TW202237702A - Liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof, and liquid crystal element wherein the liquid crystal element has low afterimage and high contrast ratio and the liquid crystal alignment film has high resilience - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent, which can obtain a liquid crystal element with low afterimage and high contrast ratio and can form a liquid crystal alignment film with high resilience. The liquid crystal alignment agent includes: polyamic acid [P], which includes a structural unit (I) derived from diamine, and has a chain structure having carbon number of 2 or more in the main chain of the structural unit (I) or a structural unit that is different from the structural unit (I), wherein the diamine has at least one acidic group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group; and a polymer [Q] (wherein, except for polyamic acid [P]), which is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.

Description

液晶配向劑、液晶配向膜及其製造方法、以及液晶元件Liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof, and liquid crystal element

本發明有關一種液晶配向劑、液晶配向膜及其製造方法、以及液晶元件。The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a manufacturing method thereof, and a liquid crystal element.

液晶元件被廣泛利用於電視或移動設備、各種監視器等中。伴隨此種多用途化，對液晶元件要求進一步的高品質化，並且在推進驅動方式或元件結構的改良的同時，推進作為液晶元件的構成材料之一的液晶配向膜的改良（例如，參照專利文獻1）。在專利文獻1中公開了：通過使用具有環式結構及經由氮原子而與所述環式結構鍵結所得的烷二基的二胺來製造聚醯胺酸、聚醯亞胺，來用作液晶配向劑的聚合物成分，從而改善殘像特性、電壓保持率、膜的透明性及對比度。 [現有技術文獻] [專利文獻] Liquid crystal elements are widely used in televisions, mobile devices, various monitors, and the like. Accompanied by this multi-purpose, liquid crystal elements are required to be further high-quality, and while promoting the improvement of the driving method or element structure, the improvement of the liquid crystal alignment film as one of the constituent materials of the liquid crystal element is promoted (for example, refer to the patent Literature 1). In Patent Document 1, it is disclosed that polyamic acid and polyimide are produced by using a diamine having a ring structure and an alkanediyl group bonded to the ring structure through a nitrogen atom to be used as The polymer component of the liquid crystal alignment agent, thereby improving the afterimage characteristics, voltage retention, film transparency and contrast. [Prior art literature] [Patent Document]

[專利文獻1]日本專利特開2017-68215號公報[Patent Document 1] Japanese Patent Laid-Open No. 2017-68215

[發明所要解決的問題] 在智能手機或平板（tablet）終端等移動設備中，為了實現器件的薄型化，在製造液晶面板時，通常進行機械研磨。另外，在觸摸面板式的顯示元件中，進行假定利用手指觸摸液晶面板的敲擊試驗（耐按壓性試驗），此時，會對液晶面板賦予過大的負荷。鑒於此種情況，對液晶配向膜要求膜強度高。因此，考慮向液晶配向膜的聚合物成分的主鏈中導入間隔物結構，由此提高液晶配向膜的韌性來改善膜強度。 [Problem to be Solved by the Invention] In mobile devices such as smartphones and tablet terminals, mechanical polishing is usually performed when manufacturing liquid crystal panels in order to reduce the thickness of the device. In addition, in a touch-panel type display element, a tap test (pressure resistance test) is performed assuming that a finger touches the liquid crystal panel, and in this case, an excessive load is applied to the liquid crystal panel. In view of this situation, high film strength is required for liquid crystal alignment films. Therefore, it is conceivable to introduce a spacer structure into the main chain of the polymer component of the liquid crystal alignment film, thereby increasing the toughness of the liquid crystal alignment film and improving the film strength.

然而，本發明人進行了研究，結果可知，由於間隔物結構的疏水性高，因此在欲通過使液晶配向劑含有具有間隔物結構的聚合物來提高膜的韌性的情況下，液晶配向性降低，在液晶元件中容易產生殘像或對比度降低。為了實現液晶元件的進一步的高品質化，而謀求一種可平衡良好地表現出液晶元件的低殘像特性及高對比度特性、膜的高韌性的液晶配向膜。However, as a result of the present inventors' investigations, it was found that since the hydrophobicity of the spacer structure is high, when the liquid crystal alignment agent contains a polymer having a spacer structure to improve the toughness of the film, the liquid crystal alignment property decreases. , it is easy to generate afterimage or decrease in contrast in the liquid crystal element. In order to further improve the quality of liquid crystal elements, a liquid crystal alignment film capable of expressing low afterimage characteristics and high contrast characteristics of liquid crystal elements and high film toughness in a well-balanced manner is desired.

本發明是鑒於所述情況而成，其主要目的在於提供一種液晶配向劑，其可獲得低殘像及高對比度的液晶元件且可形成韌性高的液晶配向膜。The present invention is made in view of the above circumstances, and its main purpose is to provide a liquid crystal alignment agent capable of obtaining a liquid crystal element with low afterimage and high contrast and forming a liquid crystal alignment film with high toughness.

[解決問題的技術手段] 本發明為了解決所述課題而採用以下手段。 [Technical means to solve the problem] In order to solve the above-mentioned problems, the present invention employs the following means.

＜1＞ 一種液晶配向劑，含有：聚醯胺酸[P]，包含源自二胺的結構單元（I），且在所述結構單元（I）或與所述結構單元（I）不同的結構單元的主鏈中具有碳數2以上的鏈狀結構，所述二胺具有選自由羧酸基、磺酸基、磷酸基及膦酸基所組成的群組中的至少一種酸性基；及聚合物[Q]（其中，所述聚醯胺酸[P]除外），為選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種。<1> A liquid crystal alignment agent comprising: polyamic acid [P], comprising a structural unit (I) derived from diamine, and the structural unit (I) or different from the structural unit (I) The main chain of the structural unit has a chain structure with more than 2 carbon atoms, and the diamine has at least one acidic group selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphoric acid groups and phosphonic acid groups; and The polymer [Q] (wherein the polyamic acid [P] is excluded) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.

＜2＞ 一種液晶配向膜，是使用所述＜1＞的液晶配向劑而形成。 ＜3＞ 一種液晶元件，包括所述＜2＞的液晶配向膜。 ＜4＞ 一種液晶配向膜的製造方法，使用所述＜1＞的液晶配向劑來形成有機膜，對所述有機膜進行光照射來賦予液晶配向能力。 ＜5＞ 一種液晶配向膜的製造方法，使用所述＜1＞的液晶配向劑來形成有機膜，對所述有機膜實施摩擦處理。 <2> A liquid crystal alignment film formed using the liquid crystal alignment agent of <1>. <3> A liquid crystal element including the liquid crystal alignment film of <2>. <4> A method for producing a liquid crystal alignment film, comprising forming an organic film using the liquid crystal alignment agent of <1>, irradiating the organic film with light, and imparting liquid crystal alignment ability. <5> A method for producing a liquid crystal alignment film, comprising forming an organic film using the liquid crystal alignment agent of <1>, and subjecting the organic film to a rubbing treatment.

[發明的效果] 根據本發明，通過製成含有所述聚醯胺酸[P]與聚合物[Q]的液晶配向劑，可獲得液晶元件的低殘像特性及對比度特性優異且膜強度（特別是膜的韌性）高的液晶配向膜。 [Effect of the invention] According to the present invention, by making the liquid crystal alignment agent containing the polyamic acid [P] and the polymer [Q], the low afterimage characteristics and contrast characteristics of the liquid crystal element can be obtained and the film strength (especially the toughness of the film) can be obtained. ) High liquid crystal alignment film.

[兩面覆金屬積層板] 以下，對與本公開的形態相關的事項進行詳細說明。此外，在本說明書中，所謂「烴基」，為包含鏈狀烴基、脂環式烴基及芳香族烴基的含義。所謂「鏈狀烴基」，是指不含環狀結構，而是僅由鏈狀結構構成的直鏈狀烴基及分支狀烴基。其中，可為飽和也可為不飽和。所謂「脂環式烴基」，是指僅包含脂環式烴的結構作為環結構，而不含芳香環結構的烴基。其中，無需僅由脂環式烴的結構構成，也包含在其一部分中具有鏈狀結構的基。所謂「芳香族烴基」，是指包含芳香環結構作為環結構的烴基。其中，無需僅由芳香環結構構成，也可在其一部分中包含鏈狀結構或脂環式烴的結構。 [Double-sided metal-clad laminate] Hereinafter, matters related to the aspects of the present disclosure will be described in detail. In addition, in this specification, a "hydrocarbon group" is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The term "chain hydrocarbon group" refers to a linear hydrocarbon group and a branched hydrocarbon group that do not contain a cyclic structure but only consist of a chain structure. Among them, it may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, it does not need to consist only of the structure of an alicyclic hydrocarbon, but also includes the group which has a chain structure in a part. The "aromatic hydrocarbon group" refers to a hydrocarbon group including an aromatic ring structure as a ring structure. However, it does not need to consist only of an aromatic ring structure, and may contain a chain structure or an alicyclic hydrocarbon structure in a part thereof.

所謂聚合物的「主鏈」，是指聚合物的原子鏈中最長的「主幹」的部分。所謂聚合物的「側鏈」，是指自聚合物的「主幹」分支的部分。所謂「有機基」，是指自包含碳的化合物（即有機化合物）中去除任意的氫原子而成的原子團。The so-called "main chain" of a polymer refers to the part of the longest "backbone" in the atomic chain of the polymer. The "side chain" of a polymer refers to a part branched from the "trunk" of the polymer. The "organic group" refers to an atomic group obtained by removing arbitrary hydrogen atoms from a compound containing carbon (ie, an organic compound).

《液晶配向劑》 本公開的液晶配向劑含有以下的聚醯胺酸[P]及聚合物[Q]。 聚醯胺酸[P]：包含源自二胺的結構單元（I），且在結構單元（I）或與結構單元（I）不同的結構單元的主鏈中具有碳數2以上的鏈狀結構的聚醯胺酸，所述二胺具有選自由羧酸基、磺酸基、磷酸基及膦酸基所組成的群組中的至少一種酸性基 聚合物[Q]：為選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種的聚合物（其中，聚醯胺酸[P]除外） 以下，對本公開的液晶配向劑中所含的聚醯胺酸[P]及聚合物[Q]、以及視需要而調配的其他成分進行說明。 "Liquid Crystal Alignment Agent" The liquid crystal alignment agent of the present disclosure contains the following polyamic acid [P] and polymer [Q]. Polyamic acid [P]: Contains a structural unit (I) derived from a diamine, and has a chain having 2 or more carbon atoms in the main chain of the structural unit (I) or a structural unit different from the structural unit (I) The polyamic acid of the structure, the diamine has at least one acidic group selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphoric acid groups and phosphonic acid groups Polymer [Q]: at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide (excluding polyamic acid [P]) Hereinafter, the polyamic acid [P] contained in the liquid crystal alignment agent of this disclosure, the polymer [Q], and other components mix|blended as needed are demonstrated.

＜聚醯胺酸[P]＞ 聚醯胺酸[P]只要具有結構單元（I），且在結構單元（I）或與結構單元（I）不同的結構單元的主鏈中具有碳數2以上的鏈狀結構即可。作為聚醯胺酸[P]的具體例，可列舉下述〔1〕及〔2〕的聚醯胺酸。 〔1〕包含結構單元（I）及源自在主鏈中具有碳數2以上的鏈狀結構的單量體的結構單元（以下，也稱為「結構單元（II）」）的聚醯胺酸 〔2〕包含源自具有所述酸性基且在主鏈中具有碳數2以上的鏈狀結構的單量體的結構單元作為結構單元（I）的聚醯胺酸 這些中，就單量體的選擇自由度高的方面而言，較佳為所述〔1〕的形態。 ＜Polyamide [P]＞ The polyamide [P] should just have a structural unit (I) and have a chain structure having 2 or more carbon atoms in the main chain of the structural unit (I) or a structural unit different from the structural unit (I). Specific examples of the polyamide acid [P] include the polyamide acids of the following [1] and [2]. [1] A polyamide comprising a structural unit (I) and a structural unit derived from a monomer having a chain structure having 2 or more carbon atoms in the main chain (hereinafter also referred to as "structural unit (II)") acid [2] A polyamic acid comprising, as a structural unit (I), a structural unit derived from a monomer having the acidic group and having a chain structure having 2 or more carbon atoms in the main chain Among these, the form of [1] above is preferable in terms of a high degree of freedom of selection of the monomer.

（結構單元（I）） 聚醯胺酸[P]所具有的結構單元（I）為源自具有選自由羧酸基、磺酸基、磷酸基及膦酸基所組成的群組中的至少一種基（以下，也簡稱為「酸性基」）的二胺（以下也稱為「特定二胺A」）的結構單元。作為特定二胺A的具體例，例如可列舉具有下述式（2）所表示的部分結構的二胺。 [化1]

（式（2）中，Y ¹為具有羧酸基、磺酸基、磷酸基或膦酸基的一價基；m1為1～4的整數；「*」表示鍵結鍵） (Structural unit (I)) The structural unit (I) contained in polyamic acid [P] is derived from at least A structural unit of diamine (hereinafter, also referred to as "specific diamine A") of one type of group (hereinafter also simply referred to as "acidic group"). As a specific example of specific diamine A, the diamine which has a partial structure represented by following formula (2), for example is mentioned. [chemical 1]

(In formula (2), ^Y1 is a monovalent group having a carboxylic acid group, a sulfonic acid group, a phosphoric acid group or a phosphonic acid group; m1 is an integer from 1 to 4; "*" represents a bond)

在所述式（2）中，Y ¹所具有的酸性基的數量並無特別限定，就可提高液晶配向膜的韌性的改善效果的方面而言，較佳為2個以上。就單體的獲取容易性的觀點而言，Y ¹所具有的酸性基的數量例如為6個以下。m1較佳為1～3。 In the formula (2), the number of acidic groups Y ¹ has is not particularly limited, and is preferably 2 or more in terms of improving the toughness of the liquid crystal alignment film. The number of acidic groups that Y ¹ has is, for example, 6 or less from the viewpoint of easy acquisition of monomers. m1 is preferably 1-3.

特定二胺A可在一分子內僅具有1個所述式（2）所表示的部分結構，也可具有2個以上。特定二胺A較佳為具有2個一級胺基直接或經由二價連結基而與所述式（2）所表示的部分結構中的苯環鍵結所得的結構。The specific diamine A may have only one partial structure represented by the formula (2) in one molecule, or may have two or more. The specific diamine A preferably has a structure in which two primary amine groups are bonded to the benzene ring in the partial structure represented by the formula (2) directly or via a divalent linking group.

作為特定二胺A的具體例，例如可列舉下述式（DA-1）～式（DA-17）各自所表示的化合物等。 [化2]

[化3]

As a specific example of specific diamine A, the compound etc. which are each represented by following formula (DA-1) - a formula (DA-17) are mentioned, for example. [Chem 2]

[Chem 3]

在聚醯胺酸[P]中，相對於源自構成聚醯胺酸[P]的二胺的結構單元的總量，結構單元（I）的含有比例較佳為2莫耳%以上，更佳為5莫耳%以上，進而較佳為10莫耳%以上。通過將聚醯胺酸[P]中的結構單元（I）的比例設為所述範圍，容易產生聚醯胺酸[P]與聚合物[Q]的層分離，可提高由調配聚醯胺酸[P]帶來的膜的韌性的提高效果，就此方面而言較佳。In polyamic acid [P], the content ratio of the structural unit (I) is preferably 2 mol% or more, more preferably It is preferably at least 5 mol%, and more preferably at least 10 mol%. By setting the ratio of the structural unit (I) in the polyamide [P] to the above-mentioned range, layer separation between the polyamide [P] and the polymer [Q] is easy to occur, and it is possible to improve The effect of improving the toughness of the film by the acid [P] is preferable in this respect.

另外，相對於源自構成聚醯胺酸[P]的二胺的結構單元的總量，結構單元（I）的含有比例較佳為95莫耳%以下，更佳為90莫耳%以下，進而較佳為85莫耳%以下。通過將聚醯胺酸[P]中的結構單元（I）的比例設為所述範圍，可將結構單元（II）充分導入聚醯胺酸[P]中，可提高所獲得的液晶配向膜的韌性的改善效果，就此方面而言較佳。在合成聚醯胺酸[P]時，作為特定二胺A，可單獨使用一種，也可組合使用兩種以上。In addition, the content ratio of the structural unit (I) is preferably 95 mol% or less, more preferably 90 mol% or less, based on the total amount of structural units derived from the diamine constituting polyamic acid [P]. Furthermore, it is more preferably 85 mol% or less. By setting the ratio of the structural unit (I) in the polyamic acid [P] to the above-mentioned range, the structural unit (II) can be sufficiently introduced into the polyamic acid [P], and the obtained liquid crystal alignment film can be improved. The improvement effect of toughness is better in this respect. When synthesizing the polyamic acid [P], as the specific diamine A, one kind may be used alone, or two or more kinds may be used in combination.

（結構單元（II）） 結構單元（II）為源自在主鏈中具有碳數2以上的鏈狀結構的單量體（以下也稱為「單量體MB」）的結構單元。單量體MB較佳為在主鏈中具有下述式（1）所表示的直鏈狀結構作為碳數2以上的鏈狀結構的化合物。 [化4]

（式（1）中，R ¹為烷二基；R ²及R ³分別獨立地為單鍵或烷二基；X ¹為單鍵、氧原子、-CO-、-COO-、-NR ⁴-、-CO-NR ⁴-、-NR ⁴-CO-NR ⁵-或-NR ⁴-COO-；X ²為氧原子、-CO-、-COO-、-NR ⁴-、-CO-NR ⁴-、-NR ⁴-CO-NR ⁵-或-NR ⁴-COO-；R ⁴及R ⁵分別獨立地為氫原子或一價有機基；n為0～4的整數；其中，在式（1）中，R ¹、R ²及R ³的碳數的合計為2以上；在R ²為烷二基，X ¹為與單鍵不同的基，且n=0的情況下，R ³為烷二基；「*1」表示與環狀結構鍵結的鍵結鍵） (Structural Unit (II)) The structural unit (II) is a structural unit derived from a monomer having a chain structure having 2 or more carbon atoms in the main chain (hereinafter also referred to as "monomer MB"). Monomer MB is preferably a compound having a linear structure represented by the following formula (1) as a chain structure having 2 or more carbon atoms in the main chain. [chemical 4]

(In formula (1), R ¹ is an alkanediyl group; R ² and R ³ are independently a single bond or an alkanediyl group; X ¹ is a single bond, an oxygen atom, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-NR ⁵ -or -NR ⁴ -COO-; X ² is an oxygen atom, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ -, -NR ⁴ -CO-NR ⁵ -or -NR ⁴ -COO-; R ⁴ and R ⁵ are independently hydrogen atoms or monovalent organic groups; n is an integer from 0 to 4; wherein, in the formula (1 ), the total carbon number of R ¹ , R ² and R ³ is 2 or more; when R ² is an alkanediyl group, X ¹ is a group different from a single bond, and n=0, R ³ is an alkane diradical; "*1" indicates a bond bonded to a ring structure)

在所述式（1）中，R ¹、R ²及R ³的烷二基較佳為直鏈狀。R ¹、R ²及R ³的烷二基的碳數分別較佳為1～20，更佳為1～10。 在R ⁴及R ⁵為一價有機基的情況下，作為所述一價有機基，可列舉碳數1～10的一價烴基及熱脫離性基。就基於熱的脫離性良好的方面及可減少膜中的殘存量的方面而言，熱脫離性基較佳為叔丁氧基羰基。R ⁴及R ⁵較佳為氫原子或碳數1～3的烷基，更佳為氫原子或甲基。 In the formula (1), the alkanediyl groups of R ¹ , R ² and R ³ are preferably linear. The carbon numbers of the alkanediyl groups of R ¹ , R ² and R ³ are preferably 1-20, more preferably 1-10. When R ⁴ and R ⁵ are monovalent organic groups, examples of the monovalent organic group include monovalent hydrocarbon groups and thermally detachable groups having 1 to 10 carbon atoms. The thermally detachable group is preferably a tert-butoxycarbonyl group from the viewpoint of good thermal detachability and the ability to reduce the residual amount in the film. R ⁴ and R ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably a hydrogen atom or a methyl group.

作為由「*1」表示的鍵結鍵所鍵結的環狀結構，可列舉脂肪族環及芳香環等。作為脂肪族環，可列舉：環戊烷環及環己烷環等脂肪族烴環；哌啶環、哌嗪環及六亞甲基亞胺環等脂肪族雜環。作為芳香環，可列舉：苯環、萘環及蒽環等芳香族烴環；吡啶環及嘧啶環等芳香族雜環。由「*1」表示的鍵結鍵所鍵結的環可在環部分具有取代基。作為所述取代基，可列舉：烷基、鹵化烷基、鹵素原子等。另外，由「*1」表示的鍵結鍵所鍵結的環也可構成稠環的一部分。Examples of the cyclic structure bonded by the bond represented by "*1" include an aliphatic ring, an aromatic ring, and the like. Examples of the aliphatic ring include aliphatic hydrocarbon rings such as a cyclopentane ring and a cyclohexane ring; and aliphatic heterocyclic rings such as a piperidine ring, a piperazine ring, and a hexamethyleneimine ring. Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring; and aromatic heterocyclic rings such as pyridine ring and pyrimidine ring. The ring to which the bond represented by "*1" is bonded may have a substituent on the ring portion. As said substituent, an alkyl group, a halogenated alkyl group, a halogen atom, etc. are mentioned. In addition, the ring bonded by the bonding bond represented by "*1" may constitute a part of the condensed ring.

所述式（1）所表示的部分結構中，所述式（1）中所含的R ¹、R ²及R ³的碳數的合計為2以上。就在所獲得的液晶配向膜中獲得膜的韌性高的膜的觀點而言，所述式（1）中所含的R ¹、R ²及R ³的碳數的合計較佳為3以上。另外，就抑制液晶配向性的降低的觀點而言，式（1）中所含的R ¹、R ²及R ³的碳數的合計較佳為15以下，更佳為12以下。 In the partial structure represented by the formula (1), the total number of carbon atoms of R ¹ , R ² , and R ³ contained in the formula (1) is 2 or more. From the viewpoint of obtaining a film with high film toughness in the obtained liquid crystal alignment film, the total number of carbon atoms of R ¹ , R ² , and R ³ contained in the formula (1) is preferably 3 or more. In addition, the total number of carbon atoms of R ¹ , R ² , and R ³ contained in formula (1) is preferably 15 or less, more preferably 12 or less, from the viewpoint of suppressing a decrease in liquid crystal alignment.

作為結構單元（II）所具有的碳數2以上的鏈狀結構的具體例，例如可列舉下述式所表示的部分結構。此外，結構單元（II）可僅具有1個碳數2以上的鏈狀結構，也可具有2個以上。 [化5]

[化6]

（式中，t分別獨立地為0～15的整數；「*」表示與環狀結構鍵結的鍵結鍵） Specific examples of the chain structure having 2 or more carbon atoms in the structural unit (II) include, for example, a partial structure represented by the following formula. In addition, the structural unit (II) may have only one chain structure having 2 or more carbon atoms, or may have two or more. [chemical 5]

[chemical 6]

(In the formula, t is an integer of 0 to 15 independently; "*" represents a bond bonded to the ring structure)

單量體MB可為在主鏈中具有碳數2以上的鏈狀結構的四羧酸二酐（以下也稱為「特定酸酐B」），也可為在主鏈中具有碳數2以上的鏈狀結構的二胺（以下也稱為「特定二胺B」）。Monomer MB may be a tetracarboxylic dianhydride having a chain structure with 2 or more carbon atoms in the main chain (hereinafter also referred to as "specific anhydride B"), or a tetracarboxylic dianhydride having 2 or more carbon atoms in the main chain. Diamine of chain structure (hereinafter also referred to as "specific diamine B").

作為特定酸酐B，例如可列舉下述式（3）所表示的化合物。 [化7]

（式（3）中，R ¹、R ²、R ³、X ¹、X ²、R ⁴、R ⁵及n與所述式（1）為相同含義） As specific acid anhydride B, the compound represented by following formula (3), for example is mentioned. [chemical 7]

(In formula (3), R ¹ , R ² , R ³ , X ¹ , X ² , R ⁴ , R ⁵ and n have the same meanings as in formula (1) above)

作為特定酸酐B的具體例，例如可列舉下述式（TB-1）～式（TB-9）各自所表示的化合物等。 [化8]

Specific examples of the specific acid anhydride B include compounds represented by each of the following formulas (TB-1) to (TB-9), and the like. [chemical 8]

作為特定二胺B，例如可列舉下述式（4）所表示的化合物。 [化9]

（式（4）中，A ¹及A ²分別獨立地為二價芳香環基；L ¹為所述式（1）所表示的二價基；r為1～3的整數） As specific diamine B, the compound represented by following formula (4), for example is mentioned. [chemical 9]

(In formula (4), A ¹ and A ² are each independently a divalent aromatic ring group; L ¹ is a divalent group represented by the formula (1); r is an integer of 1 to 3)

在所述式（4）中，A ¹及A ²的二價芳香環基為自芳香環的環部分去除2個任意氫原子而成的基。作為所述芳香環，可列舉芳香族烴環、芳香族雜環。作為芳香族烴環，可列舉：苯環、萘環、蒽環等。芳香族雜環較佳為含氮雜環，例如可列舉吡啶環、嘧啶環等。所述芳香環可在環部分具有取代基。作為取代基，可列舉：烷基、鹵化烷基、鹵素原子等。 In the formula (4), the divalent aromatic ring groups of A ¹ and A ² are groups obtained by removing two arbitrary hydrogen atoms from the ring portion of the aromatic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and the like. The aromatic heterocycle is preferably a nitrogen-containing heterocycle, for example, a pyridine ring, a pyrimidine ring, and the like. The aromatic ring may have a substituent on the ring portion. As a substituent, an alkyl group, a halogenated alkyl group, a halogen atom, etc. are mentioned.

作為特定二胺B的具體例，例如可列舉下述式（DB-1）～式（DB-23）各自所表示的化合物等。 [化10]

[化11]

[化12]

As a specific example of specific diamine B, the compound etc. which are represented by each of following formula (DB-1) - a formula (DB-23), etc. are mentioned, for example. [chemical 10]

[chemical 11]

[chemical 12]

在聚醯胺酸[P]中，相對於源自構成聚醯胺酸[P]的單量體的結構單元的總量，結構單元（II）的含有比例較佳為2莫耳%以上，更佳為5莫耳%以上，進而較佳為10莫耳%以上。若聚醯胺酸[P]中的結構單元（II）的比例為所述範圍，則可提高膜的韌性的改善效果，就此方面而言較佳。另外，相對於源自構成聚醯胺酸[P]的單量體的結構單元的總量，結構單元（II）的含有比例較佳為70莫耳%以下，更佳為60莫耳%以下，進而較佳為50莫耳%以下。通過將聚醯胺酸[P]中的結構單元（II）的比例設為所述範圍，可抑制低殘像特性及高對比度特性的降低，就此方面而言較佳。在合成聚醯胺酸[P]時，作為單量體MB，可單獨使用一種，也可組合使用兩種以上。In polyamic acid [P], the content ratio of the structural unit (II) is preferably 2 mol% or more with respect to the total amount of structural units derived from monomers constituting the polyamic acid [P]. More preferably, it is 5 mol% or more, and still more preferably, it is 10 mol% or more. When the ratio of the structural unit (II) in the polyamic acid [P] is within the above range, the effect of improving the toughness of the film can be increased, which is preferable. In addition, the content ratio of the structural unit (II) is preferably at most 70 mol %, more preferably at most 60 mol %, based on the total amount of structural units derived from monomers constituting polyamic acid [P]. , and more preferably 50 mol% or less. By setting the ratio of the structural unit (II) in the polyamide [P] to the above-mentioned range, it is preferable in this point that the reduction of the low afterimage characteristic and the high contrast characteristic can be suppressed. When synthesizing the polyamic acid [P], as the monomer MB, one kind may be used alone, or two or more kinds may be used in combination.

合成聚醯胺酸[P]的方法並無特別限定。作為合成聚醯胺酸[P]的方法，可列舉：〔1〕使包含特定酸酐B的四羧酸二酐與包含特定二胺A的二胺化合物反應的方法；〔2〕使四羧酸二酐與包含特定二胺A及特定二胺B的二胺化合物反應的方法；〔3〕使包含特定酸酐B的四羧酸二酐與包含特定二胺A及特定二胺B的二胺化合物反應的方法等。這些中，就容易合成單量體的方面及可提高膜強度的改善效果的方面而言，較佳為使用基於所述〔2〕或〔3〕的方法，更佳為使用基於所述〔2〕的方法。在使用基於所述〔2〕或〔3〕的方法的情況下，可獲得具有源自在主鏈中具有碳數2以上的鏈狀結構的二胺的結構單元作為結構單元（II）的聚合物。The method for synthesizing polyamide [P] is not particularly limited. Examples of methods for synthesizing polyamic acid [P] include: [1] a method of reacting a tetracarboxylic dianhydride containing a specific acid anhydride B with a diamine compound containing a specific diamine A; Method for reacting dianhydride with diamine compound containing specific diamine A and specific diamine B; [3] making tetracarboxylic dianhydride containing specific acid anhydride B and diamine compound containing specific diamine A and specific diamine B method of reaction, etc. Among these, it is preferable to use the method based on the above-mentioned [2] or [3], more preferably to use the method based on the above-mentioned [2] in terms of easy synthesis of the monomer and the effect of improving the film strength. 〕Methods. In the case of using the method based on the above [2] or [3], polymerization having a structural unit derived from a diamine having a chain structure having 2 or more carbon atoms in the main chain as the structural unit (II) can be obtained things.

在合成聚醯胺酸[P]時，作為四羧酸二酐，也可使用與特定酸酐B不同的化合物（以下也稱為「其他酸酐」）。作為其他酸酐的具體例，例如可列舉：1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基環丁烷-1,2,3,4-四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、5-(2,5-二氧代四氫呋喃-3-基)-3a,4,5,9b-四氫萘並[1,2-c]呋喃-1,3-二酮、5-(2,5-二氧代四氫呋喃-3-基)-8-甲基-3a,4,5,9b-四氫萘並[1,2-c]呋喃-1,3-二酮、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、3,5,6-三羧基-2-羧基甲基降冰片烷-2:3,5:6-二酐、2,4,6,8-四羧基雙環[3.3.0]辛烷-2:4,6:8-二酐、環己烷四羧酸二酐、環戊烷四羧酸二酐、均苯四甲酸二酐、4,4'-(六氟伸異丙基)二鄰苯二甲酸酐、對伸苯基雙(偏苯三甲酸單酯酐)、3,3',4,4'-二苯甲酮四羧酸二酐、4,4'-聯鄰苯二甲酸二酐、4,4'-氧基二鄰苯二甲酸酐等。作為其他酸酐，可單獨使用一種，也可組合使用兩種以上。When synthesizing the polyamic acid [P], as the tetracarboxylic dianhydride, a compound different from the specific anhydride B (hereinafter also referred to as "other anhydride") can also be used. Specific examples of other acid anhydrides include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid Dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1, 2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1, 2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride , 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2 :4,6:8-dianhydride, cyclohexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene) di-ortho Phthalic anhydride, p-phenylene bis(trimellitic monoester anhydride), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-biphthalic acid Dianhydride, 4,4'-oxydiphthalic anhydride, etc. As other acid anhydrides, one type may be used alone, or two or more types may be used in combination.

作為聚醯胺酸[P]的合成中使用的四羧酸二酐，其中，可較佳地使用選自由下述式（TA-1）～式（TA-9）各自所表示的化合物所組成的群組中的至少一種四羧酸二酐（以下也稱為「特定酸酐A」）。在使用這些特定酸酐A的情況下，通過與二胺充分反應，可獲得適合於液晶配向劑的黏度的充分分子量的聚合物。因此，在通過摩擦法來賦予液晶配向能力的情況及通過光配向法來賦予液晶配向能力的情況的任一情況下，均可獲得抑制了液晶配向性或膜強度的降低的液晶元件，就此方面而言較佳。 [化13]

As the tetracarboxylic dianhydride used in the synthesis of polyamic acid [P], among them, compounds selected from the compounds represented by the following formula (TA-1) to formula (TA-9) can be preferably used. At least one tetracarboxylic dianhydride (hereinafter also referred to as "specific anhydride A") in the group. When these specific acid anhydrides A are used, a sufficient molecular weight polymer suitable for the viscosity of a liquid crystal aligning agent can be obtained by fully reacting with diamine. Therefore, in either case of imparting the liquid crystal alignment ability by the rubbing method and the case of imparting the liquid crystal alignment ability by the photoalignment method, it is possible to obtain a liquid crystal element in which a decrease in liquid crystal alignment or film strength is suppressed. better. [chemical 13]

在聚醯胺酸[P]中，相對於源自構成聚醯胺酸[P]的四羧酸二酐的結構單元的總量，源自特定酸酐A的結構單元的含量較佳為5莫耳%以上，更佳為10莫耳%以上，進而較佳為20莫耳%以上。此外，作為特定酸酐A，可單獨使用一種，也可混合使用兩種以上。In the polyamic acid [P], the content of the structural unit derived from the specific acid anhydride A is preferably 5 moles relative to the total amount of the structural unit derived from the tetracarboxylic dianhydride constituting the polyamic acid [P]. mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more. In addition, as the specific acid anhydride A, one type may be used alone, or two or more types may be used in combination.

在合成聚醯胺酸[P]時，作為二胺，也可使用與特定二胺A及特定二胺B不同的化合物（以下也稱為「其他二胺」）。其他二胺並無特別限定，例如可列舉：脂肪族二胺、脂環式二胺、芳香族二胺及二胺基有機矽氧烷等。When synthesizing the polyamic acid [P], as the diamine, a compound different from the specific diamine A and the specific diamine B (hereinafter also referred to as "other diamine") can also be used. Other diamines are not particularly limited, and examples thereof include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes.

作為這些的具體例，脂肪族二胺例如可列舉：間苯二甲胺等；脂環式二胺例如可列舉：對環己烷二胺、4,4'-伸甲基雙(環己基胺)等；芳香族二胺例如可列舉：十二烷氧基二胺基苯、十六烷氧基二胺基苯、十八烷氧基二胺基苯、膽甾烷基氧基二胺基苯、膽甾醇基氧基二胺基苯、二胺基苯甲酸膽甾烷基酯、二胺基苯甲酸膽甾醇基酯、二胺基苯甲酸羊毛甾烷基酯、3,6-雙(4-胺基苯甲醯基氧基)膽甾烷、3,6-雙(4-胺基苯氧基)膽甾烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-丁基環己烷、2,5-二胺基-N,N-二烯丙基苯胺、下述式（E-1）所表示的化合物等側鏈型二胺； [化14]

（式（E-1）中，X ^I及X ^II分別獨立地為單鍵、-O-、*-COO-或*-OCO-（其中，「*」表示與X ^I的鍵結鍵）；R ^I為碳數1～3的烷二基；R ^II為單鍵或碳數1～3的烷二基；R ^III為碳數1～20的烷基、烷氧基、氟烷基或氟烷氧基；a為0或1；b為0～3的整數；c為0～2的整數；d為0或1；其中，1≦a+b+c≦3） 對苯二胺、4,4'-二胺基二苯基甲烷、4,4'-伸乙基二苯胺、4,4'-二胺基二苯基醚、4,4'-二胺基二苯基胺、4,4'-二胺基二苯基硫醚、4-胺基苯基-4'-胺基苯甲酸酯、4,4'-二胺基偶氮苯、N,N'-二(4-胺基苯基)-N,N'-二甲基乙二胺、雙(4-胺基苯基)胺、N,N-雙(4-胺基苯基)甲基胺、1,4-雙(4-胺基苯基)-哌嗪、N,N'-雙(4-胺基苯基)-聯苯胺、2,2'-二甲基聯苯胺、2,2'-雙(三氟甲基)-4,4'-二胺基聯苯、1,4-雙(4-胺基苯氧基)苯、4-(4-胺基苯氧基羰基)-1-(4-胺基苯基)哌啶等非側鏈型二胺。在合成聚醯胺酸[P]時，作為其他二胺，可單獨使用一種或組合使用兩種以上。 As specific examples of these, aliphatic diamines include, for example, m-xylylenediamine, etc.; examples of alicyclic diamines include: p-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine) ) and the like; examples of aromatic diamines include: dodecyloxydiaminobenzene, hexadecyloxydiaminobenzene, octadecyloxydiaminobenzene, cholestanyloxydiamine Benzene, cholesteryloxydiaminobenzene, cholestyl diaminobenzoate, cholesteryl diaminobenzoate, lanostanyl diaminobenzoate, 3,6-bis( 4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 1,1-bis(4-((aminophenyl)methyl )phenyl)-4-butylcyclohexane, 2,5-diamino-N,N-diallylaniline, compounds represented by the following formula (E-1) and other side-chain diamines; [chemical 14]

(In formula (E-1), X ^I and X ^II are independently a single bond, -O-, *-COO- or *-OCO- (wherein, "*" represents a bond with X ^I ); R ^I is an alkanediyl group with 1 to 3 carbons; R ^II is a single bond or an alkanediyl group with 1 to 3 carbons; R ^III is an alkyl, alkoxy, fluoroalkyl or fluorine with 1 to 20 carbons Alkoxy; a is 0 or 1; b is an integer from 0 to 3; c is an integer from 0 to 2; d is 0 or 1; among them, 1≦a+b+c≦3) p-phenylenediamine, 4 ,4'-Diaminodiphenylmethane, 4,4'-Ethylenediphenylamine, 4,4'-Diaminodiphenyl ether, 4,4'-Diaminodiphenylamine, 4 ,4'-Diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, N,N'-bis(4 -aminophenyl)-N,N'-dimethylethylenediamine, bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methylamine, 1,4 -bis(4-aminophenyl)-piperazine, N,N'-bis(4-aminophenyl)-benzidine, 2,2'-dimethylbenzidine, 2,2'-bis( Trifluoromethyl)-4,4'-diaminobiphenyl, 1,4-bis(4-aminophenoxy)benzene, 4-(4-aminophenoxycarbonyl)-1-(4 -Aminophenyl)piperidine and other non-side-chain diamines. When synthesizing the polyamic acid [P], as other diamines, one type may be used alone or two or more types may be used in combination.

在合成聚醯胺酸[P]時，相對於聚醯胺酸[P]的合成中使用的二胺的合計量，特定二胺A的使用比例較佳為設為2莫耳%以上，更佳為設為5莫耳%以上，進而較佳為設為10莫耳%以上。另外，相對於聚醯胺酸[P]的合成中使用的二胺的合計量，特定二胺A的使用比例較佳為95莫耳%以下，更佳為90莫耳%以下，進而較佳為85莫耳%以下。When synthesizing polyamic acid [P], the usage ratio of specific diamine A is preferably 2 mol % or more with respect to the total amount of diamines used in the synthesis of polyamic acid [P]. Preferably, it shall be 5 mol % or more, More preferably, it shall be 10 mol % or more. In addition, the usage ratio of the specific diamine A is preferably 95 mol % or less, more preferably 90 mol % or less, and still more preferably It is less than 85 mole%.

在合成聚醯胺酸[P]時，相對於聚醯胺酸[P]的合成中使用的二胺的合計量，特定二胺B的使用比例較佳為設為2莫耳%以上，更佳為設為5莫耳%以上，進而較佳為設為10莫耳%以上。另外，相對於聚醯胺酸[P]的合成中使用的二胺的合計量，特定二胺B的使用比例較佳為48莫耳%以下，更佳為45莫耳%以下。When synthesizing polyamic acid [P], the usage ratio of specific diamine B is preferably 2 mol % or more with respect to the total amount of diamines used in the synthesis of polyamic acid [P]. Preferably, it shall be 5 mol % or more, More preferably, it shall be 10 mol % or more. In addition, the usage ratio of the specific diamine B is preferably 48 mol % or less, more preferably 45 mol % or less, based on the total amount of diamines used in the synthesis of polyamic acid [P].

（聚醯胺酸的合成） 聚醯胺酸[P]可通過使如所述那樣的四羧酸二酐與二胺和視需要的分子量調整劑一起進行反應來獲得。作為分子量調整劑，例如可列舉：酸單酐、單胺化合物、單異氰酸酯化合物等。供於聚醯胺酸[P]的合成反應的四羧酸二酐與二胺的使用比例較佳為相對於二胺的胺基1莫耳當量而四羧酸二酐的酸酐基成為0.2莫耳當量～2莫耳當量的比例。 (Synthesis of polyamide acid) Polyamic acid [P] can be obtained by making tetracarboxylic dianhydride as mentioned above react with diamine, and a molecular weight modifier as needed. As a molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example. The ratio of tetracarboxylic dianhydride and diamine used in the synthesis reaction of polyamic acid [P] is preferably 0.2 mol of the anhydride group of the tetracarboxylic dianhydride relative to 1 molar equivalent of the amine group of the diamine. The ratio of ear equivalent to 2 molar equivalent.

聚醯胺酸[P]的合成反應較佳為在有機溶媒中進行。此時的反應溫度較佳為-20℃～150℃，反應時間較佳為0.1小時～24小時。作為反應中使用的有機溶媒，例如可列舉：非質子性極性溶媒、酚系溶媒、醇、酮、酯、醚、鹵化烴、烴等。特佳的有機溶媒是使用選自由N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸、γ-丁內酯、四甲基脲、六甲基磷醯三胺、間甲酚、二甲酚以及鹵化酚所組成的群組中的一種以上作為溶媒，或者為這些中的一種以上、與其他有機溶媒（例如，丁基溶纖劑、二乙二醇二***等）的混合物。有機溶媒的使用量較佳為設為相對於反應溶液的總量而四羧酸二酐及二胺化合物的合計量成為0.1質量%～50質量%的量。The synthesis reaction of polyamide acid [P] is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours. Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. A particularly preferred organic solvent is to use a solvent selected from N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrol One or more of the group consisting of ester, tetramethylurea, hexamethylphosphoryltriamine, m-cresol, xylenol and halogenated phenol as a solvent, or more than one of these, with other organic solvents ( For example, mixtures of butyl cellosolve, diethylene glycol diethyl ether, etc.). As for the usage-amount of an organic solvent, it is preferable to set it as the quantity which becomes 0.1 mass % - 50 mass % of the total amount of a tetracarboxylic dianhydride and a diamine compound with respect to the total amount of a reaction solution.

如此，可獲得溶解聚醯胺酸[P]而成的反應溶液。所獲得的反應溶液可直接供於液晶配向劑的製備，也可將反應溶液中所含的聚醯胺酸[P]分離之後供於液晶配向劑的製備。In this way, a reaction solution in which polyamic acid [P] is dissolved can be obtained. The obtained reaction solution may be directly used for the preparation of the liquid crystal alignment agent, or may be used for the preparation of the liquid crystal alignment agent after separating the polyamic acid [P] contained in the reaction solution.

＜聚合物[Q]＞ 聚合物[Q]為選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種。其中，聚合物[Q]為與聚醯胺酸[P]不同的聚合物。 ＜Polymer [Q]＞ The polymer [Q] is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide. However, polymer [Q] is a polymer different from polyamic acid [P].

聚合物[Q]較佳為結構單元（I）的含量少於聚醯胺酸[P]的聚合物。在此情況下，當形成液晶配向膜時，容易產生聚醯胺酸[P]與聚合物[Q]的層分離，可提高膜的韌性的改善效果，就此方面而言較佳。具體而言，相對於源自構成聚合物[Q]的二胺的結構單元的總量，聚合物[Q]中的結構單元（I）的含量較佳為1莫耳%以下，更佳為0.5莫耳%以下，進而較佳為0.1莫耳%以下。The polymer [Q] is preferably a polymer having a smaller content of the structural unit (I) than the polyamic acid [P]. In this case, when the liquid crystal alignment film is formed, layer separation of the polyamic acid [P] and the polymer [Q] is likely to occur, and the effect of improving the toughness of the film can be enhanced, which is preferable. Specifically, the content of the structural unit (I) in the polymer [Q] is preferably 1 mol% or less, more preferably 0.5 mol% or less, more preferably 0.1 mol% or less.

聚合物[Q]較佳為包含具有光配向性基的結構單元的聚合物。此處，所謂光配向性基，為通過基於光照射的光分解反應、光異構化反應、光二聚化反應或光重排反應等而對膜賦予各向異性的官能基。作為光配向性基的具體例，可列舉：包含偶氮苯或其衍生物作為基本骨架的含有偶氮苯的基、包含肉桂酸或其衍生物（肉桂酸結構）作為基本骨架的含有肉桂酸結構的基、包含環丁烷或其衍生物作為基本骨架的含有環丁烷結構的基、包含查耳酮或其衍生物作為基本骨架的含有查耳酮的基、包含二苯甲酮或其衍生物作為基本骨架的含有二苯甲酮的基、包含苯甲酸苯基酯或其衍生物作為基本骨架的含有苯甲酸苯基酯的基、包含香豆素或其衍生物作為基本骨架的含有香豆素的基等。The polymer [Q] is preferably a polymer containing a structural unit having a photoalignment group. Here, the photoalignment group is a functional group that imparts anisotropy to a film by photolysis reaction, photoisomerization reaction, photodimerization reaction, photorearrangement reaction, etc. by light irradiation. Specific examples of photoalignment groups include azobenzene-containing groups containing azobenzene or its derivatives as a basic skeleton, cinnamic acid-containing groups containing cinnamic acid or its derivatives (cinnamic acid structure) as a basic skeleton, structural group, a group containing cyclobutane structure containing cyclobutane or a derivative thereof as a basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a group containing benzophenone or its derivative A benzophenone-containing group containing a derivative as a basic skeleton, a phenylbenzoate-containing group containing a phenyl benzoate or a derivative thereof as a basic skeleton, a group containing coumarin or a derivative thereof as a basic skeleton The base of coumarin, etc.

就可通過聚合物[Q]與聚醯胺酸[P]的層分離來獲得光配向能力優異的有機膜的方面而言，聚合物[Q]較佳為包含源自具有環丁烷環結構的四羧酸衍生物的結構單元（以下，也稱為「結構單元（III）」）。作為結構單元（III）所具有的環丁烷環結構的具體例，可列舉下述式（5）所表示的部分結構。 [化15]

（式（5）中，R ¹¹～R ¹⁴分別獨立地為氫原子、鹵素原子、碳數1～6的烷基、碳數1～6的鹵化烷基、碳數1～6的烷氧基、碳數1～6的硫代烷基、碳數2～6的烯基、碳數2～6的炔基或「-COR ¹⁵」（其中，R ¹⁵為碳數1～6的烷基、含氟烷基、烷氧基或含氟烷氧基）；「*」表示鍵結鍵） In terms of obtaining an organic film excellent in photoalignment ability by layer separation of polymer [Q] and polyamic acid [P], polymer [Q] preferably contains The structural unit of the tetracarboxylic acid derivative (hereinafter also referred to as "structural unit (III)"). As a specific example of the cyclobutane ring structure which a structural unit (III) has, the partial structure represented by following formula (5) is mentioned. [chemical 15]

(In formula (5), R ¹¹ to R ¹⁴ are independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbons, a halogenated alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons , a thioalkyl group with 1 to 6 carbons, an alkenyl group with 2 to 6 carbons, an alkynyl group with 2 to 6 carbons, or "-COR ¹⁵ " (wherein, R ¹⁵ is an alkyl group with 1 to 6 carbons, fluorinated alkyl, alkoxy or fluorinated alkoxy); "*" indicates a bond)

作為具有所述式（5）所表示的部分結構的四羧酸衍生物，例如可列舉下述式（TC-1）～式（TC-13）各自所表示的化合物、以及這些四羧酸二酯化合物及四羧酸二酯二鹵化物等。 [化16]

Examples of tetracarboxylic acid derivatives having a partial structure represented by the formula (5) include compounds represented by each of the following formulas (TC-1) to (TC-13), and these tetracarboxylic acid bis Ester compounds and tetracarboxylic acid diester dihalides, etc. [chemical 16]

作為具有環丁烷環結構的四羧酸衍生物，這些中，較佳為所述式（TC-1）～式（TC-7）各自所表示的化合物。其中，就光分解性高的方面而言，較佳為1,2,3,4-環丁烷四羧酸二酐（所述式（TC-1）所表示的化合物）及1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐（所述式（TC-3）所表示的化合物），特佳為1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐。在合成聚合物[Q]時，具有環丁烷環結構的四羧酸衍生物可單獨使用一種或組合使用兩種以上。Among these, as a tetracarboxylic-acid derivative which has a cyclobutane ring structure, the compound represented by each of said formula (TC-1) - a formula (TC-7) is preferable. Among them, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (the compound represented by the above formula (TC-1)) and 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride (the compound represented by the formula (TC-3)), particularly preferably 1,3-dimethyl-1,2, 3,4-Cyclobutanetetracarboxylic dianhydride. When synthesizing the polymer [Q], the tetracarboxylic acid derivatives having a cyclobutane ring structure may be used alone or in combination of two or more.

在聚合物[Q]具有結構單元（III）的情況下，相對於源自構成聚合物[Q]的四羧酸衍生物的結構單元的總量，結構單元（III）的含量較佳為30莫耳%以上，更佳為50莫耳%以上，進而較佳為80莫耳%以上。若聚合物[Q]所具有的結構單元（III）的比例為80莫耳%以上，則在形成液晶配向膜時應用光配向法的情況下，可對塗膜賦予優異的液晶配向能力，可提高工藝優點，就此方面而言較佳。In the case where the polymer [Q] has the structural unit (III), the content of the structural unit (III) is preferably 30% relative to the total amount of structural units derived from tetracarboxylic acid derivatives constituting the polymer [Q]. Mole % or more, more preferably 50 Mole % or more, further preferably 80 Mole % or more. If the proportion of the structural unit (III) contained in the polymer [Q] is 80 mole % or more, when the photo-alignment method is applied when forming the liquid crystal alignment film, excellent liquid crystal alignment ability can be imparted to the coating film, which can It is better in this respect to improve the process advantages.

聚合物[Q]的合成方法並無特別限定。在聚合物[Q]為聚醯胺酸的情況下，所述聚醯胺酸（以下，也稱為「聚醯胺酸[Q]」）可通過使四羧酸二酐與二胺反應來獲得。The synthesis method of polymer [Q] is not specifically limited. When the polymer [Q] is polyamic acid, the polyamic acid (hereinafter also referred to as "polyamic acid [Q]") can be synthesized by reacting tetracarboxylic dianhydride with diamine. get.

·聚醯胺酸 作為合成聚醯胺酸[Q]時使用的四羧酸二酐，可列舉具有環丁烷環結構的四羧酸二酐及不具有環丁烷環結構的四羧酸二酐（以下，也稱為「其他酸酐」）。作為具有環丁烷環結構的四羧酸二酐的具體例，可列舉所述式（TC-1）～式（TC-13）各自所表示的化合物等。另外，作為其他酸酐，可列舉與作為可用於合成聚醯胺酸[P]的四羧酸二酐而例示的化合物中的不具有環丁烷環結構的化合物相同的化合物。在合成聚醯胺酸[Q]時，作為四羧酸二酐，可單獨使用一種，也可組合使用兩種以上。 ·Polyamide As the tetracarboxylic dianhydride used when synthesizing polyamic acid [Q], tetracarboxylic dianhydride having a cyclobutane ring structure and tetracarboxylic dianhydride not having a cyclobutane ring structure (hereinafter also referred to as referred to as "other anhydrides"). As a specific example of the tetracarboxylic dianhydride which has a cyclobutane ring structure, the compound etc. which are each represented by said formula (TC-1) - a formula (TC-13) are mentioned. Moreover, as another acid anhydride, the compound similar to the compound which does not have a cyclobutane ring structure in the compound illustrated as a tetracarboxylic dianhydride which can be used for synthesis|combining polyamide acid [P] is mentioned. When synthesizing the polyamic acid [Q], as the tetracarboxylic dianhydride, one kind may be used alone, or two or more kinds may be used in combination.

就可提高聚醯胺酸[Q]的溶解性的方面及可獲得透明性高的液晶配向膜的方面而言，其他酸酐較佳為包含選自由脂肪族四羧酸二酐及脂環式四羧酸二酐所組成的群組中的至少一種，更佳為包含脂環式四羧酸二酐。在合成聚醯胺酸[Q]時，在使用選自由脂肪族四羧酸二酐及脂環式四羧酸二酐所組成的群組中的至少一種的情況下，相對於聚醯胺酸[Q]的合成中使用的四羧酸二酐的總量，其比例較佳為設為20莫耳%以上，更佳為設為40莫耳%以上，進而較佳為設為70莫耳%以上。In terms of improving the solubility of polyamic acid [Q] and obtaining a liquid crystal alignment film with high transparency, other acid anhydrides preferably include aliphatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic acid dianhydrides. At least one of the group consisting of carboxylic dianhydrides preferably contains alicyclic tetracarboxylic dianhydrides. When synthesizing polyamic acid [Q], when at least one selected from the group consisting of aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride is used, relative to polyamic acid The ratio of the total amount of tetracarboxylic dianhydride used in the synthesis of [Q] is preferably at least 20 mol %, more preferably at least 40 mol %, further preferably at least 70 mol % %above.

合成聚醯胺酸[Q]時使用的二胺並無特別限定，例如可列舉：脂肪族二胺、脂環式二胺、芳香族二胺及二胺基有機矽氧烷等。作為這些的具體例，可列舉與作為可用於合成聚醯胺酸[P]的二胺而例示的化合物相同的化合物。在合成聚醯胺酸[Q]時，作為二胺，可單獨使用一種，也可組合使用兩種以上。The diamine used for synthesizing polyamic acid [Q] is not particularly limited, and examples thereof include aliphatic diamine, alicyclic diamine, aromatic diamine, and diaminoorganosiloxane. Specific examples of these include the same compounds as those exemplified as diamines that can be used for synthesizing polyamic acid [P]. When synthesizing the polyamic acid [Q], as the diamine, one kind may be used alone, or two or more kinds may be used in combination.

在合成聚合物[Q]時，通過使用在主鏈中具有碳數2以上的鏈狀結構的單量體，可製造液晶配向膜的韌性更高且液晶配向性優異的液晶元件，就此方面而言較佳。在聚合物[Q]中，相對於源自構成聚合物[Q]的單量體的結構單元的總量，源自在主鏈中具有碳數2以上的鏈狀結構的單量體的結構單元（即，結構單元（II））的含有比例較佳為2莫耳%以上，更佳為5莫耳%以上，進而較佳為10莫耳%以上。When synthesizing the polymer [Q], by using a monomer having a chain structure with more than 2 carbon atoms in the main chain, it is possible to manufacture a liquid crystal element with higher toughness of the liquid crystal alignment film and excellent liquid crystal alignment. Words are better. In the polymer [Q], the structure derived from the monomer having a chain structure having 2 or more carbon atoms in the main chain relative to the total amount of structural units derived from the monomer constituting the polymer [Q] The content of the unit (ie, the structural unit (II)) is preferably at least 2 mol%, more preferably at least 5 mol%, and still more preferably at least 10 mol%.

另外，聚醯胺酸[Q]也可通過使如所述那樣的四羧酸二酐與二胺和視需要的分子量調整劑一起反應來獲得。關於聚醯胺酸[Q]的合成方法的詳細情況，可引用聚醯胺酸[P]的說明。In addition, the polyamic acid [Q] can also be obtained by making the above-mentioned tetracarboxylic dianhydride react with diamine and a molecular weight modifier if necessary. For details of the synthesis method of polyamide acid [Q], the description of polyamide acid [P] can be referred to.

·聚醯胺酸酯 在聚合物[Q]為聚醯胺酸酯的情況下，所述聚醯胺酸酯例如可通過如下方法等來獲得：[I]使所述獲得的聚醯胺酸[Q]與酯化劑（例如甲醇或乙醇、N,N-二甲基甲醯胺二乙基縮醛等）進行反應的方法；[II]使四羧酸二酯與二胺較佳為在有機溶媒中並在適當的脫水催化劑（例如4-(4,6-二甲氧基-1,3,5-三嗪-2-基)-4-甲基嗎啉鎓鹵化物、羰基咪唑、磷系縮合劑等）的存在下進行反應的方法；[III]使四羧酸二酯二鹵化物與二胺較佳為在有機溶媒中並在適當的堿（例如吡啶、三乙基胺等三級胺或氫化鈉、氫化鉀、氫氧化鈉、氫氧化鉀、鈉、鉀等鹼金屬類）的存在下進行反應的方法。 ·Polyuric acid ester When the polymer [Q] is a polyamide ester, the polyamide ester can be obtained, for example, by the following method: [I] esterifying the obtained polyamide acid [Q] with (such as methanol or ethanol, N,N-dimethylformamide diethyl acetal, etc.) to react; [II] make the tetracarboxylic acid diester and diamine preferably in an organic solvent and in Appropriate dehydration catalysts (such as 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium halide, carbonylimidazole, phosphorus-based condensing agents, etc. ) in the presence of a reaction method; [III] making the tetracarboxylic acid diester dihalide and diamine preferably in an organic solvent and in an appropriate alkali (such as pyridine, triethylamine and other tertiary amines or hydrogenation A method in which the reaction is carried out in the presence of alkali metals such as sodium, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, and potassium).

在所述[II]的方法中使用的四羧酸二酯可通過使用醇類等對四羧酸二酐進行開環而獲得。在所述[III]的方法中使用的四羧酸二酯二鹵化物可通過使如所述那樣獲得的四羧酸二酯與亞硫醯氯等適當的氯化劑進行反應而獲得。The tetracarboxylic diester used in the method of [II] above can be obtained by ring-opening tetracarboxylic dianhydride using alcohols or the like. The tetracarboxylic-acid diester dihalide used in the method of [III] above can be obtained by reacting the tetracarboxylic-acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride.

聚醯胺酸酯可僅具有醯胺酸酯結構，也可為使醯胺酸結構與醯胺酸酯結構並存的部分酯化物。此外，在通過所述反應以溶液的形式獲得聚醯胺酸酯的情況下，所述溶液可直接供於液晶配向劑的製備，也可將反應溶液中所含的聚醯胺酸酯分離之後供於液晶配向劑的製備。The polyamic acid ester may have only an imidic acid ester structure, or may be a partially esterified product in which an amidic acid structure and an amidic acid ester structure coexist. In addition, when the polyamide ester is obtained in the form of a solution by the reaction, the solution may be directly used in the preparation of a liquid crystal alignment agent, or after the polyamide ester contained in the reaction solution is separated, For the preparation of liquid crystal alignment agent.

·聚醯亞胺 在聚合物[Q]為聚醯亞胺的情況下，所述聚醯亞胺例如可通過對如所述那樣合成的聚醯胺酸[Q]進行脫水閉環並加以醯亞胺化來獲得。聚醯亞胺可為將作為其前體的聚醯胺酸[Q]所具有的醯胺酸結構全部加以脫水閉環而成的完全醯亞胺化物，也可為僅將醯胺酸結構的一部分加以脫水閉環而使醯胺酸結構與醯亞胺環結構並存的部分醯亞胺化物。聚醯亞胺的醯亞胺化率較佳為40%以上，更佳為60%～90%。所述醯亞胺化率是以百分率來表示聚醯亞胺的醯亞胺環結構的數量相對於醯胺酸結構的數量與醯亞胺環結構的數量的合計而所占的比例。此外，醯亞胺環的一部分也可為異醯亞胺環。 ·Polyimide When the polymer [Q] is a polyimide, the polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid [Q] synthesized as described above, followed by imidization. The polyimide may be a complete imide obtained by dehydrating and ring-closing the entire amide acid structure of the polyamide acid [Q] as its precursor, or it may be a part of the amide acid structure. Dehydration ring closure is used to make the amido acid structure and imide ring structure coexist. The imidization rate of polyimide is preferably at least 40%, more preferably 60% to 90%. The imidization rate is a percentage representing the ratio of the number of imide ring structures of polyimide to the sum of the number of amide acid structures and the number of imide ring structures. In addition, a part of the imide ring may be an isoimide ring.

聚醯胺酸[Q]的脫水閉環較佳為通過如下方法進行：將聚醯胺酸[Q]溶解於有機溶媒中，在所述溶液中添加脫水劑及脫水閉環催化劑並視需要進行加熱。作為脫水劑，例如可使用乙酸酐、丙酸酐、三氟乙酸酐等酸酐。相對於聚醯胺酸[Q]的醯胺酸結構的1莫耳，脫水劑的使用量較佳為設為0.01莫耳～20莫耳。作為脫水閉環催化劑，例如可使用：吡啶、三甲吡啶、二甲吡啶、三乙基胺等三級胺。The dehydration ring-closure of polyamide acid [Q] is preferably carried out by dissolving polyamide acid [Q] in an organic solvent, adding a dehydrating agent and a dehydration ring-closure catalyst to the solution, and heating if necessary. As a dehydrating agent, acid anhydrides, such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride, can be used, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01 mol - 20 mol with respect to 1 mol of the amide acid structure of polyamide acid [Q]. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used.

相對於使用的脫水劑1莫耳，脫水閉環催化劑的使用量較佳為設為0.01莫耳～10莫耳。作為使用的有機溶媒，可列舉作為聚醯胺酸[Q]的合成中所使用有機溶媒而例示的有機溶媒。脫水閉環反應的反應溫度較佳為0℃～180℃，反應時間較佳為1.0小時～120小時。如此獲得的含有聚醯亞胺的反應溶液可直接供於液晶配向劑的製備，也可將聚醯亞胺分離之後供於液晶配向劑的製備。The amount of the dehydration ring-closing catalyst used is preferably 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent to be used include those exemplified as the organic solvent used in the synthesis of polyamic acid [Q]. The reaction temperature of the dehydration ring-closing reaction is preferably 0° C. to 180° C., and the reaction time is preferably 1.0 hour to 120 hours. The reaction solution containing polyimide obtained in this way can be directly used in the preparation of liquid crystal alignment agent, and can also be used in the preparation of liquid crystal alignment agent after separating polyimide.

＜其他成分＞ 本公開的液晶配向劑也可還含有聚醯胺酸[P]及聚合物[Q]以外的成分（以下也稱為「其他成分」）。作為其他成分，例如可列舉：與聚醯胺酸[P]及聚合物[Q]不同的聚合物、在分子內具有1個以上的環氧基的化合物、在分子內具有2個以上的羥甲基的化合物、官能性矽烷化合物、在分子內具有1個以上的(甲基)丙烯醯基的化合物、抗氧化劑、金屬螯合化合物、硬化促進劑、表面活性劑、填充劑、分散劑、光增感劑等。這些的調配比例可在無損本公開的效果的範圍內根據各化合物來適宜選擇。 ＜Other ingredients＞ The liquid crystal alignment agent of the present disclosure may further contain components other than polyamide [P] and polymer [Q] (hereinafter also referred to as “other components”). Examples of other components include polymers different from polyamic acid [P] and polymer [Q], compounds having one or more epoxy groups in the molecule, and compounds having two or more hydroxyl groups in the molecule. Methyl compounds, functional silane compounds, compounds having one or more (meth)acryl groups in the molecule, antioxidants, metal chelate compounds, hardening accelerators, surfactants, fillers, dispersants, photosensitizer etc. These compounding ratios can be suitably selected according to each compound in the range which does not impair the effect of this disclosure.

（溶劑） 液晶配向劑通常作為聚醯胺酸[P]、聚合物[Q]、及視需要而使用的其他成分較佳為分散或溶解於適當的溶媒中而成的液狀的組合物來製備。 (solvent) A liquid crystal alignment agent is usually prepared as a liquid composition in which polyamic acid [P], polymer [Q], and other components used as needed are preferably dispersed or dissolved in an appropriate solvent.

作為使用的有機溶媒，例如可列舉：N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、1,2-二甲基-2-咪唑烷酮、γ-丁內酯、γ-丁內醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、4-羥基-4-甲基-2-戊酮（二丙酮醇）、乙二醇單甲醚、乳酸丁酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乙二醇甲醚、乙二醇***、乙二醇-正丙醚、乙二醇-異丙醚、乙二醇-正丁醚（丁基溶纖劑）、乙二醇二甲醚、乙二醇***乙酸酯、二乙二醇二甲醚、二乙二醇二***、二乙二醇單甲醚、二乙二醇單***、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二異丁基酮、丙酸異戊酯、異丁酸異戊酯、二異戊醚、碳酸伸乙酯、碳酸伸丙酯等。這些可單獨使用或混合使用兩種以上。As the organic solvent used, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ-butyrolactone, γ- Butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethylene glycol mono Methyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol- Isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate ester, diisoamyl ether, ethyl carbonate, propylene carbonate, etc. These can be used individually or in mixture of 2 or more types.

液晶配向劑中的固體成分濃度（液晶配向劑的溶媒以外的成分的合計質量在液晶配向劑的總質量中所占的比例）可考慮黏性、揮發性等來適宜選擇。本公開的液晶配向劑的固體成分濃度較佳為1質量%～10質量%的範圍。即，將液晶配向劑如後述那樣塗布於基板表面，較佳為進行加熱，由此形成作為液晶配向膜的塗膜或者成為液晶配向膜的塗膜。此時，若固體成分濃度為1質量%以上，則可充分確保塗膜的膜厚，容易獲得良好的液晶配向膜，就此方面而言較佳。另外，若固體成分濃度為10質量%以下，則塗膜的膜厚不會過大，可獲得良好的液晶配向膜，並且可適度地確保液晶配向劑的黏性，可使塗布性良好。The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, and the like. The solid content concentration of the liquid crystal alignment agent of the present disclosure is preferably in the range of 1% by mass to 10% by mass. That is, the liquid crystal alignment agent is coated on the surface of the substrate as described later, and preferably heated to form a coating film as a liquid crystal alignment film or a coating film as a liquid crystal alignment film. At this time, if the solid content concentration is 1 mass % or more, the film thickness of a coating film can fully be securable, and it is easy to obtain a favorable liquid crystal alignment film, and it is preferable in this point. In addition, if the solid content concentration is 10% by mass or less, the film thickness of the coating film will not be too large, a good liquid crystal alignment film can be obtained, and the viscosity of the liquid crystal alignment agent can be appropriately secured, so that the coatability can be improved.

在液晶配向劑中，相對於液晶配向劑中的聚合物成分的合計100質量份，聚醯胺酸[P]的含有比例較佳為50質量份以上，更佳為55質量份以上，進而較佳為60質量份以上。若聚醯胺酸[P]的含有比例處於所述範圍內，則可充分獲得由碳數2以上的鏈狀結構的導入帶來的膜的韌性的改善效果。另外，相對於液晶配向劑中的聚合物成分的合計100質量份，聚醯胺酸[P]的含有比例較佳為95質量份以下，更佳為90質量份以下。In the liquid crystal alignment agent, with respect to the total 100 mass parts of the polymer components in the liquid crystal alignment agent, the content ratio of polyamic acid [P] is preferably 50 mass parts or more, more preferably 55 mass parts or more, and even more Preferably, it is 60 mass parts or more. When the content ratio of the polyamic acid [P] is within the above range, the effect of improving the toughness of the film due to the introduction of the chain structure having 2 or more carbon atoms can be sufficiently obtained. Moreover, the content ratio of polyamic acid [P] is preferably 95 mass parts or less with respect to a total of 100 mass parts of polymer components in the liquid crystal alignment agent, more preferably 90 mass parts or less.

相對於液晶配向劑中的聚合物成分的合計100質量份，聚合物[Q]的含有比例較佳為5質量份以上，更佳為10質量份以上。若聚合物[Q]的含有比例處於所述範圍內，則可充分獲得由聚合物[Q]帶來的液晶配向性的改善效果。另外，相對於液晶配向劑中的聚合物成分的合計100質量份，聚合物[Q]的含有比例較佳為50質量份以下，更佳為45質量份以下，進而較佳為40質量份以下。The content of the polymer [Q] is preferably at least 5 parts by mass, more preferably at least 10 parts by mass, based on a total of 100 parts by mass of the polymer components in the liquid crystal alignment agent. When the content rate of a polymer [Q] exists in the said range, the improvement effect of the liquid crystal alignment by a polymer [Q] can fully be acquired. In addition, the content of the polymer [Q] is preferably at most 50 parts by mass, more preferably at most 45 parts by mass, and still more preferably at most 40 parts by mass, based on 100 parts by mass of the total polymer components in the liquid crystal alignment agent. .

就實現低殘像特性及高對比度特性與膜強度的並存的觀點而言，液晶配向劑中的聚醯胺酸[P]與聚合物[Q]的比例以質量比（聚醯胺酸[P]/聚合物[Q]）計而較佳為95/5～50/50，更佳為95/5～55/45，進而較佳為95/5～60/40，進而更佳為95/5～75/35。From the viewpoint of achieving the coexistence of low afterimage characteristics and high contrast characteristics and film strength, the ratio of polyamide [P] to polymer [Q] in the liquid crystal alignment agent is expressed by mass ratio (polyamide [P ]/polymer [Q]) is preferably 95/5～50/50, more preferably 95/5～55/45, further preferably 95/5～60/40, and further preferably 95/5～50/50 5~75/35.

《液晶配向膜及液晶元件》 本公開的液晶配向膜可由如所述那樣製備的液晶配向劑來形成。另外，本公開的液晶元件包括使用所述說明的液晶配向劑而形成的液晶配向膜。液晶元件中的液晶的動作模式並無特別限定，例如可應用於扭曲向列（Twisted Nematic，TN）型、超扭曲向列（Super Twisted Nematic，STN）型、垂直配向（Vertical Alignment，VA）型（包含垂直配向-多域垂直配向（Vertical Alignment-Multi-domain Vertical Alignment，VA-MVA）型、垂直配向-圖案垂直配向（Vertical Alignment-Patterned Vertical Alignment，VA-PVA）型等）、共面切換（In-Plane Switching，IPS）型、邊緣場切換（Fringe Field Switching，FFS）型、光學補償彎曲（Optically Compensated Bend，OCB）型等各種模式中。液晶元件例如可通過包括以下的步驟1～步驟3的方法來製造。步驟1中，使用基板視所期望的動作模式而不同。步驟2及步驟3中各動作模式共通。 "Liquid Crystal Alignment Film and Liquid Crystal Components" The liquid crystal alignment film of the present disclosure may be formed from the liquid crystal alignment agent prepared as described. In addition, the liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, for example, it can be applied to twisted nematic (Twisted Nematic, TN) type, super twisted nematic (Super Twisted Nematic, STN) type, vertical alignment (Vertical Alignment, VA) type (including vertical alignment-multi-domain vertical alignment (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, vertical alignment-patterned vertical alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type, etc.), coplanar switching (In-Plane Switching, IPS) type, Fringe Field Switching (Fringe Field Switching, FFS) type, Optically Compensated Bend (Optically Compensated Bend, OCB) type and other modes. A liquid crystal element can be manufactured by the method including the following steps 1-3, for example. In step 1, the substrate used differs depending on the desired operation mode. The operation modes in step 2 and step 3 are common.

（步驟1：塗膜的形成） 首先，將液晶配向劑塗布於基板上，較佳為對塗布面進行加熱，由此在基板上形成有機膜。作為基板，例如可使用：浮法玻璃、鈉玻璃等玻璃；包含聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯、聚(脂環式烯烴)等塑料的透明基板。作為設置於基板的其中一面上的透明導電膜，可使用包含氧化錫（SnO ₂）的奈塞（NESA）膜（美國PPG公司注冊商標）、包含氧化銦-氧化錫（In ₂O ₃-SnO ₂）的氧化銦錫（Indium Tin Oxide，ITO）膜等。在製造TN型、STN型或VA型的液晶元件的情況下，使用2片設置有經圖案化的透明導電膜的基板。另一方面，在製造IPS型或FFS型的液晶元件的情況下，使用設置有包含經圖案化為梳齒型的透明導電膜或金屬膜的電極的基板、與未設置電極的相向基板。作為金屬膜，例如可使用包含鉻等金屬的膜。對基板的液晶配向劑的塗布是在電極形成面上較佳為利用膠版印刷法、旋轉塗布法、輥塗布機法或噴墨印刷法而進行。 (Step 1: Formation of Coating Film) First, the liquid crystal alignment agent is coated on the substrate, and the coated surface is preferably heated to form an organic film on the substrate. As the substrate, for example, glass such as float glass and soda glass can be used; polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly(alicyclic olefin) and other plastic transparent substrates. As the transparent conductive film provided on one side of the substrate, Nesser (NESA) film (registered trademark of PPG Corporation of the United States) containing tin oxide (SnO ₂ ), a film containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Indium tin oxide (Indium Tin Oxide, ITO) film, etc. When manufacturing a TN-type, STN-type, or VA-type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, when manufacturing an IPS or FFS liquid crystal element, a substrate provided with electrodes including a comb-shaped transparent conductive film or a metal film and a counter substrate provided with no electrodes are used. As the metal film, for example, a film containing metal such as chromium can be used. The coating of the liquid crystal alignment agent on the substrate is preferably carried out on the electrode formation surface by offset printing, spin coating, roll coater or inkjet printing.

塗布液晶配向劑後，出於防止所塗布的液晶配向劑的流掛等目的，較佳為實施預加熱（預烘烤）。預烘烤溫度較佳為30℃～200℃，預烘烤時間較佳為0.25分鐘～10分鐘。之後，以完全去除溶劑等為目的而實施煆燒（後烘烤）步驟。此時的煆燒溫度（後烘烤溫度）較佳為80℃～250℃，更佳為80℃～200℃。後烘烤時間較佳為5分鐘～200分鐘。如此形成的有機膜的膜厚較佳為0.001 μm～1 μm。After applying the liquid crystal alignment agent, it is preferable to perform preheating (prebaking) for the purpose of preventing the applied liquid crystal alignment agent from sagging. The pre-baking temperature is preferably 30° C. to 200° C., and the pre-baking time is preferably 0.25 minutes to 10 minutes. Thereafter, a firing (post-baking) step is performed for the purpose of completely removing the solvent and the like. The firing temperature (post-baking temperature) at this time is preferably from 80°C to 250°C, more preferably from 80°C to 200°C. The post-baking time is preferably from 5 minutes to 200 minutes. The film thickness of the organic film thus formed is preferably 0.001 μm to 1 μm.

（步驟2：配向處理） 在製造TN型、STN型、IPS型或FFS型的液晶元件的情況下，實施對所述步驟1中形成的有機膜賦予液晶配向能力的處理（配向處理）。由此，液晶分子的配向能力被賦予至有機膜而成為液晶配向膜。作為配向處理，較佳為使用對基板上所形成的塗膜的表面利用棉花等進行擦拭的摩擦處理、或者對有機膜進行光照射來賦予液晶配向能力的光配向處理。在製造垂直配向型的液晶元件的情況下，可將所述步驟1中形成的有機膜直接用作液晶配向膜，為了進一步提高液晶配向能力，也可對有機膜實施配向處理。 (Step 2: Alignment Processing) In the case of manufacturing a TN-type, STN-type, IPS-type or FFS-type liquid crystal element, a treatment (alignment treatment) for imparting liquid crystal alignment capability to the organic film formed in step 1 is performed. Thereby, the alignment ability of a liquid crystal molecule is given to an organic film, and it becomes a liquid crystal alignment film. As the alignment treatment, rubbing treatment of wiping the surface of the coating film formed on the substrate with cotton or the like, or photo-alignment treatment of imparting liquid crystal alignment ability by irradiating an organic film with light is preferably used. In the case of manufacturing a vertical alignment type liquid crystal element, the organic film formed in step 1 can be directly used as a liquid crystal alignment film, and an alignment treatment can also be performed on the organic film in order to further improve liquid crystal alignment ability.

在光配向處理中，光照射可通過如下方法等來進行：對後烘烤步驟後的有機膜進行照射的方法、對預烘烤步驟後且後烘烤步驟前的塗膜進行照射的方法、在預烘烤步驟及後烘烤步驟中的至少任一步驟中在塗膜的加熱過程中對膜進行照射的方法。作為對膜照射的放射線，例如可使用包含150 nm～800 nm的波長的光的紫外線及可見光線。較佳為包含200 nm～400 nm的波長的光的紫外線。在放射線為偏光的情況下，可為直線偏光，也可為部分偏光。在使用的放射線為直線偏光或部分偏光的情況下，照射可自與基板面垂直的方向進行，可自傾斜方向進行，或也可將這些組合來進行。非偏光的放射線時的照射方向設為傾斜方向。In the photo-alignment process, light irradiation can be performed by methods such as a method of irradiating the organic film after the post-baking step, a method of irradiating the coating film after the pre-baking step and before the post-baking step, A method of irradiating the film during heating of the coating film in at least any one of the pre-baking step and the post-baking step. As the radiation irradiated to the film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. Ultraviolet rays including light having a wavelength of 200 nm to 400 nm are preferable. When the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be combined. The irradiation direction in the case of non-polarized radiation was defined as an oblique direction.

作為使用的光源，例如可列舉：低壓水銀燈、高壓水銀燈、氘燈、金屬鹵化物燈、氬共振燈、氙燈、准分子激光等。對於基板面的放射線的照射量較佳為400 J/m ²～50,000 J/m ²，更佳為1,000 J/m ²～20,000 J/m ²。在用於賦予配向能力的光照射後，也可進行如下處理：使用例如水、有機溶媒（例如，甲醇、異丙醇、1-甲氧基-2-丙醇乙酸酯、丁基溶纖劑、乳酸乙酯等）或它們的混合物對基板表面進行清洗的處理或對基板進行加熱的處理。 As the light source used, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. are mentioned, for example. The radiation dose to the substrate surface is preferably from 400 J/m ² to 50,000 J/m ² , more preferably from 1,000 J/m ² to 20,000 J/m ² . After photoirradiation for imparting alignment ability, treatment may also be performed using, for example, water, organic solvents (e.g., methanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cellosolve, Ethyl lactate, etc.) or a mixture thereof to clean the surface of the substrate or to heat the substrate.

（步驟3：液晶單元的構築） 準備2片以所述方式形成有液晶配向膜的基板，在相向配置的2片基板間配置液晶，由此製造液晶單元。在製造液晶單元時，例如可列舉：（1）以液晶配向膜相向的方式隔著間隙（間隔物）將2片基板相向配置，並使用密封劑將2片基板的周邊部貼合，將液晶注入填充至由基板表面及密封劑劃分的單元間隙內，然後將注入孔密封的方法；（2）將密封劑塗布於形成有液晶配向膜的其中一片基板上的規定場所，進而在液晶配向膜面上的規定的幾處滴加液晶後，以液晶配向膜相向的方式貼合另一片基板，並且使液晶在基板的整面擴散的方法（液晶滴注（one drop filling，ODF）方式）等。較佳為對於所製造的液晶單元，進而進行如下處理，即加熱至所使用的液晶取得各向同性相的溫度，然後緩慢冷卻至室溫的處理，由此將液晶填充時的流動配向去除。 (Step 3: Construction of the liquid crystal cell) A liquid crystal cell was produced by preparing two substrates on which the liquid crystal alignment film was formed as described above, and disposing liquid crystals between the two substrates facing each other. When manufacturing a liquid crystal cell, for example: (1) arrange two substrates facing each other through a gap (spacer) in such a way that the liquid crystal alignment film faces each other, and use a sealant to bond the peripheral parts of the two substrates to bond the liquid crystal A method of injecting and filling into the cell gap divided by the substrate surface and sealant, and then sealing the injection hole; (2) Apply the sealant to a specified place on one of the substrates on which the liquid crystal alignment film is formed, and then apply it to the liquid crystal alignment film After dropping the liquid crystal at several places on the surface, attach another substrate with the liquid crystal alignment film facing each other, and spread the liquid crystal over the entire surface of the substrate (one drop filling (ODF) method), etc. . Preferably, the manufactured liquid crystal cell is heated to a temperature at which the used liquid crystal acquires an isotropic phase, and then slowly cooled to room temperature, thereby removing the flow alignment at the time of liquid crystal filling.

作為密封劑，例如可使用硬化劑以及含有作為間隔物的氧化鋁球的環氧樹脂等。作為間隔物，可使用光間隔物（photospacer）、珠粒間隔物等。As the sealing agent, for example, a curing agent, an epoxy resin containing alumina balls as spacers, or the like can be used. As the spacer, a photospacer, a bead spacer, or the like can be used.

作為液晶，可使用正型及負型的任一種。於在IPS型及FFS型的液晶元件中使用負型液晶的情況下，可減小電極上部的透過損失，可實現對比度提高，就此方面而言較佳。另外，作為使用的液晶，可列舉向列液晶（nematic liquid crystal）、碟狀液晶（smectic liquid crystal），其中較佳為向列液晶。作為向列液晶，例如可使用：希夫堿（Schiff base）系液晶、氧化偶氮（azoxy）系液晶、聯苯系液晶、苯基環己烷系液晶、酯系液晶、三聯苯（terphenyl）系液晶、聯苯基環己烷系液晶、嘧啶系液晶、二噁烷系液晶、雙環辛烷系液晶、立方烷（cubane）系液晶等。另外，也可在這些液晶中添加例如膽甾醇型液晶（cholesteric liquid crystal）、手性試劑、鐵電性液晶（ferroelectric liquid crystal）等來使用。As the liquid crystal, either positive type or negative type can be used. When negative type liquid crystal is used for IPS type and FFS type liquid crystal elements, the transmission loss at the upper part of an electrode can be reduced and contrast ratio can be improved, and it is preferable in this point. In addition, examples of liquid crystals used include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. As nematic liquid crystals, for example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, and terphenyl liquid crystals can be used. Biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, and the like. In addition, these liquid crystals may be used by adding, for example, cholesteric liquid crystals (cholesteric liquid crystals), chiral reagents, ferroelectric liquid crystals (ferroelectric liquid crystals), and the like.

繼而，視需要在液晶單元的外側表面貼合偏光板。作為偏光板，可列舉通過乙酸纖維素保護膜夾持被稱為「H膜」的偏光膜而成的偏光板或者包含H膜其自身的偏光板，所述「H膜」是一邊使聚乙烯基醇延伸配向一邊吸收碘而成。由此，獲得液晶元件。Next, a polarizing plate is bonded to the outer surface of the liquid crystal cell as necessary. Examples of the polarizing plate include a polarizing plate in which a polarizing film called “H film” made of polyethylene film is interposed between cellulose acetate protective films, or a polarizing plate including the H film itself. It is formed by extending the alignment of the base alcohol to one side and absorbing iodine. Thus, a liquid crystal element was obtained.

本公開的液晶元件可有效地應用於各種用途。具體而言，例如可用於時鐘、便攜型遊戲機、文字處理機、筆記型個人計算機、汽車導航系統、攝像機、個人數字助理（Personal Digital Assistant，PDA）、數字相機、移動電話、智能手機、各種監視器、液晶電視、訊息顯示器等各種顯示裝置或者調光膜等中。另外，使用本公開的液晶配向劑形成的液晶元件也可應用於相位差膜等光學膜中。 [實施例] The liquid crystal element of the present disclosure can be effectively applied to various uses. Specifically, for example, it can be used in clocks, portable game machines, word processors, notebook personal computers, car navigation systems, video cameras, personal digital assistants (Personal Digital Assistant, PDA), digital cameras, mobile phones, smart phones, various Various display devices such as monitors, LCD TVs, and information displays, or light-adjustable films, etc. In addition, the liquid crystal element formed using the liquid crystal alignment agent of the present disclosure can also be applied to optical films such as retardation films. [Example]

以下，通過實施例來更具體地說明，但本發明並不限定於這些實施例。Hereinafter, although an Example demonstrates more concretely, this invention is not limited to these Examples.

＜測定方法＞ 在以下例子中，聚合物的溶液黏度及醯亞胺化率是通過以下方法來測定。 [聚合物的溶液黏度] 聚合物的溶液黏度是使用E型黏度計在25℃下進行測定。 [聚醯亞胺的醯亞胺化率] 將聚醯亞胺的溶液投入至純水中，將所獲得的沉澱在室溫下充分減壓乾燥，然後溶解於氘化二甲基亞碸中，以四甲基矽烷為基準物質，在室溫下進行 ¹H-核磁共振（ ¹H-Nuclear Magnetic Resonance， ¹H-NMR）測定。根據所獲得的 ¹H-NMR光譜，並通過下述數式（1）來求出醯亞胺化率[%]。 醯亞胺化率[%]=（1-（β ¹/（β ²×α）））×100 …（1） （數式（1）中，β ¹為在化學位移10 ppm附近出現的源自NH基的質子的峰值面積，β ²為源自其他質子的峰值面積，α為其他質子相對於聚合物的前體（聚醯胺酸）中的NH基的1個質子的個數比例） <Measurement method> In the following examples, the solution viscosity and imidization rate of the polymer were measured by the following methods. [Solution Viscosity of Polymer] The solution viscosity of the polymer was measured at 25° C. using an E-type viscometer. [Imidation rate of polyimide] A solution of polyimide was poured into pure water, and the obtained precipitate was fully dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl oxide to obtain Tetramethylsilane is used as a reference substance, and ¹ H-NMR ( ¹ H-Nuclear Magnetic Resonance, ¹ H-NMR) measurement is performed at room temperature. From the obtained ¹ H-NMR spectrum, the imidization rate [%] was determined by the following formula (1). Imidization rate [%]=(1-(β ¹ /(β ² ×α)))×100…(1) (In formula (1), β ¹ is the source that appears near the chemical shift of 10 ppm The peak area of the proton derived from the NH group, ^β2 is the peak area derived from other protons, and α is the ratio of the number of other protons to one proton of the NH group in the polymer precursor (polyamide acid))

＜化合物的簡稱＞ 以下示出下述例中使用的化合物的簡稱。此外，以下，方便起見，有時將「式（X）所表示的化合物」簡單示為「化合物（X）」。 <Abbreviation of compound> Abbreviations of compounds used in the following examples are shown below. In addition, in the following, "the compound represented by the formula (X)" may be simply shown as "the compound (X)" for the sake of convenience.

[四羧酸二酐] [化17]

[Tetracarboxylic dianhydride] [Chemical 17]

[二胺] [化18]

[化19]

[Diamine] [Chemical 18]

[chemical 19]

[添加劑] [化20]

[Additive] [Chemical 20]

＜聚合物的合成＞＜Synthesis of Polymer＞

1.聚醯胺酸的合成 [合成例1] 將作為四羧酸二酐的1,2,3,4-環丁烷四羧酸二酐50莫耳份及2,3,5-三羧基環戊基乙酸二酐50莫耳份、以及作為二胺的化合物（D-2）90莫耳份及化合物（D-11）10莫耳份溶解於N-甲基-2-吡咯烷酮（N-methyl-2-pyrrolidone，NMP）中，在40℃下反應24小時，由此獲得含有20質量%的聚醯胺酸（將其設為聚合物（P-1））的溶液。少量分取所述溶液，加入NMP而製成濃度為10質量%的溶液，測定所得的溶液黏度為80 mPa·s。 1. Synthesis of polyamic acid [Synthesis Example 1] 50 molar parts of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 50 molar parts of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, and 90 mol parts of diamine compound (D-2) and 10 mol parts of compound (D-11) were dissolved in N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP) at 40°C The reaction was carried out for 24 hours to obtain a solution containing 20% by mass of polyamic acid (this is referred to as polymer (P-1)). A small amount of the solution was taken, and NMP was added to prepare a solution with a concentration of 10% by mass. The viscosity of the obtained solution was measured to be 80 mPa·s.

[合成例2～合成例11、合成例15～合成例17、合成例19～合成例22] 將聚合中使用的四羧酸二酐及二胺的種類及量如表1及表2中記載那樣加以變更，除此以外，與合成例1同樣地進行聚合，獲得分別含有作為聚醯胺酸的聚合物（P-2）～聚合物（P-11）、聚合物（Q-4）～聚合物（Q-6）、聚合物（R-1）～聚合物（R-4）的溶液。此外，以聚合物濃度為10質量%的NMP溶液的黏度成為80 mPa·s～100 mPa·s的方式且使二胺與四羧酸二酐的莫耳比（二胺/四羧酸二酐）與0.95～1.00相匹配地實施聚合。表1及表2中，酸酐的數值表示各化合物相對於合成中使用的四羧酸二酐的總量100莫耳份的比例（莫耳份）。二胺的數值表示各化合物相對於合成中使用的二胺的總量100莫耳份的比例（莫耳份）。 [Synthesis Example 2 to Synthesis Example 11, Synthesis Example 15 to Synthesis Example 17, Synthesis Example 19 to Synthesis Example 22] Except that the types and amounts of tetracarboxylic dianhydride and diamine used in the polymerization were changed as described in Table 1 and Table 2, polymerization was carried out in the same manner as in Synthesis Example 1 to obtain Polymer (P-2) ~ Polymer (P-11), Polymer (Q-4) ~ Polymer (Q-6), Polymer (R-1) ~ Polymer (R-4) solution . In addition, the molar ratio of diamine to tetracarboxylic dianhydride (diamine/tetracarboxylic dianhydride ) to match 0.95 to 1.00 to carry out aggregation. In Table 1 and Table 2, the numerical value of an acid anhydride represents the ratio (parts by mole) of each compound with respect to 100 parts by mole of the total amount of tetracarboxylic dianhydride used for synthesis. The numerical value of diamine represents the ratio (parts by mole) of each compound to 100 parts by mole of the total amount of diamines used for synthesis.

2.聚醯亞胺的合成 [合成例12] 將作為四羧酸二酐的1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐100莫耳份、以及作為二胺的化合物（D-1）50莫耳份及2,2'-二甲基聯苯胺50莫耳份溶解於N-甲基-2-吡咯烷酮（NMP）中，在40℃下反應24小時，由此獲得含有20質量%的聚醯胺酸的溶液。繼而，在所獲得的聚醯胺酸溶液中追加NMP，相對於聚醯胺酸的羧基添加各為1.60莫耳當量的吡啶及乙酸酐，在80℃下進行3小時脫水閉環反應。脫水閉環反應後，利用新的γ-丁內酯對系統內的溶媒進行溶媒置換，進一步濃縮，由此獲得含有20質量%的醯亞胺化率為85%的聚醯亞胺（將其設為聚合物（Q-1））的溶液。少量分取所述溶液，加入NMP而製成濃度為10質量%的溶液，測定所得的溶液黏度為100 mPa·s。 2. Synthesis of Polyimide [Synthesis Example 12] 100 mol parts of 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride as tetracarboxylic dianhydride and 50 moles of compound (D-1) as diamine Parts of ear and 50 moles of 2,2'-dimethylbenzidine were dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at 40°C for 24 hours to obtain a polyamide containing 20% by mass. Amino acid solution. Next, NMP was added to the obtained polyamic acid solution, 1.60 molar equivalents of pyridine and acetic anhydride each were added to the carboxyl groups of the polyamic acid, and a dehydration ring-closure reaction was performed at 80° C. for 3 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new gamma-butyrolactone, and further concentrated to obtain a polyimide containing 20% by mass and an imidization rate of 85% (set it as is a solution of polymer (Q-1)). A small amount of the solution was collected, NMP was added to prepare a solution with a concentration of 10% by mass, and the viscosity of the obtained solution was measured to be 100 mPa·s.

[合成例13、合成例14] 將聚合中使用的四羧酸二酐及二胺的種類及量如表2中記載那樣加以變更，除此以外，與合成例12同樣地進行聚合，分別獲得含有作為聚醯亞胺的聚合物（Q-2）、聚合物（Q-3）的溶液。 [Synthesis Example 13, Synthesis Example 14] Except that the types and amounts of tetracarboxylic dianhydride and diamine used in the polymerization were changed as described in Table 2, polymerization was carried out in the same manner as in Synthesis Example 12, and polymers containing (Q-2), a solution of polymer (Q-3).

3.聚醯胺酸酯的合成 使化合物（T-8）100莫耳份溶解於N-甲基-2-吡咯烷酮（NMP）中，然後向其中加入作為二胺的化合物（D-1）50莫耳份及對苯二胺50莫耳份並加以溶解。在所述溶液中添加4-(4,6-二甲氧基-1,3,5-三嗪-2-基)-4-甲基嗎啉鎓氯化物（DMT-MM、15±2質量%水合物）300莫耳份，在室溫下進行4小時反應，獲得含有聚合物（Q-7）作為聚醯胺酸酯的溶液。 3. Synthesis of polyamide ester Dissolve 100 molar parts of compound (T-8) in N-methyl-2-pyrrolidone (NMP), and then add 50 molar parts of compound (D-1) as diamine and 50 molar parts of p-phenylenediamine molar parts and dissolved. Add 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM, 15 ± 2 mass % hydrate) 300 mole parts, and reacted at room temperature for 4 hours to obtain a solution containing the polymer (Q-7) as polyamic acid ester.

[表1]    聚醯胺酸[P] 合成例1 合成例2 合成例3 合成例4 合成例5 合成例6 合成例7 合成例8 合成例9 合成例10 合成例11 聚合物名稱 P-1 P-2 P-3 P-4 P-5 P-6 P-7 P-8 P-9 P-10 P-11 酸衍生物 T-1          50 50          50       T-2                40    30          T-3       50          50             T-4                            80    T-5                               10 T-6 50 50 40             20    20    T-7             50 10                T-8                                  T-9    50          50                T-10 50    10 50       50          90 T-11                      50          T-12                         50       二胺 D-1                                  D-2 90 50       30             10 30 D-3       30 10                      D-4             20                   D-5                50                D-6                   50             D-7                                  D-8                      80          D-9                         60       D-10    40 60 80          20 20 80 30 D-11 10             10                D-12             50                   D-13                   40             D-14                   10          30 D-15                         10       D-16    10                   10 10 10 D-17                                  D-18       10                         D-19          10    40                [Table 1] Polyamide [P] Synthesis Example 1 Synthesis example 2 Synthesis example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Synthesis Example 11 polymer name P-1 P-2 P-3 P-4 P-5 P-6 P-7 P-8 P-9 P-10 P-11 acid derivatives T-1 50 50 50 T-2 40 30 T-3 50 50 T-4 80 T-5 10 T-6 50 50 40 20 20 T-7 50 10 T-8 T-9 50 50 T-10 50 10 50 50 90 T-11 50 T-12 50 diamine D-1 D-2 90 50 30 10 30 D-3 30 10 D-4 20 D-5 50 D-6 50 D-7 D-8 80 D-9 60 D-10 40 60 80 20 20 80 30 D-11 10 10 D-12 50 D-13 40 D-14 10 30 D-15 10 D-16 10 10 10 10 D-17 D-18 10 D-19 10 40

[表2]    聚合物[Q] 其他聚合物 合成例12 合成例13 合成例14 合成例15 合成例16 合成例17 合成例18 合成例19 合成例20 合成例21 合成例22 聚合物名稱 Q-1 Q-2 Q-3 Q-4 Q-5 Q-6 Q-7 R-1 R-2 R-3 R-4 酸衍生物 T-1             100 50                T-2                                  T-3                                  T-4                                  T-5                            100    T-6       20       50    50 50    50 T-7 100 100 80 100                      T-8                   100             T-9                                  T-10                      50 50    50 T-11                                  T-12                                  二胺 D-1 50       50    50 50             D-2             100 50    90          D-3                                  D-4    100                            D-5                                  D-6                                  D-7       50                         D-8                                  D-9                                  D-10                         90       D-11                                  D-12                                  D-13                                  D-14                                  D-15                                  D-16                            10 10 D-17       50          50 10    90 90 D-18                         10       D-19 50       50                      [Table 2] Polymer [Q] other polymers Synthesis Example 12 Synthesis Example 13 Synthesis Example 14 Synthesis Example 15 Synthesis Example 16 Synthesis Example 17 Synthesis Example 18 Synthesis Example 19 Synthesis Example 20 Synthesis Example 21 Synthesis Example 22 polymer name Q-1 Q-2 Q-3 Q-4 Q-5 Q-6 Q-7 R-1 R-2 R-3 R-4 acid derivatives T-1 100 50 T-2 T-3 T-4 T-5 100 T-6 20 50 50 50 50 T-7 100 100 80 100 T-8 100 T-9 T-10 50 50 50 T-11 T-12 diamine D-1 50 50 50 50 D-2 100 50 90 D-3 D-4 100 D-5 D-6 D-7 50 D-8 D-9 D-10 90 D-11 D-12 D-13 D-14 D-15 D-16 10 10 D-17 50 50 10 90 90 D-18 10 D-19 50 50

[實施例1：光配向FFS型液晶顯示元件] （1）液晶配向劑（AL-1）的製備 在合成例1中獲得的包含聚合物（P-1）90質量份的溶液中加入合成例12中獲得的包含聚合物（Q-1）10質量份的溶液、以及作為溶劑的NMP及丁基溶纖劑（Butyl Cellosolve，BC），製成溶劑組成為NMP/BC=70/30（質量比）、固體成分濃度為4.0質量%的溶液。利用孔徑為0.2 μm的過濾器對所述溶液進行過濾，由此製備液晶配向劑（AL-1）。 [Example 1: Photoalignment FFS type liquid crystal display element] (1) Preparation of liquid crystal alignment agent (AL-1) Add the solution containing 10 parts by mass of the polymer (Q-1) obtained in Synthesis Example 12, and NMP and butyl cellosolve as solvents to the solution containing 90 parts by mass of the polymer (P-1) obtained in Synthesis Example 1 (Butyl Cellosolve, BC) to prepare a solution with a solvent composition of NMP/BC=70/30 (mass ratio) and a solid content concentration of 4.0% by mass. The liquid crystal alignment agent (AL-1) was prepared by filtering the solution through a filter with a pore size of 0.2 μm.

（2）光配向FFS型液晶顯示元件的製造 準備在單面依序層疊有平板電極（底電極）、絕緣層及梳齒狀電極（頂電極）的玻璃基板（設為第一基板）、以及未設置電極的玻璃基板（設為第二基板）。繼而，利用旋轉器在第一基板的電極形成面及第二基板的其中一基板面上分別塗布液晶配向劑（AL-1），在80℃的加熱板上加熱（預烘烤）1分鐘。之後，在對庫內進行了氮氣置換的230℃的烘箱中進行30分鐘乾燥（後烘烤），形成平均膜厚為0.1 μm的塗膜。使用Hg-Xe燈自基板法線方向對所獲得的塗膜照射包含經直線偏光的254 nm的亮線的紫外線1,000 J/cm ²來實施光配向處理。此外，所述照射量是使用以波長254 nm基準進行測量的光量計測量而得的值。繼而，將實施了光配向處理的塗膜在230℃的潔淨烘箱中加熱30分鐘來進行熱處理，從而形成液晶配向膜。 其次，針對形成有液晶配向膜的一對基板中的其中一基板，通過絲網印刷而將放入有直徑為3.5 μm的氧化鋁球的環氧樹脂黏接劑塗布於具有液晶配向膜的面的外緣。之後，以光照射時的偏光軸在基板面上的投影方向成為逆平行的方式重疊基板並進行壓接，在150℃下歷時1小時使黏接劑熱硬化。繼而，自液晶注入口向一對基板間填充負型液晶（默克（Merck）公司製造、MLC-6608），然後利用環氧系黏接劑將液晶注入口密封，獲得液晶單元。進而，為了去除液晶注入時的流動配向，而將其在120℃下加熱後緩慢冷卻至室溫。之後，在液晶單元中的基板的外側兩面貼合偏光板，從而獲得液晶顯示元件。另外，在100 J/cm ²～10,000 J/cm ²的範圍內分別變更後烘烤後的紫外線照射量來實施所述一系列操作，由此製造紫外線照射量不同的3個以上的液晶顯示元件，將顯示出最良好的配向特性的曝光量（最佳曝光量）的液晶顯示元件用於以下評價。 (2) Manufacture of photo-alignment FFS type liquid crystal display element Prepare a glass substrate (referred to as the first substrate) on which a flat electrode (bottom electrode), an insulating layer and a comb-shaped electrode (top electrode) are sequentially laminated on one side, and A glass substrate without electrodes (set as a second substrate). Next, the liquid crystal alignment agent (AL-1) was coated on the electrode formation surface of the first substrate and one of the substrate surfaces of the second substrate with a spinner, and heated (pre-baked) on a hot plate at 80° C. for 1 minute. Thereafter, drying (post-baking) was performed for 30 minutes in an oven at 230° C. in which the inside of the chamber was replaced with nitrogen to form a coating film with an average film thickness of 0.1 μm. The obtained coating film was irradiated with 1,000 J/cm ² of ultraviolet rays including a bright line of 254 nm linearly polarized from the direction normal to the substrate using a Hg-Xe lamp to perform photoalignment treatment. In addition, the said irradiation amount is the value measured using the light meter which measures based on wavelength 254 nm. Next, the coating film subjected to the photo-alignment treatment was heated and heat-treated in a clean oven at 230° C. for 30 minutes to form a liquid crystal alignment film. Next, for one of the pair of substrates on which the liquid crystal alignment film is formed, an epoxy resin adhesive containing alumina balls with a diameter of 3.5 μm is applied to the surface with the liquid crystal alignment film by screen printing. the outer edge. Thereafter, the substrates were laminated so that the projection direction of the polarization axis on the substrate surface during light irradiation was antiparallel, and pressure-bonded, and the adhesive was thermally cured at 150° C. for 1 hour. Next, negative-type liquid crystal (MLC-6608, manufactured by Merck) was filled between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port was sealed with an epoxy-based adhesive to obtain a liquid crystal cell. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, after heating at 120 degreeC, it cooled slowly to room temperature. Thereafter, polarizing plates were bonded to both outer surfaces of the substrate in the liquid crystal cell to obtain a liquid crystal display element. In addition, the above-mentioned series of operations are performed by changing the ultraviolet irradiation amount after the post-baking within the range of 100 J/cm ² to 10,000 J/cm ² , thereby manufacturing three or more liquid crystal display elements with different ultraviolet irradiation amounts. , the liquid crystal display element at the exposure amount (optimum exposure amount) showing the best alignment characteristics was used for the following evaluation.

（3）黑亮度評價 對於所述製造的FFS型液晶單元（未貼合偏光板的液晶單元），使用在光源與光量檢測器之間配置有偏光器與檢偏器的裝置來測定下述數式（3）所表示的最小相對透過率（%）。 最小相對透過率（%）=（β ₀-B ₀）/（B ₁₀₀-B ₀）×100     …（3） （數式（3）中，B ₀為空白（blank），且為正交尼科耳（crossed nicols）下的光的透過量；B ₁₀₀為空白，且為平行尼科耳（parallel nicols）下的光的透過量；β為正交尼科耳下在偏光器與檢偏器之間夾持液晶顯示元件且成為最小的光透過量） 暗狀態的黑電平（黑亮度）是由液晶顯示元件的最小相對透過率表示，暗狀態下的黑電平越小，對比度特性越優異。將最小相對透過率未滿0.5%的情況設為「良好（○）」，將0.5%以上、未滿1.0%的情況設為「可（△）」，將1.0%以上的情況設為「不良（×）」。其結果，所述液晶顯示元件的最小相對透過率為0.9%，對比度特性被判斷為「可（△）」。 (3) Evaluation of black luminance For the FFS-type liquid crystal cell manufactured above (liquid crystal cell without a polarizing plate attached), the following data were measured using an apparatus in which a polarizer and an analyzer were disposed between the light source and the light quantity detector. The minimum relative transmittance (%) represented by formula (3). Minimum relative transmittance (%)=(β ₀ -B ₀ )/(B ₁₀₀ -B ₀ )×100...(3) (In formula (3), B ₀ is blank and is orthogonal The transmittance of light under crossed nicols; B ₁₀₀ is blank, and is the transmittance of light under parallel nicols; β is the crossed Nicols between the polarizer and analyzer The black level (black brightness) in the dark state is represented by the minimum relative transmittance of the liquid crystal display element. The smaller the black level in the dark state, the better the contrast characteristic. excellent. When the minimum relative transmittance is less than 0.5%, it is regarded as "good (○)", when it is more than 0.5% and less than 1.0%, it is regarded as "acceptable (△)", and when it is more than 1.0%, it is regarded as "poor". (×)". As a result, the minimum relative transmittance of the liquid crystal display element was 0.9%, and the contrast characteristic was judged to be "possible (Δ)".

（4）交流電（Alternating Current，AC）殘像特性的評價 通過施加交流電壓10 V而將所述製造的FFS型液晶單元（未貼合偏光板的液晶單元）驅動30小時，然後使用在光源與光量檢測器之間配置有偏光器與檢偏器的裝置來測定下述數式（4）所表示的黑亮度變化率（%）。 黑亮度變化率（%）=（β _{30 hr}-β ₀）/β ₀×100  …（4） （數式（4）中，β ₀為正交尼科耳下在偏光器與檢偏器之間夾持驅動應力前的液晶顯示元件且成為最小的光透過量；β _{30 hr}為正交尼科耳下在偏光器與檢偏器之間夾持驅動30小時後的液晶顯示元件且成為最小的光透過量） AC殘像特性是由利用交流電壓驅動30小時前的黑電平與利用交流電壓驅動30小時後的黑電平的變化率表示，可以說變化率越小，AC殘像特性越優異。將黑亮度變化率未滿10%的情況設為「良好（○）」，將10%以上、未滿30%的情況設為「可（△）」，將30%以上的情況設為「不良（×）」。其結果，所述液晶顯示元件的黑亮度變化率為9%，AC殘像特性被判斷為「良好（○）」。 (4) Evaluation of afterimage characteristics of alternating current (Alternating Current, AC) By applying an alternating current voltage of 10 V, the manufactured FFS type liquid crystal cell (a liquid crystal cell without a polarizing plate) was driven for 30 hours, and then used in a light source and A device in which a polarizer and an analyzer are disposed between the light quantity detectors measures the black luminance change rate (%) represented by the following formula (4). Black brightness change rate (%)=(β _{30 hr} -β ₀ )/β ₀ ×100 ... (4) (In the formula (4), β ₀ is the crossed Nicols between the polarizer and the analyzer β _{30 hr} is the liquid crystal display element clamped and driven between the polarizer and the analyzer for 30 hours under crossed Nicols and becomes the minimum The amount of light transmitted) The AC afterimage characteristic is expressed by the change rate of the black level before the AC voltage is driven for 30 hours and the black level after the AC voltage is driven for 30 hours. It can be said that the smaller the change rate, the AC afterimage characteristic more excellent. When the black brightness change rate is less than 10%, it is regarded as "good (○)", when it is more than 10% and less than 30%, it is regarded as "acceptable (△)", and when it is more than 30%, it is regarded as "poor". (×)". As a result, the black luminance change rate of the liquid crystal display element was 9%, and the AC afterimage characteristic was judged to be "good (◯)".

（5）密封密合性的評價（膜內強度的評價） 使用旋轉器在玻璃基板上塗布液晶配向劑（AL-1），在80℃的加熱板上進行2分鐘預烘烤，然後在對庫內進行了氮氣置換的230℃的烘箱中加熱（後烘烤）30分鐘，由此形成平均膜厚為0.10 μm的塗膜。通過重複進行與所述相同的操作而製作2片形成有塗膜的玻璃基板。在形成有塗膜的1片玻璃基板的塗膜上以寬度成為1 mm的方式塗布ODF密封劑（積水化學公司製造、S-WB42），並以另一片玻璃基板的塗膜與ODF密封劑接觸的方式貼合。之後，使用金屬鹵化物燈照射30,000 J/m ²（365 nm換算）的光，然後在120℃的烘箱中加熱1小時。之後，使用今田製作所的拉伸壓縮試驗機（型號：SDWS-0201-100SL）來測定密合力，由此評價膜對於密封劑的密合性。可以說密封密合性越高，膜的基板界面的韌性越高。評價中，將密合力為175 N/cm ²以上的情況設為「優（S）」，將150 N/cm ²以上、未滿175 N/cm ²的情況設為「良好（○）」，將125 N/cm ²以上、未滿150 N/cm ²的情況設為「可（△）」，將未滿125 N/cm ²的情況設為「不良（×）」。其結果，所述實施例的密合力為172 N/cm ²，且為密合性「良好（○）」的評價。 (5) Evaluation of seal adhesion (evaluation of film strength) Use a rotator to coat a liquid crystal alignment agent (AL-1) on a glass substrate, pre-bake it on a heating plate at 80°C for 2 minutes, and then A coating film with an average film thickness of 0.10 μm was formed by heating (post-baking) for 30 minutes in a 230° C. oven in which the chamber was replaced with nitrogen. Two glass substrates on which a coating film was formed were produced by repeating the same operation as above. Apply an ODF sealant (S-WB42, manufactured by Sekisui Chemical Co., Ltd.) to a width of 1 mm on the coating film of one glass substrate on which the coating film is formed, and bring the coating film of the other glass substrate into contact with the ODF sealant way fit. After that, 30,000 J/m ² (365 nm conversion) light was irradiated using a metal halide lamp, and then heated in an oven at 120° C. for 1 hour. Thereafter, the adhesiveness of the film to the sealant was evaluated by measuring the adhesive force using a tension-compression testing machine (model: SDWS-0201-100SL) of Imada Manufacturing Co., Ltd. It can be said that the higher the seal adhesion, the higher the toughness of the substrate interface of the film. In the evaluation, when the adhesion force was 175 N/cm ² or more, it was rated as "Excellent (S)", and when it was 150 N/cm ² or more and less than 175 N/cm ² , it was rated as "Good (○)", The case of 125 N/cm ² or more and less than 150 N/cm ² was regarded as "OK (△)", and the case of less than 125 N/cm ² was regarded as "Poor (×)". As a result, the adhesive force of the said Example was 172 N/cm ² , and it was evaluated as "good (○)" of adhesiveness.

（6）利用剝離試驗的密合性評價（基板界面強度） 使用旋轉器在形成有氮化矽膜的玻璃基板上塗布液晶配向劑（AL-1），在80℃的加熱板上進行2分鐘預烘烤，然後在對庫內進行了氮氣置換的230℃的烘箱中加熱（後烘烤）30分鐘，由此形成平均膜厚為0.10 μm的液晶配向膜。繼而，將形成有液晶配向膜的基板在溫度85℃、濕度85%的恆溫槽中放置1小時。之後，將基板自恆溫槽中取出，使用帶有導件的等間隔間隔物並利用切割刀對液晶配向膜切入切口，從而在1 cm×1 cm的範圍內形成10個×10個的格子圖案。各切口的深度設為自液晶配向膜的表面到達基板厚度的中點為止。繼而，以覆蓋所述格子圖案的整個面的方式使透明膠帶密合，然後將透明膠帶剝落。通過正交尼科耳下的目視來觀察剝落後的格子圖案的切口部並評價密合性。可以說基於所述剝離試驗的密合性越高，膜的基板界面的韌性越高。評價中，將在沿著切口線的部分及格子圖案的交叉部分未確認到剝離的情況設為密合性「良好（〇）」，將在所述部分觀察到剝離的格子眼的個數相對於格子圖案整體的個數而未滿15%的情況設為密合性「可（△）」，將在所述部分觀察到剝離的格子眼的個數相對於格子圖案整體的個數而為15%以上的情況設為密合性「不良（×）」。其結果，所述液晶配向膜的密合性為「良好（〇）」。 (6) Adhesion evaluation by peel test (substrate interface strength) Apply a liquid crystal alignment agent (AL-1) on a glass substrate formed with a silicon nitride film using a spinner, pre-bake it on a hot plate at 80°C for 2 minutes, and then place it in a chamber at 230°C with nitrogen replacement. heated (post-baked) in an oven for 30 minutes, thereby forming a liquid crystal alignment film with an average film thickness of 0.10 μm. Next, the substrate on which the liquid crystal alignment film was formed was placed in a thermostat at a temperature of 85° C. and a humidity of 85% for 1 hour. Afterwards, the substrate was taken out from the constant temperature bath, and the liquid crystal alignment film was cut into incisions using an equal-spaced spacer with guides and a dicing knife to form a grid pattern of 10 x 10 within a range of 1 cm x 1 cm . The depth of each cut was set from the surface of the liquid crystal alignment film to the midpoint of the thickness of the substrate. Next, the cellophane tape is adhered so as to cover the entire surface of the lattice pattern, and then the cellophane tape is peeled off. The notch part of the grid pattern after peeling was observed visually under the cross-Nicol, and adhesiveness was evaluated. It can be said that the higher the adhesiveness based on the peel test, the higher the toughness of the substrate interface of the film. In the evaluation, the case where peeling was not confirmed at the part along the incision line and the intersection part of the grid pattern was regarded as "good (o)" in the adhesiveness, and the number of grid holes where peeling was observed at the part was compared to The case where the number of the entire grid pattern is less than 15% is regarded as "possible (△)" in the adhesiveness, and the number of grid eyes where peeling is observed in the part is 15 with respect to the number of the entire grid pattern When % or more, the adhesiveness was regarded as "poor (×)". As a result, the adhesiveness of the said liquid crystal alignment film was "good (o)".

[實施例2～實施例4、實施例7～實施例13及比較例1～比較例4] 將調配組成如表3及表4所示那樣加以變更，除此以外，以與實施例1相同的溶劑組成及固體成分濃度來製備液晶配向劑（AL-2）～液晶配向劑（AL-4）、液晶配向劑（AL-7）～液晶配向劑（AL-13）、液晶配向劑（AR-1）～液晶配向劑（AR-4）。另外，使用各液晶配向劑，與實施例1同樣地進行而製造光配向FFS型液晶顯示元件，並且進行各種評價。將評價結果示於表3及表4中。 [Example 2-Example 4, Example 7-Example 13 and Comparative Example 1-Comparative Example 4] The preparation composition was changed as shown in Table 3 and Table 4, except that, the same solvent composition and solid content concentration as in Example 1 were used to prepare liquid crystal alignment agents (AL-2) to liquid crystal alignment agents (AL-4 ), liquid crystal alignment agent (AL-7) ~ liquid crystal alignment agent (AL-13), liquid crystal alignment agent (AR-1) ~ liquid crystal alignment agent (AR-4). Moreover, using each liquid crystal alignment agent, it carried out similarly to Example 1, manufactured the photo-alignment FFS type liquid crystal display element, and performed various evaluation. The evaluation results are shown in Table 3 and Table 4.

[實施例5：摩擦配向FFS型液晶顯示元件] （1）液晶配向劑（AL-5）的製備 將調配組成如表3所示那樣加以變更，除此以外，以與實施例1相同的溶劑組成及固體成分濃度來製備液晶配向劑（AL-5）。 [Example 5: Frictional alignment FFS type liquid crystal display element] (1) Preparation of liquid crystal alignment agent (AL-5) Except having changed the preparation composition as shown in Table 3, the liquid crystal alignment agent (AL-5) was prepared with the same solvent composition and solid content concentration as Example 1.

（2）摩擦配向FFS型液晶顯示元件的製造 準備在單面依序層疊有平板電極（底電極）、絕緣層及梳齒狀電極（頂電極）的玻璃基板（第一基板）、以及未設置電極的玻璃基板（第二基板）。繼而，利用旋轉器在第一基板的電極形成面及第二基板的單面上分別塗布液晶配向劑（AL-5），在110℃的加熱板上加熱（預烘烤）3分鐘。之後，在對庫內進行了氮氣置換的230℃的烘箱中進行30分鐘乾燥（後烘烤），形成平均膜厚為0.08 μm的塗膜。繼而，對於塗膜表面，利用具有捲繞有尼龍布的輥的摩擦機，以輥轉數1000 rpm、平臺移動速度3 cm/秒、毛壓入長度0.3 mm進行摩擦處理。之後，在超純水中進行1分鐘超聲波清洗，繼而，在100℃的潔淨烘箱中乾燥10分鐘，由此獲得具有液晶配向膜的一對基板。 繼而，針對具有液晶配向膜的一對基板，在形成有液晶配向膜的面的邊緣殘留液晶注入口，絲網印刷塗布放入有直徑為3.5 μm的氧化鋁球的環氧樹脂黏接劑。之後，重疊基板並進行壓接，在150℃下歷時1小時使黏接劑熱硬化。繼而，自液晶注入口向一對基板間的間隙填充負型液晶（默克（Merck）公司製造、MLC-6608），然後利用環氧系黏接劑將液晶注入口密封。進而，為了去除液晶注入時的流動配向，而將其在120℃下加熱後緩慢冷卻至室溫，而製造液晶單元。此外，在重疊一對基板時，以各基板的摩擦方向成為反平行的方式進行。其次，在液晶單元中的基板的外側兩面貼合偏光板，從而獲得摩擦配向FFS型液晶顯示元件。 (2) Manufacture of friction alignment FFS type liquid crystal display element Prepare a glass substrate (first substrate) on which a plate electrode (bottom electrode), an insulating layer, and a comb-shaped electrode (top electrode) are sequentially laminated on one side, and a glass substrate without electrodes (second substrate). Next, a liquid crystal alignment agent (AL-5) was coated on the electrode formation surface of the first substrate and one surface of the second substrate with a spinner, and heated (prebaked) on a hot plate at 110° C. for 3 minutes. Thereafter, drying (post-baking) was performed for 30 minutes in a 230° C. oven in which the inside of the chamber was replaced with nitrogen to form a coating film with an average film thickness of 0.08 μm. Next, the surface of the coating film was rubbed with a rubbing machine having a roller wound with a nylon cloth at a roller rotation speed of 1000 rpm, a table moving speed of 3 cm/sec, and a bristle indentation length of 0.3 mm. Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a clean oven at 100° C. for 10 minutes, thereby obtaining a pair of substrates having a liquid crystal alignment film. Next, for a pair of substrates having a liquid crystal alignment film, a liquid crystal injection port was left on the edge of the surface on which the liquid crystal alignment film was formed, and an epoxy resin adhesive containing alumina balls with a diameter of 3.5 μm was applied by screen printing. Thereafter, the substrates were laminated and bonded by pressure, and the adhesive was thermally cured at 150° C. for 1 hour. Next, negative-type liquid crystal (MLC-6608, manufactured by Merck) was filled into the gap between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port was sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, after heating at 120 degreeC, it was gradually cooled to room temperature, and the liquid crystal cell was manufactured. In addition, when a pair of substrates are stacked, it is performed so that the rubbing direction of each substrate becomes antiparallel. Next, polarizing plates are pasted on the outer sides of the substrate in the liquid crystal cell to obtain a rubbed alignment FFS type liquid crystal display element.

（3）評價 使用液晶配向劑（AL-5）及摩擦配向FFS型液晶顯示元件，與實施例1同樣地進行黑亮度評價、AC殘像特性的評價、密封密合性的評價及利用剝離試驗的密合性評價。將這些的結果示於表3中。 (3) Evaluation Using a liquid crystal alignment agent (AL-5) and a rubbed-aligned FFS-type liquid crystal display element, evaluation of black brightness, evaluation of AC afterimage characteristics, evaluation of sealing adhesion, and adhesion by peeling test were performed in the same manner as in Example 1. Evaluation. These results are shown in Table 3.

[實施例6] 將調配組成如表3所示那樣加以變更，除此以外，以與實施例1相同的溶劑組成及固體成分濃度來製備液晶配向劑（AL-6）。另外，使用液晶配向劑（AL-6），與實施例5同樣地進行而製造摩擦配向FFS型液晶顯示元件，並且進行各種評價。將評價結果示於表3中。此外，表3及表4中，括號內的數值表示製備液晶配向劑時的各化合物的調配量（質量份）。 [Example 6] Except having changed the preparation composition as shown in Table 3, the liquid crystal alignment agent (AL-6) was prepared with the same solvent composition and solid content concentration as Example 1. Moreover, using the liquid crystal alignment agent (AL-6), it carried out similarly to Example 5, manufactured the rubbing alignment FFS type liquid crystal display element, and performed various evaluation. The evaluation results are shown in Table 3. In addition, in Table 3 and Table 4, the numerical value in parentheses represents the compounding quantity (mass part) of each compound when preparing a liquid crystal alignment agent.

[表3]    實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 配向劑 配向劑名稱 AL-1 AL-2 AL-3 AL-4 AL-5 AL-6 AL-7 AL-8 AL-9 聚合物1 Q-1（10） Q-2（10） Q-3（20） Q-4（10） Q-5（40） Q-6（30） Q-7（10） Q-1（10） Q-3（10） 聚合物2 P-1（90） P-2（90） P-3（80） P-4（90） P-5（60） P-6（70） P-7（90） P-8（90） P-9（90） 添加劑1       Ad-1（5）             Ad-4（5） Ad-4（5） 添加劑2                      Ad-2（5） Ad-2（5） 配向方法 光配向 光配向 光配向 光配向 摩擦 摩擦 光配向 光配向 光配向 評價 黑亮度 △ 〇 〇 〇 〇 △ 〇 〇 〇 AC殘像 〇 〇 〇 〇 〇 〇 〇 〇 〇 密封密合性 （膜內強度） 〇 〇 〇 〇 〇 〇 〇 〇 〇 剝離試驗 （基板界面強度） 〇 〇 〇 △ 〇 〇 〇 〇 〇 [table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 alignment agent Alignment agent name AL-1 AL-2 AL-3 AL-4 AL-5 AL-6 AL-7 AL-8 AL-9 Polymer 1 Q-1 (10) Q-2 (10) Q-3 (20) Q-4 (10) Q-5 (40) Q-6 (30) Q-7 (10) Q-1 (10) Q-3 (10) Polymer 2 P-1 (90) P-2 (90) P-3 (80) P-4 (90) P-5 (60) P-6 (70) P-7 (90) P-8 (90) P-9 (90) Additive 1 Ad-1 (5) Ad-4 (5) Ad-4 (5) Additive 2 Ad-2 (5) Ad-2 (5) Alignment method Photoalignment Photoalignment Photoalignment Photoalignment friction friction Photoalignment Photoalignment Photoalignment Evaluation black brightness △ 〇 〇 〇 〇 △ 〇 〇 〇 AC afterimage 〇 〇 〇 〇 〇 〇 〇 〇 〇 Seal tightness (membrane strength) 〇 〇 〇 〇 〇 〇 〇 〇 〇 Peel test (substrate interface strength) 〇 〇 〇 △ 〇 〇 〇 〇 〇

[表4]    實施例10 實施例11 實施例12 實施例13 比較例1 比較例2 比較例3 比較例4 配向劑 配向劑名稱 AL-10 AL-11 AL-12 AL-13 AR-1 AR-2 AR-3 AR-4 聚合物1 Q-1（20） Q-3（30） Q-1（40） Q-3（30） Q-1（10） Q-3（10） Q-4（10） Q-7（10） 聚合物2 P-10（80） P-11（70） P-3（60） P-1（70） R-1（90） R-2（90） R-3（90） R-4（90） 添加劑1       Ad-3（5） Ad-3（5）    Ad-3（5）    Ad-3（5） 添加劑2       Ad-2（5） Ad-2（5）    Ad-2（5）    Ad-2（5） 配向方法 光配向 光配向 光配向 光配向 光配向 光配向 光配向 光配向 評價 黑亮度 〇 〇 〇 〇 × 〇 × 〇 AC殘像 〇 〇 〇 〇 × 〇 × 〇 密封密合性 （膜內強度） 〇 〇 〇 〇 〇 × 〇 × 剝離試驗 （基板界面強度） 〇 △ 〇 〇 〇 × 〇 × [Table 4] Example 10 Example 11 Example 12 Example 13 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 alignment agent Alignment agent name AL-10 AL-11 AL-12 AL-13 AR-1 AR-2 AR-3 AR-4 Polymer 1 Q-1 (20) Q-3 (30) Q-1 (40) Q-3 (30) Q-1 (10) Q-3 (10) Q-4 (10) Q-7 (10) Polymer 2 P-10 (80) P-11 (70) P-3 (60) P-1 (70) R-1 (90) R-2 (90) R-3 (90) R-4 (90) Additive 1 Ad-3 (5) Ad-3 (5) Ad-3 (5) Ad-3 (5) Additive 2 Ad-2 (5) Ad-2 (5) Ad-2 (5) Ad-2 (5) Alignment method Photoalignment Photoalignment Photoalignment Photoalignment Photoalignment Photoalignment Photoalignment Photoalignment Evaluation black brightness 〇 〇 〇 〇 x 〇 x 〇 AC afterimage 〇 〇 〇 〇 x 〇 x 〇 Seal tightness (membrane strength) 〇 〇 〇 〇 〇 x 〇 x Peel test (substrate interface strength) 〇 △ 〇 〇 〇 x 〇 x

如表3及表4所示，根據包含聚醯胺酸[P]與聚合物[Q]的實施例1～實施例13的液晶配向劑，可獲得AC殘像特性良好而且黑亮度低且顯示出高對比度的液晶顯示元件。另外，示出使用實施例1～實施例13的液晶配向劑而形成的液晶配向膜的密封密合性及剝離試驗的結果良好，且膜的韌性高。 與此相對，在使用不具有結構單元（I）的聚醯胺酸來代替聚醯胺酸[P]的比較例1、比較例3中，黑亮度高，AC殘像特性也差。另外，在使用不具有結構單元（II）的聚醯胺酸來代替聚醯胺酸[P]的比較例2、比較例4中，密封密合性及剝離試驗的評價不良，膜的韌性差。 As shown in Table 3 and Table 4, according to the liquid crystal alignment agents of Examples 1 to 13 containing polyamic acid [P] and polymer [Q], it is possible to obtain a display with good AC afterimage characteristics and low black brightness. A high-contrast liquid crystal display element. Moreover, it was shown that the sealing adhesiveness and the peeling test result of the liquid crystal alignment film formed using the liquid crystal alignment agent of Example 1-Example 13 were favorable, and the toughness of a film was high. On the other hand, in Comparative Examples 1 and 3 in which polyamic acid having no structural unit (I) was used instead of polyamic acid [P], black luminance was high and AC afterimage characteristics were also poor. In addition, in Comparative Examples 2 and 4 in which polyamic acid having no structural unit (II) was used instead of polyamic acid [P], the evaluation of sealing adhesion and peeling test was poor, and the toughness of the film was poor. .

根據以上結果而明確，根據包含聚醯胺酸[P]與聚合物[Q]的液晶配向劑，可形成能夠使低殘像及高對比度與膜的高韌性並存的液晶配向膜。From the above results, it is clear that a liquid crystal alignment film capable of coexisting low afterimage and high contrast with high toughness of the film can be formed by the liquid crystal alignment agent containing polyamic acid [P] and polymer [Q].

無none

Claims (13)

一種液晶配向劑，含有： 聚醯胺酸[P]，包含源自二胺的結構單元（I），且在所述結構單元（I）或與所述結構單元（I）不同的結構單元的主鏈中具有碳數2以上的鏈狀結構，所述二胺具有選自由羧酸基、磺酸基、磷酸基及膦酸基所組成的群組中的至少一種酸性基；以及 聚合物[Q]，其中，所述聚醯胺酸[P]除外，為選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種。 A liquid crystal alignment agent, containing: A polyamide acid [P] comprising a structural unit (I) derived from a diamine, and having a carbon number of 2 in the main chain of the structural unit (I) or a structural unit different from the structural unit (I) In the chain structure above, the diamine has at least one acidic group selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphonic acid groups; and The polymer [Q], except the polyamic acid [P], is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide. 如請求項1所述的液晶配向劑，其中，所述聚合物[Q]包含具有光配向性基的結構單元。The liquid crystal alignment agent according to Claim 1, wherein the polymer [Q] contains structural units having photoalignment groups. 如請求項1或請求項2所述的液晶配向劑，其中，所述聚合物[Q]包含源自具有環丁烷環結構的四羧酸衍生物的結構單元。The liquid crystal alignment agent according to Claim 1 or Claim 2, wherein the polymer [Q] comprises a structural unit derived from a tetracarboxylic acid derivative having a cyclobutane ring structure. 如請求項1或請求項2所述的液晶配向劑，其中，所述聚醯胺酸[P]包含源自選自由下述式（TA-1）～式（TA-9）各自所表示的化合物所組成的群組中的至少一種的結構單元；

。 The liquid crystal alignment agent according to claim 1 or claim 2, wherein the polyamic acid [P] is derived from the following formula (TA-1) ~ formula (TA-9) respectively represented a structural unit of at least one of the group consisting of compounds;

. 如請求項1或請求項2所述的液晶配向劑，其中，所述聚醯胺酸[P]包含所述結構單元（I）與源自在主鏈中具有碳數2以上的鏈狀結構的單量體的結構單元（II）。The liquid crystal alignment agent according to Claim 1 or Claim 2, wherein the polyamic acid [P] comprises the structural unit (I) and a chain structure derived from a chain structure having 2 or more carbon atoms in the main chain The monomeric structural unit of (II). 如請求項5所述的液晶配向劑，其中，所述結構單元（II）為源自在主鏈中具有下述式（1）所表示的部分結構的單量體的結構單元；

式（1）中，R ¹為烷二基；R ²及R ³分別獨立地為單鍵或烷二基；X ¹為單鍵、氧原子、-CO-、-COO-、-NR ⁴-、-CO-NR ⁴-、-NR ⁴-CO-NR ⁵-或-NR ⁴-COO-；X ²為氧原子、-CO-、-COO-、-NR ⁴-、-CO-NR ⁴-、-NR ⁴-CO-NR ⁵-或-NR ⁴-COO-；R ⁴及R ⁵分別獨立地為氫原子或一價有機基；n為0～4的整數；其中，在式（1）中，R ¹、R ²及R ³的碳數的合計為2以上；在R ²為烷二基，X ¹為與單鍵不同的基，且n=0的情況下，R ³為烷二基；「*1」表示與環狀結構鍵結的鍵結鍵。 The liquid crystal alignment agent according to claim 5, wherein the structural unit (II) is a structural unit derived from a monomer having a partial structure represented by the following formula (1) in the main chain;

In formula (1), R ¹ is an alkanediyl group; R ² and R ³ are independently a single bond or an alkanediyl group; X ¹ is a single bond, an oxygen atom, -CO-, -COO-, -NR ⁴ - , -CO-NR ⁴ -, -NR ⁴ -CO-NR ⁵ - or -NR ⁴ -COO-; X ² is an oxygen atom, -CO-, -COO-, -NR ⁴ -, -CO-NR ⁴ - , -NR ⁴ -CO-NR ⁵ -or -NR ⁴ -COO-; R ⁴ and R ⁵ are independently a hydrogen atom or a monovalent organic group; n is an integer from 0 to 4; wherein, in formula (1) Among them, the sum of the carbon numbers of R ¹ , R ² and R ³ is 2 or more; when R ² is an alkanediyl group, X ¹ is a group different from a single bond, and n=0, R ³ is an alkanediyl group group; "*1" indicates a bond bonded to a ring structure. 如請求項5所述的液晶配向劑，其中，所述結構單元（II）為源自在主鏈中具有碳數2以上的鏈狀結構的二胺的結構單元。The liquid crystal alignment agent according to claim 5, wherein the structural unit (II) is a structural unit derived from a diamine having a chain structure with 2 or more carbon atoms in the main chain. 如請求項1或請求項2所述的液晶配向劑，其中，相對於源自構成所述聚合物[Q]的二胺的結構單元的總量，所述聚合物[Q]中的所述結構單元（I）的含有量為1莫耳%以下。The liquid crystal alignment agent according to claim 1 or claim 2, wherein, relative to the total amount of structural units derived from the diamine constituting the polymer [Q], the The content of the structural unit (I) is 1 mol% or less. 如請求項1或請求項2所述的液晶配向劑，其中，所述聚醯胺酸[P]與所述聚合物[Q]的含有比例以質量比[P]/[Q]計而為95/5～50/50。The liquid crystal alignment agent according to claim 1 or claim 2, wherein the content ratio of the polyamic acid [P] to the polymer [Q] is calculated by mass ratio [P]/[Q] 95/5～50/50. 一種液晶配向膜，是使用如請求項1至請求項9中任一項所述的液晶配向劑而形成。A liquid crystal alignment film formed using the liquid crystal alignment agent described in any one of claim 1 to claim 9. 一種液晶元件，包括如請求項10所述的液晶配向膜。A liquid crystal element, comprising the liquid crystal alignment film as claimed in claim 10. 一種液晶配向膜的製造方法，使用如請求項1至請求項9中任一項所述的液晶配向劑來形成有機膜，對所述有機膜進行光照射來賦予液晶配向能力。A method for manufacturing a liquid crystal alignment film, using the liquid crystal alignment agent described in any one of claim 1 to claim 9 to form an organic film, and irradiating the organic film with light to impart liquid crystal alignment capability. 一種液晶配向膜的製造方法，使用如請求項1至請求項9中任一項所述的液晶配向劑來形成有機膜，對所述有機膜實施摩擦處理。A method for manufacturing a liquid crystal alignment film, using the liquid crystal alignment agent described in any one of claim 1 to claim 9 to form an organic film, and performing rubbing treatment on the organic film.