JP5614284B2 - Diamine, polyimide, liquid crystal aligning agent and liquid crystal aligning film - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent for producing a liquid crystal aligning film, a liquid crystal aligning film obtained from this liquid crystal aligning agent, and a polymer (polymer) and a monomer (monomer) for obtaining this liquid crystal aligning agent. More specifically, a liquid crystal alignment film with excellent mechanical strength that is resistant to rubbing scratches even after rubbing treatment, high voltage retention at high temperature, low ion density, and excellent reliability It is related with the liquid crystal aligning agent from which an element is obtained, and the polymer and monomer for obtaining this liquid crystal aligning agent.

  In a liquid crystal display element used for a liquid crystal television, a liquid crystal display, and the like, a liquid crystal alignment film for controlling the alignment state of liquid crystals is usually provided in the element. The liquid crystal alignment film is imparted with liquid crystal alignment by subjecting the surface of the film to various alignment treatments. At present, according to the most widespread industrial method, the liquid crystal alignment film is a so-called rubbing process in which the surface of the resin film formed on the electrode substrate is rubbed in one direction with a cloth such as cotton, nylon or polyester. It is produced by doing. As the resin film, a polyimide film obtained by applying and baking a polyimide precursor such as polyamic acid or a polyimide solution is widely used.

  The method of rubbing the polyimide film is an industrially useful method that is simple and excellent in productivity. However, when the adhesion and mechanical strength of the polyimide film formed on the electrode substrate are insufficient, the film is peeled or scratched by rubbing due to the rubbing treatment.

  As a method for suppressing the occurrence of film peeling and scratches due to such rubbing, a method using a liquid crystal aligning agent in which a compound containing an epoxy group is added to polyamic acid or polyimide (see Patent Document 1), polyamic acid or polyimide A method using a liquid crystal aligning agent in which an epoxy compound containing a nitrogen atom is added to a solution (see Patent Documents 2 and 3), a compound containing a reactive group other than an epoxy group and an epoxy group is added to a polyamic acid or polyimide solution A method using a liquid crystal aligning agent (see Patent Document 4) has been proposed.

  Thus, the mechanical strength of a polyimide film improves by adding the crosslinking agent containing reactive groups, such as an epoxy group, to a polyimide precursor or a polyimide. This originates from the reaction of a polar group such as a carboxylic acid present in a polyimide precursor or polyimide with an epoxy group.

JP-A-9-146100 JP 10-333153 A Japanese Patent Laid-Open No. 10-46151 Japanese Patent Laid-Open No. 2007-11221

  Usually, the compound used as a crosslinking agent is a low molecular compound. Therefore, it sublimes during firing, and the effect cannot be sufficiently obtained unless an excessive amount is added. Moreover, when it adds excessively, an unreacted crosslinking agent remains in a film | membrane, and when it is set as a liquid crystal display element, a voltage holding rate and an ion density may be deteriorated, and a favorable display may not be obtained.

  The present invention has been made in view of such circumstances, and a liquid crystal alignment film excellent in mechanical strength that is difficult to be subjected to rubbing scratches even by rubbing treatment without the addition of a crosslinking agent can be obtained, and at a high temperature. However, it is an object to provide a liquid crystal aligning agent capable of obtaining a highly reliable liquid crystal alignment film having a high voltage holding ratio of a liquid crystal display element and a low ion density, and a polymer and a monomer for obtaining the liquid crystal aligning agent. And

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have obtained a diamine compound and / or a tetracarboxylic acid derivative having a t-butoxycarbonyl group (hereinafter also referred to as a Boc group) that is eliminated by heating. It has been found that the above object can be achieved by a polyimide precursor obtained by using a liquid crystal or a liquid crystal aligning agent containing polyimide. Specifically, the Boc group is eliminated by heating, and a highly reactive aliphatic amine is formed. This aliphatic amine becomes a cross-linking point, and the liquid crystal has excellent mechanical properties that do not cause film peeling or scratching due to rubbing. An alignment film was obtained, and a liquid crystal display device using this liquid crystal alignment film was found to have a high voltage holding ratio and a low ion density even at high temperatures, and the present invention was completed.

That is, the gist of the present invention is as follows.
1. The liquid crystal aligning agent characterized by containing the polyimide precursor which has a substituent of the structure represented by following formula (1), or the imidation polymer of this polyimide precursor.

（式中、Ａは単結合又は２価の有機基であり、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素原子又は炭素数１〜２０の１価の有機基である。）
２．ポリイミド前駆体又は該ポリイミド前駆体のイミド化重合体が、式（１）で表される置換基を有するジアミン化合物及び式（１）で表される置換基を有するテトラカルボン酸誘導体からなる群から選ばれる少なくとも１つを用いて得られる上記１に記載の液晶配向剤。
３．式（１）で表される置換基を有するジアミン化合物及び／又は式（１）で表される置換基を有するテトラカルボン酸誘導体を、全ジアミン化合物及びテトラカルボン酸誘導体の２〜１００モル％を用いて得られるポリイミド前駆体又は該ポリイミド前駆体のイミド化重合体である上記２に記載の液晶配向剤。
４．ポリイミド前駆体が、下記式（２）の構造単位を含有する構造である上記１〜３のいずれかに記載の液晶配向剤。

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.)
2. The polyimide precursor or the imidized polymer of the polyimide precursor is selected from the group consisting of a diamine compound having a substituent represented by the formula (1) and a tetracarboxylic acid derivative having a substituent represented by the formula (1). 2. The liquid crystal aligning agent according to 1 above, which is obtained using at least one selected.
3. A diamine compound having a substituent represented by the formula (1) and / or a tetracarboxylic acid derivative having a substituent represented by the formula (1) is added in an amount of 2 to 100 mol% of the total diamine compound and the tetracarboxylic acid derivative. 3. The liquid crystal aligning agent according to 2 above, which is a polyimide precursor obtained by use or an imidized polymer of the polyimide precursor.
4). The liquid crystal aligning agent in any one of said 1-3 whose polyimide precursor is a structure containing the structural unit of following formula (2).

（式中、Ｘ_１は（４＋ａ）価の有機基であり、Ｙ_１は（２＋ｂ）価の有機基であり、Ｒ_４は水素原子又は炭素数１〜４のアルキル基であり、Ｚは上記式（１）で表される構造である。ａ及びｂは、それぞれ０〜４の整数であって、ａ＋ｂ＞０である。）
５．ポリイミド前駆体が、下記式（３）の構造単位を含有する構造である上記１〜３のいずれかに記載の液晶配向剤。

Wherein X ₁ is a (4 + a) valent organic group, Y ₁ is a (2 + b) valent organic group, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is the above (It is a structure represented by Formula (1). A and b are integers of 0-4, respectively, and a + b> 0.)
5. The liquid crystal aligning agent in any one of said 1-3 whose polyimide precursor is a structure containing the structural unit of following formula (3).

（式中、Ｘは４価の有機基であり、Ｙ_２は（２＋ｃ）価の有機基であり、Ｒ_４は水素原子又は炭素数１〜４のアルキル基であり、Ｚは上記式（１）で表される構造である。ｃは、１〜４の整数である。）
６．ポリイミド前駆体が、下記式（４）で表される構造単位を含有する構造である上記１〜３のいずれかに記載の液晶配向剤。

(Wherein X is a tetravalent organic group, Y ₂ is a (2 + c) valent organic group, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is the formula (1 And c is an integer of 1 to 4.)
6). The liquid crystal aligning agent in any one of said 1-3 whose polyimide precursor is a structure containing the structural unit represented by following formula (4).

（式中、Ｘは４価の有機基であり、Ｒ_４は水素原子又は炭素数１〜４のアルキル基であり、Ｒ_５は単結合又は炭素数１〜２０の２価の有機基であり、Ｚは上記式（１）で表される構造である。ｃは、１〜４の整数である。）
７．ポリイミド前駆体が、下記式（５）で表される構造単位を含有する構造である上記１〜３のいずれかに記載の液晶配向剤。

(In the formula, X is a tetravalent organic group, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ is a single bond or a divalent organic group having 1 to 20 carbon atoms. Z is a structure represented by the above formula (1), c is an integer of 1 to 4.)
7). The liquid crystal aligning agent in any one of said 1-3 whose polyimide precursor is a structure containing the structural unit represented by following formula (5).

（式中、Ｘは４価の有機基であり、Ｒ_４は水素原子又は炭素数１〜４のアルキル基であり、Ｚは上記式（１）で表される構造である。ｃは、１〜４の整数である。）
８．上記１〜７のいずれかに記載の液晶配向剤を１５０〜３００℃にて焼成して得られる液晶配向膜。
９．下記式（６）で表される構造単位を含有するポリイミド前駆体。

(In the formula, X is a tetravalent organic group, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is a structure represented by the above formula (1). It is an integer of ~ 4.)
8). The liquid crystal aligning film obtained by baking the liquid crystal aligning agent in any one of said 1-7 at 150-300 degreeC.
9. The polyimide precursor containing the structural unit represented by following formula (6).

（式中、Ｘは４価の有機基であり、Ｙ_２は（２＋ｃ）価の有機基であり、Ｚは下記式（１）で表される構造であり、Ｒ_４は水素原子又は炭素数１〜４のアルキル基である。ｃは、１〜４の整数である。）

(Wherein X is a tetravalent organic group, Y ₂ is a (2 + c) valent organic group, Z is a structure represented by the following formula (1), and R ₄ is a hydrogen atom or a carbon number. (It is an alkyl group of 1-4. C is an integer of 1-4.)

（式中、Ａは単結合又は２価の有機基であり、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素原子又は炭素数１〜２０の１価の有機基である。）
１０．下記式（７）で表される構造単位を含有するポリイミド。

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.)
10. Polyimide containing a structural unit represented by the following formula (7).

（式中、Ｘは４価の有機基であり、Ｙ_２は（２＋ｃ）価の有機基であり、Ｚは下記式（１）で表される構造である。ｃは、１〜４の整数である。）

(In the formula, X is a tetravalent organic group, Y ₂ is a (2 + c) valent organic group, and Z is a structure represented by the following formula (1). C is an integer of 1 to 4. .)

（式中、Ａは単結合又は２価の有機基であり、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素原子又は炭素数１〜２０の１価の有機基である。）
１１．下記式（８）で表される構造単位を含有するポリイミド前駆体。

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.)
11. The polyimide precursor containing the structural unit represented by following formula (8).

（式中、Ｘは４価の有機基であり、Ｚは下記式（１）で表される構造であり、Ｒ_４は水素原子又は炭素数１〜４のアルキル基であり、Ｒ_５は炭素数１〜２０の２価の有機基である。ｃは、１〜４の整数である。）

(In the formula, X is a tetravalent organic group, Z is a structure represented by the following formula (1), R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ is carbon. (It is a divalent organic group having a number of 1 to 20. c is an integer of 1 to 4.)

（式中、Ａは単結合又は２価の有機基であり、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素原子又は炭素数１〜２０の１価の有機基である。）
１２．下記式（９）で表される構造単位を含有するポリイミド。

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.)
12 The polyimide containing the structural unit represented by following formula (9).

（式中、Ｘは４価の有機基であり、Ｚは下記式（１）で表される構造であり、Ｒ_５は炭素数１〜２０の２価の有機基である。ｃは、１〜４の整数である。）

(In the formula, X is a tetravalent organic group, Z is a structure represented by the following formula (1), R ₅ is a divalent organic group having 1 to 20 carbon atoms, c is 1 It is an integer of ~ 4.)

（式中、Ａは単結合又は２価の有機基であり、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素原子又は炭素数１〜２０の１価の有機基である。）
１３．下記式（１０）で表される構造単位を含有するポリイミド前駆体。

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.)
13. The polyimide precursor containing the structural unit represented by following formula (10).

（式中、Ｘは４価の有機基であり、Ｚは下記式（１）で表される構造であり、Ｒ_４は水素原子又は炭素数１〜４のアルキル基である。ｃは、１〜４の整数である。）

(In the formula, X is a tetravalent organic group, Z is a structure represented by the following formula (1), R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is an integer of ~ 4.)

（式中、Ａは単結合又は２価の有機基であり、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素原子又は炭素数１〜２０の１価の有機基である。）
１４．下記式（１１）で表される構造単位を含有するポリイミド。

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.)
14 A polyimide containing a structural unit represented by the following formula (11).

（式中、Ｘは４価の有機基であり、Ｚは下記式（１）で表される構造である。ｃは、１〜４の整数である。）

(In the formula, X is a tetravalent organic group, Z is a structure represented by the following formula (1), and c is an integer of 1 to 4.)

（式中、Ａは単結合又は２価の有機基であり、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素原子又は炭素数１〜２０の１価の有機基である。）

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. )

  According to the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal aligning film excellent in mechanical strength that hardly causes peeling or scratching of the film due to rubbing without adding a crosslinking agent. By using this liquid crystal alignment film, even when liquid crystal alignment ability is imparted by irradiating polarized radiation, the liquid crystal display has excellent display characteristics because of high voltage retention at low temperatures and low ion density. An element is obtained.

  Since the highly reactive primary or secondary aliphatic amine is protected with a Boc group, the liquid crystal aligning agent of the present invention has high storage stability in a varnish state. Moreover, since the polyimide precursor and polyimide contained in the liquid crystal aligning agent of this invention have a Boc group which is a bulky substituent, they show high solubility with respect to various organic solvents, and also are reactive by heating. High-grade primary or secondary aliphatic amines are produced, and intermolecular crosslinking reaction is advanced to form a polyimide film having excellent mechanical strength.

  In addition, the diamine compound protected with a Boc group in the present invention is easily produced by reacting with a tetracarboxylic acid derivative to produce a polyimide precursor or polyimide having a primary or secondary amino group protected with a Boc group. can do.

The liquid crystal aligning agent of the present invention is characterized by containing a polyimide precursor having a primary or secondary aliphatic amino group protected with a Boc group or an imidized polymer thereof. Here, the primary or secondary aliphatic amino group protected by the Boc group means an aliphatic amino group having —NR ₃ Boc (R ₃ is defined by the above formula (1)).

  A polyimide precursor having a primary or secondary aliphatic amino group protected with a Boc group or an imidized polymer thereof is heated at 150 ° C. or more, whereby the Boc group is released and the protection of the Boc group is lost. Reactive primary or secondary aliphatic amino groups are formed. The generated primary or secondary aliphatic amino group reacts with a functional group present in the polyimide precursor or its imidized polymer to form intermolecular crosslinks. Examples of crosslinking reactions include reactions with carboxylic acids or esters (following formula (i)), reactions with acid dianhydrides generated by the reverse reaction of polyamic acids (following formula (ii)), and reactions with imides. (The following formula (iii)).

  The above cross-linking reaction proceeds in the process of forming a liquid crystal alignment film from the liquid crystal aligning agent of the present invention, so that the liquid crystal alignment film obtained in the present invention has improved mechanical strength, It is considered that a polyimide film that does not cause scratches is obtained.

  As a method for imparting liquid crystal alignment ability to the liquid crystal alignment film, in addition to the rubbing method, a photo-alignment method for imparting liquid crystal alignment ability by irradiating a polyimide film with polarized radiation is known. As the photo-alignment method, a method using a photoisomerization reaction, a method using a photocrosslinking reaction, a method using a photolysis reaction, and the like have been proposed.

  The liquid crystal aligning agent and liquid crystal aligning film of the present invention are also useful for the photo-alignment method, and are particularly useful for the photo-alignment method using a photodecomposition reaction. In the photo-alignment method using a photolysis reaction, a low molecular weight component is generated by light irradiation. For example, in a photo-alignment method using a photodecomposition reaction of a polyimide having a cyclobutane ring in the main chain, a low molecular weight component having a maleimide moiety is generated by performing an alignment treatment (the following formula (xiii)). When such a liquid crystal alignment film containing a low molecular weight component is used in a liquid crystal display device, the low molecular weight component is eluted into the liquid crystal, causing a decrease in the voltage holding ratio and an increase in ion density of the liquid crystal display device. There is a possibility of deteriorating the display characteristics of the element.

The liquid crystal aligning agent and liquid crystal aligning film of the present invention suppress the lowering of the molecular weight of the polyimide precursor and polyimide by intermolecular three-dimensional crosslinking formed by the reactions of the above formulas (i) to (iii), and into the liquid crystal. It is possible to suppress elution of low molecular weight components.
Furthermore, the maleimide produced by the photolysis reaction of the cyclobutane ring can react with a primary or secondary aliphatic amino group produced by heating (the following formula (xiv)). Even in such a crosslinking reaction, it is possible to suppress elution of low molecular weight components into the liquid crystal. Due to the progress of these cross-linking reactions, even when a liquid crystal alignment film provided with liquid crystal alignment ability by a photo-alignment method is used for a liquid crystal display element, the voltage holding ratio is high even at high temperatures, the ion density is low, and the display characteristics are excellent. It is considered that a liquid crystal display element can be obtained.

  On the other hand, also by adding a compound having two or more primary or secondary aliphatic amines to the polyimide precursor or the polyimide solution, the crosslinking reaction as described above proceeds and intermolecular crosslinking is formed. However, when a primary or secondary aliphatic amine is added to a polyimide precursor or polyimide solution, salt formation with carboxylic acid, progress of imidization reaction, ring-opening reaction of imide ring, etc. proceed, and polymer Gelation, precipitation, and molecular weight reduction occur, and it is difficult to stably store the polymer solution for a long period of time. On the other hand, since the primary or secondary aliphatic amino group is protected by the Boc group in the liquid crystal aligning agent of the present invention, the functional group in the polymer is stored when the liquid crystal aligning agent is stored in a solution state. The liquid crystal aligning agent excellent in storage stability is obtained.

  In addition, when a low molecular crosslinking agent is used, the low molecular crosslinking agent sublimes during firing in the process of forming the liquid crystal alignment film, and the effect may not be sufficiently obtained unless an excessive amount is added. is there. Moreover, when it adds excessively, an unreacted crosslinking agent remains in a film | membrane, and when it is set as a liquid crystal display element, a voltage holding rate and an ion density may be deteriorated, and a favorable display may not be obtained. Further, the sublimated crosslinking agent may contaminate the firing furnace. On the other hand, in the liquid crystal aligning agent of the present invention, since the aliphatic amine serving as a crosslinking point is incorporated in the polymer, the low-molecular compound remains in the film without being reacted, or the sublimation product is a firing furnace. Will not contaminate.

  From the above, by using the liquid crystal aligning agent of the present invention, a liquid crystal aligning film excellent in mechanical strength that does not cause peeling or scratching of the film by rubbing can be obtained, and by using this liquid crystal aligning film, alignment can be achieved. Regardless of the treatment method, a liquid crystal display element having a high voltage holding ratio and a low ion density even at high temperatures can be obtained. Furthermore, the present inventors have found that a liquid crystal aligning agent having excellent storage stability can be obtained by protecting a primary or secondary aliphatic amino group serving as a crosslinking point with a Boc group.

Hereinafter, the present invention will be described in more detail.
a. [Polyimide precursor and polyimide]
The polyimide precursor in the present invention is a polymer that becomes a polyimide by heating or the action of a catalyst, and examples thereof include polyamic acid, polyamic acid ester, polyamic acid silyl ester, and polyisoimide. As the polyimide precursor, polyamic acid or polyamic acid ester is particularly preferable from the viewpoint of ease of production and imidization reaction efficiency. The polyimide in the present invention is a polymer obtained by imidizing a polyimide precursor.

  The liquid crystal aligning agent of this invention contains the polyimide precursor which has a substituent represented by following formula (1), or its imidation polymer.

In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a carbon number of 1 to 20, preferably 1 to 10, more preferably 1 to 1. 6 is a monovalent organic group. Monovalent organic groups include monovalent hydrocarbon groups, hydroxyl groups, thiol groups, phosphate ester groups, ester groups, carboxyl groups, phosphate groups, thioester groups, amide groups, nitro groups, organooxy groups, organosilyl groups. Group, organothio group, acyl group and the like. The monovalent organic group is preferably a monovalent hydrocarbon group from the viewpoint of the reactivity of the aliphatic amine. Specific examples of monovalent hydrocarbon groups include methyl groups, ethyl groups, propyl groups, butyl groups, t-butyl groups, hexyl groups, octyl groups, decyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups, and the like. A bicycloalkyl group such as a bicyclohexyl group; a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-2-propenyl group, 1 or 2 or 3-butenyl group, hexenyl An alkenyl group such as a group; an aryl group such as a phenyl group, a xylyl group, a tolyl group, a biphenyl group and a naphthyl group; and an aralkyl group such as a benzyl group, a phenylethyl group and a phenylcyclohexyl group.
Some or all of the hydrogen atoms of these monovalent hydrocarbon groups are halogen atoms, hydroxyl groups, thiol groups, phosphate ester groups, ester groups, carboxyl groups, phosphate groups, thioester groups, amide groups, nitro groups, Group, organooxy group, organosilyl group, organothio group, acyl group, alkyl group, cycloalkyl group, bicycloalkyl group, alkenyl group, aryl group, aralkyl group, pyrrole group, imidazole group, pyrazole group, alkoxycarbonylamino group, etc. May be substituted. In addition, these may have a ring structure. Among these, a pyrrole group, an imidazole group, and a pyrazole group are preferable, and a case where the hydrogen atom on the nitrogen atom of the pyrrole group, the imidazole group, and the pyrazole group is substituted with a Boc group is more preferable.

When R ₁ and R ₂ have a bulky structure, the reaction efficiency of the crosslinking reaction is lowered. Therefore, as R ₁ and R ₂ , an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a hydrogen atom Preferably, a hydrogen atom is more preferable.
When R ₃ has a bulky structure, the reaction efficiency of the cross-linking reaction decreases. Therefore, R ₃ is preferably an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a hydrogen atom, and more preferably a hydrogen atom. preferable.
When A is a divalent organic group, the structure is represented by the following formula (12), for example.

式（１２）中、Ｂは２価の連結基であり、Ｒ_６及びＲ_１６はそれぞれ独立して単結合又は炭素数１〜２０、好ましくは１〜１０の２価の炭化水素基である。Ｂの具体的な例としては下記Ｂ−１〜Ｂ−１４が挙げられるが、これに限定されない。

In formula (12), B is a divalent linking group, and R ₆ and R ₁₆ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of B include the following B-1 to B-14, but are not limited thereto.

Specific examples of R ₆ and R _{16 in} formula (12) are shown below, but are not limited thereto. Methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-butylene group, 1,2-pentylene Group, 1,2-hexylene group, 1,2-nonylene group, 1,2-dodecylene group, 2,3-butylene group, alkylene group such as 2,4-pentylene group; 1,2-cyclopropylene group, Cycloalkylene such as 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, 1,2-cyclononylene group, 1,2-cyclododecylene Group: 1,1-ethenylene group, 1,2-ethenylene group, 1,2-ethenylenemethylene group, 1-methyl-1,2-ethenylene group, 1,2-ethenylene-1,1-ethylene group, 1 , 2-Ethenylene-1,2- Tylene group, 1,2-ethenylene-1,2-propylene group, 1,2-ethenylene-1,3-propylene group, 1,2-ethenylene-1,4-butylene group, 1,2-ethenylene-1, Alkenylene groups such as 2-butylene group, 1,2-ethenylene-1,2-heptylene group, 1,2-ethenylene-1,2-decylene group; ethynylene group, ethynylenemethylene group, ethynylene-1,1-ethylene Group, ethynylene-1,2-ethylene group, ethynylene-1,2-propylene group, ethynylene-1,3-propylene group, ethynylene-1,4-butylene group, ethynylene-1,2-butylene group, ethynylene-1 , 2-heptylene group, ethynylene-1,2-decylene group and other alkynylene groups; 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2- Butylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,3-naphthylene group, 2,6-naphthylene group, 3-phenyl-1,2-phenylene group, 2,2′-diphenylene group, Arylene groups such as 2,2′-dinaphth-1,1′-yl group; 1,2-phenylenemethylene group, 1,3-phenylenemethylene group, 1,4-phenylenemethylene group, 1,2-phenylene-1 , 1-ethylene group, 1,2-phenylene-1,2-ethylene group, 1,2-phenylene-1,2-propylene group, 1,2-phenylene-1,3-propylene group, 1,2-phenylene -1,4-butylene group, 1,2-phenylene-1,2-butylene group, 1,2-phenylene-1,2-hexylene group, methylene-1,2-phenylenemethylene group, methylene-1,3- Phenylenemethylene group And a bifunctional hydrocarbon group composed of an arylene group such as methylene-1,4-phenylenemethylene group and an alkylene group.

  In addition, a part or all of the hydrogen atoms of the divalent hydrocarbon group may be a halogen atom, a hydroxyl group, a thiol group, a phosphate ester group, an ester group, a carboxyl group, a phosphate group, a thioester group, an amide group, or a nitro group. , An organooxy group, an organosilyl group, an organothio group, an acyl group, an alkyl group, a cycloalkyl group, a bicycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, and the like. In addition, these may have a ring structure.

If R ₆ and R ₁₆ have a structure containing an aromatic ring or an alicyclic structure, the liquid crystal orientation may be lowered. Therefore, R ₆ and R ₁₆ are a single bond or an alkylene group having 1 to 10 carbon atoms, an alkenyl group. Group or an alkynyl group is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable. Moreover, it is preferable that both or one of R ₆ and R ₁₆ is a single bond.

In the structure represented by B-1 to B-14, R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ are each independently a hydrogen atom or a monovalent hydrocarbon having 1 to 20 carbon atoms. It is a group. Here, the monovalent hydrocarbon group is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group or a decyl group; a cycloalkyl such as a cyclopentyl group or a cyclohexyl group. Groups; bicycloalkyl groups such as bicyclohexyl groups; vinyl groups, 1-propenyl groups, 2-propenyl groups, isopropenyl groups, 1-methyl-2-propenyl groups, 1 or 2 or 3-butenyl groups, hexenyl groups, etc. Examples include alkenyl groups; aryl groups such as phenyl, xylyl, tolyl, biphenyl, and naphthyl groups; and aralkyl groups such as benzyl, phenylethyl, and phenylcyclohexyl.

  Some or all of the hydrogen atoms of these monovalent hydrocarbon groups are halogen atoms, hydroxyl groups, thiol groups, phosphate ester groups, ester groups, carboxyl groups, phosphate groups, thioester groups, amide groups, nitro groups, Group, organooxy group, organosilyl group, organothio group, acyl group, alkyl group, cycloalkyl group, bicycloalkyl group, alkenyl group, aryl group, aralkyl group and the like may be substituted. In addition, these may have a ring structure.

If R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ have a bulky structure such as an aromatic ring or an alicyclic structure, the liquid crystal orientation may be lowered or the solubility of the polymer may be lowered. Therefore, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a hydrogen atom is preferable, and a hydrogen atom is more preferable.
From the above, specific examples of the substituent containing the primary or secondary aliphatic amine protected by the Boc group represented by the formula (1) include structures of the following formulas (13) to (18). Is particularly preferred.

  The liquid crystal aligning agent of this invention contains the polyimide precursor which has the substituent represented by the said Formula (1) in the terminal of a polymer, or a polymer side chain, or its imidized polymer. The structural unit represented by the following formula (2) in which the substituent represented by the above formula (1) is introduced into the side chain of the polymer because the introduction amount of the substituent of the above formula (1) is easy to control. It is preferable that it is the polyimide precursor which has, and its imidation polymer.

（式中、Ｘ_１は（４＋ａ）価の有機基であり、Ｙ_１は（２＋ｂ）価の有機基であり、Ｒ_４は水素原子又は炭素数１〜４のアルキル基であり、Ｚは上記式（１）で表される構造である。ａ及びｂは、それぞれ０〜４、好ましくは０〜２の整数であって、ａ＋ｂ＞０である。）
上記式（２）のポリイミド前駆体及びそのイミド化重合体を製造する方法としては、ポリイミド前駆体の原料であるテトラカルボン酸誘導体及びジアミン化合物に、上記式（１）で表される置換基を導入した原料を用いることが好ましい。具体的には、下記式（１９）〜（２１）で表されるテトラカルボン酸誘導体及び下記式（２２）で表されるジアミン化合物を用いることが好ましい。

Wherein X ₁ is a (4 + a) valent organic group, Y ₁ is a (2 + b) valent organic group, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is the above (It is a structure represented by Formula (1). A and b are each an integer of 0-4, preferably 0-2, and a + b> 0.)
As a method for producing the polyimide precursor of the above formula (2) and the imidized polymer thereof, the substituent represented by the above formula (1) is added to the tetracarboxylic acid derivative and the diamine compound which are raw materials of the polyimide precursor. It is preferable to use the introduced raw material. Specifically, it is preferable to use a tetracarboxylic acid derivative represented by the following formulas (19) to (21) and a diamine compound represented by the following formula (22).

上記式（１９）〜（２１）において、Ｒ_４は炭素数１〜４のアルキル基である。アルキル基の具体的な例としては、メチル基、エチル基、プロピル基、２−プロピル基、ブチル基、ｔ−ブチル基が挙げられる。ポリアミック酸エステルは、アルキル基における炭素数が増えるに従ってイミド化が進行する温度が高くなるので、Ｒ_４は、熱によるイミド化のしやすさの観点から、メチル基又はエチル基が好ましく、メチル基が特に好ましい。Ｚは上記式（１）で表される構造を有する置換基であり、ａは０〜４の整数である。Ｘ_１は（４＋ａ）価の有機基である。

In the above formulas (19) to (21), R ₄ is an alkyl group having 1 to ₄ carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 2-propyl group, a butyl group, and a t-butyl group. The polyamic acid ester has a higher temperature at which imidization proceeds as the number of carbon atoms in the alkyl group increases. Therefore, R ₄ is preferably a methyl group or an ethyl group from the viewpoint of easiness of imidization by heat. Is particularly preferred. Z is a substituent having a structure represented by the above formula (1), and a is an integer of 0-4. X ₁ is a (4 + a) valent organic group.

上記式（２２）において、Ｚは上記式（１）で表される構造を有する置換基であり、ｂは０〜４の整数である。Ｙ_１は（２＋ｂ）価の有機基である。

In the above formula (22), Z is a substituent having a structure represented by the above formula (1), and b is an integer of 0-4. Y ₁ is a (2 + b) -valent organic group.

  In the present invention, together with the tetracarboxylic acid derivative represented by the above formulas (19) to (21) and the diamine compound represented by the above formula (22), the tetra represented by the following formulas (23) to (25) Using a carboxylic acid derivative and a diamine compound represented by the following formula (26), mixing these at an arbitrary ratio, and producing a polyimide precursor, containing a structural unit represented by the above formula (2) The polyimide precursor to be manufactured can be manufactured.

上記式（２３）〜（２５）において、Ｘ、Ｒ_４は、それぞれの好ましい例も含めて式（１９）〜（２１）の場合と同じである。

In the above formulas (23) to (25), X and R ₄ are the same as those in formulas (19) to (21) including preferred examples.

上記式（２６）において、Ｙは２価の有機基である。
上記式（１９）〜（２１）及び上記式（２３）〜（２５）において、Ｘ及びＸ_１の構造は特に限定されるものではない。その具体例を挙げるならば、下記Ｘ−１〜Ｘ−４６で表される構造が挙げられる。また、これらのテトラカルボン酸誘導体は２種類以上使用してもよい。
ただし、上記式（１９）〜（２１）においては、Ｚの置換数であるａによって、Ｘ_１の価数が変化する。すなわち、Ｚの置換数だけ、下記Ｘ−１〜Ｘ−４６で表される構造の任意の位置から水素原子を取り除いた構造がＸ_１の構造である。

In the above formula (26), Y is a divalent organic group.
In the above formulas (19) to (21) and the above formulas (23) to (25), the structures of X and X ₁ are not particularly limited. If the specific example is given, the structure represented by the following X-1 to X-46 will be mentioned. Two or more of these tetracarboxylic acid derivatives may be used.
However, in the above formulas (19) to (21), the valence of X ₁ varies depending on a which is the number of substitution of Z. That is, the substitution number of Z by a structure structure obtained by removing a hydrogen atom from an arbitrary position of X ₁ of the structures represented by the following X-1~X-46.

In the above formula (22) and the above formula (26), the structures of Y and Y ₁ are not particularly limited. If the specific example is given, the structure represented by following Y-1-Y-100 will be mentioned. Two or more diamine compounds may be used.
However, in the above formula (22), the valence of Y ₁ varies depending on the substitution number b (b = 0 to 4) of Z. That is, the substitution number of Z only structure obtained by removing a hydrogen atom from any position of the structure represented by the following Y-1 to Y-100 has the structure of Y _1.

本発明では、上記式（２）において、置換基Ｚは、テトラカルボン酸誘導体又はジアミン部位のどちらかに１つ以上に存在していればよい。
製造の容易さ及び単量体の扱いやすさの観点から上記式（２２）で表されるジアミン化合物を用いることが好ましい。本発明のポリイミド前駆体及びポリイミドとしては、下記式（３）で表される構造単位を含有するポリイミド前駆体、及び下記式（７）で表される構造単位を含有するポリイミドが好ましい。

In the present invention, in the above formula (2), the substituent Z may be present in one or more of either the tetracarboxylic acid derivative or the diamine moiety.
It is preferable to use the diamine compound represented by the above formula (22) from the viewpoint of ease of production and ease of handling of the monomer. The polyimide precursor and polyimide of the present invention are preferably a polyimide precursor containing a structural unit represented by the following formula (3) and a polyimide containing a structural unit represented by the following formula (7).

式（３）中、Ｘは４価の有機基であり、Ｙ_２は（２＋ｃ）価の有機基であり、Ｒ_４は水素原子又は炭素数１〜４のアルキル基である。Ｚは上記式（１）で表される構造である。ｃは、１〜４、好ましくは１〜２の整数である。

In Formula (3), X is a tetravalent organic group, Y ₂ is a (2 + c) valent organic group, and R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z is a structure represented by the above formula (1). c is an integer of 1-4, preferably 1-2.

式（７）における、Ｘ、Ｙ_２、Ｚ、ｃは、上記式（３）の場合と同じ意味である。
上記式（３）及び（７）の構造単位を含有するポリイミド前駆体又はポリイミドは、上記式（２３）〜（２５）で表されるテトラカルボン酸誘導体及び下記式（２７）で表されるジアミン化合物と上記式（２６）で表されるジアミン化合物を任意の割合で混合し、反応することで製造される。

In the formula (7), X, Y _2, Z, and c have the same meaning as in the above formula (3).
The polyimide precursor or polyimide containing the structural units of the above formulas (3) and (7) is a tetracarboxylic acid derivative represented by the above formulas (23) to (25) and a diamine represented by the following formula (27). The compound and the diamine compound represented by the above formula (26) are mixed at an arbitrary ratio and reacted.

式（２７）中、Ｙ_２、Ｚ、ｃは、上記式（３）及び（７）の場合と同じ意味である。Ｙ_２で表される構造の具体例を挙げるとするならば、前記のＹ−１〜Ｙ−１００で表される構造が挙げられる。また、ジアミン化合物は２種類以上であってもよい。
ただし、上記式（２７）においては、Ｚの置換数ｃによって、Ｙ_２の価数が変化する。すなわち、Ｚの置換数だけ、Ｙ−１〜Ｙ−１００で表される構造の任意の位置から水素原子を取り除いた構造がＹ_２の構造である。

In formula (27), Y ₂ , Z, and c have the same meanings as in the above formulas (3) and (7). If the specific examples of structures represented by Y _2, the structure represented by the Y-1 to Y-100 and the like. Two or more diamine compounds may be used.
However, in the above formula (27), the valence of Y ₂ changes depending on the substitution number c of Z. That is, the substitution number of Z only structure obtained by removing a hydrogen atom from any position of the structure represented by Y-1 to Y-100 has the structure of Y _2.

  A polyimide precursor obtained by using a diamine compound that does not contain a bulky side chain such as biphenyl, cyclohexyl, steroid, a long-chain alkyl group having 10 or more carbon atoms, or a fluoroalkyl group, and that contains an aromatic amino group When the body or polyimide is used, a liquid crystal alignment film having good liquid crystal alignment properties and excellent mechanical properties can be obtained. As a liquid crystal aligning agent of invention, it is preferable to contain the polyimide precursor containing the structural unit represented by following formula (4), or the polyimide containing the structural unit represented by following formula (9).

（式中、Ｘ、Ｒ_４、Ｚ及びｃは、上記式（３)の場合と同じ意味を表わし、Ｒ_５は単結合又は芳香族基を有する２価の有機基である。）

(In the formula, X, R ₄ , Z and c represent the same meaning as in formula (3) above, and R ₅ is a divalent organic group having a single bond or an aromatic group.)

（式中、Ｘ、Ｚ、Ｒ_５及びｃは、上記式（４）の場合と同じ意味を表わす。）
本発明においては、得られる重合体の直線性が高いほどより良好な液晶配向性を有する液晶配向膜が得られるので、置換基Ｚを含有するジアミン化合物としては、下記式（２８）〜（４４）及び下記式（５８）〜（６１）で表されるジアミン化合物がより好ましい。これらの式において、Ｚは上記式（１）で表される構造であり、ｃは、１〜４の整数であり、ｄ及びｅは、１〜２の整数である。

(In the formula, X, Z, R ₅ and c have the same meaning as in the case of the above formula (4).)
In the present invention, the higher the linearity of the polymer obtained, the more liquid crystal alignment film having better liquid crystal alignment can be obtained. As the diamine compound containing the substituent Z, the following formulas (28) to (44) ) And diamine compounds represented by the following formulas (58) to (61) are more preferable. In these formulas, Z is a structure represented by the above formula (1), c is an integer of 1 to 4, and d and e are integers of 1 to 2.

  In the present invention, if the polymer main chain is rigid, a polyimide film having excellent mechanical strength can be obtained. Therefore, the polyimide precursor and polyimide of the present invention contain a structural unit represented by the following formula (5). The polyimide precursor which performs and the polyimide containing the structural unit represented by following formula (11) are more preferable.

（式中、Ｘ、Ｒ_４、Ｚ及びｃは、上記式（３)の場合と同じ意味を表わす。）

(In the formula, X, R ₄ , Z and c have the same meaning as in the case of the above formula (3).)

（式中、Ｘ、Ｒ_４、Ｚ及びｃは、上記式（３)の場合と同じ意味を表わす。）
ｂ．［特定ジアミン化合物］
本発明では、ポリイミド前駆体を製造するための原料として、特に好ましいジアミン化合物として、下記式（Ａ）〜（Ｆ）のジアミン化合物が挙げられる。

(In the formula, X, R ₄ , Z and c have the same meaning as in the case of the above formula (3).)
b. [Specific diamine compound]
In this invention, the diamine compound of following formula (A)-(F) is mentioned as a raw material for manufacturing a polyimide precursor as a particularly preferable diamine compound.

b1. [Production of specific diamine compound]
Although the manufacturing method of the specific diamine compound represented by the said formula (A)-(E) is demonstrated below, this invention is not limited to these.
First, the diamine compound of the above formula (A) is produced, for example, through an intermediate represented by the following formula (iv) using 2-cyano-4-nitroaniline of the following formula (45) as a starting material. .

  First, 2-cyano-4-nitroaniline of the above formula (45) is dissolved in an organic solvent. Here, the organic solvent to be used is not particularly limited as long as it is an organic solvent in which 2-cyano-4-nitroaniline is dissolved and is not decomposed by a reducing agent added later, but dehydrated tetrahydrofuran (THF). Is preferred. The obtained 2-cyano-4-nitroaniline solution is cooled to −40 ° C. to 70 ° C., preferably −20 ° C. to 20 ° C., and then the reducing agent is added while stirring the reaction solution. When the reducing agent is powder, it is preferably added to the reaction solution as it is, and when the reducing agent is a solution, it is preferably added dropwise. Examples of the reducing agent include borane, borane complex, sodium borohydride, lithium aluminum hydride and the like, and borane-THF complex is preferable. After adding the reducing agent, the reaction solution is stirred for 30 minutes to 4 hours, preferably 1 to 2 hours while cooling. Thereafter, the mixture is stirred at room temperature for 12 to 72 hours, preferably 24 to 48 hours. After completion of the reaction, 1-2M inorganic acid is added to make the reaction solution acidic. Examples of inorganic acids include hydrochloric acid, hydrogen fluoride, hydrobromic acid, hydroiodic acid, phosphoric acid, nitric acid, sulfuric acid, boric acid and the like, with hydrochloric acid being more preferred. After adding the inorganic acid, the mixture is stirred at room temperature for 1 to 2 hours, the reaction solution is cooled to 0 to 10 ° C., and a 1 to 2 M inorganic alkali aqueous solution is added to make the reaction solution alkaline. Examples of the inorganic alkaline aqueous solution include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, but an aqueous sodium hydroxide solution is more preferable. After making the reaction solution alkaline, an organic solvent is added for extraction.

  As the organic solvent used for extraction, a halogen-based organic solvent is preferable, and dichloromethane is more preferable. The obtained organic layer is washed with pure water or saturated saline and dried with a desiccant. As the desiccant, sodium sulfate and magnesium sulfate are preferable. The obtained organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. When the desiccant is removed and the solvent is distilled off from the obtained filtrate, a compound represented by the following formula (46) can be obtained. The obtained compound can be used for the next reaction without purification, but may be purified by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency. As long as the organic solvent used for recrystallization is an organic solvent which can recrystallize following formula (46), the kind may be chosen and it may recrystallize with 2 or more types of mixed solvents.

次に、上記式（４６）で表される化合物から下記式（４７）を製造する方法について説明する。

Next, a method for producing the following formula (47) from the compound represented by the formula (46) will be described.

First, the compound represented by the above formula (46) is dissolved in an organic solvent, di-tert-butyl dicarbonate is added, the reaction temperature is −10 ° C. to 40 ° C., preferably 0 ° C. to 20 ° C. Stir to react for ˜48 hours, preferably 20 to 40 hours. The organic solvent used in the reaction is not limited as long as it dissolves the compound of the above formula (46) and does not react with di-tert-butyl dicarbonate, but dichloromethane and tetrahydrofuran are more preferable. . Moreover, in order to advance reaction more efficiently, you may add organic bases, such as a triethylamine and a pyridine. The addition amount is preferably 1 to 2 molar equivalents relative to the compound of the above formula (46). After completion of the reaction, an organic solvent, pure water or saturated saline is added and extracted, and a drying agent is added to the obtained organic layer and dried. The organic solvent used for the extraction is not limited as long as it is not mixed with water, but dichloromethane is preferred. Moreover, you may extract by adding water or a saturated salt solution to a reaction solution. As the desiccant, sodium sulfate and magnesium sulfate are preferable. The obtained organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. The compound represented by the above formula (47) can be obtained by removing the desiccant and distilling off the solvent from the obtained filtrate. The obtained compound can be used for the next reaction without purification, but is preferably purified by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency. As long as the organic solvent used for recrystallization is an organic solvent which can recrystallize following formula (47), the kind may be chosen and it may recrystallize with 2 or more types of mixed solvents.
Next, a method for producing a diamine compound represented by the following formula (A) from the compound represented by the above formula (47) will be described.

  First, the compound represented by the above formula (47) is dissolved in an organic solvent. Here, if the organic solvent to be used is a well-known thing, the kind will not be chosen. In order to advance the reaction more efficiently, methanol, ethanol, 2-propanol, tetrahydrofuran, and 1,4-dioxane are preferable, and methanol and ethanol are more preferable. After dissolving the compound represented by the formula (47) in an organic solvent, the inside of the reaction vessel is replaced with nitrogen, a catalyst is added, and the inside of the reaction vessel is substituted with hydrogen. Examples of the catalyst include palladium carbon, platinum carbon, platinum oxide, and the like, and platinum oxide is more preferable in order to suppress the decomposition reaction at the benzyl position. The reaction mixture is stirred at 0 to 100 ° C., preferably 10 to 60 ° C., for 10 to 48 hours, preferably 15 to 30 hours. After completion of the reaction, the diamine compound of the present invention represented by the above formula (A) can be obtained by removing the catalyst and distilling off the organic solvent. If the obtained compound is not purified, the polymerization reaction does not proceed and a high molecular weight polymer cannot be obtained. Therefore, it is preferable to purify by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency. As long as the organic solvent used for recrystallization is an organic solvent which can recrystallize the diamine of a following formula (A), the kind may be chosen and it may recrystallize with 2 or more types of mixed solvents.

  Hereinafter, although the manufacturing method of the diamine compound of the said Formula (B) and (C) is shown, it is not limited to this. The diamine compounds of the above formulas (B) and (C) are produced, for example, through the intermediates shown in the following formulas (v) and (vi) using propargylamine of the following formula (48) as a starting material. .

上記ジアミン（Ｂ）及び（Ｃ）は、それぞれ下記式（４９）及び（５０）のヨウ化アリールを用いて製造される以外は、同様の方法で製造することが可能である。また、下記式（４９）及び（５０）のヨード基の置換位置にクロル基、ブロモ基、トリフルオロメチルスルホニル基が置換した化合物を用いてもよいが、反応性の観点からヨウ化アリールが好ましい。

The diamines (B) and (C) can be produced in the same manner except that they are produced using aryl iodides of the following formulas (49) and (50), respectively. In addition, a compound in which a chloro group, a bromo group, or a trifluoromethylsulfonyl group is substituted at the substitution position of the iodo group in the following formulas (49) and (50) may be used, but aryl iodide is preferable from the viewpoint of reactivity. .

以下に、上記式（４８）のプロパルギルアミンから、下記式（５１）のＢｏｃ−プロパルギルアミンを製造する方法について説明する。

Hereinafter, a method for producing Boc-propargylamine of the following formula (51) from the propargylamine of the above formula (48) will be described.

Dissolve propargylamine in organic solvent and add organic base. Here, the organic solvent used in the reaction is not limited as long as it dissolves propargylamine and does not react with di-tert-butyl dicarbonate added later, but dichloromethane is preferable. The organic base is added for the purpose of improving the nucleophilicity of the amino group, and triethylamine or pyridine is more preferable. The reaction solution is -5 ° C to 40 ° C, preferably 0 ° C to 20 ° C, and di-tert-butyl dicarbonate is added dropwise to the reaction solution. If the dropping speed is too fast, the reaction proceeds rapidly, and thus the dropping time is preferably 10 minutes to 1 hour. The dropping speed can be changed depending on the amount of di-tert-butyl dicarbonate added. After completion of the dropwise addition, the mixture is stirred for 1 to 10 hours, preferably 2 to 4 hours, and then the reaction solution is extracted by adding water, saturated saline, or an organic solvent. The organic solvent used for extraction is not limited as long as it is not mixed with water, but it is preferable to use the same organic solvent as used for the reaction. The organic layer obtained by extraction is dried with a desiccant. As the desiccant, sodium sulfate or magnesium sulfate is preferable. The obtained organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. When the desiccant is removed and the solvent is distilled off from the obtained filtrate, the compound represented by the above formula (51) can be obtained. The obtained compound can be used for the next reaction without purification, but is preferably purified by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency. As long as the organic solvent used for recrystallization is an organic solvent which can recrystallize following formula (51), the kind may be chosen and it may recrystallize with 2 or more types of mixed solvents.
Next, a method for producing a compound represented by the following formula (52) using the compound represented by the above formula (51) will be described.

上記式（５２）で表される化合物は、上記式（５１）のＢｏｃ−プロパルギルアミンと上記式（４９）で表されるハロゲン化アリールとを園頭カップリング（Sonogashira coupling）反応させることにより製造することができる。
上記式（４９）で表されるヨウ化アリール、パラジウム触媒、銅触媒、及び塩基を加え、有機溶剤に溶解させる。パラジウム触媒としては、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロリドが好ましく、添加量は、ヨウ化アリールのヨード基に対して、０．０５〜１．０モル％、好ましくは、０．１〜０．５モル％がより好ましい。銅触媒としては、ヨウ化銅が好ましく、その添加量は、ハロゲン化アリールのヨード基に対して、０．０５〜１．０モル％、好ましくは、０．１〜０．５モル％がより好ましい。塩基としては、トリエチルアミン、ジエチルアミンが好ましく、その添加量は、ヨウ化アリールのヨード基に対して、１〜３モル等量が好ましく、１〜２モル等量がより好ましい。反応に使用する有機溶剤としては、ヨウ化アリールを溶解し、かつ、後に加える種々の試薬と反応しないものであれば、その種類を選ばないが、Ｎ，Ｎ−ジメチルホルムアミドが好ましい。

The compound represented by the above formula (52) is produced by reacting Boc-propargylamine of the above formula (51) with the aryl halide represented by the above formula (49) by Sonogashira coupling reaction. can do.
The aryl iodide represented by the above formula (49), a palladium catalyst, a copper catalyst, and a base are added and dissolved in an organic solvent. As the palladium catalyst, bis (triphenylphosphine) palladium (II) dichloride is preferable, and the addition amount is 0.05 to 1.0 mol%, preferably 0.1 to 0.1 mol% with respect to the iodo group of aryl iodide. 0.5 mol% is more preferable. As the copper catalyst, copper iodide is preferable, and the amount added is 0.05 to 1.0 mol%, preferably 0.1 to 0.5 mol%, based on the iodo group of the aryl halide. preferable. As a base, triethylamine and diethylamine are preferable, and the addition amount thereof is preferably 1 to 3 mole equivalents, and more preferably 1 to 2 mole equivalents with respect to the iodo group of aryl iodide. The organic solvent used in the reaction is not particularly limited as long as it dissolves aryl iodide and does not react with various reagents to be added later. N, N-dimethylformamide is preferred.

  The reaction solution is stirred at 0 ° C. to 30 ° C., preferably 0 ° C. to 20 ° C. for 5 to 30 minutes, and then added with Boc-propargylamine of the above formula (51) for 2 to 12 hours, preferably Stir for 4-10 hours. The amount of Boc-propargylamine added is preferably 1 to 2 molar equivalents, and more preferably 1.20 to 1.50 molar equivalents with respect to the iodo group of aryl iodide.

An organic solvent and an acidic aqueous solution are added to the reaction solution for extraction. The organic solvent used for extraction is not limited as long as it is not mixed with water, but ethyl acetate, dichloromethane, chloroform, and 1,2-dichloroethane are more preferable. As the acidic aqueous solution, an aqueous solution of ammonium chloride, hydrochloric acid, acetic acid, or formic acid is preferable. If the acidity is too high, Boc may be detached, so an aqueous ammonium chloride solution is more preferable. The concentration of the acidic solution is preferably 0.5 to 2 mol / L, and more preferably 1 to 1.5 mol / L. The obtained organic layer is washed several times with an acidic aqueous solution and then dried with a desiccant. As the desiccant, sodium sulfate and magnesium sulfate are preferable. The obtained organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. When the desiccant is removed and the solvent is distilled off from the obtained filtrate, the compound represented by the formula (52) can be obtained. The obtained compound can be used for the next reaction without purification, but is preferably purified by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency. As long as the organic solvent used for recrystallization is an organic solvent which can recrystallize said Formula (52), the kind may be chosen and it may recrystallize with 2 or more types of mixed solvents.
The diamine compound of the present invention represented by the following formula (B) can be produced by a hydrogenation reaction of the compound represented by the above formula (52).

The compound represented by the above formula (52) is dissolved in an organic solvent. Here, the organic solvent to be used is not limited as long as it is a known one, but methanol, ethanol, 2-propanol, tetrahydrofuran, and 1,4-dioxane are preferable in order to promote the reaction more efficiently. More preferred are methanol and ethanol. After dissolving the compound represented by the formula (52) in an organic solvent, the inside of the reaction vessel is replaced with nitrogen, a catalyst is added, and the inside of the reaction vessel is substituted with hydrogen. Examples of the catalyst include palladium carbon, platinum carbon, platinum oxide and the like, and palladium carbon is more preferable from the viewpoint of reaction efficiency. The reaction mixture is stirred at 0 ° C. to 100 ° C., preferably 10 to 60 ° C. for 15 to 72 hours, preferably 24 to 48 hours. After completion of the reaction, the diamine compound of the present invention represented by the above formula (B) can be obtained by removing the catalyst and distilling off the organic solvent. The obtained compound is preferably purified by various methods because the polymerization reaction does not proceed and a high molecular weight polymer cannot be obtained unless the compound is highly purified. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency. As long as the organic solvent used for recrystallization is an organic solvent that can recrystallize the diamine represented by the above formula (B), the kind thereof may be selected and recrystallization may be performed with two or more kinds of mixed solvents.
Hereinafter, although the manufacturing method of the diamine compound of the said Formula (D) and (E) is shown, it is not limited to this.

  The diamine compounds of the above formulas (D) and (E) are represented by the following formula (vii) using, for example, 2-amino-4-nitroaniline of the following formula (53) and an amino acid compound of the following formula (54) as starting materials. It is manufactured through an intermediate shown in (1). The amino acid compound of the following formula (54) is a compound in which the amino group of the amino acid is protected with Boc. The diamine compounds of the above formulas (D) and (E) can be produced using amino acid compounds in which the amino groups of glycine and histidine are protected with a Boc group, respectively. On the other hand, even if it is other amino acids, a diamine compound can be manufactured with the same manufacturing method.

上記式（５３）の２−アミノ−４−ニトロアニリンと上記式（５４）で表されるアミノ酸化合物との反応により、下記式（５５）で表される化合物を製造することができる。

A compound represented by the following formula (55) can be produced by reacting 2-amino-4-nitroaniline of the above formula (53) with an amino acid compound represented by the above formula (54).

  The amino group at position 1 of 2-amino-4-nitroaniline is reduced in nucleophilicity due to the influence of the nitro group present at position 4. Therefore, since the amino group at the 2-position reacts preferentially with the carboxylic acid of the amino acid compound, the compound represented by the above formula (55) can be produced. When the amino acid compound is added excessively, an amino group at the 4-position is formed with an amide bond, so the addition amount of the amino acid compound is 0.9 to 1.2 times mol with respect to 2-amino-4-nitroaniline. Preferably there is.

  The compound represented by the above formula (55) can be produced by a condensation reaction between the amino group at the 2-position of 2-amino-4-nitroaniline and the carboxylic acid of the amino acid compound of the above formula (54). If the condensation of an amino group and carboxylic acid is a well-known method, the kind will not be limited, but when manufacturing the diamine compound of this invention, the method using a mixed acid anhydride and the method using a condensing agent are more preferable.

  In the method using a mixed acid anhydride, for example, a carboxylic acid is reacted with an acid halide or an acid derivative in an organic solvent at −40 ° C. to 40 ° C., preferably −20 ° C. to 5 ° C. in the presence of a base. And the resulting mixed acid anhydride is reacted with 2-amino-4-nitroaniline in an organic solvent at -40 ° C to 40 ° C, preferably -20 ° C to 5 ° C.

The organic solvent used in the reaction is not limited as long as it dissolves the amino acid compound represented by the above formula (54) and does not react with each reagent used in the reaction. Chloroform, dichloromethane and tetrahydrofuran are preferred, and tetrahydrofuran is more preferred because of its solubility in amino acid compounds.
The base used in the reaction is preferably a tertiary amine, more preferably pyridine, triethylamine, dimethylaminopyridine, or N-methylmorpholine. Since removal is difficult when the amount of the base added is too large, it is preferably 2 to 4 moles relative to 2-amino-4-nitroaniline.

  As the acid halide and acid derivative, pivaloyl chloride, tosyl chloride, mesyl chloride, ethyl chloroformate, and isobutyl chloroformate are preferable. It is preferable that the addition amount of an acid halide and an acid derivative is 1.5-2 times mole with respect to 2-amino-4-nitroaniline.

  In the method using a condensing agent, 2-amino-4-nitroaniline and an amino acid compound are added in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 ° C. It can be produced by reacting for a time, preferably 3 to 15 hours.

  Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate, and the like. It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to an amino acid compound.

  As the base, tertiary amines such as pyridine and triethylamine can be used. If the amount of the base added is too large, removal is difficult, and if it is too small, the molecular weight is small. Therefore, the amount is preferably 2 to 4 times the mole of 2-amino-4-nitroaniline. In the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. It is preferable that the addition amount of a Lewis acid is 0-1.0 times mole with respect to 2-amino-4-nitroaniline.

  In the above two methods, it is preferable to remove the precipitate from the obtained reaction solution, and then add an acid or basic aqueous solution and an organic solvent to remove the acid halide or acid derivative, the condensing agent and the base by extraction. . As the acidic aqueous solution, an aqueous solution of hydrochloric acid, acetic acid, formic acid, or ammonium chloride is preferable. As the aqueous base solution, an aqueous solution of sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, or potassium carbonate is preferable. The organic solvent used for the extraction is not limited as long as the content does not cause precipitation of the contents even when added to the reaction solution and does not mix with water. Ethyl acetate, dichloromethane, chloroform, 1,2- Dichloroethane is more preferred.

The obtained organic layer is washed several times with the acidic aqueous solution or the basic aqueous solution and then dried with a desiccant. As the desiccant, sodium sulfate and magnesium sulfate are preferable. The obtained organic layer is dried for 4 to 24 hours, preferably 12 to 24 hours. When the desiccant is removed and the solvent is distilled off from the obtained filtrate, the compound represented by the formula (55) can be obtained. The obtained compound can be used for the next reaction without purification, but is preferably purified by various methods. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency. As long as the organic solvent used for recrystallization is an organic solvent which can recrystallize the compound represented by said Formula (55), it may select the kind and may recrystallize with 2 or more types of mixed solvents.
A diamine compound represented by the following formula (56) can be produced by a hydrogenation reaction of the compound represented by the above formula (55).

  First, the compound represented by the formula (55) is dissolved in an organic solvent. Here, the organic solvent to be used is not limited as long as it is a known one, but methanol, ethanol, 2-propanol, tetrahydrofuran, and 1,4-dioxane are preferable in order to promote the reaction more efficiently. More preferred are methanol and ethanol. After dissolving the compound represented by the formula (55) in an organic solvent, the inside of the reaction vessel is replaced with nitrogen, a catalyst is added, and the inside of the reaction vessel is substituted with hydrogen. Examples of the catalyst include palladium carbon, platinum carbon, platinum oxide and the like, and palladium carbon is more preferable from the viewpoint of reaction efficiency. The reaction mixture is stirred at 0 ° C. to 100 ° C., preferably 10 to 60 ° C. for 15 to 72 hours, preferably 24 to 48 hours. After completion of the reaction, the catalyst is removed and the organic solvent is distilled off to obtain the diamine compound of the present invention represented by the above formula (56). The obtained compound is preferably purified by various methods because the polymerization reaction does not proceed and a high molecular weight polymer cannot be obtained unless the compound is highly purified. Examples of the purification method include silica gel column chromatography, recrystallization, washing with an organic solvent, and the like. Recrystallization is more preferable from the viewpoint of ease of operation and high purification efficiency. As long as the organic solvent used for recrystallization is an organic solvent that can recrystallize the diamine represented by the following formula (56), the kind thereof may be selected and recrystallization may be performed with two or more kinds of mixed solvents.

c. [Production of polyimide precursor and polyimide]
The polyimide precursor and polyimide of the present invention are at least one selected from the group consisting of a diamine compound having a substituent represented by formula (1) and a tetracarboxylic acid derivative having a substituent represented by formula (1). It is produced using a compound (hereinafter also referred to as a specific monomer). Specifically, it is produced using a tetracarboxylic acid derivative represented by the above formula (19) to formula (21) and / or a diamine compound represented by formula (22). Especially, it is preferable that a specific monomer is a diamine compound which has a substituent represented by the said Formula (1).
When producing the polyimide precursor and polyimide of the present invention, as raw material monomers, tetracarboxylic acid derivatives other than specific monomers (for example, tetracarboxylic acid derivatives represented by the above formulas (23) to (25)) and A diamine compound other than the specific monomer (for example, a diamine compound represented by the above formula (26)) may be used in combination. In this case, the amount of the specific monomer used in the raw material monomer is preferably 2 to 100 mol%, more preferably 2 to 60 mol%, still more preferably 2 to 50 mol%, and particularly preferably 2 to 30 mol%.

  In this invention, a raw material monomer means the tetracarboxylic acid derivative and diamine compound which are used in order to manufacture the polyimide precursor and polyimide of this invention. However, the tetracarboxylic acid derivative and / or diamine compound used in the present invention includes a specific monomer.

c1. (Production of polyamic acid)
The polyamic acid which is a polyimide precursor can be produced from a tetracarboxylic dianhydride and a diamine compound (the following formula (viii)), but the tetracarboxylic dianhydride and / or diamine compound includes a specific monomer. Is contained.

When producing a polyimide precursor, the tetracarboxylic dianhydride and the diamine compound are preferably -20 to 140 ° C, preferably 0 to 50 ° C in the presence of an organic solvent, preferably 30 minutes to 24 hours, preferably Can be produced by reacting for 1 to 12 hours. The solvent used for the production of the polyamic acid of the above formula (viii) is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the monomer and polymer. Or you may use it in mixture of 2 or more types. If the concentration at the time of production is too high, polymer precipitation tends to occur, and if it is too low, the molecular weight does not increase. Therefore, the total amount of tetracarboxylic dianhydride and diamine compound in the reaction solution is preferably 1 to 30% by mass. 5 to 20% by mass is more preferable.
The polyamic acid obtained as described above can use the reaction solution as the liquid crystal aligning agent of the present invention, but if it is not desired to include the solvent used in the polymerization in the liquid crystal aligning agent, the polymer After being recovered as a solid, it can be used as the polyamic acid of the present invention.

By injecting the polymer into a poor solvent while thoroughly stirring the reaction solution, the polymer can be precipitated and recovered. Precipitation is performed several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified polyamic acid powder.
Although the said poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

c2. (Production of polyamic acid ester)
The polyamic acid ester can be produced by a known production method, and specifically includes the following methods (a) to (c), but is not limited thereto.
(A) When producing polyamic acid ester from polyamic acid

  The polyamic acid ester of the present invention can be produced by esterifying the above-described polyamic acid of the present invention (the above formula (ix)). Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at −20 ° C. to 140 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be manufactured by.

The esterifying agent is preferably one that can be easily removed by purification. N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethyl Formamide dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3- Examples include p-tolyltriazene. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.
The solvent used for the production of the polyamic acid ester of the above formula (ix) is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the monomer and the polymer. You may mix and use seed | species or 2 or more types. If the concentration at the time of production is too high, polymer precipitation tends to occur, and if it is too low, the molecular weight does not increase. Therefore, the total amount in the reaction solution of the polyamic acid and the esterifying agent is preferably 1 to 30% by mass, 20 mass% is more preferable.

(B) When producing a polyamic acid ester from an acid chloride and a diamine compound

ポリアミック酸エステルは、酸クロライドとジアミン化合物から製造することができる（上記式（ｘ））。本発明では、酸クロライド及び／又はジアミン化合物には特定モノマーが含まれる。
具体的には、酸クロライドとジアミン化合物とを塩基と有機溶剤の存在下で−２０℃〜１４０℃、好ましくは０℃〜５０℃において、３０分〜２４時間、好ましくは１〜４時間反応させることによって製造することができる。前記塩基には、ピリジン、トリエチルアミン、４−ジメチルアミノピリジンが使用できるが、反応が穏和に進行するためにピリジンが好ましい。塩基の添加量は、多すぎると除去が難しく、少なすぎると分子量が小さくなるため、酸クロライドに対して、２〜４倍モルであることが好ましい。

The polyamic acid ester can be produced from an acid chloride and a diamine compound (the above formula (x)). In the present invention, the acid chloride and / or diamine compound includes a specific monomer.
Specifically, an acid chloride and a diamine compound are reacted in the presence of a base and an organic solvent at −20 ° C. to 140 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be manufactured. As the base, pyridine, triethylamine, and 4-dimethylaminopyridine can be used, but pyridine is preferable because the reaction proceeds gently. If the amount of the base added is too large, removal is difficult, and if it is too small, the molecular weight is small. Therefore, the amount is preferably 2 to 4 times the mol of the acid chloride.

  The solvent used in the production of the polyamic acid ester of the above formula (x) is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the monomer and the polymer, and these may be used alone or in combination of two or more. May be used. If the concentration at the time of production is too high, polymer precipitation is likely to occur, and if it is too low, the molecular weight does not increase. Therefore, the total amount of acid chloride and diamine compound in the reaction solution is preferably 1 to 30% by mass, preferably 5 to 20%. The mass% is more preferable. In addition, in order to prevent hydrolysis of acid chloride, the solvent used for the production of the polyamic acid ester should be dehydrated as much as possible, and it is better to prevent external air from being mixed in a nitrogen atmosphere.

(C) When producing polyamic acid ester from dialkyl ester dicarboxylic acid and diamine compound

ポリアミック酸エステルは、ジアルキルエステルジカルボン酸とジアミン化合物を縮合剤により縮合することにより製造することができる（上記式（ｘｉ））。本発明では、ジアルキルエステルジカルボン酸及び／又はジアミン化合物には特定モノマーが含まれる。
具体的には、ジアルキルエステルジカルボン酸とジアミン化合物を縮合剤、塩基、及び有機溶剤の存在下で０℃〜１４０℃、好ましくは０℃〜１００℃において、３０分〜２４時間、好ましくは３〜１５時間反応させることによって製造することができる。

The polyamic acid ester can be produced by condensing a dialkyl ester dicarboxylic acid and a diamine compound with a condensing agent (the above formula (xi)). In the present invention, the dialkyl ester dicarboxylic acid and / or diamine compound includes a specific monomer.
Specifically, a dialkyl ester dicarboxylic acid and a diamine compound in the presence of a condensing agent, a base, and an organic solvent are 0 ° C. to 140 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to It can be produced by reacting for 15 hours.

  Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate, and the like. It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to dialkyl ester dicarboxylic acid.

As the base, tertiary amines such as pyridine and triethylamine can be used. If the amount of the base added is too large, removal is difficult, and if it is too small, the molecular weight is small.
In the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0 to 1.0-fold mol with respect to the diamine component.

  Among the methods for producing the above three polyamic acid esters, the production methods (a) and (b) are particularly preferred because a high molecular weight polyamic acid ester is obtained.

The polyamic acid ester solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
Although the said poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

c3. [Molecular weight]
The ratio of the diamine component used in the polymerization reaction and the tetracarboxylic acid derivative (tetracarboxylic dianhydride, acid chloride and dialkyl ester dicarboxylic acid) is 1: 0.7 to 1: 1.2 in terms of molar ratio from the viewpoint of molecular weight control. Preferably there is. The closer the molar ratio is to 1: 1, the higher the molecular weight of the resulting polyimide precursor. The molecular weight of the polyimide precursor affects the viscosity of the varnish and the physical strength of the polyimide film, and if the molecular weight of the polyimide precursor is too large, the coating workability and coating film uniformity of the varnish may deteriorate. If the molecular weight is too small, the strength of the resulting polyimide film may be insufficient. Therefore, the molecular weight of the polyamic acid ester used in the polyimide precursor composition of the present invention is preferably 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 300,000, and still more preferably, 10,000 to 100,000.

d. [Production of polyimide]
The polyimide of the present invention can be produced by imidizing the polyimide precursor. When manufacturing a polyimide from a polyimide precursor, the chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not easily decrease during the imidization process.

  Chemical imidation can be performed by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.

The temperature at which the imidization reaction is performed is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amic acid group. Is double. The imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst or the like remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below, redissolved in an organic solvent, and the liquid crystal alignment according to the present invention. It is preferable to use an agent.
The polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while thoroughly stirring. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
The poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.

e. [Liquid crystal aligning agent]
The liquid crystal aligning agent of the present invention is a coating liquid for forming a liquid crystal aligning agent in which the polyimide precursor or polyimide obtained as described above is uniformly dissolved in an organic solvent.

e1. [solvent]
As a solvent used for the liquid crystal aligning agent of the present invention, a polyimide precursor or a solvent capable of dissolving the polyimide (hereinafter referred to as a good solvent) and a coating film uniformity when applying the liquid crystal aligning agent to the substrate are improved. Two types of solvents (hereinafter referred to as poor solvents). The good solvent is not particularly limited as long as it dissolves the polyimide precursor or the polyimide. Specific examples are N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl. Caprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropane Examples include amides. You may use these 1 type or in mixture of 2 or more types. Even if the solvent alone does not dissolve the polymer, it may be mixed as long as the polymer does not precipitate.
The poor solvent is not particularly limited as long as it has low surface tension and improves coating film uniformity. Specific examples include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy. 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene Glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. And the like. Two types of these solvents may be used in combination.

[Silane coupling agent]
A silane coupling agent is an organosilicon compound having both an organic functional group chemically bonded to an organic material in a molecule and a hydrolyzable group reactive with an inorganic material, and its structure is generally represented by the following formula (57). expressed.

式（５７）中、Ｑは有機官能基であり、Ｒ_１４は２価の有機基を示し、Ｒはアルキル基であり、ＷはＯＲ_１５で示されるアルコキシ基（ここでＲ_１５は、アルキル基である）であり、ｎは１〜３の整数である。
シランカップリング剤は、電子デバイスの基板として用いられる各種無機材料と重合体との密着性を向上される目的で添加される。シランカップリング剤は、加水分解基であるアルコキシシランが加熱により加水分解してシラノールとなり、基板表面に存在する極性基と水素結合又は共有結合を形成し、密着性が付与される。

In formula (57), Q represents an organic functional group, R ₁₄ represents a divalent organic group, R represents an alkyl group, and W represents an alkoxy group represented by OR ₁₅ (where R ₁₅ represents an alkyl group). And n is an integer of 1 to 3.
The silane coupling agent is added for the purpose of improving the adhesion between various inorganic materials used as substrates for electronic devices and the polymer. In the silane coupling agent, alkoxysilane, which is a hydrolyzable group, is hydrolyzed by heating to form silanol, and forms a hydrogen bond or a covalent bond with a polar group present on the substrate surface, thereby imparting adhesion.

Although the specific example of the silane coupling agent used for this invention is put together below, it is not limited to this.
3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-phenylaminopropyltri Amine-based silane coupling agents such as methoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-aminopropyldiethoxymethylsilane; vinyltrimethoxysilane, vinyltriethoxysilane, Vinyl-based silane couplings such as vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane Agents: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxy cyclohexyl) Epoxy silane coupling agent such as ethyltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Methacrylic silane coupling agents such as ethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; Ureido silane cups such as 3-ureidopropyltriethoxysilane Sulfide-based silane coupling agents such as bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Mercapto silane coupling agents such as trimethoxysilane and 3-octanoylthio-1-propyltriethoxysilane; Isocyanate silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane; Aldehyde-based silane coupling agents such as butyraldehyde; carbamates such as triethoxysilylpropylmethylcarbamate and (3-triethoxysilylpropyl) -t-butylcarbamate Examples include mate-based silane coupling agents.

  The silane coupling agent can exhibit its effect more when the organic functional group Q is bonded to the functional group in the polymer and introduced into the polymer. That is, the silane coupling agent is preferably used depending on the composition of the polyimide precursor or polyimide used.

When a polyimide film is used in an electronic device such as a liquid crystal display element, it is preferable to introduce a silane coupling agent into the polymer terminal in order to improve adhesion without impairing its characteristics. Polyimide precursor and its imidized polymer polyimide are polymer terminal by adjusting the molar ratio of tetracarboxylic acid derivatives such as tetracarboxylic dianhydride, acid chloride, and dialkyl ester dicarboxylic acid and diamine compound. These functional groups can be amines, carboxylic acids or esters. Therefore, epoxy-based silane coupling agents, isocyanate-based silane coupling agents, aldehyde-based silane coupling agents, carbamate-based silane coupling agents, and amine-based silane coupling agents that are highly reactive with these functional groups are preferable. From the viewpoint of properties, amine-based silane coupling agents and epoxy-based silane coupling agents are particularly preferable.
Moreover, arbitrary functional groups can be introduced into the polymer by modifying the terminal of the polymer with a known functional compound. In such a case, it is preferable to add a silane coupling agent having an organic functional group Q that reacts with the introduced functional group.
When the coupling agent is blended, the adhesion can be improved by heating after the coupling agent is added and reacting with the polymer. After adding the coupling agent, the reaction may be performed at 20 to 80 ° C., more preferably at 40 to 60 ° C. for 1 to 24 hours.

e3. [Other additives]
It goes without saying that various additives such as a crosslinking agent may be further used in the liquid crystal aligning agent of the present invention. Two or more kinds of polymers may be contained in the polyimide precursor or polyimide composition of the present invention.

e4. [Polymer concentration]
Although the polymer concentration of the liquid crystal aligning agent of this invention can be suitably changed with the setting of the thickness of the polyimide film to be formed, it is preferable to set it as 1-10 mass%, and 2-8 mass% is more. preferable. If it is less than 1% by mass, it is difficult to form a uniform and defect-free coating film, and if it exceeds 10% by mass, the storage stability of the solution may be deteriorated.

f. [Method for producing liquid crystal aligning agent]
The liquid crystal aligning agent of this invention can be manufactured with the following method.
When the polymer to be used is powder, it is dissolved in the solvent to obtain a polymer solution. At this time, the polymer concentration is preferably 10 to 30% by mass, and particularly preferably 10 to 15% by mass. Further, heating may be performed when the polymer powder is dissolved. The heating temperature is preferably 20 to 140 ° C, particularly preferably 20 to 80 ° C.
By adding the solvent and the solvent for improving the coating film uniformity to the polymer reaction solution or the polymer solution obtained by re-dissolving the polymer, and diluting to a predetermined polymer concentration. The liquid crystal aligning agent of this invention is obtained. When adding a silane coupling agent, it is preferable to add before adding the solvent for improving the uniformity of the coating film in order to prevent precipitation of the polymer.
If the addition amount of the silane coupling agent is too large, the unreacted material may adversely affect the liquid crystal alignment, and if it is too small, the effect on the adhesion does not appear. -5.0 mass% is preferable, and 0.1-1.0 mass% is more preferable.

g. [Liquid crystal alignment film]
The liquid crystal alignment film of the present invention is obtained as follows. That is, the liquid crystal aligning agent of the present invention is preferably filtered, then applied to a substrate, dried and fired to form a coating film. The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like is formed. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
Examples of the method for applying the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method. After applying the liquid crystal aligning agent of the present invention, it is preferably dried and baked. In order to sufficiently remove the organic solvent contained in the liquid crystal aligning agent, it is preferably dried at 50 to 120 ° C., preferably for 1 to 10 minutes. Subsequently, it is preferably fired at 150 to 300 ° C, more preferably 150 to 250 ° C. The firing time varies depending on the firing temperature, but is preferably 5 to 120 minutes, more preferably 5 to 60 minutes.

  As described above, the liquid crystal aligning agent of the present invention has 150 primary or secondary aliphatic amino groups protected by the Boc group of the polyimide precursor or its imidized polymer in the baking process of the coating film. By heating to a temperature higher than or equal to ° C., the Boc group is eliminated, and a reactive primary or secondary aliphatic amino group in which the protection of the Boc group is lost is generated. The generated primary or secondary aliphatic amino group reacts with a functional group present in the polyimide precursor or its imidized polymer to form an intermolecular crosslink, and the liquid crystal obtained in the present invention through such a crosslink reaction. The alignment film has improved mechanical strength, and a polyimide film that does not cause peeling or scratching due to rubbing can be obtained.

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, and therefore it is 5 to 300 nm, preferably 10 to 200 nm. By subjecting the coating surface to an orientation treatment such as rubbing, it can be used as a liquid crystal orientation film.
Examples of the method for aligning the liquid crystal alignment film of the present invention include a rubbing method and a photo-alignment processing method.

As a specific example of the photo-alignment treatment method, the surface of the coating film is irradiated with radiation polarized in a certain direction, and in some cases, a heat treatment is further performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability. Is mentioned. As the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Among these, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and ultraviolet rays having a wavelength of 200 to 400 nm are particularly preferable. Moreover, in order to improve liquid crystal orientation, you may irradiate a radiation, heating a coating-film board | substrate at 50-250 degreeC. Dose of the radiation is preferably in the range of 1~10,000mJ / cm ^2, and particularly preferably in the range of 100~5,000mJ / cm ^2.
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

The abbreviations and structures of the compounds used in the examples and comparative examples are shown below.
CBDA: cyclobutanetetracarboxylic dianhydride 1,3DMCBDE-Cl: dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate p-PDA: p-phenylenediamine DA -A: diamine of the above formula (A) DA-B: diamine of the above formula (B) DA-D: diamine of the above formula (D) DA-E: diamine of the above formula (E) DA-F: above formula ( F) Diamine DA-H: Diamine of the following formula (H)

（有機溶媒）
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＢＣＳ：ブチルセロソルブ
ＤＭＦ：Ｎ，Ｎ−ジエチルホルムアミド
ＴＨＦ：テトラヒドロフラン
γ−ＢＬ：γ−ブチロラクトン

(Organic solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve DMF: N, N-diethylformamide THF: Tetrahydrofuran γ-BL: γ-butyrolactone

The measurement methods for ¹ H-NMR, viscosity, molecular weight, and rubbing resistance are shown below.
[ ¹ H-NMR]
Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz
Solvent: deuterated dimethyl sulfoxide (DMSO-d ₆ ) or deuterated chloroform (CDCl ₃ )
Standard substance: Tetramethylsilane (TMS)
[viscosity]
In the synthesis example, the viscosity of the polyamic acid ester and the polyamic acid solution is an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample amount 1.1 mL, cone rotor TE-1 (1 ° 34 ′, R24). ), Measured at a temperature of 25 ° C.
[Molecular weight]
The molecular weight of the polyamic acid ester is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and is a number average molecular weight (hereinafter also referred to as Mn) and a weight average molecular weight (hereinafter also referred to as Mw) as polyethylene glycol and polyethylene oxide equivalent values. ) Was calculated.
GPC device: manufactured by Shodex (GPC-101)
Column: manufactured by Shodex (series of KD803 and KD805)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 ml / L)
Flow rate: 1.0 ml / min

  Standard sample for preparing calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (peak top) manufactured by Polymer Laboratory Molecular weight (Mp) about 12,000, 4,000, 1,000). In order to avoid the overlapping of peaks, the measurement was performed by mixing four types of 900,000, 100,000, 12,000, and 1,000, and three types of 150,000, 30,000, and 4,000. Two samples of mixed samples are measured separately.

[Rubbing resistance of polyimide film]
A liquid crystal aligning agent is spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and baked at a temperature of 230 ° C. for 20 minutes or 60 minutes to form a polyimide film having a thickness of 100 nm. did. After this polyimide film was rubbed, the surface state of the polyimide film was observed to evaluate the presence or absence of rubbing scratches, the presence or absence of chipping residue of the polyimide film, and the presence or absence of peeling of the polyimide film.

[Voltage holding ratio]
The voltage holding ratio of the liquid crystal cell was measured as follows.
By applying a voltage of 4 V for 60 μs and measuring the voltage after 16.67 ms, the fluctuation from the initial value was calculated as the voltage holding ratio. During the measurement, the temperature of the liquid crystal cell was set to 23 ° C., 60 ° C., and 90 ° C., and the measurement was performed at each temperature.
[Ion density]
The ion density of the liquid crystal cell was measured as follows.
Measurement was performed using a 6254 type liquid crystal property evaluation apparatus manufactured by Toyo Technica. A triangular wave of 10 V and 0.01 Hz was applied, and an area corresponding to the ion density of the obtained waveform was calculated by a triangle approximation method to obtain an ion density. During the measurement, the temperature of the liquid crystal cell was set to 23 ° C. and 60 ° C., and the measurement was performed at each temperature.

Example 1 Synthesis of DA-A (Precursor Synthesis 1)

１Ｌ四つ口フラスコに、ジムロート、及び１００ｍＬ滴下漏斗をつなげ、２−シアノ−４−ニトロアニリン（１５ｇ，９２ｍｍｏｌ）を加え、系内を窒素で置換した後、ＴＨＦ４００ｍＬを加え、０℃に冷却した。次に、滴下漏斗からボラン−ＴＨＦ錯体（１Ｍ ｉｎ ＴＨＦ，１００ｍＬ，１００ｍｍｏｌ）を３０分かけて滴下した。反応系から気体の発生が確認され、黄色固体が析出した。滴下終了後、室温で、２日間撹拌した。反応終了後、塩酸水溶液（２Ｎ，２００ｍＬ）加え、室温で２時間撹拌した後、１０℃で水酸化ナトリウム水溶液（２Ｎ，２５０ｍＬ）を加え塩基性にし、ジクロロメタンで抽出した。有機層を飽和食塩水（５００ｍＬ）で洗浄し、硫酸マグネシウムで乾燥した後、濃縮、真空乾燥を行うことで黄色固体のシアノ基還元体を得た。収量は、１１．９ｇ、収率は７７％であった。

Dimroth and 100 mL dropping funnel were connected to a 1 L four-necked flask, 2-cyano-4-nitroaniline (15 g, 92 mmol) was added, the system was replaced with nitrogen, and then 400 mL of THF was added and cooled to 0 ° C. . Next, borane-THF complex (1M in THF, 100 mL, 100 mmol) was dropped from the dropping funnel over 30 minutes. Generation of gas was confirmed from the reaction system, and a yellow solid was precipitated. After completion of dropping, the mixture was stirred at room temperature for 2 days. After completion of the reaction, an aqueous hydrochloric acid solution (2N, 200 mL) was added, and the mixture was stirred at room temperature for 2 hours. Then, an aqueous sodium hydroxide solution (2N, 250 mL) was added at 10 ° C., and the mixture was extracted with dichloromethane. The organic layer was washed with saturated brine (500 mL), dried over magnesium sulfate, concentrated and vacuum dried to obtain a yellow solid cyano group reduced form. The yield was 11.9 g and the yield was 77%.

(Precursor synthesis 2)

１Ｌナスフラスコに前記シアノ基還元体（４．６０ｇ，２７．５ｍｍｏｌ）及び塩化メチレン（９００ｍＬ）を加え溶液としたところに、二炭酸ジ−ｔｅｒｔ−ブチル（Ｂｏｃ_２Ｏ）（６．００ｇ，２７．５ｍｍｏｌ）を加え、室温（２０℃）で３日間撹拌した。反応終了後、反応溶液をそのまま飽和食塩水で洗浄し、有機層を分離し、硫酸マグネシウムで乾燥した。有機層を減圧濃縮することで析出する固体を酢酸エチル―ヘキサン（体積比：２／７）で再結晶することで、黄色固体のＢｏｃ付加体を得た。収量は、５．２５ｇ，収率は、７１％であった。

The reduced cyano group (4.60 g, 27.5 mmol) and methylene chloride (900 mL) were added to a 1 L eggplant flask to give a solution, and di-tert-butyl dicarbonate (Boc ₂ O) (6.00 g, 27 0.5 mmol), and the mixture was stirred at room temperature (20 ° C.) for 3 days. After completion of the reaction, the reaction solution was washed with saturated brine as it was, and the organic layer was separated and dried over magnesium sulfate. The solid precipitated by concentrating the organic layer under reduced pressure was recrystallized from ethyl acetate-hexane (volume ratio: 2/7) to obtain a Boc adduct as a yellow solid. The yield was 5.25 g, and the yield was 71%.

(Synthesis of DA-A)

１００ｍＬナスフラスコに前記Ｂｏｃ付加体（５．０ｇ，１８．７ｍｍｏｌ）及びエタノール（４０ｍｌ）を加え、系内を窒素で置換した後、酸化白金（５００ｍｇ）を加え、系内を水素で置換した。黄色懸濁となった反応混合物を室温で１５時間撹拌した。反応終了後、エタノールを追加し、析出した白色固体を溶かし、セライトろ過により触媒を除いた。ろ液を濃縮し、得られた桃色固体を酢酸エチル−ヘキサン（体積比：１／２）で再結晶することで、薄桃色固体を得た。収量は、３．４０ｇ、収率は、７７％であった。
得られた固体の^１Ｈ−ＮＭＲを測定し、ＤＡ−Ａであることを確認した。
¹H-NMR(DMSO-d₆,δppm):1.44(s,9H)、3.87(d,J=6.3Hz,2H)、4.10〜4.30(m,4H)、6.27(dd,J=2.4Hz,8.1Hz1H)、6.31(d,J=2.4Hz,1H)、6.38(d,J=8.1Hz,1H)、7.14(t,J=6.3Hz,1H).

The Boc adduct (5.0 g, 18.7 mmol) and ethanol (40 ml) were added to a 100 mL eggplant flask, the inside of the system was replaced with nitrogen, platinum oxide (500 mg) was added, and the inside of the system was replaced with hydrogen. The reaction mixture, which became a yellow suspension, was stirred at room temperature for 15 hours. After completion of the reaction, ethanol was added to dissolve the precipitated white solid, and the catalyst was removed by Celite filtration. The filtrate was concentrated, and the resulting pink solid was recrystallized with ethyl acetate-hexane (volume ratio: 1/2) to obtain a light pink solid. The yield was 3.40 g, and the yield was 77%.
¹ H-NMR of the obtained solid was measured and confirmed to be DA-A.
¹ H-NMR (DMSO-d ₆ , δ ppm): 1.44 (s, 9H), 3.87 (d, J = 6.3 Hz, 2H), 4.10-4.30 (m, 4H), 6.27 (dd, J = 2.4 Hz, 8.1Hz1H), 6.31 (d, J = 2.4Hz, 1H), 6.38 (d, J = 8.1Hz, 1H), 7.14 (t, J = 6.3Hz, 1H).

Example 2 Synthesis of DA-B (Synthesis of N-Boc-propargylamine)

四つ口フラスコにプロパルギルアミン（２５．１８ｇ，０．４４８ｍｏｌ）、トリエチルアミン（５５．５２ｇ，０．５４９ｍｏｌ）、及びジクロロメタン４００ｍｌを加えた後、水浴（２０℃）で反応溶液を冷却しながら、二炭酸ジ−ｔｅｒｔ−ブチル（１１８．１５ｇ，０．５４１ｍｏｌ）を３０分かけて滴下した。滴下終了後、２時間撹拌した後、反応溶液に飽和食塩水３００ｍｌ、ジクロロメタン２００ｍｌを加え、抽出した。得られた有機層を硫酸マグネシウムで乾燥した。乾燥剤を除去後、得られた溶液の溶媒を留去し、淡黄色オイルを得た。再結晶（ヘキサン）にて精製し、白色固体のＮ−Ｂｏｃ−プロパルギルアミンを得た（収量：４７．０１ｇ，収率：６７．６％）。

After adding propargylamine (25.18 g, 0.448 mol), triethylamine (55.52 g, 0.549 mol) and 400 ml of dichloromethane to the four-necked flask, the reaction solution was cooled in a water bath (20 ° C.) Di-tert-butyl carbonate (118.15 g, 0.541 mol) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred for 2 hours, and then the reaction solution was extracted with 300 ml of saturated brine and 200 ml of dichloromethane. The obtained organic layer was dried over magnesium sulfate. After removing the desiccant, the solvent of the resulting solution was distilled off to obtain a pale yellow oil. Purification by recrystallization (hexane) gave N-Boc-propargylamine as a white solid (yield: 47.01 g, yield: 67.6%).

(Nitro compound synthesis)

窒素置換した四つ口フラスコに２−ヨード−４−ニトロアニリン（５．１１ｇ，１９．４ｍｍｏｌ）、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロリド（２８１．７ｍｇ，０．４０１ｍｍｏｌ）、ヨウ化銅（１６０．７ｍｇ，０．８４４ｍｍｏｌ）、及びジエチルアミン３０ｍｌを入れ、室温（２０℃）で１０分間攪拌した。その後、Ｎ−Ｂｏｃ−プロパルギルアミン（３．７２ｇ，２４．０ｍｍｏｌ）を加えて、室温（２０℃）にて、４時間攪拌した。ＨＰＬＣ（High performance liquid chromatography)にて、原料の消失を確認した後、酢酸エチル２００ｍｌ、１Ｍ塩化アンモニウム水溶液を２００ｍｌ加え、抽出した。得られた有機層を１Ｍ塩化アンモニウム水溶液で、２回洗浄し、無水硫酸マグネシウムで乾燥した。乾燥剤を除去後、ろ液を濃縮し、シリカゲルカラムクロマトグラフィー（留出液：酢酸エチル：ヘキサン＝３：７（体積比））にて精製した。収量は、４．９７ｇ、収率は８８．０％であった。

In a four-necked flask purged with nitrogen, 2-iodo-4-nitroaniline (5.11 g, 19.4 mmol), bis (triphenylphosphine) palladium (II) dichloride (281.7 mg, 0.401 mmol), copper iodide (160.7 mg, 0.844 mmol) and 30 ml of diethylamine were added and stirred at room temperature (20 ° C.) for 10 minutes. Thereafter, N-Boc-propargylamine (3.72 g, 24.0 mmol) was added, and the mixture was stirred at room temperature (20 ° C.) for 4 hours. After confirming disappearance of the raw materials by HPLC (High performance liquid chromatography), 200 ml of ethyl acetate and 200 ml of 1M aqueous ammonium chloride solution were added and extracted. The obtained organic layer was washed twice with 1M aqueous ammonium chloride solution and dried over anhydrous magnesium sulfate. After removing the desiccant, the filtrate was concentrated and purified by silica gel column chromatography (distillate: ethyl acetate: hexane = 3: 7 (volume ratio)). The yield was 4.97 g, and the yield was 88.0%.

(Synthesis of DA-B)

四つ口フラスコに前記ニトロ体（１２．４５ｇ，４２．７ｍｍｏｌ）を入れ、エタノール２００ｍｌに懸濁させた。系内を脱気、窒素置換した後、パラジウムカーボン（１．２３ｇ）を加え、水素置換し、室温（２０℃）にて２日間撹拌した。その後、セライトろ過により、パラジウムカーボンを除去し、溶媒を留去した。得られた固体をトルエン１００ｍｌに溶解させた後、ヘキサン５０ｍｌを加えて、再結晶した。得られた固体を減圧乾燥し、薄茶色固体を得た（収量：９．１３ｇ、収率：８０．６％）。得られた固体の^１Ｈ−ＮＭＲを測定し、ＤＡ−Ｂであることを確認した。
¹H-NMR(DMSO-d₆,δppm):1.38(s,9H)、1.57(ｑ,J=7.2Hz,2H)、2.30(t,J=7.2Hz,2H)、2.94(quin,J=6.0Hz,2H)、3.88〜4.22(m,4H)、6.22(dd,J=2.1Hz,8.1Hz,1H)、6.25(d,J=2.1Hz,1H)、6.37(d,J=8.1Hz,1H)、6.84(t,J=6.0Hz,1H).

The nitro compound (12.45 g, 42.7 mmol) was placed in a four-necked flask and suspended in 200 ml of ethanol. The system was degassed and purged with nitrogen, then palladium carbon (1.23 g) was added, purged with hydrogen, and stirred at room temperature (20 ° C.) for 2 days. Thereafter, palladium carbon was removed by Celite filtration, and the solvent was distilled off. The obtained solid was dissolved in 100 ml of toluene, and then 50 ml of hexane was added for recrystallization. The obtained solid was dried under reduced pressure to obtain a light brown solid (yield: 9.13 g, yield: 80.6%). ¹ H-NMR of the obtained solid was measured and confirmed to be DA-B.
¹ H-NMR (DMSO-d ₆ , δ ppm): 1.38 (s, 9H), 1.57 (q, J = 7.2 Hz, 2H), 2.30 (t, J = 7.2 Hz, 2H), 2.94 (quin, J = 6.0Hz, 2H), 3.88 ~ 4.22 (m, 4H), 6.22 (dd, J = 2.1Hz, 8.1Hz, 1H), 6.25 (d, J = 2.1Hz, 1H), 6.37 (d, J = 8.1Hz , 1H), 6.84 (t, J = 6.0Hz, 1H).

<Example 3> Synthesis of DA-D (synthesis of nitro compound)

Boc-glycine (10.17 g, 58.05 mmol) was placed in a nitrogen-substituted four-necked flask and dissolved in 150 ml of THF. N-methylmorpholine (NMM) (11.93 g, 117.9 mmol) was added there, and it cooled to -20 degreeC. To this solution was added dropwise isobutylchloroformate (9.99 g, 73.14 mmol). At this time, care was taken that the temperature of the reaction solution did not exceed 0 ° C. After dropping, the mixture was stirred at -20 ° C for 10 minutes. At this time, the reaction solution became cloudy. Ten minutes later, 360 ml of a THF solution of 2-amino-4-nitroaniline (8.86 g, 57.86 mmol) was added dropwise from a dropping funnel. After completion of dropping, the mixture was stirred at -20 ° C for 1 hour, and then stirred at room temperature (20 ° C) for 18 hours. After 18 hours, the precipitated solid was filtered off, and the solvent of the obtained filtrate was distilled off to obtain a concentrated solution. To this concentrate, 200 ml of ethyl acetate and 200 ml of 1M aqueous potassium dihydrogen phosphate solution were added for extraction. The obtained organic layer was washed once with a 1M aqueous potassium dihydrogen phosphate solution, once with a saturated saline solution, twice with a saturated aqueous sodium bicarbonate solution, and once with a saturated saline solution. The obtained organic layer was dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off from the filtrate to obtain an orange solid. This solid was suspended in 300 ml of toluene and heated and stirred for 30 minutes. The solid was collected by suction filtration, and ¹ H-NMR of the obtained solid was measured. As a result, it was confirmed to be the target nitro compound (yield: 9.85 g, yield: 54.9%).

(Synthesis of DA-D)

The nitro compound (9.85 g, 31.75 mmol) was added to an eggplant-shaped flask, and 150 ml of ethanol was added. After the reaction vessel was purged with nitrogen, palladium carbon (1.11 g, 10% by mass with respect to the mass of the nitro compound) was added, and the nitrogen was substituted again. Subsequently, the reaction vessel was replaced with hydrogen and stirred at 20 ° C. for 48 hours. After completion of the reaction, palladium carbon was removed by Celite filtration, and the solvent was distilled off from the filtrate. When 150 ml of toluene was added to the obtained concentrated liquid and heated to reflux, a solid was precipitated. The precipitated solid was filtered while hot to obtain a light purple solid. The yield was 8.05 g, and the yield was 90.4%. ¹ H-NMR of the obtained solid was measured and confirmed to be DA-C.
¹ H-NMR (DMSO-d ₆ , δ ppm): 1.40 (s, 9H), 3.70 (d, J = 6.0 Hz, 2H), 4.04 (bs, 2H), 4.35 (bs, 2H), 6.23 (dd, J = 2.4Hz, 8.0Hz, 1H), 6.48 (d, J = 8.0Hz, 1H), 6.61 (d, J = 2.4Hz, 1H), 7.05 (t, J = 6.0Hz, 1H), 8.94 (s , 1H).

<Example 4> Synthesis of DA-E (synthesis of nitro compound)

四つ口フラスコに２−アミノ−４−ニトロアニリン（４．３６ｇ，２８．４７ｍｍｏｌ）、Ｎ−α，ｉｍ−ジ−ｔ−ブトキシカルボニル−Ｌ−ヒスチジン（１４．６１ｇ，３３．７０ｍｍｏｌ）、及び４−Ｎ，Ｎ−ジメチルアミノピリジン（４−ＤＭＡＰ）（１．７８ｇ，１４．５７ｍｍｏｌ）を入れ、ＤＭＦ１５０ｍｌを加えた。窒素置換した後、１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド塩酸塩（ＥＤＡＰ）（６．５８ｇ，３４．３２ｍｍｏｌ）を加え、２０℃にて１８時間撹拌した。反応終了後、反応溶液に酢酸エチル、純水を加えて、抽出した。得られた有機層を純水で２回洗浄し、無水硫酸マグネシウムで乾燥した。乾燥剤を除去後、ろ液を濃縮し、オイル状の化合物を得た。このオイル状の化合物にトルエン１５０ｍｌを加え、加熱撹拌したところ、黄色固体が析出した。得られた黄色固体を吸引ろ取し、減圧乾燥した。^１Ｈ−ＮＭＲの測定により、得られた黄色固体は、目的のジアミン化合物ＤＡ−３であることを確認した。収量：５．７４ｇ、収率：４１．１％であった。

In a four-necked flask, 2-amino-4-nitroaniline (4.36 g, 28.47 mmol), N-α, im-di-t-butoxycarbonyl-L-histidine (14.61 g, 33.70 mmol), and 4-N, N-dimethylaminopyridine (4-DMAP) (1.78 g, 14.57 mmol) was added, and 150 ml of DMF was added. After nitrogen substitution, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDAP) (6.58 g, 34.32 mmol) was added, and the mixture was stirred at 20 ° C. for 18 hours. After completion of the reaction, the reaction solution was extracted with ethyl acetate and pure water. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the filtrate was concentrated to obtain an oily compound. When 150 ml of toluene was added to this oily compound and the mixture was heated and stirred, a yellow solid was precipitated. The resulting yellow solid was collected by suction filtration and dried under reduced pressure. ¹ H-NMR measurement confirmed that the obtained yellow solid was the target diamine compound DA-3. Yield: 5.74 g, yield: 41.1%.

(Synthesis of DA-E)

ナス型フラスコに前記ニトロ体（５．７４ｇ，１１．７０ｍｍｏｌ）を入れ、エタノール１５０ｍｌを加えた。反応容器を窒素置換した後、パラジウムカーボン（０．５９ｇ）を加え、窒素置換した。次いで、反応容器を水素置換し、２０℃にて、４８時間撹拌した。反応終了後、セライトろ過により、パラジウムカーボンを除去し、ろ液から溶媒を留去した。生成物はオイル状であったが、トルエン１００ｍｌを加え、超音波をあてると、薄紫色の固体が析出した。析出した固体を、加熱溶解した後、水浴にて冷却し、再結晶を行った。析出した固体を吸引ろ取し、減圧乾燥し、薄紫色固体を得た。収量：２．３６ｇ、収率：４３．８％であった。得られた固体の^１Ｈ−ＮＭＲを測定し、ＤＡ−Ｄであることを確認した。
¹H-NMR(DMSO-d₆,δppm):1.36(s,9H)、1.56(s,9H)、2.76〜2.96(m,3H)、4.04(bs,2H)、4.35(bs,2H)、6.25(dd,J=2.4Hz,8.4Hz,1H)、6.48(d,J=8.4Hz,1H)、6.55(d,J=2.4Hz,1H)、7.02(d,J=8.0Hz,1H)、7.29(s,1H)、8.13(s,1H)、9.11(s,1H).

The said nitro body (5.74g, 11.70mmol) was put into the eggplant type flask, and 150 ml of ethanol was added. After the reaction vessel was purged with nitrogen, palladium carbon (0.59 g) was added to purge with nitrogen. The reaction vessel was then purged with hydrogen and stirred at 20 ° C. for 48 hours. After completion of the reaction, palladium carbon was removed by Celite filtration, and the solvent was distilled off from the filtrate. Although the product was in the form of an oil, a light purple solid was precipitated when 100 ml of toluene was added and ultrasonic waves were applied. The precipitated solid was dissolved by heating, then cooled in a water bath and recrystallized. The precipitated solid was collected by suction filtration and dried under reduced pressure to obtain a pale purple solid. Yield: 2.36 g, yield: 43.8%. ¹ H-NMR of the obtained solid was measured and confirmed to be DA-D.
¹ H-NMR (DMSO-d ₆ , δ ppm): 1.36 (s, 9H), 1.56 (s, 9H), 2.76 to 2.96 (m, 3H), 4.04 (bs, 2H), 4.35 (bs, 2H), 6.25 (dd, J = 2.4Hz, 8.4Hz, 1H), 6.48 (d, J = 8.4Hz, 1H), 6.55 (d, J = 2.4Hz, 1H), 7.02 (d, J = 8.0Hz, 1H) 7.29 (s, 1H), 8.13 (s, 1H), 9.11 (s, 1H).

<Example 5> Preparation of polyamic acid (A-1) solution In a 300 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1.125 g (10.40 mmol) of p-PDA and 0 of DA-B were added. 689 g (2.596 mmol) and NMP 30.62 g were added and stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 2.424 g (12.36 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid (A-1). Solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 138.6 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 16,079 and Mw = 33,544.

<Example 6> Preparation of solution of polyamic acid (A-2) In a 300 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 1.037 g (9.589 mmol) of p-PDA and 0 of DA-D were added. .671 g (2.394 mmol) and NMP 28.37 g were added and dissolved while stirring while feeding nitrogen. While stirring this diamine solution, 2.277 g (11.61 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid (A-2). Solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 146.2 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 17,260 and Mw = 34,532.

<Example 7> Preparation of polyamic acid (A-3) solution In a 300 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 0.951 g (8.794 mmol) of p-PDA and 1 DA-E were added. .012 g (2.197 mmol) and NMP 29.10 g were added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 2.095 g (10.69 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid (A-3). Solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 157.3 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 20,610 and Mw = 40,640.

<Comparative Synthesis Example 1> Preparation of Polyamic Acid (B-1) Solution In a 300 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 1.621 g (14.99 mmol) of p-PDA and 28.96 g of NMP Was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 2.87 g (14.74 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid (B-1). Solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 152.7 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 13,972 and Mw = 30,181.

<Example 8> Preparation of liquid crystal aligning agent (A-1) 12.59 g of the solution of polyamic acid (A-1) obtained in Example 5 was dispensed into a 50 mL Erlenmeyer flask containing a stir bar, and NMP4. 21g and 4.19g of BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (A-1).

<Example 9> Preparation of liquid crystal aligning agent (A-2) 11.37 g of the solution of polyamic acid (A-2) obtained in Example 6 was dispensed into a 50 mL Erlenmeyer flask containing a stirring bar, and NMP3. 80 g and 3.79 g of BCS were added and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A-2).

<Example 10> Preparation of liquid crystal aligning agent (A-3) 11.17 g of the solution of polyamic acid (A-3) obtained in Example 7 was dispensed into a 50 mL Erlenmeyer flask containing a stir bar, and NMP3. 74g and 3.76g of BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (A-3).

<Comparative Example 1> Preparation of Liquid Crystal Alignment Agent (B-1) Comparative Synthesis Example 1 12.98 g of the obtained polyamic acid (B-1) solution was dispensed into a 50 mL Erlenmeyer flask containing a stir bar, and NMP4. 42g and 4.27g of BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (B-1).

<Example 11>
The liquid crystal aligning agent (A-1) obtained in Example 8 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. After baking for 20 minutes at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. This polyimide film was rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation amount: 0.4 mm), and then the surface condition of the polyimide film was observed. No debris or peeling of the polyimide film was observed.

<Example 12>
A polyimide film was prepared in the same manner as in Example 11 except that the liquid crystal aligning agent (A-2) obtained in Example 9 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.

<Example 13>
A polyimide film was prepared in the same manner as in Example 11 except that the liquid crystal aligning agent (A-3) obtained in Example 10 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.

<Comparative example 2>
A polyimide film was prepared in the same manner as in Example 11 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing and scraped scraps of the polyimide film were observed.

<Example 14>
The liquid crystal aligning agent (A-1) obtained in Example 8 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. After baking for 20 minutes at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. This polyimide film is rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, pushing amount: 0.4 mm), cleaned by irradiating with ultrasonic waves in pure water for 1 minute, and air blow After removing the water droplets at, the substrate was dried at 80 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two such substrates with a liquid crystal alignment film are prepared, and after a 6 μm spacer is dispersed on the liquid crystal alignment film surface of one substrate, the rubbing directions of the two substrates are combined so that the rubbing direction can be twisted by 85 degrees from antiparallel, The periphery was sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of 6 μm was produced. A liquid crystal (MLC-2003, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell, and the inlet was sealed to obtain a twisted nematic liquid crystal cell. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. As a result of measuring the voltage holding ratio of the liquid crystal cell and then measuring the ion density, the voltage holding ratio was 99.3% at a temperature of 23 ° C., 98.7% at a temperature of 60 ° C., and 94 at a temperature of 90 ° C. a .1%, the ion density of 10pC / cm ² at 23 ° C., was 18pC / cm ² at 60 ° C..

<Example 15>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 14 except that the liquid crystal aligning agent (A-2) obtained in Example 9 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density Was measured.
When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. As a result of measuring the voltage holding ratio of the liquid crystal cell and then measuring the ion density, the voltage holding ratio was 99.3% at a temperature of 23 ° C., 98.8% at a temperature of 60 ° C., and 94 at a temperature of 90 ° C. a .4%, the ion density of 5 pC / cm ² at 23 ° C., was 11pC / cm ² at 60 ° C..

<Example 16>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 14 except that the liquid crystal aligning agent (A-3) obtained in Example 10 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. Liquid crystal (MLC-2003, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. As a result of measuring the voltage holding ratio of the liquid crystal cell and then measuring the ion density, the voltage holding ratio was 99.4% at a temperature of 23 ° C., 99.1% at a temperature of 60 ° C., and 96 at a temperature of 90 ° C. a .7%, the ion density is pC / cm ² at 23 ° C., it was 4Pc / cm ² at 60 ° C..

<Comparative Example 3>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 14 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. With respect to this cell, the voltage holding ratio was measured, and then the ion density was measured. As a result, the voltage holding ratio was 99.1% at a temperature of 23 ° C., 97.4% at a temperature of 60 ° C., and 86. 7%, ion density 50pc / cm ² at 23 ° C., was 256pC / cm ² at a temperature 60 ° C..

Example 17 Synthesis of DA-F (Precursor Synthesis 1)

３−ブロモプロピルアミン臭化水素酸塩（１０５．１０ｇ，０．４８０ｍｏｌ）を２Ｌ四つ口フラスコに入れ、ジクロロメタン９７８．８８ｇ、及び二炭酸ジ−ｔｅｒｔ−ブチル（１１５．１３ｇ，０．５２８ｍｏｌ）を加え、０℃（氷浴）にて撹拌した。次いで、滴下ロートにトリエチルアミン（９２．５８ｇ，０．９１５ｍｏｌ）を入れ、四つ口フラスコ中のスラリー溶液へ３０分かけて滴下した。滴下開始後、反応溶液が激しく発泡し、白色固体が析出した。滴下終了後、２時間撹拌した。反応終了後、反応溶液に純水５００ｍｌを加え、抽出した。得られた有機層を純水で２回洗浄し、無水硫酸マグネシウムで乾燥した。乾燥剤を除去後、溶媒を留去し、無色透明のオイルを得た。このオイル状物質にヘキサン５００ｍｌを加え、−７８℃下で晶析し、白色固体を得た。固体を吸引ろ取し、減圧乾燥した。^１Ｈ−ＮＭＲの測定により、得られた白色固体がｔｅｒｔ−ブチル３−ブロモプロピルカルバメートであることを確認した。収量は８９．５５ｇ、収率は７８．３％であった。
¹H NMR (400MHz, CDCl₃,δppm)：1.44(s, 9H), 2.05(quin, J=6.4Hz, 2H), 3.27(q, J=6.4Hz, 2H), 3.45(t, J=6.4Hz,2H), 4.69(bs, 1H).

3-Bromopropylamine hydrobromide (105.10 g, 0.480 mol) was placed in a 2 L four-necked flask, 978.88 g of dichloromethane, and di-tert-butyl dicarbonate (115.13 g, 0.528 mol). And stirred at 0 ° C. (ice bath). Next, triethylamine (92.58 g, 0.915 mol) was added to the dropping funnel and added dropwise to the slurry solution in the four-necked flask over 30 minutes. After the start of dropping, the reaction solution foamed vigorously and a white solid was precipitated. It stirred for 2 hours after completion | finish of dripping. After completion of the reaction, 500 ml of pure water was added to the reaction solution and extracted. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a colorless and transparent oil. To this oily substance, 500 ml of hexane was added and crystallized at −78 ° C. to obtain a white solid. The solid was filtered off with suction and dried under reduced pressure. ¹ H-NMR measurement confirmed that the obtained white solid was tert-butyl 3-bromopropylcarbamate. The yield was 89.55 g, and the yield was 78.3%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.44 (s, 9H), 2.05 (quin, J = 6.4Hz, 2H), 3.27 (q, J = 6.4Hz, 2H), 3.45 (t, J = 6.4 Hz, 2H), 4.69 (bs, 1H).

(Precursor synthesis 2)

四つ口フラスコに１，５−ジヒドロキシ−４，８−ジニトロアントラキノン（１４．０４ｇ，４２．５２ｍｍｏｌ）を入れ、ＮＭＰ３００ｇを加えて、８０℃で加熱し、１，５−ジヒドロキシ−４，８−ジニトロアントラキノンを完全に溶解させた。前記溶液に炭酸カリウム（１２．０１ｇ，８６．９５ｍｍｏｌ）、及びヨウ化カリウム（２８．７７ｇ，１７３．３３ｍｍｏｌ）を添加した後、ｔｅｒｔ−ブチル３−ブロモプロピルカルバメート（３０．４０ｇ，１２７．７ｍｍｏｌ） を加えて、８０℃で６時間加熱撹拌した。得られた反応溶液を０．５Ｍ塩酸水溶液５００ｍｌ中に注ぎ、さらに酢酸エチル５００ｍｌを加えて、抽出した。得られた有機層を０．５Ｍ塩酸水溶液及び飽和食塩水にて洗浄し、無水硫酸マグネシウムで乾燥した。乾燥剤を除去後、溶媒を留去し、残渣をシリカゲルカラムクロマトグラフィー（留出液：１，２−ジクロロエタン：酢酸エチル＝７：３（体積比））にて精製し、黄色固体を得た。^１Ｈ−ＮＭＲの測定により、得られた黄色固体は上記ニトロ体であることを確認した。収量は、３．２１ｇ、収率は１１．７％であった。
¹H NMR (400MHz, CDCl₃,δppm)：1.42(s, 18H), 2.13(quin, J=6.0Hz, 4H), 3.41(q, J=6.0Hz, 4H), 4.289(t, J=6.0Hz,4H), 5.28 (bs, 2H), 7.23(d, J=8.8Hz, 2H), 7.93(d, J=8.8Hz, 2H).

Add 1,5-dihydroxy-4,8-dinitroanthraquinone (14.04 g, 42.52 mmol) to a four-necked flask, add 300 g of NMP, heat at 80 ° C., and heat 1,5-dihydroxy-4,8- Dinitroanthraquinone was completely dissolved. After adding potassium carbonate (12.01 g, 86.95 mmol) and potassium iodide (28.77 g, 173.33 mmol) to the solution, tert-butyl 3-bromopropylcarbamate (30.40 g, 127.7 mmol) And heated and stirred at 80 ° C. for 6 hours. The obtained reaction solution was poured into 500 ml of 0.5 M aqueous hydrochloric acid solution, and further extracted with 500 ml of ethyl acetate. The obtained organic layer was washed with 0.5 M aqueous hydrochloric acid solution and saturated brine, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off, and the residue was purified by silica gel column chromatography (distillate: 1,2-dichloroethane: ethyl acetate = 7: 3 (volume ratio)) to obtain a yellow solid. . It was confirmed by ¹ H-NMR measurement that the obtained yellow solid was the nitro form. The yield was 3.21 g and the yield was 11.7%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.42 (s, 18H), 2.13 (quin, J = 6.0Hz, 4H), 3.41 (q, J = 6.0Hz, 4H), 4.289 (t, J = 6.0 Hz, 4H), 5.28 (bs, 2H), 7.23 (d, J = 8.8Hz, 2H), 7.93 (d, J = 8.8Hz, 2H).

(Synthesis of DA-F)

四つ口フラスコに上記ジミニトロ体（１．４８ｇ、２．３０ｍｍｏｌ）、硫化ナトリウム九水和物（５．７２ｇ、２３．８２ｍｍｏｌ）を入れ、純水５０ｍｌを加えて、２時間加熱還流した。反応溶液を室温まで冷却した後、２質量％水酸化ナトリウム水溶液を５０ｍｌを加え、５０℃にて１時間撹拌した。反応溶液中の固体を吸引ろ取し、純水で洗浄した。得られた固体を再結晶（メタノール）にて精製し、紫色固体を得た。^１ＨＮＭＲより得られた紫色固体はジアミン（F）であることを確認した。収量は、０．１５ｇ、収率は１１．２％であった。
¹H NMR (400MHz, CDCl₃,δppm)：1.49(s, 18H), 2.06(quin, J=5.6Hz, 4H), 3.48(q, J=5.6Hz, 4H), 4.12(t, J=5.6Hz,4H), 6.54 (bs,42H), 6.92(d, J=9.2Hz, 2H), 7.06（ｍ，2H）7.16 (d, J=9.2Hz, 2H).

The diminitro compound (1.48 g, 2.30 mmol) and sodium sulfide nonahydrate (5.72 g, 23.82 mmol) were placed in a four-necked flask, 50 ml of pure water was added, and the mixture was heated to reflux for 2 hours. After the reaction solution was cooled to room temperature, 50 ml of a 2% by mass aqueous sodium hydroxide solution was added and stirred at 50 ° C. for 1 hour. The solid in the reaction solution was collected by suction filtration and washed with pure water. The obtained solid was purified by recrystallization (methanol) to obtain a purple solid. ^The purple solid obtained from ¹ HNMR was confirmed to be diamine (F). The yield was 0.15 g, and the yield was 11.2%.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.49 (s, 18H), 2.06 (quin, J = 5.6Hz, 4H), 3.48 (q, J = 5.6Hz, 4H), 4.12 (t, J = 5.6 Hz, 4H), 6.54 (bs, 42H), 6.92 (d, J = 9.2Hz, 2H), 7.06 (m, 2H) 7.16 (d, J = 9.2Hz, 2H).

Example 18 Synthesis of DA-H (Precursor Synthesis 1)

１Ｌ四つ口フラスコに２，６−ジヨード−４−ニトロアニリン（５０．００ｇ，１２８ｍｍｏｌ）、ビス(トリフェニルホスフィン)パラジウム(ＩＩ)ジクロリド (９００ｍｇ，１．２８ｍｍｏｌ)、ヨウ化銅(４８８ｍｇ，２．５６ｍｍｏｌ)、ジエチルアミン３２ｍｌ、及びＴＨＦ１６５ｍｌを加え、室温（２０℃）にて１０分間撹拌した。その後、四つ口フラスコ中の溶液を撹拌させながら、Ｎ−Ｂｏｃ−プロパルギルアミン（４７．６０ｇ，３０７ｍｍｏｌ）のＴＨＦ溶液（９０ｍｌ）を１５分かけて滴下した。滴下終了後、室温（２０℃）にて１２時間撹拌した。１２時間後、反応溶液を１．２８Ｌの純水に撹拌しながら投入し、析出した黒色沈殿を吸引ろ取し、水５０ｍｌで２回洗浄した。得られた固体を減圧乾燥し、茶色固体を得た。この茶色固体を再結晶（トルエン）にて精製し、黄色固体を得た。^１Ｈ−ＮＭＲの測定により、得られた黄色固体は上記ニトロ体であることを確認した。収量は、４７．０９ｇ、収率は８３．０％であった。
¹H NMR (400MHz, CDCl₃,δppm)：1.48(s, 18H), 4.16(d, J=6.0Hz, 4H), 4.93 (bs, 2H), 5.78(bs, 2H), 8.09 (s, 2H).

In a 1 L four-necked flask, 2,6-diiodo-4-nitroaniline (50.00 g, 128 mmol), bis (triphenylphosphine) palladium (II) dichloride (900 mg, 1.28 mmol), copper iodide (488 mg, 2 .56 mmol), diethylamine 32 ml, and THF 165 ml were added, and the mixture was stirred at room temperature (20 ° C.) for 10 minutes. Thereafter, a THF solution (90 ml) of N-Boc-propargylamine (47.60 g, 307 mmol) was added dropwise over 15 minutes while stirring the solution in the four-necked flask. After completion of dropping, the mixture was stirred at room temperature (20 ° C.) for 12 hours. After 12 hours, the reaction solution was added to 1.28 L of pure water with stirring, and the black precipitate that had precipitated was collected by suction filtration and washed twice with 50 ml of water. The obtained solid was dried under reduced pressure to obtain a brown solid. This brown solid was purified by recrystallization (toluene) to obtain a yellow solid. It was confirmed by ¹ H-NMR measurement that the obtained yellow solid was the nitro form. The yield was 47.09 g, and the yield was 83.0%.
¹ H NMR (400 MHz, CDCl ₃ , δ ppm): 1.48 (s, 18H), 4.16 (d, J = 6.0 Hz, 4H), 4.93 (bs, 2H), 5.78 (bs, 2H), 8.09 (s, 2H ).

(Synthesis of DA-H)

１Ｌ四つ口フラスコに前記ニトロ体（４７．０７ｇ，１０６ｍｍｏｌ)を入れ、エタノール５６０ｍｌに懸濁させた。系内を脱気、窒素置換した後、パラジウムカーボン（４．７１ｇ）を加え、水素置換し、室温（５０℃）にて８日間加熱撹拌した。セライトろ過により、パラジウムカーボンを除去し、溶媒を留去した。得られた固体を１，２−ジクロロエタン２００ｍｌに溶解させた後、ヘキサン７０ｍｌを加えて、再結晶した。得られた固体を減圧乾燥し、灰色固体を得た。収量は、３９．５４ｇ、収率は８７．５％であった。得られた固体の^１Ｈ−ＮＭＲを測定し、ＤＡ−Ｈであることを確認した。
¹H NMR (400MHz, CDCl₃,δppm)：1.45(s, 18H), 1.78(quin, J=6.4Hz, 4H), 2.48(t, J=6.4Hz, 4H), 3.45(q, J=6.4Hz, 4H), 4.69(bs, 1H), 6.36(s, 1H).

The nitro compound (47.07 g, 106 mmol) was placed in a 1 L four-necked flask and suspended in 560 ml of ethanol. The system was degassed and purged with nitrogen, then palladium carbon (4.71 g) was added, purged with hydrogen, and heated and stirred at room temperature (50 ° C.) for 8 days. The palladium carbon was removed by Celite filtration, and the solvent was distilled off. The obtained solid was dissolved in 200 ml of 1,2-dichloroethane, and then 70 ml of hexane was added for recrystallization. The obtained solid was dried under reduced pressure to obtain a gray solid. The yield was 39.54 g, and the yield was 87.5%. ¹ H-NMR of the obtained solid was measured and confirmed to be DA-H.
¹ H NMR (400MHz, CDCl ₃ , δppm): 1.45 (s, 18H), 1.78 (quin, J = 6.4Hz, 4H), 2.48 (t, J = 6.4Hz, 4H), 3.45 (q, J = 6.4 Hz, 4H), 4.69 (bs, 1H), 6.36 (s, 1H).

<Example 19> Preparation of polyamic acid (A-4) solution To a stirrer and a 100 mL four-necked flask equipped with a nitrogen introduction tube, 1.7281 g (16.47 mmol) of p-PDA and 0 of DA-A were added. .9509 g (4.007 mmol) and 46.12 g of NMP were added and stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 3.8093 g (19.43 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid (A-4 ) Was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 149 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 18,136 and Mw = 37,265.

<Example 20> Preparation of polyamic acid (A-5) solution In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 0.8665 g (8.013 mmol) of p-PDA and 0 of DA-H were added. 8442 g (1.998 mmol) and NMP 25.31 g were added and dissolved while stirring while feeding nitrogen. While stirring this diamine solution, 1.9047 g (9.713 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid (A-5). ) Was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 254.7 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 27,447 and Mw = 59,038.

<Example 21> Preparation of polyamic acid ester resin (C-1) The inside of a 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 2.00 g (18.50 mmol) of p-PDA, and 1 DA-D. 2269 g (4.624 mmol), 167.67 g of NMP, and 4.21 g (53.26 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring the diamine solution, 7.216 g (22.19 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was poured into 882 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 889 g of water, once with 882 g of ethanol, three times with 221 g of ethanol, and dried to obtain 7.22 g of white polyamic acid ester resin powder (C-1). The yield was 81.8%. Moreover, the molecular weight of this polyamic acid ester was Mn = 20,469 and Mw = 40,025.

<Example 22> Preparation of polyamic acid ester resin (C-2) A 300 mL four-necked flask with a stirrer was placed in a nitrogen atmosphere, 2.00 g (18.50 mmol) of p-PDA and 1 DA-B. 2961 g (4.624 mmol), 168.98 g of NMP and 4.21 g (53.26 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring the diamine solution, 7.216 g (22.19 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was poured into 889 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 889 g of water, once with 889 g of ethanol, three times with 222 g of ethanol, and dried to obtain 7.79 g of white polyamic acid ester resin powder C-2). The yield was 87.6%. Moreover, the molecular weight of this polyamic acid ester was Mn = 20,886 and Mw = 45,830.

<Example 23> Preparation of polyamic acid ester resin (C-3) A 300 mL four-necked flask with a stirrer was placed in a nitrogen atmosphere, p-PDA was 1.50 g (13.87 mmol), and DA-E was 1 .597 g (3.468 mmol), 65.26 g of NMP, and 3.13 g (39.53 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring the diamine solution, 5.3556 g (16.47 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 72.51 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C.) for 15 minutes. The obtained polyamic acid ester solution was poured into 725 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 725 g of water, once with 725 g of ethanol, three times with 181 g of ethanol, and dried to obtain 3.76 g of white polyamic acid ester resin powder (C-3). The yield was 51.8%. Moreover, the molecular weight of this polyamic acid ester was Mn = 20,525 and Mw = 43,395.

<Example 24> Preparation of polyamic acid ester resin (C-4) The inside of a 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 2.50 g (23.11 mmol) of p-PDA, and 1 DA-A. 3715 g (5.80 mmol), 97.16 g of NMP, and 5.21 g (65.89 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring the diamine solution, 1.926 g (27.45 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 107.95 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C.) for 15 minutes. The obtained polyamic acid ester solution was added to 1080 g of water with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 1080 g of water, once with 1080 g of ethanol, three times with 270 g of ethanol, and dried to obtain 9.17 g of white polyamic acid ester resin powder (C-4). The yield was 85.2%. Moreover, the molecular weight of this polyamic acid ester was Mn = 17,573 and Mw = 37,258.

<Example 25> Preparation of polyamic acid ester resin (C-5) A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 1.420 g (13.13 mmol) of p-PDA, and 1 DA-H. .3872 g (3.283 mmol), 59.54 g of NMP, and 2.87 g (36.24 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring this diamine solution, 4.9999 g (15.10 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 66.15 g of NMP was added to the reaction solution, and the mixture was stirred at room temperature (20 ° C.) for 15 minutes. The obtained polyamic acid ester solution was poured into 662 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 662 g of water, once with 662 g of ethanol, three times with 165 g of ethanol, and dried to obtain 5.11 g of white polyamic acid ester resin powder (C-5). The yield was 77.3%. Moreover, the molecular weight of this polyamic acid ester was Mn = 14,724 and Mw = 27,150.

Comparative Synthesis Example 2 Preparation of Polyamic Acid Ester Resin (D-1) The inside of a 50 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 0.699 g (64.64 mmol) of p-PDA, and 427. of NMP. 1 g and 11.65 g (147.38 mmol) of pyridine as a base were added and dissolved by stirring. Next, 19.9657 g (61.41 mmol) of 1,3DM-CBDE-Cl was added while stirring the diamine solution, and the mixture was reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was added to 2248 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 2248 g of water, once with 2248 g of ethanol, three times with 562 g of ethanol, and dried to obtain 22.10 g of a white polyamic acid ester resin (D-1) powder. The yield was 98.4%. Moreover, the molecular weight of this polyamic acid ester was Mn = 16,813 and Mw = 38,585.

<Example 26> Preparation of liquid crystal aligning agent (A-4) The solution 6.18g of the polyamic acid (A-4) obtained in Example 19 was fractionated into a 50 mL Erlenmeyer flask containing a stir bar, and NMP1. 60 g and 1.99 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-4).

<Example 27> Preparation of liquid crystal aligning agent (A-5) The solution of the polyamic acid (A-5) obtained in Example 20 was fractionated in a 50 mL Erlenmeyer flask containing a stir bar, and NMP1. 15g and 1.76g of BCS were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (A-5).

<Example 28> Preparation of liquid crystal aligning agent (C-1) 1.65 g of the polyamic acid ester resin powder obtained in Example 21 was placed in an Erlenmeyer flask, 14.95 g of γ-BL was added, and the mixture was stirred at room temperature for 24 hours. Dissolved. Γ-BL (5.43 g) and BCS (5.55 g) were added to this solution, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-1).

<Example 29> Preparation of liquid crystal aligning agent (C-2) 0.733 g of the polyamic acid ester resin powder obtained in Example 22 is placed in an Erlenmeyer flask, 6.60 g of γ-BL is added, and the mixture is stirred for 24 hours at room temperature to dissolve. I let you. To this solution, 2.48 g of γ-BL and 2.45 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-2).

<Example 30> Preparation of liquid crystal aligning agent (C-3) 0.907 g of the polyamic acid ester resin powder obtained in Example 23 was placed in an Erlenmeyer flask, and 8.18 g of γ-BL was added and dissolved by stirring at room temperature for 24 hours. I let you. Γ-BL3.06g and BCS3.04g were added to this solution, and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (C-3).

<Example 31> Preparation of liquid crystal aligning agent (C-4) 0.802 g of polyamic acid ester resin powder obtained in Example 24 was put into an Erlenmeyer flask, 7.23 g of γ-BL was added, and the mixture was stirred at room temperature for 24 hours to dissolve. I let you. To this solution, 2.78 g of γ-BL and 2.68 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (C-4).

<Example 32> Preparation of liquid crystal aligning agent (C-5) 0.755g of polyamic acid ester resin powder obtained in Example 25 was put into an Erlenmeyer flask, γ-BL7.57g was added, and it stirred for 24 hours at room temperature and dissolved. I let you. To this solution, 2.65 g of γ-BL and 2.55 g of BCS were added and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (C-5).

Comparative Example 4 Preparation of Liquid Crystal Alignment Agent (D-1) 1.02 g of the polyamic acid ester resin powder obtained in Comparative Synthesis Example 2 is placed in an Erlenmeyer flask, added with 9.21 g of DMF, and stirred at room temperature for 24 hours to dissolve. It was. To this solution, 3.29 g of γ-BL and 3.39 g of BCS were added and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (D-1).

<Example 33>
A polyimide film was prepared in the same manner as in Example 11 except that the liquid crystal aligning agent (A-4) obtained in Example 26 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing were observed, but the results were smaller than those of Comparative Example 2. No chipping of the polyimide film and peeling of the polyimide film were observed.

<Example 34>
A polyimide film was produced in the same manner as in Example 11 except that the liquid crystal aligning agent (A-5) obtained in Example 27 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.

<Example 35>
The liquid crystal aligning agent (C-1) obtained in Example 28 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. After baking for 1 hour at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. This polyimide film was rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation amount: 0.4 mm), and then the surface condition of the polyimide film was observed. No debris or peeling of the polyimide film was observed.

<Example 36>
A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal aligning agent (C-2) obtained in Example 29 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.

<Example 37>
A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal aligning agent (C-3) obtained in Example 30 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing and scraped scraps of the polyimide film were observed, which were less than the results of Comparative Example 5 described later. No peeling of the polyimide was observed.

<Example 38>
A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal aligning agent (C-4) obtained in Example 31 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing were observed, but they were less than the results of Comparative Example 5 described later. No chipping of the polyimide film and peeling of the polyimide film were observed.

<Example 39>
A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal aligning agent (C-5) obtained in Example 32 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.

<Comparative Example 5>
A polyimide film was produced in the same manner as in Example 35 except that the liquid crystal aligning agent (D-1) obtained in Comparative Example 4 was used, and a rubbing treatment was performed. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were observed.

<Example 40>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 14 except that the liquid crystal aligning agent (A-4) obtained in Example 26 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

<Example 41>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 14 except that the liquid crystal aligning agent (A-5) obtained in Example 27 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

<Example 42>
The liquid crystal aligning agent (C-1) obtained in Example 28 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. After baking for 1 hour at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. This polyimide film is rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, pushing amount: 0.4 mm), cleaned by irradiating with ultrasonic waves in pure water for 1 minute, and air blow After removing the water droplets at, the substrate was dried at 80 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two such substrates with a liquid crystal alignment film are prepared, and after a 6 μm spacer is dispersed on the liquid crystal alignment film surface of one substrate, the rubbing directions of the two substrates are combined so that the rubbing direction can be twisted by 85 degrees from antiparallel, The periphery was sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of 6 μm was produced. Liquid crystal (MLC-2003, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

<Example 43>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 42 except that the liquid crystal aligning agent (C-2) obtained in Example 29 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

<Example 44>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 42 except that the liquid crystal aligning agent (C-3) obtained in Example 30 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

<Example 45>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 42 except that the liquid crystal aligning agent (C-4) obtained in Example 31 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

<Example 46>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 42 except that the liquid crystal aligning agent (C-5) obtained in Example 32 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

<Comparative Example 6>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 42 except that the liquid crystal aligning agent (D-1) obtained in Comparative Example 4 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 1 described later.

  Table 1 shows the measurement results of voltage holding ratio and ion density in Examples 14 to 16, Example 40 to Example 46, Comparative Example 3, and Comparative Example 6.

<Example 47>
The liquid crystal aligning agent (A-1) obtained in Example 8 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. After baking for 20 minutes at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. The coating film surface was irradiated with 1.0 J / cm ^{2 of} 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, and a 6 μm spacer is dispersed on the liquid crystal alignment film surface of one of the substrates, and then the two substrates are combined so that the alignment directions of the two substrates are twisted from parallel to 85 degrees. The periphery was sealed leaving the inlet, and an empty cell with a cell gap of 6 μm was produced. Liquid crystal (MLC-2003, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Example 48>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal aligning agent (A-2) obtained in Example 9 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Example 49>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 47 except that the liquid crystal aligning agent (A-3) obtained in Example 10 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Example 50>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 47 except that the liquid crystal aligning agent (A-4) obtained in Example 26 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Example 51>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 47 except that the liquid crystal aligning agent (A-5) obtained in Example 27 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Comparative Example 7>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 47 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Example 52>
The liquid crystal aligning agent (C-1) obtained in Example 28 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. After baking for 1 hour at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. The coating film surface was irradiated with 1.0 J / cm ^{2 of} 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, and a 6 μm spacer is dispersed on the liquid crystal alignment film surface of one of the substrates, and then the two substrates are combined so that the alignment directions of the two substrates are twisted from parallel to 85 degrees. The periphery was sealed leaving the inlet, and an empty cell with a cell gap of 4 μm was produced. Liquid crystal (MLC-2003, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Example 53>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 52 except that the liquid crystal aligning agent (C-2) obtained in Example 29 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Example 54>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 52 except that the liquid crystal aligning agent (C-3) obtained in Example 30 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Example 55>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal aligning agent (C-4) obtained in Example 31 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Example 56>
A twisted nematic liquid crystal cell was prepared in the same manner as in Example 52 except that the liquid crystal aligning agent (C-5) obtained in Example 32 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density were performed. Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.

<Comparative Example 8>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 52 except that the liquid crystal aligning agent (D-1) obtained in Comparative Example 4 was used. Confirmation of the alignment state of the liquid crystal, voltage holding ratio, and ion density Was measured. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.
Table 2 shows the measurement results of voltage holding ratio and ion density in Examples 47 to 56 and Comparative Examples 7 to 8.

<Example 57> Preparation of polyamic acid ester resin (E-1) The inside of a 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, p-PDA was 1.50 g (13.87 mmol), and DA-B was 0. 4090 g (1.541 mmol), 107.47 g of NMP and 2.82 g (35.67 mmol) of pyridine as a base were added and dissolved by stirring. Next, while stirring this diamine solution, 4.83 g (14.86 mmol) of 1,3DMCBDE-Cl was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was poured into 565 g of water while stirring, and the precipitated white precipitate was collected by filtration. Subsequently, it was washed once with 566 g of water, once with 566 g of ethanol, three times with 141 g of ethanol, and dried to obtain 4.92 g of a white polyamic acid ester resin (E-1) powder. . The yield was 87.0%. Moreover, the molecular weight of this polyamic acid ester was Mn = 17,828 and Mw = 31,832.

<Example 58>
1.02 g of the polyamic acid ester resin powder obtained in Synthesis Example 57 was put in an Erlenmeyer flask, and 9.18 g of γ-BL was further added, and the mixture was stirred and dissolved at room temperature for 24 hours. To this solution, 1.03 g of a 1.0 mass% γ-butyllactone solution of 3-glycidoxypropylmethyldiethoxysilane (hereinafter abbreviated as GPS) was added as a silane coupling agent, and the mixture was stirred at 50 ° C. for 24 hours. did. To the obtained solution, 2.41 g of γ-Bz and 3.41 g of BCS were added, and stirred for 30 minutes with a magnetic stirrer to prepare a polyamic acid ester solution.
To 5.75 g of the above polyamic acid ester solution, N-α, N-ω1, N-ω2-tri-t-butoxycarbonyl-L-arginine (hereinafter abbreviated as Boc-Arg) was added as an imidization accelerator. 0906g (0.1 molar equivalent with respect to 1 mol of amic acid ester group) was added, and it stirred at room temperature for 30 minutes, Boc-Arg was dissolved completely, and the liquid crystal aligning agent (E-1a) of this invention was obtained. .

<Comparative Example 9>
1.04 g of the polyamic acid ester resin powder obtained in Comparative Synthesis Example 2 was put in an Erlenmeyer flask, and further 9.35 g of DMF was added, and the mixture was stirred and dissolved at room temperature for 24 hours. To this solution, 1.07 g of a 1.0 mass% γ-butyllactone solution of GPS was added as a silane coupling agent, and the mixture was heated and stirred at 50 ° C. for 24 hours. 2.71 g of γ-BL and 3.06 g of BCS were added to the obtained solution, and the mixture was stirred with a magnetic stirrer for 30 minutes to prepare a polyamic acid ester solution.
To the above polyamic acid ester solution (5.42 g), 0.0775 g of Boc-Arg as an imidization accelerator (0.1 molar equivalent with respect to 1 mol of the amic acid ester group) was added, and the mixture was stirred at room temperature for 30 minutes. Arg was completely dissolved to obtain a liquid crystal aligning agent (D-1a).

<Example 59>
The liquid crystal aligning agent (E-1a) obtained in Example 58 was filtered through a 1.0 μm filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. After baking for 20 minutes at a temperature of 230 ° C., a polyimide film having a thickness of 100 nm was obtained. The coating film surface was irradiated with 1.0 J / cm ^{2 of} 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, and a 4 μm spacer is dispersed on the surface of the liquid crystal alignment film of one of the substrates, and then combined so that the alignment directions of the two substrates are twisted by 85 degrees from parallel. The periphery was sealed leaving the inlet, and an empty cell with a cell gap of 4 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a twisted nematic liquid crystal cell. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. As a result of measuring the voltage holding ratio of the liquid crystal cell and then measuring the ion density, the voltage holding ratio was 99.4% at a temperature of 23 ° C., 98.6% at a temperature of 60 ° C., and 95 at a temperature of 90 ° C. a .3%, the ion density was 507pC / cm ² at 85pC / ^cm 2, 60 ℃ at 23 ° C..

<Comparative Example 10>
A twisted nematic liquid crystal cell was produced in the same manner as in Example 59 except that the liquid crystal aligning agent (D-1a) obtained in Comparative Example 9 was used. When the alignment state of the liquid crystal cell was observed with a polarizing microscope, it was confirmed that the liquid crystal cell had a uniform alignment without defects. As a result of measuring the voltage holding ratio of this liquid crystal cell and then measuring the ion density, the voltage holding ratio was 99.2% at a temperature of 23 ° C., 98.1% at a temperature of 60 ° C., and 94 at a temperature of 90 ° C. a .9%, ion density was 644pC / cm ² at 159pC / ^cm 2, 60 ℃ at 23 ° C..
From the above results, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can be a liquid crystal alignment film excellent in mechanical strength that is not easily damaged by rubbing treatment without adding a crosslinking agent or the like. confirmed.
Moreover, it was confirmed that the liquid crystal display element which has the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention turns into a liquid crystal display element excellent in the reliability with a high voltage holding rate and a low ion density even at high temperature.
Furthermore, the liquid crystal display having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention even when the liquid crystal alignment film of the present invention is irradiated with polarized ultraviolet light and subjected to a light distribution treatment to give the liquid crystal alignment ability It was confirmed that the device was a liquid crystal display device having a high voltage holding ratio even at high temperatures and a low ion density and excellent reliability.

  From the comparison between Example 59 and Comparative Example 10, even when a silane coupling agent or other additives were added to the liquid crystal aligning agent of the present invention, the liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention was It was confirmed that a liquid crystal display element having a high voltage holding ratio and a low ion density and excellent reliability could be obtained.

  By using the liquid crystal aligning agent of the present invention, a liquid crystal aligning film excellent in mechanical strength that is hard to be rubbed by rubbing treatment is obtained. Further, when the liquid crystal aligning film is used, a liquid crystal display element with few display defects is obtained. can get. In addition, by using the liquid crystal alignment film of the present invention, a liquid crystal display element having a high voltage holding ratio, a low ion density, and excellent reliability can be obtained regardless of the alignment treatment method. A liquid crystal aligning agent can be used suitably as a liquid crystal aligning film which is a member of a liquid crystal display element.

The polyimide precursor and polyimide of the present invention contain a primary or secondary aliphatic amine protected with a Boc group, and the Boc group is eliminated at the time of firing to promote intermolecular crosslinking reaction. An excellent polyimide film can be provided, and the polyimide film can be suitably used as a protective film or an electronic device, particularly as a liquid crystal alignment film.
In addition, the diamine compound of the present invention has a structure containing a primary or secondary aliphatic amine protected with a Boc group, and the polyimide precursor and polyimide of the present invention and a liquid crystal alignment film using them are obtained. It is optimal as a raw material.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-278317 filed on October 29, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (14)

The liquid crystal aligning agent characterized by containing the polyimide precursor which has a substituent of the structure represented by following formula (1), or the imidation polymer of this polyimide precursor.

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.)   The polyimide precursor or the imidized polymer of the polyimide precursor is selected from the group consisting of a diamine compound having a substituent represented by the formula (1) and a tetracarboxylic acid derivative having a substituent represented by the formula (1). The liquid crystal aligning agent of Claim 1 obtained using at least 1 chosen.   A diamine compound having a substituent represented by the formula (1) and / or a tetracarboxylic acid derivative having a substituent represented by the formula (1) is added in an amount of 2 to 100 mol% of the total diamine compound and the tetracarboxylic acid derivative. The liquid crystal aligning agent of Claim 2 which is the polyimide precursor obtained by using or the imidation polymer of this polyimide precursor. The liquid crystal aligning agent in any one of Claims 1-3 in which a polyimide precursor has a structural unit of following formula (2).

Wherein X ₁ is a (4 + a) valent organic group, Y ₁ is a (2 + b) valent organic group, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is the above (It is a structure represented by Formula (1). A and b are integers of 0-4, respectively, and a + b> 0.) The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the polyimide precursor has a structure containing a structural unit represented by the following formula (3).

(Wherein X is a tetravalent organic group, Y ₂ is a (2 + c) valent organic group, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is the formula (1 And c is an integer of 1 to 4.) The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the polyimide precursor has a structure containing a structural unit represented by the following formula (4).

(In the formula, X is a tetravalent organic group, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ is a single bond or a divalent organic group having 1 to 20 carbon atoms. Z is a structure represented by the above formula (1), c is an integer of 1 to 4.) The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the polyimide precursor has a structure containing a structural unit represented by the following formula (5).

(In the formula, X is a tetravalent organic group, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is a structure represented by the above formula (1). It is an integer of ~ 4.)   The liquid crystal aligning film obtained by baking the liquid crystal aligning agent in any one of Claims 1-7 at 150-300 degreeC. The polyimide precursor containing the structural unit represented by following formula (6).

(Wherein X is a tetravalent organic group, Y ₂ is a (2 + c) valent organic group, Z is a structure represented by the following formula (1), and R ₄ is a hydrogen atom or a carbon number. (It is an alkyl group of 1-4. C is an integer of 1-4.)

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.) Polyimide containing a structural unit represented by the following formula (7).

(In the formula, X is a tetravalent organic group, Y ₂ is a (2 + c) valent organic group, and Z is a structure represented by the following formula (1). C is an integer of 1 to 4. .)

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.) The polyimide precursor containing the structural unit represented by following formula (8).

(In the formula, X is a tetravalent organic group, Z is a structure represented by the following formula (1), R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ is carbon. (It is a divalent organic group having a number of 1 to 20. c is an integer of 1 to 4.)

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.) The polyimide containing the structural unit represented by following formula (9).

(In the formula, X is a tetravalent organic group, Z is a structure represented by the following formula (1), R ₅ is a divalent organic group having 1 to 20 carbon atoms, c is 1 It is an integer of ~ 4.)

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.) The polyimide precursor containing the structural unit represented by following formula (10).

(In the formula, X is a tetravalent organic group, Z is a structure represented by the following formula (1), R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is an integer of ~ 4.)

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.) A polyimide containing a structural unit represented by the following formula (11).

(In the formula, X is a tetravalent organic group, Z is a structure represented by the following formula (1), and c is an integer of 1 to 4.)

(In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a C 1-20 monovalent organic group.)