Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same

Abstract

To provide a liquid crystal aligning agent which exhibits good aligning properties and can form a liquid crystal alignment film having good adhesion to a sealing agent.SOLUTION: This liquid crystal aligning agent contains a polymer (A) having a repeating unit represented by the following formula (3) and a repeating unit represented by a specific formula (5). (R31 to R34 are each independently a hydrogen atom, a halogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C1-6 monovalent organic group having a fluorine atom, or a phenyl group, which may be the same or different from each other, provided that at least one of R31 to R34 represents a group other than a hydrogen atom within the above definitions.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element using the same.

Background Art

[0002] Conventionally, liquid crystal devices have been widely used as display units for personal computers, mobile phones, smartphones, television receivers, and the like. A liquid crystal device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, pixel electrodes and a common electrode for applying an electric field to the liquid crystal layer, an alignment film for controlling the orientation of liquid crystal molecules in the liquid crystal layer, a thin film transistor (TFT) for switching an electric signal supplied to the pixel electrodes, and the like. As driving methods for liquid crystal molecules, vertical electric field methods such as the TN method and the VA method, and horizontal electric field methods such as the IPS method and the FFS (fringe field switching) method are known.

[0003] Currently, the most industrially widespread liquid crystal alignment film is produced by performing a so-called rubbing treatment in which the surface of a film made of polyamic acid and / or polyimide obtained by imidizing the same formed on an electrode substrate is rubbed in one direction with a cloth such as cotton, nylon, or polyester. The rubbing treatment is a simple and industrially useful method with excellent productivity. However, with the high performance, high definition, and large size of liquid crystal display elements, various problems such as scratches on the surface of the alignment film generated by the rubbing treatment, dust generation, the influence of mechanical force and static electricity, and further non-uniformity within the alignment treatment surface have become apparent. As a liquid crystal alignment treatment method alternative to the rubbing treatment, a photo-alignment method for imparting liquid crystal alignment ability by irradiating polarized radiation is known. Liquid crystal alignment treatments by the photo-alignment method include those using a photo-isomerization reaction, those using a photo-crosslinking reaction, those using a photo-decomposition reaction, etc. (see Non-Patent Document 1 and Patent Document 1).

[0004] The liquid crystal alignment film, which is a component of a liquid crystal display element, is a film for uniformly aligning liquid crystals. However, not only the alignment uniformity of liquid crystals but also various characteristics are required. For example, charges accumulate in the liquid crystal alignment film due to the voltage for driving the liquid crystals, which affects the display as afterimages or image sticking (hereinafter referred to as afterimages derived from residual DC), and there is a problem that the display quality of the liquid crystal display element is significantly deteriorated. Therefore, a liquid crystal aligning agent for overcoming these problems has been proposed (see Patent Document 2).

[0005] In addition, in the IPS method and the FFS driving method, the stability of liquid crystal alignment is also important. If the stability of liquid crystal alignment is low, the liquid crystals will not return to the initial state when driven for a long time, which causes a decrease in contrast and image sticking (hereinafter referred to as AC afterimages). As a method for solving the above problems, Patent Document 3 discloses a specific liquid crystal aligning agent.

[0006] Furthermore, with the spread of tablets and smartphones, the development of a liquid crystal display element with a narrow bezel that secures the display area as wide as possible has been promoted. Due to this narrow bezel, it has become necessary to apply a sealant on the liquid crystal alignment film. Therefore, Patent Document 4 discloses a liquid crystal aligning agent that maintains good adhesion to the sealant while maintaining liquid crystal alignment.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Non-Patent Documents

[0008]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0009] Moreover, the demand for higher definition in liquid crystal display elements is increasing, and it has become even more important than before to exhibit good display quality. The present invention has been made in view of the above circumstances, and has as its major object to provide a liquid crystal alignment film having good liquid crystal alignment and good adhesion to a sealant, and a liquid crystal aligning agent capable of achieving a narrow bezel due to good adhesion between the liquid crystal alignment film and the sealant, and obtaining a liquid crystal display element exhibiting good display quality.

Means for Solving the Problems

[0010] As a result of intensive research, the present inventors have found that the above problems can be solved by using a liquid crystal aligning agent containing a polymer component having a specific repeating unit, and have completed the present invention. The present invention has the following gist. A liquid crystal aligning agent characterized by containing a polymer (A) having repeating units represented by the following formula (1), formula (2), formula (3) and formula (4).

Chemical formula

Chemical formula

[0011] According to the liquid crystal aligning agent of the present invention, a liquid crystal alignment film having good liquid crystal alignment property and good adhesion to a sealant, and further reduction of the bezel margin is possible due to the good adhesion between the liquid crystal alignment film and the sealant, and a liquid crystal display element showing good display quality can be obtained. [Embodiments for Carrying Out the Invention]

[0012] Hereinafter, each component contained in the liquid crystal aligning agent of the present invention and other components optionally blended as required will be described. [Polymer (A)] The liquid crystal aligning agent of the present invention contains a polymer (A) having repeating units represented by the above formula (1), the above formula (2), the above formula (3), and the above formula (4). By adopting such a configuration, a liquid crystal alignment film with less occurrence of AC residual images can be obtained, and a liquid crystal display element with excellent contrast can also be obtained.

[0013] In the above formulas (1) and (2), X2, Y1, Y2, R1, R2, R3, and R4 are as defined above.

[0014] Specific examples of the alkyl group having 1 to 6 carbon atoms in R1 to R4 include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, and the like. Specific examples of the alkenyl group having 2 to 6 carbon atoms in R1 to R4 include a vinyl group, a propenyl group, a butynyl group, etc., and these may be linear or branched. Specific examples of the alkynyl group having 2 to 6 carbon atoms in R1 to R4 include an ethynyl group, a 1-propynyl group, a 2-propynyl group, etc. Examples of the halogen atom in R1 to R4 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Examples of the monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom include a fluoromethyl group, a trifluoromethyl group, etc. From the viewpoint of high photoreactivity, R1 to R4 are a hydrogen atom or a methyl group, and it is preferable that at least one of R1 to R4 is a methyl group, and more preferably at least two of R1 to R4 are methyl groups. More preferably, R1 and R4 are methyl groups and R2 and R3 are hydrogen atoms.

[0015] Specific examples of the monovalent organic group that substitutes any hydrogen atom on the benzene ring in the above formula (H) include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, and the structures exemplified by the above R1 to R4 are included. As the partial structure represented by the above formula (H), partial structures represented by any of the following formulas (H-1) to (H-7) can be mentioned from the viewpoint of less generation of AC afterimages.

Chemical formula

[0016] As preferable specific examples of Y1 in the above formula (1), divalent organic groups represented by any of the following formulas (h-1) to (h-8) can be mentioned from the viewpoint of less generation of AC afterimages.

Chemical formula

[0017] From the viewpoint of enhancing heat resistance, the polymer (A) has a repeating unit represented by the above formula (2). As the tetravalent organic group of X2 in the formula (2), it is preferably a tetravalent organic group having an alicyclic structure of 5 to 8 members, and more preferably a tetravalent organic group having an alicyclic structure of 5 to 7 members. In addition, the alicyclic structure of 5 members or more means that when the alicyclic structure to which the imide group is bonded is a polycyclic structure, in each ring included in the polycyclic structure, the number of atoms constituting the ring is all 5 or more. Further, the above alicyclic structure only needs to be bonded to at least one of the two imide groups, and may have a chain hydrocarbon structure or an aromatic ring structure together with the alicyclic structure.

[0018] Preferable specific examples of X2 include tetravalent organic groups represented by any of the following formulas (X2-1) to (X2-12).

Chemical formula

[0019] Among them, X2 in the formula (2) is more preferably any of (X2-1) to (X2-4) from the viewpoint of less generation of AC afterimages and enhancing the contrast of the liquid crystal display element. Preferred specific examples of Y2 in the above formula (2) are the same as the preferred specific examples of Y1 in the above formula (1).

[0020] From the viewpoint of having few AC afterimages, the total of the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2) in the polymer (A) is preferably 1 to 95 mol%, more preferably 5 to 90 mol% based on all the repeating units. The ratio ((1):(2)) of the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (2) in the polymer (A) is preferably 70:30 to 99:1, more preferably 75:25 to 98:2, and still more preferably 80:20 to 97:3.

[0021] From the viewpoints of enhancing the contrast and seal adhesion of the liquid crystal display element, the polymer (A) has a repeating unit represented by the above formula (3) and a repeating unit represented by the above formula (4). From the viewpoint of having few AC afterimages, the total of the repeating unit represented by the above formula (3) and the repeating unit represented by the above formula (4) in the polymer (A) is preferably 5 to 99 mol%, particularly more preferably 10 to 95 mol% based on all the repeating units. The ratio ((3):(4)) of the repeating unit represented by the above formula (3) and the repeating unit represented by the above formula (4) in the polymer (A) is preferably 70:30 to 99:1, more preferably 75:25 to 98:2, and still more preferably 80:20 to 97:3.

[0022] The ratio ((1):(3)) of the repeating unit represented by the above formula (1) and the repeating unit represented by the above formula (3) in the polymer (A) is preferably 1:99 to 99:1, more preferably 5:95 to 80:20, and still more preferably 10:90 to 70:30. The ratio ((2):(4)) of the repeating unit represented by the above formula (2) and the repeating unit represented by the above formula (4) in the polymer (A) is preferably 1:99 to 99:1, more preferably 5:95 to 80:20, and still more preferably 10:90 to 70:30.

[0023] The polymer (A) preferably contains 6 to 100 mol%, particularly preferably 15 to 100 mol%, of the total of the repeating units represented by the above formulas (1), (2), (3) and (4) with respect to all the repeating units of the polymer (A).

[0024] From the viewpoint of further enhancing the adhesion to the sealing agent, the polymer (A) may have at least one repeating unit selected from the group consisting of the repeating unit represented by the following formula (5) and the repeating unit represented by the following formula (6).

Chemical formula

Chemical formula

[0025] In the above formulas (J-1) and (J-2), Q5 is a single bond, -(CH2) n -(n is an integer from 1 to 20), or -(CH2) n -where any -CH2- is not adjacent to each other, and is a group replaced by -O-, -COO-, -OCO-, -NQ9-, -NQ9CO-, -CONQ9-, -NQ9CONQ 10 -, -NQ9COO-, or -OCOO-. Q9 and Q 10 each independently represent a hydrogen atom or a monovalent organic group. Further, Q6 and Q7 each independently represent -H, -NHD, -N(D)2, a group having -NHD, or a group having -N(D)2. Q8 represents -NHD, -N(D)2, a group having -NHD, or a group having -N(D)2. D represents a carbamate-based protecting group, and examples of the carbamate-based protecting group include a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. However, at least one of Q5, Q6, and Q7 has a carbamate-based protecting group in the group. *1 represents a bond.

[0026] Preferred specific examples of Y5 and Y6 include divalent organic groups represented by any of the following formulas (J-1-a) to (J-1-d) and (J-2-1) from the viewpoint of having few AC afterimages. Boc represents a tert-butoxycarbonyl group. [Chemical formula]

[0027] In addition to the repeating units represented by the above formulas (1) to (4) and the repeating units represented by the above formulas (5) and (6), the polymer (A) may further have at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (PI-A-1) and a repeating unit represented by (PA-1). [Chemical formula]

[0028] In formula (PI-A-1), X I1 represents a tetravalent organic group, and Y I1 represents a divalent organic group. However, when X I1 is a tetravalent organic group represented by the following formula (g) or synonymous with X2 in the above formula (2), Y I1 represents a divalent organic group having a partial structure represented by the above formula (H), a divalent organic group represented by the above formula (I), a divalent organic group having a partial structure represented by the above formula (J-1), or a structure other than the divalent organic group represented by the above formula (J-2). X I1Examples include a tetravalent organic group represented by the following formula (g), in addition to the tetravalent organic groups exemplified by X2 in the above formula (2), a tetravalent organic group represented by any of the following formulas (X I1 -1) to (X I1 -13), a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride, and the like. [Chemical formula] (R1, R2, R3, and R4 have the same meanings as R1, R2, R3, and R4 in the above formula (1).)

[0029] [Chemical formula]

[0030] The aromatic tetracarboxylic dianhydride that provides the tetravalent organic group of the above X 11 is an acid dianhydride obtained by intramolecular dehydration of a carboxyl group bonded to an aromatic ring such as a benzene ring or a naphthalene ring. Specific examples include a tetravalent organic group represented by any of the following formulas (X3-1) to (X3-2), and a tetravalent organic group represented by any of the following formulas (Xr-1) to (Xr-7). [Chemical formula] (x and y are each independently a single bond, an ether (-O-), a carbonyl (-CO-), an ester (-COO-), an alkanediyl group having 1 to 5 carbon atoms, 1,4-phenylene, a sulfonyl, or an amide group. j and k are 0 or 1. * represents a bond.) [Chemical formula]

[0031] In formula (PI-A-1), Y I1Specific examples of the divalent organic group include a divalent organic group having a partial structure represented by the above formula (H), a divalent organic group represented by the above formula (I), a divalent organic group having a partial structure represented by the above formula (J-1), a divalent organic group represented by the above formula (J-2), and in addition, a divalent organic group represented by any of the following formulas (o-1) to (o-23), a group represented by any of the formulas (Y-1) to (Y-167) described in International Publication Gazette (hereinafter also referred to as WO) 2018 / 117239, and the like.

Chemical formula

[0032]

Chemical formula

[0033]

Chemical formula

[0034] In formula (PA-1), X A1 represents a tetravalent organic group, and Y A1 represents a divalent organic group. Specific examples of X A1 include the structures exemplified by X I1 in the above formula (PI-A-1). Specific examples of Y A1 include the structures exemplified by Y I1 in the above formula (PI-A-1).

[0035] In formula (PA-1), R A1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z A11 , Z A12 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, a tert-butoxycarbonyl group, or a 9-fluorenylmethoxycarbonyl group.

[0036] The above R A1Specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, and the like. From the viewpoint of ease of imidization by heating, R1 is preferably a hydrogen atom or a methyl group.

[0037] The above Z A11 and Z A12 Specific examples of the alkyl group having 1 to 10 carbon atoms include, in addition to the specific examples of the alkyl group having 1 to 5 carbon atoms exemplified by the above R1, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like. The above Z A11 and Z A12 Specific examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, a propenyl group, a butynyl group, and the like, and these may be linear or branched. The above Z A11 and Z A12 Specific examples of the alkynyl group having 2 to 10 carbon atoms include an ethynyl group, a 1-propynyl group, a 2-propynyl group, and the like. Z A11 and Z A12 may have a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a cyano group, an alkoxy group, and the like.

[0038] When the polymer A contains the repeating unit represented by the above formula (5) and the repeating unit represented by the above formula (6), the ratio ((5):(6)) is preferably 70:30 to 99:1, more preferably 75:25 to 98:2, and still more preferably 80:20 to 97:3.

[0039] In the above polymer (A), the total of the repeating unit represented by the above formula (5) and the repeating unit represented by the above formula (6) is preferably 1 to 40 mol% with respect to all the repeating units of the polymer (A), more preferably 1 to 30 mol%, and still more preferably 5 to 30 mol%. In this case, the total of the repeating units represented by the above formulas (1), (2), (3) and (4) is preferably 6 to 99 mol%, more preferably 15 to 99 mol%, still more preferably 15 to 95 mol%, based on all the repeating units of the polymer (A).

[0040] <Second polymer> The liquid crystal aligning agent of the present invention is a composition containing the above polymer (A) and an organic solvent, and two or more kinds of polymers (A) having different structures may be contained. Further, the liquid crystal aligning agent of the present invention may contain a polymer other than the polymer (A) (hereinafter also referred to as the second polymer) and various additives. When the liquid crystal aligning agent of the present invention contains the second polymer, the content ratio of the polymer (A) to all the polymer components is preferably 5% by mass or more, preferably 5 to 95% by mass, more preferably 10 to 90% by mass.

[0041] Examples of the second polymer include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or its derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate and the like.

[0042] In particular, the polyamic acid obtained from a tetracarboxylic dianhydride component and a diamine component (hereinafter also referred to as the second polyamic acid) is preferable as the second polymer.

[0043] Examples of the tetracarboxylic dianhydride component for obtaining the second polyamic acid include the compound represented by the following formula (11). The tetracarboxylic dianhydride component may be composed of two or more kinds of compounds. [Chemical formula] (A is a tetravalent organic group, preferably a tetravalent organic group having 4 to 30 carbon atoms.)

[0044] Examples of preferred A are shown below, but are not limited thereto. [Chemical formula]

[0045] Among the above, (A-1) and (A-2) are preferable from the viewpoint of further improving the photo-alignment property, (A-4) is preferable from the viewpoint of further improving the relaxation rate of the accumulated charge, and (A-15) to (A-17) etc. are preferable from the viewpoint of further improving the liquid crystal alignment property and the relaxation rate of the accumulated charge.

[0046] The diamine component for obtaining the second polyamic acid can be appropriately determined according to the purpose. For example, a diamine represented by the following formula (12) can be used. [Chemical formula] (Y9 represents a divalent organic group. Two A9s are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. From the viewpoint of liquid crystal alignment property, A9 is preferably a hydrogen atom or a methyl group.)

[0047] For the purpose of improving the electrical characteristics and relaxation characteristics, Y9 is preferably a divalent organic group having a secondary or tertiary nitrogen atom or a divalent organic group having -NH-CO-NH- in the molecule. Specific examples of the diamine represented by the formula (12) when Y9 is a divalent organic group having a secondary or tertiary nitrogen atom include any of the following diamines (a) to (d).

[0048] (a) A diamine having a pyrrole structure described in WO2017 / 126627, preferably a diamine having a structure represented by the following formula (pr). [Chemical formula] (R 1 represents a hydrogen atom, a fluorine atom, a cyano group, a hydroxy group, or a methyl group. Two Rs2 each independently represents a single bond or a group "*1-R 3 -Ph-*2", R 3 represents a single bond, -O-, -COO-, -OCO-, -(CH2) l -, -O(CH2) m O-, -CONH-, and -NHCO-, and represents a divalent organic group selected therefrom. l and m represent integers from 1 to 5. *1 represents the site of attachment to the benzene ring in formula (pr), and *2 represents the site of attachment to the amino group in formula (pr). Ph represents a phenylene group. n is from 1 to 3.)

[0049] (b) A diamine having a pyrrole structure described in WO2018 / 062197, preferably a diamine having a structure represented by the following formula (pn).

[0050]

Chemical formula

[0051] (c) A diamine having a carbazole structure described in WO2018 / 110354, preferably a diamine having a structure represented by the following formula (cz).

Chemical formula

[0052] (d) diamines having a nitrogen-containing heterocyclic ring described in

[0173] to

[0188] of WO2015 / 046374, diamines having a nitrogen-containing structure described in

[0050] of JP-A-2016-218149, diamines represented by the following formula (BP), [Chemical formula] (X is a biphenyl ring or a fluorene ring. Y is a group selected from a benzene ring, a biphenyl ring, or -Ph-Z-Ph-, where Ph represents a phenylene group. Z is a divalent group represented by -O-, -NH-, -CH2-, -SO2-, -C(CH3)2- or -C(CF3)2-. A and B are a hydrogen atom or a methyl group.), 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)piperazine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-1,3,5-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-1,3,5-triazine, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridinelactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl)-N-phenylamine, 4,4'-diphenyl-N-methylamine, 4,4'-diaminodiphenylamine, 3,6-diaminocarbazole, 9-methyl-3,6-diaminocarbazole, 9-ethyl-3,6-diaminocarbazole, diamines represented by the following formula (w1) or (w2).

[0053] [Chemical formula] (Sp represents a phenylene, pyrrolidine, piperidine, piperazine, divalent linear hydrocarbon group having 2 to 20 carbon atoms, or a group in which -CH2- of the divalent linear hydrocarbon group is -O-, -CO-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS-, -NR- (R represents a methyl group), pyrrolidine, piperidine, and a group substituted with a group selected from piperazine.)

[0054] Specific examples of the diamine represented by the above formula (12) when Y9 is a divalent organic group having -NH-CO-NH- in the molecule include the following formula (13), where A1 is -NH-CO-NH- or a group in which at least one of -CH2- of an alkylene group having 2 to 20 carbon atoms is substituted with -NH-CO-NH-, or a group in which at least one of -CH2- of an alkylene group having 2 to 20 carbon atoms is substituted with -NH-CO-NH- and at least one of the other -CH2- is substituted with a group selected from -O-, -CO-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS-, and -NR- (R represents a methyl group). More preferable specific examples of the diamine include diamines represented by any of the following formulas (U-1) to (U-9).

[0055] [Chemical formula] (A1 represents a single bond, -NH-CO-NH-, or an alkylene group having 2 to 20 carbon atoms (provided that any -CH2- in the alkylene group may be replaced by -O-, -CO-, -CO-O-, -NRCO- (where R represents a hydrogen atom or a methyl group), -NRCOO- (where R represents a hydrogen atom or a methyl group), -CONR- (where R represents a hydrogen atom or a methyl group), -COS-, -NR- (where R represents a methyl group), or -NH-CO-NH-). A2 represents a halogen atom, a hydroxy group, or an alkyl group or an alkoxy group having 1 to 5 carbon atoms (where any hydrogen atom in the alkyl group or alkoxy group may be replaced by a halogen atom). a is an integer from 0 to 4, and when a is 2 or more, A2 may be the same or different. b and c are integers of 1 or 2.)

[0056] [Chemical formula]

[0057] Preferred specific examples of the diamine represented by the above formula (w1) or (w2) include diamines represented by any of the following formulas (n3-1) to (n3-7), diamines represented by any of the following formulas (n4-1) to (n4-6), and the like. [Chemical formula]

[0058] [Chemical formula]

[0059] For the purpose of improving printability, diamines having a carboxyl group (COOH group) or a hydroxyl group (OH group) can also be used. Specifically, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, or 3,5-diaminobenzoic acid can be mentioned. Among them, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, or 3,5-diaminobenzoic acid is preferable. Further, diamines represented by the following formulas [3b-1] to [3b-4], or diamines in which these amino groups are secondary amino groups can also be used.

[0060]

Chemical formula

[0061] In formula [3b-1], Q 1 represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or N(CH3)CO-, and m 1 and m 2 each independently represent an integer from 0 to 4, and m 1 + m 2 represents an integer from 1 to 4. In formula [3b-2], m 3 and m 4 each independently represent an integer from 1 to 5. In formula [3b-3], Q 2 represents a linear or branched alkylene group having 1 to 5 carbon atoms, and m 5 represents an integer from 1 to 5. In formula [3b-4], Q 3 and Q 4Each independently represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO, -CON(CH3)- or -N(CH3)CO-, and m 6 represents an integer of 1 to 4.)

[0062] As the diamine component for obtaining the second polyamic acid, in addition to the above, the diamine used for obtaining the polymer (A) or a known diamine can be used. For the diamine component for obtaining the second polyamic acid, two or more diamines may be used in combination.)

[0063] <Method for producing polyamic acid, polyamic acid ester and polyimide> The polyamic acid ester, polyamic acid and polyimide, which are polyimide precursors used in the present invention, can be produced by a known method as described in, for example, WO2013 / 157586.)

[0064] <Liquid crystal aligning agent> The liquid crystal aligning agent of the present invention may contain the polymer (A) and, if desired, a second polymer, and further, other polymers in addition to these. Examples of the other polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or its derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, and the like.)

[0065] A liquid crystal aligning agent is used to produce a liquid crystal alignment film and takes the form of a coating solution from the viewpoint of forming a uniform thin film. In the liquid crystal aligning agent of the present invention, it is preferably a coating solution containing the above-described polymer component and an organic solvent. At that time, the concentration (content) of the polymer in the liquid crystal aligning agent can be appropriately changed according to the setting of the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, 1% by mass or more is preferable, and from the viewpoint of the storage stability of the solution, 10% by mass or less is preferable. A particularly preferable polymer concentration is 2 to 8% by mass.

[0066] The organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as it is a solvent in which the polymer component is uniformly dissolved (also referred to as a good solvent). Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide or γ-butyrolactone is preferable. The good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.

[0067] In addition, as the organic solvent contained in the liquid crystal aligning agent, it is preferable to use a mixed solvent in which a solvent (also referred to as a poor solvent) that improves the coatability and the surface smoothness of the coating film when applying the liquid crystal aligning agent is used in combination with the good solvent. Specific examples of the poor solvent are given below, but are not limited to these examples. For example, diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), etc. can be mentioned.

[0068] Poor solvents include, among others, diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and diisobutyl ketone, which are preferred.

[0069] Preferred combinations of good solvents and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, and the like. These poor solvents preferably account for 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass of the total solvents contained in the liquid crystal aligning agent. The types and contents of such solvents are appropriately selected according to the coating apparatus, coating conditions, coating environment, etc. of the liquid crystal aligning agent.

[0070] The liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the organic solvent. Such additional components include adhesion aids for enhancing the adhesion between the liquid crystal alignment film and the substrate and between the liquid crystal alignment film and the sealing material, compounds for enhancing the strength of the liquid crystal alignment film (hereinafter also referred to as crosslinkable compounds), dielectrics and conductive substances for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film, and the like.

[0071] From the viewpoint of less generation of AC residual images and high improvement effect on film strength, as the above crosslinkable compound, a compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum's acid structure, a cyclocarbonate group, a group represented by the following formula (d), or a compound represented by the following formula (e) (hereinafter, these are also collectively referred to as compound (C)) is preferable. [Chemical formula] (R 71 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or “*-CH2-OH”. R 72 and R 73 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or “*-CH2-OH”. * represents a bond. A represents an (m + n)-valent organic group having an aromatic ring. m represents an integer of 1 to 6, and n represents an integer of 0 to 4.)

[0072] Specific examples of the compound having an oxiranyl group include compounds having two or more oxiranyl groups such as the compounds described in

[0037] of JP-A-10-338880 and compounds having a triazine ring as a skeleton described in WO2017 / 170483. Among these, compounds containing a nitrogen atom such as N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-p-phenylenediamine, and compounds represented by any of the following formulas (r-1) to (r-3) are particularly preferred. [Chemical formula]

[0073] Specific examples of the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in

[0170] to

[0175] of WO2011 / 132751.

[0074] Specific examples of the compound having a protected isocyanate group include compounds having two or more protected isocyanate groups described in

[0046] to

[0047] of JP-A-2014-224978 and compounds having three or more protected isocyanate groups described in

[0119] to

[0120] of WO2015 / 141598. Among these, compounds represented by any of the following formulas (bi-1) to (bi-3) are preferred. [Chemical formula]

[0075] Specific examples of the compound having a protected isothiocyanate group include compounds having two or more protected isothiocyanate groups described in JP-A-2016-200798. Specific examples of the compound having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures described in

[0115] of JP-A-2007-286597.

[0076] Specific examples of the compound having a group containing a malonic acid structure include compounds having two or more malonic acid structures described in WO2012 / 091088. Specific examples of the compound having a cyclocarbonate group include the compounds described in WO2011 / 155577. Examples of the alkyl group having 1 to 3 carbon atoms for R1, R2, and R3 in the group represented by the above formula (d) include a methyl group, an ethyl group, and a propyl group.

[0077] Specific examples of the compound having the group represented by the above formula (d) include compounds having two or more groups represented by the above formula (d) described in WO2015 / 072554, JP-A-2016-118753

[0058] , and compounds described in JP-A-2016-200798. Among these, compounds represented by any of the following formulas (hd-1) to (hd-8) are preferred.

[0078]

Chemical formula

[0079] Examples of the (m + n)-valent organic group having an aromatic ring in A of the above formula (e) include (m + n)-valent aromatic hydrocarbon groups having 5 to 30 carbon atoms, (m + n)-valent organic groups in which an aromatic hydrocarbon group having 5 to 30 carbon atoms is bonded directly or via a linking group, and (m + n)-valent groups having an aromatic heterocyclic ring. Examples of the above aromatic hydrocarbon group include benzene, naphthalene, etc. Examples of the aromatic heterocyclic ring include pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring, carbazole ring, pyridazine ring, pyrazine ring, benzimidazole ring, indole ring, quinoxaline ring, acridine ring, etc. Examples of the above linking group include an alkylene group having 1 to 10 carbon atoms, or a group obtained by removing one hydrogen atom from the above alkylene group, a divalent or trivalent cyclohexane ring, etc. Any hydrogen atom of the above alkylene group may be substituted with an organic group such as a fluorine atom or a trifluoromethyl group. Specific examples include compounds described in WO2010 / 074269. Preferred specific examples include any of the following formulas (e-1) to (e-9).

[0080] [Chemical formula]

[0081] The above compounds are an example of crosslinkable compounds and are not limited thereto. For example, components other than the above disclosed in

[0105] to

[0116] of WO2015 / 060357 may be mentioned. Also, two or more kinds of crosslinkable compounds contained in the liquid crystal aligning agent of the present invention may be combined. In the liquid crystal aligning agent of the present invention, the content of the crosslinkable compound is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, and more preferably 1 to 15 parts by mass from the viewpoint that the crosslinking reaction proceeds to exhibit the intended effect and the generation of AC afterimages is small.

[0082] Examples of the above adhesion aids include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,Silane coupling agents such as (4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. can be mentioned. From the viewpoint of less generation of AC afterimage, the amount of these silane coupling agents used is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.,

[0083] <Method for manufacturing liquid crystal alignment film> The liquid crystal alignment film using the liquid crystal aligning agent of the present invention can be manufactured by a known method for obtaining a liquid crystal alignment film from the liquid crystal aligning agent using the above liquid crystal aligning agent of the present invention. Among them, the liquid crystal alignment film using the liquid crystal aligning agent of the present invention can be efficiently manufactured by sequentially performing the following steps (1), (2), (3), and preferably step (4) which is carried out.

[0084] <Step (1)> This is the step of applying the liquid crystal aligning agent of the present invention onto a substrate. The substrate for applying the liquid crystal aligning agent is not particularly limited as long as it has high transparency, and glass substrates, silicon nitride substrates, plastic substrates such as acrylic substrates and polycarbonate substrates can also be used. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed from the viewpoint of simplifying the process. In addition, in a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used for one side substrate, and a material that reflects light such as aluminum can also be used for the electrode in this case. Industrially, the method of applying the liquid crystal aligning agent is generally a method performed by screen printing, offset printing, flexographic printing or inkjet method. Other coating methods include dip method, roll coater method, slit coater method, spinner method or spray method, etc., and these may be used according to the purpose.

[0085] <Step (2)> Step (2) is the step of heating the coating film of the liquid crystal aligning agent obtained in step (1). After applying the liquid crystal aligning agent onto the substrate, the solvent can be evaporated or the thermal imidization of the amic acid or amic acid ester in the polymer can be performed by heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven. The drying and baking steps after applying the liquid crystal aligning agent can select any temperature and time, and can be performed multiple times. The temperature for removing the organic solvent of the liquid crystal aligning agent can be, for example, 40 to 150 °C. From the viewpoint of shortening the process, it can also be performed at 40 to 120 °C. The baking time is not particularly limited, but examples include 1 to 10 minutes or 1 to 5 minutes. When performing the thermal imidization of the amic acid or amic acid ester in the polymer, after the step of removing the above organic solvent, it can be baked at, for example, 190 to 250 °C or 200 to 240 °C. The baking time is not particularly limited, but examples include 5 to 40 minutes or 5 to 30 minutes.

[0086] <Step (3)> Step (3) is a step of irradiating the film obtained in step (2) with polarized ultraviolet light. The wavelength of the ultraviolet light is preferably 200 to 400 nm, more preferably 200 to 300 nm. In order to improve the liquid crystal alignment property, ultraviolet light may be irradiated while heating the substrate coated with the liquid crystal alignment film at 50 to 250 °C. The irradiation dose of the above radiation is preferably 1 to 10,000 mJ / cm 2 is preferable, and 100 to 5,000 mJ / cm 2 is more preferable. The liquid crystal alignment film produced in this way can stably align liquid crystal molecules in a certain direction. The higher the extinction ratio of the polarized ultraviolet light, the higher the anisotropy can be imparted, which is preferable. Specifically, the extinction ratio of the ultraviolet light polarized in a straight line is preferably 10:1 or more, more preferably 20:1 or more.

[0087] <Step (4)> Step (4) is a step of firing the film obtained in step (3) at 100 °C or higher and at a temperature higher than that in step (2). The firing temperature is not particularly limited as long as it is 100 °C or higher and higher than the firing temperature in step (2), but 150 to 300 °C is preferable, 150 to 250 °C is more preferable, and 200 to 250 °C is even more preferable. The firing time is preferably 5 to 120 minutes, more preferably 5 to 60 minutes, and even more preferably 5 to 30 minutes. If the thickness of the liquid crystal alignment film after firing is too thin, the reliability of the liquid crystal display element may decrease, so 5 to 300 nm is preferable, and 10 to 200 nm is more preferable.

[0088] Furthermore, after performing either step (3) or (4) above, the obtained liquid crystal alignment film can also be subjected to a contact treatment using water and / or a solvent. As the solvent used in the above contact treatment, any solvent that can dissolve the decomposition products generated from the liquid crystal alignment film by ultraviolet irradiation is not particularly limited. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, or cyclohexyl acetate. Among them, from the viewpoints of versatility and solvent safety, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate is preferred. More preferably, water, 1-methoxy-2-propanol, or ethyl lactate. The solvents may be combined in two or more types.

[0089] As the above contact treatment, that is, the method of treating the liquid crystal alignment film irradiated with polarized ultraviolet light with water or a solvent, dipping treatment and spraying treatment (also called spray treatment) can be mentioned. The treatment time in these treatments is preferably 10 seconds to 1 hour from the viewpoint of efficiently dissolving the decomposition products generated from the liquid crystal alignment film by ultraviolet light. Among them, it is preferable to perform dipping treatment for 1 to 30 minutes. In addition, the solvent during the above contact treatment may be at room temperature or heated, but preferably it is 10 to 80°C. Among them, 20 to 50°C is preferable. In addition, from the viewpoint of the solubility of the decomposition products, ultrasonic treatment or the like may be performed as necessary.

[0090] After the above contact treatment, it is preferable to perform rinsing (also called rinsing) with a low-boiling solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone or baking of the liquid crystal alignment film. At that time, either rinsing or baking may be performed, or both may be performed. The baking temperature is preferably 150 to 300°C, more preferably 180 to 250°C, and even more preferably 200 to 230°C. In addition, the baking time is preferably 10 seconds to 30 minutes, more preferably 1 to 10 minutes.

[0091] The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a horizontal electric field type liquid crystal display element such as an IPS method or an FFS method, and is particularly useful as a liquid crystal alignment film for an FFS method liquid crystal display element. The liquid crystal display element is obtained by preparing a substrate with a liquid crystal alignment film obtained from a liquid crystal aligning agent, then manufacturing a liquid crystal cell by a known method, and using the liquid crystal cell. As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. Note that an active matrix structure liquid crystal display element in which switching elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting the image display may also be used.

[0092] Specifically, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. These electrodes can be, for example, ITO electrodes, and are patterned so that a desired image display can be achieved. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a SiO2-TiO2 film formed by the sol-gel method. Next, a liquid crystal alignment film is formed on each substrate, one substrate is overlapped with the other substrate so that the liquid crystal alignment film surfaces face each other, and the periphery is adhered with a sealant. In the sealant, spacers are usually mixed in order to control the substrate gap, and it is also preferable to scatter spacers for controlling the substrate gap in the in-plane portion where the sealant is not provided. An opening through which liquid crystal can be filled from the outside is provided in a part of the sealant. Next, a liquid crystal material is injected into the space surrounded by the two substrates and the sealant through the opening provided in the sealant, and then this opening is sealed with an adhesive. For the injection, a vacuum injection method may be used, or a method using capillary action in the air may be used. Any of a positive type liquid crystal material and a negative type liquid crystal material may be used as the liquid crystal material. Next, polarizing plates are installed. Specifically, a pair of polarizing plates are attached to the surfaces of the two substrates opposite to the liquid crystal layer.

[0093] By using the manufacturing method of the present invention as described above, it is possible to suppress image sticking due to long-term AC driving that occurs in liquid crystal display elements of the IPS driving method or the FFS driving method. Further, in step (2), after removing the organic solvent at 40 to 150 °C and then carrying out step (3), a liquid crystal alignment film can be obtained with a smaller number of steps than in the past. The liquid crystal aligning agent of the present invention can be particularly preferably used in a method for manufacturing a liquid crystal alignment film including a step of carrying out step (3) after removing the organic solvent at 40 to 150 °C in step (2).

[0094] By using the liquid crystal aligning agent of the present invention as described above, generation of image sticking due to residual DC and AC image sticking is less, and a liquid crystal alignment film with high seal adhesion can be obtained. In particular, it is possible to obtain a liquid crystal display element excellent in contrast with suppressed variation in brightness in the plane during black display, and a liquid crystal display element having good display quality can be obtained.

Examples

[0095] Examples are given below to more specifically explain the present invention, but the present invention is not limited thereto. The abbreviations of the compounds and the measurement methods of each property in the following are as follows. (Solvent) NMP: N-methyl-2-pyrrolidone, GBL: γ-butyrolactone, BCS: Butyl cellosolve, (Diamine) DA-1 to DA-4: Compounds represented by the following formulas (DA-1) to (DA-4), respectively, (Tetracarboxylic dianhydride) CA-1, CA-2: Compounds represented by the following formulas (CA-1) and (CA-2), respectively (Additive) C-1: Compound represented by the following formula (C-1) C-2: 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane S-1: Compound represented by the following formula (S-1),

[0096] [Chemistry]

[0097] [Chemistry]

[0098] [Chemistry]

[0099] [Measurement of Viscosity] Using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL and a cone rotor TE-1 (1°34’, R24), the measurement was carried out at a temperature of 25°C.

[0100] [Measurement of Imidization Ratio] 20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) (0.53 mL) was added, and ultrasonic waves were applied to completely dissolve it. This solution was measured for proton NMR at 500 MHz using an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Ltd.). The imidization ratio was determined using the protons derived from the structure that does not change before and after imidization as the reference protons, and the integrated value of the peaks of these protons and the integrated value of the peaks of the protons derived from the NH groups of the amic acids appearing around 9.5 ppm to 10.0 ppm, and was obtained by the following formula. Imidization ratio (%) = (1 - α·x / y) × 100 In the above formula, x is the integrated value of the peaks of the protons derived from the NH groups of the amic acids, y is the integrated value of the peaks of the reference protons, and α is the ratio of the number of reference protons to one NH group proton of the amic acids in the case of polyamic acid (imidization ratio of 0%).

[0101] [Synthesis Examples of Polymers] Hereinafter, synthesis examples of polyamic acid and polyimide are shown. Note that PI represents polyimide.

[0102] <Synthesis Example 1> In a 200 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 7.33 g (0.03 mol) of DA-1 was weighed, 99.1 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution, 6.19 g (0.028 mol) of CA-1 was added, and the mixture was stirred at 40 °C for 24 hours to obtain a polyamic acid solution (A-1) (viscosity: 107 mPa·s).

[0103] <Synthesis Example 2> In a 200 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 4.10 g (0.0168 mol) of DA-1 and 8.32 g (0.0392 mol) of DA-3 were weighed, 176 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution, 11.6 g (0.0518 mol) of CA-1 was added, and the mixture was stirred at 40 °C for 24 hours to obtain a polyamic acid solution (A-2) (viscosity: 219 mPa·s).

[0104] <Synthesis Example 3> In a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 6.37 g (0.03 mol) of DA-3 was weighed, 92.3 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution, 6.22 g (0.0278 mol) of CA-1 was added, and the mixture was stirred at 40 °C for 24 hours to obtain a polyamic acid solution (A-3) (viscosity: 347 mPa·s).

[0105] <Synthesis Example 4> In a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 2.05 g (0.0084 mol) of DA-1 and 4.16 g (0.0196 mol) of DA-3 were weighed, 88.6 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution, 5.52 g (0.0246 mol) of CA-1 and 0.35 g (0.0014 mol) of CA-2 were added, and the mixture was stirred at 40 °C for 24 hours to obtain a polyamic acid solution (A-4) (viscosity: 213 mPa·s).

[0106] <Synthesis Example 5> In a 200 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 3.23 g (0.0084 mol) of DA-2 and 4.16 g (0.0196 mol) of DA-3 were weighed, 97.3 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution, 5.52 g (0.0246 mol) of CA-1 and 0.35 g (0.0014 mol) of CA-2 were added, and the mixture was stirred at 40 °C for 24 hours to obtain a polyamic acid solution (A-5) (viscosity: 198 mPa·s).

[0107] <Synthesis Example 6> In a 200 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 1.37 g (0.0056 mol) of DA-1, 4.16 g (0.0196 mol) of DA-3, and 1.56 g (0.0028 mol) of DA-4 were weighed, 95.1 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution, 5.52 g (0.0246 mol) of CA-1 and 0.35 g (0.0014 mol) of CA-2 were added, and the mixture was stirred at 40 °C for 24 hours to obtain a polyamic acid solution (A-6) (viscosity: 224 mPa·s).

[0108] <Synthesis Example 7> In a 200 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 1.37 g (0.0056 mol) of DA-1, 4.16 g (0.0196 mol) of DA-3, and 1.56 g (0.0028 mol) of DA-4 were weighed, 95.3 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution, 5.21 g (0.0232 mol) of CA-1 and 0.700 g (0.0028 mol) of CA-2 were added, and the mixture was stirred at 40 °C for 24 hours to obtain a polyamic acid solution (A-7) (viscosity: 177 mPa·s).

[0109] <Synthesis Example 8> Into a 200 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 1.37 g (0.0056 mol) of DA-1, 4.16 g (0.0196 mol) of DA-3, and 1.56 g (0.0028 mol) of DA-4 were weighed, 95.6 g of NMP was added, and while sending nitrogen, it was stirred and dissolved. While stirring this diamine solution, 4.90 g (0.0218 mol) of CA-1 and 1.05 g (0.0042 mol) of CA-2 were added, and it was stirred at 40 °C for 24 hours to obtain a polyamic acid solution (A-8) (viscosity: 176 mPa·s).

[0110] <Synthesis Example 9> 35 g (0.0093 mol) of the polyamic acid solution (A-1) obtained was taken into a 100 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, 11.7 g of NMP was added, and it was stirred for 30 minutes. To the obtained polyamic acid solution, 2.84 g of acetic anhydride (3 equivalents in terms of the molar ratio of polyamic acid) and 0.73 g of pyridine (equivalent amount in terms of the molar ratio of polyamic acid) were added, and it was heated at 50 °C for 3 hours to perform chemical imidization. The obtained reaction solution was poured into 150 ml of methanol while stirring, the precipitated precipitate was collected by filtration, and the resin powder was washed by performing the same operation twice. After drying at 60 °C for 12 hours, a polyimide resin powder was obtained. The imidization rate of this polyimide resin powder was 71%. 3.60 g of the obtained polyimide resin powder was taken into a 100 ml Erlenmeyer flask, 26.4 g of NMP was added so that the solid content concentration became 12%, and it was stirred and dissolved at 70 °C for 24 hours to obtain a polyimide solution (A-1-PI).

[0111] <Synthesis Examples 10 to 16> The same procedure was carried out in the same manner as in Synthesis Example 9 except that each raw material described in Table 1 below was used. The specifications of the polyimides obtained in Synthesis Examples 10 to 16 are shown in Table 1 together with Synthesis Example 9.

Table 1

[0112] The numerical values in parentheses in Table 1 represent, for the tetracarboxylic acid component, the blending ratio (mole parts) of each compound with respect to 100 mole parts of the total amount of the tetracarboxylic acid derivatives used in the synthesis, and for the diamine component, the blending ratio (mole parts) of each compound with respect to 100 mole parts of the total amount of the diamine used in the synthesis. For the organic solvent, it represents the blending ratio (parts by mass) of each organic solvent with respect to 100 parts by mass of the total amount of the organic solvents contained in the polyamic acid solution or the polyimide solution.

[0113] [Preparation of Liquid Crystal Alignment Agent] <Comparative Example 1> In a 20 ml sample tube containing a stir bar, 7.5 g of the polyimide solution (A-1-PI) was weighed, 2.23 g of NMP, 5.10 g of GBL, 4.0 g of BCS, 0.90 g of a GBL solution containing 1 wt% of S-1, and 0.27 g of an NMP solution containing 10 wt% of C-1 were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (R1).

[0114] <Example 1> In a 20 ml sample tube containing a stir bar, 7.5 g of the polyimide solution (A-4-PI) was taken, 2.23 g of NMP, 5.10 g of GBL, 4.0 g of BCS, 0.90 g of a GBL solution containing 1 wt% of S-1, and 0.27 g of an NMP solution containing 10 wt% of C-1 were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal alignment agent (1).

[0115] <Examples 2 to 6, Comparative Example 3> In Examples 2 to 6 and Comparative Example 3, each liquid crystal alignment agent was obtained in the same manner as in Comparative Example 1 and Example 1, except that the polyimide solutions, additives, and organic solvents described in Table 2 below were used. The specifications of the obtained liquid crystal alignment agents are shown in Table 1 together with the liquid crystal alignment agents of Example 1 and Comparative Example 1.

[0116]

Table 2

[0117] <Fabrication of Liquid Crystal Display Element> A substrate with electrodes was prepared. The substrate is a glass substrate with a size of 30 mm × 35 mm and a thickness of 0.7 mm. On the substrate, an IZO electrode with a solid pattern constituting the counter electrode is formed as the first layer. On the counter electrode of the first layer, a SiN (silicon nitride) film formed by CVD method is formed as the second layer. The film thickness of the SiN film in the second layer is 500 nm, which functions as an interlayer insulating film. On the SiN film in the second layer, comb-shaped pixel electrodes formed by patterning an IZO film are arranged as the third layer, forming two pixels, namely the first pixel and the second pixel. The size of each pixel is 10 mm in length and approximately 5 mm in width. At this time, the counter electrode in the first layer and the pixel electrode in the third layer are electrically insulated by the action of the SiN film in the second layer.

[0118] The pixel electrode in the third layer has a comb shape formed by arranging a plurality of electrode elements in a "C-shaped" configuration with a bent central portion. The width of each electrode element in the short direction is 3 μm, and the interval between electrode elements is 6 μm. Since the pixel electrode forming each pixel is composed of arranging a plurality of electrode elements in a "C-shaped" configuration with a bent central portion, the shape of each pixel is not rectangular, but has a shape similar to a thick "C" that bends at the central portion like the electrode element. And each pixel is divided into upper and lower parts with the bent portion in the center as the boundary, having a first region above the bent portion and a second region below the bent portion.

[0119] On each surface of the above-mentioned substrate with electrodes and a glass substrate having columnar spacers with a height of 4 μm and an ITO film formed on the back surface, a liquid crystal aligning agent filtered by a filter with an average pore diameter of 1.0 μm was applied by spin coating and dried on a hot plate at 80 °C for 2 minutes. Then, ultraviolet light with a wavelength of 254 nm linearly polarized with an extinction ratio of 26:1 was irradiated through a polarizing plate on the coating film surface at 150 - 350 mJ / cm 2 and then baked in a hot air circulation oven at 230 °C for 30 minutes to obtain each substrate with a liquid crystal alignment film having a film thickness of 100 nm. Next, a sealant was printed on one of the pair of glass substrates with the liquid crystal alignment film, and the other substrate was bonded so that the liquid crystal alignment film surfaces faced each other. The sealant was cured to fabricate an empty cell. Liquid crystal MLC-3019 (manufactured by Merck) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120 °C for 1 hour, left standing overnight, and then used for evaluation.

[0120] [Evaluation] [Evaluation of Liquid Crystal Alignment] Using the liquid crystal cell before ISO treatment, those with initial flow alignment were evaluated as "defective", and those without initial flow alignment were evaluated as "good".

[0121] [Evaluation of Seal Adhesion] [Sample Preparation] The liquid crystal aligning agent prepared above was applied to a 30 mm × 40 mm ITO substrate by spin coating. After drying on a hot plate at 80 °C for 2 minutes, the coating film surface was irradiated with ultraviolet light of 254 nm through a polarizing plate, and then baked in a hot air circulation oven at 230 °C for 20 minutes to form a coating film with a film thickness of 100 nm. Two substrates thus obtained were prepared. After applying 4-μm bead spacers on the liquid crystal alignment film surface of one substrate, a sealant (XN-1500T manufactured by Kyoritsu Chemical Industry Co., Ltd.) was dropped. Next, with the liquid crystal alignment film surface of the other substrate facing inward, the substrates were bonded so that the overlapping width of the substrates was 1 cm. At that time, the amount of sealant dropped was adjusted so that the diameter of the sealant after bonding was 3 mm. After fixing the two bonded substrates with clips, they were thermally cured at 150 °C for 1 hour to fabricate a sample for adhesion evaluation.

[0122] [Measurement of Seal Adhesion] The sample substrate prepared above was fixed at the end portions of the upper and lower substrates with a tabletop precision universal testing machine (AGS-X 500N, manufactured by Shimadzu Corporation), and then pushed in from above the central portion of the substrate to measure the strength (N) at the time of peeling. The value obtained by normalizing this peeling strength (N) with the adhesive area (mm 2 )(peeling strength (N) / adhesive area (mm 2)) as the seal adhesion (N / mm in each sample 2 ) and evaluated as "good" when the seal adhesion was greater than 4 N / mm 2 . When it was 4 N / mm 2 or less, it was evaluated as "bad".

[0123]

Table 3

Industrial Applicability

[0124] The liquid crystal aligning agent of the present invention is useful for forming a liquid crystal alignment film in a wide range of liquid crystal display elements such as an IPS driving method and an FFS driving method. In addition, the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2019-034305 filed on February 27, 2019 are hereby incorporated by reference and made a part of the disclosure of the specification of the present invention.

Claims

1. A liquid crystal aligning agent comprising a polymer (A) having a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (5), The liquid crystal aligning agent, wherein the polymer (A) is a polyimide having an imidization rate of 71% or more. 【Chemistry 1】 (R in formula (3) ３１ From R ３４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ３１ From R ３４ At least one of Y represents a group other than a hydrogen atom as defined above. ３ represents a divalent organic group represented by the following formula (I): 【Chemistry 2】 (* represents a bond.) 【Chemistry 3】 (R ５１ From R ５４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ５１ From R ５４ At least one of Y represents a group other than a hydrogen atom as defined above. ５ each independently represents a divalent organic group having a partial structure represented by the following formula (J-1), or a divalent organic group represented by the following formula (J-2). 【Chemistry 4】 (Q ５ is a single bond, -(CH ２ ) ｎ -(n is an integer from 1 to 20), or -(CH ２ ) ｎ Any of -CH ２ -O-, -COO-, -OCO-, -NQ, etc., provided that - is not adjacent to each other. ９ --, --NQ ９ CO-, -CONQ ９ --, --NQ ９ CONQ １０ --, --NQ ９ It is a group that can be replaced by COO- or -OCOO-. ９ and Q. １０ Each of Q independently represents a hydrogen atom or a monovalent organic group. ６ , Q ７ are each independently -H, -NHD, -N(D) ２ , a group having -NHD, or -N(D) ２ Q represents a group having the formula: ８ -NHD, -N(D) ２ , a group having -NHD, or -N(D) ２ D represents a carbamate protecting group. ５ , Q ６ and Q. ７ At least one of the groups has a carbamate-based protecting group. *1 represents a bond.)

2. Q ５ However, (CH ２ ) ｎ Any of -CH ２ -NQ under the condition that - is not adjacent to each other ９ --, --NQ ９ CO- or -CONQ ９ The liquid crystal aligning agent according to claim 1, wherein the aryl group is a group substituted with -.

3. The liquid crystal aligning agent according to claim 1 or 2, further comprising at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum's acid structure, a cyclocarbonate group, and a group represented by the following formula (d), or a compound represented by the following formula (e). 【Chemistry 5】 (R ７１ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". ７２ and R ７３ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". * indicates a bond. A represents an (m+n)-valent organic group having an aromatic ring. m represents an integer of 1 to 6, and n represents an integer of 0 to 4.

4. Seal adhesion is 4N / mm ２ The liquid crystal aligning agent according to any one of claims 1 to 3, wherein a liquid crystal alignment film having a size larger than

5. A liquid crystal aligning agent comprising a polymer (A) having a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (5), Seal adhesion is 4N / mm ２ The liquid crystal aligning agent according to claim 1, wherein a liquid crystal alignment film having a larger size than 【Chemistry 6】 (R in formula (3) ３１ From R ３４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ３１ From R ３４ At least one of Y represents a group other than a hydrogen atom as defined above. ３ represents a divalent organic group represented by the following formula (I): 【Chemistry 7】 (* represents a bond.) 【Chemistry 8】 (R ５１ From R ５４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ５１ From R ５４ At least one of Y represents a group other than a hydrogen atom as defined above. ５ each independently represents a divalent organic group having a partial structure represented by the following formula (J-1): 【Chemistry 9】 (Q ５ is a single bond, -(CH ２ ) ｎ -(n is an integer from 1 to 20), or -(CH ２ ) ｎ Any of -CH ２ -O-, -COO-, -OCO-, -NQ, etc., provided that - is not adjacent to each other. ９ CO-, -CONQ ９ --, --NQ ９ Each Q 9 independently represents a hydrogen atom or a monovalent organic group. ６ , Q ７ are each independently -H, -NHD, -N(D) ２ , a group having -NHD, or -N(D) ２ D represents a carbamate protecting group. ５ , Q ６ and Q. ７ At least one of the groups has a carbamate-based protecting group. *1 represents a bond.)

6. Q ５ However, (CH ２ ) ｎ Any of -CH ２ -NQ under the condition that - is not adjacent to each other ９ CO- or -CONQ ９ The liquid crystal aligning agent according to claim 5 , wherein the aryl group is a group substituted with -.

7. Further, the liquid crystal aligning agent according to any one of claims 5 to 6, which contains at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum's acid structure, a cyclocarbonate group, and a group represented by the following formula (d), or a compound represented by the following formula (e). 【Chemistry 10】 (R ７１ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". ７２ and R ７３ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". * indicates a bond. A represents an (m+n)-valent organic group having an aromatic ring. m represents an integer of 1 to 6, and n represents an integer of 0 to 4.

8. A liquid crystal alignment film comprising a polymer (A) obtained from the liquid crystal alignment agent according to any one of claims 1 to 4 and having a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (5): 【Chemistry 11】 (R in formula (3) ３１ From R ３４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ３１ From R ３４ At least one of Y represents a group other than a hydrogen atom as defined above. ３ represents a divalent organic group represented by the following formula (I): 【Chemistry 12】 (* represents a bond.) 【Chemistry 13】 (R ５１ From R ５４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ５１ From R ５４ At least one of Y represents a group other than a hydrogen atom as defined above. ５ each independently represents a divalent organic group having a partial structure represented by the following formula (J-1), or a divalent organic group represented by the following formula (J-2). 【Chemistry 14】 (Q ５ is a single bond, -(CH ２ ) ｎ -(n is an integer from 1 to 20), or -(CH ２ ) ｎ Any of -CH ２ -O-, -COO-, -OCO-, -NQ, etc., provided that - is not adjacent to each other. ９ --, --NQ ９ CO-, -CONQ ９ --, --NQ ９ CONQ １０ --, --NQ ９ It is a group that can be replaced by COO- or -OCOO-. ９ and Q. １０ Each of Q independently represents a hydrogen atom or a monovalent organic group. ６ , Q ７ are each independently -H, -NHD, -N(D) ２ , a group having -NHD, or -N(D) ２ Q represents a group having the formula: ８ -NHD, -N(D) ２ , a group having -NHD, or -N(D) ２ D represents a carbamate protecting group to be eliminated. ５ , Q ６ and Q. ７ At least one of the groups has a carbamate-based protecting group. *1 represents a bond.)

9. Q ５ However, (CH ２ ) ｎ Any of -CH ２ -NQ under the condition that - is not adjacent to each other ９ --, --NQ ９ CO- or -CONQ ９ The liquid crystal alignment film according to claim 8 , wherein the aryl group is a group substituted with -.

10. 10. The liquid crystal alignment film according to claim 8, wherein the polymer (A) is a polyimide having an imidization rate of 71% or more.

11. Further, a compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum's acid structure, a cyclocarbonate group, and a group represented by the following formula (d), or a compound represented by the following formula (e) (hereinafter, these are also collectively referred to as compound (C)). The liquid crystal alignment film according to any one of claims 8 to 10. 【Chemistry 15】 (R ７１ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". ７２ and R ７３ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". * indicates a bond. A represents an (m+n)-valent organic group having an aromatic ring. m represents an integer of 1 to 6, and n represents an integer of 0 to 4.

12. Seal adhesion is 4N / mm ２ The liquid crystal alignment film according to any one of claims 8 to 11, wherein

13. A liquid crystal alignment film comprising a polymer (A) obtained from the liquid crystal alignment agent according to any one of claims 5 to 7 and having a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (5): 【Chemistry 16】 (R in formula (3) ３１ From R ３４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ３１ From R ３４ At least one of Y represents a group other than a hydrogen atom as defined above. ３ represents a divalent organic group represented by the following formula (I): 【Chemistry 17】 (* represents a bond.) 【Chemistry 18】 (R ５１ From R ５４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ５１ From R ５４ At least one of Y represents a group other than a hydrogen atom as defined above. ５ each independently represents a divalent organic group having a partial structure represented by the following formula (J-1): 【Chemistry 19】 (Q ５ is a single bond, -(CH ２ ) ｎ -(n is an integer from 1 to 20), or -(CH ２ ) ｎ Any of -CH ２ -O-, -COO-, -OCO-, -NQ, etc., provided that - is not adjacent to each other. ９ CO-, -CONQ ９ --, --NQ ９ It is a group that can be replaced by COO- or -OCOO-. ９ and Q. １０ Each of Q independently represents a hydrogen atom or a monovalent organic group. ６ , Q ７ are each independently -H, -NHD, -N(D) ２ , a group having -NHD, or -N(D) ２ D represents a carbamate protecting group to be eliminated. ５ , Q ６ and Q. ７ At least one of the groups has a carbamate-based protecting group. *1 represents a bond.)

14. Q ５ However, (CH ２ ) ｎ Any of -CH ２ -NQ under the condition that - is not adjacent to each other ９ --, --NQ ９ CO- or -CONQ ９ The liquid crystal alignment film according to claim 13, wherein the aryl group is a group substituted with -.

15. Further, a compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum's acid structure, a cyclocarbonate group, and a group represented by the following formula (d), or a compound represented by the following formula (e) (hereinafter, these are also collectively referred to as compound (C)). The liquid crystal alignment film according to any one of claims 13 to 14. 【Chemistry 20】 (R ７１ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". ７２ and R ７３ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". * indicates a bond. A represents an (m+n)-valent organic group having an aromatic ring. m represents an integer of 1 to 6, and n represents an integer of 0 to 4.

16. A method for producing a liquid crystal alignment film, comprising the following steps (1) to (3): Step (1): A step of applying a liquid crystal aligning agent containing a polymer (A) which is a polyimide having a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (5) and has an imidization rate of 71% or more onto a substrate. Step (2): A step of heating the coating film of the liquid crystal alignment agent obtained in step (1). Step (3): A step of irradiating the film obtained in step (2) with polarized ultraviolet light. 【Chemistry 21】 (R in formula (3) ３１ From R ３４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ３１ From R ３４ At least one of Y represents a group other than a hydrogen atom as defined above. ３ represents a divalent organic group represented by the following formula (I): 【Chemical 22】 (* represents a bond.) 【Chemistry 23】 (R ５１ From R ５４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ５１ From R ５４ At least one of Y represents a group other than a hydrogen atom as defined above. ５ each independently represents a divalent organic group having a partial structure represented by the following formula (J-1), or a divalent organic group represented by the following formula (J-2). 【Chemistry 24】 (Q ５ is a single bond, -(CH ２ ) ｎ -(n is an integer from 1 to 20), or -(CH ２ ) ｎ Any of -CH ２ -O-, -COO-, -OCO-, -NQ, etc., provided that - is not adjacent to each other. ９ --, --NQ ９ CO-, -CONQ ９ --, --NQ ９ CONQ １０ --, --NQ ９ It is a group that can be replaced by COO- or -OCOO-. ９ and Q. １０ Each of Q independently represents a hydrogen atom or a monovalent organic group. ６ , Q ７ are each independently -H, -NHD, -N(D) ２ , a group having -NHD, or -N(D) ２ Q represents a group having the formula: ８ -NHD, -N(D) ２ , a group having -NHD, or -N(D) ２ D represents a carbamate protecting group. ５ , Q ６ and Q. ７ At least one of the groups has a carbamate-based protecting group. *1 represents a bond.)

17. Q ５ However, (CH ２ ) ｎ Any of -CH ２ -NQ under the condition that - is not adjacent to each other ９ --, --NQ ９ CO- or -CONQ ９ The method for producing a liquid crystal alignment film according to claim 16, wherein the aryl group is a group substituted with -.

18. The method for producing a liquid crystal alignment film according to claim 16 or 17, further comprising a compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum's acid structure, a cyclocarbonate group, and a group represented by the following formula (d), or a compound represented by the following formula (e) (hereinafter, these are also collectively referred to as compound (C)). 【Chemistry 25】 (R ７１ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". ７２ and R ７３ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". * indicates a bond. A represents an (m+n)-valent organic group having an aromatic ring. m represents an integer of 1 to 6, and n represents an integer of 0 to 4.

19. The seal adhesion of the liquid crystal alignment film is 4N / mm. ２ The method for producing a liquid crystal alignment film according to any one of claims 16 to 18, wherein

20. The method for producing a liquid crystal alignment film according to any one of claims 16 to 19, further comprising the following step (4): Step (4): A step of baking the film obtained in step (3) at a temperature of 100° C. or higher and at a temperature higher than that in step (2).

21. The method for producing a liquid crystal alignment film according to any one of claims 16 to 20, wherein the coating film of the liquid crystal alignment agent is heated at a temperature of 40 to 180°C in the step (2).

22. The following steps (1) to (3) are included, and the seal adhesion is 4N / mm ２ A method for producing a liquid crystal alignment film having a size larger than 100 nm. Step (1): A step of applying a liquid crystal aligning agent, which is characterized by containing a polymer (A) having a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (5), onto a substrate. Step (2): A step of heating the coating film of the liquid crystal alignment agent obtained in step (1). Step (3): A step of irradiating the film obtained in step (2) with polarized ultraviolet light. 【Chemistry 26】 (R in formula (3) ３１ From R ３４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ３１ From R ３４ At least one of Y represents a group other than a hydrogen atom as defined above. ３ represents a divalent organic group represented by the following formula (I): 【Chemistry 27】 (* represents a bond.) 【Chemistry 28】 (R ５１ From R ５４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and may be the same or different. ５１ From R ５４ At least one of Y represents a group other than a hydrogen atom as defined above. ５ each independently represents a divalent organic group having a partial structure represented by the following formula (J-1): 【Chemical Formula 29】 (Q ５ is a single bond, -(CH ２ ) ｎ -(n is an integer from 1 to 20), or -(CH ２ ) ｎ Any of -CH ２ -O-, -COO-, -OCO-, -NQ, etc., provided that - is not adjacent to each other. ９ CO-, -CONQ ９ --, --NQ ９ Each Q 9 independently represents a hydrogen atom or a monovalent organic group. ６ , Q ７ are each independently -H, -NHD, -N(D) ２ , a group having -NHD, or -N(D) ２ D represents a carbamate protecting group. ５ , Q ６ and Q. ７ At least one of the groups has a carbamate-based protecting group. *1 represents a bond.)

23. Q ５ However, (CH ２ ) ｎ Any of -CH ２ -NQ under the condition that - is not adjacent to each other ９ CO- or -CONQ ９ The method for producing a liquid crystal alignment film according to claim 22, wherein the aryl group is a group substituted with -.

24. The method for producing a liquid crystal alignment film according to claim 22 or 23, further comprising a compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum's acid structure, a cyclocarbonate group, and a group represented by the following formula (d), or a compound represented by the following formula (e) (hereinafter, these are also collectively referred to as compound (C)). 【Chemistry 30】 (R ７１ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". ７２ and R ７３ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH ２ -OH". * indicates a bond. A represents an (m+n)-valent organic group having an aromatic ring. m represents an integer of 1 to 6, and n represents an integer of 0 to 4.

25. The method for producing a liquid crystal alignment film according to any one of claims 22 to 24, further comprising the following step (4): Step (4): A step of baking the film obtained in step (3) at a temperature of 100° C. or higher and at a temperature higher than that in step (2).

26. In the step (2), the coating film of the liquid crystal alignment agent is heated at a temperature of 40 to 180° C.; The method for producing a liquid crystal alignment film according to any one of claims 22 to 25.

27. A liquid crystal display device comprising a liquid crystal alignment film obtained by the method for producing a liquid crystal alignment film according to any one of claims 16 to 21.

28. A liquid crystal display device comprising a liquid crystal alignment film obtained by the method for producing a liquid crystal alignment film according to any one of claims 22 to 26.

29. A liquid crystal display device comprising the liquid crystal alignment film according to any one of claims 8 to 12.

30. A liquid crystal display device comprising the liquid crystal alignment film according to any one of claims 13 to 15.

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