JPWO2017217465A1 - LIQUID CRYSTAL ORIENTING AGENT FOR LIQUID COATING FOR BOA SUBSTRATE OR SUBSTRATE WITH BCS AND LIQUID CRYSTAL DISPLAY ELEMENT - Google Patents

Abstract

A liquid crystal alignment agent for coating a BOA substrate or a substrate with BCS, and a liquid crystal display element provided with a BOA substrate having a good display quality or a substrate with a BCS obtained using the liquid crystal alignment agent other than two amino groups From the group consisting of a polyimide precursor obtained by reacting a diamine component containing a diamine containing nitrogen or a carboxylic acid group with a tetracarboxylic acid dianhydride component in the structure, and a polyimide obtained by imidizing the polyimide precursor A liquid crystal display device comprising a BOA substrate or a liquid crystal alignment agent for coating a substrate with BCS containing at least one selected polymer, and a BOA substrate or a substrate with BCS on which a liquid crystal alignment film obtained therefrom is formed.

Description

  The present invention relates to a liquid crystal alignment agent for coating a BOA substrate or a substrate with BCS, and a liquid crystal display device provided with the BOA substrate or a substrate with BCS obtained using the same.

Generally, the liquid crystal display device includes an array substrate on which thin film transistors are formed, and an opposite substrate on which a color filter is formed facing the array substrate, and a liquid crystal layer interposed between the array substrate and the opposite substrate Including. The color filter needs a black matrix at the boundary between colored layers such as red, green and blue for the purpose of enhancing the contrast and the coloring effect. In recent years, a color filter has been formed on an array substrate from the relationship of production yield etc., a color filter on array (COA: Color-Filter On Array), and a black matrix forming a black matrix on the COA substrate. A Black Matrix On Array (BOA) substrate has been developed.
Attempts have also been made to use a black colored resin composition as a column spacer material for supporting between an array substrate and a counter substrate, in view of further production yield etc. (Such column spacers as black column spacers (Also referred to as BCS: Black Colum Spacer), the black matrix material may also be used in the black colored resin composition.

Japanese Patent Laid-Open No. 2014-167492 Japanese Unexamined Patent Publication No. 2015-191234

Due to the structure of the BOA substrate, it is difficult to secure the reliability when manufacturing a liquid crystal display element as compared with a COA substrate, which may cause a defect in display quality of the liquid crystal display element. Furthermore, the above problem becomes more pronounced by using a BCS-attached substrate.
This invention is made in view of said situation, Comprising: The BOA board | substrate or the liquid crystal aligning agent for board | substrate application with BCS, and the said liquid crystal aligning agent, BOA board | substrate or BCS with a favorable display quality obtained An object of the present invention is to provide a liquid crystal display device provided with an attached substrate.

（式中、Ｃｙはアゼチジン、ピロリジン、ピペリジン、及びヘキサメチレンイミンからなる群から選ばれる脂肪族へテロ環を表す２価の基であり、これらの環部分に置換基が結合されていてもよい。Ｒ_１４は水素原子、単結合、カルボニル基又は＊−ＣＯＮＨ−（ただし、「＊」を付した結合手がピペリジン環と結合する。）である。Ｒ_１５は水素、又は一価の有機基を表す。Ｒ_１８及びＲ_１９は、それぞれ独立して、水素原子又は単結合である。）
３．前記ジアミンが下記式（１）〜（９）のジアミンからなる群から選ばれる少なくとも１つのジアミンである、上記１又は２に記載の液晶配向剤。
４．前記ジアミン成分が、下記式（１０）又は（１１）で示される、ジアミンを含む、上記１〜３のいずれか一項に記載の液晶配向剤。
５．前記テトラカルボン酸二無水物成分が、下記式（１２）〜（１４）からなる群から選ばれる少なくとも１つのテトラカルボン酸二無水物である、上記１〜４のいずれか一項に記載の液晶配向剤。
６．前記液晶配向剤が、前記ポリイミド前駆体以外の重合体又は該ポリイミド前駆体をイミド化したポリイミド以外の重合体を含む、上記１〜５のいずれか一項に記載の液晶配向剤。
７．前記液晶配向剤が、密着助剤、架橋剤、誘電体、導電物質及び有機溶媒からなる群から選ばれる少なくとも一つを更に含む、上記１〜６のいずれか一項に記載の液晶配向剤。
８．前記架橋剤が、後記式（１７）、式（１９）及び式（２１）から選ばれる少なくとも１つの化合物である、上記７に記載の液晶配向剤。
９．前記架橋剤が、後記式ＣＬ−１〜ＣＬ−３からなる群から選ばれる少なくとも１つの化合物である、上記８に記載の液晶配向剤。
１０．上記１〜９のいずれか一項に記載の液晶配向剤から得られる液晶配向膜を形成させたＢＯＡ基板又はＢＣＳ付き基板を具備する液晶表示素子。
１１．上記１〜９のいずれか一項に記載された液晶配向剤をＢＯＡ基板に塗布するＢＯＡ基板又はＢＣＳ付き基板上における液晶配向膜の製造方法。
１２．ＢＯＡ基板又はＢＣＳ付き基板と、上記１〜９のいずれか一項に記載されたＢＯＡ基板塗布用液晶配向剤を用いて前記ＢＯＡ基板又はＢＣＳ付き基板上に形成された液晶配向膜と、を備える液晶表示素子用基板。As a result of intensive studies, the present inventor has completed the present invention.
That is, the present invention has the following gist.
1. A polyimide precursor obtained by reacting a diamine component containing a diamine containing nitrogen or a carboxylic acid group and a tetracarboxylic acid dianhydride component in a structure other than one amino group, and the polyimide precursor The liquid crystal aligning agent for board | substrate application | coating for BOA board | substrate or a board | substrate with BCS containing at least 1 sort (s) of polymer chosen from the group which consists of an imidated polyimide.
2. The liquid crystal aligning agent according to the above 1, wherein the diamine has, as a partial structure, at least one structure selected from the group consisting of the following formulae:

(Wherein, Cy is a divalent group representing an aliphatic heterocycle selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine, and a substituent may be bound to these ring portions. R ₁₄ is a hydrogen atom, a single bond, a carbonyl group or * -CONH- (wherein the bond attached with “*” is bonded to a piperidine ring) R ₁₅ is hydrogen or a monovalent organic group R ₁₈ and R ₁₉ each independently represent a hydrogen atom or a single bond.)
3. The liquid crystal aligning agent according to the above 1 or 2, wherein the diamine is at least one diamine selected from the group consisting of diamines of the following formulas (1) to (9).
4. The liquid crystal aligning agent as described in any one of said 1-3 in which the said diamine component is shown by following formula (10) or (11) and contains diamine.
5. The liquid crystal according to any one of the above 1 to 4, wherein the tetracarboxylic acid dianhydride component is at least one tetracarboxylic acid dianhydride selected from the group consisting of the following formulas (12) to (14) Alignment agent.
6. 5. The liquid crystal aligning agent according to any one of 1 to 5, wherein the liquid crystal aligning agent contains a polymer other than the polyimide precursor or a polymer other than a polyimide obtained by imidizing the polyimide precursor.
7. 7. The liquid crystal aligning agent according to any one of the above 1 to 6, wherein the liquid crystal aligning agent further comprises at least one selected from the group consisting of an adhesion assistant, a crosslinking agent, a dielectric, a conductive substance and an organic solvent.
8. 7. The liquid crystal aligning agent according to 7 above, wherein the crosslinking agent is at least one compound selected from the following formula (17), formula (19) and formula (21).
9. 9. The liquid crystal aligning agent according to the above 8, wherein the crosslinking agent is at least one compound selected from the group consisting of the following formulas CL-1 to CL-3.
10. The liquid crystal display element which comprises the BOA substrate or the board | substrate with BCS in which the liquid crystal aligning film obtained from the liquid crystal aligning agent as described in any one of said 1-9 was formed.
11. The manufacturing method of the liquid crystal aligning film on the BOA board | substrate or the board | substrate with BCS which apply | coats the liquid crystal aligning agent described in any one of said 1-9 on a BOA board | substrate.
12. A BOA substrate or a substrate with BCS, and a liquid crystal alignment film formed on the BOA substrate or the substrate with BCS using the liquid crystal alignment agent for coating a BOA substrate according to any one of the above 1 to 9 Substrate for liquid crystal display element.

  The present invention provides a liquid crystal alignment agent for coating a BOA substrate or a substrate with BCS, and a BOA substrate or a substrate with BCS having good display quality obtained using the same.

  The liquid crystal aligning agent of the present invention comprises a diamine component containing a diamine having a nitrogen or carboxylic acid group in the structure other than two amino groups (hereinafter also referred to as a specific diamine) and a tetracarboxylic acid dianhydride BOA substrate or at least one polymer (hereinafter also referred to as a specific polymer) selected from the group consisting of a polyimide precursor obtained by reacting components and a polyimide obtained by imidizing the polyimide precursor It is a liquid crystal aligning agent for substrate coating with BCS. The liquid crystal display element of the present invention is a liquid crystal display element comprising a BOA substrate or a substrate with BCS on which a liquid crystal alignment film obtained from the liquid crystal alignment agent is formed.

上記の構造中、Ｃｙはアゼチジン、ピロリジン、ピペリジン、及びヘキサメチレンイミンからなる群から選ばれる脂肪族へテロ環を表す２価の基であり、これらの環部分に置換基が結合されていてもよい。Ｒ_１４は水素原子、単結合、カルボニル基又は＊−ＣＯＮＨ−（ただし、「＊」を付した結合手がピペリジン環と結合する。）である。Ｒ_１５は水素、又は一価の有機基を表す。Ｒ_１８及びＲ_１９は、それぞれ独立して、水素原子又は単結合である。<Diamine containing nitrogen or carboxylic acid group in structure other than two amino groups>
The diamine containing nitrogen or a carboxylic acid group in a structure other than two amino groups is at least one selected from the group consisting of the following formulas in a structure other than a structure in which two amino groups are bonded among diamine structures. It is a diamine which has one as a partial structure. The structure of the following formula is preferably monovalent or divalent, and can be bonded to a structure in which two amino groups are bonded at any position.

In the above structure, Cy is a divalent group representing an aliphatic heterocycle selected from the group consisting of azetidine, pyrrolidine, piperidine and hexamethyleneimine, and even if a substituent is bonded to these ring portions Good. R ₁₄ is a hydrogen atom, a single bond, a carbonyl group or * -CONH- (wherein the bond attached with “*” is bonded to a piperidine ring). R ₁₅ represents hydrogen or a monovalent organic group. Each of R ₁₈ and R ₁₉ independently represents a hydrogen atom or a single bond.

  Specifically, a diamine component containing at least one diamine selected from diamines represented by the following formulas (1) to (9) (hereinafter also referred to as specific diamines 1 to 9) and tetracarboxylic acid dianhydride BOA having a liquid crystal alignment film obtained from a liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyimide precursor obtained by reacting components and a polyimide obtained by imidating the polyimide precursor It is a liquid crystal display element which comprises a substrate or a substrate with BCS.

式（１）中、Ｘ^１は、単結合、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又はＮ（ＣＨ_３）ＣＯ−である。なかでも、−Ｏ−、−ＣＯＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−ＣＨ_２Ｏ−又はＯＣＯ−は、ジアミンを合成し易いので好ましい。特に好ましくは、−Ｏ−、−ＣＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−又はＣＨ_２Ｏ−である。
Ｘ^２は、炭素数１〜５のアルキル基又は窒素原子を含有する非芳香族複素環である。Ｘ^２が炭素数１〜５のアルキル基である場合は、該アルキル基は直鎖状でもよいし、分岐していてもよい。特に、アルキル基の炭素数は１〜３が好ましい。また、Ｘ^２が窒素原子を含有する非芳香族複素環である場合の例としては、ピロリジン環、ピペリジン環、ピペラジン環、ピラゾリジン環、キヌクリジン環又はイミダゾリジン環が挙げられる。特に、非芳香族複素環が５員環又は６員環のものは、液晶配向膜とした場合に良好な配向性が得られるので好ましい。また、非芳香族複素環が窒素原子を２つ含有する場合は、液晶表示素子とした場合に、液晶配向膜界面において液晶中のイオン性不純物を吸着し、液晶表示素子の良好な電気特性を保つので望ましい。
以上の観点より、窒素原子を含有する非芳香族複素環としては、ピペラジン環がとりわけ好ましい。加えて、Ｘ^２がＸ^３中の窒素原子又は該窒素原子に隣接する炭素原子と結合している場合は、液晶表示素子を形成したときに、直流電圧により蓄積する残留電荷の緩和を早くする効果に優れているため好ましい。<Specific diamine 1>
The specific diamine 1 used in the present invention is a diamine represented by the following formula (1).

In formula (1), X ¹ is a single bond, -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO- , -CON (CH ₃₎ - or _{N (CH} 3) a CO-. Among them, -O -, - COO -, - NH -, - CONH -, - NHCO -, - CON (CH 3) -, - CH 2 O- or OCO- is preferred because it is easy to synthesize the diamine. Particularly preferably, -O -, - CO -, - NH -, - CONH -, - NHCO -, - CON (CH 3) - or _CH 2 is O-.
X ² is a non-aromatic heterocycle containing an alkyl group of 1 to 5 carbon atoms or a nitrogen atom. When X ² is an alkyl group having 1 to 5 carbon atoms, the alkyl group may be linear or branched. In particular, the carbon number of the alkyl group is preferably 1 to 3. Further, examples of the case where X ² is a non-aromatic heterocyclic ring containing nitrogen atom, pyrrolidine ring, piperidine ring, piperazine ring, pyrazolidine ring, and a quinuclidine ring or imidazolidine ring. In particular, those in which the non-aromatic heterocyclic ring is a 5- or 6-membered ring are preferable because good alignment can be obtained when the liquid crystal alignment film is used. When the non-aromatic heterocycle contains two nitrogen atoms, in the case of a liquid crystal display element, ionic impurities in the liquid crystal are adsorbed at the interface of the liquid crystal alignment film, and good electrical characteristics of the liquid crystal display element are obtained. Desirable to keep.
From the above viewpoints, a piperazine ring is particularly preferable as the non-aromatic heterocycle containing a nitrogen atom. In addition, in the case where X ² is bonded to a nitrogen atom in X ³ or a carbon atom adjacent to the nitrogen atom, when the liquid crystal display element is formed, relaxation of residual charge accumulated by DC voltage is accelerated. It is preferable because the effect is excellent.

X ³ is a 5- or 6-membered aromatic heterocyclic ring containing one or two nitrogen atoms which may be substituted by an alkyl group of 1 to 5 carbon atoms. Examples of 5- or 6-membered aromatic heterocycles containing one or two nitrogen atoms include pyridine, imidazole, pyrazole, pyrazine, pyrimidine or pyridazine rings. Among them, a pyridine ring, an imidazole ring, a pyrazine ring or a pyrimidine ring is preferable. Furthermore, when the aromatic heterocycle in X ³ is substituted with an alkyl group, the carbon number of the alkyl group is preferably 1 to 3.
n is an integer of 1 to 4; Among them, an integer of 1 or 2 is preferable.

Specifically, the following compounds are exemplified, but not limited thereto.

式（２）中、Ｘ_１は炭素数６〜３０の芳香族環を有する有機基である。ｎは１〜４の整数である。式（２）で表されるジアミンの好ましい例としては、下記式（２−１）〜（２−５）が挙げられる。

<Specific diamine 2>
The specific diamine 2 used in the present invention is a diamine represented by the formula (2).

In Formula (2), X ₁ is an organic group having an aromatic ring having 6 to 30 carbon atoms. n is an integer of 1 to 4; As a preferable example of the diamine represented by Formula (2), following formula (2-1)-(2-5) is mentioned.

In formula (2-1), m1 is an integer of 1 to 4. Wherein (2-2), _{X 2} is a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, - _{O -, - CO -, -} NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH ₃₎ -, or -N _(CH 3) a CO-. m2 and m3 each represent an integer of 0 to 4, and m2 + m3 represents an integer of 1 to 4. In formula (2-3), m4 and m5 are integers of 1-5, respectively. In formula (2-4), X ₃ is a linear or branched alkyl group having 1 to 5 carbon atoms. m6 is an integer of 1 to 5; Wherein (2-5), _{X 4} is a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, - _{O -, - CO -, -} NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH ₃₎ -, or -N _(CH 3) a CO-. m7 is an integer of 1 to 4;
In formula (2-1), preferably, m1 is an integer of 1 to 2. In the formula (2-2), preferably, _{X 2} is a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - O -, - CO -, - NH-, _{-N (CH 3) -, -} CONH -, - NHCO -, - COO-, or a -OCO-, m @ 2 and m3 are both the integer 1. In formula (2-5), preferably, X ₄ is a single bond, -CH _2- , -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, - COO-, or a -OCO-, m7 is an integer of 1-2. Especially, the diamine represented by Formula (2-1) is especially preferable.

式（２−１５）中、Ｘ_５は単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、又は−ＯＣＯ−である。式（２−１６）中、Ｘ_６は単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、又は−ＯＣＯ−である。As a specific example of the diamine represented by Formula (2), following formula (2-6)-(2-16) can be mentioned.

In formula (2-15), X ₅ is a single bond, -CH _2- , -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO- or -OCO-. In formula (2-16), X ₆ is a single bond, -CH _2- , -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO- or -OCO-.

Ｑ_１は炭素原子数１〜５のアルキレンを表し、好ましくは、合成の簡便さから炭素数１〜５の直鎖アルキレンである。
Ｃｙはアゼチジン、ピロリジン、ピペリジン、及びヘキサメチレンイミンからなる群から選ばれる脂肪族へテロ環を表す２価の基である。合成の簡便さからアゼチジン、ピロリジン、又はピペリジンが好ましい。また、これらの環部分に置換基が結合されていてもよい。
Ｑ_２は下記式（３−Ｉ）又は（３−ＩＩ）の構造を表す。式（３−Ｉ）、又は（３−ＩＩ）中の＊１はＱ_１との結合を表す。＊２はベンゼン環との結合を表す。式（３−ＩＩ）中のＲ_１は水素、又は１価の有機基を表し、好ましくは、水素原子、又は炭素数１〜３の直鎖アルキル基であり、より好ましくは水素原子、又はメチル基である。
Ｒ_２、Ｒ_３は、１価の有機基である。ｑ、ｒは、それぞれ独立して、０〜４の整数である。但し、ｑあるいはｒの合計が２以上の場合、Ｒ_２及びＲ_３はそれぞれ独立している。好ましくは、合成の簡便さからＲ_２及びＲ_３はメチル基である。また、上記ジアミンを構成するベンゼン環におけるアミノ基の結合位置は限定されないが、アミノ基がそれぞれＣｙ上の窒素原子に対して３位、又は４位に、Ｑ_１とＲ_１が結合する窒素原子に対して３位、又は４位の位置にあることが好ましく、Ｃｙ上の窒素原子に対して４位に、Ｑ_１とＲ_１が結合する窒素原子に対して４位の位置にあることがより好ましい。

<Specific diamine 3>
The specific diamine 3 used in the present invention is a diamine represented by the following formula (3).

Q ₁ represents an alkylene having 1 to 5 carbon atoms, and is preferably a linear alkylene having 1 to 5 carbon atoms because of ease of synthesis.
Cy is a divalent group representing an aliphatic heterocycle selected from the group consisting of azetidine, pyrrolidine, piperidine and hexamethyleneimine. Azetidine, pyrrolidine or piperidine is preferred for ease of synthesis. In addition, substituents may be bonded to these ring portions.
Q ₂ represents a structure of the following formula (3-I) or (3-II). * 1 in formula (3-I) or (3-II) represents a bond to Q ₁ . * 2 represents a bond with a benzene ring. R ₁ in the formula (3-II) represents hydrogen or a monovalent organic group, preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or methyl It is a group.
R ₂ and R ₃ are monovalent organic groups. Each of q and r is independently an integer of 0 to 4. However, when the sum of q or r is 2 or more, R ₂ and R ₃ are each independent. Preferably, R ₂ and R ₃ are methyl groups for ease of synthesis. Further, the bonding position of the amino group in the benzene ring constituting the above diamine is not limited, but the nitrogen atom in which the amino group is bonded to Q ₁ and R _{1 at the} 3- or 4-position relative to the nitrogen atom on Cy, respectively Preferably in the 3- or 4-position relative to and in the 4-position relative to the nitrogen atom to which Q ₁ and R ₁ are attached, in the 4-position relative to the nitrogen atom on Cy More preferable.

式中、Ｒ_１６は水素原子、メチル基、又は、ｔｅｒｔ−ブトキシカルボニル基（以下、Ｂｏｃ基とも言う。）である。Ｒ_１７は水素原子又はメチル基である。Ｑ_１は炭素数１〜５の直鎖アルキレンである。It is preferable that the diamine represented by the said Formula (3) of this invention is a following formula (3-1) or (3-2).

In the formula, R ₁₆ is a hydrogen atom, a methyl group or a tert-butoxycarbonyl group (hereinafter also referred to as a Boc group). R ₁₇ is a hydrogen atom or a methyl group. Q ₁ is linear alkylene having 1 to 5 carbon atoms.

As a specific example represented by said (3-1) Formula, following formula (3-1-1)-(3-1-10) can be mentioned, for example, It represents with said (3-2) Formula As specific examples, for example, the following formulas (3-2-1) to (3-2-4) can be mentioned.

式（４）中、Ｄは２価の炭素数１〜２０の飽和炭化水素基、不飽和炭化水素基、芳香族炭化水素基又は複素環を表し、Ｄは種々の置換基を有していてもよい。ｍは１又は０である。<Specific diamine 4 to 7>
The specific diamines 4 to 7 used in the present invention are diamines represented by the following formulas (4) to (7) in which the amino group is protected by a Boc group.

In formula (4), D represents a divalent C 1 to C 20 saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring, and D has various substituents. It is also good. m is 1 or 0.

  The substitution position of the amino group in the above formula (4) is not particularly limited, but from the viewpoint of synthesis difficulty and availability of reagents, the position of meta or para is preferable based on the amide bond, and the liquid crystal alignment The position of para is particularly preferred. Also in aminobenzenes having no Boc group-protected amino group (that is, -NHBoc), the position of meta or para is preferable based on the amide bond as well, and the position of meta in terms of solubility Is preferred, and the position of para is preferred from the viewpoint of liquid crystal alignment. Further, hydrogen of aminobenzene not having —NHBoc may be substituted with an organic group or a halogen atom such as fluorine.

  D in the formula (4) is not limited, and the structure can be selected variously depending on the structure of the dicarboxylic acid or tetracarboxylic acid dianhydride used as the raw material. As D, a divalent hydrocarbon group is preferable from the viewpoint of solubility, and a linear alkylene group or a cyclic alkylene group is mentioned as a preferable example, and this hydrocarbon group may have an unsaturated bond . From the viewpoint of liquid crystal alignment and electrical properties, divalent aromatic hydrocarbon groups and heterocycles are preferred. From the viewpoint of liquid crystal alignment, D preferably has no substituent, but from the viewpoint of solubility, one in which a hydrogen atom is substituted with a carboxylic acid group, a fluorine atom or the like is preferable.

In Formula (5), E is a single bond or a divalent C1-C20 saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring. F represents a single bond, -O-, -OCO-, or -COO-.
The diamine when m in formula (4) is 0 or the diamine represented by formula (5) is a diamine of an asymmetric structure, but preferred D is the same as above, and preferred E is also the same as preferred D above. It is. In addition, regarding the diamine represented by Formula (5), the compound which both E and F are single bonds is also preferable.

Wherein (6), _{A 1} represents a single ^{bond, -O -, - NQ 1 -} , - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one selected from the group consisting of -OCO- It is a kind of bivalent organic group, or a C1-C3 alkylene group. Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ₁₆ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.

In Formula (7), X ⁴ and X ⁸ are each independently a single bond, -CH _2- or -CH ₂ CH _2- . X ^{5, X 7} are each independently, -CH ₂ -, or _-CH 2 CH ₂ -. X ⁶ is C 1 -C 6 alkylene or cyclohexylene. Y ¹ is a single bond, —O—, —NH—, —N (CH ₃ ) —, —C (= O) —, —C (= O) O—, —C (= O) NH—, — _{C (= O) N (CH} 3) -, -OC (= O) -, -NHC (= O) -, or _{-N (CH 3) C (=} O) - it is. Each R ₁₇ is independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an t-butyl group, a benzyl group or a 9-fluorenyl group. a is 0 or 1;

As a specific example of the diamine represented by said Formula (4)-(7), the formula selected from the group which consists of following formula can be mentioned, for example.

（式（８）中、Ｒ_８は水素原子、炭素数１〜６のアルキル基、炭素数６〜２０の芳香族基、炭素数７〜１３のアラルキル基又は１，３−ジオキソブチル基である。
炭素数１〜６のアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、２−ブチル基、ｉ−ブチル基、又はｔ−ブチル基などを挙げることができる。
炭素数６〜２０の芳香族基としては、炭素数６〜１２のアリール基又はその他の芳香族基を挙げることができる。前記炭素数６〜１２のアリール基としては、例えばフェニル基、３−フルオロフェニル基、３−クロロフェニル基、４−クロロフェニル基、４−ｉ−プロピルフェニル基、４−ｎ−ブチルフェニル基、又は３−クロロ−４−メチルフェニル基などを挙げることができる。前記その他の芳香族基としては、例えば４−ピリジニル基、２−フェニル−４−キノリニル基、２−（４’−ｔ−ブチルフェニル）−４−キノリニル基、又は２−（２’−チオフェニル）−４−キノリニル基などを、それぞれ挙げることができる。
炭素数７〜１３のアラルキル基としては、例えばベンジル基などを挙げることができる。<Specific diamine 8>
The specific diamine 8 used in the present invention is a diamine represented by the following formula (8).

In the formula (8), R ₈ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 1,3-dioxobutyl group.
As a C1-C6 alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-butyl group, i-butyl group, t-butyl group etc. are mentioned, for example It can be mentioned.
As a C6-C20 aromatic group, a C6-C12 aryl group or other aromatic groups can be mentioned. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, 3-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-i-propylphenyl group, 4-n-butylphenyl group, or 3 And -chloro-4-methylphenyl and the like can be mentioned. Examples of the other aromatic group include 4-pyridinyl group, 2-phenyl-4-quinolinyl group, 2- (4′-t-butylphenyl) -4-quinolinyl group, and 2- (2′-thiophenyl) group. The -4-quinolinyl group etc. can be mentioned, respectively.
As a C7-C13 aralkyl group, a benzyl group etc. can be mentioned, for example.

X ¹¹ is a single bond, a carbonyl group or * -CONH- (provided that the bond attached with “*” is bonded to a piperidine ring).
R ₆ , R ₇ , R ₉ and R ₁₀ each represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. However, the benzene ring which the said aryl group and an aralkyl group have may be substituted by the formyl group or a C1-C4 alkoxyl group.
As a C1-C6 alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-butyl group, i-butyl group, t-butyl group etc. are mentioned, for example A C 6-12 aryl group (with the proviso that the benzene ring of the aryl group may be substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms), for example, a phenyl group or a 4-formylphenyl group Or 3,4,5-trimethoxyphenyl group etc .;
Examples of the aralkyl group having 7 to 13 carbon atoms (wherein the benzene ring possessed by this aralkyl group may be substituted with a formyl group or an alkoxyl group having 1 to 4 carbon atoms) include, for example, benzyl group and the like. it can.

（式中、ａは１〜１２の整数であり、ｂは０〜５の整数である。）
で表される基（ただし以上において、「＊」を付した結合手がピペリジン環と結合する。）、メチレン基又は炭素数２〜６のアルキレン基である。
炭素数２〜６のアルキレン基としては、例えば１，３−プロピレン基、１，６−ヘキシレン基などを挙げることができる。
上記式（８）のベンゼン環に結合する２つのアミノ基は、基Ｘ^４に対して２，４−位又は３，５−位にあることが好ましい。X ⁹ , X ¹⁰ , X ¹² and X ¹³ each independently represent a single bond, a carbonyl group, * -CH ₂ -CO- or * -CH ₂ -CH (OH)-(wherein a bond with “*” attached) Is bonded to the piperidine ring).
X ¹⁴ is an oxygen atom, * -OCO-, the following formula (X ¹⁴ -1)

(Wherein, a is an integer of 1 to 12 and b is an integer of 0 to 5)
Embedded image (in the above, the bond attached with “*” is bonded to the piperidine ring), a methylene group or an alkylene group having 2 to 6 carbon atoms.
As a C2-C6 alkylene group, a 1, 3- propylene group, 1, 6 hexylene group etc. can be mentioned, for example.
The two amino groups bonded to the benzene ring of the above formula (8) are preferably in the 2,4- or 3,5-position relative to the group X ⁴ .

The following Formula (8-1)-Formula (8-4) is mentioned as a preferable specific example of the diamine shown by Formula (8).

Ｒ_１１は水素、又は一価の有機基を表す。一価の有機基としては、炭素数１〜１０のアルキル基やアルケニル基、アルコキシ基、シアノ基、ヒドロキシ基、フルオロアルキル基、トリフルオロアルコキシ基、フッ素原子及びこれらの組み合わせからなる群から選ばれる基などが挙げられる。好ましくは水素原子、又はメチル基である。
Ｒ_１２はそれぞれ独立して単結合又は以下の式（９−２）の構造を表す。また、ベンゼン環の任意の水素原子を一価の有機基に置換しても良い。<Specific diamine 9>
The specific diamine 9 used in the present invention is a diamine represented by the above formula (9).

R ₁₁ represents hydrogen or a monovalent organic group. The monovalent organic group is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, a cyano group, a hydroxy group, a fluoroalkyl group, a trifluoroalkoxy group, a fluorine atom and a combination thereof Groups and the like. Preferably it is a hydrogen atom or a methyl group.
Each R ₁₂ independently represents a single bond or a structure of the following formula (9-2). In addition, any hydrogen atom of the benzene ring may be substituted with a monovalent organic group.

Ｒ_１３は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−（ＣＨ_２）_ｌ−、−Ｏ（ＣＨ_２）_ｍＯ−、−ＣＯＮＨ−、及び−ＮＨＣＯ−からなる群から選ばれる２価の有機基を表す（ｌ、ｍは１〜５の整数を表す）。＊_１は式（９）中のベンゼン環と結合する部位を表す。＊_２は式（９）中のアミノ基と結合する部位を表す。ｎは１〜３の整数を表す。この中でも、蓄積電荷の緩和の観点から、Ｒ_１１は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、又はＮＨＣＯ−が好ましい。
ｎは、１〜３の整数を表す。好ましくは１又は２である。

R ₁₃ represents a single _{bond, -O -, - COO -,} - OCO -, - (CH 2) l -, - O (CH 2) m O -, - CONH-, and selected from the group consisting of -NHCO- (I and m each represents an integer of 1 to 5). * ₁ represents a site that binds to the benzene ring in Formula (9). * ₂ represents a site to be bound to the amino group in formula (9). n represents an integer of 1 to 3; Among these, from the viewpoint of relaxation of accumulated charge, R ₁₁ is preferably a single bond, -O-, -COO-, -OCO-, -CONH-, or NHCO-.
n represents an integer of 1 to 3; Preferably it is 1 or 2.

As a specific example of the diamine shown by said Formula (9), the diamine shown by the following formula (9-1-1)-a formula (9-1-12) can be illustrated. Among them, from the viewpoint of alleviation of stored charge, the formulas (9-1-1), (9-1-2), (9-1-3), (9-1-5), (9-1-8) , (9-1-9), (9-1-10), (9-1-11) or (9-1-12) are preferable, and the formulas (9-1-1), (9-1-2) ), (9-1-3), (9-1-11), or (9-1-12) are particularly preferable.

<Other diamine>
In the present invention, other diamines other than the specific diamine can be used in combination as part of the diamine component. Other diamines are not particularly limited, and examples thereof include side chain type diamines described in detail below. Side chain diamine is preferably used when producing a vertical alignment type liquid crystal display element.

式（１０）中、Ｙ^１は、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又はＯＣＯ−である。なかでも、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又はＣＯＯ−は、側鎖構造を合成しやすいので好ましい。より好ましくは、単結合、−（ＣＨ_２）_ａ−（ａは１〜１０の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又はＣＯＯ−である。
Ｙ^２は、単結合又は（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）である。なかでも、単結合又は（ＣＨ_２）_ｂ−（ｂは１〜１０の整数である）が好ましい。
Ｙ^３は、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又はＯＣＯ−である。なかでも、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又はＯＣＯ−が、合成しやすいので好ましい。より好ましくは、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１０の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又はＯＣＯ−である。The specific side chain type diamine is a diamine represented by the following formula (10).

In formula (10), Y ¹ is a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- . Among them, a single _{bond, - (CH 2) a -} (a is an integer of 1~15), - O -, - CH 2 O- or COO- is preferred because easy to synthesize a side chain structure. More preferably, a single _{bond, - (CH 2) a -} (a is an integer of 1 to _{10), - O -, - CH} 2 O- or COO-.
Y ² is a single bond or (CH ₂ ) _b- (b is an integer of 1 to 15). Among them, a single bond or (CH ₂ ) _b- (b is an integer of 1 to 10) is preferable.
Y ³ represents a single _{bond, - (CH 2) c -} (c is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or OCO-. Among them, a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- is preferable because it is easy to synthesize. More preferably, a single _{bond, - (CH 2) c -} (c is an integer of 1 to _{10), - O -, - CH} 2 O -, - COO- or OCO-.

Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycle. Any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl having 1 to 3 carbon atoms It may be substituted by a group or a fluorine atom. Furthermore, Y ⁴ is a C12 to C25 divalent organic group having a steroid skeleton. As Y ⁴ , an organic group having 12 to 25 carbon atoms and having a benzene ring, a cyclohexyl ring or a steroid skeleton is preferable.
Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocycle. Any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl having 1 to 3 carbon atoms It may be substituted by a group or a fluorine atom.
n is an integer of 0 to 4; Preferably, it is an integer of 0-2.
Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, it is a C1-C12 alkyl group or a C1-C12 alkoxyl group. More preferably, it is a C1-C9 alkyl group or a C1-C9 alkoxyl group.
m is an integer of 1 to 4; Preferably, it is an integer of 1.

More specifically, it is the diamine shown by following formula (10-1)-(10-31).

In formulas (10-1) to (10-3), R ¹ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or CH ₂ OCO—. R ² is an alkyl group having 1 to 22 carbon atoms, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxyl group.

In formulas (10-4) to (10-6), R ³ is —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or CH ₂ -is shown. R ⁴ is an alkyl group having 1 to 22 carbon atoms, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxyl group.

In formulas (10-7) to (10-8), R ⁵ is —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, — CH ₂ - or an O-. R ⁶ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

In formulas (10-9) to (10-10), R ⁷ is a C 3-12 alkyl group. The cis-trans isomers of 1,4-cyclohexylene are each trans isomers.

In formulas (10-11) to (10-12), R ⁸ is an alkyl group having 3 or more and 12 or less carbon atoms. The cis-trans isomers of 1,4-cyclohexylene are each trans isomers.

Wherein (10-13), ^{A 4} is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom. A ³ is a xylene group or 1,4-phenylene group 1,4-cyclohexylene. A ² is an oxygen atom or COO- * (wherein a bond with “*” is bonded to A ³ ). A ¹ is an oxygen atom or COO- * (wherein the bond attached with “*” is bonded to (CH ₂ ) a ₂ ). Moreover, a ₁ is an integer of 0 or 1. a ₂ is an integer of 2 to 10. a ₃ is an integer of 0 or 1;

  Among the above formulas (10-1) to (10-31), particularly preferable diamines are the formulas (10-1) to (10-6), the formulas (10-9) to the formulas (10-13), and the formulas (10-16), formula (10-19), formula (10-23), formula (10-25), formula (10-29) or the like.

式（１１）中、Ａｒはフェニレン、ナフチレン、及びビフェニレンからなる群から選ばれる芳香族炭化水素基を示す。それらには有機基が置換していても良く、水素原子はハロゲン原子に置き換わっていても良い。Ｒ_１、Ｒ_２はそれぞれ独立して炭素原子数１〜１０のアルキル基、アルコキシ基、ベンジル基、又はフェネチル基であり、アルキル基又はアルコキシ基の場合、Ｒ_１、Ｒ_２で環を形成していても良い。Ｔ_１、Ｔ_２はそれぞれ独立して単結合又は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＮＨ−、−ＣＨ_２Ｏ−、−Ｎ（ＣＨ_３）−、−ＣＯＮ（ＣＨ_３）−、又はＮ（ＣＨ_３）ＣＯ−の結合基である。Ｓは単結合又は非置換又はフッ素原子によって置換されている炭素原子数１〜２０のアルキレン基（ただしアルキレン基の-ＣＨ_２-又はＣＦ_２-は-ＣＨ＝ＣＨ-で任意に置き換えられていてもよく、次に挙げるいずれかの基が互いに隣り合わない場合において、これらの基に置き換えられていてもよい；−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＮＨ−、二価の炭素環、二価の複素環。）である。Ｑは下記の構造を表す。As another diamine, the diamine shown by following formula (11) is also mentioned.

In formula (11), Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene. They may be substituted with an organic group, and a hydrogen atom may be replaced by a halogen atom. 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 in the case of an alkyl group or an alkoxy group, R ₁ and R ₂ form a ring May be T ₁ and T ₂ each independently represent a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )- , -CON _(CH 3) -, or _{N (CH} 3) a linking group CO-. S is a single bond or unsubstituted or substituted or substituted by a fluorine atom, an alkylene group having 1 to 20 carbon atoms (with the proviso that -CH ₂ -or CF _{2-of the} alkylene group is optionally replaced by -CH = CH- And any of the following groups may be replaced by any of these groups if they are not adjacent to each other; -O-, -COO-, -OCO-, -NHCO-, -CONH-,- NH-, divalent carbocycle, divalent heterocycle. Q represents the following structure.

式中、Ｒは水素原子又は炭素原子数１〜４のアルキル基を表す。Ｒ_３は−ＣＨ_２−、−ＮＲ−、−Ｏ−、又はＳ−を表す。

In formula, R represents a hydrogen atom or a C1-C4 alkyl group. R ₃ is _{-CH 2 -, - NR -,} - O-, or S- represents a.

（式中、ｎは１〜８の整数を示す。）Specifically, the following diamines may be mentioned.

(Wherein, n represents an integer of 1 to 8)

上記その他のジアミンは、液晶配向膜とした際の液晶配向性、電圧保持率、蓄積電荷などの特性に応じて、１種類又は２種類以上を混合して使用することもできる。Other diamines include diamines of the following formula, or diamines described on pages 30 to 33 of WO 2014/171493 (2014.10.23 published).

The above-mentioned other diamines may be used alone or in combination of two or more, depending on the properties such as liquid crystal alignment, voltage holding ratio and accumulated charge when forming a liquid crystal alignment film.

式（１２）中、Ｚ^１は、炭素数４〜１３の４価の有機基であり、かつ炭素数４〜１０の非芳香族環状炭化水素基を含有する。<Tetracarboxylic acid dianhydride component>
The tetracarboxylic acid dianhydride used as a raw material for the polymer contained in the liquid crystal aligning agent used in the present invention is not particularly limited, but tetracarboxylic acid dianhydrides represented by the following formulas (12) to (14) It is preferable to use (also referred to as specific tetracarboxylic acid dianhydride).

Wherein (12), ^{Z 1} is a tetravalent organic group having 4 to 13 carbon atoms, and containing non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.

式（１２ａ）中、Ｚ^２〜Ｚ^５は、それぞれ独立に、水素原子、メチル基、塩素原子又はベンゼン環から選ばれる基である。式（６ｇ）中、Ｚ^６及びＺ^７は、それぞれ独立に、水素原子又はメチル基である。
式（１２）中、特に好ましいＺ^１は、重合反応性や合成の容易性から、式（１２ａ）、式（１２ｃ）、式（１２ｄ）、式（１２ｅ）、式（１２ｆ）又は式（１２ｇ）である。Specifically, it is a group represented by the following formulas (12a) to (12j).

In formula (12a), Z ^{2 to} Z ⁵ each independently represent a group selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. In formula (6 g), Z ⁶ and Z ⁷ are each independently a hydrogen atom or a methyl group.
In the formula (12), particularly preferable Z ¹ is from the formula (12a), the formula (12c), the formula (12d), the formula (12e), the formula (12f) or the formula (12g) from the viewpoint of polymerization reactivity and synthesis ease. ).

In Formula (13) or Formula (14), j and k are each independently 0 or 1. Each of x and y independently represents a single bond, a carbonyl, an ester, a phenylene, a sulfonyl or an amido group.
As specific tetracarboxylic acid dianhydrides, tetracarboxylic acid dianhydrides represented by the following formulas (12-1) to (12-5) are preferable, and among them, the residual image of the liquid crystal display element obtained (accumulated charge (12-1), (12-3) or (12-5) is preferred from the viewpoint of

<Other tetracarboxylic dianhydrides>
In the present invention, other tetracarboxylic acid dianhydrides other than the specific tetracarboxylic acid dianhydride can be used. Other tetracarboxylic acid dianhydrides include tetracarboxylic acid dianhydrides of tetracarboxylic acids shown below.
2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid Acid, 1,2,5,6-anthracenetetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4 '-Benzophenonetetracarboxylic acid, 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) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2, 3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,5 3,4-cyclobutane tetracarboxylic acid is mentioned.
The other tetracarboxylic acid dianhydrides may be used alone or in combination of two or more, depending on the properties such as liquid crystal alignment, voltage holding ratio and accumulated charge in forming a liquid crystal alignment film.

  The liquid crystal aligning agent of the present invention may additionally contain components other than the specific polymer component. As such an additional component, an adhesion aid for enhancing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealing material, and the following formula (17) for enhancing the strength of the liquid crystal alignment film And at least one crosslinking agent selected from (19) and (21), a dielectric or a conductive substance for adjusting the dielectric constant and electric resistance of the liquid crystal alignment film, or an organic solvent. Specific examples of these additional components are as variously disclosed in the known documents relating to liquid crystal aligning agents, and disclosed in [0105] on page 53 of page 2015 / [0116] on page 55 of WO 2015/060357. Ingredients and the like.

式（１７）中、Ｒ_２０、Ｒ_２１、Ｒ_２５、及びＲ_２６は、それぞれ独立して、水素原子、炭素数１〜４のアルキル基、炭素数２〜４のアルケニル基、又は炭素数２〜４のアルキニル基であり、少なくとも１つは式（１８）で表される基である。Ｒ_２２、及びＲ_２４はそれぞれ独立に芳香環を表し、該芳香環の任意の水素原子は、水酸基、炭素原子数１〜３のアルキル基、ハロゲン原子、炭素原子数１〜３のアルコキシ基又はビニル基で置換されていてもよい。Ｒ_２３は、単結合、全部又は一部が結合して環状構造を形成してもよい炭素原子数１〜１０の飽和炭化水素基である。

In formula (17), R ₂₀ , R ₂₁ , R ₂₅ and R ₂₆ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or 2 carbon atoms And an alkynyl group of to 4, at least one of which is a group represented by formula (18). R ₂₂ and R ₂₄ each independently represent an aromatic ring, and any hydrogen atom of the aromatic ring is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms or It may be substituted by a vinyl group. R ₂₃ is a single bond or a saturated hydrocarbon group having 1 to 10 carbon atoms which may be bonded in whole or in part to form a cyclic structure.

式（１９）中、Ｒ_２７は、炭素数１〜２０の脂肪族炭化水素基、又は芳香族炭化水素基を含むｎ価の有機基であり、ｃは２〜６の整数である。Ｒ_２８及びＲ_２９は、それぞれ独立して、水素原子、炭素数１〜４のアルキル基、炭素数２〜４のアルケニル基、又は炭素数２〜４のアルキニル基であり、これらの基は置換基を有していてもよい。なお、Ｒ_２８及びＲ_２９のうち少なくとも１つは、置換基としてヒドロキシ基を有する。また、Ｒ_２８及びＲ_２９のうち少なくとも１つが式（２０）で示される基で置換されているのが好ましい。式（２０）中、Ｒ_３０〜Ｒ_３３は、それぞれ独立して、水素原子、炭化水素基、又はヒドロキシ基で置換された炭化水素基である。

In formula (19), R ₂₇ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, and c is an integer of 2 to 6. R ₂₈ and R ₂₉ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, and these groups are substituted It may have a group. In addition, at least one of R ₂₈ and R ₂₉ has a hydroxy group as a substituent. In addition, it is preferable that at least one of R ₂₈ and R ₂₉ be substituted with a group represented by Formula (20). In formula (20), R _{30 to} R ₃₃ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group.

式（２１）中、Ｒ_３４、及びＲ_３８は、それぞれ独立に水素原子又は炭素原子数１〜３のアルキル基であり、Ｒ_３５、及びＲ_３７はそれぞれ独立に芳香環を表し、該芳香環の任意の水素原子は、水酸基、炭素原子数１〜３のアルキル基、ハロゲン原子、炭素原子数１〜３のアルコキシ基又はビニル基で置換されていてもよい。Ｒ_３６は、単結合、全部又は一部が結合して環状構造を形成してもよい炭素原子数１〜１０の飽和炭化水素基であり任意の水素原子はフッ素原子で置換されていてもよい、−ＮＨ−、−Ｎ（ＣＨ_３）−又は式（２２）で表される基である。式（２２）中、Ｐ_１及びＰ_２はそれぞれ独立に炭素原子数１〜５のアルキル基であり、Ｑ_１は芳香環を表す。）また式（２１）中、ｄ及びｆはそれぞれ独立に１〜３の整数であり、ｅ及びｇはそれぞれ独立に１〜３の整数である。

In formula (21), R ₃₄ and R ₃₈ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₃₅ and R ₃₇ each independently represent an aromatic ring, and the aromatic ring The optional hydrogen atom may be substituted by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a vinyl group. R ₃₆ is a single bond or a saturated hydrocarbon group having 1 to 10 carbon atoms which may form a cyclic structure by combining all or part thereof, and any hydrogen atom may be substituted by a fluorine atom , -NH -, - N (CH 3) - or a group represented by the formula (22). In Formula (22), P ₁ and P ₂ are each independently an alkyl group having 1 to 5 carbon atoms, and Q ₁ represents an aromatic ring. In the formula (21), d and f each independently represent an integer of 1 to 3, and e and g each independently represent an integer of 1 to 3.

The following three can be mentioned as a specific example of a compound represented by said Formula (17)-(22).

<Polymer>
In the present invention, a known polymerization method can be used as a method of synthesizing a polymer. For example, the method as described in pages 39-42 of international publication 2014/171493 (2014.10.23 publication) is mentioned.

<Liquid crystal alignment agent>
All of the polymer components in the liquid crystal aligning agent of the present invention may be the specific polymer used in the present invention, and other specific polymers may be mixed with the specific polymer of the present invention. At that time, the content of the other polymer with respect to the specific polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass.
As another polymer other than that, the polyimide precursor obtained from the diamine component which consists of diamine other than a specific diamine and a tetracarboxylic dianhydride component, or the polyimide which imidated this polyimide precursor is mentioned. Furthermore, as other polymers other than that, an acrylic polymer, a methacrylic polymer, a polystyrene or a polyamide etc. are mentioned.

It is preferable that content of an organic solvent is 70-99 mass% from a viewpoint that the organic solvent in the liquid crystal aligning agent of this invention forms a uniform polymer film by application | coating. This content can be suitably changed with the film thickness of the liquid crystal aligning film made into the objective. It will not specifically limit, if it is an organic solvent in which the specific polymer mentioned above is dissolved as an organic solvent in that case. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, Dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, Ethylene carbonate, propylene carbonate, diglyme or 4-hydroxy-4-methyl-2-pentanone and the like can be mentioned. These may be used alone or in combination.
The liquid crystal aligning agent of the present invention is a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group or an alkoxyl group, or A crosslinkable compound having a polymerizable unsaturated bond can also be contained.
In addition, as a compound for improving the uniformity of film thickness and surface smoothness, a fluorine-based surfactant, a silicone-based surfactant, or a nonion-based surfactant can be contained, and a liquid crystal alignment film and the like A functional silane containing compound or an epoxy group containing compound can also be contained as a compound which improves adhesiveness with a board | substrate.
In addition, a dielectric or a conductive substance may be added for the purpose of changing the electric properties such as the dielectric constant and the conductivity of the liquid crystal alignment film.
The liquid crystal aligning agent of the present invention can contain an organic solvent (also referred to as a poor solvent) or a compound that improves the uniformity of the film thickness of the polymer film and the surface smoothness when the liquid crystal aligning agent is applied. Furthermore, a compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board | substrate can also be contained.

The following specific examples may be mentioned as poor solvents for improving film thickness uniformity and surface smoothness.
For example, isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexyl, propyl ether, dihexyl Ether, n-hexane, n-pentane, n-octane, diethyl ether Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxy Ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy- 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ester Low surface tension such as l-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, or lactic acid isoamyl ester The organic solvent which it has is mentioned.
These poor solvents may be used alone or in combination of two or more. When using the above poor solvents, it is preferable that it is 5-80 mass% of the whole organic solvent contained in a liquid crystal aligning agent, More preferably, it is 20-60 mass%.

<Liquid crystal>
As a liquid crystal composition used for the liquid crystal display element of the present invention, nematic liquid crystals having positive dielectric anisotropy are used in horizontal alignment type liquid crystal display elements, and nematic liquid crystals having negative dielectric anisotropy depending on the application. Also good.
In a vertical alignment liquid crystal display device, nematic liquid crystals having negative dielectric anisotropy can be used. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, or terphenyl liquid crystal can be used. In addition, alkenyl-based liquid crystals can also be used in combination. As such alkenyl liquid crystals, conventionally known ones can be used. For example, the compound etc. which are represented by a following formula can be mentioned.

<Liquid crystal alignment film / Liquid crystal display element>
The liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a BOA substrate or a substrate with BCS, and then subjected to alignment treatment by rubbing treatment or light irradiation. Moreover, in the case of the vertical alignment application etc., it can be used as a liquid crystal aligning film, without an orientation process.
In the present invention, the BOA substrate is a substrate in which a black matrix is formed on a COA substrate. As a material used for the black matrix, a column spacer (black column spacer (BCS)) supporting between the array substrate and the counter substrate may be used.
The BCS-containing substrate is a substrate on which a black colored resin composition is used as a column spacer material for supporting the space between the array substrate and the counter substrate, and a black column spacer is formed. A black matrix material may be used.

For example, a colored resin composition is coated on a transparent substrate by spin coating or the like, dried using a vacuum dryer or a hot plate or the like, and then passed through a photomask using a superhigh pressure mercury lamp or the like. The film can be formed by exposure, development using a KOH aqueous solution and the like, and baking using a hot air circulation oven. As a coloring resin composition, the black matrix and coloring resin composition for BCS prepared according to the method as described in "0312"-"0314" of Japan Unexamined-Japanese-Patent No. 2014-67028 can be used, for example.
The transparent substrate used in this case is not particularly limited as long as it is a substrate with high transparency, and a glass substrate, or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed. In addition, in the reflection type liquid crystal display element, an opaque substrate such as a silicon wafer can be used if it is only on one substrate, and in this case, a material that reflects light such as aluminum can also be used as an electrode.

The coating method of the liquid crystal aligning agent is not particularly limited, but industrially, a method of performing by screen printing, offset printing, flexographic printing, inkjet, or the like is common. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used according to the purpose.
After the liquid crystal aligning agent is applied on a BOA substrate or a substrate with BCS, the solvent can be evaporated at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate to form a polymer film. If the thickness of the polymer film after firing is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display device, and if it is too thin, the reliability of the liquid crystal display device may be lowered. Is 10 to 100 nm. When the liquid crystal is horizontally or obliquely aligned, the fired polymer film is treated by rubbing or irradiation with polarized ultraviolet light.

In addition, in a vertical alignment type liquid crystal display element, a photopolymerizable compound is added in advance to a liquid crystal composition, and it is used together with a vertical alignment film such as polyimide to irradiate ultraviolet light while applying alternating current or direct current voltage to a liquid crystal cell. There is known a PSA (Polymer sustained Alignment) element capable of controlling the alignment of liquid crystal and improving the response speed of the liquid crystal by polymerizing a polymerizable compound, and reported in JP-A-2003-307720 and the like. There is.
Examples of the polymerizable compound include compounds having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in the molecule. At that time, the content of the polymerizable compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 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 alignment control of the liquid crystal can not be performed without polymerization of the polymerizable compound, and when the amount is more than 10 parts by mass, the amount of unreacted polymerizable compounds increases. The burn-in characteristics of the
On the other hand, the response speed of the liquid crystal display can be increased by adding the photopolymerizable compound not in the liquid crystal composition but in the liquid crystal alignment film (SC-PVA type liquid crystal display) K. Hanaoka, SID 04 Non-patent documents such as DIGEST, P. 1200-1202 have been reported.

下記式ＤＡ−Ｓ１〜ＤＡ−Ｓ３で表される垂直配向性側鎖ジアミン

下記式ＤＡ−１で表される感光性ジアミン

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
The abbreviations are as follows.
(Acid dianhydride)
BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride, CBDA: 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, PMDA: pyromellitic acid Dianhydride, TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4,2,3-dianhydride (diamine)
PDA: p-phenylenediamine, DDM: 4,4'-methylenedianiline, DBA: 3,5-diaminobenzoic acid,
Nitrogen-containing diamine represented by the following formula DA-N1 to DA-N7

Vertically Aligned Side-Chain Diamines Represented by the Following Formulas DA-S1 to DA-S3

Photosensitive diamine represented by the following formula DA-1

<Solvent>
NMP: N-methyl-2-pyrrolidone, BC: butyl cellosolve <additive>
3 AMP: 3-picolylamine <crosslinking agent>
Crosslinking agents represented by the following formulas CL-1 to CL-3

(Molecular weight measurement conditions for polyimide)
Apparatus: High temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Science Co., Ltd., column: Shodex column (KD-803, KD-805), column temperature: 50 ° C., eluent: N, N ' -Dimethylformamide (As additive: 30 mmol / L of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol / L of phosphoric acid / anhydrous crystal (o-phosphoric acid), 10 ml of tetrahydrofuran (THF) L), flow rate: 1.0 ml / min, standard sample for calibration curve preparation: Tosoh TSK standard polyethylene oxide (molecular weight about 9000, 000, 150,000, 100,000, 30,000), and Polymer Laboratory, Inc. Polyethylene glycol (molecular weight about 12,000, 4,000, 1,000).

(Imidation rate of polyimide)
Place 20 mg of polyimide powder in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Science Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture), and add ultrasonic waves. It was completely dissolved. This solution was subjected to proton NMR measurement at 500 MHz with an NMR meter (JNW-ECA500) manufactured by Nippon Denshi Datum Co., Ltd. The imidation ratio is determined using a proton derived from a structure that does not change before and after imidization as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of the amic acid appearing around 9.5 to 10.0 ppm It calculated | required by the following formula using integration value. In the following formula, x is a proton peak integrated value derived from the NH group of the amic acid, y is a peak integrated value of the reference proton, and α is a proton of the NH group of the amic acid in the case of polyamic acid (imidation ratio is 0%) It is the number ratio of reference protons to one.
Imidation ratio (%) = (1−α · x / y) × 100

Synthesis Example 1
Dissolve BODA (18.77 g, 75.0 mmol), DBA (10.65 g, 70.0 mmol), and DA-S2 (13.04 g, 30.0 mmol) in NMP (141.5 g) at 80 ° C. After reacting for 5 hours, CBDA (4.71 g, 24.0 mmol) and NMP (47.2 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5 mass%, acetic anhydride (43.1 g) and pyridine (13.4 g) are added as an imidation catalyst, and it is made to react at 100 degreeC for 3 hours The The reaction solution was poured into methanol (2700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (A). The imidation ratio of this polyimide was 78%, the number average molecular weight was 22000, and the weight average molecular weight was 56000.
NMP (44.0 g) was added to the obtained polyimide powder (A) (6.0 g), and stirred at 70 ° C. for 20 hours for dissolution. 6.0 g of 3 AMP (1 mass% NMP solution), NMP (4.0 g), and BC (40.0 g) were added to this solution, and liquid crystal aligning agent (A1) was obtained by stirring at room temperature for 5 hours.

(Composition example 2)
BODA (5.00 g, 20.0 mmol), DA-N1 (7.27 g, 30.0 mmol), DA-S1 (11.42 g, 30.0 mmol), and PDA (4.33 g, 40.0 mmol), NMP After dissolving in (113.8 g) and reacting at 60 ° C. for 3 hours, CBDA (11.37 g, 58.0 mmol) and NMP (26.3 g) are added and reacted at 40 ° C. for 1 hour. (4.36 g, 20.0 mmol) and NMP (35.00 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5 mass%, acetic anhydride (46.3 g) and a pyridine (14.3 g) are added as an imidation catalyst, and it is made to react at 50 degreeC for 3 hours The The reaction solution was poured into methanol (2700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (B). The imidation ratio of this polyimide was 76%, the number average molecular weight was 13000, and the weight average molecular weight was 32000.
A liquid crystal aligning agent (B1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (B) (6.0 g).

(Composition example 3)
BODA (5.00 g, 20.0 mmol), DA-N1 (7.27 g, 30.0 mmol), DA-S1 (11.42 g, 30.0 mmol), and DBA (6.09 g, 40.0 mmol), NMP After dissolving in (118.3 g) and reacting at 60 ° C. for 3 hours, CBDA (11.37 g, 58.0 mmol) and NMP (27.3 g) are added and reacted at 40 ° C. for 1 hour. (4.36 g, 20.0 mmol) and NMP (36.41 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5 mass%, acetic anhydride (44.5 g) and pyridine (13.8 g) are added as an imidation catalyst, and it is made to react at 50 ° C. for 3 hours The The reaction solution was poured into methanol (2700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (C). The imidation ratio of this polyimide was 79%, the number average molecular weight was 21000, and the weight average molecular weight was 49000.
A liquid crystal aligning agent (C1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (C) (6.0 g).

(Composition example 4)
TCA (22.19 g, 99.0 mmol), DDM (9.91 g, 50.0 mmol), DA-N2 (7.64 g, 25.0 mmol), and DA-S3 (12.37 g, 25.0 mmol) with NMP It was dissolved in (208.4 g) and reacted at 60 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5 mass%, acetic anhydride (37.6 g) and pyridine (11.6 g) are added as an imidation catalyst, and it is made to react at 110 ° C. for 4 hours The The reaction solution was poured into methanol (2700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (D). The imidation ratio of this polyimide was 68%, the number average molecular weight was 11,000, and the weight average molecular weight was 25000.
A liquid crystal aligning agent (D1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (D) (6.0 g).

(Composition example 5)
BODA (18.77 g, 75.0 mmol), DA-N3 (11.78 g, 30.0 mmol), DBA (3.04 g, 20.0 mmol), and DA-S1 (19.03 g, 50.0 mmol) with NMP After dissolving in (171.9 g) and reacting at 80 ° C. for 5 hours, CBDA (4.71 g, 24.0 mmol) and NMP (57.32 g) are added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution I got
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5 mass%, acetic anhydride (35.5 g) and a pyridine (11.0 g) are added as an imidation catalyst, and it is made to react at 100 degreeC for 3 hours The The reaction solution was poured into methanol (2700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (E). The imidation ratio of this polyimide was 75%, the number average molecular weight was 16000, and the weight average molecular weight was 39000.
A liquid crystal aligning agent (E5) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (E) (6.0 g).

Synthesis Example 6
Dissolve BODA (18.77 g, 75.0 mmol), DA-N4 (9.96 g, 50.0 mmol), and DA-S1 (19.03 g, 50.0 mmol) in NMP (157.4 g), 80 After 5 hours of reaction at .degree. C., CBDA (4.12 g, 21.0 mmol) and NMP (52.46 g) were added and reacted at 40.degree. C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5 mass%, acetic anhydride (38.8 g) and pyridine (12.0 g) are added as an imidation catalyst, and it is made to react at 100 ° C. for 3 hours The The reaction solution was poured into methanol (2700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (F). The imidation ratio of this polyimide was 57%, the number average molecular weight was 10000, and the weight average molecular weight was 24000.
A liquid crystal aligning agent (F1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (F) (6.0 g).

Synthesis Example 7
BODA (12.51 g, 50.0 mmol), PDA (3.24 g, 30.0 mmol), DA-N5 (11.13 g, 20.0 mmol), and DA-S1 (19.03 g, 50.0 mmol) with NMP After dissolving in (166.6 g) and reacting at 60 ° C. for 3 hours, CBDA (9.51 g, 48.5 mmol) and NMP (41.11 g) are added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution I got
After adding NMP to this polyamic acid solution (180 g) and diluting to 6.5 mass%, acetic anhydride (36.6 g) and pyridine (11.4 g) are added as an imidation catalyst, and it is made to react at 80 ° C. for 2 hours The The reaction solution was poured into methanol (2700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 80 ° C. to obtain polyimide powder (F). The imidation ratio of this polyimide was 73%, the number average molecular weight was 17000, and the weight average molecular weight was 38000.
A liquid crystal aligning agent (G1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (G) (6.0 g).

(Comparative Example 1)
Dissolve BODA (12.51 g, 50.0 mmol), DA-1 (16.52 g, 50.0 mmol), and DA-S1 (19.03 g, 50.0 mmol) in NMP (192.2 g), 60 After reacting for 3 hours at ° C, PMDA (4.36 g, 48.5 mmol), CBDA (9.61 g, 49.0 mmol) and NMP (38.4 g) are added and reacted for 10 hours at 40 ° C. to obtain a polyamic acid solution I got
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5 mass%, acetic anhydride (35.3 g) and pyridine (10.9 g) are added as an imidation catalyst, and it is made to react at 80 ° C. for 3 hours The The reaction solution was poured into methanol (2700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (H). The imidation ratio of this polyimide was 73%, the number average molecular weight was 17000, and the weight average molecular weight was 48000.
A liquid crystal aligning agent (H1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (H) (6.0 g).

(Comparative Synthesis Example 2)
Dissolve BODA (12.51 g, 50.0 mmol), PDA (5.41 g, 50.0 mmol), and DA-S1 (19.03 g, 50.0 mmol) in NMP (147.7 g) at 60 ° C. After reacting for 3 hours, BDA (9.41 g, 48.0 mmol) and NMP (37.7 g) were added, and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (200 g) and diluting to 6.5 mass%, acetic anhydride (43.7 g) and a pyridine (13.5 g) are added as an imidation catalyst, and it is made to react at 80 degreeC for 2 hours The The reaction solution was poured into methanol (2700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (I). The imidation ratio of this polyimide was 72%, the number average molecular weight was 13000, and the weight average molecular weight was 25000.
A liquid crystal aligning agent (I1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (I) (6.0 g).

Synthesis Example 8
The liquid crystal aligning agent (H1) obtained in Comparative Synthesis Example 1 is mixed with 6.0 g as a first component, and 14.0 g is mixed with the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 as a second component for 1 hour The liquid crystal aligning agent (J1) was prepared by stirring.
Synthesis Example 9
6.0 g of the liquid crystal aligning agent (I1) obtained in Comparative Synthesis Example 2 as the first component, and 14.0 g of the liquid crystal aligning agent (C1) obtained in Synthesis Example 3 as the second component are mixed for 1 hour The liquid crystal aligning agent (K1) was prepared by stirring.
Synthesis Example 10
CL-2 is added so that it becomes 10 wt% of a resin component with respect to 10.0 g of liquid crystal aligning agents (A1) obtained by the synthesis example 1, The liquid crystal aligning agent (A2) is made by stirring at room temperature for 1 hour. Prepared.

Synthesis Example 11
CL-1 was added to be 10 wt% of the resin component to 10.0 g of the liquid crystal aligning agent (D1) obtained in Synthesis Example 4, and the liquid crystal aligning agent (D2) was obtained by stirring at room temperature for 1 hour. Prepared.
Synthesis Example 12
CL-3 was added to be 10 wt% of the resin component with respect to 10.0 g of the liquid crystal aligning agent (K1) obtained in Synthesis Example 9, and the liquid crystal aligning agent (K2) was formed by stirring at room temperature for 1 hour. Prepared.

Synthesis Example 13
Dissolve BODA (2.50 g, 10.0 mmol), DA-N6 (3.97 g, 10.0 mmol), and DA-S1 (3.81 g, 10.0 mmol) in NMP (41.1 g), 60 After 3 hours of reaction at .degree. C., CBDA (1.88 g, 9.60 mmol) and NMP (7.5 g) were added and reacted at 40.degree. C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (40 g) and diluting to 6.5 mass%, acetic anhydride (6.68 g) and pyridine (2.07 g) are added as an imidation catalyst, and it is made to react at 80 ° C. for 3 hours The The reaction solution was poured into methanol (461 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C. to obtain polyimide powder (L). The imidation ratio of this polyimide was 72%, the number average molecular weight was 15000, and the weight average molecular weight was 28000.
A liquid crystal aligning agent (L1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (L) (6.0 g).

Synthesis Example 14
Dissolve BODA (2.50 g, 10.0 mmol), DA-N7 (3.41 g, 10.0 mmol), and DA-S1 (3.81 g, 10.0 mmol) in NMP (38.9 g), 60 After 3 hours of reaction at .degree. C., CBDA (1.88 g, 9.60 mmol) and NMP (7.5 g) were added and reacted at 40.degree. C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (40 g) and diluting to 6.5 mass%, acetic anhydride (6.99 g) and pyridine (2.17 g) are added as an imidation catalyst and reacted at 80 ° C. for 3 hours The The reaction solution was poured into methanol (463 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C. to obtain a polyimide powder (M). The imidation ratio of this polyimide was 70%, the number average molecular weight was 14,000, and the weight average molecular weight was 30,000.
A liquid crystal aligning agent (M1) was obtained in the same manner as in Synthesis Example 1 using the obtained polyimide powder (M) (6.0 g).

Example 1
A liquid crystal cell was produced using liquid crystal aligning agent A1 obtained in Synthesis Example 1 according to the following procedure, and measurement of pretilt angle and measurement of voltage retention were performed.
<Preparation of Colored Resin Composition>
The colored resin composition (a) for a black column spacer (BCS) used in the present invention is a resin composition also used as a black matrix material, and described in "03132" to "0314" of JP-A 2014-67028. It was prepared in the same manner as the resist (VI).
<Preparation of ITO substrate with BCS>
The above colored resin composition (a) is applied to a glass substrate with an ITO electrode on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm / 5 μm is formed, and the film thickness after firing is 4 μm. It applied by spin coating so that it might become. Then, after drying with a vacuum dryer for 60 seconds, it was dried for 2 minutes on a hot plate at 110 ° C. to obtain a pre-exposure substrate with the colored resin composition (a).
This pre-exposure substrate was exposed at 50 mJ / cm 2 using an ultrahigh pressure mercury lamp through a circular photomask with an opening of 20 μm, and then developed using a KOH aqueous solution with a concentration of 0.05% by mass and a temperature of 25 ° C. Thereafter, the substrate with the resist (VI) was baked at 230 ° C. for 30 minutes using a hot air circulation oven to obtain an ITO substrate with BCS.

<Fabrication of liquid crystal cell>
A liquid crystal cell was produced in the following procedure using the liquid crystal aligning agent (A1). The liquid crystal aligning agent (A1) is spin-coated on the ITO surface of the BCS-attached ITO substrate, dried on a hot plate at 80 ° C. for 90 seconds, and fired for 30 minutes in a hot air circulating oven at 200 ° C. A liquid crystal alignment film was formed.

The liquid crystal aligning agent (A1) is spin-coated on the ITO surface on which the electrode pattern is not formed, dried on a hot plate at 80 ° C. for 90 seconds, and baked for 30 minutes in a hot air circulating oven at 200 ° C. A liquid crystal alignment film having a thickness of 100 nm was formed.
The thermosetting sealing agent (Kyoritsu Chemical Co., Ltd. XN-1500T) was printed on the liquid crystal aligning film of one board | substrate about said 2 sheets of board | substrates. Next, with the surface of the other substrate on which the liquid crystal alignment film was formed facing inside, the substrate was bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell. A liquid crystal cell was prepared by injecting a polymerizable compound-containing liquid crystal MLC-302 (trade name: alkenyl liquid crystal, manufactured by Merck Co., Ltd.) into the empty cell by a reduced pressure injection method. The voltage holding ratio (VHR) of this liquid crystal cell was measured.

Next, in a state where a DC voltage of 15 V was applied to this liquid crystal cell, UV which was passed through a band pass filter of 365 nm from the outside of this liquid crystal cell was irradiated with 10 J / cm ² (also called primary PSA treatment). In addition, the illumination intensity of UV was measured using ORC company make UV-MO3A (attachment: UV-35). Thereafter, for the purpose of deactivating the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32 /) using a UV-FL irradiator manufactured by Toshiba Lighttech Co., Ltd. without applying a voltage. A-1) was irradiated for 30 minutes (also called secondary PSA treatment). Thereafter, the measurement of the pretilt angle of the pixel portion and the measurement of the voltage retention rate were performed on the cells after UV irradiation.
"Measurement of pretilt angle"
It measured using LCD analyzer LCA-LUV42A (made by Meiryo technicala company).
"Evaluation of voltage holding ratio"
A voltage of 1 V was applied for 60 μs in a hot air circulating oven at 60 ° C., and then the voltage after 1667 msec was measured, and how much the voltage could be held was calculated as a voltage holding ratio. For measurement of the voltage holding ratio, VHR-1 manufactured by Toyo Santechnica Co., Ltd. was used.

(Examples 2-14, Comparative Examples 1 and 2)
The same operation as in Example 1 is carried out except that the liquid crystal aligning agent (A1) used in Example 1 is changed to liquid crystal aligning agents (B1) to (M1), (A2), (D2) or (K2), Measurement of pretilt angle and measurement of voltage holding ratio were performed.
(Example 1 ')
In the same manner as in Example 1, a liquid crystal cell was prepared using a substrate with an ITO electrode without BCS attached, and the pretilt angle and the voltage holding ratio were measured. In addition, in order to maintain the cell gap, 4 μm bead spacers were used instead of the black column spacers to scatter on the liquid crystal alignment film.
(Examples 2 'to 14', comparative examples 1 'and 2')
The same operations as in Example 1 'are repeated except that the liquid crystal aligning agent (A1) used in Example 1' is changed to liquid crystal aligning agents (B1) to (M1), (A2), (D2) or (K2). The measurement of the pretilt angle and the measurement of the voltage holding ratio were performed.

As in the above results, Examples 1 to 7, 13, 14 and Examples 1 ′ to 7 ′, 13 ′, 14 ′ have BCS compared with Comparative Examples 1 and 2 and Comparative Examples 1 ′ and 2 ′. It was confirmed that high VHR characteristics were exhibited even when the substrate was used.
Further, as can be seen from Examples 8, 9 and 8 'and 9', a combination of a polymer not having a diamine containing a carboxyl group or a nitrogen-containing structure as a monomer unit and a polymer having the diamine as a monomer unit However, it has been confirmed that high VHR characteristics can be expressed. Further, as shown in Examples 10 to 12 and Examples 10 'to 12', even when a substrate with BCS is used, the addition of a crosslinking agent to a polymer exhibiting high VHR characteristics is as high as when not added. It was confirmed that VHR characteristics can be expressed.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2016-118281 filed on Jun. 14, 2016 are incorporated herein by reference and incorporated as disclosure of the specification of the present invention. It is a thing.

Claims (12)

  A polyimide precursor obtained by reacting a diamine component containing a diamine containing nitrogen or a carboxylic acid group in a structure other than two amino groups with a tetracarboxylic acid dianhydride component and imidization of the polyimide precursor A liquid crystal aligning agent for coating a BOA substrate or a substrate with BCS, comprising at least one polymer selected from the group consisting of The liquid crystal aligning agent of Claim 1 which has as a partial structure the at least 1 structure selected from the group which the said diamine becomes from the following formula.

(Wherein, Cy is a divalent group representing an aliphatic heterocycle selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine, and a substituent may be bound to these ring portions. R ₁₄ is a hydrogen atom, a single bond, a carbonyl group or * -CONH- (wherein the bond attached with “*” is bonded to a piperidine ring) R ₁₅ is hydrogen or a monovalent organic group R ₁₈ and R ₁₉ each independently represent a hydrogen atom or a single bond.) The liquid crystal aligning agent according to claim 1 or 2, wherein the diamine is at least one diamine selected from the group consisting of diamines of the following formulas (1) to (9).

(In Formula (1), X ¹ is a single bond, -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO- , -CON (CH ₃₎ - or _{N (CH} 3) a CO- .X ² is .X ³ is a non-aromatic heterocyclic ring containing alkyl group or a nitrogen atom of 1 to 5 carbon atoms, the carbon It is a 5- or 6-membered aromatic heterocyclic ring containing one or two nitrogen atoms optionally substituted by an alkyl group of 1 to 5. n is an integer of 1 to 4.)

(In the formula (2), X ₁ is an organic group having an aromatic ring having 6 to 30 carbon atoms. N is an integer of 1 to 4).

(In the formula (3), Q ₁ represents an alkylene having 1 to 5 carbon atoms. Cy represents a divalent group representing an aliphatic heterocycle selected from the group consisting of azetidine, pyrrolidine, piperidine, and hexamethyleneimine Substituents may be bonded to these ring portions, and Q ₂ represents a structure of the following formula (3-I) or (3-II): Formula (3-I), (3-II) In the formula, * ₁ represents a bond to Q ₁ and * 2 represents a bond to a benzene ring R ₁ in the formula (3-II) represents hydrogen or a monovalent organic group R ₂ , R ₃ is a monovalent organic group, and q and r are each independently an integer of 0 to 4. However, when the sum of q or r is 2 or more, R ₂ and R ₃ are each independently. Yes.)

(In the formula (4), D represents a divalent C 1 to C 20 saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocycle, and D has various substituents. M may be 1 or 0.
In Formula (5), E is a single bond or a divalent C1-C20 saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring. F represents a single bond, -O-, -OCO-, or COO-.
Wherein (6), _{A 1} represents a single ^{bond, -O -, - NQ 1 -} , - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one selected from the group consisting of OCO- Or an alkylene group having 1 to 3 carbon atoms. Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ₁₆ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.
In Formula (7), X ⁴ and X ⁸ are each independently a single bond, -CH _2- or -CH ₂ CH _2- . X ^{5, X 7} are each independently, -CH ₂ -, or _-CH 2 CH ₂ -. X ⁶ is C 1 -C 6 alkylene or cyclohexylene. Y ^{1 s} each independently represent a single bond, —O—, —NH—, —N (CH ₃ ) —, —C (= O) —, —C (= O) O— or —C (= O). _{) NH-, -C (= O)} N (CH 3) -, -OC (= O) -, -NHC (= O) -, or _{-N (CH 3) C (=} O) - it is. R ₁₇ is each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an t-butyl group, a t-butyl group, a benzyl group or a 9-fluorenyl group . a is 0 or 1; )

In Formula (8), R ⁸ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an alkyl group having 7 to 13 carbon atoms, or a 1,3-dioxobutyl group.
X ¹¹ is a single bond, a carbonyl group or * -CONH- (provided that the bond attached with “*” is bonded to a piperidine ring).
R ₆ , R ₇ , R ₉ and R ₁₀ each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 13 carbon atoms, provided that the above aryl The benzene ring which a group and an aralkyl group have may be substituted by a formyl group or a C1-C4 alkoxyl group.
X ⁹ , X ¹⁰ , X ¹² and X ¹³ each independently represent a single bond, a carbonyl group, * -CH ₂ -CO- or * -CH ₂ -CH (OH)-(where “*” is attached) The bond is bonded to the piperidine ring.
X ¹⁴ each independently represents a group represented by —O—, * —OCO— or the following formula (X ¹⁴ −1) (wherein the bond attached with “*” is represented by Formula (8) And a piperidine ring), a methylene group or an alkylene group having 2 to 6 carbon atoms. )

(In the formula (X ¹⁴ −1), a is an integer of 1 to 12. b is an integer of 0 to 5.)

(In formula (9), R ₁₁ represents hydrogen or a monovalent organic group. R ₁₂ each independently represents a single bond or a structure of the following formula (9-2): The hydrogen atom of may be substituted by a monovalent organic group, n is an integer of 1 to 3.)

(In the formula (9-2), R ₁₃ represents a single bond, —O—, —COO—, —OCO—, — (CH ₂ ) ₁ —, —O (CH ₂ ) _m O—, —CONH—, And -NHCO- represents a divalent organic group selected from the group consisting of (l and m each represents an integer of 1 to 5) * ₁ represents a site to be bonded to a benzene ring in the formula (9) * ₂ represents the site of bonding to the amino group in formula (9).) The liquid crystal aligning agent as described in any one of Claims 1-3 in which the said diamine component contains the diamine shown by following formula (10) or (11).

(In formula (10), Y ¹ is a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- is there.
Y ² is a single bond or (CH ₂ ) _b- (b is an integer of 1 to 15).
Y ³ represents a single _{bond, - (CH 2) c -} (c is an integer of _{1~15), - O -, -} CH 2 O -, - COO- or OCO-.
Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycle. Any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl having 1 to 3 carbon atoms It may be substituted by a group or a fluorine atom. Furthermore, Y ⁴ is a C12 to C25 divalent organic group having a steroid skeleton. As Y ⁴ , an organic group having 12 to 25 carbon atoms and having a benzene ring, a cyclohexyl ring or a steroid skeleton is preferable.
Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocycle. Any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl having 1 to 3 carbon atoms It may be substituted by a group or a fluorine atom.
n is an integer of 0 to 4;
Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
m is an integer of 1 to 4; )

(In the formula (11), Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene. They may be substituted with an organic group, and a hydrogen atom is replaced by a halogen atom. It is good.
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 in the case of an alkyl group or an alkoxy group, R ₁ and R ₂ form a ring May be
T ₁ and T ₂ each independently represent a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )- , -CON _(CH 3) -, or -N _(CH 3) a linking group CO-.
S is a single bond or unsubstituted or substituted or substituted by a fluorine atom, an alkylene group having 1 to 20 carbon atoms (with the proviso that -CH ₂ -or CF _{2-of the} alkylene group is optionally replaced by -CH = CH- And any of the following groups may be replaced by any of these groups if they are not adjacent to each other; -O-, -COO-, -OCO-, -NHCO-, -CONH-,- NH-, a divalent carbocyclic ring or a divalent heterocyclic ring)).
Q represents the following structure.

(Wherein each R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₃ represents -CH _2- , -NR-, -O- or S-.) The tetracarboxylic acid dianhydride component according to any one of claims 1 to 4, wherein the tetracarboxylic acid dianhydride component is at least one tetracarboxylic acid dianhydride selected from the group consisting of the following formulas (12) to (14): Liquid crystal aligning agent.

In the formula (12), Z ¹ is a tetravalent organic group having 4 to 13 carbon atoms, and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms. In 14), j and k are each independently 0 or 1. X and y are each independently a single bond, a carbonyl, an ester, a phenylene, a sulfonyl or an amido group.)   The liquid crystal aligning agent as described in any one of Claims 1-5 in which the said liquid crystal aligning agent contains polymers other than the said polyimide precursor, or polymers other than the polyimide which imidated this polyimide precursor.   The liquid crystal aligning agent according to any one of claims 1 to 6, wherein the liquid crystal aligning agent further comprises at least one selected from the group consisting of an adhesion assistant, a crosslinking agent, a dielectric, a conductive substance, and an organic solvent. . The liquid crystal aligning agent of Claim 7 whose said crosslinking agent is at least 1 compound chosen from following formula (17), Formula (19), and Formula (21).

(In formula (17), R ₂₀ , R ₂₁ , R ₂₅ and R ₂₆ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a carbon number 2 to 4 alkynyl groups, at least one of which is a group represented by formula (18) R ₂₂ and R ₂₄ each independently represent an aromatic ring, and any hydrogen atom of the aromatic ring is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group or a vinyl optionally substituted by a group .R ₂₃ of 1 to 3 carbon atoms are single bond, all or a part thereof bound It is a C1-C10 saturated hydrocarbon group which may form a cyclic structure.)

(Wherein R ₂₇ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, and c represents an integer of 2 to 6). ₂₈ and R ₂₉ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, and these groups are substituents In addition, at least one of R ₂₈ and R ₂₉ has a hydroxy group as a substituent, and at least one of R ₂₈ and R ₂₉ is a group represented by formula (20) It is preferable that R _{30 to} R _{33 be} each independently a hydrogen atom, a hydrocarbon group or a hydrocarbon group substituted with a hydroxy group in the formula (20).)

(In formula (21), R ₃₄ and R ₃₈ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₃₅ and R ₃₇ each independently represent an aromatic ring, and the aromatic any hydrogen atom in the ring, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, .R ₃₆ substituted with an alkoxy group or a vinyl group having 1 to 3 carbon atoms is a single bond, It is a C1-C10 saturated hydrocarbon group which may combine with all or one part and may form cyclic structure, and arbitrary hydrogen atoms may be substituted by the fluorine atom, -NH-, -N (CH ₃ ) — or a group represented by formula (22): In formula (22), P ₁ and P ₂ each independently represent an alkyl group having 1 to 5 carbon atoms, and Q ₁ is an aromatic ring And in the formula (21), d and f are each independently 1 to 3 Is a number, e, and g are each independently 1 to 3 integers. ) The liquid crystal aligning agent according to claim 8, wherein the crosslinking agent is at least one compound selected from the group consisting of the following formulas CL-1 to CL-3.

  A liquid crystal display device comprising a BOA substrate or a substrate with BCS on which a liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1 to 9 is formed.   The manufacturing method of the liquid crystal aligning film on a BOA board | substrate or a board | substrate with BCS which apply | coats the liquid crystal aligning agent as described in any one of Claims 1-9 on a BOA board | substrate or a board | substrate with BCS.   A liquid crystal display device comprising: a BOA substrate or a substrate with BCS; and a liquid crystal alignment film formed on the BOA substrate or the substrate with BCS using the liquid crystal alignment agent according to any one of claims 1 to 9. Board.