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

Abstract

To provide a liquid crystal alignment agent by which a liquid crystal element can be obtained which includes a liquid crystal alignment film having good dynamic characteristics and has good liquid crystal aligning property and AC afterimage characteristics.SOLUTION: The liquid crystal alignment agent contains polymer having a structural unit represented by formula (0) and derived from diamine. In the formula (0), R1 and R2 are each independently halogen atom or monovalent organic group. Ar1 and Ar2 are each independently benzene ring, naphthalene ring, or a group obtained by removing (p+2) hydrogen atoms from biphenyl ring. p and q are each independently an integer of 0 to 4. X1 and X2 are each independently single bond or divalent organic group. Y1 is -CO-CO-, -SO2-, -CO-NR5-*N, or -SO2-NR5-*N. R5 is hydrogen atom or monovalent organic group. "*N" is a bond with nitrogen atom coupled to "-COOZ1". Z1 is monovalent organic group.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Liquid crystal devices are widely used in televisions, mobile devices, various monitors, and the like. In liquid crystal devices, the alignment of liquid crystal molecules in a liquid crystal cell is controlled by a liquid crystal alignment film, which is an organic film formed on a substrate. Conventional methods for obtaining an organic film with liquid crystal alignment control power include rubbing an organic film formed using a polymer composition, obliquely vapor-depositing silicon oxide, forming a monomolecular film having a long-chain alkyl group, and irradiating a photosensitive organic film with light (photoalignment method). Of these, the rubbing method is commonly used because it is simple and provides good alignment of liquid crystal molecules. Furthermore, the photoalignment method can impart uniform liquid crystal alignment to a photosensitive organic film while suppressing the generation of static electricity and dust, and also enables precise control of the liquid crystal alignment direction, and therefore has been extensively studied in recent years.

[0003] In recent years, liquid crystal elements have been applied to a wide range of devices and applications, from large-screen liquid crystal televisions to small display devices such as smartphones and tablet PCs, and further improvements in performance are being demanded of liquid crystal elements. Against this background, further improvements in the display quality of liquid crystal elements have become more important than ever, and various liquid crystal alignment agents have been proposed to achieve this (see, for example, Patent Documents 1 and 2).

[0004] Patent Documents 1 and 2 disclose liquid crystal alignment agents containing polyimide precursors or polyimides obtained using diamines of specific structures composed of (thio)urea bonds, spacer moieties, linking groups, and two aminophenyl structures, with the aim of obtaining liquid crystal alignment films that are less likely to be scraped or scratched on the film surface during rubbing treatment (excellent rubbing resistance). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2010 / 053128 [Patent Document 2] International Publication No. 2011 / 136375 Summary of the Invention [Problem to be solved by the invention]

[0006] Conventional liquid crystal alignment agents that can form coating films with high rubbing resistance and good mechanical properties tend to produce image retention due to the application of alternating current voltage (hereinafter also referred to as "AC image retention"). In other words, there is often a trade-off between the mechanical properties of the film and the AC image retention characteristics of the liquid crystal element. AC image retention occurs when the initial alignment direction of the liquid crystal element deviates from the direction at the time of manufacturing due to long-term operation of the liquid crystal element. Furthermore, photoalignment methods tend to be more prone to AC image retention because the alignment control force of liquid crystal molecules is insufficient compared to rubbing methods. To meet the recent demand for even higher performance, there is a need for liquid crystal alignment agents that can sufficiently reduce AC image retention in liquid crystal elements while providing good mechanical properties of liquid crystal alignment films and good liquid crystal alignment.

[0007] The present invention has been made in consideration of the above circumstances, and one object of the present invention is to provide a liquid crystal alignment agent that can produce a liquid crystal alignment film with good mechanical properties and liquid crystal elements with good liquid crystal alignment properties and AC afterimage characteristics. [Means for solving the problem]

[0008] According to one aspect of the present invention, there is provided a liquid crystal aligning agent containing a polymer including a structural unit derived from a diamine represented by the following formula (0). [ka] (In formula (0), R 1 and R 2 are each independently a halogen atom or a monovalent organic group.1 and Ar 2 are each independently a group in which (p+2) hydrogen atoms have been removed from a benzene ring, a naphthalene ring, or a biphenyl ring. p and q are each independently an integer of 0 to 4. X 1 and X 2 are each independently a single bond or a divalent organic group. 1 -CO-CO-, -SO2-, -CO-NR 5 -* N , or -SO2-NR 5 -* N R 5 is a hydrogen atom or a monovalent organic group. N " is "-COOZ 1 " is the bond to the nitrogen atom to which Z is bonded. 1 is a monovalent organic group.

[0009] In another aspect, the present invention provides a liquid crystal alignment film formed using the above liquid crystal aligning agent.In another aspect, the present invention provides a liquid crystal element including the above liquid crystal alignment film.In another aspect, the present invention provides a polymer including a structural unit derived from the diamine represented by formula (0) above.In another aspect, the present invention provides a compound represented by formula (0) above. [Effects of the Invention]

[0010] According to the liquid crystal aligning agent of the present invention, the mechanical properties of the liquid crystal alignment film are good, and a liquid crystal device having good liquid crystal alignment properties and AC afterimage properties can be obtained. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 shows the results of measuring the 1H-NMR spectrum of compound (DA-1). [Figure 2] FIG. 1 shows the results of measuring the 13C-NMR spectrum of compound (DA-1). [Figure 3] FIG. 1 shows the results of measuring the 1H-NMR spectrum of compound (DA-2). [Figure 4] FIG. 1 shows the results of measuring the 13C-NMR spectrum of compound (DA-2). [Figure 5] FIG. 1 shows the results of measuring the 1H-NMR spectrum of compound (DA-3). [Figure 6] FIG. 1 shows the results of measuring the 13C-NMR spectrum of compound (DA-3). [Figure 7] FIG. 1 shows the results of measuring the 1H-NMR spectrum of compound (DA-4). [Figure 8] FIG. 1 shows the results of measuring the 13C-NMR spectrum of compound (DA-4). [Figure 9] FIG. 1 shows the results of measuring the 1H-NMR spectrum of compound (DA-6). [Figure 10] FIG. 1 shows the results of measuring the 13C-NMR spectrum of compound (DA-6). DETAILED DESCRIPTION OF THE INVENTION

[0012] Matters relating to aspects of the present disclosure will be described in detail below.

[0013] Here, in this specification, a numerical range indicated using "to" means that the numerical values ​​before and after "to" are included as the lower and upper limits. A "structural unit" refers to a unit that mainly constitutes the main chain structure, and at least two or more units are contained in the main chain structure. A structural unit is typically a repeating unit constituted based on one monomer. Note that a structural unit may be obtained by reacting a repeating unit having a reactive group with a compound having a functional group that can react with the reactive group.

[0014] As used herein, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure and is composed solely of a chain structure. However, the group may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, the group does not necessarily have to be composed solely of an alicyclic hydrocarbon structure, and may also contain a chain structure as part of the ring structure. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, the group does not necessarily have to be composed solely of an aromatic ring structure, and may contain a chain structure or an alicyclic hydrocarbon structure as part of the ring structure. The term "organic group" refers to an atomic group obtained by removing any hydrogen atom from a carbon-containing compound (i.e., an organic compound).

[0015] The "main chain" of a polymer refers to the "trunk" portion of the polymer, which is the longest chain of atoms. It is permissible for this "trunk" portion to contain a ring structure. For example, "having a specific structure in the main chain" means that the specific structure constitutes a part of the main chain. A "side chain" refers to a portion branched from the "trunk" portion of the polymer.

[0016] <Liquid crystal alignment agent> The liquid crystal aligning agent of the present disclosure and its manufacturing method will be described. The liquid crystal aligning agent of the present disclosure contains a polymer (hereinafter also referred to as "polymer (P)") containing a structural unit derived from a diamine (hereinafter also referred to as "specific diamine") represented by the following formula (0): [ka] (In formula (0), R 1 and R 2 are each independently a halogen atom or a monovalent organic group. 1 and Ar 2 are each independently a group in which (p+2) hydrogen atoms have been removed from a benzene ring, a naphthalene ring, or a biphenyl ring. p and q are each independently an integer of 0 to 4. X 1 and X 2are each independently a single bond or a divalent organic group. 1 -CO-CO-, -SO2-, -CO-NR 5 -* N , or -SO2-NR 5 -* N R 5 is a hydrogen atom or a monovalent organic group. N " is "-COOZ 1 " is the bond to the nitrogen atom to which Z is bonded. 1 is a monovalent organic group.

[0017] The polymer (P) contained in the liquid crystal aligning agent of the present disclosure and the components optionally blended as necessary will be described in detail below. Unless otherwise specified, each component may be used alone or in combination of two or more.

[0018] <Polymer (P)> Specific diamines In the above formula (0), R 1 or R 2 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 1 or R 2 The monovalent organic group represented by the formula (I) is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and any methylene group in the monovalent hydrocarbon group is -O-, -S-, -CO-, -COO-, -OCO-, -NR 10 -, -NR 10 -CO-, -CO-NR 10 - or other heteroatom-containing group (referred to as "group R a "), a monovalent hydrocarbon group or a group R a In this case, R 10 is a hydrogen atom or a monovalent hydrocarbon group.

[0019] Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkynyl group having 2 to 6 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a phenyl group. 1 or R 2 When the group represented by the formula (I) has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a primary amino group, a secondary amino group, and a tertiary amino group.

[0020] R 1 or R 2 From the viewpoint of the polymerizability of the specific diamine and ease of availability, the monovalent organic group represented by the formula (I) is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, -COR 11 or -NR 12 R 13 (However, R 11 , R 12 and R 13 are each independently an alkyl group having 1 to 3 carbon atoms.) is preferred, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a phenyl group is more preferred, and an alkyl group having 1 to 3 carbon atoms is even more preferred.

[0021] R 1 or R 2 From the viewpoints of polymerizability and availability, each of the groups is particularly preferably an alkyl group having 1 to 3 carbon atoms. p is preferably 0 to 2, and more preferably 0 or 1. q is preferably 0 to 2, and more preferably 0 or 1.

[0022] Ar 1 or Ar 2 is a group in which (p+2) hydrogen atoms have been removed from a benzene ring, a naphthalene ring, or a biphenyl ring. In terms of ease of synthesis of the specific diamine and the fact that the liquid crystal alignment property of the liquid crystal alignment film obtained by using the polymer (P) can be further improved, Ar 1 and Ar 2 is preferably a group in which (p+2) hydrogen atoms have been removed from a benzene ring or a biphenyl ring.

[0023] X 1 or X 2 The divalent organic group represented by the formula (I) includes a divalent hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, -CO-, -SO2-, -NR 6 -, -C=N-, or any methylene group in a divalent hydrocarbon group having 2 to 12 carbon atoms is replaced with an oxygen atom, a sulfur atom, -CO-, -SO2-, or -NR 6 - or -C=N- (where R 6 is a hydrogen atom or a monovalent organic group. 1 or X 2 Among these, the divalent organic group represented by the formula (I) is a divalent hydrocarbon group having 1 to 12 carbon atoms, or a divalent hydrocarbon group having 2 to 12 carbon atoms in which any methylene group is replaced with an oxygen atom, a sulfur atom, -CO-, -SO2-, -NR 6 It is preferably a divalent group substituted with - or -C=N-.

[0024] X 1 or X 2 In the divalent organic group represented by the formula (I), examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. From the viewpoint of improving the AC image retention characteristics of a liquid crystal device, among these, a divalent chain hydrocarbon group is preferred, and examples thereof include a linear or branched alkanediyl group having 1 to 12 carbon atoms, a linear or branched alkenediyl group having 2 to 12 carbon atoms, and a linear or branched alkynediyl group having 2 to 12 carbon atoms. Among these, a linear alkanediyl group or alkenediyl group having 1 to 12 carbon atoms is particularly preferred.

[0025] X 1 or X 2 is a divalent group in which any methylene group in a divalent hydrocarbon group having 2 to 12 carbon atoms is replaced with a heteroatom-containing group such as an oxygen atom, specific examples of the divalent hydrocarbon group having 2 to 12 carbon atoms in which a methylene group is replaced with a heteroatom-containing group include X 1 or X 2Among those mentioned above in the description of the case where is a divalent hydrocarbon group having 1 to 12 carbon atoms, groups having 2 or more carbon atoms are exemplified. Among these, divalent chain hydrocarbon groups are particularly preferred, and straight-chain alkanediyl groups or alkenediyl groups having 2 to 12 carbon atoms are preferred.

[0026] -NR 6 -R 6 is preferably a monovalent hydrocarbon group or a thermally eliminable group having 1 to 12 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Among these, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

[0027] Examples of thermally detachable groups include carbamate-based detachable groups, amide-based detachable groups, imide-based detachable groups, and sulfonamide-based detachable groups. Among these, carbamate-based detachable groups are preferred because of their high thermal detachability. Specific examples of carbamate-based detachable groups include an isopropyloxycarbonyl group, a tert-butoxycarbonyl group (Boc group), a 2-methyl-2-butyloxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, an allyloxycarbonyl group, a 2-(trimethylsilyl)ethoxycarbonyl group, and a 9-fluorenylmethyloxycarbonyl group (F-moc group). Among these, a branched alkyloxycarbonyl group having 3 to 6 carbon atoms is more preferred, and a tert-butoxycarbonyl group (Boc group) is particularly preferred, because they are easily removed by heat and can reduce the amount of deprotected moieties remaining in the film.

[0028] R 6 Among the above, is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a thermally labile group. Among these, a thermally labile group is more preferred, an alkyloxycarbonyl group having a branched alkyl group having 3 to 6 carbon atoms is even more preferred, and a Boc group is even more preferred, in that a liquid crystal device having excellent AC afterimage characteristics can be obtained while ensuring the solubility of the polymer.

[0029] Y 1 -CO-CO-, -SO2-, -CO-NR 5 -* N , or -SO2-NR 5 -* N Among these, -CO-CO- or -CO-NR is preferred in that it can improve the mechanical properties of the liquid crystal alignment film. 5 -* N is preferred, and —CO—NR 5 -* N is more preferable. 5 Specific and preferred examples of the monovalent organic group represented by R 6 The same groups as those described above are included. N " represents the nitrogen atom (i.e., -COOZ) in the above formula (1). 1 is a bond to the nitrogen atom to which it is bonded.

[0030] Z 1 The monovalent organic group represented by the formula 1 is preferably a group which is eliminated and replaced with a hydrogen atom. 1 From the viewpoint of improving the thermal desorption of Z 1 is preferably a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, still more preferably a branched alkyl group having 3 to 6 carbon atoms, and particularly preferably a tert-butyl group.

[0031] The specific diamine has two aminoaryl groups in one molecule, each of which has one primary amino group bonded to a substituted or unsubstituted benzene ring, naphthalene ring, or biphenyl ring (i.e., a group represented by -Ar-NH2 (where Ar is a substituted or unsubstituted benzene ring, naphthalene ring, or biphenyl ring)), and the two aminoaryl groups in one molecule are each bonded to a "-X 1 -Y 1 -N(COOZ 1 )-X 2 In this case, "-Y 1 -N(COOZ 1)-" contains multiple hydrogen-bonding functional groups (hydrogen-bonding groups). Specifically, "-Y 1 -N(COOZ 1 )-" contains a group that can be a hydrogen bond donor (-NR-, where R is a hydrogen atom or a monovalent organic group) and a group that can be a hydrogen bond acceptor (-CO-, -SO2-), and has a partial structure in which a total of three or more groups that can be hydrogen bond donors and groups that can be hydrogen bond acceptors are consecutive (hereinafter also referred to as a "multipoint hydrogen bond structure"). The polymer (P) has such a multipoint hydrogen bond structure in its main chain, which facilitates intermolecular interactions between polymers, and the chain structure derived from the multipoint hydrogen bond structure is thought to provide excellent thermal rearrangement and stretchability. Furthermore, since "-SO2-" has a structure in which two oxo groups (=O) are bonded to sulfur, it can be said to have two consecutive hydrogen bond acceptors.

[0032] For details of the multi-point hydrogen bond structure of the polymer (P), see "-Y 1 -N(COOZ 1 The partial structure represented by "Y 1 Depending on the N -, -SO2-NR N -, -CO-NR 5 -NR N -, -SO2-NR 5 -NR N -(R N Ha-COOZ 1 (The same applies hereinafter). In each of these partial structures, when the arrangement of the groups that can be hydrogen bond donors and the groups that can be hydrogen bond acceptors is represented by "D" and "A", respectively, the arrangement becomes "AAD", "AAD", "ADD", and "AADD", and the structure has two consecutive groups that can be hydrogen bond donors or groups that can be hydrogen bond acceptors. This is thought to enhance the hydrogen bonding property while maintaining a high level of thermal rearrangement property or stretchability. Furthermore, at least one of the -NR- in the multipoint hydrogen bonding structure possessed by the polymer (P) is -N(-COOZ 1)-, it is assumed that the AC afterimage characteristics of the liquid crystal element were also good.

[0033] A preferred example of the specific diamine is a compound represented by the following formula (1). [ka] (In formula (1), R 1 and R 2 are each independently a halogen atom or a monovalent organic group. p and q are each independently an integer of 0 to 4. X 1 and X 2 are each independently a single bond or a divalent organic group. 1 -CO-CO-, -SO2-, -CO-NR 5 -* N , or -SO2-NR 5 -* N R 5 is a hydrogen atom or a monovalent organic group. N " is "-COOZ 1 " is the bond to the nitrogen atom to which Z is bonded. 1 is a monovalent organic group.

[0034] In the above formula (1), R 1 , R 2 , p, q, X 1 , X 2 , Y 1 and Z 1 are the same as the symbols in the above formula (0), and the explanation for the above formula (0) can be cited for specific examples and preferred examples of each symbol.

[0035] Specific examples of the specific diamine include compounds represented by the following formulas. [ka] [ka] [ka] [ka] [ka] [ka]

[0036] Among the above, the specific diamine has a group that can become a hydrogen bond donor (-NR N A compound having a total of four or more -CO-NR N -NR N Compounds containing -CO- are more preferred. As described above, -SO2- is counted as a group having two consecutive hydrogen bond acceptors with respect to the total number of groups that can be hydrogen bond donors and groups that can be hydrogen bond acceptors per molecule of the specific diamine. In addition, from the viewpoint of the liquid crystal alignment property of the liquid crystal element and the mechanical properties of the liquid crystal alignment film, the specific diamine is selected from X in the above formula (0). 1 and X 2 Preferably, at least one of X has an alkanediyl group. 1 and X 2 and more preferably, both X and X have an alkanediyl group. 1 and X 2 It is more preferable that both of the above have a linear alkanediyl group.

[0037] [Synthesis of specific diamine] The specific diamine can be synthesized by appropriately combining standard methods in organic chemistry. One example of a method for synthesizing the specific diamine is to first synthesize a dinitro intermediate having a nitro group instead of the primary amino group in the target diamine, and then animate the nitro group of the obtained dinitro intermediate using an appropriate reduction system.

[0038] The method for synthesizing the dinitro intermediate can be appropriately selected depending on the molecular structure of the target diamine. For example, 1 The compound where is -CO-CO- is a compound containing a nitrophenyl group and a group X 1 and reacting an amine compound having the group -COOZ with oxalyl chloride, followed by 1 By introducing Y in the above formula (0), the corresponding dinitro intermediate can be obtained. 1 The compound where is -SO2- has a nitrophenyl group and a group X 1 and reacting the amine hydrochloride having the group -COOZ with sulfamide, followed by 1 By introducing Y in the above formula (0), the corresponding dinitro intermediate can be obtained. 1 Ga-CO-NR 5 - is a compound having a nitrophenyl group and a group X 1 and reacting a carboxylic acid having the group -COOZ with hydrazine, followed by 1 The corresponding dinitro intermediate can be obtained by introducing the following: Each reaction can be carried out in a suitable organic solvent, if necessary, in the presence of a catalyst.

[0039] The reduction reaction of the dinitro intermediate can be preferably carried out in an organic solvent using a catalyst such as palladium carbon or platinum carbon and a reducing agent such as hydrogen or hydrazine. Alternatively, the reduction can be carried out using a metal such as zinc, iron, tin, or nickel and a proton source such as hydrochloric acid or ammonium chloride. Examples of organic solvents used here include ethyl acetate, toluene, tetrahydrofuran, and alcohols. However, the synthesis method of the specific diamine is not limited to the above.

[0040] The type of main skeleton of the polymer (P) is not particularly limited as long as it contains a structural unit derived from the specific diamine. The polymer (P) is preferably a condensation polymer obtained by using a diamine containing the specific diamine as a monomer, and examples thereof include polymers having a polyamic acid, polyamic acid ester, polyimide, polyamine, polyenamine, polyamide, polyamideimide, polyurea, or polyimine as a main skeleton. The polyenamine is a polymer having a carbon-carbon double bond adjacent to the amino group of the polyamine, and examples thereof include polyenaminoketone, polyenaminoester, polyenaminonitrile, and polyenaminosulfonyl.

[0041] In order to obtain a liquid crystal device having excellent liquid crystal alignment properties and voltage retention characteristics, the polymer (P) is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyamide, polyamideimide, polyurea, and polyimine. Among these, the polymer (P) is more preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.

[0042] [Synthesis of polymer (P)] The synthesis method of the polymer (P) is not particularly limited and can be appropriately selected depending on the type of main skeleton. For example, 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 be obtained by a method including a step of polycondensing a tetracarboxylic acid derivative with a diamine including a specific diamine. The tetracarboxylic acid derivative includes a tetracarboxylic acid dianhydride, a tetracarboxylic acid dihalide, and a tetracarboxylic acid diester dihalide. The polyamic acid, the polyamic acid ester, and the polyimide will be described in detail below.

[0043] (Polyamic acid) When the polymer (P) is a polyamic acid, the polyamic acid (hereinafter also referred to as "polyamic acid (P)") can be obtained by reacting (polycondensation reaction) a tetracarboxylic dianhydride with a diamine.

[0044] Tetracarboxylic acid dianhydride Examples of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid (P) include aliphatic tetracarboxylic acid dianhydrides and aromatic tetracarboxylic acid dianhydrides. Examples of the aliphatic tetracarboxylic acid dianhydrides include linear tetracarboxylic acid dianhydrides and alicyclic tetracarboxylic acid dianhydrides.

[0045] Specific examples of the tetracarboxylic acid dianhydride include chain tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride and ethylenediaminetetraacetic acid dianhydride; Examples of alicyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic 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, 3-oxabicyclo[3 .2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride 2,6]undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, etc.; Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, p-phenylene bis(trimellitic acid monoester anhydride), ethylene glycol bis(anhydrotrimellitate), 1,3-propylene glycol bis(anhydrotrimellitate), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-biphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, and 4,4'-carbonyldiphthalic anhydride; and the tetracarboxylic dianhydrides described in JP-A-2010-97188 can also be used.

[0046] The tetracarboxylic acid dianhydride preferably includes an aliphatic tetracarboxylic acid dianhydride, more preferably an alicyclic tetracarboxylic acid dianhydride, in terms of increasing the solubility of the polymer (P) and enabling the formation of a liquid crystal alignment film exhibiting good voltage retention characteristics. Specifically, the tetracarboxylic acid dianhydride preferably includes at least one selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic acid dianhydride, and cyclohexanetetracarboxylic acid dianhydride.

[0047] In the polyamic acid (P), the content of structural units derived from an alicyclic tetracarboxylic dianhydride is preferably 20 mol % or more, more preferably 30 mol % or more, even more preferably 50 mol % or more, and particularly preferably 70 mol % or more, based on the total amount of structural units derived from tetracarboxylic dianhydride contained in the polyamic acid (P).

[0048] Diamine When synthesizing the polyamic acid (P), only the specific diamine may be used as the diamine. Alternatively, a diamine different from the specific diamine (hereinafter also referred to as "other diamine") may be used together with the specific diamine. Examples of other diamines include aliphatic diamines, aromatic diamines, and diaminoorganosiloxanes. Examples of aliphatic diamines include linear diamines and alicyclic diamines.

[0049] Specific examples of other diamines include chain diamines such as metaxylylenediamine and hexamethylenediamine; and alicyclic diamines such as 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine).

[0050] Specific examples of aromatic diamines include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylether, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,6-bis(4-aminophenoxy)hexane, bis[2-(4-aminophenyl)ethyl]hexanedioic acid, 1,4-bis-(4-aminophenyl)-piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl ]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, 4,4'-diaminobenzanilide, 4,4'- Main-chain diamines such as diaminostilbene, 4,4'-diaminodiphenethylurea, N,N'-di(4-amino-2-pyridyl)-N,N'-di(tert-butoxycarbonyl)ethylenediamine, N,N'-bis[2-(4-aminophenyl)ethyl]hexanediamide, and N,N'-bis[2-(4-aminophenyl)ethyl]-N,N'-di(tert-butoxycarbonyl)hexanediamide; Dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-di Cholestanyl aminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostaniyl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 5ξ-cholestan-3-yl 3,5-diaminobenzoate, the following formula (E-1): [ka] (In formula (E-1), X I and X II are each independently a single bond, -O-, *-COO-, or *-OCO- (where * indicates the bond to the diaminophenyl group). I is an alkanediyl group having 1 to 3 carbon atoms. II R is a single bond or an alkanediyl group having 1 to 3 carbon atoms. III is an alkyl group, alkoxy group, fluoroalkyl group, or fluoroalkoxy group having 1 to 20 carbon atoms. a is 0 or 1. b is an integer of 0 to 3. c is an integer of 0 to 2. d is 0 or 1, provided that 1≦a+b+c≦3. and side chain diamines such as compounds represented by the following formula:

[0051] Examples of the compound represented by formula (E-1) include compounds represented by the following formulas (E-1-1) to (E-1-4). [ka]

[0052] Specific examples of diaminoorganosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, etc. In addition to the above, other diamines that can be used include the diamines described in JP-A-2010-97188.

[0053] The proportion of the structural units derived from the specific diamine in the polymer (P) is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more, based on the total amount of the structural units derived from the diamine contained in the polymer (P). By setting the proportion of the structural units derived from the specific diamine within the above range, the mechanical properties of the film, and the liquid crystal alignment property and AC image retention property of the liquid crystal element can be improved.

[0054] When the polymer (P) contains structural units derived from other diamines, the proportion of the structural units derived from other diamines in the polymer (P) is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 15 mol % or more, based on the total amount of structural units derived from diamines contained in the polymer (P). The proportion of the structural units derived from other diamines in the polymer (P) is preferably 95 mol % or less, more preferably 90 mol % or less, and even more preferably 80 mol % or less, based on the total amount of structural units derived from diamines contained in the polymer (P).

[0055] Synthesis of polyamic acid (P) The polyamic acid (P) can be obtained by reacting a tetracarboxylic dianhydride with a diamine, optionally together with a molecular weight modifier. The ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of the polyamic acid (P) is preferably such that 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride are used per equivalent of the amino group of the diamine.

[0056] Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. The proportion of the molecular weight modifier used is preferably 20 parts by mass or less per 100 parts by mass of the total of the tetracarboxylic dianhydride and diamine used.

[0057] The synthesis reaction of the polyamic acid (P) is preferably carried out in an organic solvent, preferably at a reaction temperature of −20° C. to 150° C., and for a reaction time of 0.1 to 24 hours.

[0058] Examples of organic solvents used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents include one or more selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, and halogenated phenols. Alternatively, it is preferred to use a mixture of one or more of these solvents with other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount of organic solvent (a) used is preferably an amount such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by mass relative to the total amount (a+b) of the reaction solution.

[0059] In this manner, a reaction solution containing the polyamic acid (P) dissolved therein is obtained. This reaction solution may be used directly for the preparation of a liquid crystal aligning agent, or the polyamic acid (P) contained in the reaction solution may be isolated and then used for the preparation of a liquid crystal aligning agent, or the isolated polyamic acid (P) may be purified and then used for the preparation of a liquid crystal aligning agent. When the polyamic acid (P) is subjected to dehydration ring closure to form a polyimide, the reaction solution may be used directly for the dehydration ring closure reaction, or the polyamic acid (P) contained in the reaction solution may be isolated and then used for the dehydration ring closure reaction, or the isolated polyamic acid (P) may be purified and then used for the dehydration ring closure reaction. The isolation and purification of the polyamic acid (P) can be carried out according to known methods.

[0060] (Polyamic acid ester) The polyamic acid ester as the polymer (P) (hereinafter also referred to as "polyamic acid ester (P)") can be obtained, for example, by [I] a method of reacting the polyamic acid (P) obtained by the above synthesis reaction with an esterifying agent; [II] a method of reacting a tetracarboxylic acid diester with a diamine including a specific diamine; or [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine including a specific diamine.

[0061] In this specification, "tetracarboxylic acid diester" means a compound in which two of the four carboxy groups in a tetracarboxylic acid are esterified and the remaining two are carboxy groups. "Tetracarboxylic acid diester dihalide" means a compound in which two of the four carboxy groups in a tetracarboxylic acid are esterified and the remaining two are halogenated.

[0062] Examples of the esterifying agent used in the method [I] include hydroxyl group-containing compounds, acetal compounds, halides, epoxy group-containing compounds, etc. Specific examples of these include: hydroxyl group-containing compounds such as alcohols (e.g., methanol, ethanol, and propanol), and phenols (e.g., phenol and cresol); acetal compounds such as N,N-dimethylformamide diethyl acetal and N,N-diethylformamide diethyl acetal; halides such as methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, and 1,1,1-trifluoro-2-iodoethane; and epoxy group-containing compounds such as propylene oxide.

[0063] The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic acid dianhydride exemplified in the description of the synthesis of the polyamic acid (P) using an alcohol such as methanol, ethanol, etc. The tetracarboxylic acid derivative used in the method [II] may be a tetracarboxylic acid diester alone, or may be used in combination with a tetracarboxylic acid dianhydride.

[0064] The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. The tetracarboxylic acid derivative used in the method [III] may be the tetracarboxylic acid diester dihalide alone, or may be used in combination with a tetracarboxylic acid dianhydride.

[0065] The polyamic acid ester (P) contained in the liquid crystal aligning agent may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. The reaction solution in which the polyamic acid ester (P) is dissolved may be used directly for preparing the liquid crystal aligning agent, or the polyamic acid ester (P) contained in the reaction solution may be isolated and then used for preparing the liquid crystal aligning agent, or the isolated polyamic acid ester (P) may be purified and then used for preparing the liquid crystal aligning agent. The polyamic acid ester (P) can be isolated and purified according to known methods.

[0066] (Polyimide) The polyimide as the polymer (P) (hereinafter also referred to as "polyimide (P)") can be obtained, for example, by dehydrating and ring-closing the polyamic acid (P) synthesized as described above to thereby imidize it.

[0067] The polyimide (P) may be a fully imidized product in which all amic acid structures contained in its precursor polyamic acid (P) have been dehydrated and cyclized, or a partially imidized product in which only a portion of the amic acid structures have been dehydrated and cyclized, resulting in both amic acid structures and imide ring structures. The polyimide (P) preferably has an imidization rate of 20% or more, more preferably 30 to 99%. The imidization rate is the ratio, expressed as a percentage, of the number of imide ring structures to the total number of amic acid structures and imide ring structures in the polyimide (P). Some of the imide rings may be isoimide rings.

[0068] The dehydration ring-closure of the polyamic acid (P) is preferably carried out by heating the polyamic acid (P), or by dissolving the polyamic acid (P) in an organic solvent, adding a dehydrating agent and a dehydration ring-closure catalyst to the solution, and heating as necessary.

[0069] In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of polyamic acid (P), for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per mol of the amic acid structure of the polyamic acid (P). The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol per mol of the dehydrating agent used. Examples of organic solvents used in the dehydration ring-closing reaction include the organic solvents exemplified for use in the synthesis of polyamic acid (P). The reaction temperature for the dehydration ring-closing reaction is preferably 0 to 180°C, more preferably 10 to 150°C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

[0070] In this way, a reaction solution containing polyimide (P) is obtained. This reaction solution may be used directly for the preparation of a liquid crystal aligning agent, or may be used for the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or may be used for the preparation of a liquid crystal aligning agent after isolating polyimide (P), or may be used for the preparation of a liquid crystal aligning agent after purifying the isolated polyimide (P). These purification operations can be carried out according to known methods. Alternatively, polyimide (P) can also be obtained by imidizing polyamic acid ester (P).

[0071] Similarly to the polyamic acid (P), polyamic acid ester (P), and polyimide (P), polyamide, polyamideimide, polyurea, and polyimine as polymers (P) can be obtained by using a specific diamine as a monomer. Specifically, polyamide can be obtained by a method such as reacting a dicarboxylic acid derivative with a diamine containing a specific diamine. Polyamideimide can be obtained by a method such as reacting a tricarboxylic acid derivative with a diamine containing a specific diamine. Polyurea can be obtained by a method such as reacting an isocyanate compound with a polyamine containing a specific diamine. Polyimine can be obtained by a method such as reacting a dialdehyde compound with a diamine containing a specific diamine. In each of these reactions, the specific diamine can be the same as the compounds exemplified in the description of polyamic acid (P).

[0072] The solution viscosity of the polymer (P) contained in the liquid crystal aligning agent is preferably 10 to 800 mPa·s when made into a 10% by mass solution, and more preferably 15 to 500 mPa·s. The solution viscosity (mPa·s) is a value measured at 25°C using an E-type rotational viscometer for a 10% by mass polymer solution prepared using a good solvent for the polymer (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0073] The weight average molecular weight (Mw) of the polymer (P) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1,000 to 500,000, and more preferably 5,000 to 100,000. The molecular weight distribution (Mw / Mn), which is expressed as the ratio of Mw to the number average molecular weight (Mn) measured by GPC in terms of polystyrene, is preferably 15 or less, and more preferably 10 or less.

[0074] From the viewpoint of obtaining a liquid crystal element having excellent liquid crystal alignment properties and voltage retention characteristics, high film strength, and excellent reliability, the content of the polymer (P) in the liquid crystal alignment agent is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to the total mass of the solid content contained in the liquid crystal alignment agent (total mass of components other than the solvent of the liquid crystal alignment agent).

[0075] [Other ingredients] The liquid crystal aligning agent of the present disclosure may further contain components other than the polymer (P) (hereinafter also referred to as "other components"). Examples of the other components include a polymer different from the polymer (P) (hereinafter also referred to as "polymer (Q)"), a crosslinking agent, a solvent, etc.

[0076] Polymer (Q) The polymer (Q) is a polymer that does not contain a structural unit derived from a specific diamine. The main skeleton of the polymer (Q) is not particularly limited. Examples of the polymer (Q) include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, polyenamine, polyurea, polyamide, polyamideimide, polyimine, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, and addition polymer. Examples of the addition polymer include (meth)acrylic polymer, styrene polymer, maleimide polymer, (meth)acrylic-styrene copolymer, (meth)acrylic-maleimide copolymer, (meth)acrylic-styrene-maleimide copolymer, and styrene-maleimide copolymer.

[0077] Among these, polymer (Q) is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, and addition polymer, and more preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, in that it exhibits good liquid crystal alignment properties and voltage retention characteristics when used in combination with polymer (P).

[0078] When the polymer (Q) is contained in the liquid crystal aligning agent, the content of the polymer (Q) is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total amount of the polymer (P) and the polymer (Q). The content of the polymer (Q) is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less, based on the total amount of the polymer (P) and the polymer (Q).

[0079] Crosslinking agent The liquid crystal aligning agent of the present disclosure may further contain a crosslinking agent. By further containing a crosslinking agent, it is possible to improve the reliability of the liquid crystal element and further reduce the occurrence of AC image retention. Examples of crosslinking agents include compounds having, in the molecule, two or more of at least one group selected from the group consisting of a cyclic ether group, a cyclic thioether group, an isocyanate group, a protected isocyanate group, a methylol group, a protected methylol group, a hydroxyalkylamide group, a protected hydroxyalkylamide group, a cyclic carbonate group, a polymerizable carbon-carbon bond-containing group, a protected amino group, a silanol group, and an alkoxysilyl group.

[0080] From the viewpoint of sufficiently improving the AC image retention characteristics and reliability of a liquid crystal device, the number of crosslinkable groups contained in one molecule of the crosslinking agent is preferably 2 to 10, and more preferably 2 to 6. The molecular weight of the crosslinking agent is preferably 100 to 1,000, more preferably 100 to 800, and even more preferably 100 to 700.

[0081] Specific examples of the crosslinking agent include compounds having a cyclic ether group or a cyclic thioether group, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, triglycidyl isocyanurate, glycerol polyglycidyl ether, pentaerythritol tetraglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, N,N',N',N'-tetraglycidyl glycoluril, 1,6-hexanediol diglycidyl ether, trimethyl Examples of such glycerols include methyl glycerol propane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, and epoxidation reaction products of 2,2'-diallylbisphenol A diallyl ether with hydrogen peroxide.

[0082] Examples of compounds having an isocyanate group or a protected isocyanate group include tolylene diisocyanate, xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, compounds in which the isocyanate group of these compounds is protected with 3,6-dimethylpyrazole, methyl ethyl ketoxime, diethyl malonate, or ε-caprolactam, and compounds represented by the following formula (d1-1).

[0083] Examples of compounds having a methylol group or a protected methylol group include compounds represented by the following formulas (d2-1) to (d2-5). Examples of compounds having a hydroxyalkylamide group or a protected hydroxyalkylamide group include compounds represented by the following formulas (d3-1) to (d3-8). Examples of the compound having a cyclic carbonate group include compounds represented by the following formulas (d4-1) and (d4-2).

[0084] Examples of compounds having a polymerizable carbon-carbon bond-containing group include compounds having a (meth)acryloyl group, a maleimide group, an alkenyl group, a vinylphenyl group, a vinyl ether group, or a 3-methylenetetrahydrofuran-2(3H)-one-5-yl group. Specific examples of these include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and compounds represented by the following formulas (d5-1) to (d5-7).

[0085] Examples of compounds having a protected amino group include compounds represented by the following formulae (d6-1) to (d6-5). Examples of compounds having a silanol group or an alkoxysilyl group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and vinyltriethoxysilane.

[0086] [ka] [ka] (In formula (d2-4), Ac is an acetyl group.) [ka] [ka] [ka] [ka]

[0087] When a crosslinking agent is contained in the liquid crystal aligning agent of the present disclosure, the content of the crosslinking agent is preferably 0.5 parts by mass or more relative to 100 parts by mass of the total amount of polymer components contained in the liquid crystal aligning agent (i.e., the total amount of polymer (P) and polymer (Q)), from the viewpoints of improving the mechanical properties of the liquid crystal alignment film, improving the reliability of the liquid crystal device, and further reducing AC afterimages. From the above viewpoints, the content of the crosslinking agent is more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of the total amount of polymer components. Furthermore, from the viewpoints of obtaining a liquid crystal device with good liquid crystal alignment properties and electrical properties, and of improving the storage stability of the liquid crystal aligning agent, the content of the crosslinking agent is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the total amount of polymer components.

[0088] ·solvent The liquid crystal aligning agent of the present disclosure is prepared as a liquid composition in which the polymer (P) and components used as needed are dispersed or dissolved preferably in a suitable solvent.

[0089] Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, 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-i-propyl ether, and ethylene glycol-n-butyl ether ( butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, and the like.

[0090] In addition to the above, other components include, for example, antioxidants, metal chelate compounds, curing accelerators, surfactants, fillers, dispersants, photosensitizers, acid generators, base generators, radical generators, etc. The blending ratio of each of these components can be appropriately selected depending on each compound within a range that does not impair the effects of the present disclosure.

[0091] 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 to the total mass of the liquid crystal aligning agent) is appropriately selected taking into consideration viscosity, volatility, etc., but is preferably in the range of 1 to 10 mass %. That is, the liquid crystal aligning agent is applied to the surface of a substrate as described below, and preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that will become a liquid crystal alignment film. In this case, if the solid content concentration is 1 mass % or more, the coating film can have a sufficient thickness, and a good liquid crystal alignment film tends to be easily obtained. If the solid content concentration is 10 mass % or less, the coating film thickness does not become too large, and an increase in the viscosity of the liquid crystal aligning agent can be suppressed, tending to improve the coatability.

[0092] The particularly preferred range of solid content varies depending on the application of the liquid crystal aligning agent and the method used to apply the liquid crystal aligning agent to a substrate. For example, when applying a liquid crystal aligning agent for a liquid crystal display device to a substrate by a spinner method, the solid content (the ratio of the total mass of all components in the liquid crystal aligning agent other than the solvent to the total mass of the liquid crystal aligning agent) is particularly preferably in the range of 1.5 to 4.5 mass%. When using a printing method, the solid content is particularly preferably in the range of 3 to 9 mass%, thereby adjusting the solution viscosity to a range of 12 to 50 mPa·s. When using an inkjet method, the solid content is particularly preferably in the range of 1 to 5 mass%, thereby adjusting the solution viscosity to a range of 3 to 15 mPa·s. The temperature when preparing the liquid crystal aligning agent is preferably 10 to 50°C, more preferably 20 to 30°C. Furthermore, with regard to the liquid crystal aligning agent for the retardation film, from the viewpoint of the applicability of the liquid crystal aligning agent and the thickness of the coating film to be formed being appropriate, the solid content concentration of the liquid crystal aligning agent is preferably in the range of 0.2 to 10 mass %, more preferably in the range of 3 to 10 mass %.

[0093] <Liquid crystal alignment film and liquid crystal element> The liquid crystal alignment film of the present disclosure is formed using the liquid crystal aligning agent prepared as described above. Furthermore, the liquid crystal element of the present disclosure has 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 various modes, such as TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS (In-Plane Switching) type, FFS (Fringe Field Switching) type, OCB (Optically Compensated Bend) type, and PSA (Polymer Sustained Alignment) type, can be applied. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, different substrates are used depending on the desired operation mode. Steps 2 and 3 are common to all operation modes.

[0094] <Step 1: Formation of coating film> First, a liquid crystal alignment agent is applied to a substrate, and the coated surface is preferably heated to form a coating film on the substrate. Examples of substrates that can be used include glass, such as float glass or soda glass; and transparent substrates made of resins, such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly(alicyclic olefin). When manufacturing TN, STN, or VA liquid crystal devices, two substrates with patterned transparent conductive films are used. On the other hand, when manufacturing IPS or FFS liquid crystal devices, one substrate with comb-shaped patterned electrodes and a counter substrate without electrodes are used. Examples of transparent conductive films that can be used include NESA films (registered trademark of PPG, USA) made of tin oxide (SnO), and ITO films made of indium oxide-tin oxide (InO-SnO). The liquid crystal alignment agent is applied to the substrate surface, preferably by offset printing, flexographic printing, spin coating, roll coating, or inkjet printing. The liquid crystal aligning agent of the present disclosure is suitable as a liquid crystal aligning agent for inkjet coating because it easily forms a uniform film even by inkjet coating.

[0095] After the liquid crystal aligning agent is applied, preheating (pre-baking) is preferably carried out for the purpose of preventing dripping of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30 to 200°C, and the pre-baking time is preferably 0.25 to 10 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of removing the solvent in the applied liquid crystal aligning agent. The baking temperature (post-baking temperature) at this time is preferably 80 to 250°C, more preferably 80 to 200°C. The post-baking time is preferably 5 to 200 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm.

[0096] <Step 2: Alignment Treatment> When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal device, the coating film formed in step 1 is subjected to a treatment (alignment treatment) to impart liquid crystal alignment ability. This imparts the ability to align liquid crystal molecules to the coating film, resulting in a liquid crystal alignment film. Examples of alignment treatments that can be used include rubbing, in which the coating film formed on the substrate is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, or cotton; and photoalignment, in which the coating film formed on the substrate is irradiated with light to impart liquid crystal alignment ability to the coating film. On the other hand, when manufacturing a vertical alignment (VA)-type liquid crystal device, the coating film formed in step 1 can be used as is as a liquid crystal alignment film. Furthermore, the coating film may be subjected to an alignment treatment to further enhance the liquid crystal alignment ability. Liquid crystal alignment films suitable for vertical alignment-type liquid crystal devices are also suitable for PSA-type liquid crystal devices.

[0097] In the photo-alignment treatment, light irradiation can be performed by irradiating the coating film after the post-bake step; irradiating the coating film after the pre-bake step but before the post-bake step; or irradiating the coating film while it is being heated in at least one of the pre-bake step and the post-bake step. The radiation to be irradiated to the coating film can be, for example, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm. Preferably, ultraviolet light containing light with a wavelength of 200 to 400 nm is used. When the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these. When non-polarized radiation is used, the irradiation direction is an oblique direction.

[0098] Examples of light sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, etc. The radiation dose on the substrate surface is preferably 400 to 50,000 J / m 2 and more preferably 1,000 to 20,000 J / m 2 After the light irradiation for imparting alignment ability, the substrate surface may be washed with, for example, water, an organic solvent (e.g., methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.) or a mixture thereof, or the substrate may be heated.

[0099] <Step 3: Construction of liquid crystal cell> Two substrates with liquid crystal alignment films formed thereon are prepared as described above, and a liquid crystal cell is fabricated between the two substrates, with liquid crystal disposed adjacent to the liquid crystal alignment films. Examples of methods for fabricating a liquid crystal cell include placing two substrates facing each other with a gap between them so that the liquid crystal alignment films face each other, bonding the peripheries of the two substrates together with a sealant, injecting liquid crystal into the cell gap surrounded by the substrate surfaces and the sealant, and sealing the injection hole; an ODF method; and other methods. Examples of sealants that can be used include epoxy resins containing a curing agent and aluminum oxide spheres as spacers. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, with nematic liquid crystals being preferred. In the PSA mode, a liquid crystal cell is constructed by disposing a photopolymerizable compound together with liquid crystal between two substrates. After the liquid crystal cell is constructed, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.

[0100] For each mode of liquid crystal cell, a polarizing plate is then attached to the outer surface of the liquid crystal cell as needed to form a liquid crystal element. Examples of polarizing plates include a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine, sandwiched between cellulose acetate protective films, and a polarizing plate made of the H film itself.

[0101] The liquid crystal element of the present disclosure can be effectively applied to various applications, specifically, for example, various display devices such as watches, portable game machines, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays, as well as light control films, retardation films, and the like.

[0102] Furthermore, the polymer (P) has a multipoint hydrogen bond structure in the main chain, which facilitates intermolecular interactions between polymers, and the chain structure derived from the multipoint hydrogen bond structure is thought to provide excellent thermal rearrangement or stretchability. Such polymer (P) can also be used in optical films, flexible substrates, photosensitive resin compositions, surface protective films, interlayer insulating films, etc.

[0103] The above explanation discloses the following aspects [1] to

[10] . [1] A liquid crystal aligning agent containing a polymer containing a structural unit derived from a diamine represented by the above formula (0). [2] X in the above formula (0) 1 and X 2 are each independently a single bond, a divalent hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, -CO-, -SO2-, or -NR 6 -, -C=N-, or any methylene group in a divalent hydrocarbon group having 2 to 12 carbon atoms is replaced with an oxygen atom, a sulfur atom, -CO-, -SO2-, or -NR 6 - or -C=N- (where R 6 is a hydrogen atom or a monovalent organic group. [3] Z in the above formula (0) 1 is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms. [4] When p in the above formula (0) is 1 or more, R 1 is an alkyl group having 1 to 3 carbon atoms, and when q in the above formula (0) is 1 or more, R 2 The liquid crystal aligning agent according to any one of [1] to [3], wherein is an alkyl group having 1 to 3 carbon atoms. [5] The liquid crystal aligning agent according to any one of [1] to [4], wherein the polymer is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyamide, polyamideimide, polyurea, and polyimine. [6] The liquid crystal aligning agent according to any one of [1] to [5], further comprising a polymer not containing a structural unit derived from the diamine represented by the formula (0). [7] The liquid crystal aligning agent according to any one of [1] to [6], wherein the diamine represented by the formula (0) is represented by the formula (1). [8] A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of [1] to [7]. [9] A liquid crystal element comprising the liquid crystal alignment film according to [8].

[10] A polymer containing a structural unit derived from a diamine represented by the above formula (0).

[11] A diamine represented by the above formula (0). [Example]

[0104] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0105] The structures and abbreviations of the main compounds used in the following examples are as follows: [Tetracarboxylic acid dianhydride] Compounds (TA-1) to (TA-5): Compounds represented by the following formulas (TA-1) to (TA-5), respectively: [ka]

[0106] [Diamine] Compounds (DA-1) to (DA-8): Compounds represented by the following formulas (DA-1) to (DA-8), respectively: [ka]

[0107] Compounds (DB-1) to (DB-14): Compounds represented by the following formulas (DB-1) to (DB-14), respectively: [ka]

[0108] [Additives] Compounds (AD-1) to (AD-3): Compounds represented by the following formulas (AD-1) to (AD-3), respectively: [ka]

[0109] [solvent] NMP; N-methyl-2-pyrrolidone GBL; gamma-butyrolactone BC: Butyl cellosolve DAA: Diacetone alcohol THF: tetrahydrofuran

[0110] <Synthesis and evaluation of compounds> [Synthesis Example 1] The diamine represented by the above formula (DA-1) (compound (DA-1)) was synthesized according to the following synthesis scheme. Oxalyl chloride (30.0 mmol) and THF (40 mL) were placed in a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube. Under a nitrogen stream, a solution of 2-methyl-4-nitroaniline (63.0 mmol) dissolved in THF (40 mL) was added dropwise over 5 minutes while stirring at 0°C. The mixture was then stirred at 0°C for an additional 1 hour. After the reaction was complete, water (20 mL) was added and the mixture was stirred to precipitate a pale yellow solid. The resulting precipitate was filtered, washed with a 1 / 1 (v / v) water / isopropanol mixed solvent, and dried under reduced pressure to obtain the intermediate represented by the following formula (DA-1-1) in a 92% yield. Next, intermediate (DA-1-1) (15.0 mmol), N,N-dimethylaminopyridine (7.5 mmol), and NMP (40 mL) were placed in a three-necked flask equipped with a reflux condenser, a thermometer, and a nitrogen inlet tube. Di-tert-butyl dicarbonate (33.0 mmol) was added dropwise over 5 minutes while stirring at room temperature under a nitrogen stream, and the mixture was further stirred at 50 °C for 1 hour. After the reaction was completed, the reaction solution was added to water and stirred to precipitate a yellow solid. The resulting precipitate was filtered, washed with water, and dried under reduced pressure to obtain the intermediate represented by the following formula (DA-1-2) in a 93% yield. Furthermore, intermediate (DA-1-2) (10.0 mmol), zinc metal (200 mmol), ammonium chloride (100 mmol), THF (30 mL), and ethanol (10 mL) were placed in a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube. Water (10 mL) was added dropwise over 5 minutes while stirring at 0 °C under a nitrogen stream. The mixture was then stirred at 0 °C for 2 hours. After completion of the reaction, the reaction solution was diluted with THF, saturated aqueous sodium bicarbonate was added, and the mixture was filtered through Celite. The organic phase of the filtrate was separated and washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The resulting residue was dissolved in THF, reprecipitated by adding dropwise water, filtered, and dried under reduced pressure to obtain compound (DA-1) in 89% yield. Figures 1 and 2 show the structure of compound (DA-1). 1 H-NMR spectrum (DMSO-d6, 400 MHz) and 13 The results of measuring the C-NMR spectrum (DMSO-d6, 75 MHz) are shown respectively. [ka]

[0111] [Synthesis Example 2] The diamine represented by the above formula (DA-2) (compound (DA-2)) was synthesized according to the following synthesis scheme. 4-Nitrophenethylamine hydrochloride (20.5 mmol), sulfamide (10.0 mmol), N,N-diisopropylethylamine (21.0 mmol), and pyridine (30 mL) were placed in a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube, and stirred for 12 hours under reflux under a nitrogen stream. After the reaction was completed, water (50 mL) and hexane (50 mL) were added and stirred for 1 hour to precipitate a pale yellow solid. The resulting precipitate was filtered, washed with water, hexane, and ethanol, and dried under reduced pressure to obtain the intermediate represented by the following formula (DA-2-1) in a 75% yield. Next, intermediate (DA-2-1) (5.0 mmol), N,N-dimethylaminopyridine (0.5 mmol), and THF (20 mL) were placed in a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube. Di-tert-butyl dicarbonate (11.0 mmol) was added dropwise over 5 minutes while stirring at room temperature under a nitrogen stream, and the mixture was further stirred at 50 °C for 5 hours. After the reaction was completed, the reaction solution was added to water (80 mL) and stirred for 1 hour to precipitate a white solid. The resulting precipitate was filtered, washed with water and ethanol, and dried under reduced pressure to obtain the intermediate represented by the following formula (DA-2-2) in a 93% yield. Furthermore, intermediate (DA-2-2) (4.0 mmol), zinc metal (80 mmol), ammonium chloride (16 mmol), THF (20 mL), and ethanol (20 mL) were placed in a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube. Water (8 mL) was added dropwise over 5 minutes while stirring at room temperature under a nitrogen stream, and the mixture was further stirred at 60 °C for 2 hours. After completion of the reaction, the reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure. The residue was extracted with ethyl acetate, and the organic phase was separated and washed with water, saturated aqueous sodium bicarbonate, and saturated brine. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to precipitate a white solid. The resulting solid was slurry-washed with ethanol, filtered, and dried under reduced pressure to obtain compound (DA-2) in 79% yield. Figures 3 and 4 show the results of compound (DA-2). 1 H-NMR spectrum (CDCl3, 400 MHz) and 13 The results of measuring the C-NMR spectrum (CDCl3, 75 MHz) are shown below. [ka]

[0112] [Synthesis Example 3] The diamine represented by the above formula (DA-3) (compound (DA-3)) was synthesized according to the following synthesis scheme. A three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube was charged with 3-(4-nitrophenyl)propionic acid (21.0 mmol), N,N-dimethylformamide (0.5 mmol), and dichloromethane (25 mL). Under a nitrogen stream, thionyl chloride (30.0 mmol) was added dropwise over 5 minutes while stirring at room temperature. The mixture was then stirred at 40 °C for 3 hours. The resulting mixture was concentrated under reduced pressure and diluted with THF (10 mL) to prepare a solution of the acid chloride intermediate. Separately, a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube was charged with hydrazine monohydrate (10.0 mmol), triethylamine (30.0 mmol), and THF (25 mL). Under a nitrogen stream, the acid chloride intermediate solution was added dropwise over 5 minutes while stirring at room temperature. The mixture was then stirred for an additional 1 hour. After completion of the reaction, the reaction solution was added dropwise to water (200 mL) to precipitate a solid. The resulting precipitate was filtered, washed with water and THF, and dried under reduced pressure to obtain an intermediate represented by the following formula (DA-3-1) in a yield of 86%. Next, intermediate (DA-3-1) (10.0 mmol), N,N-dimethylaminopyridine (1.0 mmol), and NMP (25 mL) were placed in a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube. Di-tert-butyl dicarbonate (22.0 mmol) was added dropwise over 5 minutes while stirring at room temperature under a nitrogen stream, and the mixture was stirred for an additional 3 hours. After the reaction was completed, hexane (100 mL) and isopropanol (10 mL) were added and the mixture was stirred for 1 hour to precipitate a solid. The resulting precipitate was filtered and dried under reduced pressure to obtain the intermediate represented by the following formula (DA-3-2) in 72% yield. Furthermore, intermediate (DA-3-2) (5.0 mmol), zinc metal (100 mmol), ammonium chloride (50 mmol), THF (15 mL), and ethanol (5 mL) were placed in a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube. Water (5 mL) was added dropwise over 5 minutes while stirring under a nitrogen stream in an ice bath, and the mixture was further stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure. The residue was extracted with ethyl acetate, and the organic phase was separated and washed with water. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to precipitate a white solid. The resulting solid was dissolved in THF, reprecipitated by adding dropwise ethanol, filtered, and dried under reduced pressure to obtain compound (DA-3) in 64% yield. Figures 5 and 6 show the results of compound (DA-3). 1 H-NMR spectrum (DMSO-d6, 400 MHz) and 13 The results of measuring the C-NMR spectrum (DMSO-d6, 75 MHz) are shown respectively. [ka]

[0113] [Synthesis Example 4] The diamine represented by the above formula (DA-4) (compound (DA-4)) was synthesized according to the following synthesis scheme. A three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube was charged with 2-(4-nitrophenoxy)acetic acid (63.0 mmol), N,N-dimethylformamide (1.5 mmol), and dichloromethane (65 mL). Under a nitrogen stream, thionyl chloride (90.0 mmol) was added dropwise over 5 minutes while stirring at room temperature. The mixture was then stirred at 40 °C for 4 hours. The resulting mixture was concentrated under reduced pressure and diluted with THF (20 mL) to prepare a solution of the acid chloride intermediate. Separately, a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube was charged with hydrazine monohydrate (30.0 mmol), pyridine (90.0 mmol), and THF (65 mL). Under a nitrogen stream, the acid chloride intermediate solution was added dropwise over 5 minutes while stirring at room temperature. The mixture was then stirred for an additional 1 hour. After completion of the reaction, the reaction solution was added dropwise to water (400 mL) to precipitate a solid. The resulting precipitate was filtered, washed with water, isopropanol, and THF, and dried under reduced pressure to obtain an intermediate represented by the following formula (DA-4-1) in a yield of 47%. Next, intermediate (DA-4-1) (10.0 mmol), N,N-dimethylaminopyridine (1.0 mmol), and NMP (25 mL) were placed in a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube. Di-tert-butyl dicarbonate (22.0 mmol) was added dropwise over 5 minutes while stirring at room temperature under a nitrogen stream, and the mixture was further stirred at 50 °C for 8 hours. After completion of the reaction, the reaction solution was added dropwise to water to reprecipitate and then filtered. The resulting solid was slurry-washed with isopropanol at 50 °C, cooled to room temperature, filtered, and dried under reduced pressure to obtain the intermediate represented by the following formula (DA-4-2) in a 79% yield. Furthermore, intermediate (DA-4-2) (5.0 mmol), zinc metal (100 mmol), ammonium chloride (50 mmol), THF (40 mL), and ethanol (10 mL) were placed in a three-neck flask equipped with a reflux condenser, thermometer, and nitrogen inlet tube. Water (5 mL) was added dropwise over 5 minutes while stirring under a nitrogen stream in an ice bath, and the mixture was further stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure. The residue was extracted with ethyl acetate, and the organic phase was separated and washed with water. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to precipitate a white solid. The resulting solid was dissolved in THF, reprecipitated by adding dropwise ethanol, filtered, and dried under reduced pressure to obtain compound (DA-4) in a 32% yield. Figures 7 and 8 show the results of compound (DA-4). 1 H-NMR spectrum (DMSO-d6, 400 MHz) and 13 The results of measuring the C-NMR spectrum (DMSO-d6, 75 MHz) are shown respectively. [ka]

[0114] [Synthesis Example 5] The diamine represented by the above formula (DA-5) (compound (DA-5)) was synthesized according to the following synthesis scheme. [ka]

[0115] [Synthesis Example 6] The diamine represented by the above formula (DA-6) (compound (DA-6)) was synthesized according to the following synthesis scheme. A 300 mL recovery flask was charged with chloroform (60 mL) and hydrazine monohydrate (2.43 mL, 50 mmol), cooled to 0 °C, and 4-bromobutanoyl chloride (5.76 mL, 50 mmol) was added portionwise. After stirring at 0 °C for 30 minutes, a solution of sodium carbonate (5.30 g, 50 mmol) in 40 mL of distilled water was added portionwise, followed by 4-bromobutanoyl chloride (6.34 mL, 55 mmol) portionwise and stirred at room temperature for 3 hours. After the reaction, the precipitate was filtered using a Kiriyama funnel and washed with distilled water and chloroform to obtain 17.5 g of wet crystals. This was dissolved in 150 mL of methanol at 60 °C and allowed to stand overnight for recrystallization. The crystals were filtered, washed with methanol, and dried to obtain 1.23 g (3.73 mmol, 7.5% yield) of the intermediate represented by the following formula (DA-6-1) as a white powder. Intermediate (DA-6-1) (1.23 g, 3.73 mmol), THF (37.3 mL), N,N-dimethylaminopyridine (228 mg, 1.86 mmol), and di-tert-butyl dicarbonate (4.07 g, 18.6 mmol) were mixed in a 200 mL recovery flask and stirred at 50 °C for 2 days. After the reaction was completed, 1-methylpiperazine (2.07 mL, 18.6 mmol) was added and stirred at room temperature for 1 day. 100 mL of ethyl acetate was added, and the mixture was extracted and washed three times with 100 mL of distilled water. The organic layer was dried over magnesium sulfate, filtered, and concentrated to obtain 1.41 g (2.66 mmol, 71.3% yield) of the intermediate represented by the following formula (DA-6-2) as a yellow liquid. Intermediate (DA-6-2) (1.41 g, 2.66 mmol), DMAc (20 mL), 4-nitrophenol (777 mg, 5.58 mmol), and potassium carbonate (919 mg, 6.65 mmol) were added to a 200 mL recovery flask and stirred at 60 °C for 8 hours. After the reaction was complete, 100 mL of ethyl acetate was added, followed by extraction and washing with 100 mL of distilled water once, 100 mL of aqueous ammonium chloride solution and 100 mL of aqueous sodium bicarbonate solution twice each, and finally with distilled water twice. The organic layer was dried over magnesium sulfate, filtered, and concentrated to yield 1.29 g (1.99 mmol, 75.0% yield) of the intermediate represented by the following formula (DA-6-3) as a yellow liquid. A 200 mL recovery flask was charged with intermediate (DA-6-3) (1.29 g, 1.99 mmol), zinc (2.61 g, 39.9 mmol), ammonium chloride (1.07 g, 19.9 mmol), THF (30 mL), and ethanol (10 mL). The mixture was cooled to 0 °C, and distilled water (1.02 g, 56.9 mmol) was added dropwise. The mixture was then stirred at room temperature for 2 days. After the reaction was complete, the zinc was removed by filtration through Celite, and the mixture was rinsed with THF. 100 mL of ethyl acetate was added, and the mixture was extracted and washed three times with 100 mL of distilled water. The organic layer was dried over magnesium sulfate, filtered, and concentrated. The resulting yellow viscous liquid was purified using a column chromatography column with a 50 / 50 mixture of hexane and ethyl acetate. The solution was then concentrated to yield 209 mg (356 μmol, 17.9% yield) of compound (DA-6) as a yellow viscous liquid. 9 and 10 show the results of compound (DA-6). 1 H-NMR spectrum (CDCl3, 400 MHz) and 13 The results of measuring the C-NMR spectrum (CDCl3, 75 MHz) are shown below. [ka]

[0116] [Synthesis Example 7] The diamine represented by the above formula (DA-7) (compound (DA-7)) was synthesized according to the following synthesis scheme. [ka]

[0117] [Synthesis Example 8] The diamine represented by the above formula (DA-8) (compound (DA-8)) was synthesized according to the following synthesis scheme. [ka]

[0118] [Evaluation of hydrogen bonding] The charge density of each atom was calculated using the density functional method with Gaussian 16 RevB.01, a quantum chemistry calculation program manufactured by Gaussian. The calculations were performed using the density functional M06-2X and the basis set def2-TZVPP. Geometry optimization and charge density analysis were performed using CM5 (Charge Model 5). The charge densities of the hydrogen bond donors (hydrogen atoms) and hydrogen bond acceptors (oxygen atoms) for model compounds with hydrogen-bonding groups represented by the following formulae (ne-1) to (ne-8) and (nc-1) to (nc-4) are summarized in Table 1. It is believed that intermolecular interactions are stronger when the hydrogen bond donor has a large positive charge and the hydrogen bond acceptor has a large negative charge. In particular, when the polymer is a polyimide or polyamic acid, it is desirable that the absolute value of the charge density of the hydrogen bond donor or hydrogen bond acceptor contained in groups introduced into the polymer separately from the amide or imide groups is larger than the absolute value of the charge density of the groups that can become hydrogen bond donors (amide groups = +0.316) or hydrogen bond acceptors (imide groups = -0.327) that are abundant in the polymer. Calculations using N-methylsuccinimide as a model compound for polyimide revealed that the charge density of the oxygen atom of the imide group was -0.327. The hydrogen-bonding properties were evaluated as good when the compound contained a hydrogen-bond donor with a charge density greater than +0.320 and a hydrogen-bond acceptor with a charge density less than -0.330. As a result, the hydrogen-bonding properties of compounds (nc-1) to (nc-4), which consisted only of a structure in which groups that could be hydrogen-bond donors and groups that could be hydrogen-bond acceptors were alternately bonded, were poor, whereas the hydrogen-bonding properties of compounds (ne-1) to (ne-8), which contained a structure in which two groups that could be hydrogen-bond donors or groups that could be hydrogen-bond acceptors were consecutively bonded, were all good. In addition, when groups that can be hydrogen bond donors or hydrogen bond acceptors are consecutive, it is thought that the consecutive hydrogen bonding sites interact with each other, increasing the strength of each individual hydrogen bond, resulting in a cooperative effect. Therefore, the actual hydrogen bonding strength may be greater than that predicted from the charge density. [ka]

[0119] [Table 1]

[0120] In Table 1, values ​​with a charge density greater than +0.320 and values ​​with a charge density less than -0.330 are underlined.

[0121] <Synthesis and evaluation of polymers> Polymers were synthesized in the following Synthesis Examples 9 to 41. In the following examples, the imidization rate of polyimide in the polymer solution was measured by the following method. [Imidization rate of polyimide] The polyimide solution was poured into pure water, and the resulting precipitate was thoroughly dried under reduced pressure at room temperature. After that, it was dissolved in deuterated dimethyl sulfoxide and measured at room temperature using tetramethylsilane as a standard substance. 1 H-NMR was measured. 1 The imidization rate [%] was calculated from the H-NMR spectrum (400 MHz) using the following formula (1). Imidization rate [%] = (1 - α × A1 / A2) × 100 ... (1) (In formula (1), A1 is the peak area of ​​a proton derived from the amide group of the amic acid, which appears at a chemical shift of approximately 10 ppm, and A2 is the peak area of ​​a proton derived from the aromatic group, which appears at a chemical shift of approximately 6 to 9 ppm. α is the ratio of the number of protons in the aromatic group to one proton in the amide group of the amic acid in the polymer precursor (polyamic acid).)

[0122] [Synthesis Example 9] 40 molar parts of compound (DA-1), 30 molar parts of compound (DB-5), and 30 molar parts of compound (DB-7) were dissolved in N-methyl-2-pyrrolidone (NMP), and 0.95 molar equivalents of tetracarboxylic dianhydride (compound (TA-2)) relative to the total amount of diamines were added. The reaction was carried out at room temperature for 6 hours to obtain a 15% by mass solution of polyamic acid (referred to as polymer (PA-1)) having a partial structure represented by the following formula (PA-1): [ka]

[0123] [Synthesis Examples 10 to 35] The polyamic acids polymers (PA-2) to (PA-22) and polymers (PA-C1) to (PA-C5) were obtained in the same manner as in Synthesis Example 9, except that the types and molar ratios of the tetracarboxylic dianhydrides and diamines were changed as shown in Table 2 below.

[0124] [Synthesis Example 36] Compound (DA-2) was dissolved in NMP, and 0.95 molar equivalents of tetracarboxylic dianhydride (compound (TA-2)) relative to the total amount of diamines was added. The reaction was carried out at room temperature for 6 hours to obtain a polyamic acid solution. To the resulting solution, 0.50 molar equivalents of 1-methylpiperidine and acetic anhydride relative to the carboxyl groups of the polyamic acid were added as dehydrating agents, and the mixture was heated and stirred at 60°C for 3 hours. The resulting solution was repeatedly concentrated under reduced pressure and diluted with NMP to obtain a 15% by mass solution of a polyimide (referred to as polymer (PI-1)) having a partial structure represented by the following formula (PI-1). The imidization rate of polymer (PI-1) was 50%. [ka]

[0125] [Synthesis Examples 37 to 41] The polyimides polymers (PI-2) to (PI-4) and polymers (PI-C1) to (PI-C2) were obtained in the same manner as in Synthesis Example 36, except that the types and molar ratios of the tetracarboxylic dianhydrides and diamines were changed as shown in Table 2 below. [Table 2]

[0126] The numerical values ​​in Table 2 indicate the proportion (mol %) of each compound used relative to the total amount (100 mol %) of tetracarboxylic dianhydrides used in the synthesis, and the numerical values ​​in Table 2 indicate the proportion (mol %) of each compound used relative to the total amount (100 mol %) of diamines used in the synthesis.

[0127] <Preparation and Evaluation of Liquid Crystal Alignment Agent> [Example 1: Photo-aligned FFS-type liquid crystal display element] (1) Preparation of liquid crystal alignment agent The polymer components (solid content: 40 parts by mass of polymer (PA-1), 60 parts by mass of polymer (PA-10)), 10 parts by mass of compound (AD-1), and 1 part by mass of compound (AD-3) were diluted with NMP and BC to obtain a solution with a solid content of 4.0% by mass and a solvent composition ratio of NMP:BC = 60:40 (mass ratio). This solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal alignment agent (AL-1).

[0128] (2) Formation of liquid crystal alignment film by photoalignment method The liquid crystal alignment agent (AL-1) prepared in (1) above was applied to each surface of a glass substrate having a flat electrode, an insulating layer, and a comb-shaped electrode laminated in this order on one side, and an opposing glass substrate having no electrode, using a spin coater. The applied coating was then heated on a hot plate at 80°C for 1 minute, and then heated in an oven at 230°C with the interior substituted with nitrogen for 30 minutes, forming a coating film with an average thickness of 100 nm. The surface of this coating film was irradiated with 3,000 J / m of linearly polarized ultraviolet light containing a 254 nm emission line using an Hg-Xe lamp. 2The coating film subjected to the photo-alignment treatment was then heat-treated (post-baked) for 30 minutes in a nitrogen-substituted oven at 230°C to form a liquid crystal alignment film.

[0129] (3) Manufacturing of FFS type liquid crystal display elements An epoxy resin adhesive containing 3.5 μm diameter aluminum oxide spheres was dispensed onto the outer periphery of the liquid crystal alignment film-bearing surface of one of the substrates prepared in (2) above, leaving a liquid crystal injection port. The two substrates were then placed face-to-face with their alignment film-bearing surfaces facing each other and pressed together so that the alignment treatment directions of the substrates were antiparallel. The adhesive was then thermally cured at 150°C for 1 hour. Next, negative nematic liquid crystal (MLC-6608, manufactured by Merck) was injected into the gap between the substrates through the liquid crystal injection port, which was then sealed with an epoxy adhesive. The substrates were then heated to 120°C and slowly cooled to room temperature to eliminate flow alignment during liquid crystal injection. Polarizers were then attached to both outer surfaces of the substrates to produce an FFS-mode liquid crystal display device.

[0130] (4) Evaluation of mechanical properties (rubbing resistance) The liquid crystal alignment agent (AL-1) prepared in (1) above was applied using a spin coater, heated on a hot plate at 80°C for 1 minute, and then heated in a nitrogen-purged oven at 230°C for 30 minutes to form a coating film with an average thickness of 100 nm. The haze value of the coating film was measured using a haze meter. Next, the coating film was rubbed five times using a rubbing machine equipped with a roll wrapped in cotton cloth at a roll rotation speed of 1000 rpm, a stage movement speed of 30 mm / sec, and a pile indentation length of 0.3 mm. The haze value of the liquid crystal alignment film was then measured using a haze meter, and the difference from the haze value before and after rubbing (haze change) was calculated. If the haze value of the film before rubbing is Hz1 (%) and the haze value of the film after rubbing is Hz2 (%), the haze change is expressed by the following formula (z-1): Haze change value (%) = Hz2 - Hz1 ... (z-1) A haze change value of the liquid crystal alignment film of less than 0.5% was evaluated as "excellent," a haze change value of 0.5% or more but less than 1.0% was evaluated as "good," and a haze change value of 1.0% or more was evaluated as "poor." A haze change value of less than 1.0% indicates high rubbing resistance (abrasion resistance), i.e., the mechanical properties of the liquid crystal alignment film are good. As a result, this example was evaluated as "good."

[0131] (5) Evaluation of liquid crystal alignment The liquid crystal display element manufactured in (3) above was observed under a microscope at a magnification of 50x to check for the presence or absence of abnormal domains in the change in brightness when a voltage of 5V was turned on and off (applied and removed). The orientational order was evaluated as "good" when no abnormal domains were observed, and as "poor" when abnormal domains were observed. As a result, in this example, the evaluation was "good."

[0132] (6) Evaluation of liquid crystal alignment (AC image retention characteristics) The liquid crystal display element manufactured in (3) above was measured for change in liquid crystal azimuth angle before and after driving for 68 hours under backlight irradiation at an AC voltage of 11V using a birefringence meter (AXOSTEP high-precision Mueller matrix imaging polarimeter, manufactured by AXOMETRICS). The change in liquid crystal azimuth angle was evaluated as "excellent" when it was less than 0.1 degrees, "good" when it was 0.1 degrees or more but less than 0.3 degrees, and "poor" when it was 0.3 degrees or more. The smaller the change in liquid crystal azimuth angle, the less likely AC afterimages are to occur even when the liquid crystal display element is driven for a long time, and the better the liquid crystal alignment. As a result, in this example, the evaluation was "good."

[0133] [Examples 2 to 19, Comparative Examples 1 to 5] In the above Example 1, except that the polymer contained in the liquid crystal alignment agent was changed as shown in the following Table 3, a liquid crystal alignment agent was prepared in the same manner as in Example 1, a liquid crystal alignment film was formed by a photoalignment method, and an FFS-type liquid crystal display element was manufactured and various evaluations were performed. The evaluation results are shown in the following Table 3.

[0134] [Example 20: Rubbed alignment FFS type liquid crystal display element] (1) Preparation of liquid crystal alignment agent Polymer components (solid content: 30 parts by mass of polymer (PI-1), 70 parts by mass of polymer (PA-12)), 4 parts by mass of compound (AD-2), and 1 part by mass of compound (AD-3) were diluted with NMP, GBL, BC, and DAA to obtain a solution with a solid content of 4.0% by mass and a solvent composition ratio of NMP:GBL:BC:DAA = 30:40:10:20 (mass ratio). This solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal alignment agent (AL-25). (2) Formation of liquid crystal alignment film by rubbing alignment method The liquid crystal alignment agent (AL-25) prepared in (1) above was applied to a glass substrate having a flat electrode, an insulating layer, and a comb-shaped electrode laminated in this order on one side, and to a counter glass substrate without an electrode, using a spin coater. The substrate was then heated on a hot plate at 80°C for 1 minute, and then heated in a nitrogen-purged oven at 230°C for 30 minutes to form a coating film with an average thickness of 100 nm. The surface of this coating film was then rubbed twice using a rubbing machine equipped with a roll wrapped around a cotton cloth at a roll rotation speed of 1000 rpm, a stage movement speed of 30 mm / sec, and a pile depth of 0.3 mm. The rubbed coating film was then ultrasonically cleaned in ultrapure water for 1 minute and then dried in an oven at 100°C for 10 minutes to form a liquid crystal alignment film.

[0135] (3) Manufacturing of FFS type liquid crystal display elements An FFS-type liquid crystal display element was produced in the same manner as in Example 1(3). (4) Evaluation of rubbing resistance (film strength) The mechanical properties (rubbing resistance) were evaluated in the same manner as in (4) of Example 1. As a result, this example was evaluated as "good." (5) Evaluation of liquid crystal alignment The liquid crystal alignment property was evaluated in the same manner as in (5) of Example 1. As a result, this example was evaluated as "good." (6) Evaluation of AC image retention characteristics The AC afterimage characteristics were evaluated in the same manner as in (6) of Example 1. As a result, this example was evaluated as "good."

[0136] [Examples 21 to 25, Comparative Examples 6 to 7] In the same manner as in Example 20, except that the polymer contained in the liquid crystal alignment agent was changed as shown in the following Table 3, a liquid crystal alignment agent was prepared and a liquid crystal alignment film was formed by the rubbing alignment method, and an FFS-type liquid crystal display element was manufactured and various evaluations were performed. The evaluation results are shown in Table 3 below.

[0137] [Table 3]

[0138] As shown in Table 3, the liquid crystal aligning agents of Examples 1 to 25 containing polymer (P) were evaluated as "excellent" or "good" in terms of mechanical properties, liquid crystal alignment, and AC image sticking property, and thus had a good balance of various properties. In contrast, the liquid crystal aligning agents of Comparative Examples 1 to 7 not containing polymer (P) were evaluated as inferior to the Examples in terms of at least one of mechanical properties and AC image sticking property.

[0139] The results of the Examples and Comparative Examples will be discussed below, but this discussion is merely speculation and does not limit the present invention in any way.

[0140] The mechanical properties of Examples 1 to 25 were evaluated as "excellent" or "good." These liquid crystal aligning agents contain a polymer having a partial structure in the main chain in which three or more consecutive hydrogen-bonding groups (-NH-, -N(Boc)-, -C(=O)-, -SO2-) are present and two consecutive groups that can act as hydrogen bond donors or hydrogen bond acceptors. Therefore, it is presumed that multipoint hydrogen bonds can be formed via this partial structure, which strengthens intermolecular interactions in the film and results in good mechanical properties. Furthermore, the liquid crystal aligning agents (Examples 3 to 19, 21 to 25) containing a polymer having an acylhydrazine structure in the main chain exhibited particularly excellent mechanical properties.

[0141] On the other hand, the mechanical properties were evaluated as "poor" in the examples where an amide structure was introduced instead of the multi-point hydrogen-bonded structure, such as Comparative Examples 1, 5, and 7, and in the example where a nitrogen-containing heterocycle was introduced instead of the multi-point hydrogen-bonded structure, such as Comparative Example 3. It is presumed that when a nitrogen-containing heterocycle was introduced instead of the multi-point hydrogen-bonded structure, the film became embrittled due to salt formation caused by acid-base interactions in the polymer.

[0142] From the above, it is presumed that polymer (P) has a multi-point hydrogen-bonding structure in which groups that can become hydrogen bond donors or hydrogen bond acceptors are continuous, and therefore the toughness and abrasion resistance of the liquid crystal alignment film are improved through intermolecular interactions, thereby suppressing film abrasion due to rubbing treatment.

[0143] The AC image retention characteristics were evaluated as "excellent" or "good" in Examples 1 to 25. This is presumably because the polymer (P) contained in the liquid crystal alignment agent of Examples 1 to 25 has high thermal rearrangement (increased anisotropy) due to heating after exposure in the photoalignment method, and high extensibility of the film surface due to rubbing treatment in the rubbing alignment method, resulting in high alignment order of the molecular chains of the liquid crystal alignment film and excellent alignment control power for the liquid crystal. Furthermore, the liquid crystal alignment agents having an acylhydrazine structure or an amide structure in the polymer main chain (Examples 4, 6 to 13, 15 to 17, 19, 21 to 22, 24 to 25) showed particularly excellent AC image retention characteristics.

[0144] On the other hand, the liquid crystal aligning agents containing a polymer having a urea structure in the main chain (Comparative Examples 4 and 6) exhibited inferior AC image retention properties compared to Examples 1 to 25. This is thought to be because the polymers contained in the liquid crystal aligning agents of Comparative Examples 4 and 6 did not have sufficient thermal reorientation or stretchability. Furthermore, in Comparative Example 2, which contained a polymer having an oxamide structure without a thermally labile group in the main chain instead of polymer (P), the high compatibility between the polymers made it difficult for the photosensitive polymer to exist in the surface layer of the liquid crystal alignment film, presumably resulting in poor AC image retention properties. Furthermore, in Comparative Example 3, the polymer contained in the liquid crystal aligning agent had a nitrogen-containing heterocycle, which presumably reduced thermal reorientation due to acid-base interactions in the polymer, presumably resulting in poor AC image retention properties.

[0145] The arrangement of the groups (D) that can act as hydrogen bond donors and the groups (A) that can act as hydrogen bond acceptors in a multipoint hydrogen bond structure is presumed to affect the strength and directionality of the intermolecular interaction. The polymers (P) used in Examples 1 to 14 have an oxamide structure (DAAD type), a diacylhydrazine structure (ADDA type), a sulfamide structure (DAAD type, where -SO2- has two oxo groups (=O) and therefore has two consecutive hydrogen bond acceptors), or an acylhydrazine structure (DDA type). These polymers contain a structure in which either the groups (D) that can act as hydrogen bond donors or the groups (A) that can act as hydrogen bond acceptors are two consecutive groups (i.e., DD or AA). This is presumed to result in excellent mechanical properties and AC image retention, two opposing properties, and a good balance of various properties. On the other hand, it is presumed that the urea structure (DAD type) of the polymer contained in the liquid crystal alignment agent of Comparative Examples 4 and 6 lacks thermal reorientation or stretchability, and the amide structure (DA type) of the polymer contained in the liquid crystal alignment agent of Comparative Examples 1, 5, and 7 lacks intermolecular interactions, resulting in a poor balance between mechanical properties and AC afterimage properties.

[0146] It is believed that the thermally labile group can improve the solubility of the polymer by protecting the highly polar hydrogen-bonding functional group, and can also hydrophobize the polymer (lower the surface free energy) and control the phase separation. Therefore, by introducing a thermally labile group into a photosensitive or stretchable polymer, the photosensitive or stretchable polymer is unevenly distributed on the surface of the liquid crystal alignment film, which is presumed to contribute to the development of good liquid crystal alignment and AC image retention properties.

[0147] From the above, it was found that a liquid crystal aligning agent containing polymer (P) can provide a liquid crystal alignment film with good mechanical properties, and can also provide a liquid crystal device with good liquid crystal alignment properties and AC afterimage properties.

Claims

1. A liquid crystal aligning agent comprising a polymer containing a structural unit derived from a diamine represented by the following formula (0): 【Chemical 1】 (In formula (0), R １ and R ２ are each independently a halogen atom or a monovalent organic group. １ and Ar ２ are each independently a group in which (p+2) hydrogen atoms have been removed from a benzene ring, a naphthalene ring, or a biphenyl ring. p and q are each independently an integer of 0 to 4. X １ and X ２ are each independently a single bond or a divalent organic group. １ is -CO-CO-, -SO ２ --CO-NR ５ -* Ｎ , or -SO ２ -NR ５ -* Ｎ It is. ５ is a hydrogen atom or a monovalent organic group. Ｎ " is "-COOZ １ " is the bond to the nitrogen atom to which Z is bonded. １ is a monovalent organic group.

2. X in the above formula (0) １ and X ２ each independently represents a single bond, a divalent hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, a sulfur atom, —CO—, or —SO ２ -, -NR ６ -, -C=N-, or any methylene group in the divalent hydrocarbon group having 2 to 12 carbon atoms is replaced with an oxygen atom, a sulfur atom, -CO-, or -SO ２ -, -NR ６ - or -C=N- substituted divalent group (wherein R ６ The liquid crystal aligning agent according to claim 1, wherein:

3. Z in the above formula (0) １ The liquid crystal aligning agent according to claim 1, wherein is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.

4. When p in the above formula (0) is 1 or more, R １ is an alkyl group having 1 to 3 carbon atoms, When q in the above formula (0) is 1 or more, R ２ The liquid crystal aligning agent according to claim 1, wherein is an alkyl group having 1 to 3 carbon atoms.

5. 2. The liquid crystal aligning agent according to claim 1, wherein the polymer is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polyamide, polyamideimide, polyurea, and polyimine.

6. The liquid crystal aligning agent according to claim 1, further comprising a polymer not containing a structural unit derived from the diamine represented by the formula (0).

7. The liquid crystal aligning agent according to claim 1, wherein the diamine represented by the formula (0) is represented by the following formula (1): 【Chemistry 2】 (In formula (1), R １ and R ２ are each independently a halogen atom or a monovalent organic group. p and q are each independently an integer of 0 to 4. X １ and X ２ are each independently a single bond or a divalent organic group. １ is -CO-CO-, -SO ２ --CO-NR ５ -* Ｎ , or -SO ２ -NR ５ -* Ｎ It is. ５ is a hydrogen atom or a monovalent organic group. Ｎ " is "-COOZ １ " is the bond to the nitrogen atom to which Z is bonded. １ is a monovalent organic group.

8. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 7.

9. A liquid crystal device comprising the liquid crystal alignment film according to claim 8 .

10. A polymer containing a structural unit derived from a diamine represented by the following formula (0): 【Chemistry 3】 (In formula (0), R １ and R ２ are each independently a halogen atom or a monovalent organic group. １ and Ar ２ are each independently a group in which (p+2) hydrogen atoms have been removed from a benzene ring, a naphthalene ring, or a biphenyl ring. p and q are each independently an integer of 0 to 4. X １ and X ２ are each independently a single bond or a divalent organic group. １ is -CO-CO-, -SO ２ --CO-NR ５ -* Ｎ , or -SO ２ -NR ５ -* Ｎ It is. ５ is a hydrogen atom or a monovalent organic group. Ｎ " is "-COOZ １ " is the bond to the nitrogen atom to which Z is bonded. １ is a monovalent organic group.

11. A diamine represented by the following formula (0): 【Chemistry 4】 (In formula (0), R １ and R ２ are each independently a halogen atom or a monovalent organic group. １ and Ar ２ are each independently a group in which (p+2) hydrogen atoms have been removed from a benzene ring, a naphthalene ring, or a biphenyl ring. p and q are each independently an integer of 0 to 4. X １ and X ２ are each independently a single bond or a divalent organic group. １ is -CO-CO-, -SO ２ --CO-NR ５ -* Ｎ , or -SO ２ -NR ５ -* Ｎ It is. ５ is a hydrogen atom or a monovalent organic group. Ｎ " is "-COOZ １ " is the bond to the nitrogen atom to which Z is bonded. １ is a monovalent organic group.

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