Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Abstract

A liquid crystal alignment agent comprising a polymer component satisfying at least any one of conditions (i) and (ii) below. Condition (i): The polymer component comprises at least one polymer selected from the group consisting of a polyimide precursor having repeating units (a1) as shown in formula (1) and repeating units (a1') as shown in formula (1'), and a polyimide as an imide derivative of the polyimide precursor. Condition (ii): The polymer component comprises at least one polymer selected from the group consisting of a polyimide precursor having repeating units (a1) as shown in formula (1) and a polyimide as an imide derivative of the polyimide precursor; and at least one polymer selected from the group consisting of a polyimide precursor having repeating units (a1') as shown in formula (1') and a polyimide as an imide derivative of the polyimide precursor. (X1 and X) 1’ Each of these groups independently represents a tetravalent organic group. Y1 represents a divalent organic group with an oxazoline skeleton. 1’ This indicates a divalent organic group (Ah) with an aliphatic carboxyl group or a divalent organic group (ph) with a phenolic hydroxyl group. R and Z each independently represent a hydrogen atom or a monovalent organic group.

Description

Technical Field

[0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. Background Technology

[0002] Previously, various driving methods, including different electrode structures and the physical properties of the liquid crystal molecules used, have been developed for liquid crystal display elements. Examples include known TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical Alignment) type, IPS (In-Plane Switching) type, and FFS (Fringe Field Switching) type display elements. These liquid crystal display elements have a liquid crystal alignment film for aligning the liquid crystal molecules. Materials used for the liquid crystal alignment film include, for example, polyamic acid, polyamic acid ester, polyimide, and polyamide.

[0003] In VA-type liquid crystal display elements, which are one of the driving methods of liquid crystal display elements, it is known that a photopolymerizable compound is added to the liquid crystal composition in advance, and a vertical alignment film such as a polyimide-based film is used to apply voltage to the liquid crystal cell while irradiating it with ultraviolet light, thereby accelerating the response speed of the liquid crystal (PSA (Polymer Sustained Alignment) type element) (see, for example, Patent Document 1 and Non-Patent Document 1).

[0004] In recent years, large-screen and high-resolution LCD TVs have become widely used. For LCD components in such applications, the requirements are for long-term use under harsh environments, unlike displays primarily used for text and static images. The liquid crystal alignment film used needs to have higher reliability than before. For example, the electrical characteristics of the liquid crystal alignment film, known as voltage retention rate, must not only have good initial properties but also maintain good properties after prolonged exposure to high temperature and humidity. As a solution to these problems, Patent Document 2 proposes a polyimide-based liquid crystal alignment film with an oxazoline backbone.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2003-307720

[0008] Patent Document 2: International Publication No. 2019 / 054443

[0009] Non-patent literature

[0010] Non-Patent Literature 1: K. Hanaoka, SID 04 DIGEST, pp. 1200-1202 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] Furthermore, the recent demand for lower costs in liquid crystal display (LCD) components is higher than ever before, leading to the use of various liquid crystal materials in these components. In particular, the use of low-cost liquid crystal materials increases the probability of voltage retention degradation in LCD components, thus requiring liquid crystal alignment films with voltage retention rates higher than ever before.

[0013] The object of the present invention is to provide, in view of the above, a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film, wherein the liquid crystal alignment agent can produce a liquid crystal alignment film with high voltage retention even after prolonged exposure to high temperature and high humidity.

[0014] Solution for solving the problem

[0015] In order to solve the above problems, the inventors conducted in-depth research and found that liquid crystal alignment agents containing specific components are effective in achieving the above objectives, thus completing the present invention.

[0016] Based on the aforementioned insights, this invention is based on the following main points.

[0017] [1] A liquid crystal alignment agent containing a polymer component that satisfies at least any one of the following conditions (i) and (ii).

[0018] Condition (i): The polymer component contains at least one polymer selected from the group consisting of a polyimide precursor having repeating units (a1) and repeating units (a1') as shown in formula (1) and polyimides that are imide derivatives of the polyimide precursor.

[0019] Condition (ii): The polymer component contains at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1) as shown in formula (1) and a polyimide as an imide derivative of the polyimide precursor; and at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1') as shown in formula (1') and a polyimide as an imide derivative of the polyimide precursor.

[0020]

[0021] (X1 and X) 1’ Each of these groups independently represents a tetravalent organic group. Y1 represents a divalent organic group with an oxazoline skeleton. 1’ This indicates a divalent organic group (Ah) with an aliphatic carboxyl group or a divalent organic group (ph) with a phenolic hydroxyl group. R and Z each independently represent a hydrogen atom or a monovalent organic group.

[0022] [2] According to the liquid crystal alignment agent of [1], wherein the divalent organic group (ph) has a structure as having the structure of the phenolic hydroxyl group, as shown in the following formula (ph-1).

[0023]

[0024] (Ar represents a benzene ring or a naphthalene ring. R represents a hydrogen atom, a methyl group, a methoxy group, or a halogen atom. * represents a bond.)

[0025] When Ar is a benzene ring, p represents an integer from 1 to 5, q represents an integer from 0 to 4, and r represents an integer from 1 to 5. The total of p, q, and r is 6.

[0026] When Ar is a naphthalene ring, p represents an integer from 1 to 7, q represents an integer from 0 to 6, and r represents an integer from 1 to 7. The sum of p, q, and r is 8.

[0027] [3] The liquid crystal alignment agent according to [1] or [2], wherein the polymer component at least satisfies the condition (i).

[0028] [4] The liquid crystal alignment agent according to [1] or [2], wherein the polymer component at least satisfies the condition (ii).

[0029] [5] The liquid crystal alignment agent according to any one of [1] to [4], wherein the oxazoline skeleton in Y1 is located in the main chain of the polymer having Y1.

[0030] [6] The liquid crystal alignment agent according to any one of [1] to [5], wherein Y1 has a partial structure represented by the following formula (m-Ox), the partial structure represented by the formula (m-Ox) being located in the main chain of the polymer having Y1.

[0031]

[0032] (R 1 * indicates a hydrogen atom or a monovalent organic group; * indicates a bonded bond.

[0033] [7] The liquid crystal alignment agent according to any one of [1] to [6], wherein, in the aliphatic carboxyl group, the carboxyl group is bonded to the carbon atom of the methylene group or to the carbon atom forming an alicyclic structure.

[0034] [8] The liquid crystal alignment agent according to any one of [1] to [7], wherein the divalent organic group (Ah) is a group obtained by removing two amino groups from a specific diamine (Ah) that is a diamine having an aliphatic carboxyl group, the specific diamine (Ah) being "A 1’ -(L-Ah) m’ "or "(A 11’ The aromatic diamine represented by )2-Ah'”.

[0035] (A 1’ This represents an m' valence group formed by the bonding of two primary amino groups with an aromatic group.

[0036] A 11’ It represents a monovalent group formed by the bonding of a primary amino group and an aromatic group.

[0037] L represents a single bond, -O-, -CO-, -CO-O-, -NR- (R represents a hydrogen atom or a methyl group) or -NR-CO- (R represents a hydrogen atom or a methyl group).

[0038] Ah represents a monovalent aliphatic carboxyl group.

[0039] m' is an integer from 1 to 2.

[0040] Ah' represents a divalent aliphatic carboxyl group.

[0041] [9] The liquid crystal alignment agent according to any one of [1] to [8], wherein the polymer component satisfies at least any one of the following conditions (i-1), (ii-1) and (ii-2).

[0042] Condition (i-1): The polymer component contains at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1) shown in formula (1), a repeating unit (a1') shown in formula (1') and a repeating unit (a2) shown in formula (2) below, and a polyimide as an imide derivative of the polyimide precursor.

[0043] Condition (ii-1): The polymer component contains at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1) shown in Formula (1) and a repeating unit (a2) shown in Formula (2) below, and a polyimide as an imide derivative of the polyimide precursor; and at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1') shown in Formula (1') and a polyimide as an imide derivative of the polyimide precursor.

[0044] Condition (ii-2): The polymer component contains at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1) shown in Formula (1) and a polyimide as an imide derivative of the polyimide precursor; and at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1') shown in Formula (1') and a repeating unit (a2) shown in Formula (2) below and a polyimide as an imide derivative of the polyimide precursor.

[0045]

[0046] (X2 represents a tetravalent organic group. Y2 represents a divalent organic group with the group -X-J. R and Z each independently represent a hydrogen atom or a monovalent organic group.)

[0047] In the group –X-J, X represents a single bond, –(CH2). a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -COO-, -OCO-, -Ak-O-CO-CH=CH-** (** represents a bond with an aromatic hydrocarbon group. Ak represents a divalent organic group with 1 to 10 carbon atoms) or -(Al) a0 -((CH2) a1 -A1) m1 - (a0 is an integer of 0 or 1, a1 is an integer from 1 to 15, each A1 independently represents -O- or -COO-, and m1 is an integer from 1 to 2. When m1 is 2, multiple a1s independently have the above definition).

[0048] J represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an aromatic hydrocarbon group having 6 to 40 carbon atoms. Wherein, at least one of the hydrogen atoms in the alicyclic hydrocarbon group and the aromatic hydrocarbon group is substituted by a substituent (v) as a halogen atom, an alkyl group containing a halogen atom having 1 to 10 carbon atoms, an alkoxy group containing a halogen atom having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkenyl group having 3 to 10 carbon atoms. Furthermore, any carbon-carbon single bond in these substituents (v) (wherein excluding the halogen atom) is optionally interrupted by -O-.

[0049]

[10] The liquid crystal alignment agent according to any one of [1] to [9], wherein X1 and X 1’ The tetravalent organic group in the formula is a tetravalent organic group derived from tetracarboxylic dianhydride or its derivatives, wherein the tetravalent organic group is a tetravalent organic group derived from acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, or their derivatives.

[0050]

[11] A liquid crystal alignment film, which is obtained from any one of the liquid crystal alignment agents as described in [1] to

[10] .

[0051]

[12] A liquid crystal display element having a liquid crystal alignment film as described in

[11] .

[0052]

[13] A method for manufacturing a liquid crystal display element, comprising performing the following steps (1) to (3) in sequence.

[0053] Step (1): A step of coating a liquid crystal alignment agent as described in any one of [1] to

[10] onto at least one of a pair of substrates having a conductive film to form a coating film.

[0054] Process (2): The process of firing the coating film.

[0055] Process (3): Forming a liquid crystal layer between the pair of substrates to manufacture a liquid crystal cell.

[0056]

[14] The manufacturing method of the liquid crystal display element according to

[13] includes, after steps (1) to (3), the following step (4) is further performed.

[0057] Step (4): The process of irradiating the liquid crystal cell with light.

[0058] It should be noted that in this specification, * denotes a bond in all cases. Examples of halogen atoms include: fluorine, chlorine, bromine, and iodine.

[0059] Invention Effects

[0060] According to the liquid crystal alignment agent of the present invention, a liquid crystal alignment film with high voltage retention rate can be obtained even after prolonged exposure to high temperature and high humidity.

[0061] The mechanism by which the above-mentioned effects of the present invention are obtained may not be clear, but the following description is considered to be one of the reasons. The oxazoline skeleton contained in the polymer used in the present invention (e.g., the structures (s-Ox) and (m-Ox) described later) undergoes ring-opening during post-baking, and cross-links with the carboxylic acid in the amic acid. This ring-opening reaction is promoted by a catalytic effect under acidic conditions; therefore, it can be considered that the ring-opening reaction is further carried out by the presence of divalent organic groups (Ah) with aliphatic carboxyl groups or divalent organic groups (ph) with phenolic hydroxyl groups, cross-linking with carboxylic acids, resulting in increased film density of the obtained liquid crystal alignment film, thus enabling the acquisition of a liquid crystal alignment film with higher voltage retention. Detailed Implementation

[0062] The following describes the components of the liquid crystal alignment agent disclosed herein, as well as any other components that may be added as needed.

[0063] <Polymer Composition>

[0064] The liquid crystal alignment agent of the present invention contains a polymer component.

[0065] The polymer components satisfy at least any one of the following conditions (i) and (ii).

[0066] Condition (i): The polymer component contains at least one polymer (P-a1+a1') selected from the group consisting of a polyimide precursor having repeating unit (a1) shown in formula (1) and repeating unit (a1') shown in formula (1') and a polyimide as an imide derivative of the polyimide precursor (hereinafter also referred to as a copolymer).

[0067] Condition (ii): The polymer component contains at least one polymer (P-a1) selected from the group consisting of a polyimide precursor having a repeating unit (a1) as shown in formula (1) and a polyimide as an imide derivative of the polyimide precursor; and at least one polymer (P-a1') selected from the group consisting of a polyimide precursor having a repeating unit (a1') as shown in formula (1') and a polyimide as an imide derivative of the polyimide precursor (hereinafter, a mixture of polymer (P-a1) and polymer (P-a1') is also referred to as a polymer blend).

[0068] The copolymers and polymer blends described above can be used alone or in combination.

[0069] It should be noted that, in condition (i), the repeating unit (a1) shown in equation (1) and the repeating unit (a1') shown in equation (1') exist within the same molecule of the polymer.

[0070] It should be noted that the above polymer components may further contain at least one polymer selected from the group consisting of a polyimide precursor that does not have the above repeating unit (a1) and the above repeating unit (a1') and an imide derivative of the polyimide precursor.

[0071] When the polymer composition contains the copolymer, from the viewpoint of properly obtaining the effects of the present invention, the total content ratio of the repeating unit (a1), the repeating unit (a1'), and their imidized structural units in the copolymer is preferably 5 to 100 mol%, more preferably 10 to 100 mol%, and even more preferably 20 to 100 mol%.

[0072] Furthermore, from the viewpoint of properly obtaining the effects of the present invention, the total content ratio of the repeating unit (a1) and the imidized structural unit of the repeating unit (a1) in the copolymer is preferably 1 to 90 mol%, more preferably 5 to 85 mol%, and even more preferably 10 to 80 mol% of the repeating unit constituting the copolymer as a whole.

[0073] When the polymer composition contains the polymer blend, from the viewpoint of properly obtaining the effects of the present invention, the total content ratio of the repeating unit (a1) and the imidized structural unit of the repeating unit (a1) in the polymer (P-a1) is preferably 1 to 99 mol%, more preferably 2 to 95 mol%, and even more preferably 5 to 90 mol% of the repeating unit constituting the polymer (P-a1).

[0074] Furthermore, from the viewpoint of efficiently obtaining the effects of the present invention, the total content ratio of the repeating unit (a1') and the imidized structural unit of the repeating unit (a1') in the polymer (P-a1') is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, constituting the total repeating unit of the polymer (P-a1').

[0075] Furthermore, the mass ratio of the content of the polymer (P-a1) to the content of the polymer (P-a1') in the above-mentioned polymer component ((P-a1) / (P-a1')) is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10.

[0076] (Repeating unit (a1))

[0077] In formula (1) above, Y1 represents a divalent organic group having an oxazoline backbone. It is acceptable as long as at least one of the main chain and side chain of the polymer has an oxazoline backbone. When the oxazoline backbone in Y1 is located on the side chain of the polymer having Y1, the position of the oxazoline backbone in the side chain is not particularly limited; it can be in the middle or at the end of the polymer side chain. In the above case, it is more preferable that Y1 has the oxazoline backbone located at the end of the polymer side chain. Furthermore, Y1 preferably has a partial structure as shown in the following formula (s-Ox).

[0078]

[0079] (n is an integer from 1 to 3. When n is 1, R represents a single bond, -O-, or a (n+1) valence organic group. When n is 2 or 3, R represents a (n+1) valence organic group.)

[0080] Examples of (n+1) valence organic groups in the above formula (s-Ox) include: -COO-, -CONH-, (n+1) valence hydrocarbon groups ((n+1) valence acyclic chain hydrocarbon groups with 1 to 10 carbon atoms, (n+1) valence alicyclic hydrocarbon groups with 3 to 10 carbon atoms, (n+1) valence aromatic hydrocarbon groups with 6 to 18 carbon atoms), (n+1) valence organic groups formed by replacing at least one methylene group in the above hydrocarbon groups with divalent functional groups such as -O-, -S-, -CO-, -COO-, -COS-, -NR1-, -CONR1- (R1 is a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms), (n+1) valence organic groups formed by replacing at least one hydrogen atom in the above hydrocarbon groups with a halogen atom, etc., and (n+1) valence organic groups with heterocycles.

[0081] As a more preferred specific example of the partial structure shown in the above formula (s-Ox), the partial structures shown in the following formulas (s-Ox-1) to (s-Ox-5) can be listed.

[0082]

[0083] (In the formula, L represents -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -COO-, or -OCO-. n4 is an integer from 0 to 3, and n5 is an integer from 1 to 3.)

[0084] When the oxazoline backbone in Y1 is located on the side chain of a polymer having Y1, it is preferable that Y1 is a group formed by removing two amino groups from a diamine having a partial structure shown in the above formula (s-Ox) (hereinafter also referred to as a specific diamine (s-Ox)). As a specific example of the above-mentioned specific diamine (s-Ox), "A1-(Z1)" is preferred. m(A1 represents an m-valent group formed by the bonding of two primary amino groups with an aromatic group. Specific examples of aromatic ring structures in aromatic groups include: benzene rings, naphthalene rings, biphenyl structures, or aromatic ring structures formed by two benzene rings linked by alkylene groups with 1 to 3 carbon atoms. Z1 represents a partial structure shown in the above formula (s-Ox). m is an integer from 1 to 2.)

[0085] In the above diamine "A1-(Z1)" m In the case where the aromatic group of A1 represents a benzene ring, the two amino groups in the diaminophenyl are preferably located at the 2,5- or 3,5- positions relative to Z1.

[0086] When the oxazoline backbone in Y1 is located in the main chain of a polymer having Y1, Y1 preferably has a partial structure as shown in the following formula (m-Ox).

[0087]

[0088] (R 1 * indicates a hydrogen atom or a monovalent organic group; * indicates a bonded bond.

[0089] R, as in the above equation (m-Ox) 1 The monovalent organic group in the form of the aromatic group is preferably a monovalent organic group having an aromatic group (such as an aromatic ring structure, for example, a benzene ring), a monovalent chain hydrocarbon group having 1 to 10 carbon atoms (such as methyl, ethyl, propyl, etc.), or a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms. The aforementioned monovalent organic group having an aromatic group may consist only of an aromatic group, or a portion thereof may include at least one of a chain structure and the aforementioned alicyclic structure. Furthermore, the aforementioned alicyclic hydrocarbon group may consist only of an alicyclic structure (such as a cyclohexane ring), or a portion thereof may include a chain structure. It should be noted that at least one hydrogen atom in the aforementioned monovalent organic group having an aromatic group, the aforementioned chain hydrocarbon group, or the aforementioned alicyclic hydrocarbon group may optionally be replaced by a halogen atom, a hydroxyl group, a cyano group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, etc. Furthermore, any portion of the methylene group in the aforementioned monovalent organic group having an aromatic group, the aforementioned chain hydrocarbon group, or the aforementioned alicyclic hydrocarbon group is optionally replaced by -O-, -CO-, or -COO-. From the viewpoint of appropriately obtaining the effects of the present invention, the R of the above formula (m-Ox) 1 Preferably, it contains hydrogen atoms or methyl groups.

[0090] When the oxazoline skeleton in Y1 is located in the main chain of a polymer having Y1, Y1 is preferably a group formed by removing two amino groups from a diamine having the structure shown in the above formula (m-Ox) (hereinafter also referred to as a specific diamine (m-Ox)). As specific examples of the above-mentioned specific diamine (m-Ox), diamines selected from the group shown in the following formulas (m-Ox-1) to (m-Ox-3) can be listed.

[0091]

[0092] (R 1 R with equation (m-Ox) 1 They have the same meaning. R 2 Indicates single bond, -O-, -COO-, -OCO-, -CONR 11 -, -NR 11 CO-、-NR 11 - An alkylene group having 1 to 24 carbon atoms, or an alkylene group having 1 to 24 carbon atoms, inserted at at least one position between carbon-carbon bonds and at the end of the alkylene group, selected from -O-, -COO-, -OCO-, -NR-. 11 -CONR 11 -, -NR 11 CO and NR 11 -CO-NR 11 - A divalent organic group formed by the groups in the group, R 11 This indicates a hydrogen atom or a methyl group. W 1 ~W 2 W 4 Each independently represents an aromatic hydrocarbon group, W 3 Represents an aromatic hydrocarbon group or an alicyclic hydrocarbon group. 'a' is an integer, either 0 or 1. In the formula (m-Ox-2), multiple R... 1 W 1 And multiple Rs with a = 1 2 (They may be the same as or different from each other.)

[0093] As mentioned above, W 1 ~W 4 The aromatic hydrocarbon group in the W can be composed solely of an aromatic group (as an aromatic ring structure within the aromatic group, such as a benzene ring, naphthalene ring, biphenyl structure, anthracene ring, etc.), or it can be a hydrocarbon group linked by at least one of the above aromatic groups through a chain structure (e.g., a structure with an alkylene group) and an alicyclic structure (e.g., a cyclohexane ring, etc.). 1 ~W 4 Preferred examples of aromatic ring structures in aromatic hydrocarbon groups are benzene rings, naphthalene rings, and biphenyl structures. As W 3 The alicyclic hydrocarbon group in W can consist solely of an alicyclic structure, or it can contain a chain-like structure in a portion of it.3 The alicyclic hydrocarbon group is preferably cyclohexylene or bicyclohexylene. It should be noted that a portion of the hydrogen atoms in the aforementioned aromatic hydrocarbon group or alicyclic hydrocarbon group may optionally be substituted with a substituent, and furthermore, any portion of the methylene group may optionally be substituted with -O-, -CO-, or -COO-. Examples of such substituents include: halogen atoms, hydroxyl groups, cyano groups, alkyl groups with 1 to 3 carbon atoms, alkoxy groups with 1 to 3 carbon atoms, fluoroalkyl groups with 1 to 3 carbon atoms, dialkylamino groups (e.g., dimethylamino), carboxylic acid amide groups (e.g., acetate amide group, propionic acid amide group), etc.

[0094] From the viewpoint of properly obtaining the effects of the present invention, -R in the above formulas (m-Ox-1) and (m-Ox-3) 2 -W 2 - Preferably - (CH2) n -O-Ar 1 -、-(CH2) n -OCO-Ar 1 -、-(CH2) n -NR 11 CO-Ar 1 -、-(CH2) n -NR 11 -Ar 1 - (n is an integer from 1 to 6. Ar 1 It represents 1,4-phenylene or 4,4'-biphenyldiyl. R 11 (Represents a hydrogen atom or a methyl group).

[0095] From the viewpoint of properly obtaining the effects of the present invention, -R in the above formula (m-Ox-2) 2 -(W 3 -R 2 ) a - Preferably - (CH2) n -OCO-(CH2) m -COO-(CH2) n -、-(CH2) n -NR 11 CO-(CH2) m -CONR 11 -(CH2) n -、-(CH2) n -NR 11 -CO-NR 11 -(CH2) n -、-(CH2) n -OCO-Cy-COO-(CH2) n -、-(CH2) n -NR11 CO-Cy-CONR 11 -(CH2) n - (n is an integer from 1 to 6. m is an integer from 1 to 12. Cy represents 1,4-phenylene or 1,4-cyclohexylene. R 11 (Represents a hydrogen atom or a methyl group).

[0096] From the viewpoint of properly obtaining the effects of the present invention, -W in (m-Ox-3) 4 - Preferably 1,4-phenylene.

[0097] (Repeating unit (a1'))

[0098] In the above equation (1'), Y 1’ This indicates a divalent organic group (Ah) having an aliphatic carboxyl group or a divalent organic group (ph) having a phenolic hydroxyl group.

[0099] (Divalent organic group (Ah))

[0100] Here, an aliphatic carboxyl group refers to a functional group formed by the direct bonding of at least one carboxyl group with an aliphatic group. The number of carboxyl groups bonded to the aliphatic group is not particularly limited, but from an availability point of view, 1 to 8 are preferred.

[0101] As specific examples of the aforementioned aliphatic groups, there is no particular limitation as long as the group has an aliphatic structure; preferably, it is an aliphatic group in which the carboxyl group is bonded to the carbon atom of the methylene group or to the carbon atom forming an alicyclic structure. As more preferred specific examples of aliphatic groups, chain hydrocarbon groups with 1 to 30 carbon atoms or alicyclic hydrocarbon groups with 3 to 30 carbon atoms can be listed.

[0102] Here, a chain hydrocarbon group refers to a straight-chain hydrocarbon group or a branched hydrocarbon group that does not have an alicyclic structure. The chain hydrocarbon group can be saturated or unsaturated. It should be noted that the aforementioned chain hydrocarbon group may have -O-, -CO-, -CO-O-, -NR- (R represents a hydrogen atom or a methyl group), or -NR-CO- (R represents a hydrogen atom or a methyl group) inserted at least at one point between carbon-carbon bonds or at its end (hereinafter, these are also referred to as heteroatom-containing groups).

[0103] The aforementioned alicyclic hydrocarbon groups can consist solely of alicyclic structures (such as cyclobutane, cyclopentane, and cyclohexane rings), or they can include a chain structure in a portion thereof. Furthermore, this chain structure can also incorporate heteroatom-containing groups between carbon-carbon bonds.

[0104] At least one of the hydrogen atoms in the carbon atom constituting the aliphatic group is optionally replaced by a halogen atom, hydroxyl group, cyano group, phenyl group, or amino group.

[0105] The valence of the aforementioned aliphatic groups is preferably monovalent to divalent.

[0106] In Y 1’ In the case of a divalent organic group (Ah), Y 1’ Preferably, it is a group obtained by removing two amino groups from a diamine having an aliphatic carboxyl group (hereinafter also referred to as a specific diamine (Ah)). As a specific example of the above-mentioned specific diamine (Ah), it is preferably "A 1’ -(L-Ah) m’ "or "(A 11’ The aromatic diamine represented by )2-Ah'”.

[0107] Here, A 1’ This represents an m' valence group formed by the bonding of two primary amino groups with an aromatic group. A 11’ It represents a monovalent group formed by the bonding of a primary amino group and an aromatic group.

[0108] Specific examples of aromatic ring structures in aromatic groups include: benzene rings, naphthalene rings, biphenyl structures, or aromatic ring structures formed by two benzene rings linked by a linking group (-CH2-, -C(CH3)2-, -O-, -CO-, -CO-O-, -NR- (R represents a hydrogen atom or a methyl group) or -NR-CO- (R represents a hydrogen atom or a methyl group) or -N=N-, etc.).

[0109] L represents a single bond, -O-, -CO-, -CO-O-, -NR- (R represents a hydrogen atom or a methyl group), or -NR-CO- (R represents a hydrogen atom or a methyl group). Ah represents a monovalent aliphatic carboxyl group. m' is an integer from 1 to 2.

[0110] Ah' represents a divalent aliphatic carboxyl group.

[0111] As a more preferred specific example of the aforementioned specific diamine (Ah), diamines selected from the group shown in formulas (Ah-1) to (Ah-5) can be listed.

[0112]

[0113] In formulas (Ah-1) to (Ah-3), L represents a single bond, -O-, -CO-, -CO-O-, -NR- (R represents a hydrogen atom or a methyl group), or -NR-CO- (R represents a hydrogen atom or a methyl group). Ak is an alkylene group with 1 to 20 carbon atoms, wherein some of the hydrogen atoms in the alkylene group are optionally replaced by hydroxyl, halogen, or phenyl groups. In formula (Ah-3), n3 is an integer of 0 or 1. In formula (Ah-4), m4 is an integer of 1 to 5 independently. In formula (Ah-5), A 5 (m5 represents a straight-chain or branched alkyl group with 1 to 5 carbon atoms, where m5 is an integer from 1 to 5.)

[0114] (Divalent organic group (ph))

[0115] The divalent organic group (ph) has a phenolic hydroxyl group. A phenolic hydroxyl group is a hydroxyl group bonded to an aromatic hydrocarbon ring. Examples of aromatic hydrocarbon rings include the benzene ring and the naphthalene ring.

[0116] The divalent organic group (ph) preferably has the following structure (ph-1) as the structure having the phenolic hydroxyl group.

[0117]

[0118] (Ar represents a benzene ring or a naphthalene ring. R represents a hydrogen atom, a methyl group, a methoxy group, or a halogen atom. * represents a bond.)

[0119] When Ar is a benzene ring, p represents an integer from 1 to 5, q represents an integer from 0 to 4, and r represents an integer from 1 to 5. The total of p, q, and r is 6.

[0120] When Ar is a naphthalene ring, p represents an integer from 1 to 7, q represents an integer from 0 to 6, and r represents an integer from 1 to 7. The sum of p, q, and r is 8.

[0121] In Y 1’ In the case of a divalent organic group (ph), Y is preferred. 1’ Preferably, the group is formed by removing two amino groups from a diamine having the structure shown in the above formula (ph) (hereinafter also referred to as a specific diamine (ph)). As a more preferred specific example of the above specific diamine (ph), a diamine with the following formula (ph-0) can be listed.

[0122]

[0123] (P represents the structure shown in the above formula (ph-1) (where r represents 1 in the above formula (ph-1)). L represents a single bond or a divalent group.)

[0124] Examples of divalent groups representing L in the above formula (ph-0) include: divalent hydrocarbon groups with 1 to 30 carbon atoms, or groups in which at least one methylene group of the hydrocarbon group is replaced by divalent functional groups such as -O-, -S-, -CO-, -COO-, -COS-, -NR-, -CONR-, -CO-NR-CO- (where R is a hydrogen atom or an alkyl group with 1 to 3 carbon atoms). Furthermore, the hydrogen atoms in the hydrocarbon group may optionally be replaced by halogen atoms, hydroxyl groups, cyano groups, amino groups, etc. Examples of hydrocarbon groups include: chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.

[0125] Specific examples of chain-like hydrocarbon groups include: divalent straight-chain or branched hydrocarbon groups with 1 to 30 carbon atoms that do not have a cyclic structure, preferably alkylene groups with 1 to 30 carbon atoms. Specific examples of alicyclic hydrocarbon groups include those in W... 3 The structure is illustrated by an example of an alicyclic hydrocarbon group. As a specific example of an aromatic hydrocarbon group, it can be illustrated by the structure shown above in the W... 1 ~W 4 The structures exemplified are those of aromatic hydrocarbon groups in the text.

[0126] From the viewpoint of properly obtaining the effects of the present invention, the divalent group of L in the above formula (ph-0) is preferably -(CH2). n -O- (n is an integer from 1 to 6), -(CH2) n -C(=O)-NH- (n is an integer from 1 to 6), -(CH2) n -O-C(=O)-(n is an integer from 1 to 6), -(CH2) n -C(=O)-O- (n is an integer from 1 to 6), -O- (CH2) n -O- (n is an integer from 1 to 6), -C (=O)-O- (CH2) n -O- (n is an integer from 1 to 6), -(CH2) m -C(=O)-O-(CH2) n -(m and n are independent integers from 1 to 6) or -C (=O) -O -(CH2) n -O-C(=O)-(n is an integer from 1 to 6).

[0127] In the above formula (ph-0), P is preferably the structure shown in the following formulas (p-1) to (p-6).

[0128]

[0129] As specific examples of the aforementioned diamines (ph), diamines (1-18) with the following structural formulas can be listed.

[0130]

[0131] Another aspect of the present invention is a liquid crystal alignment agent in which the polymer component satisfies at least any one of the following conditions (i-1), (ii-1), and (ii-2).

[0132] Condition (i-1): The polymer component contains at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1) shown in formula (1), a repeating unit (a1') shown in formula (1') and a repeating unit (a2) shown in formula (2) and a polyimide as an imide derivative of the polyimide precursor.

[0133] Condition (ii-1): The polymer component comprises at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1) shown in formula (1) and a repeating unit (a2) shown in formula (2) below, and a polyimide as an imide derivative of the polyimide precursor; and at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1') shown in formula (1') and a polyimide as an imide derivative of the polyimide precursor.

[0134] Condition (ii-2): The polymer component comprises: at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1) shown in the above formula (1) and a polyimide as an imide derivative of the polyimide precursor; and at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit (a1') shown in the above formula (1') and a repeating unit (a2) shown in the following formula (2) and a polyimide as an imide derivative of the polyimide precursor.

[0135] It should be noted that, in condition (i-1), the repeating unit (a1) shown in equation (1), the repeating unit (a1') shown in equation (1'), and the repeating unit (a2) shown in equation (2) exist within the same molecule of the polymer.

[0136] (Repeating unit (a2))

[0137] The polymer component contained in the liquid crystal alignment agent of the present invention may further have a repeating unit (a2) as shown in formula (2) below. The polymer component may also be a polyimide that is an imide derivative of a polyimide precursor having a repeating unit (a2) as shown in formula (2) below. It should be noted that the repeating unit (a2) may be one type or more types.

[0138]

[0139] (X2 represents a tetravalent organic group. Y2 represents a divalent organic group with the group -X-J. R and Z each independently represent a hydrogen atom or a monovalent organic group.)

[0140] In the above group -X-J, X represents a single bond and -(CH2). a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -COO-, -OCO-, -Ak-O-CO-CH=CH-** (** represents a bond with an aromatic hydrocarbon group. Ak represents a divalent organic group with 1 to 10 carbon atoms) or -(Al) a0 -((CH2) a1 -A1) m1 - (a0 is an integer of 0 or 1, a1 is an integer from 1 to 15, each A1 independently represents -O- or -COO-, and m1 is an integer from 1 to 2. When m1 is 2, multiple a1s independently have the above definition).

[0141] J represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an aromatic hydrocarbon group having 6 to 40 carbon atoms. In this group, at least one of the hydrogen atoms in the alicyclic hydrocarbon group and the aromatic hydrocarbon group is substituted by a substituent (v) that is a halogen atom, an alkyl group containing a halogen atom having 1 to 10 carbon atoms, an alkoxy group containing a halogen atom having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkenyl group having 3 to 10 carbon atoms. Furthermore, any carbon-carbon single bond in these substituents (v) (wherein excluding halogen atoms) is optionally interrupted by -O-. It should be noted that, in addition to having the aforementioned alicyclic hydrocarbon group and aromatic hydrocarbon group, J optionally further has at least one group selected from the group consisting of an alicyclic hydrocarbon group and an aromatic hydrocarbon group that is unsubstituted or substituted by a substituent other than the aforementioned substituent (v).

[0142] The Y2 mentioned above is preferably a group obtained by removing two amino groups from an aromatic diamine (hereinafter also referred to as a specific diamine (V)) shown in "A-X-J".

[0143] In the specific diamine (V) mentioned above, A represents a monovalent group formed by the bonding of two primary amino groups with an aromatic group. Specific examples of aromatic ring structures within aromatic groups include: benzene rings, naphthalene rings, and biphenyl structures.

[0144] Examples of alicyclic hydrocarbon groups with 4 to 40 carbon atoms in J include cyclobutyl, cyclopentyl, cyclohexyl, cyclodecyl, and groups with a steroidal skeleton (e.g., cholesteryl, cholesterolyl, or lanostane). Examples of aromatic hydrocarbon groups with 6 to 40 carbon atoms include phenyl and naphthyl. When J has at least any one of cyclohexyl and phenyl, the following structure (S1) can be listed as the group "-X-J", and the following formulas (S1-1) to (S1-5) can be listed as more preferred structures.

[0145]

[0146] (X 1 This indicates the definition of X in the group -X-J or -O-CO-CH=CH-** (** represents a bond with a phenylene group). G 1 The term indicates a divalent cyclic group selected from phenylene and cyclohexylene. Any hydrogen atom on the cyclic group may optionally be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.

[0147] m is an integer from 1 to 4. When m is 2 or greater, there are multiple X... 1 G 1 Each of them independently possesses the above definition.

[0148] R 1 This refers to a fluorine atom, an alkyl group containing fluorine atoms with 1 to 10 carbon atoms, an alkoxy group containing fluorine atoms with 1 to 10 carbon atoms, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, or an alkoxyalkyl group with 3 to 10 carbon atoms.

[0149]

[0150] (X 1 R 1 X in the above formula (S1) 1 R 1 The meaning is the same.

[0151] Specific examples of the aforementioned diamine (V) include diamines represented by formulas (d-1) to (d-2) below. More preferred examples include diamines represented by formulas (d-1) to (d-2) whose group "-X-J" is any of the above-described structures (S1) or formulas (S1-1) to (S1-5), as well as diamines having a steroidal skeleton such as cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteryl ester of 3,5-diaminobenzoate, cholesteryl ester of 3,5-diaminobenzoate, cholesteryl ester of 3,5-diaminobenzoate, and lanostane of 3,6-bis(4-aminobenzoyloxy)cholestane. In the following formulas (d-1) to (d-2), where X represents -Ak-O-CO-CH=CH-** (** represents a bond bonded to an aromatic hydrocarbon group. Ak represents a divalent organic group with 1 to 10 carbon atoms), preferred specific examples include: [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate.

[0152]

[0153] (X and J, including preferred embodiments, have the same meaning as X and J in the above-described group -X-J. In formula (d-2), the two X and J may optionally be the same as or different from each other.)

[0154] (Repeating unit (a3))

[0155] The polymer component contained in the liquid crystal alignment agent of the present invention may further have a repeating unit (a3) ​​as shown in formula (3) below, and the polymer component contained in the liquid crystal alignment agent of the present invention may also contain a polyimide as an imide derivative having a repeating unit (a3) ​​as shown in formula (3) below. It should be noted that the repeating unit (a3) ​​may be one type or two or more types.

[0156]

[0157] (X3 represents a tetravalent organic group. Y3 represents a divalent organic group, indicating that in the above formulas Y1 and Y...) 1’Divalent organic groups other than those defined in Y2. The two R and Z groups each have the same meaning as R and Z in formula (1).

[0158] Y3 is preferably a divalent organic group obtained by removing two amino groups from a diamine described below (hereinafter also referred to as other diamines). It should be noted that other diamines are not particularly limited, and diamines other than those described below can be used.

[0159] p-Phenylenediamine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,5-Dimethyl-p-phenylenediamine, m-Phenylenediamine, 2,4-Dimethyl-m-phenylenediamine, 2,5-Diaminotoluene, 2,6-Diaminotoluene, 2,2'-Dimethyl-4,4'-Diaminobiphenyl, 3,3'-Dimethyl-4,4'-Diaminobiphenyl, 3,3'-Dimethoxy-4,4'-Diaminobiphenyl, 2,2'-Difluoro-4,4'-Diaminobiphenyl, 3,3'-Difluoro-4,4'-Diaminobiphenyl, 2,2'-Bis(trifluoromethyl)-4,4'-Diaminobiphenyl, 3,3'-Bis(trifluoromethyl)-4,4'-Diaminobiphenyl, 3,4'-Diaminobiphenyl, 4... 4'-Diaminobiphenyl, 3,3'-Diaminobiphenyl, 2,2'-Diaminobiphenyl, 2,3'-Diaminobiphenyl, 1,5-Diaminonaphthalene, 1,6-Diaminonaphthalene, 1,7-Diaminonaphthalene, 2,5-Diaminonaphthalene, 2,6-Diaminonaphthalene, 2,7-Diaminonaphthalene, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-amino-2-methylphenoxy)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,5-bis(4-aminophenoxy)pentane, 1 5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12- bis(3-aminophenoxy)dodecane, 3-[2-[2-(4-aminophenoxy)ethoxy]ethoxy]aniline, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthyl)ethane, 1,2-bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 4'-[2-(4-aminophenoxy)ethoxy]-[1,[1'-Biphenyl]-4-amine, 1,4-bis[2-(4-aminophenyl)ethyl]succinate, 1,6-bis[2-(4-aminophenyl)ethyl]adipate, 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate; diamines with photo-oriented groups such as 4,4'-diaminoazobenzene, diaminodiphenylacetylene, or 4,4'-diaminochalcone; methacrylic acid Diamines with photopolymerizable groups at the ends, such as 2-(2,4-diaminophenoxy)ethyl ester and 2,4-diamino-N,N-diallyl aniline; diamines with intramolecular groups that function as free radical polymerization initiators, such as 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropionone, 2-(4-(2-hydroxy-2-methylpropionyl)phenoxy)ethyl-3,5-diaminobenzoate, benzoin or its alkyl ethers, benzyl ketals, acetophenones, phosphine oxides, benzophenones, or aminobenzophenones (hereinafter also referred to as diamines with free radical initiation function); diamines with amide bonds, such as 4,4'-diaminobenzoylaniline, 1,3-diaminobenzoylaniline, etc. Diamines containing urea bonds, such as (4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, and 1,3-bis(4-aminophenylethyl)urea; 4,4'-sulfonyl diphenylamine, 3,3'-sulfonyl diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)phenyl]hexafluoropropane, etc. 2,2-Bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-amino-4-methylphenyl)propane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene; 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3-6-Diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-(3-(1H-imidazol-1-yl)propyl-3,5-diaminobenzamide, 1,4-bis(p-aminobenzyl)piperazine, 4,4'-[propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, diamines represented by formulas (z-1) to (z-5) below (m in formula (z-2) each has the following definition independently), 2,5-bis(4-aminophenyl)pyrrole, 4,4'-(1-methyl-1H- Pyrrole-2,5-diyl)bis[aniline], 1,4-bis-(4-aminophenyl)-piperazine, 2-N-(4-aminophenyl)pyridine-2,5-diamine, 2-N-(5-aminopyridin-2-yl)pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-6-aminobenzimidazole, 5-(1H-benzimidazole-2-yl)phenyl-1,3-diamine and other heterocyclic diamines, or 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-1,4-phenylenediamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N' -Dimethylbenzidine or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-phenylenediamine, etc., representing diamines with a diphenylamine structure, having at least one nitrogen-containing structure selected from the group consisting of nitrogen-containing heterocycles, secondary amino groups, and tertiary amino groups (hereinafter also referred to as specific nitrogen-containing structures) (wherein, the molecule does not have an amino group bonded by a protecting group that is removed by heating and substituted with a hydrogen atom. Furthermore, specific diamines (s-Ox) and specific diamines (m-Ox) are not included); 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4 Aromatic diamines with aromatic carboxyl groups, such as '-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 1,2-bis(4-aminophenyl)ethane-3,3'-dicarboxylic acid, and 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-Trimethyl-1H-indane-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indane-6-amine; N,N'-bis(2-tert-butoxycarbonylamino-4-aminophenyl)hexamethylenediamine, 4-amino-N-(2-tert-butoxycarbonylamino-4-aminophenyl)benzamide, N-[(2,5-diaminophenyl)methyl]-1,1-dimethyl ethyl ester of carbamate, N-[3-(2,5-diaminophenyl)propyl]-1,1-dimethyl ethyl ester of carbamate, N,N-[(2,5-diamino-1,3-phenylene)di-3,1-propanediyl]bis-C C-bis(1,1-dimethylethyl) ester, N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine, 4-amino-2-tert-butoxycarbonylamino-1,1'-[(1,1,3,3-tetramethyl-1,3-disiloxanediyl)di-4,1-butanediyl] ester, N-[2-(4-aminophenyl)ethyl]-N-[[[2-(4-aminophenyl)ethyl]amino]carbonyl]-1,1-dimethylethyl ester, N-(4-aminophenyl)-N-[[1-(4-aminophenyl)-4-piperidinyl]methyl]-1,1-dimethylethyl ester, etc. Diamines containing the group "-N(D)-" (D represents a protecting group that is removed and replaced by a hydrogen atom by heating, preferably tert-butoxycarbonyl); represented by 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecanyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-dodecyloxy-2,5-diaminobenzene, 1-tetradecyloxy-2,5-diaminobenzene, 1-pentadecanyloxy-2,5-diaminobenzene, 1-hexadecyloxy-2,5-diaminobenzene, and 1-octadecyloxy-2,5-diaminobenzene. Aromatic diamines having long-chain alkyl groups with 12 to 20 carbon atoms; diamines with siloxane bonds, such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis[3-(p-aminophenylcarbamoyl)propyl]tetramethyldisiloxane; and diamines with two amino groups bonded to groups represented by any of the formulas (Y-1) to (Y-167) as described in International Publication No. 2018 / 117239.

[0160]

[0161] From the perspective of accelerating the response speed of liquid crystal display elements using PSA and SC-PVA modes, one or more of the diamines having photopolymerizable groups at the ends and the diamines having free radical initiation functions can be used when manufacturing the polymer components.

[0162] As other diamines, from the viewpoint of properly obtaining the effects of the present invention, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminobiphenyl, the above-mentioned diamines having free radical initiation function, the above-mentioned diamines having a specific nitrogen-containing structure, and the above-mentioned diamines having the group "-N(D)-" are preferred.

[0163] As a specific embodiment of a polymer composition having the aforementioned repeating unit (a2) and / or repeating unit (a3), copolymers and polymer blends are examples.

[0164] Examples of the copolymers described above include at least one polymer selected from the group consisting of polyimide precursors and their imidized polymers having repeating units (a1), (a1'), (a2), and / or (a3) ​​within the same molecule.

[0165] Examples of the aforementioned polymer blends include: a mixture of polymer (P-a1+an) and polymer (P-a1'+an), wherein the polymer (P-a1+an) is selected from at least one group consisting of polyimide precursors and their imidized polymers having the aforementioned repeating unit (a1), repeating unit (a2), and / or repeating unit (a3) ​​within the same molecule; and the polymer (P-a1'+an) is selected from at least one group consisting of polyimide precursors and their imidized polymers having the aforementioned repeating unit (a1'), repeating unit (a2), and / or repeating unit (a3) ​​within the same molecule. The aforementioned copolymers or polymer blends can be used alone or in combination.

[0166] In the copolymer described above, when at least one of the repeating unit (a2) and the imidized structural unit of the repeating unit (a2) is included, from the viewpoint of properly obtaining the effects of the present invention, the total content ratio of the repeating unit (a2) and the imidized structural unit of the repeating unit (a2) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, and even more preferably 10 to 85 mol% of the repeating unit constituting the copolymer as a whole.

[0167] In this case, from the viewpoint of properly obtaining the effects of the present invention, the total content of the above-mentioned repeating unit (a1), the above-mentioned repeating unit (a1'), and their imidized structural units is preferably 95 mol% or less, more preferably 90 mol% or less.

[0168] In the polymer blend described above, when the polymer (P-a1+an) contains at least one of the repeating unit (a2) and the imidized structural unit of the repeating unit (a2), from the viewpoint of properly obtaining the effects of the present invention, the total content ratio of the repeating unit (a2) and the imidized structural unit of the repeating unit (a2) is preferably 5 to 95 mol% of the total repeating unit constituting the polymer (P-a1+an), more preferably 10 to 90 mol%, and even more preferably 10 to 85 mol%.

[0169] In this case, from the viewpoint of properly obtaining the effects of the present invention, the total content ratio of the repeating unit (a1) and the imidized structural unit of the repeating unit (a1) is preferably 95 mol% or less, more preferably 90 mol% or less.

[0170] Furthermore, in the polymer blend described above, when the polymer (P-a1'+an) contains at least one of the repeating unit (a3) ​​and the imidized structural unit of the repeating unit (a3), from the viewpoint of properly obtaining the effects of the present invention, the total content ratio of the repeating unit (a3) ​​and the imidized structural unit of the repeating unit (a3) ​​is preferably 10 to 95 mol% of the total repeating unit constituting the polymer (P-a1'+an), more preferably 20 to 90 mol%.

[0171] In this case, from the viewpoint of properly obtaining the effects of the present invention, the total content ratio of the repeating unit (a1') and the imidized structural unit of the repeating unit (a1') is preferably 95 mol% or less, more preferably 90 mol% or less.

[0172] When the polymer component is the polymer blend described above, the mass ratio of the content of the polymer (P-a1+an) to the content of the polymer (P-a1'+an) ((P-a1+an) / (P-a1'+an)) is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10.

[0173] In the above equations (1), (1') and (2) to (3), X1 and X 1’ And X2 to X3 each independently represent a tetravalent organic group. X1, X 1’X2 to X3 preferably represent tetravalent organic groups derived from tetracarboxylic dianhydrides or their derivatives (tetracarboxylic acid dihalides, tetracarboxylic acid diesters, or tetracarboxylic acid diester dihalides, etc.). Examples of such tetravalent organic groups include those derived from acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, or their derivatives. More preferably, these include tetracarboxylic dianhydrides or their derivatives having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0174] As a tetracarboxylic dianhydride or its derivative for obtaining a polyimide precursor contained in the polymer component, acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, or its derivative are preferred. More preferably, it comprises a tetracarboxylic dianhydride or its derivative having at least one partial structure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure.

[0175] It should be noted that acyclic aliphatic tetracarboxylic dianhydrides are obtained by intramolecular dehydration of the four carboxyl groups bonded to the chain hydrocarbon structure. The structure need not consist solely of a chain hydrocarbon; it can also contain alicyclic, aromatic, or heteroatom structures such as oxygen atoms in a portion of the structure.

[0176] Alicyclic tetracarboxylic dianhydrides are acidic dianhydrides obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to the alicyclic structure. None of these four carboxyl groups are bonded to an aromatic ring. Furthermore, it is not necessary for the structure to consist solely of an alicyclic structure; it can also have a chain hydrocarbon structure or an aromatic ring structure in a portion thereof.

[0177] Aromatic tetracarboxylic dianhydrides are acidic dianhydrides obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to an aromatic ring. They do not necessarily consist solely of an aromatic ring structure; a portion of them may also have a chain hydrocarbon structure or an alicyclic structure.

[0178] The above X1, X 1’ X2 to X3 are preferably tetravalent organic groups derived from the following tetracarboxylic dianhydrides or their derivatives (hereinafter also collectively referred to as specific tetracarboxylic acid derivatives).

[0179] Acyclic aliphatic tetracarboxylic anhydrides such as 1,2,3,4-butanetetracarboxylic anhydride; 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3 4-Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-Cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-Dicyclohexyltetracarboxylic dianhydride, 2,3,5-Tricarboxycyclopentylacetic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthyl-1,2-dicarboxylic 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, bicyclo[2 [2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclic [2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 2,4,6,8-tetracarboxylic bicyclic [3.3.0]octane-2:4,6:8-dianhydride and other alicyclic tetracarboxylic dianhydrides; pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-perfluoroisopropylidene dicarboxylic dianhydride Aromatic tetracarboxylic acid dianhydrides such as phthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, ethylene glycol bis(triphenylene) anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic acid anhydride, 4,4'-carbonyldiphthalic acid anhydride, 4,4'-oxydi(1,4-phenylene)bis(phthalic acid) dianhydride, or 4,4'-methylenedi(1,4-phenylene)bis(phthalic acid) dianhydride; and tetracarboxylic acid dianhydrides as described in Japanese Patent Application Publication No. 2010-97188.

[0180] Preferred examples of the aforementioned specific tetracarboxylic acid derivatives include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxylated cyclopentylacetic acid dianhydride, and 5-(2,5-dioxanetetracarboxylic acid). 5-(2,5-dioxatetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxylic acid bicyclo[3.3.0]octane-2:4,6:8-dianhydride, pyromellitic acid di Anhydrides, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, or derivatives thereof.

[0181] The proportion of the aforementioned specific tetracarboxylic acid derivative used relative to 1 mole of all tetracarboxylic acid components used to obtain the polyimide precursor contained in the polymer component is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more.

[0182] As monovalent organic groups of R and Z in the above formulas (1), (1') and (2) to (3), they can be independently listed as: monovalent hydrocarbon groups with 1 to 20 carbon atoms; the methylene group of the hydrocarbon group is surrounded by -O-, -S-, -CO-, -COO-, -COS-, -NR-. 3 -、-CO-NR 3 -, -Si(R) 3 )2-(where R 3The monovalent group A is formed by substituting hydrogen atoms or monovalent hydrocarbon groups with 1 to 10 carbon atoms, such as -SO2-; the monovalent group A is formed by substituting at least one of the hydrogen atoms bonded to the carbon atom of the monovalent hydrocarbon group or monovalent group A with a halogen atom, hydroxyl group, alkoxy group, nitro group, amino group, mercapto group, nitroso group, alkylsilyl group, alkoxysilyl group, silanol group, sulfinyl group, phospho group, carboxyl group, cyano group, sulfonyl group, acyl group, etc.; the monovalent group has a heterocyclic ring. Among them, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, tert-butoxycarbonyl groups, or 9-fluorenemethoxycarbonyl groups are preferred, alkyl groups with 1 to 3 carbon atoms are more preferred, and methyl groups are even more preferred.

[0183] From the viewpoint of achieving the effects of the present invention, R and Z are each independently preferred to be alkyl groups having 1 to 3 carbon atoms, and more preferably hydrogen atoms or methyl groups.

[0184] <Methods for manufacturing polyimide precursors and polyimides>

[0185] Examples of polyimide precursors used in this invention include polyamic acid and polyamic ester. The polyimide precursors used in this invention can be synthesized, for example, by a known method as described in International Publication No. 2013 / 157586.

[0186] Specifically, the polymer is synthesized by reacting a diamine component with a tetracarboxylic acid derivative component in a solvent via a (condensation) reaction. Examples of the tetracarboxylic acid derivative component include tetracarboxylic dianhydride or its derivatives. In cases where a portion of the polymer contains an amic acid structure, a polymer with an amic acid structure (polyamic acid) is obtained, for example, by reacting the tetracarboxylic dianhydride component with the diamine component. The solvent is not particularly limited as long as it dissolves the resulting polymer.

[0187] For example, in the case of obtaining a polymer having a repeating unit as shown in the above formula (1) with R being a hydrogen atom, as a diamine component, a diamine having the structure -N(Z)-Y1-N(Z)- (the definitions of Y1 and Z are the same as in the above formula (1)) is used; in addition, as a tetracarboxylic acid derivative component, a tetracarboxylic acid derivative having the structure of the following formula is used.

[0188]

[0189] (The definition of X1 is the same as in equation (1) above.)

[0190] Polyamates comprising a portion of an ammonate structure can be obtained, for example, by the following known methods: [I] reacting the polyamic acid obtained by the above method with an esterifying agent, [II] reacting a tetracarboxylic acid diester with a diamine, [III] reacting a tetracarboxylic acid diester dihalide with a diamine, etc.

[0191] Furthermore, polyimide can be obtained by cyclizing (imidizing) the above-mentioned polyimide precursor. It should be noted that the imidization rate mentioned in this specification refers to the proportion of imide groups in the total amount of imide groups and carboxyl groups (or their derivatives) derived from tetracarboxylic dianhydride or its derivatives. In polyimide, the imidization rate does not necessarily have to be 100% and can be adjusted arbitrarily according to the application and purpose.

[0192] From the viewpoint of ensuring solubility, the polyimide contained in the liquid crystal alignment agent of the present invention has an imidization rate of 10-95%, preferably 20-95%, and more preferably 30-90%.

[0193] Methods for imidizing polyimide precursors include: thermal imidization by heating a solution of the polyimide precursor while maintaining it in that state, and catalytic imidization by adding a catalyst (such as a basic catalyst like pyridine or an acid anhydride like acetic anhydride) to the solution of the polyimide precursor.

[0194] <End-capping agent>

[0195] When synthesizing the polymer of this invention, it can also be synthesized by using a suitable end-capping agent together with a tetracarboxylic acid component containing tetracarboxylic dianhydride or its derivative and a diamine component containing the aforementioned diamine. The end-capped polymer has the effect of improving the film hardness of the oriented film obtained from the coating and improving the adhesion properties between the sealant and the oriented film.

[0196] Examples of polyimide precursors and ends of polyimides in this invention include: amino, carboxyl, anhydride, or groups derived from the capping agents described below. Amino, carboxyl, and anhydride groups can be obtained through conventional condensation reactions or by capping with the following capping agents.

[0197] Examples of capping agents include: acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynyl phthalic anhydride, etc.; dicarbonate diester compounds such as ditert-butyl dicarbonate and diallyl dicarbonate; acryloyl chloride, methacryloyl... Chlorocarbonyl compounds such as chlorine and nicotinyl chloride; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; and isocyanates with unsaturated bonds such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, 2-acryloyloxyethyl isocyanate, and 2-methacryloyloxyethyl isocyanate.

[0198] The proportion of the capping agent used relative to 100 moles of the total diamine components used is preferably 0.01 to 20 moles, more preferably 0.01 to 10 moles.

[0199] The molecular weight of the polymer used in this invention, taking into account the strength of the liquid crystal alignment film obtained therefrom, the workability during film formation, and the coating properties, is preferably set to 5,000 to 1,000,000, more preferably 10,000 to 150,000, based on the weight-average molecular weight (Mw) determined by GPC (Gel Permeation Chromatography).

[0200] (Liquid crystal alignment agent)

[0201] The liquid crystal alignment agent of the present invention is a liquid composition of a polymer and other components used as needed, preferably dispersed or dissolved in a suitable organic solvent.

[0202] Furthermore, other polymers besides those mentioned above can also be mixed into the liquid crystal alignment agent used to manufacture liquid crystal alignment films. Specific examples of other polymers include polymers selected from the group consisting of the following substances: polysiloxanes, polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-maleic anhydride) copolymers, poly(isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, and poly(meth)acrylates. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), and GSM301 (manufactured by Gifu Shellac Manufacturing). Specific examples of poly(isobutylene-maleic anhydride) copolymers include ISOBAM-600 (manufactured by Kuraray). Specific examples of poly(vinyl ether-maleic anhydride) copolymers include Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland).

[0203] Other polymers may be used alone, or in combination of two or more. The proportion of other polymers relative to 100 parts by weight of the total polymers contained in the liquid crystal alignment agent is preferably 50 parts by weight or less, more preferably 1 to 50 parts by weight, and even more preferably 5 to 40 parts by weight.

[0204] Furthermore, the liquid crystal alignment agent of the present invention may also contain components other than those described above, as needed. Examples of such components include: at least one crosslinking compound selected from the group consisting of a crosslinking compound (c-1) having substituents and a crosslinking compound (c-2) having polymerizable unsaturated groups; functional silane compounds; metal chelating compounds; curing accelerators; surfactants; antioxidants; sensitizers; preservatives; compounds for adjusting the dielectric constant and resistance of the liquid crystal alignment film, wherein the substituents are selected from at least one of epoxy groups, oxacyclobutane groups, oxazoline structures, cyclic carbonate groups, terminal isocyanate groups, hydroxyl groups, and alkoxy groups.

[0205] Specific examples of preferred crosslinking compounds (c-1) and (c-2) mentioned above include the following compounds.As compounds with epoxy groups, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromonepentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, bisphenol A type epoxy resins such as EPIKOTE 828 (manufactured by MITSUBISHI CHEMICAL), bisphenol F type epoxy resins such as EPIKOTE 807 (manufactured by MITSUBISHI CHEMICAL), and YX-8000 (manufactured by MITSUBISHI...) are examples of such epoxy resins. Hydrogenated bisphenol A type epoxy resin (manufactured by CHEMICAL), etc.; YX6954BH30 (manufactured by MITSUBISHI CHEMICAL), etc., epoxy resin containing biphenyl backbone; EPPN-201 (manufactured by Nippon Kayaku Co.), etc., phenolic varnish type epoxy resin; EOCN-102S (manufactured by Nippon Kayaku Co.), etc., (o-, m-, p-)cresol phenolic varnish type epoxy resin; tetra(glycidyloxymethyl)methane; N,N,N',N'-tetraglycidyl-1,4-phenylenediamine; N,N Compounds in which tertiary nitrogen atoms are bonded to aromatic carbon atoms, such as N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis[4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane; N,N,N',N'-tetraglycidyl-1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,3-diaminocyclohexane, and N,N,N',N'-tetraglycidyl-1,3-diaminocyclohexane. N'-Tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-2-methyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)benzene, 1,4- Compounds in which tertiary nitrogen atoms are bonded to aliphatic carbon atoms, such as bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, and 1,3,5-tris(N,N-diglycidylaminomethyl)benzene; isocyanurate compounds such as TEPIC (manufactured by Nissan Chemical Co., Ltd.); compounds described in paragraph 0037 of Japanese Patent Application Publication No. 10-338880; and compounds described in International Publication No. 2017 / 170483, etc.

[0206] Compounds having oxetane groups include 1,4-bis{[(3-ethyl-3-oxetane)methoxy]methyl}benzene (ARON OXETANE OXT-121(XDO)), di[2-(3-oxetane)butyl] ether (ARON OXETANE OXT-221(DOX)), 1,4-bis[(3-ethyloxetane-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetane-3-yl)methoxy]benzene (CTOX), and compounds having two or more oxetane groups as described in paragraphs 0170 to 0175 of International Publication No. 2011 / 132751.

[0207] Compounds having an oxazoline structure include 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), etc.; polymers and oligomers with an oxazoline group, such as EPOCROS (trade name, Nippon Shokubai Co., Ltd.); and compounds described in paragraph 0115 of Japanese Patent Application Publication No. 2007-286597.

[0208] Compounds having a cyclic carbonate group include N,N,N',N'-tetratetra[(2-oxo-1,3-dioxolane-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N'-di[(2-oxo-1,3-dioxolane-4-yl)methyl]-1,3-phenylenediamine, and compounds described in paragraphs 0025 to 0030 and 0032 of WO2011 / 155577.

[0209] Compounds having end-capped isocyanate groups include: CORONATE AP stable M, CORONATE 2503, 2515, 2507, 2513, 2555, and MILLIONATE MS-50 (all manufactured by TOSOH); TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals); compounds having two or more protected isocyanate groups as described in paragraphs 0046 to 0047 of Japanese Patent Application Publication No. 2014-224978; and compounds having three or more protected isocyanate groups as described in paragraphs 0119 to 0120 of WO2015 / 141598.

[0210] Compounds having hydroxyl and / or alkoxy groups include N,N,N',N'-tetra(2-hydroxyethyl)hexamethylenediamine, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane, compounds described in International Publication No. 2015 / 072554, Japanese Patent Application Publication No. 2016-118753 (paragraph 0058), Japanese Patent Application Publication No. 2016-200798, and compounds described in International Publication No. 2010 / 074269.

[0211] As cross-linked compounds with polymerizable unsaturated groups, these include mono(meth)acrylates, di(meth)acrylates (a mixture of 1,2- and 1,3-type compounds), tri(meth)acrylates, glycerol 1,3-diglyceryl alcohol di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate, and hexaethylene glycol mono(meth)acrylate.

[0212] The content of the specific crosslinking group-containing compound in the liquid crystal alignment agent of the present invention is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total polymer components contained in the liquid crystal alignment agent, more preferably 0.1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass.

[0213] Examples of compounds used to adjust dielectric constant and resistance include monoamines such as 3-aminomethylpyridine, which have nitrogen-containing aromatic heterocycles. When using a monoamine with a nitrogen-containing aromatic heterocycle, the amount is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent, more preferably 0.1 to 20 parts by mass.

[0214] Preferred specific examples of functional silane compounds include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-epoxypropoxypropylmethyldimethoxysilane. Silanes, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. When using functional silane compounds, the amount is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, relative to 100 parts by weight of the polymer component contained in the liquid crystal alignment agent.

[0215] Examples of organic solvents used in the liquid crystal alignment agent of the present invention include: lactone solvents such as γ-valerolactone and γ-butyrolactone; γ-butyrolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-n-pentyl-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, and N-ethoxy Lactam solvents such as ethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, N,N-dimethyllacticamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, and tetramethylurea; cyclohexanone, cyclopentanone, etc. 4-Hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether Diethylene glycol diacetate, 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, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diisobutylmethanol (2,6-dimethyl-4-heptanol), diisobutyl ketone (2,6-dimethyl-4-heptanone), isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, etc. Two or more of these can be used in combination.

[0216] Preferred solvent combinations include: N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and diethylene glycol diethyl ether; N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, and 4-hydroxy-4-methyl-2-pentanone; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and diisobutyl ketone; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl- 2-Pentanone and dipropylene glycol monomethyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate; γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone; γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl ketone; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutylmethanol; N-methyl -2-pyrrolidone, γ-butyrolactone, and dipropylene glycol dimethyl ether; N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether; cyclohexanone and ethylene glycol monobutyl ether; cyclohexanone and propylene glycol monobutyl ether; cyclohexanone and propylene glycol monomethyl ether; cyclopentanone and propylene glycol monobutyl ether; cyclopentanone and propylene glycol monomethyl ether; cyclohexanone and diethylene glycol monoethyl ether; cyclopentanone and diethylene glycol monoethyl ether; cyclohexanone and diisobutyl ketone; cyclopentanone and diisobutyl ketone; methyl isobutyl ketone and propylene glycol monobutyl ether; methyl ethyl ketone and propylene glycol monobutyl ether; cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; cyclopentanone and 4-hydroxy-4-methyl-2-pentanone; cyclohexanone and diethylene glycol diethyl ether; cyclopentanone and diethylene glycol diethyl ether Ethyl ether; Tetramethylurea and propylene glycol diacetate; N,N-dimethylpropionamide and propylene glycol monobutyl ether; Tetramethylurea and propylene glycol monobutyl ether; Tetramethylurea, cyclohexanone and propylene glycol monomethyl ether; N,N-dimethylpropionamide and propylene glycol monomethyl ether; N,N-dimethylpropionamide and ethylene glycol monobutyl ether acetate; N,N-dimethylpropionamide and ethylene glycol monobutyl ether; N,N-diethylpropionamide and propylene glycol monomethyl ether; Tetramethylurea and propylene glycol monomethyl ether; N,N-dimethylpropionamide, cyclohexanone and diethylene glycol diethyl ether; N,N-diethylformamide and propylene glycol monomethyl ether; N,N-diethylformamide and 4-hydroxy-4-methyl-2-pentanone; Cyclohexanone and n-butyl acetate; Cyclopentanone and n-butyl acetate;4-Hydroxy-4-methyl-2-pentanone with ethylene glycol monobutyl ether; cyclohexanone with propylene glycol diacetate; and cyclopentanone with propylene glycol diacetate, etc. The type and content of such solvents are appropriately selected based on the coating equipment, coating conditions, and coating environment of the liquid crystal alignment agent.

[0217] The concentration of solid components in the liquid crystal alignment agent (the proportion of the total mass of components other than the solvent in the total mass of the liquid crystal alignment agent) is appropriately selected considering factors such as viscosity and volatility, and is preferably in the range of 1 to 10% by mass. From the perspective of forming a uniform and defect-free coating, 1% by mass or more is preferred, and from the perspective of the storage stability of the solution, 10% by mass or less is preferred. A particularly preferred concentration of solid components is 2 to 8% by mass.

[0218] <Liquid Crystal Alignment Film>

[0219] The liquid crystal alignment film of the present invention is obtained from the above-described liquid crystal alignment agent. The liquid crystal alignment film of the present invention can be used in horizontally aligned or vertically aligned liquid crystal alignment films. As a vertically aligned liquid crystal alignment film, it is preferably used in vertically aligned liquid crystal display elements such as VA-type or PSA-type liquid crystal displays.

[0220] Liquid crystal display element

[0221] The liquid crystal display element of the present invention includes the above-described liquid crystal alignment film. The liquid crystal alignment agent of the present invention is also preferably used in a liquid crystal display element manufactured by the following steps: having a liquid crystal layer between a pair of substrates having electrodes, disposing a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates, applying a voltage between the electrodes, and polymerizing the polymerizable compound by irradiation with at least one of active energy rays and heat.

[0222] The liquid crystal display element of the present invention can be manufactured, for example, by performing the following steps (1) to (3) or steps (1) to (4) in sequence.

[0223] (1) A process of coating a liquid crystal alignment agent onto at least one of a pair of substrates having a conductive film to form a coating film.

[0224] For example, the liquid crystal alignment agent of the present invention is coated onto one side of at least one of a pair of substrates having a patterned transparent conductive film by a suitable coating method such as roller coating, spin coating, printing, or inkjet coating to form a coating film. Here, there is no particular limitation on the substrate as long as it is a highly transparent substrate; it can also be used in conjunction with a glass substrate, a silicon nitride substrate, or a plastic substrate such as an acrylic substrate or a polycarbonate substrate. Furthermore, in reflective liquid crystal display elements, if the substrate is only on one side, an opaque object such as a silicon wafer can be used, and in this case, the electrode can be made of a light-reflecting material such as aluminum.

[0225] (2) The process of firing the coating film

[0226] After applying the liquid crystal alignment agent, the coating is fired to prevent liquid dripping of the applied alignment agent. Preheating (pre-baking) is preferably performed first. The pre-baking temperature is preferably 30–200°C, more preferably 40–150°C, and particularly preferably 40–100°C. The pre-baking time is preferably 0.25–10 minutes, more preferably 0.5–5 minutes. Furthermore, a heating (post-baking) process is preferably performed. The post-baking temperature is preferably 80–300°C, more preferably 120–250°C. The post-baking time is preferably 5–200 minutes, more preferably 10–100 minutes. The film thickness thus formed is preferably 5–300 nm, more preferably 10–200 nm.

[0227] The coating formed in the above steps (1) and (2) can be kept in this state and used as a liquid crystal alignment film, or the coating can be subjected to an alignment capability imparting treatment. Examples of alignment capability imparting treatments include: friction treatment in which the coating is rubbed in a certain direction using a roller made of cloth made of fibers such as nylon, rayon, or cotton; and light alignment treatment in which the coating is irradiated with polarized or unpolarized radiation.

[0228] In photo-alignment processing, the radiation used to irradiate the coating can be, for example, ultraviolet light and visible light with wavelengths ranging from 150 to 800 nm. When the radiation is polarized, it can be linearly polarized or partially polarized. Furthermore, when using linearly or partially polarized radiation, irradiation can be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When irradiating unpolarized radiation, the irradiation direction is set to an oblique direction.

[0229] (3) A liquid crystal layer is formed between the above-mentioned pair of substrates to manufacture a liquid crystal cell.

[0230] (3-1) Manufacturing of VA-type liquid crystal display elements

[0231] As described above, two substrates are prepared, on which at least one of the two substrates has a liquid crystal alignment film of the present invention formed, and liquid crystal is disposed between the two opposing substrates. Specifically, the following two methods can be listed. The first method is a conventionally known method. First, two substrates are arranged opposite each other with a gap (cell gap) between them, with their respective liquid crystal alignment films facing each other. Next, a sealant is applied to the periphery of the two substrates to make them adhere, and a liquid crystal composition is injected into the cell gap defined by the substrate surface and the sealant. After contact with the film surface, the injection hole is sealed.

[0232] In addition, a second method is known as the ODF (One Drop Fill) method. For example, a UV-curable sealant is applied to a predetermined area on one of two substrates on which a liquid crystal alignment film has been formed. A liquid crystal composition is then dropped onto several predetermined locations on the surface of the liquid crystal alignment film. The other substrate is then bonded together with the liquid crystal alignment films facing each other, and the liquid crystal composition is spread across the entire surface of the substrate, contacting the film surface. Next, the entire surface of the substrate is irradiated with UV light to cure the sealant.

[0233] Regardless of the method used, it is ideal to further heat the liquid crystal composition to a temperature at which it becomes an isotropic phase, and then slowly cool it to room temperature, thereby removing the flow orientation during liquid crystal filling.

[0234] There are no particular limitations on the liquid crystal composition described above; various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used. It should be noted that, hereinafter, liquid crystal compositions with positive dielectric anisotropy will be referred to as positive liquid crystals, and liquid crystal compositions with negative dielectric anisotropy will be referred to as negative liquid crystals.

[0235] The liquid crystal composition described above may contain liquid crystal compounds having fluorine atoms, hydroxyl groups, amino groups, fluorine-containing groups (e.g., trifluoromethyl), cyano groups, alkyl groups, alkoxy groups, alkenyl groups, isothiocyanate groups, heterocyclic groups, cycloalkanes, cycloolefins, steroidal skeletons, benzene rings, or naphthalene rings. It may also contain compounds having two or more rigid sites (mesocrystalline skeletons) that exhibit liquid crystal properties within the molecule (e.g., bimesocrystalline compounds formed by two rigid biphenyl structures or terphenyl structures linked by alkyl groups).

[0236] The liquid crystal composition can be a nematic liquid crystal composition, a smectic liquid crystal composition, or a cholesteric liquid crystal composition.

[0237] Furthermore, from the viewpoint of improving liquid crystal orientation, the above-mentioned liquid crystal composition can be further supplemented with additives. Examples of such additives include: photopolymerizable monomers such as compounds with polymerizable groups; optically active compounds (e.g., S-811 manufactured by Merck Co., Ltd.); antioxidants; ultraviolet absorbers; pigments; defoamers; polymerization initiators; or polymerization inhibitors, etc.

[0238] Examples of positive liquid crystal displays include: Merck's ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081.

[0239] Examples of negative liquid crystals include: MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, and MLC-7029 manufactured by Merck.

[0240] Furthermore, in the PSA process, an example of a liquid crystal containing a compound with polymerizable groups is MLC-3023 manufactured by Merck.

[0241] (3-2) Manufacturing of PSA-based liquid crystal display elements

[0242] The liquid crystal composition containing a compound with polymerizable groups is injected or dropped, except in this respect, in the same manner as described in (3-1). Examples of compounds with polymerizable groups include those having a mesocrystalline structure and two or more photopolymerizable or thermally polymerizable groups. Examples of mesocrystalline structures include structures formed by the linkage of two or more aromatic or aliphatic groups, such as: biphenyl structures, terphenyl structures, naphthalene rings, groups formed by removing two hydroxyl groups from bisphenol A, or structures containing fluorine atoms in which a portion of the hydrogen atoms of these structures is replaced by fluorine atoms. Specific examples of compounds include: 4,4'-dimethacryloyloxybiphenyl or 3-fluoro-1,1'-biphenyl-4,4'-dimethyldimethacrylate.

[0243] (3-3) Case where a coating is formed on a substrate using a liquid crystal alignment agent containing a compound with polymerizable groups.

[0244] Alternatively, a liquid crystal display element can be manufactured by performing the same process as described above (3-1) followed by an ultraviolet irradiation process, as described later. According to this method, similar to the manufacture of the PSA-type liquid crystal display element, a liquid crystal display element with excellent response speed can be obtained with a small amount of light irradiation. The compound having polymerizable groups can be the aforementioned compound having polymerizable groups, and its content relative to 100 parts by mass of the total polymer component is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. Furthermore, the aforementioned polymerizable groups can also be present in the polymer used as a liquid crystal alignment agent. Examples of such polymers include polymers obtained by reacting a diamine component containing the aforementioned diamine with photopolymerizable groups at the ends.

[0245] (4) The process of irradiating the liquid crystal cell with light.

[0246] The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (3-2) or (3-3) above. The applied voltage can be, for example, DC or AC of 5-50V. Furthermore, the irradiation light can be, for example, ultraviolet light or visible light containing wavelengths of 150-800nm, preferably ultraviolet light containing wavelengths of 300-400nm. The light source 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, an excimer laser, etc. The irradiation intensity is preferably 1000-200000 J / m². 2 More preferably, it is 1000 to 100000 J / m 2 .

[0247] Furthermore, a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of a liquid crystal cell. Examples of polarizing plates attached to the outer surface of a liquid crystal cell include: a polarizing plate made by sandwiching a polarizing film called an "H film" between a cellulose acetate protective film; or a polarizing plate made of the H film itself, wherein the H film is formed by absorbing iodine while extending and oriented polyvinyl alcohol.

[0248] The liquid crystal display element of this invention can be effectively applied to various devices, such as clocks, portable game consoles, word processors, laptops, car navigation systems, portable camcorders, PDAs (Personal Digital Assistants), digital cameras, mobile phones, smartphones, various monitors, LCD TVs, information displays, and other display devices. Furthermore, the aforementioned liquid crystal alignment agent can also be used in liquid crystal alignment films for retardation films; liquid crystal alignment films for scanning antennas and liquid crystal array antennas; or liquid crystal alignment films for transmission-scattering type liquid crystal dimming elements; or for other applications, such as protective films for color filters, gate insulating films for flexible displays, and substrate materials.

[0249] Example

[0250] The following detailed description is based on embodiments, but the present invention is not limited to these embodiments in any way. The abbreviations of the compounds used and the methods for determining their properties are described below.

[0251] (Organic solvents)

[0252] THF: Tetrahydrofuran.

[0253] NMP: N-methyl-2-pyrrolidone.

[0254] BCS: Butyl cellosolve (ethylene glycol monobutyl ether).

[0255] (Tetracarboxylic acid dianhydride)

[0256] (CA-1)~(CA-3): These are compounds represented by the following formulas (CA-1)~(CA-3).

[0257]

[0258] (Diamine)

[0259] (DA-1)~(DA-12): These are compounds represented by the formulas (DA-1)~(DA-12) below.

[0260]

[0261] <Viscosity Measurement>

[0262] The measurement was performed using a TVE-22H type E viscometer (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL, using a conical rotor TE-1 (1°34', R24), at a temperature of 25°C.

[0263] <Determination of molecular weight>

[0264] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were calculated using the following room-temperature GPC (gel permeation chromatography) apparatus, with conversion values ​​for polyethylene glycol and polyethylene oxide.

[0265] GPC apparatus: GPC-101 (manufactured by Showa Denko Corporation), chromatographic columns: GPC KD-803 and GPC KD-805 (manufactured by Showa Denko Corporation) in series, column temperature: 50℃, eluent: N,N-dimethylformamide (as additives, lithium bromide monohydrate (LiBr·H2O) 30 mmol / L, phosphoric acid·anhydrous crystals (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L), flow rate: 1.0 mL / min.

[0266] Standard samples used for calibration curve preparation: TSK standard polyethylene oxide (molecular weight; approximately 900,000, 150,000, 100,000 and 30,000) (manufactured by TOSOH) and polyethylene glycol (molecular weight; approximately 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories).

[0267] Synthesis of specific diamines (DA-4) to (DA-5)

[0268] The synthetic methods for the compounds represented by formulas (DA-4) to (DA-5) are described in detail below. It should be noted that the compounds represented by formulas (DA-4) to (DA-5) are novel compounds not disclosed in the literature.

[0269] < 1 H-NMR determination >

[0270] Apparatus: Fourier transform superconducting nuclear magnetic resonance (FT-NMR) device “Varian NMR System 400NB” (Varian) 400MHz, “AVANCE III” (BRUKER) 500MHz.

[0271] Solvent: Deuterated dimethyl sulfoxide (DMSO-d6, standard substance: tetramethylsilane).

[0272] <Synthetic Example 1-1: Synthesis of DA-4>

[0273] (Synthesis of DA-4-1)

[0274]

[0275] 3,5-dinitrobenzyl alcohol (19.9 g, 100 mmol), THF (118 g), and triethylamine (TEA, 12.5 g, 123 mmol) were added to a 500 mL four-necked flask. After cooling to 5 °C in an ice bath, methanesulfonyl chloride (12.5 g, 109 mmol) was added dropwise. After the reaction was complete, the precipitated triethylamine salt was removed by filtration, and the filtrate was concentrated to obtain crude DA-4-1. A mixture of crude DA-4-1 and 2-propanol (68.0 g) was stirred in a slurry at 80 °C for 1 hour, cooled to room temperature, and the crystals were recovered by filtration. The recovered crystals were dried under vacuum at 50 °C to obtain DA-4-1 (yield: 20.9 g, 75.6 mmol, 75.6% yield, yellow solid).

[0276] (Synthesis of DA-4-2)

[0277]

[0278] DA-4-1 (14.0 g, 50.7 mmol), potassium carbonate (12.4 g, 90.0 mmol), hydroquinone (90.6 g, 823 mmol), and ethanol (EtOH, 362 g) were added to a 1 L four-necked flask and reacted at 45 °C for 5 hours. After the reaction, the reaction solution and water (1200 g) were added to a 2 L beaker to precipitate crude DA-4-2. The precipitate was recovered by filtration, dried under vacuum at 50 °C, and then methanol (350 g) and ethanol (190 g) were added to the crude DA-4-2. The mixture was heated to 60 °C to dissolve the precipitate. Insoluble matter was removed by filtration, and water (1000 g) was added to the filtrate to precipitate DA-4-2. The precipitated solid was recovered by filtration and dried under vacuum at 50°C to obtain DA-4-2 (yield: 10.0 g, 34.5 mmol, yield: 68.0%, yellow solid).

[0279] (Synthesis of DA-4)

[0280]

[0281] DA-4-2 (9.98 g, 34.4 mmol), THF (120 g), and carbon-supported platinum (Pt / C, 3% by mass, 0.500 g) were added to a 500 mL four-necked flask and reacted at room temperature under a hydrogen atmosphere. After the reaction was complete, the carbon-supported platinum was removed by filtration, and the crystals precipitated from the concentrated filtrate were dried under vacuum at 50 °C to obtain DA-4 (yield: 7.71 g, 33.5 mmol, yield: 97.4%, orange solid). According to the following... 1 The H-NMR results confirmed that the solid was DA-4.

[0282] 1 H-NMR (500MHz, DMSO-d6): δ (ppm) = 8.86 (s, 1H), 6.75 (d, 2H, J = 9.0Hz), 6.64 (d, 2H, J=9.0Hz), 5.83 (d, 2H, J=1.9Hz), 5.74 (t, 1H, J=2.0Hz), 4.71 (br, 4H), 4.66 (s, 2H).

[0283] <Synthetic Examples 1-2: Synthesis of DA-5>

[0284] The diamine DA-5 was synthesized following the route shown below.

[0285]

[0286] (Synthesis of DA-5-1)

[0287] Tetrahydrofuran (361 g), ethyl 3,4-dihydroxybenzoate (90.2 g, 495 mmol), and N,N-diisopropylethylamine (iPr2EtN, 320 g, 2.48 mol) were added dropwise to a 2000 mL four-necked flask. (Chloromethyl)methyl ether (MOMCl, 179 g, 2.22 mol) was added dropwise under a nitrogen atmosphere and ice-cold conditions. After the addition, the reaction was allowed to proceed at room temperature until the starting material disappeared. After the reaction was complete, the reaction solution was diluted with ethyl acetate (1350 g), and the organic phase was washed with pure water (720 g). Then, the organic phase was washed twice with 2.0 mol / L hydrochloric acid aqueous solution (720 g) and three times with pure water (720 g). The obtained organic phase was concentrated under reduced pressure to obtain a pale yellow, oily crude product.

[0288] Ethanol (400 g) and pure water (274 g) were added to the crude product, followed by sodium hydroxide (21.8 g). The mixture was reacted at room temperature for 20 hours to hydrolyze the product. After the reaction was complete, 1.0 mol / L hydrochloric acid aqueous solution (600 mL) was added to the reaction solution to precipitate crystals. The slurry was then washed with pure water (266 g). The mixture was then filtered, washed with pure water and hexane, and dried to obtain DA-5-1 (yield: 111 g, 458 mmol, yield: 93%, white crystals).

[0289] (Synthesis of DA-5-2)

[0290] In a 2000 mL four-necked flask, 3,5-dinitrobenzyl alcohol (75.2 g, 379 mmol), DA-5-1 (106 g, 438 mmol), 4-dimethylaminopyridine (DMAP, 4.62 g), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC, 94.5 g) were added to tetrahydrofuran (452 ​​g). The reaction was carried out under a nitrogen atmosphere at room temperature for 4 hours. After the reaction was completed, the reaction solution was added to pure water (810 g), causing crystals to precipitate. The crystals were then filtered, washed with pure water, and then washed with methanol. The filtrate was then washed with methanol (180 g), filtered, and dried to obtain DA-5-2 (yield: 156 g, 369 mmol, yield: 97%, pale yellow crystals).

[0291] (Synthesis of DA-5-3)

[0292] In a 2000 mL four-necked flask, 200 g of 4.0 mol / L hydrochloric acid aqueous solution and DA-5-2 (131 g, 310 mmol) were added to tetrahydrofuran (195 g) and methanol (MeOH, 327 g). The mixture was heated at 50 °C for approximately 12 hours. After the reaction was complete, ethyl acetate (1310 g) and toluene (432 g) were added to the reaction solution to separate the two phases. After removing the hydrochloric acid phase, the organic layer was washed three times with pure water (400 g). The organic phase was concentrated under reduced pressure to a total internal weight of 555 g, and 2-propanol (262 g) was added and stirred under ice-cold conditions to precipitate crystals. The precipitated crystals were filtered and dried to obtain DA-5-3 (yield: 80.3 g, 240 mmol, yield: 78%, yellow crystals).

[0293] (Synthesis of DA-5)

[0294] DA-5-3 (39.2 g, 117 mmol) and carbon-supported platinum (3.13 g, 3 by mass) were added to a 1000 mL four-necked flask containing tetrahydrofuran (240 g) and methanol (80 g). The reaction was carried out for 2 days under a hydrogen atmosphere and heating at 40 °C. After the reaction was completed, the mixture was filtered and concentrated under reduced pressure to a total internal weight of 35 g. Then, methanol (120 g) was added to precipitate crystals, which were then filtered and dried to obtain DA-5 (yield: 28.0 g, 102 mmol, yield: 87%, pale yellow crystals). According to the following... 1 The H-NMR results confirmed that the solid was DA-5.

[0295] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 9.60 (s, 2H), 7.38 (s, 1H), 7.32-7.38 (m, 1H), 6.81 (d, 1H, J=8.0Hz), 5.83 (d, 2H, J=1.6Hz), 5.76-5.77 (m, 1H), 4.96 (s, 2H), 4.78 (s, 4H).

[0296] [Polymer Synthesis]

[0297] <Synthesis example 2-1>

[0298] DA-1 (2.97 g, 10.0 mmol), DA-4 (0.921 g, 4.00 mmol), DA-6 (2.28 g, 6.00 mmol), CA-1 (2.50 g, 10.0 mmol), and NMP (34.7 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred at 60 °C for 3 hours while nitrogen was being introduced. Then, CA-2 (1.80 g, 9.20 mmol) and NMP (7.22 g) were added, and the mixture was stirred at 40 °C for 3 hours, thus obtaining a polyamic acid solution (1) with a solid content of 20% by mass (viscosity: 690 mPa·s). The Mn of this polyamic acid was 12400, and the Mw was 28500.

[0299] <Synthesis example 2-2>

[0300] DA-1 (2.97 g, 10.0 mmol), DA-2 (0.893 g, 4.00 mmol), DA-6 (2.28 g, 6.00 mmol), CA-1 (2.50 g, 10.00 mmol), and NMP (34.8 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred at 60 °C for 3 hours while nitrogen was being introduced. Then, CA-2 (1.93 g, 9.84 mmol) and NMP (7.72 g) were added, and the mixture was stirred at 40 °C for 3 hours, thus obtaining a polyamic acid solution (2) with a solid content of 20% by mass (viscosity: 720 mPa·s). The Mn of this polyamic acid was 15600, and the Mw was 32800.

[0301] <Synthesis example 2-3>

[0302] DA-1 (2.97 g, 10.0 mmol), DA-5 (1.10 g, 4.00 mmol), DA-6 (2.28 g, 6.00 mmol), CA-1 (2.50 g, 10.00 mmol), and NMP (35.4 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred at 60 °C for 3 hours while nitrogen was being introduced. Then, CA-2 (1.91 g, 9.74 mmol) and NMP (7.62 g) were added, and the mixture was stirred at 40 °C for 3 hours, thus obtaining a polyamic acid solution (3) with a solid content of 20% by mass (viscosity: 680 mPa·s). The Mn of this polyamic acid was 16800, and the Mw was 32200.

[0303] <Synthesis example 2-4>

[0304] DA-8 (0.793 g, 4.00 mmol), DA-4 (0.921 g, 4.00 mmol), DA-9 (2.46 g, 6.00 mmol), DA-10 (1.45 g, 6.00 mmol), CA-2 (3.02 g, 15.4 mmol), and NMP (34.6 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred at 40 °C for 3 hours while nitrogen was being introduced. Then, CA-3 (0.872 g, 4.00 mmol) and NMP (3.49 g) were added, and the mixture was stirred at room temperature for 3 hours to obtain a polyamic acid solution (4) with a solid content of 20% by mass (viscosity: 780 mPa·s). The Mn of this polyamic acid was 16800, and the Mw was 32400.

[0305] <Synthesis example 2-5>

[0306] DA-8 (0.793 g, 4.00 mmol), DA-2 (0.893 g, 4.00 mmol), DA-9 (2.46 g, 6.00 mmol), DA-10 (1.45 g, 6.00 mmol), and CA-2 (3.02 g, 15.4 mmol) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred at 40 °C for 3 hours while nitrogen was being introduced. Then, NMP (34.7 g), CA-3 (0.872 g, 4.00 mmol), and NMP (3.49 g) were added, and the mixture was stirred at room temperature for 3 hours, thereby obtaining a polyamic acid solution (5) with a solid content of 20% by mass (viscosity: 740 mPa·s). The Mn of this polyamic acid was 12900, and the Mw was 23900.

[0307] <Synthesis example 2-6>

[0308] DA-8 (0.793 g, 4.00 mmol), DA-3 (1.13 g, 4.00 mmol), DA-9 (2.46 g, 6.00 mmol), DA-10 (1.45 g, 6.00 mmol), CA-2 (3.02 g, 15.4 mmol), and NMP (34.4 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred at 40 °C for 3 hours while nitrogen was being introduced. Then, CA-3 (0.872 g, 4.00 mmol) and NMP (3.49 g) were added, and the mixture was stirred at room temperature for 3 hours to obtain a polyamic acid solution (6) with a solid content of 20% by mass (viscosity: 745 mPa·s). The Mn of this polyamic acid was 11500, and the Mw was 23400.

[0309] <Synthesis example 2-7>

[0310] DA-1 (2.97 g, 10.0 mmol), DA-6 (2.28 g, 6.00 mmol), DA-12 (0.609 g, 4.00 mmol), CA-1 (2.50 g, 10.0 mmol), and NMP (33.5 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred at 60 °C for 3 hours while nitrogen was being introduced. Then, CA-2 (1.80 g, 9.20 mmol) and NMP (7.22 g) were added, and the mixture was stirred at 40 °C for 3 hours, thus obtaining a polyamic acid solution (7) with a solid content of 20% by mass (viscosity: 650 mPa·s). The Mn of this polyamic acid was 11900, and the Mw was 25600.

[0311] <Synthesis example 2-8>

[0312] DA-1 (2.08 g, 7.00 mmol), DA-7 (2.61 g, 6.00 mmol), DA-10 (0.969 g, 4.00 mmol), DA-11 (0.991 g, 3.00 mmol), CA-1 (2.50 g, 10.0 mmol), and NMP (36.6 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred at 60 °C for 3 hours while nitrogen was being introduced. Then, CA-2 (1.86 g, 9.50 mmol) and NMP (7.45 g) were added, and the mixture was stirred at 40 °C for 3 hours to obtain a polyamic acid solution (8) with a solid content of 20% by mass (viscosity: 690 mPa·s). The Mn of this polyamic acid was 10900, and the Mw was 26900.

[0313] The specifications of the polymers obtained in the above synthesis examples are shown in Table 1 below.

[0314] [Table 1]

[0315]

[0316] [Preparation of Liquid Crystal Alignment Agent]

[0317] <Example 1-1>

[0318] NMP (8.00 g) and BCS (8.00 g) were added to the polyamic acid solution (1) (4.00 g) obtained in Synthesis Example 2-1, and the mixture was stirred at room temperature for 3 hours to obtain the liquid crystal alignment agent (A-1).

[0319] <Examples 1-2 to 1-3, Comparative Example 1-1>

[0320] Polyamic acid solutions (2) to (3) and (7) were used instead of polyamic acid solution (1). Otherwise, liquid crystal alignment agents (A-2) to (A-3) and (B-1) of Examples 1-2 to 1-3 and Comparative Example 1-1 were obtained in the same manner as in Example 1-1.

[0321] <Examples 1-4>

[0322] NMP (8.00 g) and BCS (8.00 g) were added to the polyamic acid solution (8) (1.20 g) obtained in Synthesis Examples 2-8 and the polyamic acid solution (4) (2.80 g) obtained in Synthesis Examples 2-4, and the mixture was stirred at room temperature for 3 hours to obtain the liquid crystal alignment agent (A-4).

[0323] <Examples 1-5 to 1-6>

[0324] Polyamic acid solutions (5) to (6) were used instead of polyamic acid solution (4). Otherwise, liquid crystal alignment agents (A-5) to (A-6) of Examples 1-5 to 1-6 were obtained in the same manner as in Examples 1-4.

[0325] The specifications of the liquid crystal alignment agents obtained in the above embodiments and comparative examples are shown in Table 2 below.

[0326] [Table 2]

[0327] Example 1-1 A-1 Polyamic acid solution (1) Examples 1-2 A-2 Polyamic acid solution (2) Examples 1-3 A-3 Polyamic acid solution (3) Examples 1-4 A-4 Polyamic acid solution (8), polyamic acid solution (4) Examples 1-5 A-5 Polyamic acid solution (8), polyamic acid solution (5) Examples 1-6 A-6 Polyamic acid solution (8), polyamic acid solution (6) Comparative Example 1-1 B-1 Polyamic acid solution (7)

[0328] It was confirmed that the liquid crystal alignment agents (A-1) to (A-6) and (B-1) obtained as described above were free of turbidity, precipitation, or other abnormalities, and were homogeneous solutions. The voltage retention rate was evaluated using the obtained liquid crystal alignment agents.

[0329] [Fabrication of a liquid crystal cell for evaluating voltage retention rate]

[0330] The liquid crystal alignment agent obtained above was used to fabricate a liquid crystal cell in the following order. The liquid crystal alignment agent was spin-coated onto glass substrates (3cm wide x 4cm long) with ITO electrodes. After drying on a heating plate at 70°C for 90 seconds, the substrates were fired in an infrared furnace at 230°C for 20 minutes to form a liquid crystal alignment film with a thickness of 100nm. Two substrates with this liquid crystal alignment film were prepared. On one substrate, 4μm diameter bead-shaped spacers (made by Nichiki Chemicals, silk balls, SW-D1) were coated onto the liquid crystal alignment film, leaving a liquid crystal injection port. A thermosetting sealant (made by Mitsui Chemicals, XN-1500T) was printed around the port. Next, the side of the other substrate with the liquid crystal alignment film was made inside, and the substrate was bonded to the first substrate. The sealant was then cured to create an empty cell. Liquid crystal MLC-3023 (made by Merck) was injected into the empty cell using a depressurized injection method to fabricate the liquid crystal cell. Next, while applying a DC voltage of 15V to the liquid crystal cell, 10J / cm² of light was irradiated from the outside of the liquid crystal cell. 2 The UV light passed through a cutoff filter with a wavelength below 325 nm. It should be noted that the UV illuminance was measured using an ORC UV-M03A UV illuminometer / photometer. Then, to deactivate any unreacted polymeric compounds remaining in the liquid crystal cell, the sample was irradiated for 30 minutes using a TOSHIBALIGHTING & TECHNOLOGY UV-FL irradiation device (UV lamp: FLR40SUV32 / A-1) without applied voltage (hereinafter also referred to as PSA treatment).

[0331] [Evaluation of voltage retention rate]

[0332] The voltage retention rate was determined using a liquid crystal cell for evaluating voltage retention rate after PSA treatment. A voltage of 1V was applied for 60μsec in a 60°C hot air circulating oven, and the voltage was measured after 1667ms. The amount of voltage retained was calculated as the voltage retention rate. A VHR-1 meter manufactured by TOYO Corporation was used for the voltage retention rate measurement. A higher value is better. As an evaluation benchmark, a voltage retention rate of 80% or higher after PSA treatment was marked as "○", and a rate less than 80% was marked as "×".

[0333] [Evaluation of voltage retention rate after aging]

[0334] The PSA-treated liquid crystal cells were placed in a high-temperature and high-humidity oven set at 60°C and 90% relative humidity for 10 days for aging. The voltage retention rate after aging was calculated in the same manner as above. As an evaluation benchmark, cases with a voltage retention rate of 40% or higher after aging were marked as "○", and cases with a voltage retention rate of less than 40% were marked as "×".

[0335] [Table 3]

[0336]

[0337] As shown in Table 3, the liquid crystal alignment films obtained using the liquid crystal alignment agents (A-1) to (A-6) of Examples 1-1 to 1-6 showed higher voltage retention rates after PSA treatment and high temperature and humidity aging compared to the liquid crystal alignment film obtained using the liquid crystal alignment agent (B-1) of Comparative Example 1-1.

Claims

1. A liquid crystal alignment agent containing a polymer component, The polymer components satisfy at least any one of the following conditions i and ii. Condition i: The polymer component contains at least one polymer selected from the group consisting of a polyimide precursor having repeating unit a1 as shown in formula (1) and repeating unit a1' as shown in formula (1') and a polyimide as an imide derivative of the polyimide precursor. Condition ii: The polymer component comprises: at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit a1 as shown in formula (1) and a polyimide as an imide derivative of the polyimide precursor; and at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit a1' as shown in formula (1') and a polyimide as an imide derivative of the polyimide precursor. In formula (1) and formula (1'), X1and X 1’ each independently represents a tetravalent organic group; Y1represents a divalent organic group having an oxazoline skeleton; Y 1’ represents a divalent organic group Ah having an aliphatic carboxyl group or a divalent organic group ph having a phenolic hydroxyl group; R and Z each independently represent a hydrogen atom or a monovalent organic group.

2. The liquid crystal alignment agent according to claim 1, wherein, The divalent organic group ph has the following structure (ph-1) as a structure having the phenolic hydroxyl group. In formula (ph-1), Ar represents a benzene ring or a naphthalene ring; R represents a hydrogen atom, a methyl group, a methoxy group, or a halogen atom; * represents a bond. When Ar is a benzene ring, p represents an integer from 1 to 5, q represents an integer from 0 to 4, and r represents an integer from 1 to 5. The sum of p, q, and r is 6. When Ar is a naphthalene ring, p represents an integer from 1 to 7, q represents an integer from 0 to 6, and r represents an integer from 1 to 7. The sum of p, q, and r is 8.

3. The liquid crystal alignment agent according to claim 1, wherein, The polymer components must at least satisfy condition i.

4. The liquid crystal alignment agent according to claim 1, wherein, The polymer components at least satisfy condition ii.

5. The liquid crystal alignment agent according to claim 1, wherein, The oxazoline skeleton in Y1 is located in the main chain of a polymer having Y1.

6. The liquid crystal alignment agent according to claim 1, wherein, Y1 has a partial structure as shown in the following formula (m-Ox). The partial structure represented by formula (m-Ox) is located in the main chain of a polymer having Y1. In the formula (m-Ox), R 1 represents a hydrogen atom or a monovalent organic group, and * represents a bond.

7. The liquid crystal alignment agent according to claim 1, wherein, In the aliphatic carboxyl group, the carboxyl group is bonded to a carbon atom of the methylene group or to a carbon atom forming an alicyclic structure.

8. The liquid crystal alignment agent according to claim 1, wherein, The divalent organic group Ah is a group formed by removing two amino groups from a specific diamine Ah, which is a diamine having an aliphatic carboxyl group. The specific diamine Ah is "A" 1’ -(L-Ah) m’ "or"(A 11’ The aromatic diamine represented by )2-Ah'”, Among them, A 1’ This represents an m' valence group formed by the bonding of two primary amino groups with an aromatic group. A 11’ This represents a monovalent group formed by the bonding of a primary amino group and an aromatic group. L represents a single bond, -O-, -CO-, -CO-O-, -NR-, or -NR-CO-, where R represents a hydrogen atom or a methyl group in -NR- and -NR-CO-. Ah represents a monovalent aliphatic carboxyl group. m' is an integer from 1 to 2. Ah' represents a divalent aliphatic carboxyl group.

9. The liquid crystal alignment agent according to claim 1, wherein, The polymer component satisfies at least any one of the following conditions i-1, ii-1, and ii-2. Condition i-1: The polymer component contains at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit a1 as shown in formula (1), a repeating unit a1' as shown in formula (1'), and a repeating unit a2 as shown in formula (2) below, and a polyimide as an imide derivative of the polyimide precursor. Condition ii-1: The polymer component comprises: at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit a1 as shown in formula (1) and a repeating unit a2 as shown in formula (2) below, and a polyimide as an imide derivative of the polyimide precursor; and at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit a1' as shown in formula (1') and a polyimide as an imide derivative of the polyimide precursor. Condition ii-2: The polymer component comprises: at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit a1 as shown in formula (1) and a polyimide as an imide derivative of the polyimide precursor; and at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit a1' as shown in formula (1') and a repeating unit a2 as shown in formula (2) below, and a polyimide as an imide derivative of the polyimide precursor. In formula (2), X2 represents a tetravalent organic group; Y2 represents a divalent organic group with the group -X-J; R and Z each independently represent a hydrogen atom or a monovalent organic group. In the group –X-J, X represents a single bond, –(CH2). a -, -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -COO-, -OCO-, -Ak-O-CO-CH=CH-** or -(A1) a0 -((CH2) a1 -A1) m1 -, the -(CH2) a In the – , a is an integer from 1 to 15; in –Ak-O-CO-CH=CH-**, ** represents a bond bonded to an aromatic hydrocarbon group; Ak represents a divalent organic group with 1 to 10 carbon atoms; and –(Al) a0 -((CH2) a1 -A1) m1 In this context, a0 is an integer of 0 or 1, a1 is an integer from 1 to 15, each A1 independently represents -O- or -COO-, and m1 is an integer from 1 to 2; when m1 is 2, multiple a1s independently have the aforementioned definition. J represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an aromatic hydrocarbon group having 6 to 40 carbon atoms, wherein at least one of the hydrogen atoms in the alicyclic hydrocarbon group and the aromatic hydrocarbon group is substituted by a substituent v as a halogen atom, an alkyl group containing a halogen atom having 1 to 10 carbon atoms, an alkoxy group containing a halogen atom having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkenyl group having 3 to 10 carbon atoms, and any carbon-carbon single bond in these substituent v is optionally interrupted by -O-, wherein the substituent v does not include a halogen atom.

10. The liquid crystal alignment agent according to claim 1, wherein, The X1 and X 1’ The tetravalent organic group in the formula is a tetravalent organic group derived from tetracarboxylic dianhydride or its derivatives, wherein the tetravalent organic group is a tetravalent organic group derived from acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, or their derivatives.

11. A liquid crystal alignment film obtained from a liquid crystal alignment agent as described in any one of claims 1 to 10.

12. A liquid crystal display element comprising the liquid crystal alignment film as described in claim 11.

13. A method for manufacturing a liquid crystal display element, comprising sequentially performing the following steps 1 to 3, Step 1: A step of coating a liquid crystal alignment agent as described in any one of claims 1 to 10 onto at least one of a pair of substrates having a conductive film to form a coating film. Step 2: The step of firing the coating film; Step 3: Forming a liquid crystal layer between the pair of substrates to manufacture a liquid crystal cell.

14. The method for manufacturing a liquid crystal display element according to claim 13, wherein, This includes a further step, step 4, following steps 1 through 3. Step 4: The process of irradiating the liquid crystal cell with light.

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