JP2020079232A - Liquid crystal orientation agent, liquid crystal orientation membrane, and liquid crystal display device - Google Patents

Abstract

To provide: a liquid crystal orientation agent which makes a liquid crystal display device possible, the liquid crystal display device having a fast response speed and excellent after-image characteristics derived from AC; and a liquid crystal display device.SOLUTION: The liquid crystal display device is formed by incorporating a polymerizable compound represented by formula (1) in a liquid crystal orientation agent and/or a liquid crystal layer. (Xand Xrepresent a bond group such as an ether bond; Sand Srepresent a C2-9 linear alkylene group; and S, X, X, and Sare selected so that the molecule becomes left-right asymmetric.)SELECTED DRAWING: None

Description

  The present invention provides a liquid crystal aligning agent that can be suitably used for a liquid crystal display device produced by irradiating ultraviolet rays in a state where a voltage is applied to liquid crystal molecules, a liquid crystal aligning film formed from the liquid crystal aligning agent, and the liquid crystal. The present invention relates to a liquid crystal display device having an alignment film.

In a liquid crystal display device of a type (also called a vertical alignment (VA) type) in which liquid crystal molecules vertically aligned with respect to a substrate respond by an electric field, a voltage is applied to the liquid crystal molecules during the manufacturing process. However, there are some that include a step of irradiating ultraviolet rays.
In such a vertical alignment type liquid crystal display device (PSA (Polymer Sustained Alignment) type liquid crystal display or the like), a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to apply a voltage to a liquid crystal cell. There is known a technique for increasing the response speed of liquid crystal by irradiating ultraviolet rays while applying a voltage (see Patent Document 1 and Non-Patent Document 1).

Usually, the tilting direction of liquid crystal molecules in response to an electric field is controlled by a protrusion provided on a substrate or a slit provided in a display electrode, but a photopolymerizable compound is added to a liquid crystal composition, By irradiating ultraviolet rays while applying a voltage to the liquid crystal cell, a polymer structure that memorizes the tilted direction of the liquid crystal molecules is formed on the liquid crystal alignment film. It is said that the response speed of the liquid crystal display element is faster than that of the method of controlling the.
It has also been reported that the response speed of the liquid crystal display device is increased by adding the photopolymerizable compound to the liquid crystal alignment film instead of the liquid crystal composition (SC-PVA type liquid crystal display) (non- See Patent Document 2).

Japanese Patent Laid-Open No. 2003-307720.

K. Hanaoka, SID 04 DIGEST, P.1200-1202. K.H Y.-J.Lee, SID 09 DIGEST, P.666-668.

  In recent years, it has been desired that the response speed of the liquid crystal display element is further increased, and it is considered that the response speed of the liquid crystal display element is increased by increasing the addition amount of the photopolymerizable compound. The photopolymerizable compound has a property that it is difficult to dissolve in the solvent used for the liquid crystal aligning agent. Therefore, when the liquid crystal aligning agent is stored, a problem of storage stability arises in that the photopolymerizable compound is precipitated. Further, when the liquid crystal display element is exposed to a temperature change during the manufacturing process, a part of the polymerizable compound may be eluted from the liquid crystal alignment film into the liquid crystal or may be crystallized in the liquid crystal. There is. Especially, when the solubility of the polymerizable compound in the liquid crystal is low, crystallization in the liquid crystal is likely to occur. Such crystallization of the polymerizable compound in the liquid crystal serves as a bright spot source in the display device, which leads to deterioration in display quality of the device.

Another problem of the liquid crystal display element is image sticking (afterimage), which may occur when the same pattern is displayed for a long time. One of the causes of this burn-in is due to the accumulation of charges. The image sticking due to the accumulation of electric charges is also called DC image sticking, but can be suppressed to some extent by a drive for applying a voltage whose polarity is inverted, that is, a polarity inversion drive. On the other hand, burn-in occurs even if the pretilt angle changes slightly. When the pretilt angle changes, the VT characteristic is affected, and therefore the transmittance changes even if the same voltage is applied. Since the applied voltage during white display is different from the applied voltage during black display, the amount of change in tilt angle varies depending on the applied voltage. Burn-in may be recognized. Such image sticking cannot be suppressed even by performing polarity reversal drive, and is also called AC image sticking.
An object of the present invention is to solve the above-mentioned problems of the conventional technology.

（式中、Ｘ^１及びＸ^２は、それぞれ独立して、エーテル結合及びエステル結合から選ばれる結合基を表し、Ｓ^１及びＳ^２は、それぞれ独立して、炭素数２〜９の直鎖アルキレン基を表し、かつ、当該Ｓ^１、Ｘ^１、Ｘ^２及びＳ^２は、分子が左右非対称となるように選択されてなる。） The present inventor has carried out research to achieve the above object, and has reached the present invention having the following points.
1. A liquid crystal aligning agent containing a polymerizable compound represented by the following formula (1) and at least one polymer selected from the group consisting of a polyimide precursor and a polyimide.

(In the formula, X ¹ and X ² each independently represent a bonding group selected from an ether bond and an ester bond, and S ¹ and S ² each independently represent a linear alkylene having 2 to 9 carbon atoms. Represents a group, and said S ¹ , X ¹ , X ² and S ² are selected such that the molecule is bilaterally asymmetric.)

2. ^2. The liquid crystal aligning agent according to 1 above, wherein in the polymerizable compound (1), S ¹ and S ² are alkylene groups having different carbon numbers.
3. In the polymerizable compound (1), one of X ¹ and X ² is an ether bond and the other is an ester bond, or X ¹ is an ester bond bonded to S ¹ on the carbonyl side, and X ² is 3. The liquid crystal aligning agent according to 1 or 2 above, which is an ester group bonded to S ² on the oxygen atom side.
4. 4. The liquid crystal aligning agent according to any one of 1 to 3 above, wherein at least one polymer selected from the group consisting of a polyimide precursor and a polyimide has a side chain for vertically aligning liquid crystals.
5. 5. The liquid crystal aligning agent according to any one of 1 to 4 above, wherein at least one polymer selected from the group consisting of a polyimide precursor and a polyimide further has a photoreactive side chain.
6. A liquid crystal alignment film comprising the liquid crystal alignment agent according to any one of 1 to 5 above.
7. A liquid crystal display device having the liquid crystal alignment film as described in 6 above.

（式中、Ｘ^１及びＸ^２は、それぞれ独立して、エーテル結合及びエステル結合から選ばれる結合基を表し、Ｓ^１及びＳ^２は、それぞれ独立して、炭素数２〜９の直鎖アルキレン基を表し、かつ、当該Ｓ^１、Ｘ^１、Ｘ^２及びＳ^２は、分子が左右非対称となるように選択される。） 8. A liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyimide precursor and a polyimide is applied onto two substrates to form a liquid crystal aligning layer, and the liquid crystal aligning layer is made to face each other. A method for manufacturing a vertical alignment type liquid crystal display device, in which a plurality of substrates are arranged, a liquid crystal layer is sandwiched between the two substrates, and ultraviolet rays are applied while applying an electric field to the liquid crystal layer,
At least one of a liquid crystal aligning agent and a liquid crystal layer is made to contain the polymeric compound represented by Formula (1), The manufacturing method of the liquid crystal display element characterized by the above-mentioned.

(In the formula, X ¹ and X ² each independently represent a bonding group selected from an ether bond and an ester bond, and S ¹ and S ² each independently represent a linear alkylene having 2 to 9 carbon atoms. Represents a group, and said S ¹ , X ¹ , X ² and S ² are selected such that the molecule is left-right asymmetric.)

9. 9. The production method according to the above 8, wherein in the polymerizable compound (1), S ¹ and S ² are alkylene groups having different carbon numbers.
10. In the polymerizable compound (1), one of X ¹ and X ² is an ether bond and the other is an ester bond, or X ¹ is an ester bond which bonds to S ¹ on the carbonyl side, and X ² 10. The production method according to the above 8 or 9, wherein is an ester group bonded to S ² on the oxygen atom side.
11. 11. The production method according to any one of 8 to 10 above, wherein at least one polymer selected from the group consisting of a polyimide precursor and a polyimide has a side chain for vertically aligning a liquid crystal.
12. 12. The production method according to any one of 8 to 11 above, wherein at least one polymer selected from the group consisting of a polyimide precursor and a polyimide further has a photoreactive side chain.

（式中、Ｘ^１及びＸ^２は、それぞれ独立して、エーテル結合及びエステル結合から選ばれる結合基を表し、Ｓ^１及びＳ^２は、それぞれ独立して、炭素数２〜９の直鎖アルキレン基を表し、かつ、Ｓ^１、Ｘ^１、Ｘ^２及びＳ^２は、分子が左右非対称となるように選択される。） 13. A polymerizable compound represented by the following formula (1).

(In the formula, X ¹ and X ² each independently represent a bonding group selected from an ether bond and an ester bond, and S ¹ and S ² each independently represent a linear alkylene having 2 to 9 carbon atoms. Represents a group, and S ¹ , X ¹ , X ² and S ² are selected such that the molecule is left-right asymmetric.)

14. 14. The polymerizable compound according to the above 13, wherein in the formula (1), S ¹ and S ² are alkylene groups having different carbon numbers.
15. In formula (1), ^one of X ¹ and X ² is an ether bond and the other is an ester bond, or X ¹ is an ester bond bonding to S ¹ on the carbonyl side, and X ² is an oxygen atom. 15. The polymerizable compound according to 13 or 14 above, which is an ester group bonded to S ² on the side.

  According to the present invention, a liquid crystal aligning agent and/or a novel polymerizable compound which enables the provision of a liquid crystal display element having a high response speed and excellent AC afterimage characteristics by containing it in a liquid crystal layer is contained. It is possible to obtain a liquid crystal aligning agent, a liquid crystal aligning film formed by using the liquid crystal aligning agent, and a device having a high response speed, in particular, a vertical aligning type device.

式（１）中、Ｘ^１、Ｘ^２、Ｓ^１、及びＳ^２の定義は、それぞれ上記したとおりである。なかでも、Ｓ^１及びＳ^２は、それぞれ独立して、炭素数２〜６の直鎖アルキレン基が好ましい。 <Polymerizable compound>
The polymerizable compound contained in the liquid crystal aligning agent of the present invention is represented by the following formula (1).

In formula (1), the definitions of X ¹ , X ² , S ¹ , and S ² are as described above. Among them, S ¹ and S ² are preferably each independently a linear alkylene group having 2 to 6 carbon atoms.

As a preferred method for causing S ¹ , X ¹ , X ² and S ² to be bilaterally asymmetric, a method of selecting an alkylene group in which S ¹ and S ² have different carbon numbers (method 1) and a method (method 2) of selecting a bonding group in which X ¹ and X ² are left-right asymmetrical to each other. Here, it is also possible to use the method 1 and the method 2 together.
The method 2, specifically, the one ether bond X ¹ and X ^2, a method of the other ester bonds (2-1), which binds to S ¹ and X ¹ carbonyl side ester As a bond, a method (Method 2-2) in which X ² is an ester group which bonds to S ² on the oxygen atom side can be mentioned.
Among such compounds, a compound having an alkylene group having a carbon number different from each other can be obtained by the production method described in International Patent Application Publication WO 2012/002513. Moreover, when it is desired to form an ether bond on one side and an ester bond on the other side, in the production method described in International Patent Application Publication WO 2012/002513, 4-(4-hydroxyphenyl)benzoic acid is used as a raw material instead of bisphenol. It may be manufactured by using.

As a method of making the molecule asymmetrical, in addition to the above Method 1 and Method 2, a method in which the left and right polymerizable groups are different (Method 3), and a substituent is introduced so that the benzene ring becomes asymmetrical. There is a method (method 4) for doing so.
By selecting at least one method selected from Method 1 and Method 2 described above, the solubility of the polymerizable compound is improved, and the afterimage characteristics derived from AC are higher than those when Method 3 or Method 4 is selected. I found it to be excellent. Although the reason for this is not clear, it is believed that the afterimage characteristics derived from AC are caused by stacking of the ring structure of the polymerizable compound. However, when Method 1 or Method 2 is selected, Method 3 or Method 4 is selected. It is considered that stacking is not hindered as compared with the case of selection.

<Polyimide precursor and/or polymer from polyimide>
In a liquid crystal display device formed by being contained in a liquid crystal aligning agent and/or a liquid crystal layer, at least one polymer selected from the group consisting of a polyimide precursor and a polyimide that is preferably used (hereinafter, also referred to as a specific polymer). As the material, a known polyimide precursor or polyimide used as a liquid crystal aligning agent can be used. The polyimide precursor specifically includes polyamic acid and polyamic acid ester.

  The polyimide precursor or polyimide, which is a specific polymer, preferably has a side chain (I) for vertically aligning liquid crystals for PSA type liquid crystal displays, and vertically for SC-PVA type liquid crystal displays. In addition to the side chain (I) to be orientated in, it is preferable to have a photoreactive side chain (II).

<Side chain (I) for vertically aligning liquid crystal>
The side chain (I) for vertically aligning the liquid crystal (hereinafter, also referred to as side chain A) is a side chain having the ability of vertically aligning liquid crystal molecules with respect to the substrate, and if it has this ability. The structure is not limited. As such a side chain, for example, a long-chain alkyl group, a fluoroalkyl group, a cyclic group having an alkyl group or a fluoroalkyl group at the end, a steroid group, etc. are known, and are preferably used in the present invention. These groups may be directly bonded to the main chain of the specific polymer as long as they have the above-mentioned ability, or may be bonded via an appropriate bonding group.

Examples of the side chain A include those represented by the following formula (a).
In the formula (a), l, m and n each independently represent an integer of 0 or 1, and R ¹ is an alkylene group having 1 to 6 carbon atoms, —O—, —COO—, —OCO—. _{, -NH -, - NHCO -,} - CONH -, - COOCH 2 -, - CH 2 OCO -, - CH 2 COO -, - OCOCH 2 - or alkylene of 1 to 3 carbon atoms - an ether group. R ² , R ³ and R ⁴ each independently represent a phenylene group or a cycloalkylene group, and R ⁵ is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, or 1 carbon atom. ~ 24 fluorine-containing alkyl group, C 1-24 fluorine-containing alkoxy group, fluorine group, cyano group, nitro group, azo group, formyl group, acetyl group, acetoxy group, hydroxyl group, aromatic ring, aliphatic ring, hetero It represents a ring or a macrocyclic substitution product thereof.

From the viewpoint of ease of synthesis, R ¹ is preferably —O—, —COO—, —CONH—, or an alkylene-ether group having 1 to 3 carbon atoms.
R ² , R ³ and R ⁴ are the combinations of l, m, n, R ² , R ³ and R ⁴ shown in Table 1 below from the viewpoint of ease of synthesis and the ability to vertically align the liquid crystal. preferable.

[Table 1]
______________________________________________________
l mn R ² R ³ R ⁴
___________________________________________________
1 1 1 phenylene phenylene cyclohexylene 1 1 1 phenylene cyclohexylene cyclohexylene 1 1 1 cyclohexylene cyclohexylene cyclohexylene 1 1 0 phenylene phenylene
1 1 0 Phenylene cyclohexylene ―
______________________________________________________

When at least one of l, m and n is 1, R ⁵ is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group having 2 to 14 carbon atoms, and more preferably hydrogen. An atom, an alkyl group having 2 to 12 carbon atoms or a fluorine-containing alkyl group having 2 to 12 carbon atoms. When l, m and n are all 0, R ⁵ is preferably an alkyl group having 12 to 22 carbon atoms, a fluorine-containing alkyl group having 12 to 22 carbon atoms, an aromatic ring, an aliphatic ring or a heterocycle. Or a macrocyclic substituted product thereof, more preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group having 12 to 20 carbon atoms.

  The ability to vertically align the liquid crystal depends on the structure of the side chain A described above. Generally, the larger the amount of the side chain A contained in the polymer is, the higher the ability to vertically align the liquid crystal becomes, and the less it becomes. Go down. Further, the side chain A containing a cyclic structure tends to align the liquid crystal vertically even with a small content, as compared with the side chain A of a long chain alkyl group.

  The amount of the side chain A in the specific polymer is not particularly limited as long as the liquid crystal alignment film can align the liquid crystal vertically. However, in a liquid crystal display device including a liquid crystal alignment film, when it is desired to increase the response speed of the liquid crystal, it is preferable that the content of the side chain A is as small as possible within the range in which the vertical alignment can be maintained.

<Photoreactive side chain (II)>
The photoreactive side chain (II) (hereinafter, also referred to as side chain B) has a crosslinkable side chain having a functional group (hereinafter, also referred to as photocrosslinking group) capable of reacting with irradiation of ultraviolet rays to form a covalent bond. Alternatively, the structure is not limited as long as it is a photoradical-generating side chain having a functional group capable of generating a radical upon irradiation with ultraviolet rays and has this ability.
As such a side chain, for example, a side chain containing a vinyl group, an acryl group, a methacryl group, an anthracenyl group, a cinnamoyl group, a chalcone group, a coumarin group, a maleimide group, a stilbene group, etc. as a photocrosslinking group is known. And is preferably used in the present invention. Further, as a structure that generates a radical by ultraviolet irradiation, an acylphosphine oxide structure, an acetophenone structure, an alkylpenone structure, an anthraquinone structure, a carbazole structure, a xanthone structure, a thioxanthone structure, a triphenylamine structure, a fluorenone structure, a benzaldehyde structure, a benzoin structure, Examples thereof include a benzophenone structure and a fluorene structure, and a photoradical generating side chain having these structures is also suitably used. Among them, a side chain having an acetophenone structure, a benzophenone structure, or a benzoin structure is preferable.
These groups may be directly bonded to the main chain of the specific polymer as long as they have the above-mentioned ability, or may be bonded via an appropriate bonding group.

  Examples of the side chain B include the following formulas (b-1) to (b-3). The side chain represented by the formula (b-2) has a structure having a cinnamoyl group and a methacryl group, and the side chain represented by the formula (b-3) is a structure which generates a radical by ultraviolet irradiation. Have.

Wherein ^(b-1), R ₆ is -CH 2 -, - O -, - COO -, - OCO -, - NHCO -, - CONH -, - NH -, - CH 2 O -, - N (CH _{3) -, - CON (CH} 3) -, or -N _(CH 3) a CO-. From the viewpoint of ease of synthesis, R ⁶ is preferably —CH ₂ —, —O—, —COO—, —NHCO—, —NH— or —CH ₂ O—.

R ⁷ represents an alkylene group having 1 to 20 carbon atoms, which is cyclic, unsubstituted or substituted with a fluorine atom, and any —CH ₂ — of the alkylene group is replaced with —CF ₂ — or —CH═CH—. And any of the following groups may not be adjacent to each other and may be replaced with these groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-. , -NH-, carbocycle, or heterocycle.
Specific examples of the carbocycle and the heterocycle include, but are not limited to, the following structures.

R ⁸ _{is, -CH 2 -, - O -} , - CH 2 O -, - COO -, - OCO -, - NH -, - CONH -, - NHCO -, - N (CH 3) -, - CON ( _{CH 3) -, - N (} CH 3) CO-, represent either a carbocyclic or heterocyclic ring. From the viewpoint of ease of synthesis, —CH ₂ —, —O—, —COO—, —OCO—, NHCO—, —NH—, carbocycle or heterocycle is preferable. Specific examples of the carbocycle and the heterocycle are as described above.

R ⁹ is a styryl group, a —CR ¹⁸ ═CH ₂ group, a carbocycle, a heterocycle, or the following formulas (R9-1) to (R9-34), and R ¹⁸ is a hydrogen atom or a fluorine atom. Represents an optionally substituted methyl group.

Among them, R ⁹ is a styryl group, —CH═CH ₂ , —C(CH ₃ )═CH _2, or (R9-2), (R9-12) or (R9) from the viewpoint of photoreactivity. -15) is more preferable.

In the formula (b-2), R ¹⁰ is —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, or —CO—.
R ¹¹ is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a divalent heterocycle, and one or more hydrogen atoms of the alkylene group, the divalent carbocycle and the divalent heterocycle are fluorine atoms. It may be replaced by an atom or an organic group. Further, any of —CH ₂ — in R ¹¹ may be substituted with any of the following groups when they are not adjacent to each other; —O—, —NHCO—, —CONH -, -COO-, -OCO-, -NH-, -NHCONH-, or -CO-.
R ¹² is —CH ₂ —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond.
R ¹³ is a cinnamoyl group, a chalcone group, or a coumarin group, and represents a photocrosslinking group.
R ¹⁴ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a divalent heterocycle, and one or more hydrogen atoms of the alkylene group, the divalent carbocycle and the divalent heterocycle. May be replaced by a fluorine atom or an organic group. Further, any of —CH ₂ — in R ¹⁴ may be substituted with any of the groups described below when they are not adjacent to each other; —O—, —NHCO—, —CONH -, -COO-, -OCO-, -NH-, -NHCONH-, or -CO-.
R ¹⁵ is an acrylic group or a methacrylic group and represents a photopolymerizable group.
Of the side chain represented by the formula ^(b-2), specific examples of the group represented by ^{-R 13} -R 14 -R ^15, it may be mentioned the following structures, but not limited to. In the structure below, R represents a hydrogen atom or a methyl group.

In formula (b-3), Ar ₄ represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, and these groups may be substituted with an organic group, and a hydrogen atom of these groups May be substituted with a halogen atom.
R ₁₆ and R ₁₇ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a benzyl group, or a phenethyl group, and in the case of an alkyl group or an alkoxy group, R ₁₆ and R ₁₇ may form a ring.
T ₁ and T ₂ are each independently a single bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N(CH _{3 ) -, - CON (CH 3} ) - or -N _(CH 3) shows a binding group CO-.
S ⁴ represents a single bond, an unsubstituted or substituted by a fluorine atom, an alkylene group having 1 to 20 carbon atoms (provided that —CH ₂ — or —CF ₂ — of the alkylene group is —CH═CH—. It may be optionally substituted, and in the case where any of the following groups are not adjacent to each other, they may be optionally substituted with these groups; -O-, -COO-, -OCO-, -NHCO-. , -CONH-, -NH-, a divalent carbocycle, or a divalent heterocycle.).
n2 represents 0 or 1. Q represents a structure represented by the following formula.

（式中、Ｒは水素原子又は炭素数１〜４のアルキル基を表し、Ｒ_３は−ＣＨ_２−、−ＮＲ−、−Ｏ−、又は−Ｓ−を表す）

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents —CH ₂ —, —NR—, —O—, or —S—)

Among the side chains represented by formula (b-3), specific examples of the group represented by -Ar ₄ -CO-CQR ¹⁶ R ¹⁷ include the following formulas (b-3-1) to (b- The structure of 3-6) can be mentioned, but it is not limited to these.

The amount of the side chain B in the specific polymer is not particularly limited as long as it can increase the response speed of the liquid crystal in the liquid crystal display device. When it is desired to increase the response speed of the liquid crystal in the liquid crystal display element, it is preferable that the response speed of the liquid crystal is as large as possible within a range in which other characteristics are not affected.
<Polyimide precursor>
The polyimide precursor means a polyamic acid and a polyamic acid ester. Hereinafter, a method for preparing a polyamic acid will be described. The polyamic acid ester can be prepared by a conventionally known method or a method similar to or similar to the polyamic acid described below.

<Polyamic acid>
The polyamic acid having the side chain A is obtained by reacting the raw material with one of the diamine and the tetracarboxylic acid anhydride as the raw materials having the side chain A or both having the side chain A. be able to. Among these, a method using a diamine having a side chain A is preferable in terms of easiness of raw material synthesis.

  Further, the polyamic acid having the side chain A and the side chain B is a diamine and a tetracarboxylic acid anhydride which are raw materials, only one of them has the side chain A and the side chain B, or one of them has the side chain. A having only A and the other having only side chain B, either one having side chain A and side chain B, and the other having side chain A, either one having side chain A and By having the side chain B and the other side chain B, or both having the side chain A and the side chain B, it can be obtained by reacting the raw material. Of these, the side chain side chain A and the side chain B are preferably contained only in the diamine in view of the ease of synthesizing the raw materials.

<Diamine Having Side Chain A>
As the diamine having a side chain A (hereinafter, referred to as diamine A), a diamine having a diamine side chain having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocycle, or a macrocyclic substitution product thereof. Can be cited as an example. Specific examples thereof include diamines having a side chain represented by the formula (a). More specifically, diamines represented by the following formulas (1), (3), (4) and (5) can be mentioned, but the diamines are not limited thereto. The definitions of l, m, n, and R ^{1 to} R ^{5 in} the formula (1) are the same as those in the formula (a).

式（３）及び式（４）中、Ａ_１０は、各々独立に、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−、又は−ＮＨ−を表し、Ａ_１１は単結合若しくはフェニレン基を表し、ａは側鎖Ａを表し、ａ’はアルキル基、フッ素含有アルキル基、芳香環、脂肪族環、複素環、又はこれらから選ばれる任意の構造の組み合わせからなる大環状置換体を表す。

Equation (3) and the formula _{(4), A 10} are each independently, -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO-, or - Represents NH-, A ₁₁ represents a single bond or a phenylene group, a represents a side chain A, and a'is selected from an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocycle, or these. It represents a macrocyclic substituent consisting of a combination of arbitrary structures.

式（５）中、Ａ_１４は、フッ素原子で置換されていてもよい、炭素数３〜２０のアルキル基であり、Ａ_１５は、１，４−シクロへキシレン基、又は１，４−フェニレン基であり、Ａ_１６は、酸素原子、又は−ＣＯＯ−＊（ただし、「＊」を付した結合手がＡ_３と結合する）であり、Ａ_１７は酸素原子、又は−ＣＯＯ−＊（ただし、「＊」を付した結合手が（ＣＨ_２）ａ_２と結合する。）である。また、ａ_１は０、又は１の整数であり、ａ_２は２〜１０の整数であり、ａ_３は０、又は１の整数である。）

In formula (5), A ₁₄ is an alkyl group which may be substituted with a fluorine atom and has 3 to 20 carbon atoms, and A ₁₅ is a 1,4-cyclohexylene group or 1,4-phenylene. Is a group, A ₁₆ is an oxygen atom, or —COO-* (however, a bond with “*” bonds to A ₃ ), A ₁₇ is an oxygen atom, or —COO-* (however. , A bond marked with “*” binds to (CH ₂ )a _2. ). Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of ₂ to 10, and a ₃ is an integer of 0 or 1. )

The bonding positions of the two amino groups (—NH ₂ ) in formula (1) are not limited. Specifically, with respect to the bonding group of the side chain, 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, 3,4 position on the benzene ring. 5 positions. Above all, from the viewpoint of reactivity when synthesizing a polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferable. Considering the ease of synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.

Specific examples of the formula (1) include diamines represented by the following formulas [A-1] to [A-24], but are not limited thereto.

In formulas [A-1] to [A-5], A ₁ is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group having 2 to 24 carbon atoms.
In formula [A-6] and formula [A-7], A ₂ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—, and A ₃ Is an alkyl group having 1 to 22 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.
In formulas [A-8] to [A-10], A ₄ is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, or —CH ₂ O. -, - OCH ₂ -, or -CH ₂ - indicates, _{a 5} represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, a fluorine-containing alkyl group or a carbon number of 1 to 22 carbon atoms 1 to 22 are fluorine-containing alkoxy groups.

式［Ａ−１１］及び式［Ａ−１２］中、Ａ_６は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−、−Ｏ−、又は−ＮＨ−を示し、Ａ_７は、フッ素基、シアノ基、トリフルオロメタン基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基又は水酸基である。
式［Ａ−１３］及び式［Ａ−１４］中、Ａ_８は、炭素数３〜１２のアルキル基であり、１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。
式［Ａ−１５］及び式［Ａ−１６］中、Ａ_９は、炭素数３〜１２のアルキル基であり、１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。

In formula [A-11] and formula [A-12], A ₆ is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, or —CH ₂ O. _{-, - OCH 2 -, -} CH 2 -, - O-, or -NH- are shown, _{a 7} is a fluorine group, a cyano group, trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, acetoxy A group or a hydroxyl group.
In formulas [A-13] and [A-14], A ₈ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
In formulas [A-15] and [A-16], A ₉ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.

（Ａ_１２は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−、又は−ＮＨ−を示し、Ａ_１３は、炭素数１〜２２のアルキル基又は炭素数１〜２２のフッ素含有アルキル基を示す。） Specific examples of the diamine represented by the formula (3) include, but are not limited to, the diamines represented by the following formulas [A-25] to [A-30].

_(A 12 are, -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO-, or -NH- are _{shown, A 13} is 1 to 22 carbon atoms Represents an alkyl group of or a fluorine-containing alkyl group having 1 to 22 carbon atoms.)

Specific examples of the diamine represented by the formula (4) include, but are not limited to, the diamines represented by the following formulas [A-31] to [A-32].

Among these, from the viewpoint of the ability of vertically aligning the liquid crystal and the response speed of the liquid crystal, [A-1], [A-2], [A-3], [A-7], [A-14], The diamine of [A-16], [A-21] or [A-22] is preferable.
The above-mentioned diamines may be used alone or in combination of two or more, depending on the liquid crystal alignment property of the liquid crystal alignment film, the pretilt angle, the voltage holding property, the accumulated charge and the like.

  Out of 100 mol% of the diamine component used for the synthesis of the polyamic acid having the side chain A, the diamine A is 5 to 70 mol%, preferably 10 to 50 mol%, more preferably 20 to 50 mol%. ..

<Diamine Having Side Chain B>
Examples of the diamine having a side chain B (hereinafter, also referred to as diamine B) include vinyl group, acryl group, methacryl group, anthracenyl group, cinnamoyl group, chalcone group, coumarin group, maleimide group, and stilbene group in the diamine side chain. The diamine which has a photocrosslinking group and the diamine which has a functional group which generate|occur|produces a radical by ultraviolet irradiation can be mentioned. Specific examples thereof include diamines having side chains represented by the formulas (b-1) to (b-3). As a specific example, a diamine represented by the following general formula (2) (the definitions of R ⁶ , R ⁷ , R ⁸ and R ^{9 in} the formula (2) are the same as those in the formula (b-1)). However, the present invention is not limited thereto.

式（２）中における二つのアミノ基（−ＮＨ_２）の結合位置は、特に限定されない。具体的には、側鎖の結合基に対して、ベンゼン環上の２，３の位置、２，４の位置、２，５の位置、２，６の位置、３，４の位置、３，５の位置が挙げられる。なかでも、ポリアミック酸を合成する際の反応性の観点から、２，４の位置、２，５の位置、又は３，５の位置が好ましい。ジアミンを合成する際の容易性も加味すると、２，４の位置、又は３，５の位置がより好ましい。

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

Specific examples thereof include the following compounds, but are not limited thereto. In the following compounds, X represents a bonding group selected from the group consisting of ether, ester, amide and amino, R represents a hydrogen atom or a methyl group, S ³ represents a single bond, or an unsubstituted or fluorine atom. It shows a substituted alkylene group having 1 to 20 carbon atoms. Moreover, l, m, and n show the integer of 0-20 each independently.

  The diamine may be one type or two types depending on the liquid crystal alignment property when used as a liquid crystal alignment film, pretilt angle, voltage holding property, characteristics such as accumulated charge, and response speed of liquid crystal when used as a liquid crystal display device. The above may be mixed and used.

  In 100 mol% of the diamine component used for synthesizing the polyamic acid, the diamine B is 0 to 95 mol%, preferably 20 to 80 mol%, more preferably 40 to 70 mol%.

<Other diamines>
Polyamic acid used in the present invention, as long as it does not impair the effect of the present invention, a diamine having a side chain that vertically aligns the liquid crystal, and a diamine other than the diamine having a photoreactive group, a diamine component. Can be used together. Specifically, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m- Phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4- Diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3 ,3'-Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-tri Fluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane , 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis(4-aminophenyl)silane, Bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4′-thiodianiline, 3,3′-thiodianiline, 4,4′- Diaminodiphenylamine, 3,3′-diaminodiphenylamine, 3,4′-diaminodiphenylamine, 2,2′-diaminodiphenylamine, 2,3′-diaminodiphenylamine, N-methyl(4,4′-diaminodiphenyl)amine, N -Methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'- Diaminodiphenyl)amine, 4,4'-diaminobenzoph Enone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1, 6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2- Bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1, 4-bis(4aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl) ) Benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)] Dianiline, 3,4'-[1,4-phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis (Methylene)]dianiline, 3,3′-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3- Aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzoate) , 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl) terephthalate, bis (3-Aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N, N '-(1,3-Phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis (3-aminobenzamide), N,N′-bis(4-aminophenyl)terephthalamide, N,N′-bis(3-aminophenyl)terephthalamide, N,N′-bis(4-aminophenyl)isophthale Amide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 2,2'- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2′-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2′-bis(4-aminophenyl)hexafluoropropane 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis (4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4 -Bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1 ,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy) ) Heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3- Aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis( 3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane , Aromatic diamines such as 1,12-bis(3-aminophenoxy)dodecane, alicyclic diamines such as bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3 -Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Aliphatic diamines such as diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane can be mentioned.

  The above-mentioned other diamines may be used alone or in combination of two or more depending on properties such as liquid crystal orientation, pretilt angle, voltage holding characteristic and accumulated charge when used as a liquid crystal orientation film.

<Tetracarboxylic acid dianhydride>
In the synthesis of the polyamic acid used in the present invention, the tetracarboxylic dianhydride to be reacted with the above diamine component is not particularly limited. Specific examples are given below.

  Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 -Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl)ether, 3,3′,4,4′-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3 ,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl) Pyridine, 3,3′,4,4′-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid, Oxydiphthaltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2 ,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-Tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3,3,0]octane-2,4,6,6 8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic acid, Bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0.0<2,6>]undecane- 3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetra Hydrinaphthalene-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3 -Methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0,2,7]dodeca-4,5,9,10-tetracarboxylic acid, 3,5 6-tricarboxynorbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and the like can be mentioned.

  The tetracarboxylic dianhydride may be used alone or in combination of two or more types depending on the liquid crystal alignment property when formed into a liquid crystal alignment film, the voltage holding property, the accumulated charge and the like.

<Synthesis of polyamic acid>
In obtaining a polyamic acid by the reaction of a diamine component and a tetracarboxylic dianhydride, a known synthetic method can be used. Generally, it is a method of reacting a diamine component and a tetracarboxylic dianhydride in an organic solvent. The reaction between the diamine component and the tetracarboxylic acid dianhydride is advantageous in that it proceeds relatively easily in the organic solvent and that by-products are not generated.

  The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the generated polyamic acid. Furthermore, even an organic solvent that does not dissolve the polyamic acid may be used as a mixture with the above solvent as long as the generated polyamic acid does not precipitate. Since water in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the generated polyamic acid, it is preferable to use dehydrated and dried organic solvent.

  Examples of the organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2 -Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ- Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether. , Dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, Ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether Tellurium, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 -Methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl- 2-Pentanone, 2-ethyl-1-hexanol and the like can be mentioned. These organic solvents may be used alone or in combination.

  When the diamine component and the tetracarboxylic acid dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid dianhydride component is used as it is, or organically. Method of dispersing or dissolving in a solvent and adding, conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a tetracarboxylic acid dianhydride component and a diamine component Examples thereof include a method of alternately adding, and any of these methods may be used. Further, when the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually and sequentially reacted, and may be further individually reacted to have a low molecular weight. The body may be mixed and reacted to form a high molecular weight body.

  The temperature for reacting the diamine component and the tetracarboxylic dianhydride component can be selected at any temperature, and is, for example, in the range of -20 to 150°C, preferably -5 to 100°C. The reaction can be carried out at any concentration, for example, 1 to 50% by mass, preferably 5 to 30% by mass.

  In the above polymerization reaction, the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected to any value depending on the molecular weight of the polyamic acid to be obtained. Similar to the ordinary polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced. The preferable range is 0.8 to 1.2.

  The method for synthesizing the polyamic acid used in the present invention is not limited to the above method, and instead of the above tetracarboxylic acid dianhydride, as in the general polyamic acid synthesizing method, tetra of the corresponding structure is used. The corresponding polyamic acid can also be obtained by reacting a tetracarboxylic acid derivative such as a carboxylic acid or a tetracarboxylic acid dihalide with a known method.

Examples of the method for imidizing the above polyamic acid to form a polyimide include thermal imidization in which the solution of polyamic acid is heated as it is and catalytic imidization in which a catalyst is added to the solution of polyamic acid.
In the polyimide used in the present invention, the imidation ratio of polyamic acid to polyimide does not necessarily have to be 100%.

  When the polyamic acid is thermally imidized in a solution, the temperature is 100 to 400° C., preferably 120 to 250° C., and it is preferable to carry out while removing water generated by the imidization reaction from the outside of the system.

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

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

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention contains the polymerizable compound represented by the above formula (1) and at least one polymer selected from the group consisting of the above polyimide precursor and polyimide. In addition to these components, other polymer components for forming a resin film may be contained. The content of all resin components is 1 to 20% by mass, preferably 3 to 15% by mass, and more preferably 3 to 10% by mass in 100% by mass of the liquid crystal aligning agent.

The resin component in the liquid crystal aligning agent of the present invention may all be at least one polymer selected from the group consisting of a polyimide precursor having a side chain A and/or a side chain B and a polyimide. It may be a mixture of the above, and further other polymers may be mixed. At that time, the content of the other polymer in the resin component is preferably 0.5 to 15% by mass, and more preferably 1 to 10% by mass.
Examples of other polymers include a polyimide precursor or polyimide having no side chain B, a polyimide precursor or polyimide having neither side chain A nor side chain B, and the like. Not limited.

The molecular weight of the polymer of the above resin component is a weight average measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability during coating film formation, and uniformity of the coating film. The molecular weight (Mw) is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
The content of the polymerizable compound represented by the formula (1) in the liquid crystal aligning agent of the present invention is 3 to 30 parts by mass, preferably 5 to 20 parts by mass, and more preferably 5 parts by mass with respect to 100 parts by mass of the resin component. ~15 parts by mass. With such a content, the effect of the present invention can be obtained.

<Solvent>
The organic solvent used for the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component described above. This organic solvent may be one type of solvent or a mixed solvent of two or more types. Specific examples of the organic solvent include the organic solvents exemplified in the above polyamic acid synthesis. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, or 3-methoxy-N,N-dimethylpropanamide is a resin component. Is preferable from the viewpoint of solubility.
Further, the following solvents have the effect of improving the uniformity and smoothness of the coating film, and are preferably used by mixing with a solvent having a high solubility of the resin component.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether Diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene Glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether , Diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate. Monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionate Acid propyl, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propyleneglycol Monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate Esters, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, 2-ethyl-1-hexanol and the like can be mentioned. Plural kinds of these solvents may be mixed. When using these solvents, the amount is preferably 5 to 80% by mass, and more preferably 20 to 60% by mass, based on the whole solvent contained in the liquid crystal aligning agent.

  The liquid crystal aligning agent may contain components other than the above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal alignment agent is applied, compounds that improve the adhesion between the liquid crystal alignment film and the substrate, and the like.

  Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals), Fluorard FC430, FC431 (manufactured by Sumitomo 3M Ltd.). ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like. When these surfactants are used, the use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. It is a mass part.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. , N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl- 1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxy Silane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol , N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N',-tetraglycidyl -4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane and the like.
In order to further improve the rubbing resistance of the coating film obtained from the liquid crystal aligning agent, phenol compounds such as 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane and tetra(methoxymethyl)bisphenol May be added. When these compounds are used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
In the liquid crystal aligning agent of the present invention, in addition to the above, a dielectric or a conductive substance for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film may be used as long as the effect of the present invention is not impaired. You may add.

<Liquid crystal alignment film>
A cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate, and then drying and baking it as necessary can also be used as it is as a liquid crystal aligning film. Further, this cured film is rubbed, irradiated with polarized light or light of a specific wavelength, treated with an ion beam, or the like, and is applied as a SC-PVA alignment film with a voltage applied to a liquid crystal display element after liquid crystal filling. It is also possible to irradiate UV with the applied state.

  The substrate is not particularly limited as long as it is a highly transparent substrate, and a glass plate, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, Polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose and the like can be used. Further, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for driving the liquid crystal is formed, from the viewpoint of simplifying the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used if only one substrate is used, and in this case, a material that reflects light such as aluminum can also be used as an electrode.

  The method for applying the liquid crystal aligning agent is not particularly limited, and examples thereof include a printing method such as screen printing, offset printing and flexographic printing, an inkjet method, a spray method, a roll coating method, a dip, a roll coater, a slit coater, a spinner and the like. From the viewpoint of productivity, the transfer printing method is widely used industrially, and is also preferably used in the present invention.

  The coating film formed by applying the liquid crystal aligning agent by the above method can be baked to form a cured film. The step of drying after applying the liquid crystal aligning agent is not always required, but if the time from application to firing is not constant for each substrate, or if firing is not performed immediately after application, a drying step is performed. Preferably. This drying may be carried out as long as the solvent is removed to such an extent that the shape of the coating film is not deformed due to transportation of the substrate, and the drying means is not particularly limited. For example, a method of drying on a hot plate at a temperature of 40 to 150° C., preferably 60 to 100° C. for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.

  The baking temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and for example, it can be performed at any temperature of 100 to 350° C., preferably 120 to 300° C., and further preferably It is 150 to 250°C. The firing time can be any time of 5 to 240 minutes. It is preferably 10 to 90 minutes, more preferably 20 to 90 minutes. The heating can be performed by a known method, for example, a hot plate, a hot air circulating furnace, an infrared furnace, or the like.

  The thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 120 nm.

<Liquid crystal display element>
The liquid crystal display device of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then producing a liquid crystal cell by a known method.
Specific examples of the liquid crystal display device include two substrates arranged so as to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent of the present invention provided between the substrate and the liquid crystal layer. A vertical alignment type liquid crystal display device comprising a liquid crystal cell having a formed liquid crystal alignment film. Specifically, the liquid crystal aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal alignment film, and the two substrates are arranged so that the liquid crystal alignment films face each other. By sandwiching a liquid crystal layer composed of liquid crystal between two substrates, providing a liquid crystal layer in contact with the liquid crystal alignment film, and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. It is a vertical alignment type liquid crystal display device provided with a manufactured liquid crystal cell.
Using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, the liquid crystal alignment film and the liquid crystal layer are irradiated with ultraviolet rays while applying a voltage to polymerize the polymerizable compound and By reacting the side chains with each other or the photoreactive side chains of the polymer and the polymerizable compound, the alignment of the liquid crystal is more efficiently fixed, and the liquid crystal display device has a remarkably excellent response speed.

The substrate used for the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but it is usually a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples thereof include the same as the substrate described for the liquid crystal alignment film.
The liquid crystal display element of the present invention may use a substrate provided with a conventional electrode pattern or protrusion pattern, but by having a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention, For example, a line/slit electrode pattern having a size of 1 to 10 μm is formed on one side substrate, and a substrate having a structure without a slit pattern or a protrusion pattern is used as an opposite substrate. The process can be simplified and high transmittance can be obtained.

Further, in a highly functional element such as a TFT type element, an element in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.
In the case of a transmissive liquid crystal display element, the above substrate is generally used, but in a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used. Is. At that time, a material such as aluminum that reflects light can be used for the electrodes formed on the substrate.

  The liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on this substrate and then firing it, which has been described in detail above.

  The liquid crystal material forming the liquid crystal layer of the liquid crystal display device of the present invention is not particularly limited, and liquid crystal materials used in the conventional vertical alignment system, for example, negative type such as MLC-6608 and MLC-6609 manufactured by Merck & Co., Inc. Liquid crystal can be used.

  In order to manufacture the liquid crystal display device of the present invention, the polymerizable compound of the present invention may be contained in at least one of the liquid crystal aligning agent and the liquid crystal layer.

As a method for sandwiching this liquid crystal layer between two substrates, a known method can be mentioned. For example, prepare a pair of substrates on which a liquid crystal alignment film is formed, and disperse spacers such as beads on the liquid crystal alignment film on one substrate so that the surface on the side where the liquid crystal alignment film is formed is the inner side. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure to seal the liquid crystal.
In addition, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers such as beads are sprinkled on the liquid crystal alignment film on one of the substrates, and then liquid crystal is dropped, and then the side where the liquid crystal alignment film is formed. The liquid crystal cell can also be produced by a method in which the other substrate is bonded and sealed so that the surface of the liquid crystal layer faces the inside. At this time, the thickness of the spacer is preferably 1 to 30 μm, more preferably 2 to 10 μm.

The step of producing a liquid crystal cell by irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet rays while applying a voltage is, for example, by applying a voltage between the electrodes installed on the substrate. There is a method of applying an electric field to and irradiating with ultraviolet rays while maintaining this electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The dose of ultraviolet rays, for example, 1~60J / cm ^2, preferably at 40 J / cm ² or less, more preferably 20 J / cm ² or less. It is preferable that the irradiation amount of ultraviolet rays is small because it is possible to suppress a decrease in reliability caused by breakage of liquid crystal and members that constitute the liquid crystal display element, and to reduce the irradiation time of ultraviolet rays, thereby improving manufacturing efficiency.
The wavelength of the ultraviolet ray used is preferably 300 to 400 nm, more preferably 310 to 370 nm.

When ultraviolet rays are applied to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, the polymerizable compound reacts with each other to form a polymer, and the polymer stores the direction in which the liquid crystal molecules tilt, thereby obtaining a liquid crystal display. The response speed of the element can be increased.
When the liquid crystal alignment film and the liquid crystal layer are irradiated with ultraviolet rays while applying a voltage, at least one selected from the group consisting of a polyimide precursor having a reactive side chain and a polyimide obtained by imidizing the polyimide precursor. Since the photoreactive side chains of one polymer react with each other or the photoreactive side chains of the polymer react with the polymerizable compound, the response speed of the resulting liquid crystal display device can be increased.

  Further, the liquid crystal aligning agent of the present invention is not only useful as a liquid crystal aligning agent for producing a vertical alignment type liquid crystal display device such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also a rubbing treatment or an optical alignment. It can also be suitably used for producing a liquid crystal alignment film formed by the treatment.

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. The abbreviations of the compounds below are as follows.

BODA: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride.
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride.
PMDA: pyromellitic dianhydride.
TCA: 2,3,5-tricarboxycyclopentyl acetic acid-1,4,2,3-dianhydride.

DBA: 3,5-diaminobenzoic acid

NMP: N-methyl-2-pyrrolidone.
BCS: butyl cellosolve.
3AMP: 3-picolylamine.

<Synthesis example 1>

<Synthesis of RM1-A>
At room temperature, in a 500 mL (ml) four-necked flask equipped with a magnetic stirrer, 4-(4-hydroxyphenyl)benzoic acid 20 g (93.4 mmol), NMP 70.0 g (3.5 wt), potassium carbonate 38.7 g. (3.0 eq) and 0.776 g (5.0 mol%) of potassium iodide were charged, and 10.0 g (0.5 wt) of NMP was added to the reaction solution while washing the wall surface of the flask, followed by stirring. Then, the temperature was raised to 100° C., and 35.7 g (2.5 eq) of 4-chlorobutyraldehyde dimethyl acetal and 10.0 g (0.5 wt) of NMP were reacted while washing the powder adhering to the wall surface of the flask. It was poured into the system and stirred for 18 hours to react.
After the reaction, 120 g (6.0 wt) of toluene was added and filtered, and the filter cake was washed twice with 20.0 g (1 wt) of toluene. Then, the collected toluene filtrate was washed 3 times with 80.0 g (4 wt) of water. Then, it vacuum-dried at 50 degreeC and the solvent was distilled off. Ethyl acetate (30.0 g, 1.5 wt) was added to the residue, and the temperature was raised to 50° C. to dissolve it. Then, 140 g (7 wt) of heptane was added dropwise and cooled to 0°C. A small amount of seed crystals were added to precipitate crystals. The crystals were filtered, washed twice with 20.0 g (1 wt) of heptane and then vacuum dried at 30° C. to obtain 38.0 g of RM1-A (yield: 91%, property: white solid).

<Synthesis of RM1>
At room temperature, 1L four-necked flask equipped with a magnetic stirrer was charged with 35.0 g (78.4 mmol) of RM1-A and 105 g (3.0 wt) of THF, and after stirring to confirm dissolution, chlorination Tin dihydrate (38.9 g, 2.2 eq) and ethyl 2-(bromomethyl)acrylate, 33.4 g (2.2 eq) were sequentially added, and the temperature was raised to 60°C. Next, after dropping 125 g (3.6 wt) of 0.1 M hydrochloric acid, 245 g (7 wt) of THF was poured into the reaction system while washing the powder adhering to the wall surface of the flask, and stirred for 14.5 hours, It was made to react.
The reaction solution was cooled to 50° C., 350 g (10 wt) of toluene was added thereto for liquid separation, and the hydrochloric acid layer was removed. After that, the organic layer was dropped into 263 g (7.5 wt) of a 12.9 mass% potassium hydroxide aqueous solution at 50° C. over 30 minutes, and after stirring, the organic layer was separated. 262 g (7.5 wt) of a 5.2 mass% potassium hydroxide aqueous solution was added to the obtained organic layer, and the mixture was stirred and then separated at 50°C. 3.49 g (10 wt%) of activated carbon was added to the separated organic layer, and the mixture was stirred at 50°C for 30 minutes and then filtered at 50°C. The filter cake was washed twice with 17.5 g (0.5 wt) of toluene, and the combined toluene filtrate was cooled to 5° C. with stirring and aged for 1 hour. The precipitated solid was filtered and the filter cake was washed twice with 17.5 g (0.5 wt) of heptane. The filter cake was vacuum dried at 40° C. to obtain 19.7 g of RM1 (yield: 51%, property: white crystal).
¹ H-NMR(400MHz) in DMSO-d6: 1.79-1.87 ppm(m, 8H), 2.64 ppm(dd, J=7.4, 18.6 Hz, 2H), 3.10 ppm(dd, J=8.4.14.0 Hz, 2H ), 4.08 ppm(t, J=5.6 Hz, 2H), 4.31 ppm(t, J=6.8 Hz, 2H), 4.61-4.68 ppm(m, 2H), 5.73 ppm(s, 2H), 6.04 ppm(d , J=4.8 Hz, 2H), 7.06 ppm(d, J=8.8 Hz, 2H), 7.70 ppm(d, J=4.4 Hz, 2H), 7.78 ppm(d, J=4.4 Hz, 2H), 8.01 ppm (d, J=8.4 Hz, 2H).

<Synthesis example 2>

<Synthesis of RM2-A>
At room temperature, in a 500 mL four-necked flask equipped with a magnetic stirrer, 80.0 g (430 mmol) of 4,4′-biphenol and 160.0 g (2.0 wt) of DMF were charged and dissolved by stirring. Then, 77.2 g (1.3 eq) of potassium carbonate and 3.57 g (5.0 mol%) of potassium iodide were sequentially added. Then, it heated up at 80 degreeC, 4-chlorobutyraldehyde dimethyl acetal 65.6g (1.0eq) was dripped over 1 hour, and it stirred for 19.5 hours and was made to react.
The reaction solution was added dropwise to 1600 g (20 wt) of water and then stirred for 0.5 hours, and the precipitated solid was filtered. The filter cake was washed twice with 40.0 g (0.5 wt) of water. Then, the filter cake was dried under reduced pressure at 40° C. for 1.5 hours. To the dried cake, 880 g (11 wt) of methanol was added, and the crystals were washed by stirring in a suspended state (hereinafter referred to as slurry washing), and then filtered. The filter cake was washed twice with 8.00 g (0.1 wt) of methanol. The solvent of the collected filtrates such as methanol was distilled off under reduced pressure to obtain a residue. The obtained residue was slurry-washed with 1040 g (13 wt) of chloroform and filtered. The filtrate was washed twice with 16.0 g (0.2 wt) of chloroform, and the solvent of the combined chloroform filtrate was distilled off. To the obtained residue, 104 g (1.3 wt) of THF and 326 g (4.1 wt) of heptane were added and cooled to 0° C. for crystallization. 400 g (5 wt) of methanol was added to the precipitated solid to wash the slurry, and the solid was filtered. The filter cake was dried under reduced pressure at 40° C. to obtain 33.6 g of RM2-A (yield: 26%, property: white solid).

<Synthesis of RM2-B>
At room temperature, in a 500 mL four-necked flask equipped with a magnetic stirrer, 33.6 g (111 mmol) of RM2-A and 169 g (5 wt) of DMF were charged and stirred to dissolve them, and 20.0 g (1.3 eq) of potassium carbonate was added. Was added. Thereafter, the temperature was raised to 80° C., 25.6 g (1.3 eq) of 2-(4-bromobutyl)-1,3-dioxolane was added dropwise, and the mixture was stirred for 24.5 hours to cause a reaction.
The reaction liquid was added dropwise to 672 g (20 wt) of water and then stirred for 0.5 hour, and the precipitated solid was filtered. The filter cake was washed twice with 16.8 g (0.5 wt) of water. Then, the filter cake was vacuum dried at 40° C. for 1.5 hours. Toluene (100 g, 3.0 wt) was added to the dried filtrate, and the temperature was raised to 70° C. to dissolve it. Then, 198 g (6.0 wt) of heptane was added dropwise, cooled to 0° C., and the precipitated solid was filtered. The obtained filter cake was washed twice with 10.0 g (0.3 wt) of heptane. The filter cake was vacuum dried at 40° C. to obtain 35.6 g of RM2-B (yield: 75%, property: white solid).

<Synthesis of RM2>
At room temperature, 1L four-necked flask equipped with a magnetic stirrer was charged with 50.0 g (116 mmol) of RM2-B and 500 g (10 wt) of THF, and after stirring and confirming dissolution, tin chloride dihydrate was added. 57.7 g (2.2 eq) of the product and 49.3 g (2.2 eq) of ethyl 2-(bromomethyl)acrylate were sequentially added, and the temperature was raised to 60°C. Then, 179 g (3.6 wt) of 0.1 M hydrochloric acid was added dropwise, and the mixture was stirred for 26 hours for reaction.
The reaction solution was cooled to 50° C., 500 g (10 wt) of toluene was added, and the layers were separated to remove the hydrochloric acid layer. The organic layer was added dropwise to 375 g (7.5 wt) of 12.9 mass% potassium hydroxide aqueous solution at 50° C. over 30 minutes, and then the organic layer was separated. 375 g (7.5 wt) of a 5.2 mass% potassium hydroxide aqueous solution was added to the organic layer, and the layers were separated at 50°C. The separated organic layer was washed with 375 g (7.5 wt) of water. 5.12 g (10 wt%) of activated carbon was added to the washed organic layer, and the mixture was stirred at 50°C for 30 minutes and then filtered at 50°C. The filtrate was washed twice with 25.0 g (0.5 wt) of toluene, and the combined toluene filtrate was cooled to 5° C. with stirring and aged for 1 hour. The precipitated solid was filtered, and the filter cake was washed twice with 25.0 g (0.5 wt) of heptane. The filter cake was vacuum dried at 40° C. to obtain 35.6 g of RM2 (yield: 83%, property: white crystal).
¹ H-NMR(400MHz) in DMSO-d6: 1.42-1.58 ppm(m, 2H), 1.62-1.86 ppm(m, 8H), 2.58-2.67 ppm(m, 2H), 3.06-3.11 ppm(m, 2H ), 4.00-4.03 ppm(m, 4H), 4.55-4.66 ppm(m, 2H), 5.71 ppm(s, 1H), 5.73 ppm(s, 1H), 6.03 ppm(s, 1H), 6.05 ppm(s , 1H), 6.98 ppm(d, J=8.8 Hz, 4H), 7.52 ppm(d, J=8.8 Hz, 4H).

<Synthesis example 3>

<Synthesis of RM3-A>
At room temperature, in a 500 mL four-necked flask equipped with a magnetic stirrer, 4,4′-biphenol (50.0 g, 269 mmol) and DMF (175 g) were charged, stirred and dissolved, and then potassium carbonate (48.24 g, 1.3 eq). ) Was added. After that, the temperature was raised to 80° C., 48.61 g (1.0 eq) of 2-(2-bromoethyl)-1,3-dioxolane was added dropwise over 1 hour, and the mixture was stirred for 7 hours to be reacted. Then, the reaction solution was added dropwise to 1000 g of water and stirred at room temperature for 0.5 hour, and then the precipitated solid was filtered. Methanol (550 g) was added to the filtrate, and the slurry was washed at room temperature and then filtered at 0 to 5°C. To the residue obtained by distilling off the solvent of the filtrate, 650 g of chloroform was added, and the slurry was washed at room temperature and then filtered. To the residue obtained by distilling off the solvent of the filtrate, 15 g of THF was added and dissolved, 37.5 g of toluene was added, and the mixture was stirred for 0.5 hour in an ice bath. The precipitated crystals were filtered, washed (toluene 12.5 g) and dried under reduced pressure at 40° C. to obtain RM3-A 9.0 g (yield: 12%, property: gray crystal).

<Synthesis of RM3-B>
At room temperature, into a 500 mL four-necked flask equipped with a magnetic stirrer, RM3-A (8.31 g, 29 mmol) and NMP (12.5 g) were charged, and after stirring and dissolving, 6.01 g (1.5 eq. of potassium carbonate). ) Was added. Then, the temperature was raised to 80° C., 5.79 g (1.1 eq) of 2-(4-bromobutyl)-1,3-dioxolane was added dropwise over 10 minutes, and the mixture was stirred for 19 hours to be reacted. Next, 83 g of ethyl acetate was added to the reaction solution, and the precipitated inorganic salt was filtered. Then, the filtrate was separated and washed with 24 g of water three times, and the solvent of the filtrate was distilled off. Toluene (24 g) was added to the obtained residue and dissolved at 70° C., heptane (48 g) was added, and the mixture was stirred for a while in an ice bath. The precipitated crystals were filtered and dried under reduced pressure at 40° C. to obtain RM3-B 12.2 g (yield: 91%, property: white solid).

<Synthesis of RM3>
At room temperature, in a 500 mL four-necked flask equipped with a magnetic stirrer, 11.0 g (26.5 mmol) of RM3-B and 110 g of THF were charged, stirred and dissolved, and then 14.4 g of tin chloride dihydrate ( 2.4 eq) and 49.3 g (2.2 eq) of ethyl 2-(bromomethyl)acrylate were sequentially added. After that, 38.5 g of 10 mass% hydrochloric acid was added dropwise and reacted for 120 hours. The reaction solution was concentrated under reduced pressure to about one-third, cooled to 15° C., and the precipitated crystals were filtered and washed (water 44 g×3 times). Next, the crystals were dissolved in 165 g of THF, and 110 g of toluene was added to dilute the crystals. The obtained solution was added dropwise to 82.5 g of a 12.9 mass% potassium hydroxide aqueous solution at room temperature, and the aqueous layer was separated and removed. 82.5 g of a 5.2 mass% potassium hydroxide aqueous solution was added to the obtained organic layer at room temperature, and the aqueous layer was separated and removed. Thereafter, the organic layer was washed 5 times with 82.5 g of water, 0.55 g (5% by mass) of specially made Shirasagi activated carbon was added, and the mixture was stirred at room temperature for 1 hour and filtered. Then, the filtrate was concentrated under reduced pressure to about 15 g and stirred at 5° C. for a while. The precipitated crystal was filtered, washed (heptane 5.5 g×2 times), and dried under reduced pressure at 40° C. to obtain RM3 7.1 g (yield: 53%, property: white crystal).
¹ H-NMR(400MHz) in DMSO-d6: 1.40-1.82 ppm(m, 6H), 2.08-2.13 ppm(m, 2H), 2.55-2.81 ppm(m, 2H), 3.06-3.11 ppm(m, 2H ), 3.98-4.18 ppm(m, 4H), 4.55-4.85 ppm(m, 2H), 5.72 ppm(d, J=8.8 Hz, 2H), 6.05 ppm(d, J=8.8 Hz, 2H), 6.97- 7.08 ppm(m, 4H), 7.52-7.61 ppm(m, 4H).

<Synthesis example 4>
RM4 was synthesized by the method disclosed in WO2012/002513.
<Synthesis example 5>
RM5 was synthesized by the method disclosed in Japanese Patent Application No. 2014-015830.

<Synthesis example 6>

<Synthesis of RM6-A>
At room temperature, in a 1 L four-necked flask equipped with a magnetic stirrer, 5,4 g of 4,4′-biphenol (300 mmol), 2-(4-bromobutyl)-1,3-dioxolane 62.7 g (1.0 eq), And 234 g (4.2 wt) of acetone were sequentially charged, and 53.9 g (1.3 eq) of potassium carbonate was further added with stirring, and then 156 g (2.8 wt) of acetone was added to the powder attached to the wall surface of the flask. It was poured into the reaction system while being washed. Then, it heated up at 60 degreeC and stirred for 41.5 hours, and was made to react.
Then, after allowing to cool to room temperature, the reaction solution was added dropwise to 3013 g (54 wt) of water and stirred for 30 minutes. Then, the precipitated solid was filtered, and the filter cake was dried under reduced pressure at 30°C. To the dried solid, 614 g (11 wt) of methanol was added and stirred to wash the slurry. Then, it filtered and the obtained filtrate was concentrated. Chloroform (725 g, 13 wt) was added to the obtained residue, and the mixture was stirred to wash the slurry. Then, the obtained filtrate was concentrated under reduced pressure. 72.5 g (1.3 wt) of THF was added to the obtained residue, 273 g (4.9 wt) of heptane was further added dropwise, and the mixture was cooled to 0°C. The precipitated solid was filtered, washed with heptane, and dried under reduced pressure to obtain 31.6 g of RM6-A (yield: 34%, property: white solid).

<Synthesis of RM6-B>
At room temperature, in a 500 mL four-necked flask equipped with a magnetic stirrer, RM6-A 19.7 g (62.6 mmol), potassium carbonate 43.1 g (5.0 eq), potassium iodide 1.04 g (10 mol%), and DMF (148 g, 7.5 wt) was sequentially charged, stirred, and heated to 100°C. Further, 4.80 g (1.8 eq) of 4-chloro-1-butanol was added dropwise, and the mixture was stirred and reacted for 27 hours. Since the reaction became slower on the way, 2.40 g (0.3 eq) of 4-chloro-1-butanol was added twice.
Then, the reaction solution was filtered and potassium carbonate was filtered off. The filtrate was concentrated to 4.3 wt, and the residue was dropped into 400 g (20 wt) of water to precipitate crystals. To the obtained crystals, 197 g (10 wt) of THF was added, dissolved at 40° C., and 197 g (10 wt) of heptane was added dropwise to precipitate crystals. After that, the solution containing crystals was cooled to 0° C. and then filtered, and the obtained crystals were dried under reduced pressure to obtain 19.4 g of RM6-B (yield: 80%, property: pale brown solid).

<Synthesis of RM6-C>
At room temperature, 155 g (8.0 wt) of THF was added to 19.4 g (50.3 mmol) of RM6-B, and after confirming that it was dissolved with stirring, 55.4 mg (0.5 mol%) of BHT and tin chloride 2 were added. The hydrate 20.4 g (1.8 eq) and ethyl 2-(bromomethyl)acrylate 17.5 g (1.8 eq) were charged in order. Then, the temperature was raised to 60° C., 69.4 g (3.6 wt) of 0.1 M hydrochloric acid was added dropwise, and the mixture was stirred for 18 hours for reaction.
Then, the temperature was adjusted to 50° C., and then 194 g (10 wt) of toluene was added to separate the layers. The organic layer was added dropwise to 150 g (7.5 wt) of a 12.9 mass% potassium hydroxide aqueous solution at 50° C. over 30 minutes, but insoluble matter was deposited. Therefore, 637 g (32.8 wt) of 12.9 mass% potassium hydroxide aqueous solution was added to dissolve the insoluble matter, and then liquid separation was performed at 50°C. Next, the separated organic layer was washed with 150 g (7.5 wt) of a 5.2 mass% potassium hydroxide aqueous solution and further with 150 g (7.5 wt) of water. To the washed organic layer, 2.00 g of activated carbon (special white egret, 10 wt%) was added, and the mixture was stirred at 50° C. for 30 minutes and then filtered while hot. The filtrate was washed twice with 10.5 g (0.5 wt) of toluene, and the combined filtrate was aged at 5°C for 30 minutes. Then, the precipitated solid was filtered and washed twice with 10.5 g (0.5 wt) of heptane. The obtained solid was dried under reduced pressure at 40° C. to obtain 3.2 g of RM6-C (yield: 16%, property: white solid).

<Synthesis of RM6>
At room temperature, a 500 mL four-necked flask equipped with a magnetic stirrer was charged with 3.1 g (7.5 mmol) of RM6-C, 308 g (100 wt) of THF was added, and it was confirmed that the mixture was dissolved with stirring. Thereafter, 10.3 g (13.6 eq.) of triethylamine and 10.2 g (13 eq) of methacrylic acid chloride were added dropwise over 1 hour, and the mixture was stirred and reacted for 19.5 hours.
Next, 217 g (70 wt) of water was added to dissolve triethylamine hydrochloride, and 208 g (67 wt) of toluene was further added for liquid separation. The separated organic layer was washed twice with 151 g (49 wt) of water. Then, in order to prevent the polymerization reaction from occurring, the solvent was distilled off under reduced pressure at 25° C. until the amount of the solvent reached 10 g (3.3 wt). 40.3 g (13 wt) of heptane was added dropwise to the obtained residue, cooled to 0° C., and aged for 1 hour. The precipitated solid was filtered and washed twice with 9.3 g (3.0 wt) of heptane. The obtained solid was vacuum dried at 25° C. to obtain 2.4 g of RM6 (yield: 67%, property: white crystal).
¹ H-NMR(400MHz) in DMSO-d6: 1.42-1.84 ppm(m, 10H), 1.88 ppm(s, 3H), 2.60 ppm(dd, J=6.0, 17.2 Hz, 1H), 3.10 ppm(dd, J=8.0, 17.2 Hz, 1H), 3.99-4.00 ppm(m, 4H), 4.17 ppm(t, J=6.0 Hz, 2H), 4.59 ppm(quint, J=6.0 Hz, 1H), 5.69 ppm(d , J=16.4 Hz, 2H), 6.03 ppm(s, 2H), 6.97 ppm(d, J=6.0 Hz, 4H), 7.51 ppm(d, J=8.0 Hz, 4H).

In addition, the hydrogen nuclear magnetic resonance ( ¹ HNMR) of the synthesis example was measured in a deuterated dimethylsulfoxide (DMSO-d6) solvent using an NMR measuring device (JNW-ECA500 manufactured by JEOL Datum Co., Ltd.), The shift is indicated by a δ value (ppm) when tetramethylsilane is used as an internal standard.

<Polyimide molecular weight measurement>
Equipment: Senshu Scientific Co., Ltd. room temperature gel permeation chromatography (GPC) equipment (SSC-7200),
Column: Shodex column (KD-803, KD-805),
Column temperature: 50 ℃,
Eluent: N,N′-dimethylformamide (lithium bromide-hydrate (LiBr.H ₂ O) as an additive, 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid), 30 mmol/L, Tetrahydrofuran (THF) is 10 ml/L),
Flow rate: 1.0 ml/min,
Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 9,000,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight: about 12,000, manufactured by Polymer Laboratory). 4,000, and 1,000).

<Measurement of imidization ratio>
20 mg of polyimide powder was put in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Science Co., Ltd.), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05 mass% TMS mixture) was added, and ultrasonic waves were applied. It was completely dissolved by applying. This solution was measured for proton NMR at 500 MHz with an NMR measuring device (JNW-ECA500 manufactured by JEOL Datum Co., Ltd.). The imidization rate is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of amic acid that appears near 9.5 to 10.0 ppm. It was calculated by the following formula using the integrated value. In the formula below, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the proton of the NH group of the amic acid in the case of polyamic acid (imidization ratio is 0%). It is the ratio of the number of reference protons to one.
Imidization rate (%)=(1-α·x/y)×100

<Synthesis example 7>
BODA (10.0 g, 40.0 mmol), DA-1 (15.2 g, 40.0 mmol), DA-2 (4.85 g, 20.0 mmol), and DA-3 (13.2 g, 40.0 mmol). Was dissolved in NMP (164.4 g) and reacted at 60° C. for 3 hours. Then, CBDA (11.5 g, 58.6 mmol) and NMP (54.8 g) were added and reacted at 40° C. for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (250 g) and diluting it to 6.5% by mass, acetic anhydride (46.4 g) as an imidization catalyst and pyridine (14.4 g) were added and reacted at 70° C. for 3 hours. It was The deposit obtained by throwing in this reaction solution in methanol (2900g) was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder A was obtained. The imidation ratio of this polyimide was 73%, Mn was 13000 and Mw was 39000.
NMP (48.8g) was added to the obtained polyimide powder A (10.0g), and it was made to melt|dissolve by stirring at 70 degreeC for 12 hours. 3 AMP (1 wt% NMP solution) 10.0 g, NMP (31.2 g), and BCS (66.7 g) were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent A1.

<Synthesis example 8>
NMP with BODA (18.0 g, 72.0 mmol), DA-1 (13.7 g, 36.0 mmol), DA-2 (8.72 g, 36.0 mmol), and DBA (7.30 g, 48.0 mmol). It was dissolved in (173.5 g) and reacted at 60° C. for 3 hours. After that, PMDA (10.1 g, 46.3 mmol) and NMP (57.8 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (250 g) and diluting it to 10 mass %, acetic anhydride (52.6 g) and pyridine (40.8 g) were added as an imidization catalyst, and the mixture was reacted at 80° C. for 4 hours. The deposit obtained by throwing in this reaction solution in methanol (2900g) was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder B was obtained. The imidation ratio of this polyimide was 77%, Mn was 12000, and Mw was 35000. A liquid crystal aligning agent B1 was obtained in the same manner as in Synthesis Example 7 except that the polyimide powder B (10.0 g) was used instead of the polyimide powder A.

<Synthesis example 9>
Liquid crystal aligning agent C1 was obtained by adding 30.0 g of liquid crystal aligning agent B1 obtained in Synthetic Example 8 to 70.0 g of liquid crystal aligning agent A1 obtained in Synthetic Example 7 and stirring at room temperature for 5 hours. It was

<Synthesis example 10>
BODA (6.51 g, 26.0 mmol), DA-1 (14.8 g, 38.9 mmol), and DBA (13.9 g, 91.0 mmol) were dissolved in NMP (165.3 g) at 60°C. The reaction was carried out for 3 hours. After that, CBDA (19.9 g, 101.5 mmol) and NMP (55.1 g) were added and reacted at 40° C. for 12 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (250 g) and diluting it to 6.5% by mass, acetic anhydride (59.7 g) and pyridine (18.5 g) were added as an imidization catalyst and reacted at 50° C. for 3 hours. .. The deposit obtained by throwing in this reaction solution in methanol (2900g) was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder D was obtained. The imidation ratio of this polyimide was 75%, Mn was 12000, and Mw was 32000. A liquid crystal aligning agent D1 was obtained in the same manner as in Synthesis Example 7 except that polyimide powder D (10.0 g) was used instead of polyimide powder A.

<Synthesis example 11>
Liquid crystal aligning agent E1 was obtained by adding 30.0 g of liquid crystal aligning agent D1 obtained in Synthetic Example 10 to 70.0 g of liquid crystal aligning agent A1 obtained in Synthetic Example 7 and stirring at room temperature for 5 hours. It was

<Synthesis example 12>
BODA (10.0 g, 40.0 mmol), DA-1 (19.0 g, 50.0 mmol), and DA-3 (16.5 g, 50.0 mmol) were dissolved in NMP (171.1 g), 60 The reaction was carried out at ℃ for 3 hours. Then, CBDA (11.5 g, 58.6 mmol) and NMP (57.0 g) were added, and it was made to react at 40 degreeC for 12 hours, and the polyamic-acid solution was obtained.
After adding NMP to this polyamic acid solution (250 g) and diluting it to 6.5% by mass, acetic anhydride (44.5 g) and pyridine (13.8 g) were added as an imidization catalyst and reacted at 70° C. for 3 hours. .. The deposit obtained by throwing in this reaction solution in methanol (2900g) was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder F was obtained. The imidation ratio of this polyimide was 73%, Mn was 14000, and Mw was 38000. A liquid crystal aligning agent F1 was obtained in the same manner as in Synthesis Example 7, except that the polyimide powder F (10.0 g) was used instead of the polyimide powder A.

<Synthesis example 13>
To 70.0 g of the liquid crystal aligning agent F1 obtained in Synthesis Example 12, 30.0 g of the liquid crystal aligning agent B1 obtained in Synthesis Example 8 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent G1.

<Synthesis example 14>
BODA (10.0 g, 40.0 mmol), DA-1 (15.2 g, 40.0 mmol), DA-3 (9.91 g, 30.0 mmol), and DA-5 (7.93 g, 30.0 mmol). Was dissolved in NMP (163.7 g) and reacted at 60° C. for 3 hours. Then, CBDA (11.5 g, 58.6 mmol) and NMP (54.6 g) were added, and it was made to react at 40 degreeC for 10 hours, and the polyamic acid solution was obtained.
After adding NMP to this polyamic acid solution (250 g) and diluting it to 6.5% by mass, acetic anhydride (46.5 g) as an imidization catalyst and pyridine (14.4 g) were added and reacted at 70° C. for 3 hours. It was The deposit obtained by throwing in this reaction solution in methanol (2900g) was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder H was obtained. The imidation ratio of this polyimide was 74%, Mn was 16000 and Mw was 45000. A liquid crystal aligning agent H1 was obtained in the same manner as in Synthesis Example 7, except that the polyimide powder H (10.0 g) was used instead of the polyimide powder A.

<Synthesis example 15>
TCA (1.35 g, 6.0 mmol), DA-1 (2.28 g, 6.0 mmol), and DA-3 (2.97 g, 9.0 mmol) were dissolved in NMP (24.9 g), 80 The reaction was carried out at ℃ for 3 hours. After that, CBDA (1.74 g, 8.9 mmol) and NMP (8.3 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (36g) and diluting to 6 mass %, acetic anhydride (4.0g) and pyridine (2.1g) were added as an imidization catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (700 ml), and the obtained precipitate was filtered off. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder I was obtained. The imidation ratio of this polyimide was 60%, Mn was 20000, and Mw was 43000.
NMP (44.0g) was added to the obtained polyimide powder I (6.0g), and it was made to melt|dissolve by stirring at 50 degreeC for 5 hours. 3 AMP (1 wt% NMP solution) 6.0 g, NMP (14.0 g) and BCS (30.0 g) were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent I1.

<Synthesis example 16>
BODA (2.00 g, 8.0 mmol), DA-3 (4.63 g, 14.0 mmol), and DA-4 (2.61 g, 6.0 mmol) were dissolved in NMP (34.5 g), 60 The reaction was carried out at ℃ for 3 hours. After that, CBDA (2.27 g, 11.6 mmol) and NMP (11.5 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (50 g) and diluting it to 6 mass %, acetic anhydride (5.3 g) and pyridine (2.7 g) were added as an imidization catalyst, and the mixture was reacted at 50° C. for 3 hours. This reaction solution was poured into methanol (700 ml), and the obtained precipitate was filtered off. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder J was obtained. The imidation ratio of this polyimide was 60%, Mn was 17,000, and Mw was 35,000. A liquid crystal aligning agent J1 was obtained in the same manner as in Synthesis Example 15 except that the polyimide powder J (10.0 g) was used instead of the polyimide powder I.

<Synthesis example 17>
BODA (1.30 g, 5.2 mmol), DA-6 (2.03 g, 3.9 mmol), and DA-3 (3.00 g, 9.1 mmol) were dissolved in NMP (23.5 g), 60 The reaction was carried out at ℃ for 3 hours. After that, CBDA (1.43 g, 7.3 mmol) and NMP (7.8 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
After adding NMP to this polyamic acid solution (36g) and diluting to 6 mass %, acetic anhydride (3.6g) and pyridine (1.9g) were added as an imidization catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain polyimide powder K. The imidation ratio of this polyimide was 60%, Mn was 16000, and Mw was 36000. A liquid crystal aligning agent K1 was obtained in the same manner as in Synthesis Example 15 except that the polyimide powder K (10.0 g) was used instead of the polyimide powder I.

(Example 1)
To 10.0 g of the liquid crystal aligning agent C1 obtained in Synthesis Example 9, 0.042 g (7 mass% based on the solid content) of the polymerizable compound RM1 obtained in Synthesis Example 1 was added, and the mixture was stirred at room temperature for 3 hours. Liquid crystal aligning agent L1 was prepared by stirring and dissolving.

(Example 2)
A liquid crystal aligning agent L2 was prepared in the same manner as in Example 1 except that the amount of the polymerizable compound RM1 was 0.06 g (10% by mass based on the solid content).
(Example 3)
A liquid crystal aligning agent L3 was prepared in the same manner as in Example 1 except that RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.
(Example 4)
A liquid crystal aligning agent L4 was prepared in the same manner as in Example 1 except that RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.

(Example 5)
A liquid crystal aligning agent M1 was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent A1 obtained in Synthesis Example 7 was used instead of the liquid crystal aligning agent C1.
(Example 6)
A liquid crystal aligning agent N1 was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent E1 obtained in Synthesis Example 11 was used instead of the liquid crystal aligning agent C1.
(Example 7)
A liquid crystal aligning agent O1 was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent G1 obtained in Synthesis Example 13 was used instead of the liquid crystal aligning agent C1.
(Example 8)
A liquid crystal aligning agent P1 was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent H1 obtained in Synthesis Example 14 was used instead of the liquid crystal aligning agent C1.

(Example 9)
A liquid crystal aligning agent Q1 was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent I1 obtained in Synthesis Example 15 was used instead of the liquid crystal aligning agent C1.
(Example 10)
A liquid crystal aligning agent R1 was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent J1 obtained in Synthesis Example 16 was used instead of the liquid crystal aligning agent C1.
(Example 11)
A liquid crystal aligning agent S1 was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent K1 obtained in Synthesis Example 17 was used instead of the liquid crystal aligning agent C1.

(Comparative Example 1)
A liquid crystal aligning agent L5 was prepared in the same manner as in Example 1 except that RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.
(Comparative example 2)
A liquid crystal aligning agent L6 was prepared in the same manner as in Example 1 except that RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.
(Comparative example 3)
A liquid crystal aligning agent L7 was prepared in the same manner as in Example 2 except that RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.
(Comparative example 4)
A liquid crystal aligning agent L8 was prepared in the same manner as in Example 1 except that RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.
(Comparative Example 5)
A liquid crystal aligning agent L9 was prepared in the same manner as in Example 2 except that RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.

<Production of liquid crystal cell>
(Example 12)
Using the liquid crystal aligning agent L1 obtained in Example 1, a liquid crystal cell was prepared by the following procedure.
The liquid crystal aligning agent L1 was spin-coated on the IZO surface of a 4-pixel IZO electrode substrate having an IZO electrode pattern (fishbone) having a pixel size of 87 μm×89 μm and a line/space of 3 μm, and the temperature was kept at 80° C. Dry on a hot plate for 90 seconds. Then, baking was performed for 20 minutes in a hot air circulation type oven at 200° C. to form a liquid crystal alignment film having a film thickness of 100 nm.
Furthermore, the liquid crystal aligning agent L1 was spin-coated on the ITO surface of the ITO electrode substrate on which no electrode pattern was formed, and dried on a hot plate at 80° C. for 90 seconds. Then, baking was performed for 20 minutes in a hot air circulation type oven at 200° C. to form a liquid crystal alignment film having a film thickness of 100 nm.
After spraying 3.3 μm bead spacers on the liquid crystal alignment film of one of the above two substrates, a sealant (solvent-type thermosetting epoxy resin) was printed on the spacers. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was placed inside, and after bonding with the previous substrate, the sealant was cured to prepare an empty cell. Liquid crystal MLC-6608 (manufactured by Merck Ltd.) was injected into this empty cell by a reduced pressure injection method. After that, the liquid crystal was re-aligned by placing it in a hot air circulation type oven at 120° C. for 1 hour to prepare a liquid crystal cell 1.

"Bright spot observation in liquid crystal cell"
The bright spots in the obtained liquid crystal cell 1 were observed by the following method. The liquid crystal cell 1 immediately after the above reorientation treatment was left at room temperature for 2 days, and then the liquid crystal cell was observed with a polarizing microscope. When the solubility of the polymerizable compound in the liquid crystal is low, it is presumed that the polymerizable compound easily precipitates in the liquid crystal cell and a bright spot is generated. The case where no bright spot is generated is defined as good, and the case where the bright spot is generated is defined as bad.

"Evaluation of afterimage from AC"
The afterimage of AC of the obtained liquid crystal cell 1 was measured by the following method.
While applying a DC voltage of 15 V to the liquid crystal cell 1, UV of 6 J/cm ² was passed from the outside of the liquid crystal cell 1 through a 365 nm bandpass filter. The illuminance of UV was measured using UV-MO3A manufactured by ORC. After that, UV (UV lamp: FLR40SUV32/A-1) was irradiated for 30 minutes using a UV-FL irradiation device manufactured by Toshiba Lighting & Technology Co., Ltd. in a state where no voltage was applied. Polarizing films were attached to both surfaces of the liquid crystal cell 1 in a crossed Nicol state such that the polarizing axis of the polarizing film and the director of the liquid crystal form 45°. A rectangular wave of 30 Hz, 20 Vpp was applied for 70 hours to only one arbitrary pixel and one pixel diagonally located out of the four pixels. After the voltage was cut off, the electrodes of the liquid crystal cell were connected to each other to make a short circuit. Then, this liquid crystal cell was placed on a backlight, and the brightness of the voltage-applied pixels and the non-voltage-applied pixels was visually compared. When the afterimage characteristics are good, it is considered that the difference in brightness between the voltage-applied pixel and the non-voltage-applied pixel is small, and the cells were observed from the front.

"Measurement of pretilt angle"
In the production of the liquid crystal cell 1, an ITO electrode substrate having an ITO electrode pattern having a pixel size of 100 μm×300 μm and a line/space size of 5 μm is used instead of the IZO electrode substrate of 4 pixels, and the size of 3.3 μm is used. A liquid crystal cell 2 was produced in the same manner as the liquid crystal cell 1 except that a bead spacer having a thickness of 4 μm was used instead of the bead spacer.
While applying a DC voltage of 15 V to the obtained liquid crystal cell 2, UV was passed through the liquid crystal cell 2 from the outside through a bandpass filter of 365 nm at 6 J/cm ² . The illuminance of UV was measured using UV-MO3A manufactured by ORC. After that, UV (UV lamp: FLR40SUV32/A-1) was irradiated for 30 minutes using a UV-FL irradiation device (manufactured by Toshiba Lighting & Technology Co., Ltd.) in a state where no voltage was applied.
The pretilt angle of the pixel portion after UV irradiation was measured using an LCD analyzer LCA-LUV42A (manufactured by Meiryo Technica).

(Examples 13 to 22, Comparative Examples 6 to 10)
A liquid crystal cell was produced in the same manner as in Example 12 except that the liquid crystal aligning agent shown in Table 2 was used instead of the liquid crystal aligning agent L1, and the above evaluation was performed for each liquid crystal cell. . The results are summarized in Table 2.

[Table 2]
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Liquid crystal aligning agent Polymerizable compound Liquid crystal cell AC-derived pretilt angle
Luminous spot in mass% Afterimage characteristics (°)
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Example 12 L1 RM1 7 Good Good 89.1
Example 13 L2 RM1 10 Good Good 88.8
Example 14 L3 RM2 7 Good Good 89.1
Example 15 L4 RM3 7 Good Good 89.0
Example 16 M1 RM1 7 Good Good 88.8
Example 17 N1 RM1 7 Good Good 89.0
Example 18 O1 RM1 7 Good Good 88.8
Example 19 P1 RM1 7 Good Good 88.7
Example 20 Q1 RM1 7 Good Good 88.6
Example 21 R1 RM1 7 Good Good 88.6
Example 22 S1 RM1 7 Good Good 88.6
Comparative Example 6 L5 RM4 7 Poor Good 89.2
Comparative Example 7 L6 RM5 7 Good Poor 89.3
Comparative Example 8 L7 RM5 10 Good Bad 89.0
Comparative Example 9 L8 RM6 7 Good Poor 89.6
Comparative Example 10 L9 RM6 10 Good Poor 89.4
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From the results of the bright spot observation of Examples 12 to 15 and Comparative Example 6, it can be seen that the solubility in the liquid crystal is improved by making the molecular structure of the polymerizable compound used asymmetric.
Further, from the comparison between Examples 12, 14, and 15 and Comparative Examples 7 and 8, the method for asymmetry of the molecular structure of the polymerizable compound of the present invention (methods 1 and 2 described above) shows that the benzene ring is asymmetrical. It can be seen that, as compared with the method (Method 4) in which a substituent is introduced so that the residual image characteristics derived from AC are excellent.
Similarly, from the results of Examples 12, 14 and 15 and Comparative Examples 9 and 10, the method for asymmetry of the molecular structure of the polymerizable compound of the present invention was compared with the method in which the left and right polymerizable groups were different (Method 3). However, it can be seen that the afterimage characteristics derived from AC are excellent.
It is considered that this is because the stacking of the ring structure is stronger than that of the compound in which one of the polymerizable groups has a methacryl group that is not a ring structure, and thus the polymer network obtained is more rigid.

A liquid crystal display device having a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention has a high response speed of liquid crystal, and can be widely used as a vertical alignment type liquid crystal display device such as a PSA liquid crystal display. .
In addition, the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2015-22123 filed on February 6, 2015 are incorporated herein as disclosure of the specification of the present invention. It is a thing.

Claims (4)

A polymerizable compound represented by the following formula (1).

(In the formula, X ¹ and X ² each independently represent a bonding group selected from an ether bond and an ester bond, and S ¹ and S ² each independently represent a linear alkylene having 2 to 9 carbon atoms. Represents a group and S ¹ , X ¹ , X ² and S ² are selected such that the molecule is left-right asymmetric.) The polymerizable compound according to claim 1, wherein in the formula (1), S ¹ and S ² are alkylene groups having different carbon numbers. In formula (1), ^one of X ¹ and X ² is an ether bond and the other is an ester bond, or X ¹ is an ester bond bonding to S ¹ on the carbonyl side, and X ² is an oxygen atom. The polymerizable compound according to claim 1 or 2, which is an ester bond which is bonded to S ² on the side. The polymerizable compound according to any one of claims 1 to 3, which is a compound of any of the following formulas RM1 to RM3.