JPWO2019131810A1 - Manufacturing method of zero-plane anchoring film and liquid crystal display element - Google Patents

Abstract

Provided are an industrial method for manufacturing a zero-plane anchoring film, and a good liquid crystal display element and a method for manufacturing a liquid crystal display element using the same. A zero-plane anchor comprising a step of imparting sufficient energy to polymerize the radically polymerizable compound in a state where the liquid crystal composition containing the liquid crystal, the chiral dopant and the radically polymerizable compound is in contact with the radical generating film. A method for producing a ring film. A step of preparing a cell having a liquid crystal composition containing a liquid crystal, a chiral dopant, and a radically polymerizable compound between a first substrate having a radical generating film and a second substrate having no radical generating film, and a step of preparing a cell. The method for producing a functional film includes a step of imparting sufficient energy to the cell to polymerize the radically polymerizable compound.

Description

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

In recent years, liquid crystal display elements have been widely used in mobile phones, computers, television displays, and the like. Liquid crystal display elements 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 the liquid crystal display, and the liquid crystal is oriented in a desired orientation state in all modes. (Liquid crystal alignment film) is used.

In particular, IPS mode, which does not distort the display even when touched, is preferred for products equipped with a touch panel such as tablet PCs, smartphones, and smart TVs. Liquid crystal display elements using Field Switching) and technologies using non-contact technology using photoalignment have come to be used.

However, FFS has a higher substrate manufacturing cost than IPS, and has a problem that a display defect peculiar to FFS mode called Vcom shift occurs. In addition, regarding photo-orientation, compared to the rubbing method, there are merits that the size of the element that can be manufactured can be increased and the display characteristics can be greatly improved. If it is an isomerized type, it may be burned in due to insufficient orientation. At present, liquid crystal display element manufacturers and liquid crystal alignment film manufacturers are making various efforts to solve these problems.

On the other hand, in recent years, an IPS mode using what is called zero-plane anchoring has been proposed, and it has been reported that using this method enables improved contrast and significantly lower voltage drive compared to the conventional IPS mode. (See Patent Document 1).

Specifically, a liquid crystal alignment film having strong anchoring energy is used for the substrate on one side, and the substrate side provided with the electrode that generates the transverse electric field on one side has no liquid crystal orientation regulating force. This is a method of making a liquid crystal display element in IPS mode by performing various processes and using them.

In recent years, a technical proposal for a cellophane anchoring IPS mode has been made by creating a zero-plane state using a concentrated polymer brush or the like (Reference 2). This technology has realized a significant improvement in the contrast ratio and a significant reduction in the drive voltage.

Japanese Patent No. 40553530 Japanese Unexamined Patent Publication No. 2013-231757

On the other hand, this technology has problems that occur in principle, and the first is that it is necessary to perform under extremely delicate conditions in order to stably generate a polymer brush on a substrate, which is not realistic considering mass production. There is no such thing. Secondly, the alignment film plays an important role such as suppressing seizure, but it is difficult to control the electrical properties required when using a polymer brush or the like. Thirdly, due to the driving principle, the response speed when the voltage is turned off becomes very slow. It is expected that the threshold voltage will be significantly reduced by eliminating the resistance during driving applied to the liquid crystal by setting the orientation regulating force to zero, and the brightness will be improved by reducing the misaligned region during driving, but the liquid crystal will return. As for, since the power when the liquid crystal returns depends on the elastic force of the liquid crystal, it is considered that the speed is significantly reduced as compared with the case where the alignment film is present.
If such technical problems can be solved, it will be a great cost merit as a panel maker, and it is considered that it will be a merit for suppressing battery consumption and improving image quality.
The present invention has been made to solve the above-mentioned problems, and is a manufacturing method applying polymer stabilization technology capable of manufacturing a zero-plane anchoring film, and is simple and inexpensive at room temperature. It is an object of the present invention to provide a transverse electric field liquid crystal display element and a method for manufacturing the same, which can simultaneously realize non-contact orientation, lower drive voltage, and faster response speed at off.

As a result of diligent 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 gist.

（式［Ｘ−１］〜［Ｘ１４］中、＊は化合物分子の重合性不飽和結合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は水素原子又は炭素原子数１〜４のアルキル基を表し、Ｒ^１２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不飽和結合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は下記のいずれかの構造を表す。

（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請求項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−１４］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は水素原子又は炭素原子数１〜４のアルキル基を表し、Ｒ^１２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は下記のいずれかの構造を表す。

（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不飽和結合を有する化合物である、請求項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不飽和結合が以下の構造から選ばれる、請求項１０に記載の方法。

（式中、＊は化合物分子の重合性不飽和結合以外の部分との結合部位を示す）
［１２］ 前記液晶、カイラルドーパント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請求項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、カイラルドーパント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、
請求項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請求項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請求項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請求項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請求項請求項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、カイラルドーパント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不飽和結合を有する化合物であり、
重合性不飽和結合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不飽和結合以外の部分との結合部位を示す）
［１９］ 請求項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］ 請求項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、請求項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、請求項２０又は２１に記載の液晶表示素子。That is, the present invention includes the following.
[1] A step of imparting sufficient energy to polymerize the radically polymerizable compound in a state where the liquid crystal composition containing the liquid crystal, the chiral dopant and the radically polymerizable compound is in contact with the radical generating film is included. A method for producing a zero-plane anchoring film.
[2] The method according to claim 1, wherein the radical generation film contained in the first substrate is a radical generation film subjected to uniaxial orientation treatment.
[3] The method according to claim 1 or 2, wherein the step of applying energy is performed without an electric field.
[4] 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.
[5] The radical-generating film is obtained by applying a composition of a compound having a radical-generating group and a polymer and curing the film to form a film, thereby immobilizing the film. The method according to any one of claims 1 to 3.
[6] The method according to any one of claims 1 to 3, wherein the radical generating film is composed 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 claim 6, wherein the polymer is at least one kind.
[8] Claims 4, 6 in which the organic group that induces radical polymerization is an organic group represented by the following structures [X-1] to [X-14], [W], [Y], and [Z]. And the method according to any one of 7.

(In the formulas [X-1] to [X14], * indicates a bonding site with a portion other than the polymerizable unsaturated bond of the compound molecule, and S ¹ and S ² are independently -O- and -NR-, respectively. , -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² is 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. R ¹ and R ² independently represent a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms).

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

(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. Indicates the binding site with a part other than the above.)
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 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 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 an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH _2- or -CF _{2- of the} alkylene group is independent of each other. May be replaced with a group selected from -CH = CH-, a divalent carbon ring, and a divalent heterocycle, and any of the following groups, namely -O-, -COO- , -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups, provided they are not adjacent to each other;
R ⁸ is represented by the following formula:

Represents a radical polymerization reactive group selected from.
(In formulas [X-1] to [X-14], * indicates a bonding site with a portion of the compound molecule other than the radical polymerization reactive group, and S ¹ and S ² are independently -O- and-, respectively. Represents NR- and -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Represents an alkoxy group, and R ¹ and R ² independently represent a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms))

(In formula (7), T ¹ and T ² are independently single-bonded, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-,-. CH ₂ O-, -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-
S represents an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH _2- or -CF _{2- of the} alkylene group is independent of each other. It may be replaced with a group selected from −CH = CH−, a divalent carbocycle, and a divalent heterocyclic ring, and any of the following groups, namely −O−, −COO−,. -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups provided 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 the 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. Indicates 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 any of the following. Represents the 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. Indicates the binding site with a part other than the above.)
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] The invention 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 unsaturated bond in one molecule. the method of.
[11] The method according to claim 10, wherein the polymerizable unsaturated bond of the radically polymerizable compound is selected from the following structures.

(In the formula, * indicates the binding site of the compound molecule with a portion other than the polymerizable unsaturated bond)
[12] In a liquid crystal composition containing the liquid crystal, a chiral dopant and a radically polymerizable compound, the liquid crystal composition contains a radically polymerizable compound having a Tg of a polymer obtained by polymerizing the radically polymerizable compound of 100 ° C. or less. The method according to any one of claims 1 to 11, wherein a liquid crystal composition is used.
[13] A step of preparing a first substrate having a radical generating film and a second substrate having a radical generating film.
A step of creating a cell so that the radical generation film on the first substrate faces the second substrate, and
A step of filling a liquid crystal composition containing a liquid crystal, a chiral dopant and a radically polymerizable compound between the first substrate and the second substrate is included.
A method for manufacturing a liquid crystal cell using the method according to any one of claims 1 to 12.
[14] 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.
[15] The method for 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 orientation.
[16] The method for manufacturing a liquid crystal cell according to claim 15, wherein the liquid crystal alignment film having uniaxial orientation is a liquid crystal alignment film for horizontal alignment.
[17] The method for producing a liquid crystal cell according to any one of claims 13 to 16, wherein the first substrate having the radical generating film is a substrate having a comb tooth electrode.
[18] Contains liquid crystal, chiral dopant and radically polymerizable compound,
At least one of the radically polymerizable compounds is a compound having a polymerizable unsaturated bond in one molecule and having compatibility with a liquid crystal.
A liquid crystal composition in which a polymerizable unsaturated bond is selected from the following structures.

(In the formula, * indicates the binding site of the compound molecule with a portion other than the polymerizable unsaturated bond)
[19] A method for manufacturing a liquid crystal display element using a film that creates a zero-plane anchoring state obtained by using the method according to any one of claims 1 to 17.
[20] A liquid crystal display element obtained by using the method according to claim 19.
[21] The liquid crystal display element according to claim 20, wherein the first substrate or the second substrate has electrodes.
[22] The liquid crystal display element according to claim 20 or 21, which is a low voltage drive transverse 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 by an inexpensive raw material or an existing manufacturing method. Further, the liquid crystal display element obtained by the manufacturing method of the present invention has a faster response speed of the liquid crystal when it is off than the conventional technology, has a low drive voltage, has no bright spot, and can suppress Vcom shift in the IPS mode, and FFS. It is possible to provide a liquid crystal display element having excellent characteristics such that higher definition can be achieved in the mode.

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 liquid crystal composition containing a liquid crystal, a chiral dopant and a radically polymerizable compound is provided between a first substrate having a radical generating film and a second substrate having a radical generating film. A method for producing a zero-plane anchoring film, which comprises a step of preparing a cell and a step of imparting sufficient energy to the cell to carry out a polymerization reaction of the radically polymerizable compound. 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 creating a cell so that the radical generating film faces the second substrate, and a first step. A method for producing a liquid crystal cell, which comprises a step of filling a liquid crystal composition containing a liquid crystal, a chiral dopant and a radically polymerizable compound between one substrate and a second substrate. For example, a low-voltage drive IPS liquid crystal display element in which the second substrate does not have a radical generating film and has a uniaxially oriented liquid crystal alignment film, and the first substrate has a comb-tooth electrode. It is a creation method.

In the present invention, the "zero-plane anchoring film" has no or, if any, weaker intermolecular force between liquid crystal molecules in the in-plane direction, and the liquid crystal molecules can be eventually formed by this film alone. A film that is not uniaxially oriented in the direction of. Further, the zero-plane anchoring film is not limited to the solid film, but also includes a liquid film covering the solid surface. Normally, a film that regulates the orientation of liquid crystal molecules, that is, a liquid crystal alignment film, is used in a pair to align the liquid crystal in the liquid crystal display element, but when the zero-plane anchoring film and the liquid crystal alignment film are used in pairs, the liquid crystal is also used. Can be oriented. This is because the alignment restricting force of the liquid crystal alignment film is transmitted to 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 close to the zero-plane anchoring film are also oriented. 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. Horizontal orientation refers to a state in which the major axes of liquid crystal molecules are arranged substantially parallel to the liquid crystal alignment film surface, and inclined orientation of about several degrees is also included in the category of horizontal orientation.

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

（式［Ｘ−１］〜［Ｘ−１４］中、＊は化合物分子の重合性不飽和結合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は水素原子又は炭素原子数１〜４のアルキル基を表し、Ｒ^１２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不飽和結合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は下記のいずれかの構造を表す。

（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 [X-1] to [X-14], [W], [Y], and [Z] represented by the following structures. Be done.

(In the formulas [X-1] to [X-14], * indicates a bonding site with a portion other than the polymerizable unsaturated bond of the compound molecule, and S ¹ and S ² are independently -O- and-, respectively. Represents NR- and -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Represents an alkoxy group, and R ¹ and R ² independently represent a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms).

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

(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. Indicates the binding site with a part other than the above.)
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.

When a polymer having an organic group that induces radical polymerization is used to obtain the radical generation film used in the present invention, in order to obtain a polymer having a group capable of generating radicals, a methacryl group is used 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 that is decomposed by ultraviolet irradiation to generate a radical. It is preferable to produce using the monomer contained in. On the other hand, the monomer that generates radicals has a problem that it spontaneously polymerizes, and becomes an unstable compound. Therefore, it has a radical generation site in terms of ease of synthesis. A polymer derived from a diamine is preferable, and a polyimide precursor such as a polyamic acid or a polyamic acid ester, a polyimide, a polyurea, a polyamide, or the like is preferable.

（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−１４］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は水素原子又は炭素原子数１〜４のアルキル基を表し、Ｒ^１２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）Specific examples of such a radical-generating site-containing diamine are diamines having a side chain capable of generating radicals and being polymerized, and examples thereof include diamines represented by the following general formula (6). , Not limited to this.

(In 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 an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH _2- or -CF _{2- of the} alkylene group is independent of each other. May be replaced with a group selected from -CH = CH-, a divalent carbon ring, and a divalent heterocycle, and any of the following groups, namely -O-, -COO- , -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups, provided they are not adjacent to each other;
R ⁸ is represented by the following formula:

Represents a radical polymerization reactive group selected from.
(In formulas [X-1] to [X-14], * indicates a bonding site with a portion of the compound molecule other than the radical polymerization reactive group, and S ¹ and S ² are independently -O- and-, respectively. Represents NR- and -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Represents an alkoxy group, and R ¹ and R ² independently represent a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms).

The bonding position of the two amino groups (-NH ₂ ) in the formula (6) is not limited. Specifically, the positions 2, 3 and 2, 4 and 2, 5 and 2, 6 and 3, 4 and 3, 4 positions on the benzene ring with respect to the bonding group of the side chain. The position of 5 is mentioned. Of these, the 2,4 position, the 2,5 position, or the 3,5 position is preferable from the viewpoint of reactivity in synthesizing the polyamic acid. 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. Examples include, but are not limited to, compounds.

(In the formula, J ¹ is a bonding group selected from a single bond, -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は下記のいずれかの構造を表す。

（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 represented by the following general formula (7) include, but are not limited to, diamines that are decomposed by ultraviolet irradiation and have a site where radicals are generated as a side chain.

(In formula (7), T ¹ and T ² are independently single-bonded, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-,-. CH ₂ O-, -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-
S represents an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH _2- or -CF _{2- of the} alkylene group is independent of each other. It may be replaced with a group selected from −CH = CH−, a divalent carbocycle, and a divalent heterocyclic ring, and any of the following groups, namely −O−, −COO−,. -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups provided 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 the 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. Indicates 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 any of the following. Represents the 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. Indicates the binding site with a part other than the above.)
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 position of the two amino groups (-NH ₂ ) in the above formula (7) is not limited. Specifically, the positions 2, 3 and 2, 4 and 2, 5 and 2, 6 and 3, 4 and 3, 4 positions on the benzene ring with respect to the bonding group of the side chain. The position of 5 is mentioned. Of these, the 2,4 position, the 2,5 position, or the 3,5 position is preferable from the viewpoint of reactivity in synthesizing the polyamic acid. 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, in view of ease of synthesis, high versatility, characteristics, and the like, the structure represented by the following formula is most preferable, but the structure is not limited thereto.

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

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

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

When the polymer used for the radical generation film of the present invention is obtained from a diamine, other diamines other than the diamine having a site where the radical is generated are used in combination as a diamine component as long as the effect of the present invention is not 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 Benzenephenone, 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 (4 aminophenyl) 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) Benzene) 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) metanone], 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-Phenyl) 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 amines such as phenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane, 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 other aliphatic diamines; 1,3-bis [2- (p-amino) Diamine having a urea structure such as phenyl) ethyl] urea and 1,3-bis [2- (p-aminophenyl) ethyl] -1-tersary butyloxycarbonyl urea; N-p-aminophenyl-4-p- Amine having a nitrogen-containing unsaturated heterocyclic structure such as aminophenyl (tershally butyloxycarbonyl) aminomethylpiperidin; N-tersary butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4) Examples thereof include diamines having an N-Boc group such as −aminobenzyl) amine.

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

The tetracarboxylic dianhydride to be reacted with the above diamine component in the synthesis when the polymer is a polyamic acid 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'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyl Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) 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'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic 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-tetracarboxylic acid, 3,4-dicarboxy-1- Cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalen succinic acid, bicyclo [3,3,0] octane-2 , 4,6,8-Tetracarboxylic Acid, Bicyclo [4,3,0] Nonan-2,4,7,9-Tetracarboxylic Acid, Bicyclo [4,4,0] Decane-2,4,7,9 -Tetracarboxylic acid, bicyclo [4,4,0] decan-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-dioxo tetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydrinaphthalene-1,2-dicarboxylic acid, bicyclo [2,2,2] octo-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 , 5,6-Tricarboxynorbornane-2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and other tetracarboxylic acid dianhydrides.

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

The structure of the tetracarboxylic diandialkyl ester to be reacted with the above diamine component in the synthesis when the polymer is a polyamic acid ester is not particularly limited, and specific examples thereof will be given below.
Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 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 -Cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic 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 acetate dialkyl ester , Sis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 <2,5>] Nonan-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-dialkylester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1, Examples thereof include 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester.

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, and the like. 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^３３は炭素数１〜１０の脂肪族炭化水素を表す。The diisocyanate to be reacted with the above diamine component in the synthesis when the polymer is polyurea 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 ³³ represent aliphatic hydrocarbons having 1 to 10 carbon atoms.

The aliphatic diisocyanates shown in K-1 to K-5 are inferior in reactivity but have the advantage of improving solvent solubility, and the aromatic diisocyanates shown in K-6 to K-7 are highly reactive and heat resistant. However, there is a drawback that the solvent solubility is lowered. K-1, K-7, K-8, K-9, and K-10 are particularly preferable in terms of versatility and characteristics, K-12 is preferable in terms of electrical characteristics, and K-13 is preferable in terms of liquid crystal orientation. Especially preferable. One or more kinds of diisocyanates can be used in combination, and it is preferable to apply various diisocyanates according to the desired characteristics.
In addition, some diisocyanates can be replaced with the tetracarboxylic acid dianhydride described above, and may be used in the form of a copolymer of polyamic acid and polyurea, and the polyimide and polyurea can be chemically imidized. It may be used in the form of a copolymer.

The structure of the dicarboxylic acid to be reacted in the synthesis when the polymer is polyamide is not particularly limited, but specific examples are as follows. Specific examples of aliphatic dicarboxylic acids include malonic acid, suberic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladic acid, pimelic acid, 2,2-. Dicarboxylic acids such as dimethylglutaric acid, 3,3-diethylsuccinic acid, adipic 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-adamantandicarboxylic acid, 4,8- Examples thereof include dioxo-1,3-adamantandicarboxylic acid, 2,6-spiro [3.3] heptanedicarboxylic acid, 1,3-adamantandiacetic acid, and camphoric acid.

Examples of aromatic dicarboxylic acids include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, and 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-anthracendicarboxylic acid, 1,4 -Anthracinone 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'-stillbenzicarboxylic acid, 4,4'-transicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-dithiodibenzoic acid, p- Phenylene diacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxylacitic 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, (isopropyri 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-thiadiazol-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 various dicarboxylic acids described above may have an acid dihalide or an anhydrous structure. It is particularly preferable that these dicarboxylic acids are dicarboxylic acids capable of giving a polyamide having a linear structure from the viewpoint of maintaining the orientation of the 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 '-Diphenylpropandicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propandicarboxylic acid, 4,4-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 5-pyridinedicarboxylic acid or acid dihalide thereof and the like are preferably used. Some of these compounds have isomers, but they may be mixtures containing them. Further, two or more kinds of compounds may be used in combination. The dicarboxylic acids used in the present invention are not limited to the above-mentioned exemplified compounds.

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 reacting with the components. Generally, it is a method of reacting a diamine component with one or more components selected from a tetracarboxylic dianhydride component, a tetracarboxylic dianester, a diisocyanate and a dicarboxylic acid 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 no by-products are generated.

The organic solvent used in the above reaction is not particularly limited as long as the produced polymer dissolves. Further, even if the organic solvent does not dissolve the polymer, it may be mixed with the above solvent and used as long as the produced polymer does not precipitate. Since the water content in the organic solvent inhibits the polymerization reaction and further causes the produced polymer to be hydrolyzed, it is preferable to use a 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, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfoxide, hexamethylsulfoxide, γ- Butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellsolve, ethyl cellsolve, 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. Tel, 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, diglime, 4-hydroxy-4-methyl- Examples thereof include 2-pentanone and 2-ethyl-1-hexanol. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic 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 dianhydride component is used as it is or is organic. A method of adding by dispersing or dissolving in a solvent, conversely, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a method of adding a tetracarboxylic dianhydride component and a diamine component. Examples thereof include a method of alternately adding, and any of these methods may be used. 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 reacted individually in sequence, or may be reacted individually, and have a low molecular weight. The bodies may be mixed and reacted to form a high molecular weight compound.

The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted can be selected from 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, for example, the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass with respect to the reaction solution. ..

The ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component in the above polymerization reaction can be selected arbitrarily according to the molecular weight of the polyamic acid to be obtained. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced. The preferred 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, the above tetracarboxylic dianhydride is used in the same manner as a general method for synthesizing a polyamic acid. Alternatively, the corresponding polyamic acid can also be obtained by reacting by a known method using a tetracarboxylic acid having a corresponding structure or a tetracarboxylic acid derivative such as a tetracarboxylic acid dihalide. Further, when synthesizing polyurea, diamine and diisocyanate may be reacted. When producing a polyamic acid ester or polyamide, a diamine and a component selected from a tetracarboxylic acid diester and a dicarboxylic acid are induced into acid halide in the presence of a known condensing agent or by a known method. , Diamine may be reacted.

Examples of the method for imidizing the above-mentioned polyamic acid to obtain polyimide include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution. The imidization rate from the polyamic acid to the polyimide is preferably 30% or more, and more preferably 30 to 99%, because the voltage holding rate 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. Considering both properties, 40-80% is more preferable.

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

The catalytic imidization of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyamic acid and stirring 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, that of the amic acid group, and the amount of acid anhydride is usually 1 to 50 mol times, preferably 1 to 50 mol times that of the amic acid group. It is 3 to 30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like, and among them, acetic anhydride is preferable because it facilitates purification after completion of the reaction. The imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, the reaction time, and the like.

When the produced polymer is recovered from the reaction solution of the polymer, the reaction solution may be put into a poor solvent to precipitate. Examples of the poor solvent used for precipitation formation include methanol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like. The polymer which has been put into a poor solvent and precipitated can be collected by filtration and then dried at normal temperature or by heating under normal pressure or reduced pressure. Further, when the operation of redistributing the polymer recovered by precipitation in an organic solvent and repeating the operation of recovering the precipitation 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 generation film is composed of a polymer containing an organic group that induces radical polymerization, the radical generation film forming composition used in the present invention is 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 the total 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 radical generation film forming composition is GPC (GPC) when the strength of the radical generation film obtained by applying the radical generation film, workability at the time of coating film formation, uniformity of the coating film, etc. are taken into consideration. The weight average molecular weight measured by the Gel Permeation Chromatography method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

As a polymer in the case where the radical generating film used in the present invention is immobilized in the film by applying a composition of a compound having a group that generates a radical and a polymer and curing the film to form a 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., and a diamine having a site where radical polymerization occurs. , At least one polymer obtained by using the diamine component which is 0 mol% of the total diamine component used for synthesizing the polymer contained in the radical generation film forming composition may be used. Examples of the compound having a group that generates a radical to be added at that time include the following.

The compound that generates radicals by heat is a compound that generates radicals by heating to a temperature 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.), and hydroperoxides (peroxidation). Hydrogen, tert-butylhydroxide, cumenehydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketars (dibutylperoxycyclohexane, etc.) Etc.), alkyl peresters (peroxyneodecanic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, etc.) Examples thereof include sodium persulfate, ammonium persulfate, etc.) and azo compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile, etc.). As such a radical thermal polymerization initiator, one type may be used alone, or two or more types may be used in combination.

The compound that generates radicals with light is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators 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-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthron, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-Molholinophenyl) -butanone-1, 4-ethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 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 Su (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' -Bimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-bimidazole, 3- (2-methyl-2) -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (5-2,4-cyclopentadiene-1- Il) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-hexyl peroxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butyl peroxycarbonyl) benzophenone, 3,4'-di (3,4'-di ( Methylcarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3- (3-) Methyl-3H-benzothiazole-2-ylidene) -1-naphthalen-2-yl-etanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H) -iriden) -1- (2-) Benzoyl) Etanone and the like can be mentioned. These compounds may be used alone or in admixture of two or more.

Even when the radical generation film is composed of a polymer containing an organic group that induces radical polymerization, the group that generates the above radical is used for the purpose of promoting radical polymerization when energy is applied. The compound to be contained may be contained.

The radical generation film-forming composition can contain a polymer component, and if necessary, an organic solvent that dissolves or disperses a radical generator and other contained components. Such an organic solvent is not particularly limited, and examples thereof include organic solvents as 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. It is preferable from the viewpoint of. In particular, 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 for improving the uniformity and smoothness of the coating film by mixing it with an organic solvent having high solubility of the components contained in the radical generation film forming composition.

Examples of the solvent for improving the uniformity and smoothness of the coating film include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, and ethyl carvi. Thor, 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, Ethylisobutyl ether, diisobutylene, amylacetate, butylbutyrate, butyl ether, diisobutylketone, 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- (2-) Ethoxypropoxy) propanol, lactic acid methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, 2-ethyl-1-hexanol and the like can be mentioned. A plurality of types of these solvents may be mixed. When these solvents are used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.

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

Examples of compounds that improve the uniformity of film thickness and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Megafvck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M Ltd.) ), 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 ratio of their use is preferably 0.01 to 2 parts by mass, more preferably 0, with respect to 100 parts by mass of the total amount of the polymer contained in the radical generation film forming composition. It is 0.01 to 1 part by mass.

Specific examples of the compound for improving the adhesion between the radical generation film forming composition and the substrate include a functional silane-containing compound and an epoxy group-containing compound. 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-aminopropyltrimethoxy 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-xylene diamine, 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.

Further, in order to further increase the film strength of the radical generation film, a phenol compound such as 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol is added. May be good. When these compounds are used, the amount 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 generation film forming composition. Is.

Further, in addition to the above, the radical generating film forming composition includes a dielectric or a conductive material for changing the electrical characteristics such as the dielectric constant and the conductivity of the radical generating film as long as the effect of the present invention is not impaired. The substance may be added.

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

The substrate on which the radical generation 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 a liquid crystal is formed is preferable.
Specific examples include glass plate, polycarbonate, poly (meth) acrylate, polyether sulphon, poly arylate, polyurethane, poly sulphon, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, and tri. Examples thereof include a substrate in which a transparent electrode is formed on a plastic plate such as acetyl cellulose, diacetyl cellulose, or acetate butylate cellulose.

As the substrate that can be used for the IPS liquid crystal display element, an electrode pattern such as a standard IPS comb tooth electrode or a PSA fishbone electrode or a protrusion pattern such as MVA can also be used.
Further, in a high-performance element such as a TFT type element, an element having an element such as a transistor formed between an electrode for driving a liquid crystal and a substrate is used.
When a transmissive liquid crystal display element is intended, it is common to use a substrate as described above, but when a reflective liquid crystal display element is intended, silicon is used only for one side of the substrate. 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. From the viewpoint of productivity, the transfer printing method is widely used industrially. It is also suitably used in the present invention.

The step of drying after applying the radical generation film forming composition is not always necessary, but if the time from application to firing is not constant for each substrate or if it is not fired immediately after coating, it is dried. It is preferable to include the step. The drying is not particularly limited as long as the solvent is removed to the extent that the shape of the coating film is not deformed by the transportation of the substrate or the like, and the drying means thereof is not particularly limited. For example, a method of drying on a hot plate having 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 generation film forming composition by the above method can be fired to form a cured film. At that time, the firing temperature can be usually any temperature of 100 ° C. to 350 ° C., but is preferably 140 ° C. to 300 ° C., more preferably 150 ° C. to 230 ° C., and further preferably 160 ° C. to 220 ° C. ℃. The firing time is usually any time from 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 oven, or the like can be used.

The thickness of the cured film can be selected as needed, but it is preferably 5 nm or more, more preferably 10 nm or more because the reliability of the liquid crystal display element can be 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.

As described above, the first substrate having the radical generating film can be obtained, and the radical generating film can be subjected to the uniaxial orientation treatment. Examples of the method for performing the uniaxial alignment treatment include a photoalignment method, an orthorhombic deposition method, rubbing, and a uniaxial orientation treatment using a magnetic field.

When the orientation treatment is performed by 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 tooth electrode is formed, the direction is selected depending on the electrical properties of the liquid crystal, but when a liquid crystal having positive dielectric anisotropy is used, the rubbing direction is the comb tooth electrode. It is preferable that the direction is substantially the same as the extending direction of.

The second substrate of the present invention is the same as the first substrate except that it does not have a radical generation film. It is preferable to use a substrate having a conventionally known liquid crystal alignment film.

<LCD cell>
The liquid crystal cell of the present invention comprises a substrate having the radical generating film (first substrate) and a substrate having a known liquid crystal alignment film (second substrate) after forming a radical generating film on the substrate by the above method. Is arranged so that the radical generating film and the liquid crystal alignment film face each other, the spacer is sandwiched between the two, fixed with a sealant, and a liquid crystal composition containing a liquid crystal, a chiral dopant and a radically polymerizable compound is injected and sealed. Obtained by At that time, the size of the spacer used is usually 1 to 30 μm, but preferably 2 to 10 μm.
The method of injecting a liquid crystal composition containing a liquid crystal, a chiral dopant and a radically polymerizable compound is not particularly limited, and a vacuum method in which a mixture containing the liquid crystal and the polymerizable compound is injected after the inside of the produced liquid crystal cell is depressurized. Examples thereof include a dropping method in which a mixture containing a liquid crystal and a polymerizable compound is dropped and then sealed.

<Liquid crystal composition containing liquid crystal, chiral dopant and radically polymerizable compound>
In the production of the liquid crystal display element of the present invention, the polymerizable compound used together with the liquid crystal is not particularly limited as long as it is a radically polymerizable compound, but for example, a compound having one or two or more polymerizable unsaturated bonds in one molecule. Is. It is preferably a compound having one polymerizable unsaturated bond in one molecule (hereinafter, it may be referred to as "a compound having a monofunctional polymerizable group", "a compound having a monofunctional polymerizable group" or the like. ). The polymerizable unsaturated bond is preferably a radically polymerizable unsaturated bond, for example a vinyl bond.

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

（式中、＊は化合物分子の重合性不飽和結合以外の部分との結合部位を示す）As the polymerizable group of the radically polymerizable compound, a polymerizable group selected from the following structures is preferable.

(In the formula, * indicates the binding site of the compound molecule with a portion other than the polymerizable unsaturated bond)

Further, in the liquid crystal composition containing the liquid crystal, the chiral dopant and the radical polymerizable compound, the radical polymerizable compound having a Tg of 100 ° C. or less of the polymer obtained by polymerizing the radical polymerizable compound is contained. Is preferable.

A compound having a monofunctional radically polymerizable group has an unsaturated bond capable of performing radical polymerization in the presence of an organic radical, and is, for example, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, etc. Methacrylate monomers such as nonyl methacrylate, lauryl methacrylate, n-octyl methacrylate; acrylate monomers such as t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, lauryl acrylate, n-octyl acrylate; styrene, Styrene derivatives (eg, o-, m-, p-methoxystyrene, o-, m-, pt-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (eg, acetate) Vinyl, 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-vinylpyrrolidone, N-vinyl, etc.) Pyrrole, N-vinylcarbazole, N-vinylindole, etc.), (meth) acrylic acid derivatives (eg, acrylonitrile, metaacrylonitrile, acrylamide, isopropylacrylamide, methacrylicamide, etc.), vinyl halides (eg, vinyl chloride, vinylidene chloride, etc.) , Tetrachloroethylene, hexachloroprene, vinyl fluoride, etc.), but are not limited thereto. These various radically polymerizable monomers may be used alone or in combination of two or more. Moreover, it is preferable that these have compatibility with the liquid crystal.

The content of the radically polymerizable compound in the liquid crystal composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 50, based on the total mass of the liquid crystal and the radically polymerizable compound. It is mass% 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 that exhibits both solid and liquid properties, and there are nematic liquid crystal and smectic liquid crystal as typical liquid crystal phases, but the liquid crystal that can be used in the present invention is not particularly limited. One example is 4-pentyl-4'-cyanobiphenyl.

The chiral dopant refers to an optically active compound added in a small amount to a nematic liquid crystal in order to obtain a cholesteric liquid crystal. The chiral dopant does not necessarily have to be liquid crystal, but may be liquid crystal. In general, chiral dopants produce intermolecular forces that act to align nematic liquid crystal molecules at a slight angle to each other.
The spiral pitch of the cholesteric liquid crystal is variable depending on the structure of the chiral dopant and the amount of addition.
Specific examples of chiral dopants include non-polymerizable chiral compounds such as R-811, S-811, R-1011, S-1011, R-2011, S-2011, R-3011, S-3011, R. -4011, S-4011, R-5011, S-5011, or standard chiral dopants such as CB15 (Merck), sorbitols as described in WO98 / 00248A1, GB2,328,207. Hydrobenzoins, chiral binaphthols as described in WO02 / 94805A1, chiral binaphthol acetals as described in WO02 / 34739A1, chiral TADDOLs as described in WO02 / 06265A1, Alternatively, a chiral compound having a fluorinated cross-linking group as described in WO02 / 06196A1 or WO02 / 06195A1 can be mentioned. Examples of the polymerizable chiral compound include a polymerizable chiral material Pariocolor (registered trademark) LC756 (BASF).
The amount of the chiral dopant added needs to be appropriately adjusted depending on the twist angle and twist pitch, but is usually in the range of 0.001% by mass to 1% by mass.

Next, sufficient energy is given to the liquid crystal cell into which the liquid crystal, a mixture containing the chiral dopant and the radically polymerizable compound (liquid crystal composition) is introduced, to carry out the polymerization reaction of the radically polymerizable compound. This can be done, for example, by applying heat or UV irradiation, and the radically polymerizable compound is polymerized in situ to exhibit the desired properties. Among them, UV irradiation is preferable because the use of UV enables orientation patterning and the polymerization reaction can be carried out in a shorter time.

Further, heating may be performed during UV irradiation. The heating temperature at the time of UV irradiation is preferably in the temperature range in which the introduced liquid crystal exhibits liquid crystal properties, and is usually 40 ° C. or higher, preferably below a temperature at which the liquid crystal changes to an isotropic phase.

Here, as the UV irradiation wavelength in the case of UV irradiation, it is preferable to select the wavelength having the best reaction quantum yield of the reactive polymerizable compound, and the UV irradiation amount is usually 0.01 to 30 J / cm ² . However, preferably, when the UV irradiation amount is 10 J / cm ² or less and the UV irradiation amount is small, the reliability deterioration due to the destruction of the members constituting the liquid crystal display can be suppressed, and the UV irradiation time can be reduced, so that the manufacturing process can be performed. It is suitable because it improves tact. Irradiation may be performed for a long time in a wavelength range including 313 nm.

Further, it is preferable that the heating in the case of polymerizing only by heating instead of UV irradiation is performed in a temperature range in which the temperature at which the polymerizable compound reacts and is lower than the decomposition temperature of the liquid crystal. Specifically, for example, it is 40 ° C. or higher and 100 ° C. or lower.

When sufficient energy is applied to carry out the polymerization reaction of the radically polymerizable compound, it is preferable that no voltage is applied and the state is in an electric field-free state.

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

The present invention will be specifically described with reference to 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 method for evaluating the properties are as follows.

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

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

<Measurement of imidization rate>
20 mg of polyimide powder is placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Kagaku Co., Ltd.), and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) is added. Then, it was completely dissolved by applying ultrasonic waves. The 500 MHz proton NMR of this solution was measured with a measuring device (JNW-ECA500 manufactured by JEOL Datum Ltd.).
The imidization rate 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 value 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 value.
Imidization rate (%) = (1-α · x / y) × 100
In the formula, x is the integrated value of the NH-derived proton peak of the amide group, y is the integrated value of the peak of the reference proton, and α is the reference proton for one NH proton of the amide group in the case of polyamic acid (imidization rate is 0%). It is the number ratio of.

<Polymer polymerization and preparation of radical generation film forming composition>
Synthesis example 1
TC-1, TC-2 (50) / DA-1 (50), DA-2 (50) Polyimide Polymerization DA-1 is placed in a 100 ml 4-neck flask equipped with a nitrogen introduction tube, an air cooling tube, and a mechanical stirrer. 1.62 g (15.00 mmol) and DA-2 were measured at 3.96 g (15.00 mmol), NMP 48.2 g was added, and the mixture was stirred under a nitrogen atmosphere to completely dissolve it. After confirming the dissolution, 3.75 g (15.00 mmol) of TC-2 was added, and the mixture was reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. The temperature was returned 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 solution having a polyamic acid concentration of 20% by mass.
In 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 to prepare a 7 mass% solution, and add 9.10 g of anhydrous acetic acid with 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 at 55 ° C. for 3 hours for 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. The solid is collected by filtration, the solid is further added to 300 ml of methanol, and the mixture is stirred and washed twice for 30 minutes. The solid is collected by filtration, air-dried, and then dried in a vacuum oven at 60 ° C. A polyimide (PI-1) having a number average molecular weight of 11300, a weight average molecular weight of 32900, and an imidization rate of 53% was obtained.

Synthesis example 2
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-3 (50) polyimides DA-1 is placed in a 100 ml 4-neck flask equipped with a nitrogen introduction tube, an air cooling tube, and a mechanical stirrer. 1.62 g (15.00 mmol) and DA-3 were measured at 4.96 g (15.00 mmol), 51.90 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere to completely dissolve it. After confirming the dissolution, 3.75 g (15.00 mmol) of TC-2 was added, and the mixture was reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. The temperature was returned 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 solution having a polyamic acid concentration of 20% by mass.
In 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 to prepare a 7 mass% solution, and add 8.38 g of anhydrous acetic acid with 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 at 55 ° C. for 3 hours for 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. The solid is collected by filtration, the solid is further added to 300 ml of methanol, and the mixture is stirred and washed twice for 30 minutes. The solid is collected by filtration, air-dried, and then dried in a vacuum oven at 60 ° C. A polyimide (PI-2) having a number average molecular weight Mn of 13100, a weight average molecular weight Mw of 34000, and an imidization rate of 55% was obtained.

Synthesis example 3
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-4 (50) polyimides DA-1 is placed in a 100 ml 4-neck flask equipped with a nitrogen introduction tube, an air cooling tube, and a mechanical stirrer. 1.62 g (15.00 mmol) and DA-4 were weighed at 5.65 g (15.00 mmol), 55.4 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere to completely dissolve it. After confirming the dissolution, 3.75 g (15.00 mmol) of TC-2 was added, and the mixture was reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. The temperature was returned to room temperature again, 2.82 g (14.40 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 solution having a polyamic acid concentration of 20% by mass.
In 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 to prepare a 7 mass% solution, and add 8.36 g of anhydrous acetic acid with stirring. 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 at 55 ° C. for 3 hours for 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. The solid is collected by filtration, the solid is further added to 300 ml of methanol, and the mixture is stirred and washed twice for 30 minutes. The solid is collected by filtration, air-dried, and then dried in a vacuum oven at 60 ° C. A polyimide (PI-3) having a number average molecular weight Mn of 12900, a weight average molecular weight Mw of 31000, and an imidization rate of 51% was obtained.

Radical Generation Membrane Formation Composition: Preparation of AL1 Weigh 2.0 g of the polyimide powder (PI-1) obtained in Synthesis Example 1 into a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, add 18.0 g of NMP, and add 50 ° C. It was stirred with and completely dissolved. 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 radical generation film-forming composition according to the present invention: AL1 (solid content: 6.0% by mass, NMP: 66% by mass, BCS). : 30% by mass) was obtained.

Radical generation 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. It was stirred with and completely dissolved. 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 radical generation film-forming composition according to the present invention: AL2 (solid content: 6.0% by mass, NMP: 66% by mass, BCS). : 30% by mass) was obtained.

Non-radical generation film forming composition: Preparation of 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 measured, 18.0 g of NMP was added, and 50 was added. The mixture was stirred at ° C and completely dissolved. Further, 6.7 g of NMP and 6.7 g of BCS were added, and the mixture was further stirred for 3 hours to compare a non-radical generation film-forming composition: AL3 (solid content: 6.0% by mass, NMP: 66% by mass, BCS: 30% by mass) was obtained.

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

(First board)
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-tooth pattern having an electrode width of 10 μm and an electrode-to-electrode distance of 10 μm is formed on the substrate to form pixels. The size of each pixel is 10 mm in length and about 5 mm in width.
AL1 to AL3 or SE-6414 were filtered through a 1.0 μm filter, then applied to the electrode forming surface of the IPS substrate by a spin coating method, 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 obtain a coating film having a film thickness of 100 nm.
In the rubbing treatment "Yes", rubbing was performed so that the rubbing direction was parallel to the comb tooth electrode. The rubbing was performed using a rayon cloth manufactured by Yoshikawa Kako: YA-20R 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 above 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 the mixture was dried at 80 ° C. for 10 minutes.

(Second board)
The second substrate (also referred to as the back surface 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).
AL1, AL2 or SE-6414 was filtered through a 1.0 μm filter, then applied to the electrode-forming surface of the IPS substrate by a spin coating method, and dried on a hot plate at 80 ° C. for 1 minute. Next, AL1 and AL2 were fired at 150 ° C. for 20 minutes, and SE-6414 was fired at 220 ° C. for 20 minutes to obtain a coating film having a film thickness of 100 nm, and then a rubbing treatment was performed. The rubbing treatment was performed using a rayon cloth manufactured by Yoshikawa Kako: YA-20R under the conditions of a roll diameter of 120 mm, a rotation speed of 1000 rpm, a moving speed of 50 mm / sec, and a pushing amount of 0.4 mm. However, the above-mentioned rotation speed of the film coated with AL1 or AL2 was set to 300 rpm. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, and the mixture was dried at 80 ° C. for 10 minutes.

(Making a liquid crystal cell)
Using the above two types of substrates with a liquid crystal alignment film (first substrate and second substrate), the periphery was sealed leaving the liquid crystal injection port, and an empty cell having a cell gap of about 4 μm was prepared. At this time, if the first substrate is not rubbed, the direction of the comb tooth electrode of the first substrate is combined so that the rubbing direction of the second substrate is parallel, and if the first substrate is rubbed, the first substrate is rubbed. The rubbing directions of the first substrate and the second substrate were combined so as to be antiparallel.
A liquid crystal (MLC-3019 manufactured by Merck & Co., Inc. with 10 wt% HMA added) was vacuum-injected into the empty cell at room temperature, and then the injection port 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 20 minutes.
With UV treatment, the liquid crystal cell was irradiated with ultraviolet rays using a high-pressure mercury lamp through a bandpass filter having a wavelength of 313 nm so that the exposure amount was 1000 mJ / cm ² .

<Evaluation of liquid crystal orientation>
The orientation of the liquid crystal cell was confirmed using a polarizing plate set on Cross Nicol. Those that were oriented without defects were marked with ◯, those with minor orientation defects were marked with Δ, and those without orientation were marked with x.

<Measurement of VT curve and evaluation of drive 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 is set between them so that the brightness is minimized, and the voltage is applied to 8V at 1V intervals. The VT curve was measured by applying the voltage and measuring the brightness at the voltage. From the obtained VT curve, the values of the drive threshold voltage and the voltage that maximizes the brightness were estimated.

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

In the comparison of Cell-1 to Cell-20 using the horizontal alignment film rubbing on the back surface ITO substrate (second substrate) side, the cell using the radical generating film on the IPS substrate (first substrate) side and UV-treated Cell It was confirmed that in -11, Cell-12, Cell-16, and Cell-17, the orientation of the liquid crystal was good, and the drive threshold voltage and the maximum luminance voltage were lowered. Further, the Toff value is increased in Cell-11 and Cell-12 in which the radical generation film is not rubbed, whereas this Toff value is increased in Cell-16 and Cell-17 in which the radical generation film is rubbed. It was confirmed that the increase in radicals was greatly 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 surface 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, orientation defects and bright spots (flow orientation) along the flow direction at the time of liquid crystal injection were observed before UV irradiation, but the flow orientation completely disappeared after UV irradiation, and the domain derived from the liquid crystal. (Srilen) was confirmed. For this reason, when a radical generating film and a liquid crystal containing a polymerizable compound are used in combination, the radical generating film loses the liquid crystal orientation regulating force by irradiating with UV, and a zero-plane anchoring film is formed on the radical generating film. It was suggested that it would be done.

Further, in the comparison of the liquid crystal cells Cell-21 to Cell-24, Cell-21 and Cell-23 not irradiated with UV showed uniaxial orientation in the rubbing direction, but Cell-22 and Cell-24 subjected to UV irradiation. Cell-24 changed to an unoriented state, and a liquid crystal domain (schlieren) was generated. This suggests that even when the radical generation film is rubbed, a zero-plane anchoring film is formed on the radical generation film by irradiating with UV.

However, when Cell-22 and Cell-24 were observed while rotating under the cross Nicol, a slight change in brightness occurred. Therefore, this zero-plane anchoring film is not in a state where there is no orientation regulating force. Its regulatory force is weaker than the intermolecular force between liquid crystals, suggesting that this regulatory force alone does not uniaxially orient the liquid crystal molecules in either 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 above-mentioned weak regulatory force acted.

<Manufacturing of liquid crystal display element>
Using AL1 to AL3 obtained above and SE-6414 (manufactured by Nissan Chemical Industries, Ltd.), which is a liquid crystal alignment agent for horizontal alignment, a liquid crystal display element was produced with the configuration shown in Table 5.

(First board)
The first substrate (hereinafter, also referred to as FFS substrate) is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. An IZO electrode forming a counter electrode is formed on the entire surface of the substrate as a first layer. A SiN (silicon nitride) film formed by a CVD method is formed as a second layer on the IZO electrode of the first layer. The thickness of the SiN film of the second layer is 500 nm, and it functions as an interlayer insulating film. On the SiN film of the second layer, a comb-teeth-shaped pixel electrode formed by patterning an IZO film as the third layer is arranged, and the size of the pixel is 10 mm in length and about 10 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.
In the comb-shaped electrode shape of the third layer, the width of the electrodes in the lateral direction is 3 μm, and the distance between the electrodes is 6 μm.
AL1 to AL3 or SE-6414 were filtered through a 1.0 μm filter, then applied to the electrode forming surface of the FFS substrate by a spin coating method, and dried on a hot plate at 80 ° C. for 1 minute. Next, AL1 to AL3 were fired at 210 ° C. for 20 minutes, and SE-6414 was fired at 220 ° C. for 20 minutes and fired to obtain a coating film having a film thickness of 100 nm.
In the rubbing treatment “Yes”, rubbing was performed so that the rubbing directions intersected the longitudinal direction of the comb tooth electrode at an angle of 85 °. The rubbing was performed using a rayon cloth manufactured by Yoshikawa Kako: YA-20R 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 above 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 the mixture was dried at 80 ° C. for 10 minutes.

(Second board)
The second substrate (also referred to as the back surface 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).
The liquid crystal alignment agent to be applied was SE-6414, filtered through a 1.0 μm filter, then applied to the surface of the back surface ITO substrate by a spin coating method, and dried on a hot plate at 80 ° C. for 1 minute. Then, it was fired at 220 ° C. for 20 minutes to form a coating film having a film thickness of 100 nm, and then a rubbing treatment was performed. The rubbing treatment was performed using a rayon cloth manufactured by Yoshikawa Kako: YA-20R under the conditions of a roll diameter of 120 mm, a rotation speed of 1000 rpm, a moving speed of 50 mm / sec, and a pushing amount of 0.4 mm. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, and the mixture was dried at 80 ° C. for 10 minutes.

(Making a liquid crystal cell)
Using the above two types of substrates with a liquid crystal alignment film (first substrate and second substrate), the periphery was sealed leaving the liquid crystal injection port, and an empty cell having a cell gap of about 4 μm was prepared. At this time, the first substrate was combined so that the direction of the comb tooth electrode of the first substrate and the rubbing direction of the second substrate were parallel regardless of the presence or absence of the rubbing treatment.
A liquid crystal (MLC-3019 manufactured by Merck & Co., Inc. with 10 wt% of HMA added and chiral dopant S-5011) was vacuum-injected into this empty cell, and then the injection port was sealed to form a liquid crystal cell. The obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. Then, the obtained liquid crystal cell was heat-treated at 120 ° C. for 20 minutes.
With UV treatment, the liquid crystal cell was irradiated with ultraviolet rays through a high-pass filter having a wavelength of 300 nm using a high-pressure mercury lamp so that the exposure amount was 5000 mJ / cm ^{2 in} terms of energy at 365 nm.

<Evaluation of liquid crystal orientation>
The orientation of the liquid crystal cell was confirmed using a polarizing plate set on Cross Nicol. Those that were oriented without defects were marked with ◯, those with minor orientation defects were marked with Δ, and those without orientation were marked with x.

<Measurement of VT curve and evaluation of drive threshold voltage and minimum brightness 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 is set between them so that the brightness is maximized, and the voltage is applied to 8V at 1V intervals. The VT curve was measured by applying the voltage and measuring the brightness at the voltage. From the obtained VT curve, the values of the drive threshold voltage and the voltage at which the brightness was minimized were estimated.

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

When the FFS substrate side is not rubbed, the horizontal orientation cannot be confirmed even if the back surface ITO side is rubbed. Severe flow orientation was confirmed. On the other hand, when the rubbing treatment was performed, all of them showed twist orientation except those without a film.

When this twist-oriented cell was driven, the minimum luminance voltage was 10 V or more, and even if a voltage of 20 V or more was applied, a completely black display was not obtained.

The orientation of the liquid crystal could not be confirmed for those without rubbing on the FFS substrate side, but samples showing twist orientation appeared when irradiated with UV (Cell-11', Cell-12'). On the other hand, Cell-13'to Cell-15' showed no orientation and were in an unoriented state. From this, it is considered that the alignment film having an organic group exhibiting radical polymerization creates a state in which the liquid crystal is oriented. In addition, a significant decrease in the voltage that became the lowest brightness when driven was confirmed, and a black display was shown.

It was also found that among the samples subjected to the rubbing treatment + UV irradiation, in Cell-16'and Cell-17', not only the drive threshold voltage and the minimum luminance voltage were lowered, but also the Toff value was greatly improved. On the other hand, in Cell-18'to Cell-20', the results were the same as those in which UV irradiation was not performed, and it was found that no change occurred. From this, it is considered that such a characteristic behavior can be produced by UV irradiation treatment using an alignment film containing an organic group having radical polymerization property and a liquid crystal containing a polymerizable compound.

As a supplementary experiment, when a liquid crystal containing no chiral dopant was used, the cells in which UV was applied to the cells using UVAL-1 and AL-2 were horizontally oriented regardless of the presence or absence of rubbing treatment, and were twisted. It was not possible to verify the operation using.

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

Claims (22)

A zero-plane anchor comprising a step of imparting sufficient energy to polymerize the radically polymerizable compound in a state where the liquid crystal composition containing the liquid crystal, the chiral dopant and the radically polymerizable compound is in contact with the radical generating film. A method for producing a ring film. The method according to claim 1, wherein the radical generation film contained in the first substrate is a radical generation film subjected to uniaxial orientation treatment. The method according to claim 1 or 2, wherein the step of applying energy is performed without an 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. Claim 1 is characterized in that the radical-generating film is obtained by applying a composition of a compound having a radical-generating group and a polymer and curing the mixture to form a film, thereby immobilizing the film. The method according to any one of 3 to 3. The method according to any one of claims 1 to 3, wherein the radical generating film is composed of a polymer containing an organic group that induces radical polymerization. The polymer containing an organic group that induces radical polymerization is at least one 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 claim 6, wherein the polymer is a polymer. Claims 4, 6 and 7 wherein the organic group that induces radical polymerization is an organic group represented by the following structures [X-1] to [X-14], [W], [Y] and [Z]. The method according to any one item.

(In the formulas [X-1] to [X-14], * indicates a bonding site with a portion other than the polymerizable unsaturated bond of the compound molecule, and S ¹ and S ² are independently -O- and-, respectively. Represents NR- and -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Represents an alkoxy group, and R ¹ and R ² independently represent a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms).

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

(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. Indicates the binding site with a part other than the above.)
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 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 an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH _2- or -CF _{2- of the} alkylene group is independent of each other. May be replaced with a group selected from -CH = CH-, a divalent carbon ring, and a divalent heterocycle, and any of the following groups, namely -O-, -COO- , -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups, provided they are not adjacent to each other;
R ⁸ is represented by the following formula:

Represents a radical polymerization reactive group selected from.
(In formulas [X-1] to [X-14], * indicates a bonding site with a portion of the compound molecule other than the radical polymerization reactive group, and S ¹ and S ² are independently -O- and-, respectively. Represents NR- and -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Represents an alkoxy group, and R ¹ and R ² independently represent a hydrogen atom, a halogen atom, and an alkyl group having 1 to 4 carbon atoms))

(In formula (7), T ¹ and T ² are independently single-bonded, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-,-. CH ₂ O-, -N (CH ₃ )-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-
S represents an alkylene group having 1 to 20 carbon atoms which is single-bonded, or unsubstituted or substituted with a fluorine atom, and one or more of any -CH _2- or -CF _{2- of the} alkylene group is independent of each other. It may be replaced with a group selected from −CH = CH−, a divalent carbocycle, and a divalent heterocyclic ring, and any of the following groups, namely −O−, −COO−,. -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups provided 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 bond with T ^2, and Ar is phenylene, naphthylene, and biphenylene which may have an organic group and / or a halogen atom as a substituent. Indicates 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 any of the following. Represents the 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. Indicates the binding site with a part other than the above.)
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 one polymerizable unsaturated bond in one molecule, which is compatible with liquid crystal. The method according to claim 10, wherein the polymerizable unsaturated bond of the radically polymerizable compound is selected from the following structures.

(In the formula, * indicates the binding site of the compound molecule with a portion other than the polymerizable unsaturated bond) In a liquid crystal composition containing the liquid crystal, a chiral dopant and a radically polymerizable compound, a liquid crystal composition containing a radically polymerizable compound having a Tg of a polymer obtained by polymerizing the radically polymerizable compound of 100 ° C. or less. The method according to any one of claims 1 to 11, wherein the method is used. A step of preparing a first substrate having a radical generating film and a second substrate having a radical generating film may be prepared.
A step of creating a cell so that the radical generation film on the first substrate faces the second substrate, and
A step of filling a liquid crystal composition containing a liquid crystal, a chiral dopant and a radically polymerizable compound between the first substrate and the second substrate is included.
A method for manufacturing a liquid crystal cell using the method according to any one of claims 1 to 12. 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 for 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 orientation. The method for manufacturing a liquid crystal cell according to claim 15, wherein the liquid crystal alignment film having uniaxial orientation is a liquid crystal alignment film for horizontal alignment. The method for producing a liquid crystal cell according to any one of claims 13 to 16, wherein the first substrate having the radical generation film is a substrate having a comb tooth electrode. Contains liquid crystals, chiral dopants and radically polymerizable compounds
At least one of the radically polymerizable compounds is a compound having a polymerizable unsaturated bond in one molecule and having compatibility with a liquid crystal.
A liquid crystal composition in which a polymerizable unsaturated bond is selected from the following structures.

(In the formula, * indicates the binding site of the compound molecule with a portion other than the polymerizable unsaturated bond) A method for manufacturing a liquid crystal display element using a film that creates a zero-plane anchoring state obtained by using the method according to any one of claims 1 to 17. A liquid crystal display element 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 electrodes. The liquid crystal display element according to claim 20 or 21, which is a low-voltage drive transverse electric field liquid crystal display element.