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

Abstract

The present invention provides a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal element, and a polymer. A liquid crystal aligning agent is prepared, and the liquid crystal aligning agent contains a compound (P) having a partial structure (A) represented by formula (1). *-Y1-A1-A2-Y2-*...(1) In formula (1), A1 and A2 are each independently a divalent group having a condensed ring structure in which aromatic rings are condensed at the 2,3-position and 4,5-position, respectively, with at least one heteroaromatic ring selected from the group consisting of a pyrrole ring, a furan ring, and a thiophene ring. Among them, in A1 and A2, at least one carbon atom of the aromatic ring constituting the condensed ring structure is bonded to each other by a single bond. Y1 and Y2 are divalent organic groups bonded to the condensed ring structure in A1 or A2 by a carbon atom, an oxygen atom, a sulfur atom, or *5-NR5-CO-, or are *2-NR4-*3.

Description

Technical Field

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal element, and a polymer. Background Art

[0002] Liquid crystal elements are widely used in televisions, mobile devices, various monitors, etc. Along with this diversification of uses, higher quality is required for liquid crystal elements. While improving the driving method or the element structure, the improvement of the liquid crystal alignment film, which is one of the constituent materials of the liquid crystal element, is promoted.

[0003] In a liquid crystal element, if charges accumulate in the liquid crystal cell, they will be recognized as afterimages (direct current (DC) afterimages) by an observer, and the display quality of the liquid crystal element will deteriorate. Therefore, one of the characteristics required for the liquid crystal alignment film is less accumulation of charges. As a cause of charge accumulation in the liquid crystal cell, it is considered to be due to the application of a positive / negative asymmetric voltage for AC driving, the absorption of backlight light by the liquid crystal alignment film, etc. In particular, DC afterimages are likely to occur in a Fringe Field Switching (FFS) type liquid crystal display element having an asymmetric electrode structure.

[0004] Therefore, various techniques for suppressing the accumulation of charges in the liquid crystal cell and improving the display quality of the liquid crystal element have been proposed in the past (for example, refer to Patent Document 1 and Patent Document 2). Patent Document 1 discloses the following: reduction of accumulated charges is achieved by including a polyamic acid obtained by reacting a diamine compound with a tetracarboxylic dianhydride in the liquid crystal aligning agent, and the diamine compound includes a nitrogen-containing diamine such as N4,N4'-bis(4-aminophenyl)-benzidine. Patent Document 2 discloses the following: a liquid crystal alignment film with a fast relaxation of accumulated charges and less likely to flicker during driving can be obtained by including a polymer obtained from a diamine having a structure in which a carbazole structure and a benzene ring are bonded by an amino group in the liquid crystal aligning agent.

[0005] [Prior Art Documents]

[0006] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Laid-Open No. 2008-107811

[0008] [Patent Document 2] International Publication No. 2018 / 110354 Summary of the Invention

[0009] [Problems to be Solved by the Invention]

[0010] In order to meet the requirements for further high performance in recent years, a liquid crystal alignment film is needed that can further reduce the accumulation of charges in the liquid crystal cell and can more rapidly relieve the accumulated residual charges. In addition, for the liquid crystal alignment film, high transparency of the film is required.

[0011] The present invention has been made in view of the above problems, and a main object thereof is to provide a liquid crystal aligning agent that can obtain a liquid crystal alignment film having high transparency, little accumulation of charges, and rapid relief of the accumulated residual charges.

[0012] [Means for Solving the Problems]

[0013] The present invention adopts the following means to solve the above problems.

[0014] <1> A liquid crystal aligning agent containing a compound (P) having a partial structure (A) represented by the following formula (1).

[0015] *-Y 1 -A 1 -A 2 -Y 2 -*…(1)

[0016] (In formula (1), A 1 and A 2 are each independently a divalent group having a condensed ring structure in which aromatic rings are condensed at the 2,3-positions and 4,5-positions, respectively, with at least one heteroaromatic ring selected from the group consisting of a pyrrole ring, a furan ring, and a thiophene ring. Among them, A 1 and A 2 at least one carbon atom of the aromatic ring constituting the condensed ring structure is bonded to each other by a single bond. Y 1 and Y 2 are each independently a divalent organic group bonded to the condensed ring structure in A 5 -NR 5 -CO- or a divalent organic group bonded to the condensed ring structure in A 1 or A 2 , or is * 2 -NR 4 -* 3 . R 4 is a hydrogen atom or a monovalent organic group, or represents a part of a ring structure formed by bonding to another group and 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 bonding bonds bonded to the condensed ring structure in A 1 or A 2 . "* 3" represents a bonding bond bonded to -CO-. "*" represents a bonding bond.)

[0017] <2> A liquid crystal alignment film formed using the liquid crystal aligning agent of <1>.

[0018] <3> A liquid crystal element including the liquid crystal alignment film of <2>.

[0019] <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).

[0020] [Chemical formula 1]

[0021]

[0022] (In formula (5) and formula (6), X 1 is a tetravalent aliphatic hydrocarbon group. X 2 is a divalent organic group represented by the following formula (7) or formula (8). R 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.)

[0023] [Chemical formula 2]

[0024]

[0025] (In formula (7), R 1 is a halogen atom, a hydroxyl group, or a monovalent organic group, or represents a condensed ring structure formed by combining a plurality of R 1 in the formula with the ring to which they are bonded. Y 5 is a divalent organic group bonded to the condensed ring structure in the formula by a carbon atom. a1 is an integer of 0 to 3. When there are a plurality of R 1 in the formula, the plurality of R 1 are the same or different from each other. The plurality of Y 5 in the formula are the same or different from each other. The plurality of a1 in the formula are the same or different from each other. "*" represents a bonding bond.)

[0026] [Chemical formula 3]

[0027]

[0028] (In formula (8), R 2 is a halogen atom, a hydroxyl group, or a monovalent organic group. R 3 is a hydrogen atom or a monovalent organic group. Y 6 is a single bond, or is a bond using a carbon atom, an oxygen atom, a sulfur atom or * 5 -NR5 A divalent organic group bonded to the condensed ring structure in the formula through -CO-. R 5 is a hydrogen atom or a monovalent organic group. "* 5 " represents a bonding bond bonded to the condensed ring structure in the formula. a2 is an integer from 0 to 3. When there are multiple Rs 2 in the formula, the multiple Rs 2 are the same as or different from each other. The multiple Ys 6 in the formula are the same as or different from each other. The multiple a2s in the formula are the same as or different from each other. "*" represents a bonding bond.)

[0029] [Effects of the Invention]

[0030] According to the liquid crystal aligning agent of the present invention, a liquid crystal alignment film with high transparency can be obtained. In addition, a liquid crystal alignment film with less charge accumulation and rapid relaxation of the accumulated residual charge can be obtained. Description of the Drawings

[0031] Figure 1 is a diagram showing the measurement results of the hydrogen nuclear magnetic resonance ( 1 H-nuclear magnetic resonance, 1 H-NMR) spectrum of the diamine (DA-1) obtained in Synthesis Example 1.

[0032] Figure 2 is a diagram showing the measurement results of the carbon nuclear magnetic resonance ( 13 C-NMR) spectrum of the diamine (DA-1) obtained in Synthesis Example 1.

[0033] Figure 3 is a diagram showing the transmission spectra of Examples 20 to 23.

[0034] Figure 4 is a diagram showing the transmission spectra of Comparative Examples 7 to 11.

[0035] Figure 5 is a diagram showing the molecular structures and molecular orbitals (highest occupied molecular orbit, HOMO, and lowest unoccupied molecular orbit, LUMO) of bis-succinimides of Examples 20 to 23 and Comparative Examples 7 to 11. Detailed Description of the Invention

[0036] Hereinafter, matters related to the embodiments of the present disclosure will be described in detail. In addition, in this specification, the term "hydrocarbyl group" means a group including an acyclic hydrocarbyl group, an alicyclic hydrocarbyl group, and an aromatic hydrocarbyl group. The term "acyclic hydrocarbyl group" means a straight-chain or branched hydrocarbyl group having no cyclic structure in the main chain and consisting only of an acyclic structure, which may be saturated or unsaturated. The term "alicyclic hydrocarbyl group" means a hydrocarbyl group having only an alicyclic hydrocarbon structure as a ring structure and no aromatic ring structure. Herein, it does not have to be composed only of an alicyclic hydrocarbon structure, and also includes those having a chain structure in a part thereof. The term "aromatic hydrocarbyl group" means a hydrocarbyl group having an aromatic ring structure as a ring structure. Herein, it does not have to be composed only of an aromatic ring structure, and may also include a chain structure or an alicyclic hydrocarbon structure in a part thereof.

[0037] The term "aliphatic hydrocarbyl group" means a group including an acyclic hydrocarbyl group and an alicyclic hydrocarbyl group. The term "heterocyclic aromatic group" means a group formed by removing n (n is an integer) hydrogen atoms from the ring portion of an aromatic heterocycle. Herein, when the heterocyclic aromatic group has a plurality of rings, it includes a group formed by removing n hydrogen atoms from the same ring and a group formed by removing n hydrogen atoms from different rings. The "main chain" of a polymer means the longest "backbone" part in the atomic chain of the polymer. The "side chain" of a polymer means a part branched from the "backbone" of the polymer. The term "organic group" means an atomic group formed by removing any hydrogen atom from a carbon-containing compound (i.e., an organic compound).

[0038] "Liquid Crystal Alignment Agent"

[0039] The liquid crystal alignment agent of the present disclosure contains a compound (P) having a partial structure (A) represented by the following formula (1).

[0040] *-Y 1 -A 1 -A 2 -Y 2 -*…(1)

[0041] (In formula (1), A 1 and A 2 are each independently a divalent group having a condensed ring structure in which aromatic rings are condensed at the 2,3-positions and 4,5-positions, respectively, and having at least one heteroaromatic ring selected from the group consisting of a pyrrole ring, a furan ring, and a thiophene ring. Among them, in A 1 and A 2 , at least one carbon atom of the aromatic ring constituting the condensed ring structure is bonded to each other by a single bond. Y 1 and Y 2 are each independently bonded to A 5 -NR 5 -CO- through a carbon atom, an oxygen atom, a sulfur atom or * 1or A 2 a divalent organic group bonded to the condensed ring structure in, or is * 2 -NR 4 -* 3 . R 4 is a hydrogen atom or a monovalent organic group, or represents a part of a ring structure formed by bonding to other groups and 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 the bonding bonds bonded to the condensed ring structure in A 1 or A 2 . "* 3 " represents the bonding bond bonded to -CO-. "*" represents the bonding bond.)

[0042] In the formula (1) described above, regarding A 1 and A 2 The condensed ring structure possessed, the heteroaromatic ring is preferably a pyrrole ring. The aromatic ring condensed to the heteroaromatic ring is preferably a benzene ring or a naphthalene ring. In addition, substituents can also be introduced into the aromatic ring condensed to the heteroaromatic ring. As the substituents, examples include: halogen atoms, hydroxyl groups or monovalent organic groups. Among them, as the halogen atoms, examples include: fluorine atom, chlorine atom, bromine atom, iodine atom. As the monovalent organic groups, examples include: alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, fluoroalkyl groups having 1 to 10 carbon atoms, fluoroalkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, aryloxy groups having 6 to 12 carbon atoms, aralkyl groups having 6 to 12 carbon atoms, -NR 10 R 11 (wherein, R 10 and R 11 are each independently a monovalent hydrocarbon group), etc.

[0043] As the condensed ring structures respectively possessed by A 1 and A 2 , examples include: carbazole ring structure, benzocarbazole ring structure, or dibenzocarbazole ring structure. A 1 and A 2 Among the condensed ring structures possessed, the carbazole ring structure is particularly preferred.

[0044] The bonding position of the aromatic ring constituting the condensed ring structure possessed by A 1 and the aromatic ring constituting the condensed ring structure possessed by A 2 is not particularly limited. For example, in A 1 and A 2When the condensed ring structure each has is a carbazole ring structure, examples of the bonding positions of the two carbazole rings include the 3,3'-position, 4,4'-position, 3,9'-position, etc., and among them, the 3,3'-position is preferred. In A 1 and A 2 the aromatic ring constituting the condensed ring structure of A 1 and the aromatic ring constituting the condensed ring structure of A 2 can be further condensed.

[0045] As specific examples of the group "-A 1 -A 2 -", groups represented by the following formulas (a-1) to (a-5) can be cited, etc. Among them, the group "-A 1 -A 2 -" is preferably the group represented by the following formula (a-1) or formula (a-2). In addition, as an embodiment of "the aromatic ring constituting the condensed ring structure of A 1 and the aromatic ring constituting the condensed ring structure of A 2 are further condensed", groups represented by the following formulas (a-1) to (a-5) can be cited.

[0046] [Chemical formula 4]

[0047]

[0048] (In formulas (a-1) to (a-5), R a is a halogen atom, a hydroxyl group or a monovalent organic group. R b is a hydrogen atom or a monovalent organic group. r is an integer from 0 to 3. E 1 is -O-, -S-, -NR c -, or -CH=CH-. R c is a hydrogen atom or a monovalent organic group. When there are multiple R a in the formula, the multiple R a are the same or different from each other. When there are multiple E 1 in the formula, the multiple E 1 are the same or different from each other. "*" represents a bonding bond.)

[0049] In the formula (1), when Y 1 , Y 2 is * 2 -NR 4 -* 3 , R 4The monovalent organic group is preferably an alkyl group having 1 to 5 carbon atoms or a dissociable group that dissociates by at least one of heat and light, more preferably an alkyl group having 1 to 5 carbon atoms or a thermally dissociable group. In terms of simplifying the process by causing the group R to dissociate during the process of forming a liquid crystal alignment film by coating a liquid crystal aligning agent on a substrate and heating it, the thermally dissociable group is preferably a group that decomposes at a temperature of 120°C to 300°C and is replaced by a hydrogen atom. Specifically, it is preferably a tert-butoxycarbonyl group (Boc group) or a 9-fluorenylmethoxycarbonyl group, and particularly preferably a tert-butoxycarbonyl group. 4 In terms of the view of simplifying the process by dissociation, the thermally dissociable group is preferably a group that decomposes at a temperature of 120°C to 300°C and is replaced by a hydrogen atom. Specifically, it is preferably a tert-butoxycarbonyl group (Boc group) or a 9-fluorenylmethoxycarbonyl group, and particularly preferably a tert-butoxycarbonyl group.

[0050] When R 4 represents a part of a ring structure formed by bonding to another group and together with the nitrogen atom to which R 4 is bonded, specific examples of the ring structure include an imide ring structure. When R 4 represents a part of an imide ring structure formed by bonding to another group and together with the nitrogen atom, R 4 can be represented by, for example, * 6 -CO-R- (R is a single bond or a divalent organic group. * 6 represents a bonding bond bonded to the nitrogen atom).

[0051] When Y 1 and Y 2 are divalent organic groups that bond to the condensed ring structure in A 1 or A 2 through a carbon atom, an oxygen atom, a sulfur atom, or * 5 -NR 5 -CO-, examples of the divalent organic group include: a divalent linear 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, a divalent group having 1 to 20 carbon atoms in which at least one methylene group in the divalent hydrocarbon group is replaced by -O-, -S-, -CO-, or * 5 -NR 5 -CO-, a divalent group having 1 to 20 carbon atoms in which at least one hydrogen atom in the divalent hydrocarbon group is replaced by a substituent (for example, a halogen atom, a carboxyl group, a hydroxyl group, etc.), a divalent heteroaromatic group, etc. Regarding specific examples when R 5 is a monovalent organic group, the description of R 4 can be cited. As the heteroaromatic group, for example, pyridinediyl, pyrimidinediyl, etc. can be cited.

[0052] In terms of the view of sufficiently obtaining the effect of reducing the afterimage (DC afterimage) caused by accumulated charges, the compound (P) is preferably a compound having a partial structure (A) in the main chain. Specifically, the partial structure (A) is preferably at least one selected from the group consisting of a partial structure represented by the following formula (2) and a partial structure represented by the following formula (3).

[0053] [Chemical Formula 5]

[0054]

[0055] (In Formula (2), R 1 is a halogen atom, a hydroxyl group, or a monovalent organic group, or multiple Rs in the formula 1 are combined with each other and together with the ring to which they are bonded form a condensed ring structure. Y 3 is a divalent organic group bonded to the condensed ring structure in the formula through a carbon atom. a1 is an integer from 0 to 3. When there are multiple Rs in the formula 1 , the multiple Rs 1 are the same as or different from each other. The multiple Ys in the formula 3 are the same as or different from each other. The multiple a1s in the formula are the same as or different from each other. "*" represents a bonding bond.)

[0056] [Chemical Formula 6]

[0057]

[0058] (In Formula (3), R 2 is a halogen atom, a hydroxyl group, or a monovalent organic group. R 3 is a hydrogen atom or a monovalent organic group. Y 4 is a divalent organic group bonded to the condensed ring structure in the formula through a carbon atom, an oxygen atom, a sulfur atom or * 5 -NR 5 -CO-, or is * 2 -NR 4 -* 3 . R 4 is a hydrogen atom or a monovalent organic group, or represents a part of a ring structure formed by bonding with another group and 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 the bonding bonds bonded to the condensed ring structure in the formula. "* 3 " represents the bonding bond bonded to -CO-. a2 is an integer from 0 to 3. When there are multiple Rs in the formula 2 , the multiple Rs 2 are the same as or different from each other. The multiple Ys in the formula 4 are the same as or different from each other. The multiple a2s in the formula are the same as or different from each other. "*" represents a bonding bond.)

[0059] In the said Formula (2), as R 1Specific examples of the monovalent organic group include the groups exemplified as the substituents that the aromatic ring condensed to the heteroaromatic ring in the formula (1) may have.

[0060] When R 1 represents the plurality of Rs in the formula (2) 1 and they are bonded to each other and together with the ring to which they are bonded form a condensed ring structure, the condensed ring structure includes two Rs bonded to the same aromatic ring 1 bonded to each other and together with the ring to which they are bonded form a condensed ring structure, and two Rs bonded to different aromatic rings (for example, the aromatic rings in different carbazole structures) 1 bonded to each other and together with the ring to which they are bonded form a condensed ring structure. As specific examples of the plurality of Rs in the formula (2) 1 bonded to each other and together with the ring to which they are bonded form a condensed ring structure, the structures represented by the formula (a-3) to the formula (a-5) can be cited.

[0061] As specific examples of Y 3 include the groups exemplified as the divalent organic groups of Y in the formula (1) 1 and Y 2 . Y 3 is preferably a divalent organic group bonded to the condensed ring structure in the formula through a carbon atom, more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, having -O-, -S-, -CO- or * 5 -NR 5 -CO- in the carbon-carbon bond of the divalent hydrocarbon group, a divalent group having 1 to 20 carbon atoms in which at least one hydrogen atom in the divalent hydrocarbon group is substituted by a substituent (for example, a halogen atom, a carboxyl group, a hydroxyl group, etc.), or a divalent heteroaromatic group. Among them, from the viewpoint of high reduction effect on residual charge and ease of synthesis, Y 3 is preferably a group bonded to the nitrogen atom in the formula (2) through an aromatic ring (preferably a benzene ring, a naphthalene ring, a pyridine ring or a pyrimidine ring). a1 is preferably 0 or 1.

[0062] In the formula (3), as specific examples of R 2 include the groups exemplified as the substituents that the aromatic ring condensed to the heteroaromatic ring in the formula (1) may have.

[0063] In the case where Y 4 is * 2 -NR 4 -* 3 , as specific examples of the monovalent organic group of R 4 include the groups exemplified as R 4 in the formula (1). Regarding Y 4Specific examples of the divalent organic group that binds to the condensed ring structure in the formula by using a carbon atom, an oxygen atom, or a sulfur atom include Y 1 and Y 2 The divalent organic groups exemplified in the description of. Among them, from the viewpoint of high reduction effect on residual charge and ease of synthesis, Y 4 is preferably * 4 -G 3 -A 3 -(wherein G 3 is an oxygen atom or a sulfur atom. A 3 is a divalent aromatic ring group (preferably a group formed by removing two hydrogen atoms from a benzene ring, a naphthalene ring, a pyridine ring, or a pyrimidine ring). "* 4 " represents a bonding bond that binds to the condensed ring structure.).

[0064] The monovalent organic group of R 3 is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms or a dissociable group that dissociates 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 dissociable group. Regarding specific examples and preferred examples when R 3 is a thermally dissociable group, the description of the thermally dissociable group of R 4 in the formula (1) can be cited. From the viewpoint of making the transparency of the liquid crystal alignment film more excellent, R 3 is preferably a hydrogen atom or a monovalent organic group among monovalent organic groups.

[0065] a2 is preferably 0 or 1.

[0066] Compound (P) can be a polymer component contained in the liquid crystal aligning agent or an additive component separately formulated from the polymer component. Among them, from the viewpoint of more sufficiently obtaining the reduction effect on DC ghost images, compound (P) is preferably a polymer. Hereinafter, a polymer having a partial structure (A) (hereinafter, also referred to as "polymer (P)") and an additive having a partial structure (A) (hereinafter, also referred to as "additive (P)") will be described separately.

[0067] · Regarding polymer (P)

[0068] The main skeleton of polymer (P) is not particularly limited. From the viewpoint of easily introducing the partial structure (A) into the main chain of the polymer, polymer (P) is preferably obtained by using the following monomers, that is, diamines containing a partial structure represented by the formula (2) and diamines containing a partial structure represented by the formula (3) (wherein, in the formula (3), R 4A polymer obtained by polymerizing monomers of at least one diamine compound (hereinafter also referred to as "specific diamine") selected from the group consisting of a hydrogen atom or a monovalent organic group. Examples include: polyamic acid, polyamic acid ester, polyimide, polyamide, polyurea, polyamine, polyamideimide, polysiloxane, polyester, polyvinylamine, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, (meth)acrylic polymer, styrene polymer, maleimide polymer, styrene-maleimide copolymer, etc.

[0069] Among them, in terms of forming an organic film with high affinity for liquid crystal and high mechanical strength and obtaining a liquid crystal element with high reliability, the polymer (P) is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyurea, polysiloxane, and a polymer 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.

[0070] The polymer (P) may have a partial structure (A) in the main chain, may have a partial structure (A) in the side chain, or may have a partial structure (A) at the end. In terms of higher improvement effects on film transparency, reduction of accumulated charge, and mitigation of residual charge, the polymer (P) is preferably one having a partial structure (A) in the main chain. In addition, when the polymer (P) has a partial structure (A) in the main chain, it may also have a partial structure (A) not only in the main chain but also in parts other than the main chain (side chain or end).

[0071] The method for introducing the partial structure (A) into the polymer (P) is not particularly limited. For example, a polymer having a partial structure (A) in the main chain of the polymer (P) can be obtained by polymerizing a monomer having the partial structure represented by the formula (1) in the main chain. In addition, a polymer having a partial structure (A) in the side chain of the polymer (P) can be obtained, for example, by polymerizing a monomer having the partial structure represented by the formula (1) in the side chain or by side-chain modification of the polymer using a reactive compound having the partial structure represented by the formula (1). A polymer having a partial structure (A) at the end of the polymer (P) can be obtained, for example, by adding a capping agent having the partial structure represented by the formula (1) (a monofunctional compound in the case of stepwise polymerization, or a polymerization initiator or polymerization terminator in the case of chain polymerization) for polymerization.

[0072] 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 the partial structure represented by the following formula (5) and the partial structure represented by the following formula (6).

[0073] [Chemical Formula 7]

[0074]

[0075] (In Formula (5) and Formula (6), X 1 is a tetravalent organic group. X 2 is a divalent organic group represented by the following Formula (7) or Formula (8). R 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.)

[0076] [Chemical Formula 8]

[0077]

[0078] (In Formula (7), Y 5 is a divalent organic group. Multiple Ys 5 in the formula are the same as or different from each other. R 1 and a1 have the same meanings as in the aforementioned Formula (2). "*" represents a bonding bond.)

[0079] [Chemical Formula 9]

[0080]

[0081] (In Formula (8), Y 6 is a single bond or a divalent organic group bonded to the condensed ring structure in the formula by a carbon atom, an oxygen atom, a sulfur atom or * 5 -NR 5 -CO-. R 5 is a hydrogen atom or a monovalent organic group. "* 5 " represents a bonding bond bonded to the condensed ring structure in the formula. Multiple Ys 6 in the formula are the same as or different from each other. R 2 and a2 have the same meanings as in the aforementioned Formula (3). "*" represents a bonding bond.)

[0082] In the aforementioned Formula (5) and Formula (6), X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative. In addition, in this specification, "tetracarboxylic acid derivative" means a compound including a tetracarboxylic dianhydride, a tetracarboxylic diester, and a tetracarboxylic diester dihalide.

[0083] As the tetracarboxylic acid derivative constituting X 1 , 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. In terms of obtaining a liquid crystal alignment film with high transparency and in terms of obtaining a liquid crystal alignment film with less accumulated charge, X1 Preferably a tetravalent aliphatic hydrocarbon group, and as specific examples, the tetravalent groups represented by the following formulas (11) to (16) can be cited. Among them, in terms of the above view, X 1 is preferably a tetravalent alicyclic hydrocarbon group. In addition, in the case of obtaining a liquid crystal alignment film by the photo-alignment method, X 1 is preferably a tetravalent group having a cyclobutane ring structure. Specifically, particularly preferably, it is a tetravalent group represented by the following formula (11) or formula (12). Among them, if the polymer (P) has X 1 as a partial structure of a tetravalent aliphatic hydrocarbon group and X 1 as a partial structure of a tetravalent aromatic hydrocarbon group, the polarities of the accumulated charges cancel each other out. As a result, there is a tendency for the accumulated charge to become smaller, and thus it is preferred.

[0084] [Chemical formula 10]

[0085]

[0086] (In formulas (11) to (16), "*" represents a bonding bond.)

[0087] Regarding X 2 , for the specific examples of Y 5 in the formula (7), the description of Y 3 in the formula (2) can be cited. Regarding R 1 and a1, the description of the formula (2) can be cited. In addition, for the specific examples of the divalent organic group of Y 6 in the formula (8), the description of Y 4 in the formula (3) can be cited. Regarding R 2 and a2 in the formula (8), the description of the formula (3) can be cited.

[0088] When R 8 , R 9 , R 10 and R 11 are monovalent organic groups 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.

[0089] <Polyamic acid>

[0090] The synthesis method of the polymer (P) is not particularly limited and can be obtained by appropriately combining common methods of 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.

[0091] (Tetracarboxylic dianhydride)

[0092] The tetracarboxylic dianhydride used in the synthesis of polyamic acid (P) is not particularly limited. Examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, etc.

[0093] Specific examples of these include, for example, aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and ethylenediaminetetraacetic dianhydride;

[0094] alicyclic tetracarboxylic dianhydrides such as 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-furyl)-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.;

[0095] aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, p-phenylenebis(trimellitic monoester anhydride), ethylene glycol bis(trimellitic anhydride ester), 1,3-propanediol bis(trimellitic anhydride ester), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-biphthalic dianhydride, etc. In addition, tetracarboxylic dianhydrides described in Japanese Patent Laid-Open No. 2010-97188 can be cited.

[0096] In terms of obtaining a liquid crystal alignment film with high transparency and less accumulated charge in combination with a specific diamine, the tetracarboxylic dianhydride used in the synthesis of polyamic acid (P) is preferably at least one selected from the group consisting of aliphatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides (hereinafter, also referred to as "specific anhydride"), and more preferably contains at least an alicyclic tetracarboxylic dianhydride. When using a specific anhydride in the synthesis of polyamic acid (P), the proportion of the specific anhydride is preferably 30 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol% or more relative to the total amount of the tetracarboxylic dianhydride used in the synthesis. In the synthesis of polymer (P), as the tetracarboxylic dianhydride, one kind can be used alone or two or more kinds can be used in combination.

[0097] When the polymer (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, the polymer (P) can also be obtained by reacting a tetracarboxylic dianhydride including a partial structure represented by the formula (1) (wherein, in the formula (1), Y 1 and Y 2 can each independently be -CO-.) with a diamine compound. Examples of the tetracarboxylic dianhydride having the partial structure represented by the formula (1) include compounds represented by the following formula (t-1) and formula (t-2), etc. In addition, when using the tetracarboxylic dianhydride having the partial structure represented by the formula (1) to synthesize the polymer (P), as the diamine compound, either a specific diamine or other diamines can be used, and also a specific diamine and other diamines can be used in combination.

[0098] [Chemical formula 11]

[0099]

[0100] (Diamine compound)

[0101] The specific diamine preferably has a partial structure represented by the formula (2) or formula (3) and two primary amino groups. Preferred specific examples of the specific diamine include compounds represented by the following formula (d-1) to formula (d-45), etc.

[0102] [Chemical formula 12]

[0103]

[0104] [Chemical formula 13]

[0105]

[0106] [Chemical formula 14]

[0107]

[0108] [Chemical formula 15]

[0109]

[0110] [Chemical formula 16]

[0111]

[0112] [Chemical formula 17]

[0113]

[0114] [Chemical formula 18]

[0115]

[0116] [Chemical formula 19]

[0117]

[0118] As the specific diamine, among them, the compounds represented by the formula (d-1) to formula (d-27) and formula (d-34) to formula (d-40) are preferred, and the compounds represented by the formula (d-1), formula (d-15), formula (d-16), and formula (d-34) to formula (d-40) are particularly preferred. As the specific diamine, one kind can be used alone or two or more kinds can be used in combination.

[0119] Among them, the polymer (P) preferably has X in the formula (5) and formula (6) 2 is a polymer having a structural unit of a divalent group represented by any one of the following formula (x-1) to formula (x-4), and particularly preferably has X in the formula (5) and formula (6) 1 is a tetravalent aliphatic hydrocarbon group and X 2 is a polymer having a structural unit of a divalent group represented by any one of the following formula (x-1) to formula (x-4).

[0120] [Chemical formula 20]

[0121]

[0122] (In formula (x-1) to formula (x-4), G 1 and G 2 are each independently -O- or -S-. Z 3 and Z 4 are each independently -O- or -S-. R 12 and R 13 are each independently a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms. "*" represents a bonding bond.)

[0123] When synthesizing the polyamic acid (P), as the diamine compound, only the specific diamine can be used, or a diamine compound different from the specific diamine (hereinafter, also referred to as "other diamine") can be used together with the specific diamine.

[0124] As the other diamine, if it is a diamine compound that does not have the partial structure represented by the formula (1), there is no particular limitation. For example, aliphatic diamines, alicyclic diamines, aromatic diamines, and diamino organosiloxanes can be mentioned. As specific examples of these, aliphatic diamines such as m-xylylenediamine, ethylenediamine, 1,3-propanediamine, tetramethylenediamine, and hexamethylenediamine can be mentioned;

[0125] Alicyclic diamines such as cyclohexanediamine and 4,4'-methylenebis(cyclohexylamine) can be mentioned;

[0126] Examples of the aromatic diamine include side-chain diamines such as dodecyloxy diaminobenzene, hexadecyloxy diaminobenzene, octadecyloxy diaminobenzene, cholesteryloxy diaminobenzene, cholesteroloxy diaminobenzene, cholesteryl ester of diaminobenzoic acid, cholesterol ester of diaminobenzoic acid, lanosteryl ester of diaminobenzoic acid, 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 the compound represented by the following formula (E-1);

[0127] [Chemical 21]

[0128]

[0129] (In the formula (E-1), X I and X II each independently represents a single bond, -O-, *-COO- or *-OCO- (wherein, "*" represents a bonding bond with X I ). R I is an alkanediyl having 1 to 3 carbon atoms. R II is a single bond or an alkanediyl having 1 to 3 carbon atoms. R III is an alkyl, alkoxy, fluoroalkyl, or fluoroalkoxy 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. Among them, 1 ≤ a + b + c ≤ 3.)

[0130] Non-side-chain diamines such as p-phenylenediamine, 4,4'-methylenedianiline, 4,4'-ethylenedianiline, 4,4'-diaminodiphenylamine, 4,4'-thiodianiline, 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'-bis(4-aminophenyl)-N,N'-dimethylethylenediamine, bis[2-(4-aminophenyl)ethyl]adipate, bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methylamine, 1,4-bis(4-aminophenyl)piperazine, N,N'-bis(4-aminophenyl)benzidine, 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-oxydianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-(phenylenediisopropylidene)dianiline, 1,4-bis(4-aminophenoxy)benzene, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, etc.;

[0131] Examples of the diaminoorganosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, etc. In addition, the diamine compounds described in JP-A-2010-97188 can be used. Further, when synthesizing the polyamic acid (P), as other diamines, one kind can be used alone or two or more kinds can be used in combination.

[0132] Regarding the use ratio of the specific diamine, from the viewpoint of sufficiently obtaining the transparency of the liquid crystal alignment film and the effect of reducing the accumulated charge, it is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, and still more preferably 10 mol% or more, relative to the total amount of the diamine compounds used in the synthesis of the polyamic acid (P). On the other hand, from the viewpoint of ensuring the solubility of the polymer, the use ratio of the specific diamine is preferably 80 mol% or less, more preferably 70 mol% or less, relative to the total amount of the diamine compounds used in the synthesis of the polyamic acid (P).

[0133] The specific diamine can be obtained by appropriately combining common methods of organic chemistry. As an example, the following method can be cited: Synthesize a dinitro intermediate having a nitro group instead of the primary amino group in the formula (5), and then, use an appropriate reducing system to aminate the nitro group of the obtained dinitro intermediate.

[0134] The method for synthesizing the dinitro intermediate can be appropriately selected according to the target compound. For example, regarding 9,9'-bis(4-aminophenyl)-3,3'-bicarbazole (the compound represented by the formula (d-1)), 3,3'-bicarbazole can be obtained through the oxidative coupling reaction of carbazole. Subsequently, 9,9'-bis(4-nitrophenyl)-3,3'-bicarbazole can be obtained as the dinitro intermediate through the aromatic nucleophilic substitution reaction of 3,3'-bicarbazole and p-fluoronitrobenzene. Subsequently, by reducing the nitro group of the obtained dinitro intermediate, the target 9,9'-bis(4-aminophenyl)-3,3'-bicarbazole can be obtained. In addition, the synthesis method of the specific diamine is not limited to the above description.

[0135] (Synthesis of polyamic acid)

[0136] The polyamic acid (P) can be obtained by reacting a tetracarboxylic dianhydride as described above with a diamine compound and, if necessary, a molecular weight regulator (also called a capping agent). Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, etc. The usage ratio of the tetracarboxylic dianhydride and the diamine compound for the synthesis reaction of the polyamic acid (P) is preferably such that the acid anhydride group of the tetracarboxylic dianhydride becomes 0.2 to 2 molar equivalents relative to 1 molar equivalent of the amino group of the diamine compound.

[0137] The synthesis reaction of the polyamic acid (P) is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours. Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc. Particularly preferred organic solvents are those selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphoric triamide, m-cresol, xylenol, and halogenated phenols, or a mixture of one or more of these and other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The usage amount of the organic solvent is preferably set such that the total amount of the tetracarboxylic dianhydride and the diamine compound becomes 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 can be directly used for the preparation of the liquid crystal aligning agent, or the polyamic acid (P) contained in the reaction solution can be separated and then used for the preparation of the liquid crystal aligning agent.

[0138] <Polyamic acid ester>

[0139] The polyamic acid ester as the polymer (P) has R in the partial structure represented by the formula (5) 8 and R 9is a polymer of structural units in which at least one is a monovalent organic group having 1 to 8 carbon atoms. The polyamic acid ester can be obtained, for example, by the following methods: [I] a method of reacting the obtained polyamic acid (P) with an esterifying agent (for example, methanol or ethanol, N,N-dimethylformamide diethyl acetal, etc.); [II] a method of reacting a tetracarboxylic acid diester with a diamine compound containing a specific diamine, preferably in an organic solvent and in the presence of a suitable dehydration catalyst (for example, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium halide, carbonylimidazole, phosphorus-based condensing agent, etc.); [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine compound containing a specific diamine, preferably in an organic solvent and in the presence of a suitable base (for example, a tertiary amine such as pyridine or triethylamine, or an alkali metal such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, potassium, etc.).

[0140] The tetracarboxylic acid diester used in [II] can be obtained by ring-opening a tetracarboxylic dianhydride using alcohols, etc. The tetracarboxylic acid diester dihalide used in [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride.

[0141] The polyamic acid ester may have only an amic acid ester structure, or may be a partial esterified product in which an amic acid structure and an amic acid ester structure coexist. In addition, when the polyamic acid ester is obtained in the form of a solution by the above reaction, the solution can be directly used for the preparation of a liquid crystal aligning agent, or the polyamic acid ester contained in the reaction solution can be separated and then used for the preparation of a liquid crystal aligning agent.

[0142] <Polyimide>

[0143] The polyimide as the polymer (P) is a polymer having a partial structure represented by the formula (6). The polyimide can be obtained, for example, by dehydrating and cyclizing the polyamic acid (P) synthesized as described above to effect imidization. The polyimide can be a completely imidized product in which all of the amic acid structures of the polyamic acid (P) as its precursor are dehydrated and cyclized, or can be a partially imidized product in which only a part of the amic acid structure is dehydrated and cyclized and the amic acid structure and the imide ring structure coexist. The polyimide preferably has an imidization rate of 40% to 100%, more preferably 60% to 90%. The imidization rate represents the proportion of the number of imide ring structures relative to the total number of amic acid structures and imide ring structures of the polyimide as a percentage. In addition, a part of the imide ring can also be a isoimide ring.

[0144] The dehydration ring closure of polyamic acid (P) is preferably carried out by the following method: dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as required. As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably set to be 0.01 mol to 20 mol relative to 1 mol of the amic acid structure of polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring closure catalyst used is preferably set to be 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent used. As the organic solvent used, the organic solvents exemplified in the synthesis of polyamic acid (P) can be listed. The reaction temperature of the dehydration ring closure reaction is preferably 0°C to 180°C, and the reaction time is preferably 1.0 hour to 120 hours. The reaction solution containing polyimide thus obtained can be directly used for the preparation of a liquid crystal aligning agent, or can be used for the preparation of a liquid crystal aligning agent after separating polyimide.

[0145] <Polyurea>

[0146] When the polymer (P) is 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.

[0147] (Diisocyanate compound)

[0148] The diisocyanate compound used in the synthesis of polyurea (P) is not particularly limited. As specific examples of the diisocyanate compound, for example, aliphatic diisocyanates, aromatic diisocyanates, etc. can be listed.

[0149] As specific examples thereof, aliphatic diisocyanates can be listed, for example: isophorone diisocyanate, hexamethylene diisocyanate, tetramethylethylene diisocyanate, etc.; aromatic diisocyanates can be listed, for example: o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanates (for example, 2,4-toluene diisocyanate), 1,4-diisocyanato-2-methoxybenzene, 2,5-dimethylxylene diisocyanates, 2,2'-bis(4-diisocyanatophenyl)propane, 4,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanatodiphenyl ether, 4,4'-diisocyanatodiphenyl sulfone, 3,3'-diisocyanatodiphenyl sulfone, 2,2'-diisocyanatobenzophenone, etc.

[0150] Regarding the solution viscosity of the polymer (P), when a 10% by mass solution is prepared, the solution viscosity is preferably 10 mPa·s to 800 mPa·s, more preferably 15 mPa·s to 500 mPa·s. Further, 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 with a good solvent for the polymer (P) (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0151] The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the polymer (P) is preferably 1,000 to 500,000, more preferably 5,000 to 100,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less. Further, the polymer (P) contained in the liquid crystal aligning agent may be only one kind, or two or more kinds may be combined.

[0152] ·Regarding the additive (P)

[0153] As the additive (P), a low molecular compound having both a partial structure (A) and a functional group capable of forming a bond by heat or light can be preferably used. Here, in the present specification, the "low molecular compound" is a compound having no molecular weight distribution, and is a component distinguished from a polymer having a repeating unit. The molecular weight of the low molecular compound is, for example, 1500 or less, preferably 1000 or less, more preferably 800 or less.

[0154] As a preferred specific example of the additive (P), a compound represented by the following formula (9) or formula (10) can be cited.

[0155] [Chemical formula 22]

[0156]

[0157] (In formula (9), R 1 is a halogen atom, a hydroxyl group, or a monovalent organic group, or represents a condensed ring structure formed by multiple Rs 1 in the formula bonding to each other and together with the ring to which they are bonded. Y 5 is a divalent organic group bonded to the condensed ring structure in the formula via a carbon atom. Z 1 is a functional group capable of forming a bond by heat or light. Z 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. When there are multiple Rs 1 in the formula, the multiple Rs1 are the same as or different from each other. Multiple Ys in the formula 5 are the same as or different from each other. Multiple a1s in the formula are the same as or different from each other.)

[0158] [Chemical formula 23]

[0159]

[0160] (In formula (10), R 2 is a halogen atom, a hydroxyl group, or a monovalent organic group. R 3 is a hydrogen atom or a monovalent organic group. Y 6 is a single bond, or a divalent organic group bonded to the condensed ring structure in the formula by a carbon atom, an oxygen atom, a sulfur atom or * 5 -NR 5 -CO-. R 5 is a hydrogen atom or a monovalent organic group. "* 5 " represents a bonding bond bonded to the condensed ring structure in the formula. Z 3 is a functional group capable of forming a bond by heat or light. Z 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 from 0 to 3. When there are multiple Rs 2 in the formula, the multiple Rs 2 are the same as or different from each other. Multiple Ys in the formula 6 are the same as or different from each other. Multiple a2s in the formula are the same as or different from each other.)

[0161] In the above formulas (9) and (10), examples of the "functional group capable of forming a bond by heat or light" include: epoxy group, alkoxysilyl group, silanol group, group containing a polymerizable unsaturated carbon-carbon bond (vinyl group, (meth)acryloyl group), maleimide group, R 20 OOC-CR 21 =CR 22 -CONR 23 -*(wherein, R 20 to R 23 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms), etc.). Among them, in terms of high reactivity by heat or light, a group containing a polymerizable unsaturated carbon-carbon bond is preferred.

[0162] When the groups represented by Z 2 and Z 4 are monovalent hydrocarbon groups, examples of the hydrocarbon group include: chain hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, etc. In terms of improving the reduction effect on DC afterimage, Z 2 and Z 4Preferably a functional group capable of forming a bond by heat or light, more preferably a group containing a polymerizable unsaturated carbon-carbon bond.

[0163] Specific examples of the additive (P) include, for example, compounds represented by the following formulas (a-1) to (a-5).

[0164] [Chemical formula 24]

[0165]

[0166] 《Other components》

[0167] The liquid crystal aligning agent of the present disclosure may also contain components other than the compound (P) (hereinafter, also referred to as "other components"). Examples of other components include: polymers that do not have the partial structure (A) represented by the formula (1) (hereinafter, also referred to as "other polymers"), compounds having one or more epoxy groups in the molecule, functional silane compounds, compounds having one or more (meth)acryloyl groups in the molecule, antioxidants, metal chelate compounds, curing accelerators, surfactants, fillers, dispersants, photosensitizers, acid generators, base generators, radical generators, etc. The blending ratio of these can be appropriately selected according to each compound within the range that does not impair the effects of the present disclosure.

[0168] <Other polymers>

[0169] The main skeleton of the other polymer is not particularly limited, and examples 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 liquid crystal element with high reliability, the other polymer is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, and a polymer containing a structural unit derived from a monomer having a polymerizable unsaturated carbon-carbon bond. Examples of the polymer 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 kind can be used alone, or two or more kinds can be used in combination.

[0170] When the compound (P) is a polymer and the liquid crystal aligning agent contains the polymer (P) and other polymers together, the content ratio of the other polymers is preferably 1% by mass or more, more preferably 2% by mass or more, relative to the total amount of the polymer (P) and the other polymers. Further, the content ratio of the other polymers is preferably 95% by mass or less, more preferably 90% by mass or less, relative to the total amount of the polymer (P) and the other polymers.

[0171] When the compound (P) is an additive component, the liquid crystal aligning agent of the present disclosure contains the additive (P) and a polymer component together. When the polymer component is another polymer, the content ratio of the other polymers is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, relative to the total amount of the solid components of the liquid crystal aligning agent (i.e., the components other than the solvent contained in the liquid crystal aligning agent). Further, the content ratio of the other polymers is preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 95% by mass or less, relative to the total amount of the solid components of the liquid crystal aligning agent.

[0172] <Solvent>

[0173] The liquid crystal aligning agent of the present disclosure is prepared as a liquid composition in which the compound (P) and other components used as needed are preferably dispersed or dissolved in a suitable solvent.

[0174] Examples of the organic solvent 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, ethylene glycol-isopropyl 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, isopentyl propionate, isopentyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. These can be used alone or in combination of two or more.

[0175] The solid content concentration in the liquid crystal aligning agent (the proportion of the total mass of the components other than the solvent of the liquid crystal aligning agent in the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1% by mass to 10% by mass. That is, the liquid crystal aligning agent is coated on the substrate surface as described later, and heating is preferably performed to form a coating film as the liquid crystal alignment film or a coating film that becomes the liquid crystal alignment film. At this time, if the solid content concentration is 1% by mass or more, the film thickness of the coating film can be sufficiently ensured, which is suitable in terms of easily obtaining a good liquid crystal alignment film. In addition, if the solid content concentration is 10% by mass or less, the film thickness of the coating film will not be too large, a good liquid crystal alignment film can be obtained, and the viscosity of the liquid crystal aligning agent can be appropriately ensured, and the coatability can be made good.

[0176] Regarding the content ratio of the compound (P) in the liquid crystal aligning agent, in the case where the compound (P) is a polymer, from the viewpoint of sufficiently obtaining the effects brought about by blending the polymer (P), it is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass in total of the solid components (components other than the solvent) in the liquid crystal aligning agent. In the case where 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 in total of the solid components in the liquid crystal aligning agent. In addition, from the viewpoint of ensuring the liquid crystal alignment property and electrical characteristics 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 in total of the solid components in the liquid crystal aligning agent.

[0177] "Liquid Crystal Alignment Film and Liquid Crystal Element"

[0178] The liquid crystal alignment film of the present disclosure is formed from a liquid crystal aligning agent prepared as described above. In addition, the liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal aligning agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, and for example, it can be applied to various modes such as Twisted Nematic (TN) type, SuperTwisted Nematic (STN) type, Vertical Alignment (VA) type (including Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), In-Plane Switching (IPS) type, fringe field switching (FFS) type, Optically Compensated Bend (OCB) type, etc. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the substrate used varies depending on the desired operation mode. Steps 2 and 3 are common to each operation mode.

[0179] (Step 1: Formation of a coating film)

[0180] First, a liquid crystal aligning agent is coated on a substrate, and preferably the coating surface is heated to form a coating film on the substrate. As the substrate, for example, the following can be used: glass such as float glass and soda glass; transparent substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly(alicyclic olefin). As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG Industries, Inc., USA) containing tin oxide (SnO2), an Indium Tin Oxide (ITO) film containing indium oxide-tin oxide (In2O3-SnO2), etc. can be used. In the case of manufacturing a TN-type, STN-type, VA-type, or PSA-type liquid crystal element, two substrates provided with patterned transparent conductive films are used. On the other hand, in the case of manufacturing an IPS-type or FFS-type liquid crystal element, a substrate provided with electrodes and a facing substrate not provided with electrodes are used, and the electrodes include a transparent conductive film or a metal film patterned in a comb shape. As the metal film, for example, a film containing a metal such as chromium can be used. The coating of the liquid crystal aligning agent on the substrate is preferably performed on the electrode formation surface by a lithographic printing method, a spin coating method, a roll coater method, or an inkjet printing method.

[0181] After coating the liquid crystal aligning agent, preheating (pre-baking) is preferably carried out for the purpose of preventing dripping of the coated liquid crystal aligning agent. The pre-baking temperature is preferably 30°C to 200°C, and the pre-baking time is preferably 0.25 minutes to 10 minutes. Thereafter, the solvent is completely removed, and if necessary, a calcination (post-baking) process is carried out for the purpose of thermally imidizing the amic acid structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80°C to 300°C, and the post-baking time is preferably 5 minutes to 200 minutes. The thickness of the film thus formed is preferably 0.001 μm to 1 μm. After coating the liquid crystal aligning agent on the substrate, the organic solvent is removed, thereby forming a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film.

[0182] (Process 2: Alignment treatment)

[0183] In the case of manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, a treatment (alignment treatment) for imparting liquid crystal alignment ability to the coating film formed in the above Process 1 is carried out. Thus, the liquid crystal molecules' alignment ability is imparted to the coating film to become 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 wiped 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. In the case of manufacturing a vertically aligned liquid crystal element, the coating film formed in the above Process 1 can be directly used as the liquid crystal alignment film, and in order to further improve the liquid crystal alignment ability, the coating film can also be subjected to an alignment treatment.

[0184] The light irradiation in the photo-alignment treatment can be carried out by methods such as: a method of irradiating the coating film after the post-baking process, a method of irradiating the coating film after the pre-baking process and before the post-baking process, and a method of irradiating the coating film during the heating process of the coating film in at least one of the pre-baking process and the post-baking process. In the photo-alignment treatment, as the radiation for irradiating the coating film, for example, ultraviolet rays and visible light including light having a wavelength of 150 nm to 800 nm can be used. Ultraviolet rays including light having a wavelength of 200 nm to 400 nm are preferred. When the radiation is polarized light, it can be linearly polarized light or partially polarized light. In addition, when the radiation used is linearly polarized light or partially polarized light, the irradiation can be carried out from a direction perpendicular to the substrate surface, from an inclined direction, or a combination of these can be carried out. When irradiating non-polarized radiation, the irradiation direction is set to an inclined direction.

[0185] As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used. The irradiation amount of the radiation is preferably 400 J / m 2 ~20,000 J / m 2, more preferably 1,000 J / m 2 ~5,000 J / m 2 . In order to improve the reactivity, light irradiation can be performed on the coating film while heating the coating film.

[0186] When manufacturing a liquid crystal alignment film, the coating film after the light irradiation treatment can be heated in a temperature range of 120°C or higher and 280°C or lower. Through this heat treatment, a liquid crystal element with further improved liquid crystal alignment (heat reorientation) and further reduced AC afterimage can be obtained, which is preferable in this regard. The heating can be post-baking or a heat treatment performed independently of post-baking after post-baking. From the viewpoint of promoting the reorientation of molecular chains caused by heating, the heating temperature is preferably set to 140°C or higher, more preferably 150°C to 250°C. The heating time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 60 minutes.

[0187] When manufacturing a liquid crystal alignment film, it can further include a contact step of bringing the coating film after the light irradiation treatment into contact with water, a water-soluble organic solvent, or a mixed solvent of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include: methanol, ethanol, 1-propanol, isopropanol, 1-methoxy-2-propyl acetate, butyl cellosolve, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone. Examples of the method of bringing the coating film into contact with the solvent include: spray (spray) treatment, shower treatment, dipping treatment, liquid covering treatment, etc., but are not limited to these. The contact time between the coating film and the solvent is not particularly limited, for example, it is 5 seconds to 15 minutes. A heat treatment of the coating film can be performed after the contact step.

[0188] (Process 3: Construction of liquid crystal cell)

[0189] Prepare two substrates each formed with a liquid crystal alignment film as described above, and dispose liquid crystal between the two substrates arranged facing each other, thereby manufacturing a liquid crystal cell. When manufacturing a liquid crystal cell, for example, the following methods can be cited: (1) A method in which two substrates are arranged facing each other with a gap (spacer) between them with the liquid crystal alignment films facing each other, the peripheral portions of the two substrates are bonded using a sealant, the liquid crystal is injected and filled into the cell gap defined by the substrate surfaces and the sealant, and then the injection hole is sealed; (2) A method in which the sealant is applied to a specified location on one of the substrates formed with the liquid crystal alignment film, and then liquid crystal is dropped at several specified locations on the liquid crystal alignment film surface, and then the other substrate is bonded with the liquid crystal alignment films facing each other, and the liquid crystal is spread over the entire surface of the substrate (one drop filling (ODF) method) and the like. Ideally, the manufactured liquid crystal cell is further heated to the temperature at which the liquid crystal used becomes isotropic and then slowly cooled to room temperature, thereby removing the flow orientation during liquid crystal filling.

[0190] As the sealant, for example, a hardener and an epoxy resin containing alumina balls as spacers can be used. As the spacers, photo spacers, bead spacers, etc. can be used.

[0191] As the liquid crystal, either positive or negative type can be used. When a negative liquid crystal is used in an IPS-type or FFS-type liquid crystal element, the transmission loss above the electrodes can be reduced, and an improvement in contrast can be achieved, which is preferable in this regard. In addition, as the liquid crystal, nematic liquid crystals, smectic liquid crystals, etc. can be mentioned, and among them, nematic liquid crystals are preferred. As the nematic liquid crystal, for example, Schiff base type liquid crystals, azoxy type liquid crystals, biphenyl type liquid crystals, phenylcyclohexane type liquid crystals, ester type liquid crystals, terphenyl type liquid crystals, biphenylcyclohexane type liquid crystals, pyrimidine type liquid crystals, dioxane type liquid crystals, bicyclooctane type liquid crystals, cubane type liquid crystals, etc. can be used. In addition, cholesteric liquid crystals, chiral agents, ferroelectric liquid crystals, etc. can also be added to and used in these liquid crystals.

[0192] In the PSA mode, the following treatment is performed: After filling a polymerizable compound (for example, a polyfunctional (meth)acrylate compound, etc.) and a liquid crystal into the cell gap to construct a liquid crystal cell, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films provided on a pair of substrates. When manufacturing a PSA-type liquid crystal element, the usage ratio of the polymerizable compound is, for example, 0.01 part by mass to 3 parts by mass, preferably 0.1 part by mass to 1 part by mass, relative to a total of 100 parts by mass of the liquid crystal.

[0193] Subsequently, a polarizing plate is attached to the outer surface of the liquid crystal cell as needed. As the polarizing plate, a polarizing plate formed by sandwiching a polarizing film called an "H film" with a cellulose acetate protective film, or a polarizing plate including the "H film" itself can be mentioned. The "H film" is formed by stretching and orienting polyvinyl alcohol and absorbing iodine. Thus, a liquid crystal element can be obtained.

[0194] The liquid crystal element of the present disclosure can be effectively applied to various uses, for example, it can be used in various display devices such as clocks, portable game consoles, word processors, notebook computers, car navigation systems, cameras, personal digital assistants (PDAs), digital cameras, mobile phones, smart phones, various monitors, liquid crystal televisions, information displays, etc., or in dimming films, etc. In addition, the 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.

[0195] [Examples]

[0196] Hereinafter, it will be described more specifically by way of examples, but the present invention is not limited to these examples.

[0197] <Structure and Abbreviation of Compounds>

[0198] The structures and abbreviations of the main compounds used in the following examples are as described below.

[0199] [Tetracarboxylic Dianhydride]

[0200] TA-1: 1,2,3,4-Cyclobutanetetracarboxylic Dianhydride

[0201] TA-2: (1R,2R,3S,4S)-1,3-Dimethylcyclobutane-1,2,3,4-tetracarboxylic Dianhydride

[0202] TA-3: 2,3,5-Tricarboxycyclopentylacetic Dianhydride

[0203] TA-4: Pyromellitic Dianhydride

[0204] TA-5: 4,4'-Diphthalic Dianhydride

[0205] [Chemical Formula 25]

[0206]

[0207] [Diamine]

[0208] DA-1: 9,9'-Bis(4-aminophenyl)-3,3'-bicarbazole

[0209] DA-2: 9,9'-Bis(4-(4-aminophenoxy)phenyl)-3,3'-bicarbazole

[0210] DA-3: 9,9'-Diethyl-6,6'-bis(4-aminophenoxy)-3,3'-bicarbazole

[0211] DA-4: 9,9'-Diethyl-3,3'-bicarbazole-6,6'-diamine

[0212] DA-5: 4,4'-Diaminodiphenylamine

[0213] DA-6: 3,6-Diaminocarbazole

[0214] DA-7: 4,4'-Diaminotriphenylamine

[0215] DA-8: N4,N4'-Bis(4-aminophenyl)-N4,N4'-dimethylbenzidine

[0216] DA-9: 4,4'-Diaminodiphenylmethane

[0217] DA-10: 3,5-Diaminobenzoic acid

[0218] DA-11: 4,4'-Bis(4-aminophenoxy)biphenyl

[0219] DA-12: 2,2-Bis(4-(4-aminophenoxy)phenyl)propane

[0220] DA-13: 2,2'-Dimethylbenzidine

[0221] DA-14: 5(6)-Amino-1,3,3-trimethyl-1-(4-aminophenyl)indane

[0222] DA-15: N,N'-Bis(5-aminopyridin-2-yl)-N,N'-bis(tert-butoxycarbonyl)ethylenediamine

[0223] DA-16: N1,N6-Bis(4-aminophenethyl)-N1,N6-bis(tert-butoxycarbonyl)hexanediamide

[0224] DA-17: 5ξ-Cholestan-3-yl 2,4-diaminophenyl ether

[0225] [Chemical formula 26]

[0226]

[0227] [Chemical formula 27]

[0228]

[0229] [Chemical formula 28]

[0230]

[0231] [Solvent]

[0232] NMP: N-Methyl-2-pyrrolidone

[0233] NEP: N-Ethyl-2-pyrrolidone

[0234] GBL: γ-Butyrolactone

[0235] BC: Butyl Cellosolve

[0236] DAA: Diacetone Alcohol

[0237] DEDG: Diethylene Glycol Diethyl Ether

[0238] [Additive]

[0239] AD-1: N,N,N',N'-Tetraglycidyl-4,4'-Diaminodiphenylmethane

[0240] AD-2: 3-Glycidoxypropyltriethoxysilane

[0241] AD-3: Dipentaerythritol Hexaacrylate

[0242] AD-4: 2,4,6,8-Tetramethyl-2,4,6,8-Tetrakis(3-Glycidoxypropyl)-1,3,5,7,2,4,6,8-Tetraoxatetrasiloxane

[0243] AD-5: Compound Represented by the Following Formula (AD-5)

[0244] [Chemical Formula 29]

[0245]

[0246] [Chemical Formula 30]

[0247]

[0248] <Synthesis of Compound>

[0249] [Synthesis Example 1]

[0250] In a three-necked flask equipped with a nitrogen inlet tube, 3,3'-bicarbazole (3.0 mmol), p-fluoronitrobenzene (7.5 mmol), potassium carbonate (12 mmol), and NMP (20 mL) were placed, and the mixture was heated and stirred at 160 °C for 6 hours under nitrogen. After the reaction was completed, the reaction solution was poured into water to precipitate the product. The obtained precipitate was washed with water and ethyl acetate and dried under vacuum to obtain a yellowish-brown solid, the compound represented by the following formula (DA-1-1), in a yield of 90%.

[0251] In a three-necked flask equipped with a nitrogen inlet tube, compound (DA-1-1) (2.0 mmol), 5% Pd / C (0.23 g), hydrazine monohydrate (1.15 g), and NMP (20 mL) were placed, and the mixture was heated and stirred at 80 °C for 6 hours under nitrogen. After completion of the reaction, the reaction solution was filtered through diatomaceous earth, ethyl acetate was added, and the mixture was washed by liquid separation with water. The organic phase was concentrated under reduced pressure, and thus 9,9'-bis(4-aminophenyl)-3,3'-bicarbazole (the diamine represented by the formula (DA-1)), a brown solid, was obtained in a yield of 80%. In Figure 1 and Figure 2 the measurement results of the 1H-NMR spectrum (dimethylsulfoxide (DMSO)-d6, 400 MHz) and 1 13C-NMR spectrum (DMSO-d6, 75 MHz) of the diamine (DA-1) are shown, respectively. 13

[0252] [Chemical formula 31]

[0253]

[0254] [Synthesis Example 2]

[0255] In accordance with the following reaction process, 9,9'-bis(4-(4-aminophenoxy)phenyl)-3,3'-bicarbazole (the diamine represented by the formula (DA-2)) was obtained in the same manner as in Synthesis Example 1.

[0256] [Chemical formula 32]

[0257]

[0258] [Synthesis Example 3]

[0259] In accordance with the following reaction process, 9,9'-diethyl-6,6'-bis(4-aminophenoxy)-3,3'-bicarbazole (the diamine represented by the formula (DA-3)) was obtained in the same manner as in Synthesis Example 1. In addition, 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).

[0260] [Chemical formula 33]

[0261]

[0262] [Synthesis Example 4]

[0263] 9,9'-Diethyl-3,3'-bicarbazole-6,6'-diamine (the diamine represented by the formula (DA-4)) was obtained in the same manner as in Synthesis Example 1 according to the following reaction scheme. In addition, 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).

[0264] [Chemical Formula 34]

[0265]

[0266] <Polymer Synthesis and Evaluation>

[0267] Polymers were synthesized in the following Synthesis Examples 5 to 25, respectively. In addition, in the following examples, the weight average molecular weight M w and the number average molecular weight M n of the polymer, the 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.

[0268] [Weight average molecular weight M w and number average molecular weight M n

[0269] In Synthesis Examples 24 and 25, M w and M n are polystyrene conversion values measured by GPC under the following conditions.

[0270] Column: Manufactured by Tosoh Corporation, TSKgel IGRCXLII

[0271] Solvent: Tetrahydrofuran

[0272] Temperature: 40 °C

[0273] Pressure: 68 kgf / cm 2

[0274] [Imidization Rate of Polyimide]

[0275] The solution of the polyimide was poured into pure water, and the obtained precipitate was thoroughly dried under reduced pressure at room temperature and then dissolved in deuterated dimethyl sulfoxide. Using tetramethylsilane as a reference substance, 1 1H-NMR was measured at room temperature. According to the obtained 1 1H-NMR spectrum (400 MHz), the imidization rate [%] was calculated using the following formula (1).

[0276] ​Imidization rate [%] = (1 - (A1 / (A2 × α))) × 100…(1)

[0277] (In formula (1), A1 is the peak area of protons derived from amide groups that appear near a chemical shift of 10 ppm, A2 is the peak area of protons derived from aromatic groups that appear near a chemical shift of 6 ppm to 9 ppm, and α is the number ratio of protons of the aromatic group to one proton of the amide group in the precursor (polyamic acid) of the polymer.)

[0278] [Solution viscosity of polymer solution]

[0279] The solution viscosity (mPa·s) of the polymer solution is measured at 25 °C using an E-type rotational viscometer.

[0280] [Epoxy equivalent weight]

[0281] The epoxy equivalent weight is measured by the hydrochloric acid - methyl ethyl ketone method described in JIS C 2105.

[0282] [Synthesis Example 5]

[0283] Dissolve diamines (20 mol parts of diamine (DA-1) and 80 mol parts of diamine (DA-9)) in NMP, add 0.95 molar equivalents of tetracarboxylic dianhydride (TA-1) relative to the total amount of diamines, and react 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 (PA-1).

[0284] [Chemical formula 35]

[0285]

[0286] [Synthesis Examples 6 to 22]

[0287] Change the types and molar ratios of the tetracarboxylic dianhydride and diamines as described in Table 1 below. Otherwise, obtain polyamic acids (PI-2 to PI-18) in the same manner as in Synthesis Example 5. In addition, for the values in Table 1, for the acid dianhydride, it represents the usage ratio (mol%) of each compound relative to the total amount of acid dianhydride used in the synthesis (100 mol%), and for the diamine, it represents the usage ratio (mol%) of each compound relative to the total amount of diamine used in the synthesis (100 mol%).

[0288] [Synthesis Example 23]

[0289] Dissolve diamines (50 mol parts of diamine (DA-15) and 50 mol parts of diamine (DA-13)) in NMP, add 0.95 molar equivalents of tetracarboxylic dianhydride (TA-2) relative to the total amount of diamines, and react at room temperature for 6 hours to obtain a solution of polyamic acid. Add 0.80 molar equivalents of 1-methylpiperidine and acetic anhydride relative to the carboxyl groups of the polyamic acid to the obtained solution, and heat and stir at 60 °C for 3 hours. Repeatedly perform concentration under reduced pressure and dilution with NMP on the obtained solution 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) is 78%.

[0290] [Chemical Formula 36]

[0291]

[0292] [Table 1]

[0293]

[0294] [Synthesis Example 24]

[0295] Place 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (compound represented by the following formula (S-1)), 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, and mix at room temperature. Subsequently, dropwise add 100 g of deionized water from the dropping funnel over 30 minutes, and while stirring under reflux, react at 80 °C for 6 hours. After the reaction is completed, take out the organic layer, wash it with a 0.2% by mass ammonium nitrate aqueous solution until the washed water becomes neutral, and then distill off the solvent and water under reduced pressure to obtain polyorganosiloxane (ESSQ-1) containing epoxy groups in the form of a viscous transparent liquid. Perform 1 1H-NMR analysis on polyorganosiloxane (ESSQ-1). As a result, a peak based on epoxy groups was observed near the chemical shift (δ) = 3.2 ppm, confirming that no side reactions of epoxy groups occurred during the reaction. The weight average molecular weight M w of the obtained polyorganosiloxane (ESSQ-1) is 3,500, and the epoxy equivalent is 180 g / mol.

[0296] In a 200 mL three-necked flask, 10.0 g of polyorganosiloxane (ESSQ-1), 30.28 g of methyl isobutyl ketone as a solvent, a compound represented by the following formula (S-2) and a compound represented by the following formula (S-3) as modifying components (carboxylic acids) in amounts corresponding to 20 mol% and 10 mol%, respectively, of the total amount of epoxy groups in polyorganosiloxane (ESSQ-1), and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) as a catalyst were added, and the reaction was carried out with stirring at 100 °C for 48 hours. After completion of the reaction, the solution obtained by adding ethyl acetate to the reaction mixture was washed three times with water, the organic layer was dried using magnesium sulfate, and then the solvent was distilled off to obtain polyorganosiloxane (PSQ-1) containing an orienting group. The weight-average molecular weight M of the obtained polymer w was 8000.

[0297] [Chemical formula 37]

[0298]

[0299] [Synthesis Example 25]

[0300] Under nitrogen, 6.38 g of a compound represented by the following formula (M-1) as a polymerization monomer, 1.90 g of 4-(glycidyloxymethyl)styrene (a compound represented by the following formula (M-2)), 0.86 g of methacrylic acid, 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 were added to a 100 mL two-necked flask, and polymerization was carried out at 70 °C for 6 hours. After reprecipitation in methanol, the precipitate was filtered and vacuum dried at room temperature for 8 hours to obtain the target polymer (PMI-1). The weight-average molecular weight M measured by GPC in terms of polystyrene conversion w was 30000, and the molecular weight distribution M w / M n was 2.

[0301] [Chemical formula 38]

[0302]

[0303] <Preparation and Evaluation of Liquid Crystal Orienting Agent>

[0304] [Example 1: Photo-Oriented FFS-Type Liquid Crystal Display Element]

[0305] (1) Preparation of Liquid Crystal Orienting Agent

[0306] The polymer components (in terms of 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 having a solid content concentration of 4.0% by mass and a solvent composition ratio of NMP:GBL:BC = 50:25:25 (mass ratio). The solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent (AL-1).

[0307] (2) Evaluation of optical properties (transparency)

[0308] The liquid crystal aligning agent (AL-1) prepared in (1) above was coated on a quartz substrate using a spin coater, heated on a hot plate at 80°C for 1 minute, and then heated in an oven at 230°C for 30 minutes after replacing the gas in the chamber with nitrogen to form a coating film with an average film thickness of 100 nm. For the quartz substrate having the coating film formed thereon, using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation, product name “V-670”), with the same type of quartz substrate without a coating film as a reference, the absorption spectra in the ultraviolet and visible light regions were measured. In addition, by using P-polarized light through a polarizing filter and setting the incident angle to the substrate to the Brewster's angle, the influence of reflection was suppressed. When the transmittance at a wavelength of 400 nm was 98% or more, it was evaluated as “good”, and when it was less than 98%, it was evaluated as “bad”. As a result, in this example, the evaluation was “good”.

[0309] (3) Formation of a liquid crystal alignment film by photo-alignment method

[0310] The liquid crystal aligning agent (AL-1) prepared in (1) above was coated on the respective surfaces of a glass substrate having a flat electrode, an insulating layer, and a comb-shaped electrode laminated in sequence on one side and a facing glass substrate without an electrode provided thereon using a spin coater, heated on a hot plate at 80°C for 1 minute, and then heated in an oven at 230°C for 30 minutes after replacing the gas in the chamber with nitrogen to form a coating film with an average film thickness of 100 nm. The coating film surface was irradiated with ultraviolet light containing a bright line of 254 nm linearly polarized at 300 mJ / cm 2 from the substrate normal direction using a Hg-Xe lamp for photo-alignment treatment. The coating film subjected to the photo-alignment treatment was heated in an oven at 230°C for 30 minutes after replacing the gas in the chamber with nitrogen for heat treatment to form a liquid crystal alignment film.

[0311] (4) Manufacture of an FFS type liquid crystal display element

[0312] On the outer periphery of the surface of a substrate with a liquid crystal alignment film among the substrates fabricated in the above (3), a liquid crystal injection port was left, and an epoxy resin adhesive containing alumina balls with a diameter of 3.5 μm was coated using a dispenser. After that, the surfaces of a pair of substrates with liquid crystal alignment films were made to face each other, and they were pressed together in such a manner that the alignment treatment directions of the respective substrates were antiparallel, and the adhesive was thermally cured at 150 °C for 1 hour. Subsequently, a negative nematic liquid crystal (manufactured by Merck Co., Ltd., MLC20195NCMP) was filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed using an epoxy-based adhesive. Further, in order to remove the flow alignment during liquid crystal injection, after heating at 120 °C, it was slowly cooled to room temperature. Next, polarizing plates were attached to the outer two surfaces of the substrate in such a manner that their polarization directions were orthogonal to each other and at an angle of 45° with respect to the alignment treatment direction of the liquid crystal alignment film, thereby manufacturing an FFS-type liquid crystal display element.

[0313] (5) Evaluation of DC afterimage characteristics

[0314] The liquid crystal display element fabricated in the above (4) was placed in an environment of 25 °C and one atmospheric pressure. After driving with a rectangular wave (alternating current (AC)) at a frequency of 30 Hz in an intermediate tone and setting the brightness difference between any two pixels to 0, while driving with AC, a direct current (DC) of 1 V was applied to only a single pixel for 30 minutes to accumulate charges. When the application of DC 1 V was completed and the driving was returned to only AC driving, a brightness difference ΔL was generated between the two pixels due to the accumulated charges. The time-dependent change of the brightness difference ΔL was observed, and the time from the completion of the application of DC 1 V until the value obtained by dividing the brightness difference ΔL by the average brightness of the two pixels became 2% or less was defined as the afterimage elimination time. In addition, the shorter this time, the less likely it is to generate an afterimage due to the application of a DC voltage. The case where the afterimage elimination time is less than 10 minutes was defined as "excellent", the case where it is 10 minutes or more and less than 20 minutes was defined as "good", and the case where it is 20 minutes or more was defined as "poor". As a result, in this example, the evaluation was "excellent".

[0315] [Examples 2 to 12, Comparative Examples 1 to 4]

[0316] In Example 1 above, the components contained in the liquid crystal aligning agent were changed as shown in Table 2 below. Except for this, a liquid crystal aligning agent was prepared in the same manner as in Example 1, and a liquid crystal alignment film was formed by the photoalignment method, and an FFS-type liquid crystal display element was manufactured, and various evaluations were performed. The evaluation results are shown in Table 2 below.

[0317] [Example 13: Friction-aligned FFS-type liquid crystal display element]

[0318] (1) Preparation of Liquid Crystal Alignment Agent

[0319] The polymer components (in terms of 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 concentration of 4.0% by mass and a solvent composition ratio of NMP:GBL:DAA:BC = 30:30:30:10 (mass ratio). The solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal alignment agent (AL-17).

[0320] (2) Evaluation of Optical Properties (Transparency)

[0321] Regarding the liquid crystal alignment agent (AL-17) prepared in (1) above, the transparency was evaluated in the same manner as in Example 1. As a result, the evaluation in this example was "good".

[0322] (3) Formation of Liquid Crystal Alignment Film by Rubbing Method

[0323] The liquid crystal alignment agent (AL-17) prepared in (1) above was coated on the surfaces of a glass substrate having a flat electrode, an insulating layer, and a comb-shaped electrode laminated in sequence on one side, and a facing glass substrate without an electrode, using a spin coater. After heating on a hot plate at 80°C for 1 minute, it was heated in an oven at 230°C with nitrogen replacement in the chamber for 30 minutes to form a coating film with an average film thickness of 100 nm. The surface of the coating film was subjected to two rubbing treatments using a rubbing machine having a roller wound with a nylon cloth, at a roller rotation speed of 1000 rpm, a platform moving speed of 30 mm / second, and a pile penetration length of 0.3 mm. The coating film subjected to the rubbing alignment treatment 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.

[0324] (4) Manufacture of FFS-Type Liquid Crystal Display Element

[0325] Regarding a pair of substrates having the liquid crystal alignment film produced in (3) above, an FFS-type liquid crystal display element was manufactured in the same manner as in Example 1.

[0326] (5) Evaluation of DC Ghosting Characteristics

[0327] Regarding the FFS-type liquid crystal display element manufactured in (4) above, the DC ghosting characteristics were evaluated in the same manner as in Example 1. As a result, the evaluation in this example was "excellent".

[0328] [Examples 14 to 15 and Comparative Examples 5 to 6]

[0329] In Example 13, the components contained in the liquid crystal aligning agent were changed as shown in Table 2 below. Except for this, a liquid crystal aligning agent was prepared in the same manner as in Example 13, and a liquid crystal alignment film was formed by the rubbing method. Then, an FFS-type liquid crystal display element was manufactured and various evaluations were carried out. The evaluation results are shown in Table 2 below.

[0330] [Example 16: PSA-Type Liquid Crystal Display Element]

[0331] (1) Preparation of Liquid Crystal Aligning Agent

[0332] The polymer components (in terms of 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 concentration of 4.0% by mass and a solvent composition ratio of NMP:BC = 50:50 (mass ratio). The solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent (AL-22).

[0333] (2) Preparation of Liquid Crystal Composition

[0334] To 10 g of nematic liquid crystal (manufactured by Merck, MLC-6608), 5% by mass of the liquid crystalline compound represented by the following formula (L-1) and 0.3% by mass of the photopolymerizable compound represented by the following formula (L-2) were added and mixed to obtain a liquid crystal composition (LC-1).

[0335] [Chemical Formula 39]

[0336]

[0337] (3) Evaluation of Optical Properties (Transparency)

[0338] Regarding the liquid crystal aligning agent (AL-22) prepared in (1) above, the transparency was evaluated in the same manner as in Example 1. As a result, the evaluation in this example was "good".

[0339] (4) Formation of Liquid Crystal Alignment Film

[0340] The liquid crystal aligning agent (AL-22) prepared in (1) above was coated on the electrode surfaces of two glass substrates each having an ITO electrode patterned in a slit shape using a spin coater. After heating on a hot plate at 80 °C for 1 minute, it was heated in an oven at 230 °C with nitrogen replacement in the chamber for 30 minutes to form a coating film with an average film thickness of 100 nm. The 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. In addition, the pattern of the electrode used was the same as the electrode pattern in the PSA mode.

[0341] (5) Fabrication of the PSA type liquid crystal display element

[0342] On the outer periphery of the surface of one substrate among the substrates fabricated in the above (4) that has a liquid crystal alignment film, leaving a liquid crystal injection port, an epoxy resin adhesive added with alumina balls having a diameter of 3.5 μm is coated using a dispenser. Thereafter, the substrates are overlapped and pressed with the surfaces having the liquid crystal alignment films facing each other, and the adhesive is thermally cured at 150 °C for 1 hour. Subsequently, after filling the liquid crystal composition (LC-1) prepared in the above (2) into the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port is sealed using an epoxy-based adhesive, thereby fabricating a liquid crystal cell.

[0343] For the obtained liquid crystal cell, while driving the liquid crystal by applying an alternating current of 10 V at a frequency of 60 Hz between the counter electrodes, using an ultraviolet irradiation device using a metal halide lamp as a light source, ultraviolet rays are irradiated at an irradiation dose of 10,000 mJ / cm 2 . Further, the irradiation dose is a value measured using a quantum meter measured based on a wavelength of 365 nm. Next, polarizing plates are attached to the outer two surfaces of the substrate in such a manner that their polarization directions are orthogonal to each other and at an angle of 45° with respect to the alignment treatment direction of the liquid crystal alignment film, thereby fabricating a PSA type liquid crystal display element.

[0344] (6) Evaluation of DC afterimage characteristics

[0345] For the liquid crystal display element fabricated in the above (5), the DC afterimage characteristics are evaluated in the same manner as in Example 1. As a result, the evaluation in this example is "excellent".

[0346] [Example 17]

[0347] In the above Example 16, the components contained in the liquid crystal aligning agent are changed as shown in Table 2 below. Other than this, a liquid crystal aligning agent is prepared and a liquid crystal alignment film is formed in the same manner as in Example 16, and a PSA type liquid crystal display element is fabricated and various evaluations are performed. The evaluation results are shown in Table 2 below.

[0348] [Example 18: Photo-aligned VA type liquid crystal display element]

[0349] (1) Preparation of liquid crystal aligning agent

[0350] The polymer and additive components (in terms of solid components: 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)) are diluted with NMP, GBL, DEDG, and BC to obtain a solution with a solid component concentration of 4.0% by mass and a solvent composition ratio of NMP:GBL:DEDG:BC = 30:30:30:10 (mass ratio). The solution is filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent (AL-24).

[0351] (2) Evaluation of optical properties (transparency)

[0352] For the liquid crystal aligning agent (AL-24) prepared in (1) above, the transparency is evaluated in the same manner as in Example 1. As a result, the evaluation in this example is "good".

[0353] (3) Formation of a liquid crystal alignment film by photoalignment method

[0354] The liquid crystal aligning agent (AL-24) prepared in (1) above is coated on the electrode surfaces of two glass substrates each having an ITO electrode using a spin coater. After heating on a hot plate at 80 °C for 1 minute, it is heated in an oven at 230 °C with nitrogen replacement in the chamber for 30 minutes to form a coating film with an average film thickness of 100 nm. The surface of the coating film is irradiated with ultraviolet light containing a bright line of 313 nm linearly polarized light at 20 mJ / cm 2 from a direction inclined 40° with respect to the normal direction of the substrate to perform photoalignment treatment to form a liquid crystal alignment film.

[0355] (4) Manufacture of a VA type liquid crystal display element

[0356] Around the outer periphery of the surface having the liquid crystal alignment film of one of the substrates fabricated in (3) above, an epoxy resin adhesive containing alumina balls with a diameter of 3.5 μm is coated leaving a liquid crystal injection port using a dispenser. Then, the surfaces of the pair of substrates having the liquid crystal alignment films are faced to each other, and they are pressed together such that the projection directions of the optical axes of the ultraviolet light of each substrate on the substrate surface are antiparallel, and the adhesive is thermally cured at 150 °C for 1 hour.

[0357] Subsequently, a negative nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-6608) was filled into the gap between the substrates from the liquid crystal injection port. After that, the liquid crystal injection port was sealed with an epoxy-based adhesive. Further, in order to remove the flow alignment during liquid crystal injection, it was heated at 120°C and then slowly cooled to room temperature. Next, polarizing plates were attached to the outer two sides of the substrates in such a way that their polarization directions were orthogonal to each other and at an angle of 45° with respect to the alignment treatment direction of the liquid crystal alignment film, thereby manufacturing a VA-type liquid crystal display element.

[0358] (5) Evaluation of DC afterimage characteristics

[0359] For the liquid crystal display element manufactured in (4) above, the DC afterimage characteristics were evaluated in the same manner as in Example 1. As a result, the evaluation in this example was "good".

[0360] [Example 19]

[0361] In Example 18 above, the components contained in the liquid crystal aligning agent were changed as shown in Table 2 below. Other than that, a liquid crystal aligning agent was prepared in the same manner as in Example 18, and a liquid crystal alignment film was formed by the photo-alignment 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.

[0362] [Table 2]

[0363]

[0364] In Table 2, the mass ratio of each component of the liquid crystal aligning agent represents the blending ratio (parts by mass) of each compound with respect to a total of 100 parts by mass of the polymer component and the additive component used in the preparation of the liquid crystal aligning agent.

[0365] As shown in Table 2, among the liquid crystal aligning agents of Examples 1 to 19 containing the polymer (P), the optical characteristics (transparency) of the liquid crystal alignment film were "good", and the DC afterimage characteristics of the liquid crystal display element were "excellent" or "good", thus achieving a balance of various characteristics. In contrast, among the liquid crystal aligning agents of Comparative Examples 1 to 6 that did not contain the polymer (P), at least one of the optical characteristics (transparency) of the liquid crystal alignment film and the DC afterimage characteristics of the liquid crystal display element was "poor", which was inferior to the examples.

[0366] Here, the results of Examples 1 to 19 and Comparative Examples 1 to 6 were examined.

[0367] In the liquid crystal aligning agents of Examples 1 to 19, a polymer (P) having a partial structure (A) is contained. The condensed ring skeleton of the partial structure (A) has a low ionization potential, and due to the cyclic structure, the molecular chain is easily in-plane oriented (π-π stacking) in the solid. Therefore, it is speculated that when a liquid crystal alignment film is formed, intermolecular hopping conduction is promoted, and the charge (hole) transport property is likely to be high. Thus, it is considered that when a liquid crystal display element is formed, the accumulated charge is easily relaxed, and the DC residual image characteristics are excellent.

[0368] In addition, the partial structure (A) easily forms a structure in which the portion adjacent to the condensed ring is bent or distorted in the polymer (P). Therefore, in the condensed ring skeleton of the partial structure (A), the π-conjugation system of the condensed ring is not easily extended to the adjacent portion, and thus it is not easy to absorb light in the visible light region. As a result, it is considered that the optical properties (transparency) are excellent when a liquid crystal alignment film is formed. In addition, since the condensed ring skeleton in the partial structure (A) easily forms a bent or distorted structure with the adjacent portion, it is considered that although the condensed ring in the partial structure (A) has high planarity, the crystallinity is low. When a diamine or a polymer is formed, it exhibits excellent solubility in various solvents, and when a liquid crystal aligning agent is formed, it exhibits excellent coatability (spin coatability, inkjet printability, lithographic printability) and storage stability.

[0369] In addition, the polymer (P) does not easily absorb light in the visible light region, and the change in electrical properties (dielectric constant, resistivity, etc.) under backlight irradiation is small. It is speculated that when a liquid crystal display element is formed, the accumulation of charge and the occurrence of flicker are easily suppressed. Furthermore, it is considered that the deterioration of the liquid crystal alignment film when irradiating a high-brightness backlight can be suppressed, and a liquid crystal display element with excellent long-term reliability in which the deterioration of the DC residual image characteristics is suppressed can be obtained.

[0370] On the other hand, in the liquid crystal aligning agents of Comparative Examples 1 to 3 and Comparative Example 5, the DC residual image characteristics are "poor". It is speculated that the reason is that the ionization potential is high and the charge transport property in the liquid crystal alignment film is low. In addition, in the liquid crystal aligning agents of Comparative Examples 1, 2, and 5, the optical properties (transparency) are "poor". It is speculated that the reason is that the liquid crystal alignment film obtained by using the polymer (PI-5) and the polymer (PI-6) is easily oxidized and deteriorated, and the transparency becomes poor. In the liquid crystal aligning agents of Comparative Examples 4 and 6, the optical properties (transparency) are "poor". It is considered that the reason is that the π-conjugation system is easily extended to the entire repeating unit, and it is easily excited by light with lower energy, and thus it is easy to absorb light in the visible light region.

[0371] <Evaluation of Polymer by Quantum Chemical Calculation>

[0372] [Example 20]

[0373] Regarding the polyimide obtained by polycondensation of a tetracarboxylic dianhydride (TA-1) and a diamine (DA-1) (the polymer represented by the following formula (PI-20)), the physical properties of the polymer were evaluated by performing quantum chemical calculations on the bis-succinimide represented by the following formula (SI-1) as its repeating unit. As the quantum chemical calculation program, Gaussian 16 (Revision B.01) manufactured by Gaussian, Inc. in the United States was used, and the calculation was performed by the density functional theory (DFT).

[0374] [Chemical formula 40]

[0375]

[0376] (1) Evaluation of HOMO energy level and DC afterimage characteristics

[0377] Using B3LYP as the functional and 6-31G(d) as the basis function, the most stable structure of bis-succinimide (SI-1) in the ground state under vacuum was calculated. In addition, for the obtained most stable structure, the van der Waals volume V (cm 3 / mol) was obtained by the Monte Carlo method. Furthermore, single-point energy calculation was 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). In addition, it is known that the closer the energy level is to the work function of ITO (-4.5 eV to -5.0 eV), the easier it is for charge (hole) injection from the ITO electrode interface to occur, and the easier it is for charge accumulation during driving. In addition, it is known that the lower the energy level, the higher the ionization potential, the easier it is for the charge (hole) transport property to decrease, and the less likely it is for charge relaxation during driving. Regarding the evaluation of the DC afterimage characteristics of bis-succinimide (SI-1), the case where the HOMO energy level is -5.5 eV or higher and less than -5.2 eV is set as "good", and the case where it is less than -5.5 eV or -5.2 eV or higher is set as "bad". As a result, the evaluation in this example is "good".

[0378] (2) Evaluation of absorption edge and transparency

[0379] For the most stable structure obtained in (1) above, the singlet excited state was calculated by time-dependent density functional theory (TD-DFT), using B3LYP as the functional and 6-311+G(d) as the basis function. For each electronic transition (excitation energy and oscillator strength), the full width at half maximum was set to 0.25 eV, and the molar extinction coefficient ε (L / mol / cm) at each wavelength was calculated. Using the van der Waals volume V (cm 3 / mol) obtained in (1) above, the transmittance spectrum in a 100-nm-thick film was determined. Furthermore, based on the obtained transmittance spectrum, the wavelength at which the transmittance is 99% or more (absorption edge) was calculated. Comparison of the calculated results with the measured results revealed that, under the calculation conditions, the absorption edge shifted approximately 40 nm toward the longer wavelength side. Regarding the evaluation of the transparency of bis(succinimide) (SI-1), a case where the absorption edge is less than 440 nm was regarded as "good", and a case where it is 440 nm or more was regarded as "poor". As a result, the evaluation in this example was "good".

[0380] [Examples 21 to 23, Comparative Examples 7 to 11]

[0381] The diamine type was changed as described in Table 3 below, and otherwise, the physical properties of polyimide (polymers (PI-21) to (PI-28)) were evaluated in the same manner as in Example 20. The evaluation results are shown in Table 3 below. In addition, the transmittance spectra of Examples 20 to 23 and Comparative Examples 7 to 11 are shown in Figure 3 and Figure 4 respectively. Furthermore, 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 are shown in Figure 5 .

[0382] [Table 3]

[0383]

[0384] In Table 3, the diamines (DA-3a, DA-18 to DA-20) are compounds represented by the following formulas (DA-3a), (DA-18) to (DA-20), respectively.

[0385] [Chemical Formula 41]

[0386]

[0387] As shown in Table 3, according to the quantum chemical calculations of bis-succinimide, in Examples 20 to 23 using copolymers of aliphatic tetracarboxylic dianhydride and specific diamines, the transparency was "good" and the DC residual image characteristics were "good", achieving a balance of various characteristics. In contrast, in Comparative Examples 7 to 11 using copolymers of aliphatic tetracarboxylic dianhydride and specific diamines, at least one of the transparency and DC residual image characteristics was "poor", which was inferior to the Examples.

[0388] Here, the results of Examples 20 to 23 and Comparative Examples 7 to 11 are examined. The results of Example 22 (diamine (DA-3a)) and Comparative Example 10 (diamine (DA-19)), and Example 23 (diamine (DA-4)) and Comparative Example 7 (diamine (DA-6)) are compared respectively. In Examples 22 and 23 using diamines having a bi-carbazole ring, the DC residual image characteristics were "good". In contrast, in Comparative Examples 10 and 7 using diamines having a carbazole ring instead of a bi-carbazole ring, the DC residual image characteristics were "poor". It is speculated that the reason is that the charge transport property was not fully exhibited in the polymer containing a structural unit derived from a diamine having a carbazole ring, while the charge transport property was fully exhibited in the polymer containing a structural unit derived from a diamine having a bi-carbazole ring.

[0389] In addition, the results of Example 22 (diamine (DA-3a)) and Comparative Example 9 (diamine (DA-18)) are compared. In Example 22 using a diamine in which an oxygen atom is bonded to the carbon atom of the bi-carbazole ring, the transparency was "good". In contrast, in Comparative Example 9 using a diamine in which a nitrogen atom is bonded to the carbon atom of the carbazole ring, the transparency was "poor". It is speculated that the reason is that in Comparative Example 9, the π-conjugated system is extended via the nitrogen atom, and the absorption shifts to a longer wavelength.

[0390] Furthermore, low-energy electron transitions are important because they affect the absorption in the visible light region. Generally, the proportion of electron transitions from HOMO to LUMO is large. For example, in Example 20, 93% of the lowest-energy transition (S0-S1 transition) was HOMO-LUMO transition. Regarding HOMO-LUMO transition, the proportion of charge transfer (CT) transition was large in Examples 20 and 21, and the proportion of local excitation (LE) transition was large in Examples 22 and 23 and Comparative Examples 7 to 11. It is speculated that in Examples 20 and 21, since the connection was made via the nitrogen atoms at the 9,9'-positions of the bi-carbazole ring, the electronic states were very different from those in Examples 22 and 23 and Comparative Examples 7 to 11.

[0391] [Synthesis Example 26]

[0392] Dissolve diamine (DA-1) in NMP, add maleic anhydride in an amount of 2.0 molar equivalents relative to the amount of diamine, and carry out a reaction at room temperature for 6 hours to obtain a 10% by mass solution of additive (AD-5) represented by the following formula (AD-5).

[0393] [Chemical formula 42]

[0394]

[0395] [Synthesis Example 27]

[0396] Change the types and molar ratios of the tetracarboxylic dianhydride and diamine as described in Table 4 below. Otherwise, obtain polyamic acid (PI-29) in the same manner as in Synthesis Example 5. In addition, regarding the values in Table 4, for the acid dianhydride, it represents the usage ratio (mole %) of each compound relative to the total amount (100 mole %) of the acid dianhydride used in the synthesis, and for the diamine, it represents the usage ratio (mole %) of each compound relative to the total amount (100 mole %) of the diamine used in the synthesis.

[0397] [Synthesis Examples 28 and 29]

[0398] Change the types and molar ratios of the tetracarboxylic dianhydride and diamine as described in Table 4 below. Otherwise, obtain polyamic acids (PI-30 and PI-31) in the same manner as in Synthesis Example 23 respectively.

[0399] [Table 4]

[0400]

[0401] [Examples 24 to 27]

[0402] In Example 1, change the components contained in the liquid crystal aligning agent as shown in Table 5 below, and change the solvent composition ratio to NMP:BC:NEP:GBL = 50:30:10:10 (mass ratio). Otherwise, prepare a liquid crystal aligning agent in the same manner as in Example 1, form a liquid crystal alignment film by photo-alignment method, and manufacture an FFS type liquid crystal display element, and conduct various evaluations. The evaluation results are shown in Table 5 below.

[0403] [Examples 28 to 30]

[0404] In Embodiment 13, the components contained in the liquid crystal aligning 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 for this, a liquid crystal aligning agent was prepared in the same manner as in Embodiment 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.

[0405] [Table 5]

[0406]

[0407] In Table 5, the mass ratio of each component of the liquid crystal aligning agent represents the blending ratio (parts by mass) of each compound relative to 100 parts by mass in total of the polymer component and the additive component used in the preparation of the liquid crystal aligning agent.

[0408] As shown in Table 5, in the liquid crystal aligning agents of Embodiments 24 to 26, Embodiment 28, and Embodiment 29 containing the polymer (P), the optical properties (transparency) of the liquid crystal alignment film were "good", and the DC residual image characteristics of the liquid crystal display element were "excellent", and thus a balance of various characteristics was achieved.

[0409] In addition, regarding the liquid crystal aligning agents of Embodiments 27 and 30 containing the additive (AD-5), the optical properties (transparency) of the liquid crystal alignment film were also "good", and the DC residual image characteristics of the liquid crystal display element were also "good", and thus a balance of various characteristics was achieved in the same manner as the liquid crystal aligning agent containing the polymer (P). It is considered that the reason is that in the formation process of the liquid crystal alignment film, the additive (AD-5) is changed to a bismaleimide compound, and a dimerization reaction (coupling reaction) or a crosslinking reaction (Michael addition reaction with the polymer terminal amino group, etc.) of the maleimide group is carried out, or a polymer having a partial structure (A) is generated by a polymerization reaction between maleimide groups.

[0410] From the above, it can be seen that: according to the liquid crystal aligning agent of the present disclosure containing the compound (P), a liquid crystal element having good optical properties (transparency) and DC residual image characteristics can be obtained.

Claims

1. A liquid crystal aligning agent containing a compound (P) having at least one partial structure (A) selected from the group consisting of a partial structure represented by the following formula (2) and a partial structure represented by the following formula (3). In formula (2), R 1 is a halogen atom, a hydroxyl group, or a monovalent organic group, or a plurality of Rs in the formula 1 are combined with each other and form a condensed ring structure together with the ring to which they are bonded; Y 3 is a divalent organic group bonded to the condensed ring structure in the formula by using a carbon atom; a1 is an integer from 0 to 3; when there are a plurality of Rs in the formula 1 , the plurality of Rs 1 are the same group or different groups from each other; the plurality of Ys in the formula 3 are the same or different from each other; the plurality of a1s in the formula are the same or different from each other; "*" represents a bonding bond; "organic group" means an atomic group formed by removing any hydrogen atom from a carbon-containing compound; In formula (3), R 2 is a halogen atom, a hydroxyl group, or a monovalent organic group; R 3 is a hydrogen atom or a monovalent organic group; Y 4 is a divalent organic group bonded to the condensed ring structure in the formula by using a carbon atom, an oxygen atom, a sulfur atom or * 5 -NR 5 -CO-, or is * 2 -NR 4 -* 3 ; R 4 is a hydrogen atom or a monovalent organic group, or represents a part of a ring structure formed by bonding to another group and 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 bonding bonds bonded to the condensed ring structure in the formula; "* 3 ” represents a bonding bond bonded to -CO-; a2 is an integer from 0 to 3; when there are multiple R 2 in the formula, the multiple R 2 are the same as or different from each other; the multiple Y 4 in the formula are the same as or different from each other; the multiple a2 in the formula are the same as or different from each other; "*” represents a bonding bond; "organic group” represents a group formed by removing any hydrogen atom from a carbon-containing compound.

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

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

4. The liquid crystal aligning agent according to claim 1 or 2, wherein 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). In Formula (5) and Formula (6), X 1 is a tetravalent organic group; X 2 is a divalent organic group represented by the following Formula (7) or Formula (8); R 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. In formula (7), R 1 is a halogen atom, a hydroxyl group, or a monovalent organic group, or a plurality of Rs in the formula 1 are combined with each other and form a condensed ring structure together with the ring to which they are bonded; Y 5 is a divalent organic group bonded to the condensed ring structure in the formula by using a carbon atom; a1 is an integer from 0 to 3; when there are a plurality of Rs in the formula 1 , the plurality of Rs 1 are the same or different from each other; the plurality of Ys in the formula 5 are the same or different from each other; the plurality of a1s in the formula are the same or different from each other; "*" represents a bonding bond In formula (8), R 2 is a halogen atom, a hydroxyl group, or a monovalent organic group; R 3 is a hydrogen atom or a monovalent organic group; Y 6 is a single bond, or a divalent organic group bonded to the condensed ring structure in the formula by a carbon atom, an oxygen atom, a sulfur atom or * 5 -NR 5 -CO-; R 5 is a hydrogen atom or a monovalent organic group; "* 5 " represents a bonding bond bonded to the condensed ring structure in the formula; a2 is an integer from 0 to 3; when there are multiple R 2 in the formula, the multiple R 2 are the same as or different from each other; the multiple Y 6 in the formula are the same as or different from each other; the multiple a2 in the formula are the same as or different from each other; "*" represents a bonding bond.

5. The liquid crystal aligning agent according to claim 4, wherein, The said X 1 is a tetravalent aliphatic hydrocarbon group.

6. The liquid crystal aligning agent according to claim 1, containing a polymer component and an additive component. The compound (P) is an additive component.

7. The liquid crystal aligning agent according to claim 6, wherein, The compound (P) is a compound represented by the following formula (9) or formula (10). In formula (9), R 1 is a halogen atom, a hydroxyl group, or a monovalent organic group, or a condensed ring structure formed by a plurality of Rs in the formula 1 combining with each other and together with the ring to which they are bonded; Y 5 is a divalent organic group bonded to the condensed ring structure in the formula by using a carbon atom; Z 1 is a functional group capable of forming a bond by heat or light; Z 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 from 0 to 3; when there are a plurality of Rs in the formula 1 , the plurality of Rs 1 are the same or different from each other; the plurality of Ys in the formula 5 are the same or different from each other; the plurality of a1s in the formula are the same or different from each other, In formula (10), R 2 is a halogen atom, a hydroxyl group, or a monovalent organic group; R 3 is a hydrogen atom or a monovalent organic group; Y 6 is a single bond, or a divalent organic group bonded to the condensed ring structure in the formula by a carbon atom, an oxygen atom, a sulfur atom or * 5 -NR 5 -CO-; R 5 is a hydrogen atom or a monovalent organic group; "* 5 " represents a bonding bond bonded to the condensed ring structure in the formula; Z 3 is a functional group capable of forming a bond by heat or light; Z 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 from 0 to 3; when there are multiple R 2 in the formula, the multiple R 2 are the same or different from each other; the multiple Y 6 in the formula are the same or different from each other; the multiple a2 in the formula are the same or different from each other.

8. The liquid crystal aligning agent according to claim 1 or 2, further containing a polymer not having the partial structure (A).

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

10. A liquid crystal element including the liquid crystal alignment film according to claim 9.

11. 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). In Formula (5) and Formula (6), X 1 is a tetravalent aliphatic hydrocarbon group; X 2 is a divalent organic group represented by the following Formula (7) or Formula (8); R 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, In formula (7), R 1 is a halogen atom, a hydroxyl group, or a monovalent organic group, or a plurality of Rs in the formula 1 are combined with each other and form a condensed ring structure together with the ring to which they are bonded; Y 5 is a divalent organic group bonded to the condensed ring structure in the formula by using a carbon atom; a1 is an integer from 0 to 3; when there are a plurality of Rs in the formula 1 , the plurality of Rs 1 are the same or different from each other; the plurality of Ys in the formula 5 are the same or different from each other; the plurality of a1s in the formula are the same or different from each other; "*" represents a bonding bond, and "organic group" represents a group formed by removing any hydrogen atom from a carbon-containing compound; In formula (8), R 2 is a halogen atom, a hydroxyl group, or a monovalent organic group; R 3 is a hydrogen atom or a monovalent organic group; Y 6 is a single bond or a divalent organic group bonded to the condensed ring structure in the formula by a carbon atom, an oxygen atom, a sulfur atom or * 5 -NR 5 -CO-; R 5 is a hydrogen atom or a monovalent organic group; "* 5 " represents a bonding bond bonded to the condensed ring structure in the formula; a2 is an integer from 0 to 3; when there are multiple R 2 in the formula, the multiple R 2 are the same or different from each other; the multiple Y 6 in the formula are the same or different from each other; the multiple a2 in the formula are the same or different from each other; "*" represents a bonding bond; "organic group" represents a group formed by removing any hydrogen atom from a carbon-containing compound.

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