JP5041163B2 - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. More specifically, a liquid crystal aligning agent that provides a liquid crystal alignment film that exhibits excellent heat resistance and excellent voltage leakage, and a liquid crystal display in which abnormal panel lighting due to static electricity generated in the manufacturing process of the display element panel is suppressed. It relates to an element.

Currently, as a liquid crystal display element, a liquid crystal alignment film is formed on the surface of a substrate on which a transparent conductive film is provided to form a liquid crystal display element substrate. A so-called TN type (twisted) in which a layer of a nematic liquid crystal having a property is formed into a sandwich cell and the major axis of liquid crystal molecules is continuously twisted by 90 ° from one substrate to the other. A TN liquid crystal display element having a (Nematic) liquid crystal cell is widely known. In addition, an STN (Super Twisted Nematic) type liquid crystal display element capable of realizing a high contrast ratio as compared with a TN type liquid crystal display element, an IPS (In-Plane Switching) type liquid crystal display element with less viewing angle dependency, and an IPS type electrode structure FFS (Fringe Field Switching) type liquid crystal display element with improved brightness by increasing the aperture ratio of the display element portion, and OCB (Optical Compensated Bend: optical compensation with less viewing angle dependence and excellent high-speed response of moving images Bend) type liquid crystal display elements, VA (Vertical Alignment) type liquid crystal display elements using nematic liquid crystal having negative dielectric anisotropy, and the like have been developed.
As materials for the liquid crystal alignment film in these liquid crystal display elements, resin materials such as polyamic acid, imidized polymer, polyamide, and polyester are known, and in particular, liquid crystal alignment films made of polyamic acid or imidized polymer are heat resistant. It has excellent properties, mechanical strength, affinity with liquid crystal, etc., and is used in many liquid crystal display elements (see, for example, Patent Documents 1 to 3).

A liquid crystal display element having a liquid crystal alignment film made of such a resin material is designed on the assumption that its lifetime exceeds 10 years, as represented by recent liquid crystal televisions. Is required. In response to this requirement, by using an imidized polymer having a thermally and physically stable imide ring structure as a material for liquid crystal alignment, good characteristics for long-term driving, for example, due to thermal stress It is known to exhibit a voltage holding ratio and a characteristic (heat resistance) for suppressing a decrease in the liquid crystal aligning agent. However, when an imidized polymer having a large number of imide structures, for example, an imidized polymer having an imidization rate of 50% or more (hereinafter referred to as “high imidization rate imidized polymer”) is used. The panel may cause abnormal lighting due to the influence of static electricity generated from the electrostatic chuck used to fix the panel in the manufacturing process, and it takes a long time of about 24 hours to eliminate or alleviate this abnormal lighting. The problem is that the production efficiency of the liquid crystal panel is lowered. The reason why it takes a long time to eliminate or alleviate this abnormal lighting is that the high imidization rate imidized polymer has a very high electrical insulating property, so that the leakage of the charged voltage accumulated in the liquid crystal cell is low. It is considered.
As described above, it is considered that the heat resistance and the voltage leakage property in the liquid crystal panel are in a trade-off relationship. Therefore, there is a need for a liquid crystal alignment film material that has excellent voltage leakage without compromising the heat resistance exhibited by conventional high imidization ratio imidized polymers. Is hardly known. Although it is an examination example from a viewpoint different from this viewpoint, as an example of improving the afterimage characteristics of the liquid crystal display element, several improvement methods or liquid crystal alignment film materials have been proposed (for example, Patent Document 4). And 5). However, these methods and materials do not achieve improvement in the voltage leakage property in the liquid crystal panel.
JP-A-9-197411 JP 2003-149648 A JP 2003-107486 A JP-A-8-122793 JP 2005-120376 A JP-A-6-222366 JP-A-6-281937 JP-A-5-107544

The present invention has been made in view of the above circumstances, and the object thereof is generated in the manufacturing process of a liquid crystal aligning agent and a display element panel that provide a liquid crystal aligning film that exhibits excellent heat resistance and excellent voltage leakage. An object of the present invention is to provide a liquid crystal display element in which abnormal panel lighting due to static electricity is suppressed.
Still other objects and advantages of the present invention will become apparent from the following description.

In accordance with the present invention, the above objects and advantages of the present invention are primarily as follows:
Tetracarboxylic dianhydride and the following formula (A)

（式（Ｄ−ＩＩＩ）中、Ｒ ^９ は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−または−ＣＯ−であり、Ｒ ^１０ はステロイド骨格、トリフルオロメチルフェニル基、トリフルオロメトキシフェニル基およびフルオロフェニル基から選ばれる骨格もしくは基を有する１価の有機基、または炭素数６〜３０のアルキル基であり、Ｒ ^１１ は炭素数１〜４のアルキル基であり、ａ３は０〜３の整数である。）
で表される化合物ならびに
ｐ−フェニレンジアミン、３，５−ジアミノ安息香酸、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテルおよびビス［４−（４−アミノフェノキシ）フェニル］スルホンよりなる群から選択される少なくとも１種を含むジアミンとの反応により得られるポリアミック酸を脱水閉環してなるイミド化重合体を含有する液晶配向剤によって達成される。
本発明の上記目的および利点は、第二に、
上記の液晶配向剤から形成された液晶配向膜を具備する液晶表示素子により達成される。
(In formula (A), “*” indicates a bond, respectively.)
A compound having a structure represented by: and two amino groups ,
The following formula (D-III)

(In the formula (D-III), R ⁹ represents —O—, —COO—, —OCO—, —NHCO—, —CONH— or —CO—, and R ¹⁰ represents a steroid skeleton, a trifluoromethylphenyl group, A monovalent organic group having a skeleton or a group selected from a trifluoromethoxyphenyl group and a fluorophenyl group, or an alkyl group having 6 to 30 carbon atoms, R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and a3 Is an integer from 0 to 3.)
A compound represented by
at least selected from the group consisting of p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] sulfone. This is achieved by a liquid crystal aligning agent containing an imidized polymer obtained by dehydrating and ring-closing a polyamic acid obtained by reaction with a diamine containing one kind .
The above objects and advantages of the present invention are, secondly,
This is achieved by a liquid crystal display element comprising a liquid crystal alignment film formed from the above liquid crystal alignment agent.

The liquid crystal aligning agent of the present invention has heat resistance, that is, the voltage holding ratio and the liquid crystal aligning ability are not deteriorated even when a long-term heat stress is applied, and abnormal lighting due to static electricity generated in the manufacturing process of the display element is prevented. Even if it occurs, a liquid crystal alignment film having an excellent voltage leakage property is provided so that the elimination or relaxation can be performed quickly.
Such a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention can be suitably applied to various liquid crystal display elements.
The liquid crystal display element of the present invention having the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention does not deteriorate the display performance even when driven for a long time. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, cellular phones, various monitors. It can be suitably used for a display device such as a liquid crystal television.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of the present invention comprises tetracarboxylic dianhydride,
A compound having the structure represented by the above formula (A) and two amino groups, a compound represented by the above formula (D-III), p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4′- A polyamic acid obtained by reacting a diamine containing at least one selected from the group consisting of diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] sulfone Containing an imidized polymer obtained by dehydration and ring closure.
<Tetracarboxylic dianhydride>
Examples of the tetracarboxylic dianhydride used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention include alicyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, and aromatics. Group tetracarboxylic dianhydride.

  Specific examples of the alicyclic tetracarboxylic dianhydride include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic. Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6 -Tetracarbo Acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-Hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 9b-Hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 9b-Hexahydro-5-ethyl 5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl- 5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl- 5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl- 5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl- 5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -Naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [ 2.2.2] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro -3 ′-(tetrahydrofuran-2 ′, 5′-dione), the following formulas (TI) and (T-II)

(In the formulas (T-I) and (T-II), R ¹ and R ³ are each a divalent organic group having an aromatic ring, and R ² and R ⁴ are each a hydrogen atom or an alkyl group. And a plurality of R ² and R ⁴ may be the same or different.)
And the like, and the like.
Specific examples of the aliphatic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride.
Specific examples of the aromatic tetracarboxylic dianhydride include, for example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 ′. -Biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4 '-Biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-di Carboxyphenoxy Diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (tri Phenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (an Hydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydro) Remellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis ( Anhydrotrimellitate), the following formulas (T-1) to (T-4)

And the like, and the like.
These tetracarboxylic dianhydrides can be used singly or in combination of two or more.
The tetracarboxylic dianhydride used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention is an alicyclic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride. At least one selected from the group consisting of pyromellitic dianhydride and 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride (hereinafter referred to as “specific tetracarboxylic dianhydride”). It is preferable. Specific tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxy Cyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuranyl) ) -3-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic Acid dianhydride, 3-oxabicyclo [3.2.1] octane-2, - dione-6-spiro-3 '- (tetrahydrofuran-2', 5'-dione), the following formula among the compounds represented by the above formula (T-I) (T-5) ~ (T-7)

Of the compounds represented by formula (II) above, the following formula (T-8)

And at least one selected from the group consisting of a compound represented by the formula: pyromellitic dianhydride and 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, It is more preferable from the viewpoint of expression, more preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2 , 3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 1,3 3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, cis-3,7-di Tylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride 1,3,3a, 4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), represented by the above formula (T-5) At least one selected from the group consisting of a compound, pyromellitic dianhydride and 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, particularly preferably 1,2,3,4-tetra Carboxylic dianhydride, 2,3,5-tri Ruboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] At least one selected from the group consisting of furan-1,3-dione, pyromellitic dianhydride and 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 5-Tricarboxycyclopentylacetic acid dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] It is preferably at least one selected from the group consisting of furan-1,3-dione.

The tetracarboxylic dianhydride used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention is a specific tetracarboxylic dianhydride as described above with respect to the total tetracarboxylic dianhydride. It is preferable that the content is 60 mol% or more, and more preferable that the content is 80 mol% or more.
In the case where the tetracarboxylic dianhydride includes a tetracarboxylic dianhydride other than the specific tetracarboxylic dianhydride, preferred tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride are: For example, butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4 , 5,8-naphthalenetetracarboxylic dianhydride.

（式（Ａ−１）中、Ｕ^１およびＵ^２は、それぞれ独立に、炭素数２〜５のアルキレン基もしくは炭素数４〜６の２価の脂環式基であるか、または員数６〜１０の芳香環を含む２価の有機基である。）
で表される化合物を挙げることができる。
上記式（Ａ−１）におけるＵ^１およびＵ^２の炭素数２〜５のアルキレン基としては、例えば１，３−プロピレン基、１，５−ペンチレン基などを挙げることができる。Ｕ^１およびＵ^２の炭素数４〜６の２価の脂環式基としては、例えば１，４−シクロへキシレン基などを挙げることができる。Ｕ^１およびＵ^２の員数６〜１０の芳香環を含む２価の有機基における「芳香環」とは、単環の芳香族炭化水素環、多環状の芳香族炭化水素環および縮合環系を有する芳香族炭化水素環ならびにこれらの環を構成する炭素原子のうちの１個または複数をヘテロ原子で置き換えた複素芳香環を含む概念である。この員数６〜１０の芳香環を含む２価の有機基としては、炭素数６〜１０のアリーレン基が好ましい。Ｕ^１およびＵ^２の特に好ましい具体例としては、例えば１，３−プロピレン基、１，４−シクロヘキシレン基、１，４−フェニレン基、ナフタレン−１，５−ジイル基、ピリミジン−２，５−ジイル基、トリアジン−２，４−ジイル基などを挙げることができる。
化合物（Ａ）の具体例としては、Ｎ，Ｎ’−ビス（３−アミノプロピル）ピペラジン、Ｎ，Ｎ’−ビス（４−アミノシクロヘキサン）ピペラジン、Ｎ，Ｎ’−ビス（４−アミノフェニル）ピペラジンなどを挙げることができ、特にＮ，Ｎ’−ビス（４−アミノフェニル）ピペラジンが好ましい。
本発明の液晶配向剤に含有されるイミド化重合体を合成するために用いられるジアミンとしては、化合物（Ａ）とその他のジアミンとを組み合わせて用いられる。
<Diamine>
The diamine used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention is a compound represented by the above formula (A) and a compound having two amino groups (hereinafter referred to as “compound (A)”. ")"). As such a compound (A), for example, the following formula (A-1)

(In Formula (A-1), U ¹ and U ² are each independently an alkylene group having 2 to 5 carbon atoms or a divalent alicyclic group having 4 to 6 carbon atoms, or 6 to 6 members. (It is a divalent organic group containing 10 aromatic rings.)
The compound represented by these can be mentioned.
Examples of the alkylene group having 2 to 5 carbon atoms of U ¹ and U ² in the above formula (A-1) include a 1,3-propylene group and a 1,5-pentylene group. Examples of the divalent alicyclic group having 4 to 6 carbon atoms of U ¹ and U ² include a 1,4-cyclohexylene group. The “aromatic ring” in the divalent organic group containing 6 to 10 aromatic rings of U ¹ and U ² is a monocyclic aromatic hydrocarbon ring, a polycyclic aromatic hydrocarbon ring and a condensed ring system. It is a concept including aromatic hydrocarbon rings having heteroaromatic rings in which one or more of carbon atoms constituting these rings are replaced with heteroatoms. The divalent organic group containing an aromatic ring having 6 to 10 members is preferably an arylene group having 6 to 10 carbon atoms. As particularly preferred specific examples of U ¹ and U ² , for example, 1,3-propylene group, 1,4-cyclohexylene group, 1,4-phenylene group, naphthalene-1,5-diyl group, pyrimidine-2,5 -A diyl group, a triazine-2, 4-diyl group, etc. can be mentioned.
Specific examples of the compound (A) include N, N′-bis (3-aminopropyl) piperazine, N, N′-bis (4-aminocyclohexane) piperazine, N, N′-bis (4-aminophenyl). Examples include piperazine, and N, N′-bis (4-aminophenyl) piperazine is particularly preferable.
The diamine used to synthesize the imidized polymer contained in the liquid crystal aligning agent of the present invention, used in combination of compound (A) and the other diamines.

    Examples of other diamines that can be used in the present invention include p-phenylenediamine, m-phenylenediamine, 3,5-diaminobenzoic acid, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1 -(4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4 -(4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4- Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydro Anthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2 Chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3 '-Dimethoxy-4,4'-diaminobiphenyl, 1,4,4'-(p-phenyleneisopropylidene) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4 -(4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino -2-trifluoromethyl) phenoxy] -octafluorobiphenyl, di (4-aminophenyl) benzidine, the following formulas (D-1) to (D-5)

(Y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 1 to 5.)
An aromatic diamine such as a compound represented by each of the following:
1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, Tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, etc. An aliphatic or cycloaliphatic diamine;
2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4 -Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3 , 5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl -S-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6- Aminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6 Phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, 1- (3,5-diaminophenyl) -3-decylsuccinimide, 1- (3 5-Diaminophenyl) -3-octadecylsuccinimide, the following formula (DI)

(In the formula (DI), R ⁵ is a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ¹ is a divalent organic group. R ⁶ is an alkyl group having 1 to 4 carbon atoms, and a1 is an integer of 0 to 3.)
A compound represented by formula (D-II):

(In Formula (D-II), R ⁷ is a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ² is a divalent organic group, respectively. A plurality of X ² may be the same or different, R ⁸ is an alkyl group having 1 to 4 carbon atoms, and a2 is an integer of 0 to 3 respectively. is there.)
A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in a molecule such as a compound represented by:
The following formula (D-III)

(In the formula (D-III), R ⁹ represents —O—, —COO—, —OCO—, —NHCO—, —CONH— or —CO—, and R ¹⁰ represents a steroid skeleton, a trifluoromethylphenyl group, A monovalent organic group having a skeleton or a group selected from a trifluoromethoxyphenyl group and a fluorophenyl group, or an alkyl group having 6 to 30 carbon atoms, R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and a3 Is an integer from 0 to 3.)
Monosubstituted phenylenediamines such as compounds represented by:
The following formula (D-IV)

(In the formula (D-IV), each R ¹² is a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ¹² may be the same or different, and p is each 1 is an integer of 1 to 3, and q is an integer of 1 to 20.)
And diaminoorganosiloxanes such as compounds represented by the formula:
These other diamines can be used alone or in combination of two or more.
The benzene ring of the aromatic diamine may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). In the above formulas (DI), (D-II) and (D-III), R ⁶ , R ⁸ and R ¹¹ are each preferably a methyl group, and a1, a2 and a3 are each 0 Or it is preferable that it is 1, and it is more preferable that it is 0.
The steroid skeleton of R ^{10 in} the above formula (D-III) refers to a skeleton composed of a cyclopentano-perhydrophenanthrene nucleus or a skeleton in which one or more of the carbon-carbon bonds are double bonds. As the monovalent organic group of R ⁵ having such a steroid skeleton, those having 17 to 51 carbon atoms are preferable, and those having 17 to 29 carbon atoms are more preferable. Specific examples of R ¹⁰ include cholestan-3-yl group, cholesta-5-en-3-yl group, cholesta-24-en-3-yl group, and cholesta-5,24-dien-3-yl group. And lanostane-3-yl group.

  Other diamines used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention include p-phenylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diamino. Diphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4 -Aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-pheny Range isopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, , 4-cyclohexanediamine, 4,4′-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, the above formula (D-1 ) To (D-5), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, the above formula (DI) Of the compounds represented by formula (D-6)

  Of the compounds represented by formula (D-II), the following formula (D-7)

1,3-bis (-3-diaminopropyl) tetramethyldisiloxane among the compound represented by formula (D-III) and the compound represented by formula (D-IV) Preferably, it is at least one selected from the group consisting of the compound represented by the above formula (D-III) and p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4′-diaminodiphenylmethane, 4 , 4′-diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] sulfone are preferred.
Specific examples of the compound represented by the formula (D-III) include, for example, the following formulas (D-8) to (D-16):

And the like, and the like.
Among the compounds represented by the above formula (D-III), in the above formula (D-III), R ⁷ is —O— or —COO—, and R ⁸ is a monovalent organic group having a steroid skeleton. Certain compounds are preferred, especially the above formulas (D-8) to (D-13)
The compounds represented by each of the above can be mentioned as preferred ones.
The diamine used for synthesizing the imidized polymer contained in the liquid crystal aligning agent of the present invention preferably contains 1 mol% or more of the compound (A) with respect to the total diamine, and contains 10 mol% or more. It is more preferable.

The diamine used in the present invention includes the compound (A), the compound represented by the above formula (D-III), p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4′-diaminodiphenylmethane, 4 , Ru der those containing at least one selected from 4'-diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] consisting sulfone group. In this case, the proportion of each compound used relative to the total diamine is preferably 1 to 80 mol%, more preferably 5 to 70 mol% per compound (A), and per compound represented by the above formula (D-III). Preferably it is 1-50 mol%, More preferably, it is 5-30 mol%, p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and bis [ It is preferably 30 to 90 mol%, more preferably 40 to 60 mol% per at least one selected from the group consisting of 4- (4-aminophenoxy) phenyl] sulfone.

<Synthesis of imidized polymer>
The imidized polymer contained in the liquid crystal aligning agent of the present invention includes the tetracarboxylic dianhydride as described above ,
Compound (A) , compound represented by the above formula (D-III) and p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether and bis [4 The polyamic acid obtained by reacting with a diamine containing at least one selected from the group consisting of-(4-aminophenoxy) phenyl] sulfone can be synthesized by dehydrating and ring-closing.
[Synthesis of polyamic acid]
The ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group of the diamine. The ratio which becomes an equivalent is preferable, More preferably, it is a ratio which becomes 0.7-1.2 equivalent.
The polyamic acid is preferably synthesized in an organic solvent, preferably at −20 ° C. to 150 ° C., more preferably at 0 to 100 ° C., preferably 1 to 72 hours, more preferably 3 to 48 hours. Done. Here, the organic solvent is not particularly limited as long as it can dissolve the produced polyamic acid. For example, 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-butoxy Amide compounds such as -N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexa Examples include aprotic compounds such as methyl phosphortriamide; phenolic compounds such as m-cresol, xylenol, phenol, and halogenated phenol. The amount of organic solvent used (α) is such that the total amount (β) of tetracarboxylic dianhydride and diamine compound is 0.1 to 30% by weight with respect to the total amount (α + β) of the reaction solution. It is preferable. In addition, when using an organic solvent together with the poor solvent demonstrated below, the usage-amount ((alpha)) of said organic solvent should be understood as a total amount of an organic solvent and a poor solvent.

As the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents for polyamic acid, may be used in combination as long as the generated polyamic acid does not precipitate. Specific examples of such poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol. , Ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, malon Acid diethyl, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i Propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamylpropionate, isoamylisobutyrate , And the like di-iso-pentyl ether.
When the organic solvent and the poor solvent are used in combination, the amount of the poor solvent used can be appropriately set within a range in which the polyamic acid to be produced does not precipitate, but is preferably 30% by weight or less with respect to the total amount of the solvent. 20% by weight or less is more preferable.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This polyamic acid solution may be used for the dehydration ring-closing reaction in the next step as it is, may be subjected to the dehydration ring-closing reaction after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid May be subjected to a dehydration ring closure reaction after purification. The polyamic acid is isolated by pouring the above polyamic acid solution into a large amount of poor solvent to obtain a precipitate, and drying this precipitate under reduced pressure, or by distilling the polyamic acid solution under reduced pressure with an evaporator. It can be carried out. Also, the polyamic acid is purified by a method in which the polyamic acid thus obtained is dissolved again in an organic solvent and then precipitated in a poor solvent, or a method in which the step of distilling off with an evaporator under reduced pressure is performed once or several times. be able to.

[Dehydration ring closure reaction]
The imidized polymer contained in the liquid crystal aligning agent of the present invention may be a completely imidized product obtained by dehydrating and ring-closing all of the amic acid structure that the polyamic acid as a raw material had, and part of the amic acid structure It may be a partially imidized product in which only an amic acid structure and an imide ring structure coexist.
The imidized polymer contained in the liquid crystal aligning agent of the present invention preferably has an imidization ratio of 30 mol% or more. The imidation ratio is more preferably 40 mol% or more, further preferably 50 mol% or more, and particularly preferably 60 mol% or more. By using an imidized polymer having an imidization rate of 30 mol% or more, liquid crystal alignment that has excellent heat resistance surpassing the conventionally known high imidization rate imidized polymer and also has excellent voltage leakage property A liquid crystal aligning agent that gives a film can be obtained. In the liquid crystal aligning agent of the present invention, even if the imidization rate of the imidized polymer is increased, the voltage leakage of the liquid crystal alignment film to be formed is not impaired. The liquid crystal alignment can provide a liquid crystal alignment film having both high heat resistance and good voltage leakage even when the imidization ratio is 80 mol% or more, and substantially 100%, for example. An agent can be obtained.
The said imidation rate represents the ratio for which the number of the imide ring structure with respect to the sum total of the number of the amic acid structure of an imidation polymer and the number of imide ring structures is represented by a percentage. At this time, a part of the imide ring may be an isoimide ring. The imidation rate is the result of measuring ¹ H-NMR at room temperature (for example, 25 ° C.) using tetramethylsilane as a reference substance by dissolving the imidized polymer in a suitable deuterated solvent (for example, deuterated dimethyl sulfoxide). From the following equation (i), it can be obtained.

Imidation rate (%) = (1-A ¹ / A ² × α) × 100 (i)

(In Formula (i), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of an imidized polymer ( It is the number ratio of other protons to one NH group proton in the polyamic acid).

The polyamic acid is preferably dehydrated and closed by (1) heating the polyamic acid or (2) dissolving the polyamic acid in an organic solvent and adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution as necessary. This is done by heating.
The reaction temperature in the method of heating the polyamic acid (1) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. The reaction time is preferably 1 to 8 hours, more preferably 3 to 5 hours. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease.
On the other hand, in the method of adding a dehydrating agent and a dehydrating ring closure catalyst to the polyamic acid solution of (2) above, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used. Can do. Although the usage-amount of a dehydrating agent is based on the desired imidation rate, it is preferable to set it as 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. The imidation rate can be increased as the amount of the above dehydrating agent and dehydrating ring-closing agent increases. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1 to 8 hours, more preferably 3 to 5 hours.
In the method (2), a reaction solution containing an imidized polymer is obtained as described above. This reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. After separating, it may be used for preparing a liquid crystal aligning agent, or the isolated imidized polymer may be purified and then used for preparing a liquid crystal aligning agent. In order to remove the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. Isolation and purification of the imidized polymer can be performed by performing the same operations as described above as the method for isolating and purifying the polyamic acid.

[End-modified polymer]
The imidized polymer contained in the liquid crystal aligning agent of the present invention may be a terminal modified type having a molecular weight adjusted. By using the terminal-modified polymer, the coating properties of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer can be obtained by adding a molecular weight modifier to a polymerization reaction system when synthesizing a polyamic acid. Examples of molecular weight regulators include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like.
Examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n -Hexadecyl succinic anhydride etc. can be mentioned. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, Examples include n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine. it can. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid. .
[Solution viscosity]
The imidized polymer obtained as described above preferably has a solution viscosity of 20 to 800 mPa · s, and has a solution viscosity of 30 to 500 mPa · s when a 10% by weight solution is obtained. It is more preferable to have it.
The solution viscosity (mPa · s) of the polymer is a value measured at 25 ° C. using an E-type rotational viscometer for a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer. .

<Other ingredients>
The vertically aligned liquid crystal alignment film of the present invention contains the imidized polymer as described above as an essential component, but may contain other components as necessary. Examples of such other components include polymers other than the imidized polymer (hereinafter referred to as “other polymers”), adhesion improvers, and the like.
These other polymers can be used to improve solution and electrical properties. Such another polymer is a polymer other than an imidized polymer obtained by dehydrating and ring-closing a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine containing the compound (A). A polyamic acid obtained by reacting an acid dianhydride and a diamine not containing the compound (A) (hereinafter referred to as “other polyamic acid”), an imidized polymer obtained by dehydrating and ring-closing the polyamic acid (hereinafter referred to as “polyamic acid”) , "Other imidized polymers"), polyamic acid esters, polyesters, polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, etc. Can do. Of these, other polyamic acids or other imidized polymers are preferred.
As other polymer use ratios, the total polymer (imidized polymer obtained by dehydrating and ring-closing polyamic obtained by reacting the above tetracarboxylic dianhydride and the diamine containing the compound (A) and The total of other polymers, the same shall apply hereinafter)) is preferably 30% by weight or less, more preferably 20% by weight or less.

The said adhesive improvement agent can be used in order to improve the adhesiveness with respect to the substrate surface of the liquid crystal aligning film obtained. Examples of the adhesion improver include a compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound”), a functional silane compound, and the like.
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyloxy-2,4-hexanediol, N, N, N ′, N ′ -Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'- Diaminodiphenylmethane, 3- (N-allyl--N- glycidyl) aminopropyltrimethoxysilane, 3- (N, N- diglycidyl) and the like aminopropyltrimethoxysilane.
The use ratio of the epoxy compound as described above is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total polymer.

Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N- Benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis ( Examples thereof include oxyethylene) -3-aminopropyltrimethoxysilane and N-bis (oxyethylene) -3-aminopropyltriethoxysilane.
The use ratio of the functional silane compound as described above is preferably 2 parts by weight or less, more preferably 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the total amount of the polymer.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is constituted by dissolving the imidized polymer as described above and other components optionally blended as required, preferably dissolved in an organic solvent.
Examples of the organic solvent that can be used in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4. -Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, Ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide and the like can be mentioned.
The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later, and preferably, when heated, a coating film that becomes a liquid crystal aligning film is formed, but the solid content concentration is less than 1% by weight. In this case, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive. In some cases, a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal aligning agent increases, resulting in poor coating properties.
The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 to 200 degreeC, More preferably, it is 20 to 60 degreeC.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention as described above.
As a preferable operation mode in the liquid crystal display element of the present invention, TN type, STN type, VA type or IPS type can be mentioned.
The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). In the step (1), the substrate to be used, the preferred application method of the liquid crystal aligning agent, and the heating temperature after applying the liquid crystal aligning agent differ depending on the desired operation mode. Steps (2) and (3) are common to each operation mode.

(1) First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, Then, a coating film is formed on a board | substrate by heating an application surface.
(1-1) When manufacturing a TN type, STN type, or VA type liquid crystal display element, a pair of two substrates provided with a patterned transparent conductive film is used as a pair on each transparent conductive film formation surface. The liquid crystal aligning agent of the present invention is preferably applied by an offset printing method, a spin coating method or an ink jet printing method, respectively, and then each coated surface is heated to form a coating film. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or poly (alicyclic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. In order to obtain a patterned transparent conductive film which can be used, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, a mask having a desired pattern when forming the transparent conductive film The method using can be used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or functional titanium is formed on the surface of the substrate surface on which the coating film is to be formed. You may give the pretreatment which apply | coats a compound etc. previously.
The heating temperature after application of the liquid crystal alignment agent is preferably 30 to 300 ° C, more preferably 40 to 250 ° C, and the heating time is preferably 1 to 60 minutes, more preferably 10 to 30 minutes. The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

(1-2) On the other hand, when manufacturing an IPS type liquid crystal display element, the conductive film forming surface of the substrate provided with the comb-shaped transparent conductive film and the counter substrate provided with no conductive film On one surface, the liquid crystal aligning agent of the present invention is preferably applied by a roll coater method, a spinner method or an ink jet printing method, respectively, and then each coated surface is heated to form a coating film.
The material of the substrate and transparent conductive film used at this time, the patterning method of the transparent conductive film, and the pretreatment of the substrate are the same as in (1-1) above.
The heating temperature after applying the liquid crystal aligning agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C, and the heating time is preferably 1 to 60 minutes, more preferably 10 to 30 minutes. It is.
The preferable film thickness of the coating film to be formed is the same as (1-1) above.
In both cases (1-1) and (1-2), the liquid crystal aligning agent of the present invention forms a coating film that becomes an alignment film by removing the organic solvent after coating. In the case where the agent contains a polyamic acid or an imidized polymer having both an imide ring structure and an amic acid structure, the film is further heated after the coating film is formed to advance the dehydration ring-closing reaction, thereby further imidizing the coating. A film may be used.

(2) When the liquid crystal display element manufactured by the method of the present invention is a VA liquid crystal display element, the coating film formed as described above can be used as a liquid crystal alignment film as it is. If desired, it may be used after the rubbing treatment described below.
On the other hand, when manufacturing a liquid crystal display element other than the VA type, a rubbing treatment is performed on the coating film formed as described above to obtain a liquid crystal alignment film.
The rubbing treatment can be performed by rubbing the coating film surface formed as described above with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton in a certain direction. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.
Further, for example, Patent Document 6 (JP-A-6-222366) and Patent Document 7 (JP-A-6-281937) show liquid crystal alignment films formed with the liquid crystal aligning agent of the present invention. A process of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays, as disclosed in Japanese Patent Application Laid-Open No. 5-107544 After a resist film is formed on a part of the liquid crystal alignment film surface, the resist film is removed after the rubbing process in a direction different from the previous rubbing process. It is possible to improve the visual field characteristics of the liquid crystal display element obtained by having it.

(3) A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates opposed to each other. Here, when the rubbing process is performed on the coating film, the two substrates are disposed to face each other so that the rubbing directions in the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.
In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.
The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole.
The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.
Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase, and then gradually cooled to room temperature, so that the flow alignment during liquid crystal injection is achieved. It is desirable to remove.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals. Liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. In addition, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral products such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck) Agent: Ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.
As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film itself in which a polarizing film called “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of can be mentioned.
In the liquid crystal display element of the present invention, even if the panel is abnormally lit due to static electricity generated from the electrostatic chuck used in the manufacturing process, the abnormal lighting is eliminated or alleviated in a short time. Contributes to the improvement of device manufacturing efficiency.
The liquid crystal display element of the present invention manufactured as described above does not deteriorate in display performance even when it is continuously driven for a long time as compared with a conventionally known liquid crystal display element. Has an advantage that the light leakage of the backlight, which may be caused by the poor alignment of the liquid crystal due to the thermal deterioration of the liquid crystal alignment film, does not occur.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
In the following synthesis examples, N, N′-bis (4-aminophenyl) piperazine used was a commercial product of Wakayama Seika Kogyo Co., Ltd. as it was.
Moreover, the solution viscosity of the polymer in the synthesis example is a value measured at 25 ° C. using an E-type viscometer.
Synthesis Example 1 (Imidation polymer synthesis example 1)
224 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic anhydride and 96.1 g (0.89 mol) of p-phenylenediamine as diamine, 3,6-bis (4 -Aminobenzoyloxy) cholestane 2.6 g (0.010 mol) and N, N'-bis (4-aminophenyl) piperazine 27 g (0.10 mol) were dissolved in 3,100 g of N-methyl-2-pyrrolidone. The solution containing 10% by weight of polyamic acid was obtained by performing the reaction at room temperature for 6 hours. The solution viscosity of this polyamic acid solution was 90 mPa · s.
Next, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 136 g of pyridine and 105 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with new γ-butyrolactone (by this solvent substitution, pyridine and acetic anhydride used in the dehydration cyclization reaction were removed from the system, the same applies hereinafter), and then concentrated. As a result, 1,500 g of a solution containing 20% by weight of an imidized polymer (A-1) having an imidization ratio of about 88% was obtained. A small amount of this solution was collected, and γ-butyrolactone was added to measure the solution viscosity as a solution having a concentration of 6.0% by weight of 22 mPa · s.

Synthesis Example 2 (Synthesis Example 2 of imidized polymer)
112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic anhydride and 38.0 g (0.35 mol) of p-phenylenediamine as diamine, 3 (3,5-diamino Benzoyloxy) cholestane 53.0 g (0.10 mol) and N, N′-bis (4-aminophenyl) piperazine 13.4 g (0.050 mol) were dissolved in 1,900 g of N-methyl-2-pyrrolidone. The solution containing 10% by weight of polyamic acid was obtained by performing the reaction at room temperature for 6 hours. The solution viscosity of this polyamic acid solution was 58 mPa · s.
Next, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 116 g of pyridine and 90 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with fresh N-methyl-2-pyrrolidone, and then concentrated to obtain 15% by weight of imidized polymer (A-2) having an imidization ratio of about 92%. About 1,430 g of the contained solution was obtained. A small amount of this solution was collected, and γ-butyrolactone was added to measure the solution viscosity as a solution having a concentration of 6.0% by weight of 23 mPa · s.

Synthesis Example 3 (Imidation polymer synthesis example 3)
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 49 g (0.35 mol) of p-phenylenediamine as diamine, N, N′-bis (4 -Aminophenyl) piperazine 13.4 g (0.050 mol) and 3 (3,5-diaminobenzoyloxy) cholestane 26 g (0.050 mol) are dissolved in 1,800 g of N-methyl-2-pyrrolidone, By reacting at 6 ° C. for 6 hours, a solution containing 10% by weight of polyamic acid was obtained. The solution viscosity of this polyamic acid solution was 60 mPa · s.
Next, 1,800 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone, whereby a solution containing 15% by weight of an imidized polymer (A-3) having an imidization ratio of about 55%. 1,200 g was obtained.
A small amount of this solution was taken and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a 10 wt% solution was 85 mPa · s.

Synthesis Example 4 (Synthesis Example 4 of imidized polymer)
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 32 g (0.30 mol) of p-phenylenediamine as diamine, 20 g of 4,4′-diaminodiphenylmethane (0.1 mol), 13.4 g (0.050 mol) of N, N′-bis (4-aminophenyl) piperazine and 26 g (0.05 mol) of 3 (3,5-diaminobenzoyloxy) cholestane, A solution containing polyamic acid was obtained by dissolving in 1,100 g of N-methyl-2-pyrrolidone and reacting at 60 ° C. for 6 hours. A small amount of the obtained polyamic acid solution was collected, and the solution viscosity measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 60 mPa · s.
Next, 1,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80 g of pyridine and 100 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone, whereby a solution containing 15% by weight of an imidized polymer (A-4) having an imidization ratio of about 80%. 1,200 g was obtained. A small amount of this solution was collected, and γ-butyrolactone was added thereto, and the solution viscosity measured as a solution having a concentration of 10% by weight was 87 mPa · s.

Synthesis Example 5 (Synthesis Example 5 of imidized polymer)
112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic anhydride and 27.0 g (0.25 mol) of p-phenylenediamine as diamine and N, N′-bis ( 4-Aminophenyl) piperazine (67.0 g, 0.25 mol) was dissolved in 1,900 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing 10% by weight of polyamic acid. Obtained. The solution viscosity of this polyamic acid solution was 80 mPa · s.
Next, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 136 g of pyridine and 105 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new γ-butyrolactone, and then concentrated to obtain a solution 1 containing 15% by weight of an imidized polymer (A-5) having an imidization ratio of about 92%. , 100 g was obtained. A small amount of this solution was collected, and γ-butyrolactone was added to measure the solution viscosity as a solution having a concentration of 6.0% by weight of 24 mPa · s.

Synthesis Example 6 (Synthesis Example 6 of imidized polymer)
112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid anhydride and 38 g (0.45 mol) of p-phenylenediamine and N, N′-bis (4- Aminophenyl) piperazine (13 g, 0.0.50 mol) was dissolved in 1,900 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected and concentrated under reduced pressure, and the solution viscosity measured as a 10 wt% solution was 82 mPa · s.
Next, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 136 g of pyridine and 105 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new γ-butyrolactone, and then concentrated to obtain a solution 1 containing 15% by weight of an imidized polymer (A-6) having an imidization ratio of about 90%. , 100 g was obtained. A small amount of this solution was collected, and γ-butyrolactone was added to measure the solution viscosity as a solution having a concentration of 6.0% by weight of 23 mPa · s.

Synthesis Example 7 (Synthesis Example 7 of imidized polymer)
168 g (0.75 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro -2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157 g (0.25 mol) and p-phenylenediamine 32 g (0.30 mol) as diamine, 4, 80 g (0.40 mol) of 4′-diaminodiphenyl ether, 85 g (0.20 mol) of bis [4- (4-aminophenoxy) phenyl] sulfone and 27 g (0 of N, N′-bis (4-aminophenyl) piperazine .10 mol) is dissolved in 4,200 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to contain polyamic acid. To obtain a liquid. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a concentration of 10% by weight was 85 mPa · s.
Next, 1,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 150 g of pyridine and 200 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. Solution 2 containing 15% by weight of imidized polymer (A-7) having an imidization ratio of about 88% by solvent substitution of the solvent in the system with new γ-butyrolactone and subsequent concentration after dehydration and cyclization reaction , 600 g was obtained.

Synthesis Example 8 (Synthesis Example 8 of imidized polymer)
112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 38 g (0.25 mol) of 3,5-diaminobenzoic acid as diamine, N, N'- A solution containing polyamic acid was obtained by dissolving 67 g (0.25 mol) of bis (4-aminophenyl) piperazine in 2,100 g of N-methyl-2-pyrrolidone and reacting at room temperature for 6 hours. A small amount of the obtained polyamic acid solution was collected and concentrated under reduced pressure, and the solution viscosity measured as a solution having a concentration of 10% by weight was 60 mPa · s.
Next, 1,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 150 g of pyridine and 200 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new γ-butyrolactone, and then concentrated to obtain a solution 1 containing 15% by weight of an imidized polymer (A-8) having an imidization ratio of about 88%. , 400 g was obtained.

Synthesis Example 9 (Synthesis Example 8 of imidized polymer)
112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 134 g (0.50 mol) of N, N′-bis (4-aminophenyl) piperazine as diamine Was dissolved in 2100 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing 10% by weight of polyamic acid. The solution viscosity of this polyamic acid solution was 100 mPa · s.
Next, 1,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 150 g of pyridine and 200 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new γ-butyrolactone, and then concentrated to obtain a solution 1 containing 15% by weight of an imidized polymer (A-9) having an imidization ratio of about 90%. , 600 g was obtained.

Comparative Synthesis Example 1 (Synthesis example 1 of other imidized polymer)
224 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic anhydride and 107 g (0.99 mol) of p-phenylenediamine as diamine, 3,6-bis (4-amino) Benzoyloxy) cholestane 2.6 g (0.010 mol) and N, N′-bis (4-aminophenyl) piperazine 27 g (0.10 mol) were dissolved in 1,260 g of N-methyl-2-pyrrolidone, For 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a concentration of 10% by weight was 90 mPa · s.
Next, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 136 g of pyridine and 105 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with new γ-butyrolactone and then concentrated to obtain 1,800 g of a solution containing 15% by weight of polyimide (B-1) having an imidization ratio of about 88%. Obtained.
A small amount of this solution was collected, and γ-butyrolactone was added to measure the solution viscosity as a solution having a concentration of 6.0% by weight of 22 mPa · s.

Comparative Synthesis Example 2 (Synthesis example 2 of other imidized polymer)
112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic anhydride and 43.0 g (0.40 mol) of p-phenylenediamine as diamine, 3 (3,5-diamino A solution containing polyamic acid was obtained by dissolving 53.0 g (0.10 mol) of benzoyloxy) cholestane in 1,230 g of N-methyl-2-pyrrolidone and reacting at room temperature for 6 hours. A small amount of the resulting polyamic acid solution was taken, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a concentration of 10% by weight was 58 mPa · s.
Next, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 116 g of pyridine and 90 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone, and then concentrated to obtain 15% by weight of an imidized polymer (B-2) having an imidization ratio of about 92%. About 1,000 g of the contained solution was obtained. A small amount of this solution was collected, and γ-butyrolactone was added to measure the solution viscosity as a solution having a concentration of 6.0% by weight of 23 mPa · s.

Comparative Synthesis Example 3 (Synthesis example 3 of other imidized polymer)
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 56 g (0.40 mol) of p-phenylenediamine and 3 (3,5-diaminobenzoyl) as diamine A solution containing polyamic acid was obtained by dissolving 26 g (0.050 mol) of oxy) cholestane in 1,100 g of N-methyl-2-pyrrolidone and reacting at 60 ° C. for 6 hours. A small amount of the obtained polyamic acid solution was collected, and the solution viscosity measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 60 mPa · s.
Next, 1,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone, whereby a solution containing 15% by weight of an imidized polymer (B-3) having an imidization ratio of about 50%. 1,150 g was obtained.
A small amount of this solution was taken and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a 10 wt% solution was 85 mPa · s.

Comparative Synthesis Example 4 (Synthesis example 4 of other imidized polymer)
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 44 g (0.35 mol) of p-phenylenediamine as diamine, 20 g of 4,4′-diaminodiphenylmethane (0.1 mol) and 26 g (0.05 mol) of 3 (3,5-diaminobenzoyloxy) cholestane were dissolved in 800 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours to obtain polyamic acid. A solution containing acid was obtained. A small amount of the obtained polyamic acid solution was collected, and the solution viscosity measured as a solution having a concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 60 mPa · s.
Next, 1,800 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 80 g of pyridine and 100 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone, whereby a solution containing 15% by weight of an imidized polymer (B-4) having an imidization ratio of about 80%. 1,200 g was obtained.
A small amount of this solution was collected, and γ-butyrolactone was added thereto, and the solution viscosity measured as a solution having a concentration of 10% by weight was 87 mPa · s.

Comparative Synthesis Example 5 (Synthesis Example 5 of Other Imidized Polymer)
112 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic anhydride and 54 g (0.50 mol) of p-phenylenediamine as diamine were added to N-methyl-2-pyrrolidone 1, A solution containing polyamic acid was obtained by dissolving in 260 g and reacting at room temperature for 6 hours. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a concentration of 10% by weight was 80 mPa · s.
Next, 600 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 136 g of pyridine and 105 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new γ-butyrolactone, and then concentrated to obtain a solution 1 containing 15% by weight of an imidized polymer (B-5) having an imidation ratio of about 93%. , 000 g was obtained.
A small amount of this solution was collected, and γ-butyrolactone was added to measure the solution viscosity as a solution having a concentration of 6.0% by weight of 24 mPa · s.

Comparative Synthesis Example 6 (Synthesis Example 6 of Other Imidized Polymer)
168 g (0.75 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro -2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157 g (0.25 mol) and p-phenylenediamine 43 g (0.40 mol) as diamine, 4, 80 g (0.40 mol) of 4′-diaminodiphenyl ether and 85 g (0.20 mol) of bis [4- (4-aminophenoxy) phenyl] sulfone were dissolved in 2,700 g of N-methyl-2-pyrrolidone, and at room temperature. By performing the reaction for 6 hours, a solution containing polyamic acid was obtained. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a concentration of 10% by weight was 85 mPa · s.
Next, 1,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 150 g of pyridine and 200 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new γ-butyrolactone, and then concentrated to obtain a solution 2 containing 15% by weight of an imidized polymer (B-6) having an imidization ratio of about 88%. , 600 g was obtained.

Comparative Synthesis Example 7 (Synthesis example 7 of other imidized polymer)
112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 76 g (0.50 mol) of 3,5-diaminobenzoic acid as diamine were added to N-methyl-2 -A solution containing polyamic acid was obtained by dissolving in 2,100 g of pyrrolidone and reacting at room temperature for 6 hours. A small amount of the obtained polyamic acid solution was collected and concentrated under reduced pressure, and the solution viscosity measured as a 10% by weight solution was 55 mPa · s.
Next, 1,000 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 150 g of pyridine and 200 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new γ-butyrolactone, and then concentrated to obtain a solution 1 containing 15% by weight of an imidized polymer (B-7) having an imidization ratio of about 85%. , 200 g was obtained.

Example 1
Γ-butyrolactone, N-methyl-2-pyrrolidone and butyl cellosolve were added to the solution containing the imidized polymer (A-1) obtained in Synthesis Example 1, and γ-butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve. In addition to the weight ratio of 71:17:12, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, which is an epoxy compound, is used as an adhesion improver. 2 parts by weight was added to 100 parts by weight of the imidized polymer contained in the solution to prepare a solution having a solid content concentration of 3.5 weights. After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering using a filter having a pore size of 1 μm.
Evaluation was performed as follows using this liquid crystal aligning agent.
<Manufacture and evaluation of liquid crystal display elements>
[Manufacture of liquid crystal display elements]
(1) Formation of film of liquid crystal aligning agent The liquid crystal aligning agent prepared above is rotated at 2,000 rpm using a spinner on a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm. The coating was applied under the condition of a rotation time of 20 seconds, and the solvent was removed by heating at 200 ° C. for 1 hour to form a film having a thickness of 0.08 μm.
(2) Rubbing treatment With a rubbing machine having a roll in which a rayon cloth is wound around the coating film formed above, a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.4 mm The film was rubbed to give a liquid crystal alignment film by imparting liquid crystal alignment ability to the coating film.
(3) Cleaning and drying of substrate with liquid crystal alignment film The substrate having the liquid crystal alignment film obtained above was subjected to ultrasonic cleaning in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C. for 10 minutes.
By repeating the operations (1) to (3), two substrates (a pair) having a liquid crystal alignment film were prepared.
(4) Injection of liquid crystal and adhesion of polarizing plate Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm was applied to each outer edge having the liquid crystal alignment film of the substrate having the pair of liquid crystal alignment films. After that, the liquid crystal alignment film surfaces were overlapped and pressed so as to face each other, and the adhesive was cured. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) having a positive dielectric anisotropy is filled between the liquid crystal inlet and the substrate, and then the liquid crystal inlet is filled with an acrylic photo-curing adhesive. The liquid crystal display element was manufactured by sealing and bonding a polarizing plate on both surfaces of the outer side of a board | substrate.

[Evaluation of liquid crystal display elements]
(1) Evaluation of liquid crystal alignment The liquid crystal display element manufactured above was observed using an optical microscope. At this time, no liquid leakage was observed. When the liquid crystal orientation was evaluated as “poor”, the liquid crystal orientation of this liquid crystal display element was “good”.
(2) Evaluation of voltage leakage property After applying a DC voltage of 10 V to the liquid crystal display element manufactured as described above for 1 second, the circuit is opened and static value is obtained, and the temporal change in transmitted light intensity transmitted from the liquid crystal cell Was measured to measure the time required to return to the initial transmittance state before voltage application. When this time was within 20 minutes, the charge leakage property was evaluated as “good”, and when it exceeded 20 minutes, the charge leakage property was evaluated as “bad”. The charging time was 15 minutes, and the voltage leakage property was “good”.
(3) Evaluation of heat resistance (heat stress test)
For the liquid crystal display device manufactured above, a voltage of 5 V was first applied with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from the application release was measured. The numerical value at this time was defined as the initial voltage holding ratio (VHR _BF ). After the VHR _BF measurement, the liquid crystal display element was put in an oven at 100 ° C., and thermal stress was applied for 1,000 hours. Next, the liquid crystal display element was allowed to stand at room temperature and cooled to room temperature, and then the voltage holding ratio (VHR _AF ) after application of thermal stress was measured in the same manner as described above.
From the VHR _BF and VHR _AF measured above, the rate of change of the voltage holding ratio before and after application of thermal stress was obtained, and when this rate of change was less than 5.0%, heat resistance was “good”, 5.0% or more When the heat resistance was evaluated as “impossible”, this liquid crystal display device had “good” heat resistance.

Example 2
<Preparation of liquid crystal aligning agent>
An amount corresponding to 100 parts by weight in terms of the imidized polymer (A-2) of the solution containing the imidized polymer (A-2) obtained in Synthesis Example 2 was taken, and N-methyl was added thereto. 2-pyrrolidone and butyl cellosolve are added so that the ratio of N-methyl-2-pyrrolidone: butyl cellosolve is 50:50 by weight, and N, N, N ′, N, which is an epoxy compound as an adhesion improver 2 parts by weight of '-tetraglycidyl-4,4'-diaminodiphenylmethane was added to prepare a solution having a solid concentration of 3.5% by weight. After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering using a filter having a pore size of 1 μm.
<Manufacture and evaluation of liquid crystal display elements>
In Example 1, nematic liquid crystal (MLC-2038, manufactured by Merck & Co., Inc.) having a negative value of dielectric anisotropy is used as the liquid crystal. And “(3) Washing and drying the substrate with a liquid crystal alignment film” was carried out in the same manner as in Example 1 except that the liquid crystal display element was manufactured and the liquid crystal alignment and heat resistance were evaluated. It is shown in Table 1.
Examples 3 and 4
As the imidized polymer, liquid crystal aligning agents were prepared in the same manner as in Example 2 except that the types shown in Table 1 were used in the amounts shown in Table 1, and liquid crystal display elements were produced and evaluated. The results are shown in Table 1.

Example 5 (Reference Example)
<Preparation of liquid crystal aligning agent>
An amount corresponding to 100 parts by weight in terms of the imidized polymer (A-5) of the solution containing the imidized polymer (A-5) obtained in Synthesis Example 5 was taken, and this was an adhesion improver. 10 parts by weight of epoxy compound N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane and methyl 3- [2- (3-trimethoxysilylpropylamino) which is a functional silane compound ) Ethylamino] propionate, and γ-butyrolactone and butyl cellosolve are added so that the γ-butyrolactone: butyl cellosolve ratio is 80:20 by weight to obtain a solid concentration of 3.5% by weight. It was set as the solution. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 1 μm.
<Manufacture and evaluation of liquid crystal display elements>
In Example 1 above, a liquid crystal display element was produced in the same manner as in Example 1 except that nematic liquid crystal (Merck, MLC-2019) having a positive dielectric anisotropy was used as the liquid crystal. The liquid crystal orientation and heat resistance were evaluated. The results are shown in Table 1.
Examples 6-9 (all are reference examples)
As the imidized polymer, a liquid crystal aligning agent was prepared in the same manner as in Example 5 except that the types shown in Table 1 were used in the amounts shown in Table 1, and liquid crystal display elements were produced and evaluated. The results are shown in Table 1.

Comparative Example 1
As the imidized polymer, a liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the types shown in Table 1 were used in the amounts shown in Table 1, and a liquid crystal display device was produced and evaluated. The results are shown in Table 1.
Comparative Examples 2-4
As the imidized polymer, liquid crystal aligning agents were prepared in the same manner as in Example 2 except that the types shown in Table 1 were used in the amounts shown in Table 1, and liquid crystal display elements were produced and evaluated. The results are shown in Table 1.
Comparative Examples 5-7
As the imidized polymer, liquid crystal aligning agents were prepared in the same manner as in Example 5 except that the types shown in Table 1 were used in the amounts shown in Table 1, and liquid crystal display elements were produced and evaluated. The results are shown in Table 1.

In addition, the abbreviation in the “type” column of the adhesion improver in Table 1 has the following meaning.
[Epoxy compound]
GAPM: N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane [functional silane compound]
MSPP: methyl 3- [2- (3-trimethoxysilylpropylamino) ethylamino] propionate Further, the descriptions in the “Liquid Crystal Name” column have the following meanings, respectively.
6221: MLC-6221 (trade name, manufactured by Merck & Co., Inc.)
2038: MLC-2038 (trade name, manufactured by Merck & Co., Inc.)
2019: MLC-2019 (trade name, manufactured by Merck & Co., Inc.)

Claims (8)

Tetracarboxylic dianhydride;
The following formula (A)

(In formula (A), “*” indicates a bond, respectively.)
A compound having a structure represented by: and two amino groups ,
The following formula (D-III)

(In the formula (D-III), R ⁹ represents —O—, —COO—, —OCO—, —NHCO—, —CONH— or —CO—, and R ¹⁰ represents a steroid skeleton, a trifluoromethylphenyl group, A monovalent organic group having a skeleton or a group selected from a trifluoromethoxyphenyl group and a fluorophenyl group, or an alkyl group having 6 to 30 carbon atoms, R ¹¹ is an alkyl group having 1 to 4 carbon atoms, and a3 Is an integer from 0 to 3.)
A compound represented by
at least selected from the group consisting of p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether and bis [4- (4-aminophenoxy) phenyl] sulfone. A liquid crystal aligning agent comprising an imidized polymer obtained by dehydrating and ring-closing a polyamic acid obtained by a reaction with a diamine containing one kind . The structure represented by the above formula (A) and the compound having two amino groups are represented by the following formula (A-1)

(In Formula (A-1), U ¹ and U ² are each independently an alkylene group having 2 to 5 carbon atoms or a divalent alicyclic group having 4 to 6 carbon atoms, or 6 to 6 members. (It is a divalent organic group containing 10 aromatic rings.)
The liquid crystal aligning agent of Claim 1 which is a compound represented by these.   The liquid crystal aligning agent of Claim 1 or 2 whose usage-ratio of the structure represented by the said Formula (A) and the compound which has two amino groups is 1 mol% or more with respect to all the diamines. The liquid crystal according to claim 1, wherein R ⁹ in the formula (D-III) is —O— or —COO—, and R ¹⁰ is a monovalent organic group having a steroid skeleton. Alignment agent. Tetracarboxylic dianhydride is 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo- The liquid crystal according to any one of claims 1 to 4 , comprising at least one selected from the group consisting of 3-furanyl) -naphtho [1,2-c] furan-1,3-dione. Alignment agent. The liquid crystal aligning agent as described in any one of Claims 1-5 whose imidation ratio of an imidation polymer is 30% or more. The liquid crystal aligning agent of Claim 6 whose imidation ratio of an imidation polymer is 50% or more. Characterized by comprising a liquid crystal alignment film formed from the liquid crystal alignment agent according to any one of claims 1 to 7 the liquid crystal display device.