JP5012067B2 - Liquid crystal aligning agent containing polyamic acid or polyimide having naphthalene ring in side chain - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent containing a polyamic acid or polyimide having a naphthalene ring in the side chain.

  Liquid crystal display elements have been changed from Twisted Nematic (TN) to Super Twisted Nematic (STN) in response to demands for higher display quality and response speed, such as screen enlargement and colorization, contrast and color development. Furthermore, it has been developed into a TFT type display element in which a thin film transistor (TFT) is attached to each pixel. In recent years, improvements in driving methods of TFT display devices have progressed. For example, in order to further widen the viewing angle, an in-plane switching (IPS) method or a vertical alignment (vertical alignment, hereinafter abbreviated as VA) method. In addition, an optically compensated bend (OCB) method having a response speed capable of moving images has been developed.

  The liquid crystal alignment film plays two roles of aligning liquid crystal molecules in a certain direction in the liquid crystal display element and tilting the substrate plane (providing a pretilt angle). The tilt of the liquid crystal molecules with respect to the substrate plane is called the pretilt angle. This name will be used hereinafter in this specification. The liquid crystal alignment film includes a polyimide thin film with a high glass transition point (Tg) and excellent chemical resistance and heat resistance in order to minimize the deterioration of molecular alignment over time, chemical and thermal. It is mainly used as a material. The liquid crystal alignment film is usually a polyamic acid or soluble polyimide solution (hereinafter abbreviated as a liquid crystal alignment agent) applied to a glass substrate with an electrode by a spinner method or a printing method, and the substrate is heated to dehydrate and ring-close the polyamic acid. Or by evaporating the solvent of the soluble polyimide solution to obtain a polyimide thin film, and further through an alignment treatment step such as rubbing.

  The substrates with the liquid crystal alignment film formed on the surface in this way are bonded together so that they face each other, and after the pressure inside the assembled cell is reduced, the liquid crystal is injected into the cell from the opening by dipping in the liquid crystal. Thus, a liquid crystal display element is created. However, in this method, it takes time to inject liquid crystal, which has been a problem particularly when a large-screen liquid crystal display element is produced. Therefore, in order to improve productivity, “drop injection” in which a liquid crystal is directly dropped on a liquid crystal alignment film and then a cell is bonded is recently started.

Such a liquid crystal alignment film is required to have the following effects on the liquid crystal display element.
(1) Giving an appropriate pretilt angle to liquid crystal molecules. Moreover, the change in the pretilt angle due to the difference in indentation strength during rubbing and temperature during heating is small.
(2) An alignment process that does not cause alignment defects in the liquid crystal display element is possible.
(3) An appropriate voltage holding ratio (Voltage Holding Ratio: VHR (also referred to as VHR)) can be given to the liquid crystal display element.
(4) A phenomenon called “burn-in” in which an image is displayed as an afterimage when an arbitrary image is displayed on the liquid crystal display element for a long time and then changed to another image, is difficult to occur.
In particular, a high-quality liquid crystal alignment film used for a TFT display element is required to have a high voltage holding ratio and hardly cause a burn-in phenomenon.

As one of the causes of the “burn-in” phenomenon, an electric double layer generated at the interface between the liquid crystal and the liquid crystal alignment film has been pointed out. That is, since the dielectric constants of these two materials are different, static electricity is generated at the interface between them and an extra voltage is generated in the liquid crystal display element. In order to suppress this phenomenon, it is considered to introduce a substituent having a liquid crystal-like structure on the surface of the liquid crystal alignment film so as to eliminate the difference in the interface between the liquid crystal and the liquid crystal alignment film as much as possible.

ＥＰ０６７９６３３号明細書 As such a liquid crystal alignment film, a polyimide liquid crystal alignment film using a diamine of the following formula (9) is known.

EP0679633 specification

  However, in order to design a liquid crystal alignment film that satisfies the above required characteristics, development of diamines having various skeletons is required.

  An object of the present invention is to provide, for example, a liquid crystal alignment film material that suppresses the image sticking phenomenon and has a higher VHR than a known liquid crystal alignment film material.

  The inventor developed an alignment film material that suppresses the image sticking phenomenon and has a high VHR as a result of introducing a naphthalene ring into the liquid crystal structure in a liquid crystal alignment film having a liquid crystal structure (particularly a liquid crystal structure having a polar group at the end) in the side chain. Succeeded in doing.

（式中Ａ¹は単結合、フェニレン、またはナフチレンを表し、Ａ²はフェニレンまたはナフチレンを表し、Ａ¹またはＡ²のうち少なくとも１つはナフチレンであり、Ｘ¹は炭素数１〜１４のアルキレンを表し、このうちの１または隣り合わない２つのメチレンは−Ｏ−もしくは−ＣＯＯ−で置換されてもよい。Ｘ²は単結合、−ＯＣＯ−、−ＣＯＯ−、または−ＣＯＮＲ²−を表し、Ｒ²は水素またはメチルを表し、Ｒは水素、炭素数１〜１２のアルキル、−ＣＮ、−Ｆ、−ＯＨ、−ＣＯ₂Ｈ、−ＯＣＯＲ³、または−ＣＯ₂Ｒ³を表し、Ｒ³はメチルもしくはエチルを表す。）
＜２＞
前記側鎖にナフタレン環を有するポリアミック酸もしくはポリイミドが下記一般式（２）で示されるフェニレンジアミンを含むジアミンから合成されるものである＜１＞に記載の液晶配向剤。

（式中Ａ¹は単結合、フェニレン、またはナフチレンを表し、Ａ²はフェニレンまたはナフチレンを表し、Ａ¹またはＡ²のうち少なくとも１つはナフチレンであり、Ｘ¹は炭素数１〜１４のアルキレンを表し、このうちの１または隣り合わない２つのメチレンは−Ｏ−もしくは−ＣＯＯ−で置換されてもよい。Ｘ²は単結合、−ＯＣＯ−、−ＣＯＯ−、または−ＣＯＮＲ²−を表し、Ｒ²は水素またはメチルを表し、Ｒは水素、炭素数１〜１２のアルキル、−ＣＮ、−Ｆ、−ＯＨ、−ＣＯ₂Ｈ、−ＯＣＯＲ³、または−ＣＯ₂Ｒ³を表し、Ｒ³はメチルもしくはエチルを表す。）
＜３＞
前記側鎖にナフタレン環を有するポリアミック酸もしくはポリイミドが下記一般式（３）で示されるフェニレンジアミンを含むジアミンから合成されるものである＜２＞に記載の液晶配向剤。

（式中Ａ¹は単結合、フェニレン、またはナフチレンを表し、Ａ²はフェニレンまたはナフチレンを表し、Ａ¹またはＡ²のうち少なくとも１つはナフチレンであり、Ｘ³は炭素数１〜１３のアルキレンを表し、このうちのＡ¹に結合するメチレンは−Ｏ−または−ＣＯＯ−で置換されてもよい。Ｘ²は単結合、−ＣＯＯ−、または−ＣＯＮＲ²−を表し、Ｒ²は水素またはメチルを表し、Ｒは水素、炭素数１〜１２のアルキル、−ＣＮ、−Ｆ、−ＯＨ、または−ＣＯ₂Ｒ³を表し、Ｒ³はメチルもしくはエチルを表す。）
＜４＞
前記側鎖にナフタレン環を有するポリアミック酸もしくはポリイミドが下記一般式（４）で示されるフェニレンジアミンを含むジアミンから合成されるものである＜２＞に記載の液晶配向剤。

（式中Ａ¹は単結合、フェニレン、またはナフチレンを表し、Ａ²はフェニレンまたはナフチレンを表し、Ａ¹またはＡ²のうち少なくとも１つはナフチレンであり、Ｘ³は炭素数１〜１３のアルキレンを表し、このうちのＡ¹に結合するメチレンは−Ｏ−または−ＣＯＯ−で置換されてもよい。Ｘ²は単結合、−ＣＯＯ−、または−ＣＯＮＲ²−を表し、Ｒ²は水素またはメチルを表し、Ｒは水素、炭素数１〜１２のアルキル、−ＣＮ、−Ｆ、−ＯＨ、または−ＣＯ₂Ｒ³を表し、Ｒ³はメチルもしくはエチルを表す。）
＜５＞
前記一般式（３）において、Ｘ³が炭素数１〜６のアルキレンであり、このうちのＡ¹に結合するメチレンは−Ｏ−または−ＣＯＯ−で置換されてもよく、Ｘ²が単結合または−ＣＯＯ−であり、Ｒが−ＣＮ、−ＯＨ、または−ＣＯ₂Ｍｅであるフェニレンジアミンを含むジアミンから合成されるポリアミック酸もしくはポリイミドを含有する＜３＞に記載の液晶配向剤。
＜６＞
前記一般式（４）において、Ｘ³が炭素数１〜６のアルキレンであり、このうちのＡ¹に結合するメチレンは−Ｏ−または−ＣＯＯ−で置換されてもよく、Ｘ²が単結合または−ＣＯＯ−であり、Ｒが−ＣＮ、−ＯＨ、または−ＣＯ₂Ｍｅであるフェニレンジアミンを含むジアミンから合成されるポリアミック酸もしくはポリイミドを含有する＜４＞に記載の液晶配向剤。
＜７＞
下記一般式（３−１）〜（３−５２）で示されるジアミンから構成される群から選択される１種以上を含むアミン成分から合成されるポリアミック酸もしくはポリイミドをさら
に含有する＜１＞〜＜６＞のいずれかに記載の液晶配向剤。

＜８＞
前記アミン成分が４，４'−ジアミノジフェニルメタンを含む＜７＞に記載の液晶配向剤。
＜９＞
前記ポリアミック酸もしくはポリイミドが酸成分としてテトラカルボン酸二無水物を用
いて合成されるものであり、前記テトラカルボン酸二無水物は、下記式（２−１）〜（２−３８）で示される芳香族テトラカルボン酸二無水物及び脂肪族テトラカルボン酸二無水物若しくは脂環式テトラカルボン酸から選ばれる一種以上を含む＜１＞〜＜８＞のいずれかに記載の液晶配向剤。

＜１０＞
前記テトラカルボン酸二無水物が、ピロメリット酸二無水物及び／又はシクロブタンテトラカルボン酸二無水物である＜９＞に記載の液晶配向剤。
＜１１＞
下記一般式（２）で示されるフェニレンジアミン。

（式中Ａ¹は単結合、フェニレン、またはナフチレンを表し、Ａ²はフェニレンまたはナフチレンを表し、Ａ¹またはＡ²のうち少なくとも１つはナフチレンであり、Ｘ¹は炭素数１〜１４のアルキレンを表し、このうちの１または隣り合わない２つのメチレンは−Ｏ−もしくは−ＣＯＯ−で置換されてもよい。Ｘ²は単結合、−ＯＣＯ−、−ＣＯＯ−、または−ＣＯＮＲ²−を表し、Ｒ²は水素またはメチルを表し、Ｒは水素、炭素数１〜１２のアルキル、−ＣＮ、−Ｆ、−ＯＨ、−ＣＯ₂Ｈ、−ＯＣＯＲ³、または−ＣＯ₂Ｒ³を表し、Ｒ³はメチルもしくはエチルを表す。）
＜１２＞
下記一般式（３）で示されるフェニレンジアミン。

（式中Ａ¹は単結合、フェニレン、またはナフチレンを表し、Ａ²はフェニレンまたはナフチレンを表し、Ａ¹またはＡ²のうち少なくとも１つはナフチレンであり、Ｘ³は炭素数１〜１３のアルキレンを表し、このうちのＡ¹に結合するメチレンは−Ｏ−または−ＣＯＯ−で置換されてもよい。Ｘ²は単結合、−ＣＯＯ−、または−ＣＯＮＲ²−を表し、Ｒ²は水素またはメチルを表し、Ｒは水素、炭素数１〜１２のアルキル、−ＣＮ、−Ｆ、−ＯＨ、または−ＣＯ₂Ｒ³を表し、Ｒ³はメチルもしくはエチルを表す。）
＜１３＞
下記一般式（４）で示されるフェニレンジアミン。

（式中Ａ¹は単結合、フェニレン、またはナフチレンを表し、Ａ²はフェニレンまたはナフチレンを表し、Ａ¹またはＡ²のうち少なくとも１つはナフチレンであり、Ｘ³は炭素数１〜１３のアルキレンを表し、このうちのＡ¹に結合するメチレンは−Ｏ−または−ＣＯＯ−で置換されてもよい。Ｘ²は単結合、−ＣＯＯ−、または−ＣＯＮＲ²−を表し、Ｒ²は水素またはメチルを表し、Ｒは水素、炭素数１〜１２のアルキル、−ＣＮ、−Ｆ、−ＯＨ、または−ＣＯ₂Ｒ³を表し、Ｒ³はメチルもしくはエチルを表す。）
＜１４＞
前記一般式（３）において、Ｘ³が炭素数１〜６のアルキレンであり、このうちのＡ¹に結合するメチレンは−Ｏ−または−ＣＯＯ−で置換されてもよく、Ｘ²が単結合または−ＣＯＯ−であり、Ｒが−ＣＮ、−ＯＨ、または−ＣＯ₂Ｍｅである＜１２＞に記載のフェニレンジアミン。
＜１５＞
前記一般式（４）において、Ｘ³が炭素数１〜６のアルキレンであり、このうちのＡ¹に結合するメチレンは−Ｏ−または−ＣＯＯ−で置換されてもよく、Ｘ²が単結合または−ＣＯＯ−であり、Ｒが−ＣＮ、−ＯＨ、または−ＣＯ₂Ｍｅである＜１３＞に記載のフェニレンジアミン。 The present invention comprises the following.
<1>
In the liquid crystal aligning agent containing polyamic acid or polyimide having a naphthalene ring in the side chain ,
The liquid crystal aligning agent whose side chain of the polyamic acid or polyimide which has a naphthalene ring in the said side chain is group shown by following General formula (1).

Wherein A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ¹ is an alkylene having 1 to 14 carbon atoms. X ² represents a single bond, —OCO—, —COO—, or —CONR ² —, wherein one or two of the methylenes not adjacent to each other may be substituted with —O— or —COO—. , R ² represents hydrogen or methyl, R represents hydrogen, alkyl having 1 to 12 carbons, —CN, —F, —OH, —CO ₂ H, —OCOR ³ , or —CO ₂ R ³ , R ³ represents methyl or ethyl.)
< 2 >
The liquid crystal aligning agent as described in < 1 > in which the polyamic acid or polyimide which has a naphthalene ring in the said side chain is synthesize | combined from diamine containing the phenylenediamine shown by following General formula (2).

Wherein A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ¹ is an alkylene having 1 to 14 carbon atoms. X ² represents a single bond, —OCO—, —COO—, or —CONR ² —, wherein one or two of the methylenes not adjacent to each other may be substituted with —O— or —COO—. , R ² represents hydrogen or methyl, R represents hydrogen, alkyl having 1 to 12 carbons, —CN, —F, —OH, —CO ₂ H, —OCOR ³ , or —CO ₂ R ³ , R ³ represents methyl or ethyl.)
< 3 >
The liquid crystal aligning agent as described in < 2 > in which the polyamic acid or polyimide which has a naphthalene ring in the said side chain is synthesize | combined from diamine containing the phenylenediamine shown by following General formula (3).

(In the formula, A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ³ represents an alkylene having 1 to 13 carbon atoms. Of which methylene bonded to A ¹ may be substituted with —O— or —COO—, X ² represents a single bond, —COO—, or —CONR ² —, and R ² represents hydrogen or represents methyl, R represents hydrogen, alkyl having 1 to 12 carbon atoms, -CN, -F, -OH, or -CO ₂ R ^3, R ³ represents methyl or ethyl.)
< 4 >
The liquid crystal aligning agent as described in < 2 > in which the polyamic acid or polyimide which has a naphthalene ring in the said side chain is synthesize | combined from diamine containing the phenylenediamine shown by following General formula (4).

(In the formula, A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ³ represents an alkylene having 1 to 13 carbon atoms. Of which methylene bonded to A ¹ may be substituted with —O— or —COO—, X ² represents a single bond, —COO—, or —CONR ² —, and R ² represents hydrogen or represents methyl, R represents hydrogen, alkyl having 1 to 12 carbon atoms, -CN, -F, -OH, or -CO ₂ R ^3, R ³ represents methyl or ethyl.)
< 5 >
In the general formula (3), X ³ is alkylene having 1 to 6 carbon atoms, methylene bonded to A ¹ may be substituted with —O— or —COO—, and X ² is a single bond. or a -COO-, liquid crystal alignment agent according to R is -CN, -OH, or contains a polyamic acid or a polyimide synthesized from diamines containing phenylenediamine is -CO ₂ Me <3>.
< 6 >
In the general formula (4), X ³ is alkylene having 1 to 6 carbon atoms, methylene bonded to A ¹ may be substituted with —O— or —COO—, and X ² is a single bond. or a -COO-, liquid crystal alignment agent according to R is -CN, -OH, or contains a polyamic acid or a polyimide synthesized from diamines containing phenylenediamine is -CO ₂ Me <4>.
< 7 >
<1> to further containing a polyamic acid or polyimide synthesized from an amine component containing one or more selected from the group consisting of diamines represented by the following general formulas (3-1) to (3-52) The liquid crystal aligning agent in any one of < 6 >.

< 8 >
The liquid crystal aligning agent as described in < 7 > in which the said amine component contains 4,4'- diamino diphenylmethane.
< 9 >
The polyamic acid or polyimide is synthesized using tetracarboxylic dianhydride as an acid component, and the tetracarboxylic dianhydride is represented by the following formulas (2-1) to (2-38). The liquid crystal aligning agent in any one of <1>-< 8 > containing 1 or more types chosen from aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, or alicyclic tetracarboxylic acid.

< 10 >
The liquid crystal aligning agent as described in < 9 > whose said tetracarboxylic dianhydride is pyromellitic dianhydride and / or cyclobutane tetracarboxylic dianhydride.
< 11 >
Phenylenediamine represented by the following general formula (2).

Wherein A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ¹ is an alkylene having 1 to 14 carbon atoms. X ² represents a single bond, —OCO—, —COO—, or —CONR ² —, wherein one or two of the methylenes not adjacent to each other may be substituted with —O— or —COO—. , R ² represents hydrogen or methyl, R represents hydrogen, alkyl having 1 to 12 carbons, —CN, —F, —OH, —CO ₂ H, —OCOR ³ , or —CO ₂ R ³ , R ³ represents methyl or ethyl.)
< 12 >
Phenylenediamine represented by the following general formula (3).

(In the formula, A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ³ represents an alkylene having 1 to 13 carbon atoms. Of which methylene bonded to A ¹ may be substituted with —O— or —COO—, X ² represents a single bond, —COO—, or —CONR ² —, and R ² represents hydrogen or represents methyl, R represents hydrogen, alkyl having 1 to 12 carbon atoms, -CN, -F, -OH, or -CO ₂ R ^3, R ³ represents methyl or ethyl.)
< 13 >
Phenylenediamine represented by the following general formula (4).

(In the formula, A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ³ represents an alkylene having 1 to 13 carbon atoms. Of which methylene bonded to A ¹ may be substituted with —O— or —COO—, X ² represents a single bond, —COO—, or —CONR ² —, and R ² represents hydrogen or represents methyl, R represents hydrogen, alkyl having 1 to 12 carbon atoms, -CN, -F, -OH, or -CO ₂ R ^3, R ³ represents methyl or ethyl.)
< 14 >
In the general formula (3), X ³ is alkylene having 1 to 6 carbon atoms, methylene bonded to A ¹ may be substituted with —O— or —COO—, and X ² is a single bond. or a -COO-, phenylenediamine according to R is -CN, -OH or -CO ₂ Me, <12>.
< 15 >
In the general formula (4), X ³ is alkylene having 1 to 6 carbon atoms, methylene bonded to A ¹ may be substituted with —O— or —COO—, and X ² is a single bond. or a -COO-, phenylenediamine according to R is -CN, -OH or -CO ₂ Me, <13>.

  The liquid crystal display device having a liquid crystal alignment film formed from a liquid crystal alignment agent containing a polyamic acid or polyimide having a naphthalene ring in the side chain of the present invention is particularly suitable for a TN or IPS mode liquid crystal display device that requires a small pretilt angle. The burn-in phenomenon can be suppressed. Moreover, since the phenylenediamine of the present invention can be produced at a low cost by a short synthesis route, a high-functional liquid crystal display element can be provided at a lower cost according to the present invention.

  First, the liquid crystal aligning agent containing a polyamic acid or polyimide having a naphthalene ring in the side chain of the present invention will be described. The liquid crystal aligning agent of this invention is characterized by containing the polyamic acid or polyimide which has a naphthalene ring in the side chain mentioned later. Specific examples of the side chain of the polyamic acid or polyimide include those shown below.

The side chain represented by the following formula (1) will be described as a specific example of the side chain possessed by the polyamic acid or polyimide used for the production of the liquid crystal aligning agent.

In the side chain represented by the above formula (1) of the present invention, R is hydrogen, alkyl having 1 to 12 carbons, —CN, —F, —OH, —CO ₂ H, —OCOR ³ , or —CO _2. represents R ^3, R ³ represents methyl or ethyl. In this case, when a smaller pretilt angle is desired, R is preferably —CN, —OH, or —CO ₂ H, and more preferably —CN or —OH. When a higher VHR is desired, R is preferably hydrogen, alkyl having 1 to 12 carbons, or -F, and more preferably -F.

X ² represents a single bond, —OCO—, —COO—, or —CONR ² —, and R ² represents hydrogen or methyl, but a single bond or —COO— is preferable because of easy synthesis. In particular, when the liquid crystal aligning agent is baked at a temperature of 230 ° C. or higher, X ² is more preferably a single bond from the viewpoint of preventing thermal decomposition.

A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, and at least one of A ¹ or A ² is naphthylene. At this time, it is preferable that A ¹ or A ² is phenylene or naphthylene in order to make it difficult to form an electric double layer with the liquid crystal and to suppress burn-in. When a higher VHR is desired, A ¹ is preferably a single bond.

X ¹ represents alkylene having 1 to 14 carbon atoms, and one or two methylenes not adjacent to each other may be substituted with —O— or —COO—. When it is desired to impart high liquid crystal alignment ability to the liquid crystal alignment film, X ¹ preferably contains a longer alkylene. Specifically, C3 or more is preferable, and 5 or more is more preferable.

  Specific examples of the structure of the side chain represented by the formula (1) include structures represented by the following formulas 1 to 259.

The above No. of the present invention. 1-No. Any of the liquid crystal alignment films made of a liquid crystal aligning agent containing polyamic acid or polyimide having 259 side chains can suppress burn-in. At this time, no. 1, 2, 5, 6, 9, 10, 13-15, 18-20, 23-25, 28, 30, 32-34, 36-38, 40, 42-45, 47-51, 54, 55, 58, 59, 62-64, 67-69, 72-74, 77-79, 81-83, 85-99, 101-103, 105, 107-110, 113, 115, 116, 120-122, 124- 128, 130, 131, 133-136, 138, 139, 141-142, 144-148, 150-152, or 154-156, having a relatively polar functional group at the end If the alignment film is used, the surface energy of the alignment film becomes relatively large, and the pretilt angle of the liquid crystal can be reduced. Therefore, it is suitable as an alignment film for IPS and TN. Among these, particularly when X ² is a single bond, the pre-tilt angle of the liquid crystal can be particularly reduced because the side chain is shorter. Therefore, it is suitable as an alignment film for IPS.

  If a liquid crystal alignment film having a fluorine atom or a relatively long side chain other than the above is used, the surface energy of the alignment film becomes relatively small, and the pretilt angle of the liquid crystal can be increased. Therefore, it is particularly suitable as a liquid crystal alignment film for TN, OCB, or VA. In addition, since the liquid crystal alignment film having these side chains has a high VHR, it is particularly optimal when such an application is required.

Secondly, the polyamic acid having a naphthalene ring in the side chain of the present invention and a polyimide obtained by dehydrating the polyamic acid will be described.
A polyamic acid is obtained by reacting at least one diamine having a naphthalene ring in the side chain with an acid dianhydride. Alternatively, it can be obtained by reacting one or more acid dianhydrides having a naphthalene ring in the side chain with a diamine. Preferably, it can be obtained by reacting a diamine having a side chain represented by the formula (1) with an acid dianhydride in a solvent described later. As a more preferred example, it is obtained by reacting a phenylenediamine represented by formula (2) or (3) (hereinafter referred to as diamine (2) or (3)) with an acid dianhydride, for example, tetracarboxylic dianhydride. Is mentioned. Polyimide is obtained by dehydration reaction of this polyamic acid. As the tetracarboxylic dianhydride, all known tetracarboxylic dianhydrides can be used, and particularly preferable examples include compounds described in Table 2.

Table 2 Suitable acid dianhydrides

  Some of these compounds include isomers, but a mixture of these isomers may be used. Moreover, you may use it combining the acid dianhydride of the said table | surface. The tetracarboxylic dianhydride used in the present invention may be other than the above compounds.

  Liquid crystal alignment films using a liquid crystal alignment agent containing polyamic acid or polyimide composed of acid dianhydrides and diamines of these preferred examples all exhibit high VHR, prevent image sticking and have high liquid crystal alignment ability. Have. Therefore, it is particularly excellent as an alignment film for a TFT display element that contains a liquid crystal composition having a low threshold voltage and is driven at a low voltage.

  When it is particularly desired to give a high VHR to the liquid crystal display element, no. 2-2, 2-12, 2-13, 2-14, 2-15, 2-16, 2-17, 2-18, 2-20, 2-21, 2-22, 2-23, 2- By selecting one or more compounds having an alicyclic skeleton such as 24, 2-28, 2-29, 2-30, 2-31, 2-32, 2-35, 2-36, and 2-38, This can be achieved. In particular, when it is desired to prevent the image sticking phenomenon, No. Compounds such as 2-1, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 2-19 and other compounds This can be achieved by appropriately combining the two.

  In the present invention, the diamine (2), (3), or (4) may be used alone, but two or more of the diamines (2), (3), or (4) are used in combination. Alternatively, the diamine (2), (3), or (4) may be used in combination with other known diamines.

  As the diamine that can be used in combination with the phenylenediamine of the present invention, all known diamines can be used, and particularly preferred examples include the diamines described in Table 3.

Table 3 Suitable diamines

式（８）中、Ｒ¹⁰およびＲ¹¹は炭素数１〜３のアルキルまたはフェニルであり、Ｒ¹⁰とＲ¹¹は同じ基であっても異なる基であってもよい。また、Ｒ¹²はそれぞれ独立してメチレン、フェニレンまたはアルキル置換されたフェニレンである。ｍは１〜６の整数を表し、ｎは１〜１０の整数を表す。 Examples of diamines other than the diamine that can be used in combination with the phenylenediamine of the present invention include siloxane-based diamines represented by the formula (8).

In formula (8), R ¹⁰ and R ¹¹ are alkyl or phenyl having 1 to 3 carbon atoms, and R ¹⁰ and R ¹¹ may be the same group or different groups. R ¹² is independently methylene, phenylene or alkyl-substituted phenylene. m represents an integer of 1 to 6, and n represents an integer of 1 to 10.

The molecular weight of the polyamic acid or polyimide used in the liquid crystal aligning agent of the present invention, for example, the weight average molecular weight (MW), is preferably 10,000 or more from the viewpoint of preventing abrasion during rubbing and maintaining the stability of the liquid crystal alignment film against the environment. If the molecular weight is increased, the viscosity of the aligning agent is also increased. From the viewpoint of ease of handling, MW is preferably 200000 or less.

  Whether the polyamic acid or polyimide contained in the liquid crystal aligning agent has a naphthalene ring in the side chain can be analyzed using, for example, the following method. First, the contained polymer is fractionated by reprecipitation of the liquid crystal aligning agent. Next, this polymer is hydrolyzed with a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a hydrazine solution or the like. The hydrolyzed solution is made antsy, neutral, or acidic and extracted with an organic solvent such as ethyl acetate, methylene chloride, or chloroform. The degradation product of the polymer contained in the extraction solvent is analyzed by NMR, IR, or MS according to a conventional method.

Thirdly, the liquid crystal aligning agent of the present invention will be described. The liquid crystal aligning agent of this invention is a polymer solution containing the polyamic acid or polyimide which has a naphthalene ring in a side chain. Specific examples of the liquid crystal aligning agent of the present invention include a polyamic acid or polyimide solution obtained by reacting the phenylenediamine and acid dianhydride of the present invention, and removing the solvent from the polyamic acid or polyimide solution. And a polyamic acid or polyimide solution obtained by dissolving a polymer of polyamic acid or polyimide obtained in another solvent, and a mixture thereof.
In the synthesis of the polyamic acid or polyimide used for the production of the liquid crystal aligning agent, when the phenylenediamine of the present invention is used, the molar ratio of the phenylenediamine of the present invention in the diamine component is a high voltage when used in a liquid crystal display device. From the viewpoint of maintaining the retention rate and reducing residual DC, the IPS mode is preferably 20 to 100%, and more preferably 30 to 80%. In TN and OCB, the mode is preferably 10 to 50%, more preferably 10 to 30%. In the VA mode, 5 to 30% is preferable, and 5 to 20% is more preferable.

  In order to impart desired characteristics to the liquid crystal alignment film, two or more kinds of polymers having a naphthalene ring in the side chain may be arbitrarily mixed and used as the liquid crystal aligning agent of the present invention. (Blending such a plurality of polymers is called “polymer blend”.)

In order to develop better properties as a liquid crystal alignment film, one or more kinds selected from all known polymers may be polymer blended with the liquid crystal aligning agent of the present invention. At this time, the ratio of the polymer having a naphthalene ring in the side chain in the total polymer is preferably in the range of 50 to 100% by weight, more preferably in the range of 70 to 100% by weight in order to express the effect of the present invention.

  The ratio of the polymer contained in the liquid crystal aligning agent of this invention is not specifically limited, What is necessary is just to select an optimal value according to the following various coating methods. Usually, in order to suppress unevenness and pinholes during application, the content is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the weight of the liquid crystal aligning agent.

If an organosilicone compound is added to the liquid crystal aligning agent of the present invention, it becomes possible to adjust the adhesion and hardness of the liquid crystal aligning film to the glass substrate, and to improve display defects caused by rubbing the polyimide by rubbing or the like. I can do it. The organosilicone compound added to the liquid crystal aligning agent of the present invention is not particularly limited. For example, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, N- (2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 Silane coupling agents such as glycidoxypropylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and silicone oils such as dimethylpolysiloxane, polydimethylsiloxane, and polydiphenylsiloxane. .

  The addition ratio of the organosilicone compound to the liquid crystal aligning agent is not particularly limited as long as the display defect can be improved without impairing the characteristics required for the liquid crystal aligning film. However, if a large amount of these is added, alignment failure of the liquid crystal occurs when the liquid crystal alignment film is formed. Therefore, these concentrations are preferably in the range of 0.01 to 5% by weight, particularly preferably in the range of 0.1 to 3% by weight, based on the weight of the polymer contained in the liquid crystal aligning agent.

  It is also important to add a so-called cross-linking agent that reacts with the carboxylic acid residue of the polyamic acid to link the polyamic acids to the liquid crystal aligning agent of the present invention in order to prevent deterioration of characteristics over time and environmental degradation. Examples of such a crosslinking agent include polyfunctional epoxies and isocyanate materials as described in Japanese Patent No. 3049699, Japanese Patent Application Laid-Open No. 2005-275360, Japanese Patent Application Laid-Open No. 10-212484, and the like. In addition, a material that improves the strength of a liquid crystal alignment film using a liquid crystal aligning agent prepared by using a polyamic acid or polyimide may be used for the same purpose as described above. I can do it. Examples of such a crosslinking agent include polyfunctional vinyl ethers, maleimides, or bisallyl nadiimide derivatives as described in JP-A-10-310608, JP-A-2004-341030, and the like. The crosslinking agent used in the present invention may be other than these.

  The ratio of these crosslinking agents with respect to the polymer (polyamic acid or polyimide) used for the preparation of the liquid crystal aligning agent of the present invention is preferably in the range of 5 to 200% by weight, and 10 to 100% by weight in order to express the effects of the present invention. % Range is more preferred.

The solvent used in the liquid crystal aligning agent of the present invention is not particularly limited. For example, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), Examples thereof include ethylene glycol monobutyl ether (BC), ethylene glycol monoethyl ether, and γ-butyrolactone. In the present invention, two or more selected from the above solvents may be mixed and used. Further, solvents other than those described above may be used as long as the polymer of the present invention is soluble.
The viscosity of the liquid crystal aligning agent of the present invention varies depending on the application method, the concentration of the polymer, the type of polymer used, and the type and ratio of the solvent. For example, in the case of application by a printing press, it is 5 to 100 mPa · s (more preferably 10 to 70 mPa · s). If it exists in this range, sufficient film thickness will be obtained and there will be no printing nonuniformity. In the case of application by ink jet printing, it is 1 to 30 mPa · s (more preferably 5 to 20 mPa · s).

  Fourth, a liquid crystal alignment film obtained using the liquid crystal aligning agent of the present invention will be described. The liquid crystal alignment film of the present invention may be obtained by using one type selected from the liquid crystal aligning agents of the present invention, and as described above, a mixture of two or more types may be used. It may be what was made.

Thus, polymer blending is often performed for the purpose of more effectively expressing the properties required for the liquid crystal alignment film. When this is performed with a plurality of polymers having different surface energy values when the film is thinned, components having a low surface tension tend to be segregated spontaneously on the film surface. By performing such a polymer blend, a layer exhibiting good liquid crystal orientation is formed on the surface of the alignment film, and a layer expressing good electrical characteristics in the bulk is formed, and the liquid crystal alignment film excellent in both of these characteristics JP-A-8-43831 discloses a method for obtaining the above.

Polymer blending can also be performed in the liquid crystal aligning agent of the present invention. At this time, it is preferable that a polyamic acid or polyimide polymer having a naphthalene ring in the side chain is used as a component having a low surface tension, and a polymer that expresses a higher surface tension is prepared from the above known acid anhydride and diamine. Further, as one of the components that develop a large surface tension, a polymer having a naphthalene ring in the side chain may be used.

  The mixing ratio of the polymer having a lower surface tension (hereinafter referred to as polymer 1) and the polymer having a higher surface tension can be arbitrarily selected between 1 wt% and 99 wt%, respectively. However, in order to develop good electrical characteristics while maintaining good liquid crystal alignment characteristics and a pretilt angle, it is preferable to add the polymer 1 in an amount of 1 to 30% by weight based on the total polymer weight. It is more preferable to add between ˜15% by weight.

Although the manufacturing method of the liquid crystal aligning film produced using the liquid crystal aligning agent of this invention is not specifically limited, For example, the manufacturing method which has the following process can be illustrated.
(1) The liquid crystal aligning agent of the present invention is applied on a substrate by a brush coating method, a dipping method, a spinner method, a spray method, a printing method or the like.
(2) The solvent is evaporated at 50 to 150 ° C, preferably 80 to 120 ° C.
(3) The film is formed by heating at 150 to 400 ° C., preferably 180 to 280 ° C.
(4) The film surface is rubbed with a cloth or the like.
Furthermore, if the surface of the substrate is treated with a silane coupling agent before the liquid crystal aligning agent is applied and a film is formed thereon, the adhesion between the film and the substrate is improved.

  The polyamic acid or polyimide having a naphthalene ring in the side chain used for the production of the liquid crystal aligning agent of the present invention having the above structure is particularly suitable as an alignment film material for a liquid crystal display element. However, the polyamic acid or polyimide having a naphthalene ring in the side chain used for the production of the liquid crystal aligning agent of the present invention is used for various polyimide coating agents, polyimide resin molded products, films, fibers, etc. in addition to the liquid crystal aligning film. I can do it. Furthermore, it can also be used as a raw material for polyamide resin, polyamideimide resin, polyurea resin, or a curing agent for epoxy resin. The characteristics of these materials can be further improved by mixing other polymer compounds such as polyamideimide and polyamide.

Fourthly, the phenylenediamine (2), (3) or (4) of the present invention will be described.
The phenylenediamine represented by the formula (2), (3) or (4) of the present invention can be easily synthesized, for example, by the following method.

(Wherein A ¹ , A ² , X ¹ and R represent the same groups as described above, X ⁴ represents an alkyl having 1 to 12 carbon atoms, X ⁵ represents —O— or —COO—, and X ⁶ represents Represents alkyl having 2 to 12 carbon atoms, Y ¹ represents —Cl, —Br, —I, or trifluoromethylsulfonyl, Y ² represents —OH, —Cl, or —Br, and Y ³ represents —OH. or represents -COCl, Y ⁴ represents -OH or -COCl, Y ⁵ represents -Cl, -Br, -I, para-toluenesulfonyl or -OH.)

In the general formula (3) or (4), when X ³ is alkylene (Scheme 1); the compound represented by the formula (11) is commercially available according to Lambert Brandsma, Preparative Acetological Chemistry, 2nd edition, 1988. The compound represented by (13) can be synthesized by reacting with a known compound represented by (12). This (13) is a commercially available dinitro compound represented by (14), New Experimental Science Course, Volume 14, Synthesis and Reaction of Organic Compounds (I), page 567, 1977 or the same magazine, Volume 14, The compound represented by (15) can be easily synthesized by reacting using the method described in Synthesis and Reaction (II), page 1000, 1977, etc. (3) or (4) is obtained by hydrogenating this (15) according to a conventional method.

In the general formula (3) or (4), in the case of alkylene substituted with —O— or —CO— at the terminal on the A ¹ side of X ³ (Scheme 2); a compound represented by the formula (16): The compound represented by (18) can be synthesized by reacting with a commercially available or known compound represented by (17) in accordance with the above New Experimental Science Course. The target (3) or (4) can be obtained by hydrogenating this (18) in the same manner as described above.

  The compounds represented by the above formula (11) or (16) are commercially available or published in WO2006059149, JP2001-019649, JP2000-128849, JP6-025059. , Japanese Laid-Open Patent Publication No. Hei 2-164843, Helvetica Chimica Acta, 64, 1847 (1981), Helvetica Chimica Acta, 68, 1406 (1985), and the like. Details of these syntheses are described in the Examples. Moreover, the manufacturing method of this invention compound is not limited above.

  The following examples show application examples of phenylenediamines of the present invention and products obtained using the phenylenediamines, that is, resin liquid crystal alignment films using polyimide polymers having a naphthalene ring in the side chain. In the examples, all NMR was measured in deuterated chloroform (500 Hz). For the measurement of molecular weight, GPC was used, polystyrene was used as a standard solution, and DMF was used as an eluent. The viscosity was measured using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., TV-20). The present invention is not limited to these examples.

Evaluation Method of Liquid Crystal Display Element The evaluation method of the liquid crystal display element used in the examples is described below.
1. Pretilt angle It was performed by the crystal rotation method. Specifically, measurement was performed using a liquid crystal characteristic evaluation apparatus OMS-CA3 type manufactured by Chuo Seiki. The specific operation procedure is described in the manual of the measuring apparatus issued by Chuo Seiki Co., Ltd.
2. Burn-in (residual charge)
Residual DC voltage was measured by superimposing 50 mV, 1 kHz alternating current and 0.0036 Hz direct current triangular wave on the liquid crystal cell by the method described in “Miyake et al., Shingaku Giho, EID91-111, p19”. This residual charge was used as an index for image sticking. In other words, the more residual charge, the easier it is to burn.
3. Voltage holding ratio It carried out by the method as described in "Mizushima et al. The measurement conditions were a gate width of 69 μs, a frequency of 60 Hz, and a wave height of ± 4.5V. The larger this value, the better the electrical characteristics.
4). Orientation It was performed by visual observation with a polarizing microscope.
5. Measurement of ion content in liquid crystal (ion density)
According to the method described in Applied Physics, Vol. 65, No. 10, 1065 (1996), measurement was performed using a liquid crystal property measuring system 6254 type manufactured by Toyo Technica. Measurement was performed in a voltage range of ± 10 V using a triangular wave with a frequency of 0.01 Hz.
6). IR spectrum The alignment film formed on the substrate was scraped off, and tablets were prepared with KBr to prepare samples. The measurement was performed using JASCO FT / IR-7300 (JASCO) with 50 integrations.

Example 1
Synthesis of compound (A)

  A mixture of commercially available 6-cyano-2-naphthol (50 g, 300 mmol), 6-chlorohexanol (43 g, 320 mmol), potassium carbonate (45 g, 330 mmol), potassium iodide (1 g, 6 mmol) in DMF (200 ml) Stir at 100 ° C. for 8 hours. After cooling, the solution was poured into pure water (500 ml) and extracted with dichloromethane (500 ml). The organic layer was separated, washed twice with pure water (300 ml), and dried over anhydrous magnesium sulfate. After filtration and evaporation of the solvent under reduced pressure, the residue was purified by column chromatography (silica gel / methylene chloride: methanol = 20: 1 (v / v)) to give 6- (6-cyano-2-naphthoxy) -1 -Hexanol was obtained. Yield 56 g (71% yield).

  A mixture of this compound (56 g, 210 mmol) and triphenylphosphine (83 g, 250 mmol) was dissolved in dichloromethane (500 ml). To this mixture, a solution of carbon tetrabromide (60 g, 230 mmol) in dichloromethane (200 ml) was slowly added dropwise. After reacting for 1 hour, toluene (500 ml) was added to the reaction mixture, and suction filtration was performed on silica gel. After the solvent of the filtrate was distilled off under reduced pressure, the residue was purified by column chromatography (silica gel / toluene) and recrystallization (toluene-heptane) to give 1-bromo-6- (6-cyano-2-naphthoxy) hexane. Got. Yield 56 g (81% yield).

  The above compound (50 g, 150 mmol), 2,4-dinitrophenol (36 g, 160 mmol), and potassium carbonate (25 g, 180 mmol) were stirred in DMF (200 ml) at 100 ° C. for 3 hours. After cooling, the reaction mixture was poured into water (500 ml) and extracted with methylene chloride (500 ml). After the same washing, drying, filtration, and evaporation of the solvent as above, the residue was purified by column chromatography (methylene chloride) to give the desired 4- (6-cyano-2-naphthoxy) -n. -Hexyloxy-1,3-dinitrobenzene was obtained. Yield 35 g (53% yield).

This dinitro compound (35 g, 80 mmol) was hydrogenated in toluene: ethanol (1: 1 (v / v)) solvent (400 ml) using Pd / C as a catalyst. The residue was purified by column chromatography (silica gel / methylene chloride: ethyl acetate = 10: 1 (v / v)) and recrystallization (ethanol) to obtain the target compound (A). Yield 18 g (61% yield).
¹ H NMR; 8.13 (s, 1H), 7.77 (t, 2H, J = 7.86), 7.55 (dd, 1H, J = 7.02, 1.54 Hz), 7.24 (Dd, 1H, J = 6.50, 2.46 Hz), 7.13 (d, 1H, J = 2.32 Hz), 6.61 (d, 1H, J = 8.46 Hz), 6.14 ( d, 1H, J = 2.75 Hz), 6.05 (dd, 1H, J = 5.70, 2.56 Hz) 3.9-3.2 (br s, 4H), 1.90-1.88 , 1.83-1.80, 1.58-1.57 (m, 8H).
Smectic phase → isotropic phase; 59.1 ° C.
Melting point: 96.9 ° C

Example 2
Synthesis of compound (B)

  4- (3-bromopropyloxy) benzoate (40 g, 120 mmol), 5- (4-hydroxyphenylmethyl) -1,3-di synthesized according to Journal of Medicinal Chemistry, 28 (10), 1427 (1985). Nitrobenzene (33 g, 120 mmol) and potassium carbonate (20 g, 140 mmol) were stirred in DMF (100 ml) at 80 ° C. for 8 hours. Post-treatment is performed in the same manner as in Example 1, and purification is performed by column chromatography (silica gel / toluene: ethyl acetate = 10: 1 (v / v)) to obtain the target 4- (3- (4- There was obtained ethyl (1,3-dinitrophenylmethyl) phenoxy) propyloxybenzoate, yield 42 g (72% yield).

  This ester compound (40 g, 42 mmol) and 3N hydrochloric acid (20 ml) were refluxed in acetone (100 ml) for 3 hours. Acetone was distilled off under reduced pressure, and the precipitated crystals were filtered and washed with water (100 ml). The crystals were dried under reduced pressure to obtain the desired 4- (3- (4- (1,3-dinitrophenylmethyl) phenoxy) propyloxybenzoic acid, yield 36 g (yield 96%).

  To a solution of this carboxylic acid derivative (18 g, 40 mmol), 6-cyano-2-naphthol (6.6 g, 39 mmol) and 4- (N, N-dimethyl) pyridine 490 mg (4 mmol) in methylene chloride (100 ml) was added dicyclohexyl. Carbodiimide (9.9 g, 48 mmol) was added, and the mixture was stirred overnight at room temperature. After adding 10 ml of ethyl acetate and stirring for 1 hour, the precipitate was filtered. The organic layer was washed twice with pure water (100 ml) and then dried over anhydrous magnesium sulfate. After filtration and evaporation of the solvent under reduced pressure, the residue was purified by column chromatography (silica gel / toluene: ethyl acetate = 10: 1 (v / v)) to obtain the target compound. Yield 15 g (75% yield).

15 g (29 mmol) of this dinitro compound was hydrogenated according to the method of Example 1. Purification by column chromatography (silica gel / methylene chloride: methanol = 20: 1 (v / v)) and recrystallization (ethanol) gave the target compound (B). Yield 7.1 g (54% yield).
¹ H NMR; 8.15-8.18 (m, 3H), 7.79 (t, 2H, J = 7.86), 7.58 (dd, 1H, J = 7.20, 2.10 Hz) 7.34 (d, 2H, J = 8.55 Hz), 7.25 (dd, 1H, J = 6.45, 2.44 Hz), 7.14 (d, 1H, J = 2.20 Hz), 6.63 (d, 1H, J = 8.50 Hz), 6.15 (d, 1H, J = 2.51 Hz), 6.07 (dd, 1H, J = 5.66, 2.43 Hz) 9-3.1 (br s, 4H), 2.38 (m, 2H).

Example 3
Synthesis of compound (C)

Commercially available 2-acetyloxy-6-bromonaphthalene (30 g, 110 mmol), 5-hexyn-1-ol (12 g, 120 mmol), dichlorobistriphenylphosphine palladium (II) (0.39 g, 0.56 mmol), and A mixture of copper (I) iodide (0.21 g, 1.1 mmol) was added under nitrogen stream in triethylamine (70 ml).
The mixture was stirred at 45 ° C. for 1 hour and further refluxed for 30 minutes. After cooling, the reaction solution was poured into pure water (100 ml) and extracted with ethyl acetate (200 ml). The organic layer was washed twice with pure water (100 ml) and then dried over anhydrous magnesium sulfate. After filtration and distilling off the solvent under reduced pressure, the obtained crude product was purified by column chromatography (silica gel / toluene: ethyl acetate = 10: 1 (v / v)) to obtain the intended 6- (6- Acetyloxy-2-naphthyl) -5-hexyn-1-ol was obtained. Yield 21 g (67% yield)

  The above compound (21 g, 74 mmol) was brominated according to the same method as in Example 1. The obtained crude product was purified by column chromatography (silica gel / toluene) to obtain the target 1- (6-acetyloxy-2-naphthyl) -6-bromo-1-hexyne. Yield 20 g (78% yield).

  The above compound (20 g, 58 mmol) was reacted with 2,4-dinitrophenol according to the same method as in Example 1. The obtained crude product was purified by column chromatography (silica gel / toluene: ethyl acetate = 30: 1 (v / v)) to give the desired 1- (6- (6-acetyloxy-2-naphthyl). ) -1-Hexynyloxy) -2,4-dinitrophenol was obtained. Yield 14 g (55% yield).

14 g (31 mmol) of this dinitro compound was hydrogenated according to the method of Example 1. Purification by column chromatography (silica gel / methylene chloride: methanol = 20: 1 (v / v)) and recrystallization (ethanol) gave the target compound (C). Yield 5.8 g (48% yield).
¹ H NMR: 7.7-7.8 (m, 2H), 7.42 (s, 1H), 7.22 (dd, 1H, J = 8.30, 2.25 Hz), 7.16 (dd , 1H, J = 8.00, 2.32 Hz), 7.08 (s, 1H), 6.62 (d, 1H, J = 8.32 Hz), 6.13 (d, 1H, J = 2. 80 Hz), 6.08 (dd, 1H, J = 7.90, 2.40 Hz) 3.7-3.0 (brs, 4H), 1.9-1.5 (m, 8H).

上記化合物（Ｃ）（２．０ｇ、５．１ｍｍｏｌ）にエタノール（２０ｍｌ）を加え、１０重量％水酸化ナトリウム水溶液５ｍｌを加えた。２時間還流後冷却し、３ＮＨＣｌを加え、反応液を中性にした。生じた沈殿をろ過し目的物を得た。収量１．４ｇ（収率７８％）。
¹Ｈ ＮＭＲ；７．５−７．６（ｍ，２Ｈ），６．０−７．０（ｍ，４Ｈ）、６．６５（ｄ，１Ｈ，Ｊ＝８．４４Ｈｚ）、６．１１（ｄ，１Ｈ，Ｊ＝２．４３Ｈｚ）、６．１１（ｄｄ，１Ｈ，Ｊ＝８．４０，２．２３Ｈｚ）３．７−３．０（ｂｒ s，４Ｈ）、１．９−１．５（ｍ，８Ｈ）。 Example 4
Synthesis of compound (D)

Ethanol (20 ml) was added to the compound (C) (2.0 g, 5.1 mmol), and 5 ml of a 10 wt% aqueous sodium hydroxide solution was added. The mixture was refluxed for 2 hours, cooled, and 3N HCl was added to neutralize the reaction solution. The resulting precipitate was filtered to obtain the desired product. Yield 1.4 g (78% yield).
¹ H NMR: 7.5-7.6 (m, 2H), 6.0-7.0 (m, 4H), 6.65 (d, 1H, J = 8.44 Hz), 6.11 (d , 1H, J = 2.43 Hz), 6.11 (dd, 1H, J = 8.40, 2.23 Hz) 3.7-3.0 (br s, 4H), 1.9-1.5 ( m, 8H).

実施例1で合成した６−（６−シアノ−２−ナフトキシ）−１−ヘキサノール（８．０ｇ、３０ｍｍｏｌ）およびピリジン（３．５ｇ、４４ｍｍｏｌ）を塩化メチレン（５０ｍｌ）に溶解した。この混合溶液に３，５−ジニトロ安息香酸クロリド（７．３ｇ、３２ｍｍｏｌ）の塩化メチレン（５０ｍｌ）溶液を室温で滴下した。室温で１時間反応後、反応液を純水（１００ｍｌ）に加えた。有機層を分離後、実施例１と同様な後処理を行った。得られた粗生成物をカラムクロマトグラフィー（シリカゲル／トルエン）で精製することにより、目的とする３，５−ジニトロ安息香酸 ６−（６−シアノ−２−ナフトキシ）−１−ヘキシルエステルを得た。収量１２ｇ（収率８５％）。 Example 5
Synthesis of compound (E)

6- (6-Cyano-2-naphthoxy) -1-hexanol (8.0 g, 30 mmol) and pyridine (3.5 g, 44 mmol) synthesized in Example 1 were dissolved in methylene chloride (50 ml). To this mixed solution, a solution of 3,5-dinitrobenzoic acid chloride (7.3 g, 32 mmol) in methylene chloride (50 ml) was added dropwise at room temperature. After reacting at room temperature for 1 hour, the reaction solution was added to pure water (100 ml). After separating the organic layer, the same post-treatment as in Example 1 was performed. The obtained crude product was purified by column chromatography (silica gel / toluene) to obtain the desired 3,5-dinitrobenzoic acid 6- (6-cyano-2-naphthoxy) -1-hexyl ester. . Yield 12 g (85% yield).

10 g (22 mmol) of this dinitro compound was subjected to hydrogenation reaction according to the method of Example 1. Purification by column chromatography (silica gel / methylene chloride: methanol = 20: 1 (v / v)) and recrystallization (ethanol) gave the target compound (E). Yield 4.8 g (55% yield).
¹ H NMR; 8.13 (s, 1H), 7.76 (t, 2H, J = 8.40), 7.54 (dd, 1H, J = 8.00, 2.32 Hz), 7.24 (Dd, 1H, J = 7.88, 1.70 Hz), 7.14 (d, 1H, J = 2.06 Hz), 6.92 (d, 2H, J = 2.10 Hz), 6.25 ( d, 1H, J = 2.35 Hz), 3.75 (br s, 4H), 1.9-1.6 (m, 8H).

Example 6 (Synthesis of polyamic acid)
In a 100 ml three-necked flask, 3.2224 g (8.583 mmol) of the compound (A) synthesized in Example 1 was placed and dissolved in 22.5 g of NMP. Pyromellitic anhydride 0.9360g (PMDA, 4.921mmol) and cyclobutane tetracarboxylic dianhydride 0.8416g (CBDA, 4.921mmol) were added here, and it stirred for 1 hour. Thereafter, this solution was diluted with 22.5 g of BC to obtain a clear solution of about 5% by weight of polyamic acid. The weight average molecular weight of this solution was 59,000, and the viscosity at 25 ° C. was 10.2 kPa · s. Hereinafter, this solution is referred to as polymer solution A.

  In the same manner, polymer solutions shown in Table 4 were prepared.

Example 9
The polymer solution A was dropped on a transparent glass substrate provided with an ITO electrode on one side and applied by a spinner method (2200 rpm, 15 seconds). After application, the solvent was evaporated at 80 ° C. for 5 minutes, and then heat treatment was performed in an oven at 210 ° C. for 30 minutes to obtain a resin film having a thickness of about 70 nm. After rubbing the glass substrate on which this resin film has been formed (brush tip pushing amount: 0.4 mm, roller rotation speed: 300 rpm, roller feed speed: 30 mm / sec, number of times: 1), the rubbing direction becomes antiparallel. A liquid crystal cell having a cell thickness of 7 μm was assembled. A liquid crystal composition A composed of the following compounds was poured into this cell, subjected to an isotropic treatment at 110 ° C. for 30 minutes, and cooled to room temperature to obtain a liquid crystal display element.

The residual DC of this liquid crystal display element was 207 mV at 25 ° C., the VHR at 20, 60, and 90 ° C. was 94.2, 93.0, 91.7%, respectively, and the ion density was 237 pC. The pretilt angle was measured using this display element and found to be 1.7 degrees. Furthermore, as a result of observation with a polarizing microscope, no light penetration due to poor alignment was observed. When the display element was rotated with respect to the polarized light, clear light and darkness was observed (these values are the initial values). The cell was allowed to stand at 100 ° C. for 20 hours, cooled to room temperature, and then these values were measured again. (This value is regarded as the value after high temperature.) As a result, the residual DC was 213 mV (25 ° C.), the VHR was 94.0 (20), 92.8 (60), 90.9% (90 ° C.), and the ion density was 254 pC. The pretilt angle was 1.7 degrees. Furthermore, as a result of observation with a polarizing microscope, no light penetration due to poor alignment was observed. When the display element was rotated with respect to the polarized light, clear contrast was observed. In addition, “shining” as used in the present application refers to a state in which black is brighter than a practical level when the display element is rotated into a dark field when observing a polarized microscope made of crossed Nicols.

Examples 10 and 11
A liquid crystal display device was produced in the same manner as in Example 9 except that the polymer solution A was changed to the polymer solution shown below. Table 5 shows the physical property measurement results of these elements.

  IR spectra of liquid crystal alignment films prepared from these polymer solutions A to C are shown in FIGS.

Example 12
The polymer solution A is replaced with a mixture of the polymer solution A and the polymer solution D (mixing ratio 1: 1 (v / v)), and the mixture of the polymer solution is further mixed with NMP / BC = 1/1 (v / v). Diluted to 3% by weight. Using this varnish, a liquid crystal display element was produced in the same manner as in Example 7. The physical property measurement results of this display element are shown below.

Initial value residual DC; 212 mV
VHR; 98.2 (20), 97.0 (60), 94.8% (90 ° C.)
Pretilt angle; 1.0 degree Ion density; 143pC
No light.
High temperature post-residue DC: 224 mV
VHR; 98.1 (20), 96.8 (60), 94.6% (90 ° C.)
Pretilt angle; 1.1 degree Ion density; 158pC
No light.

Example 13
The polymer solution A was diluted to 3% by weight with a mixed solvent of NMP / BC = 1/1 (v / v) containing 1.7% by weight of the following compound (F) described in JP-A No. 2004-341030. A liquid crystal display element was produced in the same manner as in Example 7 using this polymer solution. The physical property measurement results of this display element are shown below.

Initial value residual DC; 212 mV
VHR; 96.2 (20), 94.6 (60), 93.6% (90 ° C.)
Pretilt angle: 1.5 degrees Ion density: 167pC
No light.
High temperature post-residue DC: 232 mV
VHR; 95.8 (20), 94.5 (60), 92.9% (90 ° C.)
Pretilt angle: 1.5 degrees Ion density: 176 pC
No light.

Comparative Example A liquid crystal display device was produced in the same manner as in Example 7 except that the liquid crystal aligning agent E having the following composition was used instead of the liquid crystal aligning agent A, and the electrical characteristics thereof were measured. The diamine (G) used here as a raw material was synthesized according to the method described in EP0679633. The results are shown below.

Initial value residual DC: 444 mV
VHR; 93.2 (20), 91.4 (60), 87.3% (90 ° C.)
Pretilt angle: 1.7 degrees Ion density: 425pC
No light.
High temperature post-residue DC: 420 mV
VHR; 92.8 (20), 90.9 (60), 86.5% (90 ° C.)
Pretilt angle; 1.8 degrees Ion density; 463pC
No light.

It is a figure which shows IR spectrum of the liquid crystal aligning film produced from the polymer solution A of this invention. It is a figure which shows IR spectrum of the liquid crystal aligning film produced from the polymer solution B of this invention. It is a figure which shows IR spectrum of the liquid crystal aligning film produced from the polymer solution C of this invention.

Claims (12)

In the liquid crystal aligning agent containing polyamic acid or polyimide having a naphthalene ring in the side chain,
Der Ru liquid crystal alignment agent which is synthesized from a diamine comprising a phenylenediamine represented by the side chains to the polyamic acid or the polyimide is represented by the following general formula having a naphthalene ring (3).

(In the formula, A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ³ represents an alkylene having 1 to 13 carbon atoms. Of which methylene bonded to A ¹ may be substituted with —O— or —COO—, X ² represents a single bond, —COO—, or —CONR ² —, and R ² represents hydrogen or represents methyl, R represents hydrogen, alkyl having 1 to 12 carbon atoms, -CN, -F, -OH, or -CO ₂ R ^3, R ³ represents methyl or ethyl.) In the liquid crystal aligning agent containing polyamic acid or polyimide having a naphthalene ring in the side chain,
Der Ru liquid crystal alignment agent which is synthesized from a diamine comprising a phenylenediamine represented by the side chains to the polyamic acid or the polyimide is represented by the following general formula having a naphthalene ring (4).

(In the formula, A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ³ represents an alkylene having 1 to 13 carbon atoms. Of which methylene bonded to A ¹ may be substituted with —O— or —COO—, X ² represents a single bond, —COO—, or —CONR ² —, and R ² represents hydrogen or represents methyl, R represents hydrogen, alkyl having 1 to 12 carbon atoms, -CN, -F, -OH, or -CO ₂ R ^3, R ³ represents methyl or ethyl.) In the general formula (3), X ³ is alkylene having 1 to 6 carbon atoms, methylene bonded to A ¹ may be substituted with —O— or —COO—, and X ² is a single bond. or a -COO-, liquid crystal alignment agent according to claim 1 wherein R is -CN, -OH, or contains a polyamic acid or a polyimide synthesized from diamines containing phenylenediamine is -CO ₂ Me. In the general formula (4), X ³ is alkylene having 1 to 6 carbon atoms, methylene bonded to A ¹ may be substituted with —O— or —COO—, and X ² is a single bond. or a -COO-, liquid crystal alignment agent according to claim 2 in which R is -CN, -OH, or contains a polyamic acid or a polyimide synthesized from diamines containing phenylenediamine is -CO ₂ Me. The polyamic acid or polyimide further synthesized from an amine component containing one or more selected from the group consisting of diamines represented by the following general formulas (3-1) to (3-52): The liquid crystal aligning agent as described in any one of 4 .

The liquid crystal aligning agent according to claim 5 , wherein the amine component contains 4,4′-diaminodiphenylmethane. The polyamic acid or polyimide is synthesized using tetracarboxylic dianhydride as an acid component, and the tetracarboxylic dianhydride is represented by the following formulas (2-1) to (2-38). The liquid crystal aligning agent as described in any one of Claims 1-6 containing 1 or more types chosen from aromatic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic acid.

The liquid crystal aligning agent according to claim 7 , wherein the tetracarboxylic dianhydride is pyromellitic dianhydride and / or cyclobutanetetracarboxylic dianhydride. Phenylenediamine represented by the following general formula (3).

(In the formula, A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ³ represents an alkylene having 1 to 13 carbon atoms. Of which methylene bonded to A ¹ may be substituted with —O— or —COO—, X ² represents a single bond, —COO—, or —CONR ² —, and R ² represents hydrogen or represents methyl, R represents hydrogen, alkyl having 1 to 12 carbon atoms, -CN, -F, -OH, or -CO ₂ R ^3, R ³ represents methyl or ethyl.) Phenylenediamine represented by the following general formula (4).

(In the formula, A ¹ represents a single bond, phenylene, or naphthylene, A ² represents phenylene or naphthylene, at least one of A ¹ or A ² is naphthylene, and X ³ represents an alkylene having 1 to 13 carbon atoms. Of which methylene bonded to A ¹ may be substituted with —O— or —COO—, X ² represents a single bond, —COO—, or —CONR ² —, and R ² represents hydrogen or represents methyl, R represents hydrogen, alkyl having 1 to 12 carbon atoms, -CN, -F, -OH, or -CO ₂ R ^3, R ³ represents methyl or ethyl.) In the general formula (3), X ³ is alkylene having 1 to 6 carbon atoms, methylene bonded to A ¹ may be substituted with —O— or —COO—, and X ² is a single bond. or a -COO-, phenylenediamine according to claim 9 R is -CN, -OH or -CO ₂ Me,. In the general formula (4), X ³ is alkylene having 1 to 6 carbon atoms, methylene bonded to A ¹ may be substituted with —O— or —COO—, and X ² is a single bond. or a -COO-, phenylenediamine of claim 10 R is -CN, -OH or -CO ₂ Me,.

Images