JP7367673B2 - Manufacturing method of zero-plane anchoring film and liquid crystal display element - Google Patents

Description

The present invention provides a manufacturing method that applies polymer stabilization technology that allows the production of zero-plane anchoring films at low cost and without complicated processes, and a further low-voltage method 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 displays for mobile phones, computers, televisions, and the like. Liquid crystal display elements have characteristics such as being thin, lightweight, 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 have been proposed for liquid crystal displays, such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment), but all modes require the liquid crystal to be aligned in a desired state. A film (liquid crystal alignment film) that induces this is used.

In particular, IPS mode is preferred for products equipped with touch panels such as tablet PCs, smartphones, and smart TVs, where the display is less distorted even when touched. Liquid crystal display elements using field switching (field switching) and non-contact technology using optical alignment have come into use.

However, FFS has a higher substrate manufacturing cost than IPS, and there is a problem in that a display defect unique to FFS mode called Vcom shift occurs. Regarding photoalignment, compared to the rubbing method, it has the advantage of increasing the size of the device that can be manufactured and greatly improving display characteristics, but there are problems with the principle of photoalignment (if it is a decomposition type, the For example, if the isomerization type is used, there may be display defects due to insufficient orientation force, etc.). In order to solve these problems, liquid crystal display element manufacturers and liquid crystal alignment film manufacturers are currently making various efforts.

On the other hand, in recent years, an IPS mode that uses something called zero-plane anchoring has been proposed, and it has been reported that using this method improves contrast and enables significantly lower voltage driving than the conventional IPS mode. (See Patent Document 1).

Specifically, a liquid crystal alignment film with strong anchoring energy is used on one side of the substrate, while the other side of the substrate, which has the electrode that generates the transverse electric field, has no liquid crystal alignment regulating force at all. This is a method of fabricating an IPS mode liquid crystal display element by subjecting it to various treatments and using them.

In recent years, a technology has been proposed for a zero- plane anchoring IPS mode in which a zero-plane state is created using a thick polymer brush or the like ( Patent Document 2). This technology has achieved a significant improvement in contrast ratio and a significant reduction in drive voltage.

Patent No. 4053530 Japanese Patent Application Publication No. 2013-231757

On the other hand, there are issues with this technology that arise in principle.The first is that in order to stably generate polymer brushes on the substrate, it must be performed under extremely delicate conditions, which is impractical when considering mass production. One example is that there is no such thing. Second, although the alignment film plays an important role such as suppressing image sticking, when using a polymer brush or the like, it is difficult to control the necessary electrical properties. Thirdly, due to the driving principle, the response speed when the voltage is turned off is extremely slow. By reducing the alignment regulating force to zero, it is expected that the resistance applied to the liquid crystal during driving will be eliminated, resulting in a significant reduction in the threshold voltage and an improvement in brightness due to the reduction of areas with poor alignment during driving. Regarding this, since the power when the liquid crystal returns depends on the elastic force of the liquid crystal, it is thought that the speed will be significantly lower than when there is an alignment film.
If these technical issues can be resolved, it will be a huge cost advantage for panel manufacturers, and it is also conceivable that it will have benefits such as reducing battery consumption and improving image quality.
The present invention has been made to solve the above-mentioned problems, and provides a manufacturing method that applies polymer stabilization technology that can manufacture a zero-plane anchoring film, and a manufacturing method that is simple and inexpensive at room temperature. An object of the present invention is to provide a transverse electric field liquid crystal display element and a method for manufacturing the same, which can simultaneously achieve non-contact alignment, lower driving voltage, and faster response speed when off.

In order to solve the above-mentioned problems, the present inventors conducted intensive studies and found that the above-mentioned problems could be solved, and completed the present invention having the following gist.

式（１）中、Ｒ^ａおよびＲ^ｂはそれぞれ独立に炭素数２～８の直鎖アルキル基を表し、Ｅは単結合、－Ｏ－、－ＮＲ^ｃ－、－Ｓ－、エステル結合、アミド結合から選ばれる結合基を表し、Ｒ^ｃは水素原子、炭素数１～４のアルキル基を示す。
［２］ 第一基板の有する前記ラジカル発生膜が一軸配向処理されたラジカル発生膜である［１］に記載の方法。
［３］ エネルギーを与えるステップを無電界で行う、［１］又は［２］に記載の方法。
［４］ 前記ラジカル発生膜が、ラジカル重合を誘発する有機基が固定化されて成る膜であることを特徴とする［１］～［３］のいずれか一項に記載の方法。
［５］ 前記ラジカル発生膜が、ラジカルを発生する基を有する化合物と重合体との組成物を塗布、硬化して膜を形成することにより膜中に固定化させて得られることを特徴とする［１］～［３］のいずれか一項に記載の方法。
［６］ 前記ラジカル発生膜が、ラジカル重合を誘発する有機基を含有する重合体から成ることを特徴とする［１］～［３］のいずれか一項に記載の方法。
［７］ 前記ラジカル重合を誘発する有機基を含有する重合体が、ラジカル重合を誘発する有機基を含有するジアミンを含むジアミン成分を用いて得られるポリイミド前駆体、ポリイミド、ポリウレアおよびポリアミドから選ばれる少なくとも一種の重合体であることを特徴とする［６］記載の方法。
［８］ 前記ラジカル重合を誘発する有機基が下記構造［Ｘ－１］～［Ｘ－１８］、［Ｗ］、［Ｙ］、［Ｚ］で表される有機基である［４］、［６］及び［７］のいずれか一項に記載の方法。

（式［Ｘ－１］～［Ｘ１８］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_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［７］記載の方法。

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

から選択されるラジカル重合反応性基を表す。
（式［Ｘ－１］～［Ｘ－１８］中、＊は化合物分子のラジカル重合反応性基以外の部分との結合部位を示し、Ｓ_１、Ｓ_２はそれぞれ独立して－Ｏ－、－ＮＲ－、－Ｓ－を表し、Ｒは水素原子又は炭素原子数１～４のアルキル基を表し、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］ 前記式（１）中のＥがエステル結合である［１］～［９］のいずれか一項に記載の方法。
［１１］ ラジカル発生膜を有する第一基板と、ラジカル発生膜を有していてもよい第二基板とを用意するステップ、
第一基板上のラジカル発生膜が第二基板に対向するようにセルを作成するステップ、および、
第一基板と第二基板との間に、液晶及びラジカル重合性化合物を含有する液晶組成物を充填するステップを含み、
［１］～［１０］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。
［１２］ 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［１１］に記載の液晶セルの製造方法。
［１３］ 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［１２］に記載の液晶セルの製造方法。
［１４］ 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［１３］に記載の液晶セルの製造方法。
［１５］ 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［１１］～［１４］のいずれか一項に記載の液晶セルの製造方法。
［１６］ 液晶及び下記式（１）で表される構造を有するラジカル重合性化合物を含有する液晶組成物。

式（１）中、Ｒ^ａおよびＲ^ｂはそれぞれ独立に炭素数２～８の直鎖アルキル基を表し、Ｅは単結合、－Ｏ－、－ＮＲ^ｃ－、－Ｓ－、エステル結合、アミド結合から選ばれる結合基を表し、Ｒ^ｃは水素原子、炭素数１～４のアルキル基を示す。
［１７］ 前記式（１）中のＥがエステル結合である［１６］に記載の液晶組成物。
［１８］ ［１］～［１５］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。
［１９］ ［１８］記載の方法を用いて得られた液晶表示素子。
［２０］ 第一基板又は第二基板が電極を有する、［１９］に記載の液晶表示素子。
［２１］ 低電圧駆動横電界液晶表示素子である、［１９］又は［２０］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 and a radically polymerizable compound having a structure represented by the following formula (1) is brought into contact with a radical generating film, and the radically polymerizable compound is subjected to a polymerization reaction. A method for producing a zero-plane anchoring membrane comprising the step of providing sufficient energy.

In formula (1), R ^a and R ^b each independently represent a straight chain alkyl group having 2 to 8 carbon atoms, and E is a single bond, -O-, -NR ^c -, -S-, an ester bond, an amide It represents a bonding group selected from bonds, and R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
[2] The method according to [1], wherein the radical generating film of the first substrate is a radical generating film subjected to uniaxial alignment treatment.
[3] The method according to [1] or [2], wherein the step of applying energy is performed without an electric field.
[4] The method according to any one of [1] to [3], wherein the radical generating film is a film on which an organic group that induces radical polymerization is immobilized.
[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 [1] to [3].
[6] The method according to any one of [1] to [3], wherein the radical generating film is made of a polymer containing an organic group that induces radical polymerization.
[7] The polymer containing an organic group that induces radical polymerization is selected from polyimide precursors, polyimides, polyureas, and polyamides obtained using a diamine component containing a diamine containing an organic group that induces radical polymerization. The method according to [6], wherein the method is at least one kind of polymer.
[8] The organic group that induces radical polymerization is an organic group represented by the following structures [X-1] to [X-18], [W], [Y], [Z] [4], [ 6] and [7].

(In formulas [X-1] to [X18], * 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-, -NR- , -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 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], and [Z], * indicates a bonding site with a part other than a polymerizable unsaturated bond in the compound molecule, and Ar has an organic group and/or a halogen atom as a substituent. R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. When R ⁹ and R ¹⁰ are alkyl groups, they may be bonded to each other at the ends to form a ring structure. Q represents any of the following structures.

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

(In 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 arbitrary -CH ₂ - or -CF ₂ - of the alkylene group are each independently may be substituted with a group selected from -CH=CH-, divalent carbocycle, and divalent heterocycle, and further, any of the following groups, namely -O-, -COO- , -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups, provided that they are not adjacent to each other;
^R8 is the following formula:

Represents a radical polymerization reactive group selected from.
(In formulas [X-1] to [X-18], * indicates a bonding site with a moiety other than the radical polymerization reactive group of the compound molecule, and S ₁ and S ₂ are each independently -O-, - NR-, -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 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 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 unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms, and one or more of -CH ₂ - or -CF ₂ - in the alkylene group are each independently It may be substituted with a group selected from -CH=CH-, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups, provided that they are not adjacent to each other,
J is an organic group represented by the following formula,

(In the formulas [W], [Y], and [Z], * represents the bonding site with _T2 , and Ar represents phenylene, naphthylene, and biphenylene which may have an organic group and/or a halogen atom as a substituent. R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q is any of the following. represents the structure of

(In the formula, R ¹¹ represents -CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents the Q of the compound molecule. (Indicates the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. ))
[10] The method according to any one of [1] to [9], wherein E in the formula (1) is an ester bond.
[11] A step of preparing a first substrate having a radical generating film and a second substrate optionally having a radical generating film,
creating a cell such that the radical generating film on the first substrate faces the second substrate, and
A step of filling a liquid crystal composition containing a liquid crystal 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 [1] to [10].
[12] The method for manufacturing a liquid crystal cell according to [11], wherein the second substrate does not have a radical generating film.
[13] The method for manufacturing a liquid crystal cell according to [12], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment.
[14] The method for manufacturing a liquid crystal cell according to [13], wherein the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment.
[15] The method for manufacturing a liquid crystal cell according to any one of [11] to [14], wherein the first substrate having the radical generating film is a substrate having comb-teeth electrodes.
[16] A liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a structure represented by the following formula (1).

In formula (1), R ^a and R ^b each independently represent a straight chain alkyl group having 2 to 8 carbon atoms, and E is a single bond, -O-, -NR ^c -, -S-, an ester bond, an amide It represents a bonding group selected from bonds, and R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
[17] The liquid crystal composition according to [16], wherein E in the formula (1) is an ester bond.
[18] A method for manufacturing a liquid crystal display element using a film that creates a zero-plane anchoring state obtained using the method according to any one of [1] to [15].
[19] A liquid crystal display element obtained using the method described in [18].
[20] The liquid crystal display element according to [19], wherein the first substrate or the second substrate has an electrode.
[21] The liquid crystal display element according to [19] or [20], which is a low voltage driven lateral electric field liquid crystal display element.

According to the present invention, a zero-plane anchoring film can be industrially produced with a high yield. Using the method of the present invention, a liquid crystal display element similar to the zero-plane anchoring IPS mode liquid crystal display element described in Patent Documents 1 and 2 can be easily manufactured 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, has a low driving voltage, has no bright spots, can suppress Vcom shift in IPS mode, and has FFS In this mode, it is possible to provide a liquid crystal display element having excellent characteristics such that even higher definition is possible.

The present invention is a method for producing a zero-plane anchoring film, which comprises polymerizing a polymerizable compound by UV or heat while bringing a liquid crystal containing a specific polymerizable compound into contact with a radical-generating film. More specifically, a cell is prepared that has a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between a first substrate having a radical generating film and a second substrate optionally having a radical generating film. and applying sufficient energy to the cell to polymerize the radically polymerizable compound. Preferably, the steps include: preparing a first substrate having a radical generating film and a second substrate not having a radical generating film; creating a cell so that the radical generating film faces the second substrate; The method for manufacturing a liquid crystal cell includes the step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between one substrate and a second substrate. For example, a low voltage drive IPS liquid crystal display element in which the second substrate does not have a radical generating film and has a liquid crystal alignment film subjected to uniaxial alignment treatment, and the first substrate has a comb-teeth electrode. This is the creation method.

In the present invention, a "zero-plane anchoring film" means that there is no alignment regulating force for liquid crystal molecules in the in-plane direction, or even if there is, it is weaker than the intermolecular force between liquid crystal molecules, and this film alone will not control the liquid crystal molecules. Refers to a film that is not uniaxially aligned in the direction of . Furthermore, this zero-plane anchoring film is not limited to a solid film, but also includes a liquid film that covers a solid surface. Normally, in a liquid crystal display element, a film that regulates the alignment of liquid crystal molecules, that is, a liquid crystal alignment film, is used as a pair to align the liquid crystal. It can be oriented. This is because the alignment regulating force of the liquid crystal alignment film is also transmitted in the thickness direction of the liquid crystal layer due to the intermolecular force between liquid crystal molecules, and as a result, liquid crystal molecules close 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 throughout the 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 a polymer and a group capable of generating radicals as components. In this case, the composition may contain a polymer to which a radical-generating group is bonded, or the composition may be a composition of a compound having a radical-generating group and a polymer serving as the base resin. It may be a thing. By coating and curing such a composition to form a film, a radical-generating film in which radical-generating groups are immobilized can be obtained. The radical-generating group is preferably an organic group that induces radical polymerization.

（式［Ｘ－１］～［Ｘ－１８］中、＊は化合物分子の重合性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_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-18], [W], [Y], and [Z] shown in the following structure. It will be done.

(In formulas [X-1] to [X-18], * 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-, - NR-, -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 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], and [Z], * indicates a bonding site with a part other than a polymerizable unsaturated bond in the compound molecule, and Ar has an organic group and/or a halogen atom as a substituent. R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. When R ⁹ and R ¹⁰ are alkyl groups, they may be bonded to each other at the ends to form a ring structure. Q represents any of the following structures.

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

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

In order to obtain the radical-generating film used in the present invention, when using a polymer having an organic group that induces radical polymerization, in order to obtain a polymer having a group capable of generating radicals, as a monomer component, a methacrylic group, A monomer with 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 side chain with a moiety that decomposes and generates radicals when exposed to ultraviolet irradiation. It is preferable to manufacture using a monomer having the following. On the other hand, monomers that generate radicals may have problems such as spontaneous polymerization, resulting in unstable compounds. Polymers derived from diamines are preferred, and polyimide precursors such as polyamic acids and polyamic acid esters, polyimides, polyureas, polyamides, and the like 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－１８］中、＊は化合物分子のラジカル重合反応性基以外の部分との結合部位を示し、Ｓ_１、Ｓ_２はそれぞれ独立して－Ｏ－、－ＮＲ－、－Ｓ－を表し、Ｒは水素原子又は炭素原子数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のアルキル基又は炭素数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） Specifically, such a diamine containing a radical generating site is, for example, a diamine having a side chain that generates a radical and can be polymerized, such as a diamine represented by the following general formula (6). , but is not limited to this.

(In formula (6), R ⁶ is a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO-,
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 arbitrary -CH ₂ - or -CF ₂ - of the alkylene group are each independently may be substituted with a group selected from -CH=CH-, divalent carbocycle, and divalent heterocycle, and further, any of the following groups, namely -O-, -COO- , -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups, provided that they are not adjacent to each other;
^R8 is the following formula:

Represents a radical polymerization reactive group selected from.
(In formulas [X-1] to [X-18], * indicates a bonding site with a moiety other than the radical polymerization reactive group of the compound molecule, and S ₁ and S ₂ are each independently -O-, - NR-, -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 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, with respect to the bonding group of the side chain, the 2,3 position, the 2,4 position, the 2,5 position, the 2,6 position, the 3,4 position, the 3, 5 positions are mentioned. Among these, the 2,4 position, the 2,5 position, or the 3,5 position are preferred from the viewpoint of reactivity when synthesizing polyamic acid. Considering the ease of synthesizing the diamine, positions 2 and 4 or positions 3 and 5 are more preferable.

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

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

（式（７）中、Ｔ_１及びＴ_２は、それぞれ独立に、単結合、－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＮＨ－、－ＣＨ_２Ｏ－、－Ｎ（ＣＨ_３）－、－ＣＯＮ（ＣＨ_３）－、又は－Ｎ（ＣＨ_３）ＣＯ－であり、
Ｓは単結合、又は非置換もしくはフッ素原子によって置換されている炭素数１～２０のアルキレン基を表し、当該アルキレン基の任意の－ＣＨ_２－又は－ＣＦ_２－の１以上は、それぞれ独立に－ＣＨ＝ＣＨ－、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＣＯＮＨ－、又は－ＮＨ－が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよく、
Ｊは下記式で表される有機基であり、

（式［Ｗ］、［Ｙ］、［Ｚ］中、＊はＴ_２との結合箇所を表し、Ａｒは有機基及び／又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、Ｒ^９及びＲ^１０は、それぞれ独立に、炭素数１～１０のアルキル基又は炭素数１～１０のアルコキシ基を表し、Ｑは下記のいずれかの構造を表す。

（式中、Ｒ^１１は－ＣＨ_２－、－ＮＲ－、－Ｏ－、又は－Ｓ－を表し、Ｒは水素原子又は炭素原子数１～４のアルキル基を表し、＊は化合物分子のＱ以外の部分との結合部位を示す。）
Ｒ_１２は水素原子、ハロゲン原子、炭素数１～１０のアルキル基又は炭素数１～１０のアルコキシ基を表す。）） Examples of the diamine having a side chain that is decomposed by ultraviolet irradiation to generate radicals include diamines represented by the following general formula (7), but are not limited thereto.

(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 unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms, and one or more of -CH ₂ - or -CF ₂ - in the alkylene group are each independently It may be substituted with a group selected from -CH=CH-, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups, provided that they are not adjacent to each other,
J is an organic group represented by the following formula,

(In the formulas [W], [Y], and [Z], * represents the bonding site with _T2 , and Ar represents phenylene, naphthylene, and biphenylene which may have an organic group and/or a halogen atom as a substituent. R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q is any of the following. represents the structure of

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

The bonding positions of the two amino groups (-NH ₂ ) in the above formula (7) are not limited. Specifically, with respect to the bonding group of the side chain, the 2,3 position, the 2,4 position, the 2,5 position, the 2,6 position, the 3,4 position, the 3, 5 positions are mentioned. Among these, the 2,4 position, the 2,5 position, or the 3,5 position are preferred from the viewpoint of reactivity when synthesizing polyamic acid. Considering the ease of synthesizing the diamine, positions 2 and 4 or positions 3 and 5 are more preferable.

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

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

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

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

In addition, when the polymer used in the radical-generating membrane of the present invention is obtained from a diamine, other diamines other than the diamine having the above-mentioned radical-generating site may be used in combination as a diamine component, 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- aminophenyl)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-amino phenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl) Methanone], 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate) -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-amino benzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl) Terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4' -bis(4-aminophenoxy)diphenylsulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane , 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexa Fluoropropane, 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-amino phenoxy)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 , 1,12-bis(3-aminophenoxy)dodecane; alicyclic diamines such as bis(4-aminocyclohexyl)methane, 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- Aliphatic diamines such as diaminodecane, 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; nitrogen-containing diamines such as N-p-aminophenyl-4-p-aminophenyl (tert-butyloxycarbonyl) aminomethylpiperidine Diamines having an unsaturated heterocyclic structure; diamines having an N-Boc group such as N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine, etc. Can be mentioned.

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

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'-benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl) sulfone, bis(3,4-dicarboxyphenyl) ether, 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, oxydiphthaletetracarboxylic 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-tricarboxycyclopentyl acetic 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- tetrahydronaphthalene -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 Examples include dianhydrides of tetracarboxylic acids such as -2:3,5:6 dicarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid.

Of course, one type or two or more types of tetracarboxylic dianhydride may be used in combination depending on the characteristics such as liquid crystal orientation, sensitivity in polymerization reaction, voltage holding characteristics, and accumulated charge when forming a radical generating film. .

In the synthesis when the polymer is a polyamic acid ester, the structure of the tetracarboxylic acid dialkyl ester to be reacted with the above-mentioned diamine component is not particularly limited, but specific examples thereof are listed 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 -Cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic 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, Examples include 2,3,4-tetrahydronaphthalene - 1,2-dicarboxylic acid dialkyl ester.

Examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3',4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2',3,3'-biphenyltetracarboxylic acid dialkyl ester, 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 -Naphthalenetetracarboxylic acid dialkyl ester, etc.

式中Ｒ_２、Ｒ_３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 above-mentioned diamine component is not particularly limited, and can be used depending on availability and the like. The specific structure of the diisocyanate is shown below.

In the formula, R ₂ and R ₃ represent an aliphatic hydrocarbon having 1 to 10 carbon atoms.

The aliphatic diisocyanates shown in K-1 to K-5 are inferior in reactivity but have the advantage of improving solvent solubility, while the aromatic diisocyanates shown in K-6 to K-7 are highly reactive and heat resistant. However, it has the disadvantage of decreasing solvent solubility. Particularly preferred are K-1, K-7, K-8, K-9, and K-10 in terms of versatility and properties, K-12 is preferred in terms of electrical properties, and K-13 is preferred in terms of liquid crystal orientation. Particularly preferred. One or more diisocyanates can be used in combination, and it is preferable to use various diisocyanates depending on the desired properties.
In addition, some diisocyanates can be replaced with the above-mentioned tetracarboxylic dianhydride, and they can also be used in the form of a copolymer of polyamic acid and polyurea, and chemical imidization can be used to create a copolymer of polyimide and polyurea. It may also be used in the form of a copolymer.

In the 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, azelaic acid, sebacic acid and suberic acid.

Examples of 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- Examples include dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro[3.3]heptane dicarboxylic acid, 1,3-adamantane diacetic acid, and camphoric acid.

Aromatic dicarboxylic acids include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butyl isophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid. Acid, tetramethyl terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-anthracene dicarboxylic 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'-diphenyletherdicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-Stilbendicarboxylic acid, 4,4'-trandicarboxylic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 4,4'-dithiodibenzoic acid, p- Phenylene diacetic acid, 3,3'-p-phenylene dipropionic acid, 4-carboxycinnamic acid, p-phenylene diacrylic 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, (isopropylene) Examples include dicarboxylic acids such as di-p-phenylenedioxy) dibutyric acid and bis(p-carboxyphenyl)dimethylsilane.

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

The various dicarboxylic acids mentioned above may have an acid dihalide or anhydride structure. These dicarboxylic acids are particularly preferably dicarboxylic acids that can provide a polyamide with a linear structure in order to maintain the orientation of liquid crystal molecules. Among these, terephthalic acid, isophthalic 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 their acid dihalides are preferably used. Although some of these compounds exist as isomers, a mixture containing them may be used. Further, two or more kinds of compounds may be used in combination. Note that the dicarboxylic acids used in the present invention are not limited to the above-mentioned exemplified compounds.

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

The reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and does not generate any 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 mixed with the above solvent and used as long as the produced polymer does not precipitate. Note that since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polymer, it is preferable to use an organic solvent that has been dehydrated and dried.

Examples of the organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2 -Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ- Butyrolactone, isopropyl alcohol, 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 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 a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride component is reacted as it is or in an organic solvent. A method in which the diamine component is added by dispersing or dissolving it in a solvent, a method in which the diamine component is added to a solution in which the tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a method in which the diamine component is added by dispersing or dissolving the tetracarboxylic dianhydride component in an organic solvent. Examples include a method of adding them alternately, and any of these methods may be used. In addition, when the diamine component or the tetracarboxylic dianhydride component consists of multiple types of compounds, they may be reacted in a pre-mixed state, they may be reacted individually in sequence, or they may be reacted individually in a low molecular weight It is also possible to make a high molecular weight product by subjecting the polymers to a mixed reaction.

Any temperature can be selected for the reaction of the diamine component and the tetracarboxylic dianhydride component, and is, for example, in the range of -20 to 100°C, preferably in the range of -5 to 80°C. Further, the reaction can be carried out at any concentration; for example, the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass, based on 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 an arbitrary value depending on the molecular weight of the polyamic acid to be obtained. Similar to normal polycondensation reactions, the closer this molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced becomes. The preferred range is 0.8 to 1.2.

The method for synthesizing the polymer used in the present invention is not limited to the above method, and when synthesizing polyamic acid, the above-mentioned tetracarboxylic dianhydride Alternatively, the corresponding polyamic acid can also be obtained by using a tetracarboxylic acid having a corresponding structure or a tetracarboxylic acid derivative such as a tetracarboxylic acid dihalide and reacting it by a known method. Moreover, when synthesizing polyurea, diamine and diisocyanate may be reacted. When producing polyamic acid esters or polyamides, components selected from diamines, tetracarboxylic diesters, and dicarboxylic acids are converted into acid halides in the presence of known condensing agents or by known methods. , may be reacted with diamine.

Examples of methods for imidizing the above-mentioned polyamic acid to produce polyimide include thermal imidization in which a polyamic acid solution is directly heated, and catalytic imidization in which a catalyst is added to a polyamic acid solution. Note that the imidization rate from polyamic acid to polyimide is preferably 30% or more, more preferably 30 to 99%, since the voltage holding rate can be increased. On the other hand, from the viewpoint of whitening properties, that is, suppressing polymer precipitation in the varnish, it is preferably 70% or less. Considering both characteristics, 40 to 80% is more preferable.

The temperature when polyamic acid is thermally imidized in a solution is usually 100 to 400°C, preferably 120 to 250°C, and it is preferable to carry out the process while removing water produced 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 solution of polyamic acid, and stirring the mixture usually at -20 to 250°C, preferably at 0 to 180°C. The amount of the basic catalyst is usually 0.5 to 30 times the mole of the amic acid group, preferably 2 to 20 times the mole, and the amount of the acid anhydride is usually 1 to 50 times the mole of the amic acid group, preferably It is 3 to 30 times the mole. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferred because it has an appropriate basicity to advance the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Among them, acetic anhydride is preferably used because it facilitates purification after the reaction is completed. The imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time, etc.

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

Further, when the radical generating film is made of a polymer containing an organic group that induces radical polymerization, the radical generating film forming composition used in the present invention is made of a polymer other than the polymer containing an organic group that induces radical polymerization. It may also contain other polymers. In this case, the content of other polymers 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 Gel Permeation Chromatography method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

When the radical-generating film used in the present invention is obtained by fixing the composition in the film by applying and curing a composition of a compound having a radical-generating group and a polymer, the polymer is , a polyimide precursor produced according to the above production method, and a polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc., and a diamine having a site where radical polymerization occurs. , at least one type of polymer obtained using a diamine component that is 0 mol % of the total diamine components used in the synthesis of the polymer to be included in the radical-generating film-forming composition may be used. Examples of the compound having a radical-generating group to be added at this time include the following.

A compound that generates radicals when heated is a compound that generates radicals when heated above the decomposition temperature. Such radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane) ), 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.), and azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.). Such radical thermal polymerization initiators can be used alone or in combination of two or more.

The compound that generates radicals when exposed to light is not particularly limited as long as it is a compound that initiates radical polymerization upon irradiation with light. 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, ethyl 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-hydroxycyclohexyl phenylketone, 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.

Note that even if the radical-generating film is made of a polymer containing an organic group that induces radical polymerization, the above-mentioned radical-generating group may be added for the purpose of promoting radical polymerization when energy is applied. You may contain a compound having.

The radical-generating film-forming composition can contain an organic solvent for dissolving or dispersing the polymer component and, if necessary, the radical generator and other components. There are no particular limitations on such organic solvents, and examples thereof include organic solvents such as those exemplified in the synthesis of polyamic acid described above. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, etc. preferred from the viewpoint of In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferred, but a mixed solvent of two or more types 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 have high solubility.

Examples of solvents that improve the uniformity and smoothness of the coating include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, and ethyl carbitol. Tall, 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 acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 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, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 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 mentioned above. Examples include compounds that improve film thickness uniformity and surface smoothness when applying the radical-generating film-forming composition, compounds that improve the adhesion between the radical-generating film-forming composition and the substrate, and compounds that improve the adhesion between the radical-generating film-forming composition and the substrate. Examples include compounds that further improve the film strength of the composition.

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorosurfactants, silicone surfactants, and nonionic surfactants. More specifically, for example, FTOP EF301, EF303, EF352 (manufactured by Tochem Products), Megafac F171, F173, R-30 (manufactured by Dainippon Ink), Florado FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard 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. .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-aminopropyltrimethoxy Silane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol , N,N,N',N'-tetraglycidyl-m-xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4 , 4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, and the like.

In addition, in order to further increase the film strength of the radical generating film, phenolic compounds such as 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane and tetra(methoxymethyl)bisphenol are added. Good too. When these compounds are used, they are preferably used in an amount of 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of polymers contained in the radical-generating film-forming composition. It is.

Furthermore, in addition to the above, the radical-generating film-forming composition may include dielectrics and conductive materials for the purpose of changing the electrical properties such as permittivity and conductivity of the radical-generating film, as long as the effects of the present invention are not impaired. Substances may also be added.

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

The substrate on which the radical-generating film-forming composition is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate on which a transparent electrode for driving a liquid crystal is formed is preferable.
Specific examples include glass plates, polycarbonates, poly(meth)acrylates, polyethersulfones, polyarylates, polyurethanes, polysulfones, polyethers, polyetherketones, trimethylpentene, polyolefins, polyethylene terephthalate, (meth)acrylonitrile, and Examples include substrates in which transparent electrodes are formed on plastic plates such as cellulose acetate, cellulose diacetate, and cellulose acetate butyrate.

Substrates that can be used in IPS type liquid crystal display elements include standard electrode patterns such as IPS comb-shaped electrodes and PSA fishbone electrodes, and protrusion patterns such as MVA.
Furthermore, in a high-performance element such as a TFT type element, an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate.
When a transmissive type liquid crystal display element is intended, it is common to use a substrate like the one described above, but when a reflective type liquid crystal display element is intended, silicon is used for only one side of the substrate. Opaque substrates such as wafers can also be used. In this case, a material such as aluminum that reflects light can also be used for the electrodes formed on the substrate.

Methods for applying the radical-generating film-forming composition include spin coating, printing, inkjet, spraying, and roll coating, but transfer printing is widely used industrially from the viewpoint of productivity. Therefore, it is suitably used in the present invention.

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

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

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

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

When performing orientation treatment 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 come into contact with each other. In the case of the first substrate of the present invention on which comb-teeth electrodes are formed, the rubbing direction is selected depending on the electrical properties of the liquid crystal, but when using a liquid crystal with positive dielectric anisotropy, the rubbing direction is determined by the comb-teeth electrodes. It is preferable that the direction is substantially the same as the extending direction of.

The second substrate of the present invention is the same as the first substrate except that it does not have a radical 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 having the radical generating film (first substrate) and a substrate having a known liquid crystal alignment film (second substrate) are combined. is obtained by arranging the radical generating film and the liquid crystal alignment film so as to face each other, sandwiching a spacer, fixing with a sealant, and sealing by injecting a liquid crystal composition containing a liquid crystal and a radically polymerizable compound. It will be done. At this time, the size of the spacer used is usually 1 to 30 μm, preferably 2 to 10 μm. Also, by making the rubbing direction of the first substrate parallel to the rubbing direction of the second substrate, it can be used in IPS mode and FFS mode, and if the rubbing directions are arranged perpendicularly, twisted nematic mode can be used. It can be used for.
The method of injecting a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is not particularly limited, and may include a vacuum method in which a mixture containing a liquid crystal and a polymerizable compound is injected after reducing the pressure in the prepared liquid crystal cell, and a method of injecting a mixture containing a liquid crystal and a polymerizable compound. Examples include a dropping method in which sealing is performed after dropping a mixture containing a sexual compound.

式（１）中、Ｒ^ａおよびＲ^ｂはそれぞれ独立に炭素数２～８の直鎖アルキル基を表し、Ｅは単結合、－Ｏ－、－ＮＲ^ｃ－、－Ｓ－、エステル結合、アミド結合から選ばれる結合基を表し、Ｒ^ｃは水素原子、炭素数１～４のアルキル基を示す。 <Liquid crystal composition containing liquid crystal and radically polymerizable compound>
In producing the liquid crystal display element of the present invention, the polymerizable compound used together with the liquid crystal is a compound represented by the following formula (1).

In formula (1), R ^a and R ^b each independently represent a straight chain alkyl group having 2 to 8 carbon atoms, and E is a single bond, -O-, -NR ^c -, -S-, an ester bond, an amide It represents a bonding group selected from bonds, and R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

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

式（１－１）及び（１－２）中、ＲａおよびＲｂはそれぞれ独立に炭素数２～８の直鎖アルキル基を表す。 The radically polymerizable compound represented by the above formula (1) is one in which E is an ester bond (a bond represented by -C(=O)-O- or -O-C(=O)-). is preferable from the viewpoint of ease of synthesis, compatibility with liquid crystals, and polymerization reactivity, and specifically, compounds having the following structures are preferable, but are not particularly limited.

In formulas (1-1) and (1-2), Ra and Rb each independently represent a straight-chain alkyl group having 2 to 8 carbon atoms.

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

These various radically polymerizable monomers may be used alone or in combination of two or more. Moreover, it is preferable that these have compatibility with liquid crystal.

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

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

Note that liquid crystal generally refers to a substance that exhibits both solid and liquid properties, and representative 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.

Next, sufficient energy is applied to the liquid crystal cell into which the mixture (liquid crystal composition) containing this liquid crystal and a radically polymerizable compound has been introduced to cause the radically polymerizable compound to undergo a polymerization reaction. This can be carried out, for example, by applying heat or UV irradiation, and the radically polymerizable compound is polymerized on the spot, thereby developing the desired properties. Among these, UV irradiation is preferable because it enables oriented patterning and allows polymerization reaction to occur in a short time. When used in the twisted nematic mode, in addition to the above liquid crystal composition, a chiral dopant may be introduced into the liquid crystal cell as necessary.

Further, heating may be performed during UV irradiation. The heating temperature during UV irradiation is preferably within a temperature range at which 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, in the case of UV irradiation, it is preferable to select the wavelength of UV irradiation that gives the best reaction quantum yield of the polymerizable compound to be reacted, and the amount of UV irradiation is usually 0.01 to 30 J. Preferably, the amount is 10 J or less, and a smaller amount of UV irradiation is preferable because it is possible to suppress a decrease in reliability due to destruction of the components constituting the liquid crystal display, and to improve the manufacturing takt time by reducing the UV irradiation time. It is.

Further, when polymerizing by heating alone instead of UV irradiation, heating is preferably carried out at a temperature at which the polymerizable compound reacts and which is lower than the decomposition temperature of the liquid crystal. Specifically, the temperature is, for example, 100°C or more and 150°C or less.

When applying sufficient energy to cause the radically polymerizable compound to undergo a polymerization reaction, it is preferable that no voltage is applied and that no electric field is applied.

<Liquid crystal display element>
A liquid crystal display element can be manufactured using the liquid crystal cell obtained in this manner.
For example, a reflective liquid crystal display element can be obtained by providing a reflective electrode, a transparent electrode, a λ/4 plate, a polarizing film, a color filter layer, etc. in accordance with a conventional method to this liquid crystal cell as necessary.
Further, by providing this liquid crystal cell with a backlight, a polarizing plate, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, etc. according to a conventional method as required, a transmissive liquid crystal display element can be obtained.

EXAMPLES The present invention will be specifically explained 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 methods of characterizing them are as follows.

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

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

<Measurement of imidization rate>
Put 20 mg of polyimide powder into an NMR sample tube (Kusano Scientific Co., Ltd. NMR sampling tube standard φ5), and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture). Then, it was completely dissolved by applying ultrasound. Proton NMR of this solution at 500 MHz was measured using a measuring device (manufactured by JEOL Datum Co., Ltd., JNW-ECA500).
The imidization rate is determined by determining a proton derived from a structure that does not change before and after imidization as a reference proton, and calculating the peak integrated value of this proton and the proton peak derived from the NH of the amide group that appears around 9.5 to 10.0 ppm. The value was calculated using the following formula.
Imidization rate (%) = (1-α・x/y)×100
In the formula, x is the integrated value of the NH-derived proton peak of the amide group, y is the integrated peak 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%). This is the number ratio of

<Polymerization of polymer 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, 48.2 g of NMP was added thereto, and the mixture was stirred under a nitrogen atmosphere to completely dissolve. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60° C. for 3 hours under a nitrogen atmosphere. The temperature was returned to room temperature again, 2.71 g (13.80 mmol) of TC-1 was added, and the mixture was reacted at 40° C. for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity was 1000 mPa·s to obtain a polymerization solution having a polyamic acid concentration of 20% by mass.
Weigh out 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 ( 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 the reaction was completed, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol with stirring to precipitate a solid. Collect the solid by filtration, then add the solid to 300 ml of methanol and wash with stirring for 30 minutes twice in total. Collect the solid by filtration, air dry, and then dry in a vacuum oven at 60°C. As a result, 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% was obtained.

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

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

1st step: Synthesis of 2-hydroxymethylacrylic acid ethyl ester In a 500 ml four-necked flask equipped with a nitrogen inlet tube, 10 mg of 4-methoxyphenol and 21 g of DABCO (1,4-diazabicyclo[2.2.2]octane) were added. .88 g (195.1 mmol) was weighed out, 50 ml of pure water was added thereto, 11.52 g (390.1 mmol) of paraformaldehyde was added while stirring at 10° C. or lower under a nitrogen atmosphere, and the mixture was stirred for 1 hour. After confirming that the slurry state had changed to a solution state, 300 ml of acetonitrile was added, 19.53 g (195.1 mmol) of ethyl acrylate was added dropwise, and the mixture was reacted at 50° C. for 5 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, and 50 ml of n-hexane was added. After confirming that the mixture had separated into three layers, the bottom two layers were collected and this operation was repeated three times. Furthermore, hydrochloric acid was added to adjust the pH to 4 to 5, and extraction was performed using ethyl acetate. Anhydrous magnesium sulfate was added to the extracted solution, and the mixture was stirred and dried, followed by filtration and concentration to obtain 22.9 g (175.6 mmol, yield 90%) of a colorless and transparent oily liquid. The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
^1H NMR (400 MHz, _CDCl3 ) δ: 6.81 (1H), 5.80 (1H), 4.31 (2H), 4.17 (1H), 1.98 (1H), 0.93 (3H)

2nd step: Synthesis of 2-(heptanoyloxymethyl)acrylic acid ethyl ester 19.9 g of 2-hydroxymethylacrylic acid ethyl ester obtained by the above method was placed in a 500 ml four-necked flask equipped with a nitrogen introduction tube. (152.9 mmol) was weighed out, 300 ml of THF and 23.2 g (229.3 mmol) of triethylamine were added, and 25.0 g (168.2 mmol) of heptanoyl chloride was added dropwise while keeping the temperature below 10°C under a nitrogen atmosphere for 6 hours. Made it react. After the reaction, precipitated triethylamine hydrochloride was removed by filtration, the reaction solution was concentrated, redissolved in 300 ml of ethyl acetate, washed 3 times with 100 ml of 10% potassium carbonate aqueous solution, and washed 3 times with 50 ml of pure water. After washing twice and drying over anhydrous magnesium sulfate, the mixture was filtered and concentrated to obtain a pale yellow viscous substance. Further purification was performed by flash column chromatography (developing solvent: ethyl acetate: n-hexane = 20:80), followed by solvent removal and vacuum drying to obtain 32.2 g (133.0 mmol) of a colorless and transparent oily liquid. 87%). The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.37 (1H), 5.80 (1H), 3.80 (2H), 4.23-4.21 (2H), 2.39-2. 37 (2H), 1.64-1.58 (2H), 1.30-1.27 (9H), 0.86 (3H)

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

1st step: Synthesis of butyl 2-hydroxymethylacrylate Ethyl acrylate was changed to butyl acrylate and synthesis was carried out in the same manner as in the above-mentioned 1st step to obtain 24.3 g of a colorless and transparent oil (26. 2g: yield 85%). The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
^1H NMR (400 MHz, _CDCl3 ) δ: 6.81 (1H), 5.80 (1H), 4.31 (2H), 4.17 (1H), 1.98 (1H), 1.67 -1.64 (2H), 1.42-1.38 (2H), 0.93 (3H)

Second step: Synthesis of 2-(heptanoyloxymethyl)butyl acrylate ethyl 2- hydroxymethylacrylate in the second step was replaced with butyl 2- hydroxymethylacrylate obtained by the above method. , Synthesis was carried out in the same manner as above to obtain 34.2 g (126.7 g, yield: 82.8%) of a colorless and transparent oily liquid. The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.36 (1H), 5.81 (1H), 4.80 (2H), 4.19-4.16 (2H), 2.35-2. 31 (2H), 1.64-1.58 (4H), 1.40-1.25 (8H), 0.96-0.83 (6H)

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

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

(first board)
The first substrate (hereinafter also referred to as an IPS substrate) is an alkali-free glass substrate measuring 30 mm x 35 mm and having 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 in height and approximately 5 mm in width.
AL1 and SE-6414 were filtered through a 1.0 μm filter, applied to the electrode formation surface of the IPS substrate using a spin coating method, dried on a hot plate at 80°C for 1 minute, and then heated at 220°C for 20 minutes. It was baked for a minute to form a coating film with 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. The rubbing was performed using YA-20R rayon cloth manufactured by Yoshikawa Kako Co., Ltd. under the conditions of a roll diameter of 120 mm, rotation speed of 300 rpm, moving speed of 50 mm/sec, and pushing amount of 0.4 mm. However, only the membrane coated with SE-6414 was rotated at 1000 rpm. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, followed by drying at 80° C. for 10 minutes.

(Second board)
The second substrate (also referred to as the back ITO substrate) is an alkali-free glass substrate with dimensions of 30 mm x 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. Moreover, columnar spacers with a height of 4 μm are formed on the surface (the surface facing inside the cell).
SE-6414 was filtered through a 1.0 μm filter, applied by spin coating, and dried on a hot plate at 80° C. for 1 minute. Next, each coating was baked for 20 minutes to form a coating film with a thickness of 100 nm, and then rubbed. The rubbing treatment was performed using YA-20R rayon cloth manufactured by Yoshikawa Kako under the conditions of a roll diameter of 120 mm, rotation speed of 1000 rpm, movement speed of 50 mm/sec, and pushing amount of 0.4 mm. After the rubbing treatment, ultrasonic irradiation was performed in pure water for 1 minute, followed by drying at 80° C. for 10 minutes.

(Preparation of liquid crystal cell)
Using the two types of substrates (first substrate and second substrate) with the liquid crystal alignment film described above, the periphery was sealed leaving a liquid crystal injection port, and an empty cell with a cell gap of about 4 μm was prepared. At this time, if the first substrate has not been subjected to rubbing treatment, the direction of the comb-teeth electrode 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.
Liquid crystal compositions LC-1 to LC-4 (merck MLC-3019 with each of the above polymerizable compounds added in the optimum amount) were placed in this empty cell at room temperature under a vacuum of about 300 Pa. A liquid crystal cell was prepared by vacuum injection and another by vacuum injection after degassing at a vacuum level of about 1 Pa for 1 hour, and the injection port was sealed to obtain a liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heat-treated at 120° C. for 10 minutes.
In the case of UV treatment, the liquid crystal cell was irradiated with ultraviolet rays using a high-pressure mercury lamp through a bandpass filter with a wavelength of 313 nm so that the exposure amount was 3000 mJ.

<Evaluation of liquid crystal orientation>
The orientation of the liquid crystal cell was confirmed using a polarizing plate set in crossed Nicols. Those that were oriented without defects were rated as ○, those with slight orientation defects were rated as △, and those that were not oriented were rated as ×.

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

The liquid crystal compositions LC-1 to LC-4 are obtained by adding the polymerizable compounds listed in the table below to MLC-3019 in the amounts introduced below.

<Orientation results>

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

<Results of electro-optical characteristics>
Next, a summary of the driving threshold voltage, maximum brightness, and response speed of the cells using the zero-anchoring aligned liquid crystal described above, in which the radical generating film was not rubbed, is shown below.

When the polymerizable compound of the present invention was used, it was confirmed that the driving voltage decreased regardless of the presence or absence of the rubbing treatment, and there was a tendency for the response speed to improve by performing the rubbing treatment.
Therefore, it was found that the polymerizable compound of the present invention can simultaneously achieve the effects of zero anchoring under high vacuum and improvement of response speed by rubbing.

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

Claims (18)

A liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a structure represented by the following formula (1) is brought into contact with a radical generating film, and energy sufficient to cause the radically polymerizable compound to undergo a polymerization reaction. A method for producing a zero-plane anchoring film, characterized in that the radical-generating film is a film on which an organic group that induces radical polymerization is immobilized.

In formula (1), R ^a and R ^b each independently represent a straight chain alkyl group having 2 to 8 carbon atoms, and E is a single bond, -O-, -NR ^c -, -S-, an ester bond, an amide It represents a bonding group selected from bonds, and R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a structure represented by the following formula (1) is brought into contact with a radical generating film, and energy sufficient to cause the radically polymerizable compound to undergo a polymerization reaction. 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 it in the film. A method for producing a characteristic zero-plane anchoring film.

In formula (1), R ^a and R ^b each independently represents a straight-chain alkyl group having 2 to 8 carbon atoms, E is a single bond, -O-, -NR ^c. -, -S-, an ester bond, and an amide bond, and R ^c. represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A liquid crystal composition containing a liquid crystal and a radically polymerizable compound having a structure represented by the following formula (1) is brought into contact with a radical generating film, and energy sufficient to cause the radically polymerizable compound to undergo a polymerization reaction. A method for producing a zero-plane anchoring film, characterized in that the radical-generating film is made of a polymer containing an organic group that induces radical polymerization.

In formula (1), R ^a and R ^b each independently represents a straight-chain alkyl group having 2 to 8 carbon atoms, E is a single bond, -O-, -NR ^c. -, -S-, an ester bond, and an amide bond, and R ^c. represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 4. The method according to claim 1, wherein the radical generating film of the first substrate is a radical generating film subjected to uniaxial alignment treatment. 5. A method according to any preceding claim, wherein the energizing step is carried out without an electric field. 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. Claims 1, 3, and 6, wherein the organic group that induces radical polymerization is an organic group represented by the following structures [X-1] to [X-18], [W], [Y], and [Z]. The method described in any one of the above.

(In formulas [X-1] to [X-18], * indicates a bonding site with a portion other than the polymerizable unsaturated bond of the compound molecule, and 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, 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], and [Z], * indicates a bonding site with a part other than a polymerizable unsaturated bond in the compound molecule, and Ar has an organic group and/or a halogen atom as a substituent. R represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, which may be 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, they may be bonded to each other at the ends to form a ring structure. Q represents any of the following structures.

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

(In formula (6), R ⁶ is a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-,-CON(CH ₃ )- or -N(CH ₃ ) 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 of the alkylene group ₂ -or-CF ₂ One or more of - may be each independently replaced with a group selected from -CH=CH-, divalent carbocycle, and divalent heterocycle, and further, any of the following groups, namely , -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups, provided that they are not adjacent to each other;
R ⁸ is the following formula:

Represents a radical polymerization reactive group selected from.
(In formulas [X-1] to [X-18], * indicates a bonding site with a portion other than the radical polymerization reactive group of the compound molecule, and 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, 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 each independently represents 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 of the alkylene group ₂ -or-CF ₂ One or more of - may be each independently replaced with a group selected from -CH=CH-, divalent carbocycle, and divalent heterocycle, and further, any of the following groups, namely , -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- may be substituted with these groups, provided that they are not adjacent to each other,
J is an organic group represented by the following formula,

(In the formulas [W], [Y], [Z], * is T ₂ , 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 of the following structures.

(In the formula, R ¹¹ Ha-CH ₂ -, -NR-, -O-, or -S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site with a portion of the compound molecule other than Q. )
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 8, wherein E in the formula (1) is an ester bond. preparing a first substrate having a radical generating film and a second substrate optionally having a radical generating film;
creating a cell such that the radical generating film on the first substrate faces the second substrate, and
A step of filling a liquid crystal composition containing a liquid crystal 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 for manufacturing a liquid crystal cell according to claim 10, wherein the second substrate does not have a 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 for manufacturing a liquid crystal cell according to claim 12, wherein the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment. 14. The method for manufacturing a liquid crystal cell according to claim 10, wherein the first substrate having the radical generating film is a substrate having comb-teeth electrodes. A method for manufacturing a liquid crystal display element using a film that creates a zero-plane anchoring state obtained using the method according to any one of claims 1 to 14. A liquid crystal display element obtained using the method according to claim 15. The liquid crystal display element according to claim 16, wherein the first substrate or the second substrate has an electrode. The liquid crystal display element according to claim 16 or 17, which is a low voltage driven lateral electric field liquid crystal display element.