JP2021071717A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device using the same, and diamine and polymer - Google Patents

Abstract

To provide a liquid crystal aligning agent which allows for producing a liquid crystal display device with a good afterimage property and contrast, and high light resistance.SOLUTION: A liquid crystal aligning agent provided herein contains one or more polymers, and at least one of the polymers is obtained by reacting tetracarboxylic dianhydrides, diamines, etc., where at least one of the diamines is a compound represented by a formula (1) below. In the formula (1), X represents an alkylene having 1 to 12 carbon atoms or the like, a through c independently represent integers of 0 to 2, Ra and Rb independently represent a hydrogen atom, -F, a specific formula, etc., and Rc independently represents a hydrogen atom, etc.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device using the same. Specifically, a liquid crystal alignment agent for forming a photoalignment type liquid crystal alignment film (hereinafter, may be abbreviated as a photoalignment film), a photoalignment type liquid crystal alignment film formed by using this liquid crystal alignment agent, Then, the present invention relates to a liquid crystal display element having this liquid crystal alignment film. Further, the present invention relates to a polymer such as polyamic acid used in the liquid crystal alignment agent, and a diamine as a raw material thereof.

As a liquid crystal display element, TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, IPS (In-Plane Switching) mode, FFS (Fringe Field Switching) mode, vertical alignment type VA (Multi-domain Vertical Alignment) mode Various drive methods are known. These liquid crystal display elements are applied to image display devices of various electronic devices such as televisions and mobile phones, and are being developed with the aim of further improving display quality. Specifically, the performance improvement of the liquid crystal display element is achieved not only by the improvement of the drive system and the element structure but also by the constituent members used in the element. Among the constituent members used in the liquid crystal display element, the liquid crystal alignment film is one of the important materials related to the display quality, and the liquid crystal alignment film is used to meet the demand for higher quality of the liquid crystal display element. Is also being actively researched.

Here, the liquid crystal alignment film is provided on a pair of substrates provided on both sides of the liquid crystal layer of the liquid crystal display element in contact with the liquid crystal layer, and the liquid crystal molecules constituting the liquid crystal layer are constant with respect to the substrate. It has the function of orienting with regularity. By using a liquid crystal alignment film having high liquid crystal alignment, it is possible to realize a liquid crystal display element having high contrast and improved afterimage characteristics (see, for example, Patent Documents 1 and 2).
Currently, a solution (varnish) in which a polyamic acid, a soluble polyimide, or a polyamic acid ester is dissolved in an organic solvent is mainly used for forming such a liquid crystal alignment film. To form a liquid crystal alignment film with these varnishes, after applying the varnish to the substrate, the coating film is solidified by heating or the like to form a polyimide-based liquid crystal alignment film, and if necessary, orientation suitable for the above-mentioned display mode. Apply processing. Alignment treatment methods include a rubbing method in which the surface of the alignment film is rubbed with a cloth to adjust the direction of the polymer molecules, and a linearly polarized ultraviolet light is applied to the alignment film to photoisomerize or dimerize the polymer molecules. A photo-orientation method that causes photochemical changes to impart anisotropy to a film is known. Of these, the photo-orientation method has higher orientation uniformity than the rubbing method, and is a non-contact orientation treatment method. Therefore, there are advantages that the film is not scratched and that the causes of display defects of the liquid crystal display element such as dust generation and static electricity can be reduced.

As a liquid crystal alignment film using such a photo-alignment method, for example, in Patent Documents 1 to 6, diaminoazobenzene or the like is used as a raw material, and by applying a photoisomerization technique, the anchoring energy is large and the liquid crystal orientation is large. It is described that a good photoalignment film was obtained.

JP 2010-197999 International release 2013/157463 JP-A-2005-275364 JP-A-2007-248637 JP-A-2009-0694993 International release 2015/016118

As described above, a liquid crystal alignment film formed by subjecting a polyimide-based liquid crystal alignment film to an alignment treatment by a photoalignment method is known. However, the polyimide-based liquid crystal alignment film obtained by the photo-alignment method is generally inferior in electrical characteristics to the polyimide-based liquid crystal alignment film obtained by the rubbing treatment, which tends to impair the display quality of the liquid crystal display element. This is because the photoreactive groups introduced to cause a photochemical reaction, especially the azo group, easily absorbs light and generates radicals, the voltage retention rate of the liquid crystal display element (hereinafter abbreviated as VHR). It is considered that this is because (may be) decreases.

Therefore, the present inventors have provided an alignment film having good afterimage characteristics and contrast, capable of forming a liquid crystal display element that maintains a high voltage retention rate and does not deteriorate the display quality even when exposed to strong light for a long time. We have been diligently studying for the purpose of providing a liquid crystal alignment agent capable of forming such a liquid crystal alignment film.

As a result of diligent studies to solve the above problems, the present inventors have represented by the formula (1) as a raw material monomer (sometimes referred to as a photosensitive monomer) that causes a photochemical change in the liquid crystal alignment agent. By using the diamine that is produced, an alignment film with high anisotropy can be obtained, and by using this alignment film, it has good afterimage characteristics and contrast, even if it is exposed to strong light for a long time. The present invention has been completed by finding that it is possible to form a liquid crystal display element in which a high voltage holding ratio is maintained and the display quality is not deteriorated.
The present invention includes the following configurations.

式（１）において、Ｘは炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、
ａ〜ｃはそれぞれ独立に０〜２の整数であり、
Ｒ^ａおよびＲ^ｂはそれぞれ独立して水素原子、式（Ｐ１−１）、式（Ｐ１−２）、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆ、または−ＣＯＯＣＨ_３であり、
Ｒ^ｃはそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆであり、

式（Ｐ１−１）および式（Ｐ１−２）において、Ｒ^６ａ〜Ｒ^８ａは、それぞれ独立して、水素原子、置換もしくは無置換のアルキル、置換もしくは無置換のアルカノイル、置換もしくは無置換のアルコキシカルボニル、または置換もしくは無置換のアリールカルボニルであり、Ｒ^６ａ〜Ｒ^８ａは互いに同一であっても異なっていてもよく、＊は、式（１）におけるベンゼン環への結合位置を表し、
式（１）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す。 [1] A liquid crystal alignment agent containing at least one polymer, wherein at least one of the polymers is a polymer obtained by reacting tetracarboxylic dianhydrides with diamines, and at least one of the diamines is of the formula (1). A liquid crystal alignment agent which is a compound represented by 1).

In the formula (1), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
a to c are independently integers of 0 to 2, respectively.
R ^a and R ^b are independently hydrogen atoms, formula (P1-1), formula (P1-2), -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ , respectively.
R ^c is a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , and -F, respectively.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a are independently hydrogen atoms, substituted or unsubstituted alkyls, substituted or unsubstituted alkanoyls, substituted or unsubstituted alkoxys, respectively. It is a carbonyl, or a substituted or unsubstituted arylcarbonyl, and R ^{6a to} R ^8a may be the same or different from each other, and * represents the bonding position to the benzene ring in the formula (1).
In formula (1), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

式（１−１）において、Ｘは炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、
Ｒ^１およびＲ^２はそれぞれ独立して水素原子、式（Ｐ１−１）、または式（Ｐ１−２）であり、Ｒ^１およびＲ^２の少なくとも１つは式（Ｐ１−１）または式（Ｐ１−２）であり、
ｃは０〜２の整数であり、Ｒ^４はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆであり、
式（１−２）において、Ｘは炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、
ａは０〜２の整数であり、Ｒ^３はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆ、または−ＣＯＯＣＨ_３であり、
ｂは０〜２の整数であり、Ｒ^５はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆ、または−ＣＯＯＣＨ_３であり、
ｃは０〜２の整数であり、Ｒ^４はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆであり、

式（Ｐ１−１）および式（Ｐ１−２）において、Ｒ^６ａ〜Ｒ^８ａは、それぞれ独立して、水素原子、置換もしくは無置換のアルキル、置換もしくは無置換のアルカノイル、置換もしくは無置換のアルコキシカルボニル、または置換もしくは無置換のアリールカルボニルであり、Ｒ^６ａ〜Ｒ^８ａは互いに同一であっても異なっていてもよく、＊は、式（１−１）におけるベンゼン環への結合位置を表し、
式（１−１）および式（１−２）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す。 [2] The liquid crystal alignment agent according to item [1], wherein at least one of the compounds represented by the formula (1) is a compound represented by the formula (1-1) or the formula (1-2).

In formula (1-1), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
R ¹ and R ² are independently hydrogen atoms, formula (P1-1), or formula (P1-2), and ^{at least one of R 1} and R ² is formula (P1-1) or formula (P1). -2) and
c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.
In formula (1-2), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
a is an integer from 0 to 2, and R ³ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ .
b is an integer from 0 to 2, and R ⁵ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ .
c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a are independently hydrogen atoms, substituted or unsubstituted alkyls, substituted or unsubstituted alkanoyls, substituted or unsubstituted alkoxys, respectively. It is a carbonyl, or a substituted or unsubstituted arylcarbonyl, and R ^{6a to} R ^8a may be the same or different from each other, and * represents the bonding position to the benzene ring in the formula (1-1).
In formulas (1-1) and (1-2), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

式（１−１−１）〜式（１−１−１２）において、Ｒ^６は炭素数１〜４のアルキル基であり、
ｌは１〜１０の整数であり、ｍは１〜１１の整数であり、ｎは１〜１２の整数である。 [3] The compound represented by the formula (1-1) is a compound represented by at least one formula selected from the group consisting of the formulas (1-1-1) to (1-1-12). , The liquid crystal alignment agent according to item [2].

In formulas (1-1-1) to (1-1-12), R ⁶ is an alkyl group having 1 to 4 carbon atoms.
l is an integer of 1 to 10, m is an integer of 1 to 11, and n is an integer of 1 to 12.

式（１−２−１）〜式（１−２−９）において、ｌは１〜１０の整数であり、ｍは１〜１１の整数であり、ｎは１〜１２の整数である。 [4] The compound represented by the formula (1-2) is a compound represented by at least one formula selected from the group consisting of the formulas (1-2-1) to (1-2-9). , The liquid crystal alignment agent according to item [2].

In equations (1-2-1) to (1-2-9), l is an integer of 1 to 10, m is an integer of 1 to 11, and n is an integer of 1 to 12.

[5] The liquid crystal alignment agent according to any one of [1] to [4], wherein all the polymers contain at least one compound represented by the formula (1) as a raw material.

[6] The liquid crystal alignment agent according to any one of [1] to [4], wherein at least one polymer does not contain a compound represented by the formula (1) as a raw material.

[7] A liquid crystal alignment film formed from the liquid crystal alignment agent according to any one of [1] to [6].

[8] A liquid crystal display element having the liquid crystal alignment film according to item [7].

[9] A method for producing a liquid crystal alignment film, which comprises a step of applying the liquid crystal aligning agent according to any one of [1] to [6] to a substrate, and a step of irradiating the coating film with polarized ultraviolet rays.

式（１）において、Ｘは炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、
ａ〜ｃはそれぞれ独立に０〜２の整数であり、
Ｒ^ａおよびＲ^ｂはそれぞれ独立して水素原子、式（Ｐ１−１）、式（Ｐ１−２）、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆ、または−ＣＯＯＣＨ_３であり、
Ｒ^ｃはそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆであり、

式（Ｐ１−１）および式（Ｐ１−２）において、Ｒ^６ａ〜Ｒ^８ａは、それぞれ独立して、水素原子、置換もしくは無置換のアルキル、置換もしくは無置換のアルカノイル、置換もしくは無置換のアルコキシカルボニルまたは置換もしくは無置換のアリールカルボニルであり、Ｒ^６ａ〜Ｒ^８ａは互いに同一であっても異なっていてもよく、＊は、式（１）におけるベンゼン環への結合位置を表し、
式（１）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す。 [10] A compound represented by the formula (1).

In the formula (1), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
a to c are independently integers of 0 to 2, respectively.
R ^a and R ^b are independently hydrogen atoms, formula (P1-1), formula (P1-2), -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ , respectively.
R ^c is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a are independently hydrogen atoms, substituted or unsubstituted alkyls, substituted or unsubstituted alkanoyls, substituted or unsubstituted alkoxys, respectively. It is a carbonyl or a substituted or unsubstituted arylcarbonyl, and R ^{6a to} R ^8a may be the same or different from each other, and * represents the bonding position to the benzene ring in the formula (1).
In formula (1), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

式（１−１）において、Ｘは炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、
Ｒ^１およびＲ^２はそれぞれ独立して水素原子、式（Ｐ１−１）、または式（Ｐ１−２）であり、Ｒ^１およびＲ^２の少なくとも１つは式（Ｐ１−１）または式（Ｐ１−２）であり、
ｃは０〜２の整数であり、Ｒ^４はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆであり、
式（１−２）において、Ｘは炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、
ａは０〜２の整数であり、Ｒ^３はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆ、または−ＣＯＯＣＨ_３であり、
ｂは０〜２の整数であり、Ｒ^５はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆ、または−ＣＯＯＣＨ_３であり、
ｃは０〜２の整数であり、Ｒ^４はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆであり、

式（Ｐ１−１）および式（Ｐ１−２）において、Ｒ^６ａ〜Ｒ^８ａは、それぞれ独立して、水素原子、置換もしくは無置換のアルキル、置換もしくは無置換のアルカノイル、置換もしくは無置換のアルコキシカルボニルまたは置換もしくは無置換のアリールカルボニルであり、Ｒ^６ａ〜Ｒ^８ａは互いに同一であっても異なっていてもよく、＊は、式（１−１）におけるベンゼン環への結合位置を表し、
式（１−１）および式（１−２）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す。 [11] The compound according to item [10], which is represented by the formula (1-1) or the formula (1-2).

In formula (1-1), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
R ¹ and R ² are independently hydrogen atoms, formula (P1-1), or formula (P1-2), and ^{at least one of R 1} and R ² is formula (P1-1) or formula (P1). -2) and
c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.
In formula (1-2), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
a is an integer from 0 to 2, and R ³ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ .
b is an integer from 0 to 2, and R ⁵ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ .
c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a are independently hydrogen atoms, substituted or unsubstituted alkyls, substituted or unsubstituted alkanoyls, substituted or unsubstituted alkoxys, respectively. It is a carbonyl or a substituted or unsubstituted arylcarbonyl, and R ^{6a to} R ^8a may be the same or different from each other, and * represents the bonding position to the benzene ring in the formula (1-1).
In formulas (1-1) and (1-2), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

式（１−１−１）〜式（１−１−１２）において、Ｒ^６は炭素数１〜４のアルキル基であり、
ｌは１〜１０の整数であり、ｍは１〜１１の整数であり、ｎは１〜１２の整数である。 [12] The compound represented by the formula (1-1) is represented by at least one formula selected from the group consisting of the formulas (1-1-1) to (1-1-12) [11]. ] The compound according to the section.

In formulas (1-1-1) to (1-1-12), R ⁶ is an alkyl group having 1 to 4 carbon atoms.
l is an integer of 1 to 10, m is an integer of 1 to 11, and n is an integer of 1 to 12.

式（１−２−１）〜式（１−２−９）において、ｌは１〜１０の整数であり、ｍは１〜１１の整数であり、ｎは１〜１２の整数である。 [13] The compound represented by the formula (1-2) is represented by at least one formula selected from the group consisting of the formulas (1-2-1) to (1-2-9) [11]. ] The compound according to the section.

In equations (1-2-1) to (1-2-9), l is an integer of 1 to 10, m is an integer of 1 to 11, and n is an integer of 1 to 12.

[14] A polymer obtained by reacting tetracarboxylic dianhydrides with diamines, wherein the diamines are at least one of the compounds according to any one of [10] to [13].

By using the liquid crystal alignment agent for photoalignment of the present invention, a liquid crystal alignment film having high anisotropy can be obtained. Further, by using this liquid crystal alignment film, it is possible to realize a liquid crystal display element which has excellent afterimage characteristics and contrast, maintains a high voltage retention rate even when exposed to strong light for a long time, and does not deteriorate the display quality. Can be done.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on typical embodiments or specific examples, but the present invention is not limited to such embodiments. The "liquid crystal alignment agent" in the present invention is a liquid crystal alignment agent that can impart anisotropy by irradiating polarized ultraviolet rays when the film is formed on a substrate, and is simply "liquid crystal" in the present specification. Sometimes it is called "aligning agent", and sometimes it is called "liquid crystal alignment agent for photo-alignment". Further, in the present invention, "tetracarboxylic dianhydrides" refers to tetracarboxylic dianhydrides, tetracarboxylic dianhydrides or tetracarboxylic dianhydrides. Further, in the present invention, diamines and dihydrazides may be referred to as "diamines".

式（１）において、Ｘは炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、
ａ〜ｃはそれぞれ独立に０〜２の整数であり、
Ｒ^ａおよびＲ^ｂはそれぞれ独立して水素原子、式（Ｐ１−１）、式（Ｐ１−２）、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆ、または−ＣＯＯＣＨ_３であり、
Ｒ^ｃはそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆであり、

式（Ｐ１−１）および式（Ｐ１−２）において、Ｒ^６ａ〜Ｒ^８ａは、それぞれ独立して、水素原子、置換もしくは無置換のアルキル、置換もしくは無置換のアルカノイル、置換もしくは無置換のアルコキシカルボニルまたは置換もしくは無置換のアリールカルボニルであり、Ｒ^６ａ〜Ｒ^８ａは互いに同一であっても異なっていてもよく、＊は、式（１）におけるベンゼン環への結合位置を表し、
式（１）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す。 <Compound represented by formula (1)>
The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent containing a polymer obtained by reacting tetracarboxylic dianhydrides with diamines, and the diamines are a group consisting of compounds represented by the following formula (1). Includes at least one selected from.

In the formula (1), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
a to c are independently integers of 0 to 2, respectively.
R ^a and R ^b are independently hydrogen atoms, formula (P1-1), formula (P1-2), -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ , respectively.
R ^c is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a are independently hydrogen atoms, substituted or unsubstituted alkyls, substituted or unsubstituted alkanoyls, substituted or unsubstituted alkoxys, respectively. It is a carbonyl or a substituted or unsubstituted arylcarbonyl, and R ^{6a to} R ^8a may be the same or different from each other, and * represents the bonding position to the benzene ring in the formula (1).
In formula (1), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

The compound represented by the formula (1) of the present invention has a structure in which a benzene ring is bonded to one side of the azobenzene structure via an alkylene or the like.

When the compound represented by the formula (1) is used as a raw material for a polymer, a monomer having an azobenzene structure but not having an alkylene or the like and a benzene ring bonded thereto (for example, diaminoazobenzene) is attached to one side of the azobenzene structure. The proportion of the azobenzene structure in the entire polymer is relatively low as compared with the case of using it as a raw material. Therefore, when a liquid crystal alignment film containing a polymer using the compound represented by the formula (1) as a raw material is used to form a liquid crystal alignment film and a liquid crystal display element is formed using this film, the process of forming this film occurs. It is considered that the decrease in VHR of the liquid crystal display element due to light irradiation is suppressed.

However, simply reducing the proportion of a monomer having an azobenzene structure (for example, diaminoazobenzene) in the raw material of the liquid crystal aligning agent suppresses the decrease in VHR, but may deteriorate the afterimage characteristics and contrast of the liquid crystal display element. ..

On the other hand, the present inventors use at least one of the compounds represented by the formula (1) as a raw material to reduce the proportion of the azobenzene structure, suppress the decrease in VHR, and have good afterimage characteristics and contrast. Was found to be feasible. The reason is not always clear, but it can be considered as follows.

In a liquid crystal alignment agent for photoalignment using photoisomerization of an azobenzene structure, when polarized ultraviolet rays are irradiated in the process of forming a liquid crystal alignment film using the liquid crystal alignment agent for photoalignment, the azobenzene structure undergoes a photoisomerization reaction. Finally, the azobenzene structure is oriented along one direction (vertical to the polarization direction). In the polyamic acid using the compound represented by the formula (1), for example, a benzene ring is bonded to one side of the azobenzene structure via an alkylene or the like as compared with the case where diaminoazobenzene is used, and there are few steric obstacles. Since this photoisomerization reaction is likely to occur, it is presumed that good afterimage characteristics and contrast can be obtained even if the proportion of the azobenzene structure is small. Furthermore, in the polymer, the ratio of alkylene to the imide bond and the ring structure is relatively high, so that the entire polymer can move easily, and high anisotropy is exhibited, which is also the reason why good afterimage characteristics and contrast can be obtained. It is presumed to be one.

式（Ａ）において、＊は結合手であり、結合手のベンゼン環に対する結合位置はそれぞれ独立して任意であり、ベンゼン環の置換可能な水素は置換基を有していてもよい。 In the present specification, the azobenzene structure means a structure represented by the following formula (A).

In the formula (A), * is a bond, the bond position of the bond with respect to the benzene ring is independent and arbitrary, and the substitutable hydrogen of the benzene ring may have a substituent.

式（１−１）において、Ｘは炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、
Ｒ^１およびＲ^２はそれぞれ独立して水素原子、式（Ｐ１−１）、または式（Ｐ１−２）であり、Ｒ^１およびＲ^２の少なくとも１つは式（Ｐ１−１）または式（Ｐ１−２）であり、
ｃは０〜２の整数であり、Ｒ^４はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆであり、
式（１−２）において、Ｘは炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、
ａは０〜２の整数であり、Ｒ^３はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆ、または−ＣＯＯＣＨ_３であり、
ｂは０〜２の整数であり、Ｒ^５はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆ、または−ＣＯＯＣＨ_３であり、
ｃは０〜２の整数であり、Ｒ^４はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆであり、

式（Ｐ１−１）および式（Ｐ１−２）において、Ｒ^６ａ〜Ｒ^８ａは、それぞれ独立して、水素原子、置換もしくは無置換のアルキル、置換もしくは無置換のアルカノイル、置換もしくは無置換のアルコキシカルボニルまたは置換もしくは無置換のアリールカルボニルであり、Ｒ^６ａ〜Ｒ^８ａは互いに同一であっても異なっていてもよく、＊は、式（１−１）におけるベンゼン環への結合位置を表し、
式（１−１）および式（１−２）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す。 <Compound represented by formula (1)>
Examples of the compound represented by the formula (1) include compounds represented by the following formula (1-1) or formula (1-2).

In formula (1-1), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
R ¹ and R ² are independently hydrogen atoms, formula (P1-1), or formula (P1-2), and ^{at least one of R 1} and R ² is formula (P1-1) or formula (P1). -2) and
c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.
In formula (1-2), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
a is an integer from 0 to 2, and R ³ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ .
b is an integer from 0 to 2, and R ⁵ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ .
c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a are independently hydrogen atoms, substituted or unsubstituted alkyls, substituted or unsubstituted alkanoyls, substituted or unsubstituted alkoxys, respectively. It is a carbonyl or a substituted or unsubstituted arylcarbonyl, and R ^{6a to} R ^8a may be the same or different from each other, and * represents the bonding position to the benzene ring in the formula (1-1).
In formulas (1-1) and (1-2), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

When the compound represented by the formula (1-1) is reacted with a raw material composition containing the compound to form a polymer, it is used in a firing step for forming a liquid crystal alignment film from a liquid crystal alignment agent containing the polymer. Causes a thermal cyclization reaction. As a result, the azobenzene structure disappears or is reduced, so that the absorption of light near 400 nm derived from the azobenzene structure is suppressed. Therefore, the compound represented by the formula (1-1) has higher transparency of the obtained alignment film.

For example, in the formula (1-1), ^{a compound having a structure in which R 1} is a hydrogen atom and R ² is represented by the above formula (P1-1) or the above formula (P1-2) is as shown in Scheme 1 below. Causes a thermal cyclization reaction.

The compound represented by the formula (1-2) is useful because of its ease of synthesis and high anisotropy of the obtained liquid crystal alignment film.

式（１−１−１）〜式（１−１−１２）において、Ｒ^６は炭素数１〜４のアルキル基であり、
ｌは１〜１０の整数であり、ｍは１〜１１の整数であり、ｎは１〜１２の整数である。
Ｒ^６の炭素数１〜４のアルキル基の好ましい具体例は、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ターシャリーブチル基である。 Specifically, the compound represented by the formula (1-1) is a compound represented by the following formulas (1-1-1) to (1-1-12).

In formulas (1-1-1) to (1-1-12), R ⁶ is an alkyl group having 1 to 4 carbon atoms.
l is an integer of 1 to 10, m is an integer of 1 to 11, and n is an integer of 1 to 12.
Preferred specific examples of the alkyl group having 1 to 4 carbon atoms of R ⁶ are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tertiary butyl group.

Specifically, the compound represented by the formula (1-2) is a compound represented by the following formulas (1-2-1) to (1-2-9).

In equations (1-2-1) to (1-2-9), l is an integer of 1 to 10, m is an integer of 1 to 11, and n is an integer of 1 to 12.

When the transparency of the formed liquid crystal alignment film is emphasized, one or more of the compounds selected from the group consisting of the formulas (1-1-1) to (1-1-12) may be used. More preferred. When emphasizing the high contrast of the formed liquid crystal display element, one or more of the compounds selected from the group consisting of the formulas (1-2-1) to (1-2-9) are selected. It is more preferable to use it. When it is important to obtain a liquid crystal alignment film having higher anisotropy, one or more of the compounds selected from the group consisting of the formulas (1-2-1) to (1-2-9). Is more preferable to use.
When it is important to obtain a liquid crystal alignment film (that is, a highly sensitive liquid crystal alignment agent) capable of forming an element having good afterimage characteristics even with a small amount of energy during the alignment treatment, the formula (1-2) 4) It is more preferable to use any one or more of the compounds selected from the group consisting of the formulas (1-2-9).

A preferred specific example of the formula (1-1) is a compound represented by the formula (1-1-9) or the formula (1-1-4). Among these, a compound in which n = 2 to 6 and R ⁶ is a methyl group or an ethyl group in the formula (1-1-9), or l = 2 to 6 in the formula (1-1-4). The compound is more preferable, and the compound in which n = 2 to 6 and R ⁶ is an ethyl group in the formula (1-1-9) or the compound in which l = 2 to 4 in the formula (1-1-4) is further preferable. ..

A preferred specific example of the formula (1-2) is a compound represented by the formula (1-2-1), the formula (1-2-4), or the formula (1-2-7), and l = 2. ~ 6 is more preferable, l = 4 is more preferable, and l = 4 of the formula (1-2-1) or the formula (1-2-4) is particularly preferable.

<Method for producing the compound represented by the formula (1)>
A method for producing the compound represented by the formula (1) of the present invention will be described.

[Method for producing compound represented by formula (1-1)]
The compound represented by the formula (1-1) is produced by Steps 1-1 to 1-3. Here, in the formula (1-1), the case where R ² is a hydrogen atom and R ³ is the formula (P1-1) is illustrated, but other compounds represented by the formula (1-1) are also described below. It can be produced by using a known reaction with reference to the examples.

The azobenzene derivative represented by the formula (1c) is produced by the step 1-1 (Scheme1-1) of reacting the aniline derivative represented by the formula (1a) with the phenol derivative represented by the formula (1b).

In formulas (1a) and (1c), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group, or an optionally substituted alkoxycarbonylamino. Is the basis.
In formulas (1b) and (1c), R ^6a is a hydrogen atom, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkanoyl, a substituted or unsubstituted alkoxycarbonyl or a substituted or unsubstituted arylcarbonyl. In formulas (1a) and (1c), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

The reaction between the aniline derivative represented by the formula (1a) and the phenol derivative represented by the formula (1b) (reaction in step 1-1) is a diazo coupling reaction, and is a general reaction condition in the diazo coupling reaction. Can be adopted. For example, a benzenediazonium salt is prepared from the aniline derivative represented by the formula (1a), and the reaction is carried out with the phenol derivative represented by the formula (1b) in the presence of a carboxylate such as sodium acetate or potassium acetate. As a result, the target azobenzene derivative represented by the formula (1c) can be obtained in good yield.

The azobenzene derivative represented by the formula (1e) is produced by the step 1-2 (Scheme1-2) of reacting the azobenzene derivative represented by the formula (1c) with the halogenated alkylbenzene derivative represented by the formula (1d).

In formulas (1c) and (1e), R ^6a is a hydrogen atom, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkanoyl, a substituted or unsubstituted alkoxycarbonyl, or a substituted or unsubstituted arylcarbonyl. ..
In formulas (1c), (1d) and (1e), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group, or an substituted alkylcarbonylamino group. It is also a good alkoxycarbonylamino group.
Y in the formula (1d) and X in the formula (1e) are alkylenes having 1 to 12 carbon atoms, and _{one or more of the alkylenes − (CH 2} ) ₂ − not adjacent to each other are −O− and −NH. It may be replaced by any of −.
In formula (1d), L is a halogen atom such as a bromine atom or an iodine atom, or a sulfonyloxy group such as a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a benzenesulfonyloxy group, or a p-toluenesulfonyloxy group. , In formulas (1d) and (1e), c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F, respectively.
In formulas (1c), (1d) and (1e), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

The reaction between the azobenzene derivative represented by the formula (1c) and the halogenated alkylbenzene derivative represented by the formula (1d) (reaction in step 1-2) is an etherification reaction, and is a general reaction condition in the etherification reaction. Can be adopted. For example, by carrying out the reaction of the azobenzene derivative represented by the formula (1c) and the halogenated alkylbenzene derivative represented by the formula (1d) in the presence of a base such as sodium hydroxide or potassium carbonate, the target product. The azobenzene derivative represented by the formula (1e) can be obtained in good yield.

式（１ｅ）および式（１−１ａ）において、Ｒ^６ａは、水素原子、置換もしくは無置換のアルキル、置換もしくは無置換のアルカノイル、置換もしくは無置換のアルコキシカルボニル、または置換もしくは無置換のアリールカルボニルである。
式（１ｅ）において、Ｒ^９は、ニトロ基、置換されていてもよいアリールメチルアミノ基、置換されていてもよいアルキルカルボニルアミノ基、または置換されていてもよいアルコキシカルボニルアミノ基である。
式（１ｅ）および式（１−１ａ）において、Ｘは、炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、ｃは０〜２の整数であり、Ｒ^４はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆである。
式（１ｅ）および式（１−１ａ）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す。 ^{The compound represented by the formula (1) is produced by converting R 9} of the azobenzene derivative represented by the formula (1e) into an amino group by the reaction of Step 1-3 (Scheme 1-3).

In formulas (1e) and (1-1a), R ^6a is a hydrogen atom, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkanoyl, a substituted or unsubstituted alkoxycarbonyl, or a substituted or unsubstituted arylcarbonyl. Is.
In formula (1e), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group, or an optionally substituted alkoxycarbonylamino group.
In formulas (1e) and (1-1a), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent _{alkylenes- (CH 2} ) _{2-are are -O- and -NH.} It may be replaced by any of −, where c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, −CH ₃ , −OCH ₃ , −CF ₃ , or −F, respectively.
In formulas (1e) and (1-1a), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

In the reaction of steps 1-3, the azobenzene derivative represented by the formula (1-1a) can be produced in good yield by using the method suitable for ^{R 9 in the formula (1e).}

In the formula (1e), when R ⁹ is a nitro group, the reaction in step 1-3 is a reduction reaction, and a sulfide such as sodium sulfide, an inorganic salt such as sodium nitionate, or the like is used as the reducing agent. Reduction with reagents, catalytic reduction with Pd / C catalyst, lane nickel, etc. in a hydrogen gas atmosphere, metal reduction with iron, zinc, tin chloride, etc. in the presence of acids such as hydrochloric acid and acetic acid, etc. Although various reduction methods can be used, since the nitro group can be reduced while suppressing the reduction of the azo bond, reduction with a reagent, which is carried out using a reducing agent such as sulfide, is preferable.

In the formula (1e), if R ⁹ is aryl methyl amino group which may be substituted, deprotection by hydrogenolysis pressurized (e.g. H _2, Pd / _C), deprotection at the oxidation conditions, a strong acid Deprotection under sexual conditions can be mentioned. Of these, deprotection under oxidizing conditions is preferable, and quinone-based oxidizing reagents such as 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), p-chloranyl, and o-chloranyl, and diammonium cerium nitrate (IV). ) And the like under mild oxidizing conditions are more preferable because they can deprotect the arylmethylamino group while suppressing the reduction of the azo bond. In addition, trifluoroacetic acid (TFA) or hydrochloric acid can be used for deprotection under strongly acidic conditions.

In the formula (1e), an alkyl carbonyl amino group R ⁹ may be substituted, or when it is an optionally substituted alkoxycarbonylamino group, by acid treatment, the easily protecting group R ⁹ Can be deprotected. Examples of the acid used for deprotection include TFA and hydrochloric acid.

式（１ｆ）において、Ｒ^９は、ニトロ基、置換されていてもよいアリールメチルアミノ基、置換されていてもよいアルキルカルボニルアミノ基、または置換されていてもよいアルコキシカルボニルアミノ基であり、Ｒ^６ａは、水素原子、置換もしくは無置換のアルキル、置換もしくは無置換のアルカノイル、置換もしくは無置換のアルコキシカルボニル、または置換もしくは無置換のアリールカルボニルである。 In the above, a method for producing a compound in which ^{R 1} is a hydrogen atom and R ^{2 is a formula (P1-1) in the formula (1-1) is shown.} Other compounds represented by the formula (1-1) can also be synthesized by a similar production method.
For example, by replacing step 1-1 with the reaction of the compound represented by the formula (1f) with the phenol derivative, R ¹ is the formula (P1-1) and R ² is the formula (1-1). A compound that is a hydrogen atom can be obtained. Further, for example, by replacing step 1-1 with the reaction of the compound represented by the formula (1f) and the formula (1b), R ¹ and R ² in the formula (1) are the formula (P1-1). Compounds can be obtained.

In formula (1f), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group, or an optionally substituted alkoxycarbonylamino group, and R ^{Reference numeral 6a} is a hydrogen atom, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkanoyl, a substituted or unsubstituted alkoxycarbonyl, or a substituted or unsubstituted arylcarbonyl.

[Method for producing compound represented by formula (1-2)]
The compound represented by the formula (1-2) is produced by Steps 2-1 to 2-3.

式（２ａ）および式（２ｃ）において、Ｒ^９は、ニトロ基、置換されていてもよいアリールメチルアミノ基、置換されていてもよいアルキルカルボニルアミノ基、または置換されていてもよいアルコキシカルボニルアミノ基である。
式（２ａ）、式（２ｂ）および式（２ｃ）において、Ｒ^３はそれぞれ独立して、水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆまたは−ＣＯＯＣＨ_３であり、Ｒ^５はそれぞれ独立して、水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆまたは−ＣＯＯＣＨ_３であり、ａは０〜２の整数であり、ｂは０〜２の整数である。
式（２ａ）、式（２ｂ）、および式（２ｃ）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す。 The azobenzene derivative represented by the formula (2c) is produced by the step 2-1 (Scheme2-1) of reacting the aniline derivative represented by the formula (2a) with the phenol derivative represented by the formula (2b).

In formulas (2a) and (2c), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group, or an optionally substituted alkoxycarbonylamino. Is the basis.
In formulas (2a), (2b) and (2c), R ³ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , and R ⁵ Are independently hydrogen atoms, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , where a is an integer of 0-2 and b is an integer of 0-2.
In formulas (2a), (2b), and (2c), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

The reaction between the aniline derivative represented by the formula (2a) and the phenol derivative represented by the formula (2b) (reaction in step 2-1) is a diazo coupling reaction, for example, see step 1-1 above. can do.

式（２ｃ）、式（２ｄ）および式（２ｅ）において、Ｒ^９は、ニトロ基、置換されていてもよいアリールメチルアミノ基、置換されていてもよいアルキルカルボニルアミノ基、または置換されていてもよいアルコキシカルボニルアミノ基である。
式（２ｃ）および式（２ｅ）において、Ｒ^３はそれぞれ独立して、水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆまたは−ＣＯＯＣＨ_３であり、Ｒ^５はそれぞれ独立して、水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆまたは−ＣＯＯＣＨ_３であり、ａは０〜２の整数であり、ｂは０〜２の整数である。
式（２ｄ）におけるＹ、および式（２ｅ）におけるＸは、炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−または−ＮＨ−のいずれかで置き換えられていてもよい。
式（２ｄ）において、Ｌは、臭素原子もしくはヨウ素原子などのハロゲン原子、またはメタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、ベンゼンスルホニルオキシ基、もしくはｐ−トルエンスルホニルオキシ基などのスルホニルオキシ基であり、ｃは０〜２の整数であり、Ｒ^４はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆである。
式（２ｃ）、式（２ｄ）および式（２ｅ）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す。 The azobenzene derivative represented by the formula (2e) is produced by the step 2-2 (Scheme2-2) of reacting the azobenzene derivative represented by the formula (2c) with the halogenated alkylbenzene derivative represented by the formula (2d).

In formulas (2c), (2d) and (2e), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group, or an substituted alkylcarbonylamino group. It is also a good alkoxycarbonylamino group.
In formulas (2c) and (2e), R ³ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , and R ⁵ is independent. , Hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , where a is an integer of 0-2 and b is an integer of 0-2.
Y in the formula (2d) and X in the formula (2e) are alkylenes having 1 to 12 carbon atoms, and _{one or more of the alkylenes − (CH 2} ) ₂ − not adjacent to each other are −O− or −NH. It may be replaced by any of −.
In formula (2d), L is a halogen atom such as a bromine atom or an iodine atom, or a sulfonyloxy group such as a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a benzenesulfonyloxy group, or a p-toluenesulfonyloxy group. , C are integers from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F, respectively.
In formulas (2c), (2d) and (2e), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.

The reaction between the azobenzene derivative represented by the formula (2c) and the halogenated alkylbenzene derivative represented by the formula (2d) (reaction in step 2-2) is an etherification reaction. Can be referred to.

式（２ｅ）において、Ｒ^９は、ニトロ基、置換されていてもよいアリールメチルアミノ基、置換されていてもよいアルキルカルボニルアミノ基、又は置換されていてもよいアルコキシカルボニルアミノ基である。
式（２ｅ）および式（１−２）において、Ｒ^３はそれぞれ独立して、水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆまたは−ＣＯＯＣＨ_３であり、Ｒ^５はそれぞれ独立して、水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−Ｆまたは−ＣＯＯＣＨ_３であり、ａは０〜２の整数であり、ｂは０〜２の整数である。
式（２ｅ）および式（１−２）において、Ｘは、炭素数１〜１２のアルキレンであり、前記アルキレンの−（ＣＨ_２）_２−の隣り合わない１つ以上が−Ｏ−および−ＮＨ−のいずれかで置き換えられていてもよく、ｃは０〜２の整数であり、Ｒ^４はそれぞれ独立して水素原子、−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、または−Ｆである。
式（２ｅ）および式（１−２）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す。
工程２−３の反応は、式（２ｅ）におけるＲ^９に適した方法を利用することにより、式（１−２）で示されるアゾベンゼン誘導体を収率よく製造することができる。詳しくは、上記の工程１−３を参照することができる。 ^{The compound represented by the formula (1-2) is produced by converting R 9} of the azobenzene derivative represented by the formula (2e) into an amino group by the reaction of step 2-3 (Scheme2-3).

In formula (2e), R ⁹ is a nitro group, an optionally substituted arylmethylamino group, an optionally substituted alkylcarbonylamino group, or an optionally substituted alkoxycarbonylamino group.
In formulas (2e) and (1-2), R ³ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , and R ⁵ is independent. Then, it is a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F or -COOCH ₃ , where a is an integer of 0 to 2 and b is an integer of 0 to 2.
In formulas (2e) and (1-2), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are −O− and −NH.} It may be replaced by any of −, where c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, −CH ₃ , −OCH ₃ , −CF ₃ , or −F, respectively.
In formulas (2e) and (1-2), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary.
In the reaction of steps 2-3, the azobenzene derivative represented by the formula (1-2) can be produced in good yield by using the method suitable for ^{R 9 in the formula (2e).} For details, the above steps 1-3 can be referred to.

<Type of polymer>
The polymer used as the liquid crystal alignment agent in the present invention is composed of polyamic acid, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide containing at least one of the compounds represented by the formula (1) as a raw material. At least one selected from the group of In the present specification, polyimide, partial polyimide, polyamic acid ester, polyamic acid-polyamide copolymer, and polyamideimide may be referred to as polyamic acid derivatives.

The details of the polyamic acid and the polyamic acid derivative will be described below.

Here, the polyamic acid is a polymer synthesized by a polymerization reaction between a diamine represented by the formula (DI) and a tetracarboxylic dianhydride represented by the formula (AN), and is represented by the formula (PAA). Has a structural unit to be. When the liquid crystal alignment agent containing the polyamic acid is heated and fired in the step of forming the liquid crystal alignment film, the polyamic acid is imidized, and a polyimide liquid crystal alignment film having a structural unit represented by the formula (PI) can be formed. ..

In formula (AN), formula (PAA), and formula (PI), X ¹ is a tetravalent organic group. In formula (DI), formula (PAA), and formula (PI), X ² is a divalent organic group. For ^{the preferred range and specific examples of the tetravalent organic group in X 1} , the corresponding structure of the tetracarboxylic dianhydride described in the column of known tetracarboxylic dianhydride below can be referred to. The preferred ranges and examples of the divalent organic group represented by X ^2, can be referred to for the corresponding structure of the diamine or dihydrazide described in the column of the formula (1) or a known diamines below.

式（ＰＡＥ）において、Ｘ^１は４価の有機基であり、Ｘ^２は２価の有機基であり、Ｙはアルキル基である。Ｘ^１、Ｘ^２の好ましい範囲と具体例については、式（ＰＡＡ）におけるＸ^１、Ｘ^２についての記載を参照することができる。Ｙにおいては、炭素数１〜６の直鎖状または分岐状のアルキル基が好ましく、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、またはターシャリーブチル基がより好ましい。 The polyamic acid derivative is a compound in which a part of the polyamic acid is replaced with another atom or atomic group to modify its properties, and it is particularly preferable that the polyamic acid derivative has high solubility in a solvent used for a liquid crystal alignment agent. Specific examples of such a polyamic acid derivative include 1) a polyimide in which all amino groups and carboxyl groups of a polyamic acid undergo a dehydration ring closure reaction, 2) a partial polyimide in which a partial dehydration ring closure reaction occurs, and 3) a polyamic acid. Polyamic acid ester in which the carboxyl group is converted to an ester, 4) Polyamic acid-polyimide copolymer obtained by replacing a part of the acid dianhydride contained in the tetracarboxylic acid dianhydride compound with an organic dicarboxylic acid and reacting. Further, 5) Polyimideimide obtained by dehydrating and ring-closing a part or all of the polyamic acid-polyimide copolymer can be mentioned. Among these derivatives, for example, polyimide may have a structural unit represented by the above formula (PI), and polyamic acid ester may have a structural unit represented by the following formula (PAE). I can mention things.

In formula (PAE), X ¹ is a tetravalent organic group, X ² is a divalent organic group, and Y is an alkyl group. The preferred ranges and examples of X ^{1, X 2,} can be referred to for ^X 1, ^{X 2} in the formula (PAA). In Y, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a tertiary butyl group is more preferable.

The polyamic acid can be obtained as a reaction product by a polymerization reaction between tetracarboxylic dianhydrides and diamines. For a description of the tetracarboxylic dianhydrides, a preferable range, and specific examples, the description in the column of tetracarboxylic dianhydrides below can be referred to. For a description of diamines, a preferable range, and specific examples, the description in the column of diamines below can be referred to.
The tetracarboxylic dianhydrides and diamines used in the synthesis of the polyamic acid may be one type or two or more types, respectively. The polyamic acid of the present invention can be obtained by using a compound represented by the formula (1) for at least one of the diamines.

When the above-mentioned polyamic acid of the present invention is a polyimide which is a polyamic acid derivative, the obtained polyamic acid solution is an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride which is a dehydrating agent. Polyimide can be obtained by subjecting it to an imidization reaction at a temperature of 20 to 150 ° C. with a tertiary amine such as triethylamine, pyridine, or colidin which is a dehydration ring-closing catalyst. Alternatively, a large amount of poor solvent (alcohol-based solvent such as methanol, ethanol, isopropanol, or glycol-based solvent) is used to precipitate the polyamic acid from the obtained polyamic acid solution, and the precipitated polyamic acid is prepared from toluene, xylene, etc. Polyimide can also be obtained by subjecting it to an imidization reaction at a temperature of 20 to 150 ° C. in a solvent together with the above-mentioned dehydrating agent and dehydration ring-closing catalyst.

In the imidization reaction, the ratio of the dehydrating agent to the dehydration ring closure catalyst is preferably 0.1 to 10 (molar ratio). The total amount of the dehydrating agent and the dehydrating ring-closing catalyst is preferably 1.5 to 10 times the total molar amount of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid. The degree of imidization can be controlled by adjusting the dehydrating agent, the amount of catalyst, the reaction temperature and the reaction time used in this imidization reaction, thereby obtaining a partial polyimide in which only a part of the polyamic acid is imidized. be able to. The obtained polyimide can be separated from the solvent used in the reaction and redissolved in another solvent to be used as a liquid crystal alignment agent, or can be used as a liquid crystal alignment agent without being separated from the solvent. ..

The polyamic acid ester can be synthesized by reacting a polyamic acid with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like, or a tetracarboxylic dianhydride or a tetracarboxylic dianester derived from a tetracarboxylic dianhydride. It can be obtained by a method of synthesizing by reacting dichloride with diamines. The tetracarboxylic dianester derived from the tetracarboxylic dianhydride can be obtained, for example, by reacting the tetracarboxylic dianhydride with 2 equivalents of an alcohol to open the ring, and the tetracarboxylic dianester dichloride is a tetracarboxylic acid. It can be obtained by reacting the diester with 2 equivalents of a chlorinating agent (eg thionyl chloride). The polyamic acid ester may have only an amic acid ester structure, or may be a partial esterified product in which an amic acid structure and an amic acid ester structure coexist. The polyamic acid ester of the present invention can be obtained by using a compound represented by the formula (1) for at least one of the diamines.

A polyamic acid or a derivative thereof using the compound represented by the formula (1) as a raw material can be produced in the same manner as a known polyamic acid or a derivative thereof used for forming a polyimide film.
The total amount of tetracarboxylic dianhydride charged is preferably 0.9 to 1.1 mol with respect to 1 mol of the total diamines.

The liquid crystal alignment agent of the present invention may contain only one of these polyamic acids, polyamic acid esters, and a polyimide obtained by imidizing them, or may contain two or more of them.

The molecular weight of the polyamic acid or its derivative of the present invention is preferably 5,000 to 500,000, more preferably 5,000 to 50,000, in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of a polyamic acid or a derivative thereof can be determined by measurement by a gel permeation chromatography (GPC) method.

The existence of the polyamic acid or its derivative of the present invention can be confirmed by analyzing the solid content obtained by precipitating with a large amount of poor solvent by IR (infrared spectroscopy) and NMR (nuclear magnetic resonance analysis). it can. Further, the extract of the decomposition product of the polyamic acid or its derivative by an aqueous solution of a strong alkali such as KOH or NaOH by an organic solvent is obtained by GC (gas chromatography), HPLC (high performance liquid chromatography) or GC-MS (gas chromatography mass spectrometry). By analyzing with, the monomer used can be confirmed.

Tetracarboxylic dianhydrides The tetracarboxylic dianhydrides used as the raw material of the polymer of the present invention can be selected from known tetracarboxylic dianhydrides without limitation.

Examples of tetracarboxylic dianhydrides are given below. These tetracarboxylic dianhydrides may be derived into a tetracarboxylic dianhydride or a tetracarboxylic dianhydride dichloride and used as a raw material for a polymer.

Such tetracarboxylic acid dianhydrides include aromatic systems (including heteroaromatic ring systems) in which the dicarboxylic acid anhydride is directly bonded to the aromatic ring, and aliphatic groups in which the dicarboxylic acid anhydride is not directly bonded to the aromatic ring. It may belong to any group of systems (including heterocyclic systems).

Examples of such tetracarboxylic dianhydrides include the following formulas (AN-1) to (AN-9), formulas (AN-11), formulas (AN-15), and formulas (AN-10-1). ), Formulas (AN-10-2), and compounds represented by formulas (AN-16-1) to formulas (AN-16-15).

式（ＡＮ−１）において、Ｇ^１１は単結合、炭素数１〜１２のアルキレン基、１，４−フェニレン基、または１，４−シクロヘキシレン基である。Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｇ^１２は独立して下記の３価の基のいずれかである。

Ｇ^１２が＞ＣＨ−であるとき、＞ＣＨ−の水素原子はメチル基で置換されていてもよい。Ｇ^１２が＞Ｎ−であるとき、Ｇ^１１は単結合および−ＣＨ_２−であることはなく、Ｘ^１１は単結合であることはない。Ｒ^１１は水素原子またはメチル基である。 [Tetracarboxylic dianhydride represented by the formula (AN-1)]

In formula (AN-1), G ¹¹ is a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group, or a 1,4-cyclohexylene group. X ¹¹ is independently single-bonded or -CH _2- . G ¹² is independently one of the following trivalent groups.

When G ¹² is> CH-, the hydrogen atom of> CH- may be substituted with a methyl group. When G ¹² is> N-, G ¹¹ is not single-bonded and -CH _2- , and X ¹¹ is not single-bonded. R ¹¹ is a hydrogen atom or a methyl group.

式（ＡＮ−１−２）および（ＡＮ−１−１４）において、ｍはそれぞれ独立して１〜１２の整数である。 Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formulas (AN-1-1) to (AN-1-15). ..

In the formulas (AN-1-2) and (AN-1-14), m is an integer of 1 to 12 independently.

式（ＡＮ−２）において、Ｒ^６１は独立して、水素原子、炭素数１〜５のアルキル基、またはフェニル基である。 [Tetracarboxylic dianhydride represented by the formula (AN-2)]

In formula (AN-2), R ⁶¹ is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formulas (AN-2-1) to (AN-2-3). ..

式（ＡＮ−３）において、環Ａ^１１はシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic dianhydride represented by the formula (AN-3)]

In formula (AN-3), ring A ¹¹ is a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formulas (AN-3-1) and (AN-3-2). ..

式（ＡＮ−４）において、Ｇ^１３は単結合、−（ＣＨ_２）_ｍ−、−Ｏ−、−Ｓ−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−ＣＯ−、−Ｃ（ＣＦ_３）_２−、または下記式（Ｇ１３−１）で表される２価の基であり、ｍは１〜１２の整数である。環Ａ^１１はそれぞれ独立してシクロヘキサン環またはベンゼン環である。Ｇ^１３は環Ａ^１１の任意の位置に結合してよい。

式（Ｇ１３−１）において、Ｇ^１３ａおよびＧ^１３ｂはそれぞれ独立して、単結合、−Ｏ−、−ＣＯＮＨ−、または−ＮＨＣＯ−で表される２価の基である。フェニレン基は、１，４−フェニレン基または１，３−フェニレン基であることが好ましい。 [Tetracarboxylic dianhydride represented by the formula (AN-4)]

In formula (AN-4), G ¹³ is a single bond,-(CH ₂ ) _m- , -O-, -S-, -C (CH ₃ ) _2- , -SO _2- , -CO-, -C. (CF ₃ ) _2- or a divalent group represented by the following formula (G13-1), and m is an integer of 1 to 12. Ring A ¹¹ is independently a cyclohexane ring or a benzene ring. G ¹³ may be coupled to any position on ring A ^11.

In formula (G13-1), G ^13a and G ^13b are independently divalent groups represented by single bonds, -O-, -CONH-, or -NHCO-, respectively. The phenylene group is preferably a 1,4-phenylene group or a 1,3-phenylene group.

式（ＡＮ−４−１７）において、ｍは１〜１２の整数である。 Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulas (AN-4-1) to (AN-4-31). ..

In equation (AN-4-17), m is an integer of 1-12.

式（ＡＮ−５）において、Ｒ^１１は独立して水素原子またはメチル基である。２つのＲ^１１のうちベンゼン環におけるＲ^１１は、ベンゼン環の置換可能な位置のいずれかに結合する。 [Tetracarboxylic dianhydride represented by the formula (AN-5)]

In formula (AN-5), R ¹¹ is independently a hydrogen atom or a methyl group. Of the two R ^{11 , R 11} on the benzene ring binds to any of the substitutable positions on the benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formulas (AN-5-1) to (AN-5-3). ..

式（ＡＮ−６）において、Ｘ^１１は独立して単結合または−ＣＨ_２−である。Ｘ^１２は−ＣＨ_２−、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−である。ｎは１または２である。ｎが２であるとき、２つのＸ^１２は互いに同一であっても異なっていてもよい。 [Tetracarboxylic dianhydride represented by the formula (AN-6)]

In formula (AN-6), X ¹¹ is independently single bond or −CH ₂₋ . X ¹² is _{-CH 2 -, - CH 2 CH} 2 - or -CH = CH-. n is 1 or 2. when n is 2, two X ¹² may be the being the same or different.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formulas (AN-6-1) to (AN-6-12). ..

式（ＡＮ−７）において、Ｘ^１１は単結合または−ＣＨ_２−である。 [Tetracarboxylic dianhydride represented by the formula (AN-7)]

In formula (AN-7), X ¹¹ is a single bond or −CH ₂₋ .

Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formulas (AN-7-1) and (AN-7-2). ..

式（ＡＮ−８）において、Ｘ^１１は単結合または−ＣＨ_２−である。Ｒ^１２は水素原子、メチル基、エチル基、またはフェニル基である。環Ａ^１２はシクロヘキサン環またはシクロヘキセン環である。 [Tetracarboxylic dianhydride represented by the formula (AN-8)]

In equation (AN-8), X ¹¹ is a single bond or −CH ₂₋ . R ¹² is a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. Ring A ¹² is a cyclohexane ring or cyclohexene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formulas (AN-8-1) and (AN-8-2). ..

式（ＡＮ−９）において、ｒはそれぞれ独立して０または１である。 [Tetracarboxylic dianhydride represented by the formula (AN-9)]

In equation (AN-9), r is independently 0 or 1, respectively.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formulas (AN-9-1) to (AN-9-3). ..

[Tetracarboxylic dianhydride represented by the formulas (AN-10-1) and (AN-10-2)]

式（ＡＮ−１１）において、環Ａ^１１は独立してシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic dianhydride represented by the formula (AN-11)]

In formula (AN-11), ring A ¹¹ is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formulas (AN-11-1) to (AN-11-3). ..

式（ＡＮ−１２）において、環Ａ^１１はそれぞれ独立してシクロヘキサン環またはベンゼン環である。 [Tetracarboxylic dianhydride represented by the formula (AN-12)]

In formula (AN-12), ring A ¹¹ is independently a cyclohexane ring or a benzene ring, respectively.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formulas (AN-12-1) to (AN-12-3). ..

式（ＡＮ−１５）において、ｗは１〜１０の整数である。 [Tetracarboxylic dianhydride represented by the formula (AN-15)]

In equation (AN-15), w is an integer of 1-10.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formulas (AN-15-1) to (AN-15-3). ..

Examples of the tetracarboxylic dianhydride other than the above include compounds represented by the following formulas (AN-16-1) to (AN-16-15).

In the above tetracarboxylic dianhydride, a suitable material for improving each property of the liquid crystal alignment film described later will be described. When it is important to further improve the liquid crystal orientation, the formula (AN-1-2), the formula (AN-4-17), the formula (AN-4-21), or the formula (AN-4-29) is used. ) Is more preferable, m = 4 to 8 is preferable in the formula (AN-1-2), and m = 4 to 8 is preferable in the formula (AN-4-17).

When it is important to improve the transmittance of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-2-1), and the formula (AN-3-3) 1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-10-1) The compound represented by AN-16-3) or the formula (AN-16-4) is preferable, and in the formula (AN-1-2), m = 4 or 8 is preferable, and the formula (AN-4-4) is preferable. In 17), m = 4 to 8 is preferable, and m = 8 is more preferable.

When it is important to improve the VHR of the liquid crystal display element, the formula (AN-1-1), the formula (AN-1-2), the formula (AN-3-1), the formula (AN-4-17) ), Equation (AN-4-30), Equation (AN-7-2), Equation (AN-10-1), Equation (AN-16-3), Equation (AN-16-4), or Equation (AN-16-4). The compound represented by AN-2-1) is preferable, m = 4 or 8 is preferable in the formula (AN-1-2), and m = 4 or 8 in the formula (AN-4-17). Is preferable, and m = 8 is more preferable.

Improving the relaxation rate of the residual charge (residual DC) in the liquid crystal alignment film by reducing the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing seizure. When this purpose is emphasized, the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), the formula (AN-4-29), or the formula (AN-) The compound represented by 11-3) is preferable.

Diamines Diamines other than the compound represented by the formula (1) used as a raw material for the polymer of the present invention can be selected from known diamines without limitation.

Diamines can be divided into two types according to their structure. That is, when the skeleton connecting two amino groups is viewed as a main chain, it is a group branched from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain type diamine. A diamine that does not have such a side chain group may be referred to as a non-side chain diamine. This side chain group is a group having an effect of increasing the pretilt angle.
By properly using the non-side chain diamine and the side chain diamine properly, it is possible to correspond to the pretilt angle required for each.

The side chain diamine is preferably used in combination to the extent that the characteristics of the present invention are not impaired. Further, it is preferable to select and use the side-chain type diamine and the non-side-chain type diamine for the purpose of improving the characteristics such as vertical orientation with respect to the liquid crystal, VHR, and afterimage characteristics.

上記の式（ＤＩ−１）において、Ｇ^２０は、−ＣＨ_２−または式（ＤＩ−１−ａ）で表される基である。Ｇ^２０が−ＣＨ_２−であるとき、ｍ個の−ＣＨ_２−の少なくとも１つは−ＮＨ−、−Ｏ−に置き換えられてもよく、ｍ個の−ＣＨ_２−の少なくとも１つの水素原子は水酸基またはメチル基で置換されてもよい。ｍは１〜１２の整数である。ＤＩ−１におけるｍが２以上であるとき、複数のＧ^２０は互いに同一であっても異なっていてもよい。ただし、Ｇ^２０が式（ＤＩ−１−ａ）であるとき、ｍは１である。

式（ＤＩ−１−ａ）において、ｖはそれぞれ独立して１〜６の整数である。 Diamines having no known side chain are shown in the following formulas (DI-1) to (DI-16).

In the above formula (DI-1), G ²⁰ is _{a group represented by −CH 2-} or the formula (DI-1-a). When it is, m number of -CH ₂ - - G ²⁰ is -CH ₂ At least one of -NH -, - may be replaced by O-, m-number of -CH ₂ - at least one hydrogen atom May be substituted with a hydroxyl group or a methyl group. m is an integer of 1-12. When m in DI-1 is 2 or more, the plurality of G ^20s may be the same or different from each other. However, when G ²⁰ is the equation (DI-1-a), m is 1.

In the formula (DI-1-a), v is an integer of 1 to 6 independently.

In equations (DI-3), (DI-6) and (DI-7), G ²¹ is independently single-bonded, -NH-, -NCH _3- , -O-, -S-, -S. -S-, -SO _2- , -CO-, -COO-, -CONCH _3- , -CONH-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m -, -O- (CH ₂ ) _m- O-, -N (CH ₃ )-(CH ₂ ) _k- N (CH ₃ )-,-( _{OC 2} H ₄ ) _m- O-, -O _{-CH 2 -C (CF 3) 2} -CH 2 -O -, - O-CO- (CH 2) m -CO-O -, - CO-O- (CH 2) m -O-CO -, - _{(CH 2) m -NH- (CH} 2) m -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH -, - CO -C ₃ H _6- (NH-C ₃ H ₆ ) _n- CO-, or -S- (CH ₂ ) _m -S-, m is an integer of 1 to 12 independently, and k is 1. It is an integer of ~ 5, and n is 1 or 2. In equation (DI-4), s is an independently integer of 0-2.

In formula (DI-5), G ³³ is a single bond, -NH-, -NCH _3- , -O-, -S-, -S-S-, -SO _{2-, -CO-, -COO-,} -CONCH _3- , -CONH-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m- O-, -N ( CH ₃ )-(CH ₂ ) _k- N (CH ₃ )-,-( _{OC 2} H ₄ ) _m -O-, -O-CH _2- C (CF ₃ ) _2- CH _{2-O-, -O-CO- (CH 2) m} -CO-O -, - CO-O- (CH 2) m -O-CO -, - (CH 2) m -NH- (CH 2) m -, - CO _{- (CH 2) k -NH- (} CH 2) k -, - (NH- (CH 2) m) k -NH -, - CO-C 3 H 6 - (NH-C 3 H 6) n -CO -, -S- (CH ₂ ) _m -S-, -N (Boc)-(CH ₂ ) _e- N (Boc)-, -NH- (CH ₂ ) _e- N (Boc)-, -N (Boc)-(CH ₂ ) _e -,-(CH ₂ ) _m- N (Boc) -CONH- (CH ₂ ) _m -,-(CH ₂ ) _m- N (Boc)-(CH ₂ ) _m- , Is a group represented by the following formula (DI-5a) or the following formula (DI-5b), m is an integer of 1 to 12 independently, and k is an integer of 1 to 5. , E is an integer of 2-10 and n is 1 or 2. Boc is a t-butoxycarbonyl group.

In formulas (DI-6) and (DI-7), G ²² is independently single-bonded, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF _3). ) _2- or an alkylene group having 1 to 10 carbon atoms.

At least one hydrogen atom of the cyclohexane ring and the benzene ring in the formulas (DI-2) to (DI-7) is -F, -Cl, an alkylene group having 1 to 3 carbon atoms, -OCH ₃ , -OH, It may be substituted with -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl group, or benzyl group, and in addition, in the formula (DI-4), at least of the cyclohexane ring and the benzene ring. One hydrogen atom may be substituted with one selected from the group of groups represented by any of the following formulas (DI-4-a) to (DI-4-i), and one hydrogen atom may be substituted with one selected from the group represented by the formula (DI-). In 5), when G ³³ is a single bond, at least one hydrogen atom of the cyclohexane ring and the benzene ring may be replaced with _{NHBoc or N (Boc) 2.}

式（ＤＩ−４−ａ）および式（ＤＩ−４−ｂ）において、Ｒ^２０は独立して水素原子または−ＣＨ_３である。式（ＤＩ−４−ｆ）および式（ＤＩ−４−ｇ）において、ｍはそれぞれ独立して０〜１２の整数であり、Ｂｏｃはｔ−ブトキシカルボニル基である。 A group whose bond position is not fixed to the carbon atom constituting the ring indicates that the bond position in the ring is arbitrary. The bond position _{of -NH 2} to the cyclohexane ring or the benzene ring is any position except the bond position of ^{G 21} , G ²² or G ^33.

In formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently a hydrogen atom or -CH ₃ . In formulas (DI-4-f) and formula (DI-4-g), m is an independently integer from 0 to 12, and Boc is a t-butoxycarbonyl group.

式（ＤＩ−５−ａ）において、ｑはそれぞれ独立して０〜６の整数である。Ｒ^４４は水素原子、−ＯＨ、炭素数１〜６のアルキル基、または炭素数１〜６のアルコキシ基である。

In the formula (DI-5a), q is an integer of 0 to 6 independently. R ⁴⁴ is a hydrogen atom, −OH, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

式（ＤＩ−１１）において、ｒは０または１である。式（ＤＩ−８）〜式（ＤＩ−１１）において、環に結合する−ＮＨ_２の結合位置は、任意の位置である。

In formula (DI-11), r is 0 or 1. In the formulas (DI-8) to (DI-11), _{the binding position of −NH 2} to be bonded to the ring is an arbitrary position.

式（ＤＩ−１２）において、Ｒ^２１およびＲ^２２は、それぞれ独立して炭素数１〜３のアルキル基またはフェニル基であり、Ｇ^２３は独立して炭素数１〜６のアルキレン基、フェニレン基またはアルキル基で置換されたフェニレン基であり、ｗは１〜１０の整数である。
式（ＤＩ−１３）において、Ｒ^２３は独立して炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基または−Ｃｌであり、ｐは独立して０〜３の整数であり、ｑは０〜４の整数である。
式（ＤＩ−１４）において、環Ｂは単環の複素環式芳香族基であり、Ｒ^２４は水素原子、−Ｆ、−Ｃｌ、炭素数１〜６のアルキル基、アルコキシ基、アルケニル基、アルキニル基であり、ｑは独立して０〜４の整数である。ｑが２以上であるとき、複数のＲ^２４は互いに同一であっても異なっていてもよい。式（ＤＩ−１５）において、環Ｃは複素環式芳香族基または複素環式脂肪族基である。式（ＤＩ−１６）において、Ｇ^２４は単結合、炭素数２〜６のアルキレン基または１，４−フェニレン基であり、ｒは０または１である。そして、環を構成する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す。式（ＤＩ−１３）〜式（ＤＩ−１６）において、環に結合する−ＮＨ_２の結合位置は、任意の位置である。

In the formula (DI-12), R ²¹ and R ²² are independently alkyl groups or phenyl groups having 1 to 3 carbon atoms, respectively, and G ²³ is independently an alkylene group having 1 to 6 carbon atoms and a phenylene group. Alternatively, it is a phenylene group substituted with an alkyl group, and w is an integer of 1 to 10.
In formula (DI-13), R ²³ is independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or −Cl, and p is independently an integer of 0 to 3. q is an integer from 0 to 4.
In the formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, and R ²⁴ is a hydrogen atom, −F, −Cl, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, an alkenyl group, and the like. It is an alkynyl group, and q is an independently integer from 0 to 4. When q is 2 or more, the plurality of R ^24s may be the same or different from each other. In formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In formula (DI-16), G ²⁴ is a single bond, an alkylene group having 2 to 6 carbon atoms or a 1,4-phenylene group, and r is 0 or 1. A group whose bond position is not fixed to the carbon atom constituting the ring indicates that the bond position in the ring is arbitrary. In the formulas (DI-13) to (DI-16), _{the binding position of -NH 2} to be bonded to the ring is an arbitrary position.

式（ＤＩ−１−７）および式（ＤＩ−１−８）において、ｋはそれぞれ独立して、１〜３の整数である。式（ＤＩ−１−９）において、ｖはそれぞれ独立して１〜６の整数である。 Examples of diamines represented by the formula (DI-1) are shown in the following formulas (DI-1-1) to (DI-1-9).

In the formula (DI-1-7) and the formula (DI-1-8), k is an integer of 1 to 3 independently. In the formula (DI-1-9), v is an integer of 1 to 6 independently.

Examples of diamines represented by the formulas (DI-2) to (DI-3) are the following formulas (DI-2-1), formulas (DI-2-2), formulas (DI-3-1) to It is shown in the formula (DI-3-3).

式（ＤＩ−４−２０）および（ＤＩ−４−２１）において、ｍはそれぞれ独立して１〜１２の整数である。

Examples of diamines represented by the formula (DI-4) are shown in the following formulas (DI-4-1) to (DI-4-27).

In equations (DI-4-20) and (DI-4-21), m is an independent integer of 1-12, respectively.

式（ＤＩ−５−１）において、ｍは１〜１２の整数である。 Examples of the diamine represented by the formula (DI-5) are shown in the following formulas (DI-5-1) to (DI-5-50).

In equation (DI-5-1), m is an integer of 1-12.

式（ＤＩ−５−１２）および式（ＤＩ−５−１３）において、ｍはそれぞれ独立して１〜１２の整数である。

In equations (DI-5-12) and (DI-5-13), m is an independent integer of 1-12, respectively.

式（ＤＩ−５−１６）において、ｖは１〜６の整数である。

In equation (DI-5-16), v is an integer of 1-6.

式（ＤＩ−５−３０）において、ｋは１〜５の整数である。

In formula (DI-5-30), k is an integer of 1-5.

式（ＤＩ−５−３５）〜式（ＤＩ−５−３７）、および式（ＤＩ−５−３９）において、ｍはそれぞれ独立して１〜１２の整数であり、式（ＤＩ−５−３８）および式（ＤＩ−５−３９）において、ｋはそれぞれ独立して１〜５の整数であり、式（ＤＩ−５−４０）において、ｎは１または２の整数である。

In formulas (DI-5-35) to (DI-5-37) and formula (DI-5-39), m is an integer of 1 to 12 independently, and formula (DI-5-38). ) And formula (DI-5-39), k is an integer of 1 to 5, respectively, and in formula (DI-5-40), n is an integer of 1 or 2.

式（ＤＩ−５−４２）〜式（ＤＩ−５−４４）において、ｅはそれぞれ独立して２〜１０の整数であり、式（ＤＩ−５−４５）においてＲ^４３は水素原子、−ＮＨＢｏｃ、または−Ｎ（Ｂｏｃ）_２である。式（ＤＩ−５−４２）〜式（ＤＩ−５−４４）において、Ｂｏｃはｔ−ブトキシカルボニル基である。

In the formulas (DI-5-42) to (DI-5-44), e is an integer of 2 to 10 independently, and in the formula (DI-5-45), R ⁴³ is a hydrogen atom, -NHBoc. , Or -N (Boc) ₂ . In formulas (DI-5-42) to (DI-5-44), Boc is a t-butoxycarbonyl group.

Examples of the diamine represented by the formula (DI-6) are shown in the following formulas (DI-6-1) to (DI-6-7).

式（ＤＩ−７−３）および式（ＤＩ−７−４）において、ｍはそれぞれ独立して１〜１２の整数であり、ｎは独立して１または２である。 Examples of the diamine represented by the formula (DI-7) are shown in the following formulas (DI-7-1) to (DI-7-11).

In the formulas (DI-7-3) and (DI-7-4), m is an integer of 1 to 12 independently, and n is 1 or 2 independently.

Examples of diamines represented by the formula (DI-8) are shown in the following formulas (DI-8-1) to (DI-8-4).

Examples of diamines represented by the formula (DI-9) are shown in the following formulas (DI-9-1) to (DI-9-3).

Examples of the diamine represented by the formula (DI-10) are shown in the following formulas (DI-10-1) and (DI-10-2).

Examples of diamines represented by the formula (DI-11) are shown in the following formulas (DI-11-1) to (DI-11-3).

An example of the diamine represented by the formula (DI-12) is shown in the following formula (DI-12-1).

Examples of the diamine represented by the formula (DI-13) are shown in the following formulas (DI-13-1) to (DI-13-13).

Examples of the diamine represented by the formula (DI-14) are shown in the following formulas (DI-14-1) to (DI-14-9).

Examples of the diamine represented by the formula (DI-15) are shown in the following formulas (DI-15-1) to (DI-5-12).

An example of the diamine represented by the formula (DI-16) is shown in the following formula (DI-16-1).

式（ＤＩＨ−１）において、Ｇ^２５は単結合、炭素数１〜２０のアルキレン基、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。
式（ＤＩＨ−２）において、環Ｄはシクロヘキサン環、ベンゼン環またはナフタレン環であり、この基の少なくとも１つの水素原子はメチル基、エチル基、またはフェニル基で置換されてもよい。式（ＤＩＨ−３）において、環Ｅはそれぞれ独立してシクロヘキサン環、またはベンゼン環であり、この基の少なくとも１つの水素原子はメチル基、エチル基、またはフェニル基で置換されてもよい。複数の環Ｅは互いに同一であっても異なっていてもよい。Ｙは単結合、炭素数１〜２０のアルキレン、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、または−Ｃ（ＣＦ_３）_２−である。式（ＤＩＨ−２）および式（ＤＩＨ−３）において、環に結合する−ＣＯＮＨＮＨ_２の結合位置は、任意の位置である。 Next, dihydrazide used as a raw material for the polymer of the present invention will be described. Examples of the dihydrazide having no known side chain include compounds represented by any of the following formulas (DIH-1) to (DIH-3).

In formula (DIH-1), G ²⁵ is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or. -C (CF ₃ ) _2- .
In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen atom of this group may be substituted with a methyl group, an ethyl group or a phenyl group. In the formula (DIH-3), the ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen atom of this group may be substituted with a methyl group, an ethyl group, or a phenyl group. The plurality of rings E may be the same as or different from each other. Y is a single bond, alkylene with 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO _2- , -C (CH ₃ ) _2- , or -C (CF ₃ ) _2-. .. In the formula (DIH-2) and the formula (DIH-3), _{the binding position of −CONHNH 2} bonded to the ring is an arbitrary position.

式（ＤＩＨ−１−２）において、ｍは１〜１２の整数である。 Examples of compounds represented by any of the formulas (DIH-1) to (DIH-3) are the following formulas (DIH-1-1), formulas (DIH-1-2), formulas (DIH-2-1). )-Formula (DIH-2-3), formula (DIH-3-1) to formula (DIH-3-6).

In the formula (DIH-1-2), m is an integer of 1-12.

A diamine suitable for the purpose of increasing the pretilt angle will be described. The compound of the present invention can be suitably used as a liquid crystal alignment agent used in a transverse electric field type liquid crystal display element, but it is also possible to increase the pretilt angle by using it in combination with the following diamines. Examples of diamines having side chain groups suitable for increasing the pretilt angle include formulas (DI-31) to (DI-35) and formulas (DI-36-1) to formulas (DI-36-8). ) Can be mentioned.

In formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH _2- , -CF ₂ O-. , -OCF _2- , or-(CH ₂ ) _ma- , where ma is an integer of 1-12. Preferred examples of G ²⁶ are single bonds, -O-, -COO-, -OCO-, -CH ₂ O-, and alkylene groups having 1-3 carbon atoms, with particularly preferred examples being single bonds, -O-,. _{-COO -, - OCO -, -} CH 2 O -, - CH 2 - and _-CH 2 CH ₂ -. R ²⁵ is an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In the alkyl group, at least one hydrogen atom may be replaced by -F, and at least one -CH ₂ - is -O -, - CH = CH- or -C≡C- may be substituted with Good. The hydrogen atom of this phenyl group is -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF _2, -OCF _3, an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. It may be replaced. _{The bond position of -NH 2} bonded to the benzene ring indicates that it is an arbitrary position in the ring, but the bond position is preferably the meta position or the para position. That is, the group "R ^{25 -G} 26 ^-" when the binding position of the 1-position, of the two coupling positions 3 and 5 positions, or preferably 2-position and 5-position.

式（ＤＩ−３１−ａ）において、Ｇ^２７、Ｇ^２８およびＧ^２９は結合基であり、これらは、それぞれ独立して単結合、または炭素数１〜１２のアルキレン基であり、このアルキレン基の１以上の−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−で置換されていてもよい。環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４は、それぞれ独立して１，４−フェニレン基、１，４−シクロへキシレン基、１，３−ジオキサン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ピリジン−２，５−ジイル基、ナフタレン−１，５−ジイル基、ナフタレン−２，７−ジイル基またはアントラセン−９，１０−ジイル基であり、環Ｂ^２１、環Ｂ^２２、環Ｂ^２３および環Ｂ^２４において、少なくとも１つの水素原子は−Ｆまたは−ＣＨ_３で置換されてもよく、ｓ、ｔ、およびｕは、それぞれ独立して０〜２の整数であって、これらの合計は１〜５であり、ｓ、ｔ、またはｕが２であるとき、各々の括弧内の２つの結合基は同じであっても異なってもよく、そして、２つの環は同じであっても異なっていてもよい。Ｒ^２６は水素原子、−Ｆ、−ＯＨ、炭素数１〜３０のアルキル基、炭素数１〜３０のフッ素置換アルキル基、炭素数１〜３０のアルコキシ基、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２、または−ＯＣＦ_３であり、この炭素数１〜３０のアルキル基の少なくとも１つの−ＣＨ_２−は下記式（ＤＩ−３１−ｂ）で表される２価の基で置換されていてもよい。

式（ＤＩ−３１−ｂ）において、Ｒ^２７およびＲ^２８は、それぞれ独立して炭素数１〜３のアルキル基であり、ｖは１〜６の整数である。Ｒ^２６の好ましい例は炭素数１〜３０のアルキル基および炭素数１〜３０のアルコキシ基である。

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are bonding groups, which are independently single bonds or alkylene groups having 1 to 12 carbon atoms, respectively. One or more −CH ₂₋ may be substituted with −O−, −COO−, −OCO−, −CONH−, −CH = CH−. Ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,3-dioxane-2,5-diyl group, respectively. Pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, naphthalene-1,5-diyl group, naphthalene-2,7-diyl group or anthracene-9,10-diyl group, ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ , at least one hydrogen atom may _{be substituted with -F or -CH 3} , where s, t, and u are independently integers of 0-2. And the sum of these is 1-5, and when s, t, or u is 2, the two linking groups in each parenthesis may be the same or different, and the two. The rings may be the same or different. R ²⁶ is a hydrogen atom, -F, -OH, alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, - It is OCHF ₂ or −OCF _{3 , and at least one −CH 2} − of the alkyl group having 1 to 30 carbon atoms is substituted with a divalent group represented by the following formula (DI-31-b). May be good.

In the formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl groups having 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferred examples of R ²⁶ are an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.

式（ＤＩ−３２）および式（ＤＩ−３３）において、Ｇ^３０は独立して単結合、−ＣＯ−または−ＣＨ_２−であり、Ｒ^２９は独立して水素原子または−ＣＨ_３であり、Ｒ^３０は独立して水素原子、炭素数１〜２０のアルキル基、または炭素数２〜２０のアルケニル基である。式（ＤＩ−３３）におけるベンゼン環の少なくとも１つの水素原子は、炭素数１〜２０のアルキル基またはフェニル基で置換されてもよい。そして、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す。式（ＤＩ−３２）における２つの基「−フェニレン−Ｇ^３０−Ｏ−」の一方はステロイド核の３位に結合し、もう一方はステロイド核の６位に結合していることが好ましい。式（ＤＩ−３３）における２つの基「−フェニレン−Ｇ^３０−Ｏ−」のベンゼン環への結合位置は、ステロイド核の結合位置に対して、それぞれメタ位またはパラ位であることが好ましい。式（ＤＩ−３２）および式（ＤＩ−３３）において、ベンゼン環に結合する−ＮＨ_２はその環における結合位置が任意であることを示す。

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH _2- , and R ²⁹ is independently a hydrogen atom or -CH ₃ . R ³⁰ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. At least one hydrogen atom of the benzene ring in the formula (DI-33) may be substituted with an alkyl group or a phenyl group having 1 to 20 carbon atoms. Then, a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary. It is preferable that one of the two groups "-phenylene-G ^30- O-" in the formula (DI-32) is bound to the 3-position of the steroid nucleus and the other is bound to the 6-position of the steroid nucleus. The binding positions of the two groups "-phenylene-G ^30- O-" in the formula (DI-33) to the benzene ring are preferably meta-positions or para-positions, respectively, with respect to the binding position of the steroid nucleus. In formulas (DI-32) and (DI-33), -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

式（ＤＩ−３４）および式（ＤＩ−３５）において、Ｇ^３１は独立して−Ｏ−または炭素数１〜６のアルキレン基であり、Ｇ^３２は単結合または炭素数１〜３のアルキレン基である。Ｒ^３１は水素原子または炭素数１〜２０のアルキル基であり、このアルキル基の少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。Ｒ^３２は炭素数６〜２２のアルキル基であり、Ｒ^３３は水素原子または炭素数１〜２２のアルキル基である。環Ｂ^２５は１，４−フェニレン基または１，４−シクロヘキシレン基であり、ｒは０または１である。そしてベンゼン環に結合する−ＮＨ_２はその環における結合位置が任意であることを示すが、独立してＧ^３１の結合位置に対してメタ位またはパラ位であることが好ましい。

In formulas (DI-34) and (DI-35), G ³¹ is independently -O- or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms. Is. R ³¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and at least one −CH ₂ − of this alkyl group may be replaced with −O−, −CH = CH− or −C≡C−. Good. R ³² is an alkyl group having 6 to 22 carbon atoms, and R ³³ is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. Ring B ²⁵ is a 1,4-phenylene group or a 1,4-cyclohexylene group, where r is 0 or 1. _{Then, -NH 2} bonded to the benzene ring indicates that the bonding position in the ring is arbitrary, but it is preferably in the meta position or the para position ^{independently with respect to the bonding position of G 31.}

Examples of the compound represented by the formula (DI-31) are shown in the following formulas (DI-31-1) to (DI-31-55).

In formulas (DI-31-1) to (DI-31-11), R ³⁴ is independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably having 1 to 30 carbon atoms. It is an alkyl group of 5 to 25 or an alkoxy group having 5 to 25 carbon atoms. R ³⁵ is independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

In the formulas (DI-31-12) to (DI-31-17), R ³⁶ is an alkyl group having 4 to 30 carbon atoms independently, preferably an alkyl group having 6 to 25 carbon atoms. Each of R ³⁷ is an alkyl group having 6 to 30 carbon atoms independently, and is preferably an alkyl group having 8 to 25 carbon atoms.

In formulas (DI-31-18) to (DI-31-43), R ³⁸ is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, preferably having 1 to 20 carbon atoms. It is an alkyl group of 3 to 20 or an alkoxy group having 3 to 20 carbon atoms. R ³⁹ is independently a hydrogen atom, -F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , and is preferable. Is an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms. And G ³³ is an alkylene group having 1 to 20 carbon atoms.

Examples of the compound represented by the formula (DI-32) are shown in the following formulas (DI-32-1) to (DI-32-4).

Examples of the compound represented by the formula (DI-33) are shown in the following formulas (DI-33-1) to (DI-33-8).

式（ＤＩ−３４−１）〜式（ＤＩ−３４−１２）において、Ｒ^４０はそれぞれ独立して水素原子または炭素数１〜２０のアルキル基、好ましくは水素原子または炭素数１〜１０のアルキル基であり、そしてＲ^４１はそれぞれ独立して水素原子または炭素数１〜１２のアルキル基である。 Examples of the compound represented by the formula (DI-34) are shown in the following formulas (DI-34-1) to (DI-34-12).

In formulas (DI-34-1) to (DI-34-12), R ⁴⁰ is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl atom having a hydrogen atom or 1 to 10 carbon atoms. It is a group, and ^{each R 41} is an independent hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

式（ＤＩ−３５−１）〜式（ＤＩ−３５−３）において、Ｒ^３７はそれぞれ独立して炭素数６〜３０のアルキル基であり、Ｒ^４１はそれぞれ独立して水素原子または炭素数１〜１２のアルキル基である。 Examples of the compound represented by the formula (DI-35) are shown in the following formulas (DI-35-1) to (DI-35-3).

In formulas (DI-35-1) to (DI-35-3), R ³⁷ is an independently alkyl group having 6 to 30 carbon atoms, and R ⁴¹ is independently a hydrogen atom or 1 carbon atom. ~ 12 alkyl groups.

式（ＤＩ−３６−１）〜式（ＤＩ−３６−８）において、Ｒ^４２はそれぞれ独立して炭素数３〜３０のアルキル基である。 The compounds represented by the formulas (DI-36-1) to (DI-36-8) are shown below.

In formulas (DI-36-1) to (DI-36-8), R ⁴² is an alkyl group having 3 to 30 carbon atoms independently.

Among the above diamines, suitable materials for improving each property of the liquid crystal alignment film described later will be described. When it is important to improve the liquid crystal orientation, the formula (DI-1-3), the formula (DI-5-1), the formula (DI-5-5), the formula (DI-5-9), Equation (DI-5-12), Equation (DI-5-13), Equation (DI-5-29), Equation (DI-6-7), Equation (DI-7-3), or Equation (DI- It is preferable to use the compound represented by 11-2). In the formula (DI-5-1), m = 2 to 8 is preferable, and m = 4 to 8 is more preferable. In the formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable.

When it is important to improve the transmittance, Eq. (DI-1-3), Eq. (DI-2-1), Eq. (DI-5-1), Eq. (DI-5-5), Eq. It is preferable to use the diamine represented by (DI-5-24) or the formula (DI-7-3), and the compound represented by the formula (DI-2-1) is more preferable. In the formula (DI-5-1), m = 2-8 is preferable, and m = 8 is more preferable. In the formula (DI-7-3), m = 2 or 3, n = 1 or 2, is preferable, and m = 3, n = 1 is more preferable.

When it is important to improve the VHR of the liquid crystal display element, the formula (DI-2-1), the formula (DI-4-1), the formula (DI-4-2), and the formula (DI-4-10) ), Equation (DI-4-15), Equation (DI-4-22), Equation (DI-5-1), Equation (DI-5-28), Equation (DI-5-30), or Equation (DI-5-30), or Equation (DI-5-30). It is preferable to use the compound represented by DI-13-1), and the diamine represented by the formula (DI-2-1), the formula (DI-5-1), or the formula (DI-13-1) is used. More preferred. In the formula (DI-5-1), m = 1 is preferable. In the formula (DI-5-30), k = 2 is preferable.

Improving the relaxation rate of the residual charge (residual DC) in the liquid crystal alignment film by reducing the volume resistance value of the liquid crystal alignment film is effective as one of the methods for preventing seizure. When this purpose is emphasized, the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-4-15), the formula (DI-5) -1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-4-20), formula (DI-4-21), formula It is preferable to use the compound represented by (DI-7-12) or the formula (DI-16-1), and the formula (DI-4-1), the formula (DI-5-1), or the formula (DI). The compound represented by -5-13) is more preferable. In the formula (DI-5-1), m = 2 to 8 is preferable, and m = 4 to 8 is more preferable. In the formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In the formula (DI-7-12), m = 3 or 4 is preferable, and m = 4 is more preferable.

[Amount of compound represented by formula (1) in the raw material]
In the raw material composition used as a raw material for the polymer of the present invention, the compound represented by the formula (1) is preferably 40 to 100 mol%, preferably 50 to 100 mol%, based on the total amount of diamines used as the raw material. More preferred.

In the raw material composition used as a raw material for the polymer of the present invention, a part of diamines may be replaced with at least one selected from the group consisting of monoamines and monohydrazides. The replacement ratio is preferably in the range of 40 mol% or less of at least one selected from the group consisting of monoamines and monohydrazides to diamines. Such replacement can cause termination of the polymerization reaction when producing a polyamic acid, and can suppress further progress of the polymerization reaction. Therefore, by such replacement, the molecular weight of the obtained polymer (polyamic acid or a derivative thereof) can be easily controlled, and for example, the coating property of the liquid crystal alignment agent can be improved without impairing the effect of the present invention. Can be done. The diamines which may be replaced with monoamines or monohydrazides may be one kind or two or more kinds as long as the effect of the present invention is not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and n-. Undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, Paraaminophenyltrimethoxysilane and 3-aminopropyltriethoxysilane can be mentioned.

When the polymer of the present invention is a polyamic acid or a derivative thereof, the raw material thereof may further contain a monoisocyanate compound as a monomer. By including the monoisocyanate compound in the monomer, the terminal of the obtained polyamic acid or its derivative is modified and the molecular weight is adjusted. By using this terminal-modified polyamic acid or a derivative thereof, for example, the coating characteristics of the liquid crystal alignment agent can be improved without impairing the effect of the present invention. The content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% with respect to the total amount of the diamine and the tetracarboxylic dianhydride in the monomer from the above viewpoint. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

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す。式（Ｖ−２）において、Ｒ^６はそれぞれ独立して−ＣＨ_３、−ＯＣＨ_３、−ＣＦ_３、−ＣＯＯＣＨ_３であり、ａはそれぞれ独立して０〜２の整数である。式（Ｖ−４）において、Ｒ^１およびＲ^２は、それぞれ独立して、水素、式（Ｐ１−１）または式（Ｐ１−２）で表される基であり、Ｒ^１およびＲ^２の少なくとも１つは、式（Ｐ１−１）または式（Ｐ１−２）で表される基である。式（ＶＩＩ−１）において、Ｒ^４およびＲ^６は、それぞれ独立して炭素数１〜２０の直鎖アルキレン、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＮ（ＣＨ_３）−、または単結合であり、Ｒ^４およびＲ^６において、直鎖アルキレンの−ＣＨ_２−の１つまたは隣接しない２つは−Ｏ−で置き換えられてもよく、Ｒ^５およびＲ^７は、独立して、単環式炭化水素環、縮合多環式炭化水素環、複素環、または単結合である。

式（Ｐ１−１）および式（Ｐ１−２）において、Ｒ^６ａ〜Ｒ^８ａは、それぞれ独立して、水素原子、置換もしくは無置換のアルキル、置換もしくは無置換のアルカノイル、置換もしくは無置換のアルコキシカルボニル、または置換もしくは無置換のアリールカルボニルである。Ｒ^６ａ〜Ｒ^８ａは互いに同一であっても異なっていてもよい。＊は、式（Ｖ−４）におけるベンゼン環への結合位置を表す。 A photosensitive monomer other than the photosensitive monomer of the present invention can be used in combination as long as the effect of the present invention is not impaired. Examples of photosensitive monomers that can be used in combination are shown below, but the present invention is not limited thereto.

In each of the above equations, a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary. In the formula (V-2), R ⁶ is independently -CH ₃ , -OCH ₃ , -CF ₃ , and -COOCH ₃ , and a is an integer of 0 to 2 independently. In formula (V-4), R ¹ and R ² are independently represented by hydrogen, formula (P1-1) or formula (P1-2), and are at least ^{R 1} and R ^2. One is a group represented by the formula (P1-1) or the formula (P1-2). In the formula (VII-1), ^{R 4} and ^{R 6} are each independently a straight-chain alkylene having 1 to 20 carbon atoms, -COO -, - OCO -, - NHCO -, - CONH -, - N (CH 3 ) CO-, -CON (CH ₃ )-, or single bond, and in R ⁴ and R ⁶ , one or two non-adjacent linear alkylene -CH _{2- can be replaced with -O-.} Often, R ⁵ and R ⁷ are independently monocyclic hydrocarbon rings, fused polycyclic hydrocarbon rings, heterocycles, or single bonds.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a independently represent a hydrogen atom, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkanoyl, and a substituted or unsubstituted alkoxy. It is a carbonyl, or a substituted or unsubstituted arylcarbonyl. R ^{6a to} R ^8a may be the same or different from each other. * Represents the bond position to the benzene ring in the formula (V-4).

When the transparency of the alignment film of the present invention is emphasized, it is preferable to use it in combination with the photosensitive monomer represented by the formula (V-4). More preferable examples of the photosensitive monomer represented by the formula (V-4) include the formula (V-4-1) and the formula (V-4-2).

<Liquid crystal alignment agent>
Hereinafter, the polymer-based liquid crystal alignment agent of the present invention will be described in detail.
The liquid crystal aligning agent of the present invention may be composed of one kind of the polymer of the present invention, or may be a mixture of the polymer of the present invention and a polymer other than the present invention. In the present specification, the liquid crystal alignment agent composed of one kind of the above polymer may be referred to as a single-layer liquid crystal alignment agent. A liquid crystal alignment agent in which two or more of the above polymers are mixed may be referred to as a blended liquid crystal alignment agent. Blended liquid crystal alignment agents are used especially when VHR reliability and other electrical properties are important.

As the polymer other than the present invention used for the blended liquid crystal alignment agent, any one or more of a polyamic acid and a polyamic acid derivative is preferable. As the polymer other than the present invention, with respect to the polyamic acid and the polyamic acid derivative, the above description of the polymer of the present invention can be referred to except that the compound represented by the formula (1) is not contained as a raw material.

When using a two-component polymer, for example, select a polymer having excellent performance in liquid crystal alignment ability on one side, and select a polymer having excellent performance in improving the electrical characteristics of the liquid crystal display element on the other side. It is suitable for obtaining an orienting agent having a good balance between liquid crystal orientation and electrical characteristics.

In this case, by controlling the structure and molecular weight of each polymer, a liquid crystal aligning agent in which these polymers are dissolved in a solvent is applied to a substrate and pre-dried to form a thin film, as described later. A polymer having excellent performance in liquid crystal alignment ability can be segregated in the upper layer of the thin film, and a polymer having excellent performance in improving the electrical characteristics of the liquid crystal display element can be segregated in the lower layer of the thin film. For this, a phenomenon in which 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 can be applied to a mixed polymer. The confirmation of such layer separation is that the surface energy of the formed liquid crystal alignment film is equal to or close to the surface energy of the film formed by the liquid crystal alignment agent containing only the polymer intended to segregate in the upper layer. It can be confirmed by the value.

As a method for expressing layer separation, it is also possible to reduce the molecular weight of the polymer to be segregated in the upper layer.

In a liquid crystal alignment agent composed of a mixture of polymers, layer separation can be exhibited by using polyimide as the polymer to be segregated in the upper layer.

The compound represented by the formula (1) may be used as a raw material monomer of a polymer segregating in the upper layer of the thin film, may be used as a raw material monomer of a polymer segregating in the lower layer of the thin film, or may be used as a raw material monomer of a polymer segregating in the lower layer of the thin film. Although it may be used as a raw material monomer, it is more preferable to use it as a raw material monomer for a polymer that segregates on the upper layer of a thin film.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or a derivative thereof that segregates on the upper layer of the thin film can be selected without limitation from the known tetracarboxylic dianhydrides exemplified above. it can.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative that segregates on the upper layer of the thin film is the formula (AN-1-1), the formula (AN-1-2), and the formula (AN-2-). The compound represented by 1), the formula (AN-3-1), the formula (AN-4-5), the formula (AN-4-17), or the formula (AN-4-21) is preferable, and the compound represented by the formula (AN-4-21) is preferable. AN-4-17) or formula (AN-4-21) is more preferred. In the formula (AN-4-17), m = 4 to 8 is preferable.

The diamines other than the compound represented by the formula (1) used for synthesizing the polyamic acid or its derivative segregating on the upper layer of the thin film are selected from the known diamines exemplified above without limitation. be able to.

Examples of diamines used for synthesizing a polyamic acid or a derivative thereof that segregates on the upper layer of a thin film include formulas (DI-4-1), formulas (DI-4-13), and formulas (DI-4-15). It is preferable to use a compound represented by the formula (DI-5-1), the formula (DI-7-3), or the formula (DI-13-1). Of these, it is more preferable to use a compound represented by the formula (DI-4-13), the formula (DI-4-15), the formula (DI-5-1), or the formula (DI-13-1). In the formula (DI-5-1), m = 4 to 8 is preferable. In the formula (DI-7-3), m = 3 and n = 1 are preferable.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative segregating in the lower layer of the thin film can be selected without limitation from the known tetracarboxylic dianhydrides exemplified above. ..

Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative segregating in the lower layer of the thin film include the formula (AN-1-1), the formula (AN-1-13), and the formula (AN-2). -1), the compound represented by the formula (AN-3-2), or the formula (AN-4-21) is preferable, and the formula (AN-1-1), the formula (AN-2-1), or the formula is preferable. (AN-3-2) is more preferable.

The tetracarboxylic dianhydride used for synthesizing the polyamic acid or its derivative segregating in the lower layer of the thin film shall contain 10 mol% or more of the aromatic tetracarboxylic dianhydride in the total amount of the tetracarboxylic dianhydride. Is preferable, and it is more preferable to contain 30 mol% or more.

The diamines other than the compound represented by the formula (1) used for synthesizing the polyamic acid or its derivative segregating in the lower layer of the thin film are selected from the known diamines exemplified above without limitation. be able to.

Examples of the diamines used for synthesizing the polyamic acid or its derivative segregating in the lower layer of the thin film include the formula (DI-4-1), the formula (DI-4-2), and the formula (DI-4-10). Equation (DI-4-18), Equation (DI-4-19), Equation (DI-5-1), Equation (DI-5-9), Equation (DI-5-28), Equation (DI-5) -30), the compound represented by the formula (DI-13-1), or the formula (DIH-1-2) is preferable. In the formula (DI-5-1), a compound having m = 1 or 2 is preferable, and in the formula (DI-5-30), a compound having k = 2 is preferable. Among them, the formula (DI-4-1), the formula (DI-4-18), the formula (DI-4-19), the formula (DI-5-9), the formula (DI-13-1), or the formula ( The compound represented by DIH-1-2) is more preferable.

The diamines used for synthesizing the polyamic acid or its derivative that segregates in the lower layer of the thin film are at least one selected from the group consisting of aromatic diamines and aromatic dihydrazides, and 30 mol with respect to all diamines. It is preferably contained in an amount of% or more, and more preferably contained in an amount of 50 mol% or more.

The ratio of the polyamic acid or its derivative segregated in the upper layer of the thin film to the total amount of the polyamic acid or its derivative segregated in the upper layer of the thin film and the polyamic acid or its derivative segregated in the lower layer of the thin film is 5% by weight to 50% by weight. % Is preferable, and 10% by weight to 40% by weight is more preferable.

The polyamic acid of the present invention or a derivative thereof may be a block polymer containing a first polymer chain and a second polymer chain having a structure different from that of the first polymer chain. Further, the block polymer may further contain other polymer chains having a structure different from that of the first polymer chain and the second polymer chain. For example, a block polymer of polyamic acid, a solution of formula (PAA) specific polyamic acid represented by (PAA1), a solution of polyamic acid (PAA1) and ^{X 1} and ^X combinations of ^two different polyamic acid (PAA2) It can be formed by mixing and heating. The polyamic acid block polymer thus formed includes _{a block represented by (PAA1) n1} and a block represented by (PAA2) _n2 . _{(PAA1) n1} and _{(PAA2) n2} in n1 and n2 are each independently an integer of 1 or more, preferably each independently an integer of 2 or more. In the block polymer, the polymer chains using the compound represented by the formula (1) in the raw material composition may be any one, two or more, or all polymer chains. You may.

Here, the polyamic acid block polymer may be synthesized by mixing two or more kinds of polyamic acids independently and then mixing them and heating them, or after synthesizing two or more kinds of polyamic acids in the same reaction vessel. , May be heated and synthesized.

Further, the liquid crystal alignment agent of the present invention may further contain a solvent from the viewpoint of the coatability of the liquid crystal alignment agent and the adjustment of the concentration of the polyamic acid or its derivative. The solvent can be applied without any particular limitation as long as it is a solvent having an ability to dissolve a polymer component. The solvent includes a wide range of solvents usually used in the manufacturing process and application of polymer components such as polyamic acid and soluble polyimide, and can be appropriately selected depending on the purpose of use. The solvent may be one kind or a mixed solvent of two or more kinds.

Examples of the solvent include a parent solvent of 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 a derivative thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, and N-methylpropion. Examples thereof include amide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, N, N-dimethylisobutylamide, γ-butyrolactone, and γ-valerolactone. ..
Of these, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, or γ-valerolactone is preferable.

Examples of other solvents for the purpose of improving coatability include ethylene glycol monobutyl ether such as ethylene glycol monobutyl ether and ethylene glycol monoternary butyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, and diethylene glycol ethyl methyl ether. , Diethylene glycol dialkyl ether, diethylene glycol butyl methyl ether and the like. In addition, propylene glycol monomethyl ether, propylene glycol monoalkyl ether such as 1-butoxy-2-propanol, dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, triethylene glycol monoalkyl ether, butyl cellosolve acetate, phenyl acetate, and Examples thereof include ester compounds such as these acetates. Further, examples thereof include dialkyl malonate such as diethyl malonate, alkyl lactate, diisobutyl ketone, diacetone alcohol, 3-methyl-3-methoxybutanol, 4-methyl-2-pentanol, diisobutylcarbinol, tetraline, and isophorone.

Among these, diisobutylketone, 4-methyl-2-pentanol, diisobutylcarbinol, ethylene glycol monobutyl ether, ethylene glycol monotersial butyl ether, diethylene glycol monoethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether, diethylene glycol butylmethyl Ether, 1-butoxy-2-propanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, or butyl cellosolve acetate are preferred.

The solid content concentration in the liquid crystal alignment agent of the present invention is not particularly limited, and the optimum value may be selected according to the various coating methods described below. Usually, it is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the weight of the varnish in order to suppress unevenness and pinholes during coating.

The viscosity of the liquid crystal aligning agent of the present invention varies in a preferable range depending on the method of application, the concentration of the polyamic acid or its derivative, the type of the polyamic acid or its derivative used, and the type and ratio of the solvent. For example, in the case of coating by a printing machine, it is 5 to 100 mPa · s (more preferably 10 to 80 mPa · s). If it is 5 mPa · s or more, it becomes easy to obtain a sufficient film thickness, and if it is 100 mPa · s or less, it becomes easy to suppress printing unevenness. In the case of application by spin coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable. When coating using an inkjet coating device, 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, for example, a rotational viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25 ° C.).

The liquid crystal alignment agent of the present invention may further contain various additives. Various additives can be selected and used according to their respective purposes in order to improve various properties of the alignment film. An example is shown below.

<Alkenyl-substituted nadiimide compound>
For example, the liquid crystal alignment 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 for a long period of time. The alkenyl-substituted nadiimide compound may be used alone or in combination of two or more. For the above purpose, the content of the alkenyl-substituted nadiimide compound is preferably 1 to 50% by weight, more preferably 1 to 30% by weight, and 1 to 20% by weight with respect to the polyamic acid or its derivative. Is more preferable. The alkenyl-substituted nadiimide compound is preferably a compound that can be dissolved in a solvent that dissolves the polyamic acid or its derivative used in the present invention. Preferred alkenyl-substituted nadiimide compounds include alkenyl-substituted nadiimide compounds disclosed in JP-A-2008-096979, JP-A-2009-109987, and JP-A-2013-242526. Particularly preferred alkenyl-substituted nadiimide compounds include bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, N, N'-m-xylylene-. Bis (allylbicyclo [2.2.1] hept-5-en-2,3-dicarboxyimide) or N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hept-5- En-2,3-dicarboxyimide).

<Compound with radically polymerizable unsaturated double bond>
For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radically 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 kind of compound or two or more kinds of compounds. The compound having a radically polymerizable unsaturated double bond does not include an alkenyl-substituted nadiimide compound. Compounds having a radically polymerizable unsaturated double bond are preferably N, N'-methylenebisacrylamide, N, N'-dihydroxyethylene-bisacrylamide, ethylenebis acrylate, and 4,4'-methylenebis (N). , N-dihydroxyethylene acrylate aniline), triallyl cyanurate, and radical polymerization disclosed in JP-A-2009-109987, JP-A-2013-242526, International Publication No. 2014/119682, International Publication No. 2015/152014. Examples include compounds having sex unsaturated double bonds. For the above purpose, the content of the compound having a radically polymerizable unsaturated double bond is preferably 1 to 50% by weight, more preferably 1 to 30% by weight, based on the polyamic acid or its derivative. preferable.

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

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 polymerizable property is preferable. Preferred oxazine compounds include oxazine compounds represented by the formulas (OX-3-1), formulas (OX-3-9), and formulas (OX-3-10), and Japanese Patent Application Laid-Open No. 2007-286597. Examples thereof include oxazine compounds disclosed in JP2013-242526A.

<Oxazoline compound>
For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electrical characteristics of the 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 kind of compound or two or more kinds of compounds. For the above purpose, the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and 1 to 20% by weight with respect to the polyamic acid or its derivative. Is more preferable. Preferred oxazoline compounds include oxazoline compounds disclosed in JP-A-2010-054872 and JP-A-2013-242526. More preferably, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene can be mentioned.

<Epoxy compound>
For example, the liquid crystal alignment agent of the present invention further contains an epoxy compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time, improving the hardness of the film, or improving the adhesion with the sealant. You may be. The epoxy compound may be one kind of compound or two or more kinds of compounds. For the above purpose, the content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight, and 1 to 10% by weight with respect to the polyamic acid or its derivative. Is more preferable.

As the epoxy compound, various compounds having one or more epoxy rings in the molecule can be used.
For the purpose of improving the hardness of the film or improving the adhesion to the sealant, a compound having two or more epoxy rings in the molecule is preferable, and a compound having three or four epoxy rings is more preferable.

Examples of the epoxy compound include epoxy compounds disclosed in JP-A-2009-175715, JP-A-2013-242526, JP-A-2016-170409, and International Publication No. 2017/217413. Preferred epoxy compounds include N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (3,3', 4,4'-diepoxy) bicyclohexyl, 1,4-butanediol glycidyl ether, tris isocyanurate (2,3-) Epoxypropyl), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, or N, N, N', N'-tetraglycidyl-m-xylene diamine.
In addition to the above, oligomers and polymers having an epoxy ring can also be added. As the oligomer or polymer having an epoxy ring, the oligomer or polymer disclosed in JP2013-242526A can be used.

<Silane compound>
For example, the liquid crystal alignment agent of the present invention may further contain a silane compound for the purpose of improving the adhesion between the substrate and the sealant. For the above purpose, the content of the silane compound is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, more preferably 0.5, based on the polyamic acid or its derivative. It is more preferably from 10% by weight.

As the silane coupling agent, the silane coupling agents disclosed in JP2013-242526, JP2015-212807, JP2018-173545, and International Publication 2018/181566 can be used.
Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, paraaminophenyltrimethoxysilane, 3-. Aminopropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-isocyanatepropyltriethoxysilane, or 3-ureidopropyltriethoxysilane can be mentioned.

In addition to the above-mentioned additives, a compound having a cyclocarbonate group, a compound having a hydroxyalkylamide moiety or a hydroxyl group is added for the purpose of increasing the strength of the alignment film or stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. You can also do it. Specific examples of the compound include compounds disclosed in Japanese Patent Application Laid-Open No. 2016-118753 and International Publication No. 2017/110976. Preferred compounds include the following formulas (HD-1) to (HD-4). These compounds are preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight, still more preferably 1 to 10% by weight, based on the polyamic acid or its derivative.

Further, when it is necessary to improve the antistatic property, an antistatic agent can be used, and when the imidization proceeds at a low temperature, an imidization catalyst can be used. Examples of the imidization catalyst include imidization catalysts disclosed in Japanese Patent Application Laid-Open No. 2013-242526.

<Liquid crystal alignment film>
Next, the liquid crystal alignment film of the present invention will be described.
The liquid crystal alignment film of the present invention is formed by using the liquid crystal alignment agent of the present invention. When heated and fired in the process of forming a liquid crystal alignment film using the liquid crystal alignment agent of the present invention, an imidization reaction can occur to form a polyimide-based liquid crystal alignment film. The liquid crystal alignment agent of the present invention is suitable as a liquid crystal alignment agent for photoalignment, and the photoalignment method can be applied to the alignment treatment in the process of forming the liquid crystal alignment film.

Hereinafter, a method for forming a liquid crystal alignment film using the liquid crystal alignment agent for photoalignment of the present invention will be described.

The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent for photoalignment. The liquid crystal alignment film of the present invention is, for example, a step of forming a coating film of the liquid crystal alignment agent for photoalignment of the present invention, a step of heating and drying the coating film to form a film of the liquid crystal alignment agent, and a liquid crystal alignment agent. It can be obtained by going through a step of irradiating the film with light to impart anisotropy and a step of heating and firing the film of the liquid crystal aligning agent to which the anisotropy is imparted. It is preferable that the liquid crystal alignment film of the present invention is irradiated with light after the coating film step and the heat drying step to impart anisotropy, and then undergoes the heating and firing step.

The coating film can be formed by applying the liquid crystal alignment agent of the present invention to the substrate of the liquid crystal display element in the same manner as in the production of a normal liquid crystal alignment film. The substrate may be provided with electrodes such as ITO (Indium TinOxide), IZO (In ₂ O _3- ZnO), and IGZO (In-Ga-ZnO ₄ ) electrodes, a color filter, and the like. Examples thereof include substrates made of acrylic, polycarbonate, polyimide, and the like.

As a method of applying the liquid crystal alignment agent to the substrate, a spinner method, a printing method, a dipping method, a dropping method, an inkjet method and the like are generally known. These methods are similarly applicable to the present invention.

As the heat-drying step, a method of heat-treating in an oven or an infrared furnace, a method of heat-treating on a hot plate, and the like are generally known. The heat-drying step is preferably carried out at a temperature within a range in which the solvent can be evaporated, and more preferably carried out at a temperature relatively lower than the temperature in the heating-baking step. Specifically, the heating and 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 firing step can be performed under the conditions necessary for the polyamic acid or a derivative thereof to exhibit an imidization reaction. For firing the coating film, a method of heat-treating in an oven or an infrared furnace, a method of heat-treating on a hot plate, and the like are generally known. These methods are similarly applicable in the present invention. Generally, it is preferably carried out at a temperature of about 90 to 300 ° C. for 1 minute to 3 hours, more preferably 120 to 280 ° C., and even more preferably 150 to 250 ° C.

When it is important to improve the anisotropy of the film and the afterimage characteristics when the liquid crystal display element is manufactured, it is preferable to slowly raise the temperature in the heating step, for example, while raising the temperature stepwise. , It can be heated and fired multiple times at different temperatures, or it can be heated by changing the temperature from low temperature to high temperature. Moreover, you may perform by combining both heating methods.

When heating and firing at different temperatures a plurality of times, a plurality of heating devices set to different temperatures may be used, or one heating device may be used while sequentially changing to different temperatures.

When firing at different temperatures a plurality of times, the initial firing temperature is preferably 90 to 180 ° C., and the final firing temperature is preferably 185 ° C. to 300 ° C. For example, after heating and firing at 110 ° C, heating and firing at 220 ° C, heating and firing at 110 ° C, then heating and firing at 230 ° C, heating and firing at 130 ° C, then heating and firing at 220 ° C, heating and firing at 150 ° C, and then 200 ° C. It is preferable to heat-fire at 150 ° C., heat-fire at 220 ° C., heat-fire at 150 ° C., then heat-fire at 230 ° C., or heat-fire at 170 ° C. and then heat-fire at 200 ° C. It is also preferable to heat and bake while increasing the number of steps and gradually raising the temperature. When the heating temperature is changed and the heating and firing is performed in two or more steps, the heating time in each heating step is preferably 5 minutes to 30 minutes.

When firing is performed by changing the temperature from a low temperature to a high temperature, the initial temperature is preferably 90 to 180 ° C. The final temperature is preferably 185 to 300 ° C, more preferably 190 to 230 ° C. The heating time is preferably 5 to 60 minutes, more preferably 20 to 60 minutes. The heating speed can be, for example, 0.5 ° C./min to 40 ° C./min. The temperature rise speed during the temperature rise does not have to be constant.

In the method for forming a liquid crystal alignment film of the present invention, a known photoalignment method is preferably used as a means for imparting anisotropy to a thin film in order to orient the liquid crystal in one direction with respect to the horizontal and / or vertical directions. be able to.

The method for forming the liquid crystal alignment film of the present invention by the photoalignment method will be described in detail. The liquid crystal alignment film of the present invention using the photoalignment method imparts anisotropy to the thin film by irradiating the thin film after heating and drying the coating film with linearly polarized light or non-polarized light, and forms the film. It can be formed by heating and firing. Alternatively, it can be formed by heating and drying the coating film, heating and firing, and then irradiating the thin film with linearly polarized light or unpolarized light. From the viewpoint of liquid crystal orientation, it is preferable that the light irradiation step is performed before the heating and firing step.

Further, in order to increase the liquid crystal alignment ability of the liquid crystal alignment film, it is possible to irradiate the coating film with linearly polarized light or unpolarized light while heating the coating film. The light irradiation may be performed in a step of heating and drying the coating film or a step of heating and firing, or may be performed between the heat drying step and the heating and firing step.
The heating temperature when irradiating light in the step of heating and drying the coating film or the step of heating and firing can refer to the above description of the heating and drying step or the heating and firing step. The heating temperature when irradiating light between the heat-drying step and the heat-baking step is preferably in the range of 30 ° C. to 150 ° C., and more preferably in the range of 50 ° C. to 110 ° C.

As the light, for example, ultraviolet rays containing light having a wavelength of 150 to 800 nm or visible light can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. Further, linearly polarized light or unpolarized light can be used. These lights are not particularly limited as long as they can impart a liquid crystal alignment ability to the thin film, but linearly polarized light is preferable when it is desired to exert a strong orientation regulating force on the liquid crystal.

Preferably the dose of linearly polarized light in the light irradiation step is 0.05~10J / cm ^2, more preferably 0.1~5J / cm ^2. The wavelength of linearly polarized light is preferably 200 to 400 nm, more preferably 300 to 400 nm. The irradiation angle of the linearly polarized light on the film surface is not particularly limited, but when it is desired to exert a strong orientation-regulating force on the liquid crystal, it is preferable that the linearly polarized light is perpendicular to the film surface as much as possible from the viewpoint of shortening the orientation processing time. Further, the liquid crystal alignment film of the present invention can orient the liquid crystal in a direction perpendicular to the polarization direction of the linearly polarized light by irradiating the liquid crystal alignment film with linearly polarized light.

Light sources used in the process of irradiating linearly polarized or unpolarized light include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, Deep UV lamps, halogen lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and mercury. A xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, a mercury-excited electrodeless lamp, and the like can be used without limitation.

The liquid crystal alignment film of the present invention can be preferably obtained by a method further including steps other than the above-mentioned steps.

The liquid crystal alignment film of the present invention does not require a step of cleaning the film after firing or light irradiation with a cleaning liquid, but a cleaning step can be provided for the convenience of other steps. Examples of the cleaning method using a cleaning liquid include brushing, jet spraying, steam cleaning, ultrasonic cleaning and the like. These methods may be performed alone or in combination. As the cleaning liquid, pure water or various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen-based solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone are used. It can be used, but 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 forming 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, an annealing treatment with heat or light can be used before and after the heating and firing step, or before and after irradiation with polarized or unpolarized light. 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. Further, examples of the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, and an LED lamp. The irradiation amount of light is preferably 0.3 to 10 J / cm ^2.

The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300 nm, and more preferably 30 to 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 characterized by having a particularly large orientation anisotropy. The magnitude of such anisotropy can be evaluated by the method using polarized IR described in JP-A-2005-275364 and the like. It can also be evaluated 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.

The liquid crystal alignment film of the present invention can be used for controlling the orientation of a liquid crystal composition for a liquid crystal display such as a smartphone, a tablet, an in-vehicle monitor, and a television. In addition to the orientation of liquid crystal compositions for liquid crystal displays, it can be used for orientation control of all other liquid crystal materials such as optical compensating materials and wideband variable phase shifters in the microwave / millimeter wave band using liquid crystals. Further, since the liquid crystal alignment film of the present invention has a large anisotropy, it can be used alone as an optical compensating material.

<Liquid crystal display element>
Next, the liquid crystal display element of the present invention will be described.
The liquid crystal display element of the present invention is characterized in that it has the liquid crystal alignment film of the present invention, and high display quality can be realized due to its afterimage characteristics and good contrast.

The liquid crystal display element of the present invention will be described in detail. The present invention is formed on a pair of substrates arranged to face each other, electrodes formed on one or both of the facing surfaces of the pair of substrates, and facing surfaces of the pair of substrates. In a liquid crystal display element having a liquid crystal alignment film formed, a liquid crystal layer formed between the pair of substrates, a pair of polarizing films installed so as to sandwich the opposing substrates, a backlight, and a driving device. The liquid crystal alignment film is composed of the liquid crystal 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 an electrode include an ITO or a metal vapor deposition film. Further, the electrodes 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. The desired shape of the electrode includes, for example, a comb shape or a zigzag structure. The electrodes may be formed on one of the pair of substrates, or may be formed on both substrates. The form of electrode formation differs depending on the type of liquid crystal display element. For example, in the case of an IPS type liquid crystal display element (transverse electric field type liquid crystal display element), an electrode is arranged on one of the pair of substrates, and the other liquid crystal display element. In the case of, electrodes are arranged on both of the pair of substrates. The liquid crystal alignment film is formed on the substrate or the electrode.

In the case of a homogeneously oriented liquid crystal display element (for example, IPS, FFS, etc.), at least from the backlight side, the backlight, the first polarizing film, the first substrate, the first liquid crystal alignment film, the liquid crystal layer, It has a second substrate and a second polarizing film, and the polarizing axis of the polarizing film is such that the polarizing axis of the first polarizing film (direction of polarization absorption) and the polarizing axis of the second polarizing film intersect (preferably). It is installed so as to be (orthogonal). At this time, it can be installed so that the polarization axis of the first polarizing film and the liquid crystal orientation direction are parallel to each other or orthogonal to each other. The liquid crystal display element installed so that the polarization axis of the first polarizing film and the liquid crystal orientation direction are parallel to each other is called O-mode, and the liquid crystal display element installed so as to be orthogonal to each other is called E-mode. The liquid crystal alignment film of the present invention can be applied to both O-mode and E-mode, and can be selected according to the purpose.

Dichroic compounds are used in many photoisomerized materials. Therefore, the polarization axis of the polarized light irradiated to add anisotropy to the liquid crystal alignment agent is aligned with the polarization axis of the polarization from the polarizing film arranged on the backlight side (the liquid crystal alignment agent of the present invention is used. When used, the O-mode arrangement is used), and the transmittance of the liquid crystal alignment film in the light absorption wavelength range increases. Therefore, the transmittance of the liquid crystal display element can be further improved.

The liquid crystal layer is formed so that the liquid crystal composition is sandwiched between the pair of substrates on which the surfaces on which the liquid crystal alignment film is formed face each other. In the formation of the liquid crystal layer, spacers such as fine particles and resin sheets that are interposed between the pair of substrates to form an appropriate interval can be used as needed.

As a method for forming the liquid crystal layer, a vacuum injection method and an ODF (One Drop Fill) method are known.

In the vacuum injection method, a gap (cell gap) is provided so that the liquid crystal alignment film surfaces face each other, and the sealant is printed and the substrates are bonded together, leaving the liquid crystal injection port. A liquid crystal display element is manufactured by injecting and filling a liquid crystal in a substrate surface and a cell gap partitioned by a sealant using a vacuum differential pressure, and then sealing the injection port.

In the ODF method, a sealant is printed on the outer periphery of the liquid crystal alignment film surface of one of the pair of substrates, liquid crystal is dropped on the inner region of the sealant, and then the other substrate is opposed so that the liquid crystal alignment film surfaces face each other. Stick together. Then, the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant to manufacture a liquid crystal display element.

As a sealing agent used for bonding substrates, a thermosetting type is also known in addition to the UV curing type. Printing of the sealant can be performed by, for example, a screen printing method.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy include Patent No. 3086228, Patent No. 2635435, No. 5-501735, JP-A-8-157826, JP-A-8-231960, JP-A-9-241644 (EP885272A1), Square root extraction 9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), Square root extraction 9-235552, Square root extraction 9-255956, Square root extraction 9-241643 (EP885271A1), Square root extraction 10-204016 (EP844229A1), Square root extraction 10 Examples thereof include liquid crystal compositions disclosed in −204436, JP-A-10-231482, JP-A-2000-087404, JP-A-2001-48822 and the like.

Preferred examples of the liquid crystal composition having a negative permittivity anisotropy are JP-A-57-114532, JP-A-2-4725, JP-A-4-224885, JP-A-8-40953, JP-A-8-104869, and Japanese Patent Application Laid-Open No. Kaihei 10-168076, JP-A-10-168453, JP-A-10-236998, JP-A-10-236990, JP-A-10-236992, JP-A-10-2369999, JP-A-10-236994, JP-A-10-237000, JP-A-10. -237004, Japanese Patent Application Laid-Open No. 10-237024, Japanese Patent Application Laid-Open No. 10-237035, Japanese Patent Application Laid-Open No. 10-237075, Japanese Patent Application Laid-Open No. 10-237076, Japanese Patent Application Laid-Open No. 10-237448 (EP967261A1) 10-291945, JP-A-11-029581, JP-A-11-080049, JP-A-2000-256307, JP-A-2001-019965, JP-A-2001-072626, JP-A-2001-192657, JP-A-2010-037428, International Publication 2011 / Examples thereof include liquid crystal compositions disclosed in 024666, International Publication 2010/072370, Japanese Patent Application Laid-Open No. 2010-537010, Japanese Patent Application Laid-Open No. 2012-077201, Japanese Patent Application Laid-Open No. 2009-08432.

It is also permissible to add one or more kinds of optically active compounds to the liquid crystal composition having a positive or negative dielectric anisotropy.

Further, for example, in the liquid crystal composition used for the liquid crystal display element of the present invention, additives may be further added from the viewpoint of improving the orientation, for example. Such additives include photopolymerizable monomers, optically active compounds, antioxidants, UV absorbers, dyes, defoamers, polymerization initiators, polymerization inhibitors and the like. Preferred photopolymerizable monomers, optically active compounds, antioxidants, UV absorbers, dyes, defoamers, polymerization initiators, polymerization inhibitors include compounds disclosed in International Publication 2015/146330 and the like. ..

Polymerizable compounds can be mixed into the liquid crystal composition to accommodate the liquid crystal display element in PSA (polymer sustained alignment) mode. Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxylane, oxetane) and vinyl ketone. Preferred compounds include compounds disclosed in International Publication 2015/146330 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.

<Weight average molecular weight (Mw)>
The weight average molecular weight of the polyamic acid was measured by the GPC method using a 2695 separation module and a 2414 differential refractometer (manufactured by Waters), and was determined 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 used was HSPgel RT MB-M (manufactured by Waters), and the measurement was carried out under the conditions of a column temperature of 50 ° C. and a flow velocity 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.

<AC afterimage measurement / contrast measurement>
The AC afterimage was measured according to the method described in Pamphlet 2000/43833.
Specifically, the luminance-voltage characteristic (BV characteristic) of the produced liquid crystal cell was measured, and this was defined as the luminance-voltage characteristic: B (before) before stress was applied. Next, an alternating current of 4.5 V and 60 Hz was applied to the liquid crystal cell for 20 minutes, short-circuited for 1 second, and the luminance-voltage characteristic (BV characteristic) was measured again. This was defined as the brightness-voltage characteristic after stress application: B (after). Here, the brightness change rate ΔB (%) was calculated by the following formula using the measured brightness of each brightness-voltage characteristic at a voltage of 1.3 V. The smaller the value of ΔB (%), the more the occurrence of AC afterimage can be suppressed, that is, the better the afterimage characteristic. If ΔB is 3% or less, it can be said that the afterimage characteristic is good, but in recent years, the demand for the afterimage characteristic has been further increased, and it is preferable that it is lower.
ΔB (%) = {[B (after) -B (before)] / B (before)} × 100
In addition, the contrast (CR) was determined using the ratio of the minimum brightness to the maximum brightness in the BV characteristics before stress was applied. The larger the CR value, the clearer the light and dark display and the better the contrast, and it can be said that the contrast is excellent at 3000 or more.
CR = B (before) _max / B (before) _min
In the equation, B (before) _max indicates the maximum luminance in the BV _{characteristic before stress application, and B (before) min} indicates the minimum luminance in the BV characteristic before stress application.

<Evaluation of voltage retention (VHR) reliability>
The voltage retention rate (VHR) of the liquid crystal display element is determined by applying a square wave having a wave height of ± 5 V to the cell at 60 ° C. according to the method described in “Mizushima et al. Was measured. The VHR at this time was set to VHR (before). The voltage holding ratio is an index showing how much the applied voltage is held after the frame cycle, and if this value is 100%, it means that all the charges are held. The cell was exposed to an LED backlight for 300 hours and VHR was measured again. The VHR at this time was defined as VHR (after).
The VHR reliability was evaluated by the VHR reduction rate calculated using the following formula. It can be said that the smaller the VHR reduction rate, the higher the VHR reliability and the higher the stability to light.
VHR reduction rate (%)
= {[VHR (after) -VHR (before)] / VHR (before)} x 100

<Re measurement>
Ellipsometry at 589 nm was measured using a spectroscopic ellipsometer. It can be said that the larger the Re, the more the directions of the polymer chains forming the alignment film are aligned, and the higher the anisotropy of the film.

<Tetracarboxylic dianhydride>

式（１−１−４）、式（１−２−１）、式（１−２−４）、式（ＤＩ−５−１）または式（ＤＩＨ−１−２）におけるｌ、ｍの値は、表１または２に記載した。 <Diamines>

Values of l and m in formula (1-1-4), formula (1-2-1), formula (1-2-4), formula (DI-5-1) or formula (DIH-1-2) Are listed in Table 1 or 2.

<Solvent>
NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve (ethylene glycol monobutyl ether)
<Additives>
Ad. 1: 1,3-bis (4,5-dihydro-2-oxazolyl) benzene

４−ニトロフェノール(50.0 g, 359 mmol）、１，４−ジブロモブタン(310.4 g, 1438 mmol）、および炭酸カリウム(74.5 g, 539 mmol)のＤＭＦ（500 mL）溶液を60度で2時間反応させた。反応混合物を室温まで冷却し、酢酸エチル（1 L）を加え、水（1 L）で3回洗浄し、硫酸ナトリウムで乾燥させた後、溶媒を減圧留去して粗体を得た。この粗体をヘプタン：酢酸エチル＝100:1の混合溶媒を溶離液に用いてシリカゲルカラムクロマトグラフィーで精製し、１−（４−ブロモ−ブトキシ）−４−ニトロベンゼンを収量45.9ｇ、収率47％で得た。 [Synthesis Example 1] Synthesis of compound of formula (1-2-1), l = 4

Reaction of 4-nitrophenol (50.0 g, 359 mmol), 1,4-dibromobutane (310.4 g, 1438 mmol), and potassium carbonate (74.5 g, 539 mmol) in DMF (500 mL) at 60 ° C. for 2 hours I let you. The reaction mixture was cooled to room temperature, ethyl acetate (1 L) was added, the mixture was washed 3 times with water (1 L), dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give a crude product. This crude product was purified by silica gel column chromatography using a mixed solvent of heptane: ethyl acetate = 100: 1 as an eluent, and 1- (4-bromo-butoxy) -4-nitrobenzene was obtained in a yield of 45.9 g and a yield of 47. Obtained in%.

４−ニトロアニリン（29.4 g, 213 mmol）の水（130 mL）溶液に、濃塩酸（53 mL）を氷冷下（氷浴）で加えた。次いで、この溶液に、亜硝酸ナトリウム（14.7 g, 213 mmol）の水（45 mL）溶液を氷冷下（氷浴）で滴下後、30分間撹拌し、４−ニトロベンゼンジアゾニウム塩酸塩の水溶液を調製した。
得られた４−ニトロベンゼンジアゾニウム塩酸塩の水溶液を、氷冷したフェノール(20.0 g, 213 mmol）と酢酸ナトリウム(139.5 g, 1700 mmol）のエタノール（10 mL）と水(400 mL)の混合溶液に撹拌しながらゆっくりと加えた。反応溶液を氷冷下（氷浴）で2時間撹拌した後、ろ過した。得られた固体を酢酸エチル(2 L)に溶解し、水（1 L）で3回洗浄し、硫酸ナトリウムで乾燥させた後、溶媒を減圧留去して、アゾベンゼン誘導体１を収量40.1ｇ、収率78％で得た。

To a solution of 4-nitroaniline (29.4 g, 213 mmol) in water (130 mL) was added concentrated hydrochloric acid (53 mL) under ice-cooling (ice bath). Next, a solution of sodium nitrite (14.7 g, 213 mmol) in water (45 mL) was added dropwise to this solution under ice-cooling (ice bath), and the mixture was stirred for 30 minutes to prepare an aqueous solution of 4-nitrobenzenediazonium hydrochloride. did.
The obtained aqueous solution of 4-nitrobenzene diazonium hydrochloride was added to a mixed solution of ice-cooled phenol (20.0 g, 213 mmol), sodium acetate (139.5 g, 1700 mmol) in ethanol (10 mL) and water (400 mL). Add slowly with stirring. The reaction solution was stirred under ice-cooling (ice bath) for 2 hours and then filtered. The obtained solid was dissolved in ethyl acetate (2 L), washed 3 times with water (1 L), dried over sodium sulfate, and the solvent was evaporated under reduced pressure to yield 40.1 g of the azobenzene derivative 1. It was obtained in a yield of 78%.

１−（４−ブロモ−ブトキシ）−４−ニトロベンゼン(20.0 g, 73 mmol）、アゾベンゼン誘導体１(17.7 g, 73 mmol）、および炭酸カリウム(15.1 g, 109 mmol)のＤＭＦ（200 mL）溶液を60度で6時間反応させた。反応混合物を室温まで冷却し、ジクロロメタン（4 L）を加え、水（2 L）で3回洗浄し、硫酸ナトリウムで乾燥させた後、溶媒を減圧留去して粗体を得た。この粗体を、ジクロロメタンを溶離液に用いてシリカゲルカラムクロマトグラフィーで精製し、アゾベンゼン誘導体２を収量30.5ｇ、収率96％で得た。

A solution of 1- (4-bromo-butoxy) -4-nitrobenzene (20.0 g, 73 mmol), azobenzene derivative 1 (17.7 g, 73 mmol), and potassium carbonate (15.1 g, 109 mmol) in DMF (200 mL). It was reacted at 60 degrees for 6 hours. The reaction mixture was cooled to room temperature, dichloromethane (4 L) was added, the mixture was washed 3 times with water (2 L), dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give a crude product. This crude product was purified by silica gel column chromatography using dichloromethane as an eluent to obtain an azobenzene derivative 2 in a yield of 30.5 g and a yield of 96%.

アゾベンゼン誘導体２（29.4 g, 67 mmol）のエタノール（60 mL）溶液に、水（60 mL）及び硫化ナトリウム九水和物（97.2 g, 405 mmol）を加え、2時間加熱還流した。反応混合物を室温まで冷却し、減圧濃縮した後、酢酸エチル（3 L）を加え、水（1 L）で3回洗浄し、硫酸ナトリウムで乾燥させた後、溶媒を減圧留去して粗体を得た。この粗体をトルエン：酢酸エチル＝3:1の混合溶媒を溶離液に用いてシリカゲルカラムクロマトグラフィーで精製し、式（１−２−１）、ｌ＝４の化合物を収量3.9ｇ、収率15％で得た。
¹H-NMR (500MHz, DMSO-D₆): δ 7.72 (d, J = 8.9Hz, 2H), 7.61 (d, J = 8.7Hz, 2H), 7.05 (d, J = 9.0Hz, 2H), 6.64-6.66 (m, 4H), 6.49 (d, J = 8.8Hz, 2H), 5.97 (br, 2H), 4.59 (br, 2H), 4.09 (t, J = 6.2Hz, 2H) , 3.89 (t, J = 6.1Hz, 2H) , 1.80-1.87 (m, 4H).

Water (60 mL) and sodium sulfide nine hydrate (97.2 g, 405 mmol) were added to a solution of azobenzene derivative 2 (29.4 g, 67 mmol) in ethanol (60 mL), and the mixture was heated under reflux for 2 hours. The reaction mixture is cooled to room temperature, concentrated under reduced pressure, ethyl acetate (3 L) is added, the mixture is washed 3 times with water (1 L), dried over sodium sulfate, and the solvent is distilled off under reduced pressure to prepare a crude product. Got This crude product was purified by silica gel column chromatography using a mixed solvent of toluene: ethyl acetate = 3: 1 as an eluent, and the compound of formula (1-2-1), l = 4 was obtained in a yield of 3.9 g. Obtained at 15%.
^{1 1} H-NMR (500MHz, DMSO-D ₆ ): δ 7.72 (d, J = 8.9Hz, 2H), 7.61 (d, J = 8.7Hz, 2H), 7.05 (d, J = 9.0Hz, 2H), 6.64-6.66 (m, 4H), 6.49 (d, J = 8.8Hz, 2H), 5.97 (br, 2H), 4.59 (br, 2H), 4.09 (t, J = 6.2Hz, 2H), 3.89 (t) , J = 6.1Hz, 2H), 1.80-1.87 (m, 4H).

４’−ヒドロキシアセトアニリド(60.0 g, 397 mmol）、１，２−ジブロモエタン(298 g, 1590 mmol）、および炭酸カリウム(82.3 g, 595 mmol)のＤＭＦ（600 mL）溶液を80度で8時間反応させた。反応混合物を室温まで冷却し、酢酸エチル（1.5 L）を加え、水（1 L）で3回洗浄し、硫酸ナトリウムで乾燥させた後、溶媒を減圧留去して粗体を得た。この粗体をヘプタン：酢酸エチル＝2:3の混合溶媒を溶離液に用いてシリカゲルカラムクロマトグラフィーで精製し、１−（２−ブロモ−エトキシ）−４−アセトアニリドを収量5.95ｇ、収率6％で得た。 [Synthesis Example 2] Synthesis of compound of formula (1-2-1), l = 2

A solution of 4'-hydroxyacetanilide (60.0 g, 397 mmol), 1,2-dibromoethane (298 g, 1590 mmol), and potassium carbonate (82.3 g, 595 mmol) in DMF (600 mL) at 80 ° C. for 8 hours. It was reacted. The reaction mixture was cooled to room temperature, ethyl acetate (1.5 L) was added, the mixture was washed 3 times with water (1 L), dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give a crude product. This crude product was purified by silica gel column chromatography using a mixed solvent of heptane: ethyl acetate = 2: 3 as an eluent, and 1- (2-bromo-ethoxy) -4-acetoanilide was obtained in a yield of 5.95 g and a yield of 6 Obtained in%.

４−アミノアセトアニリド（63.8 g, 425 mmol）の水（250 mL）溶液に、濃塩酸（106 mL）を氷冷下（氷浴）で加えた。次いで、この溶液に、亜硝酸ナトリウム（29.3 g, 425 mmol）の水（90 mL）溶液を氷冷下（氷浴）で滴下後、30分間撹拌し、ジアゾニウム塩の水溶液を調製した。
得られたジアゾニウム塩の水溶液を、氷冷したフェノール(40.0 g, 425 mmol）と酢酸ナトリウム(279 g, 3400 mmol）のエタノール（20 mL）と水(800 mL)の混合溶液に撹拌しながらゆっくりと加えた。反応溶液を氷冷下（氷浴）で2時間撹拌した後、ろ過した。得られた固体を酢酸エチル(4 L)に溶解し、水（2 L）で3回洗浄し、硫酸ナトリウムで乾燥させた後、溶媒を減圧留去して、アゾベンゼン誘導体３を収量31.2ｇ、収率29％で得た。

To a solution of 4-aminoacetanilide (63.8 g, 425 mmol) in water (250 mL) was added concentrated hydrochloric acid (106 mL) under ice-cooling (ice bath). Then, a solution of sodium nitrite (29.3 g, 425 mmol) in water (90 mL) was added dropwise to this solution under ice-cooling (ice bath), and the mixture was stirred for 30 minutes to prepare an aqueous solution of a diazonium salt.
The obtained aqueous solution of the diazonium salt is slowly mixed with a mixed solution of ice-cooled phenol (40.0 g, 425 mmol) and sodium acetate (279 g, 3400 mmol) in ethanol (20 mL) and water (800 mL) while stirring slowly. Added. The reaction solution was stirred under ice-cooling (ice bath) for 2 hours and then filtered. The obtained solid was dissolved in ethyl acetate (4 L), washed 3 times with water (2 L), dried over sodium sulfate, and the solvent was evaporated under reduced pressure to yield 31.2 g of the azobenzene derivative 3. Obtained in a yield of 29%.

１−（２−ブロモ−エトキシ）−４−アセトアニリド(5.95 g, 23.1 mmol）、アゾベンゼン誘導体３(5.30 g, 20.8 mmol）、および炭酸カリウム(4.78 g, 34.6 mmol)のＤＭＦ（30 mL）溶液を80度で4時間反応させた。反応混合物を室温まで冷却し、水（50 mL）を加え、析出した固形物をろ過し、アゾベンゼン誘導体４を収量8.66ｇ、収率87％で得た。

A solution of 1- (2-bromo-ethoxy) -4-acetanilide (5.95 g, 23.1 mmol), azobenzene derivative 3 (5.30 g, 20.8 mmol), and potassium carbonate (4.78 g, 34.6 mmol) in DMF (30 mL). It was reacted at 80 degrees for 4 hours. The reaction mixture was cooled to room temperature, water (50 mL) was added, and the precipitated solid was filtered to obtain an azobenzene derivative 4 in a yield of 8.66 g and a yield of 87%.

アゾベンゼン誘導体４（8.66 g, 20.0 mmol）のメタノール（90 mL）とＴＨＦ(210 mL)の混合溶液に、濃塩酸（41.7 mL）を加え、30時間加熱還流した。反応混合物を室温まで冷却し、1 mol/L水酸化ナトリウム水溶液で塩基性化した。得られた固形分をろ過して粗体を得た。この粗体を酢酸エチルを溶離液に用いてシリカゲルカラムクロマトグラフィーで精製し、式（１−２−１）、ｌ＝２の化合物を収量5.08ｇ、収率73％で得た。
¹H-NMR (500MHz, DMSO-D₆): δ 7.73 (d, J = 8.9Hz, 2H), 7.61 (d, J = 8.7Hz, 2H), 7.10 (d, J = 9.0Hz, 2H), 6.70 (d, J = 8.7Hz, 2H), 6.65 (d, J = 8.7Hz, 2H),6.51 (d, J = 8.7Hz, 2H), 5.97 (br, 2H), 4.63 (br, 2H), 4.32 (t, J = 4.4Hz, 2H) , 4.18 (t, J = 4.4Hz, 2H).

Concentrated hydrochloric acid (41.7 mL) was added to a mixed solution of azobenzene derivative 4 (8.66 g, 20.0 mmol) in methanol (90 mL) and THF (210 mL), and the mixture was heated under reflux for 30 hours. The reaction mixture was cooled to room temperature and basified with 1 mol / L aqueous sodium hydroxide solution. The obtained solid content was filtered to obtain a crude product. This crude product was purified by silica gel column chromatography using ethyl acetate as an eluent to obtain a compound of formula (1-2-1), l = 2 in a yield of 5.08 g and a yield of 73%.
¹ H-NMR (500MHz, DMSO-D ₆ ): δ 7.73 (d, J = 8.9Hz, 2H), 7.61 (d, J = 8.7Hz, 2H), 7.10 (d, J = 9.0Hz, 2H), 6.70 (d, J = 8.7Hz, 2H), 6.65 (d, J = 8.7Hz, 2H), 6.51 (d, J = 8.7Hz, 2H), 5.97 (br, 2H), 4.63 (br, 2H), 4.32 (t, J = 4.4Hz, 2H), 4.18 (t, J = 4.4Hz, 2H).

４’−ヒドロキシアセトアニリド(60.0 g, 397 mmol）、１，４−ジブロモブタン(343 g, 1590 mmol）、および炭酸カリウム(82.3 g, 595 mmol)のＤＭＦ（600 mL）溶液を80度で8時間反応させた。反応混合物を室温まで冷却し、酢酸エチル（1.5 L）を加え、水（1 L）で3回洗浄し、硫酸ナトリウムで乾燥させた後、溶媒を減圧留去して粗体を得た。この粗体をヘプタン：酢酸エチル＝2:3の混合溶媒を溶離液に用いてシリカゲルカラムクロマトグラフィーで精製し、１−（４−ブロモ−ブトキシ）−４−アセトアニリドを収量31.9 ｇ、収率28％で得た。 [Synthesis Example 3] Synthesis of compound of formula (1-2-4), l = 4

A solution of 4'-hydroxyacetanilide (60.0 g, 397 mmol), 1,4-dibromobutane (343 g, 1590 mmol), and potassium carbonate (82.3 g, 595 mmol) in DMF (600 mL) at 80 ° C. for 8 hours. It was reacted. The reaction mixture was cooled to room temperature, ethyl acetate (1.5 L) was added, the mixture was washed 3 times with water (1 L), dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give a crude product. This crude product was purified by silica gel column chromatography using a mixed solvent of heptane: ethyl acetate = 2: 3 as an eluent to yield 1- (4-bromo-butoxy) -4-acetoanilide in a yield of 31.9 g and a yield of 28. Obtained in%.

４−アミノアセトアニリド（26.8 g, 178 mmol）の水（130 mL）溶液に、濃塩酸（45 mL）を氷冷下（氷浴）で加えた。次いで、この溶液に、亜硝酸ナトリウム（12.3 g, 178 mmol）の水（40 mL）溶液を氷冷下（氷浴）で滴下後、30分間撹拌し、ジアゾニウム塩の水溶液を調製した。
得られたジアゾニウム塩の水溶液を、氷冷した２−フルオロフェノール(20.0 g, 178 mmol）と酢酸ナトリウム(117 g, 1430 mmol）のエタノール（10 mL）と水(400 mL)の混合溶液に撹拌しながらゆっくりと加えた。反応溶液を氷冷下（氷浴）で3時間撹拌した後、ろ過し、アゾベンゼン誘導体５を収量27.9ｇ、収率57％で得た。

To a solution of 4-aminoacetanilide (26.8 g, 178 mmol) in water (130 mL) was added concentrated hydrochloric acid (45 mL) under ice-cooling (ice bath). Then, a solution of sodium nitrite (12.3 g, 178 mmol) in water (40 mL) was added dropwise to this solution under ice-cooling (ice bath), and the mixture was stirred for 30 minutes to prepare an aqueous solution of a diazonium salt.
The obtained aqueous solution of the diazonium salt is stirred in a mixed solution of ice-cooled 2-fluorophenol (20.0 g, 178 mmol) and sodium acetate (117 g, 1430 mmol) in ethanol (10 mL) and water (400 mL). While adding slowly. The reaction solution was stirred under ice-cooling (ice bath) for 3 hours and then filtered to obtain an azobenzene derivative 5 in a yield of 27.9 g and a yield of 57%.

１−（４−ブロモ−ブトキシ）−４−アセトアニリド(20.0 g, 69.9 mmol）、アゾベンゼン誘導体５(19.1 g, 69.9 mmol）、および炭酸カリウム(14.5 g, 105 mmol)のＤＭＦ（100 mL）溶液を80度で4時間反応させた。反応混合物を室温まで冷却し、水（200 mL）を加え、析出した固形物をろ過し、アゾベンゼン誘導体６を収量29.5 ｇ、収率92％で得た。

A solution of 1- (4-bromo-butoxy) -4-acetanilide (20.0 g, 69.9 mmol), azobenzene derivative 5 (19.1 g, 69.9 mmol), and potassium carbonate (14.5 g, 105 mmol) in DMF (100 mL). It was reacted at 80 degrees for 4 hours. The reaction mixture was cooled to room temperature, water (200 mL) was added, and the precipitated solid was filtered to obtain an azobenzene derivative 6 in a yield of 29.5 g and a yield of 92%.

アゾベンゼン誘導体６（29.5 g, 61.6 mmol）のメタノール（300 mL）とＴＨＦ(740 mL)の混合溶液に、濃塩酸（128 mL）を加え、170時間加熱還流した。反応混合物を室温まで冷却し、1 mol/L水酸化ナトリウム水溶液で塩基性化した。得られた固形分をろ過して粗体を得た。この粗体を酢酸エチルを溶離液に用いてシリカゲルカラムクロマトグラフィーで精製し、式（１−２−４）、ｌ＝４の化合物を収量13.0ｇ、収率54％で得た。
¹H-NMR (500MHz, DMSO-D₆): δ 9.78-10.9 (br, 2H), 7.61 (d, J = 8.8Hz, 2H), 7.60 (s, 1H), 7.55 (m, 1H), 7.31 (m, 1H), 7.29 (dd, J = 8.9Hz, 2H), 7.04 (d, J = 8.9Hz, 2H), 6.66 (d, J = 8.8Hz, 2H), 5.95-6.28 (br, 2H), 4.20 (t, J = 5.8Hz, 2H) , 4.07 (t, J = 5.9Hz, 2H), 1.91 (m, 4H).

Concentrated hydrochloric acid (128 mL) was added to a mixed solution of azobenzene derivative 6 (29.5 g, 61.6 mmol) in methanol (300 mL) and THF (740 mL), and the mixture was heated under reflux for 170 hours. The reaction mixture was cooled to room temperature and basified with 1 mol / L aqueous sodium hydroxide solution. The obtained solid content was filtered to obtain a crude product. This crude product was purified by silica gel column chromatography using ethyl acetate as an eluent to obtain a compound of formula (1-2-4) with a yield of 13.0 g and a yield of 54%.
¹ H-NMR (500MHz, DMSO-D ₆ ): δ 9.78-10.9 (br, 2H), 7.61 (d, J = 8.8Hz, 2H), 7.60 (s, 1H), 7.55 (m, 1H), 7.31 (m, 1H), 7.29 (dd, J = 8.9Hz, 2H), 7.04 (d, J = 8.9Hz, 2H), 6.66 (d, J = 8.8Hz, 2H), 5.95-6.28 (br, 2H) , 4.20 (t, J = 5.8Hz, 2H), 4.07 (t, J = 5.9Hz, 2H), 1.91 (m, 4H).

４−ニトロアニリン（55.6 g, 403 mmol）の水（330 mL）溶液に、濃塩酸（100 mL）を氷冷下（氷浴）で加えた。次いで、この溶液に、亜硝酸ナトリウム（27.8 g, 403 mmol）の水（100 mL）溶液を氷冷下（氷浴）で滴下後、30分間撹拌し、４−ニトロベンゼンジアゾニウム塩酸塩の水溶液を調製した。
得られた４−ニトロベンゼンジアゾニウム塩酸塩の水溶液を、氷冷した３−ヒドロキシベンジルアルコール(50.0 g, 403 mmol）と酢酸ナトリウム(264 g, 3220 mmol）のエタノール（30 mL）と水(1000 mL)の混合溶液に撹拌しながらゆっくりと加えた。反応溶液を氷冷下（氷浴）で2時間撹拌した後、ろ過した。得られた固体を酢酸エチル(10 L)に溶解し、水（5 L）で3回洗浄し、硫酸ナトリウムで乾燥させた後、溶媒を減圧留去して、アゾベンゼン誘導体７を収量103 ｇ、収率94％で得た。 [Synthesis Example 4] Synthesis of compound of formula (1-1-4), l = 4

To a solution of 4-nitroaniline (55.6 g, 403 mmol) in water (330 mL) was added concentrated hydrochloric acid (100 mL) under ice-cooling (ice bath). Next, a solution of sodium nitrite (27.8 g, 403 mmol) in water (100 mL) was added dropwise to this solution under ice-cooling (ice bath), and the mixture was stirred for 30 minutes to prepare an aqueous solution of 4-nitrobenzenediazonium hydrochloride. did.
The obtained aqueous solution of 4-nitrobenzene diazonium hydrochloride was ice-cooled with 3-hydroxybenzyl alcohol (50.0 g, 403 mmol), sodium acetate (264 g, 3220 mmol) in ethanol (30 mL), and water (1000 mL). Was added slowly to the mixed solution of the above with stirring. The reaction solution was stirred under ice-cooling (ice bath) for 2 hours and then filtered. The obtained solid was dissolved in ethyl acetate (10 L), washed 3 times with water (5 L), dried over sodium sulfate, and the solvent was evaporated under reduced pressure to yield 103 g of the azobenzene derivative 7. Obtained in a yield of 94%.

１−（４−ブロモ−ブトキシ）−４−ニトロベンゼン(50.0 g, 182 mmol）、アゾベンゼン誘導体７(49.8 g, 182 mmol）、および炭酸カリウム(37.8 g, 274 mmol)のＤＭＦ（500 mL）溶液を60度で6時間反応させた。反応混合物を室温まで冷却し、酢酸エチル（5 L）を加え、水（3 L）で3回洗浄し、硫酸ナトリウムで乾燥させた後、溶媒を減圧留去して粗体を得た。この粗体を、酢酸エチルを溶離液に用いてシリカゲルカラムクロマトグラフィーで精製し、アゾベンゼン誘導体８を収量26.5ｇ、収率31％で得た。

A solution of 1- (4-bromo-butoxy) -4-nitrobenzene (50.0 g, 182 mmol), azobenzene derivative 7 (49.8 g, 182 mmol), and potassium carbonate (37.8 g, 274 mmol) in DMF (500 mL). It was reacted at 60 degrees for 6 hours. The reaction mixture was cooled to room temperature, ethyl acetate (5 L) was added, the mixture was washed 3 times with water (3 L), dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give a crude product. This crude product was purified by silica gel column chromatography using ethyl acetate as an eluent to obtain an azobenzene derivative 8 in a yield of 26.5 g and a yield of 31%.

アゾベンゼン誘導体８（20.0 g, 43 mmol）のエタノール（300 mL）溶液に、水（100 mL）及び硫化ナトリウム九水和物（41.2 g, 172 mmol）を加え、2時間加熱還流した。反応混合物を室温まで冷却し、ろ過して粗体を得た。この粗体をトルエン：酢酸エチル＝4:1の混合溶媒を溶離液に用いてシリカゲルカラムクロマトグラフィーで精製し、式（１−１−４）、ｌ＝４の化合物を収量1.23 ｇ、収率7％で得た。
¹H-NMR (500MHz, DMSO-D₆): δ 7.59 (d, J = 8.8Hz, 2H), 7.53 (d, J = 8.9Hz, 1H), 7.17 (d, J = 2.8Hz, 1H), 6.87 (dd, J = 2.7, 8.9 Hz, 1H), 6.63-6.66 (m, 4H), 6.49 (d, J = 8.8Hz, 2H), 5.96 (br, 2H), 5.20 (t, J = 5.7Hz, 1H), 4.99 (d, J = 5.7 Hz, 2H), 4.59 (br, 2H), 4.09 (t, J = 6.0Hz, 2H) , 3.89 (t, J = 6.3Hz, 2H) , 1.82-1.88 (m, 4H).

Water (100 mL) and sodium sulfide nine hydrate (41.2 g, 172 mmol) were added to a solution of azobenzene derivative 8 (20.0 g, 43 mmol) in ethanol (300 mL), and the mixture was heated under reflux for 2 hours. The reaction mixture was cooled to room temperature and filtered to obtain a crude product. This crude product was purified by silica gel column chromatography using a mixed solvent of toluene: ethyl acetate = 4: 1 as an eluent, and the compound of formula (1-1-4) and l = 4 was obtained in a yield of 1.23 g. Obtained at 7%.
¹ H-NMR (500MHz, DMSO-D ₆ ): δ 7.59 (d, J = 8.8Hz, 2H), 7.53 (d, J = 8.9Hz, 1H), 7.17 (d, J = 2.8Hz, 1H), 6.87 (dd, J = 2.7, 8.9 Hz, 1H), 6.63-6.66 (m, 4H), 6.49 (d, J = 8.8Hz, 2H), 5.96 (br, 2H), 5.20 (t, J = 5.7Hz) , 1H), 4.99 (d, J = 5.7 Hz, 2H), 4.59 (br, 2H), 4.09 (t, J = 6.0Hz, 2H), 3.89 (t, J = 6.3Hz, 2H), 1.82-1.88 (m, 4H).

<Preparation of varnish>
The varnish used in this example was prepared by the following procedure. Here, the varnishes A1 to A11 prepared in Preparation Examples 1 to 11 of the varnish are a solution of a polyamic acid obtained by reacting with at least one compound having photoreactivity as one of the raw materials. Varnish Preparation Examples 12 to 14 for blending varnishes B1 to B3 are solutions of polyamic acid obtained without using a photoreactive compound as a raw material, and are used by blending with varnishes A1 to A11. It is a thing.

[Varnish Preparation Example 1] Preparation of Varnish A1 1.665 g of the compound represented by the formula (1-2-1-2) was placed in a 100 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube, and N-methyl was added. -2-Pyrrolidone was added in an amount of 17.0 g, and the mixture was stirred. To this solution, 0.175 g of the compound represented by the formula (AN-2-1), 0.263 g of the compound represented by the formula (AN-1-1) and (AN-4-17) (m = 8). ) Was added, and the mixture was stirred at room temperature for 12 hours. 15.0 g of NMP and 15.0 g of BC are added thereto, and the solution is heated and stirred at 70 ° C. until the weight average molecular weight of the solute polymer reaches the desired weight average molecular weight, and the weight average molecular weight of the solute is about 13,000. A varnish A1 having a resin content of 6% by weight was obtained.

[Preparation Examples 2 to 17 of Varnish] Preparation of Varnish A2 to A14 and Varnish B1 to B3 Preparation Example 1 and the compounds used as diamines and tetracarboxylic dianhydride were changed as shown in Table 1. Similarly, varnishes A2 to A14 having a resin content of 6% by weight were prepared. Varnishes B1 to B3 were prepared in the same manner as in Preparation Example 1 except that the compounds used as diamines and tetracarboxylic dianhydride were changed as shown in Table 2. In the varnishes B1 to B3, the heating and stirring conditions were adjusted so that the weight average molecular weight of the polymer was about 50,000. The weight average molecular weight of the produced polymer is shown in Tables 1 and 2 together with the results of Adjustment Example 1. In addition, in the preparation example in which 2 or more compounds are listed as diamines in Table 1, it means that all the compounds were used together as diamines, and 2 or more compounds as tetracarboxylic dianhydrides. In the preparation examples listed, it means that all the compounds were used together as a tetracarboxylic dianhydride. The numerical value in square brackets represents the compounding ratio (mol%), and the blank means that the compound corresponding to the column is not used. The same applies to Tables 2 and 3.

[Table 1]

[Table 2]

[Varnish Preparation Example 18] Preparation of Varnish C1 In this preparation example, a polyamic acid block polymer was synthesized by performing a two-step polymerization step.
(1) First-stage polymerization step Diamine compound (DI-5-9) (0.226 g) and diamine compound (DI-13-1) were placed in a 200 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube. (0.910 g), diamine compound (DI-4-19) (0.308 g), and NMP (20.0 g) were added and stirred. Tetracarboxylic dianhydride (AN-2-1) (0.665 g), tetracarboxylic dianhydride (AN-3-2) (0.740 g), and NMP (10.0 g) were added to this solution. The mixture was charged and stirred at room temperature for 6 hours to obtain a first polyamic acid solution.

(2) Second-stage polymerization step Diamine compound (1-2-1, l = 4) (1.28 g) and diamine compound (V-2-1) (0) were placed in the flask subjected to the first-stage polymerization. .120 g), diamine compound (DI-13-1) (0.152 g), tetracarboxylic dianhydride (AN-4-17, m = 8) (1.38 g), tetracarboxylic dianhydride (AN) -2-1) (0.111 g), tetracarboxylic dianhydride (AN-1-1) (0.112 g), and NMP (34.0 g) were added, and stirring was continued at room temperature for 24 hours. A mixed solution of the polyamic acid of No. 1 and the second polyamic acid was obtained. BC (30.0 g) was added to this reaction solution, and the mixture was stirred for 8 hours while heating at 60 ° C. to obtain a polyamic acid block polymer solution having a polymer solid content concentration of 6% by weight. This polyamic acid block polymer solution is referred to as varnish C1.

[Preparation Examples 19 to 22 of Varnish] Preparation of Varnish C2 to C5 Resin content in the same manner as in Preparation Example 18 except that the compounds used as diamines and tetracarboxylic dianhydride were changed as shown in Table 3. Varnishes C2 to C5 having a concentration of 6% by weight were prepared. The weight average molecular weight of the produced polymer is shown in Table 3 together with the results of Adjustment Example 18.

[Table 3]

[Example 1]
<Varnish preparation and AC afterimage measurement>
Varnish A1 was diluted with an NMP / BC mixed solution (NMP / BC = 7/3 weight ratio) so as to be 4% by weight and stirred to prepare an orienting agent 1.
The alignment agent 1 was applied to the glass substrate with the FFS electrode and the glass substrate with the column spacer by the spinner method. After coating, the substrate is heated at 60 ° C. for 80 seconds to evaporate the solvent, and then ultraviolet rays are emitted from the vertical direction with respect to the substrate via a polarizing plate using Multilite ML-501C / B manufactured by Ushio, Inc. Was irradiated with linearly polarized light. ^{The exposure energy at this time was 2.0 ± 0.1 J / cm 2} at a wavelength of 365 nm by measuring the amount of light using an ultraviolet integrated light meter UIT-150 (receiver: UVD-S365) manufactured by Ushio, Inc. The exposure time was adjusted so as to be. Then, it was fired at 220 ° C. for 30 minutes to form an alignment film having a film thickness of about 100 nm.
Next, the two substrates on which these alignment films are formed are opposed to each other on the surfaces on which the liquid crystal alignment films are formed, and a gap for injecting the liquid crystal composition is provided between the facing liquid crystal alignment films. I pasted them together. At this time, the polarization directions of the linearly polarized light applied to each liquid crystal alignment film were made parallel. A positive liquid crystal composition A was injected into these cells to prepare a liquid crystal cell (liquid crystal display element) having a cell thickness of 5 μm.

（物性値）
相転移温度ＮＩ：１００．１℃、誘電率異方性Δε：５．１、屈折率異方性Δｎ：０．０９３、粘度η：２５．６ｍＰａ・ｓ． <Positive liquid crystal composition A>

(Physical characteristic value)
Phase transition temperature NI: 100.1 ° C., permittivity anisotropy Δε: 5.1, refractive index anisotropy Δn: 0.093, viscosity η: 25.6 mPa · s.

Using the prepared liquid crystal cell, AC afterimage measurement and contrast measurement were performed according to the above-mentioned evaluation method "AC afterimage measurement / contrast measurement". As a result, ΔB was 1.3% and CR was 3200.

<VHR reliability evaluation>
The alignment agent 1 was applied to the glass substrate with the IPS electrode and the glass substrate with the column spacer by the spinner method. After coating, the substrate is heated at 60 ° C. for 80 seconds to evaporate the solvent, and then ultraviolet rays are emitted from the vertical direction with respect to the substrate via a polarizing plate using Multilite ML-501C / B manufactured by Ushio, Inc. Was irradiated with linearly polarized light. ^{The exposure energy at this time was 2.0 ± 0.1 J / cm 2} at a wavelength of 365 nm by measuring the amount of light using an ultraviolet integrated light meter UIT-150 (receiver: UVD-S365) manufactured by Ushio, Inc. The exposure time was adjusted so as to be. Then, it was fired at 220 ° C. for 30 minutes to form an alignment film having a film thickness of about 100 nm.

Next, the two substrates on which the liquid crystal alignment film is formed face each other on the surface on which the liquid crystal alignment film is formed, and a gap for injecting the liquid crystal composition is formed between the facing liquid crystal alignment films. It was pasted together. At this time, the orientation of the substrate was set so that the polarization directions of the linearly polarized light irradiated to each liquid crystal alignment film during the photoalignment treatment were parallel to each other. A negative liquid crystal composition A having the following composition was injected into the gap between the bonded substrates to prepare a liquid crystal cell (liquid crystal display element) having a cell thickness of 7 μm.

（物性値）
相転移温度ＮＩ：７５．７℃、誘電率異方性Δε：−４．１、屈折率異方性Δｎ：０．１０１、粘度η：１４．５ｍＰａ・ｓ． <Negative liquid crystal composition A>

(Physical characteristic value)
Phase transition temperature NI: 75.7 ° C., permittivity anisotropy Δε: -4.1, refractive index anisotropy Δn: 0.101, viscosity η: 14.5 mPa · s.

Using the prepared liquid crystal cell, the VHR reliability was evaluated according to the above-mentioned evaluation method "Evaluation of voltage retention (VHR) reliability". As a result, the VHR reduction rate was -4%.

[Example 2] to [Example 7], [Comparative Example 1] to [Comparative Example 3]
The same operations as in Example 1 were carried out except that the varnishes shown in Table 4 were used instead of the varnish 1, to prepare alignment agents 2 to 7 and comparative alignment agents 1 to 3. Using the prepared alignment agent, the same operation as in Example 1 was carried out, and AC afterimage measurement, contrast measurement, and VHR reliability evaluation were performed. The results are shown in Table 4 together with the results of Example 1.

[Table 4]

In Examples 1 to 7 using the compound of the present invention, the value of ΔB was small and excellent afterimage characteristics were exhibited. The contrast was also high, showing excellent contrast. Further, a liquid crystal display element having a small VHR reduction rate and high VHR reliability was obtained. On the other hand, in Comparative Example 1 using diaminoazobenzene, ΔB and contrast were about the same as in Examples 1 to 7, but the VHR reduction rate was large and high VHR reliability could not be obtained.
In Comparative Examples 2 and 3 in which diaminoazobenzene and a diamine having an alkyl chain structure are used in combination, the VHR reduction rate becomes about the same as in Examples 1 to 7 by lowering the ratio of the azobenzene structure, and the VHR reliability is improved. I was able to do it. However, the value of ΔB was larger and the contrast was lower than in Examples 1 to 7, and excellent afterimage characteristics and contrast could not be obtained.

[Example 8]
Varnish A1 and varnish B1 are blended so as to have a weight ratio of 3: 7, further diluted with an NMP / BC mixed solution (NMP / BC = 7/3 weight ratio) to a weight ratio of 4%, stirred, and an orienting agent. 8 was prepared.
Using the aligning agent 8, the same operation as in Example 1 was carried out, and AC afterimage measurement, contrast measurement, and VHR reliability evaluation were performed.

[Example 9] to [Example 12], [Comparative Example 4] to [Comparative Example 6]
The varnishes shown in Table 5 were used instead of the varnishes A1 and B1, and the blending ratios shown in Table 5 were changed. 6 was prepared. To the alignment agent 10, 3 parts by weight of 1,3-bis (4,5-dihydro-2-oxazolyl) benzene was added as an additive to the solid content, and this was used for the subsequent evaluation. Using the prepared aligning agent, AC afterimage measurement, contrast measurement, and VHR reliability evaluation were performed in the same manner as in Example 8. The varnishes used, blend ratios and results are shown in Table 5 with Example 8.

[Table 5]

Even in the blended liquid crystal alignment agent, when the liquid crystal alignment agent of the present invention was used, ΔB was small and excellent afterimage characteristics were exhibited. In addition, the contrast was high and the contrast was excellent. Further, a liquid crystal display element having a small VHR reduction rate and high VHR reliability was obtained. On the other hand, in Comparative Example 4 in which diaminoazobenzene was used instead of the compound of the present invention, the same ΔB and contrast values were shown. However, although the VHR reduction rate was smaller than that of Comparative Example 1 due to the blended type, there was still a 10% reduction, and high VHR reliability could not be obtained. In Comparative Example 5 in which diaminoazobenzene and a diamine having an alkyl chain structure were used in combination, the VHR reduction rate was about the same as when the compound of the present invention was used, but the value of ΔB was large, the contrast was low, and the afterimage characteristics were low. The result was that the contrast was inferior. In Comparative Example 6 in which the compound represented by the formula (V-4-2) was used instead of the compound of the present invention, the VHR reduction rate and the value of ΔB were similar to those in the case of using the compound of the present invention. , The contrast was low.
As described above, it was not possible to obtain a liquid crystal display device having excellent afterimage characteristics, contrast and high VHR reliability with the comparative orientation agent not using the compound of the present invention.

[Example 13] to [Example 16], [Comparative Example 7]
The same procedure as in Example 1 was carried out except that the varnishes shown in Table 6 were used instead of the varnish 1, to prepare the aligning agents 13 to 16 and the comparative aligning agent 7. Using the prepared alignment agent, the same operation as in Example 1 was carried out, and AC afterimage measurement, contrast measurement, and VHR reliability evaluation were performed. The results are shown in Table 6.

[Table 6]

Even in the block polymer, when the liquid crystal alignment agent of the present invention was used, ΔB was small and excellent afterimage characteristics were exhibited. In addition, the contrast was high and the contrast was excellent. Further, a liquid crystal display element having a small VHR reduction rate and high VHR reliability was obtained. On the other hand, in Comparative Example 7 in which diaminoazobenzene was used instead of the compound of the present invention, the same ΔB and contrast values were shown. However, VHR decreased by 12%, and high VHR reliability could not be obtained.
As described above, it was not possible to obtain a liquid crystal display device having excellent afterimage characteristics, contrast and high VHR reliability with the comparative orientation agent not using the compound of the present invention.

[Example 17]
The alignment agent 1 was applied to the glass substrate by the spinner method. After coating, the substrate was heated at 60 ° C. for 80 seconds to evaporate the solvent to form a film of alignment agent. This substrate was irradiated with linear knitting light. For irradiation, Multilite ML-501C / B manufactured by Ushio, Inc. was used, and the substrate was irradiated with linearly polarized ultraviolet rays from the vertical direction via a polarizing plate. ^{The exposure energy at this time was 1.0 ± 0.1 J / cm 2} at a wavelength of 365 nm by measuring the amount of light using an ultraviolet integrated light meter UIT-150 (receiver: UVD-S365) manufactured by Ushio, Inc. The exposure time was adjusted so as to be. Then, it was fired at 220 ° C. for 30 minutes to form an alignment film having a film thickness of about 100 nm.
The retardation value (Re value) of this substrate at 589 nm was measured using a spectroscopic ellipsometer. As a result, it was 34 nm.

[Comparative Example 8] and [Comparative Example 9]
The same operation as in Example 17 was performed except that the alignment agent shown in Table 7 was used instead of the alignment agent 1, and the Re value was measured. The measured values are shown in Table 7 together with the results of Example 17.

[Table 7]

In Example 17 using the compound represented by the formula (1-2-1) of the present invention, Comparative Example 8 using diaminoazobenzene and Comparative Example 9 using diaminoazobenzene and a diamine having an alkyl chain structure in combination. The Re value was significantly higher than that of the above. When it is important to obtain a liquid crystal alignment film with high anisotropy, it is effective to use a compound selected from the group consisting of formulas (1-2-1) to (1-2-9). I found out.

[Example 18]
A liquid crystal cell was prepared according to Example 1 except that the alignment agent 4 was used as the liquid crystal alignment agent and the exposure energy in the linearly polarized light irradiation of ultraviolet rays was changed. Adjust the exposure time so that the exposure energy is 0.5 ± 0.1, 1.0 ± 0.1, and 2.0 ± 0.1 J / cm ² at a wavelength of 365 nm, respectively, and use three liquid crystal cells. Created.
Using the above three liquid crystal cells, AC afterimage measurement was performed according to Example 1. As a result, ΔB was 1.4%, 1.5%, and 1.1%, respectively, when the exposure energies were 0.5 ± 0.1, 1.0 ± 0.1, and 2.0 ± 0.1 J / cm ^2. Met.

[Comparative Example 10]
AC afterimage measurement was performed in the same manner as in Example 14 using the comparative alignment agent 1 as the liquid crystal alignment agent. As a result, ΔB was 4.0%, 1.9%, and 1.0%, respectively, when the exposure energies were 0.5 ± 0.1, 1.0 ± 0.1, and 2.0 ± 0.1 J / cm ^2. Met.

The liquid crystal cell of Example 18 shows a sufficiently low ΔB value as compared with the liquid crystal cell of Comparative Example 10 even at a relatively low exposure energy of ^{0.5 and 1.0 J / cm 2, and the liquid crystal cell has good afterimage characteristics.} Has been obtained. When the sensitivity of the liquid crystal aligning agent is emphasized, it has been found that it is effective to use a compound selected from the group consisting of the formulas (1-2-4) to (1-2-9).

If a liquid crystal alignment film formed by using the liquid crystal alignment agent of the present invention is used, it has good afterimage characteristics and contrast, and even when exposed to strong light for a long time, a high voltage retention rate is maintained and display quality is maintained. It is possible to obtain a liquid crystal display element that does not decrease. The liquid crystal alignment agent of the present invention can be suitably applied to a transverse electric field type liquid crystal display element. Further, by using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having high anisotropy can be obtained, and it can be used as an optical compensating material or the like.

Claims (14)

A liquid crystal alignment agent containing at least one polymer, wherein at least one of the polymers is a polymer obtained by reacting tetracarboxylic dianhydrides with diamines, and at least one of the diamines is represented by the formula (1). A liquid crystal alignment agent which is a represented compound.

In the formula (1), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
a to c are independently integers of 0 to 2, respectively.
R ^a and R ^b are independently hydrogen atoms, formula (P1-1), formula (P1-2), -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ , respectively.
R ^c is a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , and -F, respectively.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a are independently hydrogen atoms, substituted or unsubstituted alkyls, substituted or unsubstituted alkanoyls, substituted or unsubstituted alkoxys, respectively. It is a carbonyl, or a substituted or unsubstituted arylcarbonyl, and R ^{6a to} R ^8a may be the same or different from each other, and * represents the bonding position to the benzene ring in the formula (1).
In formula (1), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary. The liquid crystal alignment agent according to claim 1, wherein at least one of the compounds represented by the formula (1) is a compound represented by the formula (1-1) or the formula (1-2).

In formula (1-1), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
R ¹ and R ² are independently hydrogen atoms, formulas (P1-1), or (P1-2), and ^{at least one of R 1} and R ² is formula (P1-1) or formula (P1-). 2) and
c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.
In formula (1-2), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
a is an integer from 0 to 2, and R ³ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ .
b is an integer from 0 to 2, and R ⁵ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ .
c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a are independently hydrogen atoms, substituted or unsubstituted alkyls, substituted or unsubstituted alkanoyls, substituted or unsubstituted alkoxys, respectively. It is a carbonyl, or a substituted or unsubstituted arylcarbonyl, and R ^{6a to} R ^8a may be the same or different from each other, and * represents the bonding position to the benzene ring in the formula (1-1).
In formulas (1-1) and (1-2), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary. Claimed that the compound represented by the formula (1-1) is a compound represented by at least one formula selected from the group consisting of the formulas (1-1-1) to (1-1-12). 2. The liquid crystal alignment agent according to 2.

In formulas (1-1-1) to (1-1-12), R ⁶ is an alkyl having 1 to 4 carbon atoms.
l is an integer of 1 to 10, m is an integer of 1 to 11, and n is an integer of 1 to 12. Claimed that the compound represented by the formula (1-2) is a compound represented by at least one formula selected from the group consisting of the formulas (1-2-1) to (1-2-9). 2. The liquid crystal alignment agent according to 2.

In equations (1-2-1) to (1-2-9), l is an integer of 1 to 10, m is an integer of 1 to 11, and n is an integer of 1 to 12. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein all the polymers contain at least one compound represented by the formula (1) as a raw material. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein at least one polymer does not contain a compound represented by the formula (1) as a raw material. A liquid crystal alignment film formed from the liquid crystal alignment agent according to any one of claims 1 to 6. A liquid crystal display element having the liquid crystal alignment film according to claim 7. A method for producing a liquid crystal alignment film, which comprises a step of applying the liquid crystal alignment agent according to any one of claims 1 to 6 to a substrate and a step of irradiating the coating film with polarized ultraviolet rays. A compound represented by the formula (1).

In the formula (1), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
a to c are independently integers of 0 to 2, respectively.
R ^a and R ^b are independently hydrogen atoms, formula (P1-1), formula (P1-2), -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ , respectively.
R ^c is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a are independently hydrogen atoms, substituted or unsubstituted alkyls, substituted or unsubstituted alkanoyls, substituted or unsubstituted alkoxys, respectively. It is a carbonyl or a substituted or unsubstituted arylcarbonyl, and R ^{6a to} R ^8a may be the same or different from each other, and * represents the bonding position to the benzene ring in the formula (1).
In formula (1), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary. The compound according to claim 10, which is represented by the formula (1-1) or the formula (1-2).

In formula (1-1), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
R ¹ and R ² are independently hydrogen atoms, formula (P1-1), or formula (P1-2), and ^{at least one of R 1} and R ² is formula (P1-1) or formula (P1). -2) and
c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.
In formula (1-2), X is an alkylene having 1 to 12 carbon atoms, and one or more non-adjacent ones or more _{of − (CH 2} ) _{2 − of the alkylene are replaced with either −O− or −NH−.} May be
a is an integer from 0 to 2, and R ³ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ .
b is an integer from 0 to 2, and R ⁵ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , -F, or -COOCH ₃ .
c is an integer from 0 to 2, and R ⁴ is independently a hydrogen atom, -CH ₃ , -OCH ₃ , -CF ₃ , or -F.

In formulas (P1-1) and (P1-2), R ^{6a to} R ^8a are independently hydrogen atoms, substituted or unsubstituted alkyls, substituted or unsubstituted alkanoyls, substituted or unsubstituted alkoxys, respectively. It is a carbonyl or a substituted or unsubstituted arylcarbonyl, and R ^{6a to} R ^8a may be the same or different from each other, and * represents the bonding position to the benzene ring in the formula (1-1).
In formulas (1-1) and (1-2), a group whose bond position is not fixed to any of the carbon atoms constituting the ring indicates that the bond position in the ring is arbitrary. 11. The compound according to claim 11, wherein the compound represented by the formula (1-1) is represented by at least one formula selected from the group consisting of the formulas (1-1-1) to (1-1-12). Compound.

In formulas (1-1-1) to (1-1-12), R ⁶ is an alkyl group having 1 to 4 carbon atoms.
l is an integer of 1 to 10, m is an integer of 1 to 11, and n is an integer of 1 to 12. 11. The compound according to claim 11, wherein the compound represented by the formula (1-2) is represented by at least one formula selected from the group consisting of the formulas (1-2-1) to (1-2-9). Compound.

In equations (1-2-1) to (1-2-9), l is an integer of 1 to 10, m is an integer of 1 to 11, and n is an integer of 1 to 12. A polymer obtained by reacting tetracarboxylic dianhydrides with diamines, wherein the diamines are at least one of the compounds according to any one of claims 10 to 13.