WO2011115077A1 - Liquid crystal alignment agent containing end-modified polyamic acid ester, and liquid crystal alignment film - Google Patents

Abstract

Disclosed is a liquid crystal alignment agent which can reduce microscopic irregularities on the surface of liquid crystal alignment films, improves liquid crystal alignment properties, and has improved electrical characteristics, such as the relaxation of residual DC voltage, and VHR/ion density. The liquid crystal alignment agent is characterised in containing: a polyamic acid ester having a structural unit represented by general formula (1), and having an end modified such that an amino group on the end has a specific structure represented by general formula (3); a polyamic acid having a structural unit represented by general formula (2); and an organic solvent. (R1 represents a C1-5 alkyl group, A1 and A2 independently represent a hydrogen atom or an optionally substituted C1-10 alkyl group, alkenyl group or alkynyl group, X1 and X2 represent a tetravalent organic group, and Y1 and Y2 represent a divalent organic group.) (In general formula (3), A represents a single bond, -O-, -S-, or -NR3-, and R2 and R3 independently represent a methyl group, an ethyl group, a vinyl group, a 1-propenyl group, an isopropenyl group, a C3-6 cycloalkyl group, a phenyl group, a naphthyl group, or a heterocyclic ring.)

Description

Terminally-modified polyamic acid ester-containing liquid crystal aligning agent and liquid crystal aligning film

The present invention relates to a liquid crystal aligning agent containing a polyamic acid ester having a terminal modified and a polyamic acid, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element.

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. Conventionally, as the liquid crystal alignment film, a polyimide liquid crystal alignment film obtained by applying a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide to a glass substrate or the like and baking it is mainly used. It is used.
As liquid crystal display elements have become higher in definition, liquid crystal alignment films have high liquid crystal alignment characteristics and stable pretilt angles in addition to the demands for suppressing the decrease in contrast and reducing the afterimage phenomenon. Characteristics such as a voltage holding ratio, suppression of an afterimage generated by AC driving, a small residual charge when a DC voltage is applied, and / or an early relaxation of a residual charge accumulated by a DC voltage are becoming increasingly important.

Various proposals have been made for polyimide-based liquid crystal alignment films in order to meet the above requirements. For example, as a liquid crystal alignment film having a short time until an afterimage generated by a DC voltage disappears, a liquid crystal alignment agent containing a tertiary amine having a specific structure in addition to polyamic acid or imide group-containing polyamic acid (for example, Patent Document 1), and those using a liquid crystal aligning agent containing a soluble polyimide using a specific diamine compound having a pyridine skeleton as a raw material have been proposed (for example, see Patent Document 2). In addition to polyamic acid and its imidized polymer, it contains one carboxylic acid group in the molecule as a liquid crystal alignment film with a high voltage holding ratio and a short time until the afterimage generated by direct current voltage disappears. Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amino group in the molecule ( For example, see Patent Document 3). In addition, a tetracarboxylic acid having a specific structure of tetracarboxylic dianhydride and cyclobutane as a liquid crystal alignment film having excellent liquid crystal alignment, high voltage holding ratio, low afterimage, excellent reliability, and high pretilt angle Known is a liquid crystal alignment agent containing a polyamic acid obtained from a dianhydride and a specific diamine compound or an imidized polymer thereof (for example, see Patent Document 4). In addition, as a method of suppressing an afterimage caused by alternating current driving in a liquid crystal display element of a lateral electric field driving method, a method of using a specific liquid crystal alignment film that has good liquid crystal alignment and large interaction with liquid crystal molecules (patent) Document 5) has been proposed.

However, in recent years, liquid crystal televisions with large screens and high-definition are mainly used, and the demand for afterimages has become more severe, and characteristics that can withstand long-term use in harsh usage environments are required. At the same time, liquid crystal alignment films to be used are required to have higher reliability than conventional liquid crystal alignment films. Not only the initial characteristics of the liquid crystal alignment films are good, but also, for example, they are longer at high temperatures. There is a need to maintain good properties even after time exposure.
On the other hand, as a polymer component that constitutes a polyimide-based liquid crystal aligning agent, polyamic acid ester is highly reliable, and heat treatment when imidizing it does not cause a decrease in molecular weight. It has been reported that it is excellent in reliability (see Patent Document 6). However, polyamic acid esters generally have problems such as high volume resistivity and a large amount of residual charge when a DC voltage is applied, but the characteristics of polyimide liquid crystal aligning agents containing such polyamic acid esters are improved. How to do is not yet known.

JP-A-9-316200 JP-A-10-104633 JP-A-8-76128 Japanese Patent Laid-Open No. 9-138414 JP 11-38415 A JP 2003-26918 A

The present invention paid attention to a liquid crystal aligning agent obtained by blending a polyamic acid ester and a polyamic acid excellent in electrical characteristics as a method for improving the characteristics of the liquid crystal aligning agent containing the polyamic acid ester. However, a liquid crystal alignment film obtained from a liquid crystal aligning agent obtained by blending such a polyamic acid ester and a polyamic acid is not satisfactory in terms of both liquid crystal alignment properties and electrical characteristics.
That is, a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid causes white turbidity, a decrease in voltage holding ratio when the film is used at a high temperature, and direct current Problems such as generation of afterimages due to voltage accumulation and generation of afterimages due to AC driving occur.
The present invention relates to a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid, in which both the liquid crystal alignment property and the electrical characteristics are good, and a liquid crystal alignment film having transparency without white turbidity is obtained. An object is to provide an alignment agent.

According to the research of the present inventor, when a liquid crystal alignment film formed from a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid was analyzed, it was confirmed that fine irregularities were generated on the film surface. However, the present inventor has modified the terminals so that the fine irregularities generated on the film surface have a specific structure as described below at least part of the terminal amino group of the polyamic acid ester. It is found that the use of a polyamic acid ester can significantly suppress the above, and when the fine unevenness generated on the film surface is reduced, the above-mentioned difficulties of the liquid crystal aligning agent containing the polyamic acid ester and the polyamic acid Has been found to be resolved.
Further, according to the present inventor, the polyamic acid ester having a modified end is improved in solubility in an organic solvent even when it has a high molecular weight, and the polyamic acid ester having a modified end and a polyamic acid are added. The liquid crystal aligning agent to be contained can be a liquid crystal aligning agent having a relatively low viscosity even when contained in a high concentration in an organic solvent, which makes it easy to produce a liquid crystal aligning film by, for example, an inkjet method, It has also been found that it is easy to produce a liquid crystal alignment film having a large thickness.

Thus, the present invention is based on the above findings and has the following gist.
1. A polyamic acid ester having a structural unit of the following formula (1) and having a terminal modified so that the terminal amino group has a structure of the following formula (3), and a polyamic acid having a structural unit of the following formula (2) And a liquid crystal aligning agent characterized by containing an organic solvent.

（Ｒ_１は、炭素数１～５のアルキル基であり、Ａ_１～Ａ_２はそれぞれ独立して水素原子、又は置換基を有してもよい炭素数１～１０のアルキル基、アルケニル基若しくはアルキニル基であり、Ｘ_１、Ｘ_２は４価の有機基であり、Ｙ_１、Ｙ_２は２価の有機基である。）

(R ₁ is an alkyl group having 1 to 5 carbon atoms, and A ₁ to A ₂ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group, or An alkynyl group, X ₁ and X ₂ are tetravalent organic groups, and Y ₁ and Y ₂ are divalent organic groups.)

（式中、Ａは単結合、－Ｏ－、－Ｓ－、又は－ＮＲ_３－であり、Ｒ_２、Ｒ_３は、それぞれ独立して、炭素数１～１０のアルキル基、アルケニル基若しくはアルキニル基、炭素数３～６のシクロアルキル基、又は置換基を有していてもよいアリール基若しくは複素環基である。）
２．前記ポリアミック酸エステルの含有量と前記ポリアミック酸の含有量が、（ポリアミック酸エステルの含有量／ポリアミック酸）の質量比率で、１／９～９／１である上記１に記載の液晶配向剤。
３．前記ポリアミック酸エステル及びポリアミック酸と有機溶剤とを含有し、前記ポリアミック酸エステルとポリアミック酸の合計量が、有機溶媒に対して０．５質量％～１５質量％である上記１又は２に記載の液晶配向剤。
４．前記末端を修飾したポリアミック酸エステルが、下記式（Ｃ－１）～(Ｃ－１７)から選ばれる少なくとも1種類のクロロカルボニル化合物とポリアミック酸エステルの主鎖末端アミンを反応させて得られるポリアミック酸エステルである上記１～３のいずれかに記載の液晶配向剤。

(Wherein A is a single bond, —O—, —S—, or —NR ₃ —, and R ₂ and R ₃ each independently represents an alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms. Group, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group or heterocyclic group which may have a substituent.)
2. 2. The liquid crystal aligning agent according to 1 above, wherein the content of the polyamic acid ester and the content of the polyamic acid are 1/9 to 9/1 in terms of a mass ratio of (polyamic acid ester content / polyamic acid).
3. 3. The polyamic acid ester, the polyamic acid, and an organic solvent, wherein the total amount of the polyamic acid ester and the polyamic acid is 0.5% by mass to 15% by mass with respect to the organic solvent. Liquid crystal aligning agent.
4). A polyamic acid obtained by reacting the terminal polyamic acid ester with at least one chlorocarbonyl compound selected from the following formulas (C-1) to (C-17) and a main chain terminal amine of the polyamic acid ester: 4. The liquid crystal aligning agent according to any one of the above 1 to 3, which is an ester.

５．式（１）及び式（２）におけるＸ_１及びＸ_２が、それぞれ独立して、下記式で表される構造からなる群から選ばれる少なくとも１種である上記１～４のいずれかに記載の液晶配向剤。

5. X ₁ and X ₂ in Formula (1) and Formula (2) are each independently at least one selected from the group consisting of structures represented by the following formulas: Liquid crystal aligning agent.

６．式（１）において、Ｙ_１が下記式で表される構造からなる群から選ばれる少なくとも１種類である上記１～５のいずれかに記載の液晶配向剤。

6). 6. The liquid crystal aligning agent according to any one of 1 to 5 above, wherein in formula (1), Y ₁ is at least one selected from the group consisting of structures represented by the following formula.

７．前記式（２）において、Ｙ_２が下記式で表される構造から選ばれる少なくとも1種である上記１～６のいずれかに記載の液晶配向剤。

7). 7. The liquid crystal aligning agent according to any one of 1 to 6, wherein in the formula (2), Y ₂ is at least one selected from structures represented by the following formula.

８．上記１～７のいずれかに記載の液晶配向剤を塗布、焼成して得られる液晶配向膜。
９．上記１～７のいずれかに記載の液晶配向剤を塗布、焼成して得られる被膜に、偏光された放射線を照射して得られる液晶配向膜。

8). 8. A liquid crystal alignment film obtained by applying and baking the liquid crystal aligning agent according to any one of 1 to 7 above.
9. 8. A liquid crystal alignment film obtained by irradiating a film obtained by applying and baking the liquid crystal aligning agent according to any one of 1 to 7 above with polarized radiation.

According to the present invention, fine irregularities on the surface can be reduced, the interface characteristics of the liquid crystal alignment film such as an afterimage caused by alternating current drive can be improved, and electrical characteristics such as voltage holding ratio, ion density, and residual DC voltage can be obtained. The liquid crystal aligning agent which improved the physical characteristic and improved reliability is provided.
In the present invention, by using a polyamic acid ester whose terminal amino group is modified to have a specific structure as described below, it is possible to reduce the fine irregularities generated on the surface of the film and reduce the polyamic acid. Although it is not necessarily clear whether the difficulty of the liquid crystal aligning agent containing acid ester and polyamic acid is solved, it is considered as follows.

That is, in the liquid crystal alignment film formed by removing the solvent from the liquid crystal aligning agent in which the polyamic acid ester and the polyamic acid are dissolved in the organic solvent, the polyamic acid ester having a surface free energy lower than that of the polyamic acid is unevenly distributed on the surface. However, when the polyamic acid ester and the polyamic acid undergo phase separation, an aggregate of polyamic acid is formed in the polyamic acid ester phase, and / or an aggregate of polyamic acid ester in the polyamic acid phase Therefore, a film having a large number of fine irregularities on the film surface is formed.

On the other hand, in the liquid crystal aligning agent of the present invention, by using a polyamic acid ester whose end is modified so as to have the above specific structure, the solvent is removed from the liquid crystal aligning agent to form a liquid crystal aligning film. Phase separation between the polyamic acid ester and the polyamic acid is promoted, the polyamic acid ester is present near the film surface without being mixed with the polyamic acid, and the polyamic acid is mixed with the polyamic acid ester inside the film and at the substrate interface. Will exist without. Therefore, the surface of the obtained liquid crystal alignment film is smooth because unevenness due to phase separation of the polyamic acid ester and the polyamic acid is not formed. A liquid crystal alignment film having a smooth surface without unevenness is formed by a polyamic acid ester having excellent orientation stability and reliability covering the surface of the film, and a polyamic acid having excellent electrical characteristics is formed inside the film. And at the electrode interface, it is considered to have excellent characteristics. In addition, the liquid crystal alignment film having a smooth surface also reduces the cloudiness of the film due to the occurrence of unevenness.

<Polyamic acid ester and polyamic acid>
The polyamic acid ester and polyamic acid used in the present invention are polyimide precursors for obtaining a polyimide, and are polymers having sites capable of undergoing an imidation reaction shown below by heating.

　本発明の液晶配向剤に含有するポリアミック酸エステル及びポリアミック酸は、それぞれ、下記式（１）及び下記式（２）を有する。

The polyamic acid ester and polyamic acid contained in the liquid crystal aligning agent of the present invention have the following formula (1) and the following formula (2), respectively.

In the formula (1), R ₁ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms. In the polyamic acid ester, the temperature at which imidization proceeds increases as the number of carbon atoms in the alkyl group increases. Therefore, R ₁ is particularly preferably a methyl group from the viewpoint of ease of imidization by heat.
In Formula (1) and Formula (2), A ₁ and A ₂ are each independently a hydrogen atom or an alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms that may have a substituent. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, and a bicyclohexyl group. Examples of the alkenyl group include those in which one or more CH ₂ —CH ₂ structures existing in the above alkyl group are replaced with a CH═CH structure, and more specifically, vinyl groups, allyl groups, 1- Examples include propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like. Alkynyl groups include those in which one or more CH ₂ —CH ₂ structures present in the alkyl group are replaced with C≡C structures, and more specifically, ethynyl groups, 1-propynyl groups, 2 -Propynyl group and the like.
The above alkyl group, alkenyl group, and alkynyl group may have a substituent as long as it has 1 to 10 carbon atoms as a whole, and may further form a ring structure by the substituent. Note that forming a ring structure with a substituent means that the substituents or a substituent and a part of the mother skeleton are bonded to form a ring structure.

Examples of such substituents are halogen groups, hydroxyl groups, thiol groups, nitro groups, aryl groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, alkyls. A group, an alkenyl group and an alkynyl group.
Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the aryl group as a substituent include a phenyl group. This aryl group may be further substituted with the other substituent described above.
The organooxy group which is a substituent can have a structure represented by OR. The R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above. Specific examples of the alkyloxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.

The organothio group as a substituent can have a structure represented by —S—R. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.
The organosilyl group as a substituent can have a structure represented by —Si— (R) ₃ . The R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above. Specific examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, and a hexyldimethylsilyl group.
The acyl group as a substituent can have a structure represented by —C (O) —R. Examples of R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above. Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.

As the ester group which is a substituent, a structure represented by —C (O) O—R or —OC (O) —R can be shown. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.
The thioester group which is a substituent can have a structure represented by —C (S) O—R or —OC (S) —R. Examples of R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.
The phosphate group which is a substituent can have a structure represented by —OP (O) — (OR) ₂ . The R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
Examples of the substituent amide group include —C (O) NH ₂ , —C (O) NHR, —NHC (O) R, —C (O) N (R) ₂ , —NRC (O) R. The structure represented by can be shown. The R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.

Examples of the aryl group as a substituent include the same aryl groups as described above. This aryl group may be further substituted with the other substituent described above.
Examples of the alkyl group as a substituent include the same alkyl groups as described above. This alkyl group may be further substituted with the other substituent described above.
Examples of the alkenyl group as a substituent include the same alkenyl groups as described above. This alkenyl group may be further substituted with the other substituent described above.
Examples of the alkynyl group that is a substituent include the same alkynyl groups as described above. This alkynyl group may be further substituted with the other substituent described above.
In general, when a bulky structure is introduced, there is a possibility that the reactivity of the amino group and the liquid crystal orientation may be lowered. Therefore, as A ₁ and A ₂ , a hydrogen atom or a carbon atom that may have a substituent is 1 An alkyl group of 1 to 5 is more preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

In the above formulas (1) and (2), X ₁ and X ₂ are tetravalent organic groups and are not particularly limited. Two or more kinds of X ₁ and X ₂ may be mixed in the polyimide precursor. If specific examples of X ₁ and X ₂ are shown, X-1 to X-46 shown below can be mentioned independently.

Among these, X ₁ and X ₂ are each independently X-1, X-2, X-3, X-4, X-5, X-6, X-8, X from the availability of monomers. -16, X-19, X-21, X-25, X-26, X-27, X-28 or X-32 are preferred. The amount of tetracarboxylic dianhydride having these preferable X ₁ and X ₂ is preferably 20 to 100 mol%, more preferably 40 to 100 mol% of the total tetracarboxylic dianhydride.

In the above formulas (1) and (2), Y ₁ and Y ₂ are each independently a divalent organic group and are not particularly limited. Specific examples of Y ₁ and Y ₂ include the following Y-1 to Y-103. As Y ₁ and Y ₂ , two or more kinds may be mixed independently.

Among them, in order to obtain good liquid crystal orientation, in order to introduce a highly linear diamine into the polyamic acid ester, Y ₁ is represented by Y-7, Y-10, Y-11, Y-12, Y -13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y-46 Diamines having Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, or Y-98 are preferred. The amount of these diamines preferably used as Y ₁ is preferably 1 to 100 mol%, more preferably 50 to 100 mol% of the total diamine.
Among them, when it is desired to increase the pretilt angle, it is preferable to introduce a diamine having a long-chain alkyl group, aromatic ring, aliphatic ring, steroid skeleton, or a combination thereof in the side chain into the polyamic acid ester. In this case, Y ₁ is Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y- 86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, or Y-97 are more preferred.
Such Y ₁ is preferably at least one selected from the group consisting of structures represented by the following formulae.

By reducing the volume resistivity of the polyamic acid, it is possible to reduce the afterimage due to the accumulation of DC voltage, so in order to introduce a diamine having a structure having a hetero atom, a polycyclic aromatic structure, or a biphenyl skeleton into the polyamic acid, Y ₂ is Y-19, Y-23, Y-25, Y-26, Y-27, Y-30, Y-31, Y-32, Y-33, Y-34, Y-35, Y- 36, Y-40, Y-41 Y-42, Y-44, Y-45, Y-49, Y-50, Y-51, or Y-61 are more preferred, and Y-31 or Y-40 diamine Is preferred. The amount of these diamines preferably used as Y ₂ is preferably 1 to 100 mol%, more preferably 50 to 100 mol% of the total diamine.
Among these, by increasing the surface free energy of the polyamic acid, the phase separation between the polyamic acid ester and the polyamic acid is further promoted, and the surface of the liquid crystal alignment film obtained by coating and baking becomes smoother. It is preferable to introduce a diamine containing a primary amino group, a hydroxyl group, an amide group, a ureido group, or a carboxyl group into the polyamic acid. Therefore, Y- ₂ is more preferably Y-19, Y-31, Y-40, Y-45, Y-98, or Y-99, particularly Y-98 or Y-99 containing a carboxyl group. preferable. In particular, Y ₂ is preferably at least one selected from structures represented by the following formula.

<Method for producing polyamic acid ester>
The polyamic acid ester represented by the above formula (1) is obtained by reaction of any of the tetracarboxylic acid derivatives represented by the following formulas (6) to (8) with the diamine compound represented by the formula (9). be able to.

(In the formulas (6) to (9), X ₁ , Y ₁ , R ₁ , A ₁ and A ₂ are the same as defined in the above formula (1).)
The polyamic acid ester represented by the above formula (1) can be synthesized by the following methods (1) to (3) using the above monomer.

(1) Method to manufacture from polyamic acid A polyamic acid ester can be manufactured by esterifying the polyamic acid obtained from tetracarboxylic dianhydride and diamine.

Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be manufactured.
As the esterifying agent, those that can be easily removed by purification are preferable. N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like. 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 in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the polymer, and these may be used alone or in combination of two or more. . The concentration at the time of production is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.

(2) Method to manufacture by reaction with tetracarboxylic-acid diester dichloride and diamine Polyamic acid ester can be manufactured by polycondensing tetracarboxylic-acid diester dichloride and diamine.

Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be produced by reacting.
As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently. The addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination. The concentration of the polymer during production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight polymer is easily obtained. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the production of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.

(3) Method for producing polyamic acid from tetracarboxylic acid diester and diamine Polyamic acid ester can be produced by polycondensation of tetracarboxylic acid diester and diamine.
Specifically, tetracarboxylic acid diester and diamine 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 hours, preferably 3 to 15 hours. It can be produced by reacting.

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, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like. The addition amount of the condensing agent is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.
As the base, tertiary amines such as pyridine and triethylamine can be used. The addition amount of the base is preferably 2 to 4 moles relative to the diamine component from the viewpoint that it can be easily removed and a high molecular weight product can be easily obtained.

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 times mol with respect to the diamine component.
Among the methods for producing the three polyamic acid esters, since the high molecular weight polyamic acid ester is obtained, the production method of (1) or (2) is particularly preferable.
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 a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

<Method for producing polyamic acid>
The polyamic acid represented by the above formula (2) can be obtained by a reaction between a tetracarboxylic dianhydride represented by the following formula (10) and a diamine compound represented by the formula (11).

Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be manufactured.
The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone in view of the solubility of the monomer and polymer. These are used alone or in combination. May be. The concentration of the produced polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
The polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine | purified by performing precipitation several times, washing | cleaning with a poor solvent, and normal temperature or heat-drying can be obtained. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

　式（１２）において、Ａは単結合、－Ｏ－、－Ｓ－、又は－ＮＲ_３－である。Ｒ_２、Ｒ_３は、それぞれ独立して、炭素数１～１０のアルキル基、アルケニル基若しくはアルキニル基、炭素数３～６のシクロアルキル基、又は置換基を有していてもよいアリール基若しくは複素環基である。炭素数１～１０のアルキル基の具体例としては、メチル基、エチル基、ビニル基、１－プロペニル基、又はイソプロペニル基が挙げられる。なかでも、炭素数１～３の短いアルキル基であり、また、分岐よりも直鎖状のアルキル基が好ましい。炭素数３～６のシクロアルキル基としてはシクロプロピル基又はシクロブチル基が好ましい。アリール基としては、フェニル基、ナフチル基が好ましい。複素環基としては、ピリジン、イミダゾール、イソオキサゾール、チオフェン、フラン、インドール、ベンズイミダゾール、ピロール、又はピぺリジンが好ましい。
　本発明のクロロカルボニル化合物の例を挙げるならば、以下の（Ｃ－１）～（Ｃ－３６）のクロロカルボニル化合物が挙げられるが、これに限定されない。 <Chlorocarbonyl compound used for terminal modification>
The polyamic acid ester whose terminal is modified is obtained by reacting the polyamic acid ester having an amino group at the terminal obtained as described above with a chlorocarbonyl compound represented by the following formula (12).

In the formula (12), A is a single bond, —O—, —S—, or —NR ₃ —. R ₂ and R ₃ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkynyl group, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group which may have a substituent, It is a heterocyclic group. Specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a vinyl group, a 1-propenyl group, and an isopropenyl group. Among these, a short alkyl group having 1 to 3 carbon atoms is preferable, and a linear alkyl group is preferable to a branched group. The cycloalkyl group having 3 to 6 carbon atoms is preferably a cyclopropyl group or a cyclobutyl group. As the aryl group, a phenyl group and a naphthyl group are preferable. As the heterocyclic group, pyridine, imidazole, isoxazole, thiophene, furan, indole, benzimidazole, pyrrole, or piperidine is preferable.
Examples of the chlorocarbonyl compound of the present invention include, but are not limited to, the following (C-1) to (C-36) chlorocarbonyl compounds.

As the chlorocarbonyl compound, the smaller the number of carbon atoms, the smaller the interaction between the ends, and the aggregation of the polyamic acid ester can be suppressed. Therefore, as the chlorocarbonyl compound, C-1, C-2, C-3, C-16, C-17, C-19, C-20, C-21, C-27, or C-29 is more preferred. Preferably, C-1, C-2, C-3, C-16, or C-17 is more preferable.

<Method for producing polyamic acid ester whose terminal is modified>
The terminal of the polyamic acid ester having a repeating unit of the formula (1) having an amino group at the terminal is modified so that the amino group has the structure of the formula (3).
This terminal-modified polyamic acid ester can be obtained by several methods, but after dissolving the polyamic acid ester powder having an amino group at the terminal in an organic solvent, a chlorocarbonyl compound is added in the presence of a base. When reacting a diamine component and a tetracarboxylic acid dialkyl ester derivative (bis (chlorocarbonyl) compound, dialkyl ester dicarboxylic acid, etc.) in an organic solvent to obtain a polyamic acid ester having an amino group at the terminal And a method of adding a chlorocarbonyl compound to the reaction system without isolating the polyamic acid ester and reacting it with a polyamic acid ester having an amino group at the terminal existing in the reaction system. Among them, the method of adding a chlorocarbonyl compound to the latter reaction system is more preferable because the polyamic acid ester can be purified by reprecipitation only once and the production process can be shortened.

In order to obtain a polyamic acid ester having a modified terminal according to the present invention, it is necessary to produce a polyamic acid ester having an amino group at the end of the main chain. Therefore, the molar ratio of the diamine component to the tetracarboxylic acid dialkyl ester derivative is preferably 1: 0.7 to 1: 1, and more preferably 1: 0.8 to 1: 1.
As a method of adding a chlorocarbonyl compound to the above reaction system, a method of adding a tetracarboxylic acid dialkyl ester derivative and reacting with a diamine, a reaction of a tetracarboxylic acid dialkyl ester derivative and a diamine sufficiently, There is a method of adding a chlorocarbonyl compound after producing a polyamic acid ester in which is an amino group. The latter method is more preferable because the molecular weight of the polymer can be easily controlled.

When a polyamic acid ester having a terminal modified is obtained, the reaction between the polyamic acid ester having an amino group at the terminal and the chlorocarbonyl compound is carried out at −20 to 150 ° C., preferably 0 to 50 ° C. in the presence of a base and an organic solvent. 30 minutes to 24 hours, preferably 30 minutes to 4 hours.
The addition amount of the chlorocarbonyl compound is preferably 0.5 to 60 mol%, more preferably 1 to 40 mol%, based on one repeating unit of the polyamic acid ester having an amino group at the end. When the addition amount is large, unreacted chlorocarbonyl compound remains and is difficult to remove, so that it is more preferably 1 to 20 mol%.
As the base, pyridine, triethylamine, and 4-dimethylaminopyridine can be preferably used, but pyridine is preferable because the reaction proceeds gently. If the amount of the base 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 chlorocarbonyl compound.

The organic solvent used for the production of the terminal polyamic acid ester is preferably N-methyl-2-pyrrolidone or γ-butyrolactone in view of the solubility of the monomer and polymer. These may be used alone or in combination of two or more. Also good. 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, so 1 to 30% by mass is preferable, and 5 to 20% by mass is more preferable. Further, in order to prevent hydrolysis of the chlorocarbonyl compound, it is preferable to dehydrate the organic solvent used in the production of the polyamic acid ester whose end is modified as much as possible, and store it in a nitrogen atmosphere to prevent outside air from being mixed.
In this way, a polyamic acid ester having a terminal modified can be obtained. In the liquid crystal aligning agent of the present invention, the polyamic acid ester modified in the terminal has a total amount of the polyamic acid ester contained in the liquid crystal aligning agent. It is not necessarily required to be modified, but it is preferably 15% or more, more preferably 40% or more, particularly preferably 60% or more, based on the total amount of polyamic acid ester contained. . When the content of the terminal amino group-modified polyamic acid ester is small, it is not preferable because sufficient effects aimed at in the present invention cannot be obtained.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention has the form of the solution by which the polyamic acid ester and polyamic acid which modified the said terminal were melt | dissolved in the organic solvent. The molecular weight of the terminal polyamic acid ester is preferably 2,000 to 500,000, more preferably 5,000 to 300,000 in terms of its weight average molecular weight even when the terminal amino group is not modified. More preferably, it is 10,000 to 100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
On the other hand, the weight average molecular weight of the polyamic acid is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
By making the molecular weight of the polyamic acid ester whose terminal is modified smaller than that of the polyamic acid, micro unevenness due to phase separation can be further reduced. The difference in weight average molecular weight between the terminal polyamic acid ester and the polyamic acid is preferably 1,000 to 1200,000, more preferably 3,000 to 80,000, and 5,000 to 60,000. Is particularly preferred.
The mass ratio of the polyamic acid ester to the polyamic acid (polyamic acid ester / polyamic acid) contained in the liquid crystal aligning agent of the present invention is preferably 1/9 to 9/1. The ratio is more preferably 2/8, and particularly preferably 3/7 to 7/3. By setting the ratio within this range, it is possible to provide a liquid crystal aligning agent having good liquid crystal alignment properties and electrical characteristics.

As long as the liquid crystal aligning agent of this invention has the form of the solution in which the polyamic acid ester and polyamic acid which modified the terminal were melt | dissolved in the organic solvent, the manufacture is not ask | required. For example, a method of mixing a polyamic acid ester and a polyamic acid powder and dissolving in an organic solvent, a method of mixing a polyamic acid ester powder and a polyamic acid solution, a method of mixing a polyamic acid ester solution and a polyamic acid powder, There is a method of mixing a polyamic acid ester solution and a polyamic acid solution. Even when the good solvent in which the polyamic acid ester and the polyamic acid are dissolved is different, a uniform polyamic acid ester-polyamic acid mixed solution can be obtained. Therefore, a method of mixing the polyamic acid ester solution and the polyamic acid solution is more preferable.
Further, when the polyamic acid ester and / or polyamic acid having a modified terminal are produced in an organic solvent, the reaction solution obtained may be used, or the reaction solution may be diluted with an appropriate solvent. There may be. Moreover, when the polyamic acid ester which modified the terminal is obtained as a powder, it may be dissolved in an organic solvent to form a solution. At this time, the polymer concentration is preferably 10 to 30% by mass, particularly preferably 10 to 15% by mass. Moreover, you may heat when melt | dissolving the powder of polyamic acid ester and / or polyamic acid. The heating temperature is preferably 20 to 150 ° C, particularly preferably 20 to 80 ° C.

The content (concentration) of the end-modified polyamic acid ester in the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of the liquid crystal alignment film to be formed, but it is uniform and has no defect. From the viewpoint of forming a film, it is preferably 0.5% by mass or more with respect to the organic solvent, and from the viewpoint of storage stability of the solution, it is preferably 15% by mass or less, particularly preferably 1 to 10% by mass.
In the liquid crystal aligning agent of this invention, the other liquid crystal aligning agent which is a compound which has liquid crystal aligning property other than the polyamic acid ester which modified the terminal may contain. Examples of these other liquid crystal aligning agents include various types such as a polyamic acid ester whose terminal amino group is not modified, a soluble polyimide, and / or a liquid crystal aligning agent containing polyamic acid.
Among them, the polyamic acid ester whose end is modified has a high solubility in an organic solvent, so it has excellent alignment characteristics and electrical characteristics, but has a low solubility in an organic solvent, for example, a liquid crystal aligning agent containing polyamic acid or soluble polyimide. It is particularly useful when it is contained.
The said organic solvent contained in the liquid crystal aligning agent of this invention will not be specifically limited if the polymer component of the amic acid ester and polyamic acid which modified at least one part of the terminal amino group melt | dissolves uniformly. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, Examples include 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. it can. You may use these 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which cannot melt | dissolve a polymer component uniformly by itself, if it is a range which a polymer does not precipitate, you may mix with said organic solvent.

As will be described later, when adding a silane coupling agent to the liquid crystal aligning agent of the present invention, before mixing the polyamic acid ester solution and the polyamic acid solution, the polyamic acid ester solution, the polyamic acid solution, or the polyamic acid ester solution And polyamic acid solution. The silane coupling agent can be added to the polyamic acid ester-polyamic acid mixed solution. Since the silane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate, as a method for adding the silane coupling agent, the silane coupling agent is added to a polyamic acid solution that can be unevenly distributed in the film and the substrate interface, and the polymer is added. A method in which the silane coupling agent is sufficiently reacted with the polyamic acid ester solution is more preferable. If the addition amount of the silane coupling agent is too large, unreacted ones may adversely affect the liquid crystal orientation. If the addition amount is too small, the effect on the adhesion does not appear. The content is preferably from 01 to 5.0% by mass, and more preferably from 0.1 to 1.0% by mass.

The liquid crystal aligning agent of this invention may contain the solvent for improving the coating-film uniformity at the time of apply | coating a liquid crystal aligning agent to a board | substrate other than the organic solvent for dissolving a polymer component. As such a solvent, a solvent having a surface tension lower than that of the organic solvent is generally used. Specific examples thereof 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, butyl cellosolve acetate, di Propylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactic acid Isoamyl ester, and the like. Two kinds of these solvents may be used in combination.
The liquid crystal aligning agent of this invention may contain various additives, such as a silane coupling agent and a crosslinking agent. When adding a silane coupling agent or a crosslinking agent, in order to prevent polymer precipitation, it is preferable to add a poor solvent before adding a poor solvent to the liquid crystal aligning agent. Moreover, in order to advance imidation of polyamic acid ester efficiently when baking a coating film, you may add an imidation promoter.

Specific examples of the silane coupling agent are given below, but the silane coupling agent that can be used in the liquid crystal aligning agent of the present invention is not limited thereto. 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 agents 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; triethoxysilyl Aldehyde-based silane coupling agents such as butyraldehyde; carbamates such as triethoxysilylpropylmethylcarbamate and (3-triethoxysilylpropyl) -t-butylcarbamate Mate silane coupling agent.

The addition amount of the silane coupling agent is 0.01 to 5.0% by mass with respect to the polymer component from the viewpoint that the unreacted agent does not adversely affect the liquid crystal orientation and the effect of adhesion appears. Preferably, 0.1 to 1.0% by mass is more preferable. When adding a silane coupling agent, in order to prevent polymer precipitation, it is preferable to add before adding the solvent for improving the above-mentioned coating film uniformity.
Specific examples of the imidization accelerator for polyamic acid ester are given below, but the imidization accelerator that can be used in the liquid crystal aligning agent of the present invention is not limited thereto.

　上記式（Ｂ－１）～（Ｂ－１７）におけるＤは、それぞれ独立してtert-ブトキシカルボニル基、又は９－フルオレニルメトキシカルボニル基である。なお、（Ｂ－１４）～（Ｂ－１７）には、ひとつの式に複数のＤが存在するが、これらは互いに同一であっても異なってもよい。
　ポリアミック酸エステルの熱イミド化を促進する効果が得られる範囲であれば、イミド化促進剤の含有量は特に制限されるものではない。あえてその下限を示すならば、ポリアミック酸エステルに含まれる下記式（１３）のアミック酸エステル部位１モルに対して、好ましくは０．０１モル以上、より好ましくは０．０５モル以上、更に好ましくは０．１モル以上が挙げられる。また、焼成後の膜中に残留するイミド化促進剤自体が、液晶配向膜の諸特性に及ぼす悪影響を最小限に留めるという観点から、あえてその上限を示すならば、本発明のポリアミック酸エステルに含まれる下記式（１３）のアミック酸エステル部位１モルに対して、好ましくはイミド化促進剤が２モル以下、より好ましくは１モル以下、更に好ましくは０．５モル以下が挙げられる。

D in the above formulas (B-1) to (B-17) is each independently a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. In (B-14) to (B-17), there are a plurality of D's in one formula, but these may be the same or different.
The content of the imidization accelerator is not particularly limited as long as the effect of promoting thermal imidation of the polyamic acid ester is obtained. If the lower limit is deliberately shown, it is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably with respect to 1 mol of the amic acid ester moiety of the following formula (13) contained in the polyamic acid ester. 0.1 mol or more is mentioned. In addition, from the viewpoint that the imidization accelerator remaining in the film after baking itself has an adverse effect on various properties of the liquid crystal alignment film, the upper limit of the polyamic acid ester of the present invention can be determined. Preferably, the imidization accelerator is 2 mol or less, more preferably 1 mol or less, and still more preferably 0.5 mol or less with respect to 1 mol of the amic acid ester moiety of the following formula (13) contained.

　イミド化促進剤を添加する場合は、加熱することでイミド化が進行する可能性があるため、良溶媒及び貧溶媒で希釈した後に加えるのが好ましい。

When adding an imidization accelerator, since imidation may advance by heating, it is preferable to add after diluting with a good solvent and a poor solvent.

<Liquid crystal alignment film>
The liquid crystal alignment film of the present invention is a coating film obtained by applying the liquid crystal aligning agent obtained as described above to a substrate, drying and baking, and if necessary, this coating film surface is rubbed or the like. Alignment treatment is performed.
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.
Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent of the present invention. Usually, in order to sufficiently remove the organic solvent contained, the film is dried at 50 to 120 ° C. for 1 to 10 minutes, and then baked at 150 to 300 ° C. for 5 to 120 minutes. The thickness of the coating film after baking 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.

Examples of the method for aligning the coating film include a rubbing method and a photo-alignment method, but the liquid crystal aligning agent of the present invention is particularly useful when used in the photo-alignment method.
As a specific example of the photo-alignment treatment method, there is a method in which 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. Can be mentioned. As the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Of these, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and those having a wavelength of 200 to 400 nm are particularly preferable. Further, in order to improve the liquid crystal orientation, radiation may be irradiated while heating the coated substrate at 50 to 250 ° C. 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 liquid crystal alignment film produced as described above can stably align liquid crystal molecules in a certain direction.

Hereinafter, the present invention will be specifically described with reference to examples. However, it goes without saying that the present invention is not construed as being limited to these examples.
The abbreviations used in the examples and the measurement methods for each property are as follows.
1,3DMCBDE-Cl: Dimethyl-1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate BDA: 1,2,3,4-butanetetracarboxylic dianhydride CBDA : 1,2,3,4-cyclobutanetetracarboxylic dianhydride NMP: N-methyl-2-pyrrolidone γ-BL: γ-butyrolactone BCS: butyl cellosolve PAE: polyamic acid ester PAA: polyamic acid DA-7: (DA-7)
DA-8: The following formula (DA-8)

[viscosity]
In the synthesis examples, the viscosity of the polyamic acid ester and the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample amount of 1.1 mL, and 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 crystals (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) of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polymer laboratory Polyethylene glycol manufactured by the company (peak top molecular weight (Mp) of 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 the mixed sample were measured separately.

[Center line average roughness measurement]
The coating film of the liquid crystal aligning agent obtained by spin coating is dried for 5 minutes on a hot plate at a temperature of 80 ° C. and baked for 1 hour in a hot air circulation oven at a temperature of 250 ° C. to form a coating film having a film thickness of 100 nm. Obtained. The film surface of this coating film was observed with an atomic force microscope (AFM), the center line average roughness (Ra) of the film surface was measured, and the flatness of the film surface was evaluated.
Measuring device: L-trace probe microscope (manufactured by SII Technology)
[Voltage holding ratio]
A liquid crystal aligning agent was 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 for 60 minutes in a hot air circulation oven at 250 ° C. to be imidized with a film thickness of 100 nm. A membrane was obtained. The coating surface was irradiated with 100 mJ / 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 sprayed on the liquid crystal alignment film surface of one of the substrates, and then the two substrates are combined so that the alignment is antiparallel. The periphery was sealed and the empty cell having a cell gap of 6 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the inlet was sealed to obtain a liquid crystal cell.
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 measurement of the ion density of the liquid crystal cell was performed 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. At the time of measurement, the temperature of the liquid crystal cell was 23 ° C. and 60 ° C., and the measurement was performed at each temperature.
[AC drive burn-in of FFS drive liquid crystal cell]
On a glass substrate, a 50 nm thick ITO electrode having the shape shown in FIG. 1 is used as the first layer as an electrode, and a 500 nm thick silicon nitride having a shape shown in FIG. Comb-shaped ITO electrodes (electrode width: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm) shown in FIG. 3 as electrodes in the layer are fringe field switching (hereinafter referred to as FFS) driving electrodes. The liquid crystal aligning agent was apply | coated to the glass substrate in which was formed by spin coat application | coating. After drying on an 80 ° C. hot plate for 5 minutes, baking was performed in a hot air circulation oven at 250 ° C. for 60 minutes to form a coating film having a thickness of 100 nm. The coating surface was irradiated with 100 mJ / cm ^{2 of} 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. In addition, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm on which no electrode was formed as a counter substrate, and an orientation treatment was performed.
The two substrates are combined as a set, a sealant is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, and then the sealant is added. An empty cell was produced by curing. Liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell.
After measuring the VT characteristic (voltage-transmittance characteristic) of this FFS drive liquid crystal cell at a temperature of 58 ° C., a rectangular wave of ± 4 V / 120 Hz was applied for 4 hours. After 4 hours, the voltage was turned off and left at a temperature of 58 ° C. for 60 minutes, and then the VT characteristics were measured again, and the difference in voltage at which the transmittance before and after the rectangular wave application was 50% was calculated.
[Evaluation of charge storage characteristics]
Place the FFS drive liquid crystal cell on the light source, measure the VT characteristics (voltage-transmittance characteristics), and then measure the transmittance (T _a ) with _a square wave of ± 1.5 V / 60 Hz applied. did. Then, after applying a square wave of ± 1.5 V / 60 Hz for 10 minutes, DC 1 V was superimposed and driven for 30 minutes. Off a DC voltage, the transmittance after passage AC drive 10 minutes (T _b) were measured, to calculate the difference in transmittance caused by the voltage remaining in the liquid crystal display device from the difference between T _b and T _a.

Synthesis of dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate (1,3DMCBDE-Cl) a-1: Synthesis of dialkyl ester of tetracarboxylic acid

Under a nitrogen stream, a 3-liter (liter) four-necked flask was charged with 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-1), hereinafter 1, When 220 g (0.981 mol) of 3-DM-CBDA) and 2200 g of methanol (6.87 mol, 10 wt times with respect to 1,3-DM-CBDA) were charged and heated to reflux at 65 ° C. A uniform solution was obtained in 30 minutes. The reaction solution was stirred for 4 hours and 30 minutes under heating and reflux. This reaction solution was measured by high performance liquid chromatography (hereinafter abbreviated as HPLC). The analysis of the measurement result will be described later.
After evaporating the solvent from the reaction solution with an evaporator, 1301 g of ethyl acetate was added, heated to 80 ° C., and refluxed for 30 minutes. Thereafter, the mixture was cooled at a rate of 2 to 3 ° C. for 10 minutes until the internal temperature reached 25 ° C., and stirred at 25 ° C. for 30 minutes. The precipitated white crystals were taken out by filtration, washed twice with 141 g of ethyl acetate, and then dried under reduced pressure to obtain 103.97 g of white crystals.
This crystal was confirmed to be the compound (1-1) by the results of ¹ H NMR analysis and X-ray crystal structure analysis (HPLC relative area 97.5%) (yield 36.8%).
¹ H NMR (DMSO-d6, δ ppm); 12.82 (s, 2H), 3.60 (s, 6H), 3.39 (s, 2H), 1.40 (s, 6H).
Synthesis of a-2.1,3-DM-CBDE-C1

In a nitrogen stream, 234.15 g (0.81 mol) of compound (1-1) and 1117.77 g (11.68 mol.5 wt times) of n-heptane were charged into a 3 L four-necked flask, and then pyridine 0 .64 g (0.01 mol) was added, and the mixture was heated to 75 ° C. with magnetic stirrer stirring. Subsequently, 289.93 g (11.68 mol) of thionyl chloride was added dropwise over 1 hour. Foaming started immediately after the dropping, and the reaction solution became uniform 30 minutes after the completion of the dropping, and the foaming stopped. Subsequently, the mixture was stirred as it was at 75 ° C. for 1 hour and 30 minutes, and then the solvent was distilled off with an evaporator until the internal volume reached 924.42 g in a water bath at 40 ° C. This was heated to 60 ° C., the crystals precipitated when the solvent was distilled off were dissolved, the insoluble matter was filtered by performing hot filtration at 60 ° C., and then the filtrate was heated to 25 ° C. at a rate of 1 ° C. for 10 minutes. It was cooled with. After stirring for 30 minutes at 25 ° C., the precipitated white crystals were taken out by filtration, and the crystals were washed with 264.21 g of n-heptane. This was dried under reduced pressure to obtain 226.09 g of white crystals.
Subsequently, 226.009 g of the white crystals obtained above and 454.18 g of n-heptane were charged in a 3 L four-necked flask in a nitrogen stream, and the crystals were dissolved by heating to 60 ° C. with stirring. . Thereafter, the mixture was cooled and stirred at a rate of 1 ° C. for 10 minutes to 25 ° C. to precipitate crystals. After stirring for 1 hour at 25 ° C., the precipitated white crystals were taken out by filtration, washed with 113.04 g of n-hexane, and dried under reduced pressure to obtain 203.91 g of white crystals. According to the results of 1H NMR analysis, this crystal was found to be compound (3-1), that is, dimethyl-1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate (1,3-DM -CBDE-C1) (HPLC relative area 99.5%) (yield 77.2%).
¹ H NMR (CDCl ₃ , δ ppm): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H).

(Production Example 1)
A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 6.40 g (32.3 mmol) of 4,4′-diaminodiphenylmethane was added, 131 g of NMP, and 6.16 g (77.86 mmol) of pyridine as a base were added. Stir to dissolve. Next, while stirring this diamine solution, 9.8641 g (27.16 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.380 g (4.20 mmol) of acryloyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 144.33 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 1443 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by 1443 g of water once, 1443 g of ethanol once, and 361 g of ethanol. After washing 3 times and drying, 14.37 g of polyamic acid ester resin powder having a modified white end was obtained. The yield was 99.6%. Moreover, the molecular weight of the polyamic acid ester modified at this end was Mn = 13,335 and Mw = 23,824.
The obtained end-modified polyamic acid ester resin powder (3.3076 g) was placed in a 50 ml Erlenmeyer flask, NMP (30.4854 g) was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-1).

(Production Example 2)
A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 5.00 g (25.22 mmol) of 4,4′-diaminodiphenylmethane was added, 102 g of NMP, and 4.81 g (60.83 mmol) of pyridine as a base were added. Stir to dissolve. Next, while stirring this diamine solution, 7.707 g (23.71 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. Four hours later, 0.4302 g (3.30 mmol) of 2-furanyl chloride was added, and the mixture was reacted for 30 minutes under water cooling. After 30 minutes, 114 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 1141 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by 1141 g of water, 1141 g of ethanol once, and 285 g of ethanol. By washing three times and drying, 11.12 g of a polyamic acid ester resin powder having a modified white end was obtained. The yield was 97.5%. Moreover, the molecular weight of the polyamic acid ester modified at this end was Mn = 12,864 and Mw = 22,513.
3.1266 g of the resulting polyamic acid ester resin powder having a modified end was placed in a 50 ml Erlenmeyer flask, 28.1581 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-2).

(Production Example 3)
A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 5.00 g (25.22 mmol) of 4,4′-diaminodiphenylmethane was added, 103 g of NMP, and 4.81 g (60.83 mmol) of pyridine as a base were added. Stir to dissolve. Next, while stirring the diamine solution, 7.7075 g (23.71 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.4702 g (3.35 mmol) of benzoyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 114 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 1144 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then once with 1144 g of water, once with 1144 g of ethanol, and 286 g of ethanol. The white polyamic acid ester resin powder 11.10g was obtained by wash | cleaning 3 times and drying. The yield was 97.0%. Moreover, the molecular weight of the polyamic acid ester modified at this end was Mn = 11,260 and Mw = 19,060.
The obtained end-modified polyamic acid ester resin powder 3.6625 g was placed in a 50 ml Erlenmeyer flask, NMP 32.9616 g was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-3).

(Production Example 4)
A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 5.00 g (25.22 mmol) of 4,4′-diaminodiphenylmethane was added, 103 g of NMP, and 4.81 g (60.83 mmol) of pyridine as a base were added. Stir to dissolve. Next, while stirring this diamine solution, 7.7014 g (23.70 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.5140 g (3.28 mmol) of phenyl chloroformate was added and reacted for 30 minutes under water cooling. After 30 minutes, 115 g of NMP was added to the reaction solution and stirred at room temperature (20 ° C.) for 15 minutes. The obtained polyamic acid ester solution was poured into 1149 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by 1503 g of water once, 1149 g of ethanol once, and 287 g of ethanol. By washing three times and drying, 11.01 g of a polyamic acid ester resin powder having a modified white end was obtained. The yield was 95.8%. Further, the molecular weight of the polyamic acid ester modified at this end was Mn = 11,772 and Mw = 20,564.
The obtained end-modified polyamic acid ester resin powder 3.6176 g was placed in a 50 ml Erlenmeyer flask, NMP 32.597 g was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-4).

(Production Example 5)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2.7469 g (13.79 mmol) of 4,4′-diaminodiphenylamine and 1.4007 g (9.206 mmol) of 3,5-diaminobenzoic acid were placed. NMP (38.85 g) was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 4.4319 g (22.60 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid (PAA-1). Solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 1055 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 21,482 and Mw = 49,280.

(Production Example 6)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 7.9719 g (40.01 mmol) of 4,4′-diaminodiphenylamine and 1.5246 g (10.02 mmol) of 3,5-diaminobenzoic acid were added. Then, 40.64 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 9.8377 g (49.65 mmol) of BDA was added, NMP was further added so that the solid content concentration was 25% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution. . The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 14550 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 16,230 and Mw = 34,539.
45.1642 g of the obtained polyamic acid solution was placed in a 100 ml Erlenmeyer flask, 33.87 g of NMP was added, and the mixture was stirred at room temperature for 4 hours to obtain a 15% by mass polyamic acid solution (PAA-2).

(Comparative Production Example 1)
A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 8.0102 g (40.35 mmol) of 4,4′-diaminodiphenylmethane was added, 158.1 g of NMP, and 7.20 g (91.03 mmol) of pyridine as a base. ) Added and stirred to dissolve. Next, while stirring this diamine solution, 12.3419 g (37.93 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 1757 g of water with stirring, and the precipitated white precipitate was collected by filtration, followed by 1757 g of water once, 1757 g of ethanol once, and 439 g of ethanol. After washing 3 times and drying, 16.63 g of white polyamic acid ester resin powder was obtained. The yield was 94.6%. Moreover, the molecular weight of this polyamic acid ester was Mn = 10,180 and Mw = 21,476.
The obtained polyamic acid ester resin powder 14.8252 was placed in a 200 ml Erlenmeyer flask, NMP 99.3048 g was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-5).

Example 1
In a 20 ml sample tube containing a stirrer, 1.5016 g of the polyamic acid ester solution (PAE-1) obtained in Production Example 1 and 1.0469 g of the polyamic acid solution (PAA-1) obtained in Production Example 5 were triangular. It took to the flask, NMP1.4916g and BCS1.0249g were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained liquid crystal aligning agent (I).
(Example 2)
In a 20 ml sample tube containing a stirrer, 1.5050 g of the polyamic acid ester solution (PAE-2) obtained in Production Example 2 and 0.9091 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were triangular. Into the flask, 1.6291 g of NMP and 1.0032 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II).
(Example 3)
In a 20 ml sample tube containing a stirrer, 1.5138 g of the polyamic acid ester solution (PAE-3) obtained in Production Example 3 and 0.8932 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were triangular. It took to the flask, NMP1.6438g and BCS1.0231g were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained liquid crystal aligning agent (III).
Example 4
In a 20 ml sample tube containing a stir bar, 1.5097 g of the polyamic acid ester solution (PAE-4) obtained in Production Example 4 and 0.8953 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were triangular. It took to the flask, NMP1.6372g and BCS1.0101g were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained liquid crystal aligning agent (IV).

(Comparative Example 1)
In a 20 ml sample tube containing a stir bar, 1.4911 g of the polyamic acid ester solution (PAE-5) obtained in Comparative Production Example 1 and 1.1118 g of the polyamic acid solution (PAA-1) obtained in Production Example 5 were added. Then, 1.4881 g of NMP and 1.0315 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (a).
(Comparative Example 3)
In a 20 ml sample tube containing a stir bar, 1.0391 g of the polyamic acid ester solution (PAE-5) obtained in Comparative Production Example 1 and 1.5095 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were added. Then, NMP1.4964g and BCS 1.0011g were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (c).

(Example 5)
The liquid crystal aligning agent (I) obtained in Example 1 was filtered through a 1.0 μm filter, 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 a temperature of 250 An imidized film having a film thickness of 100 nm was obtained after baking for 60 minutes in a hot air circulating oven at 0 ° C. The centerline average roughness (Ra) of this film was measured. About a measurement result, it shows in Table 1 mentioned later.
(Example 6)
An imidized film was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (II) obtained in Example 2 was used. The centerline average roughness (Ra) of this film was measured. About a measurement result, it shows in Table 1 mentioned later.
(Example 7)
An imidized film was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (III) obtained in Example 3 was used. The centerline average roughness (Ra) of this film was measured. About a measurement result, it shows in Table 1 mentioned later.
(Example 8)
An imidized film was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (IV) obtained in Example 4 was used. The centerline average roughness (Ra) of this film was measured. About a measurement result, it shows in Table 1 mentioned later.

(Comparative Example 4)
An imidized film was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (a) obtained in Comparative Example 1 was used. The centerline average roughness (Ra) of this film was measured. About a measurement result, it shows in Table 1 mentioned later.
(Comparative Example 6)
An imidized film was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (c) obtained in Comparative Example 3 was used. The centerline average roughness (Ra) of this film was measured. About a measurement result, it shows in Table 1 mentioned later.

From the results of Example 5 and Comparative Example 4 and from the results of Examples 6 to 8 and Comparative Example 6, the liquid crystal aligning agent containing terminally modified polyamic acid ester and polyamic acid was phase-separated between polyamic acid ester and polyamic acid. It was confirmed that the micro unevenness generated by the above is suppressed.
Example 9
The liquid crystal aligning agent (I) obtained in Example 1 was filtered through a 1.0 μm filter, 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 a temperature of 250 An imidized film having a film thickness of 100 nm was obtained after baking for 60 minutes in a hot air circulating oven at 0 ° C. The coating surface was irradiated with 100 mJ / 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 sprayed on the liquid crystal alignment film surface of one of the substrates, and then the two substrates are combined so that the alignment is antiparallel. The periphery was sealed and the empty cell having a cell gap of 6 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the inlet was sealed to obtain a liquid crystal cell. 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 liquid crystal cell was produced in the same manner as in Example 9 except that the liquid crystal aligning agent (a) obtained in Comparative Example 1 was used. 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.

　実施例９と比較例７の結果より、本発明の液晶配向剤から得られる液晶配向膜は、信頼性の高い液晶配向膜であることが確認された。

From the results of Example 9 and Comparative Example 7, it was confirmed that the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention was a highly reliable liquid crystal alignment film.

(Example 10)
After filtering the liquid crystal aligning agent (I) obtained in Example 1 with a 1.0 μm filter, an ITO electrode having a film thickness of 50 nm as a first layer and an insulating film as a second layer on a glass substrate. A silicon nitride film having a thickness of 500 nm is used as a third layer of a fringe field switching (hereinafter referred to as FFS) having comb-shaped ITO electrodes (electrode width: 3 μm, electrode interval: 6 μm, electrode height: 50 nm). ) It was applied by spin coating to a glass substrate on which driving electrodes were formed. After drying on an 80 ° C. hot plate for 5 minutes, baking was performed in a hot air circulation oven at 250 ° C. for 60 minutes to form a coating film having a thickness of 130 nm. The coating surface was irradiated with 100 mJ / cm ^{2 of} 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. In addition, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm on which no electrode was formed as a counter substrate, and an orientation treatment was performed.
The two substrates are combined as a set, a sealant is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, and then the sealant is added. An empty cell was produced by curing. Liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell.
The FFS drive liquid crystal cell was measured for AC drive and evaluated for charge storage characteristics. The results are shown in Table 3 described later.
(Comparative Example 8)
An FFS drive liquid crystal cell was produced in the same manner as in Example 10 except that the liquid crystal aligning agent (a) obtained in Comparative Example 1 was used. This FFS drive liquid crystal cell was evaluated for AC drive burn-in and charge storage characteristics. The results are shown in Table 3 described later.

　実施例１０と比較例８の結果より、本発明の液晶配向剤から得られる液晶配向膜は、交流駆動焼き付きの程度が小さく、且つ残留電圧が少ない液晶配向膜が得られることが確認された。

From the results of Example 10 and Comparative Example 8, it was confirmed that the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can obtain a liquid crystal alignment film having a small degree of AC drive burn-in and a small residual voltage.

Synthesis of diamine compound (DA-1) The diamine compound (DA-1) was synthesized by the following four-step route.
First step: Synthesis of compound (A5)

　５００ｍＬ のナスフラスコにプロパルギルアミン (8.81 g, 160 mmol) 、N,N-ジメチルホルムアミド (112 mL) 、炭酸カリウム (18.5 g, 134 mmol) の順に入れ、0 ℃ にし、ブロモ酢酸t-ブチル (21.9 g, 112 mmol) をN,N-ジメチルホルムアミド (80 mL) に溶かした溶液を約1時間で、撹拌しながら滴下した。滴下終了後、反応溶液を室温にし、20時間撹拌した。その後、固形物をろ過により除去し、ろ液に酢酸エチルを 1 L 加え、300 mL の水で 4 回、300 mL の飽和食塩水で 1 回洗浄した。その後、有機層を硫酸マグネシウムで乾燥し、溶媒を減圧留去した。最後に、残留した油状物を 0.6 Torr, 70 ℃で減圧蒸留することにより、無色液体のN-プロパルギルアミノ酢酸t-ブチル（化合物（Ａ５））を得た。収量は 12.0 g、収率は63% であった。

第２ステップ：化合物（Ａ６）の合成

Into a 500 mL eggplant flask, put propargylamine (8.81 g, 160 mmol), N, N-dimethylformamide (112 mL), potassium carbonate (18.5 g, 134 mmol) in this order, bring it to 0 ° C., and add t-butyl bromoacetate (21.9 g, 112 mmol) in N, N-dimethylformamide (80 mL) was added dropwise with stirring over about 1 hour. After completion of the dropwise addition, the reaction solution was brought to room temperature and stirred for 20 hours. Thereafter, the solid matter was removed by filtration, 1 L of ethyl acetate was added to the filtrate, and the mixture was washed 4 times with 300 mL of water and once with 300 mL of saturated saline. Thereafter, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Finally, the remaining oil was distilled under reduced pressure at 0.6 Torr and 70 ° C. to obtain t-butyl N-propargylaminoacetate (compound (A5)) as a colorless liquid. The yield was 12.0 g, and the yield was 63%.

Second step: Synthesis of compound (A6)

　1 L のナスフラスコに上記N-プロパルギルアミノ酢酸t-ブチル (12.0 g, 70.9 mmol)、ジクロロメタン (600 mL) を入れて溶液とし、攪拌氷冷しながら、二炭酸ジt-ブチル (15.5 g, 70.9 mmol) をジクロロメタン (100 mL) に溶かした溶液を１時間で滴下した。滴下終了後、反応溶液を室温にし、20時間攪拌した。反応終了後、反応溶液を300 mL の飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。その後、溶媒を減圧留去することで、薄黄色液体のN-プロパルギル-N-t-ブトキシカルボニルアミノ酢酸t-ブチル（化合物（Ａ６））を得た。収量は 18.0 g、収率は 94% であった。
第３ステップ：化合物（Ａ７）の合成

In a 1 L eggplant flask, the above N-propargylaminoacetic acid t-butyl (12.0 g, 70.9 mmol) and dichloromethane (600 mL) were added to form a solution. While stirring and cooling with ice, di-t-butyl dicarbonate (15.5 g, A solution of 70.9 mmol) in dichloromethane (100 mL) was added dropwise over 1 hour. After completion of the dropwise addition, the reaction solution was brought to room temperature and stirred for 20 hours. After completion of the reaction, the reaction solution was washed with 300 mL of saturated brine and dried over magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure to obtain N-propargyl-Nt-butoxycarbonylaminoacetic acid t-butyl (compound (A6)) as a light yellow liquid. The yield was 18.0 g, and the yield was 94%.
Third step: Synthesis of compound (A7)

2-Iodo-4-nitroaniline (22.5 g, 85.4 mmol), bis (triphenylphosphine) palladium dichloride (1.20 g, 1.71 mmol), copper iodide (0.651 g, 3.42 mmol) in a 300 mL four-necked flask After adding nitrogen and replacing with nitrogen, diethylamine (43.7 g, 598 mmol) and N, N-dimethylformamide (128 mL) were added, and while stirring on ice, the N-propargylamino-Nt-butoxycarbonyl acetate t-butyl was added. (27.6 g, 102 mmol) was added and stirred at room temperature for 20 hours. After completion of the reaction, 1 L of ethyl acetate was added, washed with 150 mL of a 1 mol / L aqueous ammonium chloride solution three times and once with 150 mL of saturated brine, and dried over magnesium sulfate. Thereafter, the solvent was distilled off under reduced pressure, and the precipitated solid was dissolved in 200 mL of ethyl acetate and recrystallized by adding 1 L of hexane. This solid was collected by filtration and dried under reduced pressure to give 2- {3- (Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino) -1-propynyl)}-4-nitroaniline (compound (A7)) as a yellow solid. ) The yield was 23.0 g, and the yield was 66%.
Fourth Step: Reduction of Compound (A7) Into a 500 mL four-necked flask, the 2- {3- (Nt-butoxycarbonyl-Nt-butoxycarbonylmethylamino) -1-propynyl)}-4-nitroaniline (22.0 g, 54.2 mmol) and ethanol (200 g) were added, and the inside of the system was replaced with nitrogen. Then, palladium carbon (2.20 g) was added, the inside of the system was replaced with hydrogen, and the mixture was stirred at 50 ° C. for 48 hours. After completion of the reaction, palladium carbon was removed by Celite filtration, activated carbon was added to the filtrate, and the mixture was stirred at 50 ° C. for 30 minutes. Thereafter, the activated carbon was filtered, the organic solvent was distilled off under reduced pressure, and the remaining oil was dried under reduced pressure to obtain a diamine compound (DA-1). The yield was 19.8 g, and the yield was 96%.
The diamine compound (DA-1) was confirmed by ¹ H NMR.
¹ H NMR (DMSO-d ₆ ): δ 6.54-6.42 (m, 3H, Ar), 3.49, 3.47 (each s, 2H, NCH ₂ CO ₂ t-Bu), 3.38-3.30 (m, 2H, CH ₂ CH ₂ N), 2.51-2.44 (m, 2H, ArCH ₂ ), 1.84-1.76 (m, 2H, CH ₂ CH ₂ CH ₂ ), 1.48-1.44 (m, 18H, NCO ₂ t-Bu and CH ₂ CO ₂ t-Bu).
(Production Example 7)
A four-necked flask with a stirrer is placed in a nitrogen atmosphere, and 2.000 g (10.0878 mmol) of 4,4'-diaminodiphenylmethane is added. It was. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.192 g (1.3114 mmol) of 2-thenoyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 45.2499 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 498 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 226 g of ethanol once, 452 g of water twice, and 453 g of ethanol 1 This was washed 3 times with 113 g of ethanol and dried to obtain 4.4587 g of white polyamic acid ester resin powder. The yield was 98.53%. The molecular weight of this polyamic acid ester was Mn = 12256 and Mw = 21405.
2.1520 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 19.3658 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-7).
(Production Example 8)
A 100 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. Four hours later, 0.1555 g (1.3114 mmol) of 3,3-dimethylacryloyl chloride was added, and the mixture was reacted for 30 minutes under water cooling. After 30 minutes, 44.9236 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 494 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 225 g of ethanol once, 449 g of water twice, and 449 g of ethanol 1 This was washed 3 times with 112 g of ethanol and dried to obtain 3.9916 g of white polyamic acid ester resin powder. The yield was 88.98%. The molecular weight of this polyamic acid ester was Mn = 13673 and Mw = 22739.
2.3883 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 21.5218 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-8).
(Production Example 9)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. Four hours later, 0.2185 g (1.3114 mmol) of cinnamoyl chloride was added, and the mixture was reacted for 30 minutes under water cooling. After 30 minutes, 45.54 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 500 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 455 g of water twice, and 455 g of ethanol 1 This was washed 3 times with 114 g of ethanol and dried to obtain 4.2721 g of white polyamic acid ester resin powder. The yield was 93.91%. The molecular weight of this polyamic acid ester was Mn = 13033 and Mw = 23520.
2.4517 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 22.0656 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-9).
(Production Example 10)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. Four hours later, 0.1725 g (1.3114 mmol) of isoxazole-5-carboxylic acid chloride was added, and the mixture was reacted for 30 minutes under water cooling. After 30 minutes, 45.06 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 495 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 226 g of ethanol once, 451 g of water twice, and 451 g of ethanol 1 This was washed 3 times with 113 g of ethanol and dried to obtain 4.3714 g of white polyamic acid ester resin powder. The yield was 96.99%. The molecular weight of this polyamic acid ester was Mn = 13418 and Mw = 22819.
2.2172 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 19.9964 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-10).

(Production Example 11)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere, and 2.000 g (10.0878 mmol) of 4,4'-diaminodiphenylmethane is added. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.1948 g (1.3114 mmol) of 2-oxo-1-imidazolidinecarbonyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 45.23 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 498 g of ethanol with stirring, and the precipitated white precipitate was collected by filtration, followed by 226 g of ethanol once, 453 g of water twice, and 453 g of ethanol 1 This was washed 3 times with 113 g of ethanol and dried to obtain 3.98 g of white polyamic acid ester resin powder. The yield was 87.92%. Further, the molecular weight of this polyamic acid ester was Mn = 12119 and Mw = 23633.
2.1446 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 19.2937 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-11).
(Production Example 12)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere, and 2.000 g (10.0878 mmol) of 4,4'-diaminodiphenylmethane is added. Dissolved. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.1213 g (1.3114 mmol) of propionyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 44.60 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 491 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 223 g of ethanol once, 446 g of water twice, and 446 g of ethanol 1 This was washed 3 times with 111 g of ethanol and dried to obtain 3.74 g of white polyamic acid ester resin powder. The yield was 83.86%. The molecular weight of this polyamic acid ester was Mn = 13082 and Mw = 23048.
2.1867 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 19.6897 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-12).
(Production Example 13)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere, and 2.000 g (10.0878 mmol) of 4,4'-diaminodiphenylmethane is added. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.2079 g (1.3114 mmol) of 4-fluorobenzoyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 45.39 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 499 g of ethanol with stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 454 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 3.87 g of white polyamic acid ester resin powder. The yield was 85.26%. The molecular weight of this polyamic acid ester was Mn = 12207 and Mw = 22609.
1.9882 g of the resulting polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 17.908 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-13).
(Production Example 14)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere, and 2.000 g (10.0878 mmol) of 4,4'-diaminodiphenylmethane is added. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.2841 g (1.3114 mmol) of 4-phenylbenzoyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 46.10 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 507 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, and then once with 230 g of ethanol, twice with 461 g of water, and 1 with 461 g of ethanol. This was washed 3 times with 115 g of ethanol and dried to obtain 4.02 g of white polyamic acid ester resin powder. The yield was 87.20%. The molecular weight of this polyamic acid ester was Mn = 11563 and Mw = 22120.
2.1231 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 19.1000 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-14).
(Production Example 15)
A 100 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 2.000 g (10.0878 mmol) of 4,4'-diaminodiphenylmethane was added. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.2079 g (1.3114 mmol) of cyclopropanecarbonyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 45.39 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 499 g of ethanol with stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 454 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 3.8463 g of white polyamic acid ester resin powder. The yield was 84.7%. The molecular weight of this polyamic acid ester was Mn = 12995 and Mw = 23470.
2.3403 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 21.0717 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-15).

(Manufacturing 16)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.2079 g (0.897 mmol) of diphenylcarbamoyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 45.39 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 499 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 454 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 3.7689 g of white polyamic acid ester resin powder. The yield was 83.0%. The molecular weight of this polyamic acid ester was Mn = 9543 and Mw = 21337.
2.0849 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 18.7717 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-16).
(Production Example 17)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. Four hours later, 0.2079 g (2.6484 mmol) of acetyl chloride was added, and the mixture was reacted for 30 minutes under water cooling. After 30 minutes, 45.39 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 499 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 454 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 4.2288 g of white polyamic acid ester resin powder. The yield was 93.2%. The molecular weight of this polyamic acid ester was Mn = 13739 and Mw = 24113.
2.2812 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 20.5236 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-17).
(Production Example 18)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. Four hours later, 0.2079 g (1.9889 mmol) of methacryloyl chloride was added, and the mixture was reacted for 30 minutes under water cooling. After 30 minutes, 45.39 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 499 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 454 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 4.5616 g of white polyamic acid ester resin powder. The yield was 99.0%. The molecular weight of this polyamic acid ester was Mn = 14046 and Mw = 23471.
2.2641 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 20.3711 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-18).
(Production Example 19)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere. Dissolved. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.2079 g (1.8804 mmol) of methyl chlorothioformate was added and reacted for 30 minutes under water cooling. After 30 minutes, 45.39 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 499 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 454 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 4.2667 g of white polyamic acid ester resin powder. The yield was 94.0%. The molecular weight of this polyamic acid ester was Mn = 13857 and Mw = 24200.
2.2436 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 20.1778 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-19).

(Production Example 20)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.2079 g (1.2187 mmol) of 4-methoxybenzoyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 45.39 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 499 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 454 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 4.2667 g of white polyamic acid ester resin powder. The yield was 95.7%. The molecular weight of this polyamic acid ester was Mn = 12439 and Mw = 23256.
2.4178 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 21.7607 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-20).
(Production Example 21)
A 100 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 2.000 g (10.0878 mmol) of 4,4′-diaminodiphenylmethane was added. 40.86 g of NMP and 2.0759 g (26.2443 mmol) of pyridine as a base were added and dissolved by stirring. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.6003 g (2.90528 mmol) of 2-naphthylchloroformate was added and reacted for 30 minutes under water cooling. After 30 minutes, 45.98 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 552 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 460 g of water twice, and 228 g of ethanol 1 This was washed three times with 115 g of ethanol and dried to obtain 4.24 g of white polyamic acid ester resin powder. The yield was 92.2%. The molecular weight of this polyamic acid ester was Mn = 12498 and Mw = 22829.
1.9683 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 17.7163 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-21).
(Production Example 22)
A 100 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere, and 2.000 g (10.0878 mmol) of 4,4′-diaminodiphenylmethane is added, and 40.86 g of NMP and 2.0759 g (26.2443 mmol) of pyridine as a base are added and stirred. Dissolved. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.4726 g (2.90528 mmol) of 2-n-propyl-n-valeryl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 45.44 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 545 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 227 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 3.89 g of white polyamic acid ester resin powder. The yield was 85.7%. The molecular weight of this polyamic acid ester was Mn = 15211 and Mw = 25954.
2.6046 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 18.5329 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-22).
(Production Example 23)
A 100 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 2.000 g (10.0878 mmol) of 4,4′-diaminodiphenylmethane was added. 40.86 g of NMP and 2.0759 g (26.2443 mmol) of pyridine as a base were added and dissolved by stirring. I let you. Next, while stirring this diamine solution, 3.0831 g (9.4825 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.4637 g (2.90528 mmol) of diallylcarbamyl chloride was added and reacted for 30 minutes under water cooling. After 30 minutes, 45.41 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 545 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 227 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 3.83 g of white polyamic acid ester resin powder. The yield was 84.3%. The molecular weight of this polyamic acid ester was Mn = 9243 and Mw = 20232.
2.2187 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 19.9635 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-23).
(Production Example 24)
In a 100 ml four-necked flask equipped with a stirrer, 4.9034 g (18.84 mmol) of 2,4-bis (methoxycarbonyl) cyclobutane-1,3-dicarboxylic acid was taken, and 68.12 g of NMP was added and dissolved by stirring. Subsequently, 4.45 g (43.98 mmol) of triethylamine, 1.7315 g (16.01 mmol) of p-phenylenediamine, and 0.7922 g (4.00 mmol) of 4,4′-diaminodiphenylmethane were added and dissolved by stirring. While stirring this solution, 16.90 g (44.08 mmol) of diphenyl (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphonate was added, and 9.67 g of NMP was further added, followed by reaction under water cooling for 4 hours. It was. After 4 hours, 0.2607 g (2.88 mmol) of acryloyl chloride was added and reacted for 30 minutes under water cooling. The obtained polyamic acid ester solution was poured into 650 g of 2-propanol with stirring, and the deposited precipitate was collected by filtration, then washed with 210 g of 2-propanol five times and dried to obtain a polyamic acid ester. A resin powder was obtained.
The molecular weight of this polyamic acid ester was Mn = 3189 and Mw = 4783.
2.3389 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 22.6242 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-24).
(Production Example 25)
A 100 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 3.0000 g (15.13 mmol) of 4,4′-diaminodiphenylmethane, 1.38 g (10.13 mmol) of 3-amino-N-methylbenzylamine were added, and NMP was 94.65. g, 5.75 g (56.89 mmol) of triethylamine as a base was added and dissolved by stirring. Next, while stirring this diamine solution, 7.7149 g (23.73 mmol) of 1,3DM-CBDE-Cl was added and reacted for 4 hours under water cooling. After 4 hours, 0.0.6574 g (7.2632 mmol) of acryloyl chloride was added and reacted for 30 minutes under water cooling. The obtained polyamic acid ester solution was added to 450 g of 2-propanol with stirring, and the precipitated white precipitate was collected by filtration, subsequently washed 5 times with 220 g of 2-propanol, and dried to give a white solution. A polyamic acid ester resin powder was obtained. The molecular weight of this polyamic acid ester was Mn = 8861 and Mw = 20627.
1.5913 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 14.5979 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-25).

(Production Example 26)
In a 100 ml four-necked flask equipped with a stirrer, 1.2654 g (4.48 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid and 2.6157 g of 2,4-bis (methoxycarbonyl) cyclobutane-1,3-dicarboxylic acid ( 10.05 mmol), and 73.16 g of NMP was added and dissolved by stirring. Subsequently, 3.34 g (33.01 mmol) of triethylamine and 3.8784 g (15.01 mmol) of 1,3-bis (4-aminophenoxy) propane were added and dissolved by stirring. While stirring this solution, 12.68 g (33.08 mmol) of (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphonate diphenyl was added, and further 10.05 g of NMP was added, followed by reaction under water cooling for 4 hours. It was. Four hours later, 0.1508 g (1.07 mmol) of acryloyl chloride was added, and the mixture was reacted for 30 minutes under water cooling. The obtained polyamic acid ester solution was poured into 650 g of 2-propanol with stirring, and the deposited precipitate was collected by filtration, then washed with 210 g of 2-propanol five times and dried to obtain a polyamic acid ester. A resin powder was obtained. The molecular weight of this polyamic acid ester was Mn = 15633 and Mw = 32874.
1.2264 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 11.4164 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-26).
(Production Example 28)
A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 3.1516 g (29.14 mmol) of p-phenylenediamine, 1.2301 g (3.24 mmol) of DA-1 were added, 58.11 g of NMP, γ- 174.34 g of BL and 5.78 g (73.13 mmol) of pyridine as a base were added and dissolved by stirring. Next, 9.9137 g (30.49 mmol) of 1,3DM-CBDE-Cl was added while stirring the diamine solution, and the mixture was reacted for 4 hours under water cooling. After 4 hours, 0.7329 g (9.34 mmol) of acetyl chloride was added and reacted for 30 minutes under water cooling. The obtained polyamic acid ester solution was poured into 1012 g of 2-propanol with stirring, and the deposited precipitate was collected by filtration, then washed with 823 g of 2-propanol five times and dried to obtain a polyamic acid ester. A resin powder was obtained.
The molecular weight of this polyamic acid ester was Mn = 17834 and Mw = 33755.
10.18 g of the obtained polyamic acid ester resin powder was placed in a 200 ml Erlenmeyer flask, 91.61 g of γ-BL was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-27).
(Production Example 28)
A 300 mL four-necked flask equipped with a stirrer was put in a nitrogen atmosphere, 3.1524 g (29.15 mmol) of p-phenylenediamine, 1.2301 g (3.24 mmol) of DA-1, 60.48 g of NMP, γ- 181.44 g of BL and 5.78 g (73.13 mmol) of pyridine as a base were added and dissolved by stirring. Next, 9.9032 g (30.46 mmol) of 1,3DM-CBDE-Cl was added while stirring the diamine solution, and the mixture was reacted for 4 hours under water cooling. After 4 hours, 1.9290 g (9.34 mmol) of 2-naphthylchloroformate was added and reacted for 30 minutes under water cooling. The obtained polyamic acid ester solution was added to 1055 g of 2-propanol with stirring, and the deposited precipitate was collected by filtration, then washed with 522 g of 2-propanol five times and dried to obtain a polyamic acid ester. A resin powder was obtained.
The molecular weight of this polyamic acid ester was Mn = 16701 and Mw = 33541.
10.21 g of the obtained polyamic acid ester resin powder was placed in a 200 ml Erlenmeyer flask, 92.52 g of γ-BL was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-28).
(Production Example 29)
A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 2.9935 g (27.68 mmol) of p-phenylenediamine, 1.1674 g (3.08 mmol) of DA-1, and 56.89 g of NMP, γ- 170.68 g of BL and 12.62 g (104.1 mmol) of 2,4,6-trimethylpyridine as a base were added and dissolved by stirring. Next, 9.4058 g (28.93 mmol) of 1,3DM-CBDE-Cl was added while stirring the diamine solution, and the mixture was reacted for 4 hours under water cooling. After 4 hours, 1.5772 g (8.86 mmol) of isonicotyl chloride hydrochloride was added and reacted for 30 minutes under water cooling. The obtained polyamic acid ester solution was added to 1004 g of 2-propanol with stirring, and the deposited precipitate was collected by filtration, then washed with 497 g of 2-propanol five times and dried to obtain a polyamic acid ester. A resin powder was obtained.
The molecular weight of this polyamic acid ester was Mn = 14972 and Mw = 31405.
1.6073 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, and 14.4534 g of γ-BL was added and stirred at room temperature for 24 hours to dissolve to obtain a polyamic acid ester solution (PAE-29).
(Production Example 30)
To a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, was added 1.848 g (9.23 mmol) of 4,4′-diaminodiphenyl ether and 2.1025 g (13.82 mmol) of 3,5-diaminobenzoic acid. 39.7 g of NMP was added, and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 4.8162 g (22.08 mmol) of pyromellitic dianhydride was added, NMP was further added so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid. A solution of (PAA-3) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 257 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 13,620 and Mw = 28,299.
(Production Example 31)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2.4301 g (15.97 mmol) of 3,5-diaminobenzoic acid, 9.4204 g (24.0 mmol) of DA-8, and 44 NMP were added. .60 g was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 4.7505 g (23.98 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 44.59 g of NMP was added, and 3.1054 g (15.84 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added. Further, NMP was added so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at a temperature of 25 ° C. was 802 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 13261 and Mw = 32578.
Further, 0.0590 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution and stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-4).

(Production Example 32)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 20.0838 g (132.0 mmol) of 3,5-diaminobenzoic acid and 21.3254 g (88.0 mmol) of DA-7 were taken, and 268 NMP was added. .48 g was added and dissolved by stirring while feeding nitrogen. While stirring the diamine solution, 42.4946 g (216.7 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was further added so that the solid content concentration was 20% by mass. The mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-5). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 2156 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 18794 and Mw = 63387.
(Production Example 33)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.6536 g (24.01 mmol) of 3,5-diaminobenzoic acid, 3.8715 g (15.98 mmol) of DA-7, and NMP 31 .75 g was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 3.9621 g (20.0 mmol) of BDA was added and stirred at room temperature for 2 hours. Next, 25.42 g of NMP was added, and 4.44776 (19.97 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added. Further, NMP was added so that the solid content concentration was 20% by mass, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at a temperature of 25 ° C. was 417 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 13291 and Mw = 54029.
Further, 0.0476 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, followed by stirring at room temperature for 24 hours to obtain a polyamic acid solution (PAA-6).
(Production Example 34)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.6516 g (24.0 mmol) of 3,5-diaminobenzoic acid and 2.4070 g (16.02 mmol) of 4-amino-N-methylphenethylamine were added. Then, 66.21 g of NMP was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 8.5972 g (39.42 mmol) of pyromellitic dianhydride was added. Further, NMP was added so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at a temperature of 25 ° C. was 488 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 13205 and Mw = 33511.
Further, 0.0438 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution and stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-7).
(Production Example 35)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.6603 g (24.06 mmol) of 3,5-diaminobenzoic acid and 4.7740 g of 1,3-bis (4-aminophenethyl) urea ( 16.0 mmol), 28.59 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring the diamine solution, 2.3782 g (12.0 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 38.13 g of NMP was added, and 6.0903 g (27.92 mmol) of pyromellitic dianhydride was added. Further, NMP was added so that the solid content concentration was 15% by mass, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at a temperature of 25 ° C. was 744 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 17771 and Mw = 38991.
Furthermore, 0.0505 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution and stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-8).

(Production Example 36)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.2080 g (16.02 mmol) of 4,4′-diaminodiphenyl ether, 5.8147 (24.0 mmol) of DA-7, and NMP of 60 .42 g was added and dissolved by stirring while feeding nitrogen. While stirring the diamine solution, 7.7658 g (39.60 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was further added so that the solid content concentration was 20% by mass. Stir at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at a temperature of 25 ° C. was 1972 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 15159 and Mw = 38251.
Further, 0.0504 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, followed by stirring at room temperature for 24 hours to obtain a polyamic acid solution (PAA-9).
(Production Example 37)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1.2133 g (7.97 mmol) of 3,5-diaminobenzoic acid and 6.8216 g of 4,4′-diaminodiphenyl-N-methyl-amine were added. (31.98 mmol) was taken, 44.03 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 7.1310 g (36.0 mmol) of BDA was added and stirred at room temperature for 2 hours. Next, 14.62 g of NMP was added, and 0.8713 g (3.99 mmol) of pyromellitic dianhydride was added. Further, NMP was added so that the solid content concentration was 18% by mass, and the mixture was stirred at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at a temperature of 25 ° C. was 577 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 1656 and Mw = 28487.
Further, 0.0480 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, followed by stirring at room temperature for 24 hours to obtain a polyamic acid solution (PAA-10).
(Production Example 38)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.5843 g (17.99 mmol) of 4,4′-diaminodiphenylamine and 2.9004 g (12.0 mmol) of DA-7 were added, and NMP was added 55 .58 g was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 5.7653 g (29.40 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was further added so that the solid content concentration was 15% by mass. Stir at room temperature for 24 hours. The viscosity of the obtained polyamic acid solution at a temperature of 25 ° C. was 1269 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 15559 and Mw = 43490.
Further, 0.0368 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-11).
(Production Example 39)
In a 500 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 6.087 g (40.01 mmol) of 3,5-diaminobenzoic acid was added, 71.04 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. . Next, 31.88 g (160 mmol) of 4,4′-diaminodiphenylamine and 124.30 g of γ-BL were added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 31.70 g (160 mmol) of BDA was added and stirred for 2 hours under water cooling. Next, 88.78 g of γ-BL was added and stirred for 10 minutes. Then, while stirring the reaction solution, 8.51 g (39.0 mmol) of pyromellitic dianhydride was added, and the solid content concentration was 18 mass. Γ-BL was added so that the concentration became% and the mixture was stirred for 24 hours under water cooling. The viscosity of the obtained polyamic acid solution at a temperature of 25 ° C. was 2864 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 14435 and Mw = 30525.
Further, 77.81 g of a 3-glycidoxypropylmethyldiethoxysilane solution diluted to 0.3% by mass with a mixed solvent having an NMP / γ-BL ratio of 2/8 was added to this solution, and a polyamic acid solution (PAA-12) was added. )
(Production Example 40)
To a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.6533 g (24.02 mmol) of 3,5-diaminobenzoic acid and 18.82 g of NMP were added, and stirred and dissolved while feeding nitrogen. Next, 3.8765 g (16.0 mmol) of DA-7 and 18.82 g of γ-BL were added and dissolved while stirring while feeding nitrogen. While stirring this diamine solution, 5.4708 g (27.61 mmol) of BDA was added, and the mixture was stirred for 2 hours under water cooling. Next, 4.71 g of γ-BL was added and stirred for 10 minutes, and then 2.700 g (12.04 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added while stirring the reaction solution. Further, γ-BL was added so that the solid content concentration was 20% by mass, and the mixture was stirred under water cooling for 24 hours. The viscosity of the obtained polyamic acid solution at a temperature of 25 ° C. was 2142 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 6509 and Mw = 11481.
Further, 0.0470 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution and stirred at room temperature for 24 hours to obtain a polyamic acid solution (PAA-13).

(Comparative Production Example 3)
In a 100 ml four-necked flask equipped with a stirrer, 5.1844 g (19.82 mmol) of 2,4-bis (methoxycarbonyl) cyclobutane-1,3-dicarboxylic acid was added, and 68.12 g of NMP was added and stirred to dissolve. It was. Subsequently, 4.45 g (43.98 mmol) of triethylamine, 1.7315 g (16.01 mmol) of p-phenylenediamine and 0.7922 g (3.99 mmol) of 4,4′-diaminodiphenylmethane were added and dissolved by stirring. I let you. While stirring this solution, 16.90 g (44.08 mmol) of (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphonic acid diphenyl was added, and 9.67 g of NMP was further added. Reacted for hours. The obtained polyamic acid ester solution was poured into 650 g of 2-propanol with stirring, and the deposited precipitate was collected by filtration, washed with 210 g of 2-propanol five times, and dried to obtain a polyamic acid ester. A resin powder was obtained.
The molecular weight of this polyamic acid ester was Mn = 3860 and Mw = 5384.
2.0332 g of the resulting polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 18.4708 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-30).
(Comparative Production Example 4)
A 100 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 2.01 g (10.09 mmol) of 4,4′-diaminodiphenylmethane and 0.92 g (6.73 mmol) of 3-amino-N-methylbenzylamine were added. 131.14 g of NMP and 3.83 g (37.93 mmol) of triethylamine as a base were added and dissolved by stirring. Next, while stirring this diamine solution, 5.1407 g (15.81 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 690 g of 2-propanol with stirring, and the precipitated white precipitate was collected by filtration, washed with 220 g of 2-propanol five times, and dried to obtain a white precipitate. A polyamic acid ester resin powder was obtained. The molecular weight of this polyamic acid ester was Mn = 5064 and Mw = 1348.
2.0014 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 18.29212 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-31).
(Comparative Production Example 5)
In a 200 ml four-necked flask equipped with a stirrer, 1.7779 g (6.30 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid and 3 of 2,4-bis (methoxycarbonyl) cyclobutane-1,3-dicarboxylic acid were added. .7712 g (14.49 mmol) was taken, 146.71 g of NMP was added, and dissolved by stirring. Subsequently, 4.25 g (42.0 mmol) of triethylamine and 5.4239 g (21.0 mmol) of 1,3-bis (4-aminophenoxy) propane were added and dissolved by stirring. While stirring this solution, 16.91 g (44.11 mmol) of (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphonic acid diphenyl was added, and further 25.81 g of NMP was added. Reacted for hours. The obtained polyamic acid ester solution was added to 1224 g of methanol while stirring, and the deposited precipitate was collected by filtration, then washed with 408 g of methanol four times and dried to obtain a polyamic acid ester resin powder. It was. The molecular weight of this polyamic acid ester was Mn = 15103 and Mw = 32483.
1.0172 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 9.4167 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-32).

(Comparative Production Example 6)
A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and p-phenylenediamine (3.0968 g, 28.64 mmol), DA-1 (1.2067 g, 3.18 mmol) were added, NMP (58.81 g), γ- 176.42 g of BL and 5.67 g (71.73 mmol) of pyridine as a base were added and dissolved by stirring. Next, 9.7184 g (29.89 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 poured into 1018 g of 2-propanol with stirring, and the deposited precipitate was collected by filtration, then washed with 504 g of 2-propanol five times and dried to obtain a polyamic acid ester. A resin powder was obtained.
The molecular weight of this polyamic acid ester was Mn = 16123 and Mw = 32976.
1.8932 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 17.0436 g of γ-BL was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-33).
(Example 11)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4106 g of the polyamic acid ester solution (PAE-7) obtained in Production Example 7 and 1.6477 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. Then, 2.3811 g of NMP and 1.5934 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-1).
(Example 12)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.3986 g of the polyamic acid ester solution (PAE-10) obtained in Production Example 10 and 1.6926 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3700 g) and BCS (1.6042 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-2).
(Example 13)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4102 g of the polyamic acid ester solution (PAE-11) obtained in Production Example 11 and 1.6552 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3643 g) and BCS (1.6339 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-3).
(Example 14)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4153 g of the polyamic acid ester solution (PAE-12) obtained in Production Example 12 and 1.6606 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3594 g) and BCS (1.6607 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-4).
(Example 15)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4079 g of the polyamic acid ester solution (PAE-13) obtained in Production Example 13 and 1.6504 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3762 g) and BCS (1.6062 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-5).

(Example 16)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.3990 g of the polyamic acid ester solution (PAE-9) obtained in Production Example 9 and 1.6445 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3564 g) and BCS (1.6084 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-6).
(Example 17)
A stir bar was placed in a 50 ml Erlenmeyer flask, and 2.3984 g of the polyamic acid ester solution (PAE-14) obtained in Production Example 14 and 1.663 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3651 g) and BCS (1.6102 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-7).
(Example 18)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.3983 g of the polyamic acid ester solution (PAE-21) obtained in Production Example 21 and 1.6284 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3625 g) and BCS (1.5973 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-8).
(Example 19)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4288 g of the polyamic acid ester solution (PAE-22) obtained in Production Example 22 was taken, and 1.6277 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 was taken. NMP (2.3674 g) and BCS (1.6044 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-9).
(Example 20)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4073 g of the polyamic acid ester solution (PAE-15) obtained in Production Example 15 and 1.4266 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5623 g of NMP and 1.6037 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-1).

(Example 21)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4315 g of the polyamic acid ester solution (PAE-8) obtained in Production Example 8 and 1.4539 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5771 g of NMP and 1.6047 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-2).
(Example 22)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4080 g of the polyamic acid ester solution (PAE-16) obtained in Production Example 16 was taken, and 1.5842 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 was taken. 2.5699 g of NMP and 1.6067 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-3).
(Example 23)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4016 g of the polyamic acid ester solution (PAE-20) obtained in Production Example 20 and 1.5320 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5650 g of NMP and 1.5970 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-4).
(Example 24)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4105 g of the polyamic acid ester solution (PAE-19) obtained in Production Example 19 and 1.4186 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5900 g of NMP and 1.6034 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-5).
(Example 25)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4208 g of the polyamic acid ester solution (PAE-17) obtained in Production Example 17 and 1.4416 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5948 g of NMP and 1.6192 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-6).

(Example 26)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4128 g of the polyamic acid ester solution (PAE-18) obtained in Production Example 18 and 1.4003 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5658 g of NMP and 1.6040 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-7).
(Example 27)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4003 g of the polyamic acid ester solution (PAE-23) obtained in Production Example 23 and 1.4214 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5769 g of NMP and 1.6258 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-8).
(Example 28)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 1.4970 g of the polyamic acid ester solution (PAE-14) obtained in Production Example 14 and 0.6867 g of the polyamic acid solution (PAA-13) obtained in Production Example 40 were taken. Then, 1.8321 g of NMP and 0.9933 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VII-1).
(Example 29)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 1.4939 g of the polyamic acid ester solution (PAE-20) obtained in Production Example 20 was taken, and 0.6778 g of the polyamic acid solution (PAA-13) obtained in Production Example 40 was taken. Then, 1.8243 g of NMP and 0.9970 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VII-2).
(Example 30)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 1.4923 g of the polyamic acid ester solution (PAE-17) obtained in Production Example 17 and 0.6527 g of the polyamic acid solution (PAA-13) obtained in Production Example 40 were taken. Further, 1.8424 g of NMP and 1.0093 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VII-3).

(Example 31)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4514 g of the polyamic acid ester solution (PAE-24) obtained in Production Example 24 was taken, and 2.6079 g of the polyamic acid solution (PAA-4) obtained in Production Example 31 was taken. Then, N294 (3.2294 g), BCS (2.0193 g), 4- (t-butoxycarbonylamino) pyridine (hereinafter abbreviated as Boc-AP) as an imidization accelerator (0.0745 g) were added, and a magnetic stirrer was added. The mixture was stirred for a minute to obtain a liquid crystal aligning agent (VIII-1).
(Example 32)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4389 g of the polyamic acid ester solution (PAE-25) obtained in Production Example 25 was taken, and 2.0025 g of the polyamic acid solution (PAA-6) obtained in Production Example 33 was taken. NMP (3.8213 g), BCS (2.0747 g), and N-α- (9-fluorenylmethoxycarbonyl) -Nt-butoxycarbonyl-L-histidine (hereinafter referred to as Fmoc-His) as an imidization accelerator. Abbreviation) was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-2).
(Example 33)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4317 g of the polyamic acid ester solution (PAE-26) obtained in Production Example 26 and 2.4209 g of the polyamic acid solution (PAA-7) obtained in Production Example 34 were taken. Further, 3.2161 g of NMP, 2.0138 g of BCS, and 0.0443 g of Fmoc-His as an imidization accelerator were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-3).
(Example 34)
A stir bar was placed in a 50 ml Erlenmeyer flask, and 2.44033 g of the polyamic acid ester solution (PAE-24) obtained in Production Example 24 and 1.8146 g of the polyamic acid solution (PAA-5) obtained in Production Example 32 were taken. NMP (3.8062 g) and BCS (2.0598 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-4).
(Example 35)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4133 g of the polyamic acid ester solution (PAE-25) obtained in Production Example 25 and 2.4596 g of the polyamic acid solution (PAA-8) obtained in Production Example 35 were taken. NMP (3.2232 g) and BCS (2.0172 g) were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-5).

(Example 36)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4188 g of the polyamic acid ester solution (PAE-25) obtained in Production Example 25 and 1.8056 g of the polyamic acid solution (PAA-9) obtained in Production Example 36 were taken. 3.8213 g of NMP and 2.0016 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-6).
(Example 37)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4086 g of the polyamic acid ester solution (PAE-25) obtained in Production Example 25 and 2.0296 g of the polyamic acid solution (PAA-10) obtained in Production Example 37 were taken. NMP (3.6425 g) and BCS (2.0192 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-7).
(Example 38)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4038 g of the polyamic acid ester solution (PAE-26) obtained in Production Example 26 and 2.4958 g of the polyamic acid solution (PAA-11) obtained in Production Example 38 were taken. NMP (3.2333 g) and BCS (2.0473 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-8).
(Example 39)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4592 g of the polyamic acid ester solution (PAE-27) obtained in Production Example 27 and 2.3451 g of the polyamic acid solution (PAA-12) obtained in Production Example 39 were taken. In addition, 0.3698 g of NMP, 3.0082 g of γ-BL, and 2.0164 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-9).
(Example 40)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4180 g of the polyamic acid ester solution (PAE-28) obtained in Production Example 28 and 2.2640 g of the polyamic acid solution (PAA-12) obtained in Production Example 39 were taken. , N912 (0.3912 g), γ-BL (2.9920 g) and BCS (2.0276 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-10).

(Example 41)
A stirrer was placed in a 50 ml Erlenmeyer flask and 2.4290 g of the polyamic acid ester solution (PAE-29) obtained in Production Example 29 was taken, and 2.1331 g of the polyamic acid solution (PAA-13) obtained in Production Example 40 was taken. 1.1458 g of NMP, 2.4939 g of γ-BL, and 2.0804 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-11).
(Comparative Example 9)
A stirrer was placed in a 50 ml Erlenmeyer flask, 1.5206 g of the polyamic acid ester solution (PAE-2) obtained in Comparative Production Example 1 and the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken, and NMP1. 4838g and BCS1.0418g were added and it stirred for 30 minutes with the magnetic stirrer, and obtained the liquid crystal aligning agent (d).
(Comparative Example 10)
A stirrer was placed in a 50 ml Erlenmeyer flask, 2.4052 g of the polyamic acid ester solution (PAE-30) obtained in Comparative Production Example 3, and 2.5709 g of the polyamic acid solution (PAA-4) obtained in Production Example 31. NMP (3.2177 g), BCS (2.0115 g), and Boc-AP (0.0466 g) as an imidization accelerator were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (e-1). .
(Comparative Example 11)
A stirrer was placed in a 50 ml Erlenmeyer flask, 2.4477 g of the polyamic acid ester solution (PAE-31) obtained in Comparative Production Example 4, and 2.0163 g of the polyamic acid solution (PAA-6) obtained in Production Example 31. NMP (3.8281 g), BCS (2.0238 g) and Fmoc-His (0.0567 g) as an imidization accelerator were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (e-2). .
(Comparative Example 12)
A stirrer was placed in a 50 ml Erlenmeyer flask, 2.4343 g of the polyamic acid ester solution (PAE-32) obtained in Comparative Production Example 5, and 2.4192 g of the polyamic acid solution (PAA-7) obtained in Production Example 34. NMP (3.2408 g), BCS (2.0078 g), and Fmoc-His (0.0493 g) as an imidization accelerator were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (e-3). .
(Comparative Example 13)
A stirrer was placed in a 50 ml Erlenmeyer flask, 2.4670 g of the polyamic acid ester solution (PAE-30) obtained in Comparative Production Example 3, and 1.8052 g of the polyamic acid solution (PAA-5) obtained in Production Example 32. Then, 3.8260 g of NMP and 1.994 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (e-4).
(Comparative Example 14)
A stirrer was placed in a 50 ml Erlenmeyer flask, 1.2196 g of the polyamic acid ester solution (PAE-32) obtained in Comparative Production Example 5, and 1.2191 g of the polyamic acid solution (PAA-11) obtained in Production Example 38. Then, 1.6214 g of NMP and 1.0094 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (e-8).
(Comparative Example 15)
A stirrer was placed in a 50 ml Erlenmeyer flask, 2.4001 g of the polyamic acid ester solution (PAE-33) obtained in Comparative Production Example 6 and 2.3161 g of the polyamic acid solution (PAA-12) obtained in Production Example 39. NMP (0.3740 g), γ-BL (3.0250 g), and BCS (2.0167 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (e-9).

(Comparative Example 16)
A stirrer was placed in a 50 ml Erlenmeyer flask, 2.4239 g of the polyamic acid ester solution (PAE-33) obtained in Comparative Production Example 6, and 2.1307 g of the polyamic acid solution (PAA-13) obtained in Production Example 40. Then, 1.1709 g of NMP, 2.5186 g of γ-BL, and 2.0286 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (e-11).
(Example 42)
The liquid crystal aligning agent (V-1) obtained in Example 11 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. An imidized film having a film thickness of 100 nm was obtained after baking for 20 minutes in a warm air circulating oven at 230 ° C. The centerline average roughness (Ra) of this imidized film was measured. About a measurement result, it shows in Table 4 mentioned later.
(Examples 43 to 69 and Comparative Examples 17 to 24)
Each coating film was formed in the same manner as in Example 42 except that the respective liquid crystal aligning agents obtained in Examples 12 to 34, 38 to 41, and Comparative Examples 9 to 16 were used. The film surface of each coating film was observed with AFM. Further, the center line average roughness (Ra) was measured for each coating film. These measurement results are shown in Table 4 described later.

According to the present invention, the surface irregularities of the liquid crystal and the liquid crystal alignment film, such as the reduction of fine irregularities on the surface and the reduction of the afterimage due to alternating current drive, are improved, and the voltage holding ratio, the ion density, the residual DC voltage, etc. The electrical characteristics of the are also improved. As a result, the present invention is widely useful for TN elements, STN elements, TFT liquid crystal elements, and vertical alignment type liquid crystal display elements.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2010-058556 filed on March 15, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (9)

A polyamic acid ester having a structural unit of the following formula (1) and having a terminal modified so that the terminal amino group has a structure of the following formula (3), and a polyamic acid having a structural unit of the following formula (2) And a liquid crystal aligning agent comprising an organic solvent.

(R ₁ is an alkyl group having 1 to 5 carbon atoms, and A ₁ and A ₂ are each independently a hydrogen atom, or an optionally substituted alkyl group, alkenyl group having 1 to 10 carbon atoms, or An alkynyl group, X ₁ and X ₂ are tetravalent organic groups, and Y ₁ and Y ₂ are divalent organic groups.)

(Wherein A is a single bond, —O—, —S—, or —NR ₃ —, and R ₂ and R ₃ each independently represents an alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms. Group, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group or heterocyclic group which may have a substituent.) 2. The liquid crystal aligning agent according to claim 1, wherein the content of the polyamic acid ester and the content of the polyamic acid are 1/9 to 9/1 in mass ratio of (content of polyamic acid ester / polyamic acid). . 3. The polyamic acid ester, the polyamic acid, and an organic solvent, wherein the total amount of the polyamic acid ester and the polyamic acid is 0.5% by mass to 15% by mass with respect to the organic solvent. Liquid crystal aligning agent. A polyamic acid obtained by reacting at least one chlorocarbonyl compound selected from the following formulas (C-1) to (C-36) with a main chain terminal amine of the polyamic acid ester is a polyamic acid ester having a modified terminal. 4. The liquid crystal aligning agent according to claim 1, which is an ester.

5. The liquid crystal aligning agent according to claim 1, wherein in the formula (1) and the formula (2), the structures of X ₁ and X ₂ are at least one selected from the following structures.

6. The liquid crystal aligning agent according to any one of 1 to 5 above, wherein in formula (1), Y ₁ is at least one selected from the group consisting of structures represented by the following formula.

7. The liquid crystal aligning agent according to claim 1, wherein in the formula (2), Y ₂ is at least one selected from structures represented by the following formula.

A liquid crystal alignment film obtained by applying and baking the liquid crystal aligning agent according to any one of claims 1 to 7. A liquid crystal alignment film obtained by irradiating a film obtained by applying and baking the liquid crystal aligning agent according to any one of claims 1 to 7 with polarized radiation.