WO2019244821A1 - Production method for zero azimuthal anchoring film, and liquid crystal display element - Google Patents

Abstract

The present invention provides an industrial production method for a zero azimuthal anchoring film, and an excellent liquid crystal display element and liquid crystal display element production method which employ the aforementioned method. Provided is a production method for a patterned zero azimuthal anchoring film that includes: a step for irradiating a specific region of a radical generating film with radiation to form a patterned radical generating film; and a step for bringing a liquid crystal composition containing a liquid crystal and a radical-polymerizable compound into contact with the patterned radical generating film and, while maintaining this state, applying sufficient energy to the liquid crystal composition to cause the polymerization of the radical-polymerizable compound. Also provided is a method for creating a functional film that includes a step for preparing a cell in which a liquid crystal composition containing a liquid crystal and a radical-polymerizable compound is sandwiched between a first substrate having a radical generating film and a second substrate not having a radical generating film, and a step for applying, to the cell, sufficient energy to cause the polymerization of the radical polymerizable compound.

Description

Method for manufacturing zero plane anchoring film and liquid crystal display device

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

{Recently, liquid crystal display elements have been widely used in displays of mobile phones, computers and televisions. Liquid crystal display elements have characteristics such as thinness, light weight, and low power consumption, and are expected to be applied to further contents such as VR and ultra-high-definition displays in the future. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment) have been proposed as display modes of a liquid crystal display. In all modes, the liquid crystal is in a desired alignment state. (Liquid crystal alignment film) is used.

In particular, products equipped with a touch panel such as a tablet PC, a smartphone, and a smart TV have preferred an IPS mode in which a display is not easily disturbed even when touched. In recent years, an FFS (Fringe) has been used in view of improvement in contrast and viewing angle characteristics. A liquid crystal display device using Field (Switching) and a technology using a non-contact technology using optical alignment have come to be used.

However, the FFS has a problem that the manufacturing cost of the substrate is higher than that of the IPS, and a display defect peculiar to the FFS mode called Vcom shift occurs. In addition, optical alignment has the advantage of being able to increase the size of a device that can be manufactured and greatly improving display characteristics as compared with the rubbing method. Display failure, isomerization type, burn-in due to insufficient alignment force, etc.). At present, liquid crystal display element makers and liquid crystal alignment film makers have made various efforts to solve these problems.

On the other hand, in recent years, an IPS mode using zero plane anchoring has been proposed, and it has been reported that the use of this method makes it possible to improve the contrast and drastically lower the voltage compared to the conventional IPS mode. (See Patent Document 1).

Specifically, a liquid crystal alignment film having a strong anchoring energy is used for one of the substrates, and one of the substrates having an electrode for generating a lateral electric field has no liquid crystal alignment regulating force. This is a method for producing an IPS mode liquid crystal display element by using various processes.

In recent years, a zero-plane state has been created using a thick polymer brush or the like, and a technical proposal has been made for a cello-plane anchoring IPS mode (Reference Document 2). With this technology, a great improvement in the contrast ratio and a great decrease in the driving voltage have been realized.
On the other hand, there is a problem that the response speed, particularly the response speed when the voltage is turned off, is significantly reduced. This is due to the fact that the drive voltage is low, the effect of responding with a weak electric field as compared with the normal drive method, and the fact that the anchoring force of the alignment film is extremely small, so that it takes time to restore the liquid crystal. . As a method for solving this, a method of performing zero anchoring only on the pixel electrode has been proposed (Patent Document 3). It has been reported that this makes it possible to improve both luminance and response speed.

Japanese Patent No. 4053530 JP 2013-231775 A JP-A-2017-212566

By setting the zero plane anchoring only on the electrode of the IPS comb-teeth electrode, the response speed delay at the time of driving is suppressed. On the other hand, in order to achieve the zero anchoring state only on the electrode, a different material is used in a very fine region. It is necessary to prepare a difficult technique such as painting differently, and it is considered that it will be a big problem in actual industrialization.
If such a technical problem can be solved, it will be a great cost merit as a panel maker, and it will be a merit for suppressing battery consumption and improving image quality.
The present invention has been made in order to solve the above problems, and a method of creating a zero plane anchoring site and a site having an anchoring force in the plane of a liquid crystal alignment film, and an anchoring energy. A method for controlling an arbitrary state, a non-contact alignment, a low driving voltage, and a high response speed at the time of off at the same time at a room temperature by a simple and inexpensive method at the same time. The purpose is to provide.

(4) The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved, and have completed the present invention having the following points.

That is, the present invention includes the following.
[1] A step of irradiating a specific region with radiation to the radical generating film to form a patterned radical generating film, and applying a liquid crystal composition containing a liquid crystal and a radical polymerizable compound to the patterned radical generating film. A method for producing a patterned zero-plane anchoring film, comprising the step of: applying a sufficient energy to the liquid crystal composition to cause a polymerization reaction of the radically polymerizable compound while contacting and maintaining the state.
[2] The method according to [1], wherein the radical generating film is a uniaxially oriented radical generating film.
[3] The method according to [1] or [2], wherein the step of applying energy is performed without an electric field.
[4] The method according to any one of [1] to [3], wherein the radical generating film is a film in which an organic group that induces radical polymerization is fixed.
[5] The radical-generating film is obtained by applying and curing a composition of a compound having a radical-generating group and a polymer to form a film, thereby fixing the film in the film. The method according to any one of [1] to [3].
[6] The method according to any one of [1] to [3], wherein the radical generating film is made of a polymer containing an organic group that induces radical polymerization.
[7] The polymer containing an organic group that induces radical polymerization is selected from a polyimide precursor, polyimide, polyurea, and polyamide 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 polymer.
[8] The organic group that induces radical polymerization is an organic group represented by any of the following structures [X-1] to [X-18], [W], [Y] and [Z]. ], The method of any one of [6] and [7].

(In the formulas [X-1] to [X-18], * represents a bonding site to a part other than the polymerizable unsaturated bond of the compound molecule, and S ₁ and S ₂ are each independently —O—, − R 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; R ₁ and R ₂ each independently represent a hydrogen atom; Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms)

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

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

(In the formula (6), R ⁶ is a single bond, —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, —CON (CH ₃ ) —, or —N (CH ₃ ) CO—,
R ⁷ represents a single bond or an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, wherein at least one of —CH ₂ — or —CF ₂ — in the alkylene group is independently May be replaced by a group selected from —CH ＝ CH—, a divalent carbocyclic ring, and a divalent heterocyclic ring. Further, any of the following groups: —O—, —COO— , —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups provided that they are not adjacent to each other;
R ⁸ has the following formula:

Represents a radical polymerization reactive group selected from
(In the formulas [X-1] to [X-18], * indicates a bonding site to a part other than the radical polymerization reactive group of the compound molecule, and S ₁ and S ₂ are each independently -O-,- R 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; R ¹ and R ² each independently represent a hydrogen atom; Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms))

(In the 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 ⁰ represents a single bond or an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, wherein at least one of —CH ₂ — or —CF ₂ — in the alkylene group is independently May be replaced by a group selected from —CH ＝ CH—, a divalent carbocyclic ring, and a divalent heterocyclic ring. Further, any of the following groups: —O—, —COO— , —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups provided that they are not adjacent to each other;
J is an organic group represented by any of the following formulas,

(Wherein [W], [Y], [Z] in which * represents a bonding site to T _2, Ar is may have an organic group and / or a halogen atom as a substituent phenylene, naphthylene, and biphenylene And 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 represents any of the following: Represents the structure of

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

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

(In the formula, * represents a bonding site to a portion other than the polymerizable unsaturated bond of the compound molecule. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-,- Represents a bonding group selected from NR ^c- , -S-, an ester bond and an amide bond, wherein R ^c is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
[19] A method for manufacturing a liquid crystal display element using a film that creates a zero-plane anchoring state obtained by using the method according to any one of [1] to [17].
[20] A liquid crystal display device obtained by using the method according to [19].
[21] The liquid crystal display element according to [20], wherein the first substrate or the second substrate has an electrode.
[22] The liquid crystal display element according to [20] or [21], 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. By using the method of the present invention, a liquid crystal display element similar to the zero-plane anchoring IPS mode liquid crystal display element described in Patent Documents 1 and 2 can be easily manufactured with inexpensive raw materials and existing manufacturing methods. Further, the liquid crystal display device obtained by the manufacturing method of the present invention has a higher response speed of the liquid crystal at the time of Off than the conventional technology, has a low driving voltage, has no bright spot, can suppress the Vcom shift in the IPS mode, and has a high FFS. In the mode, it is possible to provide a liquid crystal display device having excellent characteristics such as higher definition.

FIG. 3 is a diagram of a TN cell having a substrate on which a film having a zero-plane anchoring region and a non-zero-plane anchoring region is formed by having a region irradiated with UV and a region not irradiated with UV. In the cell, a transparent region is a region without UV irradiation, and an opaque region is a region with UV irradiation.

The present invention includes forming a radical-generating film having an anchoring force on a substrate, and irradiating the radical-generating film with radiation in a region where the anchoring force is desired to be maintained. A method for producing a film in which a zero-plane anchoring region and a strong anchoring region are patterned, wherein a polymerizable compound is polymerized by UV or heat in a state where the liquid crystal is brought into contact. More specifically, a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is placed between a first substrate having a radical generating film treated with radiation and a second substrate which may have a radical generating film. Preparing a cell having a zero-plane anchoring region and a strong anchoring region patterned, comprising the steps of: preparing a cell having the same; and applying sufficient energy to the cell to cause a polymerization reaction of the radical polymerizable compound. Is the way. Preferably, a step of preparing a first substrate having a radical generating film subjected to a radiation irradiation treatment and a second substrate not having a radical generating film, creating a cell such that the radical generating film faces the second substrate. And a step of filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between a first substrate and a second substrate. For example, a low-voltage-driven IPS liquid crystal display device in which the second substrate has no radical generating film, is a substrate having a liquid crystal alignment film that has been subjected to uniaxial alignment treatment, and the first substrate is a substrate that has a comb electrode. How to create.

In the present invention, the “zero plane anchoring film” means that there is no or little if any force regulating the alignment of liquid crystal molecules in the in-plane direction. In which the film is not uniaxially oriented. The zero-plane anchoring film is not limited to a solid film, but includes a liquid film covering a solid surface. Normally, a liquid crystal display element aligns liquid crystals using a film that regulates the alignment of liquid crystal molecules, that is, a liquid crystal alignment film is used as a pair. 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 by the intermolecular force between the liquid crystal molecules, and as a result, the liquid crystal molecules near the zero-plane anchoring film are also aligned. Therefore, when a liquid crystal alignment film for horizontal alignment is used as the liquid crystal alignment film, a horizontal alignment state can be created in the entire liquid crystal cell. The horizontal alignment refers to a state in which the major axes of the liquid crystal molecules are arranged substantially parallel to the liquid crystal alignment film surface, and a tilt alignment of about several degrees is also included in the category of the horizontal alignment.

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

Such an organic group that induces radical polymerization is an organic group represented by any of [X-1] to [X-18], [W], [Y] and [Z] represented by the following structure. Groups.

(In the formulas [X-1] to [X-18], * represents a bonding site to a part other than the polymerizable unsaturated bond of the compound molecule, and S ₁ and S ₂ are each independently —O—, − R 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; R ₁ and R ₂ each independently represent a hydrogen atom; Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms)

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

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

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

In order to obtain a radical-generating film used in the present invention, when using a polymer having an organic group that induces the radical polymerization, to obtain a polymer having a group capable of generating a radical, as a monomer component, a methacryl group, A monomer having a photoreactive side chain containing at least one selected from an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group, and a site which decomposes by ultraviolet irradiation to generate a radical. It is preferable to use the monomer having the above. On the other hand, monomers that generate radicals may have problems such as spontaneous polymerization themselves and become unstable compounds, so they have radical generating sites in terms of ease of synthesis. Preferred are polymers derived from diamines, and more preferred are polyimide precursors such as polyamic acids and polyamic acid esters, polyimides, polyureas, and polyamides.

Specifically, such a radical-generating site-containing diamine is, for example, a diamine having a polymerizable side chain that generates a radical and includes a diamine represented by the following general formula (6). However, the present invention is not limited to this.

(In the formula (6), R ⁶ is a single bond, —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, —CON (CH ₃ ) —, or —N (CH ₃ ) CO—,
R ⁷ represents a single bond or an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, wherein at least one of —CH ₂ — or —CF ₂ — in the alkylene group is independently May be replaced by a group selected from —CH ＝ CH—, a divalent carbocyclic ring, and a divalent heterocyclic ring. Further, any of the following groups: —O—, —COO— , —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups provided that they are not adjacent to each other;
R ⁸ is the following formula:

Represents a radical polymerization reactive group selected from
(In the formulas [X-1] to [X-18], * indicates a bonding site to a part other than the radical polymerization reactive group of the compound molecule, and S ₁ and S ₂ are each independently -O-,- R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms 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 position of the two amino groups (—NH ₂ ) in the formula (6) is not limited. Specifically, with respect to the bonding group in the side chain, the positions of 2, 3 on the benzene ring, the positions of 2, 4, the positions of 2, 5, the positions of 2, 6, the positions of 3, 4, and 3, 5 positions. Among them, the 2,4 position, the 2,5 position, or the 3,5 position is preferred from the viewpoint of reactivity when synthesizing the polyamic acid. Taking into account the ease of synthesizing the diamine, the positions of 2, 4 or 3, 5 are more preferable.

Examples of the diamine having a photoreactive group containing at least one selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group include the following. Compounds include, but are not limited to.

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

Examples of the diamine having a site where a radical is generated by being decomposed by irradiation with ultraviolet rays as a side chain include a diamine represented by the following general formula (7), but are not limited thereto.

(In the 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 ⁰ represents a single bond or an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, wherein at least one of —CH ₂ — or —CF ₂ — in the alkylene group is independently May be replaced by a group selected from —CH ＝ CH—, a divalent carbocyclic ring, and a divalent heterocyclic ring. Further, any of the following groups: —O—, —COO— , —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups provided that they are not adjacent to each other;
J is an organic group represented by any of the following formulas,

(Wherein [W], [Y], [Z] in which * represents a bonding site to T _2, Ar is may have an organic group and / or a halogen atom as a substituent phenylene, naphthylene, and biphenylene And 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 represents any of the following: Represents the structure of

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

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

In particular, in view of ease of synthesis, high versatility, characteristics, and the like, a structure represented by any of the following formulas is most preferable, but not limited thereto.

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

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

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

When the polymer used for the radical generating film of the present invention is obtained from a diamine, other diamines other than the diamine having a site where the radical is generated are used 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'- Aminobiphenyl, 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'-diaminodiphenylether, 3,3'-diaminodiphenylether, 3,4'-diaminodiphenylether, 2,2'-diaminodiphenylether, 2,3'-diaminodiphenylether, 4,4 ' -Sulfonyldianiline, 3,3'-sulfonyl Aniline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, , 3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl ( 4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) Amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diamino Benzophenone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1, 6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2 -Bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis ( , 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)] di Nirin, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4 -Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3- Aminophenyl) isophthalate, N, N '-(1,4-phenylene) bis (4-aminobenzami C), N, N '-(1,3-phenylene) bis (4-aminobenzamide), N, N'-(1,4-phenylene) bis (3-aminobenzamide), N, N '-(1 , 3-Phenylene) bis (3-aminobenzamide), N, N'-bis (4-aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'-bis ( 4-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenylsulfone 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2′-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, trans-1, 4-bis (4-aminophenyl) cyclohexane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis (4-aminophenoxy) methane, 1,2-bis (4-aminophenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) Hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7-bis (3-aminophenoxy) heptane, 1,8-bis (4 -Aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, 1,10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 1,11-bis (3-amido) Aromatic diamines such as nophenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane and 1,12-bis (3-aminophenoxy) dodecane; bis (4-aminocyclohexyl) methane, bis (4-amino Alicyclic diamines such as -3-methylcyclohexyl) methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, Aliphatic diamines such as 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane; 1,3-bis [2- (p- Aminophenyl) ethyl] urea, 1,3-bis [2- (p-aminophenyl) ethyl] -1-tert-butyl Diamine having a urea structure such as cyclocarbonyl urea; diamine having a nitrogen-containing unsaturated heterocyclic structure such as Np-aminophenyl-4-p-aminophenyl (tert-butyloxycarbonyl) aminomethylpiperidine; N-tersha And diamines having an N-Boc group such as riboxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4-aminobenzyl) amine.

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

テ ト ラ In the synthesis where 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, 2,2 3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyl Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-di Carboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) Nyl) 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-1,2,3,3 4-cyclobutanetetracarboxylic acid, oxydiphthaltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexane Tetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,3 -Cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic Acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4 0] decane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2 6>] Undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydrinaphthalene-1,2-dicarboxylic acid, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0 <2,7>] dodeca-4,5,9,10-tetracarboxylic acid, 3 , 5,6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and other dianhydrides of tetracarboxylic acids.

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

In the synthesis where the polymer is a polyamic acid ester, the structure of the tetracarboxylic acid dialkyl ester to be reacted with the above diamine component is not particularly limited, but specific examples thereof are shown below.
Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,2 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 -Dialkyl cyclohexylsuccinate, 3,4-dicarboxy- 2,2,3,4-tetrahydro-1-naphthalene dialkyl succinate, 1,2,3,4-butanetetracarboxylic dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8- Dialkyl tetracarboxylate, dialkyl 3,3 ', 4,4'-dicyclohexyltetracarboxylate, dialkyl 2,3,5-tricarboxycyclopentylacetic acid, cis-3,7-dibutylcycloocta-1,5- Diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 <2,5>] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7 , 8-dialkyl ester, hexacyclo [6.6.0.1 <2,7>. 0 <3,6>. 1 <9, 14>. 0 <10,13>] hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester and the like.

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

In the synthesis where the polymer is a polyurea, the diisocyanate to be reacted with the above diamine component is not particularly limited, and can be used according to 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.

Aliphatic diisocyanates represented by K-1 to K-5 are inferior in reactivity but have the merit of improving solvent solubility. Aromatic diisocyanates represented by K-6 to K-7 are rich in reactivity and heat resistance. Has the effect of improving the solubility, but has the disadvantage of lowering the solvent solubility. From the viewpoint of versatility and characteristics, K-1, K-7, K-8, K-9 and K-10 are particularly preferable, K-12 from the viewpoint of electric characteristics, and K-13 from the viewpoint of liquid crystal alignment. Particularly preferred. One or more diisocyanates can be used in combination, and it is preferable to use various types according to the properties to be obtained.
In addition, some diisocyanates can also be replaced with the tetracarboxylic dianhydride described above, and may be used in the form of a copolymer of a polyamic acid and a polyurea. It may be used in the form of a copolymer.

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

Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, and 1,3-cyclobutanedicarboxylic acid. Acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid Acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4- (2-nor Lenene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1,4-dicarboxylic acid, bicyclo [2.2.2] octane-2,3-dicarboxylic acid, 2, 5-dioxo-1,4-bicyclo [2.2.2] octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro [3. 3] Heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid and the like.

Examples of aromatic dicarboxylic acids include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, and 2,5-dimethylterephthalic acid Acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4 -Anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4 "-terphenyl dicarboxylic acid, 4,4'-diphenyl methane dicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diph Nylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-bibenzyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'- Tolandicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylene diacetate, 3,3'-p-phenylenedipropion Acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3 ′-[4,4 ′-(methylenedi-p-phenylene)] dipropionic acid, 4,4 ′-[4,4 ′-( Oxydi-p-phenylene)] dipropionic acid, 4,4 ′-[4,4 ′-(oxydi-p-phenylene)] dibutyric acid, (isopropylidenedi-p-phenylenedioate) Shi) Secondary acid, and bis (p- carboxyphenyl) dicarboxylic acids such as dimethyl silane.

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

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

It is selected from diamine as a raw material (also described as “diamine component”), tetracarboxylic dianhydride as a raw material (also described as “tetracarboxylic dianhydride component”), tetracarboxylic diester, diisocyanate and dicarboxylic acid. In order to obtain a polyamic acid, a polyamic acid ester, a polyurea, or a polyamide by a reaction with the components, a known synthesis technique can be used. In general, a diamine component is reacted with one or more components selected from a tetracarboxylic dianhydride component, a tetracarboxylic diester, a diisocyanate, and a dicarboxylic acid in an organic solvent.

(4) The reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous in that the reaction proceeds relatively easily in an organic solvent and no by-product is generated.

有機 The organic solvent used in the above reaction is not particularly limited as long as the produced polymer can be dissolved. Furthermore, even if it is an organic solvent in which the polymer is not dissolved, the organic solvent may be mixed with the above solvent as long as the produced polymer does not precipitate. Since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polymer, it is preferable to use a dehydrated organic solvent.

Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, -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 Ter, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 -Methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl- 2-pentanone, 2-ethyl-1-hexanol and the like. These organic solvents may be used alone or as a mixture.

When reacting a diamine component and a tetracarboxylic dianhydride component in an organic solvent, a solution obtained by dispersing or dissolving the diamine component in the organic solvent is stirred, and the tetracarboxylic dianhydride component is allowed to stand as it is or the organic component is dissolved. Dispersing or dissolving in a solvent and adding the dicarboxylic acid to the solution obtained by dispersing or dissolving the tetracarboxylic dianhydride component in the organic solvent, and adding the diamine component to the solution. A method of alternately adding them and the like are mentioned, and any of these methods may be used. When the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of types of compounds, they may be reacted in a mixed state in advance, may be individually reacted sequentially, or may be separately reacted in a low molecular weight. The polymers may be mixed and reacted to form a high molecular weight product.

The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted can be selected at any temperature, and is, for example, in the range of -20 to 100 ° C, preferably -5 to 80 ° C. The reaction can be performed at any concentration. For example, the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, and preferably 5 to 30% by mass, based on the reaction solution. .

比率 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 arbitrarily according to the molecular weight of the polyamic acid to be obtained. As in the ordinary polycondensation reaction, the molecular weight of the generated polyamic acid increases as the molar ratio approaches 1.0. The preferred range is 0.8 to 1.2.

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

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

The temperature at which the polyamic acid is thermally imidized in the solution is usually from 100 to 400 ° C., preferably from 120 to 250 ° C., and is preferably carried out while removing water generated by the imidization reaction out of the system.

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

場合 When recovering the produced polymer from the reaction solution of the polymer, the reaction solution may be put into a poor solvent to precipitate. Examples of the poor solvent used for precipitation generation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer that has been put into the poor solvent and precipitated can be collected by filtration and then dried at normal temperature or under reduced pressure at normal temperature or under normal pressure. In addition, by repeating the operation of re-dissolving the polymer recovered by precipitation in an organic solvent and recovering and recovering the precipitate 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, and hydrocarbons. It is preferable to use three or more poor solvents selected from these, because the purification efficiency is further increased.

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

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

When the radical-generating film used in the present invention is obtained by coating and curing a composition of a compound having a radical-generating group and a polymer to form a film and immobilizing the polymer in the film, A polyimide precursor produced according to the above production method, and a polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, and polymethacrylate, and a diamine having a site where radical polymerization occurs. Alternatively, at least one kind of polymer obtained by using a diamine component that is 0 mol% of the entire diamine component used for synthesizing the polymer to be contained in the radical generating film forming composition may be used. Examples of the compound having a group generating a radical to be added at that time include the following.

化合物 The compound that generates a radical by heat is a compound that generates a radical by heating to a temperature equal to or higher than the decomposition temperature. Examples of such a radical thermal polymerization initiator include ketone peroxides (eg, methyl ethyl ketone peroxide, cyclohexanone peroxide), diacyl peroxides (eg, acetyl peroxide, benzoyl peroxide), and hydroperoxides (eg, peroxides). Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides {(di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy-2-ethylcyclohexane) Sannic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2′-di (2-hydroxyethyl) Azobisisobutyronitrile). One of these radical thermal polymerization initiators can be used alone, or two or more can be used in combination.

The compound that generates a radical by light is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, and 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-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- [pN, 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) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylamino Coumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bi (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2 ' -Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2 -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (5-2,4-cyclopentadi 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, -(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 can be used alone or in combination of two or more.

In addition, even when the radical generating film is made of a polymer containing an organic group that induces radical polymerization, the radical-generating group is used for the purpose of promoting radical polymerization when energy is applied. May be contained.

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

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

Solvents for improving the uniformity and smoothness of the coating film include, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, 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 monomer Diether glycol, 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, Sobutylene, 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, acetic acid Ethyl, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1 -Phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2 -Ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-ethyl-1-hexanol and the like. These solvents may be used in combination of two or more. When these solvents are used, the content 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 the above. Examples of the compound include a compound that improves the film thickness uniformity and surface smoothness when the radical generating film forming composition is applied, a compound that improves the adhesion between the radical generating film forming composition and the substrate, and a radical generating film formation. Compounds that further improve the film strength of the composition are included.

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

Specific examples of the compound that improves the adhesion between the radical-generating film-forming composition and the substrate include a functional silane-containing compound and an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, 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, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N' , N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane and the like. .

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

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

[Radical generation film]
The radical generating film of the present invention is obtained by using the above-mentioned composition for forming a radical generating film. 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 be used as a radical-generating film as it is. The cured film may be rubbed, irradiated with polarized light or light of a specific wavelength, treated with an ion beam, or irradiated with UV on a liquid crystal display element after filling the liquid crystal 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 substrate having high transparency, but a substrate on which a transparent electrode for driving liquid crystal is formed is preferred.
Specific examples include a glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, A substrate on which a transparent electrode is formed, such as a plastic plate of acetylcellulose, diacetylcellulose, acetate butyrate cellulose, or the like can be given.

As a substrate that can be used for an IPS mode liquid crystal display element, an electrode pattern such as a standard IPS comb electrode or a PSA fishbone electrode, or a projection pattern such as MVA can be used.
In the case of a high-performance element such as a TFT element, an element such as a transistor formed between an electrode for driving liquid crystal and a substrate is used.
When a transmissive liquid crystal display element is intended, a substrate as described above is generally used.However, when a reflective liquid crystal display element is intended, silicon is used if only one substrate is used. An opaque substrate such as a wafer can also be used. At this time, a material such as aluminum which reflects light can be used for the electrode formed on the substrate.

Examples of the method of applying the radical-generating film forming composition include a spin coating method, a printing method, an ink jet method, a spray method, and a roll coating method. From the viewpoint of productivity, the transfer printing method is widely used industrially. 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 when the time from application to baking is not constant for each substrate, or when baking is not performed immediately after application, drying is performed. It is preferable to include a step. 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 by the transfer of the substrate or the like, 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.

塗膜 A coating film formed by applying the radical-generating film-forming composition by the above method can be fired to form a cured film. At that time, the calcination temperature can be usually performed at any temperature of 100 ° C. to 350 ° C., preferably 140 ° C. to 300 ° C., more preferably 150 ° C. to 230 ° C., and still more preferably 160 ° C. to 220 ° C. ° C. The calcination time can be usually from 5 minutes to 240 minutes. Preferably it is 10 to 90 minutes, more preferably 20 to 90 minutes. The heating can be performed by a generally known method, for example, a hot plate, a hot air circulation oven, an IR oven, a belt furnace, or the like.

(4) The thickness of the cured film can be selected as necessary, but is preferably 5 nm or more, more preferably 10 nm or more, because the reliability of the liquid crystal display element is easily obtained. When the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, it is preferable because the power consumption of the liquid crystal display element does not become extremely large.

第一 The first substrate having the radical generating film can be obtained as described above, and the radical generating film can be subjected to a uniaxial orientation treatment. Examples of the method for performing the uniaxial orientation treatment include a photo-alignment method, an oblique deposition method, rubbing, and a uniaxial orientation treatment using a magnetic field.

In the case of performing the alignment treatment by performing the rubbing treatment in one direction, for example, the substrate is moved so that the rubbing cloth and the film are in contact with each other while rotating a rubbing roller around which the rubbing cloth is wound. In the case of the first substrate of the present invention in which a comb-shaped electrode is formed, the direction is selected depending on the electrical properties of the liquid crystal. However, when a liquid crystal having positive dielectric anisotropy is used, the rubbing direction is set to the comb-shaped electrode. Is preferably substantially the same as the direction in which

As a process for producing the zero anchoring portion and the strong anchoring portion, there is a method of irradiating radiation in an arbitrary pattern via a photomask or the like. This is a step of irradiating the radical generating film in advance with radiation to eliminate the radical generating site and prevent a zero anchoring state. Radiation for performing this step includes polarized light or light of a specific wavelength, an ion beam, and the like. It is particularly preferable to irradiate light having a wavelength at which the absorbance of the portion corresponding to the photoradical generation site is the highest.

第二 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>
The liquid crystal cell of the present invention comprises, 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 arranged so that the radical generating film and the liquid crystal alignment film face each other, fixed with a sealant across a spacer, and injected and sealed with a liquid crystal composition containing a liquid crystal and a radical polymerizable compound. Can be At this time, the size of the spacer used is usually 1 to 30 μm, preferably 2 to 10 μm.
The method of injecting the liquid crystal composition containing the liquid crystal and the radical polymerizable compound is not particularly limited, and a vacuum method of injecting a mixture containing the liquid crystal and the polymerizable compound after reducing the pressure in the manufactured liquid crystal cell, Dropping method in which sealing is performed after dropping a mixture containing a reactive compound and the like.

<Liquid crystal composition containing liquid crystal and radical polymerizable compound>
In the production of the liquid crystal display device of the present invention, the polymerizable compound used together with the liquid crystal is not particularly limited as long as it is a radical polymerizable compound, for example, a compound having one or two or more polymerizable unsaturated bonds in one molecule It is. Preferred are compounds having one polymerizable unsaturated bond in one molecule (hereinafter referred to as "compounds having a monofunctional polymerization reactive group", "compounds having a monofunctional polymerization reactive group", etc.) There). The polymerizable unsaturated bond is preferably a radical polymerizable unsaturated bond, for example, a vinyl bond.

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

The polymerization reactive group of the radical polymerizable compound is preferably a polymerizable group selected from the following structures.

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

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

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

Further, as the radical polymerizable compound, a compound represented by the following formula (1) is also preferable.

In the formula (1), R ^a and R ^b each independently represent a linear alkyl group having 2 to 8 carbon atoms, and E represents a single bond, —O—, —NR ^c —, —S—, an ester bond, an amide 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 compatible with a liquid crystal, and is preferably a compound having one polymerizable unsaturated bond in one molecule, that is, a compound having a monofunctional radical polymerizable group. .

The radical polymerizable compound represented by the formula (1) is a compound in which E is an ester bond (a bond represented by —C (＝ O) —O— or —OC (＝ O) —). Is preferred from the viewpoint of easiness of synthesis, compatibility with liquid crystal, and polymerization reactivity. Specifically, compounds having the following structures are preferred, but there is no particular limitation.

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

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

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

The content of the radical 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 radical polymerizable compound. Or less, more preferably 20% by mass or less.

ポ リ マ ー The polymer obtained by polymerizing the radical polymerizable compound preferably has a Tg of 100 ° C or lower.

液晶 Note that the liquid crystal generally refers to a substance exhibiting properties of both a solid and a liquid. Representative liquid crystal phases include a nematic liquid crystal and a smectic liquid crystal, but the liquid crystal that can be used in the present invention is not particularly limited. An example is 4-pentyl-4'-cyanobiphenyl.

Next, sufficient energy is applied to a liquid crystal cell into which a mixture (liquid crystal composition) containing the liquid crystal and the radical polymerizable compound has been introduced to cause the radical polymerizable compound to undergo a polymerization reaction. This can be carried out, for example, by applying heat or UV irradiation, and the desired properties are exhibited by the radical polymerizable compound being polymerized in situ. Above all, UV irradiation is preferable because UV irradiation enables patterning of orientation and allows a polymerization reaction to be performed in a shorter time.

In addition, heating may be performed at the time of UV irradiation. The heating temperature at the time of performing the UV irradiation is preferably a temperature range in which the introduced liquid crystal exhibits liquid crystallinity, and is usually 40 ° C. or higher, and is preferably heating at a temperature lower than the temperature at which the liquid crystal changes to an isotropic phase.

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

加熱 In addition, in the case of performing polymerization only by heating, not by UV irradiation, the heating is preferably performed at a temperature at which the polymerizable compound reacts and 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.

(4) It is preferable that no voltage is applied and no electric field is applied when energy sufficient to cause a polymerization reaction of the radical polymerizable compound is given.

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

The present invention will be described specifically 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 for evaluating the properties are as follows.

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

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

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

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

Synthesis Example 2
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-3 (50) polyimide DA-1 was placed in a 100 ml four-necked flask equipped with a nitrogen inlet tube, an air cooling tube, and a mechanical stirrer. 1.62 g (15.00 mmol) and 4.96 g (15.00 mmol) of DA-3 were weighed out, 51.90 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere and completely dissolved. After confirming dissolution, 3.75 g (15.00 mmol) of TC-2 was added and reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. The temperature was returned to room temperature, 2.64 g (13.5 mmol) of TC-1 was added, and the mixture was reacted at 40 ° C. for 12 hours under a nitrogen atmosphere. After confirming the polymerization viscosity, TC-1 was further added so that the polymerization viscosity became 1000 mPa · s, to obtain a polymerization solution having a polyamic acid concentration of 20% by mass.
In a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, 60 g of the polyamic acid solution obtained above was weighed, 111.4 g of NMP was added, and a 7% by mass solution was prepared. (81.4 mmol) and 3.62 g (45.8 mmol) of pyridine were added, and the mixture was stirred at room temperature for 30 minutes and then reacted at 55 ° C. for 3 hours. After the completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol while stirring to precipitate a solid. The solid is collected by filtration, and the solid is further poured into 300 ml of methanol and stirred and washed twice for 30 minutes. The solid is collected by filtration, air-dried, and then dried in a vacuum oven at 60 ° C. As a result, a polyimide (PI-2) having a number average molecular weight Mn of 13100, a weight average molecular weight Mw of 34000, and an imidization ratio of 55% was obtained.

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

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

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

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

<Production of polymerizable compound>
Synthesis example 1 of polymerizable compound
Synthesis of ethyl 2- (heptanoyloxymethyl) acrylate

First step: Synthesis of ethyl 2-hydroxymethyl acrylate In a 500 ml four-necked flask equipped with a nitrogen inlet tube, 10 mg of 4-methoxyphenol and DABCO (1,4-diazabicyclo [2.2.2] octane) 21 were added. 0.88 g (195.1 mmol) was weighed out, 50 ml of pure water was added, and 11.52 g (390.1 mmol) of paraformaldehyde was added while stirring at 10 ° C. or lower under a nitrogen atmosphere, followed by stirring for 1 hour. After confirming the change from the slurry state to the solution state, 300 ml of acetonitrile was added, 19.53 g (195.1 mmol) of ethyl acrylate was added dropwise, and the mixture was reacted at 50 ° C. for 5 hours. After the completion of the reaction, the reaction solution was transferred to a separating funnel, and 50 ml of n-hexane was added. After confirming that the layers were separated into three layers, the lower two layers were collected, and this operation was performed three times. Further, hydrochloric acid was added so that the pH became 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, and then filtered and concentrated 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 a nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.81 (1H), 5.80 (1H), 4.31 (2H), 4.17 (1H), 1.98 (1H), 0.93 (3H)

Second step: Synthesis of ethyl 2- (heptanoyloxymethyl) acrylate In a 500 ml four-necked flask equipped with a nitrogen inlet tube, 19.9 g (152) of 2-hydroxymethylacrylic acid obtained by the above method was placed. 2.9 mmol), THF (300 ml) and triethylamine (23.2 g, 229.3 mmol) were added, and while keeping the temperature at 10 ° C. or lower under a nitrogen atmosphere, heptanoyl chloride (25.0 g, 168.2 mmol) was added dropwise and reacted for 6 hours. Was. After completion of the reaction, the precipitated triethylamine hydrochloride was removed by filtration, the reaction solution was concentrated, redissolved in 300 ml of ethyl acetate, washed three times with 100 ml of a 10% aqueous potassium carbonate solution, and washed with 50 ml of pure water. After washing twice and drying over anhydrous magnesium sulfate, filtration and concentration were performed to obtain a pale yellow viscous body. Further, the product is purified by flash column chromatography (developing solvent: ethyl acetate: n-hexane = 20: 80), and the solvent is removed and dried under vacuum to obtain 32.2 g (133.0 mmol: yield) of a colorless and transparent oily liquid. 87%). The structure was confirmed to be the desired product by a 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)

Synthesis example 3 of polymerizable compound
Synthesis of dihexyl itaconate

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

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

(First substrate)
The first substrate (hereinafter also referred to as an IPS substrate) is a non-alkali glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. On the substrate, an ITO (Indium-Tin-Oxide) electrode having a comb-shaped pattern with an electrode width of 10 μm and an interval between the electrodes of 10 μm is formed to form a pixel. Each pixel is about 10 mm long and about 5 mm wide.
After filtering through a filter of AL1 to AL3 or 1.0 μm, the solution was applied to the electrode forming surface of the IPS substrate by spin coating, and dried on a hot plate at 80 ° C. for 1 minute. Then, AL1 to AL3 were baked at 220 ° C. for 20 minutes, and SE-6414 was baked at 220 ° C. for 20 minutes.

The substrate with the coating film was shielded from light by a metal plate so that half of the substrate was not exposed to light, and was irradiated with ultraviolet light using a high-pressure mercury lamp through a band-pass filter having a wavelength of 313 nm so that the exposure amount was 5000 mJ. Hereinafter, this operation is referred to as primary UV processing.
After the exposure treatment, rubbing was performed so that the rubbing direction was inclined by 5 ° from the longitudinal direction of the comb-shaped electrode. Rubbing was performed using rayon cloth: YA-20R manufactured by Yoshikawa Kako Co., Ltd. under the conditions of a roll diameter of 120 mm, a rotation speed of 300 rpm, a moving speed of 50 mm / sec, and a pushing amount of 0.4 mm. After the rubbing treatment, the substrate was irradiated with ultrasonic waves in pure water for 1 minute and dried at 80 ° C. for 10 minutes.

(Second substrate)
The second substrate (also referred to as a back surface ITO substrate) is a non-alkali glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm, and an ITO film is formed on a back surface (a surface facing the outside of the cell). ing. Further, a columnar spacer having a height of 4 μm is formed on the surface (the surface facing the inside of the cell).
SE-6414 was filtered through a 1.0 μm filter onto the glass surface of the backside ITO substrate, applied by spin coating, and dried on a hot plate at 80 ° C. for 1 minute. Next, AL1 and AL2 were baked at 220 ° C. for 20 minutes, and SE-6414 was baked at 220 ° C. for 20 minutes to form a coating film having a thickness of 100 nm, respectively, and then rubbed. The rubbing treatment was performed using rayon cloth: YA-20R manufactured by Yoshikawa Kako Co., Ltd. under the conditions of a roll diameter of 120 mm, a rotation speed of 1000 rpm, a moving speed of 50 mm / sec, and a pushing amount of 0.4 mm. After the rubbing treatment, the substrate was irradiated with ultrasonic waves in pure water for 1 minute and dried at 80 ° C. for 10 minutes.

(Production of liquid crystal cell)
Using two kinds of substrates (the first substrate and the second substrate) with the liquid crystal alignment film, the periphery was sealed except for the liquid crystal injection port, and an empty cell having a cell gap of about 4 μm was produced. At this time, a substrate in which the rubbing directions of the first substrate and the second substrate are antiparallel and a substrate in which the rubbing directions intersect at 85 ° were prepared.
Liquid crystal (a liquid obtained by adding each additive to a positive liquid crystal MLC-3019 for IPS manufactured by Merck and a liquid crystal MLC3018U for TN manufactured by Merck under optimum conditions) is vacuum-injected into the empty cell at room temperature, and then the injection port is sealed. The liquid crystal cell was stopped. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element and a TN mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was subjected to a heat treatment at 120 ° C. for 10 minutes.
As a secondary UV treatment, irradiation was performed using a high-pressure mercury lamp through a band-pass filter having a wavelength of 313 nm. The liquid crystal cell was irradiated with ultraviolet rays so that the exposure amount was 5000 mJ. Table 4 below shows details of the prepared cells.

<Visual evaluation of liquid crystal orientation>
The orientation of the TN mode liquid crystal cell was confirmed using a polarizing plate set in crossed Nicols. When the UV treatment is not performed, the alignment regulating force of the one-sided alignment film is lost (that is, the film becomes a zero anchoring state), and is not sufficiently twisted by the regulating force of the chiral dopant in the liquid crystal. I do. On the other hand, the UV-treated area loses the polymerization reactivity, so that the anchoring force is maintained. Therefore, twist orientation occurs. As a result, two types of alignment states occur in the pixel. As shown in FIG. 1, the region where the film was irradiated with UV was TN oriented (white), the region where UV was not irradiated was horizontally oriented (black), and the case where there was no change in each region. X.

(4) When a liquid crystal having no additive in the liquid crystal was used, and when a material that did not generate radicals by light was used, alignment patterning, that is, a change in alignment control force did not occur even when the primary UV treatment was performed. This indicates that the combination of the photo-radical generating film of the present invention and the additive is important.

<Electro-optical property evaluation>
Using cells 13 to 24 (horizontal alignment cells), the VT curve was measured to measure the change in threshold voltage and the mode efficiency. For the measurement of the VT curve, a white LED backlight and a luminance meter are set so that the optical axes are aligned, and a liquid crystal cell (liquid crystal display element) having a polarizing plate attached thereto is set between the white LED backlight and the luminance meter so as to minimize the luminance. This was performed by applying a voltage up to 8 V at 1 V intervals and measuring the luminance at the voltage. The value of the driving threshold voltage was estimated from the obtained VT curve. The mode efficiency was measured by calculating the ratio of the luminance of the liquid crystal cell at Vmax to the luminance of the LED transmitted light at the time of parallel Nicols of the polarizing plate.
In the anchoring measurement, an approximate value was estimated from the magnitude of the threshold voltage by the Freedericksz transfer method.

Because the cells 13 to 24 are horizontal alignment cells, there is no visual change even when the alignment becomes zero anchoring alignment. On the other hand, the threshold voltage and luminance of the VT curve were changed between the primary UV exposed portion and the unexposed portion. It can be seen from this verification that regions having different anchoring forces can be created in the pixel by performing the primary exposure.

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

Claims (22)

1. Forming a patterned radical generating film by irradiating a specific region with radiation to the radical generating film, and contacting a liquid crystal composition containing a liquid crystal and a radical polymerizable compound with the patterned radical generating film, A method for producing a patterned zero-plane anchoring film, comprising a step of applying sufficient energy to the liquid crystal composition to cause a polymerization reaction of the radically polymerizable compound while maintaining the state.
2. The method according to claim 1, wherein the radical generating film is a uniaxially oriented radical generating film.
3. The method according to claim 1 or 2, wherein the step of applying energy is performed without an electric field.
4. (4) The method according to any one of (1) to (3), wherein the radical generating film is a film in which an organic group that induces radical polymerization is fixed.
5. 2. 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 film in the film. The method according to any one of claims 1 to 3.
6. (4) 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 a polyimide precursor obtained using a diamine component containing a diamine containing an organic group that induces radical polymerization, at least one kind selected from polyimide, polyurea, and polyamide. 7. The method according to claim 6, wherein the method is a polymer.
8. 7. The organic group which induces radical polymerization is an organic group represented by any of the following structures [X-1] to [X-18], [W], [Y] and [Z]. The method according to any one of claims 1 to 7.
   

   

   
   (In the formulas [X-1] to [X-18], * represents a bonding site to a part other than the polymerizable unsaturated bond of the compound molecule, and S ₁ and S ₂ are each independently —O—, − R 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; R ₁ and R ₂ each independently represent a hydrogen atom; Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms)
   

   

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

   

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

   

   
   (In the formula (6), R ⁶ is a single bond, —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N (CH ₃ ) —, —CON (CH ₃ ) —, or —N (CH ₃ ) CO—,
   R ⁷ represents a single bond or an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, wherein at least one of —CH ₂ — or —CF ₂ — in the alkylene group is independently May be replaced by a group selected from —CH ＝ CH—, a divalent carbocyclic ring, and a divalent heterocyclic ring. Further, any of the following groups: —O—, —COO— , —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups provided that they are not adjacent to each other;
   R ⁸ is the following formula:
   

   

   Represents a radical polymerization reactive group selected from
   (In the formulas [X-1] to [X-18], * indicates a bonding site to a part other than the radical polymerization reactive group of the compound molecule, and S ¹ and S ² are each independently -O-,- R 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; R ₁ and R ₂ each independently represent a hydrogen atom; Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms))
   

   

   
   (In the 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 ⁰ represents a single bond or an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, wherein at least one of —CH ₂ — or —CF ₂ — in the alkylene group is independently May be replaced by a group selected from —CH ＝ CH—, a divalent carbocyclic ring, and a divalent heterocyclic ring. Further, any of the following groups: —O—, —COO— , —OCO—, —NHCO—, —CONH—, or —NH— may be replaced by these groups provided that they are not adjacent to each other;
   J is an organic group represented by any of the following formulas,
   

   

   
   (Wherein [W], [Y], [Z] in which * represents a bonding site to T _2, Ar is may have an organic group and / or a halogen atom as a substituent phenylene, naphthylene, and biphenylene And 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 represents any of the following: Represents the structure of
   

   

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

    

    
    (In the formula, * represents a bonding site to a portion other than the polymerizable unsaturated bond of the compound molecule. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-,- Represents a bonding group selected from NR ^c- , -S-, an ester bond and an amide bond, wherein R ^c is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
12. In the liquid crystal composition containing the liquid crystal and the radical polymerizable compound, a liquid crystal composition containing a radical polymerizable compound having a Tg of 100 ° C. or lower is obtained by polymerizing the radical polymerizable compound. The method according to any one of claims 1 to 11, characterized in that:
13. Preparing a first substrate having a radical generating film and a second substrate that may have a radical generating film,
    Creating a cell such that the radical generating film on the first substrate faces the second substrate, and
    Filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between the first substrate and the second substrate,
    A method for manufacturing a liquid crystal cell using the method according to any one of claims 1 to 12.
14. 14. The method for manufacturing a liquid crystal cell according to claim 13, wherein the second substrate is a second substrate having no radical generating film.
15. The method according to claim 14, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment.
16. 16. The method according to claim 15, wherein the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment.
17. 17. The method for manufacturing a liquid crystal cell according to claim 13, wherein the first substrate having the radical generating film is a substrate having a comb electrode.
18. Contains liquid crystal and radical polymerizable compound,
    At least one of the radically polymerizable compounds is compatible with a liquid crystal, a compound having one polymerizable unsaturated bond in one molecule,
    A liquid crystal composition wherein the polymerization reactive group is selected from the following structures.
    

    

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

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