JPWO2019004433A1 - Method for manufacturing zero plane anchoring film and liquid crystal display device - Google Patents

Abstract

Provided are a method for industrially producing a zero-plane anchoring film, a good liquid crystal display device using the same, and a method for producing a liquid crystal display device. A liquid crystal composition containing a liquid crystal and a radically polymerizable compound, in a state of being in contact with the radical generating film, including a step of giving sufficient energy to cause a polymerization reaction of the radically polymerizable compound, a zero plane anchoring film Production method. And a step of preparing a cell having a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between a first substrate having a radical generating film and a second substrate having no radical generating film, and the cell The method for producing a functional film includes the step of applying sufficient energy to cause a polymerization reaction of the radically polymerizable compound.

Description

  The present invention is a method of applying a polymer stabilization technology capable of producing a zero-plane anchoring film by a method that is inexpensive and does not include complicated steps, and further low voltage using the method. The present invention relates to a liquid crystal display device for realizing driving and a manufacturing method thereof.

  2. Description of the Related Art In recent years, liquid crystal display devices have been widely used in mobile phones, computers, televisions, and the like. Liquid crystal display devices have characteristics such as thinness, light weight, and low power consumption, and are expected to be applied to further contents such as VR and ultra-high definition displays in the future. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment) have been proposed as display methods for liquid crystal displays, but the liquid crystal has a desired alignment state in all modes. A film (liquid crystal alignment film) that induces to (1) is used.

  In particular, for products equipped with a touch panel such as a tablet PC, a smart phone, and a smart TV, an IPS mode in which the display is not disturbed even when touched is preferred, and in recent years, FFS (Frindge) has been improved in terms of improving contrast and viewing angle characteristics. A liquid crystal display element using Field Switching and a technique using a non-contact technique using optical alignment have come to be used.

  However, FFS has a problem that the manufacturing cost of the substrate is higher than that of IPS, and a display defect peculiar to the FFS mode called Vcom shift occurs. Regarding photo-alignment, there is a merit that the size of the element that can be manufactured can be increased and the display characteristics can be greatly improved as compared with the rubbing method, but there is a problem in the principle of photo-alignment (in the case of a decomposition type, it is derived from decomposed products. (2) display failure, and if it is an isomerization type, image sticking due to insufficient orientation force). At present, manufacturers of liquid crystal display elements and manufacturers of liquid crystal alignment films are making various efforts to solve these problems.

  On the other hand, in recent years, an IPS mode using zero plane anchoring has been proposed, and it has been reported that this method can improve the contrast and drastically reduce the voltage as compared with the conventional IPS mode. (See Patent Document 1).

  Specifically, a liquid crystal alignment film having a strong anchoring energy is used on one side of the substrate, and one side of the substrate equipped with an electrode for generating a horizontal electric field has no liquid crystal alignment regulating force. It is a method of producing an IPS mode liquid crystal display element by using various treatments.

  In recent years, a zero-plane state is created using a thick polymer brush or the like, and a technical proposal for a cello-plane anchoring IPS mode has been made (reference 2). With this technology, the contrast ratio is significantly improved and the drive voltage is significantly reduced.

Japanese Patent No. 4053530 JP, 2013-231757, A

On the other hand, there is a problem that occurs in principle in this technology. Firstly, it is necessary to carry out under extremely delicate conditions in order to stably generate the polymer brush on the substrate, and it is not realistic considering mass production. There is no thing. Secondly, the alignment film has an important function of suppressing image sticking, but it is difficult to control the electrical properties required when using a polymer brush or the like. Thirdly, the response speed when the voltage is turned off is very slow due to the driving principle. It is expected that by reducing the alignment control force to zero, the resistance applied to the liquid crystal during driving will be drastically lowered and the brightness will be improved by reducing the alignment failure area during driving. With regard to (2), since the power for returning the liquid crystal depends on the elastic force of the liquid crystal, it is considered that the speed is greatly reduced as compared with the case where the alignment film is provided.
If such a technical problem can be solved, it will be a great cost advantage for a panel maker, and it can be considered to have a merit in suppressing battery consumption and improving image quality.
The present invention has been made to solve the above problems, a manufacturing method applying a polymer stabilization technology capable of manufacturing a zero plane anchoring film, and a simple and inexpensive method at room temperature. It is an object of the present invention to provide a lateral electric field liquid crystal display device and a method for manufacturing the same, which can simultaneously realize non-contact alignment, lower driving voltage, and faster response speed when off.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved, and have completed the present invention having the following points.

（式［Ｘ−１］〜［Ｘ−１８］中、＊は化合物分子の重合性反応基以外の部分との結合部位を示し、Ｓ^１、Ｓ^２はそれぞれ独立して−Ｏ−、−ＮＲ−、−Ｓ−を表し、Ｒは水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基を表し、Ｒ^１，Ｒ^２はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜４のアルキル基を表す）

（式［Ｗ］、［Ｙ］、［Ｚ］中、＊は化合物分子の重合性反応基以外の部分との結合部位を示し、Ａｒは有機基及び／又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、Ｒ^９及びＲ^１０は、それぞれ独立に、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基を表し、Ｒ^９とＲ^１０がアルキル基の場合、末端で互いに結合し環構造を形成していても良い。Ｑは下記の構造を表す。

（式中、Ｒ^１１は−ＣＨ_２−、−ＮＲ−、−Ｏ−、又は−Ｓ−を表し、Ｒは水素原子又は炭素原子数１〜４のアルキル基を表し、＊は化合物分子のＱ以外の部分との結合部位を示す。）
Ｒ^１２は水素原子、ハロゲン原子、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基を表す。）
［９］ 前記ラジカル重合を誘発する有機基を含有するジアミンが下記一般式（６）又は下記一般式（７）で表される構造を有するジアミンであることを特徴とする［７］記載の方法。

（式（６）中、Ｒ^６は単結合、−ＣＨ_２−、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＮＨ−、−ＣＨ_２Ｏ−、−Ｎ（ＣＨ_３）−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−を表し、
Ｒ^７は単結合、又は非置換もしくはフッ素原子によって置換されている炭素数１〜２０のアルキレン基を表し、当該アルキレン基の任意の−ＣＨ_２−又は−ＣＦ_２−の１以上は、それぞれ独立に−ＣＨ＝ＣＨ−、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、又は−ＮＨ−が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよい；
Ｒ^８は、下記式:

から選択されるラジカル重合反応性基を表す。
（式［Ｘ−１］〜［Ｘ−１８］中、＊は化合物分子のラジカル重合反応性基以外の部分との結合部位を示し、Ｓ^１、Ｓ^２はそれぞれ独立して−Ｏ−、−ＮＲ−、−Ｓ−を表し、Ｒは水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基を表し、Ｒ^１，Ｒ^２はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜４のアルキル基を表す）)

（式（７）中、Ｔ^１及びＴ^２は、それぞれ独立に、単結合、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＮＨ−、−ＣＨ_２Ｏ−、−Ｎ（ＣＨ_３）−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−であり、
Ｓは単結合、又は非置換もしくはフッ素原子によって置換されている炭素数１〜２０のアルキレン基を表し、当該アルキレン基の任意の−ＣＨ_２−又は−ＣＦ_２−の１以上は、それぞれ独立に−ＣＨ＝ＣＨ−、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、又は−ＮＨ−が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよく、
Ｊは下記式で表される有機基であり、

（式［Ｗ］、［Ｙ］、［Ｚ］中、＊はＴ^２との結合箇所を表し、Ａｒは有機基及び／又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、Ｒ^９及びＲ^１０は、それぞれ独立に、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基を表し、Ｑは下記の構造を表す。

（式中、Ｒ^１１は−ＣＨ_２−、−ＮＲ−、−Ｏ−、又は−Ｓ−を表し、Ｒは水素原子又は炭素原子数１〜４のアルキル基を表し、＊は化合物分子のＱ以外の部分との結合部位を示す。）
Ｒ^１２は水素原子、ハロゲン原子、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基を表す。）)
［１０］ 前記ラジカル重合性化合物のうち少なくとも一種が、液晶と相溶性を有する、一分子中に一個の重合性反応基を有する化合物である、［１］〜［９］のいずれか一項に記載の方法。
［１１］ 前記ラジカル重合性化合物の重合性反応基が以下の構造から選ばれる、［１０］に記載の方法。

（式中、＊は化合物分子の重合性反応基以外の部分との結合部位を示す。Ｒ^ｂは炭素数２〜８の直鎖アルキル基を表し、Ｅは単結合、−Ｏ−、−ＮＲ^ｃ−、−Ｓ−、エステル結合及びアミド結合から選ばれる結合基を表す。Ｒ^ｃは水素原子、炭素数１〜４のアルキル基を示す。）
［１２］ 前記液晶及びラジカル重合性化合物を含有する液晶組成物において、前記ラジカル重合性化合物を重合させて得られるポリマーのＴｇが１００℃以下のものになるラジカル重合性化合物を含有する液晶組成物を用いることを特徴とする［１］〜［１１］のいずれか一項に記載の方法。
［１３］ ラジカル発生膜を有する第一基板と、ラジカル発生膜を有していてもよい第二基板とを用意するステップ、
第一基板上のラジカル発生膜が第二基板に対向するようにセルを作成するステップ、および、
第一基板と第二基板との間に、液晶及びラジカル重合性化合物を含有する液晶組成物を充填するステップを含み、
［１］〜［１２］のいずれか一項に記載の方法を用いる液晶セルの製造方法。
［１４］ 前記第二基板がラジカル発生膜を有さない第二基板である［１３］に記載の液晶セルの製造方法。
［１５］ 前記第二基板が、一軸配向性を有する液晶配向膜がコーティングされた基板であることを特徴とする［１４］に記載の液晶セルの製造方法。
［１６］ 前記一軸配向性を有する液晶配向膜が水平配向用の液晶配向膜であることを特徴とする［１５］に記載の液晶セルの製造方法。
［１７］ 前記ラジカル発生膜を有する第一基板が櫛歯電極を有する基板である［１３］〜［１６］のいずれか一項に記載の液晶セルの製造方法。
［１８］ 液晶及びラジカル重合性化合物を含有し、
前記ラジカル重合性化合物のうち少なくとも一種が、液晶と相溶性を有する、一分子中に一個の重合性反応基を有する化合物であり、
重合性反応基が以下の構造から選ばれる、液晶組成物。

（式中、＊は化合物分子の重合性反応基以外の部分との結合部位を示す。Ｒ^ｂは炭素数２〜８の直鎖アルキル基を表し、Ｅは単結合、−Ｏ−、−ＮＲ^ｃ−、−Ｓ−、エステル結合及びアミド結合から選ばれる結合基を表す。Ｒ^ｃは水素原子、炭素数１〜４のアルキル基を示す。）
［１９］ ［１］〜［１７］のいずれか一項に記載の方法を用いて得られたゼロ面アンカリング状態を作り出す膜を用いる液晶表示素子の製造方法。
［２０］ ［１９］記載の方法を用いて得られた液晶表示素子。
［２１］ 第一基板又は第二基板が電極を有する、［２０］に記載の液晶表示素子。
［２２］ 低電圧駆動横電界液晶表示素子である、［２０］又は［２１］に記載の液晶表示素子。That is, the present invention includes the following.
[1] A zero-plane anchor including a step of applying sufficient energy for causing a polymerization reaction of the radical-polymerizable compound in a state where the liquid-crystal composition containing the liquid crystal and the radical-polymerizable compound is brought into contact with the radical-generating film. Ring film manufacturing method.
[2] The method according to [1], wherein the radical generating film of the first substrate is a uniaxially oriented radical generating film.
[3] The method according to [1] or [2], wherein the step of applying energy is performed without an electric field.
[4] The method according to any one of [1] to [3], wherein the radical generating film is a film formed by fixing an organic group that induces radical polymerization.
[5] The radical-generating film is obtained by applying a composition of a compound having a radical-generating group and a polymer to form a film and fixing the composition in the film. The method according to any one of [1] to [3].
[6] The method according to any one of [1] to [3], wherein the radical generating film is made of a polymer containing an organic group that induces radical polymerization.
[7] The polymer containing an organic group that induces radical polymerization is selected from a polyimide precursor, a polyimide, a polyurea and a polyamide obtained by using a diamine component containing a diamine containing an organic group that induces radical polymerization. The method according to [6], which is at least one polymer.
[8] The organic group that induces radical polymerization is an organic group represented by the following structures [X-1] to [X-18], [W], [Y], and [Z] [4], [ 6] and the method according to any one of [7].

(In the formulas [X-1] to [X-18], * represents a binding site to a part other than the polymerizable reactive group of the compound molecule, and S ¹ and S ² are each independently —O— or —NR. Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom or halogen. Atom, represents an alkyl group having 1 to 4 carbon atoms)

(In the formulas [W], [Y], and [Z], * represents a binding site to a portion of the compound molecule other than the polymerizable reactive group, and Ar has an organic group and / or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, wherein R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. When R ⁹ and R ¹⁰ are alkyl groups, they may be bonded to each other at the ends to form a ring structure, and Q represents the following structure.

(In the formula, R ¹¹ represents —CH ₂ —, —NR—, —O—, or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents Q of the compound molecule. Shows the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )
[9] The method according to [7], wherein the diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7). ..

(In the formula (6), R ⁶ is a single bond, —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N. _{(CH 3) -, - CON} (CH 3) -, or -N _(CH 3) CO- represents,
R ⁷ represents a single bond, or an alkylene group having 1 to 20 carbon atoms, which is unsubstituted or substituted by a fluorine atom, and any one or more of —CH ₂ — or —CF ₂ — of the alkylene group is independent. May be replaced with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, i.e., -O-, -COO- , -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups provided that they are not adjacent to each other;
R ⁸ is the following formula:

Represents a radical polymerization reactive group selected from
(In the formulas [X-1] to [X-18], * represents a binding site to a moiety other than the radical-polymerization reactive group of the compound molecule, and S ¹ and S ² are independently -O- and-. NR- and -S- are represented, R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, R ¹ and R ² are each independently a hydrogen atom, Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms))

(In Formula (7), T ¹ and T ² are each independently a single bond, —O—, —S—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —. _{CH 2 O -, - N (} CH 3) -, - CON (CH 3) -, or -N _(CH 3) a CO-,
S represents a single bond or an alkylene group having 1 to 20 carbon atoms, which is unsubstituted or substituted by a fluorine atom, and any one or more of —CH ₂ — or —CF ₂ — of the alkylene group is independently. It may be substituted with a group selected from —CH═CH—, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, namely, —O—, —COO—, -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups provided that they are not adjacent to each other,
J is an organic group represented by the following formula,

(In the formulas [W], [Y], and [Z], * represents a bonding site with T ^2, and Ar represents phenylene, naphthylene, and biphenylene which may have an organic group and / or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group consisting of, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q is the structure below. Represents.

(In the formula, R ¹¹ represents —CH ₂ —, —NR—, —O—, or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents Q of the compound molecule. Shows the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ))
[10] In any one of [1] to [9], at least one of the radically polymerizable compounds is a compound having compatibility with a liquid crystal and having one polymerizable reactive group in one molecule. The method described.
[11] The method according to [10], wherein the polymerizable reactive group of the radically polymerizable compound is selected from the following structures.

(In the formula, * represents a binding site to a portion other than the polymerizable reactive group of the compound molecule. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, —O—, —NR. represents a linking group selected from ^c- , -S-, an ester bond and an amide bond. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
[12] A liquid crystal composition containing a liquid crystal and a radical polymerizable compound, wherein the polymer obtained by polymerizing the radical polymerizable compound has a Tg of 100 ° C. or less. Is used, The method as described in any one of [1]-[11].
[13] a step of preparing a first substrate having a radical generating film and a second substrate which may have a radical generating film,
Creating a cell so that the radical-generating film on the first substrate faces the second substrate, and
Between the first substrate and the second substrate, including a step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound,
A method for manufacturing a liquid crystal cell, which uses the method according to any one of [1] to [12].
[14] The method for producing a liquid crystal cell according to [13], wherein the second substrate is a second substrate having no radical generating film.
[15] The method for producing a liquid crystal cell according to [14], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial orientation.
[16] The method for producing a liquid crystal cell according to [15], wherein the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment.
[17] The method for producing a liquid crystal cell according to any one of [13] to [16], wherein the first substrate having the radical generating film is a substrate having comb-teeth electrodes.
[18] containing a liquid crystal and a radically polymerizable compound,
At least one of the radically polymerizable compounds is a compound having compatibility with liquid crystal, having one polymerizable reactive group in one molecule,
A liquid crystal composition in which the polymerizable reactive group is selected from the following structures.

(In the formula, * represents a binding site to a portion other than the polymerizable reactive group of the compound molecule. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, —O—, —NR. represents a linking group selected from ^c- , -S-, an ester bond and an amide bond. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
[19] A method for manufacturing a liquid crystal display device, which uses a film that produces a zero-plane anchoring state, which is obtained by using the method according to any one of [1] to [17].
[20] A liquid crystal display device obtained by using the method described in [19].
[21] The liquid crystal display element according to [20], wherein the first substrate or the second substrate has an electrode.
[22] The liquid crystal display element according to [20] or [21], which is a low-voltage driven horizontal electric field liquid crystal display element.

  According to the present invention, a zero plane anchoring film can be industrially produced with a high yield. By using the method of the present invention, a liquid crystal display element similar to the zero-plane anchoring IPS mode liquid crystal display element described in Patent Documents 1 and 2 can be easily manufactured with inexpensive raw materials and existing manufacturing methods. In addition, the liquid crystal display device obtained by the manufacturing method of the present invention has excellent characteristics that the response speed of the liquid crystal at the time of Off is faster than that of the prior art, and that the driving voltage is low, there is no bright spot, and Vcom shift does not easily occur. It is possible to provide a liquid crystal display device having the same.

  The present invention is a method for producing a zero-plane anchoring film, which comprises polymerizing a polymerizable compound by UV or heat in a state where a liquid crystal containing a specific polymerizable compound is brought into contact with the radical generating film. More specifically, a cell having a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between a first substrate having a radical generating film and a second substrate that may have a radical generating film is prepared. And a step of applying sufficient energy to the cell to cause a polymerization reaction of the radically polymerizable compound, and a method for producing a zero-plane anchoring film. Preferably, a step of preparing a first substrate having a radical generating film and a second substrate having no radical generating film, a step of forming a cell so that the radical generating film faces the second substrate, and A method for producing a liquid crystal cell, comprising a step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between a first substrate and a second substrate. For example, a low-voltage driven IPS liquid crystal display device in which the second substrate is a substrate having a radical-generating film and a uniaxially aligned liquid crystal alignment film, and the first substrate is a substrate having comb-teeth electrodes. It is a creation method.

  In the present invention, the "zero plane anchoring film" means that there is no alignment regulating force of liquid crystal molecules in the in-plane direction, or if any, it is weaker than the intermolecular force between liquid crystals. A film that is not uniaxially oriented in the direction of. Further, the zero-plane anchoring film is not limited to the solid film, and includes a liquid film covering the solid surface. Normally, in a liquid crystal display element, a film that controls the alignment of liquid crystal molecules, that is, a liquid crystal alignment film is used as a pair to orient the liquid crystal, but even when this zero-plane anchoring film and the liquid crystal alignment film are used as a pair, the liquid crystal is aligned. It can be oriented. This is because the alignment control force of the liquid crystal alignment film is also transmitted in the thickness direction of the liquid crystal layer by the intermolecular force between the liquid crystal molecules, and as a result, the liquid crystal molecules adjacent to the zero plane anchoring film are also aligned. Therefore, when a liquid crystal alignment film for horizontal alignment is used as the liquid crystal alignment film, a horizontal alignment state can be created in the entire liquid crystal cell. The horizontal alignment refers to a state in which the long axes of liquid crystal molecules are aligned substantially parallel to the surface of the liquid crystal alignment film, and a tilted alignment of about several degrees is also included in the category of horizontal alignment.

[Radical generating film forming composition]
The radical-generating film-forming composition for forming the radical-generating film used in the present invention contains, as a component, a polymer and a group capable of generating a radical. At that time, the composition may contain a polymer having a radical-generating group bonded thereto, or a composition of a compound having a radical-generating group and a polymer serving as a base resin. It may be a thing. By coating and curing such a composition to form a film, a radical-generating film in which radical-generating groups are immobilized in the film can be obtained. The group capable of generating a radical is preferably an organic group that induces radical polymerization.

（式［Ｘ−１］〜［Ｘ−１８］中、＊は化合物分子の重合性反応基以外の部分との結合部位を示し、Ｓ^１、Ｓ^２はそれぞれ独立して−Ｏ−、−ＮＲ−、−Ｓ−を表し、Ｒは水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基を表し、Ｒ^１，Ｒ^２はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜４のアルキル基を表す）

（式［Ｗ］、［Ｙ］、［Ｚ］中、＊は化合物分子の重合性反応基以外の部分との結合部位を示し、Ａｒは有機基及び／又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、Ｒ^９及びＲ^１０は、それぞれ独立に、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基を表し、Ｒ^９とＲ^１０がアルキル基の場合、末端で互いに結合し環構造を形成していても良い。Ｑは下記の構造を表す。

（式中、Ｒ^１１は−ＣＨ_２−、−ＮＲ−、−Ｏ−、又は−Ｓ−を表し、Ｒは水素原子又は炭素原子数１〜４のアルキル基を表し、＊は化合物分子のＱ以外の部分との結合部位を示す。）
Ｒ^１２は水素原子、ハロゲン原子、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基を表す。）Examples of such an organic group that induces radical polymerization include organic groups represented by the following structures [X-1] to [X-18], [W], [Y], and [Z]. Be done.

(In the formulas [X-1] to [X-18], * represents a binding site to a part other than the polymerizable reactive group of the compound molecule, and S ¹ and S ² are each independently —O— or —NR. Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom or halogen. Atom, represents an alkyl group having 1 to 4 carbon atoms)

(In the formulas [W], [Y], and [Z], * represents a binding site to a portion of the compound molecule other than the polymerizable reactive group, and Ar has an organic group and / or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, wherein R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. When R ⁹ and R ¹⁰ are alkyl groups, they may be bonded to each other at the ends to form a ring structure, and Q represents the following structure.

(In the formula, R ¹¹ represents —CH ₂ —, —NR—, —O—, or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents Q of the compound molecule. Shows the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )

  As the polymer, for example, a polyimide precursor and at least one polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate and the like are preferable.

  In order to obtain a radical-generating film used in the present invention, when a polymer having an organic group that induces radical polymerization is used, in order to obtain a polymer having a group capable of generating a radical, a methacryl group as a monomer component, A monomer having a photoreactive side chain containing at least one selected from an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group, and a side chain at a site that generates a radical by decomposing by ultraviolet irradiation It is preferable that the monomer is used. On the other hand, a monomer that generates a radical may have a problem that it spontaneously polymerizes, and becomes an unstable compound. Therefore, it has a radical generation site in terms of ease of synthesis. Polymers derived from diamines are preferable, and more preferable are polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, polyurea, and polyamide.

（式（６）中、Ｒ^６は単結合、−ＣＨ_２−、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＮＨ−、−ＣＨ_２Ｏ−、−Ｎ（ＣＨ_３）−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−を表し、
Ｒ^７は単結合、又は非置換もしくはフッ素原子によって置換されている炭素数１〜２０のアルキレン基を表し、当該アルキレン基の任意の−ＣＨ_２−又は−ＣＦ_２−の１以上は、それぞれ独立に−ＣＨ＝ＣＨ−、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、又は−ＮＨ−が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよい；
Ｒ^８は、下記式:

から選択されるラジカル重合反応性基を表す。
（式［Ｘ−１］〜［Ｘ−１８］中、＊は化合物分子のラジカル重合反応性基以外の部分との結合部位を示し、Ｓ^１、Ｓ^２はそれぞれ独立して−Ｏ−、−ＮＲ−、−Ｓ−を表し、Ｒは水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基を表し、Ｒ^１，Ｒ^２はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜４のアルキル基を表す）Such a radical-generating site-containing diamine is specifically, for example, a diamine having a side chain capable of generating radicals and polymerizing, and examples thereof include a diamine represented by the following general formula (6). , But is not limited to this.

(In the formula (6), R ⁶ is a single bond, —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N. _{(CH 3) -, - CON} (CH 3) -, or -N _(CH 3) CO- represents,
R ⁷ represents a single bond, or an alkylene group having 1 to 20 carbon atoms, which is unsubstituted or substituted by a fluorine atom, and any one or more of —CH ₂ — or —CF ₂ — of the alkylene group is independent. May be replaced with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, i.e., -O-, -COO- , -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups provided that they are not adjacent to each other;
R ⁸ is the following formula:

Represents a radical polymerization reactive group selected from
(In the formulas [X-1] to [X-18], * represents a binding site to a moiety other than the radical-polymerization reactive group of the compound molecule, and S ¹ and S ² are independently -O- and-. NR- and -S- are represented, R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, R ¹ and R ² are each independently a hydrogen atom, Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms)

The bonding positions of the two amino groups (—NH ₂ ) in formula (6) are not limited. Specifically, with respect to the bonding group of the side chain, 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,4 position on the benzene ring. 5 positions. Above all, from the viewpoint of reactivity when synthesizing the polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferable. Considering the ease of synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.

（式中、Ｊ^１は単結合、−Ｏ−、−ＣＯＯ−、−ＮＨＣＯ−、又は−ＮＨ−より選ばれる結合基であり、Ｊ^２は単結合、又は非置換もしくはフッ素原子によって置換されている炭素数１〜２０のアルキレン基を表す。）Specific examples of the diamine having a photoreactive group containing at least one selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group are as follows. Compounds include, but are not limited to.

(In the formula, J ¹ is a single bond, a bonding group selected from —O—, —COO—, —NHCO—, or —NH—, and J ² is a single bond or unsubstituted or substituted with a fluorine atom. Represents an alkylene group having 1 to 20 carbon atoms.)

（式（７）中、Ｔ^１及びＴ^２は、それぞれ独立に、単結合、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＮＨ−、−ＣＨ_２Ｏ−、−Ｎ（ＣＨ_３）−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−であり、
Ｓは単結合、又は非置換もしくはフッ素原子によって置換されている炭素数１〜２０のアルキレン基を表し、当該アルキレン基の任意の−ＣＨ_２−又は−ＣＦ_２−の１以上は、それぞれ独立に−ＣＨ＝ＣＨ−、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−、又は−ＮＨ−が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよく、
Ｊは下記式で表される有機基であり、

（式［Ｗ］、［Ｙ］、［Ｚ］中、＊はＴ^２との結合箇所を表し、Ａｒは有機基及び／又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、Ｒ^９及びＲ^１０は、それぞれ独立に、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基を表し、Ｑは下記の構造を表す。

（式中、Ｒ^１１は−ＣＨ_２−、−ＮＲ−、−Ｏ−、又は−Ｓ−を表し、Ｒは水素原子又は炭素原子数１〜４のアルキル基を表し、＊は化合物分子のＱ以外の部分との結合部位を示す。）
Ｒ^１２は水素原子、ハロゲン原子、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基を表す。））Examples of the diamine having a side chain having a site where a radical is generated by being decomposed by irradiation with ultraviolet rays include, but are not limited to, the diamine represented by the following general formula (7).

(In Formula (7), T ¹ and T ² are each independently a single bond, —O—, —S—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —. _{CH 2 O -, - N (} CH 3) -, - CON (CH 3) -, or -N _(CH 3) a CO-,
S represents a single bond or an alkylene group having 1 to 20 carbon atoms, which is unsubstituted or substituted by a fluorine atom, and any one or more of —CH ₂ — or —CF ₂ — of the alkylene group is independently. It may be substituted with a group selected from —CH═CH—, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, namely, —O—, —COO—, -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups provided that they are not adjacent to each other,
J is an organic group represented by the following formula,

(In the formulas [W], [Y], and [Z], * represents a bonding site with T ^2, and Ar represents phenylene, naphthylene, and biphenylene which may have an organic group and / or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group consisting of, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q is the structure below. Represents.

(In the formula, R ¹¹ represents —CH ₂ —, —NR—, —O—, or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents Q of the compound molecule. Shows the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ))

The bonding positions of the two amino groups (—NH ₂ ) in the above formula (7) are not limited. Specifically, with respect to the bonding group of the side chain, 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,4 position on the benzene ring. 5 positions. Above all, from the viewpoint of reactivity when synthesizing the polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferable. Considering the ease of synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.

（式中、ｎは２〜８の整数である。）In particular, the structure represented by the following formula is most preferable in view of ease of synthesis, high versatility, characteristics, etc., but is not limited thereto.

(In the formula, n is an integer of 2 to 8.)

  The above diamines may be used alone or in combination of two or more, depending on the liquid crystal orientation when used as a radical generating film, sensitivity in polymerization reaction, voltage holding characteristics, accumulated charge and the like.

  The diamine having a site where such radical polymerization occurs is preferably used in an amount of 5 to 50 mol% of the total diamine component used in the synthesis of the polymer contained in the radical-generating film forming composition, and more preferably It is 10 to 40 mol%, and particularly preferably 15 to 30 mol%.

  When the polymer used for the radical-generating film of the present invention is obtained from diamine, other diamines other than the diamine having a site where the radical is generated are used together as a diamine component unless the effects of the present invention are impaired. be able to. Specifically, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl , 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3 ' -Trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'- Diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, 2,3′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether , 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) Silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, 3,3′-thiodianiline, 4,4 '-Diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine , N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3 '-Diaminodiphenyl) amine, 4,4'-diamino Benzophenone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1, 6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2 -Bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1 , 4-bis (4aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-amino) Benzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′-[1,4-phenylenebis (methylene)] dianiline, 4,4 ′-[1,3-phenylenebis (methylene) ] Dianiline, 3,4 '-[1,4-phenylenebis (methylene)] dianiline, 3,4'-[1,3-phenylenebis (methylene)] dianiline, 3,3 '-[1,4-phenylene Bis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3 -Aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate ), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, Bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-aminobenzamide) ), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N ′-(1, 3-phenylene) bis (3-aminobenzamide), N, N'-bis (4-aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'-bis (4 -Aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-amino Phenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4 -Aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, trans-1,4-bis (4-aminophenyl) ) Cyclohexane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis (4-aminophenoxy) methane, 1,2-bis (4-aminophenoxy) ethane, 1,3-bis (4-amino) Phenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4 -Aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7 -Bis (4-aminophenoxy) heptane, 1,7-bis (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1 , 9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, 1,10-bis (3-aminophenoxy) decane 1,11-bis (4-aminophenoxy) undecane, 1,11-bis (3-amino Aromatic diamines such as phenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane and 1,12-bis (3-aminophenoxy) dodecane; bis (4-aminocyclohexyl) methane, bis (4-amino-) Alicyclic diamines such as 3-methylcyclohexyl) methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 , 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and the like; 1,3-bis [2- (p-amino) Diamine having urea structure such as phenyl) ethyl] urea and 1,3-bis [2- (p-aminophenyl) ethyl] -1-tert-butyloxycarbonylurea; Np-aminophenyl-4-p- A diamine having a nitrogen-containing unsaturated heterocyclic structure such as aminophenyl (tertiarybutyloxycarbonyl) aminomethylpiperidine; N-tert-butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4 Examples include diamines having an N-Boc group such as -aminobenzyl) amine.

  The above-mentioned other diamines may be used alone or in combination of two or more, depending on liquid crystal orientation when used as a radical generating film, sensitivity in polymerization reaction, voltage holding characteristics, accumulated charge and the like. ..

  In the synthesis when the polymer is a polyamic acid, the tetracarboxylic dianhydride to be reacted with the above diamine component is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ′, 4,4′-biphenyl tetracarboxylic acid, 2,3,3 ′, 4′-biphenyl Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-di) Carboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) Propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4) -Dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4- Cyclobutanetetracarboxylic acid, oxydiphthaltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid Acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl -1,2,3,4-Cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1- Cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [3,3,0] octane-2 , 4,6,8-Tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,7,9 -Tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2,6>] Undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydrinaphthalene-1,2-dicarboxylic acid, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-Methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0 <2,7>] dodeca-4,5,9,10-tetracarboxylic acid, 3 5,5,6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and other tetracarboxylic acid dianhydrides.

  Of course, the tetracarboxylic dianhydride may be used alone or in combination of two or more depending on the liquid crystal orientation when used as a radical generating film, the sensitivity in the polymerization reaction, the voltage holding characteristic, the accumulated charge and the like. ..

In the synthesis when the polymer is a polyamic acid ester, the structure of the tetracarboxylic acid dialkyl ester to be reacted with the diamine component is not particularly limited, but specific examples thereof are given below.
Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, and 1 , 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2, 3,4-Cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1 -Cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-butane tetracarboxylic acid dialkyl ester, bicyclo [3 , 3,0] Octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetic acid dialkyl ester , Cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 <2,5>] nonane-3, 4,7,8-Tetracarboxylic acid-3,4: 7,8-dialkyl ester, hexacyclo [6.6.0.1 <2,7>. 0 <3,6>. 1 <9,14>. 0 <10,13>] hexadecane-4,5,11,12-tetracarboxylic acid-4,5,11,12-dialkyl ester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester and the like can be mentioned.

  Examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyltetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-biphenyltetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ′, 4′-benzophenone tetracarboxylic acid dialkyl ester, Bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7 -Naphthalene tetracarboxylic acid dialkyl ester and the like.

式中Ｒ^２２、Ｒ^２３は炭素数１〜１０の脂肪族炭化水素を表す。In the synthesis in the case where the polymer is polyurea, the diisocyanate to be reacted with the diamine component is not particularly limited and can be used depending on availability and the like. The specific structure of diisocyanate is shown below.

In the formula, R ²² and R ²³ represent an aliphatic hydrocarbon having 1 to 10 carbon atoms.

The aliphatic diisocyanates represented by K-1 to K-5 are inferior in reactivity, but have an advantage of improving solvent solubility, and the aromatic diisocyanates represented by K-6 to K-7 are highly reactive and have heat resistance. However, there is a drawback that the solvent solubility is lowered. From the viewpoint of versatility and characteristics, K-1, K-7, K-8, K-9, and K-10 are particularly preferable, K-12 is added from the viewpoint of electric characteristics, and K-13 is added from the viewpoint of liquid crystal alignment. Particularly preferred. One or more diisocyanates may be used in combination, and various applications are preferable depending on the desired properties.
Further, it is also possible to replace some of the diisocyanate with the tetracarboxylic acid dianhydride described above, may be used in the form of a copolymer of polyamic acid and polyurea, of the polyimide and polyurea by chemical imidization. You may use it in the form of a copolymer.

  In the synthesis when the polymer is a polyamide, the structure of the dicarboxylic acid to be reacted is not particularly limited, but the following are specific examples of them. Specific examples of the aliphatic dicarboxylic acid include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2- Dicarboxylic acids such as dimethyl glutaric acid, 3,3-diethyl succinic acid, azelaic acid, sebacic acid and suberic acid can be mentioned.

  Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid and 1,3-cyclobutanedicarboxylic acid. Acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid Acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1,4-dicarboxylic acid, bicyclo [2.2.2] Octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo [2.2.2] octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8- Examples thereof include dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro [3.3] heptanedicarboxylic acid, 1,3-adamantanediacetic acid and camphoric acid.

  Aromatic dicarboxylic acids include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid. Acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4 -Anthraquinone dicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4 "-terphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4 , 4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 4,4'-transdicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-dithiodibenzoic acid, p- Phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3 '-[4,4'-(methylenedi-p-phenylene)] dipropion Acid, 4,4 ′-[4,4 ′-(oxydi-p-phenylene)] dipropionic acid, 4,4 ′-[4,4 ′-(oxydi-p-phenylene)] dibutyric acid, (isopropylidene) Examples thereof include dicarboxylic acids such as dendi-p-phenylenedioxy) dibutyric acid and bis (p-carboxyphenyl) dimethylsilane.

  Examples of the dicarboxylic acid containing a heterocycle include 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2, Examples thereof include 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid and 3,5-pyridinedicarboxylic acid.

  The above various dicarboxylic acids may have an acid dihalide or anhydrous structure. These dicarboxylic acids are particularly preferably dicarboxylic acids capable of giving a polyamide having a linear structure, from the viewpoint of maintaining the orientation of liquid crystal molecules. Among these, terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylethanedicarboxylic acid, 4,4 '-Diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propanedicarboxylic acid, 4,4-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 5-Pyridinedicarboxylic acid or these acid dihalides are preferably used. Some of these compounds have isomers, but they may be a mixture containing them. Moreover, you may use together 2 or more types of compounds. The dicarboxylic acids used in the present invention are not limited to the above exemplified compounds.

  It is selected from the raw material diamine (also referred to as "diamine component") and the raw material tetracarboxylic dianhydride (also referred to as "tetracarboxylic dianhydride component"), tetracarboxylic acid diester, diisocyanate and dicarboxylic acid. A known synthetic method can be used to obtain a polyamic acid, a polyamic acid ester, a polyurea, or a polyamide by the reaction with the components. Generally, it is a method in which a diamine component and one or more components selected from tetracarboxylic dianhydride component, tetracarboxylic acid diester, diisocyanate and dicarboxylic acid are reacted in an organic solvent.

  The reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and that by-products are not generated.

  The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the produced polymer. Furthermore, even an organic solvent in which the polymer is not dissolved may be used as a mixture with the above-mentioned solvent as long as the produced polymer is not deposited. Since water in the organic solvent hinders the polymerization reaction and causes hydrolysis of the produced polymer, it is preferable to use dehydrated and dried organic solvent.

  Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2 -Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ- Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether. , Dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, Ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether Tellurium, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 -Methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl- 2-Pentanone, 2-ethyl-1-hexanol and the like can be mentioned. These organic solvents may be used alone or in combination.

  When the diamine component and the tetracarboxylic acid dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid dianhydride component is used as it is, or organically. Method of dispersing or dissolving in a solvent and adding, conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a tetracarboxylic acid dianhydride component and a diamine component Examples thereof include a method of alternately adding, and any of these methods may be used. Further, when the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually and sequentially reacted, and may be further individually reacted to have a low molecular weight. The body may be mixed and reacted to form a high molecular weight body.

  The temperature for reacting the diamine component and the tetracarboxylic dianhydride component can be selected at any temperature, and is, for example, in the range of -20 to 100 ° C, preferably -5 to 80 ° C. The reaction can be carried out at any concentration, and for example, the total amount of the diamine component and the tetracarboxylic dianhydride component with respect to the reaction solution is 1 to 50% by mass, preferably 5 to 30% by mass. ..

  In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected to any value depending on the molecular weight of the polyamic acid to be obtained. Similar to the ordinary polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced. The preferable range is 0.8 to 1.2.

  The method for synthesizing the polymer used in the present invention is not limited to the above method, and when synthesizing a polyamic acid, similar to a general polyamic acid synthesis method, the above tetracarboxylic dianhydride is used. Alternatively, the corresponding polyamic acid can also be obtained by using a tetracarboxylic acid derivative having a corresponding structure or a tetracarboxylic acid derivative such as a tetracarboxylic acid dihalide and reacting by a known method. When synthesizing polyurea, diamine and diisocyanate may be reacted. When producing a polyamic acid ester or polyamide, a diamine, a component selected from tetracarboxylic acid diester and dicarboxylic acid, in the presence of a known condensing agent, or, after induction into an acid halide by a known method , It may be reacted with a diamine.

  Examples of the method for imidizing the above polyamic acid to form a polyimide include thermal imidization in which the solution of polyamic acid is heated as it is and catalytic imidization in which a catalyst is added to the solution of polyamic acid. The imidation ratio of polyamic acid to polyimide is preferably 30% or more, and more preferably 30 to 99%, because the voltage holding ratio can be increased. On the other hand, 70% or less is preferable from the viewpoint of whitening characteristics, that is, from the viewpoint of suppressing precipitation of the polymer in the varnish. Taking both characteristics into consideration, 40 to 80% is more preferable.

  The temperature at which the polyamic acid is subjected to thermal imidization in a solution is usually 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to remove water generated by the imidization reaction outside the system.

  Catalytic imidization of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring the mixture at usually -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is usually 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is usually 1 to 50 mol times of the amic acid group, preferably It is 3 to 30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferable because purification after the reaction is easy. The imidization ratio by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time, and the like.

  When the produced polymer is recovered from the reaction solution of the polymer, the reaction solution may be poured into a poor solvent to cause precipitation. Examples of the poor solvent used for forming the precipitate include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by pouring it into a poor solvent can be collected by filtration and then dried at room temperature or under normal pressure or reduced pressure by heating. Further, by repeating the operation of re-dissolving the precipitated and recovered polymer in an organic solvent and re-precipitating and recovering it 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of poor solvents selected from these, because the purification efficiency is further improved.

  When the radical-generating film is composed of a polymer containing an organic group that induces radical polymerization, the radical-generating film-forming composition used in the present invention contains a polymer other than a polymer containing an organic group that induces radical polymerization. It may contain other polymers. At that time, the content of the other polymer in all the components of the polymer is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.

  The molecular weight of the polymer contained in the composition for forming a radical-generating film is determined by GPC (GPC (GPC) considering the strength of the radical-generating film obtained by coating the radical-generating film, workability during coating film formation, uniformity of the coating film, The weight average molecular weight measured by the Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

  The radical-generating film used in the present invention is a polymer in the case of being obtained by applying a composition of a compound having a radical-generating group and a polymer, and curing the composition to form a film to be immobilized in the film. , A polyimide precursor produced according to the above production method, and a polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc., wherein the diamine having a site where radical polymerization occurs It is also possible to use at least one polymer obtained by using a diamine component that is 0 mol% of the entire diamine component used for the synthesis of the polymer contained in the radical-generating film forming composition. Examples of the compound having a radical-generating group added at that time include the following.

  The compound that generates a radical by heat is a compound that generates a radical when heated to a temperature equal to or higher than the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxides). Hydrogen, tert-butyl hydroxide peroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane) Etc.), alkyl peresters (peroxy neodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, Sodium persulfate, ammonium persulfate, etc.) and azo compounds (azobisisobutyronitrile, 2,2′-di (2-hydroxyethyl) azobisisobutyronitrile, etc.) can be mentioned. Such radical thermal polymerization initiators may be used alone or in combination of two or more.

  The compound that generates a radical by light is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such a radical photopolymerization initiator include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, and 2-hydroxy. -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1,4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate isoamyl, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri ( t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ' , 4'-Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [P-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s- Triazine, 1,3-bis (trichloromethyl) -5- (4′-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2 , 2'-bi Sus (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2 ' -Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2) -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (5-2,4-cyclopentadiene-1- Yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-Tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di ( Methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3- Methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H) -ylidene) -1- (2- Examples thereof include benzoyl) ethanone. These compounds may be used alone or in a mixture of two or more.

  Even when the radical-generating film is made of a polymer containing an organic group that induces radical polymerization, the radical-generating group described above is used for the purpose of promoting radical polymerization when energy is applied. You may include the compound which has.

  The radical-generating film-forming composition may contain an organic solvent that dissolves or disperses a polymer component and, if necessary, a radical generator and other contained components. The organic solvent is not particularly limited, and examples thereof include the organic solvents exemplified in the above-mentioned synthesis of polyamic acid. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like are soluble. From the viewpoint of. Especially, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferable, but two or more kinds of mixed solvents may be used.

  Further, it is preferable to use a solvent which improves the uniformity and smoothness of the coating film, by mixing it with an organic solvent having a high solubility of the components contained in the radical-generating film forming composition.

  As a solvent for improving the uniformity and smoothness of the coating film, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol. Tol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether. , Dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol Monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, Ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate , Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3 -Ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1 − Phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2- Ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, 2-ethyl-1-hexanol and the like can be mentioned. Plural kinds of these solvents may be mixed. When using these solvents, the amount is preferably 5 to 80% by mass, and more preferably 20 to 60% by mass, based on the whole solvent contained in the liquid crystal aligning agent.

  The radical-generating film forming composition may contain components other than the above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when the radical generating film forming composition is applied, compounds that improve the adhesion between the radical generating film forming composition and the substrate, and radical generating film forming. Examples thereof include compounds that further improve the film strength of the composition.

  Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (manufactured by Sumitomo 3M Limited). ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like. When these surfactants are used, the use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0, based on 100 parts by mass of the total amount of the polymer contained in the radical-generating film forming composition. 0.01 to 1 part by mass.

  Specific examples of the compound that improves the adhesiveness between the radical-generating film forming composition and the substrate include functional silane-containing compounds and epoxy group-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. , N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl- 1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane Silane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol , N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-4 4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane and the like can be mentioned.

  Further, in order to further increase the film strength of the radical generating film, a phenol compound such as 2,2′-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol is added. Good. When these compounds are used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the polymer contained in the radical-generating film forming composition. Is.

  Further, in addition to the above, the radical-generating film-forming composition contains a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the radical-generating film, as long as the effects of the present invention are not impaired. Substances may be added.

[Radical generation film]
The radical generating film of the present invention is obtained by using the above radical generating film forming composition. For example, a cured film obtained by applying the composition for forming a radical-generating film used in the present invention to a substrate and then performing drying and baking can be used as it is as a radical-generating film. In addition, rubbing the cured film, irradiating polarized light or light having a specific wavelength, treating with an ion beam, or irradiating the liquid crystal display element after filling the liquid crystal with UV as an alignment film for PSA with UV. Is also possible.

The substrate on which the radical generating film forming composition is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate on which a transparent electrode for driving liquid crystal is formed is preferable.
Specific examples include glass plate, polycarbonate, poly (meth) acrylate, polyether sulfone, polyarylate, polyurethane, polysulfone, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, tri A substrate having a transparent electrode formed on a plastic plate such as acetyl cellulose, diacetyl cellulose, or acetate butyrate cellulose can be used.

For a substrate that can be used for an IPS type liquid crystal display device, an electrode pattern such as a standard IPS comb-teeth electrode or a PSA fishbone electrode or a protrusion pattern such as MVA can be used.
Further, in a high-performance element such as a TFT type element, an element in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.
When a transmissive liquid crystal display element is intended, it is common to use the substrate as described above, but when a reflective liquid crystal display element is intended, if only one substrate is used, silicon is used. An opaque substrate such as a wafer can also be used. At that time, a material such as aluminum that reflects light can be used for the electrodes formed on the substrate.

  Examples of the method for applying the radical-generating film forming composition include a spin coating method, a printing method, an inkjet method, a spray method, and a roll coating method, but from the viewpoint of productivity, the transfer printing method is widely used industrially. Therefore, it is also preferably used in the present invention.

  The step of drying after applying the radical generating film forming composition is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, drying is performed. It is preferable to include a step. This drying may be carried out as long as the solvent is removed to such an extent that the shape of the coating film is not deformed due to transportation of the substrate, and the drying means is not particularly limited. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C. for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.

  The coating film formed by applying the radical-generating film forming composition by the above method can be baked to form a cured film. At that time, the firing temperature may be any temperature generally from 100 ° C to 350 ° C, preferably from 140 ° C to 300 ° C, more preferably from 150 ° C to 230 ° C, further preferably from 160 ° C to 220 ° C. ℃. The firing time can be normally 5 minutes to 240 minutes. It is preferably 10 to 90 minutes, more preferably 20 to 90 minutes. For heating, a generally known method, for example, a hot plate, a hot air circulation oven, an IR oven, a belt furnace or the like can be used.

  The thickness of this cured film can be selected as necessary, but it is preferably 5 nm or more, and more preferably 10 nm or more, since the reliability of the liquid crystal display element is easily obtained. Further, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large, which is preferable.

  Although the first substrate having the radical generating film can be obtained as described above, the radical generating film can be subjected to the uniaxial alignment treatment. Examples of the method for performing the uniaxial alignment treatment include a photoalignment method, an oblique vapor deposition method, rubbing, and a uniaxial alignment treatment with a magnetic field.

  In the case of performing the alignment treatment by performing the rubbing treatment in one direction, for example, the substrate is moved so that the rubbing cloth and the film come into contact with each other while rotating the rubbing roller around which the rubbing cloth is wound. In the case of the first substrate of the present invention in which the comb-teeth electrode is formed, the direction is selected according to the electrical properties of the liquid crystal, but when the liquid crystal having positive dielectric anisotropy is used, the rubbing direction is the comb-teeth electrode. It is preferable that the direction is substantially the same as the extending direction.

  The second substrate of the present invention is the same as the above-mentioned first substrate except that it has no radical-generating film. It is preferable to use a substrate having a conventionally known liquid crystal alignment film.

<Liquid crystal cell>
The liquid crystal cell of the present invention comprises a substrate (first substrate) having the radical generating film and a substrate (second substrate) having a known liquid crystal alignment film after the radical generating film is formed on the substrate by the above method. Is obtained by arranging so that the radical generation film and the liquid crystal alignment film face each other, sandwiching a spacer, fixing with a sealant, and injecting and sealing a liquid crystal composition containing a liquid crystal and a radically polymerizable compound. Be done. At that time, the size of the spacer used is usually 1 to 30 μm, preferably 2 to 10 μm. Further, by making the rubbing direction of the first substrate and the rubbing direction of the second substrate parallel to each other, it can be used in the IPS mode and the FFS mode. If the rubbing directions are orthogonal to each other, the twisted nematic mode can be used. Can be used for
The method of injecting a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is not particularly limited, and a vacuum method of injecting a mixture containing a liquid crystal and a polymerizable compound after reducing the pressure inside the prepared liquid crystal cell, a liquid crystal and a polymerization A dropping method in which sealing is performed after dropping a mixture containing a functional compound can be used.

<Liquid Crystal Composition Containing Liquid Crystal and Radical Polymerizable Compound>
In the production of the liquid crystal display device of the present invention, the polymerizable compound used with the liquid crystal is not particularly limited as long as it is a radically polymerizable compound, for example, a compound having one or two or more polymerizable reactive groups in one molecule. is there. Preferably, it is a compound having one polymerizable reactive group in one molecule (hereinafter, it may be referred to as “compound having a monofunctional polymerizable group”, “compound having a monofunctional polymerizable group”, etc.) .. The polymerizable reactive group is preferably a radical polymerizable reactive group, for example, a vinyl bond.

  At least one of the radically polymerizable compounds is preferably a compound having compatibility with liquid crystal and having one polymerizable reactive group in one molecule, that is, a compound having a monofunctional radically polymerizable group.

（式中、＊は化合物分子の重合性反応基以外の部分との結合部位を示す。Ｒ^ｂは炭素数２〜８の直鎖アルキル基を表し、Ｅは単結合、−Ｏ−、−ＮＲ^ｃ−、−Ｓ−、エステル結合及びアミド結合から選ばれる結合基を表す。Ｒ^ｃは水素原子、炭素数１〜４のアルキル基を示す。）The polymerizable group of the radically polymerizable compound is preferably a polymerizable group selected from the structures below.

(In the formula, * represents a binding site to a portion other than the polymerizable reactive group of the compound molecule. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, —O—, —NR. represents a linking group selected from ^c- , -S-, an ester bond and an amide bond. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  In addition, in the liquid crystal composition containing the liquid crystal and the radically polymerizable compound, it is preferable that the polymer obtained by polymerizing the radically polymerizable compound contains a radically polymerizable compound having a Tg of 100 ° C. or less.

  The compound having a monofunctional radically polymerizable group has a reactive group capable of performing radical polymerization in the presence of an organic radical, and examples thereof include t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate and nonyl. Methacrylate, lauryl methacrylate, n-octyl methacrylate and other methacrylate monomers; t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, lauryl acrylate, n-octyl acrylate and other acrylate monomers; styrene, styrene Derivatives (for example, o-, m-, p-methoxystyrene, o-, m-, p-t-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (for example, vinyl acetate) , Vinyl propionate, vinyl benzoate, vinyl acetate, etc., vinyl ketones (eg, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (eg, N-vinyl pyrrolidone, N-vinyl pyrrole) , N-vinylcarbazole, N-vinylindole, etc.), (meth) acrylic acid derivatives (eg, acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), vinyl halides (eg, vinyl chloride, vinylidene chloride, Vinyl monomers such as, but not limited to, tetrachloroethylene, hexachloroprene, vinyl fluoride, etc.). These various radically polymerizable monomers may be used alone or in combination of two or more. Further, it is preferable that these have compatibility with the liquid crystal.

式（１）中、Ｒ^ａおよびＲ^ｂはそれぞれ独立に炭素数２〜８の直鎖アルキル基を表し、Ｅは単結合、−Ｏ−、−ＮＲ^ｃ−、−Ｓ−、エステル結合、アミド結合から選ばれる結合基を表す。文中Ｒ^ｃは水素原子、炭素数１〜４のアルキル基を示す。Further, as the radically polymerizable compound, a compound represented by the following formula (1) is also preferable.

In formula (1), R ^a and R ^b each independently represent a linear alkyl group having 2 to 8 carbon atoms, and E is a single bond, —O—, —NR ^c —, —S—, ester bond, or amide. Represents a linking group selected from a bond. In the text, R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  At least one of the radically polymerizable compounds is preferably a compound having compatibility with liquid crystal and having one polymerizable reactive group in one molecule, that is, a compound having a monofunctional radically polymerizable group.

  The radically polymerizable compound represented by the formula (1) is a compound in which E is an ester bond (a bond represented by -C (= O) -O- or -OC (= O)-). Is preferable from the viewpoints of easiness of synthesis, compatibility with liquid crystal, and polymerization reactivity. Specifically, compounds having the following structures are preferable, but not particularly limited.

In formulas (1-1) and (1-2), R ^a and R ^b each independently represent a linear alkyl group having 2 to 8 carbon atoms.

  The content of the radically polymerizable compound in the liquid crystal composition is preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 50% by mass, based on the total mass of the liquid crystal and the radically polymerizable compound. Or less, more preferably 20 mass% or less.

  The Tg of the polymer obtained by polymerizing the radically polymerizable compound is preferably 100 ° C. or lower.

  The liquid crystal generally refers to a substance in the state of exhibiting both solid and liquid properties, and typical liquid crystal phases include nematic liquid crystal and smectic liquid crystal, but the liquid crystal usable in the present invention is not particularly limited. An example is 4-pentyl-4'-cyanobiphenyl.

  Next, sufficient energy is applied to the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radically polymerizable compound is introduced so that the radically polymerizable compound is polymerized. This can be carried out, for example, by applying heat or irradiating with UV, and the radically polymerizable compound concerned is polymerized in situ, whereby desired properties are exhibited. Among them, UV irradiation is preferable because UV allows the orientational patterning and enables the polymerization reaction in a shorter time. When used in the twisted nematic mode, a chiral dopant may be introduced into the liquid crystal cell, if necessary, in addition to the above liquid crystal composition.

  Moreover, you may heat at the time of UV irradiation. The heating temperature for UV irradiation is preferably within a temperature range in which the introduced liquid crystal exhibits liquid crystallinity, and is usually 40 ° C. or higher, and heating below the temperature at which the liquid crystal changes to an isotropic phase is preferable.

  Here, in the case of UV irradiation, it is preferable to select the wavelength having the best reaction quantum yield of the reactive polymerizable compound as the UV irradiation wavelength, and the UV irradiation amount is usually 0.01 to 30 J, It is preferably 10 J or less, and the smaller the UV irradiation amount, the more it is possible to suppress the decrease in reliability due to the destruction of the members constituting the liquid crystal display, and the shorter the UV irradiation time is, which improves the tact time in manufacturing, which is preferable. Is.

  Further, when the polymerization is carried out only by heating, not by UV irradiation, heating is preferably carried out at a temperature at which the polymerizable compound reacts and is below the decomposition temperature of the liquid crystal. Specifically, for example, the temperature is 100 ° C. or higher and 150 ° C. or lower.

  When applying sufficient energy to polymerize the radically polymerizable compound, it is preferable to apply no voltage and be in an electric field-free state.

<Liquid crystal display element>
A liquid crystal display device can be manufactured using the liquid crystal cell thus obtained.
For example, a reflection type liquid crystal display element can be obtained by providing a reflection electrode, a transparent electrode, a λ / 4 plate, a polarizing film, a color filter layer and the like in this liquid crystal cell according to a conventional method.
Further, if necessary, a backlight, a polarizing plate, a λ / 4 plate, a transparent electrode, a polarizing film, a color filter layer and the like are provided in this liquid crystal cell according to a conventional method to obtain a transmissive liquid crystal display device.

  The present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The abbreviations of the compounds used in the polymerization of the polymer and the preparation of the film-forming composition, and the characterization methods are as follows.

NMP: N-methyl-2-pyrrolidone,
GBL: γ-butyl lactone,
BCS: Butyl cellosolve

<Viscosity measurement>
For the polyamic acid solution, an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity at 25 ° C. with a sample amount of 1.1 mL and a cone rotor TE-1 (1 ° 34 ′, R24). ..

<Measurement of imidization ratio>
20 mg of polyimide powder was put into an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Science Co., Ltd.), and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) was added. Then, ultrasonic waves were applied to completely dissolve it. The 500-MHz proton NMR of this solution was measured with the measuring device (JNW-ECA500 by JEOL Datum).
The imidization ratio is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integrated value of this proton and the proton peak integrated derived from NH of the amide group appearing in the vicinity of 9.5 to 10.0 ppm. It was calculated by the following formula using the values and.
Imidization rate (%) = (1-α · x / y) × 100
In the formula, x is an integrated value of proton peaks derived from NH of the amide group, y is an integrated value of peaks of the reference protons, α is a reference proton for one NH proton of the amide group in the case of polyamic acid (imidization ratio is 0%) Is the number ratio of

<Polymer polymerization and preparation of radical-generating film-forming composition>
Synthesis example 1
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-2 (50) Polyimide DA-1 was placed in a 100 ml four-necked flask equipped with a nitrogen introduction tube, an air cooling tube, and a mechanical stirrer. 1.62 g (15.00 mmol) and 3.96 g (15.00 mmol) of DA-2 were measured, 48.2 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere and completely dissolved. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. After returning to room temperature again, 2.71 g (13.80 mmol) of TC-1 was added, and the mixture was reacted at 40 ° C. for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity became 1000 mPa · s, to obtain a polymerization liquid having a polyamic acid concentration of 20% by mass.
In a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, 60 g of the polyamic acid solution obtained above was weighed out, 111.4 g of NMP was added, a 7 mass% solution was adjusted, and 9.10 g of acetic anhydride while stirring ( 88.52 mmol) and 3.76 g (47.53 mmol) of pyridine were added, and the mixture was stirred at room temperature for 30 minutes and then stirred at 55 ° C. for 3 hours to cause a reaction. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol with stirring to precipitate a solid. Individuals are collected by filtration, and the solids are further put into 300 ml of methanol and stirred and washed for 30 minutes twice in total. The solids are collected by filtration, air-dried, and then dried in a vacuum oven 60 ° C. Thus, a polyimide (PI-1) having a number average molecular weight of 11,300, a weight average molecular weight of 32,900 and an imidation ratio of 53% was obtained.

Synthesis example 2
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-3 (50) Polyimide DA-1 was placed in a 100 ml four-necked flask equipped with a nitrogen introduction tube, an air cooling tube, and a mechanical stirrer. 1.62 g (15.00 mmol) and 4.96 g (15.00 mmol) of DA-3 were measured, 51.90 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere to completely dissolve it. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. After returning to room temperature again, 2.64 g (13.5 mmol) of TC-1 was added, and the mixture was reacted at 40 ° C. for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity became 1000 mPa · s, to obtain a polymerization liquid having a polyamic acid concentration of 20% by mass.
To a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, weigh 60 g of the polyamic acid solution obtained above, add 111.4 g of NMP, add 71.4% by weight of the solution, and stir 8.38 g of acetic anhydride while stirring. (81.4 mmol) and 3.62 g (45.8 mmol) of pyridine were added, and the mixture was stirred at room temperature for 30 minutes and then stirred at 55 ° C. for 3 hours to cause a reaction. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol with stirring to precipitate a solid. Individuals are collected by filtration, and the solids are further put into 300 ml of methanol and stirred and washed for 30 minutes twice in total. The solids are collected by filtration, air-dried, and then dried in a vacuum oven 60 ° C. Thus, a polyimide (PI-2) having a number average molecular weight Mn of 13,100, a weight average molecular weight Mw of 34,000 and an imidization ratio of 55% was obtained.

Synthesis example 3
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-4 (50) Polyimide DA-1 was placed in a 100 ml four-necked flask equipped with a nitrogen introduction tube, an air cooling tube, and a mechanical stirrer. 1.62 g (15.00 mmol) and 5.65 g (15.00 mmol) of DA-4 were measured, 55.4 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere to completely dissolve it. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. It returned to room temperature again, 2.82 g (14.40 mmol) of TC-1 was added, and it was made to react at 40 degreeC under nitrogen atmosphere for 12 hours. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity became 1000 mPa · s, to obtain a polymerization liquid having a polyamic acid concentration of 20% by mass.
In a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, 60 g of the polyamic acid solution obtained above was weighed, 111.4 g of NMP was added, a 7 mass% solution was prepared, and 8.36 g of acetic anhydride was stirred ( 81.2 mmol) and 3.65 g (46.1 mmol) of pyridine were added, and the mixture was stirred at room temperature for 30 minutes and then stirred at 55 ° C. for 3 hours to cause a reaction. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol with stirring to precipitate a solid. Individuals are collected by filtration, and the solids are further put into 300 ml of methanol and stirred and washed for 30 minutes twice in total. The solids are collected by filtration, air-dried, and then dried in a vacuum oven 60 ° C. Thus, a polyimide (PI-3) having a number average molecular weight Mn of 12,900, a weight average molecular weight Mw of 31,000 and an imidization ratio of 51% was obtained.

Radical generating film forming composition: Preparation of AL1 In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-1) obtained in Synthesis Example 1 was measured, 18.0 g of NMP was added, and the temperature was 50 ° C. Stir at to dissolve completely. Furthermore, 6.7 g of NMP and 6.7 g of BCS were added, and the mixture was further stirred for 3 hours to form a radical-generating film-forming composition: AL1 (solid content: 6.0% by mass, NMP: 66% by mass, BCS : 30 mass%) was obtained.

Radical generating film forming composition: Preparation of AL2 In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-2) obtained in Synthesis Example 2 was measured, 18.0 g of NMP was added, and the temperature was 50 ° C. Stir at to dissolve completely. Furthermore, 6.7 g of NMP and 6.7 g of BCS were added, and the mixture was further stirred for 3 hours to form a radical-generating film-forming composition of the present invention: AL2 (solid content: 6.0% by mass, NMP: 66% by mass, BCS : 30 mass%) was obtained.

Preparation of non-radical generating film forming composition: AL3 In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-3) obtained in Synthesis Example 3 was weighed, 18.0 g of NMP was added, and 50 Stir at 0 ° C. to completely dissolve. Further, 6.7 g of NMP and 6.7 g of BCS were added, and the mixture was further stirred for 3 hours to form a non-radical generating film forming composition: AL3 (solid content: 6.0% by mass, NMP: 66% by mass, BCS: 30% by mass) was obtained.

<Production of liquid crystal display element>
Using AL1 to AL3 and the liquid crystal aligning agent SE-6414 (manufactured by Nissan Chemical Industries, Ltd.) for horizontal alignment obtained as described above, a liquid crystal display device having a configuration shown in Table 3 was produced.

(First substrate)
The first substrate (hereinafter also referred to as IPS substrate) is a non-alkali glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. An ITO (Indium-Tin-Oxide) electrode having a comb-teeth pattern with an electrode width of 10 μm and an electrode-to-electrode spacing of 10 μm is formed on a substrate to form a pixel. The size of each pixel is 10 mm in length and about 5 mm in width.
After filtering AL1 to AL3 or SE-6414 with a 1.0 μm filter, they were applied to the electrode formation surface of the IPS substrate by spin coating and dried on a hot plate at 80 ° C. for 1 minute. Next, AL1 to AL3 were fired at 150 ° C. for 20 minutes, and SE-6414 was fired at 220 ° C. for 20 minutes, and fired to form coating films each having a film thickness of 100 nm.
In the “with” rubbing treatment, rubbing was performed so that the rubbing direction was parallel to the comb-teeth electrode. Rubbing was performed using a rayon cloth: YA-20R manufactured by Yoshikawa Kako, under the conditions of a roll diameter of 120 mm, a rotation speed of 300 rpm, a moving speed of 50 mm / sec, and a pushing amount of 0.4 mm. However, the rotation speed was set to 1000 rpm only for the film coated with SE-6414. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, and drying was performed at 80 ° C. for 10 minutes.

(Second substrate)
The second substrate (also called back ITO substrate) is a non-alkali glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm, and an ITO film is formed on the back surface (the surface facing the outside of the cell). ing. Further, a columnar spacer having a height of 4 μm is formed on the surface (the surface facing the inside of the cell).
After filtering AL1, AL2 or SE-6414 with a 1.0 μm filter, it was applied on the electrode formation surface of the IPS substrate by spin coating and dried on a hot plate at 80 ° C. for 1 minute. Then, AL1 and AL2 were fired at 150 ° C. for 20 minutes, and SE-6414 was fired at 220 ° C. for 20 minutes to form coating films having a film thickness of 100 nm, respectively, and then subjected to rubbing treatment. The rubbing treatment was performed using a rayon cloth: YA-20R manufactured by Yoshikawa Kako, under the conditions of a roll diameter of 120 mm, a rotation speed of 1000 rpm, a moving speed of 50 mm / sec, and an indentation amount of 0.4 mm. However, the rotation speed of the film coated with AL1 or AL2 was 300 rpm. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, and drying was performed at 80 ° C. for 10 minutes.

(Production of liquid crystal cell)
Using two types of substrates (first substrate and second substrate) with the above liquid crystal alignment film, the periphery was sealed leaving a liquid crystal injection port, and an empty cell with a cell gap of about 4 μm was produced. At this time, when the first substrate is not rubbed, the comb-shaped electrodes of the first substrate and the rubbing direction of the second substrate are combined in parallel, and when the first substrate is rubbed, the first substrate is rubbed. The first substrate and the second substrate were assembled so that the rubbing directions were antiparallel.
A liquid crystal (MLC-3019 manufactured by Merck & Co., containing 10 wt% of HMA) was vacuum-injected into the empty cell at room temperature, and then the injection port was sealed to obtain a liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Then, the obtained liquid crystal cell was heat-treated at 120 ° C. for 20 minutes.
With the UV treatment, a high-pressure mercury lamp was used to irradiate the liquid crystal cell with ultraviolet rays through a bandpass filter having a wavelength of 313 nm so that the exposure amount was 1000 mJ.

<Evaluation of liquid crystal alignment>
The orientation of the liquid crystal cell was confirmed using a polarizing plate set in crossed Nicols. Those with no defects were marked with ◯, those with slight alignment defects were marked with Δ, and those without alignment were marked with x.

<Measurement of VT curve and evaluation of driving threshold voltage and maximum luminance voltage>
A white LED backlight and a luminance meter are set so that the optical axes are aligned, and a liquid crystal cell (liquid crystal display element) with a polarizing plate attached so that the luminance is minimized is set between them, and a voltage of 1V is applied up to 8V. The VT curve was measured by applying the voltage and measuring the luminance at the voltage. The driving threshold voltage and the value of the voltage at which the brightness was maximized were estimated from the obtained VT curve.

<Evaluation of response speed of liquid crystal display>
Using the device used in the measurement of the VT curve, a luminance meter was connected to an oscilloscope, and a response speed (Ton) when a voltage that maximizes the brightness was applied and a response speed (Toff) when the voltage was set to 0 Was measured.

  In comparison of Cell-1 to Cell-20 using a horizontal alignment film that is rubbed on the back ITO substrate (second substrate) side, a cell that uses a radical generating film on the IPS substrate (first substrate) side and is UV-treated It was confirmed that -11, Cell-12, Cell-16, and Cell-17 had good liquid crystal orientation and reduced drive threshold voltage and maximum luminance voltage. In addition, while the Toff value is increased in Cell-11 and Cell-12 where the radical generation film is not rubbed, the Toff value is increased in Cell-16 and Cell-17 where the radical generation film is rubbed. It has been confirmed that the increase of the is significantly improved.

  As a supplementary experiment in addition to the above, a liquid crystal cell was prepared in which AL1 was used for both the back ITO substrate (second substrate) and the IPS substrate (first substrate), and neither the first substrate nor the second substrate was rubbed. In this liquid crystal cell, alignment defects and bright spots (fluid alignment) along the flow direction at the time of liquid crystal injection were observed before UV irradiation, but after UV irradiation, the flow alignment completely disappeared, and domains derived from the liquid crystal were observed. (Schlieren) was confirmed. From this fact, when the radical generating film and the liquid crystal containing the polymerizable compound are used together, the radical generating film loses the liquid crystal alignment regulating force by UV irradiation, and a zero plane anchoring film is formed on the radical generating film. It was suggested to be done.

  Further, in the comparison of the liquid crystal cells Cell-21 to Cell-24, Cell-21 and Cell-23 which were not UV-irradiated showed uniaxial orientation in the rubbing direction, but Cell-22 and UV-irradiated Cell-22 were shown. Cell-24 changed to a non-aligned state and liquid crystal domains (Schlieren) were generated. From this, it was suggested that even when the radical generating film was rubbed, the zero plane anchoring film was formed on the radical generating film by UV irradiation.

  However, when the Cell-22 and Cell-24 were observed while rotating under crossed Nicols, a slight change in light and dark occurred, so this zero-plane anchoring film is not in a state where there is no alignment regulating force, The regulating force is weaker than the intermolecular force between liquid crystals, and it is suggested that the regulating force alone does not cause the liquid crystal molecules to be uniaxially aligned in any direction. From this, it is considered that the reason why the Toff value was greatly improved in Cell-16 and Cell-17 was that the weak regulation force acted.

第１工程：２−ヒドロキシメチルアクリル酸エチルエステルの合成
窒素導入管を取り付けた５００ｍｌの四口フラスコに、４−メトキシフェノール１０ｍｇ、ＤＡＢＣＯ（１，４−ジアザビシクロ［２．２．２］オクタン）２１．８８ｇ（１９５．１ｍｍｏｌ）を計り取り、純水を５０ｍｌ加え、窒素雰囲気下で１０℃以下で攪拌しながらパラホルムアルデヒド１１．５２ｇ（３９０．１ｍｍｏｌ）を加え、１時間攪拌した。スラリー状態から溶液状態に変化したのを確認し、アセトニトリルを３００ｍｌ加え、アクリル酸エチル１９．５３ｇ（１９５．１ｍｍｏｌ）を滴下しながら加え、５０℃で５時間反応させた。反応終了後、分液ロートに反応溶液を移し、ｎ−ヘキサン５０ｍｌを加えた。３層に分かれたのを確認し、下の２層を回収し、この操作を３回行った。更にｐＨが４〜５になるように塩酸を加え、酢酸エチルを用いて抽出を行った。抽出した溶液に無水硫酸マグネシウムを加え攪拌し乾燥させた後、濾過・濃縮を行い、無色透明のオイル状液体２２．９ｇ（１７５．６ｍｍｏｌ、収率９０％）を得た。構造は核磁気共鳴スペクトル（^１Ｈ−ＮＭＲスペクトル）にて目的物であることを確認した。測定データを以下に示す。
^１Ｈ ＮＭＲ （４００ ＭＨｚ，ＣＤＣｌ_３）δ：６．８１（１Ｈ）、５．８０（１Ｈ）、４．３１（２Ｈ）、４．１７（１Ｈ）、１．９８（１Ｈ）、０．９３（３Ｈ）Polymerizable compound synthesis example 1
Synthesis of 2- (heptanoyloxymethyl) acrylic acid ethyl ester

First step: Synthesis of 2-hydroxymethylacrylic acid ethyl ester In a 500 ml four-necked flask equipped with a nitrogen introducing tube, 4-methoxyphenol 10 mg, DABCO (1,4-diazabicyclo [2.2.2] octane) 21. 0.88 g (195.1 mmol) was weighed out, 50 ml of pure water was added, and 11.52 g (390.1 mmol) of paraformaldehyde was added with stirring at 10 ° C or lower under a nitrogen atmosphere, and the mixture was stirred for 1 hour. After confirming the change from the slurry state to the solution state, 300 ml of acetonitrile was added, 19.53 g (195.1 mmol) of ethyl acrylate was added dropwise, and the mixture was reacted at 50 ° C. for 5 hours. After completion of the reaction, the reaction solution was transferred to a separating funnel and 50 ml of n-hexane was added. After confirming that the layer was divided into three layers, the lower two layers were collected and this operation was repeated three times. Further, hydrochloric acid was added so that the pH became 4 to 5, and extraction was performed with ethyl acetate. Anhydrous magnesium sulfate was added to the extracted solution, and the mixture was stirred, dried, filtered, and concentrated to obtain 22.9 g (175.6 mmol, yield 90%) of a colorless transparent oily liquid. The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.81 (1H), 5.80 (1H), 4.31 (2H), 4.17 (1H), 1.98 (1H), 0.93. (3H)

Second step: Synthesis of 2- (heptanoyloxymethyl) acrylic acid ethyl ester In a 500 ml four-necked flask equipped with a nitrogen inlet tube, 19.9 g (152 g) of 2-hydroxymethylacrylic acid obtained by the above method was added. 9.9 mmol), THF (300 ml) and triethylamine (23.2 g, 229.3 mmol) were added, and 25.0 g (168.2 mmol) of heptanoyl chloride was added dropwise while keeping the temperature at 10 ° C. or lower under a nitrogen atmosphere, followed by reaction for 6 hours. It was After completion of the reaction, the precipitated triethylamine hydrochloride was removed by filtration, the reaction solution was concentrated, redissolved in 300 ml of ethyl acetate, washed 3 times with 100 ml of 10% aqueous potassium carbonate solution, and washed with 50 ml of pure water. It was washed twice, dried over anhydrous magnesium sulfate, filtered and concentrated to give a pale yellow viscous body. Purification by flash column chromatography (developing solvent: ethyl acetate: n-hexane = 20:80), and removal of the solvent / vacuum drying gave a colorless and transparent oily liquid 32.2 g (133.0 mmol: yield). 87%). The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.37 (1H), 5.80 (1H), 3.80 (2H), 4.23-4.21 (2H), 2.39-2. 37 (2H), 1.64-1.58 (2H), 1.30-1.27 (9H), 0.86 (3H)

第１工程：２−ヒドロキシメチルアクリル酸ブチルエステルの合成
前記第１工程と同様の操作にて、エチルアクリレートをブチルアクリレートに変更し合成を行い、無色透明のオイル２４．３ｇを得た（２６．２ｇ：収率８５％）。構造は核磁気共鳴スペクトル（^１Ｈ−ＮＭＲスペクトル）にて目的物であることを確認した。測定データを以下に示す。
^１Ｈ ＮＭＲ （４００ ＭＨｚ，ＣＤＣｌ_３）δ：６．８１（１Ｈ）、５．８０（１Ｈ）、４．３１（２Ｈ）、４．１７（１Ｈ）、１．９８（１Ｈ）、１．６７−１．６４（２Ｈ）、１．４２−１．３８（２Ｈ）、０．９３（３Ｈ） Polymerizable compound synthesis example 2
Synthesis of 2- (heptanoyloxymethyl) acrylic acid butyl ester

First Step: Synthesis of 2-Hydroxymethylacrylic Acid Butyl Ester By the same operation as in the first step, ethyl acrylate was changed to butyl acrylate for synthesis, and 24.3 g of a colorless transparent oil was obtained (26. 2 g: yield 85%). The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.81 (1H), 5.80 (1H), 4.31 (2H), 4.17 (1H), 1.98 (1H), 1.67. -1.64 (2H), 1.42-1.38 (2H), 0.93 (3H)

Second step: Synthesis of 2- (heptanoyloxymethyl) acrylic acid butyl ester 2-((heptanoyloxy) methyl) acrylic acid butyl ester obtained by the above method from 2-hydroxymethylacrylic acid of the second step Instead, the synthesis was performed in the same manner to obtain 34.2 g (126.7: yield 82.8%) of a colorless transparent oily liquid. The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.36 (1H), 5.81 (1H), 4.80 (2H), 4.19-4.16 (2H), 2.35-2. 31 (2H), 1.64-1.58 (4H), 1.40-1.25 (8H), 0.96-0.83 (6H)

ディーンスターク管を取り付けた４口フラスコに、イタコン酸２３．８ｇ（１８２．９ｍｍｏｌ）、１−ヘキサノール３５．５ｇ（３４７．５ｍｍｏｌ）を計り取り、シクロヘキサン５００ｍｌ、濃硫酸０．９ｇ（９．１ｍｍｏｌ）、ジブチルヒドロキシトルエン（ＢＨＴ）０．０４ｇ（１．８２ｍｍｏｌ）を加え、窒素雰囲気にし、１１０℃にて２４時間脱水縮合反応させた。反応終了後、反応溶液にｎ−ヘキサンを１００ｍｌ加え、１０％炭酸ナトリウム水溶液１００ｇで３回、純水１００ｍｌにて３回洗浄し、無水硫酸マグネシウムで乾燥させた。濾過・濃縮後真空乾燥させることで無色透明のオイル状液体４８．６ｇ（１６２．８ｍｍｏｌ：収率８９％）を得た。構造は核磁気共鳴スペクトル（^１Ｈ−ＮＭＲスペクトル）にて目的物であることを確認した。測定データを以下に示す。
^１Ｈ ＮＭＲ （４００ ＭＨｚ，ＣＤＣｌ_３）δ：６．３０（１Ｈ）、５．６５（１Ｈ）、４．２０―４．００（４Ｈ）、３．３２（２Ｈ）、１．６４−１．５８（４Ｈ）、１．４０−１．２５（１２Ｈ）、０．９６−０．８３（６Ｈ）Polymerizable compound synthesis example 3
Synthesis of dihexyl itaconate

In a four-necked flask equipped with a Dean-Stark tube, 23.8 g (182.9 mmol) of itaconic acid and 35.5 g (347.5 mmol) of 1-hexanol were weighed out, 500 ml of cyclohexane and 0.9 g (9.1 mmol) of concentrated sulfuric acid. , Dibutylhydroxytoluene (BHT) (0.04 g, 1.82 mmol) were added, and the mixture was placed in a nitrogen atmosphere and subjected to dehydration condensation reaction at 110 ° C. for 24 hours. After completion of the reaction, 100 ml of n-hexane was added to the reaction solution, washed with 100 g of 10% sodium carbonate aqueous solution three times and with 100 ml of pure water three times, and dried with anhydrous magnesium sulfate. After filtration, concentration, and vacuum drying, 48.6 g (162.8 mmol: yield 89%) of a colorless transparent oily liquid was obtained. The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.30 (1H), 5.65 (1H), 4.20-4.00 (4H), 3.32 (2H), 1.64-1. 58 (4H), 1.40-1.25 (12H), 0.96-0.83 (6H)

(Production of liquid crystal cell)
After preparing an empty cell according to the above (Preparation of liquid crystal cell), the liquid crystal composition LC-1 to LC-4 (MLC-3019 manufactured by Merck & Co., Inc.) was added to each of the empty cells in the optimum amount. (Injected at room temperature) and vacuum-injected at room temperature at a vacuum degree of about 300 Pa, and vacuum-injected after deaeration at a vacuum degree of about 1 Pa for 1 hour. Was sealed to form a liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Then, the obtained liquid crystal cell was heat-treated at 120 ° C. for 10 minutes. After that, the test was conducted in the same manner as described above.

The liquid crystal compositions LC-1 to LC-4 are prepared by adding the polymerizable compounds described in the following table to MLC-3019 in the following introduction amounts.

<Evaluation result of orientation>

  The liquid crystals in which IDBu and IDHex were introduced (LC-1, LC-2) and the liquid crystals in which C2C6 and C4C6 were introduced showed very good orientation even when performed at a relatively high degree of vacuum.

<Evaluation result of electro-optical characteristics>
Next, the following is a summary of the driving threshold voltage, the voltage at the maximum luminance, and the response speed of the cell using the liquid crystal having the zero anchoring orientation described above, in which the radical generating film is not rubbed. ..

When a polymerizable compound was used, a decrease in driving voltage was confirmed regardless of the presence or absence of rubbing treatment, and it was observed that the response speed tended to be improved by performing rubbing treatment.
Therefore, it was found that the polymerizable compound can simultaneously achieve the effect of zero anchoring under high vacuum and the response speed improvement by rubbing.

  According to the present invention, a zero-plane anchoring film can be industrially produced with a high yield from an inexpensive raw material. The liquid crystal display device obtained by the method of the present invention is useful as a vertical alignment type liquid crystal display device such as a PSA type liquid crystal display and an SC-PVA type liquid crystal display.

Claims (22)

  A liquid crystal composition containing a liquid crystal and a radically polymerizable compound, in the state of being in contact with the radical generating film, including a step of giving sufficient energy to cause a polymerization reaction of the radically polymerizable compound, a zero plane anchoring film of Production method.   The method according to claim 1, wherein the radical generating film of the first substrate is a uniaxially oriented radical generating film.   The method according to claim 1, wherein the step of applying energy is performed without electric field.   The method according to any one of claims 1 to 3, wherein the radical-generating film is a film formed by immobilizing an organic group that induces radical polymerization.   2. The radical-generating film is obtained by applying a composition of a compound having a radical-generating group and a polymer and curing the composition to form a film, thereby immobilizing the composition in the film. 4. The method according to any one of 3 to 3.   The method according to claim 1, wherein the radical generating film is made of a polymer containing an organic group that induces radical polymerization.   Polymer containing an organic group that induces the radical polymerization, a polyimide precursor obtained by using a diamine component containing a diamine containing an organic group that induces radical polymerization, polyimide, at least one selected from polyurea and polyamide. The method according to claim 6, which is a polymer. The organic group which induces the radical polymerization is an organic group represented by the following structures [X-1] to [X-18], [W], [Y], and [Z]. The method according to any one of items.

(In the formulas [X-1] to [X-18], * represents a binding site to a part other than the polymerizable reactive group of the compound molecule, and S ¹ and S ² are each independently —O— or —NR. Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom or halogen. Atom, represents an alkyl group having 1 to 4 carbon atoms)

(In the formulas [W], [Y], and [Z], * represents a binding site to a portion of the compound molecule other than the polymerizable reactive group, and Ar has an organic group and / or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, wherein R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. When R ⁹ and R ¹⁰ are alkyl groups, they may be bonded to each other at the ends to form a ring structure, and Q represents the following structure.

(In the formula, R ¹¹ represents —CH ₂ —, —NR—, —O—, or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents Q of the compound molecule. Shows the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ) The method according to claim 7, wherein the diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7).

(In the formula (6), R ⁶ is a single bond, —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N. _{(CH 3) -, - CON} (CH 3) -, or -N _(CH 3) CO- represents,
R ⁷ represents a single bond, or an alkylene group having 1 to 20 carbon atoms, which is unsubstituted or substituted by a fluorine atom, and any one or more of —CH ₂ — or —CF ₂ — of the alkylene group is independent. May be replaced with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, i.e., -O-, -COO- , -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups provided that they are not adjacent to each other;
R ⁸ is the following formula:

Represents a radical polymerization reactive group selected from
(In the formulas [X-1] to [X-18], * represents a binding site to a moiety other than the radical-polymerization reactive group of the compound molecule, and S ¹ and S ² are independently -O- and-. NR- and -S- are represented, R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, R ¹ and R ² are each independently a hydrogen atom, Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms))

(In Formula (7), T ¹ and T ² are each independently a single bond, —O—, —S—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —. _{CH 2 O -, - N (} CH 3) -, - CON (CH 3) -, or -N _(CH 3) a CO-,
S represents a single bond or an alkylene group having 1 to 20 carbon atoms, which is unsubstituted or substituted by a fluorine atom, and any one or more of —CH ₂ — or —CF ₂ — of the alkylene group is independently. It may be substituted with a group selected from —CH═CH—, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, namely, —O—, —COO—, -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups provided that they are not adjacent to each other,
J is an organic group represented by the following formula,

(In the formulas [W], [Y], and [Z], * represents a bonding site with T ^2, and Ar represents phenylene, naphthylene, and biphenylene which may have an organic group and / or a halogen atom as a substituent. Represents an aromatic hydrocarbon group selected from the group consisting of, R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q is the structure below. Represents.

(In the formula, R ¹¹ represents —CH ₂ —, —NR—, —O—, or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents Q of the compound molecule. Shows the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ))   The method according to any one of claims 1 to 9, wherein at least one of the radically polymerizable compounds is a compound having compatibility with a liquid crystal and having one polymerizable reactive group in one molecule. The method according to claim 10, wherein the polymerizable reactive group of the radically polymerizable compound is selected from the following structures.

(In the formula, * represents a binding site to a portion other than the polymerizable reactive group of the compound molecule. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, —O—, —NR. represents a linking group selected from ^c- , -S-, an ester bond and an amide bond. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)   In the liquid crystal composition containing the liquid crystal and the radical polymerizable compound, the liquid crystal composition containing the radical polymerizable compound having a Tg of 100 ° C. or less of the polymer obtained by polymerizing the radical polymerizable compound is used. The method according to any one of claims 1 to 11, characterized in that A step of preparing a first substrate having a radical generating film, and a second substrate which may have a radical generating film,
Creating a cell so that the radical-generating film on the first substrate faces the second substrate, and
Between the first substrate and the second substrate, including a step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound,
A method for manufacturing a liquid crystal cell, which uses the method according to claim 1.   The method for manufacturing a liquid crystal cell according to claim 13, wherein the second substrate is a second substrate having no radical generation film.   The method of manufacturing a liquid crystal cell according to claim 14, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment.   The method for manufacturing a liquid crystal cell according to claim 15, wherein the liquid crystal alignment film having the uniaxial alignment is a liquid crystal alignment film for horizontal alignment.   The method for producing a liquid crystal cell according to claim 13, wherein the first substrate having the radical generating film is a substrate having comb-teeth electrodes. Contains a liquid crystal and a radically polymerizable compound,
At least one of the radically polymerizable compounds is a compound having compatibility with liquid crystal, having one polymerizable reactive group in one molecule,
A liquid crystal composition in which the polymerizable reactive group is selected from the following structures.

(In the formula, * represents a binding site to a portion other than the polymerizable reactive group of the compound molecule. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, —O—, —NR. represents a linking group selected from ^c- , -S-, an ester bond and an amide bond. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)   A method for manufacturing a liquid crystal display device, which uses a film for producing a zero-plane anchoring state, which is obtained by using the method according to claim 1.   A liquid crystal display device obtained by using the method according to claim 19.   The liquid crystal display element according to claim 20, wherein the first substrate or the second substrate has an electrode.   The liquid crystal display element according to claim 20 or 21, which is a low voltage driving lateral electric field liquid crystal display element.