JP5900344B2 - Liquid crystal aligning agent suitable for photo-alignment treatment method, and liquid crystal aligning film using the same - Google Patents

Description

  The present invention relates to a liquid crystal alignment agent for producing a liquid crystal alignment film and a liquid crystal alignment film obtained from the liquid crystal alignment agent. More specifically, a photo-alignment treatment method that replaces the rubbing treatment, that is, a liquid crystal alignment agent suitable for forming a liquid crystal alignment film capable of imparting liquid crystal alignment ability by irradiation with polarized ultraviolet rays, and the liquid crystal alignment agent. The liquid crystal alignment film is obtained.

In a liquid crystal display element used for a liquid crystal television, a liquid crystal display, and the like, a liquid crystal alignment film for controlling the alignment state of liquid crystals is usually provided in the element.
At present, according to the most widespread industrial method, the liquid crystal alignment film is made of a polyamic acid formed on an electrode substrate and / or a surface of a film made of polyimide obtained by imidizing this with cotton, nylon, It is produced by carrying out a so-called rubbing process that rubs in one direction with a cloth such as polyester.

  The method of rubbing the film surface in the alignment process of the liquid crystal alignment film is an industrially useful method that is simple and excellent in productivity. However, demands for higher performance, higher definition, and larger size of liquid crystal display elements are increasing, and in the case of rubbing treatment, the surface of the alignment film generated by the rubbing, dust generation, the influence of mechanical force and static electricity In addition, various problems such as non-uniformity in the orientation processing surface have been clarified.

  As a method for replacing the rubbing treatment, a photo-alignment method for imparting liquid crystal alignment ability by irradiating polarized ultraviolet rays is known. The liquid crystal alignment treatment by the photo-alignment method has been proposed mechanically using a photoisomerization reaction, using a photocrosslinking reaction, using a photolysis reaction, etc. (see Non-Patent Document 1). . Patent Document 1 proposes that a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain is used for the photo-alignment method. When used for an alignment film for photo-alignment using polyimide, its usefulness is expected because it has higher heat resistance than others.

  The photo-alignment method has an advantage that it can be produced by a simple manufacturing process industrially as a rubbing-less alignment treatment method. In addition, in a liquid crystal display element of an IPS driving method or a fringe field switching (hereinafter referred to as FFS) driving method. By using the liquid crystal alignment film obtained by the above-mentioned photo-alignment method, the liquid crystal display element performance can be expected to improve the contrast and viewing angle characteristics of the liquid crystal display element compared to the liquid crystal alignment film obtained by the rubbing treatment method. Therefore, it has attracted attention as a promising liquid crystal alignment method.

  The liquid crystal alignment film used in the liquid crystal display element of the IPS driving method or the FFS driving method is generated in the liquid crystal display element of the IPS driving method or the FFS driving method in addition to the basic characteristics such as excellent liquid crystal alignment property and electrical characteristics. There is a need for such characteristics as suppressing afterimages due to AC driving and fast relaxation of residual charges accumulated by DC voltage. However, the liquid crystal alignment film obtained by the photo-alignment method has insufficient liquid crystal alignment control power, electrical characteristics as a liquid crystal display element, and stability of these characteristics, and it has been difficult to satisfy the above characteristics.

JP-A-9-297313

"Liquid crystal alignment film" Kidowaki, Ichimura Functional Materials November 1997, Vol. 17 No. 11 pages 13-22

  The present invention provides a liquid crystal alignment film that suppresses an afterimage caused by alternating current drive generated in a liquid crystal display element of an IPS drive method or an FFS drive method, and that quickly relaxes residual charges accumulated by a direct current voltage, and the liquid crystal alignment film It aims at providing the liquid crystal aligning agent suitable for the photo-alignment processing method for this.

In order to achieve the above object, the inventor of the present invention has a component with excellent liquid crystal alignment and a strong alignment regulating force of liquid crystal (hereinafter also referred to as a liquid crystal alignment component) and a component that quickly relaxes residual charges accumulated by a DC voltage. Attention was focused on a liquid crystal aligning agent blended with (hereinafter also referred to as a charge relaxation component).
However, such a liquid crystal aligning agent does not necessarily solve the above problems. That is, the liquid crystal alignment film obtained from the liquid crystal aligning agent containing the above two components generates an afterimage generated by AC driving even if the residual charge accumulated by the DC voltage is quickly relaxed. The characteristics are not compatible.

  The present inventor has intensively studied to achieve the above object. As a liquid crystal alignment component, a tetracarboxylic dianhydride having a specific structure having a cyclobutane skeleton, p-phenylenediamines, and hydrogen by heating are used. At least one selected from a polyamic acid composed of a polyamic acid obtained by a reaction with a diamine compound containing a specific diamine having a diamine having an amino group protected by a thermal leaving group to be replaced, and an imidized polymer thereof And a polyamic acid comprising a polyamic acid obtained by a reaction of a tetracarboxylic dianhydride as a charge relaxation component and a diamine compound containing a diamine having an aromatic heterocyclic ring having a nitrogen atom. Using at least one polymer selected from acids and imidized polymers thereof It found that it is possible to achieve the above object by a liquid crystal aligning agent was allowed containing these components.

Thus, the present invention has the following gist.
1. The liquid crystal aligning agent characterized by including the following (A) component, (B) component, and an organic solvent.
Component (A): at least one selected from the group consisting of a tetracarboxylic dianhydride represented by the following formula (1) and a structure represented by the following formulas (D-1) and (D-2) The at least 1 sort (s) of polymer chosen from the polyamic acid obtained from diamine and the diamine represented by following formula (2), and its imidized polymer.

（式（１）において、Ｒ_１、Ｒ_２、Ｒ_３、及びＲ_４はそれぞれ独立して、水素原子、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基若しくはアルキニル基、又はフェニル基であり、同一でも異なっていてもよい。）
（式（２）において、Ａ_１は単結合、−Ｏ−、−ＮＱ^１−、−ＣＯＮＱ^１−、−ＮＱ^１ＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−からなる群より選ばれる少なくとも１種類の２価の有機基、又は炭素数１〜３のアルキレン基であり、Ｑ^１は水素原子、又は炭素数１〜３のアルキル基であり、Ｒ_５は水素原子、又は炭素数１〜８の２価の有機基である。）

In (Equation _{(1), R 1, R} 2, R 3, and _{R 4} are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, alkenyl or alkynyl group having 2 to 6 carbon atoms, or A phenyl group, which may be the same or different.)
(In formula (2), _{A 1} represents a single ^{bond, -O -, - NQ 1 -} , - CONQ 1 -, - NQ 1 CO -, - CH 2 O -, - OCO- least one selected from the group consisting of A divalent organic group of a kind, or an alkylene group having 1 to 3 carbon atoms, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₅ is a hydrogen atom or 1 to 8 carbon atoms. Divalent organic group.)

（式（Ｄ−２）において、Ｚ_１は単結合、エステル結合、アミド結合、チオエステル結合、又は炭素数２〜６の２価の有機基である。）
（Ｂ）成分：テトラカルボン酸二無水物と、下記式（３）で表されるジアミンを含有するジアミン化合物から得られるポリアミック酸及びそのイミド化重合体から選ばれる少なくとも１種の重合体。

(In Formula (D-2), Z ₁ is a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 6 carbon atoms.)
Component (B): at least one polymer selected from a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine compound containing a diamine represented by the following formula (3) and an imidized polymer thereof.

（式（３）において、Ｂ_１は−Ｏ−、−ＮＱ^２−、−ＣＯＮＱ^２−、−ＮＱ^２ＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−からなる群より選ばれる少なくとも１種類の２価の有機基であり、Ｑ^２は水素原子又は炭素数１〜３のアルキル基であり、Ｂ_２は単結合、又は炭素数１〜４のアルキレン基であり、Ｂ_３は窒素原子含有複素環であり、ｎは１〜４の整数である。）

(In the formula (3), _{B 1} is ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - CH 2 O -, - at least one member selected from the group consisting of OCO- 2 Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, B ₂ is a single bond or an alkylene group having 1 to 4 carbon atoms, and B ₃ is a nitrogen atom-containing heterocyclic ring. And n is an integer of 1 to 4.)

2. The content ratio of the component (A) and the component (B) is 3/7 to 7/3 in mass ratio (A / B), and the content of the component (A) and the component (B) is ( The liquid crystal aligning agent of said 1 which is 1 to 10 weight% with respect to the total amount of A) component, (B) component, and an organic solvent.
3. (A) component tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride The liquid crystal aligning agent in any one of said 1 or 2 which is at least 1 type of tetracarboxylic dianhydride chosen from.
4). The liquid crystal aligning agent in any one of said 1-3 whose tetracarboxylic dianhydride of (A) component is 1,3-dimethyl- 1,2,3,4-cyclobutane tetracarboxylic dianhydride.
5. (A) Liquid crystal alignment in any one of said 1-4 whose diamine is a diamine which contains 5-30 mol% of diamine represented by the said Formula (2) with respect to all the diamines of (A) component. Agent.

6). The diamine represented by the above formula (2) contained in the component (A) is at least one selected from formulas (DA-1) to (DA-3) described later, according to any one of the above 1 to 5. Liquid crystal aligning agent.
7). (B) Liquid crystal aligning agent in any one of said 1-6 whose diamine is a diamine which contains 30-100 mol% of diamine represented by said Formula (3) with respect to all the diamines of (B) component. .
8). The diamine represented by the formula (3) contained in the component (B) is at least one selected from formulas (DB-1) to (DB-6) to be described later, Liquid crystal aligning agent.
9. (B) The tetracarboxylic dianhydride of the component is a structure represented by the following formula (4), and in the formula, the structure of X ₁ is at least one selected from the following structures: The liquid crystal aligning agent in any one.

10. (B) The tetracarboxylic dianhydride as the component is at least one selected from 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride The liquid crystal aligning agent in any one of said 1-9 which is 50-100 mol% with respect to all the tetracarboxylic dianhydrides of (B) component.
11. The liquid crystal aligning agent in any one of said 1-10 whose tetracarboxylic dianhydride of (B) component is 1,2,3,4-cyclobutane tetracarboxylic dianhydride.
12 (B) Liquid crystal in any one of said 1-11 which is diamine containing the carboxylic acid containing diamine represented by following formula (5) other than the diamine represented by said formula (3). Alignment agent.

（式（５）において、Ｂ_３は、Ｂ_１と同様であり、Ｂ_４は単結合、又は炭素数１〜４のアルキレン基であり、ｍは１〜４の整数である。）

(In the formula (5), _{B 3} is the same as _{B 1, B 4} is a single bond, or an alkylene group having 1 to 4 carbon atoms, m is an integer from 1 to 4.)

13. (B) The diamine of a component contains the diamine represented by the said Formula (3) and the diamine represented by the said Formula (5), The total amount is 40 with respect to all the diamines of (B) component. The liquid crystal aligning agent in any one of said 1-12 which is -100 mol%.
14 14. The liquid crystal aligning agent according to 1 to 13, wherein the diamine represented by the formula (5) is at least one selected from 3,5-diaminobenzoic acid and 2,5-diaminobenzoic acid.
15. The manufacturing method of the liquid crystal aligning film which apply | coats and bakes the liquid crystal aligning agent in any one of said 1-14.
16. The manufacturing method of the liquid crystal aligning film which apply | coats and bakes the liquid crystal aligning agent in any one of said 1-14, and also irradiates the polarized radiation.

  According to the present invention, a liquid crystal alignment film that suppresses an afterimage due to alternating current drive generated in a liquid crystal display element of an IPS drive method or an FFS drive method, and quickly relaxes residual charges accumulated by a direct current voltage, and the liquid crystal alignment film A novel liquid crystal aligning agent suitable for use in the photo-alignment treatment method for obtaining the above is provided.

In the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention, the reason why the above effect is obtained is not necessarily clear, but is considered as follows.
In general, when two components having different surface energies are blended, it is known that a component having a low surface energy is unevenly distributed on the film surface, and a component having a high surface energy is unevenly distributed in the film or at the interface with the substrate. Since the component (A) of the liquid crystal aligning agent of the present invention uses a low-polarity t-butyl group, it is a polyamic acid having a low surface energy and becomes a liquid crystal aligning component. On the other hand, since the charge relaxation component has a nitrogen-containing aromatic heterocycle such as a pyridine ring, it becomes a polyamic acid having a surface energy higher than that of the liquid crystal alignment component. Therefore, the liquid crystal alignment film in which the liquid crystal alignment component is unevenly distributed on the film surface and the charge relaxation component is unevenly distributed inside the film and at the interface with the substrate is obtained by applying and baking the liquid crystal aligning agent of the present invention. When a low-polarity substituent such as a t-butyl group is not included, the internal structure of the film does not have the structure as described above, and a charge relaxation component exists on the film surface. Deteriorates and an afterimage due to AC driving occurs.
However, a bulky structure such as a t-butyl group deteriorates the liquid crystal alignment because the interaction between the liquid crystal and the alignment film is inhibited, but the t-butyl group contained in the liquid crystal alignment component of the present invention is Since the -butyl group is replaced with a hydrogen atom by heating in the subsequent baking process, it no longer exists in the obtained liquid crystal alignment film. For this reason, the obtained liquid crystal aligning film has excellent liquid crystal aligning properties as in the case of using a polyamic acid that does not have a bulky structure such as a t-butyl group.
Thus, in the surface layer of the liquid crystal alignment film obtained in the present invention, the liquid crystal alignment component having excellent liquid crystal alignment is unevenly distributed, and the charge relaxation component that rapidly relaxes the residual charge accumulated by the DC voltage is contained in the film and the electrode. Since it exists at the interface, it is considered to have excellent characteristics.

<(A) component>
(A) component contained in the liquid crystal aligning agent of this invention is the tetracarboxylic dianhydride which has a cyclobutane ring represented by following formula (1), and following formula (D-1) and (D-2). A diamine having at least one highly linear diamine selected from the group consisting of the structures represented by the formula and a t-butoxycarbonyl group which is a protecting group for an amino group that is replaced by a hydrogen atom by heating represented by the following formula (2) And at least one polymer selected from a polyamic acid obtained by reaction and an imidized polymer thereof.

上記式（１）において、Ｒ_１、Ｒ_２、Ｒ_３、及びＲ_４はそれぞれ独立して、水素原子、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基若しくはアルキニル基、又はフェニル基であり、同一でも異なっていてもよい。
Ｒ_１、Ｒ_２、Ｒ_３、及びＲ_４が、立体的に嵩高い構造である場合、液晶配向性を低下させてしまう。よって、Ｒ_１、Ｒ_２、Ｒ_３，及びＲ_４は、水素原子、メチル基又はエチル基が好ましく、水素原子、又はメチル基がより好ましい。

In the above formula (1), R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group or alkynyl group having 2 to 6 carbon atoms, or It is a phenyl group and may be the same or different.
When R ₁ , R ₂ , R ₃ , and R ₄ have a three-dimensionally bulky structure, the liquid crystal orientation is deteriorated. Therefore, R ₁ , R ₂ , R ₃ , and R ₄ are preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.

  Specific examples of the tetracarboxylic dianhydride having a cyclobutane ring represented by the above formula (1) include the following formulas (1-1) to (1-5). From the viewpoint of liquid crystal orientation, (1-1) and (1-2) are more preferable, and (1-2) is more preferable.

上記式（Ｄ−２）において、Ｚ_１は単結合、エステル結合、アミド結合、チオエステル結合、又は炭素数２〜４の２価の有機基である。
Ｚ_１において、エステル結合としては、−Ｃ（Ｏ）Ｏ−、又は−ＯＣ（Ｏ）−で表される。アミド結合としては、−Ｃ（Ｏ）ＮＨ−、又は、−Ｃ（Ｏ）ＮＲ−、−ＮＨＣ（Ｏ）−、−ＮＲＣ（Ｏ）−で表される構造を示すことができる。Ｒは炭素数１〜４のアルキル基である。
上記アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ｔ−ブチル基などが挙げられる。
Ｚ_１が炭素数２〜４の有機基である場合、下記式（Ｄ２）の構造で表すことができる。

In the above formula (D-2), Z ₁ is a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 4 carbon atoms.
In Z _1, the ester bond, -C (O) O-, or -OC (O) - represented by. As an amide bond, the structure represented by -C (O) NH- or -C (O) NR-, -NHC (O)-, -NRC (O)-can be shown. R is an alkyl group having 1 to 4 carbon atoms.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a t-butyl group.
When Z ₁ is an organic group having 2 to 4 carbon atoms, it can be represented by the structure of the following formula (D2).

上記式（Ｄ−２）における、Ｚ₄、Ｚ_５はそれぞれ独立して、単結合、又は、−Ｏ−、−Ｓ−、−ＮＲ_１１−、エステル結合、アミド結合、チオエステル結合、ウレア結合、カーボネート結合、カルバメート結合である。Ｒ_１１の水素原子、メチル基である。
Ｚ_４、Ｚ_５、Ｚ_６において、エステル結合、アミド結合、及び、チオエステル結合については、前記のエステル結合、アミド結合、及び、チオエステル結合の同様の構造を示すことができる。
ウレア結合としては、−ＮＨ−Ｃ（Ｏ）ＮＨ−、又は−ＮＲ−Ｃ（Ｏ）ＮＲ−で表される構造を示すことができる。Ｒは炭素数１〜３のアルキル基であり、前記のアルキル基と同様の例を挙げることができる。
カーボネート結合としては、−Ｏ−Ｃ（Ｏ）−Ｏ−で表される構造を示すことができる。
カルバメート結合としては、−ＮＨ−Ｃ（Ｏ）−Ｏ−、−Ｏ−Ｃ（Ｏ）−ＮＨ−、−ＮＲ−Ｃ（Ｏ）−Ｏ−、又は−Ｏ−Ｃ（Ｏ）−ＮＲ−で表される構造を示すことができる。Ｒは炭素数１〜４のアルキル基であり、前記のアルキル基と同様の例を挙げることができる。
式（Ｄ−２）中のＲ_６は、それぞれ独立して単結合、又は炭素数１〜４のアルキレン基、アルケニレン基、アルキニレン基、アリーレン基、及びこれらを組み合わせた基から選ばれる構造である。
上記アルキレン基としては、メチレン基、１，１−エチレン基、１，２−エチレン基、１，２−プロピレン基、１，３−プロピレン基、１，４−ブチレン基、１，２−ブチレン基などが挙げられる。
アルケニレン基としては、１，１−エテニレン基、１，２−エテニレン基、１，２−エテニレンメチレン基、１−メチル−１，２−エテニレン基、１，２−エテニレン−１，１−エチレン基、１，２−エテニレン−１，２−エチレン基などが挙げられる。
アルキニレン基としては、エチニレン基、エチニレンメチレン基、エチニレン−１，１−エチレン基、エチニレン−１，２−エチレン基などが挙げられる。
アリーレン基としては、１，２−フェニレン基、１，３−フェニレン基、１，４−フェニレン基などが挙げられる。
ジアミンの構造が、直線性が高い構造や剛直な構造である場合、良好な液晶配向性を有する液晶配向膜が得られるため、Ｚ_１の構造としては、単結合、又は下記式（Ａ１−１）〜（Ａ１−１８）の構造がより好ましい。

In the above formula (D-2), Z ₄ and Z ₅ are each independently a single bond, or —O—, —S—, —NR ₁₁ —, an ester bond, an amide bond, a thioester bond, a urea bond, Carbonate bond and carbamate bond. R _{11 is} a hydrogen atom or a methyl group.
In Z ₄ , Z ₅ , and Z ₆ , the ester bond, amide bond, and thioester bond can have the same structures as the ester bond, amide bond, and thioester bond described above.
As a urea bond, the structure represented by -NH-C (O) NH- or -NR-C (O) NR- can be shown. R is an alkyl group having 1 to 3 carbon atoms, and examples similar to the above alkyl group can be given.
As a carbonate bond, the structure represented by -O-C (O) -O- can be shown.
The carbamate bond is -NH-C (O) -O-, -O-C (O) -NH-, -NR-C (O) -O-, or -O-C (O) -NR-. The structure represented can be shown. R is an alkyl group having 1 to 4 carbon atoms, and examples similar to the above alkyl group can be given.
R ₆ in the formula (D-2) is a structure independently selected from a single bond or a C 1-4 alkylene group, an alkenylene group, an alkynylene group, an arylene group, and a combination thereof. .
Examples of the alkylene group include methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, and 1,2-butylene group. Etc.
Alkenylene groups include 1,1-ethenylene group, 1,2-ethenylene group, 1,2-ethenylenemethylene group, 1-methyl-1,2-ethenylene group, 1,2-ethenylene-1,1-ethylene Group, 1,2-ethenylene-1,2-ethylene group and the like.
Examples of the alkynylene group include ethynylene group, ethynylene methylene group, ethynylene-1,1-ethylene group, ethynylene-1,2-ethylene group and the like.
Examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.
When the structure of diamine is a structure with high linearity or a rigid structure, a liquid crystal alignment film having good liquid crystal alignment can be obtained. Therefore, as the structure of Z ₁ , a single bond or the following formula (A1-1) ) To (A1-18) are more preferred.

ジアミンの構造が直線性が高い構造や剛直な構造であるほど、液晶配向性に優れた液晶配向膜が得られるため、下記式（Ｄ−１）及び（Ｄ−２）で表される構造からなる群から選ばれる少なくとも1種類のジアミンとしては、上記式（Ｄ−１）で表されるジアミン、又は下記式（Ｄ２−１）〜（Ｄ２−７）で表されるジアミンがより好ましく、式（Ｄ−１）で表されるジアミンが特に好ましい。

Since the liquid crystal alignment film having excellent liquid crystal alignment is obtained as the structure of the diamine has a higher linearity or a rigid structure, the structure represented by the following formulas (D-1) and (D-2) The at least one diamine selected from the group consisting of diamines represented by the above formula (D-1) or diamines represented by the following formulas (D2-1) to (D2-7) is more preferred. The diamine represented by (D-1) is particularly preferable.

In the above formula (2), _{A 1} is a single bond or ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - at least selected from _CH 2 O- and the group consisting of -OCO- One type of divalent organic group or an alkylene group having 1 to 3 carbon atoms, wherein Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ₅ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.
If Q ¹ is a bulky structure, thereby reducing the liquid crystal alignment property. Therefore, Q ¹ is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
A ₁ is preferably a single bond or an alkylene group having 1 to 3 carbon atoms, more preferably a single bond, a methylene group or an ethylene group.
In R ₅ , specific examples of the monovalent organic group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, Alkyl group such as bicyclohexyl group; vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclo An alkenyl group such as a pentenyl group and a cyclohexenyl group, an ethynyl group, a 1-propynyl group and a 2-propynyl group; an aryl group such as a phenyl group; or the following formulas (R-1) to (R-2) Examples thereof include a structure having a thermally desorbable group that replaces a hydrogen atom by heating.
Even in R ₅ , the liquid crystal orientation is deteriorated if the structure is bulky like Q ¹ . Therefore, R ₅ is preferably (R-1) or (R-2) having a hydrogen atom, a methyl group, an ethyl group, and a thermally leaving group, and is preferably a hydrogen atom, a methyl group, (R-1) or (R-2) is more preferable.

  If the specific example of the diamine represented by the said Formula (2) is given, the diamine of the following formula (DA-1)-(DA-3) can be mentioned. From the viewpoint of liquid crystal orientation, (DA-1) or (DA-2) is preferable, and (DA-1) is more preferable.

本発明の液晶配向剤に含有する（Ａ）成分は、使用されるジアミン化合物中のｐ−フェニレンジアミンの比率が高いほど、液晶配向性が良好で、液晶分子との相互作用も強いため、交流駆動により発生する残像を低減することができる。一方、ジアミン化合物中の上記式（２）で表されるジアミンの比率が高いほど、（Ａ）成分の表面エネルギーが低くなり、（Ａ）成分が、膜表面に偏在しやすくなる。
上記のような観点から、本発明に使用される（Ａ）成分を形成するｐ−フェニレンジアミンの含有量は、ジアミン化合物の７０〜９５ｍｏｌ％が好ましく、８０〜９５ｍｏｌ％がより好ましく、９０〜９５ｍｏｌ％がさらに好ましい。一方、上記式（２）で表されるジアミンの含有量は、ジアミン化合物の３０〜５ｍｏｌ％が好ましく、２０〜５ｍｏｌ％がより好ましく、１０〜５ｍｏｌ％がさらに好ましい。

The component (A) contained in the liquid crystal aligning agent of the present invention has a higher liquid crystal alignment property and stronger interaction with liquid crystal molecules as the ratio of p-phenylenediamine in the diamine compound used is higher. Afterimages generated by driving can be reduced. On the other hand, the higher the ratio of the diamine represented by the above formula (2) in the diamine compound, the lower the surface energy of the (A) component, and the (A) component tends to be unevenly distributed on the film surface.
From the above viewpoint, the content of the p-phenylenediamine forming the component (A) used in the present invention is preferably 70 to 95 mol%, more preferably 80 to 95 mol%, and 90 to 95 mol% of the diamine compound. % Is more preferable. On the other hand, the content of the diamine represented by the formula (2) is preferably 30 to 5 mol%, more preferably 20 to 5 mol%, and still more preferably 10 to 5 mol% of the diamine compound.

<(B) component>
The (B) component contained in the liquid crystal aligning agent of this invention is obtained from the diamine compound containing the tetracarboxylic dianhydride represented by following formula (6), and the diamine represented by following formula (3). It is at least one polymer selected from polyamic acids and imidized polymers thereof.

In the formula (3), _{B 1} is ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - CH 2 O-, and at least one 2 selected from the group consisting of -OCO- Here, Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Q ² includes the same structure as Q ¹ , including preferred examples. B ₂ is a single bond or an alkylene group having 1 to 4 carbon atoms, B ₃ is a nitrogen atom-containing heterocyclic ring, and n is an integer of 1 to 4.
The B _1, it is possible to increase the surface energy of the component (B) is preferably highly polar ^{structure, -O -, - NQ 2 -} , - CONQ 2 -, and -OCO- are more preferred. B ₂ is preferably an alkylene group having 1 to 4 carbon atoms, preferably 1 or 2, for ease of synthesis.
Specific examples of the nitrogen atom-containing aromatic heterocycle of B ₃ include pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring. Is mentioned. From the viewpoint of availability of raw materials, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring is more preferable, and an imidazole ring, a pyridine ring, or a pyrimidine ring is more preferable.
If the specific example of the diamine which has a nitrogen atom containing aromatic heterocyclic ring represented by the said Formula (3) is given, following formula (DB-1)-(DB-6) will be mentioned.
As content of the diamine which has a nitrogen atom containing aromatic heterocyclic ring represented by the said Formula (3), 30-100 mol% of a diamine compound is preferable, More preferably, 40-100 mol%, More preferably, 50-100 mol %.

In the above formula (6), X is a tetravalent organic group, and its structure is not particularly limited. If a specific example is given, the structure of following formula (X-1)-(X-46) will be mentioned. From the viewpoint of availability of the compound, the structure of X is X-1, X-2. X-3, X-4, X-5, X-6, X-8, X-16, X-17, X-19, X-21, X-25, X-26, X-27, X- 28, X-32, or X-46 is preferred. In order to improve the transparency of the obtained liquid crystal alignment film, it is preferable to use a tetracarboxylic dianhydride having an aliphatic or aliphatic ring structure. As the structure of X, X-1, X-2, or X -25 is more preferable, and X-1 is more preferable from the viewpoint of reactivity with diamine.
In the tetracarboxylic dianhydride of the component (B), when X in the formula (6) includes a tetracarboxylic dianhydride represented by X-1, X-2, or X-25, It is preferable to contain 50 to 100 mol% of tetracarboxylic dianhydride. More preferably, it is 70-100 mol%, More preferably, it is 80-100 mol%.

本発明の液晶配向剤に含有される（Ｂ）成分は、上記式（３）で表されるジアミン以外に、下記式（５）で表されるカルボン酸を有するジアミン化合物を用いることで、液晶配向膜とした場合に、直流電圧による蓄積した残留電荷の緩和をさらに早くすることができる。また、下記式（５）で表されるジアミン化合物を用いることにより、（Ｂ）成分の表面エネルギーがさらに高くなり、（Ａ）成分が膜表面により偏在し、（Ｂ）成分が膜内部及び基板界面により偏在させることができる。

(B) component contained in the liquid crystal aligning agent of this invention uses a diamine compound which has carboxylic acid represented by following formula (5) other than the diamine represented by the said Formula (3), and is liquid crystal. When the alignment film is used, the residual charge accumulated by the DC voltage can be further relaxed. Moreover, by using the diamine compound represented by the following formula (5), the surface energy of the component (B) is further increased, the component (A) is unevenly distributed on the film surface, and the component (B) is contained in the film and the substrate. It can be unevenly distributed by the interface.

In the formula (5), _{B 3} is the same definition as _{B 1} in the formula (3), a single ^{bond, -O -, - NQ 3 -} , - CONQ 3 -, - NQ 3 CO -, - CH 2 It is at least one kind of divalent organic group selected from the group consisting of O- and -OCO-. Here, Q ³ includes the same structure as Q ¹ including preferred examples. B ₄ is a single bond or an alkylene group having 1 to 4 carbon atoms, and m is an integer of 1 to 4.
The B _3, (B) it is possible to increase the surface energy of the component, preferably highly polar structure, a single bond, -CONQ ² -, or -OCO- are more preferred.
If the specific example of the diamine which has carboxylic acid represented by the said Formula (5) is given, 3, 5- diamino benzoic acid or 2, 5- diamino benzoic acid will be mentioned.
(B) As a diamine which forms a component, it is preferable to contain both the diamine represented by the said Formula (3) and the diamine represented by the said Formula (5). When both the diamine represented by the above formula (3) and the diamine represented by the above formula (5) are contained, the total content of these diamines is preferably 40 to 100 mol% with respect to the total diamines, 50-100 mol% is more preferable, and 60-100 mol% is further more preferable.
As the diamine component of the component (B), the diamine other than the above formula (3) and the above formula (5) may include a diamine represented by the following formula (7). In the formula, Y ₁ is a divalent organic group, and its structure is not particularly limited. If Y ₁ Specific examples include the following structures following formula (Y-1) ~ (Y -75).

In order to improve the solubility of the component (B) of the liquid crystal aligning agent of the present invention in an organic solvent, the structure of Y ₁ is Y-8, Y-20, Y-21, Y-22, Y-28, Y -29 and Y-30.
If the (B) component pomic acid is unevenly distributed on the film surface, the orientation of the liquid crystal may be hindered. Therefore, the surface energy of the (B) component is increased, and the (B) component is used inside the film and at the substrate interface. For the purpose of uneven distribution, it is preferable to use a diamine having a highly polar substituent. As the diamine having a highly polar substituent, a diamine containing a secondary or tertiary amino group, hydroxyl group, amide group or urea group is preferable. Therefore, as the _{Y 1} in the formula (7), Y-19, Y-31, Y-40, Y-45, Y-49~Y-51, or Y-61 are more preferred.

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

<Production method of polyimide>
The imidized polymer (polyimide) of the polyamic acid used in the present invention can be produced by imidizing the polyamic acid.
When manufacturing a polyimide from a polyamic acid, chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction with a diamine component and tetracarboxylic dianhydride is simple. Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not easily decrease during the imidization process.
Chemical imidation can be performed by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
The temperature at which the imidization reaction is performed is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amic acid group. Is double. The imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.
In the solution after the imidation reaction of polyamic acid ester or polyamic acid, the added catalyst and the like remain, so the obtained imidized polymer is recovered by the means described below, and redissolved in an organic solvent. Thus, the liquid crystal aligning agent of the present invention is preferable.
The polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
The poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention contains (A) component, (B) component, and the organic solvent, and has the form of the solution in which (A) component and (B) component were melt | dissolved in the organic solvent.
The molecular weight of the polyamic acid of component (A) and component (B) is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 in terms of weight average molecular weight. ~ 100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
In the liquid crystal aligning agent of the present invention, the ratio of the component (A) to the component (B) is preferably 3/7 to 7/3 in terms of the mass ratio of ((A) component / (B) component). Such a ratio is more preferably 4/6 to 6/4. By setting the ratio within this range, it is preferable to obtain a liquid crystal alignment film in which afterimages due to AC driving are suppressed and the residual charges accumulated by DC voltage are quickly relaxed.

  As long as the liquid crystal aligning agent of this invention has the form of the solution in which (A) component and (B) component were melt | dissolved in the organic solvent, the manufacturing method is not ask | required. For example, a method of mixing the powder of the component (A) and the component (B) and dissolving in an organic solvent, a method of mixing the powder of the component (A) and the solution of the component (B), and a solution of the component (A) ( There are a method of mixing the powder of component B) and a method of mixing the solution of component (A) and component (B). Since a uniform mixed solution can be obtained even when the good solvent in which the component (A) and the component (B) are dissolved is different, a method of mixing the solution of the component (A) and the component (B) is more preferable.

The polymer concentration of the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but it is 1% by weight or more from the viewpoint of forming a uniform and defect-free coating film. In view of storage stability of the solution, it is preferably 10% by weight or less.
The said organic solvent contained in the liquid crystal aligning agent of this invention will not be specifically limited if (A) component and (B) component melt | dissolve uniformly. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, Examples include 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. You may use these 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which cannot melt | dissolve a polymer component uniformly by itself, if it is a range which a polymer does not precipitate, you may mix with said organic solvent.

  The liquid crystal aligning agent of this invention may contain the solvent for improving the coating-film uniformity at the time of apply | coating a liquid crystal aligning agent to a board | substrate other than the organic solvent for dissolving a polymer component. As such a solvent, a solvent having a surface tension lower than that of the organic solvent is generally used. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2 -Propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, di Propylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactic acid Isoamyl ester, and the like. Two types of these solvents may be used in combination.

  In the liquid crystal aligning agent of the present invention, in addition to the above, as long as the effects of the present invention are not impaired, polymers other than the polymers of the components (A) and (B), the dielectric constant and conductivity of the liquid crystal aligning film The dielectric or conductive material for the purpose of changing the electrical properties such as the property, the silane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, the hardness and density of the film when the liquid crystal alignment film is made A target crosslinkable compound, and further an imidization accelerator for the purpose of efficiently proceeding imidization of the polyamic acid when the coating film is baked may be added.

<Liquid crystal alignment film>
The liquid crystal alignment film of the present invention is a coating film obtained by applying the liquid crystal aligning agent obtained as described above to a substrate, drying and baking.
The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like is formed. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as aluminum can be used. Examples of the method for applying the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method.

Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent of the present invention. Usually, in order to sufficiently remove the organic solvent contained, the organic solvent is dried at 50 ° C. to 120 ° C. for 1 minute to 10 minutes, and then baked at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes. Although the thickness of the coating film after baking is not specifically limited, Since the reliability of a liquid crystal display element may fall when too thin, it is 5-300 nm, Preferably it is 10-200 nm.
The liquid crystal aligning agent of the present invention can be subjected to conventional rubbing alignment treatment, but is particularly useful when used in a photo-alignment processing method.

As a specific example of the photo-alignment treatment method, there is a method in which the surface of the coating film is irradiated with radiation polarized in a certain direction, and in some cases, a heat treatment is further performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability. Can be mentioned. As the wavelength of radiation, ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used. Among these, ultraviolet rays having a wavelength of 100 nm to 400 nm are preferable, and those having a wavelength of 200 nm to 400 nm are particularly preferable. Moreover, in order to improve liquid crystal orientation, you may irradiate a radiation, heating a coating-film board | substrate at 50-250 degreeC. Dose of the radiation is preferably in the range of 1~10,000mJ / cm ^2, and particularly preferably in the range of 100~5,000mJ / cm ^2.
The liquid crystal alignment film produced as described above can stably align liquid crystal molecules in a certain direction.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
Below, the symbol of the compound used by the present Example and the comparative example, and the measuring method of each characteristic are as follows.
DA-1, DA-2, and DB-1: as defined above.
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve [viscosity]
In the synthesis example, the viscosity of the polyamic acid ester and the polyamic acid solution is an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.). ), Measured at a temperature of 25 ° C.
[Molecular weight]
The molecular weight of the polymer is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight (hereinafter also referred to as Mn) and the weight average molecular weight (hereinafter also referred to as Mw) as polyethylene glycol and polyethylene oxide converted values. Calculated.
GPC device: manufactured by Shodex (GPC-101)
Column: manufactured by Shodex (series of KD803 and KD805)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polymer laboratory Polyethylene glycol manufactured by the company (peak top molecular weight (Mp) of about 12,000, 4,000, 1,000). In order to avoid the overlapping of peaks, the measurement was performed by mixing four types of 900,000, 100,000, 12,000, and 1,000, and three types of 150,000, 30,000, and 4,000. Two samples of mixed samples are measured separately.

[AC drive image sticking characteristics of FFS drive liquid crystal cell]
An ITO electrode with a thickness of 50 nm as an electrode in the first layer, a silicon nitride with a thickness of 500 nm as an insulating film in the second layer, and a comb-like ITO electrode (electrode) as an electrode in the third layer Applying a liquid crystal aligning agent to a glass substrate on which a fringe field switching (hereinafter referred to as FFS) driving electrode having a width: 3 μm, an electrode interval: 6 μm, and an electrode height: 50 nm is formed by spin coating. And applied. After drying on an 80 ° C. hot plate for 5 minutes, baking was performed in a hot air circulation oven at 250 ° C. for 60 minutes to form a coating film having a thickness of 100 nm.
The coated film surface was irradiated with ultraviolet light having a wavelength of 254 nm via a polarizing plate to obtain a substrate with a liquid crystal alignment film. In addition, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm on which no electrode was formed as a counter substrate, and an orientation treatment was performed.
The two substrates are combined as a set, a sealant is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, and then the sealant is added. An empty cell was produced by curing. Liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell.
After measuring the VT characteristic (voltage-transmittance characteristic) of the FFS driving liquid crystal cell at a temperature of 58 ° C., a rectangular wave of ± 4 V / 120 Hz was applied for 4 hours. After 4 hours, the voltage was turned off and left at a temperature of 58 ° C. for 60 minutes, and then the VT characteristics were measured again to calculate the voltage difference (ΔV ₅₀ ) that gave a transmittance of 50% before and after the rectangular wave application. .
[Charge relaxation characteristics]
After placing the liquid crystal cell on a light source and measuring VT characteristics (voltage-transmittance characteristics), the transmittance (T _a ) of the liquid crystal cell in a state where a square wave of ± 1.5 V / 60 Hz is applied. It was measured. Then, after applying a square wave of ± 1.5 V / 60 Hz for 10 minutes, DC 2 V was superimposed and driven for 180 minutes. Measure the transmittance (T _b ) of the liquid crystal cell when the DC voltage is turned off and driven again for 20 minutes, 60 minutes, and 90 minutes with only ± 1.5 V / 60 Hz rectangular wave. From the difference (ΔT) between (T _b ) and the initial transmittance (T _a ), the difference in transmittance caused by the voltage remaining in the liquid crystal display element was calculated.

(Synthesis Example 1)
To a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2.92 g (27.0 mmol) of p-phenylenediamine and 0.67 g (3.0 mmol) of DA-1 were taken, and 52.27 g of NMP was added. The mixture was stirred and dissolved while feeding nitrogen. While stirring the diamine solution, 6.66 g (29.7 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride is added, and the solid content concentration is further 15% by weight. NMP was added as described above and stirred at room temperature for 24 hours to obtain a polyamic acid (PAA-1) solution. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 680 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 9,279 and Mw = 21,886.
(Synthesis Example 2)
To a 100 mL four-necked flask with a stirrer and a nitrogen inlet tube, take 2.60 g (24.0 mmol) of p-phenylenediamine and 1.34 g (6.0 mmol) of DA-1 and add 52.65 g of NMP. The mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 6.59 g (29.4 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and the solid content concentration became 15% by weight. NMP was added as described above and stirred at room temperature for 24 hours to obtain a polyamic acid (PAA-2) solution. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 357 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 9,042 and Mw = 19,958.

(Synthesis Example 3)
1.94 g (17.9 mmol) of p-phenylenediamine and 0.44 g (1.97 mmol) of DA-1 are added to a 100 mL four-necked flask with a stirrer and a nitrogen inlet tube, and 49.86 g of NMP is added. The mixture was stirred and dissolved while feeding nitrogen. While stirring the diamine solution, 3.77 g (19.2 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was further added so that the solid concentration was 10% by weight. The mixture was stirred at room temperature for 24 hours to obtain a polyamic acid (PAA-3) solution. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 142 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 11,494 and Mw = 24,376.

(Synthesis Example 4)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.11 g (28.8 mmol) of p-phenylenediamine and 0.85 g (3.20 mmol) of DA-2 were added, and 51.89 g of NMP was added. The mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 6.21 g (31.7 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was further added so that the solid content concentration was 15% by weight. The mixture was stirred at room temperature for 24 hours to obtain a polyamic acid (PAA-4) solution. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 10010 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 21,525 and Mw = 58,007.

(Synthesis Example 5)
To a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 2.16 g (20.0 mmol) of p-phenylenediamine was taken, 52.02 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 4.43 g (19.8 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and the solid content concentration became 10% by weight. NMP was added and stirred at room temperature for 24 hours to obtain a polyamic acid (PAA-5) solution. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 89.1 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 7,048 and Mw = 16,664.
(Synthesis Example 6)
To a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 2.16 g (20.0 mmol) of p-phenylenediamine was taken, 47.70 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 3.84 g (19.6 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was further added so that the solid content concentration was 10% by weight. The mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-6). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 303 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 19,188 and Mw = 49,182.

(Synthesis Example 7)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2.74 g (18.0 mmol) of 3,5-diaminobenzoic acid and 2.92 g (12.1 mmol) of DB-1 were taken and 58 NMP was added. .77 g was added and dissolved by stirring while feeding nitrogen. While stirring the diamine solution, 5.88 g (30.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added, and NMP was further added so that the solid content concentration was 15% by weight. The solution was stirred at room temperature for 24 hours to obtain a polyamic acid (PAA-7) solution. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 256 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 11,589 and Mw = 36,055.
(Synthesis Example 8)
In a 300 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 9.13 g (60.0 mmol) of 3,5-diaminobenzoic acid and 9.69 g (40.0 mmol) of DB-1 were taken, and NMP was 55 .83 g was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 9.91 g (50.0 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added, and NMP was further added so that the solid content concentration was 25% by weight. And stirred at room temperature for 2 hours. After 2 hours, 10.69 g (49.0 mmol) of pyromellitic dianhydride was added to the polymerization solution, NMP was further added so that the solid content concentration was 15% by weight, and the mixture was stirred at room temperature for 24 hours. A solution of acid (PAA-8) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 860 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 11,319 and Mw = 28,237.

(Synthesis Example 9)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1.83 g (12.0 mmol) of 3,5-diaminobenzoic acid and 1.93 g (7.97 mmol) of DB-1 were taken, and 12 NMP were added. .33 g was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 9.91 g (10.0 mmol) of 1,2,3,4-butanetetracarboxylic dianhydride was added, and NMP was further added so that the solid content concentration was 25% by weight. And stirred at room temperature for 2 hours. After 2 hours, 3.06 g (9.99 mmol) of 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride was added to this polymerization solution, and the solid content concentration was further adjusted to 20% by weight. NMP was added and stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-9). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 760 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 10,635 and Mw = 28,670.
(Synthesis Example 10)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, 3.66 g (24.0 mmol) of 3,5-diaminobenzoic acid and 3.88 g (16.0 mmol) of DB-1 were taken and 57 NMP was added. .56 g was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 8.58 g (39.3 mmol) of pyromellitic dianhydride was added, NMP was further added so that the solid concentration was 20% by weight, and the mixture was stirred at room temperature for 24 hours to be polyamic acid. A solution of (PAA-10) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 2221 mPa · s. Moreover, the molecular weight of this polyamic acid was Mn = 18,343 and Mw = 47,290.

(Example 1)
In a 20 ml sample tube containing a stir bar, 2.12 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 and 2.81 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 7 were taken. Then, 5.04 g of NMP and 2.49 g of BCS were added and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A-1).
(Example 2)
In a 50 ml sample tube containing a stir bar, 3.41 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 and 5.22 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 7 were taken. 7.39 g of NMP and 4.07 g of BCS were added and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A-2).
(Example 3)
In a 20 ml sample tube containing a stir bar, 3.12 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 3 and 2.82 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 7 were taken. Then, 4.09 g of NMP and 2.50 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-3).
Example 4
In a 20 ml sample tube containing a stir bar, 2.09 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 4 and 2.81 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 7 were taken. Then, 5.11 g of NMP and 2.49 g of BCS were added and stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A-4).

(Comparative Example 1)
In a 50 ml sample tube containing a stir bar, 8.52 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2 was taken, 7.47 g of NMP and 3.99 g of BCS were added, and 30 minutes with a magnetic stirrer. The liquid crystal aligning agent (B-1) was obtained by stirring.
(Comparative Example 2)
In a 50 ml sample tube containing a stir bar, 12.39 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 5 was taken, 3.62 g of NMP and 4.07 g of BCS were added, and 30 minutes with a magnetic stirrer. The liquid crystal aligning agent (B-2) was obtained by stirring.
(Comparative Example 3)
In a 50 ml sample tube containing a stir bar, 5.96 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 6 was taken, 1.93 g of NMP and 1.98 g of BCS were added, and 30 minutes with a magnetic stirrer. The liquid crystal aligning agent (B-3) was obtained by stirring.
(Comparative Example 4)
In a 50 ml sample tube containing a stir bar, 4.96 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 5 and 5.22 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 7 were taken. Then, 5.81 g of NMP and 4.01 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (B-4).

(Example 5)
On a glass substrate, an ITO electrode having a film thickness of 50 nm is used as the first layer, a silicon nitride film having a film thickness of 500 nm is used as the second layer, and a comb-shaped ITO electrode is used as the third layer (electrode width: 3 μm). The liquid crystal aligning agent (A-1) obtained in Example 1 is filtered through a 1.0 μm filter on a glass substrate on which an FFS driving electrode having an electrode interval of 6 μm and an electrode height of 50 nm is formed. Then, it was applied by spin coating. Subsequently, after drying for 5 minutes on an 80 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 30 minutes, and the coating film with a film thickness of 120 nm was formed. The coated surface was irradiated with 500 mJ / cm ^{2 of} 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm on which no electrode was formed as a counter substrate, and an orientation treatment was performed.
The two substrates are combined as a set, a sealant is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, and then the sealant is added. An empty cell was produced by curing. Liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell.
As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ΔV ₅₀ was 1.0 mV. As a result of evaluating the charge relaxation characteristics, ΔT after 20 minutes, 60 minutes, and 90 minutes of AC driving were 8%, 0%, and 0%, respectively.

(Example 6)
An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-2) obtained in Example 2 was used and irradiated with 400 mJ / cm ² polarized ultraviolet light. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ΔV ₅₀ was 4.3 mV. As a result of evaluating the charge relaxation characteristics, ΔT after 20 minutes, 60 minutes, and 90 minutes of AC driving were 1.5%, 0%, and 0%, respectively.
(Example 7)
An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-3) obtained in Example 3 was used and irradiated with polarized ultraviolet rays at 750 mJ / cm ² . As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, the voltage difference at which the transmittance was 50% before and after the rectangular wave application was 2.2 mV. As a result of evaluating the charge relaxation characteristics, ΔT after 20 minutes, 60 minutes, and 90 minutes of AC driving were 0%, 0%, and 0%, respectively.
(Example 8)
An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-4) obtained in Example 4 was used and irradiated with 1000 mJ / cm ² of polarized ultraviolet light. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ΔV ₅₀ was 3.6 mV. As a result of evaluating the charge relaxation characteristics, ΔT after 20 minutes, 60 minutes, and 90 minutes of AC driving were 0%, 0%, and 0%, respectively.

(Comparative Example 5)
An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used and irradiated with 400 mJ / cm ² polarized ultraviolet light. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ΔV ₅₀ was 3.5 mV. As a result of evaluating the charge relaxation characteristics, ΔT after 20 minutes, 60 minutes, and 90 minutes of AC driving were 0.6%, 0.3%, and 0.3%, respectively.
(Comparative Example 6)
An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (B-2) obtained in Comparative Example 2 was used and irradiated with polarized ultraviolet rays of 400 mJ / cm ² . As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ΔV ₅₀ was 1.0 mV. Moreover, as a result of evaluating the charge relaxation characteristics, ΔT after 20 minutes, 60 minutes, and 90 minutes of AC driving were 0.6%, 0.3%, and 0.4%, respectively.
(Comparative Example 7)
An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (B-3) obtained in Comparative Example 3 was used and irradiated with 1000 mJ / cm ² of polarized ultraviolet light. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ΔV ₅₀ was 0.8 mV. In addition, as a result of evaluating the charge relaxation characteristics, ΔT after 20 minutes, 60 minutes, and 90 minutes of AC driving were 2.1%, 0.4%, and 0.1%, respectively.
(Comparative Example 8)
An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (B-4) obtained in Comparative Example 4 was used and irradiated with 400 mJ / cm ² polarized ultraviolet light. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ΔV ₅₀ was 5.2 mV. As a result of evaluating the charge relaxation characteristics, ΔT after 20 minutes, 60 minutes, and 90 minutes of AC driving were 4%, 0%, and 0%, respectively.

As is apparent from Table 1 above, from the result of Comparative Example 5, when the component (A) of the aligning agent of the present invention is used alone, the AC drive burn-in characteristics are good, but the accumulated charge is slowly relieved. . On the other hand, from the results of Examples 5 to 8, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention exhibits almost the same AC drive burn-in characteristics as when the component (A) is used alone, and It was confirmed that the liquid crystal alignment film had good charge relaxation characteristics.
On the other hand, from the results of Comparative Examples 6 and 7, the polyamic acid obtained by using the component (A) of the liquid crystal aligning agent of the present invention alone and without using the diamine represented by the formula (2) was obtained. When used, the AC drive burn-in characteristic is degraded, and the accumulated charge is slowly relieved. Moreover, from the result of Comparative Example 8, when the component (B) is mixed as a charge relaxation component in the polyamic acid obtained without using the diamine represented by the formula (2) as the component (A) of the liquid crystal aligning agent, Although the charge relaxation characteristics are improved, it has been confirmed that the AC drive image sticking characteristics are greatly deteriorated.

Example 9
In a 50 ml sample tube containing a stir bar, 3.20 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 and 3.98 g of the polyamic acid solution (PAA-8) obtained in Synthesis Example 8 were taken. NMP (8.85 g) and BCS (4.02 g) were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-5).
(Example 10)
In a 50 ml sample tube containing a stir bar, 3.22 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 and 3.77 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 9 were taken. Then, 9.04 g of NMP and 4.02 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-6).
(Example 11)
In a 50 ml sample tube containing a stir bar, 3.21 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 and 3.62 g of the polyamic acid solution (PAA-10) obtained in Synthesis Example 10 were taken. NMP (9.28 g) and BCS (4.01 g) were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-7).

(Example 12)
An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-5) obtained in Example 9 was used and irradiated with 400 mJ / cm ² polarized ultraviolet light. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ΔV ₅₀ was 0.9 mV.
(Example 13)
An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-6) obtained in Example 10 was used and irradiated with 400 mJ / cm ² polarized ultraviolet light. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ΔV ₅₀ was 1.5 mV.
(Example 14)
An FFS drive liquid crystal cell was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (A-7) obtained in Example 11 was used and irradiated with 400 mJ / cm ² polarized ultraviolet light. As a result of evaluating the AC drive burn-in characteristics of this FFS drive liquid crystal cell, ΔV ₅₀ was 1.1 mV.

  The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2010-234933 filed on Oct. 19, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (16)

The liquid crystal aligning agent characterized by including the following (A) component, (B) component, and an organic solvent.
Component (A): at least one selected from the group consisting of a tetracarboxylic dianhydride represented by the following formula (1) and a structure represented by the following formulas (D-1) and (D-2) The at least 1 sort (s) of polymer chosen from the polyamic acid obtained by reaction with diamine and the diamine compound containing the diamine represented by following formula (2), and its imidation polymer.

(In the formula _{(1), R 1, R} 2, R 3, and _{R 4} are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, alkenyl or alkynyl group having 2 to 6 carbon atoms, Or a phenyl group.)
(In formula (2), _{A 1} is a single bond or ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O -, - OCO-, and 1 to 3 carbon atoms At least one divalent organic group selected from the group consisting of alkylene groups, wherein Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₅ is a hydrogen atom or 1 carbon atom. It is a monovalent organic group of ˜8.)

(In Formula (D-2), Z ₁ is a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 6 carbon atoms.)
(B) component: at least 1 sort (s) chosen from the polyamic acid obtained by reaction of tetracarboxylic dianhydride and the diamine compound containing the diamine represented by following formula (3), and its imidized polymer Polymer.

(In the formula _{(3), B} 1 ^{is, -O -, - NQ 2 -} , - CONQ 2 -, - NQ 2 CO -, - CH 2 O-, and at least one selected from the group consisting of -OCO- Q ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, B ₂ is a single bond or an alkylene group having 1 to 4 carbon atoms, and B ₃ is (It is a nitrogen atom-containing heterocyclic ring, and n is an integer of 1 to 4.)   The content weight ratio (A / B) between the component (A) and the component (B) is 3/7 to 7/3, and the total content of the component (A) and the component (B) is (A The liquid crystal aligning agent of Claim 1 which is 1 to 10 weight% with respect to the total amount of a component), (B) component, and an organic solvent.   (A) component tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride The liquid crystal aligning agent according to claim 1, which is at least one tetracarboxylic dianhydride selected from the group consisting of:   The liquid crystal aligning agent according to any one of claims 1 to 3, wherein the tetracarboxylic dianhydride as the component (A) is 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride. .   (A) The diamine compound of a component is a diamine containing 5-30 mol% of diamine represented by the said Formula (2), The liquid crystal aligning agent in any one of Claims 1-4. The diamine represented by the above formula (2) contained in the component (A) is at least one selected from the following formulas (DA-1), (DA-2) and (DA-3). The liquid crystal aligning agent in any one of -5.

  (B) The diamine compound of a component is a diamine which contains 30-100 mol% of diamine represented by the said Formula (3), The liquid crystal aligning agent in any one of Claims 1-6. The diamine represented by the formula (3) contained in the component (B) is at least one selected from the following formulas (DB-1) to (DB-6). Liquid crystal aligning agent.

The tetracarboxylic dianhydride as the component (B) is represented by the following formula (4), wherein X ₁ is at least one selected from the following structures. Liquid crystal aligning agent.

  (B) The tetracarboxylic dianhydride as the component is at least one selected from 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride The liquid crystal aligning agent according to any one of claims 1 to 9, wherein the content is 50 to 100 mol% with respect to the total tetracarboxylic dianhydride of component (B). .   The liquid crystal aligning agent in any one of Claims 1-10 whose tetracarboxylic dianhydride of (B) component is 1,2,3,4-cyclobutane tetracarboxylic dianhydride. The diamine compound as the component (B) contains a carboxylic acid-containing diamine represented by the following formula (5) in addition to the diamine represented by the above formula (3). Alignment agent.

(In the formula (5), _{B 3} has the same meaning as the _{B 1, B 4} is a single bond or an alkylene group having 1 to 4 carbon atoms, m is an integer from 1 to 4.)   (B) The diamine of a component contains the diamine represented by the said Formula (3) and the diamine represented by the said Formula (5), The total amount is 40 with respect to all the diamines of (B) component. It is-100 mol%. The liquid crystal aligning agent in any one of Claims 1-12.   The liquid crystal aligning agent according to claim 1, wherein the diamine represented by the formula (5) is at least one selected from 3,5-diaminobenzoic acid and 2,5-diaminobenzoic acid. The manufacturing method of the liquid crystal aligning film which apply | coats and bakes the liquid crystal aligning agent in any one of Claims 1-14 . The manufacturing method of the liquid crystal aligning film which apply | coats and bakes the liquid crystal aligning agent in any one of Claims 1-14, and also irradiates the polarized radiation.