TW202110946A - Diamine compound, polymer, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

A diamine compound, a polymer, a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display device are provided. The diamine compound is a diamine compound (b1-1) represented by formula (I). The polymer (A-1) is obtained by reacting a first mixture. The first mixture includes a tetracarboxylic dianhydride compound (a1) and a diamine compound (b1), wherein the diamine compound (b1) includes the diamine compound (b1-1) represented by formula (I). A liquid crystal alignment agent includes the polymer (A-1) and a solvent (B).

Description

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

The 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 that can produce a liquid crystal display element with an electric field memory effect and good environmental resistance. Materials, liquid crystal alignment agents, liquid crystal alignment films and liquid crystal display elements.

Conventionally, as the operating mode of liquid crystal display elements, there are known twisted nematic (Twisted Nematic, TN) type or super twisted nematic (Super Twisted Nematic, STN) type, using liquid crystal molecules with positive dielectric anisotropy, 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 perform alignment control 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 molecules of the TN type, STN type and other liquid crystal alignment films have a high-speed response, and the tilt direction of the VA type and other liquid crystal alignment films during liquid crystal driving is constant, each of them needs to have a pretilt angle characteristic. As a method of imparting the pretilt angle characteristics, in the former case, the rubbing method is generally used, and in the latter case, the rubbing method is generally used, or a method of providing protrusions on the surface of the substrate, or the like. The dust or static electricity generated in the rubbing method may sometimes cause display failure or circuit damage. On the other hand, the method of providing protrusions on the surface of the substrate sometimes impairs the brightness of the obtained liquid crystal display element. Therefore, these methods are all There is a problem.

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 film from a direction inclined with respect to the film normal has been proposed (Patent Document 5). However, the liquid crystal display element manufactured using the liquid crystal alignment 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 conducive to application.

On the other hand, as a method for imparting liquid crystal alignment ability to a coating film formed of a liquid crystal alignment agent containing polyamide acid or the like, in recent years, a photo-alignment method using photoisomerization, photodimerization, and photolysis has been proposed. As an alternative to the friction method. The photo-alignment method is a method of irradiating a radiation-sensitive organic thin film formed on a substrate with polarized or non-polarized radiation to impart anisotropy to the film, thereby controlling the alignment of liquid crystal molecules. According to this method, compared with the conventional rubbing method, the generation of dust or static electricity in the step can be suppressed, and therefore, the generation of display defects or the decrease in yield caused by dust or the like can be suppressed. In addition, it also has the advantages of uniformly imparting liquid crystal alignment ability to the organic thin film formed on the substrate.

Specifically, the technical documents of the photo-alignment method are described in Patent Document 6. Patent Document 6 proposes a liquid crystal alignment agent having a repeating unit of conjugated enone and an imine structure. However, the liquid crystal display element manufactured using the liquid crystal alignment agent described in Patent Document 6 also has the problem of poor electric field memory effect and environmental resistance of the liquid crystal display element. [Prior Technical Literature] [Patent Literature] [Patent Document 1] Japanese Patent Application Laid-Open No. 56-91277 [Patent Document 2] Japanese Patent Laid-Open No. 1-120528 [Patent Document 3] Japanese Patent Application Laid-Open No. 11-258605 [Patent Document 4] JP 2002-250924 A [Patent Document 5] JP 2004-83810 A [Patent Document 6] JP 2005-037654 A

Therefore, how to improve the electric field memory effect and poor environmental resistance of liquid crystal display elements to meet the current industry requirements is a problem that those skilled in the art want to solve.

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

式(I) 式(I)中， X¹ 及X² 各自獨立表示單鍵、

、

、

、

、

、

、

、

、

、

或

，其中R¹⁴ 表示氫或碳數為1至4的烷基； x表示0或1； y表示0至4的整數； R¹ 表示亞甲基或碳數為2至4的伸烷基； R³ 各自獨立表示碳數為1至6的烷基、碳數為1至6的烷氧基、鹵素原子或氰基； R² 表示由式(I-A)表示的有機基團或碳數為17至40的具有類固醇骨架的一價有機基團；

式(I-A) 式(I-A)中， R⁴ 表示氟或甲基； R⁵ 、R⁶ 及R⁷ 各自獨立表示單鍵、－O－、

、

、

、

、

、亞甲基或碳數為2至3的伸烷基； R⁸ 表示

或

，其中R¹⁰ 及R¹¹ 各自獨立表示氟或甲基，*表示鍵結位置； R⁹ 表示氫、氟、碳數為1至12的烷基、碳數為1至12的氟烷基、碳數為1至12的烷氧基、經氟取代的碳數為1至12的烷氧基、-OCH₂ F、-OCHF₂ 、-OCF₃ ； a表示0至2的整數； b、c及d各自獨立表示0至4的整數； e、f及g各自獨立表示0至3的整數； i及j各自獨立表示0至2的整數； *表示鍵結位置； 當R⁴ 、R⁵ 、R⁶ 、R⁷ 、R⁸ 、R¹⁰ 或R¹¹ 為多個時，各自獨立表示相同或不同的基團。The present invention provides a diamine compound which is a diamine compound (b1-1) represented by formula (I).

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

,

,

,

,

,

,

,

,

,

or

, 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 of 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 a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, a halogen atom or a cyano group; R ² represents an organic group represented by formula (IA) or a carbon number of 17 to 40 monovalent organic groups with a steroid skeleton;

Formula (IA) In formula (IA), 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 represents

or

, Where R ¹⁰ and R ¹¹ each independently represent fluorine or methyl, * represents the bonding position; R ⁹ represents hydrogen, fluorine, an alkyl group having 1 to 12 carbons, a fluoroalkyl group having 1 to 12 carbons, carbon An alkoxy group having a number of 1 to 12, an alkoxy group having a carbon number of 1 to 12 substituted by fluorine, -OCH ₂ F, -OCHF ₂ , -OCF ₃ ; a represents an integer from 0 to 2; b, c, and d each independently represents 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; * represents the bonding position; when R ⁴ , R ⁵ , R ^{When there are a plurality of 6} , R ⁷ , R ⁸ , R ¹⁰ or R ¹¹ , each independently represents the same or different groups.

、

、

、

、

、

、

、

、

、

或

，其中R¹⁴ 表示氫或碳數為1至4的烷基；當x為1時，X¹ 為單鍵。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

,

,

,

,

,

,

,

,

,

or

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

、

、

、

或

。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

,

,

,

or

.

、

、

、

、亞甲基或碳數為2至3的伸烷基。In an embodiment of the present invention, in the diamine compound (b1-1) represented by formula (I), R ⁵ , R ⁶ and R ⁷ each independently represent a single bond,

,

,

,

, Methylene or alkylene having 2 to 3 carbons.

In an embodiment of the present invention, in the diamine compound (b1-1) represented by the formula (I), when e+f+g<3, f and g are not equal to 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 includes 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.

式(II) 式(II)中， R¹⁵ 及R¹⁷ 各自獨立表示

、

、

、

、

或

； R¹⁶ 表示碳數為2至10的伸烷基； R¹⁸ 表示單鍵、亞甲基或伸乙基； Y¹ 表示碳數為17至40的具有類固醇骨架的一價有機基團。In an embodiment of the present invention, the above-mentioned diamine compound (b1) further includes a diamine compound (b1-2) represented by formula (II).

Formula (II) In formula (II), R ¹⁵ and R ¹⁷ each independently represent

,

,

,

,

or

; R ¹⁶ represents an alkylene group having a carbon number of 2 to 10; R ¹⁸ represents a single bond, a methylene group or an ethylene group; Y ¹ represents a monovalent organic group having a carbon number of 17 to 40 having a steroid skeleton.

式(III) 式(III)中， Y² 各自獨立表示

、

、

、

、

、

、

、

或

； Y³ 各自獨立表示單鍵、碳數為1至20的二價脂肪族烴基、二價脂環族烴基或二價芳香族烴基； Y⁴ 各自獨立表示單鍵、

、

、

、

、

、

、

、

、

或

，其中m表示1至5的整數； Y⁵ 各自獨立表示含氮的芳香族雜環基； k表示1至4的整數。In an embodiment of the present invention, the above-mentioned diamine compound (b1) further includes a diamine compound (b1-3) represented by formula (III).

Formula (III) In formula (III), Y ² each independently represents

,

,

,

,

,

,

,

or

; 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,

,

,

,

,

,

,

,

,

or

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

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

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

In an embodiment of the present invention, based on the usage amount of the diamine compound (b1) being 100 mol parts, the usage amount of the diamine compound (b1-3) represented by the formula (III) is 1 mol part to 20 mol parts. Moer part.

The present invention also provides a liquid crystal alignment agent comprising the above-mentioned polymer (A-1) and 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 prepared 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 usage amount of the polymer (A-1) is 100 parts by weight, the usage amount of the solvent (B) is 1000 parts by weight 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 the polymer (A-1) and the polymer (A-2) being 100 parts by weight, the usage amount of the solvent (B) is 1000 parts by weight to 3500 parts by weight.

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

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

Based on the above, when the present invention applies a 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 made by using the liquid crystal alignment agent can have good electric field memory effect and environmental resistance. It is further 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 comprehensible, the following specific embodiments are described in detail in conjunction with the accompanying drawings.

> Diamine compound >

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

Formula (I)

、

、

、

、

、

、

、

、

、

或

，其中R¹⁴ 表示氫或碳數為1至4的烷基。In formula (I), X ¹ and X ² each independently represent a single bond,

,

,

,

,

,

,

,

,

,

or

, Wherein R ¹⁴ represents hydrogen or an alkyl group having 1 to 4 carbon atoms.

、

、

、

、

、

、

、

、

、

或

；更佳為

、

、

、

或

，其中R¹⁴ 表示氫或碳數為1至4的烷基。當x為1時，X¹ 較佳為表示單鍵。In formula (I), x represents 0 or 1. When x is 0, X ¹ preferably represents

,

,

,

,

,

,

,

,

,

or

; Better

,

,

,

or

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

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

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

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

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

式(I-A)

Formula (IA)

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

、

、

、

、

、亞甲基或碳數為2至3的伸烷基；較佳為各自獨立表示單鍵、－O－、

、

、

、亞甲基或碳數為2至3的伸烷基。In formula (IA), R ⁵ , R ⁶ and R ⁷ each independently represent a single bond, -O-,

,

,

,

,

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

,

,

, Methylene or alkylene having 2 to 3 carbons.

或

，其中R¹⁰ 及R¹¹ 各自獨立表示氟或甲基；*表示鍵結位置。i及j各自獨立表示0至2的整數。In formula (IA), R ⁸ represents

or

, Where R ¹⁰ and R ¹¹ each independently represent fluorine or methyl; * represents the bonding position. i and j each independently represent an integer from 0 to 2.

In formula (IA), 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 The integer of 3 is preferably an integer of 0 to 2 each independently. 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 the formula (I-A), * represents the 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 group.

Specifically, when f and g are not 0, when a represents 2, each of the plurality of R ⁴ may represent the same or different group; when b, c, and d each independently represent 2 to 4 In the case of an integer, each of the multiple R ⁵ may represent the same or different group, each of the multiple R ⁶ may represent the same or different group, and each of the multiple 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 the plurality of R ¹⁰ may represent the same or different group. When j represents 2, each of the plurality of R ¹¹ may represent the same or different group.

In formula (IA), R ⁹ represents hydrogen, fluorine, an alkyl group having 1 to 12 carbons, a fluoroalkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and a carbon substituted with fluorine. Alkoxy groups with numbers from 1 to 12, -OCH ₂ F, -OCHF ₂ , and -OCF ₃ .

式(I-A-1)

式(I-A-2)

式(I-A-3)

式(I-A-4)

式(I-A-5)

式(I-A-6)

式(I-A-7)

式(I-A-8)

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

Formula (IA-1)

Formula (IA-2)

Formula (IA-3)

Formula (IA-4)

Formula (IA-5)

Formula (IA-6)

Formula (IA-7)

Formula (IA-8)

Formula (IA-9)

To the formula (IA-9), the same formula (IA-1) in the group represented by R ⁹ in formula (IA) R ⁹ group represented, which is not otherwise described herein.

式(I-B-a)

式(I-B-b)

式(I-B-c)

式(I-B-d)The steroid skeleton in the monovalent organic group having a steroid skeleton with a carbon number of 17 to 40 refers to the cyclopentano-perhydro phenanthrene skeleton or one or more of the carbon-carbon bonds contained therein Change to the skeleton of the double bond. Examples of the monovalent organic group having this kind of sterol skeleton include groups represented by the following formula (IBa), formula (IBb), formula (IBc), or formula (IBd), where * represents a bonding position.

Formula (IBa)

Formula (IBb)

Formula (IBc)

Formula (IBd)

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 formulae, and * 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 (IB-1), formula (IB-2), formula (IB-3) or formula (IB-4) Organic groups, where * represents the bonding position.

式(I-1)

式(I-2)

式(I-3)

式(I-4)

式(I-5)

式(I-6)

式(I-7)

式(I-8)

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

Formula (I-1)

Formula (I-2)

Formula (I-3)

Formula (I-4)

Formula (I-5)

Formula (I-6)

Formula (I-7)

Formula (I-8)

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 formed by the liquid crystal alignment agent and the liquid crystal display element have an electric field memory effect and poor environmental resistance problem. > Liquid crystal alignment agent >

The present invention provides a liquid crystal alignment agent, which includes 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, if necessary, the liquid crystal alignment agent may further include an additive (C). Hereinafter, each component of the liquid crystal alignment agent used in the present invention will be described in detail. Polymer (A-1)

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

The polymer (A-1) is prepared by reacting a first mixture containing a tetracarboxylic dianhydride compound (a1) and a diamine compound (b1). Hereinafter, the tetracarboxylic dianhydride compound (a1), the diamine compound (b1), and the method for preparing the polymer (A-1) will be described in detail. 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 formula (1-1) to formula (1) -6) Tetracarboxylic dianhydride compounds such as tetracarboxylic dianhydride compounds represented.

Specific examples of the aliphatic tetracarboxylic dianhydride compound include aliphatic tetracarboxylic dianhydrides such as ethane tetracarboxylic dianhydride or butane tetracarboxylic dianhydride. However, the present invention is not limited to this, 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-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetra Carboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic 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 to this, and the alicyclic tetracarboxylic dianhydride compound may further include other suitable alicyclic tetracarboxylic dianhydride compounds.

Specific examples of aromatic tetracarboxylic dianhydride compounds 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'-biphenyl tetracarboxylic acid dianhydride 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 dianhydride Anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 2,3,3',4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3' ,4,4'-Diphenylsulfide tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl dianhydride, 4,4'-bis(3,4- Dicarboxyphenoxy) diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid 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'-Diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis(dehydrate trimellitate), propylene glycol -Bis (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro trimellitate), 1,8 -Octyldiol-bis(dehydrated trimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(dehydrated trimellitate), 2,3,4,5-tetrahydrofuran tetracarboxylic acid Acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-diside oxy-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-dioxo-3-furyl)-naphtho[1 ,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5-(tetrahydro-2,5-di-side oxy- 3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-methyl-5-(tetrahydro -2,5-di-side oxy-3-furanyl )-Naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5 -Di-side oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl -5-(Tetrahydro-2,5-diside oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5 ,9b-Hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]-furan-1,3-dione , 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1, 2-c]-furan-1,3-dione or 5-(2,5-di-side oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, etc. Aromatic tetracarboxylic dianhydride compound. However, the present invention is not limited to this, and the aromatic tetracarboxylic dianhydride compound may further include other suitable aromatic tetracarboxylic dianhydride compounds.

式(1-1)

式(1-2)

式(1-3)

式(1-4)

式(1-5) 式(1-5)中，A¹ 表示含有芳香環的二價基團；r表示1或2；A² 及A³ 各自獨立表示氫或烷基。

式(1-6) 式(1-6)中，A⁴ 表示含有芳香環的二價基團；A⁵ 及A⁶ 可各自獨立表示氫或烷基。The tetracarboxylic dianhydride compounds represented by formula (1-1) to formula (1-6) are shown below.

Formula (1-1)

Formula (1-2)

Formula (1-3)

Formula (1-4)

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

Formula (1-6) 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.

式(1-5-1)

式(1-5-2)

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

Formula (1-5-1)

Formula (1-5-2)

Formula (1-5-3)

式(1-6-1)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).

Formula (1-6-1)

The above-mentioned tetracarboxylic dianhydride compound (a1) can be used individually by 1 type or in combination of multiple types.

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 (2,3,5-tricarboxycyclopentylacetic acid dianhydride), 1,2,4,5-cyclohexane Alkyltetracarboxylic 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'-biphenyl tetracarboxylic dianhydride or a combination 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 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 also include other diamine compounds (b1-4). Hereinafter, the diamine compound (b1-1), the diamine compound (b1-2), the diamine compound (b1-3), and other diamine compounds (b1-4) will be described in detail. Diamine compound (b1-1)

The diamine compound (b1-1) has already 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 .

Based on the usage amount of the diamine compound (b1) being 100 mol parts, the usage amount of the diamine compound (b1-1) represented by the formula (I) may be 50 mol parts to 100 mol parts, preferably 55 mol parts It is from 65 mol to 100 mol, more preferably from 65 mol to 100 mol. Diamine compound (b1-2)

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

Formula (II)

、

、

、

、

或

。In the 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

,

,

,

,

or

.

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

In the 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 the 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 repeated here.

式(II-1)

式(II-2)

式(II-3)

式(II-4)

式(II-5)

式(II-6)

式(II-7)

式(II-8)

式(II-9)

式(II-10)

式(II-11)

式(II-12)

式(II-13)

式(II-14)

式(II-15)

式(II-16)

式(II-17)

式(II-18)

式(II-19)

式(II-20)

式(II-21)

式(II-22)

式(II-23)

式(II-24)

式(II-25)

式(II-26)

式(II-27)

式(II-28)

式(II-29)Specific examples of the diamine compound (b1-2) include diamine compounds represented by formula (II-1) to formula (II-29), preferably including 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).

Formula (II-1)

Formula (II-2)

Formula (II-3)

Formula (II-4)

Formula (II-5)

Formula (II-6)

Formula (II-7)

Formula (II-8)

Formula (II-9)

Formula (II-10)

Formula (II-11)

Formula (II-12)

Formula (II-13)

Formula (II-14)

Formula (II-15)

Formula (II-16)

Formula (II-17)

Formula (II-18)

Formula (II-19)

Formula (II-20)

Formula (II-21)

Formula (II-22)

Formula (II-23)

Formula (II-24)

Formula (II-25)

Formula (II-26)

Formula (II-27)

Formula (II-28)

Formula (II-29)

The diamine compound (b1-2) represented by the formula (II) can be synthesized by a well-known organic synthesis method. For example, the synthesis of the compound represented by formula (II-1), formula (II-2), formula (II-7) or formula (II-8) is to combine anhydrous succinic acid with cholesterol or cholesterol, respectively After the addition reaction of cholestanol, for example, thionyl chloride is used to form thionyl chloride, and dinitrophenol is reacted with thionyl chloride in the presence of a larger equivalent of base based on the chloride, and thereafter , Use a suitable reducing agent such as tin chloride to carry out the reduction reaction to complete the above synthesis.

The synthesis of the compound represented by formula (II-3), formula (II-4), formula (II-9) or formula (II-10) can be the addition of anhydrous succinic acid with cholesterol or cholesterol or cholesterol, respectively After the reaction, in the presence of potassium carbonate, the aforementioned adduct and dinitrobenzoyl chloride (dinitrobenzoyl chloride) are subjected to an esterification reaction, and then a suitable reducing agent such as tin chloride is used to carry out a reduction reaction to complete the above synthesis.

The compound represented by formula (II-5) or formula (II-11) can be synthesized by tosylating cholesterol or cholesterol with tosyl chloride to obtain tosyl chloride. Tosylation of cholesterol or tosylation of cholesterol, followed by the reaction of butanediol and excess dinitrobenzyl chloride in the presence of a base to obtain dinitrobenzylbutanediol mono The ester is combined with the aforementioned tosylated cholestanol, and then heated in a suitable organic solvent to form an ether group. After that, a suitable reducing agent such as tin chloride is used to perform a reduction reaction to complete the above synthesis.

The compound represented by formula (II-6) or formula (II-12) can be synthesized by adding anhydrous succinic acid to cholesterol or cholesterol or cholestanol, respectively, and then converting the carbonyl group of the aforementioned adduct to lithium aluminum hydride. Reduction to methylene, in the presence of a base such as potassium tert-butoxide, the aforementioned reduction product and 2,4-dinitrochlorobenzene (2,4-dinitrochlorobenzene) are subjected to an esterification reaction, and then an appropriate A reducing agent such as tin chloride is used for the reduction reaction; or in the presence of a base such as potassium tertiary butoxide, 1-(4-hydroxybutane) is obtained by reacting 2,4-dinitrochlorobenzene with excess butanediol Oxy)-2,4-dinitrobenzene (1-(4-hydroxybutoxy)-2,4-dinitrobenzene), tosylated cholesterol or tosylated cholesterol prepared by the aforementioned method The alcohol 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 perform a reduction reaction to complete the above synthesis.

The compound represented by 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, 1-(4 -Hydroxyethoxy)-2,4-dinitro benzene (1-(4-hydroxyethoxy)-2,4-dinitro benzene), and toluene sulfonated cholesteryl alcohol prepared by the method described above , Heat in a suitable organic solvent to form an ether group, and then use a suitable reducing agent such as tin chloride to perform a reduction reaction to complete the above synthesis.

The synthesis of the compound represented by formula (II-14), formula (II-15) or formula (II-16) can be based on the use of lanosterol, lumisterol or ergosterol, respectively. The starting materials are synthesized according to the synthesis method of formula (II-6).

The compound represented by formula (II-17) or formula (II-18) can be synthesized by methanesulfonyl chloride (methanesulfonyl chloride), cholesterol or cholesterol, and excess Ethylene glycol undergoes substitution reaction to synthesize a monoether compound, and then in the presence of a base, the aforementioned monoether compound and 3,5-dinitrobenzoyl chloride (3,5-dinitrobenzoyl chloride) are reacted to synthesize dinitro After compounding, use a suitable reducing agent such as palladium carbon to perform a reduction reaction to complete the above synthesis.

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

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

The synthesis of the compound represented by the formula (II-23) or the formula (II-24) can be carried out by addition reaction of anhydrous succinic acid with cholesterol or cholestanol, respectively, and then using Borane-tetrahydrofuran complex (Borane-tetrahydrofuran complex). oxolane complex) The carbonyl group is reduced 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 then a suitable reducing agent such as palladium carbide is used. Reduction reaction to complete the above-mentioned synthesis.

The synthesis of the compound represented by the formula (II-25) or the formula (II-26) can be carried out by adding anhydrous glutaric acid to replace succinic acid with cholesterol or cholestanol, respectively, and then according to the 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 according to formula (II-14), formula (II-15) or formula (II-16) synthesis method.

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 properties. The electric field memory effect.

Based on the use amount of the diamine compound (b1) being 100 mole parts, the use amount of the diamine compound (b1-2) represented by the formula (II) may be 5 mole parts to 30 mole parts, preferably 7 It is between 27 mol and 10 mol and more preferably between 10 and 25 mol. Diamine compound (b1-3)

式(III) 式(III)中，Y² 各自獨立表示

、

、

、

、

、

、

、

或

；Y³ 各自獨立表示單鍵、碳數為1至20的二價脂肪族烴基、二價脂環族烴基或二價芳香族烴基；Y⁴ 各自獨立表示單鍵、

、

、

、

、

、

、

、

、

或

，其中m表示1至5的整數；Y⁵ 各自獨立表示含氮的芳香族雜環基；k表示1至4的整數。The diamine compound (b1-3) is a diamine compound (b1-3) represented by formula (III).

Formula (III) In formula (III), Y ² each independently represents

,

,

,

,

,

,

,

or

; 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,

,

,

,

,

,

,

,

,

or

, Wherein m represents an integer from 1 to 5; Y ⁵ each independently represents a nitrogen-containing aromatic heterocyclic group; 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.} Specific examples include the binding group (Y ² ) relative to the side chain. The two amine groups on the benzene ring are respectively 2,3 positions, 2,4 positions, 2,5 positions, 2,6 positions, 3,4 positions. Or 3,5 positions, etc. From the viewpoint of reactivity when synthesizing polyamide acid, the bonding position of the two amine groups is preferably 2,4 position, 2,5 position or 3,5 position. In terms of ease of synthesis of the diamine compound, the bonding position of the two amine groups is more preferably 2,4 position or 2,5 position.

、

、

、

、

、

、

、

或

。就合成二胺化合物時的容易性而言，Y² 較佳為各自獨立表示

、

、

、

、

、

或

。In formula (III), Y ² each independently represents

,

,

,

,

,

,

,

or

. In terms of ease of synthesizing the diamine compound, Y ^{2 is} preferably each independently represented

,

,

,

,

,

or

.

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, and 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, cycloheptadecan ring, cyclooctadecane ring , Cyclonadecane ring, cycloeicosane ring, tricycloicosane ring, tricyclodocosane ring, bicycloheptane ring, decahydronaphthalene ring ( decahydronaphthalene ring), norbornene ring (norbornene ring) or adamantane ring (adamantane ring), etc.

Specific examples of the aromatic ring in the divalent aromatic hydrocarbon group include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, and phenanthrene ring. Or phenalene ring, etc.

Specifically, in the formula (III), Y ³ preferably each independently represents a single bond, a methylene group, a linear or branched alkylene group having 2 to 10 carbons, and a straight chain having 2 to 10 carbons. Or branched alkenylene, straight chain or branched alkynylene with carbon number of 2 to 10, divalent alicyclic hydrocarbon group or divalent aromatic hydrocarbon group, wherein the alicyclic ring 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, tetralin Ring, fluorene ring or anthracene ring. Y ^{3 is more} preferably each independently representing a single bond, a methylene group, a linear or branched alkylene group having a carbon number of 2 to 10, a linear or branched alkenylene group having a carbon number of 2 to 10, and a divalent lipid Cyclic hydrocarbon group or divalent aromatic hydrocarbon group, where 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 linear or branched alkylene group having a carbon number of 2 to 10, a cyclohexylene group, a phenylene group or a naphthylene group. Y ^{3 is} particularly preferably each independently representing a single bond, a methylene group, a linear or branched alkylene group having 2 to 5 carbon atoms, or a phenylene group.

、

、

、

、

、

、

、

、

或

，其中m表示1至5的整數。Y⁴ 較佳為各自獨立表示單鍵、

、

、

、

、

或

，其中m表示1至5的整數。In formula (III), Y ⁴ each independently represents a single bond,

,

,

,

,

,

,

,

,

or

, Where m represents an integer from 1 to 5. Y ^{4 is} preferably each independently representing a single bond,

,

,

,

,

or

, Where m represents an integer from 1 to 5.

式(III-C)中，R¹⁹ 表示碳數為1至5的直鏈或分支的烷基。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 aromatic containing at least one structure selected from the group consisting of formula (III-A), formula (III-B) and formula (III-C) Group heterocyclic group.

In the 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 heterocyclic ring in Y ⁵ include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, and pyrazole ring. ), pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, Purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring , Triazole ring, pyrazine ring, benzimidazole ring, phenanthroline ring, indole ring, quinoxaline ring ), benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring. Specifically, Y ⁵ preferably each independently represents pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, triazinyl, triazolyl, pyrazinyl, or benzimidazolyl. 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 bonded to a substituent that is 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. In addition, from the viewpoint of reactivity with the tetracarboxylic dianhydride compound, k preferably represents an integer of 1 to 3. In addition, when k represents an integer from 2 to 4, each of the plural Y ² , Y ³ , Y ⁴ , and Y ^{5 in the plural "-Y 2} -Y ³ -Y ⁴ -Y ⁵ "may represent the same Or different groups.

、

、

、

、

、

或

；Y³ 為亞甲基、碳數為2至10的直鏈或分支的伸烷基、碳數為2至10的直鏈或分支的伸烯基、二價脂環族烴基或二價芳香族烴基，其中二價脂環族烴基中的脂環為環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、降冰片烯環或金剛烷環，二價芳香族烴基中的芳香環為苯環、萘環、四氫萘環、芴環或蒽環；Y⁴ 為單鍵、

、

、

、

、

、

或

（m為1至5的整數）；Y⁵ 中的含氮的芳香族雜環為吡咯環、咪唑環、噁唑環、噻唑環、吡唑環、吡啶環、嘧啶環、喹啉環、吡唑啉環、異喹啉環、咔唑環、嘌呤環、噻二唑環、噠嗪環、吡唑啉環、三嗪環、吡唑啉烷環、三唑環、吡嗪環、苯並咪唑環、二氮菲環、吲哚環、喹噁啉環、苯並噻唑環、酚噻嗪環、噁二唑環或吖啶環；並且k為1或2。In formula (III), ^{the preferred combination of Y 2} , Y ³ , Y ⁴ , Y ⁵ and k is: Y ² is

,

,

,

,

,

or

; Y ³ is a methylene group, a linear or branched alkylene group having a carbon number of 2 to 10, a linear or branched alkenylene group having a carbon number of 2 to 10, a divalent alicyclic hydrocarbon group or a divalent aromatic group Alicyclic hydrocarbon group, wherein the alicyclic ring in the divalent alicyclic hydrocarbon group is cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring, divalent The aromatic ring in the aromatic 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,

,

,

,

,

,

or

(M is an integer from 1 to 5); ^{the nitrogen-containing aromatic heterocycle in Y 5} is pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyridine ring Oxazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolinidine ring, triazole ring, pyrazine ring, benzo Imidazole ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring; and k is 1 or 2.

、

、

、

、

或

；Y³ 為亞甲基、碳數為2至10的直鏈或分支的伸烷基、碳數為2至10的直鏈或分支的伸烯基、二價脂環族烴基或二價芳香族烴基，其中二價脂環族烴基中的脂環為環己烷環、降冰片烯環或金剛烷環，二價芳香族烴基中的芳香環為苯環、萘環、芴環或蒽環；Y⁴ 為單鍵、

、

、

、

、

、

或

（m為1至5的整數）；Y⁵ 為吡咯基、咪唑基、吡唑基、吡啶基、嘧啶基、吡唑啉基、咔唑基、噠嗪基、吡唑啉基、三嗪基、吡唑啉烷基、三唑基、吡嗪基或苯並咪唑基；並且k為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

,

,

,

,

or

; Y ³ is a methylene group, a linear or branched alkylene group having a carbon number of 2 to 10, a linear or branched alkenylene group having a carbon number of 2 to 10, a divalent alicyclic hydrocarbon group or a divalent aromatic group A group of hydrocarbon groups, where the alicyclic ring in the divalent alicyclic hydrocarbon group is a cyclohexane ring, norbornene ring or 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,

,

,

,

,

,

or

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

、

、

、

、

、或

；Y³ 為亞甲基、碳數為2至5的直鏈或分支的伸烷基或伸苯基；Y⁴ 為單鍵、

、

、

、

、

、或

（m為1至5的整數）；Y⁵ 為吡咯基、咪唑基、吡唑基、吡啶基或嘧啶基；並且k為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

,

,

,

,

,or

; Y ³ is a methylene group, a linear or branched alkylene group or phenylene group having a carbon number of 2 to 5; Y ⁴ is a single bond,

,

,

,

,

,or

(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.}

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡咯基 2

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 咪唑基 3

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡唑基 4

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡啶基 5

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 嘧啶基 6

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡咯基 7

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 咪唑基 8

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡唑基 9

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡啶基 10

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 嘧啶基 11

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡咯基 12

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 咪唑基 13

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡唑基 14

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡啶基 15

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 嘧啶基 16

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡咯基 17

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 咪唑基 18

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡唑基 19

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡啶基 20

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 嘧啶基 Table I Diamine compound (b1-3) NO. Y ² Y ³ Y ⁴ Y ⁵ 1

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrrolyl 2

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Imidazolyl 3

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrazolyl 4

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyridyl 5

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrimidinyl 6

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrrolyl 7

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Imidazolyl 8

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrazolyl 9

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyridyl 10

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrimidinyl 11

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrrolyl 12

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Imidazolyl 13

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrazolyl 14

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyridyl 15

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrimidinyl 16

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrrolyl 17

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Imidazolyl 18

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrazolyl 19

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyridyl 20

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrimidinyl

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡咯基 22

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 咪唑基 23

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡唑基 24

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡啶基 25

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 嘧啶基 26

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡咯基 27

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 咪唑基 28

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡唑基 29

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 吡啶基 30

亞甲基、碳數為2至5的直鏈或分支的伸烷基 單鍵 嘧啶基 Table II Diamine compound (b1-3) NO. Y ² Y ³ Y ⁴ Y ⁵ twenty one

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrrolyl twenty two

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Imidazolyl twenty three

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrazolyl twenty four

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyridyl 25

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrimidinyl 26

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrrolyl 27

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Imidazolyl 28

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrazolyl 29

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyridyl 30

Methylene, linear or branched alkylene having 2 to 5 carbons single bond Pyrimidinyl

伸苯基

吡咯基 32

伸苯基

咪唑基 33

伸苯基

吡唑基 34

伸苯基

吡啶基 35

伸苯基

嘧啶基 36

伸苯基

吡咯基 37

伸苯基

咪唑基 38

伸苯基

吡唑基 39

伸苯基

吡啶基 40

伸苯基

嘧啶基 41

伸苯基

吡咯基 42

伸苯基

咪唑基 43

伸苯基

吡唑基 44

伸苯基

吡啶基 45

伸苯基

嘧啶基 46

伸苯基

吡咯基 47

伸苯基

咪唑基 48

伸苯基

吡唑基 49

伸苯基

吡啶基 50

伸苯基

嘧啶基 51

伸苯基

（m：1~5） 吡咯基 52

伸苯基

（m：1~5） 咪唑基 53

伸苯基

（m：1~5） 吡唑基 54

伸苯基

（m：1~5） 吡啶基 55

伸苯基

吡咯基 56

伸苯基

咪唑基 57

伸苯基

吡唑基 58

伸苯基

吡啶基 59

伸苯基

嘧啶基 60

伸苯基

吡咯基 Table III Diamine compound (b1-3) NO. Y ² Y ³ Y ⁴ Y ⁵ 31

Phenylene

Pyrrolyl 32

Phenylene

Imidazolyl 33

Phenylene

Pyrazolyl 34

Phenylene

Pyridyl 35

Phenylene

Pyrimidinyl 36

Phenylene

Pyrrolyl 37

Phenylene

Imidazolyl 38

Phenylene

Pyrazolyl 39

Phenylene

Pyridyl 40

Phenylene

Pyrimidinyl 41

Phenylene

Pyrrolyl 42

Phenylene

Imidazolyl 43

Phenylene

Pyrazolyl 44

Phenylene

Pyridyl 45

Phenylene

Pyrimidinyl 46

Phenylene

Pyrrolyl 47

Phenylene

Imidazolyl 48

Phenylene

Pyrazolyl 49

Phenylene

Pyridyl 50

Phenylene

Pyrimidinyl 51

Phenylene

(M: 1~5) Pyrrolyl 52

Phenylene

(M: 1~5) Imidazolyl 53

Phenylene

(M: 1~5) Pyrazolyl 54

Phenylene

(M: 1~5) Pyridyl 55

Phenylene

Pyrrolyl 56

Phenylene

Imidazolyl 57

Phenylene

Pyrazolyl 58

Phenylene

Pyridyl 59

Phenylene

Pyrimidinyl 60

Phenylene

Pyrrolyl

伸苯基

咪唑基 62

伸苯基

吡唑基 63

伸苯基

吡啶基 64

伸苯基

嘧啶基 65

伸苯基

吡咯基 66

伸苯基

咪唑基 67

伸苯基

吡唑基 68

伸苯基

吡啶基 69

伸苯基

嘧啶基 70

伸苯基

吡咯基 71

伸苯基

咪唑基 72

伸苯基

吡唑基 73

伸苯基

吡啶基 74

伸苯基

嘧啶基 75

伸苯基

（m：1~5） 吡咯基 76

伸苯基

（m：1~5） 咪唑基 77

伸苯基

（m：1~5） 吡唑基 78

伸苯基

（m：1~5） 吡啶基 Table IV Diamine compound (b1-3) NO. Y ² Y ³ Y ⁴ Y ⁵ 61

Phenylene

Imidazolyl 62

Phenylene

Pyrazolyl 63

Phenylene

Pyridyl 64

Phenylene

Pyrimidinyl 65

Phenylene

Pyrrolyl 66

Phenylene

Imidazolyl 67

Phenylene

Pyrazolyl 68

Phenylene

Pyridyl 69

Phenylene

Pyrimidinyl 70

Phenylene

Pyrrolyl 71

Phenylene

Imidazolyl 72

Phenylene

Pyrazolyl 73

Phenylene

Pyridyl 74

Phenylene

Pyrimidinyl 75

Phenylene

(M: 1~5) Pyrrolyl 76

Phenylene

(M: 1~5) Imidazolyl 77

Phenylene

(M: 1~5) Pyrazolyl 78

Phenylene

(M: 1~5) Pyridyl

伸苯基

吡咯基 80

伸苯基

咪唑基 81

伸苯基

吡唑基 82

伸苯基

吡啶基 83

伸苯基

嘧啶基 84

伸苯基

吡咯基 85

伸苯基

咪唑基 86

伸苯基

吡唑基 87

伸苯基

吡啶基 88

伸苯基

嘧啶基 89

伸苯基

吡咯基 90

伸苯基

咪唑基 91

伸苯基

吡唑基 92

伸苯基

吡啶基 93

伸苯基

嘧啶基 94

伸苯基

吡咯基 95

伸苯基

咪唑基 96

伸苯基

吡唑基 97

伸苯基

吡啶基 98

伸苯基

嘧啶基 99

伸苯基

（m：1~5） 吡咯基 100

伸苯基

（m：1~5） 咪唑基 101

伸苯基

（m：1~5） 吡唑基 102

伸苯基

（m：1~5） 吡啶基 103

伸苯基

吡咯基 104

伸苯基

咪唑基 105

伸苯基

吡唑基 106

伸苯基

吡啶基 107

伸苯基

嘧啶基 108

伸苯基

吡咯基 109

伸苯基

咪唑基 110

伸苯基

吡唑基 Table V Diamine compound (b1-3) NO. Y ² Y ³ Y ⁴ Y ⁵ 79

Phenylene

Pyrrolyl 80

Phenylene

Imidazolyl 81

Phenylene

Pyrazolyl 82

Phenylene

Pyridyl 83

Phenylene

Pyrimidinyl 84

Phenylene

Pyrrolyl 85

Phenylene

Imidazolyl 86

Phenylene

Pyrazolyl 87

Phenylene

Pyridyl 88

Phenylene

Pyrimidinyl 89

Phenylene

Pyrrolyl 90

Phenylene

Imidazolyl 91

Phenylene

Pyrazolyl 92

Phenylene

Pyridyl 93

Phenylene

Pyrimidinyl 94

Phenylene

Pyrrolyl 95

Phenylene

Imidazolyl 96

Phenylene

Pyrazolyl 97

Phenylene

Pyridyl 98

Phenylene

Pyrimidinyl 99

Phenylene

(M: 1~5) Pyrrolyl 100

Phenylene

(M: 1~5) Imidazolyl 101

Phenylene

(M: 1~5) Pyrazolyl 102

Phenylene

(M: 1~5) Pyridyl 103

Phenylene

Pyrrolyl 104

Phenylene

Imidazolyl 105

Phenylene

Pyrazolyl 106

Phenylene

Pyridyl 107

Phenylene

Pyrimidinyl 108

Phenylene

Pyrrolyl 109

Phenylene

Imidazolyl 110

Phenylene

Pyrazolyl

伸苯基

吡啶基 112

伸苯基

嘧啶基 113

伸苯基

吡咯基 114

伸苯基

咪唑基 115

伸苯基

吡唑基 116

伸苯基

吡啶基 117

伸苯基

嘧啶基 118

伸苯基

吡咯基 119

伸苯基

咪唑基 120

伸苯基

吡唑基 121

伸苯基

吡啶基 122

伸苯基

嘧啶基 123

伸苯基

（m：1~5） 吡咯基 124

伸苯基

（m：1~5） 咪唑基 125

伸苯基

（m：1~5） 吡唑基 126

伸苯基

（m：1~5） 吡啶基 Table VI Diamine compound (b1-3) NO. Y ² Y ³ Y ⁴ Y ⁵ 111

Phenylene

Pyridyl 112

Phenylene

Pyrimidinyl 113

Phenylene

Pyrrolyl 114

Phenylene

Imidazolyl 115

Phenylene

Pyrazolyl 116

Phenylene

Pyridyl 117

Phenylene

Pyrimidinyl 118

Phenylene

Pyrrolyl 119

Phenylene

Imidazolyl 120

Phenylene

Pyrazolyl 121

Phenylene

Pyridyl 122

Phenylene

Pyrimidinyl 123

Phenylene

(M: 1~5) Pyrrolyl 124

Phenylene

(M: 1~5) Imidazolyl 125

Phenylene

(M: 1~5) Pyrazolyl 126

Phenylene

(M: 1~5) Pyridyl

伸苯基

吡咯基 128

伸苯基

咪唑基 129

伸苯基

吡唑基 130

伸苯基

吡啶基 131

伸苯基

嘧啶基 132

伸苯基

吡咯基 133

伸苯基

咪唑基 134

伸苯基

吡唑基 135

伸苯基

吡啶基 136

伸苯基

嘧啶基 137

伸苯基

吡咯基 138

伸苯基

咪唑基 139

伸苯基

吡唑基 140

伸苯基

吡啶基 141

伸苯基

嘧啶基 142

伸苯基

吡咯基 143

伸苯基

咪唑基 144

伸苯基

吡唑基 145

伸苯基

吡啶基 146

伸苯基

嘧啶基 147

伸苯基

（m：1~5） 吡咯基 148

伸苯基

（m：1~5） 咪唑基 149

伸苯基

（m：1~5） 吡唑基 150

伸苯基

（m：1~5） 吡啶基 151

伸苯基

吡咯基 152

伸苯基

咪唑基 153

伸苯基

吡唑基 154

伸苯基

吡啶基 155

伸苯基

嘧啶基 Table VII Diamine compound (b1-3) NO. Y ² Y ³ Y ⁴ Y ⁵ 127

Phenylene

Pyrrolyl 128

Phenylene

Imidazolyl 129

Phenylene

Pyrazolyl 130

Phenylene

Pyridyl 131

Phenylene

Pyrimidinyl 132

Phenylene

Pyrrolyl 133

Phenylene

Imidazolyl 134

Phenylene

Pyrazolyl 135

Phenylene

Pyridyl 136

Phenylene

Pyrimidinyl 137

Phenylene

Pyrrolyl 138

Phenylene

Imidazolyl 139

Phenylene

Pyrazolyl 140

Phenylene

Pyridyl 141

Phenylene

Pyrimidinyl 142

Phenylene

Pyrrolyl 143

Phenylene

Imidazolyl 144

Phenylene

Pyrazolyl 145

Phenylene

Pyridyl 146

Phenylene

Pyrimidinyl 147

Phenylene

(M: 1~5) Pyrrolyl 148

Phenylene

(M: 1~5) Imidazolyl 149

Phenylene

(M: 1~5) Pyrazolyl 150

Phenylene

(M: 1~5) Pyridyl 151

Phenylene

Pyrrolyl 152

Phenylene

Imidazolyl 153

Phenylene

Pyrazolyl 154

Phenylene

Pyridyl 155

Phenylene

Pyrimidinyl

伸苯基

吡咯基 157

伸苯基

咪唑基 158

伸苯基

吡唑基 159

伸苯基

吡啶基 160

伸苯基

嘧啶基 161

伸苯基

吡咯基 162

伸苯基

咪唑基 163

伸苯基

吡唑基 164

伸苯基

吡啶基 165

伸苯基

嘧啶基 166

伸苯基

吡咯基 167

伸苯基

咪唑基 168

伸苯基

吡唑基 169

伸苯基

吡啶基 170

伸苯基

嘧啶基 171

伸苯基

吡咯基 172

伸苯基

（m：1~5） 咪唑基 173

伸苯基

（m：1~5） 吡唑基 174

伸苯基

（m：1~5） 吡啶基 Table VIII Diamine compound (b1-3) NO. Y ² Y ³ Y ⁴ Y ⁵ 156

Phenylene

Pyrrolyl 157

Phenylene

Imidazolyl 158

Phenylene

Pyrazolyl 159

Phenylene

Pyridyl 160

Phenylene

Pyrimidinyl 161

Phenylene

Pyrrolyl 162

Phenylene

Imidazolyl 163

Phenylene

Pyrazolyl 164

Phenylene

Pyridyl 165

Phenylene

Pyrimidinyl 166

Phenylene

Pyrrolyl 167

Phenylene

Imidazolyl 168

Phenylene

Pyrazolyl 169

Phenylene

Pyridyl 170

Phenylene

Pyrimidinyl 171

Phenylene

Pyrrolyl 172

Phenylene

(M: 1~5) Imidazolyl 173

Phenylene

(M: 1~5) Pyrazolyl 174

Phenylene

(M: 1~5) Pyridyl

式(III-D) 式(III-D)中，Y² 、Y³ 、Y⁴ 、Y⁵ 及k分別與式(III)中的Y² 、Y³ 、Y⁴ 、Y⁵ 及k同義，在此不另行贅述。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: first synthesize the dinitro compound represented by the formula (III-D), then, in the catalyst, The nitro group is reduced to an amine group in the presence of a solvent and hydride.

Formula (III-D) of formula ^{(III-D), Y 2} , Y 3, Y 4, Y 5 , and k, respectively in formula ^{(III) Y 2, Y 3} , Y 4, Y 5 and k are synonymous, I will not repeat them here.

The specific examples of the catalyst are not particularly limited but may include palladium-carbon, platinum dioxide, raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, or a combination of the above-mentioned catalysts. The 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. The specific examples of the hydride are not particularly limited but may include hydrogen, hydrazine, hydrogen chloride, or a combination of the foregoing compounds.

The dinitro compound represented by the formula (III-D) is synthesized by bonding Y ³ to Y ^{5 via Y 4} ; then Y ³ is bonded to a dinitro group-containing benzene ring via Y ^{2; or} so dinitro phenyl ring by Y ² and Y ³ are bonded and, then, Y ³ and Y ⁴ was synthesized via method Y ⁵ and bonded.

、

、

、

、

、

、

、

或

等結合基，這些結合基可藉由周知的有機合成方法來形成。Y ² is

,

,

,

,

,

,

,

or

Such as binding groups, these binding groups can be formed by well-known organic synthesis methods.

或

的情況下，由式(III-D)表示的二硝基化合物可藉由使含有二硝基的鹵素衍生物與含有Y³ 、Y⁴ 及Y⁵ 的羥基衍生物於鹼存在下進行反應而得；或者藉由使含有二硝基的羥基衍生物與含有Y³ 、Y⁴ 及Y⁵ 的鹵素取代衍生物於鹼存在下進行反應而得。For example, in Y ² is

or

In the case, the dinitro compound represented by the formula (III-D) can be obtained by reacting a halogen derivative containing a dinitro group with a ^{hydroxyl derivative containing Y 3} , Y ⁴ and Y ⁵ in the presence of a base Obtained; or by reacting a dinitro-containing hydroxy derivative and a ^{halogen-substituted derivative containing Y 3} , Y ⁴ and Y ⁵ in the presence of a base.

的情況下，由式(III-D)表示的二硝基化合物可藉由使含有二硝基的鹵素衍生物與含有Y³ 、Y⁴ 及Y⁵ 的胺基取代衍生物於鹼存在下進行反應而得。At Y ² for

In the case, the dinitro compound represented by the formula (III-D) can be carried out by making a halogen derivative containing a dinitro group ^{and an amino substituted derivative containing Y 3} , Y ⁴ and Y ⁵ in the presence of a base From the reaction.

的情況下，由式(III-D)表示的二硝基化合物可藉由使含有二硝基的羥基衍生物與含有Y³ 、Y⁴ 及Y⁵ 的醯氯（acid chloride）化合物於鹼存在下進行反應而得。At Y ² for

In the case of the formula (III-D), the dinitro compound represented by the formula (III-D) can be prepared by making a hydroxyl derivative containing a dinitro group and an ^{acid chloride compound containing Y 3} , Y ⁴ and Y ⁵ exist in a base Derived from the next reaction.

的情況下，由式(III-D)表示的二硝基化合物可藉由使含有二硝基的醯氯化合物與含有Y³ 、Y⁴ 及Y⁵ 的經胺基取代的化合物於鹼存在下進行反應而得。At Y ² for

In the case of the formula (III-D), the dinitro compound represented by formula (III-D) can be obtained by making a dinitro-containing chlorinated compound and ^{an amino-substituted compound containing Y 3} , Y ⁴ and Y ⁵ in the presence of a base Derived from the reaction.

的情況下，由式(III-D)表示的二硝基化合物可藉由使經胺基取代的化合物與含有Y³ 、Y⁴ 及Y⁵ 的含有二硝基的醯氯化合物於鹼存在下進行反應而得。At Y ² for

In the case of the formula (III-D), the dinitro compound represented by the formula (III-D) can be prepared by combining a compound substituted with an amine group and a dinitro group-containing chlorinated compound ^{containing Y 3} , Y ⁴ and Y ^{5 in the presence of a base} Derived from the reaction.

Specific examples of dinitro-containing halogen derivatives and dinitro-containing derivatives include 3,5-dinitrochlorobenzene (3,5-dinitrochlorobenzene), 2,4-dinitrochlorobenzene (2,4 -dinitrochlorobenzene, 2,4-dinitro fluorobenzene, 3,5-dinitro benzoyl chloride, 3,5-dinitro Benzoic acid (3,5-dinitrobenzoic acid), 2,4-dinitrobenzoyl chloride (2,4-dinitrobenzoyl chloride), 2,4-dinitrobenzoic acid (2,4-dinitrobenzoic acid), 3 ,5-Dinitro benzyl chloride (3,5-dinitro benzyl chloride), 2,4-dinitrobenzyl chloride (2,4-dinitrobenzyl chloride), 3,5-dinitrobenzyl chloride (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-dinitroaniline (2,5 -dinitrophenol), 2,6-dinitrophenol (2,6-dinitrophenol) or 2,4-dinitrophenylacetic acid (2,4-dinitrophenylacetic acid). The dinitro group-containing halogen derivatives and dinitro group-containing derivatives can be used singly or in combination of multiple types in consideration of the availability and reactivity of raw materials.

式(III-1)

式(III-2)

式(III-3)

式(III-4)

式(III-5)

式(III-6)The specific example of the diamine compound (b1-3) preferably includes at least one of the diamine compounds represented by the formula (III-1) to the formula (III-6).

Formula (III-1)

Formula (III-2)

Formula (III-3)

Formula (III-4)

Formula (III-5)

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 formed by the liquid crystal alignment agent and the liquid crystal display element can have better properties. Environmental resistance.

Based on the usage amount of the diamine compound (b1) being 100 mol parts, the usage amount of the diamine compound (b1-3) represented by the formula (III) may be 1 mol part to 20 mol parts, preferably 3 It is from 5 mol to 15 mol, more preferably from 5 mol to 15 mol. 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 Alkane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane Alkane, 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1, 7-diamino-2,5-dimethylheptane, 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), isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclic [6.2.1.0 ^2,7 ]-undecene two Methyldiamine, 4,4'-methylenebis(cyclohexylamine) (4,4'-methylenebis(cyclohexylamine)), 4,4'-diaminodiphenylmethane, 4,4'-di Amino diphenylethane, 4,4'-diaminodiphenyl benzene, 4,4'-diaminobenzaniline, 4,4'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroindene, 6- Amino-1-(4'-aminophenyl)-1,3,3-trimethylindenyl, hexahydro-4,7-methane-bridged indenyldimethylene diamine, 3,3 '-Diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminobenzene Oxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2 ,2-Bis[4-(4-aminophenoxy)phenyl]sulfuric acid, 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-diamino fluorene, 9,9-bis(4-aminophenyl) fluorene, 4,4'-methylene-bis (2-Chloroaniline), 4,4'-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylene) bisaniline, 2,2'- Bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy ]-Octafluoro Biphenyl, 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 diamine compounds (b1-4) such as diamine compounds represented by formulas (2-1) to (2-25) . However, the present invention is not limited to this, 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.

式(2-1) 式(2-1)中，B¹ 表示

、

、

、

、

或

；B² 表示含甾基團、三氟甲基、氟基、碳數為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環狀結構的一價基團。

Formula (2-1) In formula (2-1), B ¹ means

,

,

,

,

or

; B ² represents one containing a steroid group, a trifluoromethyl group, a fluoro group, an alkyl group having a carbon number of 2 to 30, or a nitrogen atom-containing cyclic structure derived from pyridine, pyrimidine, triazine, piperidine and piperazine Valence group.

式(2-1-1)

式(2-1-2)

式(2-1-3)

式(2-1-4)Specific examples of other diamine compounds represented by the formula (2-1) include 2,4-diaminophenyl ethyl formate (2,4-diaminophenyl ethyl formate), 3,5-diaminophenyl ethyl formate Ester (3,5-diaminophenyl ethyl formate), 2,4-diaminophenyl propyl formate (2,4-diaminophenyl propyl formate), 3,5-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 from formula (2-1-1) to formula (2-1-4) Other diamine compounds represented by.

Formula (2-1-1)

Formula (2-1-2)

Formula (2-1-3)

Formula (2-1-4)

式(2-2) 式(2-2)中，B³ 表示

、

、

、

、

或

；B⁴ 及B⁵ 表示伸脂肪族環、伸芳香族環或伸雜環基團；B⁶ 表示碳數為3至18的烷基、碳數為3至18的烷氧基、碳數為1至5的氟烷基、碳數為1至5的氟烷氧基、氰基或鹵素原子。

Formula (2-2) In formula (2-2), B ³ represents

,

,

,

,

or

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

式(2-2-1)

式(2-2-2)

式(2-2-3)

式(2-2-4)

式(2-2-5)

式(2-2-6)

式(2-2-7)

式(2-2-8)

式(2-2-9)

式(2-2-10)

式(2-2-11)

式(2-2-12)

式(2-2-13) 式(2-2-10)至式(2-2-13)中，q表示3至12的整數。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).

Formula (2-2-1)

Formula (2-2-2)

Formula (2-2-3)

Formula (2-2-4)

Formula (2-2-5)

Formula (2-2-6)

Formula (2-2-7)

Formula (2-2-8)

Formula (2-2-9)

Formula (2-2-10)

Formula (2-2-11)

Formula (2-2-12)

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

式(2-3) 式(2-3)中，B⁷ 表示氫、碳數為1至5的醯基、碳數為1至5的烷基、碳數為1至5的烷氧基或鹵素；s表示1至3的整數。當s表示2或3的整數時，多個B⁷ 可為相同或不同。

Formula (2-3) In formula (2-3), B ⁷ represents hydrogen, an acyl group having 1 to 5 carbons, an alkyl group having 1 to 5 carbons, an alkoxy group having 1 to 5 carbons, or Halogen; s represents an integer from 1 to 3. 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 the formula (2-3) include (1) when s is 1: p-diaminobenzene, m-diaminobenzene, o-diaminobenzene or 2,5- Diaminotoluene, 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'-diamino diphenyl, 3,3'-dimethoxy-4,4'-diamino diphenyl Benzene, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2',5,5'- Tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamine 2,2'-bis(trifluoromethyl)biphenyl, etc.; (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.

式(2-4) 式(2-4)中，t表示2至12的整數。

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

式(2-5) 式(2-5)中，v表示1至5的整數。

Formula (2-5) In the 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.

式(2-6) 式(2-6)中，B⁸ 及B¹⁰ 各自獨立表示二價有機基團，B⁹ 表示衍生自吡啶、嘧啶、三嗪、哌啶及哌嗪等含氮原子環狀結構的二價基團。

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

式(2-7) 式(2-7)中，B¹¹ 、B¹² 、B¹³ 及B¹⁴ 各自獨立表示碳數為1至12的烴基；w表示1至3的整數；z表示1至20的整數。

Formula (2-7) 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; z represents 1 to 20 Integer.

式(2-8) 式(2-8)中，B¹⁵ 表示

或伸環己基；B¹⁶ 表示亞甲基；B¹⁷ 表示伸苯基或伸環己基；B¹⁸ 表示氫或庚烷基。

Formula (2-8) In formula (2-8), B ¹⁵ represents

Or cyclohexylene; B ¹⁶ represents methylene; B ¹⁷ represents phenyl or cyclohexylene; B ¹⁸ represents hydrogen or heptyl.

式(2-8-1)

式(2-8-2)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).

Formula (2-8-1)

Formula (2-8-2)

式(2-9)

式(2-10)

式(2-11)

式(2-12)

式(2-13)

式(2-14)

式(2-15)

式(2-16)

式(2-17)

式(2-18)

式(2-19)

式(2-20)

式(2-21)

式(2-22)

式(2-23)

式(2-24)

式(2-25) 式(2-17)至式(2-25)中，B¹⁹ 表示碳數為1至10的烷基或碳數為1至10的烷氧基；B²⁰ 表示氫、碳數為1至10的烷基或碳數為1至10的烷氧基。Other diamine compounds represented by formula (2-9) to formula (2-25) are shown below.

Formula (2-9)

Formula (2-10)

Formula (2-11)

Formula (2-12)

Formula (2-13)

Formula (2-14)

Formula (2-15)

Formula (2-16)

Formula (2-17)

Formula (2-18)

Formula (2-19)

Formula (2-20)

Formula (2-21)

Formula (2-22)

Formula (2-23)

Formula (2-24)

Formula (2-25) In formula (2-17) to formula (2-25), B ¹⁹ represents an alkyl group having 1 to 10 carbons or an alkoxy group having 1 to 10 carbons; B ²⁰ represents hydrogen, An alkyl group having 1 to 10 carbons or an alkoxy group having 1 to 10 carbons.

Specific examples of other diamine compounds (b1-4) may also include 3,3'-diaminochalcone (3,3'-diaminochalcone), 4,4'-diaminochalcone (4,4 '-diaminochalcone), 3,4'-diaminochalcone (3,4'-diaminochalcone) or 3,4-diaminochalcone (3,4-diaminochalcone) have chalcone (chalcone) Structure of diamine compounds; 3,3'-diaminostilbene (3,3'-diaminostilbene), 4,4'-diaminostilbene (4,4'-diaminostilbene), 4, 4'-diaminostilbene-2,2'-sulfonic acid (4,4'-diaminostilbene-2,2'-sulfonic acid) or 4,4'-bis(4-amino-1-naphthalene) Azo)-2,2'-stilbene sulfonic acid (4,4'-bis(4-amino-1-naphthylazo)-2,2'-stilbene sulfonic acid) ) Structure of diamine compounds; 1,2-diamino anthraquinone (1,2-diamino anthraquinone), 1,4-diamino anthraquinone (1,4-diamino anthraquinone), 1,5-diamino anthraquinone Anthraquinone (1,5-diamino anthraquinone) or 1,4-diamino anthraquinone-2,3-dicyano-9,10-anthraquinone (1,4-diamino anthraquinone-2,3-dicyano-9 , 10-anthraquinone) and other diamine compounds with anthraquinone structure; or 3,6-diaminocarbazole and other diamine compounds with carbazole structure.

Specific examples of other diamine compounds (b1-4) preferably include 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenyl Methane, 4,4'-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'-methylene bis(cyclohexylamine), 1,4-diaminocyclohexane, from formula (2-1-1 ), the diamine compound represented by the formula (2-1-2), the diamine compound represented by the formula (2-2-1), the diamine represented by the formula (2-2-11) Compound, p-diaminobenzene, m-diaminobenzene, o-diaminobenzene, diamine compound represented by formula (2-8-1), 3,3'-diaminochalcone or 4,4'-Diamino stilbene, etc.

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

Based on the usage amount of the diamine compound (b1) being 100 mol parts, the usage amount of other diamine compounds (b1-4) may be 0 mol parts to 70 mol parts, preferably 0 mol parts to 60 mol parts The ear portion is more preferably 0 mol portion to 50 mol portion. Method for preparing polymer (A-1) Method for preparing polyamide acid polymer

The method for preparing the polyamide acid polymer is to first dissolve the first mixture in a solvent, where the first mixture includes the tetracarboxylic dianhydride compound (a1) and the diamine compound (b1), and is heated at 0°C to 100°C. The polycondensation reaction proceeds at temperature. After reacting for 1 hour to 24 hours, the above reaction solution is distilled under reduced pressure with an evaporator to obtain a polyamide acid polymer. Alternatively, the above reaction solution is poured into a large amount of poor solvent to obtain a precipitate. Next, the precipitate is dried by means of reduced pressure drying to obtain a polyamide acid polymer. Based on the usage amount of the tetracarboxylic dianhydride compound (a1) being 100 mol parts, the usage amount of the diamine compound (b1) may be 20 mol parts to 200 mol parts, preferably 30 mol parts to 120 mol parts Ear parts.

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the following liquid crystal alignment agent, and the solvent used in the polycondensation reaction is not particularly limited, as long as it can dissolve the reactants and products. Specific examples of solvents include (1) aprotic polar solvents, such as: N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), N,N-dimethylacetamide, N,N -Dimethylformamide, dimethyl sulfide, γ-butyrolactone, tetramethylurea or hexamethylphosphoric triamine and other aprotic polar solvents; (2) Phenolic solvents, such as meta-methyl Phenolic solvents such as phenol, xylenol, phenol, or halogenated phenols; or a combination of the above solvents. However, the present invention is not limited to this, and the solvent may further include other suitable solvents. Based on the total usage amount of the first mixture being 100 parts by weight, the usage amount of the solvent used in the polycondensation reaction may be 200 parts by weight to 2000 parts by weight, preferably 300 parts by weight to 1800 parts by weight.

In the polycondensation reaction, an appropriate amount of poor solvent can be used in combination with the solvent, and the poor solvent will not cause the precipitation of the polyamide acid polymer. Specific examples of poor solvents 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, two oxalates 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, ethyl 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-mentioned poor solvents. However, the present invention is not limited to this, and the poor solvent may further include other suitable solvents. Based on the total usage amount of the first mixture being 100 parts by weight, the usage amount of the poor solvent may be 0 parts by weight to 60 parts by weight, preferably 0 parts by weight to 50 parts by weight. Polyimide polymer

The method for preparing the polyimide polymer is to first dissolve the first mixture in a solvent, where the first mixture includes a tetracarboxylic dianhydride compound (a1) and a diamine compound (b1), and undergoes a polycondensation reaction to form Polyamide acid polymer. Then, in the presence of a dehydrating agent and a catalyst, further heating and dehydration and ring-closing reaction are carried out, so that the amide functional group in the polyamide acid polymer is converted into an amide functional group (ie, amide acid) through the dehydration ring-closing reaction. Amination) to obtain a polyimide polymer.

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

In order to obtain a better degree of imidization of the polyamide acid polymer, the operation 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 polyamide acid polymer is reduced. However, if the operating temperature of the dehydration and ring-closure reaction is higher than 200°C, the weight average molecular weight of the obtained polyimide polymer is low.

The range of the imidization rate of the polymer (A-1) is generally 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, and specific examples of the acid anhydride compounds include acetic anhydride, propionic anhydride, trifluoroacetic anhydride or a combination thereof. Based on 1 mol part of the polyamide acid polymer, the amount of the dehydrating agent used may be 0.01 mol part to 20 mol part. Specific examples of the catalyst used in the dehydration ring-closure reaction include (1) pyridine compounds, such as pyridine, collidine, or lutidine; (2) tertiary amine compounds, such as tris Tertiary amine compounds such as ethylamine; or a combination of the above-mentioned compounds. Based on the usage amount of the dehydrating agent being 1 mol part, the usage amount of the catalyst may be 0.5 mol part to 10 mol part. Polyimide block copolymer

Polyimide-based block copolymers include polyimide block copolymers, polyimide block copolymers, polyimide-polyimine block copolymers, or the above-mentioned copolymers The combination.

The method for preparing polyimide-based block copolymers is preferably to first dissolve the starting material in a solvent and perform a polycondensation reaction, wherein the starting material includes at least one polyimide 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 materials include the tetracarboxylic dianhydride compound (a1) and the diamine compound (b1) used in the preparation of the polyamide acid polymer, and the solvent used in the polycondensation reaction can be used in the following liquid crystal alignment agent The solvent is the same, so I won’t repeat it here.

Based on the usage amount of the starting material being 100 parts by weight, the usage amount of the solvent used in the polycondensation reaction may be 200 parts by weight to 2000 parts by weight, preferably 300 parts by weight to 1800 parts by weight. 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 polyimide polymers with different end groups and different structures; (2) two kinds of polyimide polymers with different end groups and different structures; 3) Polyamide acid polymers and polyimide polymers with different end groups and different structures; (4) Polyamide acid polymers, tetracarboxylic dianhydride compounds and diamine compounds, of which tetracarboxylic acid At least one of the dianhydride compound and the diamine compound is different in structure from the tetracarboxylic dianhydride compound and the diamine compound used to form the polyamide acid polymer; (5) polyimide polymer, tetracarboxylic acid Acid dianhydride compounds and diamine compounds, 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) Polyamide acid polymer, polyimide polymer, tetracarboxylic dianhydride compound and diamine compound, wherein at least one of the tetracarboxylic dianhydride compound and diamine compound is polymerized with the polyamide acid The structure of the tetracarboxylic dianhydride compound and the diamine compound used in the polyimide polymer is different; (7) the two structurally different polyimide polymers, the tetracarboxylic dianhydride compound and the two Amine compounds; (8) Two kinds of polyimide polymers with different structures, tetracarboxylic dianhydride compounds and diamine compounds; (9) Two kinds of polyimide polymers with different structure and end groups are acid anhydride groups (10) Two kinds of polyamide acid polymers and tetracarboxylic dianhydride compounds whose end groups are amine groups and have different structures; (11) Two kinds of end groups are acid anhydride groups and have different structures Polyimide polymer and diamine compound; or (12) Two kinds of polyimide polymer and tetracarboxylic dianhydride compound whose terminal groups are amine groups and have different structures.

In the range that does not affect the efficacy of the present invention, the polyamide acid polymer, polyimide polymer and polyimine-based block copolymer may preferably be terminal-modified polymers with molecular weight adjustment first. By using end-modified polymers, the coating performance of the liquid crystal alignment agent can be improved. The method of preparing the terminal modified polymer can be prepared by adding a monofunctional compound while the polycondensation reaction of the polyamide acid polymer is carried out. Specific examples of monofunctional compounds include (1) monobasic acid anhydrides, such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic 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-eicosanamine; (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 to this, and the monofunctional compound may further include other suitable monofunctional compounds.

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

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

The tetracarboxylic dianhydride compound (a2) is not particularly limited, and may be the same or different from 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), diamine compound (b1-3) or diamine compound (b1-4) in the above 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 the polymer (A-1) and the polymer (A-2) being 100 parts by weight, the usage amount of the polymer (A-1) can be 5 parts by weight to 70 parts by weight , Preferably 10 parts by weight to 60 parts by weight, more preferably 10 parts by weight to 50 parts by weight. Solvent (B)

Specific examples of the solvent (B) include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactone, 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, ethylene glycol n-butyl ether (Ethylene glycol n-butyl ether), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol two Ethyl 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-dimethyl acetamide, N,N-dimethyl acetamide, 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 to this, and the solvent (B) may further include other suitable solvents. The solvent (B) can be used singly or in combination of multiple types.

When the liquid crystal alignment agent includes the polymer (A-1) and the solvent (B), the usage amount based on the polymer (A-1) is 100 parts by weight, and the usage amount of the solvent (B) can be 1000 parts by weight to 3,500 parts by weight Parts, preferably 1000 parts by weight to 3200 parts by weight, more preferably 1000 parts by weight to 3000 parts by weight.

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

In the range that does not affect the efficacy of the present invention, the liquid crystal alignment agent may optionally add an additive (C). The additive (C) may be an epoxy compound, a silane compound having a functional group, or a combination thereof. The function of the additive (C) is to improve the adhesion of the liquid crystal alignment film to the surface of the substrate. The additives (C) can be used alone or in combination of multiple types.

Specific examples of epoxy compounds 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 two Glycidyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxypropyl-m-xylene diamine , 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodi Phenylmethane, N,N-diglycidyl-p-glycidoxyaniline, 3-(N-allyl-N-glycidoxypropyl)aminopropyltrimethoxysilane or 3- (N,N-Diepoxypropyl)aminopropyltrimethoxysilane or a combination thereof. However, the present invention is not limited to this, and the epoxy compound may further include other suitable epoxy compounds.

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

Specific examples of the silane compound having a functional group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyl Propyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyl two Methoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane , N-ethoxycarbonyl-3-aminopropyl triethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N-trimethoxysilylpropyl triethylenetriamine , 10-Trimethoxysilyl-1,4,7-triazedane, 10-triethoxysilyl-1,4,7-triazedane, 9-trimethoxysilyl-3, 6-Diazinonyl acetate, 9-triethoxysilyl-3,6-diazenyl 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(oxyethylene)-3-aminopropyltriethoxysilane, or a combination thereof. However, the present invention is not limited to this, and the silane compound having functional groups may further include other suitable silane compounds having functional groups.

Based on the usage amount of the polymer (A-1) being 100 parts by weight, the usage amount of the silane compound is generally 10 parts by weight or less, preferably 0.5 to 10 parts by weight. > 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: Add the solvent (B) to polymer (A-1) or a mixture of polymer (A-1) and polymer (A-2) at a temperature of 0°C to 200°C, and optionally Add additive (C); then continue to stir with a stirring device until it is 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 15 cps to 35 cps, preferably 17 cps to 33 cps, more preferably 20 cps to 30 cps. > 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, coating a liquid crystal alignment agent on a substrate to form a coating film, and irradiating the coating film with polarized or non-polarized ultraviolet rays in a direction inclined with respect to the coating film surface; or A method of irradiating the coating film with polarized ultraviolet rays in a direction perpendicular to the film surface, thereby imparting liquid crystal alignment energy to the coating film.

First, the liquid crystal alignment agent of the present invention is coated on the transparent conductive layer of the substrate provided with the patterned transparent conductive film by an appropriate coating method such as a roll coating method, a spin coating method, a printing method or an ink-jet method (ink-jet). One side of the membrane. 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. The conditions of the pre-bake treatment are, for example, at a temperature of 40°C to 120°C for 0.1 to 5 minutes. The temperature of the post-baking treatment may be 120°C to 300°C, preferably 150°C to 250°C. The time for the post-baking treatment may be 5 to 200 minutes, more preferably 10 to 100 minutes. The 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 and soda lime glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether or polycarbonate, etc. The formed transparent substrate, etc.

The transparent conductive film may be used Naisai (a NESA) made of SnO ₂ is formed by a film or an indium tin oxide In ₂ O ₃ -SnO ₂ formed (Indium Tin Oxide, ITO) film. In order to form these transparent conductive film patterns, a photo-etching technique (photo-etching), a method of using a mask when forming a transparent conductive film, and the like can be used.

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

Next, the coating film is irradiated with polarized or non-polarized ultraviolet rays to impart a liquid crystal alignment ability, and a liquid crystal alignment film is formed from the coating film. Here, the radiation may use, for example, ultraviolet rays and visible light including light with a wavelength of 150 to 800 nm, and preferably ultraviolet rays including light with a wavelength of 300 to 400 nm. 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, and in order to provide a pretilt angle, it may be irradiated from an oblique direction. On the other hand, when irradiating non-polarized radiation, it is necessary to irradiate from a direction oblique to the surface of the coating film.

As the 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 aforementioned preferable wavelength range can be obtained by a method of using the aforementioned light source together with, for example, a filter, a diffraction grating, and the like.

The radiation dose is preferably 1 J/m ² or more and less than 10000 J/m ² , and more preferably 10 J/m ² to 3000 J/m ² . In addition, when imparting liquid crystal alignment ability to a coating film formed of a conventionally known liquid crystal alignment agent by a photo-alignment method, a radiation irradiation dose of ^{10,000 J/m 2 or more is required.} However, if the liquid crystal alignment agent of the present invention is used, even if the radiation exposure in the photo-alignment method is 3000 J/m ² or less, further 1000 J/m ² or less, and still further 300 J/m ² or less, it can be Gives good liquid crystal alignment ability, thereby helping to reduce the manufacturing cost of liquid crystal display elements. > Method of manufacturing 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 manufactured as follows.

Prepare two substrates on which the liquid crystal alignment film is formed as described above, and arrange liquid crystal between the two substrates to produce a liquid crystal cell. In order to manufacture a liquid crystal cell (cell), for example, the following two methods can be cited.

The first method: First, the two substrates are arranged opposite each other with a gap (cell gap), so that the respective liquid crystal alignment films face each other; the peripheral parts of the two substrates are bonded together using a sealant; The liquid crystal is injected into the cell gap 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 One Drop Fill (ODF). First, apply an ultraviolet curable sealing material, for example, to a predetermined position on one of the two substrates forming the liquid crystal alignment film; drop liquid crystal on the liquid crystal alignment film; then, glue the other substrate so that the liquid crystal alignment film faces each other. Next, the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealant, whereby liquid crystal cells can be produced.

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

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

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

Specific examples of liquid crystals include nematic liquid crystals, disc-shaped 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 and phenylcyclohexane-based liquid crystals ( phenyl cyclohexane-based liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane-based liquid crystals, pyrimidine-based liquid crystals, 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 can be further added to the aforementioned liquid crystal; 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.

On the other hand, in the case of vertical alignment type liquid crystal cells, specific examples of nematic liquid crystals with negative dielectric anisotropy preferably include dicyanobenzene-based liquid crystals and pyridazine-based liquid crystals. (Pyridazine-based liquid crystals), Schiff base-based liquid crystal, azoxy-based liquid crystals, biphenyl-based liquid crystals, phenyl ring Phenyl cyclohexane-based liquid crystals or a combination thereof.

The polarizing plate used on the outside of the liquid crystal cell can be a polarizing film called "H film" which is formed by sandwiching a protective film of cellulose acetate to stretch and align polyvinyl alcohol while absorbing iodine. Polarizing plate or polarizing plate formed by the H film itself.

The liquid crystal display element of the present invention manufactured in this way has excellent display performance, and the display performance does not deteriorate even if it is 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. 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 transparent materials and other materials, wherein the transparent materials include non-alkali glass, soda lime glass, hard glass (Peles glass), quartz glass, and polyethylene used in liquid crystal display devices. Terephthalate, polybutylene terephthalate, polyether 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 material of the first conductive film 114 and the second conductive film 124 is 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 can 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 the liquid crystal molecules in the liquid crystal cell 130. Preparation example of diamine compound (b1-1)

Hereinafter, Preparation Example 1 to Preparation Example 6 of the diamine compound (b1-1) will be described. Preparation Example 1

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

Put 105 g of hydroquinone, 135 g of potassium carbonate (K ₂ CO ₃ ) and 700 ml of acetonitrile (ACN) into a 3-liter four-necked flask, stir and raise the temperature to 80°C. Then, drop a mixed solution of 100 g of 4,4,4-trifluorobutyl methanesulfonate (4,4,4-trifluorobutyl methanesulfonate) and 500 ml of acetonitrile into the four-neck flask. After dripping, keep the temperature at 80°C for 4 hours. Next, 190 g of 25 wt% sodium hydroxide aqueous solution was added, and refluxed at 80°C for 30 minutes. Then, 415 ml of water was added, and the temperature was maintained at 80°C for 1 hour. After the reaction is completed, filtration is performed, and the filtered filtrate is collected and drained, and then separated by column chromatography to obtain about 65 g of R1OH solid.

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

Then, 64 grams of R3A solid and 560 milliliters of dimethylformamide (DMF) were placed in a 3-liter three-necked flask and stirred to dissolve, and then 150 grams of Potassium peroxymonosulfate (Oxone) was added. And react at room temperature for 3 hours. After the reaction was completed, the solution was drained, and the solid was washed three times with 1,300 ml of water. After that, it was washed once with 1300 ml of methanol. The washed solid was collected and dried under vacuum to obtain about 55 g of R3B solid.

Next, 67 g of R3B solid, 60 g of 2-(N,N-di-third 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 5-liter four-necked flask and stirred. Add 40 grams of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) during the stirring process, and after the addition, the temperature is raised to 40°C, and the temperature is kept at 40°C. The reaction was refluxed for 6 hours. After the completion of the reaction, it was extracted twice with 2500 ml of water, the organic layer was collected and the water was removed with anhydrous magnesium sulfate and then filtered and drained. The solid obtained after being sucked dry was heated to dissolve with 370 g of isopropanol, and allowed to stand for crystallization after cooling. The crystals were collected by filtration and sucked dry to obtain about 100 g of R4B solid.

Then, 100 g of R4B solid and 1,400 ml of dichloromethane were put into a four-necked flask with a capacity of 5 liters and stirred. During stirring, 135 g of 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, 1600 ml of ethyl acetate was poured into the flask and stirred. Then, 970 ml of 2.5M sodium hydroxide aqueous solution was poured into the flask and stirred for 30 minutes. Next, pour the solution into a 2 liter separatory bottle, let it stand and collect the upper organic layer. Subsequently, it was extracted 4 times with 970 ml of 2.5 M sodium hydroxide aqueous solution, and 10 times with 970 ml of water. The extracted organic layer was filtered and drained with anhydrous magnesium sulfate, and then washed with 200 g of methanol, filtered and drained to collect the solid. The solid was then heated to dissolve with 300 g of acetonitrile, and allowed to stand for crystallization 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 formula (I-1)). 1-1). Preparation Example 2

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

Put 65 grams of 4-methanylcinnamic acid, 100 grams of 4-(4-heptylcyclohexyl)phenol (4-(4-heptylcyclohexyl)phenol, 7CPO) and 4.5 grams of 4-dimethylaminopyridine into the volume It is a 2-liter four-necked flask. Then add 730 ml of dichloromethane into the four-necked flask, and add 84 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) during the stirring process. . Thereafter, the reaction was carried out at 40°C for 6 hours. After the reaction is over, water is added for extraction, the organic layer is collected and the water is removed with anhydrous magnesium sulfate, and then filtered and drained. The solid obtained after suction was dried, and then heated and washed with isopropanol, and then filtered and collected the solid to obtain about 130 g of R3CHO solid.

Next, 80 g of R3CHO solid and 620 ml of dimethylformamide were put into a three-necked flask with a capacity of 1 liter 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 drained to obtain a solid, and the solid was washed with pure water and methanol. After washing, vacuum drying was performed to obtain about 75 g 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 dropped, and after the dropping, the temperature was raised to 80° C. and reacted for 5 minutes. Next, the temperature was lowered to 40°C. Dissolve 26.5 g of 2,4-dinitrophenyl-ethanol (2,4-dinitrophenyl-ethanol) and 0.6 g of 4-dimethylaminopyridine in 12.4 g of Pyridine and drop them into the above three-necked flask Inside, continue to stir for 12 hours. Thereafter, the temperature was raised to 60°C, and 20 ml of methanol was added, and the temperature was continuously maintained at 45°C for 1 hour. Finally, the solvent was drained, and then washed with methanol to obtain about 57 g of precipitated R3DiNO-L solid.

Next, 48.4 grams of R3DiNO-L solid and 440 milliliters of anisole were placed in a three-liter four-necked flask and stirred. In addition, prepare 186 milliliters of pure water and 7.7 grams of Pt/C into a beaker with a capacity of 2 liters and stir, then add 0.13 grams of ammonium metavanadate (NH ₄ VO ₃ ) and 0.7 grams of hypophosphorous acid (H ₃ PO ₂ ) Aqueous solution (50 wt%), prepared as a mixed solution. Pour the above-mentioned mixture into a four-necked flask and raise the temperature to 65°C. Subsequently, 30 g of hydrazine (NH ₂ NH ₂ ) was dropped. After all the drops were dropped, the temperature was raised to 80° C. and reacted 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, and then filtered and collected the solid 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 formula (I-3) (hereinafter referred to as "diamine compound (b1-1-3)") was synthesized according to the following synthetic route 3. [Synthesis Route 3]

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

Next, 270 grams of R5THP solids, 65 milliliters of methanol and 1200 milliliters of dichloromethane were put into a 2-liter four-necked flask and stirred. During the stirring, 170 grams of 12 wt% p-toluenesulfonic acid acetic acid solution was dropped. After the addition, react at room temperature for 2 hours. After the reaction, 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 solids, 36 grams of 4-methanylcinnamic 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 were added and stirred. Subsequently, 47.3 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) was added dropwise while stirring. After the addition, react at 40°C for 8 hours. After the reaction is over, water is added for extraction, the organic layer is collected and the water is removed with anhydrous magnesium sulfate, and then filtered and drained. The solid obtained after draining is washed with isopropanol and heated. After washing, the solid was collected by filtration and vacuum dried to obtain about 87 g of R5BCHO solid.

Next, 87 g of R5BCHO solid and 583 ml of dimethylformamide were put into a 3-necked flask with a capacity of 1 liter and stirred to dissolve. Then add 160 g of potassium hydrogen persulfate (Oxone), and react at room temperature for 3 hours. After the reaction was completed, the solution was drained, 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 solid was collected and dried under vacuum to obtain about 44 g of R5BCOOH solid.

Then, 44 grams of R5BCOOH solid, 30 grams of 2-(N,N-di-third butoxycarbonyl-2,4-diaminophenyl)-1-ethanol (t-Boc DPE), 2 grams of 4-bis Methylaminopyridine 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 refluxed at room temperature for 6 hours. After the reaction was completed, it was extracted with 350 ml of water, the organic layer was collected, and the water was removed with anhydrous magnesium sulfate, and then filtered and drained. The solid obtained after being sucked dry was heated to dissolve with isopropanol, and allowed to stand for crystallization after cooling. The crystals were collected by filtration and drained to obtain about 70 g of R5BBoc solid.

Next, 50 g of R5BBoc solid and 1200 ml of dichloromethane were put into a 5-liter four-necked flask and stirred. During stirring, 62 g of tin(II) trifluoromethanesulfonate (Sn(OTf) ₂ ) was added. After the addition, the temperature was raised to 40°C in 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. Then, another 450 ml of 2.5M sodium hydroxide aqueous solution was poured into the flask and stirred for 30 minutes. Next, pour the solution into a 2 liter separatory bottle, let it stand and collect the upper organic layer. Subsequently, it was extracted 4 times with 450 ml of 2.5 M sodium hydroxide aqueous solution, and then with 200 ml of water 4 times. The extracted organic layer was filtered and drained with anhydrous magnesium sulfate, and then washed with methanol, filtered and drained to collect the solid. The solid was then heated to dissolve with acetonitrile, and allowed to stand for crystallization 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 formula (I-3)). 3). Preparation Example 4

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

Put 285 grams of 4-hydroxycinnamic acid, 293 grams of dihydropyran (3,4-Dihydro-2H-pyran, DHP) and 1,800 ml of dichloromethane into a 3-liter four-necked flask Inside and stir evenly, and in the process of stirring, add 20.6 grams of trifluoroacetic acid (2,2,2-Trifluoroacetic acid, TFA). Thereafter, the reaction was carried out at 40°C for 6 hours. After the reaction, the solid was collected by suction filtration. The collected solid was washed with 1300 g of methanol at 50° C., and then the solid was dried to obtain about 345 g of R4-COOH solid.

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

Then, 110 grams of R4-7CPO solid and 670 milliliters of dichloromethane were put into a 3 liter flask and stirred. During the stirring process, 140 grams of 12 wt% p-toluenesulfonic acid acetic acid solution was dropped. After that, the reaction was carried out at room temperature for 2 hours. After the reaction is over, a little methanol is added. Subsequently, the solvent was drained, and extracted with dichloromethane and saturated sodium bicarbonate aqueous solution, and finally extracted with water to collect the organic layer. The organic layer was filtered and sucked dry with anhydrous magnesium sulfate to remove water, and about 80 g of R4-OH solid was obtained.

Next, 20.7 g of 2,4-dinitrophenylethanol and 96.5 g of toluene were placed in a three-necked flask with a capacity of 0.5 liters, and 0.1 g of dimethylformamide was added, and the temperature was raised to 75°C. Then, slowly add 12 grams of sulphurous chloride. After the addition, keep the temperature at 80°C and continue the reaction. After the solution turns yellow and clear, the temperature is reduced to 30°C. 46 g of R4-OH solid and 0.56 g of 4-dimethylaminopyridine were dissolved in 22 g of pyridine, and then dropped into a three-necked flask. After the addition, after stirring for 12 hours at room temperature, the temperature was raised to 60°C and 80 g of methanol was added. After holding the temperature at 45°C for 1 hour, the solvent was drained to obtain about 44 g of R4-DiNO 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 five-liter four-necked flask, and 950 grams of water and 1050 grams of ethyl acetate were added to the flask. (EA), stir evenly, heat up to 70°C, and react at 70°C for 2 hours. After the reaction, filter through Celite at 70°C, remove the water layer after the filtrate is separated, collect the organic layer, remove water with anhydrous magnesium sulfate, filter and drain, and obtain about 35 grams of RPADA4 solid (ie, The diamine compound b1-1-4 represented by formula (I-6)). Preparation Example 5

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

Put 65 grams of 4-methanylcinnamic acid, 100 grams of 4-(4-heptylcyclohexyl)phenol (7CPO) and 4.5 grams of 4-dimethylaminopyridine into a four-necked flask with a capacity of 2 liters. Then add 730 ml of dichloromethane into the four-necked flask, and add 84 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) during the stirring process. . Thereafter, the reaction was carried out at 40°C for 6 hours. After the reaction is over, water is added for extraction, the organic layer is collected and the water is removed with anhydrous magnesium sulfate, and then filtered and drained. The solid obtained after draining is then heated and cleaned with isopropanol. After that, the solid was filtered and collected, and about 130 g of R3CHO solid was obtained.

Next, 80 g of R3CHO solid and 620 ml of dimethylformamide were placed in a three-necked flask with a capacity of 1 liter 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 drained to obtain a solid, and the solid was washed with pure water and methanol. After washing, the solid was collected by filtration and vacuum dried to obtain about 75 g of R3COOH as a pale yellow solid.

Then, 68.5 g of R3COOH light yellow solid, 28.1 g of 2,4-dinitrophenol, 3.73 g of 4-dimethylaminopyridine and 1,250 ml of 0.125M 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 hydrochloric acid (EDC.HCl) was added. Thereafter, the reaction was refluxed at 40°C for 6 hours. After the reaction is over, water is added for extraction, the organic layer is collected and the water is removed with anhydrous magnesium sulfate, and then filtered and drained. The solid obtained after draining is washed with isopropanol and heated. After washing, the solid was collected by filtration and vacuum dried to obtain about 50 g of R3DiNO solid.

Next, put 28.3 g of R3DiNO solid and 270 ml of anisole into a 2-liter four-neck flask and stir; in addition, prepare 115 ml of pure water and 6 g of Pt/C into a 2-liter beaker and stir. Subsequently, 0.08 g of ammonium metavanadate and 0.42 g of hypophosphorous acid aqueous solution (50 wt%) were added to prepare a mixed solution. Pour the above-mentioned mixture into a four-necked flask and raise the temperature to 65°C. Subsequently, 18.4 g of hydrazine was dropped, and after all the drops were dropped, the temperature was raised to 80° C. and reacted 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, and then filtered and collected the solid to obtain about 10 g of RPADA3M solid (ie, the diamine compound b1-1-5 represented by formula (I-7)). Preparation Example 6

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

Put 45 grams of 4-methanylcinnamic acid, 100 grams of 5α-cholestane-3β-ol (5α-Cholestan-3β-ol) and 3.2 grams of 4-dimethylaminopyridine into the four Inside the flask. Then add 520 ml of dichloromethane into the four-necked flask, and add 60 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloric acid (EDC.HCl) during the stirring process. . Thereafter, the reaction was carried out at 40°C for 6 hours. After the reaction is over, water is added for extraction, the organic layer is collected and the water is removed with anhydrous magnesium sulfate, and then filtered and drained. The solid obtained after draining is then heated and cleaned with isopropanol. After that, the solid was filtered and collected, and about 120 g of R6CHO solid was obtained.

Next, 80 g of R6CHO solid and 500 ml of dimethylformamide were placed in a three-necked flask with a capacity of 1 liter 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 the reaction was completed, the solvent was drained to obtain a solid, and the solid was washed with pure water and methanol. After washing, the solid was collected by filtration and vacuum dried to obtain about 60 g of R6COOH solid.

Then, 120 grams of R6COOH solid and 200 milliliters of toluene were placed in a 3-necked flask with a capacity of 1 liter and stirred to dissolve, then 0.2 grams of dimethylformamide was added, and the temperature was raised to 75°C. Subsequently, 23 g of sulphurous chloride was slowly dropped, and after the dropping, the temperature was raised to 80°C and reacted 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 stirring was continued for 12 hours. Thereafter, the temperature was raised to 60°C, and 150 ml of methanol was added, and the temperature was continuously maintained at 45°C for 1 hour. Finally, the solvent was drained, and then washed with methanol to obtain about 90 g of precipitated R6DiNO solid.

Next, put 50 g of R6DiNO solid and 400 ml of anisole into a four-necked flask with a capacity of 1 liter and stir; in addition, prepare 160 ml of pure water and 10 g of Pt/C in a beaker with a capacity of 2 liters and stir. Then, 0.12 g of ammonium metavanadate and 0.6 g of hypophosphorous acid aqueous solution (50 wt%) were added to prepare a mixed solution. Pour the above-mentioned mixture into a four-necked flask and raise the temperature to 65°C. Subsequently, 26 g of hydrazine was dropped, and after all the drops, the temperature was raised to 80° C. and reacted 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, and then filtered and collected the solid to obtain about 20 g of RPADA6 solid (ie, diamine compound b1-1-6 represented by formula (I-9)). Preparation example of diamine compound (b1-2)

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

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

The following describes synthesis example A-1-1-1 to synthesis example A-1-1-6, synthesis example A-1-2-1 to synthesis example A-1-2-6 of polymer (A-1), 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 are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is 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 other diamine compounds (b1- 4-1) 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 acid dianhydride (abbreviated as a1-1) and 20 g of NMP were added, and reacted at room temperature for 2 hours. After the reaction is over, the reaction solution is 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 are prepared by the same steps as Synthesis Example A-1-1-1, with the differences It lies in: changing the type of polymer raw materials and their usage (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 by the same steps as Synthesis Example A-1-1-1, but the difference lies in: changing the type of polymer material and its usage (such as 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 are prepared by the same steps as Synthesis Example A-1-1-1, but the difference lies in: changing the type of polymer material and Usage (as shown in Table 3).

式(I-1) b1-1-2

式(I-2) b1-1-3

式(I-3) b1-1-4

式(I-6) b1-1-5

式(I-7) b1-1-6

式(I-9) b1-2-1

 式(II-10) b1-2-2

式(II-18) b1-2-3

 式(II-24) b1-2-4

 式(II-22) b1-2-5

 式(II-26) b1-3-1

式(III-1) b1-3-2

式(III-2) b1-3-3

式(III-3) b1-3-4

式(III-4) b1-3-5

式(III-5) b1-3-6

式(III-6) b1-4-1 對-二胺基苯（p-diaminobenzene） b1-4-2 2,2’-二甲基-4,4’-二胺基聯苯（2,2’-dimethyl-4,4’-diamino diphenyl） b1-4-3 4,4’-亞甲基雙(環己基胺) （4,4’-methylenebis(cyclohexylamine)） b1-4-4 1,4-二胺基環己烷（1,4-diaminocyclohexane） b1-4-5 3,3’-二胺基查耳酮（3,3’-diaminochalcone） b1-4-6

b1-4-7

b1-4-8

b1-4-9

式(2-1-1) a2-1 2,3,5-三羧基環戊基醋酸二酐（2,3,5-tricarboxycyclopentylacetic acid dianhydride） a2-2 1,2,3,4-環丁烷四羧酸二酐（1,2,3,4-cyclobutane tetracarboxylic acid dianhydride） a2-3 苯均四羧酸二酐（pyromellitic dianhydride） b2-1 對-二胺基苯（p-diaminobenzene） b2-2 2,2’-二甲基-4,4’-二胺基聯苯（2,2’-dimethyl-4,4’-diamino diphenyl） b2-3 4,4’-亞甲基雙(環己基胺) （4,4’-methylenebis(cyclohexylamine)） b2-4 1,4-二胺基環己烷（1,4-diaminocyclohexane） The compounds corresponding to the numbers in Tables 1 to 3 are shown below. Abbreviation ingredient a1-1 2,3,5-tricarboxycyclopentylacetic acid dianhydride (2,3,5-tricarboxycyclopentylacetic acid dianhydride) a1-2 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride (1,2,3,4-cyclobutane tetracarboxylic acid dianhydride) a1-3 Pyromellitic dianhydride (pyromellitic dianhydride) b1-1-1

Formula (I-1) b1-1-2

Formula (I-2) b1-1-3

Formula (I-3) b1-1-4

Formula (I-6) b1-1-5

Formula (I-7) b1-1-6

Formula (I-9) b1-2-1

Formula (II-10) b1-2-2

Formula (II-18) b1-2-3

Formula (II-24) b1-2-4

Formula (II-22) b1-2-5

Formula (II-26) b1-3-1

Formula (III-1) b1-3-2

Formula (III-2) b1-3-3

Formula (III-3) b1-3-4

Formula (III-4) b1-3-5

Formula (III-5) b1-3-6

Formula (III-6) b1-4-1 P-diaminobenzene b1-4-2 2,2'-dimethyl-4,4'-diamino diphenyl (2,2'-dimethyl-4,4'-diamino diphenyl) b1-4-3 4,4'-methylenebis(cyclohexylamine) (4,4'-methylenebis(cyclohexylamine)) b1-4-4 1,4-diaminocyclohexane (1,4-diaminocyclohexane) b1-4-5 3,3'-diaminochalcone (3,3'-diaminochalcone) b1-4-6

b1-4-7

b1-4-8

b1-4-9

Formula (2-1-1) a2-1 2,3,5-tricarboxycyclopentylacetic acid dianhydride (2,3,5-tricarboxycyclopentylacetic acid dianhydride) a2-2 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride (1,2,3,4-cyclobutane tetracarboxylic acid dianhydride) a2-3 Pyromellitic dianhydride (pyromellitic dianhydride) b2-1 P-diaminobenzene b2-2 2,2'-dimethyl-4,4'-diamino diphenyl (2,2'-dimethyl-4,4'-diamino diphenyl) b2-3 4,4'-methylenebis(cyclohexylamine) (4,4'-methylenebis(cyclohexylamine)) b2-4 1,4-diaminocyclohexane (1,4-diaminocyclohexane)

Table 1 Ingredients (unit: mole%) Synthesis example A-1-1-1 A-1-1-2 A-1-1-3 A-1-1-4 A-1-1-5 A-1-1-6 Tetracarboxylic dianhydride compound (a1) a1-1 100 100 a1-2 100 100 a1-3 100 100 Diamine compound (b1) Diamine compound (b1-1) b1-1-1 50 b1-1-2 60 b1-1-3 70 b1-1-4 80 b1-1-5 90 b1-1-6 100 Diamine compound (b1-2) b1-2-1 b1-2-2 b1-2-3 b1-2-4 b1-2-5 Diamine compound (b1-3) b1-3-1 b1-3-2 b1-3-3 b1-3-4 b1-3-5 b1-3-6 Other diamine compounds (b1-4) b1-4-1 50 30 b1-4-2 30 b1-4-3 20 b1-4-4 10 10 b1-4-5 b1-4-6 b1-4-7 b1-4-8 b1-4-9

Table 1 (continued) Ingredients (unit: mole%) Synthesis example A-1-2-1 A-1-2-2 A-1-2-3 A-1-2-4 A-1-2-5 A-1-2-6 Tetracarboxylic dianhydride compound (a1) a1-1 a1-2 100 100 100 a1-3 100 100 100 Diamine compound (b1) Diamine compound (b1-1) b1-1-1 80 b1-1-2 70 b1-1-3 50 b1-1-4 60 b1-1-5 75 b1-1-6 65 Diamine compound (b1-2) b1-2-1 5 b1-2-2 10 b1-2-3 15 30 b1-2-4 20 b1-2-5 25 Diamine compound (b1-3) b1-3-1 b1-3-2 b1-3-3 b1-3-4 b1-3-5 b1-3-6 Other diamine compounds (b1-4) b1-4-1 20 25 10 b1-4-2 5 b1-4-3 30 b1-4-4 5 b1-4-5 b1-4-6 b1-4-7 b1-4-8 b1-4-9

Table 1 (continued) Ingredients (unit: mole%) Synthesis example A-1-3-1 A-1-3-2 A-1-3-3 A-1-3-4 A-1-3-5 A-1-3-6 Tetracarboxylic dianhydride compound (a1) a1-1 100 100 100 a1-2 100 100 a1-3 100 Diamine compound (b1) Diamine compound (b1-1) b1-1-1 80 b1-1-2 85 b1-1-3 75 b1-1-4 60 b1-1-5 50 b1-1-6 60 Diamine compound (b1-2) b1-2-1 b1-2-2 b1-2-3 b1-2-4 b1-2-5 Diamine compound (b1-3) b1-3-1 1 b1-3-2 3 b1-3-3 5 b1-3-4 10 b1-3-5 15 b1-3-6 20 Other diamine compounds (b1-4) b1-4-1 14 40 b1-4-2 15 b1-4-3 25 b1-4-4 twenty two 20 b1-4-5 b1-4-6 b1-4-7 b1-4-8 b1-4-9

Table 1 (continued) Ingredients (unit: mole%) Synthesis example A-1-4-1 A-1-4-2 A-1-4-3 A-1-4-4 A-1-4-5 A-1-4-6 Tetracarboxylic dianhydride compound (a1) a1-1 100 a1-2 100 100 100 a1-3 100 100 Diamine compound (b1) Diamine compound (b1-1) b1-1-1 80 b1-1-2 90 b1-1-3 70 b1-1-4 60 b1-1-5 50 b1-1-6 70 Diamine compound (b1-2) b1-2-1 10 b1-2-2 5 b1-2-3 30 b1-2-4 20 b1-2-5 25 10 Diamine compound (b1-3) b1-3-1 5 b1-3-2 10 b1-3-3 5 b1-3-4 20 b1-3-5 5 b1-3-6 10 Other diamine compounds (b1-4) b1-4-1 5 b1-4-2 10 b1-4-3 b1-4-4 10 b1-4-5 b1-4-6 b1-4-7 b1-4-8 b1-4-9

Table 2 Ingredients (unit: mole%) Synthesis example A-2-1 A-2-2 A-2-3 A-2-4 A-2-5 A-2-6 Tetracarboxylic dianhydride compound (a2) a2-1 100 50 a2-2 100 100 100 a2-3 100 50 Diamine compound (b2) b2-1 100 70 10 b2-2 100 20 80 b2-3 100 90 b2-4 10 20

table 3 Ingredients (unit: mole%) Comparative synthesis example A'-1-1 A'-1-2 A'-1-3 A'-1-4 A'-1-5 Tetracarboxylic dianhydride compound (a1) a1-1 100 100 a1-2 100 100 a1-3 100 Diamine compound (b1) Diamine compound (b1-1) b1-1-1 b1-1-2 b1-1-3 b1-1-4 b1-1-5 b1-1-6 Diamine compound (b1-2) b1-2-1 30 b1-2-2 b1-2-3 b1-2-4 b1-2-5 Diamine compound (b1-3) b1-3-1 20 b1-3-2 b1-3-3 b1-3-4 b1-3-5 b1-3-6 Other diamine compounds (b1-4) b1-4-1 50 b1-4-2 30 b1-4-3 b1-4-4 10 10 b1-4-5 50 b1-4-6 60 70 b1-4-7 70 b1-4-8 80 b1-4-9 20 Examples and comparative examples of liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

Hereinafter, 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. 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 (abbreviated as B-1) and 800 parts by weight of ethylene glycol n-butyl ether (abbreviated as In B-2), the liquid crystal alignment agent of Example 1 can be prepared by stirring and mixing at room temperature to dissolve. b. Liquid crystal alignment film and liquid crystal display element

The above-mentioned liquid crystal alignment agent was coated on two glass substrates with conductive films composed of ITO (indium-tin-oxide) using a printer (manufactured by Nippon Photographic Printing Co., Ltd., model S15-036) to form a pre- coating. After that, the glass substrate was placed on a hot plate and pre-baked under 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 glass substrates with liquid crystal alignment films formed thereon were obtained above, one of which was coated with hot pressing glue, and the other was sprinkled with 4 μm spacers. Next, the two glass substrates were bonded together, and a pressure of 10 kg was applied by a heat press, and the heat and pressure bonding was performed under the condition of a temperature of 150°C. Then, a liquid crystal injection machine (manufactured by Shimadzu Corporation, model ALIS-100X-CH) was used for liquid crystal injection. Next, seal the liquid crystal injection port with ultraviolet light hardening glue, and harden the ultraviolet light hardening glue with ultraviolet light, and perform liquid crystal annealing treatment 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.

The liquid crystal display element of Example 1 was evaluated in each evaluation method described later, and the results are shown in Table 4. Example 2 to Example 36

The liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element of Example 2 to Example 36 were prepared separately in the same steps as in Example 1, with the difference that: the types of ingredients and their usage amount were changed, as shown in Table 4. . The liquid crystal display elements prepared in Examples 2 to 36 were evaluated in the following evaluation methods. The results are shown in Table 4. Comparative example 1 to comparative example 8

The liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element of Comparative Example 1 to Comparative Example 8 were prepared separately in the same steps as in Example 1, except that the types of components and the amounts used were changed, as shown in Table 5. . The liquid crystal display elements produced in Comparative Examples 1 to 8 were evaluated in the following evaluation methods. The results are shown in Table 5.

The compounds corresponding to the numbers in Table 4 and Table 5 are as follows. Abbreviation ingredient A-1-1-1 Polymer A-1-1-1 A-1-1-2 Polymer A-1-1-2 A-1-1-3 Polymer A-1-1-3 A-1-1-4 Polymer A-1-1-4 A-1-1-5 Polymer A-1-1-5 A-1-1-6 Polymer A-1-1-6 A-1-2-1 Polymer A-1-2-1 A-1-2-2 Polymer A-1-2-2 A-1-2-3 Polymer A-1-2-3 A-1-2-4 Polymer A-1-2-4 A-1-2-5 Polymer A-1-2-5 A-1-2-6 Polymer A-1-2-6 A-1-3-1 Polymer A-1-3-1 A-1-3-2 Polymer A-1-3-2 A-1-3-3 Polymer A-1-3-3 A-1-3-4 Polymer A-1-3-4 A-1-3-5 Polymer A-1-3-5 A-1-3-6 Polymer A-1-3-6 A-1-4-1 Polymer A-1-4-1 A-1-4-2 Polymer A-1-4-2 A-1-4-3 Polymer A-1-4-3 A-1-4-4 Polymer A-1-4-4 A-1-4-5 Polymer A-1-4-5 A-1-4-6 Polymer A-1-4-6 A'-1-1 Polymer A'-1-1 A'-1-2 Polymer A'-1-2 A'-1-3 Polymer A'-1-3 A'-1-4 Polymer A'-1-4 A'-1-5 Polymer A'-1-5 A-2-1 Polymer A-2-1 A-2-2 Polymer A-2-2 A-2-3 Polymer A-2-3 A-2-4 Polymer A-2-4 A-2-5 Polymer A-2-5 A-2-6 Polymer A-2-6 B-1 N-methyl-2-pyrrolidone (NMP) B-2 Ethylene glycol n-butyl ether B-3 N,N-dimethylacetamide (N,N-dimethylacetamide) C-1 N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenyl methane (N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenyl methane) C-2 N,N-epoxypropyl-p-glycidoxyaniline (N,N-epoxypropyl-p-glycidoxyaniline) Evaluation method > Electric field memory effect >

Based on the method described in " TJScheffer, et.al., J.Appl.Phys., vol.19, 2013 (1980) ", using a liquid crystal evaluation device (CHUO PRECISION INDUSTRIAL CO., LTD.) The model number 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 . Then, it was applied with 60 Hz, 16 volt alternating current and placed on a light emitting diode (LED) backlight. After 36 hours, the pretilt angle was measured again 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. Conversely, the greater the change in the pretilt angle, the worse the electric field memory effect of the liquid crystal display element, and the problem of inability to perform optical alignment may even occur. Pretilt angle change=︱P _m －P _n ︱

The evaluation criteria of the pretilt angle change are as follows: ◎: pretilt angle change≦0.3°; ○: 0.3°<pretilt angle change≦0.6°; △: 0.6°<pretilt angle change≦1.0°; ╳: 1.0°<pretilt angle Change, or unable to perform optical alignment. > Environmental resistance >

The liquid crystal display elements of Example 1 to Example 36 and Comparative Example 1 to Comparative Example 8 were respectively placed in an environment with a temperature of 65° C. and a relative humidity of 85%. After 120 hours, the ion density of the liquid crystal display elements of Example 1 to Example 36 and Comparative Example 1 to Comparative Example 8 were measured by an electrical measuring machine (manufactured by Toyo Co., Model 6254). The test condition is to apply a 1.7 volt voltage and a 0.01 Hz triangle wave 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 volt to 1 volt. The lower the ion density, the better the environmental resistance. Conversely, the higher the ion density, the worse the environmental resistance.

The evaluation criteria of ion density are as follows: ◎: Ion density <20; ○: 20≦Ion density<40; △: 40≦Ion density＜50; ╳: 50≦Ion density.

Table 4 Ingredients (unit: parts by weight) Example 1 2 3 4 5 6 7 8 9 10 11 12 Polymer (A-1) A-1-1-1 100 30 A-1-1-2 100 40 A-1-1-3 100 50 A-1-1-4 100 70 A-1-1-5 100 90 A-1-1-6 100 95 A-1-2-1 A-1-2-2 A-1-2-3 A-1-2-4 A-1-2-5 A-1-2-6 A-1-3-1 A-1-3-2 A-1-3-3 A-1-3-4 A-1-3-5 A-1-3-6 A-1-4-1 A-1-4-2 A-1-4-3 A-1-4-4 A-1-4-5 A-1-4-6 A'-1-1 A'-1-2 A'-1-3 A'-1-4 A'-1-5 Polymer (A-2) A-2-1 70 A-2-2 60 A-2-3 50 A-2-4 30 A-2-5 10 A-2-6 5 Solvent (B) B-1 1200 800 1000 900 850 1500 800 B-2 800 1000 800 1500 300 850 2000 1000 750 B-3 1000 800 100 600 300 500 1500 Additive (C) C-1 C-2 Evaluation results Electric field memory effect ○ ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ Environmental resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

Table 4 (continued) Ingredients (unit: parts by weight) Example 13 14 15 16 17 18 19 20 twenty one twenty two twenty three twenty four Polymer (A-1) A-1-1-1 A-1-1-2 A-1-1-3 A-1-1-4 A-1-1-5 A-1-1-6 A-1-2-1 100 A-1-2-2 100 A-1-2-3 100 A-1-2-4 100 A-1-2-5 100 A-1-2-6 100 A-1-3-1 100 A-1-3-2 100 A-1-3-3 100 A-1-3-4 100 A-1-3-5 100 A-1-3-6 100 A-1-4-1 A-1-4-2 A-1-4-3 A-1-4-4 A-1-4-5 A-1-4-6 A'-1-1 A'-1-2 A'-1-3 A'-1-4 A'-1-5 Polymer (A-2) A-2-1 A-2-2 A-2-3 A-2-4 A-2-5 A-2-6 Solvent (B) B-1 1000 1200 800 1000 1000 1500 B-2 1000 600 1000 800 1500 300 1000 2000 1000 B-3 1000 800 100 600 500 1000 350 1500 Additive (C) C-1 C-2 Evaluation results Electric field memory effect ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ○ ○ ○ ○ Environmental resistance ○ ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎

Table 4 (continued) Ingredients (unit: parts by weight) Example 25 26 27 28 29 30 31 32 33 34 35 36 Polymer (A-1) A-1-1-1 A-1-1-2 A-1-1-3 A-1-1-4 A-1-1-5 A-1-1-6 A-1-2-1 30 A-1-2-2 40 A-1-2-3 A-1-2-4 A-1-2-5 A-1-2-6 A-1-3-1 A-1-3-2 A-1-3-3 60 A-1-3-4 70 A-1-3-5 A-1-3-6 A-1-4-1 100 A-1-4-2 100 A-1-4-3 100 A-1-4-4 100 A-1-4-5 100 95 A-1-4-6 100 90 A'-1-1 A'-1-2 A'-1-3 A'-1-4 A'-1-5 Polymer (A-2) A-2-1 70 5 A-2-2 30 A-2-3 A-2-4 40 A-2-5 60 A-2-6 10 Solvent (B) B-1 800 1000 1200 800 1000 1000 1500 1500 B-2 750 1000 600 1000 800 1500 300 2000 1000 B-3 1000 800 100 600 300 350 Additive (C) C-1 3 2 C-2 1 3 Evaluation results Electric field memory effect ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Environmental resistance ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ ◎ ◎ ◎

table 5 Ingredients (unit: parts by weight) Comparative example 1 2 3 4 5 6 7 8 Polymer (A-1) A-1-1-1 A-1-1-2 A-1-1-3 A-1-1-4 A-1-1-5 A-1-1-6 A-1-2-1 A-1-2-2 A-1-2-3 A-1-2-4 A-1-2-5 A-1-2-6 A-1-3-1 A-1-3-2 A-1-3-3 A-1-3-4 A-1-3-5 A-1-3-6 A-1-4-1 A-1-4-2 A-1-4-3 A-1-4-4 A-1-4-5 A-1-4-6 A'-1-1 100 A'-1-2 100 50 A'-1-3 100 70 A'-1-4 100 80 A'-1-5 100 Polymer (A-2) A-2-1 50 A-2-2 30 A-2-3 20 A-2-4 A-2-5 A-2-6 Solvent (B) B-1 1000 1200 800 1000 1000 B-2 1000 600 1000 800 1500 300 B-3 1000 800 100 600 500 Additive (C) C-1 C-2 Evaluation results Electric field memory effect ╳ ╳ ╳ ╳ ╳ ╳ ╳ ╳ Environmental resistance ╳ ╳ ╳ ╳ ╳ ╳ ╳ ╳ > Evaluation Results >

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

When the usage 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 (Example 7 to Example 12), the liquid crystal alignment film formed by the liquid crystal alignment agent can be made 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 alignment agent includes the diamine compound (b1-2) (Example 13 to Example 18, Example 31 and Example 32), The liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent have a better electric field memory effect.

When the diamine compound (b1) in the polymer (A-1) in the liquid crystal alignment agent includes the diamine compound (b1-3) (Example 19 to Example 24, Example 33, and Example 34), 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 embodiment 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.

In summary, 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 At this time, 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 liquid crystal alignment film and liquid crystal display element.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the relevant technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be determined by the scope of the attached patent application.

100: liquid crystal display element 110: Unit One 112: First substrate 114: The first conductive film 116: The first liquid crystal alignment film 120: Unit 2 122: second substrate 124: second conductive film 126: second liquid crystal alignment film 130: LCD unit

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

100: liquid crystal display element

110: Unit One

112: First substrate

114: The first conductive film

116: The first liquid crystal alignment film

120: Unit 2

122: second substrate

124: second conductive film

126: second liquid crystal alignment film

130: LCD unit

Claims (18)

A diamine compound, which is a diamine compound (b1-1) represented by formula (I):

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

,

,

,

,

,

,

,

,

,

or

, 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 of 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 a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, a halogen atom or a cyano group; R ² represents an organic group represented by formula (IA) or a carbon number of 17 to 40 monovalent organic groups with a steroid skeleton;

Formula (IA) In formula (IA), 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 represents

or

, Where R ¹⁰ and R ¹¹ each independently represent fluorine or methyl, * represents the bonding position; R ⁹ represents hydrogen, fluorine, an alkyl group having 1 to 12 carbons, a fluoroalkyl group having 1 to 12 carbons, carbon An alkoxy group having a number of 1 to 12, an alkoxy group having a carbon number of 1 to 12 substituted by fluorine, -OCH ₂ F, -OCHF ₂ , -OCF ₃ ; a represents an integer from 0 to 2; b, c, and d each independently represents 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; * represents the bonding position; when R ⁴ , R ⁵ , R ^{When there are a plurality of 6} , R ⁷ , R ⁸ , R ¹⁰ or R ¹¹ , each independently represents the same or different groups. The diamine compound described in item 1 of the scope of patent application, wherein in the diamine compound (b1-1) represented by formula (I), when x is 0, X ¹ is

,

,

,

,

,

,

,

,

,

or

, Where 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. The diamine compound described in item 1 of the scope of patent application, wherein in the diamine compound (b1-1) represented by formula (I), when x is 0, X ¹ is

,

,

,

or

. The diamine compound described in the first item of the scope of patent application, wherein in the diamine compound (b1-1) represented by formula (I), R ⁵ , R ⁶ and R ⁷ each independently represent a single bond,

,

,

,

, Methylene or alkylene having 2 to 3 carbons. The diamine compound described in the first item of the scope of patent application, wherein in the diamine compound (b1-1) represented by formula (I), When e+f+g<3, f and g are not equal to 0; When f≧1, b≧1; When g≧1, c+d≧1. A polymer (A-1), which is prepared by reacting a first mixture, and the first mixture includes a tetracarboxylic dianhydride compound (a1) and a diamine compound (b1), wherein the diamine The compound (b1) includes the diamine compound (b1-1) represented by formula (I) as described in any one of items 1 to 5 in the scope of patent application. The polymer (A-1) described in item 6 of the scope of patent application, wherein the diamine compound (b1) further includes a diamine compound (b1-2) represented by formula (II):

Formula (II) In formula (II), R ¹⁵ and R ¹⁷ each independently represent

,

,

,

,

or

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

Formula (III) In formula (III), Y ² each independently represents

,

,

,

,

,

,

,

or

; 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,

,

,

,

,

,

,

,

,

or

, Wherein m represents an integer from 1 to 5; Y ⁵ each independently represents a nitrogen-containing aromatic heterocyclic group; k represents an integer from 1 to 4. The polymer (A-1) described in item 6 of the scope of patent application, wherein the diamine compound (A-1) represented by the formula (I) is 100 mole parts based on the usage amount of the diamine compound (b1) The usage amount of b1-1) is 50 mol parts to 100 mol parts. The polymer (A-1) described in the seventh item of the scope of patent application, wherein the diamine compound (A-1) represented by the formula (II) is 100 mole parts based on the usage amount of the diamine compound (b1) The usage amount of b1-2) is 5 mol parts to 30 mol parts. The polymer (A-1) described in item 8 of the scope of patent application, wherein the diamine compound (A-1) represented by the formula (III) is 100 mole parts based on the usage amount of the diamine compound (b1) The usage amount of b1-3) is 1 mol part to 20 mol part. A liquid crystal alignment agent, comprising the polymer (A-1) and the solvent (B) as described in any one of items 6 to 11 in the scope of the patent application. The liquid crystal alignment agent described in item 12 of the scope of the patent application further includes a polymer (A-2), which is prepared by reacting a second mixture, and the second mixture Contains tetracarboxylic dianhydride compound (a2) and diamine compound (b2). The liquid crystal alignment agent according to item 12 of the scope of patent application, wherein the usage amount based on the polymer (A-1) is 100 parts by weight, and the usage amount of the solvent (B) is 1000 parts by weight to 3,500 parts by weight . The liquid crystal alignment agent as described in item 13 of the scope of patent application, wherein based on the total usage amount of the polymer (A-1) and the polymer (A-2) is 100 parts by weight, the polymer (A-2) -1) The usage amount is 30 parts by weight to 95 parts by weight. The liquid crystal alignment agent described in item 13 of the scope of patent application, wherein the solvent (B) is based on 100 parts by weight based on the total usage amount of the polymer (A-1) and the polymer (A-2) The usage amount is 1000 parts by weight to 3500 parts by weight. A liquid crystal alignment film is formed by the liquid crystal alignment agent according to any one of the 12th to 16th patent applications. A liquid crystal display element includes the liquid crystal alignment film as described in item 17 of the scope of patent application.

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