TW201932508A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

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

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TW201932508A
TW201932508A TW107141486A TW107141486A TW201932508A TW 201932508 A TW201932508 A TW 201932508A TW 107141486 A TW107141486 A TW 107141486A TW 107141486 A TW107141486 A TW 107141486A TW 201932508 A TW201932508 A TW 201932508A
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芦澤亮一
福田一平
長谷川直史
豊田美希
藤枝司
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日商日產化學股份有限公司
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Abstract

A liquid crystal aligning agent with excellent filtering and printing properties, a liquid crystal alignment film with excellent liquid crystal alignment properties obtained from said liquid crystal aligning agent, and a liquid crystal display element provided with said liquid crystal alignment film are provided. This liquid crystal aligning agent is characterized by containing: at least one polymer selected from the group consisting of polyamic acid or polyamic acid ester having the structure of formula [1], and a polyimide that is an imide compound thereof; and a solvent containing at least one solvent A selected from the group consisting of formulae (d-1) to (d-5) and formula (e) and at least one solvent B selected from the group consisting of formulae (B-1) to (B-4).

Description

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

本發明係關於濾過性及印刷性優異之液晶配向劑、由該液晶配向劑所獲得之液晶配向性優異之液晶配向膜及其製造方法，以及液晶顯示元件。The present invention relates to a liquid crystal alignment agent excellent in filterability and printability, a liquid crystal alignment film excellent in liquid crystal alignment property obtained from the liquid crystal alignment agent, a method for producing the same, and a liquid crystal display device.

作為液晶顯示元件之液晶配向膜，係將以聚醯胺酸(聚醯胺酸)等的聚醯亞胺前驅物或可溶性聚醯亞胺之溶液作為主成分之液晶配向劑塗布並進行燒結，所謂的聚醯亞胺系之液晶配向膜正廣泛地被使用。所述液晶配向劑之製造中，為了去除液晶配向劑之溶液中包含之異物，以往皆使用於使聚醯亞胺前驅物或聚醯亞胺溶解於溶劑之狀態下，使用過濾用過濾器進行過濾之手法(專利文獻1)。

[先前技術文獻]
[專利文獻]The liquid crystal alignment film which is a liquid crystal display element is coated and sintered by a liquid crystal alignment agent containing a solution of a polyamidiamine precursor such as polylysine (polyglycine) or a solution of a soluble polyimine. So-called polyimine-based liquid crystal alignment films are widely used. In the production of the liquid crystal alignment agent, in order to remove foreign matter contained in the solution of the liquid crystal alignment agent, it has been conventionally used in a state in which a polyimide precursor or a polyimine is dissolved in a solvent, and a filter for filtration is used. Method of filtration (Patent Document 1).

[Previous Technical Literature]
[Patent Literature]

[專利文獻1] 日本特開平08-262450號公報[Patent Document 1] Japanese Patent Publication No. 08-262450

[發明所欲解決之課題][Problems to be solved by the invention]

液晶配向膜之領域中，以往使用數百nm程度之薄膜，液晶配向劑中夾雜微小異物並不會成為太大的問題。然而，最近更薄之薄膜之必要性係提升，同時，微小的異物之去除係比以往更需要。去除溶液中之微小的異物，係若藉由孔徑小之過濾器進行過濾則可達成，但異物量多的情況，若以大規模進行製造，則花費時間過濾，而成為製造上的問題。又，對於顯示品質提升之要求係變得更加嚴格，除了針孔或塌凹之少之液晶配向劑以外，針對液晶配向性亦要求具有至今以上之特性之液晶配向膜。In the field of liquid crystal alignment films, conventionally, a film having a thickness of several hundred nm has been used, and the inclusion of minute foreign matter in the liquid crystal alignment agent does not become a problem too much. However, the need for thinner films has recently increased, and the removal of tiny foreign objects is more desirable than ever. The removal of minute foreign matter in the solution can be achieved by filtration through a filter having a small pore size. However, when the amount of foreign matter is large, it is time-consuming to filter when it is produced on a large scale, which causes a problem in production. Further, the demand for display quality improvement has become stricter. In addition to liquid crystal alignment agents having few pinholes or depressions, liquid crystal alignment films having the above-mentioned characteristics are also required for liquid crystal alignment.

本發明之目的係鑑於上述課題，提供濾過性及印刷性優異之液晶配向劑及由該液晶配向劑所獲得之液晶配向性優異之液晶配向膜，以及具備該液晶配向膜之液晶顯示元件。

[解決課題之手段]In view of the above-mentioned problems, a liquid crystal alignment agent excellent in filterability and printability, a liquid crystal alignment film excellent in liquid crystal alignment property obtained from the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film are provided.

[Means for solving the problem]

本發明人等，為了解決上述課題而進行積極檢討之結果，發現藉由使導入特定結構之聚合物與含有特定溶劑之溶劑組合，種種特性係同時地被改善。
本發明係基於所述見解者，要點係如下述。
一種液晶配向劑，其係含有由具有下述式[1]之結構之聚醯胺酸、聚醯胺酸酯(以下，亦將聚醯胺酸、聚醯胺酸酯總稱而稱為聚醯亞胺前驅物。)及作為其醯亞胺化物之聚醯亞胺所選出之至少1種聚合物及溶劑之液晶配向劑，其中，前述溶劑係包含由下述式(d-1)~(d-5)及下述式(e)所構成之群組所選出之至少1種溶劑A，及由下述式(B-1)~(B-4)所構成之群組所選出之至少1種溶劑B。As a result of conducting a positive review to solve the above problems, the present inventors have found that various characteristics are simultaneously improved by combining a polymer having a specific structure and a solvent containing a specific solvent.
The present invention is based on the above-mentioned insights, and the main points are as follows.
A liquid crystal alignment agent containing a polyglycolic acid or a polyglycolate having a structure of the following formula [1] (hereinafter, polyacrylic acid, polyglycolate is also collectively referred to as polyfluorene) An imine precursor.) and a liquid crystal alignment agent selected from the group consisting of at least one polymer and a solvent selected from the group consisting of a ruthenium imide, wherein the solvent comprises the following formula (d-1) to ( At least one solvent A selected from the group consisting of d-5) and the following formula (e), and at least one selected from the group consisting of the following formulas (B-1) to (B-4) 1 solvent B.


X係表示由單鍵、-O-、-C(CH3 )2 -、-NH-、-CO-、
-NHCO-、-COO-、-(CH2 )m -、-SO2 -、-O-(CH2 )m -O-、
-O-C(CH3 )2 -、-CO-(CH2 )m -、-NH-(CH2 )m -、
-SO2 -(CH2 )m -、-CONH-(CH2 )m -、-CONH-(CH2 )m -NHCO-及-COO-(CH2 )m -OCO-所構成之群組所選出之2價之有機基，m為1~8之整數。2個Y係獨立表示由下述式[S1]~[S3]或生育酚所衍生之結構所選出之側鏈結構。
X is represented by a single bond, -O-, -C(CH 3 ) 2 -, -NH-, -CO-,
-NHCO-, -COO-, -(CH 2 ) m -, -SO 2 -, -O-(CH 2 ) m -O-,
-OC(CH 3 ) 2 -, -CO-(CH 2 ) m -, -NH-(CH 2 ) m -,
a group consisting of -SO 2 -(CH 2 ) m -, -CONH-(CH 2 ) m -, -CONH-(CH 2 ) m -NHCO- and -COO-(CH 2 ) m -OCO- The selected two-valent organic group, m is an integer from 1 to 8. The two Y lines independently represent the side chain structure selected by the structure derived from the following formulas [S1] to [S3] or tocopherol.


X1 及X2 係獨立表示單鍵、-(CH2 )a -(a為1~15之整數)、
-CONH-、-NHCO-、-CON(CH3 )-、-NH-、-O-、-COO-、
-OCO-或((CH2 )a1 -A1 )m1 -(複數a1係獨立表示1~15之整數，複數A1 係獨立表示氧原子、-COO或OCO，m1 為1~2。)，G1 及G2 係獨立為由碳數6~12之2價之芳香族基或碳數3~8之2價之脂環式基所選出之2價之環狀基，前述環狀基上之任意的氫原子可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟烷基、碳數1~3之含氟烷氧基或氟原子取代，m及n係獨立為0~3之整數，其中，此等之合計為1~4，R1 為碳數1~20之烷基、碳數1~20之烷氧基或碳數2~20之烷氧烷基，此等之基中之任意的氫可被氟原子取代。
X3 係表示單鍵、-CONH-、-NHCO-、-CON(CH3 )-、
-NH-、-O-、-CH2 O-、-COO-或OCO-，R2 為碳數1~20之烷基或碳數2~20之烷氧烷基，此等之基中之任意的氫可被氟原子取代。
X4 係表示-CONH-、-NHCO-、-O-、-COO-或OCO-，R3 係表示具有類固醇骨架之結構。
X 1 and X 2 independently represent a single bond, -(CH 2 ) a - (a is an integer from 1 to 15),
-CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -COO-,
-OCO- or ((CH 2 ) a1 -A 1 ) m1 - (The plural a1 is an integer from 1 to 15, and the plural A 1 independently represents an oxygen atom, -COO or OCO, and m 1 is 1 to 2.) , G 1 and G 2 are independently a bivalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms, and the above cyclic group. Any of the above hydrogen atoms may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or Substituted by a fluorine atom, m and n are independently an integer of 0 to 3, wherein the total of these is 1 to 4, and R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or carbon. Alkoxyalkyl groups of 2 to 20, any of which may be substituted by a fluorine atom.
X 3 represents a single bond, -CONH-, -NHCO-, -CON(CH 3 )-,
-NH-, -O-, -CH 2 O-, -COO- or OCO-, R 2 is an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, in which Any hydrogen can be replaced by a fluorine atom.
X 4 represents -CONH-, -NHCO-, -O-, -COO- or OCO-, and R 3 represents a structure having a steroid skeleton.


R1a 係表示碳數1~8之1價之烴基，或該烴基中之碳-碳鍵結間具有「-O-」之1價之基，R2a 及R2b 係獨立表示碳數1~6之烷基，R3a 係表示甲基或乙基，R5a 係表示碳數1~6之烷基，R5b 及R5c 係獨立表示氫原子、碳數1~6之1價之烴基，或該烴基之碳-碳鍵結間具有「-O-」之1價之基，r1a 及r1b 係獨立表示氫原子、碳數1~6之烷基，m為2~6之整數，n為1或2。
R 1a represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a carbon-carbon bond in the hydrocarbon group having a monovalent group of "-O-", and R 2a and R 2b independently represent a carbon number of 1 to 2; 6 alkyl, R 3a represents a methyl group or an ethyl group, R 5a represents an alkyl group having 1 to 6 carbon atoms, and R 5b and R 5c each independently represent a hydrogen atom and a monovalent hydrocarbon group having 1 to 6 carbon atoms. Or the carbon-carbon bond of the hydrocarbon group has a monovalent group of "-O-", and r 1a and r 1b independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and m is an integer of 2 to 6. n is 1 or 2.


Ap1 、Ap2 係獨立表示碳數1~6之烷基，Ap5 係表示氫原子或碳數1~6之烷基，Aq1 係表示-O-或-COO-，Aq2 係表示單鍵或羰基，Aq3 係表示-O-，Ak1 、Ak2 、Ak6 係獨立表示碳數2~4之烷二基，n1係表示1~3。Ap3 、Ap4 係表示氫原子或碳數1~6之烷基，Ax 係表示-C(OH)Ra -、-CHRb -(Ra 、Rb 係獨立為氫、甲基或乙基。)、-CO-或-COO-＊(惟，＊係表示與Ak4 鍵結之位置。)，Ak4 、Ak5 係獨立表示碳數1~4之烷基，m係表示0~1，n4係表示1~3。惟，n4為1，且Ak6 為碳數2之烷二基，且Ap5為碳數4之烷基之情況除外。惟，n4為1，且Ak6為碳數2之烷二基，且Ap5為碳數4之烷基之情況除外。

[發明效果]
A p1 and A p2 are each independently represent an alkyl group having 1 to 6 carbon atoms, A p5 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A q1 is -O- or -COO-, and A q2 is a single A bond or a carbonyl group, A q3 represents -O-, A k1 , A k2 , and A k6 independently represent an alkanediyl group having 2 to 4 carbon atoms, and n1 represents 1 to 3. A p3 and A p4 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A x represents -C(OH)R a -, -CHR b - (R a and R b are independently hydrogen, methyl or Ethyl.), -CO- or -COO-* (except that * represents the position bonded to A k4 .), A k4 and A k5 are each independently represent an alkyl group having 1 to 4 carbon atoms, and m is 0. ~1, n4 means 1~3. However, the case where n4 is 1, and A k6 is a carbon number 2 alkanediyl group, and Ap5 is a carbon number 4 alkyl group. However, the case where n4 is 1, and Ak6 is a carbon number 2 alkanediyl group, and Ap5 is a carbon number 4 alkyl group.

[Effect of the invention]

若依據本發明，則可獲得濾過性及印刷性優異之液晶配向劑、由該液晶配向劑所獲得之液晶配向性優異之液晶配向膜，及具備該液晶配向膜之液晶顯示元件。According to the present invention, a liquid crystal alignment agent excellent in filterability and printability, a liquid crystal alignment film excellent in liquid crystal alignment property obtained from the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film can be obtained.

本發明之液晶配向劑係含有具有下述式[1]之結構之聚醯亞胺前驅物及作為其醯亞胺化物之聚醯亞胺所構成之群組所選出之至少1種聚合物(以下，亦稱為特定聚合物。)。

＜特定聚合物＞
其中，由合成的容易性來看，特定聚合物係由其於聚合物之主鏈具有式[1]之結構係較佳。此處，所謂聚合物之主鏈，係指由聚合物之中最長之原子之鏈所構成之部分。又，於特定聚合物中，並不排除前述式[1]之結構亦存在於主鏈以外之部分(例如聚合物之側鏈部分)之情況。The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of a polyimine precursor having the structure of the following formula [1] and a polyimine which is a quinone imide thereof ( Hereinafter, it is also referred to as a specific polymer.).

<specific polymer>
Among them, from the viewpoint of easiness of synthesis, the specific polymer is preferably a structure having the formula [1] in the main chain of the polymer. Here, the main chain of the polymer means a portion composed of a chain of the longest atoms among the polymers. Further, in the specific polymer, the case where the structure of the above formula [1] is also present in a portion other than the main chain (for example, a side chain portion of the polymer) is not excluded.

式[1]中之X係如同上述之定義。
其中，X係較佳為單鍵、-O-、-NH-、或-O-(CH2 )m -O-。The X in the formula [1] is as defined above.
Among them, the X system is preferably a single bond, -O-, -NH-, or -O-(CH 2 ) m -O-.

式[1]中之Y係具有由具有下述式[S1]~[S3]或生育酚骨架之結構所選出之側鏈結構。

式[S1]中之X1 及X2 係如同上述之定義。其中尤其由原料之取得性或合成的難易度之觀點來看，較佳為單鍵、
-(CH2 )a -(a為1~15之整數)、-O-、-CH2 O-或COO-。更佳為單鍵、-(CH2 )a -(a為1~10之整數)、-O-、-CH2 O-或COO-。The Y system in the formula [1] has a side chain structure selected from a structure having the following formula [S1] to [S3] or a tocopherol skeleton.

X 1 and X 2 in the formula [S1] are as defined above. Especially from the viewpoint of the availability of raw materials or the ease of synthesis, it is preferably a single bond,
-(CH 2 ) a - (a is an integer from 1 to 15), -O-, -CH 2 O- or COO-. More preferably, it is a single bond, -(CH 2 ) a - (a is an integer of 1 to 10), -O-, -CH 2 O- or COO-.

G1 及G2 係如同上述之定義。
作為上述碳數6~12之2價之芳香族基，係可舉出例如，伸苯基、亞聯苯基、萘等。又，作為碳數3~8之2價之脂環式基，係可舉出例如，環丙烯基、環己亞基等。G 1 and G 2 are as defined above.
Examples of the aromatic group having a valence of from 2 to 12 carbon atoms include a phenyl group, a biphenylylene group, and a naphthalene group. In addition, examples of the alicyclic group having a carbon number of 3 to 8 include a cyclopropenyl group and a cyclohexylene group.

作為式[S1]之較佳具體例，可舉出下述式[S1-x1]~[S1-x7]之結構。
A preferred embodiment of the formula [S1] is a structure of the following formula [S1-x1] to [S1-x7].

式[S1-x1]~[S1-x7]中，R1 為碳數1~20之烷基、碳數1~20之烷氧基或碳數2~20之烷氧基烷基。Xp 為
-(CH2 )a -(a為1~15之整數)、-CONH-、-NHCO-、
-CON(CH3 )-、-NH-、-O-、-CH2 O-、-CH2 OCO-、-COO-或
-OCO-。A1 為氧原子或-COO-＊(附有＊之鍵結鍵係與(CH2 )a2 鍵結。)，A2 為氧原子或＊-COO-(惟，附有「＊」之鍵結鍵係與(CH2 )a2 鍵結)。a1 、a3 係獨立為0或1之整數，a2 為1~10之整數。Cy為1,4-伸環己基或1,4-伸苯基。In the formula [S1-x1]~[S1-x7], R 1 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms. X p is
-(CH 2 ) a - (a is an integer from 1 to 15), -CONH-, -NHCO-,
-CON(CH 3 )-, -NH-, -O-, -CH 2 O-, -CH 2 OCO-, -COO- or
-OCO-. A 1 is an oxygen atom or -COO-* (bonding bond with * and (CH 2 ) a2 bonding), and A 2 is an oxygen atom or *-COO- (only, with a "*" bond The knot bond is bonded to (CH 2 ) a2 ). a 1 and a 3 are independently an integer of 0 or 1, and a 2 is an integer of 1 to 10. Cy is 1,4-cyclohexylene or 1,4-phenylene.


式[S2]中之X3 係如同上述之定義。其中尤其以液晶配向性之觀點來看較佳為-CONH-、-NHCO-、-O-、-CH2 O-、-COO-或OCO-。
R2 係如同上述之定義。其中尤其以液晶配向性之觀點來看，碳數3~20之烷基或碳數2~20之烷氧烷基係較佳。
作為式[S2]之較佳具體例，係舉出-CONH-(CH2 )n -CH3 (n=2~17)、-NHCO-(CH2 )n -CH3 (n=2~17)、-O-(CH2 )n -CH3 (n=2~17)、-COO-(CH2 )n -CH3 (n=2~17)、-CH2 O-(CH2 )n -CH3 (n=2~17)。
The X 3 in the formula [S2] is as defined above. Among them, in particular, from the viewpoint of liquid crystal alignment, it is preferably -CONH-, -NHCO-, -O-, -CH 2 O-, -COO- or OCO-.
R 2 is as defined above. Among them, in particular, from the viewpoint of liquid crystal alignment, an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms is preferred.
Preferred examples of the formula [S2] are -CONH-(CH 2 ) n -CH 3 (n=2~17), -NHCO-(CH 2 ) n -CH 3 (n=2~17) ), -O-(CH 2 ) n -CH 3 (n=2~17), -COO-(CH 2 ) n -CH 3 (n=2~17), -CH 2 O-(CH 2 ) n -CH 3 (n=2~17).


式[S3]中之X4 係如同上述之定義。其中尤其以液晶配向性之觀點來看較佳為-O-、-COO-或-OCO-。
作為具有類固醇骨架之結構，可舉出由β-穀固醇或麥角固醇等之化合物去除羥基後之結構、由日本特開平4-281427號之[0024]所記載之類固醇化合物去除羥基後之結構、由[0030]所記載之類固醇化合物去除醯氯基後之結構、由[0038]所記載之類固醇化合物去除氨基後之結構、由[0042]之類固醇化合物去除鹵素基後之結構，或日本特開平8-146421之[0018]~[0022]記載之結構。
The X 4 in the formula [S3] is as defined above. Among them, in particular, from the viewpoint of liquid crystal alignment, it is preferably -O-, -COO- or -OCO-.
The structure having a steroid skeleton is a structure in which a hydroxyl group is removed by a compound such as β-sitosterol or ergosterol, and the steroid compound described in [0024] of JP-A-4-281427 is used to remove a hydroxyl group. a structure obtained by removing a chloro group from the steroid compound described in [0030], a structure obtained by removing an amino group from the steroid compound described in [0038], a structure obtained by removing a halogen group from a steroid compound of [0042], or The structure described in [0018] to [0022] of Japanese Patent Laid-Open No. Hei 8-146421.

作為式[S3]之較佳具體例，可舉出下述式[S3-x]。又，式[S3-x]中之X、Col、G之定義，係各自如同下述內容。

(式中，＊係顯示鍵結位置)A preferred specific example of the formula [S3] is exemplified by the following formula [S3-x]. Further, the definitions of X, Col, and G in the formula [S3-x] are as follows.

(where, * shows the key position)

作為式[S3]之更佳結構，可舉出下述式[S3-1]~[S3-6]所示之結構。

(式中，＊係顯示鍵結位置)A more preferable structure of the formula [S3] is a structure represented by the following formulas [S3-1] to [S3-6].

(where, * shows the key position)

作為具有式[1]中之生育酚骨架之結構，例如可舉出由α-生育酚、β-生育酚、γ-生育酚、δ-生育酚等之化合物所衍生之結構。作為具有生育酚骨架之結構之具體例，可舉出例如下述式[T]所示之結構。此外，「＊」係顯示鍵結位置。
The structure having the tocopherol skeleton in the formula [1] may, for example, be a structure derived from a compound such as α-tocopherol, β-tocopherol, γ-tocopherol or δ-tocopherol. Specific examples of the structure having a tocopherol skeleton include a structure represented by the following formula [T]. In addition, "*" shows the key position.

本發明之液晶配向劑中含有之特定聚合物若為由具有前述式[1]所表示之2價基之聚醯亞胺前驅物及作為該聚醯亞胺前驅物之醯亞胺化物之聚醯亞胺所成之群所選出之至少1種以上之聚合物，則為藉由任何方法所合成者皆可。
其中，特定聚合物為由使具有前述式[1]之結構之四羧酸二酐或者其衍生物(以下，亦稱為特定四羧酸化合物。)、或包含該特定四羧酸化合物之四羧酸成分與二胺成分反應而獲得之聚醯亞胺前驅物；作為該聚醯亞胺前驅物之醯亞胺化物之聚醯亞胺；使上述四羧酸成分，與具有式[1]之結構之二胺(以下，亦稱為特定二胺。)或包含特定二胺之二胺成分反應而獲得之聚醯亞胺前驅物；以及作為該聚醯亞胺前驅物之醯亞胺化物之聚醯亞胺所成之群所選出之1種以上係較佳。The specific polymer contained in the liquid crystal alignment agent of the present invention is a polyimine precursor having a divalent group represented by the above formula [1] and a polyamidiamine which is a precursor of the polyimine. At least one or more polymers selected from the group consisting of ruthenium imines may be synthesized by any method.
Here, the specific polymer is a tetracarboxylic dianhydride having a structure of the above formula [1] or a derivative thereof (hereinafter, also referred to as a specific tetracarboxylic acid compound), or a fourth compound containing the specific tetracarboxylic acid compound. a polyimine precursor obtained by reacting a carboxylic acid component with a diamine component; a polyimine which is a ruthenium imide of the polyimide precursor; and the tetracarboxylic acid component and the formula [1] a diamine of the structure (hereinafter, also referred to as a specific diamine) or a polyimine precursor obtained by reacting a diamine component containing a specific diamine; and a ruthenium imide as a precursor of the polyimine One or more selected from the group consisting of polyimine are preferred.

[四羧酸成分]
用於合成特定聚合物所使用之四羧酸成分，係含有特定四羧酸化合物、其他四羧酸化合物中之任一者、或兩者。

＜特定四羧酸化合物＞
特定四羧酸化合物為具有上述式[1]結構之四羧酸化合物，例如，可舉出下述式[T]所表示之化合物或其衍生物。[tetracarboxylic acid component]
The tetracarboxylic acid component used for synthesizing a specific polymer contains either a specific tetracarboxylic acid compound or another tetracarboxylic acid compound, or both.

<Specific tetracarboxylic acid compound>
The specific tetracarboxylic acid compound is a tetracarboxylic acid compound having the structure of the above formula [1], and examples thereof include a compound represented by the following formula [T] or a derivative thereof.


式[T]中，A係表示3價之基，2個A可為相同亦可為不同。作為A的例子，可舉出具有由環丁烷環結構、環戊烷環結構、環己烷環結構、苯環結構及下述式(A-1)所成之群所選出之至少一種之3價之有機基。P係表示具有式[1]之結構之2價之有機基。

作為前述四羧酸化合物之衍生物，可舉出四羧酸二酐、四羧酸二鹵化物、四羧酸二烷基酯或四羧酸二烷基酯二鹵化物。
In the formula [T], the A system represents a trivalent group, and the two A groups may be the same or different. Examples of A include at least one selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, a cyclohexane ring structure, a benzene ring structure, and a group of the following formula (A-1). The organic base of 3 valence. P represents a divalent organic group having the structure of the formula [1].

The derivative of the tetracarboxylic acid compound may, for example, be a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dihalide.

＜其他四羧酸化合物＞
作為其他四羧酸化合物，可舉出由1,2,5,6-萘四羧酸、1,4,5,8-萘四羧酸、1,2,5,6-蒽四羧酸、3,3’,4,4’-聯苯基四羧酸、2,3,3’,4-聯苯基四羧酸、雙(3,4-二羧苯基)醚、3,3’,4,4’-二苯甲酮四羧酸、雙(3,4-二羧苯基)碸、雙(3,4-二羧苯基)甲烷、2,2-雙(3,4-二羧苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3,4-二羧苯基)丙烷、雙(3,4-二羧苯基)二甲基矽烷、雙(3,4-二羧苯基)二苯基矽烷、2,3,4,5-吡啶四羧酸、2,6-雙(3,4-二羧苯基)吡啶、3,3’,4,4’-二苯基碸基四羧酸、3,4,9,10-苝四羧酸或1,3-二苯基-1,2,3,4-環丁烷四羧酸等之四羧酸所獲得之酸二酐、下述式[4]所示之四羧酸二酐、或作為其衍生物之四羧酸二鹵化物化合物、四羧酸二烷基酯化合物或四羧酸二烷基酯二鹵化物化合物。<Other tetracarboxylic acid compounds>
Examples of the other tetracarboxylic acid compound include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and 1,2,5,6-nonanedicarboxylic acid. 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3' , 4,4'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4- Dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl) Dimethyldecane, bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine , 3,3',4,4'-diphenylmercaptotetracarboxylic acid, 3,4,9,10-nonanedicarboxylic acid or 1,3-diphenyl-1,2,3,4-ring An acid dianhydride obtained from a tetracarboxylic acid such as butane tetracarboxylic acid, a tetracarboxylic dianhydride represented by the following formula [4], or a tetracarboxylic acid dihalide compound as a derivative thereof, or a tetracarboxylic acid An alkyl ester compound or a dialkyl tetracarboxylate dihalide compound.

其中尤其由聚合物之溶解性高之觀點來看，式[4]所示之結構之四羧酸二酐及其四羧酸衍生物中之至少1種以上係較佳。
In particular, at least one or more of the tetracarboxylic dianhydride and the tetracarboxylic acid derivative of the structure represented by the formula [4] are preferred from the viewpoint of high solubility of the polymer.

Z係表示由下述[4a]~[4k]所選出之結構。

(＊1為鍵結於其中之一之酸酐基之鍵結位置，＊2為鍵結於另一酸酐基之鍵結位置。)The Z series indicates the structure selected by the following [4a] to [4k].

(*1 is the bonding position of the acid anhydride group bonded to one of them, and *2 is the bonding position bonded to the other acid anhydride group.)

式[4a]中，Z1 ~Z4 係獨立表示氫原子、甲基、乙基、丙基、氯原子或苯環。作為Z1 ~Z4 之較佳具體例，可舉出下述式[4a-1]、[4a-2]之結構。

(＊1、＊2係如同上述之定義。)In the formula [4a], Z 1 to Z 4 independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring. Preferred examples of Z 1 to Z 4 include the structures of the following formulas [4a-1] and [4a-2].

(*1, *2 are as defined above.)

式[4g]中，Z5 及Z6 係獨立為氫原子或甲基。
式[4]中之Z之中，由合成的難易度或製造聚合物時之聚合反應性之容易度之觀點來看，式[4a]、式[4c]~式[4g]或式[4k]係較佳。式[4a]或式[4e]~式[4g]係更佳，[4a]、式[4e]或式[4f]係特佳。作為較佳具體例，可舉出[4a-1]、式[4a-2]、式[4e]、式[4f]所示之結構之四羧酸二酐或其衍生物。In the formula [4g], Z 5 and Z 6 are independently a hydrogen atom or a methyl group.
Among the Z in the formula [4], from the viewpoint of the ease of synthesis or the ease of polymerization reactivity in the production of a polymer, the formula [4a], the formula [4c] to the formula [4g] or the formula [4k] ] is preferred. The formula [4a] or the formula [4e] to the formula [4g] is more preferable, and the [4a], the formula [4e] or the formula [4f] is particularly preferable. Preferred examples of the tetracarboxylic dianhydride or a derivative thereof represented by the formula [4a-1], the formula [4a-2], the formula [4e], and the formula [4f] are exemplified.

本發明之聚合物中之式[4]所示之四羧酸化合物於所有的四羧酸化合物100莫耳%中為1莫耳%以上，係以提高聚合物之溶解性之觀點來看為較佳。其中，5莫耳%以上係較佳，更佳為10莫耳%以上。
四羧酸化合物係因應本發明之聚合物之對於溶劑之溶解性或液晶配向劑之塗布性、作為液晶配向膜之情況之液晶之配向性、電壓保持率、蓄積電荷等的特性，亦可將1種或2種以上混合使用。The tetracarboxylic acid compound represented by the formula [4] in the polymer of the present invention is 1 mol% or more in 100 mol% of all tetracarboxylic acid compounds, from the viewpoint of improving the solubility of the polymer. Preferably. Among them, 5 mol% or more is preferable, and more preferably 10 mol% or more.
The tetracarboxylic acid compound may also have characteristics such as solubility in a solvent of the polymer of the present invention, coating property of a liquid crystal alignment agent, alignment property of a liquid crystal as a liquid crystal alignment film, voltage retention ratio, and charge accumulation. One type or two or more types are used in combination.

[二胺成分]
用於合成特定聚合物所使用之二胺係含有特定二胺。特定二胺係具有上述式[1]結構之二胺，例如，可舉出下述式[2]所表示之化合物。

＜特定二胺＞
本發明之液晶配向劑所使用之特定二胺係由下述式[2]所表示。

式[2]中之X、Y係各自與上述式[1]中之X、Y為相同意義。[Diamine component]
The diamine used to synthesize a specific polymer contains a specific diamine. The specific diamine is a diamine having a structure of the above formula [1], and examples thereof include a compound represented by the following formula [2].

<specific diamine>
The specific diamine used in the liquid crystal alignment agent of the present invention is represented by the following formula [2].

The X and Y systems in the formula [2] have the same meanings as X and Y in the above formula [1].

X係以容易合成特定二胺之觀點來看，較佳為單鍵、-O-、-NH-、-O-(CH2 )m -O-。m為1~8之整數。
式[2]中，Y係由X之位置而言可為間位亦可為鄰位，但，以特定二胺之反應性為高之觀點來看，鄰位係較佳。具體而言，式[2]較佳為下述式[2’]。
X is preferably a single bond, -O-, -NH-, or -O-(CH 2 ) m -O- from the viewpoint of easily synthesizing a specific diamine. m is an integer from 1 to 8.
In the formula [2], Y may be a meta position or an ortho position from the position of X, but the ortho system is preferred from the viewpoint that the reactivity of the specific diamine is high. Specifically, the formula [2] is preferably the following formula [2'].

上述式[2]係以特定二胺之反應性為高之觀點來看，較佳為下述式中之任一結構，為式[2]-a1-1所表示之結構係更佳。
The above formula [2] is preferably one of the following formulas from the viewpoint of high reactivity of a specific diamine, and is more preferably a structure represented by the formula [2]-a1-1.

作為上述式[2]中之Y之較佳形態，可適用前述式[1]中之Y之較佳形態。其中，由前述式[S1-x3]~[S1-x4]、[S1-x6]及式[S3-x]所選出之結構係由提高液晶配向性之觀點來看為較佳，作為較佳具體例可舉出下述式[W-1]~[W-6]之結構。
As a preferred embodiment of Y in the above formula [2], a preferred embodiment of Y in the above formula [1] can be applied. Among them, the structure selected by the above formulas [S1-x3] to [S1-x4], [S1-x6], and the formula [S3-x] is preferable from the viewpoint of improving liquid crystal alignment, and is preferable. Specific examples include the structures of the following formulas [W-1] to [W-6].

式中，Xp1 ~Xp8 係獨立表示-(CH2 )a -(a為1~15之整數)、-CONH-、-NHCO-、-CON(CH3 )-、-NH-、-O-、
-CH2 O-、-CH2 OCO-、-COO-或-OCO-。Xs1 ~Xs4 係獨立表示-O-、-COO-或-OCO-。Xa ~Xf 係表示單鍵、-O-、-NH-、
-O-(CH2 )m -O-。R1a ~R1h 係獨立表示碳數1~20之烷基、碳數1~20之烷氧基或碳數2~20之烷氧基烷基。m為1~8之整數。
特定二胺，係因應液晶配向劑之噴墨塗布性、作為液晶配向膜時之液晶配向性、電壓保持特性、蓄積電荷等的特性、作為液晶顯示元件時之液晶之應答速度等，可混合1種或2種以上使用。In the formula, X p1 ~X p8 are independently represented by -(CH 2 ) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O -,
-CH 2 O-, -CH 2 OCO-, -COO- or -OCO-. X s1 ~X s4 independently represent -O-, -COO- or -OCO-. X a ~ X f represents a single bond, -O-, -NH-,
-O-(CH 2 ) m -O-. R 1a to R 1h independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms. m is an integer from 1 to 8.
The specific diamine can be mixed in accordance with the inkjet coating property of the liquid crystal alignment agent, the liquid crystal alignment property when the liquid crystal alignment film is used, the voltage retention characteristics, the charge accumulation property, and the like, and the response speed of the liquid crystal when the liquid crystal display element is used. Use of two or more species.

特定二胺較佳係使用特定聚合物之合成中使用之二胺成分之1~100莫耳%，更佳為2~100莫耳%，特佳為5~90莫耳%。
作為用於合成聚醯胺酸或聚醯胺酸酯之二胺，可僅使用特定二胺，亦可併用其他二胺與特定二胺共同使用。此處，作為其他二胺，可舉出例如上述(2)以外之具有預傾斜角顯現性之二胺、具有藉由光照射聚合或者產生自由基之機能之二胺或WO(國際公開公報)2015/046374之[0169]所記載之二胺、[0171]~[0172]所記載具有之羧基或羥基之二胺、具有[0173]~[0188]所記載之具有含氮雜環之二胺或日本特開2016-218149號公報之[0050]所記載之具有含氮結構之二胺、1,3-雙(3-胺基丙基)-1,1,3,3-四甲基二矽氧烷、1,3-雙(4-氨基丁基)-1,1,3,3-四甲基二矽氧烷等的含有有機矽氧烷之二胺。其中尤其藉由PSA(Polymer Sustained Alignment)方式之液晶顯示元件中，由提高應答速度之觀點來看，較佳係具有藉由光照射聚合或者產生自由基之機能之二胺。The specific diamine is preferably used in an amount of from 1 to 100 mol%, more preferably from 2 to 100 mol%, particularly preferably from 5 to 90 mol%, of the diamine component used in the synthesis of the specific polymer.
As the diamine for synthesizing polyglycolic acid or polyglycolate, only a specific diamine may be used, or another diamine may be used in combination with a specific diamine. Here, as the other diamine, for example, a diamine having a pretilt angle developability other than the above (2), a diamine having a function of polymerizing by light irradiation or generating a radical, or WO (International Publication) The diamine described in [0169] of 2015/046374, the diamine having a carboxyl group or a hydroxyl group as described in [0171] to [0172], and the diamine having a nitrogen-containing heterocyclic ring described in [0173] to [0188] Or a diamine having a nitrogen-containing structure, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldi as described in [0050] of JP-A-2016-218149 An organooxane-containing diamine such as a decane or a 1,3-bis(4-aminobutyl)-1,1,3,3-tetramethyldioxane. Among them, in the liquid crystal display device of the PSA (Polymer Sustained Alignment) type, it is preferred to have a diamine which is polymerized by light irradiation or generates radicals from the viewpoint of improving the response speed.

作為其他二胺之較佳具體例，可舉出m-苯二胺、p-苯二胺、4,4’-二胺基聯苯、3,3’-二甲基-4,4’-二胺基聯苯、3,3’-二氟-4,4’-二胺基聯苯、4,4’-二氨基二苯基甲烷、4,4’-二胺基二苯基醚、4,4’-二氨基二苯胺、N-甲基(4,4’-二氨基二苯基)胺、4,4’-二氨基二苯甲酮、1,4-二氨基萘、2,6-二氨基萘、1,2-雙(4-氨苯基)乙烷、1,3-雙(4-氨苯基)丙烷、1,4-雙(4-氨苯基)丁烷、1,4-雙(4-氨基苯氧基)苯、1,4-雙(4-氨苯基)苯、1,3-雙(4-氨苯基)苯、1,4-雙(4-氨基苄基)苯、1,3-雙(4-氨基苯氧基)苯、4,4’-[1,4-伸苯基雙(亞甲基)]二苯胺、1,4-伸苯基雙[(4-氨苯基)甲酮]、1,4-伸苯基雙(4-氨基苯甲酸酯)、雙(4-氨苯基)對苯二甲酸酯、雙(4-氨苯基)間苯二甲酸酯、N,N’-(1,4-伸苯基)雙(4-氨基苯甲醯胺)、N,N’-雙(4-氨苯基)對苯二甲醯胺、N,N’-雙(4-氨苯基)間苯二甲醯胺、9,10-雙(4-氨苯基)蒽、2,2’-雙[4-(4-氨基苯氧基)苯基]丙烷、2,2’-雙(4-氨苯基)丙烷、1,3-雙(4-氨基苯氧基)丙烷、1,4-雙(4-氨基苯氧基)丁烷、1,5-雙(4-氨基苯氧基)戊烷、1,6-雙(4-氨基苯氧基)己烷、1,7-雙(4-氨基苯氧基)庚烷、1,8-雙(4-氨基苯氧基)辛烷、1,9-雙(4-氨基苯氧基)壬烷、1,10-(4-氨基苯氧基)癸烷、雙(4-氨基環己基)甲烷、1,3-二氨基丙烷、1,4-二氨基丁烷、1,5-二氨基戊烷、1,6-二氨基己烷、2,4-二氨基安息香酸、2,5-二氨基安息香酸、3,5-二氨基安息香酸、4,4’-二胺基聯苯基-3-羧酸、4,4’-二氨基二苯基甲烷-3-羧酸、4,4’-二氨基二苯基乙烷-3-羧酸、4,4’-二胺基聯苯基-3,3’-二羧酸、4,4’-二胺基聯苯基-2,2’-二羧酸、3,3’-二胺基聯苯基-4,4’-二羧酸、3,3’-二胺基聯苯基-2,4’-二羧酸、4,4’-二氨基二苯基甲烷-3,3’-二羧酸、4,4’-二氨基二苯基乙烷-3,3’-二羧酸、4,4’-二胺基二苯基醚-3,3’-二羧酸、2,6-二氨基吡啶、3,4-二氨基吡啶、2,4-二氨基嘧啶、3,6-二氨基咔唑、N-甲基-3,6-二氨基咔唑、1,4-雙-(4-氨苯基)-哌嗪、3,6-二氨基吖啶、N-乙基-3,6-二氨基咔唑、N-苯基-3,6-二氨基咔唑、N,N’-雙(4-氨苯基)-聯苯胺、N,N’-雙(4-氨苯基)-N,N’-二甲基聯苯胺、下述式(D-2-1)~式(D-2-8)各自所表示之化合物，Preferred examples of the other diamines include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, and 3,3'-dimethyl-4,4'-. Diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2, 6-Diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4) -aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]diphenylamine, 1,4-stretch Phenylbis[(4-aminophenyl)methanone], 1,4-phenylene bis(4-aminobenzoate), bis(4-aminophenyl)terephthalate, double ( 4-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-bis(4-aminophenyl) ) p-xylguanamine, N,N'-bis(4-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)fluorene, 2,2'-bis[4] -(4 -aminophenoxy)phenyl]propane, 2,2'-bis(4-aminophenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-amino) Phenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy) Heptane, 1,8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,10-(4-aminophenoxy)anthracene Alkane, bis(4-aminocyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 2,4 -diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenyl Methane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4 '-Diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl -2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3,3'-di Carboxylic acid, 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid, 2 ,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4- Bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, the following formula (D-2- 1)~ the compound represented by the formula (D-2-8),


此外，可舉出此等之氨基為2級氨基之二胺化合物。
Further, a diamine compound in which the amino group is a 2-stage amino group may be mentioned.

作為上述式(2)以外之具有預傾斜角顯現性之二胺，可舉出下述式[V-1]~[V-7]之結構式所表示之二胺。
Examples of the diamine having a pretilt angle developability other than the above formula (2) include diamines represented by the following structural formulae [V-1] to [V-7].

上述式中，Xv1 ~Xv4 係獨立表示-(CH2 )a -(a為1~15之整數)、-CONH-、-NHCO-、-CON(CH3 )-、-NH-、
-O-、-CH2 O-、-CH2 OCO-、-COO-，或-OCO-。Xv5 係表示
-O-、-CH2 O-、-CH2 OCO-、-COO-，或-OCO-。XV6 ~XV7 係獨立表示-O-、-COO-或-OCO-。
作為具有藉由光照射聚合之機能之二胺，可舉出例如下述式[p1]~[p7]所表示之結構直接或藉由連結基鍵結於苯環等的芳香族環之二胺。
In the above formula, X v1 to X v4 independently represent -(CH 2 ) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH 3 )-, -NH-,
-O-, -CH 2 O-, -CH 2 OCO-, -COO-, or -OCO-. X v5 system representation
-O-, -CH 2 O-, -CH 2 OCO-, -COO-, or -OCO-. X V6 ~X V7 stands for -O-, -COO- or -OCO- independently.
Examples of the diamine having a function of polymerization by light irradiation include a structure represented by the following formulas [p1] to [p7], or a diamine bonded to an aromatic ring such as a benzene ring by a linking group. .

作為具體例，可舉出下述式[P-a]或[P-b]所示之二胺。

式[P-a]、式[P-b]中之2個氨基(-NH2 )的鍵結位置並未被限定，但由二胺之反應性之觀點來看，2,4位之位置、2,5位之位置，或3,5位之位置係較佳。若將合成二胺時之容易性也一同考慮進去，則2,4位之位置，或3,5位之位置係更佳。Specific examples thereof include a diamine represented by the following formula [Pa] or [Pb].

The bonding position of the two amino groups (-NH 2 ) in the formula [Pa] and the formula [Pb] is not limited, but from the viewpoint of the reactivity of the diamine, the position of the 2, 4 position, 2, 5 The position of the bit, or the position of 3, 5 bits is preferred. If the easiness of synthesizing the diamine is also taken into consideration, the position of the 2, 4 position, or the position of the 3, 5 position is better.

式[P-a]中，R8 係表示單鍵、-O-、-COO-、
-OCO-、-NHCO-、-CONH-、-NH-、-CH2 O-、-N(CH3 )-、
-CON(CH3 )-或-N(CH3 )CO-，由合成的容易性來看，較佳為單鍵、-O-、-COO-、-NHCO-或-CONH-。
R9 係表示單鍵、可被氟原子取代之碳數1~20之伸烷基、由苯環、萘環等之碳數6~12之芳香族環所選出之2價基、環己烷環等之碳數3~8之2價之脂環式基、由吡咯、咪唑、吡啶、嘧啶、吡嗪、噠嗪、三嗪、吲哚、喹啉、咔唑、噻唑、嘌呤、四氫呋喃、噻吩等的5員環以上之雜環所選出之2價之環狀基。此處，伸烷基之-CH2 -，係可被-CF2 -或-CH=CH-任意地取代。由合成的容易性來看，單鍵或碳數1~12之伸烷基係較佳。K為0~4之整數。In the formula [Pa], R 8 represents a single bond, -O-, -COO-,
-OCO-, -NHCO-, -CONH-, -NH-, -CH 2 O-, -N(CH 3 )-,
-CON(CH 3 )- or -N(CH 3 )CO- is preferably a single bond, -O-, -COO-, -NHCO- or -CONH- from the viewpoint of ease of synthesis.
R 9 represents a single bond, an alkylene group having 1 to 20 carbon atoms which may be substituted by a fluorine atom, a divalent group selected from an aromatic ring having 6 to 12 carbon atoms such as a benzene ring or a naphthalene ring, and cyclohexane. An alicyclic group having a carbon number of from 3 to 8 such as a pyrrole, an imidazole, a pyridine, a pyrimidine, a pyrazine, a pyridazine, a triazine, an anthracene, a quinoline, an oxazole, a thiazole, an anthracene, a tetrahydrofuran, or the like. A bivalent cyclic group selected from a heterocyclic ring of a 5-membered ring or the like of thiophene or the like. Here, the alkyl-CH 2 - group may be optionally substituted by -CF 2 - or -CH=CH-. From the standpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferred. K is an integer from 0 to 4.

R10 係表示由上述式[p1]~[p7]所選出之結構。由光反應性之觀點來看，較佳為[p1]、[p2]、[p4]。
式[P-b]中，Y1 、Y3 係獨立表示-CH2 -、-O-、-CONH-、-NHCO-、-COO-、-OCO-、-NH-或-CO-。Y2 、Y5 係獨立為與上述[P-a]中之R9 為相同意義。Y4 係表示桂皮醯基。Y6 係表示由上述式[p1]~[p7]所選出之結構。由光反應性之觀點來看，[p1]、[p2]、[p4]係較佳。m係表示0或1。
具有藉由光照射聚合之機能之二胺，係因應作為液晶配向膜時之液晶配向性、預傾斜角、電壓保持特性、蓄積電荷等的特性、作為液晶顯示元件時之液晶之應答速度等，可混合1種或2種以上使用。R 10 represents the structure selected by the above formulas [p1] to [p7]. From the viewpoint of photoreactivity, [p1], [p2], and [p4] are preferred.
In the formula [Pb], Y 1 and Y 3 independently represent -CH 2 -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH- or -CO-. Y 2 and Y 5 are independently the same as R 9 in the above [Pa]. Y 4 represents cinnabarinyl. Y 6 represents the structure selected by the above formula [p1] to [p7]. From the viewpoint of photoreactivity, [p1], [p2], and [p4] are preferred. The m system represents 0 or 1.
The diamine having a function of polymerization by light irradiation is a liquid crystal alignment property, a pretilt angle, a voltage holding property, a charge accumulation property, and the like, and a response speed of a liquid crystal when used as a liquid crystal display element. It can be used in combination of 1 type or 2 types or more.

具有藉由光照射聚合之機能之二胺，較佳係使用特定聚合物之合成中使用之二胺成分之10~70莫耳%，更佳為10~60莫耳%、特佳為10~50莫耳%。
作為具有藉由光照射產生自由基之機能之二胺，可舉出例如，於側鏈具有下述部位之二胺，該部位係具有藉由紫外線照射分解並產生自由基之自由基產生結構，例如可舉出下述式(R)所示之二胺。
The diamine having a function of polymerization by light irradiation is preferably 10 to 70 mol%, more preferably 10 to 60 mol%, particularly preferably 10 to 10% of the diamine component used in the synthesis of the specific polymer. 50% by mole.
The diamine having a function of generating a radical by light irradiation may, for example, be a diamine having a site in which a side chain has a radical generating structure which is decomposed by ultraviolet irradiation and generates a radical. For example, a diamine represented by the following formula (R) can be mentioned.

上述式(R)中之Ar、R1 、R2 、T1 、T2 、S及Q係具有以下之定義。
亦即，Ar係表示由伸苯基、伸萘基、及亞聯苯基所選出之芳香族烴基，該等中亦可被有機基取代，氫原子亦可取代為鹵素原子。
R1 、R2 係獨立為碳原子數1~10之烷基或者烷氧基。
T1 、T2 係獨立為單鍵或-O-、-COO-、-OCO-、-NHCO-、
-CONH-、-NH-、-CH2 O-、-N(CH3 )-、-CON(CH3 )-、
-N(CH3 )CO-之鍵結基。
S係與上述[P-a]中之R9 為相同意義。Ar, R 1 , R 2 , T 1 , T 2 , S and Q in the above formula (R) have the following definitions.
That is, the Ar system represents an aromatic hydrocarbon group selected from a stretching phenyl group, a stretching naphthyl group, and a biphenylylene group, and these may be substituted by an organic group, and a hydrogen atom may be substituted with a halogen atom.
R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group.
T 1 and T 2 are independently a single bond or -O-, -COO-, -OCO-, -NHCO-,
-CONH-, -NH-, -CH 2 O-, -N(CH 3 )-, -CON(CH 3 )-,
a bond group of -N(CH 3 )CO-.
The S system has the same meaning as R 9 in the above [Pa].

Q係表示由下述式[q-1]~[q-4]所選出之結構(結構式中，R係表示氫原子或碳原子數1~4之烷基，R3 係表示-CH2 -、-NR-、-O-、或-S-。)。

(式中，＊係顯示鍵結位置。)
上述式(R)中，由使羰基所鍵結之Ar之紫外線之吸收成為有效率之觀點來看，伸萘基、亞聯苯基等的共軛長為長之結構係較佳。又，Ar中亦可具有取代基，所述取代基為如烷基、羥基、烷氧基、氨基等的電子供給性之有機基係較佳。若紫外線之波長為250~380nm之範圍內，則由於苯基亦可獲得充分的特性，故苯基係最佳。The Q system represents a structure selected by the following formula [q-1] to [q-4] (in the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 3 represents -CH 2 -, -NR-, -O-, or -S-.).

(In the formula, * shows the key position.)
In the above formula (R), the structure in which the conjugate length of the naphthyl group or the biphenylylene group is long is preferable from the viewpoint of efficient absorption of the ultraviolet light of Ar bonded by the carbonyl group. Further, Ar may have a substituent, and the substituent is preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group or an amino group. When the wavelength of the ultraviolet ray is in the range of 250 to 380 nm, since the phenyl group can also obtain sufficient characteristics, the phenyl group is optimal.

又，R1 、R2 係獨立為碳原子數1~10之烷基、烷氧基、苄基或苯乙基，為烷基或烷氧基時，亦可以R1 、R2 形成環。
Q係由容易製造特定聚合物之觀點來看，更佳為羥基或烷氧基。
式(R)中之二胺苯可為o-苯二胺、m-苯二胺、或p-苯二胺中之任一之結構，但以與四羧酸成分之反應性高之觀點來看，較佳為m-苯二胺或p-苯二胺。Further, R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group, and when it is an alkyl group or an alkoxy group, R 1 and R 2 may form a ring.
The Q is more preferably a hydroxyl group or an alkoxy group from the viewpoint of easy production of a specific polymer.
The diamine benzene in the formula (R) may be any one of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine, but is highly reactive with the tetracarboxylic acid component. Preferably, it is m-phenylenediamine or p-phenylenediamine.

具體而言，由合成的難易度、通用性的強度、特性等的觀點來看，下述式[R-1]~[R-4]所表示之結構係最佳。此外，式中，n為2~8之整數。
Specifically, the structure represented by the following formulas [R-1] to [R-4] is the best from the viewpoints of ease of synthesis, strength of versatility, characteristics, and the like. Further, in the formula, n is an integer of 2 to 8.

具有藉由光照射產生自由基之機能之二胺較佳係使用特定聚合物之合成中使用之二胺成分之5~70莫耳%，由保持液晶配向性之觀點來看，更佳為10~60莫耳%，特佳為10~50莫耳%。The diamine having a function of generating a radical by light irradiation is preferably 5 to 70 mol% of a diamine component used in the synthesis of a specific polymer, and more preferably 10 from the viewpoint of maintaining liquid crystal alignment. ~60% by mole, especially preferably 10~50% by mole.

＜特定聚合物之合成＞
特定聚合物係如同上述使二胺及四羧酸化合物反應而獲得。作為獲得聚醯胺酸之方法，可舉出使四羧酸二酐與二胺聚縮合而獲得聚醯胺酸之方法，或使四羧酸二鹵化物化合物及二胺化合物聚縮合而獲得聚醯胺酸之方法。
特定聚合物，因應需要可藉由使其與分子量調整劑反應而獲得。作為分子量調整劑，可舉出例如馬來酸酐、鄰苯二甲酸酐、衣康酸酐等的酸一酐、苯胺、環己基胺、n-丁基胺等的單胺化合物、苯基異氰酸酯、異氰酸萘酯等的單異氰酸酯化合物等。分子量調整劑之使用比例係相對於使用之四羧酸化合物及二胺之合計100質量份，作為20質量份以下係較佳，作為10質量份以下係更佳。<Synthesis of specific polymers>
The specific polymer is obtained by reacting a diamine and a tetracarboxylic acid compound as described above. As a method of obtaining a polyamic acid, a method of obtaining a poly-proline by polycondensing a tetracarboxylic dianhydride with a diamine, or polycondensing a tetracarboxylic acid dihalide compound and a diamine compound to obtain a poly The method of proline.
A specific polymer can be obtained by reacting it with a molecular weight modifier as needed. Examples of the molecular weight modifier include an acid monoanhydride such as maleic anhydride, phthalic anhydride or itaconic anhydride, a monoamine compound such as aniline, cyclohexylamine or n-butylamine, phenyl isocyanate or the like. A monoisocyanate compound such as naphthyl cyanate. The use ratio of the molecular weight modifier is preferably 100 parts by mass or less based on 100 parts by mass of the total of the tetracarboxylic acid compound and the diamine to be used, and more preferably 10 parts by mass or less.

作為獲得聚醯胺酸酯之方法，可舉出將羧酸基二烷基酯化之四羧酸二烷基酯化合物與二胺聚縮合之方法、將羧酸基二烷基酯化及二鹵化物化之四羧酸二烷基酯二鹵化物化合物與1級或2級之二胺聚縮合之方法或聚醯胺酸之羧基轉換為酯之方法。
作為獲得聚醯亞胺之方法，可舉出使前述之聚醯亞胺前驅物閉環，作為聚醯亞胺之方法。As a method of obtaining a polyphthalate, a method of polycondensing a dialkyl ester of a carboxylic acid dialkyl ester with a diamine, a dialkyl esterification of a carboxylic acid group, and a A method of polycondensation of a halogenated dicarboxylic acid dialkyl ester dihalide compound with a 1 or 2 grade diamine or a method of converting a carboxyl group of polylysine to an ester.
As a method of obtaining a polyimine, a method of ring-closing the above-mentioned polyimine precursor as a polyimine is mentioned.

二胺與四羧酸化合物之反應較佳係於溶劑中進行。作為溶劑，若為可溶解所生成之聚合物者則未特別限定。以下舉出溶劑之具體例，但並不限定於此等例子。
例如，可舉出N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮或γ-丁內酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸或1,3-二甲基-2-咪唑啉酮。又，聚合物之溶劑溶解性高的情況，可使用甲基乙酮、環己酮、環戊酮、4-羥基-4-甲基-2-戊酮或下述式[D-1]~式[D-3]所示之溶劑。The reaction of the diamine with the tetracarboxylic acid compound is preferably carried out in a solvent. The solvent is not particularly limited as long as it is a polymer which can be dissolved. Specific examples of the solvent are given below, but are not limited thereto.
For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide , dimethyl hydrazine or 1,3-dimethyl-2-imidazolidinone. Further, when the solvent solubility of the polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D-1]~ can be used. A solvent represented by the formula [D-3].


(式[D-1]中，D1 係表示碳數1~3之伸烷基，式[D-2]中，D2 係表示碳數1~3之伸烷基，式[D-3]中，D3 係表示碳數1~4之伸烷基)。
此等溶劑可單獨使用，亦可混合使用。此外，即使為無法溶解聚合物之溶劑，在生成之聚合物不析出之範圍內，亦可於前述溶劑中混合使用。又，溶劑中之水分係阻礙聚合反應，且進一步成為所生成之聚合物水解之原因，故較佳係使用經脫水乾燥之溶劑。
(In the formula [D-1], D 1 represents an alkylene group having 1 to 3 carbon atoms, and in the formula [D-2], D 2 represents an alkylene group having 1 to 3 carbon atoms, and the formula [D-3] In the formula, D 3 represents an alkylene group having 1 to 4 carbon atoms.
These solvents may be used singly or in combination. Further, even if it is a solvent in which the polymer cannot be dissolved, it may be used in combination in the above solvent within a range in which the produced polymer does not precipitate. Further, since the water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polymer, it is preferred to use a solvent which is dehydrated and dried.

使二胺與四羧酸化合物於溶劑中反應時，反應係可以任意的濃度進行，但濃度若過低，則變得難以獲得高分子量之聚合物，濃度若過高，則反應液之黏性變得過高，均勻的攪拌係變得困難。因此，較佳為1~50質量%，更佳為5~30質量%。反應初期係以高濃度進行，之後，可追加溶劑。
聚縮合反應中，二胺之合計莫耳數及四羧酸化合物之合計莫耳數之比為0.8~1.2係較佳。與一般的聚縮合反應相同，此莫耳比越接近1.0，所生成之特定聚合物之分子量越大。
聚醯亞胺係使前述聚醯亞胺前驅物閉環所獲得之聚醯亞胺，此聚醯亞胺中，醯胺基之閉環率(亦稱為醯亞胺化率)係不必要為100%，可依據用途或目的任意地調整。When the diamine and the tetracarboxylic acid compound are reacted in a solvent, the reaction system can be carried out at any concentration. However, if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction solution is too high. It becomes too high and a uniform stirring system becomes difficult. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then a solvent can be added.
In the polycondensation reaction, the ratio of the total number of moles of the diamine to the total number of moles of the tetracarboxylic acid compound is preferably from 0.8 to 1.2. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the particular polymer produced.
The polyimine is a polyimine obtained by ring-closing the polyimine precursor. In the polyimine, the ring closure ratio (also referred to as oxime imidization ratio) of the guanamine group is not necessarily 100. % can be arbitrarily adjusted depending on the purpose or purpose.

作為使聚醯亞胺前驅物醯亞胺化之方法，可舉出直接將聚醯亞胺前驅物之溶液加熱之熱醯亞胺化或於聚醯亞胺前驅物之溶液中添加觸媒之觸媒醯亞胺化。
使聚醯亞胺前驅物於溶液中熱醯亞胺化時之溫度為100~400℃，較佳為120~250℃，較佳為一邊將藉由醯亞胺化反應生成之水排除至系統外部，一邊進行。
聚醯亞胺前驅物之觸媒醯亞胺化，可藉由於聚醯亞胺前驅物之溶液中，添加鹼性觸媒及酸酐，於-20℃~250℃，較佳為0~180℃攪拌來進行。鹼性觸媒的量為醯胺酸基的0.5~30莫耳倍，較佳為2~20莫耳倍，酸酐的量為醯胺酸基的1~50莫耳倍，較佳為3~30莫耳倍。作為鹼性觸媒，可舉出吡啶、三乙胺、三甲基胺、三丁基胺或三辛基胺等，其中，吡啶具有使反應進行所需之適度鹼性故較佳。作為酸酐，可舉出乙酸酐、偏苯三甲酸酐或苯四酸酐等，其中，若使用乙酸酐則使反應結束後之純化變得容易故較佳。觸媒醯亞胺化所致之醯亞胺化率可藉由調節觸媒量與反應溫度、反應時間而控制。As a method for imidating the polyimine precursor ruthenium, a hot hydrazine imidization of a solution of a polyimide precursor is directly added or a catalyst is added to a solution of a polyimide precursor. The catalyst is imidized.
The temperature at which the polyimine precursor is thermally imidized in the solution is 100 to 400 ° C, preferably 120 to 250 ° C, preferably the water formed by the hydrazine imidization reaction is excluded to the system. External, one side.
The catalyst of the polyimine precursor is imidized by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, at -20 ° C to 250 ° C, preferably 0 to 180 ° C. Stir it. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate alkalinity required for the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, purification after completion of the reaction is facilitated, which is preferable. The imidization rate of the oxime imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

由聚醯亞胺前驅物或聚醯亞胺之反應溶液回收所生成之聚醯亞胺前驅物或聚醯亞胺的情況，若將反應溶液投入溶劑中使其沉澱即可。作為沉澱中使用之溶劑，可舉出甲醇、乙醇、異丙醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙酮、甲基異丁酮、甲苯、苯、水等。投入溶劑中而使其沉澱之聚合物在濾過回收後，可於常壓或者減壓下，常溫或者進行加熱來乾燥。又，若重複2次~10次使沉澱回收之聚合物再溶解於溶劑中並再次沉澱回收之操作，則可使聚合物中之雜質減少。作為此時之溶劑，可舉出例如，醇類、酮類或烴等，若使用由此等之中選出之3種類以上之溶劑，則純化效率係進一步提高，故較佳。When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be added to a solvent to precipitate. Examples of the solvent used in the precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. The polymer which has been introduced into the solvent and precipitated is filtered and recovered, and then dried at normal temperature or under reduced pressure at normal temperature or under heating. Further, if the operation of re-dissolving the precipitate-recovered polymer in a solvent and re-precipitating and recovering is repeated two to ten times, the impurities in the polymer can be reduced. The solvent in this case may, for example, be an alcohol, a ketone or a hydrocarbon. When the solvent of three or more types selected from the above is used, the purification efficiency is further improved, which is preferable.

聚醯亞胺前驅物及聚醯亞胺之藉由凝膠滲透層析法(GPC)所測定之聚苯乙烯換算之重量平均分子量(Mw)較佳為1,000~500,000，更佳為2,000~300,000。又，Mw及藉由GPC所測定之聚苯乙烯換算之數平均分子量(Mn)之比所表示之分子量分布(Mw/Mn)較佳為15以下，更佳為10以下。由於界於此分子量範圍內，可確保液晶顯示元件之良好的配向性。The polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyimide precursor and the polyimine is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. . Further, the molecular weight distribution (Mw/Mn) expressed by the ratio of Mw and the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less. Since it is within the molecular weight range, good alignment of the liquid crystal display element can be ensured.

＜液晶配向劑＞
本發明之液晶配向劑係如同上述將由聚醯亞胺前驅物及聚醯亞胺所成之群所選出之至少1種聚合物，以及因應需要使用之任意添加成分溶解並含有於溶劑所構成。
本發明之液晶配向劑中使用之溶劑，係如同上述含有由前述式(d-1)~(d-5)及(e)所構成之群組所選出之至少1種溶劑A，及由前述式(B-1)~(B-3)所構成之群組所選出之至少1種溶劑B。
藉由含有溶劑A，特定聚合物係變得易溶解於溶劑中，可獲得濾過性或印刷性優異之液晶配向劑。又，藉由含有溶劑B，將液晶配向劑塗布於基板時之針孔或塌凹係被抑制，故可獲得印刷性優異之液晶配向劑。又，藉由組合溶劑A及溶劑B，將液晶配向劑之塗膜乾燥時，具有特定聚合物之側鏈成分彼此不會產生凝集，故配向成分之面內均勻性係提高，可獲得液晶配向性優異之液晶配向膜。又，藉由組合2種以上，特定聚合物中包含之單體成分即使變為複數種，亦可獲得濾過性及印刷性優異之液晶配向劑及液晶配向性優異之液晶配向膜。<Liquid alignment agent>
The liquid crystal alignment agent of the present invention is composed of at least one polymer selected from the group consisting of a polyimide intermediate and a polyimine, and any optional component to be used as needed, and dissolved in a solvent.
The solvent used in the liquid crystal alignment agent of the present invention is at least one solvent A selected from the group consisting of the above formulas (d-1) to (d-5) and (e), and the foregoing At least one solvent B selected from the group consisting of formulas (B-1) to (B-3).
By containing the solvent A, the specific polymer is easily dissolved in a solvent, and a liquid crystal alignment agent excellent in filterability or printability can be obtained. Further, by containing the solvent B, the pinhole or the collapsing system when the liquid crystal alignment agent is applied to the substrate is suppressed, so that a liquid crystal alignment agent excellent in printability can be obtained. Further, when the coating film of the liquid crystal alignment agent is dried by combining the solvent A and the solvent B, the side chain components having the specific polymer do not aggregate, and the in-plane uniformity of the alignment component is improved, and liquid crystal alignment can be obtained. Excellent liquid crystal alignment film. In addition, when a plurality of the monomer components contained in the specific polymer are used in combination, a liquid crystal alignment agent having excellent filterability and printability and a liquid crystal alignment film having excellent liquid crystal alignment properties can be obtained.

前述溶劑，由更進一步提高印刷性之觀點來看，較佳係含有由1種以上之溶劑A及1種以上之溶劑B所構成之3種以上，更佳係含有4種以上，特佳係含有5種以上。
式(d-1)中，作為R1a 之碳數1~8之1價之烴基，可舉出鏈狀烴基、脂環烴基，可舉出例如碳數1~8之鏈狀烷基、碳數3~8之環烷基等。又，作為該烴基中之碳-碳鍵結間具有「-O-」之1價之基，例如，可舉出碳數2~8之烷氧基烷基等。
作為此等之具體例，作為碳數1~8之鏈狀烷基，可舉出例如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基等，作為碳數3~8之環烷基，可舉出環丙基、環丁基、環戊基、環己基等。作為碳數2~8之烷氧基烷基，可舉出例如甲氧基甲基、甲氧基乙基、甲氧基丙基、甲氧基丁基、乙氧基甲基、乙氧基乙基等。此等之基可為直鏈狀亦可為分枝狀。In view of further improving the printability, the solvent is preferably one or more selected from the group consisting of one or more solvents A and one or more solvents B, and more preferably four or more. Contains 5 or more types.
In the formula (d-1), the monovalent hydrocarbon group having 1 to 8 carbon atoms of R 1a may, for example, be a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples thereof include a chain alkyl group having 1 to 8 carbon atoms and carbon. A number of 3 to 8 cycloalkyl groups and the like. In addition, as a group having a monovalent "-O-" between the carbon-carbon bonds in the hydrocarbon group, for example, an alkoxyalkyl group having 2 to 8 carbon atoms may be mentioned.
Specific examples of such a chain include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like as the carbon number of the chain alkyl group having 1 to 8 carbon atoms. Examples of the cycloalkyl group of 3 to 8 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the alkoxyalkyl group having 2 to 8 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, and an ethoxy group. Ethyl and the like. These groups may be linear or branched.

式(d-2)、(d-5)及式(e)中，作為R2a 、R2b 、R5a 、r1a 及r1b 之碳數1~6之烷基，可舉出例如甲基、乙基、丙基、丁基、戊基、己基等，此等可為直鏈狀亦可為分枝狀。
式(d-3)中，R3a 係表示甲基或乙基。
式(d-5)中，作為R5b 及R5c 之碳數1~6之1價之烴基，可舉出鏈狀烴基、脂環烴基，例如可舉出碳數1~6之鏈狀烷基、碳數3~6之環烷基等。又，作為該烴基中之碳-碳鍵結間具有「-O-」之1價之基，可舉出例如碳數1~6之烷氧基烷基等。作為此等之具體例，作為碳數1~6之鏈狀烷基，可舉出例如甲基、乙基、丙基、丁基、戊基、己基等；作為碳數3~6之環烷基，可舉出環丙基、環丁基、環戊基、環己基等。In the formulae (d-2), (d-5) and (e), examples of the alkyl group having 1 to 6 carbon atoms of R 2a , R 2b , R 5a , r 1a and r 1b include, for example, a methyl group. Ethyl, propyl, butyl, pentyl, hexyl, etc., which may be linear or branched.
In the formula (d-3), R 3a represents a methyl group or an ethyl group.
In the formula (d-5), the monovalent hydrocarbon group having 1 to 6 carbon atoms of R 5b and R 5c may, for example, be a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples thereof include a chain alkyl group having 1 to 6 carbon atoms. A group, a cycloalkyl group having a carbon number of 3 to 6, and the like. In addition, as a group having a monovalent "-O-" between the carbon-carbon bonds in the hydrocarbon group, for example, an alkoxyalkyl group having 1 to 6 carbon atoms may be mentioned. Specific examples of such a chain include, as a chain alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc.; and a cycloalkane having a carbon number of 3 to 6 Examples of the group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.

作為式(d-1)之具體例，可舉出N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-(n-丙基)-2-吡咯烷酮、N-異丙基-2-吡咯烷酮、N-(n-丁基)-2-吡咯烷酮、N-(tert-丁基)-2-吡咯烷酮、N-(n-戊基)-2-吡咯烷酮、N-(n-己基)-2-吡咯烷酮、N-環己基-2-吡咯烷酮、N-(n-辛基)-2-吡咯烷酮、N-甲氧基丙基-2-吡咯烷酮、N-乙氧基乙基-2-吡咯烷酮、N-甲氧基丁基-2-吡咯烷酮等。此等之中，由提高液晶配向劑之濾過性之觀點來看，特佳係可使用N-乙基-2-吡咯烷酮、N-(n-戊基)-2-吡咯烷酮、N-(t-丁基)-2-吡咯烷酮、N-(n-丁基)-2-吡咯烷酮、N-環己基-2-吡咯烷酮、N-(n-己基)-2-吡咯烷酮、N-甲氧基丙基-2-吡咯烷酮。Specific examples of the formula (d-1) include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, and N-isopropyl group. -2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-(n-hexyl) -2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-(n-octyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2- Pyrrolidone, N-methoxybutyl-2-pyrrolidone, and the like. Among these, from the viewpoint of improving the filtration property of the liquid crystal alignment agent, N-ethyl-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-(t- can be used. Butyl)-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-(n-hexyl)-2-pyrrolidone, N-methoxypropyl- 2-pyrrolidone.

作為式(d-2)之具體例，可舉出1,3-二甲基-2-咪唑啉酮(以下，以記號DMI記載。)、1,3-二乙基-2-咪唑啉酮、1,3-二丙基-2-咪唑啉酮、1,3-二異丙基-2-咪唑啉酮等。由提高液晶配向劑之濾過性之觀點來看，DMI係較佳。
作為式(d-5)之具體例，可舉出3-丁氧基-N,N-二甲基丙醯胺、3-甲氧基-N,N-二甲基丙醯胺、3-己氧基-N,N-二甲基丙醯胺、異丙氧基-N-異丙基-丙醯胺、n-丁氧基-N-異丙基-丙醯胺等。其中尤其、由提高液晶配向劑之濾過性之觀點來看，3-丁氧基-N,N-二甲基丙醯胺、或3-甲氧基-N,N-二甲基丙醯胺係較佳。Specific examples of the formula (d-2) include 1,3-dimethyl-2-imidazolidinone (hereinafter, referred to as DMI), and 1,3-diethyl-2-imidazolidinone. , 1,3-dipropyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, and the like. From the viewpoint of improving the filterability of the liquid crystal alignment agent, DMI is preferred.
Specific examples of the formula (d-5) include 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, and 3- Hexyloxy-N,N-dimethylpropionamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide, and the like. In particular, from the viewpoint of improving the filterability of the liquid crystal alignment agent, 3-butoxy-N,N-dimethylpropionamide, or 3-methoxy-N,N-dimethylpropanamide It is preferred.

作為式(e)之具體例，可舉出碳酸伸乙酯、碳酸丙烯酯、碳酸丁二酯、碳酸戊二酯、碳酸己二酯、2-甲基-1,3-碳酸丙烯酯、2,2-二甲基-1,3-碳酸丙烯酯等。其中，由提高液晶配向劑之濾過性之觀點來看，碳酸丙烯酯、碳酸伸乙酯，或碳酸丁二酯係較佳。
溶劑A之中，尤其以提高液晶配向性及濾過性之觀點來看，由N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-(n-戊基)-2-吡咯烷酮、N-環己基-2-吡咯烷酮、N-(n-己基)-2-吡咯烷酮、N-甲氧基丙基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、γ-丁內酯、γ-戊內酯、γ-己內酯、3-丁氧基-N,N-二甲基丙醯胺、3-甲氧基-N,N-二甲基丙醯胺所構成之群組所選出之至少1種係較佳。Specific examples of the formula (e) include ethyl carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, hexylene carbonate, 2-methyl-1,3-propylene carbonate, and 2 , 2-dimethyl-1,3-propylene carbonate, and the like. Among them, propylene carbonate, ethyl carbonate, or butylene carbonate is preferred from the viewpoint of improving the filterability of the liquid crystal alignment agent.
Among the solvents A, especially N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, from the viewpoint of improving liquid crystal alignment and filtration properties , N-cyclohexyl-2-pyrrolidone, N-(n-hexyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ- Butyrolactone, γ-valerolactone, γ-caprolactone, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide At least one selected from the group consisting of is preferred.

溶劑中之溶劑A之含有比例，由提高濾過性之觀點來看，相對於液晶配向劑中包含之溶劑全體，為5~99質量%係較佳，10~90質量%係更佳，20~90質量%再更佳。
作為上述式(B-1)之Ap1 及Ap2 之烷基，以及上述式(B-2)之Ap3 及Ap4 之烷基、上述式(B-4)之Ap5 之烷基，可舉出碳數1~6之直鏈狀之烷基、碳數3~6之分枝狀之烷基等。
Ak1 、Ak2 、Ak6 之烷二基可為直鏈狀亦可為分枝狀，例如，可舉出亞甲基、伸乙基、1,3-丙二基、1,2-丙二基、1,4-丁二基、1,3-丁二基等。Ak1 係較佳為伸乙基、1,3-丙二基或1,4-丁二基。n為1或2係較佳。作為上述式(B-3)之Ak4 及Ak5 之烷基，可舉出碳數1~4之直鏈狀之烷基、碳數3~4之分枝狀之烷基等。The content ratio of the solvent A in the solvent is preferably from 5 to 99% by mass, more preferably from 10 to 90% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent, from the viewpoint of improving the filtration property, and more preferably 20 to 90% by mass. 90% by mass is even better.
The alkyl group of A p1 and A p2 of the above formula (B-1), and the alkyl group of A p3 and A p4 of the above formula (B-2), and the alkyl group of A p5 of the above formula (B-4), Examples thereof include a linear alkyl group having 1 to 6 carbon atoms and a branched alkyl group having 3 to 6 carbon atoms.
The alkanediyl groups of A k1 , A k2 and A k6 may be linear or branched, and examples thereof include a methylene group, an ethylidene group, a 1,3-propanediyl group, and a 1,2-propane group. Dibasic, 1,4-butanediyl, 1,3-butanediyl and the like. The A k1 is preferably an exoethyl group, a 1,3-propanediyl group or a 1,4-butanediyl group. It is preferred that n is 1 or 2. Examples of the alkyl group of A k4 and A k5 in the above formula (B-3) include a linear alkyl group having 1 to 4 carbon atoms and a branched alkyl group having 3 to 4 carbon atoms.

作為上述式(B-1)所表示之較佳化合物，可舉出例如，乙二醇二甲基醚、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、二乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、二乙二醇乙基丙基醚、二乙二醇丙基甲基醚、二乙二醇丁基甲基醚、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二丙二醇二甲基醚、丙二醇二乙酸酯、乙二醇、1,4-丁二醇等。Preferred examples of the compound represented by the above formula (B-1) include ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol ethyl ether. Acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl propyl Ether, diethylene glycol propyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol dimethyl Ether, propylene glycol diacetate, ethylene glycol, 1,4-butanediol, and the like.

作為上述式(B-2)所表示之化合物，可舉出例如乙醇酸甲基、乙醇酸乙基、乙醇酸丁酯、乳酸乙基、乳酸n-丁酯、乳酸異戊酯、乙基-3-乙氧基丙酸酯等。
作為上述式(B-3)所表示之化合物，可舉出例如二丙酮醇、乙醯丙酮、乙醯乙酸乙酯、二異丁酮、4,6-二甲基-2-庚酮、二異丁基甲醇等。
作為上述式(B-4)所表示之化合物，可舉出例如乙二醇單甲基醚、乙二醇單乙基醚、乙二醇-n-丙基醚、乙二醇-i-丙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、丙二醇單丁基醚、二丙二醇單甲基醚等。Examples of the compound represented by the above formula (B-2) include methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, n-butyl lactate, isoamyl lactate, and ethyl group. 3-ethoxypropionate and the like.
Examples of the compound represented by the above formula (B-3) include diacetone alcohol, acetamidineacetone, ethyl acetate, diisobutylketone, 4,6-dimethyl-2-heptanone, and Isobutyl methanol and the like.
Examples of the compound represented by the above formula (B-4) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, and ethylene glycol-i-propyl. Ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and the like.

溶劑B之中，尤其由使印刷性及濾過性雙雙成立之觀點來看，較佳係由二異丁酮、二異丁基甲醇、4,6-二甲基-2-庚酮、二丙酮醇、乳酸n-丁酯、乳酸異戊酯、乙醇酸丁酯、乙基-3-乙氧基丙酸酯、乙二醇單丁基醚、丙二醇單丁基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、二乙二醇乙基丙基醚、二乙二醇丙基甲基醚、二乙二醇丁基甲基醚、二丙二醇單甲基醚、二丙二醇二甲基醚、乙二醇單丁基醚乙酸酯及丙二醇二乙酸酯所選出之至少1種。
溶劑中之溶劑B之含有比例，係相對於液晶配向劑中包含之溶劑全體為1~95質量%係較佳，10~90質量%係更佳，20~90質量%係再更佳。Among the solvents B, in particular, from the viewpoint of establishing both printability and filterability, diisobutyl ketone, diisobutyl carbamide, 4,6-dimethyl-2-heptanone, diacetone are preferred. Alcohol, n-butyl lactate, isoamyl lactate, butyl glycolate, ethyl-3-ethoxypropionate, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol methyl Ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl propyl ether, diethylene glycol propyl methyl ether, diethylene glycol butyl methyl ether, dipropylene glycol monomethyl ether, dipropylene glycol At least one selected from the group consisting of dimethyl ether, ethylene glycol monobutyl ether acetate, and propylene glycol diacetate.
The content ratio of the solvent B in the solvent is preferably from 1 to 95% by mass, more preferably from 10 to 90% by mass, even more preferably from 20 to 90% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.

本發明之液晶配向劑中含有之溶劑，由使液晶配向劑之印刷性及濾過性雙雙成立之觀點來看，較佳係包含由下述ms1~ms10所選出之1種組合，更佳係包含由MS1~MS29所選出之1種組合。
・ms1：N-甲基-2-吡咯烷酮及丙二醇單丁基醚
・ms2：N-甲基-2-吡咯烷酮及二丙二醇單甲基醚
・ms3：N-甲基-2-吡咯烷酮及二丙二醇二甲基醚
・ms4：N-甲基-2-吡咯烷酮及丙二醇單甲基醚
・ms5：N-乙基-2-吡咯烷酮及丙二醇單丁基醚
・ms6：N-乙基-2-吡咯烷酮及二丙二醇單甲基醚
・ms7：N-乙基-2-吡咯烷酮及二丙二醇二甲基醚
・ms8：N-乙基-2-吡咯烷酮及丙二醇單甲基醚
・ms9：N-甲基-2-吡咯烷酮及乳酸異戊酯
・ms10：N-甲基-2-吡咯烷酮及二丙酮醇
・ms11：γ-丁內酯及乙基-3-乙氧基丙酸酯
・ms12：N-乙基-2-吡咯烷酮及二異丁酮The solvent contained in the liquid crystal alignment agent of the present invention preferably includes one combination selected from the following ms1 to ms10 from the viewpoint of establishing both the printability and the filterability of the liquid crystal alignment agent, and more preferably contains One combination selected by MS1~MS29.
・ms1: N-methyl-2-pyrrolidone and propylene glycol monobutyl ether, ms2: N-methyl-2-pyrrolidone and dipropylene glycol monomethyl ether, ms3: N-methyl-2-pyrrolidone and dipropylene glycol Methyl ether, ms4: N-methyl-2-pyrrolidone and propylene glycol monomethyl ether, ms5: N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, ms6: N-ethyl-2-pyrrolidone and two Propylene glycol monomethyl ether, ms7: N-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether, ms8: N-ethyl-2-pyrrolidone and propylene glycol monomethyl ether, ms9: N-methyl-2- Pyrrolidone and isoamyl lactate, ms10: N-methyl-2-pyrrolidone and diacetone alcohol, ms11: γ-butyrolactone and ethyl-3-ethoxypropionate, ms12: N-ethyl-2 -pyrrolidone and diisobutanone

・MS1：N-甲基-2-吡咯烷酮及γ-丁內酯及丙二醇單丁基醚
・MS2：N-甲基-2-吡咯烷酮及γ-丁內酯及二丙二醇單甲基醚
・MS3：N-甲基-2-吡咯烷酮及γ-丁內酯及二丙二醇二甲基醚
・MS4：N-甲基-2-吡咯烷酮及γ-丁內酯及丙二醇單甲基醚
・MS5：N-乙基-2-吡咯烷酮及γ-丁內酯及丙二醇單丁基醚
・MS6：N-乙基-2-吡咯烷酮及γ-丁內酯及二丙二醇單甲基醚
・MS7：N-乙基-2-吡咯烷酮及γ-丁內酯及二丙二醇二甲基醚
・MS8：N-乙基-2-吡咯烷酮及γ-丁內酯及丙二醇單甲基醚・MS1: N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether·MS2: N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol monomethyl ether·MS3: N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether·MS4: N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monomethyl ether·MS5: N-B Base-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether·MS6: N-ethyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol monomethyl ether·MS7: N-ethyl-2 -pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether·MS8: N-ethyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monomethyl ether

・MS9：N-乙基-2-吡咯烷酮及N-甲基-2-吡咯烷酮及丙二醇單丁基醚
・MS10：N-乙基-2-吡咯烷酮及N-甲基-2-吡咯烷酮及二丙二醇單甲基醚
・MS11：N-乙基-2-吡咯烷酮及N-甲基-2-吡咯烷酮及二丙二醇二甲基醚
・MS12：N-乙基-2-吡咯烷酮及N-甲基-2-吡咯烷酮及γ-丁內酯及丙二醇單甲基醚
・MS13：N-甲基-2-吡咯烷酮及二丙酮醇及二乙二醇二乙基醚
・MS14：N-甲基-2-吡咯烷酮及丙二醇單丁基醚及二丙二醇單甲基醚
・MS15：N-甲基-2-吡咯烷酮及N-乙基-2-吡咯烷酮及二異丁基甲醇
・MS16：N-乙基-2-吡咯烷酮及丙二醇單丁基醚及二異丁酮・MS9: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and propylene glycol monobutyl ether · MS10: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and dipropylene glycol Methyl ether, MS11: N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and dipropylene glycol dimethyl ether, MS12: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone And γ-butyrolactone and propylene glycol monomethyl ether·MS13: N-methyl-2-pyrrolidone and diacetone alcohol and diethylene glycol diethyl ether·MS14: N-methyl-2-pyrrolidone and propylene glycol Butyl ether and dipropylene glycol monomethyl ether, MS15: N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and diisobutyl carbamide, MS16: N-ethyl-2-pyrrolidone and propylene glycol Butyl ether and diisobutyl ketone

・MS17：N-乙基-2-吡咯烷酮及乙二醇單丁基醚乙酸酯及二丙二醇單甲基醚
・MS18：N-乙基-2-吡咯烷酮及N-甲基-2-吡咯烷酮及二丙酮醇
・MS19：γ-丁內酯及1,3-二甲基-2-咪唑啉酮及乙基-3-乙氧基丙酸酯
・MS20：N-甲基-2-吡咯烷酮及3-甲氧基-N,N-二甲基丙醯胺及二丙酮醇
・MS21：N-甲基-2-吡咯烷酮及碳酸丙烯酯及二丙酮醇
・MS22：N-甲基-2-吡咯烷酮及乙醇酸丁酯及二丙二醇二甲基醚・MS17: N-ethyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate and dipropylene glycol monomethyl ether, MS18: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone Diacetone alcohol·MS19: γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone and ethyl-3-ethoxypropionate·MS20: N-methyl-2-pyrrolidone and 3 -methoxy-N,N-dimethylpropanamide and diacetone alcohol, MS21: N-methyl-2-pyrrolidone and propylene carbonate and diacetone alcohol, MS22: N-methyl-2-pyrrolidone and Butyl glycolate and dipropylene glycol dimethyl ether

・MS23：N-乙基-2-吡咯烷酮及二丙酮醇及丙二醇單丁基醚
・MS24：N-乙基-2-吡咯烷酮及二丙酮醇及乙基-3-乙氧基丙酸酯
・MS25：γ-戊內酯及γ-丁內酯及乙基-3-乙氧基丙酸酯
・MS26：N-甲基-2-吡咯烷酮及二乙二醇二乙基醚及二丙二醇單甲基醚
・MS27：N-甲基-2-吡咯烷酮及丙二醇單丁基醚及二乙二醇丁基甲基醚
・MS28：N-乙基-2-吡咯烷酮及二乙二醇乙基甲基醚及二異丁酮
・MS29：N-甲基-2-吡咯烷酮及二丙酮醇及丙二醇二乙酸酯・MS23: N-ethyl-2-pyrrolidone, diacetone alcohol and propylene glycol monobutyl ether, MS24: N-ethyl-2-pyrrolidone, diacetone alcohol and ethyl-3-ethoxypropionate·MS25 : γ-valerolactone and γ-butyrolactone and ethyl-3-ethoxypropionate·MS26: N-methyl-2-pyrrolidone, diethylene glycol diethyl ether and dipropylene glycol monomethyl Ether, MS27: N-methyl-2-pyrrolidone, propylene glycol monobutyl ether and diethylene glycol butyl methyl ether, MS28: N-ethyl-2-pyrrolidone, diethylene glycol ethyl methyl ether and diiso Butanone MS29: N-methyl-2-pyrrolidone and diacetone alcohol and propylene glycol diacetate

本發明之液晶配向劑中，作為溶劑，亦可併用其他溶劑與上述同時使用。作為此處可使用之其他溶劑，可舉出例如N,N-二甲基丙烯尿素、N,N,2-三甲基丙醯胺、乙二醇單丁基醚(丁基溶纖劑)、甲基甲氧基丙酸酯、異戊基丙酸酯、異戊基異丁酸酯、二異戊基醚、環己酮、3-甲基環己酮、4-甲基環己酮、2-羥基異酪酸甲基、WO2011/132751之[0203]所記載之具有低表面張力之溶劑，但並不被此等之限定。In the liquid crystal alignment agent of the present invention, as a solvent, other solvents may be used in combination with the above. Examples of other solvents which can be used herein include N,N-dimethyl propylene urea, N,N,2-trimethyl propyl amide, ethylene glycol monobutyl ether (butyl cellosolve), and A. Methoxy propionate, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2 a solvent having a low surface tension as described in [0203] of WO2011/132751, but is not limited by these.

本發明之液晶配向劑中之固體成分濃度(係指液晶配向劑中之溶劑以外之成分之合計重量佔液晶配向劑之全重量之比例。)係考慮黏性、揮發性等所選擇，但特佳之固體成分濃度之範圍係依於基板塗布液晶配向劑時所使用之方法而有所不同。例如藉由柔版印刷法來進行時，將固體成分濃度設為3~9重量%之範圍，藉此將溶液黏度設為12~50mPa・s之範圍內係特佳。藉由噴墨法來進行時，將固體成分濃度設為1~5重量%之範圍，藉此將溶液黏度設為3~15mPa・s之範圍係特佳。
本發明之液晶配向劑中亦可導入具有環氧基、異氰酸酯基、氧環丁烷基或環碳酸酯基之交聯性化合物、具有由羥基、羥基烷基及低級烷氧基烷基所選出之至少1種取代基之交聯性化合物，或具有聚合性不飽和鍵結之交聯性化合物。此等取代基或聚合性不飽和鍵結，係於交聯性化合物中具有2個以上為較佳。The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is selected in consideration of viscosity, volatility, etc. The range of the solid content concentration is preferably different depending on the method used when the substrate is coated with the liquid crystal alignment agent. For example, when it is carried out by the flexographic printing method, the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is particularly preferably in the range of 12 to 50 mPa·s. When the inkjet method is carried out, the solid content concentration is in the range of 1 to 5% by weight, and the solution viscosity is preferably in the range of 3 to 15 mPa·s.
The liquid crystal alignment agent of the present invention may also be introduced with a crosslinking compound having an epoxy group, an isocyanate group, an oxycyclobutane group or a cyclic carbonate group, and having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group selected. A crosslinkable compound having at least one substituent or a crosslinkable compound having a polymerizable unsaturated bond. These substituents or polymerizable unsaturated bonds are preferably two or more of the crosslinkable compounds.

作為具有環氧基或異氰酸酯基之交聯性化合物，可舉出例如，WO2015/008846之[0087]所記載之化合物等。
具有氧環丁烷基之交聯性化合物係具體而言，可舉出WO2011/132751之58~59頁所揭載之式[4a]~式[4k]所示之交聯性化合物。作為更佳具體例，可舉出式[4b]、式[4d]、式[4k]中n=5之化合物。
作為具有環碳酸酯基之交聯性化合物，具體而言，可舉出WO2012/014898之76~82頁所揭載之式[5-1]~式[5-42]所示之交聯性化合物。The cross-linking compound having an epoxy group or an isocyanate group may, for example, be a compound described in [0087] of WO2015/008846.
Specific examples of the crosslinkable compound having an oxycyclobutane group include the crosslinkable compounds represented by the formula [4a] to the formula [4k] disclosed in pages 58 to 59 of WO2011/132751. More preferable specific examples include compounds of the formula [4b], the formula [4d], and the formula [4k] wherein n=5.
Specific examples of the crosslinkable compound having a cyclic carbonate group include the crosslinkability represented by the formula [5-1] to the formula [5-42] disclosed in pages 76 to 82 of WO2012/014898. Compound.

作為具有由羥基及烷氧基所構成之群組所選出之至少1種取代基之交聯性化合物，可舉出WO2015/ 008846之[0090]~[0092]所記載之化合物、具有WO2015/ 072554之[0054]所記載之羥基烷基醯胺基之化合物、WO2015/156314之[0126]所記載之化合物等。作為更佳具體例，可舉出WO2011/132751之[181]~[185]所揭載之式[6-1]~[6-48]所表示之交聯性化合物、具有WO2015/072554之[0054]所記載之羥基烷基醯胺基之化合物、WO2015/ 156314之[0126]所記載之化合物。
作為具有聚合性不飽和鍵結之交聯性化合物，可舉出例如WO2011/132751之[0186]所記載之化合物。Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group include the compounds described in [0090] to [0092] of WO2015/008846, and having WO2015/072554 The compound of the hydroxyalkylguanamine group described in [0054], the compound described in [0126] of WO2015/156314, and the like. Further, as a more specific example, a crosslinkable compound represented by the formula [6-1] to [6-48] disclosed in [181] to [185] of WO2011/132751, having WO2015/072554 [ The compound of the hydroxyalkylguanamine group described in [0126], and the compound of [0126] of WO2015/156314.
The crosslinkable compound having a polymerizable unsaturated bond may, for example, be a compound described in [0186] of WO2011/132751.

此外，亦可使用WO2011/132751之[0188]所記載之式[5]所示之化合物。
上述化合物為交聯性化合物的一個例子，但並不限定為此等。又，本發明之液晶配向劑中使用之交聯性化合物可為1種，亦可為2種以上之組合。
本發明之液晶配向劑中之交聯性化合物之含量，係相對於所有的聚合物成分100質量份，為0.1~150質量份係較佳。其中尤其為了交聯反應之進行並使目的之效果顯現，較佳為相對於所有的聚合物成分100質量份，為0.1~100質量份。更佳為1質量份~50質量份。Further, a compound represented by the formula [5] described in [0188] of WO2011/132751 can also be used.
The above compound is an example of a crosslinkable compound, but is not limited thereto. Further, the crosslinkable compound to be used in the liquid crystal alignment agent of the present invention may be one type or a combination of two or more types.
The content of the crosslinkable compound in the liquid crystal alignment agent of the present invention is preferably 0.1 to 150 parts by mass based on 100 parts by mass of all the polymer components. In particular, in order to carry out the crosslinking reaction and to exhibit the effect of the object, it is preferably 0.1 to 100 parts by mass based on 100 parts by mass of all the polymer components. More preferably, it is 1 part by mass to 50 parts by mass.

本發明之液晶配向劑，可使用塗布液晶配向劑時使液晶配向膜之膜厚均勻性或表面平滑性提高之化合物。
作為使液晶配向膜之膜厚均勻性或表面平滑性提高之化合物，可舉出氟系界面活性劑、矽酮系界面活性劑、非離子系界面活性劑等。更具體而言，可舉出例如，Eftop EF301、EF303、EF352(以上為Tohkem products Corporation製)、Megafac F171、F173、R-30(以上為DIC Corporation製)、Fluorad FC430、FC431(以上為住友3M公司製)、AsahiGuard AG710、Surflon S-382、SC101、SC102、SC103、SC104、SC105、SC106(以上為旭硝子公司製)等。
此等之界面活性劑之使用比例，係相對於液晶配向劑中含有之所有的聚合物成分100質量份，較佳為0.01~2質量份，更佳為0.01~1質量份。In the liquid crystal alignment agent of the present invention, a compound which improves the film thickness uniformity or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied can be used.
Examples of the compound which improves the film thickness uniformity or the surface smoothness of the liquid crystal alignment film include a fluorine-based surfactant, an anthrone-based surfactant, and a nonionic surfactant. More specifically, Eftop EF301, EF303, EF352 (above, manufactured by Tohkem Products Corporation), Megafac F171, F173, R-30 (above, DIC Corporation), Fluorad FC430, FC431 (above Sumitomo 3M) Company system), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (the above is manufactured by Asahi Glass Co., Ltd.).
The ratio of use of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.

此外，本發明之液晶配向劑中，作為促進液晶配向膜中之電荷移動，使元件之去電荷被促進之化合物，亦可添加WO2011/132751(2011.10.27公開)之69~73頁所揭載之式[M1]~式[M156]所示之含氮雜環胺化合物。此胺化合物直接添加於液晶配向劑亦無妨，但較佳係於以適當的溶劑其成為濃度為0.1~10質量%、較佳為1~7質量%之溶液後再添加。作為此溶劑，若為可使上述特定聚合物溶解之溶劑，則未被特別限定。
本發明之液晶配向劑中，除了上述之貧溶劑、交聯性化合物、樹脂被膜或使液晶配向膜之膜厚均勻性或表面平滑性提高之化合物及使去電荷被促進之化合物以外，亦可添加以使液晶配向膜之誘電率或導電性等的電特性變化為目的之介電體或導電物質。Further, in the liquid crystal alignment agent of the present invention, as a compound which promotes the movement of charges in the liquid crystal alignment film and promotes the decharge of the element, it may be added as disclosed in WO2011/132751 (2011.10.27), pages 69-73. A nitrogen-containing heterocyclic amine compound represented by the formula [M1] to the formula [M156]. The amine compound may be added directly to the liquid crystal alignment agent, but it is preferably added after a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, in a suitable solvent. The solvent is not particularly limited as long as it is a solvent capable of dissolving the above specific polymer.
In the liquid crystal alignment agent of the present invention, in addition to the above-mentioned poor solvent, crosslinkable compound, resin film, or a compound which improves film thickness uniformity or surface smoothness of the liquid crystal alignment film, and a compound which promotes decharge charging, A dielectric or conductive material for the purpose of changing the electrical characteristics such as the electric conductivity or conductivity of the liquid crystal alignment film is added.

＜液晶配向膜・液晶顯示元件＞
本發明之液晶配向劑係於基板上塗布且進行燒結後，以摩擦處理或光照射等進行配向處理後，可作為液晶配向膜使用。又，垂直配向用途等的場合中，即使不進行配向處理亦可作為液晶配向膜使用。作為此時所使用之基板，若為透明性高之基板則無特別限定，除了玻璃基板以外，亦可使用壓克力基板或聚碳酸酯基板等的塑膠基板等。由製程之精簡化之觀點來看，較佳係使用用於液晶驅動之形成有ITO電極等之基板。又，反射型之液晶顯示元件中，若僅為單側之基板，則矽晶圓等的不透明基板亦可使用，作為此情況之電極，亦可使用鋁等將光反射之材料。<Liquid alignment film and liquid crystal display element>
The liquid crystal alignment agent of the present invention is applied to a substrate and sintered, and then subjected to an alignment treatment by rubbing treatment or light irradiation, and then used as a liquid crystal alignment film. Further, in the case of vertical alignment use or the like, it can be used as a liquid crystal alignment film even without alignment treatment. The substrate to be used in this case is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to the glass substrate. From the viewpoint of simplification of the process, it is preferred to use a substrate on which an ITO electrode or the like is formed for liquid crystal driving. Further, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the substrate on one side, and as the electrode in this case, a material that reflects light such as aluminum can be used.

液晶配向劑之塗布方法可舉出網版印刷、膠版印刷、柔版印刷或噴墨法、浸漬法、輥塗布法、狹縫塗布法、旋轉塗布法或噴霧法等，但由提高液晶配向膜之製造效率之觀點來看，以柔版印刷或噴墨法塗布之方法係較佳。
將液晶配向劑於基板上塗布後，可藉由加熱板、熱循環型烤箱或IR(紅外線)型烤箱等的加熱手段，因應液晶配向劑中使用之溶劑，於30~300℃、較佳為30~250℃之溫度使溶劑蒸發，作為液晶配向膜。燒結後之液晶配向膜之厚度若過厚，則於液晶顯示元件之消費電力之方面係變得不利，若過薄，則有液晶顯示元件之信賴性低下之情況，故較佳為5~300nm，更佳為10~100nm。Examples of the method for applying the liquid crystal alignment agent include screen printing, offset printing, flexographic printing or ink jet method, dipping method, roll coating method, slit coating method, spin coating method, spray method, and the like, but the liquid crystal alignment film is improved. From the viewpoint of manufacturing efficiency, a method of coating by flexographic printing or inkjet printing is preferred.
After the liquid crystal alignment agent is applied onto the substrate, it can be heated at 30 to 300 ° C, preferably by a heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven, in accordance with the solvent used in the liquid crystal alignment agent. The solvent is evaporated at a temperature of 30 to 250 ° C to serve as a liquid crystal alignment film. When the thickness of the liquid crystal alignment film after sintering is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element is low, so it is preferably 5 to 300 nm. More preferably, it is 10~100nm.

應被製造之液晶顯示元件之表示模式為VA型的情況，如同上述之方式被形成之塗膜可直接作為液晶配向膜使用，但亦可因應需要進行摩擦處理或後述之PSA處理。另一方面，應被製造之液晶顯示元件之表示模式為VA型以外之垂直電場方式的情況及為橫電場方式的情況，對於所形成之塗膜面，以摩擦處理或偏光紫外線照射等處理，並進行配向處理。
本發明之液晶配向劑亦較佳用於在具備電極的一對基板之間具有液晶層而成且經由下述步驟而製造的液晶顯示元件，該步驟為：在一對基板之間配置液晶組合物，該液晶組合物包含因活性能量線和熱中的至少一者而聚合的聚合性化合物，邊對電極之間施加電壓，邊藉由照射活性能量線和加熱中的至少一者使聚合性化合物聚合之步驟。此處，施加之電壓可作為例如5~50V之直流或交流電。又，作為活性能量線，紫外線為適宜。作為紫外線，為包含波長為300~400nm之波長之光之紫外線，較佳為包含310~ 360nm之波長之光之紫外線。作為光之照射量，較佳為0.1 ~20J/cm2 ，更佳為1~20J/cm2 。In the case where the display mode of the liquid crystal display element to be manufactured is the VA type, the coating film formed as described above can be directly used as the liquid crystal alignment film, but the rubbing treatment or the PSA treatment described later may be performed as needed. On the other hand, in the case where the display mode of the liquid crystal display element to be manufactured is a vertical electric field method other than the VA type and the case of the horizontal electric field method, the formed film surface is treated by rubbing treatment or polarized ultraviolet light irradiation. And the alignment process is performed.
The liquid crystal alignment agent of the present invention is also preferably used for a liquid crystal display device which has a liquid crystal layer between a pair of substrates including electrodes and is produced through the following steps: a liquid crystal combination is disposed between a pair of substrates The liquid crystal composition comprising a polymerizable compound polymerized by at least one of an active energy ray and heat, and a polymerizable compound is irradiated by at least one of an active energy ray and a heating while applying a voltage between the electrodes. The step of polymerization. Here, the applied voltage can be used as, for example, a direct current of 5 to 50 V or an alternating current. Further, as the active energy ray, ultraviolet rays are suitable. The ultraviolet light is ultraviolet light containing light having a wavelength of 300 to 400 nm, preferably ultraviolet light containing light having a wavelength of 310 to 360 nm. The amount of irradiation of light is preferably 0.1 to 20 J/cm 2 , more preferably 1 to 20 J/cm 2 .

上述之液晶顯示元件係藉由PSA方式，來控制液晶分子之預傾斜者。在PSA方式中，預先於液晶材料中混入少量之光聚合性化合物，例如光聚合性單體，組裝成液晶胞後，於對液晶層施加特定的電壓之狀態下，對光聚合性化合物照射紫外線等，藉由所生成之聚合物控制液晶分子之預傾斜。聚合物生成時之液晶分子之配向狀態係即使在去除電壓後亦被記憶，因此藉由控制形成於液晶層中的電場等，能夠調整液晶分子的預傾斜。又，在PSA方式中，不需要摩擦處理，因此適合於難以藉由摩擦處理來控制預傾斜的垂直配向型之液晶層的形成。The above liquid crystal display element controls the pretilt of the liquid crystal molecules by the PSA method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is incorporated in a liquid crystal material, and a liquid crystal cell is assembled, and a photopolymerizable compound is irradiated with ultraviolet rays while applying a specific voltage to the liquid crystal layer. Etc., the pretilt of the liquid crystal molecules is controlled by the generated polymer. The alignment state of the liquid crystal molecules at the time of polymer formation is memorized even after the voltage is removed. Therefore, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. Further, in the PSA method, since the rubbing treatment is not required, it is suitable for the formation of the vertical alignment type liquid crystal layer which is difficult to control the pretilt by the rubbing treatment.

本發明之液晶顯示元件，係藉由上述之手法，由本發明之液晶配向劑獲得附有液晶配向膜之基板後，以公知之方法製作液晶胞作為液晶顯示元件者。
作為液晶胞之製作方法，可例示如下方法：準備形成有液晶配向膜之一對基板，在其中一個基板的液晶配向膜上散布間隔物，以液晶配向膜面成為內側的方式黏貼另一個基板，減壓注入液晶並密封之方法，或在對散布有間隔物的液晶配向膜面滴加液晶後，黏貼基板並進行密封的方法等。
液晶中，亦可混合如同前述之藉由紫外線照射或熱聚合之聚合性化合物。作為聚合性化合物，可舉一分子內具有1個以上丙烯酸酯基或甲基丙烯酸酯基等的聚合性不飽和基之化合物，例如如同下述式(M-1)~(M-3)所表示之聚合性化合物。In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above-described method, and a liquid crystal cell is produced as a liquid crystal display element by a known method.
As a method of producing the liquid crystal cell, a method in which one of the liquid crystal alignment films is formed is prepared, a spacer is spread on the liquid crystal alignment film of one of the substrates, and the other substrate is adhered so that the liquid crystal alignment film surface is inside. A method of injecting a liquid crystal and sealing it under reduced pressure, or a method of adhering a liquid crystal to a liquid crystal alignment film surface on which a spacer is dispersed, and adhering the substrate and sealing it.
In the liquid crystal, a polymerizable compound which is irradiated with ultraviolet rays or thermally polymerized as described above may also be mixed. The polymerizable compound may be a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in one molecule, and is, for example, in the following formulas (M-1) to (M-3). A polymerizable compound represented.

聚合性化合物係相對於液晶成分之100質量份，為0.01~10質量份係較佳，更佳為0.1~5質量份。聚合性化合物若未滿0.01質量份，則聚合性化合物不會聚合而變得無法控制液晶之配向，或若超過10質量份，則未反應之聚合性化合物變多而液晶顯示元件的圖像保留特性降低。製作液晶胞後一邊對液晶胞施加交流或直流之電壓，一邊加熱或照射紫外線而將聚合性化合物聚合。藉此，可控制液晶分子之配向。
此外，本發明之液晶配向劑亦可用於在具備電極的一對基板之間具有液晶層而成，且經由下述步驟而製造之液晶顯示元件，該步驟為：在前述一對基板之間配置液晶配向膜，該液晶配向膜包含因活性能量線和熱中的至少一者而聚合之聚合性基，並對電極間施加電壓之步驟，亦即，可用於SC-PVA模式。此處，作為活性能量線，紫外線為適宜。作為紫外線，可將於前述PSA方式使用之紫外線包含在較佳態樣而適用。藉由加熱所進行聚合時，加熱溫度為40~120℃、較佳為60~80℃。又，紫外線及加熱亦可同時進行。The polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and the alignment of the liquid crystal is not controlled, or if it exceeds 10 parts by mass, the unreacted polymerizable compound increases and the image of the liquid crystal display element remains. Reduced characteristics. After the liquid crystal cell is produced, a voltage of alternating current or direct current is applied to the liquid crystal cell, and the polymerizable compound is polymerized by heating or irradiating ultraviolet rays. Thereby, the alignment of the liquid crystal molecules can be controlled.
Further, the liquid crystal alignment agent of the present invention may be used for a liquid crystal display device which is formed by providing a liquid crystal layer between a pair of substrates including an electrode and which is produced by the following steps: arranging between the pair of substrates A liquid crystal alignment film comprising a polymerizable group polymerized by at least one of an active energy ray and heat, and a step of applying a voltage between the electrodes, that is, a SC-PVA mode. Here, as the active energy ray, ultraviolet rays are suitable. As the ultraviolet ray, the ultraviolet ray used in the above PSA method can be applied in a preferred embodiment. When the polymerization is carried out by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, ultraviolet rays and heating can be simultaneously performed.

為了獲得包含因活性能量線和熱中的至少一者聚合之聚合性基之液晶配向膜，可舉出將包含此聚合性基之化合物添加於液晶配向劑中之方法，或使用包含聚合性基之聚合物成分之方法。作為包含聚合性基之聚合物之具體例，可舉出使用前述具有藉由光照射聚合之機能之二胺所獲得之聚合物。

[實施例]In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, a method of adding a compound containing the polymerizable group to a liquid crystal alignment agent, or a method comprising a polymerizable group may be mentioned. Method of polymer composition. Specific examples of the polymer containing a polymerizable group include a polymer obtained by using the above-described diamine having a function of polymerization by light irradiation.

[Examples]

以下，藉由實施例更具體地說明本發明，但本發明係不受此等之實施例所限定者。

(特定二胺)
W-A1：式[W-A1]所表示之化合物、W-A2：式[W-A2]所表示之化合物
W-A3：式[W-A3]所表示之化合物Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples.

(specific diamine)
W-A1: a compound represented by the formula [W-A1], W-A2: a compound represented by the formula [W-A2]
W-A3: a compound represented by the formula [W-A3]

(其他側鏈型二胺化合物)
A1：式[A1]所表示之化合物
(Other side chain type diamine compounds)
A1: a compound represented by the formula [A1]

C1：式[C1]所表示之化合物、C2：式[C2]所表示之化合物
C3：式[C3]所表示之化合物、C4：式[C4]所表示之化合物
C1: a compound represented by the formula [C1], C2: a compound represented by the formula [C2]
C3: a compound represented by the formula [C3], C4: a compound represented by the formula [C4]

(四羧酸化合物)
D1：1,2,3,4-環丁烷四羧酸二酐
D2：二環[3,3,0]辛烷-2,4,6,8-四羧酸二酐
D3：苯均四酸酐、D4：2,3,5-三羧基環戊基乙酸二酐
(tetracarboxylic acid compound)
D1:1,2,3,4-cyclobutane tetracarboxylic dianhydride
D2: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride
D3: pyromellitic anhydride, D4: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

＜溶劑A＞
NMP：N-甲基-2-吡咯烷酮、NEP：N-乙基-2-吡咯烷酮
DMI：1,3-二甲基-2-咪唑啉酮、GVL：γ-戊內酯
GBL：γ-丁內酯、CHP：N-環己基-2-吡咯烷酮
NHP：N-(n-己基)-2-吡咯烷酮、
3MMP：3-甲氧基-N,N-二甲基丙醯胺<solvent A>
NMP: N-methyl-2-pyrrolidone, NEP: N-ethyl-2-pyrrolidone
DMI: 1,3-dimethyl-2-imidazolidinone, GVL: γ-valerolactone
GBL: γ-butyrolactone, CHP: N-cyclohexyl-2-pyrrolidone
NHP: N-(n-hexyl)-2-pyrrolidone,
3MMP: 3-methoxy-N,N-dimethylpropanamide

＜溶劑B＞
IAL：乳酸異戊酯、nBL：乳酸n-丁酯、HBA：乙醇酸丁酯
EEP：乙基-3-乙氧基丙酸酯、DIBC：二異丁基甲醇
DIBK：二異丁酮、DAA：二丙酮醇
BCA：乙二醇單丁基醚乙酸酯
PB：丙二醇單丁基醚、PGDA：丙二醇二乙酸酯
PC：碳酸丙烯酯、DEME：二乙二醇甲基乙基醚
DEDE：二乙二醇二乙基醚
DPM：二丙二醇單甲基醚
DME：二丙二醇二甲基醚
DEBM：二乙二醇丁基甲基醚<Solvent B>
IAL: isoamyl lactate, nBL: n-butyl lactate, HBA: butyl glycolate
EEP: ethyl-3-ethoxypropionate, DIBC: diisobutylmethanol
DIBK: diisobutyl ketone, DAA: diacetone alcohol
BCA: ethylene glycol monobutyl ether acetate
PB: propylene glycol monobutyl ether, PGDA: propylene glycol diacetate
PC: propylene carbonate, DEME: diethylene glycol methyl ethyl ether
DEDE: Diethylene glycol diethyl ether
DPM: dipropylene glycol monomethyl ether
DME: dipropylene glycol dimethyl ether
DEBM: diethylene glycol butyl methyl ether

(分子量測定)
聚醯亞胺前驅物及聚醯亞胺之分子量係使用常溫膠體滲透層析(GPC)裝置(GPC-101)(昭和電工公司製)、管柱(KD-803，KD-805)(Shodex公司製)，以如下之方式測定。
管柱溫度：50℃
溶離液：N,N’-二甲基甲醯胺(作為添加劑，溴化鋰-水合物(LiBr・H2 O)為30mmol/L(公升)、磷酸・無水結晶(o-磷酸)為30mmol/L、四氫呋喃(THF)為10ml/L)、流速：1.0ml/分鐘
用於作成校正曲線之標準試樣：TSK 標準聚環氧乙烷(分子量；約900,000、150,000、100,000及30,000)(東曹公司製)及聚乙二醇(分子量；約12,000、4,000及1,000) (Polymer Laboratories Ltd.製)。(molecular weight determination)
The molecular weight of the polyimine precursor and the polyimine is a normal temperature colloidal permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD-805) (Shodex Corporation) (system), measured in the following manner.
Column temperature: 50 ° C
Dissolution: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr·H 2 O) is 30 mmol/L (liter), phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L , tetrahydrofuran (THF) 10ml / L), flow rate: 1.0ml / min used to make a calibration curve of the standard sample: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (Tosoh Corporation And polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories Ltd.).

(醯亞胺化率之測定)
將聚醯亞胺粉末20mg放入NMR(核磁共振)試樣管(NMR標準採樣管，f5(草野科學公司製))中，添加重氫化二甲基亞碸(DMSO-d6，0.05質量%TMS(四甲基矽烷)混合品)(0.53ml)，施加超音波使其完全地溶解。將此溶液以NMR測定機(JNW-ECA500)(日本電子Datum公司製)，測定500MHz之質子NMR。醯亞胺化率，係以源自醯亞胺化前後未變化之結構的質子為基準質子，使用該質子之峰值積算值及源自出現在9.5~10.0ppm附近之醯胺酸之NH基之質子峰值積算值，藉由以下之式求得。

上述式中，x為源自醯胺酸之NH基之質子峰值積算值、y為基準質子之峰值積算值、α為聚醯胺酸(醯亞胺化率為0%)時之相對於1個醯胺酸之NH基的質子的基準質子之個數比例。(Measurement of sulfhydrylation rate)
20 mg of polyimine powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR standard sampling tube, f5 (manufactured by Kusano Scientific Co., Ltd.)), and dimethyl-hydrazine (DMSO-d6, 0.05% by mass of TMS) was added. (tetramethyl decane) (0.53 ml), ultrasonic waves were applied to completely dissolve them. This solution was measured by a NMR measuring machine (JNW-ECA500) (manufactured by JEOL Ltd., Japan), and a proton NMR of 500 MHz was measured. The imidization ratio of ruthenium is based on a proton derived from a structure which has not changed before and after imidization, and the peak value of the proton is used and the NH group derived from proline which is present in the vicinity of 9.5 to 10.0 ppm The proton peak value is obtained by the following formula.

In the above formula, x is the proton peak value of the NH group derived from proline, y is the peak value of the reference proton, and α is the polyamine (the imidization ratio is 0%) relative to 1 The ratio of the number of reference protons of protons of the NH group of proline.

(黏度)
聚醯亞胺系聚合物之黏度係使用E型黏度計TVE-22H(東機產業股份公司製)，以試樣量1.1mL、錐形轉子TE-1(1°34’、R24)、溫度25℃進行測定。(viscosity)
The viscosity of the polyimide-based polymer is E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL, a conical rotor TE-1 (1°34', R24), and a temperature. The measurement was carried out at 25 °C.

＜特定二胺之合成＞
W-A1~W-A3為文獻等中未公開之新穎化合物，以如下之方式合成。
下述合成例1~3所記載之生成物係藉由1 H-NMR分析，以下述之條件確定。
裝置：Varian NMR System 400 NB (400 MHz)。
測定溶劑：CDCl3 、DMSO-d6 。
基準物質：四甲基矽烷(TMS)(δ0.0 ppm for1 H)。<Synthesis of specific diamines>
W-A1 to W-A3 are novel compounds not disclosed in the literature and the like, and are synthesized in the following manner.
The products described in the following Synthesis Examples 1 to 3 were determined by 1 H-NMR analysis under the following conditions.
Device: Varian NMR System 400 NB (400 MHz).
The solvent was measured: CDCl 3 , DMSO-d 6 .
Reference material: tetramethyl decane (TMS) (δ0.0 ppm for 1 H).

＜合成例1 W-A1之合成＞

＜化合物[1]、[2]之合成＞
於反應容器中添加四氫呋喃(165.6g)、4,4’-二硝基-1,1’-聯苯基-2,2’-二甲醇(41.1g、135mmol)及三乙胺(31.5g)，於氮環境冰冷條件下將甲磺醯氯(33.2g)滴下，使其反應1小時藉此獲得化合物[1]。接下來，添加使其溶解於四氫呋喃(246.6g)中之p-(trans-4-庚基環己基)酚(77.8g)，於40℃攪拌1小時後，於同溫度下添加使其溶解於純水(233g)中之氫氧化鉀(41.0g)，使其反應21小時。反應結束後，添加1.0M鹽酸水溶液(311ml)及純水(1050g)，使粗產物析出，藉由過濾將粗產物回收。藉由使獲得之粗產物於四氫呋喃(574g)中50℃加熱溶解、添加甲醇(328g)使結晶析出並過濾、乾燥而獲得化合物[2] (產量：97.9g、產率：89%)。<Synthesis Example 1 Synthesis of W-A1>

<Synthesis of Compounds [1], [2] >
Tetrahydrofuran (165.6 g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (41.1 g, 135 mmol) and triethylamine (31.5 g) were added to the reaction vessel. Methanesulfonium chloride (33.2 g) was dropped under ice-cooling under a nitrogen atmosphere, and allowed to react for 1 hour to thereby obtain a compound [1]. Next, p-(trans-4-heptylcyclohexyl)phenol (77.8 g) dissolved in tetrahydrofuran (246.6 g) was added, and the mixture was stirred at 40 ° C for 1 hour, and then dissolved at the same temperature to dissolve it. Potassium hydroxide (41.0 g) in pure water (233 g) was allowed to react for 21 hours. After completion of the reaction, 1.0 M aqueous hydrochloric acid (311 ml) and pure water (1050 g) were added to precipitate a crude product, which was collected by filtration. The obtained crude product was dissolved by heating in tetrahydrofuran (574 g) at 50 ° C, and methanol (328 g) was added to precipitate crystals, which were filtered and dried to give compound [2] (yield: 97.9 g, yield: 89%).

1 H-NMR(400MHz) in CDCl3 :0.87-0.90ppm(m, 6H), 0.96-1.05ppm(m, 4H), 1.19-1.39ppm(m, 30H), 1.80-1.85ppm(m, 8H), 2.33-2.40ppm(m, 2H), 4.77ppm(s, 4H), 6.66-6.70ppm (m, 4H), 7.02-7.06ppm(m, 4H), 7.40ppm(d, 2H, 8.4), 8.25ppm(dd, 2H,J =2.4Hz,J =8.4Hz), 8.54ppm(d, 2H,J =2.4Hz). 1 H-NMR (400 MHz) in CDCl 3 : 0.87-0.90 ppm (m, 6H), 0.96-1.05 ppm (m, 4H), 1.19-1.39 ppm (m, 30H), 1.80-1.85 ppm (m, 8H) , 2.33-2.40ppm(m, 2H), 4.77ppm(s, 4H), 6.66-6.70ppm (m, 4H), 7.02-7.06ppm(m, 4H), 7.40ppm(d, 2H, 8.4), 8.25 Ppm (dd, 2H, J = 2.4 Hz, J = 8.4 Hz), 8.54 ppm (d, 2H, J = 2.4 Hz).

＜W-A1之合成＞
於反應容器中添加四氫呋喃(1783g)、化合物[2](74.3 g，90.9mmol)及3%鉑碳(5.94g)，於氫環境室溫條件下使其反應。反應結束後，將反應混合物過濾，將過濾液減壓濃縮藉此使內部總重量成為145g。接下來，於濃縮溶液中添加甲醇(297g)，進行冰冷攪拌，並過濾、乾燥，藉此獲得W-A1 (產量：59.2g、產率：86%)。
1 H-NMR(400MHz) in CDCl3 :0.87-0.90ppm(m, 6H), 0.96-1.05ppm(m, 4H), 1.19-1.40ppm(m, 30H), 1.81-1.84ppm(m, 8H), 2.32-2.38ppm(m, 2H), 3.67ppm(s, 4H), 4.69ppm(d, 2H,J =12.0Hz), 4.74ppm(d, 2H,J =11.6Hz), 6.62ppm(dd, 2H,J =2.4Hz,J =8.0Hz), 6.70-6.75ppm(m, 4H), 6.91ppm(d, 2H,J =2.4Hz), 6.97-7.03ppm(m, 6H).<Synthesis of W-A1>
Tetrahydrofuran (1783 g), compound [2] (74.3 g, 90.9 mmol) and 3% platinum carbon (5.94 g) were added to the reaction vessel, and the mixture was reacted under a hydrogen atmosphere at room temperature. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to give a total internal weight of 145 g. Next, methanol (297 g) was added to the concentrated solution, and the mixture was ice-cooled, filtered, and dried, whereby W-A1 (yield: 59.2 g, yield: 86%) was obtained.
1 H-NMR (400 MHz) in CDCl 3 : 0.87-0.90 ppm (m, 6H), 0.96-1.05 ppm (m, 4H), 1.19-1.40 ppm (m, 30H), 1.81-1.84 ppm (m, 8H) , 2.32-2.38ppm(m, 2H), 3.67ppm(s, 4H), 4.69ppm(d, 2H, J = 12.0Hz), 4.74ppm(d, 2H, J = 11.6Hz), 6.62ppm(dd, 2H, J = 2.4 Hz, J = 8.0 Hz), 6.70-6.75 ppm (m, 4H), 6.91 ppm (d, 2H, J = 2.4 Hz), 6.97-7.03 ppm (m, 6H).

＜合成例2 W-A2之合成＞
<Synthesis Example 2 Synthesis of W-A2>

＜化合物[3]之合成＞
於反應容器中添加四氫呋喃(327.2g)、4,4’-二硝基-2,2’-聯苯二甲酸(40.9g、123mmol)及p-(trans-4-庚基環己基)酚(72.1g)、4-二甲基氨基吡啶(1.50g)，於氮環境室溫條件下，投入1-(3-二甲基胺基丙基)-3-乙基碳二亞胺鹽酸鹽(56.6g)，使其反應3小時。反應結束後，於純水(1226g)中注入反應液，使粗產物析出，藉由過濾進行回收。接下來，使粗產物以甲醇(245g)進行漿液洗淨後，進行過濾，使獲得之粗產物於四氫呋喃(245g)中60℃加熱溶解。藉由過濾將不溶物去除後，藉由減壓濃縮使內部總重量成為232g後，添加甲醇(163g)使結晶析出，於冰冷條件下攪拌後，並過濾、乾燥藉此獲得化合物[3](產量：73.9g、產率：71%)。
1 H-NMR(400MHz) in CDCl3 : 0.87-0.90ppm(m, 6H), 0.98-1.06ppm(m, 4H), 1.18-1.43ppm(m, 30H), 1.83-1.86ppm(m, 8H), 2.41-2.47ppm(m, 2H), 6.89-6.92ppm(m, 4H), 7.17-7.20ppm(m, 4H), 7.48ppm(d, 2H, 8.4), 8.49ppm(dd, 2H,J =2.4Hz,J =8.4Hz), 9.11ppm(d, 2H,J =2.4Hz).<Synthesis of Compound [3]>
Tetrahydrofuran (327.2 g), 4,4'-dinitro-2,2'-diphenyl phthalate (40.9 g, 123 mmol) and p-(trans-4-heptylcyclohexyl) phenol were added to the reaction vessel. 72.1 g), 4-dimethylaminopyridine (1.50 g), charged with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride under nitrogen at room temperature (56.6 g), allowed to react for 3 hours. After completion of the reaction, the reaction liquid was poured into pure water (1226 g) to precipitate a crude product, which was recovered by filtration. Next, the crude product was washed with methanol (245 g), and then filtered, and the obtained crude product was dissolved in tetrahydrofuran (245 g) at 60 ° C. After the insoluble matter was removed by filtration, the total internal weight was 232 g by concentration under reduced pressure, and then methanol (163 g) was added to precipitate crystals, and the mixture was stirred under ice-cooling conditions, followed by filtration and drying to obtain a compound [3] ( Yield: 73.9 g, yield: 71%).
1 H-NMR (400 MHz) in CDCl 3 : 0.87-0.90 ppm (m, 6H), 0.98-1.06 ppm (m, 4H), 1.18-1.43 ppm (m, 30H), 1.83-1.86 ppm (m, 8H) , 2.41-2.47ppm(m, 2H), 6.89-6.92ppm(m, 4H), 7.17-7.20ppm(m, 4H), 7.48ppm(d, 2H, 8.4), 8.49ppm(dd, 2H, J = 2.4Hz, J = 8.4Hz), 9.11ppm (d, 2H, J = 2.4Hz).

＜W-A2之合成＞
於反應容器中添加四氫呋喃(443g)及甲醇(73.9g)、化合物[3](73.9g、87.4mmol)及5%鈀碳(8.80g)，於氫環境室溫條件下使其反應。反應結束後，藉由過濾將鈀碳去除，藉由減壓濃縮使內部總重量成為171g。接下來，於濃縮溶液中添加甲醇(222g)，使結晶析出，進行冰冷攪拌，並過濾、乾燥，藉此獲得W-A2(產量：66.6g、產率：97%)。
1 H-NMR(400MHz) in CDCl3 :0.87-0.90ppm(m, 6H), 0.96-1.05ppm(m, 4H), 1.17-1.42ppm(m, 30H), 1.82-1.85ppm(m, 8H), 2.38-2.44ppm(m, 2H), 3.77ppm(s, 4H), 6.80-6.87ppm(m, 6H), 7.08-7.13ppm(m, 6H), 7.41ppm(d, 2H,J =2.4Hz).<Synthesis of W-A2>
Tetrahydrofuran (443 g), methanol (73.9 g), compound [3] (73.9 g, 87.4 mmol), and 5% palladium carbon (8.80 g) were added to the reaction vessel, and the mixture was reacted under a hydrogen atmosphere at room temperature. After completion of the reaction, palladium carbon was removed by filtration, and the total internal weight was 171 g by concentration under reduced pressure. Next, methanol (222 g) was added to the concentrated solution to precipitate crystals, and the mixture was ice-cooled, filtered, and dried to obtain W-A2 (yield: 66.6 g, yield: 97%).
1 H-NMR (400 MHz) in CDCl 3 : 0.87-0.90 ppm (m, 6H), 0.96-1.05 ppm (m, 4H), 1.17-1.42 ppm (m, 30H), 1.82-1.85 ppm (m, 8H) , 2.38-2.44ppm(m, 2H), 3.77ppm(s, 4H), 6.80-6.87ppm(m, 6H), 7.08-7.13ppm(m, 6H), 7.41ppm(d, 2H, J =2.4Hz ).

＜合成例3 W-A3之合成＞
<Synthesis Example 3 Synthesis of W-A3>

＜化合物[4]、[5]之合成＞
於反應容器中添加甲苯(366g)、4-(trans-4-庚基環己基)-安息香酸(73.1g、242mmol)及N,N-二甲基甲醯胺(0.73g)，於氮環境50℃條件下，將亞硫醯氯(35.9g)滴下。滴下後，於同溫度下使其反應1小時後，將反應溶液減壓濃縮藉此獲得化合物[4]。接下來，於四氫呋喃(210g)中，加入4,4’-二硝基-1,1’-聯苯基-2,2’-二甲醇(35.0g、115mmol)及三乙胺(26.8g)，於氮環境冰冷條件下，將使其溶解於四氫呋喃(73.1g)中之化合物[4]滴下。滴下結束後，將反應溫度設為室溫使其反應18小時。反應結束後，藉由過濾將三乙胺鹽酸鹽去除後，藉由減壓濃縮獲得油狀化合物。藉由將獲得之油狀化合物添加於純水(1015g)中，使結晶析出，並藉由過濾來回收粗產物。接下來，藉由將獲得之粗產物以甲醇(291g)進行室溫漿液洗淨，以乙酸乙酯(175g)進行室溫漿液洗淨並過濾、乾燥，獲得化合物[5](產量：92.7g、產率：92%)。
1 H-NMR(400MHz) in CDCl3 :0.89-0.91ppm(m, 6H), 0.99-1.09ppm(m, 4H), 1.20-1.47ppm(m, 30H), 1.85-1.88ppm(m, 8H), 2.46-2.52ppm(m, 2H), 5.14ppm(s, 4H), 7.23-7.26ppm(m, 4H), 7.45ppm(d, 2H,J =8.4Hz), 7.83-7.86ppm(m, 4H), 8.27ppm(dd, 2H,J =2.4Hz,J =8.4Hz), 8.47ppm (d, 2H,J =2.4Hz).<Synthesis of Compounds [4], [5]
Toluene (366g), 4-(trans-4-heptylcyclohexyl)-benzoic acid (73.1g, 242mmol) and N,N-dimethylformamide (0.73g) were added to the reaction vessel in a nitrogen atmosphere. Thionylene chloride (35.9 g) was dropped at 50 °C. After the dropwise addition, the mixture was allowed to react at the same temperature for 1 hour, and then the reaction solution was concentrated under reduced pressure to give Compound [4]. Next, 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (35.0 g, 115 mmol) and triethylamine (26.8 g) were added to tetrahydrofuran (210 g). The compound [4] dissolved in tetrahydrofuran (73.1 g) was dropped under ice-cooling under nitrogen. After the completion of the dropwise addition, the reaction was allowed to proceed to room temperature for 18 hours. After completion of the reaction, the triethylamine hydrochloride was removed by filtration, and the oily compound was obtained by concentration under reduced pressure. The obtained oily compound was added to pure water (1015 g) to precipitate crystals, and the crude product was recovered by filtration. Next, the obtained crude product was washed with methanol (291 g) at room temperature, washed with ethyl acetate (175 g) at room temperature, filtered, and dried to give compound [5] (yield: 92.7 g) , yield: 92%).
1 H-NMR (400 MHz) in CDCl 3 : 0.89-0.91 ppm (m, 6H), 0.99-1.09 ppm (m, 4H), 1.20-1.47 ppm (m, 30H), 1.85-1.88 ppm (m, 8H) , 2.46-2.52ppm(m, 2H), 5.14ppm(s, 4H), 7.23-7.26ppm(m, 4H), 7.45ppm(d, 2H, J =8.4Hz), 7.83-7.86ppm(m, 4H ), 8.27ppm (dd, 2H, J = 2.4Hz, J = 8.4Hz), 8.47ppm (d, 2H, J = 2.4Hz).

＜W-A3之合成＞
於反應容器中添加四氫呋喃(484g)及甲醇(161g)、化合物[5](80.5g、92.2mmol)及3%鉑碳(6.44g)，於氫環境室溫條件下使其反應。反應結束後，藉由過濾將鉑碳去除，藉由減壓濃縮將溶劑去除，使內部總重量成為96.6g。接下來，藉由於濃縮溶液中添加甲醇(322g)，使結晶析出、進行冰冷攪拌、過濾而獲得粗產物。接下來，使獲得之粗產物以乙酸乙酯(322g)60℃加熱溶解，添加甲醇(700g)，於冰冷條件下使結晶析出，並過濾、乾燥藉此獲得W-A3(產量：67.9g、產率：91%)。
1 H-NMR(400MHz) in CDCl3 : 0.87-0.91ppm(m, 6H), 0.98-1.08ppm(m, 4H), 1.19-1.47ppm(m, 30H), 1.84-1.87ppm(m, 8H), 2.44-2.51ppm(m, 2H), 3.71ppm(s, 4H), 5.02ppm(d, 2H,J =12.8Hz), 5.09ppm(d, 2H,J =12.4Hz), 6.66ppm(dd, 2H,J =2.4Hz,J =8.0Hz), 6.84ppm(d, 2H,J =2.4Hz), 7.03ppm(d, 2H,J =8.0Hz), 7.19-7.25ppm (m, 4H), 7.89-7.92ppm(m, 4H).<Synthesis of W-A3>
Tetrahydrofuran (484 g), methanol (161 g), compound [5] (80.5 g, 92.2 mmol), and 3% platinum carbon (6.44 g) were added to the reaction vessel, and the mixture was reacted under a hydrogen atmosphere at room temperature. After completion of the reaction, the platinum carbon was removed by filtration, and the solvent was removed by concentration under reduced pressure to give a total internal weight of 96.6 g. Next, methanol (322 g) was added to the concentrated solution to precipitate crystals, followed by ice-cooling stirring and filtration to obtain a crude product. Next, the obtained crude product was dissolved by heating with ethyl acetate (322 g) at 60 ° C, methanol (700 g) was added, and crystals were precipitated under ice-cooling conditions, and filtered and dried to obtain W-A3 (yield: 67.9 g, Yield: 91%).
1 H-NMR (400 MHz) in CDCl 3 : 0.87-0.91 ppm (m, 6H), 0.98-1.08 ppm (m, 4H), 1.19-1.47 ppm (m, 30H), 1.84-1.87 ppm (m, 8H) , 2.44-2.51ppm(m, 2H), 3.71ppm(s, 4H), 5.02ppm(d, 2H, J = 12.8Hz), 5.09ppm(d, 2H, J = 12.4Hz), 6.66ppm(dd, 2H, J = 2.4 Hz, J = 8.0 Hz), 6.84 ppm (d, 2H, J = 2.4 Hz), 7.03 ppm (d, 2H, J = 8.0 Hz), 7.19-7.25 ppm (m, 4H), 7.89 -7.92ppm (m, 4H).

＜特定聚合物之合成＞
[合成例1]
將D2(2.50g，10.0mmol)、W-A1(3.03g，4.00mmol)及C1(1.73g，16.0mmol)溶解於NMP(18.1g)與NEP(18.1g)之混合溶劑中，於60℃使其反應3小時後，添加D1(1.78g，9.10mmol)，於40℃使其反應3小時，獲得樹脂固體成分濃度20質量%之聚醯胺酸溶液(黏度：840mPa・s)。
於獲得之聚醯胺酸溶液(20.0g)中添加NMP，稀釋為6.5質量%後，添加乙酸酐(4.43g)及吡啶(1.37g) 作為醯亞胺化觸媒，於80℃使其反應3小時。將此反應溶液投入甲醇(382ml)中，將獲得之沉澱物過濾分離。將此沉澱物以甲醇洗淨，於100℃減壓乾燥，獲得聚醯亞胺粉末(PI-1)。此聚醯亞胺之醯亞胺化率為76.4%，Mn為16,165，Mw為49,988。<Synthesis of specific polymers>
[Synthesis Example 1]
D2 (2.50 g, 10.0 mmol), W-A1 (3.03 g, 4.00 mmol) and C1 (1.73 g, 16.0 mmol) were dissolved in a mixed solvent of NMP (18.1 g) and NEP (18.1 g) at 60 ° C After reacting for 3 hours, D1 (1.78 g, 9.10 mmol) was added, and the mixture was reacted at 40 ° C for 3 hours to obtain a polyamic acid solution (viscosity: 840 mPa·s) having a resin solid concentration of 20% by mass.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6.5% by mass, acetic anhydride (4.43 g) and pyridine (1.37 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 80 ° C. 3 hours. This reaction solution was poured into methanol (382 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (PI-1). The polyimide imineization rate of this polyimine was 76.4%, Mn was 16,165, and Mw was 49,988.

[合成例2]
將D2(2.50g，10.0mmol)、W-A2(3.14g，4.00mmol)及C1(1.84g，16.0mmol)溶解於NMP(11.1g)及PC(25.8g)之混合溶劑中，於60℃使其反應3小時後，添加D1(1.84g，9.38mmol)，於40℃使其反應3小時，獲得樹脂固體成分濃度20質量%之聚醯胺酸溶液(黏度：658mPa・s)。
於獲得之聚醯胺酸溶液(20.0g)中添加NMP，稀釋為6.5質量%後，添加乙酸酐(4.38g)及吡啶(1.36g)作為醯亞胺化觸媒，於80℃使其反應3小時。將此反應溶液投入甲醇(382ml)中，將獲得之沉澱物過濾分離。將此沉澱物以甲醇洗淨，於100℃減壓乾燥，獲得聚醯亞胺粉末(PI-2)。此聚醯亞胺之醯亞胺化率為75.8%，Mn為15,430，Mw為45,756。[Synthesis Example 2]
D2 (2.50 g, 10.0 mmol), W-A2 (3.14 g, 4.00 mmol) and C1 (1.84 g, 16.0 mmol) were dissolved in a mixed solvent of NMP (11.1 g) and PC (25.8 g) at 60 ° C After reacting for 3 hours, D1 (1.84 g, 9.38 mmol) was added, and the mixture was reacted at 40 ° C for 3 hours to obtain a polyamic acid solution (viscosity: 658 mPa·s) having a resin solid concentration of 20% by mass.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6.5% by mass, acetic anhydride (4.38 g) and pyridine (1.36 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 80 ° C. 3 hours. This reaction solution was poured into methanol (382 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (PI-2). The polyimide imidization ratio of this polyimine was 75.8%, the Mn was 15,430, and the Mw was 45,756.

[合成例3]
將D2(2.50g，10.0mmol)、W-A3(3.25g，4.00mmol)及C1(1.73g，16.0mmol)於GBL(37.3g)中混合，於60℃使其反應3小時後，添加D1(1.84g，9.38mmol)，於40℃使其反應3小時，獲得樹脂固體成分濃度20質量%之聚醯胺酸溶液(黏度：656mPa・s)。
於獲得之聚醯胺酸溶液(20.0g)中添加GBL，稀釋為6.5質量%後，添加乙酸酐(4.32g)及吡啶(1.34g)作為醯亞胺化觸媒，於80℃使其反應3小時。將此反應溶液投入甲醇(382ml)中，將獲得之沉澱物過濾分離。將此沉澱物以甲醇洗淨，於100℃減壓乾燥，獲得聚醯亞胺粉末(PI-3)。此聚醯亞胺之醯亞胺化率為74.7%，Mn為13,340，Mw為41,948。[Synthesis Example 3]
D2 (2.50 g, 10.0 mmol), W-A3 (3.25 g, 4.00 mmol) and C1 (1.73 g, 16.0 mmol) were mixed in GBL (37.3 g), and reacted at 60 ° C for 3 hours, then D1 was added. (1.84 g, 9.38 mmol) was reacted at 40 ° C for 3 hours to obtain a polyamic acid solution (viscosity: 656 mPa·s) having a resin solid content concentration of 20% by mass.
After adding GBL to the obtained polyamic acid solution (20.0 g) and diluting it to 6.5% by mass, acetic anhydride (4.32 g) and pyridine (1.34 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 80 ° C. 3 hours. This reaction solution was poured into methanol (382 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (PI-3). The polyimide imidization ratio of this polyimine was 74.7%, Mn was 13,340, and Mw was 41,948.

[比較合成例1]
添加A1(0.63g，1.2mmol)、C4(2.36g，21.8mmol)及NMP將二胺溶解後，添加D4(4.12g，22.4mmol)及NMP作為設定濃度20質量%。於60℃使其反應3小時後，獲得樹脂固體成分濃度20質量%之聚醯胺酸溶液(黏度：250mPa・s)。
於獲得之聚醯胺酸溶液(20.0g)中添加NMP，稀釋為6.5質量%後，添加乙酸酐(4.64g)及吡啶(1.44g)作為醯亞胺化觸媒，於80℃使其反應3小時。將此反應溶液投入甲醇(382ml)中，將獲得之沉澱物過濾分離。將此沉澱物以甲醇洗淨，於100℃減壓乾燥，獲得聚醯亞胺粉末(PI-R1)。此聚醯亞胺之醯亞胺化率為75%，Mn為13,100，Mw為33,200。[Comparative Synthesis Example 1]
After adding A1 (0.63 g, 1.2 mmol), C4 (2.36 g, 21.8 mmol) and NMP to dissolve the diamine, D4 (4.12 g, 22.4 mmol) and NMP were added as a set concentration of 20% by mass. After reacting at 60 ° C for 3 hours, a polyaminic acid solution (viscosity: 250 mPa·s) having a resin solid content concentration of 20% by mass was obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6.5% by mass, acetic anhydride (4.64 g) and pyridine (1.44 g) were added as a ruthenium catalyzed catalyst, and the reaction was carried out at 80 ° C. 3 hours. This reaction solution was poured into methanol (382 ml), and the obtained precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (PI-R1). The polyimide imineization rate of this polyimine was 75%, Mn was 13,100, and Mw was 33,200.

[比較合成例2]
除了將使用之二胺之種類及組成各自如下述表1之記載進行變更以外，藉由與上述聚合物比較合成例1相同之方法，獲得聚醯亞胺粉末(PI-R2)。此聚醯亞胺之醯亞胺化率為55%，Mn為10,500，Mw為20,900。[Comparative Synthesis Example 2]
The polyimine powder (PI-R2) was obtained by the same method as in Comparative Example 1 except that the type and composition of the diamine to be used were changed as described in the following Table 1. The polyamidimide had an imidization ratio of 55%, an Mn of 10,500, and a Mw of 20,900.

[實施例1]
於以上述之聚合物合成例1獲得之聚醯亞胺(PI-1)中添加NMP至聚醯亞胺成為12質量%為止後，於70℃攪拌24小時使其溶解。接著，以NMP及PB之混合溶液稀釋，獲得固體成分濃度為3質量%、溶劑組成為NMP：PB=50：50(質量比)之液晶配向劑(S-1)。將此供給於以下之濾過性、印刷性及液晶配向性之評估中。[Example 1]
After the NMP was added to the polyimine (PI-1) obtained in the above-mentioned polymer synthesis example 1, the polyimine was added to 12% by mass, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Subsequently, it was diluted with a mixed solution of NMP and PB to obtain a liquid crystal alignment agent (S-1) having a solid content concentration of 3% by mass and a solvent composition of NMP:PB=50:50 (mass ratio). This was supplied to the following evaluations of filterability, printability, and liquid crystal alignment.

＜濾過性之評估＞
測定將液晶配向劑100ml以孔徑0.2μm及直徑13mm之針筒過濾器(whatman公司製)濾過後之產量，依據下述之基準進行濾過性之判定。

(評估基準)
優良：液晶配向劑之產量為40ml以上
良：液晶配向劑之產量為5ml以上、未滿40ml
不可：液晶配向劑之產量為未滿5ml<Evaluation of filtration>
The yield of 100 ml of the liquid crystal alignment agent filtered through a syringe filter (manufactured by Whatman Co., Ltd.) having a pore diameter of 0.2 μm and a diameter of 13 mm was measured, and the filtration property was determined based on the following criteria.

(assessment basis)
Excellent: the output of the liquid crystal alignment agent is 40ml or more. The yield of the liquid crystal alignment agent is 5ml or more and less than 40ml.
No: The output of the liquid crystal alignment agent is less than 5ml.

＜印刷性之評估＞
將以上述濾過性之評估所獲得之液晶配向劑於40mm×30mm之附有ITO電極之玻璃基板(縱：40mm、橫：30mm、厚度：1.1mm)之ITO面上使用噴墨塗布裝置HIS-200(Hitachi Plant Technologies, Ltd.製)，製作塗膜。此時之塗布條件係塗布面積為70mm×70mm、噴嘴間距為0.423mm、掃描間距為0.5mm、塗布速度為40mm/秒。塗布後靜置60秒鐘後，依據下述之基準進行濾過性之判定。

(評估基準)
優良：皆未看見針孔及塌凹。
良：可看見針孔或塌凹中之任一者。
不可：針孔及塌凹皆可看見。<Evaluation of printability>
The liquid crystal alignment agent obtained by the above evaluation of the filterability was applied to an ITO surface of a glass substrate (length: 40 mm, width: 30 mm, thickness: 1.1 mm) of an ITO electrode of 40 mm × 30 mm using an inkjet coating device HIS- 200 (manufactured by Hitachi Plant Technologies, Ltd.) to prepare a coating film. The coating conditions at this time were a coating area of 70 mm × 70 mm, a nozzle pitch of 0.423 mm, a scanning pitch of 0.5 mm, and a coating speed of 40 mm/sec. After standing for 60 seconds after coating, the filtration property was judged based on the following criteria.

(assessment basis)
Excellent: no pinholes and collapses were seen.
Good: You can see any of the pinholes or collapses.
No: pinholes and collapses are visible.

＜液晶胞之製造＞
於上述印刷性之評估所記載之條件下進行塗布後，於加熱板上於70℃進行加熱處理90秒鐘，於熱循環型潔淨烤箱於230℃進行加熱處理30分鐘，獲得膜厚為80nm之附有液晶配向膜之ITO基板。準備2枚獲得之附有液晶配向膜之ITO基板，於其中之一之基板之液晶配向膜面上，塗布直徑4μm之珠粒間隔物(日揮觸媒化成公司製、真絲球、SW-D1)。
接著，以密封劑(三井化學公司製、XN-1500T)塗布周圍。接著，使另一基板之形成有液晶配向膜之側的面作為內側，與前述之基板黏合後，使密封材硬化製作空胞。於此空胞中，將負型液晶MLC-3023(Merck公司製商品名)藉由減壓注入法注入，製作液晶胞。
其後，於對獲得之液晶胞施加15V之直流電壓後之狀態下，使用於光源使用高壓水銀燈之紫外線照射裝置，照射通過波長365nm之帶通濾光器之紫外線15J/cm2 ，獲得垂直配向型液晶顯示元件。此外，紫外線照射量之測定中，於ORC公司製UV-M03A中連接UV-35之受光器使用。<Manufacture of liquid crystal cells>
After coating on the conditions described in the evaluation of the printability, the film was heat-treated at 70 ° C for 90 seconds on a hot plate, and heat-treated at 230 ° C for 30 minutes in a heat cycle type clean oven to obtain a film thickness of 80 nm. An ITO substrate with a liquid crystal alignment film. Two ITO substrates with a liquid crystal alignment film were prepared, and a bead spacer having a diameter of 4 μm was applied to the liquid crystal alignment film surface of one of the substrates (Nikkei Chemical Co., Ltd., silk ball, SW-D1) .
Next, the periphery was coated with a sealant (manufactured by Mitsui Chemicals, Inc., XN-1500T). Next, the surface of the other substrate on the side where the liquid crystal alignment film is formed is made to be inside, and after bonding to the substrate, the sealing material is cured to form a hollow cell. In this empty cell, a negative liquid crystal MLC-3023 (trade name, manufactured by Merck Co., Ltd.) was injected by a reduced pressure injection method to prepare a liquid crystal cell.
Thereafter, after applying a direct current voltage of 15 V to the obtained liquid crystal cell, the ultraviolet light irradiation device using a high-pressure mercury lamp for the light source is irradiated with ultraviolet rays 15 J/cm 2 passing through a band pass filter having a wavelength of 365 nm to obtain a vertical alignment. Type liquid crystal display element. Further, in the measurement of the amount of ultraviolet irradiation, a UV-35 light-receiver was used in UV-M03A manufactured by ORC Corporation.

＜液晶配向性之評估＞
液晶顯示元件之液晶配向性係以偏光顯微鏡(ECLIPSE E600WPOL)(Nikon公司製)進行觀察，確認液晶是否垂直地配向。具體而言，係將未看見因液晶之流動所造成之不良或因配向缺陷所造成之亮點者視為良好。

[實施例2~30及比較例1~4]
除了將使用之聚合物以及溶劑之種類及組成各自如下述表2之記載進行變更以外，藉由與上述實施例1相同之方法各自調製液晶配向劑(S-2)~(S-30)、(RS-1)~(RS-4)。又，針對各自之液晶配向劑評估濾過性。此等之中，針對液晶配向劑(S-2)~(S-3)、(S-6)~(S-7)、(S-9)~(S-19)、(S-23)~(S-30)，係與實施例1相同，於附有ITO電極之玻璃基板塗布，進行印刷性及液晶配向性之評估。針對液晶配向劑(S-4)、(S-5)、(S-8)、(S-20)~(S-22)，係使用配向膜印刷機(Nissha Co., Ltd.製「Angstromer」)，進行液晶配向劑之塗布以外，與實施例1相同，進行印刷性及液晶配向性之評估。將該等之結果示於下述表2。<Evaluation of liquid crystal alignment>
The liquid crystal alignment of the liquid crystal display element was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Co., Ltd.) to confirm whether or not the liquid crystal was vertically aligned. Specifically, it is considered that the defect caused by the flow of the liquid crystal or the bright spot caused by the alignment defect is not considered good.

[Examples 2 to 30 and Comparative Examples 1 to 4]
The liquid crystal alignment agents (S-2) to (S-30) were prepared by the same method as in the above Example 1, except that the type and composition of the polymer to be used and the solvent were changed as described in the following Table 2. (RS-1)~(RS-4). Further, the filterability was evaluated for each liquid crystal alignment agent. Among these, liquid crystal alignment agents (S-2) to (S-3), (S-6) to (S-7), (S-9) to (S-19), and (S-23) ~(S-30) was applied to a glass substrate with an ITO electrode in the same manner as in Example 1, and evaluation of printability and liquid crystal alignment was performed. For liquid crystal alignment agents (S-4), (S-5), (S-8), (S-20) to (S-22), an alignment film printer ("Angstromer" manufactured by Nissha Co., Ltd.) was used. In the same manner as in Example 1, except for the application of the liquid crystal alignment agent, the printability and the liquid crystal alignment property were evaluated. The results of these are shown in Table 2 below.

表2中，聚合物之數值係表示相對於液晶配向劑之調製中使用之聚合物之合計量，各聚合物之摻混比例(質量比)。溶劑組成之數值係表示相對於液晶配向劑之調製中使用之溶劑之合計量，各化合物之摻混比例(質量比)。
如同由上述之結果所知，由實施例之液晶配向劑所獲得之液晶配向膜相較於由比較例之液晶配向劑所獲得之液晶配向膜，可獲得液晶配向性優異之液晶配向膜。又，實施例之液晶配向劑相較於比較例之液晶配向劑，可獲得濾過性及印刷性優異之液晶配向劑。

[產業上之可利用性]In Table 2, the numerical value of the polymer indicates the blending ratio (mass ratio) of each polymer with respect to the total amount of the polymer used in the preparation of the liquid crystal alignment agent. The value of the solvent composition is a total amount of the solvent used in the preparation of the liquid crystal alignment agent, and the blending ratio (mass ratio) of each compound.
As is apparent from the above results, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the example can obtain a liquid crystal alignment film excellent in liquid crystal alignment properties as compared with the liquid crystal alignment film obtained from the liquid crystal alignment agent of the comparative example. Further, the liquid crystal alignment agent of the example can obtain a liquid crystal alignment agent excellent in filterability and printability as compared with the liquid crystal alignment agent of the comparative example.

[Industrial availability]

本發明之液晶配向劑係濾過性及印刷性優異，且可獲得液晶配向性優異之液晶配向膜。又，具有此液晶配向膜之液晶顯示元件，使高品質的影像顯示成為可能，可適宜利用於大畫面且高精密之液晶電視等，對於TN元件、STN元件、TFT液晶元件等，特別是垂直配向型之液晶顯示元件為有用。The liquid crystal alignment agent of the present invention is excellent in filterability and printability, and a liquid crystal alignment film excellent in liquid crystal alignment property can be obtained. Moreover, the liquid crystal display element having the liquid crystal alignment film enables high-quality image display, and can be suitably used for a large-screen and high-precision liquid crystal television, and is particularly vertical for TN elements, STN elements, TFT liquid crystal elements, and the like. An alignment type liquid crystal display element is useful.

此外，將於2017年11月21日申請之日本專利出願2017-223900號之說明書、申請專利範圍、圖式及摘要之全部內容引用於此，納入作為本發明之說明書之揭示內容。In addition, the entire contents of the specification, the scope of the application, the drawings and the abstract of the Japanese Patent Application No. Hei.

Claims (17)

一種液晶配向劑，其係含有 由具有下述式[1]之結構之聚醯胺酸或者聚醯胺酸酯、及作為其醯亞胺化物之聚醯亞胺所構成之群組所選出之至少1種聚合物，及 包含由下述式(d-1)～(d-5)及下述式(e)所構成之群組所選出之至少1種溶劑A，及由下述式(B-1)～(B-4)所構成之群組所選出之至少1種溶劑B之溶劑， 式[1]中，X係表示由單鍵、-O-、-C(CH3 )2 -、-NH-、-CO-、 -NHCO-、-COO-、-(CH2 )m -、-SO2 -、-O-(CH2 )m -O-、-O-C(CH3 )2 -、-CO-(CH2 )m -、-NH-(CH2 )m -、-SO2 -(CH2 )m -、-CONH-(CH2 )m -、-CONH-(CH2 )m -NHCO-及-COO-(CH2 )m -OCO-所構成之群組所選出之2價之有機基，m係表示1～8之整數；2個Y係獨立表示由下述式[S1]～[S3]或生育酚所衍生之側鏈結構， 惟，X1 及X2 係獨立表示單鍵、-(CH2 )a -(a為1～15之整數)、-CONH-、-NHCO-、-CON(CH3 )-、-NH-、-O-、-COO-、-OCO-或((CH2 )a1 -A1 )m1 -(a1係表示1～15之整數，A1 係表示氧原子、-COO或OCO，m1 為1～2)；G1 及G2 係獨立為由碳數6～12之2價之芳香族基或碳數3～8之2價之脂環式基所選出之2價之環狀基，前述環狀基上之任意的氫原子可被碳數1～3之烷基、碳數1～3之烷氧基、碳數1～3之含氟烷基、碳數1～3之含氟烷氧基或氟原子取代；m及n係獨立為0～3之整數，其中，此等之合計為1～4；R1 為碳數1～20之烷基、碳數1～20之烷氧基或碳數2～20之烷氧烷基，此等之基中之任意的氫可被氟原子取代； X3 係表示單鍵、-CONH-、-NHCO-、-CON(CH3 )-、 -NH-、-O-、-CH2 O-、-COO-或OCO-，R2 為碳數1～20之烷基或碳數2～20之烷氧烷基，此等之基中之任意的氫可被氟原子取代； X4 係表示-CONH-、-NHCO-、-O-、-COO-或OCO-，R3 係表示具有類固醇骨架之結構； 惟，R1a 係表示碳數1～8之1價之烴基，或該烴基中之碳-碳鍵結間具有-O-之1價之基；R2a 及R2b 係獨立表示碳數1～6之烷基；R3a 係表示甲基或乙基，R5a 係表示碳數1～6之烷基，R5b 及R5c 係獨立表示氫原子、碳數1～6之1價之烴基，或該烴基之碳-碳鍵結間具有-O-之1價之基；r1a 及r1b 係獨立表示氫原子或碳數1～6之烷基，m為2～6之整數，n為1或2之整數； 惟，Ap1 、Ap2 係獨立表示碳數1～6之烷基，Ap5 係表示氫原子或碳數1～6之烷基，Aq1 係表示-O-或-COO-，Aq2 係表示單鍵或羰基，Aq3 係表示-O-，Ak1 、Ak2 、Ak6 係獨立表示碳數2～4之烷二基，n1係表示1～3；Ap3 、Ap4 係獨立表示氫原子或碳數1～6之烷基，Ax 係表示-C(OH)Ra -、 -CHRb -(Ra 、Rb 係獨立表示氫、甲基或乙基)、-CO-或 -COO-＊(＊係表示與Ak4 鍵結之位置)，Ak4 、Ak5 係獨立表示碳數1～4之烷基；M為0或1之整數，n4為1～3之整數；惟，n4為1，且Ak6 為碳數2之烷二基，且Ap5 為碳數4之烷基之情況除外。A liquid crystal alignment agent which is selected from the group consisting of polylysine or polyglycolate having the structure of the following formula [1] and polyamidene as its ruthenium imide At least one polymer, and at least one solvent A selected from the group consisting of the following formulas (d-1) to (d-5) and the following formula (e), and the following formula ( a solvent of at least one solvent B selected from the group consisting of B-1) to (B-4), In the formula [1], X represents a single bond, -O-, -C(CH 3 ) 2 -, -NH-, -CO-, -NHCO-, -COO-, -(CH 2 ) m -, -SO 2 -, -O-(CH 2 ) m -O-, -OC(CH 3 ) 2 -, -CO-(CH 2 ) m -, -NH-(CH 2 ) m -, -SO 2 - (CH 2 ) m -, -CONH-(CH 2 ) m -, -CONH-(CH 2 ) m -NHCO- and -COO-(CH 2 ) m -OCO- The organic group, m represents an integer of 1 to 8; and the two Y groups independently represent a side chain structure derived from the following formulas [S1] to [S3] or tocopherol, However, X 1 and X 2 independently represent a single bond, -(CH 2 ) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -COO-, -OCO- or ((CH 2 ) a1 -A 1 ) m1 - (a1 represents an integer from 1 to 15, and A 1 represents an oxygen atom, -COO or OCO, and m 1 is 1 ～2); G 1 and G 2 are each a bivalent cyclic group selected from an aromatic group having a carbon number of 6 to 12 or an alicyclic group having a carbon number of 3 to 8; Any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkyl group having 1 to 3 carbon atoms. The oxy group or the fluorine atom is substituted; m and n are each independently an integer of 0 to 3, wherein the total of these is 1 to 4; and R 1 is an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms. a base or an alkoxyalkyl group having 2 to 20 carbon atoms, wherein any hydrogen in the group may be substituted by a fluorine atom; X 3 represents a single bond, -CONH-, -NHCO-, -CON(CH 3 )- , -NH-, -O-, -CH 2 O-, -COO- or OCO-, and R 2 is an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms. Any hydrogen may be replaced by a fluorine atom; X 4 represents -CONH-, -NHCO-, -O-, -COO - or OCO-, R 3 means a structure having a steroid skeleton; However, R 1a represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a monovalent group having -O- in the carbon-carbon bond in the hydrocarbon group; and R 2a and R 2b independently represent a carbon number of 1 to 6 alkyl; R 3a represents a methyl group or an ethyl group; R 5a represents an alkyl group having 1 to 6 carbon atoms; and R 5b and R 5c each independently represent a hydrogen atom and a hydrocarbon group having a valence of 1 to 6 carbon atoms; Or the carbon-carbon bond of the hydrocarbon group has a monovalent group of -O-; r 1a and r 1b independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 2 to 6, and n is An integer of 1 or 2; However, A p1 and A p2 independently represent an alkyl group having 1 to 6 carbon atoms, A p5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A q1 represents -O- or -COO-, and A q2 is a system. Represents a single bond or a carbonyl group, A q3 represents -O-, A k1 , A k2 , and A k6 independently represent a C 2 to 4 alkanediyl group, n 1 represents 1 to 3; A p3 and A p4 are independently represented a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A x represents -C(OH)R a -, -CHR b - (R a , R b independently represents hydrogen, methyl or ethyl), -CO- Or -COO-* (* indicates the position bonded to A k4 ), A k4 and A k5 independently represent an alkyl group having 1 to 4 carbon atoms; M is an integer of 0 or 1, and n4 is an integer of 1 to 3 However, except that n4 is 1, and A k6 is a carbon number 2 alkanediyl group, and A p5 is a carbon number 4 alkyl group. 如請求項1所記載之液晶配向劑，其中，前述式[1]中之X為單鍵、-O-、-NH-、或-O-(CH2 )m -O-(m係表示1～8之整數)。The liquid crystal alignment agent according to claim 1, wherein X in the above formula [1] is a single bond, -O-, -NH-, or -O-(CH 2 ) m -O- (m represents 1) ～8 integer). 如請求項1或2所記載之液晶配向劑，溶劑A為由N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-(n-戊基)-2-吡咯烷酮、N-環己基-2-吡咯烷酮、N-(n-己基)-2-吡咯烷酮、N-甲氧基丙基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、γ-丁內酯、γ-戊內酯、γ-己內酯、3-丁氧基-N,N-二甲基丙醯胺、3-甲氧基-N,N-二甲基丙醯胺、碳酸伸乙酯、及碳酸丙烯酯所構成之群組所選出之至少1種溶劑。The liquid crystal alignment agent according to claim 1 or 2, wherein the solvent A is N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N- Cyclohexyl-2-pyrrolidone, N-(n-hexyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone , γ-valerolactone, γ-caprolactone, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, carbonic acid At least one solvent selected from the group consisting of esters and propylene carbonate. 如請求項1～3中之任1項記載之液晶配向劑，前述式(B-1)中之Ak1 為伸乙基、1,3-丙二基或1,4-丁二基。The liquid crystal alignment agent according to any one of claims 1 to 3, wherein A k1 in the above formula (B-1) is an exoethyl group, a 1,3-propanediyl group or a 1,4-butanediyl group. 如請求項1～4中之任1項記載之液晶配向劑，其中，溶劑中之溶劑A之含有比例為5～99質量%，溶劑中之溶劑B之含有比例為1～95質量%。The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the solvent A in the solvent is contained in an amount of from 5 to 99% by mass, and the solvent B in the solvent is contained in an amount of from 1 to 95% by mass. 如請求項1～5中之任1項記載之液晶配向劑，其中，溶劑B群為由二異丁酮、二異丁基甲醇、4,6-二甲基-2-庚酮、二丙酮醇、乳酸n-丁酯、乳酸異戊酯、乙醇酸丁酯、乙基-3-乙氧基丙酸酯、丙二醇單甲基醚、丙二醇單丁基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、二乙二醇乙基丙基醚、二乙二醇丙基甲基醚、二乙二醇丁基甲基醚、二丙二醇單甲基醚、二丙二醇二甲基醚、乙二醇單丁基醚乙酸酯及丙二醇二乙酸酯所構成之群組所選出之至少1種溶劑。The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the solvent B group is diisobutyl ketone, diisobutyl methoxide, 4,6-dimethyl-2-heptanone, diacetone Alcohol, n-butyl lactate, isoamyl lactate, butyl glycolate, ethyl-3-ethoxypropionate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol diethyl ether, diethylene glycol ethyl propyl ether, diethylene glycol propyl methyl ether, diethylene glycol butyl methyl ether, dipropylene glycol monomethyl ether, dipropylene glycol At least one solvent selected from the group consisting of a group of ethers, ethylene glycol monobutyl ether acetate, and propylene glycol diacetate. 如請求項1～6中之任1項記載之液晶配向劑，其中，前述溶劑係包含由下述ms1～ms12所構成之群組所選出之1種組合： ・ms1：N-甲基-2-吡咯烷酮及丙二醇單丁基醚 ・ms2：N-甲基-2-吡咯烷酮及二丙二醇單甲基醚 ・ms3：N-甲基-2-吡咯烷酮及二丙二醇二甲基醚 ・ms4：N-甲基-2-吡咯烷酮及丙二醇單甲基醚 ・ms5：N-乙基-2-吡咯烷酮及丙二醇單丁基醚 ・ms6：N-乙基-2-吡咯烷酮及二丙二醇單甲基醚 ・ms7：N-乙基-2-吡咯烷酮及二丙二醇二甲基醚 ・ms8：N-乙基-2-吡咯烷酮及丙二醇單甲基醚 ・ms9：N-甲基-2-吡咯烷酮及乳酸異戊酯 ・ms10：N-甲基-2-吡咯烷酮及二丙酮醇 ・ms11：γ-丁內酯及乙基-3-乙氧基丙酸酯 ・ms12：N-乙基-2-吡咯烷酮及二異丁酮。The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the solvent includes one combination selected from the group consisting of the following ms1 to ms12: ・ms1: N-methyl-2-pyrrolidone and propylene glycol monobutyl ether ・ms2: N-methyl-2-pyrrolidone and dipropylene glycol monomethyl ether ・ms3: N-methyl-2-pyrrolidone and dipropylene glycol dimethyl ether ・ms4: N-methyl-2-pyrrolidone and propylene glycol monomethyl ether ・ms5: N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether ・ms6: N-ethyl-2-pyrrolidone and dipropylene glycol monomethyl ether ・ms7: N-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether ・ms8: N-ethyl-2-pyrrolidone and propylene glycol monomethyl ether ・ms9: N-methyl-2-pyrrolidone and isoamyl lactate ・ms10: N-methyl-2-pyrrolidone and diacetone alcohol ・ms11: γ-butyrolactone and ethyl-3-ethoxypropionate ・ms12: N-ethyl-2-pyrrolidone and diisobutylketone. 如請求項1～7中之任1項記載之液晶配向劑，其中，前述溶劑係包含由1種以上之溶劑A及1種以上之溶劑B所構成之3種以上。The liquid crystal alignment agent according to any one of Claims 1 to 7, wherein the solvent contains three or more kinds of the solvent A and one or more solvents B. 請求項8所記載之液晶配向劑，其中，前述溶劑係包含由下述MS1～MS23所構成之群組所選出之1種組合： ・MS1：N-甲基-2-吡咯烷酮及γ-丁內酯及丙二醇單丁基醚 ・MS2：N-甲基-2-吡咯烷酮及γ-丁內酯及二丙二醇單甲基醚 ・MS3：N-甲基-2-吡咯烷酮及γ-丁內酯及二丙二醇二甲基醚 ・MS4：N-甲基-2-吡咯烷酮及γ-丁內酯及丙二醇單甲基醚 ・MS5：N-乙基-2-吡咯烷酮及γ-丁內酯及丙二醇單丁基醚 ・MS6：N-乙基-2-吡咯烷酮及γ-丁內酯及二丙二醇單甲基醚 ・MS7：N-乙基-2-吡咯烷酮及γ-丁內酯及二丙二醇二甲基醚 ・MS8：N-乙基-2-吡咯烷酮及γ-丁內酯及丙二醇單甲基醚 ・MS9：N-乙基-2-吡咯烷酮及N-甲基-2-吡咯烷酮及丙二醇單丁基醚 ・MS10：N-乙基-2-吡咯烷酮及N-甲基-2-吡咯烷酮及二丙二醇單甲基醚 ・MS11：N-乙基-2-吡咯烷酮及N-甲基-2-吡咯烷酮及二丙二醇二甲基醚 ・MS12：N-乙基-2-吡咯烷酮及N-甲基-2-吡咯烷酮及γ-丁內酯及丙二醇單甲基醚 ・MS13：N-甲基-2-吡咯烷酮及二丙酮醇及二乙二醇二乙基醚 ・MS14：N-甲基-2-吡咯烷酮及丙二醇單丁基醚及二丙二醇單甲基醚 ・MS15：N-甲基-2-吡咯烷酮及N-乙基-2-吡咯烷酮及二異丁基甲醇 ・MS16：N-乙基-2-吡咯烷酮及丙二醇單丁基醚及二異丁酮 ・MS17：N-乙基-2-吡咯烷酮及乙二醇單丁基醚乙酸酯及二丙二醇單甲基醚 ・MS18：N-乙基-2-吡咯烷酮及N-甲基-2-吡咯烷酮及二丙酮醇 ・MS19：γ-丁內酯及1,3-二甲基-2-咪唑啉酮及乙基-3-乙氧基丙酸酯 ・MS20：N-甲基-2-吡咯烷酮及3-甲氧基-N,N-二甲基丙醯胺及二丙酮醇 ・MS21：N-甲基-2-吡咯烷酮及碳酸丙烯酯及二丙酮醇 ・MS22：N-甲基-2-吡咯烷酮及乙醇酸丁酯及二丙二醇二甲基醚 ・MS23：N-乙基-2-吡咯烷酮及二丙酮醇及丙二醇單丁基醚 ・MS24：N-乙基-2-吡咯烷酮及二丙酮醇及乙基-3-乙氧基丙酸酯 ・MS25：γ-戊內酯及γ-丁內酯及乙基-3-乙氧基丙酸酯 ・MS26：N-甲基-2-吡咯烷酮及二乙二醇二乙基醚及二丙二醇單甲基醚 ・MS27：N-甲基-2-吡咯烷酮及丙二醇單丁基醚及二乙二醇丁基甲基醚 ・MS28：N-乙基-2-吡咯烷酮及二乙二醇乙基甲基醚及二異丁酮 ・MS29：N-甲基-2-吡咯烷酮及二丙酮醇及丙二醇二乙酸酯。The liquid crystal alignment agent according to claim 8, wherein the solvent includes one combination selected from the group consisting of the following MS1 to MS23: ・MS1: N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether ・MS2: N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol monomethyl ether ・MS3: N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether ・MS4: N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monomethyl ether ・MS5: N-ethyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether ・MS6: N-ethyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol monomethyl ether ・MS7: N-ethyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether ・MS8: N-ethyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monomethyl ether ・MS9: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and propylene glycol monobutyl ether ・MS10: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and dipropylene glycol monomethyl ether ・MS11: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and dipropylene glycol dimethyl ether ・MS12: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monomethyl ether ・MS13: N-methyl-2-pyrrolidone and diacetone alcohol and diethylene glycol diethyl ether ・MS14: N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol monomethyl ether ・MS15: N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone and diisobutylmethanol ・MS16: N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and diisobutyl ketone ・MS17: N-ethyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate and dipropylene glycol monomethyl ether ・MS18: N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and diacetone alcohol ・MS19: γ-butyrolactone and 1,3-dimethyl-2-imidazolidinone and ethyl-3-ethoxypropionate ・MS20: N-methyl-2-pyrrolidone and 3-methoxy-N,N-dimethylpropanamide and diacetone alcohol ・MS21: N-methyl-2-pyrrolidone and propylene carbonate and diacetone alcohol ・MS22: N-methyl-2-pyrrolidone and butyl glycolate and dipropylene glycol dimethyl ether ・MS23: N-ethyl-2-pyrrolidone and diacetone alcohol and propylene glycol monobutyl ether ・MS24: N-ethyl-2-pyrrolidone and diacetone alcohol and ethyl-3-ethoxypropionate ・MS25: γ-valerolactone and γ-butyrolactone and ethyl-3-ethoxypropionate ・MS26: N-methyl-2-pyrrolidone and diethylene glycol diethyl ether and dipropylene glycol monomethyl ether ・MS27: N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and diethylene glycol butyl methyl ether ・MS28: N-ethyl-2-pyrrolidone and diethylene glycol ethyl methyl ether and diisobutyl ketone ・MS29: N-methyl-2-pyrrolidone, diacetone alcohol and propylene glycol diacetate. 如請求項1～9中之任1項記載之液晶配向劑，其中，前述聚醯胺酸或者聚醯胺酸酯係藉由使四羧酸化合物與包含下述式[2]所表示之二胺之二胺或者包含下述式[2]所表示之二胺及其他二胺之二胺化合物反應而獲得， 惟，X及Y係與前述式[1]中之X及Y為相同意義。The liquid crystal alignment agent according to any one of claims 1 to 9, wherein the polyamic acid or the polyphthalamide is a compound represented by the following formula [2] The amine diamine is obtained by reacting a diamine compound represented by the following formula [2] with a diamine compound of another diamine, However, the X and Y systems have the same meanings as X and Y in the above formula [1]. 如請求項10所記載之液晶配向劑，其中，前述其他二胺係具有藉由光照射聚合或者產生自由基之機能之二胺。The liquid crystal alignment agent according to claim 10, wherein the other diamine has a diamine which is polymerized by light irradiation or generates a radical. 如請求項10或11所記載之液晶配向劑，其中，前述四羧酸化合物係含有下述式[4]所示之結構之四羧酸二酐或者其衍生物， 惟，Z係表示由下述[4a]～[4k]所選出之結構， 惟，＊1係鍵結於其中之一之酸酐基之鍵結位置，＊2係鍵結於另一酸酐基之鍵結位置；式[4a]中，Z1 ～Z4 係獨立表示氫原子、甲基、乙基、丙基、氯原子或苯環。The liquid crystal alignment agent according to claim 10, wherein the tetracarboxylic acid compound contains a tetracarboxylic dianhydride having the structure represented by the following formula [4] or a derivative thereof. However, the Z system represents the structure selected by the following [4a] to [4k], However, *1 is bonded to the bonding position of one of the acid anhydride groups, and *2 is bonded to the bonding position of another acid anhydride group; in the formula [4a], Z 1 to Z 4 independently represent a hydrogen atom. , methyl, ethyl, propyl, chlorine or benzene ring. 如請求項12所記載之液晶配向劑，前述四羧酸化合物係於該四羧酸化合物100莫耳%中，含有下述式[4]所示之結構之四羧酸二酐或者其衍生物5莫耳%以上。The liquid crystal alignment agent according to claim 12, wherein the tetracarboxylic acid compound is contained in 100% by mole of the tetracarboxylic acid compound, and contains a tetracarboxylic dianhydride having the structure represented by the following formula [4] or a derivative thereof. 5 moles above. 一種液晶配向膜之製造方法，其係將請求項1～13中之任1項記載之液晶配向劑以柔版印刷或噴墨法於基板表面塗布且進行燒結。A method for producing a liquid crystal alignment film, which is obtained by applying a liquid crystal alignment agent according to any one of claims 1 to 13 to a surface of a substrate by flexographic printing or ink jet method. 一種液晶配向膜，其係由請求項1～13中之任一項所記載之液晶配向劑所獲得。A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of claims 1 to 13. 如請求項15所記載之液晶配向膜，其被用於在具備電極的一對基板之間具有液晶層而成且經由下述步驟而製造的液晶顯示元件，該步驟為：在前述一對基板之間配置液晶組合物，該液晶組合物包含因活性能量線和熱中的至少一者而聚合的聚合性化合物，邊對前述電極間施加電壓邊使前述聚合性化合物聚合。The liquid crystal alignment film according to claim 15, wherein the liquid crystal display element is formed by providing a liquid crystal layer between a pair of substrates including electrodes, and the liquid crystal display element is formed by the following steps: A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the electrodes, and the polymerizable compound is polymerized while applying a voltage between the electrodes. 一種液晶顯示元件，其係具備請求項15所記載之液晶配向膜。A liquid crystal display device comprising the liquid crystal alignment film described in claim 15.
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