JPWO2013073636A1 - Silicon-based liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Improved response speed after UV irradiation without reducing the vertical alignment force even in liquid crystal display elements that use a liquid crystal to which no polymerizable compound is added and treat it in the same way as the PSA method to improve response speed after UV irradiation. A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element that can form a liquid crystal alignment film that can be formed are provided. Liquid crystal aligning agent containing polysiloxane (A) obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (3). R1Si (OR2) 3 (1) (R1 represents the structure of the following formula (2), R2 represents an alkyl group having 1 to 5 carbon atoms) [Chemical Formula 1] (Y1, Y2, and Y3 are single bonds, etc.) Y4 and Y5 are benzene rings, Y6 is a hydrogen atom, n is an integer of 0 to 4) R3Si (OR4) 3 (3) (R3 is an acrylic group, R4 is an alkyl group having 1 to 5 carbon atoms, etc.)

Description

  The present invention relates to a liquid crystal alignment agent containing polysiloxane obtained by hydrolysis and polycondensation of alkoxysilane, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display device having the liquid crystal alignment film.

In recent years, among liquid crystal display element display methods, vertical (VA) liquid crystal display elements are widely used for large-screen liquid crystal televisions and high-definition mobile applications (display units of digital cameras and mobile phones). . The VA method includes an MVA method (Multi Vertical Alignment) in which protrusions for controlling the direction in which the liquid crystal is tilted are formed on the TFT substrate or the color filter substrate, and a direction in which the liquid crystal is tilted by an electric field by forming a slit in the ITO electrode of the substrate. A PVA (Patterned Vertical Alignment) system to be controlled is known. As another orientation method, there is a PSA (Polymer Sustained Alignment) method. Among VA systems, the PSA system is a technology that has attracted attention in recent years. In this method, a photopolymerizable compound is added to the liquid crystal, and after the liquid crystal panel is produced, an electric field is applied to irradiate the liquid crystal panel with UV in a state where the liquid crystal is tilted. As a result, the polymerizable compound is photopolymerized to fix the alignment direction of the liquid crystal, causing a pretilt and improving the response speed. It is possible to operate with a structure in which a slit is made in one electrode constituting the liquid crystal panel, and the electrode pattern on the opposite side is not provided with a protrusion such as MVA or a slit such as PVA, and the manufacturing is simplified and excellent. The panel transmittance is obtained. (See Patent Document 1.)
However, in this type of liquid crystal display element, the solubility of the polymerizable compound added to the liquid crystal is low, and there is a problem that when the addition amount is increased, it precipitates at a low temperature. On the other hand, when the addition amount of the polymerizable compound is reduced, a good alignment state and response speed cannot be obtained. Further, the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity in the liquid crystal, and there is a problem that the reliability of the liquid crystal display element is lowered.

Therefore, a liquid crystal alignment agent using a polymer in which a photoreactive side chain is introduced into a polymer molecule is applied to a substrate, and a liquid crystal layer in contact with the liquid crystal alignment film obtained by baking is provided. There has been proposed a technique capable of obtaining a liquid crystal display element having a high response speed without adding a polymerizable compound to the liquid crystal by producing a liquid crystal display element by irradiating ultraviolet rays while applying a voltage. (See Patent Document 2)
On the other hand, inorganic liquid crystal alignment film materials are also known along with conventionally used organic liquid crystal alignment film materials such as polyimide. For example, as a material for a coating-type inorganic alignment film, an alignment agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, alcohol, and oxalic acid has been proposed. It has been reported that a liquid crystal alignment film excellent in vertical alignment, heat resistance and uniformity is formed. (See Patent Document 3)

Japanese Unexamined Patent Publication No. 2004-302061 Japanese Unexamined Patent Publication No. 2011-95697 Japanese Unexamined Patent Publication No. 09-281502

  In the VA mode in which the vertical alignment is performed, a strong vertical alignment force is required for the vertical alignment. However, in this method without using a polymerizable compound, the response speed after UV irradiation becomes slow when the vertical alignment force is improved. Thus, when the response speed after UV irradiation is improved, the vertical alignment force decreases. There is a trade-off relationship between the vertical alignment force and the response speed improvement after UV irradiation.

  The object of the present invention is to use a liquid crystal to which no polymerizable compound is added, and also in a liquid crystal display element of a method that improves the response speed after UV irradiation by treating in the same manner as the PSA method, without reducing the vertical alignment force, By providing a liquid crystal alignment agent capable of forming a liquid crystal alignment film capable of improving the response speed after UV irradiation, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. is there.

The gist of the present invention is as follows.
[1] A liquid crystal aligning agent containing the following polysiloxane (A).
Polysiloxane (A): Polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane represented by formula (1) and an alkoxysilane represented by formula (3).
R ¹ Si (OR ² ) ₃ (1)
(R ¹ represents the structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)

（式（２）中、Ｙ^１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である。）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又はＯＣＯ−である。Ｙ^２は単結合、二重結合を含有する炭素数３〜８の直鎖状又は分岐状の２価の炭化水素基、又は（ＣR¹⁷R¹⁸）_ｂ−（ｂは１〜１５の整数であり、Ｒ^１７、Ｒ^１８はそれぞれ独立に、水素原子又は炭素数１〜３のアルキル基を表す。）である。Ｙ^３は単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である。）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−又はＯＣＯ−である。Ｙ^４はベンゼン環、シクロへキシル環、及び複素環からなる群から選ばれる２価の環状基、又は、ステロイド骨格を有する炭素数１２〜２５の２価の有機基を示し、これらの環状基上の任意の水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシ基、及びフッ素原子からなる群から選ばれるもので置換されていても良い。Ｙ^５はベンゼン環、シクロへキシル環及び複素環からなる群から選ばれる２価の環状基であって、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシ基又はフッ素原子で置換されていてもよい。ｎは０〜４の整数である。Ｙ^６は水素原子、炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシ基又は炭素数１〜１８のフッ素含有アルコキシ基を表す。）
Ｒ^３Ｓｉ（ＯＲ^４）_３ （３）
（Ｒ^３は、アクリル基、アクリロキシ基、メタクリル基、メタクリロキシ基、又はスチリル基で置換された炭素数５〜１０のアルキル基である。Ｒ^４は炭素数１〜５のアルキル基を表す。）

(In Formula (2), Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO—, or OCO—. Y ² is a straight or branched divalent hydrocarbon group having 3 to 8 carbon atoms containing a single bond or a double bond, or (CR ¹⁷ R ¹⁸ ) _b — (b is 1 to 15 And each of R ¹⁷ and R ¹⁸ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) Y ³ is a single bond, — (CH ₂ ) _c — (c is 1 to 15 is an integer of 15.), —O—, —CH ₂ O—, —COO—, or OCO—, Y ⁴ is a divalent group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a heterocyclic ring. A cyclic group or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton is shown, and an arbitrary hydrogen atom on these cyclic groups has a carbon number of 1 to 1 Substituted with a group selected from the group consisting of 3 alkyl groups, 1 to 3 alkoxy groups, 1 to 3 fluorine-containing alkyl groups, 1 to 3 fluorine-containing alkoxy groups, and fluorine atoms. Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has 1 to 3 carbon atoms. It may be substituted with an alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Represents.)
R ³ Si (OR ⁴ ) ₃ (3)
(R ³ is an acrylic group, an acryloxy group, .R ⁴ is a methacryl group, a methacryloxy group, or an alkyl group having 5 to 10 carbon atoms which is substituted with a styryl group represents an alkyl group having 1 to 5 carbon atoms.)

[2] The liquid crystal aligning agent according to the above [1], further comprising a polysiloxane (B).
Polysiloxane (B): A polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing 50 to 100 mol% of the alkoxysilane represented by the formula (5).
Si (OR ¹⁵ ) ₄ (5)
(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms.)
[3] The liquid crystal alignment according to the above [2], wherein the polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (3). Agent.
[4] In the above [2] or [3], the polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (6). The liquid crystal aligning agent of description.
R ¹⁶ Si (OR ¹⁷ ) ₃ (6)
^{(R 16} is, ^{.R 17} is an alkyl group having 1 to 5 carbon atoms is an alkyl group having 1 to 5 carbon atoms.)

[5] At least one of polysiloxane (A) and polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (4): The liquid crystal aligning agent in any one of said [2]-[4].
(R ¹³ ) _n Si (OR ¹⁴ ) _4-n (4)
(In formula (4), R ¹³ is a carbon atom having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. R ¹⁴ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.)
[6] The alkoxysilane represented by the formula (1) is contained in an amount of 2 to 20 mol% in the total alkoxysilane used in the polysiloxane (A), and the alkoxysilane represented by the formula (3) The liquid crystal aligning agent in any one of said [1]-[5] contained in 5-70 mol% in all the alkoxysilanes used for polysiloxane (A).
[7] The liquid crystal alignment according to any one of the above [1] to [6], further comprising a solvent and having a total polysiloxane content of 0.5 to 15% by weight in terms of SiO _2. Agent.
[8] A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of [1] to [7] to a substrate, drying and baking.
[9] A liquid crystal display device having the liquid crystal alignment film according to [8].
[10] The liquid crystal aligning agent according to any one of [1] to [7] is applied, and UV is irradiated in a state where a voltage is applied to a liquid crystal cell in which the liquid crystal is sandwiched between two baked substrates. Liquid crystal display element.
[11] A liquid crystal display element that applies the liquid crystal aligning agent according to any one of the above [1] to [7], sandwiches liquid crystal between two baked substrates, and irradiates UV with a voltage applied. Production method.

  According to the present invention, it is possible to improve the response speed after UV irradiation without reducing the vertical alignment force by irradiating UV with a liquid crystal to which no polymerizable compound is added in the same manner as the PSA method. A liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal aligning film can be provided.

The present invention is described in detail below.
This invention is invention about the liquid crystal aligning agent containing the following polysiloxane (A).
Polysiloxane (A): Polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane represented by formula (1) and an alkoxysilane represented by formula (3).
R ¹ Si (OR ² ) ₃ (1)
(R ¹ represents the structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)

Ｒ^３Ｓｉ（ＯＲ^４）_３ （３）
（Ｒ^３は、アクリル基、アクリロキシ基、メタクリル基、メタクリロキシ基、又はスチリル基で置換された炭素数５〜１０のアルキル基である。Ｒ^４は炭素数１〜５のアルキル基を表す。）
また、本発明は、ポリシロキサン（Ａ）及び下記のポリシロキサン（Ｂ）を含有する液晶配向剤についての発明である。
ポリシロキサン（Ｂ）：式（５）で表されるアルコキシシランを５０〜１００モル％含有するアルコキシシランを加水分解・重縮合して得られるポリシロキサン。
Ｓｉ（ＯＲ^１５）_４ （５）
（Ｒ^１５は炭素数１〜５のアルキル基を表す。）

R ³ Si (OR ⁴ ) ₃ (3)
(R ³ is an acrylic group, an acryloxy group, .R ⁴ is a methacryl group, a methacryloxy group, or an alkyl group having 5 to 10 carbon atoms which is substituted with a styryl group represents an alkyl group having 1 to 5 carbon atoms.)
Moreover, this invention is invention about the liquid crystal aligning agent containing polysiloxane (A) and the following polysiloxane (B).
Polysiloxane (B): A polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing 50 to 100 mol% of the alkoxysilane represented by the formula (5).
Si (OR ¹⁵ ) ₄ (5)
(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms.)

<Polysiloxane (A)>
The polysiloxane (A) contained in the liquid crystal aligning agent of the present invention hydrolyzes and polycondenses the alkoxysilane containing the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3). It is a polysiloxane obtained.
R ¹ Si (OR ² ) ₃ (1)
(R ¹ represents the structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)

Ｒ^３Ｓｉ（ＯＲ^４）_３ （３）
（Ｒ^３は、アクリル基、アクリロキシ基、メタクリル基、メタクリロキシ基又はスチリル基で置換された炭素数５〜１０のアルキル基である。Ｒ^４は炭素数１〜５のアルキル基を表す。）
式（１）で表されるアルコキシシランのＲ^１（以下、特定有機基ともいう）は、上記式（２）で表す構造を表す。

R ³ Si (OR ⁴ ) ₃ (3)
(R ³ is an acrylic group, an acryloxy group, .R ⁴ is a methacryl group, an alkyl group has been C5-10 substituted by a methacryloxy group or a styryl group represents an alkyl group having 1 to 5 carbon atoms.)
R ¹ (hereinafter also referred to as a specific organic group) of the alkoxysilane represented by the formula (1) represents a structure represented by the above formula (2).

In formula (2), Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—. Either. Among them, Y ¹ is selected from a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, or COO—. Is preferable from the viewpoint of facilitating the synthesis of the side chain structure. Y ¹ may be selected from a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O—, or COO—. More preferred. Y ¹ is particularly preferably _a single bond or (CH ₂ ) _a — (a is an integer of 1 to 10).

In Formula (2), Y ² is a straight or branched divalent hydrocarbon group having 3 to 8 carbon atoms containing a single bond or a double bond, or (CR ¹⁷ R ¹⁸ ) _b — (b is It is an integer of 1-15, and R < ¹⁷ >, R < ¹⁸ > represents a hydrogen atom or a C1-C3 alkyl group each independently. Among these, Y ² is preferably — (CH ₂ ) _b — (b is an integer of 1 to 10) from the viewpoint of significantly improving the response speed of the liquid crystal display element. Y ² is preferably a single bond.

In formula (2), Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—. Either. Among them, Y ³ is any one of a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or OCO—. It is preferable to select from the viewpoint of facilitating the synthesis of the side chain structure. Y ³ represents a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO— or OCO—. More preferably, it is selected. Y ³ is particularly preferably a single bond or O—.

In formula (2), Y ⁴ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 to 1 carbon atoms. Or an alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. . Further, Y ⁴ may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. Among these, Y ⁴ is preferably an organic group having 12 to 25 carbon atoms having any one of a benzene ring, a cyclohexyl ring, and a steroid skeleton. Y ⁴ is particularly preferably a divalent cyclic group consisting of a benzene ring.

In Formula (2), Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups has a carbon number of 1 to Or an alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. . Y ⁵ is particularly preferably a divalent cyclic group consisting of a cyclohexyl ring.
In formula (2), n is an integer of 0-4. Preferably, it is an integer of 0 to 2, and 1 is particularly preferable.

In formula (2), Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. One of them. Among them, ^{Y 6} is any of an alkyl group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group or a fluorine-containing alkoxy group having 1 to 10 carbon atoms having 1 to 18 carbon atoms having 1 to 18 carbon atoms It is preferable that Y ⁶ is more preferably any one of an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Y ⁶ is more preferably any of an alkyl group having 1 to 9 carbon atoms and an alkoxy group having 1 to 9 carbon atoms. Y ⁶ is particularly preferably an alkyl group having 1 to 9 carbon atoms.

R ² of the alkoxysilane represented by the formula (1) has 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. More preferably, R ² is a methyl group or an ethyl group.
Such alkoxysilane represented by the formula (1) can be synthesized by a known synthesis method (Japanese Patent Laid-Open No. 61-286393). Although the specific example is given to the following, it is not limited to this.

（式［１−１９］〜式［１−２１］中、Ｒ^５は−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−又はＣＨ_２ＯＣＯ−を示し、Ｒ^６は炭素数１〜２２のアルキル基、アルコキシ基、フッ素含有アルキル基又はフッ素含有アルコキシ基である。）

(In the formulas [1-19] to [1-21], R ⁵ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or CH ₂ OCO—, and R ⁶ represents carbon. The alkyl group, the alkoxy group, the fluorine-containing alkyl group, or the fluorine-containing alkoxy group represented by formulas 1 to 22.

（式［１−２２］〜式［１−２４］中、Ｒ^７は単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−（ＣＨ_２）_ｎＯ−（nは１〜5の整数）、−ＯＣＨ_２−又はＣＨ_２−を示し、Ｒ^８は炭素数１〜２２のアルキル基、アルコキシ基、フッ素含有アルキル基又はフッ素含有アルコキシ基である。）

(In Formula [1-22] to Formula [1-24], R ⁷ represents a single bond, —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, — (CH ₂ ) _n O— ( n is an integer of 1 to 5), -OCH ₂ -or CH _2- , and R ⁸ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

（式［１−２５］及び式［１−２６］中、Ｒ^９は−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−又はＯ−を示し、Ｒ^１０はフッ素基、シアノ基、トリフルオロメタン基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基又は水酸基である。）

(In Formula [1-25] and Formula [1-26], R ⁹ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, — CH ₂ — or O— is shown, and R ¹⁰ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.

（式［１−２７］及び式［１−２８］中、Ｒ^１１は炭素数３〜１２のアルキル基であり、１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。）

(In Formula [1-27] and Formula [1-28], R ¹¹ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. )

（式［１−２９］及び式［１−３０］中、Ｒ^１２は、炭素数３〜１２のアルキル基であり、１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。）

(In the formulas [1-29] and [1-30], R ¹² is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .)

（式［１−３１］中、Ｂ_４はフッ素原子で置換されていてもよい炭素数３〜２０のアルキル基であり、Ｂ_３は１，４−シクロへキシレン基又は１，４−フェニレン基であり、Ｂ_２は酸素原子又はＣＯＯ−＊（但し、「＊」を付した結合手がＢ_３と結合する。）であり、Ｂ_１は酸素原子又はＣＯＯ−＊（但し、「＊」を付した結合手が（ＣＨ_２）ａ_２）と結合する。）である。また、ａ_１は０又は１の整数であり、ａ_２は２〜１０の整数であり、ａ_３は０又は１の整数である。）
上記の化合物は、シロキサンポリマーとした際の溶媒への溶解性、液晶配向膜とした場合における液晶の配向性、プレチルト角特性、電圧保持率、蓄積電荷などの特性に応じて、１種類又は２種類以上を混合して使用することもできる。また、炭素数１０〜１８の長鎖アルキル基を含有するアルコキシシランとの併用も可能である。

(In the formula [1-31], B ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and B ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group. B ₂ is an oxygen atom or COO- * (where a bond marked with “*” is bonded to B ₃ ), and B ₁ is an oxygen atom or COO- * (where “*” is The bond attached is bonded to (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of ₂ to 10, and a ₃ is an integer of 0 or 1. )
One or two of the above compounds may be used depending on properties such as solubility in a solvent when used as a siloxane polymer, alignment properties of liquid crystal when used as a liquid crystal alignment film, pretilt angle characteristics, voltage holding ratio, accumulated charge, and the like. A mixture of more than one can also be used. Moreover, combined use with the alkoxysilane containing a C10-C18 long-chain alkyl group is also possible.

The alkoxysilane represented by the formula (1) having the specific organic group described above can be produced by a known method.
The alkoxysilane represented by the formula (1) having the specific organic group described above is preferably 2 mol% or more in order to obtain good liquid crystal alignment in all alkoxysilanes used for obtaining polysiloxane. More preferably, the alkoxysilane represented by Formula (1) is 3 mol% or more. Further, the alkoxysilane represented by the formula (1) is preferably 20 mol% or less in order to obtain sufficient curing characteristics of the liquid crystal alignment film to be formed. More preferably, it is 15 mol% or less.
R ³ of the alkoxysilane represented by the formula (3) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
The alkoxysilane represented by the formula (3) is preferably 5 mol% or more in order to obtain a good liquid crystal response speed in all alkoxysilanes used for obtaining the polysiloxane. The alkoxysilane represented by the formula (3) is more preferably 10 mol% or more, still more preferably 20 mol% or more, preferably 70 mol% or less, more preferably 50 mol% or less.

For the production of polysiloxane (A), in addition to the alkoxysilanes represented by the formulas (1) and (3), the effects of the present invention are intended for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules. As long as the above is not impaired, one or more alkoxysilanes represented by the following formula (4) may be used. Since the alkoxysilane represented by the formula (4) can impart various properties to the polysiloxane, one or more types can be selected and used according to the required properties.
(R ¹³ ) _n Si (OR ¹⁴ ) _4-n (4)
(In formula (4), R ¹³ is a carbon atom having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. R ¹⁴ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, n is 0 to 3, and preferably represents an integer of 0 to 2.)
R ¹³ of the alkoxysilane represented by the formula (4) is a hydrogen atom or an organic group having 1 to 10 carbon atoms (hereinafter also referred to as a third organic group). Examples of the third organic group include aliphatic hydrocarbons; ring structures such as aliphatic rings, aromatic rings and heterocycles; unsaturated bonds; and heteroatoms such as oxygen atoms, nitrogen atoms and sulfur atoms. It is an organic group having 1 to 6 carbon atoms, which may be included and may have a branched structure. In addition, the organic group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureido group, or the like.

  Although the specific example of the alkoxysilane represented by such Formula (4) is given, it is not limited to this. For example, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) Triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, diphenyl Diethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane and γ-ureidopropyltri And propoxysilane.

In the alkoxysilane represented by the formula (4), the alkoxysilane in which n is 0 is tetraalkoxysilane. Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention because it easily condenses with the alkoxysilane represented by the formulas (1) and (3).
As such alkoxysilane in which n is 0 in the formula (4), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
In the present invention, the alkoxysilane represented by the formula (1) is preferably contained in an amount of 2 to 20 mol%, particularly preferably 3 to 15 mol% in the total alkoxysilane used for the production of the polysiloxane (A). In addition, it is preferable that the alkoxysilane represented by the formula (3) is contained in an amount of 5 to 70 mol%, particularly preferably 10 to 50 mol%, in the total alkoxysilane used for the production of the polysiloxane (A).

<Polysiloxane (B)>
The polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing 50 to 100 mol% of the alkoxysilane represented by the formula (5).
Si (OR ¹⁵ ) ₄ (5)
(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms.)
As specific examples of the alkoxysilane represented by the formula (5), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.

The polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (3) in addition to the alkoxysilane represented by the formula (5). There may be.
The polysiloxane (B) is a polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (6) in addition to the alkoxysilane represented by the formula (5). There may be.
R ¹⁶ Si (OR ¹⁷ ) ₃ (6)
^{(R 16} is, ^{.R 17} is an alkyl group having 1 to 5 carbon atoms is an alkyl group having 1 to 5 carbon atoms.)
R ¹⁶ of the alkoxysilane represented by the formula (6) is an alkyl group having 1 to 5 carbon atoms. 1-4 are preferable, as for carbon number of an alkyl group, More preferably, it is 1-3.
R ¹⁷ of the alkoxysilane represented by the formula (6) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
Although the specific example of the alkoxysilane represented by Formula (6) is given, it is not limited to these. For example, methyltriethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxysilane.
In particular, in addition to the alkoxysilane represented by the formula (5), it further contains a polysiloxane (B) obtained by hydrolysis and polycondensation of an alkoxysilane containing the alkoxysilane represented by the formula (6). A liquid crystal aligning agent is desirable because of its high vertical alignment force.

  In order to improve the response speed of the liquid crystal display element by applying UV light while applying a voltage using a liquid crystal to which no polymerizable compound is added, it is represented by the formula (3) having the second specific organic group. The alkoxysilane to be used is preferably 10 mol% or more in all alkoxysilanes used for obtaining the polysiloxane. More preferably, it is 20 mol% or more. More preferably, it is 30 mol% or more. Moreover, in order to fully harden the liquid crystal aligning film formed, 75 mol% or less is preferable.

In addition to the alkoxysilanes represented by the formulas (3), (5), and (6), the production of the polysiloxane (B) is intended to improve adhesion with the substrate and affinity with the liquid crystal molecules. As long as the effects of the present invention are not impaired, one or more alkoxysilanes represented by the above formula (4) can be used. Since the alkoxysilane represented by the formula (4) can impart various properties to the polysiloxane, one or more types can be selected and used according to the required properties.
When manufacturing the liquid crystal aligning agent which mixed polysiloxane (A) and polysiloxane (B), about the mixing ratio of polysiloxane (A) and polysiloxane (B), (A) and ( The weight ratio of B) is preferably 10:90 to 50:50.

<Method for producing polysiloxane>
The method for obtaining the polysiloxane used in the present invention is not particularly limited. The polysiloxane (A) of the present invention is obtained by condensing an alkoxysilane having the above-described formulas (1) and (3) as essential components in an organic solvent. Usually, polysiloxane is obtained as a solution in which such alkoxysilane is hydrolyzed and polycondensed to be uniformly dissolved in an organic solvent.
Examples of the method for hydrolyzing and polycondensing polysiloxane include a method for hydrolyzing and polycondensing alkoxysilane in a solvent such as alcohol or glycol. At that time, the hydrolysis / polycondensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 times mole of water of all alkoxy groups in the alkoxysilane, but it is usually preferable to add an excess amount of water more than 0.5 times mole.
In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 moles of all alkoxy groups in the alkoxysilane.

  Usually, for the purpose of promoting hydrolysis and polycondensation reaction, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid; ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc. Catalysts such as alkali; metal salts of acids such as hydrochloric acid, sulfuric acid, and nitric acid; are used. In addition, it is also common to further promote hydrolysis and polycondensation reactions by heating a solution in which alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, heating and stirring at 50 ° C. for 24 hours, heating and stirring for 1 hour under reflux, and the like can be mentioned.

As another method, for example, a method of heating and hydrolyzing / polycondensing a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the alkoxysilane is mixed while the solution is heated. In that case, it is preferable that the quantity of the oxalic acid to be used shall be 0.2-2 mol with respect to 1 mol of all the alkoxy groups which alkoxysilane has. Heating in this method can be performed at a liquid temperature of 50 to 180 ° C. Preferably, it is a method of heating for several tens of minutes to several tens of hours under reflux so that evaporation or volatilization of the liquid does not occur.
When obtaining multiple types of alkoxysilane when obtaining polysiloxane, you may mix as a mixture which mixed alkoxysilane beforehand, and may mix multiple types of alkoxysilane sequentially.
The solvent used when hydrolyzing and polycondensing alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it dissolves alkoxysilane. Moreover, even when alkoxysilane does not melt | dissolve, what melt | dissolves with the progress of hydrolysis and polycondensation reaction of alkoxysilane should just be used. In general, since alcohol is generated by hydrolysis / polycondensation reaction of alkoxysilane, alcohols, glycols, glycol ethers, or organic solvents having good compatibility with alcohols are used.

  Specific examples of such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1 , 5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol and the like glycols: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether , Ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Glycol ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone , Dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol and the like.

In the present invention, a plurality of the above polymerization solvents may be mixed and used.
The polysiloxane polymerization solution (hereinafter also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO ₂ (hereinafter referred to as SiO ₂ conversion concentration). ) Is preferably 20% by weight or less, more preferably 5 to 15% by weight. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.

<Polysiloxane solution>
In the present invention, the polymerization solution obtained by the above method may be used as a polysiloxane solution as it is, or if necessary, the solution obtained by the above method may be concentrated or diluted by adding a solvent. Or may be substituted with another solvent to form a polysiloxane solution.
In that case, the solvent to be used (hereinafter also referred to as additive solvent) may be the same as the polymerization solvent, or may be another solvent. The additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one kind or plural kinds can be arbitrarily selected and used.
Specific examples of such an additive solvent include, in addition to the solvents mentioned as examples of the polymerization solvent described above, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and ethyl lactate. Can be mentioned.
These solvents can improve the applicability when the liquid crystal aligning agent is applied onto the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, ink jetting or the like.

<Other ingredients>
In the present invention, other components other than polysiloxane, such as inorganic fine particles, metalloxane oligomers, metalloxane polymers, leveling agents, and surfactants are included as long as the effects of the present invention are not impaired. May be.
As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those in the state of a colloidal solution are particularly preferable. This colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution. In the present invention, the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions. The inorganic fine particles preferably have an average particle size of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed using the prepared coating liquid may be lowered.
Examples of the dispersion medium for the inorganic fine particles include water and organic solvents. As a colloidal solution, it is preferable that pH or pKa is adjusted to 1-10 from the viewpoint of the stability of the coating liquid for forming a film. More preferably, it is 2-7.

  Examples of the organic solvent used for the dispersion medium of the colloidal solution include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Examples include ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols or ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.

As the metalloxane oligomer and metalloxane polymer, single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used. The metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from a monomer such as a metal alkoxide, nitrate, hydrochloride, or carboxylate by a conventional method such as hydrolysis.
Specific examples of commercially available metalloxane oligomers and metalloxane polymers include siloxane oligomers or siloxanes such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat. Examples thereof include titanoxane oligomers such as a polymer and titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. You may use these individually or in mixture of 2 or more types.
Moreover, a leveling agent, surfactant, etc. can use a well-known thing, and since a commercial item is easy to acquire especially, it is preferable.
Moreover, the method of mixing the above-mentioned other components with polysiloxane may be simultaneous with or after polysiloxane, and is not particularly limited.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is a solution containing the above-described polysiloxane and, if necessary, other components. In this case, as the solvent, a solvent selected from the group consisting of the above-mentioned polysiloxane polymerization solvent and additive solvent is used. The content of polysiloxane in the liquid crystal aligning agent is preferably 0.5 to 15% by weight, more preferably 1 to 6% by weight in terms of SiO ₂ concentration. Be in the range of such terms of SiO ₂ concentration, easy to obtain a desired film thickness by a single coating, easy pot life sufficient solution is obtained.
The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited. The polysiloxane used in the present invention may be in a state where other components added as necessary are uniformly mixed. Since polysiloxane is usually hydrolyzed and polycondensed in a solvent, it is convenient to use the polysiloxane solution as it is or to add other components to the polysiloxane solution as necessary. Furthermore, the most convenient method is to use the polysiloxane polymerization solution as it is.
Moreover, when adjusting content of polysiloxane in a liquid crystal aligning agent, the solvent chosen from the group which consists of the polymerization solvent and addition solvent of the polysiloxane mentioned above can be used.

<Liquid crystal alignment film>
The liquid crystal aligning film of this invention is obtained using the liquid crystal aligning agent of this invention. For example, after applying the liquid crystal aligning agent of this invention to a board | substrate, the cured film obtained by drying and baking can also be used as a liquid crystal aligning film as it is. In addition, the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, processed with an ion beam, etc., or irradiated with UV in a state where a voltage is applied to the liquid crystal display element after filling the liquid crystal. It is also possible.
The substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate is preferable.

  Specific examples include glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, tri Examples thereof include a substrate in which a transparent electrode is formed on a plastic plate such as acetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose.

Examples of the method for applying the liquid crystal aligning agent include spin coating, printing, ink jet, spraying, roll coating, and the like.In terms of productivity, the transfer printing method is widely used industrially. The present invention is also preferably used.
The drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, a drying process is included. Is preferred. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or 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 liquid crystal aligning agent by the above method can be baked to obtain a cured film. At that time, the firing temperature can be carried out at an arbitrary 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. It is. Firing can be performed at an arbitrary time of 5 minutes to 240 minutes. Preferably it is 10 to 90 minutes, More preferably, it is 20 to 80 minutes. For the heating, a generally known method such as a hot plate, a hot air circulation oven, an IR oven, a belt furnace or the like can be used.

The polysiloxane in the liquid crystal alignment film undergoes polycondensation in the firing step. However, in the present invention, it is not necessary to completely polycondense unless the effects of the present invention are impaired. However, firing is preferably performed at a temperature higher by 10 ° C. or more than the heat treatment temperature required for the liquid crystal cell production process, such as curing of the sealant.
The thickness of the cured film can be selected as necessary, but is preferably 5 nm or more, more preferably 10 nm or more, because the reliability of the liquid crystal display element can be easily obtained. Moreover, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large, which is suitable.

<Liquid crystal display element>
The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then preparing a liquid crystal cell by a known method. As an example of manufacturing a liquid crystal cell, a method is generally employed in which a pair of substrates on which a liquid crystal alignment film is formed are fixed with a sealant with a spacer interposed therebetween, and liquid crystal is injected and sealed. In this case, the size of the spacer used is 1 to 30 μm, preferably 2 to 10 μm.
The method for injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method for injecting liquid crystal after the inside of the manufactured liquid crystal cell is decompressed, and a dropping method for sealing after dropping the liquid crystal.

  By irradiating UV with a voltage applied between the electrodes on both sides of the liquid crystal cell in which the liquid crystal is introduced, crosslinkable groups such as acryl groups and methacryl groups in the alignment film are polymerized and cross-linked in situ. This increases the response speed of the liquid crystal display. Here, although the voltage to apply is AC5-50Vp-p or DC5-30V, Preferably, it is 5-30Vp-p or DC5-20V. The UV irradiation amount to be irradiated is 1 to 60 J using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, or the like, preferably 40 J or less, and a smaller UV irradiation amount constitutes a liquid crystal display. It is preferable because a reduction in reliability due to the destruction of the member can be suppressed, and the manufacturing tact can be increased by reducing the UV irradiation time.

The substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate. A specific example is the same as the substrate described in [Liquid crystal alignment film]. Standard electrode patterns such as PVA and MVA and protrusion patterns can also be used. Similar to the PSA type liquid crystal display, it can be operated even in a structure in which a line / slit electrode pattern of 1 to 10 μm is formed on one side substrate and a slit pattern or a projection pattern is not formed on the opposite substrate. The liquid crystal display can simplify the manufacturing process and provide high transmittance.
As a high-performance element such as a TFT element, an element in which a transistor element is formed between an electrode for driving a liquid crystal and a substrate is used.
In the case of a transmissive liquid crystal element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, a material such as aluminum that reflects light only on one substrate may be used. It is possible to use an opaque substrate such as a silicon wafer.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Synthesis Example 1 of Compound 8>
A 500 ml four-necked flask equipped with a magnetic stirrer was charged with 1.71 g of metallic magnesium, and the inside of the container was purged with nitrogen and sealed. After 2 ml of THF (dehydrated) was added, a solution prepared by dissolving 20.68 g of compound 7 in 155 ml of THF (dehydrated) was added dropwise over 1 hour with vigorous stirring. Then, it heated up at 55 degreeC and made it stir for 2 hours, and confirmed that the magnesium metal was lose | disappeared. Next, under ice-cooling (internal temperature 4 ° C.), 30.53 g of tetramethoxysilane was added all at once, and then heated to reflux and stirred for 3 hours. After cooling the reaction solution to room temperature, 210 ml of a saturated aqueous ammonium chloride solution was added, and the insoluble matter produced was removed by filtration under reduced pressure. Further, the filtrate was washed with 260 ml of n-hexane. The aqueous phase portion of the filtrate was removed, and the organic phase was washed with 200 ml of pure water. The organic phase was concentrated and dried to obtain 21.65 g of a crude product. This was distilled under reduced pressure and distilled under conditions of an external temperature of 220 to 230 ° C./pressure of 0.8 torr to obtain 5.74 g of Compound 8 (yield 25%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.90 ppm (t, J = 7.2 Hz, 3H), 1.00-1.09 ppm (m, 2H), 1.20-1.34 ppm (m, 9H), 1.40-1.52 ppm (m , 2H), 1.83-1.91ppm (m, 4H), 2.41-2.51ppm (m, 1H), 3.62ppm (s, 9H), 7.23ppm (d, J = 8.2 Hz, 2H), 7.56ppm (d, (J = 8.2 Hz, 2H)

<Synthesis Example 2 of Compound 10>
A 500 ml four-necked flask equipped with a magnetic stirrer was charged with 30.00 g of compound 9, 25.24 g of potassium carbonate, and 120 g of DMF, and 22.10 g of allyl bromide was added dropwise at room temperature. Then, it stirred at 50 degreeC for 11 hours. The reaction solution was diluted with 500 g of ethyl acetate, and the organic phase was washed 3 times with 200 g of pure water. The organic phase was dried over sodium sulfate and filtered, and then the filtrate was concentrated and dried to obtain 34.80 g of compound 10 (yield 100%).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.90 ppm (t, J = 7.2 Hz, 3H), 0.99-1.09 ppm (m, 2H), 1.18-1.46 ppm (m, 11H), 1.84-1.89 ppm (m , 4H), 2.37-2.44ppm (m, 1H), 4.51ppm (dt, J = 5.4 Hz, 1.6 Hz, 2H), 5.26ppm (dq, J = 10.6 Hz, 1.6 Hz, 1H), 5.40ppm (dq , J = 17.2 Hz, 1.6 Hz, 1H), 6.07 ppm (ddd, J = 17.2 Hz, 10.6 Hz, 5.4 Hz, 1H), 6.83 ppm (dd, J = 8.8 Hz, 2.9 Hz, 2H), 7.10 ppm ( (dd, J = 8.8 Hz, 2.9 Hz, 2H)

<Synthesis Example 3 of Compound 11>
A 300 ml four-necked flask equipped with a magnetic stirrer was charged with 20.00 g of compound 10 and 120 g of toluene and stirred at room temperature. Next, after adding 700 μl of a karstedt catalyst (platinum (0) -1,1,3,3-tetramethyldisiloxane complex 0.1 mol / L xylene solution), 12.4 ml of trimethoxysilane was dropped. After stirring at room temperature for 29 hours, the reaction solution was concentrated and dried to obtain a crude product. This was distilled under reduced pressure and distilled under conditions of an external temperature of 245 ° C./pressure of 0.8 torr to obtain 12.15 g of Compound 11 (43% yield).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.76-0.82 ppm (m, 2H), 0.89 ppm (t, J = 7.2 Hz, 3H), 0.98-1.08 ppm (m, 2H), 1.18-1.45 ppm (m , 11H), 1.84-1.93ppm (m, 6H), 2.36-2.43ppm (m, 1H), 3.58ppm (s, 9H), 3.91ppm (t, J = 6.8 Hz, 2H), 6.81ppm (d, J = 8.8 Hz, 2H), 7.08 ppm (d, J = 8.8 Hz, 2H)

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Abbreviations in the compounds used in the examples are as follows.
TEOS: tetraethoxysilane C18: octadecyltriethoxysilane MPMS: 3-methacryloxypropyltrimethoxysilane M8MS: 3-methacryloxyoctyltrimethoxysilane MTES: methyltriethoxysilane HG: 2-methyl-2,4-pentanediol ( (Alternative name: hexylene glycol)
BCS: 2-butoxyethanol UPS: 3-ureidopropyltriethoxysilane

<Execution synthesis example 1>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 20.5 g of HG, 6.8 g of BCS, 22.5 g of TEOS, 4.1 g of compound 11 obtained in Compound Synthesis Example 3, and 19 of MPMS .9 g was mixed to prepare an alkoxysilane monomer solution. To this solution, a solution prepared by previously mixing 10.2 g of HG, 3.4 g of BCS, 10.8 g of water and 1.3 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92 wt%, 0.3 g of HG and 0.1 g of BCS was previously added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, and mixed BCS20.0g, SiO ₂ conversion concentration was obtained 4 wt% liquid crystal aligning agent intermediates [S1].
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 23.8 g of HG, 7.9 g of BCS, 37.1 g of TEOS, and 3.6 g of MTES were mixed to prepare a solution of an alkoxysilane monomer. A solution prepared by previously mixing 1.9 g of HG, 4.0 g of BCS, 10.8 g of water, and 0.4 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by weight, 0.3 g of HG and 0.1 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, were mixed BCS20.0G, give in terms of SiO ₂ concentration of 4 wt% liquid crystal aligning agent intermediates of (U1).
The obtained liquid crystal aligning agent intermediate (S1) and liquid crystal aligning agent intermediate (U1) were mixed at a weight ratio of 2: 8 to obtain a liquid crystal aligning agent [K1] having a SiO ₂ equivalent concentration of 4% by weight. .

<Execution synthesis example 2>
In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 17.9 g of HG, 6.0 g of BCS, 25.0 g of TEOS, 8.2 g of compound 11 obtained in Compound Synthesis Example 3, and 19 of M8MS 0.1 g was mixed to prepare an alkoxysilane monomer solution. A solution prepared by mixing 9.0 g of HG, 3.0 g of BCS, 10.8 g of water and 1.1 g of oxalic acid as a catalyst in advance over 30 minutes was added dropwise to this solution over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 60 minutes, and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, were mixed BCS20.0g, SiO ₂ conversion concentration was obtained 4 wt% liquid crystal aligning agent intermediates [S2].
The obtained liquid crystal aligning agent intermediate (S2) and the liquid crystal aligning agent intermediate (U1) obtained in Synthesis Example 1 were mixed at a weight ratio of 2: 8, and the liquid crystal aligning concentration was 4% by weight in terms of SiO _2. Agent [K2] was obtained.

<Execution synthesis example 3>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 19.4 g of HG, 6.5 g of BCS, 22.5 g of TEOS, 8.2 g of Compound 11 obtained in Compound Synthesis Example 3, and 14.14 of MPMS. 9 g and 3.2 g of M8MS were mixed to prepare an alkoxysilane monomer solution. To this solution, a solution in which 9.7 g of HG, 3.2 g of BCS, 10.8 g of water and 1.1 g of oxalic acid as a catalyst were mixed dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by weight, 0.3 g of HG and 0.1 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, were mixed BCS20.0G, give in terms of SiO ₂ concentration of 4 wt% liquid crystal aligning agent intermediate of (S3).
The obtained liquid crystal aligning agent intermediate (S3) and the liquid crystal aligning agent intermediate (U1) obtained in Synthesis Example 1 were mixed at a weight ratio of 2: 8, and the liquid crystal alignment having a SiO ₂ equivalent concentration of 4% by weight. Agent [K3] was obtained.

<Comparative Synthesis Example 1>
A solution of alkoxysilane monomer was prepared by mixing 4.2 g of HG 22.6 g, BCS 7.5 g, TEOS 39.2 g, and C18 in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. A solution prepared by previously mixing 11.3 g of HG, 3.8 g of BCS, 10.8 g of water and 0.2 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by weight, 0.3 g of HG and 0.1 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, were mixed BCS20.0G, give in terms of SiO ₂ concentration of 4 wt% liquid crystal aligning agent intermediates of (S4).
The obtained liquid crystal aligning agent intermediate (S4) and the liquid crystal aligning agent intermediate (U1) obtained in Synthesis Example 1 were mixed at a weight ratio of 2: 8, and the liquid crystal aligning concentration was 4% by weight in terms of SiO _2. Agent [L1] was obtained.

<Comparative Synthesis Example 2>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 20.4 g of HG, 6.8 g of BCS, 22.5 g of TEOS, 4.2 g of C18, and 19.9 g of MPMS are mixed to obtain a solution of an alkoxysilane monomer. Was prepared. To this solution, a solution prepared by previously mixing 10.2 g of HG, 3.4 g of BCS, 10.8 g of water and 1.3 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a mixed solution of 0.6 g of a methanol solution having a UPS content of 92% by weight, 0.3 g of HG and 0.1 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.
The resulting polysiloxane solution 10.0 g, were mixed BCS20.0G, give in terms of SiO ₂ concentration of 4 wt% liquid crystal aligning agent intermediates of (S5).
The obtained liquid crystal aligning agent intermediate (S5) and the liquid crystal aligning agent intermediate (U1) obtained in Synthesis Example 1 were mixed at a weight ratio of 2: 8, and the liquid crystal alignment having a SiO ₂ equivalent concentration of 4% by weight. Agent [L2] was obtained.

<Example 1>
The liquid crystal aligning agent [K1] obtained in Example 1 was spin-coated on the ITO surface of the ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 × 300 microns and a line / space of 5 microns was formed. did. After drying for 2 minutes on an 80 ° C. hot plate, baking was performed in a hot air circulation oven at 200 ° C. or 220 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. The liquid crystal aligning agent [K1] obtained in Example Synthesis Example 1 was spin-coated on the ITO surface on which no electrode pattern was formed, dried on a hot plate at 80 ° C. for 2 minutes, and then 200 ° C. or Firing was performed in a hot air circulation oven at 220 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. These two substrates were prepared, 4 μm bead spacers were sprayed on the liquid crystal alignment film surface of one substrate, and a sealant was printed thereon. The liquid crystal alignment film surface of the other substrate was placed inside and bonded together, and then the sealing agent was cured to produce an empty cell. A liquid crystal cell was prepared by injecting liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) into the empty cell by vacuum injection.
The response speed characteristics of these liquid crystal cells were measured by the method described later.
After that, in the state where a DC voltage of 20 V was applied to the liquid crystal cell, 20 J of UV was irradiated from the outside of the liquid crystal cell in terms of 365 nm using an ultrahigh pressure mercury lamp. Thereafter, the response speed characteristic was measured again, and the response speed before and after UV irradiation was compared. The results are shown in Table 1.
Thereafter, the obtained liquid crystal cell was annealed in a circulation oven at 100 ° C. for 30 minutes. The extracted cell was observed with a microscope in a state where the polarizing plate was in a crossed Nicol state, and the state of the domain, which was an alignment disorder of the liquid crystal, was observed. The results are also shown in Table 1.

<Example 2>
A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K2] obtained in Example of Synthesis Example 2, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
<Example 3>
A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K3] obtained in Example Synthesis Example 3, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.

<Comparative Example 1>
A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L1] obtained in Comparative Synthesis Example 1, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
<Comparative Example 2>
A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L2] obtained in Comparative Synthesis Example 2, and the response speed was measured. A domain that is turbulent was observed. The results are shown in Table 1.
[Response speed characteristics]
The change in luminance of the liquid crystal panel over time when an AC voltage of ± 5 V and a rectangular wave with a frequency of 1 kHz was applied to the liquid crystal cell was captured with an oscilloscope. When no voltage was applied, the luminance was 0%, a voltage of ± 5 V was applied, the saturated luminance value was 100%, and the time for the luminance to change from 10% to 90% was defined as the rising response speed.

応答速度の判定 ○：早い（良好） ×：遅い（悪い）
アニール後のドメイン観察結果
×：ドメインが多数観察される
○：良好
◎：非常に良好
表１からわかるように、実施例１ではＵＶ照射後の応答速度が速く、かつアニール後のドメイン観察結果でも、良好な結果であった。一方比較例１においては、アニール後のドメイン観察結果は非常に良好であるが、応答速度が遅かった。比較例２においては、応答速度は速かったが、アニール後にドメインが多数観察された。更に実施例２、３においても、ＵＶ照射後の応答速度が速く、且つアニール後のドメイン観察結果でも非常に良好な結果を示した。

Judgment of response speed ○: Fast (good) ×: Slow (bad)
Domain observation result after annealing ×: Many domains are observed ○: Good ◎: Very good As can be seen from Table 1, in Example 1, the response speed after UV irradiation is high, and the domain observation result after annealing is also It was a good result. On the other hand, in Comparative Example 1, the domain observation result after annealing was very good, but the response speed was slow. In Comparative Example 2, the response speed was fast, but many domains were observed after annealing. Furthermore, in Examples 2 and 3, the response speed after UV irradiation was fast, and the results of domain observation after annealing showed very good results.

The liquid crystal display element produced using the liquid crystal aligning agent of the present invention is a liquid crystal display element of a system that improves the response speed after UV irradiation by using a liquid crystal to which a polymerizable compound is not added and treating in the same manner as the PSA system. , A liquid crystal alignment agent capable of forming a liquid crystal alignment film capable of improving the response speed after UV irradiation without reducing the vertical alignment force, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and the liquid crystal alignment film The liquid crystal display element which has can be provided. Therefore, it is useful for a TFT liquid crystal display device, a TN liquid crystal display device, a VA liquid crystal display device and the like manufactured by the above method.
It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-251377 filed on November 17, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (11)

A liquid crystal aligning agent comprising the following polysiloxane (A).
Polysiloxane (A): Polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane represented by formula (1) and an alkoxysilane represented by formula (3).
R ¹ Si (OR ² ) ₃ (1)
(R ¹ represents the structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)

(In Formula (2), Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO—, or OCO—. Y ² is a linear or branched divalent hydrocarbon group having 3 to 8 carbon atoms containing a single bond or a double bond, or (CR ¹⁷ R ¹⁸ ) _b — (b is 1 to 15 And each of R ¹⁷ and R ¹⁸ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) Y ³ is a single bond, — (CH ₂ ) _c — (c is 1 to 15 is an integer of 15.), —O—, —CH ₂ O—, —COO—, or OCO—, Y ⁴ is a divalent group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a heterocyclic ring. A cyclic group or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, and any hydrogen atom on these cyclic groups is a carbon atom; It is selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, and a fluorine atom. Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has 1 carbon atom. Or an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. And Y ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine atom having 1 to 18 carbon atoms. Represents an alkoxy group.)
R ³ Si (OR ⁴ ) ₃ (3)
(R ³ is an acrylic group, an acryloxy group, .R ⁴ is a methacryl group, a methacryloxy group, or an alkyl group having 5 to 10 carbon atoms which is substituted with a styryl group represents an alkyl group having 1 to 5 carbon atoms.) Furthermore, the liquid crystal aligning agent of Claim 1 containing polysiloxane (B).
Polysiloxane (B): A polysiloxane obtained by hydrolysis and polycondensation of an alkoxysilane containing 50 to 100 mol% of the alkoxysilane represented by the formula (5).
Si (OR ¹⁵ ) ₄ (5)
(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms.)   The liquid crystal aligning agent of Claim 2 whose polysiloxane (B) is polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane further represented by Formula (3). The liquid crystal aligning agent of Claim 2 or 3 whose polysiloxane (B) is polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane further represented by Formula (6).
R ¹⁶ Si (OR ¹⁷ ) ₃ (6)
^{(R 16} is, ^{.R 17} is an alkyl group having 1 to 5 carbon atoms is an alkyl group having 1 to 5 carbon atoms.) At least one of the polysiloxane (A) and the polysiloxane (B) is a polysiloxane obtained by further hydrolyzing and polycondensing an alkoxysilane containing an alkoxysilane represented by the following formula (4): Item 5. The liquid crystal aligning agent according to any one of Items 2 to 4.
(R ¹³ ) _n Si (OR ¹⁴ ) _4-n (4)
(In formula (4), R ¹³ is a carbon atom having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. R ¹⁴ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.)   The alkoxysilane represented by the formula (1) is contained in an amount of 2 to 20 mol% in the total alkoxysilane used in the polysiloxane (A), and the alkoxysilane represented by the formula (3) is a polysiloxane. The liquid crystal aligning agent in any one of Claims 1-5 contained in 5-70 mol% in all the alkoxysilanes used for (A). Moreover, the solvent contained, and the content of total polysiloxane, in terms of SiO _2, 0.5 to 15 wt%, the liquid crystal alignment agent according to any one of claims 1 to 6.   The liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent in any one of Claims 1-7 to a board | substrate, drying and baking.   The liquid crystal display element which has a liquid crystal aligning film of Claim 8.   The liquid crystal display element which apply | coated the liquid crystal aligning agent in any one of Claims 1-7, and irradiated UV in the state which applied the voltage to the liquid crystal cell by which the liquid crystal was pinched | interposed with the board | substrate baked.   A method for producing a liquid crystal display element, wherein the liquid crystal aligning agent according to claim 1 is applied, the liquid crystal is sandwiched between two baked substrates, and UV is irradiated in a state where a voltage is applied.