TW201300439A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent comprising a polyamic acid produced by the reaction of a diamine component with a tetracarboxylic acid dianhydride, wherein the diamine component contains 5 to 60 mol% of a diamine compound represented by formula (1) and 40 to 95 mol% of at least one diamine compound selected from the group consisting of p-phenylenediamine and diamine compounds having structures analogous to the structure of p-phenylenediamine. (In formula (1), X represents an oxygen atom or a sulfur atom; Y1 and Y2 independently represent a single bond, -O-, -S-, -OCO- or -COO-; and R1 and R2 independently represent an alkylene group having 1 to 3 carbon atoms.)

Description

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

本發明係有關液晶配向劑、液晶配向膜及液晶顯示元件。The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.

液晶顯示元件係作為顯示裝置現在被廣泛使用。液晶顯示元件之構成都材的液晶配向膜係使液晶均勻排列的膜，但是液晶配向性不足時，容易產生顯示不均或被稱為殘像的顯示不良。顯示不良之發生有時是因為液晶中之離子性雜質的影響，為了降低此雜質的方法，例如有如專利文獻1之提案。Liquid crystal display elements are now widely used as display devices. The liquid crystal alignment film of the constituent material of the liquid crystal display device is a film in which the liquid crystal is uniformly aligned. However, when the liquid crystal alignment property is insufficient, display unevenness or display failure called an afterimage is likely to occur. The occurrence of display failure is sometimes caused by the influence of ionic impurities in the liquid crystal, and a method for reducing the impurity is, for example, a proposal of Patent Document 1.

又，液晶配向膜一般係使用布擦拭高分子膜表面之摩擦進行配向處理。但是液晶配向膜之摩擦耐性不足時，膜被切削或產生傷痕或粉塵，或產生膜剝離，造成液晶顯示元件之顯示品位降低。因此，液晶配向膜被要求高的摩擦耐性，而提案如專利文獻2～5所示的方法。Further, the liquid crystal alignment film is generally subjected to an alignment treatment by rubbing the surface of the polymer film with a cloth. However, when the friction resistance of the liquid crystal alignment film is insufficient, the film is cut or scratched or dust is generated, or film peeling occurs, and the display quality of the liquid crystal display element is lowered. Therefore, the liquid crystal alignment film is required to have high friction resistance, and the methods shown in Patent Documents 2 to 5 are proposed.

為了得到高顯示品質的液晶顯示元件時，顯示高的亮度是很重要。因此，液晶配向膜也被要求具有更高的透過率。In order to obtain a liquid crystal display element of high display quality, it is important to display high brightness. Therefore, the liquid crystal alignment film is also required to have higher transmittance.

此外，液晶配向膜之體積電阻率較高時，有蓄積電荷不易緩和，殘像之消除費時的問題。為了縮短殘像消除的時間的方法，例如專利文獻6提案使用體積電阻率較低之液晶配向膜的方法。但是近年，關於殘像，不僅液晶配向膜之體積電阻率要低，且不會因光使體積電阻率變化也很重要。例如液晶顯示元件內之液晶配向膜中有配線或黑色聚陣等之存在，相較於其他部分，有時存在著不易受背光等光照射的部分。此時，液晶配向膜之體積電阻率因光而變化時，因受光的場所與未受光的場所，或光量不同的場所，而造成各自液晶配向膜之體積電阻率不同。因此，造成在液晶顯示元件內，存在著殘留DC容易蓄積的場所與不易蓄積的場所、或殘留DC容易緩和的場所與不易緩和的場所，結果造成可看見殘像或顯示不均等之顯示不良。Further, when the volume resistivity of the liquid crystal alignment film is high, there is a problem that the accumulated charge is not easily alleviated, and the afterimage is eliminated. In order to shorten the time of the afterimage removal, for example, Patent Document 6 proposes a method of using a liquid crystal alignment film having a low volume resistivity. However, in recent years, regarding the afterimage, not only the volume resistivity of the liquid crystal alignment film is low, but also the volume resistivity is not changed by light. For example, in the liquid crystal alignment film in the liquid crystal display device, there are wirings, black polyarrays, and the like, and portions which are less likely to be irradiated with light such as a backlight may be present in comparison with other portions. At this time, when the volume resistivity of the liquid crystal alignment film changes due to light, the volume resistivity of each liquid crystal alignment film is different depending on the place where the light is received, the place where the light is not received, or the place where the amount of light is different. Therefore, in the liquid crystal display element, there is a place where the residual DC is likely to be accumulated, a place where the residual DC is difficult to accumulate, a place where the residual DC is easily relaxed, and a place where the residual DC is not easily alleviated, and as a result, display defects such as residual images or display unevenness are observed.

[先行技術文獻][Advanced technical literature] [專利文獻][Patent Literature]

[專利文獻1]特開2002-323701號公報[Patent Document 1] JP-A-2002-323701

[專利文獻2]特開平7-120769號公報[Patent Document 2] Japanese Patent Publication No. 7-120769

[專利文獻3]特開平9-146100號公報[Patent Document 3] JP-A-9-146100

[專利文獻4]特開2008-90297號公報[Patent Document 4] JP-A-2008-90297

[專利文獻5]特開平9-258229號公報[Patent Document 5] JP-A-9-258229

[專利文獻6]國際公開第2004/053583號[Patent Document 6] International Publication No. 2004/053583

本發明係以提供兼備上述特性之液晶配向膜為目的而完成者。換言之，本發明之目的係提供一種顯示體積電阻率不易因光而變化之低體積電阻率，同時兼具良好的液晶配向性、良好的摩擦耐性、較少之離子密度特性、高的透過率的液晶配向膜。The present invention has been completed for the purpose of providing a liquid crystal alignment film having the above characteristics. In other words, the object of the present invention is to provide a low volume resistivity which exhibits a volume resistivity which is not easily changed by light, and which has good liquid crystal alignment, good friction resistance, less ion density characteristics, and high transmittance. Liquid crystal alignment film.

又，本發明之目的係提供可得到上述液晶配向膜的液晶配向劑。Further, an object of the present invention is to provide a liquid crystal alignment agent which can obtain the above liquid crystal alignment film.

本發明之目的係提供顯示品質優異之液晶顯示元件。An object of the present invention is to provide a liquid crystal display element excellent in display quality.

本發明之其他目的及優點係由下述記載可知。Other objects and advantages of the present invention will be apparent from the description below.

本發明之第1態樣係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸的液晶配向劑，其特徵係前述二胺成分係以式(1)表示之二胺化合物含有5~60莫耳%，選自式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物含有40~95莫耳%。The first aspect of the present invention is a liquid crystal alignment agent containing a polyamic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component, wherein the diamine component is a diamine compound represented by the formula (1). Containing 5 to 60 mol%, at least one diamine compound selected from the group consisting of diamine compounds represented by formula (2-1), formula (2-2) and formula (2-3) contains 40 to 95 mols %.

式(1)中，X係氧原子或硫原子，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-或-COO-，R¹及R²係各自獨立為碳數1~3之伸烷基。In the formula (1), the X-based oxygen atom or the sulfur atom, and the Y ¹ and Y ² systems are each independently a single bond, -O-, -S-, -OCO- or -COO-, and the R ¹ and R ² systems are each independently It is an alkyl group having a carbon number of 1 to 3.

本發明之第1態樣中，二胺成分較佳為含有20莫耳%以下之量之式(3)表示的二胺化合物。In the first aspect of the invention, the diamine component is preferably a diamine compound represented by the formula (3) in an amount of 20 mol% or less.

式(3)中，X¹係選自由-CONQ¹-、-O-、-NQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種2價有機基，Q¹係氫原子或碳數1~3之烷基，X²係選自碳數1~20之脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群之至少一種2價有機基或單鍵，X³係單鍵或選自由-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種2價有機基，Q²係氫原子或碳數1~3之烷基，X⁴係1價含氮芳香族雜環，n係1~4之整數。Of formula (3), X ¹ is selected from the group consisting of ^{-CONQ 1 -, - O -,} - NQ 1 -, - NQ 1 CO -, - CH 2 O- and -OCO- groups of the at least one divalent organic group , Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ² is at least one divalent organic group selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon groups, and aromatic hydrocarbon groups. group or a single bond, X ³ or selected from the group consisting of a single bond based ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH _{2) m} - ( m is an integer of 1 to 5) at least one divalent organic group in a group, Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ⁴ is a monovalent nitrogen-containing aromatic heterocyclic ring, and n is a 1~ An integer of 4.

本發明之第2態樣係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸的液晶配向劑，其特徵係前述二胺成分係以式(1)表示之二胺化合物含有40~70莫耳%，以式(4)表示之二胺化合物含有30莫耳%以上者。The second aspect of the present invention is a liquid crystal alignment agent containing a polyamic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component, wherein the diamine component is a diamine compound represented by the formula (1). It contains 40 to 70 mol%, and the diamine compound represented by the formula (4) contains 30 mol% or more.

式(1)中，X係氧原子或硫原子，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-或-COO-，R¹及R²係各自獨立為碳數1~3之伸烷基。In the formula (1), the X-based oxygen atom or the sulfur atom, and the Y ¹ and Y ² systems are each independently a single bond, -O-, -S-, -OCO- or -COO-, and the R ¹ and R ² systems are each independently It is an alkyl group having a carbon number of 1 to 3.

式(4)中，X⁵係具有碳數6~30之芳香族環的有機基，n係1~4之整數。In the formula (4), X ⁵ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.

本發明之第2態樣中，二胺成分較佳為含有20莫耳%以下之量之式(3)表示的二胺化合物。In the second aspect of the present invention, the diamine component is preferably a diamine compound represented by the formula (3) in an amount of 20 mol% or less.

式(3)中，X¹係選自由-CONQ¹-、-O-、-NQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種2價有機基，Q¹係氫原子或碳數1~3之烷基，X²係選自由碳數1~20之脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群之至少一種2價有機基或單鍵，X³係單鍵，或選自由-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種2價有機基，Q²係氫原子或碳數1~3之烷基，X⁴係1價含氮芳香族雜環，n係1~4之整數。Of formula (3), X ¹ is selected from the group consisting of ^{-CONQ 1 -, - O -,} - NQ 1 -, - NQ 1 CO -, - CH 2 O- and -OCO- groups of the at least one divalent organic group And Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ² is at least one divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. group or a single bond, X ³ system single bond, or selected from the group consisting of ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH _{2) m} - (m is an integer of 1 to 5) at least one divalent organic group, Q ² hydrogen atom or alkyl group having 1 to 3 carbon atoms, X ⁴ is a monovalent nitrogen-containing aromatic heterocyclic ring, and n is 1 An integer of ~4.

本發明之第3態樣係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸的液晶配向劑，其特徵係前述二胺成分係以式(1)表示之二胺化合物含有20~60莫耳%，及選自式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與式(4)表示之二胺化合物以95：5~40：60之莫耳比，含有合計40~80莫耳%者。The third aspect of the present invention is a liquid crystal alignment agent containing a polyamic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component, wherein the diamine component is a diamine compound represented by the formula (1). At least one diamine compound and a formula (4) containing 20 to 60 mol% and selected from the group consisting of diamine compounds represented by formula (2-1), formula (2-2) and formula (2-3) The diamine compound is represented by a molar ratio of 95:5 to 40:60, and contains 40 to 80 mol% in total.

式(1)中，X係氧原子或硫原子，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-或-COO-，R¹及R²係各自獨立為碳數1~3之伸烷基。In the formula (1), the X-based oxygen atom or the sulfur atom, and the Y ¹ and Y ² systems are each independently a single bond, -O-, -S-, -OCO- or -COO-, and the R ¹ and R ² systems are each independently It is an alkyl group having a carbon number of 1 to 3.

式(4)中，X⁵係具有碳數6~30之芳香族環的有機基，n係1~4之整數。In the formula (4), X ⁵ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.

本發明之第3態樣中，二胺成分較佳為含有20莫耳%以下之量之式(3)表示的二胺化合物。In the third aspect of the present invention, the diamine component is preferably a diamine compound represented by the formula (3) in an amount of 20 mol% or less.

式(3)中，X¹係選自由-CONQ¹-、-O-、-NQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種2價有機基，Q¹係氫原子或碳數1~3之烷基，X²係選自碳數1~20之脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群之至少一種2價有機基或單鍵，X³係單鍵或選自由-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種2價有機基，Q²係氫原子或碳數1~3之烷基，X⁴係1價含氮芳香族雜環，n係1~4之整數。Of formula (3), X ¹ is selected from the group consisting of ^{-CONQ 1 -, - O -,} - NQ 1 -, - NQ 1 CO -, - CH 2 O- and -OCO- groups of the at least one divalent organic group , Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ² is at least one divalent organic group selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon groups, and aromatic hydrocarbon groups. group or a single bond, X ³ or selected from the group consisting of a single bond based ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH _{2) m} - ( m is an integer of 1 to 5) at least one divalent organic group in a group, Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ⁴ is a monovalent nitrogen-containing aromatic heterocyclic ring, and n is a 1~ An integer of 4.

本發明之第4態樣係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸的液晶配向劑，其特徵係前述二胺成分係以式(1)表示之二胺化合物含有50莫耳%以上，及剩餘的成分為含有90：10~40：60之莫耳比之式(4)表示之二胺化合物與式(3)表示之二胺化合物。The fourth aspect of the present invention is a liquid crystal alignment agent containing a polyaminic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component, wherein the diamine component is a diamine compound represented by the formula (1). The diamine compound represented by the formula (4) and the diamine compound represented by the formula (3) are contained in an amount of 50 mol% or more, and the remaining component is a molar ratio of 90:10 to 40:60.

式(1)中，X係氧原子或硫原子，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-或-COO-，R¹及R²係各自獨立為碳數1~3之伸烷基。In the formula (1), the X-based oxygen atom or the sulfur atom, and the Y ¹ and Y ² systems are each independently a single bond, -O-, -S-, -OCO- or -COO-, and the R ¹ and R ² systems are each independently It is an alkyl group having a carbon number of 1 to 3.

式(4)中，X⁵係具有碳數6~30之芳香族環的有機基，n係1~4之整數。In the formula (4), X ⁵ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.

式(3)中，X¹係選自由-CONQ¹-、-O-、-NQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種2價有機基，Q¹係氫原子或碳數1~3之烷基，X²係選自碳數1~20之脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群之至少一種2價有機基或單鍵，X³係單鍵或選自由-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種2價有機基，Q²係氫原子或碳數1~3之烷基，X⁴係1價含氮芳香族雜環，n係1~4之整數。Of formula (3), X ¹ is selected from the group consisting of ^{-CONQ 1 -, - O -,} - NQ 1 -, - NQ 1 CO -, - CH 2 O- and -OCO- groups of the at least one divalent organic group , Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ² is at least one divalent organic group selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon groups, and aromatic hydrocarbon groups. group or a single bond, X ³ or selected from the group consisting of a single bond based ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH _{2) m} - ( m is an integer of 1 to 5) at least one divalent organic group in a group, Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ⁴ is a monovalent nitrogen-containing aromatic heterocyclic ring, and n is a 1~ An integer of 4.

本發明之第5態樣係一種液晶配向膜，其特徵係由本發明之第1~第4態樣之液晶配向劑所得者。The fifth aspect of the present invention is a liquid crystal alignment film characterized by being obtained from the liquid crystal alignment agents of the first to fourth aspects of the present invention.

本發明之第6態樣係一種液晶顯示元件，其特徵係具有本發明之第5態樣之液晶配向膜者。A sixth aspect of the invention is a liquid crystal display device characterized by having the liquid crystal alignment film of the fifth aspect of the invention.

依據本發明之第1~第4態樣時，可提供一種液晶配向劑，此液晶配向劑可得到具有對液晶之高的配向控制機能，同時可減低液晶顯示元件之殘像現象，此外可得到具備高的摩擦特性與高的透過率的液晶配向膜。According to the first to fourth aspects of the present invention, it is possible to provide a liquid crystal alignment agent which can have a high alignment control function for liquid crystals and at the same time reduce the afterimage of the liquid crystal display element, and further obtain A liquid crystal alignment film having high friction characteristics and high transmittance.

依據本發明之第5態樣時，可得到具有對液晶之高的配向控制機能，同時可減低液晶顯示元件之殘像現象，此外可得到具備高的摩擦特性與高的透過率的液晶配向膜。According to the fifth aspect of the present invention, it is possible to obtain a high alignment control function for liquid crystal, and at the same time, to reduce the afterimage phenomenon of the liquid crystal display element, and to obtain a liquid crystal alignment film having high friction characteristics and high transmittance. .

依據本發明之第6態樣時，可提供顯示品質優異之液晶顯示元件。According to the sixth aspect of the present invention, a liquid crystal display element excellent in display quality can be provided.

[實施發明的形態][Formation of the Invention]

本實施形態的液晶配向劑係含有使二胺成分與四羧酸二酐成分反應所得的聚醯胺酸。聚醯胺酸原料之二胺成分係含有下述式(1)表示之特定二胺(以下也稱為第1必須成分)與二胺化合物(以下也稱為第2必須成分)。第2必須成分之二胺化合物係選自由下述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與下述式(4)表示之二胺化合物，此等係各自獨立或併用來使用。The liquid crystal alignment agent of the present embodiment contains a polylysine obtained by reacting a diamine component with a tetracarboxylic dianhydride component. The diamine component of the polyaminic acid raw material contains a specific diamine (hereinafter also referred to as a first essential component) represented by the following formula (1) and a diamine compound (hereinafter also referred to as a second essential component). The diamine compound of the second essential component is at least one diamine compound selected from the group consisting of diamine compounds represented by the following formula (2-1), formula (2-2), and formula (2-3), and the following The diamine compound represented by the formula (4) is used independently or in combination.

又，二胺成分非必須，但是下述式(3)表示之二胺化合物可含有作為第3之二胺成分。此外，二胺成分除了下述式(1)、(2-1)~(2-3)、(3)、(4)表示之二胺化合物外，可含有另外的二胺化合物。Further, the diamine component is not essential, but the diamine compound represented by the following formula (3) may contain the diamine component as the third. Further, the diamine component may contain another diamine compound in addition to the diamine compound represented by the following formulas (1), (2-1) to (2-3), (3), and (4).

以下詳細說明二胺成分中作為必須成分而含有的二胺化合物與可含有之二胺化合物。Hereinafter, the diamine compound contained as an essential component in the diamine component and the diamine compound which may be contained are described in detail.

<特定二胺(1)><specific diamine (1)>

聚醯胺酸原料之二胺成分中，含有作為第1必須成分之特定二胺係以下式(1)表示。又，本說明書中，具有式(1)之構造的特定二胺有時以「特定二胺(1)」表示。Among the diamine components of the polyproline raw material, the specific diamine which is the first essential component is represented by the following formula (1). Further, in the present specification, the specific diamine having the structure of the formula (1) may be represented by "specific diamine (1)".

式(1)中，X係氧原子或硫原子，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-、或-COO-，R¹及R²係各自獨立為碳數1~3之伸烷基。式(1)中，X為氧原子時表示脲基，硫原子時表示硫脲基(以下有時脲基及硫脲基統稱為(硫)脲基)。氧原子與硫原子均為電負度高的原子。又，氮原子上存在著2個施予性高的氫原子。因此，(硫)脲基之氧或硫原子係因與其他之(硫)脲基之2個氫原子非共價鍵結，比較強的自行集合。本發明中，式(1)中之X較佳為氧原子。此乃是相較於氧原子與硫原子時，電負度係氧原子較高，因此脲構造比硫脲構造更容易進行較強的自行集合。In the formula (1), the X-based oxygen atom or the sulfur atom, and the Y ¹ and Y ² systems are each independently a single bond, -O-, -S-, -OCO-, or -COO-, and R ¹ and R ² are each independently Independently an alkylene group having a carbon number of 1 to 3. In the formula (1), when X is an oxygen atom, it means a urea group, and when it is a sulfur atom, it means a thiourea group (hereinafter, a urea group and a thiourea group are collectively referred to as a (thio)ureido group). Both the oxygen atom and the sulfur atom are atoms with a high electronegativity. Further, two highly hydrogen atoms are present on the nitrogen atom. Therefore, the oxygen or sulfur atom of the (thio)urea group is relatively non-covalently bonded to two hydrogen atoms of the other (thio)ureido group, and is relatively self-assembled. In the present invention, X in the formula (1) is preferably an oxygen atom. This is because when the oxygen atom and the sulfur atom are compared, the electronegativity oxygen atom is higher, so the urea structure is easier to carry out a stronger self-assembly than the thiourea structure.

本實施形態之液晶配向劑係在高分子鏈中，具有來自特定二胺(1)之(硫)脲基。因此，因(硫)脲基彼此之靜電相互作用，可提高摩擦耐性。關於此點，本發明係與在液晶配向膜領域一般使用之高分子鏈間以交聯劑連結，以提高摩擦耐的方法不同。式(1)中，R¹及R²係各自獨立表示碳數1~3之伸烷基，其構造可為直鏈或支鏈。具體例有亞甲基、伸乙基、伸丙基、1-甲基伸乙基、2-甲基伸乙基等。其中，從液晶之配向性與摩擦耐性的觀點，儘可能具有自由旋轉部位，立體障礙較小的構造為佳，具體而言，較佳為亞甲基、伸乙基、伸丙基。The liquid crystal alignment agent of the present embodiment has a (thio)ureido group derived from a specific diamine (1) in a polymer chain. Therefore, the friction resistance can be improved by the electrostatic interaction of the (thio)urea groups. In this regard, the present invention differs from a method in which a polymer chain generally used in the field of liquid crystal alignment films is connected by a crosslinking agent to improve friction resistance. In the formula (1), R ¹ and R ² each independently represent an alkylene group having 1 to 3 carbon atoms, and the structure thereof may be a straight chain or a branched chain. Specific examples are methylene, ethyl, propyl, 1-methylethyl, 2-methylethyl and the like. Among them, from the viewpoint of the alignment property of the liquid crystal and the friction resistance, it is preferable to have a freely rotating portion as much as possible, and a structure having a small steric hindrance is preferable. Specifically, a methylene group, an ethyl group, and a propyl group are preferable.

式(1)中，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-、或-COO-。Y¹及Y²之構造，從液晶之配向性與摩擦耐性的觀點，儘可能柔軟且立體障礙小的構造為佳，較佳為單鍵、-O-、或-S-。In the formula (1), each of Y ¹ and Y ² is independently a single bond, -O-, -S-, -OCO-, or -COO-. The structure of Y ¹ and Y ² is preferably as soft as possible and has a small steric hindrance from the viewpoint of the alignment property of the liquid crystal and the friction resistance, and is preferably a single bond, -O-, or -S-.

形成膜密度高的膜，形成更強固之液晶配向膜的觀點，(硫)脲基與苯環之間的構造較佳為以(硫)脲基為中心而對稱者，-R¹-Y¹-與-R²-Y²-較佳為相同構造。又，以式(1)表示之特定二胺之中，較佳為以下式(1-a)~式(1-c)表示之化合物。但是式(1-a)中，R¹¹及R²¹係碳數均為相等之碳數1~3之伸烷基。又，式(1-b)中，R¹²及R²²係彼此碳數不同的碳數1~3之伸烷基。式(1-c)中，R¹³及R²³係各自獨立為碳數1~3之伸烷基。From the viewpoint of forming a film having a high film density and forming a stronger liquid crystal alignment film, the structure between the (thio)ureido group and the benzene ring is preferably symmetrical with respect to the (thio)ureido group, -R ¹ -Y ¹ - preferably the same configuration as -R ² -Y ² -. Further, among the specific diamines represented by the formula (1), preferred are compounds represented by the following formulas (1-a) to (1-c). However, in the formula (1-a), R ¹¹ and R ²¹ each have an alkylene group having an equivalent carbon number of 1 to 3. Further, in the formula (1-b), R ¹² and R ²² are each a C 1 to 3 alkyl group having a carbon number different from each other. In the formula (1-c), each of R ¹³ and R ²³ is independently an alkylene group having 1 to 3 carbon atoms.

式(1)中，苯環上之胺基之鍵結位置無特別限定，從液晶之配向性的觀點，較佳為3-胺基苯基構造或4-胺基苯基構造，特佳為4-胺基苯基構造。例如式(1)較佳為下述式(1-1)、式(1-2)或式(1-3)中任一者，特佳為式(1-1)。又，式(1-1)、式(1-2)、及式(1-3)中，Y¹、Y²、R¹及R²係與式(1)之定義相同的定義。In the formula (1), the bonding position of the amine group on the benzene ring is not particularly limited, and from the viewpoint of the alignment property of the liquid crystal, a 3-aminophenyl structure or a 4-aminophenyl structure is preferred, and particularly preferably 4-aminophenyl structure. For example, the formula (1) is preferably any one of the following formula (1-1), formula (1-2) or formula (1-3), and particularly preferably the formula (1-1). Further, in the formulae (1-1), (1-2), and (1-3), Y ¹ , Y ² , R ¹ and R ² are the same definitions as defined in the formula (1).

式(1)之具體例為式(1-4)~式(1-15)表示之化合物。Specific examples of the formula (1) are compounds represented by the formula (1-4) to the formula (1-15).

式(1-7)~(1-11)之化合物係以往未知的化合物，因此使用此等化合物之聚醯胺酸也是以往未知的化合物。此外，式(1-7)~(1-11)以外之二胺化合物係已知的化合物，但是使用此等二胺化合物之聚醯胺酸係以往未知的化合物。本實施形態之液晶配向劑，特佳為使用係上述式(1-4)、(1-8)~式(1-11)表示之特定二胺作為聚醯胺酸原料之二胺成分。Since the compounds of the formulae (1-7) to (1-11) are compounds which are not known in the past, polyamines using these compounds are also conventionally unknown compounds. Further, the diamine compounds other than the formulae (1-7) to (1-11) are known compounds, but the polyamines using these diamine compounds are conventionally unknown compounds. In the liquid crystal alignment agent of the present embodiment, it is particularly preferable to use a specific diamine represented by the above formula (1-4), (1-8) to formula (1-11) as a diamine component of a polyglycine raw material.

<特定二胺之合成方法><Synthesis method of specific diamine>

以下敘述式(1)表示之特定二胺(1)之合成方法。The synthesis method of the specific diamine (1) represented by the formula (1) will be described below.

特定二胺(1)係藉由苯胺骨架、間隔部(R¹、R²)、連結基(Y¹、Y²)及(硫)脲基所構成，其合成方法無特別限定，例如可藉由下述方法合成。The specific diamine (1) is composed of an aniline skeleton, a spacer (R ¹ , R ² ), a linking group (Y ¹ , Y ² ), and a (thio)ureido group, and the synthesis method thereof is not particularly limited, and for example, It was synthesized by the following method.

式(1)表示之特定二胺係合成式(1A)表示之二硝基化合物，接著使硝基還原，轉化成胺基而得。式(1A)中，R¹、R²、Y¹、Y²及X係與式(1)的情形同義。The specific diamine represented by the formula (1) is a synthetic dinitro compound represented by the formula (1A), which is obtained by reducing a nitro group and converting it into an amine group. In the formula (1A), R ¹ , R ² , Y ¹ , Y ² and X are synonymous with the case of the formula (1).

使二硝基化合物還原的方法並無特別限制，通常為以鈀-碳、氧化鉑、阮尼鎳、鐵、氯化錫、鉑黑、銠-氧化鋁或硫化鉑碳等作為觸媒使用，於乙酸乙酯、甲苯、四氫呋喃、二噁烷或醇系等溶劑中，藉由使用氫氣、聯胺、氯化氫或氯化銨等之反應進行還原的方法。The method for reducing the dinitro compound is not particularly limited, and it is usually used as a catalyst using palladium-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, lanthanum-alumina or platinum sulfide carbon. A method of reducing by a reaction using hydrogen, hydrazine, hydrogen chloride or ammonium chloride in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol.

式(1)中，X係氧原子或硫原子，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-、或-COO-，R¹及R²係各自獨立為碳數1~3之伸烷基。又，苯環上之胺基之鍵結位置無特別限定。In the formula (1), the X-based oxygen atom or the sulfur atom, and the Y ¹ and Y ² systems are each independently a single bond, -O-, -S-, -OCO-, or -COO-, and R ¹ and R ² are each independently Independently an alkylene group having a carbon number of 1 to 3. Further, the bonding position of the amine group on the benzene ring is not particularly limited.

式(1A)表示之二硝基化合物之合成方法無特別限定，可使用任意的方法。例如有以下之圖解(I)所示之方法。The method for synthesizing the dinitro compound represented by the formula (1A) is not particularly limited, and any method can be used. For example, there is a method shown in the following diagram (I).

圖解(I)中，式(1A)表示之二硝基化合物係可藉由將硝基苯化合物(α)、(α’)與(硫)羰基化合物(羰基化合物與硫羰基化合物之總稱)(β)在有機溶劑中，鹼存在下進行反應而合成。In the scheme (I), the dinitro compound represented by the formula (1A) can be obtained by using a nitrobenzene compound (α), (α') and a (thio)carbonyl compound (general name of a carbonyl compound and a thiocarbonyl compound) ( β) is synthesized by reacting in an organic solvent in the presence of a base.

上述之硝基苯化合物(α)及(α’)中，R¹、R²、Y¹及Y²係與式(1)相同，NH₂表示之胺基也可形成鹽酸鹽(NH₂‧HCl)等的鹽。例如有硝基苄胺或其鹽酸鹽、2-(硝基苯基)乙胺或其鹽酸鹽、3-(硝基苯基)丙胺或其鹽酸鹽等。又，苯環上之硝基之取代位置可適當選擇可得到目的之二胺化合物之取代位置者。此處所示之化合物係一例，無特別限定。In the above nitrobenzene compounds (α) and (α'), R ¹ , R ² , Y ¹ and Y ² are the same as in the formula (1), and the amine group represented by NH ₂ can also form a hydrochloride (NH _{2 ).} ‧ HCl) and other salts. For example, there may be mentioned nitrobenzylamine or its hydrochloride, 2-(nitrophenyl)ethylamine or its hydrochloride, 3-(nitrophenyl)propylamine or its hydrochloride. Further, the position of substitution of the nitro group on the benzene ring can be appropriately selected to obtain the substitution position of the diamine compound of interest. The compound shown here is an example, and is not specifically limited.

(硫)羰基化合物(β)中，X係與式(1)相同，Z係1~2價有機基。(硫)羰基化合物(β)例如有光氣、硫光氣、二苯基碳酸酯、二苯基硫碳酸酯、雙(硝基苯基)碳酸酯、雙(硝基苯基)硫碳酸酯、二甲基碳酸酯、二甲基硫碳酸酯、二乙基碳酸酯、二乙基硫碳酸酯、伸乙基碳酸酯、伸乙基硫碳酸酯、1,1’-羰基雙-1H-咪唑或1,1’-硫羰基雙-1H-咪唑等。又，可使用碳氧化物(一氧化碳或二氧化碳)取代羰基化合物(β)。此處所示之化合物係一例，無特別限定。In the (thio)carbonyl compound (β), the X system is the same as the formula (1), and the Z system is a 1 to 2 valent organic group. The (thio)carbonyl compound (β) is, for example, phosgene, thiophosgene, diphenyl carbonate, diphenyl thiocarbonate, bis(nitrophenyl) carbonate, bis(nitrophenyl)thiocarbonate. , dimethyl carbonate, dimethyl thiocarbonate, diethyl carbonate, diethyl thiocarbonate, ethyl ethyl carbonate, ethyl thiocarbonate, 1,1 '-carbonyl bis-1H- Imidazole or 1,1'-thiocarbonyl bis-1H-imidazole. Further, a carbonyl compound (β) may be substituted with a carbon oxide (carbon monoxide or carbon dioxide). The compound shown here is an example, and is not specifically limited.

上述圖解(I)中，為了得到以(硫)脲基為中心，構造對稱之化合物時，使硝基苯化合物(α)及(α’)相同即可，為了得到非對稱之化合物時，使硝基苯化合物(α)相對於(硫)羰基化合物(β)，以等莫耳反應後，添加與硝基苯化合物(α)不同構造之硝基苯化合物(α’)即可。In the above-described diagram (I), in order to obtain a compound having a symmetrical structure centered on a (thio)ureido group, the nitrobenzene compound (α) and (α') may be the same, and in order to obtain an asymmetric compound, The nitrobenzene compound (α) may be added to the (thio)carbonyl compound (β) in a molar reaction, and then a nitrobenzene compound (α') having a structure different from that of the nitrobenzene compound (α) may be added.

鹼例如有三乙胺、二異丙基乙胺及DMAP(4-N,N-二甲基胺基吡啶)等之鹼性有機化合物、氫氧化鈉及碳酸鉀等之無機鹼化合物及氫氧化鈉等之金屬氫化物等。此處所示之化合物係一例，無特別限定。Examples of the base include basic organic compounds such as triethylamine, diisopropylethylamine and DMAP (4-N,N-dimethylaminopyridine), inorganic base compounds such as sodium hydroxide and potassium carbonate, and sodium hydroxide. Such as metal hydrides and the like. The compound shown here is an example, and is not specifically limited.

有機溶劑係不影響反應的溶劑，具體而言，例如有甲苯及二甲苯等之芳香族系溶劑、己烷及庚烷等之脂肪族烴系溶劑、二氯甲烷及1，2-二氯乙烷等之鹵素系溶劑、四氫呋喃及1，4-二噁烷等之醚系溶劑及N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯烷酮及二甲基亞碸等之非質子性極性溶劑以單獨或複數混合使用。此等之使用量為任意。The organic solvent is a solvent which does not affect the reaction, and specifically, for example, an aromatic solvent such as toluene or xylene, an aliphatic hydrocarbon solvent such as hexane or heptane, dichloromethane or 1,2-dichloroethane. a halogen solvent such as an alkane, an ether solvent such as tetrahydrofuran or 1,4-dioxane, and N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and The aprotic polar solvent such as dimethyl hydrazine is used alone or in combination. The usage amount of these is arbitrary.

如上述合成之二胺可作為聚醯亞胺前驅物之聚醯胺酸的原料使用。除聚醯胺酸酯等之聚醯亞胺前驅物或聚醯亞胺外，也可作為聚醯胺或聚胺基甲酸酯的原料使用，此等聚合物可作為各種電子材料用的素材使用。The diamine synthesized as described above can be used as a raw material of polylysine which is a polyimide precursor. In addition to polyimide precursors such as polyamidomate or polyimine, it can also be used as a raw material for polyamines or polyurethanes. These polymers can be used as materials for various electronic materials. use.

<選自由式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物><at least one diamine compound selected from the group consisting of diamine compounds represented by formula (2-1), formula (2-2) and formula (2-3)>

本實施形態之液晶配向劑含有聚醯胺酸，但是聚醯胺酸原料之二胺成分為含有上述式(1)表示之特定二胺及選自由下述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物。The liquid crystal alignment agent of the present embodiment contains polyamic acid, but the diamine component of the polyproline raw material contains the specific diamine represented by the above formula (1) and is selected from the following formula (2-1) and formula (2). -2) and at least one diamine compound in a group of diamine compounds represented by formula (2-3).

本實施形態之液晶配向劑係如上述，含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸。聚醯胺酸原料之二胺成分可含有上述式(1)表示之特定二胺與選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物。此時，特定二胺(1)與選自由式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物之各自的含量係當作為液晶配向膜時，考慮可得到充分之摩擦耐性、液晶配向性、高透過率、膜電阻較佳的光感度來決定。此外，也可從此液晶配向膜可實現使用於液晶顯示元件時之液晶之預傾角之最佳化、離子密度之降低、蓄積電荷之降低及良好的殘像特性等的觀點來考慮。As described above, the liquid crystal alignment agent of the present embodiment contains a polyamic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component. The diamine component of the polyaminic acid raw material may contain a specific diamine represented by the above formula (1) and a diamine compound selected from the above formula (2-1), formula (2-2) and formula (2-3). Groups of at least one diamine compound. At this time, the content of the specific diamine (1) and at least one diamine compound selected from the group consisting of the diamine compounds represented by the formula (2-1), the formula (2-2), and the formula (2-3) When it is used as a liquid crystal alignment film, it is determined in consideration of sufficient light resistance, liquid crystal alignment property, high transmittance, and light sensitivity of film resistance. Further, from the viewpoint of optimizing the pretilt angle of the liquid crystal used in the liquid crystal display element, reducing the ion density, reducing the accumulated charge, and excellent afterimage characteristics, the liquid crystal alignment film can be considered.

本實施形態中，全二胺成分(100莫耳%)中，較佳為式(1)表示之特定二胺含有5~60莫耳%、選自由式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物含有40~95莫耳%。全二胺成分(100莫耳%)中，更佳為式(1)表示之特定二胺含有10~50莫耳%、選自由式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物含有50~90莫耳%。全二胺成分(100莫耳%)中，更佳為式(1)表示之特定二胺含有20~40莫耳%、選自由式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物含有60~80莫耳%。選自由式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物，較佳為p-苯二胺(2-1)。In the present embodiment, in the total diamine component (100% by mole), the specific diamine represented by the formula (1) preferably contains 5 to 60 mol%, and is selected from the formula (2-1) and the formula (2-). 2) The at least one diamine compound in a group of the diamine compounds represented by the formula (2-3) contains 40 to 95 mol%. In the total diamine component (100 mol%), it is more preferred that the specific diamine represented by the formula (1) contains 10 to 50 mol%, which is selected from the formula (2-1), the formula (2-2), and the formula (1). 2-3) The at least one diamine compound represented by the diamine compound is contained in an amount of 50 to 90 mol%. In the total diamine component (100 mol%), it is more preferred that the specific diamine represented by the formula (1) contains 20 to 40 mol%, which is selected from the formula (2-1), the formula (2-2), and the formula (1). 2-3) The at least one diamine compound represented by the diamine compound is contained in an amount of 60 to 80 mol%. Selecting at least one diamine compound, preferably p-phenylenediamine (2-1), of the diamine compound represented by the formula (2-1), the formula (2-2) and the formula (2-3) .

本實施形態之液晶配向劑中，成為聚醯胺酸原料之二胺成分含有式(1)表示之特定二胺及二胺化合物(2-1)~(2-3)中之至少一種時，也可併用與此等不同之其他的二胺化合物。此其他之二胺化合物係含有含氮原子之雜環的二胺化合物，具體而言，例如有下述式(3)表示之二胺化合物(3)。同時含有二胺化合物(3)、特定二胺(1)、及選自由p-苯二胺等之式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物時，全二胺成分(100莫耳%)中，較佳為含有20莫耳%以下之量的二胺化合物(3)。<二胺化合物(3)>In the liquid crystal alignment agent of the present embodiment, when the diamine component of the polyglycine raw material contains at least one of the specific diamine and the diamine compound (2-1) to (2-3) represented by the formula (1), Other diamine compounds different from these may also be used in combination. The other diamine compound is a diamine compound containing a hetero ring containing a nitrogen atom, and specifically, for example, a diamine compound (3) represented by the following formula (3). A diamine compound (3), a specific diamine (1), and a diamine represented by the formula (2-1), the formula (2-2), and the formula (2-3) derived from p-phenylenediamine or the like. In the case of at least one diamine compound in which the compound is a group, the diamine compound (3) is preferably contained in an amount of 20 mol% or less of the total diamine component (100 mol%). <Diamine compound (3)>

式(3)中，X¹係選自由-O-、-NQ¹-、-CONQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種2價有機基，Q¹係氫原子或碳數1~3之烷基，X²係單鍵、或選自由碳數1~20之脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群之至少一種2價有機基，X³係單鍵、或選自由-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種2價有機基，Q²係氫原子或碳數1~3之烷基，X⁴係1價含氮芳香族雜環，n係1~4之整數。式(3)中之2個胺基(-NH₂)之鍵結位置未限定。具體而言，n為整數1時，相對於側鏈之鍵結基(X¹)，例如有苯環上之2，3之位置、2，4之位置、2，5之位置、2，6之位置、3，4之位置、3，5之位置。Of formula (3), X ¹ is selected from the group consisting of ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O- and -OCO- groups of the at least one divalent organic group And Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the X ² -based single bond or at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group; one kind of a bivalent organic group, X ³ system single bond, or selected from the group consisting of ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH _{2) m} - (m is an integer of 1 to 5) at least one divalent organic group, Q ² hydrogen atom or alkyl group having 1 to 3 carbon atoms, X ⁴ is a monovalent nitrogen-containing aromatic heterocyclic ring, and n is a system An integer from 1 to 4. The bonding position of the two amine groups (-NH ₂ ) in the formula (3) is not limited. Specifically, when n is an integer 1, the bonding group (X ¹ ) with respect to the side chain has, for example, a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, and 2, 6 Position, 3, 4 position, 3, 5 position.

n為整數2時，例如有以下的位置。相對於側鏈之鍵結基(X¹)，在苯環上之2位置有側鏈之鍵結基(X¹)時，2個胺基之鍵結位置，例如有3，4之位置、3，5之位置、3，6之位置、4，5之位置。又，相對於側鏈之鍵結基(X¹)，在苯環上之3的位置具有側鏈之鍵結基(X¹)時，2個胺基之鍵結位置，例如有2，4之位置、2，5之位置、4，5之位置、4，6之位置。此外，相對於側鏈之鍵結基(X¹)，在苯環上之4的位置具有側鏈之鍵結基(X¹)時，2個胺基之鍵結位置，例如有2，3之位置、2，5之位置、2，6之位置、3，5之位置。n為整數3時，例如有以下的位置。相對於側鏈之鍵結基(X¹)，在苯環上之2，3的位置具有側鏈之鍵結基(X¹)時，2個胺基之鍵結位置，例如有4，5之位置、4，6之位置。此外，相對於側鏈之鍵結基(X¹)，在苯環上之2，4的位置具有側鏈之鍵結基(X¹)時，2個胺基之鍵結位置，例如有3，5之位置、3，6之位置、5，6之位置。相對於側鏈之鍵結基(X¹)，在苯環上之3，5的位置具有側鏈之鍵結基(X¹)時，2個胺基之鍵結位置，例如有2，4的位置。When n is an integer 2, for example, the following positions are available. With respect to the side chain of the bonding group (X ^1), the side chain bonding group (X ¹⁾ in the second position on the benzene ring, bonding positions of the two amine groups of, for example, the 3,4 position, 3, 5 position, 3, 6 position, 4, 5 position. Further, when the bonding group (X ¹ ) at the position of 3 on the benzene ring has a bonding group (X ¹ ) of a side chain with respect to the bonding group (X ¹ ) of the side chain, the bonding position of the two amine groups is, for example, 2, 4 Position, 2, 5 position, 4, 5 position, 4, 6 position. Further, with respect to the bonding group (X ¹ ) of the side chain, when the position of 4 on the benzene ring has a bonding group (X ¹ ) of a side chain, the bonding position of the two amine groups, for example, 2, 3 Position, 2, 5 position, 2, 6 position, 3, 5 position. When n is an integer 3, for example, the following positions are available. With respect to the bonding group (X ¹ ) of the side chain, when the position of 2, 3 on the benzene ring has a bonding group (X ¹ ) of a side chain, the bonding position of two amine groups, for example, 4, 5 Position, 4, 6 position. Further, with respect to the bonding group (X ¹ ) of the side chain, when the position of 2, 4 on the benzene ring has a bonding group (X ¹ ) of a side chain, the bonding position of the two amine groups, for example, 3 , 5 position, 3, 6 position, 5, 6 position. With respect to the bonding group (X ¹ ) of the side chain, when the position of 3, 5 on the benzene ring has a bonding group (X ¹ ) of a side chain, the bonding position of two amine groups, for example, 2, 4 s position.

n為整數4時，例如有以下的位置。相對於側鏈之鍵結基(X¹)，在苯環上之2，3，4之位置具有側鏈之鍵結基(X¹)時，2個胺基之鍵結位置例如有5，6之位置。相對於側鏈之鍵結基(X¹)，在苯環上之2，4，5的位置具有側鏈之鍵結基(X¹)時，2個胺基之鍵結位置，例如有3，6之位置。相對於側鏈之鍵結基(X¹)，在苯環上之2，4，6之位置具有側鏈之鍵結基(X¹)時，2個胺基之鍵結位置，例如有3，5之位置。此等中，從合成聚醯胺酸時之反應性的觀點及考慮合成二胺化合物時之容易性時，n為整數1時，2個胺基之鍵結位置較佳為2，4之位置、2，5之位置、3，5之位置。此外，相對於n為整數2時之側鏈的鍵結基(X¹)，在苯環上之3的位置具有側鏈之鍵結基(X¹)時，2個胺基之鍵結位置較佳為4，6之位置。When n is an integer 4, for example, the following positions are available. With respect to the side chain of the bonding group (X ^1), having a side chain of the bonding group (X ¹⁾ at a position on the benzene ring of 2,3,4, bonding positions of the two amine groups of the example 5, 6 position. With respect to the bonding group (X ¹ ) of the side chain, when the position of 2, 4, 5 on the benzene ring has a bonding group (X ¹ ) of a side chain, the bonding position of two amine groups, for example, 3 , the location of 6. With respect to the side chain of the bonding group (X ^1), having a side chain of the bonding group (X ¹⁾ at a position on the benzene ring of 2,4,6, bonding positions of the two amine groups of, for example, 3 , the location of 5. In the above, from the viewpoint of the reactivity in synthesizing polyamic acid and the easiness in synthesizing the diamine compound, when n is an integer 1, the bonding position of the two amine groups is preferably 2, 4 , 2, 5 position, 3, 5 position. Further, with respect to the side chain n is an integer of 2 of the bonding group (X ^1), has a side chain of the bonding group (X ^1), 2 amine groups of the bonding position of the phenyl ring in position 3 of It is preferably at the position of 4, 6.

式(3)中，X¹係選自由-O-、-NQ¹-、-CONQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種2價有機基。其中，較佳為-O-、-NQ¹-、-CONQ¹-、-NQ¹CO-。Q¹係如上述為氫原子或碳數1~3之烷基。具體記載X¹之式(3)的例，例如有下述式(3a)~式(3f)。Of formula (3), X ¹ is selected from the group consisting of ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O- and -OCO- groups of the at least one divalent organic group . Wherein, preferably ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO-. Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms as described above. Specifically, an example of the formula (3) of X ¹ is described, for example, the following formulas (3a) to (3f).

上述化合物中，較佳為式(3a)、式(3b)、式(3c)及式(3d)。Q¹係與式(3)之定義相同。式(3)中，X²係單鍵、碳數1~20脂肪族烴基、非芳香族環式烴基或芳香族烴基。碳數1~20之脂肪族烴基可為直鏈狀或支鏈狀。又，可具有不飽和鍵。較佳為碳數1~10之脂肪族烴基。非芳香族環式烴基之具體例有環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、環壬烷環、環癸烷環、環十一烷環、環十二烷環、環十三烷環、環十四烷環、環十五烷環、環十六烷環、環十七烷環、環十八烷環、環十九烷環、環二十烷環、三環二十烷環、三環癸烷環、雙環庚烷環、十氫萘環、降冰片烯環或金剛烷環等。Among the above compounds, preferred are the formula (3a), the formula (3b), the formula (3c) and the formula (3d). The Q ¹ system is the same as the definition of the formula (3). In formula (3), X ² is a single bond, and the carbon number is 1-20. An aliphatic hydrocarbon group, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Also, it may have an unsaturated bond. It is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Specific examples of the non-aromatic cyclic hydrocarbon group are a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, and a ring. Undecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, ring nineteen An alkane ring, a cyclohexadecane ring, a tricyclohexadecane ring, a tricyclodecane ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring or an adamantane ring.

芳香族烴基之具體例有苯環、萘環、四氫萘環、薁環、茚環、芴環、蒽環、菲環或非那烯(Phenalene)環等。Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring or a phenalene ring.

式(3)中之X²，較佳為單鍵、碳數1~10之直鏈或支鏈之伸烷基、碳數1~10之不飽和伸烷基、環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、降冰片烯環、金剛烷環、苯環、萘環、四氫萘環、芴環或蒽環，更佳為單鍵、碳數1~10之直鏈或支鏈之伸烷基、碳數1~10之不飽和伸烷基、環己烷環、降冰片烯環、金剛烷環、苯環、萘環、芴環或蒽環，更佳為單鍵、碳數1~10之直鏈或支鏈之伸烷基、環己烷環、苯環或萘環。特佳為單鍵、碳數1~5之直鏈或支鏈之伸烷基或苯環。最佳為單鍵、碳數1~3之直鏈伸烷基或苯環。X ² in the formula (3) is preferably a single bond, a linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring or a cyclobutane. Ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, anthracene ring or anthracene ring, more preferably single bond, carbon a straight or branched alkyl group of 1 to 10, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, an anthracene ring or The anthracene ring is more preferably a single bond, a linear or branched alkyl group having a carbon number of 1 to 10, a cyclohexane ring, a benzene ring or a naphthalene ring. Particularly preferred is a single bond, a linear or branched alkyl or benzene ring having a carbon number of 1 to 5. It is preferably a single bond, a linear alkyl group having a carbon number of 1 to 3 or a benzene ring.

式(3)中，X³係單鍵、或選自由-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種2價有機基，較佳為單鍵、-O-、-CONQ²-、-NQ²CO-、-COO-、-OCO-或-O(CH₂)_m-(m係1~5之整數)。最佳為單鍵、-OCO-或-OCH₂-。Q²係如上述為氫原子或碳數1~3之烷基。式(3)中，X⁴係1價之含氮芳香族雜環，含有選自由下述式(31a)、式(31b)及式(31c)所成群之至少1個構造的含氮芳香族雜環。但是式(31c)中，Y³係碳數1~5之直鏈或支鏈之烷基。Of formula (3), X ³ system single bond, or selected from the group consisting of ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH _{2) m} - (m is an integer from 1 to 5) of at least one divalent organic group, preferably a single bond, -O-, -CONQ ² -, -NQ ² CO-, -COO-, -OCO- or -O(CH ₂ ) _m - (m is an integer of 1 to 5). The best is a single bond, -OCO- or -OCH ₂ -. The Q ^{2 group} is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms as described above. In the formula (3), the X ⁴ -based monovalent nitrogen-containing aromatic heterocyclic ring contains a nitrogen-containing aromatic compound selected from at least one of the following groups (31a), (31b), and (31c). Family heterocycle. However, in the formula (31c), Y ³ is a linear or branched alkyl group having 1 to 5 carbon atoms.

式(3)中之X⁴，例如有吡咯環、咪唑環、噁唑環、噻唑環、吡唑環、吡啶環、嘧啶環、喹啉環、吡唑啉環、異喹啉環、咔唑環、嘌呤環、噻二唑環、噠嗪環、吡唑啉環、三嗪環、吡唑烷環、***環、吡嗪環、苯並咪唑環(benzimidazole)、苯並咪唑(benzoimidazole)環、喹啉環、菲繞啉環、吲哚環、喹喔啉環、苯並噻唑環、吩噻嗪環、噁二唑環或吖啶環，更佳為吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、吡唑啉環、咔唑環、噠嗪環、吡唑啉環、三嗪環、吡唑烷環、***環、哌啶環、苯并咪唑環或苯并咪唑環，更佳為吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、噠嗪環、三嗪環、***環、哌啶環、苯并咪唑環或苯并咪唑環，特佳為吡咯環、咪唑環、吡唑環、吡啶環或嘧啶環。又最佳為咪唑環、吡啶環或嘧啶環。X³較佳為鍵結於不與包含於X⁴之式(31a)、式(31b)及式(31c)所示之構造相鄰的部位。式(3)中，n係1~4之整數，從與四羧酸二酐成分之反應性的觀點，較佳為1~3之整數。最佳為n係1或2之整數。式(3)中之較佳的X¹、X²、X³、X⁴及n之組合如下述。X ⁴ in the formula (3), for example, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, an oxazole Ring, anthracene ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole Ring, quinoline ring, phenanthroline ring, anthracene ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring, more preferably pyrrole ring, imidazole ring, pyrazole Ring, pyridine ring, pyrimidine ring, pyrazoline ring, indazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, piperidine ring, benzimidazole ring or benzo The imidazole ring is more preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a piperidine ring, a benzimidazole ring or a benzimidazole ring. It is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring. Also preferably, it is an imidazole ring, a pyridine ring or a pyrimidine ring. X ^{3 is} preferably bonded to a portion not adjacent to the structure represented by the formula (31a), the formula (31b), and the formula (31c) of X ⁴ . In the formula (3), n is an integer of from 1 to 4, and is preferably an integer of from 1 to 3 from the viewpoint of reactivity with the tetracarboxylic dianhydride component. Most preferably an integer of n series 1 or 2. Preferred combinations of X ¹ , X ² , X ³ , X ⁴ and n in the formula (3) are as follows.

X¹係選自由-O-、-NQ¹-、-CONQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種。X²係選自由碳數1~10之直鏈或支鏈伸烷基、碳數1~10之不飽和伸烷基、環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、降冰片烯環、金剛烷環、苯環、萘環、四氫萘環、芴環及蒽環所成群之至少一種。X³係選自由單鍵、-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種。X⁴係選自由吡咯環、咪唑環、噁唑環、噻唑環、吡唑環、吡啶環、嘧啶環、喹啉環、吡唑啉環、異喹啉環、咔唑環、嘌呤環、噻二唑環、噠嗪環、吡唑啉環、三嗪環、吡唑烷環、***環、吡嗪環、苯並咪唑環(benzimidazole)、苯並咪唑(benzoimidazole)環、喹啉環、菲繞啉環、吲哚環、喹喔啉環、苯並噻唑環、吩噻嗪環、噁二唑環或吖啶環所成群之至少一種。n係1或2之整數。更佳之式(3)中之X¹、X²、X³、X⁴及n之組合如下述。X ¹ selected from the group consisting of ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O- , and the groups of at least one -OCO-. X ² is selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. At least one of a group consisting of a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring, and an anthracene ring. X ³ selected from the group consisting of a single ^{bond, -O -, - NQ 2 -} , - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and _{-O (CH 2) m - (} m lines 1-5 Integer) at least one of the groups. X ⁴ is selected from the group consisting of a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, an indazole ring, an anthracene ring, and a thiophene ring. Diazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, quinoline ring, At least one of a group consisting of a phenanthroline ring, an anthracene ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring or an acridine ring. n is an integer of 1 or 2. More preferably, the combination of X ¹ , X ² , X ³ , X ⁴ and n in the formula (3) is as follows.

X¹係選自由-O-、-NQ¹-、-CONQ¹-、-NQ¹CO-及-CH₂O-所成群之至少一種。X²係選自由碳數1~10之直鏈或支鏈伸烷基、碳數1~10之不飽和伸烷基、環己烷環、降冰片烯環、金剛烷環、苯環、萘環、芴環及蒽環所成群之至少一種。X³係選自由單鍵、-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種。X ¹ selected from the group consisting of ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO- -CH ₂ O- and at least one of the groups. X ² is selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, and naphthalene. At least one of a group of rings, ankle rings and an anthracene ring. X ³ selected from the group consisting of a single ^{bond, -O -, - NQ 2 -} , - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and _{-O (CH 2) m - (} m lines 1-5 Integer) at least one of the groups.

X⁴係選自由吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、吡唑啉環、咔唑環、噠嗪環、吡唑啉環、三嗪環、吡唑烷環、***環、吡嗪環、苯並咪唑環(benzimidazole)及苯並咪唑(benzoimidazole)環所成群之至少一種。n係1或2之整數。更佳之式(3)中之X¹、X²、X³、X⁴及n之組合如下述，X¹係選自由-O-、-NQ¹-、-CONQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種。X²係選自由碳數1~10之直鏈或支鏈伸烷基、環己烷環、苯環及萘環所成群之至少一種。X³係選自由單鍵、-O-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種。X ⁴ is selected from the group consisting of pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, indazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole At least one of a ring, a pyrazine ring, a benzimidazole ring, and a benzoimidazole ring. n is an integer of 1 or 2. More preferably of the formula (3) in the ^{X 1, X 2, X 3} , X ^4, and a combination of n as follows, X ¹ selected from the group consisting of ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO- At least one of -CH ₂ O- and -OCO-. X ² is at least one selected from the group consisting of a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring, and a naphthalene ring. X ³ selected from the group consisting of a single ^{bond, -O -, - CONQ 2 -} , - NQ 2 CO -, - COO -, - OCO- and _{-O (CH 2) m - (} m an integer of 1 to 5 of the system) into the At least one of the groups.

X⁴係選自由吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、噠嗪環、三嗪環、***環、吡嗪環、苯並咪唑環(benzimidazole)及苯並咪唑(benzoimidazole)環所成群之至少一種。n係1或2之整數。特佳之式(3)中之X¹、X²、X³、X⁴及n之組合係如下述。X ⁴ is selected from the group consisting of pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring and benzimidazole. At least one of the rings. n is an integer of 1 or 2. The combination of X ¹ , X ² , X ³ , X ⁴ and n in the preferred formula (3) is as follows.

X¹係選自由-O-、-NQ¹-、-CONQ¹-、-NQ¹CO-及-CH₂O-所成群之至少一種。X²係選自由單鍵、碳數1~5之直鏈或支鏈之伸烷基及苯環所成群之至少一種。X ¹ selected from the group consisting of ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO- -CH ₂ O- and at least one of the groups. X ² is at least one selected from the group consisting of a single bond, a linear or branched alkyl group having 1 to 5 carbon atoms, and a benzene ring.

X³係選自由單鍵、-O-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種。X⁴係選自由吡咯環、咪唑環、吡唑環、吡啶環及嘧啶環所成群之至少一種。n係1或2之整數。最佳之式(3)中之X¹、X²、X³、X⁴及n之組合係如下述。X¹係選自由-O-、-NQ¹-、-CONQ¹-及-NQ¹CO-所成群之至少一種。X²係選自由單鍵、碳數1~3之直鏈伸烷基及苯環所成群之至少一種。X³係選自由單鍵、-OCO-及-OCH₂-所成群之至少一種。X⁴係選自由咪唑環、吡啶環及嘧啶環所成群之至少一種。X ³ selected from the group consisting of a single ^{bond, -O -, - CONQ 2 -} , - NQ 2 CO -, - COO -, - OCO- and _{-O (CH 2) m - (} m an integer of 1 to 5 of the system) into the At least one of the groups. X ⁴ is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring. n is an integer of 1 or 2. The combination of X ¹ , X ² , X ³ , X ⁴ and n in the most preferred formula (3) is as follows. X ¹ selected from the group consisting of ^{-O -, - NQ 1 -,} - CONQ 1 - -NQ ¹ CO- and at least one of the groups. X ² is at least one selected from the group consisting of a single bond, a linear alkyl group having 1 to 3 carbon atoms, and a benzene ring. X ³ is at least one selected from the group consisting of a single bond, -OCO-, and -OCH ₂ -. X ⁴ is at least one selected from the group consisting of an imidazole ring, a pyridine ring, and a pyrimidine ring.

n係1或2之整數。特佳之式(3)中之X¹、X²、X³、X⁴及n之組合係如下述表1~表3之301~393所示。Q¹及Q²係與式(3)之定義相同意義。n is an integer of 1 or 2. The combination of X ¹ , X ² , X ³ , X ⁴ and n in the preferred formula (3) is shown in Tables 301 to 393 of Tables 1 to 3 below. The Q ¹ and Q ² systems have the same meaning as the definition of the formula (3).

<二胺化合物(3)之合成方法>製造二胺化合物(3)的方法無特別限定，較佳的方法例如有以下的方法。<Synthesis Method of Diamine Compound (3)> The method for producing the diamine compound (3) is not particularly limited, and a preferred method is, for example, the following method.

二胺化合物(3)係合成以式[N]表示之二硝基體，接著使二硝基還原，轉換成胺基而得。使二硝基化合物還原的方法並無特別限制，通常為以鈀-碳、氧化鉑、阮尼鎳、鉑黑、銠-氧化鋁、硫化鉑碳等作為觸媒使用，於乙酸乙酯、甲苯、四氫呋喃、二噁烷或醇系等溶劑中，使用氫氣、聯胺或氯化氫等進行還原的方法。又，式(N)中，X¹、X²、X³、X⁴及n係與式(3)之定義相同意義。The diamine compound (3) is obtained by synthesizing a dinitro group represented by the formula [N], followed by reduction of a dinitro group to be converted into an amine group. The method for reducing the dinitro compound is not particularly limited, and it is usually used as a catalyst using palladium-carbon, platinum oxide, ruthenium nickel, platinum black, ruthenium-alumina, and platinum sulfide carbon in ethyl acetate or toluene. A method of reducing with hydrogen, hydrazine or hydrogen chloride in a solvent such as tetrahydrofuran, dioxane or an alcohol. Further, in the formula (N), X ¹ , X ² , X ³ , X ⁴ and n have the same meanings as defined in the formula (3).

式[N]表示之二硝基體係介於X³連結X²與X⁴，其後介於X¹鍵結二硝基部的方法或介於連結部X¹使二硝基部與X²鍵結，然後，介於X³與X⁴鍵結之方法等而得。X¹係選自由-O-(醚鍵)、-NQ¹-(胺基鍵)、-CONQ¹-(醯胺鍵)、-NQ¹CO-(逆醯胺鍵)、-CH₂O-(亞甲基醚鍵)及-OCO-(逆酯鍵)所成群之至少一種鍵結基，此等鍵結基可以通常有機合成方法形成。各鍵結基之Q¹係與式(1)之定義相同意義。例如，X¹為醚或亞甲基醚鍵時，例如有使對應之含有二硝基之鹵素衍生物與含有X²、X³及X⁴之羥基衍生物，在鹼存在下反應的方法，或使含有二硝基之羥基衍生物與含有X²、X³及X⁴之鹵素取代之衍生物，在鹼存在下反應的方法等。Represented by the formula [N] dinitro system coupled between X ² and X ³ X ^4, X ¹ thereafter bonded between A method dinitro portion or between the connecting portion so that X ¹ and X ² dinitro bonded portion Then, the method of bonding X ³ and X ^{4 is} obtained. X ¹ is selected from -O-(ether bond), -NQ ¹ -(amino bond), -CONQ ¹ -(deuterium bond), -NQ ¹ CO-(inverse amide bond), -CH ₂ O- At least one of a bonding group (methylene ether bond) and -OCO- (reverse ester bond) may be formed by a general organic synthesis method. The Q ¹ system of each bonding group has the same meaning as the definition of the formula (1). For example, when X ¹ is an ether or a methylene ether bond, for example, a method of reacting a corresponding halogen derivative containing a dinitro group with a hydroxy derivative containing X ² , X ³ and X ⁴ in the presence of a base, Or a method of reacting a dinitro group-containing hydroxy derivative with a halogen-substituted derivative containing X ² , X ³ and X ⁴ in the presence of a base.

胺基鍵的情況，例如有使對應之含有二硝基之鹵素衍生物與含有X²、X³及X⁴之胺基衍生物，在鹼存在下反應的方法等。逆酯鍵的情況，例如有使對應之含有二硝基之羥基衍生物與含有X²、X³及X⁴之醯氯(acid chloride)體，在鹼存在下反應的方法等。醯胺鍵係使對應之含有二硝基之醯氯體與含有X²、X³及X⁴之胺基取代體，在鹼存在下反應的方法等。逆醯胺鍵的情況，例如有使對應之含有二硝基之胺基取代體與含有X²、X³及X⁴之醯氯體，在鹼存在下反應的方法等。In the case of the amino group bond, for example, a method in which a halogen derivative containing a dinitro group and an amine derivative containing X ² , X ³ and X ⁴ are reacted in the presence of a base are used. In the case of the reverse ester bond, for example, there is a method in which a corresponding dinitro group-containing hydroxy derivative and an acid chloride containing X ² , X ³ and X ⁴ are reacted in the presence of a base. The guanamine bond is a method in which a corresponding dinitro-containing ruthenium chloride and an amine substituent containing X ² , X ³ and X ⁴ are reacted in the presence of a base. In the case of the reverse amide bond, for example, a method in which a corresponding dinitro group-containing amino group substituent and a chlorobenzene group containing X ² , X ³ and X ⁴ are reacted in the presence of a base are used.

含有二硝基之鹵素衍生物及含有二硝基之衍生物之具體例有3,5-二硝基氯苯、2,4-二硝基氯苯、2,4-二硝基氟苯、3,5-二硝基苯甲酸氯、3,5-二硝基苯甲酸、2,4-二硝基苯甲醯氯、2,4-二硝基苯甲酸、3,5-二硝基苄基氯、2,4-二硝基苄基氯、3,5-二硝基苄基醇、2,4-二硝基苄基醇、2,4-二硝基苯胺、3,5-二硝基苯胺、2,6-二硝基苯胺、2,4-二硝基酚、2,5-二硝基酚、2,6-二硝基酚或2,4-二硝基苯基乙酸等。考量原料之取得性或反應性，可選擇一種或複數種來使用。Specific examples of the dinitro-containing halogen derivative and the dinitro-containing derivative are 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, and 2,4-dinitrofluorobenzene. 3,5-dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzylidene chloride, 2,4-dinitrobenzoic acid, 3,5-dinitro Benzyl chloride, 2,4-dinitrobenzyl chloride, 3,5-dinitrobenzyl alcohol, 2,4-dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5- Dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol or 2,4-dinitrophenyl Acetic acid, etc. Considering the availability or reactivity of the raw materials, one or more kinds may be selected and used.

本實施形態之液晶配向劑係如上述，含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸。聚醯胺酸原料之二胺成分係含有以上述式(1)表示之特定二胺作為第1必須成分，此外，可含有下述式(4)表示之二胺化合物(4)作為第2必須成分的二胺化合物。As described above, the liquid crystal alignment agent of the present embodiment contains a polyamic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component. The diamine component of the polyaminic acid raw material contains the specific diamine represented by the above formula (1) as the first essential component, and may contain the diamine compound (4) represented by the following formula (4) as the second necessity. a diamine compound of the composition.

<二胺化合物(4)>二胺化合物(4)係分子內具有羰基之二胺化合物，具體而言係式(4)表示之化合物。式(4)中，X⁵係具有碳數6~30之芳香族環的有機基，n係1~4之整數。<Diamine Compound (4)> The diamine compound (4) is a diamine compound having a carbonyl group in the molecule, and specifically, a compound represented by the formula (4). In the formula (4), X ⁵ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.

式(4)例如有下述式(4-3)~(4-7)的構造。The formula (4) has a structure of the following formulas (4-3) to (4-7), for example.

式(4-3)中，m1係1~4之整數。式(4-4)中，X⁶係單鍵、-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-，m2及m3係分別為0~4之整數，且m2+m3係表示1~4之整數。式(4-5)中，m4及m5係分別為1~5之整數。In the formula (4-3), m1 is an integer of 1 to 4. In the formula (4-4), the X ⁶ series single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-, m2 and m3 are each an integer from 0 to 4, and m2+m3 represents an integer from 1 to 4. In the formula (4-5), m4 and m5 are each an integer of 1 to 5.

式(4-6)中，X⁷係碳數1~5之直鏈或支鏈烷基，m6係1~5之整數。式(4-7)中，X⁸係單鍵、-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-或-N(CH₃)CO-，m7係1~4之整數。式(4-3)~式(4-7)之構造中，較佳為如下述。式(4-3)中，m1較佳為1~2之整數。式(4-4)中，X⁶係單鍵、-CH₂-、-C₂H₄-、-C(CH₃)₂-、-O-、-CO-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-COO-或-OCO-，m2及m3較佳為均為1的整數。式(4-7)中，X⁸係單鍵、-CH₂-、-O-、-CO-、-NH-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-或-OCO-，m7較佳為1~2之整數。二胺化合物(4)之具體例有下述式(4-8)~式(4-18)的化合物。In the formula (4-6), X ⁷ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m6 is an integer of 1 to 5. In the formula (4-7), X ⁸ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-, m7 is an integer from 1 to 4. In the structure of the formula (4-3) to the formula (4-7), it is preferably as follows. In the formula (4-3), m1 is preferably an integer of 1 to 2. In the formula (4-4), the X ⁶ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, -N ( CH ₃ )-, -CONH-, -NHCO-, -COO- or -OCO-, m2 and m3 are preferably integers each. In the formula (4-7), X ⁸ is a single bond, -CH ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-, m7 is preferably an integer of 1 to 2. Specific examples of the diamine compound (4) include compounds of the following formula (4-8) to formula (4-18).

式(4-17)中，X⁹係單鍵、-CH₂-、-O-、-CO-、-NH-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-或-OCO-，式(4-18)中，X¹⁰係單鍵、-CH₂-、-O-、-CO-、-NH-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-或-OCO-。本實施形態中，為了得到聚醯胺酸用之二胺成分，特佳為併用式(1)表示之特定二胺與作為其他二胺之上述式(4-8)~式(4-12)及式(4-15)~式(4-18)表示之分子內具有羰基的二胺化合物。In the formula (4-17), X ⁹ is a single bond, -CH ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-, in the formula (4-18), the X ¹⁰ series single bond, -CH ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. In the present embodiment, in order to obtain a diamine component for polyphthalic acid, it is particularly preferred to use a specific diamine represented by the formula (1) in combination with the above formula (4-8) to formula (4-12) as another diamine. And a diamine compound having a carbonyl group in the molecule represented by the formula (4-15) to the formula (4-18).

本實施形態之液晶配向劑係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸，該聚醯胺酸原料之二胺成分如上述，可使用式(1)表示之特定二胺與式(4)表示之二胺化合物。此時，特定二胺(1)與二胺化合物(4)之各自之含量係當作為液晶配向膜時，考慮以得到充分之摩擦耐性、液晶配向性、高的透過率、膜電阻較佳的光感度等來決定。同時也要從實現此液晶配向膜使用於液晶顯示元件時之液晶之預傾角之最佳化、離子密度之降低、蓄積電荷之降低及良好的殘像特性等的觀點來考慮。本實施之形態係全二胺成分(100莫耳%)中，較佳為式(1)表示之特定二胺含有40~70莫耳%、式(4)表示之二胺化合物(4)含有30莫耳%以上。此外，全二胺成分(100莫耳%)中，更佳為式(1)表示之特定二胺含有50~70莫耳%、式(4)表示之二胺化合物(4)含有30~50莫耳%含有。The liquid crystal alignment agent of the present embodiment contains a polyamic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component, and the diamine component of the polyaminic acid raw material can be represented by the formula (1) as described above. A diamine and a diamine compound represented by the formula (4). In this case, the content of each of the specific diamine (1) and the diamine compound (4) is considered to be sufficient as the liquid crystal alignment film to obtain sufficient friction resistance, liquid crystal alignment, high transmittance, and film resistance. The light sensitivity is determined. At the same time, it is also considered from the viewpoints of optimization of the pretilt angle of the liquid crystal when the liquid crystal alignment film is used for the liquid crystal display element, reduction in ion density, reduction in accumulated charge, and good afterimage characteristics. In the embodiment of the present invention, the total diamine component (100% by mole) is preferably 40 to 70 mol% of the specific diamine represented by the formula (1), and the diamine compound (4) represented by the formula (4) is contained. 30% or more. Further, in the total diamine component (100 mol%), it is more preferred that the specific diamine represented by the formula (1) contains 50 to 70 mol%, and the diamine compound (4) represented by the formula (4) contains 30 to 50. Mole% contains.

本實施之形態的液晶配向劑中，含有特定二胺(1)與二胺化合物(4)時，另外的態樣為可併用與此等不同之另外的二胺化合物。另外的二胺化合物係如上述，例如具有含有氮原子之雜環的二胺化合物。此具有含有氮原子之雜環之二胺化合物的具體構造無特別限定，較佳為上述式(3)表示之二胺化合物(3)。二胺化合物(3)係由聚醯胺酸得到液晶配向膜時，與二胺化合物(4)組合，有助於膜之低電阻化。又，使用此液晶配向膜所得之液晶顯示元件中，也有助於改善離子密度特性。二胺化合物(3)不與二胺化合物(4)組合，以單獨用於聚醯胺酸之構成，成為液晶配向膜時，幾乎無助於膜之低電阻化。同時含有二胺化合物(3)、特定二胺(1)及二胺化合物(4)時，全二胺成分(100莫耳%)中，較佳為含有20莫耳%以下之量的二胺化合物(3)。本實施形態之液晶配向劑係成為聚醯胺酸之原料的二胺成分如上述，含有特定二胺(1)與二胺化合物(4)時，可含有二胺化合物(3)作為必須成分。藉此可具有更確實性，實現液晶配向膜之低電阻化。When the liquid crystal alignment agent of the embodiment of the present invention contains a specific diamine (1) and a diamine compound (4), it is also possible to use a different diamine compound different from the above. The other diamine compound is, for example, a diamine compound having a hetero ring containing a nitrogen atom as described above. The specific structure of the diamine compound having a hetero ring containing a nitrogen atom is not particularly limited, and the diamine compound (3) represented by the above formula (3) is preferred. When the diamine compound (3) is obtained by a polyphthalic acid to obtain a liquid crystal alignment film, it is combined with the diamine compound (4) to contribute to lowering the resistance of the film. Moreover, in the liquid crystal display element obtained by using this liquid crystal alignment film, it also contributes to the improvement of ion density characteristics. The diamine compound (3) is not used in combination with the diamine compound (4), and is used alone in the form of polyphthalic acid. When it is a liquid crystal alignment film, it hardly contributes to the reduction in resistance of the film. When the diamine compound (3), the specific diamine (1), and the diamine compound (4) are contained together, the diamine component (100 mol%) preferably contains 20 mol% or less of the diamine. Compound (3). In the liquid crystal alignment agent of the present embodiment, the diamine component which is a raw material of polylysine is as described above, and when the specific diamine (1) and the diamine compound (4) are contained, the diamine compound (3) may be contained as an essential component. Thereby, it is possible to have more certainty and achieve low resistance of the liquid crystal alignment film.

成為聚醯胺酸之原料的二胺成分含有特定二胺(1)、二胺化合物(4)及二胺化合物(3)時，特定二胺(1)較佳為含有50莫耳%以上，且少於100莫耳%的量。此時，全二胺成分(100莫耳%)之剩餘成分中，含有二胺化合物(4)與二胺化合物(3)。此時，二胺化合物(4)與二胺化合物(3)係以二胺化合物(4)：二胺化合物(3)=90：10~40：60之莫耳比含有較佳。如上述，本實施形態之液晶配向劑係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸，其中聚醯胺酸原料之二胺成分為含有上述式(1)表示之特定二胺作為第1必須成分。又，二胺成分可使用選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物作為第2必須成分及上述式(4)表示之二胺化合物。此時，如上述，選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與上述式(4)表示之二胺化合物，可各自獨立使用。或選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與上述式(4)表示之二胺化合物，也可各自同時使用。When the diamine component which is a raw material of the polyamic acid contains the specific diamine (1), the diamine compound (4), and the diamine compound (3), the specific diamine (1) preferably contains 50 mol% or more. And less than 100% by mole. At this time, the remaining components of the total diamine component (100 mol%) contain the diamine compound (4) and the diamine compound (3). In this case, the diamine compound (4) and the diamine compound (3) are preferably contained in a molar ratio of the diamine compound (4):diamine compound (3)=90:10 to 40:60. As described above, the liquid crystal alignment agent of the present embodiment contains a polyamic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component, wherein the diamine component of the polyproline raw material contains the formula (1). A specific diamine is used as the first essential component. Further, as the diamine component, at least one diamine compound selected from the group consisting of the diamine compounds represented by the above formula (2-1), formula (2-2) and formula (2-3) can be used as the second essential component and The diamine compound represented by the above formula (4). In this case, as described above, at least one diamine compound selected from the group consisting of the diamine compounds represented by the above formula (2-1), formula (2-2), and formula (2-3) is represented by the above formula (4). The diamine compounds can be used independently of each other. Or at least one diamine compound selected from the group consisting of the diamine compounds represented by the above formula (2-1), formula (2-2) and formula (2-3), and the diamine compound represented by the above formula (4), They can also be used at the same time.

聚醯胺酸原料之二胺成分同時含有特定二胺(1)與選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與二胺化合物(4)時，各自之含量係作為液晶配向膜時，考慮以可得到充分之摩擦耐性、液晶配向性、高的透過率、膜電阻較佳的光感度等來決定。同時也要從實現此液晶配向膜使用於液晶顯示元件時之液晶之預傾角之最佳化、離子密度之降低、蓄積電荷之降低及良好的殘像特性等的觀點來考慮。本實施形態係全二胺成分(100莫耳%)中，較佳為式(1)表示之特定二胺含有20~60莫耳%，選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與式(4)表示之二胺化合物，以選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物：式(4)表示之二胺化合物=95：5~40：60之莫耳比表示，合計含有40~80莫耳%較佳。全二胺成分(100莫耳%)中，更佳為式(1)表示之特定二胺含有30~50莫耳%，及選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與式(4)表示之二胺化合物，以選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物：式(4)表示之二胺化合物=95：5~60：40之莫耳比表示，合計含有50~70莫耳%。此外，全二胺成分(100莫耳%)中，特佳為式(1)表示之特定二胺含有30~50莫耳%，及選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與式(4)表示之二胺化合物，以選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物：式(4)表示之二胺化合物=95：5~70：30之莫耳比表示，合計含有50~70莫耳%。此外，選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物中，較佳為使用p-苯二胺(2-1)。本實施形態之液晶配向劑係含有式(1)表示之特定二胺與選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與式(4)表示之二胺化合物(4)，此外可併用與此等不同之另外的二胺化合物。The diamine component of the polyproline raw material contains a specific diamine (1) and a group selected from the diamine compounds represented by the above formula (2-1), formula (2-2) and formula (2-3). When at least one of the diamine compound and the diamine compound (4) is used as the liquid crystal alignment film, it is considered that sufficient friction resistance, liquid crystal alignment, high transmittance, and light resistance of the film resistance can be obtained. To decide. At the same time, it is also considered from the viewpoints of optimization of the pretilt angle of the liquid crystal when the liquid crystal alignment film is used for the liquid crystal display element, reduction in ion density, reduction in accumulated charge, and good afterimage characteristics. In the present embodiment, the total diamine component (100% by mole) is preferably 20 to 60 mol% of the specific diamine represented by the formula (1), and is selected from the above formula (2-1), formula (2- 2) and at least one diamine compound represented by the formula (2-3) and the diamine compound represented by the formula (4), which are selected from the above formula (2-1), formula (2-2) And at least one diamine compound represented by the formula (2-3): the diamine compound represented by the formula (4) = 95:5 to 40:60, and the molar ratio is 40~ 80% by mole is preferred. In the total diamine component (100 mol%), it is more preferred that the specific diamine represented by the formula (1) contains 30 to 50 mol%, and is selected from the above formula (2-1) and formula (2-2). At least one diamine compound represented by the formula (2-3) and the diamine compound represented by the formula (4) are selected from the above formula (2-1), formula (2-2) and (2-3) at least one diamine compound represented by a diamine compound: a diamine compound represented by the formula (4) = 95:5 to 60:40 molar ratio, and a total of 50 to 70 m %. Further, among the total diamine components (100 mol%), it is particularly preferable that the specific diamine represented by the formula (1) contains 30 to 50 mol%, and is selected from the above formula (2-1) and formula (2-2). And at least one diamine compound represented by the formula (2-3) and the diamine compound represented by the formula (4), which are selected from the above formula (2-1), formula (2-2) And at least one diamine compound represented by the formula (2-3): the diamine compound represented by the formula (4) = 95:5 to 70:30, and the molar ratio is 50 to 70 in total Moer%. Further, among at least one diamine compound selected from the group consisting of the diamine compounds represented by the above formula (2-1), formula (2-2) and formula (2-3), p-phenylenediamine is preferably used. (2-1). The liquid crystal alignment agent of the present embodiment contains a specific diamine represented by the formula (1) and a group selected from the diamine compounds represented by the above formula (2-1), formula (2-2) and formula (2-3). At least one of the diamine compound and the diamine compound (4) represented by the formula (4) may be used in combination with an additional diamine compound different from the above.

另外的二胺化合物係如上述，例如具有含有氮原子之雜環的二胺化合物，具體例有上述式(3)表示之二胺化合物(3)。二胺化合物(3)係由聚醯胺酸得到液晶配向膜時，與二胺化合物(4)組合，有助於膜之低電阻化。又，使用此液晶配向膜所得之液晶顯示元件中，也有助於改善離子密度特性。二胺化合物(3)不與二胺化合物(4)組合，以單獨用於聚醯胺酸之構成，成為液晶配向膜時，幾乎無助於膜之低電阻化。Further, the diamine compound is, for example, a diamine compound having a hetero ring containing a nitrogen atom, and a diamine compound (3) represented by the above formula (3). When the diamine compound (3) is obtained by a polyphthalic acid to obtain a liquid crystal alignment film, it is combined with the diamine compound (4) to contribute to lowering the resistance of the film. Moreover, in the liquid crystal display element obtained by using this liquid crystal alignment film, it also contributes to the improvement of ion density characteristics. The diamine compound (3) is not used in combination with the diamine compound (4), and is used alone in the form of polyphthalic acid. When it is a liquid crystal alignment film, it hardly contributes to the reduction in resistance of the film.

同時含有二胺化合物(3)、特定二胺(1)、選自由式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物及二胺化合物(4)時，全二胺成分(100莫耳%)中，較佳為含有20莫耳%以下之量的二胺化合物(3)。The diamine compound (3), the specific diamine (1), and at least one selected from the group consisting of the diamine compounds represented by the formula (2-1), the formula (2-2), and the formula (2-3) In the case of the amine compound and the diamine compound (4), the diamine compound (3) is preferably contained in an amount of 20 mol% or less in the total diamine component (100 mol%).

綜合上述，本實施形態之液晶配向劑係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸。聚醯胺酸原料之二胺成分係含有特定二胺(1)作為第1必須成分，含有二胺化合物作為第2必須成分。此二胺化合物係選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與式(4)表示之二胺化合物。此等係各自獨立使用或各自併用來使用。又，聚醯胺酸原料之二胺成分可含有作為非必須成分之以式(3)表示之二胺化合物。或可含有以式(3)表示之二胺化合物作為第3必須成分，與選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物之組合。In summary, the liquid crystal alignment agent of the present embodiment contains a polyamic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component. The diamine component of the polyproline raw material contains a specific diamine (1) as a first essential component and a diamine compound as a second essential component. The diamine compound is selected from the group consisting of at least one diamine compound represented by the diamine compound represented by the above formula (2-1), formula (2-2) and formula (2-3), and the formula (4) Amine compound. These are used independently or individually and for use. Further, the diamine component of the polyproline raw material may contain a diamine compound represented by the formula (3) as an optional component. Or a diamine compound represented by the formula (3) may be contained as a third essential component, and may be formed from a diamine compound selected from the above formula (2-1), formula (2-2) and formula (2-3). A combination of at least one diamine compound of the group.

本實施形態之液晶配向劑除上述式(1)、(2-1)~(2-3)、(3)、(4)表示之二胺化合物外，可含有其他之二胺化合物，作為聚醯胺酸的原料。In addition to the diamine compound represented by the above formulas (1), (2-1) to (2-3), (3), and (4), the liquid crystal alignment agent of the present embodiment may contain other diamine compounds as a poly A raw material for proline.

<其他之二胺化合物>本實施形態之液晶配向劑係如上述，含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸。聚醯胺酸原料之二胺成分係含有式(1)表示之特定二胺作為第1必須成分，其中第2必須成分為含有選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物或式(4)表示之二胺化合物或其兩者。又，二胺成分也可含有式(3)表示之二胺化合物作為第3之二胺成分。此外，二胺成分在不影響本發明之效果的範圍內，除了式(1)、(2-1)~(2-3)、(3)、(4)表示之二胺化合物外，也可含有其他之二胺化合物。其他之二胺無特別限定。其他之二胺化合物可以下述式(7)表示。<Other diamine compound> The liquid crystal alignment agent of the present embodiment contains a polylysine obtained by reacting a diamine component with a tetracarboxylic dianhydride component as described above. The diamine component of the polyaminic acid raw material contains a specific diamine represented by the formula (1) as a first essential component, and the second essential component contains a compound selected from the above formula (2-1) and formula (2-2). The formula (2-3) represents at least one diamine compound represented by the diamine compound or the diamine compound represented by the formula (4) or both. Further, the diamine component may contain the diamine compound represented by the formula (3) as the third diamine component. Further, the diamine component may be in addition to the diamine compound represented by the formulas (1), (2-1) to (2-3), (3), and (4), within a range not affecting the effects of the present invention. Contains other diamine compounds. The other diamine is not particularly limited. The other diamine compound can be represented by the following formula (7).

上述式(7)中，R⁵係表示2價有機基，R³及R⁴係各自獨立表示氫原子或1價有機基。R⁵之具體例有以下表[4-1]~表[4-4]所記載之2價有機基。In the above formula (7), R ⁵ represents a divalent organic group, and R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group. Specific examples of R ⁵ include the divalent organic groups described in the following Tables [4-1] to [4-4].

其他之二胺化合物例如有二胺側鏈上具有烷基、含氟烷基、芳香環、脂肪族環、雜環、及由彼等所構成之大環狀取代基的二胺，具體而言，例如有以下述式[DA1]~式[DA26]表示之二胺化合物。Other diamine compounds include, for example, a diamine having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a macrocyclic substituent composed of the same on the side chain of the diamine, specifically For example, there is a diamine compound represented by the following formula [DA1] to formula [DA26].

式[DA1]~式[DA5]中，R₁係碳數1以上22以下之烷基或含氟烷基。In the formula [DA1] to the formula [DA5], R ₁ is an alkyl group having 1 or more and 22 or less carbon atoms or a fluorine-containing alkyl group.

式[DA6]~式[DA9]中，R₂係表示-COO-、-OCO-、-CONH-、-NHCO-、-CH₂-、-O-、-CO-、或-NH-，R₃係表示碳數1以上22以下之烷基或含氟烷基。In the formula [DA6]~[DA9], R ₂ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or -NH-, R ₃ is an alkyl group or a fluorine-containing alkyl group having 1 or more and 22 or less carbon atoms.

式[DA10]及式[DA11]中，R₄係表示-O-、-OCH₂-、-CH₂O-、-COOCH₂-、或-CH₂OCO-，R₅係表示碳數1以上22以下之烷基、烷氧基、含氟烷基或含氟烷氧基。In the formula [DA10] and the formula [DA11], R ₄ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, or -CH ₂ OCO-, and R ₅ represents a carbon number of 1 or more. An alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group of 22 or less.

式[DA12]~式[DA14]中，R₆係表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、或-CH₂-，R₇係表示碳數1以上22以下之烷基、烷氧基、含氟烷基或含氟烷氧基。In the formula [DA12]~[DA14], R ₆ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ -, and R ₇ represents an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 or more and 22 or less carbon atoms.

式[DA15]及式[DA16]中，R₈係表示-COO-、-OCO-、-CONH-、-NHCO-、-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂-、-O-、或-NH-，R₉係表示氟基、氰基、三氟甲基、硝基、偶氮基、甲醯基、乙醯基、乙醯氧基或羥基。In the formula [DA15] and the formula [DA16], R ₈ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O-, or -NH-, R ₉ represents a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, an ethoxy group. Base or hydroxyl group.

此外，其他之二胺化合物，例如有下述式[DA27]表示之二胺基矽氧烷等。Further, the other diamine compound is, for example, a diamine siloxane such as represented by the following formula [DA27].

式[DA27]中，m係1~10之整數。以上所列舉之其他之二胺化合物係配合作為液晶配向膜時之體積電阻率對光之感度、低體積電阻率、摩擦耐性、離子密度特性、透過率、液晶配向性、電壓保持特性及蓄積電荷等之特性，可使用1種類或混合2種類以上使用。In the formula [DA27], m is an integer of 1 to 10. The other diamine compounds listed above are used in combination with a volume resistivity, a low volume resistivity, a friction resistance, an ion density characteristic, a transmittance, a liquid crystal alignment property, a voltage holding property, and an accumulated charge when used as a liquid crystal alignment film. The characteristics can be used in one type or in two or more types.

<四羧酸二酐成分>本實施形態之液晶配向劑所含有之聚醯胺酸係二胺成分與四羧酸二酐成分反應所得。二胺成分係如上述，含有上述式(1)表示之特定二胺與上述其他之二胺化合物者。四羧酸衍生物較佳為四羧酸二酐成分。四羧酸二酐成分係以下述式(5)表示。其中，R⁶係表示可含有氧原子、硫原子、氟原子之4價烴基。R⁶之具體例有以下之[A-1]~[A-48]表示之4價基。<Tetracarboxylic acid dianhydride component> The polyphthalic acid type diamine component contained in the liquid crystal alignment agent of this embodiment is obtained by reacting with a tetracarboxylic dianhydride component. The diamine component contains the specific diamine represented by the above formula (1) and the other diamine compound as described above. The tetracarboxylic acid derivative is preferably a tetracarboxylic dianhydride component. The tetracarboxylic dianhydride component is represented by the following formula (5). Here, R ⁶ means a tetravalent hydrocarbon group which may contain an oxygen atom, a sulfur atom or a fluorine atom. Specific examples of R ⁶ include the following four-valent groups represented by [A-1] to [A-48].

本實施形態係四羧酸二酐成分之50莫耳%以上，較佳為80莫耳%以上為R⁶具有如式[A-1]~式[A-25]之脂環式構造或脂肪族構造之式(5)表示的四羧酸二酐較佳。藉由形成這種成分組成，可提高液晶配向膜之電壓保持率，對光之感度降低。R⁶為此等脂環式構造或脂肪族構造中，使用選自式[A-1]、式[A-16]及式[A-19]所成群之四羧酸二酐時，可得到電荷之緩和更快速之液晶配向膜，故較佳。四羧酸二酐成分較佳為含有芳香族四羧酸二酐。藉此可提高液晶配向膜之配向性，可降低蓄積電荷。此時，相對於四羧酸二酐成分之全量，使用太多的量時，對光之感度變高，成為引起顯示不良的原因。因此，相對於四羧酸二酐之全量，芳香族四羧酸二酐較佳為50莫耳%以下，更佳為20莫耳%以下。上述二胺成分與四羧酸二酐成分(以下有時僅稱為四羧酸二酐)反應欲得到聚醯胺酸時，可使用公知的方法。以下說明使用四羧酸二酐的反應。本實施形態中，四羧酸二酐與二胺成分之聚合反應方法無特別限定。一般而言，藉由在有機溶劑中進行混合，產生聚合反應可成為聚醯胺酸。In the present embodiment, 50 mol% or more of the tetracarboxylic dianhydride component, preferably 80 mol% or more, R ⁶ has an alicyclic structure or fat of the formula [A-1] to formula [A-25]. The tetracarboxylic dianhydride represented by the formula (5) of the family structure is preferred. By forming such a component composition, the voltage holding ratio of the liquid crystal alignment film can be increased, and the sensitivity to light is lowered. R ^{6 may be} used in the alicyclic structure or the aliphatic structure, and the tetracarboxylic dianhydride selected from the group consisting of the formula [A-1], the formula [A-16], and the formula [A-19] may be used. It is preferred to obtain a liquid crystal alignment film in which the charge is more relaxed. The tetracarboxylic dianhydride component preferably contains an aromatic tetracarboxylic dianhydride. Thereby, the alignment of the liquid crystal alignment film can be improved, and the accumulated charge can be reduced. In this case, when too much amount is used with respect to the total amount of the tetracarboxylic dianhydride component, the sensitivity to light is increased, which causes a display failure. Therefore, the aromatic tetracarboxylic dianhydride is preferably 50 mol% or less, more preferably 20 mol% or less, based on the total amount of the tetracarboxylic dianhydride. When the diamine component and the tetracarboxylic dianhydride component (hereinafter sometimes referred to simply as tetracarboxylic dianhydride) are reacted to obtain polyglycine, a known method can be used. The reaction using tetracarboxylic dianhydride will be described below. In the present embodiment, the polymerization reaction method of the tetracarboxylic dianhydride and the diamine component is not particularly limited. In general, the polymerization reaction can be made into polylysine by mixing in an organic solvent.

使四羧酸二酐與二胺成分在有機溶劑中混合的方法，例如有使二胺成分分散或溶解於有機溶劑的溶液進行攪拌，且直接添加四羧酸二酐或將四羧酸二酐分散或溶解於有機溶劑中而進行添加的方法；將二胺成分添加於使四羧酸二酐分散或溶解於有機溶劑之溶液中的方法；交互添加四羧酸二酐與二胺成分的方法等。另外，四羧酸二酐及二胺成分中至少一方為由複數種化合物所構成時，可在預先混合此等複數種成分的狀態下進行聚合反應，或也可個別依序反應。A method of mixing a tetracarboxylic dianhydride and a diamine component in an organic solvent, for example, a solution in which a diamine component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride or a tetracarboxylic dianhydride is directly added thereto. a method of dispersing or dissolving in an organic solvent for addition; a method of adding a diamine component to a solution for dispersing or dissolving a tetracarboxylic dianhydride in an organic solvent; and a method of alternately adding a tetracarboxylic dianhydride and a diamine component Wait. In addition, when at least one of the tetracarboxylic dianhydride and the diamine component is composed of a plurality of compounds, the polymerization reaction may be carried out in a state in which the plurality of components are mixed in advance, or may be sequentially reacted individually.

使四羧酸二酐與二胺成分在有機溶劑中進行聚合反應時之溫度，通常為0℃~150℃，較佳為5℃~100℃，更佳為10℃~80℃。溫度越高，聚合反應越快結束，但是溫度太高時，有時無法得到高分子量之聚合物。另外，聚合反應可在任意濃度下進行，但由於濃度太低時難以獲得高分子量的聚合物，濃度太高時，反應液體之黏性過高，使得均勻攪拌變得困難，因此較佳為1~50質量%，更佳為5~30質量%。反應初期可在高濃度下進行，之後，再追加有機溶劑。投入濃度係指四羧酸二酐與二胺成分之合計質量的濃度。The temperature at which the tetracarboxylic dianhydride and the diamine component are polymerized in an organic solvent is usually from 0 ° C to 150 ° C, preferably from 5 ° C to 100 ° C, more preferably from 10 ° C to 80 ° C. The higher the temperature, the faster the polymerization reaction ends, but when the temperature is too high, a high molecular weight polymer may not be obtained. Further, the polymerization reaction can be carried out at any concentration, but it is difficult to obtain a polymer having a high molecular weight because the concentration is too low, and when the concentration is too high, the viscosity of the reaction liquid is too high, so that uniform stirring becomes difficult, so it is preferably 1 ~50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent is added. The input concentration means the concentration of the total mass of the tetracarboxylic dianhydride and the diamine component.

上述反應時所用的有機溶劑，只要是可溶解生成之聚醯胺酸者時，無特別限定。具體例有N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸或γ-丁內酯等。此等可單獨使用或混合使用。此外，可為不溶解聚醯胺酸的溶劑或在生成之聚醯胺酸不會析出的範圍內，可與上述溶劑混合使用。The organic solvent used in the above reaction is not particularly limited as long as it is a polylysine which can be produced by dissolution. Specific examples are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl alum , tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene or γ-butyrolactone. These can be used alone or in combination. Further, it may be used in combination with the above solvent in a range in which the solvent which does not dissolve the polyamic acid or the polyamic acid which is formed does not precipitate.

有機溶劑中之水分會妨礙聚合反應，且成為使生成後之聚醯胺酸水解之原因，因此有機溶劑盡可能使用經脫水乾燥者。The water in the organic solvent hinders the polymerization reaction and causes hydrolysis of the produced polyglycolic acid. Therefore, the organic solvent is desiccated as much as possible.

欲得到聚醯胺酸用之聚合反應用的四羧酸二酐與二胺成分之比率，以莫耳比表示，較佳為1：0.8~1：1.2，此莫耳比越接近1：1時，由其所得之聚醯胺酸之分子量越大。聚醯胺酸之分子量過小時，所得之塗膜強度有時不足，相反的，聚醯胺酸之分子量過大時，由其所製造之液晶配向劑之黏度過高，有時塗膜形成時之作業性、塗膜之均勻性變差。因此，本發明之液晶配向劑用之聚醯胺酸的重量平均分子量，較佳為2,000~500,000，更佳為5,000~300,000。The ratio of the tetracarboxylic dianhydride to the diamine component for the polymerization reaction for polyproline is expressed by the molar ratio, preferably 1:0.8 to 1:1.2, and the molar ratio is closer to 1:1. At the time, the molecular weight of the polylysine obtained therefrom is larger. When the molecular weight of the poly-proline is too small, the obtained coating film strength may be insufficient. Conversely, when the molecular weight of the poly-proline is too large, the viscosity of the liquid crystal alignment agent produced by the liquid is too high, and sometimes the coating film is formed. Workability and uniformity of the coating film deteriorate. Therefore, the weight average molecular weight of the polyamic acid for use in the liquid crystal alignment agent of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000.

本實施形態中，為了得到聚醯胺酸時，使用四羧酸二酐與二胺成分，其中二胺成分為使用含有上述式(1)表示之特定二胺與上述選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物的二胺成分、或含有上述式(1)表示之特定二胺與上述選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與上述式(3)表示之二胺的二胺成分等之上述二胺成分。以使用選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物為例，進行以下說明。In the present embodiment, in order to obtain polyamic acid, a tetracarboxylic dianhydride and a diamine component are used, wherein the diamine component is a specific diamine represented by the above formula (1) and is selected from the above formula (2- 1) a diamine component of at least one diamine compound in a group of diamine compounds represented by formula (2-2) and formula (2-3), or a specific diamine represented by the above formula (1) and the above-mentioned selection Free diamine component of at least one diamine compound represented by the above diamine compound represented by the above formula (2-1), formula (2-2) and formula (2-3) and the diamine represented by the above formula (3) And the above diamine component. The following description will be made by taking, as an example, at least one type of diamine compound selected from the group consisting of the diamine compounds represented by the above formula (2-1), formula (2-2) and formula (2-3).

使用選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物時，較適合使用之四羧酸二酐係上述式(5)中之R⁶為式[A-1]、式[A-2]、式[A-3]、式[A-5]、式[A-6]、式[A-8]、式[A-16]、式[A-18]、式[A-19]、式[A-21]、式[A-25]、式[A-26]、式[A-27]、式[A-31]、式[A-32]、式[A-35]、式[A-38]、式[A-46]或式[A-47]。When at least one diamine compound selected from the group consisting of the diamine compounds represented by the above formula (2-1), formula (2-2) and formula (2-3) is used, a tetracarboxylic dianhydride system which is preferably used is used. R ⁶ in the above formula (5) is a formula [A-1], a formula [A-2], a formula [A-3], a formula [A-5], a formula [A-6], and a formula [A-8]. ], formula [A-16], formula [A-18], formula [A-19], formula [A-21], formula [A-25], formula [A-26], formula [A-27] , [A-31], formula [A-32], formula [A-35], formula [A-38], formula [A-46] or formula [A-47].

如此所得之聚醯胺酸可以下述式(6)之重複單位表示。The polylysine thus obtained can be represented by the repeating unit of the following formula (6).

上述式(6)中，R^a、R^b、R^c係來自上述式(1)、選自由上述式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物或式(4)表示之二胺化合物等之基團，使用式(1)表示之二胺時，R^a及R^b係氫、R^c係-伸苯基-Y¹-R¹-NH-CX-HN-R²-Y²-伸苯基，使用式(4)表示之二胺時，R^a係H，R^b係H，R^c係X⁵。R⁶係與上述式(5)表示之四羧酸二酐中之R⁶相同意義。In the above formula (6), R ^a , R ^b and R ^c are derived from the above formula (1) and are selected from the diamines represented by the above formula (2-1), formula (2-2) and formula (2-3). When a diamine compound represented by the formula (4) or a group represented by the formula (1) is used as a group of the compound, the R ^a and the R ^b are hydrogen, and the R ^c system is a benzene derivative. -Y ¹ -R ¹ -NH-CX-HN-R ² -Y ² -phenylene, when using the diamine represented by the formula (4), R ^a is H, R ^b is H, and R ^c is X ⁵ . The R ⁶ system has the same meaning as R ⁶ in the tetracarboxylic dianhydride represented by the above formula (5).

<液晶配向劑><Liquid alignment agent>

本實施形態之液晶配向劑係含有如上述所得之聚醯胺酸者，通常為將此等之聚合物溶解於有機溶劑後的塗佈液。此液晶配向劑所含有之聚合物，除上述聚醯胺酸外，可含有具有其他構造的聚合物。液晶配向劑所含有之有機溶劑，只要是容藉含有之聚合物者，即無特別限定。The liquid crystal alignment agent of the present embodiment contains the polyamic acid obtained as described above, and is usually a coating liquid obtained by dissolving such a polymer in an organic solvent. The polymer contained in the liquid crystal alignment agent may contain a polymer having another structure in addition to the above polyamic acid. The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as it is contained in the polymer.

有機溶劑之具體例有N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-甲基己內醯胺、2-吡咯烷酮、N-乙基吡咯烷酮、N-乙烯基吡咯烷酮、二甲基亞碸、四甲基脲、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯或1,3-二甲基-咪唑酮等。此等可單獨1種或混合2種以上使用。Specific examples of the organic solvent are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethylurea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone or 1,3-dimethyl- Imidazolium and the like. These may be used alone or in combination of two or more.

又，即使單獨使用也無法溶解聚合物之溶劑，只要於聚合物不析出的範圍內，亦可與本實施形態之液晶配向劑混合。特別是乙基溶纖素、丁基溶纖素、乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯及乳酸異戊酯等具有低表面張力的溶劑，藉由混合此溶劑可提高對基板之塗膜均勻性。此等溶劑可單獨1種或混合2種以上使用。Further, the solvent of the polymer cannot be dissolved even if it is used alone, and it may be mixed with the liquid crystal alignment agent of the present embodiment as long as it does not precipitate in the polymer. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1- Ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl Ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, lactate n A solvent having a low surface tension such as propyl ester, n-butyl lactate or isoamyl lactate, and the uniformity of coating film on the substrate can be improved by mixing the solvent. These solvents may be used alone or in combination of two or more.

具有低表面張力的溶劑的使用量較佳為液晶配向劑所含之全部溶劑之5~80質量%，更佳為20~60質量%。The amount of the solvent having a low surface tension is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass based on the total of the solvent contained in the liquid crystal alignment agent.

本實施形態之液晶配向劑，除了上述聚合物及有機溶劑外，可含有各種添加劑。The liquid crystal alignment agent of the present embodiment may contain various additives in addition to the above polymer and organic solvent.

例如提高膜厚之均勻性或表面平滑性的添加劑，例如有氟系界面活性劑、矽氧系界面活性劑或非離子系界面活性劑等。For example, an additive which improves the uniformity of the film thickness or the surface smoothness may be, for example, a fluorine-based surfactant, a ruthenium-based surfactant, or a nonionic surfactant.

例如有F TOP EF301、EF303、EF352(TOHKEMPRODUCTS公司製造)、Megafac F171、F173、R-30(大日本油墨公司製造)、Fluorad FC430、FC431(住友3M公司製造)、ASAHIGUARD AG710、Suflon S-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子公司製造)等。此等界面活性劑之使用比例係相對於液晶配向劑中所含之聚合物成分100質量份，較佳為0.01~2質量份，更佳為0.01~1質量份。For example, F TOP EF301, EF303, EF352 (manufactured by TOHKEMPRODUCTS), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), ASAHIGUARD AG710, Suflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The ratio of use of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.

提高液晶配向膜與基板之密著性之添加劑的具體例有含有官能性矽烷之化合物、含有環氧基之化合物等。Specific examples of the additive for improving the adhesion between the liquid crystal alignment film and the substrate include a compound containing a functional decane, a compound containing an epoxy group, and the like.

例如有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-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基三胺、N-三甲氧基矽烷基丙基三伸乙基三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、N-苄基-3-胺基丙基三甲氧基矽烷、N-苄基-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(氧伸乙基)-3-胺基丙基三甲氧基矽烷、N-雙(氧伸乙基)-3-胺基丙基三乙氧基矽烷、乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、丙三醇二縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、1,3,5,6-四縮水甘油基-2,4-己二醇、N,N,N’,N’-四縮水甘油基-間-二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷或N,N,N’,N’-四縮水甘油基-4,4’-二胺基二苯基甲烷等。此等化合物之添加量係相對於液晶配向劑中所含之聚合物成分100質量份，較佳為0.1~30質量份，更佳為1~20質量份。未達0.1質量份時，則無法期待密著性提高的效果，若多於30質量份時，則有液晶之配向性變差的情形。For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxy decane, 3-ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyltrimethoxy decane, N-ethoxycarbonyl-3-aminopropyl three Ethoxy decane, N-triethoxydecyl propyl triethylidene triamine, N-trimethoxydecyl propyl triethylidene triamine, 10-trimethoxydecyl-1,4, 7-triazanonane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltri Ethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethyl)-3- Aminopropyltrimethoxydecane, N-bis(oxyethyl)-3- Aminopropyl triethoxy decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-four Glycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino) Methyl)cyclohexane or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like. The amount of the compound to be added is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. When it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and when it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

本實施形態之液晶配向劑中，除上述以外，在不損及本發明效果的範圍內，可添加聚合物以外之聚合物成分。又，為了改變液晶配向膜之介電率或導電性等之電特性，亦可添加介電體或導電物質，為了提高作為液晶配向膜時之膜的硬度或緊密度，可添加交聯性化合物等。In addition to the above, the liquid crystal alignment agent of the present embodiment may contain a polymer component other than the polymer within a range that does not impair the effects of the present invention. Further, in order to change the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film, a dielectric or a conductive material may be added, and a crosslinkable compound may be added in order to improve the hardness or tightness of the film as a liquid crystal alignment film. Wait.

本實施形態之液晶配向劑中之固體成分的濃度可依據目的之液晶配向膜的膜厚來適當變更，但是為了形成無缺陷之塗膜，且可得到作為液晶配向膜適當的膜厚，較佳為1~20質量%，更佳為2~10質量%。The concentration of the solid component in the liquid crystal alignment agent of the present embodiment can be appropriately changed depending on the film thickness of the intended liquid crystal alignment film. However, in order to form a coating film having no defect, it is preferable to obtain a film thickness suitable as the liquid crystal alignment film. It is 1 to 20% by mass, more preferably 2 to 10% by mass.

本發明之液晶配向劑可摻合含有上述聚醯胺酸與由不同分子構造所構成之可溶性聚醯亞胺、聚醯胺酸、聚醯胺酸酯等。此時，考慮所得之聚醯亞胺膜實現所要的特性時，上述聚醯胺酸之含量相對於其他含有之可溶性聚醯亞胺、聚醯胺酸、聚醯胺酸酯等合併的全量(100莫耳%)，較佳為10莫耳%~90莫耳%。The liquid crystal alignment agent of the present invention may be blended with the above polylysine and soluble polyimine, polylysine, polyamine or the like which are composed of different molecular structures. At this time, in consideration of the desired properties of the obtained polyimide film, the total amount of the polylysine is combined with other soluble polyimine, polylysine, polyamine, and the like ( 100 mol%), preferably 10 mol% to 90 mol%.

<液晶配向劑><Liquid alignment agent>

本實施形態之液晶配向劑係塗佈於基板上進行燒成後，以摩擦處理或光照射等進行配向處理。或於垂直配向性之液晶顯示元件用途時等，可未經配向處理，作為液晶配向膜使用。此時，使用的基板只要是透明性高的基板，則無特別限制，可使用玻璃基板或丙烯酸基板或聚碳酸酯基板等之塑膠基板等，但是從製程簡單化的觀點，較佳為使用形成驅動液晶用之ITO(Indium Tin Oxide)電極等的基板。又，反射型液晶顯示元件時，僅為單側基板時，也可使用矽晶圓等之不透明的基板。此時之電極亦可使用將鋁等的光反射的材料。The liquid crystal alignment agent of the present embodiment is applied onto a substrate and fired, and then subjected to alignment treatment by rubbing treatment or light irradiation. Or when it is used for a liquid crystal display element of a vertical alignment, it can be used as a liquid crystal alignment film without alignment treatment. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. However, from the viewpoint of simplification of the process, it is preferably used. A substrate such as an ITO (Indium Tin Oxide) electrode for driving a liquid crystal. Further, in the case of a reflective liquid crystal display device, when it is only a single-sided substrate, an opaque substrate such as a germanium wafer can be used. A material that reflects light such as aluminum can also be used as the electrode at this time.

液晶配向劑之塗佈方法並無特別限定，工業上一般為以網版印刷、膠版印刷、彈性凸版印刷或噴墨等進行的方法。其他塗佈方法例如有浸漬法或使用輥塗佈機、狹縫塗佈機、旋轉器等的方法，可配合目的來使用這些塗佈機。The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, it is generally a method of performing screen printing, offset printing, elastic relief printing, or inkjet. Other coating methods include, for example, a dipping method or a method using a roll coater, a slit coater, a spinner, etc., and these coaters can be used for the purpose.

塗佈有液晶配向劑之基板的燒成，可藉由溫度100~350℃之任意溫度進行，較佳為溫度150~300℃，更佳為溫度180~250℃。液晶配向劑中含有聚醯胺酸或聚醯胺酸酯時，因此燒成溫度，對聚醯亞胺之轉化率會產生變化，但是本發明之液晶配向劑不一定需要100%醯亞胺化。因此。燒成時間可設定為任意時間，但是燒成時間過短時，因殘存溶劑之影響，有時會發生顯示不良，因此較佳為5~60分鐘，更佳為10~40分鐘。The baking of the substrate coated with the liquid crystal alignment agent can be carried out at any temperature of 100 to 350 ° C, preferably 150 to 300 ° C, more preferably 180 to 250 ° C. When the liquid crystal alignment agent contains polylysine or polyphthalate, the firing temperature changes with respect to the conversion rate of the polyimine, but the liquid crystal alignment agent of the present invention does not necessarily require 100% ruthenium. . therefore. The firing time can be set to any time. However, when the baking time is too short, the display failure may occur due to the influence of the residual solvent. Therefore, it is preferably 5 to 60 minutes, more preferably 10 to 40 minutes.

燒成後之塗膜厚度，太厚時，對於液晶顯示元件之消耗電力較不利，過薄時，液晶顯示元件之可靠性有時會降低，因此較佳為5~300nm，更佳為10~100nm。使液晶水平配向或傾斜配向時，燒成後的塗膜以摩擦或偏光紫外線照射等進行處理。When the thickness of the coating film after firing is too thick, the power consumption of the liquid crystal display element is unfavorable. When the thickness is too thin, the reliability of the liquid crystal display element may be lowered, so that it is preferably 5 to 300 nm, more preferably 10 to 10. 100nm. When the liquid crystal is aligned horizontally or obliquely, the coating film after firing is treated by rubbing or polarized ultraviolet irradiation or the like.

<液晶顯示元件><Liquid crystal display element>

本實施形態之液晶顯示元件係藉由上述方法，由本實施形態之液晶配向劑得到附液晶配向膜之基板後，以公知方法製作液晶胞(cell)，作成液晶顯示元件者。In the liquid crystal display device of the present embodiment, the substrate to which the liquid crystal alignment film is attached is obtained from the liquid crystal alignment agent of the present embodiment, and a liquid crystal cell is produced by a known method to form a liquid crystal display element.

舉出液晶胞製作之一例，如下述。首先，準備形成有液晶配向膜的一對基板。接著，在其一之基板的液晶配向膜上散佈間隔物，使液晶配向膜面成為內側，貼合另一基板後，減壓注入液晶進行封閉。或於散佈有間隔物的液晶配向膜面上滴入液晶後，貼合基板，進行封閉。此時之間隔物的厚度較佳為1~30μm，更佳為2~10μm。An example of the production of liquid crystal cells is as follows. First, a pair of substrates on which a liquid crystal alignment film is formed are prepared. Next, a spacer is spread on the liquid crystal alignment film of one of the substrates, and the liquid crystal alignment film surface is placed inside. After bonding the other substrate, the liquid crystal is injected under reduced pressure to be sealed. Or, the liquid crystal is dripped on the liquid crystal alignment film surface in which the spacer is spread, and the board|substrate is bonded, and it is sealing. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

使用本實施形態之液晶配向劑製作的液晶顯示元件係顯示品質及信賴性優異，可適用於大畫面且高精細之液晶電視等。The liquid crystal display element produced by using the liquid crystal alignment agent of the present embodiment is excellent in display quality and reliability, and can be applied to a large-screen, high-definition liquid crystal television or the like.

如上述，藉由使用本發明之液晶配向劑時，體積電阻率不易因光而變化，且顯示低的體積電阻率，摩擦處理時對膜表面之傷害或切削較少，液晶之配向性良好，可得到高透過率的液晶配向膜。又，使用本發明之液晶配向劑所得之液晶配向膜係低電阻，使用此等之液晶胞之殘留DC特性良好，離子密度也低，可提供殘像等級低之高品質的液晶顯示元件。又，本發明之液晶配向劑也可用於構成光配向性之配向膜。As described above, when the liquid crystal alignment agent of the present invention is used, the volume resistivity is not easily changed by light, and the volume resistivity is low, and the film surface is less damaged or cut during the rubbing treatment, and the alignment of the liquid crystal is good. A liquid crystal alignment film having a high transmittance can be obtained. Further, the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention has low resistance, and the liquid crystal cell using these has good residual DC characteristics and low ion density, and can provide a high quality liquid crystal display element having a low afterimage level. Further, the liquid crystal alignment agent of the present invention can also be used as an alignment film constituting a photoalignment.

[實施例][Examples]

以下舉實施例，詳細說明本實施形態，但是本發明不限於此等實施例。The present embodiment will be described in detail below with reference to examples, but the present invention is not limited to the embodiments.

下述實施例及比較例所使用的簡稱如下述。The abbreviations used in the following examples and comparative examples are as follows.

DA-1：對苯二胺DA-1: p-phenylenediamine

DA-2：1,3-雙(4-胺基苯乙基)脲DA-2: 1,3-bis(4-aminophenethyl)urea

DA-3：3,5-二胺基苯甲酸DA-3: 3,5-diaminobenzoic acid

DA-4：下述合成例2所記載之二胺化合物DA-4DA-4: Diamine compound DA-4 described in Synthesis Example 2 below

DA-5：4,4’-二胺基二苯基胺DA-5: 4,4'-diaminodiphenylamine

DA-6：4,4’-二胺基二苯基甲烷DA-6: 4,4'-diaminodiphenylmethane

CA-1：1,2,3,4-環丁烷四羧酸二酐CA-1:1,2,3,4-cyclobutane tetracarboxylic dianhydride

CA-2：苯均四酸二酐CA-2: pyromellitic dianhydride

CA-3：雙環[3,3,0]辛烷-2,4,6,8-四羧酸二酐CA-3: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

DMSO：二甲基亞碸DMSO: dimethyl hydrazine

又，合成例中，¹H-NMR係指分子內氫原子之核磁共振光譜，表示所得之化合物之光譜數據。Further, in the synthesis example, ¹ H-NMR refers to a nuclear magnetic resonance spectrum of a hydrogen atom in the molecule, and represents spectral data of the obtained compound.

[合成例1][Synthesis Example 1]

DA-2：1,3-雙(4-胺基苯乙基)脲之合成DA-2: Synthesis of 1,3-bis(4-aminophenethyl)urea

室溫下，經氮取代後之四口燒瓶中，加入2-(4-硝基苯基)乙胺鹽酸鹽[C](52.50g、259mmol)、碳酸雙(4-硝基苯基)酯[D](37.53g、123mmol)及THF(四氫呋喃)(1877g)，其中再添加三乙胺(74.90g、740mmol)及4-N,N-二甲基胺基吡啶(3.01g、24.7mmol)，以機械攪拌子攪拌。以HPLC(高速液體層析)追蹤反應，反應終了後，將反應溶液添加於純水(9L)中，攪拌30分鐘。然後，過濾，以純水(1L)洗淨，得到白色固體之粗物。此所得之白色固體以甲醇(488g)，且使用超音波裝置分散洗淨後，進行過濾、乾燥，得到白色固体之二硝基化合物[E](得量42.3g、收率96%)。2-(4-Nitrophenyl)ethylamine hydrochloride [C] (52.50 g, 259 mmol), bis(4-nitrophenyl) carbonate was added to a four-necked flask after nitrogen substitution at room temperature. Ester [D] (37.53 g, 123 mmol) and THF (tetrahydrofuran) (1877 g), further adding triethylamine (74.90 g, 740 mmol) and 4-N,N-dimethylaminopyridine (3.01 g, 24.7 mmol) ), stirring with a mechanical stirrer. The reaction was followed by HPLC (High Speed Liquid Chromatography). After the reaction was completed, the reaction solution was added to purified water (9 L) and stirred for 30 minutes. Then, it was filtered, and washed with pure water (1 L) to obtain a crude solid of white solid. The obtained white solid was methanol (488 g), and washed with an ultrasonic apparatus, and then filtered and dried to obtain a dinitro compound [E] as a white solid (yield: 42.3 g, yield: 96%).

¹H-NMR(400MHz，DMSO-d6，δ_ppm)：8.11-8.08(4H,m)，7.43-7.40(4H,m)，5.89(2H,t)，3.24-3.19(4H,q)，2.76(4H,t)。 ¹ H-NMR (400 MHz, DMSO-d6, δ _ppm ): 8.11-8.08 (4H, m), 7.43-7.40 (4H, m), 5.89 (2H, t), 3.24 - 3.19 (4H, q), 2.76 (4H, t).

將化合物[E](42.32g、118mmol)、5%鈀碳(5%Pd/C)(4.23g)及1，4-二噁烷(2031g)之混合物以氮取代後，再以氫重新取代，在氫存在下，以室溫攪拌。以HPLC追蹤反應，反應終了後，以矽藻土過濾觸媒。然後，減壓下，餾除濾液之溶劑，得到白色固體之粗物。所得之粗物中添加2-丙醇(85g)，以超音波裝置分散洗淨後，進行過濾、乾燥得到白色固體之二胺化合物[DA-2](得量31.9g、收率91%)。A mixture of the compound [E] (42.32 g, 118 mmol), 5% palladium carbon (5% Pd/C) (4.23 g) and 1,4-dioxane (2031 g) was replaced with nitrogen and then replaced with hydrogen. Stir at room temperature in the presence of hydrogen. The reaction was followed by HPLC, and after the reaction was completed, the catalyst was filtered with diatomaceous earth. Then, the solvent of the filtrate was evaporated under reduced pressure to give a white solid. 2-propanol (85 g) was added to the obtained crude product, and the mixture was washed with an ultrasonic device, and then filtered and dried to obtain a white solid diamine compound [DA-2] (yield: 31.9 g, yield: 91%) .

¹H-NMR(400MHz，DMSO-d6，δ_ppm)：6.85-6.82(4H,m)，6.51-6.48(4H,m)，5.78(2H,t)，4.83(4H,s)，3.14-3.09(4H,m)，2.50-2.45(4H,m)。 ^{1 H-NMR (400MHz, DMSO} -d6, δ ppm): 6.85-6.82 (4H, m), 6.51-6.48 (4H, m), 5.78 (2H, t), 4.83 (4H, s), 3.14-3.09 (4H, m), 2.50-2.45 (4H, m).

[合成例2]二胺化合物DA-4之合成[Synthesis Example 2] Synthesis of Diamine Compound DA-4

二胺化合物DA-4之合成係依據以下反應式進行。The synthesis of the diamine compound DA-4 was carried out in accordance with the following reaction formula.

將化合物[G](29.92g，277mmol)及三乙胺(28.03g，277mmol)之四氫呋喃(300g)溶液冷卻至10℃以下，在注意發熱的狀態下，將化合物[F](60.76g，263mmol)之四氫呋喃(150g)溶液滴下。滴下終了後，使反應溫度提高至23℃，再進行反應。以HPLC(高速液體層析)確認反應終了後，將反應液全部倒入蒸餾水(2L)中，將析出的固体進行濾過、水洗後，以乙醇(450g)分散洗淨得到化合物[H](得量：72.91g，得率：92%)。A solution of the compound [G] (29.92 g, 277 mmol) and triethylamine (28.03 g, 277 mmol) in tetrahydrofuran (300 g) was cooled to 10 ° C or less, and the compound [F] (60.76 g, 263 mmol. The tetrahydrofuran (150 g) solution was dropped. After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction by HPLC (high-speed liquid chromatography), the reaction solution was poured into distilled water (2 L), and the precipitated solid was filtered, washed with water, and then washed with ethanol (450 g) to obtain compound [H] (obtained) Amount: 72.91 g, yield: 92%).

¹H-NMR(400MHz,DMSO-d6,δ_ppm)：9.79(1H,t)，9.10-9.09(2H,m)，9.00-8.96(1H,m)，8.61(1H,broad)，8.50-8.48(1H,m)，7.79-7.76(1H,m)，7.40-7.36(1H,m)，4.57(2H,s)。 ¹ H-NMR (400 MHz, DMSO-d6, δ _ppm ): 9.79 (1H, t), 9.10-9.09 (2H, m), 9.00-8.96 (1H, m), 8.61 (1H, broad), 8.50-8.48 (1H, m), 7.79-7.76 (1H, m), 7.40-7.36 (1H, m), 4.57 (2H, s).

接著，將化合物[H](72.00g，238mmol)、5%鈀碳(含水型，7.2g，10wt%)及1，4-二噁烷(720g)之混合物在氫存在下，以60℃攪拌。反應終了後，以矽藻土過濾觸媒後，使用蒸發器餾除溶劑得到粗物。所得之粗物以乙醇(360g)分散洗淨，得到二胺化合物[DA-4](得量：43.62g，得率：76%)。Next, a mixture of the compound [H] (72.00 g, 238 mmol), 5% palladium on carbon (aqueous form, 7.2 g, 10 wt%) and 1,4-dioxane (720 g) was stirred at 60 ° C in the presence of hydrogen. . After the completion of the reaction, the catalyst was filtered with diatomaceous earth, and the solvent was distilled off using an evaporator to obtain a crude material. The obtained crude product was washed with ethanol (360 g) to give a diamine compound [DA-4] (yield: 43.62 g, yield: 76%).

¹H-NMR(400MHz,DMSO-d6,δ_ppm)：8.64(1H,t)，8.50(1H,d)，8.44(1H,d)，7.67(1H,d)，7.34(1H,q)，6.23(2H,d)，5.94(1H,s)，4.87(4H,s)，4.39(2H,d)。 ^{1 H-NMR (400MHz, DMSO} -d6, δ ppm): 8.64 (1H, t), 8.50 (1H, d), 8.44 (1H, d), 7.67 (1H, d), 7.34 (1H, q), 6.23 (2H, d), 5.94 (1H, s), 4.87 (4H, s), 4.39 (2H, d).

實施例1Example 1

在附攪拌裝置及氮導入管之100ml之四口燒瓶中，加入DA-1 2.65g(24.5mmol)及DA-2 3.14g(10.5mmol)，再添加N-甲基-2-吡咯烷酮71g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 6.55g(33.4mmol)，再使固體成分濃度成為12質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌4小時得到聚醯胺酸(A1)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為274mPa‧s。此聚醯胺酸溶液20.09g中添加N-甲基-2-吡咯烷酮8.64g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液2.32g及丁基溶纖素7.76g，得到A1之濃度為6.0質量%的液晶配向劑。To a four-necked flask of 100 ml with a stirring device and a nitrogen introduction tube, 2.65 g (24.5 mmol) of DA-1 and 3.14 g (10.5 mmol) of DA-2 were added, and 71 g of N-methyl-2-pyrrolidone was added thereto. Stir and dissolve in the state of nitrogen. When the diamine solution was stirred, 6.55 g (33.4 mmol) of CA-1 was added, and the solid content concentration was adjusted to 12% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stirring was carried out for 4 hours to obtain a solution of polylysine (A1). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 274 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To the 20.09 g of the polyaminic acid solution, 8.64 g of N-methyl-2-pyrrolidone and 2.32 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 7.76 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A1 of 6.0% by mass.

表5係表示聚醯胺酸A1之合成使用之各二胺的量(莫耳)與四羧酸二酐的量(莫耳)及所得之聚醯胺酸溶液的黏度。同樣的，表5也表示以下說明之各實施例2~12及比較例1~3中，聚醯胺酸(A2~A12及B1~B3)之合成使用之各二胺的量(莫耳)與四羧酸的量(莫耳)及所得之聚醯胺酸溶液的黏度。Table 5 shows the amounts of each diamine (mol) used in the synthesis of polyamic acid A1 and the amount of tetracarboxylic dianhydride (mol) and the viscosity of the resulting polyamine solution. Similarly, Table 5 also shows the amounts of each diamine used in the synthesis of polyglycine (A2 to A12 and B1 to B3) in each of Examples 2 to 12 and Comparative Examples 1 to 3 described below (mole). The viscosity of the tetracarboxylic acid (mole) and the resulting polyamine solution.

(摩擦耐性)(frictional resistance)

將上述實施例1所得之液晶配向劑以1.0μm之過濾器過濾後，旋轉塗佈於附透明電極之玻璃基板上，在80℃之加熱板上乾燥5分鐘後，以220℃進行燒成20分鐘，得到膜厚100nm之聚醯亞胺膜。此聚醯亞胺膜以生絲布摩擦(輥徑120mm、轉數1000rpm、移動速度20mm/sec、押入量0.4mm)。此膜表面使用共焦點雷射顯微鏡觀察表面狀態，以倍率10倍觀察有無切削屑與有無傷痕。結果為無切削屑與無傷痕。此結果如表6所示。The liquid crystal alignment agent obtained in the above Example 1 was filtered through a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C for 5 minutes, and then fired at 220 ° C. In a minute, a polyimide film having a film thickness of 100 nm was obtained. This polyimide film was rubbed with a green cloth (roller diameter: 120 mm, number of revolutions: 1000 rpm, moving speed: 20 mm/sec, and pushing amount: 0.4 mm). The surface of the film was observed using a confocal laser microscope, and the presence or absence of chips and presence or absence of scratches was observed at a magnification of 10 times. The result is no chips and no scratches. The results are shown in Table 6.

(體積電阻率之測定)(Measurement of volume resistivity)

將上述所得之液晶配向劑以1.0μm之過濾器過濾後，旋轉塗佈於附ITO透明電極之玻璃基板上，在80℃之加熱板上乾燥5分鐘後，以220℃進行燒成20分鐘，形成膜厚200nm之塗膜(聚醯亞胺膜)。使此塗膜表面介於光罩蒸鍍鋁，形成1.0mmΦ之上部電極，作為體積電阻率測定用的試料。此試料之ITO電極與鋁電極之間施加10V的電壓，測定施加電壓180秒後之電流值，由此值與電極面積、膜厚之測定值計算得到體積電阻率。又，試料基板之下設置LED之背光，在亮燈下與熄燈下分別進行測定，測定因光造成之體積電阻率之變化。體積電阻率之值為未達1×10¹⁴Ω‧cm，且LED熄燈時之值(ρ1)除以LED亮燈時之值(ρ2)所得者(ρ1/ρ2)為0.7~1.5時，表示「良好」，此範圍以外表示「不良」。此結果如表7所示。ρ1/ρ2係1.1，表示「良好」。The liquid crystal alignment agent obtained above was filtered through a 1.0 μm filter, and then spin-coated on a glass substrate with an ITO transparent electrode, dried on a hot plate at 80° C. for 5 minutes, and then fired at 220° C. for 20 minutes. A coating film (polyimine film) having a film thickness of 200 nm was formed. The surface of the coating film was vapor-deposited with aluminum in a mask to form an upper electrode of 1.0 mm Φ , which was used as a sample for volume resistivity measurement. A voltage of 10 V was applied between the ITO electrode and the aluminum electrode of the sample, and the current value after the application of the voltage for 180 seconds was measured. From this value, the volume resistivity was calculated from the measured values of the electrode area and the film thickness. Further, a backlight of the LED was placed under the sample substrate, and measurement was performed under both the lighting and the light-off, and the change in volume resistivity due to light was measured. The value of the volume resistivity is less than 1 × 10 ¹⁴ Ω ‧ cm, and the value (ρ1) when the LED is turned off is divided by the value (ρ2) when the LED is turned on (ρ1 / ρ2) is 0.7 to 1.5, indicating "Good", outside this range means "bad". The results are shown in Table 7. Ρ1/ρ2 is 1.1, indicating "good".

(透過率測定)(transmittance measurement)

將上述所得之液晶配向劑以1.0μm之過濾器過濾後，配向劑旋轉塗佈於石英基板上，在80℃之加熱板上乾燥5分鐘後，以220℃進行燒成20分鐘，形成膜厚100nm之塗膜(聚醯亞胺膜)。試料基板藉由島津製作所製UV-3100PC測定透過率。由所得之數據計算得到350nm-750nm之平均透過率，該值為95%以上者，表示「良好」，未達95%者定義為「不良」。此結果如表6所示為「良好」。The liquid crystal alignment agent obtained above was filtered through a 1.0 μm filter, and then the alignment agent was spin-coated on a quartz substrate, dried on a hot plate at 80° C. for 5 minutes, and then fired at 220° C. for 20 minutes to form a film thickness. 100 nm coating film (polyimine film). The transmittance of the sample substrate was measured by UV-3100PC manufactured by Shimadzu Corporation. The average transmittance of 350 nm to 750 nm was calculated from the obtained data. If the value is 95% or more, it means "good", and if it is less than 95%, it is defined as "bad". This result is shown as "good" in Table 6.

(液晶胞之製作)(production of liquid crystal cell)

將上述所得之液晶配向劑以1.0μm之過濾器過濾後，旋轉塗佈於附透明電極之玻璃基板上，在80℃之加熱板上乾燥5分鐘後，以220℃進行燒成20分鐘，得到膜厚100nm之塗膜(聚醯亞胺膜)。此聚醯亞胺膜以生絲布摩擦(輥徑120mm、轉數1000rpm、移動速度30mm/sec、押入量0.2mm)後，於純水中進行1分鐘超音波照射，以80℃乾燥10分鐘。這種附液晶配向膜之基板準備2片，其一基板之液晶配向膜面設置6μm之間隔件後，2片基板之摩擦方向成為逆平行的方式予以組合，剩下液晶注入口，將周圍密封，製作晶胞間隙為6μm之空晶胞。將液晶(MLC-2041、Merk公司製)以常溫真空注入於此晶胞中，封閉注入口，作成液晶配向為逆平行配向的液晶胞。The liquid crystal alignment agent obtained above was filtered through a 1.0 μm filter, and then spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80° C. for 5 minutes, and then fired at 220° C. for 20 minutes to obtain a film. A coating film (polyimine film) having a film thickness of 100 nm. This polyimide film was rubbed with a green cloth (roller diameter: 120 mm, number of revolutions: 1000 rpm, moving speed: 30 mm/sec, and the amount of impregnation was 0.2 mm), and then subjected to ultrasonic irradiation for 1 minute in pure water, and dried at 80 ° C for 10 minutes. Two substrates of the liquid crystal alignment film are prepared, and a spacer of 6 μm is disposed on the liquid crystal alignment film surface of one substrate, and the rubbing directions of the two substrates are combined in an anti-parallel manner, leaving the liquid crystal injection port to seal the periphery. An empty cell with a cell gap of 6 μm was fabricated. Liquid crystal (MLC-2041, manufactured by Merk) was injected into the cell at room temperature, and the injection port was closed to form a liquid crystal cell in which the liquid crystal alignment was reversed.

(液晶配向性)(liquid crystal alignment)

以偏光顯微鏡觀察上述所得之液晶胞之配向狀態，有配向缺陷者表示「不良」，無配向缺陷者表示「良好」，結果液晶配向性為良好。此結果如表6所示。When the alignment state of the liquid crystal cell obtained above was observed by a polarizing microscope, those who had a mismatched defect indicated "poor", and those who did not have an alignment defect showed "good", and as a result, the liquid crystal alignment property was good. The results are shown in Table 6.

(離子密度測定)(Ion Density Measurement)

使用與上述同樣製作之液晶胞，使用東陽Technica公司製之6254型液晶物性評價裝置進行測定。測定係施加10V、0.01Hz之三角波，藉由三角形近似法算出相當於所得之波形之離子密度的面積，作為離子密度。測定時，液晶胞之溫度為60℃。此結果如表6所示。The liquid crystal cells produced in the same manner as described above were measured using a 6254 liquid crystal physical property evaluation device manufactured by Toyo Technica Co., Ltd. In the measurement, a triangular wave of 10 V and 0.01 Hz was applied, and an area corresponding to the ion density of the obtained waveform was calculated by a triangular approximation as an ion density. At the time of measurement, the temperature of the liquid crystal cell was 60 °C. The results are shown in Table 6.

(殘留DC之測定)(Measurement of residual DC)

使用與上述同樣製作之液晶胞，使用東陽Technica公司製之6254型液晶物性評價裝置之誘電吸收法進行測定。測定係在60℃之環境下進行，對晶胞施加30分鐘之10V之直流電壓後，經過1秒放電，其20分鐘後之殘留DC量未達500mV者表示「良好」，而500mV以上者表示「不良」。此結果如表6所示為「良好」。The liquid crystal cell produced in the same manner as above was measured by the electric absorption absorption method of the 6254 liquid crystal physical property evaluation apparatus manufactured by Dongyang Technica Co., Ltd. The measurement was carried out in an environment of 60 ° C. After applying a DC voltage of 10 V for 30 minutes to the unit cell, after 1 second of discharge, the residual DC amount after 20 minutes was less than 500 mV, indicating "good", and those above 500 mV were expressed. "bad". This result is shown as "good" in Table 6.

由以上評價結果得知，使用本實施例之液晶配向劑形成的聚醯亞胺膜，其摩擦耐性良好，透過率也良好。此外，體積電阻率也顯示低的值，且不易因光而變化，體積電阻率良好。作為液晶配向膜使用於液晶胞時，液晶之配向性良好，離子密度也低，殘留DC特性也良好。From the results of the above evaluation, it was found that the polyimide film formed using the liquid crystal alignment agent of the present example had good friction resistance and good transmittance. Further, the volume resistivity also shows a low value, and is not easily changed by light, and the volume resistivity is good. When the liquid crystal alignment film is used for a liquid crystal cell, the alignment of the liquid crystal is good, the ion density is also low, and the residual DC characteristics are also good.

實施例2Example 2

在附攪拌裝置及氮導入管之50ml之四口燒瓶中，加入DA-12.39g(8.0mmol)及DA-20.87g(8.0mmol)，再添加N-甲基-2-吡咯烷酮30g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 2.92g(14.9mmol)，再使固體成分濃度成為12質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌4小時得到聚醯胺酸(A2)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為281mPa‧s。此聚醯胺酸溶液16.98g中添加N-甲基-2-吡咯烷酮8.09g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液2.03g及丁基溶纖素6.77g，得到A2之濃度為6.0質量%的液晶配向劑。DA-12.39g (8.0mmol) and DA-20.87g (8.0mmol) were added to a 50ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, and 30 g of N-methyl-2-pyrrolidone was added thereto, and nitrogen was fed thereto. Stir and dissolve in the state. 2.92 g (14.9 mmol) of CA-1 was added to the state in which the diamine solution was stirred, and the solid content concentration was adjusted to 12% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stirring was carried out for 4 hours to obtain a solution of polyamic acid (A2). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 281 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To the 16.98 g of the polyaminic acid solution, 8.09 g of N-methyl-2-pyrrolidone and 2.03 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 6.77 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A2 of 6.0% by mass.

實施例3Example 3

在附攪拌裝置及氮導入管之100ml之四口燒瓶中，加入DA-1 2.65g(24.5mmol)及DA-2 3.14g(10.5mmol)，再添加N-甲基-2-吡咯烷酮85g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 5.25g(26.8mmol)，於氮氣氛下，以水溫攪拌2小時。然後添加CA-3 1.76g(7.0mmol)，再使固體成分濃度成為12質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以50℃攪拌16小時得到聚醯胺酸(A3)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為289mPa‧s。此聚醯胺酸溶液15.55g中添加N-甲基-2-吡咯烷酮7.02g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液1.83g及丁基溶纖素6.10g，得到A3之濃度為6.0質量%的液晶配向劑。In a 100 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.65 g (24.5 mmol) of DA-1 and 3.14 g (10.5 mmol) of DA-2 were added, and then 85 g of N-methyl-2-pyrrolidone was added thereto. Stir and dissolve in the state of nitrogen. After the diamine solution was stirred, 5.25 g (26.8 mmol) of CA-1 was added, and the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere. Then, 1.76 g (7.0 mmol) of CA-3 was added, and the solid content concentration was adjusted to 12% by mass, and N-methyl-2-pyrrolidone was added thereto, and the mixture was stirred at 50 ° C for 16 hours in a nitrogen atmosphere to obtain polylysine. Solution of (A3). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 289 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To the 15.55 g of the polyaminic acid solution, 7.02 g of N-methyl-2-pyrrolidone and 1.83 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 6.10 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A3 of 6.0% by mass.

實施例4Example 4

在附攪拌裝置及氮導入管之50ml之四口燒瓶中，加入DA-1 1.37g(12.6mmol)及DA-2 1.62g(5.4mmol)，再添加N-甲基-2-吡咯烷酮36.93g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 2.98g(15.2mmol)，於氮氣氛下，以水溫攪拌2小時。然後添加CA-2 0.39g(1.8mmol)，再使固體成分濃度成為12質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌3小時得到聚醯胺酸(A4)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為261mPa‧s。此聚醯胺酸溶液16.09g中添加N-甲基-2-吡咯烷酮6.96g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液1.86g及丁基溶纖素6.22g，得到A4之濃度為6.0質量%的液晶配向劑。1. In a 50 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.37 g (12.6 mmol) of DA-1 and 1.62 g (5.4 mmol) of DA-2 were added, and 36.93 g of N-methyl-2-pyrrolidone was further added. The mixture was stirred and dissolved while feeding nitrogen. 2.98 g (15.2 mmol) of CA-1 was added while stirring the diamine solution, and the mixture was stirred at a water temperature for 2 hours under a nitrogen atmosphere. Then, 0.39 g (1.8 mmol) of CA-2 was added, and the solid content concentration was adjusted to 12% by mass, and N-methyl-2-pyrrolidone was added thereto, and the mixture was stirred at a water temperature for 3 hours under a nitrogen atmosphere to obtain polylysine. Solution of (A4). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 261 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To the 16.09 g of the polyaminic acid solution, 6.96 g of N-methyl-2-pyrrolidone and 1.86 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 6.22 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A4 of 6.0% by mass.

實施例5Example 5

在附攪拌裝置及氮導入管之100ml之四口燒瓶中，加入DA-1 1.94g(18.0mmol)、DA-2 2.69g(9.0mmol)及DA-4 0.72g(3.0mmol)，再添加N-甲基-2-吡咯烷酮64.5g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 5.67g(28.8mmol)，再使固體成分濃度成為12質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌3小時得到聚醯胺酸(A5)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為281mPa‧s。此聚醯胺酸溶液15.58g中添加N-甲基-2-吡咯烷酮6.47g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液1.78g及丁基溶纖素5.95g，得到A5之濃度為6.0質量%的液晶配向劑。In a 100 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.94 g (18.0 mmol) of DA-1, 2.69 g (9.0 mmol) of DA-2, and 0.72 g (3.0 mmol) of DA-4 were added, followed by addition of N. 64.5 g of methyl-2-pyrrolidone was stirred and dissolved while being fed with nitrogen. When the diamine solution was stirred, 5.67 g (28.8 mmol) of CA-1 was added, and the solid content concentration was adjusted to 12% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stirring for 3 hours gave a solution of polyamine acid (A5). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 281 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To the 15.58 g of the polyaminic acid solution, 1.47 g of N-methyl-2-pyrrolidone and 1.78 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 5.90 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A5 of 6.0% by mass.

實施例6Example 6

在附攪拌裝置及氮導入管之50ml之四口燒瓶中，加入DA-1 0.64g(6.0mmol)、DA-2 2.98g(10.0mmol)及DA-30.60g(4.0mmol)，再添加N-甲基-2-吡咯烷酮33.5g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 3.72g(19.0mmol)，再使固體成分濃度成為15質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌4小時得到聚醯胺酸(A6)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為514mPa‧s。此聚醯胺酸溶液12.07g中添加N-甲基-2-吡咯烷酮10.14g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液1.79g及丁基溶纖素5.99g，得到A6之濃度為6.0質量%的液晶配向劑。In a 50 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-1 0.64 g (6.0 mmol), DA-2 2.98 g (10.0 mmol) and DA-30.60 g (4.0 mmol) were added, and N- was added. 33.5 g of methyl-2-pyrrolidone was stirred and dissolved while being fed with nitrogen. When the diamine solution was stirred, 3.72 g (19.0 mmol) of CA-1 was added, and the solid content concentration was changed to 15% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stirring was carried out for 4 hours to obtain a solution of polyamic acid (A6). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 514 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To the 12.07 g of the polyaminic acid solution, 10.14 g of N-methyl-2-pyrrolidone and 1.79 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 5.94 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A6 of 6.0% by mass.

實施例7Example 7

在附攪拌裝置及氮導入管之100ml之四口燒瓶中，加入DA-2 6.27g(21.0mmol)、DA-3 1.07g(7.0mmol)及DA-4 1.70g(7.0mmol)，再添加N-甲基-2-吡咯烷酮60.3g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 6.67g(34.0mmol)，再使固體成分濃度成為15質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌3小時得到聚醯胺酸(A7)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為433mPa‧s。此聚醯胺酸溶液14.94g中添加N-甲基-2-吡咯烷酮14.6g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液2.39g及丁基溶纖素7.98g，得到A7之濃度為6.0質量%的液晶配向劑。To a four-necked flask of 100 ml with a stirring device and a nitrogen introduction tube, 6.27 g (21.0 mmol) of DA-2, 1.07 g (7.0 mmol) of DA-3, and 1.70 g (7.0 mmol) of DA-4 were added, and N was further added. 60.3 g of -methyl-2-pyrrolidone was stirred and dissolved while being fed with nitrogen. 6.67 g (34.0 mmol) of CA-1 was added to the state in which the diamine solution was stirred, and the solid content concentration was changed to 15% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. The mixture was stirred for 3 hours to obtain a solution of polyamic acid (A7). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 433 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To 14.94 g of the polyaminic acid solution, 14.6 g of N-methyl-2-pyrrolidone and 2.39 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 7.08 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A7 of 6.0% by mass.

實施例8Example 8

在附攪拌裝置及氮導入管之100ml之四口燒瓶中，加入DA-2 8.96g(30.0mmol)、DA-3 3.04g(20.0mmol)，再添加N-甲基-2-吡咯烷酮83.0g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 9.41g(48.0mmol)，再使固體成分濃度成為15質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌6小時得到聚醯胺酸(A8)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為399mPa‧s。此聚醯胺酸溶液20.20g中添加N-甲基-2-吡咯烷酮22.22g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液3.18g及丁基溶纖素10.61g，得到A8之濃度為5.5質量%的液晶配向劑。To a four-necked flask of 100 ml with a stirring device and a nitrogen introduction tube, 8.96 g (30.0 mmol) of DA-2 and 3.04 g (20.0 mmol) of DA-3 were added, and 83.0 g of N-methyl-2-pyrrolidone was added thereto. The mixture was stirred and dissolved while feeding nitrogen. When the diamine solution was stirred, 9.41 g (48.0 mmol) of CA-1 was added, and the solid content concentration was adjusted to 15% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. The mixture was stirred for 6 hours to obtain a solution of polyamine acid (A8). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 399 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To 20.20 g of the polyaminic acid solution, 22.22 g of N-methyl-2-pyrrolidone and 3.18 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane were added. 10.61 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A8 of 5.5% by mass.

實施例9Example 9

在附攪拌裝置及氮導入管之50ml之四口燒瓶中，加入DA-1 1.55g(14.4mmol)、DA-2 0.48g(1.6mmol)，再添加N-甲基-2-吡咯烷酮31.2g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 3.04g(15.5mmol)，再使固體成分濃度成為10質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌6小時得到聚醯胺酸(A9)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為180mPa‧s。此聚醯胺酸溶液20.20g中添加N-甲基-2-吡咯烷酮4.89g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液2.02g及丁基溶纖素6.74g，得到A9之濃度為6.0質量%的液晶配向劑。To a 50 ml four-necked flask equipped with a stirrer and a nitrogen introduction tube, 1.55 g (14.4 mmol) of DA-1, 0.48 g (1.6 mmol) of DA-2, and 31.2 g of N-methyl-2-pyrrolidone were added. The mixture was stirred and dissolved while feeding nitrogen. When the diamine solution was stirred, 3.04 g (15.5 mmol) of CA-1 was added, and the solid content concentration was changed to 10% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stirring was carried out for 6 hours to obtain a solution of polyamic acid (A9). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 180 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To 20.20 g of the polyaminic acid solution, 4.89 g of N-methyl-2-pyrrolidone and 2.02 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 6.74 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A9 of 6.0% by mass.

實施例10Example 10

在附攪拌裝置及氮導入管之200ml之四口燒瓶中，加入DA-1 4.41g(40.8mmol)、DA-2 6.09g(20.4mmol)、DA-5 1.35g(6.8mmol)，再添加N-甲基-2-吡咯烷酮144.5g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 9.89g(50.5mmol)，再使固體成分濃度成為12質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌2小時。然後，攪拌的狀態下，添加CA-2 2.96g(13.4mmol)，再攪拌4小時得到聚醯胺酸(A10)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為288mPa‧s。此聚醯胺酸溶液57.14g中添加N-甲基-2-吡咯烷酮24.26g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液6.60g及丁基溶纖素22g，得到A10之濃度為6.0質量%的液晶配向劑。In a 200 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, 4.41 g (40.8 mmol) of DA-1, 6.09 g (20.4 mmol) of DA-2, and 1.35 g (6.8 mmol) of DA-5 were added, and N was further added. 144.5 g of -methyl-2-pyrrolidone was stirred and dissolved while being fed with nitrogen. When the diamine solution was stirred, 9.89 g (50.5 mmol) of CA-1 was added, and the solid content concentration was adjusted to 12% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stir for 2 hours. Then, 2.76 g (13.4 mmol) of CA-2 was added while stirring, and the mixture was further stirred for 4 hours to obtain a solution of polyamine acid (A10). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 288 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To the 57.14 g of the polyamidamine solution, 24.26 g of N-methyl-2-pyrrolidone and 6.60 g of a solution of 1.0% by weight of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 22 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A10 of 6.0% by mass.

實施例11Example 11

在附攪拌裝置及氮導入管之200ml之四口燒瓶中，加入DA-13.67g(33.9mmol)、DA-26.08g(20.4mmol)、DA-52.70g(13.6mmol)，再添加N-甲基-2-吡咯烷酮148.1g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 9.86g(49.8mmol)，再使固體成分濃度成為12質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌2小時。然後，攪拌的狀態下，添加CA-22.96g(13.4mmol)，再攪拌4小時得到聚醯胺酸(A11)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為307mPa‧s。此聚醯胺酸溶液57.54g中添加N-甲基-2-吡咯烷酮23.86g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液6.60g及丁基溶纖素22g，得到A11之濃度為6.0質量%的液晶配向劑。DA-13.67 g (33.9 mmol), DA-26.08 g (20.4 mmol), DA-52.70 g (13.6 mmol), and N-methyl group were added to a 200 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube. 148.1 g of -2-pyrrolidone was stirred and dissolved while being fed with nitrogen. When the diamine solution was stirred, 9.86 g (49.8 mmol) of CA-1 was added, and the solid content concentration was adjusted to 12% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stir for 2 hours. Then, while stirring, CA-22.96 g (13.4 mmol) was added, and the mixture was further stirred for 4 hours to obtain a solution of polyglycine (A11). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 307 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). 57.54g of the polyaminic acid solution was added with 6.86 g of N-methyl-2-pyrrolidone, and 6.60 g of a solution of 1.0% by weight of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 22 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A11 of 6.0% by mass.

實施例12Example 12

在附攪拌裝置及氮導入管之200ml之四口燒瓶中，加入DA-14.41g(40.8mmol)、DA-26.09g(20.4mmol)、DA-51.35g(6.8mmol)，再添加N-甲基-2-吡咯烷酮144.1g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 11.23g(57.3mmol)，再使固體成分濃度成為12質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌2小時。然後，攪拌的狀態下，添加CA-2 1.49g(6.8mmol)，再攪拌4小時得到聚醯胺酸(A12)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為288mPa‧s。此聚醯胺酸溶液57.84g中添加N-甲基-2-吡咯烷酮23.56g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液6.60g及丁基溶纖素22g，得到A12之濃度為6.0質量%的液晶配向劑。In a 200 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, DA-14.41 g (40.8 mmol), DA-26.09 g (20.4 mmol), DA-51.35 g (6.8 mmol) were added, and N-methyl group was further added. 144.1 g of -2-pyrrolidone was stirred and dissolved while being fed with nitrogen. When the diamine solution was stirred, 11.23 g (57.3 mmol) of CA-1 was added, and the solid content concentration was adjusted to 12% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stir for 2 hours. Then, 1.47 g (6.8 mmol) of CA-2 was added while stirring, and the mixture was further stirred for 4 hours to obtain a solution of polyamine acid (A12). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 288 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To the 57.84 g of the polyamidamine solution, 23.56 g of N-methyl-2-pyrrolidone and 6.60 g of a solution of 1.0% by weight of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 22 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of A12 of 6.0% by mass.

實施例13Example 13

在附攪拌裝置及氮導入管之300ml之四口燒瓶中，加入DA-619.83g(100.0mmol)，再添加N-甲基-2-吡咯烷酮111.0g、γ-丁內酯111.0g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 8.43g(43.0mmol)，以水溫攪拌2小時。然後，攪拌的狀態下，添加CA-210.91g(50.0mmol)，再攪拌6小時得到聚醯胺酸(PA1)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為323mPa‧s。此聚醯胺酸溶液25.00g中添加γ-丁內酯25.1g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液3.58g及丁基溶纖素9.38g，得到PA1之濃度為6.0質量%的溶液。然後，將所得之PA1之濃度為6.0質量%之溶液5.0g與實施例1所得之A1之濃度為6.0質量%的溶液20.0g予以混合，得到PA1與A1之混合比為PA1：A1=1：4(重量比)的液晶配向劑。DA-619.83 g (100.0 mmol) was added to a 300 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, and 111.0 g of N-methyl-2-pyrrolidone and 111.0 g of γ-butyrolactone were added thereto, and nitrogen was fed thereto. Stir and dissolve in the state. 8.43 g (43.0 mmol) of CA-1 was added while stirring the diamine solution, and the mixture was stirred at room temperature for 2 hours. Then, CA-210.91 g (50.0 mmol) was added while stirring, and the mixture was further stirred for 6 hours to obtain a solution of polyglycine (PA1). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 323 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To 25.00 g of this polyaminic acid solution, 25.1 g of γ-butyrolactone, 3.5% of N-methyl-2-pyrrolidone solution containing 3-aminopropyltriethoxysilane as 1.0% by weight, and butyl cellosolve were added. 9.38 g, a solution having a concentration of PA1 of 6.0% by mass was obtained. Then, 5.0 g of a solution having a concentration of PA1 of 6.0% by mass and 20.0 g of a solution having a concentration of A1 obtained in Example 1 of 6.0% by mass were mixed, and a mixing ratio of PA1 to A1 was obtained as PA1: A1=1: 4 (by weight) liquid crystal alignment agent.

比較例1Comparative example 1

在附攪拌裝置及氮導入管之100ml之四口燒瓶中，加入DA-13.78g(35.0mmol)，再添加N-甲基-2-吡咯烷酮83.0g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 6.52g(33.3mmol)，再使固體成分濃度成為10質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌4小時，得到聚醯胺酸(B1)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為110mPa‧s。此聚醯胺酸溶液15.00g中添加N-甲基-2-吡咯烷酮4.31g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液1.47g及丁基溶纖素3.67g，得到B1之濃度為6.0質量%的液晶配向劑。DA-13.78g (35.0mmol) was added to a 100-ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, and 83.0 g of N-methyl-2-pyrrolidone was further added thereto, and the mixture was stirred and dissolved while supplying nitrogen. 6.52 g (33.3 mmol) of CA-1 was added to the state in which the diamine solution was stirred, and the solid content concentration was 10% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stirring was carried out for 4 hours to obtain a solution of polylysine (B1). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 110 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To 15.00 g of the polyaminic acid solution, 4.31 g of N-methyl-2-pyrrolidone and 1.70 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 3.87 g of butyl cellosolve gave a liquid crystal alignment agent having a B1 concentration of 6.0% by mass.

比較例2Comparative example 2

在附攪拌裝置及氮導入管之100ml之四口燒瓶中，加入DA-26.27g(21.0mmol)，再添加N-甲基-2-吡咯烷酮83.0g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 3.92g(20.0mmol)，再使固體成分濃度成為10質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌4小時，得到聚醯胺酸(B2)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為129mPa‧s。此聚醯胺酸溶液24.00g中添加N-甲基-2-吡咯烷酮2.40g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液1.60g及丁基溶纖素12.00g，得到B2之濃度為6.0質量%的液晶配向劑。DA-26.27 g (21.0 mmol) was added to a 100 ml four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, and 83.0 g of N-methyl-2-pyrrolidone was further added thereto, and the mixture was stirred and dissolved while supplying nitrogen. When the diamine solution was stirred, 3.92 g (20.0 mmol) of CA-1 was added, and the solid content concentration was changed to 10% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stirring was carried out for 4 hours to obtain a solution of polylysine (B2). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 129 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). 2.00 g of N-methyl-2-pyrrolidone was added to 24.00 g of the polyamidamine solution, and 1.60 g of a solution of 1.0% by weight of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane was added. 12.00 g of butyl cellosolve gave a liquid crystal alignment agent having a concentration of B2 of 6.0% by mass.

比較例3Comparative example 3

在附攪拌裝置及氮導入管之100ml之四口燒瓶中，加入DA-5 4.58g(23.0mmol)，再添加N-甲基-2-吡咯烷酮65.0g，送入氮的狀態下攪拌溶解。將此二胺溶液進行攪拌的狀態下添加CA-1 4.33g(22.1mmol)，再使固體成分濃度成為10質量%的狀態，添加N-甲基-2-吡咯烷酮，於氮氣氛下，以水溫攪拌4小時，得到聚醯胺酸(B3)之溶液。此聚醯胺酸溶液在25℃時之黏度以E型黏度計(東機產業公司製)確認為223mPa‧s。此聚醯胺酸溶液15.11g中添加N-甲基-2-吡咯烷酮7.74g、含有3-胺基丙基三乙氧基矽烷為1.0重量%的N-甲基-2-吡咯烷酮溶液1.52g及丁基溶纖素6.09g，得到B3之濃度為5.0質量%的液晶配向劑。To a four-necked flask of 100 ml in a stirring apparatus and a nitrogen inlet tube, 4.58 g (23.0 mmol) of DA-5 was added, and 65.0 g of N-methyl-2-pyrrolidone was further added thereto, and the mixture was stirred and dissolved while supplying nitrogen. When the diamine solution was stirred, 4.33 g (22.1 mmol) of CA-1 was added, and the solid content concentration was changed to 10% by mass, and N-methyl-2-pyrrolidone was added thereto to give water under a nitrogen atmosphere. Stirring was carried out for 4 hours to obtain a solution of polyamic acid (B3). The viscosity of the polyamic acid solution at 25 ° C was confirmed to be 223 mPa ‧ by an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd.). To the 15.11 g of the polyaminic acid solution, 7.74 g of N-methyl-2-pyrrolidone and 1.52 g of a 1.0% by weight solution of N-methyl-2-pyrrolidone containing 3-aminopropyltriethoxydecane and 6.09 g of butyl cellosolve gave a liquid crystal alignment agent having a B3 concentration of 5.0% by mass.

使用實施例2~實施例13及比較例1~比較例3所得之液晶配向膜處理劑，與實施例1同樣製作聚醯亞胺膜及液晶胞等之評價試料，測定摩擦耐性、液晶配向性、離子密度、殘留DC及體積電阻率。所得結果如表6及表7所示。Using the liquid crystal alignment film treating agent obtained in Example 2 to Example 13 and Comparative Example 1 to Comparative Example 3, an evaluation sample such as a polyimide film or a liquid crystal cell was prepared in the same manner as in Example 1, and the friction resistance and the liquid crystal alignment property were measured. , ion density, residual DC and volume resistivity. The results obtained are shown in Tables 6 and 7.

使用實施例2~實施例13之液晶配向劑所形成之聚醯亞胺膜係摩擦耐性良好，透過率也良好。體積電阻率也低，且不易因光而變化，體積電阻率良好。此外，作為液晶配向膜使用於液晶胞時，液晶之配向性良好，離子密度也低，殘留DC特性也良好。因此得知本實施例之液晶配向膜可有效降低或防止殘像顯示不良。The polyimide film formed using the liquid crystal alignment agents of Examples 2 to 13 was excellent in friction resistance and also excellent in transmittance. The volume resistivity is also low, and it is not easily changed by light, and the volume resistivity is good. Further, when the liquid crystal alignment film is used for a liquid crystal cell, the alignment of the liquid crystal is good, the ion density is also low, and the residual DC characteristics are also good. Therefore, it is known that the liquid crystal alignment film of the present embodiment can effectively reduce or prevent the afterimage display failure.

而二胺成分僅使用DA-1之比較例1得知摩擦耐性低，且離子密度也顯示高的值。二胺成分僅使用DA-2之比較例2係作為液晶配向膜使用於液晶胞時，殘留DC特性差，且體積電阻率評價也差。二胺成分僅使用DA-5之比較例3係透過率特性不良，上述體積電阻率評價也不良。此外，作為液晶配向膜使用於液晶胞時，液晶之配向特性不良，且離子密度也顯示高的值。On the other hand, in Comparative Example 1 in which the diamine component was only DA-1, it was found that the friction resistance was low and the ion density also showed a high value. When Comparative Example 2 using only DA-2 as the diamine component was used as a liquid crystal alignment film as a liquid crystal alignment film, residual DC characteristics were inferior and volume resistivity evaluation was also inferior. In Comparative Example 3 in which only the DA-5 component of the diamine component was used, the transmittance characteristics were poor, and the volume resistivity evaluation was also poor. Further, when the liquid crystal alignment film is used for a liquid crystal cell, the alignment characteristics of the liquid crystal are poor, and the ion density also shows a high value.

產業上之利用性Industrial use

使用本發明之液晶配向劑可得到摩擦耐性優異，液晶之配向性也良好的液晶配向膜。此外，本發明之液晶配向膜係具有高的透過率，低電阻，電阻對光之感度也低，此外，使用於液晶胞時之離子密度也低，殘留DC特性良好，因此可用於要求高的顯示品質的液晶顯示元件。By using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film which is excellent in friction resistance and excellent in alignment property of liquid crystal can be obtained. Further, the liquid crystal alignment film of the present invention has high transmittance, low resistance, low sensitivity to light, and low ion density when used for liquid crystal cells, and good residual DC characteristics, so that it can be used for high requirements. Display quality liquid crystal display elements.

Claims (9)

一種液晶配向劑，其係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸的液晶配向劑，其特徵係前述二胺成分係以式(1)表示之二胺化合物含有5~60莫耳%，選自式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物含有40~95莫耳%， (式(1)中，X係氧原子或硫原子，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-或-COO-，R¹及R²係各自獨立為碳數1~3之伸烷基) A liquid crystal alignment agent which is a liquid crystal alignment agent containing a polyaminic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component, wherein the diamine component is a diamine compound represented by the formula (1). 5 to 60 mol%, at least one diamine compound selected from the group consisting of the diamine compounds represented by the formula (2-1), the formula (2-2) and the formula (2-3), containing 40 to 95 mol% , (In the formula (1), the X-based oxygen atom or the sulfur atom, and the Y ¹ and Y ² systems are each independently a single bond, -O-, -S-, -OCO- or -COO-, and R ¹ and R ² are each Independently an alkyl group having a carbon number of 1 to 3) 如申請專利範圍第1項之液晶配向劑，其中前述二胺成分為含有20莫耳%以下之量之式(3)表示的二胺化合物， (式(3)中，X¹係選自由-CONQ¹-、-O-、-NQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種2價有機基，Q¹係氫原子或碳數1~3之烷基，X²係選自碳數1~20之脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群之至少一種2價有機基或單鍵，X³係單鍵或選自由-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種2價有機基，Q²係氫原子或碳數1~3之烷基，X⁴係1價含氮芳香族雜環，n係1~4之整數)。The liquid crystal alignment agent of claim 1, wherein the diamine component is a diamine compound represented by the formula (3) in an amount of 20 mol% or less. (In the formula (3), X ¹ system selected from the group consisting of ^{-CONQ 1 -, - O -,} - NQ 1 -, - NQ 1 CO -, - CH 2 O- -OCO- and at least one of the groups of the divalent organic a group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ^{2 is} at least one selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon groups, and aromatic hydrocarbon groups. an organic group or a single bond, X ³ or selected from the group consisting of a single bond based ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH _{2) m} - (m is an integer of 1 to 5) at least one divalent organic group, Q ² hydrogen atom or alkyl group having 1 to 3 carbon atoms, X ⁴ is a monovalent nitrogen-containing aromatic heterocyclic ring, and n is 1 An integer of ~4). 一種液晶配向劑，其係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸的液晶配向劑，其特徵係前述二胺成分係式(1)表示之二胺化合物含有40~70莫耳%，以式(4)表示之二胺化合物含有30莫耳%以上者， (式(1)中，X係氧原子或硫原子，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-或-COO-，R¹及R²係各自獨立為碳數1~3之伸烷基) (式(4)中，X⁵係具有碳數6~30之芳香族環的有機基，n係1~4之整數)。A liquid crystal alignment agent which is a liquid crystal alignment agent containing a polyaminic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride component, wherein the diamine component represented by the formula (1) contains 40 ~70 mol%, the diamine compound represented by the formula (4) contains 30 mol% or more, (In the formula (1), the X-based oxygen atom or the sulfur atom, and the Y ¹ and Y ² systems are each independently a single bond, -O-, -S-, -OCO- or -COO-, and R ¹ and R ² are each Independently an alkyl group having a carbon number of 1 to 3) (In the formula (4), X ⁵ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4). 如申請專利範圍第3項之液晶配向劑，其中前述二胺成分為含有20莫耳%以下之量之式(3)表示的二胺化合物， (式(3)中，X¹係選自由-CONQ¹-、-O-、-NQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種2價有機基，Q¹係氫原子或碳數1~3之烷基，X²係選自由碳數1~20之脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群之至少一種2價有機基或單鍵，X³係單鍵，或選自由-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種2價有機基，Q²係氫原子或碳數1~3之烷基，X⁴係1價含氮芳香族雜環，n係1~4之整數)。The liquid crystal alignment agent of claim 3, wherein the diamine component is a diamine compound represented by the formula (3) in an amount of 20 mol% or less. (In the formula (3), X ¹ selected from the group consisting of ^{-CONQ 1 -, - O -,} - NQ 1 -, - NQ 1 CO -, - CH 2 O- and -OCO- groups of the at least one divalent organic a group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ² is at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. an organic group or a single bond, X ³ system single bond, or selected from the group consisting of ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH _{2) m} - (m is an integer of 1 to 5) at least one divalent organic group, Q ² hydrogen atom or alkyl group having 1 to 3 carbon atoms, X ⁴ is a monovalent nitrogen-containing aromatic heterocyclic ring, and n is a system An integer from 1 to 4). 如申請專利範圍第4項之液晶配向劑，其係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸的液晶配向劑，前述二胺成分含有以式(1)表示之二胺化合物20~60莫耳%，並且選自式(2-1)、式(2-2)及式(2-3)表示之二胺化合物所成群之至少一種二胺化合物與式(4)表示之二胺化合物以95：5~40：60之莫耳比，含有合計40~80莫耳%， (式(1)中，X係氧原子或硫原子，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-或-COO-，R¹及R²係各自獨立為碳數1~3之伸烷基) (式(4)中，X⁵係具有碳數6~30之芳香族環的有機基，n係1~4之整數)。A liquid crystal alignment agent according to claim 4, which comprises a liquid crystal alignment agent obtained by reacting a diamine component with a tetracarboxylic dianhydride component, wherein the diamine component is represented by the formula (1). a diamine compound of 20 to 60 mol%, and at least one diamine compound and a formula selected from the group consisting of diamine compounds represented by formula (2-1), formula (2-2) and formula (2-3) 4) The diamine compound is represented by a molar ratio of 95:5 to 40:60, and contains 40 to 80 mol% in total. (In the formula (1), the X-based oxygen atom or the sulfur atom, and the Y ¹ and Y ² systems are each independently a single bond, -O-, -S-, -OCO- or -COO-, and R ¹ and R ² are each Independently an alkyl group having a carbon number of 1 to 3) (In the formula (4), X ⁵ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4). 如申請專利範圍第5項之液晶配向劑，其中前述二胺成分為含有20莫耳%以下之量之以式(3)表示的二胺化合物， (式(3)中，X¹係選自由-CONQ¹-、-O-、-NQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種2價有機基，Q¹係氫原子或碳數1~3之烷基，X²係選自碳數1~20之脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群之至少一種2價有機基或單鍵，X³係單鍵或選自由-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種2價有機基，Q²係氫原子或碳數1~3之烷基，X⁴係1價含氮芳香族雜環，n係1~4之整數)。The liquid crystal alignment agent of claim 5, wherein the diamine component is a diamine compound represented by the formula (3) in an amount of 20 mol% or less. (In the formula (3), X ¹ selected from the group consisting of ^{-CONQ 1 -, - O -,} - NQ 1 -, - NQ 1 CO -, - CH 2 O- and -OCO- groups of the at least one divalent organic a group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ^{2 is} at least one selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon groups, and aromatic hydrocarbon groups. an organic group or a single bond, X ³ or selected from the group consisting of a single bond based ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH _{2) m} - (m is an integer of 1 to 5) at least one divalent organic group, Q ² hydrogen atom or alkyl group having 1 to 3 carbon atoms, X ⁴ is a monovalent nitrogen-containing aromatic heterocyclic ring, and n is 1 An integer of ~4). 一種液晶配向劑，其係含有使二胺成分與四羧酸二酐成分反應所得之聚醯胺酸的液晶配向劑，其特徵係前述二胺成分含有50莫耳%以上之以式(1)表示之二胺化合物，並且剩餘的成分為以90：10~40：60之莫耳比含有式(4)表示之二胺化合物與式(3)表示之二胺化合物， (式(1)中，X係氧原子或硫原子，Y¹及Y²係各自獨立為單鍵、-O-、-S-、-OCO-或-COO-，R¹及R²係各自獨立為碳數1~3之伸烷基) (式(4)中，X⁵係具有碳數6~30之芳香族環的有機基，n係1~4之整數) (式(3)中，X¹係選自由-CONQ¹-、-O-、-NQ¹-、-NQ¹CO-、-CH₂O-及-OCO-所成群之至少一種2價有機基，Q¹係氫原子或碳數1~3之烷基，X²係選自碳數1~20之脂肪族烴基、非芳香族環式烴基及芳香族烴基所成群之至少一種2價有機基或單鍵，X³係單鍵或選自由-O-、-NQ²-、-CONQ²-、-NQ²CO-、-COO-、-OCO-及-O(CH₂)_m-(m係1~5之整數)所成群之至少一種2價有機基，Q²係氫原子或碳數1~3之烷基，X⁴係1價含氮芳香族雜環，n係1~4之整數)。A liquid crystal alignment agent comprising a polyphthalic acid liquid crystal alignment agent obtained by reacting a diamine component and a tetracarboxylic dianhydride component, wherein the diamine component contains 50 mol% or more of the formula (1) a diamine compound represented by the formula (4) and a diamine compound represented by the formula (3), wherein the remaining component is a molar ratio of 90:10 to 40:60. (In the formula (1), the X-based oxygen atom or the sulfur atom, and the Y ¹ and Y ² systems are each independently a single bond, -O-, -S-, -OCO- or -COO-, and R ¹ and R ² are each Independently an alkyl group having a carbon number of 1 to 3) (In the formula (4), X ⁵ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4) (In the formula (3), X ¹ selected from the group consisting of ^{-CONQ 1 -, - O -,} - NQ 1 -, - NQ 1 CO -, - CH 2 O- and -OCO- groups of the at least one divalent organic a group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ^{2 is} at least one selected from the group consisting of aliphatic hydrocarbon groups having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon groups, and aromatic hydrocarbon groups. an organic group or a single bond, X ³ or selected from the group consisting of a single bond based ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO- and -O (CH _{2) m} - (m is an integer of 1 to 5) at least one divalent organic group, Q ² hydrogen atom or alkyl group having 1 to 3 carbon atoms, X ⁴ is a monovalent nitrogen-containing aromatic heterocyclic ring, and n is 1 An integer of ~4). 一種液晶配向膜，其特徵係由如申請專利範圍第1~7項中任一項之液晶配向劑所得者。A liquid crystal alignment film which is obtained by the liquid crystal alignment agent according to any one of claims 1 to 7. 一種液晶顯示元件，其特徵係具有如申請專利範圍第8項之液晶配向膜。A liquid crystal display element characterized by having a liquid crystal alignment film according to item 8 of the patent application.