JPWO2015008846A1 - Liquid crystal display element, liquid crystal alignment treatment agent, and liquid crystal alignment film - Google Patents

Abstract

A liquid crystal composition comprising a liquid crystal and a polymerizable compound that is polymerized by active energy rays or heat is disposed between two substrates provided with electrodes, and has a liquid crystal alignment film on at least one of the substrates, A liquid crystal display element obtained by curing in a state where a part or the whole of a liquid crystal composition exhibits liquid crystallinity to form a cured product composite of a liquid crystal and a polymerizable compound, wherein the liquid crystal alignment film has the following components: The liquid crystal display element formed from the liquid-crystal aligning agent containing (A) and a component (B). Component (A): Cellulosic polymer having a specific structure. Component (B): a polysiloxane polymer having a specific structure.

Description

  The present invention relates to a transmission / scattering type liquid crystal display element that becomes transparent when no voltage is applied and is in a scattering state when a voltage is applied, a liquid crystal aligning agent for the element, and a liquid crystal alignment film.

A TN (Twisted Nematic) mode has been put to practical use as a liquid crystal display element using a liquid crystal material. In this mode, light is switched by utilizing the optical rotation characteristics of the liquid crystal, and it is necessary to use a polarizing plate when used as a liquid crystal display element. However, it is known that the use efficiency of light is lowered by using a polarizing plate.
As a liquid crystal display element having a high light utilization efficiency without using a polarizing plate, there is a liquid crystal display element that switches between a liquid crystal transmission state (also referred to as a transparent state) and a scattering state. A liquid crystal using a dispersion liquid crystal (PDLC (Polymer Dispersed Liquid Crystal)) or a polymer network liquid crystal (PNLC (Polymer Network Liquid Crystal)) is known.

A liquid crystal display element using these includes a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates. The liquid crystal composition is disposed, and the liquid crystal composition is cured in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and is manufactured through a process of forming a cured product composite of the liquid crystal and the polymerizable compound. It is a liquid crystal display element. And this liquid crystal display element controls the permeation | transmission state and scattering state of a liquid crystal by application of a voltage.
As a conventional liquid crystal display element using PDLC or PNLC, liquid crystal molecules are in a random direction when no voltage is applied, and thus becomes clouded (scattered). There is known a normal type element that is transmitted and becomes a transmission state. However, in a normal type element, it is necessary to always apply a voltage in order to obtain a transmissive state. large.
A reverse type element has been reported that is in a transmission state when no voltage is applied to a normal type element and in a scattering state when a voltage is applied (see Patent Documents 1 and 2).

Japanese Patent No. 2885116 Japanese Patent No. 4132424

In the reverse type element, since the liquid crystal must be vertically aligned, a liquid crystal alignment film (also referred to as a vertical liquid crystal alignment film) that aligns the liquid crystal vertically is used. At that time, since the vertical liquid crystal alignment film is a highly hydrophobic film, the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered. Therefore, a large amount of a polymerizable compound (also referred to as a curing agent) for improving the adhesion between the liquid crystal layer and the liquid crystal alignment film must be introduced into the liquid crystal composition used for the reverse type element. However, when a large amount of the polymerizable compound is introduced, the vertical alignment property of the liquid crystal is hindered, and there is a problem that transparency when no voltage is applied and scattering characteristics when a voltage is applied are greatly deteriorated. Therefore, the liquid crystal alignment film used for the reverse element needs to have a high vertical alignment property of the liquid crystal.
Accordingly, an object of the present invention is to provide a liquid crystal display element having the above-described characteristics. That is, the object of the present invention is that the vertical alignment of the liquid crystal is high and has good optical properties, that is, transparency when no voltage is applied and scattering property when a voltage is applied. It is to provide a liquid crystal display element having high adhesion. Furthermore, the present invention provides a liquid crystal alignment film for the liquid crystal display element and a liquid crystal alignment treatment agent used for forming the liquid crystal alignment film.

  As a result of earnest research, the present inventor has a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a cellulose polymer having a specific structure and a polysiloxane polymer having a side chain having a specific structure. A liquid crystal display element having high adhesion between a layer and a liquid crystal alignment film, high vertical alignment of liquid crystal, and good optical characteristics, that is, transparency when no voltage is applied and scattering characteristics when a voltage is applied It was found that it can be obtained.

（Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５及びＸ^６は、それぞれ独立して、下記の式［１ａ］〜［１ｍ］からなる群から選ばれる少なくとも１種の基を示す。ｎは１００〜１００００００の整数を示す。）The present invention is based on such knowledge and has the following gist.
(1) A liquid crystal composition comprising a liquid crystal and a polymerizable compound that is polymerized by active energy rays or heat is disposed between two substrates provided with electrodes, and a liquid crystal alignment film is provided on at least one of the substrates. And a liquid crystal display element in which a cured product composite of a liquid crystal and a polymerizable compound is formed by curing a part or the whole of the liquid crystal composition exhibiting liquid crystallinity. A liquid crystal display element, which is formed from a liquid crystal aligning agent containing the components (A) and (B).
Component (A): Cellulosic polymer having a structure represented by the following formula [1].

(X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent at least one group selected from the group consisting of the following formulas [1a] to [1m]. Represents an integer of 100 to 1000000.)

（Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１、Ｘ^１２、Ｘ^１３、及びＸ^１４は、それぞれ独立して、ベンゼン環、メチル基、エチル基、ｎ−プロピル基、イソプロピル基及びブチル基からなる群から選ばれる少なくとも１種を示す。ｎは０〜３の整数を示す。ｍは０〜３の整数を示す。）

(X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , and X ¹⁴ are each independently a benzene ring, methyl group, ethyl group, n-propyl group, isopropyl group, and butyl. And at least one selected from the group consisting of groups, n represents an integer of 0 to 3, and m represents an integer of 0 to 3.)

（Ａ^１は、下記の式［２−１］及び式［２−２］で示される構造からなる群から選ばれる少なくとも１種の構造を示す。Ａ^２は、水素原子又は炭素数１〜５のアルキル基を示す。Ａ^３は、炭素数１〜５のアルキル基を示す。ｍは１又は２の整数を示す。ｎは０〜２の整数を示す。ｐは０〜３の整数を示す。ただし、ｍ＋ｎ＋ｐは４である。）Component (B): at least one selected from the group consisting of an alkoxysilane represented by the following formula [2a], an alkoxysilane represented by the following formula [2b], and an alkoxysilane represented by the following formula [2c] A polysiloxane polymer obtained by polycondensation.

(A ¹ represents at least one structure selected from the group consisting of structures represented by the following formulas [2-1] and [2-2]. A ² represents a hydrogen atom or a carbon number of 1 to 5. A ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3. (However, m + n + p is 4.)

（Ｙ^１は、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−及び−ＯＣＯ−からなる群から選ばれる少なくとも１種を示す。Ｙ^２は、単結合又は−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示す。Ｙ^３は、単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−及び−ＯＣＯ−からなる群から選ばれる少なくとも１種を示す。Ｙ^４は、ベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる少なくとも１種の２価の環状基、又はステロイド骨格を有する炭素数１７〜５１の２価の有機基を示し、前記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のアルコキシル基、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ル基又はフッ素原子で置換されていてもよい。Ｙ^５は、ベンゼン環、シクロヘキサン環及び複素環からなる群から選ばれる少なくとも１種の環状基を示し、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のアルコキシル基、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ル基又はフッ素原子で置換されていてもよい。ｎは０〜４の整数を示す。Ｙ^６は、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のアルコキシル基及び炭素数１〜１８のフッ素含有アルコキシル基からなる群から選ばれる少なくとも１種を示す。ｎは０〜４の整数を示す。）

(Y ¹ is selected from the group consisting of a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO—, and —OCO—. Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15.) Y ³ represents a single bond, — (CH ₂ ) _c — (c Is an integer of 1 to 15, and represents at least one selected from the group consisting of —O—, —CH ₂ O—, —COO—, and —OCO—, Y ⁴ represents a benzene ring, a cyclohexane ring, and a heterocycle. At least one divalent cyclic group selected from the group consisting of a ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, wherein any hydrogen atom on the cyclic group has 1 carbon atom -3 alkyl group, C 1-3 alkoxyl group, C 1-3 fluorine-containing amine Kill group may .Y ⁵ be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms represents at least one cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic And any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine containing group having 1 to 3 carbon atoms. It may be substituted with an alkoxyl group or a fluorine atom, n represents an integer of 0 to 4. Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, or 1 carbon atom. -At least 1 sort (s) chosen from the group which consists of a C-18 alkoxy group and a C1-C18 fluorine-containing alkoxyl group is shown, n shows the integer of 0-4.)

（Ｙ^７は、単結合、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−及び−ＯＣＯ−からなる群から選ばれる少なくとも１種の結合基を示す、Ｙ^８は、炭素数８〜２２のアルキル基又は炭素数６〜１８のフッ素含有アルキル基を示す。）

(Y ⁷ is a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and —OCO—. Y ⁸ represents at least one linking group selected from the group consisting of: an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.)

（Ｂ^１は、ビニル基、エポキシ基、アミノ基、メルカプト基、イソシアネート基、メタクリル基、アクリル基、ウレイド基及びシンナモイル基からなる群から選ばれる少なくとも１種を有する炭素数２〜１２の有機基を示す。Ｂ^２は、水素原子又は炭素数１〜５のアルキル基を示す。Ｂ^３は、炭素数１〜５のアルキル基を示す。ｍは１又は２の整数を示す。ｎは０〜２の整数を示す。ｐは０〜３の整数を示す。ただし、ｍ＋ｎ＋ｐは４である。）

(B ¹ include a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacrylic group, an organic group having 2 to 12 carbon atoms and having at least one selected from the group consisting of acrylic group, a ureido group, and a cinnamoyl group B ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, and n represents 0 to 0. Represents an integer of 2. p represents an integer of 0 to 3, where m + n + p is 4.)

（Ｄ^１は、水素原子又は炭素数１〜５のアルキル基を示す。Ｄ^２は、炭素数１〜５のアルキル基を示す。ｎは０〜３の整数を示す。）

^{(D 1} is, .D ² represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, .n represents an alkyl group having 1 to 5 carbon atoms is an integer of 0 to 3.)

(2) The liquid crystal according to (1), wherein the ratio of the component (A) to the component (B) is 0.1 to 9 parts by mass with respect to 1 part by mass of the component (B). Display element.
(3) The alkoxysilane represented by the formula [2b] of the component (B) is allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris ( The above (1) which is at least one selected from the group consisting of 2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate and 3- (trimethoxysilyl) propyl methacrylate Or a liquid crystal display device according to (2).

(4) The alkoxysilane represented by the formula [2b] of the component (B) is 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane and 2 The liquid crystal display device according to (1) or (2), which is at least one selected from the group consisting of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane.
(5) The component (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula [2a], or an alkoxy represented by the formula [2a] and the formula [2b] or the formula [2c] The liquid crystal display element according to any one of the above (1) to (4), which is a polysiloxane obtained by polycondensation with silane.

（Ａ^１は、炭素数１〜３のアルキル基を示す。Ａ^２は、炭素数１〜３のアルキル基を示す。Ａ^３は、炭素数１〜４のアルキル基を示す。）(6) Furthermore, the liquid crystal display element in any one of said (1)-(5) which contains a solvent in the said liquid-crystal aligning agent.
(7) As the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1,3-propanediol, 1,3-butanediol, 1, 4-butanediol, 2,3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene The liquid crystal display according to the above (6), which contains at least one solvent selected from the group consisting of recall methyl ether, dipropylene glycol dimethyl ether, furfuryl alcohol and solvents represented by the following formulas [A1] to [A3]. element.

(A ¹ represents an alkyl group having 1 to 3 carbon atoms. A ² represents an alkyl group having 1 to 3 carbon atoms. A ³ represents an alkyl group having 1 to 4 carbon atoms.)

（Ｂ^１は、水素原子又はベンゼン環を示す。Ｂ^２は、ベンゼン環、シクロへキサン環及び複素環からなる群から選ばれる少なくとも１種の環状基を示す。Ｂ^３は、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のアルコキシル基及び炭素数１〜１８のフッ素含有アルコキシル基からなる群から選ばれる少なくとも１種を示す。）(8) Further, the liquid crystal aligning agent contains an adhesive compound having at least one selected from the group consisting of structures represented by the following formulas [B1] to [B8]. (7) The liquid crystal display element in any one of.

(B ¹ represents a hydrogen atom or a benzene ring. B ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. B ³ represents a carbon number of 1 to 1. And at least one selected from the group consisting of an 18 alkyl group, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.)

(9) Furthermore, the liquid crystal alignment treatment agent further contains at least one generator selected from the group consisting of a photo radical generator, a photo acid generator and a photo base generator. The liquid crystal display element in any one.
(10) The liquid crystal display element according to any one of (1) to (9), wherein the substrate is a glass substrate or a plastic substrate.
(11) A liquid crystal alignment film used for the liquid crystal display element according to any one of (1) to (10) above, and a liquid crystal formed from a liquid crystal alignment treatment agent containing the component (A) and the component (B). Alignment film.
(12) The liquid crystal alignment film according to (11), wherein the film thickness is 5 to 300 nm.
(13) A liquid crystal alignment treatment agent for forming a liquid crystal alignment film according to the above (11) or (12), which contains the component (A) and the component (B).

  According to the present invention, a liquid crystal layer and a vertical liquid crystal alignment are obtained by using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a cellulose polymer having a specific structure and a polysiloxane polymer having a side chain having a specific structure. It is possible to provide a liquid crystal display device having high adhesion to a film, high liquid crystal vertical alignment, and good optical characteristics, that is, good transparency when no voltage is applied and good scattering characteristics when a voltage is applied. In particular, the liquid crystal display element of the present invention can be suitably used for a reverse type element that is in a transmissive state when no voltage is applied and is in a scattering state when a voltage is applied. It is used as a dimming window or an optical shutter element for controlling blocking.

The liquid-crystal aligning agent used for the liquid crystal display element of this invention is the cellulose polymer (it is also called a specific cellulose polymer) which is a component (A), and the polysiloxane polymer (specific) which is a component (B). (Also referred to as polysiloxane polymer).
This specific cellulosic polymer has high transparency. Therefore, the vertical liquid crystal alignment film obtained from the liquid crystal alignment treatment agent is difficult to absorb light such as ultraviolet rays, and promotes the reaction of the polymerizable compound in the liquid crystal composition by irradiation of active energy rays when producing a liquid crystal display element. can do.
Further, among the specific side chain structures contained in the specific polysiloxane polymer, the structure represented by the formula [2-1] is at least selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring at the side chain site. It has one kind of cyclic group or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. Since the side chain structure of these cyclic groups and organic groups shows a rigid structure, a liquid crystal display element using a vertical liquid crystal alignment film having a specific side chain structure represented by Formula [2-1] is expensive. Stable liquid crystal vertical alignment can be obtained. Furthermore, for the above reasons, the specific side chain structure represented by the formula [2-1] can obtain high vertical alignment even if the amount of the side chain structure introduced is small. Therefore, the liquid crystal display element using the vertical liquid crystal alignment film having the specific side chain structure represented by the formula [2-1] has higher adhesion between the liquid crystal layer and the vertical liquid crystal alignment film.

<Liquid crystal display element>
The liquid crystal display element of the present invention uses a vertical liquid crystal alignment film obtained from a liquid crystal aligning agent containing a specific cellulose polymer and a specific polysiloxane polymer having a specific side chain structure, and the vertical alignment of the liquid crystal is high. High, good optical properties, that is, transparency when no voltage is applied and scattering property when a voltage is applied, and further, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high.
The liquid crystal display element of the present invention comprises a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound that is polymerized by liquid crystal and ultraviolet light between the pair of substrates. Further, the liquid crystal composition is formed by irradiating with ultraviolet rays in a state where at least one of the substrates has a liquid crystal alignment film that aligns liquid crystal vertically and part or all of the liquid crystal composition exhibits liquid crystallinity. It is manufactured through a process of curing a product and forming a cured product composite of liquid crystal and a polymerizable compound. it can.

式［１］中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５及びＸ^６は、それぞれ独立して、下記の式［１ａ］〜［１ｍ］からなる群から選ばれる少なくとも１種の基を示す。
ｎは１００〜１００００００の整数を示す。なかでも、特定セルロース系重合体の溶媒への溶解性や、液晶配向処理剤として調製した際の取り扱い性の点から、ｎは１００〜５００，０００が好ましい。より好ましいのは１００〜１００，０００である。<Specific cellulose polymer>
The specific cellulose polymer is a polymer having a structure represented by the following formula [1].

In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently at least one selected from the group consisting of the following formulas [1a] to [1m]. Indicates a group.
n shows the integer of 100-1 million. Among these, n is preferably 100 to 500,000 from the viewpoint of the solubility of the specific cellulose polymer in a solvent and the handleability when it is prepared as a liquid crystal aligning agent. More preferred is 100 to 100,000.

Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１、Ｘ^１２、Ｘ^１３及びＸ^１４は、それぞれ独立して、ベンゼン環、メチル基、エチル基、ｎ−プロピル基、イソプロピル基及びブチル基からなる群から選ばれる少なくとも１種を示す。

X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently a benzene ring, methyl group, ethyl group, n-propyl group, isopropyl group and butyl group. At least one selected from the group consisting of

n represents an integer of 0 to 3. Among these, an integer of 0 or 1 is preferable.
m shows the integer of 0-3. Among these, an integer of 0 or 1 is preferable.
X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent at least one group selected from the group consisting of formulas [1a] to [1m]. May be one type or two or more types. In particular, it is preferable to use two or more types from the viewpoint of the solubility of the specific cellulose polymer in a solvent and the coating properties of the liquid crystal aligning agent.
Particularly preferably, the formulas [1a] and [1b] to [1m] are used. Furthermore, it is preferable to use Formula [1a], Formula [1c], Formula [1d], Formula [1e], Formula [1h], or Formula [1i].

Specific examples of the specific cellulose polymer include the following, but are not limited to these examples.
For example, cellulose, methylcellulose, ethylcellulose, propylcellulose, butylcellulose, methylethylcellulose, acetylcellulose, cellulose propionate, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose Phthalate, methylaminocellulose, ethylaminocellulose, propylaminocellulose, benzylcellulose, tribenzoylcellulose, cellulose acetate butyrate, cellulose acetate propionate, carboxymethylcellulose, carboxymethylethylcellulose or carboxymethyl Such as hydroxyethyl cellulose, and the like. Among them, methylcellulose, ethylcellulose, propylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate, benzylcellulose, cellulose acetate propionate, carboxymethylethylcellulose or carboxy Methyl hydroxyethyl cellulose is preferred. More preferred are methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate or carboxymethylethylcellulose. Particularly preferred are methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose or hydroxypropylmethylcellulose phthalate.

These cellulose derivatives are generally available. Moreover, there is no restriction | limiting in particular in the method of introduce | transducing the structure represented by Formula [1b]-[1m], The existing method can be used.
For example, when formula [1b] is introduced, a method of reacting cellulose and benzyl chloride in the presence of an alkali,
When introducing the formula [1c], a method of reacting cellulose and a halogen compound having X ⁷ in the presence of an alkali,
When introducing the formula [1d], a method of reacting cellulose and an acid chloride compound having X ⁸ in the presence of an alkali, a method of reacting cellulose and acetic anhydride,
In the case of introducing the formula [1e], a method of reacting cellulose and a halogen compound having X ⁹ -OH in the presence of an alkali,
When introducing the formula [1f], a method of reacting cellulose and a halogen compound having X ¹⁰ —COOH in the presence of an alkali,
When introducing the formula [1g], a method of reacting cellulose and a halogen compound having X ¹¹ —NH ₂ in the presence of an alkali,
When introducing the formula [1h], a method of reacting cellulose and phthalic acid,
METHOD case, the reaction of a halogen compound having a cellulose and X ¹² and phthalic acid skeleton in the presence of an alkali to introduce the formula [1i],
In the case of introducing the formula [1k], a method of reacting cellulose and maleic anhydride can be mentioned.
The specific cellulose polymer is soluble in the solvent of the specific cellulose polymer, the coating property of the liquid crystal aligning agent, and the optical properties of the liquid crystal display element and the adhesion properties between the liquid crystal layer and the vertical liquid crystal alignment film. Depending on the type, one type or a mixture of two or more types can be used.

式[２ａ]中、Ａ^１は、下記の式［２−１］又は式［２−２］で示される構造からなる群から選ばれる少なくとも１種の構造を示す。なかでも、高くて安定な液晶の垂直配向性を得ることができる点から、式［２−１］で示される構造が好ましい。
Ａ^２は、水素原子又は炭素数１〜５のアルキル基を示す。なかでも、水素原子又は炭素数１〜３のアルキル基が好ましい。
Ａ^３は、炭素数１〜５のアルキル基を示す。なかでも、重縮合の反応性の観点から、炭素数１〜３のアルキル基が好ましい。
ｍは１又は２の整数を示す。なかでも、合成の観点から、１が好ましい。
ｎは０〜２の整数を示す。
ｐは０〜３の整数を示す。なかでも、重縮合の反応性の観点から、１〜３の整数が好ましい。より好ましくは、２又は３である。
なお、ｍ＋ｎ＋ｐは４である。<Polysiloxane polymer>
The polysiloxane polymer is at least selected from the group consisting of an alkoxysilane represented by the following formula [2a], an alkoxysilane represented by the following formula [2b], and an alkoxysilane represented by the following formula [2c]. It is a polysiloxane obtained by polycondensing one kind.

In formula [2a], A ¹ represents at least one structure selected from the group consisting of structures represented by the following formula [2-1] or formula [2-2]. Among these, the structure represented by the formula [2-1] is preferable from the viewpoint that a high and stable vertical alignment of liquid crystal can be obtained.
A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
A ³ represents an alkyl group having 1 to 5 carbon atoms. Among these, from the viewpoint of polycondensation reactivity, an alkyl group having 1 to 3 carbon atoms is preferable.
m represents an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis.
n shows the integer of 0-2.
p shows the integer of 0-3. Especially, the integer of 1-3 is preferable from the reactive viewpoint of polycondensation. More preferably, it is 2 or 3.
Note that m + n + p is 4.

式[２−１]中、Ｙ^１は、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−及び−ＯＣＯ−からなる群から選ばれる少なくとも１種の結合基を示す。なかでも、原料の入手性や合成の容易さの点から、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−が好ましい。より好ましいのは、単結合、−（ＣＨ_２）_ａ−（ａは１〜１０の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−である。

In Formula [2-1], Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO—, and —OCO. -At least 1 type of coupling group chosen from the group which consists of-is shown. Among these, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, or —COO. -Is preferred. More preferred is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.
Y ³ is at least selected from the group consisting of a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO—, and —OCO—. One kind of linking group is shown. Among these, from the viewpoint of ease of synthesis, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, or —COO— is preferable. More preferred is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

Y ⁴ is at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Further, X ⁴ may be an organic group selected from organic groups having 17 to 51 carbon atoms having a steroid skeleton. Among these, from the viewpoint of ease of synthesis, an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable.
Y ⁵ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms. , An alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring is preferable.

Y ⁶ is at least selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. One type is shown. Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxyl group. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
n shows the integer of 0-4. Especially, 0-3 are preferable from the point of the availability of a raw material and the ease of a synthesis | combination. More preferably, it is 0-2.

As preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n, Tables 6 to 47 on pages 13 to 34 of International Publication No. WO2011-132751 (2011.10.27 published) (2-1) to (2-629) listed in (1). Incidentally, Y1 to Y6 in the tables of WO is to be replaced with ^Y 1 to Y ⁶ of the present invention.
Moreover, in (2-605)-(2-629) published in each table | surface of an international publication gazette, all the C12-25 organic groups which have a steroid skeleton are carbon which has a steroid skeleton of this invention. It shall be read as an organic group of formulas 17 to 51.
Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) are preferred. Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).

式[２−２]中、Ｙ^７は、単結合、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＣＯＯ−及び−ＯＣＯ−からなる群から選ばれる少なくとも１種の結合基を示す。なかでも、単結合、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＮＨ−、−ＣＯＮ（ＣＨ_３）−又は−ＣＯＯ−が好ましい。より好ましくは、単結合、−Ｏ−、−ＣＯＮＨ−又は−ＣＯＯ−である。
Ｙ^８は、炭素数８〜２２のアルキル基又は炭素数６〜１８のフッ素含有アルキル基を示す。なかでも、炭素数８〜１８のアルキル基が好ましい。
本発明における特定側鎖構造としては、前記の通り、高くて安定な液晶の垂直配向性を得ることができる点から、式［２−１］で示される特定側鎖構造を用いることが好ましい。

In formula [2-2], Y ⁷ represents a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, At least one linking group selected from the group consisting of —COO— and —OCO—; Among these, a single bond, —O—, —CH ₂ O—, —CONH—, —CON (CH ₃ ) —, or —COO— is preferable. More preferably, they are a single bond, -O-, -CONH-, or -COO-.
Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. Of these, an alkyl group having 8 to 18 carbon atoms is preferable.
As the specific side chain structure in the present invention, as described above, it is preferable to use the specific side chain structure represented by the formula [2-1] from the viewpoint of obtaining high and stable liquid crystal vertical alignment.

Specific examples of the alkoxysilane represented by the formula [2a] include alkoxysilanes represented by the following formulas [2a-1] to [2a-32].

（Ｒ^１は、炭素数１〜３のアルキル基を示す。Ｒ^２は、炭素数１〜３のアルキル基を示す。ｍは２又は３の整数を示す。ｎは０又は１の整数を示す。）

(R ¹ represents an alkyl group having 1 to 3 carbon atoms. R ² represents an alkyl group having 1 to 3 carbon atoms. M represents an integer of 2 or 3. n represents an integer of 0 or 1. .)

（Ｒ^１は、炭素数１〜３のアルキル基を示す。Ｒ^２は、炭素数１〜３のアルキル基を示す。Ｒ^３は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−及び−ＣＨ_２ＯＣＯ−からなる群から選ばれる少なくとも１種の結合基を示す。Ｒ^４は、炭素数１〜１２のアルキル基、アルコキシ基、フッ素含有アルキル基及びフッ素含有アルコキシ基からなる群から選ばれる少なくとも１種を示す。ｍは２又は３の整数を示す。ｎは０又は１の整数を示す。）

(R ¹ represents an alkyl group having 1 to 3 carbon atoms. R ² represents an alkyl group having 1 to 3 carbon atoms. R ³ represents —O—, —COO—, —OCO—, —CONH—. , —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, and —CH ₂ OCO—. R ⁴ represents at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, and a fluorine-containing alkoxy group, and m is 2 or 3. (N represents an integer of 0 or 1)

（Ｒ^１は、炭素数１〜３のアルキル基を示す。Ｒ^２は、炭素数１〜３のアルキル基を示す。Ｒ^３は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−及び−ＣＨ_２ＯＣＯ−からなる群から選ばれる少なくとも１種の結合基を示す。Ｒ^４は、炭素数１〜１２のアルキル基、アルコキシ基、フッ素含有アルキル基、フッ素含有アルコキシ基、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、アセトキシ基及び水酸基からなる群から選ばれる少なくとも１種を示す。ｍは２又は３の整数を示す。ｎは０又は１の整数を示す。）

(R ¹ represents an alkyl group having 1 to 3 carbon atoms. R ² represents an alkyl group having 1 to 3 carbon atoms. R ³ represents —O—, —COO—, —OCO—, —CONH—. , —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, and —CH ₂ OCO—. R ⁴ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, a fluorine-containing alkoxy group, a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, This represents at least one selected from the group consisting of a formyl group, an acetyl group, an acetoxy group and a hydroxyl group, m represents an integer of 2 or 3, and n represents an integer of 0 or 1.

(In the formulas [2a-25] to [2a-31], R ¹ represents an alkyl group having 1 to 3 carbon atoms. R ² represents an alkyl group having 1 to 3 carbon atoms. R ³ represents − O -, - COO -, - OCO -, - CONH -, - NHCO -, - CON (CH 3) -, - N (CH 3) CO -, - OCH 2 -, - CH 2 O -, - COOCH 2 And at least one selected from the group consisting of — and —CH ₂ OCO—, wherein R ⁴ is selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, and a fluorine-containing alkoxy group. (At least 1 type is shown, m shows the integer of 2 or 3. n shows the integer of 0 or 1.)

（Ｒ_１は、炭素数１〜３のアルキル基を示す。Ｒ_２は、炭素数１〜３のアルキル基を示す。ｍは２又は３の整数を示す。ｎは０又は１の整数を示す。Ｂ^４は、フッ素原子で置換されていてもよい炭素数３〜２０のアルキル基を示す。Ｂ^３は、１，４−シクロへキシレン基又は１，４−フェニレン基を示す。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。）を示す。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。）を示す。ａ^１は０又は１の整数を示す。ａ^２は２〜１０の整数を示す。ａ^３は０又は１の整数を示す。）
上記の式［２ａ］で示されるアルコキシシランは、特定ポリシロキサン系重合体の溶媒への溶解性、液晶配向膜にした際の液晶の垂直配向性、さらには、液晶表示素子の光学特性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ができる。

(R ₁ represents an alkyl group having 1 to 3 carbon atoms. R ₂ represents an alkyl group having 1 to 3 carbon atoms. M represents an integer of 2 or 3. n represents an integer of 0 or 1. B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and B ² represents , An oxygen atom or —COO— * (where a bond marked with “*” binds to B ³ ) B ¹ is an oxygen atom or —COO— * (note that “*” is attached) The bond is bonded to (CH ₂ ) a ² ). a ¹ represents 0 or an integer of 1; a2 represents an integer of ² to 10. a ³ represents an integer of 0 or 1. )
The alkoxysilane represented by the above formula [2a] is used for the solubility of the specific polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.

式［２ｂ］中、Ｂ^１は、ビニル基、エポキシ基、アミノ基、メルカプト基、イソシアネート基、メタクリル基、アクリル基、ウレイド基又はシンナモイル基を有する炭素数２〜１２の有機基を示す。なかでも、入手の容易さの点から、置換基としてはビニル基、エポキシ基、アミノ基、メタクリル基、アクリル基又はウレイド基が好ましい。より好ましくは、メタクリル基、アクリル基又はウレイド基である。
Ｂ^２は、水素原子又は炭素数１〜５のアルキル基を示す。なかでも、水素原子又は炭素数１〜３のアルキル基が好ましい。

In the formula [2b], B ¹ represents an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acrylic group, a ureido group, or a cinnamoyl group. Among these, a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, or a ureido group is preferable as a substituent from the viewpoint of availability. More preferably, they are a methacryl group, an acryl group, or a ureido group.
B ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.

B ³ represents an alkyl group having 1 to 5 carbon atoms. Among these, from the viewpoint of polycondensation reactivity, an alkyl group having 1 to 3 carbon atoms is preferable.
m represents an integer of 1 or 2. Among these, 1 is preferable from the viewpoint of synthesis.
n shows the integer of 0-2. Of these, 0 or 1 is preferable.
p shows the integer of 0-3. Especially, the integer of 1-3 is preferable from the reactive viewpoint of polycondensation. More preferably, it is 2 or 3.
In the formula [2b], m + n + p is 4.

  Specific examples of the alkoxysilane represented by the formula [2b] include, for example, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxy Ethoxy) silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) Propyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, 2- 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyl Trimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, 3-mercaptopropyl (dimethoxy) methylsilane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoate) Sisilyl) propyl methacrylate, 3- (triethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (triethoxysilyl) ethyl methacrylate, 3- (trimethoxysilyl) ethyl methacrylate, 3- (triethoxy Silyl) ethyl acrylate, 3- (trimethoxysilyl) ethyl acrylate, 3- (triethoxysilyl) methyl methacrylate, 3- (trimethoxysilyl) methyl methacrylate, 3- (triethoxysilyl) methyl acrylate, 3- (trimethoxy Silyl) methyl acrylate, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N′— Riethoxysilylpropylurea, (R) -N-1-phenylethyl-N′-trimethoxysilylpropylurea, bis [3- (trimethoxysilyl) propyl] urea, bis [3- (tripropoxysilyl) propyl] Examples include urea and 1- [3- (trimethoxysilyl) propyl] urea.

Among them, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3- (trimethylsilane), which undergoes radical reaction by light. Ethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate or 3- (trimethoxysilyl) propyl methacrylate is preferred.
Furthermore, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxy which undergoes a crosslinking reaction by heat Silane is preferred.
The alkoxysilane represented by the formula [2b] has properties such as the solubility of the specific polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the situation, one kind or a mixture of two or more kinds can be used.

式［２ｃ］中、Ｄ^１は、水素原子又は炭素数１〜５のアルキル基を示す。これらのアルキル基の水素原子は、ハロゲン原子、窒素原子、酸素原子又は硫黄原子で置換されていても良い。なかでも、水素原子又は炭素数１〜３のアルキル基が好ましい。
Ｄ^２は、炭素数１〜５のアルキル基を示す。なかでも、重縮合の反応性の観点から、炭素数１〜３のアルキル基が好ましい。
ｎは０〜３の整数を示す。なかでも、０又は１が好ましい。

In the formula [2c], D ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The hydrogen atom of these alkyl groups may be substituted with a halogen atom, a nitrogen atom, an oxygen atom or a sulfur atom. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
D ² represents an alkyl group having 1 to 5 carbon atoms. Among these, from the viewpoint of polycondensation reactivity, an alkyl group having 1 to 3 carbon atoms is preferable.
n represents an integer of 0 to 3. Of these, 0 or 1 is preferable.

  Specific examples of the alkoxysilane represented by the formula [2c] include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Ethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dibutoxydimethylsilane, (chloromethyl) triethoxysilane, 3-chloropropyldimethoxy Methylsilane, 3-chloropropyltriethoxysilane, 2-cyanoethyltriethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane, hexyltri Tokishishiran, 3-trimethoxysilylpropyl chloride.

In the formula [2c], examples of the alkoxysilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like, and examples of the alkoxysilane represented by the formula [2c] include these It is preferable to use alkoxysilane.
The alkoxysilane represented by the formula [2c] has properties such as the solubility of the specific polysiloxane polymer in the solvent, the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed, and the optical characteristics of the liquid crystal display element. Depending on the situation, one type or a mixture of two or more types can be used.

  The specific polysiloxane polymer includes at least one selected from the group consisting of the alkoxysilane represented by the formula [2a], the alkoxysilane represented by the formula [2b], and the alkoxysilane represented by the formula [2c]. It is a polysiloxane obtained by condensation. Specifically, it is obtained by polycondensing polysiloxane obtained by polycondensation of one kind of alkoxysilane represented by the formula [2a] and two kinds of alkoxysilanes represented by the formulas [2a] and [2b]. Polysiloxane, polysiloxane obtained by polycondensation of two alkoxysilanes represented by formula [2a] and formula [2c], and 3 represented by formula [2a], formula [2b] and formula [2c] It is a polysiloxane obtained by polycondensation of a kind of alkoxysilane.

  Among these, from the viewpoint of polycondensation reactivity and solubility of the specific polysiloxane polymer in a solvent, polysiloxane obtained by polycondensation of plural types of alkoxysilanes is preferable. That is, polysiloxane obtained by polycondensation of two types of alkoxysilanes represented by the formulas [2a] and [2b], and two types of alkoxysilanes represented by the formulas [2a] and [2c] Or a polysiloxane obtained by polycondensation of three types of alkoxysilanes represented by the formulas [2a], [2b] and [2c]. Of these, polysiloxanes obtained by polycondensation of three types of alkoxysilanes represented by formula [2a], formula [2b] and formula [2c] are preferred.

When producing a specific polysiloxane-type polymer, when using multiple types of alkoxylane, it is preferable that the alkoxysilane represented by Formula [2a] is 1-40 mol% in all the alkoxysilanes. Especially, 1-30 mol% is preferable.
Moreover, it is preferable that the alkoxysilane represented by Formula [2b] is 1-70 mol% in all the alkoxysilanes. Especially, 1-60 mol% is preferable.
Furthermore, it is preferable that the alkoxysilane represented by Formula [2c] is 1-99 mol% in all the alkoxysilanes. Especially, 1-80 mol% is preferable.

The method for producing the specific polysiloxane polymer is not particularly limited. For example, a method obtained by polycondensing an alkoxysilane represented by formula [2a] in a solvent, a method obtained by polycondensing two types of alkoxysilanes represented by formula [2a] and formula [2b], A method obtained by polycondensation of two types of alkoxysilanes represented by formula [2a] and formula [2c] in a solvent, and three types represented by formula [2a], formula [2b] and formula [2c] Examples thereof include a method obtained by polycondensation of alkoxysilane in a solvent. The specific polysiloxane polymer of the present invention can be obtained as a solution obtained by polycondensing these alkoxysilanes and uniformly dissolved in a solvent.
The method for polycondensing the specific polysiloxane polymer is not particularly limited. For example, a method in which an alkoxysilane is hydrolyzed and polycondensed in an alcohol solvent or a glycol solvent can be mentioned. At that time, the hydrolysis / polycondensation reaction may be partially hydrolyzed or completely hydrolyzed. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 times the molar amount of water of all alkoxy groups in the alkoxysilane, but it is possible to add an excessive amount of water more than 0.5 times the molar amount. preferable. In order to obtain a specific polysiloxane-based polymer, the amount of water used in the hydrolysis / polycondensation reaction can be appropriately selected according to the purpose, but 0.5% of all alkoxy groups in the alkoxysilane can be selected. It is preferable that it is -2.5 times molar amount.

Also, for the purpose of promoting hydrolysis and polycondensation reaction, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid; alkaline such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine Catalysts such as compounds; metal salts such as hydrochloric acid, nitric acid, oxalic acid, etc. can be used.
Furthermore, the hydrolysis / polycondensation reaction can also be promoted by heating a solution in which the alkoxysilane is dissolved. The heating temperature and heating time in that case can be suitably selected according to the objective. For example, conditions such as heating and stirring at 50 ° C. for 24 hours and then stirring for 1 hour under reflux conditions may be mentioned.

As another method for polycondensation, a method in which a polycondensation reaction is carried out by heating a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to a solvent to prepare a solution of oxalic acid in advance, alkoxysilane is mixed in a state where the solution is heated.
The amount of succinic acid used in the reaction is preferably 0.2 to 2.0 mol with respect to 1 mol of all alkoxy groups in the alkoxysilane. This reaction can be carried out at a solution temperature of 50 to 180 ° C., but is preferably carried out under reflux for several tens of minutes to several tens of hours so that the solvent does not evaporate or volatilize.
In the polycondensation reaction for preparing the specific polysiloxane polymer, when a plurality of alkoxysilanes represented by the formula [2a], the formula [2b] and the formula [2c] are used, a plurality of the alkoxysilanes are mixed in advance. Even if it reacts using a mixture, you may react, adding multiple types of alkoxysilane sequentially.

  The solvent used for the polycondensation reaction of alkoxysilane is not particularly limited as long as it can dissolve alkoxysilane. Moreover, even if it is a solvent in which an alkoxysilane does not melt | dissolve, what is melt | dissolved will be sufficient as long as the polycondensation reaction of alkoxysilane progresses. As the solvent used at that time, an alcohol is generally generated by a polycondensation reaction of alkoxysilane, and therefore, an alcohol solvent, a glycol solvent, a glycol ether solvent, a solvent having good compatibility with alcohol, and the like are used.

  Specific examples of the solvent used in such a polycondensation reaction include alcohol solvents such as methanol, ethanol, propanol, butanol, 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 -Glycol solvents such as pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Cole 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 Glycol ether solvents such as monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, And solvents having good compatibility with alcohols such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, and m-cresol. In the polycondensation reaction, the above solvents may be used alone or in combination of two or more.

In the polysiloxane polymer solution obtained by the above method, the concentration of silicon atoms contained in all alkoxysilanes charged as raw materials in terms of SiO ₂ (also referred to as SiO ₂ conversion concentration) is 20% by mass or less. Is preferred. Especially, it is preferable that it is 5-15 mass%. By selecting an arbitrary concentration within this concentration range, the generation of gel in the solution can be suppressed, and a uniform polysiloxane polymer solution can be obtained.
In the present invention, the polysiloxane polymer solution obtained by the above method may be used as the specific polysiloxane polymer as it is, or if necessary, the polysiloxane polymer obtained by the above method. These solutions can be concentrated, diluted by adding a solvent, or substituted with another solvent to be used as a specific polysiloxane polymer.

As a solvent (also referred to as an additive solvent) used for dilution, a solvent used for a polycondensation reaction or other solvents may be used. The additive solvent is not particularly limited as long as the polysiloxane polymer is uniformly dissolved, and one or two or more types can be arbitrarily selected and used. Examples of such an additional solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvent used in the polycondensation reaction.
Further, in the present invention, when a polysiloxane polymer and other polymers are used as the specific polysiloxane polymer, the polysiloxane polymer is mixed before mixing the other polymer with the polysiloxane polymer. The alcohol generated during the polycondensation reaction of the coalescer is preferably distilled off at normal pressure or reduced pressure.

<Liquid crystal alignment agent>
The liquid crystal aligning agent in this invention is a coating solution for forming a liquid crystal aligning film, the specific cellulose polymer which is a component (A), the said formula [2-1] and a formula [B] which are a component (B). 2-2] is a coating solution containing a specific polysiloxane polymer having at least one specific side chain structure selected from the group consisting of the structure represented by 2-2] and a solvent.
The ratio of the specific cellulose polymer and the specific polysiloxane polymer in the liquid crystal aligning agent is 0.01 to 99 masses with respect to 1 part by mass of the specific polysiloxane polymer. Part is preferred. Especially, 0.1-9 mass parts is more preferable, and 0.1-3 mass parts is more preferable.

All the polymer components in the liquid crystal aligning agent may all be a specific cellulose polymer and a specific polysiloxane polymer, or other polymers may be mixed. Examples of other polymers include polysiloxane polymers having no specific side chain represented by the formula [2-1] or the formula [2-2]. Further, at least one polymer selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyamide, polyester, polyamic acid and polyimide can also be mixed.
The content of other polymers is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of all the polymers including the specific cellulose polymer and the specific polysiloxane polymer. Especially, 1-10 mass parts is preferable.

Content of the solvent in a liquid-crystal aligning agent can be suitably selected from a viewpoint of obtaining the coating method of a liquid-crystal aligning agent, and the target film thickness. Especially, it is preferable that content of the solvent in a liquid-crystal aligning agent is 50-99.9 mass% from a viewpoint that a uniform liquid crystal aligning film is formed by application | coating. Especially, 60-99 mass% is preferable, and 65-99 mass% is more preferable.
The solvent used for the liquid crystal aligning agent is not particularly limited as long as the solvent dissolves the specific cellulose polymer and the specific polysiloxane polymer.
The solvent used for the liquid crystal aligning agent may be a polycondensation solution of the specific polysiloxane polymer as it is, or a new solvent may be added to the polycondensation solution of the specific polysiloxane polymer, Furthermore, the polycondensation solution of the specific polysiloxane polymer may be replaced with a new solvent. The new solvent is not particularly limited as long as it is a solvent that dissolves the specific cellulose polymer and the specific polysiloxane polymer. Although the specific example is given to the following, it is not limited to these examples.

  For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl 2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 -Butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, Dioxane, ethylene glycol dimethyl ether, ethylene glycol Recall diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- Heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- ( Methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether Ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, Tylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- ( 2-Ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol Monoethyl ether, 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, methyl lactate, ethyl lactate, Examples include lactic acid n-propyl ester, lactic acid n-butyl ester, and lactic acid isoamyl ester. Furthermore, the solvent shown by the following formula [A1]-a formula [A3] is also mentioned.

（Ａ^１は、炭素数１〜３のアルキル基を示す。Ａ^２は、炭素数１〜３のアルキル基を示す。Ａ^３は、炭素数１〜４のアルキル基を示す。）

(A ¹ represents an alkyl group having 1 to 3 carbon atoms. A ² represents an alkyl group having 1 to 3 carbon atoms. A ³ represents an alkyl group having 1 to 4 carbon atoms.)

  Among them, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 2-methyl-1-butanol, 1-hexanol, cyclohexanol, 1, 3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol monobutyl ether, ethylene glycol methyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol isobutyl ether Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, furfuryl alcohol, or formula [A1] to A solvent represented by the formula [A3] is preferable.

More preferred are methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1,3-propanediol, 1,3-butanediol, 1,4- Butanediol, 2,3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol Lumpur methyl ether, dipropylene glycol dimethyl ether, and the like solvents represented by the furfuryl alcohol, or formula [A1] ~ formula [A3].
One or two kinds of the above-mentioned solvents are used depending on the solubility of the specific cellulose polymer and the specific polysiloxane and the coating properties and surface smoothness characteristics of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied. The above can be mixed and used.

The liquid crystal aligning agent in the present invention includes at least one selected from the group consisting of structures represented by the following formulas [B1] to [B8] for the purpose of enhancing the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. It is preferable to introduce a compound (also referred to as a specific adhesion compound).
It is preferable that two or more structures represented by these formulas [B1] to [B8] are included in the adhesive compound.

（Ｂ^１は、水素原子又はベンゼン環を示す。Ｂ^２は、ベンゼン環、シクロへキサン環及び複素環からなる群から選ばれる少なくとも１種の環状基を示す。Ｂ^３は、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のアルコキシル基及び炭素数１〜１８のフッ素含有アルコキシル基からなる群から選ばれる少なくとも１種を示す。）

(B ¹ represents a hydrogen atom or a benzene ring. B ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. B ³ represents a carbon number of 1 to 1. And at least one selected from the group consisting of an 18 alkyl group, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.)

式［６］中、Ｍ^１は、下記の式［ａ−１］〜［ａ−７］で示される構造からなる群から選ばれる少なくとも１種の構造を示す。なかでも、本発明の密着性化合物の製造の容易さの点から、式［ａ−１］、式［ａ−２］、式［ａ−３］、式［ａ−５］又は式［ａ−６］で示される構造が好ましい。より好ましくは、式［ａ−１］、式［ａ−３］、式［ａ−５］又は式［ａ−６］で示される構造である。As a more specific specific adhesive compound, it is preferable to use a compound represented by the following formula [6].

In the formula [6], M ¹ represents at least one structure selected from the group consisting of structures represented by the following formulas [a-1] to [a-7]. Especially, from the point of the ease of manufacture of the adhesive compound of the present invention, the formula [a-1], the formula [a-2], the formula [a-3], the formula [a-5] or the formula [a- 6] is preferable. A structure represented by the formula [a-1], the formula [a-3], the formula [a-5] or the formula [a-6] is more preferable.

In the formula [a-2], A ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound. More preferably, they are a hydrogen atom or a methyl group.
In the formula [a-3], A ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound. More preferably, they are a hydrogen atom or a methyl group.
In formula [a-5] and formula [a-6], A ³ , A ⁵ , A ⁶ and A ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound. More preferably, they are a hydrogen atom or a methyl group.
In formula [a-5] and [a-6], A ⁴ , A ⁷ and A ⁸ each independently represent an alkylene group having 1 to 3 carbon atoms. Among these, an alkylene group having 1 to 2 carbon atoms is preferable from the viewpoint of easy production of the adhesive compound.

In formula [6], M ² represents a single bond, —CH ₂ —, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH. _{2 -, - COO -, -} OCO -, - CON (CH 3) - and exhibits at least one bond group selected from -N _(CH 3) group consisting of CO-. Among these, from the viewpoint of easy synthesis of the adhesive compound, a single bond, —CH ₂ —, —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, -COO -, - OCO -, - CON (CH 3) - or -N _(CH 3) CO- is preferred. More preferably, they are a single bond, —CH ₂ —, —O—, —NH—, —CONH—, —CH ₂ O—, —OCH ₂ —, —COO— or —OCO—. Particularly preferred is a single bond, —O—, —CONH—, —OCH ₂ —, —COO— or —OCO—.

In Formula [6], M ³ represents an alkylene group having 1 to 20 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p represents an integer of 1 to 10), — (CH ₂ —O—). ) _Q- (q represents an integer of 1 to 10) and at least one selected from the group consisting of organic groups having a benzene ring or a cyclohexane ring having 6 to 20 carbon atoms. In this case, any —CH ₂ — group of the alkylene group is —COO—, —OCO—, —CONH—, NHCO—, —CO—, —S—, —SO ₂ —, —CF ₂ —, — _{C (CF 3) 2 -,} - Si (CH 3) 2 -, - OSi (CH 3) 2 - or -Si _{(CH 3)} may be replaced by 2 O-, bonded to any carbon atom The hydrogen atom may be replaced by a hydroxyl group (OH group), a carboxyl group (COOH group) or a halogen atom.

From the standpoint of ease of manufacture of the adhesion compound, an alkylene group having 1 to 20 carbon _atoms, - (indicating p is an integer of from 1 to _{10), - - (CH 2 -CH} 2 -O) p ( A structure represented by CH ₂ —O—) _q — (q represents an integer of 1 to 10) or the following formulas [c-1] to [c-5] is preferable. More preferably, an alkylene group having 1 to 15 carbon _{atoms, - (CH 2 -CH 2 -O} ) p - (p is an integer of _{1~10), - (CH 2 -O-} ) q - (q is 1 to 10), and a structure represented by the following formula [c-1], formula [c-3], formula [c-4], or formula [c-5]. Particularly preferably, an alkylene group having 1 to 15 carbon atoms, — (CH ₂ —CH ₂ —O) _p — (p represents an integer of 1 to 10), Formula [c-1], Formula [c-4] Or it is a structure shown by Formula [c-5].

式［６］中、Ｍ^４は、単結合、−ＣＨ_２−、−ＯＣＨ_２−及びＯ−ＣＨ_２−ＣＨ_２−からなる群から選ばれる少なくとも１種の結合基を示す。なかでも、密着性化合物の合成の容易さの点から、単結合、−ＣＨ_２−又は−ＯＣＨ_２−で示される構造が好ましい。
式［６］中、Ｍ^５は、前記式［ｂ−１］〜［ｂ−８］で示される構造からなる群から選ばれる少なくとも１種の構造を示す。なかでも、密着性化合物の合成の容易さの点から、式［ｂ−１］、式［ｂ−２］又は式［ｂ−６］で示される構造が好ましい。より好ましくは、式［ｂ−１］又は式［ｂ−２］で示される構造である。
式［６］中、ｎは１〜３の整数を示す。なかでも、密着性化合物の合成の容易さの点から、１又は２が好ましい。より好ましいのは、１である。
式［６］中、ｍは１〜３の整数を示す。なかでも、密着性化合物の合成の容易さの点から、１又は２が好ましい。

In formula [6], M ⁴ represents at least one linking group selected from the group consisting of a single bond, —CH ₂ —, —OCH ₂ —, and O—CH ₂ —CH ₂ —. Among these, a structure represented by a single bond, —CH ₂ — or —OCH ₂ — is preferable from the viewpoint of easy synthesis of the adhesive compound.
In Formula [6], M ⁵ represents at least one structure selected from the group consisting of the structures represented by Formulas [b-1] to [b-8]. Especially, the structure shown by Formula [b-1], Formula [b-2], or Formula [b-6] is preferable from the point of the ease of the synthesis | combination of an adhesive compound. A structure represented by formula [b-1] or formula [b-2] is more preferable.
In formula [6], n shows the integer of 1-3. Especially, 1 or 2 is preferable from the point of the ease of the synthesis | combination of an adhesive compound. More preferred is 1.
In formula [6], m shows the integer of 1-3. Especially, 1 or 2 is preferable from the point of the ease of the synthesis | combination of an adhesive compound.

（ｎは１〜１０の整数を示す。ｍは１〜１０の整数を示す。）As the specific adhesion compound, it is preferable to use at least one compound selected from the group consisting of compounds represented by the following formulas [6-1] and [6-5].

(N represents an integer of 1 to 10. m represents an integer of 1 to 10.)

  Further, specific adhesive compounds include those shown below. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, etc. Compounds having three polymerizable unsaturated groups in the molecule; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate Rate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate , Ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, etc. Compounds having two groups in the molecule; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylic 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, And compounds having one polymerizable unsaturated group in the molecule, such as 2- (meth) acryloyloxyethyl phosphate ester and N-methylol (meth) acrylamide.

The content of the specific adhesive compound in the liquid crystal aligning agent is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. In order for the crosslinking reaction to proceed and to achieve the desired effect, 0.1 to 100 parts by weight is more preferable, and 1 to 50 parts by weight is most preferable, with respect to 100 parts by weight of all polymer components.
The specific adhesion compound may be used singly or in combination of two or more depending on the vertical alignment property of the liquid crystal when the vertical liquid crystal alignment film is formed, and the characteristics such as the optical characteristics of the liquid crystal display element. it can.

The liquid crystal alignment treatment agent in the present invention has at least one specific selected from the group consisting of a photo radical generator, a photo acid generator and a photo base generator for the purpose of improving the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. It is preferable to introduce a generator.
The photoradical generator is not particularly limited as long as it generates radicals by ultraviolet rays. For example, tert-butylperoxy-iso-butrate, 2,5-dimethyl-2,5-bis (benzoyldioxy) Xanthine, 1,4-bis [α- (tert-butyldioxy) -iso-propoxy] benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, α- (iso-propylphenyl) -iso-propylhydroperoxide, 2,5-dimethylhexane, tert-butylhydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane , Butyl-4,4-bis (tert-butyldioxy) valley Cyclohexanone peroxide, 2,2 ′, 5,5′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 3, 3 ′, 4,4′-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3′-bis (tert-butylperoxycarbonyl) ) -4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, organic peroxides such as di-tert-butyldiperoxyisophthalate; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octa Methylanthraquinone, 1,2-be Quinones such as nesanthraquinone; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin; and the like.

  The photoacid generator and photobase generator are not particularly limited as long as they generate an acid or a base by ultraviolet rays. For example, triazine compounds, acetophenone derivative compounds, disulfone compounds, diazomethane compounds, sulfonic acid derivatives Examples thereof include compounds, diaryl iodonium salts, triaryl sulfonium salts, triaryl phosphonium salts, and iron arene complexes. More specifically, for example, diphenyl iodonium chloride, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium mesylate, diphenyl iodonium tosylate, diphenyl iodonium bromide, diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium hexafluoroarsenate. Bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) ) Iodonium trifluoromethanesulfonate, bis (p-tert-butylphenol) L) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenyl (P-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxy Phenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophos , Tri (p-ethoxyphenyl) phosphonium tetrafluoroborate, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexyl carbamate, di (methoxybenzyl) hexamethylene Examples thereof include dicarbamate, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexyl carbamate, and di (methoxybenzyl) hexamethylene dicarbamate.

Especially, it is preferable to use a photoradical generator for a specific generator from a viewpoint which can improve the adhesiveness of a liquid crystal layer and a liquid crystal aligning film efficiently.
It is preferable that content of the specific generating agent in a liquid-crystal aligning agent is 0.01-50 mass parts with respect to 100 mass parts of all the polymer components. Especially, in order for a crosslinking reaction to advance and to express the target effect, 0.01-30 mass parts is more preferable with respect to 100 mass parts of all the polymer components, and more preferable is 0.1-30 mass parts. 20 parts by mass.
The specific generating agent can be used singly or in combination of two or more depending on the vertical alignment property of the liquid crystal when the vertical liquid crystal alignment film is formed, and further the optical characteristics of the liquid crystal display element. .

  From the viewpoint of increasing the film hardness of the vertical liquid crystal alignment film, the liquid crystal aligning agent in the present invention is selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group. It is preferable to introduce a compound having at least one selected substituent (collectively referred to as a specific crosslinking compound). It is necessary to have two or more of these substituents in the crosslinkable compound.

  Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, Liglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3 -Epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

具体的には、国際公開公報ＷＯ２０１１／１３２７５１（２０１１．１０．２７公開）の５８頁〜５９頁に掲載される式［４ａ］〜［４ｋ］で示される架橋性化合物が挙げられる。The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

Specific examples include crosslinkable compounds represented by formulas [4a] to [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).

具体的には、国際公開公報ＷＯ２０１２／０１４８９８（２０１２．２．２公開）の７６頁〜８２頁に掲載される式［５−１］〜［５−４２］で示される架橋性化合物が挙げられる。The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

Specific examples include crosslinkable compounds represented by the formulas [5-1] to [5-42] published on pages 76 to 82 of International Publication No. WO2012 / 014898 (2012.2.2 publication). .

  Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin, ethylene urea-formaldehyde resin, etc. are mentioned. Specifically, a melamine derivative in which a hydrogen atom of an amino group is substituted with a methylol group and / or an alkoxymethyl group, a benzoguanamine derivative, glycoluril, or the like can be used. The melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

  As an example of such a melamine derivative or a benzoguanamine derivative, MX-750 in which an average of 3.7 methoxymethyl groups is substituted per one triazine ring in a commercially available product, and an average of 5. methoxymethyl groups per one triazine ring. Methoxy-methylated melamines such as 8 substituted MW-30 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712; Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254; butoxymethylated melamine such as Cymel 506, 508; carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141; Methoxymethylated ethoxy A methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10; a butoxymethylated benzoguanamine such as Cymel 1128; a carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 And the like. Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170; methylolated glycoluril such as Cymel 1172; methoxymethylolated glycoluril such as Powderlink 1174;

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.
More specifically, the crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed on pages 62 to 66 of International Publication No. WO2011 / 132751.

  It is preferable that content of the crosslinkable compound in a liquid-crystal aligning agent is 0.1-100 mass parts with respect to 100 mass parts of all the polymer components. In order for the crosslinking reaction to proceed and to exhibit the desired effect, the amount is more preferably 0.1 to 50 parts by weight, and most preferably 1 to 30 parts by weight with respect to 100 parts by weight of all polymer components.

  In the present invention, as a compound that promotes charge transfer in the vertical liquid crystal alignment film and promotes charge release of the device, it is published on pages 69 to 73 of International Publication No. WO2011 / 132751 (published 2011.10.20). The nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156] can also be added to the liquid crystal aligning agent. The amine compound may be added directly to the liquid crystal aligning agent, but it is preferable to add the amine compound after forming a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent. The solvent is not particularly limited as long as it is an organic solvent that dissolves the specific cellulose polymer and the specific polysiloxane polymer.

Moreover, the compound which improves the uniformity of the film thickness of liquid crystal aligning film at the time of apply | coating a liquid crystal aligning agent, and surface smoothness can be used for a liquid-crystal aligning agent, unless the effect of this invention is impaired. Furthermore, a compound that improves the adhesion between the vertical liquid crystal alignment film and the substrate can also be used.
Examples of the compound that improves the film thickness uniformity and surface smoothness of the vertical liquid crystal alignment film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink, Inc.), Florard FC430, FC431 (or more) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. It is.

  Specific examples of the compound that improves the adhesion between the vertical liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like.

When using the compound to adhere to these substrates, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. 20 parts by mass. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the storage stability of the liquid crystal aligning agent may be deteriorated.
In addition to the compounds other than the above, the liquid crystal alignment treatment agent includes a dielectric material for changing the electrical properties such as the dielectric constant and conductivity of the vertical liquid crystal alignment film, as long as the effects of the present invention are not impaired. A conductive substance may be added.

<Liquid crystal composition>
The liquid crystal composition in the present invention is a liquid crystal composition containing at least a liquid crystal and a polymerizable compound that undergoes a polymerization reaction with ultraviolet rays.
As the liquid crystal, nematic liquid crystal, smectic liquid crystal, or cholesteric liquid crystal can be used. Among these, those having negative dielectric anisotropy are preferable. From the viewpoint of low voltage driving and scattering characteristics, those having a large dielectric anisotropy and a large refractive index anisotropy are preferred. Further, two or more kinds of liquid crystals can be mixed and used according to the respective physical property values of the phase transition temperature, dielectric anisotropy and refractive index anisotropy.

In order to drive a liquid crystal display element as an active element such as a TFT (Thin Film Transistor), it is required that the liquid crystal has a high electric resistance and a high voltage holding ratio (also referred to as VHR). Therefore, as the liquid crystal, it is preferable to use a fluorine-based or chlorine-based liquid crystal that has high electrical resistance and does not decrease VHR due to active energy rays such as ultraviolet rays.
Furthermore, the liquid crystal display element can also be made into a guest-host type element by dissolving a dichroic dye in a liquid crystal composition. In this case, an element is obtained that is transparent when no voltage is applied and absorbs (scatters) when a voltage is applied. In this liquid crystal display element, the direction of the liquid crystal director (orientation direction) changes by 90 degrees depending on the presence or absence of voltage application. Therefore, this liquid crystal display element can obtain a higher contrast than the conventional guest-host type element that switches between random alignment and vertical alignment by utilizing the difference in light absorption characteristics of the dichroic dye. In addition, in the guest-host type element in which the dichroic dye is dissolved, the liquid crystal is colored when aligned in the horizontal direction and becomes opaque only in the scattering state. Therefore, as the voltage is applied, it is possible to obtain an element that switches from colorless and transparent when no voltage is applied to a colored opaque and colored transparent state.

Any polymerizable compound may be used as long as it can form a cured product of the liquid crystal composition (for example, a polymer network) by a polymerization reaction with ultraviolet rays. At that time, a monomer of the polymerizable compound may be introduced into the liquid crystal composition, or a polymer obtained by polymerizing this monomer in advance may be introduced into the liquid crystal composition. However, even when a polymer is used, it is necessary to have a site that undergoes a polymerization reaction with ultraviolet rays. More preferably, from the viewpoint of handling the liquid crystal composition, that is, suppressing the increase in viscosity of the liquid crystal composition and solubility in the liquid crystal, a monomer is introduced into the liquid crystal composition, and irradiation of ultraviolet rays at the time of preparing the liquid crystal display device is performed. Thus, a method of forming a cured product by polymerization reaction is preferred.
The polymerizable compound may be any compound as long as it dissolves in the liquid crystal. However, when the polymerizable compound is dissolved in the liquid crystal, it is necessary that a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase exists. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, it is sufficient that the liquid crystal display element is confirmed with the naked eye and almost uniform transparency and scattering characteristics are obtained throughout the element.

The polymerizable compound may be a compound that causes a polymerization reaction by ultraviolet rays. At that time, the polymerization may proceed in any reaction form to form a cured product (cured product composite) of the liquid crystal composition. Specific reaction formats include radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction.
Especially, it is preferable that the reaction form of a polymeric compound is radical polymerization. In that case, the following radical type polymerizable compounds (monomers) and oligomers thereof can be used as the polymerizable compounds. Further, as described above, a polymer obtained by polymerizing these monomers can also be used.

  Examples of monofunctional polymerizable compounds (also referred to as monofunctional monomers) include 2-ethylhexyl acrylate, butyl ethyl acrylate, butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, hydroxyethyl acrylate, and 2-hydroxypropyl acrylate. 2-ethoxyethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, isodecyl Acrylate, lauryl acrylate, morpholine acrylate, phenoxyethyl acrylate, pheno Sidiethylene glycol acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,4 , 4,4-hexafluorobutyl acrylate, 2-ethylhexyl methacrylate, butylethyl methacrylate, butoxyethyl methacrylate, 2-cyanoethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethoxyethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, dicyclopentanyl methacrylate, dicyclopenteni Methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, isodecyl methacrylate, lauryl methacrylate, morpholine methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3 Examples thereof include monomers such as 3-tetrafluoropropyl methacrylate and 2,2,3,4,4,4-hexafluorobutyl methacrylate and oligomers thereof.

  Examples of the bipolymerizable compound (also referred to as bifunctional monomer) include 4,4′-diaacryloyloxystilbene, 4,4′-diaacryloyloxydimethylstilbene, 4,4′-diaacryloyloxydiethylstilbene, 4 , 4'-Diacryloyloxydipropylstilbene, 4,4'-Diacryloyloxydibutylstilbene, 4,4'-Diacryloyloxydipentylstilbene, 4,4'-Diacryloyloxydihexylstilbene, 4,4'-di Acryloyloxydifluorostilbene, 2,2,3,3,4,4-hexafluoropentanediol-1,5-diacrylate, 1,1,2,2,3,3-hexafluoropropyl-1,3-diacrylate Acrylate, diethylene glycol dimethacrylate, 1,4-butane Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, 4,4'-biphenyl diacrylate, diethylstilbestrol diacrylate 1,4-bisacryloyloxybenzene, 4,4′-bisacryloyloxydiphenyl ether, 4,4′-bisacryloyloxydiphenylmethane, 3,9- [1,1-dimethyl-2-acryloyloxyethyl] -2, 4,8,10-tetraspiro [5,5] undecane, α, α′-bis [4-acryloyloxyphenyl] -1,4-diisopropylbenzene, 1,4-bisacryloyloxytetrafluorobenzene, 4,4 ′ Bisacryloyloxyoctafluorobiphenyl, diethylene glycol acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, dicyclopentanyl diacrylate, glycerol diacrylate, 1,6-hexanediol diacrylate, neo Pentyl glycol diacrylate, tetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,9-nonanediol dimethacrylate, polyethylene glycol dimethacrylate or polypropylene glycol dimethacrylate, or These oligomers are mentioned.

Examples of the polyfunctional polymerizable compound (also referred to as polyfunctional monomer) include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy. Pentaacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate or 2,2,3,3,4,4 -Hexafluoropentanediol-1,5-dimeta Relate, or the like of these oligomers and the like.
The radical type polymerizable compound may be used alone or in combination of two or more depending on the optical characteristics of the liquid crystal display element and the adhesion characteristics between the liquid crystal layer and the vertical liquid crystal alignment film.

In order to promote the formation of a cured product of the liquid crystal composition, a radical initiator that generates radicals by ultraviolet rays (also referred to as a polymerization initiator) is introduced into the liquid crystal composition for the purpose of promoting radical polymerization of the polymerizable compound. It is preferable. For example, tert-butylperoxy-iso-butarate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [α- (tert-butyldioxy) -iso-propoxy] benzene, Di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, α- (iso-propylphenyl) -iso-propyl hydroperoxide, 2,5-dimethylhexane , Tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4-bis (tert-butyldioxy) valerate, cyclohexanone peroxide, 2 , 2 ′, 5,5′-tetra (tert-butylperoxy Carbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3 ′, 4 , 4'-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3'-bis (tert-butylperoxycarbonyl) -4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxy Organic peroxides such as isophthalate; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone; benzoin methyl, benzoin ethyl ether, α-me Le benzoin, benzoin derivatives such as α- phenylbenzoin; and the like.
These radical initiators can be used alone or in combination of two or more depending on the optical properties of the liquid crystal display element and the adhesion properties between the liquid crystal layer and the vertical liquid crystal alignment film.

As the polymerizable compound, the following ionic polymerizable compounds can also be used. Specifically, it is a compound having at least one cross-linking group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group.
More specifically, a melamine derivative, a benzoguanamine derivative, glycoluril, etc. in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group or both are mentioned. These melamine derivatives and benzoguanamine derivatives may be oligomers. These preferably have an average of 3 or more and less than 6 methylol groups or alkoxymethyl groups per one triazine ring.

  Specific examples of such melamine derivatives and benzoguanamine derivatives include, for example, MX-750 in which an average of 3.7 methoxymethyl groups are substituted per commercially available triazine ring; methoxymethyl per triazine ring MW-30 substituted with an average of 5.8 groups (manufactured by Sanwa Chemical Co., Ltd.); methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 Methoxymethylated butoxymethylated melamines such as Cymel 235, 236, 238, 212, 253, 254; butoxymethylated melamines such as Cymel 506, 508; methoxymethylated isobutoxymethylated containing carboxyl groups such as Cymel 1141; Melamine; Methoxy like Cymel 1123 Titrated ethoxymethylated benzoguanamine; methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128; methoxymethylated ethoxymethylated benzoguanamine containing carboxyl groups such as Cymel 1125-80 (Mitsui Cytec Co., Ltd.). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and the like.

Examples of the benzene having a hydroxyl group or an alkoxyl group or a phenolic compound include 1,3,5-tris (methoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, and 1,4-bis. (Sec-butoxymethoxy) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.
In addition, as the ionic polymerizable compound, a compound containing an epoxy group or an isocyanate group and having a crosslinking group can also be used.

  Specifically, for example, bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis ( Aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2, 2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglyce Zirmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3-epoxypropoxyphenyl) -1-methyl) And ethyl) phenyl) ethyl) phenoxy) -2-propanol.

When an ionic polymerizable compound is used, an ion initiator that generates an acid or a base by the following ultraviolet rays can be introduced for the purpose of promoting the polymerization reaction. Specifically, for example, a triazine compound, an acetophenone derivative compound, a disulfone compound, a diazomethane compound, a sulfonic acid derivative compound, a diaryliodonium salt, a triarylsulfonium salt, a triarylphosphonium salt, an iron arene complex, or the like may be used. However, it is not limited to these.
More specifically, for example, diphenyl iodonium chloride, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium mesylate, diphenyl iodonium tosylate, diphenyl iodonium bromide, diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium hexafluoroarsenate. Bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) ) Iodonium trifluoromethanesulfonate, bis (p-tert-butylphenol) L) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenyl (P-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxy Phenyl) phosphonium tetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophos , Tri (p-ethoxyphenyl) phosphonium tetrafluoroborate, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexyl carbamate, di (methoxybenzyl) hexamethylene Examples thereof include dicarbamate, bis [[(2-nitrobenzyl) oxy] carbonylhexane-1,6-diamine], nitrobenzylcyclohexyl carbamate, and di (methoxybenzyl) hexamethylene dicarbamate.
In the liquid crystal display element of the present invention, it is preferable to use a radical type polymerizable compound among the above polymerizable compounds from the viewpoint of optical characteristics.

The amount of the polymerizable compound introduced into the liquid crystal composition is not particularly limited, but when the amount of the polymerizable compound introduced is large, the polymerizable compound does not dissolve in the liquid crystal or the temperature at which the liquid crystal composition exhibits a liquid crystal phase. Or the change between the transparent state and the scattering state of the element becomes small, and the optical characteristics deteriorate. Further, when the amount of the polymerizable compound introduced is small, the curability of the liquid crystal layer is lowered, and further, the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered, and the liquid crystal orientation is not affected by mechanical external pressure. It becomes easy to get confused. Therefore, the introduction amount of the polymerizable compound is preferably 1 to 50 parts by mass, and more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the liquid crystal. Especially preferably, it is 11-30 mass parts.
The amount of radical initiator or ion initiator that accelerates the reaction of the polymerizable compound is not particularly limited, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the liquid crystal. 0.05 to 5 parts by mass is more preferable. Particularly preferably, it is 0.05 to 3 parts by mass.

<Method for Manufacturing Vertical Liquid Crystal Alignment Film and Liquid Crystal Display Element>
The substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, and a PET (polyethylene terephthalate) substrate, and those The film can be used. When the liquid crystal display element is used as a reverse type element for a light control window or the like, a plastic substrate or a film is preferable. From the viewpoint of simplification of the process, a substrate on which an ITO (Indium Tin Oxide) electrode, an IZO (Indium Zinc Oxide) electrode, an IGZO (Indium Gallium Zinc Oxide) electrode, an organic conductive film, etc. are formed. Is preferably used. In the case of a reflective reverse element, a substrate on which a metal or dielectric multilayer film such as a silicon wafer or aluminum is formed can be used as long as the substrate is only on one side.

In the liquid crystal display element of the present invention, at least one of the substrates has a vertical liquid crystal alignment film that vertically aligns liquid crystal molecules. This vertical liquid crystal alignment film can be obtained by applying a liquid crystal alignment treatment agent on a substrate and baking it, followed by alignment treatment by rubbing treatment or light irradiation. However, the vertical liquid crystal alignment film in the present invention can be used as the vertical liquid crystal alignment film without these alignment treatments.
The application method of the liquid crystal aligning agent is not particularly limited, but industrially includes screen printing, offset printing, flexographic printing, ink jet method, dipping method, roll coater method, slit coater method, spinner method, spray method, etc. Depending on the kind of the substrate and the desired thickness of the vertical liquid crystal alignment film, it can be appropriately selected.

After the liquid crystal alignment treatment agent is applied on the substrate, the heating means such as a hot plate, a thermal circulation oven, an IR (infrared) oven, or the like is used, depending on the type of substrate and the solvent used for the liquid crystal alignment treatment agent. The vertical liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 300 ° C., preferably 30 to 250 ° C. In particular, when a plastic substrate is used as the substrate, the treatment is preferably performed at a temperature of 30 to 150 ° C.
If the thickness of the vertical liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the element may be lowered. More preferably, it is 10-300 nm, Especially preferably, it is 10-250 nm.
The liquid crystal composition used in the liquid crystal display element of the present invention is the liquid crystal composition as described above, and a spacer for controlling the electrode gap (also referred to as a gap) of the liquid crystal display element may be introduced therein. it can.

Although the injection method of a liquid crystal composition is not specifically limited, For example, the following method is mentioned. That is, when a glass substrate is used as a substrate, a pair of substrates on which a vertical liquid crystal alignment film is formed is prepared, and a sealant is applied to four pieces of one side of the substrate except for a part, and then the vertical liquid crystal alignment film is formed. An empty cell is manufactured by attaching the substrate on the other side so that the surface is on the inside. A method of obtaining a liquid crystal composition injection cell by injecting the liquid crystal composition under reduced pressure from a place where the sealant is not applied can be mentioned. Furthermore, when a plastic substrate or film is used as the substrate, a pair of substrates with a vertical liquid crystal alignment film is prepared, and the liquid crystal composition is formed on one substrate by ODF (One Drop Filling) method or inkjet method. There is a method in which a liquid crystal composition injection cell is obtained by dropping an object and then bonding the other substrate together.
In the liquid crystal display element of the present invention, since the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is high, it is not necessary to apply the sealing agent to the four pieces of the substrate.

The gap of the liquid crystal display element can be controlled by the spacer or the like. Examples of the method include a method of introducing a spacer having a target size into the liquid crystal composition as described above, and a method of using a substrate having a column spacer having a target size. In addition, when a plastic or film substrate is used as a substrate and the substrates are bonded together by lamination, the gap can be controlled without introducing a spacer.
As for the magnitude | size of the gap of a liquid crystal display element, 1-100 micrometers is preferable, More preferably, it is 2-50 micrometers. Especially preferably, it is 5-20 micrometers. If the gap is too small, the contrast of the liquid crystal display element is lowered. If the gap is too large, the driving voltage of the element is increased.

The liquid crystal display element of the present invention can be obtained by curing the liquid crystal composition in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of liquid crystal and a polymerizable compound. The liquid crystal composition is cured by at least one of ultraviolet irradiation and heating in the liquid crystal composition injection cell.
Examples of the light source of the ultraviolet irradiation device used at that time include a metal halide lamp and a high-pressure mercury lamp. The wavelength of the ultraviolet light is preferably 250 to 400 nm. Especially, 310-370 nm is preferable. Moreover, in the case of heat processing, the temperature is 40-120 degreeC, Preferably it is 60-80 degreeC. Further, both the ultraviolet treatment and the heat treatment may be performed simultaneously, or the heat treatment may be performed after the ultraviolet treatment. In the present invention, it is preferable to cure the liquid crystal composition only by ultraviolet treatment.

As described above, a liquid crystal display element using a vertical liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a cellulose polymer having a specific structure and a polysiloxane polymer having a side chain having a specific structure according to the present invention is a liquid crystal display element. Liquid crystal display element with high adhesion between the layer and the vertical liquid crystal alignment film, and further with high vertical alignment of the liquid crystal and good optical characteristics, that is, transparency when no voltage is applied and scattering characteristics when a voltage is applied It becomes. In particular, this device can be suitably used for reverse-type devices that become transparent when no voltage is applied, and scatter when voltage is applied, and control the transmission and blocking of light for display purposes. It is useful as a light control window or an optical shutter element. In this case, it is preferable to use a plastic substrate or a film as the substrate.
In addition, the liquid crystal display element of the present invention is a liquid crystal display element used in transportation equipment and transportation machines such as automobiles, railways, and aircrafts, specifically, light used for light control windows and room mirrors that control transmission and blocking of light. It can be suitably used for a shutter element or the like. In particular, this element has good transparency when no voltage is applied and good scattering characteristics when a voltage is applied, so when used for a glass window of a vehicle, compared to using a conventional reverse type element, The efficiency of taking in light at night is high, and the effect of preventing glare from outside light is also enhanced. Therefore, it is possible to further improve the safety when driving a vehicle and the comfort when riding. Also, when this element is made of film and pasted on a vehicle glass window, the low reverse adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is less likely to cause defects and deterioration. Reliability is higher than

  Furthermore, the liquid crystal display element of the present invention can also be used for a light guide plate of a display device such as an LCD (Liquid Crystal Display) or an OLED (Organic Light-emitting Diode) display, or a back plate of a transparent display using these displays. . Specifically, when the transparent display and the present element are combined and screen display is performed on the transparent display, the entry of light from the back surface can be suppressed by the present element. At that time, this element is applied with a voltage when performing screen display on a transparent display and becomes in a scattering state, and the screen display can be clarified. After the screen display is finished, a transparent state in which no voltage is applied. It becomes.

The present invention will be described in more detail with reference to the following examples, but should not be construed as being limited thereto. In addition, the abbreviation of the compound used by the synthesis example, the Example, and the comparative example is as follows.
<Liquid crystal composition>
(Liquid crystal) L1: MLC-6608 (Merck)
(Polymerizable compound) R1: Compound represented by the following formula [R1] (photoinitiator) P1: Compound represented by the following formula [P1]

(Specific cellulose polymer)
CE-1: Hydroxyethyl cellulose (manufactured by WAKO)
CE-2: Hydroxypropyl methylcellulose phthalate (manufactured by ACROS)
(Alkoxysilane monomer)
E1: Alkoxysilane represented by the following formula [E1] E2: Octadecyltriethoxysilane E3: 3-methacryloxypropyltrimethoxysilane E4: 3-ureidopropyltriethoxysilane E5: Tetraethoxysilane

(Specific generation agent)
S1: Photoradical generator represented by the following formula [S1] S2: Photoradical generator represented by the following formula [S2]

(Specific adhesive compound)
M1: Compound represented by the following formula [M1] M2: Compound represented by the following formula [M2] M3: Compound represented by the following formula [M3]

(Specific crosslinkable compound)
K1: Compound represented by the following formula [K1]

(solvent)
PGME: propylene glycol monomethyl ether ECS: ethylene glycol monoethyl ether BCS: ethylene glycol monobutyl ether PB: propylene glycol monobutyl ether EC: diethylene glycol monoethyl ether

"Synthesis of polysiloxane polymers"
<Synthesis Example 1>
In a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube, ECS (28.3 g), E1 (4.10 g), E3 (7.45 g) and E5 (32.5 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, a solution prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise at 25 ° C. over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 g) with an E4 content of 92 mass% and ECS (0.90 g) was added. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (1) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 2>
In a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube, PGME (28.3 g), E1 (8.20 g), E3 (19.9 g) and E5 (20.0 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, a solution prepared by mixing PGME (19.1 g), water (10.8 g) and oxalic acid (1.10 g) as a catalyst in advance was added dropwise at 25 ° C. over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 g) containing 92% by mass of E4 and PGME (0.90 g) was added. It was. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (2) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 3>
Prepare a solution of alkoxysilane monomer by mixing ECS (29.2 g), E1 (4.10 g) and E5 (38.8 g) in a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube. did. To this solution, a solution prepared by mixing ECS (12.1 g), water (10.8 g) and oxalic acid (0.50 g) as a catalyst in advance at 25 ° C. was added dropwise over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of methanol solution (1.20 g) containing 92% by mass of E4 and ECS (0.90 g) was added. It was. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (3) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 4>
In a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube, PGME (28.3 g), E2 (4.07 g), E3 (7.45 g) and E5 (32.5 g) were mixed, A solution of alkoxysilane monomer was prepared. To this solution, a solution prepared by mixing PGME (14.2 g), water (10.8 g) and oxalic acid (0.70 g) as a catalyst was added dropwise at 25 ° C. over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 g) having a content of E4 of 92% by mass and PGME (0.90 g) was added. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (4) having a SiO ₂ equivalent concentration of 12% by mass.

<Synthesis Example 5>
Prepare a solution of alkoxysilane monomer by mixing ECS (27.7 g), E3 (7.45 g) and E5 (32.5 g) in a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube. did. To this solution, ECS (10.0 g), water (10.8 g) and a solution prepared by mixing oxalic acid (0.70 g) as a catalyst were added dropwise at 25 ° C. over 30 minutes, The mixture was further stirred at 25 ° C. for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 g) with an E4 content of 92 mass% and ECS (0.90 g) was added. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (5) having a SiO ₂ equivalent concentration of 12% by mass.
Table 1 shows the composition of the polysiloxane polymer (polysiloxane solution) obtained in each synthesis example and the alkoxysilane monomer used.

"Production of liquid crystal composition"
(Preparation of liquid crystal composition (1))
L1 (11.5 g), R1 (1.73 g) and P1 (0.12 g) were mixed, heated to 80 ° C., and then cooled to 25 ° C. to obtain a liquid crystal composition (1).
(Preparation of liquid crystal composition (2))
L1 (12.0 g), R1 (2.40 g) and P1 (0.12 g) were mixed, heated to 80 ° C. and then cooled to 25 ° C. to obtain a liquid crystal composition (2).

"Manufacture of liquid crystal alignment treatment agent"
Examples 1 to 15 and Comparative Examples 1 to 5 are production examples of a liquid crystal alignment treatment agent. This liquid crystal alignment treatment agent was also used for the production of a liquid crystal display element and its evaluation.
Tables 2 to 4 collectively show the liquid crystal alignment treatment agents, composition content ratios, and the like obtained in Examples and Comparative Examples.

"Production of liquid crystal display elements (glass substrate)"
The liquid crystal aligning agents obtained in Examples and Comparative Examples were pressure filtered through a membrane filter having a pore diameter of 1 μm to produce a liquid crystal display element. Specifically, this liquid crystal aligning agent was washed with pure water and IPA (isopropyl alcohol) and 100 × 100 mm ITO electrode-attached glass substrate (vertical: 100 mm, horizontal: 100 mm, thickness: 0.7 mm) ITO Spin coat on the surface, heat treatment at 100 ° C. for 5 minutes on a hot plate, and heat treatment at 200 ° C. for 15 minutes in a thermal circulation clean oven to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm. It was. Two ITO substrates with the obtained liquid crystal alignment film were prepared, and a 6 μm spacer was applied to the liquid crystal alignment film surface of one of the substrates. Then, the liquid crystal composition is dropped on the surface of the liquid crystal alignment film coated with the spacer of the substrate by ODF (One Drop Filling) method, and then bonded so that the liquid crystal alignment film interface of the other substrate faces. A liquid crystal display element before processing was obtained.
The liquid crystal display element before this treatment was irradiated with ultraviolet rays of 7 J / cm ^{2 in} terms of 365 nm using a metal halide lamp with an illuminance of 60 mW while cutting a wavelength of 350 nm or less. At this time, the temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled to 25 ° C. Thereby, a liquid crystal display element (reverse type element) was obtained.

"Production of liquid crystal display elements (plastic substrates)"
The liquid crystal aligning agents obtained in Examples and Comparative Examples were pressure filtered through a membrane filter having a pore diameter of 1 μm to produce a liquid crystal display element. Specifically, this liquid crystal aligning agent is washed with pure water on a 150 × 150 mm PET (polyethylene terephthalate) substrate with ITO electrodes (length: 150 mm, width: 150 mm, thickness: 0.2 mm) on the ITO surface. An ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm is coated with a bar coater and heat-treated on a hot plate at 100 ° C. for 5 minutes and in a heat-circulating clean oven at 150 ° C. for 1 minute. Got. Two ITO substrates with the obtained liquid crystal alignment film were prepared, and a 6 μm spacer was applied to the liquid crystal alignment film surface of one of the substrates. Thereafter, the liquid crystal composition is dropped onto the surface of the liquid crystal alignment film coated with the spacer of the substrate by the ODF method, and then bonded so that the interface of the liquid crystal alignment film of the other substrate faces. A display element was obtained.
The liquid crystal display element before this treatment was irradiated with ultraviolet rays of 7 J / cm ^{2 in} terms of 365 nm using a metal halide lamp with an illuminance of 60 mW while cutting a wavelength of 350 nm or less. At this time, the temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled to 25 ° C. Thereby, a liquid crystal display element (reverse type element) was obtained.

"Evaluation of liquid crystal alignment (glass substrate)"
The liquid crystal orientation was evaluated using the liquid crystal display element (glass substrate) obtained by the above method. The liquid crystal orientation was observed with a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corporation) to confirm whether or not the liquid crystal was vertically aligned. Specifically, the liquid crystal aligned vertically is considered excellent in this evaluation (good display in Tables 5 to 7).
Thereafter, the liquid crystal display element (glass substrate) for which the evaluation of the liquid crystal orientation was completed was stored in a high temperature bath at a temperature of 100 ° C. for 336 hours. Thereafter, the liquid crystal alignment was evaluated under the same conditions as described above. Specifically, the liquid crystal orientation is not disturbed, and the liquid crystal is uniformly oriented, and this evaluation is excellent (good display in Tables 5 to 7).

"Evaluation of liquid crystal alignment (plastic substrate)"
The liquid crystal alignment was evaluated using the liquid crystal display element (plastic substrate) obtained by the above method. The liquid crystal orientation was observed with a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corporation) to confirm whether or not the liquid crystal was vertically aligned. Specifically, the liquid crystal aligned vertically is considered excellent in this evaluation (good display in Tables 5 and 6).
Thereafter, the liquid crystal display element (plastic substrate) for which the evaluation of the liquid crystal orientation was completed was stored in a high temperature bath at a temperature of 100 ° C. for 336 hours. Thereafter, the liquid crystal alignment was evaluated under the same conditions as described above. Specifically, the liquid crystal orientation is not disturbed and the liquid crystal is uniformly oriented, and this evaluation is excellent (good display in Tables 5 and 6).

"Evaluation of optical properties (transparency and scattering properties) (glass substrate)"
Optical characteristics (transparency and scattering characteristics) were evaluated using the liquid crystal display element (glass substrate) obtained by the above method.
Transparency when no voltage was applied was measured by measuring the transmittance of the liquid crystal display element when no voltage was applied. Specifically, UV-3600 (manufactured by Shimadzu Corporation) was used as a measurement device, and the glass substrate with an ITO electrode was used as a reference, and the transmittance was measured under conditions of a temperature of 25 ° C. and a scan wavelength of 300 to 800 nm. The evaluation was performed at a transmittance of a wavelength of 450 nm, and the higher the transmittance, the better the evaluation (the transmittance values are shown in Tables 8 to 10).
The scattering characteristics at the time of voltage application were performed by applying 40V to the liquid crystal display element by AC driving and visually observing the alignment state of the liquid crystal. Specifically, the element in which the present element becomes clouded, that is, the element in which the scattering characteristic is obtained is considered to be excellent in the present evaluation (good display in Tables 8 to 10).

"Evaluation of optical properties (transparency and scattering properties) (plastic substrate)"
Optical characteristics (transparency and scattering characteristics) were evaluated using the liquid crystal display element (plastic substrate) obtained by the above method.
Transparency when no voltage was applied was measured by measuring the transmittance of the liquid crystal display element when no voltage was applied. Specifically, UV-3600 (manufactured by Shimadzu Corporation) was used as a measurement device, and the PET substrate with an ITO electrode was used as a reference, and the transmittance was measured under conditions of a temperature of 25 ° C. and a scan wavelength of 300 to 800 nm. The evaluation was performed at a transmittance of a wavelength of 450 nm, and the higher the transmittance, the better this evaluation was (the transmittance values are shown in Tables 8 and 9).
The scattering characteristics at the time of voltage application were performed by applying 40V to the liquid crystal display element by AC driving and visually observing the alignment state of the liquid crystal. Specifically, the element in which the element was clouded, that is, the element in which the scattering characteristics were obtained was considered to be excellent in the present evaluation (good display in Tables 8 and 9).

"Evaluation of adhesion between liquid crystal layer and (vertical) liquid crystal alignment film (glass substrate)"
Using the liquid crystal display element on which the optical characteristics were evaluated, the adhesion between the liquid crystal layer and the liquid crystal alignment film was evaluated. Specifically, the liquid crystal display element was stored in a high-temperature and high-humidity tank having a temperature of 80 ° C. and a humidity of 90% RH for 96 hours, and presence or absence of bubbles in the element and peeling of the element were confirmed. At that time, the case where no bubbles were observed in the device and the device was not peeled (the liquid crystal layer and the liquid crystal alignment film were peeled off) was considered excellent in this evaluation (in Tables 8 to 10). Good display).

"Evaluation of adhesion between liquid crystal layer and (vertical) liquid crystal alignment film (plastic substrate)"
Using the liquid crystal display element on which the optical characteristics were evaluated, the adhesion between the liquid crystal layer and the liquid crystal alignment film was evaluated. Specifically, the liquid crystal display element was stored in a high-temperature and high-humidity tank having a temperature of 80 ° C. and a humidity of 90% RH for 96 hours, and presence or absence of bubbles in the element and peeling of the element were confirmed. At that time, the case where no bubbles were observed in the device and the device was not peeled (the liquid crystal layer and the liquid crystal alignment film were peeled off) was considered excellent in this evaluation (in Tables 8 and 9). Good display).

<Example 1>
EC-2 (11.0 g) and PB (14.2 g) were added to CE-2 (1.10 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (1) (13.8 g) obtained in Synthesis Example 1 was added to this solution, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (1). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 2>
Using the liquid crystal aligning agent (1) obtained in Example 1 and the liquid crystal composition (2), a liquid crystal display element (glass substrate, plastic substrate) was produced and evaluated.
<Example 3>
To CE-2 (1.40 g), ECS (15.1 g), PGME (15.1 g) and BCS (10.7 g) were added and stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (1) (14.3 g), S2 (0.156 g) and M2 (0.467 g) obtained in Synthesis Example 1 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours. A liquid crystal aligning agent (2) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 4>
To CE-2 (1.65 g), ECS (33.3 g), BCS (6.00 g) and EC (5.30 g) were added and stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (1) (13.8 g), S1 (0.165 g) and M2 (0.165 g) obtained in Synthesis Example 1 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours. A liquid crystal aligning agent (3) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 5>
PGME (28.7 g), BCS (5.70 g) and EC (5.70 g) were added to CE-2 (1.00 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (2) (19.4 g) obtained in Synthesis Example 2 was added to this solution and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (4). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 6>
PGME (21.8 g), ECS (10.9 g) and EC (5.40 g) were added to CE-2 (0.95 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (2) (18.5 g), S2 (0.159 g) and M1 (0.634 g) obtained in Synthesis Example 2 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours. A liquid crystal aligning agent (5) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 7>
PGME (27.9 g) and BCS (8.60 g) were added to CE-1 (0.50 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (2) (23.6 g), S2 (0.233 g) and M3 (0.500 g) obtained in Synthesis Example 2 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours. A liquid crystal aligning agent (6) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 8>
PGME (28.4 g) and PB (8.40 g) were added to CE-1 (0.65 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (2) (21.7 g), S2 (0.033 g), M2 (0.975 g) and K1 (0.163 g) obtained in Synthesis Example 2 were added to this solution at 25 ° C. Was stirred for 5 hours to obtain a liquid crystal aligning agent (7). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 9>
EC-2 (11.0 g) and PB (14.2 g) were added to CE-2 (1.10 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, to this solution, the polysiloxane solution (3) (13.8 g) obtained in Synthesis Example 3 was added and stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (8). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 10>
Using the liquid crystal aligning agent (8) obtained in Example 9 and the liquid crystal composition (2), a liquid crystal display element (glass substrate, plastic substrate) was produced and evaluated.
<Example 11>
ECS (35.6 g) and EC (5.30 g) were added to CE-2 (1.40 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (3) (14.3 g), S2 (0.311 g), M2 (0.778 g) and K1 (0.062 g) obtained in Synthesis Example 3 were added to this solution at 25 ° C. Was stirred for 5 hours to obtain a liquid crystal aligning agent (9). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 12>
ECS (17.8 g), PGME (17.8 g) and EC (5.30 g) were added to CE-2 (1.65 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (3) (11.3 g) obtained in Synthesis Example 3 was added to this solution, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (10). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 13>
PGME (25.6 g) and BCS (11.2 g) were added to CE-2 (0.65 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (4) (21.7 g) obtained in Synthesis Example 4 was added to this solution, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal aligning agent (11). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 14>
PGME (34.3 g) and PB (11.7 g) were added to CE-2 (1.70 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (4) (14.2 g), S1 (0.170 g) and M2 (0.170 g) obtained in Synthesis Example 4 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours. A liquid crystal aligning agent (12) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Example 15>
PGME (22.2 g) and BCS (14.3 g) were added to CE-1 (0.50 g), and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the polysiloxane solution (4) (23.6 g) and M3 (0.666 g) obtained in Synthesis Example 4 were added to this solution, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal alignment treatment agent (13). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 1>
ECS (6.50 g) and PB (8.50 g) were added to the polysiloxane solution (5) (15.0 g) obtained in Synthesis Example 5, and the mixture was stirred at 25 ° C. for 5 hours to obtain a liquid crystal alignment treatment agent ( 14) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 2>
ECS (6.80 g) and PB (8.70 g) were added to the polysiloxane solution (1) (15.5 g) obtained in Synthesis Example 1, and the mixture was stirred at 25 ° C. for 5 hours. 15) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 3>
Using the liquid crystal aligning agent (15) and liquid crystal composition (2) obtained in Comparative Example 2, production of a liquid crystal display element (glass substrate), evaluation of liquid crystal alignment (glass substrate), optical characteristics (transmittance) And scattering characteristics) (glass substrate) and adhesion between the liquid crystal layer and the liquid crystal alignment film (glass substrate) were evaluated.

<Comparative example 4>
ECS (6.50 g) and PB (8.50 g) were added to the polysiloxane solution (3) (15.0 g) obtained in Synthesis Example 3, and the mixture was stirred at 25 ° C. for 5 hours. 16) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.

<Comparative Example 5>
Using the liquid crystal aligning agent (16) obtained in Comparative Example 4 and the liquid crystal composition (2), a liquid crystal display element (glass substrate) was produced and evaluated.

<Evaluation of liquid crystal display elements of Examples 1 to 18 and Comparative Examples 1 to 5> As shown in Table 5, Table 6, Table 7, Table 8, Table 9, and Table 10 below, the liquid crystal display elements were obtained in the above examples. The liquid crystal alignment processing agents (1) to (13) or the liquid crystal alignment processing agents (14) to (16) obtained in Comparative Examples, respectively, and the liquid crystal composition (1) or (2) are used. The above-mentioned liquid crystal display device was prepared and the liquid crystal alignment was evaluated, the optical characteristics (transparency and scattering characteristics) were evaluated, and the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film was evaluated.
In addition, Examples 1, 2, 4, 6, 7, 9, 10, 11, 12, and 14 are performed using both glass substrate elements and plastic substrate elements, and Examples 3, 5, 8, 13, 15 And Comparative Examples 1-5 were performed with the element of the glass substrate. The results of these evaluations are summarized in Table 5, Table 6, Table 7, Table 8, Table 9, and Table 10.

  Further, in the evaluation of adhesion between the liquid crystal layer and the vertical liquid crystal alignment film in Examples 2, 3, 9, 11 and Comparative Examples 3 and 4, as an emphasis test together with the standard test, a temperature of 80 ° C. and a humidity of 90 Evaluation was also performed when stored in a high-temperature, high-humidity tank of% RH for 168 hours (other conditions were the same as those described above). As a result, in Examples 3 and 11, no bubbles were observed in the element, but in Examples 2 and 9, a small amount of bubbles were observed in the element. In Comparative Examples 3 and 4, many bubbles were observed in the element. Bubbles were observed, and peeling of the element was observed at some locations.

＊１：液晶が垂直に配向していなかった。
＊２：液晶配向性に乱れが見られた。
＊３：液晶が垂直に配向していないため、測定できなかった。
＊４：素子が、液晶層と液晶配向膜との間で剥離した。
＊５：素子内に、気泡が見られた。

* 1: The liquid crystal was not aligned vertically.
* 2: Disturbance was observed in liquid crystal alignment.
* 3: Since the liquid crystal was not vertically aligned, measurement was not possible.
* 4: The element peeled between the liquid crystal layer and the liquid crystal alignment film.
* 5: Bubbles were observed in the element.

As can be seen from the above results, the liquid crystal display element of the example has higher adhesion between the liquid crystal layer and the liquid crystal alignment film than the liquid crystal display element of the comparative example, and further, the vertical alignment property of the liquid crystal is high and good. Excellent optical characteristics, that is, transparency when no voltage was applied and scattering characteristics when a voltage was applied were good.
On the other hand, the liquid crystal display element of the comparative example has poor adhesion between the liquid crystal layer and the liquid crystal alignment film, and bubbles are observed in the element after being stored in a high-temperature and high-humidity tank, or the liquid crystal layer and the vertical alignment film peel off. To be observed. Further, in the liquid crystal display element of the comparative example, disordered liquid crystal alignment due to insufficient vertical alignment of liquid crystal was observed after storage in a high temperature bath.
Specifically, Examples containing the same specific polysiloxane-based polymer and not including the specific cellulose-based polymer as component (A) and comparative examples not included, ie, Example 1, Comparative Example 2, and Example 2 In comparison between Comparative Example 3, Comparative Example 3, Example 9 and Comparative Example 4, and Comparative Example 10 and Comparative Example 5, clear differences were observed.
In Comparative Example 1 using a polysiloxane polymer that does not contain a specific side chain, the liquid crystal was not vertically aligned.
Further, when a specific generator, a specific adhesion compound and a specific crosslinkable compound are introduced into the liquid crystal alignment treatment agent, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film is better in the formed liquid crystal display element. there were. Specifically, a clear difference was observed in the comparison between Example 2 and Example 3 and Example 9 and Example 11.

The liquid crystal display element of the present invention can be suitably used for a reverse type element that is in a transmission state when a voltage is applied and is in a scattering state when a voltage is applied. It is useful for light control windows and optical shutter elements that control the interruption. In addition, when the liquid crystal display element of the present invention is made of a plastic substrate such as a film substrate, it can be used by being attached to a glass substrate or window glass used as a support.
It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-150498 filed on July 19, 2013 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (13)

A liquid crystal composition comprising a liquid crystal and a polymerizable compound that is polymerized by active energy rays or heat is disposed between two substrates provided with electrodes, and has a liquid crystal alignment film on at least one of the substrates, A liquid crystal display element in which a cured product composite of a liquid crystal and a polymerizable compound is formed by curing in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity, and the liquid crystal alignment film includes the following components (A ) And a liquid crystal aligning agent containing the component (B).
Component (A): Cellulosic polymer having a structure represented by the following formula [1].

(X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent at least one group selected from the group consisting of the following formulas [1a] to [1m]. Represents an integer of 100 to 1000000.)

(X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , and X ¹⁴ are each independently a benzene ring, methyl group, ethyl group, n-propyl group, isopropyl group, and butyl. And at least one selected from the group consisting of groups, n represents an integer of 0 to 3, and m represents an integer of 0 to 3.)
Component (B): at least one selected from the group consisting of an alkoxysilane represented by the following formula [2a], an alkoxysilane represented by the following formula [2b], and an alkoxysilane represented by the following formula [2c] A polysiloxane polymer obtained by polycondensation.

(A ¹ represents at least one structure selected from the group consisting of structures represented by the following formulas [2-1] and [2-2]. A ² represents a hydrogen atom or a carbon number of 1 to 5. A ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3. (However, m + n + p is 4.)

(Y ¹ is selected from the group consisting of a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO—, and —OCO—. Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15.) Y ³ represents a single bond, — (CH ₂ ) _c — (c Is an integer of 1 to 15, and represents at least one selected from the group consisting of —O—, —CH ₂ O—, —COO—, and —OCO—, Y ⁴ represents a benzene ring, a cyclohexane ring, and a heterocycle. At least one divalent cyclic group selected from the group consisting of a ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, wherein any hydrogen atom on the cyclic group has 1 carbon atom -3 alkyl group, C 1-3 alkoxyl group, C 1-3 fluorine-containing amine Kill group may .Y ⁵ be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms represents at least one cyclic group selected from the group consisting of benzene ring, cyclohexane ring and heterocyclic And any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine containing group having 1 to 3 carbon atoms. It may be substituted with an alkoxyl group or a fluorine atom, n represents an integer of 0 to 4. Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, or 1 carbon atom. -At least 1 sort (s) chosen from the group which consists of a C-18 alkoxy group and a C1-C18 fluorine-containing alkoxyl group is shown, n shows the integer of 0-4.)

(Y ⁷ is a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and —OCO—. Y ⁸ represents at least one linking group selected from the group consisting of: an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.)

(B ¹ include a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacrylic group, an organic group having 2 to 12 carbon atoms and having at least one selected from the group consisting of acrylic group, a ureido group, and a cinnamoyl group B ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, and n represents 0 to 0. Represents an integer of 2. p represents an integer of 0 to 3, where m + n + p is 4.)

^{(D 1} is, .D ² represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, .n represents an alkyl group having 1 to 5 carbon atoms is an integer of 0 to 3.)   The liquid crystal display element according to claim 1, wherein the ratio of the component (A) to the component (B) is 0.1 to 9 parts by mass of the component (A) with respect to 1 part by mass of the component (B).   The alkoxysilane represented by the formula [2b] of the component (B) is allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxy). The ethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate and 3- (trimethoxysilyl) propyl methacrylate are at least one selected from the group consisting of The liquid crystal display element as described.   The alkoxysilane represented by the formula [2b] of the component (B) is 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane and 2- (3 The liquid crystal display element according to claim 1, wherein the liquid crystal display element is at least one selected from the group consisting of, 4-epoxycyclohexyl) ethyltrimethoxysilane.   The component (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula [2a], or an alkoxysilane represented by the formula [2b] or the formula [2c]. The liquid crystal display element according to claim 1, which is a polysiloxane obtained by polycondensation.   Furthermore, the liquid crystal display element of any one of Claims 1-5 which contains a solvent in the said liquid-crystal aligning agent. As the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-hexanol, cyclohexanol, 1,3-propanediol, 1,3-butanediol, 1,4-butane Diol, 2,3-butanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol The liquid crystal display element according to claim 6, comprising at least one solvent selected from the group consisting of rumethyl ether, dipropylene glycol dimethyl ether, furfuryl alcohol, and solvents represented by the following formulas [A1] to [A3]. .

(A ¹ represents an alkyl group having 1 to 3 carbon atoms. A ² represents an alkyl group having 1 to 3 carbon atoms. A ³ represents an alkyl group having 1 to 4 carbon atoms.) Furthermore, in the said liquid-crystal aligning agent, the adhesive compound which has at least 1 chosen from the group which consists of a structure shown by following formula [B1]-[B8] is contained in any one of Claims 1-7. 2. A liquid crystal display element according to item 1.

(B ¹ represents a hydrogen atom or a benzene ring. B ² represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. B ³ represents a carbon number of 1 to 1. And at least one selected from the group consisting of an 18 alkyl group, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.)   The liquid crystal alignment treatment agent further comprises at least one generator selected from the group consisting of a photo radical generator, a photo acid generator, and a photo base generator. Liquid crystal display element.   The liquid crystal display element according to claim 1, wherein the substrate is a glass substrate or a plastic substrate.   It is a liquid crystal aligning film used for the liquid crystal display element of any one of Claims 1-10, and the liquid crystal aligning film formed from the liquid-crystal aligning agent containing said component (A) and component (B).   The liquid crystal alignment film according to claim 11, wherein the film thickness is 5 to 500 nm.   The liquid-crystal aligning agent for forming the liquid-crystal aligning film of Claim 11 or 12 containing the said component (A) and a component (B).