TWI550025B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element Download PDF

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TWI550025B
TWI550025B TW103134374A TW103134374A TWI550025B TW I550025 B TWI550025 B TW I550025B TW 103134374 A TW103134374 A TW 103134374A TW 103134374 A TW103134374 A TW 103134374A TW I550025 B TWI550025 B TW I550025B
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liquid crystal
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crystal alignment
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polymer
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TW201614005A (en
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梁育豪
張維倫
許立道
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奇美實業股份有限公司
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Description

液晶配向劑、液晶配向膜以及液晶顯示元件 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

本發明是關於一種液晶配向劑、液晶配向膜及液晶顯示元件，特別是關於一種可形成框膠攤平性佳的液晶配向膜的液晶配向劑、由上述液晶配向劑形成的液晶配向膜以及具有上述液晶配向膜的液晶顯示元件。 The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element, and more particularly to a liquid crystal alignment agent capable of forming a liquid crystal alignment film having good flatness of a sealant, a liquid crystal alignment film formed of the above liquid crystal alignment agent, and A liquid crystal display element of the above liquid crystal alignment film.

近年來，由於對液晶顯示器的顯示品質要求日益提升，液晶配向劑的品質與特性，例如液晶配向性及離子密度等特性，其要求變得比以往更為嚴苛。其中，當離子密度過高時，容易產生殘影等問題，而造成顯示品質嚴重下降。 In recent years, as the display quality requirements for liquid crystal displays have been increasing, the quality and characteristics of liquid crystal alignment agents, such as liquid crystal alignment properties and ion density, have become more demanding than ever. Among them, when the ion density is too high, problems such as image sticking tend to occur, and the display quality is seriously degraded.

日本專利特開第2009-175684號公報揭示一種低離子密度的液晶配向膜以及一種用來製備液晶配向膜的含哌嗪(piperazine)結構的二胺化合物。藉由使用含哌嗪結構的二胺化合物所製成的液晶配向膜可改善以往液晶顯示器因離子密度過高而造成顯示品質下降的問題。然而，液晶配向膜卻有框膠攤平性 不佳的問題，而使得後續加工製程的良率降低。 Japanese Laid-Open Patent Publication No. 2009-175684 discloses a low ion density liquid crystal alignment film and a diamine compound containing a piperazine structure for preparing a liquid crystal alignment film. By using a liquid crystal alignment film made of a diamine compound containing a piperazine structure, the problem of deterioration in display quality due to excessive ion density in a conventional liquid crystal display can be improved. However, the liquid crystal alignment film has a flatness of the sealant. Poor problems, resulting in lower yields for subsequent processing.

因此，如何解決液晶配向膜存在框膠攤平性不佳的問題，乃為目前本領域技術人員積極研究的目標之一。 Therefore, how to solve the problem that the liquid crystal alignment film has poor flatness of the sealant is one of the objects actively studied by those skilled in the art.

有鑑於此，本發明提供一種液晶配向劑，其可形成框膠攤平性佳的液晶配向膜、由上述液晶配向劑形成的液晶配向膜以及具有上述液晶配向膜的液晶顯示元件。 In view of the above, the present invention provides a liquid crystal alignment agent which can form a liquid crystal alignment film having a good sealer flatness, a liquid crystal alignment film formed of the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

本發明提供一種液晶配向劑，其包括：聚合物(A)以及溶劑(B)，其中聚合物(A)是由包括四羧酸二酐組份(a)及二胺組份(b)的混合物反應而獲得。四羧酸二酐組份(a)包括至少一種由式(1)表示的四羧酸二酐化合物(a-1)。二胺組份(b)包括至少一種由式(2)表示的二胺化合物(b-1)。 The present invention provides a liquid crystal alignment agent comprising: a polymer (A) and a solvent (B), wherein the polymer (A) is composed of a component (a) comprising a tetracarboxylic dianhydride and a component (b) of a diamine. The mixture is obtained by reaction. The tetracarboxylic dianhydride component (a) includes at least one tetracarboxylic dianhydride compound (a-1) represented by the formula (1). The diamine component (b) includes at least one diamine compound (b-1) represented by the formula (2).

具體而言，由式(1)表示的四羧酸二酐化合物(a-1)如下所示。 Specifically, the tetracarboxylic dianhydride compound (a-1) represented by the formula (1) is as follows.

式(1)中，a表示2至20的整數；另外，由式(2)表示的二胺化合物(b-1)如下所示。 In the formula (1), a represents an integer of 2 to 20, and the diamine compound (b-1) represented by the formula (2) is shown below.

式(2)中，W1及W2各自獨立表示單鍵、-CO-、-COO-或-OCO-；Y1表示碳數為1至10的烷基、碳數為3至12的脂環族基、碳數為6至12的芳香族基、羥基、鹵素原子、硝基或氰基，其中，烷基、脂環族基及芳香族基中的亞甲基(methylene，-CH2-)可經氧原子、-CO-、-COO-或-OCO-取代，且亞甲基的氫原子可經至少1個鹵素原子取代；Y2及Y3各自獨立表示碳數為1至10的烷基、碳數為1至10的烷氧基或鹵素原子；b及c各自獨立表示大於等於1的整數，且b+c≧3；d表示0至5的整數；e及f各自獨立表示0至4的整數。 In the formula (2), W 1 and W 2 each independently represent a single bond, -CO-, -COO- or -OCO-; Y 1 represents an alkyl group having 1 to 10 carbon atoms and a fat having 3 to 12 carbon atoms. a cycloradical group having 6 to 12 carbon atoms, a hydroxyl group, a halogen atom, a nitro group or a cyano group, wherein the alkyl group, the alicyclic group and the methylene group in the aromatic group (methylene, -CH 2 ) -) may be substituted by an oxygen atom, -CO-, -COO- or -OCO-, and the hydrogen atom of the methylene group may be substituted with at least one halogen atom; Y 2 and Y 3 each independently represent a carbon number of 1 to 10 The alkyl group, the alkoxy group having a carbon number of 1 to 10 or a halogen atom; b and c each independently represent an integer of 1 or more, and b+c≧3; d represents an integer of 0 to 5; and e and f are each independently An integer representing 0 to 4.

在本發明的一實施例中，基於四羧酸二酐組份(a)的總使用量為100莫耳，四羧酸二酐化合物(a-1)的使用量為15至100莫耳。 In an embodiment of the present invention, the total amount of the tetracarboxylic dianhydride component (a) used is 100 mol, and the tetracarboxylic dianhydride compound (a-1) is used in an amount of 15 to 100 mol.

在本發明的一實施例中，基於二胺組份(b)的總使用量為100莫耳，二胺化合物(b-1)的使用量為5至80莫耳。 In an embodiment of the invention, the total amount used based on the diamine component (b) is 100 moles, and the diamine compound (b-1) is used in an amount of 5 to 80 moles.

在本發明的一實施例中，二胺化合物(b-1)包括由式(3)表示的二胺化合物。 In an embodiment of the invention, the diamine compound (b-1) includes a diamine compound represented by the formula (3).

式(3)中，W1及W2各自獨立表示單鍵、-CO-、-COO-或-OCO-；Y1表示碳數為1至10的烷基、碳數為3至12的脂環族基、碳數為6至12的芳香族基、羥基、鹵素原子、硝基或氰基，其中，烷基、脂環族基及芳香族基中的亞甲基可經氧原子、-CO-、-COO-或-OCO-取代，且亞甲基的氫原子可經至少1個鹵素原子取代；Y2及Y3各自獨立表示碳數為1至10的烷基、碳數為1至10的烷氧基或鹵素原子；b及c各自獨立表示大於等於1的整數，且b+c≧3；d表示0至5的整數；e及f各自獨立表示0至4的整數。 In the formula (3), W 1 and W 2 each independently represent a single bond, -CO-, -COO- or -OCO-; Y 1 represents an alkyl group having 1 to 10 carbon atoms and a fat having 3 to 12 carbon atoms. a cycloradical group having 6 to 12 carbon atoms, a hydroxyl group, a halogen atom, a nitro group or a cyano group, wherein the methylene group in the alkyl group, the alicyclic group and the aromatic group may be via an oxygen atom, CO-, -COO- or -OCO-substituted, and the hydrogen atom of the methylene group may be substituted with at least one halogen atom; Y 2 and Y 3 each independently represent an alkyl group having a carbon number of 1 to 10 and a carbon number of 1 Alkoxy or a halogen atom to 10; b and c each independently represent an integer of 1 or more, and b+c≧3; d represents an integer of 0 to 5; and e and f each independently represent an integer of 0 to 4.

在本發明的一實施例中，上述的聚合物(A)的醯亞胺化率為30%至90%。 In an embodiment of the invention, the above polymer (A) has a ruthenium iodide ratio of 30% to 90%.

本發明還提供一種液晶配向膜，其是由上述的液晶配向劑而形成。 The present invention also provides a liquid crystal alignment film which is formed by the above liquid crystal alignment agent.

本發明另提供一種液晶顯示元件，其包括如上述的液晶配向膜。 The present invention further provides a liquid crystal display element comprising the liquid crystal alignment film as described above.

基於上述，在本發明的液晶配向劑中，形成聚合物的混合物由於含有特定的四羧酸二酐化合物與特定的二胺化合物，因此使用本發明的液晶配向劑所製造液晶配向膜的框膠攤平性佳，而可進一步提高後續加工製程的良率。 Based on the above, in the liquid crystal alignment agent of the present invention, since the mixture forming the polymer contains a specific tetracarboxylic dianhydride compound and a specific diamine compound, the sealant of the liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention is used. It has good leveling and can further improve the yield of subsequent processing.

為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。 The above described features and advantages of the invention will be apparent from the following description.

100‧‧‧液晶顯示元件 100‧‧‧Liquid display components

110‧‧‧第一單元 110‧‧‧ first unit

112‧‧‧第一基板 112‧‧‧First substrate

114‧‧‧第一導電膜 114‧‧‧First conductive film

116‧‧‧第一液晶配向膜 116‧‧‧First liquid crystal alignment film

120‧‧‧第二單元 120‧‧‧Second unit

122‧‧‧第二基板 122‧‧‧second substrate

124‧‧‧第二導電膜 124‧‧‧Second conductive film

126‧‧‧第二液晶配向膜 126‧‧‧Second liquid crystal alignment film

130‧‧‧液晶單元 130‧‧‧Liquid Crystal Unit

圖1是根據本發明一實施例的液晶顯示元件的側視圖。 1 is a side view of a liquid crystal display element in accordance with an embodiment of the present invention.

<液晶配向劑><Liquid alignment agent>

本發明提供一種液晶配向劑，其包括聚合物(A)以及溶劑(B)。此外，若需要，液晶配向劑可更包括添加劑(C)。 The present invention provides a liquid crystal alignment agent comprising a polymer (A) and a solvent (B). Further, the liquid crystal alignment agent may further include the additive (C), if necessary.

在下文中，將詳細說明用於本發明的液晶配向劑的各個成分。 Hereinafter, the respective components of the liquid crystal alignment agent used in the present invention will be described in detail.

在此說明的是，以下是以(甲基)丙烯酸表示丙烯酸及/或甲基丙烯酸，並以(甲基)丙烯酸酯表示丙烯酸酯及/或甲基丙烯酸酯；同樣地，以(甲基)丙烯醯基表示丙烯醯基及/或甲基丙烯醯基。 Here, the following description means that acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, and acrylate and/or methacrylate is represented by (meth)acrylate; similarly, (meth) The acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group.

聚合物(A)Polymer (A)

聚合物(A)是由混合物反應而獲得，混合物包括四羧酸二酐組份(a)及二胺組份(b)。 The polymer (A) is obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a) and a diamine component (b).

詳細而言，聚合物(A)包括聚醯胺酸、聚醯亞胺、聚醯 胺酸-聚醯亞胺嵌段共聚合物或這些聚合物的組合。其中，聚醯亞胺系嵌段共聚合物包括聚醯胺酸嵌段共聚合物、聚醯亞胺嵌段共聚合物、聚醯胺酸-聚醯亞胺嵌段共聚合物或上述聚合物的組合。聚醯胺酸聚合物、聚醯亞胺聚合物及聚醯胺酸-聚醯亞胺嵌段共聚合物皆可由四羧酸二酐組份(a)及二胺組份(b)的混合物反應所製得。 In detail, the polymer (A) includes polylysine, polyimine, polyfluorene Amino acid-polyimine block copolymers or combinations of these polymers. Wherein the polyamidene block copolymer comprises a polyphthalic acid block copolymer, a polyamidiene block copolymer, a poly-proline-polyimine block copolymer or the above polymerization a combination of things. The polyaminic acid polymer, the polyimine polymer, and the polyamido-polyimide block copolymer may be a mixture of the tetracarboxylic dianhydride component (a) and the diamine component (b). The reaction was prepared.

四羧酸二酐組份(a)Tetracarboxylic dianhydride component (a)

四羧酸二酐組份(a)包括至少一種四羧酸二酐化合物(a-1)。此外，四羧酸二酐組份(a)亦可包括其他四羧酸二酐化合物(a-2)。 The tetracarboxylic dianhydride component (a) includes at least one tetracarboxylic dianhydride compound (a-1). Further, the tetracarboxylic dianhydride component (a) may also include other tetracarboxylic dianhydride compound (a-2).

四羧酸二酐化合物(a-1)Tetracarboxylic dianhydride compound (a-1)

四羧酸二酐化合物(a-1)為由式(1)表示的化合物。 The tetracarboxylic dianhydride compound (a-1) is a compound represented by the formula (1).

式(1)中，a表示2至20的整數。 In the formula (1), a represents an integer of 2 to 20.

四羧酸二酐化合物(a-1)的具體例包括乙二醇雙(偏苯三酸酐)(ethyleneglycol-bis(trimellitic anhydride))、1,3-丙二醇 雙(偏苯三酸酐)(1,3-propanediol-bis(trimellitic anhydride))、1,4-丁二醇雙(偏苯三酸酐)(1,4-butanediol-bis(trimellitic anhydride))、1,5-戊二醇雙(偏苯三酸酐)(1,5-pentanediol-bis(trimellitic anhydride))、1,6-己二醇雙(偏苯三酸酐)(1,6-hexanediol-bis(trimellitic anhydride))、1,8-辛二醇雙(偏苯三酸酐)(1,8-octanediol-bis(trimellitic anhydride))、1,10-癸烷二醇雙(偏苯三酸酐)(1,10-decanediol-bis(trimellitic anhydride))、1,12-十二烷二醇雙(偏苯三酸酐)(1,12-dodecanediol-bis(trimellitic anhydride))、1,16-十六烷二醇雙(偏苯三酸酐)(1,16-hexadecanediol-bis(trimellitic anhydride))、1,18-十八烷二醇雙(偏苯三酸酐)(1,18-octadecanediol-bis(trimellitic anhydride))、1,20-二十烷二醇雙(偏苯三酸酐)(1,20-eicosanediol-bis(trimellitic anhydride))，或上述化合物的組合。 Specific examples of the tetracarboxylic dianhydride compound (a-1) include ethyleneglycol-bis (trimellitic anhydride) and 1,3-propanediol. 1,3-propanediol-bis (trimellitic anhydride), 1,4-butanediol-bis (trimellitic anhydride), 1,5-pentanediol 1,5-pentanediol-bis (trimellitic anhydride), 1,6-hexanediol-bis (trimellitic anhydride), 1,8-octanediol 1,8-octanediol-bis (trimellitic anhydride), 1,10-decanediol-bis (trimellitic anhydride), 1,12-12 1,1,12-dodecanediol-bis (trimellitic anhydride), 1,16-hexadecanediol-bis (trimellitic anhydride), 1, 18-octadecanediol bis(trimellitic anhydride), 1,20-eicosanediol bis(trimellitic anhydride) (1,20-eicosanediol-bis (trimellitic anhydride) ), or a combination of the above compounds.

四羧酸二酐組份(a-1)的具體例較佳為包括乙二醇雙(偏苯三酸酐)、1,3-丙二醇雙(偏苯三酸酐)、1,4-丁二醇雙(偏苯三酸酐)、1,6-己二醇雙(偏苯三酸酐)、1,8-辛二醇雙(偏苯三酸酐)、1,10-癸烷二醇雙(偏苯三酸酐)、1,18-十八烷二醇雙(偏苯三酸酐)、1,20-二十烷二醇雙(偏苯三酸酐)或上述化合物的組合。 Specific examples of the tetracarboxylic dianhydride component (a-1) preferably include ethylene glycol bis(trimellitic anhydride), 1,3-propanediol bis(trimellitic anhydride), 1,4-butanediol bis(trimellitic anhydride), and 1 , 6-hexanediol bis(trimellitic anhydride), 1,8-octanediol bis(trimellitic anhydride), 1,10-decanediol bis(trimellitic anhydride), 1,18-octadecanediol bis(trimellitic anhydride), 1,20-Eicosanediol bis(trimellitic anhydride) or a combination of the above compounds.

基於四羧酸二酐組份(a)的總使用量為100莫耳，四羧酸二酐化合物(a-1)的使用量可為15莫耳至100莫耳，較佳為20莫耳至90莫耳，更佳為30莫耳至80莫耳。當液晶配向劑不使 用四羧酸二酐化合物(a-1)時，則液晶配向膜有框膠攤平性不佳的問題。 The tetracarboxylic dianhydride compound (a-1) may be used in an amount of from 15 moles to 100 moles, preferably 20 moles, based on the total amount of the tetracarboxylic dianhydride component (a) used in an amount of 100 moles. Up to 90 moles, more preferably 30 moles to 80 moles. When the liquid crystal alignment agent does not make When the tetracarboxylic dianhydride compound (a-1) is used, the liquid crystal alignment film has a problem that the flatness of the sealant is not good.

其他四羧酸二酐化合物(a-2)Other tetracarboxylic dianhydride compound (a-2)

其他四羧酸二酐化合物(a-2)包括脂肪族四羧酸二酐化合物、脂環族四羧酸二酐化合物、芳香族四羧酸二酐化合物、由式(I-1)至式(I-6)表示的四羧酸二酐化合物中的至少一種，或上述化合物的組合。 The other tetracarboxylic dianhydride compound (a-2) includes an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, and the formula (I-1) to At least one of the tetracarboxylic dianhydride compounds represented by (I-6) or a combination of the above compounds.

以下列舉脂肪族四羧酸二酐化合物、脂環族四羧酸二酐化合物、芳香族四羧酸二酐化合物的具體例，但本發明並不限於這些具體例。 Specific examples of the aliphatic tetracarboxylic dianhydride compound, the alicyclic tetracarboxylic dianhydride compound, and the aromatic tetracarboxylic dianhydride compound are listed below, but the present invention is not limited to these specific examples.

脂肪族四羧酸二酐化合物的具體例可包括但不限於乙烷四羧酸二酐(ethane tetracarboxylic dianhydride)、丁烷四羧酸二酐(butane tetracarboxylic dianhydride)或上述化合物的組合。 Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride or a combination of the above compounds.

脂環族四羧酸二酐化合物的具體例可包括但不限於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、順式-3,7-二丁基環庚基-1,5-二烯-1,2,5,6-四羧酸二酐、2,3,5-三羧基環戊基醋 酸二酐、雙環[2.2.2]-辛-7-烯-2,3,5,6-四羧酸二酐或上述化合物的組合。 Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-ring Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl ring Heptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl vinegar Acid dianhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride or a combination of the above compounds.

芳香族四羧酸二酐化合物的具體例可包括但不限於、3,4-二羧基-1,2,3,4-四氫萘-1-琥珀酸二酐、苯均四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、3,3’,4,4’-聯苯碸四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、3,3’-4,4’-二苯基乙烷四羧酸二酐、3,3’,4,4’-二甲基二苯基矽烷四羧酸二酐、3,3’,4,4’-四苯基矽烷四羧酸二酐、1,2,3,4-呋喃四羧酸二酐、4,4’-雙(3,4-二羧基苯氧基)二苯硫醚二酐、4,4’-雙(3,4-二羧基苯氧基)二苯碸二酐、4,4’-雙(3,4-二羧基苯氧基)二苯丙烷二酐(4,4’-bis(3,4-dicarboxy phenoxy)diphenylpropane dianhydride)、3,3’,4,4’-全氟異亞丙基二苯二酸二酐、3,3’,4,4’-二苯基四羧酸二酐、雙(苯二酸)苯膦氧化物二酐、對-伸苯基-雙(三苯基苯二酸)二酐、間-伸苯基-雙(三苯基苯二酸)二酐、雙(三苯基苯二酸)-4,4’-二苯基醚二酐、雙(三苯基苯二酸)-4,4’-二苯基甲烷二酐、2,2-雙(4-羥苯基)丙烷-雙(脫水偏苯三酸酯)、2,3,4,5-四氫呋喃四羧酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮{(1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione)}、1,3,3a,4,5,9b-六氫-5-甲基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]- 呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-5-乙基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-7-甲基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-7-乙基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-乙基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-5,8-二甲基-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-c]-呋喃-1,3-二酮、5-(2,5-二側氧基四氫呋喃基)-3-甲基-3-環己烯-1,2-二羧酸二酐等芳香族四羧酸二酐化合物，或上述化合物的組合。 Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid dianhydride, benzene tetracarboxylic dianhydride. , 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalene Carboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-diphenylethane tetracarboxylic dianhydride, 3,3',4,4' - dimethyldiphenylnonanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4 , 4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4' -4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoro Propylene diphthalic acid dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis ( Triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, Bis(triphenylphthalic acid)-4,4' -diphenylmethane dianhydride, 2,2-bis(4-hydroxyphenyl)propane-bis(hydroper trimellitate), 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3 ,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-di Ketone {(1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione)}, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c] - Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)- Naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro-2,5-di Oxyloxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5 -(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b -hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1 ,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]- Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-di-oxy-3-furan -Naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-di- oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1, An aromatic tetracarboxylic dianhydride compound such as 2-dicarboxylic dianhydride or a combination of the above compounds.

由式(I-1)至式(I-6)表示的四羧酸二酐化合物如下所示。 The tetracarboxylic dianhydride compound represented by the formula (I-1) to the formula (I-6) is as follows.

式(I-5)中，A1表示含有芳香環的二價基團；r表示1至2的整數；A2及A3可為相同或不同，且可各自獨立表示氫原子或烷基。由式(I-5)表示的四羧酸二酐化合物的具體例包括由式(I-5-1)至式(I-5-3)表示的化合物中的至少一種。 In the formula (I-5), A 1 represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; and A 2 and A 3 may be the same or different and each independently represents a hydrogen atom or an alkyl group. Specific examples of the tetracarboxylic dianhydride compound represented by the formula (I-5) include at least one of the compounds represented by the formula (I-5-1) to the formula (I-5-3).

式(I-6)中，A4表示含有芳香環的二價基團；A5及A6可為相同或不同，且各自獨立表示氫原子或烷基。由式(I-6)表示的四羧酸二酐化合物較佳為由式(I-6-1)表示的化合物。 In the formula (I-6), A 4 represents a divalent group containing an aromatic ring; and A 5 and A 6 may be the same or different and each independently represents a hydrogen atom or an alkyl group. The tetracarboxylic dianhydride compound represented by the formula (I-6) is preferably a compound represented by the formula (I-6-1).

四羧酸二酐組份(a)可以單獨使用或者組合多種來使用。 The tetracarboxylic dianhydride component (a) may be used singly or in combination of two or more.

其他四羧酸二酐組份(a-2)的具體例較佳為包括1,2,3,4-環丁烷四羧酸二酐(1,2,3,4-cyclobutane tetracarboxylic acid dianhydride)、1,2,3,4-環戊烷四羧酸二酐、2,3,5-三羧基環戊基醋酸二酐(2,3,5-tricarboxy cyclopentylacetic acid dianhydride)、1,2,4,5-環己烷四羧酸二酐、3,4-二羧基-1,2,3,4-四氫萘-1-琥珀酸二酐、苯均四羧酸二酐(pyromellitic dianhydride)、3,3’,4,4’-二苯甲酮四羧酸二酐、3,3’,4,4’-聯苯碸四羧酸二酐，或上述化合物的組合。 Specific examples of the other tetracarboxylic dianhydride component (a-2) preferably include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride (1,2,3,4-cyclobutane tetracarboxylic acid dianhydride) 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, or a combination of the above compounds.

基於四羧酸二酐組份(a)的總使用量為100莫耳，其他四羧酸二酐化合物(a-2)的使用量可為0至85莫耳，較佳為10至80莫耳，更佳為20至70莫耳。 The total amount of the tetracarboxylic dianhydride component (a) used is 100 moles, and the other tetracarboxylic dianhydride compound (a-2) may be used in an amount of 0 to 85 moles, preferably 10 to 80 moles. Ears are preferably 20 to 70 moles.

基於二胺組份(b)的總莫耳數為100莫耳，四羧酸二酐組份(a)的使用量範圍較佳為20莫耳至200莫耳；四羧酸二酐組份(a)的使用量範圍更佳為30莫耳至120莫耳。 The total mole number based on the diamine component (b) is 100 moles, and the tetracarboxylic dianhydride component (a) is preferably used in an amount ranging from 20 moles to 200 moles; the tetracarboxylic dianhydride component The range of use of (a) is preferably from 30 moles to 120 moles.

二胺組份(b)Diamine component (b)

二胺組份(b)包括至少一種二胺化合物(b-1)。此外，二胺組份(b)亦可包括其他二胺化合物(b-2)。 The diamine component (b) includes at least one diamine compound (b-1). Further, the diamine component (b) may also include other diamine compounds (b-2).

二胺化合物(b-1)Diamine compound (b-1)

二胺化合物(b-1)為由式(2)表示的化合物。 The diamine compound (b-1) is a compound represented by the formula (2).

式(2)中，W1及W2各自獨立表示單鍵、-CO-、-COO-或-OCO-。 In the formula (2), W 1 and W 2 each independently represent a single bond, -CO-, -COO- or -OCO-.

式(2)中，Y1表示碳數為1至10的烷基、碳數為3至12的脂環族基、碳數為6至12的芳香族基、羥基、鹵素原子(氟 原子、氯原子、溴原子或碘原子)、硝基或氰基，其中，所述烷基、所述脂環族基及所述芳香族基中的亞甲基可經氧原子、-CO-、-COO-或-OCO-取代，且亞甲基的氫原子可經至少1個鹵素原子取代。 In the formula (2), Y 1 represents an alkyl group having 1 to 10 carbon atoms, an alicyclic group having 3 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, a hydroxyl group, a halogen atom (fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a nitro group or a cyano group, wherein the alkyl group, the alicyclic group and the methylene group in the aromatic group may be via an oxygen atom, -CO-, - COO- or -OCO-substituted, and the hydrogen atom of the methylene group may be substituted with at least one halogen atom.

當Y1表示碳數為1至10的烷基時，碳數為1至10的烷基例如可列舉甲基、乙基、正丙基、異丙基、正丁基、2-丁基、異丁基、第三丁基、正戊基、正己基、正庚基、正辛基、正壬基或正癸基等。當Y1表示碳數為3至12的脂環族烴基時，碳數為3至12的脂環族烴基例如可列舉環戊基或環己基等。當Y1表示碳數為6至12的芳香族基時，碳數為6至12的芳香族基例如可列舉苯基、甲苯基或苄基等。Y1較佳為表示碳數為1至10的烷基，更佳為碳數為1至3的烷基，且特別佳為甲基。當存在多個Y1的情況下，多個Y1各自可相同亦可不同。 When Y 1 represents an alkyl group having a carbon number of 1 to 10, the alkyl group having 1 to 10 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or a 2-butyl group. Isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl or n-decyl. When Y 1 represents an alicyclic hydrocarbon group having 3 to 12 carbon atoms, the alicyclic hydrocarbon group having 3 to 12 carbon atoms may, for example, be a cyclopentyl group or a cyclohexyl group. When Y 1 represents an aromatic group having 6 to 12 carbon atoms, examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, and a benzyl group. Y 1 is preferably an alkyl group having a carbon number of 1 to 10, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. When a plurality of Y 1 are present, each of the plurality of Y 1 may be the same or different.

式(2)中，Y2及Y3各自獨立表示碳數為1至10的烷基、碳數為1至10的烷氧基或鹵素原子。當Y2及Y3表示碳數為1至10的烷基或鹵素原子時，碳數為1至10的烷基及鹵素原子例如可列舉與上述Y1相同。當Y2及Y3表示碳數為1至10的烷氧基時，碳數為1至10的烷氧基例如可列舉甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基或癸氧基等。Y2及Y3較佳為碳數為1至3的烷基、碳數為1至3的烷氧基、氟原子、氯原子或溴原子。當存在多個Y2及Y3的情況下，多個Y2及Y3各自可相同亦可不同。 In the formula (2), Y 2 and Y 3 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen atom. When Y 2 and Y 3 represent an alkyl group having 1 to 10 carbon atoms or a halogen atom, the alkyl group having 1 to 10 carbon atoms and a halogen atom are, for example, the same as Y 1 described above. When Y 2 and Y 3 represent an alkoxy group having a carbon number of 1 to 10, the alkoxy group having a carbon number of 1 to 10 may, for example, be a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentyloxy group. Base, hexyloxy, heptyloxy, octyloxy, decyloxy or decyloxy. Y 2 and Y 3 are preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom, a chlorine atom or a bromine atom. When a plurality of Y 2 and Y 3 are present, each of Y 2 and Y 3 may be the same or different.

式(2)中，b及c各自獨立表示大於等於1的整數(其中b=c=1除外)，且b+c≧3，較佳為3≦b+c≦11。另外，b及c的組合特別佳為b=1、c=2或b=2、c=2。 In the formula (2), b and c each independently represent an integer greater than or equal to 1 (where b = c = 1), and b + c ≧ 3, preferably 3 ≦ b + c ≦ 11. Further, a combination of b and c is particularly preferably b=1, c=2 or b=2, and c=2.

式(2)中，d表示0至5的整數，較佳為表示0至2的整數，更佳為表示0或1的整數。 In the formula (2), d represents an integer of 0 to 5, preferably an integer of 0 to 2, more preferably an integer of 0 or 1.

式(2)中，e及f各自獨立表示0至4的整數，較佳為0至2的整數，更佳為0或1的整數。 In the formula (2), e and f each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably an integer of 0 or 1.

值得注意的是，鍵結於苯環上的各個胺基(amino group)的位置相對於W1、W2而言可為鄰位、間位或對位，鍵結於不同苯環上的2個胺基較佳為相對於W1、W2而言均為鄰位、、均為對位或均為間位，特別佳為相對於W1、W2而言均為對位。 It is worth noting that the positions of the respective amino groups bonded to the benzene ring may be ortho, meta or para to W 1 and W 2 and may be bonded to different benzene rings. with respect to amine groups is preferably W 1, W 2 are in terms ,, are ortho or meta to the position are particularly good with respect to W 1, W 2 both in terms of alignment.

具體而言，鍵結於不同苯環上的2個胺基較佳為相對於W1、W2而言均為對位的二胺化合物為由式(3)表示的二胺化合物。 Specifically, the diamine compound which is bonded to a different benzene ring and which is preferably para-position with respect to W 1 and W 2 is a diamine compound represented by the formula (3).

式(3)中的W1、W2、Y1、Y2、Y3、b、c、d、e及f與式(2)中的W1、W2、Y1、Y2、Y3、b、c、d、e及f同義，在此不另行贅述。 W 1 , W 2 , Y 1 , Y 2 , Y 3 , b, c, d, e, and f in the formula (3) and W 1 , W 2 , Y 1 , Y 2 , Y in the formula (2) 3 , b, c, d, e and f are synonymous and will not be further described here.

由式(3)表示的二胺化合物例如是後述由式(2-1)、式(2-4)、式(2-7)、式(2-10)、式(2-11)、式(2-13)至式(2-18) 表示的二胺化合物。 The diamine compound represented by the formula (3) is, for example, a formula (2-1), a formula (2-4), a formula (2-7), a formula (2-10), a formula (2-11), and a formula, which will be described later. (2-13) to formula (2-18) A diamine compound represented.

二胺化合物(b-1)的具體例包括由式(2-1)至式(2-18)表示的二胺化合物的至少其中一者。 Specific examples of the diamine compound (b-1) include at least one of the diamine compounds represented by the formula (2-1) to the formula (2-18).

基於二胺組份(b)的總使用量為100莫耳，二胺化合物(b-1)的使用量可為5至80莫耳，較佳為10莫耳至75莫耳，更佳為15莫耳至70莫耳。當液晶配向劑不使用二胺化合物(b-1)時，則液晶配向膜有框膠攤平性不佳的問題。 The total amount of the diamine component (b) used may be 100 moles, and the diamine compound (b-1) may be used in an amount of 5 to 80 moles, preferably 10 moles to 75 moles, more preferably 15 moles to 70 moles. When the liquid crystal alignment agent does not use the diamine compound (b-1), the liquid crystal alignment film has a problem that the sealant is not flat.

當二胺化合物(b-1)包括由式(3)表示的二胺化合物時，可進一步提升液晶配向劑所製造的液晶配向膜的框膠攤平性。 When the diamine compound (b-1) includes the diamine compound represented by the formula (3), the sealant uniformity of the liquid crystal alignment film produced by the liquid crystal alignment agent can be further improved.

其他二胺化合物(b-2)Other diamine compounds (b-2)

其他二胺化合物(b-2)包括脂肪族二胺化合物、脂環族二胺化合物、芳香族二胺化合物、具有結構式(II-1)至(II-30)的二胺化合物、或其組合。 The other diamine compound (b-2) includes an aliphatic diamine compound, an alicyclic diamine compound, an aromatic diamine compound, a diamine compound having the structural formula (II-1) to (II-30), or combination.

脂肪族二胺化合物的具體例包括但不限於1,2-二胺基乙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、4,4’-二胺基庚烷、1,3-二胺基-2,2-二甲基丙烷、1,6-二胺基-2,5-二甲基己烷、1,7-二胺基-2,5-二甲基庚烷、1,7-二胺基-4,4-二甲基庚烷、1,7-二胺基-3-甲基庚烷、1,9-二胺基-5-甲基壬烷、2,11-二胺基十二烷、1,12-二胺基十八烷、1,2-雙(3-胺基丙氧基)乙烷，或上述化合物的組合。 Specific examples of the aliphatic diamine compound include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane 1,6-Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane , 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1, 9-Diamino-5-methyldecane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy)B Alkane, or a combination of the above compounds.

脂環族二胺化合物的具體例包括但不限於4,4’-二胺基二環己基甲烷、4,4’-二胺基-3,3’-二甲基二環己基胺、1,3-二胺基環己烷、1,4-二胺基環己烷、異佛爾酮二胺、四氫二環戊二烯二胺、三環[6.2.1.02,7]-十一碳烯二甲基二胺、4,4’-亞甲基雙(環己基胺)，或上述化合物的組合。 Specific examples of the alicyclic diamine compound include, but are not limited to, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1, 3-diaminocyclohexane, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene diamine, tricyclo[6.2.1.0 2,7 ]- eleven Carboxydimethyldiamine, 4,4'-methylenebis(cyclohexylamine), or a combination of the above compounds.

芳香族二胺化合物的具體例包括但不限於4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基乙烷、4,4’-二胺基二苯基碸、4,4’-二胺基苯甲醯苯胺、4,4’-二胺基二苯基醚、3,4’-二胺基二苯基醚、1,5-二胺基萘、5-胺基-1-(4’-胺基苯基)-1,3,3-三甲基氫茚、6-胺基 -1-(4’-胺基苯基)-1,3,3-三甲基氫茚、六氫-4,7-甲橋伸氫茚基二亞甲基二胺、3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、4,4’-二胺基二苯甲酮、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]碸、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、9,9-雙(4-胺基苯基)-10-氫蒽、9,10-雙(4-胺基苯基)蒽[9,10-bis(4-aminophenyl)anthracene]、2,7-二胺基茀、9,9-雙(4-胺基苯基)茀、4,4’-亞甲基-雙(2-氯苯胺)、4,4’-(對-伸苯基異亞丙基)雙苯胺、4,4’-(間-伸苯基異亞丙基)雙苯胺、2,2’-雙[4-(4-胺基-2-三氟甲基苯氧基)苯基]六氟丙烷、4,4’-雙[(4-胺基-2-三氟甲基)苯氧基]-八氟聯苯、5-[4-(4-正戊烷基環己基)環己基]苯基-亞甲基-1,3-二胺基苯{5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene}、1,1-雙[4-(4-胺基苯氧基)苯基]-4-(4-乙基苯基)環己烷{1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane}，或上述化合物的組合。 Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Bismuth, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroquinone, 6-amino group -1-(4'-aminophenyl)-1,3,3-trimethylhydroquinone, hexahydro-4,7-methyl bridge hydroquinone dimethylene diamine, 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]anthracene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 9,10-bis(4-aminophenyl)anthracene [9,10-bis(4-aminophenyl)anthracene], 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis (2 -Chloroaniline), 4,4'-(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene)diphenylamine, 2,2'-double [ 4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]- Octafluorobiphenyl, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenyl-methylene-1,3-diaminobenzene {5-[4-(4-n-pentylcyclohexyl) )cyclohexyl]phenylmethylene-1, 3-diaminobenzene}, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane {1,1-bis[4-(4 -aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane}, or a combination of the above compounds.

具有結構式(II-1)至(II-30)的二胺化合物如下所示。 The diamine compounds having the structural formulae (II-1) to (II-30) are shown below.

式(II-1)中，B1表示 ，或；B2表示具有甾(類固醇)骨架的基、三 氟甲基、氟基、碳數為2至30的烷基、或衍生自吡啶、嘧啶、三嗪、哌啶或哌嗪等含氮原子環狀結構的一價基團。 In the formula (II-1), B 1 represents ,or ; B 2 represents a group having a quinone (steroid) skeleton, a trifluoromethyl group, a fluorine group, an alkyl group having 2 to 30 carbon atoms, or a nitrogen atom derived from a pyridine, pyrimidine, triazine, piperidine or piperazine; A monovalent group of a cyclic structure.

由式(II-1)表示的化合物的具體例包括但不限於2,4-二胺基苯基甲酸乙酯(2,4-diaminophenyl ethyl formate)、3,5-二胺基苯基甲酸乙酯(3,5-diaminophenyl ethyl formate)、2,4-二胺基苯基甲酸丙酯(2,4-diaminophenyl propyl formate)、3,5-二胺基苯基甲酸丙酯(3,5-diaminophenyl propyl formate)、1-十二烷氧基-2,4-二胺基苯(1-dodecoxy-2,4-diaminobenzene)、1-十六烷氧基-2,4-二胺基苯(1-hexadecoxy-2,4-diaminobenzene)、1-十八烷氧基-2,4-二胺基苯(1-octadecoxy-2,4-diaminobenzene)、由式(II-1-1)至式(II-1-6)表示的化合物中的至少其中一種，或上述化合物的組合。 Specific examples of the compound represented by the formula (II-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diaminophenylethylate B 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate (3,5- Diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene 1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene, from formula (II-1-1) to formula At least one of the compounds represented by (II-1-6), or a combination of the above compounds.

由式(II-1-1)至式(II-1-6)表示的化合物如下所示。 The compound represented by the formula (II-1-1) to the formula (II-1-6) is shown below.

式(II-2)中，B1與式(II-1)中的B1相同，B3及B4各自獨立表示二價脂肪族環、二價芳香族環或二價雜環基團；B5表示碳數為3至18的烷基、碳數為3至18的烷氧基、碳數為1至5的氟烷基、碳數為1至5的氟烷氧基、氰基或鹵素原子。 , B 1 same formula (II-2) with the formula B (II-1) is 1, B 3 and B 4 each independently represents a divalent aliphatic ring, a divalent aromatic ring or a divalent heterocyclic group; B 5 represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, a fluoroalkoxy group having 1 to 5 carbon atoms, or a cyano group or Halogen atom.

由式(II-2)表示的化合物的具體例包括由式(II-2-1)至式(II-2-13)表示的化合物中的至少其中一種。具體而言，由式(II-2-1)至式(II-2-13)表示的化合物如下所示。 Specific examples of the compound represented by the formula (II-2) include at least one of the compounds represented by the formula (II-2-1) to the formula (II-2-13). Specifically, the compound represented by the formula (II-2-1) to the formula (II-2-13) is as follows.

式(II-2-10)至式(II-2-13)中，s表示3至12的整數。 In the formula (II-2-10) to the formula (II-2-13), s represents an integer of from 3 to 12.

式(II-3)中，B6各自獨立表示氫原子、碳數為1至5的醯基、碳數為1至5的烷基、碳數為1至5的烷氧基或鹵素原子，且每個重複單元中的B6可為相同或不同；u表示1至3的整數。 In the formula (II-3), B 6 each independently represents a hydrogen atom, a fluorenyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom. And B 6 in each repeating unit may be the same or different; u represents an integer of 1 to 3.

由式(II-3)表示的化合物的具體例包括當u為1時：對-二胺苯、間-二胺苯、鄰-二胺苯或2,5-二胺基甲苯等；當u為2時：4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、2,2’-二氯-4,4’-二胺基聯苯、3,3’-二氯-4,4’-二胺基 聯苯、2,2’,5,5’-四氯-4,4’-二胺基聯苯、2,2’-二氯-4,4’-二胺基-5,5’-二甲氧基聯苯或4,4’-二胺基-2,2’-雙(三氟甲基)聯苯等；或當u為3時：1,4-雙(4’-胺基苯基)苯等。 Specific examples of the compound represented by the formula (II-3) include when p is 1: p-diamine benzene, m-diamine benzene, o-diamine benzene or 2,5-diaminotoluene, etc.; 2 hours: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'- Dichloro-4,4'-diamino Biphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-di Methoxybiphenyl or 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl; or when u is 3: 1,4-bis(4'-aminobenzene Base) benzene, etc.

由式(II-3)表示的化合物的具體例較佳為包括對-二胺苯、2,5-二胺基甲苯、4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、1,4-雙(4’-胺基苯基)苯或上述化合物的組合。 Specific examples of the compound represented by the formula (II-3) preferably include p-diamine benzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl Alkoxy-4,4'-diaminobiphenyl, 1,4-bis(4'-aminophenyl)benzene or a combination of the above compounds.

式(II-4)中，v表示2至12的整數。 In the formula (II-4), v represents an integer of 2 to 12.

式(II-5)中，w表示1至5的整數。由式(II-5)表示的化合物較佳為4,4’-二胺基-二苯基硫醚。 In the formula (II-5), w represents an integer of 1 to 5. The compound represented by the formula (II-5) is preferably 4,4'-diamino-diphenyl sulfide.

式(II-6)中，B7及B9各自獨立表示二價有機基團，且B7及B9可為相同或不同；B8表示衍生自吡啶、嘧啶、三嗪、哌啶或哌嗪等含氮原子的環狀結構的二價基團。 In the formula (II-6), B 7 and B 9 each independently represent a divalent organic group, and B 7 and B 9 may be the same or different; B 8 represents a derivative derived from pyridine, pyrimidine, triazine, piperidine or piperidine. a divalent group of a cyclic structure containing a nitrogen atom such as a azine.

式(II-7)中，B10、B11、B12及B13各自獨立表示碳數為1至12的烴基，且B10、B11、B12及B13可為相同或不同；X1各自獨立表示1至3的整數；X2表示1至20的整數。 In the formula (II-7), B 10 , B 11 , B 12 and B 13 each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and B 10 , B 11 , B 12 and B 13 may be the same or different; X1 Each represents an integer from 1 to 3; X2 represents an integer from 1 to 20.

式(II-8)中，B14表示氧原子或伸環己烷基；B15表示亞甲基；B16表示伸苯基或伸環己烷基；B17表示氫原子或庚基。 In the formula (II-8), B 14 represents an oxygen atom or a cyclohexane group; B 15 represents a methylene group; B 16 represents a phenyl or cyclohexane group; and B 17 represents a hydrogen atom or a heptyl group.

由式(II-8)表示的化合物的具體例包括由式(II-8-1)表示的化合物、由式(II-8-2)表示的化合物或上述化合物的組合。 Specific examples of the compound represented by the formula (II-8) include a compound represented by the formula (II-8-1), a compound represented by the formula (II-8-2) or a combination of the above compounds.

由式(II-9)至式(II-30)表示的化合物如下所示。 The compound represented by the formula (II-9) to the formula (II-30) is shown below.

式(II-17)至式(II-25)中，B18較佳為表示碳數為1 至10的烷基或碳數為1至10的烷氧基；B19較佳為表示氫原子、碳數為1至10的烷基或碳數為1至10的烷氧基。 In the formulae (II-17) to (II-25), B 18 preferably represents an alkyl group having a carbon number of 1 to 10 or an alkoxy group having a carbon number of 1 to 10; and B 19 preferably represents a hydrogen atom. An alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

上述的其他二胺化合物(b-2)可單獨使用或組合多種來使用。 The other diamine compound (b-2) described above may be used singly or in combination of two or more.

其他二胺化合物(b-2)的具體例較佳為包括但不限於1,2-二胺基乙烷、4,4’-二胺基二環己基甲烷、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、5-[4-(4-正戊烷基環己基)環己基]苯基亞甲基-1,3-二胺基苯、1,1-雙[4-(4-胺基苯氧基)苯基]-4-(4-乙基苯基)環己烷、2,4-二胺基苯基甲酸乙酯、由式(II-1-1)表示的化合物、由式(II-1-2)表示的化合物、由式(II-1-5)表示的化合物、由式(II-2-1)表示的化合物、由式(II-2-11)表示的化合物、對-二胺苯、間-二胺苯、鄰-二胺苯、由式(II-8-1)表示的化合物、由式(II-26)表示的化合物、由式(II-29)表示的化合物，或上述化合物的組合。 Specific examples of the other diamine compound (b-2) preferably include, but are not limited to, 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamine group. Diphenylmethane, 4,4'-diaminodiphenyl ether, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane, ethyl 2,4-diaminophenylcarboxylate, a compound represented by the formula (II-1-1), a compound represented by the formula (II-1-2), a compound represented by the formula (II-1-5), and a compound represented by the formula (II-2-1) a compound represented by the formula (II-2-11), p-diamine benzene, m-diamine benzene, o-diamine benzene, a compound represented by the formula (II-8-1), and a formula (II- 26) a compound represented by the formula, a compound represented by the formula (II-29), or a combination of the above compounds.

基於二胺組份(b)的總使用量為100莫耳，其他二胺化合物(b-2)的使用量可為20至95莫耳，較佳為25莫耳至90莫耳，更佳為30莫耳至85莫耳。 The total amount of the diamine component (b) used may be 100 moles, and the other diamine compound (b-2) may be used in an amount of 20 to 95 moles, preferably 25 to 90 moles, more preferably It ranges from 30 to 85 mu.

製備聚合物(A)的方法Method for preparing polymer (A)

聚合物(A)可包括聚醯胺酸及聚醯亞胺中的至少一者。另外，聚合物(A)可更包括聚醯亞胺系嵌段共聚合物。以下進一 步說明上述各種聚合物的製備方法。 The polymer (A) may include at least one of polyamic acid and polyimine. Further, the polymer (A) may further include a polyimide-based block copolymer. Following one The steps for preparing the various polymers described above are described.

製備聚醯胺酸的方法Method for preparing polylysine

製備聚醯胺酸的方法為先將混合物溶解於溶劑中，其中混合物包括四羧酸二酐組份(a)與二胺組份(b)，並於0℃至100℃的溫度下進行聚縮合反應。反應1小時至24小時後，以蒸發器對反應溶液進行減壓蒸餾，即可得到聚醯胺酸。或者，將反應溶液倒入大量的貧溶劑中，以得到析出物。接著，以減壓乾燥的方式乾燥析出物，即可得到聚醯胺酸。 The method for preparing polylysine is to first dissolve the mixture in a solvent, wherein the mixture comprises the tetracarboxylic dianhydride component (a) and the diamine component (b), and is polymerized at a temperature of 0 ° C to 100 ° C. Condensation reaction. After reacting for 1 hour to 24 hours, the reaction solution is subjected to distillation under reduced pressure with an evaporator to obtain a polyamic acid. Alternatively, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate. Next, the precipitate is dried by drying under reduced pressure to obtain polylysine.

用於聚縮合反應中的溶劑可與下述液晶配向劑中的溶劑相同或不同，且用於聚縮合反應中的溶劑並無特別的限制，只要是可溶解反應物與生成物即可。溶劑較佳為包括但不限於(1)非質子系極性溶劑，例如：N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidinone；NMP)、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸、γ-丁內酯、四甲基尿素或六甲基磷酸三胺等的非質子系極性溶劑；或(2)酚系溶劑，例如：間-甲酚、二甲苯酚、酚或鹵化酚類等的酚系溶劑。基於混合物的總使用量為100重量份，用於聚縮合反應中的溶劑的使用量較佳為200重量份至2000重量份，且更佳為300重量份至1800重量份。 The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal alignment agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it is a soluble reactant and a product. The solvent preferably includes, but is not limited to, (1) an aprotic polar solvent such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide, An aprotic polar solvent such as N,N-dimethylformamide, dimethylhydrazine, γ-butyrolactone, tetramethylurea or hexamethylphosphoric acid triamide; or (2) a phenolic solvent, For example, a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The solvent used in the polycondensation reaction is preferably used in an amount of from 200 parts by weight to 2000 parts by weight, and more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the total amount of the mixture.

值得注意的是，於聚縮合反應中，溶劑可併用適量的貧溶劑，其中貧溶劑不會造成聚醯胺酸析出。貧溶劑可以使用單獨一種或者組合多種來使用，且其包括但不限於(1)醇類，例如： 甲醇、乙醇、異丙醇、環己醇、乙二醇、丙二醇、1,4-丁二醇或三乙二醇等的醇類；(2)酮類，例如：丙酮、甲基乙基酮、甲基異丁基酮、環己酮等的酮類；(3)酯類，例如：醋酸甲酯、醋酸乙酯、醋酸丁酯、草酸二乙酯、丙二酸二乙酯或乙二醇乙基醚醋酸酯等的酯類；(4)醚類，例如：二乙基醚、乙二醇甲基醚、乙二醇乙基醚、乙二醇正丙基醚、乙二醇異丙基醚、乙二醇正丁基醚、乙二醇二甲基醚或二乙二醇二甲基醚等的醚類；(5)鹵化烴類，例如：二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯或鄰-二氯苯等的鹵化烴類；或(6)烴類，例如：四氫呋喃、己烷、庚烷、辛烷、苯、甲苯或二甲苯等的烴類或上述溶劑的任意組合。基於二胺組份(b)的使用量為100重量份，貧溶劑的用量較佳為0重量份至60重量份，且更佳為0重量份至50重量份。 It is worth noting that in the polycondensation reaction, the solvent may be used in combination with an appropriate amount of a poor solvent, wherein the poor solvent does not cause precipitation of the polyamic acid. The poor solvent may be used singly or in combination of two or more, and includes, but is not limited to, (1) an alcohol, for example: Alcohols such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol or triethylene glycol; (2) ketones such as acetone and methyl ethyl ketone a ketone such as methyl isobutyl ketone or cyclohexanone; or (3) an ester such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate or ethylene Esters such as alcohol ethyl ether acetate; (4) ethers such as diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl Ethers such as ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether; (5) halogenated hydrocarbons such as dichloromethane, 1,2-dichloro a halogenated hydrocarbon such as ethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichlorobenzene; or (6) a hydrocarbon such as tetrahydrofuran, hexane, heptane or octane Any hydrocarbon such as benzene, toluene or xylene or any combination of the above solvents. The amount of the poor solvent is preferably from 0 part by weight to 60 parts by weight, and more preferably from 0 part by weight to 50 parts by weight, based on 100 parts by weight of the diamine component (b).

製備聚醯亞胺的方法Method for preparing polyimine

製備聚醯亞胺的方法為將上述製備聚醯胺酸的方法所製的聚醯胺酸在脫水劑及觸媒的存在下進行加熱而得。在加熱過程中，聚醯胺酸中的醯胺酸官能基可經由脫水閉環反應轉變成醯亞胺官能基(即醯亞胺化)。 The method for preparing the polyimine is obtained by heating the polylysine prepared by the above method for preparing polyamic acid in the presence of a dehydrating agent and a catalyst. During heating, the proline functional group in the polylysine can be converted to a quinone imine functional group (ie, hydrazide) via a dehydration ring closure reaction.

用於脫水閉環反應中的溶劑可與液晶配向劑中的溶劑(B)相同，故在此不另贅述。基於聚醯胺酸的使用量為100重量份，用於脫水閉環反應中的溶劑的使用量較佳為200重量份至2000重量份，且更佳為300重量份至1800重量份。 The solvent used in the dehydration ring closure reaction may be the same as the solvent (B) in the liquid crystal alignment agent, and therefore will not be further described herein. The amount of the solvent used in the dehydration ring-closure reaction is preferably from 200 parts by weight to 2000 parts by weight, and more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the polylysine.

為獲得較佳的聚醯胺酸的醯亞胺化程度，脫水閉環反應的操作溫度較佳為40℃至200℃，更佳為40℃至150℃。若脫水閉環反應的操作溫度低於40℃時，醯亞胺化的反應不完全，而降低聚醯胺酸的醯亞胺化程度。然而，若脫水閉環反應的操作溫度高於200℃時，所得的聚醯亞胺的重量平均分子量偏低。 In order to obtain a preferred degree of ruthenium iodide, the operating temperature of the dehydration ring closure reaction is preferably from 40 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C. If the operating temperature of the dehydration ring-closing reaction is lower than 40 ° C, the reaction of ruthenium imidization is incomplete, and the degree of ruthenium iodide of poly-proline is lowered. However, if the operating temperature of the dehydration ring-closure reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyimine is low.

用於脫水閉環反應中的脫水劑可選自於酸酐類化合物，其具體例如：醋酸酐、丙酸酐或三氟醋酸酐等的酸酐類化合物。基於聚醯胺酸為1莫耳，脫水劑的使用量為0.01莫耳至20莫耳。用於脫水閉環反應中的觸媒可選自於(1)吡啶類化合物，例如：吡啶、三甲基吡啶或二甲基吡啶等的吡啶類化合物；(2)三級胺類化合物，例如：三乙基胺等的三級胺類化合物。基於脫水劑的使用量為1莫耳，觸媒的使用量可為0.5莫耳至10莫耳。 The dehydrating agent used in the dehydration ring-closure reaction may be selected from acid anhydride compounds, and specific examples thereof include acid anhydride compounds such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The dehydrating agent is used in an amount of from 0.01 mol to 20 mol based on 1 mol of the polyglycolic acid. The catalyst used in the dehydration ring closure reaction may be selected from (1) a pyridine compound such as a pyridine compound such as pyridine, trimethylpyridine or lutidine; and (2) a tertiary amine compound, for example: A tertiary amine compound such as triethylamine. The amount of the dehydrating agent used is 1 mole, and the catalyst can be used in an amount of 0.5 mole to 10 moles.

聚合物(A)的醯亞胺化率可為30%至90%，較佳為35%至85%，且更佳為40%至80%。當液晶配向劑中聚合物(A)的醯亞胺化率在上述範圍內時，可進一步提升液晶配向膜的框膠攤平性。 The ruthenium amination rate of the polymer (A) may be from 30% to 90%, preferably from 35% to 85%, and more preferably from 40% to 80%. When the ruthenium imidation ratio of the polymer (A) in the liquid crystal alignment agent is within the above range, the sealant flatness of the liquid crystal alignment film can be further improved.

製備聚醯亞胺系嵌段共聚合物的方法Method for preparing polyamidene block copolymer

聚醯亞胺系嵌段共聚合物為選自聚醯胺酸嵌段共聚合物、聚醯亞胺嵌段共聚合物、聚醯胺酸-聚醯亞胺嵌段共聚合物或上述聚合物的任意組合。 The polyamidene block copolymer is selected from the group consisting of polyphthalic acid block copolymers, polyamidiene block copolymers, polyamido acid-polyimine block copolymers or the above polymerizations. Any combination of objects.

製備聚醯亞胺系嵌段共聚合物的方法較佳為先將起 始物溶解於溶劑中，並進行聚縮合反應，其中起始物包括至少一種聚醯胺酸及/或至少一種聚醯亞胺，且可進一步包括羧酸酐組份與二胺組份。 The method for preparing the polyamidene block copolymer is preferably first The starting material is dissolved in a solvent and subjected to a polycondensation reaction, wherein the starting material comprises at least one polyamic acid and/or at least one polyimine, and may further comprise a carboxylic anhydride component and a diamine component.

起始物中的羧酸酐組份與二胺組份可與製備聚醯胺酸的方法中所使用的四羧酸二酐組份(a)與二胺組份(b)相同，且用於聚縮合反應中的溶劑可與下述液晶配向劑中的溶劑相同，在此不另贅述。 The carboxylic anhydride component and the diamine component in the starting material may be the same as the tetracarboxylic dianhydride component (a) and the diamine component (b) used in the method for preparing the polyamic acid, and used for The solvent in the polycondensation reaction may be the same as the solvent in the liquid crystal alignment agent described below, and will not be further described herein.

基於起始物的使用量為100重量份，用於聚縮合反應中的溶劑的使用量較佳為200重量份至2000重量份，且更佳為300重量份至1800重量份。聚縮合反應的操作溫度較佳為0℃至200℃，且更佳為0℃至100℃。 The solvent used in the polycondensation reaction is preferably used in an amount of from 200 parts by weight to 2000 parts by weight, and more preferably from 300 parts by weight to 1800 parts by weight, based on 100 parts by weight of the starting material. The operation temperature of the polycondensation reaction is preferably from 0 ° C to 200 ° C, and more preferably from 0 ° C to 100 ° C.

起始物較佳為包括但不限於(1)二種末端基相異且結構相異的聚醯胺酸；(2)二種末端基相異且結構相異的聚醯亞胺；(3)末端基相異且結構相異的聚醯胺酸及聚醯亞胺；(4)聚醯胺酸、羧酸酐組份與二胺組份，其中，羧酸酐組份與二胺組份之中的至少一種與形成聚醯胺酸所使用的羧酸酐組份與二胺組份的結構相異；(5)聚醯亞胺、羧酸酐組份與二胺組份，其中，羧酸酐組份與二胺組份中的至少一種與形成聚醯亞胺所使用的羧酸酐組份與二胺組份的結構相異；(6)聚醯胺酸、聚醯亞胺、羧酸酐組份與二胺組份，其中，羧酸酐組份與二胺組份中的至少一種與形成聚醯胺酸或聚醯亞胺所使用的羧酸酐組份與二胺組份的結構相異；(7)二種結構相異的 聚醯胺酸、羧酸酐組份與二胺組份；(8)二種結構相異的聚醯亞胺、羧酸酐組份與二胺組份；(9)二種末端基為酸酐基且結構相異的聚醯胺酸以及二胺組份；(10)二種末端基為胺基且結構相異的聚醯胺酸以及羧酸酐組份；(11)二種末端基為酸酐基且結構相異的聚醯亞胺以及二胺組份；或者(12)二種末端基為胺基且結構相異的聚醯亞胺以及羧酸酐組份。 Preferably, the starting material comprises, but is not limited to, (1) two polyamido acids having different terminal groups and different structures; (2) two kinds of polyamidiamines having different terminal groups and different structures; a poly-proline and a polyamidiamine having different terminal groups and different structures; (4) a poly-proline, a carboxylic anhydride component and a diamine component, wherein the carboxylic anhydride component and the diamine component At least one of the structure is different from the structure of the carboxylic anhydride component and the diamine component used to form the polyamic acid; (5) a polyimine, a carboxylic anhydride component and a diamine component, wherein the carboxylic anhydride group At least one of the diamine component and the carboxylic anhydride component used in forming the polyimine are different from the structure of the diamine component; (6) poly-proline, polyimine, and carboxylic anhydride components And a diamine component, wherein at least one of the carboxylic anhydride component and the diamine component is different from the structure of the carboxylic anhydride component and the diamine component used to form the polyamic acid or the polyimine; 7) Two different structures a poly-proline, a carboxylic anhydride component and a diamine component; (8) two structurally different polyimine, a carboxylic anhydride component and a diamine component; (9) the two terminal groups are anhydride groups and a structurally different poly-proline and a diamine component; (10) a poly-proline and a carboxylic anhydride component having two terminal groups which are amine groups and different in structure; (11) the two terminal groups are anhydride groups and a structurally different polyimine and a diamine component; or (12) a polyimine and a carboxylic anhydride component in which the terminal groups are amine groups and structurally different.

在不影響本發明的功效的範圍內，聚醯胺酸、聚醯亞胺以及聚醯亞胺系嵌段共聚合物較佳為先進行分子量調節後的末端修飾型聚合物。藉由使用末端修飾型的聚合物，可改善液晶配向劑的塗佈性能。製備末端修飾型聚合物的方式可藉由在聚醯胺酸進行聚縮合反應的同時，加入單官能性化合物來製得。 The polyproline, the polyimine, and the polyimide block copolymer are preferably end-modified polymers having a molecular weight adjusted first, within a range that does not impair the efficacy of the present invention. The coating property of the liquid crystal alignment agent can be improved by using a terminal-modified polymer. The manner of preparing the terminal-modified polymer can be obtained by adding a monofunctional compound while carrying out a polycondensation reaction of poly-proline.

單官能性化合物的具體例包括但不限於(1)一元酸酐，例如：馬來酸酐、鄰苯二甲酸酐、衣康酸酐、正癸基琥珀酸酐、正十二烷基琥珀酸酐、正十四烷基琥珀酸酐或正十六烷基琥珀酸酐等一元酸酐；(2)單胺化合物，例如：苯胺、環己胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、正十一烷胺、正十二烷胺、正十三烷胺、正十四烷胺、正十五烷胺、正十六烷胺、正十七烷胺、正十八烷胺或正二十烷胺等單胺化合物；或(3)單異氰酸酯化合物，例如：異氰酸苯酯或異氰酸萘基酯等單異氰酸酯化合物。 Specific examples of the monofunctional compound include, but are not limited to, (1) a monobasic acid anhydride such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, ortho-fourth a monobasic anhydride such as an alkyl succinic anhydride or n-hexadecyl succinic anhydride; (2) a monoamine compound such as aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, N-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, A monoamine compound such as n-octadecylamine or n-icosylamine; or (3) a monoisocyanate compound such as a monoisocyanate compound such as phenyl isocyanate or naphthyl isocyanate.

溶劑(B)Solvent (B)

本發明的液晶配向劑中所使用的溶劑並無特別的限制，只要是可溶解聚合物(A)與其他任意成份且並不與其產生反應即可，較佳為同前述合成聚醯胺酸中所使用的溶劑，同時，亦可併用合成該聚醯胺酸時所使用的貧溶劑。 The solvent to be used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can dissolve the polymer (A) and other optional components and does not react therewith, and is preferably the same as the above-mentioned synthetic polylysine. The solvent to be used may be used in combination with the poor solvent used in the synthesis of the polyamic acid.

溶劑(B)的具體例包括但不限於N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone，NMP)、γ-丁內酯、γ-丁內醯胺、4-羥基-4-甲基-2-戊酮、乙二醇單甲基醚、乳酸丁酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乙二醇甲基醚、乙二醇乙基醚、乙二醇正丙基醚、乙二醇異丙基醚、乙二醇正丁基醚(ethylene glycol n-butyl ether)、乙二醇二甲基醚、乙二醇乙基醚乙酸酯、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯或N,N-二甲基甲醯胺或N,N-二甲基乙醯胺(N,N-dimethyl acetamide)等。溶劑(B)可以單獨使用或者組合多種來使用。 Specific examples of the solvent (B) include, but are not limited to, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4- Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol Ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate Ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate or N,N-dimethylformamide or N,N-dimethylacetamide or the like. The solvent (B) may be used singly or in combination of two or more.

基於聚合物(A)的使用量為100重量份，溶劑(B)的使用量為800至4000重量份，較佳為900至3500重量份，且更佳為1000至3000重量份。 The solvent (B) is used in an amount of 800 to 4000 parts by weight, preferably 900 to 3500 parts by weight, and more preferably 1,000 to 3,000 parts by weight, based on 100 parts by weight of the polymer (A).

添加劑(C)Additive (C)

在不影響本發明的功效的範圍內，液晶配向劑還可選擇性地添加添加劑(C)，其中添加劑(C)包括具有至少兩個環氧 基的化合物、具有官能性基團的矽烷化合物，或其組合。 The liquid crystal alignment agent may also optionally add the additive (C), wherein the additive (C) includes at least two epoxy resins, within a range not affecting the efficacy of the present invention. a compound of a group, a decane compound having a functional group, or a combination thereof.

具有至少兩個環氧基的化合物包括但不限於乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、三丙二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、新戊二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、丙三醇二環氧丙基醚、2,2-二溴新戊二醇二環氧丙基醚、1,3,5,6-四環氧丙基-2,4-己二醇、N,N,N’,N’-四環氧丙基-間-二甲苯二胺、1,3-雙(N,N-二環氧丙基胺基甲基)環己烷、N,N,N’,N’-四環氧丙基-4,4’-二胺基二苯基甲烷、N,N-環氧丙基-對-環氧丙氧基苯胺、3-(N-烯丙基-N-環氧丙基)胺基丙基三甲氧基矽烷、3-(N,N-二環氧丙基)胺基丙基三甲氧基矽烷，或上述化合物的組合。 Compounds having at least two epoxy groups include, but are not limited to, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether , polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, 2,2-di Bromo neopentyl glycol diepoxypropyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxypropyl- M-xylylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4 '-Diaminodiphenylmethane, N,N-epoxypropyl-p-glycidoxyaniline, 3-(N-allyl-N-epoxypropyl)aminopropyltrimethoxy A decyl, 3-(N,N-diepoxypropyl)aminopropyltrimethoxydecane, or a combination of the above.

上述具有至少兩個環氧基的化合物可單獨使用或組合多種來使用。 The above compounds having at least two epoxy groups may be used singly or in combination of two or more.

基於聚合物(A)的使用量為100重量份，具有至少兩個環氧基的化合物的使用量可為0至40重量份，且較佳為0.1重量份至30重量份。 The compound having at least two epoxy groups may be used in an amount of from 0 to 40 parts by weight, and preferably from 0.1 part by weight to 30 parts by weight, based on 100 parts by weight of the polymer (A).

具有官能性基團的矽烷化合物的具體例包括但不限於3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷(3-ureidopropyltrimethoxy silane)、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三 甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽烷基丙基三伸乙三胺、N-三甲氧基矽烷基丙基三伸乙三胺、10-三甲氧基矽烷基-1,4,7-三吖癸烷、10-三乙氧基矽烷基-1,4,7-三吖癸烷、9-三甲氧基矽烷基-3,6-二吖壬基醋酸酯、9-三乙氧基矽烷基-3,6-二吖壬基醋酸酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧化乙烯)-3-胺基丙基三甲氧基矽烷、N-雙(氧化乙烯)-3-胺基丙基三乙氧基矽烷，或上述化合物的組合。 Specific examples of the decane compound having a functional group include, but are not limited to, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2 -Aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, 3-ureidopropyltrimethoxy silane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyl three Methoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriamine, N-trimethoxydecylpropyltri Ethylenetriamine, 10-trimethoxydecyl-1,4,7-trioxane, 10-triethoxydecyl-1,4,7-trioxane, 9-trimethoxydecane Base-3,6-dimercaptoacetate, 9-triethoxydecyl-3,6-dimercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-Benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane N-bis(ethylene oxide)-3-aminopropyltrimethoxydecane, N-bis(ethylene oxide)-3-aminopropyltriethoxydecane, or a combination of the above compounds.

添加劑(C)可以單獨使用或組合多種來使用。 The additive (C) may be used singly or in combination of two or more.

基於聚合物(A)的使用量為100重量份，具有官能性基團的矽烷化合物的使用量可為0至10重量份，且較佳為0.5重量份至10重量份。 The decane compound having a functional group may be used in an amount of from 0 to 10 parts by weight, and preferably from 0.5 part by weight to 10 parts by weight, based on 100 parts by weight of the polymer (A).

基於聚合物(A)的總使用量為100重量份，添加劑(C)的使用量較佳為0.5重量份至50重量份，且更佳為1重量份至45重量份。 The additive (C) is preferably used in an amount of from 0.5 part by weight to 50 parts by weight, based on the total amount of the polymer (A) used, and more preferably from 1 part by weight to 45 parts by weight.

<液晶配向劑的製備方法><Preparation method of liquid crystal alignment agent>

本發明的液晶配向劑的製備方法並無特別的限制，可採用一般的混合方法來製備。舉例而言，先將以上述方式製備而成的聚合物(A)於溫度為0℃至200℃的條件下添加溶劑(B)，並選擇性地加入添加劑(C)，最後以攪拌裝置持續攪拌至溶解即可。 另外，較佳的是於20℃至60℃的溫度下添加溶劑(B)。 The preparation method of the liquid crystal alignment agent of the present invention is not particularly limited, and it can be produced by a general mixing method. For example, the polymer (A) prepared in the above manner is first added with a solvent (B) at a temperature of 0 ° C to 200 ° C, and optionally added with an additive (C), and finally with a stirring device. Stir until dissolved. Further, it is preferred to add the solvent (B) at a temperature of from 20 ° C to 60 ° C.

<液晶配向膜的形成方法><Method of Forming Liquid Crystal Alignment Film>

本發明的液晶配向膜的形成方法包含下列步驟：首先，利用輥塗佈法、旋轉塗佈法、印刷法、噴墨法(ink-jet)等方法，將上述製得的液晶配向劑塗佈在基板的表面上，以形成預塗層；接著，使該預塗層經受預烤處理(pre-bake treatment)、後烤處理(post-bake treatment)以及配向處理(alignment treatment)。 The method for forming a liquid crystal alignment film of the present invention comprises the steps of first coating a liquid crystal alignment agent prepared by a roll coating method, a spin coating method, a printing method, an inkjet method, or the like. A precoat layer is formed on the surface of the substrate; then, the precoat layer is subjected to a pre-bake treatment, a post-bake treatment, and an alignment treatment.

預烤處理的目的在於使該預塗層中的有機溶劑揮發。該預烤處理的操作溫度通常為30℃至120℃，較佳為40℃至110℃，更佳為50℃至100℃。預烤處理可於0.1分鐘至30分鐘的任意時間內進行，較佳為進行0.5分鐘至15分鐘，更佳為進行1分鐘至5分鐘。預烤處理可藉由一般公知方法，例如可以加熱板、烘箱、熱風循環爐或紅外線爐進行加熱。 The purpose of the pre-baking treatment is to volatilize the organic solvent in the precoat layer. The prebaking treatment is usually carried out at a temperature of from 30 ° C to 120 ° C, preferably from 40 ° C to 110 ° C, more preferably from 50 ° C to 100 ° C. The pre-baking treatment can be carried out at any time from 0.1 minutes to 30 minutes, preferably from 0.5 minutes to 15 minutes, more preferably from 1 minute to 5 minutes. The pre-baking treatment can be carried out by a generally known method such as heating in a hot plate, an oven, a hot air circulating furnace or an infrared furnace.

後烤處理的目的在於使該預塗層中的聚合物再進一步進行脫水閉環(醯亞胺化)反應。後烤處理的操作溫度範圍通常為150℃至300℃，較佳為180℃至280℃，更佳為200℃至250℃。後烤處理可於5分鐘至240分鐘的任意時間內進行，較佳為進行10分鐘至100分鐘，更佳為進行20分鐘至90分鐘。後烤處理可以與上述預烤處理相同的方法來進行。 The purpose of the post-baking treatment is to further subject the polymer in the precoat layer to a dehydration ring-closing (deuteration) reaction. The operating temperature range of the post-baking treatment is usually from 150 ° C to 300 ° C, preferably from 180 ° C to 280 ° C, more preferably from 200 ° C to 250 ° C. The post-baking treatment can be carried out at any time from 5 minutes to 240 minutes, preferably from 10 minutes to 100 minutes, more preferably from 20 minutes to 90 minutes. The post-baking treatment can be carried out in the same manner as the above-described pre-baking treatment.

配向處理並無特別的限制，例如可採用尼龍、人造絲、棉類等纖維所製成的布料纏繞在滾筒上，並以一定方向摩擦 (rubbing)進行配向。上述配向處理為本技術領域者所周知，在此不另贅述。 The alignment treatment is not particularly limited. For example, a fabric made of fibers such as nylon, rayon, or cotton may be wound around the drum and rubbed in a certain direction. (rubbing) to perform the alignment. The alignment processing described above is well known to those skilled in the art and will not be further described herein.

<液晶顯示元件及其製造方法><Liquid crystal display element and method of manufacturing the same>

本發明的液晶顯示元件包括由本發明的液晶配向劑所形成的液晶配向膜。 The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention.

本發明的液晶顯示元件可以如下述方法製造。 The liquid crystal display element of the present invention can be produced by the following method.

準備兩片如上述形成了液晶配向膜的基板，並在這兩片基板間配置液晶，並製造液晶胞。為了製造液晶胞(cell)，可以列舉例如以下兩種方法。 Two sheets of the substrate on which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal was placed between the two substrates to produce a liquid crystal cell. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

第一種方法：首先，將兩片基板隔著間隙(胞間隙)相對配置，使各自的液晶配向膜相對向；使用密封劑將兩片基板的周邊部位貼合在一起；向由基板表面和密封劑所劃分的胞間隙內注入填充液晶；並且封閉注入孔，如此可以製造液晶胞。 The first method: first, the two substrates are arranged opposite each other with a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other; the peripheral portions of the two substrates are bonded together by using a sealant; The filling liquid crystal is injected into the cell gap divided by the sealant; and the injection hole is closed, so that the liquid crystal cell can be manufactured.

第二種方法：被稱作為滴注(One Drop Fill，ODF)方式的方法。首先，在形成液晶配向膜的兩片基板中的一片基板上的規定部位，塗布例如紫外線固化性密封材料；在液晶配向膜面上滴下液晶；然後，貼合另一片基板，使液晶配向膜相對向；接著，對基板整面照射紫外線，以使密封劑固化，藉此可以製造液晶胞。 The second method: a method called the One Drop Fill (ODF) method. First, for example, an ultraviolet curable sealing material is applied to a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface; then, the other substrate is bonded to make the liquid crystal alignment film relatively Then, the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealant, whereby the liquid crystal cell can be produced.

在採用上述任一方法的情況下，都希望接著將液晶胞加熱至所用液晶呈各向同性相的溫度後，緩慢冷卻至室溫，藉此除去填充液晶時的流動配向。 In the case of any of the above methods, it is desirable to subsequently heat the liquid crystal cell to a temperature at which the liquid crystal used is in an isotropic phase, and then slowly cool to room temperature, thereby removing the flow alignment when the liquid crystal is filled.

然後，通過在液晶胞的外側表面上貼合偏光板(polarizer)，由此可以得到本發明的液晶顯示元件。 Then, a liquid crystal display element of the present invention can be obtained by laminating a polarizer on the outer surface of the liquid crystal cell.

密封劑例如可使用含有固化劑和作為間隔物(spacer)的氧化鋁球的環氧樹脂等。 As the sealant, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer or the like can be used.

液晶胞外側使用的偏光板可以列舉用乙酸纖維素(cellulose acetate)保護膜夾住使聚乙烯醇(polyvinyl alcohol)拉伸配向的同時吸收碘所得的稱作為「H膜」的偏光膜(polarizing film)而形成的偏光板或者H膜自身所形成的偏光板。 The polarizing plate used for the outer side of the liquid crystal cell is a polarizing film called "H film" obtained by sandwiching a polyvinyl acetate (vinyl acetate) protective film while absorbing iodine. a polarizing plate formed by the polarizing plate or the H film itself.

圖1是根據本發明一實施例的液晶顯示元件的側視圖。液晶顯示元件100包括第一單元110、第二單元120及液晶單元130，其中第二單元120與第一單元110分離配置，且液晶單元130設置在第一單元110與第二單元120之間。 1 is a side view of a liquid crystal display element in accordance with an embodiment of the present invention. The liquid crystal display element 100 includes a first unit 110, a second unit 120, and a liquid crystal unit 130, wherein the second unit 120 is disposed separately from the first unit 110, and the liquid crystal unit 130 is disposed between the first unit 110 and the second unit 120.

第一單元110包括第一基板112、第一導電膜114及第一液晶配向膜116，其中第一導電膜114形成在第一基板112的表面。另外，第一導電膜114位於第一基板112與第一液晶配向膜116之間，並且第一液晶配向膜116位於液晶單元130的一側。 The first unit 110 includes a first substrate 112, a first conductive film 114, and a first liquid crystal alignment film 116, wherein the first conductive film 114 is formed on a surface of the first substrate 112. In addition, the first conductive film 114 is located between the first substrate 112 and the first liquid crystal alignment film 116 , and the first liquid crystal alignment film 116 is located at one side of the liquid crystal cell 130 .

第二單元120包括第二基板122、第二導電膜124及第二液晶配向膜126，其中第二導電膜124形成在第二基板122的表面。另外，第二導電膜124位於第二基板122與第二液晶配向膜126之間，並且第二液晶配向膜126位於液晶單元130的另一側。換言之，液晶單元130是位於第一液晶配向膜116與第二液晶配向膜126之間。 The second unit 120 includes a second substrate 122, a second conductive film 124, and a second liquid crystal alignment film 126, wherein the second conductive film 124 is formed on the surface of the second substrate 122. In addition, the second conductive film 124 is located between the second substrate 122 and the second liquid crystal alignment film 126, and the second liquid crystal alignment film 126 is located on the other side of the liquid crystal cell 130. In other words, the liquid crystal cell 130 is located between the first liquid crystal alignment film 116 and the second liquid crystal alignment film 126.

第一基板112與第二基板122是選自於透明材料等，其中，透明材料包括但不限於用於液晶顯示裝置的無鹼玻璃、鈉鈣玻璃、硬質玻璃(派勒斯玻璃)、石英玻璃、聚乙烯對苯二甲酸酯、聚丁烯對苯二甲酸酯、聚醚碸或聚碳酸酯等。 The first substrate 112 and the second substrate 122 are selected from a transparent material or the like, and the transparent material includes, but is not limited to, an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), a quartz glass for a liquid crystal display device. , polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate.

第一導電膜114與第二導電膜124的材質是擇自於氧化錫(SnO2)、氧化銦-氧化錫(In2O3-SnO2)等。 The material of the first conductive film 114 and the second conductive film 124 is selected from tin oxide (SnO 2 ), indium oxide-tin oxide (In 2 O 3 -SnO 2 ), or the like.

第一液晶配向膜116及第二液晶配向膜126各自為上述的液晶配向膜，其作用在於使液晶單元130形成預傾角。此外，當施予第一導電膜114與第二導電膜124電壓時，第一導電膜114與第二導電膜124之間可產生電場。此電場可驅動液晶單元130，進而使液晶單元130中的液晶分子的排列發生改變。 Each of the first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 is the liquid crystal alignment film described above, and functions to form the liquid crystal cell 130 to have a pretilt angle. In addition, when the voltages of the first conductive film 114 and the second conductive film 124 are applied, an electric field can be generated between the first conductive film 114 and the second conductive film 124. This electric field can drive the liquid crystal cell 130, thereby changing the alignment of the liquid crystal molecules in the liquid crystal cell 130.

液晶單元130所使用的液晶可單獨使用或混合使用，液晶包括但不限於二胺基苯類液晶、噠嗪(pyridazine)類液晶、希夫氏鹼(shiff Base)類液晶、氧化偶氮基(azoxy)類液晶、聯苯(biphenyl)類液晶、苯基環己烷(phenylcyclohexane)類液晶、酯(ester)類液晶、三聯苯(terphenyl)、聯苯環己烷(biphenylcyclohexane)類液晶、嘧啶(pyrimidine)類液晶、二氧六環(dioxane)類液晶、雙環辛烷(bicyclooctane)類液晶或立方烷(cubane)類液晶等，且可視需求再添加例如是氯化膽固醇(cholesteryl chloride)、膽固醇壬酸酯(cholesteryl nonanoate)、膽固醇碳酸酯(cholesteryl carbonate)等的膽固醇型液晶、或是以商品名「C-15」、「CB-15」(默克公司製造)的對掌(chiral)劑等， 或者是對癸氧基苯亞甲基-對胺基-2-甲基丁基肉桂酸酯等強介電性(ferroelectric)類液晶。 The liquid crystal used in the liquid crystal cell 130 may be used singly or in combination, and the liquid crystal includes, but not limited to, a diamino benzene liquid crystal, a pyridazine liquid crystal, a shiff base liquid crystal, an azo group ( Azoxy) liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl, biphenylcyclohexane liquid crystal, pyrimidine ( Pyrimidine) liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal or cubane liquid crystal, etc., and further added, for example, cholesteryl chloride, cholesterol 可视A cholesteric liquid crystal such as cholesteryl nonanoate or cholesteryl carbonate, or a chiral agent such as "C-15" or "CB-15" (manufactured by Merck). , Alternatively, it is a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate.

聚合物(A)的合成例Synthesis example of polymer (A)

以下說明聚合物(A)的合成例A-1-1至合成例A-1-5、合成例A-2-1至合成例A-2-10以及比較合成例A-3-1至比較合成例A-3-6： The synthesis examples A-1-1 to Synthesis A-1-5, Synthesis Example A-2-1 to Synthesis Example A-2-10, and Comparative Synthesis Example A-3-1 of the polymer (A) are described below. Synthesis Example A-3-6:

合成例A-1-1Synthesis Example A-1-1

在容積500毫升的四頸燒瓶上設置氮氣入口、攪拌器、冷凝管及溫度計，並導入氮氣。然後，在四頸燒瓶中，加入1.41克(0.005莫耳)的由式(2-2)表示的二胺化合物(簡稱為b-1-1)、8.92克(0.045莫耳)的4,4’-二胺基二苯基甲烷(簡稱為b-2-1)以及80克的N-甲基-2-吡酪烷酮(簡稱為NMP)，並於室溫下攪拌至溶解。接著，加入41.03克(0.01莫耳)的乙二醇雙(偏苯三酸酐)(簡稱為a-1-1)、8.96克(0.04莫耳)的2,3,5-三羧基環戊基醋酸二酐(簡稱為a-2-1)及20克的NMP，並於室溫下反應2小時。待反應結束後，將反應溶液倒入1500毫升水中，以使聚合物析出。然後，過濾所得的聚合物，並重複以甲醇清洗及過濾三次，置入真空烘箱中，以溫度60℃進行乾燥後，即可得聚合物(A-1-1)。 A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed in a 500-mL four-necked flask, and nitrogen gas was introduced. Then, in a four-necked flask, 1.41 g (0.005 mol) of a diamine compound represented by the formula (2-2) (abbreviated as b-1-1) and 8.92 g (0.045 mol) of 4, 4 were added. '-Diaminodiphenylmethane (abbreviated as b-2-1) and 80 g of N-methyl-2-pyrrolidone (abbreviated as NMP) and stirred until dissolved at room temperature. Next, 41.03 g (0.01 mol) of ethylene glycol bis(trimellitic anhydride) (abbreviated as a-1-1) and 8.96 g (0.04 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride were added. (abbreviated as a-2-1) and 20 g of NMP, and reacted at room temperature for 2 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, washed repeatedly with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer (A-1-1).

合成例A-1-2至合成例A-1-5Synthesis Example A-1-2 to Synthesis Example A-1-5

合成例A-1-2至合成例A-1-5是以與合成例A-1-1相同的步驟來分別製備聚合物(A-1-2)至聚合物(A-1-5)，並且其不同處在於：改變單體的種類及其使用量(如表1所示)。 Synthesis Example A-1-2 to Synthesis Example A-1-5 were prepared in the same manner as in Synthesis Example A-1-1, respectively, to prepare a polymer (A-1-2) to a polymer (A-1-5). And the difference is: change the type of monomer and its use (as shown in Table 1).

合成例A-2-1Synthesis Example A-2-1

在容積500毫升的四頸燒瓶上設置氮氣入口、攪拌器、冷凝管及溫度計，並導入氮氣。然後，在四頸燒瓶中，加入1.41克(0.005莫耳)的由式(2-2)表示的二胺化合物(簡稱為b-1-1)、8.92克(0.045莫耳)的4,4’-二胺基二苯基甲烷(簡稱為b-2-1)以及80克的N-甲基-2-吡酪烷酮(簡稱為NMP)，並於室溫下攪拌至溶解。接著，加入41.03克(0.01莫耳)的乙二醇雙(偏苯三酸酐)(簡稱為a-1-1)、8.96克(0.04莫耳)的2,3,5-三羧基環戊基醋酸二酐(簡稱為a-2-1)及20克的NMP。於室溫下反應6小時後，加入97克的NMP、2.55克的醋酸酐及19.75克的吡啶，升溫至60℃，且持續攪拌2小時，以進行醯亞胺化反應。待反應結束後，將反應溶液倒入1500毫升水中，以使聚合物析出。然後，過濾所得的聚合物，並重複以甲醇清洗及過濾三次，置入真空烘箱中，以溫度60℃進行乾燥後，即可得聚合物(A-2-1)。 A nitrogen inlet, a stirrer, a condenser, and a thermometer were placed in a 500-mL four-necked flask, and nitrogen gas was introduced. Then, in a four-necked flask, 1.41 g (0.005 mol) of a diamine compound represented by the formula (2-2) (abbreviated as b-1-1) and 8.92 g (0.045 mol) of 4, 4 were added. '-Diaminodiphenylmethane (abbreviated as b-2-1) and 80 g of N-methyl-2-pyrrolidone (abbreviated as NMP) and stirred until dissolved at room temperature. Next, 41.03 g (0.01 mol) of ethylene glycol bis(trimellitic anhydride) (abbreviated as a-1-1) and 8.96 g (0.04 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride were added. (abbreviated as a-2-1) and 20 grams of NMP. After reacting at room temperature for 6 hours, 97 g of NMP, 2.55 g of acetic anhydride and 19.75 g of pyridine were added, the temperature was raised to 60 ° C, and stirring was continued for 2 hours to carry out the oxime imidization reaction. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, washed repeatedly with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60 ° C to obtain a polymer (A-2-1).

合成例A-2-2至合成例A-2-10Synthesis Example A-2-2 to Synthesis Example A-2-10

合成例A-2-2至合成例A-2-10是以與合成例A-2-1相同 的步驟來分別製備聚合物(A-2-2)至聚合物(A-2-10)，並且其不同處在於：改變單體的種類及其使用量(如表1所示)。 Synthesis Example A-2-2 to Synthesis Example A-2-10 are the same as Synthesis Example A-2-1 The procedure was to separately prepare the polymer (A-2-2) to the polymer (A-2-10), and the difference was that the kind of the monomer and the amount thereof were changed (as shown in Table 1).

比較合成例A-3-1至比較合成例A-3-3Comparative Synthesis Example A-3-1 to Comparative Synthesis Example A-3-3

比較合成例A-3-1至比較合成例A-3-3是以與合成例A-1-1相同的步驟來分別製備聚合物(A-3-1)至聚合物(A-3-3)，並且其不同處在於：改變單體的種類及其使用量(如表2所示)。 Comparative Synthesis Example A-3-1 to Comparative Synthesis Example A-3-3 The same procedure as in Synthesis Example A-1-1 was carried out to prepare a polymer (A-3-1) to a polymer (A-3-, respectively). 3), and the difference is: change the type of monomer and its use (as shown in Table 2).

比較合成例A-3-4至比較合成例A-3-6Comparative Synthesis Example A-3-4 to Comparative Synthesis Example A-3-6

比較合成例A-3-4至比較合成例A-3-6是以與合成例A-2-1相同的步驟來分別製備聚合物(A-3-4)至聚合物(A-3-6)，並且其不同處在於：改變單體的種類及其使用量(如表2所示)。 Comparative Synthesis Example A-3-4 to Comparative Synthesis Example A-3-6 The same procedure as in Synthesis Example A-2-1 was carried out to prepare a polymer (A-3-4) to a polymer (A-3-, respectively). 6), and the difference is: change the type of monomer and its use (as shown in Table 2).

表1及表2中簡稱所對應的化合物如下所示。 The compounds corresponding to the abbreviations in Tables 1 and 2 are as follows.

簡稱 成分 Abbreviation

a-1-1 乙二醇雙(偏苯三酸酐)(ethylene glycol-bis(trimellitic anhydride)) A-1-1 ethylene glycol-bis(trimellitic anhydride)

a-1-2 1,6-己二醇雙(偏苯三酸酐)(1,6-hexanediol-bis(trimellitic anhydride)) A-1-2 1,6-hexanediol-bis(trimellitic anhydride)

a-1-3 1,10-癸烷二醇雙(偏苯三酸酐)(1,10-decanediol-bis(trimellitic anhydride)) A-1-3 1,10-decanediol-bis(trimellitic anhydride)

a-1-4 1,20-二十烷二醇雙(偏苯三酸酐)(1,20-eicosanediol-bis(trimellitic anhydride)) A-1-4 1,20-eicosanediol bis(trimellitic anhydride)

a-2-1 2,3,5-三羧基環戊基醋酸二酐(2,3,5-tricarboxycyclopentylacetic acid dianhydride) A-2-1 2,3,5-tricarboxycyclopentylacetic acid dianhydride

a-2-2 1,2,3,4-環丁烷四羧酸二酐(1,2,3,4-cyclobutane tetracarboxylic dianhydride) A-2-2 1,2,3,4-cyclobutane tetracarboxylic dianhydride (1,2,3,4-cyclobutane tetracarboxylic dianhydride)

a-2-3 苯均四羧酸二酐(pyromellitic dianhydride) A-2-3 pyromellitic dianhydride

a-2-4 3,4-二羧基-1,2,3,4-四氫萘-1-琥珀酸二酐(3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride) A-2-4 3,4-Dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride (3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic Dianhydride)

b-2-1 4,4’-二胺基二苯基甲烷(4,4’-diaminodiphenylmethane) B-2-1 4,4'-diaminodiphenylmethane

b-2-2 對-二胺苯(p-diaminobezene) B-2-2 p-diaminobezene

b-2-3 1-十八烷氧基-2,4-二胺基苯(1-octadecoxy-2,4-diaminobenzene) B-2-3 1-octadecoxy-2,4-diaminobenzene

b-2-6 1,4-雙(4-胺基苯基)哌嗪(1,4-bis(4-amino-phenyl)piperazine) B-2-6 1,4-bis(4-aminophenyl) piperazine (1,4-bis(4-amino-phenyl)piperazine)

液晶配向劑及液晶配向膜的實施例與比較例Embodiments and Comparative Examples of Liquid Crystal Aligning Agent and Liquid Crystal Alignment Film

以下說明液晶配向劑及液晶配向膜的實施例1至實施例15以及比較例1至比較例6： Hereinafter, Examples 1 to 15 and Comparative Examples 1 to 6 of the liquid crystal alignment agent and the liquid crystal alignment film will be described:

實施例1 Example 1 a.液晶配向劑a. Liquid crystal alignment agent

秤取100重量份的聚合物(A-1-1)、1200重量份的N-甲 基-2-吡咯烷酮(簡稱為B-1)以及600重量份的乙二醇正丁基醚(簡稱為B-2)，並且在室溫下，以攪拌裝置持續攪拌至溶解，即可形成實施例1的液晶配向劑。 Weigh 100 parts by weight of polymer (A-1-1) and 1200 parts by weight of N-A Phen-2-pyrrolidone (abbreviated as B-1) and 600 parts by weight of ethylene glycol n-butyl ether (abbreviated as B-2), and continuously stirred to dissolve at room temperature with a stirring device to form an example 1 liquid crystal alignment agent.

b.液晶配向膜b. Liquid crystal alignment film

將上述液晶配向劑以印刷機(由日本寫真印刷株式會社製造，型號為S15-036)分別塗佈於兩片具有由ITO(indium tin oxide)構成的導電膜的玻璃基板，以形成預塗層。之後，將玻璃基板放置於加熱板上，並以溫度為100℃、時間為5分鐘的條件進行預烤。接著，在循環烘箱中，以溫度為220℃、時間為30分鐘的條件進行後烤。最後，經過配向處理後，即可獲得上面形成了實施例1的液晶配向膜的玻璃基板。 The liquid crystal alignment agent was applied to a glass substrate having a conductive film made of ITO (indium tin oxide) by a printing machine (manufactured by Nippon Photo Printing Co., Ltd., model No. S15-036) to form a precoat layer. . Thereafter, the glass substrate was placed on a hot plate, and prebaked at a temperature of 100 ° C for 5 minutes. Next, post-baking was carried out in a circulating oven at a temperature of 220 ° C for 30 minutes. Finally, after the alignment treatment, the glass substrate on which the liquid crystal alignment film of Example 1 was formed was obtained.

將實施例1的液晶配向膜以後述各評價方式進行評價，其結果如表3所示。 The liquid crystal alignment film of Example 1 was evaluated for each evaluation method described later, and the results are shown in Table 3.

實施例2至實施例15Embodiment 2 to Embodiment 15

實施例2至實施例15的液晶配向劑及液晶配向膜是以與實施例1相同的步驟分別製備，並且其不同處在於：改變成分的種類及其使用量，如表3所示。將實施例2至15所製得的液晶配向膜以後述評價方式進行評價，其結果如表3所示。 The liquid crystal alignment agent and the liquid crystal alignment film of Example 2 to Example 15 were separately prepared in the same manner as in Example 1, and were different in that the kind of the component and the amount thereof were changed, as shown in Table 3. The liquid crystal alignment films obtained in Examples 2 to 15 were evaluated in the evaluation methods described later, and the results are shown in Table 3.

比較例1至比較例6Comparative Example 1 to Comparative Example 6

比較例1至比較例6的液晶配向劑及液晶配向膜是以與實施例1相同的步驟分別製備，並且其不同處在於：改變成分的種類及其使用量，如表4所示。將比較例1至比較例6所製得的液晶配向膜以後述評價方式進行評價，其結果如表4所示。 The liquid crystal alignment agent and the liquid crystal alignment film of Comparative Example 1 to Comparative Example 6 were separately prepared in the same manner as in Example 1, and were different in that the kind of the component and the amount thereof were changed, as shown in Table 4. The liquid crystal alignment films obtained in Comparative Examples 1 to 6 were evaluated in the evaluation methods described later, and the results are shown in Table 4.

表3及表4中簡稱所對應的化合物如下所示。 The compounds corresponding to the abbreviations in Tables 3 and 4 are as follows.

簡稱 成分 Abbreviation

A-1-1 聚合物(A-1-1) A-1-1 polymer (A-1-1)

A-1-2 聚合物(A-1-2) A-1-2 Polymer (A-1-2)

A-1-3 聚合物(A-1-3) A-1-3 Polymer (A-1-3)

A-1-4 聚合物(A-1-4) A-1-4 polymer (A-1-4)

A-1-5 聚合物(A-1-5) A-1-5 polymer (A-1-5)

A-2-1 聚合物(A-2-1) A-2-1 polymer (A-2-1)

A-2-2 聚合物(A-2-2) A-2-2 polymer (A-2-2)

A-2-3 聚合物(A-2-3) A-2-3 polymer (A-2-3)

A-2-4 聚合物(A-2-4) A-2-4 polymer (A-2-4)

A-2-5 聚合物(A-2-5) A-2-5 polymer (A-2-5)

A-2-6 聚合物(A-2-6) A-2-6 polymer (A-2-6)

A-2-7 聚合物(A-2-7) A-2-7 polymer (A-2-7)

A-2-8 聚合物(A-2-8) A-2-8 polymer (A-2-8)

A-2-9 聚合物(A-2-9) A-2-9 polymer (A-2-9)

A-2-10 聚合物(A-2-10) A-2-10 polymer (A-2-10)

A-3-1 聚合物(A-2-1) A-3-1 polymer (A-2-1)

A-2-2 聚合物(A-2-2) A-2-2 polymer (A-2-2)

A-2-3 聚合物(A-2-3) A-2-3 polymer (A-2-3)

A-2-4 聚合物(A-2-4) A-2-4 polymer (A-2-4)

A-2-5 聚合物(A-2-5) A-2-5 polymer (A-2-5)

A-2-6 聚合物(A-2-6) A-2-6 polymer (A-2-6)

B-1 N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone) B-1 N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone)

B-2 乙二醇正丁基醚(ethylene glycol n-butyl ether) B-2 ethylene glycol n-butyl ether

B-3 γ-丁內酯(γ-butyrolactone) B-3 γ-butyrolactone (γ-butyrolactone)

C-1 N,N,N’,N’-四環氧丙基-4,4’-二胺基二苯基甲烷(N,N,N’,N’-tetraepoxypropyl-4,4’-diaminodiphenyl methane) C-1 N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane (N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenyl Methane)

C-2 N,N-環氧丙基-對-環氧丙氧基苯胺(N,N-epoxypropyl-p-glycidoxyaniline) C-2 N,N-epoxypropyl-p-glycidoxyaniline (N,N-epoxypropyl-p-glycidoxyaniline)

C-3 丙二醇二環氧丙基醚(propylene glycol diglycidyl ether) C-3 propylene glycol diglycidyl ether

<評價方式><Evaluation method> a.醯亞胺化率a. oxime imidization rate

醯亞胺化率是指透過聚合物中的醯胺酸官能基數目和醯亞胺環數目的合計量為基準，計算醯亞胺環數目所佔的比例，以百分率表示。 The ruthenium amination rate means the ratio of the number of ruthenium rings calculated as a percentage based on the total number of guanamine functional groups and the number of quinone rings in the polymer, expressed as a percentage.

檢測的方法是將合成例的聚合物分別進行減壓乾燥後，溶解於適當的氘化溶劑(deuteration solvent)，例如：氘化二甲基亞碸中，以四甲基矽烷作為基準物質，從室溫(例如25℃)下測定1H-核磁共振(1H-Nuclear magnetic resonance，1H-NMR)的結果，再由數學式(1)即可求得醯亞胺化率(%)。 The detection method is that the polymer of the synthesis example is dried under reduced pressure, and then dissolved in a suitable deuteration solvent, for example, deuterated dimethyl hydrazine, using tetramethyl decane as a reference material, 1 H-NMR measurement results (1 H-Nuclear magnetic resonance, 1 H-NMR) at room temperature (e.g. 25 ℃), then from equation (1) can be obtained (PEI) ratio (%).

△1：NH基質子在10ppm附近的化學位移(chemical shift)所產生的峰值(peak)面積；△2：其他質子的峰值面積；α：聚合物的前驅物(聚醯胺酸)中的NH基的1個質子相對於其他質子的個數比例。 Δ1: the peak area of the chemical shift of the NH proton near 10 ppm; Δ2: the peak area of other protons; α: the NH of the precursor of the polymer (polyproline) The ratio of the number of protons of a radical to the number of other protons.

b.框膠攤平性b. Frame rubber flatness

將框膠(型號WR723，協立化學製)分別塗佈於實施例及比較例的液晶配向膜上，並於10分鐘後使用50倍的顯微鏡觀察該框膠的收縮率。框膠攤平性的評價基準如下所示。收縮率越低，代表液晶配向膜的框膠攤平性越佳。 The sealant (Model WR723, manufactured by Kyoritsu Chemical Co., Ltd.) was applied to the liquid crystal alignment films of the examples and the comparative examples, respectively, and the shrinkage ratio of the sealant was observed using a 50-fold microscope after 10 minutes. The evaluation criteria for the flatness of the frame rubber are as follows. The lower the shrinkage ratio, the better the flatness of the sealant representing the liquid crystal alignment film.

◎：收縮率<10% ◎: Shrinkage rate <10%

○：10%≦收縮率<15% ○: 10% ≦ shrinkage rate <15%

△：5%≦收縮率<20% △: 5% ≦ shrinkage rate <20%

×：收縮率≧20% ×: shrinkage ≧ 20%

<評價結果><evaluation result>

由表3以及表4得知，與同時使用四羧酸二酐化合物(a-1)及二胺化合物(b-1)製備的聚合物(A)的液晶配向劑所製得的液晶配向膜(實施例1至實施例15)相比，比較例1至13的液晶配向膜有框膠攤平性不佳的問題。 From the Tables 3 and 4, the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the polymer (A) prepared by using the tetracarboxylic dianhydride compound (a-1) and the diamine compound (b-1) simultaneously. The liquid crystal alignment films of Comparative Examples 1 to 13 have a problem that the flatness of the sealant is not good as compared with (Example 1 to Example 15).

當使用由式(3)表示的二胺化合物(即聚合物(A-1-3)、聚合物(A-1-4)、聚合物(A-2-3)、聚合物(A-2-4)、聚合物(A-2-7)、聚合物(A-2-8)及聚合物(A-2-10))時(實施例3、4、8、9、12、13及15)，液晶配向膜的框膠攤平性更佳。 When a diamine compound represented by the formula (3) (i.e., polymer (A-1-3), polymer (A-1-4), polymer (A-2-3), polymer (A-2) is used -4), polymer (A-2-7), polymer (A-2-8) and polymer (A-2-10)) (Examples 3, 4, 8, 9, 12, 13 and 15), the sealing film of the liquid crystal alignment film is more flat.

另外，當醯亞胺化率為30%至90%的聚合物(A)(即聚合物(A-2-4)至聚合物(A-2-9))時(實施例9至實施例14)時，液晶配向膜的框膠攤平性更佳。 In addition, when the oxime imidization ratio is 30% to 90% of the polymer (A) (that is, the polymer (A-2-4) to the polymer (A-2-9)) (Examples 9 to 1) 14), the sealant of the liquid crystal alignment film is more flat.

綜上所述，本發明的液晶配向劑中，由含有特定四羧酸二酐化合物與特定二胺化合物的混合物所形成的聚合物，因此使用本發明的液晶配向劑所製造液晶配向膜的框膠攤平性佳，而可進一步提高後續加工製程的良率。 As described above, in the liquid crystal alignment agent of the present invention, a polymer comprising a mixture of a specific tetracarboxylic dianhydride compound and a specific diamine compound is used, and thus a frame of a liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention is used. The glue has good flatness and can further improve the yield of subsequent processing.

雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

100‧‧‧液晶顯示元件 100‧‧‧Liquid display components

110‧‧‧第一單元 110‧‧‧ first unit

112‧‧‧第一基板 112‧‧‧First substrate

114‧‧‧第一導電膜 114‧‧‧First conductive film

116‧‧‧第一液晶配向膜 116‧‧‧First liquid crystal alignment film

120‧‧‧第二單元 120‧‧‧Second unit

122‧‧‧第二基板 122‧‧‧second substrate

124‧‧‧第二導電膜 124‧‧‧Second conductive film

126‧‧‧第二液晶配向膜 126‧‧‧Second liquid crystal alignment film

130‧‧‧液晶單元 130‧‧‧Liquid Crystal Unit

Claims (6)

一種液晶配向劑，其包括：聚合物(A)，由包括四羧酸二酐組份(a)及二胺組份(b)的混合物反應而獲得；以及溶劑(B)，其中，所述四羧酸二酐組份(a)包括至少一種由式(1)表示的四羧酸二酐化合物(a-1)；所述二胺組份(b)包括至少一種由式(2)表示的二胺化合物(b-1)，其中，基於所述四羧酸二酐組份(a)的總使用量為100莫耳，所述四羧酸二酐化合物(a-1)的使用量為15至100莫耳； 式(1)中，a表示2至20的整數； 式(2)中，W1及W2各自獨立表示單鍵、-CO-、-COO-或-OCO-；Y1表示碳數為1至10的烷基、碳數為3至12的脂環族 基、碳數為6至12的芳香族基、羥基、鹵素原子、硝基或氰基，其中，所述烷基、所述脂環族基及所述芳香族基中的亞甲基可經氧原子、-CO-、-COO-或-OCO-取代，且所述亞甲基的氫原子可經至少1個鹵素原子取代；Y2及Y3各自獨立表示碳數為1至10的烷基、碳數為1至10的烷氧基或鹵素原子；b及c各自獨立表示大於等於1的整數，且b+c≧3；d表示0至5的整數；e及f各自獨立表示0至4的整數。 A liquid crystal alignment agent comprising: a polymer (A) obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a) and a diamine component (b); and a solvent (B), wherein The tetracarboxylic dianhydride component (a) includes at least one tetracarboxylic dianhydride compound (a-1) represented by the formula (1); the diamine component (b) includes at least one compound represented by the formula (2) The diamine compound (b-1), wherein the total amount of the tetracarboxylic dianhydride compound (a-1) used is 100 mol based on the total amount of the tetracarboxylic dianhydride component (a). 15 to 100 moles; In the formula (1), a represents an integer of 2 to 20; In the formula (2), W 1 and W 2 each independently represent a single bond, -CO-, -COO- or -OCO-; Y 1 represents an alkyl group having 1 to 10 carbon atoms and a fat having 3 to 12 carbon atoms. a cycloalkyl group, an aromatic group having 6 to 12 carbon atoms, a hydroxyl group, a halogen atom, a nitro group or a cyano group, wherein the alkyl group, the alicyclic group and the methylene group in the aromatic group It may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and the hydrogen atom of the methylene group may be substituted with at least one halogen atom; Y 2 and Y 3 each independently represent a carbon number of 1 to 10 The alkyl group, the alkoxy group having a carbon number of 1 to 10 or a halogen atom; b and c each independently represent an integer of 1 or more, and b+c≧3; d represents an integer of 0 to 5; and e and f are each independently An integer representing 0 to 4. 如專利申請範圍第1項所述的液晶配向劑，其中，基於所述二胺組份(b)的總使用量為100莫耳，所述二胺化合物(b-1)的使用量為5至80莫耳。 The liquid crystal alignment agent according to the above aspect of the invention, wherein the total amount of the diamine component (b) is 100 mol, and the diamine compound (b-1) is used in an amount of 5 To 80 moles. 如專利申請範圍第1項所述的液晶配向劑，其中，所述二胺化合物(b-1)包括由式(3)表示的二胺化合物， 式(3)中，W1及W2各自獨立表示單鍵、-CO-、-COO-或-OCO-；Y1表示碳數為1至10的烷基、碳數為3至12的脂環族基、碳數為6至12的芳香族基、羥基、鹵素原子、硝基或氰基，其中，所述烷基、所述脂環族基及所述芳香族基中的亞甲基可經氧原子、-CO-、-COO-或-OCO-取代，且所述亞甲基的氫原子可經至少1個鹵素原子取代；Y2及Y3各自獨立表示碳數為1至10的 烷基、碳數為1至10的烷氧基或鹵素原子；b及c各自獨立表示大於等於1的整數，且b+c≧3；d表示0至5的整數；e及f各自獨立表示0至4的整數。 The liquid crystal alignment agent according to the first aspect of the invention, wherein the diamine compound (b-1) comprises a diamine compound represented by the formula (3), In the formula (3), W 1 and W 2 each independently represent a single bond, -CO-, -COO- or -OCO-; Y 1 represents an alkyl group having 1 to 10 carbon atoms and a fat having 3 to 12 carbon atoms. a cycloalkyl group, an aromatic group having 6 to 12 carbon atoms, a hydroxyl group, a halogen atom, a nitro group or a cyano group, wherein the alkyl group, the alicyclic group and the methylene group in the aromatic group It may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and the hydrogen atom of the methylene group may be substituted with at least one halogen atom; Y 2 and Y 3 each independently represent a carbon number of 1 to 10 The alkyl group, the alkoxy group having a carbon number of 1 to 10 or a halogen atom; b and c each independently represent an integer of 1 or more, and b+c≧3; d represents an integer of 0 to 5; and e and f are each independently An integer representing 0 to 4. 如專利申請範圍第1項所述的液晶配向劑，其中，所述聚合物(A)的醯亞胺化率為30%至90%。 The liquid crystal alignment agent according to the above aspect of the invention, wherein the polymer (A) has a ruthenium azide ratio of 30% to 90%. 一種液晶配向膜，其是由如專利申請範圍第1項至第4項中任一項所述的液晶配向劑而形成。 A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of the first to fourth aspects of the invention. 一種液晶顯示元件，其包括如專利申請範圍第5項所述的液晶配向膜。 A liquid crystal display element comprising the liquid crystal alignment film according to item 5 of the patent application.
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