TWI746423B - Diamine, and aligning agent of liquid crystal using the same - Google Patents

Diamine, and aligning agent of liquid crystal using the same Download PDF

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TWI746423B
TWI746423B TW104116282A TW104116282A TWI746423B TW I746423 B TWI746423 B TW I746423B TW 104116282 A TW104116282 A TW 104116282A TW 104116282 A TW104116282 A TW 104116282A TW I746423 B TWI746423 B TW I746423B
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dianhydride
diamino
furan
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崔珍郁
尹星壹
姜少熙
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南韓商東進世美肯股份有限公司
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Abstract

本發明揭露一種垂直配向劑用聚醯亞胺樹脂及其製備方法，並提供一種具備均勻且較高預傾角而可作為聚醯亞胺配向膜的原料使用的側鏈型二胺聚醯亞胺化合物的製備方法、利用它的具有90°預傾角且均勻穩定的配向性的垂直配向劑用聚醯亞胺樹脂及其製作方法。The present invention discloses a polyimide resin for vertical alignment agent and a preparation method thereof, and provides a side-chain type diamine polyimide resin having a uniform and high pretilt angle that can be used as a raw material for a polyimide alignment film A preparation method of the compound, a polyimide resin for a vertical alignment agent with a 90° pretilt angle and uniform and stable alignment using the compound, and a preparation method thereof.

Description

二胺合成及用其製備的液晶配向劑Synthesis of diamine and liquid crystal alignment agent prepared from it

本發明是有關於一種液晶配向劑用聚醯亞胺樹脂及其製備方法，特別是有關於一種能夠簡便控制預傾角而具備良好的液晶配向性的可作為聚醯亞胺配向膜的原料使用的二胺化合物的製備方法、用其製備的液晶配向劑用聚醯胺酸或聚醯亞胺、包含其的液晶配向劑The present invention relates to a polyimide resin for liquid crystal alignment agents and a preparation method thereof, in particular to a polyimide resin that can be used as a raw material for polyimide alignment films that can simply control the pretilt angle and have good liquid crystal alignment. Preparation method of diamine compound, polyamide acid or polyimide for liquid crystal alignment agent prepared therewith, and liquid crystal alignment agent containing the same

為了提高顯示器性能，曾提議、開發出了多種多樣液晶驅動模式。液晶顯示元件的驅動方式分為，在透明電極上塗布配向膜而成的兩張透明電極基板之間排列向列型液晶分子的扭轉向列（Twist Nematic，下稱“TN”）模式；超級扭轉向列（Super Twist Nematic，下稱“STN”）模式；平面轉換(下稱“IPS”)模式；垂直配向（Vertical Alignment，下稱“VA”）模式；使用薄膜電晶體（Thin Film Transistor，下稱“TFT”）的TFT型。In order to improve display performance, various liquid crystal drive modes have been proposed and developed. The driving method of the liquid crystal display element is divided into a twisted nematic (Twist Nematic, hereinafter referred to as "TN") mode in which nematic liquid crystal molecules are arranged between two transparent electrode substrates formed by coating an alignment film on a transparent electrode; super twist Nematic (Super Twist Nematic, hereinafter referred to as "STN") mode; In-plane conversion (hereinafter referred to as "IPS") mode; Vertical Alignment (hereinafter referred to as "VA") mode; Uses thin film transistors (Thin Film Transistor, below) Called "TFT") TFT type.

根據如上不同驅動模式而需要特定的預傾角，從而用於穩定產生這種預傾角的配向膜，則成為決定LCD性能的重要因素。According to the above-mentioned different driving modes, a specific pretilt angle is required, so that the alignment film used to stably generate this pretilt angle becomes an important factor in determining the performance of the LCD.

作為配向膜的材料，曾經應用了從無機物到有機高分子的很多種。其中最為普遍使用的典型高分子化合物是將聚醯胺轉變成亞胺而使用的聚醯胺類及可溶性聚醯亞胺類等聚合物。由於其具備良好的耐熱性及耐化學性，從而作為配向液晶的配向劑得到了工業上的廣泛應用。另一方面，這種高分子化合物是聚合二胺與四羧酸二酐而成的，單體的結構實現了高分子化合物的物質特徵。As the material of the alignment film, many kinds of inorganic substances to organic polymers have been used. Among them, the most commonly used typical polymer compounds are polymers such as polyamides and soluble polyimines used to convert polyamides into imines. Because of its good heat resistance and chemical resistance, it has been widely used in industry as an alignment agent for aligning liquid crystals. On the other hand, this polymer compound is formed by polymerizing diamine and tetracarboxylic dianhydride, and the structure of the monomer realizes the material characteristics of the polymer compound.

對配向膜的基本要求是控制預傾角。正如所知配向膜表面的形狀、側鏈的長度會顯著影響液晶分子的預傾角。主要在二胺或四羧酸二酐上導入側鏈結構，而大多數情況下會使用能夠簡易連接側鏈的二胺。例如、日本公開專利公報昭64-25126號、日本公開專利公報平5-27244號中，公開了一種作為原料使用具備長鏈烷基等二胺的由聚醯胺酸或聚醯亞胺而成的液晶配向劑。The basic requirement for the alignment film is to control the pretilt angle. As known, the shape of the surface of the alignment film and the length of the side chain will significantly affect the pretilt angle of the liquid crystal molecules. The side chain structure is mainly introduced to diamine or tetracarboxylic dianhydride, and in most cases, a diamine that can easily connect the side chain is used. For example, Japanese Laid-open Patent Publication No. 64-25126 and Japanese Laid-open Patent Publication No. 5-27244 disclose a material made of polyamide acid or polyimide using diamines such as long-chain alkyl groups as a raw material. The liquid crystal alignment agent.

此外另一聚醯亞胺液晶配向劑也廣為所知，其作為單體使用了將直線烷氧基、烷基酯或全氟烷基用於側鏈的脂肪族側鏈型二胺。側鏈型聚醯亞胺根據芳香族或脂肪族成分，具備不同的配向膜的特徵。芳香族成分在高分子鏈中作為堅硬的核使用，在有機溶劑中其溶解性低，因此工業加工性欠佳。相反富含脂肪族或環脂肪族的配向膜則能夠改善上述缺陷。然而脂肪族聚醯胺類配向劑，具備液晶配向性欠佳並且脂肪族可溶性聚醯亞胺對基板的粘附性欠佳，從而輕微摩擦（Rubbing）其塗膜也輕易脫離的缺點。為了彌補這種缺點，還有一種混合聚醯亞胺與聚醯胺酸的配向劑，然而存在由於熱而兩者分離的問題，尤其利用嵌段共聚方法製備的液晶配向劑，存在其製備方法過於繁瑣的問題。In addition, another polyimide liquid crystal alignment agent is also widely known, which uses an aliphatic side chain type diamine in which a linear alkoxy group, an alkyl ester or a perfluoroalkyl group is used as a side chain as a monomer. The side chain polyimide has different characteristics of the alignment film according to the aromatic or aliphatic component. Aromatic components are used as hard cores in the polymer chain, and their solubility in organic solvents is low, so the industrial processability is poor. On the contrary, an alignment film rich in aliphatic or cycloaliphatic can improve the above-mentioned defects. However, the aliphatic polyamide-based alignment agent has the disadvantages of poor liquid crystal alignment and poor adhesion of the aliphatic soluble polyimide to the substrate, so that the coating film is easily detached due to slight rubbing. In order to make up for this shortcoming, there is also an alignment agent that mixes polyimine and polyamide acid. However, there is a problem of separation between the two due to heat. In particular, the liquid crystal alignment agent prepared by the block copolymerization method has its preparation method Too cumbersome question.

以前提出的具備側鏈的二胺，存在根據導入量的預傾角控制效率、或聚合反應效率差的問題。若二胺反應效率差，聚合高分子化合物所需時間拖長，甚至有時幾乎不發生聚合。若聚合時間拉長就會引發工業生產問題，若高分子化合物聚合不足，作為液晶配向膜其耐久性上就會發生問題。The previously proposed diamines having side chains have problems in that the pretilt angle control efficiency based on the amount of introduction or the polymerization reaction efficiency is poor. If the diamine reaction efficiency is poor, the time required to polymerize the high molecular compound is prolonged, and sometimes the polymerization hardly occurs. If the polymerization time is prolonged, it will cause problems in industrial production. If the polymer compound is insufficiently polymerized, problems will occur in the durability of the liquid crystal alignment film.

針對上述問題，本發明目的在於提供一種用少量導入量即可增加預傾角調節效果，並且聚合反應效率優秀的新型二胺化合物、及用該二胺合成的聚醯胺酸或聚醯亞胺、以及包含該聚合物而成的液晶配向劑。In view of the above problems, the purpose of the present invention is to provide a novel diamine compound that can increase the pretilt angle adjustment effect with a small amount of introduction and has excellent polymerization efficiency, and a polyamide acid or polyimide synthesized using the diamine. And a liquid crystal alignment agent containing the polymer.

為實現上述目的，本發明提供一種能夠簡易控制預傾角而具備良好的液晶配向性的可作為聚醯亞胺配向膜的原料使用的如下述化學式1所示的二胺化合物及其製備方法。 【化學式1】

Figure 02_image001
(上述化學式1中R1 為
Figure 02_image003
； 當n=0時，X1 為碳數12至20的烷基末端基，當n=1時，X1 為CH2 連接基；n為0或1；X2 為選自-O-或-COO-、-OCO-、-CH2 O-、-OCH2 -、-CF2 O-、-OCF2 -、-CH2 CH2 -的連接基； Z1 及Z2 分別為單鍵，
Figure 02_image005
或
Figure 02_image007
； Y1 、Y2 、Y3 、Y4 分別為H或F； Z3 選自烷基、氟基、烷氧基、全氟烷基、全氟烷氧基；a為0至5之間的值）。In order to achieve the above object, the present invention provides a diamine compound represented by the following chemical formula 1 that can easily control the pretilt angle and has good liquid crystal alignment and can be used as a raw material of a polyimide alignment film, as shown in the following chemical formula 1, and a preparation method thereof. 【Chemical formula 1】
Figure 02_image001
(R 1 in the above chemical formula 1 is
Figure 02_image003
; When n=0, X 1 is an alkyl end group with 12 to 20 carbons; when n=1, X 1 is a CH 2 linking group; n is 0 or 1; X 2 is selected from -O- or -COO-, -OCO-, -CH 2 O-, -OCH 2 -, -CF 2 O-, -OCF 2 -, -CH 2 CH 2 -linking groups; Z 1 and Z 2 are respectively single bonds,
Figure 02_image005
or
Figure 02_image007
; Y 1 , Y 2 , Y 3 , Y 4 are respectively H or F; Z 3 is selected from alkyl, fluoro, alkoxy, perfluoroalkyl, perfluoroalkoxy; a is between 0 and 5 Value).

根據本發明，可製備能夠簡易控制液晶的預傾角的二胺化合物、用上述二胺化合物而成最大限度提高液晶分子與聚醯亞胺側鏈之間的相互作用效果而具備均勻穩定的配向性的液晶配向劑。並且提供一種利用上述配向劑而成的液晶配向膜、及具備上述液晶配向膜的液晶顯示元件。According to the present invention, a diamine compound that can easily control the pretilt angle of the liquid crystal can be prepared, and the above-mentioned diamine compound can be used to maximize the interaction effect between the liquid crystal molecule and the polyimide side chain and have uniform and stable alignment. The liquid crystal alignment agent. Furthermore, there is provided a liquid crystal alignment film using the above-mentioned alignment agent, and a liquid crystal display element provided with the above-mentioned liquid crystal alignment film.

本發明的一些實施例將詳細描述如下。然而，除了如下描述外，本發明還可以廣泛地在其他的實施例施行，且本發明的範圍並不受實施例之限定，其以之後的專利範圍為準。Some embodiments of the present invention will be described in detail as follows. However, in addition to the following description, the present invention can also be widely implemented in other embodiments, and the scope of the present invention is not limited by the embodiments, and the scope of the following patents shall prevail.

若無其他定義，在本說明書中使用的所有技術及科學詞彙具備與本發明所屬技術領域專業工作人員通常所知的相同的意思。本說明書中使用的命名法使用了本技術領域習知並通用的方式。If there is no other definition, all technical and scientific words used in this specification have the same meaning as those commonly known by professionals in the technical field to which the present invention belongs. The nomenclature used in this specification uses a well-known and common method in this technical field.

本發明揭露一種能夠簡易控制預傾角從而具備良好的液晶配向性的可作為聚醯亞胺配向膜的原料使用的二胺化合物及其製備方法、用其製備的液晶配向劑用聚醯胺酸或聚醯亞胺、及其製備方法。The present invention discloses a diamine compound that can be used as a raw material for a polyimide alignment film and a preparation method thereof that can easily control the pretilt angle to have good liquid crystal alignment and a preparation method thereof, and a polyamide acid or Polyimide and its preparation method.

為實現上述目的，提供一種如下述化學式1所示的苯二胺衍生物其製備方法。 【化學式1】

Figure 02_image001
(上述化學式1中R1 為
Figure 02_image003
； 當n=0時，X1 為碳數12至20的烷基末端基，當n=1時，X1 為CH2 連接基；n為0或1；X2 為選自-O-或-COO-、-OCO-、-CH2 O-、-OCH2 -、-CF2 O-、-OCF2 -、-CH2 CH2 -的連接基； Z1 及Z2 分別為單鍵，
Figure 02_image005
或
Figure 02_image007
； Y1 、Y2 、Y3 、Y4 分別為H或F； Z3 選自烷基、氟基、烷氧基、全氟烷基、全氟烷氧基；a為0至5之間的值）。In order to achieve the above objective, a method for preparing a phenylenediamine derivative represented by the following chemical formula 1 is provided. 【Chemical formula 1】
Figure 02_image001
(R 1 in the above chemical formula 1 is
Figure 02_image003
; When n=0, X 1 is an alkyl end group with 12 to 20 carbons; when n=1, X 1 is a CH 2 linking group; n is 0 or 1; X 2 is selected from -O- or -COO-, -OCO-, -CH 2 O-, -OCH 2 -, -CF 2 O-, -OCF 2 -, -CH 2 CH 2 -linking groups; Z 1 and Z 2 are respectively single bonds,
Figure 02_image005
or
Figure 02_image007
; Y 1 , Y 2 , Y 3 , Y 4 are respectively H or F; Z 3 is selected from alkyl, fluoro, alkoxy, perfluoroalkyl, perfluoroalkoxy; a is between 0 and 5 Value).

提供一種液晶顯示裝置的垂直配向劑用聚醯亞胺樹脂的製備方法，其包括： （a）在溶劑中，將上述化學式1所示側鏈型二胺化合物與、下述化學式2所示的四羧酸酐及化學式3所示無側鏈的二胺化合物進行反應，而製備聚醯胺酸類嵌段共聚物的步驟；及 【化學式2】

Figure 104116282-A0305-003-006-001
上述化學式2所示的環脂肪族酸二酐為選自： 1,2,3,4-環丁烷四羧酸二酐、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二氯-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、3,3',4,4'-雙環己基四羧酸二酐、反-3,7-二丁基環辛-1,5-二烯-1,2,5,6-四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、5-(2,5-二氧基四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、3,5,6-三羧基-2-羧基降冰片烯-2:3、5:6-二酐、2,3,4,5-四氫呋喃四羧酸二酐、1,3,3a,4,5,9b-六氫基-5（四氫基-2,5-二氧基-3-呋喃）-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-5-甲基-5（四氫基-2,5-二氧基-3-呋喃）-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-5-乙基-5（四氫基-2,5-二氧基-3-呋喃）-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-7-甲基-5（四氫基-2,5-二氧基-3-呋喃）-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-7-乙基-5（四氫基-2,5-二氧基-3-呋喃）-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-8-甲基-5（四氫基-2,5-二氧基-3-呋喃）-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-8-乙基-5（四氫基-2,5-二氧基-3-呋喃）-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-5,8-二甲基-5（四氫基-2,5-二氧基-3-呋喃）-萘並[1,2-c]-呋喃-1，3-二酮、5-(2,5-二氧基四氫呋喃)-3-甲基-3-環己烯-1,2-二羧酸酐、雙環[2.2.2]-辛-7-烯-2,3,5,6-四羧酸二酐、3-氧雜雙環[3.2.1]辛烷-2,4-二酮-6-螺-3'-(四氫呋喃-2',5'-二酮)的一種或其組合，但並不限於此。Provided is a method for preparing a polyimide resin for a vertical alignment agent of a liquid crystal display device, which comprises: (a) In a solvent, a side chain diamine compound represented by the above chemical formula 1 and a side chain diamine compound represented by the following chemical formula 2 are combined in a solvent. The step of reacting tetracarboxylic anhydride and the diamine compound without side chains shown in Chemical Formula 3 to prepare a polyamide-based block copolymer; and [Chemical Formula 2]
Figure 104116282-A0305-003-006-001
The cycloaliphatic acid dianhydride represented by the above chemical formula 2 is selected from: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-ring Butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane Alkyltetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, trans-3,7-dibutylcyclooctane- 1,5-Diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxytetrahydro-3 -Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornene-2:3, 5:6-dianhydride , 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxy-3-furan) -Naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5(tetrahydro-2,5 -Dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl- 5(Tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b- Hexahydro-7-methyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3 ,3a,4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1 ,3-Diketone, 1,3,3a,4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxy-3-furan)-naphtho[1 ,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5(tetrahydro-2,5-dioxy- 3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5 ( Tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-dioxytetrahydrofuran)-3 -Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] One or a combination of octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), but not limited thereto.

並且，上述化學式2所示的芳香族酸二酐為選自： 均苯四甲酸二酐、4,4'-鄰苯二甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、3,3',4,4'-二苯基碸四甲酸二酸酐、1,4,5,8-萘四甲酸二酐、2,3,6,7-萘四甲酸二酐、3 3' 4 4'-聯苯醚四甲酸二酐、3,3',4,4'-二甲基二苯基矽烷四甲酸二酐、3,3',4,4'-四苯基矽烷四甲酸二酐、1,2,3,4-呋喃四甲酸二酐、4,4'-雙（3,4-二羧酸基苯氧基）二苯硫醚二酐、4,4'-雙（3,4-二羧酸基苯氧基）二苯基碸二酐、4,4'-雙（3,4-二羧酸基苯氧基）二苯基丙烷二酐、3,3',4,4'-全氟異丙基二酞酸二酐、3,3',4,4'-聯苯四甲酸二酐、雙（鄰苯二甲酸）氧化膦二酐、對苯-雙（三苯基鄰苯二甲酸）二酐、間苯-雙（三苯基鄰苯二甲酸）二酐、雙（三苯基鄰苯二甲酸）-4,4'-二苯醚二酐、雙（三苯基鄰苯二甲酸）-4,4'-二苯甲烷二酐、乙二醇-雙(脫水偏苯三酸酯）、丙二醇-雙(脫水偏苯三酸酯）、1,4-丁二醇-雙(脫水偏苯三酸酯）、1,6-己二醇-雙(脫水偏苯三酸酯）、1,8-辛二醇-雙(脫水偏苯三酸酯）、2,2-雙(4-羥苯基)丙烷-雙(脫水偏苯三酸酯）的一種或其組合，但並不限於此。In addition, the aromatic acid dianhydride represented by the above chemical formula 2 is selected from: pyromellitic dianhydride, 4,4'-phthalic dianhydride, 3,3',4,4'-benzophenone Tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride Anhydride, 3 3'4 4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetra Phenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxylic phenoxy) diphenyl sulfide dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropyl diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phosphine oxide dianhydride, P-benzene-bis(triphenylphthalic acid) dianhydride, iso-benzene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl Ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(dehydrate trimellitate), propylene glycol-bis(dehydrate trimellitate) ), 1,4-butanediol-bis(dehydrated trimellitate), 1,6-hexanediol-bis(dehydrated trimellitate), 1,8-octanediol-bis(dehydrated trimellitate) Trimellitic acid ester), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydro trimellitate) or a combination thereof, but not limited thereto.

【化學式3】

Figure 02_image012
上述化學式3所示的二胺為選自： 對苯二胺、間苯二胺、4,4'-二氨基二苯甲烷、4,4'-二氨基二苯乙烷、4,4'-二氨基二苯硫醚、4,4'-二氨基二苯碸、3,3'-二甲基-4,4'-二氨基聯苯、4,4'-二氨基苯醯替苯胺、4,4'-二氨基二苯醚、1,5-二氨基萘、2,2'-二甲基-4,4'-二氨基聯苯、5-氨基-1-(4'-氨基苯基)-1,3,3-三甲基茚滿、6-氨基-1-(4'-氨基苯基)-1,3,3-三甲基茚滿、3,4'-二氨基二苯醚、3,3'-二氨基二苯甲酮、3,4'-二氨基二苯甲酮、4,4'-二氨基二苯甲酮、2,2-雙[4-(4-氨基苯氧基)苯基]丙烷、2,2-雙[4-(4-氨基苯氧基)苯基]六氟丙烷、2,2-雙(4-氨基苯基)六氟丙烷、2,2-雙[4-(4-氨基苯氧基)苯基]碸、1,4-雙(4-氨基苯氧基)苯、1,3-雙(4-氨基苯氧基)苯、1,3-雙(3-氨基苯氧基)苯、9,9-雙(4-氨基苯基)-10-氫基蒽、2,7-二氨基芴、9,9-雙(4-氨基苯基)芴、4,4'-亞甲基-雙(2-氯苯胺)、2,2',5,5'-四氯-4,4'-二氨基聯苯、2,2'-二氯-4,4'-二氨基-5,5'-二甲氧基聯苯、3,3'-二甲氧-4,4'-二氨基聯苯、1,4,4'-(對苯異丙酯)雙苯胺、4,4'-(間苯異丙酯)雙苯胺、2,2'-雙[4-(4-氨基-2-三氟苯氧基)苯]六氟丙烷、4,4'-二氨基-2,2'-雙(三氟甲基)聯苯、4,4'-雙[(4-氨基-2-三氟甲基)苯氧基]-八氟聯苯、二(4-氨基苯)聯苯胺、1-(4-氨苯基)-1,3,3-三甲基-1H-茚-5-胺、1,1-間苯二甲胺、1,3-丙二胺、四甲撐二胺、戊撐二胺、已撐二胺、庚二胺、辛二胺、壬二胺、1,4-二氨基環己烷、異佛爾酮二胺、四氫二聚環戊二烯基二胺、三環[6.2.1.02,7]-十一碳烯二甲基二胺、4,4'-亞基雙環己胺、1,3-雙（氨甲基)環己烷等脂肪族或環脂肪族二胺； 2,3-二氨基吡啶、2,6-二氨基吡啶、3,4-二氨基吡啶、2,4-二氨基吡啶、5,6-二氨基-2,3-二氰基吡嗪、5,6-二氨基-2,4-二羥基吡啶、2,4-二氨基-6-二甲基氨基-1,3,5-三嗪、1,4-雙(3-氨丙基) 呱嗪、2,4-二氨基-6-異丙氧基-1,3,5-三嗪、2,4-二氨基-6-甲氧基-1,3,5-三嗪、2,4-二氨基-6-苯基-1,3,5-三嗪、2,4-二氨基-6-甲基-s-三嗪、2,4-二氨基-1,3,5-三嗪、2,4-二氨基-2-乙烯基-s-三嗪、2,4-二氨基-5-苯基噻唑、2,6-二氨基嘌呤、5,6-二氨基-1,3-二甲基脲嘧啶、3,5-二氨基-1,2,4-***、6,9-二氨基-2-乙氧基丫啶乳酸、3,8-二氨基-6-苯基菲啶、1,4-二氨基呱水合物、3,6-二氨基吖啶、雙(4-氨基苯基)苯胺、1-(3，5-二氨基苯基)-3-十二烷基琥珀醯亞胺、1-(3，5-二氨基苯基)-3-十八烷基琥珀醯亞胺的一種或其組合。 （上述化學式2及化學式3中，A為構成四羧酸的四價有機基；R2 為無側鏈的二價有機基。）【Chemical formula 3】
Figure 02_image012
The diamine represented by the above chemical formula 3 is selected from: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'- Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-dimethyl-4,4'-diaminodiphenyl, 4,4'-diaminophenylaniline, 4 ,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl) )-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl Ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-amino) Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2, 2-bis[4-(4-aminophenoxy)phenyl] benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1 ,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis(4-amino Phenyl) fluorene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'- Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-( P-phenylisopropyl ester) bisaniline, 4,4'-(m-phenylisopropyl ester) bisaniline, 2,2'-bis[4-(4-amino-2-trifluorophenoxy)benzene]hexafluoro Propane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octa Fluorobiphenyl, bis(4-aminophenyl)benzidine, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indene-5-amine, 1,1-m-xylylene Amine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, ethylenediamine, heptanediamine, octanediamine, nonanediamine, 1,4-diaminocyclohexane, isophor Ketone diamine, tetrahydrodicyclopentadienyl diamine, tricyclic [6.2.1.02,7]-undecene dimethyl diamine, 4,4'-ylidene dicyclohexylamine, 1, Aliphatic or cycloaliphatic diamines such as 3-bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-bis Aminopyridine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyridine, 2,4-diamino-6-dimethylamino-1 ,3,5-triazine, 1,4-bis(3-aminopropyl)piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4- Diamino-6-methoxy-1,3,5-triazine, 2,4-di Amino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 2 ,4-Diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyl Yluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactic acid, 3,8-diamino-6-phenylphenanthridine, 1,4-Diamino hydrate, 3,6-diaminoacridine, bis(4-aminophenyl)aniline, 1-(3,5-diaminophenyl)-3-dodecyl succinate One of imine, 1-(3,5-diaminophenyl)-3-octadecyl succinimidyl or a combination thereof. (In the above Chemical Formula 2 and Chemical Formula 3, A is a tetravalent organic group constituting a tetracarboxylic acid; R 2 is a divalent organic group without a side chain.)

（b）將反應上述化學式2及化學式3而製備的聚醯胺酸類嵌段共聚物進行熱處理，通過脫水閉環反應轉變成聚醯亞胺的步驟。(B) A step of heat-treating the polyamide-based block copolymer prepared by reacting the above-mentioned chemical formula 2 and chemical formula 3, and converting it into a polyimide by a dehydration ring-closing reaction.

並且，本發明提供一種包括上述液晶配向膜的液晶顯示元件。Furthermore, the present invention provides a liquid crystal display element including the above-mentioned liquid crystal alignment film.

下面詳細說明本發明。The present invention will be described in detail below.

本發明的液晶配向材料為了減少聚合時由於側鏈而發生的立體阻礙，如上述化學式1所示在各個苯環上將兩個氨基取代，並在氨基被取代的兩個苯環上連接甲基以使液晶更為均勻地配向，並顯著提高了對有機溶劑的可溶性及透明性。此時側鏈為了簡易調節預傾角，具備如上述化學式1所示的烷基鏈、芳香族、環脂肪族。通過這種結構，使側鏈具備環脂肪結構時，可改善由於摩擦（Rubbing）而粘附性降低的問題，具有這種效果。In order to reduce the steric hindrance due to side chains during polymerization, the liquid crystal alignment material of the present invention replaces two amino groups on each benzene ring as shown in the above chemical formula 1, and connects methyl groups to the two benzene rings where the amino groups are substituted. In order to make the liquid crystal more uniformly aligned, and significantly improve the solubility and transparency of organic solvents. In this case, in order to easily adjust the pretilt angle, the side chain includes an alkyl chain, aromatic, and cycloaliphatic as shown in the above chemical formula 1. With this structure, when the side chain is provided with a cycloaliphatic structure, the problem of reduced adhesion due to rubbing can be improved, which has such an effect.

上述化學式1中這些側鏈設計成能夠實現本發明目的。位於側鏈末端的烷基鏈可減少表面張力，並且在高分子鏈之間形成有機溶劑滲入的空間從而增加溶解性。These side chains in the above chemical formula 1 are designed to achieve the purpose of the present invention. The alkyl chain at the end of the side chain can reduce the surface tension and form a space between the polymer chains for the organic solvent to penetrate to increase the solubility.

並且脂肪族的環不僅能夠支撐液晶分子，還將堅硬的核與末端的烷基連接成如液晶一樣的條形，而液晶位於側鏈周圍時，通過與液晶側面的相互作用提高液晶配向性。In addition, the aliphatic ring can not only support the liquid crystal molecules, but also connect the hard core and the terminal alkyl group into a strip like liquid crystal. When the liquid crystal is located around the side chain, the liquid crystal alignment can be improved by the interaction with the side surface of the liquid crystal.

並且具備側鏈的聚醯亞胺樹脂，根據液晶分子長軸的平均長度與所需預傾角大小，決定二胺側鏈的長度及側鏈間隔的長度。本發明可通過調節這些因素，而調節聚醯亞胺類共聚物的性質。In addition, the polyimide resin with side chains determines the length of the diamine side chain and the length of the side chain interval according to the average length of the long axis of the liquid crystal molecule and the required pretilt angle. The present invention can adjust the properties of the polyimide copolymer by adjusting these factors.

上述製備方法的步驟（a）中的溶劑為選自由N-甲基-2-吡咯烷酮（NMP）、N,N-二甲基甲醯胺（DMF）、二甲基亞碸（DMSO）、二甲基乙醯胺、γ-丁內酯、六甲基磷醯三胺、六甲基磷醯胺、四氫噻吩碸、四甲基脲、對氯苯酚、對溴苯酚、2-氯-4-羥基甲苯、二噁烷、四氫呋喃（THF）、以及環己酮組成的組中的一種以上的非活性溶劑。有機溶劑的使用量，通常調節成固形粉（二胺及二酐化合物）的總量占反應溶液總量的0.1至30重量百分比為佳。The solvent in step (a) of the above preparation method is selected from N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethyl sulfide (DMSO), two Methyl acetamide, γ-butyrolactone, hexamethylphosphoramide, hexamethylphosphoramide, tetrahydrothiophene, tetramethylurea, p-chlorophenol, p-bromophenol, 2-chloro-4 -One or more inactive solvents in the group consisting of hydroxytoluene, dioxane, tetrahydrofuran (THF), and cyclohexanone. The amount of organic solvent used is usually adjusted so that the total amount of solid powder (diamine and dianhydride compounds) accounts for 0.1 to 30 weight percent of the total amount of the reaction solution.

特徵在於，通過本發明的上述製備方法製備的聚醯亞胺樹脂，重均分子量為1,000至200,000的液晶顯示裝置的液晶配向劑用聚醯亞胺樹脂。It is characterized in that the polyimide resin prepared by the above-mentioned preparation method of the present invention is a polyimide resin for a liquid crystal alignment agent of a liquid crystal display device with a weight average molecular weight of 1,000 to 200,000.

並且，特徵在於，本發明中上述聚醯亞胺樹脂的側鏈長度為液晶分子長軸長度的0.8倍至1.5倍，側鏈間的長度為液晶分子長軸長度的1.5倍至3.5倍。Furthermore, it is characterized in that the length of the side chains of the polyimide resin in the present invention is 0.8 to 1.5 times the length of the long axis of the liquid crystal molecules, and the length between the side chains is 1.5 to 3.5 times the length of the long axis of the liquid crystal molecules.

並且，本發明提供一種利用上述液晶顯示裝置的液晶配向劑用聚醯亞胺樹脂而製備的液晶配向膜及包含它的液晶顯示元件。In addition, the present invention provides a liquid crystal alignment film prepared by using the polyimide resin for a liquid crystal alignment agent of the liquid crystal display device and a liquid crystal display element containing the same.

下面詳細說明本發明的液晶配向劑用側鏈型二胺聚醯亞胺樹脂的製備方法。The preparation method of the side chain diamine polyimide resin for liquid crystal alignment agent of the present invention will be described in detail below.

上述化學式1的二胺化合物可通過反應式1或反應式2的方法製備。The diamine compound of the above Chemical Formula 1 can be prepared by the method of Reaction Formula 1 or Reaction Formula 2.

首先，當化學式1中n=1時，反應式1中各步驟的製備方法如下。 【反應式1】

Figure 02_image014
First, when n=1 in Chemical Formula 1, the preparation method of each step in Reaction Formula 1 is as follows. 【Reaction Formula 1】
Figure 02_image014

第一步驟 在反應容器中加入4-(2,2-雙(4-氨基苯基)乙基)苯並加入二氯甲烷進行溶解。滴加二碳酸二叔丁酯後攪拌，在反應容器中加水而完成反應後，提取二氯甲烷，然後蒸發全部有機溶劑。將製得混合物用柱層析法(column chromatography)（二氧化矽，己烷/醋酸乙酯=1/1）進行分離而製取嫩黃色固體二叔丁基(2-(4-羥基苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸。 The first step Add 4-(2,2-bis(4-aminophenyl)ethyl)benzene to the reaction vessel and add dichloromethane to dissolve. After dropping di-tert-butyl dicarbonate and stirring, add water to the reaction vessel to complete the reaction, extract dichloromethane, and then evaporate all the organic solvents. The obtained mixture was separated by column chromatography (silica dioxide, hexane/ethyl acetate = 1/1) to prepare a bright yellow solid di-tert-butyl (2-(4-hydroxyphenyl) ) Ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid.

第二步驟 連接部X2 為醚基團（-O-），酯基團（-COO-）等連接基，這些連接基可通過通常使用的有機合成法製備。 The second step The connecting portion X 2 is a connecting group such as an ether group (-O-), an ester group (-COO-), etc., and these connecting groups can be prepared by a commonly used organic synthesis method.

具體來說，在醚及酯中對應的鹵素X3 被取代的苯衍生物、或鹵素X3 被取代的烷基衍生物、與包括連接部X2 的羥基衍生物，在鹼性條件下進行反應。Specifically, in ethers and esters, the corresponding halogen X 3 substituted benzene derivatives, or halogen X 3 substituted alkyl derivatives, and the hydroxy derivative including the linking part X 2 are carried out under basic conditions. reaction.

作為典型的合成例，若要製備醚基團，在反應容器中將二叔丁基(2-(4-羥基苯基)乙烷-1，1-二基)雙(4,1-亞苯基)-二羧酸溶解在二甲基甲醯胺(DMF)中，加入氫氧化鈉（NaOH），在室溫進行反應，然後將要連接的鹵元素取代化合物溶解在二甲基甲醯胺(DMF)中後，進行反應而製備。若要製備酯基團，則在反應容器中將二叔丁基(2-(4-羥基苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸溶解在氯甲烷中，加入羧酸取代化合物、二環己基碳二亞胺(DCC)(3.68g，17.86mmol)、4-二甲氨基吡啶(DMAP)（0.22g，1.79mmol），在室溫進行反應而製備。As a typical synthesis example, to prepare ether groups, di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene) Yl)-dicarboxylic acid is dissolved in dimethylformamide (DMF), sodium hydroxide (NaOH) is added, and the reaction is carried out at room temperature, and then the halogen element substituted compound to be connected is dissolved in dimethylformamide ( After DMF), it is prepared by reaction. To prepare ester groups, di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid Dissolve in methyl chloride, add carboxylic acid substituted compound, dicyclohexylcarbodiimide (DCC) (3.68g, 17.86mmol), 4-dimethylaminopyridine (DMAP) (0.22g, 1.79mmol), at room temperature Prepared by reaction.

第三步驟 在前一步驟中在叔丁氧羰基保護基中加入三氟乙酸(TFA)後，脫保護基而製取所需二胺化合物。 The third step In the previous step, after adding trifluoroacetic acid (TFA) to the tert-butoxycarbonyl protective group, the protective group is removed to prepare the desired diamine compound.

並且，當化學式1中n=0時，反應式2的各步驟的製備方法如下。 【反應式2】

Figure 02_image015
And, when n=0 in Chemical Formula 1, the preparation method of each step of Reaction Formula 2 is as follows. [Reaction formula 2]
Figure 02_image015

第一步驟 加入雙(4-硝基苯基)甲烷後用N2 取代後，溶解在甲苯中，並降溫為0℃。將乙醇鉀溶解在5ml乙醇(EtOH)中後，緩慢滴加到降溫為0℃的溶液中。升溫為室溫後攪拌4小時，然後過濾並將濾出的固體用甲苯清洗後，在真空乾燥箱中乾燥14小時，而製取青紫色固體即雙(4-硝基苯基)甲烷、鉀鹽。After a first step of adding bis (4-nitrophenyl) methane, N 2 After substitution, dissolved in toluene, and cooled to 0 ℃. After dissolving potassium ethoxide in 5 ml of ethanol (EtOH), it was slowly added dropwise to the solution whose temperature was lowered to 0°C. Warm up to room temperature and stir for 4 hours, then filter and wash the filtered solid with toluene, and then dry it in a vacuum drying oven for 14 hours to prepare a blue-purple solid, namely bis(4-nitrophenyl)methane and potassium Salt.

第二步驟 構築單鍵可使用很多種方法，例如可使用格氏（Grinard）反應、傅-克反應（Friedel-Crafts）醯化方法、凱惜納（Kishner）還原方法等普通有機合成法，進行適當連接。 In the second step, many methods can be used to construct single bonds. For example, ordinary organic synthesis methods such as Grignard reaction, Friedel-Crafts reaction, Kishner reduction method, etc. can be used. Connect appropriately.

具體說，將雙(4-硝基苯基)甲烷、鉀鹽溶解在二甲基甲醯胺(DMF)後，降溫為0℃。緩慢滴加1-溴十六烷。升溫為室溫攪拌12小時。用柱層析法製取(4,4'-十七烷-1,1-二基)雙(硝基苯)。Specifically, after dissolving bis(4-nitrophenyl)methane and potassium salt in dimethylformamide (DMF), the temperature is lowered to 0°C. Slowly add 1-bromohexadecane dropwise. The temperature was raised to room temperature and stirred for 12 hours. Prepare (4,4'-heptadecan-1,1-diyl) bis(nitrobenzene) by column chromatography.

第三步驟 用於將二硝基化合物還原的方法沒有特別限制，通常作為催化劑使用鈀碳、二氧化鉑、雷尼鎳、鉑黑、銠鋁、硫化鉑碳等，並在乙酸乙酯、甲苯、四氫呋喃、二噁烷、醇類等溶劑中，通過氫氣、聯氨、氯化氫等進行。 The method for reducing the dinitro compound in the third step is not particularly limited. Usually, palladium carbon, platinum dioxide, Raney nickel, platinum black, rhodium aluminum, platinum sulfide carbon, etc. are used as a catalyst. , Tetrahydrofuran, dioxane, alcohols and other solvents, using hydrogen, hydrazine, hydrogen chloride, etc.

具體說，將(4,4'-十七烷-1,1-二基)雙(硝基苯)溶解在乙醇（EtOH）中後，緩慢加入5重量百分比Pd/C。滴加多量水合肼。在室溫攪拌2小時後進行過濾除去Pd/C後，減壓蒸餾溶劑而去除，並用水（H2 O）與乙酸乙酯（EA）進行提取後，用柱層析法製取(4,4'-十七烷-1,1-二基)雙(二苯胺)。Specifically, after dissolving (4,4'-heptadecan-1,1-diyl)bis(nitrobenzene) in ethanol (EtOH), 5 weight percent Pd/C is slowly added. Drop a large amount of hydrazine hydrate. After stirring at room temperature for 2 hours, filtering to remove Pd/C, the solvent was distilled under reduced pressure to remove, and after extraction with water (H 2 O) and ethyl acetate (EA), column chromatography was used to prepare (4,4 '-Heptadecan-1,1-diyl)bis(diphenylamine).

下面，提供使用化學式1的二胺化合物製備的聚醯亞胺樹脂及其製備方法。 根據本發明的用化學式1製備聚醯亞胺樹脂的步驟，其特徵在於，包括： （a）在溶劑中，將上述化學式1所示側鏈型二胺化合物與、化學式2所示的四羧酸酐及化學式3所示無側鏈的二胺化合物進行反應，而製備下述化學式4的聚醯胺酸類嵌段共聚物的步驟；及 【化學式4】

Figure 02_image017
（b）將上述聚醯胺酸類嵌段共聚物進行熱處理，通過脫水閉環反應轉變成化學式5所示的聚醯亞胺的步驟。 【化學式5】
Figure 02_image019
（上述化學式4及化學式5中A為構成四羧酸的四價有機基；B為構成來自化學式1及化學式3的二胺的二價有機基）Below, a polyimide resin prepared using the diamine compound of Chemical Formula 1 and a preparation method thereof are provided. The step of preparing a polyimide resin by using Chemical Formula 1 according to the present invention is characterized in that it comprises: (a) In a solvent, the side chain diamine compound shown in the above Chemical Formula 1 is combined with the tetracarboxylic acid shown in Chemical Formula 2 The step of reacting the acid anhydride with the side chain-free diamine compound shown in Chemical Formula 3 to prepare the polyamide acid-based block copolymer of the following Chemical Formula 4; and [Chemical Formula 4]
Figure 02_image017
(B) A step of heat-treating the polyamide-based block copolymer described above to convert it into a polyimide represented by Chemical Formula 5 through a dehydration ring-closure reaction. 【Chemical formula 5】
Figure 02_image019
(In the above chemical formula 4 and chemical formula 5, A is the tetravalent organic group constituting the tetracarboxylic acid; B is the divalent organic group constituting the diamine from the chemical formula 1 and 3)

作為具體的例，將上述化學式1的側鏈型二胺化合物與上述化學式3的二胺，溶解在N-甲基-2-吡咯烷酮的反應溶液，維持5℃，並在氮氣氣氛下緩慢滴加上述化學式2的四羧酸二酐後，在室溫攪拌6小時而製備聚醯胺酸類嵌段共聚物。此時，可利用乙二醇單甲醚、乙二醇單***、乙二醇單丁醚等纖維素溶劑調節粘度。As a specific example, the side chain diamine compound of the above chemical formula 1 and the diamine of the above chemical formula 3 are dissolved in a reaction solution of N-methyl-2-pyrrolidone, maintained at 5°C, and slowly added dropwise under a nitrogen atmosphere After the tetracarboxylic dianhydride of the above chemical formula 2, it was stirred at room temperature for 6 hours to prepare a polyamide-based block copolymer. In this case, cellulose solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether can be used to adjust the viscosity.

然後，本發明將聚醯胺酸類嵌段共聚物用100至250℃溫度熱處理30分至2小時，通過脫水閉環反應轉變成聚醯亞胺。Then, in the present invention, the polyamide-based block copolymer is heat-treated at a temperature of 100 to 250° C. for 30 minutes to 2 hours, and converted into a polyimide by a dehydration ring-closing reaction.

並且，也可以在有鹼性催化劑與酸酐的條件下，將聚醯胺酸在0至180℃下攪拌1至100小時，通過化學的二胺化反應而轉變成聚醯亞胺。製得的聚醯亞胺溶液利用如在合成上述聚醯胺酸時所提及一樣的沉澱分離法為佳。In addition, under the condition of a basic catalyst and an acid anhydride, the polyamide acid may be stirred at 0 to 180° C. for 1 to 100 hours, and converted into polyimide by a chemical diamination reaction. The prepared polyimide solution preferably uses the same precipitation separation method as mentioned in the synthesis of the above-mentioned polyimide acid.

在製備上述聚醯胺酸時使用的溶劑，只要是能夠溶解聚醯胺酸就沒有特別限制，作為具體的例子，有N-甲基-2-吡咯烷酮（NMP）、N,N-二甲基甲醯胺（DMF）、二甲基亞碸（DMSO）、二甲基乙醯胺、γ-丁內酯、六甲基磷醯三胺、六甲基磷醯胺、四氫噻吩碸、四甲基脲、對氯苯酚、對溴苯酚、2-氯-4-羥基甲苯、二噁烷、四氫呋喃（THF）、環己酮等。並且即使是不能溶解聚醯胺酸的溶劑，只要不會析出生成的聚醯胺酸，可與上述溶劑混合使用。進而由於有機溶劑中的水會阻礙聚合反應並對所生成的聚醯胺酸進行水解，因此使用脫水乾燥的有機溶劑為佳。The solvent used in the preparation of the above polyamide acid is not particularly limited as long as it can dissolve the polyamide acid. Specific examples include N-methyl-2-pyrrolidone (NMP) and N,N-dimethyl Formamide (DMF), dimethyl sulfide (DMSO), dimethylacetamide, γ-butyrolactone, hexamethylphosphoramide, hexamethylphosphoramide, tetrahydrothiophene, tetrahydrothiophene Methylurea, p-chlorophenol, p-bromophenol, 2-chloro-4-hydroxytoluene, dioxane, tetrahydrofuran (THF), cyclohexanone, etc. Moreover, even if it is a solvent that cannot dissolve polyamic acid, as long as the generated polyamic acid does not precipitate, it can be used in combination with the above-mentioned solvent. Furthermore, since water in the organic solvent hinders the polymerization reaction and hydrolyzes the produced polyamide acid, it is preferable to use a dehydrated and dried organic solvent.

在聚醯胺酸製備步驟中的四羧酸酐中A是四價有機基。作為具體的例子，有3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)、4,4'-氧雙鄰苯二甲酸酐(ODPA)、3,3',4,4'-聯苯四甲酸二酐（BPDA）、1,2,4,5-均苯四甲酸二酐（PMDA）、環丁烷四甲酸二酐（CBDA）及4-(2,5-二氧代四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二甲酸酐（TDA）等。In the tetracarboxylic anhydride in the polyamide acid preparation step, A is a tetravalent organic group. As specific examples, there are 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3',4 ,4'-Biphenyltetracarboxylic dianhydride (BPDA), 1,2,4,5-pyromellitic dianhydride (PMDA), cyclobutanetetracarboxylic dianhydride (CBDA) and 4-(2,5- Dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA), etc.

並且，上述化學式4或化學式5中帶氮原子的二胺是構成上述化學式1的二價有機基。與位於二胺側鏈末端的亞甲基相連接的苄基衍生物可具備液晶配向性，大量包括芳香族的主鏈與側鏈二胺、及四羧酸酐可增加表面極性，同時降低配向膜的表面張力從而對預傾角的調節有影響。並且，與二胺相連的苄基形成有機溶劑能夠滲入鏈之間的空間，從而增加溶解性。In addition, the diamine with a nitrogen atom in the above Chemical Formula 4 or Chemical Formula 5 is a divalent organic group constituting the above Chemical Formula 1. The benzyl derivative connected to the methylene group at the end of the diamine side chain can have liquid crystal alignment. A large number of aromatic main chain and side chain diamines, and tetracarboxylic anhydride can increase the surface polarity and reduce the alignment film. The surface tension thus has an effect on the adjustment of the pretilt angle. In addition, the benzyl group connected to the diamine can form an organic solvent that can penetrate into the space between the chains, thereby increasing solubility.

並且，上述化學式4或化學式5中帶氮原子的二胺化合物，可使用來自化學式3（無側面取代基的二胺化合物）中的二價有機基。具體有4,4'-二氨基二苯醚(ODA)、4,4'-亞甲基雙環己烷胺(PACM)、4,4'-亞甲基-2-甲基環己胺(ANCAMINE)、4,4'-亞甲基二苯胺、二氨基二苯甲酮、4,4'-亞甲基二苯基二胺(MDA)、4,4'-六氟異丙基二苯基二胺(6FDA)、對苯二胺(p-PDA)等。In addition, the diamine compound with a nitrogen atom in the above Chemical Formula 4 or Chemical Formula 5 may use a divalent organic group from the Chemical Formula 3 (diamine compound without side substituents). Specifically, 4,4'-diaminodiphenyl ether (ODA), 4,4'-methylene bicyclohexaneamine (PACM), 4,4'-methylene-2-methylcyclohexylamine (ANCAMINE ), 4,4'-methylenediphenylamine, diaminobenzophenone, 4,4'-methylenediphenyldiamine (MDA), 4,4'-hexafluoroisopropyldiphenyl Diamine (6FDA), p-phenylenediamine (p-PDA), etc.

為了製取聚醯胺酸而在有機溶劑中反應四羧酸二酐成分與二胺成分時，通常保持5℃至100℃為佳。若溫度很高，雖然可快速完成聚合，但高分子分子量會變得過高，因此要慎重。並且，反應濃度在5%至30%重量百分比時，可進行均勻地攪拌而製取所需分子量。製備的聚醯胺酸可利用反應溶液稀釋後使用，也可通過沉澱分離進行再溶解後使用。對於沉澱分離中使用的不良溶劑沒有特別限制，可舉例甲醇、乙醇、己烷、丙酮、丁基溶纖劑、丁酮、甲苯、苯、***等。通過加入不良溶劑而形成的聚醯胺酸沉澱，進行過濾、清洗而分離後，在常壓或減壓條件下，室溫乾燥或加熱乾燥而製得固形粉。When the tetracarboxylic dianhydride component and the diamine component are reacted in an organic solvent in order to prepare polyamide acid, it is generally preferable to keep the temperature at 5°C to 100°C. If the temperature is high, although the polymerization can be completed quickly, the molecular weight of the polymer will become too high, so be cautious. Moreover, when the reaction concentration is 5% to 30% by weight, uniform stirring can be carried out to obtain the desired molecular weight. The prepared polyamide acid can be used after being diluted with the reaction solution, or can be used after being re-dissolved through precipitation separation. The poor solvent used in precipitation separation is not particularly limited, and examples include methanol, ethanol, hexane, acetone, butyl cellosolve, methyl ethyl ketone, toluene, benzene, ether, and the like. The polyamide acid precipitate formed by adding a poor solvent is filtered, washed and separated, and then dried at room temperature or heated under normal pressure or reduced pressure to obtain a solid powder.

在上述聚醯亞胺側鏈型中二價有機基R2 用於對聚醯亞胺增添液晶配向性、溶解性及模穿透性等功能，無側鏈的二價有機基R2 則用於調節側鏈間的間距而決定側鏈基團的分佈率。上述化學式7及化學式8中n為1至10中的整數，更優先為2至4。In the above-mentioned polyimide side chain type, the divalent organic group R 2 is used to add the functions of liquid crystal alignment, solubility and mode penetration to the polyimide, and the divalent organic group R 2 without side chain is used The spacing between the side chains is adjusted to determine the distribution rate of the side chain groups. In the above Chemical Formula 7 and Chemical Formula 8, n is an integer from 1 to 10, more preferably from 2 to 4.

上述側鏈型中二價有機基R2 的側鏈長度，設計成液晶分子長軸平均長度的0.8至1.5倍為佳，並且側鏈間的長度設計成液晶分子長軸長度的1.5倍至3.5倍，並且需要選擇性地決定無側鏈的二價有機基R2 的類型與使用量。通過上述方法聚醯亞胺具備良好的配向性，並且可製備在溶解性、膜穿透性、化學穩定性上具備良好的性質的特定結構的聚醯亞胺樹脂。上述聚醯亞胺樹脂的重均分子量優先為1,000至200,000。The side chain length of the divalent organic group R 2 in the side chain type is preferably designed to be 0.8 to 1.5 times the average length of the long axis of the liquid crystal molecules, and the length between the side chains is designed to be 1.5 times to 3.5 times the length of the long axis of the liquid crystal molecules. It is necessary to selectively determine the type and usage amount of the divalent organic group R 2 without side chains. By the above method, the polyimide has good alignment properties, and a polyimide resin with a specific structure with good properties in terms of solubility, membrane penetration, and chemical stability can be prepared. The weight average molecular weight of the above-mentioned polyimide resin is preferably 1,000 to 200,000.

並且，本發明提供一種利用上述聚醯亞胺樹脂的液晶配向膜，上述液晶配向膜在圖案化的基板上塗布包括上述聚醯亞胺化合物的配向液後進行燒制而成。在上述配向液中使用的溶劑，只要是通常用於液晶配向液且可溶解上述聚醯亞胺化合物即可，沒有特別限制，在配向液中包含1至30重量百分比的上述聚醯亞胺化合物為佳。In addition, the present invention provides a liquid crystal alignment film using the polyimide resin, which is formed by coating an alignment solution including the polyimide compound on a patterned substrate and firing the liquid crystal alignment film. The solvent used in the above-mentioned alignment liquid is not particularly limited as long as it is usually used in the liquid crystal alignment liquid and can dissolve the above-mentioned polyimide compound. The alignment liquid contains 1 to 30% by weight of the above-mentioned polyimide compound. Better.

本發明的液晶配向膜具有良好的液晶配向性與磨擦（Rubbing）耐性，並且電壓保持率、對比度高，並且用於降低電荷累積的液晶預傾角的調節比較簡易，利用側鏈型二胺化合物可最大限度提高液晶分子與聚醯亞胺側鏈之間的相互作用效果，而具備90℃預傾角，從而可獲得均勻穩定的配向性。The liquid crystal alignment film of the present invention has good liquid crystal alignment and rubbing resistance, and has high voltage retention and contrast, and the adjustment of the liquid crystal pretilt angle for reducing charge accumulation is relatively simple. The side chain diamine compound can be used It maximizes the interaction effect between the liquid crystal molecules and the polyimide side chain, and has a pretilt angle of 90°C, so that uniform and stable alignment can be obtained.

下面，參照下述實施例詳細敘述本發明，但本發明的範圍並不限於上述實施例。Hereinafter, the present invention will be described in detail with reference to the following embodiments, but the scope of the present invention is not limited to the above-mentioned embodiments.

【合成例1】 合成二叔丁基（2-（4-羥基苯基）乙烷-1，1-二基）雙（4，1-亞苯基）二羧酸 (di-tert-butyl((2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene))dicarbamate)

Figure 02_image021
在反應容器中加入4-(2,2-雙(4-氨基苯)乙基)苯（15.0，49.3mmol）後，再加入二氯甲烷（20mL）進行溶解。在冰浴的反應容器中滴加二羧酸二叔丁酯（24.9mL，108.4mmol）後室溫攪拌12小時。在反應容器中加水而完成反應後，提取二氯甲烷，然後蒸發全部有機溶劑。將製得混合物用柱層析法（二氧化矽，己烷/醋酸乙酯=1/1）進行分離而製取嫩黃色固體（14.9g，61%）。1 H NMR (300 MHz, CDCl3 ) δ7.20 (d, 4H), 7.06 (d, 4H), 6.81 (d, 2H), 6.61 (d, 2H), 6.35 (s, 2H), 4.50 (s, 1H), 1.53 (s, 18H)。[Synthesis Example 1] Synthesis of di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (di-tert-butyl( (2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene))dicarbamate)
Figure 02_image021
After adding 4-(2,2-bis(4-aminophenyl)ethyl)benzene (15.0, 49.3 mmol) to the reaction vessel, dichloromethane (20 mL) was added to dissolve. Di-tert-butyl dicarboxylate (24.9 mL, 108.4 mmol) was added dropwise to a reaction vessel in an ice bath, and then stirred at room temperature for 12 hours. After adding water to the reaction vessel to complete the reaction, extract the dichloromethane, and then evaporate all the organic solvents. The obtained mixture was separated by column chromatography (silica dioxide, hexane/ethyl acetate = 1/1) to obtain a bright yellow solid (14.9 g, 61%). 1 H NMR (300 MHz, CDCl 3 ) δ7.20 (d, 4H), 7.06 (d, 4H), 6.81 (d, 2H), 6.61 (d, 2H), 6.35 (s, 2H), 4.50 (s , 1H), 1.53 (s, 18H).

合成4-(2,2-雙(4-氨基苯)甲基)苯4-(4,4,4-三氟丁氧基)苯甲酸 （ 4-(2,2-bis(4-aminophenyl)methyl)phenyl 4-(4,4,4-trifluorobutoxy)benzoate）

Figure 02_image023
在反應容器將二叔丁基(2-(4-羥基苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸(9g，17.86mmol)溶解在二氯甲烷(200mL)中，加入4-(4,4,4-三氟丁氧基)苯甲酸(4.43，17.86mmol）、二環己基碳二亞胺(DCC)(3.68g，17.86mmol)、4-二甲氨基吡啶(DMAP)(0.22g，1.79mmol)，在室溫反應12小時而製備4-(2,2-雙(4-叔丁氧羰基)甲基)苯4-(4,4,4-三氟丁氧基)苯甲酸（9g，68%）。在0℃下加入4-(2,2-雙(4-叔丁氧羰基)甲基)苯 4-(4,4,4-三氟丁氧基)苯甲酸(7g，9.5mmol)與三氟乙酸(TFA)(40mL)後，反應1小時製取4-(2,2-雙(4-氨基苯)甲基)苯 4-(4,4,4-三氟丁氧基)苯甲酸（4g，78%）。1 H NMR (300 MHz, DMSO) δ8.01 (d, 2H), 7.12 (m, 4H), 6.99 (d, 2H), 6.88 (d, 4H), 6.40 (d, 4H), 4.75 (s, 4H), 4.13 (t, 2H), 3.90 (t, 1H), 3.16 (d, 2H), 2.41 (m, 2H), 1.95 (m, 2H)。Synthesis of 4-(2,2-bis(4-aminophenyl)methyl)benzene 4-(4,4,4-trifluorobutoxy)benzoic acid (4-(2,2-bis(4-aminophenyl) methyl)phenyl 4-(4,4,4-trifluorobutoxy)benzoate)
Figure 02_image023
Dissolve di-tert-butyl (2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (9g, 17.86mmol) in the reaction vessel To methyl chloride (200mL), add 4-(4,4,4-trifluorobutoxy)benzoic acid (4.43, 17.86mmol), dicyclohexylcarbodiimide (DCC) (3.68g, 17.86mmol), 4-Dimethylaminopyridine (DMAP) (0.22g, 1.79mmol) was reacted at room temperature for 12 hours to prepare 4-(2,2-bis(4-tert-butoxycarbonyl)methyl)benzene 4-(4, 4,4-Trifluorobutoxy)benzoic acid (9g, 68%). Add 4-(2,2-bis(4-tert-butoxycarbonyl)methyl)benzene 4-(4,4,4-trifluorobutoxy)benzoic acid (7g, 9.5mmol) and tris After fluoroacetic acid (TFA) (40mL), react for 1 hour to prepare 4-(2,2-bis(4-aminophenyl)methyl)benzene 4-(4,4,4-trifluorobutoxy)benzoic acid (4g, 78%). 1 H NMR (300 MHz, DMSO) δ8.01 (d, 2H), 7.12 (m, 4H), 6.99 (d, 2H), 6.88 (d, 4H), 6.40 (d, 4H), 4.75 (s, 4H), 4.13 (t, 2H), 3.90 (t, 1H), 3.16 (d, 2H), 2.41 (m, 2H), 1.95 (m, 2H).

【合成例2】 合成4-(2,2-雙(4-氨基苯)乙基)苯2,3',4',5'-四氯-[1,1'-聯苯]-4-羧酸 （4-(2,2-bis(4-aminophenyl)ethyl)phenyl2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-carboxylate)

Figure 02_image025
在反應容器中將二叔丁基(2-(4-羥基苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸(9g，17.86mmol)溶解在二氯甲烷（200mL）中，加入2,3',4',5'-四氟-[1,1'-聯苯]-4-羧酸（4.83g，17.86mmol）、二環己基碳二亞胺(DCC)（3.68g，17.86mmol）、4-二甲氨基吡啶(DMAP)（0.22g，1.79mmol），在室溫反應12小時而製備4-(2,2-雙(4-叔丁氧羰基)乙基)苯2,3',4',5'-四氟-[1,1'-聯苯]-4-羧酸（9g，67%）。 在0℃下加入4-(2,2-雙((4-叔丁氧羰基)氨基)苯基)乙基)苯2,3',4',5'-四氟-[1,1'-聯苯]-4-羧酸（9g，11.97mmol）與三氟乙酸(TFA)（50mL）後，反應1小時製取4-(2,2-雙(4-氨基苯基)乙基)苯2,3',4',5'-四氟-[1,1'-聯苯]-4-羧酸（5g，74%）。1 H NMR (300 MHz, CDCl3 ) δ8.19 (dd, 1H), 7.99 (d, 1H), 7.88 (d, 1H), 7.27-7.21 (m, 6H), 6.95 (d, 4H), 6.34 (d, 4H), 4.44 (t, 1H), 3.9(s, 4H, NH), 3.17(d, 2H)。[Synthesis Example 2] Synthesis of 4-(2,2-bis(4-aminophenyl)ethyl)benzene 2,3',4',5'-tetrachloro-[1,1'-biphenyl]-4- Carboxylic acid (4-(2,2-bis(4-aminophenyl)ethyl)phenyl2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-carboxylate)
Figure 02_image025
Dissolve di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (9g, 17.86mmol) in the reaction vessel In dichloromethane (200mL), add 2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-carboxylic acid (4.83g, 17.86mmol), dicyclohexyl carbon two Imine (DCC) (3.68g, 17.86mmol), 4-dimethylaminopyridine (DMAP) (0.22g, 1.79mmol), react at room temperature for 12 hours to prepare 4-(2,2-bis(4-tert Butoxycarbonyl)ethyl)benzene 2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-carboxylic acid (9g, 67%). Add 4-(2,2-bis((4-tert-butoxycarbonyl)amino)phenyl)ethyl)benzene 2,3',4',5'-tetrafluoro-[1,1' at 0℃ -Biphenyl]-4-carboxylic acid (9g, 11.97mmol) and trifluoroacetic acid (TFA) (50mL), react for 1 hour to prepare 4-(2,2-bis(4-aminophenyl)ethyl) Benzene 2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-carboxylic acid (5g, 74%). 1 H NMR (300 MHz, CDCl 3 ) δ8.19 (dd, 1H), 7.99 (d, 1H), 7.88 (d, 1H), 7.27-7.21 (m, 6H), 6.95 (d, 4H), 6.34 (d, 4H), 4.44 (t, 1H), 3.9(s, 4H, NH), 3.17(d, 2H).

【合成例3】 合成4,4’-(2-(4-(3,4,5-三氟苯氧基）苯基）乙烷-1,1-二基)二苯胺 （4,4'-(2-(4-(3,4,5-trifluorophenoxy)phenyl)ethane-1,1-diyl)dianiline）

Figure 02_image027
在反應容器將二叔丁基(2-(4-羥基苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸(5g，9.9mmol)溶解在二甲基甲醯胺(DMF)（100mL）中，加入氫氧化鈉(NaOH)（1.6g，39.6mmol）並在室溫反應1小時後，將5-溴-1,2,3-三氟苯（2.1g，9.9mmol）用二甲基甲醯胺(DMF)溶解後加入，反應5小時而製備二叔丁基(2-(4(3,4,5-三氟苯氧基)苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸（5.5g，87%）。在0℃下加入將二叔丁基(2-(4(3,4,5-三氟苯氧基)苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸（5.5g，8.66mmol）與三氟乙酸(TFA)（30mL）後，反應1小時而製取4,4’-(2-(4-(3,4,5-三氟苯氧基）苯基）乙烷-1,1-二基)二苯胺化合物（3g，80%）。1 H NMR (300 MHz, DMSO) δ7.58 (t, 1H), 7.09 (d, 2H), 6.88 (m, 7H), 6.34 (d, 4H), 4.75 (s, 4H), 3.86 (t, 1H), 3.13 (d, 2H)。[Synthesis Example 3] Synthesis of 4,4'-(2-(4-(3,4,5-trifluorophenoxy)phenyl)ethane-1,1-diyl)diphenylamine (4,4' -(2-(4-(3,4,5-trifluorophenoxy)phenyl)ethane-1,1-diyl)dianiline)
Figure 02_image027
Dissolve di-tert-butyl (2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5g, 9.9mmol) in the reaction vessel Methylformamide (DMF) (100mL), sodium hydroxide (NaOH) (1.6g, 39.6mmol) was added and reacted at room temperature for 1 hour, then 5-bromo-1,2,3-trifluorobenzene (2.1g, 9.9mmol) dissolved in dimethylformamide (DMF) and added, reacted for 5 hours to prepare di-tert-butyl (2-(4(3,4,5-trifluorophenoxy)phenyl) ) Ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5.5g, 87%). Add di-tert-butyl(2-(4(3,4,5-trifluorophenoxy)phenyl)ethane-1,1-diyl)bis(4,1-phenylene) at 0℃ ) Dicarboxylic acid (5.5g, 8.66mmol) and trifluoroacetic acid (TFA) (30mL) are reacted for 1 hour to prepare 4,4'-(2-(4-(3,4,5-trifluorobenzene) (Oxy)phenyl)ethane-1,1-diyl)diphenylamine compound (3g, 80%). 1 H NMR (300 MHz, DMSO) δ7.58 (t, 1H), 7.09 (d, 2H), 6.88 (m, 7H), 6.34 (d, 4H), 4.75 (s, 4H), 3.86 (t, 1H), 3.13 (d, 2H).

【合成例4】 合成4,4'-(2-(4-((2,3',4',5'-四氟-[1,1'-聯苯]-4-基)氧基)苯基)乙烷-1,1-二基)二苯胺 (4,4'-(2-(4-((2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-yl)oxy)phenyl)ethane-1,1-diyl)dianiline)

Figure 02_image029
在反應容器中將二叔丁基(2-(4-羥基苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸(5g，9.9mmol)溶解在二甲基甲醯胺(DMF)（100mL）中，加入氫氧化鈉(NaOH)（1.6g，39.6mmol）並在室溫反應1小時後，將4-溴-2,3’,4’,5’-四氟-1-1’-聯苯（3.02g，9.9mmol）用二甲基甲醯胺(DMF)溶解後加入，反應5小時而製備二叔丁基(2-(4(2,3’,4’,5’-四氟-[1,1’-聯苯]-4-基)氧基)苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸（5g，73%）。在0℃下加入二叔丁基(2-(4(2,3’,4’,5’-四氟-[1,1’-聯苯]-4-基)氧基)苯基)乙烷-1,1-二基）雙（4,1-亞苯基）二羧酸（5g，7.23mmol）與三氟乙酸(TFA)（30mL）後，反應1小時製取4,4'-(2-(4-((2,3',4',5'-四氟-[1,1'-聯苯]-4-基)氧基)苯基)乙烷-1,1-二基)二苯胺（3g，72%）化合物。1 H NMR (300 MHz, CDCl3 ) δ8.00 (dd, 1H), 7.36-7.27 (m, 5H), 7.14 (d, 2H), 7.02-6.95 (m, 5H), 6.34 (d, 4H), 4.44 (t, 1H), 3.9(s, 4H, NH), 3.17(d, 2H)。[Synthesis Example 4] Synthesis of 4,4'-(2-(4-((2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-yl)oxy) Phenyl)ethane-1,1-diyl)diphenylamine (4,4'-(2-(4-((2,3',4',5'-tetrafluoro-[1,1'-biphenyl] -4-yl)oxy)phenyl)ethane-1,1-diyl)dianiline)
Figure 02_image029
Dissolve di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5g, 9.9mmol) in the reaction vessel To dimethylformamide (DMF) (100mL), sodium hydroxide (NaOH) (1.6g, 39.6mmol) was added and reacted at room temperature for 1 hour, then 4-bromo-2,3',4', 5'-tetrafluoro-1-1'-biphenyl (3.02g, 9.9mmol) was dissolved in dimethylformamide (DMF) and added, and reacted for 5 hours to prepare di-tert-butyl (2-(4(2) ,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-yl)oxy)phenyl)ethane-1,1-diyl)bis(4,1-ylidene) Phenyl) dicarboxylic acid (5 g, 73%). Add di-tert-butyl(2-(4(2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-yl)oxy)phenyl)ethyl at 0℃ Alkyl-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5g, 7.23mmol) and trifluoroacetic acid (TFA) (30mL), react for 1 hour to prepare 4,4'- (2-(4-((2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-yl)oxy)phenyl)ethane-1,1-di Base) diphenylamine (3g, 72%) compound. 1 H NMR (300 MHz, CDCl 3 ) δ8.00 (dd, 1H), 7.36-7.27 (m, 5H), 7.14 (d, 2H), 7.02-6.95 (m, 5H), 6.34 (d, 4H) , 4.44 (t, 1H), 3.9(s, 4H, NH), 3.17(d, 2H).

【合成例5】 合成4,4'-(2-(4-(4-(4-戊基環己基)苯氧基)苯基)乙烷-1,1-二基)二苯胺 (4,4'-(2-(4-(4-(4-pentylcyclohexyl)phenoxy)phenyl)ethane-1,1-diyl)dianiline)

Figure 02_image031
在反應容器中將二叔丁基(2-(4-羥基苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸(5g，9.9mmol)溶解在二甲基甲醯胺(DMF)（100mL）中，加入氫氧化鈉(NaOH)（1.6g，39.6mmol）並在室溫反應1小時後，將1-碘-4-(4-戊基環己基)苯（3.53g，9.9mmol）用二甲基甲醯胺(DMF)溶解後加入，反應5小時而製備二叔丁基(2-(4-(4-(4-戊基環己基)苯氧基)苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸（6g，81%）。在0℃下加入二叔丁基(2-(4-(4-(4-戊基環己基)苯氧基)苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸（6g，8.02mmol）與三氟乙酸(TFA)（30mL）後，反應1小時製取4,4'-(2-(4-(4-(4-戊基環己基)苯氧基)苯基)乙烷-1,1-二基)二苯胺（3g，77%）化合物。1 H NMR (300 MHz, CDCl3 ) δ7.33-7.35 (m, 6H), 7.14 (d, 2H), 6.95 (d, 4H), 6.34 (d, 4H), 4.44 (t, 1H), 3.9(s, 4H, NH), 3.17(d, 2H), 2.72 (m, 1H), 1.86-1.25 (m, 17H), 0.89 (t, 3H)。[Synthesis Example 5] Synthesis of 4,4'-(2-(4-(4-(4-(4-pentylcyclohexyl)phenoxy)phenyl)ethane-1,1-diyl)diphenylamine (4, 4'-(2-(4-(4-(4-pentylcyclohexyl)phenoxy)phenyl)ethane-1,1-diyl)dianiline)
Figure 02_image031
Dissolve di-tert-butyl(2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5g, 9.9mmol) in the reaction vessel To dimethylformamide (DMF) (100mL), sodium hydroxide (NaOH) (1.6g, 39.6mmol) was added and reacted at room temperature for 1 hour, the 1-iodo-4-(4-pentyl ring Hexyl)benzene (3.53g, 9.9mmol) was dissolved in dimethylformamide (DMF) and added, and reacted for 5 hours to prepare di-tert-butyl (2-(4-(4-(4-pentylcyclohexyl)) Phenoxy)phenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (6g, 81%). Add di-tert-butyl(2-(4-(4-(4-pentylcyclohexyl)phenoxy)phenyl)ethane-1,1-diyl)bis(4,1-ylidene) at 0℃ Phenyl) dicarboxylic acid (6g, 8.02mmol) and trifluoroacetic acid (TFA) (30mL), react for 1 hour to prepare 4,4'-(2-(4-(4-(4-pentylcyclohexyl) )Phenoxy)phenyl)ethane-1,1-diyl)diphenylamine (3g, 77%) compound. 1 H NMR (300 MHz, CDCl 3 ) δ7.33-7.35 (m, 6H), 7.14 (d, 2H), 6.95 (d, 4H), 6.34 (d, 4H), 4.44 (t, 1H), 3.9 (s, 4H, NH), 3.17(d, 2H), 2.72 (m, 1H), 1.86-1.25 (m, 17H), 0.89 (t, 3H).

【合成例6】 合成4,4'-(2-(4-(辛氧基)苯基)乙烷-1,1-二基)二苯胺 (4,4'-(2-(4-(octyloxy)phenyl)ethane-1,1-diyl)dianiline)

Figure 02_image033
在反應容器中將二叔丁基((2-(4-羥基苯基)乙烷-1,1-二基)雙（4，1-亞苯基）二羧酸(5g，9.9mmol)溶解在二甲基甲醯胺(DMF)（100mL）中，加入氫氧化鈉(NaOH)（1.6g，39.6mmol）在室溫反應1小時後，將1-溴辛烷（1.91g，9.9mmol）用二甲基甲醯胺(DMF)溶解後加入，反應5小時而製備二叔丁基(2-(4-(辛氧基)苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸（4g，66%）。在0℃下加入二叔丁基((2-(4-(辛氧基)苯基)乙烷-1,1-二基)雙(4,1-亞苯基)二羧酸（4g，6.53mmol）與三氟乙酸(TFA)（30mL）後，反應1小時製取4,4'-(2-(4-(辛氧基)苯基)乙烷-1,1-二基)二苯胺（2g，80%）化合物。1 H NMR (300 MHz, CDCl3 ) δ7.18 (d, 2H), 6.95 (d, 4H), 6.86 (d, 2H), 6.34 (d, 4H), 4.44 (t, 1H), 4.11 (t, 2H), 3.9(s, 4H, NH), 3.17(d, 2H), 1.74 (m, 2H), 1.43-1.26 (m, 10H), 0.89 (t, 3H)。[Synthesis Example 6] Synthesis of 4,4'-(2-(4-(octyloxy)phenyl)ethane-1,1-diyl)diphenylamine (4,4'-(2-(4-( octyloxy)phenyl)ethane-1,1-diyl)dianiline)
Figure 02_image033
Dissolve di-tert-butyl((2-(4-hydroxyphenyl)ethane-1,1-diyl)bis(4,1-phenylene)dicarboxylic acid (5g, 9.9mmol) in the reaction vessel In dimethylformamide (DMF) (100mL), sodium hydroxide (NaOH) (1.6g, 39.6mmol) was added and reacted at room temperature for 1 hour, then 1-bromooctane (1.91g, 9.9mmol) Dissolve with dimethylformamide (DMF) and add, react for 5 hours to prepare di-tert-butyl(2-(4-(octyloxy)phenyl)ethane-1,1-diyl)bis(4 ,1-phenylene)dicarboxylic acid (4g, 66%). Add di-tert-butyl((2-(4-(octyloxy)phenyl)ethane-1,1-diyl at 0℃ ) Bis(4,1-phenylene)dicarboxylic acid (4g, 6.53mmol) and trifluoroacetic acid (TFA) (30mL), react for 1 hour to prepare 4,4'-(2-(4-(octane) (Oxy)phenyl)ethane-1,1-diyl)diphenylamine (2g, 80%) compound. 1 H NMR (300 MHz, CDCl 3 ) δ7.18 (d, 2H), 6.95 (d, 4H ), 6.86 (d, 2H), 6.34 (d, 4H), 4.44 (t, 1H), 4.11 (t, 2H), 3.9(s, 4H, NH), 3.17(d, 2H), 1.74 (m, 2H), 1.43-1.26 (m, 10H), 0.89 (t, 3H).

【合成例7】 合成4,4'-(十七烷-1,1-二基)二苯胺 （4,4'-(heptadecane-1,1-diyl)dianiline）

Figure 02_image015
在反應容器中，將雙(4-硝基苯基)甲烷(10g，38.7mmol)，用N2 取代後，溶解在甲苯（100ml），降溫為0℃。將乙醇鉀（3.25g，38.7mmol）用乙醇(EtOH)(5ml)溶解後，緩慢滴加到降溫為0℃的溶液中。升溫為室溫並攪拌4小時後過濾，將濾出的固體用甲苯清洗後，在真空乾燥箱中乾燥14小時而製取青紫色的固體雙(4-硝基苯基)甲烷、鉀鹽(10.35g，90%)。將雙(4-硝基苯基)甲烷與鉀鹽（10g，33.6mmol）溶解在二甲基甲醯胺(DMF)後降溫為0℃。緩慢滴加1-溴十六烷（11.29g，36.99mmol）。升溫為室溫攪拌12小時。用柱層析法製取4,4'-(十七烷-1,1-二基）雙（硝基苯基）(11.37g，70%)。將4,4'-(十七烷-1,1-二基)雙（硝基苯基）(10g，20.7mmol)溶解在乙醇(EtOH)（100ml）中，緩慢加入Pd/C（5wt.%）。大量滴加水合肼(hydrazine)（41.44g，828mmol）。在室溫攪拌2小時後過濾而去除Pd/C，然後通過減壓蒸餾而去除溶劑，用水(H2 0)與乙酸乙酯(EA)提取三次後，用柱層析法製取4,4'-(十七烷-1,1-二基)二苯胺（7g，89%）。1 H NMR (300 MHz, CDCl3 ) δ6.95 (d, 4H), 6.34 (d, 4H), 3.96 (t, 1H), 3.9 (s, 4H), 1.89 (q, 2H), 1.33-1.25 (m, 14H), 0.8 (t, 3H)。[Synthesis Example 7] Synthesis of 4,4'-(heptadecane-1,1-diyl)diphenylamine (4,4'-(heptadecane-1,1-diyl)dianiline)
Figure 02_image015
In the reaction vessel, bis(4-nitrophenyl)methane (10 g, 38.7 mmol) was substituted with N 2 and dissolved in toluene (100 ml), and the temperature was lowered to 0°C. After dissolving potassium ethoxide (3.25g, 38.7mmol) with ethanol (EtOH) (5ml), it was slowly added dropwise to the solution cooled to 0°C. The temperature was raised to room temperature and stirred for 4 hours, and then filtered. After the filtered solid was washed with toluene, it was dried in a vacuum drying oven for 14 hours to prepare a blue-purple solid bis(4-nitrophenyl)methane and potassium salt ( 10.35g, 90%). Dissolve bis(4-nitrophenyl)methane and potassium salt (10g, 33.6mmol) in dimethylformamide (DMF) and then lower the temperature to 0°C. Slowly add 1-bromohexadecane (11.29g, 36.99mmol) dropwise. The temperature was raised to room temperature and stirred for 12 hours. Prepare 4,4'-(heptadecan-1,1-diyl)bis(nitrophenyl) (11.37g, 70%) by column chromatography. Dissolve 4,4'-(heptadecan-1,1-diyl)bis(nitrophenyl) (10g, 20.7mmol) in ethanol (EtOH) (100ml), and slowly add Pd/C (5wt. %). A large amount of hydrazine (41.44g, 828mmol) was added dropwise. After stirring for 2 hours at room temperature, the Pd/C was removed by filtration, and then the solvent was removed by distillation under reduced pressure. After three extractions with water (H 2 0) and ethyl acetate (EA), 4,4' was obtained by column chromatography. -(Heptadecan-1,1-diyl)diphenylamine (7g, 89%). 1 H NMR (300 MHz, CDCl 3 ) δ6.95 (d, 4H), 6.34 (d, 4H), 3.96 (t, 1H), 3.9 (s, 4H), 1.89 (q, 2H), 1.33-1.25 (m, 14H), 0.8 (t, 3H).

【實施例1】 將4,4'-亞甲基二苯胺（2.97g，15.0mmol）及在上述合成例1中製取的二苯胺（2.00g，3.7mmol）溶解在N-甲基-2-吡咯烷酮（31.41g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.83g，9.4mmol）及均苯四甲酸二酐（2.04g，9.4mmol）溶解在γ-丁內酯（18.69g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 1] 4,4'-methylene diphenylamine (2.97g, 15.0mmol) and the diphenylamine (2.00g, 3.7mmol) prepared in Synthesis Example 1 above were dissolved in N-methyl-2 -A reaction solution of pyrrolidone (31.41g), keeping room temperature, and slowly adding dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.83g, 9.4mmol) and pyromellitic acid for 2 hours Anhydride (2.04g, 9.4mmol) was dissolved in a reaction solution of γ-butyrolactone (18.69g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例2】 將對苯二胺（1.62g，15.0mmol）及在上述合成例1中製取的二苯胺（2.00g，3.7mmol）溶解在N-甲基-2-吡咯烷酮（26.62g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.83g，9.4mmol）及均苯四甲酸二酐（2.04g，9.4mmol）溶解在γ-丁內酯（15.84g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 2] p-Phenylenediamine (1.62g, 15.0mmol) and the diphenylamine (2.00g, 3.7mmol) prepared in Synthesis Example 1 above were dissolved in N-methyl-2-pyrrolidone (26.62g) 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.83g, 9.4mmol) and pyromellitic dianhydride (2.04g, 9.4mmol) mmol) was dissolved in a reaction solution of γ-butyrolactone (15.84g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例3】 將4,4'-亞甲基二苯胺（1.48g，7.5mmol）、對苯二胺（0.81g，7.5mmol）及在上述合成例1中製取的二苯胺（2.00g，3.7mmol）溶解在N-甲基-2-吡咯烷酮（29.02g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.83g，9.4mmol）及均苯四甲酸二酐（2.04g，9.4mmol）溶解在γ-丁內酯（17.26g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 3] 4,4'-methylene diphenylamine (1.48g, 7.5mmol), p-phenylenediamine (0.81g, 7.5mmol) and the diphenylamine prepared in the above synthesis example 1 (2.00g , 3.7mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (29.02g), kept at room temperature, and slowly added dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride ( 1.83g, 9.4mmol) and pyromellitic dianhydride (2.04g, 9.4mmol) were dissolved in a reaction solution of γ-butyrolactone (17.26g), and reacted for 6 hours to prepare a polyamide acid solution.

【實施例4】 將4,4'-亞甲基二苯胺（1.48g，7.5mmol）、對苯二胺（0.81g，7.5mmol）及在上述合成例1中製取的二苯胺（2.00g，3.7mmol）溶解在N-甲基-2-吡咯烷酮（29.02g）的反應溶液，保持室溫，並且2小時緩慢滴加將2,3,5-環四羧酸二酐（2.10g，9.4mmol）及均苯四甲酸二酐（2.04g，9.4mmol）溶解在γ-丁內酯（17.82g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 4] 4,4'-methylene diphenylamine (1.48g, 7.5mmol), p-phenylenediamine (0.81g, 7.5mmol) and the diphenylamine prepared in the above synthesis example 1 (2.00g , 3.7mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (29.02g), kept at room temperature, and slowly added dropwise 2,3,5-cyclotetracarboxylic dianhydride (2.10g, 9.4 mmol) and pyromellitic dianhydride (2.04g, 9.4mmol) were dissolved in a reaction solution of γ-butyrolactone (17.82g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例5】 將4,4'-亞甲基二苯胺（2.85g，14.4mmol）及在上述合成例2中製取的二苯胺（2.00g，3.6mmol）溶解在N-甲基-2-吡咯烷酮（30.45g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.76g，9.0mmol）及均苯四甲酸二酐（1.96g，9.0mmol）溶解在γ-丁內酯（18.12g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 5] 4,4'-methylenediphenylamine (2.85g, 14.4mmol) and the diphenylamine (2.00g, 3.6mmol) prepared in Synthesis Example 2 above were dissolved in N-methyl-2 -The reaction solution of pyrrolidone (30.45g), keep at room temperature, and slowly add dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.76g, 9.0mmol) and pyromellitic acid for 2 hours Anhydride (1.96g, 9.0mmol) was dissolved in a reaction solution of γ-butyrolactone (18.12g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例6】 將對苯二胺（1.55g，14.4mmol）及在上述合成例2中製取的二苯胺（2.00g，3.6mmol）溶解在N-甲基-2-吡咯烷酮（25.85g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.76g，9.0mmol）及均苯四甲酸二酐（1.96g，9.0mmol）溶解在γ-丁內酯（15.38g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 6] p-Phenylenediamine (1.55g, 14.4mmol) and the diphenylamine (2.00g, 3.6mmol) prepared in Synthesis Example 2 above were dissolved in N-methyl-2-pyrrolidone (25.85g) 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.76g, 9.0mmol) and pyromellitic dianhydride (1.96g, 9.0 mmol) was dissolved in a reaction solution of γ-butyrolactone (15.38g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例7】 將4,4'-亞甲基二苯胺（1.42g，7.2mmol）、對苯二胺（0.78g，7.2mmol）及在上述合成例2中製取的二苯胺（2.00g，3.6mmol）溶解在N-甲基-2-吡咯烷酮（28.15g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.76g，9.0mmol）及均苯四甲酸二酐（1.96g，9.0mmol）溶解在γ-丁內酯（16.75g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 7] 4,4'-methylene diphenylamine (1.42g, 7.2mmol), p-phenylenediamine (0.78g, 7.2mmol) and the diphenylamine prepared in Synthesis Example 2 above (2.00g , 3.6mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (28.15g), kept at room temperature, and slowly added dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride ( 1.76g, 9.0mmol) and pyromellitic dianhydride (1.96g, 9.0mmol) were dissolved in a reaction solution of γ-butyrolactone (16.75g), and reacted for 6 hours to prepare a polyamide acid solution.

【實施例8】 將4,4'-亞甲基二苯胺（1.42g，7.2mmol）、對苯二胺（0.78g，7.2mmol）及在上述合成例2中製取的二苯胺（2.00g，3.6mmol）溶解在N-甲基-2-吡咯烷酮（28.15g）的反應溶液，保持室溫，並且2小時緩慢滴加將2,3,5-環四羧酸二酐（2.01g，9.0mmol）及均苯四甲酸二酐（1.96g，9.0mmol）溶解在γ-丁內酯（17.28g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 8] 4,4'-methylene diphenylamine (1.42g, 7.2mmol), p-phenylenediamine (0.78g, 7.2mmol) and the diphenylamine prepared in the above synthesis example 2 (2.00g , 3.6mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (28.15g), kept at room temperature, and slowly added dropwise 2,3,5-cyclotetracarboxylic dianhydride (2.01g, 9.0 mmol) and pyromellitic dianhydride (1.96g, 9.0mmol) were dissolved in a reaction solution of γ-butyrolactone (17.28g), and reacted for 6 hours to prepare a polyamide acid solution.

【實施例9】 將4,4'-亞甲基二苯胺（3.65g，18.4mmol）及在上述合成例3中製取的二苯胺（2.00g，4.6mmol）溶解在N-甲基-2-吡咯烷酮（37.01g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（2.26g，11.5mmol）及均苯四甲酸二酐（2.51g，11.5mmol）溶解在γ-丁內酯（22.02g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 9] 4,4'-methylene diphenylamine (3.65g, 18.4mmol) and the diphenylamine (2.00g, 4.6mmol) prepared in the above synthesis example 3 were dissolved in N-methyl-2 -The reaction solution of pyrrolidone (37.01g), keep it at room temperature, and slowly add dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.26g, 11.5mmol) and pyromellitic acid for 2 hours Anhydride (2.51g, 11.5mmol) was dissolved in a reaction solution of γ-butyrolactone (22.02g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例10】 將對苯二胺（1.99g，18.4mmol）及在上述合成例3中製取的二苯胺（2.00g，4.6mmol）溶解在N-甲基-2-吡咯烷酮（31.12g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（2.26g，11.5mmol）及均苯四甲酸二酐（2.51g，11.5mmol）溶解在γ-丁內酯（18.51g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 10] p-Phenylenediamine (1.99g, 18.4mmol) and the diphenylamine (2.00g, 4.6mmol) prepared in Synthesis Example 3 above were dissolved in N-methyl-2-pyrrolidone (31.12g) 1,2,3,4-cyclobutane tetracarboxylic dianhydride (2.26g, 11.5mmol) and pyromellitic dianhydride (2.51g, 11.5 mmol) was dissolved in a reaction solution of γ-butyrolactone (18.51g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例11】 將4,4'-亞甲基二苯胺（1.83g，9.2mmol）、對苯二胺（1.00g，9.2mmol）及在上述合成例3中製取的二苯胺（2.00g，4.6mmol）溶解在N-甲基-2-吡咯烷酮（34.07g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（2.26g，11.5mmol）及均苯四甲酸二酐（2.51g，11.5mmol）溶解在γ-丁內酯（20.27g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 11] 4,4'-methylene diphenylamine (1.83g, 9.2mmol), p-phenylenediamine (1.00g, 9.2mmol) and the diphenylamine prepared in the above synthesis example 3 (2.00g , 4.6mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (34.07g), kept at room temperature, and slowly added dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride ( 2.26g, 11.5mmol) and pyromellitic dianhydride (2.51g, 11.5mmol) were dissolved in a reaction solution of γ-butyrolactone (20.27g), and reacted for 6 hours to prepare a polyamide acid solution.

【實施例12】 將4,4'-亞甲基二苯胺（1.83g，9.2mmol）、對苯二胺（1.00g，9.2mmol）及在上述合成例3中製取的二苯胺（2.00g，4.6mmol）溶解在N-甲基-2-吡咯烷酮（34.07g）的反應溶液，保持室溫，並且2小時緩慢滴加將2,3,5-環四羧酸二酐（2.58g，11.5mmol）及均苯四甲酸二酐（2.51g，11.5mmol）溶解在γ-丁內酯（20.95g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 12] 4,4'-methylene diphenylamine (1.83g, 9.2mmol), p-phenylenediamine (1.00g, 9.2mmol) and the diphenylamine prepared in the above synthesis example 3 (2.00g , 4.6mmol) dissolved in the reaction solution of N-methyl-2-pyrrolidone (34.07g), kept at room temperature, and slowly added dropwise 2,3,5-cyclotetracarboxylic dianhydride (2.58g, 11.5 mmol) and pyromellitic dianhydride (2.51g, 11.5mmol) were dissolved in a reaction solution of γ-butyrolactone (20.95g), and reacted for 6 hours to prepare a polyamide acid solution.

【實施例13】 將4,4'-亞甲基二苯胺（3.00g，15.1mmol）及在上述合成例4中製取的二苯胺（2.00g，3.8mmol）溶解在N-甲基-2-吡咯烷酮（31.69g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.86g，9.5mmol）及均苯四甲酸二酐（2.06g，9.5mmol）溶解在γ-丁內酯（18.85g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 13] 4,4'-methylenediphenylamine (3.00g, 15.1mmol) and the diphenylamine (2.00g, 3.8mmol) prepared in Synthesis Example 4 above were dissolved in N-methyl-2 -The reaction solution of pyrrolidone (31.69g), keep it at room temperature, and slowly add dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.86g, 9.5mmol) and pyromellitic acid for 2 hours Anhydride (2.06g, 9.5mmol) was dissolved in a reaction solution of γ-butyrolactone (18.85g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例14】 將對苯二胺（1.64g，15.1mmol）及在上述合成例4中製取的二苯胺（2.00g，3.8mmol）溶解在N-甲基-2-吡咯烷酮（26.84g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.86g，9.5mmol）及均苯四甲酸二酐（2.06g，9.5mmol）溶解在γ-丁內酯（15.97g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 14] p-phenylenediamine (1.64g, 15.1mmol) and the diphenylamine (2.00g, 3.8mmol) prepared in Synthesis Example 4 above were dissolved in N-methyl-2-pyrrolidone (26.84g) 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.86g, 9.5mmol) and pyromellitic dianhydride (2.06g, 9.5mmol) mmol) was dissolved in a reaction solution of γ-butyrolactone (15.97g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例15】 將4,4'-亞甲基二苯胺（1.50g，7.6mmol）、對苯二胺（0.82g，7.6mmol）及在上述合成例4中製取的二苯胺（2.00g，3.8mmol）溶解在N-甲基-2-吡咯烷酮（29.27g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.86g，9.5mmol）及均苯四甲酸二酐（2.06g，9.5mmol）溶解在γ-丁內酯（17.41g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 15] 4,4'-methylene diphenylamine (1.50g, 7.6mmol), p-phenylenediamine (0.82g, 7.6mmol) and the diphenylamine prepared in the above synthesis example 4 (2.00g , 3.8mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (29.27g), kept at room temperature, and slowly added dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride ( 1.86g, 9.5mmol) and pyromellitic dianhydride (2.06g, 9.5mmol) were dissolved in a reaction solution of γ-butyrolactone (17.41g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例16】 將4,4'-亞甲基二苯胺（1.50g，7.6mmol）、對苯二胺（0.82g，7.6mmol）及在上述合成例4中製取的二苯胺（2.00g，3.8mmol）溶解在N-甲基-2-吡咯烷酮（29.27g）的反應溶液，保持室溫，並且2小時緩慢滴加將2,3,5-環四羧酸二酐（2.12g，9.5mmol）及均苯四甲酸二酐（2.06g，9.5mmol）溶解在γ-丁內酯（17.97g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 16] 4,4'-methylene diphenylamine (1.50g, 7.6mmol), p-phenylenediamine (0.82g, 7.6mmol) and the diphenylamine prepared in the above synthesis example 4 (2.00g , 3.8mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (29.27g), kept at room temperature, and slowly added dropwise 2,3,5-cyclotetracarboxylic dianhydride (2.12g, 9.5 mmol) and pyromellitic dianhydride (2.06g, 9.5mmol) were dissolved in a reaction solution of γ-butyrolactone (17.97g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例17】 將4,4'-亞甲基二苯胺（2.98g，15.0mmol）及在上述合成例5中製取的二苯胺（2.00g，3.8mmol）溶解在N-甲基-2-吡咯烷酮（31.50g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.84g，9.4mmol）及均苯四甲酸二酐（2.05g，9.4mmol）溶解在γ-丁內酯（18.74g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 17] 4,4'-methylenediphenylamine (2.98g, 15.0mmol) and the diphenylamine (2.00g, 3.8mmol) prepared in Synthesis Example 5 above were dissolved in N-methyl-2 -A reaction solution of pyrrolidone (31.50g), keeping room temperature, and slowly adding dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.84g, 9.4mmol) and pyromellitic acid for 2 hours Anhydride (2.05g, 9.4mmol) was dissolved in a reaction solution of γ-butyrolactone (18.74g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例18】 將對苯二胺（1.62g，15.0mmol）及在上述合成例5中製取的二苯胺（2.00g，3.8mmol）溶解在N-甲基-2-吡咯烷酮（26.69g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.84g，9.4mmol）及均苯四甲酸二酐（2.05g，9.4mmol）溶解在γ-丁內酯（15.88g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 18] p-Phenylenediamine (1.62g, 15.0mmol) and the diphenylamine (2.00g, 3.8mmol) prepared in Synthesis Example 5 above were dissolved in N-methyl-2-pyrrolidone (26.69g) 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.84g, 9.4mmol) and pyromellitic dianhydride (2.05g, 9.4mmol) mmol) was dissolved in a reaction solution of γ-butyrolactone (15.88g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例19】 將4,4'-亞甲基二苯胺（1.49g，7.5mmol）、對苯二胺（0.81g，7.5mmol）及在上述合成例5中製取的二苯胺（2.00g，3.8mmol）溶解在N-甲基-2-吡咯烷酮（29.09g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.84g，9.4mmol）及均苯四甲酸二酐（2.05g，9.4mmol）溶解在γ-丁內酯（17.31g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 19] 4,4'-methylene diphenylamine (1.49g, 7.5mmol), p-phenylenediamine (0.81g, 7.5mmol) and the diphenylamine prepared in the above synthesis example 5 (2.00g , 3.8mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (29.09g), kept at room temperature, and slowly added dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride ( 1.84g, 9.4mmol) and pyromellitic dianhydride (2.05g, 9.4mmol) were dissolved in a reaction solution of γ-butyrolactone (17.31g), and reacted for 6 hours to prepare a polyamide acid solution.

【實施例20】 將4,4'-亞甲基二苯胺（1.49g，7.5mmol）、對苯二胺（0.81g，7.5mmol）及在上述合成例5中製取的二苯胺（2.00g，3.8mmol）溶解在N-甲基-2-吡咯烷酮（29.09g）的反應溶液，保持室溫，並且2小時緩慢滴加將2,3,5-環四羧酸二酐（2.10g，9.4mmol）及均苯四甲酸二酐（2.05g，9.4mmol）溶解在γ-丁內酯（17.86g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 20] 4,4'-methylene diphenylamine (1.49g, 7.5mmol), p-phenylenediamine (0.81g, 7.5mmol) and the diphenylamine prepared in the above Synthesis Example 5 (2.00g , 3.8mmol) dissolved in the reaction solution of N-methyl-2-pyrrolidone (29.09g), kept at room temperature, and slowly added dropwise 2,3,5-cyclotetracarboxylic dianhydride (2.10g, 9.4 mmol) and pyromellitic dianhydride (2.05g, 9.4mmol) were dissolved in a reaction solution of γ-butyrolactone (17.86g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例21】 將4,4'-亞甲基二苯胺（3.81g，19.2mmol）及在上述合成例6中製取的二苯胺（2.00g，4.8mmol）溶解在N-甲基-2-吡咯烷酮（38.30g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（2.35g，12.0mmol）及均苯四甲酸二酐（2.62g，12.0mmol）溶解在γ-丁內酯（22.78g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 21] 4,4'-methylenediphenylamine (3.81g, 19.2mmol) and the diphenylamine (2.00g, 4.8mmol) prepared in Synthesis Example 6 above were dissolved in N-methyl-2 -The reaction solution of pyrrolidone (38.30g), keep it at room temperature, and slowly add dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.35g, 12.0mmol) and pyromellitic acid for 2 hours Anhydride (2.62g, 12.0mmol) was dissolved in a reaction solution of γ-butyrolactone (22.78g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例22】 將對苯二胺（2.08g，19.2mmol）及在上述合成例6中製取的二苯胺（2.00g，4.8mmol）溶解在N-甲基-2-吡咯烷酮（32.15g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（2.35g，12.0mmol）及均苯四甲酸二酐（2.62g，12.0mmol）溶解在γ-丁內酯（19.12g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 22] p-phenylenediamine (2.08g, 19.2mmol) and the diphenylamine (2.00g, 4.8mmol) prepared in the above Synthesis Example 6 were dissolved in N-methyl-2-pyrrolidone (32.15g) 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.35g, 12.0mmol) and pyromellitic dianhydride (2.62g, 12.0 mmol) was dissolved in a reaction solution of γ-butyrolactone (19.12g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例23】 將4,4'-亞甲基二苯胺（1.90g，9.6mmol）、對苯二胺（1.04g，9.6mmol）及在上述合成例6中製取的二苯胺（2.00g，4.8mmol）溶解在N-甲基-2-吡咯烷酮（35.22g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（2.35g，12.0mmol）及均苯四甲酸二酐（2.62g，12.0mmol）溶解在γ-丁內酯（20.95g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 23] 4,4'-methylene diphenylamine (1.90g, 9.6mmol), p-phenylenediamine (1.04g, 9.6mmol) and the diphenylamine prepared in the above synthesis example 6 (2.00g , 4.8mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (35.22g), kept at room temperature, and slowly added dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride ( 2.35g, 12.0mmol) and pyromellitic dianhydride (2.62g, 12.0mmol) were dissolved in a reaction solution of γ-butyrolactone (20.95g), and reacted for 6 hours to prepare a polyamide acid solution.

【實施例24】 將4,4'-亞甲基二苯胺（1.90g，9.6mmol）、對苯二胺（1.04g，9.6mmol）及在上述合成例6中製取的二苯胺（2.00g，4.8mmol）溶解在N-甲基-2-吡咯烷酮（35.22g）的反應溶液，保持室溫，並且2小時緩慢滴加將2,3,5-環四羧酸二酐（2.69g，12.0mmol）及均苯四甲酸二酐（2.62g，12.0mmol）溶解在γ-丁內酯（21.67g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 24] 4,4'-methylene diphenylamine (1.90g, 9.6mmol), p-phenylenediamine (1.04g, 9.6mmol) and the diphenylamine prepared in the above synthesis example 6 (2.00g , 4.8mmol) dissolved in the reaction solution of N-methyl-2-pyrrolidone (35.22g), kept at room temperature, and slowly added dropwise 2,3,5-cyclotetracarboxylic dianhydride (2.69g, 12.0 mmol) and pyromellitic dianhydride (2.62g, 12.0mmol) were dissolved in a reaction solution of γ-butyrolactone (21.67g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例25】 將4,4'-亞甲基二苯胺（3.75g，18.9mmol）及在上述合成例7中製取的二苯胺（2.00g，4.7mmol）溶解在N-甲基-2-吡咯烷酮（37.85g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（2.32g，11.8mmol）及均苯四甲酸二酐（2.58g，11.8mmol）溶解在γ-丁內酯（22.51g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 25] 4,4'-methylenediphenylamine (3.75g, 18.9mmol) and the diphenylamine (2.00g, 4.7mmol) prepared in Synthesis Example 7 above were dissolved in N-methyl-2 -A reaction solution of pyrrolidone (37.85g), keeping room temperature, and slowly adding dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.32g, 11.8mmol) and pyromellitic acid for 2 hours Anhydride (2.58g, 11.8mmol) was dissolved in a reaction solution of γ-butyrolactone (22.51g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例26】 將對苯二胺（2.05g，18.9mmol）及在上述合成例7中製取的二苯胺（2.00g，4.7mmol）溶解在N-甲基-2-吡咯烷酮（31.79g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（2.32g，11.8mmol）及均苯四甲酸二酐（2.58g，11.8mmol）溶解在γ-丁內酯（18.91g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 26] p-Phenylenediamine (2.05g, 18.9mmol) and the diphenylamine (2.00g, 4.7mmol) prepared in Synthesis Example 7 above were dissolved in N-methyl-2-pyrrolidone (31.79g) 1,2,3,4-cyclobutanetetracarboxylic dianhydride (2.32g, 11.8mmol) and pyromellitic dianhydride (2.58g, 11.8 mmol) was dissolved in a reaction solution of γ-butyrolactone (18.91g) and reacted for 6 hours to prepare a polyamide acid solution.

【實施例27】 將4,4'-亞甲基二苯胺（1.88g，9.5mmol）、對苯二胺（1.02g，9.5mmol）及在上述合成例7中製取的二苯胺（2.00g，4.7mmol）溶解在N-甲基-2-吡咯烷酮（34.82g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（2.32g，11.8mmol）及均苯四甲酸二酐（2.58g，11.8mmol）溶解在γ-丁內酯（20.71g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 27] 4,4'-methylene diphenylamine (1.88g, 9.5mmol), p-phenylenediamine (1.02g, 9.5mmol) and the diphenylamine prepared in the above synthesis example 7 (2.00g , 4.7mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (34.82g), kept at room temperature, and slowly added dropwise 1,2,3,4-cyclobutanetetracarboxylic dianhydride ( 2.32g, 11.8mmol) and pyromellitic dianhydride (2.58g, 11.8mmol) were dissolved in a reaction solution of γ-butyrolactone (20.71g), and reacted for 6 hours to prepare a polyamide acid solution.

【實施例28】 將4,4'-亞甲基二苯胺（1.88g，9.5mmol）、對苯二胺（1.02g，9.5mmol）及在上述合成例7中製取的二苯胺（2.00g，4.7mmol）溶解在N-甲基-2-吡咯烷酮（36.00g）的反應溶液，保持室溫，並且2小時緩慢滴加將2,3,5-環四羧酸二酐（2.65g，11.8mmol）及均苯四甲酸二酐（2.58g，11.8mmol）溶解在γ-丁內酯（21.41g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Example 28] 4,4'-methylene diphenylamine (1.88g, 9.5mmol), p-phenylenediamine (1.02g, 9.5mmol) and the diphenylamine prepared in the above Synthesis Example 7 (2.00g , 4.7mmol) dissolved in a reaction solution of N-methyl-2-pyrrolidone (36.00g), kept at room temperature, and slowly added dropwise 2,3,5-cyclotetracarboxylic dianhydride (2.65g, 11.8 mmol) and pyromellitic dianhydride (2.58g, 11.8mmol) were dissolved in a reaction solution of γ-butyrolactone (21.41g), and reacted for 6 hours to prepare a polyamide acid solution.

【實施例29至56】 將實施例1至28中製取的聚醯胺酸溶液用混合γ-丁內酯及丁基溶纖劑而成的溶劑進行溶解，形成濃度5重量百分比的溶液，並用0.1㎛的篩檢程式過濾而製備聚醯亞胺液晶配向劑。[Examples 29 to 56] The polyamide acid solutions prepared in Examples 1 to 28 were dissolved in a solvent formed by mixing γ-butyrolactone and butyl cellosolve to form a solution with a concentration of 5 weight percent, and use 0.1 ㎛'s screening program filters to prepare polyimide liquid crystal alignment agent.

【比較例1】 將4,4'-亞甲基二苯胺（1.52g，7.7mmol）、對苯二胺（0.83g，7.7mmol）及膽甾烷-3-醇、3,5-二氨基苯甲酸甲酯（2.00g，3.8mmol）溶解在N-甲基-2-吡咯烷酮（29.51g）的反應溶液，保持室溫，並且2小時緩慢滴加將1,2,3,4-環丁烷四羧酸二酐（1.88g，9.6mmol）及均苯四甲酸二酐（2.09g，9.6mmol）溶解在γ-丁內酯（17.56g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Comparative example 1] 4,4'-methylene diphenylamine (1.52g, 7.7mmol), p-phenylenediamine (0.83g, 7.7mmol) and cholestan-3-ol, 3,5-diamino Methyl benzoate (2.00g, 3.8mmol) was dissolved in the reaction solution of N-methyl-2-pyrrolidone (29.51g), kept at room temperature, and slowly added dropwise 1,2,3,4-cyclobutane for 2 hours. Alkyltetracarboxylic dianhydride (1.88g, 9.6mmol) and pyromellitic dianhydride (2.09g, 9.6mmol) were dissolved in a reaction solution of γ-butyrolactone (17.56g), and reacted for 6 hours to prepare polyamide Amino acid solution.

【比較例2】 將4,4'-亞甲基二苯胺（1.52g，7.7mmol）、對苯二胺（0.83g，7.7mmol）及膽甾烷-3-醇、3,5-二氨基苯甲酸甲酯（2.00g，3.8mmol）溶解在N-甲基-2-吡咯烷酮（30.46g）的反應溶液，保持室溫，並且2小時緩慢滴加將2,3,5-環四羧酸二酐（2.14g，9.6mmol）及均苯四甲酸二酐（2.09g，9.6mmol）溶解在γ-丁內酯（18.12g）的反應溶液，反應6小時而製取聚醯胺酸溶液。[Comparative Example 2] 4,4'-methylenediphenylamine (1.52g, 7.7mmol), p-phenylenediamine (0.83g, 7.7mmol) and cholestan-3-ol, 3,5-diamino Methyl benzoate (2.00g, 3.8mmol) was dissolved in the reaction solution of N-methyl-2-pyrrolidone (30.46g), kept at room temperature, and slowly added dropwise 2,3,5-cyclotetracarboxylic acid for 2 hours The dianhydride (2.14g, 9.6mmol) and pyromellitic dianhydride (2.09g, 9.6mmol) were dissolved in a reaction solution of γ-butyrolactone (18.12g), and reacted for 6 hours to prepare a polyamide acid solution.

【比較例3至4】 將比較例1至2中製取的聚醯胺酸溶液，利用與實施例29至56的製備方法相同的方法而製備液晶配向劑。[Comparative Examples 3 to 4] The polyamide acid solutions prepared in Comparative Examples 1 to 2 were prepared using the same method as the preparation method of Examples 29 to 56 to prepare a liquid crystal alignment agent.

【實施例57】 1）形成聚醯亞胺配向膜 將上述實施例29至56及比較例3至4中製取的液晶配向劑，利用旋轉塗布法（spinner），塗布在透明導電膜被圖案化的玻璃基板上。塗布後，在100℃下預燒30分鐘，在250℃下燒制1小時而製取具備膜厚為700Å的聚醯亞胺配向膜的基板。[Example 57] 1) Formation of polyimide alignment film The liquid crystal alignment agents prepared in the above Examples 29 to 56 and Comparative Examples 3 to 4 were coated on the transparent conductive film by a spinner method. On a glass substrate. After coating, it was pre-fired at 100°C for 30 minutes and fired at 250°C for 1 hour to prepare a substrate with a polyimide alignment film with a film thickness of 700 Å.

2）  製備液晶顯示元件 如上製作的具備液晶配向膜的兩張基板的配向膜面不進行摩擦（Rubbing），而相隔一定間隔（液晶層間隙）面向佈置兩張基板，用密封劑粘接兩張基板的邊緣部，通過基板表面及密封劑形成的盒間隙內注入並充填液晶，封閉注入孔而完成了液晶面板。並且液晶面板的表面即構成液晶面板的各個基板的反對面上，粘接偏光板而使其偏光軸方向相互垂直，而製得液晶顯示元件。在此作為密封劑使用了熱固性樹脂及作為隔離件使用了含有氧化鋁的環氧樹脂等。通過下述方法，評價了應用本發明中製備的聚醯亞胺樹脂而成的液晶配向劑的①預傾角、②配向性等特徵，該結果如下表1所示。 ①液晶顯示元件的預傾角 按照文獻（T.J. Schffer, et.al.,J., Appl., Phys.,vol.19, 2013 (1980）)中記載的方法，利用氦氖鐳射通過旋轉結晶法進行了測定。 ②液晶的配向均勻性 用顯微鏡觀察了當開/關液晶顯示元件的電壓時液晶面板中有無異常象限，若沒有異常象限，就判定為“良好”。

Figure AA1
Figure AA1-1
2) Preparation of liquid crystal display elements. The alignment film surfaces of the two substrates with liquid crystal alignment films made as above are not rubbed, and two substrates are arranged facing each other at a certain interval (liquid crystal layer gap), and the two substrates are bonded with a sealant. The edge of the substrate is injected and filled with liquid crystal through the cell gap formed by the surface of the substrate and the sealant, and the injection hole is closed to complete the liquid crystal panel. In addition, on the surface of the liquid crystal panel, that is, the opposite surface of each substrate constituting the liquid crystal panel, the polarizing plates are bonded so that the directions of their polarization axes are perpendicular to each other, thereby fabricating a liquid crystal display element. Here, a thermosetting resin is used as a sealing agent, and an epoxy resin containing alumina, etc., is used as a separator. The following methods were used to evaluate the characteristics of ① pretilt angle and ② alignment properties of the liquid crystal alignment agent prepared by applying the polyimide resin prepared in the present invention. The results are shown in Table 1 below. ①The pretilt angle of the liquid crystal display element is performed by the method described in the literature (TJ Schffer, et.al., J., Appl., Phys., vol.19, 2013 (1980)) using a helium-neon laser by rotating crystallization了定。 The determination. ②The alignment uniformity of the liquid crystal was observed with a microscope whether there were abnormal quadrants in the liquid crystal panel when the voltage of the liquid crystal display element was turned on/off. If there were no abnormal quadrants, it was judged as "good".
Figure AA1
Figure AA1-1

上述實施例中，用合成例2的二胺而成的聚醯亞胺樹脂的實施例29至32，適用于扭轉向列（TN）模式（4至5°），用合成例4的二胺而成的聚醯亞胺樹脂的實施例37至40（1至2°），則適用於平面轉換（IPS）模式。In the above examples, Examples 29 to 32 of the polyimide resin made of the diamine of Synthesis Example 2 are suitable for twisted nematic (TN) mode (4 to 5°), using the diamine of Synthesis Example 4 Examples 37 to 40 (1 to 2°) of the resulting polyimide resin are suitable for in-plane switching (IPS) mode.

比較實施例與比較例的性能值，除了根據本發明的實施例29至32、37至40以外，其他聚醯胺酸比比較例中記載的聚醯胺酸具備更為均勻的配向性，形成了垂直配向（VA）模式（89至90°）所需較高預傾角。The performance values of the comparative example and the comparative example, except for the examples 29 to 32 and 37 to 40 according to the present invention, other polyamides have a more uniform alignment than the polyamides described in the comparative examples, forming The vertical alignment (VA) mode (89 to 90°) requires a higher pretilt angle.

上述之實施例僅係為說明本發明之技術思想及特點，其目的在使熟悉此技藝之人士能了解本發明之內容並據以實施，當不能據以限定本發明之專利範圍，即凡其他未脫離本發明所揭示精神所完成之各種等效改變或修飾都涵蓋在本發明所揭露的範圍內，均應包含在以下之申請專利範圍內。The above-mentioned embodiments are only to illustrate the technical ideas and features of the present invention, and their purpose is to enable those who are familiar with the art to understand the content of the present invention and implement them accordingly. When the scope of the patent of the present invention cannot be limited, that is, everything else Various equivalent changes or modifications made without departing from the spirit of the present invention are all covered by the scope of the present invention, and should be included in the scope of the following patent applications.

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Claims (12)

一種苯二胺衍生物，上述苯二胺衍生物如下述化學式1所示，
Figure 104116282-A0305-02-0040-1
 (上述化學式1中R1為
Figure 104116282-A0305-02-0040-14
；n為1；X1為CH2連接基；X2為選自-O-或-OCO-的連接基；Z1及Z2分別為單鍵、
Figure 104116282-A0305-02-0040-4
或
Figure 104116282-A0305-02-0040-15
；Y1、Y2、Y3、Y4分別為H或F；Z3選自烷基、氟基、烷氧基、全氟烷氧基；a為0至5之間的值)；以及其中上述化學式1選自下列群組的其中之一：
Figure 104116282-A0305-02-0041-16
Figure 104116282-A0305-02-0041-17
，以及
Figure 104116282-A0305-02-0041-18
。 A phenylenediamine derivative, the above-mentioned phenylenediamine derivative is shown in the following chemical formula 1.
Figure 104116282-A0305-02-0040-1
 (R 1 in the above chemical formula 1 is
Figure 104116282-A0305-02-0040-14
; N is 1; X 1 is a CH 2 linking group; X 2 is a linking group selected from -O- or -OCO-; Z 1 and Z 2 are respectively a single bond,
Figure 104116282-A0305-02-0040-4
or
Figure 104116282-A0305-02-0040-15
; Y 1 , Y 2 , Y 3 , and Y 4 are respectively H or F; Z 3 is selected from alkyl, fluoro, alkoxy, perfluoroalkoxy; a is a value between 0 and 5); and Wherein the above chemical formula 1 is selected from one of the following groups:
Figure 104116282-A0305-02-0041-16
Figure 104116282-A0305-02-0041-17
,as well as
Figure 104116282-A0305-02-0041-18
. 一種液晶顯示裝置的垂直配向劑用聚醯亞胺樹脂的製備方法，包含：(a)在溶劑中，將化學式1所示側鏈型二胺化合物與、下述化學式2所示的四羧酸酐及化學式3所示無側鏈的二胺化合物進行反應而製備聚醯胺酸類嵌段共聚物的步驟；及(b)將步驟(a)的聚醯胺酸類嵌段共聚物進行熱處理，通過脫水閉環反應轉變成聚醯亞胺的步驟，
Figure 104116282-A0305-02-0041-19
 (上述化學式1中的取代基與申請專利範圍1中記載的內容相同。)[化學式2]
Figure 104116282-A0305-02-0042-7
 [化學式3]H2N-R 2 ．NH2(上述化學式2及化學式3中，A為構成四羧酸的四價有機基；R2為無側鏈的二價有機基。) A preparation method of a polyimide resin for a vertical alignment agent of a liquid crystal display device, comprising: (a) in a solvent, a side chain diamine compound shown in chemical formula 1 and a tetracarboxylic anhydride shown in chemical formula 2 below And the step of reacting the diamine compound without side chains shown in chemical formula 3 to prepare a polyamide-acid block copolymer; The step of turning the ring-closing reaction into polyimide,
Figure 104116282-A0305-02-0041-19
 (The substituents in the above chemical formula 1 are the same as those described in the scope 1 of the patent application.) [Chemical formula 2]
Figure 104116282-A0305-02-0042-7
 [Chemical formula 3] H 2 N- R 2 . NH 2 (In the above Chemical Formula 2 and Chemical Formula 3, A is a tetravalent organic group constituting a tetracarboxylic acid; R 2 is a divalent organic group without a side chain.) 如申請專利範圍第2項所述的液晶顯示裝置的垂直配向劑用聚醯亞胺樹脂的製備方法，其中上述化學式3所示的二胺為選自：對苯二胺、間苯二胺、4,4'-二氨基二苯甲烷、4,4'-二氨基二苯乙烷、4,4'-二氨基二苯硫醚、4,4'-二氨基二苯碸、3,3'-二甲基-4,4'-二氨基聯苯、4,4'-二氨基苯醯替苯胺、4,4'-二氨基二苯醚、1,5-二氨基萘、2,2'-二甲基-4,4'-二氨基聯苯、5-氨基-1-(4'-氨基苯基)-1,3,3-三甲基茚滿、6-氨基-1-(4'-氨基苯基)-1,3,3-三甲基茚滿、3,4'-二氨基二苯醚、3,3'-二氨基二苯甲酮、3,4'-二氨基二苯甲酮、4,4'-二氨基二苯甲酮、2,2-雙[4-(4-氨基苯氧基)苯基]丙烷、2,2-雙[4-(4-氨基苯氧基)苯基]六氟丙烷、2,2-雙(4-氨基苯基)六氟丙烷、2,2-雙[4-(4-氨基苯氧基)苯基]碸、1,4-雙(4-氨基苯氧基)苯、1,3-雙(4-氨基苯氧基)苯、1,3-雙(3-氨基苯氧基)苯、9,9-雙(4-氨基苯基)-10-氫基蒽、2,7-二氨基芴、9,9-雙(4-氨基苯基)芴、4,4'-亞甲基-雙(2-氯 苯胺)、2,2',5,5'-四氯-4,4'-二氨基聯苯、2,2'-二氯-4,4'-二氨基-5,5'-二甲氧基聯苯、3,3'-二甲氧-4,4'-二氨基聯苯、1,4,4'-(對苯異丙酯)雙苯胺、4,4'-(間苯異丙酯)雙苯胺、2,2'-雙[4-(4-氨基-2-三氟苯氧基)苯]六氟丙烷、4,4'-二氨基-2,2'-雙(三氟甲基)聯苯、4,4'-雙[(4-氨基-2-三氟甲基)苯氧基]-八氟聯苯、二(4-氨基苯)聯苯胺、1-(4-氨苯基)-1,3,3-三甲基-1H-茚-5-胺、1,1-間苯二甲胺、1,3-丙二胺、四甲撐二胺、戊撐二胺、已撐二胺、庚二胺、辛二胺、壬二胺、1,4-二氨基環己烷、異佛爾酮二胺、四氫二聚環戊二烯基二胺、三環[6.2.1.02,7]-十一碳烯二甲基二胺、4,4'-亞基雙環己胺、1,3-雙(氨甲基)環己烷等脂肪族或環脂肪族二胺；2,3-二氨基吡啶、2,6-二氨基吡啶、3,4-二氨基吡啶、2,4-二氨基吡啶、5,6-二氨基-2,3-二氰基吡嗪、5,6-二氨基-2,4-二羥基吡啶、2,4-二氨基-6-二甲基氨基-1,3,5-三嗪、1,4-雙(3-氨丙基)呱嗪、2,4-二氨基-6-異丙氧基-1,3,5-三嗪、2,4-二氨基-6-甲氧基-1,3,5-三嗪、2,4-二氨基-6-苯基-1,3,5-三嗪、2,4-二氨基-6-甲基-s-三嗪、2,4-二氨基-1,3,5-三嗪、4,6-二氨基-2-乙烯基-s-三嗪、2,4-二氨基-5-苯基噻唑、2,6-二氨基嘌呤、5,6-二氨基-1,3-二甲基脲嘧啶、3,5-二氨基-1,2,4-***、6,9-二氨基-2-乙氧基丫啶乳酸、3,8-二氨基-6-苯基菲啶、1,4-二氨基呱水合物、3,6-二氨基吖啶、雙(4-氨基苯基)苯胺、1-(3,5-二氨基苯基)-3-十二烷基琥珀醯亞胺、1-(3，5-二氨基苯基)-3-十八烷基琥珀醯亞胺的一種或其組合。 As described in item 2 of the scope of patent application, the method for preparing polyimide resin for vertical alignment agent of liquid crystal display device, wherein the diamine shown in the above chemical formula 3 is selected from: p-phenylenediamine, m-phenylenediamine, 4,4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylethane, 4,4'-Diaminodiphenylsulfide, 4,4'-Diaminodiphenylsulfide, 3,3' -Dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminophenylaniline, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2' -Dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4 '-Aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenyl Benzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminobenzene) Oxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl] chrysene, 1,4 -Bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4- Aminophenyl)-10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylene-bis(2-chloro Aniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxy Biphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-(p-phenylisopropyl) dianiline, 4,4'-(m-phenylisopropyl) Ester) bisaniline, 2,2'-bis[4-(4-amino-2-trifluorophenoxy)benzene]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoro Methyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, bis(4-aminobenzene)benzidine, 1-(4- Aminophenyl)-1,3,3-trimethyl-1H-indene-5-amine, 1,1-m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine Amine, alkylene diamine, heptane diamine, octane diamine, nonane diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienyl diamine, tricyclic [6.2.1.02,7]-Undecene dimethyl diamine, 4,4'-dicyclohexylamine, 1,3-bis (aminomethyl) cyclohexane and other aliphatic or cycloaliphatic two Amine; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyridine, 5,6-diamino-2,3-dicyanopyrazine , 5,6-diamino-2,4-dihydroxypyridine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl )Piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2 ,4-Diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5- Triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1, 3-Dimethyluracil, 3,5-Diamino-1,2,4-triazole, 6,9-Diamino-2-ethoxyacridine lactic acid, 3,8-Diamino-6-benzene Glyphenanthridine, 1,4-diaminopyridine, 3,6-diaminoacridine, bis(4-aminophenyl)aniline, 1-(3,5-diaminophenyl)-3-12 One or a combination of alkyl succinimidyl and 1-(3,5-diaminophenyl)-3-octadecyl succinimidyl. 如申請專利範圍第2項所述的液晶顯示裝置的垂直配向劑用聚醯亞胺樹脂的製備方法，其中上述化學式2所示的環脂肪族酸二酐為選自：1,2,3,4-環丁烷四羧酸二酐、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二氯-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-四甲 基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、3,3',4,4'-雙環己基四羧酸二酐、反-3,7-二丁基環辛-1,5-二烯-1,2,5,6-四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、5-(2,5-二氧基四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、3,5,6-三羧基-2-羧基降冰片烯-2：3、5：6-二酐、2,3,4,5-四氫呋喃四羧酸二酐、1,3,3a,4,5,9b-六氫基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-5-甲基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-5-乙基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-7-甲基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-7-乙基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-8-甲基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-8-乙基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-5,8-二甲基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、5-(2,5-二氧基四氫呋喃)-3-甲基-3-環己烯-1,2-二羧酸酐、雙環[2.2.2]-辛-7-烯-2,3,5,6-四羧酸二酐、3-氧雜雙環[3.2.1]辛烷-2,4-二酮-6-螺-3'-(四氫呋喃-2',5'-二酮)的一種或其組合；並且，上述化學式2所示的芳香族酸二酐為選自：均苯四甲酸二酐、4,4'-鄰苯二甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、3,3',4,4'-二苯基碸四甲酸二酸酐、1,4,5,8-萘四甲酸二酐、2,3,6,7-萘四甲酸二酐、3 3' 4 4'-聯苯醚四甲酸二酐、3,3',4,4'-二甲基二苯基矽烷四甲酸二酐、3,3',4,4'-四苯基矽烷四甲酸二酐、1,2,3,4-呋喃四甲酸二酐、4,4'-雙(3,4-二羧酸基苯氧基)二苯硫醚二酐、4,4'-雙(3,4-二羧酸基苯氧基)二苯基碸二酐、4,4'-雙(3,4-二羧 酸基苯氧基)二苯基丙烷二酐、3,3',4,4'-全氟異丙基二酞酸二酐、3,3',4,4'-聯苯四甲酸二酐、雙(鄰苯二甲酸)氧化膦二酐、對苯-雙(三苯基鄰苯二甲酸)二酐、間苯-雙(三苯基鄰苯二甲酸)二酐、雙(三苯基鄰苯二甲酸)-4,4'-二苯醚二酐、雙(三苯基鄰苯二甲酸)-4,4'-二苯甲烷二酐、乙二醇-雙(脫水偏苯三酸酯)、丙二醇-雙(脫水偏苯三酸酯)、1,4-丁二醇-雙(脫水偏苯三酸酯)、1,6-己二醇-雙(脫水偏苯三酸酯)、1,8-辛二醇-雙(脫水偏苯三酸酯)、2,2-雙(4-羥苯基)丙烷-雙(脫水偏苯三酸酯)的一種或其組合。 The method for preparing a polyimide resin for a vertical alignment agent of a liquid crystal display device as described in item 2 of the scope of patent application, wherein the cycloaliphatic acid dianhydride represented by the above chemical formula 2 is selected from: 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid Dianhydride, 3,3',4,4'-biscyclohexyltetracarboxylic dianhydride, trans-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid Acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5-(2,5-dioxytetrahydro-3-furyl)-3-methyl-3-cyclohexene-1 ,2-Dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornene-2:3,5:6-dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1 ,3,3a,4,5,9b-Hexahydro-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3- Dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2- c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5(tetrahydro-2,5-dioxy-3-furan )-Naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5(tetrahydro-2, 5-Dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl -5(Tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b -Hexahydro-8-methyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1, 3,3a,4,5,9b-hexahydro-8-ethyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan- 1,3-Diketone, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxy-3-furan)- Naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-dioxytetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride , Bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6- One or a combination of spiro-3'-(tetrahydrofuran-2',5'-dione); and the aromatic acid dianhydride represented by the above chemical formula 2 is selected from: pyromellitic dianhydride, 4,4 '-Phthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 1,4 ,5,8-Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3 3'4 4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'- Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetra Phenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxylic phenoxy) diphenyl sulfide dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl dianhydride, 4,4'-bis(3,4-dicarboxy Acid group phenoxy) diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropyl diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride , Bis(phthalic acid) phosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-benzene-bis(triphenylphthalic acid) dianhydride, bis(triphenyl) Phthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(anhydrotrimellitic acid) Ester), Propylene Glycol-Bis (Anhydro trimellitate), 1,4-Butanediol-Bis (Anhydro trimellitate), 1,6-Hexanediol-Bis (Anhydro trimellitate) One or a combination of 1,8-octanediol-bis(dehydrated trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(dehydrated trimellitate). 如申請專利範圍第2項所述的液晶顯示裝置的液晶配向劑用聚醯亞胺樹脂的製備方法，其中上述溶劑為選自由N-甲基-2-吡咯烷酮(NMP)、N,N-二甲基甲醯胺(DMF)、二甲基亞碸(DMSO)、六甲基磷醯胺、環丁碸、對氯苯酚、對溴苯酚、2-氯-4-羥基甲苯、二噁烷、四氫呋喃(THF)、以及環己酮組成的組中的一種以上的非活性溶劑。 As described in item 2 of the scope of patent application, the method for preparing polyimide resin for liquid crystal alignment agent of liquid crystal display device, wherein the above-mentioned solvent is selected from N-methyl-2-pyrrolidone (NMP), N,N-two Methylformamide (DMF), dimethyl sulfide (DMSO), hexamethylphosphoramide, cyclobutene, p-chlorophenol, p-bromophenol, 2-chloro-4-hydroxytoluene, dioxane, One or more inert solvents in the group consisting of tetrahydrofuran (THF) and cyclohexanone. 一種液晶顯示裝置的液晶配向劑用聚醯亞胺樹脂，根據申請專利範圍第2項所述的製備方法製備成重均分子量為1,000至200,000。 A polyimide resin for a liquid crystal alignment agent of a liquid crystal display device is prepared with a weight average molecular weight of 1,000 to 200,000 according to the preparation method described in item 2 of the scope of patent application. 如申請專利範圍第6項所述的聚醯亞胺樹脂，該聚醯亞胺樹脂的側鏈長度為液晶分子長軸長度的0.8倍至1.5倍，而側鏈間的長度為液晶分子長軸長度的1.5倍至3.5倍。 For the polyimide resin described in item 6 of the scope of the patent application, the side chain length of the polyimide resin is 0.8 to 1.5 times the length of the long axis of the liquid crystal molecule, and the length between the side chains is the long axis of the liquid crystal molecule 1.5 to 3.5 times the length. 一種液晶配向膜，其利用申請專利範圍第6項所述的液晶顯示裝置的液晶配向劑用聚醯亞胺樹脂製成。 A liquid crystal alignment film is made of polyimide resin using the liquid crystal alignment agent of the liquid crystal display device described in item 6 of the scope of patent application. 一種液晶顯示元件，包含申請專利範圍第8項所述的液晶配向膜。 A liquid crystal display element includes the liquid crystal alignment film described in item 8 of the scope of patent application. 一種用作液晶顯示裝置的液晶液晶配向劑的聚醯亞胺樹脂，包含化學式1所示的側鏈型二胺化合物，以及化學式2所示的環脂肪族酸二酐，以及化學式3所示的無側鏈的二胺；
Figure 104116282-A0305-02-0046-8
 (上述化學式1中R1為
Figure 104116282-A0305-02-0046-20
；n為1；X1為CH2連接基；X2為選自-O-或-OCO-的連接基；Z1及Z2分別為單鍵、
Figure 104116282-A0305-02-0046-10
或
Figure 104116282-A0305-02-0046-21
；Y1、Y2、Y3、Y4分別為H或F；Z3選自烷基、氟基、烷氧基、全氟烷氧基；a為0至5之間的值)；以及其中上述化學式1為選自下列群組中的其中之一：
Figure 104116282-A0305-02-0047-22
Figure 104116282-A0305-02-0047-24
、以及
Figure 104116282-A0305-02-0047-25
；
Figure 104116282-A0305-02-0047-26
 [化學式3]H2N-R 2 ．NH2(上述化學式2及化學式3中，A為構成四羧酸的四價有機基；R2為無側鏈的二價有機基。) A polyimide resin used as a liquid crystal alignment agent of a liquid crystal display device, comprising a side chain diamine compound shown in chemical formula 1, a cycloaliphatic acid dianhydride shown in chemical formula 2, and a polyimide resin shown in chemical formula 3. Diamines without side chains;
Figure 104116282-A0305-02-0046-8
 (R 1 in the above chemical formula 1 is
Figure 104116282-A0305-02-0046-20
; N is 1; X 1 is a CH 2 linking group; X 2 is a linking group selected from -O- or -OCO-; Z 1 and Z 2 are respectively a single bond,
Figure 104116282-A0305-02-0046-10
or
Figure 104116282-A0305-02-0046-21
; Y 1 , Y 2 , Y 3 , and Y 4 are respectively H or F; Z 3 is selected from alkyl, fluoro, alkoxy, perfluoroalkoxy; a is a value between 0 and 5); and Wherein the above chemical formula 1 is selected from one of the following groups:
Figure 104116282-A0305-02-0047-22
Figure 104116282-A0305-02-0047-24
,as well as
Figure 104116282-A0305-02-0047-25
；
Figure 104116282-A0305-02-0047-26
 [Chemical formula 3] H 2 N- R 2 . NH 2 (In the above Chemical Formula 2 and Chemical Formula 3, A is a tetravalent organic group constituting a tetracarboxylic acid; R 2 is a divalent organic group without a side chain.) 如申請專利範圍第10項所述的聚醯亞胺樹脂，其中上述化學式3所示的二胺為選自：對苯二胺、間苯二胺、4,4'-二氨基二苯甲烷、4,4'-二氨基二苯乙烷、4,4'-二氨基二苯硫醚、4,4'-二氨基二苯碸、3,3'-二甲基-4,4'-二氨基聯苯、4,4'-二氨基苯醯替苯胺、4,4'-二氨基二苯醚、1,5-二氨基萘、2,2'-二甲基-4,4'-二氨基聯苯、5- 氨基-1-(4'-氨基苯基)-1,3,3-三甲基茚滿、6-氨基-1-(4'-氨基苯基)-1,3,3-三甲基茚滿、3,4'-二氨基二苯醚、3,3'-二氨基二苯甲酮、3,4'-二氨基二苯甲酮、4,4'-二氨基二苯甲酮、2,2-雙[4-(4-氨基苯氧基)苯基]丙烷、2,2-雙[4-(4-氨基苯氧基)苯基]六氟丙烷、2,2-雙(4-氨基苯基)六氟丙烷、2,2-雙[4-(4-氨基苯氧基)苯基]碸、1,4-雙(4-氨基苯氧基)苯、1,3-雙(4-氨基苯氧基)苯、1,3-雙(3-氨基苯氧基)苯、9,9-雙(4-氨基苯基)-10-氫基蒽、2,7-二氨基芴、9,9-雙(4-氨基苯基)芴、4,4'-亞甲基-雙(2-氯苯胺)、2,2',5,5'-四氯-4,4'-二氨基聯苯、2,2'-二氯-4,4'-二氨基-5,5'-二甲氧基聯苯、3,3'-二甲氧-4,4'-二氨基聯苯、1,4,4'-(對苯異丙酯)雙苯胺、4,4'-(間苯異丙酯)雙苯胺、2,2'-雙[4-(4-氨基-2-三氟苯氧基)苯]六氟丙烷、4,4'-二氨基-2,2'-雙(三氟甲基)聯苯、4,4'-雙[(4-氨基-2-三氟甲基)苯氧基]-八氟聯苯、二(4-氨基苯)聯苯胺、1-(4-氨苯基)-1,3,3-三甲基-1H-茚-5-胺、1,1-間苯二甲胺、1,3-丙二胺、四甲撐二胺、戊撐二胺、已撐二胺、庚二胺、辛二胺、壬二胺、1,4-二氨基環己烷、異佛爾酮二胺、四氫二聚環戊二烯基二胺、三環[6.2.1.02,7]-十一碳烯二甲基二胺、4,4'-亞基雙環己胺、1,3-雙(氨甲基)環己烷等脂肪族或環脂肪族二胺；2,3-二氨基吡啶、2,6-二氨基吡啶、3,4-二氨基吡啶、2,4-二氨基吡啶、5,6-二氨基-2,3-二氰基吡嗪、5,6-二氨基-2,4-二羥基吡啶、2,4-二氨基-6-二甲基氨基-1,3,5-三嗪、1,4-雙(3-氨丙基)呱嗪、2,4-二氨基-6-異丙氧基-1,3,5-三嗪、2,4-二氨基-6-甲氧基-1,3,5-三嗪、2,4-二氨基-6-苯基-1,3,5-三嗪、2,4-二氨基-6-甲基-s-三嗪、2,4-二氨基-1,3,5-三嗪、4,6-二氨基-2-乙烯基-s-三嗪、2,4-二氨基-5-苯基噻唑、2,6-二氨基嘌呤、5,6-二氨基-1,3-二甲基脲嘧啶、3,5-二氨基-1,2,4-***、6,9-二氨基-2-乙氧基丫啶乳酸、3,8-二氨基-6-苯基菲啶、1,4-二氨基呱水合物、3,6-二氨基 吖啶、雙(4-氨基苯基)苯胺、1-(3,5-二氨基苯基)-3-十二烷基琥珀醯亞胺、1-(3，5-二氨基苯基)-3-十八烷基琥珀醯亞胺的一種或其組合。 The polyimide resin as described in item 10 of the scope of patent application, wherein the diamine shown in the above chemical formula 3 is selected from: p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-Diaminodiphenylethane, 4,4'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfide, 3,3'-Dimethyl-4,4'-di Aminobiphenyl, 4,4'-diaminophenylaniline, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-di Aminobiphenyl, 5- Amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane Full, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2 ,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4 -Aminophenyl) hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl] sulfide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis (4-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 2,7-diamino Fluorene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4' -Diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 1,4,4'-(p-phenylisopropyl) bisaniline, 4,4'-(m-phenylisopropyl) bisaniline, 2,2'-bis[4-(4-amino-2 -Trifluorophenoxy)benzene]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2- (Trifluoromethyl)phenoxy)-octafluorobiphenyl, bis(4-aminobenzene)benzidine, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indene-5 -Amine, 1,1-m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, 1 ,4-Diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienyl diamine, tricyclic [6.2.1.02,7]-undecene dimethyl diamine, 4, Aliphatic or cycloaliphatic diamines such as 4'-subunit biscyclohexylamine, 1,3-bis(aminomethyl)cyclohexane; 2,3-diaminopyridine, 2,6-diaminopyridine, 3, 4-diaminopyridine, 2,4-diaminopyridine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyridine, 2,4- Diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)piperazine, 2,4-diamino-6-isopropoxy-1, 3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-Diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-Diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4 -Triazole, 6,9-diamino-2-ethoxyacridine lactic acid, 3,8-diamine 6-phenylphenanthridine, 1,4-diamino hydrate, 3,6-diamino Acridine, bis(4-aminophenyl)aniline, 1-(3,5-diaminophenyl)-3-dodecylsuccinimide, 1-(3,5-diaminophenyl)- One or a combination of 3-octadecyl succinimidyl. 如申請專利範圍第10項所述的聚醯亞胺樹脂，其中上述化學式2所示的環脂肪族酸二酐為選自：1,2,3,4-環丁烷四羧酸二酐、1,2-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、1,3-二氯-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-四甲基-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、3,3',4,4'-雙環己基四羧酸二酐、反-3,7-二丁基環辛-1,5-二烯-1,2,5,6-四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、5-(2,5-二氧基四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、3,5,6-三羧基-2-羧基降冰片烯-2：3、5：6-二酐、2,3,4,5-四氫呋喃四羧酸二酐、1,3,3a,4,5,9b-六氫基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-5-甲基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-5-乙基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-7-甲基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-7-乙基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-8-甲基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-8-乙基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、1,3,3a,4,5,9b-六氫基-5,8-二甲基-5(四氫基-2,5-二氧基-3-呋喃)-萘並[1,2-c]-呋喃-1，3-二酮、5-(2,5-二氧基四氫呋喃)-3-甲基-3-環己烯-1,2-二羧酸酐、雙環[2.2.2]-辛-7-烯-2,3,5,6-四羧酸二酐、3-氧雜雙環[3.2.1]辛烷-2,4-二酮-6-螺-3'-(四氫呋喃-2',5'-二酮)的一種或其組合； 並且，上述化學式2所示的芳香族酸二酐為選自：均苯四甲酸二酐、4,4'-鄰苯二甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、3,3',4,4'-二苯基碸四甲酸二酸酐、1,4,5,8-萘四甲酸二酐、2,3,6,7-萘四甲酸二酐、3 3' 4 4'-聯苯醚四甲酸二酐、3,3',4,4'-二甲基二苯基矽烷四甲酸二酐、3,3',4,4'-四苯基矽烷四甲酸二酐、1,2,3,4-呋喃四甲酸二酐、4,4'-雙(3,4-二羧酸基苯氧基)二苯硫醚二酐、4,4'-雙(3,4-二羧酸基苯氧基)二苯基碸二酐、4,4'-雙(3,4-二羧酸基苯氧基)二苯基丙烷二酐、3,3',4,4'-全氟異丙基二酞酸二酐、3,3',4,4'-聯苯四甲酸二酐、雙(鄰苯二甲酸)氧化膦二酐、對苯-雙(三苯基鄰苯二甲酸)二酐、間苯-雙(三苯基鄰苯二甲酸)二酐、雙(三苯基鄰苯二甲酸)-4,4'-二苯醚二酐、雙(三苯基鄰苯二甲酸)-4,4'-二苯甲烷二酐、乙二醇-雙(脫水偏苯三酸酯)、丙二醇-雙(脫水偏苯三酸酯)、1,4-丁二醇-雙(脫水偏苯三酸酯)、1,6-己二醇-雙(脫水偏苯三酸酯)、1,8-辛二醇-雙(脫水偏苯三酸酯)、2,2-雙(4-羥苯基)丙烷-雙(脫水偏苯三酸酯)的一種或其組合。 The polyimide resin as described in item 10 of the scope of patent application, wherein the cycloaliphatic acid dianhydride represented by the above chemical formula 2 is selected from: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-Dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-Dichloro-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetra Carboxylic dianhydride, trans-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid Dianhydride, 5-(2,5-dioxytetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy- 2-Carboxynorbornene-2: 3, 5: 6-dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5 (Tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexa Hydroxy-5-methyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3, 3a,4,5,9b-hexahydro-5-ethyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1, 3-Diketone, 1,3,3a,4,5,9b-hexahydro-7-methyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1, 2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5(tetrahydro-2,5-dioxy-3 -Furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5(tetrahydro- 2,5-Dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8- Ethyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5 ,9b-hexahydro-5,8-dimethyl-5(tetrahydro-2,5-dioxy-3-furan)-naphtho[1,2-c]-furan-1,3- Dione, 5-(2,5-dioxytetrahydrofuran)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2, 3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione ) Or a combination thereof; In addition, the aromatic acid dianhydride represented by the above chemical formula 2 is selected from: pyromellitic dianhydride, 4,4'-phthalic dianhydride, 3,3',4,4'-benzophenone Tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride Anhydride, 3 3'4 4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetra Phenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxylic phenoxy) diphenyl sulfide dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenyl dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropyl diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phosphine oxide dianhydride, P-benzene-bis(triphenylphthalic acid) dianhydride, iso-benzene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl Ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(dehydrate trimellitate), propylene glycol-bis(dehydrate trimellitate) ), 1,4-butanediol-bis(dehydrated trimellitate), 1,6-hexanediol-bis(dehydrated trimellitate), 1,8-octanediol-bis(dehydrated trimellitate) Trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydro trimellitate) or a combination thereof.
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