JP6048143B2 - Liquid crystal aligning agent and liquid crystal aligning film containing polyamic acid ester and polyamic acid - Google Patents

Description

  The present invention relates to a liquid crystal alignment agent containing a polyamic acid ester and a polyamic acid, and a liquid crystal alignment film obtained from the liquid crystal alignment agent.

In a liquid crystal display element used for a liquid crystal television, a liquid crystal display, and the like, a liquid crystal alignment film for controlling the alignment state of liquid crystals is usually provided in the element. 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). Further, as a liquid crystal alignment film having a high voltage holding ratio and a short time until an afterimage generated by a direct current voltage disappears, in addition to polyamic acid or an imidized polymer thereof, one carboxylic acid group is included in the molecule. Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing, a compound containing one carboxylic anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (See, for example, 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 DC voltage is applied. However, the characteristics of polyimide-based liquid crystal aligning agents containing such polyamic acid esters are improved. How to do is not yet known.

JP 9-316200 A JP-A-10-104633 JP-A-8-76128 JP 9-138414 A JP 11-38415 A JP 2003-26918 A

The present inventors 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 study by the present inventors, 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. Furthermore, the present inventors can suppress the fine irregularities generated on the film surface to be small by making the weight average molecular weight of the polyamic acid ester contained in the liquid crystal aligning agent smaller than the weight average molecular weight of the polyamic acid. I found it. In addition, the present inventors have found that when the fine unevenness generated on the film surface is reduced, the difficulty of the liquid crystal aligning agent containing polyamic acid ester and polyamic acid is solved.

Thus, the present invention is based on the above findings and has the following gist.
1. A polyamic acid ester having a repeating unit represented by the following formula (1), a polyamic acid having a repeating unit represented by the following formula (2), and an organic solvent, the weight average molecular weight of the polyamic acid ester Is smaller than the weight-average molecular weight of the polyamic acid.

（式（１）及び式（２）において、Ｘ_１及びＸ₂は、それぞれ独立して４価の有機基であり、Ｙ_１及びＹ_２はそれぞれ独立して２価の有機基である。Ｒ_１は、炭素数１〜５のアルキル基であり、Ａ_１及び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／ポリアミック酸の含有量）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の合計含有量が、有機溶媒に対して０．５〜１５質量％である上記１又は２に記載の液晶配向剤。
４．前記ポリアミック酸エステルの重量平均分子量が前記ポリアミック酸の重量平均分子量よりも１０００〜１０００００小さい上記１〜３のいずれかに記載の液晶配向剤。

(In Formula (1) and Formula (2), X ₁ and X ₂ are each independently a tetravalent organic group, and Y ₁ and Y ₂ are each independently a divalent organic group. 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, or alkynyl group having 1 to 10 carbon atoms. Group.)
2. 2. The liquid crystal 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 mass ratio of (content of polyamic acid ester / content of polyamic acid). Alignment agent.
3. The liquid crystal aligning agent of said 1 or 2 whose sum total content of the said polyamic acid ester and polyamic acid is 0.5-15 mass% with respect to the organic solvent.
4). The liquid crystal aligning agent in any one of said 1-3 whose weight average molecular weight of the said polyamic acid ester is 1000-100,000 smaller than the weight average molecular weight of the said polyamic acid.

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

７．式（２）において、Ｙ_２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種である上記１〜６のいずれかに記載の液晶配向剤。

7). In the formula (2), the liquid crystal alignment agent according to any one of the above 1 to 6 is at least one Y ₂ is selected from the group consisting of 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から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基板に塗布し、焼成する液晶配向膜の製造方法。
１０．上記１〜７のいずれかに記載の液晶配向剤を基板に塗布し、焼成し、得られる被膜に偏光させた放射線を照射する液晶配向膜の製造方法。

8). The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of said 1-7.
9. The liquid crystal alignment agent according to any one of the above 1 to 7 applied to a substrate, the manufacturing method of firing to the liquid crystal alignment film.
10. The manufacturing method of the liquid crystal aligning film which irradiates the radiation which polarized the liquid crystal aligning agent in any one of said 1-7 on a board | substrate, baked, and obtained the film.

According to the present invention, fine irregularities on the surface of the obtained liquid crystal alignment film can be reduced, liquid crystal alignment is improved, and electrical characteristics such as voltage holding ratio, ion density, afterimage due to alternating current, and residual DC voltage are provided. And a liquid crystal aligning agent with improved reliability is provided.
By reducing the weight average molecular weight of the polyamic acid ester to be smaller than the weight average molecular weight of the polyamic acid, the fine irregularities generated on the surface of the film are reduced, and a liquid crystal containing the polyamic acid ester and the polyamic acid. Although it is not necessarily clear whether the difficulty which an orientation agent has 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 lower surface free energy than 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, or an aggregate of polyamic acid ester is formed in the polyamic acid phase. Since it is formed, the film surface has a large number of fine irregularities.

On the other hand, in the liquid crystal aligning agent of the present invention, by making the weight average molecular weight of the polyamic acid ester smaller than the weight average molecular weight of the polyamic acid, the liquid crystal aligning agent is formed by removing the solvent from the liquid crystal aligning agent. In this case, the phase separation between the polyamic acid ester and the polyamic acid is promoted, the polyamic acid ester is present in the vicinity of 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. It will exist without.
Therefore, the surface of the obtained liquid crystal alignment film has a smooth surface because unevenness due to phase separation between the polyamic acid ester and the polyamic acid is not formed, and the cloudiness of the film due to the occurrence of unevenness is reduced. And the liquid crystal alignment film having a smooth surface without unevenness, the polyamic acid ester excellent in orientation stability and reliability covers the film surface, and the polyamic acid excellent in electrical properties is present in the film and at the electrode interface. Since it exists, it is considered to have excellent characteristics.

<Polyamic acid ester and polyamic acid>
The polyamic acid ester used for this invention is a polyimide precursor for obtaining a polyimide, and is a polymer which has the site | part which can perform the 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 above 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 optionally substituted alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms. . Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, decyl group, cyclopentyl group, cyclohexyl group, and bicyclohexyl group. Examples of the alkenyl group include those obtained by replacing one or more CH ₂ —CH ₂ structures present in the above alkyl group 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, and cyclohexenyl group. 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 -A propynyl group etc. are mentioned.
The above alkyl group, alkenyl group, or 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 with 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.
A phenyl group is mentioned as an aryl group which is a substituent. 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 —O—R. 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 organooxy group include methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
As the organothio group which is a substituent, the structure represented by -S-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. Specific examples of the organothio 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.
As the organosilyl group which is a substituent, a structure represented by -Si- (R) ₃ 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. Specific examples of the organosilyl 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.

As an acyl group which is a substituent, the structure represented by -C (O) -R can be shown. 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 an ester group which is a substituent, the 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.
As a thioester group which is a substituent, the structure represented by -C (S) O-R or -OC (S) -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.
As a phosphate group which is a substituent, the structure represented by -OP (O)-(OR) ₂ 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.

As the amide group as a substituent, —C (O) NH ₂ , or —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 The alkyl group of ˜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 each independently a tetravalent organic group, and Y ₁ and Y ₂ are each independently a divalent organic group. 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,} each independently, include X-1 to X-46 shown below.

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 2 to 100 mol%, more preferably 40 to 100 mol% of the total tetracarboxylic dianhydride.

In Formula (1), 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 types may be mixed independently.

Among them, in order to obtain a good liquid crystal orientation in order to introduce highly linear diamine to the polyamic acid ester, as _{Y 1, 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 , 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 all diamines.
Among them, when it is desired to increase the pretilt angle, it is preferable to introduce a diamine having a long chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination thereof in the side chain into the polyamic acid ester, in this case, the _{Y 1, 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 preferable.
Especially, it is especially preferable that it is at least 1 type chosen from the structure represented by the following Formula.

By reducing the volume resistivity of the polyamic acid, it is possible to reduce the afterimage due to the accumulation of DC voltage. as _{Y 2, 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 is more preferable, and Y-31 or Y-40 diamine Is preferred. Preferred Y ₂ The amount of these diamines are preferably 1 to 100 mole percent of total diamine, and more preferably from 50 to 100 mol% added.
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, as the _{Y 2, Y-19, Y} -31, Y-40, Y-45, Y-98, or Y-99 are more preferable, Y-98 or Y-99 containing a carboxyl group is particularly 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.

（式中、Ｘ_１、Ｙ_１、Ｒ_１、Ａ_１及びＡ_２はそれぞれ上記式（１）中の定義と同じである。）
上記式（１）で表されるポリアミック酸エステルは、上記モノマーを用いて、以下に示す（１）〜（３）の方法で合成することができる。
（１）ポリアミック酸から合成する場合
ポリアミック酸エステルは、テトラカルボン酸二無水物とジアミンから得られるポリアミック酸をエステル化することによって合成することができる。

(In the formula, X ₁ , Y ₁ , R ₁ , A ₁ and A ₂ are the same as defined in the formula (1)).
The polyamic acid ester represented by the above formula (1) can be synthesized by the following methods (1) to (3) using the monomer.
(1) When synthesizing from polyamic acid The polyamic acid ester can be synthesized by esterifying a 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 synthesized.
As the esterifying agent, those that can be easily removed by purification are preferred, and 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. Good. The concentration at the time of synthesis 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 body is easily obtained.

(2) When synthesized by reaction of tetracarboxylic acid diester dichloride and diamine Polyamic acid ester can be synthesized from tetracarboxylic acid diester dichloride and diamine.

Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent are −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized 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 moles with respect to the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and easy obtaining of a high molecular weight product.

  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 polymer concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation hardly occurs and a high molecular weight body is easily obtained. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis 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) When a polyamic acid is synthesized from a tetracarboxylic acid diester and a diamine The polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine.
Specifically, tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base and an organic solvent are 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., 30 minutes to 24 hours, preferably 3 to 15 hours. It can be synthesized 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, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate, and the like. It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to 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 the mole of the diamine component.
Among the methods for synthesizing the three polyamic acid esters, since a high molecular weight polyamic acid ester is obtained, the synthesis method (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).

（式中、Ｘ_２、Ｙ_２、Ａ_１及びＡ_２はそれぞれ上記式（２）中の定義と同じである。）

(In the formula, X ₂ , Y ₂ , A ₁ and A ₂ are the same as defined in the above formula (2).)

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 synthesized.
The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the monomer and the polymer, and these may be used alone or in combination of two or more. It may be used. The concentration of the polymer is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that the polymer is hardly precipitated and a high molecular weight body 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.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention contains the polyamic acid ester represented by the above formula (1) and the polyamic acid represented by the formula (2).
The weight average molecular weight of the polyamic acid ester is preferably 5,000 to 300,000, and more preferably 10,000 to 200,000. The number average molecular weight is preferably 2,500 to 150,000, more preferably 5,000 to 100,000.
On the other hand, the weight average molecular weight of the polyamic acid is preferably 10,000 to 305,000, and more preferably 20,000 to 210,000. Further, the number average molecular weight is preferably 5,000 to 152,500, more preferably 10,000 to 105,000.

In the present invention, the weight average molecular weight of the polyamic acid ester must be smaller than the weight average molecular weight of the polyamic acid. The difference in weight average molecular weight between the polyamic acid ester and the polyamic acid is preferably 1,000 to 100,000, more preferably 3,000 to 80,000, and more preferably 5,000 to 60,000. Particularly preferred. When the difference in the weight average molecular weight is in the range of 1,000 to 100,000, it is preferable because fine irregularities generated by phase separation of the polyamic acid ester and the polyamic acid are particularly remarkably controlled.
The content of the polyamic acid ester and the content of the polyamic acid in the liquid crystal liquid crystal aligning agent of the present invention is preferably 1/9 to 9/1 in terms of mass ratio of (polyamic acid ester / polyamic acid). More preferably, it is 2/8 to 8/2, and particularly preferably 3/7 to 7/3. By setting the ratio in the range of 1/9 to 9/1, it is possible to provide a liquid crystal aligning agent having good liquid crystal alignment properties and electrical characteristics.

The liquid crystal aligning agent of this invention is a form of the solution which said polyamic acid ester and polyamic acid melt | dissolved in the organic solvent. As long as it has such a form, for example, when a polyamic acid ester and / or polyamic acid is synthesized in an organic solvent, it may be the reaction solution obtained, or the reaction solution is diluted with an appropriate solvent. It may be a thing. When the polyamic acid ester and / or polyamic acid is obtained as a powder, it may be dissolved in an organic solvent to form a solution.
The content (concentration) of the polyamic acid and polyamic acid ester (hereinafter also referred to as polymer) in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the setting of the thickness of the polyimide film to be formed. From the viewpoint of forming a uniform and defect-free coating film, the content of the polymer component is preferably 0.5% by mass or more with respect to the organic solvent, and 15% by mass or less from the viewpoint of storage stability of the solution. More preferably, it is 1-10 mass% especially preferably. In this case, a concentrated solution of the polymer may be prepared in advance, and diluted when such a concentrated solution is used as the liquid crystal alignment agent. The concentration of the concentrated solution of the polymer component is preferably 10 to 30% by mass, and more preferably 10 to 15% by mass. Alternatively, the polymer component powder may be heated when dissolved in an organic solvent to prepare a solution. The heating temperature is preferably 20 ° C to 150 ° C, particularly preferably 20 ° C to 80 ° C.

  The said organic solvent contained in the liquid crystal aligning agent of this invention will not be specifically limited if a polymer component 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-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. 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.

  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, butyl cellosolve acetate, 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, 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 types 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. The silane coupling agent is added for the purpose of improving the adhesion between the substrate on which the liquid crystal alignment agent is applied and the liquid crystal alignment film formed thereon. Although the specific example of a silane coupling agent is given to the following, it is not limited to this.

  3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-phenylaminopropyltri Amine-based silane coupling agents such as methoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-aminopropyldiethoxymethylsilane; vinyltrimethoxysilane, vinyltriethoxysilane, Vinyl-based silane couplings such as vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane Agents: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxy cyclohexyl) Epoxy silane coupling agent such as ethyltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Methacrylic silane coupling agents such as ethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; Ureido silane cups such as 3-ureidopropyltriethoxysilane Sulfide-based silane coupling agents such as bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Mercapto silane coupling agents such as trimethoxysilane and 3-octanoylthio-1-propyltriethoxysilane; Isocyanate silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane; Aldehyde-based silane coupling agents such as butyraldehyde; carbamates such as triethoxysilylpropylmethylcarbamate and (3-triethoxysilylpropyl) -t-butylcarbamate Mate silane coupling agent.

If the amount of the silane coupling agent added is too large, unreacted ones may adversely affect the liquid crystal orientation, and if too small, the effect on adhesion will not appear, so the amount of the silane coupling agent is 0 with respect to the solid content of the polymer. 0.01 to 5.0% by weight is preferable, and 0.1 to 1.0% by weight is more preferable.
When adding the said silane coupling agent, in order to prevent precipitation of a polymer, it is preferable to add before adding the solvent for improving the above-mentioned coating-film uniformity. Also, when adding a silane coupling agent, add it to the polyamic acid ester solution, the polyamic acid solution, or both the polyamic acid ester solution and the polyamic acid solution before mixing the polyamic acid ester solution and the polyamic acid solution. Can do. Moreover, it can add to a 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.
An imidization accelerator may be added to efficiently advance imidization of the polyamic acid ester when the coating film is baked. Although the specific example of the imidation promoter of polyamic acid ester is given to the following, it is not limited to this.

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 Ds 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 imidization of the polyamic acid ester is obtained, but the following formula (included in the polyamic acid ester in the liquid crystal aligning agent ( The amount is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more with respect to 1 mol of the amic acid ester moiety of 12). Further, from the point that the imidization accelerator itself remaining in the fired film minimizes adverse effects on various properties of the liquid crystal alignment film, the following formula (12) contained in the polyamic acid ester in the liquid crystal aligning agent is used. ) Is preferably 2 mol or less, more preferably 1 mol or less, and even more preferably 0.5 mol or less, per 1 mol of the amic acid ester moiety.

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 film obtained by applying the liquid crystal aligning agent to a substrate, drying and baking. The substrate on 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, an acrylic substrate, a polycarbonate substrate such as 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. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light, such as aluminum, can also 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 organic solvent is dried at 50 ° C. to 120 ° C. for 1 minute to 10 minutes, and then baked at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes. Although the thickness of the coating film after baking is not specifically limited, Since the reliability of a liquid crystal display element may fall when too thin, it is 5-300 nm, Preferably it is 10-200 nm.

Examples of a method for aligning the obtained liquid crystal alignment film include a rubbing method and a photo-alignment processing method. The liquid crystal aligning agent of the present invention is particularly useful when used in the photo-alignment processing 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 deflected 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 nm to 800 nm can be used. Among these, ultraviolet rays having a wavelength of 100 nm to 400 nm are preferable, and those having a wavelength of 200 nm to 400 nm are particularly preferable. Moreover, in order to improve liquid crystal orientation, you may irradiate a radiation, heating a coating-film board | substrate at 50-250 degreeC. Dose of the radiation is preferably ^{1~10,000mJ / cm 2, 100~5,000mJ / cm} 2 is particularly preferred. The liquid crystal alignment film produced as described above can stably align liquid crystal molecules in a certain direction.

[Liquid crystal display element]
The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the above-described method, performing an alignment treatment, and then preparing a liquid crystal cell by a known method. It is.
The manufacturing method of the liquid crystal cell is not particularly limited, but for example, a pair of substrates on which the liquid crystal alignment film is formed is preferably 1 to 30 μm, more preferably 2 to 10 μm with the liquid crystal alignment film surface inside. A method is generally employed in which the spacer is fixed with a sealing agent after the spacer is sandwiched, and liquid crystal is injected and sealed. The method for enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method of injecting liquid crystal after reducing the pressure inside the produced liquid crystal cell, and a dropping method of sealing after dropping the liquid crystal.

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.
In addition, the symbol used by an Example and a comparative example and the measuring method of each characteristic are as follows.
1,3DMCBDE-Cl: dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate ODA: 4,4′-diaminodiphenyl ether 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

[viscosity]
In the synthesis example, the viscosity of the polyamic acid ester and the polyamic acid solution is an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample amount 1.1 mL, cone rotor TE-1 (1 ° 34 ′, R24). ), Measured at a temperature of 25 ° C.
[Molecular weight]
The molecular weight of the polyamic acid ester is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and is a number average molecular weight (hereinafter also referred to as Mn) and a weight average molecular weight (hereinafter also referred to as Mw) as polyethylene glycol and polyethylene oxide equivalent values. ) Was calculated.
GPC device: manufactured by Shodex (GPC-101)
Column: manufactured by Shodex (series of KD803 and KD805)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) 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 mixed samples are measured separately.

[Center line average roughness measurement]
The coating film of the liquid crystal aligning agent obtained by spin coating is dried on a hot plate at a temperature of 80 ° C. for 5 minutes and then baked for 1 hour in a hot air circulation oven at a temperature of 250 ° C. Got. 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 is spin-coated on a glass substrate with a transparent electrode, dried for 5 minutes on a hot plate at a temperature of 80 ° C., and baked for 60 minutes in a hot air circulation oven at 250 ° C. to obtain a polyimide film having a thickness of 100 nm. It was. 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, an ITO electrode having a thickness of 50 nm as an electrode in the first layer, a silicon nitride film having a thickness of 500 nm as an insulating film in the second layer, and a comb-like ITO electrode as an electrode in the third layer ( Liquid crystal alignment by spin coating on a glass substrate on which a fringe field switching (hereinafter referred to as FFS) driving electrode having an electrode width: 3 μm, an electrode interval: 6 μm, and an electrode height: 50 nm is formed. The agent was applied. 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 the FFS driving 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 characteristic was measured again, and the difference in voltage at which the transmittance was 50% before and after applying the rectangular wave was calculated.

[Evaluation of charge storage characteristics]
After placing the FFS drive liquid crystal cell on the light source and measuring the VT characteristics (voltage-transmittance characteristics), measure the transmittance (T _a ) in the state where a square wave of ± 1.5 V / 60 Hz is 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 tetracarboxylic acid dialkyl ester

Under a nitrogen stream, a 3-L four-necked flask was charged with 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride (compound of formula (5-1), hereinafter referred to as 1,3-DM. -CBDA) 220 g (0.981 mol) and methanol 2200 g (68.7 mol, 10 wt times with respect to 1,3-DM-CBDA) were charged and heated to reflux at 65 ° C. for 30 minutes. A homogeneous solution was obtained. 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. Then, it cooled until the internal temperature became 25 degreeC at the speed | rate of 2-3 degreeC in 10 minutes, and stirred for 30 minutes as it was at 25 degreeC. 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 compound (1-1) from the results of 1H NMR analysis and X-ray crystal structure analysis (HPLC relative area 97.5%) (yield 36.8%).
1H NMR (DMSO-d6, δppm); 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, after charging 234.15 g (0.81 mol) of compound (1-1) and 117.77 g (11.68 mol.5 wt times) of n-heptane in a 3 L four-necked flask, the pyridine was mixed with 0.1. 64 g (0.01 mol) was added, and the mixture was heated and stirred to 75 ° C. while stirring with a magnetic stirrer. Subsequently, 289.93 g (2.44 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 as it was at 25 ° C. for 30 minutes, the precipitated white crystal was taken out by filtration, and this crystal was washed with 264.21 g of n-heptane. This was dried under reduced pressure to obtain 226.09 g of white crystals.
Subsequently, 226.09 g of the white crystals obtained above and 454.18 g of n-heptane were charged into a 3 L four-necked flask in a nitrogen stream, and heated and stirred at 60 ° C. to dissolve the crystals. Thereafter, the mixture was cooled and stirred at a rate of 1 ° C. for 10 minutes to 25 ° C. to precipitate crystals. After stirring as it was at 25 ° C. for 1 hour, the precipitated white crystals were taken out by filtration, washed with 113.04 g of n-hexane, and then dried under reduced pressure to obtain 203.91 g of white crystals. 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, based on 1H NMR analysis results. -CBDE-C1) (HPLC relative area 99.5%) (yield 77.2%).
1H NMR (CDCl3, δppm): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H).

(Synthesis Example 1)
A 300 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere, 8.029 g (40.02 mmol) of ODA is added, 157.25 g of NMP and 7.13 g (90.13 mmol) of pyridine as a base are added and dissolved by stirring. I let you. Next, 12.295 g (37.61 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 1747 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by 1 time of 1747 g of water, 1 time of 1747 g of ethanol, and 437 g of ethanol. The white polyamic acid ester resin powder 16.65g was obtained by wash | cleaning 3 times and drying. The yield was 95.3%. Moreover, the molecular weight of this polyamic acid ester was Mn = 13,104 and Mw = 29,112.
1.8731 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 16.89 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 (A-1).

(Synthesis Example 2)
A 300 mL four-necked flask equipped with a stirrer is placed in a nitrogen atmosphere, 7.015 g (35.03 mmol) of ODA is added, 140.77 g of NMP, and 6.50 g (82.22 mmol) of pyridine as a base are added and stirred. Dissolved. Next, 11.3392 g (34.26 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 1564 g of water with stirring, and the precipitated white precipitate was collected by filtration, followed by once with 1564 g of water, once with 1564 g of ethanol, and 391 g of ethanol. After washing 3 times and drying, 14.33 g of white polyamic acid ester resin powder was obtained. The yield was 91.6%. Moreover, the molecular weight of this polyamic acid ester was Mn = 24,228 and Mw = 61,076.
The obtained polyamic acid ester resin powder (1.7324 g) was placed in a 50 ml Erlenmeyer flask, NMP (15.65 g) was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (A-2).

(Synthesis Example 3)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 4.583 g (23.0 mmol) of 4,4′-diaminodiphenylamine is added, 62.9 g of NMP is added, and the mixture is stirred and dissolved while feeding nitrogen. It was. While stirring this diamine solution, 4.335 g (22.10 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 10% by mass, and the mixture was stirred at room temperature for 24 hours to polyamic acid (B-1). Solution was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 165.1 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 17,171 and Mw = 35,201.

Example 1
Take 1.5114 g of the polyamic acid ester solution (A-1) obtained in Synthesis Example 1 and 1.5048 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 in an Erlenmeyer flask, 1.028 g of NMP, BCS 1.0016 g was added and stirred with a magnetic stirrer for 30 minutes to obtain liquid crystal aligning agent (I).
(Comparative Example 1)
1.5145 g of the polyamic acid ester solution (A-2) obtained in Synthesis Example 2 and 1.5241 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 are placed in an Erlenmeyer flask, 1.0331 g of NMP, BCS 1.0012 g was added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II).
(Comparative Example 2)
Take 4.2010 g of the polyamic acid ester solution (A-1) obtained in Synthesis Example 1 in an Erlenmeyer flask, add 0.5993 g of NMP and 1.2519 g of BCS, and stir with a magnetic stirrer for 30 minutes. III) was obtained.
(Example 2)
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 circulation oven at 0 ° C. The centerline average roughness (Ra) of this imidized film was measured. About a measurement result, it shows in Table 1 mentioned later.
(Comparative Example 3)
An imidized film was produced in the same manner as in Example 2 except that the liquid crystal aligning agent (II) obtained in Comparative Example 1 was used. The centerline average roughness (Ra) of this imidized film was measured. About a measurement result, it shows in Table 1 mentioned later.

実施例２と比較例３の結果より、ＰＡＥの重量平均分子量をＰＡＡよりも小さくすることにより、ポリアミック酸エステルとポリアミック酸の相分離により発生する微小な凹凸が小さく抑制され、より平滑な膜が得られることが確認された。

From the results of Example 2 and Comparative Example 3, by making the weight average molecular weight of PAE smaller than that of PAA, fine irregularities generated by phase separation of polyamic acid ester and polyamic acid are suppressed to be small, and a smoother film is obtained. It was confirmed that it was obtained.

Example 3
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 80 ° C. for 5 minutes, and 250 ° C. After being fired for 60 minutes in a hot air circulation oven, an imidized film having a film thickness of 100 nm 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. 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 4)
A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (II) 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.
(Comparative Example 5)
A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (III) obtained in Comparative Example 2 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３及び比較例４の結果より、より平滑な膜とすることで、高温時の電圧保持率及びイオン密度が良好であることが確認された。また、実施例３と比較例５の結果より、ポリアミック酸エステルとポリアミック酸をブレンドし、且つ平滑な膜が得られた場合、ポリアミック酸エステル単独よりも、高温時の電圧保持率及びイオン密度がより良好となり、信頼性の高い液晶配向膜が得られることが確認された。

From the results of Example 3 and Comparative Example 4, it was confirmed that the voltage holding ratio and ion density at high temperatures were good by making the film smoother. Further, from the results of Example 3 and Comparative Example 5, when a polyamic acid ester and a polyamic acid were blended and a smooth film was obtained, the voltage holding ratio and ion density at high temperature were higher than those of the polyamic acid ester alone. It was confirmed that a liquid crystal alignment film with higher reliability and higher reliability was obtained.

Example 4
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. Fringe Field Switching (hereinafter referred to as “Fringe Field Switching”) having a comb-like ITO electrode (electrode width: 3 μm, electrode interval: 6 μm, electrode height: 50 nm) as a third layer of silicon nitride having a thickness of 500 nm. It was applied by spin coating to a glass substrate on which driving electrodes (called FFS) 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.
With respect to this FFS drive liquid crystal cell, the liquid crystal alignment regulating force was measured and the charge storage characteristics were evaluated. The results are shown in Table 3 described later.

(Comparative Example 6)
An FFS drive liquid crystal cell was produced in the same manner as in Example 4 except that the liquid crystal aligning agent (II) obtained in Comparative Example 1 was used. With respect to this FFS drive liquid crystal cell, the liquid crystal alignment regulating force was measured and the charge storage characteristics were evaluated. The results are shown in Table 3 described later.

実施例４と比較例６の結果より、本発明の液晶配向膜を用いることにより、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 4 and Comparative Example 6, it was confirmed that by using the liquid crystal alignment film of the present invention, a liquid crystal alignment film having a small degree of AC drive burn-in and a small residual voltage can be obtained.

・ Synthesis of (AD-4)

５００ｍＬ反応容器に化合物（ｂ）（５０．００ｇ，２２９ｍｍｏｌ）、ピリジン（０．５００ｇ，０．６３２ｍｍｏｌ）、化合物（ｃ）（６３．０２, ５０４ｍｍｏｌ）、アセトノトリル（３００ｇ）を加え、窒素雰囲気下、加熱還流で反応を行った。反応終了後、２０℃まで冷却した後、ろ過、アセトニトリル（１００ｇ）で洗浄を行い、粗物を得た。次に、粗物に２−プロパノール（３００ｇ）、蒸留水（１００ｇ）を加え、加熱還流した。その後、２０℃に冷却し、固体をろ過、２−プロパノール（１００ｇ）で洗浄、乾燥し化合物（ｄ）を得た（収量：３７．８ｇ，収率：３７％）。
^１Ｈ−ＮＭＲ（^１Ｈ核磁気共鳴分光）（４００ＭＨｚ，ＤＭＳＯ−ｄ_６，σ（ｐｐｍ））：８．０７（２Ｈ，ｓ），５．１５−５．１４（２Ｈ，ｍ），４．６２（２Ｈ，ｔ），４．５９−４．４９（４Ｈ，ｍ），４．３８（２Ｈ，ｑ）．

Compound (b) (50.00 g, 229 mmol), pyridine (0.500 g, 0.632 mmol), compound (c) (63.02, 504 mmol), and acetonotolyl (300 g) were added to a 500 mL reaction vessel, and under a nitrogen atmosphere, The reaction was conducted with heating to reflux. After the completion of the reaction, the reaction mixture was cooled to 20 ° C., filtered and washed with acetonitrile (100 g) to obtain a crude product. Next, 2-propanol (300 g) and distilled water (100 g) were added to the crude product and heated to reflux. Thereafter, the mixture was cooled to 20 ° C., the solid was filtered, washed with 2-propanol (100 g), and dried to obtain compound (d) (yield: 37.8 g, yield: 37%).
¹ H-NMR ( ¹ H nuclear magnetic resonance spectroscopy) (400 MHz, DMSO-d ₆ , σ (ppm)): 8.07 (2H, s), 5.15-5.14 (2H, m), 4. 62 (2H, t), 4.59-4.49 (4H, m), 4.38 (2H, q).

Compound (d) (20.00 g, 44.0 mmol) and thionyl chloride (120.0 g, 1.01 mol) were added to a 500 mL reaction vessel, and the mixture was heated to reflux. After 30 minutes, after cooling to 20 ° C., thionyl chloride (120.0 g, 1.01 mol) was added, and the mixture was further heated under reflux for 2 hours. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure and washed with hexane (200 g). Next, dichloromethane (200 g) was added to the crude product at 20 ° C. and stirred, and a solution of compound (c) (12.1 g, 96.8 mmol), pyridine (13.93 g, 176 mmol), dichloromethane (100 g) was added thereto. Was slowly added dropwise. After stirring for 1 hour, compound (c) (12.1 g, 96.8 mmol) and pyridine (13.93 g, 176 mmol) were further added. After completion of the reaction, the solvent was distilled off and washed with distilled water (144 g) to obtain a crude product. Tetrahydrofuran (144 g) was added to this crude product, dispersed and washed at 23 ° C., filtered, washed with tetrahydrofuran (130 g), distilled water (170 g), and methanol (150 g), and then dried (AD-4). Obtained (yield: 17.72 g, yield: 62%).
¹ H-NMR ( ¹ H nuclear magnetic resonance spectroscopy) (400 MHz, DMSO-d ₆ , σ (ppm)): 8.17 (2H, s), 5.18-5.13 (2H, m), 4. 64-4.53 (6H, m), 4.37 (2H, q).

(Synthesis Example 4)
A 300 mL four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 5.0284 g (25.11 mmol) of ODA was added, 202.80 g of NMP and 4.72 g (59.63 mmol) of pyridine as a base were added and dissolved by stirring. I let you. Next, 8.0794 g (24.85 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 1127 g of water while stirring, and the precipitated white precipitate was collected by filtration, followed by 1127 g of water once, 1127 g of ethanol once, and 282 g of ethanol. The white polyamic acid ester resin powder was obtained by washing 3 times and drying. The molecular weight of this polyamic acid ester was Mn = 6,394 and Mw = 13,794.
4.5796 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 41.20 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 (A-3).
(Synthesis Example 5)
In a 100 ml four-necked flask equipped with a stirrer, 5.184 g (19.82 mmol) of 2,4-bis (methoxycarbonyl) cyclobutane-1,3-dicarboxylic acid was taken, 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 obtained 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 (A-4).
(Synthesis Example 6)
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, 5.1407 g (15.81 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 690 g of 2-propanol while stirring, and the precipitated white precipitate was collected by filtration, subsequently washed with 220 g of 2-propanol for 5 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 (A-5).
(Synthesis Example 7)
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. , 135.18 g of NMP and 4.04 g (39.95 mmol) of triethylamine as a base were added and dissolved by stirring. Next, 5.4260 g (16.69 mmol) of 1,3DM-CBDE-Cl was added while stirring the diamine solution, and the mixture was reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was added to 711 g of 2-propanol with stirring, and the precipitated white precipitate was collected by filtration, washed with 230 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 = 111820 and Mw = 28719.
2.4381 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 21.224 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 (A-6).

(Synthesis Example 8)
In a 300 ml four-necked flask equipped with a stirrer, 2.2617 g (8.01 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid and 2 of 2,4-bis (methoxycarbonyl) cyclobutane-1,3-dicarboxylic acid were added. 0.7808 g (10.61 mmol) was taken and 102.82 g of NMP was added and dissolved by stirring. Subsequently, 4.45 g (43.98 mmol) of triethylamine, 3.4396 g (12.01 mmol) of 1,5-bis (4-aminophenoxy) pentane, and 2 of 1,3-bis (4-aminophenethyl) urea were added. 3914 g (8.01 mmol) was added and dissolved by stirring. While stirring this solution, 16.60 g of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (15 ± 2 wt% hydrate) was added. Further, 14.12 g of NMP was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was poured into 890 g of 2-propanol with stirring, the deposited precipitate was collected by filtration, washed with 300 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 = 9450 and Mw = 22258.
1.1487 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 19.1544 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 (A-7).
(Synthesis Example 9)
In a 300 ml four-necked flask equipped with a stirrer, 2.289 g (8.00 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid and 3 of 2,4-bis (methoxycarbonyl) cyclobutane-1,3-dicarboxylic acid were added. 0.0710 g (11.80 mmol) was taken, 105.54 g of NMP was added, and dissolved by stirring. Subsequently, 4.45 g (43.98 mmol) of triethylamine, 3.4376 g (12.00 mmol) of 1,5-bis (4-aminophenoxy) pentane, and 2 of 1,3-bis (4-aminophenethyl) urea were added. 3862 g (8.00 mmol) was added and dissolved by stirring. While stirring this solution, 16.73 g of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (15 ± 2 wt% hydrate) was added. Further, 14.50 g of NMP was added and reacted for 4 hours under water cooling. The obtained polyamic acid ester solution was added to 910 g of 2-propanol with stirring, the deposited precipitate was collected by filtration, washed with 300 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 = 18067 and Mw = 46973.
1.3221 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 24.8708 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 (A-8) .

(Synthesis Example 11)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 6.0854 g (40.0 mmol) of 3,5-diaminobenzoic acid is taken, 65.56 g of NMP is added, and the mixture is stirred and dissolved while feeding nitrogen. It was. While stirring this diamine solution, 8.5449 g (39.18 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. The viscosity of the obtained polyamic acid solution at a temperature of 25 ° C. was 523 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 20565 and Mw = 47912.
Further, 13.79 g of an NMP solution of 0.3 mass% 3-glycidoxypropylmethyldiethoxysilane was added to this solution to obtain a polyamic acid solution (B-3).
(Synthesis Example 12)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3,6541 g (24.02 mmol) of 3,5-diaminobenzoic acid and 4.2931 g of 1,4-bis (4-aminophenyl) piperazine ( 16.00 mmol), 36.48 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 4.722 g (23.99 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 36.50 g of NMP was added, and 3.4084 g (15.63 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 1166 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 19307 and Mw = 42980.
Further, 0.0483 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution and stirred at room temperature for 24 hours to obtain a polyamic acid solution (B-4).
(Synthesis Example 13)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 3.6516 g (24.0 mmol) of 3,5-diaminobenzoic acid and 2.4070 g of 4-((2-methylamino) ethyl) aniline ( 16.02 mmol) was taken, 66.21 g of NMP was added, and the mixture was stirred and dissolved 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, followed by stirring at room temperature for 24 hours to obtain a polyamic acid solution (B-5).
(Synthesis Example 14)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 0.6123 g (4.00 mmol) of 3,5-diaminobenzoic acid and 3.199 g (16.06 mmol) of 4,4-diaminodiphenylamine were taken, 19.64 g of NMP was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 3.1780 g (16.04 mmol) of BDA was added, and the mixture was stirred at room temperature for 2 hours. Next, 8.93 g of NMP was added, and 0.8736 g (4.01 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 8100 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 22537 and Mw = 72601.
Further, 0.0235 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution and stirred at room temperature for 24 hours to obtain a polyamic acid solution (B-6).
(Synthesis Example 15)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction 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.
Further, 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 (B-7).

(Synthesis Example 16)
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 and 3.8715 g (15.98 mmol) of DA-1 were taken, and 31 NMP was added. .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 4.44766 g (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, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (B-8).
(Synthesis Example 17)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction 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 (B-9).
(Synthesis Example 18)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introducing tube, 2,365 g (17.99 mmol) of 3,5-diaminobenzoic acid and 2.5471 g of 2,2′-dimethyl-4,4′-diaminobiphenyl were added. (12.0 mmol) was taken, 27.32 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 2.2562 g (9.02 mmol) of bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride was added and stirred at 80 ° C. for 3 hours. After cooling the reaction solution to room temperature, 27.32 g of NMP was added, and 4.5715 g (20.96 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 2190 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 23632 and Mw = 56881.
Further, 0.0360 g of 3-glycidoxypropylmethyldiethoxysilane was added to this solution, followed by stirring at room temperature for 24 hours to obtain a polyamic acid solution (B-10).
(Example 5)
A stirrer was placed in a 50 ml Erlenmeyer flask, 3.0443 g of the polyamic acid ester solution (A-3) obtained in Synthesis Example 4 and 3.0126 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 were taken. In addition, 1.7670 g of NMP, 2.00083 g of BCS, and 0.2380 g of a 5 mass% NMP solution of (AD-1) which is a polyfunctional epoxy compound as a crosslinking agent were added, and stirred for 30 minutes with a magnetic stirrer. A liquid crystal aligning agent (I-1) was obtained.

(Example 6)
A stirrer was placed in a 50 ml Erlenmeyer flask, 3.0160 g of the polyamic acid ester solution (A-3) obtained in Synthesis Example 4 and 3.1313 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 were taken. , 2.0339 g of NMP, 2.0099 g of BCS, and 0.0274 g of a polyfunctional hydroxy group-containing compound (AD-2) as a crosslinking agent were added and stirred for 30 minutes with a magnetic stirrer. I-2) was obtained.
(Example 7)
A stirrer was placed in a 50 ml Erlenmeyer flask, 3.0328 g of the polyamic acid ester solution (A-3) obtained in Synthesis Example 4 and 3.0058 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 were taken. , 2.0417 g of NMP, 2.0125 g of BCS, and 0.0366 g of a polyfunctional cyclocarbonate compound (AD-4) as a crosslinking agent were added, and the mixture was stirred with a magnetic stirrer for 30 minutes. -3) was obtained.
(Example 8)
A stirrer was placed in a 50 ml Erlenmeyer flask, 3.0463 g of the polyamic acid ester solution (A-3) obtained in Synthesis Example 4 and 3.0433 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 were taken. , 2.0306 g of NMP, 2.0367 g of BCS, and 0.0454 g of polyfunctional oxetane compound (AD-3) as a cross-linking agent were added, and the mixture was stirred for 30 minutes with a magnetic stirrer. 4) was obtained.
Example 9
A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0073 g of the polyamic acid ester solution (A-3) obtained in Synthesis Example 4 and 3.0197 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 were taken. , 2.0436 g of NMP, 2.0364 g of BCS, and 0.0701 g of N-α- (9-fluorenylmethoxycarbonyl) -Nt-butoxycarbonyl-L-histidine as an imidization accelerator, The mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (I-5).
(Example 10)
A stirrer was placed in a 50 ml Erlenmeyer flask, 3.0210 g of the polyamic acid ester solution (A-3) obtained in Synthesis Example 4 and 3.0105 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 were taken. , 2.0140 g of NMP, 2.0246 g of BCS, and 0.0341 g of 4- (t-butoxycarbonylamino) pyridine as an imidization accelerator were added, and the mixture was stirred with a magnetic stirrer for 30 minutes. -6) was obtained.

(Example 11)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0021 g of the polyamic acid ester solution (A-3) obtained in Synthesis Example 4 and 3.17995 g of the polyamic acid solution (B-1) obtained in Synthesis Example 3 were taken. Further, 2.0480 g of NMP and 2.0062 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (I-7) .
( Example 13)
A stirrer was placed in a 50 ml Erlenmeyer flask and 1.8212 g of the polyamic acid ester solution (A-4) obtained in Synthesis Example 5 and 2.8206 g of the polyamic acid solution (B-3) obtained in Synthesis Example 11 were taken. Then, 3.4198 g of NMP and 2.0629 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (III-1).
(Example 14)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 4.2276 g of the polyamic acid ester solution (A-4) obtained in Synthesis Example 5 and 1.2331 g of the polyamic acid solution (B-4) obtained in Synthesis Example 12 were taken. Then, 2.6302 g of NMP and 2.0189 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (III-2).
(Example 15)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0022 g of the polyamic acid ester solution (A-4) obtained in Synthesis Example 5 was taken and 2.3359 g of the polyamic acid solution (B-5) obtained in Synthesis Example 13 was taken. 2.9918 g of NMP and 20168 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (III-3).

(Example 16)
A stirrer was placed in a 50 ml Erlenmeyer flask, 3.0145 g of the polyamic acid ester solution (A-5) obtained in Synthesis Example 6 and 1.7284 g of the polyamic acid solution (B-6) obtained in Synthesis Example 14 were taken. , 3.310 g of NMP and 2.0155 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (IV-1).
(Example 17)
A stirrer was placed in a 50 ml Erlenmeyer flask, 3.0186 g of the polyamic acid ester solution (A-6) obtained in Synthesis Example 7 and 1.7640 g of the polyamic acid solution (B-6) obtained in Synthesis Example 14 were taken. NMP (3.3171 g) and BCS (2.0344 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (IV-2).
(Example 18)
A stirrer was placed in a 50 ml Erlenmeyer flask, 3.0250 g of the polyamic acid ester solution (A-5) obtained in Synthesis Example 6 and 2.1211 g of the polyamic acid solution (B-7) obtained in Synthesis Example 15 were taken. , 3.0711 g of NMP and 2.0720 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (IV-3).
(Example 19)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.0026 g of the polyamic acid ester solution (A-6) obtained in Synthesis Example 7 and 2.0594 g of the polyamic acid solution (B-7) obtained in Synthesis Example 15 were taken. , 3.0194 g of NMP and 2.0030 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (IV-4).
(Example 20)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 1.2318 g of the polyamic acid ester solution (A-5) obtained in Synthesis Example 6 and 3.2286 g of the polyamic acid solution (B-8) obtained in Synthesis Example 16 were taken. NMP (3.6275 g) and BCS (2.0178 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (IV-5).

(Example 21)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 4.8328 g of the polyamic acid ester solution (A-7) obtained in Synthesis Example 8 and 2.1984 g of the polyamic acid solution (B-9) obtained in Synthesis Example 17 were taken. 1.2268 g of NMP and 2.0307 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-1).
(Comparative Example 8)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 4.8426 g of the polyamic acid ester solution (A-8) obtained in Synthesis Example 9 and 2.0480 g of the polyamic acid solution (B-9) obtained in Synthesis Example 17 were taken. , 1.2241 g of NMP and 2.0380 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-2).
(Example 22)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 4.8210 g of the polyamic acid ester solution (A-7) obtained in Synthesis Example 8 and 2.4526 g of the polyamic acid solution (B-5) obtained in Synthesis Example 14 were taken. NMP (0.8197 g) and BCS (2.0452 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-3).
(Comparative Example 9)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 4.7940 g of the polyamic acid ester solution (A-8) obtained in Synthesis Example 9 and 2.5558 g of the polyamic acid solution (B-5) obtained in Synthesis Example 14 were taken. In addition, 0.8545 g of NMP and 2.0254 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-4).
(Example 23)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.6281 g of the polyamic acid ester solution (A-7) obtained in Synthesis Example 8 and 2.8751 g of the polyamic acid solution (B-10) obtained in Synthesis Example 18 were taken. 1.602 g of NMP and 2.0514 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-5).

(Example 24)
A stirrer was placed in a 50 ml Erlenmeyer flask, and 3.6507 g of the polyamic acid ester solution (A-8) obtained in Synthesis Example 9 and 2.8195 g of the polyamic acid solution (B-10) obtained in Synthesis Example 18 were taken. 1.6288 g of NMP and 1.9982 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-6).
(Example 25)
The liquid crystal aligning agent (I-1) obtained in Example 5 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 26 to 31, 33 to 44 and Comparative Examples 11 and 12)
Each coating film was formed in the same manner as in Example 25 except that the respective liquid crystal aligning agents obtained in Examples 6 to 24 and Comparative Examples 8 and 9 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.

The liquid crystal aligning agent of the present invention can improve the liquid crystal alignment through reducing the fine irregularities on the surface of the liquid crystal alignment film to be obtained. Electrical characteristics 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. 2010-058554 filed on Mar. 15, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (10)

A polyamic acid ester having a repeating unit represented by the following formula (1), a polyamic acid having a repeating unit represented by the following formula (2), and an organic solvent, the weight average of the polyamic acid ester The liquid crystal aligning agent characterized by the molecular weight being smaller than the weight average molecular weight of the said polyamic acid.

(In Formula (1) and Formula (2), X ₁ and X ₂ are each independently a tetravalent organic group, and Y ₁ and Y ₂ are each independently a divalent organic group. 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, or alkynyl group having 1 to 10 carbon atoms. Group.)   The content of the polyamic acid ester and the content of the polyamic acid are 1/9 to 9/1 in a mass ratio of (content of polyamic acid ester / content of polyamic acid). Liquid crystal aligning agent.   The liquid crystal aligning agent of Claim 1 or 2 whose total content of the said polyamic acid ester and polyamic acid is 0.5-15 mass% with respect to the organic solvent.   The liquid crystal aligning agent in any one of Claims 1-3 whose weight average molecular weight of the said polyamic acid ester is 1000-100,000 smaller than the weight average molecular weight of the said polyamic acid. 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.

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

In the formula (2), the liquid crystal alignment agent according to any one of claims 1 to 6, Y ₂ is at least one selected from the group consisting of structures represented by the following formula.

The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-7. Method for manufacturing a liquid crystal alignment film a liquid crystal alignment agent according to any one of claims 1 to 7 is applied to a substrate and baked. The manufacturing method of the liquid crystal aligning film which irradiates the radiation which polarized the liquid crystal aligning agent in any one of Claims 1-7 on a board | substrate, baked, and obtained the film.