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

Abstract

Provided is a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film having a high voltage retention rate even after long-term exposure to high temperature and high humidity, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film. A liquid crystal alignment agent contains at least one polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit (a1) of a unit represented by the following formula (1) and a repeating unit (a2) of a unit represented by the following formula (2), and a polyimide which is an imidized product of the polyimide precursor. The polymer (A) does not have a repeating unit (b3) of a unit represented by the following formula (3). At least one polymer (B) is selected from the group consisting of a polyimide precursor having a repeating unit (b3) of a unit represented by the following formula (3), and a polyimide which is an imidized product of the polyimide precursor.(X1, X2 represent a tetravalent organic group. Y1 represents a divalent organic group having an oxazoline skeleton. Y2 represents a divalent organic group having a group -X-J. R, Z each independently represent a hydrogen atom or a monovalent organic group. In the group -X-J, X represents a single bond, -(CH2) a -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -COO-, -OCO-, -Ak-O-CO-CH=CH- (** represents a bonding bond to be bonded to a carbon atom number of 6 to 40 of an aromatic hydrocarbon group in J. Ak represents a divalent organic group having a carbon atom number of 1 to 10), or -(A1) a0 -(CH2) a1 -(A1) m1 -(a0 is an integer of 0 or 1, a1 is an integer of 1 to 15, A1 represents -O- or -COO-, in the case where a plurality of A1 are present, each of the A1 independently has the above definition. m1 is an integer of 1 to 2. In the case where m1 is 2, a plurality of a1 each independently have the definition). J represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having a carbon atom number of 4 to 40 and an aromatic hydrocarbon group having a carbon atom number of 6 to 40. In the alicyclic hydrocarbon group and the aromatic hydrocarbon group, at least one of the hydrogen atoms is substituted with a halogen atom, a halogen atom-containing alkyl group having a carbon atom number of 1 to 10, a halogen atom-containing alkoxy group having a carbon atom number of 1 to 10, an alkyl group having a carbon atom number of 3 to 10, an alkoxy group having a carbon atom number of 3 to 10, an alkenyl group having a carbon atom number of 3 to 10, and optionally, a carbon-carbon bond of any methylene group is interrupted by -O-.)(X3 represents a tetravalent organic group. Y3 represents a divalent organic group having an aromatic carboxyl group. Two R, Z each have the same meaning as R, Z of formula (1).)

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) (for example, see 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] A liquid crystal alignment agent comprising the following components (A) and (B).

[0018] (A) Composition: At least one polymer (A) selected from the group consisting of a polyimide precursor having repeating units (a1) of the unit shown in formula (1) and repeating units (a2) of the unit shown in formula (2) below, and a polyimide as an imide derivative of the polyimide precursor. Wherein, polymer (A) does not have repeating units (b3) of the unit shown in formula (3) below.

[0019] (B) Component: At least one polymer (B) selected from the group consisting of a polyimide precursor having a repeating unit (b3) of the unit shown in the following formula (3) and a polyimide as an imide derivative of the polyimide precursor.

[0020]

[0021] (X1 and X2 represent tetravalent organic groups. Y1 represents a divalent organic group with an oxazoline skeleton. 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.)

[0022] 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 having 6 to 40 carbon atoms in J. Ak represents a divalent organic group having 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, A1 represents -O- or -COO-, and in the case of multiple A1s, each A1 independently has the above definition. m1 is an integer from 1 to 2. In the case of m1 being 2, multiple a1s independently have the above definition).

[0023] 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 hydrogen atom of the aforementioned alicyclic hydrocarbon group and aromatic hydrocarbon group is substituted with 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 the carbon-carbon bond of any methylene group in these groups is optionally interrupted by -O-.

[0024]

[0025] (X3 represents a tetravalent organic group. Y3 represents a divalent organic group with an aromatic carboxyl group. The two R and Z have the same meaning as R and Z in formula (1).)

[0026] It should be noted that in this specification, * denotes a bond in all cases. Examples of halogen atoms include: fluorine, chlorine, bromine, and iodine.

[0027] Invention Effects

[0028] 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.

[0029] The mechanism by which the above-mentioned effects of the present invention are obtained may not be clear, but it can be considered that the following description is one of the reasons. The (s-Ox) and (m-Ox) structures (hereinafter also referred to as (Ox)) contained in the polymer of the present invention undergo ring-opening during post-baking and cross-link 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 by using the polymer (B) having aromatic carboxyl groups, the ring-opening reaction proceeds further, thereby cross-linking with the carboxylic acid, and the film density of the resulting liquid crystal alignment film is increased. On the other hand, since the liquid crystal composition tends to decrease in voltage retention rate when exposed to acidic conditions, the present invention uses a liquid crystal alignment agent containing a polymer (A) without aromatic carboxyl groups and a polymer (B) having aromatic carboxyl groups. Polymer (B) tends to be biased towards the substrate side opposite to the liquid crystal layer side, therefore the acidity of polymer (B) does not easily affect the liquid crystal composition. Based on the above, it can be considered that a liquid crystal alignment film with a higher voltage retention rate has been obtained. Detailed Implementation

[0030] 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.

[0031] <Polymer Composition>

[0032] The liquid crystal alignment agent of the present invention contains the following components (A) and (B).

[0033] (A) Composition: At least one polymer (A) selected from the group consisting of a polyimide precursor having repeating units (a1) of the unit shown in formula (1) and repeating units (a2) of the unit shown in formula (2) above, and a polyimide as an imide derivative of the polyimide precursor. Wherein, polymer (A) does not have repeating units (b3) of the unit shown in formula (3) above.

[0034] (B) Component: At least one polymer (B) selected from the group consisting of a polyimide precursor having a repeating unit (b3) of the unit shown in the above formula (3) and a polyimide as an imide derivative of the polyimide precursor.

[0035] From the viewpoint of efficiently obtaining the effects of the present invention, the total of the repeating unit (a1) and the imidized structural unit of the repeating unit (a1) is preferably 5 to 95 mol% of the total repeating unit constituting the polymer (A), more preferably 10 to 90 mol%.

[0036] From the perspective of improving liquid crystal orientation, the total 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 polymer (A).

[0037] From the viewpoint of efficiently obtaining the effects of the present invention, the total of the repeating unit (b3) and the imidized structural unit of the repeating unit (b3) is preferably 5 to 90 mol% of the total repeating unit constituting the polymer (B), more preferably 10 to 80 mol%.

[0038] Furthermore, the mass ratio of the content of polymer (A) to the content of polymer (B) (polymer (A) / polymer (B)) is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10.

[0039] (Repeating unit (a1))

[0040] In formula (1) above, Y1 represents a divalent organic group having an oxazoline skeleton. The oxazoline skeleton only needs to be present at least once in the main chain or side chain of the polymer. When Y1 is a divalent organic group having an oxazoline skeleton in the side chain of the polymer, the position of the oxazoline skeleton 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, Y1 is more preferably having an oxazoline skeleton at the end of the polymer side chain, and even more preferably having a partial structure as shown in the following formula (s-Ox).

[0041]

[0042] (R represents a single bond, -O-, or (n+1) valence organic group. n is an integer from 1 to 3.)

[0043] 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.

[0044] 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.

[0045]

[0046] (In the formula, L represents -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -COO-, and -OCO-. n4 is an integer from 0 to 3, and n5 is an integer from 1 to 3.)

[0047] When Y1 is a divalent organic group having an oxazoline backbone in the side chain of the polymer, Y1 is preferably a group obtained 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 groups include: benzene rings, naphthalene rings, biphenyl structures, or aromatic compounds 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.)

[0048] In the above diamine "A1-(Z1)" m In the case where m is 1 and A1 represents diaminophenyl, the two amino groups in diaminophenyl are preferably located at the 2,5- or 3,5- positions relative to Z1.

[0049] When Y1 is a divalent organic group having an oxazoline backbone in the main chain of the polymer, Y1 is preferably a divalent organic group having a partial structure as shown in the following formula (m-Ox) in the main chain of the polymer.

[0050]

[0051] (R 1 (This represents hydrogen or a monovalent organic group.)

[0052] R, as in the above equation (m-Ox) 1The monovalent organic group in the form of the chain is preferably a monovalent organic group having an aromatic group (such as a benzene ring), a monovalent chain hydrocarbon group having 1 to 10 carbon atoms (e.g., 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 (e.g., 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 chain hydrocarbon group, the aforementioned alicyclic hydrocarbon group, or the aforementioned aromatic ring structure may optionally be substituted with 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, a portion of the methylene group in the aforementioned chain hydrocarbon group, the aforementioned alicyclic hydrocarbon group, or the aforementioned aromatic ring structure may optionally be substituted with -O-, -CO-, or -COO-. From the viewpoint of properly obtaining the effects of the present invention, R of the above formula (m-Ox) 1 Preferably, it contains hydrogen atoms or methyl groups.

[0053] When Y1 is a divalent organic group having an oxazoline backbone in the polymer backbone, Y1 is preferably a group obtained 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)). Specific examples of the above specific diamine (Ox) include diamines selected from the group shown in formulas (m-Ox-1) to (m-Ox-3).

[0054]

[0055] (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 (L) formed from the groups in the group, R 11 This indicates a hydrogen atom or a methyl group. W 1 ~W 2 W 4W represents an aromatic hydrocarbon group. 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 when a is 1 2 They may be identical or different from each other, optionally. In equation (m-Ox-3), the two Rs... 1 R 2 and W 2 (They may be the same as or different from each other.)

[0056] As mentioned above, W 1 ~W 4 The aromatic hydrocarbon group in the W can be composed solely of aromatic groups (e.g., benzene ring, naphthalene ring, biphenyl structure, anthracene ring), or it can be a hydrocarbon group linked by at least one of the above aromatic groups through a chain structure (e.g., alkylene ring) and an alicyclic structure (e.g., cyclohexane ring). 1 ~W 4 Preferred examples of aromatic hydrocarbon groups in W include benzene rings, naphthalene rings, and biphenyl structures. 3 The alicyclic hydrocarbon group in it can consist solely of an alicyclic structure (e.g., a cyclohexane ring), or it can contain a chain-like structure in a portion thereof. 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 be substituted, and a portion of the methylene group may 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), carboxamide groups (e.g., acetamido, propionamido), etc.

[0057] 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-, -(CH2) n -OCO-Ar-, -(CH2) n -NR 11 CO-Ar-、-(CH2) n -NR 11 -Ar- (n is an integer from 1 to 6. Ar represents 1,4-phenylene or 4,4'-biphenyldiyl. R 11 (Represents a hydrogen atom or a methyl group).

[0058] 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 -NR 11 CO-Cy-CONR 11 -(CH2) n - (n is an integer from 1 to 6, each n independently having the above definition. 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. Two R's 11 (Optional, they may be the same as or different from each other).

[0059] From the viewpoint of properly obtaining the effects of the present invention, -W in (m-Ox-3) 4 - Preferably 1,4-phenylene.

[0060] (Repeating unit (a2))

[0061] In formula (2) above, Y2 represents a divalent organic group having the group -X-J. Preferably, Y2 is a group obtained by removing two amino groups from an aromatic diamine (hereinafter also referred to as a specific diamine (V)) represented by "A-X-J".

[0062] 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 groups include: benzene rings, naphthalene rings, and biphenyl structures.

[0063] 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 having 6 to 40 carbon atoms in J. Ak represents a divalent organic group having 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, A1 represents -O- or -COO-, and in the case of multiple A1s, each A1 independently has the above definition. m1 is an integer from 1 to 2. In the case of m1 being 2, multiple a1s independently have the above definition).

[0064] For X, the preferred options are: -O-, -COO-, -OCO-, or -(A1). a0 -((CH2) a1 -A1) m1 -.

[0065] 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 with 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 the carbon-carbon bond of any methylene group in these groups 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 unsubstituted alicyclic hydrocarbon group and an aromatic hydrocarbon group substituted with substituents other than the aforementioned substituents.

[0066] Examples of alicyclic hydrocarbon groups with 4 to 40 carbon atoms in J include cyclobutane rings, cyclopentane rings, cyclohexane rings, cyclodecane rings, and steroidal skeletons (e.g., cholesteryl, cholesterol, or lanostane). Examples of aromatic hydrocarbon groups with 6 to 40 carbon atoms include benzene rings and naphthalene rings. When J has at least any one of cyclohexane rings and benzene rings, the group "-X-J" can be represented by structures such as (S1), and more preferably by formulas (S1-1) to (S1-5).

[0067]

[0068] (X 1This indicates the definition of X in the group -X-J or -O-CO-CH=CH-*** (*** indicates interaction with G). 1 (The bond of the phenylene bond in 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.

[0069] m is an integer from 1 to 4. When m is 2 or greater, there are multiple X... 1 G 1 Each possesses the above definition independently.

[0070] R 1 It 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.

[0071]

[0072] (X 1 R 1 X in the above formula (S1) 1 R 1 The meaning is the same.

[0073] 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 with 6 to 40 carbon atoms in J; Ak represents a divalent organic group with 1 to 10 carbon atoms), a preferred specific example is: [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-ene] [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)benzoyl

[0074]

[0075] (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.)

[0076] (Repeating unit (b3))

[0077] In formula (3) above, Y3 represents a divalent organic group having an aromatic carboxyl group. Here, an aromatic carboxyl group refers to a functional group formed by the direct bonding of at least one carboxyl group with an aromatic group. The number of carboxyl groups bonded to the aromatic group is preferably 1 to 8. Specific examples of aromatic groups include: benzene rings, naphthalene rings, biphenyl structures, or structures formed by bonding two or more benzene rings through connecting groups such as -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-. Among them, Y3 is preferably a group formed by removing two amino groups from an aromatic diamine (hereinafter also referred to as a specific diamine (B)) having an aromatic carboxyl group.

[0078] Preferred examples of the specific diamine (B) described above include: 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and the diamines shown in formulas (3b-1) to (3b-2) below. Preferred specific examples of the diamines shown in formulas (3b-1) to (3b-2) above are 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-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, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, and 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid, etc.

[0079]

[0080] (where A is in the formula) 1 A 21 And A 22 This represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-. m11 and m12 are each independent integers from 0 to 4, and m11 + m12 is an integer from 1 to 4. m2 is an integer from 1 to 4.

[0081] (Repeating unit (c4))

[0082] At least one of the polyimide precursors in polymers (A) and (B) may further have a repeating unit (c4) of the unit shown in formula (4) below. Polymers (A) and (B) may also be polyimides of imide derivatives having a repeating unit (c4) of the unit shown in formula (4) below. It should be noted that the repeating unit (c4) may be one type or more than two types.

[0083]

[0084] (X4 represents a tetravalent organic group. Y4 represents a divalent organic group, which is an organic group other than a divalent organic group with an oxazoline skeleton, a divalent organic group with a -X-J group, or a divalent organic group with an aromatic carboxyl group. The two R and Z have the same meaning as R and Z in formula (1).)

[0085] When the polymer (A) contains the repeating unit (c4) or the imidized structural unit of the repeating unit (c4), the total of the repeating unit (a1), the repeating unit (a2) and their imidized structural units is preferably 90 mol% or less, more preferably 80 mol% or less, constituting the total repeating unit of the polymer (A).

[0086] When polymer (B) contains the repeating unit (c4) or the imidized structural unit of the repeating unit (c4), the total amount of the repeating unit (c4) or the imidized structural unit of the repeating unit (c4) is preferably 10 to 95 mol% of the total repeating unit of polymer (B), more preferably 20 to 90 mol%.

[0087] Y4 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 may also be diamines other than those described below.

[0088] 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; 4,4'-diaminoazobenzene, diaminodiphenylacetylene, or 4,4-diaminochalcone and other diamines with photo-oriented groups; 2-( Diamines with photopolymerizable groups at the ends, such as 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, and 1,3-bis(4-amino) Diamines containing urea bonds, such as phenyl(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)hexafluoropropane, etc. Fluoropropane, 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'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, diamines of formulas (z-1) to (z-5) below, 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'-dimethylbenzidine Diamines having a diphenylamine structure, such as (-aminophenyl)-N,N'-dimethyl-1,4-phenylenediamine, are diamines having at least one nitrogen-containing structure (hereinafter also referred to as specific nitrogen-containing structures) selected from the group consisting of nitrogen-containing heterocycles, secondary amino groups, and tertiary amino groups (wherein, the molecule does not contain an amino group bonded to a protecting group that is removed by heating and substituted with a hydrogen atom. Furthermore, specific diamines (Ox) are not included); 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamino-3,3'-dihydroxybiphenyl; 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; N1,N4-bis(2-tert-butoxycarbonylamino-4-aminophenyl)hexamethylenediamine, 4-amino-N-(2-tert-butoxycarbonylamino-4-aminophenyl)benzamide, N-[(2,5-diaminophenyl)methyl]-1,1-dimethylethyl ester of carbamate, N-[3-(2,5-diaminophenyl)propyl]-1,1-dimethylethyl 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 Esters, carbamates, N-(4-aminophenyl)-N-[[1-(4-aminophenyl)-4-piperidinyl]methyl]-1,1-dimethyl ethyl ester, and other diamines having the group "-N(D)-" (D represents a protecting group that is removed and replaced by a hydrogen atom by heating, preferably tert-butoxycarbonyl); 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecanyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene Aromatic diamines with long-chain alkyl groups having 12 to 20 carbon atoms, represented by 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; 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, bis(p-aminobenzene) Diamines containing siloxane bonds, such as (-(aminomethyl)propyl)tetramethyldisiloxane; diamines containing 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, including m-phenylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and diamines containing 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.

[0089]

[0090] 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.

[0091] 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.

[0092] In formulas (1) to (4) above, X1 to X4 represent tetravalent organic groups. X1 to X4 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 tetravalent organic groups derived from acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, or their derivatives. More preferably, tetracarboxylic dianhydrides or their derivatives contain at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0093] As a tetracarboxylic dianhydride or its derivative for obtaining polymer (A), acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, or their derivatives are preferred. More preferably, a tetracarboxylic dianhydride or its derivative comprising at least one partial structure selected from the group consisting of cyclobutane ring structures, cyclopentane ring structures, and cyclohexane ring structures is preferred.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] The above-mentioned X1 to X4 are preferably tetravalent organic groups derived from the following tetracarboxylic dianhydrides or their derivatives (hereinafter also collectively referred to as specific tetracarboxylic acid derivatives).

[0098] 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.

[0099] 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.

[0100] The proportion of the aforementioned specific tetracarboxylic acid derivative used relative to 1 mole of all tetracarboxylic acid components used to obtain polymer (A) or (B) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more.

[0101] As monovalent organic groups R and Z in the above formulas (1) to (4), examples include: 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 a monovalent hydrocarbon group having 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 with 1 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, alkynyl with 2 to 10 carbon atoms, tert-butoxycarbonyl or 9-fluorenemethoxycarbonyl are preferred, alkyl with 1 to 3 carbon atoms are more preferred, and methyl is even more preferred.

[0102] 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.

[0103] <Methods for manufacturing polyimide precursors and polyimides>

[0104] 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 WO2013 / 157586.

[0105] 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.

[0106] For example, in the case of obtaining a polymer having a repeating unit of the unit 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 dianhydride having the structure of the following formula is used.

[0107]

[0108] (The definition of X1 is the same as in equation (1) above.)

[0109] 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.

[0110] 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.

[0111] 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%.

[0112] 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.

[0113] <End-capping agent>

[0114] When synthesizing polymers (A) and (B) of this invention, they can also be synthesized using a suitable capping agent together with a tetracarboxylic acid component containing tetracarboxylic dianhydride or its derivative and a diamine component containing the aforementioned diamine. The capped polymers have the effect of improving the film hardness of the liquid crystal alignment film obtained from the coating and improving the adhesion properties between the sealant and the liquid crystal alignment film.

[0115] 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.

[0116] 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, or 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate.

[0117] 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.

[0118] The molecular weight of each polymer (A) and (B) 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 determined by GPC (Gel Permeation Chromatography).

[0119] (Liquid crystal alignment agent)

[0120] The liquid crystal alignment agent of the present invention is a liquid composition of polymers (A), (B) and other components used as needed, preferably dispersed or dissolved in a suitable organic solvent.

[0121] Furthermore, other polymers besides polymers (A) and (B) 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).

[0122] 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.

[0123] 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.

[0124] The following compounds can be listed as preferred examples of the aforementioned crosslinking compound (c-1).

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] Compounds having end-capped isocyanate groups include: CORONATE AP stable M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS-50 (all manufactured by TOSOH); TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, 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 International Patent Publication No. 2015 / 141598.

[0130] 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.

[0131] The following compounds can be listed as preferred examples of the aforementioned crosslinking compound (c-2).

[0132] Glyceryl mono(meth)acrylate, glyceryl di(meth)acrylate (a mixture of 1,2- and 1,3-type meth)acrylate, glyceryl 1,3-diglyceryl glycol 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, hexaethylene glycol mono(meth)acrylate, etc.

[0133] The content of the crosslinking compound contained 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.

[0134] 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.

[0135] 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, 3-epoxypropoxypropylmethyldimethoxysilane. Silane compounds include oxy-based silanes, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane. 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.

[0136] 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.

[0137] 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-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone; N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, and ethylene glycol monobutyl ether; 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-ethyl-2-pyrrolidone, dipropylene glycol monomethyl ether and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone 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 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; N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether; γ-butyrolactone, ethylene 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 with propylene glycol monobutyl ether; cyclopentanone with propylene glycol monomethyl ether; cyclohexanone with diethylene glycol monoethyl ether; cyclopentanone with diethylene glycol monoethyl ether; cyclohexanone with diisobutyl ketone; cyclopentanone with diisobutyl ketone; methyl isobutyl ketone with propylene glycol monobutyl ether; methyl ethyl ketone with propylene glycol monobutyl ether; cyclohexanone with 4-hydroxy-4-methyl-2-pentanone; cyclopentanone with 4-hydroxy-4-methyl-2-pentanone; cyclohexanone with diethylene glycol diethyl ether; cyclopentanone with diethylene glycol diethyl ether; tetramethylurea with propylene glycol diacetate; N,N-dimethylpropionamide with propylene glycol monobutyl ether; tetramethylurea with propylene glycol monobutyl ether; tetramethylurea, cyclohexanone and propylene glycol monomethyl ether; N,N-dimethylpropionamide with propylene glycol monomethyl ether;N,N-Dimethylpropionamide with ethylene glycol monobutyl ether acetate; N,N-Dimethylpropionamide with ethylene glycol monobutyl ether; N,N-Diethylpropionamide with propylene glycol monomethyl ether; tetramethylurea with propylene glycol monomethyl ether; N,N-Dimethylpropionamide, cyclohexanone, and diethylene glycol diethyl ether; N,N-Diethylformamide with propylene glycol monomethyl ether; N,N-Diethylformamide with 4-hydroxy-4-methyl-2-pentanone; N,N-Diethylformamide with propylene glycol monomethyl ether; cyclohexanone with n-butyl acetate; cyclopentanone with 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.

[0138] The concentration of the solid component in the liquid crystal alignment agent (the proportion of the total mass of the 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, it is preferably 1% by mass or more, and from the perspective of the storage stability of the solution, it is preferably 10% by mass or less. A particularly preferred polymer concentration is 2 to 8% by mass.

[0139] <Liquid Crystal Alignment Film>

[0140] 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.

[0141] Liquid crystal display element

[0142] 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.

[0143] 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.

[0144] (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.

[0145] 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.

[0146] (2) The process of firing the coating film

[0147] 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.

[0148] 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.

[0149] 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.

[0150] (3) A liquid crystal layer is formed between the above-mentioned pair of substrates to manufacture a liquid crystal cell.

[0151] (3-1) Manufacturing of VA-type liquid crystal display elements

[0152] 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.

[0153] 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.

[0154] 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 naphthyl rings. It may also contain compounds having two or more rigid sites (mesocrystalline skeletons) within the molecule that exhibit liquid crystal properties (e.g., bimesocrystalline compounds formed by two rigid biphenyl structures or terphenyl structures linked by alkyl groups). The liquid crystal composition may be a nematic liquid crystal composition, a smectic liquid crystal composition, or a cholesteric liquid crystal composition.

[0155] Furthermore, from the viewpoint of improving liquid crystal orientation, the above-mentioned liquid crystal composition may be further supplemented with additives. Such additives include: photopolymerizable monomers such as compounds having 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.

[0156] Examples of positive liquid crystal displays include: Merck's ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081.

[0157] Examples of negative liquid crystals include: MLC-3023, MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, and MLC-7029 manufactured by Merck.

[0158] In addition, in PSA mode, as a liquid crystal containing a compound with polymerizable groups, Merck's MLC-3023 can be cited as an example.

[0159] 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.

[0160] 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.

[0161] (3-2) Manufacturing of PSA-based liquid crystal display elements

[0162] 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.

[0163] (3-3) Case where a coating is formed on a substrate using a liquid crystal alignment agent containing a compound with polymerizable groups.

[0164] 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.

[0165] (4) The process of irradiating the liquid crystal cell with light

[0166] 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 .

[0167] 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.

[0168] The liquid crystal display element of the present 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, portable telephones, smartphones, various monitors, LCD TVs, information displays, and other display devices. Furthermore, the polymer composition contained in 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, liquid crystal array antennas, or 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.

[0169] Example

[0170] 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.

[0171] (Organic solvents)

[0172] NMP: N-methyl-2-pyrrolidone.

[0173] BCS: Butyl cellosolve (ethylene glycol monobutyl ether).

[0174] (Tetracarboxylic acid dianhydride)

[0175] (CA-1)~(CA-3): These are compounds represented by the following formulas (CA-1)~(CA-3).

[0176]

[0177] (Diamine)

[0178] (DA-1)~(DA-9): These are compounds represented by the formulas (DA-1)~(DA-9) below.

[0179]

[0180] <Viscosity Measurement>

[0181] 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.

[0182] <Determination of molecular weight>

[0183] 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.

[0184] 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.

[0185] Standard samples used for calibration curve preparation: TSK standard polyethylene oxide (molecular weight; approx. 900,000, approx. 150,000, approx. 100,000 and approx. 30,000) (manufactured by TOSOH) and polyethylene glycol (molecular weight; approx. 12,000, approx. 4,000 and approx. 1,000) (manufactured by Polymer Laboratories).

[0186] [Polymer Synthesis]

[0187] <Synthesis example 1>

[0188] DA-1 (2.97 g, 10.0 mmol), DA-2 (0.610 g, 4.0 mmol), DA-3 (2.28 g, 6.0 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, 9.2 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 (PAA-1) with a solid content of 20% by mass (viscosity: 657 mPa·s). The Mn of this polyamic acid was 12300, and the Mw was 32500.

[0189] <Synthesis example 2>

[0190] DA-1 (2.97 g, 10.0 mmol), DA-4 (0.430 g, 4.0 mmol), DA-3 (2.28 g, 6.0 mmol), CA-1 (2.50 g, 10.0 mmol), and NMP (32.8 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 (1.84 g, 9.4 mmol) and NMP (7.37 g) were added, and the mixture was stirred at 40 °C for 3 hours, thus obtaining a polyamic acid solution (PAA-2) with a solid content of 20% by mass (viscosity: 720 mPa·s). The Mn of this polyamic acid was 14500, and the Mw was 32600.

[0191] <Synthesis Example 3>

[0192] DA-2 (1.22 g, 8.0 mmol), DA-4 (1.30 g, 12.0 mmol), CA-2 (3.84 g, 19.6 mmol), and NMP (25.5 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred at 40 °C for 3 hours while nitrogen was being introduced, thus obtaining a polyamic acid solution (PAA-3) with a solid content of 20% by mass (viscosity: 780 mPa·s). The Mn of this polyamic acid was 15600, and the Mw was 32300.

[0193] <Synthesis example 4>

[0194] DA-5 (0.970 g, 4.0 mmol), DA-1 (2.08 g, 7.0 mmol), DA-6 (0.990 g, 3.0 mmol), DA-7 (2.61 g, 6.0 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 (1.93 g, 9.8 mmol) and NMP (7.72 g) were added, and the mixture was stirred at 40 °C for 3 hours to obtain a polyamic acid solution (PAA-4) with a solid content of 20% by mass (viscosity: 650 mPa·s). The Mn of this polyamic acid was 12400, and the Mw was 26700.

[0195] <Synthesis example 5>

[0196] DA-8 (0.790 g, 4.0 mmol), DA-2 (0.610 g, 4.0 mmol), DA-5 (1.45 g, 6.0 mmol), DA-9 (2.46 g, 6.0 mmol), CA-2 (3.07 g, 15.7 mmol), and NMP (34.3 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 (0.870 g, 4.0 mmol) and NMP (3.49 g) were added, and the mixture was stirred at room temperature for 3 hours, thus obtaining a polyamic acid solution (PAA-5) with a solid content of 20% by mass (viscosity: 780 mPa·s). The Mn of this polyamic acid was 11500, and the Mw was 24500.

[0197] <Synthesis Example 6>

[0198] DA-8 (1.59 g, 8.0 mmol), DA-5 (1.45 g, 6.0 mmol), DA-9 (2.46 g, 6.0 mmol), CA-2 (3.07 g, 15.7 mmol), and NMP (34.3 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 (0.870 g, 4.0 mmol) and NMP (3.49 g) were added, and the mixture was stirred at room temperature for 3 hours, thus obtaining a polyamic acid solution (PAA-6) with a solid content of 20% by mass (viscosity: 720 mPa·s). The Mn of this polyamic acid was 15600, and the Mw was 23400.

[0199] <Synthesis Example 7>

[0200] DA-8 (0.790 g, 4.0 mmol), DA-2 (0.610 g, 4.0 mmol), DA-5 (1.45 g, 6.0 mmol), DA-9 (2.46 g, 6.0 mmol), CA-2 (3.89 g, 19.8 mmol), and NMP (36.9 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, thus obtaining a polyamic acid solution (PAA-7) with a solid content of 20% by mass (viscosity: 820 mPa·s). The Mn of this polyamic acid was 16200, and the Mw was 29200.

[0201] <Synthesis example 8>

[0202] DA-2 (0.610 g, 4.00 mmol), DA-8 (0.790 g, 4.00 mmol), DA-5 (1.45 g, 6.00 mmol), DA-9 (2.46 g, 6.00 mmol), CA-1 (2.50 g, 10.00 mmol), and NMP (31.3 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, 9.76 mmol) and NMP (7.66 g) were added, and the mixture was stirred at 40 °C for 3 hours to obtain a polyamic acid solution (PAA-8) with a solid content of 20% by mass (viscosity: 697 mPa·s). The Mn of this polyamic acid was 13430, and the Mw was 39640.

[0203] The specifications of the polymers obtained in the above synthesis examples are shown in Table 1 below.

[0204] [Table 1]

[0205]

[0206] [Preparation of Liquid Crystal Alignment Agent]

[0207] <Example 1>

[0208] NMP (8.00 g) and BCS (8.00 g) were added to PAA-2 (1.20 g) obtained in Synthesis Example 2 and PAA-3 (2.80 g) obtained in Synthesis Example 3, and the mixture was stirred at room temperature for 3 hours to obtain liquid crystal alignment agent (A-1).

[0209] <Comparative Example 1>

[0210] NMP (8.00 g) and BCS (8.00 g) were added to PAA-1 (4.00 g) obtained in Synthesis Example 1, and the mixture was stirred at room temperature for 3 hours to obtain liquid crystal alignment agent (B-1).

[0211] <Examples 2, 3, 4, and Comparative Example 2>

[0212] PAA-4 and PAA-5, PAA-4 and PAA-7, PAA-4 and PAA-8, PAA-4 and PAA-6 were used to replace PAA-2 and PAA-3, respectively. Otherwise, the liquid crystal alignment agents (A-2), (A-3), (A-4), and (B-2) of Examples 2, 3, 4, and Comparative Example 2 were obtained in the same manner as in Example 1.

[0213] The specifications of the liquid crystal alignment agents obtained in the above embodiments and comparative examples are shown in Table 2 below.

[0214] [Table 2]

[0215]

[0216] It was confirmed that the liquid crystal alignment agents (A-1) to (A-4) and (B-1) to (B-2) 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.

[0217] [Fabrication of a liquid crystal cell for evaluating voltage retention rate]

[0218] Liquid crystal cells were fabricated using the liquid crystal alignment agents obtained in Examples 1-4 and Comparative Examples 1-2 as shown below. The liquid crystal alignment agents were spin-coated onto glass substrates (3cm × 4cm) with ITO electrodes, dried on a heating plate at 70°C for 90 seconds, and then fired in an infrared furnace at 230°C for 20 minutes to produce glass substrates with a 100nm thick liquid crystal alignment film (substrate with liquid crystal alignment film). Two substrates with liquid crystal alignment films were prepared. On the surface of one substrate with the liquid crystal alignment film, 4μm diameter bead-shaped spacers (made by Nichibukai Chemicals, silk balls, SW-D1) were coated to leave a liquid crystal injection port. A thermosetting sealant (made by Mitsui Chemicals, XN-1500T) was printed around the bead. Next, the surface of the other substrate with the liquid crystal alignment film, with the liquid crystal alignment film side facing inwards, was bonded to the first substrate. The sealant was then cured to produce an empty cell. A liquid crystal cell was fabricated by injecting MLC-3023 liquid crystal (manufactured by Merck) into the empty cell using a reduced-pressure injection method. Then, while applying a 15V DC voltage to the liquid crystal cell, it was irradiated from the outside with 10J / cm² liquid crystal. 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 illuminometer equipped with an ultraviolet light meter (ORC Corporation, UV-MO3A). Then, to deactivate unreacted polymeric compounds remaining in the liquid crystal cell, the sample was irradiated for 30 minutes with a UV-FL irradiation unit (TOSHIBA LIGHTING & TECHNOLOGY Corporation) without applied voltage (UV lamp: FLR40SUV32 / A-1) (hereinafter also referred to as PSA treatment).

[0219] [Evaluation of voltage retention rate]

[0220] 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 16.67ms. 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 85% or higher after PSA treatment was marked as "○", and a rate less than 85% was marked as "×".

[0221] [Evaluation of voltage retention rate after aging]

[0222] The PSA-treated liquid crystal cells were placed in a high-temperature and high-humidity oven set at 60°C and 90% humidity for 12 days for aging. The voltage retention rate of the aged liquid crystal cells was calculated in the same manner as above. As an evaluation benchmark, cases with a voltage retention rate of 50% or higher after aging were marked as "○", and cases with a voltage retention rate of less than 50% were marked as "×".

[0223] The evaluation results of voltage retention rate after PSA treatment and aging are shown in Table 3.

[0224] [Table 3]

[0225]

[0226] As shown in Table 3, the liquid crystal alignment films obtained using the liquid crystal alignment agents (A-1) to (A-4) of Examples 1 to 4 exhibited high voltage retention rates after PSA treatment. Furthermore, the liquid crystal alignment films obtained using the liquid crystal alignment agents (A-1) to (A-4) of Examples 1 to 4 also exhibited high voltage retention rates after high-temperature and high-humidity aging, compared to the liquid crystal alignment films obtained using the liquid crystal alignment agents (B-1) to (B-2) of Comparative Examples 1 to 2.

[0227] It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2021-124164, filed on July 29, 2021, are incorporated herein as a disclosure of the specification of this invention.

Claims

1. A liquid crystal alignment agent comprising components A and B as described below, Component A: At least one polymer A selected from the group consisting of a polyimide precursor having repeating unit a1 of the unit shown in formula (1) and repeating unit a2 of the unit shown in formula (2) below, and a polyimide as an imide derivative of the polyimide precursor, wherein, Polymer A does not have the repeating unit b3 of the unit shown in equation (3) below. Component B: At least one polymer B selected from the group consisting of a polyimide precursor having a repeating unit b3 as shown in formula (3) below and a polyimide as an imide derivative of the polyimide precursor. The mass ratio of the content of polymer A to the content of polymer B is 5 / 95 to 95 / 5, calculated as polymer A / polymer B. In formulas (1) and (2), X1 and X2 represent tetravalent organic groups derived from tetracarboxylic dianhydride or its derivatives, and the tetravalent organic groups are tetravalent organic groups derived from acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, or their derivatives; Y1 represents a divalent organic group having an oxazoline skeleton; Y2 represents a divalent organic group having the group -X-J; R and Z represent hydrogen atoms. In the group –X-J, X represents a single bond and –(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 with 6 to 40 carbon atoms in J; in – (A1) a0 - (CH2) a1 -A1) m1 In the given text, a0 is an integer of 0 or 1, a1 is an integer from 1 to 15, A1 represents -O- or -COO-, and in the case of multiple A1s, each A1 independently has the aforementioned definition; m1 is an integer from 1 to 2; when m1 is 2, multiple a1s independently have the aforementioned definition, and -Ak-O-CO-CH=CH-** is [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo [-propyl-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, or [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]propyl-2-enyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-propyl-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 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 with 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 the carbon-carbon bond of any methylene group in these groups is optionally interrupted by -O-. In formula (3), X3 represents a tetravalent organic group derived from tetracarboxylic dianhydride or its derivatives, and the tetravalent organic group is a tetravalent organic group derived from acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, or their derivatives; Y3 represents a divalent organic group having an aromatic carboxyl group; the two R and Z have the same meaning as R and Z in formula (1).

2. The liquid crystal alignment agent according to claim 1, wherein, Y1 is a divalent organic group with an oxazoline backbone in the polymer backbone.

3. The liquid crystal alignment agent according to claim 1 or 2, wherein, Y1 is a divalent organic group having a partial structure shown in the following formula (m-Ox) in the main chain of the polymer. In the formula (m-Ox), R 1 * indicates hydrogen or a monovalent organic group, and * indicates a bonded bond.

4. The liquid crystal alignment agent according to claim 3, wherein, Y1 is a group formed by removing two amino groups from a specific diamine m-Ox having the structure shown in formula (m-Ox), wherein the specific diamine m-Ox is a diamine selected from the group consisting of formulas (m-Ox-1) to (m-Ox-3). In equations (m-Ox-1) to (m-Ox-3), R 1 R with equation (m-Ox) 1 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 - Divalent organic groups L and R formed from the groups in the group. 11 Indicates a hydrogen atom or a methyl group; W 1 ~W 2 W 4 W represents an aromatic hydrocarbon group. 3 Represents an aromatic hydrocarbon group or an alicyclic hydrocarbon group; a is an integer of 0 or 1; in the formula (m-Ox-2), multiple R... 1 W 1 And multiple Rs when a is 1 2 They may be identical or different from each other; in equation (m-Ox-3), the two Rs 1 R 2 and W 2 They may be the same as or different from each other.

5. The liquid crystal alignment agent according to claim 1 or 2, wherein, Y2 is a group formed by removing two amino groups from an aromatic diamine, i.e., a specific diamine V, as shown in A-X-J. In A-X-J, A represents a monovalent group formed by the bonding of two primary amino groups with an aromatic group.

6. The liquid crystal alignment agent according to claim 1 or 2, wherein, The aromatic carboxyl group is a functional group formed by direct bonding of at least one carboxyl group with an aromatic group. The aromatic group is a benzene ring, a naphthalene ring, a biphenyl structure, or a structure formed by bonding two or more benzene rings through a linking group represented by -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-.

7. The liquid crystal alignment agent according to claim 1 or 2, wherein, At least one of the polyimide precursors in polymers A and B further comprises a repeating unit c4 of the unit shown in formula (4) below. In formula (4), X4 represents a tetravalent organic group derived from tetracarboxylic dianhydride or its derivatives, and the tetravalent organic group is a tetravalent organic group derived from acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, or their derivatives; Y4 is a group obtained by removing two amino groups from a diamine having at least one nitrogen-containing structure selected from the group consisting of nitrogen-containing heterocycles, secondary amino groups, and tertiary amino groups, wherein the diamine does not have an amino group bonded to a protecting group that is removed by heating and replaced by a hydrogen atom, and does not include diamines that provide a divalent organic group having an oxazoline skeleton; the two R and Z have the same meaning as R and Z in formula (1).

8. A liquid crystal alignment film obtained from a liquid crystal alignment agent as described in any one of claims 1 to 7.

9. A liquid crystal display element comprising the liquid crystal alignment film as described in claim 8.

10. 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 7 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.

11. The method for manufacturing a liquid crystal display element according to claim 10, wherein, This includes the following step 4, which is performed after steps 1-3. Step 4: The process of irradiating the liquid crystal cell with light.

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