Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal device

Abstract

To provide a liquid crystal alignment agent capable of achieving a liquid crystal device excellent in reliability and impurity resistance while difficult to cause a deposition of a polymer at idling while applying an inkjet coating.SOLUTION: A liquid crystal alignment agent includes a polymer (P) including a structural unit derived from a diamine expressed by formula (1) and being at least one kind selected from a group including a polyamic acid, a polyamic acid ester and a polyimide. In formula (1), R1 and R2 are a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. However, at least one of R1 and R2 is a monovalent organic group having 1 to 6 carbon atoms. R3 and R4 are a hydrogen atom or a monovalent group having a nitrogen-containing heterocycle structure. However, at least one of R3 and R4 is a monovalent group having a nitrogen-containing heterocycle structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal device. [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] In recent years, large-screen, high-definition LCD televisions have become mainstream, and small display devices such as smartphones and tablet PCs have become increasingly popular, resulting in a greater demand for higher quality liquid crystal elements. Liquid crystal elements are also required to be highly reliable and less susceptible to deterioration with use. To address this, it has been proposed to use a diamine capable of introducing a nitrogen-containing aromatic heterocycle, such as a pyridine ring, into the side chain of a polymer, and to incorporate a polymer containing a structural unit derived from the diamine into a liquid crystal aligning agent (see Patent Document 1).

[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 enabling the LCD display elements themselves to grow in size. However, the disadvantage is that larger substrates make 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.

[0005] The advantages of the inkjet coating method include the possibility of uniform coating, for example, that the amount of liquid crystal alignment agent used during printing is substantially equal to the amount actually applied, so that the amount of liquid crystal alignment agent used can be reduced. Furthermore, since no printing plate is used, there is no need to replace or clean the printing plate, so the time, labor, and cost required for maintenance can be reduced, and the method has the flexibility to accommodate a variety of panel sizes. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-026052 Summary of the Invention [Problem to be solved by the invention]

[0007] The performance of liquid crystal elements (such as voltage holding ratio and film transmittance) is easily affected by impurities in the element. For example, if impurities exist in the liquid crystal alignment film that contacts the liquid crystal molecules and dissolve into the liquid crystal, this can lead to a decrease in the performance of the liquid crystal element and reduce the reliability of the element.

[0008] Furthermore, high-resolution liquid crystal panels such as 4K and 8K panels often have an insulating film. In liquid crystal panels with an insulating film, ionic impurities from the insulating film can leach into the liquid crystal through the liquid crystal alignment film. If ionic impurities leach into the liquid crystal, there is a concern that the quality of the liquid crystal element will deteriorate, such as by reducing the voltage holding ratio. Therefore, liquid crystal alignment films are required to have excellent performance (hereinafter also referred to as "impurity resistance") that prevents impurities generated within the element from penetrating into the liquid crystal and prevents a decrease in the voltage holding ratio due to impurities.

[0009] Furthermore, when attempting to improve the performance of liquid crystal devices by introducing a nitrogen-containing aromatic heterocycle into a liquid crystal alignment film, as in Patent Document 1, it is thought that the interaction between the functional groups (e.g., carboxy groups) of the polymer component and the nitrogen-containing aromatic heterocycle may cause a decrease in solubility. Therefore, when forming a liquid crystal alignment film on a substrate by inkjet coating, there is a concern that the polymer component in the liquid crystal alignment agent may be prone to precipitation at the inkjet head during idling of the inkjet coating device. Furthermore, if the polymer component precipitates at the head, there is a concern that the inkjet may become clogged, reducing coating performance, or that the precipitates may reduce the surface uniformity of the film.

[0010] The present invention has been made in view of the above problems, and an object of the present invention is to provide a liquid crystal aligning agent which is unlikely to cause polymer precipitation during idling during inkjet coating and which can provide a liquid crystal device which is excellent in reliability and impurity resistance. [Means for solving the problem]

[0011] 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 which contains a structural unit derived from a diamine represented by the following formula (1): [ka] (In formula (1), R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, provided that R 1 and R 2 At least one of R is a monovalent organic group having 1 to 6 carbon atoms. 3 and R 4 are each independently a hydrogen atom or a monovalent group having a nitrogen-containing heterocyclic structure. 3 and R 4 At least one of is a monovalent group having a nitrogen-containing heterocyclic structure.

[0012] According to another aspect of the present invention, there is provided a liquid crystal alignment film formed using the liquid crystal aligning agent according to the above [1]. Also, according to another aspect of the present invention, there is provided a liquid crystal element including the liquid crystal alignment film according to the above [2].

[0013] In another aspect, the present invention provides a polymer that is a polyamic acid, a polyamic acid ester, or a polyimide, and that includes a structural unit derived from the diamine represented by the above formula (1). In another aspect, the present invention provides a diamine represented by the above formula (1). [Effects of the Invention]

[0014] The liquid crystal aligning agent of the present invention can suppress the precipitation of polymers on the inkjet head during idling during inkjet coating. In addition, the liquid crystal aligning agent of the present invention can provide a liquid crystal device having excellent reliability and impurity resistance. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 2 is a diagram showing an electrode pattern of a transparent electrode film used in Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0016] Matters relating to aspects of the present disclosure will be described in detail below.

[0017] 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.

[0018] 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 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).

[0019] 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.

[0020] <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 containing a structural unit derived from a diamine represented by the following formula (1) (hereinafter also referred to as "specific diamine"). [ka] (In formula (1), R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, provided that R 1 and R 2 At least one of R is a monovalent organic group having 1 to 6 carbon atoms. 3 and R 4are each independently a hydrogen atom or a monovalent group having a nitrogen-containing heterocyclic structure. 3 and R 4 At least one of is a monovalent group having a nitrogen-containing heterocyclic structure.

[0021] 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.

[0022] <Polymer (P)> The polymer (P) is a polymer having a polyamic acid, a polyamic acid ester, or a polyimide as a main skeleton, and contains a structural unit derived from a specific diamine. 1 or R 2 The monovalent organic group having 1 to 6 carbon atoms represented by the formula (I) includes a monovalent hydrocarbon group having 1 to 6 carbon atoms, and any methylene group in the monovalent hydrocarbon group may be -O-, -S-, -CO-, -COO-, -OCO-, -NR 10 -, -NR 10 -CO-, -CO-NR 10 -, -O-CO-NR 10 -, -NR 10 -CO-O- or -NR 10 -CO-NR 11 - or other heteroatom-containing group (referred to as "group R a "), a monovalent hydrocarbon group or a group R a In this case, R 10 and R 11 are each independently a hydrogen atom or a monovalent hydrocarbon group.

[0023] Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkynyl group having 2 to 6 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a phenyl group.

[0024] Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, and isohexyl. Examples of linear or branched alkenyl groups having 2 to 6 carbon atoms include ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, and 2-butenyl. Examples of linear or branched alkynyl groups having 2 to 6 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl.

[0025] Examples of the monovalent alicyclic hydrocarbon group having 3 to 6 carbon atoms include groups having a saturated or unsaturated alicyclic monocyclic hydrocarbon structure having 3 to 6 carbon atoms as a ring structure. Specific examples of the ring in the alicyclic hydrocarbon group include cyclopentane, cyclohexane, cyclopentene, and cyclohexene.

[0026] R 1 or R 2 When the group represented by the formula (I) has a substituent, the substituent may be a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, a cyano group, a nitro group, a carboxyl group, -NR 12 R 13 (However, R 12 and R 13 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 12 and R 13 Specific examples of when R is an alkyl group include 1 or R 2 When is an alkyl group having 1 to 6 carbon atoms, the same groups as those given as specific examples can be mentioned.

[0027] R 1 or R 2The monovalent organic group having 1 to 6 carbon atoms, represented by the formula (I), is highly effective in suppressing the precipitation of the polymer in the liquid crystal alignment agent at the head portion during idling of the inkjet coating device when forming a liquid crystal alignment film on a substrate by inkjet coating, while maintaining high reactivity (i.e., polymerizability) when synthesizing the polymer (P), and is also effective in improving the reliability and impurity resistance of the liquid crystal element, and is therefore preferred over an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, -COR 5 or -NR 6 R 7 (However, R 5 , R 6 and R 7 are each independently an alkyl group having 1 to 3 carbon atoms. The same applies hereinafter.) is preferable. From the viewpoints of polymerizability and availability, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a phenyl group is more preferable, a methyl group, an ethyl group or a methoxy group is even more preferable, and a methyl group is even more preferable.

[0028] In the following, when a liquid crystal alignment agent is applied to a substrate by inkjet coating to form a liquid crystal alignment film, the property of the liquid crystal alignment agent that suppresses polymer precipitation in the head portion while the inkjet coating device is idling is also referred to as "idling resistance during inkjet coating" or simply "idling resistance."

[0029] R 1 and R 2 One or both of R is a monovalent organic group having 1 to 6 carbon atoms. 1 and R 2 As a combination of 1 is a monovalent organic group having 1 to 6 carbon atoms, and R 2 is a hydrogen atom; R 1 is a hydrogen atom, and R 2 is a monovalent organic group having 1 to 6 carbon atoms; R 1 and R 2and R are both monovalent organic groups having 1 to 6 carbon atoms. Even when a base component (more specifically, a nitrogen-containing heterocycle) is introduced into the polymer side chain, the polymer is less likely to precipitate, and as a result, a liquid crystal aligning agent having excellent idling resistance during inkjet coating can be obtained. 1 is preferably a monovalent organic group having 1 to 6 carbon atoms. 2 may be either a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. From the viewpoint of the balance between the effect of introducing a structural unit derived from the specific diamine and the ease of synthesis of the specific diamine, R 2 is preferably a hydrogen atom.

[0030] The introduction of specific diamine units has the advantage of improving idling resistance during inkjet coating, reliability of liquid crystal elements, and impurity resistance. 1 and R 2 At least one of the groups is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, -COR 5 or -NR 6 R 7 Preferably, R 1 is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, -COR 5 or -NR 6 R 7 and R 2 is more preferably a hydrogen atom. From the viewpoint of polymerizability and ease of compound availability, R 2 is a hydrogen atom, R 1 is more preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a phenyl group, and further preferably a methyl group, an ethyl group or a methoxy group.

[0031] R 3 or R 4In a monovalent group having a nitrogen-containing heterocyclic structure (hereinafter also referred to as a "monovalent heterocyclic structure-containing group") represented by the following formula, the nitrogen-containing heterocyclic ring of the nitrogen-containing heterocyclic structure may have only a nitrogen atom as a heteroatom constituting the ring, or may further have a heteroatom other than a nitrogen atom (for example, an oxygen atom or a sulfur atom). In addition, the nitrogen-containing heterocyclic ring may be an aromatic ring or a non-aromatic ring.

[0032] Specific examples of the aromatic ring include pyrrole, indole, imidazole, benzimidazole, oxazole, thiazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline, carbazole, azatropylidene, purine, benzo[d]oxazole, benzo[d]thiazole, and the following formula: [ka] Examples include rings represented by the following formula:

[0033] Specific examples of the non-aromatic ring structure include an ethyleneimine ring structure, a pyrrolidine ring structure, a piperidine ring structure, a piperazine ring structure, a hexamethyleneimine ring structure, a 3-pyrroline ring structure, a 2-pyrroline ring structure, a 2-imidazoline ring structure, an indoline ring structure, a 2-pyrazoline ring structure, and a succinimide ring structure.

[0034] The nitrogen-containing heterocyclic structure may have only one nitrogen-containing heterocycle, or may have two or more nitrogen-containing heterocycles. When the nitrogen-containing heterocyclic structure has two or more nitrogen-containing heterocycles, the two or more nitrogen-containing heterocycles may be connected to each other by a single bond, or may be connected to each other by a divalent linking group (for example, -NR 12 -Ya, -NR 12 -R 13 -NR 12 -(However, R 12 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a tert-butoxycarbonyl group, and R 13 may be linked via an alkanediyl group having 1 to 3 carbon atoms).

[0035] The nitrogen-containing heterocyclic ring in the monovalent heterocyclic structure-containing group may have a substituent, such as a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, or -NR 13 R 14 (However, R 13 and R 14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the like.

[0036] R 3 or R 4 The monovalent heterocyclic structure-containing group represented by the formula (I) preferably has a nitrogen-containing aromatic heterocycle. In order to improve the reliability and impurity resistance of the liquid crystal device, the nitrogen-containing aromatic heterocyclic structure preferably has at least one ring selected from the group consisting of pyrrole, indole, benzimidazole, oxazole, thiazole, triazole, pyridine, pyrimidine, quinoline, isoquinoline, azatropylidene, and purine, more preferably has at least one ring selected from the group consisting of pyridine, benzimidazole, triazole, and purine, and even more preferably has at least one of pyridine and benzimidazole.

[0037] Specific examples of the monovalent heterocyclic structure-containing group include groups represented by the following formula (2). [ka] (In formula (2), X 1 Y is a single bond or an (n+1)-valent linking group. 1 is X 1 is a monovalent group bonded to X via a nitrogen-containing heterocycle. n is 1 or 2. 1 If is a single bond, n is 1.)

[0038] In the above formula (2), Y 1Examples of the monovalent group represented by the formula include a group in which one hydrogen atom has been removed from a substituted or unsubstituted nitrogen-containing heterocycle; and a group in which two or more (preferably two) substituted or unsubstituted nitrogen-containing heterocycles are bonded by a single bond or a divalent linking group, and one hydrogen atom has been removed from any one of the nitrogen-containing heterocycles. Examples of the nitrogen-containing heterocycle include the rings exemplified above. The nitrogen-containing heterocycle is preferably a nitrogen-containing aromatic heterocycle.

[0039] Y 1 Specific examples of the monovalent group represented by the formula include partial structures represented by the formulas below. [ka] (In the formula, "*" represents a bond.)

[0040] X 1 As the (n+1)-valent linking group represented by the formula (1), when n is 1 (i.e., X 1 is a divalent linking group), specific examples include, for example, -O-, -CO-, *-CO-O-, *-O-CO-, -NH-, *-CO-NH-, *-NH-CO-, *-(CH2) r -O-, *-O-(CH2) r -, *-(CH2) r -CO-, *-CO-(CH2) r -, *-(CH2) r -NH-, *-NH-(CH2) r -, *-(CH2) r -CO-NH-, *-CO-NH-(CH2) r -, *-CO-NH-R 14 -O-, *-OR 14 -CO-NH-, an alkanediyl group having 1 to 10 carbon atoms, a phenyl group, or a group in which two or more of these groups are bonded (wherein r is an integer of 1 to 3. R 14 is a divalent hydrocarbon group having 1 to 10 carbon atoms. "*" represents a bond to the benzene ring in the above formula (1). When n is 2 (i.e., X 1 is a trivalent linking group), specific examples include *-N<, *-CO-N<, *-(CH2)r -CO-N<, *-OR 14 -CO-N< etc.

[0041] R 3 and R 4 In view of the balance between the effect of introducing a structural unit derived from a specific diamine and the ease of synthesis of the specific diamine, one or both of R 3 and R 4 It is preferred that one of the groups is a monovalent heterocyclic structure-containing group and the other is a hydrogen atom.

[0042] Preferable specific examples of the specific diamine include a compound represented by the following formula (1-A) and a compound represented by the following formula (1-B). [ka] (In the above formula (1-A) and formula (1-B), R 1 is the same as in the above formula (1). 1 , Y 1 and n have the same meanings as in formula (2) above.

[0043] Specific examples of the specific diamine include compounds represented by the following formulas (1-1) to (1-28). [ka] [ka]

[0044] The content of the structural units derived from the specific diamine in the polymer (P) is preferably 2 mol% or more, more preferably 5 mol% or more, based on the total amount of structural units derived from the diamine compounds contained in the polymer (P). The content of the structural units derived from the specific diamine 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 the diamine compounds contained in the polymer (P). By setting the content of the structural units derived from the specific diamine within the above range, the liquid crystal aligning agent can be made to have excellent idling resistance during inkjet coating, as well as excellent reliability and impurity resistance of the liquid crystal element, while ensuring polymerizability.

[0045] [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.

[0046] 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 (1-A) or (1-B) can be prepared by adding R to the benzene ring of the dinitrophenyl group. 1 and a first compound having a first reactive group (e.g., a carboxy group, a hydroxyl group, a halocarbonyl group, etc.) bonded thereto, and a second reactive group capable of reacting with the first reactive group and Y 1 The dinitro intermediate can be obtained by reacting a dinitro intermediate with a second compound having the formula: 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.

[0047] [Synthesis of polymer (P)] The synthesis method of the polymer (P) is not particularly limited. The polymer (P) can be obtained, for example, by polycondensation of a tetracarboxylic acid derivative and a diamine compound. The tetracarboxylic acid derivative includes tetracarboxylic acid dianhydrides, tetracarboxylic acid dihalides, and tetracarboxylic acid diester dihalides. The polyamic acid, polyamic acid ester, and polyimide will be described below.

[0048] (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 compound containing a specific diamine.

[0049] 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.

[0050] 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.

[0051] The tetracarboxylic dianhydride preferably includes an aliphatic tetracarboxylic dianhydride, more preferably an alicyclic tetracarboxylic dianhydride, in that a liquid crystal alignment film exhibiting good voltage retention characteristics can be obtained. Specifically, the tetracarboxylic dianhydride preferably includes at least one selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride.

[0052] In synthesizing the polyamic acid (P), the amount of the alicyclic tetracarboxylic dianhydride used is preferably 20 mol % or more, more preferably 30 mol % or more, and even more preferably 50 mol % or more, based on the total amount of the tetracarboxylic dianhydrides constituting the polyamic acid (P).

[0053] Diamine compounds When synthesizing the polyamic acid (P), only the specific diamine may be used as the diamine compound. Alternatively, the specific diamine may be used in combination with a diamine different from the specific diamine (hereinafter also referred to as "other diamine"). Examples of other diamines include aliphatic diamines, aromatic diamines, and diaminoorganosiloxanes. Examples of aliphatic diamines include linear diamines and alicyclic diamines.

[0054] 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.

[0055] 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:

[0056] Examples of the compound represented by formula (E-1) include compounds represented by the following formulas (E-1-1) to (E-1-4). [ka]

[0057] 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 diamine compounds described in JP-A-2010-97188.

[0058] The polyamic acid (P) can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound, optionally together with a molecular weight modifier. The ratio of the tetracarboxylic dianhydride and the diamine compound 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 compound.

[0059] Examples of molecular weight modifiers 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 compounds used.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] (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 compound, or [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine compound.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] (Polyimide) The polyimide as the polymer (P) (hereinafter also referred to as "polyimide (P)") can be obtained, for example, by dehydrating and cyclizing the polyamic acid (P) synthesized as described above to form an imidized polymer.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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).

[0074] 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.).

[0075] 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.

[0076] The content of the polymer (P) in the liquid crystal aligning agent is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by 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).

[0077] [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.

[0078] Polymer (Q) The polymer (Q) is a polymer that does not have a structural unit derived from a diamine having a 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 polymers, styrene polymers, maleimide polymers, (meth)acrylic-styrene copolymers, (meth)acrylic-maleimide copolymers, (meth)acrylic-styrene-maleimide copolymers, and styrene-maleimide copolymers.

[0079] Among these, the polymer (Q) is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane and addition polymer, in that it exhibits good liquid crystal alignment properties when used in combination with the polymer (P).

[0080] When the polymer (Q) is contained in the liquid crystal aligning agent, the content of the polymer (Q) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% 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 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less, based on the total amount of the polymer (P) and the polymer (Q).

[0081] When a photoalignment method is used to impart liquid crystal alignment ability to an organic film formed using a liquid crystal alignment agent, at least a part of the polymer (P) and the polymer (Q) may be a polymer having a photoalignment group. The photoalignment group is a functional group that can impart anisotropy to a film by a photoreaction such as a photoisomerization reaction, a photodimerization reaction, a photo-Fries rearrangement reaction, or a photodecomposition reaction due to light irradiation.

[0082] Specific examples of the photoalignment group include an azobenzene-containing group containing azobenzene or a derivative thereof as the basic skeleton, a cinnamic acid structure-containing group containing cinnamic acid or a derivative thereof (cinnamic acid structure) as the basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as the basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as the basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as the basic skeleton, a cyclobutane-containing group containing cyclobutane or a derivative thereof as the basic skeleton, a stilbene-containing group having stilbene or a derivative thereof as the basic skeleton, and a phenylbenzoate-containing group containing phenylbenzoate or a derivative thereof as the basic skeleton. Of these, the photoalignment group is preferably at least one selected from the group consisting of an azobenzene-containing group, a cinnamic acid structure-containing group, a chalcone-containing group, a stilbene-containing group, a cyclobutane-containing structure, and a phenylbenzoate-containing group. A cinnamic acid structure-containing group or a cyclobutane-containing structure is preferred in terms of high sensitivity to light and ease of incorporation into a polymer.

[0083] The synthesis method of a polymer having a photo-alignment group is not particularly limited. The polymer having a photo-alignment group can be obtained, for example, by (1) a method of obtaining by polymerization using a monomer having a photo-alignment group; (2) a method of synthesizing a polymer having a first functional group (e.g., an epoxy group) in a side chain, and reacting the first functional group-containing polymer obtained by the synthesis with a reactive compound having a second functional group (e.g., a carboxy group) that forms a bond with the first functional group and a photo-alignment group; or the like.

[0084] Crosslinking agent The liquid crystal aligning agent of the present disclosure preferably contains a crosslinking agent. By further containing a crosslinking agent in the liquid crystal aligning agent of the present disclosure, the film density of the liquid crystal alignment film can be increased, and the effect of suppressing the generation of impurities originating from the liquid crystal alignment film can be further enhanced. Furthermore, by suppressing the generation of impurities in the element, the intrusion of impurities into the liquid crystal can be minimized.

[0085] As a crosslinking agent, -OY 2(wherein Y 2 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a monovalent leaving group.), an amino group, a protected amino group, a mercapto group, a protected mercapto group, -Si(OR 21 ) k (R 22 ) 3-k (wherein R 21 and R 22 are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, k is an integer of 1 to 3, and when k is 2 or 3, multiple R 21 are the same or different, and when k is 1, multiple R 22 are the same or different), an oxiranyl group, an oxetanyl group, and a compound having at least one group selected from the group consisting of a polymerizable carbon-carbon double bond group (hereinafter also referred to as a "specific crosslinkable group") can be preferably used.

[0086] Y 2 The monovalent leaving group represented by the following formula is preferably a group that is released by heat or light and is replaced with a hydrogen atom. 2 Specific examples of the leaving group represented by the formula (I) include ether-based leaving groups such as alkyl groups having 7 or less carbon atoms, benzyl groups, and p-methoxybenzyl groups; acetal-based leaving groups such as methoxymethyl groups, ethoxyethyl groups, and 2-tetrahydropyranyl groups; acyl-based leaving groups such as acetyl groups and benzoyl groups; allyl-based leaving groups such as allyl groups and methallyl groups; and silyl ether-based leaving groups such as trimethylsilyl groups, triethylsilyl groups, and tert-butyldimethylsilyl groups. From the viewpoint of achieving both ease of leaving and storage stability, Y 2 Of these, the leaving group represented by Y is preferably an ether-based leaving group, an acetal-based leaving group, or an acetyl group, more preferably an alkyl group having 4 to 7 carbon atoms, a 2-tetrahydropyranyl group, a methoxymethyl group, a 1-ethoxyethyl group, or an acetyl group, and even more preferably a 2-tetrahydropyranyl group, a methoxymethyl group, a 1-ethoxyethyl group, or an acetyl group. 2Among the above, is particularly preferably a hydrogen atom, an alkyl group having 7 or less carbon atoms, an acetyl group, a 2-tetrahydropyranyl group, a methoxymethyl group, or a 1-ethoxyethyl group.

[0087] -OY 2 The group represented by the formula (I) is preferably bonded to a carbon atom, more preferably bonded to an alkanediyl group, and even more preferably is a group constituting a part of a methylol group or a hydroxyalkylamide group.

[0088] In the protected amino group, examples of the leaving group bonded to the nitrogen atom include carbamate-based leaving groups, amide-based leaving groups, imide-based leaving groups, and sulfonamide-based leaving groups. Among these, carbamate-based leaving groups are preferred because of their high thermal elimination properties. Specific examples include tert-butoxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethyloxycarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethoxycarbonyl, and 9-fluorenylmethyloxycarbonyl (F-moc) groups. Among these, the tert-butoxycarbonyl (Boc) group is particularly preferred because of its excellent thermal elimination properties and its ability to reduce the amount of deprotected moieties remaining in the film. In the protected mercapto group, the leaving group bonded to the sulfur atom is Y 2 Examples of the groups include the same groups as those exemplified as above.

[0089] When the specific crosslinkable group of the crosslinking agent is an amino group or a protected amino group, the crosslinking agent is preferably a chain compound. Note that when the crosslinking agent has a group in which a primary amino group is protected as the protected amino group, the protected amino group may be a group in which only one of the two hydrogen atoms in the primary amino group is replaced with a leaving group, or may be a group in which both hydrogen atoms are replaced with leaving groups.

[0090] -Si(OR 21 ) k(R 22 ) 3-k In the group represented by 21 or R 22 Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by the formula (I) include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. From the viewpoint of photoreactivity, R 21 R is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group or an ethyl group. 22 is preferably an alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted phenyl group, more preferably a methyl group, an ethyl group or a phenyl group. From the viewpoint of increasing the crosslinking reactivity, k is preferably 2 or 3, and more preferably 3.

[0091] When the crosslinking agent has a polymerizable carbon-carbon double bond group, the polymerizable carbon-carbon double bond group is preferably an unsaturated bond contained in a group represented by the following formulas (g1-1) to (g1-10), in that it has high crosslinking reactivity and can provide a liquid crystal alignment film with more excellent electrical properties. [ka] (In formulas (g1-1) to (g1-10), "*" represents a bond.)

[0092] When the crosslinking agent has a polymerizable carbon-carbon double bond group, it preferably has a group represented by the above formulas (g1-1) to (g1-7).Of these, it is more preferable that the crosslinking agent has a group represented by the above formulas (g1-1) to (g1-4) in terms of high crosslinking reactivity and ease of introduction of functional groups.

[0093] The number of specific crosslinkable groups possessed by the crosslinking agent is not particularly limited. From the viewpoint of increasing the crosslinking reactivity between the polymer (P) and the crosslinking agent and obtaining a liquid crystal alignment film with higher film density, the number of specific crosslinkable groups possessed by the crosslinking agent in one molecule is preferably 2 or more, more preferably 2 to 10. The crosslinking agent is preferably a compound (non-polymer) different from a polymer. The molecular weight of the crosslinking agent is, for example, 1,200 or less, preferably 1,000 or less, more preferably 800 or less.

[0094] Specific examples of the crosslinking agent include -OY 2 Examples of compounds having a group represented by the formula (5A-1) to (5A-34) include compounds represented by the formula (5A-1) to (5A-34) below: As the compound having a mercapto group or a protected mercapto group, compounds represented by each of the following formulae (5B-1) to (5B-6) and the like are included: As the compound having an amino group or a protected amino group, compounds represented by the following formulae (5C-1) to (5C-13) are mentioned: -Si(OR 21 ) r (R 22 ) 3-r Examples of compounds having a group represented by the formula (I) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and vinyltriethoxysilane; Examples of compounds having an oxiranyl group or an oxetanyl group include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, triglycidyl isocyanurate, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-oxygenase, and the like. Silylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl ether, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, epoxidation products of pentaerythritol tetraallyl ether with hydrogen peroxide, -Si(OR 21 ) r (R 22 ) 3-r Among the compounds exemplified as compounds having a group represented by the formula: Examples of compounds having a polymerizable carbon-carbon double bond group include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and compounds represented by the following formulas (5D-1) to (5D-7). [ka] [ka] [ka] [ka] [ka] [ka]

[0095] From the viewpoint of crosslinking reactivity with the polymer (P), the crosslinking agent is, among the above, -OY 2 and at least one selected from the group consisting of a compound having a group represented by the formula: -OY 2

[0039] At least one compound selected from the group consisting of a compound having a group represented by the formula (I), a compound having an amino group, a compound having a protected amino group, a compound having an oxiranyl group, and a compound having an oxetanyl group is more preferred.

[0096] 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 film density of the liquid crystal alignment film and improving the durability of the liquid crystal alignment film. 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 having 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.

[0097] ·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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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 %.

[0102] Although the reasons why the use of a liquid crystal aligning agent containing polymer (P) improved the idling resistance during inkjet coating of the liquid crystal aligning agent and also resulted in a liquid crystal device with excellent reliability and impurity resistance are unclear, the following is speculated. First, regarding the reliability and impurity resistance of the liquid crystal device, the introduction of a nitrogen-containing heterocycle (base component) into the side chain of the polymer suppressed the depolymerization reaction of the amic acid moiety of polymer (P). As a result, it is thought that the durability of the liquid crystal alignment film was improved and the generation of impurities derived from the alignment film was suppressed. Furthermore, the suppression of the generation of impurities derived from the alignment film suppressed the intrusion of impurities into the liquid crystal layer. Furthermore, because polymer (P) has a nitrogen-containing heterocycle in the side chain, impurities derived from the insulating film and other materials were adsorbed by the liquid crystal alignment film and retained within the film, which is thought to have enhanced the effect of suppressing the intrusion of impurities into the liquid crystal layer. As a result, it is thought that the deterioration of the reliability and voltage holding ratio of the liquid crystal device due to the generation of impurities was sufficiently suppressed.

[0103] On the other hand, when a nitrogen-containing heterocycle is introduced into the side chain of the polymer, intermolecular pseudo-crosslinking due to acid-base interaction is likely to occur, and the polymer component in the liquid crystal alignment agent is likely to precipitate, which is thought to result in a decrease in idling resistance during inkjet coating. In this regard, the structural unit derived from a diamine having a nitrogen-containing heterocycle introduced into the polymer (P) is R 1 and R 2 It is believed that the rotational freedom of the main chain skeleton (in other words, the mobility of the molecular chain) is reduced because at least one of the groups has a monovalent organic group having 1 to 6 carbon atoms. This makes it difficult for intermolecular pseudo-crosslinking due to acid-base interactions to occur, and as a result, it is believed that a liquid crystal aligning agent that is resistant to drying and moisture absorption even during idling can be obtained. However, the above speculation does not limit the present disclosure.

[0104] <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.

[0105] <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 has excellent idling resistance during inkjet coating, and is therefore suitable as a liquid crystal aligning agent for inkjet coating.

[0106] 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.

[0107] <Step 2: Alignment Treatment> When manufacturing a TN-, STN-, IPS-, 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, turning it into 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.

[0108] 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.

[0109] 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 2 After 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.

[0110] <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.

[0111] When a PSA type liquid crystal element is manufactured, the liquid crystal element can be manufactured by a method including the following steps [1] to [3]. [1] A step of applying the liquid crystal aligning agent of the present disclosure onto each conductive film of a pair of substrates having a conductive film to form a coating film. [2] A process of constructing a liquid crystal cell by arranging a pair of substrates coated with a liquid crystal alignment agent so that the coating films face each other, sandwiching a liquid crystal layer between them. [3] A process of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films.

[0112] Specifically, a liquid crystal cell is constructed in the same manner as in steps 1 to 3 above, except that a photopolymerizable compound is injected or dropped between a pair of substrates having a conductive film together with liquid crystal. Any conventionally known compound can be used as the photopolymerizable compound. A polyfunctional (meth)acrylic compound is preferred.

[0113] 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 (step [3]). The voltage applied here can be, for example, a direct current or alternating current of 5 to 50 V. The light to be irradiated can be, for example, ultraviolet light containing light with a wavelength of 150 to 800 nm and visible light. Of these, ultraviolet light containing light with a wavelength of 300 to 400 nm is preferred. The light source for the irradiation light can be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or an excimer laser. The light irradiation dose is preferably 1,000 to 200,000 J / m 2 and more preferably 1,000 to 100,000 J / m 2 is.

[0114] 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.

[0115] 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.

[0116] The present disclosure described above includes the following aspects [1] to

[10] . [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 which contains a structural unit derived from a diamine represented by the above formula (1). [2] R in the above formula (1) 1 is a monovalent organic group having 1 to 6 carbon atoms. [3] R in the above formula (1) 1 and R 2 At least one of the above is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, -COR 5 or -NR 6 R 7 (However, R 5 , R 6 and R 7 are each independently an alkyl group having 1 to 3 carbon atoms. [4] R in the above formula (1) 1 is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, -COR 5 or -NR 6 R 7 (However, R 5 , R 6 and R 7 are each independently an alkyl group having 1 to 3 carbon atoms, and R in the above formula (1) 2 The liquid crystal aligning agent according to any one of [1] to [3], wherein is a hydrogen atom. [5] The liquid crystal aligning agent according to any one of [1] to [4], wherein the monovalent group having a nitrogen-containing heterocyclic structure has a nitrogen-containing aromatic heterocyclic ring. [6] The liquid crystal aligning agent according to any one of [1] to [5], further comprising a crosslinking agent. [7] A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of [1] to [6]. [8] A liquid crystal element comprising the liquid crystal alignment film according to [7]. [9] A polymer which is a polyamic acid, a polyamic acid ester or a polyimide and contains a structural unit derived from a diamine represented by the above formula (1).

[10] A diamine represented by the above formula (1). [Example]

[0117] 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.

[0118] In the following examples, the weight average molecular weight (Mw), number average molecular weight (Mn), imidization ratio of polyimide, and epoxy equivalent of polyorganosiloxane were measured by the following methods. <Weight average molecular weight (Mw) and number average molecular weight (Mn)> 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) Column temperature: 40℃ Flow rate: 1.0mL / min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Detector: differential refractometer Standard material: monodisperse polystyrene <Imidization rate of polyimide> The polyimide solution was poured into pure water, and the resulting precipitate was thoroughly dried under reduced pressure at room temperature. After that, it was dissolved in deuterated dimethyl sulfoxide and measured at room temperature using tetramethylsilane as a standard substance. 1 H-NMR measurement was carried out. 1 The imidization rate [%] was calculated from the H-NMR spectrum using the following formula (1). Imidization rate [%] = (1-(β 1 / (β 2 ×α)))×100 …(1) (In formula (1), β 1 is the peak area due to the proton of the NH group that appears at a chemical shift of around 10 ppm, and β 2 is the peak area due to other protons, and α is the ratio of the number of other protons to one proton of the NH group in the polymer precursor (polyamic acid).

[0119] <Epoxy equivalent of polyorganosiloxane> Measurement was performed in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

[0120] The abbreviations of 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 "compound (X)." In the examples and comparative examples, "parts" and "%" are by mass unless otherwise specified.

[0121] Tetracarboxylic acid dianhydride [ka]

[0122] Diamine compounds [ka] [ka] [ka] [ka]

[0123] Siloxane monomers and carboxylic acids [ka]

[0124] Monomers with polymerizable carbon-carbon unsaturated bonds [ka]

[0125] Additives [ka]

[0126] <Polymer synthesis> 1. Synthesis of polyamic acid [Synthesis Example 1] 70 molar parts of compound (CA-2) and 30 molar parts of compound (CA-1) as tetracarboxylic dianhydrides, and 30 molar parts of compound (DA-1), 20 molar parts of compound (DB-2), 20 molar parts of compound (DB-4), and 30 molar parts of compound (DB-8) as diamine compounds were dissolved in N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at 60°C for 6 hours to obtain a solution containing 20 mass% of polyamic acid (referred to as polymer (PAA-1)).

[0127] [Synthesis Examples 2 to 19] Polyamic acids (referred to as polymers (PAA-2) to (PAA-19)) were obtained by the same procedure as in Synthesis Example 1, except that the types and amounts of the tetracarboxylic dianhydrides and diamine compounds used were changed as shown in Table 1. In Table 1, the numerical values for the tetracarboxylic dianhydrides represent the ratio (molar ratio) of each compound to 100 parts by mole of the total amount of the tetracarboxylic dianhydrides used in the synthesis of the polyamic acid. The numerical values for the diamine compounds represent the ratio (molar ratio) of each compound to 100 parts by mole of the total amount of the diamine compounds used in the synthesis of the polyamic acid.

[0128] 2. Polyimide Synthesis [Synthesis Example 20] 100 moles of compound (CA-2) as a tetracarboxylic dianhydride, and 30 moles of compound (DA-1), 20 moles of compound (DB-2), 20 moles of compound (DB-4), and 30 moles of compound (DB-8) as diamine compounds were dissolved in NMP and reacted at 60 °C for 6 hours to obtain a solution containing 20 mass% polyamic acid. Next, NMP was added to the resulting polyamic acid solution to obtain a solution with a polyamic acid concentration of 10 mass%, and pyridine and acetic anhydride were added, followed by a dehydration ring-closing reaction at 80 °C for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with fresh NMP to obtain a solution containing 15 mass% polyimide (referred to as polymer (PI-1)) with an imidization rate of approximately 62%.

[0129] [Synthesis Examples 21 to 28] Polyimides (referred to as polymers (PI-2) to (PI-9)) were obtained in the same manner as in Synthesis Example 20, except that the types and amounts of the tetracarboxylic dianhydrides and diamine compounds used were changed as shown in Table 1.

[0130] [Table 1]

[0131] 3. Synthesis of polyorganosiloxane [Synthesis Example 29] A reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux condenser was charged with 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (the compound represented by the above formula (S-1)), 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine, and mixed at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was stirred under reflux at 80 °C for 6 hours. After the reaction was completed, the organic layer was removed and washed with a 0.2% by mass aqueous solution of ammonium nitrate until the water after washing was neutral. The solvent and water were then distilled off under reduced pressure to obtain an epoxy-containing polyorganosiloxane (ESSQ-1) as a viscous, transparent liquid. Regarding polyorganosiloxane (ESSQ-1), 1 H-NMR analysis revealed a peak at a chemical shift (δ) of 3.2 ppm due to the epoxy group, confirming that no side reactions of the epoxy groups occurred during the reaction. The weight-average molecular weight (Mw) of the resulting polyorganosiloxane (ESSQ-1) was 3,500, and the epoxy equivalent was 180 g / mol. A 200 mL three-neck flask was charged with 10.0 g of polyorganosiloxane (ESSQ-1), 30.28 g of methyl isobutyl ketone as a solvent, and the modified components (carboxylic acids) of the compound represented by the formula (S-2) and the compound represented by the formula (S-3) in amounts corresponding to 20 mol% and 10 mol%, respectively, based on the total amount of epoxy groups possessed by the polyorganosiloxane (ESSQ-1). Also, 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) was added as a catalyst, and the reaction was carried out at 100 °C for 48 hours with stirring. After the reaction was completed, ethyl acetate was added to the reaction mixture, and the resulting solution was washed three times with water. The organic layer was dried over magnesium sulfate, and the solvent was then distilled off to obtain a polyorganosiloxane containing an orienting group (referred to as polymer (PSQ-1)). The weight-average molecular weight (Mw) of the resulting polymer was 8,000.

[0132] 4. Synthesis of styrene-maleimide copolymer [Synthesis Example 30] Under nitrogen, a 100 mL two-neck flask was charged with 18.7 mmol of compound (MA-2), 18.7 mmol of compound (MA-4), 10.6 mmol of compound (MA-6), and 5.3 mmol of compound (MA-7) as monomers with polymerizable carbon-carbon unsaturated bonds, 0.98 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator, and 50 mL of N-methyl-2-pyrrolidone (NMP) as a solvent, and polymerized at 70 °C for 6 hours. After reprecipitation in methanol, the precipitate was filtered and dried under vacuum at room temperature for 8 hours to obtain a styrene-maleimide copolymer (referred to as polymer (MI-1)). The weight-average molecular weight (Mw) measured by GPC (reduced to polystyrene equivalent) was 35,000, and the molecular weight distribution (Mw / Mn) was 2.

[0133] [Synthesis Example 31] A styrene-maleimide copolymer (referred to as polymer (MI-2)) was obtained in the same manner as in Synthesis Example 30, except that the types and amounts of the polymerization monomers used were changed as shown in Table 2.

[0134] [Table 2]

[0135] <Evaluation> <Preparation and Evaluation of Liquid Crystal Alignment Agent> [Example 1: PSA type liquid crystal display element] 1. Preparation of Liquid Crystal Alignment Agent A solution containing 100 parts by mass of the polymer (PAA-1) obtained in Synthesis Example 1 was diluted with NMP, γ-butyl lactone (GBL), ethylene glycol monobutyl ether (BC), diacetone alcohol (DAA), and diethylene glycol diethyl ether (DEDG), and 7 parts by mass of compound (AD-3) was added to obtain a solution with a solvent composition of NMP:GBL:BC:DAA:DEDG=30:30:20:10:10 (mass ratio) and a solids concentration of 4.0% by mass. This solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal alignment agent (AL-1).

[0136] 2. Preparation of Liquid Crystal Composition A liquid crystal composition LC1 was obtained by adding 0.3% by mass of a photopolymerizable compound represented by the following formula (L-1) to 10 g of nematic liquid crystal (MLC-6608, negative liquid crystal manufactured by Merck) and mixing them. [ka]

[0137] 3. Preparation of PSA-type liquid crystal cells The liquid crystal alignment agent (AL-1) prepared above was applied to each electrode surface of two glass substrates each having an ITO electrode patterned into slits and partitioned into multiple regions as shown in Figure 1, using a liquid crystal alignment film printer (manufactured by Nissha Printing Co., Ltd.). Next, the substrate was heated on a hot plate at 80°C for 1 minute (pre-baked) to remove the solvent, and then heated on a hot plate at 150°C for 10 minutes (post-baked) to form a coating film with an average film thickness of 0.06 μm. This coating film was ultrasonically cleaned in ultrapure water for 1 minute, and then dried in a clean oven at 100°C for 10 minutes to obtain a substrate with a coating film that would become a liquid crystal alignment film. This procedure was repeated to obtain a pair (two substrates) with a coating film. The electrode pattern used was the same type as the electrode pattern in the PSA mode. Next, an epoxy resin adhesive containing aluminum oxide spheres with a diameter of 5.5 μm was applied to the outer edges of each of the coated films of the pair of substrates, and then the substrates were placed together with the coated surfaces facing each other and pressed together, and the adhesive was cured. Next, the liquid crystal composition LC1 prepared above was filled between the pair of substrates through the liquid crystal injection port, and the liquid crystal injection port was sealed with an acrylic photocurable adhesive. Thereafter, a voltage of 100,000 J / m was applied between the conductive films of the obtained liquid crystal cell. 2 The sample was irradiated with light at an irradiation dose of .

[0138] 4. Reliability Assessment The reliability of the liquid crystal element was evaluated using the liquid crystal cell (liquid crystal cell after light irradiation) produced in the above 3. The evaluation was carried out as follows. First, a voltage of 5 V was applied to the liquid crystal cell for 60 microseconds over a span of 167 milliseconds, and the voltage holding ratio (VHR1) was measured 167 milliseconds after the voltage was removed. The liquid crystal cell was then placed in an 80°C oven under LED lamp irradiation for 200 hours, and then allowed to cool naturally to room temperature. After cooling, a voltage of 5 V was applied to the liquid crystal cell for 60 microseconds over a span of 167 milliseconds, and the voltage holding ratio (VHR2) was measured 167 milliseconds after the voltage was removed. The measurement device used was a "VHR-1" manufactured by Toyo Corporation. The rate of change in VHR (ΔVHR) was calculated using the following formula (I): ΔVHR[%]=(VHR1-VHR2) / (VHR1)×100…(I) The reliability of the liquid crystal element was evaluated based on the ΔVHR calculated as above. The evaluation was as follows: if ΔVHR was less than 1.0%, the reliability was rated as "very good (◎)", if it was 1.0% or more and less than 2.5%, the reliability was rated as "good (○)", and if it was 2.5% or more, the reliability was rated as "poor (×)". As a result, in this example, ΔVHR = 0.8%, and the reliability was rated as "very good (◎)".

[0139] 5. Idling resistance during inkjet (IJ) application An idling resistance test was conducted as follows using an inkjet device (manufactured by Shibaura Mechatronics Corporation) equipped with a head having a total of 256 ejection holes adjusted so that the ejection volume per dot was 50 pL. First, the liquid crystal alignment agent (AL-1) was filled into the inkjet device, and dummy ejection was performed under conditions that allowed all 256 ejection holes to eject the liquid crystal alignment agent (AL-1) without any problems. The head was then left in this state for a certain period of time. An ejection test was performed on a substrate that had been treated with a water-repellent surface to prevent droplets from wetting and spreading after the head was left in this state, and the number of droplets that were ejected successfully was counted visually. If 90% or more of the droplets were ejected successfully from all ejection holes, the head's idling resistance was judged to pass; otherwise, it was judged to fail. The test was started three hours after the head was left in this state, and continued every three hours thereafter until the idling resistance test failed. If the idling resistance test time was 15 hours or more, the idling resistance was judged to be "good (○)," if it was 9 hours or more but less than 15 hours, the idling resistance was judged to be "fair (△)," and if it was less than 9 hours, the idling resistance was judged to be "poor (×)." As a result, the idling resistance of this example was judged to be "good (○)."

[0140] 6. Impurity resistance (1) Preparation of insulating film-forming composition A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 15 parts by weight of methacrylic acid, 30 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, 5 parts by weight of 2-hydroxyethyl acrylate, and 30 parts by weight of isobornyl acrylate. After purging with nitrogen, gentle stirring was initiated. The reaction solution was heated to 62°C and maintained at this temperature for 5 hours to obtain a polymer solution containing acrylic copolymer (R-1). The obtained polymer solution was added dropwise to 900 parts by weight of hexane to precipitate the acrylic copolymer (R-1). The precipitated acrylic copolymer (R-1) was separated, and 150 parts by weight of propylene glycol monomethyl ethyl acetate was added. The mixture was heated to 40°C and distilled under reduced pressure to obtain a polymer solution containing the acrylic copolymer (R-1). The solid concentration of the obtained polymer solution containing the acrylic copolymer (R-1) was 30% by mass, and as a result of GPC analysis, the area of unreacted monomer and polymerization initiator was 2.3%, and the weight average molecular weight (Mw) was 12,800. For an amount equivalent to 100 parts by mass (solid content) of the acrylic copolymer (R-1), 25 parts by mass of a condensation product of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol) was used as a photosensitizer, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("KAYARAD" manufactured by Nippon Kayaku Co., Ltd.) was used as a polymerizable compound. A mixture of 5 parts by mass of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Kyowanol M manufactured by Kyowa Hakko Kirin Co., Ltd.) as a film-forming aid, 10 parts by mass of SH28PA (manufactured by Dow Corning Toray Co., Ltd.) as a leveling agent, and diethylene glycol ethyl methyl ether was added to the mixture to give a solids concentration of 18% by mass. The mixture was then dissolved and filtered through a membrane filter with a pore size of 0.2 μm to prepare an insulating film-forming composition (RD-1).

[0141] (2) Preparation of a substrate with an insulating film The insulating film-forming composition (RD-1) was applied to a glass substrate using a spin coater, and then prebaked on a hot plate at 90°C for 2 minutes. Then, a proximity exposure machine (Canon's "MA-1200" (ghi-ray mixed)) was used to apply 300 mJ / cm 2 After irradiating the entire surface of the substrate with this light, the coating was cured by heating (post-baking) in an oven at 230° C. for 30 minutes, forming an insulating film with a film thickness of 3 μm on the glass substrate.

[0142] (3) Manufacture of liquid crystal cells for impurity tolerance evaluation A liquid crystal alignment agent (AL-1) was applied using a spinner to the electrode formation surface of a substrate with a comb-shaped patterned ITO electrode and the insulating film formation surface of a substrate with an insulating film, and then heated (pre-baked) on a hot plate at 80°C for 1 minute.Then, the substrate was heated (post-baked) at 230°C for 1 hour in an oven with the interior replaced with nitrogen, to produce a pair (2 substrates) with a liquid crystal alignment film 0.1 μm thick. 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 the insulating substrate bearing the liquid crystal alignment film. The pair of substrates were then pressed together with the liquid crystal alignment film surfaces facing each other, and the adhesive was thermally cured at 150°C for 1 hour. Next, liquid crystal composition LC1 was filled into the gap between the substrates through the liquid crystal injection port, which was then sealed with an epoxy adhesive. Furthermore, to eliminate flow alignment during liquid crystal injection, the liquid crystal cell was heated to 130°C and then slowly cooled to room temperature to produce a liquid crystal cell. Because substrate preparation is simple, the liquid crystal cell used to evaluate impurity tolerance was prepared using electrode substrates for IPS-mode liquid crystal cells.

[0143] (4) Evaluation of impurity tolerance The liquid crystal cell for evaluating impurity tolerance manufactured in 6.(3) above was placed in a 60°C oven, and then the voltage holding ratio (VHR) was measured under conditions of 1V and 1670 milliseconds using a VHR measuring device "VHR-1" manufactured by Toyo Corporation. A VHR of more than 60% was rated "good (○)", a VHR of 60% or less but 45% or more was rated "fair (△)", and a VHR of less than 45% was rated "poor (×)". As a result, the electrical characteristics of this example were rated "good (○)".

[0144] [Examples 2 to 4, 6 to 11, 13 to 23 and Comparative Examples 1 to 10] Liquid crystal alignment agents (AL-2) to (AL-4), (AL-6) to (AL-11), (AL-13) to (AL-23), and (AR-1) to (AR-10) were 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 3. Liquid crystal cells were produced using the obtained liquid crystal alignment agents in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 3. In Table 3, the values in the mass ratio column represent the solid content ratio (parts by mass) of each compound (polymer, additive) relative to 100 parts by mass of the total amount of the polymer components used in preparing the liquid crystal alignment agent. The values in parentheses in the reliability (ΔVHR) column represent the ΔVHR values calculated using the above formula (I).

[0145] [Example 5: Optical VA type liquid crystal display element] 1. Preparation of Liquid Crystal Alignment Agent A liquid crystal aligning agent (AL-5) was prepared in the same manner as in Example 1, except that the composition of the liquid crystal aligning agent was changed as shown in Table 3. 2. Evaluation In Example 1, the substrate used to prepare the liquid crystal cell was a glass substrate with a transparent electrode made of an ITO film, a liquid crystal alignment agent (AL-5) was used, and polarized ultraviolet light of 1,000 J / m containing a 313 nm emission line was applied to the coating surface after post-baking using an Hg-Xe lamp and a Glan-Taylor prism. 2A photo-VA liquid crystal cell was prepared in the same manner as in Example 1, except that the liquid crystal composition LC1 was irradiated with light from a direction tilted 40° from the substrate normal to impart liquid crystal alignment ability, and a negative liquid crystal (MLC-6608, manufactured by Merck) was used instead of liquid crystal composition LC1. Reliability was evaluated in the same manner as in Example 1. Furthermore, using a liquid crystal alignment agent (AL-5), idling resistance and impurity resistance were evaluated in the same manner as in Example 1. For the evaluation of impurity resistance, a liquid crystal cell for evaluating impurity resistance was prepared in the same manner as in Example 1, except that the same substrates (substrates having an electrode substrate and an insulating film for an IPS-type liquid crystal cell) were used instead of a pair of glass substrates with transparent electrodes made of ITO films. The impurity resistance was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[0146] [Example 12] A liquid crystal aligning agent (AL-12) was prepared in the same manner as in Example 1, except that the composition of the liquid crystal aligning agent was changed as shown in Table 3. In addition, various evaluations were carried out in the same manner as in Example 5 using the obtained liquid crystal aligning agent (AL-12). The results are shown in Table 3.

[0147] [Example 24: Optical horizontal type liquid crystal display element] 1. Preparation of Liquid Crystal Alignment Agent A liquid crystal aligning agent (AL-24) was prepared in the same manner as in Example 1, except that the composition of the liquid crystal aligning agent was changed as shown in Table 3.

[0148] 2. Fabrication of Optically Operated Horizontal Liquid Crystal Cell The liquid crystal alignment agent (AL-24) prepared above was applied to each transparent electrode surface of a pair (two sheets) of glass substrates with transparent electrodes made of ITO film using a spinner and heated (pre-baked) on a hot plate at 80°C for 1 minute. It was then heated (post-baked) for 30 minutes in an oven at 230°C with the interior replaced with nitrogen, forming a coating film with an average thickness of 0.1 μm. The resulting coating film was irradiated with 1,000 J / m of linearly polarized ultraviolet light containing a 254 nm emission line using an Hg-Xe lamp. 2The coating film was then irradiated with light from the normal direction of the substrate to perform a photo-alignment treatment. The irradiation dose was measured using an actinometer measuring at a wavelength of 254 nm. The photo-aligned coating film was then heat-treated in a clean oven at 230°C for 30 minutes to form a liquid crystal alignment film. Next, for one of the pair of substrates on which the liquid crystal alignment film was formed, an epoxy resin adhesive containing 3.5 μm diameter aluminum oxide spheres was applied by screen printing to the outer edge of the surface bearing the liquid crystal alignment film. The substrates were then stacked and pressed together so that the polarization axes projected onto the substrate surfaces during light irradiation were antiparallel, and the adhesive was thermally cured at 150°C for 1 hour. Next, negative liquid crystal (MLC-6608, manufactured by Merck) was injected between the pair of 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 at 120°C and then slowly cooled to room temperature to obtain a liquid crystal cell.

[0149] 3. Evaluation Using the optically aligned horizontal liquid crystal cell prepared in 2 above, reliability was evaluated in the same manner as in Example 1. Furthermore, using a liquid crystal alignment agent (AL-24), idling resistance and impurity resistance were evaluated in the same manner as in Example 1. For the evaluation of impurity resistance, a liquid crystal cell for evaluating impurity resistance was prepared by the same procedure as in the preparation of the optically aligned horizontal liquid crystal cell, except that the same substrates as in Example 1 (substrates comprising an electrode substrate and an insulating film for an IPS-type liquid crystal cell) were used instead of the pair of substrates consisting of the first and second substrates, and impurity resistance was evaluated by the same procedure as in Example 1. The evaluation results are shown in Table 3.

[0150] Example 25: Rubbed horizontal liquid crystal display element 1. Preparation of Liquid Crystal Alignment Agent A liquid crystal aligning agent (AL-25) was prepared in the same manner as in Example 1, except that the composition of the liquid crystal aligning agent was changed as shown in Table 3.

[0151] 2. Fabrication of Rubbed Horizontal Liquid Crystal Cell The liquid crystal alignment agent (AL-25) prepared above was applied to each transparent electrode surface of a pair of glass substrates (two substrates) with transparent electrodes made of ITO films using a spinner and heated (pre-baked) on a hot plate at 80°C for 1 minute. This was then heated (post-baked) for 1 hour at 230°C in a nitrogen-purged oven to form a coating film with a thickness of 0.1 μm. This coating film was then rubbed using a rubbing machine equipped with a roll wrapped around a rayon cloth at a roll rotation speed of 400 rpm, a stage movement speed of 3 cm / sec, and a pile depth of 0.1 mm. This was followed by ultrasonic cleaning in ultrapure water for 1 minute and then drying in a clean oven at 100°C for 10 minutes to obtain a substrate with 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 substrates were then stacked with the liquid crystal alignment film surfaces facing each other and pressed together. 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 to obtain a liquid crystal cell.

[0152] 3. Evaluation Using the rubbed horizontal liquid crystal cell prepared in 2 above, reliability was evaluated in the same manner as in Example 1. In addition, using a liquid crystal alignment agent (AL-25), idling resistance and impurity resistance were evaluated in the same manner as in Example 1. In the evaluation of impurity resistance, a liquid crystal cell for evaluating impurity resistance was prepared by the same operation as in the preparation of the rubbed horizontal liquid crystal cell, except that the same substrates as in Example 1 (substrates having an electrode substrate and an insulating film for an IPS-type liquid crystal cell) were used instead of the pair of glass substrates with transparent electrodes made of ITO films, and impurity resistance was evaluated by the same operation as in Example 1. The evaluation results are shown in Table 3.

[0153] [Table 3]

[0154] As shown in Table 3, in Examples 1 to 25, the reliability, idling resistance, and impurity resistance were all evaluated as "very good (◎)," "good (○)," or "fair (△)." Furthermore, even in the examples (Examples 8 to 17 and 21 to 23) where the evaluation result included "fair (△)," only one of the three items (reliability, idling resistance, and impurity resistance) was evaluated as "fair (△)," indicating a good balance of various characteristics. In contrast, in Comparative Examples 1 to 10, one or more of the evaluations of reliability, idling resistance, and impurity resistance were rated as "poor (×)", or multiple evaluations were rated as "fair (△)", and were inferior to Examples 1 to 25.

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 which contains a structural unit derived from a diamine represented by the following formula (1): 【Chemical 1】 (In formula (1), R １ and R ２ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. １ and R ２ At least one of R is a monovalent organic group having 1 to 6 carbon atoms. ３ and R ４ are each independently a hydrogen atom or a monovalent group having a nitrogen-containing heterocyclic structure. ３ and R ４ At least one of is a monovalent group having a nitrogen-containing heterocyclic structure.

2. R in the above formula (1) １ The liquid crystal aligning agent according to claim 1, wherein is a monovalent organic group having 1 to 6 carbon atoms.

3. R in the above formula (1) １ and R ２ At least one of the above is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, or —COR ５ or -NR ６ R ７ (However, R ５ , R ６ and R ７ and each independently represent an alkyl group having 1 to 3 carbon atoms.

4. R in the above formula (1) １ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, -COR ５ or -NR ６ R ７ (However, R ５ , R ６ and R ７ are each independently an alkyl group having 1 to 3 carbon atoms; R in the above formula (1) ２ The liquid crystal aligning agent according to claim 3 , wherein is a hydrogen atom.

5. The liquid crystal aligning agent according to claim 1 , wherein the monovalent group having a nitrogen-containing heterocyclic structure has a nitrogen-containing aromatic heterocyclic ring.

6. The liquid crystal aligning agent according to claim 1 , further comprising a crosslinking agent.

7. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 6.

8. A liquid crystal device comprising the liquid crystal alignment film according to claim 7 .

9. A polymer which is a polyamic acid, a polyamic acid ester or a polyimide and which contains a structural unit derived from a diamine represented by the following formula (1): 【Chemistry 2】 (In formula (1), R １ and R ２ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. １ and R ２ At least one of R is a monovalent organic group having 1 to 6 carbon atoms. ３ and R ４ are each independently a hydrogen atom or a monovalent group having a nitrogen-containing heterocyclic structure. ３ and R ４ At least one of is a monovalent group having a nitrogen-containing heterocyclic structure.

10. A diamine represented by the following formula (1): 【Chemistry 3】 (In formula (1), R １ and R ２ are each independently a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms. １ and R ２ At least one of R is a monovalent organic group having 1 to 6 carbon atoms. ３ and R ４ are each independently a hydrogen atom or a monovalent group having a nitrogen-containing heterocyclic structure. ３ and R ４ At least one of is a monovalent group having a nitrogen-containing heterocyclic structure.

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