Polymer composition, liquid crystal aligning agent, resin film, liquid crystal alignment film, method for producing liquid crystal display element, and liquid crystal display element

Abstract

To provide a new polymer composition suitable for a liquid crystal aligning agent capable of obtaining a liquid crystal display element having a high relaxation rate of accumulated charge and little afterimage.SOLUTION: A polymer (A) having a partial structure represented by any one of Formulae (i-1) to (i-3) and having, in a main chain, a structure obtained by removing R from the partial structure. Wherein R is a monovalent organic group having two aromatic hydrocarbon rings and a nitrogen atom (A). In the monovalent organic group, each of the two aromatic hydrocarbon rings satisfies at least one of the condition (I) that one of carbon atoms of the aromatic hydrocarbon ring and the nitrogen atom (A) are directly bonded to each other, and the condition (II) that when the nitrogen atom (A) is contained in the aromatic heterocyclic ring, the aromatic hydrocarbon ring and the aromatic heterocyclic ring form a condensed ring. One of the two aromatic hydrocarbon rings is conjugated with the nitrogen atom (B) marked with * 1. *Represents a bond. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer composition, a liquid crystal aligning agent, a resin film, a liquid crystal alignment film, a method for producing a liquid crystal display element, and a liquid crystal display element. [Background technology]

[0002] Liquid crystal display devices are widely used as displays for personal computers, mobile phones, smartphones, televisions, and the like. Liquid crystal display devices include, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, pixel electrodes and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the orientation of liquid crystal molecules in the liquid crystal layer, and thin-film transistors (TFTs) that switch electrical signals supplied to the pixel electrodes. Known methods for driving liquid crystal molecules include vertical electric field methods such as twisted nematic (TN) and vertical alignment (VA) methods, and horizontal electric field methods such as in-plane switching (IPS) and fringe field switching (FFS) methods. The horizontal electric field method, in which electrodes are formed on only one side of the substrate and an electric field is applied parallel to the substrate, is known for its wide viewing angle and high-quality display characteristics compared to conventional vertical electric field methods, in which liquid crystal is driven by applying a voltage to electrodes formed on the top and bottom substrates.

[0003] Polyimide resin films are widely used as liquid crystal alignment films for use in liquid crystal display elements, etc. These polyimide liquid crystal alignment films are produced by applying a liquid crystal alignment agent, whose main components are a polymer such as polyamic acid (also called polyamic acid), polyamic acid ester, or polyimide, and a solvent, to a substrate.

[0004] The in-plane switching mode, which has excellent viewing angle characteristics, is widely adopted, mainly in mobile phones and tablet devices. With the recent rapid advancement in resolution of panels, high display quality is becoming increasingly important, and specifications for preventing display defects known as "image retention" or simply "image persistence" are becoming increasingly stringent. One known cause of image retention is charge accumulation within the liquid crystal cell due to the application of asymmetric positive and negative voltages during driving, and several technologies have been proposed to quickly alleviate this accumulation (Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2004 / 021076 [Patent Document 2] International Publication No. 2018 / 062440 [Patent Document 3] International Publication No. 2018 / 110354 Summary of the Invention [Problem to be solved by the invention]

[0006] However, there are not many known methods for increasing the rate at which accumulated charges are relaxed. An object of the present invention is to provide a novel polymer composition suitable as a liquid crystal aligning agent, which can provide a liquid crystal display device with a high relaxation rate of accumulated charges and little afterimage. [Means for solving the problem]

[0007] The present inventors have conducted extensive research and have found that the above-mentioned problems can be solved by forming a resin film using a polymer composition having a specific blending composition, and have thus completed the present invention. Specifically, the present invention is summarized as follows.

[0008] A polymer composition comprising: a polymer (A) having a partial structure represented by any one of the following formulas (i-1) to (i-3), and a polymer (A) having a structure in a main chain obtained by removing R from the partial structure, The polymer composition, wherein the polymer (A) is a polymer obtained by reacting a diamine component containing a diamine (c) having a partial structure represented by any one of the following formulas (i-1) to (i-3) with a tetracarboxylic acid derivative component: [ka] (In the formulas (i-1) to (i-3), R is a monovalent organic group having two aromatic hydrocarbon rings and a nitrogen atom (A). In the monovalent organic group, each of the two aromatic hydrocarbon rings satisfies at least one of the following conditions (I) and (II): Condition (I): One of the carbon atoms of the aromatic hydrocarbon ring and the nitrogen atom (A) are directly bonded to each other. Condition (II): When the nitrogen atom (A) is contained in an aromatic heterocycle, the aromatic hydrocarbon ring and the aromatic heterocycle form a condensed ring. One of the two aromatic hydrocarbon rings is conjugated with the nitrogen atom (B) marked with *1. * represents a bond.) [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a novel polymer composition suitable as a liquid crystal aligning agent, which can provide a liquid crystal display device with a high rate of relaxation of accumulated charges and little afterimage. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view showing an example of a liquid crystal display element of the present invention. [Figure 2] FIG. 2 is a schematic cross-sectional view showing another example of a liquid crystal display element of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] In this specification, halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0012] <Polymer (A)> The polymer composition of the present invention contains a polymer (A). The polymer (A) has a partial structure represented by any one of the following formulas (i-1) to (i-3). The polymer (A) has, in its main chain, a structure obtained by removing R from the partial structure. Furthermore, the polymer (A) is a polymer obtained by reacting a diamine component containing a diamine (c) having a partial structure represented by any one of the following formulas (i-1) to (i-3) with a tetracarboxylic acid component. [ka] (In formulas (i-1) to (i-3), R is a monovalent organic group having two aromatic hydrocarbon rings and a nitrogen atom (A). In the monovalent organic group, each of the two aromatic hydrocarbon rings satisfies at least one of the following conditions (I) and (II). Condition (I): One of the carbon atoms of the aromatic hydrocarbon ring is directly bonded to the nitrogen atom (A). Condition (II): When the nitrogen atom (A) is contained in an aromatic heterocycle, the aromatic hydrocarbon ring and the aromatic heterocycle form a condensed ring. One of the two aromatic hydrocarbon rings is conjugated with the nitrogen atom (B) marked with *1. * represents a bond.) Hereinafter, a structure consisting of an aromatic hydrocarbon and a nitrogen atom (A) that satisfies at least one of the conditions (I) and (II) may be referred to as a "specific aromatic amine structure."

[0013] Examples of the main skeleton of the polymer (A) include a skeleton formed from a polyimide precursor such as polyamic acid or polyamic acid ester, or an imide compound of the polyimide precursor, such as polyimide, polyamide, or polyurea. The polymer (A) can be one or more polymers selected from these, appropriately selected depending on the intended use of the polymer composition. The main skeleton of the polymer (A) is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.

[0014] In the present invention, the "main chain" of a polymer refers to the "backbone" portion of the polymer consisting of the longest chain of atoms. Therefore, "having in the main chain a structure obtained by removing R from a partial structure represented by any one of formulas (i-1) to (i-3)" means that the structure obtained by removing R from the partial structure constitutes a part of the main chain of the polymer. On the other hand, in the present invention, R corresponds to a side chain, and therefore, hereinafter, R may be referred to as a side chain R.

[0015] Here, in the present invention, the aromatic hydrocarbon ring when defining R in the above formulas (i-1) to (i-3) refers to a monocyclic (e.g., benzene ring) or condensed (e.g., naphthalene ring) aromatic hydrocarbon ring. For example, R may have a biphenyl structure, but when R has a biphenyl structure, the biphenyl structure in the aromatic hydrocarbon ring when defining R is considered to consist of two aromatic hydrocarbon rings. Specifically, when R is a monovalent organic group represented by the following formula (r2), if the nitrogen atom marked with *3 is a nitrogen atom (A), the benzene ring marked with *4 and the benzene ring marked with *5 may together constitute a biphenyl structure. However, in the present invention, the benzene ring marked with *4 and the benzene ring marked with *5 each correspond to one aromatic hydrocarbon ring defining R. Therefore, even if R2 in the monovalent organic group represented by the following formula (r2) is not an aromatic hydrocarbon ring, the monovalent organic group represented by the following formula (r2) is a monovalent organic group having two aromatic hydrocarbon rings and a nitrogen atom (A), and each of the two aromatic hydrocarbon rings satisfies the above condition (I). Therefore, a structure obtained by removing R2 from the monovalent organic group represented by the following formula (r2) corresponds to a specific aromatic amine structure. [ka] (R2 is a hydrogen atom or a monovalent organic group. * represents a bond to the nitrogen atom (B).)

[0016] The hydrogen atoms on the two aromatic hydrocarbon rings of R may each independently be substituted with a hydroxy group, a halogen atom, or a monovalent organic group. Among these, from the viewpoint of efficiently obtaining the effects of the present invention, it is preferable that the two aromatic hydrocarbon rings are each independently a benzene ring or a naphthalene ring. Examples of monovalent organic groups include monovalent hydrocarbon groups and monovalent groups in which functional groups such as -O-, -COO-, -CO-, -NHCO-, and -S- have been introduced between carbon-carbon bonds in monovalent hydrocarbon groups.

[0017] The number of nitrogen atoms contained in R in the above formulas (i-1) to (i-3) is 1 or 2 or more, and from the viewpoint of ease of synthesis, it is preferably 1 or 2 to 4, and more preferably 1 or 2. Furthermore, the number of carbon atoms contained in R is not particularly limited, but it is preferably 12 to 40, and more preferably 12 to 30. In the above formulas (i-1) to (i-3), R may have three or more aromatic hydrocarbon rings. In that case, at least two of the three or more aromatic hydrocarbon rings should satisfy at least one of the above conditions (I) and (II). Such R also corresponds to R in the above formulas (i-1) to (i-3) in the present invention. The number of aromatic hydrocarbon rings contained in R is not particularly limited. In addition, in R, not only one of the two aromatic hydrocarbon rings may be conjugated with the nitrogen atom (B), but both of the two aromatic hydrocarbon rings may be conjugated with the nitrogen atom (B).

[0018] In the partial structure represented by any one of the above formulas (i-1) to (i-3), the two aromatic hydrocarbon rings in R satisfy at least one of the above conditions (I) and (II), and one of the two aromatic hydrocarbon rings is conjugated with the nitrogen atom (B) marked with *1. This causes the HOMO (Highest Occupied Molecular Orbital) to extend from the main chain of the polymer (A) to at least a part of the specific aromatic amine structure of the side chain R, and electric charges generated or accumulated on the main chain are efficiently transferred to the specific aromatic amine structure on the side chain R, thereby achieving the effect of accelerating the relaxation characteristics of the accumulated electric charges. The present inventors have found that when the two aromatic hydrocarbon rings in R in the partial structure represented by any one of the above formulae (i-1) to (i-3) satisfy at least one of the above conditions (I) and (II), the absolute value of the Mulliken charge of the nitrogen atom (A) is 0.550 or more. The absolute value of the Mulliken charge is 0.550 or more, and further, one of the two aromatic hydrocarbon rings in the partial structure represented by any one of the above formulae (i-1) to (i-3) is conjugated with the nitrogen atom (B) marked with *1, which is thought to result in efficient charge transfer from the main chain to the side chain R. Here, the Mulliken charge is a charge determined from the electron density distribution calculated by molecular orbital calculation, and the larger the absolute value of the charge, the easier the charge transfer to the atom being calculated. The Mulliken charge can be determined, for example, by calculating the most stable structure in the ground state of the molecule being calculated in vacuum using B3LYP as the functional and 6-31G* as the basis function. As the molecular orbital calculation software used for the molecular orbital calculation, for example, Gaussian09 (Revision C.01, M.J. Frisch, et al., Gaussian, Inc., 2010.) manufactured by Gaussian, Inc., USA, can be used. However, the means for performing the molecular orbital calculation is not limited to this.

[0019] The above R satisfies the relationship that one of the two aromatic hydrocarbon rings in the specific aromatic amine structure is conjugated with the nitrogen atom (B). Examples of a mode that satisfies such a relationship include the following (i) and (ii). (i) One of the two aromatic hydrocarbon rings is directly bonded to the nitrogen atom (B), thereby conjugating one of the two aromatic hydrocarbon rings with the nitrogen atom (B). (ii) One of the two aromatic hydrocarbon rings is conjugated to the nitrogen atom (B) via one aromatic hydrocarbon ring, thereby conjugating one of the two aromatic hydrocarbon rings to the nitrogen atom (B). The one intervening aromatic hydrocarbon ring in (ii) above is not particularly limited as long as it is a divalent aromatic hydrocarbon ring, and examples thereof include a phenylene group. Each hydrogen atom of the phenylene group may be independently substituted with a hydroxy group, a halogen atom, or a monovalent organic group. Examples of the monovalent organic group include a monovalent hydrocarbon group and a monovalent group in which a functional group such as -O-, -COO-, -CO-, -NHCO-, or -S- has been introduced between the carbon-carbon bonds of the monovalent hydrocarbon group. From the viewpoint of obtaining the effects of the present invention, it is preferable that one of the two aromatic hydrocarbon rings is directly bonded to the nitrogen atom (B), thereby conjugating one of the two aromatic hydrocarbon rings with the nitrogen atom (B).

[0020] R in the above formulas (i-1) to (i-3) is preferably a monovalent organic group represented by any one of the following formulas (r1) to (r3), more preferably a monovalent organic group represented by (r2). [ka] (R1 and R2 are hydrogen atoms or monovalent organic groups. R3 is a monovalent organic group. n represents an integer of 1 to 3. However, when n is 1, R3 is an organic group having an aromatic hydrocarbon group directly bonded to the pyridine ring of the quinoline ring marked with *2, and when n is 2 or 3, at least one R3 is an organic group having an aromatic hydrocarbon group directly bonded to the pyridine ring of the quinoline ring marked with *2. * represents a bond, and the * in formula (r3) is bonded to the benzene ring constituting the quinoline ring. The hydrogen atom on the benzene ring may be substituted with a hydroxy group, a halogen atom, or a monovalent organic group.)

[0021] Examples of the monovalent organic group in R1, R2, and R3 include a monovalent hydrocarbon group, a monovalent group in which a functional group such as -O-, -COO-, -CO-, -NHCO-, -S-, or -NH- has been introduced between the carbon-carbon bonds of a monovalent hydrocarbon group, a monovalent aromatic heterocyclic group, and a protecting group for an amino group. In R1, R2, and R3, the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group and aromatic heterocyclic group may be substituted with a halogen atom, a hydroxy group, or the like. Examples of the monovalent aromatic heterocyclic group include a monovalent nitrogen-containing aromatic heterocyclic group such as a pyridyl group. In R3, examples of the organic group having an aromatic hydrocarbon group directly bonded to the pyridine ring of the quinoline ring marked with *2 include aryl groups such as phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include monovalent hydrocarbon groups, monovalent groups in which functional groups such as -O-, -COO-, -CO-, -NHCO-, -S-, and -NH- have been introduced between the carbon-carbon bonds of a monovalent hydrocarbon group, monovalent aromatic heterocyclic groups, and protecting groups for amino groups. Examples of the monovalent aromatic heterocyclic groups include monovalent nitrogen-containing aromatic heterocyclic groups such as pyridyl. Specific examples of the above-mentioned amino-protecting group include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, a 1,1-dimethyl-2-cyanoethyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, and a 2-(trimethylsilyl)ethoxycarbonyl group, and preferably a tert-butoxycarbonyl group. Furthermore, examples of the monovalent organic group that may replace a hydrogen atom on a benzene ring include monovalent hydrocarbon groups and monovalent groups in which a functional group such as -O-, -COO-, -CO-, -NHCO-, or -S- has been introduced between the carbon-carbon bonds of a monovalent hydrocarbon group.

[0022] As used herein, the term "hydrocarbon group" refers to a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the chain hydrocarbon group include alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; alkenyl groups having 2 to 30 carbon atoms, such as ethenyl, propenyl, and butenyl; and alkynyl groups having 2 to 30 carbon atoms, such as ethynyl and propynyl. These may be linear or branched. Examples of the alicyclic hydrocarbon group include cyclopentyl and cyclohexyl; and examples of the aromatic hydrocarbon group include phenyl, tolyl, benzyl, and phenethyl. A monovalent hydrocarbon group refers to a group obtained by removing one hydrogen atom from the above hydrocarbon group.

[0023] Specific examples of the monovalent organic group represented by (r2) above include monovalent organic groups represented by the following formulae (r2-1) to (r2-2). [ka]

[0024] <Diamine (c)> The diamine (c) preferably has a structure that allows the partial structure represented by any one of the above formulas (i-1) to (i-3) to be introduced into the main chain of the polymer (A), and has one or more of the partial structures represented by any one of the above formulas (i-1) to (i-3). More specifically, the diamine (c) is preferably a compound represented by any one of the following formulas (d1-1) to (d1-3). [ka]

[0025] In formula (d1-1), when n is 1, R has the same meaning as R in formula (i-1) above, and when n is 2 or 3, n R each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or the same monovalent organic group as R in formula (i-1) above, and at least one of the n R represents the same monovalent organic group as R in formula (i-1) above. Furthermore, when at least one R is the same monovalent organic group as R in formula (i-1) above, the preferred aspects of R are the same as R in formula (i-1) above. In formulas (d1-2) to (d1-3), R is the same as R in the above formulas (i-2) to (i-3). Preferred embodiments of R in (d1-2) to (d1-3) are the same as R in the above formulas (i-2) to (i-3). L2 and L3 each represent a single bond, -NR'-, -O-, -NR'-CO-, -CO-NR'-, -O-CO-, or -CO-O-, and R' represents a hydrogen atom or a monovalent organic group. Specific examples of the monovalent organic group R' include the structures exemplified for R1 and R2 in the above formulas (r1) to (r2). Ar2 and Ar3 represent an aromatic ring group. Specific examples of the aromatic ring group include groups in which two hydrogen atoms have been removed from the ring portion of an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a benzimidazole ring, an indole ring, a quinoxaline ring, or an acridine ring. The hydrogen atoms on the aromatic ring may be replaced by a hydroxy group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Of these, a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, and a carbazole ring are more preferred. In formula (d1-1), when n is 2 or 3, the n m2's may be the same or different. In formula (d1-2), when there are two or more Ar2's, the two or more Ar2's may be the same or different. In formula (d1-2), when there are two or more L2s, the two or more L2s may be the same or different. In formula (d1-3), two or more Ar3s may be the same or different. In formula (d1-3), two or more L3s may be the same or different.

[0026] Among the diamines (c), when n is 1 in the formula (d1-1), R in the formula (d1-1) represents a monovalent organic group represented by the formula (r2) above, and when n is 2 or 3, the n R in the formula (d1-1) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a monovalent organic group represented by the formula (r2) above, and at least one of the n R represents a monovalent organic group represented by the formula (r2) above. Furthermore, in the formulas (d1-2) to (d1-3), R in the formulas (d1-2) to (d1-3) is preferably a monovalent organic group represented by the formula (r2). It is more preferred that the orbital coefficient of the nitrogen atom (A) in the formula (r2) in the highest occupied molecular orbital (described below) is less than 0.01.

[0027] As the resolution of LCD panels increases, the display area becomes smaller, and therefore, LCD alignment films are required to have higher transparency than ever before. Methods proposed for increasing the transparency of LCD alignment films include making arylamines into tertiary structures (WO 2020 / 166623) and introducing linear metharylene structures (WO 2019 / 093037). However, the inventors have found through their investigations that the method of changing the structure in the main chain direction as described in WO 2019 / 093037 has the disadvantage of reducing the relaxation characteristics of accumulated charges compared to the techniques described in Patent Documents 1 to 3. In addition, although the method described in WO 2020 / 166623 is also effective, there is room for improvement in terms of increasing the relaxation rate of accumulated charges while obtaining high transparency. To increase the relaxation rate of the accumulated charges and obtain high transparency, the diamine (c) used in the present invention preferably has an orbital coefficient of the nitrogen atom (A) in the highest occupied molecular orbital of less than 0.01, more preferably less than 0.005, and even more preferably less than 0.0025. This configuration suppresses the absorption intensity due to the nitrogen atom (A) on the conjugated side chain R, thereby increasing the transmittance of the resin film obtained from the polymer composition. Here, the orbital coefficients can be determined from the electron density distribution of the target molecule (e.g., diamine (c)) after structural optimization, obtained by molecular orbital calculations. Specifically, the orbital coefficients are derived using B3LYP as the functional and 6-31G* as the basis function in molecular orbital calculations that perform structural optimization and electron density analysis. Examples of software that can be used for molecular orbital calculations include Gaussian 09 (Revision C.01, M.J. Frisch, et al., Gaussian, Inc., 2010) manufactured by Gaussian, Inc., USA. However, the means for performing the molecular orbital calculations are not limited to this.

[0028] Here, the orbital coefficient of the nitrogen atom is the sum of the squares of the expansion coefficients of the corresponding nitrogen atom among the orbital coefficients of the HOMO of the target molecule. The method for calculating the orbital coefficients of the target atom in the highest occupied molecular orbital is shown below. The i-th molecular orbital Ψ i is expanded as follows:

number

[0029] The orbital coefficient of the nitrogen atom in the HOMO is C HOMO,N Then, C HOMO,Ncan be calculated using the following formula:

number

[0030] From the viewpoint of obtaining the effects of the present invention, the diamine (c) is preferably a compound represented by any one of the following formulas (d-1) to (d-8): The orbital coefficients of each compound are d-1 (0.0023), d-3 (0.0018), d-4 (0.0016), d-5 (0.0009), d-6 (0.0013), d-7 (0.0018), and d-8 (0.0007). [ka]

[0031] <Diamine component> When the polymer (A) is a polyimide precursor (hereinafter also referred to as polyimide precursor (A)), the polymer (A) can be obtained by a polymerization reaction between a diamine component containing the diamine (c) and a tetracarboxylic acid derivative component. Among these, the polymer (A) is preferably a polyimide precursor obtainable by a polymerization reaction of a diamine component and a tetracarboxylic acid derivative component, the polyimide precursor containing at least one compound selected from the group consisting of: a compound in which, when n is 1 in the formula (d1-1), R in the formula (d1-1) represents a monovalent organic group represented by the formula (r2); a compound in which, when n is 2 or 3, the n R in the formula (d1-1) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a monovalent organic group represented by the formula (r2) and at least one of the n R represents a monovalent organic group represented by the formula (r2); and a compound in which, when n is 2 or 3, R in the formula (d1-2) to (d1-3) is a monovalent organic group represented by the formula (r2). To achieve high transparency while increasing the relaxation rate of accumulated charges, it is preferable that the orbital coefficient of the nitrogen atom of the carbazole skeleton of the above formula (r2) in the highest occupied molecular orbital is less than 0.01. More preferable is a polyimide precursor obtainable by a polymerization reaction between a diamine component containing at least one compound selected from the group consisting of compounds represented by any one of the above formulae (d-1) to (d-8) and a tetracarboxylic acid derivative component. In any of the above cases, the amount of diamine (c) used is preferably 1 to 100 mol %, more preferably 1 to 99 mol %, and even more preferably 5 to 95 mol %, based on the diamine component reacted with the tetracarboxylic acid derivative component.

[0032] The diamine component used in the production of the polyimide precursor (A) may contain diamines other than the diamine (c) (hereinafter also referred to as other diamines). Examples of other diamines are listed below, but the present invention is not limited to these.

[0033] 4,4'-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone, 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl 3,5-diaminobenzoate, 1,4-bis(4-aminobenzyl)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene; diamines having a photoalignment group such as diamines represented by the following formulas (g-1) to (g-9); diamines having a urea bond such as diamines represented by the following formulas (u-1) to (u-3); diamines having an amide bond such as diamines represented by the following formulas (u-4) to (u-6) Diamines: 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, diamines represented by the following formulae (Dp-1) to (Dp-8), diamines represented by the following formulae (z-1) to (z-8), Diamines represented by formula (z-28); 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; diamines having a carboxy group such as 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and diamine compounds represented by the following formulas (3b-1) to (3b-4); 4-(2-(methylamino)ethoxy)-2-methyl-2-propanol; diamines having a photopolymerizable group at the end, such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallylaniline;Diamines having a radical initiating function such as those represented by the following formulae (Ra-1) to (Ra-5), diamines having a photosensitizing function that exhibits a sensitizing effect upon irradiation with light such as 9,9-bis(4-aminophenyl)fluorene; diamines having a steroid skeleton such as cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestanyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane; diamines represented by the following formulae (V-1) to (V-6), diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; diamines having an oxazoline ring structure such as those of the following formulae (Ox-1) to (Ox-2), diamines having the group "-N(D)-" (D represents a protecting group that is eliminated by heating and replaced with a hydrogen atom, preferably a tert-butoxycarbonyl group) represented by the following formulae (5-1) to (5-10), diamines represented by the following formula (2) or formula (2i), and diamines having two amino groups bonded to a group represented by any of formulae (Y-1) to (Y-167) described in WO2018 / 117239;

[0034] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, Py represents a pyridine ring or a pyrimidine ring.) [ka] (n is an integer from 1 to 6.) [ka] (In (3b-1) above, A 1 represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -C2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-; m1 and m2 each independently represent an integer of 0 to 4, and m1 + m2 represents an integer of 1 to 4. In formula (3b-2), m3 and m4 each independently represent an integer of 1 to 5. In formula (3b-3), A 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 represents an integer of 1 to 5. In formula (3b-4), A 3 and A 4 each independently represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -C2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-, and m6 represents an integer of 1 to 4.

[0035] [ka] (In the above formulas (V-1) to (V-6), X v1 ~X v4 , and X p1 ~X p2 are each independently -(CH2) a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CHO-, -CHOCO-, -COO-, or -OCO-; X v5 represents -O-, -CHO-, -CHOCO-, -COO-, or -OCO-. a represents a single bond, -O-, -NH-, -O-(CH2) m-O- (m represents an integer of 1 to 6), -C(CH3)2-, -CO-, -(CH2) m -, -SO2-, -OC(CH3)2-, -CO-(CH2) m - (m represents an integer of 1 to 6), -NH-(CH2) m - (m represents an integer of 1 to 6), -SO2-(CH2) m -(m represents an integer of 1 to 6), -CONH-(CH2) m -(m represents an integer of 1 to 6), -CONH-(CH2) m -NHCO- (m represents an integer of 1 to 6), -COO-(CH2) m -OCO- (m represents an integer of 1 to 6), -CONH-, -NH-(CH2) m -NH- (wherein m represents an integer of 1 to 6), or -SO2-(CH2) m -SO2- (m represents an integer of 1 to 6), and R v1 ~R v4 , and R 1a ~R 1b each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms.

[0036] [ka]

[0037] [ka] (Boc represents a tert-butoxycarbonyl group.)

[0038] [ka] (Y2 represents a divalent organic group represented by the following formula (O). R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Y 2i represents a divalent organic group represented by the following formula (O'): [ka] (Ar represents a divalent benzene ring, a biphenyl structure, or a naphthalene ring. Two Ar may be the same or different, and any hydrogen atom on the benzene ring or naphthalene ring of Ar may be substituted with a monovalent substituent. p is an integer of 0 or 1. Q2 is -(CH2) n -(n is an integer of 2 to 18), or the -(CH2) n represents a group in which at least a portion of the -CH2- groups in - is replaced with either -O-, -C(=O)-, or -OC(=O)-. * represents a bond. [ka] (Ar' represents a divalent benzene ring or a biphenyl structure. Two Ar's may be the same or different, and any hydrogen atom on the benzene ring of Ar' may be substituted with a monovalent substituent. p' is an integer of 0 or 1. Q 2’ Ha-(CH2) n -(n is an integer of 2 to 18), or the above -(CH2) n represents a group in which at least a portion of the -CH2- groups in - is replaced with either -O-, -C(=O)-, or -OC(=O)-. * represents a bond.

[0039] Examples of the substituent on the benzene ring or naphthalene ring in the above formulae (O) and (O') include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a carboxy group, a hydroxy group, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group, and a nitro group.

[0040] When the polymer composition is used as a liquid crystal aligning agent, the diamine represented by the above formula (2) or formula (2i) is, from the viewpoint of enhancing the liquid crystal alignment property of the liquid crystal alignment film, p-phenylenediamine, m-phenylenediamine, 4-(2-(methylamino)ethyl)aniline, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,2-bis(4-aminophenoxy)ethane, 1,2-bis(4-amino-2-methylphenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy) ) butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 4-(2-(4-aminophenoxy)ethoxy)-3-fluoroaniline, bis(2-(4-aminophenoxy)ethyl)ether, 4-amino-4'-(2-(4-aminophenoxy)ethoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, and diamines represented by any of the following formulas (nh-1) to (nh-8) are preferred. [ka]

[0041] Among the other diamines, from the viewpoint of suitably obtaining the effects of the present invention, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, diamines having a carboxy group, diamines having a urea bond, diamines having an amide bond, diamines represented by the above formulas (Dp-1) to (Dp-8), and diamines represented by the above formulas (z-1) to (z-28) are preferred.

[0042] When other diamines are used in addition to the diamine (c), the amount of the other diamines used is preferably 1 to 99 mol %, more preferably 5 to 95 mol %, based on the total diamine components used.

[0043] <Tetracarboxylic acid derivative component> When producing the polyimide precursor (A), the tetracarboxylic acid derivative component to be reacted with the diamine component may be not only a tetracarboxylic acid dianhydride but also a derivative of a tetracarboxylic acid dianhydride such as a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester, or a tetracarboxylic acid dialkyl ester dihalide.

[0044] The tetracarboxylic acid dianhydride or its derivative may be an aromatic, aliphatic, or alicyclic tetracarboxylic acid dianhydride, or a derivative thereof. The aromatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an aromatic ring. The aliphatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it is not necessary for the tetracarboxylic acid dianhydride to be composed solely of a chain hydrocarbon structure, and it may also have an alicyclic structure or an aromatic ring structure as part of it.

[0045] Alicyclic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. Furthermore, they do not necessarily have to be composed solely of an alicyclic structure, and may partially contain a chain hydrocarbon structure or an aromatic ring structure.

[0046] In the present invention, from the viewpoints of achieving high transmittance and accelerating the relaxation of accumulated charges, the tetracarboxylic acid derivative component is preferably an aliphatic or alicyclic tetracarboxylic acid dianhydride or a derivative thereof. Among these, a tetracarboxylic acid dianhydride having at least one partial structure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, or a derivative thereof, is more preferred. The amount used is preferably 1 mol % or more, more preferably 5 mol % or more, and even more preferably 10 mol % or more, based on 1 mol of the total tetracarboxylic acid derivative components used. When the tetracarboxylic acid derivative contains a tetracarboxylic acid dianhydride other than an aliphatic or alicyclic tetracarboxylic acid dianhydride or a derivative thereof, or a derivative thereof, the upper limit is preferably 95 mol % or less, more preferably 90 mol % or less.

[0047] Among these, the tetracarboxylic dianhydride or derivative thereof is preferably one represented by the following formula (T). [ka] In the formula (T), X represents a structure selected from the group consisting of the following (x-1) to (x-13):

[0048] [ka]

[0049] In the above formulas (x-1) to (x-13), R 1 ~R 4 R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group. 5 and R 6each independently represents a hydrogen atom or a methyl group. j and k are integers of 0 or 1, and A1 and A2 each independently represent a single bond, an ether (-O-), a carbonyl (-CO-), an ester (-COO-), a phenylene group, a sulfonyl group (-SO2-), or an amide group (-CONH-). *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group. In formula (x-13), the two A2 may be the same or different.

[0050] More preferred examples of the formula (x-1) include the following formulae (X1-1) to (X1-6): In the formulae, * represents a bond. [ka]

[0051] Preferred specific examples of the above formulae (x-12) and (x-13) include the following formulae (x-14) to (x-29), where * represents a bond. [ka]

[0052] [ka]

[0053] In the tetracarboxylic dianhydride or derivative thereof represented by the formula (T), X is preferably selected from (x-1) to (x-11), more preferably from (x-1) to (x-7), from the viewpoint of obtaining high transmittance and accelerating the relaxation characteristic of accumulated charges. Also, from the viewpoint of accelerating the relaxation characteristic of accumulated charges, X is preferably selected from (x-11) to (x-13).

[0054] The proportion of the tetracarboxylic dianhydride represented by the above formula (T) or a derivative thereof used is preferably 1 mol % or more, more preferably 5 mol % or more, and even more preferably 10 mol % or more, relative to 1 mol of the total tetracarboxylic acid derivative components used. The tetracarboxylic dianhydride and its derivatives used in the production of the polyimide precursor (A) may contain a tetracarboxylic dianhydride or its derivative other than that of the above formula (T).

[0055] The polyamic acid, which is a polyimide precursor, is produced by, for example, reacting the diamine component with a tetracarboxylic dianhydride in a solvent (condensation polymerization). The solvent is not particularly limited as long as it dissolves the produced polymer. Specific examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. When the polymer has high solubility in the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or solvents represented by the following formulas [D-1] to [D-3] can be used.

[0056] [ka] (In formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D 3 represents an alkyl group having 1 to 4 carbon atoms.

[0057] These solvents may be used alone or in combination. Furthermore, even if a solvent does not dissolve the polymer, it may be mixed with the above-mentioned solvent to the extent that the produced polymer does not precipitate. When the diamine component and the tetracarboxylic dianhydride are reacted in a solvent, the reaction can be carried out at any concentration, preferably 1 to 50 mass %, more preferably 5 to 30 mass %. The reaction can be carried out at a high concentration in the early stage, and then additional solvent can be added. In the reaction, the ratio of the total number of moles of the diamine components to the total number of moles of the tetracarboxylic dianhydride is preferably 0.8 to 1.2. As in a typical polycondensation reaction, the closer this molar ratio is to 1.0, the higher the molecular weight of the polymer produced will be.

[0058] The polyamic acid ester, which is a polyimide precursor, can be obtained by known methods such as [I] a method of reacting the polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, or [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine.

[0059] [Polyimide] The polyimide used in the polymer composition of the present invention is a polyimide obtained by ring-closing the polyimide precursor (A). In the polyimide, the ring-closure rate of amic acid groups (the ratio of ring-closed repeating units to all repeating units in the polyimide precursor, also called the imidization rate) does not necessarily need to be 100% and can be adjusted as desired depending on the application or purpose.

[0060] Methods for obtaining polyimide by imidizing a polyimide precursor include thermal imidization, in which a solution of the polyimide precursor is heated as is, and catalytic imidization, in which a catalyst is added to a solution of the polyimide precursor. When thermally imidizing a polyimide precursor in a solution, the temperature is usually 100 to 400°C, preferably 120 to 250°C, and it is preferable to carry out the thermal imidization while removing water generated by the imidization reaction from the system.

[0061] Catalytic imidization of polyimide precursors can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring the mixture at temperatures typically between -20°C and 250°C, preferably between 0°C and 180°C. The amount of the basic catalyst is typically 0.5 to 30 times, and preferably 2 to 20 times, the molar ratio of the amic acid groups, and the amount of the acid anhydride is typically 1 to 50 times, and preferably 3 to 30 times, the molar ratio of the amic acid groups. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, pyridine is preferred because it has adequate basicity for promoting the reaction. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, acetic anhydride is preferred because it facilitates purification after the reaction. The imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0062] To recover the polyimide produced from the reaction solution of the imidization of a polyimide precursor, the reaction solution may be precipitated by pouring the reaction solution into a solvent. Examples of solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by pouring into the solvent can be recovered by filtration and then dried at room temperature or by heating under atmospheric or reduced pressure. Furthermore, the polymer precipitated and recovered can be redissolved in a solvent and reprecipitated and recovered 2 to 10 times to reduce the amount of impurities in the polymer. Examples of solvents used in this process include alcohols and hydrocarbon ketones. Using three or more solvents selected from these solvents is preferred because it further increases the efficiency of purification.

[0063] The polyimide precursor (A) and its imide compound polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa·s, and more preferably 15 to 500 mPa·s, when made into a 10% by mass solution. The solution viscosity (mPa·s) of the polyimide precursor (A) and its imide compound polyimide 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 these polymers (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0064] <End-capping agent> In the production of the polymer (A) of the present invention, an appropriate terminal-capping agent may be used together with the tetracarboxylic acid derivative component and the diamine component to form a terminal-capping polymer, which has the effect of improving the film hardness of the resulting resin film and improving the adhesion between the sealant and the resin film. Examples of the terminal of the polymer (A) in the present invention include an amino group, a carboxy group, an acid anhydride group, or a derivative thereof. The amino group, carboxy group, acid anhydride group, or a derivative thereof can be obtained by a conventional condensation reaction or by using the following terminal-capping agents. The derivatives can be obtained, for example, by using the following terminal-capping agents.

[0065] Examples of the end-capping agent include acid anhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, compounds represented by any of the following formulae (m-1) to (m-6), 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, and 4-ethynylphthalic anhydride;

[0066] [ka]

[0067] Examples of the alkyl esters include dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride and nicotinic acid chloride; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine and n-octylamine; and monoisocyanate compounds such as ethyl isocyanate, phenyl isocyanate and naphthyl isocyanate.

[0068] The proportion of the end-capping agent used is preferably 0.01 to 20 parts by mole, and more preferably 0.01 to 10 parts by mole, per 100 parts by mole of the total of the diamine components used.

[0069] The polymer composition of the present invention may contain a polymer other than the polymer (A). Specific examples of the other polymer include a polyimide precursor obtained using a tetracarboxylic acid derivative component and a diamine component not containing the diamine (c), polyimide, polysiloxane, polyester, polyamide obtained using a diamine component not containing the diamine (c), polyurea obtained using a diamine component not containing the diamine (c), polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, and a polymer selected from the group consisting of poly(meth)acrylate. Specific examples of the polyimide precursor include polyamic acid and polyamic acid ester. The other polymer may be used alone or in combination of two or more. The content of the other polymer is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and even more preferably 20 to 80 parts by mass, per 100 parts by mass of the total polymers contained in the polymer composition.

[0070] The polymer composition according to the present invention is preferably a liquid composition in which the polymer (A) is dissolved or dispersed in an organic solvent. Specifically, the organic solvent contained in the polymer composition is not particularly limited as long as it can uniformly dissolve the polymer components, but examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethyl Examples of suitable solvents include propanamide, 3-butoxy-N,N-dimethylpropanamide, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone (collectively referred to as "good solvents"). Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99 mass %, more preferably 20 to 90 mass %, and particularly preferably 30 to 80 mass %, of the total solvent contained in the polymer composition.

[0071] Furthermore, the organic solvent contained in the polymer composition is preferably a mixed solvent containing, in addition to the above solvent, a solvent (also referred to as a poor solvent) that improves the coatability when coating the polymer composition and the surface smoothness of the coating film. Specific examples of the poor solvent to be used in combination are listed below, but are not limited to these. The content of the poor solvent is preferably 1 to 80 mass %, more preferably 10 to 80 mass %, and particularly preferably 20 to 70 mass %, of the total solvent contained in the polymer composition. The type and content of the poor solvent are appropriately selected depending on the coater, coating conditions, coating environment, etc. of the liquid crystal aligning agent.

[0072] For example, diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propyl propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), etc.

[0073] Of these, diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferred.

[0074] Preferred solvent combinations of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone and propylene glycol diacetate, and N,N-di Methyl lactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate, N-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether, N,N-dimethyl lactamide and ethylene glycol monobutyl ether, N,N-dimethyl lactamide and propylene glycol diacetate, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether, N,N-dimethyl lactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and diisopropyl ether butyl ketone, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and diisobutyl ketone, γ-butyrolactone, and 4-hydroxy-4-methyl-2-pentanone Tanone and propylene glycol diacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl carbinol, N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and propylene glycol diacetate, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and diisobutyl ketone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and diisobutyl ketone, N-ethyl-2-pyrrolidone and N,Examples include N-dimethyl lactamide and diisobutyl ketone.

[0075] The polymer composition of the present invention may additionally contain components other than the polymer component and the organic solvent (hereinafter also referred to as additive components). Examples of such additive components include at least one compound selected from the group consisting of crosslinkable compounds having at least one substituent selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group, and an alkoxy group, and crosslinkable compounds having a polymerizable unsaturated group, a functional silane compound, a metal chelate compound, a curing accelerator, a surfactant, an antioxidant, a sensitizer, a preservative, and a compound for adjusting the dielectric constant or electrical resistance of the resin film.

[0076] Preferred specific examples of the crosslinkable compound include compounds represented by any of the following formulas (CL-1) to (CL-11). [ka]

[0077] Examples of the compound for adjusting the dielectric constant and electrical resistance of the resin film include monoamines having a nitrogen-containing aromatic heterocycle, such as 3-picolylamine. When using a monoamine having a nitrogen-containing aromatic heterocycle, the amount is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the polymer composition.

[0078] Preferred specific examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Examples of functional silane compounds include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane. When a functional silane compound is used, the amount used is preferably 0.1 to 30 parts by mass, and more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the polymer composition.

[0079] The solids concentration in the polymer composition (the proportion of the total mass of the components other than the solvent in the polymer composition to the total mass of the polymer composition) is appropriately selected taking into consideration viscosity, volatility, etc., but is preferably in the range of 1 to 10 mass %. That is, the polymer composition is applied to the surface of a substrate as described below, and is preferably heated to form a resin film.

[0080] The particularly preferred range of solid content varies depending on the method used to apply the polymer composition to a substrate. For example, when using a spin coating method, a solid content of 1.5 to 4.5 mass% is particularly preferred. When using a printing method, a solid content of 3 to 9 mass% is particularly preferred, thereby resulting in a solution viscosity of 12 to 50 mPa·s. When using an inkjet method, a solid content of 1 to 5 mass% is particularly preferred, thereby resulting in a solution viscosity of 3 to 15 mPa·s. The temperature during preparation of the polymer composition is preferably 10 to 50°C, more preferably 20 to 30°C.

[0081] <Applications and resin films> The polymer composition described above can be applied to a substrate, for example, and the solvent component can be volatilized, preferably by heat treatment, to form a resin film. The polymer composition and resin film according to the present invention can be effectively applied to a variety of technical applications, such as alignment film materials, electronic circuit materials, semiconductor materials, electrical insulating materials, wire coating materials, lighting applications, and molding materials. Specific examples include various resin films used in display elements, semiconductor elements, actuators such as motors, and various sensors such as piezoelectric sensors and pyroelectric sensors, including liquid crystal alignment films, protective films, spacer films, interlayer insulating films, antireflection films, wiring coating films, antistatic films, and motor insulating films. Among these, the polymer composition according to the present invention can be preferably used as a liquid crystal alignment agent.

[0082] <Liquid crystal alignment agent> The liquid crystal aligning agent according to the present invention contains the polymer (A). It is preferable that the liquid crystal aligning agent further contains at least one of other polymers, organic solvents, and additive components. The details of the polymer (A), other polymers, organic solvents, and additive components, such as specific examples, blending ratios, and solids concentrations, can be applied to the description of the polymer composition.

[0083] [Liquid crystal alignment film and liquid crystal display element] By using the polymer composition or the liquid crystal aligning agent, a liquid crystal alignment film can be produced as a resin film. Furthermore, a liquid crystal display element according to the present invention includes a liquid crystal alignment film formed using the polymer composition or the liquid crystal aligning agent. The operation mode of the liquid crystal display element according to the present invention is not particularly limited, and it can be applied to various operation modes, such as TN type, STN (Super Twisted Nematic) type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type (IPS type), FFS type, and optically compensated bend type (OCB type).

[0084] The liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (4), a method including steps (1) to (2) and (4), a method including steps (1) to (3), (4-2) and (4-4), or a method including steps (1) to (3), (4-3) and (4-4).

[0085] <Step (1): Step of applying a liquid crystal alignment agent onto a substrate> Step (1) is a step of applying the liquid crystal aligning agent of the present invention onto a substrate. Specific examples of step (1) are as follows. The liquid crystal aligning agent of the present invention is applied to one side of a substrate having a patterned transparent conductive film by an appropriate application method, such as a roll coater method, a spin coat method, a printing method, or an inkjet method. The substrate is not particularly limited as long as it is highly transparent; glass substrates, silicon nitride substrates, and plastic substrates such as acrylic substrates and polycarbonate substrates can also be used. In addition, in reflective liquid crystal display devices, an opaque material such as a silicon wafer can be used for only one substrate, and in this case, a light-reflecting material such as aluminum can also be used for the electrode. Furthermore, when manufacturing IPS or FFS liquid crystal display devices, a substrate having an electrode made of a comb-shaped patterned transparent conductive film or metal film and an opposing substrate having no electrode are used.

[0086] Examples of a method for applying the liquid crystal alignment agent to a substrate and forming a film include screen printing, offset printing, flexographic printing, an inkjet method, and a spray method. Among these, the application and film formation method by the inkjet method is preferably used.

[0087] <Step (2): Step of baking the applied liquid crystal alignment agent> In step (2), the liquid crystal alignment agent applied to the substrate is baked to form a film. Specific examples of step (2) are as follows. After applying the liquid crystal aligning agent to the substrate in step (1), the solvent can be evaporated or the polyamic acid or polyamic acid ester can be thermally imidized using a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven. The drying and baking steps after applying the liquid crystal aligning agent of the present invention can be performed at any temperature and for any time, and may be performed multiple times. The temperature for reducing the solvent in the liquid crystal aligning agent can be, for example, 40 to 180°C. To shorten the process, the baking can be performed at 40 to 150°C. The baking time is not particularly limited, but may be 1 to 10 minutes or 1 to 5 minutes. When thermally imidizing the polyamic acid or polyamic acid ester, a baking step at a temperature range of, for example, 150 to 300°C or 150 to 250°C may be added after the above steps. The baking time is not particularly limited, but may be 5 to 40 minutes or 5 to 30 minutes. If the film-like material after firing is too thin, the reliability of the liquid crystal display element may decrease, so the thickness is preferably 5 to 300 nm, more preferably 10 to 200 nm.

[0088] <Step (3): Step of subjecting the film obtained in step (2) to alignment treatment> Step (3) is a step of optionally performing an alignment treatment on the film obtained in step (2). That is, in horizontal alignment type liquid crystal display devices such as IPS mode or FFS mode, the coating film is subjected to an alignment ability imparting treatment. On the other hand, in vertical alignment type liquid crystal display devices such as VA mode or PSA mode, the formed coating film can be used as a liquid crystal alignment film as is, or the coating film may be subjected to an alignment ability imparting treatment. Alignment treatment methods for liquid crystal alignment films include rubbing treatment and photo-alignment treatment. Photo-alignment treatment methods include a method in which the surface of the film-like material is irradiated with radiation polarized in a certain direction and, optionally, subjected to heat treatment at a temperature preferably of 150 to 250°C to impart liquid crystal alignment properties (also referred to as liquid crystal alignment ability). As the radiation, ultraviolet light or visible light having a wavelength of 100 to 800 nm can be used. Among these, ultraviolet light having a wavelength of 100 to 400 nm is preferred, and more preferably 200 to 400 nm is more preferred.

[0089] The radiation dose is 1 to 10,000 mJ / cm 2 Among these, 100 to 5,000 mJ / cm is preferable. 2 In addition, when irradiating with radiation, the substrate having the film-like material may be irradiated while being heated at 50 to 250° C. in order to improve the liquid crystal alignment. The liquid crystal alignment film prepared in this manner can stably align liquid crystal molecules in a certain direction. Furthermore, the liquid crystal alignment film irradiated with polarized radiation by the above method can be contact-treated with water or a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.

[0090] The solvent used in the contact treatment is not particularly limited as long as it dissolves the decomposition products generated from the film-like material by irradiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. Among these, water, 2-propanol, 1-methoxy-2-propanol, and ethyl lactate are preferred, with water, 1-methoxy-2-propanol, and ethyl lactate being more preferred, from the standpoint of versatility and solvent safety. The solvent may be used alone or in combination of two or more.

[0091] The temperature for the heat treatment of the coating film irradiated with the radiation is more preferably 50 to 300° C., and even more preferably 120 to 250° C. The heat treatment time is preferably 1 to 30 minutes.

[0092] <Step (4): Step of Producing a Liquid Crystal Cell> Two substrates on which the liquid crystal alignment film is formed are prepared as described above, and liquid crystal is placed between the two substrates arranged opposite each other. Specifically, there are two methods as follows. In the first method, two substrates are placed opposite each other with a gap (cell gap) between them so that their liquid crystal alignment films face each other. Next, the two substrates are bonded together around their peripheries using a sealant. A liquid crystal composition is injected into the substrate surfaces and the cell gap defined by the sealant so that it comes into contact with the film surface, and then the injection hole is sealed.

[0093] The second method is called the ODF (One Drop Fill) method. A UV-curable sealant, for example, is applied to a predetermined location on one of two substrates on which a liquid crystal alignment film has been formed, and a liquid crystal composition is then dropped onto several predetermined locations on the liquid crystal alignment film. The other substrate is then attached so that the liquid crystal alignment film faces the other substrate, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with UV light to cure the sealant. In either method, it is desirable to further heat the substrate to a temperature at which the liquid crystal composition is in an isotropic phase, and then slowly cool it to room temperature to remove flow alignment that occurs during liquid crystal filling. When the coating films are subjected to a rubbing treatment, the two substrates are placed opposite each other so that the rubbing directions of the coating films are at a predetermined angle, for example, perpendicular or anti-parallel to each other. The sealing agent may be, for example, an epoxy resin containing a hardener and aluminum oxide spheres as spacers. The liquid crystal may be a nematic liquid crystal or a smectic liquid crystal, with a nematic liquid crystal being preferred.

[0094] The liquid crystal aligning agent of the present invention is also preferably used for a liquid crystal display element (PSA type liquid crystal display element) which has a liquid crystal layer between a pair of substrates provided with electrodes, and is produced through a process of disposing a liquid crystal composition containing a polymerizable compound which is polymerized by at least one of active energy rays and heat between the pair of substrates, and polymerizing the polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between the electrodes. The liquid crystal aligning agent of the present invention is also preferably used for a liquid crystal display element (SC-PVA mode liquid crystal display element) which has a liquid crystal layer between a pair of substrates equipped with electrodes, and is manufactured by disposing a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates, and applying a voltage between the electrodes.

[0095] (4-2) PSA type LCD element The procedure is the same as in (4) above, except that a liquid crystal composition containing a polymerizable compound is injected or dropped. Examples of the polymerizable compound include polymerizable compounds represented by the following formulas (M-1) to (M-7).

[0096] [ka]

[0097] (4-3) SC-PVA mode LCD element A method for producing a liquid crystal display element may be employed in which a process similar to that described in (4) above is followed by a step of irradiating with ultraviolet light, which will be described later. This method, similar to the production of the PSA-type liquid crystal display element, allows for the production of a liquid crystal display element with excellent response speed with a small amount of light irradiation. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups, such as acrylate or methacrylate groups, in the molecule, as represented by the above formulas (M-1) to (M-7). The content of the compound is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of all polymer components. The polymerizable group may also be contained in a polymer used in a liquid crystal aligning agent. Examples of such polymers include polymers obtained by reacting a diamine component containing a diamine having the above photopolymerizable group at its terminal.

[0098] Step (4-4): Step of irradiating with ultraviolet light The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (4-2) or (4-3) above. The voltage applied here can be, for example, 5 to 50 V DC or AC. The light to be irradiated can be, for example, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferred. The light source for the irradiation light can be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or an excimer laser. The light irradiation dose is preferably 1,000 to 200,000 J / m 2and more preferably 1,000 to 100,000 J / m 2 is.

[0099] A liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell as needed. Examples of the polarizing plate to be attached to the outer surface of the liquid crystal cell 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.

[0100] FIG. 1 is a schematic cross-sectional view showing an example of the liquid crystal display element of the present invention, which is an example of an IPS mode liquid crystal display element. In the IPS LCD element 1 illustrated in FIG. 1, liquid crystal 3 is sandwiched between a comb-shaped electrode substrate 2 having a liquid crystal alignment film 2c and a counter substrate 4 having a liquid crystal alignment film 4a. The comb-shaped electrode substrate 2 has a base material 2a, a plurality of linear electrodes 2b formed on the base material 2a and arranged in a comb-like pattern, and a liquid crystal alignment film 2c formed on the base material 2a so as to cover the linear electrodes 2b. The counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2c is, for example, a liquid crystal alignment film of the present invention. The liquid crystal alignment film 4c is also a liquid crystal alignment film of the present invention. In this IPS LCD element 1, when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as indicated by electric force lines L.

[0101] FIG. 2 is a schematic cross-sectional view showing another example of the liquid crystal display element of the present invention, which is an example of an FFS mode liquid crystal display element. In the IPS LCD element 1 shown in FIG. 2, liquid crystal 3 is sandwiched between a comb-shaped electrode substrate 2 having a liquid crystal alignment film 2h and a counter substrate 4 having a liquid crystal alignment film 4a. The comb-shaped electrode substrate 2 has a base 2d, a surface electrode 2e formed on the base 2d, an insulating film 2f formed on the surface electrode 2e, a plurality of linear electrodes 2g formed on the insulating film 2f and arranged in a comb-like pattern, and a liquid crystal alignment film 2h formed on the insulating film 2f so as to cover the linear electrodes 2g. The counter substrate 4 has a base 4b and a liquid crystal alignment film 4a formed on the base 4b. The liquid crystal alignment film 2h is, for example, a liquid crystal alignment film of the present invention. The liquid crystal alignment film 4a is also a liquid crystal alignment film of the present invention. In this IPS LCD element 1, when a voltage is applied to the surface electrodes 2e and the linear electrodes 2g, an electric field is generated between the surface electrodes 2e and the linear electrodes 2g as indicated by electric force lines L.

[0102] The liquid crystal display element of the present invention can be effectively applied to various devices, and can be used in various display devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, information displays, etc. In addition, the polymer composition contained in the liquid crystal aligning agent can be used as a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmissive / scattering liquid crystal dimming element, or for other applications such as a protective film for a color filter, a gate insulating film for a flexible display, or a substrate material. [Example]

[0103] The present invention will be described in more detail below with reference to examples, but is not limited to these examples. The abbreviations for the compounds used and the methods for measuring their physical properties are as follows. In the quantum chemical calculations of diamines described below, the Mulliken charge and orbital coefficients on the nitrogen atoms indicated by arrows in the chemical structural formulas were calculated.

[0104] (diamine) The compounds corresponding to the above-mentioned diamine (c) are the following diamines (WA-1) to (WA-15), (WB-1) to (WB-3), and (WD-5). Diamines (WB-4), (WC-1) to (WC-8), and (WD-1) to (WD-4) are comparative examples. Diamines (WA-16) to (WA-17) are reference examples. WA-1 to WA-17: Compounds represented by the following formulas (WA-1) to (WA-17), respectively

[0105] [ka] [ka]

[0106] WB-1 to WB-4: Compounds represented by the following formulas (WB-1) to (WB-4), respectively

[0107] [ka]

[0108] WC-1 to WC-8: Compounds represented by the following formulas (WC-1) to (WC-8), respectively

[0109] [ka]

[0110] WD-1 to WD-5: Compounds represented by the following formulas (WD-1) to (WD-5), respectively

[0111] [ka]

[0112] (Other diamines) DA-1 to DA-2: Compounds represented by the following formulas (DA-1) to (DA-2), respectively

[0113] [ka]

[0114] (Tetracarboxylic acid dianhydride) CA-1: A compound represented by the following formula (CA-1):

[0115] [ka]

[0116] (solvent) NMP: N-methyl-2-pyrrolidone BCS: Ethylene glycol monobutyl ether

[0117] (Viscosity measurement) The viscosity of the solution was measured at 25°C using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a cone rotor TE-1 (1°34', R24).

[0118] <Evaluation of physical properties of diamines by molecular orbital calculations> The physical properties of diamines were evaluated by molecular orbital calculations. Gaussian 09 (Revision C.01, M.J. Frisch, et al., Gaussian, Inc., 2010) was used as molecular orbital calculation software to calculate the electron density distribution after structural optimization.

[0119] (1)Mulliken charge The most stable structures of diamines in the ground state under vacuum were calculated using the B3LYP functional and the 6-31G* basis set. For the diamines listed in Table 1, the Mulliken charges on the nitrogen atoms indicated by the arrows were calculated for these most stable structures. Diamines with a Mulliken charge of 0.550 or greater, while satisfying the requirement that the nitrogen atom on the side chain be conjugated with the diamine moiety in the main chain, were judged to have "efficient charge transfer from the main chain to the side chain R." Furthermore, diamines with a Mulliken charge of less than 0.550, even if the nitrogen atom on the side chain be conjugated with the diamine moiety in the main chain, were judged to have "difficult charge transfer from the main chain to the side chain R." As a result, diamines WA-1 to WA-15, WB-1 to WB-3, and WD-5, which have two or three aromatic rings directly attached to the target nitrogen atom, were judged to have efficient charge transfer from the main chain to the side chain R.

[0120] (2) Orbital coefficient Using the most stable structure obtained in (1), single-point energy calculations were performed using the B3LYP functional and 6-31G* basis set to determine the distribution of the highest occupied molecular orbital (HOMO orbital). The distribution of the HOMO on the nitrogen atoms contained in the arylamine or aromatic heterocycle on the diamine side chain can be quantified from the orbital coefficients of the corresponding nitrogen atoms. The orbital coefficient of the corresponding nitrogen atom is calculated by squaring and adding up the expansion coefficients of the corresponding nitrogen atoms among the HOMO orbital coefficients. Orbital coefficients less than 0.0025 were evaluated as "◎", those between 0.0025 and 0.005 as "〇", those between 0.005 and 0.01 as "△", and those greater than 0.01 as "×". Diamines in which the nitrogen atom in the side chain R forms a ring with the aromatic ring and forms a metharylene configuration via the nitrogen atom in the main chain and the aromatic ring are considered to have particularly excellent transparency.

[0121] [Table 1] *1): The number of aromatic hydrocarbon rings that satisfy at least one of the conditions (I) and (II). *2): Indicates whether or not the amine moiety (-NH2) in the main chain is conjugated with the nitrogen atom indicated by the arrow in the chemical structure.

[0122] Here, the orbital coefficients of the nitrogen atoms in the molecules of some of the diamines selected from those mentioned in this example are shown below. The orbital coefficients of the nitrogen atoms shown in [1] to [8] are values ​​that far exceed 0.01. [ka]

[0123] [Monomer synthesis] < 1 H-NMR Measurement Equipment: Fourier transform superconducting nuclear magnetic resonance spectrometer (FT-NMR) "AVANCE III" (BRUKER) 500MHz. Solvent: deuterated dimethyl sulfoxide ([D6]-DMSO). Standard: tetramethylsilane (TMS).

[0124] <Monomer Synthesis Example 1 (Example A)> [Synthesis of WA-3a] WA-3a was synthesized according to the route shown below. [ka]

[0125] Under a nitrogen atmosphere, 9-benzyl-2-bromo-9H-carbazole (10.8 g, 32.1 mmol), Pd2(dba)3 (Tris(dibenzylideneacetone)dipalladium(0)) (0.534 g, 0.583 mmol), and t-BuXPhos (2-Di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl) (0.991 g, 2.33 mmol) were added to bis-(4-nitrophenyl)amine (7.56 g, 29.1 mmol). Then, toluene (226 g) was added, which had been degassed by blowing nitrogen gas into it. The mixture was further degassed under reduced pressure and then re-pressurized with nitrogen gas to thoroughly remove oxygen. After that, t-BuONa(sodium After adding 4.20 g of tert-butoxide (43.7 mmol), the mixture was again degassed under reduced pressure with oxygen and then nitrogen gas pressure was restored, and the reaction was initiated under reflux temperature conditions in a nitrogen atmosphere. After 72 hours of reaction, the reaction stopped and the workup was carried out. The reaction mixture was neutralized by adding 200 g of 1N hydrochloric acid, and the resulting organic layer was then separated. The resulting organic layer was washed again with 200 g of 1N hydrochloric acid, and the organic layer was separated. 1.60 g of specially prepared Shirasagi activated carbon was added to the resulting organic layer and stirred for 30 minutes. The activated carbon was then removed by filtration, and the resulting solution was concentrated to obtain a black oil. This black oil was purified using a column of ethyl acetate:heptane = 1:6 (volume ratio) as a developing solvent. The resulting crystals were then recrystallized from toluene to obtain the target product (WA-3a) (4.87 g, 9.46 mmol, yield: 32.5%) as an orange solid.

[0126] [Synthesis of WA-3] WA-3 was synthesized according to the route shown below. [ka]

[0127] Tetrahydrofuran (THF) (100 g) was added to WA-3a (4.74 g, 9.21 mmol), and Pd-C (palladium-carbon) (NE Chemcat, 50% water content) (0.970 g) was added, and nitro reduction was carried out at room temperature under a hydrogen atmosphere. After the reaction, the Pd-C was filtered off, and the filtrate was concentrated. The crude product obtained was recrystallized from isopropyl alcohol to obtain the target product (WA-3) (3.52 g, 7.74 mmol, yield: 84.0%) as a yellow-green solid. As shown below 1 The results of H-NMR confirmed that this solid was WA-3. 1 H-NMR(500MHz,[D6]-DMSO):δ(ppm)=7.91(d,1H,J=7.7Hz),7.79(d,1H,J=8.6Hz),7.51(d,1H,J=8.2Hz),7.27-7.20 (m,4H),7.11-7.06(m,3H),6.80(d,4H,J=8.6Hz),6.76(d,1H,J=1.8Hz),6.57-6.52(m,5H),5.32(s,2H),4.95(s,4H)

[0128] <Polymer synthesis> (Comparative Synthesis Example 1) DA-1 (0.638 g, 3.20 mmol), DA-2 (0.239 g, 0.801 mmol), and NMP (10.0 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube and dissolved by stirring at room temperature. After cooling to room temperature, CA-1 (0.737 g, 3.76 mmol) and NMP (4.66 g) were added and stirred at room temperature for 4 hours to obtain a 10% polyamic acid solution (PAA-R1) (viscosity: 204.8 mPa s).

[0129] (Comparative Synthesis Example 2, Reference Synthesis Example 1, Synthesis Examples 1 and 2 (Examples B and C)) Polyamic acid solutions (PAA-R2, PAA-S1, PAA-1 to PAA-2) having the viscosities shown in Table 2 were obtained in the same manner as in Comparative Synthesis Example 1, except that the types and amounts of the diamine compound and tetracarboxylic dianhydride were changed as shown in Table 2 below.

[0130]

Table 2

[0131] <Preparation of Liquid Crystal Alignment Agent> (Example 1) To the polyamic acid solution (PAA-1) (5.00 g) obtained in Synthesis Example 1, NMP (3.00 g) and BCS (2.00 g) were added, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent (V-1). No abnormalities such as turbidity or precipitation were observed in this liquid crystal alignment agent, and it was confirmed that it was a uniform solution.

[0132] (Examples 2, Comparative Examples 1-2, Reference Example 1) The liquid crystal alignment agents V-2, VR-1-VR-2, and VS-1 shown in Table 3 were obtained by carrying out the same procedure as in Example 1 except that the polyamic acid solution was changed to PAA-2, PAA-R1-PAA-R2, or PAA-S1.

[0133]

Table 3

[0134] <Fabrication of FFS-Type Liquid Crystal Display Element> A liquid crystal cell having the structure of a fringe field switching (FFS) mode liquid crystal display element was fabricated. First, a substrate with electrodes was prepared. The substrate was a 30 mm x 35 mm, 0.7 mm thick glass substrate. A solid-patterned ITO electrode, which constituted the counter electrode, was formed on the substrate. A second layer, a silicon nitride (SiN) film deposited by chemical vapor deposition (CVD), was formed on top of the first counter electrode. The second SiN film had a thickness of 500 nm and functioned as an interlayer insulating film. A comb-shaped pixel electrode, formed by patterning an ITO film, was placed on top of the second SiN film. Two pixels, the first and second, were formed, each measuring 10 mm long and approximately 5 mm wide. The first counter electrode and the third pixel electrode were electrically insulated by the second SiN film.

[0135] The pixel electrode on the third layer had a comb-like shape with multiple 3 μm-wide electrode elements bent at an internal angle of 160° in the center and arranged parallel to each other with 6 μm gaps between them. Each pixel had a first region and a second region, separated by a line connecting the bent portions of the multiple electrode elements.

[0136] Comparing the first and second regions of each pixel, the electrode elements of the pixel electrodes constituting them were formed in different directions. That is, based on the rubbing direction of the liquid crystal alignment film described below, the electrode elements of the pixel electrodes in the first region of the pixel were formed to form a 10° clockwise angle, while the electrode elements of the pixel electrodes in the second region of the pixel were formed to form a 10° counterclockwise angle. That is, the first and second regions of each pixel were configured such that the directions of rotational movement (in-plane switching) of the liquid crystal within the substrate plane induced by application of a voltage between the pixel electrode and the counter electrode were opposite to each other.

[0137] Next, the liquid crystal alignment agent obtained in Example 1 was filtered through a 1.0 μm pore size filter and then spin-coated onto the prepared electrode-attached substrate and a glass substrate with 4 μm-high columnar spacers and an ITO film formed on the backside. After drying for 2 minutes on a hot plate at 80°C, it was baked for 20 minutes in a hot air circulating oven at 230°C to obtain a 100 nm-thick polyimide film. This polyimide film was rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 1000 rpm, movement speed: 20 mm / sec, indentation length: 0.4 mm, rubbing direction: tilted 10° relative to the third layer ITO comb electrode), then ultrasonically washed in pure water for 1 minute, and water droplets were removed by air blowing. The substrate was then dried for 15 minutes at 80°C to obtain a substrate with a liquid crystal alignment film. These two substrates with liquid crystal alignment films were combined into a pair. A sealant was printed on one substrate, leaving a liquid crystal injection port. Another substrate was then attached, with the liquid crystal alignment film facing each other and the rubbing directions antiparallel. The sealant was then cured to create an empty cell with a cell gap of 4 μm. Positive liquid crystal MLC-3019 (Merck) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain an FFS-mode liquid crystal cell. The resulting liquid crystal cell was then heated at 120°C for 1 hour and left overnight at 23°C before being used to evaluate the liquid crystal alignment properties.

[0138] <Measurement of the relaxation rate of accumulated charges> The liquid crystal cell prepared above was placed between two polarizers arranged so that their polarization axes were perpendicular to each other, and with the pixel electrode and the counter electrode shorted to give them the same potential, an LED backlight was irradiated from below the two polarizers, and the angle of the liquid crystal cell was adjusted so that the brightness of the LED backlight transmitted through the two polarizers was minimized. This evaluation was performed under a temperature condition where the liquid crystal cell temperature was 23°C. Next, a VT curve (voltage-transmittance curve) was measured while applying an AC voltage of 30 Hz to the liquid crystal cell, and the AC voltage at which the relative transmittance became 23% was calculated as the driving voltage. Next, a square wave of 20 mV at 1 kHz was applied to the liquid crystal cell at 23°C for 10 minutes. Next, an AC voltage with a frequency of 30 Hz and a square wave that gave a relative transmittance of 23% was applied for 5 minutes, and then a DC voltage of +1.0 V was superimposed and the film was driven for 30 minutes. After that, the DC voltage was turned off, and an AC voltage with a frequency of 30 Hz and a square wave that gave a relative transmittance of 23% was applied again for 30 minutes. The faster the charge relaxation, the faster the charge accumulation in the liquid crystal cell when a DC voltage is applied. Therefore, the relaxation characteristics of the accumulated charge were evaluated by the time required for the relative transmittance to decrease from over 30% immediately after DC voltage application to 30%. The shorter this time, the better the charge relaxation characteristics. Specifically, the time it took for the relative transmittance to decrease to 30% or less within 30 minutes after DC voltage application was quantified. A sample that decreased to 30% or less within 4 minutes was evaluated as "◎." A sample that decreased to 30% or less within 8 minutes was evaluated as "○." A sample that decreased to 30% or less within 8 minutes was evaluated as "△." A sample that did not decrease to 30% or less within 30 minutes was evaluated as "×."

[0139] <Evaluation of optical properties (transparency of liquid crystal alignment film)> A quartz substrate measuring 40 mm x 40 mm and 1.0 mm thick was prepared. Next, the liquid crystal alignment agent was filtered through a filter with a pore size of 1.0 μm and then spin-coated onto the quartz substrate. Next, the substrate was dried on a hot plate at 80°C for 2 minutes and then baked at 230°C for 20 minutes, obtaining a polyimide film with a thickness of 100 nm on each substrate. Transparency was evaluated by measuring the transmittance of the substrate obtained by the above method. Specifically, the transmittance was measured using a UV-3600 (Shimadzu Corporation) measuring device at a temperature of 25°C and a scanning wavelength of 300 to 800 nm. An uncoated quartz substrate was used as a reference (reference example). The average transmittance in the wavelength range of 400 to 800 nm was calculated, and the higher the transmittance, the better the transparency.

[0140] The liquid crystal display elements using the liquid crystal alignment agents of Examples 1 and 2, Comparative Examples 1 and 2, and Reference Example 1 were evaluated as described above for the relaxation characteristics of accumulated charges and the optical characteristics, and the results are shown in Table 4 below.

[0141] [Table 4]

[0142] As can be seen from the above results, the liquid crystal alignment film obtained from the liquid crystal alignment agent using the diamine (c) having a specific aromatic amine structure exhibits transparency equal to or higher than that obtained from the liquid crystal alignment agent not using the diamine having a specific aromatic amine structure, and has a faster relaxation rate of accumulated charges. Specifically, this is shown in the comparison between Example 1 and Example 2 and Comparative Example 1 shown in Table 4. Note that a difference of 0.5% in transmittance is a significant difference in the technical field. Furthermore, a comparison between Comparative Example 2 and Comparative Example 1 revealed that the liquid crystal alignment film obtained from the liquid crystal alignment agent using a diamine that does not have a specific aromatic amine structure had improved transparency but a worsening rate of relaxation of accumulated charges. Comparison between Reference Example 1 and Comparative Example 1 shows that the liquid crystal alignment film obtained from the liquid crystal alignment agent using diamine WB-4 had a faster relaxation rate of accumulated charges but a worsening transparency. Comparing Reference Example 1, which uses a diamine in which the orbital coefficient of the nitrogen atom to be calculated is 0.01 or more, with Examples 1 and 2, which uses a diamine (c) in which the orbital coefficient of the nitrogen atom to be calculated is less than 0.01 and has a specific aromatic amine structure, the liquid crystal alignment films of Examples 1 and 2 had superior transparency to the liquid crystal alignment film of Reference Example 1. [Industrial Applicability]

[0143] By using the polymer composition of the present invention as a liquid crystal aligning agent, a liquid crystal display device can be obtained in which the relaxation rate of accumulated charges is fast and there is little image retention, and therefore the polymer composition is expected to be used in liquid crystal display devices that require high display quality.

Claims

1. A compound represented by any one of the following formulas (d1-1) to (d1-3): 【Chemistry 1】 In formula (d1-1), when n is 1, R is a monovalent organic group represented by the following formula (r2); when n is 2 or 3, n R each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a monovalent organic group represented by the following formula (r2); and at least one of the n R represents a monovalent organic group represented by the following formula (r2). In formulas (d1-2) and (d1-3), R is a monovalent organic group represented by the following formula (r2): ２ , and L ３ represents a single bond, —NR′—, —O—, —NR′—CO—, —CO—NR′—, —O—CO—, or —CO—O—, and R′ represents a hydrogen atom or a monovalent organic group. ２ , and Ar ３ represents an aromatic ring group, wherein a hydrogen atom on the aromatic ring may be replaced by a hydroxy group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. In formula (d1-1), when n is 2 or 3, the n m2's may be the same or different. In formula (d1-2), Ar ２ If there are two or more, there are two or more Ar ２ may be the same or different. In formula (d1-2), L ２ If there are two or more, there are two or more L ２ may be the same or different. In formula (d1-3), two or more Ar ３ may be the same or different. In formula (d1-3), two or more L ３ may be the same or different.) 【Chemistry 2】 (R ２ represents a hydrogen atom or a monovalent organic group. However, the orbital coefficient of the nitrogen atom in the carbazole skeleton of formula (r2) in the highest occupied molecular orbital is less than 0.

01. * represents a bond.

2. A compound represented by any one of the following formulas (d-1) to (d-8): 【Transformation 3】

3. A polyimide precursor obtainable by a polymerization reaction between a diamine component containing at least one compound selected from the group consisting of compounds represented by any one of formulas (d1-1) to (d1-3) according to claim 1 and a tetracarboxylic acid derivative component.

4. A polyimide precursor obtainable by a polymerization reaction of a diamine component containing at least one compound selected from the group consisting of compounds represented by any one of formulas (d-1) to (d-8) according to claim 2, and a tetracarboxylic acid derivative component.

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