyl assay 'glycerol diglycidyl ether, 2,2-dibrominated neopentyl glycol diglycidyl ether 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N,,N,-ra glycidyl m-diphenylene diamine, 1,3-double (N , N-diglycidylaminoalkyl)cyclohexene, N,N,N',N'-tetraglycidyl-4,4'-diaminodi-34- 201239069 : bisglycidyl Indoleamine, n, n-diglycidyl-moon-female methylcyclohexane. [Surfactant] Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, a living agent, a polyoxyalkylene surfactant, a polyalkylene oxide surfactant, and the like. Fluorinated surfactants and the like. Month <Preparation method of liquid crystal alignment agent> As described above, the liquid crystal alignment agent contains [A] polymer as a component, and can be formed according to the ancient requirements of the snow person. It is prepared as a solution in the form of a solution dissolved in an organic solvent. Preferably, it is used to prepare the liquid crystal alignment agent. Preferably, the [A] polymer and other optional components are dissolved. As the organic solvent, for example, an organic solvent exemplified above for use as a synthon for such a retinoic acid can be mentioned. Further, the above-mentioned organic solvent may be used alone or two kinds of agents may be used as exemplified for use as a synthesizer for poly-aracine. Preferred solvents for use in the preparation of the liquid crystal alignment agent are: under the preferred solid content, the liquid crystal alignment is not analyzed, and the surface of the liquid crystal alignment agent is 25 mN/ The range of m~40mN/m. The force is selected as the solid content concentration of the liquid crystal alignment agent, that is, the ratio of the weight of all components other than the solvent in the solvent to the alignment ratio of the liquid crystal alignment agent, preferably in consideration of purity, volatility, and the like. Weight range of 0/❶. The liquid crystal alignment agent is applied to the substrate table = 〜U) and is used as a coating film for the liquid crystal alignment film of -35-201239069. When the solid content concentration is 丨% by mass, the film thickness of the S-coating film is not easily made. Too small and get

Ba配向膜。另一方面，在固體成分濃度為10質量％以下時，可抑制塗膜的膜厚變得過大而獲得良膜。s1 又好的液晶配向另外’可防止液晶配向劑的黏性增大而使塗布特性為良好。作為更較佳的固體成分濃度的範圍，例如在利用旋轉器時為1.5質量％〜4·5質量％。在利用印刷法時，為3質量％〜9質量％。在利用喷墨法時，為i質量〇/ 質量％。 <液晶顯示元件> 本發明的液晶顯示元件，其驅動方式沒有特別限制’可將本技術適用於TN、STN、IPS、FFS、Ba alignment film. On the other hand, when the solid content concentration is 10% by mass or less, it is possible to suppress the film thickness of the coating film from becoming excessive and obtaining a good film. S1 is also good for liquid crystal alignment. It can prevent the viscosity of the liquid crystal alignment agent from increasing and the coating properties are good. The range of the more preferable solid content concentration is, for example, 1.5% by mass to 4.5% by mass in the case of using a rotator. When using the printing method, it is 3 mass% to 9 mass%. When using the ink jet method, it is i mass 〇 / mass%. <Liquid Crystal Display Element> The liquid crystal display element of the present invention is not particularly limited in its driving method. The present technology can be applied to TN, STN, IPS, FFS,

Ht-VACVA-IPS)、VA(包含 VA-MVA 方式、VA-PVA 方式等）等習知的各種方式；具備由上述液晶配向劑形成的上迷液晶配向膜。如上述般，根據該液晶配向劑，可製作出可高速回應且電壓保持率、殘影特性、均勻塗布性、耐光性等諸性能優異的液晶顯示元件。一般而言，液晶顯示元件具備在表面依序層疊有透明電極及液晶配向膜的—對基板，這一對基板對向配設於内側，將液晶填充於這一對基板間，用密封劑將周邊部密封。 <^液晶顯示元件的製造方法> 本發明的液晶顯示元件，可例如以下而製造。該液晶顯示元件所具備的液晶配向膜，藉由在基板上塗布該液晶配向劑，接著加熱塗布面而形成於基板上β作為基板’例如可使用漂浮玻璃、鈉玻璃等玻璃；包含聚對苯 -36- 201239069 —匕一酿、聚對苯二曱酸丁二酯、聚醚砜、聚碳酸酯、脂環式平秘^ & Λ歸紅荨的塑膠之透明基板。準備2張如上述之形成有液曰締人 π收日日配向膜的基板，藉由在這2張基板間配置液晶，而制批、* β 表^液Β曰胞。作為液晶胞的製造方法，例如可列舉出以下的方法等。作為第 s —種方法’可藉由使各個液晶配向膜為對向地隔著間隙(胞間隙)對向配置2張基板，並使用密封劑張基板的周邊部貼合，且在由基板表面及密封劑區劃的胞間隙内、、* λ 4古+ '内左入填充液晶後，密封注入孔，而製造液晶胞。 —種方法’可列舉出被稱為ODF(液晶滴下）弋的手法。可藉由在形成液晶配向膜的2張基板之中張基板上之規定的部位塗布例如紫外光硬化性的密 ί材進步在液晶配向膜面上滴加了液晶後，照液晶配向膜對向地貼合另一張萁为張基板’接耆在基板的整面照射 1外光使密封劑硬化，而製造液晶胞。無論藉由任一種方法時，都可望藉由接下來將液晶 λ ϋ，、至所使用的液晶採取各向同性相的溫度，然後緩緩冷卻至室溫，而去除注入時的流動配向。而且，在液晶胞的外侧表面貼合偏光板，而獲得該液晶顯示元件。作為上述密封劑，例如可夕彳舉出含有作為間隔物之氣化鋁球及硬化劑的環氧樹脂等。作為上述液晶’例如可你用a 该曰0 』使用向列型液晶、近晶相型液日日等。若為TN型液晶胞哎Various methods, such as Ht-VACVA-IPS) and VA (including VA-MVA method, VA-PVA method, etc.), and a liquid crystal alignment film formed of the above liquid crystal alignment agent. As described above, according to the liquid crystal alignment agent, it is possible to produce a liquid crystal display element which is excellent in various properties such as high-speed response, voltage holding ratio, image sticking property, uniform coating property, and light resistance. In general, a liquid crystal display device includes a counter substrate on which a transparent electrode and a liquid crystal alignment film are sequentially laminated on a surface, and the pair of substrates are disposed opposite to each other, and liquid crystal is filled between the pair of substrates, and a sealing agent is used. The peripheral part is sealed. <^Method for Producing Liquid Crystal Display Element> The liquid crystal display element of the present invention can be produced, for example, as follows. The liquid crystal alignment film provided in the liquid crystal display device is formed by applying the liquid crystal alignment agent onto the substrate, and then heating the coated surface to form a substrate. β is used as a substrate. For example, glass such as floating glass or soda glass can be used. -36- 201239069 —Plastic, transparent polybutylene terephthalate, polyethersulfone, polycarbonate, alicyclic flat gel ^ & Two sheets of the liquid crystal forming π receiving day alignment film were prepared as described above, and liquid crystal was placed between the two substrates to prepare a liquid crystal cell. Examples of the method for producing the liquid crystal cell include the following methods. As the sth method, two liquid crystal alignment films can be disposed opposite to each other with a gap (cell gap) therebetween, and the peripheral portion of the sealant substrate can be bonded and used on the surface of the substrate. And in the interstitial space of the sealant division, * λ 4 ancient + 'inside left into the filling liquid crystal, the injection hole is sealed to manufacture a liquid crystal cell. A method called 'ODF (liquid crystal dropping) 可 is exemplified. The liquid crystal alignment film may be opposed to the liquid crystal alignment film by applying a liquid crystal to the liquid crystal alignment film by applying, for example, a UV curable material to a predetermined portion of the two substrates formed on the liquid crystal alignment film. The other substrate is bonded to the other substrate, and the outer surface of the substrate is irradiated with 1 external light to harden the sealant to produce a liquid crystal cell. When either method is used, it is expected that the liquid crystal λ 接下来 will be used, and the liquid crystal used will take the temperature of the isotropic phase, and then slowly cooled to room temperature, thereby removing the flow alignment at the time of injection. Further, a polarizing plate is attached to the outer surface of the liquid cell to obtain the liquid crystal display element. As the above-mentioned sealant, for example, an epoxy resin containing a vaporized aluminum ball as a spacer and a curing agent can be given. As the liquid crystal ', for example, you can use a nematic liquid crystal, a smectic liquid type, or the like. If it is a TN type liquid crystal cell

r 1、 A STN型液晶胞時，較佳A 形成向列型液晶之具有正的介 ’’’、 1電各向導性者。作為此般 -37- 201239069 液晶’ 1 系液晶液晶、. 晶等。. 氣、膽 ^ C-15 對癸氧. 電性液; 另向列型: 晶，例. 系液晶晶等。作垣可列被稱作1 1亥Η膜貧施例以愛限於在 (Mw)係管溶溫壓系液晶、酉旨晶、。密°定系立方院系液如膽g烯基型液晶；如的手性劑；酯等的強介較佳為形成為這樣的液晶、希夫驗環己烷系液 ^如可使用聯苯系以、苯基環己貌、聯三苯系液晶、聯笨基環己烧系液晶、雙環辛^液晶、正弓外也可在上述液晶中進—步添㈣畜醇壬酸醋、膽留醇碳酸酿等膽留醇、CB-l5(MerckLtd.)作為商品名販售基亞节基-對胺基_2_甲基丁基肉桂酸 fa而使用。方面，若為垂直配向型液晶胞時，疚晶之具有負的介電各向導性者。作 b可使用二氰基苯系液晶、嗒哜系液、氧偶氮系液晶、聯笨系液晶、苯基岛液晶胞的外側所使用的偏光板沒有特別限定，择出使聚乙浠醇薄膜一邊拉伸配向一邊吸收碰之 ‘H膜”的偏光Μ，而以乙酸纖維素保護膜夹住了的偏光板；或由Η膜本身所形成的偏光板等。 Τ，藉由實施例更具體說明本發明，但本發明不這些實施例。以下的實施例中獲得的[Α]聚合物的重均分子量以下述規格的GPC所測定的聚苯乙烯換算Λ值。 :東曹公司、TSKgelGRCXLII 劏：四氫呋喃度：40〇C 力：68kgf/cm2 -38- 201239069 [合成例1 ] 按照下述反應路徑合成了化合物1、2和3。In the case of r 1 and A STN type liquid crystal cells, it is preferred that A forms a nematic liquid crystal having a positive dielectric ’’. As such -37-201239069 liquid crystal ' 1 type liquid crystal liquid crystal, crystal, etc. Gas, cholesteric ^ C-15 癸 oxygen. Electrolyte; Another Nematic type: Crystal, for example. Liquid crystal crystal. It is called the 1 1 Η Η 以以以以以以以以以以以以以以以以以以以以以以以以以以以以以以以以以以A densely defined cubic system liquid such as a biliary alkenyl type liquid crystal; such as a chiral agent; a strong medium such as an ester is preferably formed into such a liquid crystal, a Schiff test cyclohexane system liquid, such as biphenyl can be used. It can also be added to the above liquid crystal in the above liquid crystal, phenyl ring appearance, triphenyl liquid crystal, biphenyl ring liquid crystal, double ring octane liquid crystal, or straight bow. Cholesterol such as mercaptan carbonated or CB-l5 (Merck Ltd.) is used as a commercial name for the sale of phenyl-2-phenylbutyl cinnamic acid fa. On the other hand, in the case of a vertically aligned liquid crystal cell, the twin crystal has a negative dielectric inductivity. The polarizing plate used for the outer side of the dicyanobenzene liquid crystal, the lanthanide liquid, the oxy azo liquid crystal, the biphenyl liquid crystal, and the phenyl island liquid crystal cell is not particularly limited, and the polyethyl decyl alcohol is selected. The polarizing plate sandwiched by the cellulose acetate protective film while absorbing the polarizing enthalpy of the 'H film' while stretching the film, or the polarizing plate formed by the enamel film itself, etc. Τ, by way of example The present invention will be specifically described. However, the present invention is not limited to these examples. The weight average molecular weight of the [Α] polymer obtained in the following examples is a polystyrene equivalent value measured by GPC of the following specifications: Tosoh Corporation, TSKgelGRCXLII劏: Tetrahydrofuran degree: 40 〇C Force: 68 kgf/cm 2 -38 - 201239069 [Synthesis Example 1] Compounds 1, 2 and 3 were synthesized according to the following reaction route.

化合«Β1 COCI OjN-^^NOj合合«Β1 COCI OjN-^^NOj

nc-〇-〇-°h -►Nc-〇-〇-°h -►

K2C〇3. DMFK2C〇3. DMF

化合Compound

O~C^"cn 在備有冷凝管的500mL的三口燒瓶中加入4_氰基 -4’-羥基聯苯12.6g(〇.〇645莫耳）、ι〇·溴-1_癸醇 17.0g(0.0717莫耳）、碳酸鉀28.4g以及N，N-二甲基甲醯胺350mL，在160°C下加熱攪拌5小時。利用TLC確認反應終止後’將反應溶液冷卻至室溫。將反應溶液投入 1000mL水中，混合攪拌。將所析出的白色固體過濾分離’用水進一步洗滌。在8 0 °C下真空乾燥所獲得的固體，而獲得20_6g上述化合物1。接著將所獲得的2〇g(〇〇569 莫耳）化合物1溶解於150mL的脫水四氫吱喃（thf)，加入了三乙胺7.49g(0.0740莫耳）後，在冰冷下費時3〇分鐘緩慢地滴入溶解於150mL的THF的3,5·二硝基苯甲醯氯14.4g(〇.〇625莫耳），其後，在室溫下攪拌3小時。反應終止後’藉由過濾將三乙胺鹽酸鹽去除，並藉由減壓蒸館將TUF去除後’加入氯仿4〇〇mL。冑此溶液水洗，以硫酸鎂乾燥有機層後，藉由減壓蒸餾去除氯仿。其後 -39- 201239069 用乙醇實施再結晶，在8 0 °C下真空乾燥而獲得2 3.8 g上述化合物2。氮氣流下，將20g(〇.0367莫耳）的上述化合物2以及lg(相對於化合物2為5wt.%)的5%Pd/C加入乙醇500mL中’進一步添加了 28%氨水4.2g(相對於化合物2為2倍莫耳）。一邊將此溶液保持於1 5 ± 5。(：一邊緩慢滴入水合肼（8 0 %純度）2 1 g後，攪拌約2 0小時使其反應。其後’將反應液一邊熱過濾一邊滴入純水cjj，在室溫下撥拌洗蘇後過濾而獲得白色〜淡黃色固體。將其在3 5 °C 下真空乾燥而獲得了 16.8g上述化合物3。 [合成例2] 按照下述反應路徑合成化合物4。 .ch3 ?ra 化合^ 化合«4O~C^"cn Add 4_cyano-4'-hydroxybiphenyl 12.6g (〇.〇645mol), 〇〇·bromo-1_sterol to a 500mL three-neck flask equipped with a condenser 17.0 g (0.0717 mol), potassium carbonate 28.4 g, and N,N-dimethylformamide 350 mL were stirred under heating at 160 ° C for 5 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 1000 mL of water and mixed and stirred. The precipitated white solid was separated by filtration and washed further with water. The obtained solid was vacuum dried at 80 ° C to obtain 20-6 g of the above compound 1. Next, the obtained 2 〇g (〇〇569 摩尔) Compound 1 was dissolved in 150 mL of dehydrated tetrahydrofuran (thf), and after adding 7.49 g (0.0740 mol) of triethylamine, it took 3 hours under ice cooling. In a minute, 14.4 g of 3,5-dinitrobenzamide chloride dissolved in 150 mL of THF was added dropwise, and the mixture was stirred at room temperature for 3 hours. After the reaction was terminated, the triethylamine hydrochloride was removed by filtration, and TUF was removed by a vacuum distillation to remove 〇〇4 mL of chloroform. After the solution was washed with water and the organic layer was dried over magnesium sulfate, chloroform was removed by distillation under reduced pressure. Thereafter, -39-201239069 was recrystallized from ethanol, and dried under vacuum at 80 ° C to obtain 2 3.8 g of the above compound 2. Under nitrogen flow, 20 g (〇.0367 mol) of the above compound 2 and lg (5 wt.% relative to compound 2) of 5% Pd/C were added to ethanol 500 mL to further add 28% of ammonia water 4.2 g (relative to Compound 2 is 2 times Mo). Keep this solution at 1 5 ± 5 while maintaining. (: Slowly drip hydrated hydrazine (80% purity) 2 1 g, stir for about 20 hours to react. After that, 'the reaction solution was filtered while being hot, and dripped into pure water cjj, and mixed at room temperature. After washing with Celite, a white-yellow-yellow solid was obtained, which was dried under vacuum at 35 ° C to obtain 16.8 g of the above compound 3. [Synthesis Example 2] Compound 4 was synthesized according to the following reaction route. .ch3 ?ra compound ^ Combination «4

將藉由與合成例1同樣的操作而獲得的化合物J 20g(0.0569莫耳）溶解於3〇〇mL的THF，加入了 =乙胺 7,49g(0.0740莫耳）後’在冰冷下費時3〇分鐘緩慢滴入甲基丙烯醯氣6.53g(〇.〇625莫耳）後，在室溫下攪拌3小時。反應終止後，藉由過濾將三乙胺鹽酸鹽去除、並且藉由減壓蒸館去除THF後加入氯仿將此溶液水洗，以硫酸鎂乾燥有機層後，藉由減壓蒸餾去除氯仿。其後以乙醇實施再結晶，在8〇t下真空乾燥而獲得17刀上述化合物4。 g -40- 201239069 [合成例3]Compound J 20g (0.0569 mol) obtained by the same operation as in Synthesis Example 1 was dissolved in 3 mL of THF, and =49 g (0.0740 mol) of ethylamine was added, and it took 3 hours under ice cooling. After slowly dropping 6.5 g of methacrylic acid helium (〇.〇625 mol) in 〇, the mixture was stirred at room temperature for 3 hours. After the reaction was terminated, the triethylamine hydrochloride was removed by filtration, and the THF was removed by evaporation under reduced pressure, and then the mixture was washed with chloroform, and the organic layer was dried over magnesium sulfate. Thereafter, recrystallization was carried out with ethanol, and vacuum drying was carried out at 8 Torr to obtain 17 knives of the above compound 4. G -40- 201239069 [Synthesis Example 3]

化合tt6 ^ BS *7^述反應路徑合成了化合物5及 nc-Q-Q-ohCompound tt6 ^ BS *7^ reaction pathway synthesized compound 5 and nc-Q-Q-oh

K2C03, DMF HSifOCHais -^ H,PtCl6-6H2〇在備有冷凝管的500 mL的三口燒瓿中加入4-氰基 -4’-經基聯苯12.6g(0.0645莫耳）、11-漠.-1-十一碳烯 16.7g(0.07l7莫耳）、碳酸鉀28.4g以及N，N-二甲基曱醯胺3 50mL，在160°C下加熱攪拌5小時。利用TLC確認反應終止後，將反應溶液冷卻至室溫。將反應溶液投入於1000mL水中，混合攪拌。將所析出的白色固體過濾分離，用水進一步洗滌。在8(rc下真空乾燥所獲得的固體’而獲得了 1 9.8 g上述化人物$。/甚士 r-» +斤 G 13物5。在備有回流管及氮氣導入管的100mL的三口捧也士壯 0 麂瓶中裝入8.69g(0.0250莫耳）化合物6、15g三曱氧基矽烷、 s ^ ^ ^ ,λ τ 烷以及〇.2M六水合氯鉑酸的、六丁，隹―G虚肌矾後，在氮氣下在10小時回々丨L下進仃反應。藉由使反 ,u , 應'扣合物藉由矽膠的45典刼進一步去 (short colume)後，以二氧胗的紐&柱除溶劑，從而獲得了 3.5 退仃積1 [合成例4] …化合物6。按照下述路徑合成了化合物7〜"。 '41- .201239069K2C03, DMF HSifOCHais -^ H, PtCl6-6H2〇 Add 4-cyano-4'-transphenyl phthalate 12.6g (0.0645 mol), 11- desert in a 500 mL three-burning crucible equipped with a condenser. There were 16.7 g (0.07 l7 mol) of 1-undecene, potassium carbonate 28.4 g, and N,N-dimethylguanamine 3 50 mL, and the mixture was stirred under heating at 160 ° C for 5 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 1000 mL of water and mixed and stirred. The precipitated white solid was separated by filtration and washed with water. The solid obtained by vacuum drying at 8 (rc) obtained 1 9.8 g of the above-mentioned character $. / 士士r-» + kg G 13 substance 5. In the 100 mL three-necked with a return tube and a nitrogen introduction tube士士壮0 麂 bottle filled with 8.69g (0.0250 mol) compound 6, 15g trimethoxy decane, s ^ ^ ^, λ τ alkane and 〇. 2M chloroplatinic acid hexahydrate, Liu Ding, 隹 ― After the G-deficiency tendon, the sputum reaction was carried out under nitrogen for 10 hours. By making the reverse, u, the conjugate compound was further slid by the 45 formula of the sputum, and then Oxygen oxime & column was removed from the solvent to obtain 3.5 retort 1 [Synthesis Example 4] Compound 6. The compound 7~" was synthesized according to the following route. '41-.201239069

在備有冷凝管的500 mL的三口燒瓶中加入4_[二氟 (4-戊基環己基）曱氧基]-2,3-二氟笨酚12 5g、u溴化十一烧酸f酯10g、碳酸鉀14.2g、沐…二曱基甲醯胺 20 0mL ’在160°C下加熱攪拌5小時。利用TLC確認反應終止後’將反應溶液冷卻至室溫。將反應溶液投入 500mL水中，混合攪拌。將所析出的白色固體過濾分離，用水進一步洗滌。在80。(：下將所獲得的固體真空乾燥，而獲得了 14.8g化合物7。在備有冷凝管的200mL的三口燒瓶中，加入1〇g化〇物7、l.6g —水合風氧化裡、3〇mL甲醇、i5mL水，在8(TC下加熱攪拌4小時。利用TLC確認反應終止後，將反應溶液冷卻至室溫。使反應溶液在攪拌的狀態下，將稀鹽酸慢慢滴入反應溶液。過濾析出固體，以水、乙醇的順序洗滌。在8〇。(：下真空乾燥所獲得的固體，而獲得了 6 g化合物8。 -42- 201239069 在備有冷凝管的1 0 0 m L的三口燒瓶中，混合5 g化合物8、5mL亞硫醯氣，在80°C下加熱搜拌反應1小時。以水流式吸氣機減壓並去除未反應的亞硫醯氣後，與四氫呋喃5〇mL混合，製成了溶液（1)。接著在備有滴液漏斗的2〇Oml三口燒瓶中混合乙二醇8 9g、四氫呋喃 20mL、二乙胺2 2g，在冰浴中攪拌。在其中滴加溶液（〇後，在室溫下攪拌反應3小時。反應後加入乙酸乙酯 3〇〇mL，利用分液精製水洗°其後，濃縮有機層而獲得 0 乙醇/蒸餾水中再結晶所獲得的固體，過渡、乾燥所析出的固體，而獲得了 4.3g化合物9。 μ p在具備有滴液漏斗的1 〇〇mL三口燒瓶中，在冰浴中擾摔4 · 〇 g j卜八4 g化合物9、35mL四氫呋喃、u三乙胺。在直 ^ 入3,5_二硝基苯甲醯氣1.8g後，在室溫下攪伴反應3小昧 C rtr 液精製U、加入乙酸乙自旨则社，利用分 J 。其後，濃縮有機層而獲得固體。用乙醇再、’Ό日日所獲得的田 4 s ^ 固粗，過濾、乾燥所析出的固體，而獲得 4.8g化合物1〇。又τ 物U)、7g鋅斗的1GGmL三口燒瓶中混合4化合加入四氫咬喊广亂化銨，真空脫氣、氮氣置換。接著，接著計从〇社、乙醇1〇社且在冰浴中授拌混合。 ==滴：:水7。又，反應的溶劑已預後在室溫下反鹿了 4主冰浴冷卻一邊攪拌’其除催化劑。接：，著，將反應液過據並且去行分液精製。接著1=&乙s、0 3GC)mL ’利用蒸鶴水進者展縮有機層並去除溶劑從而獲得了固 -43- 201239069 體。在乙醇中再結晶，過濾固體、減壓乾燥，而過濾並將其在35°C下進行真空乾燥，而獲得2.4g化合物1 1。 [合成例5] 按照下述路徑合成了化合物1 2〜1 4。In a 500 mL three-necked flask equipped with a condenser, 4_[difluoro(4-pentylcyclohexyl)decyloxy]-2,3-difluoroindophenol 12 5 g, u-brominated undecanoic acid f-ester 10 g, potassium carbonate 14.2 g, m-dimercaptocaramine 20 0 mL 'heated and stirred at 160 ° C for 5 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water and mixed and stirred. The precipitated white solid was separated by filtration and washed with water. At 80. (: The obtained solid was vacuum-dried to obtain 14.8 g of Compound 7. In a 200 mL three-necked flask equipped with a condenser, 1 g of mash 7 and 1.6 g of hydrated wind oxide were added, 3 〇 mL methanol, i5 mL of water, and stirred under heating at 8 (TC for 4 hours. After confirming the termination of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was slowly added dropwise to the reaction solution while stirring. The solid was separated by filtration and washed in the order of water and ethanol. The solid obtained was dried under vacuum, and 6 g of compound 8 was obtained. -42- 201239069 In the case of a condenser with a condenser of 100 m In a three-necked flask, mix 5 g of compound 8, 5 mL of sulfinium gas, and heat the mixture for 1 hour at 80 ° C. Depressurize with a water flow aspirator and remove unreacted sulphurous sulphur gas, then with tetrahydrofuran. 5 〇 mL was mixed to prepare a solution (1), and then 8 9 g of ethylene glycol, 20 mL of tetrahydrofuran, and 2 g of diethylamine were mixed in a 2 〇Oml three-necked flask equipped with a dropping funnel, and stirred in an ice bath. The solution was added dropwise (after stirring, the reaction was stirred at room temperature for 3 hours. 3 mL of ethyl acetate was washed with water by fractional purification. Thereafter, the organic layer was concentrated to obtain a solid obtained by recrystallization from 0 ethanol/distilled water, and the precipitated solid was transferred and dried to obtain 4.3 g of compound 9. μ p in a 1 〇〇 mL three-necked flask equipped with a dropping funnel, disturbed in an ice bath 4 · 〇gj 八 4 g compound 9, 35 mL of tetrahydrofuran, u triethylamine. Into the 3,5_ After 1.8 g of dinitrobenzamide gas, the reaction was stirred at room temperature for 3 hours, and the liquid was purified by adding the acetic acid to the company, and the fraction was J. Then, the organic layer was concentrated to obtain a solid. Ethanol was further solidified in the field of 4 s ^ obtained on the day of the day, and the precipitated solid was filtered and dried to obtain 4.8 g of compound 1 〇. τ U), 7 g of zinc hopper in a 1 GGmL three-necked flask was mixed 4 Adding tetrahydrogen to bite the ammonium, vacuum degassing, and nitrogen replacement. Then, it is counted from the 〇社, ethanol 1〇社 and mixed in an ice bath. == Drop:: Water 7. Again, the reaction The solvent has prognosis at room temperature, anti-deer has 4 main ice bath cooling while stirring 'the catalyst is removed. The liquid was passed and the liquid was refined. Then 1 = & s, 0 3 GC) mL 'The organic layer was expanded by the steaming crane water and the solvent was removed to obtain the solid -43-201239069. Recrystallization in ethanol. The solid was filtered, dried under reduced pressure, and filtered and dried under vacuum at 35 ° C to obtain 2.4 g of Compound 11. [Synthesis Example 5] Compounds 1 2 to 14 were synthesized according to the following procedures.

在備有冷凝管的500mL的三口燒瓶中混合3,5-二硝基氟苯18.6g、11-溴十一醇24.4g、三乙胺20g、四氫呋喃100mL，在氮氣氣體環境下在100°C下反應了 30小時。反應後，加入乙酸乙酯200mL，以50mL蒸餾水進行4次分液精製。接著濃縮有機層並去除溶劑而獲得了黃褐色的液體。在其中加入少量乙醇並且在0°C以下冷卻以析出固體。接著，過濾、乾燥所析出的固體而獲得 3 0 g化合物1 2。在備有冷凝管的300mL的三口燒瓶中混合8.3g化合物12、6g的2,3-二氟-4-(4-戊基環己基）苯酚、6g碳酸鉀、 lOOmL二曱基曱醯胺，在80°C下反應了 5小時。確認反應終止，加入乙酸乙醋2 0 0 m L，以5 0 m L蒸餾水進行4 次分液精製。接著濃縮有機層並去除溶劑以獲得黃褐色的液體。在其中加入少量乙醇並且在0 °C以下冷卻以析出固體。接著，過濾、乾燥所析出的固體而獲得1 Og化合物1 3。 -44- 201239069 在備有滴液漏斗的物 13、 2〇g 鋅、34g 著，加入四氫呋喃3( 漏斗的200mL三口燒瓶中混合9.8g化合 3.4g氯化銨，真空脫氣、氮氣置換。接南30mL、乙醇30mL並且在冰浴中搜拌混合。接著慢慢地滴入蒸餾水1 OmL。又，用於反應的溶劑已預先氮氣起泡。滴入時，一邊利用冰浴冷卻一邊攪摔’其後在室溫反應了 6小時。接著，過濾反應液並去除催化劑。接著，加入乙酸乙酯300niL，以蒸潑水進行分液洗滌。接著將濃縮有機層並去除溶劑獲得固體。以乙醇再結晶，將固體過濾、減壓乾燥以獲得了 5 g化合物 14° [合成例6 ] 按照下述路徑合成了化合物1 5〜]7。In a 500 mL three-necked flask equipped with a condenser, 18.6 g of 3,5-dinitrofluorobenzene, 24.4 g of 11-bromoundecyl alcohol, 20 g of triethylamine, and 100 mL of tetrahydrofuran were mixed at 100 ° C under a nitrogen atmosphere. The reaction was carried out for 30 hours. After the reaction, 200 mL of ethyl acetate was added, and the liquid separation was carried out four times with 50 mL of distilled water. The organic layer was then concentrated and the solvent was removed to give a tan liquid. A small amount of ethanol was added thereto and cooled below 0 ° C to precipitate a solid. Next, the precipitated solid was filtered and dried to obtain 30 g of the compound 1 2 . In a 300 mL three-necked flask equipped with a condenser, 8.3 g of compound 12, 6 g of 2,3-difluoro-4-(4-pentylcyclohexyl)phenol, 6 g of potassium carbonate, and 100 mL of decyl decylamine were mixed. The reaction was carried out at 80 ° C for 5 hours. It was confirmed that the reaction was terminated, and 200 ml of ethyl acetate was added, and the liquid separation was carried out four times with 50 m of distilled water. The organic layer was then concentrated and the solvent was removed to obtain a tan liquid. A small amount of ethanol was added thereto and cooled at 0 ° C or lower to precipitate a solid. Next, the precipitated solid was filtered and dried to obtain 1 Og of the compound 13. -44- 201239069 Into the dropping funnel 13, 13 g of zinc, 34 g, and tetrahydrofuran 3 (mixing 9.8 g of 3.4 g of ammonium chloride in a 200 mL three-neck flask of a funnel, vacuum degassing, and nitrogen replacement. 30 mL of the south, 30 mL of ethanol, and mixing in an ice bath. Then, 1 mL of distilled water was slowly added dropwise. Further, the solvent used for the reaction was bubbled with nitrogen in advance, and when it was dripped, it was stirred while cooling with an ice bath. After reacting for 6 hours at room temperature, the reaction solution was filtered and the catalyst was removed. Then, 300 niL of ethyl acetate was added, and the liquid was washed with tap water. The organic layer was concentrated and the solvent was removed to obtain a solid. The solid was filtered and dried under reduced pressure to give 5 g of compound 14° [Synthesis Example 6] Compounds 1 5 to 7 were synthesized according to the following procedures.

，人應24小時。接著，People should be 24 hours. then,

6g化合物加入乙酸乙酯200mL， 15(淡黃色的液體二确基氟苯、50mL I應10小時。加入機層並去除溶劑而獲得了 6g化合物混合5g化合物15、2.9g的2,4_二$ 四氫呋喃、1.9g三乙胺’在80°C下反應 -45- 201239069 乙酸乙醋200mL，以蒸餾水進行分液精製。濃縮有機層並去除溶劑而獲得了 4 · 8 g化合物1 6。在備有滴液漏斗的100niL三口燒瓶中混合4g化合物16、l〇g辞、i.6g氯化銨，真空脫氣、氮氣置換。接著，在氮氣流下，加入四氫呋喃1〇ml、乙醇1〇ml且在冰浴中攪拌混合。接著，慢慢地滴入5ml蒸餾水。又，用於反應的溶劑已預先氮氣起泡。滴入時，一邊在冰浴中冷部一邊攪拌，其後在室溫下反應2小時。接著，過濾反應液並去除催化劑。接著，加入乙酸乙酯3〇〇爪卜以蒸餾水進行分液精製。接著濃縮有機層並去除溶劑以獲得了固體。以乙醇再結晶，過濾、減壓乾燥固體以過濾並將其乾燥而獲得3.3g化合物17。 [合成例7] 按照下土路徑合成了化合物1S以及19 K2C〇3 _ f6g of compound was added to ethyl acetate 200mL, 15 (light yellow liquid di- fluorobenzene, 50mL I should be 10 hours. Add to the machine layer and remove the solvent to obtain 6g compound mixed 5g compound 15, 2.9g of 2,4_two $tetrahydrofuran, 1.9 g of triethylamine 'reacted at 80 ° C -45-201239069 Acetate vinegar 200 mL, liquid separation and purification with distilled water. The organic layer was concentrated and the solvent was removed to obtain 4 · 8 g of compound 16. A 100 niL three-necked flask equipped with a dropping funnel was mixed with 4 g of compound 16, lg, i. 6 g of ammonium chloride, vacuum degassing, and nitrogen substitution. Then, under a nitrogen stream, 1 〇ml of tetrahydrofuran and 1 〇ml of ethanol were added. The mixture was stirred and stirred in an ice bath, and then 5 ml of distilled water was slowly added dropwise. Further, the solvent used for the reaction was bubbled with nitrogen in advance, and while stirring, the mixture was stirred while being cooled in an ice bath, and then at room temperature. The reaction was carried out for 2 hours. Then, the reaction solution was filtered and the catalyst was removed. Then, ethyl acetate 3 〇〇〇〇卜 was added to distillate water for liquid separation purification. The organic layer was then concentrated and the solvent was removed to obtain a solid, which was recrystallized from ethanol, filtered, Drying under reduced pressure Filtered and dried to obtain 3.3g Compound 17. [Synthesis Example 7] Synthesis of a compound according to Soil path K2C〇3 _ 19 F 1S and

CsHuCsHu

0H Bf— DMF 〇5Ητ C5H”.0H Bf— DMF 〇5Ητ C5H”.

〇*"Ci1H22-〇H 化合物1〇*"Ci1H22-〇H Compound 1

TEATEA

THF c5h Ό-〇^Ηη~〇THF c5h Ό-〇^Ηη~〇

化合物1 混合4_[二氣（4-戊基環己基）甲氧基] 3· 50g、11-溴十—酿ώ 齓本酚 ιη〇 T . ^酵 g、奴酉夂鉀6〇g、二甲基甲醯胺 1〇〇mL，在乳氧氣體環境下在85。〇下及廄* 加入乙酸…00mL，^ C應小時。接著，德居if本…u餾水進行分液精製。濃縮有機層並去除〉谷劑以獲得38.7g化合物18。將1〇g化合物18溶解於2〇mL四氫咬喃一乙胺3.9g後，名、士六丁盎 ’― / 7費時1 5分鐘緩慢地滴入將2.6g 201239069 丙烯醯氯溶解於l〇mL四氫呋喃之溶液，其後在室溫下攪拌2小時。反應終止後，藉由過濾去除三乙胺鹽酸鹽，藉由減壓蒸餾去除溶劑後加入氣仿4〇〇mL。將此溶液水洗，以硫酸鎂乾燥有機層後，藉由減壓蒸餾去除氣仿。其後以乙醇實施再結晶，在8〇t下真空乾燥以獲得了 11 g化合物1 9。 < [A]聚合物的合成〉 [聚醯胺酸的合成] [合成例8] 將1，2,3,4-%_丁烧四酸一奸26.08g、以下述式表示的二胺（G-l)7.90g以及上述化合物3的二胺66.0g溶解於 NMP40 0g，在室溫下反應6小時。接著，將反應混合物注入於過量的甲醇中，使反應產物沉澱。用曱醇洗務沉澱物，藉由在減壓下在40°C下乾燥15小時，從而獲得 78.5g聚醯胺酸（PA-1)。Compound 1 is mixed with 4_[diqi(4-pentylcyclohexyl)methoxy] 3·50g, 11-bromo-tanning ώ 齓酚 ι ι 〇 ^ ^ ^ ^ 、、、、、、、、、、 Methylformamide 1 〇〇 mL, at 85 in a milk oxygen atmosphere. Underarm and 廄* Add acetic acid...00mL, ^C should be hour. Next, Deju is used to distill the liquid. The organic layer was concentrated and the granules were removed to obtain 38.7 g of compound 18. After dissolving 1 〇g of compound 18 in 3.9 g of 2 〇mL tetrahydromanate-ethylamine, the name, hexadine ang's / 7 was slowly added dropwise for 15 minutes, and 2.6 g of 201239069 propylene sulfonium chloride was dissolved in l. A solution of 〇mL tetrahydrofuran was stirred at room temperature for 2 hours. After the reaction was terminated, triethylamine hydrochloride was removed by filtration, and the solvent was removed by distillation under reduced pressure. The solution was washed with water and the organic layer was dried over magnesium sulfate. Thereafter, recrystallization was carried out with ethanol, and vacuum drying was carried out at 8 °t to obtain 11 g of compound 19. < Synthesis of [A] Polymer> [Synthesis of Polyamide] [Synthesis Example 8] 26.08 g of 1,2,3,4-%-butyric acid, a diamine represented by the following formula (Gl) 7.90 g and 66.0 g of the diamine of the above compound 3 were dissolved in NMP 40 g, and reacted at room temperature for 6 hours. Next, the reaction mixture was poured into an excess of methanol to precipitate a reaction product. The precipitate was washed with decyl alcohol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 78.5 g of poly phthalic acid (PA-1).

[合成例9] 除使用96.6g化合物11來代替化合物3以外，藉由與合成例8同樣地操作，而獲得100. lg聚醯胺酸（PA-2)。 -47- 201239069 [聚醯亞胺的合成] [合成例10] 將作為四羧酸二酐的2,3,5_三羧基環戊基乙酸 13.45g、作為二胺化合物的3,5_二胺基苯甲酸3 72g 下述式表示的二胺（G-2)3.02g以及化合物3的. 14.8 1 g溶解於NMP 1 40g，在60。(：下反應4小時。測 ’合液的黏度為2,200mPa.s。將反應溶液注入於過甲醇中使反應產物沉澱。其後，用甲醇洗滌，藉由壓下在40°C下乾燥24小時而獲得聚醯胺酸。將全獲得的聚醯胺酸再溶解於465g的NMP中，添加 7.12g以及乙酸酐9.19g並且在110。(：下脫水閉環時’與上述同樣地操作，進行沉澱、洗滌、減壓乾而獲得21.5g醯亞胺化率為68%的聚醯亞胺（PI-1)。二酐、以二胺定此量的在減部所 0比啶 4小燥，[Synthesis Example 9] 100 g of poly-proline (PA-2) was obtained in the same manner as in Synthesis Example 8 except that 96.6 g of the compound 11 was used instead of the compound 3. -47-201239069 [Synthesis of Polyimine] [Synthesis Example 10] 13.45 g of 2,3,5-tricarboxycyclopentyl acetic acid as tetracarboxylic dianhydride, 3,5_2 as a diamine compound Aminobenzoic acid 3 72 g 3.02 g of diamine (G-2) represented by the following formula and 14.8 1 g of compound 3 were dissolved in NMP 1 40 g at 60. (The reaction was carried out for 4 hours. The viscosity of the mixed solution was 2,200 mPa·s. The reaction solution was poured into methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried by pressing at 40 ° C. The poly-proline was obtained in an hour. The fully obtained poly-proline was redissolved in 465 g of NMP, and 7.12 g and 9.19 g of acetic anhydride were added and at 110 (when the dehydration ring was closed), the operation was carried out in the same manner as above. Precipitation, washing, and drying under reduced pressure to obtain 21.5 g of polyimine (PI-1) having a ruthenium iodide ratio of 68%. The dianhydride and the amount of the diamine were determined to be less than 0 in the minus part. ,

[合成例1 1] 將作為四羧酸二酐的2,3,5-三羧基環戊基乙酸 iO.Mg、作為二胺化合物的上述二胺（G_2)7.33g以合物3的二胺i6 78g溶解於NMP中，在60。(：下反小時。測定此聚合液的黏度為1,250mPa.s。將反應二酐及化應4 溶液 -48- 201239069 庄入於過里的曱醇中使反應產物沉澱。其後，用甲醇洗滌，藉由在減壓下在4(rc下乾燥24小時而獲得聚醯胺酉欠。將全部所獲得的聚醯胺酸再溶解於NMP465g，添加吡啶3.84g以及乙酸酐4 96g，並且在11〇。〇下脫水閉環 4小時，與上述同樣地操作，進行沉澱、洗滌、減壓乾燥，而獲得23.1g醯亞胺化率為49%的聚醯亞胺（ρι_2)。 [合成例12] 將作為四鲮酸二肝的2,3,5_三叛基環戊基乙酸二肝 15.17g、作為二胺化合物的上述二胺（G i)3 6〇g、化合物 3的二胺6.68g以& 4,4’_二胺基二苯基甲烷9 “g溶解於丽P14〇g，在6(TC下反應4小時。測定此聚合液㈣度為2,700mPa.s。將反應溶液注入於過量的甲醇中使反應產物沉殿。其後，用甲醇洗務’藉由在減壓下在贼 :乾小時而獲得聚醯胺酸。將全部所獲得的聚醯胺西夂再洛解於NMP465g，添加η比。定 < iU‘7〇g以及乙酸酐 nwg並且在ηπ下脫水閉環4小時，與上述同樣地操作’進行沉澱、洗務、減壓乾燥，而獲得22々醯亞胺化率為76%的聚醯亞胺（PI-3)» [合成例13] 除使用7.69g化合物14來代替化合物3以外，藉由與合成例1 0同樣地操作，而獲得了 9 9 η 又打1 22.9g醯亞胺化率為 76%的聚醯亞胺（PI-4)。 [合成例14] 除使用6.36g化合物17來代替化合物3以外，藉由與合成例1 0同樣地操作，而獲得τ 0 Ψ ] 2 Ug醯亞胺化率 76%的聚醯亞胺（PI-5)。 -49- 201239069 [甲基丙稀酸聚合物的合成] [合成例15] 按照下述反應路徑合成甲基丙烯酸膽留烷酯[Synthesis Example 1 1] 2,3,5-tricarboxycyclopentyl acetic acid iO.Mg as a tetracarboxylic dianhydride, 7.3% of the above diamine (G 2) as a diamine compound, and a diamine of the compound 3. I6 78g is dissolved in NMP at 60. (: the next time is small. The viscosity of the polymerization solution is determined to be 1,250 mPa.s. The reaction dianhydride and the chemical solution 4 solution -48-201239069 are placed in the sterols in the excess to precipitate the reaction product. Thereafter, methanol is used. The washing was carried out by drying under reduced pressure at 4 (rc for 24 hours to obtain polyamine oxime. The obtained polylysine was redissolved in NMP 465 g, pyridine 3.84 g and acetic anhydride 4 96 g were added, and 11〇. The dehydration ring was closed for 4 hours, and the same operation as above was carried out, followed by precipitation, washing, and drying under reduced pressure to obtain 23.1 g of polyimine (ρι 2) having a ruthenium iodide ratio of 49%. [Synthesis Example 12 15.17 g of 2,3,5-trisole-cyclopentyl acetic acid di-hepatic liver as tetracapric acid di-hepatic, the above-mentioned diamine (G i) 36 〇g as a diamine compound, and diamine 6.68 of compound 3. g was dissolved in < 4,4'-diaminodiphenylmethane 9"g in Lithium P14〇g, and reacted at 6 (TC for 4 hours). The polymerization solution was measured at a degree of 2,700 mPa·s. The reaction product was infused into an excess of methanol. Thereafter, it was washed with methanol to obtain polylysine by thief at dry time under reduced pressure. The obtained polyamidoxime was further dissolved in NMP 465 g, and an η ratio was added, and <iU'7〇g and acetic anhydride nwg were dehydrated and dehydrated and closed at ηπ for 4 hours, and the same operation as above was carried out to carry out precipitation, washing, and It was dried under reduced pressure to obtain a polyfluorene imine (PI-3) having a 22 hydrazine imidation ratio of 76%. [Synthesis Example 13] In addition to the use of 7.69 g of the compound 14 instead of the compound 3, 0 was operated in the same manner, and 9 9 η and 1 22.9 g of polyimine (PI-4) having a ruthenium imidation ratio of 76% were obtained. [Synthesis Example 14] In addition to using 6.36 g of compound 17 instead of compound 3 In the same manner as in Synthesis Example 10, a polyimine (PI-5) having a τ 0 Ψ ] 2 Ug醯 imidization ratio of 76% was obtained. -49- 201239069 [Methylacrylic acid polymerization Synthesis of the product] [Synthesis Example 15] Synthesis of choline alkyl methacrylate according to the following reaction route

將β-膽甾烷醇80g溶解於8〇〇mL的THF，加入了二乙胺27.2g後’緩慢地滴入甲基丙烯醯氯35 6g，在室：下搜拌3小時。反應終止後，藉由過濾去除三乙胺鹽= 鹽並藉由減壓蒸餾去除THF後加入氣仿4〇〇mL。將此溶液水洗，用硫酸鎂乾燥有機層後，藉由減壓蒸餾去除2 仿。其後，以乙醇實施再結晶’獲得上述反應式所示之白色固體的曱基丙烯酸膽留烷酯54g(生產率·· 57 4%)。在配置有攪拌棒、三通旋塞、溫度計的四口燒瓶中置入作為單體的上述曱基丙烯酸膽留烷酯l516g(〇〇33莫耳）、曱基丙烯酸縮水甘油酯12.8g(〇〇9莫耳）、曱基丙烯酸7.2g(0.084莫耳）以及45.85g(0.1〇9莫耳）上述化合物4 ’並添加作為溶劑的二乙二醇乙基曱基醚52 8g、作為聚合反應起始劑的2,2，-偶氮雙（2,4-二曱基戊腈）2.24g 以及作為鏈轉移劑的α_甲基苯乙烯二聚物〇 96g。用氮氣氣流對其起泡約1 〇分鐘進行系統内的氮氣置換後，在氮氣氣體環境下在7CTC下反應5小時，而獲得曱基丙烯酸聚合物（PM-1)。藉由GPC進行甲基丙烯酸聚合物（PM-1) 的分子量測定時，Mw = 96,000、Mw/Mn=7.87，未確認 -50- 201239069 有起因於殘留單體的峰。又，假設在聚合物溶液中所置入之單體全部轉換為曱基丙烯酸聚合物（PM-ι)，而直接稀釋用於製備本發明的液晶配向劑。 [合成例16] 除置入10.0g (0.0219莫耳）甲基丙烯酸膽甾烷酯、 15-〇g(〇.1055莫耳）甲基丙浠酸縮水甘油酯、9.〇g(〇.l〇45 莫耳）曱基丙稀酸以及19.3g(0.046莫耳）化合物4，使用作為溶劑的二乙二醇乙基甲基醚43 〇g、作為聚合反應起始劑的2,2，-偶氮雙（2,4-二甲基戊腈）1.83g以及作為鏈轉移劑的α-甲基苯乙烯二聚物0.78g以外，與合成例15同樣地操作，而獲得甲基丙烯酸聚合物（PM_2)。藉由GPC 進行曱基丙稀酸聚合物（PM-2)的分子量測定時， Mw=125,0〇〇、Mw/Mn = 9.54，未綠認有起因於殘留單體的峰。又，假設本該聚合物溶液中所置入之單體全部轉換為甲基丙烯酸聚合物（PM-2)，而直接稀釋用於製成本發明的液晶配向劑。 [合成例1 7 ] 除使用25.6g(0.046莫耳）化合物19代替化合物4以外’藉由與合成例丨6同樣地操作而獲得甲基丙烯酸聚合物（PM-3)。藉由GPC進行曱基丙烯酸聚合物（PM_3)的分子里測定’ Mw= 1 3 1000、Mw/Mn=9.43，未確認有起因於殘留單體的峰。又，假設在該聚合物溶液中所置入之單體全部轉換為甲基丙烯酸聚合物（PM-3)，而直接稀釋用於製成本發明的液晶配向劑。 -51 - 201239069 [聚♦氧炫的合成j [合成例1 8 ] 在備有攪拌器、溫度計、的反應容器中，投入乙二酸12 :商液漏斗以及回流冷凝管製備乙二酸的乙醇溶液。接著；？及乙醇22‘2㈣掉、饬Λ鈾$ %。俠者在氮氣氣體環境下將此溶液加熱至7 0。(：德，右苴φ、、在χ 自八η〗 ’、'作為原料即矽烷化合物之包含ll_lg四乙氧基矽烷及1 ·6§化合物6的混合物。滴入，，»束後，使7 0。(：的溫度維持6 ^ M , 予6小時後冷卻至25°C，接者藉由加入丁基溶纖素4〇〇 fPS ΜίΛ - y- 8而I備含有聚有機矽氧烷 (卩3-1)的 >谷液。此溶液中含80 g of β-cholestyl alcohol was dissolved in 8 mL of THF, and 27.2 g of diethylamine was added, and then 35 6 g of methacrylonitrile chloride was slowly dropped, and the mixture was mixed for 3 hours. After the reaction was terminated, triethylamine salt = salt was removed by filtration and THF was removed by distillation under reduced pressure, followed by the addition of 4 mL of a gas. The solution was washed with water, and the organic layer was dried over magnesium sulfate. Thereafter, recrystallization was carried out in ethanol to obtain 54 g of mercapto phthalic acid choline alkoxide (yield: 57 4%) as a white solid represented by the above reaction formula. Into a four-necked flask equipped with a stir bar, a three-way cock, and a thermometer, the above-mentioned cholesteryl thioglycolate (1,516 g (〇〇33 mol), glycidyl methacrylate, 12.8 g (〇〇) was placed as a monomer. 9 mol), ruthenium acrylate 7.2 g (0.084 mol) and 45.85 g (0.1 〇 9 mol) of the above compound 4' and adding 52 g of diethylene glycol ethyl decyl ether as a solvent, as a polymerization reaction The initiator 2,2,-azobis(2,4-dioxyl valeronitrile) 2.24 g and the α-methylstyrene dimer 〇 96 g as a chain transfer agent. The mixture was bubbled with a nitrogen gas stream for about 1 Torr for nitrogen substitution in the system, and then reacted at 7 CTC for 5 hours under a nitrogen gas atmosphere to obtain a mercaptoacrylic acid polymer (PM-1). When the molecular weight of the methacrylic acid polymer (PM-1) was measured by GPC, Mw = 96,000 and Mw/Mn = 7.87, and it was not confirmed that -50 - 201239069 had a peak due to residual monomers. Further, it is assumed that all of the monomers placed in the polymer solution are converted into a mercaptoacrylic acid polymer (PM-I), and are directly diluted for use in preparing the liquid crystal alignment agent of the present invention. [Synthesis Example 16] In addition to 10.0 g (0.0219 mol) of cholesteryl methacrylate, 15-〇g (〇.1055 mol) methyl glycidyl glycidyl ester, 9.〇g (〇. L〇45 摩尔) mercapto acrylate and 19.3 g (0.046 mol) of compound 4, using diethylene glycol ethyl methyl ether as a solvent, 43 〇g, as a polymerization initiator 2, 2, Methyl methacrylate polymerization was carried out in the same manner as in Synthesis Example 15 except that 1.83 g of azobis(2,4-dimethylvaleronitrile) and 0.78 g of α-methylstyrene dimer as a chain transfer agent were used. Matter (PM_2). When the molecular weight of the mercaptopropionic acid polymer (PM-2) was measured by GPC, Mw = 125, 0 〇〇 and Mw / Mn = 9.54, and the chlorotic group was found to have a peak due to residual monomers. Further, it is assumed that all of the monomers placed in the polymer solution are converted into a methacrylic acid polymer (PM-2), and are directly diluted to prepare a liquid crystal alignment agent of the present invention. [Synthesis Example 1 7] A methacrylic acid polymer (PM-3) was obtained by the same operation as in Synthesis Example 6 except that 25.6 g (0.046 mol) of Compound 19 was used instead of Compound 4. When the molecular weight of the methacrylic acid polymer (PM_3) was measured by GPC, 'Mw = 1 3 1000 and Mw/Mn = 9.43, and no peak due to the residual monomer was confirmed. Further, it is assumed that all of the monomers placed in the polymer solution are converted into a methacrylic acid polymer (PM-3), and the direct dilution is used to prepare the liquid crystal alignment agent of the present invention. -51 - 201239069 [Synthesis of polyoxoxime j [Synthesis Example 1 8] In a reaction vessel equipped with a stirrer and a thermometer, oxalic acid 12 was introduced into a commercial funnel and a reflux condenser was used to prepare ethanol of oxalic acid. Solution. then;? And ethanol 22 '2 (four) off, 饬Λ uranium $%. The man heated the solution to 70 in a nitrogen atmosphere. (: German, right 苴, χ from η η ', ' as a raw material, a mixture of 矽 lg 化合物化合物化合物 lg lg lg lg lg lg 。。。。。。。。。。。。。。。。。 70. (: The temperature is maintained at 6 ^ M, and after 6 hours, it is cooled to 25 ° C. The solution is prepared by adding butyl cellosolve 4〇〇fPS ΜίΛ - y-8 and containing polyorganosiloxane. 3-1) > Valley liquid. This solution contains

Mw為9000。之聚有機矽氧烷（PS-i)的 [合成例1 9 ] 有備有攪拌器、溫度計、滴 &〔 *〜同夜漏+以及回流冷凝管的反應谷器中，投入乙二酸139 ^ ^ T 7 , g以及乙醇19.5g，攪拌、 ^ ^ ^ 者在氣軋氣體環境下將此洛液加熱至70。(：後，在其中滴入作Α 四乙氧基#以及3.95g化合物6的混合物。滴入結束後，冑7〇。⑶溫度維持M、時後冷卻至乃 C，接著’藉由加入丁基溶纖素4〇.〇g而製備含有聚有機石夕氧烧（仏2)的溶液。此溶液中含有之聚有機石夕氧烧 (PS-2)的 Mw 為 12000。 [合成例2 0 ] 在備有攪拌器、溫度計、滴液漏斗以及回流冷凝管的反應容器中，投入乙二酸10.2g以及乙醇％ 3g，攪拌，製備乙二酸的乙醇溶液。接著在氮氣氣體環境下將此溶 -52- 201239069 液加熱至7(TC後，在其中滴加了作為原料即矽烷化合物之包含四乙氧基矽烷5.54g、化合物6為i2.49g以及十八烧基二乙氧基石夕烧2 · 5 g的混合物。滴加結束後，將7 〇 °C的溫度維持6小時後冷卻至25。(：，接著，藉由加入丁基溶纖素4〇.〇g而製備含有聚有機石夕氧烧（pg_3)的溶液。此溶液中含有之的聚有機石夕氧烧（PS_3)的Mw為 6,000 〇 [合成例21] 將作為四羧酸二酐的2,3,5-三羧基環戊基乙酸二酐 19.8 8g，作為二胺化合物的對苯二胺6.83g、二胺基二苯基甲烧3.58g以及上述二胺（G-l)4.72g溶解於NMP140g 中’在6〇 °C反應4小時。測定此聚合液的黏度為 2 10 0mPa·s。接著，將反應溶液注入於過量的曱醇中使反應產物沉澱。其後，用甲醇洗滌，藉由在減壓下在40°C 下乾燥24小時而獲得聚醯胺酸32·8g。將所獲得的聚醯月女酸3 0g溶解於NMP400g中，添加。比啶12.0g以及乙酸針15.5g並在110它下脫水閉環4小時，與上述同樣地進行沉殿、洗滌、減壓乾燥，獲得25g醯亞胺化率為79% 的聚醯亞胺（PI-6)。 [合成例2 2 ] 在配置有攪拌棒、三通旋塞、溫度計的四口燒瓶中置入作為單體的甲基丙烯酸膽甾烷酯15.16g(0.〇332莫耳）、甲基丙烯酸縮水甘油酯l2_8g(〇〇9莫耳）、甲基丙烯酸7.2g(〇.〇836莫耳）、苯乙烯72g(0 0691莫耳）以及 N-%己基馬來醯亞胺7 2g(〇〇4〇2莫耳），進一步添加作 -53- 201239069 為溶劑的二乙二醇乙基甲基醚52 8g、作為聚合反應起始劑的2,2’-偶氮雙（2,4-二甲基戊腈）2 24§以及作為鏈轉移劑的α -甲基苯乙烯二聚物〇. 9 6 g。用氮氣氣流對其起泡約1 0分鐘而進行系統内的氮氣置換後，在氮氣氣體環境下在70°C下反應5小時，而獲得具有預傾角表現成分的曱基丙烯酸聚合物（PM-4)。藉由GPc進行甲基丙稀酸聚合物（PM-4)的分子量測定時，Mw = 96,〇〇〇、 Mw/Mn = 7.87，未確認有起因於殘留單體的峰。又，假嗖在該聚合物溶液中所置入之單體全部轉換為甲基丙歸酸聚合物（PM-4) ’而直接稀釋用於製備本發明的液晶配向劑。 [合成例23] 在備有攪拌器、溫度計、滴液漏斗以及回流冷凝管的反應容器中，投入乙二酸l〇.2g以及乙醇26.3g，搜掉，製備乙二酸的乙if·》谷液。接著在氣氣氣體環境下將此、,六液加熱至70°C後，在其中滴入作為原料即矽烷化合物之包含四乙氧基石夕炫· 11.lg以及十八烧基三乙氧基石夕烧 2.5g的混合物。滴入結束後，將70°C的溫度維持6小時後冷卻至2 5 °C ’接著’藉由加入丁基》谷纖素4 〇〇 g，而製備含有聚有機矽氧烷（PS-4)的溶液。此溶液中含有之聚有機矽氧烷（PS-4)的Mw為6,900。 <液晶配向劑的製備〉 [實施例1 ] 在上述聚醯胺酸（PA-1)中，使溶劑組成成為NMp: 丁基溶纖素=50:50(質量比）而加入NMP以及丁基溶纖 -54- 201239069 素’製成固體成分濃度為3_5質量％(液晶胞製成用）的溶液以及固體成分濃度為7.0 % (均勻塗布性評價用）的溶液。充分攪拌這些溶液後’藉由分別用孔徑〇 2μπι的過濾器過濾，而製備液晶配向劑（S -1)。 [實施例2] 除使用上述聚醯胺酸（ΡΑ-2)代替上述聚醢胺酸（pa-1) 以外，藉由與實施例1同樣地操作’而製備液晶配向劑 (S-2)。 [實施例3 ] 在上述聚醯亞胺（ΡΙ-1)中’使溶劑組成成為ΝΜΡ: 丁基/谷纖素=50:50(質量比）而加入ΝΜρ以及丁基溶纖素，製成固體成分濃度為3·5質量％(液晶胞製成用）的溶液以及固體成分濃度為7.0%(均勻塗布性評價用）的溶液。充刀攪拌3^些洛液後，藉由分別用孔徑〇. 2卜爪的過濾器過慮，而製備了液晶配向劑（§_3)。 [實施例4 ] 在上述聚醯亞胺（ΡΙ-2)中，使溶劑組成成為ΝΜρ: 丁基溶纖素=50:50(質量比）而加人ΝΜρ以及丁基溶纖素，製成固體成分濃度為3.5質量％(液晶胞製成用）的溶液以及固體成分濃度為7·〇%(均句塗布性評價用）的溶液。充 /刀攪拌迫些溶液後’藉由分別用孔徑〇 2叫的過濾器過濾’而製備了液晶配向劑（s_4)。 [實施例5] 在上述聚醯亞胺（PI_3)中基溶纖素=70:30(質量比）而加，使溶劑組成成為NMP: 丁入NMP以及丁基溶纖素， '55- 201239069 製成固體成分濃度為3 · 5質量％ (液晶胞製成用）的溶液以及固體成分濃度為7.0%(均勻塗布性評價用）的溶液。充分攪拌這些溶液後’藉由分別用孔徑0.2 μιη的過濾器過濾，而製備了液晶配向劑（S-5)。 [實施例6] 除使用上述聚醯亞胺（Ρ1-4)代替上述聚醯亞胺（ρ 1_1) 以外，藉由與實施例3同樣地操作，而製備了液晶配向劑（S-6)。 [實施例7] 除使用上述聚醯亞胺（ΡΙ-5)代替上述聚醯亞胺（pi-i) 以外，藉由與實施例3同樣地操作，而製備了液晶配向劑（S-7)。 [實施例8] 進一步在上述甲基丙烯酸聚合物（ΡΜ-1)溶液中添加二乙二醇甲基乙基鍵’製成固體成分濃度為3.5質量 %(液晶胞製成用）的溶液以及固體成分濃度為7.0%(均勻塗布性評價用）的溶液。充分攪拌這些溶液後，分別使用孔徑0.2 μ m的過遽、器過渡’製備液晶配向劑（S - 8)。 [實施例9] 進一步在上述甲基丙烯酸聚合物（PM-2)溶液中添加二乙二醇曱基乙基醚，製成固體成分濃度為3.5質量 % (液晶胞製成用）的溶液以及固體成分濃度為7 . 〇 % (均勻塗布性評價用）的溶液。充分攪拌這些溶液後，分別使用孔徑0.2μιη的過濾器過濾’製備液晶配向劑（S-9)。 -56- 201239069 [實施例ίο] 除使用上述曱基丙烯酸聚合物（pM_3)代替上述甲基丙烯酸聚合物（PM-1)以外，藉由與實施例8同樣地操作，而製備液晶配向劑（S -1 〇)。 [實施例11] 在含有上述聚有機矽氧烷（PS-1}的溶液中加入丁基溶纖素’而製成固體成分濃度5重量％(液晶胞製成用）的溶液以及固體成分濃度為10.0〇/。（均勻塗布性評價用）的溶液。充分攪拌這些溶液後，藉由分別使用孔徑i μπ1 的過濾器過滤’而製備液晶配向劑（S _丨1 )。 [實施例12] 在含有上述聚有機矽氧烷（PS_2)的溶液中加入丁基溶纖素，而製成固體成分濃度5重量％(液晶胞製成用）的溶液以及固體成分濃度為1〇〇%(均勻塗布性評價用）的溶液。充分攪拌這些溶液後，藉由分別使用孔徑1μπι 的過濾器過濾’而製備液晶配向劑（s_丨2)。 [實施例13] 在含有上述聚有機矽氧烷（PS_3)的溶液中加入丁基溶纖素，而製成固體成分濃度5重量％(液晶胞製成用）的溶液以及固體成分濃度為丨〇〇%(均勻塗布性評價用）的溶液。充分攪拌這些溶液後，藉由分別使用孔徑1μιη 的過;慮器過濾，而製備液晶配向劑（S _ 1 3)。 [比較例1 ] 在上述聚醯亞胺（ΡΙ-6)中，使溶劑組成成為ΝΜρ:丁基溶纖素=50:50(質量比）而分別加入ΝΜρ以及丁基溶纖 -57- 201239069 素，製成固體成分濃度為3.5質量％(液晶胞製成用）的> 液以及固體成分濃度為7.0%(均勻塗布性評價用）的、〜液》充分攪拌這些溶液後，藉由分別用孔徑0.2gm的過濾器過濾，而製備了液晶配向劑（CS-1)。 [比較例2 ] 進一步在上述曱基丙烯酸聚合物（ΡΜ-4)溶液中泰为二乙二醇曱基乙基醚，製成固體成分濃度為3.5陆負量 %(液晶胞製成用）的溶液以及固體成分濃度為7.0%(# $ 塗布性評價用）的溶液。充分攪拌這些溶液後，藉由田分別使用孔徑〇.2μιη的過濾器過濾，而獲得液晶配向Mw is 9000. [Synthesis Example 19] of polyorganosiloxane (PS-i) There is a reaction vessel equipped with a stirrer, a thermometer, a drop & [*~ same night drain + and a reflux condenser, and the input of oxalic acid 139 ^ ^ T 7 , g and 19.5 g of ethanol were stirred, and ^ ^ ^ was heated to 70 in a gas-rolled gas atmosphere. (: After that, a mixture of Αtetraethoxy # and 3.95 g of compound 6 was added dropwise thereto. After the completion of the dropwise addition, 胄7 〇. (3) The temperature was maintained at M, and then cooled to be C, followed by 'addition of butyl group A solution containing polyorganophosphorus (仏2) was prepared by using fibrin 4〇.〇g. The Mw of the polyorganusite (PS-2) contained in this solution was 12,000. [Synthesis Example 2 0 ] In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 10.2 g of oxalic acid and 3 g of ethanol were charged and stirred to prepare an ethanol solution of oxalic acid, which was then dissolved in a nitrogen atmosphere. -52- 201239069 After the liquid was heated to 7 (TC), 5.54 g of tetraethoxysilane as a raw material, that is, a decane compound, and 2.49 g of compound 6 and octadecylate diethoxy zebra 2 were added dropwise thereto. · 5 g of the mixture. After the completion of the dropwise addition, the temperature of 7 ° C was maintained for 6 hours and then cooled to 25. (:, then, by adding butyl cellosolve 4 〇. a solution of (pg_3) burned. The Mw of the polyorganismite (PS_3) contained in this solution is 6,000.合成 [Synthesis Example 21] 19.8 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 6.83 g of p-phenylenediamine as a diamine compound, and diaminodiphenyl group 3.58 g of the above-mentioned calcination and 4.72 g of the above diamine (G1) were dissolved in NMP (140 g) and reacted at 6 ° C for 4 hours. The viscosity of the polymerization solution was measured to be 2 100 mPa·s. Next, the reaction solution was injected into an excess of sterol. The reaction product was precipitated, and then washed with methanol, and dried under reduced pressure at 40 ° C for 24 hours to obtain 32. 8 g of polylysine. The obtained polyglycolic acid was dissolved in 30 g. In a 400 g of NMP, 12.0 g of a pyridine and 15.5 g of an acetic acid needle were added, and the mixture was dehydrated and closed for 4 hours at 110° C., and the chamber was washed, washed, and dried under reduced pressure to obtain 25 g of a polyamidation rate of 79%.醯iminoamine (PI-6) [Synthesis Example 2 2 ] 15.16 g of cholesteryl methacrylate as a monomer was placed in a four-necked flask equipped with a stir bar, a three-way cock, and a thermometer (0. 332 moles, glycidyl methacrylate l2_8g (〇〇9 mole), 7.2g of methacrylic acid (〇.〇836), styrene 72g (0 0691 Mo And N-% hexylmaleimine 7 2g (〇〇4〇2 mole), further added as -53-201239069 solvent diethylene glycol ethyl methyl ether 52 8g, as the polymerization initiation 2,2'-azobis(2,4-dimethylvaleronitrile) 2 24 § and α-methylstyrene dimer 〇. 9 6 g as a chain transfer agent. After foaming for about 10 minutes and nitrogen substitution in the system, the reaction was carried out at 70 ° C for 5 hours in a nitrogen gas atmosphere to obtain a mercaptoacrylic polymer (PM-4) having a pretilt performance component. When the molecular weight of the methyl methacrylate polymer (PM-4) was measured by GPC, Mw = 96, 〇〇〇 and Mw/Mn = 7.87, and a peak due to residual monomers was not confirmed. Further, all of the monomers placed in the polymer solution were converted into a methylpropionic acid polymer (PM-4)' and directly diluted to prepare a liquid crystal alignment agent of the present invention. [Synthesis Example 23] In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, bismuth oxalate (2 g) and ethanol (6.33 g) were charged and found to be acetonitrile. Valley liquid. Then, in the gas atmosphere, the six liquids are heated to 70 ° C, and then the tetraethoxy-containing sulphate 11.lg and octadecyl triethoxy stone are added dropwise as a raw material, that is, a decane compound. Burn a mixture of 2.5 g on the evening. After the completion of the dropwise addition, the temperature of 70 ° C was maintained for 6 hours, and then cooled to 25 ° C. Then, by adding butyl glutamic acid 4 〇〇g, a polyorganosiloxane (PS-4) was prepared. )The solution. The Mw of the polyorganosiloxane (PS-4) contained in this solution was 6,900. <Preparation of Liquid Crystal Aligning Agent> [Example 1] In the above polylysine (PA-1), the solvent composition was changed to NMp: butyl celloside = 50:50 (mass ratio), and NMP and butyl cellosolve were added. 54- 201239069 A solution of a solid content concentration of 3 to 5% by mass (for liquid crystal cell production) and a solution having a solid concentration of 7.0% (for uniform coating property evaluation). After thoroughly stirring these solutions, a liquid crystal alignment agent (S-1) was prepared by filtering with a filter having a pore size of μ 2 μm, respectively. [Example 2] A liquid crystal alignment agent (S-2) was prepared by the same operation as in Example 1 except that the above polylysine (ΡΑ-2) was used instead of the above polyamic acid (pa-1). . [Example 3] In the above polyimine (ΡΙ-1), the solvent composition was changed to ΝΜΡ: butyl/silicin = 50:50 (mass ratio), and ΝΜρ and butyl cellosolve were added to prepare a solid component. A solution having a concentration of 3.5% by mass (for liquid crystal cell production) and a solution having a solid content concentration of 7.0% (for uniform coating property evaluation). After the slurry was stirred by a knife, the liquid crystal alignment agent (§_3) was prepared by using a filter of the aperture 〇. 2 claws, respectively. [Example 4] In the above polyimine (ΡΙ-2), the solvent composition was changed to ΝΜρ: butyl celloside = 50:50 (mass ratio), and ΝΜρ and butyl cellosolve were added to prepare a solid content concentration of A solution of 3.5% by mass (for liquid crystal cell production) and a solution having a solid content concentration of 7·〇% (for evaluation of uniform coating properties). After the solution was stirred by a knife/knife, the liquid crystal alignment agent (s_4) was prepared by filtering through a filter called a pore size 分别 2 respectively. [Example 5] In the above polyethylenimine (PI_3), the amount of cellosolvin = 70:30 (mass ratio) was added to make the solvent composition NMP: Dilute NMP and butyl cellosolve, '55-201239069 A solution having a solid content concentration of 3 · 5 mass % (for liquid crystal cell production) and a solution having a solid content concentration of 7.0% (for uniform coating property evaluation). After thoroughly stirring the solutions, a liquid crystal alignment agent (S-5) was prepared by filtration through a filter having a pore size of 0.2 μm, respectively. [Example 6] A liquid crystal alignment agent (S-6) was prepared in the same manner as in Example 3 except that the above polyimine (Ρ1-4) was used instead of the above polyimine (ρ 1_1). . [Example 7] A liquid crystal alignment agent (S-7) was prepared by the same operation as in Example 3 except that the above polyimine (ΡΙ-5) was used instead of the above polyimine (pi-i). ). [Example 8] Further, a diethylene glycol methyl ethyl bond was added to the above methacrylic acid polymer (ΡΜ-1) solution to prepare a solution having a solid concentration of 3.5% by mass (for liquid crystal cell production) and A solution having a solid content concentration of 7.0% (for uniform coating property evaluation). After thoroughly stirring these solutions, a liquid crystal alignment agent (S-8) was prepared by using a pass-through of a pore size of 0.2 μm. [Example 9] Further, diethylene glycol decyl ethyl ether was added to the above methacrylic acid polymer (PM-2) solution to prepare a solution having a solid concentration of 3.5% by mass (for liquid crystal cell production) and A solution having a solid content concentration of 7% by weight (for uniform coating property evaluation). After thoroughly stirring the solutions, the liquid crystal alignment agent (S-9) was prepared by filtration using a filter having a pore size of 0.2 μm. -56-201239069 [Examples] A liquid crystal alignment agent was prepared by the same operation as in Example 8 except that the above methacrylic acid polymer (pM_3) was used instead of the above methacrylic acid polymer (PM-1). S -1 〇). [Example 11] A solution having a solid content concentration of 5% by weight (for liquid crystal cell production) and a solid content concentration of 10.0 were added to a solution containing the above polyorganosiloxane (PS-1). A solution of 〇/. (for uniform coating property evaluation). After sufficiently stirring these solutions, a liquid crystal alignment agent (S _ 丨 1 ) was prepared by filtering using a filter having a pore diameter of i μπ 1 , respectively. [Example 12] To the solution of the above polyorganosiloxane (PS 2 ), butyl cellosolve was added to prepare a solution having a solid concentration of 5 wt% (for liquid crystal cell production) and a solid concentration of 1% by weight (for uniform coating evaluation). A solution of the liquid crystal alignment agent (s_丨2) was prepared by thoroughly filtering the solutions by using a filter having a pore size of 1 μm. [Example 13] In the above-mentioned polyorganosiloxane (PS_3) To the solution, butyl cellosolve was added to prepare a solution having a solid concentration of 5 wt% (for liquid crystal cell production) and a solution having a solid concentration of 丨〇〇% (for uniform coating property evaluation). After sufficiently stirring the solutions, By A liquid crystal alignment agent (S _ 13) was prepared by filtration using a pore size of 1 μm each. [Comparative Example 1] In the above polyimine (ΡΙ-6), the solvent composition was changed to ΝΜρ:butyl cellosolve. = 50:50 (mass ratio) and ΝΜρ and butyl cello-57-201239069 were added to prepare a solid concentration of 3.5% by mass (for liquid crystal cell production) and a solid concentration of 7.0% (uniform) After the solution was sufficiently stirred, the solution was filtered through a filter having a pore diameter of 0.2 gm to prepare a liquid crystal alignment agent (CS-1). [Comparative Example 2] Further on the above-mentioned sulfhydryl group In the acrylic polymer (ΡΜ-4) solution, the solution is diethylene glycol decyl ethyl ether, and the solution has a solid concentration of 3.5 lan by weight (for liquid crystal cell preparation) and a solid concentration of 7.0% ( a solution for the evaluation of the coating property. After thoroughly stirring the solutions, the liquid crystal alignment was obtained by filtering the filter with a pore size of 2.2 μm.

齊1J (CS-2) 〇 [比較例3 ] 在含有上述聚有機矽氧烷（PS-4)的溶液中加入^ 溶纖素’從而製成固體成分濃度5重量％(液晶胞製成^ 的溶液以及固體成分濃度為10.0%(均勻塗布性評價用的溶液。充分攪拌這些溶液後，藉由分別使用孔徑的過濾器過濾’而製備液晶配向劑（c S - 3)。 <液晶顯示元件的製造> 使用旋轉器將所製備的各液晶配向劑塗布在付八 ^ 〇 ITO膜之透明電極的玻璃基板之透明電極面上，用8〇t 的熱板進行了 1分鐘預烘烤後，在置換為氮氣的烘箱中’藉由在200 C下加熱1小時而去除溶劑，而形成膜厚〇 _ 〇 8 μηι的塗膜（液晶配向膜）。重複進行此操作，製成一對（2張）具有液晶配向膜的基板。藉由網版印刷，在上 -58- 201239069 述基板中的1張基板之具有液晶配向膜的面的外周塗布含直徑3.5 μιη的氧化鋁球之環氧樹脂接著劑後，使一對基板的液晶配向膜面對向地重疊而壓接，在1 5(TC下加熱1小時使接著劑熱硬化。接著，從液晶注入口在基板的間隙中填充負型液晶（Merck制，MLC-6608)後，用環氧系接著劑密封液晶注入口，進一步為了去除液晶注入時的流動配向’將其在i 5 〇〇c下加熱1 〇分鐘後緩緩冷卻至室溫。進一步’藉由在基板的外側兩面使2張偏光板的偏光方向如相互成為正交地貼合，而製造液晶顯示元件。 <評價> 對於製造的液晶顯示元件進行了以下的評價。將結果示於表1。 [回應速度（msec·)] 以包含偏光顯微鏡、光檢測器、以及脈衝產生器的裝置測定回應速度（液晶回應的開始的時間）。此處液晶回應速度係設為，對所製作的液晶顯示元件，由無施加電壓的狀態到施加最大為丨秒鐘之的5 V的電壓時，透射率從10%變化至90%所需要的時間（msec [電壓保持率（％)] 以60微秒的施加時間、1 67毫秒的間距對上述所製造的液晶顯示元件施加5V的電壓後，測定由施加解除起 167毫秒後的電壓保持率（％)。测定裝置使用了東陽 Corporation 製的 VHR-1。 -59- 201239069 [殘影特性（mV)] 對於與上述同樣地操作而製造的液晶顯示元件’在 1 〇〇°C的環境溫度下施加20小時直流1 7V的電壓、藉由閃爍消除法（flicker elimination)來求出，切斷直流電塵後即刻在液晶胞内殘留的電壓（殘留DC電壓（mV))。 [均勻塗布性] π 〇呎T吵日-曰圆上敢布罝徑約4 · 1 μιη的樹脂間隔材 (積水化學製’ Micropear EX-0041-AC4)，在設定為12〇 C的熱板上進行1 〇分鐘加熱處理，準備了具有固著間隔材的矽晶圓。另外關於前述液晶配向劑組成，使用液晶配向膜印刷機（日本寫真印刷製）將調製為印刷用之液晶配向劑(固體成分濃度為7.0%〜1〇〇%)塗布於上述付有：著=隔物的石夕晶圓上’在8〇t的熱板上預供肖工分鐘去除〉谷劑後，在200。(：的熱板上後供烤1〇分鐘，形成膜厚8〇〇A的塗膜。以倍率2〇倍的顯微鏡觀察此進订了均句塗布性的評價。依據印刷不均句及n s 物部分中凹陷的有無實施評價，完全觀者3隔勻和固著間隔物部分之凹陷者為：刷不均觀察到塗布不良，但是可判斷為幾手沒良），略微 B (判斷為良好），印刷不均勾不良者為的:-方被大量觀察者為“C= [耐光性] 7 P «格）。與上述同樣地操作而測定以驗機照射3_小時後的電壓广光源利用耐候試相比電壓保持率的變化量5、j照射前的測定值 •5“下時為“A，，(判斯為優 -60- 201239069 良），超過0.5%而在1 %以下時為“B”（判斷為良好），超過 1%而在3%以下時為“C”（判斷為稍稍良好），超過3%時為 “D”（判斷為不良）。表1齐1J (CS-2) 〇 [Comparative Example 3] Adding fibrin to a solution containing the above polyorganosiloxane (PS-4) to prepare a solid concentration of 5 wt% (liquid crystal cell formation ^ The solution and the solid content concentration were 10.0% (solution for uniform coating property evaluation. After sufficiently stirring the solutions, the liquid crystal alignment agent (c S - 3) was prepared by filtering using a filter having a pore size, respectively. Manufacture of the device> Each of the prepared liquid crystal alignment agents was applied onto the transparent electrode surface of the glass substrate of the transparent electrode of the ITO film using a spinner, and prebaked for 1 minute using a hot plate of 8 〇t for 1 minute. Thereafter, the solvent was removed by heating at 200 C for 1 hour in an oven substituted with nitrogen to form a coating film (liquid crystal alignment film) having a film thickness of 〇〇 8 μm. This operation was repeated to prepare a pair. (2 sheets) A substrate having a liquid crystal alignment film, which is coated with a ring of alumina having a diameter of 3.5 μm on the outer periphery of a surface having a liquid crystal alignment film of one substrate in the substrate of the above-mentioned publication No. 58-201239069 by screen printing. After the oxy resin adhesive, make a pair of substrates The crystals were superposed on the film facing each other and pressed, and the adhesive was thermally cured by heating at 15 °C for 1 hour. Then, a negative liquid crystal (manufactured by Merck, MLC-6608) was filled in the gap of the substrate from the liquid crystal injection port. Thereafter, the liquid crystal injection port is sealed with an epoxy-based adhesive, and further, in order to remove the flow alignment during liquid crystal injection, it is heated at i 5 〇〇c for 1 minute and then slowly cooled to room temperature. Further 'by the substrate On the outer side of the two polarizing plates, the polarizing directions of the two polarizing plates were bonded to each other to form a liquid crystal display element. <Evaluation> The following evaluations were performed on the manufactured liquid crystal display elements. The results are shown in Table 1. [Response speed (msec·)] The response speed (the time at which the liquid crystal response starts) is measured by a device including a polarizing microscope, a photodetector, and a pulse generator. Here, the liquid crystal response speed is set to the liquid crystal display produced. The time required for the component to change from 10% to 90% from the state where no voltage is applied until the voltage of 5 V is applied for a maximum of 丨 seconds (msec [voltage holding ratio (%)] is 60 microseconds) Shi After a voltage of 5 V was applied to the liquid crystal display element manufactured as described above, the voltage holding ratio (%) after 167 ms from the release of the application was measured. The measuring device used VHR-1 manufactured by Dongyang Corporation. -59-201239069 [Residual image characteristic (mV)] The liquid crystal display element manufactured in the same manner as described above was applied with a voltage of 1 to 7 V for 20 hours at an ambient temperature of 1 ° C, by the scintillation elimination method ( The flicker elimination is used to determine the residual voltage (residual DC voltage (mV)) immediately after the DC dust is cut off in the liquid crystal cell. [Uniform coating property] π 〇呎T Nostalgic - A resin spacer (Daichi Chemical's Micropear EX-0041-AC4) with a diameter of about 4 · 1 μm on a round plate, set to a thermal plate of 12 ° C The crucible wafer having the fixing spacer was prepared by performing heat treatment for 1 minute. In addition, the composition of the liquid crystal alignment agent is applied to a liquid crystal alignment agent for printing (solid content concentration: 7.0% to 1% by weight) using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). On the Shi Xi wafer on the partition, 'pre-supplied with the Xiaogong minutes on the hot plate of 8〇t> after the granules, at 200. (: The hot plate was baked for 1 minute, and a coating film having a film thickness of 8 〇〇A was formed. The evaluation of the coating property of the uniform sentence was observed by a microscope with a magnification of 2 〇. According to the printing unevenness sentence and ns The presence or absence of the depression in the object portion was evaluated. The complete depression of the spacer and the spacer portion of the spacer was: poor coating was observed, but it was judged to be a few hands, and slightly B (determined to be good) ), the printing unevenness is poor: - The square is obscured by a large number of observers as "C = [light resistance] 7 P « cell). The same operation as above is performed to measure the voltage wide light source after 3 hours of exposure to the inspection machine. The amount of change in the voltage holding ratio of the weathering test is 5, and the measured value before the irradiation of the lens is 5, and the time is 5, when it is "A," (the sentence is excellent -60 - 201239069), when it is more than 0.5% and is less than 1%. When it is "B" (determined to be good), it is "C" when it is more than 1% and is 3% or less (it is judged to be slightly good), and when it exceeds 3%, it is "D" (it is judged to be bad).

液晶配向劑所使用的[A]成分的種類回應速度 (msec.) 電壓保持率 (%) 殘影特性 (mV) 均勻塗布性耐光性實施例1 S-1 聚醯胺酸(PA-1) 14 98 80 A C 實施例2 S-2 聚醯胺酸(PA-2) 10 98 90 A C 實施例3 S-3 聚醯亞胺(PI-1) 14 99 150 B B 實施例4 S-4 聚醯亞胺(PI-2) 15 99 220 B B 實施例5 S-5 聚醯亞胺(PI-3) 19 99 280 B B 實施例6 S-6 聚醯亞胺(PI-4) 10 99 200 B B 實施例7 S-7 聚醯亞胺(PI-5) 10 99 220 B B 實施例8 S-8 甲基丙烯酸聚合物(PM-1) 16 98 290 A B 實施例9 S-9 甲基丙烯酸聚合物(PM-2) 22 98 240 A B 實施例10 S-10 甲基丙烯酸聚合物(PM-3) 16 98 280 A B 實施例11 S-11 聚矽氧烷(PS-1) 17 99 75 B A 實施例12 S-12 聚矽氧烷(PS-2) 19 99 50 B A 實施例13 S-13 聚矽氧烷(PS-3) 21 99 80 B A 比較例1 CS-1 聚醯亞胺(PI-6) 57 99 310 B B 比較例2 CS-2 曱基丙烯酸聚合物(PM-4) 62 98 330 A B 比較例3 CS-3 聚矽氧烷(PS-4) 48 99 65 B A 根據表1的結果可知，具備使用實施例1〜1 3之液晶配向劑而形成的液晶配向膜之液晶顯示元件，顯示出良好的液晶回應速度。具備由含有聚醯亞胺或聚矽氧烷的該液晶配向劑所形成的液晶配向膜之液晶顯示元件，顯示出高的電壓保持率。另外，含有聚醯胺酸或曱基丙烯酸聚合物的該液晶配向劑，顯示出優異的均勻塗布性。進一步，具備由含有聚矽氧烷或聚醯胺酸的該液晶配向劑所形成之液晶配向膜的液晶顯示元件，顯示出優異的殘影特性。具備由含有聚矽氧烷的該液晶配向劑所形成之液晶配向膜的液晶顯示元件，顯示出優異的对光性。因此，該液晶配向劑可實現液晶顯示元件的高速回應性、且透過適當選擇聚合物主鏈結構，可使所希望的特 -6 1- 201239069 性（電壓保持率、殘影特性、均勻塗布性、耐光性）更加優異。產業上的可利用性根據本發明可提供一種可製作出可高速回應且電壓保持率、殘影特性、耐光性等諸性能優異的液晶顯示元件，並且均勻塗布性亦優異的液晶配向劑。因此，該液晶顯示元件可適合用於 TN、STN、IPS、FFS、 Ht-VA(VA-IPS)、VA(包括 MVA、PVA、光垂直配向、PS A 等方式）等驅動模式。【圖式簡單說明】無。【主要元件符號說明】無。 -62-Type response speed (msec.) of the component [A] used for the liquid crystal alignment agent. Voltage retention (%) Image retention (mV) Uniform coating light resistance Example 1 S-1 Polylysine (PA-1) 14 98 80 AC Example 2 S-2 Polylysine (PA-2) 10 98 90 AC Example 3 S-3 Polyimine (PI-1) 14 99 150 BB Example 4 S-4 Polyfluorene Imine (PI-2) 15 99 220 BB Example 5 S-5 Polyimine (PI-3) 19 99 280 BB Example 6 S-6 Polyimine (PI-4) 10 99 200 BB Implementation Example 7 S-7 Polyimine (PI-5) 10 99 220 BB Example 8 S-8 Methacrylic Acid Polymer (PM-1) 16 98 290 AB Example 9 S-9 Methacrylic Acid Polymer ( PM-2) 22 98 240 AB Example 10 S-10 Methacrylic Acid Polymer (PM-3) 16 98 280 AB Example 11 S-11 Polyoxane (PS-1) 17 99 75 BA Example 12 S-12 Polyoxane (PS-2) 19 99 50 BA Example 13 S-13 Polyoxane (PS-3) 21 99 80 BA Comparative Example 1 CS-1 Polyimine (PI-6) 57 99 310 BB Comparative Example 2 CS-2 Mercaptoacrylic acid polymer (PM-4) 62 98 330 AB Comparative Example 3 CS-3 Polyoxane (PS-4) 48 99 65 BA According to the results of Table 1, 1~1 Preparation of Example 3 of the liquid crystal alignment agent to form a liquid crystal alignment film of the liquid crystal display element, the liquid crystal exhibits good good response speed. A liquid crystal display element having a liquid crystal alignment film formed of the liquid crystal alignment agent containing polyimine or polysiloxane, exhibits a high voltage holding ratio. Further, the liquid crystal alignment agent containing a polyamic acid or a mercapto acryl polymer exhibits excellent uniform coating properties. Further, a liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal alignment agent containing polysiloxane or polyglycolic acid exhibits excellent afterimage characteristics. A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal alignment agent containing polyoxyalkylene exhibits excellent light transmittance. Therefore, the liquid crystal alignment agent can achieve high-speed responsiveness of the liquid crystal display element, and can appropriately select a polymer main chain structure, and can achieve a desired characteristic of -6 1- 201239069 (voltage retention, afterimage characteristics, uniform coating property) , light resistance) is more excellent. Industrial Applicability According to the present invention, it is possible to provide a liquid crystal display element which is excellent in various properties such as voltage retention, image retention, and light resistance, and which is excellent in uniform coating properties. Therefore, the liquid crystal display element can be suitably used in driving modes such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), VA (including MVA, PVA, optical vertical alignment, PS A, etc.). [Simple description of the diagram] None. [Main component symbol description] None. -62-

Claims

201239069 七、申請專利範圍： 1 · 一種液晶配向劑，其含有[A]選自包含聚醯胺酸、聚醯亞胺、（甲基）丙稀酸聚合物、聚石夕氧院以及聚酿胺酸醋之群組中的至少1種聚合物，且上述聚合物具有以下述式（1)表示的基團， (式（1)中，R1為亞甲技 (r ^ T基、奴數為2〜30的伸烷基、 (cbH2b〇)e-、伸苯基或伸产為〇~ια 0 m ^ n 长己基，b為0〜20的整數，c 勺υ 10的整數，並且這此部可被取代， &基團的虱原子的一部分或全環結構的基液晶配向劑 R2為包含碳-碳雙鍵酿胺鍵的連結基， R為至少具有兩個單 a為0或1的整數）。如申請專利範圍第丨項之下述·式（2)表示的基團，碳-碳三鍵、醚鍵、酯鍵或團，，其中該R3為以 (R7)rR6如(2 (式（2)中，R4及r6 基、萘基、伸環己基、或雜環’並且這些基團取代，各自獨立地為伸苯基、伸聯苯 •^伸環己基、伸環己基伸苯基的氣原子的一部分或全部可被碳-碳雙並且上 R5為包含亞曱基、碳鍵、碳-碳三鍵、醚鍵、的伸烷1 述連結基的氫原？的、5雜％的連結 °P分或全部可被取十 '63- 201239069 R7為氫原子、氰基、氟原子、三氟曱基、烷氧基叛基、烧基、烧氧基、三氟甲氧基或炫基截氧基， b為0或1，c為1〜9的整數，其中，R7為多個的情況下，多個R7可以相同也可不同）。 3. —種液晶配向膜，其係由如申請專利範圍第1或2項之液晶配向劑形成。 4 · 一種液晶顯示元件，其係具備如申請專利範圍第3項之液晶配向膜。 -64- 5 201239069 四、指定代表圖： (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明：無。五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：201239069 VII. Patent application scope: 1 · A liquid crystal alignment agent containing [A] selected from the group consisting of polylysine, polyimine, (meth)acrylic acid polymer, poly-stone compound, and poly brewing At least one polymer in the group of amic acid vinegar, and the above polymer has a group represented by the following formula (1), (in the formula (1), R1 is a sub-technique (r ^ T group, slave number) 2 to 30 alkylene, (cbH2b〇)e-, phenyl or extended to 〇~ια 0 m ^ n long hexyl, b is an integer from 0 to 20, c scoop υ 10 integer, and this This portion may be substituted, a part of the ruthenium atom of the & group or a basal liquid crystal alignment agent R2 of the all-ring structure is a linking group containing a carbon-carbon double bond, and R is at least two single a's being 0 or An integer represented by the following formula (2), a carbon-carbon triple bond, an ether bond, an ester bond or a group, wherein R3 is such as (R7)rR6 (2 (in the formula (2), R4 and r6 groups, naphthyl, cyclohexylene, or heterocyclic ring') and these groups are substituted, each independently being a phenylene group, a phenylene group, a cyclohexylene group, and a stretching group. A part or all of the gas atom of the phenylene group may be a carbon-carbon double and the upper R5 is a hydrogen atom containing a sulfhydryl group, a carbon bond, a carbon-carbon triple bond, an ether bond, or a hydrogen group. , 5 % by % of the link °P or all can be taken from 10'63-201239069 R7 is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxy group, a decyl group, an alkoxy group, a trifluoro group a methoxy group or a thiol cleavage group, b is 0 or 1, and c is an integer of 1 to 9, wherein when R 7 is plural, a plurality of R 7 's may be the same or different). A film formed of a liquid crystal alignment agent according to claim 1 or 2. 4 A liquid crystal display element having a liquid crystal alignment film as in the third application of the patent application. -64- 5 201239069 IV. Designation Representative diagram: (1) The representative representative of the case is: No. (2) The symbol of the symbol of the representative figure is simple: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: