JP2017003965A - Liquid crystal aligning agent for forming liquid crystal alignment film for photo-alignment, liquid crystal alignment film and liquid crystal display element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal display element that prevents degradation in display quality even when the element is exposed to intense light for a long time, and to provide a liquid crystal aligning agent capable of giving the above display element, and a liquid crystal alignment film.SOLUTION: A liquid crystal aligning agent for photo-alignment is provided, comprising at least one polymer selected from a group consisting of a polyamic acid, a polyamic acid ester and a polyimide obtained by imidizing the polyamic acid or the polyamic acid ester, where the polyamic acid is obtained by reacting at least one compound selected from a tetracarboxylic acid dianhydride and its derivative with diamine. At least one raw material monomer of the polymer has a photoisomerization structure; and the diamine comprises at least one compound represented by formula (1) below. In formula (1), n independently represents an alkylene having 1 to 6 carbon atoms.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal aligning agent for photo-alignment used in a photo-alignment method, a photo-alignment film using the same, and a liquid crystal display element.

Various display devices such as personal computer monitors, LCD TVs, video camera viewfinders, and projection displays, as well as optoelectronic devices such as optical printer heads, optical Fourier transform elements, and light valves, have been commercialized today. Generally used liquid crystal display elements are display elements using nematic liquid crystals. As a display system of the nematic liquid crystal display element, a TN (Twisted Nematic) mode and an STN (Super Twisted Nematic) mode are well known. In recent years, in order to improve the narrow viewing angle, which is one of the problems of these modes, a TN liquid crystal display device using an optical compensation film, MVA (Multi -domain Vertical Alignment) mode, IPS (In-Plane Switching) mode of horizontal electric field method, FFS (Fringe Field Switching) mode, etc. have been proposed and put to practical use.

The development of the technology of the liquid crystal display element is achieved not only by simply improving these driving methods and element structures but also by improving the components used in the elements. Among the components used in liquid crystal display elements, the liquid crystal alignment film is one of important materials related to display quality, and the performance of the alignment film can be improved with the improvement in quality of the liquid crystal display element. It is becoming important.

The liquid crystal alignment film is formed from a liquid crystal aligning agent. The liquid crystal aligning agent mainly used at present is a solution (varnish) obtained by dissolving polyamic acid or soluble polyimide in an organic solvent. After this solution is applied to the substrate, it is formed by means such as heating to form a polyimide-based liquid crystal alignment film. After film formation, an orientation treatment suitable for the above-described display mode is performed as necessary.

Industrially, a rubbing method that is simple and capable of high-speed processing of a large area is widely used as an alignment processing method. The rubbing method is a process of rubbing the surface of the liquid crystal alignment film in one direction using a cloth in which fibers of nylon, rayon, polyester, or the like are planted, and this makes it possible to obtain uniform alignment of liquid crystal molecules. However, problems such as dust generation due to the rubbing method and generation of static electricity have been pointed out, and in recent years, an alignment treatment method that replaces the rubbing method has been actively developed.

A photo alignment treatment method in which alignment treatment is performed by irradiating light is attracting attention as an alignment treatment method replacing the rubbing method. Many alignment mechanisms such as a photodecomposition method, a photoisomerization method, a photodimerization method, and a photocrosslinking method have been proposed for the photoalignment treatment method (see, for example, Non-Patent Document 1, Patent Documents 1 and 2). The photo-alignment method has higher uniformity of alignment than the rubbing method, and it is a non-contact alignment method, so the film is not damaged and causes the display defects of liquid crystal display elements such as dust generation and static electricity. There are advantages such as reduction.
So far, studies have been made on photo-alignment films having photoreactive groups that cause photoisomerization or photodimerization in the polyamic acid structure (see, for example, Patent Documents 1 to 7). Especially, the photo-alignment film | membrane which applied the technique of the photoisomerization described in patent documents 3-5 had large anchoring energy, and its orientation was favorable.

On the other hand, a low ion density is an important characteristic required for the liquid crystal alignment film in order to improve the display quality of the liquid crystal display element. When the ion density is high, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, which may hinder normal gradation display. Even if the initial ion density is low, it is not preferable that the ion density after the high-temperature test increases.
As an attempt to solve this problem, a method of introducing a diamine having a cyclic secondary amine structure such as piperazine into a raw material and introducing the structure into a polyimide chain (see Patent Documents 7 and 8). It has been known.

In recent years, the use of liquid crystal display elements has been wide-ranging, such as monitors for personal computers, liquid crystal televisions, mobile phones, smartphone displays, and liquid crystal projectors. The liquid crystal display elements for these applications have specifications that increase the brightness of the backlight as a light source compared to conventional products in consideration of improvement of display quality and outdoor use. Therefore, there is a demand for a liquid crystal alignment film in which the ion density does not increase even when exposed to intense light for a long time as well as heat.

JP-A-9-297313 JP-A-10-251646 JP-A-2005-275364 JP2007-248637 JP2009-069493 JP2008-233713 JP2009-175684A JP2011-028223

Liquid Crystal, Vol. 3, No. 4, 262 pages, 1999

An object of the present invention is to provide a liquid crystal alignment film for photoalignment in which the ion density does not increase even when exposed to intense light for a long time, and photoalignment capable of forming such a liquid crystal alignment film for photoalignment A liquid crystal aligning agent for use is provided. A further object of the present invention is to provide a liquid crystal display element that does not deteriorate the display quality even when exposed to strong light for a long time by the liquid crystal alignment film for photo-alignment.

As a result of intensive studies, the present inventors have used the diamine represented by the formula (1) as a raw material for the liquid crystal aligning agent for photo-alignment, so that the liquid crystal aligning film for photo-alignment obtained thereby is resistant to heat. In addition, the present inventors have found that the ion density does not increase even when exposed to intense light for a long time, and completed the present invention.

式（１）において、ｎは独立して炭素数１〜６のアルキレンであり；そして、
前記テトラカルボン酸二無水物の誘導体とは、テトラカルボン酸ジエステルまたはテトラカルボン酸ジエステルジクロリドである。 The present invention comprises the following.
[1] Selected from the group consisting of polyamic acid, polyamic acid ester obtained by reacting diamine with at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof, and polyimide obtained by imidizing these. A liquid crystal aligning agent for photoalignment comprising at least one polymer selected from the group consisting of:
The liquid crystal aligning agent for photo-alignment in which at least 1 of the raw material monomer of the said polymer has a photoreactive structure, and the said diamine contains at least 1 of the compound represented by following formula (1).

In formula (1), n is independently alkylene having 1 to 6 carbons; and
The derivative of tetracarboxylic dianhydride is tetracarboxylic acid diester or tetracarboxylic acid diester dichloride.

[2] A compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof, and diamines, and at least one of the compounds represented by formula (1) Containing at least one polymer obtained by reacting a raw material monomer containing one; or
At least one polymer obtained by reacting a raw material monomer containing a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof, and diamine;
None of tetracarboxylic dianhydride and derivatives thereof, and diamines have a photoreactive structure, and a raw material monomer containing at least one compound represented by formula (1) is reacted with diamine. The liquid crystal aligning agent for photo-alignment according to item [1], comprising at least one of the obtained polymers.

[3] A compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof, and diamines, and at least one of the compounds represented by formula (1) Including at least one polymer obtained by reacting raw material monomers including one and another polymer used by mixing with the polymer,
The liquid crystal aligning agent for photo-alignment according to item [2], wherein all of tetracarboxylic dianhydride and derivatives thereof, and diamine are polymers obtained by reacting raw material monomers having no photoreactive structure. .

[4] A compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof and diamine, and at least one of the compounds represented by formula (1) Including at least one polymer obtained by reacting raw material monomers including one and another polymer used by mixing with the polymer,
None of tetracarboxylic dianhydride and its derivatives, and diamines have a photoreactive structure, and are obtained by reacting raw material monomers containing at least one compound represented by formula (1). The liquid crystal aligning agent for photo-alignment according to item [2], which is a polymer obtained.

[5] At least one polymer obtained by reacting a raw material monomer containing a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof, and diamine;
None of tetracarboxylic dianhydride and derivatives thereof, and diamines have a photoreactive structure, and a raw material monomer containing at least one compound represented by formula (1) is reacted with diamine. The liquid crystal aligning agent for photo-alignment according to item [1], comprising at least one of the obtained polymers.

[6] The liquid crystal aligning agent for photoalignment according to any one of [1] to [5], wherein the photoreactive structure of the raw material monomer is a photoisomerized structure.

[7] The liquid crystal aligning agent for photoalignment according to any one of [1] to [5], wherein the photoreactive structure of the raw material monomer is a structure in which a bond is cleaved by ultraviolet rays.

[8] The liquid crystal aligning agent for photo alignment according to any one of [1] to [5], wherein the photoreactive structure of the raw material monomer is a photodimerization structure.

式（ＩＩ）〜（Ｖ）において、Ｒ^２およびＲ^３は独立して−ＮＨ_２を有する１価の有機基または−ＣＯ−Ｏ−ＣＯ−を有する１価の有機基であり、式（ＩＶ）においてＲ^４は２価の有機基であり、式（ＶＩ）においてＲ^５は独立して−ＮＨ_２または−ＣＯ−Ｏ−ＣＯ−を有する芳香環である。 [9] The liquid crystal alignment for photoalignment according to the item [6], wherein the tetracarboxylic dianhydride or diamine having a photoisomerization structure is at least one of the compounds represented by formulas (II) to (VI). Agent;

In formulas (II) to (V), R ² and R ³ are each independently a monovalent organic group having —NH ₂ or a monovalent organic group having —CO—O—CO—, in) ^{R 4} is a divalent organic group, and ^{R 5} in formula (VI) is an aromatic ring having a -NH ₂ or -CO-O-CO- independently.

上記各式において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し；
式（Ｖ−２）において、Ｒ^６は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ａは０〜２の整数であり；
式（Ｖ−３）において、環Ａおよび環Ｂはそれぞれ独立して、単環式炭化水素、縮合多環式炭化水素および複素環から選ばれる少なくとも１つであり、
Ｒ^１１は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｎ（ＣＨ_３）ＣＯ−、または−ＣＯＮ（ＣＨ_３）−であり、
Ｒ^１２は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｎ（ＣＨ_３）ＣＯ−、または−ＣＯＮ（ＣＨ_３）−であり、
Ｒ^１１およびＲ^１２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは−Ｏ−で置換されてもよく、
Ｒ^７〜Ｒ^１０は、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり、そして、
ｂ〜ｅは、それぞれ独立して、０〜４の整数である。 [10] A tetracarboxylic dianhydride or diamine having a photoisomerization structure is represented by the formula (II-1), (II-2), (III-1), (III-2), (IV-1), ( In item [9], which is at least one selected from the group of compounds represented by IV-2), (V-1) to (V-3), (VI-1), and (VI-2): The liquid crystal aligning agent for optical alignment as described;

In the above formulas, a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;
In formula (V-2), R ⁶ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and a is an integer of 0 to 2;
In formula (V-3), ring A and ring B are each independently at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocyclic rings,
R ¹¹ is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, —CONH—, —N (CH ₃ ) CO—, or —CON (CH ₃ ) —,
R ¹² is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, —CONH—, —N (CH ₃ ) CO—, or —CON (CH ₃ ) —,
In R ¹¹ and R ¹² , one or two of the linear alkylene —CH ₂ — may be substituted with —O—,
R ^{7 to} R ¹⁰ are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , or —OH; and
b to e are each independently an integer of 0 to 4.

[11] It further contains at least one selected from the group consisting of an alkenyl-substituted nadiimide compound, a compound having a radical polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. 10] The liquid crystal aligning agent for photo-alignment of any one of [10].

[12] The liquid crystal aligning agent for photo-alignment according to any one of [1] to [11], which is used for producing a horizontal electric field type liquid crystal display element.

[13] A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of [1] to [12].

[14] A liquid crystal display device having the liquid crystal alignment film according to the item [13].

[15] A horizontal electric field type liquid crystal display device having the liquid crystal alignment film according to the item [13].

The liquid crystal display element having the liquid crystal alignment film for photo-alignment formed by the liquid crystal aligning agent for photo-alignment of the present invention does not increase in ion density even when used for a long time, and exhibits high display quality even when exposed to strong light. Can be maintained.

<Liquid crystal aligning agent for photo-alignment>
The liquid crystal aligning agent for photo-alignment of the present invention is a reaction product of at least one selected from tetracarboxylic dianhydride and derivatives thereof and diamine, polyamic acid, polyamic acid ester, and polyimide obtained by imidizing them At least one polymer selected from the group consisting of: at least one of the raw material monomers of the polymer having a photoreactive structure, and at least one of the compounds represented by formula (1), It is characterized by including. The polyamic acid, polyamic acid ester, and polyimide obtained by imidizing them are components that dissolve in a solvent when the liquid crystal aligning agent containing a solvent is described later, and the liquid crystal aligning film that describes the liquid crystal aligning agent described later Is a component capable of forming a liquid crystal alignment film containing polyimide as a main component. The polyamic acid ester can be synthesized by reacting the above-mentioned polyamic acid with a hydroxyl group-containing compound, halide, epoxy group-containing compound or the like, or a tetracarboxylic acid diester or tetracarboxylic acid diester derived from an acid dianhydride. It can be synthesized by a method of synthesizing by reacting dichloride and diamine. A tetracarboxylic acid diester derived from an acid dianhydride can be obtained, for example, by reacting an acid dianhydride with 2 equivalents of an alcohol to cause ring opening, and a tetracarboxylic acid diester dichloride is obtained by 2 equivalents of a tetracarboxylic acid diester. It can be obtained by reacting with a chlorinating agent such as thionyl chloride. The polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. The liquid crystal aligning agent for photo-alignment of the present invention may contain one or more of these polyamic acids, polyamic acid esters, and polyimides obtained by imidizing them.

In the liquid crystal aligning agent for photo-alignment of the present invention, at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof, and diamine has a photoreactive structure, and the diamine is represented by the above formula (1). At least one selected from the group consisting of tetracarboxylic acid and derivatives thereof, and diamine, which contains at least one polymer obtained by reacting a raw material monomer containing at least one of the represented compounds None of the polymer obtained by reacting the raw material monomer having a reactive structure, tetracarboxylic dianhydride and its derivative, and diamine have a photoreactive structure, and the diamine has the following formula: Light comprising at least one polymer obtained by reacting a raw material monomer containing at least one of the compounds represented by (1) It is a direction for the liquid crystal alignment agent.

<Photoreactive structure>
In the present invention, the photoreactive structure means, for example, a photoisomerization structure that undergoes isomerization by ultraviolet irradiation, a photolytic structure that cleaves a bond, or a photodimerization structure that undergoes dimerization. A raw material monomer having a structure that causes a photoreaction upon irradiation with ultraviolet rays can be appropriately used.

式（ＩＩ）〜（Ｖ）において、Ｒ^２およびＲ^３は独立して−ＮＨ_２を有する１価の有機基または−ＣＯ−Ｏ−ＣＯ−を有する１価の有機基であり、式（ＩＶ）においてＲ^４は２価の有機基であり、式（ＶＩ）においてＲ^５は独立して−ＮＨ_２もしくは−ＣＯ−Ｏ−ＣＯ−を有する芳香環である。 Examples of the monomer having a photoisomerization structure include a tetracarboxylic dianhydride having a photoisomerization structure or a diamine having a photoisomerization structure, and the following formulas (II) to (VI) having good photosensitivity. It is preferably at least one selected from the group of compounds represented by formula (V), more preferably a compound represented by formula (V).

In formulas (II) to (V), R ² and R ³ are each independently a monovalent organic group having —NH ₂ or a monovalent organic group having —CO—O—CO—, R ⁴ is a divalent organic group, and in formula (VI), R ⁵ is independently an aromatic ring having —NH ₂ or —CO—O—CO—.

The photoisomerization structure may be incorporated in either the main chain or the side chain of the polyamic acid or derivative thereof in the present invention, but can be suitably used for a horizontal electric field type liquid crystal display element by incorporating it in the main chain.

上記各式において、環を構成するいずれかの炭素原子に結合位置が固定されていない基は、その環における結合位置が任意であることを示し、式（Ｖ−２）において、Ｒ^６は独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＣＯＯＣＨ_３であり、ａは０〜２の整数であり、式（Ｖ−３）において、環Ａおよび環Ｂはそれぞれ独立して、単環式炭化水素、縮合多環式炭化水素および複素環から選ばれる少なくとも１つであり、Ｒ^１１は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｎ（ＣＨ_３）ＣＯ−、または−ＣＯＮ（ＣＨ_３）−であり、Ｒ^１２は、炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｎ（ＣＨ_３）ＣＯ−、または−ＣＯＮ（ＣＨ_３）−であり、Ｒ^１１およびＲ^１２において、直鎖アルキレンの−ＣＨ_２−の１つまたは２つは−Ｏ−で置換されてもよく、Ｒ^７〜Ｒ^１０は、それぞれ独立して、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−ＯＨであり、そして、ｂ〜ｅは、それぞれ独立して、０〜４の整数である。 Examples of the material having the photoisomerized structure include the following formulas (II-1), (II-2), (III-1), (III-2), (IV-1), (IV-2), ( V-1) to (V-3), (VI-1), and at least one selected from the group of compounds represented by (VI-2) can be preferably used.

In each of the above formulas, a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary, and in formula (V-2), R ⁶ is independently _-CH 3 _and, -OCH 3, a -CF ₃ or -COOCH _3,, a is an integer of 0 to 2, in the formula (V-3), ring a and ring B are each independently, It is at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons, and heterocyclic rings, and R ¹¹ is linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, —CONH—, —N (CH ₃ ) CO—, or —CON (CH ₃ ) —, wherein R ¹² is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, _{-CONH -, - N (CH 3} ) CO-, or —CON (CH ₃ ) —, and in R ¹¹ and R ¹² , one or two of —CH ₂ — of the linear alkylene may be substituted with —O—, and each of R ^{7 to} R ¹⁰ is _{independently,} -F, -CH _3, -OCH 3, a -CF ₃ or -OH,, and, b to e are each independently an integer of 0 to 4.

The compounds represented by the above formulas (V-1), (V-2) and (VI-2) can be particularly preferably used from the viewpoint of their photosensitivity. In the formulas (V-2) and (VI-2), the compound in which the amino group is bonded to the para-position, and in the formula (V-2), the compound in which a = 0 is selected from the viewpoint of the orientation. It can be used more suitably.

Acid dianhydrides or diamines having a structure capable of causing isomerization by ultraviolet irradiation shown in the formulas (II-1) to (VI-2) are represented by the following formulas (II-1-1) to (VI-2-3). It can be expressed specifically.

Among these, by using the compounds represented by the formulas (V-1-1) to (V-3-8), it is possible to obtain a liquid crystal aligning agent for photo-alignment with higher sensitivity to ultraviolet irradiation. it can. Formula (V-1-1), Formula (V-2-1), Formula (V-2-4) to Formula (V-2-11), and Formula (V-3-1) to Formula (V-3) By using the compound represented by -8), it is possible to obtain a liquid crystal aligning agent for photoalignment capable of aligning liquid crystal molecules more uniformly. By using the compounds represented by the formulas (V-2-4) to (V-3-8), it is possible to obtain a liquid crystal aligning agent for photo-alignment in which the formed alignment film can be less colored. .

式（ＰＡ−３）〜式（ＰＡ−６）において、Ｒ^１１は独立して、炭素数１〜５のアルキル基である。 Examples of the monomer having a photolytic structure include compounds represented by the following formulas (PA-1) to (PA-6).

In formula (PA-3) to formula (PA-6), R ¹¹ is independently an alkyl group having 1 to 5 carbon atoms.

Among these, formula (PA-1), formula (PA-2), and formula (PA-5) are preferably used.

The compounds represented by the formulas (PA-1) to (PA-6) are materials for liquid crystal aligning agents using liquid crystal aligning ability based on photoisomerization reaction and liquid crystal aligning agents using liquid crystal aligning ability based on photodimerization. When used as a tetracarboxylic dianhydride having no photoreactive structure as described above.

式（ＰＤＩ−１２）において、Ｒ^１２は炭素数１〜１０のアルキルまたはアルコキシであり、アルキルまたはアルコキシの少なくとも１つの水素はフッ素に置き換えられていてもよい。 Examples of the monomer having a photodimerization structure include diamine compounds represented by the following formulas (PDI-9) to (PDI-13).

In Formula (PDI-12), R ¹² is alkyl or alkoxy having 1 to 10 carbons, and at least one hydrogen of alkyl or alkoxy may be replaced by fluorine.

Among these, the diamine represented by Formula (PDI-9) and Formula (PDI-11) can be used suitably.

In an embodiment in which a tetracarboxylic dianhydride having no photoreactive structure (non-photosensitive) and a (photosensitive) tetracarboxylic dianhydride having a photoreactive structure are used in combination, the alignment film is sensitive to light. In order to prevent the decrease, the photosensitive tetracarboxylic dianhydride is preferably 30 to 100 mol% based on the total amount of the tetracarboxylic dianhydride used as a raw material when producing the polyamic acid or derivative thereof of the present invention. 50 to 100 mol% is particularly preferable. Further, two or more photosensitive tetracarboxylic dianhydrides may be used in combination in order to improve the above-described various characteristics such as sensitivity to light, electrical characteristics, and afterimage characteristics.

In an embodiment in which a diamine having no photoreactive structure (non-photosensitive) and a (photosensitive) diamine having a photoreactive structure are used in combination, the polyamic of the present invention is used to prevent a decrease in sensitivity of the alignment film to light. The photosensitive diamine is preferably from 20 to 100 mol%, particularly preferably from 50 to 100 mol%, based on the total amount of diamine used as a raw material for producing the acid or derivative thereof. Two or more photosensitive diamines may be used in combination in order to improve the above-described various characteristics such as sensitivity to light and afterimage characteristics. As described above, the embodiment of the present invention includes the case where the total amount of the tetracarboxylic dianhydride is occupied by the non-photosensitive tetracarboxylic dianhydride. Even in this case, at least 20 mol% of the total amount of the diamine is photosensitive. It is required to be a functional diamine.

In order to improve the above-described various characteristics such as sensitivity to light and afterimage characteristics, a photosensitive tetracarboxylic dianhydride and a photosensitive diamine may be used in combination, or two or more of each may be used in combination.

式（１）において、ｎは独立して炭素数１〜６のアルキレンである。 The diamine represented by Formula (1) of this invention is demonstrated.

In formula (1), n is independently a C1-C6 alkylene.

Among the formulas (1), a diamine represented by n = 3 can be preferably used from the viewpoint of easy availability of raw materials, ease of polymer polymerization, and reliability of the obtained alignment film.

The non-photosensitive tetracarboxylic dianhydride used for producing the liquid crystal aligning agent for photo-alignment containing at least one selected from the polyamic acid, polyamic acid ester and polyimide of the present invention is a known non-photosensitive The tetracarboxylic dianhydride can be selected without limitation. Such a non-photosensitive tetracarboxylic dianhydride has an aromatic system (including a heteroaromatic ring system) in which a dicarboxylic acid anhydride is directly bonded to an aromatic ring, and a dicarboxylic acid anhydride directly bonded to an aromatic ring. It may belong to any group of non-aliphatic (including heterocyclic) systems.

A non-photosensitive diamine other than the diamine represented by formula (1) used for producing a liquid crystal aligning agent for photo-alignment containing at least one selected from the polyamic acid, polyamic acid ester and polyimide of the present invention Can be selected without limitation from known non-photosensitive diamines.

In each diamine, the ratio of the monoamine to the diamine may be 40 mol% or less, and a part of the diamine may be replaced with the monoamine. Such replacement can cause termination of the polymerization reaction when the polyamic acid is produced, and further progress of the polymerization reaction can be suppressed. For this reason, the molecular weight of the resulting polymer (polyamic acid, polyamic acid ester or polyimide) can be easily controlled by such replacement, for example, the coating characteristics of the liquid crystal aligning agent without impairing the effects of the present invention. Can be improved. As long as the effect of the present invention is not impaired, one or more diamines may be substituted for the monoamine. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n- Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine Is mentioned.

The polyamic acid, polyamic acid ester and polyimide of the present invention may further contain a monoisocyanate compound in the monomer. By including the monoisocyanate compound in the monomer, the terminal of the resulting polyamic acid or derivative thereof is modified, and the molecular weight is adjusted. By using this terminal-modified polyamic acid or a derivative thereof, for example, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. It is preferable from said viewpoint that content of the monoisocyanate compound in a monomer is 1-10 mol% with respect to the total amount of the diamine and tetracarboxylic dianhydride in a monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyamic acid, polyamic acid ester and polyimide of the present invention can be obtained by reacting a mixture of the above acid anhydrides with a diamine in a solvent. In this synthesis reaction, no special conditions other than the selection of the raw materials are required, and the conditions for normal polyamic acid synthesis can be applied as they are. The solvent to be used will be described later.

The liquid crystal aligning agent for photo-alignment of the present invention may further contain components other than the polyamic acid, the polyamic acid ester and the polyimide of the present invention. The other component may be one type or two or more types. Examples of other components include other polymers and compounds described below.

Examples of other polymers include polyamic acid, polyamic acid ester, or polyimide (hereinafter referred to as “other polyamic acid or a polyamic acid” obtained by reacting a raw material monomer having no photoisomerization structure and not containing the diamine of formula (1). Derivatives thereof ”), polyesters, polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like. 1 type or 2 types or more may be sufficient. Of these, other polyamic acids or derivatives thereof and polysiloxanes are preferred, and other polyamic acids or derivatives thereof are more preferred.

The diamine used for synthesizing other polyamic acid or a derivative thereof preferably contains 30% by mole or more, and more preferably 50% or more of the aromatic diamine with respect to the total diamine.

Other polyamic acids or derivatives thereof can be synthesized according to the method described below as a method for synthesizing polyamic acid or derivatives thereof, which are essential components of the liquid crystal aligning agent of the present invention.

As described above, in the liquid crystal aligning agent for photo-alignment of the present invention, at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof and diamine has a photoreactive structure, and diamine is It contains at least one polymer obtained by reacting a raw material monomer containing at least one compound represented by the formula (1), or is selected from the group consisting of tetracarboxylic acid and derivatives thereof, and diamine None of the polymer obtained by reacting at least one raw material monomer having a photoreactive structure, tetracarboxylic dianhydride and its derivative, and diamine have a photoreactive structure. And at least one polymer obtained by reacting a raw material monomer containing at least one compound represented by the following formula (1) with diamine. Including simultaneously, it is for photo-alignment liquid crystal aligning agent.

The liquid crystal aligning agent for photo-alignment of the present invention may contain at least two polymers. Of the two polymers, [A] is a polymer having a photoreactive structure, and [B] is a polymer having no photoreactive structure, and the weight average molecular weight of [B] is the weight average molecular weight of [B]. In the process of applying a liquid crystal aligning agent containing a mixture of both polymers to the substrate and performing preliminary drying, the photopolymerization structure [A] is formed on the upper layer of the formed polymer film. It is considered that [B] having no photoreactive structure in the lower layer can be segregated. Therefore, the presence of the polymer [A] having the photoreactive structure is dominant on the surface of the alignment film, and the content of the polymer [A] having the photoreactive structure based on the total amount of the polymer forming the alignment film. Even if there is little, the alignment film formed with the liquid crystal aligning agent for photo-alignment of this invention shows high liquid crystal aligning property.

In the process of forming a thin film using a liquid crystal aligning agent containing two polymers as described above, it is known that a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer. Whether the alignment film is layer-separated is, for example, the surface energy of the formed film is measured and is the same as the value of the surface energy of the film formed by the liquid crystal aligning agent containing only the polymer [A]. It can be confirmed by being close to it.

In order to exhibit good photoalignment as described above, the content of [A] in the liquid crystal aligning agent for photoalignment of the present invention is 20% by weight or more when the total amount of the polymer contained is 100. It is necessary and is preferably 30% by weight or more, more preferably 50% by weight or more. Further, in order to keep the transmittance of the liquid crystal alignment film good, the content of [A] needs to be 90% by weight or less, preferably 70% by weight or less, and preferably 50% by weight or less. It is more preferable. However, the preferable content of [A] described here is one guideline and may vary depending on the combination of tetracarboxylic dianhydride or diamine used as a raw material. In particular, when a raw material compound having an azobenzene structure is used, the content of [A] is set to be approximately 10 to 20% by weight less than the above ratio in order to maintain good permeability.

The weight average molecular weight of the polymer is preferably adjusted so that the molecular weight (MW) of [A] is 10, by adjusting [A] to 8,000 to 40,000 and [B] to 50,000 to 200,000. The layer separation as described above can be caused by adjusting the molecular weight (MW) of [B] to 80,000 to 160,000 to 000 to 30,000. The weight average molecular weight of the polymer can be adjusted by, for example, the time for reacting tetracarboxylic dianhydride and diamine. A small amount of the reaction solution during the polymerization reaction is collected, the weight average molecular weight of the polymer contained therein is determined by measurement by gel permeation chromatography (GPC) method, and the end point of the reaction can be determined by the measured value. In addition, a method of controlling the weight average molecular weight by causing the termination of the polymerization reaction by replacing the corresponding amount of tetracarboxylic dianhydride and diamine with monocarboxylic acid or monoamine at the start of the reaction is well known. .

Examples of the polysiloxane include JP2009-036966, JP2010-185001, JP2011-109633, JP2011-253175, JP2012-159825, International Publication 2008/044644, International Publication 2009/148099, International Publication. 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, International Publication 2012/165354, etc. The polysiloxane may be further contained.

<Alkenyl-substituted nadiimide compound>
For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadiimide compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element over a long period of time. An alkenyl substituted nadiimide compound may be used by 1 type, and may use 2 or more types together. For the above purpose, the content of the alkenyl-substituted nadiimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight with respect to the polyamic acid or derivative thereof. More preferably.

式（ＮＡ）において、Ｌ^１およびＬ^２は独立して水素、炭素数１〜１２のアルキル、炭素数３〜６のアルケニル、炭素数５〜８のシクロアルキル、炭素数６〜１２のアリールまたはベンジルであり、ｎは１または２である。 The nadiimide compound will be specifically described below.
The alkenyl-substituted nadiimide compound is preferably a compound that can be dissolved in a solvent that dissolves the polyamic acid or derivative thereof used in the present invention. Examples of such alkenyl-substituted nadiimide compounds include compounds represented by the following formula (NA).

In the formula (NA), L ¹ and L ² are independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, or Benzyl and n is 1 or 2.

In the formula (NA), when n = 1, W is alkyl having 1 to 12 carbons, alkenyl having 2 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl,- Z ^1- (O) _r- (Z ² O) _k -Z ³ -H (wherein Z ¹ , Z ² and Z ³ are independently alkylene having 2 to 6 carbon atoms, and r is 0 or 1 And k is an integer of 1 to 30.), a group represented by — (Z ⁴ ) _r —BZ ⁵ —H, wherein Z ⁴ and Z ⁵ are independently A group represented by the formula: -B-T-B-H (which is an alkylene having 1 to 4 carbon atoms or a cycloalkylene having 5 to 8 carbon atoms, B is phenylene, and r is 0 or 1) B is phenylene, and T is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —CO—, — S— or —SO ₂ —), or a group in which 1 to 3 hydrogens of these groups are substituted with —OH.

At this time, preferable W is alkyl having 1 to 8 carbons, alkenyl having 3 to 4 carbons, cyclohexyl, phenyl, benzyl, poly (ethyleneoxy) ethyl having 4 to 10 carbons, phenyloxyphenyl, phenylmethylphenyl, Phenylisopropylidenephenyl and groups in which one or two hydrogens of these groups are replaced by —OH.

Wherein in (NA), when n = 2, W is alkylene of 2 to 20 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, arylene having 6 to 12 carbon ^{atoms, -Z 1 -O- (Z 2 O} ) a group represented by _k— Z ³ — (wherein Z ^{1 to} Z ³ and k are as defined above), —Z ⁴ —BZ ⁵ — (where Z ⁴ , Z defining ⁵ and B are as defined above. groups represented _{by), -B- (O-B)} r -T- (B-O) r -B- ( wherein, B is phenylene, T is alkylene having 1 to 3 carbon atoms, —O— or —SO ₂ —, and the definition of r is as described above), or 1 to 3 hydrogens of these groups are It is a group replaced by —OH.

In this case, preferable W is alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, —C ₃ H ₆ —O— (Z ² —O) _n —O—C ₃ H ₆ — (where, Z ² is alkylene having 2 to 6 carbon atoms, and n is 1 or 2.) —B—T—B— (where B is phenylene, and T is — A group represented by CH ₂ —, —O— or —SO ₂ —), —B—O—B—C ₃ H ₆ —B—O—B—, wherein B is phenylene. And a group in which one or two hydrogens of these groups are replaced by —OH.

Such an alkenyl-substituted nadiimide compound is synthesized, for example, by maintaining an alkenyl-substituted nadic acid anhydride derivative and a diamine at a temperature of 80 to 220 ° C. for 0.5 to 20 hours as described in Japanese Patent No. 2729565. Or a commercially available compound can be used. Specific examples of the alkenyl-substituted nadiimide compound include the following compounds.

N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-methallylmethylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,

N- (2-ethylhexyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-methallylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl- Allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxyl N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenyl-allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide,

N-phenyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-methallylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (2-hydroxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2- Hydroxyethyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-hydroxyethyl) -methallylbicyclo [2.2.1] hept -5-ene- , 3-dicarboximide,

N- (2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,2-dimethyl-3-hydroxy Propyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2,3-dihydroxypropyl) -allylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (2,3-dihydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxycyclohexyl) -allyl (methyl) bicycle [2.2.1] hept-5-ene-2,3-dicarboximide,

N- (4-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -allyl (methyl) bicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3-hydroxyphenyl) -allylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide, N- (3-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide , -(P-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl} -allylbicyclo [2. 2.1] hept-5-ene-2,3-dicarboximide,

N- {2- (2-hydroxyethoxy) ethyl} -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ) Ethyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2- (2-hydroxyethoxy) ethyl} -methallylmethylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- 2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenyl) Isopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allyl (methyl) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, and oligomers thereof,

N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5- Ene-2,3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′— Cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

1,2-bis {3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethane, 1,2-bis {3 ′-(allylmethylbicyclo) [2.2.1] Hept-5-ene-2,3-dicarboximido) propoxy} ethane, 1,2-bis {3 ′-(methallylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximido) propoxy} ethane, bis [2 '-{3'-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] Ether, bis [2 ′-{3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether, 1,4-bis {3 ′ -(Allylbicyclo [2.2.1] he To-5-ene-2,3-dicarboximido) propoxy} butane, 1,4-bis {3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido) propoxy} butane,

N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2] 2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4 -(Ant Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} sulfone,

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, 1,6-bis (allylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide) -3-hydroxy-hexane, 1,12-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)- 3,6-dihydroxy-dodecane, 1,3-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-cyclohexane, 1,5-bis { 3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} -3-hydroxy-pentane, 1,4-bis (allylbicyclo [2.2.1 ] Hept-5-ene 2,3-dicarboximide) -2-hydroxy - benzene,

1,4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2,5-dihydroxy-benzene, N, N′-p- (2-hydroxy ) Xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p- (2-hydroxy) xylylene-bis (allylmethylcyclo [2] 2.1] hept-5-ene-2,3-dicarboximide), N, N′-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide), N, N'-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) , N, N′-p- (2,3-dihi Proxy) xylylene - bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) -2-hydroxy-phenoxy} phenyl] propane, bis {4- (Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-phenyl} methane, bis {3- (allylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide) -4-hydroxy-phenyl} ether, bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-phenyl} sulfone, 1,1,1-tri {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)} phenoxymethylpropane, N , N , N "- tri (ethylene methallyl ruby [2.2.1] hept-5-ene-2,3-dicarboximide) isocyanurate, and the like of these oligomers.

Furthermore, the alkenyl-substituted nadiimide compound used in the present invention may be a compound represented by the following formula containing an asymmetric alkylene / phenylene group.

Of the alkenyl-substituted nadiimide compounds, preferred compounds are shown below.
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide), 2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane 2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4 -{4- (methallylbicyclo 2.2.1] Hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4 -(Ant Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2, 3-Dicarboximido) phenyl} sulfone.

Further preferred alkenyl-substituted nadiimide compounds are shown below.
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2] 2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylbicyclo [2] 2.1] Hept 5-ene-2,3-dicarboximide) phenyl} methane, bis {4- (methallyl methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane.

And as a particularly preferable alkenyl substituted nadiimide compound, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the following formula (NA-1): Phenyl} methane, N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the formula (NA-2), and N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) represented by the formula (NA-3) may be mentioned.

<Compound having radically polymerizable unsaturated double bond>
For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The compound having a radically polymerizable unsaturated double bond may be one type of compound or two or more types of compounds. The compound having a radical polymerizable unsaturated double bond does not include an alkenyl-substituted nadiimide compound. The content of the compound having a radically polymerizable unsaturated double bond is preferably 1 to 100% by weight, more preferably 1 to 70% by weight with respect to the polyamic acid or derivative thereof for the above purpose. Preferably, it is 1 to 50% by weight.

The ratio of the compound having a radical polymerizable unsaturated double bond to the alkenyl-substituted nadiimide compound reduces the ion density of the liquid crystal display element, suppresses the increase in ion density over time, and further suppresses the occurrence of afterimages. Therefore, the compound / alkenyl-substituted nadiimide compound having a radically polymerizable unsaturated double bond is preferably 0.1 to 10 and more preferably 0.5 to 5 in weight ratio.

The compound having a radical polymerizable unsaturated double bond will be specifically described below.
Examples of the compound having a radical polymerizable unsaturated double bond include (meth) acrylic acid esters, (meth) acrylic acid derivatives such as (meth) acrylic acid amide, and bismaleimide. The compound having a radically polymerizable unsaturated double bond is more preferably a (meth) acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylic acid ester include, for example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Examples include oxyethyl, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.

Specific examples of the bifunctional (meth) acrylic acid ester include, for example, ethylene bisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, which are products of Toa Gosei Chemical Co., Ltd., Nippon Kayaku Co., Ltd. ) Products KAYARADHDDA, KAYAARADHX-220, KAYARADR-604 and KAYARADR-684, Osaka Organic Chemicals Co., Ltd. products V260, V312 and V335HP, and Kyoeisha Oil & Chemicals Co., Ltd. light acrylates BA-4EA, light acrylate BP-4PA and light acrylate BP-2PA.

Specific examples of the trifunctional or higher polyfunctional (meth) acrylic acid ester include, for example, 4,4'-methylenebis (N, N-dihydroxyethylene acrylate aniline), Aronix M-, a product of Toa Gosei Chemical Co., Ltd. 400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, Nippon Kayaku Co., Ltd. products KAYARADTMPTA, KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60 , KAYARADDPCA-120, and VGPT which is a product of Osaka Organic Chemical Industry Co., Ltd.

Specific examples of the (meth) acrylic acid amide derivative include, for example, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropyl. Methacrylamide, N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide, N-tetrahydrofurfurylmethacrylamide, N-ethylacrylamide, N-ethyl-N-methylacrylamide, N, N-diethyl Acrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylpyrrolidine, N, N′-methyl Nbisacrylamide, N, N′-ethylenebisacrylamide, N, N′-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N- (iso -Butoxymethyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- ( Methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N′-methylenebismethacrylamide.

Among the above (meth) acrylic acid derivatives, N, N′-methylenebisacrylamide, N, N′-dihydroxyethylene-bisacrylamide, ethylenebisacrylate, and 4,4′-methylenebis (N, N-dihydroxyethyleneacrylate) Aniline) is particularly preferred.

Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by Kay Kasei Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI- manufactured by Daiwa Kasei Kogyo Co., Ltd. 7000.

<Oxazine compound>
For example, the liquid crystal aligning agent of this invention may further contain the oxazine compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long period of time. The oxazine compound may be one type of compound or two or more types of compounds. The content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof for the above purpose. More preferably.

The oxazine compound will be specifically described below.
The oxazine compound is soluble in a solvent that dissolves the polyamic acid or a derivative thereof, and in addition, an oxazine compound having ring-opening polymerizability is preferable.

Further, the number of oxazine structures in the oxazine compound is not particularly limited.

Various structures are known for the structure of oxazine. In the present invention, the structure of oxazine is not particularly limited, but examples of the oxazine structure in the oxazine compound include an oxazine structure having an aromatic group containing a condensed polycyclic aromatic group such as benzoxazine and naphthoxazine.

式（ＯＸ−１）〜式（ＯＸ−３）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、式（ＯＸ−１）〜式（ＯＸ−６）において、Ｌ^５〜Ｌ^８は水素または炭素数１〜６の炭化水素基であり、式（ＯＸ−３）、式（ＯＸ−４）および式（ＯＸ−６）において、Ｑ^１は単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｖ−、−Ｏ−（ＣＨ_２）_ｖ−Ｏ−、−Ｓ−（ＣＨ_２）_ｖ−Ｓ−であり、ここでｖは１〜６の整数であり、式（ＯＸ−５）および式（ＯＸ−６）において、Ｑ^２は独立して単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−または炭素数１〜３のアルキレンであり、Ｑ^２におけるベンゼン環、ナフタレン環に結合している水素は独立して−Ｆ、−ＣＨ_３、−ＯＨ、−ＣＯＯＨ、−ＳＯ_３Ｈ、−ＰＯ_３Ｈ_２と置き換えられていてもよい。 Examples of the oxazine compound include compounds represented by the following formulas (OX-1) to (OX-6). In the following formula, the bond displayed toward the center of the ring indicates that it is bonded to any carbon that forms the ring and can be bonded to a substituent.

In Formula (OX-1) to Formula (OX-3), L ³ and L ⁴ are organic groups having 1 to 30 carbon atoms, and in Formula (OX-1) to Formula (OX-6), L ⁵ to L ⁸ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. In the formula (OX-3), the formula (OX-4), and the formula (OX-6), Q ¹ is a single bond, —O—, — _{S -, - S-S -} , - SO 2 -, - CO -, - CONH -, - NHCO -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) v _{-, - O- (CH 2)} v -O -, - S- (CH 2) v is -S-, where v is an integer from 1 to 6, formula (OX-5) and formula (OX −6), Q ² is independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or C 1-3. Is alkylene And hydrogen bonded to the benzene ring and naphthalene ring in Q ² may be independently replaced with —F, —CH ₃ , —OH, —COOH, —SO ₃ H, —PO ₃ H _2. .

The oxazine compound includes an oligomer or polymer having an oxazine structure in the side chain, and an oligomer or polymer having an oxazine structure in the main chain.

Examples of the oxazine compound represented by the formula (OX-1) include the following oxazine compounds.

In Formula (OX-1-2), L ³ is preferably alkyl having 1 to 30 carbons, and more preferably alkyl having 1 to 20 carbons.

Examples of the oxazine compound represented by the formula (OX-2) include the following oxazine compounds.

In the formula, L ³ is preferably alkyl having 1 to 30 carbons, and more preferably alkyl having 1 to 20 carbons.

式（ＯＸ−３−Ｉ）において、Ｌ^３およびＬ^４は炭素数１〜３０の有機基であり、Ｌ^５からＬ^８は水素または炭素数１〜６の炭化水素基であり、Ｑ^１は単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。式（ＯＸ−３−Ｉ）で表されるオキサジン化合物としては、例えば以下のオキサジン化合物が挙げられる。 As the oxazine compound represented by the formula (OX-3), an oxazine compound represented by the following formula (OX-3-I) can be given.

In Formula (OX-3-I), L ³ and L ⁴ are each an organic group having 1 to 30 carbon atoms, L ⁵ to L ⁸ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ is A single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —SO ₂ —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ —. . Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

式中、Ｌ^３およびＬ^４は炭素数１〜３０のアルキルが好ましく、炭素数１〜２０のアルキルがさらに好ましい。

In the formula, L ³ and L ⁴ are preferably alkyl having 1 to 30 carbon atoms, more preferably alkyl having 1 to 20 carbon atoms.

Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-5) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-6) include the following oxazine compounds.

Of these, more preferably, the formula (OX-2-1), the formula (OX-3-1), the formula (OX-3-3), the formula (OX-3-5), and the formula (OX-3- 7), formula (OX-3-9), formula (OX-4-1) to formula (OX-4-6), formula (OX-5-3), formula (OX-5-4), and formula Oxazine compounds represented by (OX-6-6-2) to formula (OX-6-4) can be given.

The oxazine compound can be produced by the same method as described in International Publication No. 2004/009708, JP-A-11-12258, and JP-A-2004-352670.

The oxazine compound represented by the formula (OX-1) is obtained by reacting a phenol compound, a primary amine, and an aldehyde (see International Publication 2004/009708).

The oxazine compound represented by the formula (OX-2) is obtained by reacting by a method of gradually adding a primary amine to formaldehyde, and then adding and reacting a compound having a naphthol-based hydroxyl group (International Publication 2004 / (See 009708.)

The oxazine compound represented by the formula (OX-3) is a secondary aliphatic compound in which 1 mol of a phenol compound, at least 2 mol or more of an aldehyde, and 1 mol of a primary amine are added to one phenolic hydroxyl group in an organic solvent. It can be obtained by reacting in the presence of an amine, a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound (see International Publication No. 2004/009708 and JP-A-11-12258).

The oxazine compound represented by the formula (OX-4) to the formula (OX-6) is a diamine having a plurality of benzene rings and an organic group that binds them, such as 4,4′-diaminodiphenylmethane, and formalin. It can be obtained by subjecting an aldehyde and phenol to a dehydration condensation reaction in n-butyl alcohol at a temperature of 90 ° C. or higher (see JP 2004-352670 A).

<Oxazoline compound>
For example, the liquid crystal aligning agent of this invention may further contain the oxazoline compound from the objective of stabilizing the electrical property in a liquid crystal display element for a long period of time. An oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one type of compound or two or more types of compounds. The content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or a derivative thereof for the above purpose. More preferably. Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight with respect to the polyamic acid or a derivative thereof when the oxazoline structure in the oxazoline compound is converted to oxazoline.

The oxazoline compound will be specifically described below.
The oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more. The oxazoline compound may be a polymer having an oxazoline structure in the side chain, or may be a copolymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure It may be. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more monomers having an oxazoline structure in the side chain, or two or more monomers having an oxazoline structure in the side chain and an oxazoline structure. It may also be a copolymer with a monomer that does not have.

The oxazoline structure is preferably a structure present in the oxazoline compound so that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polyamic acid.

Examples of the oxazoline compound include 2,2′-bis (2-oxazoline), 1,2,4-tris- (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene-2-phenyl-4H—. Oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene, 2,3-bis (4- Isopropenyl-2-oxazolin-2-yl) butane, 2,2′-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl-2-oxazolin-2-yl) pyridine, 2,2 ′ -Isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2-oxazoline), 2,2'-methylenebi (4-tert-butyl-2-oxazoline), and 2,2'-methylenebis (4-phenyl-2-oxazoline) and the like. In addition to these, polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Shokubai Co., Ltd.) are also included. Of these, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene is more preferable.

<Epoxy compound>
For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The epoxy compound may be one type of compound or two or more types of compounds. The content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight with respect to the polyamic acid or derivative thereof for the above purpose. More preferably.

The epoxy compound will be specifically described below.
Examples of the epoxy compound include various compounds having one or more epoxy rings in the molecule. Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclohexene oxide, 3-glycidoxy Propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidylaniline, and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.

Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl. Ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, celloxide 8000 (trade name, manufactured by Daicel Corporation), and 3- (N, N-diglycidyl) aminopropyltrimethoxysilane It is.

Examples of the compound having three epoxy rings in the molecule include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- Epoxypropoxy] phenyl)] ethyl] phenyl] propane (trade name “Techmore VG3101L” (manufactured by Mitsui Chemicals, Inc.)).

Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, and 3- (N-allyl-N-glycidyl) Aminopropyltrimethoxysilane is mentioned.

In addition to the above, examples of the compound having an epoxy ring in the molecule include oligomers and polymers having an epoxy ring. Examples of the monomer having an epoxy ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Examples of other monomers copolymerized with a monomer having an epoxy ring include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and iso-butyl. (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethyl Styrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

Preferable specific examples of the monomer polymer having an epoxy ring include polyglycidyl methacrylate. Preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate. Copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer Coalescence is mentioned.

Among these examples, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′— Tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L”, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, celoxide 8000 (trade name, manufactured by Daicel Corporation) and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are particularly preferred.

More systematically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound. Is mentioned. In addition, an epoxy compound means the compound which has an epoxy group, and an epoxy resin means resin which has an epoxy group.

Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic aliphatic epoxy compound.

Examples of the glycidyl ether include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy compound, hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol. -S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, brominated phenol novolak type epoxy compound Brominated cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound, naphthalene skeleton-containing epoxy compound, aromatic polymer Glycidyl ether compounds, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compounds, aliphatic polyglycidyl ether compound, a polysulfide-type diglycidyl ether compound, and biphenol type epoxy compound.

Examples of the glycidyl ester include a diglycidyl ester compound and a glycidyl ester epoxy compound.

Examples of the glycidylamine include polyglycidylamine compounds and glycidylamine type epoxy resins.

Examples of the epoxy group-containing acrylic compound include homopolymers and copolymers of monomers having oxiranyl.

Examples of glycidyl amide include glycidyl amide type epoxy compounds.

Examples of the chain aliphatic epoxy compound include compounds containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound.

Examples of the cycloaliphatic epoxy compound include a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.

Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (all trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER -331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epicron 840, Epicron 850, Epicron 1050 (all trade names, manufactured by DIC Corporation), Epomic R-140, Epomic R-301 , And Epomic R-304 (both trade names, manufactured by Mitsui Chemicals, Inc.).

Examples of the bisphenol F type epoxy compound include jER806, jER807, jER4004P (all trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001 (all trade names, Toto Kasei) DER-354 (trade name, manufactured by Dow Chemical Company), Epicron 830, and Epicron 835 (all trade names, manufactured by DIC Corporation).

Examples of the bisphenol type epoxy compound include epoxidized products of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

Examples of the hydrogenated bisphenol-A type epoxy compound include Santo Tote ST-3000 (trade name, manufactured by Toto Kasei Co., Ltd.), Rica Resin HBE-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), and Denacol EX-252. (Trade name, manufactured by Nagase ChemteX Corporation).

Examples of the hydrogenated bisphenol type epoxy compound include an epoxidized product of hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

Examples of brominated bisphenol-A type epoxy compounds include jER5050, jER5051 (both trade names, manufactured by Mitsubishi Chemical Corporation), Epototo YDB-360, Epototo YDB-400 (both trade names, manufactured by Toto Kasei Co., Ltd.). ), DER-530, DER-538 (all are trade names, manufactured by The Dow Chemical Company), Epicron 152, and Epicron 153 (all are trade names, manufactured by DIC Corporation).

Examples of the phenol novolac type epoxy compound include jER152, jER154 (both trade names, manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade names, manufactured by Tohto Kasei Co., Ltd.), DEN431, DEN438 (both trade names, The Dow Chemical Company), Epicron N-770 (trade name, manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all trade names, manufactured by Nippon Kayaku Co., Ltd.).

Examples of the cresol novolac type epoxy compound include jER180S75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all trade names, manufactured by Tohto Kasei Co., Ltd.), Epicron N-665, Epicron N-695. (All trade names, manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) ).

Examples of the bisphenol A novolac type epoxy compound include jER157S70 (trade name, manufactured by Mitsubishi Chemical Corporation), and Epicron N-880 (trade name, manufactured by DIC Corporation).

As the naphthalene skeleton-containing epoxy compound, for example, Epicron HP-4032, Epicron HP-4700, Epicron HP-4770 (all trade names, manufactured by DIC Corporation), and NC-7000 (trade names, manufactured by Nippon Kayaku Co., Ltd.) Is mentioned.

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (following formula EP-1), catechol diglycidyl ether (following formula EP-2), resorcinol diglycidyl ether (following formula EP-3), 2- [4 -(2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl)] ethyl] phenyl] propane (formula EP-4 below) , Tris (4-glycidyloxyphenyl) methane (following formula EP-5), jER1031S, jER1032H60 (all trade names, manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (trade name, manufactured by The Dow Chemical Company), Denacol EX-201 (trade name, manufactured by Nagase ChemteX Corporation), DPPN-503, DPPN-50 H, DPPN-501H, NC6000 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (trade names, manufactured by Mitsui Chemicals, Inc.), a compound represented by the following formula EP-6, and the following formula The compound represented by EP-7 is mentioned.

Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (trade name, manufactured by The Dow Chemical Company), and Epicron HP-7200 (trade name, manufactured by DIC Corporation).

Examples of the alicyclic diglycidyl ether compound include cyclohexane dimethanol diglycidyl ether compound and licarresin DME-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (following formula EP-8), diethylene glycol diglycidyl ether (following formula EP-9), polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (following formula EP). -10), tripropylene glycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (following formula EP-12), 1,4-butanediol diglycidyl ether (following formula EP-13), 1,6-hexanediol diglycidyl ether (following formula EP-14), dibromoneopentyl glycol diglycidyl ether (following formula EP-15), Denacol EX 810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 (all trade names, Nagase Chemtex) Co., Ltd.), DD-503 (trade name, manufactured by ADEKA Co., Ltd.), Rica Resin W-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), 1,3,5,6-tetraglycidyl-2, 4-hexanediol (following formula EP-16), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, And de Call EX-411 (trade names, manufactured by Nagase Chemtex Co., Ltd.) and the like.

Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (both are trade names, manufactured by Toraythiol Co., Ltd.).

Examples of the biphenol type epoxy compound include YX-4000, YL-6121H (all trade names, manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). ).

Examples of the diglycidyl ester compound include diglycidyl terephthalate (following formula EP-17), diglycidyl phthalate (following formula EP-18), bis (2-methyloxiranylmethyl) phthalate (following formula EP-19), di Examples include glycidyl hexahydrophthalate (following formula EP-20), a compound represented by the following formula EP-21, a compound represented by the following formula EP-22, and a compound represented by the following formula EP-23.

Examples of the glycidyl ester epoxy compound include jER871, jER872 (both trade names, manufactured by Mitsubishi Chemical Corporation), Epicron 200, Epicron 400 (all trade names, manufactured by DIC Corporation), Denacol EX-711, and Denacol. EX-721 (all are trade names, manufactured by Nagase ChemteX Corporation).

Examples of the polyglycidylamine compound include N, N-diglycidylaniline (following formula EP-24), N, N-diglycidyl-o-toluidine (following formula EP-25), N, N-diglycidyl-m-toluidine ( The following formula EP-26), N, N-diglycidyl-2,4,6-tribromoaniline (the following formula EP-27), 3- (N, N-diglycidyl) aminopropyltrimethoxysilane (the following formula EP-28 ), N, N, O-triglycidyl-p-aminophenol (following formula EP-29), N, N, O-triglycidyl-m-aminophenol (following formula EP-30), N, N, N ′ , N′-tetraglycidyl-4,4′-diaminodiphenylmethane (following formula EP-31), N, N, N ′, N′-tetraglycidyl-m-xylylenediamine (TETRAD) X (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-32), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (TETRAD-C (trade name, Mitsubishi Gas Chemical Co., Ltd.) )), Following formula EP-33), 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (following formula EP-34), 1,3-bis (N, N-diglycidylamino) cyclohexane (Formula EP-35), 1,4-bis (N, N-diglycidylamino) cyclohexane (Formula EP-36), 1,3-bis (N, N-diglycidylamino) benzene (Formula EP -37), 1,4-bis (N, N-diglycidylamino) benzene (the following formula EP-38), 2,6-bis (N, N-diglycidylaminomethyl) bicyclo [2.2.1] Heptane (Formula EP- 39), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodicyclohexylmethane (the following formula EP-40), 2,2′-dimethyl- (N, N, N ′, N′- Tetraglycidyl) -4,4′-diaminobiphenyl (following formula EP-41), N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenyl ether (following formula EP-42), 1,3 , 5-Tris (4- (N, N-diglycidyl) aminophenoxy) benzene (following formula EP-43), 2,4,4′-tris (N, N-diglycidylamino) diphenyl ether (following formula EP-44) ), Tris (4- (N, N-diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3 ′, 4′-tetrakis (N, N-diglycidylamino) biphenyl (following formula EP) -46), 3, 4, 3 Examples include ', 4'-tetrakis (N, N-diglycidylamino) diphenyl ether (the following formula EP-47), a compound represented by the following formula EP-48, and a compound represented by the following formula EP-49.

Examples of the homopolymer of the monomer having oxiranyl include polyglycidyl methacrylate. Examples of the copolymer of monomers having oxiranyl include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer. Examples thereof include 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

Examples of the monomer having oxiranyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Examples of the monomer other than the monomer having oxiranyl in the copolymer of the monomer having oxiranyl include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth). Acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, Examples include methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

Examples of glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (the following formula EP-50), 1,3. -Diglycidyl-5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (following formula EP-51) and glycidyl isocyanurate type epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and epolide PB3600 (trade name, manufactured by Daicel Corporation).

Examples of the cycloaliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel Corporation), the following formula EP-52), 2-methyl -3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (following formula EP-53), 2,3-epoxycyclopentane-2', 3'-epoxycyclopentane ether (Formula EP-54), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2: 8,9-diepoxy limonene (Celoxide 3000 (trade name, ( Manufactured by Daicel Corporation), the following formula EP-55), a compound represented by the following formula EP-56, LOXIDE 8000 (trade name, manufactured by Daicel Corporation, the following formula EP-57), CY-175, CY-177, CY-179 (all trade names, manufactured by The Ciba-Geigy Chemical Corp. (Huntsman Japan Co., Ltd.) )), EHPD-3150 (trade name, manufactured by Daicel Corporation), and cycloaliphatic epoxy resins.

The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac type epoxy compound, a cresol novolac type epoxy compound, and a cyclic aliphatic type epoxy compound, and N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, trade name “Techmore VG3101L” 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolak type Epoxy compounds, And it is more preferably one or more cresol novolac type epoxy compound.

For example, the liquid crystal aligning agent of this invention may further contain various additives. Examples of the various additives include high molecular compounds other than polyamic acid and its derivatives, and low molecular compounds, which can be selected and used according to their respective purposes.

For example, the polymer compound includes a polymer compound that is soluble in an organic solvent. It is preferable to add such a polymer compound to the liquid crystal aligning agent of the present invention from the viewpoint of controlling the electrical characteristics and orientation of the liquid crystal alignment film to be formed. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

Examples of the low molecular weight compound include 1) a surfactant in accordance with the purpose when improvement in coatability is desired, 2) an antistatic agent when improvement in antistatic is required, and 3) adhesion to the substrate. In the case where it is desired to improve the properties, a silane coupling agent or a titanium-based coupling agent, and 4) an imidization catalyst in the case where imidization proceeds at a low temperature can be mentioned.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyltri Methoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, and N, N′-bis [3- (trimethoxysilyl) Propyl] ethylenediamine. A preferred silane coupling agent is 3-aminopropyltriethoxysilane.

Examples of imidation catalysts include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl-substituted aniline, and hydroxy-substituted aniline. And cyclic amines such as pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy-substituted isoquinoline, imidazole, methyl-substituted imidazole, and hydroxy-substituted imidazole. . The imidation catalyst may be one or more selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline. preferable.

The addition amount of the silane coupling agent is usually 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or its derivative.

The amount of the imidation catalyst added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or derivative thereof.

The addition amount of other additives varies depending on the application, but is usually 0 to 100% by weight, preferably 0.1 to 50% by weight, based on the total weight of the polyamic acid or derivative thereof.

The polyamic acid or derivative thereof of the present invention can be produced in the same manner as a known polyamic acid or derivative thereof used for forming a polyimide film. The total amount of tetracarboxylic dianhydride is preferably approximately equimolar to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).

The molecular weight of the polyamic acid or derivative thereof according to the present invention is preferably 7,000 to 500,000, more preferably 10,000 to 200,000 in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the polyamic acid or derivative thereof can be determined from measurement by gel permeation chromatography (GPC).

The presence of the polyamic acid or derivative thereof of the present invention can be confirmed by analyzing the solid content obtained by precipitation with a large amount of poor solvent by IR or NMR. It is also possible to confirm the monomer used by analyzing the extract of the decomposition product of the polyamic acid or its derivative with an aqueous solution of strong alkali such as KOH or NaOH by an organic solvent by GC, HPLC or GC-MS. it can.

For example, the liquid crystal aligning agent of this invention may further contain the solvent from a viewpoint of the applicability | paintability of a liquid crystal aligning agent, and the adjustment of the density | concentration of the said polyamic acid or its derivative (s). The solvent can be applied without any particular limitation as long as it has a capability of dissolving the polymer component. The said solvent contains the solvent normally used in the manufacturing process and use surface of polymer components, such as a polyamic acid and a soluble polyimide, and can be suitably selected according to the intended purpose. The solvent may be one type or a mixed solvent of two or more types.

Examples of the solvent include a parent solvent for the polyamic acid or a derivative thereof, and other solvents for the purpose of improving coatability.

Examples of the aprotic polar organic solvent that is a parent solvent for polyamic acid or its derivatives include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, and N-methylpropion. Examples include amides, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyrolactone, and other lactones.

Examples of other solvents for the purpose of improving coating properties include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, etc. Diethylene glycol monoalkyl ether, diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diisobutyl ketone, dipentyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether , Propylene glycol monobutyl ether Propylene glycol monoalkyl ethers such as ether, dialkyl malonate diethyl malonate, dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, ester compounds such as those acetates and the like.

Among these, the solvent is N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether. Diethylene glycol propyl methyl ether, diethylene glycol butyl methyl ether, diisobutyl ketone, dipentyl ether, and dipropylene glycol monomethyl ether are preferred.

Moreover, when printing a coating film by the inkjet method, the other solvent for the purpose of the said parent solvent and coating property improvement can be selected suitably. By using the following first to fourth solvents in combination, a liquid crystal aligning agent with better coating properties can be obtained.

As the first solvent, at least one selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, and the second solvent , At least one selected from the group consisting of butyl cellosolve, 1-butoxy-2-propanol, diethylene glycol ethyl methyl ether, diethylene glycol propyl methyl ether, and at least selected from the group consisting of diisobutyl ketone and dipentyl ether as the third solvent. One and the fourth solvent preferably contains at least one selected from the group consisting of diethylene glycol ethyl propyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, and The proportion of one solvent is 20 to 89% by weight with respect to the total solvent weight, the proportion of the second solvent is 10 to 60% by weight with respect to the total solvent weight, and the proportion of the third solvent is with respect to the total solvent weight. It is more preferable that the ratio of the fourth solvent is 0.1 to 15% by weight with respect to the total solvent weight.

The concentration of the polyamic acid in the liquid crystal aligning agent of the present invention is preferably 0.1 to 40% by weight. When this liquid crystal aligning agent is applied to the substrate, an operation of diluting the contained polyamic acid with a solvent in advance may be required to adjust the film thickness.

The solid content concentration in the liquid crystal aligning agent of the present invention is not particularly limited, and an optimum value may be selected in accordance with the following various coating methods. Usually, in order to suppress unevenness and pinholes at the time of application, the content is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the varnish weight.

The preferred range of the viscosity of the liquid crystal aligning agent of the present invention varies depending on the coating method, the concentration of the polyamic acid or derivative thereof, the type of polyamic acid or derivative 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 80 mPa · s). If it is less than 5 mPa · s, it is difficult to obtain a sufficient film thickness, and if it exceeds 100 mPa · s, printing unevenness may increase. In the case of application by spin coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable. In the case of coating using an inkjet coating apparatus, 5 to 50 mPa · s (more preferably 5 to 20 mPa · s) is suitable. The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measuring method, and is measured using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25 ° C.).

The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of this invention is a film | membrane formed by heating the coating film of the liquid crystal aligning agent of this invention mentioned above. The liquid crystal alignment film of the present invention can be obtained by an ordinary method for producing a liquid crystal alignment film from a liquid crystal aligning agent. For example, the liquid crystal alignment film of the present invention can be obtained through a step of forming a coating film of the liquid crystal alignment agent of the present invention, a step of drying by heating, and a step of baking by heating. About the liquid crystal aligning film of this invention, as later mentioned as needed, it irradiates light after a coating-film process and a heat-drying process, or irradiates light after a heat-firing process, and provides anisotropy. Also good.

A coating film can be formed by apply | coating the liquid crystal aligning agent of this invention to the board | substrate in a liquid crystal display element similarly to preparation of a normal liquid crystal aligning film. Examples of the substrate include a glass substrate in which electrodes such as ITO (Indium Tin Oxide), IZO (In ₂ O ₃ —ZnO), and IGZO (In—Ga—ZnO ₄ ) electrodes and a color filter may be provided. .

As a method for applying a liquid crystal aligning agent to a substrate, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method and the like are generally known. These methods are similarly applicable in the present invention.

As the heat drying step, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. The heat drying step is preferably performed at a temperature within a range where the solvent can be evaporated, and more preferably at a temperature relatively lower than the temperature in the heat baking step. Specifically, the heat drying temperature is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C.

The heating and baking step can be performed under conditions necessary for the polyamic acid or its derivative to exhibit a dehydration / ring-closure reaction. As for the baking of the coating film, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are equally applicable in the present invention. In general, it is preferably performed at a temperature of about 100 to 300 ° C for 1 minute to 3 hours, more preferably 120 to 280 ° C, and further preferably 150 to 250 ° C.

The method for forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo-alignment method gives the film anisotropy by irradiating with linearly polarized light or non-polarized light after the coating film is heated and dried, and the film is heated and fired. Can be formed. Or it can form by irradiating the linearly polarized light or non-polarized light of a radiation, after heating-drying and heating-baking a coating film. From the viewpoint of orientation, the radiation irradiation step is preferably performed before the heating and baking step.

Furthermore, in order to raise the liquid crystal aligning ability of a liquid crystal aligning film, a linearly polarized light or non-polarized light can be irradiated while heating a coating film. Irradiation may be performed in a step of heating and drying the coating film or a step of heating and baking, or may be performed between the heating and drying step and the heating and baking step. The heating and drying temperature in this step is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C. Moreover, it is preferable that the heat-firing temperature in this process is the range of 30 degreeC-300 degreeC, Furthermore, it is preferable that it is the range of 50 degreeC-250 degreeC.

As the radiation, for example, ultraviolet light or visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light of 300 to 400 nm is preferable. Further, linearly polarized light or non-polarized light can be used. These lights are not particularly limited as long as they can impart a liquid crystal alignment ability to the coating film, but linearly polarized light is preferable when it is desired to develop a strong alignment regulating force for liquid crystals.

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even with low energy light irradiation. Dose of linearly polarized light in the irradiation step is preferably from 0.05~20J / cm ^2, more preferably 0.5~10J / cm ^2. The wavelength of linearly polarized light is preferably 200 to 400 nm, and more preferably 300 to 400 nm. Although the irradiation angle with respect to the film surface of linearly polarized light is not particularly limited, it is preferable from the viewpoint of shortening the alignment processing time that it is as perpendicular as possible to the film surface in order to develop a strong alignment regulating force for the liquid crystal. The liquid crystal alignment film of the present invention can align liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating linearly polarized light.

When the pretilt angle is to be expressed, the light applied to the film may be linearly polarized light or non-polarized light as described above. Dose of light applied to the film when it is desired to express a pre-tilt angle is preferably from 0.05~20J / cm ^2, particularly preferably 0.5~10J / cm ^2, its wavelength is 250 400 nm is preferable, and 300 to 380 nm is particularly preferable. When it is desired to develop a pretilt angle, the irradiation angle of the light applied to the film with respect to the film surface is not particularly limited, but is preferably 30 to 60 degrees from the viewpoint of shortening the alignment processing time.

The light source used in the process of irradiating linearly polarized light or non-polarized light includes ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, deep UV lamp, halogen lamp, metal halide lamp, high power metal halide lamp, xenon lamp, mercury A xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, a microwave excitation electrodeless lamp, and the like can be used without limitation.

The liquid crystal alignment film of the present invention can be suitably obtained by a method that further includes steps other than the steps described above. For example, the liquid crystal alignment film of the present invention does not require a process of cleaning the film after baking or radiation irradiation with a cleaning liquid, but a cleaning process can be provided for convenience of other processes.

Examples of the cleaning method using the cleaning liquid include brushing, jet spray, steam cleaning, and ultrasonic cleaning. These methods may be performed alone or in combination. The cleaning liquid is pure water, various alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone. Although it can be used, it is not limited to these. Of course, these cleaning liquids are sufficiently purified and have few impurities. Such a cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film of the present invention.

In order to enhance the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, annealing treatment with heat or light can be used before or after the heating and baking step or before or after irradiation with polarized or non-polarized radiation. In the annealing treatment, the annealing temperature is 30 to 180 ° C., preferably 50 to 150 ° C., and the time is preferably 1 minute to 2 hours. Examples of the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, and an LED lamp. The light irradiation amount is preferably 0.3 to 10 J / cm ² .

Although the film thickness of the liquid crystal aligning film of this invention is not specifically limited, It is preferable that it is 10-300 nm, and it is more preferable that it is 30-150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a step meter or an ellipsometer.

The liquid crystal alignment film of the present invention is particularly characterized by having a large alignment anisotropy. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in JP-A-2005-275364. Further, as shown in the following examples, evaluation can also be made by a method using ellipsometry. Specifically, the retardation value of the liquid crystal alignment film can be measured by a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, those having a large retardation value have a large degree of alignment, and when used as a liquid crystal alignment film, an alignment film having a greater anisotropy is considered to have a large alignment regulating force on the liquid crystal composition.

The liquid crystal alignment film of the present invention can be suitably used for a horizontal electric field type liquid crystal display element. When used in a horizontal electric field type liquid crystal display element, the smaller the Pt angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark state and the better the contrast. The Pt angle is preferably 0.1 ° or less.

The liquid crystal alignment film of the present invention can be used for alignment control of an optical compensation material and all other liquid crystal materials in addition to the alignment use of a liquid crystal composition for a liquid crystal display. Further, since the alignment film of the present invention has large anisotropy, it can be used alone for an optical compensator application.

The liquid crystal display element of the present invention will be described in detail.
The present invention is formed on a pair of substrates disposed opposite to each other, an electrode formed on one or both of the surfaces opposed to each of the pair of substrates, and a surface opposed to each of the pair of substrates. A liquid crystal display element having a liquid crystal alignment film formed and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the alignment film of the present invention.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such electrodes include ITO and metal vapor deposition films. Further, the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape that is patterned, for example. Examples of the desired shape of the electrode include a comb shape or a zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both substrates. The form of electrode formation varies depending on the type of liquid crystal display element. For example, in the case of an IPS liquid crystal display element, an electrode is disposed on one of the pair of substrates, and in the case of other liquid crystal display elements, the electrodes of the pair of substrates are arranged. Electrodes are arranged on both sides. The liquid crystal alignment film is formed on the substrate or electrode.

The liquid crystal layer is formed in such a manner that the liquid crystal composition is sandwiched between the pair of substrates facing each other on which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a spacer such as fine particles or a resin sheet that is interposed between the pair of substrates to form an appropriate interval can be used as necessary.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having a positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application Laid-Open No. 5-501735, Japanese Patent Application Laid-Open No. 8-157826, Japanese Patent Application Laid-Open No. 8-231960, Japanese Patent Application Laid-Open No. 9-241644 (EP 8852272A1), Kaihei 9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-255556, JP-A-9-241643 (EP885271A1), JP-A-10-204016 (EP844229A1), JP-A-10 -204436, JP-A-10-231482, JP-A-2000-087040, JP-A-2001-48822, and the like.

Preferred examples of the liquid crystal composition having negative dielectric anisotropy are disclosed in JP-A-57-114532, JP-A-2-4725, JP-A-4-224855, JP-A-8-40953, JP-A-8-104869, Kaihei 10-168076, JP-A-10-168453, JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10-236993, JP-A-10-236994, JP-A-10-237000, JP-A-10-237000 -237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076, JP-A-10-237448 (EP967261A1), JP-A-10-287874, JP-A-10-287875, JP-A-10-287875. 10-291945, JP-A-11-029581, Kaihei 11-080049, JP 2000-256307, JP 2001-019965, JP 2001-072626, JP 2001-192657, JP 2010-037428, International Publication 2011/024666, International Publication 2010/072370, Special Table 2010. Examples thereof include liquid crystal compositions disclosed in Japanese Patent No. 5370010, Japanese Patent Application Laid-Open No. 2012-0702201, Japanese Patent Application Laid-Open No. 2009-084362, and the like.

One or more optically active compounds may be added to a liquid crystal composition having a positive or negative dielectric anisotropy.

Further, for example, the liquid crystal composition used in the device of the present invention may further contain an additive from the viewpoint of improving the orientation. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.

Hereinafter, the present invention will be described with reference to examples. The evaluation methods and compounds used in the examples are as follows.

1. Weight average molecular weight (Mw)
The weight average molecular weight of the polyamic acid was measured by GPC method using a 2695 separation module / 2414 differential refractometer (manufactured by Waters) and calculated by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration was about 2% by weight. The column was HSPgel RT MB-M (manufactured by Waters), and measurement was performed under the conditions of a column temperature of 50 ° C. and a flow rate of 0.40 mL / min using the mixed solution as a developing agent. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.
2. The voltage holding ratio was measured by the method described in “Mizushima et al., 14th Liquid Crystal Discussion Group Proceedings p78 (1988)”. The measurement was performed by applying a rectangular wave having a wave height of ± 5 V to the cell. The measurement was performed at 60 ° C. This value is an index indicating how much the applied voltage is retained after the frame period. If this value is 100%, it indicates that all charges are retained. A liquid crystal display element having a good display quality is obtained when the cell having the positive type liquid crystal is 99.0% or more and the cell having the negative type liquid crystal is 97.5% or more.
3. 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. Using a triangular wave with a frequency of 0.01 Hz, measurement was performed at a voltage range of ± 10 V and a temperature of 60 ° C. (electrode area is 1 cm ² ). If the ion density is high, defects such as seizure due to ionic impurities are likely to occur. That is, the ion density is a physical property value that serves as an index for predicting the occurrence of image sticking. If this value is 40 pC or less, a liquid crystal display element with good display quality is obtained.

<Tetracarboxylic dianhydride>

<Diamine>

<Solvent>
NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve (ethylene glycol monobutyl ether)
BP: 1-butoxy-2-propanol GBL: γ-butyrolactone EDM: diethylene glycol ethyl methyl ether BDM: diethylene glycol butyl methyl ether DIBK: diisobutyl ketone DPE: dipentyl ether

<Additives>
Ad1: N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane Ad2: 1,3-bis (4,5-dihydro-2-oxazolyl) benzene Ad3: 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane Ad4: Celoxide 8000 (trade name, manufactured by Daicel Corporation)

[Synthesis Example 1] Synthesis of varnish Stirring blades, Compound (0) represented by Formula (D-8) and Compound 0 represented by Formula (D-8) were added to a 100 mL three-necked flask equipped with a nitrogen inlet tube. 1946 g was added, and 34.0 g of N-methyl-2-pyrrolidone (NMP) was added. The solution was ice-cooled and the liquid temperature was adjusted to 5 ° C., and then 3.9492 g of the compound represented by the formula (AN-5) (m = 8) was added, followed by stirring at room temperature for 12 hours. Thereto was added 30.0 g of γ-butyrolactone (GBL) and 30.0 g of butyl cellosolve (BC), and the solution was heated and stirred at 60 ° C. until the weight average molecular weight of the solute polymer reached the desired weight average molecular weight. A varnish 1 having a weight average molecular weight of approximately 11,000 and a resin concentration of 6% by weight was obtained.

[Synthesis Examples 2 to 18]
Varnish 2 to Varnish 18 having a polymer solid content concentration of 6 wt% were prepared in accordance with Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed. The weight average molecular weight was approximately 11,000 to 13,000 for the polymer using the raw material having the photoreactive structure, and 45,000 to 50,000 for the polymer not using the raw material having the photoreactive structure. Table 1 shows the tetracarboxylic dianhydride and diamine used and the weight average molecular weight of the polymer obtained. Synthesis example 1 is also shown in Table 1.

[Example 1] Preparation of single-layer type liquid crystal aligning agent, creation of electric characteristic measurement cell and electric characteristic measurement 10.0 g of varnish 1 synthesized in Synthesis Example 1 in a 50 mL eggplant flask equipped with a stirring blade and a nitrogen introduction tube Weighing, 5.0 g of N-methyl-2-pyrrolidone (NMP) and 5.0 g of butyl cellosolve (BC) were added thereto and stirred at room temperature for 1 hour to obtain a liquid crystal aligning agent 1 having a resin content concentration of 3% by weight. This liquid crystal aligning agent was applied to a glass substrate with an IPS electrode and a glass substrate with a column spacer by a spinner method (2,000 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C. for 3 minutes to evaporate the solvent, and then UV light was passed through the polarizing plate from the vertical direction with respect to the substrate using Multilight ML-501C / B manufactured by USHIO INC. The linearly polarized light was irradiated. The exposure energy at this time is 1.3 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using a UV integrated light meter UIT-150 (receiver: UVD-S365) manufactured by USHIO INC. The exposure time was adjusted so that A baking treatment was performed at 230 ° C. for 20 minutes to form a film with a thickness of about 100 nm. Next, the two substrates on which these alignment films are formed are bonded together with the surfaces on which the alignment films are formed facing each other and with a gap for injecting the liquid crystal composition between the facing alignment films. It was. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films were made parallel. The negative liquid crystal composition A was injected into these cells to produce a liquid crystal cell (liquid crystal display element) having a cell thickness of 7 μm.

物性値：ＮＩ ７５．７℃； Δε −４．１； Δｎ ０．１０１； η １４．５ｍＰａ・ｓ． <Negative liquid crystal composition A>

Physical property values: NI 75.7 ° C .; Δε-4.1; Δn 0.101; η 14.5 mPa · s.

The voltage holding ratio of this liquid crystal cell was 99.4% at 5 V-30 Hz, and the ion density was 15 pC. The cell was mounted on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; brightness 2,700 cd / m ² ) for 1,000 hours. The voltage holding ratio of the measurement cell after 1,000 hours was 99.4%, and the ion density was 15 pC. The light exposure of the cell by the above backlight tester for 1,000 hours and the voltage holding ratio and ion density measurement before and after that are collectively referred to as a reliability test.

[Examples 2 to 5]
A liquid crystal cell was produced in accordance with Example 1 except that the varnish to be used was changed, and a reliability test was performed. The measurement results are shown in Table 2 together with Example 1.

[Example 6]
The varnish to be used and the exposure energy were measured using a UV integrated light meter UIT-150 (receiver: UVD-S254) manufactured by Ushio Electric Co., Ltd., and 0.5 ± 0.02 J / cm at a wavelength of 254 nm. Except that the exposure time was changed so as to be ² , a liquid crystal cell was produced according to Example 1 and subjected to a reliability test.

[Example 7]
The varnish to be used and the exposure energy were measured with a UV integrated light meter UIT-150 (receiver: UVD-S313) manufactured by Ushio Electric Co., Ltd., and 0.5 ± 0.02 J / cm at a wavelength of 313 nm. Except that the exposure time was changed so as to be ² , a liquid crystal cell was produced according to Example 1 and subjected to a reliability test.

In all the cells of Examples 1 to 7, good results were obtained in the initial value and the value after the reliability test. Here, the initial value is a result obtained by measuring the cell without mounting it on the backlight tester.

[Example 8] Preparation of blend-type liquid crystal aligning agent, creation of electric characteristic measurement cell and electric characteristic measurement 3.0 g of varnish 2 synthesized in Synthesis Example 2 in a 50 mL eggplant flask equipped with a stirring blade and a nitrogen introduction tube 7.0 g of varnish 8 synthesized in Synthesis Example 8 was weighed, 5.0 g of N-methyl-2-pyrrolidone (NMP) and 5.0 g of butyl cellosolve (BC) were added thereto, and the mixture was stirred at room temperature for 1 hour, and the resin content concentration was 3 A weight% liquid crystal aligning agent 8 was obtained. A liquid crystal cell was produced according to the method described in Example 1. The voltage holding ratio of this liquid crystal cell was 99.7% at 5 V-30 Hz, and the ion density was 10 pC. The voltage holding ratio of the measurement cell after exposure to light for 1,000 hours was 99.6%, and the ion density was 15 pC.

[Examples 9 to 11, 14 to 17, 20]
A liquid crystal cell was prepared according to Example 8 except that the varnish to be used was changed, and voltage holding ratio, ion density measurement and reliability test were performed. The varnish used and the measurement results are shown in Table 3 together with Example 8. In Table 3, varnish A represents a varnish containing a polymer using a raw material having a photoreactive structure, and varnish B represents a varnish containing a polymer not using a raw material having a photoreactive structure.

[Examples 12 and 18]
The varnish to be used and the exposure energy were measured using a UV integrated light meter UIT-150 (receiver: UVD-S254) manufactured by Ushio Electric Co., Ltd., and 0.5 ± 0.02 J / cm at a wavelength of 254 nm. Except that the exposure time was changed so as to be ² , a liquid crystal cell was produced according to Example 1 and subjected to a reliability test. Table 3 shows the measurement results.

[Examples 13 and 19]
The varnish to be used and the exposure energy were measured with a UV integrated light meter UIT-150 (receiver: UVD-S313) manufactured by Ushio Electric Co., Ltd., and 0.5 ± 0.02 J / cm at a wavelength of 313 nm. Except that the exposure time was changed so as to be ² , a liquid crystal cell was produced according to Example 1 and subjected to a reliability test. Table 3 shows the measurement results.

Good results were obtained in all the cells of Examples 8 to 20 at the initial value and the value after 1,000 hours of light exposure.

[Example 21]
5 parts by weight of the additive (Ad1) was added to 100 parts by weight of the polymer with respect to the liquid crystal aligning agent 8 having a polymer solid content concentration of 3% by weight prepared in Example 8. Using the obtained liquid crystal aligning agent, the liquid crystal cell was produced by the method according to Example 1, and the reliability test was done.

[Example 22]
5 parts by weight of the additive (Ad2) was added to 100 parts by weight of the polymer with respect to the liquid crystal aligning agent 8 having a polymer solid content concentration of 3% by weight prepared in Example 8. Using the obtained liquid crystal aligning agent, the liquid crystal cell was produced by the method according to Example 1, and the reliability test was done.

[Example 23]
5 parts by weight of the additive (Ad3) was added to 100 parts by weight of the polymer with respect to the liquid crystal aligning agent 8 having a polymer solid content concentration of 3% by weight prepared in Example 8. Using the obtained liquid crystal aligning agent, the liquid crystal cell was produced by the method according to Example 1, and the reliability test was done.

[Example 24]
5 parts by weight of the additive (Ad4) was added to 100 parts by weight of the polymer with respect to the liquid crystal aligning agent 8 having a polymer solid content concentration of 3% by weight prepared in Example 8. Using the obtained liquid crystal aligning agent, the liquid crystal cell was produced by the method according to Example 1, and the reliability test was done.

[Example 25]
5 parts by weight of the additive (Ad1) per 100 parts by weight of the polymer was added to the liquid crystal aligning agent 11 having a polymer solid content concentration of 3% by weight prepared in Example 11. Using the obtained liquid crystal aligning agent, the liquid crystal cell was produced by the method according to Example 1, and the reliability test was done.

[Example 26]
5 parts by weight of the additive (Ad2) was added to 100 parts by weight of the polymer with respect to the liquid crystal aligning agent 11 having a polymer solid content concentration of 3% by weight prepared in Example 11. Using the obtained liquid crystal aligning agent, the liquid crystal cell was produced by the method according to Example 1, and the reliability test was done.

[Example 27]
5 parts by weight of the additive (Ad3) was added to 100 parts by weight of the polymer with respect to the liquid crystal aligning agent 11 having a polymer solid content concentration of 3% by weight prepared in Example 11. Using the obtained liquid crystal aligning agent, the liquid crystal cell was produced by the method according to Example 1, and the reliability test was done.

[Example 28]
5 parts by weight of the additive (Ad4) was added to 100 parts by weight of the polymer with respect to the liquid crystal aligning agent 11 having a polymer solid content concentration of 3% by weight prepared in Example 11. Using the obtained liquid crystal aligning agent, the liquid crystal cell was produced by the method according to Example 1, and the reliability test was done.

The measurement results of Examples 21 to 28 are shown in Table 4.

In all the cells of Examples 21 to 28, even when the additive was added, good results were obtained at the initial value and the value after 1,000 hours of light exposure.

[Comparative Examples 1-2]
A liquid crystal cell was produced according to the method described in Example 1 except that the liquid crystal aligning agent 1 was replaced with the liquid crystal aligning agent 21 or 22, and a reliability test was performed. Table 5 shows the measurement results.

In all the cells of Comparative Examples 1 and 2, particularly, the value after 1,000 hours of light exposure was greatly reduced.

[Comparative Example 3]
A liquid crystal cell was produced according to the method described in Example 6 except that the liquid crystal aligning agent 6 was replaced with the liquid crystal aligning agent 23, and a reliability test was performed. Table 5 shows the measurement results.

[Comparative Example 4]
A liquid crystal cell was prepared according to the method described in Example 7 except that the liquid crystal aligning agent 7 was replaced with the liquid crystal aligning agent 24, and a reliability test was performed. Table 5 shows the measurement results.

[Comparative Examples 5-6, 9-10]
A liquid crystal cell was produced according to Example 8 except that the varnish to be used was changed, and a reliability test was performed. Table 6 shows the varnish used and the measurement results.

[Comparative Examples 7 and 11]
A liquid crystal cell was produced according to Example 18 except that the varnish to be used was changed, and a reliability test was performed. Table 6 shows the varnish used and the measurement results.

[Comparative Examples 8 and 12]
A liquid crystal cell was produced according to Example 19 except that the varnish to be used was changed, and a reliability test was performed. Table 6 shows the varnish used and the measurement results.

In all the cells of Comparative Examples 1 to 12, the value after exposure to light for 1,000 hours was greatly reduced.

[Synthesis Examples 19 to 28] Synthesis of Varnishes Varnish 19 to varnish 28 having a polymer solid concentration of 6% by weight were prepared according to Synthesis Example 1 except that tetracarboxylic dianhydride and diamine were changed. The weight average molecular weight was approximately 11,000 to 13,000 for the polymer using the raw material having the photoreactive structure, and 45,000 to 50,000 for the polymer not using the raw material having the photoreactive structure. Table 7 shows the tetracarboxylic dianhydride and diamine used and the weight average molecular weight of the polymer obtained.

[Examples 29 to 34] A liquid crystal cell was prepared according to Example 1 except that the preparation of a single-layer liquid crystal aligning agent, the creation of an electrical property measurement cell, and the electrical property measurement were changed, except that the varnish used was changed. Measurement of voltage holding ratio and ion density and reliability test were performed. Table 8 shows the measurement results.

実施例２９〜３４のすべてのセルにおいて初期値、信頼性試験後の値において良好な結果が得られた。ここで初期値とは、セル作製後、上記バックライト試験機に載せずに測定した結果である。

In all the cells of Examples 29 to 34, good results were obtained in the initial value and the value after the reliability test. Here, the initial value is a result obtained by measuring the cell without mounting it on the backlight tester.

[Examples 35 to 44]
A liquid crystal cell was prepared according to Example 8 except that the varnish to be used was changed, and voltage holding ratio, ion density measurement and reliability test were performed. Table 9 shows the varnish used and the measurement results. In Table 9, varnish A represents a varnish containing a polymer using a raw material having a photoreactive structure, and varnish B represents a varnish containing a polymer not using a raw material having a photoreactive structure.

In all the cells of Examples 35 to 44, good results were obtained in the initial value and the value after the reliability test.

[Example 45]
The varnish synthesized in Synthesis Example 1 was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 3 g of polyamic acid. In this polyamic acid, 48.0 g of NMP, 12.0 g of γ-butyrolactone (GBL), 16.0 g of 1-butoxy-2-propanol (BP), 15.0 g of diethylene glycol ethyl methyl ether (EDM), diethylene glycol 3.0 g of butyl methyl ether (BDM) and 3.0 g of diisobutyl ketone (DIBK) were added, the solid content concentration was 3.0% by weight, and the solvent composition was NMP / GBL / BP / EDM / BDM / DIBK = 48/12 / The liquid crystal aligning agent 49 used as 16/15/3/3 was prepared. This liquid crystal aligning agent was apply | coated to the glass substrate with the inkjet coating apparatus (inkjet apparatus EB100XY100 made from Konica Minolta). After coating, the substrate was heated at 80 ° C. for 3 minutes to evaporate the solvent, and then UV light was passed through the polarizing plate from the vertical direction with respect to the substrate using Multilight ML-501C / B manufactured by USHIO INC. The linearly polarized light was irradiated. The exposure energy at this time is 1.3 ± 0.1 J / cm ² at a wavelength of 365 nm by measuring the amount of light using a UV integrated light meter UIT-150 (receiver: UVD-S365) manufactured by USHIO INC. The exposure time was adjusted so that A baking treatment was performed at 230 ° C. for 20 minutes to form a film with a thickness of about 100 nm. Next, the two substrates on which these alignment films are formed are bonded together with the surfaces on which the alignment films are formed facing each other and with a gap for injecting the liquid crystal composition between the facing alignment films. It was. At this time, the polarization directions of the linearly polarized light irradiated to the respective alignment films were made parallel. The negative liquid crystal composition A was injected into these cells to produce a liquid crystal cell (liquid crystal display element) having a cell thickness of 7 μm.

The voltage holding ratio of this liquid crystal cell was 99.3% at 5 V-30 Hz, and the ion density was 15 pC. The cell was mounted on a backlight tester (Fuji Film Co., Ltd., FujiCOLOR LED Viewer Pro HR-2; brightness 2,700 cd / m ² ) for 1,000 hours. The voltage holding ratio of the measurement cell after 1,000 hours was 99.3%, and the ion density was 15 pC.

[Example 46]
In accordance with Example 45 except that the solvent composition was changed to NMP / GBL / butyl cellosolve (BC) / EDM / BDM / dipentyl ether (DPE) = 48/12/12/15/3/7, the liquid crystal A cell was fabricated, and voltage holding ratio and ion density were measured and a reliability test was performed. The voltage holding ratio of this liquid crystal cell was 99.4% at 5 V-30 Hz, and the ion density was 15 pC. Further, the voltage holding ratio of the measuring cell after exposure to light for 1,000 hours was 99.3%, and the ion density was 15 pC.

[Example 47]
A liquid crystal cell was prepared in accordance with Example 45 except that the varnish used was changed to varnish 3 synthesized in Synthesis Example 3, and voltage holding ratio, ion density measurement and reliability test were performed. The voltage holding ratio of this liquid crystal cell was 99.4% at 5 V-30 Hz, and the ion density was 15 pC. Further, the voltage holding ratio of the measurement cell after 1,000 hours of light exposure was 99.4%, and the ion density was 15 pC.

[Example 48]
A liquid crystal cell was prepared in accordance with Example 46 except that the varnish used was changed to varnish 3 synthesized in Synthesis Example 3, and voltage holding ratio, ion density measurement and reliability test were performed. The voltage holding ratio of this liquid crystal cell was 99.4% at 5 V-30 Hz, and the ion density was 15 pC. Further, the voltage holding ratio of the measuring cell after exposure to light for 1,000 hours was 99.3%, and the ion density was 15 pC.

[Example 49]
The varnish synthesized in Synthesis Example 1 was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 0.9 g of polyamic acid. Furthermore, 2.1 g of polyamic acid was obtained in the same procedure for the varnish 11 synthesized in Synthesis Example 11. In this polyamic acid, 48.0 g of NMP, 12.0 g of γ-butyrolactone (GBL), 16.0 g of 1-butoxy-2-propanol (BP), 15.0 g of diethylene glycol ethyl methyl ether (EDM), diethylene glycol 3.0 g of butyl methyl ether (BDM) and 3.0 g of diisobutyl ketone (DIBK) were added, the solid content concentration was 3.0% by weight, and the solvent composition was NMP / GBL / BP / EDM / BDM / DIBK = 48/12 / The liquid crystal aligning agent 53 used as 16/15/3/3 was prepared. A liquid crystal cell was prepared according to Example 45 except that this liquid crystal aligning agent was used, and voltage holding ratio and ion density were measured and a reliability test was performed. The voltage holding ratio of this liquid crystal cell was 99.8% at 5 V-30 Hz, and the ion density was 10 pC. The voltage holding ratio of the measurement cell after 1,000 hours of light exposure was 99.6%, and the ion density was 15 pC.

[Example 50]
A liquid crystal cell was prepared according to Example 49 except that the solvent composition was changed to NMP / GBL / BC / EDM / BDM / DPE = 48/12/12/15/3/7, and the voltage was maintained. The rate and ion density were measured and the reliability test was performed. The voltage holding ratio of this liquid crystal cell was 99.7% at 5 V-30 Hz, and the ion density was 10 pC. The voltage holding ratio of the measurement cell after 1,000 hours of light exposure was 99.6%, and the ion density was 15 pC.

[Example 51]
The varnish synthesized in Synthesis Example 3 was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 0.9 g of polyamic acid. Furthermore, 2.1 g of polyamic acid was obtained with the same procedure for the varnish 10 synthesized in Synthesis Example 11. In this polyamic acid, 48.0 g of NMP, 12.0 g of γ-butyrolactone (GBL), 16.0 g of 1-butoxy-2-propanol (BP), 15.0 g of diethylene glycol ethyl methyl ether (EDM), diethylene glycol 3.0 g of butyl methyl ether (BDM) and 3.0 g of diisobutyl ketone (DIBK) were added, the solid content concentration was 3.0% by weight, and the solvent composition was NMP / GBL / BP / EDM / BDM / DIBK = 48/12 / The liquid crystal aligning agent 55 used as 16/15/3/3 was prepared. A liquid crystal cell was prepared according to Example 45 except that this liquid crystal aligning agent was used, and voltage holding ratio and ion density were measured and a reliability test was performed. The voltage holding ratio of this liquid crystal cell was 99.8% at 5 V-30 Hz, and the ion density was 10 pC. The voltage holding ratio of the measurement cell after 1,000 hours of light exposure was 99.5%, and the ion density was 15 pC.

[Example 52]
A liquid crystal cell was prepared according to Example 51 except that the solvent composition was changed to NMP / GBL / BC / EDM / BDM / DPE = 48/12/12/15/3/7, and the voltage was maintained. The rate and ion density were measured and the reliability test was performed. The voltage holding ratio of this liquid crystal cell was 99.8% at 5 V-30 Hz, and the ion density was 10 pC. The voltage holding ratio of the measurement cell after 1,000 hours of light exposure was 99.6%, and the ion density was 10 pC.

If the liquid crystal aligning agent for photo-alignment of the present invention is used, a high voltage holding ratio and light resistance can be maintained even when used for a long time, and a liquid crystal display element with high display quality can be provided. The liquid crystal aligning agent for photo-alignment of the present invention can be suitably applied to a lateral electric field type liquid crystal display element.

Claims (15)

At least one selected from the group consisting of polyamic acid, polyamic acid ester obtained by reacting diamine with at least one selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof, and polyimide obtained by imidizing these. A liquid crystal aligning agent for photo-alignment comprising two polymers;
The liquid crystal aligning agent for photo-alignment in which at least 1 of the raw material monomer of the said polymer has a photoreactive structure, and the said diamine contains at least 1 of the compound represented by following formula (1).

In formula (1), n is independently alkylene having 1 to 6 carbons; and
The derivative of tetracarboxylic dianhydride is tetracarboxylic acid diester or tetracarboxylic acid diester dichloride. A compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof, and diamines, and the diamine includes at least one compound represented by formula (1) Contains at least one polymer obtained by reacting raw material monomers; or
At least one polymer obtained by reacting a raw material monomer containing a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof, and diamine;
None of tetracarboxylic dianhydride and derivatives thereof, and diamines have a photoreactive structure, and a raw material monomer containing at least one compound represented by formula (1) is reacted with diamine. The liquid crystal aligning agent for photo-alignment of Claim 1 containing at least 1 of the polymer obtained simultaneously. A compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof, and diamines, and the diamine includes at least one compound represented by formula (1) Including at least one polymer obtained by reacting raw material monomers and another polymer used by mixing with the polymer, the other polymer,
The liquid crystal aligning agent for photo-alignment according to claim 2, wherein all of tetracarboxylic dianhydride and its derivative and diamine are polymers obtained by reacting raw material monomers not having a photoreactive structure. A compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof, and diamines, and the diamine includes at least one compound represented by formula (1) Including at least one polymer obtained by reacting raw material monomers and another polymer used by mixing with the polymer, the other polymer,
None of tetracarboxylic dianhydride and its derivatives, and diamines have a photoreactive structure, and are obtained by reacting raw material monomers containing at least one compound represented by formula (1). The liquid crystal aligning agent for photo-alignment of Claim 2 which is a polymer obtained. At least one polymer obtained by reacting a raw material monomer containing a compound having at least one photoreactive structure selected from the group consisting of tetracarboxylic dianhydride and derivatives thereof, and diamine;
None of tetracarboxylic dianhydride and derivatives thereof, and diamines have a photoreactive structure, and a raw material monomer containing at least one compound represented by formula (1) is reacted with diamine. The liquid crystal aligning agent for photo-alignment of Claim 1 containing at least 1 of the obtained polymer simultaneously. The liquid crystal aligning agent for photo-alignment of any one of Claims 1-5 whose photoreactive structure of a raw material monomer is a photoisomerization structure. The liquid crystal aligning agent for photo-alignment of any one of Claims 1-5 whose photoreactive structure of a raw material monomer is a structure where a coupling | bonding cleaves with an ultraviolet-ray. The liquid crystal aligning agent for photo-alignment of any one of Claims 1-5 whose photoreactive structure of a raw material monomer is a photodimerization structure. The liquid crystal aligning agent for photo-alignment of Claim 6 whose tetracarboxylic dianhydride or diamine which has a photoisomerization structure is at least one of the compounds represented by Formula (II)-(VI);

In formulas (II) to (V), R ² and R ³ are each independently a monovalent organic group having —NH ₂ or a monovalent organic group having —CO—O—CO—, in) ^{R 4} is a divalent organic group, and ^{R 5} in formula (VI) is an aromatic ring having a -NH ₂ or -CO-O-CO- independently. A tetracarboxylic dianhydride or diamine having a photoisomerization structure is represented by formulas (II-1), (II-2), (III-1), (III-2), (IV-1), (IV-2). ), (V-1) to (V-3), (VI-1), and photoalignment according to claim 9, which is at least one selected from the group of compounds represented by (VI-2). Liquid crystal aligning agent;

In the above formulas, a group whose bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;
In formula (V-2), R ⁶ is independently —CH ₃ , —OCH ₃ , —CF ₃ , or —COOCH ₃ , and a is an integer of 0 to 2;
In formula (V-3), ring A and ring B are each independently at least one selected from monocyclic hydrocarbons, condensed polycyclic hydrocarbons and heterocyclic rings,
R ¹¹ is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, —CONH—, —N (CH ₃ ) CO—, or —CON (CH ₃ ) —,
R ¹² is a linear alkylene having 1 to 20 carbon atoms, —COO—, —OCO—, —NHCO—, —CONH—, —N (CH ₃ ) CO—, or —CON (CH ₃ ) —,
In R ¹¹ and R ¹² , one or two of the linear alkylene —CH ₂ — may be substituted with —O—,
R ^{7 to} R ¹⁰ are each independently —F, —CH ₃ , —OCH ₃ , —CF ₃ , or —OH; and
b to e are each independently an integer of 0 to 4. The alkenyl-substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and at least one selected from the group consisting of epoxy compounds, further comprising any one of claims 1 to 10. The liquid crystal aligning agent for photo-alignment of 1 item | term. The liquid crystal aligning agent for photo-alignment of any one of Claims 1-11 used for manufacture of a horizontal electric field type liquid crystal display element. The liquid crystal aligning film formed with the liquid crystal aligning agent for photo-alignment of any one of Claims 1-12. The liquid crystal display element which has a liquid crystal aligning film of Claim 13. A lateral electric field type liquid crystal display device having the liquid crystal alignment film according to claim 13.