JP6418317B2 - Liquid crystal display element - Google Patents

Description

  The present invention relates to a transmission / scattering type liquid crystal display element that is transparent when no voltage is applied and is in a scattering state when a voltage is applied.

As a liquid crystal display element using a liquid crystal material, a TN mode has been put into practical use. 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, the use efficiency of light becomes low 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 type liquid crystal (also referred to as PDLC) or a polymer network type liquid crystal (also referred to as PNLC) is known.

  In a liquid crystal display device using these, a liquid crystal composition containing a polymerizable compound that is polymerized by ultraviolet rays is disposed between a pair of substrates provided with electrodes, and the liquid crystal composition is cured by irradiation with ultraviolet rays, whereby a liquid crystal layer That is, a cured product composite (for example, a polymer network) of a liquid crystal and a polymerizable compound is formed. This liquid crystal display element controls the transmission state and the scattering state of the liquid crystal by applying a voltage.

Conventional liquid crystal display elements using PDLC and PNLC are in a cloudy (scattering) state because the liquid crystal molecules are in a random direction when no voltage is applied, and the liquid crystal is aligned in the direction of the electric field and transmits light when voltage is applied. Thus, the liquid crystal display element (also referred to as a normal type element) is in a transmissive state. However, in a normal type element, it is necessary to always apply a voltage in order to obtain a transmissive state. Therefore, power consumption is often used in applications that are often used in a transparent state, such as a window glass. Will become bigger.
On the other hand, a liquid crystal display element using PDLC (also referred to as a reverse type element) that is in a transmission state when no voltage is applied and is in a scattering state when a voltage is applied has been reported (see Patent Documents 1 and 2).

Japanese Patent No. 2885116 Japanese Patent No. 4132424

  The polymerizable compound in the liquid crystal composition in the reverse type element has a role of forming a polymer network to obtain desired optical characteristics and a role of a curing agent for improving the adhesion between the liquid crystal layer and the liquid crystal alignment film. In order to increase the adhesion with the liquid crystal alignment film, it is necessary to make the polymer network denser. However, when the polymer network is made dense, the vertical alignment property of the liquid crystal is inhibited, and the optical characteristics of the reverse type element, that is, There is a problem that the transparency when no voltage is applied and the scattering characteristics when a voltage is applied are deteriorated. Therefore, the liquid crystal composition used for the reverse type element needs to have a high vertical alignment property of the liquid crystal when the liquid crystal layer is formed.

  Furthermore, since the liquid crystal alignment film used for the reverse type element is a highly hydrophobic film for aligning the liquid crystal vertically, the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered. Therefore, a large amount of a polymerizable compound that functions as a curing agent must be introduced into the liquid crystal composition used for the reverse type device. 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 the transparency when no voltage is applied and the scattering characteristics when a voltage is applied are greatly deteriorated.

  Furthermore, when using a reverse type | mold element sticking to the window glass of a motor vehicle or an architectural building, an element may be used for a long time in the environment exposed to high temperature, high humidity, and light irradiation. Therefore, even in a harsh environment, it is necessary that the vertical alignment property of the liquid crystal does not deteriorate and the adhesion between the liquid crystal layer and the liquid crystal alignment film is high.

  The present invention has high liquid crystal vertical alignment, good optical properties, that is, good transparency when no voltage is applied and good scattering properties when no voltage is applied, and adhesion between the liquid crystal layer and the liquid crystal alignment film. Furthermore, an object of the present invention is to provide a liquid crystal display element that can maintain these characteristics even in an environment exposed to high temperature and high humidity or light irradiation for a long time.

（Ｔ^１は炭素数１〜２０のアルキレン基、及びベンゼン環若しくはシクロヘキサン環を有する炭素数６〜２４の有機基からなる群から選ばれる少なくとも１種を示し、前記炭素数１〜２０のアルキレン基の任意の−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−ＣＯＮ（ＣＨ_３）−、−Ｓ−又は−ＳＯ_２−で置き換えられても良い。Ｔ^２は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−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種を示す。Ｔ^３は下記式［１−ａ］〜式［１−ｇ］の構造からなる群から選ばれる少なくとも１種を示す。）

（Ｔ^Ａは水素原子又はベンゼン環を示す。Ｔ^Ｂ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。Ｔ^Ｃ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。）

（Ｓ^１は下記式［１−ａ］〜式［１−ｌ］の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。Ｓ^２は単結合又は炭素数１〜２４のアルキレン基を示し、前記アルキレン基の任意の−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＮＨ−、−ＣＯＮ（ＣＨ_３）−、−Ｓ−又は−ＳＯ_２−で置き換えられても良い。Ｓ^３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。Ｓ^４は単結合、−Ｏ−、−ＯＣＨ_２−、−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。Ｓ^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が、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。ｓＡは０〜４の整数を示す。Ｓ^６は炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、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。）

（Ｓ^Ａは水素原子又はベンゼン環を示す。Ｓ^Ｂ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。Ｓ^Ｃ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。Ｓ^Ｄ〜Ｓ^Ｆはそれぞれ、炭素数１〜５のアルキル基を示す。）

（Ｙ^１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−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^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が、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２〜１８のアルケニル基、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。）

（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。）


As a result of diligent research in order to achieve the above object, the present inventor has completed the present invention having the following gist.
1. A liquid crystal composition including a liquid crystal and a polymerizable compound disposed between a pair of substrates provided with electrodes has a liquid crystal layer cured by irradiating ultraviolet rays, and at least one of the substrates vertically aligns the liquid crystal A transmission / scattering type liquid crystal display element that is transparent when no voltage is applied and is in a scattering state when a voltage is applied , wherein the liquid crystal alignment film contains the following components: A liquid crystal display element obtained from an agent.
Component (A): at least one compound selected from the group consisting of a compound of the following formula [1-1] and a compound of the following formula [1-2].
Component (B): a polymer having at least one structure selected from the group consisting of the following formula [2-1] and formula [2-2].

(T ¹ represents at least one selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and an organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, and the alkylene group having 1 to 20 carbon atoms. Any —CH ₂ — represents —O—, —CO—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —CON (CH ₃ ) —, —S— or —. SO ₂ — may be substituted, and T ² is a single bond, —O—, —NH—, —N (CH ₃ ) —, —CH ₂ O—, —OCH ₂ —, —CONH—, —NHCO—. , —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO—, and —OCO—, wherein T ³ represents the following formula [1-a] to [[ 1-g] is at least one selected from the group consisting of structures. )

(T ^A is a hydrogen atom or an benzene ring .T ^B is a benzene ring, .T ^C indicating at least one cyclic group selected from the group consisting of hexane ring and heterocyclic cycloheteroalkyl alkyl having 1 to 18 carbon atoms And at least one selected from the group consisting of a 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.)

(S ¹ represents at least one structure selected from the group consisting of the structures of the following formulas [1-a] to [1-l]. S ² represents a single bond or an alkylene group having 1 to 24 carbon atoms. , Any —CH ₂ — in the alkylene group is —O—, —CO—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —CON (CH ₃ ) —, — S ³ may be replaced by S— or —SO ₂ —, and S ³ has at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number of 17 to 17 having a steroid skeleton. 51 represents a divalent organic group, and an arbitrary hydrogen atom on the cyclic group 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, C1-C3 fluorine-containing alkoxyl group or fluorine Good .S ⁴ be substituted with atoms is a single _{bond, -O -, - OCH 2 -} , - CH 2 O -, - COO- and at least one bond group selected from the group consisting of -OCO- S ⁵ represents at least one 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, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group with 1 to 3 carbon atoms, a fluorine-containing alkoxyl group with 1 to 3 carbon atoms, or a fluorine atom, and sA represents an integer of 0 to 4. S ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 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 having 1 to 18 carbon atoms. From the base That indicates at least one selected from the group.)

(S ^A is a hydrogen atom or an benzene ring .S ^B is a benzene ring, .S ^C indicating at least one cyclic group selected from the group consisting of hexane ring and heterocyclic cycloheteroalkyl alkyl having 1 to 18 carbon atoms And at least one selected from the group consisting of a 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, S ^{D to} S ^F Each represents an alkyl group having 1 to 5 carbon atoms.)

(Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ). —, —N (CH ₃ ) CO—, —COO— and —OCO— represent at least one linking group selected from the group consisting of Y ² is a single bond or — (CH ₂ ) _b — (b is 1 Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— and —. Y ⁴ represents at least one selected from the group consisting of OCO-, and Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number of 17 to 17 having a steroid skeleton. 51 represents a divalent organic group, and an arbitrary hydrogen atom on the cyclic group has 1 carbon atom. 3 alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, good .Y ⁵ be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms benzene At least one cyclic group selected from the group consisting of a ring, a cyclohexane ring and a heterocyclic ring, wherein any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl having 1 to 3 carbon atoms Group, 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, n represents an integer of 0 to 4. Y ⁶ represents 1 carbon atom. -18 alkyl group, alkenyl group having 2 to 18 carbon atoms, fluorine-containing alkyl group having 1 to 18 carbon atoms, alkoxyl group having 1 to 18 carbon atoms and fluorine-containing alkoxyl group having 1 to 18 carbon atoms. At least one selected from the group of

(Y ⁷ is a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and —OCO—. And Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.

（Ｔａ及びＴｂはそれぞれ、１〜１２の整数を示す。Ｔｃ〜Ｔｆはそれぞれ、１〜１０の整数を示す。）2. The liquid crystal display according to claim 1, wherein the compound (1-1) of the component (A) is at least one selected from the group consisting of compounds of the following formulas [1a-1] to [1a-6]. element.

(Ta and Tb are each an integer of 1 to 12. Tc to Tf are each an integer of 1 to 10.)

3. 2. S ¹ in formula [1-2] is at least one structure selected from the group consisting of formula [1-a] to formula [1-d] and formula [1-f]. Liquid crystal display element.
4). 2. The liquid crystal display element according to 1 above, wherein S ¹ in formula [1-2] is at least one structure selected from the group consisting of structures of formula [1-h] to formula [1-l].
5. The above (1), wherein the polymer of component (B) is at least one selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose, and polysiloxane. 4. The liquid crystal display element according to any one of 3.
6). (B) The polyimide precursor obtained by making the polymer of a component react the diamine component and tetracarboxylic acid component containing the diamine compound which has a structure of the said Formula [2-1] or Formula [2-2], or 5. The liquid crystal display element according to any one of the above 1 to 4, which is a polyimide obtained by imidizing the polyimide precursor.

（Ｙは前記式［２−１］又は式［２−２］を示す。ｎ１は１〜４の整数を示す。）
８．前記ジアミン成分が、下記式［３ａ］で示されるジアミンを含む上記６又は７に記載の液晶表示素子。

（Ｗは下記式［３］の構造を示す。ｍ１は１〜４の整数を示す。）

（Ｗ^１は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−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。Ｗ^２は単結合、炭素数１〜１８のアルキレン基、又はベンゼン環、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種の環状基を有する炭素数６〜２４の有機基を示し、これら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で置換されていても良い。Ｗ^３は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−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種を示す。Ｗ^４は下記式［３−ａ］〜式［３−ｇ］の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。）

（Ｗ^Ａは水素原子又はベンゼン環を示す。Ｗ^Ｂ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。Ｗ^Ｃ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。）7). 7. The liquid crystal display element according to 6 above, wherein the diamine component contains a diamine represented by the following formula [2a].

(Y represents Formula [2-1] or Formula [2-2]. N1 represents an integer of 1 to 4.)
8). 8. The liquid crystal display device according to 6 or 7, wherein the diamine component contains a diamine represented by the following formula [3a].

(W represents the structure of the following formula [3]. M1 represents an integer of 1 to 4.)

(W ¹ is a single bond, —O—, —NH—, —N (CH ₃ ) —, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO -, - COO- and .W ² indicating at least one bond group selected from the group consisting of -OCO- a single bond, an alkylene group having 1 to 18 carbon atoms, or a benzene ring, cyclohexane ring and heterocyclic An organic group having 6 to 24 carbon atoms having at least one cyclic group selected from the group consisting of: an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms. Or a fluorine-containing alkyl group having 1 to 3 carbon atoms or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, and W ³ is a single bond, —O—, —NH—, —N ( _{CH 3) -, - CH 2} O -, - CONH -, - NHC _{-, - CON (CH 3)} -, - N (CH 3) CO -, - COO- and .W ⁴ the following formula exhibits at least one selected from the group consisting of -OCO- [3-a] ~ formula It shows at least one structure selected from the group consisting of the structure [3-g].)

(W ^A represents a hydrogen atom or a benzene ring. W ^B represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. W ^C represents an alkyl having 1 to 18 carbon atoms. And at least one selected from the group consisting of a 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.)

（Ｚは下記式［４ａ］〜式［４ｋ］の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。）

（Ｚ^１〜Ｚ^４はそれぞれ独立して、水素原子、メチル基、塩素原子及びベンゼン環からなる群から選ばれる少なくとも１種を示す。Ｚ^５及びＺ^６はそれぞれ独立して、水素原子又はメチル基を示す。）9. The liquid crystal display element according to any one of the above 6 to 8, wherein the tetracarboxylic acid component contains a tetracarboxylic dianhydride represented by the following formula [4].

(Z represents at least one structure selected from the group consisting of the structures of the following formulas [4a] to [4k].)

(Z ^{1 to} Z ⁴ each independently represents at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group. Group.)

（Ａ^１は前記式［２−１］又は式［２−２］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。）

（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。）

（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。）10. The polymer of the component (B) is a polysiloxane obtained by polycondensation of an alkoxysilane of the following formula [A1], or an alkoxysilane of the formula [A1] and an alkoxy of the following formula [A2] or formula [A3] 5. The liquid crystal display element according to any one of the above 1 to 4, comprising polysiloxane obtained by polycondensation with silane.

(A ¹ represents the structure of the above formula [2-1] or [2-2]. A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ³ represents an alkyl having 1 to 5 carbon atoms. M represents an integer of 1 or 2. n represents an integer of 0 to 2. p represents an integer of 0 to 3. However, m + n + p is 4.

(B ¹ is a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, methacryl group, acryl group, an organic group having 2 to 12 carbon atoms and having at least one selected from the group consisting of 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 an integer of 0 to 2. P represents an integer of 0 to 3, where m + n + p is 4.)

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

（Ｄ^ａ、Ｄ^ｂ及びＤ^ｃはそれぞれ、炭素数１〜４のアルキル基を示す。）
１４．前記液晶配向処理剤が、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン及びγ−ブチロラクトンからなる群から選ばれる少なくとも１種の溶媒を含有する上記１〜１３のいずれか一項に記載の液晶表示素子。
１５．前記液晶組成物が、上記１に記載の式［１−１］の化合物又は式［１−２］の化合物を含有する上記１〜１４０のいずれか１項に記載の液晶表示素子。
１６．前記液晶表示素子の基板が、ガラス基板又はプラスチック基板である上記１〜１５のいずれか一項に記載の液晶表示素子。11. The liquid crystal according to any one of claims 1 to 10, wherein the liquid crystal alignment treatment agent contains at least one generator selected from the group consisting of a photo radical generator, a photo acid generator, and a photo base generator. Display element.
12 The liquid crystal aligning agent has at least one substituent 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 an alkoxyalkyl group having 1 to 3 carbon atoms. The liquid crystal display element according to any one of the above 1 to 11, comprising a compound.
13. The liquid crystal aligning agent is 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone and the following: The liquid crystal display element according to any one of the above 1 to 12, comprising at least one solvent selected from the group consisting of the solvents of the formulas [D1] to [D3].

(D ^a , D ^b and D ^c each represents an alkyl group having 1 to 4 carbon atoms.)
14 The liquid crystal alignment treatment agent according to any one of 1 to 13 above, containing at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone. The liquid crystal display element as described.
15. 141. The liquid crystal display element according to any one of 1 to 140, wherein the liquid crystal composition contains the compound of formula [1-1] or the compound of formula [1-2] described in 1.
16. The liquid crystal display element according to any one of 1 to 15, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.

  According to the present invention, good optical properties, that is, transparency when no voltage is applied and scattering property when voltage is applied, and the adhesion between the liquid crystal layer and the liquid crystal alignment film is high. It is possible to provide a reverse element capable of maintaining these characteristics even in an environment exposed to high temperature and high humidity or light irradiation for a long time. The mechanism by which the liquid crystal display device having the above-described excellent characteristics is obtained by the present invention is not necessarily clear, but is estimated as follows.

The liquid crystal aligning film in the element of the present invention is obtained from a liquid crystal aligning agent containing the compound of the formula [1-1] (also referred to as the specific compound (1-1)). T ^{3 in the} formula [1-1] is a site that undergoes a polymerization reaction with ultraviolet rays. Therefore, the polymerizable compound in the liquid crystal composition reacts with the specific compound (1) by irradiation with ultraviolet rays when producing a liquid crystal display element, and the adhesion between the liquid crystal layer and the liquid crystal alignment film can be enhanced. . Moreover, the isocyanate group which the specific compound (1-1) has reacts with polar groups, such as an amino group and a hydroxyl group, thermally. Therefore, the isocyanate group reacts with the polar group of the polymer (B) component polymer (also referred to as a specific polymer) in the liquid crystal aligning agent by heating during the production of the liquid crystal alignment film. Thereby, the bond between the specific polymer and the liquid crystal layer is formed via the specific compound (1-1), and the adhesion between the liquid crystal layer and the liquid crystal alignment film is considered to be further improved.

Further, S ¹ of the compound of the formula [1-2] (also referred to as the specific compound (1-2)) is a portion having a polar group, and the structure of S ^{3 to} S ⁶ aligns the liquid crystal vertically. It shows a rigid structure with high effect. Therefore, it is considered that when the liquid crystal alignment film is used, the specific compound (1-2) has the S ¹ polar group, so that the portions S ^{3 to} S ⁶ are efficiently transferred to the liquid crystal alignment film interface. Thereby, it is considered that the vertical alignment property of the liquid crystal is further enhanced together with the rigid structure contained in the polymer.

In addition, the liquid crystal alignment film in the present invention includes a polymer (also referred to as a specific polymer) having the structure of the above formula [2-1] or formula [2-2] (also referred to as a specific side chain structure). Obtained from the treating agent. In particular, since the formula [2-1] indicates a rigid structure, when this structure is used, a liquid crystal display element that exhibits high and stable vertical alignment of liquid crystals can be obtained. Therefore, in particular, when the formula [2-1] is used, a reverse element that exhibits good optical characteristics can be obtained.
Thus, the liquid crystal display element of the present invention is a liquid crystal display element that exhibits good optical characteristics, has high adhesion between the liquid crystal layer and the liquid crystal alignment film, and can maintain these characteristics for a long time.

<Specific compound (1-1)>
It is a compound shown by the above formula [1-1]. In formula [1-1], T ¹ , T ² , T ³ and T ⁴ are as defined above. Among these, T ¹ is from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film. An alkylene group having 1 to 12 carbon atoms is preferred. Moreover, the C6-C18 organic group which has a benzene ring or a cyclohexane ring is also preferable.

T ² is preferably a single bond, —O—, —CH ₂ O—, —OCH ₂ —, —CONH—, —NHCO—, —COO— or —OCO—.
T ³ represents the formula [1-a], the formula [1-b], the formula [1-c], the formula [1-d], or the formula [1] from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film. -F] is preferred. The formula [1-a], the formula [1-b], the formula [1-d], or the formula [1-f] is more preferable.
Preferred combinations of T ^{1 to} T ³ in the formula [1] are shown in Tables 1 and 2 below.

  Among these, (1-1a) to (1-8a), (1-10a), (1-15a) to (1-17a), (1-22a) or (1-23a) is preferable. More preferable are (1-1a) to (1-4a) from the above-mentioned points.

Specific examples of the specific compound (1-1) include the compounds of the above-described formulas [1a-1] to [1a-6].
In formula [1a-1] to formula [1a-6], Ta to Tf are as defined above, and among them, Ta and Tb are preferably integers of 1 to 10, respectively. More preferred is an integer of 1-8. Tc to Tf are each preferably an integer of 1 to 8. An integer of 1 to 6 is more preferable.
As the specific compound (1-1) in the present invention, a compound of the formula [1a-1], the formula [1a-2], the formula [1a-5] or the formula [1a-6] is preferable.

  The amount of the specific compound (1-1) used in the liquid crystal aligning agent is preferably 0.1 to 80 parts by mass with respect to 100 parts by mass of the specific polymer from the viewpoint of optical characteristics of the liquid crystal display element. More preferred is 0.1 to 60 parts by mass, and particularly preferred is 1 to 50 parts by mass. Moreover, these specific compounds can also be used 1 type or in mixture of 2 or more types according to each characteristic.

<Specific compound (1-2)>
It is a compound represented by said Formula [1-2]. In formula [1-2], S ¹ , S ² , S ³ , S ⁴ , S ⁵ , S ⁶ and sA are as defined above. Among these, S ¹ is a formula [1-a] to a formula [1-d], a formula [1-f], a formula [1-h] to a formula [1-l] from the viewpoint of optical characteristics in a liquid crystal display element. Is preferred. More preferred are structures of the formula [1-a], the formula [1-b], the formula [1-d], the formula [1-f], or the formula [1-h] to the formula [1-j]. . Particularly preferred is the formula [1-a], the formula [1-b], the formula [1-d], the formula [1-h] or the formula [1-i].

S ² is preferably a single bond or an alkylene group having 1 to 18 carbon atoms. Among these, a single bond or an alkylene group having 1 to 12 carbon atoms is preferable. S ³ is preferably a divalent organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton from the viewpoint of the optical characteristics of the liquid crystal display element. S ⁴ is preferably a single bond, —O—, —COO— or —OCO— from the viewpoint of ease of synthesis. More preferred is a single bond, —COO— or —OCO—. S ⁵ is preferably a benzene ring or a cyclohexane ring from the viewpoint of the optical characteristics of the liquid crystal display element. S ⁶ is preferably an alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms from the viewpoint of the optical characteristics of the liquid crystal display element. More preferred is an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms. sA is preferably an integer of 0 to 2 in terms of availability of raw materials and ease of synthesis. An integer of 1 or 2 is more preferable.

Preferred combinations of S ^{1 to} S ⁶ and sA in the formula [1-2] are shown in Tables 3 to 43 below.

More specific specific compound (1-2) is preferably a compound of the following formula [1a-1] to formula [1a-24].

In the above formula, each s ¹ represents an integer of 1 to 12. Especially, the point of the optical characteristic of a liquid crystal display element has a preferable integer of 1-8. s ^2, respectively, an integer of 0-4. Especially, the integer of 1 or 2 is preferable from the point of the optical characteristic of a liquid crystal display element. S ^a represents a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— or —OCO—. Show. Of these, —O— or —COO— is preferable from the viewpoint of availability of raw materials and ease of synthesis.
Each S ^b represents alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms having 1 to 18 carbon atoms. Especially, a C1-C12 alkyl group or a C1-C12 alkoxyl group is preferable. More preferred is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

In the above formula, each s ³ represents an integer of 1 to 12. Especially, the point of the optical characteristic of a liquid crystal display element has a preferable integer of 1-8. Each S ^c represents a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. Among these, —COO— or —OCO— is preferable from the viewpoint of availability of raw materials and ease of synthesis. S ^d represents a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— or —OCO—. Show. Of these, —O— or —COO— is preferable from the viewpoint of availability of raw materials and ease of synthesis.
Each S ^e represents alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms having 1 to 18 carbon atoms. Especially, a C1-C12 alkyl group or a C1-C12 alkoxyl group is preferable. More preferred is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

In the above formula, each s ⁴ represents an integer of 0 to 4. Especially, the integer of 1 or 2 is preferable from the point of the optical characteristic of a liquid crystal display element.
S ^f represents 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, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Especially, a C1-C12 alkyl group or a C1-C12 alkoxyl group is preferable. More preferred is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

In the above formula, each s ⁵ represents an integer of 1 to 12. Especially, the point of the optical characteristic of a liquid crystal display element has a preferable integer of 1-8. s ⁶ represents an integer of 0 to 4, respectively. Especially, the integer of 1 or 2 is preferable from the point of the optical characteristic of a liquid crystal display element.
^Sg shows a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group, respectively. Especially, a C1-C12 alkyl group or a C1-C12 alkoxyl group is preferable. More preferred is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

In the above formula, ^{S h} are each a single _{bond, - (CH 2) c -} (c is an integer of _{1~15), - O -, -} CH 2 O -, - shows a COO- or -OCO- . Among these, —COO— or —OCO— is preferable from the viewpoint of availability of raw materials and ease of synthesis.
S ⁱ represents 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, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Especially, a C1-C12 alkyl group or a C1-C12 alkoxyl group is preferable. More preferred is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

In the above formula, each s ⁷ represents an integer of 1 to 12. Especially, the point of the optical characteristic of a liquid crystal display element has a preferable integer of 1-8.
S ^j represents a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—, respectively. Among these, —COO— or —OCO— is preferable from the viewpoint of availability of raw materials and ease of synthesis.
S ^k represents 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, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Especially, a C1-C12 alkyl group or a C1-C12 alkoxyl group is preferable. More preferred is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms.

  The use ratio of the specific compound (1-2) in the liquid crystal aligning agent is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the specific polymer from the viewpoint of the optical characteristics of the liquid crystal display element. More preferred is 0.5 to 20 parts by mass, and particularly preferred is 1 to 10 parts by mass. Moreover, these specific compounds can be used 1 type or in mixture of 2 or more types according to each characteristic.

<Specific side chain structure>
The specific side chain structure is selected from the group consisting of the formula [2-1] and the formula [2-2].
In formula [2-1], Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are as defined above, and among them, the following are preferable.
Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, or — from the viewpoint of availability of raw materials and ease of synthesis. 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 is preferably a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 10).

Y ³ is preferably a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O— or —COO— from the viewpoint of ease of synthesis. 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 preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton from the viewpoint of ease of synthesis. Y ⁵ is preferably a benzene ring or a cyclohexane ring.
Y ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine containing group having 1 to 10 carbon atoms. Alkoxyl groups are preferred. More preferred is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms. n is preferably 0 to 3 and more preferably 0 to 2 from the viewpoint of availability of raw materials and ease of synthesis.

Preferred combinations of Y ^{1 to} Y ⁶ and n are listed in Tables 6 to 47 on pages 13 to 34 of International Publication WO2011 / 132751 (published 2011.10.27) (2-1) to (2- 629) and the same combination. In each table of International Publication, ^Y 1 to Y ⁶ in the present invention is shown as Y1 to Y6, Y1 to ^Y6, shall read Y 1 to Y ^6. Moreover, in (2-605)-(2-629) published in each table | surface of international publication gazette, the C17-C51 organic group which has a steroid skeleton in this invention has 12-12 carbon atoms which have a steroid skeleton. An organic group having 25 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.

  Among them, (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315), A combination of (2-364) to (2-387), (2-436) to (2-483) or (2-603) to (2-615) is preferable. Particularly preferred 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).

Y ⁷ and Y ⁸ in the formula [2-2] are as defined above, and among them, the following are preferable.
Y ⁷ is preferably a single bond, —O—, —CH ₂ O—, —CONH—, —CON (CH ₃ ) — or —COO—. More preferably, they are a single bond, -O-, -CONH-, or -COO-. Y ⁸ is preferably an alkyl group having 8 to 18 carbon atoms.
The specific side chain structure in the present invention preferably uses the formula [2-1] from the viewpoint that a high and stable liquid crystal vertical alignment can be obtained.

<Specific polymer>
The specific polymer having a specific side chain structure is at least one polymer selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane. Is preferred. More preferred are polyimide precursors, polyimides or polysiloxanes.
When a polyimide precursor or polyimide (also collectively referred to as a polyimide polymer) is used as the specific polymer, they are preferably a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component. .

（Ｒ^１は４価の有機基を示す。Ｒ^２は２価の有機基を示す。Ａ^１及びＡ^２はそれぞれ独立して、水素原子又は炭素数１〜８のアルキル基を示す。Ａ^３及びＡ^４はそれぞれ独立して、水素原子、炭素数１〜５のアルキル基又はアセチル基を示す。ｎは正の整数を示す。）The polyimide precursor has a structure of the following formula [A].

(R ¹ represents a tetravalent organic group. R ² represents a divalent organic group. A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A ³ And A ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group, and n represents a positive integer.)

  The diamine component is a diamine compound having two primary or secondary amino groups in the molecule, and the tetracarboxylic acid component is a tetracarboxylic acid compound, tetracarboxylic dianhydride, tetracarboxylic acid dihalide compound, A tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound may be mentioned.

（Ｒ^１及びＲ^２は、式［Ａ］で定義したものと同意義である。）The polyimide polymer can be obtained relatively easily by using a tetracarboxylic dianhydride of the following formula [B] and a diamine compound of the following formula [C] as raw materials. A polyamic acid having a repeating unit of or a polyimide obtained by imidizing the polyamic acid is preferable.

(R ¹ and R ² have the same meaning as defined in formula [A].)

（Ｒ^１及びＲ^２は、式［Ａ］で定義したものと同意義である。）
また、通常の合成手法で、上記で得られた式［Ｄ］の重合体に、式［Ａ］中のＡ^１及びＡ^２の炭素数１〜８のアルキル基、及び式［Ａ］中のＡ^３及びＡ^４の炭素数１〜５のアルキル基又はアセチル基を導入することもできる。

(R ¹ and R ² have the same meaning as defined in formula [A].)
In addition, the polymer of the formula [D] obtained above by the usual synthesis method, the alkyl group having 1 to 8 carbon atoms of A ¹ and A ^{2 in} the formula [A], and the polymer in the formula [A] It is also possible to introduce an alkyl group having 1 to 5 carbon atoms or an acetyl group of A ³ and A ⁴ .

As a method for introducing the specific side chain structure into the polyimide polymer, a diamine compound having a specific side chain structure is preferably used as a part of the raw material. In particular, it is preferable to use the diamine compound of the formula [2a] (also referred to as the specific diamine compound (1)).
In the formula [2a], Y represents the formula [2-1] or the formula [2-2]. The details and preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in Formula [2-1] are as in Formula [2-1], and Formula [2] The details and preferred combinations of Y ⁷ and Y ⁸ in -2] are as shown in the formula [2-2].
m shows the integer of 1-4. Among these, an integer of 1 is preferable.

（Ｒ^１及びＲ^２はそれぞれ、炭素数３〜１２のアルキル基を示す。）

（Ｒ^３及びＲ^４はそれぞれ、炭素数３〜１２のアルキル基を示し、１,４-シクロヘキシレンのシス−トランス異性は、トランス異性体である。）
最も好ましいのは、液晶表示素子の光学特性の点から、前記式［２ａ−３５］〜式［２ａ−３７］、式［２ａ−４０］又は式［２ａ−４１］で示されるジアミン化合物である。Specific examples of the specific diamine compound having the specific side chain structure represented by the formula [2-1] include those represented by the formula [2] described on pages 15 to 19 of International Publication WO2013 / 125595 (published 2013.8.29). -1] to formula [2-6] and formula [2-9] to formula [2-36] diamine compounds. In the description of International Publication WO2013 / 125595, _{R 4} in the formula [2-1] _{R 2} and wherein in ~ formula [2-3] [2-4] to the formula [2-6], the carbon It shows at least one 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 alkoxy group having 1 to 18 carbon atoms, and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Moreover, _{A 4} in the formula [2-13] is a straight or branched alkyl group having 3 to 18 carbon atoms. In addition, R ₃ in the formulas [2-4] to [2-6] represents at least one selected from the group consisting of —O—, —CH ₂ O—, —COO—, and —OCO—. .
Among these, preferred diamine compounds are those represented by the formula [2-1] to the formula [2-6], the formula [2-9] to the formula [2-13] or the formula [2−2] described in International Publication WO2013 / 125595. 22] to diamine compound represented by formula [2-31].
More preferable are diamine compounds represented by the following formulas [2a-32] to [2a-41] from the viewpoint of optical characteristics of the liquid crystal display element.

(R ¹ and R ² each represent an alkyl group having 3 to 12 carbon atoms.)

(R ³ and R ⁴ each represent an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)
Most preferred is a diamine compound represented by the formula [2a-35] to formula [2a-37], formula [2a-40] or formula [2a-41] from the viewpoint of the optical characteristics of the liquid crystal display element. .

The specific diamine compound (1) having the specific side chain structure of the formula [2-2] is specifically described on pages 23 to 24 of International Publication No. WO2015 / 012368 (published 2015.1.29). Examples thereof include diamine compounds of the formula [2a-37] to the formula [2a-46].
The specific diamine compound (1) is used in an amount of 10 to 10% of the total diamine component from the viewpoint of the vertical alignment of the liquid crystal when the liquid crystal alignment film is formed and the adhesion between the liquid crystal layer and the liquid crystal alignment film in the liquid crystal display element. 80 mol% is preferable and 20-70 mol% is more preferable. Moreover, the specific diamine compound (1) can be used 1 type or in mixture of 2 or more types according to each characteristic.

As the diamine component for producing the polyimide polymer, the diamine compound of the formula [3a] (also referred to as the specific diamine compound (2)) is preferably used as the second diamine compound.
In the formula [3a], W ¹ , W ² , W ³ and W ⁴ are as defined above, and among them, the following are preferable.
W ¹ is preferably a single bond, —O—, —CH ₂ O—, —CONH—, —CON (CH ₃ ) — or —COO— from the viewpoint of availability of raw materials and ease of synthesis. More preferred is —O—, —CH ₂ O— or —COO—. W ² is preferably a single bond, an alkylene group having 1 to 18 carbon atoms, or an organic group having 6 to 12 carbon atoms having a benzene ring or a cyclohexane ring. More preferred is an alkylene group having 2 to 10 carbon atoms from the viewpoint of the optical characteristics of the liquid crystal display element.

W ³ is preferably a single bond, —O—, —CH ₂ O—, —CO— or —OCO— from the viewpoint of availability of raw materials and ease of synthesis. W ⁴ is preferably a structure of the formula [3-a], the formula [3-b], the formula [3-c] or the formula [3-e] from the viewpoint of the optical characteristics of the liquid crystal display element. m shows the integer of 1-4. Among these, an integer of 1 is preferable.

Specific examples of the specific diamine compound (2) include diamine compounds represented by the following formulas [3a-1] to [3a-27], and these are preferably used.

（式［３ａ−１］〜式［３ａ−２７］中、ｄ１は、２〜１０の整数を示す。）

(In formula [3a-1] to formula [3a-27], d1 represents an integer of 2 to 10.)

The proportion of the specific diamine compound (2) used is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, based on the total diamine component, from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film in the liquid crystal display element. . Moreover, the specific diamine compound (2) can be used alone or in combination of two or more according to the respective characteristics.
As a diamine component for producing a polyimide polymer, a diamine compound other than the specific diamine compound (1) and the specific diamine compound (2) (also referred to as other diamine compound) is used as long as the effects of the present invention are not impaired. You can also

Specifically, the second diamine compound of the formula [2b] described on pages 25 to 26 of International Publication No. WO2015 / 012368 (published on 2015. 1.29), described on pages 27 to 30 of the publication. Other diamine compounds and the diamine compounds of the formula [DA1] to the formula [DA14] described on pages 30 to 32 of the publication can be mentioned. In addition, other diamine compounds may be used alone or in combination of two or more depending on the characteristics.
Examples of the tetracarboxylic acid component for producing the polyimide-based polymer include tetracarboxylic dianhydride of the above formula [4] and tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester which are tetracarboxylic acid derivatives thereof. Alternatively, tetracarboxylic acid dialkyl ester dihalide (all are collectively referred to as a specific tetracarboxylic acid component) is preferable.

In the formula [4], Z is as defined above. Above all, from the ease of synthesis and the ease of polymerization reactivity in producing a polyimide polymer, the formula [4a] and the formula A structure of [4c], formula [4d], formula [4e], formula [4f], formula [4g] or formula [4k] is preferable. More preferable is the formula [4a], the formula [4e], the formula [4f], the formula [4g], or the formula [4k] from the viewpoint of the optical characteristics of the liquid crystal display element.
The use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more with respect to the total tetracarboxylic acid component. More preferably, it is 5 mol% or more, and still more preferably 10 mol% or more. Among these, 10 to 90 mol% is particularly preferable from the viewpoint of the optical characteristics of the liquid crystal display element.

Moreover, when using the specific tetracarboxylic acid component of said Formula [4e], Formula [4f], Formula [4g], or Formula [4k], the usage-amount shall be 20 mol% or more of the whole tetracarboxylic acid component. Thus, a desired effect can be obtained. More preferably, it is 30 mol% or more. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid component of the formula [4e], the formula [4f], the formula [4g], or the formula [4k].
As long as the effects of the present invention are not impaired, other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used for the polyimide polymer. Examples of other tetracarboxylic acid components include the following tetracarboxylic acids, tetracarboxylic dianhydrides, dicarboxylic acid dihalides, dicarboxylic acid dialkyl esters, and dialkyl ester dihalides.

Specific examples include other tetracarboxylic acid components described on pages 34 to 35 of International Publication No. WO2015 / 012368 (published 2015.1.29). Moreover, the specific tetracarboxylic acid component and other tetracarboxylic acid components can be used alone or in combination of two or more according to the respective characteristics.
The method for synthesizing the polyimide polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Specifically, the method described in pages 35 to 36 of International Publication No. WO2015 / 012368 (2015.1.19 publication) can be mentioned.
The reaction between the diamine component and the tetracarboxylic acid component is usually performed in a solvent containing the diamine component and the tetracarboxylic acid component. As a solvent, if the produced | generated polyimide precursor melt | dissolves, it will not specifically limit.

  Specifically, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolide Non etc. are mentioned. Further, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the solvent of the above formula [D1] to formula [D3] can be used. These may be used alone or in combination. Further, even a solvent that does not dissolve the polyimide precursor may be used by mixing with the above-mentioned solvent as long as the generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

Polyimide is a polyimide obtained by ring closure of a polyimide precursor, and in this polyimide, the ring closure rate (also referred to as imidation rate) of the amic acid group does not necessarily need to be 100%, and is arbitrary depending on the application and purpose Can be prepared. Especially, 30-80% is preferable from the point of the solubility to the solvent of a polyimide-type polymer. More preferably, it is 40 to 70%.
The molecular weight of the polyimide polymer is 5,000 in terms of Mw (weight average molecular weight) measured by the GPC method in consideration of the strength of the liquid crystal alignment film obtained therefrom, workability at the time of forming the liquid crystal alignment film, and coating properties. It is preferable to set it to -1,000,000, More preferably, it is 10,000-150,000.

<Polysiloxane polymer>
When polysiloxane is used for the specific polymer, the polysiloxane obtained by polycondensation of the alkoxysilane of the formula [A1], or the alkoxysilane of the formula [A1], and the formula [A2] or the formula [A3 The polysiloxane obtained by polycondensation with an alkoxysilane is generally preferred (the above polysiloxanes are collectively referred to as a polysiloxane polymer).

Alkoxylanes of the formula [A1]:
In the formula [A1], ^{A 1} represents a structure of the formula [2-1] or Formula [2-2]. The details and preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2-1] are as described above, and Y ⁷ in the formula [2-2]. And the details and preferred combinations of Y ⁸ are as described above.
In the present invention, the specific side chain structure of the formula [2-1] is preferable from the viewpoint of the vertical alignment property of the liquid crystal when the liquid crystal alignment film is formed and the optical characteristics of the liquid crystal display element.

In the formula [A1], A ² , A ³ , m, n, and p are as defined above. Among these, the following are preferable. A ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. A ³ is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of polycondensation reactivity. m is preferably an integer of 1 from the viewpoint of synthesis. n shows the integer of 0-2. p is preferably an integer of 1 to 3, more preferably an integer of 2 or 3, from the point of polycondensation reactivity. m + n + p is an integer of 4.

  As an alkoxysilane having a specific side chain structure of the formula [2-1], specifically, the formula [2a-1 described on pages 17 to 21 of International Publication No. 2015/008846 (published 2015.1.22). ] To alkoxysilanes of the formula [2a-32]. Among them, from the point that high and stable vertical alignment of liquid crystal can be obtained, the formula [2a-9] to the formula [2a-21], the formula [2a-25] to the formula [2a-28] or the formula [2a -32] is preferred. The alkoxysilane of the formula [A1] can be used by mixing two or more kinds according to each characteristic.

Alkoxylanes of the formula [A2]:
In the formula [A2], B ¹ , B ² , B ³ , m, n, and p are as defined above. Among these, the following are preferable.
B ¹ is preferably an organic group having a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, or a ureido group in view of availability. More preferred is an organic group having a methacryl group, an acryl group or a ureido group. B ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. B ³ is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of polycondensation reactivity. m is preferably an integer of 1 from the viewpoint of synthesis. n shows the integer of 0-2. p is preferably an integer of 1 to 3, and more preferably an integer of 2 or 3, from the viewpoint of polycondensation reactivity. m + n + p is 4.

Specific examples of the alkoxysilane of the formula [A2] include the alkoxysilane of the formula [2b] described on pages 22 to 23 of International Publication No. 2015/008846 (published 2015.1.22).
Among them, from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, 3-glycidyloxy Propyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferred.
The alkoxysilane of the formula [A2] can be used alone or in combination of two or more according to each property.

Alkoxylanes of the formula [A3]:
In the formula [A3], D ¹ , D ² and n are as defined above, and among them, the following are preferable. D ¹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. From the viewpoint of polycondensation reactivity, D ² is preferably an alkyl group having 1 to 3 carbon atoms. n shows the integer of 0-3.
Specific examples of the alkoxysilane of the formula [A3] include the alkoxysilane of the formula [2c] described on page 24 of International Publication No. 2015/008846 (published 2015.1.22).
In the formula [A3], examples of the alkoxysilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. The alkoxysilane of the formula [A3] includes these alkoxysilanes. It is preferable to use it. Moreover, the alkoxysilane of a formula [A3] can be used 1 type or in mixture of 2 or more types according to each characteristic.

  The polysiloxane polymer is a polysiloxane obtained by polycondensation of the alkoxysilane of the formula [A1], or the alkoxysilane of the formula [A1], and the alkoxysilane of the formula [A2] or the formula [A3] Is a polysiloxane obtained by polycondensation. That is, the polysiloxane polymer is a polysiloxane obtained by polycondensation of only the alkoxysilane of the formula [A1], and a polysiloxane obtained by polycondensation of two types of alkoxysilanes of the formulas [A1] and [A2]. Polysiloxane obtained by polycondensation of siloxane, two types of alkoxysilanes of formula [A1] and formula [A3], and three types of alkoxysilanes of formula [A1], formula [A2] and formula [A3] Any one of polysiloxanes obtained by condensation.

  Of these, polysiloxanes obtained by polycondensation of a plurality of types of alkoxysilanes are preferred in terms of polycondensation reactivity and solubility of polysiloxane polymers in a solvent. That is, polysiloxane obtained by polycondensation of two types of alkoxysilanes of the formulas [A1] and [A2], and polypolyester obtained by polycondensation of two types of alkoxysilanes of the formulas [A1] and [A3]. It is preferable to use any one of siloxane and polysiloxane obtained by polycondensation of three types of alkoxysilanes of the formulas [A1], [A2] and [A3].

In the case of using a plurality of types of alkoxysilanes in preparing the polysiloxane polymer, the use of the alkoxysilane of the formula [A1] is preferably 1 to 40 mol%, and 1 to 30 mol% in all alkoxysilanes. More preferred. The use of the alkoxysilane of the formula [A2] is preferably 1 to 70 mol%, more preferably 1 to 60 mol% in all alkoxysilanes. Furthermore, the use of the alkoxysilane of the formula [A3] is preferably 1 to 99 mol%, more preferably 1 to 80 mol% in all alkoxysilanes.
The method for polycondensing the polysiloxane polymer is not particularly limited. Specifically, the method described in pages 26 to 29 of International Publication No. 2015/008846 (published 2015.1.22) can be mentioned.

In the present invention, the polysiloxane polymer solution obtained by the above method may be used as a specific polymer as it is, or the polysiloxane polymer solution obtained by the above method may be used as necessary. The polymer may be concentrated, diluted by adding a solvent, or substituted with another solvent to be used as a specific polymer.
The solvent used for dilution (also referred to as an additive solvent) may be a solvent used for the polycondensation reaction or other solvents. The additive solvent is not particularly limited as long as the polysiloxane polymer is uniformly dissolved, and one or two or more kinds can be arbitrarily selected and used. Examples of such an additive solvent include, in addition to the solvent used in the polycondensation reaction, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate. . Furthermore, when a polysiloxane polymer and other polymers are used as the specific polymer, the polysiloxane polymer is subjected to a polycondensation reaction before mixing the other polymer with the polysiloxane polymer. The generated alcohol is preferably distilled off at normal pressure or reduced pressure.

<Liquid crystal alignment agent>
A liquid crystal aligning agent is a solution for forming a liquid crystal aligning film, and is a solution containing a specific compound, a specific polymer having a specific side chain structure, and a solvent.
As for content of the specific compound (1-1) in a liquid-crystal aligning agent, 0.1-80 mass parts is preferable with respect to 100 mass parts of specific polymers. Among these, 0.1 to 60 parts by mass is preferable from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film. Most preferred is 1 to 50 parts by weight. Moreover, a specific compound can be used 1 type or in mixture of 2 or more types.
As for content of the specific compound (1-2) in a liquid-crystal aligning agent, 0.1-30 mass parts is preferable with respect to 100 mass parts of specific polymers from the point of the optical characteristic of a liquid crystal display element. More preferred is 0.5 to 20 parts by mass, and particularly preferred is 1 to 10 parts by mass.

  The specific compounds (1-1) and (1-2) may be added directly to the solution of the specific polymer. However, the specific compounds (1-1) and (1-2) should be added after making the solution 0.1 to 10% by mass with an appropriate solvent. Is preferred. The solvent in this case is not particularly limited as long as it is a solvent that dissolves the above-mentioned specific polymer. Yes. In addition, the specific compound and the specific polymer are mixed because the reaction between the isocyanate group in the specific compound and the polar group in the specific polymer is promoted and the adhesion between the liquid crystal layer and the liquid crystal alignment film can be improved. Then, the reaction is preferably carried out with stirring. The temperature at that time is preferably 0 to 100 ° C, and more preferably 10 to 60 ° C. The time is preferably 1 to 24 hours.

  The specific polymer is preferably at least one polymer selected from the group consisting of acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane. More preferred are polyimide precursors, polyimides or polysiloxanes, and most preferred are polyimide precursors or polyimides. Moreover, 2 or more types can be used for a specific polymer.

The polymer component in the liquid crystal aligning agent may all be a specific polymer, or other polymers may be mixed. 0.5-15 mass parts is preferable with respect to 100 mass parts of specific polymers, and, as for content of other polymers, 1-10 mass parts is more preferable. Examples of other polymers include the above-mentioned polymers having no specific side chain structure.
Content of the solvent in a liquid-crystal aligning agent can be suitably selected from the point of obtaining the coating method of a liquid-crystal aligning agent, and the target film thickness. Especially, since uniform liquid crystal aligning film is formed by application | coating, 50-99.9 mass% is preferable in a liquid-crystal aligning agent, and, as for content of a solvent, 60-99 mass% is more preferable, and 65-99. Mass% is particularly preferred.

  The solvent used for the liquid crystal aligning agent is not particularly limited as long as the solvent dissolves the specific polymer. Above all, when the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility of acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, cellulose or polysiloxane is low, it will be published internationally. It is preferable to use the solvent A described on page 58 of the publication 2014/171493 (published 2014.10.23). Among these, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone. These may be used alone or in combination.

  When the specific polymer is an acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, cellulose, or polysiloxane, the specific polymer is a polyimide precursor, polyimide, polyamide, or polyester. When the solubility in a solvent is high, the solvent B described in pages 58 to 60 of International Publication No. 2014/171493 (published 2014.10.23) can be used. Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone or the above formula [D1] to It is preferable to use a solvent of the formula [D3].

When these solvents B are used, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone of the solvent A is used in combination for the purpose of improving the coating property of the liquid crystal aligning agent. It is preferable. More preferably, γ-butyrolactone is used in combination.
Since these solvents B can improve the coating properties and surface smoothness of the liquid crystal alignment film when applying the liquid crystal alignment treatment agent, when a polyimide precursor, polyimide, polyamide or polyester is used for the specific polymer The solvent A is preferably used in combination. The solvent B is preferably 1 to 99% by mass of the entire solvent contained in the liquid crystal aligning agent. Especially, 10-99 mass% is preferable. More preferably, it is 20-95 mass%.

It is preferable to introduce at least one generator (also referred to as a specific generator) selected from the group consisting of a photo radical generator, a photo acid generator and a photo base generator into the liquid crystal alignment treatment agent. Specific examples of the specific generator include specific generators described on pages 54 to 56 of International Publication No. 2014/171493 (published 2014.10.23). Among these, as the specific generator, a photo radical generator is preferably used from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film.
As the liquid crystal aligning agent, compounds of the following formulas [7a-1] to [7a-5] (also referred to as adhesive compounds) can be used for the purpose of enhancing the adhesion between the liquid crystal layer and the liquid crystal alignment film.

（ｎ２は１〜１０の整数を示す。ｍ２は１〜１０の整数を示す。）

(N2 represents an integer of 1 to 10. m2 represents an integer of 1 to 10.)

Furthermore, as the adhesive compound, compounds described on pages 61 to 63 of International Publication No. 2014/171493 (2014.10.23 publication) can also be used.
As for content of the adhesive compound in a liquid-crystal aligning agent, 0.1-150 mass parts is preferable with respect to 100 mass parts 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 mass is more preferable, and 1 to 50 parts by mass is most preferable, with respect to 100 parts by mass of all polymer components. Moreover, 1 type or 2 types or more can be mixed and used for an adhesive compound according to each characteristic.

The liquid crystal aligning agent includes compounds having at least one group 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 (generic name). And also referred to as a specific crosslinkable compound). It is necessary to have two or more of these groups in the compound.
Specific examples of the crosslinkable compound having an epoxy group or an isocyanate group include compounds described on pages 63 to 64 of International Publication No. 2014/171493 (published 2014.10.23).

Specific examples of the crosslinkable compound having an oxetane group include compounds of the formula [4a] to the formula [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27). It is done.
Specific examples of the crosslinkable compound having a cyclocarbonate group include the formula [5-1] to the formula [5-42] published on pages 76 to 82 of International Publication WO2012 / 014898 (2012.2.2 publication). ] Of the compound.

  As a crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, specifically, a melamine derivative or benzoguanamine described on pages 65 to 66 of International Publication No. 2014/171493 (published 2014.10.23) Derivatives, and compounds of formula [6-1] to formula [6-48], which are listed on pages 62 to 66 of International Publication No. WO2011 / 132751 (published 2011.10.27).

As for content of the specific crosslinkable compound in a liquid-crystal aligning agent, 0.1-100 mass parts is preferable 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, 0.1 to 50 parts by mass is more preferable, and 1 to 30 parts by mass is particularly preferable with respect to 100 parts by mass of all the polymer components.
The liquid crystal aligning agent is published on pages 69 to 73 of International Publication No. WO2011 / 132751 (published 2011.10.27) in order to promote charge transfer in the liquid crystal alignment film and promote charge release of the device. A nitrogen-containing heterocyclic amine compound of the formulas [M1] to [M156] can also be added.

As long as the effects of the present invention are not impaired, a compound that improves the uniformity of the thickness of the liquid crystal alignment film and the surface smoothness when the liquid crystal alignment treatment agent is applied can be used as the liquid crystal alignment treatment agent. Furthermore, a compound that improves the adhesion between the liquid crystal alignment film and the substrate can be used.
Examples of the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples include surfactants described on page 67 of International Publication No. 2014/171493 (published 2014.10.23). Moreover, the use ratio is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent. is there.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include compounds described on pages 67 to 69 of International Publication No. 2014/171493 (published 2014.10.23). Moreover, 0.1-30 mass parts is preferable with respect to 100 mass parts of all the polymer components contained in a liquid-crystal aligning agent, and, as for the use ratio, 1-20 mass parts is more preferable.
In addition to the compounds other than those described above, a dielectric or conductive material may be added to the liquid crystal alignment treatment agent for the purpose of changing electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film.

<Liquid crystal composition>
The liquid crystal composition contains a polymerizable compound that is polymerized by liquid crystal and ultraviolet rays, and this polymerizable compound plays a role of forming a polymer network (curable resin). Further, the liquid crystal layer is a cured product composite of liquid crystal and a polymerizable compound, and the cured product composite here is, for example, a liquid crystal in a polymer network formed of a polymerizable compound as described above. It means a state that exists.
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, it is required that the liquid crystal has a high electric resistance and a high voltage holding ratio (VHR). For this reason, it is preferable to use a fluorine-based or chlorine-based liquid crystal that has high electrical resistance and does not lower VHR by active energy rays such as ultraviolet rays.
Furthermore, in the liquid crystal display element, a dichroic dye can be dissolved in the liquid crystal composition to form a guest-host type element. 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. A guest-host type element in which a dichroic dye is dissolved is colored when the liquid crystal is aligned in the horizontal direction, and is 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 (for example, a polymer network) of the liquid crystal composition by a polymerization reaction with ultraviolet rays. A monomer of a 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 of 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 ultraviolet rays during the production of the liquid crystal display element are reduced. A method of forming a cured product by performing a polymerization reaction by irradiation is preferable.

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 only needs to be a compound that undergoes a polymerization reaction by ultraviolet rays. At that time, the polymerization may proceed in any reaction form to form a cured product of the liquid crystal composition. Specific reaction formats include radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction. Among these, radical polymerization is preferable as the reaction mode of the polymerizable compound. As the polymerizable compound, it is preferable to use a radical type polymerizable compound (monomer) and an oligomer thereof. Further, as described above, a polymer obtained by polymerizing these monomers can also be used.

Specific examples include monofunctional polymerizable compounds, bifunctional polymerizable compounds and polyfunctional polymerizable compounds described on pages 58 to 60 of International Publication No. 2015/012368 (published 2015.1.29). It is done. Further, the radical type polymerizable compound may be used alone or in combination of two or more depending on each characteristic.
Further, in order to promote the formation of a cured product of the liquid crystal composition, a radical initiator (also referred to as a polymerization initiator) that generates radicals by ultraviolet rays is used in the liquid crystal composition for the purpose of promoting radical polymerization of the polymerizable compound. It is preferable to introduce. Specific examples include radical initiators described on pages 13 to 14 of International Publication No. 2014/171493 (published 2014.10.23). Moreover, a radical initiator can also be used 1 type or in mixture of 2 or more types according to each characteristic.

As the polymerizable compound, an ionic polymerizable compound 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.
Specifically, melamine derivatives and benzoguanamine derivatives described in International Publication No. 2014/171493 (published 2014.10.23), benzoguanamine derivatives, 1,3,5-tris (methoxymethoxy) benzene, 1,2 , 4-tris (isopropoxymethoxy) benzene, 1,4-bis (sec-butoxymethoxy) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and International Publication No. 2014/171493 (2014.10.23). The compounds containing epoxy and isocyanate groups described on pages 15 to 16 of (Publication).

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. Specific examples include ion initiators described on pages 16 to 17 of International Publication No. 2014/171493 (published 2014.10.23).
The liquid crystal composition of the present invention preferably contains the compound of the formula [1-2] described above. In formula [1-2], S ¹ , S ² , S ³ , S ⁴ , S ⁵ , S ⁶ and sA are as defined above, and among them, the following are preferable. S ¹ is preferably the formula [1-a] to the formula [1-f] and the formula [1-h] to the formula [1-j] from the viewpoint of the optical characteristics of the liquid crystal display element. The formula [1-a], the formula [1-b], the formula [1-d], the formula [1-i], or the formula [1-j] is more preferable. S ² is preferably a single bond or an alkylene group having 1 to 18 carbon atoms. Among these, a single bond or an alkylene group having 1 to 12 carbon atoms is preferable. Arbitrary —CH ₂ — in the alkylene group is —O—, —CO—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —CON (CH ₃ ) —, —S. - or -SO ₂ - may be replaced by.

S ³ is preferably a divalent organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton from the viewpoint of the optical characteristics of the liquid crystal display element. S ⁴ is preferably a single bond, —O—, —COO— or —OCO— from the viewpoint of ease of synthesis. More preferred is a single bond, —COO— or —OCO—. S ⁵ is preferably a benzene ring or a cyclohexane ring from the viewpoint of the optical characteristics of the liquid crystal display element. S ⁶ is preferably an alkyl group, an alkoxyl group, or an alkenyl group having 1 to 18 carbon atoms from the viewpoint of the optical characteristics of the liquid crystal display element. More preferably, it is an alkyl group, an alkoxyl group or an alkenyl group having 1 to 12 carbon atoms. sA is preferably an integer of 0 to 2, more preferably an integer of 1 or 2, from the viewpoint of availability of raw materials and ease of synthesis.

As a compound of the formula [1-2] added to the liquid crystal composition of the present invention (hereinafter also referred to as a liquid crystal additive compound), including the preferred ones, the formula [1-2] It is the same as the compound of]. That is, the compound of said formula [1a-1]-a formula [1a-24] is mentioned.
The amount of the liquid crystal additive compound used in the liquid crystal composition is preferably from 0.1 to 30 parts by mass, more preferably from 0 to 100 parts by mass of the liquid crystal composition excluding the liquid crystal additive compound, from the viewpoint of the optical properties of the device. It is 5-30 mass parts, Most preferably, it is 1-20 mass parts. Two or more liquid crystal additive compounds can be mixed and used.

<Method for Producing Liquid Crystal Alignment Film and Liquid Crystal Display Element>
The substrate used for the liquid crystal display element 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, a PET (polyethylene terephthalate) substrate, or a film thereof. Can be used. When the liquid crystal display element is used as a reverse 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 such as a silicon wafer or aluminum or a dielectric multilayer film is formed can be used as long as the substrate is only on one side.

In the liquid crystal display element, at least one of the substrates has a liquid crystal alignment film that aligns liquid crystal molecules vertically. This 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 liquid crystal alignment film in the present invention can be used as a liquid crystal alignment film without these alignment treatments.
The application method of the liquid crystal alignment treatment 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 film thickness of the target liquid crystal alignment film, it can be appropriately selected.
After the liquid crystal aligning agent is applied on the substrate, the heating means such as a hot plate, a thermal circulation oven, an IR (infrared) oven, etc., depending on the type of the substrate and the solvent used for the liquid crystal aligning agent, The 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 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. Therefore, it is preferably 5 to 500 nm, more preferably 10 to 300 nm. Particularly preferably, the thickness is 10 to 250 nm.
In the liquid crystal composition used for the liquid crystal display element, a spacer for controlling an electrode gap (also referred to as a gap) of the liquid crystal display element can be introduced.
Examples of the method for injecting the liquid crystal composition include the following methods. That is, when a glass substrate is used as a substrate, a pair of substrates on which a 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 surface of the liquid crystal alignment film is An empty cell is produced by bonding the other substrate to 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. Further, when a plastic substrate or a film is used as a substrate, a pair of substrates having a liquid crystal alignment film is prepared, and a liquid crystal composition is formed on one substrate by an ODF (One Drop Filling) method or an inkjet method. Is dropped, and then the other substrate is bonded to obtain a liquid crystal composition injection cell. In this invention, since the adhesiveness of a liquid crystal layer and a liquid crystal aligning film is high, it is not necessary to apply | coat a sealing compound to four pieces of a board | substrate.

The gap of the liquid crystal display element can be controlled by a spacer or the like. Examples of the method include a method of introducing a spacer having a desired size into the liquid crystal composition and a method using a substrate having a column spacer of a desired size. In addition, when a plastic or film substrate is used as the substrate and the substrates are laminated together, the gap can be controlled without introducing a spacer.
The size of the gap is preferably 1 to 100 μm, more preferably 2 to 50 μm, and particularly preferably 5 to 20 μm. If the gap is too small, the contrast of the liquid crystal display element decreases, and if it is too large, the driving voltage increases.

  The liquid crystal display element cures the liquid crystal composition by irradiation with ultraviolet rays to form a liquid crystal layer of a cured product composite of liquid crystal and a polymerizable compound. The liquid crystal composition is cured by irradiating the liquid crystal composition injection cell with ultraviolet rays. Examples of the light source of the ultraviolet irradiation device include a metal halide lamp and a high-pressure mercury lamp. The wavelength of the ultraviolet light is preferably 250 to 400 nm, and preferably 310 to 370 nm. Heat treatment may be performed after irradiation with ultraviolet rays, and the temperature at that time is preferably 40 to 120 ° C, more preferably 40 to 80 ° C.

（液晶）Ｌ１：ＭＬＣ−６６０８（メルク社製）The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited to these examples.
<Example A series>
The meanings of the abbreviations of the compounds etc. used below are as follows.
<Liquid crystal composition>

(Liquid crystal) L1: MLC-6608 (Merck)

（光開始剤）

(Polymerizable compound)

(Photoinitiator)

A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene A2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclo) Hexyl) phenoxymethyl] benzene A3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene A4: the following formula [A4 A5: 1,3-diamino-4-octadecyloxybenzene

Ｃ１：ｍ−フェニレンジアミン
Ｃ２：３，５−ジアミノ安息香酸

C1: m-phenylenediamine C2: 3,5-diaminobenzoic acid

D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride D2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

＜特定発生剤＞

<Specific compounds>

<Specific generator>

<Adhesive compound>

<Crosslinkable compound>

<Solvent>
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone BCS: ethylene glycol monobutyl ether PB: propylene glycol monobutyl ether PGME: propylene glycol monomethyl ether

"Molecular weight measurement of polyimide polymer"
It measured as follows using the normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (made by Showa Denko KK) and the column (KD-803, KD-805) (made by Shodex).
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, 10 ml / L of tetrahydrofuran (THF))
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

"Measurement of imidization rate of polyimide polymer"
20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100
(X is the accumulated proton peak value derived from NH group of amic acid, y is the accumulated peak value of reference proton, α is the reference proton for one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) The number ratio.

<Synthesis Example 1>
D2 (6.89 g, 27.5 mmol), A1 (8.49 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) were mixed in NMP (38.9 g) and reacted at 50 ° C. for 5 hours. After that, D1 (1.80 g, 9.18 mmol) and NMP (19.5 g) were added and reacted at 40 ° C. for 6 hours. The resin solid content concentration was 25% by mass (hereinafter referred to as C _R 25%). A polyamic acid solution (1) was obtained. The number average molecular weight (Mn) of this polyamic acid was 21,300, and the weight average molecular weight (Mw) was 67,700.

<Synthesis Example 2>
After adding NMP to the polyamic acid solution (1) (30.0 g) obtained in Synthesis Example 1 and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (2.40 g) were used as imidization catalysts. In addition, the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (2). The imidation ratio of this polyimide was 55%, Mn was 19,000 and Mw was 50,200.

<Synthesis Example 3>
D2 (6.12 g, 24.5 mmol), A1 (7.55 g, 19.8 mmol), B1 (2.62 g, 9.91 mmol) and C2 (0.50 g, 3.29 mmol) NMP (36.8 g) were mixed at medium and allowed to react for 5 hours at 50 ℃, D1 (1.60g, 8.16mmol ) and NMP of (18.4 g) was added, reacted for 6 hours at 40 _℃, C R 25% of a polyamic acid A solution (3) was obtained. Mn of this polyamic acid was 20,200, and Mw was 63,500.

<Synthesis Example 4>
After adding NMP to the polyamic acid solution (3) (30.0 g) obtained in Synthesis Example 3 and diluting to 6% by mass, acetic anhydride (2.51 g) and pyridine (2.42 g) were used as imidization catalysts. In addition, the mixture was reacted at 50 ° C. for 4 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 54%, Mn was 17,500, and Mw was 48,800.

<Synthesis Example 5>
D2 (0.80 g, 3.20 mmol), A2 (2.55 g, 6.46 mmol) and B1 (2.56 g, 9.69 mmol) were mixed in PGME (16.8 g) and reacted at 50 ° C. for 12 hours. after, D1 (2.50 g, 12.7 mmol) and PGME a (8.40 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (5). Mn of this polyamic acid was 17,100 and Mw was 40,800.

<Synthesis Example 6>
D1 (3.30 g, 16.8 mmol), A2 (3.36 g, 8.52 mmol), B1 (1.80 g, 6.81 mmol) and C1 (0.18 g, 1.66 mmol) to PGME (26.0 g) And mixed at 50 ° C. for 12 hours to obtain a 25% C 2 _R polyamic acid solution (6). Mn of this polyamic acid was 15,900, and Mw was 39,200.

<Synthesis Example 7>
D2 (6.89 g, 27.5 mmol), A5 (8.40 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) were mixed in NMP (38.7 g) and reacted at 50 ° C. for 5 hours. after, D1 (1.80 g, 9.18 mmol) and NMP of (19.4 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (7). Mn of this polyamic acid was 20,500, and Mw was 65,300.

<Synthesis Example 8>
D3 (3.50 g, 15.6 mmol), A2 (2.50 g, 6.34 mmol) and B1 (2.51 g, 9.50 mmol) were mixed in PGME (25.5 g) and reacted at 50 ° C. for 15 hours. is allowed _to obtain a C R 25% polyamic acid solution (8). Mn of this polyamic acid was 14,800, and Mw was 37,900.

<Synthesis Example 9>
D3 (3.50 g, 15.6 mmol), A4 (1.56 g, 3.17 mmol), B1 (2.51 g, 9.50 mmol) and C2 (0.48 g, 3.15 mmol) NEP (24.1 g) And mixed at 50 ° C. for 12 hours to obtain a 25% C 2 _R polyamic acid solution.
To the obtained polyamic acid solution (30.0 g), NEP was added to dilute to 6% by mass, and then acetic anhydride (2.50 g) and pyridine (2.38 g) were added as an imidization catalyst, followed by 2 hours at 50 ° C. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (9). The imidation ratio of this polyimide was 48%, Mn was 16,500, and Mw was 44,200.

<Synthesis Example 10>
D4 (3.37 g, 11.2 mmol), A3 (2.46 g, 5.69 mmol), B1 (1.50 g, 5.68 mmol) and C2 (0.43 g, 2.83 mmol) to NMP (16.6 g) were mixed at medium and allowed to react for 5 hours at 50 ℃, D1 (0.55g, 2.80mmol ) and NMP of (8.31 g) was added, reacted for 6 hours at 40 _℃, C R 25% of a polyamic acid A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (2.38 g) were added as imidization catalysts, and the mixture was stirred at 50 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 57%, Mn was 17,300, and Mw was 45,800.

<Synthesis Example 11>
D5 (1.30 g, 6.13 mmol), A2 (3.67 g, 9.30 mmol) and B1 (1.64 g, 6.21 mmol) were mixed in PGME (16.8 g) and reacted at 50 ° C. for 12 hours. after, D1 (1.80 g, 9.18 mmol) and PGME a (8.42 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (11). Mn of this polyamic acid was 15,500, and Mw was 35,100.

<Synthesis Example 12>
D5 (1.70 g, 8.01 mmol), A4 (1.60 g, 3.25 mmol) and B1 (3.43 g, 13.0 mmol) were mixed in PGME (16.6 g) and reacted at 50 ° C. for 12 hours. after, D1 (1.57 g, 8.01 mmol) and PGME a (8.30 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (12). Mn of this polyamic acid was 13,800, and Mw was 32,500.
Table 44 shows the polyimide polymers obtained in the respective synthesis examples.

＊１はポリアミド酸を表す。

* 1 represents polyamic acid.

"Production of liquid crystal composition"
(Preparation of liquid crystal composition (1))
L1 (2.40 g), R1 (1.20 g), R2 (1.20 g) and P1 (0.012 g) were mixed to obtain a liquid crystal composition (1).
(Preparation of liquid crystal composition (2))
L1 (2.40 g), R1 (1.20 g), R2 (1.20 g), P1 (0.012 g), and S1 (0.024 g) were mixed to obtain a liquid crystal composition (2).
(Preparation of liquid crystal composition (3))
L1 (2.40 g), R1 (1.20 g), R2 (1.20 g), P1 (0.012 g), and S1 (0.12 g) were mixed to obtain a liquid crystal composition (3).
(Preparation of liquid crystal composition (4))
L1 (2.40 g), R1 (1.20 g), R2 (1.20 g), P1 (0.012 g), and S2 (0.048 g) were mixed to obtain a liquid crystal composition (4).

"Manufacture of liquid crystal alignment treatment agent"
In Examples 1 to 15 and Comparative Examples 1 to 3 described later, production examples of the liquid crystal aligning agent were described. These liquid crystal aligning agents were also used for the production of liquid crystal display elements and their evaluation. Tables 45 to 47 show the liquid crystal aligning agents obtained in these examples and comparative examples.

"Production of liquid crystal display elements and evaluation of liquid crystal orientation (glass substrate)"
A liquid crystal display element was produced using the liquid crystal aligning agents obtained in Examples 1 to 4, 10 and Comparative Examples 1 and 2. Specifically, these liquid crystal aligning agents were pressure filtered through a membrane filter having a pore diameter of 1 μm, and washed with pure water and IPA (isopropyl alcohol) 100 × 100 mm glass substrate with ITO electrode (length: 100 mm, width : 100 mm, thickness: 0.7 mm) is spin-coated on the ITO surface, and heat-treated on a hot plate at 100 ° C. for 5 minutes and in a heat-circulating clean oven at 210 ° C. for 30 minutes. Obtained an ITO substrate with a liquid crystal alignment film of 100 nm. 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 liquid crystal alignment film surface coated with the spacer of the substrate by the ODF method, and then bonded so that the liquid crystal alignment film interface of the other substrate faces. A liquid crystal display element was obtained.

The liquid crystal display element before this treatment was cut at a wavelength of 350 nm or less using a metal halide lamp with an illuminance of 20 mW and irradiated with ultraviolet rays for an irradiation time of 90 seconds. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled at 25 ° C. Thereby, a liquid crystal display element (reverse type element) was obtained.
The liquid crystal orientation was evaluated using this liquid crystal display element. The liquid crystal orientation was observed with a polarizing microscope (Nikon Corporation, ECLIPSE E600WPOL) to confirm whether or not the liquid crystal was vertically aligned. As a result, the liquid crystal was vertically aligned in any of the liquid crystal display elements of Examples and Comparative Examples.

"Production of liquid crystal display elements and evaluation of liquid crystal orientation (plastic substrate)"
Using the liquid crystal aligning agents obtained in Examples 5-9, 11-15 and Comparative Example 3, liquid crystal display elements were produced. Specifically, a liquid crystal alignment treatment agent was pressure-filtered with a membrane filter having a pore diameter of 1 μm, and washed with pure water, and a 150 × 150 mm ITO (polyethylene terephthalate) substrate with an ITO electrode (length: 150 mm, width: 150 mm, The coating is applied on the ITO surface with a thickness of 0.2 mm) with a bar coater, and is heated on a hot plate at 100 ° C. for 5 minutes and in a heat-circulating clean oven at 120 ° C. for 2 minutes to form a film. An ITO substrate with a liquid crystal alignment film having a thickness of 100 nm was obtained. 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 by the ODF method on the liquid crystal alignment film surface coated with the spacer of the substrate, and then bonded so that the liquid crystal alignment film interface of the other substrate faces, and the liquid crystal display before processing An element was obtained.
A liquid crystal display element (reverse type element) was obtained as the liquid crystal display element before this treatment by the same method as the above-mentioned “Preparation of liquid crystal display element and evaluation of liquid crystal alignment (glass substrate)”.
Using this liquid crystal display element, the liquid crystal alignment was evaluated in the same manner as in “Preparation of liquid crystal display element and evaluation of liquid crystal alignment (glass substrate)”. As a result, the liquid crystal was vertically aligned in any of the liquid crystal display elements of Examples and Comparative Examples.

"Evaluation of optical properties (transparency and scattering properties)"
Optical characteristics (transparency and scattering characteristics) were evaluated using the liquid crystal display element (glass substrate / plastic substrate) obtained by the above method.
The evaluation of transparency when no voltage was applied was performed by measuring the transmittance of the liquid crystal display element when no voltage was applied. Specifically, the transmittance was measured under the conditions of UV-3600 (manufactured by Shimadzu Corporation), temperature of 25 degrees, and scan wavelength of 300 to 800 nm. In the case of a liquid crystal display element (glass substrate), the glass substrate with an ITO electrode was used as a reference, and in the case of a liquid crystal display element (plastic substrate), a PET substrate with an ITO electrode was used. In the evaluation, the higher the transmittance based on the transmittance at a wavelength of 450 nm, the better the transparency.

Moreover, the transmittance | permeability after storing the liquid crystal display element produced by the said method for 12 hours in the 60 degreeC and 70% humidity constant temperature and humidity chamber was also evaluated. Specifically, the lower the rate of decrease in transmittance after storage in a constant temperature and humidity chamber with respect to the transmittance (initial value) immediately after the production of the liquid crystal display element, the better the evaluation.
Furthermore, the evaluation of the transmittance after irradiating the liquid crystal display element produced by the above method with ultraviolet rays of ² J / cm ^{2 in} terms of 365 nm using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite) is also possible. went. Specifically, the lower the transmittance decrease rate after ultraviolet irradiation with respect to the transmittance (initial value) immediately after manufacturing the liquid crystal display element, the better the evaluation.

Furthermore, in Examples 1-8, in addition to the above standard test, as an emphasis test, the transmittance was evaluated after being stored in a thermostatic chamber at a temperature of 60 ° C. and a humidity of 70% for 24 hours. It was. The evaluation method has the same conditions as described above.
Tables 48 to 50 show the transmittance (%) values immediately after the production of the liquid crystal display element (initial stage), after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet irradiation (ultraviolet light).
Evaluation of the scattering characteristic at the time of voltage application was performed by applying 30V by alternating current drive to a liquid crystal display element (glass substrate), and visually observing the orientation state of a liquid crystal. Specifically, the liquid crystal display element that was clouded, that is, the one that obtained the scattering characteristics was considered excellent in this evaluation (good display in the table).

In addition, the alignment state of the liquid crystal after the liquid crystal display element produced by the above method was stored for 12 hours in a constant temperature and humidity chamber having a temperature of 60 ° C. and a humidity of 70% was also confirmed. Specifically, the liquid crystal display element that was clouded, that is, the one that obtained the scattering characteristics was considered excellent in this evaluation (good display in the table).
Furthermore, the liquid crystal display element produced by the above method was irradiated with ² J / cm ² of ultraviolet rays in terms of 365 nm using a desktop UV curing device (HCT3B28HEX-1) (manufactured by Senlite). Confirmation was also performed. Specifically, the liquid crystal display element that was clouded, that is, the one that obtained the scattering characteristics was considered excellent in this evaluation (good display in the table).
Tables 48 to 50 show the results of the scattering characteristics immediately after the production of the liquid crystal display element (initial stage), after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet irradiation (ultraviolet light).

"Evaluation of adhesion between liquid crystal layer and liquid crystal alignment film"
Using the liquid crystal display element (glass substrate / plastic substrate) obtained by the above method, the adhesion between the liquid crystal layer and the liquid crystal alignment film was evaluated.
The liquid crystal display element was stored in a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 70% for 30 hours, and presence of bubbles in the liquid crystal display element and peeling of the element were confirmed. Specifically, it is considered that this device is excellent in this evaluation when no bubbles are observed in the device and the device is not peeled off (the liquid crystal layer and the liquid crystal alignment film are peeled off) (good display in the table). .

In addition, the presence or absence of bubbles in the liquid crystal display element after irradiation with ultraviolet rays of 5 J / cm ^{2 in} terms of 365 nm using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlite) on the liquid crystal display element and the element The peeling of was also confirmed. Specifically, in the same manner as described above, those in which no bubbles were observed in the device and the device was not peeled were considered to be excellent in this evaluation (good display in the table).
Furthermore, in Examples 1 to 4, 7, 8, and 10, in addition to the above standard test, as an emphasis test, the adhesion after being stored in a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 70% for 72 hours. Evaluation was also performed. The evaluation method has the same conditions as described above.
Tables 51 to 53 show the adhesion results (adhesiveness) between the liquid crystal layer and the liquid crystal alignment film after storage in a constant temperature and humidity chamber (constant temperature and humidity) and after irradiation with ultraviolet rays (ultraviolet rays).

<Example 1>
NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (1) (6.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25 ° C. for 24 hours. Then, BCS (19.5g) was added and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (1).

<Example 2>
NEP (21.6 g) is added to the polyimide powder (2) (1.50 g) obtained in Synthesis Example 2, and the mixture is stirred at 60 ° C. for 24 hours, and then Z1 (0.300 g) is added thereto at 24 ° C. for 24 hours. Stir for hours. Thereafter, PB (14.4 g) was added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (2).

<Example 3>
NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (3) (6.50 g) obtained in Synthesis Example 3, and the mixture was stirred at 25 ° C. for 24 hours. Then, BCS (19.5g) was added and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (3).

<Example 4>
NEP (21.6 g) was added to the polyimide powder (4) obtained in Synthesis Example 4 (1.50 g), and the mixture was stirred at 60 ° C. for 24 hours. Then, Z1 (0.300 g) was added, and 24 ° C. at 25 ° C. Stir for hours. Thereafter, PB (14.4 g) was added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (4).

<Example 5>
Γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.188 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was added at 25 ° C. for 24 hours. The liquid crystal aligning agent (5) was obtained by stirring.

<Example 8>
Γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.188 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was added at 25 ° C. for 24 hours. Stir. Then, N1 (0.063g), M1 (0.063g), and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (6).

<Example 9>
Γ-BL (8.08 g), PGME (28.6 g) and Z1 (0.125 g) were added to the polyamic acid solution (6) (5.00 g) obtained in Synthesis Example 6, and the mixture was added at 40 ° C. for 12 hours. Stir. Then, N1 (0.038g) and K1 (0.125g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (7).

<Example 10>
NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (7) (6.50 g) obtained in Synthesis Example 7, and the mixture was stirred at 25 ° C. for 24 hours. Then, BCS (19.5g) was added and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (8).

<Example 11>
To the polyamic acid solution (8) (5.00 g) obtained in Synthesis Example 8, γ-BL (4.04 g), PB (4.04 g), PGME (28.6 g) and Z2 (0.375 g) were added. In addition, the mixture was stirred at 25 ° C. for 24 hours. Then, N1 (0.088g) and K1 (0.063g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (9).

<Example 12>
Γ-BL (8.41 g) and PGME (33.6 g) were added to the polyimide powder (9) (1.30 g) obtained in Synthesis Example 9, and the mixture was stirred at 60 ° C. for 24 hours. 260 g) was added and stirred at 40 ° C. for 12 hours. Then, N1 (0.065g) and K1 (0.039g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (10).

<Example 13>
Γ-BL (6.31 g) and PGME (35.7 g) were added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10, and the mixture was stirred at 60 ° C. for 24 hours. 455 g) was added and stirred at 25 ° C. for 24 hours. Then, N1 (0.065g) and K1 (0.130g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (11).

<Example 14>
Γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.125 g) were added to the polyamic acid solution (11) (5.00 g) obtained in Synthesis Example 11, and 24 hours at 25 ° C. Stir. Then, N1 (0.063g) and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (12).

<Example 15>
Γ-BL (4.04 g), PGME (32.6 g), and Z2 (0.063 g) were added to the polyamic acid solution (12) (5.00 g) obtained in Synthesis Example 12, and the mixture was added at 25 ° C. for 24 hours. Stir. Then, N1 (0.063g) and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13).

<Comparative Example 1>
NMP (14.6 g) and BCS (19.5 g) were added to the polyamic acid solution (1) (6.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent ( 14) was obtained.
<Comparative example 2>
NEP (21.6 g) and PB (14.4 g) are added to the polyimide powder (2) (1.50 g) obtained in Synthesis Example 2, and the mixture is stirred at 60 ° C. for 24 hours. 15) was obtained.

<Comparative Example 3>
Γ-BL (6.06 g) and PGME (30.6 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal alignment treatment. Agent (16) was obtained.

It was confirmed that the liquid crystal aligning agents obtained in Examples 1 to 15 and Comparative Examples 1 to 3 were uniform solutions without any abnormality such as turbidity and precipitation.
These liquid crystal aligning agents (1) to (16) and the liquid crystal compositions (1) to (4) described above are used in combinations shown in Tables 48 to 51. Fabrication and evaluation were performed. The results are shown in Table 48 to Table 51. In addition, Example 6 is a liquid crystal display element using a liquid crystal aligning agent (5) and a liquid crystal composition (2), and Example 7 is a liquid crystal aligning agent (5) and a liquid crystal composition (3). ).

＊１〜＊５は、いずれも、全重合体100質量部に対する含有量（質量部）を示す。

* 1- * 5 show content (mass part) with respect to 100 mass parts of all the polymers, all.

＊１：素子内の数箇所に、液晶配向性の乱れが見られた。

* 1: Disturbance of liquid crystal alignment was observed at several locations in the device.

＊１：素子内に極少量の気泡が見られた。＊２：素子内に少量の気泡が見られた（＊１よりも多い）。＊３：素子内に多くの気泡が見られた（＊２よりも多い）。

* 1: A very small amount of bubbles was observed in the device. * 2: A small amount of bubbles was observed in the element (more than * 1). * 3: Many bubbles were observed in the element (more than * 2).

As can be seen from the above, the example was a device having better transparency when no voltage was applied, particularly after storage in a constant temperature and humidity chamber and after ultraviolet irradiation, as compared with the comparative example. Furthermore, an element having high adhesion between the liquid crystal layer and the liquid crystal alignment film was obtained. Further, even when a plastic substrate was used as the element substrate, these characteristics were good.
Specifically, the element of the example containing the specific compound in the liquid crystal alignment treatment agent has a higher transparency than that of the comparative example not containing the compound, particularly under high temperature and high humidity or after irradiation with ultraviolet rays. It became. More specifically, in the comparison under the same conditions, the comparison between Example 1 and Comparative Example 1, the comparison between Example 2 and Comparative Example 2, and the comparison between Example 5 and Comparative Example 3 are shown.

  In the specific side chain structure, when the formula [2-1] is used, the transparency of the device when no voltage is applied is higher than when the formula [2-2] is used. Even after being stored in a constant temperature and humidity chamber for a long time in the emphasis test, the transparency when no voltage was applied was higher. Further, in the evaluation of the adhesion between the liquid crystal layer and the liquid crystal alignment film, when the specific side chain structure of the formula [2-1] is used, after storing in a constant temperature and humidity chamber for a long time performed in the emphasis test. As a result, the adhesion was higher. Specifically, it is a comparison between Examples 1 and 10 under the same conditions in the standard test and the enhancement test.

In addition, when a specific compound is introduced into the liquid crystal composition, the transparency of the device when no voltage is applied is increased, and even after being stored in a constant temperature and humidity chamber for a long time in an emphasis test, The result was higher transparency when no voltage was applied. The effect became larger as the amount of the specific compound introduced was larger. Specifically, it is a comparison between Example 5 and 6 or 7 under the same conditions in the standard test and the enhancement test.
Furthermore, when a specific generator, an adhesive compound and a specific crosslinkable compound were introduced into the liquid crystal alignment treatment agent, the adhesion between the liquid crystal layer and the liquid crystal alignment film in the device was further improved. Specifically, it is a comparison between Examples 7 and 8 under the same conditions in the enhancement test.
Furthermore, in the case where a polyimide polymer is used as the specific polymer, when the specific diamine compound (2) is used as the diamine component, the adhesion between the liquid crystal layer and the liquid crystal alignment film in the device is further improved. It was. Specifically, a comparison between Examples 1 and 3 and a comparison between Examples 2 and 4 under the same conditions in the enhancement test.

<Example B series>
The meanings of the abbreviations used below are as follows. In addition, the rough outline used by Example A series is the same, respectively.
<Monomer>
E2: Octadecyltriethoxysilane
E3: 3-methacryloxypropyltrimethoxysilane,
E4: 3-ureidopropyltriethoxysilane, E5: tetraethoxysilane

＜溶媒＞
ＥＣＳ：エチレングリコールモノエチルエーテル
ＥＣ：ジエチレングリコールモノエチルエーテル

<Solvent>
ECS: Ethylene glycol monoethyl ether EC: Diethylene glycol monoethyl ether

"Synthesis of polyimide polymers"
<Synthesis Example 1>
D2 (6.89 g, 27.5 mmol), A1 (8.49 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) were mixed in NMP (38.9 g) and reacted at 50 ° C. for 5 hours. after, D1 (1.80 g, 9.18 mmol) and NMP of (19.5 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (1). Mn of this polyamic acid was 21,300 and Mw was 67,700.

<Synthesis Example 2>
After adding NMP to the polyamic acid solution (1) (30.0 g) obtained in Synthesis Example 1 and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (2.40 g) were used as imidization catalysts. In addition, the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (2). The imidation ratio of this polyimide was 55%, Mn was 19,000 and Mw was 50,200.

<Synthesis Example 3>
D2 (6.12 g, 24.5 mmol), A1 (7.55 g, 19.8 mmol), B1 (2.62 g, 9.91 mmol) and C2 (0.50 g, 3.29 mmol) NMP (36.8 g) were mixed at medium and allowed to react for 5 hours at 50 ℃, D1 (1.60g, 8.16mmol ) and NMP of (18.4 g) was added, reacted for 6 hours at 40 _℃, C R 25% of a polyamic acid A solution (3) was obtained. Mn of this polyamic acid was 20,200, and Mw was 63,500.

<Synthesis Example 4>
After adding NMP to the polyamic acid solution (3) (30.0 g) obtained in Synthesis Example 3 and diluting to 6% by mass, acetic anhydride (2.51 g) and pyridine (2.42 g) were used as imidization catalysts. In addition, the mixture was reacted at 50 ° C. for 4 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 54%, Mn was 17,500, and Mw was 48,800.

<Synthesis Example 5>
D2 (0.80 g, 3.20 mmol), A2 (2.55 g, 6.46 mmol) and B1 (2.56 g, 9.69 mmol) were mixed in PGME (16.8 g) and reacted at 50 ° C. for 12 hours. after, D1 (2.50 g, 12.7 mmol) and PGME a (8.40 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (5). Mn of this polyamic acid was 17,100 and Mw was 40,800.

<Synthesis Example 6>
D1 (3.30 g, 16.8 mmol), A2 (3.36 g, 8.52 mmol), B1 (1.80 g, 6.81 mmol) and C1 (0.18 g, 1.66 mmol) to PGME (26.0 g) And mixed at 50 ° C. for 12 hours to obtain a 25% C 2 _R polyamic acid solution (6). Mn of this polyamic acid was 15,900, and Mw was 39,200.

<Synthesis Example 7>
D2 (6.89 g, 27.5 mmol), A5 (8.40 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) were mixed in NMP (38.7 g) and reacted at 50 ° C. for 5 hours. after, D1 (1.80 g, 9.18 mmol) and NMP of (19.4 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (7). Mn of this polyamic acid was 20,500, and Mw was 65,300.

<Synthesis Example 8>
D3 (3.50 g, 15.6 mmol), A2 (2.50 g, 6.34 mmol) and B1 (2.51 g, 9.50 mmol) were mixed in PGME (25.5 g) and reacted at 50 ° C. for 15 hours. is allowed _to obtain a C R 25% polyamic acid solution (8). Mn of this polyamic acid was 14,800, and Mw was 37,900.

<Synthesis Example 9>
D3 (3.50 g, 15.6 mmol), A4 (1.56 g, 3.17 mmol), B1 (2.51 g, 9.50 mmol) and C2 (0.48 g, 3.15 mmol) NEP (24.1 g) And mixed at 50 ° C. for 12 hours to obtain a 25% C 2 _R polyamic acid solution.
To the obtained polyamic acid solution (30.0 g), NEP was added to dilute to 6% by mass, and then acetic anhydride (2.50 g) and pyridine (2.38 g) were added as an imidization catalyst, and the mixture was stirred at 50 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (9). The imidation ratio of this polyimide was 48%, Mn was 16,500, and Mw was 44,200.

<Synthesis Example 10>
D4 (3.37 g, 11.2 mmol), A3 (2.46 g, 5.69 mmol), B1 (1.50 g, 5.68 mmol) and C2 (0.43 g, 2.83 mmol) to NMP (16.6 g) were mixed at medium and allowed to react for 5 hours at 50 ℃, D1 (0.55g, 2.80mmol ) and NMP of (8.31 g) was added, reacted for 6 hours at 40 _℃, C R 25% of a polyamic acid A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (2.38 g) were added as imidization catalysts, and the mixture was stirred at 50 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 57%, Mn was 17,300, and Mw was 45,800.

<Synthesis Example 11>
D5 (1.30 g, 6.13 mmol), A2 (3.67 g, 9.30 mmol) and B1 (1.64 g, 6.21 mmol) were mixed in PGME (16.8 g) and reacted at 50 ° C. for 12 hours. after, D1 (1.80 g, 9.18 mmol) and PGME a (8.42 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (11). Mn of this polyamic acid was 15,500, and Mw was 35,100.

<Synthesis Example 12>
D5 (1.70 g, 8.01 mmol), A4 (1.60 g, 3.25 mmol) and B1 (3.43 g, 13.0 mmol) were mixed in PGME (16.6 g) and reacted at 50 ° C. for 12 hours. after, D1 (1.57 g, 8.01 mmol) and PGME a (8.30 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (12). Mn of this polyamic acid was 13,800, and Mw was 32,500.
Table 42 shows the polyimide polymers obtained in the respective synthesis examples.

＊１はポリアミド酸を表す。

* 1 represents polyamic acid.

<Synthesis Example 13>
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. A solution prepared by previously mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise to this solution 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 14>
In a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube, EC (25.4 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, EC (12.7 g), water (10.8 g), and a solution prepared by mixing oxalic acid (1.10 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 methanol solution (1.20 g) with an E4 content of 92 mass% and EC (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 15>
Prepare a solution of alkoxysilane monomer by mixing EC (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 EC (14.6 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) with an E4 content of 92 mass% and EC (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 16>
In a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube, ECS (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. A solution prepared by previously mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise to this solution 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 (4) having a SiO ₂ equivalent concentration of 12% by mass.
Table 43 shows the polysiloxane polymers obtained in the respective synthesis examples.

"Production of liquid crystal composition"
Liquid crystal compositions (1) to (4) were produced in the same manner as in the above A series of examples.

"Manufacture of liquid crystal alignment treatment agent"
In Examples 1 to 20 and Comparative Examples 1 to 5 to be described later, production examples of the liquid crystal alignment treatment agent were described. These liquid crystal aligning agents were also used for the production of liquid crystal display elements and their evaluation. Tables 54 to 56 show the liquid crystal aligning agents obtained in these examples and comparative examples.

"Production of liquid crystal display elements and evaluation of liquid crystal orientation (glass substrate)"
Using the liquid crystal aligning agents obtained in Examples 1-4, 10, 16, 17, 20, and Comparative Examples 1, 2, and 4, according to the same procedure as in the above-described A series examples, Fabrication was performed. Note that the liquid crystal was vertically aligned in any of the liquid crystal display elements of these Examples and Comparative Examples.

"Production of liquid crystal display elements and evaluation of liquid crystal orientation (plastic substrate)"
Using the liquid crystal aligning agents obtained in Examples 5-9, 11-15, 18, 19 and Comparative Examples 3 and 5, liquid crystal display elements were prepared according to the same procedure as in the above A series of examples. went.

"Evaluation of optical properties (transparency and scattering properties)"
The obtained liquid crystal display element (glass substrate / plastic substrate) was evaluated for optical properties (transparency and scattering properties).
Furthermore, in Examples 1-8, 10, 16, 17, and 20, after being stored in a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 70% for 24 hours as an emphasis test in addition to the above standard test. The transmittance was also evaluated. The evaluation method is under the same conditions as in the A series examples.
Tables 57 to 59 show the transmittance (%) values of the liquid crystal display element and immediately after production (initial), after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet irradiation (ultraviolet light).

"Evaluation of adhesion between liquid crystal layer and liquid crystal alignment film"
The obtained liquid crystal display element (glass substrate / plastic substrate) was evaluated for adhesion between the liquid crystal layer and the liquid crystal alignment film.
Further, in Examples 1 to 4, 7, 8, 10, 16, and 20, after being stored in a constant temperature and humidity chamber at a temperature of 60 ° C. and a humidity of 70% for 72 hours as an emphasis test in addition to the above standard test. The adhesion was also evaluated. In addition, the evaluation method is the same conditions as the examples of the A series. Tables 57 to 59 show the adhesion results (adhesion) between the liquid crystal layer and the liquid crystal alignment film after storage in a constant temperature and humidity chamber (constant temperature and humidity) and after irradiation with ultraviolet rays (ultraviolet rays).

<Example 1>
T3 (0.069 g), NMP (12.4 g) and BCS (16.5 g) were added to the polyamic acid solution (1) (5.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25 ° C. for 4 hours. Thus, a liquid crystal aligning agent (1) was obtained.

<Example 2>
NEP (16.8 g) and PB (16.8 g) were added to the polyimide powder (2) (1.40 g) obtained in Synthesis Example 2, and the mixture was stirred at 60 ° C. for 24 hours. Then, T3 (0.070g) was added and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (2).

<Example 3>
T3 (0.069 g), NMP (12.4 g) and BCS (16.5 g) were added to the polyamic acid solution (3) (5.50 g) obtained in Synthesis Example 3, and the mixture was stirred at 25 ° C. for 4 hours. Thus, 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. Using the obtained liquid crystal aligning agent (3) and the liquid crystal composition (1), a liquid crystal display element was produced and evaluated.

<Example 4>
NEP (16.8 g) and PB (16.8 g) were added to the polyimide powder (4) (1.40 g) obtained in Synthesis Example 4, and the mixture was stirred at 60 ° C. for 24 hours. Then, T3 (0.070g) was added and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (4).

<Example 5>
T3 (0.030 g), γ-BL (4.85 g) and PGME (24.5 g) were added to the polyamic acid solution (5) (4.00 g) obtained in Synthesis Example 5, and 4 hours at 25 ° C. The liquid crystal aligning agent (5) was obtained by stirring.

<Example 8>
To the polyamic acid solution (5) (4.00 g) obtained in Synthesis Example 5, T3 (0.030 g), N1 (0.050 g), M1 (0.050 g), K1 (0.070 g), γ- BL (4.85 g) and PGME (24.5 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal aligning agent (6).

<Example 9>
To the polyamic acid solution (6) (4.00 g) obtained in Synthesis Example 6, T1 (0.070 g), N1 (0.030 g), K1 (0.100 g), γ-BL (6.47 g) and PGME (22.9g) was added and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (7).

<Example 10>
T3 (0.050 g), NMP (9.00 g) and BCS (12.0 g) were added to the polyamic acid solution (7) (4.00 g) obtained in Synthesis Example 7, and the mixture was stirred at 25 ° C. for 4 hours. Thus, a liquid crystal aligning agent (8) was obtained.

<Example 11>
To the polyamic acid solution (8) obtained in Synthesis Example 8 (4.00 g), T3 (0.010 g), N1 (0.070 g), K1 (0.050 g), γ-BL (6.47 g), PB (1.62g) and PGME (21.3g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (9).

<Example 12>
Γ-BL (6.47 g) and PGME (25.9 g) were added to the polyimide powder (9) (1.00 g) obtained in Synthesis Example 9, and the mixture was stirred at 60 ° C. for 24 hours. Then, T2 (0.050g), N1 (0.050g), and K1 (0.030g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (10).

<Example 13>
Γ-BL (6.47 g) and PGME (25.9 g) were added to the polyimide powder (10) (1.00 g) obtained in Synthesis Example 10, and the mixture was stirred at 60 ° C. for 24 hours. Then, T3 (0.030g), N1 (0.050g), and K1 (0.100g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (11).

<Example 14>
To the polyamic acid solution (11) (4.00 g) obtained in Synthesis Example 11, T3 (0.030 g), N1 (0.050 g), K1 (0.070 g), γ-BL (4.85 g) and PGME (24.5g) was added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (12).

<Example 15>
To the polyamic acid solution (12) (4.00 g) obtained in Synthesis Example 12, T2 (0.070 g), N1 (0.050 g), K1 (0.070 g), γ-BL (3.23 g) and PGME (26.1 g) was added, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal aligning agent (13).

<Example 16>
T3 (0.066 g), BCS (9.50 g), PB (3.17 g) and ECS (9.33 g) were added to the polysiloxane solution (1) (11.0 g) obtained in Synthesis Example 13. It stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (14).

<Example 18>
T2 (0.071 g), PB (9.89 g), PGME (9.89 g) and EC (5.71 g) were added to the polysiloxane solution (2) (8.50 g) obtained in Synthesis Example 14. It stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (15).

<Example 19>
To the polysiloxane solution (3) (8.50 g) obtained in Synthesis Example 15, T1 (0.071 g), N1 (0.051 g), M1 (0.204 g), PB (9.89 g), PGME ( 9.89 g) and EC (5.71 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal aligning agent (16).

<Example 20>
T3 (0.066 g), BCS (9.50 g), PB (3.17 g) and ECS (9.33 g) were added to the polysiloxane solution (4) (11.0 g) obtained in Synthesis Example 16. It stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (17).

<Comparative Example 1>
NMP (12.4 g) and BCS (16.5 g) were added to the polyamic acid solution (1) (5.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25 ° C. for 4 hours. 18) was obtained.

<Comparative example 2>
NEP (16.8 g) and PB (16.8 g) are added to the polyimide powder (2) (1.40 g) obtained in Synthesis Example 2, and the mixture is stirred at 60 ° C. for 24 hours to obtain a liquid crystal alignment treatment agent ( 19) was obtained.

<Comparative Example 3>
Γ-BL (4.85 g) and PGME (24.5 g) were added to the polyamic acid solution (5) (4.00 g) obtained in Synthesis Example 5, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal alignment treatment. Agent (20) was obtained.

<Comparative example 4>
BCS (9.50 g), PB (3.17 g) and ECS (9.33 g) were added to the polysiloxane solution (1) (11.0 g) obtained in Synthesis Example 13, and the mixture was stirred at 25 ° C. for 4 hours. Thus, a liquid crystal aligning agent (21) was obtained.
<Comparative Example 5>
PB (9.89 g), PGME (9.89 g) and EC (5.71 g) were added to the polysiloxane solution (2) (8.50 g) obtained in Synthesis Example 14, and the mixture was stirred at 25 ° C. for 4 hours. Thus, a liquid crystal aligning agent (22) was obtained.

All of the liquid crystal aligning agents obtained in Examples 1 to 20 and Comparative Examples 1 to 5 were confirmed to be uniform solutions without any abnormality such as turbidity or precipitation.
These liquid crystal aligning agents (1) to (20) and the liquid crystal compositions (1) to (4) described above are used in combinations shown in Tables 47 to 52. Fabrication and evaluation were performed. The results are shown in Table 47 to Table 52.
In addition, Example 6 is a liquid crystal display element using a liquid crystal aligning agent (5) and a liquid crystal composition (2), and Example 7 is a liquid crystal aligning agent (5) and a liquid crystal composition (3). Example 17 is a liquid crystal display element using the liquid crystal aligning agent (14) and the liquid crystal composition (3).

＊１〜＊５は、いずれも、全重合体100質量部に対する含有量（質量部）を示す。

* 1- * 5 show content (mass part) with respect to 100 mass parts of all the polymers, all.

＊１：素子内の数箇所に、液晶配向性の乱れが見られた。

* 1: Disturbance of liquid crystal alignment was observed at several locations in the device.

＊１：素子内に極少量の気泡が見られた。＊２：素子内に少量の気泡が見られた（＊１よりも多い）。＊３：素子内に多くの気泡が見られた（＊２よりも多い）。

* 1: A very small amount of bubbles was observed in the device. * 2: A small amount of bubbles was observed in the element (more than * 1). * 3: Many bubbles were observed in the element (more than * 2).

Compared with the comparative example, the example was an element having better optical characteristics, that is, transparency in the initial stage, after storage in a constant temperature and humidity chamber, and after irradiation with ultraviolet light when no voltage was applied. Furthermore, the device has high adhesion between the liquid crystal layer and the liquid crystal alignment film. In particular, even when a plastic substrate was used as the element substrate, these characteristics were good.
Specifically, the device of the example containing the specific compound in the liquid crystal aligning agent has higher transparency when no voltage is applied immediately after the device is produced, compared to the comparative example not containing the compound. The results showed high transparency even under high temperature and high humidity or after irradiation with ultraviolet rays. More specifically, in the comparison under the same conditions, the comparison between Example 1 and Comparative Example 1, the comparison between Example 2 and Comparative Example 2, the comparison between Example 5 and Comparative Example 3, and the Example 16 And comparison between Comparative Example 4 and Example 18 and Comparative Example 5.

  Among the specific side chain structures, when the formula [2-1] is used, the transparency of the device when no voltage is applied is higher than when the formula [2-2] is used. Even after being stored in a constant temperature and humidity chamber for a long time in the emphasis test, the transparency when no voltage was applied was higher. Furthermore, in the evaluation of the adhesion between the liquid crystal layer and the liquid crystal alignment film, when the formula [2-1] is used, the adhesion is maintained even after being stored in a constant temperature and humidity chamber for a long time in the emphasis test. Higher results. Specifically, in the comparison under the same conditions in the standard test and the emphasis test, it is a comparison between Examples 1 and 10 and a comparison between Examples 16 and 20.

  In addition, when a specific compound is introduced into the liquid crystal composition, the transparency of the device when no voltage is applied increases, and even after being stored in a constant temperature and humidity chamber for a long time in an emphasis test. As a result, the transparency when no voltage was applied was higher. The effect became larger as the amount of the specific compound introduced was larger. Specifically, in the comparison under the same conditions in the standard test and the emphasis test, it is a comparison between Example 5 and 6 or 7, and a comparison between Examples 16 and 17.

Furthermore, when a specific generator, an adhesive compound and a specific crosslinkable compound were introduced into the liquid crystal alignment treatment agent, the adhesion between the liquid crystal layer and the liquid crystal alignment film in the device was further improved. Specifically, it is a comparison between Examples 7 and 8 in the comparison under the same conditions in the enhancement test.
Furthermore, in the case where a polyimide polymer is used as the specific polymer, when the specific second diamine compound is used as the diamine component, the adhesion between the liquid crystal layer and the liquid crystal alignment film in the device is further improved. It was. Specifically, in the comparison under the same conditions in the emphasis test, the comparison between Examples 1 and 3 and the comparison between Examples 2 and 4.

<Example C series>
The meanings of the abbreviations used below are the same as the meanings of the abbreviations defined in Example A series and Example B series.
<Synthesis Example 1>
D2 (6.89 g, 27.5 mmol), A1 (8.49 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) were mixed in NMP (38.9 g) and reacted at 50 ° C. for 5 hours. after, D1 (1.80 g, 9.18 mmol) and NMP of (19.5 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (1). The number average molecular weight (also referred to as Mn) of this polyamic acid was 21,300, and the weight average molecular weight (also referred to as Mw) was 67,700.

<Synthesis Example 2>
After adding NMP to the polyamic acid solution (1) (30.0 g) obtained in Synthesis Example 1 and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (2.40 g) were used as imidization catalysts. In addition, the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (2). The imidation ratio of this polyimide was 55%, Mn was 19,000 and Mw was 50,200.

<Synthesis Example 3>
D2 (6.12 g, 24.5 mmol), A1 (7.55 g, 19.8 mmol), B1 (2.62 g, 9.91 mmol) and C2 (0.50 g, 3.29 mmol) NMP (36.8 g) were mixed at medium and allowed to react for 5 hours at 50 ℃, D1 (1.60g, 8.16mmol ) and NMP of (18.4 g) was added, reacted for 6 hours at 40 _℃, C R 25% of a polyamic acid A solution (3) was obtained. Mn of this polyamic acid was 20,200, and Mw was 63,500.

<Synthesis Example 4>
After adding NMP to the polyamic acid solution (3) (30.0 g) obtained in Synthesis Example 3 and diluting to 6% by mass, acetic anhydride (2.51 g) and pyridine (2.42 g) were used as imidization catalysts. In addition, the mixture was reacted at 50 ° C. for 4 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 54%, Mn was 17,500, and Mw was 48,800.

<Synthesis Example 5>
D2 (0.80 g, 3.20 mmol), A2 (2.55 g, 6.46 mmol) and B1 (2.56 g, 9.69 mmol) were mixed in PGME (16.8 g) and reacted at 50 ° C. for 12 hours. after, D1 (2.50 g, 12.7 mmol) and PGME a (8.40 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (5). Mn of this polyamic acid was 17,100 and Mw was 40,800.

<Synthesis Example 6>
D1 (3.30 g, 16.8 mmol), A2 (3.36 g, 8.52 mmol), B1 (1.80 g, 6.81 mmol) and C1 (0.18 g, 1.66 mmol) to PGME (26.0 g) And mixed at 50 ° C. for 12 hours to obtain a 25% C 2 _R polyamic acid solution (6). Mn of this polyamic acid was 15,900, and Mw was 39,200.

<Synthesis Example 7>
D2 (6.89 g, 27.5 mmol), A5 (8.40 g, 22.3 mmol) and C2 (2.26 g, 14.9 mmol) were mixed in NMP (38.7 g) and reacted at 50 ° C. for 5 hours. after, D1 (1.80 g, 9.18 mmol) and NMP of (19.4 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (7). Mn of this polyamic acid was 20,500, and Mw was 65,300.

<Synthesis Example 8>
D3 (3.50 g, 15.6 mmol), A2 (2.50 g, 6.34 mmol) and B1 (2.51 g, 9.50 mmol) were mixed in PGME (25.5 g) and reacted at 50 ° C. for 15 hours. is allowed _to obtain a C R 25% polyamic acid solution (8). Mn of this polyamic acid was 14,800, and Mw was 37,900.

<Synthesis Example 9>
D3 (3.50 g, 15.6 mmol), A4 (1.56 g, 3.17 mmol), B1 (2.51 g, 9.50 mmol) and C2 (0.48 g, 3.15 mmol) NEP (24.1 g) And mixed at 50 ° C. for 12 hours to obtain a 25% C 2 _R polyamic acid solution.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (2.38 g) were added as imidization catalysts, and the mixture was stirred at 50 ° C. for 2 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (9). The imidation ratio of this polyimide was 48%, Mn was 16,500, and Mw was 44,200.

<Synthesis Example 10>
D4 (3.37 g, 11.2 mmol), A3 (2.46 g, 5.69 mmol), B1 (1.50 g, 5.68 mmol) and C2 (0.43 g, 2.83 mmol) to NMP (16.6 g) were mixed at medium and allowed to react for 5 hours at 50 ℃, D1 (0.55g, 2.80mmol ) and NMP of (8.31 g) was added, reacted for 6 hours at 40 _℃, C R 25% of a polyamic acid A solution was obtained.
After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (2.38 g) were added as imidization catalysts, and the mixture was stirred at 50 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 57%, Mn was 17,300, and Mw was 45,800.

<Synthesis Example 11>
D5 (1.30 g, 6.13 mmol), A2 (3.67 g, 9.30 mmol) and B1 (1.64 g, 6.21 mmol) were mixed in PGME (16.8 g) and reacted at 50 ° C. for 12 hours. after, D1 (1.80 g, 9.18 mmol) and PGME a (8.42 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (11). Mn of this polyamic acid was 15,500, and Mw was 35,100.

<Synthesis Example 12>
D5 (1.70 g, 8.01 mmol), A4 (1.60 g, 3.25 mmol) and B1 (3.43 g, 13.0 mmol) were mixed in PGME (16.6 g) and reacted at 50 ° C. for 12 hours. after, D1 (1.57 g, 8.01 mmol) and PGME a (8.30 g) was added, reacted for 6 hours at 40 ° _C., to obtain a C R 25% polyamic acid solution (12). Mn of this polyamic acid was 13,800, and Mw was 32,500.
Table 63 shows the polyimide polymers obtained in the respective synthesis examples.

＊１はポリアミド酸を表す。

* 1 represents polyamic acid.

"Production of liquid crystal composition"
Liquid crystal compositions (1) to (4) were produced in the same manner as in the above A series of examples.

"Manufacture of liquid crystal alignment treatment agent"
In Examples 1 to 15 and Comparative Examples 1 to 9 described later, production examples of the liquid crystal alignment treatment agent were described. These liquid crystal aligning agents were also used for the production of liquid crystal display elements and their evaluation. Tables 64 to 66 show the liquid crystal aligning agents obtained in these examples and comparative examples.

"Production of liquid crystal display elements and evaluation of liquid crystal orientation (glass substrate)"
Using the liquid crystal aligning agents obtained in Examples 1 to 4 and 10 and Comparative Examples 1 to 6, liquid crystal display elements were produced according to the same procedure as in the above-described A series examples. Note that the liquid crystal was vertically aligned in any of the liquid crystal display elements of these Examples and Comparative Examples.

"Production of liquid crystal display elements and evaluation of liquid crystal orientation (plastic substrate)"
Using the liquid crystal aligning agents obtained in Examples 5 to 9, 11 to 15 and Comparative Examples 6 to 9, liquid crystal display elements were produced according to the same procedure as the above-described A series examples.

"Evaluation of optical properties (transparency and scattering properties)"
Optical characteristics (transparency and scattering characteristics) were evaluated using the obtained liquid crystal display elements (glass substrate / plastic substrate).
Furthermore, in Examples 1 to 8 and Example 10, in addition to the above standard test, as an emphasis test, the transmittance after being stored in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 90% for 24 hours. Was also evaluated. The evaluation method is the same conditions as in the A-series examples.
Tables 67 to 69 show transmittances (%) immediately after the liquid crystal display device is manufactured (initial stage), after storage in a constant temperature and humidity chamber (constant temperature and humidity), and after ultraviolet irradiation (ultraviolet light).

"Evaluation of adhesion between liquid crystal layer and liquid crystal alignment film"
Using the obtained liquid crystal display element (glass substrate / plastic substrate), the adhesion between the liquid crystal layer and the liquid crystal alignment film was evaluated.
Furthermore, in Examples 1-4, 7, 8, and 10, in addition to the above standard test, as an emphasis test, the adhesion after being stored in a thermostatic chamber at a temperature of 80 ° C. and a humidity of 90% for 60 hours. Was also evaluated. The evaluation method is the same conditions as in the A-series examples.
Tables 70 to 72 show the results of adhesion (adhesion) between the liquid crystal layer and the liquid crystal alignment film after storage in a constant temperature and humidity chamber (constant temperature and humidity) and after irradiation with ultraviolet rays (ultraviolet rays).

<Example 1>
NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (1) (6.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25 ° C. for 24 hours. Then, T3 (0.082g) and BCS (19.5g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (1).

<Example 2>
NEP (21.6 g) is added to the polyimide powder (2) (1.50 g) obtained in Synthesis Example 2, and the mixture is stirred at 60 ° C. for 24 hours, and then Z1 (0.300 g) is added thereto at 24 ° C. for 24 hours. Stir for hours. Then, T3 (0.075g) and PB (14.4g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (2).
<Example 3>
NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (3) (6.50 g) obtained in Synthesis Example 3, and the mixture was stirred at 25 ° C. for 24 hours. Then, T3 (0.082g) and BCS (19.5g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (3).

<Example 4>
NEP (21.6 g) was added to the polyimide powder (4) obtained in Synthesis Example 4 (1.50 g), and the mixture was stirred at 60 ° C. for 24 hours. Then, Z1 (0.300 g) was added, and 24 ° C. at 25 ° C. Stir for hours. Then, T3 (0.075g) and PB (14.4g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (4).

<Example 5>
Γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.188 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was added at 25 ° C. for 24 hours. Stir. Then, T3 (0.038g) was added and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (5).

<Example 8>
Γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.188 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was added at 25 ° C. for 24 hours. Stir. Thereafter, T3 (0.038 g), N1 (0.063 g), M1 (0.063 g) and K1 (0.088 g) were added, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal aligning agent (6). .

<Example 9>
Γ-BL (8.08 g), PGME (28.6 g) and Z1 (0.125 g) were added to the polyamic acid solution (6) (5.00 g) obtained in Synthesis Example 6, and the mixture was added at 40 ° C. for 12 hours. Stir. Then, T1 (0.088g), N1 (0.038g), and K1 (0.125g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (7).
<Example 10>
NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (7) (6.50 g) obtained in Synthesis Example 7, and the mixture was stirred at 25 ° C. for 24 hours. Then, T3 (0.082g) and BCS (19.5g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (8).

<Example 11>
To the polyamic acid solution (8) (5.00 g) obtained in Synthesis Example 8, γ-BL (4.04 g), PB (4.04 g), PGME (28.6 g) and Z2 (0.375 g) were added. In addition, the mixture was stirred at 25 ° C. for 24 hours. Then, T3 (0.013g), N1 (0.088g), and K1 (0.063g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (9).

<Example 12>
Γ-BL (8.41 g) and PGME (33.6 g) were added to the polyimide powder (9) (1.30 g) obtained in Synthesis Example 9, and the mixture was stirred at 60 ° C. for 24 hours. 260 g) was added and stirred at 40 ° C. for 12 hours. Then, T2 (0.065g), N1 (0.065g) and K1 (0.039g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (10).

<Example 13>
Γ-BL (6.31 g) and PGME (35.7 g) were added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10, and the mixture was stirred at 60 ° C. for 24 hours. 455 g) was added and stirred at 25 ° C. for 24 hours. Then, T3 (0.039g), N1 (0.065g), and K1 (0.130g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (11).

<Example 14>
Γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.125 g) were added to the polyamic acid solution (11) (5.00 g) obtained in Synthesis Example 11, and 24 hours at 25 ° C. Stir. Then, T3 (0.038g), N1 (0.063g), and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (12).

<Example 15>
Γ-BL (4.04 g), PGME (32.6 g), and Z2 (0.063 g) were added to the polyamic acid solution (12) (5.00 g) obtained in Synthesis Example 12, and the mixture was added at 25 ° C. for 24 hours. Stir. Then, T2 (0.088g), N1 (0.063g) and K1 (0.088g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13).

<Comparative Example 1>
NMP (14.6 g) and BCS (19.5 g) were added to the polyamic acid solution (1) (6.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent ( 14) was obtained.

<Comparative example 2>
NMP (14.6 g) and Z2 (0.163 g) were added to the polyamic acid solution (1) (6.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25 ° C. for 24 hours. Then, BCS (19.5g) was added and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (15).

<Comparative Example 3>
T3 (0.082 g), NMP (14.6 g) and BCS (19.5 g) were added to the polyamic acid solution (1) (6.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 25 ° C. for 8 hours. Thus, a liquid crystal aligning agent (16) was obtained.

<Comparative example 4>
NEP (21.6 g) and PB (14.4 g) are added to the polyimide powder (2) (1.50 g) obtained in Synthesis Example 2, and the mixture is stirred at 60 ° C. for 24 hours. 17) was obtained.

<Comparative Example 5>
NEP (21.6 g) is added to the polyimide powder (2) (1.50 g) obtained in Synthesis Example 2, and the mixture is stirred at 60 ° C. for 24 hours, and then Z1 (0.300 g) is added thereto at 24 ° C. for 24 hours. Stir for hours. Then, PB (14.4g) was added and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (18).

<Comparative Example 6>
T3 (0.075 g), NEP (21.6 g) and PB (14.4 g) were added to the polyimide powder (2) (1.50 g) obtained in Synthesis Example 2, and the mixture was stirred at 60 ° C. for 24 hours. Thus, a liquid crystal aligning agent (19) was obtained.

<Comparative Example 7>
Γ-BL (6.06 g) and PGME (30.6 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal alignment treatment. Agent (20) was obtained.

<Comparative Example 8>
Γ-BL (6.06 g), PGME (30.6 g) and Z2 (0.188 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was added at 25 ° C. for 24 hours. The liquid crystal aligning agent (21) was obtained by stirring.
<Comparative Example 9>
T3 (0.038 g), γ-BL (6.06 g) and PGME (30.6 g) were added to the polyamic acid solution (5) (5.00 g) obtained in Synthesis Example 5, and the mixture was added at 25 ° C. for 8 hours. The liquid crystal aligning agent (22) was obtained by stirring.

All of the liquid crystal aligning agents obtained in Examples 1 to 15 and Comparative Examples 1 to 9 were confirmed to be uniform solutions without any abnormality such as turbidity and precipitation.
These liquid crystal aligning agents (1) to (22) and the liquid crystal compositions (1) to (4) described above are used in combinations shown in Tables 67 to 72. Fabrication and evaluation were performed. In addition, Example 6 is a liquid crystal display element using a liquid crystal aligning agent (5) and a liquid crystal composition (2), and Example 7 is a liquid crystal aligning agent (5) and a liquid crystal composition (3). ).

＊１〜＊５は、いずれも、全重合体100質量部に対する含有量（質量部）を示す。

* 1- * 5 show content (mass part) with respect to 100 mass parts of all the polymers, all.

＊１：素子内の数箇所に、液晶配向性の乱れが見られた。

* 1: Disturbance of liquid crystal alignment was observed at several locations in the device.

＊１：素子内に極少量の気泡が見られた。＊２：素子内に少量の気泡が見られた（＊１よりも多い）。＊３：素子内に多くの気泡が見られた（＊２よりも多い）。

* 1: A very small amount of bubbles was observed in the device. * 2: A small amount of bubbles was observed in the element (more than * 1). * 3: Many bubbles were observed in the element (more than * 2).

The example was a liquid crystal display element having better optical properties than the comparative example, that is, transparency when no voltage was applied, particularly after storage in a high-temperature and high-humidity tank and after ultraviolet irradiation. Furthermore, the device has high adhesion between the liquid crystal layer and the liquid crystal alignment film. Further, even when a plastic substrate was used as the element substrate, these characteristics were good.
Specifically, the example element containing the specific compound (1) and the specific compound (2) in the liquid crystal alignment treatment agent does not contain it, or in comparison with the comparative example containing either one, the temperature is particularly high. As a result, the transparency after exposure to moisture or ultraviolet rays increased, and the adhesion between the liquid crystal layer and the liquid crystal alignment film also increased. More specifically, it is a comparison between Example 1 and Comparative Examples 1 to 3 under the same conditions, a comparison between Example 2 and Comparative Examples 4 to 6, and a comparison between Example 5 and Comparative Examples 7 to 9. .

  Among the specific side chain structures, when the formula [3-1] is used, the liquid crystal display element is more transparent when no voltage is applied than when the formula [3-2] is used. The results show that the transparency when no voltage is applied becomes higher even after being stored in a constant temperature and humidity chamber for a long time in the emphasis test. In addition, in the evaluation of the adhesion between the liquid crystal layer and the liquid crystal alignment film, when the specific side chain structure of the formula [3-1] is used, it is stored in a constant temperature and humidity chamber for a long time in the emphasis test. Also, the results showed that these adhesion properties were higher. Specifically, it is a comparison between Example 1 and Example 10 under the same conditions in the standard test and the enhancement test.

  In addition, when a specific liquid crystal additive compound is introduced into the liquid crystal composition, the liquid crystal display element becomes more transparent when no voltage is applied, and further, after being stored in a constant temperature and humidity chamber for a long time in an emphasis test. As a result, the transparency when no voltage was applied was higher. The effect was greater as the amount of the specific liquid crystal additive compound introduced was larger. Specifically, it is a comparison between Example 5 and 6 or 7 under the same conditions in the standard test and the enhancement test. Furthermore, when the specific generator, the adhesive compound and the specific crosslinkable compound were introduced into the liquid crystal alignment treatment agent, the adhesion between the liquid crystal layer and the liquid crystal alignment film in the liquid crystal display element was further improved. . Specifically, it is a comparison between Examples 7 and 8 under the same conditions in the enhancement test.

  Furthermore, in the case where a polyimide polymer is used as the specific polymer, when the specific diamine compound (2) is used as the diamine component, the adhesion between the liquid crystal layer and the liquid crystal alignment film in the device is further improved. It was. Specifically, a comparison between Examples 1 and 3 and a comparison between Examples 2 and 4 under the same conditions in the enhancement test.

The liquid crystal display element of the present invention can be suitably used for a liquid crystal display for display purposes, a dimming window for controlling transmission and blocking of light, an optical shutter element, and the like.
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, when this element is used as a reverse-type element, transparency when no voltage is applied and scattering characteristics when voltage is applied are good. The efficiency of taking light in time is high, and the effect of preventing glare from outside light is also high. Therefore, the safety when driving a vehicle and the comfort during riding can be further improved. Moreover, when producing this element with a film and sticking it on the glass window of a vehicle and using it, the reliability of an element becomes high compared with the past.

  Furthermore, this element can be used for a light guide plate of a display device such as an LCD or an OLED or a back plate of a transparent display using these displays. Specifically, when used for the back plate of a transparent display, for example, when the screen is displayed on the transparent display by combining the transparent display and the present element, to prevent light from entering from the back by the present element. Can be used for This element is in a scattering state in which a voltage is applied when screen display is performed on a transparent display, and the screen display can be sharpened. After the screen display is completed, the device is in a transparent state in which no voltage is applied.

  The entire contents of the specifications, claims, and abstracts of Japanese Patent Applications Nos. 2015-040263, 2015-040264 and Japanese Patent Application No. 2015-040265 filed on March 2, 2015 are here. It is incorporated by reference as a disclosure of the specification of the present invention.

Claims (14)

A liquid crystal composition including a liquid crystal and a polymerizable compound disposed between a pair of substrates provided with electrodes has a liquid crystal layer cured by irradiating ultraviolet rays, and at least one of the substrates vertically aligns the liquid crystal A transmission scattering type liquid crystal display element that is in a transparent state when no voltage is applied and is in a scattering state when a voltage is applied.
A liquid crystal display element, wherein the liquid crystal alignment film is obtained from a liquid crystal aligning agent containing the following components.
Component (A): at least one compound selected from the group consisting of a compound of the following formula [1-1] and a compound of the following formula [1-2].
Component (B): a polymer having at least one structure selected from the group consisting of the following formula [2-1] and formula [2-2].

(T ¹ represents at least one selected from the group consisting of an alkylene group having 1 to 20 carbon atoms, or an organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring, and the alkylene group having 1 to 20 carbon atoms. Any —CH ₂ — represents —O—, —CO—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —CON (CH ₃ ) —, —S— or —. SO ₂ — may be substituted, and T ² is a single bond, —O—, —NH—, —N (CH ₃ ) —, —CH ₂ O—, —OCH ₂ —, —CONH—, —NHCO—. , —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO—, and —OCO—, wherein T ³ represents the following formula [1-a] to [[ 1-g] represents at least one structure selected from the group consisting of:

(T ^A is a hydrogen atom or an benzene ring .T ^B is a benzene ring, .T ^C indicating at least one cyclic group selected from the group consisting of hexane ring and heterocyclic cycloheteroalkyl alkyl having 1 to 18 carbon atoms And at least one selected from the group consisting of a 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.)

(S ¹ represents at least one structure selected from the group consisting of the structures of the following formulas [1-a] to [1-l]. S ² represents a single bond or an alkylene group having 1 to 24 carbon atoms. , Any —CH ₂ — in the alkylene group is —O—, —CO—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —CON (CH ₃ ) —, — S ³ may be replaced by S— or —SO ₂ —, and S ³ has at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number of 17 to 17 having a steroid skeleton. 51 represents a divalent organic group, and an arbitrary hydrogen atom on the cyclic group 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, C1-C3 fluorine-containing alkoxyl group or fluorine Good .S ⁴ be substituted with atoms is a single _{bond, -O -, - OCH 2 -} , - CH 2 O -, - COO- and at least one bond group selected from the group consisting of -OCO- S ⁵ represents at least one 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, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group with 1 to 3 carbon atoms, a fluorine-containing alkoxyl group with 1 to 3 carbon atoms, or a fluorine atom, and sA represents an integer of 0 to 4. S ⁶ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 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 having 1 to 18 carbon atoms. From the base That indicates at least one selected from the group.)

(S ^A is a hydrogen atom or an benzene ring .S ^B is a benzene ring, .S ^C indicating at least one cyclic group selected from the group consisting of hexane ring and heterocyclic cycloheteroalkyl alkyl having 1 to 18 carbon atoms And at least one selected from the group consisting of a 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, S ^{D to} S ^F Each represents an alkyl group having 1 to 5 carbon atoms.)

(Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ). —, —N (CH ₃ ) CO—, —COO— and —OCO— represent at least one linking group selected from the group consisting of Y ² is a single bond or — (CH ₂ ) _b — (b is 1 Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— and —. Y ⁴ represents at least one selected from the group consisting of OCO-, and Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number of 17 to 17 having a steroid skeleton. 51 represents a divalent organic group, and an arbitrary hydrogen atom on the cyclic group has 1 carbon atom. 3 alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, good .Y ⁵ be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms benzene At least one cyclic group selected from the group consisting of a ring, a cyclohexane ring and a heterocyclic ring, wherein any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl having 1 to 3 carbon atoms Group, 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, n represents an integer of 0 to 4. Y ⁶ represents 1 carbon atom. -18 alkyl group, alkenyl group having 2 to 18 carbon atoms, fluorine-containing alkyl group having 1 to 18 carbon atoms, alkoxyl group having 1 to 18 carbon atoms and fluorine-containing alkoxyl group having 1 to 18 carbon atoms. At least one selected from the group of

(Y ⁷ is a single bond, —O—, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, —COO— and —OCO—. And Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. 2. The liquid crystal display device according to claim 1, wherein the compound [1-1] of component (A) is at least one selected from the group consisting of compounds of the following formulas [1a-1] to [1a-6]. .

(Ta and Tb are each an integer of 1 to 12, Tc and Td are each an integer of 1 to 10, and Te and Tf are integers of 1 to 6, respectively .) (A) S ¹ in the formula [1-2] of the component is at least one structure selected from the group consisting of the formula [1-a] to the formula [1-d] and the formula [1-f]. The liquid crystal display element according to claim 1. 2. The liquid crystal according to claim 1, wherein S ¹ in the formula [1-2] of the component (A) is at least one structure selected from the group consisting of the formulas [1-h] to [1-l]. Display element.   The polymer of component (B) is at least one selected from the group consisting of acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane. The liquid crystal display element of any one of -4.   The polymer of (B) component is a polyimide precursor obtained by reacting a diamine component containing a diamine compound having the structure of formula [2-1] or formula [2-2] and a tetracarboxylic acid component, or the The liquid crystal display element according to claim 1, which is a polyimide obtained by imidizing a polyimide precursor. The liquid crystal display element according to claim 6, wherein the diamine compound is represented by the following formula [2a].

(Y represents Formula [2-1] or Formula [2-2]. N1 represents an integer of 1 to 4.) The liquid crystal display element of Claim 6 or 7 in which the said diamine component contains the diamine compound of following formula [3a].

(W represents the structure of the following formula [3]. M1 represents an integer of 1 to 4.)

(W ¹ is a single bond, —O—, —NH—, —N (CH ₃ ) —, —CH ₂ O—, —CONH—, —NHCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO -, - COO- and .W ² indicating at least one bond group selected from the group consisting of -OCO- a single bond, an alkylene group having 1 to 18 carbon atoms, or a benzene ring, cyclohexane ring and heterocyclic An organic group having 6 to 24 carbon atoms having at least one cyclic group selected from the group consisting of: an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms. Or a fluorine-containing alkyl group having 1 to 3 carbon atoms or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, and W ³ is a single bond, —O—, —NH—, —N ( _{CH 3) -, - CH 2} O -, - CONH -, - NHC _{-, - CON (CH 3)} -, - N (CH 3) CO -, - COO- and .W ⁴ the following formula exhibits at least one selected from the group consisting of -OCO- [3-a] ~ formula It shows at least one structure selected from the group consisting of [3-g].)

(W ^A represents a hydrogen atom or a benzene ring. W ^B represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. W ^C represents an alkyl having 1 to 18 carbon atoms. And at least one selected from the group consisting of a 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 display element according to any one of claims 6 to 8, wherein the tetracarboxylic acid component includes a tetracarboxylic dianhydride represented by the following formula [4].

(Z represents at least one structure selected from the group consisting of the structures of the following formulas [4a] to [4k].)

(Z ^{1 to} Z ⁴ each independently represents at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group. Group.) The polymer of the component (B) is a polysiloxane obtained by polycondensation of an alkoxysilane of the following formula [A1], or the alkoxysilane of the formula [A1] and the following formula [A2] or formula [A3] The liquid crystal display element of any one of Claims 1-4 containing the polysiloxane obtained by polycondensing with alkoxysilane.

(A ¹ represents the structure of the above formula [2-1] or [2-2]. A ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. A ³ represents an alkyl having 1 to 5 carbon atoms. M represents an integer of 1 or 2. n represents an integer of 0 to 2. p represents an integer of 0 to 3. However, m + n + p is 4.

(B ¹ is a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, methacryl group, acryl group, an organic group having 2 to 12 carbon atoms and having at least one selected from the group consisting of 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 an integer of 0 to 2. P represents an integer of 0 to 3, where m + n + p is 4.)

^{(D 1} is .D ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is an integer of .n 0-3 represents an alkyl group having 1 to 5 carbon atoms.)   The liquid crystal according to any one of claims 1 to 10, wherein the liquid crystal alignment treatment agent contains at least one generator selected from the group consisting of a photo radical generator, a photo acid generator, and a photo base generator. Display element.   The liquid crystal aligning agent has at least one substituent 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 an alkoxyalkyl group having 1 to 3 carbon atoms. The liquid crystal display element as described in any one of Claims 1-11 containing a compound. The liquid crystal composition, the formula [1-1] The liquid crystal display device according to any one of claims 1 to 12 containing a compound or compounds of the formula [1-2] in. The liquid crystal display element according to any one of claims 1 to 13 , wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate.