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

Abstract

Provided are a liquid crystal alignment film and a liquid crystal alignment agent that provide a liquid crystal display element having a high pretilt angle. The liquid crystal aligning agent is characterized by containing the following component (B). Component (B): a polymer (B) having a repeating unit structure represented by formula (1). (W represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having 4-40 carbon atoms and an aromatic hydrocarbon group having 6-40 carbon atoms. R and R'independently represent a hydrogen atom or a monovalent organic group, Ar represents a divalent structure having an aromatic ring (wherein Ar is a group other than carbonyl carbon and is bonded to-NR-or-NR '), and * represents a bond.

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] In the past, various driving methods have been developed for liquid crystal display elements, including different electrode structures and the physical properties of liquid crystal molecules. For example, various display elements such as TN (Twisted Nematic), STN (Super Twisted Nematic), VA (Vertical Alignment), IPS (In-Plane Switching), and FFS (fringe field switching) are known.

[0003] These liquid crystal display elements typically have a liquid crystal alignment film for aligning liquid crystal molecules. Materials known as liquid crystal alignment films include polyamic acid, polyamic acid esters, polyimide, poly(meth)acrylate, or polymers containing a triazine structure in their backbone (see, for example, Patent Documents 1 and 2).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: WO2021 / 205736

[0007] Patent Document 2: WO2020 / 045549 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] Due to their high contrast and wide viewing angle, VA-type liquid crystal display elements are increasingly used in various applications such as televisions and automotive displays, which raises the requirements for display quality levels compared to the past.

[0010] In particular, in response to display defects caused by low pretilt angles of liquid crystal display elements, it is ideal to develop a liquid crystal alignment film and liquid crystal alignment agent that provide liquid crystal display elements with higher pretilt angles than before.

[0011] On the other hand, when using photo-alignment processing to fabricate liquid crystal alignment films, the liquid crystal alignment films require the ability to freely control the angle of liquid crystal molecules.

[0012] In view of the above, one object of the present invention is to provide a liquid crystal alignment film and a liquid crystal alignment agent, wherein the liquid crystal alignment film and the liquid crystal alignment agent provide a liquid crystal display element having a high pretilt angle. Furthermore, another object of the present invention is to provide a liquid crystal alignment film and a liquid crystal alignment agent, wherein the pretilt angle of the liquid crystal molecules can be easily controlled even when the liquid crystal alignment film is fabricated using a photoalignment process.

[0013] Solution for solving the problem

[0014] In order to solve the above-mentioned technical problems, the inventors conducted in-depth research and found that liquid crystal alignment agents containing specific polymers are effective in achieving the above-mentioned objectives, thus completing the present invention.

[0015] The present invention includes the following solutions.

[0016] [1] A liquid crystal alignment agent, characterized in that it contains the following component (B).

[0017] (B) Component: Polymer (B) having the repeating unit structure shown in the following formula (1).

[0018]

[0019] (W represents a monovalent organic group having at least one group selected from the group consisting of alicyclic hydrocarbon groups with 4 to 40 carbon atoms and aromatic hydrocarbon groups with 6 to 40 carbon atoms.)

[0020] R and R' represent hydrogen atoms or monovalent organic groups independently of each other.

[0021] Ar represents a divalent structure with an aromatic ring (where Ar is a group other than the carbonyl carbon, bonded to -NR- or -NR'-).

[0022] It should be noted that, in this invention, halogen atoms can include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., and * indicates a bond.

[0023] Invention Effects

[0024] According to the present invention, a liquid crystal alignment film and a liquid crystal alignment agent, as well as a liquid crystal display element having the above-described liquid crystal alignment film, can be provided, wherein the liquid crystal alignment film and the liquid crystal alignment agent provide a liquid crystal display element having a high pretilt angle. Furthermore, according to the present invention, a liquid crystal alignment film and a liquid crystal alignment agent, as well as a liquid crystal display element having the liquid crystal alignment film, can be provided, wherein the liquid crystal alignment film and the liquid crystal alignment agent can easily control the pretilt angle of the liquid crystal molecules even when the liquid crystal alignment film is fabricated using a photo-alignment process.

[0025] The mechanism by which the above-mentioned effects of the present invention are obtained may not be clear, but the following may be considered as one of the reasons.

[0026] That is, it is believed that the reason is that the liquid crystal alignment film has a rigid triazine structure in the parent core framework, which can suppress the alignment film disorder caused by heat during heat treatment such as sealant curing after photoalignment treatment, and maintain a low pretilt angle during photoalignment treatment. Detailed Implementation

[0027] Hereinafter, the liquid crystal alignment agent of the present invention, the liquid crystal alignment film obtained from the liquid crystal alignment agent, and the liquid crystal display element having the liquid crystal alignment film will be described in detail. The description of the necessary conditions for the construction described below is an example of an embodiment of the present invention and is not specific to these contents.

[0028] (Liquid crystal alignment agent)

[0029] The liquid crystal alignment agent of the present invention contains the above-described component (B). Hereinafter, the polymer (B), which is component (B), will be described in detail.

[0030] <Polymer (B)>

[0031] (B) Component: Polymer (B) having the repeating unit structure shown in the following formula (1).

[0032]

[0033] R and R' represent hydrogen atoms or monovalent organic groups independently of each other.

[0034] As monovalent organic groups in R and R' of the above formula (1), examples include: monovalent hydrocarbon groups with 1 to 20 carbon atoms, and the methylene groups of such hydrocarbon groups being -O-, -S-, -CO-, -COO-, -COS-, -NR-. 3 -、-CO-NR 3 -, -Si(R) 3 Monovalent group A is formed by substitution with 2−, -SO2−, etc. (wherein, R in group A is...) 3 It is a monovalent hydrocarbon group with 1 to 10 carbon atoms, and has multiple R atoms. 3 In the case of each R 3(Optionally the same or different) At least one of the hydrogen atoms bonded to a carbon atom in the monovalent hydrocarbon group or monovalent group A described above is replaced by 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., forming a monovalent group or a heterocyclic monovalent group. As the monovalent organic group in R and R' of the above formula (1), preferably an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, a tert-butoxycarbonyl group, or a 9-fluorenemethoxycarbonyl group, more preferably an alkyl group with 1 to 3 carbon atoms, and even more preferably a methyl group.

[0035] From the viewpoint of obtaining the appropriate effects of the present invention, R and R' in the above formula (1) are each preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, more preferably hydrogen atoms or methyl groups.

[0036] Ar represents a divalent structure with an aromatic ring (wherein Ar is a group other than the carbonyl carbon, bonded to -NR- or -NR'-. More preferably Ar is bonded to at least one of -NR- or -NR'- via an aromatic ring, and even more preferably to both -NR- and -NR'- via an aromatic ring).

[0037] There are no particular restrictions on the divalent aromatic ring structure in Ar, as long as it is formed by removing two hydrogen atoms from the aromatic ring structure.

[0038] Ar structures containing aromatic rings include, for example: aromatic rings; structures containing aromatic rings and chain structures; polycyclic structures containing aromatic rings and other cyclic structures (a1); polycyclic structures (a2) consisting of at least two cyclic groups selected from the group consisting of aromatic rings and polycyclic structures (a1) bonded by a linking group; and polycyclic structures (a3) ​​consisting of at least one cyclic structure selected from the group consisting of aromatic rings and polycyclic structures (a1) bonded to a cyclic structure other than an aromatic ring via a linking group.

[0039] As the aforementioned chain structure, any type of chain hydrocarbon group, whether saturated or unsaturated, straight-chain or branched, can be listed. Specific examples of chain structures include: alkylene groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, or ynylene groups with 2 to 20 carbon atoms.

[0040] Other cyclic structures besides the aforementioned aromatic rings include saturated heterocyclic or alicyclic hydrocarbons.

[0041] Specific examples of saturated heterocycles include: oxazoline rings, pyrazolidine rings, piperidine rings, piperazine rings, etc.

[0042] As specific examples of alicyclic hydrocarbons, the structures illustrated in the alicyclic hydrocarbon groups of W described later can be listed.

[0043] Specific examples of aromatic rings in Ar mentioned above include: monocyclic aromatic carbon rings, monocyclic aromatic heterocycles, or condensation rings formed by the condensation of two or more rings selected from the group consisting of monocyclic aromatic carbon rings and monocyclic aromatic heterocycles, wherein these rings optionally have substituents. Examples of such substituents include: alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkyl carbonyl groups having 2 to 10 carbon atoms, alkoxy carbonyl groups having 2 to 10 carbon atoms, alkoxy carbonyl groups having 2 to 10 carbon atoms, halogen atoms, cyano groups, nitro groups, amino groups, thiols, etc.

[0044] Specific examples of monocyclic aromatic carbon rings include the benzene ring. Specific examples of monocyclic aromatic heterocycles include: pyridine rings, pyrimidine rings, pyrazine rings, pyridazine rings, triazine rings, pyrrole rings, imidazole rings, or pyrazole rings.

[0045] Specific examples of condensed rings formed by the condensation of two or more rings selected from the group consisting of monocyclic aromatic carbon rings and monocyclic aromatic heterocycles include: naphthalene rings, anthracene rings, quinoline rings, isoquinoline rings, carbazole rings, benzimidazole rings, indole rings, quinoxaline rings, or acridine rings.

[0046] Specific examples of the aforementioned polycyclic structure (a1) include polycyclic compounds containing alicyclic hydrocarbons such as fluorene and indane. More preferably, the aforementioned polycyclic structures (a2) and (a3) ​​are structures formed by the cyclic groups being bonded together by divalent linking groups (L).

[0047] Specific examples of the linking group (L) mentioned above include: single bond, -O-, -S-, -SO2-, -Si(R”)2-, -C(=O)-, -O-C(=O)-, -NR-C(=O)-, -NR- or -NR-C(=O)-NR-, chain hydrocarbon group with 1 to 20 carbon atoms, or divalent organic group formed by inserting a heteroatom-containing group at least at one of the carbon-carbon bonds of the chain hydrocarbon group or at the end of the chain hydrocarbon group (wherein, in the case where a heteroatom-containing group is inserted into the carbon-carbon bond of the chain hydrocarbon group, the inserted chain hydrocarbon group forms a carbon atom number of 2 or more on the main chain of the polymer).

[0048] The aforementioned chain hydrocarbon groups having 1 to 20 carbon atoms can be any type of straight-chain or branched chain. Specific examples of chain hydrocarbon groups having 1 to 20 carbon atoms include: alkylene groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, or ynylene groups having 2 to 20 carbon atoms.

[0049] Specific examples of this heteroatom-containing group include: -O-, -S-, -SO2-, -Si(R”)2-, -Si(R”)2-(O-Si(R”)2-). n - (n is an integer greater than or equal to 1, preferably an integer from 1 to 6), -C(=O)-, -O-C(=O)-, -NR-C(=O)-, -NR- or -NR-C(=O)-NR-.

[0050] In the above -NR-C(=O)-, -NR-, or -NR-C(=O)-NR-, the R independently represents a hydrogen atom or a monovalent organic group. Examples of such monovalent organic groups include alkyl, phenyl, or tert-butoxycarbonyl groups with 1 to 5 carbon atoms. Similarly, in the above -Si(R”)2-, -Si(R”)2-(O-Si(R”)2-) n In the symbol "-", "R" represents a hydrogen atom or a monovalent organic group. Examples of monovalent organic groups include methyl and phenyl. Multiple "R"s can each independently have the above definition.

[0051] Ar, which has the structure of the aromatic ring, is preferably the structure shown in the following formula (3).

[0052]

[0053] (L is -CH2-, -O-, -C(=O)-, -N(R)- (R represents a hydrogen atom, methyl or tert-butyloxycarbonyl), cyclohexene, or an alkylene group having 2 to 18 carbon atoms. Optionally, any -CH2- group of this alkylene group is replaced by -O-, -O-C(=O)-, -C(=O)-, -N(R)- (R represents a hydrogen atom, methyl or tert-butyloxycarbonyl), -N(R)-C(=O)- (R represents a hydrogen atom, methyl or tert-butyloxycarbonyl), cyclohexene, or a phenylene group. Furthermore, the hydrogen atom on the phenylene group is optionally replaced by a halogen atom or an alkyl or alkoxy group having 1 to 5 carbon atoms.

[0054] R3 represents a halogen atom or an alkyl or alkoxy group having 1 to 5 carbon atoms, wherein any hydrogen atom of the alkyl or alkoxy group is optionally substituted with a halogen atom, and any hydrocarbon group is optionally substituted with an amino group protected by a tert-butoxycarbonyl group.

[0055] Multiple 'a's are independently integers from 0 to 4, 'b' is an integer from 1 to 2, and 'c' is an integer from 0 to 1. In the case of multiple 'R3's' and 'a's, they can be chosen to be the same or different.

[0056] More specific examples of the aforementioned L can be listed as: -O-, -O-C(=O)-, -C(=O)-, -N(R)- (R represents a hydrogen atom, methyl, or tert-butyloxycarbonyl), -N(R)-C(=O)- (R represents a hydrogen atom, methyl, or tert-butyloxycarbonyl), -N(R)-C(=O)-N(R)- (R represents a hydrogen atom, methyl, or tert-butyloxycarbonyl. The two Rs may optionally be the same or different), -(CH2). p -、-O-(CH2) p -O-, -(CH2) p -O-C(=O)-(CH2) q -、-(CH2) p -N(R)-(CH2) q - (R represents a hydrogen atom, methyl, or tert-butyloxycarbonyl), - (CH2) p -N(R)-C(=O)-N(R)-(CH2) q - (R represents a hydrogen atom, methyl, or tert-butyloxycarbonyl. The two Rs may be the same or different), -O-(CH2) p -O-(CH2) q -O-, -(CH2) p’ -O-C(=O)-(CH2) q -C(=O)-O-(CH2) r’ -、-(CH2) p’ -C(=O)-O-(CH2) q -O-C(=O)-(CH2) r’ -、-(CH2) p’ -O-C(=O)-Q-C(=O)-O-(CH2) q’ -(Q represents phenylene or cyclohexene), -(CH2) p’ -C(=O)-O-Q-O-C(=O)-(CH2) q’ - (Q represents phenylene or cyclohexene).

[0057] Here, p is an integer from 1 to 6, preferably an integer from 2 to 6. q is an integer from 1 to 6, more preferably an integer from 2 to 6, and even more preferably an integer from 2 to 4.

[0058] p', q', and r' are integers from 0 to 6. Furthermore, 0 ≤ p' + q' ≤ 10 and 2 ≤ p' + q + r' ≤ 16 are satisfied.

[0059] In formula (1), W represents a monovalent organic group having at least one group selected from the group consisting of alicyclic hydrocarbon groups with 4 to 40 carbon atoms and aromatic hydrocarbon groups with 6 to 40 carbon atoms.

[0060] Examples of alicyclic hydrocarbon groups (W) include cyclobutane rings, cyclopentane rings, cyclohexane rings, cyclodecane rings, and steroidal skeletons (e.g., cholesteryl, cholesterol, or lanostane), whose cyclic structures optionally have substituents. Examples of aromatic hydrocarbon groups include benzene rings and naphthyl rings, whose rings optionally have substituents. Examples of substituents include alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkyl carbonyl groups with 2 to 10 carbon atoms, alkoxy carbonyl groups with 2 to 10 carbon atoms, alkoxy carbonyl groups with 2 to 10 carbon atoms, halogen atoms, cyano groups, nitro groups, amino groups, and thiols.

[0061] At least one of the hydrogen atoms in the aforementioned alicyclic hydrocarbon group and aromatic hydrocarbon group is more preferably substituted by a substituent (F) selected from the group consisting of a halogen atom, a halogen-containing alkyl group, a halogen-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, and an alkenyl group having 3 to 10 carbon atoms.

[0062] It should be noted that -O- may be inserted between carbon-carbon bonds in any methylene group of the halogen-containing alkyl group, halogen-containing alkoxy group, alkyl group with 3 to 10 carbon atoms, alkoxy group with 3 to 10 carbon atoms, and alkenyl group with 3 to 10 carbon atoms in the above-mentioned substituent (F).

[0063] Furthermore, when W is a monovalent organic group having at least one group selected from the group consisting of two or more alicyclic hydrocarbon groups with 4 to 40 carbon atoms and aromatic hydrocarbon groups with 6 to 40 carbon atoms, it is sufficient that at least one alicyclic hydrocarbon group or aromatic hydrocarbon group has the above-mentioned substituent (F), and the other alicyclic hydrocarbon groups or aromatic hydrocarbon groups may be unsubstituted or may have substituents other than substituent (F).

[0064] W is more preferably a monovalent organic group having an alicyclic hydrocarbon group bonded with a substituent (F).

[0065] In formula (1), W has at least any one of a cyclohexane ring and a benzene ring, for example more preferably the structure shown by the group "-X-J".

[0066] J represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group with 4 to 40 carbon atoms and an aromatic hydrocarbon group with 6 to 40 carbon atoms.

[0067] X represents a single bond, -(CH2) a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -COO-, -OCO-, -CH=CH-COO-CH2-Q- (Q represents a single bond or an alkylene group with 1 to 17 carbon atoms, wherein a portion of the methylene group in Q is optionally replaced by -O-, -CONH-, -COO-, or -OCO-) or -(A0). m0 -((CH2) a1 -A1) m1 —(A0 and A1 each independently represent —O— or —COO—. a1 is an integer from 1 to 10, m0 is an integer of 0 or 1, and m1 is an integer from 1 to 2. When m1 is 2, multiple a1 and A1 independently have the above definitions).

[0068] The above-mentioned group "-X-J" is more preferably the structure described below (S1), and as a further preferred structure, the following formulas (S1-1) to (S1-5) can be listed.

[0069]

[0070] (where X) 1 The meaning of X is the same as in the group "-X-J".

[0071] G 1 This indicates a divalent cyclic group selected from phenylene and cyclohexene. Any hydrogen atom on the aforementioned 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.

[0072] m is an integer from 1 to 4. When m is 2 or greater, there are multiple X... 1 and G 1 Each of them independently possesses the above definition.

[0073] R 1 This refers to a fluorine atom, an alkyl group containing fluorine atoms with 1 to 10 carbon atoms, an alkoxy group containing fluorine atoms with 1 to 10 carbon atoms, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, or an alkoxyalkyl group with 3 to 10 carbon atoms.

[0074]

[0075] (where X) 1 and R 1 X in the above formula (S1) 1 and R 1 The meaning is the same.

[0076] From the viewpoint of achieving the appropriate effects of the present invention, X in the above formulas (S1-1) to (S1-5) 1 More preferably, it is -(CH2). a - (a is an integer from 1 to 15), -O-, -COO-, -OCO-, -CH2-O-, -CH2-O- or *1-CH=CH-COO-CH2-*2 (*1 and *2 represent bonding bonds, which are bonded to the benzene ring through *1).

[0077] The repeating unit shown in the above formula (1) is obtained, for example, by using the diamine "H-NR-Ar-NR'-H" (R, R', and Ar are defined in the same way as in formula (1). Hereinafter, this diamine will also be referred to as a specific diamine) as a raw material component.

[0078] The following are examples of specific diamines, but are not limited to these. The aforementioned specific diamines can be used alone or in combination of two or more.

[0079] Aromatic diamines (d) represented by “A-X'-J'” (X' and J' will be described later), 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, 3,3'-dihydroxy-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 Alkane, 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-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-naphthoxy)ethane, 1,2-Di(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]hexadiate, 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis... (3-Aminophenyl) isophthalate; diamines with photooriented groups such as 4,4'-diaminoazobenzene, diaminodiphenylacetylene, and 4,4-diaminochalcone; diamines with photopolymerizable groups at the ends such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallylaniline; diamines with photopolymerizable groups at the ends such as 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropionanone and 2-(4-(2-hydroxy-2-methylpropionyl)phenoxy)ethyl-3,5-diaminobenzoate, benzoin or its alkyl ethers, benzyl ketals, acetophenones, phosphine oxides, benzophenones, or aminobenzophenones, etc. Diamines with functional groups that function as polymerization initiators (hereinafter also referred to as diamines with free radical initiation functions); diamines with amide bonds such as 4,4'-diaminobenzoylaniline; diamines with urea bonds such as 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, and 1,3-bis(4-aminophenylethyl)urea; 4,4'-sulfonyl diphenylamine, 3,3'-sulfonyl diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino Diphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 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, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-aniline, 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-( Diamines with a diphenylamine structure, such as 1H-benzimidazol-2-yl)phenyl-1,3-diamine, or 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-1,4-phenylenediamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-phenylenediamine, are diamines having a diphenylamine structure and possessing at least one nitrogen-containing structure selected from the group consisting of nitrogen-containing heterocycles, secondary amino groups, and tertiary amino groups (hereinafter also referred to as specific nitrogen-containing structures). (Wherein the molecule does not contain a bond that can be released by heating.) (Amino groups replaced by hydrogen protecting groups); 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 1,2-bis(4-aminophenyl)ethane-3,3'-dicarboxylic acid, and 4,4'-diaminodiphenyl ether-3...Diamines with carboxyl groups, such as 3'-dicarboxylic acids; 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)adiazine, Butyloxycarbonylamino-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 of carbamate, N-tert-butyloxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine, 4-amino-2-tert-butyloxycarbonylamino-1,1'-[(1,1,3,3-tetramethyl-1,3-disiloxanediyl)di- Diamines containing the group "-N(D)-" (D represents a protecting group that is removed and replaced by a hydrogen atom by heating, preferably tert-butoxycarbonyl); 4,1-butanediyl] ester, N-[2-(4-aminophenyl)ethyl]-N-[[[2-(4-aminophenyl)ethyl]amino]carbonyl]-1,1-dimethyl ethyl ester, N-(4-aminophenyl)-N-[[1-(4-aminophenyl)-4-piperidinyl]methyl]-1,1-dimethyl ethyl ester, etc.; 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecanyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, etc. Aromatic diamines (tn) with long-chain alkyl groups having 12 to 20 carbon atoms, represented by 4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-dodecyloxy-2,5-diaminobenzene, 1-tetradecyloxy-2,5-diaminobenzene, 1-pentadecanyloxy-2,5-diaminobenzene, 1-hexadecyloxy-2,5-diaminobenzene, and 1-octadecyloxy-2,5-diaminobenzene; diamines with a fluorene skeleton, such as 2,7-diaminofluorene or 9,9-bis(4-aminophenyl)fluorene; and diamines formed by bonding two amino groups to groups represented by any of the formulas (Y-1) to (Y-167) as described in WO2018 / 117239.

[0080]

[0081] (In equation (z-2), each of the two m independently possesses the above definition.)

[0082] In the above aromatic diamine (d), A represents a monovalent group formed by the bonding of two primary amino groups with a structure having an aromatic ring. Specific examples of structures having an aromatic ring include: benzene rings, naphthalene rings, and biphenyl structures. Regarding X', specific examples include the structure exemplified in X of the above group "-X-J".

[0083] J' represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an aromatic hydrocarbon group having 6 to 40 carbon atoms. In this group, at least one of the hydrogen atoms in the alicyclic hydrocarbon group and the aromatic hydrocarbon group is substituted by a substituent (v) that is a halogen atom, a halogen-containing alkyl group, a halogen-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkenyl group having 3 to 10 carbon atoms. Furthermore, any carbon-carbon single bond in these substituents (v) (excluding halogen atoms) is optionally interrupted by -O-. It should be noted that, in addition to having the aforementioned alicyclic hydrocarbon group and aromatic hydrocarbon group, J optionally further has at least one group selected from the group consisting of an unsubstituted alicyclic hydrocarbon group and an aromatic hydrocarbon group substituted by a substituent other than the aforementioned substituent (v).

[0084] Examples of alkyl groups containing halogen atoms include alkyl groups with 1 to 10 carbon atoms.

[0085] Examples of alkoxy groups containing halogen atoms include alkoxy groups with 1 to 10 carbon atoms.

[0086] As the alicyclic hydrocarbon group of J', the alicyclic hydrocarbon group exemplified in J can be listed. As the aromatic hydrocarbon group of J', the aromatic hydrocarbon group exemplified in J can be listed. When J' has at least any one of a cyclohexane ring and a benzene ring, as a more preferred specific example of the group "-X'-J'", the above structure (S1) can be listed. As a more preferred structure, the above formulas (S1-1) to (S1-5) can be listed.

[0087] Specific examples of the aforementioned aromatic diamines (d) include diamines represented by formulas (d-1) to (d-2) below. More preferably, examples include diamines represented by formulas (d-1) to (d-2) whose group "-X'-J'" is any of the structures (S1) or formulas (S1-1) to (S1-5) described above, 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.

[0088]

[0089] (X and J, including preferred embodiments, have the same meaning as X' and J' in the above-described aromatic diamine (d). In the formula (d-2), the two X and J may optionally be the same or different from each other.)

[0090] The polymer (B) of the present invention may further have a repeating unit structure as shown in the following formula (2).

[0091]

[0092] (Ar, R, and R' have the same meaning as in formula (1). CL represents a monovalent organic group with a crosslinking group (T).)

[0093] Specific examples of crosslinking groups (T) in CL include: hydroxyl, vinyl, epoxy, oxetyl, carboxyl, sulfonyl, thiol, and (meth)acryloyl. CL may have one or more crosslinking groups.

[0094] CL more preferably has an aromatic ring, and specific examples of such an aromatic ring include the structures illustrated in the aromatic rings of Ar above. The aromatic ring of CL is preferably a benzene ring, wherein any hydrogen atom on the benzene ring may optionally be substituted.

[0095] CL is preferably the structure shown in the following formula (CL1).

[0096]

[0097] In formula (CL1), L1 represents -NR- (R represents a hydrogen atom or a monovalent organic group). Examples of monovalent organic groups in -NR- include: hydrocarbon groups with 1 to 10 carbon atoms, and organic groups formed by inserting heteroatom-containing groups into any carbon-carbon bonds of the hydrocarbon group. The hydrogen atoms in the aforementioned hydrocarbon group or the organic group formed by inserting heteroatom-containing groups are optionally replaced by halogen atoms. Specific examples of heteroatom-containing groups include the structures exemplified in the heteroatom-containing groups of the linking group (L) described above.

[0098] Q represents a crosslinking group (T). n is an integer from 1 to 4. In the presence of multiple Qs, they may be identical or different. Ar represents an (n+1) valence organic group with an aromatic ring.

[0099] Ar in the above formula (2) can be formed by an aromatic ring alone, or it can be an organic group having an aromatic ring and a linking group L2 that bonds the group Q to the aromatic ring.

[0100] If we list specific examples of the linking group L2 mentioned above, we can list: single bonds, chain hydrocarbon groups with 1 to 20 carbon atoms, or divalent organic groups formed by inserting a heteroatom-containing group at least at one of the carbon-carbon bonds of the chain hydrocarbon group or at the end of the chain hydrocarbon group (wherein, in the case where a heteroatom-containing group is inserted into the carbon-carbon bond of the chain hydrocarbon group, the inserted chain hydrocarbon group forms a carbon atom number of 2 or more on the main chain of the polymer).

[0101] The aforementioned chain hydrocarbon groups having 1 to 20 carbon atoms can be any type of straight-chain or branched chain. Specific examples of chain hydrocarbon groups having 1 to 20 carbon atoms include: alkylene groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, or ynylene groups having 2 to 20 carbon atoms.

[0102] Specific examples of the aforementioned heteroatom-containing groups include: -O-, -S-, -SO2-, -Si(R”)2-, -Si(R”)2- (O-Si(R”)2-). n - (n is an integer greater than or equal to 1, preferably an integer from 1 to 6), -C(=O)-, -O-C(=O)-, -NR-C(=O)-, -NR-, -NR-C(=O)-O- or -NR-C(=O)-NR-.

[0103] In the above -NR-C(=O)-, -NR-, -NR-C(=O)-O-, or -NR-C(=O)-NR-, the R independently represents a hydrogen atom or a monovalent organic group. Examples of such monovalent organic groups include alkyl, phenyl, or tert-butoxycarbonyl groups with 1 to 5 carbon atoms. Similarly, in the above -Si(R”)2-, -Si(R”)2-(O-Si(R”)2-)n In the symbol "-", "R" represents a hydrogen atom or a monovalent organic group. Examples of monovalent organic groups include methyl and phenyl. Multiple "R"s can each independently have the above definition.

[0104] CL is preferably the structure shown in any of the following formulas (2-1) to (2-8).

[0105]

[0106] The weight-average molecular weight of the polymer (B) in this invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000. Furthermore, it is preferably 2,000 or more, and from the viewpoint of further improving solubility and reducing the viscosity of the resulting solution, it is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 15,000 or less, and particularly preferably 10,000 or less.

[0107] It should be noted that the weight-average molecular weight of the present invention is the average molecular weight calculated based on standard polystyrene using gel permeation chromatography (hereinafter referred to as GPC).

[0108] <Method for manufacturing polymer (B)>

[0109] The polymer (B) of the present invention can be manufactured, for example, according to the method for obtaining a linear polymer disclosed in WO2010 / 128661.

[0110] In the case of obtaining a polymer having the repeating unit shown in the above formula (1), it can be obtained, for example, by reacting the monomer components of the trihalomethane triazine compound, the compound shown in H-NR-Ar-NR'-H (Ar, R, R' have the same meaning as in formula (1)) and the compound shown in H-W (W has the same meaning as in formula (1)) in a solvent.

[0111] The compounds shown in H-W are preferably amine compounds.

[0112] As a manufacturing method for obtaining a polymer having the repeating unit shown in formula (1) above, a manufacturing method including the following steps (i) to (ii) can be listed as an example. In step (i) above, the case where H-W is an amine compound is shown as an example.

[0113] Furthermore, in the case of obtaining a polymer having the repeating unit shown in the above formula (2), the target polymer can be obtained by replacing the compound shown in H-W in step (i) with H-CL (CL has the same meaning as CL in formula (2)).

[0114] <Process (i)>

[0115] Compound (d-1-1) is reacted with the compound shown in formula (d-1) to give the compound shown in formula (d-2).

[0116]

[0117] (In the formula, X represents halogen atoms independently. W has the same meaning as W in formula (1).)

[0118] In step (i), the reaction temperature can be appropriately set within the range of the melting point to the boiling point of the solvent used, especially, more preferably -50 to 50°C, more preferably -20 to 50°C, even more preferably -10 to 50°C, and even more preferably -10 to 10°C.

[0119] <Process (ii)>

[0120] The compound (d-2-1) was reacted with the compound shown in the following formula (d-2) to obtain a polymer having the repeating unit shown in formula (1).

[0121]

[0122] (In the formula, X represents halogen atoms independently. W has the same meaning as W in formula (1). Ar, R, and R' have the same meaning as Ar, R, and R' in formula (1).)

[0123] In step (ii) above, the proportion of compound (d-2-1) used is arbitrary as long as the target polymer can be obtained. More preferably, the amount of compound (d-2-1) is 0.01 to 10 equivalents relative to 1 equivalent of triazine compound (d-2) used to manufacture polymer (B). More preferably, it is 1 to 5 equivalents.

[0124] The compound (d-2-1) can be added either in a solvent-free manner or as a solution prepared by dissolving it in a solvent. Considering the ease of operation and the ease of controlling the reaction, the latter method is preferred.

[0125] The reaction temperature can be appropriately set within the range of the melting point to the boiling point of the solvent used. From the viewpoint of obtaining a linear polymer, it is more preferably -50 to 50°C, further preferably -20 to 50°C, and most preferably -20 to 10°C.

[0126] The above steps (i) and (ii) are preferably carried out in a solvent, and more preferably in an organic solvent. Various solvents commonly used in this reaction can be used as organic solvents, such as: tetrahydrofuran (THF), 1,4-dioxane, dimethyl sulfoxide; N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N,N-dimethylethylurea, N,N,N',N'-tetramethylmalondiamide, N-methyl-ε-caprolactam, N-acetylpyrrolidone, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N-dimethylpropionamide, N,N'-dimethylisobutyramide, N-methylformamide, N,N'-dimethylpropyleneurea, and other amide solvents and mixtures thereof.

[0127] Among them, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide and mixtures thereof are preferred, especially N,N-dimethylacetamide and N-methyl-2-pyrrolidone.

[0128] In the reaction of step (ii) above, various bases that are usually used during or after polymerization can be added.

[0129] Specific examples of this alkali include: potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, etc.

[0130] The amount of alkali added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, relative to the amount of triazine compound (d-2) used to manufacture polymer (B). It should be noted that these alkalis can be prepared as an aqueous solution for use.

[0131] Ideally, no raw material components should remain in the obtained polymer, but some raw materials may remain.

[0132] After the reaction is complete, the product can be easily purified by methods such as reprecipitation.

[0133] The polymer (B) mentioned above can be a capped polymer obtained using a suitable capping agent. Capped polymers have the effect of increasing the film hardness of the liquid crystal alignment film obtained from the coating and improving the adhesion between the sealant and the liquid crystal alignment film.

[0134] Examples of the ends of the polymer (B) in this invention include, for example, amino or crosslinking groups. The crosslinking group is preferably the aforementioned crosslinking group (T).

[0135] The end-capped polymer can be obtained by reaction including the steps (i) to (ii) above, or by reacting the end-capping agent described later with the polymer obtained by reaction including steps (i) to (ii) to end-cap.

[0136] The process of obtaining the end-capped polymer can be a single process or consist of two or more processes.

[0137] Specific examples of end-capping agents used include: monoamine compounds (E) having the aforementioned crosslinking groups (T); (meth)acryloyl halides; (meth)acrylate glycidyl esters; isocyanate compounds; monoamine compounds without substituents (T); acid anhydrides, etc.

[0138] Preferred specific examples of monoamine compounds (E) include, for example, 2-aminophenol, 3-aminophenol, 2-(4-aminophenyl)ethanol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, or 4-aminobenzoic acid.

[0139] Specific examples of the aforementioned (meth)acryloyl halides include, for example, (meth)acryloyl chloride, (meth)acryloyl bromide, or (meth)acryloyl iodide.

[0140] Specific examples of the aforementioned isocyanate compounds include, for instance, ethyl 2-isocyanate acrylate, ethyl 2-isocyanate methacrylate, or 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0141] Specific examples of monoamine compounds that do not have substituents (T) include: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc.

[0142] Specific examples of acid anhydrides include: acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-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-ethynylphthalic anhydride, etc.

[0143] If we take an example of the process of obtaining a capped polymer, in the case of obtaining a capped polymer with a crosslinking group of hydroxyl, we can take the following step (e1): reacting a monoamine compound (E) having a hydroxyl group with a polymer obtained by the reaction including the above steps (i) to (ii).

[0144] Furthermore, in the case of obtaining a capped polymer with a crosslinking group of (meth)acryloyl, the target polymer can be obtained by further performing a step (e2) after the above step (e1), wherein the isocyanate compound having a (meth)acryloyl group is reacted.

[0145] The amount of capping agent used is preferably 0.05 to 500 equivalents relative to the amount of triazine compound (d-2)1 used to manufacture polymer (B), more preferably 0.05 to 120 equivalents, and even more preferably 0.05 to 50 equivalents.

[0146] The reaction temperature for the capping agent reaction can be appropriately set within the range of the melting point to the boiling point of the solvent used. From the viewpoint of improving reactivity, 0 to 150°C is more preferred, and 60 to 100°C is even more preferred.

[0147] (Liquid crystal alignment agent)

[0148] The liquid crystal alignment agent is used to manufacture liquid crystal alignment films, and from the viewpoint of forming a uniform thin film, it is preferably in the form of a coating liquid. In the liquid crystal alignment agent of the present invention, a coating liquid containing the aforementioned polymer (B) and organic solvent is also preferred.

[0149] The content of the polymer component in the liquid crystal alignment agent of the present invention can also be appropriately changed according to the desired thickness of the coating film. From the perspective of forming a uniform and defect-free coating film, 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.

[0150] The content of polymer (B) used in this invention is preferably 1 to 100 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent, and more preferably 3 to 100 parts by mass.

[0151] Furthermore, other polymers besides polymer (B) can also be mixed into the liquid crystal alignment agent. Specific examples of other polymers include polymers selected from the group consisting of the following substances: polyimide precursors (e.g., polyamic acid, polyamic acid ester, etc.), polyimide, polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene derivatives, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, and poly(meth)acrylate. 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).

[0152] 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.

[0153] 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.

[0154] The following compounds can be listed as preferred examples of the aforementioned crosslinking compound (c-1).

[0155] 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 resins such as those manufactured by CHEMICAL (Made by CHEMICAL), epoxy resins containing a biphenyl backbone such as YX6954BH30 (Made by MITSUBISHI CHEMICAL), phenolic varnish type epoxy resins such as EPPN-201 (Made by Nippon Kayaku Co., Ltd.), (o-, m-, and p-)cresol varnish type epoxy resins such as EOCN-102S (Made by Nippon Kayaku Co., Ltd.), tetra(glycidyloxymethyl)methane, N,N,N',N'-tetraglycidyl-1,4-phenylenediamine, N, Compounds in which tertiary nitrogen atoms are bonded to aromatic carbon atoms, such as N,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-1,4-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 WO2017 / 170483, etc.

[0156] Compounds having oxetyl groups include 1,4-bis{[(3-ethyl-3-oxetyl)methoxy]methyl}benzene (ARON OXETANE OXT-121(XDO)), di[2-(3-oxetyl)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 oxetyl groups as described in paragraphs 0170 to 0175 of WO2011 / 132751.

[0157] 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.

[0158] 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.

[0159] 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 WO2015 / 141598.

[0160] 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 paragraph 0058 of Japanese Patent Application Publication No. 2015 / 072554 and No. 2016-118753, compounds described in Japanese Patent Application Publication No. 2016-200798, and compounds described in WO2010 / 074269.

[0161] The following compounds can be listed as preferred examples of the aforementioned crosslinking compound (c-2).

[0162] 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.

[0163] The content of the compound containing the crosslinking group 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.

[0164] 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.

[0165] 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-isocyanatepropyltriethoxysilane. 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.

[0166] 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.

[0167] 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.

[0168] The concentration of solid components in the liquid crystal alignment agent (the proportion of the total mass of components other than the solvent in the total mass of the liquid crystal alignment agent) is appropriately selected considering viscosity, volatility, etc., and is preferably 0.5 to 15% by mass, more preferably in the range of 1 to 10% by mass.

[0169] The particularly preferred range of solid component concentration varies depending on the method used to coat the liquid crystal alignment agent onto the substrate. For example, when using spin coating, the solid component concentration is particularly preferably in the range of 1.5 to 4.5% by mass. When using printing, the solid component concentration is particularly preferably in the range of 3 to 9% by mass, thereby setting the solution viscosity in the range of 12 to 50 mPa·s. When using inkjet printing, the solid component concentration is particularly preferably in the range of 1 to 5% by mass, thereby setting the solution viscosity in the range of 3 to 15 mPa·s.

[0170] <Liquid Crystal Alignment Film>

[0171] 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 for horizontally aligned or vertically aligned liquid crystal alignment films, wherein, it is preferred for use in vertically aligned liquid crystal display elements.

[0172] Furthermore, the liquid crystal alignment film of the present invention can preferably be used in a liquid crystal display element manufactured by a method comprising: a step of coating a liquid crystal alignment agent onto a pair of substrates having conductive films to form a coating film; and a step of arranging the coating films opposite each other in such a way that the layers of liquid crystal molecules are separated by a layer to form a liquid crystal cell. The method further comprises the step of: under a state in which a voltage is applied between the conductive films of the pair of substrates, polymerizing a compound having polymerizable groups in at least one of the liquid crystal layer and the coating film by irradiation with active energy rays (more preferably ultraviolet or visible light) and heating.

[0173] More specifically, it refers to liquid crystal display elements using the PSA (Polymer Sustained Alignment) method and the SC-PVA (Surface-Controlled Patterned Vertical Alignment) method, which will be discussed later.

[0174] Liquid crystal display element

[0175] The liquid crystal display element of the present invention includes the liquid crystal alignment film described above.

[0176] The liquid crystal display element of the present invention can be manufactured, for example, by performing the following steps (1) to (3); steps (1) to (2), steps (2)' and steps (3); or steps (1) to (4) in sequence.

[0177] (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.

[0178] 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 has high transparency; it can also be used in conjunction with glass substrates, silicon nitride substrates, or plastic substrates such as acrylic substrates or polycarbonate substrates. 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.

[0179] (2) The process of firing the coating film

[0180] After applying the liquid crystal alignment agent, the coating is fired to prevent liquid sagging 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.

[0181] The coating formed in the above steps (1) and (2) can be maintained in this state and used as a liquid crystal alignment film, or an alignment processing step (step (2')) can be added to impart liquid crystal alignment capability to the coating. Examples of alignment processing in the above alignment processing steps include: friction processing, in which the coating is rubbed in a certain direction using a roller made of a cloth made of fibers such as nylon, rayon, or cotton; and light alignment processing, in which the coating is irradiated with polarized or unpolarized radiation.

[0182] In photoalignment 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 the radiation used is linearly or partially polarized, 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.

[0183] (3) A liquid crystal layer is formed between the above-mentioned pair of substrates to manufacture a liquid crystal cell.

[0184] (3-1) Manufacturing of VA-type liquid crystal display elements

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] Examples of positive liquid crystal displays include: Merck's ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081.

[0190] 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.

[0191] Furthermore, among PSA-type liquid crystal display elements, Merck's MLC-3023 is an example of a liquid crystal containing a compound with polymerizable groups.

[0192] 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.

[0193] 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.

[0194] (3-2) Manufacturing of PSA-based liquid crystal display elements

[0195] 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.

[0196] (3-3) Manufacturing of SC-PVA liquid crystal display elements

[0197] 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.

[0198] (4) The process of irradiating the liquid crystal cell with light.

[0199] 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 .

[0200] 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.

[0201] The liquid crystal display element of this invention can be effectively applied to various devices, such as clocks, portable game consoles, word processors, laptops, car navigation systems, portable camcorders, PDAs (Personal Digital Assistants), digital cameras, mobile phones, smartphones, various monitors, LCD TVs, information displays, and other display devices. Furthermore, the aforementioned liquid crystal alignment agent can also be used in liquid crystal alignment films for retardation films; liquid crystal alignment films for scanning antennas and liquid crystal array antennas; or liquid crystal alignment films for transmission-scattering type liquid crystal dimming elements; or for other applications, such as protective films for color filters, gate insulating films for flexible displays, and substrate materials.

[0202] Example

[0203] The present invention will be further described in detail below with reference to examples, but the invention is not limited thereto. The abbreviations of the compounds used in the examples are shown below.

[0204] (Organic solvents)

[0205] DMAc: N,N-dimethylacetamide.

[0206] THF: Tetrahydrofuran.

[0207] NMP: N-methyl-2-pyrrolidone.

[0208] BCS: Ethylene glycol monobutyl ether.

[0209] [ 1 H-NMR]

[0210] Device: Bruker NMR System AVANCE III HD 500 (500MHz).

[0211] Solvent used for determination: DMSO-d6.

[0212] Reference material: Tetramethylsilane (TMS) (δ 0.0 ppm).

[0213] [GPC]

[0214] Apparatus: HLC-8200GPC manufactured by TOSOH Corporation.

[0215] Chromatographic column: TOSOH TSKgelα-3000+TOSOH TSKgelα-4000.

[0216] Column temperature: 40℃.

[0217] Solvent: Dimethylformamide (DMF).

[0218] Detector: UV (271nm).

[0219] Calibration curve: Standard polystyrene.

[0220] [Pre-tilt angle]

[0221] Axometrics Corporation's AxoScan TM Mueller Matrix Polarimeter.

[0222] [1] Polymer synthesis

[0223] [Synthetic Example 1] Synthesis of a triazine ring-containing polymer [PMA-1]

[0224]

[0225] Add 2-(4-aminophenyl)ethanol[1] (2-(4-aminophenyl)ethanol, 2.60 g, 19.0 mmol), (E)-3-(4-(4-pentylcyclohexyl)phenyl)acrylate-3-aminobenzyl(E)-3-(4-(4-pentylcyclohexyl)phenyl)acrylate, 3.30 g, 8.14 mmol), and DMAc (41.3 g) to a 500 mL four-necked flask. After nitrogen replacement, stir to dissolve [1] and [2] in DMAc. Then, cool to -5 °C using an ethanol-dry ice bath. While confirming that the internal temperature will not exceed 5 °C, add 2,4,6-trichloro-1,3,5-triazine[3] (2,4,6-trichloro-1,3,5-triazine, 5.00 g, 27.1 mmol) and rinse with DMAc (3.4 g). After stirring for 30 minutes, 4,4'-methylenediphenylamine[4] (4,4'-methylenedianiline, 4.84 g, 24.4 mmol) dissolved in DMAc (13.8 g) was added dropwise. After rinsing with DMAc (3.4 g), the mixture was transferred to an oil bath along with the reaction vessel and stirred for 1 hour at an internal temperature of 85 ± 5 °C. Then, 0.74 g (5.4 mmol) dissolved in DMAc (10.3 g)[1] was added dropwise, followed by rinsing with DMAc (3.4 g) and stirring for 3 hours. Then, 2-aminoethanol (4.97 g, 81.4 mmol) was added dropwise, and stirring was stopped after 30 minutes. THF (36 g), ammonium acetate (40.6 g), and deionized water (40.6 g) were added to the reaction solution and stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel to separate into an organic layer and an aqueous layer. The organic layer was recovered. The recovered organic layer was added dropwise to a mixture of methanol (90 g) and deionized water (181 g) to allow it to precipitate again. The resulting precipitate was filtered off and dried at 150 °C for 8 hours using a vacuum dryer to obtain the target polymer (9.80 g). NMP was added to the obtained polymer at a solids concentration of 20% by mass, and the mixture was stirred at 25 °C for 15 hours to dissolve it, thus obtaining a polymer (PMA-1) solution with a solids concentration of 20% by mass.

[0226] The weight-average molecular weight (Mw) of PMA-1, determined by GPC based on polystyrene conversion, is 6759, and the polydispersity (Mw / Mn) is 3.0.

[0227] [Synthetic Example 2] Synthesis of the triazine ring-containing polymer [PMA-2]

[0228]

[0229] 2-(4-aminophenyl)ethanol[1] (5.21 g, 38.0 mmol), 4-(4-(4'-pentyl-[1,1'-bis(cyclohexane)]-4-yl)phenoxy)aniline[5] (4-(4-(4'-pentyl-[1,1'-bi(cyclohexan)]-4-yl)phenoxy)aniline, 6.71 g, 16.0 mmol) and DMAc (118.1 g) were added to a 1000 mL four-necked flask. After nitrogen replacement, the mixture was heated to 40 °C while stirring to dissolve [1] and [5] in DMAc. Then, the mixture was cooled to 10 °C using an ethanol-dry ice bath. While confirming that the internal temperature would not exceed 10 °C, 2,4,6-trichloro-1,3,5-triazine[3] (10.00 g, 54.2 mmol) was added and the mixture was rinsed with DMAc (9.8 g). After stirring for 30 minutes, 4,4'-methylenediphenylamine[4] (9.68 g, 48.8 mmol) dissolved in DMAc (39.4 g) was added dropwise. After rinsing with DMAc (9.8 g), the mixture was transferred to an oil bath along with the reaction vessel and stirred for 1 hour at an internal temperature of 85 ± 5 °C. Then, 1.49 g (10.9 mmol) dissolved in DMAc (29.5 g) was added dropwise. After rinsing with DMAc (9.84 g), the mixture was stirred for 3 hours. Then, 2-aminoethanol (9.94 g, 163 mmol) was added dropwise. After stirring for 30 minutes, the stirring was stopped. THF (96 g), ammonium acetate (108 g), and deionized water (108 g) were added to the reaction solution and stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel to separate into an organic layer and an aqueous layer. The organic layer was recovered. The recovered organic layer was added dropwise to a mixture of methanol (240 g) and deionized water (480 g) to allow for reprecipitation. The resulting precipitate was filtered off and dried at 150 °C for 8 hours using a vacuum dryer to obtain the target polymer (25.6 g). NMP was added to the obtained polymer at a solids concentration of 20% by mass, and the mixture was stirred at 25 °C for 15 hours to dissolve it, thus obtaining a polymer (PMA-2) solution with a solids concentration of 20% by mass.

[0230] The weight-average molecular weight (Mw) of PMA-2, determined by GPC based on polystyrene conversion, is 7874, and the polydispersity (Mw / Mn) is 5.7.

[0231] [Synthesis Example 3] Methacrylate Polymer [PMA-C1]

[0232]

[0233] Weigh (E)-4-(3-(2-(methacryloyloxy)ethoxy)-3-oxoprop-1-en-1-yl)phenyl-4-(4,4,4-trifluorobutoxy)benzoate[6] ((E)-4-(3-(2-(methacryloyloxy)ethoxy)-3-oxoprop-1-en-1-yl)phenyl4-(4,4,4-trifluorobutoxy)benzoate, 10.12 g, 20.0 mmol), methacrylic acid[7] (methacrylic acid, 2.58 g, 30.0 mmol) and glycidyl methacrylate[8] (glycidyl methacrylate, 2.35 g, 16.5 mmol) into a four-necked flask and add NMP to a solid concentration of 20% by mass. After dissolving the monomer components and degassing them using a diaphragm pump, azobisisobutyronitrile (AIBN, 0.55 g, 3.33 mmol) was added as a polymerization initiator, followed by further degassing. The mixture was then reacted at 60 °C for 13 hours to obtain a polymer solution (PMA-C1) with a solid content of 20% by mass. The weight-average molecular weight (Mw) of PMA-C1, determined by GPC based on polystyrene conversion, was 58671, and the polydispersity (Mw / Mn) was 4.6.

[0234] [2][Preparation of liquid crystal alignment agent]

[0235] <Example 1>

[0236] NMP (3.00 g) and BCS (4.00 g) were added to a solution (3.00 g) of polymer PMA-1 obtained in Synthesis Example 1, and the mixture was stirred at room temperature for 2 hours to obtain liquid crystal alignment agent AL-1. It was confirmed that no abnormalities such as turbidity or precipitation were found in the above-mentioned liquid crystal alignment agent AL-1, and the resin components were uniformly dissolved.

[0237] <Example 2, Comparative Example 1>

[0238] As shown in Table 1, the polymer solution used was changed, but the process was carried out in the same manner as in Example 1 above, thereby obtaining the liquid crystal alignment agent AL-2 of Example 2 and the liquid crystal alignment agent AL-C1 of Comparative Example 1. It was confirmed that no abnormalities such as turbidity or precipitation were found in the above-mentioned liquid crystal alignment agents AL-2 and AL-C1, and the resin components were uniformly dissolved.

[0239] [Table 1]

[0240] Liquid crystal alignment agent polymer solution Example 1 AL-1 PMA-1 Example 2 AL-2 PMA-2 Comparative Example 1 AL-C1 PMA-C1

[0241] [Fabrication of Liquid Crystal Display Components]

[0242] The obtained liquid crystal alignment agent was spin-coated onto the ITO surface of a glass substrate with transparent electrodes made of ITO film. After drying on a heating plate at 70°C for 90 seconds, it was fired on a heating plate at 200°C for 30 minutes to form a liquid crystal alignment film with a thickness of 100 nm.

[0243] Next, the coating surface was irradiated with an intensity of 4.3 mW / cm², the irradiation amount shown in Table 2, at an angle of 40° relative to the substrate normal, through a polarizing plate. 2 A substrate with a liquid crystal alignment film was obtained by using linearly polarized ultraviolet light with a wavelength of 313 nm. The linearly polarized ultraviolet light was prepared by passing ultraviolet light from a high-pressure mercury lamp through a bandpass filter with a wavelength of 313 nm and then through a polarizing plate.

[0244] Two substrates were prepared. 4μm bead-like spacers were dispersed on the liquid crystal alignment film of one substrate, followed by the application of a sealant (Mitsui Chemicals, XN-1500T). Next, the other substrate was bonded together with the liquid crystal alignment film surfaces facing each other and the alignment direction at 180°. The sealant was then thermo-cured at 120°C for 90 minutes. After cooling to room temperature, liquid crystal (Merck, MLC-3022) was injected using a reduced-pressure injection method.

[0245] [Determination of pretilt angle]

[0246] The pretilt angle of the liquid crystal display element fabricated above was determined using the Mueller matrix method with an AxoScan manufactured by Axometrics. The evaluation results are shown in Table 2.

[0247] [Table 2]

[0248]

[0249] According to Table 2, under conditions of zero UV irradiation (i.e., no photoalignment treatment), the liquid crystal alignment agents AL-1 and AL-2 prepared using the polymers obtained in Examples 1 and 2 exhibit high pretilt angles. These liquid crystal alignment agents are preferably used in liquid crystal display elements requiring high contrast.

[0250] According to Table 2, the liquid crystal alignment agent AL-1 at a UV irradiation dose of 50 mJ / cm²... 2 Below, with 0mJ / cm 2 In comparison, it exhibits a low pretilt angle. With a UV irradiation dose of 50 mJ / cm², it demonstrates this. 2Compared to the liquid crystal alignment agent AL-C1 obtained in Comparative Example 1, which underwent photoalignment treatment, AL-1 exhibits a lower pretilt angle. This demonstrates that, according to the liquid crystal alignment agent of the present invention, when fabricating a liquid crystal alignment film using photoalignment treatment, the pretilt angle of the liquid crystal molecules can be easily controlled. The liquid crystal alignment agent of the present invention, and liquid crystal display elements using liquid crystal alignment films obtained from this liquid crystal alignment agent, are preferably used in photoaligned film liquid crystal display elements requiring high transmittance characteristics.

[0251] It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2023-048546, filed on March 24, 2023, are incorporated herein as a disclosure of the specification of this invention.

Claims

1. A liquid crystal alignment agent, characterized in that, Contains component B below, Component B: Polymer B having the repeating unit structure shown in formula (1) below, In formula (1), W represents a monovalent organic group having at least one group selected from the group consisting of alicyclic hydrocarbon groups with 4 to 40 carbon atoms and aromatic hydrocarbon groups with 6 to 40 carbon atoms. R and R' represent hydrogen atoms or monovalent organic groups independently of each other. Ar represents a divalent structure with an aromatic ring, where Ar is a group other than the carbonyl carbon and is bonded to -NR- or -NR'-; * indicates a bonded bond.

2. The liquid crystal alignment agent according to claim 1, wherein, In formula (1), W represents the structure indicated by the group "-X-J". 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. X represents a single bond, -(CH2) a -, -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -COO-, -OCO-, -CH=CH-COO-CH2-Q- or -(A0) m0 -((CH2) a1 -A1) m1 -, the -(CH2) a In the – , a is an integer from 1 to 15; in –CH=CH-COO-CH2-Q-, Q represents a single bond or an alkylene group with 1 to 17 carbon atoms, and a portion of the methylene group in Q is optionally replaced by –O-, –CONH-, –COO-, or –OCO-; in –(A0) m0 -((CH2) a1 -A1) m1 In the given text, A0 and A1 each independently represent -O- or -COO-; a1 is an integer from 1 to 10, m0 is an integer of 0 or 1, and m1 is an integer from 1 to 2; when m1 is 2, multiple a1 and A1 independently have the aforementioned definitions.

3. The liquid crystal alignment agent according to claim 2, wherein, The group "-X-J" has the following structure (S1), In the formula, X 1 The X in the group "-X-J" has the same meaning. G 1 The term indicates a divalent cyclic group selected from phenylene and cyclohexene; any hydrogen atom on the cyclic group is optionally 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. m is an integer from 1 to 4; when m is 2 or more, multiple X 1 and G 1 Each has its own definition. 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.

4. The liquid crystal alignment agent according to claim 1, wherein, Ar in formula (1) is bonded to at least one of -NR- or -NR'- through an aromatic ring.

5. The liquid crystal alignment agent according to claim 1, wherein, The structure having an aromatic ring is an aromatic ring; a structure containing an aromatic ring and a chain structure; a polycyclic structure a1 containing an aromatic ring and a cyclic structure; a polycyclic structure a2 selected from the group consisting of an aromatic ring and a polycyclic structure a1, wherein at least two cyclic groups are bonded via a linking group; or a polycyclic structure a3 selected from the group consisting of an aromatic ring and a polycyclic structure a1, wherein at least one cyclic structure other than an aromatic ring is bonded via a linking group to a cyclic structure other than an aromatic ring.

6. The liquid crystal alignment agent according to claim 1, wherein, Ar in equation (1) has the structure shown in equation (3) below. In formula (3), L is -CH2-, -O-, -C(=O)-, -N(R)-, cyclohexene, or an alkylene group having 2 to 18 carbon atoms; in -N(R)-, R represents a hydrogen atom, methyl, or tert-butyloxycarbonyl; wherein, any -CH2- of the alkylene group is optionally replaced by -O-, -O-C(=O)-, -C(=O)-, -N(R)-, -N(R)-C(=O)-, cyclohexene, or phenylene; in -N(R)-, R represents a hydrogen atom, methyl, or tert-butyloxycarbonyl; in -N(R)-C(=O)-, R represents a hydrogen atom, methyl, or tert-butyloxycarbonyl; furthermore, the hydrogen atom on the phenylene group is optionally replaced by a halogen atom or an alkyl or alkoxy group having 1 to 5 carbon atoms. R3 represents a halogen atom or an alkyl or alkoxy group having 1 to 5 carbon atoms, wherein any hydrogen atom of the alkyl or alkoxy group is optionally substituted with a halogen atom, and any hydrocarbon group is optionally substituted with an amino group protected by a tert-butoxycarbonyl group. Each of the multiple 'a's is an integer from 0 to 4, b is an integer from 1 to 2, and c is an integer from 0 to 1; in the case of multiple R3s and a, they can be chosen to be the same or different.

7. The liquid crystal alignment agent according to claim 1, wherein, The polymer B further has a repeating unit structure as shown in formula (2). In equation (2), Ar, R and R' have the same meaning as in equation (1), and CL represents a monovalent organic group with a crosslinking group T.

8. The liquid crystal alignment agent according to claim 7, wherein, The crosslinking group T is selected from hydroxyl, vinyl, epoxy, oxobutyl, carboxyl, sulfonyl, thiol, and (meth)acryloyl.

9. The liquid crystal alignment agent according to claim 7, wherein, In equation (2), CL has the structure shown in equation (CL1) below. In formula (CL1), L1 represents -NR-, where R represents a hydrogen atom or a monovalent organic group; Q represents a crosslinking group T; n is an integer from 1 to 4; in the presence of multiple Qs, they may be the same or different; Ar represents an (n+1) valent organic group with an aromatic ring.

10. The liquid crystal alignment agent according to claim 7, wherein, In equation (2), CL can be any of the structures shown in equations (2-1) to (2-8) below.

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

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

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

14. The method for manufacturing a liquid crystal display element according to claim 13, wherein, include: Following step 2, the following step 2' is performed. Step 2': An alignment process that imparts liquid crystal alignment capability to the sintered film obtained in Step 2.

15. The method for manufacturing a liquid crystal display element according to claim 14, wherein, The orientation process is a light orientation process involving the illumination of polarized or unpolarized radiation.

Images