CN114507149A - Diamine compound, polymer, alignment agent, alignment film, and liquid crystal display element - Google Patents

Abstract

The invention provides a diamine compound, a polymer, a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element. The invention provides a diamine compound with a specific structure, which is applied to forming a polymer, a liquid crystal alignment agent and a liquid crystal display element, and the liquid crystal display element manufactured by using the liquid crystal alignment agent has good electric field memory effect and environmental resistance. The diamine compound is a diamine compound b1-1 represented by the formula (I). The polymer a-1 is prepared by reacting a first mixture comprising a tetracarboxylic dianhydride compound a1 and a diamine compound b1, wherein the diamine compound b1 comprises a diamine compound b1-1 represented by formula (I). The liquid crystal aligning agent comprises a polymer A-1 and a solvent B.

Description

Diamine compound, polymer, alignment agent, alignment film and liquid crystal display element

technical field

The present invention relates to a diamine compound, a polymer, a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element, in particular to a diamine compound and a polymer that can produce a liquid crystal display element with good electric field memory effect and environmental resistance , liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element.

Background technique

Conventionally, a twisted nematic (TN) type or a super twisted nematic (STN) type using liquid crystal molecules having positive dielectric anisotropy has been known as an operation method of a liquid crystal display element. Various liquid crystal display elements such as Vertical Alignment (VA) type, In Plane Switching (IPS) type, Fringe Field Switching (FFS) type, Optically Compensated Bend (OCB) type, etc. However, in order to control the alignment of each liquid crystal molecule, a liquid crystal alignment film formed of an organic film is mainly used (Patent Documents 1 to 4).

Since the liquid crystal alignment films of the TN type and STN type have a high-speed response of liquid crystal molecules, and the liquid crystal alignment films of the VA type and other liquid crystal alignment films have a certain tilt direction during liquid crystal driving, they each need to have a pretilt angle characteristic. As a method of imparting the pretilt angle characteristic, in the case of the former, a rubbing method is usually used, and in the case of the latter, a rubbing method or a method of providing protrusions on the surface of the substrate is usually used. Dust or static electricity generated in the rubbing process may cause problems such as poor display or circuit damage. On the other hand, the method of providing protrusions on the surface of the substrate may impair the brightness of the resulting liquid crystal display element. Therefore, these methods have problems. .

Therefore, as a pretilt angle imparting method instead of these methods, a so-called photo-alignment method in which ultraviolet rays are irradiated to a photosensitive thin film from a direction inclined with respect to the film normal has been proposed (Patent Document 5). However, the liquid crystal display element produced with the liquid crystal aligning agent described in Patent Document 5 has the problems of poor electric field memory effect and environmental resistance of the liquid crystal display element, which is not suitable for application.

On the other hand, as a method of imparting liquid crystal alignment ability to a coating film formed of a liquid crystal aligning agent containing polyamic acid or the like, in recent years, photo-alignment methods such as photoisomerization, photodimerization, and photolysis have been proposed. A technique that replaces the friction method. The photo-alignment method is a method of controlling the alignment of liquid crystal molecules by irradiating a radiation-sensitive organic thin film formed on a substrate with polarized or non-polarized radiation to impart anisotropy to the film. According to this method, the generation of dust and static electricity in the step can be suppressed compared with the conventional rubbing method, so that the occurrence of display defects and the decrease in yield due to dust and the like can be suppressed. In addition, there is also an advantage that liquid crystal alignment ability can be uniformly imparted to the organic thin film formed on the substrate.

Specifically, there are technical documents on the photo-alignment method such as Patent Document 6. Patent Document 6 proposes a liquid crystal aligning agent having a repeating unit of a conjugated enone and an imide structure. However, the liquid crystal display element produced by using the liquid crystal aligning agent described in Patent Document 6 also has problems that the electric field memory effect and environmental resistance of the liquid crystal display element are not good.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 56-91277

[Patent Document 2] Japanese Patent Application Laid-Open No. 1-120528

[Patent Document 3] Japanese Patent Application Laid-Open No. 11-258605

[Patent Document 4] Japanese Patent Laid-Open No. 2002-250924

[Patent Document 5] Japanese Patent Laid-Open No. 2004-83810

[Patent Document 6] Japanese Patent Laid-Open No. 2005-037654

Therefore, how to improve the problems of the electric field memory effect and the poor environmental resistance of the liquid crystal display element in order to meet the requirements of the current industry is an urgent problem to be solved by those skilled in the art at present.

SUMMARY OF THE INVENTION

In view of this, the present invention provides a diamine compound, which can form a polymer, and the polymer can make a liquid crystal alignment agent and a liquid crystal alignment film for a liquid crystal display element, which can improve the electric field memory effect and the liquid crystal display element of the above-mentioned liquid crystal display element. The problem of poor environmental resistance.

The present invention provides a diamine compound, which is a diamine compound (b1-1) represented by formula (I).

In formula (I),

其中R¹⁴表示氢或碳数为1至4的烷基；X ¹ and X ² each independently represent a single bond, -O-,

wherein R ¹⁴ represents hydrogen or an alkyl group having a carbon number of 1 to 4;

x represents 0 or 1;

y represents an integer from 0 to 4;

R ¹ represents a methylene group or an alkylene group having a carbon number of 2 to 4;

R ³ each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group;

R ² represents an organic group represented by formula (IA) or a monovalent organic group having a steroid skeleton having a carbon number of 17 to 40;

In formula (I-A),

R ⁴ represents fluorine or methyl;

亚甲基或碳数为2至3的亚烷基；R ⁵ , R ⁶ and R ⁷ each independently represent a single bond, -O-,

Methylene or alkylene having 2 to 3 carbons;

其中R¹⁰及R¹¹各自独立表示氟或甲基，*表示键结位置；R ⁸ means

wherein R ¹⁰ and R ¹¹ each independently represent fluorine or methyl, and * represents the bonding position;

R ⁹ represents hydrogen, fluorine, alkyl having 1 to 12 carbons, fluoroalkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, fluorine-substituted alkoxy having 1 to 12 carbons Alkoxy, -OCH ₂ F, -OCHF ₂ , -OCF ₃ ;

a represents an integer from 0 to 2;

b, c and d each independently represent an integer from 0 to 4;

e, f and g each independently represent an integer from 0 to 3;

i and j each independently represent an integer from 0 to 2;

* indicates the bond position;

When R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ or R ¹¹ are plural, each independently represents the same or different groups.

其中R¹⁴表示氢或碳 数为1至4的烷基；当x为1时，X¹为单键。In an embodiment of the present invention, in the above-mentioned diamine compound (b1-1) represented by formula (I), when x is 0, X ¹ is -O-,

wherein R ¹⁴ represents hydrogen or an alkyl group having a carbon number of 1 to 4; when x is 1, X ¹ is a single bond.

In an embodiment of the present invention, in the above-mentioned diamine compound (b1-1) represented by formula (I), when x is 0, X ¹ is -O-,

亚甲基或碳数为2至3的亚 烷基。In one embodiment of the present invention, in the above-mentioned diamine compound (b1-1) represented by formula (I), R ⁵ , R ⁶ and R ⁷ each independently represent a single bond, -O-,

A methylene group or an alkylene group having 2 to 3 carbon atoms.

In one embodiment of the present invention, in the above-mentioned diamine compound (b1-1) represented by formula (I), when e+f+g<3, f and g are different, it is 0; when f≧1 , b≧1; when g≧1, c+d≧1.

The present invention provides a polymer (A-1) prepared by reacting a first mixture, and the first mixture comprises a tetracarboxylic dianhydride compound (a1) and a diamine compound (b1). The diamine compound (b1) includes the diamine compound (b1-1) represented by the formula (I) as described above.

In an embodiment of the present invention, the above-mentioned diamine compound (b1) further includes a diamine compound (b1-2) represented by formula (II).

In formula (II),

R ¹⁵ and R ¹⁷ each independently represent -O-, -S-,

R ¹⁶ represents an alkylene group having a carbon number of 2 to 10;

R ¹⁸ represents a single bond, methylene or ethylene;

Y ¹ represents a monovalent organic group having a carbon number of 17 to 40 having a steroid skeleton.

In an embodiment of the present invention, the above-mentioned diamine compound (b1) further includes a diamine compound (b1-3) represented by formula (III).

In formula (III),

-CH₂O-、

Y ² each independently represents -O-, -NH-,

-CH ₂ O-,

Y ³ each independently represents a single bond, a divalent aliphatic hydrocarbon group with a carbon number of 1 to 20, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group;

其中m表示 1至5的整数；Y ⁴ each independently represents a single bond, -O-, -NH-,

where m represents an integer from 1 to 5;

Y ⁵ each independently represents a nitrogen-containing aromatic heterocyclic group;

k represents an integer of 1 to 4.

In an embodiment of the present invention, the amount of the diamine compound (b1-1) represented by the formula (I) is 50 to 100 parts by mole based on 100 parts by mole of the diamine compound (b1) .

In an embodiment of the present invention, the amount of the diamine compound (b1-2) represented by the formula (II) is 5 to 30 parts by mole based on 100 parts by mole of the diamine compound (b1) .

In one embodiment of the present invention, the amount of the diamine compound (b1-3) represented by the formula (III) is 1 to 20 parts by mole based on 100 parts by mole of the diamine compound (b1) .

The present invention also provides a liquid crystal alignment agent comprising the above-mentioned polymer (A-1) and a solvent (B).

In an embodiment of the present invention, the above-mentioned liquid crystal alignment agent further includes a polymer (A-2). The polymer (A-2) is obtained by reacting the second mixture. The second mixture contains the tetracarboxylic dianhydride compound (a2) and the diamine compound (b2).

In an embodiment of the present invention, based on the polymer (A-1) in an amount of 100 parts by weight, the solvent (B) in an amount of 1000 to 3500 parts by weight.

In an embodiment of the present invention, based on the total usage amount of the polymer (A-1) and the polymer (A-2) being 100 parts by weight, the usage amount of the polymer (A-1) is 30 parts by weight to 95 parts by weight parts by weight.

In an embodiment of the present invention, based on the total usage amount of polymer (A-1) and polymer (A-2) is 100 parts by weight, the usage amount of solvent (B) is 1000 parts by weight to 3500 parts by weight.

The present invention further provides a liquid crystal alignment film, which is formed from the above-mentioned liquid crystal alignment agent.

The present invention also provides a liquid crystal display element comprising the above-mentioned liquid crystal alignment film.

Based on the above, when the present invention applies the diamine compound with a specific structure to form a polymer, a liquid crystal alignment agent and a liquid crystal display element, the liquid crystal display element produced by using the liquid crystal alignment agent can have good electric field memory effect and environmental resistance. It is suitable for liquid crystal alignment films and liquid crystal display elements.

In order to make the above-mentioned features and advantages of the present invention more obvious and easy to understand, the following embodiments are given and described in detail in conjunction with the accompanying drawings as follows.

Description of drawings

FIG. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention.

DESCRIPTION OF REFERENCE NUMERALS 100: Liquid crystal display element

110: Unit 1

112: first substrate

114: first conductive film

116: The first liquid crystal alignment film

120: Unit Two

122: Second substrate

124: Second conductive film

126: Second liquid crystal alignment film

130: Liquid crystal cell

Detailed ways

<Diamine compound>

The diamine compound is a diamine compound (b1-1) represented by formula (I).

其中R¹⁴表示氢或碳数为1至4的烷基。In formula (I), X ¹ and X ² each independently represent a single bond, -O-,

wherein R ¹⁴ represents hydrogen or an alkyl group having 1 to 4 carbons.

更佳为-O-、

其中R¹⁴表示氢或碳数为1至4的烷基。当x为1时，X¹较佳为表示单键。In formula (I), x represents 0 or 1. When x is 0, X ¹ preferably represents -O-,

More preferably -O-,

wherein R ¹⁴ represents hydrogen or an alkyl group having 1 to 4 carbons. When x is 1, X ¹ preferably represents a single bond.

In formula (I), y represents an integer of 0 to 4; preferably, an integer of 0 to 3; more preferably, an integer of 0 to 2.

In formula (I), R ¹ represents a methylene group or an alkylene group with a carbon number of 2 to 4; preferably a methylene group or an alkylene group with a carbon number of 2 to 3; more preferably a methylene group .

In formula (I), R ³ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group; preferably an alkyl group having 1 to 4 carbon atoms, An alkoxy group having a carbon number of 1 to 4, a fluorine atom or a cyano group.

In the formula (I), R ² represents an organic group represented by the formula (IA) or a monovalent organic group having a steroid skeleton having a carbon number of 17 to 40.

In formula (IA), R ⁴ represents fluorine or methyl.

亚甲基或碳数为2至3的亚烷基；较佳为各 自独立表示单键、－O－、

亚甲基或碳数为2 至3的亚烷基。In formula (IA), R ⁵ , R ⁶ and R ⁷ each independently represent a single bond, -O-,

Methylene group or alkylene group having 2 to 3 carbon atoms; preferably each independently represents a single bond, -O-,

A methylene group or an alkylene group having 2 to 3 carbon atoms.

其中R¹⁰及R¹¹各自独立表示氟或甲基；*表示键结位置。i及j各自独立表示0至2的整数。In formula (IA), R ⁸ represents

wherein R ¹⁰ and R ¹¹ each independently represent fluorine or methyl; * represents a bonding position. i and j each independently represent an integer of 0 to 2.

In formula (I-A), a represents an integer from 0 to 2; b, c and d each independently represent an integer from 0 to 4, preferably each independently represents an integer from 0 to 2; e, f and g each independently represent 0 to 2 The integer of 3 is preferably an integer each independently representing 0 to 2. When e+f+g<3, f and g cannot be 0 at the same time. When f≧1, b≧1. When g≧1, c+d≧1.

In formula (I-A), * represents a bonding position.

In formula (IA), when R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ or R ¹¹ are plural, each independently represents the same or different groups.

Specifically, in the case where f and g are not 0, when a represents 2, each of the plurality of R ⁴ may represent the same or different groups; when b, c and d each independently represent 2 to 4 In the case of integers, each of the plurality of R ⁵ may represent the same or different groups, each of the plurality of R ⁶ may represent the same or different groups, and each of the plurality of R ⁷ may represent the same or different groups; when e represents 2 or 3, each of the plurality of R ⁸ may represent the same or different groups. In addition, when i represents 2, each of a plurality of R ¹⁰ may represent the same or different groups. When j represents 2, each of the plurality of R ¹¹ may represent the same or different groups.

In formula (IA), R ⁹ represents hydrogen, fluorine, alkyl having 1 to 12 carbons, fluoroalkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, carbon substituted by fluorine Alkoxy groups of 1 to 12, -OCH ₂ F, -OCHF ₂ , -OCF ₃ .

Specific examples of the organic group represented by the formula (I-A) include at least one of the organic groups represented by the formula (I-A-1) to the formula (I-A-9).

In the formula (IA-1) to the formula (IA-9), the group represented by R ⁹ is the same as the group represented by R ⁹ in the formula (IA), and will not be repeated here.

The steroid skeleton in the monovalent organic group having a steroid skeleton having a carbon number of 17 to 40 refers to a cyclopentano-perhydro phenanthrene skeleton or one or more of the carbon-carbon bonds contained therein Change to double bond skeleton. Examples of the monovalent organic group having such a steroid skeleton include groups represented by the following formula (I-B-a), formula (I-B-b), formula (I-B-c) or formula (I-B-d), wherein * represents a bonding position.

In formula (IBa), formula (IBb), formula (IBc) and formula (IBd), A ^I each independently represents a group represented by any one of the following structural formulas, wherein * represents a bonding position.

Specific examples of the monovalent organic group having a steroid skeleton having a carbon number of 17 to 40 include those represented by formula (I-B-1), formula (I-B-2), formula (I-B-3) or formula (I-B-4) Organic groups, where * denotes the bonding position.

Specific examples of the diamine compound (b1-1) represented by formula (I) preferably include compounds represented by formula (I-1) to formula (I-9), more preferably include compounds represented by formula (I-1) ) to compounds represented by formula (I-3), formula (I-6), formula (I-7), and formula (I-9).

When the polymer (A-1) in the following liquid crystal alignment agent does not use the diamine compound (b1-1), the liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent have electric field memory effect and poor environmental resistance. question.

<Liquid crystal alignment agent>

The present invention provides a liquid crystal alignment agent, comprising a polymer (A-1) and a solvent (B). In other embodiments, the liquid crystal alignment agent may further include the polymer (A-2). In addition, the liquid crystal aligning agent may further include an additive (C) if necessary. The individual components of the liquid crystal aligning agent used in the present invention will be described in detail below.

Polymer (A-1)

The polymer (A-1) includes a polyamic acid polymer, a polyimide polymer, a polyimide-based block copolymer or a combination of the above polymers, wherein the polyimide-based block copolymer includes A polyamic acid block copolymer, a polyimide block copolymer, a polyamic acid-polyimide block copolymer, or a combination of the foregoing copolymers.

The polymer (A-1) is obtained by reacting the first mixture containing the tetracarboxylic dianhydride compound (a1) and the diamine compound (b1). The tetracarboxylic dianhydride compound (a1), the diamine compound (b1) and the method for producing the polymer (A-1) will be described in detail below.

Tetracarboxylic dianhydride compound (a1)

The tetracarboxylic dianhydride compound (a1) includes an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound or the following formulas (1-1) to (1) -6) Tetracarboxylic dianhydride compounds such as the tetracarboxylic dianhydride compounds represented.

Specific examples of the aliphatic tetracarboxylic dianhydride compound include aliphatic tetracarboxylic dianhydrides such as ethanetetracarboxylic dianhydride and butane tetracarboxylic dianhydride. However, the present invention is not limited thereto, and the aliphatic tetracarboxylic dianhydride compound may further include other suitable aliphatic tetracarboxylic dianhydride compounds.

Specific examples of the alicyclic tetracarboxylic dianhydride compound include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetra Carboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylate Acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-Cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloheptyl-1,5 - Diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride or bicyclo[2.2.2]-oct-7-ene-2,3 , 5,6-tetracarboxylic dianhydride and other alicyclic tetracarboxylic dianhydride compounds. However, the present invention is not limited thereto, and the alicyclic tetracarboxylic dianhydride compound may further include other suitable alicyclic tetracarboxylic dianhydride compounds.

Specific examples of the aromatic tetracarboxylic dianhydride compound include 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 2,2' ,3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetra Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'-4,4'-diphenylethane Tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1 ,2,3,4-furan tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid di Anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 2,3,3',4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3' ,4,4'-diphenyl sulfide tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4- Dicarboxyphenoxy) diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylene diphthalic acid dianhydride, 2,2',3,3'-diphenyltetracarboxyl Acid dianhydride, 2,3,3',4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine Oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid) -4,4'-diphenylether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(anhydrotrimellitate), propylene glycol -Bis(anhydrotrimellitate), 1,4-Butanediol-bis(anhydrotrimellitate), 1,6-hexanediol-bis(anhydrotrimellitate), 1,8 -Octanediol-bis(anhydrotrimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydrotrimellitate), 2,3,4,5-tetrahydrofuran tetracarboxylate Acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]- Furan-1,3-dione (1,3,3a,4,5,9b-Hexahydro-5-(tetrahydro-2,5-dioxofuran-3-yl)naphtho[1,2-c]furan-1, 3-dione), 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1 ,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxy- 3-Furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrakis Hydro-2,5-di-oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro -7-Ethyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3, 3a,4,5,9b-Hexahydro-8-methyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1 ,3-Dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[ 1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dione pendant oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione or 5-(2,5-dioxytetrahydrofuranyl)-3-methyl-3 -Aromatic tetracarboxylic dianhydride compounds such as cyclohexene-1,2-dicarboxylic dianhydride. However, the present invention is not limited thereto, and the aromatic tetracarboxylic dianhydride compound may further include other suitable aromatic tetracarboxylic dianhydride compounds.

The tetracarboxylic dianhydride compounds represented by formula (1-1) to formula (1-6) are shown below.

In formula (1-5), A ¹ represents a divalent group containing an aromatic ring; r represents 1 or 2; and A ² and A ³ each independently represent hydrogen or an alkyl group.

In formula (1-6), A ⁴ represents a divalent group containing an aromatic ring; A ⁵ and A ⁶ may each independently represent hydrogen or an alkyl group.

Specific examples of the tetracarboxylic dianhydride compound (a1) represented by the formula (1-5) include the tetracarboxylic dianhydride compounds represented by the formula (1-5-1) to the formula (1-5-3).

Specific examples of the tetracarboxylic dianhydride compound (a1) represented by the formula (1-6) include the tetracarboxylic dianhydride compound represented by the formula (1-6-1).

The above-mentioned tetracarboxylic dianhydride compound (a1) may be used alone or in combination of two or more.

Specific examples of the tetracarboxylic dianhydride compound (a1) preferably include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride (1,2,3,4-cyclobutane tetracarboxylic acid dianhydride), 1,2 ,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,4,5-cyclohexane Alkanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride or combinations thereof, more preferably including 1,2,3,4-ring Butanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, pyromellitic dianhydride, or a combination thereof.

Diamine compound (b1)

The diamine compound (b1) includes at least one diamine compound (b1-1) represented by the formula (I). In addition, the diamine compound (b1) may further include at least one of the diamine compound (b1-2) represented by the formula (II) and the diamine compound (b1-3) represented by the formula (III). In addition, the diamine compound (b1) may include other diamine compounds (b1-4). Hereinafter, the diamine compound (b1-1), the diamine compound (b1-2), the diamine compound (b1-3) and the other diamine compounds (b1-4) will be described in detail.

Diamine compound (b1-1)

The diamine compound (b1-1) has been described in the above <Diamine compound>, and will not be repeated here. When the polymer (A-1) in the liquid crystal alignment agent does not use the diamine compound (b1-1), the liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent have the problems of electric field memory effect and poor environmental resistance .

The diamine compound (b1-1) represented by the formula (I) may be used in an amount of 50 to 100 parts by mole, preferably 55 to 100 parts by mole, based on 100 parts by mole of the diamine compound (b1). 100 mol parts, more preferably 65 mol parts to 100 mol parts.

Diamine compound (b1-2)

The diamine compound (b1-2) is a diamine compound represented by formula (II).

In formula (II), R ¹⁵ and R ¹⁷ each independently represent an ether group, a thioether group, a thioester group, or an ester group. Specifically, R ¹⁵ and R ¹⁷ each independently represent -O-, -S-,

In formula (II), R ¹⁶ represents an alkylene group having 2 to 10 carbon atoms; preferably, it represents an alkylene group having 2 to 4 carbon atoms.

In formula (II), R ¹⁸ represents a single bond, a methylene group or an ethylene group; preferably, it represents a single bond or a methylene group.

In formula (II), Y ¹ represents a monovalent organic group having a carbon number of 17 to 40 having a steroid skeleton. The steroid skeleton is the same as the steroid skeleton represented by R ² in formula (I), and will not be described in detail here.

Specific examples of the diamine compound (b1-2) include diamine compounds represented by formula (II-1) to formula (II-29), preferably include formula (II-10), formula (II-18) , at least one of the diamine compounds represented by formula (II-24), formula (II-22), and formula (II-26).

The diamine compound (b1-2) represented by the formula (II) can be synthesized by an existing organic synthesis method. For example, compounds represented by formula (II-1), formula (II-2), formula (II-7) or formula (II-8) are synthesized by combining anhydrous succinic acid with cholesterol or cholestane, respectively After addition reaction of cholestanol to form acid chloride with, for example, thionyl chloride, dinitrophenol is reacted with acid chloride in the presence of more equivalents of base based on acid chloride, and thereafter, using appropriate A reducing agent such as tin chloride is used for reduction reaction, so as to complete the above synthesis.

The compound represented by formula (II-3), formula (II-4), formula (II-9) or formula (II-10) can be synthesized by adding anhydrous succinic acid to cholesterol or cholestanol, respectively. After the formation reaction, in the presence of potassium carbonate, the aforementioned adduct is subjected to an esterification reaction with dinitrobenzoyl chloride, and thereafter, a reduction reaction is performed using a suitable reducing agent such as tin chloride, so as to complete the above-mentioned reaction. synthesis.

The compound represented by the formula (II-5) or the formula (II-11) can be synthesized by tosylation of cholesterol or cholestanol with tosyl chloride, respectively, to obtain a tosyl chloride. Tosylation (tosylation) cholesterol or tosylation of cholestanol, followed by dinitrobenzoyl butanediol monoester obtained by reacting butanediol and excess dinitrobenzoyl chloride in the presence of a base, with The aforementioned tosylation of cholestanol is heated in a suitable organic solvent to form an ether group, and then a suitable reducing agent such as tin chloride is used to carry out a reduction reaction, thereby completing the above synthesis.

The compound represented by the formula (II-6) or the formula (II-12) can be synthesized by adding anhydrous succinic acid to cholesterol or cholestanol, respectively, and then converting the carbonyl group of the adduct to aluminum hydride. Lithium is reduced to a methylene group, and in the presence of a base such as potassium tert-butoxide, the aforementioned reduced product is subjected to an esterification reaction with 2,4-dinitrochlorobenzene (2,4-dinitrochlorobenzene), and thereafter, an appropriate A reducing agent such as tin chloride is used for reduction reaction; or in the presence of a base such as potassium 3-butoxide, the 1-(4-hydroxyl group obtained by reacting 2,4-dinitrochlorobenzene with excess butanediol Butoxy)-2,4-dinitrobenzene (1-(4-hydroxybutoxy)-2,4-dinitrobenzene), tosylated cholesterol or tosylated cholesterol prepared as previously described The alkanol is heated in a suitable organic solvent to form an ether group, and then a reduction reaction is carried out using a suitable reducing agent such as tin chloride to complete the above synthesis.

The compound represented by the formula (II-13) can be synthesized by reacting 2,4-dinitrochlorobenzene with excess ethylene glycol in the presence of a base such as potassium tert-butoxide. -Hydroxyethoxy)-2,4-dinitrobenzene (1-(4-hydroxyethoxy)-2,4-dinitrobenzene), and tosylated cholestanol as previously described , heated in a suitable organic solvent to form an ether group, and then used a suitable reducing agent such as tin chloride to carry out a reduction reaction, thereby completing the above synthesis.

The synthesis of the compound represented by formula (II-14), formula (II-15) or formula (II-16) can be started using lanosterol, lumisterol or ergosterol, respectively raw materials, and synthesized according to the synthetic method of formula (II-6).

The compound represented by formula (II-17) or formula (II-18) can be synthesized by methanesulfonylation of cholesterol or cholestanol with methanesulfonyl chloride, respectively, and then with excess amount. Ethylene glycol undergoes a substitution reaction to synthesize a monoether compound, and in the presence of a base, the aforementioned monoether compound and 3,5-dinitrobenzoyl chloride are reacted to synthesize a dinitro compound Afterwards, the above synthesis is completed by performing a reduction reaction using a suitable reducing agent such as palladium carbon.

The compound represented by formula (II-19) or formula (II-20) can be synthesized by using potassium hydride to form alkoxide with cholesterol or cholesterol, respectively, and then form an ether group with excess dibromopropane to form an alkoxide. The intermediate is obtained, followed by the presence of potassium carbonate, this intermediate is reacted with 3,5-dinitrobenzoic acid (3,5-dinitrobenzoic acid) to synthesize a dinitro compound, and a suitable reducing agent such as palladium carbide is used to carry out reduction reaction to complete the above synthesis.

The compound represented by the formula (II-21) or the formula (II-22) can be synthesized by adding anhydrous succinic acid to cholesterol or cholestanol, respectively, and then adding N,N-dicyclohexylcarbon two. In the presence of imine (N,N-dicyclohexylcarbodiimide), this adduct is reacted with 3,5-(N,N-diallyl)aminophenol (3,5-(N,N-diallyl)aminophenol), It is obtained by removing allyl groups with 1,3-dimethylbarbituric acid and tetrakistriphenyl phosphinepalladium.

The compound represented by formula (II-23) or formula (II-24) can be synthesized by adding anhydrous succinic acid to cholesterol or cholestanol, respectively, and then using borane-tetrahydrofuran complex (Borane tetrahydrofuran complex). -oxolane complex) to reduce the carbonyl group to alcohol as an intermediate; in the presence of a base, the aforementioned intermediate is reacted with 3,5-dinitrobenzoyl chloride to synthesize a dinitro compound, and a suitable reducing agent such as palladium carbide is used. A reduction reaction is carried out to complete the above synthesis.

The compound represented by formula (II-25) or formula (II-26) can be synthesized by adding anhydrous glutaric acid substituted succinic acid to cholesterol or cholestanol, respectively, and according to formula (II- 4) or the synthesis method of formula (II-10).

The compound represented by formula (II-27), formula (II-28) or formula (II-29) can be synthesized by hydrogenating lanosterol, photosterol or ergosterol using a suitable hydrogenation catalyst as a starting material, and It is synthesized according to the synthesis method of formula (II-14), formula (II-15) or formula (II-16).

When the diamine compound (b1) in the polymer (A-1) in the liquid crystal alignment agent includes the diamine compound (b1-2), the liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent can have better performance The electric field memory effect.

The diamine compound (b1-2) represented by the formula (II) may be used in an amount of 5 to 30 parts by mole, preferably 7 to 7 parts by mole, based on 100 parts by mole of the diamine compound (b1) used. 27 mol parts, more preferably 10 mol parts to 25 mol parts.

Diamine compound (b1-3)

The diamine compound (b1-3) is the diamine compound (b1-3) represented by the formula (III).

-CH₂O-、

Y³各自独立表示单键、碳数为1 至20的二价脂肪族烃基、二价脂环族烃基或二价芳香族烃基；Y⁴各自独立表示单键、 -O-、-NH-、

其中m表示1至5的整数；Y⁵各自独立 表示含氮的芳香族杂环基；k表示1至4的整数。In formula (III), Y ² each independently represents -O-, -NH-,

-CH ₂ O-,

Y ³ each independently represents a single bond, a divalent aliphatic hydrocarbon group with a carbon number of 1 to 20, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group; Y ⁴ each independently represents a single bond, -O-, -NH-,

wherein m represents an integer from 1 to 5; Y ⁵ each independently represents a nitrogen-containing aromatic heterocyclic group; and k represents an integer from 1 to 4.

Specifically, the bonding position of the two amino groups (—NH ₂ ) in the formula (III) is not particularly limited. Specifically, with respect to the binding group (Y ² ) of the side chain, the two amino groups on the benzene ring are respectively 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position or 3,5 positions etc. From the viewpoint of reactivity at the time of synthesizing a polyamic acid, the bonding positions of the two amino groups are preferably 2,4 positions, 2,5 positions, or 3,5 positions. On the other hand, the bonding position of the two amino groups is more preferably the 2,4 position or the 2,5 position in consideration of the easiness of synthesizing the diamine compound.

-CH₂O-、

就合成二胺化合物时的容 易性而言，Y²较佳为各自独立表示-O-、-NH-、

-CH₂O-、

In formula (III), Y ² each independently represents -O-, -NH-,

-CH ₂ O-,

In terms of easiness in synthesizing the diamine compound, Y ² preferably independently represents -O-, -NH-,

-CH ₂ O-,

In formula (III), Y ³ each independently represents a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched, or may have an unsaturated bond, and is preferably a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. Specific examples of the alicyclic ring in the divalent alicyclic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, and a cyclodecane ring Alkane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring , cyclononadecane ring, cycloeicosane ring, tricycloicosane ring, tricyclodocosane ring, bicycloheptane ring, decahydronaphthalene ring ( decahydronaphthalene ring), norbornene ring (norbornene ring) or adamantane ring (adamantanering) and the like.

Specific examples of the aromatic ring in the divalent aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azuene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, or a Sepia ring (phenalene ring) and so on.

Specifically, in formula (III), Y ³ preferably each independently represents a single bond, a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, and a linear chain having 2 to 10 carbon atoms. Or branched alkenylene group, straight-chain or branched alkynylene group with carbon number of 2 to 10, divalent alicyclic hydrocarbon group or divalent aromatic hydrocarbon group, wherein the alicyclic in the divalent alicyclic hydrocarbon group is cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring, the aromatic ring in the divalent aromatic hydrocarbon group is benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring. More preferably, Y ³ each independently represents a single bond, a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, a linear or branched alkenylene group having 2 to 10 carbon atoms, a divalent lipid Cyclic hydrocarbon group or divalent aromatic hydrocarbon group, wherein the alicyclic ring in the divalent alicyclic hydrocarbon group is cyclohexane ring, norbornene ring or adamantane ring, and the aromatic ring in the divalent aromatic hydrocarbon group is benzene ring, naphthalene ring ring, fluorene ring or anthracene ring. More preferably, Y ³ each independently represents a single bond, a methylene group, a straight-chain or branched alkylene group having 2 to 10 carbon atoms, a cyclohexylene group, a phenylene group, or a naphthylene group. It is particularly preferable that Y ³ each independently represents a single bond, a methylene group, a linear or branched alkylene group having 2 to 5 carbon atoms, or a phenylene group.

In formula (III), Y ⁴ each independently represents a single bond, -O-, -NH-,

其中m表示1至5的整数。wherein m represents an integer from 1 to 5. Y ⁴ preferably each independently represents a single bond, -O-,

wherein m represents an integer from 1 to 5.

In formula (III), Y ⁵ each independently represents a nitrogen-containing aromatic heterocyclic group. Specifically, the nitrogen-containing aromatic heterocyclic group is a nitrogen-containing heterocyclic group containing at least one structure selected from the group consisting of formula (III-A), formula (III-B) and formula (III-C). Aromatic heterocyclic group.

In formula (III-C), R ¹⁹ represents a linear or branched alkyl group having 1 to 5 carbon atoms.

Specific examples of the nitrogen-containing aromatic heterocycle in Y ⁵ include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole ring. , pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole Triazole ring, pyrazine ring, benzimidazole ring, phenanthroline ring, indole ring, quinoxalinering, benzothiazole benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring. Specifically, Y ⁵ preferably each independently represents a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a triazolyl group, a pyrazinyl group, or a benzimidazolyl group. More preferably, Y ⁵ each independently represents a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group or a pyrimidinyl group.

In addition, Y ⁴ is preferably a substituent not adjacent to formula (III-A), formula (III-B), and formula (III-C) contained in Y ⁵ .

In formula (III), k represents an integer of 1 to 4. Moreover, k is preferably an integer representing 1 to 3 from the viewpoint of reactivity with the tetracarboxylic dianhydride compound. In addition, when k represents an integer of 2 to 4, each of the plurality of Y ² , Y ³ , Y ⁴ , and Y ⁵ in the plurality of "-Y ² -Y ³ -Y ⁴ -Y ⁵ " may represent the same or different groups.

-CH₂O-或

Y³为亚甲基、碳数为2至10的直 链或分支的亚烷基、碳数为2至10的直链或分支的亚烯基、二价脂环族烃基或二价芳香族 烃基，其中二价脂环族烃基中的脂环为环丙烷环、环丁烷环、环戊烷环、环己烷环、环庚 烷环、降冰片烯环或金刚烷环，二价芳香族烃基中的芳香环为苯环、萘环、四氢萘环、芴 环或蒽环；Y⁴为单键、-O-、-NH-、

(m为1至5的整数)；Y⁵中的含氮的芳香族杂环为吡咯环、 咪唑环、恶唑环、噻唑环、吡唑环、吡啶环、嘧啶环、喹啉环、吡唑啉环、异喹啉环、咔 唑环、嘌呤环、噻二唑环、哒嗪环、吡唑啉环、三嗪环、吡唑啉烷环、三唑环、吡嗪环、 苯并咪唑环、二氮菲环、吲哚环、喹恶啉环、苯并噻唑环、酚噻嗪环、恶二唑环或吖啶环； 并且k为1或2。In formula (III), the preferred combination of Y ² , Y ³ , Y ⁴ , Y ⁵ and k is: Y ² is -O-, -NH-,

-CH ₂ O- or

Y ³ is a methylene group, a straight-chain or branched alkylene group having a carbon number of 2 to 10, a straight-chain or branched alkenylene group having a carbon number of 2 to 10, a divalent alicyclic hydrocarbon group or a divalent aromatic group Hydrocarbon group, wherein the alicyclic ring in the divalent alicyclic hydrocarbon group is a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring, divalent aromatic The aromatic ring in the hydrocarbon group is a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring; Y ⁴ is a single bond, -O-, -NH-,

(m is an integer of 1 to 5); the nitrogen-containing aromatic heterocyclic ring in Y ⁵ is a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyridine ring oxazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolinane ring, triazole ring, pyrazine ring, benzo an imidazole ring, a phenanthrene ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, or an acridine ring; and k is 1 or 2.

-CH₂O-或

Y³为亚甲基、碳数为2至10的直链或分支的亚 烷基、碳数为2至10的直链或分支的亚烯基、二价脂环族烃基或二价芳香族烃基，其中二 价脂环族烃基中的脂环为环己烷环、降冰片烯环或金刚烷环，二价芳香族烃基中的芳香环 为苯环、萘环、芴环或蒽环；Y⁴为单键、-O-、-NH-、

(m为1至5的整数)；Y⁵为吡咯基、咪唑基、 吡唑基、吡啶基、嘧啶基、吡唑啉基、咔唑基、哒嗪基、吡唑啉基、三嗪基、吡唑啉烷基、 三唑基、吡嗪基或苯并咪唑基；并且k为1或2。In formula (III), a more preferable combination of Y ² , Y ³ , Y ⁴ , Y ⁵ and k is: Y ² is -O-, -NH-,

-CH ₂ O- or

Y ³ is a methylene group, a straight-chain or branched alkylene group having a carbon number of 2 to 10, a straight-chain or branched alkenylene group having a carbon number of 2 to 10, a divalent alicyclic hydrocarbon group or a divalent aromatic group Hydrocarbon group, wherein the alicyclic ring in the divalent alicyclic hydrocarbon group is a cyclohexane ring, a norbornene ring or an adamantane ring, and the aromatic ring in the divalent aromatic hydrocarbon group is a benzene ring, a naphthalene ring, a fluorene ring or an anthracene ring; Y ⁴ is a single bond, -O-, -NH-,

(m is an integer from 1 to 5); Y ⁵ is pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazolinyl, carbazolyl, pyridazinyl, pyrazolinyl, triazinyl , pyrazolinyl, triazolyl, pyrazinyl, or benzimidazolyl; and k is 1 or 2.

或-CH₂O-；Y³为亚甲基、碳数为2至5的直链或分支 的亚烷基或亚苯基；Y⁴为单键、-O-、

(m为1至5的整数)；Y⁵为吡咯基、咪唑基、吡唑基、吡啶基或嘧啶 基；并且k为1、2或3。In formula (III), a more preferable combination of Y ² , Y ³ , Y ⁴ , Y ⁵ and k is: Y ² is -O-, -NH-,

or -CH ₂ O-; Y ³ is a methylene group, a straight-chain or branched alkylene group with a carbon number of 2 to 5 or a phenylene group; Y ⁴ is a single bond, -O-,

(m is an integer from 1 to 5); Y ⁵ is pyrrolyl, imidazolyl, pyrazolyl, pyridyl or pyrimidinyl; and k is 1, 2 or 3.

Specific examples of the diamine compound (b1-3) include diamine compounds of combinations of Y ² , Y ³ , Y ⁴ , Y ⁵ and k described in Tables I to VIII.

Table I

Table II

Table III

Table IV

Table V

Table VI

Table VII

Table VIII

The method for producing the diamine compound (b1-3) of the present invention is not particularly limited. For example, it can be produced by the following method. and the reduction of the nitro group to the amino group in the presence of a hydride.

In formula (III-D), Y ² , Y ³ , Y ⁴ , Y ⁵ and k are respectively synonymous with Y ² , Y ³ , Y ⁴ , Y ⁵ and k in formula (III), and will not be repeated here. .

Specific examples of the catalyst are not particularly limited but may include palladium-carbon, platinum dioxide, Raneynickel, platinum black, rhodium-alumina, platinum sulfide carbon, or a combination of the above catalysts. Specific examples of the solvent are not particularly limited but may include ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohols, or a combination of the above solvents. Specific examples of the hydride are not particularly limited but may include hydrogen, hydrazine, hydrogen chloride, or a combination of the above compounds.

The dinitro compound represented by the formula (III-D) is synthesized by a method in which Y ³ is bonded to Y ⁵ via Y ⁴ ; then Y ³ is bonded to a benzene ring containing a dinitro group via Y ² ; or It is synthesized by a method in which a dinitro group-containing benzene ring is bonded to Y ³ via Y ² , and then Y ³ is bonded to Y ⁵ via Y ⁴ .

-CH₂O-、

等结合基，这些结合基可通过现有的有机合成方法来形成。Y ² is -O-, -NH-,

-CH ₂ O-,

and other binding groups, which can be formed by existing organic synthesis methods.

For example, in the case where Y ² is -O- or -CH ₂ O-, the dinitro compound represented by formula (III-D) can be obtained by combining a halogen derivative containing a dinitro group with a compound containing Y ³ , The hydroxy derivatives of Y ⁴ and Y ⁵ are obtained by reacting in the presence of a base; or by reacting a hydroxy derivative containing a dinitro group with a halogen-substituted derivative containing Y ³ , Y ⁴ and Y ⁵ in the presence of a base And get.

In the case where Y ² is -NH-, the dinitro compound represented by the formula (III-D) can be obtained by substituting a halogen derivative containing a dinitro group with an amino-substituted derivative containing Y ³ , Y ⁴ and Y ⁵ It is obtained by reacting in the presence of a base.

的情况下，由式(III-D)表示的二硝基化合物可通过使含有二硝基的 羟基衍生物与含有Y³、Y⁴及Y⁵的酰氯(acid chloride)化合物于碱存在下进行反应而得。at Y ² for

In the case of , the dinitro compound represented by the formula (III-D) can be carried out by making a hydroxy derivative containing a dinitro group and an acid chloride compound containing Y ³ , Y ⁴ and Y ⁵ in the presence of a base response.

的情况下，由式(III-D)表示的二硝基化合物可通过使含有二硝基的 酰氯化合物与含有Y³、Y⁴及Y⁵的经氨基取代的化合物于碱存在下进行反应而得。at Y ² for

In this case, the dinitro compound represented by the formula (III-D) can be obtained by reacting a dinitro-containing acid chloride compound with an amino-substituted compound containing Y ³ , Y ⁴ and Y ⁵ in the presence of a base. have to.

的情况下，由式(III-D)表示的二硝基化合物可通过使经氨基取代的 化合物与含有Y³、Y⁴及Y⁵的含有二硝基的酰氯化合物于碱存在下进行反应而得。at Y ² for

In this case, the dinitro compound represented by the formula (III-D) can be obtained by reacting an amino-substituted compound with a dinitro-containing acid chloride compound containing Y ³ , Y ⁴ and Y ⁵ in the presence of a base. have to.

Specific examples of dinitro-containing halogen derivatives and dinitro-containing derivatives include 3,5-dinitrochlorobenzene (3,5-dinitrochlorobenzene), 2,4-dinitrochlorobenzene (2,4-dinitrochlorobenzene) -dinitrochlorobenzene), 2,4-dinitro fluorobenzene, 3,5-dinitro benzoylchloride, 3,5-dinitrobenzoic acid (3,5-dinitrobenzoic acid), 2,4-dinitrobenzoyl chloride, 2,4-dinitrobenzoic acid, 3,5- Dinitrobenzyl chloride (3,5-dinitro benzyl chloride), 2,4-dinitrobenzyl chloride (2,4-dinitrobenzylchloride), 3,5-dinitrobenzyl alcohol (3,5-dinitrobenzyl alcohol) ), 2,4-dinitrobenzyl alcohol (2,4-dinitrobenzyl alcohol), 2,4-dinitroaniline (2,4-dinitroaniline), 3,5-dinitroaniline (3,5-dinitroaniline) ), 2,6-dinitroaniline (2,6-dinitroaniline), 2,4-dinitrophenol (2,4-dinitrophenol), 2,5-dinitrophenol (2,5-dinitrophenol), 2,6-dinitrophenol or 2,4-dinitrophenylacetic acid. The dinitro group-containing halogen derivatives and the dinitro group-containing derivatives may be used alone or in combination of two or more from the viewpoints of availability of raw materials and reactivity.

Specific examples of the diamine compound (b1-3) preferably include at least one of the diamine compounds represented by formula (III-1) to formula (III-6).

When the diamine compound (b1) in the polymer (A-1) in the liquid crystal alignment agent includes the diamine compound (b1-3), the liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent can have better performance environmental resistance.

The diamine compound (b1-3) represented by formula (III) may be used in an amount of 1 to 20 parts by mole, preferably 3 to 3 parts by mole, based on 100 parts by mole of the diamine compound (b1) used. 18 mole parts, more preferably 5 mole parts to 15 mole parts.

Other diamine compounds (b1-4)

Specific examples of other diamine compounds (b1-4) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,5-diaminopentane, 6-Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 4,4'-diamino Heptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethyl Heptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 2, 11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, 4,4'-diaminodicyclohexylmethane, 4,4'-Diamino-3,3'-dimethyldicyclohexylamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane (1,4-diaminocyclohexane), isophoronediamine , tetrahydrodicyclopentadiene diamine, tricyclo[6.2.1.0 ^2,7 ]-undecenedimethyldiamine, 4,4'-methylenebis(cyclohexylamine)(4,4 '-methylenebis(cyclohexylamine)), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfone, 4,4'- Diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1-(4'-amino Phenyl)-1,3,3-trimethylhydroindene, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroindene, hexahydro-4,7- Tolylidene indenyl dimethylenediamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 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[4-(4-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis (4-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 9,10-bis(4 -Aminophenyl)anthracene (9,10-bis(4-aminophenyl)anthracene), 2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylene -Bis(2-chloroaniline), 4,4'-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene) bisaniline, 2,2 '-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-bis[(4-amino-2-trifluoromethyl) ) phenoxy]-octafluorobiphenyl, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene (5-[4-(4 -n-pentylcyclohexyl)cyclohexyl]phenyl methylene-1,3-diaminobenzene), 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane (1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane) or other diamines such as diamine compounds represented by formulas (2-1) to (2-25) Compound (b1-4). However, the present invention is not limited thereto, and other diamine compounds (b1-4) may further include other suitable diamine compounds.

Other diamine compounds represented by formula (2-1) to formula (2-25) are shown below.

B²表示含甾基团、三氟甲基、氟基、碳数为2至30的烷基或衍生自吡啶、嘧啶、 三嗪、哌啶及哌嗪等含氮原子环状结构的一价基团。In formula (2-1), B ¹ represents -O-,

B ² represents a steroid group, a trifluoromethyl group, a fluoro group, an alkyl group with a carbon number of 2 to 30, or a monovalent cyclic structure derived from a nitrogen atom-containing ring structure such as pyridine, pyrimidine, triazine, piperidine and piperazine group.

Specific examples of other diamine compounds represented by formula (2-1) include 2,4-diaminophenyl ethyl formate, 3,5-diaminophenyl ethyl formate ( 3,5-diaminophenyl ethylformate), 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate, 1-Dodecoxy-2,4-diaminobenzene (1-dodecoxy-2,4-diaminobenzene), 1-hexadecoxy-2,4-diaminobenzene (1-hexadecoxy-2,4 -diaminobenzene), 1-octadecoxy-2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene), or represented by formula (2-1-1) to formula (2-1-4) of other diamine compounds.

B⁴及B⁵表示亚脂肪族环、亚芳香族环或亚杂环基团；B⁶表示碳数为3至18的烷 基、碳数为3至18的烷氧基、碳数为1至5的氟烷基、碳数为1至5的氟烷氧基、氰基或 卤素原子。In formula (2-2), B ³ represents -O-,

B ⁴ and B ⁵ represent an aliphatic, aromatic, or heterocyclic group; B ⁶ represents an alkyl group having 3 to 18 carbon atoms, an alkoxy group having 3 to 18 carbon atoms, and a carbon number of 1 A fluoroalkyl group to 5, a fluoroalkoxy group having a carbon number of 1 to 5, a cyano group or a halogen atom.

Specific examples of other diamine compounds represented by formula (2-2) include diamine compounds represented by formula (2-2-1) to formula (2-2-13).

In formula (2-2-10) to formula (2-2-13), q represents an integer of 3 to 12.

In formula (2-3), B ⁷ represents hydrogen, an acyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen; s represents 1 to 3 the integer. When s represents an integer of 2 or 3, a plurality of B ⁷ may be the same or different.

Specific examples of the diamine compound represented by formula (2-3) include (1) when s is 1: p-diaminobenzene, m-diaminobenzene, o-diaminobenzene, or 2,5-diaminetoluene etc.; (2) When s is 2: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'-dimethyl-4,4 '-diamino diphenyl), 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'- Dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2',5,5'-tetrachloro-4,4'-diphenyl Aminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis(trifluoromethyl) (3) When s is 3: 1,4-bis(4'-aminophenyl)benzene or a combination thereof. Specific examples of the diamine compound represented by the formula (2-3) preferably include p-diaminobenzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, or a combination thereof.

In formula (2-4), t represents an integer of 2 to 12.

In formula (2-5), v represents an integer of 1 to 5.

Specific examples of the diamine compound represented by formula (2-5) include 4,4'-diaminodiphenyl sulfide.

In formula (2-6), B ⁸ and B ¹⁰ each independently represent a divalent organic group, and B ⁹ represents a divalent group derived from a nitrogen atom-containing cyclic structure such as pyridine, pyrimidine, triazine, piperidine, and piperazine group.

In formula (2-7), B ¹¹ , B ¹² , B ¹³ and B ¹⁴ each independently represent a hydrocarbon group having 1 to 12 carbon atoms; w represents an integer of 1 to 3; and z represents an integer of 1 to 20.

Formula (2-8)

In formula (2-8), B ¹⁵ represents -O- or cyclohexylene; B ¹⁶ represents methylene; B ¹⁷ represents phenylene or cyclohexylene; B ¹⁸ represents hydrogen or heptyl.

Specific examples of the diamine compound represented by formula (2-8) include diamine compounds represented by formula (2-8-1) to formula (2-8-2).

Other diamine compounds represented by formula (2-9) to formula (2-25) are shown below.

In formula (2-17) to formula (2-25), B ¹⁹ represents an alkyl group having a carbon number of 1 to 10 or an alkoxy group having a carbon number of 1 to 10; B ²⁰ represents hydrogen and a carbon number of 1 to 10 or an alkoxy group with a carbon number of 1 to 10.

Specific examples of other diamine compounds (b1-4) may also include 3,3'-diaminochalcone, 4,4'-diaminochalcone (4,4'- diaminochalcone), 3,4'-diaminochalcone (3,4'-diaminochalcone) or 3,4-diaminochalcone (3,4-diaminochalcone) and other diamines with chalcone structure Compounds; 3,3'-diaminostilbene, 4,4'-diaminostilbene, 4,4'-diaminostilbene 4,4'-diaminostilbene-2,2'-sulfonic acid or 4,4'-bis(4-amino-1-naphthylazo)-2,2 '-Stilbene sulfonic acid (4,4'-bis(4-amino-1-naphthylazo)-2,2'-stilbene sulfonic acid) and other diamine compounds with stilbene structure; 1 , 1,2-diaminoanthraquinone, 1,4-diamino anthraquinone, 1,5-diamino anthraquinone, or 1 ,4-diaminoanthraquinone-2,3-dicyano-9,10-anthraquinone (1,4-diaminoanthraquinone-2,3-dicyano-9,10-anthraquinone) etc. with anthraquinone structure A diamine compound; or a diamine compound having a carbazole structure such as 3,6-diaminocarbazole.

Specific examples of other diamine compounds (b1-4) preferably include 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane ,4'-Diaminodiphenyl ether, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene, 1,1-bis[4 -(4-Aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane, ethyl 2,4-diaminophenylcarboxylate, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 4,4'-methylenebis(cyclohexylamine), 1,4-diaminocyclohexane, diamine compound represented by formula (2-1-1), formula The diamine compound represented by (2-1-2), the diamine compound represented by the formula (2-2-1), the diamine compound represented by the formula (2-2-11), p-diaminobenzene, m -Diaminobenzene, o-diaminobenzene, a diamine compound represented by formula (2-8-1), 3,3'-diaminochalcone or 4,4'-diaminostilbene, and the like.

Specific examples of other diamine compounds (b1-4) more preferably include p-diaminobenzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebis (cyclohexylamine), 1,4-diaminocyclohexane, 3,3'-diaminochalcone, or a combination thereof.

Based on 100 mole parts of the diamine compound (b1), the other diamine compounds (b1-4) may be used in an amount of 0 to 70 mole parts, preferably 0 to 60 mole parts, more preferably 0 to 50 mole parts.

Process for producing polymer (A-1)

Method for preparing polyamic acid polymer

The method for preparing a polyamic acid polymer is to first dissolve the first mixture in a solvent, wherein the first mixture includes a tetracarboxylic dianhydride compound (a1) and a diamine compound (b1), and dissolve the mixture at a temperature of 0°C to 100°C. The polycondensation reaction was carried out under the following conditions. After reacting for 1 to 24 hours, the above-mentioned reaction solution is distilled under reduced pressure with an evaporator to obtain a polyamic acid polymer. Alternatively, the above-mentioned reaction solution is poured into a large amount of poor solvent to obtain a precipitate. Next, the precipitate is dried under reduced pressure to obtain a polyamic acid polymer. The diamine compound (b1) may be used in an amount of 20 to 200 parts by mole, preferably 30 to 120 parts by mole, based on 100 parts by mole of the tetracarboxylic dianhydride compound (a1).

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the following liquid crystal aligning agent, and the solvent used in the polycondensation reaction is not particularly limited, as long as it can dissolve the reactant and the product. Specific examples of the solvent include (1) aprotic polar solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide, N,N - aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea or hexamethyl phosphate triamine; (2) phenolic solvents, such as m-methyl phosphate Phenol-based solvents such as phenol, xylenol, phenol, or halogenated phenols; or a combination of the above solvents. However, the present invention is not limited thereto, and the solvent may also include other suitable solvents. The solvent used in the polycondensation reaction may be used in an amount of 200 to 2000 parts by weight, preferably 300 to 1800 parts by weight, based on 100 parts by weight of the first mixture.

In the polycondensation reaction, the solvent can be used in combination with an appropriate amount of poor solvent, wherein the poor solvent will not cause the precipitation of polyamic acid polymer. Specific examples of the poor solvent include (1) alcohols such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, or triethylene glycol; (2) ) ketones, such as: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; (3) esters, such as: methyl acetate, ethyl acetate, butyl acetate, oxalic acid Esters such as ethyl ester, diethyl malonate or ethylene glycol ethyl ether acetate; (4) ethers, such as: diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol Ethers such as glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether; (5) Halogenated hydrocarbons, such as: Halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichlorobenzene; (6) Hydrocarbons, such as tetrahydrofuran, Hydrocarbons such as hexane, heptane, octane, benzene, toluene or xylene, or a combination of the above poor solvents. However, the present invention is not limited thereto, and the lean solvent may further include other suitable solvents. The use amount of the lean solvent may be 0 to 60 parts by weight, preferably 0 to 50 parts by weight, based on 100 parts by weight of the total used amount of the first mixture.

Polyimide polymer

The method for preparing a polyimide polymer is to first dissolve a first mixture in a solvent, wherein the first mixture includes a tetracarboxylic dianhydride compound (a1) and a diamine compound (b1), and perform a polycondensation reaction to form Polyamic acid polymer. Next, in the presence of a dehydrating agent and a catalyst, further heating is performed, and a dehydration ring closure reaction is performed, so that the amic acid functional group in the polyamic acid polymer is converted into an imide functional group (ie, imidization) through the dehydration ring closure reaction. , to obtain a polyimide polymer.

The solvent used in the polycondensation reaction and the dehydration ring-closure reaction can be the same as the solvent in the following liquid crystal alignment agent, so it will not be repeated here. The amount of the solvent used in the dehydration ring-closure reaction can be 200 to 2000 parts by weight, preferably 300 to 1800 parts by weight, based on 100 parts by weight of the polyamic acid polymer.

In order to obtain a better degree of imidization of the polyamic acid polymer, the operating temperature of the dehydration ring-closure reaction is preferably 40°C to 200°C, more preferably 40°C to 150°C. If the operating temperature of the dehydration ring-closure reaction is lower than 40°C, the imidization reaction is incomplete, and the degree of imidization of the polyamic acid polymer is reduced. However, if the operating temperature of the dehydration ring-closure reaction is higher than 200°C, the weight-average molecular weight of the obtained polyimide polymer is relatively low.

The range of the imidization rate of the polymer (A-1) is usually 30% or less, preferably 20% or less, and more preferably 10% or less.

The dehydrating agent used in the dehydration ring-closure reaction can be selected from acid anhydride compounds, wherein specific examples of the acid anhydride compounds include acetic anhydride, propionic anhydride, trifluoroacetic anhydride or a combination thereof. The dehydrating agent may be used in an amount of 0.01 to 20 parts by mole based on 1 part by mole of the polyamic acid polymer. Specific examples of catalysts used in the dehydration ring-closure reaction include (1) pyridine-based compounds, such as pyridine-based compounds such as pyridine, collidine, or lutidine; (2) tertiary amine-based compounds, such as: triethyl tertiary amine compounds such as base amine; or a combination of the above compounds. The catalyst may be used in an amount of 0.5 to 10 parts by mole based on 1 part by mole of the dehydrating agent.

Polyimide based block copolymer

Polyimide-based block copolymers include polyamic acid block copolymers, polyimide block copolymers, polyamic acid-polyimide block copolymers, or a combination of the above copolymers .

The method for preparing the polyimide-based block copolymer is preferably to first dissolve the starting material in a solvent and carry out a polycondensation reaction, wherein the starting material includes the above-mentioned at least one polyamic acid polymer and/or The above-mentioned at least one polyimide polymer may further include a tetracarboxylic dianhydride compound (a1) and a diamine compound (b1).

The starting material includes the tetracarboxylic dianhydride compound (a1) and the diamine compound (b1) used in the above-mentioned preparation of the polyamic acid polymer, and the solvent used in the polycondensation reaction can be used with the following liquid crystal aligning agent. The solvent is the same and will not be repeated here.

The solvent used in the polycondensation reaction may be used in an amount of 200 to 2000 parts by weight, preferably 300 to 1800 parts by weight, based on 100 parts by weight of the starting material. The operating temperature of the polycondensation reaction is preferably 0°C to 200°C, more preferably 0°C to 100°C.

Specific examples of the starting materials include (1) two kinds of polyamic acid polymers with different end groups and different structures; (2) two kinds of polyimide polymers with different end groups and different structures; (3) ) Polyamic acid polymers and polyimide polymers with different terminal groups and different structures; (4) Polyamic acid polymers, tetracarboxylic dianhydride compounds and diamine compounds, among which tetracarboxylic dianhydride compounds and at least one of the diamine compounds are different in structure from the tetracarboxylic dianhydride compound and the diamine compound used to form the polyamic acid polymer; (5) polyimide polymer, tetracarboxylic dianhydride A compound and a diamine compound, wherein at least one of the tetracarboxylic dianhydride compound and the diamine compound has a different structure from the tetracarboxylic dianhydride compound and the diamine compound used to form the polyimide polymer; (6 ) polyamic acid polymer, polyimide polymer, tetracarboxylic dianhydride compound and diamine compound, wherein at least one of the tetracarboxylic dianhydride compound and the diamine compound forms a polyamic acid polymer or polyamide The tetracarboxylic dianhydride compounds and diamine compounds used in the imide polymer have different structures; (7) two kinds of polyamic acid polymers, tetracarboxylic dianhydride compounds and diamine compounds with different structures; ( 8) Two kinds of polyimide polymers, tetracarboxylic dianhydride compounds and diamine compounds with different structures; (9) Two kinds of polyamic acid polymers and diamine compounds with different end groups as acid anhydride groups and different structures (10) Two kinds of polyamic acid polymers and tetracarboxylic dianhydride compounds whose end groups are amino groups and different structures; (11) Two kinds of polyimide polymers whose end groups are acid anhydride groups and different structures and A diamine compound; or (12) two types of polyimide polymers having amino groups at their end groups and different structures, and a tetracarboxylic dianhydride compound.

The polyamic acid polymer, the polyimide polymer, and the polyimide-based block copolymer may preferably be terminal-modified polymers whose molecular weight is first adjusted within the scope of not affecting the efficacy of the present invention. By using terminal-modified polymers, the coating properties of the liquid crystal aligning agent can be improved. The method for preparing the terminal-modified polymer can be prepared by adding a monofunctional compound at the same time as the polycondensation reaction of the polyamic acid polymer. Specific examples of the monofunctional compound include (1) monobasic acid anhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride Monobasic acid anhydrides such as acid anhydride or n-hexadecyl succinic anhydride; (2) Monoamine compounds, such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine , n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine Monoamine compounds such as alkylamine or n-eicosylamine; (3) monoisocyanate compounds, for example: monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate; or a combination of the above-mentioned monofunctional compounds. However, the present invention is not limited thereto, and the monofunctional compound may further include other suitable monofunctional compounds.

In the liquid crystal aligning agent, based on the total usage amount of the polymer (A-1) and the polymer (A-2) described later being 100 parts by weight, the usage amount of the polymer (A-1) may be 30 parts by weight to 95 parts by weight The weight part is preferably 40 to 90 parts by weight, more preferably 50 to 90 parts by weight. When the amount of the polymer (A-1) in the liquid crystal alignment agent falls within the above range, the liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent can have a better electric field memory effect.

Polymer (A-2)

The liquid crystal aligning agent may further include a polymer (A-2) other than the polymer (A-1). The polymer (A-2) is obtained by reacting the second mixture containing the tetracarboxylic dianhydride compound (a2) and the diamine compound (b2).

The tetracarboxylic dianhydride compound (a2) is not particularly limited, and may be the same or different compound as the tetracarboxylic dianhydride compound (a1) in the above-mentioned polymer (A-1).

The diamine compound (b2) is not particularly limited, and may be the same as the diamine compound (b1-2), the diamine compound (b1-3) or the diamine compound (b1-4) in the above-mentioned polymer (A-1). the same or different compounds.

The method for preparing the polymer (A-2) is not particularly limited, for example, it can be the same as the method for preparing the polymer (A-1), so it will not be repeated here.

In the liquid crystal alignment agent, based on the total usage amount of polymer (A-1) and polymer (A-2) being 100 parts by weight, the usage amount of polymer (A-1) may be 5 parts by weight to 70 parts by weight , preferably 10 to 60 parts by weight, more preferably 10 to 50 parts by weight.

Solvent (B)

Specific examples of the solvent (B) include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether , butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether Propyl ether, Ethylene glycol n-butyl ether, Ethylene glycol dimethyl ether, Ethylene glycol ethyl ether acetate, Diethylene glycol dimethyl ether, Diethylene glycol diethyl ether base ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, ethylene glycol n-butyl ether diethylene glycol monoethyl ether acetate, N,N - Dimethylformamide, N,N-dimethylacetamide, or any combination of the above solvents. The solvent (B) is preferably N-methyl-2-pyrrolidone, ethylene glycol n-butyl ether, N,N-dimethylacetamide, or a combination of the above solvents. However, the present invention is not limited thereto, and the solvent (B) may further include other suitable solvents. The solvent (B) may be used alone or in combination.

When the liquid crystal alignment agent includes the polymer (A-1) and the solvent (B), based on the polymer (A-1) used in an amount of 100 parts by weight, the solvent (B) can be used in an amount of 1000 to 3500 parts by weight parts, preferably 1000 to 3200 parts by weight, more preferably 1000 to 3000 parts by weight.

When the liquid crystal alignment agent includes the polymer (A-1), the polymer (A-2) and the solvent (B), the total usage amount based on the polymer (A-1) and the polymer (A-2) is 100 weight The solvent (B) can be used in an amount of 1000 to 3500 parts by weight, preferably 1000 to 3200 parts by weight, more preferably 1000 to 3000 parts by weight.

Additives (C)

Within the scope of not affecting the efficacy of the present invention, the liquid crystal alignment agent can also optionally add additives (C). The additive (C) may be an epoxy compound, a silane compound having a functional group, or a combination thereof. The role of the additive (C) is to improve the adhesion of the liquid crystal alignment film to the surface of the substrate. The additive (C) may be used alone or in combination of two or more.

Specific examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diepoxy propyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether glycidyl 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'-diaminodiphenyl Methane, N,N-diglycidyl-p-glycidoxyaniline, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane or 3-(N, N-diglycidyl)aminopropyltrimethoxysilane or a combination thereof. However, the present invention is not limited thereto, and the epoxy compound may further include other suitable epoxy compounds.

The use amount of the epoxy compound is generally 40 parts by weight or less, preferably 0.1 parts by weight to 30 parts by weight, based on 100 parts by weight of the polymer (A-1).

Specific examples of the silane compound having a functional group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethyl Oxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-urea 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3 -Aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 ,7-triazadecane, 10-triethoxysilyl-1,4,7-triazdecane, 9-trimethoxysilyl-3,6-diaznonyl acetate, 9-triazide Ethoxysilyl-3,6-diaznonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(ethylene oxide)-3-aminopropyltrimethoxysilane, N- -Bis(ethylene oxide)-3-aminopropyltriethoxysilane or a combination thereof. However, the present invention is not limited thereto, and the silane compound having a functional group may further include other suitable silane compounds having a functional group.

The used amount of the silane compound is generally 10 parts by weight or less, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer (A-1).

<Preparation method of liquid crystal alignment agent>

The preparation method of the liquid crystal alignment agent of the present invention is not particularly limited, and it can be prepared by a general mixing method. For example: the polymer (A-1) or the mixture of the polymer (A-1) and the polymer (A-2) is added to the solvent (B) at a temperature of 0°C to 200°C, and optionally Add the additive (C); then continue stirring with a stirring device until dissolved. The temperature at which the polymer is added to the solvent (B) is preferably 20°C to 60°C.

At 25° C., the viscosity of the liquid crystal alignment agent of the present invention is usually 15cps to 35cps, preferably 17cps to 33cps, more preferably 20cps to 30cps.

<Preparation method of liquid crystal alignment film>

The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film by a photo-alignment method.

The method of forming a liquid crystal alignment film is, for example, applying a liquid crystal alignment agent to a substrate to form a coating film, and irradiating the coating film with polarized or unpolarized ultraviolet rays from a direction inclined relative to the surface of the coating film; or A method of imparting liquid crystal alignment energy to the coating film by irradiating the coating film with polarized ultraviolet rays in a direction perpendicular to the film surface.

First, the liquid crystal aligning agent of the present invention is coated on the substrate provided with the patterned transparent conductive film by an appropriate coating method such as roll coating, spin coating, printing, or ink-jet. Transparent conductive film side. After coating, the coated surface is subjected to a pre-bake treatment, followed by a post-bake treatment, thereby forming a coating film. The purpose of the above-mentioned pre-baking treatment is to volatilize the organic solvent in the pre-coating layer. The conditions for the prebaking treatment are, for example, 0.1 to 5 minutes at a temperature of 40°C to 120°C. The temperature of the post-baking treatment may be 120°C to 300°C, preferably 150°C to 250°C. The post-baking treatment time may be 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 µm to 1 µm, more preferably 0.005 µm to 0.5 µm.

The substrate can be made of glass such as float glass, soda lime glass, etc.; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate. formed transparent substrates, etc.

As the transparent conductive film, a NESA (NESA) film formed of SnO ₂ , an indium tin oxide (ITO) film formed of In ₂ O ₃ -SnO ₂ , or the like can be used. In order to form these transparent conductive film patterns, a photo-etching technique, a method of using a mask when forming the transparent conductive film, or the like can be used.

When coating the liquid crystal aligning agent, in order to improve the adhesion between the substrate or the transparent conductive film and the coating film, functional silane compounds, titanate compounds, etc. may be pre-coated on the substrate and the transparent conductive film.

Next, a liquid crystal alignment film is formed from the coating film by irradiating the coating film with polarized or unpolarized ultraviolet rays to impart alignment capability to the liquid crystal. Here, as the radiation, for example, ultraviolet rays and visible light including light having a wavelength of 150 to 800 nm, and preferably ultraviolet rays including light having a wavelength of 300 to 400 nm can be used. When the radiation used is polarized light (linearly polarized light or partially polarized light), it may be irradiated from a direction perpendicular to the coating film surface, or may be irradiated from an oblique direction in order to impart a pretilt angle. On the other hand, when irradiating non-polarized radiation, it is necessary to irradiate from a direction inclined with respect to the surface of the coating film.

As a light source for irradiating radiation, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or an excimer laser can be used. The ultraviolet rays in the above-mentioned preferable wavelength region can be obtained by a method of using the above-mentioned light source in combination with, for example, a filter, a diffraction grating, or the like.

The irradiation dose of radiation is preferably 1 J/m ² or more and less than 10000 J/m ² , more preferably 10 J/m ² to 3000 J/m ² . In addition, in order to impart liquid crystal alignment ability to a coating film formed of a conventionally known liquid crystal aligning agent by a photo-alignment method, a radiation exposure amount of 10000 J/m ² or more is required. However, when the liquid crystal aligning agent of the present invention is used, even if the radiation exposure amount in the photo-alignment method is 3000 J/m ² or less, further 1000 J/m ² or less, and further 300 J/m ² or less, a good Liquid crystal alignment ability, thereby helping to reduce the manufacturing cost of liquid crystal display elements.

<Manufacturing method of liquid crystal display element>

The liquid crystal display element of the present invention includes a liquid crystal alignment film formed of the above-mentioned liquid crystal alignment agent. The liquid crystal display element of the present invention can be produced as follows.

Two substrates on which the liquid crystal alignment films were formed as described above were prepared, and liquid crystal was arranged between the two substrates to manufacture a liquid crystal cell. In order to manufacture a liquid crystal cell (cell), the following two methods are mentioned, for example.

The first method: first, arrange the two substrates with a gap (cell gap) facing each other, so that the respective liquid crystal alignment films face each other; use a sealant to attach the peripheral parts of the two substrates together; The liquid crystal is injected into the interstitial space divided by the sealant; and the injection hole is closed, so that the liquid crystal cell can be manufactured.

The second method: a method called the One Drop Fill (ODF) method. First, apply, for example, a UV-curable sealing material to a predetermined position on one of the two substrates forming the liquid crystal alignment film; drop liquid crystal on the surface of the liquid crystal alignment film; then, attach the other substrate to make the liquid crystal alignment film Opposite to each other; then, the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealant, whereby a liquid crystal cell can be produced.

In the case of using any of the above methods, it is desirable to subsequently heat the liquid crystal cell to a temperature at which the liquid crystal to be used exhibits an isotropic phase, and then slowly cool to room temperature, thereby removing the flow alignment when the liquid crystal is filled.

Then, the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to the outer surface of a liquid crystal cell. Here, when the liquid crystal alignment film is horizontally aligned, by adjusting the angle formed by the polarization directions of the linearly polarized radiation irradiated on the two substrates on which the liquid crystal alignment film is formed, and the angle between each substrate and the polarizing plate, a TN can be obtained. type or STN type liquid crystal display element. On the other hand, when the liquid crystal alignment film is vertically aligned, the liquid crystal cells are formed so that the directions of the easy-to-align axes of the two substrates on which the liquid crystal alignment film is formed are parallel, and the polarizing plate is aligned with the The liquid crystal cells are bonded together so that the polarization direction is at an angle of 45° with the alignment easy axis, and a liquid crystal display element having a vertical alignment type liquid crystal cell can be formed.

Specific examples of the sealant include an epoxy resin containing alumina balls as spacers or a curing agent, and the like.

Specific examples of liquid crystals include nematic liquid crystals, discotic liquid crystals, and the like.

In the case of TN-type or STN-type liquid crystal cells, specific examples of nematic liquid crystals with positive dielectric anisotropy preferably include biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals ( phenylcyclohexane-based liquid crystal), ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane-based liquid crystal, pyrimidine-based liquid crystals, dioxin Dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, etc. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonabenzoate, and cholesteryl carbonate may be further added to the aforementioned liquid crystals; Chiral agents sold under the trade names "C-15" and "CB-15" (manufactured by Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate (p- decyloxybenzylidene-p-amino-2-methyl butyl cinnamate) and other additives such as ferroelectric liquid crystal are used.

On the other hand, in the case of vertically aligned liquid crystal cells, specific examples of nematic liquid crystals with negative dielectric anisotropy preferably include dicyanobenzene-based liquid crystals, pyridazine liquid crystals (pyridazine-based liquid crystals), Schiff base-based liquid crystal, azoxy-based liquid crystals, biphenyl-based liquid crystals, phenylcyclohexane Phenyl cyclohexane-based liquidcrystals or combinations thereof.

The polarizing plate used on the outside of the liquid crystal cell includes a polarizing film called "H film" obtained by sandwiching a cellulose acetate protective film and absorbing iodine while aligning polyvinyl alcohol in Raya. The polarizing plate or the polarizing plate formed by the H film itself.

The thus-produced liquid crystal display element of the present invention is excellent in display performance and does not deteriorate in display performance even when used for a long time.

FIG. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention. The liquid crystal display element 100 includes a first cell 110, a second cell 120 and a liquid crystal cell 130, wherein the second cell 120 and the first cell 110 are arranged separately, and the liquid crystal cell 130 is disposed between the first cell 110 and the second cell 120.

The first unit 110 includes a first substrate 112 , a first conductive film 114 and a first liquid crystal alignment film 116 , wherein the first conductive film 114 is located between the first substrate 112 and the first liquid crystal alignment film 116 . In addition, the first liquid crystal alignment film 116 in the first cell 110 is located on the side of the first cell 110 close to the liquid crystal cell 130 .

The second unit 120 includes a second substrate 122, a second conductive film 124 and a second liquid crystal alignment film 126, wherein the second conductive film 124 is located between the second substrate 122 and the second liquid crystal alignment film 126. In addition, the second liquid crystal alignment film 126 in the second cell 120 is located on the side of the second liquid crystal alignment film 126 close to the liquid crystal cell 130 . In other words, the liquid crystal cell 130 is located between the first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 .

The first substrate 112 and the second substrate 122 are selected from materials such as transparent materials, wherein the transparent materials include alkali-free glass, soda lime glass, hard glass (Pyles glass), quartz glass, polystyrene for liquid crystal display devices. Ethylene terephthalate, polybutylene terephthalate, polyethersulfone or polycarbonate, etc. However, the present invention is not limited to this, and the materials of the first substrate 112 and the second substrate 122 can also be selected from other suitable materials.

The materials of the first conductive film 114 and the second conductive film 124 are selected from materials such as tin oxide (SnO ₂ ) or indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). However, the present invention is not limited to this, and the materials of the first conductive film 114 and the second conductive film 124 can also be selected from other suitable materials.

Each of the first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 is the above-mentioned liquid crystal alignment film, and its function is to make the liquid crystal cell 130 form a pretilt angle. In addition, when a voltage is applied to the first conductive film 114 and the second conductive film 124, an electric field may be generated between the first conductive film 114 and the second conductive film 124. The electric field can drive the liquid crystal cell 130 , thereby changing the arrangement of liquid crystal molecules in the liquid crystal cell 130 .

Preparation example of diamine compound (b1-1)

Preparation Examples 1 to 6 of the diamine compound (b1-1) will be described below.

Preparation Example 1

The compound represented by the formula (I-1) (hereinafter referred to as "diamine compound (b1-1-1)") was synthesized according to the following synthesis route 1.

[Synthetic route 1]

105 g of hydroquinone, 135 g of potassium carbonate (K ₂ CO ₃ ) and 700 ml of acetonitrile (ACN) were placed in a 3-liter four-necked flask, stirred and heated to 80°C. Then, a mixed solution of 100 g of 4,4,4-trifluorobutyl methanesulfonate (4,4,4-trifluorobutyl methanesulfonate) and 500 ml of acetonitrile was dropped into the four-necked flask. After dropping, the temperature was maintained at 80°C for 4 hours. Next, 190 g of a 25 wt % sodium hydroxide aqueous solution was added, and the mixture was refluxed at 80° C. for 30 minutes. Next, 415 ml of water were added and the temperature was maintained at 80°C for 1 hour. Filtration was performed after the reaction was completed, and the filtered filtrate was collected and drained, followed by separation by column chromatography to obtain about 65 g of R1OH solid.

Next, 120 g of R1OH solid, 95 g of 4-formylcinnamic acid, 12 g of 4-dimethylaminopyridine (DMAP) and 1080 ml of dichloromethane (CH ₂ Cl ₂ ) were placed in a volume of 2 liters in the four-necked flask and stirred. 125 g of 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide Hydrochloride (EDC.HCl) was added during stirring, and After the addition, the temperature was raised to 40°C, and the reaction was refluxed at 40°C for 6 hours. After the reaction, extracted twice with 540 ml of water, collected the organic layer, removed water with anhydrous magnesium sulfate, filtered and drained. The solid obtained after draining was heated and dissolved with 300 g of isopropanol, and allowed to stand for crystallization after cooling. The crystallization was collected by filtration and dried to obtain about 130 g of R3A solid.

Then, 64 grams of R3A solid and 560 milliliters of dimethylformamide (DMF) were placed in a three-necked flask with a capacity of 3 liters and stirred to dissolve, and then 150 grams of potassium hydrogen persulfate (Potassium peroxymonosulfate, Oxone) was added, and React at room temperature for 3 hours. After the reaction was completed, the solution was sucked dry, and the solid was washed three times with 1300 mL of water. After that, it was washed once with 1300 ml of methanol. The washed solids were collected and dried in vacuo to obtain about 55 grams of R3B solids.

Next, 67 grams of R3B solid, 60 grams of 2-(N,N-di-tert-butoxycarbonyl-2,4-diaminophenyl)-1-ethanol (2-(N,N-di-Boc-2 , 4-diaminophenyl)-1-ethanol, t-Boc DPE), 2 g of 4-dimethylaminopyridine and 340 ml of dichloromethane were placed in a four-necked flask with a capacity of 5 liters and stirred. 40 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) was added during stirring, and the temperature was raised to 40°C after the addition, and refluxed at 40°C The reaction was carried out for 6 hours. After the reaction was completed, the mixture was extracted twice with 2500 ml of water, the organic layer was collected, and the water was removed with anhydrous magnesium sulfate, followed by filtration and suction. The solid obtained after draining was heated and dissolved with 370 grams of isopropanol, and was allowed to stand for crystallization after cooling, and the crystallization was collected by filtration and drained to obtain about 100 grams of R4B solid.

Then, 100 g of R4B solid and 1400 ml of dichloromethane were placed in a four-necked flask with a capacity of 5 liters and stirred. During the stirring process, 135 g of tin(II) trifluoromethanesulfonate (Tin(II) trifluoromethanesulfonate, Sn(OTf) ₂ ) was added, and after the addition, the temperature was raised to 40° C. under nitrogen and the reaction was refluxed for 1.5 hours. After the reaction was completed, 1600 mL of ethyl acetate was poured into the flask and stirred. Next, 970 ml of 2.5M aqueous sodium hydroxide solution was poured into the flask and stirred for 30 minutes. Next, the solution was poured into a 2-liter separatory flask, left to stand and the upper organic layer was collected. Subsequently, it was extracted 4 times with 970 ml of 2.5M aqueous sodium hydroxide solution and 10 times with 970 ml of water. The extracted organic layer was dewatered with anhydrous magnesium sulfate, filtered and drained, washed with 200 g of methanol, filtered and drained to collect solids. The solid was then dissolved by heating with 300 g of acetonitrile, and allowed to crystallize after cooling. The crystals were collected by filtration and drained to obtain about 48 g of RPADA solid (ie, the diamine compound b1-represented by the formula (I-1). 1-1).

Preparation Example 2

The compound represented by the formula (I-2) (hereinafter referred to as "diamine compound (b1-1-2)") was synthesized according to the following synthesis route 2.

[Synthetic route 2]

Put 65 grams of 4-formylcinnamic acid, 100 grams of 4-(4-heptylcyclohexyl)phenol (4-(4-heptylcyclohexyl)phenol, 7CPO) and 4.5 grams of 4-dimethylaminopyridine into a volume of 2 liter four-necked flask. Then, 730 ml of dichloromethane was added into the four-necked flask, and 84 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) was added during the stirring process. Then, it was made to react at 40 degreeC for 6 hours. After the reaction was completed, water was added for extraction, the organic layer was collected, and the water was removed with anhydrous magnesium sulfate, followed by filtration and draining. The solid obtained after draining was heated and washed with isopropanol, after which the solid was filtered and collected to obtain about 130 g of R3CHO as a solid.

Next, 80 g of R3CHO solid and 620 ml of dimethylformamide were placed in a 1-liter three-necked flask and stirred. After the R3CHO solid was dissolved, 170 g of potassium hydrogen persulfate (Oxone) was added and reacted at room temperature for 3 hours. After the reaction was completed, the solvent was sucked dry to obtain a solid, and the solid was washed with pure water and methanol. After washing, vacuum drying was performed to obtain about 75 grams of R3COOH solid.

Then, 46.7 g of R3COOH solid and 250 ml of toluene were placed in a 0.5-liter three-necked flask and stirred to dissolve. Then, 0.09 g of dimethylformamide (DMF) was added, and the temperature was raised to 75°C. Subsequently, 13.6 g of thionyl chloride (SOCl ₂ ) was slowly added dropwise, and the temperature was raised to 80° C. after the drop was completed, and the reaction was carried out for 5 minutes. Next, the temperature was lowered to 40°C. 26.5 g of 2,4-dinitrophenyl-ethanol (2,4-dinitrophenyl-ethanol) and 0.6 g of 4-dimethylaminopyridine were dissolved in 12.4 g of pyridine (Pyridine) and dropped into the above three-necked flask. , continue stirring for 12 hours. Thereafter, the temperature was raised to 60°C, and 20 mL of methanol was added, followed by maintaining the temperature at 45°C for 1 hour. Finally, the solvent was drained and washed with methanol to obtain about 57 g of solid R3DiNO-L precipitated.

Next, 48.4 g of R3DiNO-L solid and 440 ml of anisole were placed in a four-necked flask with a capacity of 3 liters and stirred. In addition, prepare 186 ml of pure water and 7.7 g of Pt/C into a beaker with a capacity of 2 liters and stir, then add 0.13 g of ammonium metavanadate (NH ₄ VO ₃ ) and 0.7 g of hypophosphorous acid (H ₃ PO ₂ ) An aqueous solution (50 wt%) was prepared as a mixed solution. The above mixture was poured into a four-necked flask, and the temperature was raised to 65°C. Subsequently, 30 g of hydrazine (NH ₂ NH ₂ ) was added dropwise, and after all the dropwise addition, the temperature was raised to 80° C. and the reaction was performed for 4 hours. Subsequently, the solution was filtered, and the filtrate was extracted with ethyl acetate and water and then sucked dry to obtain a solid. Next, the solid was heated and washed with ethyl acetate, after which the solid was filtered and collected to obtain about 30 g of RPADA3 solid (ie, the diamine compound b1-1-2 represented by the formula (I-2)).

Preparation Example 3

The compound represented by the formula (I-3) (hereinafter referred to as "diamine compound (b1-1-3)") was synthesized according to the following synthesis route 3.

[Synthetic route 3]

Combine 140 g of Tetrahydropyranyloxy Phenol, 180 g of 4-(4,4,4-trifluorobutoxy)benzoic acid with 8.8 grams of 4-dimethylaminopyridine were placed in a four-necked flask with a capacity of 3 liters. Then, 1600 g of dichloromethane was added into the four-necked flask, and 150 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) was added during the stirring process. After the addition, the reaction was carried out at room temperature for 8 hours. After the reaction was completed, water was added for extraction, the organic layer was collected, and the water was removed with anhydrous magnesium sulfate, followed by filtration and suction. The solid obtained after draining was washed with isopropanol and heated. After washing, the solid was collected by filtration and vacuum dried to obtain about 270 grams of R5THP as a solid.

Next, 270 g of R5THP solid, 65 ml of methanol and 1200 ml of dichloromethane were placed in a four-necked flask with a capacity of 2 liters and stirred. During the stirring process, 170 g of a 12 wt% p-toluenesulfonic acid acetic acid solution was added dropwise. After the addition, the reaction was carried out at room temperature for 2 hours. After the reaction was completed, water was added for extraction, and after extraction, the solvent was drained to obtain about 210 g of R5OH solid.

Then, 70 grams of R5OH solid, 36 grams of 4-formylcinnamic acid and 2.5 grams of 4-dimethylaminopyridine were placed in a four-necked flask with a capacity of 1 liter, and 550 grams of dichloromethane was added and stirred. Subsequently, 47.3 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) was added dropwise during stirring. After the addition, the reaction was carried out at 40°C for 8 hours. After the reaction was completed, water was added for extraction, the organic layer was collected and removed with anhydrous magnesium sulfate, filtered and drained. The solid obtained after draining was washed with isopropanol and heated. After washing, the solid was collected by filtration and vacuum dried to obtain about 87 grams of R5BCHO as a solid.

Next, put 87 grams of R5BCHO solid and 583 milliliters of dimethylformamide into a 1-liter three-necked flask and stir to dissolve. 160 g of potassium hydrogen persulfate (Oxone) was added, and the reaction was carried out at room temperature for 3 hours. After the reaction was completed, the solution was sucked dry, and the solid was washed three times with 1600 mL of water. After that, it was washed once with 800 ml of methanol. The washed solids were collected and dried in vacuo to yield about 44 grams of R5BCOOH solids.

Then, 44 grams of R5BCOOH solid, 30 grams of 2-(N,N-di-tert-butoxycarbonyl-2,4-diaminophenyl)-1-ethanol (t-Boc DPE), 2 grams of 4-dimethyl Aminopyridine and 850 ml of dichloromethane were placed in a four-necked flask with a capacity of 1 liter and stirred. During stirring, 20 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) was added, and the reaction was carried out under reflux for 6 hours at room temperature. After the completion of the reaction, extract with 350 ml of water, collect the organic layer, remove water with anhydrous magnesium sulfate, filter and drain. The solid obtained after being sucked dry was dissolved by heating with isopropanol, and allowed to stand for crystallization after cooling, and the crystallization was collected by filtration and sucked dry to obtain about 70 grams of R5BBoc solid.

Next, 50 g of R5BBoc solid and 1200 ml of dichloromethane were placed in a four-necked flask with a capacity of 5 liters and stirred. 62 grams of tin(II) triflate (Sn(OTf) ₂ ) was added during stirring. After the addition, the temperature was raised to 40°C under nitrogen and the reaction was refluxed for 1.5 hours. After the reaction was completed, 2000 ml of ethyl acetate was poured into the flask and stirred. Next, 450 ml of 2.5M aqueous sodium hydroxide solution was poured into the flask, and stirred for 30 minutes. Next, the solution was poured into a 2-liter separatory flask, left to stand and the upper organic layer was collected. Subsequently, it was extracted 4 times with 450 ml of 2.5M aqueous sodium hydroxide solution and 4 times with 200 ml of water. The extracted organic layer was dewatered with anhydrous magnesium sulfate, filtered and drained, washed with methanol, filtered and drained to collect solids. The solid was then dissolved by heating with acetonitrile, and allowed to crystallize after cooling. The crystals were collected by filtration and drained to obtain about 28 g of RPADA5B solid (ie, the diamine compound b1-1- represented by the formula (I-3)) 3).

Preparation Example 4

The compound represented by the formula (I-6) (hereinafter referred to as "diamine compound (b1-1-4)") was synthesized according to the following synthesis route 4.

[Synthetic route 4]

Put 285 g of 4-hydroxycinnamic acid (4-hydroxycinnamic acid), 293 g of dihydropyran (3,4-Dihydro-2H-pyran, DHP) and 1800 ml of dichloromethane into a four-necked flask with a capacity of 3 liters The mixture was stirred evenly, and 20.6 g of trifluoroacetic acid (2,2,2-Trifluoroacetic acid, TFA) was added dropwise during the stirring. Then, it was made to react at 40 degreeC for 6 hours. After the reaction was completed, the solid was collected by suction filtration. The collected solid was further washed with 1300 g of methanol at 50°C, followed by further drying of the solid to obtain about 345 g of R4-COOH solid.

Next, 124 g of R4-COOH solid, 137 g of 4-(4-heptylcyclohexyl)phenol (7CPO) and 6.1 g of 4-dimethylaminopyridine were placed in a 3-liter four-necked flask. Then, 830 ml of dichloromethane was added to the four-necked flask, and 105 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) was added during stirring. Then, it was made to react at 40 degreeC for 8 hours. After the reaction was completed, water was added for extraction, and the organic layer was collected and removed by anhydrous magnesium sulfate, filtered and dried. The solid obtained after draining was washed with isopropanol and heated. After washing, the solids were collected by filtration and vacuum dried to obtain about 210 grams of R4-7CPO solids.

Then, 110 g of R4-7CPO solid and 670 mL of dichloromethane were added to a 3-liter flask and stirred. During the stirring process, 140 g of a 12 wt% p-toluenesulfonic acid acetic acid solution was added dropwise. Thereafter, the reaction was carried out at room temperature for 2 hours. After the reaction was over, a little methanol was added. Then, the solvent was sucked dry, and extracted with dichloromethane and saturated aqueous sodium bicarbonate solution, and finally with water, and the organic layer was collected. The organic layer was dewatered with anhydrous magnesium sulfate, filtered and drained to obtain about 80 g of R4-OH as a solid.

Next, 20.7 g of 2,4-dinitrophenylethanol and 96.5 g of toluene were placed in a 0.5-liter three-necked flask, 0.1 g of dimethylformamide was added, and the temperature was raised to 75°C. Subsequently, 12 grams of thionyl chloride was slowly added. After the addition, the temperature was maintained at 80°C and the reaction was continued. After the solution became yellow and clear, the temperature was lowered to 30°C. 46 g of R4-OH solid and 0.56 g of 4-dimethylaminopyridine were dissolved in 22 g of pyridine, which was then dropped into a three-necked flask. After the addition was complete, after stirring at room temperature for 12 hours, the temperature was raised to 60°C and 80 g of methanol was added. After a subsequent 1 hour hold at 45°C, the solvent was pumped dry to obtain about 44 grams of R4-DiNO as a solid.

Then, 80 grams of R4-DiNO solid, 85 grams of reduced iron and 40 grams of ammonium chloride (NH ₄ Cl) were placed in a four-necked flask with a capacity of 5 liters, and 950 grams of water and 1050 grams of ethyl acetate were added to the flask. (EA), stirred uniformly, heated to 70°C, and reacted at 70°C for 2 hours. After the reaction is completed, filter through diatomaceous earth at 70 ° C, remove the water layer after the filtrate is layered, collect the organic layer and remove water with anhydrous magnesium sulfate, filter and drain, and obtain about 35 grams of RPADA4 solid (i.e. , the diamine compound b1-1-4) represented by the formula (I-6).

Preparation Example 5

The compound represented by the formula (I-7) (hereinafter referred to as "diamine compound (b1-1-5)") was synthesized according to the following synthesis route 5.

[Synthetic route 5]

65 grams of 4-formylcinnamic acid, 100 grams of 4-(4-heptylcyclohexyl)phenol (7CPO) and 4.5 grams of 4-dimethylaminopyridine were placed in a four-necked flask with a capacity of 2 liters. In the four-necked flask, add 730 milliliters of dichloromethane, and in the stirring process, add 84 grams of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl). Then, it was made to react at 40 degreeC for 6 hours. After the reaction was completed, water was added for extraction, the organic layer was collected and removed with anhydrous magnesium sulfate, filtered and drained. The solid obtained after draining was heated and washed with isopropanol. After that, the solid was filtered again and collected to obtain about 130 g of R3CHO as a solid.

Next, 80 g of R3CHO solid and 620 ml of dimethylformamide were placed in a 1-liter three-necked flask and stirred. After the R3CHO solid was dissolved, 170 g of potassium hydrogen persulfate (Oxone) was added and reacted at room temperature for 3 hours. After completion of the reaction, the solvent was sucked dry to obtain a solid, which was washed with pure water and methanol. After washing, the solid was collected by filtration and dried in vacuo to obtain about 75 g of R3COOH as a pale yellow solid.

Then, 68.5 g of R3COOH pale yellow solid, 28.1 g of 2,4-dinitrophenol, 3.73 g of 4-dimethylaminopyridine and 1250 ml of 0.125 M dichloromethane were added to a four-necked flask with a capacity of 1 liter and Stir. During stirring, 34.5 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC.HCl) was added. Thereafter, the reaction was refluxed at 40°C for 6 hours. After the reaction was completed, water was added for extraction, the organic layer was collected, and the water was removed with anhydrous magnesium sulfate, then filtered and drained. The solid obtained after draining was washed with isopropanol and heated. After washing, the solid was collected by filtration and vacuum dried to obtain about 50 grams of R3DiNO as a solid.

Then, put 28.3 grams of R3DiNO solid and 270 milliliters of anisole into a four-necked flask with a capacity of 2 liters and stir; in addition, prepare 115 milliliters of pure water and 6 grams of Pt/C and put them into a beaker with a capacity of 2 liters and stir, Subsequently, 0.08 g of ammonium metavanadate and 0.42 g of an aqueous solution of hypophosphorous acid (50 wt %) were added to prepare a mixed solution. The above mixed solution was poured into a four-necked flask, and the temperature was raised to 65°C. Subsequently, 18.4 g of hydrazine was added dropwise, and after all the dropwise addition, the temperature was raised to 80° C. and the reaction was performed for 4 hours. Subsequently, the solution was filtered, and the filtrate was extracted with ethyl acetate and water and then sucked dry to obtain a solid. Next, the solid was heated and washed with ethyl acetate, after which the solid was filtered and collected to obtain about 10 g of RPADA3M solid (i.e., the diamine compound b1-1-5 represented by the formula (I-7)).

Preparation Example 6

The compound represented by the formula (I-9) (hereinafter referred to as "diamine compound (b1-1-6)") was synthesized according to the following synthesis route 6.

[Synthetic route 6]

Put 45 grams of 4-formylcinnamic acid, 100 grams of 5α-cholestan-3β-ol (5α-Cholestan-3β-ol) and 3.2 grams of 4-dimethylaminopyridine into a four-necked flask with a capacity of 2 liters Inside. Then 520 ml of dichloromethane was added to the four-necked flask, and 60 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) was added during stirring. Then, it was made to react at 40 degreeC for 6 hours. After the reaction was completed, water was added for extraction, and the organic layer was collected and removed by anhydrous magnesium sulfate, filtered and dried. The solid obtained after draining was heated and washed with isopropanol. After that, the solid was filtered again and collected to obtain about 120 grams of R6CHO solid.

Next, 80 g of R6CHO solid and 500 ml of dimethylformamide were placed in a 1-liter three-necked flask and stirred. After the R6CHO solid was dissolved, 135 g of potassium hydrogen persulfate (Oxone) was added and reacted at room temperature for 3 hours. After completion of the reaction, the solvent was sucked dry to obtain a solid, which was washed with pure water and methanol. After washing, the solid was collected by filtration and vacuum dried to obtain about 60 grams of R6COOH as a solid.

Then, 120 g of R6COOH solid and 200 ml of toluene were placed in a three-necked flask with a capacity of 1 liter and stirred to dissolve, then 0.2 g of dimethylformamide was added, and the temperature was raised to 75°C. Subsequently, 23 g of thionyl chloride was slowly added dropwise, and the temperature was raised to 80°C after the dropping, and the reaction was carried out at 80°C for 5 minutes. Next, the temperature was lowered to 30°C. 40 g of 2,4-dinitrophenylethanol and 1 g of 4-dimethylaminopyridine were dissolved in 40 g of pyridine, and dropped into the above three-necked flask, and the stirring was continued for 12 hours. Thereafter, the temperature was raised to 60°C, and 150 mL of methanol was added, followed by maintaining the temperature at 45°C for 1 hour. Finally, the solvent was sucked dry and washed with methanol to obtain about 90 grams of precipitated R6DiNO solid.

Then, put 50 grams of R6DiNO solid and 400 milliliters of anisole into a four-necked flask with a capacity of 1 liter and stir; in addition, prepare 160 milliliters of pure water and 10 grams of Pt/C and put them into a beaker with a capacity of 2 liters and stir, Subsequently, 0.12 g of ammonium metavanadate and 0.6 g of an aqueous solution of hypophosphorous acid (50 wt %) were added to prepare a mixed solution. The above mixture was poured into a four-necked flask, and the temperature was raised to 65°C. Subsequently, 26 g of hydrazine was added dropwise, and after all the dropwise addition, the temperature was raised to 80° C. and the reaction was carried out for 4 hours. Subsequently, the solution was filtered, and the filtrate was extracted with ethyl acetate and water and then sucked dry to obtain a solid. Next, the solid was heated and washed with ethyl acetate, after which the solid was filtered and collected to obtain about 20 g of RPADA6 solid (i.e., the diamine compound b1-1-6 represented by the formula (I-9)).

Preparation example of diamine compound (b1-2)

For the preparation example of the diamine compound (b1-2), reference can be made to the content of Taiwan Patent Publication No. TW201536862A. In detail, for the preparation method of the compound represented by the formula (II-10) (hereinafter referred to as "diamine compound (b1-2-1)"), reference can be made to pages 40, lines 8 to 41 of the aforementioned Patent Publication The content of line 21; for the preparation method of the compound represented by formula (II-18) (hereinafter referred to as "diamine compound (b1-2-2)"), reference may be made to page 41, line 22 to The content of page 44, line 1; for the preparation method of the compound represented by formula (II-24) (hereinafter referred to as "diamine compound (b1-2-3)"), reference may be made to page 44, line 2 of the aforementioned patent publication To the content of page 45, line 25; for the preparation method of the compound represented by formula (II-22) (hereinafter referred to as "diamine compound (b1-2-4)"), please refer to page 45 of the aforementioned patent publication. The contents of line 26 to page 47, line 11; and the preparation method of the compound represented by the formula (II-26) (hereinafter referred to as "diamine compound (b1-2-5)") can be referred to the aforementioned Patent Publication No. Contents from page 47, line 12 to page 49, line 4.

Preparation example of diamine compound (b1-3)

For the preparation example of the diamine compound (b1-3), reference can be made to the content of Taiwan Patent Publication No. TW201546120A. In detail, for the preparation method of the compound represented by the formula (III-1) (hereinafter referred to as "diamine compound (b1-3-1)"), reference can be made to the contents of paragraphs [0144] to [0146] of the aforementioned Patent Publication For the preparation method of the compound represented by formula (III-2) (hereinafter referred to as "diamine compound (b1-3-2)"), reference can be made to the contents of paragraphs [0147] to [0149] of the aforementioned patent publication; For the preparation method of the compound represented by (III-3) (hereinafter referred to as "diamine compound (b1-3-3)"), reference can be made to the contents of paragraphs [0150] to [0152] of the aforementioned patent publication; For the preparation method of the compound represented by 4) (hereinafter referred to as "diamine compound (b1-3-4)"), reference can be made to the contents of paragraphs [0153] to [0155] of the aforementioned patent publication; it is represented by formula (III-5) For the preparation method of the compound (hereinafter referred to as "diamine compound (b1-3-5)"), reference can be made to the contents of paragraphs [0156] to [0158] of the aforementioned patent publication; and the compound represented by the formula (III-6) For the preparation method of (hereinafter referred to as "diamine compound (b1-3-6)"), reference can be made to the contents of paragraphs [0159] to [0161] of the aforementioned patent publication.

Synthesis example of polymer (A-1)

Synthesis Examples A-1-1-1 to A-1-1-6, Synthesis Examples A-1-2-1 to A-1-2-6, Synthesis Examples A-1-2-6, Synthesis Example A-1-3-1 to Synthesis Example A-1-3-6 and Synthesis Example A-1-4-1 to Synthesis Example A-1-4-6.

Synthesis Example A-1-1-1

A nitrogen inlet, a stirrer, a condenser and a thermometer were set on a four-necked conical flask with a volume of 500 ml, and nitrogen was introduced. Then, 0.025 mol (50 mol %) of the diamine compound b1-1-1 obtained in Preparation Example 1 and 0.025 mol (50 mol %) of the other diamine compound (b1-4-1) were added to the four-necked conical flask And 80 grams of N-methyl-2-pyrrolidone (abbreviated as NMP), and stirred at room temperature until dissolved. Next, 0.05 mol (100 mol %) of 2,3,5-tricarboxycyclopentylacetic dianhydride (abbreviated as a1-1) and 20 g of NMP were added and reacted at room temperature for 2 hours. After the reaction was completed, the reaction solution was poured into 1500 ml of water to precipitate the polymer. Then, the obtained polymer was filtered, washed with methanol and filtered three times, placed in a vacuum oven, and dried at a temperature of 60°C to obtain polymer A-1-1-1.

Synthesis Example A-1-1-2 to Synthesis Example A-1-1-6, Synthesis Example A-1-2-1 to Synthesis Example A-1-2-6, Synthesis Example A-1-3-1 to Synthesis Example A-1-3-6 and Synthesis Example A-1-4-1 to Synthesis Example A-1-4-6

Synthesis Example A-1-1-2 to Synthesis Example A-1-1-6, Synthesis Example A-1-2-1 to Synthesis Example A-1-2-6, Synthesis Example A-1-3-1 to Synthesis Example A-1-3-6 and Synthesis Example A-1-4-1 to Synthesis Example A-1-4-6 were prepared in the same procedure as Synthesis Example A-1-1-1, except for the difference It lies in: changing the raw material types of polymers and their usage amounts (as shown in Table 1).

Synthesis example of polymer (A-2)

Synthesis Example A-2-1 to Synthesis Example A-2-6

Synthesis Example A-2-1 to Synthesis Example A-2-6 are prepared in the same steps as Synthesis Example A-1-1-1, except that: shown in Table 2).

Comparative Synthesis Example of Polymer (A-1)

Comparative Synthesis Example A'-1-1 to Comparative Synthesis Example A'-1-5

Comparative Synthesis Example A'-1-1 to Comparative Synthesis Example A'-1-5 were prepared in the same steps as those of Synthesis Example A-1-1-1, except that the types of raw materials and The amount used (as shown in Table 3).

The compounds corresponding to the symbols in Tables 1 to 3 are shown below.

Table 1

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 2

table 3

Examples and Comparative Examples of Liquid Crystal Alignment Agent, Liquid Crystal Alignment Film, and Liquid Crystal Display Element

Examples 1 to 36 and Comparative Examples 1 to 8 of the liquid crystal alignment agent, the liquid crystal alignment film, and the liquid crystal display element will be described below.

Example 1

a. Liquid crystal alignment agent

Add 100 parts by weight of polymer (A-1-1-1) to 1200 parts by weight of N-methyl-2-pyrrolidone (referred to as B-1) and 800 parts by weight of ethylene glycol n-butyl ether (referred to as B-2), and stirring and mixing at room temperature until dissolved, the liquid crystal alignment agent of Example 1 can be obtained.

b. Liquid crystal alignment film and liquid crystal display element

The above-mentioned liquid crystal alignment agent was applied to two glass substrates with a conductive film composed of ITO (indium-tin-oxide) by a printer (manufactured by Nippon Photo Printing Co., Ltd., model S15-036), to form a pre-preg. coating. Then, the glass substrate was placed on a hot plate and pre-baked on the conditions of a temperature of 100° C. and a time of 5 minutes. Next, in a circulating oven, post-baking was performed under the conditions of a temperature of 220° C. and a time of 30 minutes. Finally, after the alignment treatment, the glass substrate on which the liquid crystal alignment film of Example 1 is formed can be obtained.

Two of the above-obtained glass substrates with the liquid crystal alignment film formed thereon were coated with thermocompression glue, and the other was sprinkled with a 4 µm spacer. Next, two glass substrates were bonded together, and a pressure of 10 kg was applied with a hot press, and the thermocompression bonding was performed under the condition of a temperature of 150°C. Then, liquid crystal injection was performed using a liquid crystal injector (manufactured by Shimadzu Corporation, model ALIS-100X-CH). Next, the liquid crystal injection port was sealed with a UV light curing glue, and the UV light curing glue was cured by illuminating the UV light, and the liquid crystal annealing treatment was performed in an oven at a temperature of 60° C. and a time of 30 minutes. , the liquid crystal display element of Example 1 can be obtained.

Table 4 shows the results of evaluating the liquid crystal display element of Example 1 by the following evaluation methods.

Example 2 to Example 36

The liquid crystal alignment agents, liquid crystal alignment films and liquid crystal display elements of Examples 2 to 36 were prepared in the same steps as those of Example 1, except that the types of components and their usage amounts were changed, as shown in Table 4. . The liquid crystal display elements produced in Examples 2 to 36 were evaluated in the following evaluation method, and Table 4 shows the results.

Comparative Example 1 to Comparative Example 8

The liquid crystal alignment agents, liquid crystal alignment films and liquid crystal display elements of Comparative Examples 1 to 8 were prepared in the same steps as in Example 1, except that the types of components and their usage amounts were changed, as shown in Table 5. . The liquid crystal display elements produced in Comparative Examples 1 to 8 were evaluated by the evaluation method described later, and Table 5 shows the results.

The compounds corresponding to the symbols in Tables 4 and 5 are shown below.

Evaluation method

<Electric Field Memory Effect>

According to the method described in "T J Scheffer, et. al., J. Appl. Phys., vol. 19, 2013 (1980)", a liquid crystal evaluation device (manufactured by Chuo Precision Industry Co., Ltd.) was used. , the model is OMS-CM4RD) The liquid crystal display elements of Examples 1 to 36 and Comparative Examples 1 to 8 were evaluated. Specifically, the pretilt angle was measured by the crystal rotation method of He-Ne laser light, and recorded as P _m . Next, the alternating current of 60 Hz and 16 volts was applied, and it was placed on a light emitting diode (LED) backlight, and the pretilt angle was measured again after 36 hours, and recorded as P _n . And calculate the pretilt angle change with the following formula. The smaller the change of the pretilt angle, the better the electric field memory effect of the liquid crystal display element. On the contrary, the larger the change of the pretilt angle, the worse the electric field memory effect of the liquid crystal display element, and may even cause the problem that photo-alignment cannot be performed.

Pretilt angle change = ︱P _m -P _n ︱

The evaluation criteria for pretilt angle change are as follows:

◎: Pre-tilt angle change ≦0.3°;

○: 0.3°＜pre-tilt angle change≦0.6°;

△: 0.6°＜pre-tilt angle change≦1.0°;

╳: 1.0°<pre-tilt angle change, or photo-alignment cannot be performed.

<Environmental resistance>

The liquid crystal display elements of Examples 1 to 36 and Comparative Examples 1 to 8 were placed in an environment with a temperature of 65° C. and a relative humidity of 85%, respectively. After 120 hours, the ion densities of the liquid crystal display elements of Examples 1 to 36 and Comparative Examples 1 to 8 were measured using an electrical measuring machine (manufactured by Toyo Corporation, model 6254). The test condition is to apply a triangular wave of 1.7 volts and 0.01 Hz at a temperature of 60°C. In the current-voltage waveform, the ion density (pC) can be measured by calculating the peak area in the range of 0 volts to 1 volts. The lower the ion density, the better the environmental resistance. Conversely, the higher the ion density, the worse the environmental resistance.

The evaluation criteria for ion density are as follows:

◎: ion density <20;

○: 20≦Ion density＜40;

△: 40≦Ion density<50;

╳: 50≦Ion density.

Table 4

Table 4 (continued)

Table 4 (continued)

table 5

<Evaluation result>

As can be seen from Table 4 and Table 5, compared with the liquid crystal aligning agents without the diamine compound (b1-1) (Comparative Examples 1 to 8), the liquid crystal aligning agents using the diamine compound (b1-1) (Example The liquid crystal alignment films and liquid crystal display elements formed in Examples 1 to 36) have good electric field memory effect and environmental resistance. Furthermore, the liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent (Comparative Example 1 to Comparative Example 8) without using the diamine compound (b1-1) have the problems of electric field memory effect and poor environmental resistance. .

When the use amount of the polymer (A-1) in the liquid crystal alignment agent falls within the range of 30 parts by weight to 95 parts by weight (Examples 7 to 12), the liquid crystal alignment film formed by the liquid crystal alignment agent can be And the liquid crystal display element has better electric field memory effect.

When the diamine compound (b1) in the polymer (A-1) in the liquid crystal aligning agent includes the diamine compound (b1-2) (Example 13 to Example 18, Example 31 and Example 32), it can be The liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent have better electric field memory effect.

When the diamine compound (b1) in the polymer (A-1) in the liquid crystal aligning agent includes the diamine compound (b1-3) (Example 19 to Example 24, Example 33 and Example 34), it can be The liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent have better environmental resistance.

When the diamine compound (b1) in the polymer (A-1) in the liquid crystal alignment agent includes the diamine compound (b1-2) and the diamine compound (b1-3) (Example 25 to Example 30, Example 35 and 36), the liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent can have better electric field memory effect and better environmental resistance.

To sum up, the polymer in the liquid crystal alignment agent of the present invention is prepared by reacting a tetracarboxylic dianhydride compound and a diamine compound with a specific structure, so the liquid crystal alignment agent is used to form a liquid crystal alignment film When the liquid crystal alignment film is used, the liquid crystal display element using the liquid crystal alignment film has good electric field memory effect and environmental resistance, so it is suitable for the liquid crystal alignment film and the liquid crystal display element.

Although the present invention has been disclosed above with examples, it is not intended to limit the present invention. Any person skilled in the art can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection shall be subject to what is defined in the claims.

Claims (18)

1. a diamine compound is characterized in that, it is the diamine compound b1-1 represented by formula (I):

In formula (I), X ¹ and X ² each independently represent a single bond, -O-,

wherein R ¹⁴ represents hydrogen or an alkyl group having a carbon number of 1 to 4; x represents 0 or 1; y represents an integer from 0 to 4; R ¹ represents a methylene group or an alkylene group having a carbon number of 2 to 4; R ³ each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group; R ² represents an organic group represented by formula (IA) or a monovalent organic group having a steroid skeleton having a carbon number of 17 to 40;

In formula (I-A), R ⁴ represents fluorine or methyl; R ⁵ , R ⁶ and R ⁷ each independently represent a single bond, -O-,

Methylene or alkylene having 2 to 3 carbons; R ⁸ means

wherein R ¹⁰ and R ¹¹ each independently represent fluorine or methyl, and * represents the bonding position; R ⁹ represents hydrogen, fluorine, alkyl having 1 to 12 carbons, fluoroalkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, fluorine-substituted alkoxy having 1 to 12 carbons Alkoxy, -OCH ₂ F, -OCHF ₂ , -OCF ₃ ; a represents an integer from 0 to 2; b, c and d each independently represent an integer from 0 to 4; e, f and g each independently represent an integer from 0 to 3; i and j each independently represent an integer from 0 to 2; * indicates the bond position; When R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ or R ¹¹ are plural, each independently represents the same or different groups. 2. The diamine compound according to claim 1, wherein in the diamine compound b1-1 represented by the formula (I), When x is 0, X ¹ is -O-,

wherein R ¹⁴ represents hydrogen or an alkyl group having a carbon number of 1 to 4; When x is 1, X ¹ is a single bond. 3. The diamine compound according to claim 1, wherein in the diamine compound b1-1 represented by the formula (I), When x is 0, X ¹ is -O-,

4. The diamine compound according to claim 1, wherein in the diamine compound b1-1 represented by the formula (I), R ⁵ , R ⁶ and R ⁷ each independently represent a single bond, -O-,

A methylene group or an alkylene group having 2 to 3 carbon atoms. 5. The diamine compound according to claim 1, wherein in the diamine compound b1-1 represented by the formula (I), When e+f+g<3, f and g are different from 0; When f≧1, b≧1; When g≧1, c+d≧1. 6. A polymer A-1, characterized in that it is prepared by reacting a first mixture, and the first mixture comprises a tetracarboxylic dianhydride compound a1 and a diamine compound b1, wherein the diamine compound The amine compound b1 includes the diamine compound b1-1 represented by the formula (I) according to any one of claims 1 to 5. 7. The polymer A-1 according to claim 6, wherein the diamine compound b1 further comprises a diamine compound b1-2 represented by formula (II):

In formula (II), R ¹⁵ and R ¹⁷ each independently represent -O-, -S-,

R ¹⁶ represents an alkylene group having a carbon number of 2 to 10; R ¹⁸ represents a single bond, methylene or ethylene; Y ¹ represents a monovalent organic group having a carbon number of 17 to 40 having a steroid skeleton. 8. The polymer A-1 according to claim 6, wherein the diamine compound b1 further comprises a diamine compound b1-3 represented by formula (III):

In formula (III), Y ² each independently represents -O-, -NH-,

-CH ₂ O-,

Y ³ each independently represents a single bond, a divalent aliphatic hydrocarbon group with a carbon number of 1 to 20, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group; Y ⁴ each independently represents a single bond, -O-, -NH-,

where m represents an integer from 1 to 5; Y ⁵ each independently represents a nitrogen-containing aromatic heterocyclic group; k represents an integer of 1 to 4. 9. The polymer A-1 according to claim 6, wherein the amount of the diamine compound b1-1 represented by the formula (I) used is 100 parts by mole based on the amount of the diamine compound b1 used. 50 mole parts to 100 mole parts. 10. The polymer A-1 according to claim 7, wherein the amount of the diamine compound b1-2 represented by the formula (II) used is 100 parts by mole based on the amount of the diamine compound b1 used 5 to 30 mole parts. 11. The polymer A-1 according to claim 8, wherein the used amount of the diamine compound b1-3 represented by the formula (III) is 100 mole parts based on the used amount of the diamine compound b1 1 to 20 mole parts. 12 . A liquid crystal alignment agent, comprising the polymer A-1 according to any one of claims 6 to 11 and a solvent B. 13 . 13. The liquid crystal alignment agent according to claim 12, further comprising polymer A-2 prepared by reacting a second mixture comprising tetracarboxylic acid dibasic Anhydride compound a2 and diamine compound b2. 14 . The liquid crystal alignment agent according to claim 12 , wherein the solvent B is used in an amount of 1000 to 3500 parts by weight based on 100 parts by weight of the polymer A-1. 15 . 15. The liquid crystal alignment agent according to claim 13, wherein based on the total usage amount of the polymer A-1 and the polymer A-2 is 100 parts by weight, the usage amount of the polymer A-1 is 30 to 95 parts by weight. 16. The liquid crystal alignment agent according to claim 13, wherein based on the total usage amount of the polymer A-1 and the polymer A-2 is 100 parts by weight, the usage amount of the solvent B is 1000 parts by weight to 3500 parts by weight. 17 . A liquid crystal alignment film, characterized in that, it is formed of the liquid crystal alignment agent according to any one of claims 12 to 16 . 18. A liquid crystal display element comprising the liquid crystal alignment film according to claim 17.

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