JP7276149B2 - Manufacturing method of zero plane anchoring film and liquid crystal display element - Google Patents

Description

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

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 content such as VR and ultra-high-definition displays in the future. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment) have been proposed as display methods for liquid crystal displays. A film (liquid crystal alignment film) that induces the

Especially for products equipped with touch panels such as tablet PCs, smartphones, and smart TVs, IPS mode is preferred because the display is less likely to be disturbed even when touched. A liquid crystal display element using field switching and a technique using a non-contact technique using photo-alignment have come to be used.

However, the FFS has a problem in that the manufacturing cost of the substrate is higher than that in the IPS, and a display defect peculiar to the FFS mode called Vcom shift occurs. As for photo-alignment, compared to the rubbing method, there are advantages in that the size of the device that can be manufactured can be increased and display characteristics can be greatly improved. display failure, and if it is an isomerization type, burn-in due to insufficient orientation force, etc.). At present, liquid crystal display device manufacturers and liquid crystal alignment film manufacturers are devising various ways to solve these problems.

On the other hand, in recent years, an IPS mode using a so-called zero-plane anchoring has been proposed, and it has been reported that using this method makes it possible to improve the contrast and drive at a significantly lower voltage than the conventional IPS mode. (see Patent Document 1).

Specifically, a liquid crystal alignment film having a strong anchoring energy is used for one of the substrates, and the substrate provided with electrodes for generating a horizontal electric field has no liquid crystal alignment regulating force at all. It is a method of making an IPS mode liquid crystal display device by applying various treatments and using them.

In recent years, technical proposals have been made for a cello-plane anchoring IPS mode by creating a zero-plane state using a dense polymer brush or the like (Reference 2). This technology significantly improves the contrast ratio and significantly lowers the drive voltage.

Japanese Patent No. 4053530 JP 2013-231757 A

On the other hand, this technology has its own problems in principle. First, in order to stably generate polymer brushes on the substrate, it must be performed under very delicate conditions, which is not realistic in terms of mass production. There is no Secondly, although the alignment film plays an important role such as suppression of image sticking, it is difficult to control necessary electrical properties when a polymer brush or the like is used. The third is that the response speed becomes very slow when the voltage is turned off due to the driving principle. It is expected that the threshold voltage will be greatly reduced by eliminating the resistance applied to the liquid crystal during driving by reducing the alignment control force to zero, and the luminance will be improved due to the reduction of the poor alignment region during driving. As for , the return power of the liquid crystal depends on the elastic force of the liquid crystal, so it is conceivable that the speed is greatly reduced compared to when there is an alignment film.
If such technical issues can be resolved, it will be a significant cost advantage for the panel manufacturer, and it is thought that it will also be advantageous in terms of reducing battery consumption and improving image quality.
The present invention has been made in order to solve the above-described problems, and a manufacturing method that applies a polymer stabilization technology that can manufacture a zero-plane anchoring film, and a simple and inexpensive method at room temperature. It is an object of the present invention to provide a lateral electric field liquid crystal display device and a method for manufacturing the same, which can simultaneously achieve non-contact alignment, lower drive voltage, and faster response speed when the device is off.

In order to solve the above problems, the present inventors conducted intensive studies, found that the above problems can be solved, and 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 liquid crystal composition containing a liquid crystal, a chiral dopant, and a radically polymerizable compound is brought into contact with a radical-generating film, and a step of applying sufficient energy to polymerize the radically polymerizable compound is provided. A method for manufacturing a zero-plane anchoring membrane.
[2] The method according to [1], wherein the radical generating film of the first substrate is a uniaxially oriented radical generating film.
[3] The method of claim 1 or 2, wherein the step of applying energy is performed without an electric field.
[4] The method according to any one of [1] to [3], wherein the radical-generating film is a film in which an organic group that induces radical polymerization is fixed.
[5] The radical-generating film is obtained by applying and curing a composition of a compound having a radical-generating group and a polymer to form a film, thereby fixing the composition in the film. The method according to any one of claims 1-3.
[6] The method according to any one of [1] to [3], wherein the radical-generating film comprises a polymer containing an organic group that induces radical polymerization.
[7] The polymer containing an organic group that induces radical polymerization is selected from polyimide precursors, polyimides, polyureas and polyamides obtained using a diamine component containing a diamine containing an organic group that induces radical polymerization. 7. A method according to claim 6, characterized in that it is at least one polymer.
[8] The organic groups that induce radical polymerization are organic groups represented by the following structures [X-1] to [X-14], [W], [Y] and [Z]. and 8. The method of 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 each independently -O- and -NR- , -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms)

(In the formulas [W], [Y], [Z], * indicates a bonding 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. an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, wherein R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms When R ⁹ and R ¹⁰ are alkyl groups, they may be bonded to each other at the ends to form a ring structure, Q represents any one of the following structures.

(Wherein, 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 the Q of the compound molecule. It shows the binding site with moieties other than.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )
[9] The method according to [7], wherein the diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following general formula (6) or (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—,
R ⁷ represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and one or more of any —CH ₂ — or —CF ₂ — in the alkylene group are each independently may be substituted with a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and any of the following groups, i.e., -O-, -COO- , —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups, provided that these groups are not adjacent to each other;
R ⁸ has the formula:

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

(In formula (7), T ¹ and T ² are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, - CH ₂ O—, —N(CH ₃ )—, —CON(CH ₃ )—, or —N(CH ₃ )CO—;
S represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and any one or more of —CH ₂ — or —CF ₂ — in the alkylene group are each independently -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and any of the following groups, i.e., -O-, -COO-, —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups provided that they are not adjacent to each other;
J is an organic group represented by the following formula,

(In the formulas [W], [Y], and [Z], * represents the bonding site with T ² , and Ar is phenylene, naphthylene, and biphenylene, which may have an organic group and/or a halogen atom as a substituent. represents an aromatic hydrocarbon group selected from the group consisting of R ⁹ and R ¹⁰ each independently represents 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 of

(Wherein, 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 the Q of the compound molecule. It shows the binding site with moieties other than.)
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] At least one of the radically polymerizable compounds is a compound having compatibility with liquid crystals and having one polymerizable unsaturated bond in one molecule. the method of.
[11] The method according to [10], wherein the polymerizable unsaturated bond of the radically polymerizable compound is selected from the following structures.

(Wherein, * indicates a bonding site with a portion other than the polymerizable unsaturated bond of the compound molecule)
[12] The liquid crystal composition containing the liquid crystal, the chiral dopant and the radically polymerizable compound contains a radically polymerizable compound such that the Tg of the polymer obtained by polymerizing the radically polymerizable compound is 100° C. or less. A method according to any one of claims 1 to 11, characterized in that a liquid crystal composition is used.
[13] A step of preparing a first substrate having a radical-generating film and a second substrate which may have a radical-generating film;
creating a cell such that the radical-generating film on the first substrate faces the second substrate;
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;
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 [13], wherein the second substrate is a second substrate having no radical-generating film.
[15] The method for manufacturing a liquid crystal cell according to [14], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment.
[16] The method for producing a liquid crystal cell according to [15], wherein the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment.
[17] The method for producing a liquid crystal cell according to any one of [13] to [16], wherein the first substrate having the radical generating film is a substrate having a comb-teeth electrode.
[18] containing a liquid crystal, a chiral dopant and a radically polymerizable compound,
At least one of the radically polymerizable compounds is a compound having compatibility with the liquid crystal and having one polymerizable unsaturated bond in one molecule,
A liquid crystal composition in which the polymerizable unsaturated bond is selected from the following structures.

(Wherein, * indicates a bonding site with a portion other than the polymerizable unsaturated bond of the compound molecule)
[19] A method for manufacturing a liquid crystal display element using a film that produces a zero-plane anchoring state obtained by using the method according to any one of [1] to [17].
[20] A liquid crystal display device obtained by using the method according to [19].
[21] The liquid crystal display element according to [20], wherein the first substrate or the second substrate has an electrode.
[22] The liquid crystal display device according to [20] or [21], which is a low-voltage horizontal electric field liquid crystal display device.

According to the present invention, a zero-plane anchoring film can be produced industrially with a high yield. Using the method of the present invention, a liquid crystal display device similar to the zero plane anchoring IPS mode liquid crystal display devices described in Patent Documents 1 and 2 can be easily manufactured using inexpensive raw materials and existing manufacturing methods. In addition, the liquid crystal display element obtained by the manufacturing method of the present invention has a faster liquid crystal response speed when turned off than the conventional technology, a low driving voltage, no bright spots, can suppress Vcom shift in the IPS mode, and has an FFS. It is possible to provide a liquid crystal display element having excellent characteristics such as the ability to achieve even higher definition in the mode.

The present invention is a method for producing a zero-plane anchoring film, wherein the polymerizable compound is polymerized by UV or heat while the 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 optionally having a radical generating film. A method for producing a zero-plane anchoring film, comprising the steps of: preparing a cell; and applying sufficient energy to the cell to polymerize the radically polymerizable compound. Preferably, a step of preparing a first substrate having a radical-generating film and a second substrate not having a radical-generating film, forming a cell so that the radical-generating film faces the second substrate, and A method for manufacturing a liquid crystal cell, comprising the 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 driven IPS liquid crystal display device 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-teeth electrode. It is the method of creation.

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

[Radical generating film forming composition]
The radical-generating film-forming composition for forming the radical-generating film used in the present invention contains, as components, a polymer and a radical-generating group. 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 can be a thing. By coating and curing such a composition to form a film, a radical-generating film in which groups capable of generating radicals are fixed in the film can be obtained. The radical-generating group 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 organic groups that induce 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 each independently -O-, - represents NR-, -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, represents an alkoxy group, and R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms)

(In the formulas [W], [Y], [Z], * indicates a bonding 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. an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, wherein R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; When R ⁹ and R ¹⁰ are alkyl groups, they may be bonded to each other at the ends to form a ring structure, Q represents any one of the following structures.

(Wherein, 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 the Q of the compound molecule. It shows the binding site with moieties other than.)
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. )

Preferred polymers are, for example, polyimide precursors and at least one polymer selected from the group consisting of polyimides, polyureas, polyamides, polyacrylates, polymethacrylates, and the like.

In order to obtain the radical-generating film used in the present invention, when a polymer having an organic group that induces radical polymerization is used, in order to obtain a polymer having a radical-generating group, a methacryl group, 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, or a site that is decomposed by ultraviolet irradiation to generate a radical is a side chain. It is preferable to manufacture using a monomer having On the other hand, monomers that generate radicals have the potential to spontaneously polymerize themselves, resulting in unstable compounds. Polymers derived from diamines are preferred, and polyimide precursors such as polyamic acids and polyamic acid esters, polyimides, polyureas, and polyamides are more preferred.

（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 radical-generating site-containing diamines are diamines having side chains capable of generating radicals and polymerizing, and diamines represented by the following general formula (6) can be mentioned. , but not limited to.

(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—,
R ⁷ represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and one or more of any —CH ₂ — or —CF ₂ — in the alkylene group are each independently may be substituted with a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and any of the following groups, i.e., -O-, -COO- , —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups, provided that these groups are not adjacent to each other;
R ⁸ has the formula:

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

The bonding positions of the two amino groups (—NH ₂ ) in formula (6) are not limited. Specifically, the 2,3-positions, 2,4-positions, 2,5-positions, 2,6-positions, 3,4-positions, 3, 4-positions, and 3,4-positions on the benzene ring are 5 positions are included. Among them, the 2,4-position, the 2,5-position, or the 3,5-position is preferable from the viewpoint of reactivity when synthesizing the polyamic acid. The 2,4-position or the 3,5-position is more preferable considering the ease in synthesizing the diamine.

（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 acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group include the following. compounds include, but are not limited to.

(Wherein, J ¹ is a single bond, —O—, —COO—, —NHCO—, or a bonding group selected from —NH—; J ² is a single bond, or an unsubstituted or substituted 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 having a side chain that is decomposed by ultraviolet irradiation to generate radicals include, but are not limited to, diamines represented by the following general formula (7).

(In formula (7), T ¹ and T ² are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, - CH ₂ O—, —N(CH ₃ )—, —CON(CH ₃ )—, or —N(CH ₃ )CO—;
S represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and any one or more of —CH ₂ — or —CF ₂ — in the alkylene group are each independently -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and any of the following groups, i.e., -O-, -COO-, —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups provided that they are not adjacent to each other;
J is an organic group represented by the following formula,

(In the formulas [W], [Y], and [Z], * represents the bonding site with T ² , and Ar is phenylene, naphthylene, and biphenylene, which may have an organic group and/or a halogen atom as a substituent. represents an aromatic hydrocarbon group selected from the group consisting of R ⁹ and R ¹⁰ each independently represents 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 of

(Wherein, 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 the Q of the compound molecule. It shows the binding site with moieties other than.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ))

The bonding positions of the two amino groups (—NH ₂ ) in the above formula (7) are not limited. Specifically, the 2,3-positions, 2,4-positions, 2,5-positions, 2,6-positions, 3,4-positions, 3, 4-positions, and 3,4-positions on the benzene ring are 5 positions are included. Among them, the 2,4-position, the 2,5-position, or the 3,5-position is preferable from the viewpoint of reactivity when synthesizing the polyamic acid. The 2,4-position or the 3,5-position is more preferable considering the ease in synthesizing the diamine.

（式中、ｎは２～８の整数である。）In particular, in view of ease of synthesis, high versatility, properties, etc., the structures represented by the following formulas are most preferable, but are not limited to these.

(Wherein, n is an integer of 2 to 8.)

The above diamines may be used singly or in combination of two or more depending on properties such as liquid crystal alignment when forming a radical-generating film, sensitivity in polymerization reaction, voltage holding properties, and accumulated charge.

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

When the polymer used in the radical-generating film of the present invention is obtained from diamine, other diamines than the diamine having a radical-generating site are used in combination as diamine components as long as the effects of the present invention are 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'-diaminobenzophenone, 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-amino phenyl)benzene, 1,4-bis(4-aminobenzyl)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-phenylenebis(methylene)]dianiline, 3,3′-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl ) methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone ], 1,4-phenylene bis (4-aminobenzoate), 1,4-phenylene bis (3-aminobenzoate), 1,3-phenylene bis (4-aminobenzoate), 1,3-phenylene bis (3- aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1, 4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide) ), N,N′-(1,3-phenylene)bis(3-aminobenzamide), N,N′-bis(4-aminophenyl)terephthalamide, N,N′-bis(3-aminophenyl)terephthalamide Amide, 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-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoro Propane, 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-aminophenoxy)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-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, aromatic diamines such as 1,12-bis(3-aminophenoxy)dodecane; alicyclic diamines such as bis(4-aminocyclohexyl)methane and bis(4-amino-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-diamino Aliphatic diamines such as decane, 1,11-diaminoundecane, 1,12-diaminododecane; 1,3-bis[2-(p-aminophenyl)ethyl]urea, 1,3-bis[2-(p- diamines having a urea structure such as aminophenyl)ethyl]-1-tert-butyloxycarbonyl urea; diamines having a saturated heterocyclic structure; diamines having an N-Boc group such as N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine be done.

The above-mentioned other diamines may be used singly or in combination of two or more according to properties such as liquid crystal orientation when forming a radical generating film, sensitivity in polymerization reaction, voltage holding properties, and accumulated charge. .

In the synthesis when the polymer is a polyamic acid, the tetracarboxylic dianhydride to be reacted with the diamine component is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyl Tetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-di carboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl) Propane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4 -dicarboxyphenyl)pyridine, 3,3′,4,4′-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-tetrahydrofurantetracarboxylic acid, 3,4-dicarboxy-1- Cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo[3,3,0]octane-2 ,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,7,9 -tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane-3,5,9, 11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydrinaphthalene-1,2 -dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclo Hexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0<2,7>]dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane tetracarboxylic acid dianhydrides such as -2:3,5:6 dicarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid.

Of course, the tetracarboxylic dianhydride may be used alone or in combination of two or more depending on the characteristics such as the liquid crystal alignment when forming the radical generating film, the sensitivity in the polymerization reaction, the voltage retention characteristics, and the accumulated charge. .

In the synthesis when the polymer is a polyamic acid ester, the structure of the tetracarboxylic acid dialkyl ester to be reacted with the diamine component is not particularly limited, but specific examples are given below.
Specific examples of aliphatic tetracarboxylic acid diesters 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-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1 -cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-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 acetic acid dialkyl ester , cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0<2,5>]nonane-3, 4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl ester, hexacyclo[6.6.0.1<2,7>. 0<3,6>. 1<9, 14>. 0<10,13>]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 4-(2,5-dioxotetrahydrofuran-3-yl)-1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester and the like.

Examples of aromatic tetracarboxylic acid dialkyl esters include pyromellitic acid dialkyl ester, 3,3′,4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2′,3,3′-biphenyltetracarboxylic acid dialkyl ester, 2,3,3′,4-biphenyltetracarboxylic acid dialkyl ester, 3,3′,4,4′-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3′,4′-benzophenonetetracarboxylic 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。In the synthesis when the polymer is polyurea, the diisocyanate to be reacted with the diamine component is not particularly limited, and can be used according to availability and the like. Specific structures of diisocyanates are shown below.

In the formula, R ²² and R ³³ represent aliphatic hydrocarbons having 1 to 10 carbon atoms.

Aliphatic diisocyanates shown in K-1 to K-5 are inferior in reactivity but have the advantage of improving solvent solubility, and aromatic diisocyanates shown in K-6 to K-7 are highly reactive and heat resistant. However, it has the disadvantage of lowering solvent solubility. K-1, K-7, K-8, K-9, and K-10 are particularly preferable in terms of versatility and characteristics, K-12 in terms of additional electrical characteristics, and K-13 in terms of liquid crystal orientation. Especially preferred. One or more kinds of diisocyanates can be used in combination, and it is preferable to apply various kinds of diisocyanates according to desired properties.
Also, part of the diisocyanate can be replaced with the tetracarboxylic dianhydride described above, and it may be used in the form of a copolymer of polyamic acid and polyurea, and chemical imidization can be used to convert polyimide and polyurea. It may be used in the form of a copolymer.

In synthesis when the polymer is polyamide, the structure of the dicarboxylic acid to be reacted is not particularly limited, but specific examples are as follows. Specific examples of aliphatic dicarboxylic acids include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2- Mention may be made of dicarboxylic acids such as dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaiic acid, sebacic acid and suberic acid.

Alicyclic dicarboxylic acids include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, and 1,3-cyclobutanedicarboxylic acid. acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-(2-norbornene)dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, bicyclo [2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8- Dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid and the like can be mentioned.

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-anthracenedicarboxylic acid, 1,4 -anthraquinonedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4''-terphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4 , 4′-diphenylethanedicarboxylic acid, 4,4′-diphenylpropanedicarboxylic acid, 4,4′-diphenylhexafluoropropanedicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-bibenzyldicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 4,4'-trandicarboxylic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 4,4'-dithio dibenzoic acid, p- Phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3'-[4,4'-(methylenedi-p-phenylene)]dipropion acid, 4,4′-[4,4′-(oxydi-p-phenylene)]dipropionic acid, 4,4′-[4,4′-(oxydi-p-phenylene)]dibutyric acid, (isopropyl Dicarboxylic acids such as dendi-p-phenylenedioxy)dibutyric acid and bis(p-carboxyphenyl)dimethylsilane can be mentioned.

Dicarboxylic acids containing a heterocyclic ring include 1,5-(9-oxofluorene)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid and the like can be mentioned.

The various dicarboxylic acids mentioned above may be of the acid dihalide or anhydrous structure. These dicarboxylic acids are preferably dicarboxylic acids capable of giving a polyamide having a linear structure, in order to maintain the orientation of liquid crystal molecules. Among these, terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylethanedicarboxylic acid, 4,4 '-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis(phenyl)propanedicarboxylic acid, 4,4-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 5-pyridinedicarboxylic acid or acid dihalides thereof are preferably used. Although some of these compounds have isomers, mixtures containing them may also be used. Moreover, you may use together 2 or more types of compounds. The dicarboxylic acids used in the present invention are not limited to the compounds exemplified above.

Selected from raw material diamine (also referred to as "diamine component") and raw material tetracarboxylic dianhydride (also referred to as "tetracarboxylic dianhydride component"), tetracarboxylic acid diester, diisocyanate and dicarboxylic acid In obtaining polyamic acids, polyamic acid esters, polyureas, and polyamides by reaction with components, known synthesis techniques can be used. Generally, it is a method of reacting a diamine component with one or more components selected from a tetracarboxylic dianhydride component, a tetracarboxylic acid diester, 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 does not generate by-products.

The organic solvent used in the above reaction is not particularly limited as long as it dissolves the produced polymer. Furthermore, even an organic solvent in which the polymer does not dissolve may be used by being mixed with the above solvent within a range in which the produced polymer is not precipitated. The water content in the organic solvent inhibits the polymerization reaction and further hydrolyzes the polymer produced. Therefore, it is preferable to use the organic solvent after dehydration and drying.

Examples of organic solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2 -pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ- Butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether , dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, Ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, 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, methyl 3-ethoxypropionate ethyl, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2 -ethyl-1-hexanol and the like. 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, a solution obtained by dispersing or dissolving the diamine component in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent. 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, and a method of adding a tetracarboxylic dianhydride component and a diamine component. A method of adding them alternately and the like can be mentioned, and any of these methods may be used. Further, when the diamine component or the tetracarboxylic dianhydride component consists of a plurality of types of compounds, the reaction may be performed in a mixed state in advance, or may be reacted individually in sequence, or may be reacted individually. may be mixed and reacted to form a high molecular weight product.

Any temperature can be selected for the reaction of the diamine component and the tetracarboxylic dianhydride component, for example, in the range of -20 to 100°C, preferably -5 to 80°C. Further, the reaction can be performed 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, relative to the reaction solution. .

In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected as desired depending on the molecular weight of the polyamic acid to be obtained. As in ordinary polycondensation reactions, the closer this molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced. A preferable range is 0.8 to 1.2.

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

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

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

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

In the case of recovering the produced polymer from the reaction solution of the polymer, the reaction solution may be put into a poor solvent to precipitate. Poor solvents used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by putting it into a poor solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure. In addition, the impurities in the polymer can be reduced by redissolving the precipitated and recovered polymer in an organic solvent and repeating the operation of reprecipitating and recovering 2 to 10 times. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons, and the like. It is preferable to use three or more poor solvents selected from these, because the purification efficiency is further improved.

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

The molecular weight of the polymer contained in the radical-generating film-forming composition is determined by GPC ( 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 the polymer for obtaining the radical generating film used in the present invention by applying and curing a composition of a compound having a radical generating group and a polymer to form a film and fixing it in the film , a polyimide precursor produced according to the above production method, and a polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc., wherein the diamine having a site where radical polymerization occurs At least one polymer obtained by using a diamine component that is 0 mol % of the total diamine component used in synthesizing the polymer to be contained in the radical-generating film-forming composition may be used. Examples of the compound having a radical-generating group to be added at that time include the following.

The compound that generates radicals by heat is a compound that generates radicals when heated to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxide hydrogen, tert-butyl hydroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane etc.), alkyl peresters (peroxyneodecanoic acid -tert-butyl ester, peroxypivalic acid -tert-butyl ester, peroxy 2-ethylcyclohexanoic acid -tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.). Such radical thermal polymerization initiators can be used singly or in combination of two or more.

The compound that generates radicals by 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, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate, 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'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl )-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl- 1,2′-biimidazole, 2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 3-(2 -methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis(5-2,4-cyclo Pentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone , 3,3′,4,4′-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3′-di(methoxycarbonyl)-4,4′-di(t-butylperoxycarbonyl)benzophenone, 3,4 '-di(methoxycarbonyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2 -(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone or 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1 -(2-benzoyl)ethanone and the like. These compounds may be used alone or in combination of two or more.

Even when the radical-generating film is composed of a polymer containing an organic group that induces radical polymerization, the groups that generate radicals are added for the purpose of promoting radical polymerization when energy is applied. You may contain the compound which has.

The radical-generating film-forming composition can contain an organic solvent for dissolving or dispersing the polymer component and, if necessary, the radical-generating agent and other ingredients. Such an organic solvent is not particularly limited, and examples thereof include the organic solvents exemplified in the above 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 is preferable from the viewpoint of N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is particularly preferable, but a mixed solvent of two or more kinds may be used.

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

Solvents that improve the uniformity and smoothness of coating films include, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, and ethyl carb. 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, Ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate , methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3 -ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1 -phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2 -ethoxypropoxy)propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, 2-ethyl-1-hexanol and the like. A plurality of types of these solvents may be mixed. When using these solvents, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass of the total solvent contained in the liquid crystal aligning agent.

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

Compounds that improve film thickness uniformity 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)), Megaface F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) ), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). When these surfactants are used, the proportion used is preferably 0.01 to 2 parts by mass, more preferably 0 parts by mass, based on 100 parts by mass of the total amount of the polymer contained in the radical-generating film-forming composition. 0.01 to 1 part by mass.

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

In addition, in order to further increase the film strength of the radical generation film, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, tetra(methoxymethyl)bisphenol, or other phenol compounds may be added. good too. 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-generating film-forming composition. is.

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

[Radical generation film]
The radical-generating film of the present invention is obtained using the radical-generating film-forming composition. For example, the radical-generating film-forming composition used in the present invention may be applied to a substrate, dried and baked, and the resulting cured film may be used as it is as the radical-generating film. In addition, the cured film may be rubbed, irradiated with polarized light or light of a specific wavelength, treated with an ion beam, or used as an alignment film for PSA to irradiate a liquid crystal display element after liquid crystal filling with UV. is also possible.

The substrate on which the radical-generating film-forming composition is applied is not particularly limited as long as it is highly transparent, but a substrate having a transparent electrode for driving liquid crystal formed thereon is preferable.
Specific examples include glass plate, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, tri Substrates in which a transparent electrode is formed on a plastic plate of acetylcellulose, diacetylcellulose, acetate butyrate cellulose, or the like can be mentioned.

Substrates that can be used in IPS mode liquid crystal display devices may have electrode patterns such as standard IPS comb-teeth electrodes and PSA fishbone electrodes, and protruding patterns such as MVA.
Further, in a highly functional element such as a TFT type element, a device in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.
When a transmissive liquid crystal display device is intended, the substrates as described above are generally used. Opaque substrates such as wafers can also be used. At that time, a material such as aluminum that reflects light can also be used for the electrodes formed on the substrate.

Examples of methods for applying the radical-generating film-forming composition include spin coating, printing, ink jet, spraying, and roll coating, but transfer printing is widely used industrially from the standpoint of productivity. and is preferably used in the present invention.

The step of drying after coating the radical-generating film-forming composition is not necessarily required. It is preferable to include steps. The drying means is not particularly limited as long as the solvent is removed to such an extent that the coating film shape is not deformed by transportation of the substrate or the like. For example, it may be dried on a hot plate at a temperature of 40°C to 150°C, preferably 60°C to 100°C for 0.5 to 30 minutes, preferably 1 to 5 minutes.

The coating film formed by applying the radical-generating film-forming composition by the above method can be baked to form a cured film. At that time, the firing temperature can be generally any temperature of 100° C. to 350° C., preferably 140° C. to 300° C., more preferably 150° C. to 230° C., still more preferably 160° C. to 220° C. °C. Firing can be carried out for an arbitrary period of time, usually 5 minutes to 240 minutes. It is preferably 10 to 90 minutes, more preferably 20 to 90 minutes. Heating can be performed by a commonly known method such as a hot plate, hot air circulation oven, IR oven, belt furnace and the like.

The thickness of this cured film can be selected according to need, 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 device does not become extremely large, which is preferable.

A first substrate having a radical generating film can be obtained as described above, and the radical generating film can be subjected to a uniaxial orientation treatment. Examples of the method for uniaxial orientation treatment include a photo-alignment method, an oblique vapor deposition method, rubbing, and a uniaxial orientation treatment using a magnetic field.

When the orientation treatment is performed by rubbing in one direction, for example, while rotating a rubbing roller around which a rubbing cloth is wound, the substrate is moved so that the rubbing cloth and the film are in contact with each other. In the case of the first substrate of the present invention on which comb-teeth electrodes are formed, the direction is selected according to the electrical properties of the liquid crystal. It is preferable that the direction is substantially the same as the direction in which the .

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

<Liquid crystal cell>
In the liquid crystal cell of the present invention, after forming a radical generating film on a substrate by the above method, a substrate (first substrate) having the radical generating film and a substrate (second substrate) having a known liquid crystal alignment film are formed. are placed so that the radical generating film and the liquid crystal alignment film face each other, sandwiching a spacer and fixing with a sealing agent, and injecting a liquid crystal composition containing a liquid crystal, a chiral dopant and a radically polymerizable compound for sealing. obtained by In that case, the size of the spacer to be used is usually 1 to 30 μm, preferably 2 to 10 μm.
The method of injecting the liquid crystal composition containing the liquid crystal, chiral dopant and radically polymerizable compound is not particularly limited. A dropping method in which sealing is performed after dropping a mixture containing a liquid crystal and a polymerizable compound can be exemplified.

<Liquid Crystal Composition Containing Liquid Crystal, Chiral Dopant and Radically Polymerizable Compound>
In preparing the liquid crystal display device 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. For example, a compound having one or more polymerizable unsaturated bonds in one molecule. is. Preferably, it is a compound having one polymerizable unsaturated bond in one molecule (hereinafter sometimes referred to as "a compound having a monofunctional polymerizable group", "a compound having a monofunctional polymerizable group", etc. ). The polymerizable unsaturated bond is preferably a radically polymerizable unsaturated bond, such as a vinyl bond.

At least one of the radically polymerizable compounds is preferably a compound having one polymerizable unsaturated bond in one molecule, which is compatible with the 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.

(Wherein, * indicates a bonding site with a portion other than the polymerizable unsaturated bond of the compound molecule)

Further, the liquid crystal composition containing the liquid crystal, the chiral dopant and the radically polymerizable compound contains a radically polymerizable compound such that the Tg of the polymer obtained by polymerizing the radically polymerizable compound is 100° C. or lower. is preferred.

A compound having a monofunctional radically polymerizable group has an unsaturated bond capable of undergoing radical polymerization in the presence of an organic radical. Examples thereof include t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, methacrylate monomers such as nonyl methacrylate, lauryl methacrylate and n-octyl methacrylate; acrylate monomers such as t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, lauryl acrylate and n-octyl acrylate; styrene, Styrene derivatives (e.g. o-, m-, p-methoxystyrene, o-, m-, pt-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (e.g., acetic acid vinyl, vinyl propionate, vinyl benzoate, vinyl acetate, etc.), vinyl ketones (e.g., vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (e.g., N-vinylpyrrolidone, N-vinyl pyrrole, N-vinylcarbazole, N-vinylindole, etc.), (meth)acrylic acid derivatives (e.g., acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), vinyl halides (e.g., vinyl chloride, vinylidene chloride , tetrachloroethylene, hexachloroprene, vinyl fluoride, etc.). These various radically polymerizable monomers may be used alone or in combination of two or more. Moreover, it is preferable that these have liquid crystal and compatibility.

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% by mass, based on the total mass of the liquid crystal and the radically polymerizable compound. % by mass or less, more preferably 20% by mass or less.

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

Liquid crystal generally refers to a substance that exhibits both solid and liquid properties, and typical liquid crystal phases include nematic liquid crystal and smectic liquid crystal, but the liquid crystal that can be used in the present invention is not particularly limited. One example is 4-pentyl-4'-cyanobiphenyl.

A chiral dopant is an optically active compound added in a small amount to a nematic liquid crystal to obtain a cholesteric liquid crystal. The chiral dopant does not necessarily have to exhibit liquid crystallinity, but may have liquid crystallinity. In general, chiral dopants create intermolecular forces that force nematic liquid crystal molecules to align at small angles to each other.
The helical pitch of cholesteric liquid crystals is variable depending on the structure and amount of chiral dopants.
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 - standard chiral dopants such as 4011, S-4011, R-5011, S-5011, or CB15 (Merck); sorbitols as described in WO 98/00428 A1; chiral binaphthols as described in WO02/94805A1; chiral binaphthol acetals as described in WO02/34739A1; chiral TADDOLs as described in WO02/06265A1; Or chiral compounds having a fluorinated bridging group as described in WO02/06196A1 or WO02/06195A1. Examples of the polymerizable chiral compound include polymerizable chiral material Paliocolor (registered trademark) LC756 (BASF Corporation).
The amount of the chiral dopant to be added must be appropriately adjusted according to the degree of twist angle and twist pitch, but is usually in the range of 0.001% by mass to 1% by mass.

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

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

Here, for the UV irradiation wavelength in the case of UV irradiation, it is preferable to select a wavelength with the best reaction quantum yield of the reacting polymerizable compound, and the UV irradiation dose is usually 0.01 to 30 J/cm ² . However, it is preferably 10 J/cm ² or less, and the smaller the amount of UV irradiation, the more it is possible to suppress the decrease in reliability due to the destruction of the members constituting the liquid crystal display, and the shorter the UV irradiation time, the more difficult it is to manufacture. This is preferable because it improves the takt time. Long-term irradiation may be performed in a wavelength range that includes 313 nm.

Moreover, when polymerizing only by heating instead of UV irradiation, the heating is preferably performed within a temperature range at which the polymerizable compound reacts and is lower than the decomposition temperature of the liquid crystal. Specifically, for example, the temperature is 40° C. or higher and 100° C. or lower.

It is preferable that no voltage is applied and no electric field is applied when sufficient energy is applied to cause the polymerization reaction of the radically polymerizable compound.

<Liquid crystal display element>
A liquid crystal display element can be produced 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, and the like according to a conventional method.
In addition, 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.

EXAMPLES 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 of characterization are as follows.

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

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

<Measurement of imidization rate>
Put 20 mg of polyimide powder in an NMR sample tube (manufactured by Kusano Kagaku NMR sampling tube standard φ5), and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture). and completely dissolved by applying ultrasonic waves. 500 MHz proton NMR of this solution was measured with a measurement device (JNW-ECA500, manufactured by JEOL Datum Co., Ltd.).
For the imidization rate, a proton derived from a structure that does not change before and after imidization is determined as a reference proton. It was obtained by the following formula using the value and
Imidation rate (%) = (1-α x/y) x 100
In the formula, x is the NH-derived proton peak integrated value of the amide group, y is the peak integrated value 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%). is the number ratio of

<Polymer Polymerization and Preparation of Radical-Generating Film-Forming Composition>
Synthesis example 1
TC-1, TC-2 (50) / DA-1 (50), DA-2 (50) Polymerization of polyimide DA-1 was added to a 100 ml four-necked flask equipped with a nitrogen introduction tube, an air cooling tube, and a mechanical stirrer. 1.62 g (15.00 mmol) and 3.96 g (15.00 mmol) of DA-2 were weighed out, and 48.2 g of NMP was added and stirred under a nitrogen atmosphere to completely dissolve them. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60° C. for 3 hours under 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. After confirming the polymerization viscosity, TC-1 was further added so that the polymerization viscosity reached 1000 mPa·s to obtain a polymerization liquid having a polyamic acid concentration of 20% by mass.
Weigh 60 g of the polyamic acid solution obtained above into a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP to prepare a 7% by mass solution, and add 9.10 g of acetic anhydride while stirring ( 88.52 mmol) and 3.76 g (47.53 mmol) of pyridine were added, and the mixture was stirred at room temperature for 30 minutes and then stirred at 55°C for 3 hours to react. After completion of the reaction, the solution was returned to room temperature and poured into 500 ml of methanol with stirring to precipitate a solid. Collect the solid by filtration, put the solid into 300 ml of methanol, wash with stirring for 30 minutes twice in total, collect the solid by filtration, air-dry it, and then dry it in a vacuum oven at 60°C. to obtain a polyimide (PI-1) having a number average molecular weight of 11,300, a weight average molecular weight of 32,900 and an imidization rate of 53%.

Synthesis example 2
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-3 (50) polyimide A 100 ml four-necked flask equipped with a nitrogen inlet tube, an air cooling tube, and a mechanical stirrer was charged with DA-1. 1.62 g (15.00 mmol) and 4.96 g (15.00 mmol) of DA-3 were weighed, 51.90 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere to dissolve completely. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60° C. for 3 hours under 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. After confirming the polymerization viscosity, TC-1 was further added so that the polymerization viscosity reached 1000 mPa·s to obtain a polymerization liquid having a polyamic acid concentration of 20% by mass.
Weigh 60 g of the polyamic acid solution obtained above into a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP to prepare a 7% by mass solution, and add 8.38 g of acetic anhydride while stirring. (81.4 mmol) and 3.62 g (45.8 mmol) of pyridine were added, stirred at room temperature for 30 minutes, and then stirred at 55° C. for 3 hours to react. After completion of the reaction, the solution was returned to room temperature and poured into 500 ml of methanol with stirring to precipitate a solid. Collect the solid by filtration, put the solid into 300 ml of methanol, wash with stirring for 30 minutes twice in total, collect the solid by filtration, air-dry it, and then dry it in a vacuum oven at 60°C. A polyimide (PI-2) having a number average molecular weight Mn of 13,100, a weight average molecular weight Mw of 34,000 and an imidization rate of 55% was obtained.

Synthesis example 3
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-4 (50) polyimide A 100 ml four-necked flask equipped with a nitrogen inlet tube, an air cooling tube, and a mechanical stirrer was charged with DA-1. 1.62 g (15.00 mmol) and 5.65 g (15.00 mmol) of DA-4 were weighed, 55.4 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere to dissolve completely. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60° C. for 3 hours under 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. After confirming the polymerization viscosity, TC-1 was further added so that the polymerization viscosity reached 1000 mPa·s to obtain a polymerization liquid having a polyamic acid concentration of 20% by mass.
Weigh 60 g of the polyamic acid solution obtained above into a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP to prepare a 7% by mass solution, and add 8.36 g of acetic anhydride while 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 stirred at 55°C for 3 hours to react. After completion of the reaction, the solution was returned to room temperature and poured into 500 ml of methanol with stirring to precipitate a solid. Collect the solid by filtration, put the solid into 300 ml of methanol, wash with stirring for 30 minutes twice in total, collect the solid by filtration, air-dry it, and then dry it in a vacuum oven at 60°C. A polyimide (PI-3) having a number average molecular weight Mn of 12,900, a weight average molecular weight Mw of 31,000 and an imidization rate of 51% was obtained.

Radical-Generating Film-Forming Composition: Preparation of AL1 2.0 g of the polyimide powder (PI-1) obtained in Synthesis Example 1 was weighed into a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 18.0 g of NMP was added, and the mixture was heated to 50°C. was stirred to completely dissolve. Further, 6.7 g of NMP and 6.7 g of BCS were added, and the radical-generating film-forming composition according to the present invention: AL1 (solid content: 6.0% by mass, NMP: 66% by mass, BCS) was stirred for 3 hours. : 30% by mass).

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

Non-Radical Generation Film-Forming Composition: Preparation of AL3 2.0 g of the polyimide powder (PI-3) obtained in Synthesis Example 3 was weighed into a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, and 18.0 g of NMP was added. Stir at 0 C until completely dissolved. Further, 6.7 g of NMP and 6.7 g of BCS were added, and the mixture was stirred for 3 hours to give a non-radical generating film-forming composition for comparison: AL3 (solid content: 6.0% by mass, NMP: 66% by mass, BCS: 30% by mass) was obtained.

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

(First substrate)
A first substrate (hereinafter also referred to as an 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-shaped pattern with an electrode width of 10 μm and an electrode-to-electrode spacing of 10 μm is formed on the substrate to form a pixel. The size of each pixel is 10 mm long and about 5 mm wide.
AL1 to AL3 or SE-6414 was filtered through a 1.0 μm filter, applied to the electrode-forming surface of the IPS substrate by spin coating, and dried on a hot plate at 80° C. for 1 minute. Next, AL1 to AL3 were baked at 150° C. for 20 minutes, and SE-6414 was baked at 220° C. for 20 minutes, and baked to form coating films each having a thickness of 100 nm.
In the case of "with rubbing treatment", rubbing was performed so that the rubbing direction was parallel to the comb-teeth electrode. Rubbing was performed using a rayon cloth: YA-20R manufactured by Yoshikawa Kako under the conditions of a roll diameter of 120 mm, a rotation speed of 300 rpm, a moving speed of 50 mm/sec, and a pushing depth of 0.4 mm. However, only the film coated with SE-6414 was rotated at 1000 rpm. After the rubbing treatment, ultrasonic waves were applied in pure water for 1 minute and dried at 80° C. for 10 minutes.

(Second substrate)
The second substrate (also referred to as a back ITO substrate) is an alkali-free 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. A columnar spacer with 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, applied to the electrode-forming surface of the IPS substrate by spin coating, and dried on a hot plate at 80° C. for 1 minute. Next, AL1 and AL2 were baked at 150° C. for 20 minutes, and SE-6414 was baked at 220° C. for 20 minutes. The rubbing treatment was performed using Yoshikawa Kako's rayon cloth: 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 depth of 0.4 mm. However, the film coated with AL1 or AL2 was rotated at 300 rpm. After the rubbing treatment, ultrasonic waves were applied in pure water for 1 minute and dried at 80° C. for 10 minutes.

(Production of liquid crystal cell)
An empty cell with a cell gap of about 4 μm was produced by using two types of substrates (first substrate and second substrate) with the above-mentioned liquid crystal alignment film and sealing the surroundings except for the liquid crystal injection port. At this time, when the first substrate is not rubbed, the direction of the comb-tooth electrodes of the first substrate and the rubbing direction of the second substrate are parallel to each other. The first substrate and the second substrate were combined so that the rubbing directions were antiparallel.
A liquid crystal (MLC-3019 manufactured by Merck Co., Ltd. to which 10 wt % of HMA was added) was vacuum-injected into this empty cell at normal temperature, and then the injection port was sealed to obtain a liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. After that, 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 light through a band-pass filter with a wavelength of 313 nm using a high-pressure mercury lamp 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 in crossed Nicols. Those which were oriented without defects were evaluated as ◯, those which had slight orientation defects were evaluated as Δ, and those which were not oriented were evaluated as ×.

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

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

In the comparison of Cell-1 to Cell-20 using a rubbed horizontal alignment film on the back ITO substrate (second substrate) side, a UV-treated cell using a radical generation film on the IPS substrate (first substrate) side -11, Cell-12, Cell-16, and Cell-17 were confirmed to have good liquid crystal orientation and lowered drive threshold voltage and luminance maximum voltage. Cell-11 and Cell-12, in which the radical-generating film was not rubbed, showed an increased Toff value. It was confirmed that the increase in

In addition to the above, as a supplementary experiment, AL1 was used for both the back ITO substrate (second substrate) and the IPS substrate (first substrate), and neither the first substrate nor the second substrate was rubbed to prepare a liquid crystal cell. In this liquid crystal cell, alignment defects and bright spots (flow alignment) along the flow direction of the liquid crystal during injection were observed before UV irradiation. (schlieren) was confirmed. From this fact, when a radical generating film and a liquid crystal containing a polymerizable compound are used together, the radical generating film loses the ability to regulate liquid crystal alignment by UV irradiation, and a zero-plane anchoring film is formed on the radical generating film. It was suggested that

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

However, when Cell-22 and Cell-24 were observed while rotating under crossed Nicols, a slight change in brightness occurred. The regulating force is weaker than the intermolecular force between liquid crystal molecules, suggesting that the regulating force alone does not uniaxially align the liquid crystal molecules in any direction. From this, it is considered that the large improvement in the Toff value in Cell-16 and Cell-17 is due to the weak regulatory force described above.

<Production 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 aligning agent for horizontal alignment, a liquid crystal display element having the configuration shown in Table 5 was produced.

(First substrate)
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 constituting 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 SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. Comb-shaped pixel electrodes formed by patterning an IZO film as a third layer are arranged on the SiN film of the second layer, and the pixel size is 10 mm long and about 10 mm wide. 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 electrodes 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 was filtered through a 1.0 μm filter, applied to the electrode formation surface of the FFS substrate by spin coating, and dried on a hot plate at 80° C. for 1 minute. Next, AL1 to AL3 were baked at 210° C. for 20 minutes, and SE-6414 was baked at 220° C. for 20 minutes, and baked to form coating films each having a thickness of 100 nm.
In the case of "with rubbing treatment", rubbing was performed so that the rubbing direction crossed the longitudinal direction of the comb-teeth electrode at an angle of 85°. Rubbing was performed using a rayon cloth: YA-20R manufactured by Yoshikawa Kako under the conditions of a roll diameter of 120 mm, a rotation speed of 300 rpm, a moving speed of 50 mm/sec, and a pushing depth of 0.4 mm. However, only the film coated with SE-6414 was rotated at 1000 rpm. After the rubbing treatment, ultrasonic waves were applied in pure water for 1 minute and dried at 80° C. for 10 minutes.

(Second substrate)
The second substrate (also referred to as a back ITO substrate) is an alkali-free 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. A columnar spacer with a height of 4 μm is formed on the surface (the surface facing the inside of the cell).
SE-6414 was used as the liquid crystal aligning agent to be applied, and after filtering through a 1.0 μm filter, it was applied to the surface of the back ITO substrate by a spin coating method and dried on a hot plate at 80° C. for 1 minute. Then, they were baked at 220° C. for 20 minutes to form coating films having a film thickness of 100 nm, and then subjected to rubbing treatment. The rubbing treatment was performed using Yoshikawa Kako's rayon cloth: 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 depth of 0.4 mm. After the rubbing treatment, ultrasonic waves were applied in pure water for 1 minute and dried at 80° C. for 10 minutes.

(Production of liquid crystal cell)
An empty cell with a cell gap of about 4 μm was produced by using two types of substrates (first substrate and second substrate) with the above-mentioned liquid crystal alignment film and sealing the surroundings except for the liquid crystal injection port. At this time, regardless of whether or not the first substrate was subjected to rubbing treatment, the first substrate was combined so that the direction of the comb-tooth electrodes of the first substrate and the rubbing direction of the second substrate were parallel to each other.
A liquid crystal (MLC-3019 manufactured by Merck Co., Ltd. to which 10 wt % of HMA was added and chiral dopant S-5011) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to obtain a liquid crystal cell. The obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. After that, 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 light through a high-pass filter with a wavelength of 300 nm using a high-pressure mercury lamp so that the exposure amount would be 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 in crossed Nicols. Those which were oriented without defects were evaluated as ◯, those which had slight orientation defects were evaluated as Δ, and those which were not oriented were evaluated as ×.

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

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

If the FFS substrate side is not rubbed, horizontal alignment cannot be confirmed even if the back ITO side is rubbed. Severe flow orientation was confirmed. On the other hand, when the rubbing treatment was performed, all of them exhibited twisted orientation except for the one without the film.

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

Although no alignment of the liquid crystal could be confirmed for the samples on which the FFS substrate side was not rubbed, samples showing twisted alignment appeared when irradiated with UV (Cell-11', Cell-12'). On the other hand, Cell-13' to Cell-15' showed no orientation and were in a non-oriented state. From this, it is considered that the alignment film having an organic group exhibiting radical polymerizability creates a state in which the liquid crystal is aligned. In addition, a large drop in the voltage at which the minimum luminance was obtained was confirmed when the device was driven, and a black display was exhibited.

In addition, it was found that in Cell-16' and Cell-17' among the samples subjected to rubbing treatment and UV irradiation, not only the drive threshold voltage and the luminance minimum voltage decreased, 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 without UV irradiation, 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 polymerizability and a liquid crystal containing a polymerizable compound.

As a complementary experiment, when a liquid crystal containing no chiral dopant was used, the cells using UVAL-1 and AL-2 were subjected to UV irradiation, with or without rubbing, resulting in horizontal alignment and twisted alignment. It was not possible to verify the operation using

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

Claims (17)

A liquid crystal composition containing a liquid crystal, a chiral dopant, and a radically polymerizable compound is in contact with a radical-generating film that has undergone a uniaxial orientation treatment , and energy sufficient to polymerize the radically polymerizable compound is applied without an electric field. A method of manufacturing a zero-plane anchoring film, comprising the step of providing. 2. The method according to claim 1, wherein the radical-generating film is a film in which an organic group that induces radical polymerization is fixed. 3. The method according to claim 1, wherein the radical-generating film comprises 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 polyimide precursors, polyimides, polyureas and polyamides obtained using a diamine component containing a diamine containing an organic group that induces radical polymerization. 4. A method according to claim 3, characterized in that it is a polymer. Any one of claims 2 to 4, 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 item 1.

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

(In the formulas [W], [Y], [Z], * indicates a bonding 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. may represent an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene; ⁹ and R ¹⁰ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ When is an alkyl group, the terminals may be bonded to each other to form a ring structure. Q represents one of the following structures.

(In the formula, R ¹¹ Ha-CH ₂ represents -, -NR-, -O- or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site. )
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. ) 5. The method according to claim 4, 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 (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 ) represents CO-,
R. ⁷ represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and any —CH ₂ - or - CF ₂ One or more of - may each independently be replaced with a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and further any one of the following groups, i.e. , -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may be replaced by these groups provided that they are not adjacent to each other;
R. ⁸ is the following formula:

represents a radically polymerizable group selected from
(In the formulas [X-1] to [X-14], * indicates a binding site, S ¹ , S ² each independently represents -O-, -NR-, -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and R ¹ , R ² each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms))

(In formula (7), T ¹ and T ² are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-,-CON(CH ₃ )-, or -N(CH ₃ ) CO—,
S represents a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a fluorine atom, and any —CH ₂ - or - CF ₂ One or more of - may each independently be replaced with a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and further any one of the following groups, i.e. , —O—, —COO—, —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups provided that they are not adjacent to each other;
J is an organic group represented by the following formula,

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

(In the formula, R ¹¹ Ha-CH ₂ represents -, -NR-, -O- or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site. )
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 6, wherein at least one of the radically polymerizable compounds is a compound having compatibility with liquid crystals and having one polymerizable unsaturated bond in one molecule. 8. The method according to claim 7, wherein the polymerizable unsaturated bond of said radically polymerizable compound is selected from the following structures.

(Wherein, * indicates a bonding site with a portion other than the polymerizable unsaturated bond of the compound molecule) A liquid crystal composition containing the liquid crystal, a chiral dopant, and a radically polymerizable compound, wherein the polymer obtained by polymerizing the radically polymerizable compound has a Tg of 100° C. or less. The method according to any one of claims 1 to 8, characterized in that using preparing a first substrate having a radical generating film and a second substrate having a liquid crystal alignment film;
creating a cell such that the radical-generating film on the first substrate faces the second substrate;
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;
A method for manufacturing a liquid crystal cell using the method according to any one of claims 1 to 9. 11. The method of manufacturing a liquid crystal cell according to claim 10, wherein the second substrate is a second substrate having no radical-generating film. 12. The method of manufacturing a liquid crystal cell according to claim 11, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment. 13. The method of manufacturing a liquid crystal cell according to claim 12, wherein the uniaxially aligned liquid crystal alignment film is a liquid crystal alignment film for horizontal alignment. 14. The method for manufacturing a liquid crystal cell according to any one of claims 10 to 13, wherein the first substrate having the radical generating film is a substrate having a comb-teeth electrode. A method for manufacturing a liquid crystal display device using a film that produces a zero-plane anchoring state obtained by using the method according to any one of claims 1 to 14. 16. The method of manufacturing a liquid crystal display element according to claim 15, wherein the liquid crystal display element has electrodes on the first substrate or the second substrate. 16. The method of manufacturing a liquid crystal display element according to claim 15, wherein the liquid crystal display element is a low-voltage driven horizontal electric field liquid crystal display element.