WO2019004433A1

WO2019004433A1 - Method for producing zero-azimuthal anchoring film, and liquid crystal display element

Info

Publication number: WO2019004433A1
Application number: PCT/JP2018/024824
Authority: WO
Inventors: 尚宏野田; 正人森内
Original assignee: 日産化学株式会社
Priority date: 2017-06-30
Filing date: 2018-06-29
Publication date: 2019-01-03
Also published as: CN110785698A; TWI782997B; KR20200023307A; CN110785698B; JPWO2019004433A1; JP7234924B2; TW201905178A

Abstract

Provided are: a method for producing a zero-azimuthal anchoring film on an industrial scale; and a good liquid crystal display element and a method for producing a liquid crystal display element, in each of which the aforementioned method is employed. A method for producing a zero-azimuthal anchoring film, the method including a step of applying an energy sufficient to cause a polymerization reaction of a radical-polymerizable compound while coming a liquid crystal composition containing a liquid crystal and the radical-polymerizable compound into contact with a radical generation film; and a method for producing a functional film, the method including a step of preparing a cell in which a liquid crystal composition containing a liquid crystal and a radical-polymerizable compound is arranged between a first substrate having a radical generation film and a second substrate having no radical generation film and a step of applying an energy sufficient to cause a polymerization reaction of the radical-polymerizable compound to the cell.

Description

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

The present invention is a manufacturing method applying a polymer stabilization technology capable of manufacturing a zero plane anchoring film in a cheap and complicated method, and a further low voltage using the manufacturing method. The present invention relates to a liquid crystal display element for realizing driving and a method of manufacturing the same.

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

In particular, products equipped with touch panels such as tablet PCs, smartphones, and smart TVs are favored by the IPS mode in which the display is less likely to be disturbed by touch, and in recent years FFS (Frindge) in terms of improvement in contrast and viewing angle characteristics. Technologies using liquid crystal display elements using Field Switching) and non-contact technologies using optical alignment have come to be used.

However, FFS has a problem that the manufacturing cost of the substrate is larger than IPS, and a display defect specific to FFS mode called Vcom shift occurs. With regard to photoalignment, there are advantages in that the size of the device that can be manufactured can be increased and the display characteristics can be greatly improved compared to the rubbing method. In the case of an isomerization type, there is a problem such as burn-in due to lack of orientation. At present, liquid crystal display element manufacturers and liquid crystal alignment film manufacturers are making various efforts to solve those problems.

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

Specifically, a liquid crystal alignment film having strong anchoring energy is used as the substrate on one side, and the substrate side provided with an electrode for generating one of the lateral electric fields has no ability to control the alignment of the liquid crystal at all. Treatment to make an IPS mode liquid crystal display element using them.

In recent years, a zero-surface state is created using a thick polymer brush or the like, and a technical proposal for a cell-surface anchoring IPS mode has been made (Reference 2). This technology achieves a significant improvement in contrast ratio and a significant reduction in drive voltage.

Patent No. 4053530 JP, 2013-231757, A

On the other hand, there is a problem that occurs in principle in this technology, and firstly, in order to stably generate a polymer brush on a substrate, it is necessary to carry out under very delicate conditions, and considering mass production it is realistic Not to mention. Second, the alignment film plays an important role such as suppression of image sticking, but it is difficult to control the required electric properties when using a polymer brush or the like. The third reason is that the response speed at the time of setting the voltage to Off in driving principle becomes very slow. By eliminating the resistance at the time of driving applied to the liquid crystal by making the alignment control force zero, it is expected that the luminance can be improved by the drastic drop of the threshold voltage and the decrease of the alignment failure area at the time of driving. As for the power of the liquid crystal to be returned depends on the elastic force of the liquid crystal, it is considered that the speed is greatly reduced as compared with the case where the alignment film is present.
If such a technical problem can be solved, it will be a great cost advantage also as a panel maker, and it may be a merit also to the consumption control of a battery, the improvement of an image quality, etc.
The present invention has been made to solve the above problems, and a manufacturing method applying a polymer stabilization technology capable of manufacturing a zero plane anchoring film, and a simple and inexpensive method at normal temperature. It is an object of the present invention to provide an in-plane switching mode liquid crystal display device and a method of manufacturing the same, which can simultaneously realize non-contact alignment, low driving voltage and high response speed at the time of Off.

MEANS TO SOLVE THE PROBLEM As a result of conducting earnest examination, in order to solve said subject, the present inventors find out that said subject can be solved, and completed this invention which has the following summary.

That is, the present invention includes the following.
[1] A zero plane anchor comprising a step of providing sufficient energy for causing a polymerization reaction of the radically polymerizable compound in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is in contact with the radical generating film. Method of manufacturing ring film.
[2] The method according to [1], wherein the radical generating film of the first substrate is a uniaxially oriented radical generating film.
[3] The method according to [1] or [2], wherein the step of applying energy is performed without an electric field.
[4] The method according to any one of [1] to [3], wherein the radical generating film is a film formed by fixing an organic group that induces radical polymerization.
[5] The radical generating film is characterized in that it is obtained by applying and curing a composition of a compound having a radical generating group and a polymer to form a film, thereby immobilizing 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 comprises a polymer containing an organic group that induces radical polymerization.
[7] The polymer containing an organic group that induces radical polymerization is selected from polyimide precursors, polyimides, polyureas, and polyamides obtained using a diamine component containing a diamine containing an organic group that induces radical polymerization. The method according to [6], which is at least one polymer.
[8] The organic group inducing the radical polymerization is an organic group represented by the following structures [X-1] to [X-18], [W], [Y] and [Z] [4] and [8] 6] and the method as described in any one of [7].

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

(In the formulas [W], [Y] and [Z], * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule, Ar has an organic group and / or a halogen atom as a substituent R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, each of which is an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene. When R ⁹ and R ¹⁰ are alkyl groups, they may be bonded to each other at their ends 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 Indicates the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. )
[9] The method according to [7], wherein the diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7) .

(In the formula (6), R ⁶ represents a single bond, —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N _{(CH 3) -, - CON} (CH 3) -, or -N _(CH 3) CO- represents,
R ⁷ represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more of any —CH ₂ — or —CF ₂ — of the alkylene group are each independently And may be substituted with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, ie, -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:

And a radical polymerization reactive group selected from
(In formulas [X-1] to [X-18], * represents a binding site to a moiety other than the radical polymerization reactive group of the compound molecule, and S ¹ and S ² are each independently —O—, — And 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, and R ¹ and R ² each independently represent a hydrogen atom, Halogen atom, represents an alkyl group having 1 to 4 carbon atoms))

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

(In the formulas [W], [Y] and [Z], * represents a bonding site to T ² , Ar represents an organic group and / or a phenylene, naphthylene, and biphenylene which may have a halogen atom as a substituent) 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 a structure shown below Represents

(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 Indicates the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. )))
[10] In any one of [1] to [9], at least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule, which is compatible with liquid crystal. Method described.
[11] The method according to [10], wherein the polymerizable reactive group of the radically polymerizable compound is selected from the following structures.

(Wherein, * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule. R ^b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR ^c represents a linking group selected from-, -S-, an ester bond and an amide bond, and R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
[12] A liquid crystal composition containing a liquid crystal and a radical polymerizable compound, wherein the polymer obtained by polymerizing the radical polymerizable compound has a Tg of 100 ° C. or less. The method according to any one of [1] to [11], which is characterized in that
[13] preparing a first substrate having a radical generation film and a second substrate which may have the radical generation film;
Creating a cell such that the radical generating film on the first substrate faces the second substrate;
Filling the liquid crystal composition containing a liquid crystal and a radically polymerizable compound between the first substrate and the second substrate,
A method for producing a liquid crystal cell using the method according to any one of [1] to [12].
[14] The method for producing a liquid crystal cell according to [13], wherein the second substrate is a second substrate not having a radical generation film.
[15] The method for producing a liquid crystal cell according to [14], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial orientation.
[16] The method for producing a liquid crystal cell according to [15], wherein the liquid crystal alignment film having uniaxial alignment property 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 radically polymerizable compound,
At least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule, which is compatible with liquid crystal,
A liquid crystal composition, wherein the polymerizable reactive group is selected from the following structures.

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

According to the present invention, a zero plane anchoring film can be industrially produced with high yield. By using the method of the present invention, it is possible to easily manufacture a liquid crystal display element similar to the zero plane anchoring IPS mode liquid crystal display element described in Patent Documents 1 and 2 by using inexpensive raw materials or existing manufacturing methods. In addition, the liquid crystal display device obtained by the manufacturing method of the present invention has excellent characteristics such that the response speed of the liquid crystal at the time of Off is faster than the prior art, and the low driving voltage, no bright spot, and Vcom shift hardly occur. It is possible to provide a liquid crystal display element having the same.

The present invention is a method for producing a zero plane anchoring film, which comprises polymerizing a polymerizable compound by UV or heat in a state in which a liquid crystal containing a specific polymerizable compound is in contact with a radical generating film. More specifically, a cell having a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is provided between a first substrate having a radical generating film and a second substrate which may have a radical generating film. And a step of providing the cell with sufficient energy to polymerize the radically polymerizable compound. Preferably, a step of preparing a first substrate having a radical generating film and a second substrate not having a radical generating film, a step of forming a cell so that the radical generating film faces the second substrate, and A method of manufacturing a liquid crystal cell, comprising the step of filling a liquid crystal composition containing a liquid crystal and a radically polymerizable compound between one substrate and a second substrate. For example, in a low voltage drive IPS liquid crystal display device, the second substrate does not have a radical generation film, and is a substrate having a liquid crystal alignment film subjected to uniaxial alignment processing, and the first substrate has a comb electrode. It is a creation method.

In the present invention, the "zero-surface anchoring film" means that there is no alignment control force of liquid crystal molecules in the in-plane direction, or if any, it is weaker than the intermolecular force between liquid crystals. A film that does not allow uniaxial orientation in the direction of Also, the zero plane anchoring film is not limited to a solid film, and includes a liquid film covering a solid surface. Normally, in the liquid crystal display element, a film that regulates the alignment of liquid crystal molecules, ie, a liquid crystal alignment film is used as a pair to align the liquid crystal, but even when this zero plane anchoring film and the liquid crystal alignment film are used as a pair It can be oriented. This is because the alignment control force of the liquid crystal alignment film is transmitted also to the thickness direction of the liquid crystal layer by the intermolecular force of liquid crystal molecules, and as a result, the liquid crystal molecules close to the zero plane anchoring film are also aligned. Therefore, when a liquid crystal alignment film for horizontal alignment is used as the liquid crystal alignment film, it is possible to create a horizontal alignment state in the entire liquid crystal cell. Horizontal alignment refers to a state in which the major axes of liquid crystal molecules are aligned substantially parallel to the liquid crystal alignment film surface, and inclined alignment of several degrees is included in the category of horizontal alignment.

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

Such organic groups that induce radical polymerization include organic groups represented by the following structures [X-1] to [X-18], [W], [Y], and [Z]. Be

(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 Indicates the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. )

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

When a polymer having an organic group capable of inducing radical polymerization is used to obtain a radical generating film used in the present invention, to obtain a polymer having a group capable of generating a radical, a methacryl group as a monomer component, A monomer having a photoreactive side chain containing at least one selected from an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group, or a site which is decomposed by ultraviolet irradiation to generate a radical is a side chain It is preferable to manufacture using the monomer which it has. On the other hand, since monomers that generate radicals are considered to have problems such as spontaneous polymerization by themselves and become unstable compounds, they have radical generation sites in terms of easiness of synthesis Polymers derived from diamines are preferred, and more preferred are polyimide precursors such as polyamic acids and polyamic acid esters, polyimides, polyureas and polyamides.

Specifically, such a radical generation site-containing diamine is, for example, a diamine having a side chain capable of generating a radical and capable of polymerization, and examples thereof include diamines represented by the following general formula (6). Not limited to this.

And a radical polymerization reactive group selected from
(In formulas [X-1] to [X-18], * represents a binding site to a moiety other than the radical polymerization reactive group of the compound molecule, and S ¹ and S ² are each independently —O—, — And 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, and 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)

The bonding position of the two amino groups (-NH ₂ ) in the formula (6) is not limited. Specifically, with respect to the linking group of the side chain, the 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, 3, 4 positions on the benzene ring There are 5 positions. Among them, from the viewpoint of reactivity when synthesizing a polyamic acid, the positions of 2, 4, 2, 5, or 3, 5 are preferable. The positions of 2, 4 or 3, 5 are more preferable in consideration of the ease of synthesis of the diamine.

Specific examples of the diamine having a photoreactive group containing at least one selected from the group consisting of methacryl group, acryl group, vinyl group, allyl group, coumarin group, styryl group and cinnamoyl group include the following: Compounds include but are not limited to these.

(Wherein, J ¹ is a bonding group selected from a single bond, -O-, -COO-, -NHCO-, or -NH-, and J ² is a single bond, or unsubstituted or substituted by a fluorine atom) (C 1 to C 20 alkylene group)

Examples of the diamine which is decomposed by irradiation with ultraviolet light and which has a site where a radical is generated as a side chain include, but not limited to, diamines represented by the following general formula (7).

(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 Indicates the binding site with other parts.)
R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. )))

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

In particular, in view of easiness of synthesis, height of versatility, characteristics and the like, a structure represented by the following formula is most preferable, but is not limited thereto.

(Wherein n is an integer of 2 to 8)

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

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

When the polymer used 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 may be used as a diamine component as long as the effect of the present invention is not impaired. be able to. Specifically, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl , 3,3'-Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'- 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, 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 , 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, 6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2 -Bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1 , 4-bis (4 aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3 5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenylene Bis (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)] dia Phosphorus, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylene bis [(3-aminophenyl) methanone], 1,4-phenylene bis (4-aminobenzoate), 1,4-phenylene bis (3-aminobenzoate), 1,3-phenylene bis (4 -Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) terephthalate Aminophenyl) isophthalate, N, N '-(1,4-phenylene) bis (4-aminobenzamide) ), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N ′-(1,1) 3-phenylene) bis (3-aminobenzamido), 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) diphenyl sulfone, 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, To, 4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) Xan, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7-bis (3-aminophenoxy) heptane, 1,8-bis (4- Aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10-bis 4-Aminophenoxy) decane, 1,10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 1,11-bis (3-amino Aromatic diamines such as phenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane, 1,12-bis (3-aminophenoxy) dodecane; bis (4-aminocyclohexyl) methane, bis (4-amino-) Alicyclic diamines such as 3-methylcyclohexyl) methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 Aliphatic diamines such as 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane; 1,3-bis [2- (p-amino) Phenyl) ethyl] urea, 1,3-bis [2- (p-aminophenyl) ethyl] -1-tert-butyl ester A diamine having a urea structure such as carbonylurea; a diamine having a nitrogen-containing unsaturated heterocyclic ring structure such as Np-aminophenyl-4-p-aminophenyl (tertiary butyloxycarbonyl) aminomethylpiperidine; an N-tertiary Examples thereof include diamines having an N-Boc group such as butoxycarbonyl-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 according to the properties such as liquid crystal alignment, sensitivity in polymerization reaction, voltage holding property, and accumulated charge when forming a radical generating film. .

There is no particular limitation on the tetracarboxylic acid dianhydride to be reacted with the above-mentioned diamine component in the synthesis when the polymer is a polyamic acid. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyl tetracarboxylic acid, 2,3,3', 4'-biphenyl Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-diphenyl) Carboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxy) ) Propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3 3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, 1,3-diphenyl-1,2,3,3, 4-Cyclobutane tetracarboxylic acid, oxydiphthalic tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexane Tetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,3 -Cyclobutane tetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid Acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4, 0] decane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2, 6>] Undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydrylnaphthalene-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 And dianhydrides of tetracarboxylic acids such as 5,6,6-tricarboxy norbornane-2: 3,5: 6 dicarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid.

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

The structure of the tetracarboxylic acid dialkyl ester to be reacted with the above diamine component is not particularly limited in the synthesis in the case where the polymer is a polyamic acid ester, but specific examples thereof will be given below.
Specific examples of aliphatic tetracarboxylic acid diesters include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1 , 3-Dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester 3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexane tetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1 -Cyclohexyl succinic acid dialkyl ester, 3,4- dicarboxy- 2,2,3,4-Tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8- Tetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5- Diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 <2,5>] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7 , 8-dialkyl esters, 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: 1,12-dialkyl ester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester and the like.

As the aromatic tetracarboxylic acid dialkyl ester, pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyl tetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyl tetracarboxylic acid dialkyl ester, 2,3,3 ', 4-biphenyltetracarboxylic acid dialkyl ester, 3,3', 4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3 ', 4'-benzophenonetetracarboxylic acid dialkyl ester, Bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7 -Naphthalenetetracarboxylic acid dialkyl ether Tel and the like.

There is no particular limitation on the diisocyanate to be reacted with the above-mentioned diamine component in the synthesis when the polymer is polyurea, and it can be used according to the availability etc. The specific structure of diisocyanate is shown below.

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

Aliphatic diisocyanates shown in K-1 to K-5 are inferior in reactivity but have the merit of improving solvent solubility, and aromatic diisocyanates such as K-6 to K-7 are rich in reactivity and heat resistance Although it has the effect of improving the solvent, it has the disadvantage of reducing the solvent solubility. Particularly preferred are K-1, K-7, K-8, K-9, and K-10 in terms of versatility and properties, K-12 in terms of added electrical characteristics, and K-13 in terms of liquid crystal alignment. Particularly preferred. Diisocyanate can be used in combination of one or more kinds, and it is preferable to apply variously according to the characteristics to be obtained.
In addition, some of the diisocyanates can be replaced with the tetracarboxylic acid dianhydride described above, and may be used in the form of a copolymer of polyamic acid and polyurea, and chemical imidation can be used to convert polyimide and polyurea. You may use in a form like a copolymer.

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

Examples of 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 Runene) 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, 5-dioxo-1,4-bicyclo [2.2.2] octane dicarboxylic acid, 1,3-adamantane dicarboxylic acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro [3. 3] Heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid and the like can be mentioned.

As aromatic dicarboxylic acid, o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid Acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4 -Anthraquinonedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4 "-terphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4 , 4'-Diphenylethanedicarboxylic acid, 4,4'-Diphenyl Nylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 4,4'- Transdicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-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, (isopropylidene di-p-phenylenedio) Shi) Secondary acid, and bis (p- carboxyphenyl) dicarboxylic acids such as dimethyl silane.

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

The various dicarboxylic acids described above may be acid dihalides or those of anhydrous structure. These dicarboxylic acids are preferably dicarboxylic acids that can give a polyamide having a particularly linear structure, from the viewpoint of maintaining the alignment of liquid crystal molecules. Among these, terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4 '-Diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propanedicarboxylic acid, 4,4-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 5-pyridinedicarboxylic acid or their acid dihalides are preferably used. Although some of these compounds have isomers, they may be a mixture containing them. Also, two or more compounds may be used in combination. The dicarboxylic acids used in the present invention are not limited to the above exemplified compounds.

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

The reaction of the diamine component with the tetracarboxylic acid dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.

The organic solvent used for the above reaction is not particularly limited as long as it can dissolve the produced polymer. Furthermore, even if it is an organic solvent in which a polymer does not melt | dissolve, you may use it, mixing with the said solvent in the range which the produced | generated polymer does not precipitate. In addition, since water in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the produced polymer, it is preferable to use the organic solvent which has been dehydrated and dried.

Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2 -Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ- Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve Cetate, 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, methylcyclohexyl, propyl ether, dihexyl ether , Dioxane, n-hexane, n-pentane, n-octane, diethyl ether Ter, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, ethyl acetate, ethyl 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 in combination.

When reacting a diamine component and a tetracarboxylic acid dianhydride component in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid dianhydride component is used as it is or as an organic solvent. A method of dispersing or dissolving in a solvent and adding it, conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a tetracarboxylic acid dianhydride component and a diamine component A method of alternately adding may be mentioned, and any of these methods may be used. In addition, when the diamine component or the tetracarboxylic acid dianhydride component is composed of a plurality of types of compounds, it may be reacted in a mixed state in advance, or may be reacted separately one after another, and further it is a low molecular weight individually reacted. The body may be mixed and reacted to form a high molecular weight product.

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

The ratio of the total number of moles of tetracarboxylic acid dianhydride component to the total number of moles of diamine components in the above polymerization reaction can be selected to be any value depending on the molecular weight of the polyamic acid to be obtained. As in the conventional polycondensation reaction, the molecular weight of the formed polyamic acid increases as the molar ratio approaches 1.0. The preferred range is 0.8 to 1.2.

The method of synthesizing the polymer used in the present invention is not limited to the above-mentioned method, and in the case of synthesizing a polyamic acid, the above-mentioned tetracarboxylic acid dianhydride may be used in the same manner as a general polyamic acid synthesis method. Alternatively, the corresponding polyamic acid can be obtained also by reacting using a tetracarboxylic acid or a tetracarboxylic acid derivative such as a tetracarboxylic acid dihalide having a corresponding structure by a known method. Moreover, what is necessary is just to make diamine and diisocyanate react, when synthesize | combining polyurea. When producing a polyamic acid ester or polyamide, a component selected from a diamine, a tetracarboxylic acid diester and a dicarboxylic acid is induced to an acid halide in the presence of a known condensing agent or by a known method. And may be reacted with a diamine.

As a method of imidating the above-mentioned polyamic acid and setting it as a polyimide, the thermal imidization which heats the solution of polyamic acid as it is, the catalyst imidization which adds a catalyst to the solution of polyamic acid are mentioned. The imidation ratio from polyamic acid to polyimide is preferably 30% or more, and more preferably 30 to 99%, because the voltage holding ratio can be increased. On the other hand, 70% or less is preferable from the viewpoint of suppressing precipitation of the polymer in the varnish of whitening property. 40 to 80% is more preferable considering both properties.

The temperature for thermally imidizing the polyamic acid in the solution is usually 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidization reaction out of the system.

Catalytic imidization of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring at a temperature of generally −20 to 250 ° C., preferably 0 to 180 ° C. The amount of basic catalyst is usually 0.5 to 30 times by mole, preferably 2 to 20 times by mole of the amic acid group, and the amount of acid anhydride is usually 1 to 50 times by mole of the amic acid group, preferably It is 3 to 30 molar times. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferable because it has an adequate basicity to allow the reaction to proceed. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned. Among them, acetic anhydride is preferable because it facilitates purification after completion of the reaction. The imidation ratio by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time and the like.

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

When the radical generating film is made of a polymer containing an organic group that induces radical polymerization, the composition for forming a radical generating film used in the present invention is a polymer 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 the total components of the polymer is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.

The molecular weight of the polymer possessed by the radical generating film-forming composition is preferably GPC (per mass) in consideration of the strength of the radical generating film obtained by applying the radical generating film, the workability at the time of coating film formation, the uniformity of the coating film, etc. 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 applying and curing a composition of a compound having a radical generating group and a polymer to form a film and immobilizing it in the film A polyimide precursor produced according to the above production method, and a polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate and the like, which is a diamine having a site where radical polymerization occurs Alternatively, at least one polymer obtained using a diamine component that is 0 mol% of the entire diamine component used for the synthesis of the polymer to be contained in the radical generating film-forming composition may be used. As a compound which has the group which generate | occur | produces the radical which is added in that case, the following are mentioned.

The compound that generates radicals by heat is a compound that generates radicals by heating to a temperature higher than the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide etc., dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide etc), peroxy ketals (dibutyl peroxycyclohexane Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethyl cyclohexene Acid-tert-amyl ester etc., persulfates (potassium persulfate, sodium persulfate, ammonium persulfate etc.), azo compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) Azobisisobutyronitrile etc.). One of such radical thermal polymerization initiators may be used alone, or two or more thereof may be used in combination.

It will not specifically limit, if it is a compound which starts radical polymerization by light irradiation as a compound which generate | occur | produces a radical by light. As such radical photopolymerization initiators, benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 2-Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- Ndidyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate isoamyl, 4,4'-di (t-butylperoxycarbonyl) benzophenone 3,4,4'-tri (t-butylperoxy carbonyl) benzophenone, 2,4,6-trimethyl benzoyl diphenyl phosphine 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 (trichlorometh) ) -S-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl)]-2, 6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 ′ -Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylamino) Coumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-biimidazole (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2 ' -Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2 -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl 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, 2 -(3-Methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl-1 3- benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

Even when the radical generating film is made of a polymer containing an organic group which induces radical polymerization, the group which generates the above radical for the purpose of promoting radical polymerization when energy is given is You may contain the compound which it has.

The radical generating film-forming composition can contain an organic solvent in which the polymer component and, if necessary, the radical generator and other components contained therein are dissolved or dispersed. There is no limitation in particular in such an organic solvent, For example, the organic solvent which was illustrated by the synthesis | combination of said polyamic acid can be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, etc. have solubility. It is preferable from the viewpoint of In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferred, but two or more mixed solvents may be used.

Moreover, it is preferable to mix and use the solvent which improves the uniformity and smoothness of a coating film with the organic solvent with high solubility of the component of a radical generating film formation composition.

As a solvent for improving the uniformity and smoothness of the coating film, for example, isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbiol Toll, 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 monome Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether , Dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, Sobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, 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 (2) And -ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, 2-ethyl-1-hexanol and the like. A plurality of these solvents may be mixed. When these solvents are used, the content is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, of the total amount of solvents contained in the liquid crystal aligning agent.

The radical generating film-forming composition may contain components other than the above. Examples thereof include a compound that improves the film thickness uniformity and surface smoothness when the radical 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 formed. The compound etc. which further improve the film strength of a composition are mentioned.

As a compound which improves the uniformity of a film thickness, and surface smoothness, a fluorochemical surfactant, silicone type surfactant, nonion type surfactant etc. are mentioned. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, FC431 (manufactured by Sumitomo 3M Limited) And Asahi Guard AG 710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like. When these surfactants are used, their use ratio is preferably 0.01 to 2 parts by mass, more preferably 0 based on 100 parts by mass of the total amount of polymers contained in the radical generating film-forming composition. .01 to 1 part by mass.

As a specific example of a compound which improves the adhesiveness of a radical generating film formation composition and a board | substrate, a functional silane containing compound, an epoxy group containing compound, etc. are mentioned. 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-aminopropyl tri 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-dibromo neopentyl 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' And 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 may be added. It 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 with respect to 100 parts by mass of the total amount of polymers contained in the radical generating film-forming composition. It is.

Furthermore, in addition to the above, if the effect of the present invention is not impaired, the composition for forming a radical generating film may be a dielectric or conductivity for the purpose of changing the electric characteristics such as the dielectric constant or conductivity of the radical generating film. Substances may be added.

[Radical generation film]
The radical generating film of the present invention can be obtained using the above radical generating film forming composition. For example, after the composition for forming a radical generation film used in the present invention is applied to a substrate, a cured film obtained by drying and baking can be used as a radical generation film as it is. The cured film may be rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or irradiated with UV to a liquid crystal display element filled with 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 highly transparent substrate, but a substrate on which a transparent electrode for driving liquid crystal is formed is preferable.
Specific examples include glass plate, polycarbonate, poly (meth) acrylate, polyether sulfone, polyarylate, polyurethane, polysulfone, polyether, polyether ketone, trimethyl pentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, tri There can be mentioned a substrate in which a transparent electrode is formed on a plastic plate of acetyl cellulose, diacetyl cellulose, acetate butyrate cellulose or the like.

As a substrate that can be used for a liquid crystal display element of the IPS system, an electrode pattern such as a standard IPS comb electrode or a PSA fish bone electrode or a projection pattern such as MVA can be used.
In addition, as a highly functional element such as a TFT type element, one in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.
When a transmission type liquid crystal display device is intended, it is general to use a substrate as described above, but when a reflection type liquid crystal display device is intended, silicon is used if it is only on one side of the substrate. An opaque substrate such as a wafer can also be used. At that time, a material such as aluminum that reflects light can also be used for the electrode formed on the substrate.

Examples of the method of applying the radical generating film-forming composition include spin coating method, printing method, ink jet method, spray method and roll coating method, but from the viewpoint of productivity, transfer printing method is widely used industrially. And are suitably used in the present invention.

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

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

The thickness of the cured film can be selected according to need, but is preferably 5 nm or more, more preferably 10 nm or more, since the reliability of the liquid crystal display element can be easily obtained. When the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element is not extremely large, which is preferable.

As described above, the first substrate having a radical generation film can be obtained, but the radical generation film can be subjected to uniaxial alignment treatment. As a method of performing uniaxial alignment processing, a photo alignment method, an oblique deposition method, rubbing, uniaxial alignment processing by a magnetic field, etc. may be mentioned.

In the case of performing alignment processing by rubbing in one direction, for example, the substrate is moved so that the rubbing cloth and the film come in contact with each other while rotating the rubbing roller around which the rubbing cloth is wound. In the case of the first substrate of the present invention in which the comb electrode is formed, the direction is selected depending on the electrical properties of the liquid crystal, but in the case of using liquid crystal having positive dielectric anisotropy, the rubbing direction is the comb electrode Preferably, the direction is substantially the same as the direction in which the

The second substrate of the present invention is the same as the first substrate except that it does not have a radical generating film. It is preferable to set it as the board | substrate which has the liquid crystal aligning film conventionally known.

<Liquid crystal cell>
In the liquid crystal cell of the present invention, after the radical generation film is formed on the substrate by the above method, a substrate (first substrate) having the radical generation film and a substrate (second substrate) having a known liquid crystal alignment film Obtained by arranging the radical generating film and the liquid crystal alignment film to face each other, fixing the spacer with a sealing agent with the spacer interposed therebetween, and injecting and sealing a liquid crystal composition containing a liquid crystal and a radically polymerizable compound. Be In this case, the size of the spacer used is usually 1 to 30 μm, preferably 2 to 10 μm. Also, by making the rubbing direction of the first substrate parallel to the rubbing direction of the second substrate, it can be used for IPS mode or FFS mode, and if arranged so that the rubbing direction is orthogonal, a twisted nematic mode It can be used for
The method for injecting a liquid crystal and a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is not particularly limited, and a vacuum method in which a mixture containing liquid crystal and a polymerizable compound is injected after reducing the pressure in the produced liquid crystal cell, liquid crystal and polymerization The dropping method etc. which seal after dripping the mixture containing an organic compound can be mentioned.

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

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

And as a polymeric group of the said radically polymerizable compound, the polymeric group chosen from the following structures is preferable.

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

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

The compound having a monofunctional radically polymerizable group is a compound having a reactive group capable of performing radical polymerization in the presence of an organic radical, and examples thereof include t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate and nonyl Methacrylate monomers such as methacrylate, lauryl methacrylate and n-octyl methacrylate; acrylate monomers such as t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, lauryl acrylate and n-octyl acrylate; styrene, styrene Derivatives (eg, o-, m-, p-methoxystyrene, o-, m-, p-t-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), 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-vinyl compounds Vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole etc., (meth) acrylic acid derivatives (eg, acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide etc.), halogenated vinyls (eg, And vinyl monomers such as vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloroprene, vinyl fluoride and the like, but not limited thereto. These various radically polymerizable monomers may be used alone or in combination of two or more. Moreover, it is preferable that these have compatibility with a liquid crystal.

Moreover, as said radically polymerizable compound, the compound represented by following formula (1) is also preferable.

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

And, as a radically polymerizable compound represented by the above-mentioned formula (1), one in which E is an ester bond (a bond represented by -C (= O) -O- or -O-C (= O)-) Is preferable from the viewpoint of easiness of synthesis, compatibility with liquid crystals, and polymerization reactivity. Specifically, compounds having the following structures are preferable, but they are not particularly limited.

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

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

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

The liquid crystal generally means a substance in a state showing both solid and liquid properties, and there are nematic liquid crystal and smectic liquid crystal as typical liquid crystal phases, but the liquid crystal usable in the present invention is not particularly limited. One example is 4-pentyl-4'-cyanobiphenyl.

Next, energy sufficient to cause a polymerization reaction of the radically polymerizable compound is given to the liquid crystal cell in which a mixture (liquid crystal composition) containing the liquid crystal and the radically polymerizable compound is introduced. This can be carried out, for example, by applying heat or UV irradiation, and the desired properties appear when the radically polymerizable compound is polymerized in situ. Among them, UV irradiation is preferable in that the use of UV enables orientation patterning and allows a polymerization reaction in a short time. In addition to the liquid crystal composition described above, a chiral dopant may be introduced into the liquid crystal cell as necessary when used in the twisted nematic mode.

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

Here, in the case of UV irradiation, it is preferable to select the best wavelength of the reaction quantum yield of the reacting polymerizable compound, and the UV irradiation amount is usually 0.01 to 30 J, Preferably, it is 10 J or less, and a smaller amount of UV irradiation is preferable because it can suppress the decrease in reliability resulting from the destruction of the members constituting the liquid crystal display, and the tact upon manufacturing can be improved by reducing the UV irradiation time. It is.

Further, heating in the case of polymerization by heating only, not UV irradiation, is preferably performed at a temperature at which the polymerizable compound reacts and which is lower than the decomposition temperature of the liquid crystal. Specifically, for example, the temperature is 100 ° C. or more and 150 ° C. or less.

When energy sufficient to cause a radical polymerizable compound to undergo a polymerization reaction is given, it is preferable that no electric field be applied and no electric field be applied.

<Liquid crystal display element>
A liquid crystal display element can be manufactured using the liquid crystal cell obtained in this manner.
For example, a reflective liquid crystal display element can be obtained by providing a reflective electrode, a transparent electrode, a λ / 4 plate, a polarizing film, a color filter layer and the like according to a conventional method to the liquid crystal cell as necessary.
In addition, 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 to the liquid crystal cell according to need, a transmissive liquid crystal display device can be obtained.

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

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

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

<Measurement of imidation ratio>
20 mg of polyimide powder is placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Science Co., Ltd.), and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixed product) is added The solution was sonicated and completely dissolved. The 500 MHz proton NMR of this solution was measured by a measuring apparatus (JNW-ECA500 manufactured by Nippon Denshi Datum Co., Ltd.).
The imidation ratio is determined based on a proton derived from a structure which does not change before and after imidization as a reference proton, and a proton integrated value derived from the peak integrated value of this proton and NH of the amide group appearing in the vicinity of 9.5 to 10.0 ppm It calculated | required by the following formula using value and.
Imidation ratio (%) = (1−α · x / y) × 100
In the formula, x is an integrated value of the proton peak derived from NH of the amide group, y is a peak integrated value of the reference proton, and α is a reference proton for one NH proton of the amide group in the case of polyamic acid (imidation ratio is 0%) The percentage of

<Polymerization of Polymer and Preparation of Radical Generating Film Forming Composition>
Synthesis example 1
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-2 (50) Polyimide In a 100 ml four-necked flask equipped with a nitrogen inlet tube, air-cooled tube, and mechanical stirrer, DA-1 was added. 1.62 g (15.00 mmol) and 3.96 g (15.00 mmol) of DA-2 were weighed, 48.2 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere and completely dissolved. After confirmation of dissolution, 3.75 g (15.00 mmol) of TC-2 is added, and the mixture is reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. The temperature was returned to room temperature again, 2.71 g (13.80 mmol) of TC-1 was added, and reaction was performed at 40 ° C. for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity was 1000 mPa · s, to obtain a polymerization solution having a polyamic acid concentration of 20% by mass.
Measure 60 g of the polyamic acid solution obtained above in a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP, prepare a 7% by mass solution, and 9.10 g of acetic anhydride while stirring 88.52 mmol) and 3.76 g (47.53 mmol) of pyridine were added and stirred at room temperature for 30 minutes and then reacted at 55 ° C. for 3 hours with stirring. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol with stirring to precipitate a solid. The solid is recovered by filtration, and the solid is further poured into 300 ml of methanol, stirred and washed for a total of 30 minutes twice, collected by filtration, air-dried, and then dried in a vacuum oven at 60 ° C. The 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 In a 100 ml 4-neck flask equipped with a nitrogen inlet tube, air-cooled tube, and mechanical stirrer, DA-1 was added. 1.62 g (15.00 mmol) and 4.96 g (15.00 mmol) of DA-3 were weighed, 51.90 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere and completely dissolved. After confirmation of dissolution, 3.75 g (15.00 mmol) of TC-2 is added, and the mixture is reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. The temperature was returned to room temperature again, 2.64 g (13.5 mmol) of TC-1 was added, and reacted at 40 ° C. for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity was 1000 mPa · s, to obtain a polymerization solution having a polyamic acid concentration of 20% by mass.
Measure 60 g of the polyamic acid solution obtained above into a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP, add a 7% by mass solution, and while stirring, 8.38 g of acetic anhydride (81.4 mmol) and 3.62 g (45.8 mmol) of pyridine were added and stirred at room temperature for 30 minutes and then reacted at 55 ° C. for 3 hours with stirring. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol with stirring to precipitate a solid. The solid is recovered by filtration, and the solid is further poured into 300 ml of methanol, stirred and washed for a total of 30 minutes twice, collected by filtration, air-dried, and then dried in a vacuum oven at 60 ° C. Polyimide (PI-2) having a number average molecular weight Mn of 13100, a weight average molecular weight Mw of 34000, and an imidation ratio of 55% was obtained.

Synthesis example 3
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-4 (50) Polyimide In a 100 ml 4-neck flask equipped with a nitrogen inlet tube, air-cooled tube, and mechanical stirrer, DA-1 was added. 1.62 g (15.00 mmol) and 5.65 g (15.00 mmol) of DA-4 were weighed, 55.4 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere and completely dissolved. After confirmation of dissolution, 3.75 g (15.00 mmol) of TC-2 is added, and the mixture is reacted at 60 ° C. for 3 hours under a nitrogen atmosphere. The temperature was returned to room temperature again, 2.82 g (14.40 mmol) of TC-1 was added, and the reaction was performed at 40 ° C. for 12 hours under a nitrogen atmosphere. The polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity was 1000 mPa · s, to obtain a polymerization solution having a polyamic acid concentration of 20% by mass.
Measure 60 g of the polyamic acid solution obtained above in a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP, prepare a 7% by mass solution, and while stirring, 8.36 g of acetic anhydride ( 81.2 mmol) and 3.65 g (46.1 mmol) of pyridine were added, stirred at room temperature for 30 minutes and then reacted at 55 ° C. for 3 hours with stirring. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol with stirring to precipitate a solid. The solid is recovered by filtration, and the solid is further poured into 300 ml of methanol, stirred and washed for a total of 30 minutes twice, collected by filtration, air-dried, and then dried in a vacuum oven at 60 ° C. 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: Preparation of AL1 In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-1) obtained in Synthesis Example 1 was weighed out, 18.0 g of NMP was added, and the temperature was 50.degree. The solution was completely dissolved. Further, 6.7 g of NMP and 6.7 g of BCS are added, and the mixture is further stirred for 3 hours to form a radical generating film-forming composition according to the present invention: AL1 (solid content: 6.0 mass%, NMP: 66 mass%, BCS : 30% by mass) was obtained.

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

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

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

(First board)
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. An ITO (Indium-Tin-Oxide) electrode having a comb-like pattern having an electrode width of 10 μm and an electrode-to-electrode distance of 10 μm is formed on the substrate to form a pixel. The size of each pixel is about 10 mm in height and about 5 mm in width.
After filtering through a 1.0 μm filter, AL1 to AL3 or SE-6414 were applied by spin coating on the electrode-forming surface of the IPS substrate, and dried on a hot plate at 80 ° C. for 1 minute. Subsequently, AL1 to AL3 were baked at 150 ° C. for 20 minutes, and SE-6414 was baked at 220 ° C. for 20 minutes, and baked to form a coating film having a film thickness of 100 nm.
In the rubbing process “present”, rubbing was performed so that the rubbing direction was parallel to the comb electrode. Rubbing was performed using Yoshikawa Kako Rayon cloth: YA-20R, under conditions of 120 mm roll diameter, 300 rpm rotation speed, 50 mm / sec moving speed, and 0.4 mm pushing amount. However, the above-mentioned rotational speed was set to 1000 rpm only for the film coated with SE-6414. After rubbing treatment, ultrasonic wave irradiation was performed in pure water for 1 minute, and dried at 80 ° C. for 10 minutes.

(Second board)
The second substrate (also referred to as the back surface ITO substrate) is a non-alkali glass substrate of 30 mm × 35 mm in size and 0.7 mm in thickness, and an ITO film is formed on the back surface (surface facing the outside of the cell) ing. In addition, columnar spacers having a height of 4 μm are formed on the surface (surface facing the inside of the cell).
After filtering AL1, AL2 or SE-6414 with a filter of 1.0 μm, it was applied by spin coating on the electrode formation surface of the IPS substrate and dried on a hot plate at 80 ° C. for 1 minute. Next, AL1 and AL2 were baked at 150 ° C. for 20 minutes, and SE-6414 was baked at 220 ° C. for 20 minutes, and baked to form a coating having a film thickness of 100 nm, and then rubbing was performed. The rubbing process was performed using Yoshikawa Kako Rayon cloth: YA-20R under the conditions of 120 mm roll diameter, 1000 rpm rotation speed, 50 mm / sec moving speed, and 0.4 mm pushing amount. However, the film coated with AL1 or AL2 had the above-mentioned rotational speed of 300 rpm. After rubbing treatment, ultrasonic wave irradiation was performed in pure water for 1 minute, and dried at 80 ° C. for 10 minutes.

(Preparation of liquid crystal cell)
Using the two types of substrates (first and second substrates) with the liquid crystal alignment film, the periphery was sealed leaving a liquid crystal injection port, and a vacant cell having a cell gap of about 4 μm was produced. At this time, in the case where the first substrate is not subjected to the rubbing process, the first substrate is rubbed in combination such that the direction of the comb electrode of the first substrate and the rubbing direction of the second substrate become parallel. The rubbing directions of one substrate and the second substrate were combined so as to be antiparallel.
A liquid crystal (a product obtained by adding 10 wt% of HMA to MLC-3019 manufactured by Merck & Co., Inc.) was vacuum injected into this empty cell at normal temperature, and then the inlet was sealed to form a liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was subjected to heat treatment at 120 ° C. for 20 minutes.
In the presence of UV treatment, the liquid crystal cell was irradiated with ultraviolet light through a band pass filter with a wavelength of 313 nm using a high pressure mercury lamp so that the exposure amount would be 1000 mJ.

<Evaluation of liquid crystal alignment>
The orientation of the liquid crystal cell was confirmed using the polarizing plate set in cross nicol. Those with no defects were rated ○, those with minor orientation defects were △, and those without orientation were x.

<Measurement of VT curve and drive threshold voltage, maximum luminance voltage evaluation>
Set the white LED backlight and the luminance meter so that the optical axis is aligned, and set the liquid crystal cell (liquid crystal display element) attached with the polarizing plate between them so that the luminance is the smallest. The VT curve was measured by applying and measuring the luminance at the voltage. From the obtained VT curve, values of the driving threshold voltage and the voltage at which the luminance is maximum were estimated.

<Evaluation of response speed of liquid crystal display>
Using the device used to measure the VT curve above, connect a luminance meter to an oscilloscope and respond speed (Ton) when applying a voltage that produces maximum luminance and response speed (Toff) when voltage is set to 0. Was measured.

In comparison with Cell-1 to Cell-20, which uses a horizontal alignment film rubbed on the back side ITO substrate (second substrate) side, a UV generation treated cell using a radical generating film on the IPS substrate (first substrate) side It was confirmed that the alignment property of the liquid crystal is good, and that the drive threshold voltage and the maximum luminance voltage are lowered in each of -11, Cell-12, Cell-16 and Cell-17. Moreover, while the value of Toff increases in Cell-11 and Cell-12 in which the radical generation film is not rubbed, this Toff value is in Cell-16 and Cell-17 where the radical generation film is rubbed. It has been confirmed that the increase in

In addition to the above, as a supplementary experiment, a liquid crystal cell was prepared in which AL1 was used for both the back surface ITO substrate (second substrate) and the IPS substrate (first substrate) and both the first and second substrates were not rubbed. In this liquid crystal cell, alignment defects and bright spots (flow alignment) along the flow direction at the time of injection of liquid crystal were observed before UV irradiation, but after UV irradiation, the flow alignment disappeared completely, and domains derived from liquid crystal (Schlieren) was confirmed. From this, when the radical generating film and the liquid crystal containing the polymerizable compound are used in combination, the radical generating film loses the liquid crystal alignment control power by irradiating UV, and a zero plane anchoring film is formed on the radical generating film. It was suggested that

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

However, when observed while rotating Cell-22 and Cell-24 under crossed nicols, slight changes in light and dark occurred, so this zero plane anchoring film is not in a state where there is no alignment control force, The regulatory force is weaker than the intermolecular force between the liquid crystals, and this regulatory force alone suggests that the liquid crystal molecules are not uniaxially aligned in any direction. From this, it is thought that the above-mentioned weak regulatory force acts as a factor that the value of Toff improved greatly in Cell-16 and Cell-17.

Polymerizable Compound Synthesis Example 1
Synthesis of 2- (Heptanoyloxymethyl) acrylic acid ethyl ester

Step 1: Synthesis of 2-hydroxymethyl acrylic acid ethyl ester In a 500 ml four-necked flask fitted with a nitrogen introduction tube, 10 mg of 4-methoxyphenol, DABCO (1,4-diazabicyclo [2.2.2] octane) 21 .88 g (195.1 mmol) was weighed, 50 ml of pure water was added, and 11.52 g (390.1 mmol) of paraformaldehyde was added while stirring at 10 ° C. or less under a nitrogen atmosphere, and stirred for 1 hour. It was confirmed that the slurry state changed to a solution state, 300 ml of acetonitrile was added, 19.53 g (195.1 mmol) of ethyl acrylate was added dropwise, and the reaction was allowed to proceed at 50 ° C. for 5 hours. After completion of the reaction, the reaction solution was transferred to a separatory funnel, and 50 ml of n-hexane was added. It confirmed that it divided into 3 layers, 2 lower layers were collect | recovered, and this operation was performed 3 times. Further, hydrochloric acid was added so that the pH was 4-5, and extraction was performed using ethyl acetate. The extracted solution was added with anhydrous magnesium sulfate, stirred, dried, 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 nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.81 (1 H), 5.80 (1 H), 4.31 (2 H), 4.17 (1 H), 1.98 (1 H), 0.93 (3H)

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

Polymerizable Compound Synthesis Example 2
Synthesis of 2- (heptanoyloxymethyl) acrylic acid butyl ester

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

Second Step: Synthesis of 2- (Heptanoyloxymethyl) Acrylic Acid Butyl Ester The 2-hydroxymethyl acrylic acid of the second step is converted to the 2-((heptanoyloxy) methyl) acrylic acid butyl ester obtained by the above method. In the same manner, synthesis was carried out using the same procedure to obtain 34.2 g (126.7: yield 82.8%) of a colorless and transparent oily liquid. The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.36 (1 H), 5.81 (1 H), 4.80 (2 H), 4.19-4.16 (2 H), 2.35-2. 31 (2H), 1.64-1.58 (4H), 1.40-1.25 (8H), 0.96-0.83 (6H)

Polymerizable Compound Synthesis Example 3
Synthesis of dihexyl itaconate

In a four-necked flask fitted with a Dean-Stark tube, 23.8 g (182.9 mmol) of itaconic acid and 35.5 g (347.5 mmol) of 1-hexanol were weighed, 500 ml of cyclohexane, 0.9 g (9.1 mmol) of concentrated sulfuric acid Then, 0.04 g (1.82 mmol) of dibutylhydroxytoluene (BHT) was added, and a nitrogen atmosphere was set, and a dehydration condensation reaction was performed at 110 ° C. for 24 hours. 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 and concentration, vacuum drying was carried out to obtain 48.6 g (162.8 mmol: yield 89%) of a colorless and transparent oily liquid. The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum). The measurement data is shown below.
¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.30 (1 H), 5.65 (1 H), 4.20 to 4.00 (4 H), 3.32 (2 H), 1.64-1. 58 (4H), 1.40-1.25 (12H), 0.96-0.83 (6H)

(Preparation of liquid crystal cell)
After preparing an empty cell according to the above (preparation of liquid crystal cell), the above-mentioned polymerizable compounds are respectively added to the optimum amount of liquid crystal compositions LC-1 to LC-4 (Merck MLC-3019) in this empty cell. Added at a vacuum of about 300 Pa at room temperature, and after vacuum degassing at a vacuum of about 1 Pa for 1 hour, and then the injection port Was sealed to form a liquid crystal cell. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was subjected to heat treatment at 120 ° C. for 10 minutes. The rest was tested in the same manner as described above.

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

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

<Evaluation result of electro-optical characteristics>
Next, among the cells using the liquid crystal with zero anchoring orientation described above, the driving threshold voltage, the voltage at the maximum luminance, and the response speed are summarized below although the radical generating film is not rubbed. .

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

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

Claims

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

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

(In the formulas [W], [Y] and [Z], * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule, Ar has an organic group and / or a halogen atom as a substituent R 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, each of which is an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene. When R 9 and R 10 are alkyl groups, they may be bonded to each other at their ends 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 Indicates the binding site with other parts.)
R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. )
The method according to claim 7, wherein the diamine containing an organic group capable of inducing 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 represents a single bond, —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3) -, - CON (CH 3) -, or -N (CH 3) CO- represents,
R 7 represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more of any —CH 2 — or —CF 2 — of the alkylene group are each independently And may be substituted with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, ie, -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:

And a radical polymerization reactive group selected from
(In formulas [X-1] to [X-18], * represents a binding site to a moiety other than the radical polymerization reactive group of the compound molecule, and S 1 and S 2 are each independently —O—, — And 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, and R 1 and R 2 each independently represent a hydrogen atom, Halogen atom, represents an alkyl group having 1 to 4 carbon atoms))

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

(In the formulas [W], [Y] and [Z], * represents a bonding site to T 2 , Ar represents an organic group and / or a phenylene, naphthylene, and biphenylene which may have a halogen atom as a substituent) 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 a structure shown below Represents

(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 Indicates the binding site with other parts.)
R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. )))
The method according to any one of claims 1 to 9, wherein at least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule, which is compatible with liquid crystal.
The method according to claim 10, wherein the polymerizable reactive group of the radically polymerizable compound is selected from the following structures.

(Wherein, * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule. R b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR c represents a linking group selected from-, -S-, an ester bond and an amide bond, and R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
A liquid crystal composition containing the liquid crystal and a radical polymerizable compound, wherein the polymer obtained by polymerizing the radical polymerizable compound has a Tg of 100 ° C. or less. A method according to any one of the preceding claims, characterized in that
Preparing a first substrate having a radical generating film and a second substrate which may have a radical generating film;
Creating a cell such that the radical generating film on the first substrate faces the second substrate;
Filling the liquid crystal composition containing a liquid crystal and a radically polymerizable compound between the first substrate and the second substrate,
A method of manufacturing a liquid crystal cell using the method according to any one of claims 1 to 12.
The method of manufacturing a liquid crystal cell according to claim 13, wherein the second substrate is a second substrate not having a radical generating film.
The method for manufacturing a liquid crystal cell according to claim 14, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment property.
The method for producing a liquid crystal cell according to claim 15, wherein the liquid crystal alignment film having uniaxial alignment property is a liquid crystal alignment film for horizontal alignment.
The method of manufacturing a liquid crystal cell according to any one of claims 13 to 16, wherein the first substrate having the radical generating film is a substrate having a comb electrode.
Contains liquid crystal and radically polymerizable compounds,
At least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule, which is compatible with liquid crystal,
A liquid crystal composition, wherein the polymerizable reactive group is selected from the following structures.

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