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

Abstract

To provide a liquid crystal alignment agent capable of acquiring a liquid crystal alignment film having high transparency, little charge accumulation and high relaxation of accumulated residual charges.SOLUTION: A liquid crystal alignment agent contains a compound (P) having a partial structure (A) represented by a formula (1). *-Y1-A1-A2-Y2-* ...(1). In the formula (1), A1 and A2 are a divalent group having a condensed ring structure in which an aromatic ring is condensed to each of 2, 3-positions and 4, 5-positions of at least one aromatic hydrocarbon ring selected from a group respectively independently constituting of a pyrrole ring, a furan ring, and a thiophene ring, where in the A1 and A2, at least one carbon atoms of the aromatic ring constituting of the condensed ring structure are bonded by a single bond. Y1 and Y2 are a divalent organic group bonded by a carbon atom, an oxygen atom, a sulfur atom or *5-NR5-CO- to the condensed ring structure in A1 or A2, or *2-NR4-*3.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal device. [Background technology]

[0002] Liquid crystal elements are widely used in televisions, mobile devices, various monitors, etc. As their applications become more diverse, there is a demand for even higher quality liquid crystal elements, and progress is being made in improving the liquid crystal alignment film, one of the materials that make up liquid crystal elements, as well as improving the driving method and element structure.

[0003] In liquid crystal devices, if electric charge accumulates in the liquid crystal cell, it is perceived by the viewer as an afterimage (DC afterimage), which reduces the display quality of the liquid crystal device. Therefore, one of the characteristics required for liquid crystal alignment films is that they must have low electric charge accumulation. Possible causes of electric charge accumulation in liquid crystal cells include the application of asymmetric positive and negative voltages due to AC drive and the absorption of backlight light by the liquid crystal alignment film. DC afterimages are particularly likely to occur in FFS (Fringe Field Switching) type liquid crystal display devices, which have an asymmetric electrode structure.

[0004] Therefore, various techniques have been proposed to suppress the accumulation of electric charges in liquid crystal cells and improve the display quality of liquid crystal elements (see, for example, Patent Documents 1 and 2). Patent Document 1 discloses that the accumulation of electric charges can be reduced by incorporating a polyamic acid obtained by reacting a diamine compound containing a nitrogen-containing diamine such as N4,N4'-bis(4-aminophenyl)-benzidine with a tetracarboxylic dianhydride into a liquid crystal aligning agent. Patent Document 2 discloses that the accumulation of electric charges can be quickly relaxed and a liquid crystal alignment film that is less likely to flicker during operation can be obtained by incorporating a polymer obtained from a diamine having a structure in which a carbazole structure and a benzene ring are bonded via an amino group into a liquid crystal aligning agent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-107811 [Patent Document 2] International Publication No. 2018 / 110354 Summary of the Invention [Problem to be solved by the invention]

[0006] In order to meet the recent demand for higher performance, a liquid crystal alignment film that can further reduce the accumulation of electric charges in a liquid crystal cell and can more quickly relieve the accumulated residual electric charges is required. In addition, the liquid crystal alignment film is required to have high transparency.

[0007] The present invention has been made in consideration of the above-mentioned problems, and has as its main object to provide a liquid crystal aligning agent that can obtain a liquid crystal alignment film that is highly transparent, has little charge accumulation, and quickly relaxes accumulated residual charge. [Means for solving the problem]

[0008] The present invention employs the following means to solve the above problems.

[0009] <1> A liquid crystal aligning agent comprising a compound (P) having a partial structure (A) represented by the following formula (1): *-Y 1 -A 1 -A 2 -Y 2 -* …(1) (In formula (1), A 1 and A 2 are each independently a divalent group having a fused ring structure in which aromatic rings are fused to the 2,3-position and the 4,5-position of at least one heteroaromatic ring selected from the group consisting of a pyrrole ring, a furan ring, and a thiophene ring, respectively. 1 and A 2 At least one carbon atom of the aromatic ring constituting the fused ring structure is bonded to another carbon atom of the aromatic ring by a single bond. 1 and Y 2are each independently, A 1 or A 2 Carbon atom, oxygen atom, sulfur atom or * for the fused ring structure in 5 -NR 5 A divalent organic group bonded with -CO-, or * 2 -NR 4 -* 3 R 4 is a hydrogen atom or a monovalent organic group, or is bonded to another group to form R 4 represents a part of a ring structure formed together with the nitrogen atom to which R is attached. 5 is a hydrogen atom or a monovalent organic group. 2 " and "* 5 " is A 1 or A 2 It represents a bond that is bonded to the fused ring structure in the ring. 3 " represents a bond bonded to -CO-. "*" represents a bond.)

[0010] <2> the above <1> A liquid crystal alignment film formed using the liquid crystal alignment agent of the above. <3> the above <2> A liquid crystal element comprising the liquid crystal alignment film. <4> A polymer having at least one selected from the group consisting of a partial structure represented by the following formula (5) and a partial structure represented by the following formula (6): [ka] (In formula (5) and formula (6), X 1 is a tetravalent aliphatic hydrocarbon group. 2 R is a divalent organic group represented by the following formula (7) or formula (8). 8 , R 9 , R 10 and R 11 are each independently a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms. [ka] (In formula (7), R 1 is a halogen atom, a hydroxy group, or a monovalent organic group, or a plurality of R1 represents a fused ring structure formed by combining together with the ring to which they are attached. 5 is a divalent organic group bonded to the fused ring structure in the formula via a carbon atom. a1 is an integer of 0 to 3. In the formula, R 1 If there are multiple R 1 are the same or different. 5 are the same or different. Multiple a1's in the formula are the same or different. "*" represents a bond. [ka] (In formula (8), R 2 is a halogen atom, a hydroxy group, or a monovalent organic group. 3 is a hydrogen atom or a monovalent organic group. 6 is a single bond or a carbon atom, oxygen atom, sulfur atom or * to the fused ring structure in the formula 5 -NR 5 It is a divalent organic group bonded by -CO-. 5 is a hydrogen atom or a monovalent organic group. 5 " represents a bond bonded to the fused ring structure in the formula. a2 is an integer of 0 to 3. In the formula, R 2 If there are multiple R 2 are the same or different. 6 are the same or different. Multiple a2's in the formula are the same or different. "*" represents a bond. [Effects of the Invention]

[0011] The liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film with high transparency, and can also provide a liquid crystal alignment film with little charge accumulation and rapid relaxation of accumulated residual charge. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 shows the results of measuring the 1H-NMR spectrum of the diamine (DA-1) obtained in Synthesis Example 1. [Figure 2] FIG. 1 shows the results of measuring the 13C-NMR spectrum of the diamine (DA-1) obtained in Synthesis Example 1. [Figure 3] FIG. 10 shows the transmission spectra of Examples 20 to 23. [Figure 4] FIG. 10 is a graph showing the transmission spectra of Comparative Examples 7 to 11. [Figure 5] FIG. 1 shows the molecular structures and molecular orbitals (HOMO and LUMO) of the bissuccinimides of Examples 20 to 23 and Comparative Examples 7 to 11. DETAILED DESCRIPTION OF THE INVENTION

[0013] Matters related to the embodiments of the present disclosure will be described in detail below. In this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a straight-chain hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed only of a chain structure. However, it may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, it does not have to be composed only of an alicyclic hydrocarbon structure and may include one that has a chain structure as part of it. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, it does not have to be composed only of an aromatic ring structure and may contain a chain structure or an alicyclic hydrocarbon structure as part of it.

[0014] The term "aliphatic hydrocarbon group" encompasses both linear hydrocarbon groups and alicyclic hydrocarbon groups. The term "heteroaromatic group" refers to a group formed by removing n hydrogen atoms (n is an integer) from the ring portion of an aromatic heterocycle. However, when a heteroaromatic group has multiple rings, it includes groups formed by removing n hydrogen atoms from the same ring and groups formed by removing n hydrogen atoms from different rings. The "main chain" of a polymer refers to the longest "trunk" portion of the atomic chain of the polymer. The "side chain" of a polymer refers to the portion branched from the "trunk" of the polymer. The term "organic group" refers to an atomic group formed by removing any hydrogen atoms from a carbon-containing compound (i.e., an organic compound).

[0015] Liquid crystal alignment agent The liquid crystal aligning agent of the present disclosure contains a compound (P) having a partial structure (A) represented by the following formula (1). *-Y 1 -A 1 -A 2 -Y 2 -* …(1) (In formula (1), A 1 and A 2 are each independently a divalent group having a fused ring structure in which aromatic rings are fused to the 2,3-position and the 4,5-position of at least one heteroaromatic ring selected from the group consisting of a pyrrole ring, a furan ring, and a thiophene ring, respectively. 1 and A 2 At least one carbon atom of the aromatic ring constituting the fused ring structure is bonded to another carbon atom of the aromatic ring by a single bond. 1 and Y 2 are each independently, A 1 or A 2 Carbon atom, oxygen atom, sulfur atom or * for the fused ring structure in 5 -NR 5 A divalent organic group bonded with -CO-, or * 2 -NR 4 -* 3 R 4 is a hydrogen atom or a monovalent organic group, or is bonded to another group to form R 4 represents a part of a ring structure formed together with the nitrogen atom to which R is attached. 5 is a hydrogen atom or a monovalent organic group. 2 " and "* 5 " is A 1 or A 2 It represents a bond that is bonded to the fused ring structure in the ring. 3 " represents a bond bonded to -CO-. "*" represents a bond.)

[0016] In the above formula (1), A 1 and A 2In the fused ring structure of the heteroaromatic ring, the heteroaromatic ring is preferably a pyrrole ring. The aromatic ring fused to the heteroaromatic ring is preferably a benzene ring or a naphthalene ring. The aromatic ring fused to the heteroaromatic ring may have a substituent introduced therein. Examples of the substituent include a halogen atom, a hydroxy group, or a monovalent organic group. Among these, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, -NR 10 R 11 (However, R 10 and R 11 are each independently a monovalent hydrocarbon group).

[0017] A 1 and A 2 The fused ring structure contained in each of A may be a carbazole ring structure, a benzocarbazole ring structure, or a dibenzocarbazole ring structure. 1 and A 2 The fused ring structure of the formula (I) is particularly preferably a carbazole ring structure.

[0018] A 1 and an aromatic ring constituting a fused ring structure of A 2 The bonding position of A to the aromatic ring constituting the fused ring structure is not particularly limited. 1 and A 2 When the fused ring structure possessed by each of A is a carbazole ring structure, the bonding positions of the two carbazole rings may be the 3,3'-positions, the 4,4'-positions, or the 3,9'-positions, among which the 3,3'-positions are preferred. 1 and A 2 In A 1 and an aromatic ring constituting a fused ring structure of A 2 The aromatic ring constituting the fused ring structure may be further fused.

[0019] Group “-A 1 -A 2 Specific examples of "-" include groups represented by the following formulae (a-1) to (a-5). 1 -A 2 "-" is preferably a group represented by the following formula (a-1) or (a-2). 1 and an aromatic ring constituting a fused ring structure of A 2 Examples of the aromatic rings constituting the fused ring structure of the above group are further fused, including groups represented by the following formulae (a-3) to (a-5). [ka] (In formulas (a-1) to (a-5), R a R is a halogen atom, a hydroxy group, or a monovalent organic group. b is a hydrogen atom or a monovalent organic group. r is an integer of 0 to 3. E 1 -O-, -S-, -NR c - or -CH=CH-. R c is a hydrogen atom or a monovalent organic group. a If there are multiple R a are the same or different. 1 If there are multiple E 1 are the same or different. "*" indicates a bond.)

[0020] In the above formula (1), Y 1 , Y 2 but* 2 -NR 4 -* 3 If R 4 The monovalent organic group is preferably an alkyl group having 1 to 5 carbon atoms or a leaving group which is left by at least one of heat and light, and more preferably an alkyl group having 1 to 5 carbon atoms or a thermally leaving group. 4From the viewpoint of eliminating the thermally eliminable group and thereby simplifying the process, the thermally eliminable group is preferably a group that decomposes at a temperature of 120 to 300° C. and is replaced with a hydrogen atom. Specifically, a tert-butoxycarbonyl group (Boc group) or a 9-fluorenylmethoxycarbonyl group is preferred, and a tert-butoxycarbonyl group is particularly preferred.

[0021] R 4 is bonded to another group, R 4 When R represents a part of a ring structure formed together with the nitrogen atom to which it is bonded, a specific example of the ring structure is an imide ring structure. 4 When R is bonded to another group and represents a part of an imide ring structure formed together with the nitrogen atom, 4 For example, * 6 -CO-R- (where R is a single bond or a divalent organic group.) 6 represents a bond bonded to a nitrogen atom).

[0022] Y 1 and Y 2 But, A 1 or A 2 Carbon atom, oxygen atom, sulfur atom or * for the fused ring structure in 5 -NR 5 In the case of a divalent organic group bonded by -CO-, the divalent organic group is a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent hydrocarbon group in which at least one methylene group is -O-, -S-, -CO- or * 5 -NR 5 Examples of R include a divalent group having 1 to 20 carbon atoms in which at least one hydrogen atom in a divalent hydrocarbon group has been replaced with a substituent (for example, a halogen atom, a carboxy group, a hydroxy group, etc.), and a divalent heterocyclic aromatic group. 5 Specific examples of when is a monovalent organic group are as described above for R 4 Examples of the heterocyclic aromatic group include a pyridinediyl group and a pyrimidinediyl group.

[0023] From the viewpoint of obtaining a sufficient effect of reducing the afterimage (DC afterimage) caused by accumulated charge, the compound (P) preferably has a partial structure (A) in its main chain. Specifically, the partial structure (A) is preferably at least one selected from the group consisting of the partial structure represented by the following formula (2) and the partial structure represented by the following formula (3). [ka] (In formula (2), R 1 is a halogen atom, a hydroxy group, or a monovalent organic group, or a plurality of R 1 represents a fused ring structure formed by combining together with the ring to which they are attached. 3 is a divalent organic group bonded to the fused ring structure in the formula via a carbon atom. a1 is an integer of 0 to 3. In the formula, R 1 If there are multiple R 1 are the same or different. 3 are the same or different. Multiple a1's in the formula are the same or different. "*" represents a bond. [ka] (In formula (3), R 2 is a halogen atom, a hydroxy group, or a monovalent organic group. 3 is a hydrogen atom or a monovalent organic group. 4 represents a carbon atom, an oxygen atom, a sulfur atom, or * to the fused ring structure in the formula. 5 -NR 5 A divalent organic group bonded with -CO-, or * 2 -NR 4 -* 3 R 4 is a hydrogen atom or a monovalent organic group, or is bonded to another group to form R 4 represents a part of a ring structure formed together with the nitrogen atom to which R is attached. 5 is a hydrogen atom or a monovalent organic group. 2 " and "* 5" represents a bond bonded to the fused ring structure in the formula. 3 " represents a bond bonded to -CO-. a2 is an integer of 0 to 3. In the formula, R 2 If there are multiple R 2 are the same or different. 4 are the same or different. Multiple a2's in the formula are the same or different. "*" represents a bond.

[0024] In the above formula (2), R 1 Specific examples of the monovalent organic group include the groups exemplified as the substituents that may be possessed by the aromatic ring fused to the heteroaromatic ring in the above formula (1). R 1 is a plurality of R in the above formula (2) 1 When two R 1 and two R bonded to different aromatic rings (e.g., aromatic rings in different carbazole structures). 1 The R in the formula (2) includes a fused ring structure formed by combining them with each other together with the ring to which they are attached. 1 Specific examples of the fused ring structure formed by combining with each other together with the rings to which they are bonded include the structures represented by the above formulae (a-3) to (a-5).

[0025] Y 3 Specific examples of the above include Y 1 and Y 2 Examples of the divalent organic group in Y include the groups exemplified above. 3 is preferably a divalent organic group bonded to the fused ring structure in the formula via a carbon atom, and is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent hydrocarbon group having -O-, -S-, -CO- or * between the carbon-carbon bonds. 5 -NR 5More preferably, Y is a divalent group having 2 to 20 carbon atoms and containing -CO-, a divalent group having 1 to 20 carbon atoms in which at least one hydrogen atom in a divalent hydrocarbon group has been replaced with a substituent (for example, a halogen atom, a carboxy group, a hydroxy group, etc.), or a divalent heterocyclic aromatic group. 3 is preferably a group that is bonded to the nitrogen atom in the above formula (2) via an aromatic ring (preferably a benzene ring, a naphthalene ring, a pyridine ring or a pyrimidine ring).

[0026] In the above formula (3), R 2 Specific examples of include the groups exemplified as the substituents that the aromatic ring fused to the heteroaromatic ring in the above formula (1) may have. Y 4 but* 2 -NR 4 -* 3 If R 4 Specific examples of the monovalent organic group include R 4 Examples of the groups exemplified as Y 4 is a divalent organic group bonded to the fused ring structure in the formula via a carbon atom, an oxygen atom, or a sulfur atom, and specific examples thereof include Y 1 and Y 2 In terms of the high effect of reducing residual charge and ease of synthesis, the divalent organic groups Y 4 Among them, * 4 -G 3 -A 3 -(However, G 3 is an oxygen atom or a sulfur atom. 3 is a divalent aromatic ring group (preferably a group in which two hydrogen atoms have been removed from a benzene ring, a naphthalene ring, a pyridine ring, or a pyrimidine ring). 4 " represents a bond bonded to a fused ring structure.) is preferred.

[0027] R 3The monovalent organic group R is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms or a leaving group that is released by at least one of heat and light, and more preferably an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, a phenyl group or a thermally releasing group. 3 Specific and preferred examples of when is a thermally eliminable group are as follows: R 4 The explanation of the thermally eliminable group R 3 Among the hydrogen atoms and monovalent organic groups, a monovalent organic group is preferred in that it can further improve the transparency of the liquid crystal alignment film. a2 is preferably 0 or 1.

[0028] The compound (P) may be a polymer component contained in the liquid crystal aligning agent, or may be an additive component blended separately from the polymer component. The compound (P) is preferably a polymer, in that it can more fully reduce DC afterimages. The polymer having the partial structure (A) (hereinafter also referred to as "polymer (P)") and the additive having the partial structure (A) (hereinafter also referred to as "additive (P)") will be described below.

[0029] About polymer (P) The main skeleton of the polymer (P) is not particularly limited. In terms of facilitating the introduction of the partial structure (A) into the main chain of the polymer, the polymer (P) is preferably a diamine having a partial structure represented by the above formula (2) and a diamine having a partial structure represented by the above formula (3) (wherein, in the above formula (3), R 4 is a hydrogen atom or a monovalent organic group.) and examples thereof include polyamic acid, polyamic acid ester, polyimide, polyamide, polyurea, polyamine, polyamideimide, polyorganosiloxane, polyester, polyenamine, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, (meth)acrylic polymer, styrene polymer, maleimide polymer, styrene-maleimide copolymer, etc.

[0030] In terms of being able to form an organic film that has high affinity with liquid crystal and high mechanical strength, and being able to obtain a highly reliable liquid crystal device, the polymer (P) is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyurea, polyorganosiloxane, and polymers containing a structural unit derived from a monomer having a polymerizable unsaturated carbon-carbon bond, and more preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.

[0031] The polymer (P) may have the partial structure (A) in the main chain, in the side chain, or at the terminal. In terms of improving the transparency of the film, reducing accumulated charge, and alleviating residual charge, it is preferable that the polymer (P) have the partial structure (A) in the main chain. When the polymer (P) has the partial structure (A) in the main chain, the partial structure (A) may be present not only in the main chain but also in parts other than the main chain (side chains or terminals).

[0032] The method for introducing the partial structure (A) into the polymer (P) is not particularly limited. For example, a polymer having the partial structure (A) in its main chain can be obtained by polymerizing a monomer having the partial structure represented by the above formula (1) in its main chain. Furthermore, a polymer having the partial structure (A) in its side chain can be obtained by, for example, polymerizing a monomer having the partial structure represented by the above formula (1) in its side chain, or by modifying the side chain of the polymer with a reactive compound having the partial structure represented by the above formula (1). A polymer having the partial structure (A) at the end of the polymer (P) can be obtained by, for example, adding an end-capping agent (a monofunctional compound in the case of step-growth polymerization, or a polymerization initiator or polymerization terminator in the case of chain polymerization) having the partial structure represented by the above formula (1) and polymerizing the polymer.

[0033] When the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, the polymer (P) is preferably a polymer having at least one selected from the group consisting of a partial structure represented by the following formula (5) and a partial structure represented by the following formula (6): [ka] (In formula (5) and formula (6), X 1 is a tetravalent organic group. 2 R is a divalent organic group represented by the following formula (7) or formula (8). 8 , R 9 , R 10 and R 11 are each independently a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms. [ka] (In formula (7), Y 5 is a divalent organic group. 5 are the same or different. R 1 and a1 are the same as in formula (2). "*" represents a bond. [ka] (In formula (8), Y 6 is a single bond or a carbon atom, oxygen atom, sulfur atom or * to the fused ring structure in the formula 5 -NR 5 It is a divalent organic group bonded by -CO-. 5 is a hydrogen atom or a monovalent organic group. 5 " represents a bond bonded to the fused ring structure in the formula. 6 are the same or different. R 2 and a2 are the same as in formula (3). "*" represents a bond.

[0034] In the above formulas (5) and (6), X 1is a tetravalent organic group derived from a tetracarboxylic acid derivative. In this specification, the term "tetracarboxylic acid derivative" includes tetracarboxylic acid dianhydrides, tetracarboxylic acid diesters, and tetracarboxylic acid diester dihalides.

[0035] X 1 As the tetracarboxylic acid derivative constituting X, a compound known as a tetracarboxylic acid derivative that can be used in the production of polyamic acid, polyamic acid ester, and polyimide can be used. X is advantageous in that it can provide a liquid crystal alignment film with high transparency and a liquid crystal alignment film with less accumulated charge. 1 is preferably a tetravalent aliphatic hydrocarbon group, and specific examples include the tetravalent groups represented by the following formulas (11) to (16). 1 In particular, X is preferably a tetravalent alicyclic hydrocarbon group. 1 is preferably a tetravalent group having a cyclobutane ring structure, and specifically, is particularly preferably a tetravalent group represented by the following formula (11) or formula (12): 1 a partial structure in which X is a tetravalent aliphatic hydrocarbon group; 1 is a tetravalent aromatic hydrocarbon group, the polarities of the accumulated charges tend to cancel each other out, resulting in a small accumulated charge. [ka] (In formulas (11) to (16), "*" represents a bond.)

[0036] X 2 Regarding Y in the above formula (7), 5 For specific examples, see Y in the above formula (2). 3 The explanation of R can be used. 1 The explanation for the above formula (2) can be applied to a1 and a2. 6 Specific examples of the divalent organic group include Y in the above formula (3).4 The explanation of R in the above formula (8) can be used. 2 For a2, the explanation for the above formula (3) can be applied. R 8 , R 9 , R 10 and R 11 When is a monovalent organic group having 1 to 8 carbon atoms, the monovalent organic group is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

[0037] <Polyamic acid> The synthesis method of the polymer (P) is not particularly limited, and the polymer (P) can be obtained by appropriately combining standard methods in organic chemistry. When the polymer (P) is a polyamic acid, the polyamic acid (hereinafter also referred to as "polyamic acid (P)") can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine compound containing a specific diamine.

[0038] (Tetracarboxylic acid dianhydride) The tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid (P) is not particularly limited, and examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aromatic tetracarboxylic acid dianhydrides.

[0039] Specific examples of these include aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and ethylenediaminetetraacetic dianhydride; Examples of alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5, 9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclohexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, etc.; Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, p-phenylene bis(trimellitic monoester anhydride), ethylene glycol bis(anhydrotrimellitate), 1,3-propylene glycol bis(anhydrotrimellitate), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 4,4'-biphthalic dianhydride; as well as the tetracarboxylic dianhydrides described in JP-A-2010-97188.

[0040] In terms of being able to obtain a liquid crystal alignment film with high transparency and less accumulated charge when combined with a specific diamine, the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid (P) preferably contains at least one selected from the group consisting of aliphatic tetracarboxylic acid dianhydrides and alicyclic tetracarboxylic acid dianhydrides (hereinafter also referred to as "specific acid anhydride"), and more preferably contains at least an alicyclic tetracarboxylic acid dianhydride. When a specific acid anhydride is used in the synthesis of the polyamic acid (P), the proportion of the specific acid anhydride is preferably 30 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% or more, based on the total amount of tetracarboxylic acid dianhydrides used in the synthesis. When synthesizing the polymer (P), one tetracarboxylic acid dianhydride can be used alone, or two or more tetracarboxylic acid dianhydrides can be used in combination.

[0041] When the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, the polymer (P) is a tetracarboxylic acid dianhydride having a partial structure represented by the above formula (1) (wherein, in the above formula (1), Y 1 and Y 2 may each independently be -CO-.) can also be obtained by reacting a tetracarboxylic dianhydride containing the partial structure represented by the above formula (1) with a diamine compound. Examples of the tetracarboxylic dianhydride having the partial structure represented by the above formula (1) include compounds represented by the following formulas (t-1) and (t-2). When synthesizing the polymer (P) using a tetracarboxylic dianhydride having the partial structure represented by the above formula (1), either the specific diamine or another diamine may be used as the diamine compound, or the specific diamine and another diamine may be used in combination. [ka]

[0042] (Diamine compounds) The specific diamine preferably has a partial structure represented by the above formula (2) or (3) and two primary amino groups. Preferred specific examples of the specific diamine include compounds represented by each of the following formulas (d-1) to (d-45).

[0043] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0044] Among these, the specific diamine is preferably a compound represented by each of the above formulas (d-1) to (d-27) and (d-34) to (d-40), and particularly preferably a compound represented by each of the above formulas (d-1), (d-15), (d-16), and (d-34) to (d-40).The specific diamine may be used alone or in combination of two or more.

[0045] The polymer (P) is, among others, a polymer represented by X in the above formula (5) and formula (6). 2 is preferably a polymer having a structural unit which is a divalent group represented by any one of the following formulas (x-1) to (x-4), and X in the above formulas (5) and (6) 1 is a tetravalent aliphatic hydrocarbon group, and X 2is particularly preferably a polymer having a structural unit that is a divalent group represented by any one of the following formulas (x-1) to (x-4). [ka] (In formulas (x-1) to (x-4), G 1 and G 2 are each independently -O- or -S-. 3 and Z 4 are each independently -O- or -S-. 12 and R 13 are each independently a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms. "*" represents a bond.

[0046] When synthesizing the polyamic acid (P), only the specific diamine may be used as the diamine compound, but a diamine compound different from the specific diamine (hereinafter also referred to as "other diamine") may also be used together with the specific diamine.

[0047] The other diamines are not particularly limited as long as they are diamine compounds that do not have the partial structure represented by the above formula (1), and examples thereof include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples of these include aliphatic diamines such as metaxylylenediamine, ethylenediamine, 1,3-propanediamine, tetramethylenediamine, and hexamethylenediamine; Alicyclic diamines such as p-cyclohexanediamine and 4,4'-methylenebis(cyclohexylamine); Examples of aromatic diamines include dodecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholestanyl diaminobenzoate, cholesteryl diaminobenzoate, lanostannyl diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 2,5-diamino-N,N-diallylaniline, and compounds represented by the following formula (E-1): [ka] (In formula (E-1), X I and X II are each independently a single bond, -O-, *-COO- or *-OCO- (where "*" represents X I It shows the bond with R. I is an alkanediyl group having 1 to 3 carbon atoms. II R is a single bond or an alkanediyl group having 1 to 3 carbon atoms. III is an alkyl group, alkoxy group, fluoroalkyl group, or fluoroalkoxy group having 1 to 20 carbon atoms. a is 0 or 1. b is an integer of 0 to 3. c is an integer of 0 to 2. d is 0 or 1, provided that 1≦a+b+c≦3. Side chain diamines such as compounds represented by the formula: paraphenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-ethylenedianiline, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1,2-bis(4-aminophenoxy)ethane, 1,5-bis(4-aminophenoxy)pentane, N,N'-di(4-aminophenyl)-N,N'-dimethylethylenediamine, bis[2-(4-aminophenyl)ethyl]hexanedioic acid, bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methylamine, 1,4-bis non-side chain diamines such as (4-aminophenyl)-piperazine, N,N'-bis(4-aminophenyl)-benzidine, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, and 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline; Examples of diaminoorganosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, and the diamine compounds described in JP-A-2010-97188 can also be used. In synthesizing the polyamic acid (P), the other diamines can be used alone or in combination of two or more.

[0048] From the viewpoint of obtaining sufficient transparency of the liquid crystal alignment film and the effect of reducing accumulated charge, the proportion of the specific diamine used is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total amount of diamine compounds used in the synthesis of the polyamic acid (P). Furthermore, from the viewpoint of ensuring the solubility of the polymer, the proportion of the specific diamine used is preferably 80 mol% or less, more preferably 70 mol% or less, based on the total amount of diamine compounds used in the synthesis of the polyamic acid (P).

[0049] The specific diamine can be obtained by appropriately combining standard methods in organic chemistry, such as synthesizing a dinitro intermediate having a nitro group instead of the primary amino group in the above formula (5), and then amminating the nitro group of the obtained dinitro intermediate using an appropriate reduction system.

[0050] The method for synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. For example, in the case of 9,9'-bis(4-aminophenyl)-3,3'-bicarbazole (the compound represented by the above formula (d-1)), 3,3'-bicarbazole is obtained by an oxidative coupling reaction of carbazole, and then 3,3'-bicarbazole is subjected to an aromatic nucleophilic substitution reaction with p-fluoronitrobenzene to obtain 9,9'-bis(4-nitrophenyl)-3,3'-bicarbazole as a dinitro intermediate. Next, the nitro group of the obtained dinitro intermediate is reduced to obtain the target 9,9'-bis(4-aminophenyl)-3,3'-bicarbazole. Note that the synthesis method for the specific diamine is not limited to the above.

[0051] (Synthesis of polyamic acid) The polyamic acid (P) can be obtained by reacting the above-mentioned tetracarboxylic dianhydride with a diamine compound, optionally together with a molecular weight modifier (also referred to as an end-capping agent). Examples of the molecular weight modifier include acid monoanhydrides, monoamine compounds, and monoisocyanate compounds. The ratio of the tetracarboxylic dianhydride and diamine compound used in the synthesis reaction of the polyamic acid (P) is preferably such that 0.2 to 2 molar equivalents of the acid anhydride group of the tetracarboxylic dianhydride are used per 1 molar equivalent of the amino group of the diamine compound.

[0052] The synthesis reaction of the polyamic acid (P) is preferably carried out in an organic solvent. The reaction temperature is preferably −20° C. to 150° C., and the reaction time is preferably 0.1 to 24 hours. Examples of organic solvents used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents include one or more solvents selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, and halogenated phenols, or a mixture of one or more of these solvents with other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount of organic solvent used is preferably such that the total amount of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 50% by mass relative to the total amount of the reaction solution. The reaction solution in which the polyamic acid (P) is dissolved may be used as it is for preparing a liquid crystal aligning agent, or the polyamic acid (P) contained in the reaction solution may be isolated and then used for preparing a liquid crystal aligning agent.

[0053] <Polyamic acid ester> The polyamic acid ester as the polymer (P) has a partial structure represented by the above formula (5), in which R 8 and R 9and (III) a method of reacting a tetracarboxylic acid diester dihalide with a diamine compound containing a specific diamine, preferably in an organic solvent, in the presence of a suitable dehydration catalyst (e.g., 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium halide, carbonylimidazole, a phosphorus-based condensing agent, etc.), or a method of reacting a tetracarboxylic acid diester dihalide with a diamine compound containing a specific diamine, preferably in an organic solvent, in the presence of a suitable base (e.g., a tertiary amine such as pyridine or triethylamine, or an alkali metal such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, or potassium).

[0054] The tetracarboxylic acid diester used in the above [II] can be obtained by ring-opening a tetracarboxylic acid dianhydride with an alcohol, etc. The tetracarboxylic acid diester dihalide used in the above [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. The polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. When the polyamic acid ester is obtained as a solution by the above reaction, the solution may be used for preparing a liquid crystal aligning agent as it is, or the polyamic acid ester contained in the reaction solution may be isolated and then used for preparing a liquid crystal aligning agent.

[0055] <Polyimide> The polyimide as the polymer (P) is a polymer having a partial structure represented by the above formula (6). The polyimide can be obtained, for example, by imidizing the polyamic acid (P) synthesized as described above through dehydration and cyclization. The polyimide may be a fully imidized product in which all of the amic acid structures contained in the precursor polyamic acid (P) have been dehydrated and cyclized, or a partially imidized product in which only a portion of the amic acid structures have been dehydrated and cyclized, resulting in both amic acid structures and imide ring structures. The polyimide preferably has an imidization rate of 40 to 100%, more preferably 60 to 90%. The imidization rate is the ratio, expressed as a percentage, of the number of imide ring structures to the total number of amic acid structures and imide ring structures in the polyimide. Some of the imide rings may be isoimide rings.

[0056] The dehydration ring-closing of the polyamic acid (P) is preferably carried out by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as necessary. Examples of the dehydrating agent that can be used include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent used is preferably 0.01 to 20 moles per mole of the amic acid structure of the polyamic acid. Examples of the dehydration ring-closing catalyst that can be used include tertiary amines such as pyridine, collidine, lutidine, and triethylamine. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. Examples of the organic solvent used include the organic solvents exemplified for use in synthesizing the polyamic acid (P). The reaction temperature for the dehydration ring-closing reaction is preferably 0 to 180°C, and the reaction time is preferably 1.0 to 120 hours. The reaction solution containing the polyimide thus obtained may be used as it is for the preparation of a liquid crystal aligning agent, or the polyimide may be isolated and then used for the preparation of a liquid crystal aligning agent.

[0057] <Polyurea> When the polymer (P) is a polyurea, the polyurea (hereinafter also referred to as "polyurea (P)") can be obtained, for example, by reacting a diisocyanate compound with a diamine compound containing a specific diamine.

[0058] (Diisocyanate compounds) The diisocyanate compound used in the synthesis of the polyurea (P) is not particularly limited, and specific examples of the diisocyanate compound include aliphatic diisocyanates and aromatic diisocyanates.

[0059] Specific examples of these include aliphatic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, and tetramethylethylene diisocyanate; and aromatic diisocyanates such as o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanates (e.g., 2,4-tolylene diisocyanate), 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 2,2'-bis(4-diisocyanate phenyl)propane, 4,4'-diisocyanate diphenylmethane, 4,4'-diisocyanate diphenyl ether, 4,4'-diisocyanate diphenyl sulfone, 3,3'-diisocyanate diphenyl sulfone, and 2,2'-diisocyanate benzophenone.

[0060] The solution viscosity of the polymer (P) is preferably 10 to 800 mPa·s when made into a 10% by mass solution, and more preferably 15 to 500 mPa·s. The solution viscosity (mPa·s) is a value measured at 25°C using an E-type rotational viscometer for a 10% by mass polymer solution prepared using a good solvent for the polymer (P) (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0061] The weight average molecular weight (Mw) of the polymer (P) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1,000 to 500,000, more preferably 5,000 to 100,000. The molecular weight distribution (Mw / Mn), which is the ratio of Mw to the number average molecular weight (Mn) measured by GPC in terms of polystyrene, is preferably 15 or less, more preferably 10 or less. The polymer (P) contained in the liquid crystal aligning agent may be one type alone, or two or more types may be combined.

[0062] Additives (P) The additive (P) can preferably be a low molecular weight compound having a functional group capable of forming a bond by heat or light together with the partial structure (A). Here, in this specification, the term "low molecular weight compound" refers to a compound that does not have a molecular weight distribution and is a component that is distinguished from a polymer having a repeating unit. The molecular weight of the low molecular weight compound is, for example, 1500 or less, preferably 1000 or less, and more preferably 800 or less.

[0063] Preferred specific examples of the additive (P) include compounds represented by the following formula (9) or formula (10). [ka] (In formula (9), R 1 is a halogen atom, a hydroxy group, or a monovalent organic group, or a plurality of R 1 represents a fused ring structure formed by combining together with the ring to which they are attached. 5 is a divalent organic group bonded to the fused ring structure in the formula via a carbon atom. 1 is a functional group capable of forming a bond by heat or light. 2 is a hydrogen atom, a monovalent hydrocarbon group, or a functional group capable of forming a bond by heat or light. a1 is an integer of 0 to 3. In the formula, R 1 If there are multiple R 1 are the same or different. 5are the same or different from each other. Multiple a1's in the formula are the same or different from each other. [ka] (In formula (10), R 2 is a halogen atom, a hydroxy group, or a monovalent organic group. 3 is a hydrogen atom or a monovalent organic group. 6 is a single bond or a carbon atom, oxygen atom, sulfur atom or * to the fused ring structure in the formula 5 -NR 5 It is a divalent organic group bonded by -CO-. 5 is a hydrogen atom or a monovalent organic group. 5 " represents a bond bonded to the fused ring structure in the formula. 3 is a functional group capable of forming a bond by heat or light. 4 is a hydrogen atom, a monovalent hydrocarbon group, or a functional group capable of forming a bond by heat or light. a2 is an integer of 0 to 3. In the formula, R 2 If there are multiple R 2 are the same or different. 6 are the same or different. Multiple a2's in the formula are the same or different.

[0064] In the above formulas (9) and (10), examples of the "functional group capable of forming a bond by heat or light" include an epoxy group, an alkoxysilyl group, a silanol group, a polymerizable unsaturated carbon-carbon bond-containing group (vinyl group, (meth)acryloyl group, maleimide group, R 20 OOC-CR 21 =CR 22 -CONR 23 -*(However, R 20 ~R 23 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Of these, a polymerizable unsaturated carbon-carbon bond-containing group is preferred because of its high reactivity with heat or light.

[0065] Z 2 and Z dWhen the group represented by the formula (I) is a monovalent hydrocarbon group, examples of the hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. 2 and Z 4 is preferably a functional group capable of forming a bond by heat or light, and more preferably a polymerizable unsaturated carbon-carbon bond-containing group.

[0066] Specific examples of the additive (P) include compounds represented by the following formulas (a-1) to (a-5). [ka]

[0067] <Other ingredients> The liquid crystal aligning agent of the present disclosure may further contain components other than the compound (P) (hereinafter also referred to as "other components"). Examples of other components include a polymer not having the partial structure (A) represented by the above formula (1) (hereinafter also referred to as "other polymers"), a compound having one or more epoxy groups in the molecule, a functional silane compound, a compound having one or more (meth)acryloyl groups in the molecule, an antioxidant, a metal chelate compound, a curing accelerator, a surfactant, a filler, a dispersant, a photosensitizer, an acid generator, a base generator, a radical generator, etc. The blending ratio of these components can be appropriately selected depending on each compound, as long as the effects of the present disclosure are not impaired.

[0068] <Other polymers> The main skeleton of the other polymer is not particularly limited, but examples thereof include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyenamine, polyurea, polyamide, polyamideimide, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, (meth)acrylic polymer, styrene polymer, maleimide polymer, styrene-maleimide copolymer, etc. From the viewpoint of obtaining a highly reliable liquid crystal device, the other polymer is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, and polymers containing a structural unit derived from a monomer having a polymerizable unsaturated carbon-carbon bond. Examples of polymers containing a structural unit derived from a monomer having a polymerizable unsaturated carbon-carbon bond include (meth)acrylic polymer, styrene polymer, maleimide polymer, and styrene-maleimide copolymer. As the other polymer, one type may be used alone, or two or more types may be used in combination.

[0069] When the compound (P) is a polymer and other polymers are contained in the liquid crystal aligning agent together with the polymer (P), the content of the other polymers is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total amount of the polymer (P) and the other polymers, and is preferably 95% by mass or less, more preferably 90% by mass or less, based on the total amount of the polymer (P) and the other polymers.

[0070] When the compound (P) is an additive component, the liquid crystal aligning agent of the present disclosure contains a polymer component together with the additive (P). When the polymer component is another polymer, the content of the other polymer is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on the total amount of the solid components of the liquid crystal aligning agent (i.e., components other than the solvent contained in the liquid crystal aligning agent). Furthermore, the content of the other polymer is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 95% by mass or less, based on the total amount of the solid components of the liquid crystal aligning agent.

[0071] <Solvent> The liquid crystal aligning agent of the present disclosure is preferably prepared as a liquid composition in which the compound (P) and other components used as needed are dispersed or dissolved in a suitable solvent.

[0072] Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, and ethylene glycol-i-propyl ether. ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. These may be used alone or in combination of two or more.

[0073] The solids concentration in the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected taking into consideration viscosity, volatility, etc., but is preferably in the range of 1 to 10 mass%. That is, the liquid crystal aligning agent is applied to the surface of a substrate as described below, and preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that will become a liquid crystal alignment film. In this case, a solids concentration of 1 mass% or more is preferable because it ensures a sufficient coating film thickness and makes it easy to obtain a good liquid crystal alignment film. Furthermore, a solids concentration of 10 mass% or less allows the coating film to have an unduly thick thickness, thereby making it possible to obtain a good liquid crystal alignment film, and also ensures an appropriate viscosity of the liquid crystal aligning agent, resulting in good applicability.

[0074] When the compound (P) is a polymer, the content of the compound (P) in the liquid crystal aligning agent is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the total solid components (components other than the solvent) in the liquid crystal aligning agent, from the viewpoint of fully obtaining the effects of blending the polymer (P). When the compound (P) is an additive, the blending ratio of the additive (P) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, relative to 100 parts by mass of the total solid components in the liquid crystal aligning agent. Furthermore, from the viewpoint of ensuring the liquid crystal alignment properties and electrical properties of the liquid crystal alignment film, the blending ratio of the additive (P) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, relative to 100 parts by mass of the total solid components in the liquid crystal aligning agent.

[0075] <Liquid crystal alignment film and liquid crystal element> The liquid crystal alignment film of the present disclosure is formed using the liquid crystal alignment agent prepared as described above. Furthermore, the liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, and various modes such as TN (Twisted Nematic), STN (Super Twisted Nematic), VA (Vertical Alignment) (including VA-MVA, VA-PVA, etc.), IPS (In-Plane Switching), FFS (Fringe Field Switching), and OCB (Optically Compensated Bend) can be applied. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, different substrates are used depending on the desired operation mode. Steps 2 and 3 are common to all operation modes.

[0076] (Step 1: Formation of coating film) First, a liquid crystal alignment agent is applied to a substrate, and the coated surface is preferably heated to form a coating film on the substrate. Examples of substrates that can be used include transparent substrates made of glass, such as float glass or soda glass; or plastics, such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly(alicyclic olefin). Examples of transparent conductive films that can be provided on one side of the substrate include NESA films (registered trademarks of PPG, Inc., USA) made of tin oxide (SnO2) and ITO films made of indium oxide-tin oxide (In2O3-SnO2). When manufacturing TN, STN, VA, or PSA liquid crystal devices, two substrates with patterned transparent conductive films are used. On the other hand, when manufacturing IPS or FFS liquid crystal devices, one substrate is provided with electrodes made of a comb-shaped patterned transparent conductive film or metal film, and another substrate with no electrodes is used. Examples of metal films that can be used include films made of metals such as chromium. The liquid crystal alignment agent is applied to the substrate on the electrode-forming surface, preferably by offset printing, spin coating, roll coating or inkjet printing.

[0077] After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably performed to prevent dripping of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30 to 200°C, and the pre-baking time is preferably 0.25 to 10 minutes. Thereafter, the solvent is completely removed, and if necessary, a baking (post-baking) step is performed to thermally imidize the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time is preferably 80 to 300°C, and the post-baking time is preferably 5 to 200 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm. After applying the liquid crystal aligning agent to the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film that will become a liquid crystal alignment film.

[0078] (Step 2: Alignment treatment) When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal device, the coating film formed in step 1 above is subjected to a treatment (alignment treatment) to impart liquid crystal alignment ability. This imparts the ability to align liquid crystal molecules to the coating film, turning it into a liquid crystal alignment film. As the alignment treatment, a rubbing treatment in which the surface of the coating film formed on the substrate is rubbed with cotton or the like, or a photo-alignment treatment in which the coating film is irradiated with light to impart liquid crystal alignment ability, is preferably used. When manufacturing a vertical alignment type liquid crystal device, the coating film formed in step 1 above may be used as a liquid crystal alignment film as is, or the coating film may be subjected to an alignment treatment to further enhance the liquid crystal alignment ability.

[0079] The light irradiation in the photo-alignment treatment can be performed by irradiating the coating film after the post-bake step, irradiating the coating film after the pre-bake step but before the post-bake step, or irradiating the coating film while it is being heated in at least one of the pre-bake and post-bake steps. In the photo-alignment treatment, the radiation to be irradiated to the coating film can be, for example, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm. Preferably, ultraviolet light containing light with a wavelength of 200 to 400 nm is used. When the radiation is polarized, it may be linearly polarized or partially polarized. Furthermore, when the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these. When irradiating with unpolarized radiation, the irradiation direction is an oblique direction.

[0080] Examples of light sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, and excimer lasers. The radiation dose is preferably 400 to 20,000 J / m 2 and more preferably 1,000 to 5,000 J / m 2 The coating film may be irradiated with light while being heated in order to enhance the reactivity.

[0081] In producing a liquid crystal alignment film, the coating film that has been subjected to light irradiation treatment may be heated within a temperature range of 120°C or higher and 280°C or lower. Such a heat treatment is preferable in that it further improves the liquid crystal alignment (thermal realignment) and allows for the production of a liquid crystal device with reduced AC afterimages. This heating may be post-baking, or may be a heat treatment carried out separately from or after post-baking. The heating temperature is preferably 140°C or higher, more preferably 150°C to 250°C, from the viewpoint of promoting realignment of molecular chains by heating. The heating time is preferably 5 to 200 minutes, more preferably 10 to 60 minutes.

[0082] The production of a liquid crystal alignment film may further include a contacting step of contacting the light-irradiated coating film with water, a water-soluble organic solvent, or a mixed solvent of water and a water-soluble organic solvent. Examples of water-soluble organic solvents include methanol, ethanol, 1-propanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone. Methods for contacting the coating film with the solvent include, but are not limited to, spraying, showering, immersion, and puddling. The contact time between the coating film and the solvent is not particularly limited, but is, for example, 5 seconds to 15 minutes. The coating film may be heat-treated after the contacting step.

[0083] (Step 3: Construction of liquid crystal cell) Two substrates with liquid crystal alignment films formed thereon are prepared as described above, and a liquid crystal cell is fabricated by disposing a liquid crystal between the two opposing substrates. Examples of methods for fabricating a liquid crystal cell include: (1) placing the two substrates facing each other with a spacer between them so that the liquid crystal alignment films face each other, bonding the peripheries of the two substrates together using a sealant, injecting liquid crystal into the substrate surfaces and the cell gap defined by the sealant, and then sealing the injection hole; and (2) applying a sealant to a predetermined location on one of the substrates with a liquid crystal alignment film, dropping liquid crystal onto several predetermined locations on the liquid crystal alignment film, and then bonding the other substrate so that the liquid crystal alignment film faces the other substrate, while spreading the liquid crystal over the entire surface of the substrate (ODF method). It is desirable to further heat the fabricated liquid crystal cell to a temperature at which the liquid crystal used assumes an isotropic phase and then slowly cool it to room temperature to remove flow alignment that occurs during liquid crystal filling.

[0084] The sealing agent may be, for example, an epoxy resin containing a hardener and aluminum oxide spheres as spacers, such as photospacers and bead spacers.

[0085] The liquid crystal may be either positive or negative. The use of negative liquid crystal in IPS and FFS liquid crystal elements is preferred because it reduces transmission loss above the electrode and improves contrast. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, with nematic liquid crystals being preferred. Examples of nematic liquid crystals include Schiff-based liquid crystals, azoxy-based liquid crystals, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, and cubane-based liquid crystals. These liquid crystals may also be used with the addition of, for example, cholesteric liquid crystals, chiral agents, or ferroelectric liquid crystals.

[0086] In the PSA mode, a polymerizable compound (e.g., a polyfunctional (meth)acrylate compound) is filled into the cell gap together with liquid crystal to construct a liquid crystal cell, and then the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of a pair of substrates. In producing a PSA type liquid crystal element, the proportion of the polymerizable compound used is, for example, 0.01 to 3 parts by mass, preferably 0.1 to 1 part by mass, per 100 parts by mass of the total liquid crystal.

[0087] Next, if necessary, a polarizing plate is attached to the outer surface of the liquid crystal cell. Examples of polarizing plates include a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine, sandwiched between cellulose acetate protective films, or a polarizing plate made of the H film itself. This produces a liquid crystal device.

[0088] The liquid crystal element of the present disclosure can be effectively applied to various uses, for example, various display devices such as watches, portable game machines, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays, as well as light control films, etc. Furthermore, a liquid crystal element formed using the liquid crystal aligning agent of the present disclosure can also be applied to optical films such as retardation films. [Example]

[0089] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0090] <Compound structure and abbreviation> The structures and abbreviations of the main compounds used in the following examples are as follows: [Tetracarboxylic acid dianhydride] TA-1; 1,2,3,4-Cyclobutanetetracarboxylic dianhydride TA-2; (1R,2R,3S,4S)-1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid dianhydride TA-3; 2,3,5-tricarboxycyclopentylacetic dianhydride TA-4; Pyromellitic dianhydride TA-5; 4,4'-biphthalic dianhydride [ka]

[0091] [Diamine] DA-1; 9,9'-bis(4-aminophenyl)-3,3'-bicarbazole DA-2; 9,9'-bis(4-(4-aminophenoxy)phenyl)-3,3'-bicarbazole DA-3; 9,9'-diethyl-6,6'-bis(4-aminophenoxy)-3,3'-bicarbazole DA-4; 9,9'-diethyl-3,3'-bicarbazole-6,6'-diamine DA-5; 4,4'-diaminodiphenylamine DA-6; 3,6-diaminocarbazole DA-7; 4,4'-diaminotriphenylamine DA-8; N4,N4'-bis(4-aminophenyl)-N4,N4'-dimethylbenzidine DA-9; 4,4'-diaminodiphenylmethane DA-10; 3,5-diaminobenzoic acid DA-11; 4,4'-bis(4-aminophenoxy)biphenyl DA-12; 2,2-bis(4-(4-aminophenoxy)phenyl)propane DA-13; 2,2'-dimethylbenzidine DA-14; 5(6)-amino-1,3,3-trimethyl-1-(4-aminophenyl)indan DA-15; N,N'-bis(5-aminopyridin-2-yl)-N,N'-di(tert-butoxycarbonyl)ethylenediamine DA-16; N1,N6-bis(4-aminophenethyl)-N1,N6-di(tert-butoxycarbonyl)adipamide DA-17; 5ξ-Cholestan-3-yl 2,4-diaminophenyl ether [ka] [ka] [ka]

[0092] [solvent] NMP; N-methyl-2-pyrrolidone NEP; N-ethyl-2-pyrrolidone GBL; gamma-butyrolactone BC: Butyl cellosolve DAA; Diacetone alcohol DEDG: Diethylene glycol diethyl ether

[0093] [Additives] AD-1: N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane AD-2;3-Glycidyloxypropyltriethoxysilane AD-3: Dipentaerythritol hexaacrylate AD-4; 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(3-glycidyloxypropyl)-1,3,5,7,2,4,6,8-tetraoxatetrasilocane AD-5: A compound represented by the following formula (AD-5): [ka]

[0094] [ka]

[0095] <Synthesis of Compounds> [Synthesis Example 1] 3,3'-bicarbazole (3.0 mmol), p-fluoronitrobenzene (7.5 mmol), potassium carbonate (12 mmol), and NMP (20 mL) were placed in a three-neck flask equipped with a nitrogen inlet tube and stirred under nitrogen at 160°C for 6 hours. After the reaction was completed, the reaction solution was poured into water to precipitate the product. The resulting precipitate was washed with water and ethyl acetate and dried under vacuum to obtain a yellow-brown solid compound represented by the following formula (DA-1-1) in a 90% yield. Compound (DA-1-1) (2.0 mmol), 5% Pd / C (0.23 g), hydrazine monohydrate (1.15 g), and NMP (20 mL) were placed in a three-necked flask equipped with a nitrogen inlet tube and stirred at 80°C under nitrogen for 6 hours. After the reaction was completed, the reaction solution was filtered through Celite, ethyl acetate was added, and the mixture was separated and washed with water. The organic phase was concentrated under reduced pressure to obtain a brown solid, 9,9'-bis(4-aminophenyl)-3,3'-bicarbazole (the diamine represented by the above formula (DA-1)), in an 80% yield. Figures 1 and 2 show the structure of diamine (DA-1). 1 H-NMR spectrum (DMSO-d6, 400 MHz) and 13 The results of measuring the C-NMR spectrum (DMSO-d6, 75 MHz) are shown. [ka]

[0096] [Synthesis Example 2] According to the following reaction scheme, in the same manner as in Synthesis Example 1, 9,9'-bis(4-(4-aminophenoxy)phenyl)-3,3'-bicarbazole (diamine represented by the above formula (DA-2)) was obtained. [ka]

[0097] [Synthesis Example 3] According to the following reaction scheme, 9,9'-diethyl-6,6'-bis(4-aminophenoxy)-3,3'-bicarbazole (diamine represented by the above formula (DA-3)) was obtained in the same manner as in Synthesis Example 1. The compound represented by the following formula (DA-3-1) was synthesized according to a known literature (Journal of Photochemistry and Photobiology A: Chemistry (2004), 162, 187-191). [ka]

[0098] [Synthesis Example 4] According to the following reaction scheme, 9,9'-diethyl-3,3'-bicarbazole-6,6'-diamine (diamine represented by the above formula (DA-4)) was obtained in the same manner as in Synthesis Example 1. The compound represented by the following formula (DA-4-1) was synthesized according to a known literature (Journal of Organic Chemistry (2019), 84, 73-93). [ka]

[0099] <Synthesis and evaluation of polymers> Polymers were synthesized in the following Synthesis Examples 5 to 25. In the following examples, the weight average molecular weight M w and number average molecular weight M nThe imidization rate of the polyimide in the polymer solution, the solution viscosity of the polymer solution, and the epoxy equivalent were measured by the following methods. [Weight average molecular weight M w and number average molecular weight M n ] In Synthesis Examples 24 and 25, M w and M n is a polystyrene equivalent value measured by GPC under the following conditions. Column: TSKgel GRCXLII, manufactured by Tosoh Corporation Solvent: tetrahydrofuran Temperature: 40℃ Pressure: 68kgf / cm 2

[0100] [Imidization rate of polyimide] The polyimide solution was poured into pure water, and the resulting precipitate was thoroughly dried under reduced pressure at room temperature. After that, it was dissolved in deuterated dimethyl sulfoxide and measured at room temperature using tetramethylsilane as a standard substance. 1 H-NMR was measured. 1 The imidization rate [%] was calculated from the H-NMR spectrum (400 MHz) using the following formula (1). Imidization rate [%] = (1 - (A1 / (A2 × α))) × 100 ... (1) (In formula (1), A1 is the peak area derived from the protons of the amide group appearing at a chemical shift of approximately 10 ppm, A2 is the peak area derived from the protons of the aromatic group appearing at a chemical shift of approximately 6 to 9 ppm, and α is the ratio of the number of protons of the aromatic group to one proton of the amide group in the polymer precursor (polyamic acid).) [Solution viscosity of polymer solution] The solution viscosity (mPa·s) of the polymer solution was measured at 25°C using an E-type rotational viscometer. [Epoxy equivalent] The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

[0101] [Synthesis Example 5] Diamine (20 molar parts of diamine (DA-1) and 80 molar parts of diamine (DA-9)) was dissolved in NMP, and 0.95 molar equivalents of tetracarboxylic dianhydride (TA-1) relative to the total amount of diamine was added. The reaction was carried out at room temperature for 6 hours to obtain a 15% by mass solution of polyamic acid (PI-1) having a partial structure represented by the following formula (PI-1). [ka]

[0102] [Synthesis Examples 6 to 22] Polyamic acids (PI-2 to PI-18) were obtained in the same manner as in Synthesis Example 5, except that the types and molar ratios of the tetracarboxylic dianhydrides and diamines were changed as shown in Table 1. Note that the values ​​in Table 1 indicate the proportion (mol %) of each compound used relative to the total amount (100 mol %) of the dianhydrides used in the synthesis, and the values ​​in Table 1 indicate the proportion (mol %) of each compound used relative to the total amount (100 mol %) of the diamines used in the synthesis.

[0103] [Synthesis Example 23] Diamines (50 molar parts of diamine (DA-15) and 50 molar parts of diamine (DA-13)) were dissolved in NMP, and 0.95 molar equivalents of tetracarboxylic dianhydride (TA-2) based on the total amount of diamines was added. The reaction was carried out at room temperature for 6 hours to obtain a polyamic acid solution. To the resulting solution, 0.80 molar equivalents of 1-methylpiperidine and acetic anhydride based on the carboxyl groups of the polyamic acid were added as dehydrating agents, and the mixture was heated and stirred at 60°C for 3 hours. The resulting solution was repeatedly concentrated under reduced pressure and diluted with NMP to obtain a 10% by mass solution of polyimide (PI-19) having a partial structure represented by the following formula (PI-19). The imidization rate of polyimide (PI-19) was 78%. [ka]

[0104] [Table 1]

[0105] [Synthesis Example 24] A reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux condenser was charged with 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (a compound represented by the following formula (S-1)), 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine, and mixed at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was stirred under reflux at 80°C for 6 hours. After the reaction was completed, the organic layer was removed and washed with a 0.2% by mass aqueous solution of ammonium nitrate until the water after washing was neutral. The solvent and water were then distilled off under reduced pressure, yielding an epoxy-containing polyorganosiloxane (ESSQ-1) as a viscous, transparent liquid. Regarding polyorganosiloxane (ESSQ-1), 1 H-NMR analysis revealed a peak due to the epoxy group at a chemical shift (δ) of approximately 3.2 ppm, confirming that no side reactions of the epoxy group occurred during the reaction. The weight-average molecular weight M of the resulting polyorganosiloxane (ESSQ-1) was w The epoxy equivalent was 180 g / mol. A 200 mL three-neck flask was charged with 10.0 g of polyorganosiloxane (ESSQ-1), 30.28 g of methyl isobutyl ketone as a solvent, and modified components (carboxylic acids) of the compound represented by the following formula (S-2) and the compound represented by the following formula (S-3), in amounts corresponding to 20 mol% and 10 mol%, respectively, relative to the total amount of epoxy groups possessed by the polyorganosiloxane (ESSQ-1). Also, 0.10 g of UCAT 18X ​​(trade name, manufactured by San-Apro Co., Ltd.) was added as a catalyst, and the reaction was carried out at 100 °C for 48 hours with stirring. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the resulting solution was washed three times with water. The organic layer was dried using magnesium sulfate, and the solvent was then distilled off to obtain a polyorganosiloxane (PSQ-1) containing an orienting group. The weight-average molecular weight M of the resulting polymer was 1.0 mol. w was 8000. [ka]

[0106] [Synthesis Example 25] Under nitrogen, 6.38 g of the compound represented by the following formula (M-1), 1.90 g of 4-(glycidyloxymethyl)styrene (a compound represented by the following formula (M-2)), and 0.86 g of methacrylic acid were added to a 100 mL two-neck flask as polymerization monomers, 0.46 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator, and 40 mL of N-methyl-2-pyrrolidone (NMP) as a solvent, and the mixture was polymerized at 70 °C for 6 hours. After reprecipitation in methanol, the precipitate was filtered and dried in vacuum at room temperature for 8 hours to obtain the target polymer (PMI-1). The weight-average molecular weight M measured in terms of polystyrene by GPC was 0.46 g. w is 30,000, molecular weight distribution M w / M n was 2. [ka]

[0107] <Preparation and Evaluation of Liquid Crystal Alignment Agent> [Example 1: Photo-aligned FFS-type liquid crystal display element] (1) Preparation of liquid crystal alignment agent The polymer components (solid content: 80 parts by mass of polymer (PI-1) and 20 parts by mass of polymer (PI-19)) were diluted with NMP, GBL, and BC to obtain a solution with a solid content of 4.0% by mass and a solvent composition ratio of NMP:GBL:BC = 50:25:25 (mass ratio). This solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal alignment agent (AL-1).

[0108] (2) Evaluation of optical properties (transparency) The liquid crystal alignment agent (AL-1) prepared in (1) above was applied to a quartz substrate using a spin coater, heated on a hot plate at 80°C for 1 minute, and then heated in a nitrogen-purged oven at 230°C for 30 minutes to form a coating film with an average thickness of 100 nm. The quartz substrate on which this coating film was formed was subjected to absorption spectrum measurement in the ultraviolet-visible-near-infrared region using a UV-Vis-NIR spectrophotometer (manufactured by JASCO Corporation, product name "V-670"), with a quartz substrate of the same type without a coating film as a reference. The effects of reflection were suppressed by using P-polarized light through a polarizing filter and setting the incident angle to the substrate at Brewster's angle. A transmittance of 98% or higher at a wavelength of 400 nm was rated "good," and a transmittance of less than 98% was rated "poor." As a result, this example was rated "good."

[0109] (3) Formation of liquid crystal alignment film by photoalignment method The liquid crystal alignment agent (AL-1) prepared in (1) above was applied to each surface of a glass substrate having a flat electrode, an insulating layer, and a comb-shaped electrode laminated in this order on one side, and an opposing glass substrate having no electrode, using a spin coater. The applied coating was then heated on a hot plate at 80°C for 1 minute, and then heated in an oven at 230°C with the interior substituted with nitrogen for 30 minutes, forming a coating film with an average thickness of 100 nm. The surface of this coating film was irradiated with 300 mJ / cm2 of linearly polarized ultraviolet light containing a 254 nm emission line using an Hg-Xe lamp. 2 The coating film subjected to this photo-alignment treatment was then heat-treated in a nitrogen-substituted oven at 230°C for 30 minutes to form a liquid crystal alignment film.

[0110] (4) Manufacturing of FFS type liquid crystal display elements An epoxy resin adhesive containing 3.5 μm diameter aluminum oxide spheres was dispensed onto the outer periphery of the liquid crystal alignment film-bearing surface of one of the substrates prepared in (3) above, leaving a liquid crystal injection port. The pair of substrates were then placed face-to-face with their liquid crystal alignment film-bearing surfaces facing each other and pressed together so that the alignment treatment directions of each substrate were antiparallel. The adhesive was then thermally cured at 150°C for 1 hour. Next, negative nematic liquid crystal (Merck, MJ20195NCMP) was filled into the gap between the substrates through the liquid crystal injection port, which was then sealed with an epoxy adhesive. The substrate was then heated to 120°C and slowly cooled to room temperature to eliminate flow alignment during liquid crystal injection. Next, polarizers were attached to both outer surfaces of the substrates so that their polarization directions were perpendicular to each other and at a 45° angle to the alignment treatment direction of the liquid crystal alignment film, producing an FFS-mode liquid crystal display device.

[0111] (5) Evaluation of DC image retention characteristics The liquid crystal display device fabricated in (4) above was placed in an environment of 25°C and 1 atmosphere. It was driven at intermediate tones using a 30 Hz square wave (AC) to set the luminance difference between any two pixels to zero. Then, while driving with AC, 1 V direct current (DC) was applied to only one pixel for 30 minutes to accumulate charge. When the application of 1 V DC was terminated and the device was returned to AC-only driving, a luminance difference ΔL between the two pixels was generated due to the accumulated charge. The change in this luminance difference ΔL over time was observed, and the time from the end of application of 1 V DC until the luminance difference ΔL divided by the average luminance of the two pixels fell below 2% was defined as the image retention time. The shorter this time, the less likely image retention caused by the application of DC voltage. An image retention time of less than 10 minutes was rated "excellent," a time between 10 and 20 minutes was rated "good," and a time of 20 minutes or more was rated "poor." As a result, this example was rated "excellent."

[0112] [Examples 2 to 12, Comparative Examples 1 to 4] In the above Example 1, except that the components contained in the liquid crystal alignment agent were changed as shown in the following Table 2, a liquid crystal alignment agent was prepared and a liquid crystal alignment film was formed by a photoalignment method in the same manner as in Example 1, and an FFS-type liquid crystal display element was manufactured and various evaluations were performed. The evaluation results are shown in the following Table 2.

[0113] [Example 13: Rubbed alignment FFS type liquid crystal display element] (1) Preparation of liquid crystal alignment agent The polymer components (solid content: 70 parts by mass of polymer (PI-1) and 30 parts by mass of polymer (PI-18)) were diluted with NMP, GBL, DAA, and BC to obtain a solution with a solid content of 4.0% by mass and a solvent composition ratio of NMP:GBL:DAA:BC = 30:30:30:10 (mass ratio). This solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal alignment agent (AL-17).

[0114] (2) Evaluation of optical properties (transparency) The liquid crystal aligning agent (AL-17) prepared in (1) above was evaluated for transparency in the same manner as in Example 1. As a result, the transparency of this example was evaluated as "good." (3) Formation of liquid crystal alignment film by rubbing method The liquid crystal alignment agent (AL-17) prepared in (1) above was applied to a glass substrate having a flat electrode, an insulating layer, and a comb-shaped electrode laminated in this order on one side, and to a counter glass substrate without an electrode, using a spin coater. The substrate was then heated on a hot plate at 80°C for 1 minute, followed by heating in a nitrogen-purged oven at 230°C for 30 minutes to form a coating film with an average thickness of 100 nm. The surface of this coating film was then rubbed twice using a rubbing machine equipped with a roll wrapped around a nylon cloth at a roll rotation speed of 1000 rpm, a stage movement speed of 30 mm / sec, and a pile depth of 0.3 mm. The rubbed coating film was then ultrasonically cleaned in ultrapure water for 1 minute and then dried in an oven at 100°C for 10 minutes to form a liquid crystal alignment film. (4) Manufacturing of FFS type liquid crystal display elements An FFS-mode liquid crystal display element was produced in the same manner as in Example 1 using a pair of substrates having the liquid crystal alignment film prepared in (3) above. (5) Evaluation of DC image retention characteristics The FFS-type liquid crystal display element manufactured in (4) above was evaluated for DC afterimage characteristics in the same manner as in Example 1. As a result, the present example was evaluated as "excellent."

[0115] [Examples 14 to 15 and Comparative Examples 5 to 6] In the above Example 13, except that the components contained in the liquid crystal alignment agent were changed as shown in the following Table 2, a liquid crystal alignment agent was prepared and a liquid crystal alignment film was formed by a rubbing method in the same manner as in Example 13, and an FFS-type liquid crystal display element was manufactured and various evaluations were performed. The evaluation results are shown in the following Table 2.

[0116] [Example 16: PSA type liquid crystal display element] (1) Preparation of liquid crystal alignment agent The polymer components (solid content: 95 parts by mass of polymer (PI-13) and 5 parts by mass of polymer (PSQ-1)) were diluted with NMP and BC to obtain a solution with a solid content of 4.0% by mass and a solvent composition ratio of NMP:BC = 50:50 (mass ratio). This solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal alignment agent (AL-22).

[0117] (2) Preparation of liquid crystal composition A liquid crystal composition (LC-1) was obtained by adding 5% by mass of a liquid crystal compound represented by the following formula (L-1) and 0.3% by mass of a photopolymerizable compound represented by the following formula (L-2) to 10 g of nematic liquid crystal (MLC-6608, manufactured by Merck). [ka]

[0118] (3) Evaluation of optical properties (transparency) The liquid crystal aligning agent (AL-22) prepared in (1) above was evaluated for transparency in the same manner as in Example 1. As a result, the transparency of this example was evaluated as "good." (4) Formation of liquid crystal alignment film The liquid crystal alignment agent (AL-22) prepared in (1) above was applied to the electrode surface of each of two glass substrates with slit-shaped ITO electrodes using a spin coater. The substrate was then heated on a hot plate at 80°C for 1 minute, and then heated in a nitrogen-purged oven at 230°C for 30 minutes to form a coating film with an average thickness of 100 nm. This coating film was ultrasonically cleaned in ultrapure water for 1 minute and then dried in an oven at 100°C for 10 minutes to form a liquid crystal alignment film. The electrode pattern used was the same as the electrode pattern in the PSA mode.

[0119] (5) Manufacturing of PSA type liquid crystal display elements An epoxy resin adhesive containing 3.5 μm diameter aluminum oxide spheres was dispensed onto the outer periphery of the surface of one of the substrates prepared in (4) above, bearing the liquid crystal alignment film, leaving a liquid crystal injection port, and then the pair of substrates were stacked with the surfaces bearing the liquid crystal alignment film facing each other and pressed together, and the adhesive was thermally cured for 1 hour at 150° C. Next, the liquid crystal composition (LC-1) prepared in (2) above was filled into the gap between the substrates through the liquid crystal injection port, and the liquid crystal injection port was sealed with an epoxy adhesive to produce a liquid crystal cell. A 10 V AC voltage with a frequency of 60 Hz was applied between the electrodes of the obtained liquid crystal cell, and while the liquid crystal was in a driving state, ultraviolet light was irradiated at 10,000 mJ / cm using an ultraviolet light irradiation device with a metal halide lamp as the light source. 2 The exposure dose was measured using an actinometer with a wavelength of 365 nm as the reference. Next, polarizing plates were attached to both outer surfaces of the substrate so that their polarization directions were perpendicular to each other and formed an angle of 45° with the alignment treatment direction of the liquid crystal alignment film, thereby producing a PSA-type liquid crystal display element. (6) Evaluation of DC image retention characteristics The liquid crystal display element manufactured in (5) above was evaluated for DC afterimage characteristics in the same manner as in Example 1. As a result, the liquid crystal display element in this example was evaluated as "excellent."

[0120] [Example 17] In the same manner as in Example 16, except that the components contained in the liquid crystal alignment agent were changed as shown in the following Table 2, a liquid crystal alignment agent was prepared, a liquid crystal alignment film was formed, and a PSA-type liquid crystal display element was manufactured and various evaluations were performed. The evaluation results are shown in Table 2 below.

[0121] [Example 18: Photo-aligned VA-type liquid crystal display element] (1) Preparation of liquid crystal alignment agent The polymer and additive components (solid content: 85 parts by mass of polymer (PI-15), 10 parts by mass of polymer (PMI-1), and 5 parts by mass of additive (AD-4)) were diluted with NMP, GBL, DEDG, and BC to obtain a solution with a solid content of 4.0% by mass and a solvent composition ratio of NMP:GBL:DEDG:BC = 30:30:30:10 (mass ratio). This solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal alignment agent (AL-24).

[0122] (2) Evaluation of optical properties (transparency) The liquid crystal aligning agent (AL-24) prepared in (1) above was evaluated for transparency in the same manner as in Example 1. As a result, the transparency of this example was evaluated as "good." (3) Formation of liquid crystal alignment film by photoalignment method The liquid crystal alignment agent (AL-24) prepared in (1) above was applied to the electrode surface of each of two glass substrates having ITO electrodes using a spin coater, heated on a hot plate at 80°C for 1 minute, and then heated in an oven at 230°C with nitrogen purging for 30 minutes to form a coating film with an average thickness of 100 nm. A Hg-Xe lamp was used to irradiate the surface of this coating film with 20 mJ / cm of linearly polarized ultraviolet light containing a 313 nm emission line. 2 The liquid crystal alignment film was formed by irradiating the substrate with the light from a direction tilted by 40° from the normal to the substrate. (4) Manufacture of VA type liquid crystal display elements An epoxy resin adhesive containing 3.5 μm diameter aluminum oxide spheres was dispensed onto the outer periphery of the surface of one of the substrates prepared in (3) above, bearing the liquid crystal alignment film, leaving a liquid crystal injection port.Then, the surfaces of the pair of substrates bearing the liquid crystal alignment film were placed facing each other and pressed together so that the projection directions of the ultraviolet light axes of each substrate onto the substrate surface were antiparallel, and the adhesive was thermally cured at 150°C for 1 hour. Next, negative nematic liquid crystal (MLC-6608, manufactured by Merck) was filled into the gap between the substrates through the liquid crystal filling port, which was then sealed with an epoxy adhesive. To eliminate flow alignment during liquid crystal injection, the substrate was heated to 120°C and then slowly cooled to room temperature. Polarizing plates were then attached to both outer surfaces of the substrates so that their polarization directions were perpendicular to each other and at a 45° angle with the alignment treatment direction of the liquid crystal alignment film, producing a VA-type liquid crystal display device. (5) Evaluation of DC image retention characteristics The liquid crystal display element manufactured in (4) above was evaluated for DC afterimage characteristics in the same manner as in Example 1. As a result, the liquid crystal display element in this example was evaluated as "good."

[0123] [Example 19] In the same manner as in Example 18, except that the components contained in the liquid crystal alignment agent were changed as shown in the following Table 2, a liquid crystal alignment agent was prepared, a liquid crystal alignment film was formed by a photoalignment method, and a VA-type liquid crystal display element was manufactured and various evaluations were performed. The evaluation results are shown in Table 2 below.

[0124] [Table 2]

[0125] In Table 2, the mass ratio of each component of the liquid crystal alignment agent indicates the blending ratio (parts by mass) of each compound relative to 100 parts by mass of the total of the polymer components and additive components used in preparing the liquid crystal alignment agent.

[0126] As shown in Table 2, the liquid crystal aligning agents of Examples 1 to 19 containing polymer (P) had a "good" optical property (transparency) of the liquid crystal alignment film and an "excellent" or "good" DC afterimage characteristic of the liquid crystal display element, showing a good balance of various properties. In contrast, the liquid crystal aligning agents of Comparative Examples 1 to 6 not containing polymer (P) had a "poor" optical property (transparency) of the liquid crystal alignment film and / or an "poor" DC afterimage characteristic of the liquid crystal display element, showing inferior properties to the Examples.

[0127] Here, the results of Examples 1 to 19 and Comparative Examples 1 to 6 will be considered. The liquid crystal aligning agents of Examples 1 to 19 contain a polymer (P) having a partial structure (A). The fused ring skeleton of the partial structure (A) has a low ionization potential, and the cyclic structure facilitates in-plane alignment of molecular chains (π-π stacking) in a solid. Therefore, when formed into a liquid crystal alignment film, it is presumed that intermolecular hopping conduction is promoted, and charge (hole) transport properties are likely to be enhanced. Therefore, when formed into a liquid crystal display device, accumulated charges are likely to be relaxed, improving DC image retention characteristics.

[0128] Furthermore, in the polymer (P), the partial structure (A) tends to have a bent or twisted structure at the site adjacent to the fused ring. Therefore, in the fused ring skeleton in the partial structure (A), the π-conjugated system of the fused ring is unlikely to extend to the adjacent site, making it difficult to absorb light in the visible light region. This is thought to result in improved optical properties (transparency) when the partial structure (A) is used as a liquid crystal alignment film. Additionally, because the fused ring skeleton in the partial structure (A) tends to have a bent or twisted structure with the adjacent site, the fused ring in the partial structure (A) has low crystallinity despite its high planarity. When the partial structure (A) is used as a diamine or polymer, it exhibits excellent solubility in various solvents, and when used as a liquid crystal alignment agent, it is thought to exhibit excellent coating properties (spin coating, inkjet printing, offset printing) and storage stability.

[0129] Furthermore, polymer (P) is unlikely to absorb light in the visible light range, and its electrical properties (dielectric constant, resistivity, etc.) change little under backlight irradiation, so it is thought that when used in a liquid crystal display device, it will be easy to suppress charge accumulation and flicker. Furthermore, it is thought that it will be possible to suppress deterioration of the liquid crystal alignment film when irradiated with a high-brightness backlight, and to obtain a liquid crystal display device with excellent long-term reliability and suppressed deterioration of DC afterimage characteristics.

[0130] On the other hand, the liquid crystal aligning agents of Comparative Examples 1 to 3 and 5 had "poor" DC afterimage characteristics. This is presumably due to their high ionization potential and low charge transportability in the liquid crystal alignment film. Furthermore, the liquid crystal aligning agents of Comparative Examples 1, 2 and 5 had "poor" optical properties (transparency). This is presumably due to the liquid crystal alignment films obtained using the polymers (PI-5) and (PI-6) being prone to oxidative degradation, resulting in poor transparency. The liquid crystal aligning agents of Comparative Examples 4 and 6 had "poor" optical properties (transparency). This is presumably due to the π-conjugated system easily extending throughout the repeating unit, making them more easily excited by lower-energy light and more easily absorbing light in the visible light region.

[0131] <Evaluation of polymers by quantum chemical calculations> [Example 20] The properties of polyimide (polymer represented by formula (PI-20) below) obtained by polycondensation of tetracarboxylic dianhydride (TA-1) and diamine (DA-1) were evaluated by quantum chemical calculation of its repeating unit, bissuccinimide represented by formula (SI-1) below. Calculations were performed using density functional theory (DFT) with Gaussian 16 (Revision B.01) manufactured by Gaussian Corporation, USA, as the quantum chemical calculation program. [ka]

[0132] (1) Evaluation of HOMO level and DC lag characteristics The most stable structure of bissuccinimide (SI-1) in the ground state under vacuum was calculated using the B3LYP functional and the 6-31G(d) basis set. The van der Waals volume V (cm) was calculated for the obtained most stable structure by the Monte Carlo method. 3 / mol) was calculated. Furthermore, single-point energy calculations were performed using B3LYP as the functional and 6-311+G(d) as the basis function to calculate the energy level (eV) of the highest occupied molecular orbital (HOMO orbital). It has been found that the closer this energy level is to the ITO work function (-4.5 to -5.0 eV), the more likely charge (hole) injection occurs from the ITO electrode interface, and charge accumulation during operation is more likely. It has also been found that the lower this energy level is, the higher the ionization potential becomes, the more likely charge (hole) transportability decreases, and charge relaxation during operation is less likely to occur. Regarding the evaluation of the DC image retention characteristics of bissuccinimide (SI-1), a HOMO level of -5.5 eV or more but less than -5.2 eV was rated as "good," and a HOMO level of less than -5.5 eV or more than -5.2 eV was rated as "poor." As a result, this example was rated as "good."

[0133] (2) Absorption edge and transparency evaluation For the most stable structure obtained in (1) above, the singlet excited state was calculated using the time-dependent density functional theory (TD-DFT) with the functional B3LYP and the basis set 6-311+G(d). For each electronic transition (excitation energy and oscillator strength), the molar extinction coefficient ε (L / mol / cm) at each wavelength was calculated with a half-width at half maximum of 0.25 eV, and the van der Waals volume V (cm) obtained in (1) above was used. 3The transmittance spectrum of a 100 nm thin film was determined using a 100 nm thick film (100 nm thick film thickness). Furthermore, the wavelength (absorption edge) at which the transmittance was 99% or higher was calculated from the obtained transmittance spectrum. Comparing the calculated results with the actual measurement results, it was found that the absorption edge was shifted to the longer wavelength side by about 40 nm under these calculation conditions. Regarding the evaluation of the transparency of bissuccinimide (SI-1), an absorption edge of less than 440 nm was rated as "good," and an absorption edge of 440 nm or higher was rated as "poor." As a result, the evaluation of this example was "good."

[0134] [Examples 21 to 23, Comparative Examples 7 to 11] The physical properties of polyimides (polymers (PI-21) to (PI-28)) were evaluated in the same manner as in Example 20, except that the type of diamine was changed as shown in Table 3 below. The evaluation results are shown in Table 3 below. Also, Figs. 3 and 4 show the transmittance spectra of Examples 20 to 23 and Comparative Examples 7 to 11, respectively. Furthermore, Fig. 5 shows the molecular structures and molecular orbitals (HOMO and LUMO) of compounds (SI-1) to (SI-9) in Examples 20 to 23 and Comparative Examples 7 to 11.

[0135] [Table 3]

[0136] In Table 3, diamines (DA-3a, DA-18 to DA-20) are compounds represented by the following formulas (DA-3a), (DA-18) to (DA-20), respectively. [ka]

[0137] As shown in Table 3, Examples 20 to 23, which used a copolymer of an aliphatic tetracarboxylic dianhydride and a specific diamine, had a "good" transparency and a "good" DC image retention characteristic based on quantum chemical calculations of the bissuccinimide, and were well-balanced in various characteristics. In contrast, Comparative Examples 7 to 11, which used a copolymer of an aliphatic tetracarboxylic dianhydride and a specific diamine, were "poor" in at least one of the transparency and the DC image retention characteristic, and were inferior to the Examples.

[0138] Here, the results of Examples 20 to 23 and Comparative Examples 7 to 11 will be considered. Comparing the results of Example 22 (diamine (DA-3a)) with Comparative Example 10 (diamine (DA-19)), and Example 23 (diamine (DA-4)) with Comparative Example 7 (diamine (DA-6)), Examples 22 and 23, which used a diamine having a bicarbazole ring, exhibited "good" DC image retention characteristics, whereas Comparative Examples 10 and 7, which used a diamine having a carbazole ring instead of a bicarbazole ring, exhibited "poor" DC image retention characteristics. This is presumably because the polymer having a structural unit derived from a diamine having a carbazole ring did not exhibit sufficient charge transport properties, whereas the polymer having a structural unit derived from a diamine having a bicarbazole ring exhibited sufficient charge transport properties.

[0139] Furthermore, when the results of Example 22 (diamine (DA-3a)) and Comparative Example 9 (diamine (DA-18)) were compared, Example 22, which used a diamine in which an oxygen atom was bonded to the carbon atom of the bicarbazole ring, had "good" transparency, whereas Comparative Example 9, which used a diamine in which a nitrogen atom was bonded to the carbon atom of the bicarbazole ring, had "poor" transparency. This is presumably because in Comparative Example 9, the π-conjugated system was expanded via the nitrogen atom, resulting in a shift in absorption to longer wavelengths.

[0140] Low-energy electronic transitions are important because they affect absorption in the visible light region, and the contribution of electronic transitions from HOMO to LUMO is generally large. For example, in Example 20, 93% of the lowest energy transitions (S0-S1 transitions) were HOMO-LUMO transitions. Regarding the HOMO-LUMO transitions, charge transfer (CT) transitions contributed significantly in Examples 20 and 21, while localized excitation (LE) transitions contributed significantly in Examples 22 and 23 and Comparative Examples 7 to 11. In Examples 20 and 21, the bicarbazole rings are linked via nitrogen atoms at the 9,9'-positions, and it is presumed that the electronic states are significantly different from those in Examples 22 and 23 and Comparative Examples 7 to 11.

[0141] [Synthesis Example 26] Diamine (DA-1) was dissolved in NMP, and 2.0 molar equivalents of maleic anhydride relative to the amount of diamine was added. The reaction was carried out at room temperature for 6 hours to obtain a 10% by mass solution of additive (AD-5) represented by the following formula (AD-5). [ka]

[0142] [Synthesis Example 27] Polyamic acid (PI-29) was obtained in the same manner as in Synthesis Example 5, except that the types and molar ratios of the tetracarboxylic dianhydrides and diamines were changed as shown in Table 4. Note that the values ​​in Table 4 indicate the proportion (mol %) of each compound used relative to the total amount (100 mol %) of the dianhydrides used in the synthesis, and the values ​​in Table 4 indicate the proportion (mol %) of each compound used relative to the total amount (100 mol %) of the diamines used in the synthesis.

[0143] [Synthesis Examples 28 and 29] Polyimides (PI-30, PI-31) were obtained in the same manner as in Synthesis Example 23, except that the types and molar ratios of the tetracarboxylic dianhydrides and diamines were changed as shown in Table 4 below.

[0144] [Table 4]

[0145] [Examples 24 to 27] In the above Example 1, the components contained in the liquid crystal alignment agent were changed as shown in Table 5 below, and the solvent composition ratio was changed to NMP:BC:NEP:GBL=50:30:10:10 (mass ratio), except that the liquid crystal alignment agent was prepared in the same manner as in Example 1, and a liquid crystal alignment film was formed by a photoalignment method, and an FFS-type liquid crystal display element was manufactured and various evaluations were performed. The evaluation results are shown in Table 5 below.

[0146] [Examples 28 to 30] In the above Example 13, the components contained in the liquid crystal alignment agent were changed as shown in Table 5 below, and the solvent composition ratio was changed to NMP:BC:NEP:GBL=50:30:10:10 (mass ratio), except that the liquid crystal alignment agent was prepared in the same manner as in Example 13, and a liquid crystal alignment film was formed by a rubbing method, and an FFS-type liquid crystal display element was manufactured and various evaluations were performed. The evaluation results are shown in Table 5 below.

[0147] [Table 5]

[0148] In Table 5, the mass ratio of each component of the liquid crystal aligning agent indicates the blending ratio (parts by mass) of each compound relative to 100 parts by mass in total of the polymer components and additive components used in preparing the liquid crystal aligning agent.

[0149] As shown in Table 5, the liquid crystal alignment agents of Examples 24 to 26, 28 and 29 containing polymer (P) had "good" optical properties (transparency) of the liquid crystal alignment film and "excellent" DC afterimage properties of the liquid crystal display element, and the various properties were well balanced.

[0150] Furthermore, for the liquid crystal alignment agents of Examples 27 and 30 containing additive (AD-5), the optical properties (transparency) of the liquid crystal alignment film were "good," and the DC image retention characteristics of the liquid crystal display element were "good," showing a balance of various properties similar to that of the liquid crystal alignment agent containing polymer (P). This is thought to be because, during the liquid crystal alignment film formation process, additive (AD-5) was converted to a bismaleimide compound, and a dimerization reaction (coupling reaction) or crosslinking reaction (Michael addition reaction with the amino group at the polymerization terminal of the polymer) of the maleimide group progressed, or a polymer having partial structure (A) was produced by a polymerization reaction between maleimide groups.

[0151] From the above, it was found that a liquid crystal aligning agent of the present disclosure containing the compound (P) can provide a liquid crystal device having good optical properties (transparency) and DC afterimage properties.

Claims

1. A liquid crystal aligning agent comprising a compound (P) having, as the partial structure (A) represented by the following formula (1), at least one selected from the group consisting of a partial structure represented by the following formula (x-1), a partial structure represented by the following formula (x-2), and a partial structure represented by the following formula (3): *-Y １ —A １ —A ２ -Y ２ — …(1) (In formula (1), A １ and A ２ are each independently a divalent group having a fused ring structure in which aromatic rings are fused to the 2,3-position and the 4,5-position of at least one heteroaromatic ring selected from the group consisting of a pyrrole ring, a furan ring, and a thiophene ring. １ and A ２ At least one carbon atom of the aromatic ring constituting the fused ring structure is bonded to another carbon atom of the aromatic ring by a single bond. １ and Y ２ are each independently A １ or A ２ A carbon atom, an oxygen atom, a sulfur atom or * for the fused ring structure in ５ -NR ５ A divalent organic group bonded by -CO-, or * ２ -NR ４ -* ３ It is. ４ is a hydrogen atom or a monovalent organic group, or is bonded to another group to form R ４ represents a part of a ring structure formed together with the nitrogen atom to which R is attached. ５ is a hydrogen atom or a monovalent organic group. ２ " and "* ５ " is A １ or A ２ This indicates that the bond is bonded to the fused ring structure in the ring. ３ " represents a bond bonded to --CO--. "*" represents a bond.) 【Chemistry 1】 (In formulas (x-1) to (x-2), G 1 and G 2 each independently represent —O— or —S—. “*” represents a bond.) 【Chemistry 2】 (In formula (3), R 2 is a halogen atom, a hydroxy group, or a monovalent organic group. R 3 is a hydrogen atom or a monovalent organic group. Y 4 is a carbon atom, an oxygen atom, a sulfur atom, or a divalent organic group bonded to the fused ring structure in the formula via * 5 -NR 5 -CO-, or is * 2 -NR 4 -* 3 . R 4 is a hydrogen atom or a monovalent organic group, or is bonded to another group to represent a part of a ring structure formed together with the nitrogen atom to which R 4 is bonded. R 5 is a hydrogen atom or a monovalent organic group. "* 2 " and "* 5 " represent bonds bonded to the fused ring structure in the formula. "* 3 " represents a bond bonded to -CO-. a2 is an integer of 0 to 3. When a plurality of R 2 s are present in the formula, the plurality of R 2 s may be the same or different. The plurality of Y 4 are the same or different. Multiple a2's in the formula are the same or different. "*" represents a bond.

2. The liquid crystal aligning agent according to claim 1, wherein the partial structure (A) is at least one selected from the group consisting of the following formulas (x-1) to (x-4): 【Transformation 6】 (In formulas (x-1) to (x-4), G 1 and G 2 each independently represent —O— or —S—. Z 3 and Z 4 each independently represent —O— or —S—. R 12 and R 13 each independently represent a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms. “*” represents a bond.)

3. The liquid crystal aligning agent according to claim 1 or 2, wherein the compound (P) is a polymer.

4. The compound (P) is a diamine having a partial structure represented by the above formula (x-1), a diamine having a partial structure represented by the above formula (x-2), and a diamine having a partial structure represented by the above formula (3) (wherein, in the above formula (3), R ４ is a hydrogen atom or a monovalent organic group.) The liquid crystal aligning agent according to any one of claims 1 to 3, which is a polymer having a structural unit derived from at least one selected from the group consisting of:

5. The compound (P) is a polymer having at least one partial structure selected from the group consisting of a partial structure represented by the following formula (5) and a partial structure represented by the following formula (6): A liquid crystal aligning agent according to any one of claims 1 to 4. 【Transformation 3】 (In formula (5) and formula (6), X １ is a tetravalent organic group. ２ R is a divalent organic group represented by the above formula (x-1), the above formula (x-2), or the following formula (8). ８ , R ９ , R １０ and R １１ are each independently a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms. 【Transformation 5】 (In formula (8), R ２ is a halogen atom, a hydroxy group, or a monovalent organic group. ３ is a hydrogen atom or a monovalent organic group. ６ is a single bond, or a carbon atom, an oxygen atom, a sulfur atom, or * to the fused ring structure in the formula. ５ -NR ５ It is a divalent organic group bonded by -CO-. ５ is a hydrogen atom or a monovalent organic group. ５ " represents a bond bonded to the fused ring structure in the formula. a2 is an integer of 0 to 3. In the formula, R ２ If there are multiple R ２ are the same or different. ６ are the same or different. Multiple a2's in the formula are the same or different. "*" represents a bond.

6. The X １ The liquid crystal aligning agent according to claim 5 , wherein is a tetravalent aliphatic hydrocarbon group.

7. Contains a polymer component and an additive component, The liquid crystal aligning agent according to claim 1 , wherein the compound (P) is an additive component.

8. The liquid crystal aligning agent according to any one of claims 1 to 7, further comprising a polymer not having the partial structure (A).

9. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 8.

10. A liquid crystal device comprising the liquid crystal alignment film according to claim 9 .

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