Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, polymer, and compound

Abstract

To provide a liquid crystal alignment agent exhibiting excellent coating properties and allowing formation of a highly reliable liquid crystal element with suppressed performance degradation during prolonged use under high-temperature conditions.SOLUTION: A liquid crystal alignment agent comprises at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, the agent containing a polymer (P) having a partial structure represented by formula (1), where R1 represents an alkyl group or fluoroalkyl group having 2 to 20 carbon atoms, R2 represents an (n1+1)-valent aromatic ring group, an (n1+1)-valent alicyclic group, or an (n1+1)-valent heterocyclic group, R4 represents a divalent aromatic ring group, Z1 and Z2 each represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms, Z1 and Z2 are not simultaneously hydrogen atoms, and R5 represents a linear alkanediyl group having 1 to 12 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal element, a polymer and a compound. [Background technology]

[0002] A liquid crystal element has a liquid crystal alignment film that functions to align liquid crystal molecules in a liquid crystal layer in a specific direction. A liquid crystal alignment film is generally formed on a substrate by applying a liquid crystal alignment agent, which is a polymer component dissolved in an organic solvent, to the substrate surface and preferably by heating.

[0003] Conventionally, methods for obtaining an organic film having liquid crystal alignment regulating power include a method of rubbing an organic film, a method of obliquely depositing silicon oxide, a method of forming a monomolecular film having a long-chain alkyl group, and a method of irradiating a photosensitive organic film with light (photo-alignment method). Of these, the photo-alignment method has been extensively studied in recent years because it can uniformly impart liquid crystal alignment properties to a film while suppressing the generation of static electricity and dust (see, for example, Patent Document 1 and Patent Document 2). Patent Document 1 and Patent Document 2 disclose the formation of a liquid crystal alignment film by the photo-alignment method using a polymer having a cinnamate structure.

[0004] In recent years, LCD televisions have become increasingly popular, and large-scale production lines known as "8th generation" and "10th generation" production lines are now in operation. The advantages of using large-scale production lines to produce larger substrates include the ability to produce multiple panels from a single substrate, reducing process time and costs, and the ability to accommodate larger LCD display elements. On the other hand, larger substrates have the disadvantage of making it difficult to ensure uniform printing of the liquid crystal alignment agent over a large area. To address this issue, the use of inkjet coating methods to form liquid crystal alignment films is being considered, as this method is expected to produce uniform coating. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-100099 [Patent Document 2] Japanese Patent Publication No. 2022-173076 Summary of the Invention [Problem to be solved by the invention]

[0006] While the main market for liquid crystal elements has traditionally been televisions, in recent years their use as display devices has expanded. Liquid crystal elements are used in a wide range of applications and in a variety of settings, including in-vehicle devices, digital signage, mobile phones, and tablets. Furthermore, as the range of applications for liquid crystal elements expands, they are increasingly being used in harsh environments that were previously unimaginable.

[0007] Therefore, liquid crystal devices are required to be highly reliable and not lose performance even when used for long periods of time in high-temperature environments. To ensure the reliability necessary to withstand long periods of use in high-temperature environments (hereinafter also referred to as "high-temperature reliability"), it is considered effective to introduce a rigid mesogen structure into the polymer. However, introducing a rigid mesogen structure into the polymer may reduce the solubility of the polymer, making it difficult to ensure the coatability of the liquid crystal alignment agent. This may result in a decrease in the performance of the liquid crystal device or a decrease in product yield.

[0008] The present invention has been made in view of the above-mentioned problems, and a main object of the present invention is to provide a liquid crystal aligning agent that exhibits excellent coatability and is resistant to deterioration in performance even when used for a long period of time in a high-temperature environment, and that can provide a highly reliable liquid crystal device. [Means for solving the problem]

[0009] According to one aspect of the present invention, there is provided a liquid crystal aligning agent containing a polymer (P) which is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide and has a partial structure represented by the following formula (1): [ka] (In formula (1), R 1 is an alkyl group, a fluoroalkyl group or a cyanated alkyl group having 2 to 20 carbon atoms. 1 is a single bond, an oxygen atom, * 1 -COO- or * 1 -OCO-. 1 " is R 1 Represents a bond with R. 2 R is an (n1+1)-valent aromatic ring group, an (n1+1)-valent alicyclic group, or an (n1+1)-valent heterocyclic group. 3 is a single bond, a divalent aromatic ring group, a divalent alicyclic group, or a divalent heterocyclic group. 2 is a single bond, an oxygen atom, * 2 -COO-, * 2 -OCO-, * 2 -R 6 O-, * 2 -OR 6 -, an alkanediyl group having 1 to 3 carbon atoms, or a vinylene group. 6 is an alkanediyl group having 1 to 3 carbon atoms. 2 " is R 3 Represents a bond with R. 4 is a divalent aromatic ring group. 1 and Z 2 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms. 1 and Z 2 At the same time, X does not become a hydrogen atom. 3 is an oxygen atom, a sulfur atom, or -NR 7 -R 7 is a hydrogen atom or a monovalent organic group. 5 is a linear alkanediyl group having 1 to 12 carbon atoms, or one or more methylene groups in the linear alkanediyl group having 1 to 12 carbon atoms are -O-, -COO-, or -NR 8 Replaced by CO- and -CH2- with X 3 R is a divalent group bonded to8 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3. However, when n1 is 2 or more, multiple X 1 are the same or different, and multiple R 1 are the same or different. If n2 is 2 or more, multiple X 2 are the same or different, and multiple R 3 are the same or different. "*" represents a bond.)

[0010] In another aspect, the present invention provides a liquid crystal alignment film formed using the above liquid crystal aligning agent. In another aspect, the present invention provides a liquid crystal element including the above liquid crystal alignment film. Furthermore, in another aspect, the present invention provides a polymer of any one of polyamic acid, polyamic acid ester, and polyimide, which includes a structural unit derived from a diamine having a partial structure represented by formula (1) above.

[0011] In another aspect, the present invention provides a compound represented by any one of the following formulas (2-1) to (2-3). [ka] (In formulas (2-1) to (2-3), R 1 is an alkyl group, a fluoroalkyl group or a cyanated alkyl group having 2 to 20 carbon atoms. 1 is a single bond, an oxygen atom, * 1 -COO- or * 1 -OCO-. 1 " is R 1 Represents a bond with R. 2 R is an (n1+1)-valent aromatic ring group, an (n1+1)-valent alicyclic group, or an (n1+1)-valent heterocyclic group. 3 is a single bond, a divalent aromatic ring group, a divalent alicyclic group, or a divalent heterocyclic group. 2 is a single bond, an oxygen atom, * 2 -COO-, * 2 -OCO-, * 2 -R 6 O-, *2 -OR 6 -, an alkanediyl group having 1 to 3 carbon atoms, or a vinylene group. 6 is an alkanediyl group having 1 to 3 carbon atoms. 2 " is R 3 Represents a bond with R. 4 is a divalent aromatic ring group. 1 and Z 2 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms. 1 and Z 2 At the same time, they do not become hydrogen atoms. X 3 is an oxygen atom, a sulfur atom, -NR 7 -R 7 is a hydrogen atom or a monovalent organic group. 5 is a linear alkanediyl group having 1 to 12 carbon atoms, or one or more methylene groups in the linear alkanediyl group having 1 to 12 carbon atoms are -O-, -COO-, or -NR 8 Replaced by CO- and -CH2- with X 3 R is a divalent group bonded to 8 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3. R 10 , R 11 , R 12 , R 13 and R 14 are each independently a substituent. n3 is an integer of 0 to 3. n4 and n5 are each independently an integer of 0 to 3. n6 and n7 are each independently an integer of 0 to 5. n8 and n9 are each independently an integer of 0 to 4. However, when n1 is 2 or more, multiple X 1 are the same or different, and multiple R 1 are the same or different. If n2 is 2 or more, multiple X 2 are the same or different, and multiple R 3 are the same or different. When n3 is 2 or more, multiple R 10 are the same or different, and when n6 is 2 or more, multiple R 11are the same or different, and when n7 is 2 or more, multiple R 12 are the same or different, and when n8 is 2 or more, multiple R 13 are the same or different, and when n9 is 2 or more, multiple R 14 are the same or different.) [Effects of the Invention]

[0012] The liquid crystal aligning agent of the present invention exhibits excellent coating properties, and is resistant to deterioration in performance even when used for a long period of time in a high-temperature environment, so that a highly reliable liquid crystal device can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0013] Matters relating to aspects of the present disclosure will be described in detail below.

[0014] Here, in this specification, a numerical range indicated using "to" means that the numerical values ​​before and after "to" are included as the lower and upper limits. A "structural unit" refers to a unit that mainly constitutes the main chain structure, and at least two or more units are contained in the main chain structure. A structural unit is typically a repeating unit constituted based on one monomer. Note that a structural unit may be obtained by reacting a repeating unit having a reactive group with a compound having a functional group that can react with the reactive group.

[0015] As used herein, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed solely of a chain structure. However, the group may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, the group does not necessarily have to be composed solely of an alicyclic hydrocarbon structure, and may also contain a chain structure as part of the ring structure. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, the group does not necessarily have to be composed solely of an aromatic ring structure, and may contain a chain structure or an alicyclic hydrocarbon structure as part of the ring structure. The term "organic group" refers to an atomic group obtained by removing any hydrogen atom from a carbon-containing compound (i.e., an organic compound).

[0016] The "main chain" of a polymer refers to the "trunk" portion of the polymer, which is the longest chain of atoms. It is permissible for this "trunk" portion to contain a ring structure. For example, "having a specific structure in the main chain" means that the specific structure constitutes a part of the main chain. A "side chain" refers to a portion branched from the "trunk" portion of the polymer.

[0017] <Liquid crystal alignment agent> The liquid crystal aligning agent of the present disclosure contains at least one polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, and having a partial structure represented by the following formula (1). [ka] (In formula (1), R 1 is an alkyl group, a fluoroalkyl group or a cyanated alkyl group having 2 to 20 carbon atoms. 1 is a single bond, an oxygen atom, * 1 -COO- or * 1 -OCO-. 1 " is R 1 Represents a bond with R. 2R is an (n1+1)-valent aromatic ring group, an (n1+1)-valent alicyclic group, or an (n1+1)-valent heterocyclic group. 3 is a single bond, a divalent aromatic ring group, a divalent alicyclic group, or a divalent heterocyclic group. 2 is a single bond, an oxygen atom, * 2 -COO-, * 2 -OCO-, * 2 -R 6 O-, * 2 -OR 6 -, an alkanediyl group having 1 to 3 carbon atoms, or a vinylene group. 6 is an alkanediyl group having 1 to 3 carbon atoms. 2 " is R 3 Represents a bond with R. 4 is a divalent aromatic ring group. 1 and Z 2 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms. 1 and Z 2 At the same time, X does not become a hydrogen atom. 3 is an oxygen atom, a sulfur atom, or -NR 7 -R 7 is a hydrogen atom or a monovalent organic group. 5 is a linear alkanediyl group having 1 to 12 carbon atoms, or one or more methylene groups in the linear alkanediyl group having 1 to 12 carbon atoms are -O-, -COO-, or -NR 8 Replaced by CO- and -CH2- with X 3 R is a divalent group bonded to 8 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3. However, when n1 is 2 or more, multiple X 1 are the same or different, and multiple R 1 are the same or different. If n2 is 2 or more, multiple X 2 are the same or different, and multiple R 3 are the same or different. "*" represents a bond.)

[0018] The polymer (P) contained in the liquid crystal aligning agent of the present disclosure and the components optionally blended as necessary will be described in detail below. Unless otherwise specified, each component may be used alone or in combination of two or more.

[0019] <Polymer (P)> A partial structure represented by the above formula (1) In the above formula (1), R 1 Examples of the alkyl group having 2 to 20 carbon atoms represented by the formula (I) include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group, and these may be linear or branched. 1 Examples of the fluoroalkyl group having 2 to 20 carbon atoms represented by the formula: 1 Examples of the alkyl group having 2 to 20 carbon atoms and represented by the formula: R 1 The cyanide alkyl group represented by R 1 Examples of the alkyl group having 2 to 20 carbon atoms include groups in which at least one hydrogen atom in the groups exemplified as the alkyl group having 2 to 20 carbon atoms represented by the following formula is substituted with a cyano group.

[0020] R 1 has preferably 3 or more carbon atoms, more preferably 4 or more carbon atoms. From the viewpoint of ensuring the solubility of the polymer (P) and the coatability of the liquid crystal aligning agent, R 1 R preferably has 18 or less carbon atoms, more preferably 15 or less carbon atoms. 1 The straight chain structure is preferred from the viewpoint of obtaining a liquid crystal device with better liquid crystal alignment properties.

[0021] X 1 is a single bond, an oxygen atom, * 1 -COO- or * 1 -OCO-. Of these, X 1is preferably a single bond or an oxygen atom. 1 When is a single bond or an oxygen atom, a liquid crystal device with improved high temperature reliability can be obtained.

[0022] R 2 is an (n1+1)-valent aromatic ring group, an (n1+1)-valent alicyclic group, or an (n1+1)-valent heterocyclic group. Of these, the (n1+1)-valent aromatic ring group is a group in which (n1+1) hydrogen atoms have been removed from the ring portion of a substituted or unsubstituted aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon rings and aromatic heterocycles. Specific examples of these aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of aromatic heterocycles include nitrogen-containing aromatic heterocycles such as a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and an imidazole ring; oxygen-containing aromatic heterocycles such as a furan ring; and sulfur-containing aromatic heterocycles such as a thiophene ring. R 2 From the viewpoint of improving the liquid crystal alignment property of a liquid crystal element and the solubility of the polymer (P), the aromatic ring constituting the (n1+1)-valent aromatic ring group represented by the following formula is preferably an aromatic hydrocarbon ring or a nitrogen-containing aromatic heterocycle, more preferably a benzene ring, a naphthalene ring or a pyridine ring, and even more preferably a benzene ring.

[0023] An (n1+1)-valent alicyclic group is a group obtained by removing (n1+1) hydrogen atoms from the ring portion of a substituted or unsubstituted alicyclic ring. Examples of the alicyclic ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, a cyclopentene ring, and a cyclohexene ring. Among these, a cyclohexane ring is preferred because it can provide a liquid crystal device with excellent liquid crystal alignment properties.

[0024] An (n1+1)-valent heterocyclic group is a group obtained by removing (n1+1) hydrogen atoms from the ring portion of a substituted or unsubstituted heterocycle. The heterocycle may be an aliphatic heterocycle or an aromatic heterocycle. Specific examples of the aliphatic heterocycle include nitrogen-containing aliphatic heterocycles such as piperidine ring and piperazine ring; oxygen-containing aliphatic heterocycles such as tetrahydrofuran and tetrahydropyran; and sulfur-containing aliphatic heterocycles such as tetrahydrothiophene. Specific examples of the aromatic heterocycle include the rings exemplified in the description of the (n1+1)-valent aromatic ring group. R 2 Of these, the heterocycle in the (n1+1)-valent heterocyclic group represented by the following formula is more preferably a pyrrole ring, a pyridine ring, a pyrimidine ring, a piperidine ring or a piperazine ring.

[0025] R 2 When the ring portion has a substituent, examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, and a fluoroalkyl group having 1 to 6 carbon atoms.

[0026] R is advantageous in that it can provide a liquid crystal element with less AC image retention while ensuring good coating properties of the liquid crystal alignment agent and reliability of the liquid crystal element (especially high temperature reliability). 2 is preferably an (n1+1)-valent alicyclic group or an (n1+1)-valent aliphatic heterocyclic group, more preferably an (n1+1)-valent alicyclic group, and particularly preferably a group in which (n1+1) hydrogen atoms have been removed from the ring portion of a substituted or unsubstituted cyclohexane ring. As liquid crystal elements become more versatile, further improvements in display quality are required of liquid crystal elements, and therefore, there is a demand for liquid crystal elements to be less susceptible to AC image retention. In this regard, R 2 is preferably an (n1+1)-valent alicyclic group or an (n1+1)-valent aliphatic heterocyclic group, more preferably an (n1+1)-valent alicyclic group, it is possible to obtain a liquid crystal device in which the occurrence of AC afterimages is further reduced.

[0027] R 3 is a single bond, a divalent aromatic ring group, a divalent alicyclic group, or a divalent heterocyclic group. Specific examples of these include R2 Among the groups exemplified in the explanation of R, groups corresponding to a divalent aromatic ring group, a divalent alicyclic group, and a divalent heterocyclic group can be mentioned. 3 is preferably a divalent alicyclic group or a divalent aliphatic heterocyclic group, more preferably a divalent alicyclic group, and particularly preferably a substituted or unsubstituted cyclohexylene group.

[0028] X 2 is a single bond, an oxygen atom, * 2 -COO-, * 2 -OCO-, * 2 -R 6 O-, * 2 -OR 6 -, an alkanediyl group having 1 to 3 carbon atoms or a vinylene group, and R 6 is an alkanediyl group having 1 to 3 carbon atoms. 6 The alkanediyl group having 1 to 3 carbon atoms represented by the formula (I) may be linear or branched. 2 is a single bond, an oxygen atom, * 2 -R 6 O-, * 2 -OR 6 -, an alkanediyl group having 1 to 3 carbon atoms or a vinylene group is preferred, and a single bond, an oxygen atom, * is preferred in that the solubility of the polymer (P) and the liquid crystal alignment property of the liquid crystal element can be further improved. 2 -CH2O-, * 2 More preferably, it is -OCH2-, a methylene group, or an ethylene group.

[0029] R 4 As the divalent aromatic ring group represented by R 2 Among the (n1+1)-valent groups exemplified in the explanation of R, groups corresponding to divalent aromatic ring groups are exemplified. 4 is particularly preferably a substituted or unsubstituted phenylene group.

[0030] Z 1 and Z 2are each a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms, provided that Z 1 and Z 2 and are not simultaneously hydrogen atoms. Among these, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of alkoxy groups having 1 to 5 carbon atoms include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, and pentoxy groups. These may be linear or branched. Specific examples of alkyl groups or fluoroalkyl groups having 1 to 6 carbon atoms include R 2 Among the groups exemplified in the explanation of (1), groups corresponding to alkyl groups or fluoroalkyl groups having 1 to 6 carbon atoms are exemplified.

[0031] Even when backlight is irradiated for a long time in a high-temperature environment, there is little decrease in the voltage holding ratio, and liquid crystal elements with excellent high-temperature reliability can be obtained. 1 and Z 2 and one of them is preferably a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms, and Z 1 is a hydrogen atom, and Z 2 is particularly preferably a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms. 1 and Z 2 In the formula (I), the group other than a hydrogen atom is preferably a halogen atom, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

[0032] X 3 Ga-NR 7 -If R 7Examples of the monovalent organic group represented by the formula (I) include monovalent hydrocarbon groups having 1 to 10 carbon atoms and monovalent leaving groups. The monovalent leaving group is preferably a group that is eliminated by heat or light and replaced with a hydrogen atom. Specific examples of the monovalent leaving group include carbamate-based leaving groups, amide-based leaving groups, imide-based leaving groups, and sulfonamide-based leaving groups. Of these, carbamate-based leaving groups are preferred because of their high thermal elimination properties, and examples thereof include tert-butoxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethyloxycarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethoxycarbonyl, and 9-fluorenylmethyloxycarbonyl (F-moc) groups. Of these, the tert-butoxycarbonyl group (Boc group) is particularly preferred because it has excellent thermal desorption properties and can reduce the amount of deprotected portions remaining in the film.

[0033] X 3 is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom, in that it can further increase the photoreactivity of the partial structure represented by the above formula (1).

[0034] R 5 is a linear alkanediyl group having 1 to 12 carbon atoms, or one or more methylene groups in the linear alkanediyl group having 1 to 12 carbon atoms are -O-, -COO-, or -NR 8 Replaced by CO- and -CH2- with X 3 R is a divalent group bonded to the polymer (P). R is advantageous in that it can increase the solubility of the polymer (P) while providing a liquid crystal device with excellent liquid crystal alignment properties. 5 is a linear alkanediyl group having 1 to 8 carbon atoms, or one or more methylene groups in the linear alkanediyl group having 1 to 8 carbon atoms are -O-, -COO-, or -NR 8 Replaced by CO- and -CH2- with X 3 and is preferably a linear alkanediyl group having 1 to 6 carbon atoms, or one or more methylene groups in the linear alkanediyl group having 1 to 6 carbon atoms are -O-, -COO-, or -NR 8Replaced by CO- and -CH2- with X 3 Of these, a linear alkanediyl group having 1 to 6 carbon atoms is more preferred, and an alkanediyl group having 1 to 4 carbon atoms is particularly preferred. R 8 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0035] n1 is preferably 1 or 2, more preferably 1, from the viewpoint of ease of introduction of the partial structure represented by the above formula (1). n2 is preferably 0 to 2, and more preferably 0 or 1, from the viewpoint of ensuring the solubility of the polymer (P) and facilitating the introduction of the partial structure represented by the above formula (1).

[0036] The bond (*) in the above formula (1) may be bonded to an atom constituting the main chain of the polymer, or may be bonded to an atom constituting the side chain. In terms of being more effective in improving the coatability of the liquid crystal aligning agent and the high-temperature reliability of the liquid crystal element in a well-balanced manner, the bond (*) in the above formula (1) is preferably bonded to the main chain of the polymer, and more preferably to an aromatic ring constituting a part of the main chain of the polymer. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.

[0037] R in the above formula (1) is preferred in that it can improve the liquid crystal alignment property, high temperature reliability, and AC image retention characteristics of the liquid crystal element. 2 is an (n1+1)-valent alicyclic group, and X 2 single bond, oxygen atom, * 2 -R 6 O-, * 2 -OR 6 -, an alkanediyl group having 1 to 3 carbon atoms or a vinylene group, and Z 1 and Z 2 Among these, a combination in which one of R in the above formula (1) is a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms, and the other is a hydrogen atom is preferred.2 is an (n1+1)-valent alicyclic group, and X 2 single bond, oxygen atom, * 2 -R 6 O-, * 2 -OR 6 - or an alkanediyl group having 1 to 3 carbon atoms, Z 2 is a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms, and Z 1 is a hydrogen atom is particularly preferred.

[0038] Specific examples of the partial structure represented by the above formula (1) include the partial structure represented by the following formula, and partial structures in which the terminal alkyl group, terminal alkoxy group, terminal fluoroalkyl group, or terminal fluoroalkoxy group in the partial structure represented by the following formula is replaced with an alkyl group, alkoxy group, fluoroalkyl group, or fluoroalkoxy group having 2 to 20 carbon atoms. [ka] [ka] (In the formula, "*" represents a bond.)

[0039] In the polymer (P), the content of the partial structure represented by the above formula (1) is preferably 15 mol % or more, more preferably 20 mol % or more, and even more preferably 25 mol % or more, based on the total amount of structural units derived from the monomers contained in the polymer (P). By setting the content of the partial structure represented by the above formula (1) within the above range, it is possible to improve the balance between the coatability of the liquid crystal aligning agent and the high-temperature reliability of the liquid crystal element.

[0040] [Specific embodiment of polymer (P)] The form of the polymer (P) having the partial structure represented by the above formula (1) is not particularly limited. For example, the polymer (P) may have the partial structure represented by the above formula (1) at the polymer terminal or in the side chain of the polymer. In order to fully obtain the effects of introducing the partial structure represented by the above formula (1) to improve the liquid crystal alignment property and reliability of the liquid crystal element and the coatability of the liquid crystal alignment agent, the polymer (P) preferably has the partial structure represented by the above formula (1) in the side chain of the polymer, and more preferably contains a structural unit derived from a diamine having the partial structure represented by the above formula (1) (hereinafter also referred to as a "specific diamine").

[0041] Specific diamines The specific diamine may have any structure represented by the above formula (1), and the structure is not particularly limited. From the viewpoints of ease of synthesis of the specific diamine and affinity with liquid crystals, the specific diamine is preferably an aromatic diamine. Here, the aromatic diamine refers to a compound in which two primary amino groups in the diamine are bonded to the same or different aromatic rings. The number of the partial structure represented by the above formula (1) in one molecule of the specific diamine may be one or more, and is preferably one or two.

[0042] Preferable specific examples of the specific diamine include compounds represented by any one of the following formulas (2-1) to (2-3). [ka] (In formulas (2-1) to (2-3), R 1 , X 1 , R 2 , R 3 , X 2 , R 4 , Z 1 , Z 2 , X 3 , R 5 , n1 and n2 have the same meanings as in formula (1). 10 , R 11 , R 12 , R 13 and R 14are each independently a substituent. n3 is an integer of 0 to 3. n4 and n5 are each independently an integer of 0 to 3. n6 and n7 are each independently an integer of 0 to 5. n8 and n9 are each independently an integer of 0 to 4. When n3 is 2 or more, multiple R 10 are the same or different, and when n6 is 2 or more, multiple R 11 are the same or different, and when n7 is 2 or more, multiple R 12 are the same or different, and when n8 is 2 or more, multiple R 13 are the same or different, and when n9 is 2 or more, multiple R 14 are the same or different.)

[0043] In the above formulas (2-1) to (2-3), R 10 , R 11 , R 12 , R 13 or R 14 Examples of the substituent represented by the formula (I) include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a hydroxy group, and a carboxy group. n3 is preferably 0 or 1. n4 and n5 each preferably represent 0 to 2, and more preferably 0 or 1. n6 and n7 each preferably represent 0 to 2, and more preferably 0 or 1. Each of n8 and n9 is preferably 0 or 1.

[0044] Specific examples of the specific diamine include compounds represented by the following formulas (1-1) to (1-17), and compounds in which the terminal alkyl group, terminal alkoxy group, terminal fluoroalkyl group, or terminal fluoroalkoxy group in the compounds represented by the following formulas (1-1) to (1-17) is replaced with an alkyl group, alkoxy group, cyanated alkyl group, fluoroalkyl group, or fluoroalkoxy group having 2 to 20 carbon atoms. [ka] [ka] [ka]

[0045] The content of the structural units derived from the specific diamine in the polymer (P) is preferably 30 mol % or more, more preferably 40 mol % or more, and even more preferably 50 mol % or more, based on the total amount of the structural units derived from the diamine contained in the polymer (P). By setting the content of the structural units derived from the specific diamine within the above range, it is possible to form an organic film with good photoalignment properties while achieving both the coatability of the liquid crystal aligning agent and the high-temperature reliability of the liquid crystal element.

[0046] [Synthesis of specific diamine] The specific diamine can be synthesized by appropriately combining standard methods in organic chemistry. One example of a method for synthesizing the specific diamine is to first synthesize a dinitro intermediate having a nitro group instead of the primary amino group in the target diamine, and then animate the nitro group of the obtained dinitro intermediate using an appropriate reduction system.

[0047] The method for synthesizing the dinitro intermediate can be appropriately selected depending on the molecular structure of the target diamine. For example, the compound represented by the above formula (2-1) can be synthesized by the following method: 5 and a hydroxyl group-containing compound having the group "-CZ 1 =CZ 2 -R 4 -(X 2 -R 3 ) n2 -R 2 -(X 1 -R 1 ) n1 a method of reacting a carboxylic acid having a dinitrophenyl group and R 5 and an amine compound having the group "-CZ 1 =CZ 2 -R 4 -(X 2 -R 3 ) n2 -R2 -(X 1 -R 1 ) n1 a method of reacting a carboxylic acid having a dinitrophenyl group and R 5 and a thiol compound having the group "-CZ 1 =CZ 2 -R 4 -(X 2 -R 3 ) n2 -R 2 -(X 1 -R 1 ) n1 Each reaction can be carried out in a suitable organic solvent, if necessary, in the presence of a catalyst.

[0048] The reduction reaction of the dinitro intermediate can be preferably carried out in an organic solvent using a catalyst such as palladium on carbon, platinum on carbon, zinc, iron, tin, or nickel. Examples of the organic solvent used here include ethyl acetate, toluene, tetrahydrofuran, and alcohols. However, the synthesis method of the specific diamine is not limited to the above.

[0049] [Synthesis of polymer (P)] The polymer (P) has a polyamic acid, a polyamic acid ester, or a polyimide as its main skeleton. Such a polymer (P) can be obtained, for example, by polycondensation of a tetracarboxylic acid derivative and a diamine. The tetracarboxylic acid derivative includes a tetracarboxylic acid dianhydride, a tetracarboxylic acid dihalide, and a tetracarboxylic acid diester dihalide. The polyamic acid, the polyamic acid ester, and the polyimide will be described below.

[0050] (Polyamic acid) When the polymer (P) is a polyamic acid, the polyamic acid (hereinafter also referred to as "polyamic acid (P)") can be obtained by reacting (polycondensation reaction) a tetracarboxylic dianhydride with a diamine.

[0051] Tetracarboxylic acid dianhydride Examples of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid (P) include aliphatic tetracarboxylic acid dianhydrides and aromatic tetracarboxylic acid dianhydrides. Examples of the aliphatic tetracarboxylic acid dianhydrides include linear tetracarboxylic acid dianhydrides and alicyclic tetracarboxylic acid dianhydrides.

[0052] Specific examples of the tetracarboxylic acid dianhydride include chain tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride and ethylenediaminetetraacetic acid dianhydride; Examples of alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3 .2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride 2,6 ]undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, etc.; Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, p-phenylene bis(trimellitic acid monoester anhydride), ethylene glycol bis(anhydrotrimellitate), 1,3-propylene glycol bis(anhydrotrimellitate), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-biphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, and 4,4'-carbonyldiphthalic anhydride; and the tetracarboxylic dianhydrides described in JP-A-2010-97188 can also be used.

[0053] The tetracarboxylic acid dianhydride preferably includes an aliphatic tetracarboxylic acid dianhydride, more preferably an alicyclic tetracarboxylic acid dianhydride, in terms of increasing the solubility of the polymer (P) and enabling the formation of a liquid crystal alignment film exhibiting good voltage retention characteristics. Specifically, the tetracarboxylic acid dianhydride preferably includes at least one selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic acid dianhydride, and cyclohexanetetracarboxylic acid dianhydride.

[0054] In the polyamic acid (P), the content of structural units derived from an alicyclic tetracarboxylic dianhydride is preferably 20 mol % or more, more preferably 30 mol % or more, even more preferably 50 mol % or more, and particularly preferably 70 mol % or more, based on the total amount of structural units derived from tetracarboxylic dianhydride contained in the polyamic acid (P).

[0055] Diamine In synthesizing the polyamic acid (P), only the specific diamine may be used as the diamine. Alternatively, a diamine not having the partial structure represented by the above formula (1) (hereinafter also referred to as "other diamines") may be used together with the specific diamine. Polyamic acids, polyamic acid esters, or polyimides containing structural units derived from the specific diamine can be obtained by condensation polymerization of a diamine containing the specific diamine and a tetracarboxylic acid derivative. Polyamic acids, polyamic acid esters, or polyimides containing structural units derived from the specific diamine and structural units derived from the other diamine can be obtained by condensation polymerization of a diamine containing the specific diamine and another diamine with a tetracarboxylic acid derivative.

[0056] The other diamine is not particularly limited as long as it does not have the partial structure represented by the above formula (1). Examples of the other diamine include aliphatic diamines, aromatic diamines, and diaminoorganosiloxanes. Examples of the aliphatic diamine include linear diamines and alicyclic diamines.

[0057] Specific examples of other diamines include chain diamines such as metaxylylenediamine and hexamethylenediamine; alicyclic diamines such as 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine); and diaminoorganosiloxanes such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane.

[0058] Specific examples of aromatic diamines include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,6-bis(4-aminophenoxy)hexane, bis[2-(4-aminophenyl)ethyl]hexanedioic acid, 1,4-bis-(4-aminophenyl)-piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 -Bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, 4,4'-diaminobenzanilide, 4,4'-diaminostilbene, 1, Main-chain diamines such as 4-bis(4-aminophenyl)-piperazine, bis[2-(4-aminophenyl)ethyl]hexanedioic acid, 4,4'-diaminodiphenethyl urea, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, and 4,4'-bis(4-aminophenoxy)biphenyl; Dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-di Cholestanyl aminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostaniyl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 5ξ-cholestan-3-yl 3,5-diaminobenzoate, the following formula (E-1): [ka] (In formula (E-1), X I and X II are each independently a single bond, -O-, *-COO-, or *-OCO- (where * indicates the bond to the diaminophenyl group). I is an alkanediyl group having 1 to 3 carbon atoms. II R is a single bond or an alkanediyl group having 1 to 3 carbon atoms. III is an alkyl group, alkoxy group, fluoroalkyl group, or fluoroalkoxy group having 1 to 20 carbon atoms. a is 0 or 1. b is an integer of 0 to 3. c is an integer of 0 to 2. d is 0 or 1, provided that 1≦a+b+c≦3. and side chain diamines such as compounds represented by the following formula:

[0059] Examples of the compound represented by formula (E-1) include compounds represented by the following formulas (E-1-1) to (E-1-4). [ka]

[0060] Specific examples of diaminoorganosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, etc. In addition to the above, other diamines that can be used include the diamines described in JP-A-2010-97188.

[0061] When the polymer (P) contains structural units derived from other diamines, the content of the structural units derived from other diamines is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 5 mol% or more, based on the total amount of structural units derived from diamines contained in the polymer (P). The content of the structural units derived from other diamines is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, based on the total amount of structural units derived from diamines contained in the polymer (P). By setting the content of the structural units derived from other diamines within the above range, an organic film with good photoalignment properties can be formed while achieving both the coatability of the liquid crystal aligning agent and the high-temperature reliability of the liquid crystal element.

[0062] In order to adjust the pretilt angle of the liquid crystal molecules controlled by the liquid crystal alignment film, other diamines having a photoalignment group and a partial structure represented by the above formula (1) (hereinafter also referred to as "other photoalignment diamines") may be used. Here, the photoalignment group refers to a functional group that can impart anisotropy to a film through a photoreaction such as photoisomerization, photodimerization, photo-Fries rearrangement, or photodecomposition upon light irradiation. Specific examples of photoalignment groups include azobenzene-containing groups containing azobenzene or a derivative thereof as a basic skeleton, cinnamic acid structure-containing groups containing cinnamic acid or a derivative thereof (cinnamic acid structure) as a basic skeleton, chalcone-containing groups containing chalcone or a derivative thereof as a basic skeleton, benzophenone-containing groups containing benzophenone or a derivative thereof as a basic skeleton, coumarin-containing groups containing coumarin or a derivative thereof as a basic skeleton, stilbene-containing groups containing stilbene or a derivative thereof as a basic skeleton, and phenylbenzoate-containing groups containing phenylbenzoate or a derivative thereof as a basic skeleton. However, when other photo-alignable diamines are used, from the viewpoint of obtaining a liquid crystal alignment film exhibiting a desired pretilt angle, the amount of other photo-alignable diamines used is preferably 30 mol % or less, more preferably 25 mol % or less, and even more preferably 20 mol % or less, relative to the total amount of diamines used in the synthesis of polymer (P).

[0063] Synthesis of polyamic acid (P) The polyamic acid (P) can be obtained by reacting a tetracarboxylic dianhydride with a diamine, optionally together with a molecular weight modifier. The ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of the polyamic acid (P) is preferably such that 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride are used per equivalent of the amino group of the diamine.

[0064] Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The proportion of the molecular weight modifier used is preferably 20 parts by mass or less per 100 parts by mass of the total of the tetracarboxylic dianhydride and diamine used.

[0065] The synthesis reaction of the polyamic acid (P) is preferably carried out in an organic solvent, preferably at a reaction temperature of −20° C. to 150° C., and for a reaction time of 0.1 to 24 hours.

[0066] Examples of organic solvents used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents include one or more selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, and halogenated phenols. Alternatively, it is preferred to use a mixture of one or more of these solvents with other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount of organic solvent (a) used is preferably an amount such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by mass relative to the total amount (a+b) of the reaction solution.

[0067] In this manner, a reaction solution containing the polyamic acid (P) dissolved therein is obtained. This reaction solution may be used directly for the preparation of a liquid crystal aligning agent, or the polyamic acid (P) contained in the reaction solution may be isolated and then used for the preparation of a liquid crystal aligning agent, or the isolated polyamic acid (P) may be purified and then used for the preparation of a liquid crystal aligning agent. When the polyamic acid (P) is subjected to dehydration ring closure to form a polyimide, the reaction solution may be used directly for the dehydration ring closure reaction, or the polyamic acid (P) contained in the reaction solution may be isolated and then used for the dehydration ring closure reaction, or the isolated polyamic acid (P) may be purified and then used for the dehydration ring closure reaction. The isolation and purification of the polyamic acid (P) can be carried out according to known methods.

[0068] (Polyamic acid ester) The polyamic acid ester as the polymer (P) (hereinafter also referred to as "polyamic acid ester (P)") can be obtained, for example, by [I] a method of reacting the polyamic acid (P) obtained by the above synthesis reaction with an esterifying agent; [II] a method of reacting a tetracarboxylic acid diester with a diamine; or [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine.

[0069] In this specification, "tetracarboxylic acid diester" means a compound in which two of the four carboxy groups in a tetracarboxylic acid are esterified and the remaining two are carboxy groups. "Tetracarboxylic acid diester dihalide" means a compound in which two of the four carboxy groups in a tetracarboxylic acid are esterified and the remaining two are halogenated.

[0070] Examples of the esterifying agent used in the method [I] include hydroxyl group-containing compounds, acetal compounds, halides, epoxy group-containing compounds, etc. Specific examples of these include: hydroxyl group-containing compounds such as alcohols (e.g., methanol, ethanol, and propanol), and phenols (e.g., phenol and cresol); acetal compounds such as N,N-dimethylformamide diethyl acetal and N,N-diethylformamide diethyl acetal; halides such as methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, and 1,1,1-trifluoro-2-iodoethane; and epoxy group-containing compounds such as propylene oxide.

[0071] The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic acid dianhydride exemplified in the description of the synthesis of the polyamic acid (P) using an alcohol such as methanol, ethanol, etc. The tetracarboxylic acid derivative used in the method [II] may be a tetracarboxylic acid diester alone, or may be used in combination with a tetracarboxylic acid dianhydride.

[0072] The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. The tetracarboxylic acid derivative used in the method [III] may be the tetracarboxylic acid diester dihalide alone, or may be used in combination with a tetracarboxylic acid dianhydride.

[0073] The polyamic acid ester (P) contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. The reaction solution in which the polyamic acid ester (P) is dissolved may be used directly for preparing the liquid crystal aligning agent, or the polyamic acid ester (P) contained in the reaction solution may be isolated and then used for preparing the liquid crystal aligning agent, or the isolated polyamic acid ester (P) may be purified and then used for preparing the liquid crystal aligning agent. The polyamic acid ester (P) can be isolated and purified according to known methods.

[0074] (Polyimide) The polyimide as the polymer (P) (hereinafter also referred to as "polyimide (P)") can be obtained, for example, by dehydrating and ring-closing the polyamic acid (P) synthesized as described above to thereby imidize it.

[0075] The polyimide (P) may be a fully imidized product in which all amic acid structures contained in its precursor polyamic acid (P) have been dehydrated and cyclized, or a partially imidized product in which only a portion of the amic acid structures have been dehydrated and cyclized, resulting in both amic acid structures and imide ring structures. The polyimide (P) preferably has an imidization rate of 20% or more, more preferably 30 to 99%. The imidization rate is the ratio, expressed as a percentage, of the number of imide ring structures to the total number of amic acid structures and imide ring structures in the polyimide (P). Some of the imide rings may be isoimide rings.

[0076] The dehydration ring-closure of the polyamic acid (P) is preferably carried out by heating the polyamic acid (P), or by dissolving the polyamic acid (P) in an organic solvent, adding a dehydrating agent and a dehydration ring-closure catalyst to the solution, and heating as necessary.

[0077] In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of polyamic acid (P), for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per mol of the amic acid structure of the polyamic acid (P). The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol per mol of the dehydrating agent used. Examples of organic solvents used in the dehydration ring-closing reaction include the organic solvents exemplified for use in the synthesis of polyamic acid (P). The reaction temperature for the dehydration ring-closing reaction is preferably 0 to 180°C, more preferably 10 to 150°C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

[0078] In this way, a reaction solution containing polyimide (P) is obtained. This reaction solution may be used directly for the preparation of a liquid crystal aligning agent, or may be used for the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or may be used for the preparation of a liquid crystal aligning agent after isolating polyimide (P), or may be used for the preparation of a liquid crystal aligning agent after purifying the isolated polyimide (P). These purification operations can be carried out according to known methods. Alternatively, polyimide (P) can also be obtained by imidizing polyamic acid ester (P).

[0079] The polymer (P) obtained as described above preferably has a solution viscosity of 20 to 1,800 mPa·s, and more preferably 50 to 1,500 mPa·s, when made into a 15% by mass solution. The solution viscosity (mPa·s) of the polymer (P) is a value measured at 25°C using an E-type rotational viscometer for a 15% by mass polymer solution prepared using a good solvent for the polymer (P) (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0080] The weight average molecular weight (Mw) of the polymer (P) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn) of the polymer (P), expressed as the ratio of Mw to the number average molecular weight (Mn) measured by GPC in terms of polystyrene, is preferably 8 or less, more preferably 7 or less. When the Mw and Mw / Mn of the polymer (P) are within the above ranges, good liquid crystal alignment properties of the liquid crystal element can be ensured.

[0081] The content of the polymer (P) in the liquid crystal aligning agent is preferably 2 mass% or more, more preferably 5 mass% or more, and even more preferably 7 mass% or more, based on the total amount of solids contained in the liquid crystal aligning agent (i.e., the total mass of components other than the solvent of the liquid crystal aligning agent).

[0082] [Other ingredients] The liquid crystal aligning agent of the present disclosure may further contain components other than the polymer (P) (hereinafter also referred to as "other components"). Examples of the other components include a polymer different from the polymer (P) (hereinafter also referred to as "polymer (Q)"), a crosslinking agent, a solvent, etc.

[0083] Polymer (Q) The polymer (Q) is a polymer that does not have the partial structure represented by the above formula (1). The main skeleton of the polymer (Q) is not particularly limited. Examples of the polymer (Q) include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyenamine, polyurea, polyamide, polyamideimide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, and addition polymer. Examples of the addition polymer include (meth)acrylic polymer, styrene polymer, maleimide polymer, (meth)acrylic-styrene copolymer, (meth)acrylic-maleimide copolymer, (meth)acrylic-styrene-maleimide copolymer, and styrene-maleimide copolymer.

[0084] Among these, polymer (Q) is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, and addition polymer, and more preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, in that it exhibits good liquid crystal alignment properties and voltage retention characteristics when used in combination with polymer (P).

[0085] When the polymer (Q) is contained in the liquid crystal aligning agent, the content of the polymer (Q) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 50% by mass or more, based on the total amount of the polymer (P) and the polymer (Q). The content of the polymer (Q) is preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 93% by mass or less, based on the total amount of the polymer (P) and the polymer (Q).

[0086] Crosslinking agent The liquid crystal aligning agent of the present disclosure may further contain a crosslinking agent. By further containing a crosslinking agent, it is possible to further improve the high-temperature reliability of the liquid crystal element and further reduce the occurrence of AC image retention. Examples of crosslinking agents include compounds having two or more groups in the molecule, each of which is at least one type of group selected from the group consisting of a cyclic ether group, a cyclic thioether group, an isocyanate group, a protected isocyanate group, a methylol group, a protected methylol group, a cyclic carbonate group, a polymerizable carbon-carbon bond-containing group, a protected amino group, a hydroxyalkylamide group, a protected hydroxyalkylamide group, a silanol group, and an alkoxysilyl group.

[0087] From the viewpoint of sufficiently improving the AC image retention characteristics and high-temperature reliability of the liquid crystal device, the number of crosslinkable groups contained in one molecule of the crosslinking agent is preferably 2 to 10, more preferably 2 to 6. The molecular weight of the crosslinking agent is preferably 100 to 1,000, more preferably 100 to 800, and even more preferably 100 to 700.

[0088] Specific examples of the crosslinking agent include compounds having a cyclic ether group or a cyclic thioether group, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, triglycidyl isocyanurate, glycerol polyglycidyl ether, pentaerythritol tetraglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, N,N',N',N'-tetraglycidyl glycoluril, 1,6-hexanediol diglycidyl ether, trimethyl Examples of such glycerols include methyl glycerol propane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, and epoxidation reaction products of 2,2'-diallylbisphenol A diallyl ether with hydrogen peroxide.

[0089] Examples of compounds having an isocyanate group or a protected isocyanate group include tolylene diisocyanate, xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, compounds in which the isocyanate group of these compounds is protected with 3,6-dimethylpyrazole, methyl ethyl ketoxime, diethyl malonate, or ε-caprolactam, and compounds represented by the following formula (d1-1).

[0090] Examples of compounds having a methylol group or a protected methylol group include compounds represented by the following formulas (d2-1) to (d2-10). Examples of the compound having a cyclic carbonate group include compounds represented by the following formulas (d3-1) and (d3-2).

[0091] Examples of compounds having a polymerizable carbon-carbon bond-containing group include compounds having a (meth)acryloyl group, a maleimide group, an alkenyl group, a vinylphenyl group, a vinyl ether group, or a 3-methylenetetrahydrofuran-2(3H)-one-5-yl group. Specific examples of these include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and compounds represented by the following formulas (d4-1) to (d4-7).

[0092] Examples of compounds having a protected amino group include compounds represented by the following formulae (d5-1) to (d5-5). Examples of compounds having a hydroxyalkylamide group or a protected hydroxyalkylamide group include compounds represented by the following formulas (d6-1) to (d6-7). Examples of compounds having a silanol group or an alkoxysilyl group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and vinyltriethoxysilane.

[0093] [ka] [ka] (In formula (d2-4), Ac is an acetyl group.) [ka] [ka] [ka] [ka] [ka]

[0094] When a crosslinking agent is contained in the liquid crystal aligning agent of the present disclosure, the content of the crosslinking agent is preferably 0.5 parts by mass or more relative to 100 parts by mass of the total amount of polymer components contained in the liquid crystal aligning agent (i.e., the total amount of polymer (P) and polymer (Q)), from the viewpoints of increasing the mechanical strength of the liquid crystal alignment film, improving the reliability of the liquid crystal element, and further reducing AC afterimages. From the above viewpoints, the content of the crosslinking agent is more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of the total amount of polymer components. Furthermore, from the viewpoints of obtaining a liquid crystal element with good liquid crystal alignment properties and electrical properties, and improving the storage stability of the liquid crystal aligning agent, the content of the crosslinking agent is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the total amount of polymer components.

[0095] ·solvent The liquid crystal aligning agent of the present disclosure is prepared as a liquid composition in which the polymer (P) and components used as needed are dispersed or dissolved preferably in a suitable solvent.

[0096] Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 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-i-propyl ether, and ethylene glycol-n-butyl ether ( butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, and the like.

[0097] In addition to the above, other components include, for example, antioxidants, metal chelate compounds, curing accelerators, surfactants, fillers, dispersants, photosensitizers, acid generators, base generators, radical generators, etc. The blending ratio of each of these components can be appropriately selected depending on each compound within a range that does not impair the effects of the present disclosure.

[0098] The solid content concentration in the liquid crystal aligning agent (the proportion of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected taking into consideration viscosity, volatility, etc., but is preferably in the range of 1 to 10 mass %. That is, the liquid crystal aligning agent is applied to the surface of a substrate as described below, and preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that will become a liquid crystal alignment film. In this case, if the solid content concentration is 1 mass % or more, the coating film can have a sufficient thickness, and a good liquid crystal alignment film tends to be easily obtained. If the solid content concentration is 10 mass % or less, the coating film thickness does not become too large, and an increase in the viscosity of the liquid crystal aligning agent can be suppressed, tending to improve the coatability.

[0099] The particularly preferred range of solid content varies depending on the application of the liquid crystal aligning agent and the method used to apply the liquid crystal aligning agent to a substrate. For example, when applying a liquid crystal aligning agent for a liquid crystal display device to a substrate by a spinner method, the solid content (the ratio of the total mass of all components in the liquid crystal aligning agent other than the solvent to the total mass of the liquid crystal aligning agent) is particularly preferably in the range of 1.5 to 4.5 mass%. When using a printing method, the solid content is particularly preferably in the range of 3 to 9 mass%, thereby adjusting the solution viscosity to a range of 12 to 50 mPa·s. When using an inkjet method, the solid content is particularly preferably in the range of 1 to 5 mass%, thereby adjusting the solution viscosity to a range of 3 to 15 mPa·s. The temperature when preparing the liquid crystal aligning agent is preferably 10 to 50°C, more preferably 20 to 30°C. Furthermore, with regard to the liquid crystal aligning agent for the retardation film, from the viewpoint of the applicability of the liquid crystal aligning agent and the thickness of the coating film to be formed being appropriate, the solid content concentration of the liquid crystal aligning agent is preferably in the range of 0.2 to 10 mass %, more preferably in the range of 3 to 10 mass %.

[0100] The reason why the liquid crystal alignment agent containing the polymer (P) can achieve both the coatability of the liquid crystal alignment agent and the high-temperature reliability of the liquid crystal element is not clear, but it is thought that the substituted cinnamate structure in the above formula (1) ("-CO-CZ" in the above formula (1)) 1 =CZ 2 -R 4The partial structure represented by "-" in the above formula (1) shortens the wavelength of light absorption, thereby improving high-temperature reliability. 5 It is presumed that the melting point of the polymer (P) is lowered by the addition of the hydroxybenzoate, which improves the solubility of the polymer (P), and that this combination contributes to the improvement of the polymer (P). However, this presumption does not limit the present invention.

[0101] <Liquid crystal alignment film and liquid crystal element> The liquid crystal alignment film of the present disclosure is formed using the liquid crystal aligning agent prepared as described above. Furthermore, the liquid crystal element of the present disclosure has a liquid crystal alignment film formed using the liquid crystal aligning agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, and various modes, such as TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS (In-Plane Switching) type, FFS (Fringe Field Switching) type, OCB (Optically Compensated Bend) type, and PSA (Polymer Sustained Alignment) type, can be applied. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, different substrates are used depending on the desired operation mode. Steps 2 and 3 are common to all operation modes.

[0102] <Step 1: Formation of coating film> First, a liquid crystal alignment agent is applied to a substrate, and the coated surface is preferably heated to form a coating film on the substrate. Examples of substrates that can be used include glass, such as float glass or soda glass; and transparent substrates made of resins, such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly(alicyclic olefin). When manufacturing TN, STN, or VA liquid crystal devices, two substrates with patterned transparent conductive films are used. On the other hand, when manufacturing IPS or FFS liquid crystal devices, one substrate with comb-shaped patterned electrodes and a counter substrate without electrodes are used. Examples of transparent conductive films that can be used include NESA films (registered trademark of PPG, USA) made of tin oxide (SnO), and ITO films made of indium oxide-tin oxide (InO-SnO). The liquid crystal alignment agent is applied to the substrate surface, preferably by offset printing, flexographic printing, spin coating, roll coating, or inkjet printing. The liquid crystal aligning agent of the present disclosure is suitable as a liquid crystal aligning agent for inkjet coating because it easily forms a uniform film even by inkjet coating.

[0103] After the liquid crystal aligning agent is applied, preheating (pre-baking) is preferably carried out for the purpose of preventing dripping of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30 to 200°C, and the pre-baking time is preferably 0.25 to 10 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of removing the solvent in the applied liquid crystal aligning agent. The baking temperature (post-baking temperature) at this time is preferably 80 to 250°C, more preferably 80 to 200°C. The post-baking time is preferably 5 to 200 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm.

[0104] <Step 2: Alignment Treatment> When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal device, the coating film formed in step 1 is subjected to a treatment (alignment treatment) to impart liquid crystal alignment ability. This imparts the ability to align liquid crystal molecules to the coating film, resulting in a liquid crystal alignment film. Examples of alignment treatments that can be used include rubbing, in which the coating film formed on the substrate is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, or cotton; and photoalignment, in which the coating film formed on the substrate is irradiated with light to impart liquid crystal alignment ability to the coating film. On the other hand, when manufacturing a vertical alignment (VA)-type liquid crystal device, the coating film formed in step 1 can be used as is as a liquid crystal alignment film. Furthermore, the coating film may be subjected to an alignment treatment to further enhance the liquid crystal alignment ability. Liquid crystal alignment films suitable for vertical alignment-type liquid crystal devices are also suitable for PSA-type liquid crystal devices.

[0105] In the photo-alignment treatment, light irradiation can be performed by irradiating the coating film after the post-bake step; irradiating the coating film after the pre-bake step but before the post-bake step; or irradiating the coating film while it is being heated in at least one of the pre-bake step and the post-bake step. The radiation to be irradiated to the coating film can be, for example, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm. Preferably, ultraviolet light containing light with a wavelength of 200 to 400 nm is used. When the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these. When non-polarized radiation is used, the irradiation direction is an oblique direction.

[0106] Examples of light sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, etc. The radiation dose on the substrate surface is preferably 400 to 50,000 J / m 2 and more preferably 1,000 to 20,000 J / m 2After the light irradiation for imparting alignment ability, the substrate surface may be washed with, for example, water, an organic solvent (e.g., methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.) or a mixture thereof, or the substrate may be heated.

[0107] <Step 3: Construction of liquid crystal cell> Two substrates with liquid crystal alignment films formed thereon are prepared as described above, and a liquid crystal cell is fabricated between the two substrates, with liquid crystal disposed adjacent to the liquid crystal alignment films. Examples of methods for fabricating a liquid crystal cell include placing two substrates facing each other with a gap between them so that the liquid crystal alignment films face each other, bonding the peripheries of the two substrates together with a sealant, injecting liquid crystal into the cell gap surrounded by the substrate surfaces and the sealant, and sealing the injection hole; an ODF method; and other methods. Examples of sealants that can be used include epoxy resins containing a curing agent and aluminum oxide spheres as spacers. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, with nematic liquid crystals being preferred. In the PSA mode, a liquid crystal cell is constructed by disposing a photopolymerizable compound together with liquid crystal between two substrates. After the liquid crystal cell is constructed, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.

[0108] For each mode of liquid crystal cell, a polarizing plate is then attached to the outer surface of the liquid crystal cell as needed to form a liquid crystal element. Examples of polarizing plates include a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine, sandwiched between cellulose acetate protective films, and a polarizing plate made of the H film itself.

[0109] The liquid crystal element of the present disclosure can be effectively applied to various applications, specifically, for example, various display devices such as watches, portable game machines, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays, as well as light control films, retardation films, and the like.

[0110] The present disclosure described above includes the following aspects [1] to

[14] . [1] A liquid crystal aligning agent comprising a polymer (P) which is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide and has a partial structure represented by the above formula (1). [2] R in the above formula (1) 2 A liquid crystal aligning agent of [1], wherein is an (n1+1)-valent alicyclic group. [3] X in the above formula (1) 2 single bond, oxygen atom, * 2 -R 6 O-, * 2 -OR 6 The liquid crystal aligning agent of [1] or [2], wherein the alkanediyl group is an alkanediyl group having 1 to 3 carbon atoms. [4] Z in the above formula (1) 1 and Z 2 The liquid crystal aligning agent according to any one of [1] to [3], wherein one of the groups is a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms, and the other is a hydrogen atom. [5] In the above formula (1), R 2 is an (n1+1)-valent alicyclic group, and X 2 single bond, oxygen atom, * 2 -R 6 O-, * 2 -OR 6 - or an alkanediyl group having 1 to 3 carbon atoms, Z 1 and Z 2 The liquid crystal aligning agent of [1], wherein one of the groups is a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms, and the other is a hydrogen atom. [6] The liquid crystal aligning agent according to any one of [1] to [5], wherein the polymer (P) contains a structural unit derived from a diamine having a partial structure represented by the above formula (1). [7] The liquid crystal aligning agent according to [6], wherein the diamine is represented by any one of the above formulas (2-1) to (2-3). [8] The liquid crystal aligning agent according to [6] or [7], wherein the polymer (P) further contains a structural unit derived from a diamine that does not have the partial structure represented by the formula (1). [9] The liquid crystal aligning agent according to any one of [1] to [8], further comprising a polymer (Q) that does not have the partial structure represented by the above formula (1).

[10] The liquid crystal aligning agent according to any one of [1] to [9], further containing a compound having two or more groups in the molecule of at least one selected from the group consisting of a cyclic ether group, a cyclic thioether group, an isocyanate group, a protected isocyanate group, a methylol group, a protected methylol group, a cyclic carbonate group, a polymerizable carbon-carbon bond-containing group, a protected amino group, a silanol group, and an alkoxysilyl group.

[11] A liquid crystal alignment film formed using the liquid crystal alignment agent according to any one of [1] to

[10] .

[12] A liquid crystal element comprising the liquid crystal alignment film of

[11] .

[13] A polymer of any one of polyamic acid, polyamic acid ester, and polyimide, which contains a structural unit derived from a diamine having a partial structure represented by the above formula (1).

[14] A compound represented by any one of the above formulas (2-1) to (2-3). [Example]

[0111] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0112] In the following examples, the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer were measured by the following methods. <Weight average molecular weight, number average molecular weight and molecular weight distribution> Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution (Mw / Mn) was calculated from the obtained Mw and Mn. Equipment: Showa Denko "GPC-101" GPC column: Shimadzu GLC's "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804" Mobile phase: Tetrahydrofuran (THF) or N,N-dimethylformamide solution containing lithium bromide and phosphoric acid Column temperature: 40°C, flow rate: 1.0 mL / min, sample concentration: 1.0 mass%, sample injection volume: 100 μL, detector: differential refractometer, standard substance: monodisperse polystyrene

[0113] The compounds used in the following examples are shown below. For convenience, hereinafter, a "compound represented by formula (X)" may be simply referred to as a "compound (X)". [ka] Photo-aligned diamine [ka]

[0114] Tetracarboxylic acid dianhydride [ka]

[0115] Diamines other than photo-alignable diamines [ka]

[0116] Crosslinking agent [ka]

[0117] 1. Synthesis of diamine [Synthesis Example 1-1] The compound (PRDA-1) was synthesized according to the following scheme. [ka]

[0118] Synthesis of compound (PRDA-1-1) Methyl 4-hydroxybenzoate (82.2 g, 540 mmol), potassium carbonate (166 g, 1.20 mmol), and N,N-dimethylacetamide (500 mL) were added and stirred at room temperature for 1 hour. 4,4,4-trifluoro-1-iodobutane (95.2 g, 400 mmol) was then added. After stirring at room temperature for 5 hours, 400 mL of water was added and the resulting precipitate was collected by filtration. The precipitate was mixed with sodium hydroxide (32.0 g) and water (400 mL). The mixture was refluxed for 4 hours, then neutralized with hydrochloric acid. The resulting precipitate was recrystallized from ethanol to obtain 84.1 g of compound (PRDA-1-1).

[0119] Synthesis of compounds (PRDA-1-2) To 7.45 g (30.0 mmol) of the compound (PRDA-1-1), 50 mL of thionyl chloride and a catalytic amount of DMF were added, and the mixture was stirred at 60° C. for 2 hours, and then the thionyl chloride was distilled off under reduced pressure. In a flask separate from the container containing compound (PRDA-1-1), 5.19 g (30.0 mmol) of 4-bromophenol and 10 mL of triethylamine were dissolved in 100 mL of THF and cooled to 0°C on ice. A THF solution (100 mL) of the reaction product of compound (PRDA-1-1) and thionyl chloride was added dropwise and allowed to react at room temperature overnight. After that, the reaction solution was washed with 1N hydrochloric acid and water, and the organic layer was collected and evaporated under reduced pressure to obtain 10.7 g of compound (PRDA-1-2).

[0120] Synthesis of compounds (PRDA-1-3) Compound (PRDA-1-2) 20.2 g (50.0 mmol), crotonic acid 12.9 g (150.0 mmol), P(o-tolyl) 31.52 g (5.00 mmol), iPr2NEt 25.9 mL (150 mmol), palladium acetate 561 mg (2.50 mmol), and DMF 250 mL were added and thoroughly purged with nitrogen. The mixture was heated to 100 °C and stirred for 6 hours. After cooling to room temperature, 200 mL of ethyl acetate was added, and the precipitate was filtered off. 200 mL of hexane was added to the filtrate, which was then washed sequentially with 1N hydrochloric acid, water, and saturated brine. The organic layer was dried over sodium sulfate, the solvent was removed under reduced pressure using a rotary evaporator, and the precipitated solid was dried to obtain compound (PRDA-1-3) 2.33 g.

[0121] Synthesis of compounds (PRDA-1-4) Compound (PRDA-1-3) 4.08 g (10.0 mmol) and 2.12 g (10.0 mmol) of 2,4-dinitrophenylethanol were dissolved in 100 mL of dichloromethane and cooled to 0 °C. Then, 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide 2.30 g (12.0 mmol) and 4-dimethylaminopyridine 0.611 g (5.00 mmol) were added, the mixture was returned to room temperature, and stirred overnight. The mixture was then washed with 1N hydrochloric acid and water. The collected organic layer was evaporated using a rotary evaporator to obtain 4.89 g of compound (PRDA-1-4).

[0122] Synthesis of compound (PRDA-1) To 6.025 g (10.0 mmol) of compound (PRDA-1-4), 30 mL each of THF and water was added, and 10 equivalents of tin chloride was added. The mixture was stirred at 60 °C for 2 hours, extracted with ethyl acetate, washed with water, and the solvent was removed using a rotary evaporator. The resulting solid was dissolved in 50 mL of THF, and 30 mL of ethanol and 10 mL of water were added. The good solvent was then slowly removed using a rotary evaporator. The precipitated solid was collected by filtration and dried to obtain 4.03 g of compound (PRDA-1).

[0123] [Synthesis Example 1-2] Compound (PRDA-2) was synthesized according to the following scheme. [ka]

[0124] Compound (PRDA-2-1) was synthesized in the same manner as compound (PRDA-1-3), except for changing the raw materials. Compounds (PRDA-1-4) and (PRDA-2) were then synthesized in the same manner as compound (PRDA-1).

[0125] [Synthesis Example 1-3] Compound (PRDA-3) was synthesized according to the following scheme. [ka]

[0126] Compound (PRDA-3-1) was synthesized in the same manner as compound (PRDA-1-3), except for changing the raw materials. Compounds (PRDA-1-4) and compound (PRDA-3) were then synthesized in the same manner as compound (PRDA-1).

[0127] [Synthesis Example 1-4] Compound (PRDA-4) was synthesized according to the following scheme. [ka]

[0128] Synthesis of compound (PRDA-4-1) 19.6 g (50.0 mmol) of 1-bromo-4-[-4-pentyl[1,1'-bicyclohexyl]-4-yl]benzene and 11.3 g (60.0 mmol) of triisopropyl borate were added to 30 mL of THF and cooled to -78 °C. Then, n-butyllithium was slowly added dropwise and stirred for 1 hour. The solution was returned to room temperature, 100 mL of 2N hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic phase was washed with water and dried over sodium sulfate. The solvent was then evaporated under reduced pressure to obtain compound (PRDA-4-1).

[0129] Synthesis of compound (PRDA-4-2) To 21.4 g (60.0 mmol) of compound (PRDA-4-1), 4.20 g (50.0 mmol) of methyl propiolate, 13.8 g (100 mmol) of potassium carbonate, 17.4 g (75.0 mmol) of silver oxide, 561 mg (2.5 mmol) of palladium acetate, and 200 mL of acetonitrile were added and stirred at 70 °C for 6 hours. The precipitate was filtered, extracted with ethyl acetate, and the organic phase was washed with water and dried over sodium sulfate. The solvent was evaporated under reduced pressure, and the resulting solid was purified by silica gel column chromatography to yield 8.52 g of compound (PRDA-4-2).

[0130] Synthesis of compound (PRDA-4-3) Compound (PRDA-4-2), 11.84 g (30.0 mmol), was mixed with 9.52 g (75.0 mmol) of silver fluoride, 270 μg (15.0 μmol) of water, and 100 mL of acetonitrile. The mixture was stirred at 90 °C for 6 hours, extracted with ethyl acetate, and the organic phase was washed with water and dried over sodium sulfate. The solvent was removed under reduced pressure, and the resulting viscous liquid was dissolved in 50 mL of ethanol. 100 mL of 40% aqueous sodium hydroxide was added and stirred at 100 °C for 3 hours. The pH was adjusted to 3 with 1N hydrochloric acid. The precipitated crystals were collected by filtration and washed with hexane to obtain compound (PRDA-4-3), 7.33 g. Compound (PRDA-4) was synthesized using the same method as compounds (PRDA-1-4) and (PRDA-1).

[0131] [Synthesis Example 1-5] Compound (PRDA-5) was synthesized according to the following scheme. [ka]

[0132] Compound (PRDA-5) was synthesized in the same manner as compound (PRDA-1-3), compound (PRDA-1-4), and compound (PRDA-1), except that the raw materials were changed.

[0133] [Synthesis Example 1-6] Compound (PRDA-6) was synthesized according to the following scheme. [ka]

[0134] Compound (PRDA-6) was synthesized by the same method as compound (PRDA-1-2), compound (PRDA-1-3), compound (PRDA-1-4), and compound (PRDA-1), except that the raw materials were changed.

[0135] [Synthesis Example 1-7] Compound (PRDA-7) was synthesized according to the following scheme. [ka]

[0136] Compound (PRDA-7) was synthesized in the same manner as compound (PRDA-1-3), compound (PRDA-1-4), and compound (PRDA-1), except that the raw materials were changed.

[0137] [Synthesis Example 1-8] Compound (PRDA-8) was synthesized according to the following scheme. [ka]

[0138] Compound (PRDA-8) was synthesized in the same manner as compound (PRDA-1-3), compound (PRDA-1-4), and compound (PRDA-1), except that the raw materials were changed.

[0139] [Synthesis Example 1-9] Compound (PRDA-9) was synthesized according to the following scheme. [ka]

[0140] Compound (PRDA-9) was synthesized in the same manner as compound (PRDA-1-4) and compound (PRDA-1), except that the raw materials were changed.

[0141] [Synthesis Example 1-10] Compound (PRDA-10) was synthesized according to the following scheme. [ka]

[0142] Compound (PRDA-10) was synthesized in the same manner as compound (PRDA-1-4) and compound (PRDA-1), except that the raw materials were changed.

[0143] [Synthesis Example 1-11] Compound (PRDA-11) was synthesized according to the following scheme. [ka]

[0144] Synthesis of compound (PRDA-11-1) Meldrum's acid (81.0 g, 375 mmol), potassium carbonate (68.4 g, 495 mmol), and DMF (200 mL) were added to 4-nitrobenzyl bromide (21.6 g, 150 mmol), and the mixture was stirred at room temperature for 24 hours. Water (800 mL) was then added, and the precipitate was collected by filtration. The solid was washed with water and recrystallized from methanol / dichloromethane to give compound (PRDA-1-1) (56.7 g).

[0145] Synthesis of compound (PRDA-11-2) 8.29 g (20.0 mmol) of compound (PRDA-11-1) was mixed with 1.68 g (40.0 mmol) of lithium hydroxide monohydrate, 100 mL of ethanol, and 50 mL of water, and stirred at room temperature for 24 hours. 100 mL of 1N hydrochloric acid was then added, and the precipitate was collected by filtration. The solid was washed with water and dried under reduced pressure to obtain 7.05 g of compound (PRDA-11-2).

[0146] Synthesis of compound (PRDA-11-3) and compound (PRDA-11) 8.29 g (20.0 mmol) of compound (PRDA-11-3) was added to 100 mL of THF and cooled to 0°C. Then, 1000 mL of a 1M tetrahydrofuran-borane-tetrahydrofuran solution was added dropwise. After returning the mixture to room temperature and stirring for 24 hours, 30 mL of water was added dropwise, followed by 70 mL of 1N hydrochloric acid. The mixture was extracted with ethyl acetate, washed with water, dried over sodium sulfate, and the solvent was removed under reduced pressure to yield 4.53 g of compound (PRDA-11-3). Compound (PRDA-11) was then synthesized using the same method as for compounds (PRDA-1-4) and (PRDA-1).

[0147] [Synthesis Example 1-12]: Synthesis of Compound (PRDA-12) Compound (PRDA-12) was synthesized according to the description in JP 2022-173076 A. [Synthesis Example 1-13]: Synthesis of Compound (PRDA-13) Compound (PRDA-13) was synthesized according to the description in JP 2017-187600 A. [Synthesis Example 1-14]: Synthesis of Compound (PRDA-14) Compound (PRDA-14) was synthesized according to JP 2011-18025 A. [Synthesis Example 1-15]: Synthesis of Compound (PRDA-15) Compound (PRDA-15) was synthesized as described in WO 2023 / 174773.

[0148] [Synthesis Example 1-16]: Synthesis of Compound (PRDA-16) 4.19 g of compound (PRDA-16) was obtained in the same manner as in Synthesis Example 1-1, except that 6-bromohexanenitrile was used instead of 4,4,4-trifluoro-1-iodobutane.

[0149] 2. Polymer synthesis [Synthesis Example 2-1: Synthesis of polymer (PI-1)] Under a dry nitrogen stream, 100 moles of compound (PRDA-1) as a diamine were dissolved in 20 g of N-methyl-2-pyrrolidone (NMP), and 100 moles of compound (TA-1) as a tetracarboxylic dianhydride were added thereto and reacted for 6 hours at 40° C. A solution containing 20 mass % of the target polyamic acid (referred to as "polymer (PI-1)") was obtained.

[0150] [Synthesis Examples 2-2 to 2-16 and Comparative Synthesis Examples 1 to 4: Synthesis of Polymers (PI-2 to PI-11, PI-16 to PI-20, PI-12 to PI-15)] Polymerization was carried out in the same manner as in Synthesis Example 2-1, except that the types and amounts of tetracarboxylic dianhydrides and diamines used in polymerization were changed as shown in Table 1, to obtain polyamic acid polymers (PI-2) to (PI-11), (PI-16) to (PI-20), and (PI-12) to (PI-15), respectively.

[0151] [Table 1]

[0152] 3. Fabrication and evaluation of optical vertical type liquid crystal display elements [Example 1] (1) Preparation of liquid crystal alignment agent (AL-1) To a mixture of 20 parts by mass of the polymer (P-1) obtained in Synthesis Example 2-1 and 100 parts by mass of the polymer (PI-18) (solid content of the polymer), N-methylpyrrolidone (NMP), gamma butyrolactone (GBL), diethylene glycol diethyl ether (DEDG) and diisobutyl ketone (DIBK) were added as solvents, to obtain a solution with a solvent composition of NMP / GBL / DEDG / DIBK=30 / 20 / 40 / 10 (mass ratio) and a solid content of 4.0% by mass. This solution was filtered through a filter with a pore size of 0.5 μm to prepare a liquid crystal alignment agent (AL-1).

[0153] (2) Manufacturing of optical vertical type liquid crystal display elements The liquid crystal alignment agent (AL-1) prepared above was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner and pre-baked on a hot plate at 80°C for 1 minute. It was then heated at 230°C for 1 hour in an oven with the interior replaced with nitrogen to form a coating film with a thickness of 0.1 μm. Next, the surface of this coating film was irradiated with polarized ultraviolet light at 200 J / m², including a 313 nm emission line, using an Hg-Xe lamp and a Glan-Taylor prism. 2 The substrate was irradiated with light from a direction tilted by 40° from the normal to the substrate to impart liquid crystal alignment ability. The same procedure was repeated to prepare a pair (two substrates) having a liquid crystal alignment film. Next, an epoxy resin adhesive containing 3.5 μm diameter aluminum oxide spheres was applied by screen printing to the outer periphery of the surface of one of the substrates bearing the liquid crystal alignment film. The pair of substrates were then placed with the liquid crystal alignment film surfaces facing each other and pressed together so that the projection directions of the UV light axes of each substrate were antiparallel. The adhesive was then thermally cured at 150°C for 1 hour. Next, a negative liquid crystal (MLC-6608, manufactured by Merck) was filled into the gap between the substrates through the liquid crystal injection port, which was then sealed with an epoxy adhesive. To eliminate flow alignment during liquid crystal injection, the substrate was heated to 130°C and then slowly cooled to room temperature. Next, polarizers were attached to both outer surfaces of the substrates so that their polarization directions were perpendicular to each other and at a 45° angle with the projection direction of the UV light axis of the liquid crystal alignment film onto the substrate surface, thereby producing a liquid crystal display device.

[0154] (3) Evaluation of liquid crystal alignment The vertically-optical liquid crystal display element obtained above was observed under a microscope at a magnification of 50x to check for the presence or absence of abnormal domains in the change in brightness when a voltage of 5V was turned on and off (applied and removed). The evaluation was "good (○)" when no abnormal domains were observed, and "poor (×)" when abnormal domains were observed. As a result, the evaluation of this example was "good (○)."

[0155] (4) Evaluation of AC image lag (pretilt angle difference) The obtained vertical-light LCD device was subjected to an AC voltage (AC) of 7V at room temperature for 20 hours. The pretilt angle difference before and after the voltage application was measured, and the AC image retention characteristics were evaluated based on the pretilt angle difference. The pretilt angle was measured by a crystal rotation method using a He-Ne laser beam, in accordance with the method described in the non-patent document "T.J. Scheffer et al. J. Appl. Phys. vol. 19, p. 2013 (1980)," and the tilt angle of the liquid crystal molecules from the substrate surface was measured and defined as the pretilt angle [°]. The resulting pretilt angle difference was 0.08°. The smaller the pretilt angle difference, the less likely an image retention caused by the AC voltage application will occur after the voltage application is released, indicating a better display. A pretilt angle difference of less than 0.1° was evaluated as "good (○)," a difference of 0.1° to less than 0.2° was evaluated as "fair (△)," and a difference of 0.2° or more was evaluated as "poor (×)."

[0156] (5) Evaluation of voltage holding ratio (VHR) A voltage of 5V was applied to the vertically-illuminated LCD element obtained above for a time of 60 microseconds over a span of 167 milliseconds, and the voltage holding ratio was measured 167 milliseconds after the application was removed. A VHR measuring device "VHR-1" manufactured by Toyo Corporation was used for the measurement. A voltage holding ratio of 95% or more was rated "good (○)," a voltage holding ratio of 80% or more but less than 95% was rated "passable (△)," and a voltage holding ratio of less than 80% was rated "poor (×)." As a result, the voltage holding ratio in this example was rated "good (○)."

[0157] (6) Evaluation of reliability due to backlight irradiation in a high-temperature environment (high-temperature BL reliability) The reliability of the vertically lit LCD device obtained above under backlight irradiation in a high-temperature environment was evaluated by its voltage holding ratio. The evaluation was performed as follows. First, a voltage of 1 V was applied to the liquid crystal cell for 60 microseconds, and the voltage holding ratio (VHR1) was measured 1670 milliseconds after the application was removed. Next, the liquid crystal cell was irradiated with CCFL (backlight) at 60°C for one week, and then left to cool naturally at room temperature. After cooling, a voltage of 1 V was applied to the liquid crystal cell for 60 microseconds, and the voltage holding ratio (VHR2) was measured 1670 milliseconds after the application was removed. The measurement was performed using a VHR measurement device "VHR-1" manufactured by Toyo Corporation. The rate of change in VHR (ΔVHR) at this time was calculated as the difference between VHR1 and VHR2 (ΔVHR = VHR1 - VHR2), and reliability was evaluated based on ΔVHR. When ΔVHR was less than 5%, it was judged as "excellent (◎)", when it was 5% or more and less than 10%, it was judged as "good (○)", when it was 10% or more and 20% or less, it was judged as "fair (△)", and when it was more than 20%, it was judged as "poor (×)". As a result, the reliability of this example when irradiated with backlight in a high temperature environment was rated as "good (○)".

[0158] (7) Evaluation of film uniformity by inkjet coating (IJ coating uniformity) The liquid crystal alignment agent (AL-1) prepared above was applied to the transparent electrode surface of a glass substrate with a transparent electrode using an inkjet coater (Shibaura Mechatronics Corporation). The application conditions were 2,500 times / (nozzle / min), a discharge amount of 250 mg / 10 seconds, and two round trips (a total of four applications). The substrate to which the liquid crystal alignment agent was applied was a glass substrate with a transparent electrode made of ITO, which had been heated on a hot plate at 200°C for 1 minute and then cleaned with ultraviolet light and ozone, so that the water contact angle of the transparent electrode surface was reduced to 10° or less. After coating, the film was left to stand for 1 minute, then pre-baked at 80°C for 1 minute, and then post-baked at 200°C for 40 minutes in a clean oven under a nitrogen atmosphere. The periphery and center of the liquid crystal alignment film were then observed under a 20x microscope. A film with no pinholes or coating irregularities (such as uneven film thickness) was evaluated as "excellent (◎)." A film with 1 to 3 pinholes and coating irregularities was evaluated as "good (○)." A film with 3 or more pinholes and coating irregularities was evaluated as "poor (×)." Good polymer solubility tends to improve film uniformity during inkjet coating. As a result, the inkjet coating uniformity of the liquid crystal alignment agent of this example was evaluated as "excellent (◎)."

[0159] [Examples 2 to 16 and Comparative Examples 1 to 4] A liquid crystal alignment agent was prepared in the same manner as in Example 1, except that the composition of the liquid crystal alignment agent was changed as shown in Table 2. In addition, a vertically oriented liquid crystal display element was manufactured using the obtained liquid crystal alignment agent in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 2.

[0160] [Table 2]

[0161] In Table 2, the abbreviations for the solvents represent the following compounds. NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone GBL: gamma butyrolactone BC: Butyl cellosolve DIBK: Diisobutyl ketone DEDG: Diethylene glycol diethyl ether DMM: Dipropylene glycol dimethyl ether MB: 3-methoxy-1-butanol DAA: Diacetone alcohol IB: Isobutyl isobutyrate

[0162] As shown in Table 2, the liquid crystal alignment agents of Examples 1 to 16 containing polymer (P) were all evaluated as excellent, good or fair in terms of liquid crystal alignment, AC afterimage characteristics, voltage holding ratio, high-temperature BL reliability and IJ coating uniformity, and various properties were improved in a well-balanced manner. Among these, when Example 5 and Example 6 are compared, it is found that X in the above formula (1) 2 The liquid crystal aligning agent of Example 5, in which X is a single bond, 2 The high-temperature BL reliability was superior to that of Example 6 in which the terminal ring structure of the partial structure represented by the above formula (1) was a cyclohexane ring. Furthermore, when Example 1 and Example 9 were compared, the liquid crystal alignment agent of Example 9 in which the terminal ring structure of the partial structure represented by the above formula (1) was a cyclohexane ring had reduced AC image retention compared to Example 1 in which the terminal ring structure was a benzene ring. Furthermore, when Example 7 and Example 10 were compared, Example 7 in which the substituted cinnamate structure was β-substituted had superior high-temperature BL reliability to Example 10 in which the substituted cinnamate structure was α-substituted.

[0163] In contrast, the liquid crystal alignment agents of Comparative Examples 1 to 4, which used only a polymer not having the partial structure represented by the above formula (1) instead of the polymer (P), were evaluated as poor in either the high-temperature BL reliability or the IJ coating uniformity.

Claims

1. A liquid crystal aligning agent comprising a polymer (P) which is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide and has a partial structure represented by the following formula (1): 【Chemical 1】 (In formula (1), R １ is an alkyl group, a fluoroalkyl group or a cyanated alkyl group having 2 to 20 carbon atoms. １ is a single bond, oxygen atom, * １ -COO- or * １ -OCO-. １ " is R １ Represents a bond with R. ２ is an (n1+1)-valent aromatic ring group, an (n1+1)-valent alicyclic group, or an (n1+1)-valent heterocyclic group. ３ represents a single bond, a divalent aromatic ring group, a divalent alicyclic group, or a divalent heterocyclic group. ２ is a single bond, oxygen atom, * ２ -COO-, * ２ -OCO-, * ２ -R ６ O-, * ２ -OR ６ -, an alkanediyl group having 1 to 3 carbon atoms, or a vinylene group. ６ is an alkanediyl group having 1 to 3 carbon atoms. ２ " is R ３ Represents a bond with R. ４ is a divalent aromatic ring group. １ and Z ２ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms. １ and Z ２ At the same time, X does not become a hydrogen atom. ３ represents an oxygen atom, a sulfur atom, or —NR ７ - is. R ７ is a hydrogen atom or a monovalent organic group. ５ is a linear alkanediyl group having 1 to 12 carbon atoms, or one or more methylene groups in the linear alkanediyl group having 1 to 12 carbon atoms is —O—, —COO—, or —NR ８ is replaced by —CO— and —CH ２ - and X ３ is a divalent group bonded to R ８ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3. However, when n1 is 2 or more, multiple X １ are the same or different, and multiple R １ are the same or different. When n2 is 2 or more, multiple X ２ are the same or different, and multiple R ３ are the same or different. "*" represents a bond.)

2. R in the above formula (1) ２ The liquid crystal aligning agent according to claim 1 , wherein is an (n1+1)-valent alicyclic group.

3. X in the above formula (1) ２ is a single bond, an oxygen atom, * ２ -R ６ O-, * ２ -OR ６ 2. The liquid crystal aligning agent according to claim 1, wherein the alkyl group is an alkanediyl group having 1 to 3 carbon atoms or a vinylene group.

4. Z in the above formula (1) １ and Z ２ The liquid crystal aligning agent according to claim 1, wherein one of the is a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms, and the other is a hydrogen atom.

5. In the above formula (1), R ２ is an (n1+1)-valent alicyclic group, X ２ is a single bond, an oxygen atom, * ２ -R ６ O-, * ２ -OR ６ an alkanediyl group having 1 to 3 carbon atoms or a vinylene group, Z １ and Z ２ The liquid crystal aligning agent according to claim 1, wherein one of the is a halogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms, and the other is a hydrogen atom.

6. The liquid crystal aligning agent according to claim 1, wherein the polymer (P) contains a structural unit derived from a diamine having a partial structure represented by the formula (1).

7. The liquid crystal aligning agent according to claim 6, wherein the diamine is represented by any one of the following formulas (2-1) to (2-3): 【Chemistry 2】 (In formulas (2-1) to (2-3), R １ , X １ , R ２ , R ３ , X ２ , R ４ , Z １ , Z ２ , X ３ , R ５ , n1 and n2 have the same meanings as in formula (1). １０ , R １１ , R １２ , R １３ and R １４ are each independently a substituent. n3 is an integer of 0 to 3. n4 and n5 are each independently an integer of 0 to 3. n6 and n7 are each independently an integer of 0 to 5. n8 and n9 are each independently an integer of 0 to 4. When n3 is 2 or more, multiple R １０ are the same or different, and when n6 is 2 or more, a plurality of R １１ are the same or different, and when n7 is 2 or more, a plurality of R １２ are the same or different, and when n8 is 2 or more, a plurality of R １３ are the same or different, and when n9 is 2 or more, a plurality of R １４ are the same or different.)

8. The liquid crystal aligning agent according to claim 6, wherein the polymer (P) further contains a structural unit derived from a diamine that does not have the partial structure represented by the formula (1).

9. The liquid crystal aligning agent according to claim 1, further comprising a polymer (Q) that does not have the partial structure represented by the formula (1).

10. The liquid crystal aligning agent according to claim 1, further comprising a compound having two or more groups in the molecule, at least one of which is selected from the group consisting of a cyclic ether group, a cyclic thioether group, an isocyanate group, a protected isocyanate group, a methylol group, a protected methylol group, a cyclic carbonate group, a polymerizable carbon-carbon bond-containing group, a protected amino group, a silanol group, and an alkoxysilyl group.

11. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 10.

12. A liquid crystal device comprising the liquid crystal alignment film according to claim 11.

13. A polymer of any one of polyamic acid, polyamic acid ester, and polyimide, A polymer comprising a structural unit derived from a diamine having a partial structure represented by the following formula (1): 【Chemistry 3】 (In formula (1), R １ is an alkyl group, a fluoroalkyl group or a cyanated alkyl group having 2 to 20 carbon atoms. １ is a single bond, oxygen atom, * １ -COO- or * １ -OCO-. １ " is R １ Represents a bond with R. ２ is an (n1+1)-valent aromatic ring group, an (n1+1)-valent alicyclic group, or an (n1+1)-valent heterocyclic group. ３ represents a single bond, a divalent aromatic ring group, a divalent alicyclic group, or a divalent heterocyclic group. ２ is a single bond, oxygen atom, * ２ -COO-, * ２ -OCO-, * ２ -R ６ O-, * ２ -OR ６ -, an alkanediyl group having 1 to 3 carbon atoms, or a vinylene group. ６ is an alkanediyl group having 1 to 3 carbon atoms. ２ " is R ３ Represents a bond with R. ４ is a divalent aromatic ring group. １ and Z ２ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms. １ and Z ２ At the same time, they do not become hydrogen atoms. ３ represents an oxygen atom, a sulfur atom, -NR ７ - is. R ７ is a hydrogen atom or a monovalent organic group. ５ is a linear alkanediyl group having 1 to 12 carbon atoms, or one or more methylene groups in the linear alkanediyl group having 1 to 12 carbon atoms is —O—, —COO—, or —NR ８ is replaced by —CO— and —CH ２ - and X ３ is a divalent group bonded to R ８ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3. However, when n1 is 2 or more, multiple X １ are the same or different, and multiple R １ are the same or different. When n2 is 2 or more, multiple X ２ are the same or different, and multiple R ３ are the same or different. "*" represents a bond.)

14. A compound represented by any one of the following formulas (2-1) to (2-3): 【Chemistry 4】 (In formulas (2-1) to (2-3), R １ is an alkyl group, a fluoroalkyl group or a cyanated alkyl group having 2 to 20 carbon atoms. １ is a single bond, oxygen atom, * １ -COO- or * １ -OCO-. １ " is R １ Represents a bond with R. ２ is an (n1+1)-valent aromatic ring group, an (n1+1)-valent alicyclic group, or an (n1+1)-valent heterocyclic group. ３ represents a single bond, a divalent aromatic ring group, a divalent alicyclic group, or a divalent heterocyclic group. ２ is a single bond, oxygen atom, * ２ -COO-, * ２ -OCO-, * ２ -R ６ O-, * ２ -OR ６ -, an alkanediyl group having 1 to 3 carbon atoms, or a vinylene group. ６ is an alkanediyl group having 1 to 3 carbon atoms. ２ " is R ３ Represents a bond with R. ４ is a divalent aromatic ring group. １ and Z ２ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or a fluoroalkyl group having 1 to 6 carbon atoms. １ and Z ２ At the same time, they do not become hydrogen atoms. ３ represents an oxygen atom, a sulfur atom, -NR ７ - is. R ７ is a hydrogen atom or a monovalent organic group. ５ is a linear alkanediyl group having 1 to 12 carbon atoms, or one or more methylene groups in the linear alkanediyl group having 1 to 12 carbon atoms is —O—, —COO—, or —NR ８ is replaced by —CO— and —CH ２ - and X ３ is a divalent group bonded to R ８ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. n1 is an integer of 1 to 3. n2 is an integer of 0 to 3. R １０ , R １１ , R １２ , R １３ and R １４ are each independently a substituent. n3 is an integer of 0 to 3. n4 and n5 are each independently an integer of 0 to 3. n6 and n7 are each independently an integer of 0 to 5. n8 and n9 are each independently an integer of 0 to 4. However, when n1 is 2 or more, a plurality of X １ are the same or different, and multiple R １ are the same or different. When n2 is 2 or more, multiple X ２ are the same or different, and multiple R ３ are the same or different. When n3 is 2 or more, multiple R １０ are the same or different, and when n6 is 2 or more, a plurality of R １１ are the same or different, and when n7 is 2 or more, a plurality of R １２ are the same or different, and when n8 is 2 or more, a plurality of R １３ are the same or different, and when n9 is 2 or more, a plurality of R １４ are the same or different.)

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