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

Abstract

The present invention provides a liquid crystal alignment agent that forms a liquid crystal alignment film exhibiting a high voltage retention rate, suppressing the occurrence of afterimages, and exhibiting low liquid crystal pretilt angle characteristics, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. The liquid crystal alignment agent is characterized by containing a polymer having at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1). [Chemical Formula 1] (In Equation (1), X1 represents a tetravalent organic group. Y1 is a divalent organic group represented by "-Ar1-OWO-Ar2-". Ar1 and Ar2 each independently represent either a divalent aromatic group of a divalent benzene ring or a biphenyl structure, and any hydrogen atom of the aromatic group may be substituted with a monovalent group. W represents *-(CH2)mLA-* (L represents -OC(=O)- or -C(=O)-O-, and A represents -(CH2)n-. m is an integer from 1 to 6. n is an integer from 1 to 16. If n is 2 or greater, any -CH2- constituting A is -O-, -C(=O)-, -NH-, -OC(=O)-, -C(=O)-O-, -C=C-, phenylene group, or It may be substituted with a cyclohexylene group. Also, some of the hydrogen atoms in W may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.) It is a divalent organic group having 4 to 20 carbon atoms represented by *. * indicates a bond loss. R and Z each independently represent a hydrogen atom or a monovalent organic group.)

Description

Technology Field

[0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, a liquid crystal display device having the liquid crystal alignment film, and a novel diamine and polymer suitable for the same. Background Technology

[0002] Liquid crystal display devices are widely used for applications ranging from small devices such as mobile phones and smartphones to relatively large devices such as televisions and monitors. Furthermore, various driving methods have been developed that differ in electrode structure and the physical properties of the liquid crystal molecules used. For example, liquid crystal display devices using various modes such as TN (Twisted Nematic), STN (Super Twisted Nematic), VA (Vertical Alignment), IPS (In-Plane Switching), and FFS (Fringe Field Switching) are known. These liquid crystal display devices generally have a liquid crystal alignment layer, which is indispensable for controlling the arrangement state of liquid crystal molecules. Polyamic acid and polyimide are generally used as materials for the liquid crystal alignment layer due to their good various properties, such as heat resistance, mechanical strength, and affinity with liquid crystals.

[0003] Liquid crystal display devices require high display quality, and for example, exhibiting a high voltage retention rate is one of the required characteristics. For this purpose, Patent Document 1 discloses a composition for a liquid crystal alignment film comprising an aromatic diamine such as 1,5-bis(4-aminophenoxy)pentane. In addition, Patent Document 2 discloses using a polyamic acid, obtained by reacting a tetracarboxylic acid derivative with a diamine in which two aromatic rings are connected by a specific alkylene group, as a polymer component of a liquid crystal alignment agent. Prior art literature

[0004] Japan Japanese Published Patent Application No. Hei 06-194670 Japan Japanese Published Patent Application No. 2014-132326 The problem to be solved

[0005] Recently, with the advancement of high-performance liquid crystal display (LCD) devices, applications are being considered not only for large-screen, high-definition LCD televisions but also for automotive use, such as in-car navigation systems, meter panels, and monitors for surveillance or medical cameras. Consequently, the demand for high performance, particularly in high-definition LCDs, is increasing, and liquid crystal alignment films are required to further improve various characteristics of the LCD device.

[0006] One objective of the present invention is to form a liquid crystal alignment film having a high voltage retention rate, which is a condition for providing long-term reliability of so-called display quality, by suppressing the occurrence of display defects such as image burn-in (image burn-in of sections and lines), non-uniformity, or contamination that occur over time due to external stimuli such as light or temperature. Another objective of the present invention is to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film exhibiting low liquid crystal tilt angle characteristics that can meet the demand for viewing angle characteristics by suppressing afterimages (hereinafter also referred to as AC afterimages) generated by long-term AC driving, a liquid crystal display device having said liquid crystal alignment film, and novel diamines and polymers suitable for said liquid crystals. means of solving the problem

[0007] As a result of conducting diligent research to achieve the above objective, the inventors discovered that a liquid crystal orientation agent containing a specific polymer is effective for achieving the above objective, and thus completed the present invention.

[0008] The present invention is characterized by the following.

[0009] A liquid crystal orientation agent characterized by containing at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1).

[0010] [Chemical Formula 1]

[0011]

[0012] (In Equation (1), X1 represents a tetravalent organic group. Y1 is a divalent organic group represented as "-Ar1-OWO-Ar2-".)

[0013] Ar1 and Ar2 each independently represent either a divalent aromatic group of a divalent benzene ring or a biphenyl structure, and any hydrogen atom of the aromatic group may be substituted with a monovalent group.

[0014] W is, *-(CH2) m -LA-* ( L represents -OC(=O)- or -C(=O)-O-, and A is -(CH2) n - represents.

[0015] m is an integer from 1 to 6. n is an integer from 1 to 16. When n is 2 or greater, any -CH2- constituting A may be substituted with -O-, -C(=O)-, -NH-, -OC(=O)-, -C(=O)-O-, -C=C-, phenylene group, or cyclohexylene group.

[0016] Also, some of the hydrogen atoms of W may be substituted with halogen atoms, methyl groups, trifluoromethyl groups, or hydroxyl groups.) It is a divalent organic group having 4 to 20 carbon atoms represented by *. * indicates a bond loss.

[0017] R and Z each independently represent a hydrogen atom or a monovalent organic group.

[0018] In addition, in the present invention, halogen atoms may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., and * indicates bond loss. Effects of the invention

[0019] According to the present invention, a liquid crystal alignment agent is obtained that forms a liquid crystal alignment film exhibiting a high voltage retention rate, suppressing the generation of afterimages, and exhibiting low liquid crystal pretilt angle characteristics; a liquid crystal alignment film obtained from the liquid crystal alignment agent; a high-performance liquid crystal display device having the liquid crystal alignment film; and a novel diamine and polymer used in the manufacture thereof.

[0020] Although the mechanism by which the above effect of the present invention is obtained is not necessarily clear, it is generally presumed as follows. First, since the specific diamine described below has a structure in which an oxygen atom is bonded to an aromatic group, it can be assumed that when used as a liquid crystal alignment film, the voltage retention rate is improved through a trapping phenomenon that suppresses the diffusion of impurities by interacting with ionic impurities that cause display defects. Furthermore, it can be assumed that the above effect is obtained because the same trapping phenomenon for impurities also occurs in the ester bonds of the specific diamine. Moreover, it can be assumed that a liquid crystal alignment film in which the generation of AC afterimages is suppressed is obtained because the specific diamine has ester bonds or alkylene chains, thereby increasing the elongation of the polymer during the alignment process and obtaining high liquid crystal alignment. Brief explanation of the drawing

[0021] FIG. 1 is a schematic partial cross-sectional view showing an example of a transverse electric field liquid crystal display element of the present invention. FIG. 2 is a schematic partial cross-sectional view showing another example of a transverse electric field liquid crystal display element of the present invention. Specific details for implementing the invention

[0022] <Polymers contained in liquid crystal alignment agents>

[0023] The liquid crystal alignment agent of the present invention is characterized by containing a polymer having at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1), as described above.

[0024] [Chemical Formula 2]

[0025]

[0026] (In Equation (1), X1, Y1, R, and Z are each as defined above.)

[0027] Ar1, W, and Ar2 in Y1("-Ar1-OWO-Ar2-") in the above formula (1) are, including a preferred embodiment, the formula (D) described below. A It is identical to Ar1, W, and Ar2 in ).

[0028] The “-N(Z)-Ar1-OWO-Ar2-N(Z)-” in the above formula (1) can be formed, for example, by using a diamine component containing the following specific diamine as a raw material for the polymer, but is not limited to this method.

[0029] As the monovalent organic group in R and Z in the above formula (1), it is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the methylene group of said hydrocarbon group is -O-, -S-, -CO-, -COO-, -COS-, -NR 3 -, -CO-NR 3 -, -Si(R 3 )2- (where R 3Examples include a monovalent group A formed by substituting at least one hydrogen atom bonded to the carbon atom of the monovalent hydrocarbon group having 1 to 6 carbon atoms, -SO2-, etc., a monovalent group formed by substituting at least one hydrogen atom bonded to the carbon atom of the monovalent hydrocarbon group or the monovalent group A by substituting it with a halogen atom, a hydroxyl group, an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxysilyl group, a silanol group, a sulfino group, a phosphino group, a carboxyl group, a cyano group, a sulfo group, an acyl group, etc., and a monovalent group having a complex ring.

[0030] Among the monovalent organic groups in R and Z in the above formula (1), a carbon 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, or a tert-butoxycarbonyl group is preferred, an carbon alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred.

[0031] R and Z are each preferably, independently, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group, in order to obtain the effects of the present invention.

[0032] As X1 in the above formula (1), for example, a tetravalent organic group derived from the tetracarboxylic acid dihydride or its derivative described later may be cited. As a preferred embodiment of the tetracarboxylic acid dihydride or its derivative in the above X1, a preferred embodiment of the tetracarboxylic acid dihydride or its derivative that can be used in the synthesis of the polymer (P) described later may be cited.

[0033] <Specific Diamines>

[0034] The polymer contained in the liquid crystal orientation agent of the present invention is, for example, of the following formula (D AIt is at least one polymer (P) selected from the group consisting of a polyimide precursor obtained using a diamine component containing a diamine (O) represented by ) (hereinafter also referred to as a specific diamine) and a polyimide which is an imid of the polyimide precursor.

[0035] [Chemical Formula 3]

[0036]

[0037] The above equation (D A In ), Ar1, Ar2, and W are each as defined above.

[0038] The above equation (D A In ), W is, *-(CH2) m The organic group is a divalent organic group having 4 to 20 carbon atoms represented by -LA-*, but from the viewpoint of obtaining the effects of the present invention, a divalent organic group having 4 to 18 carbon atoms is more preferable, and a divalent organic group having 4 to 16 carbon atoms is even more preferable.

[0039] Also, L in the above W is preferably -OC(=O)-. A is preferably -(CH2) n - (n is an integer from 1 to 16), or -(CH2) n' - (n' is an integer from 2 to 16.) It is a divalent organic group formed by substituting any -CH2- with -O-, -C(=O)-, -NH-, -OC(=O)-, -C(=O)-O-, -C=C-, phenylene group, or cyclohexylene group.

[0040] m is more preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and even more preferably an integer of 2 or 4 from the perspective of obtaining high liquid crystal orientation. n is preferably 1 to 13. In addition, a fluorine atom is preferred as the halogen atom substituting the hydrogen atom of W.

[0041] A more preferred specific example of the above W is *-(CH2) p -OC(=O)-(CH2) q -*, *-(CH2) p -OC(=O)-(CH2) q -C(=O)-O-(CH2) r -, *-(CH2) p -C(=O)-O-(CH2) q -OC(=O)-(CH2) r -*, *-(CH2) p -OC(=O)-QC(=O)-O-(CH2) q -* (Q represents a phenylene group or a cyclohexylene group.), *-(CH2) p -C(=O)-OQOC(=O)-(CH2) q -* (Q represents a phenylene group or a cyclohexylene group.) may be used. Here, p is an integer from 1 to 6, preferably an integer from 2 to 6. q is an integer from 1 to 6, more preferably an integer from 2 to 6, and even more preferably an integer from 2, 4, or 6. r is an integer from 1 to 6, preferably an integer from 2 to 6.

[0042] The above equation (D A Examples of monovalent groups substituting hydrogen atoms of the divalent aromatic groups Ar1 and Ar2 in ) include halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, fluoroalkyl groups having 1 to 10 carbon atoms, fluoroalkenyl groups having 2 to 10 carbon atoms, fluoroalkoxy groups having 1 to 10 carbon atoms, carboxyl groups, hydroxyl groups having 1 to 10 carbon atoms, cyano groups, nitro groups, etc. Among these, halogen atoms, alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, fluoroalkyl groups having 1 to 5 carbon atoms, or fluoroalkoxy groups having 1 to 5 carbon atoms are preferred.

[0043] Preferred examples of divalent aromatic groups represented by Ar1 and Ar2 include 1,4-phenylene, 1,3-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 2-butyl-1,4-phenylene, 2-isopropyl-1,4-phenylene, 2-tert-butyl-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-ethoxy-1,4-phenylene, 2-propoxy-1,4-phenylene, 2-butoxy-1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, and 4-fluoro-1,3-phenylene. 2,3,5,6-tetramethyl-1,4-phenylene, 4,4'-biphenylylene, 2-methyl-4,4'-biphenylylene, 2-ethyl-4,4'-biphenylylene, 2-propyl-4,4'-biphenylylene, 2-butyl-4,4'-biphenylylene, 2-tert-butyl-4,4'-biphenylylene, 2-methoxy-4,4'-biphenylylene, 2-ethoxy-4,4'-biphenylylene, 2-fluoro-4,4'-biphenylylene, 3-methyl-4,4'-biphenylylene, 3-ethyl-4,4'-biphenylylene, 3-propyl-4,4'-biphenylylene, 3-butyl-4,4'-biphenylylene, 3-tert-butyl-4,4'-biphenylylene, Examples include 3-methoxy-4,4'-biphenylylene, 3-ethoxy-4,4'-biphenylylene, 3-fluoro-4,4'-biphenylylene, 2,2'-dimethyl-4,4'-biphenylylene, 3,3'-dimethyl-4,4'-biphenylylene, 3,3'-biphenylylene, 5-methyl-3,3'-biphenylylene, 5,5'-dimethyl-3,3'-biphenylylene, etc.

[0044] The above equation (D A A desirable example of ) is the following formula (d A -1) ∼ (d A -5) can be cited. Also, the following equation (d A -1) ∼ (d A -5) The hydrogen atoms on the benzene ring may be replaced with monovalent substituents, and as a preferred specific example of the substituent, the above formula (D AExamples of structures can be given as monovalent groups that substitute hydrogen atoms of the divalent aromatic groups Ar1 and Ar2.

[0045] [Chemical Formula 4]

[0046]

[0047] (Polymer (P))

[0048] The polymer (P) contained in the liquid crystal orientation agent of the present invention is, for example, a polyimide precursor obtained using a diamine component containing the diamine (O), or a polyimide that is an imid of the polyimide precursor. Here, the polyimide precursor is a polymer that can obtain polyimide by imidizing a polyamic acid, a polyamic acid ester, etc.

[0049] The polyamic acid (P'), which is a polyimide precursor of the above polymer (P), can be obtained by a polymerization reaction between a diamine component containing the above diamine (O) and a tetracarboxylic acid component. The above diamine (O) may be used as a single type or in combination of two or more types.

[0050] The amount of diamine (O) used is preferably 5 mol% or more with respect to the total diamine component, more preferably 10 mol% or more, and even more preferably 20 mol% or more.

[0051] In order to obtain the effects of the present invention in a desirable manner, the polymer (P) preferably contains at least 5 mol% of the total repeating unit (p1) and the imidized structure of the repeating unit (p1), more preferably at least 10 mol%, and even more preferably at least 20 mol% of the total repeating unit having the polymer (P). Furthermore, the sum described herein includes cases where either the repeating unit (p1) or the imidized structure of the repeating unit (p1) is 0 mol%. In the following, when referring to the sum, cases where one or two or more of the components are 0 mol% are also included.

[0052] The diamine component used in the manufacture of the above polyamic acid (P') may contain a diamine other than the diamine (O) (hereinafter also referred to as other diamine). When other diamines are used in combination with the above diamine (O), the amount of diamine (O) used relative to the diamine component is preferably 90 mol% or less, and more preferably 80 mol% or less.

[0053] Examples of other diamines are given below, but are not limited to these. The above other diamines may be used alone or in combination of two or more types. p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2.2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2.2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, the following formula (d AL -1) ∼ (d AL-10) Diamine represented as, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, 1,4-bis(4-aminophenoxy)benzene, 1,3-Bis(4-aminophenoxy)benzene, 4,4'-Bis(4-aminophenoxy)biphenyl, 4,4'-Bis(4-aminophenoxy)diphenyl ether, 1,4-Bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-Bis(6-amino-2-naphthyloxy)ethane, 1,2-Bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), Bis(4-aminophenyl)terephthalate, Bis(3-aminophenyl)terephthalate, Bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate; diamine having a photopolymerizable group such as 4,4'-diaminoazobenzene or diaminotrans; diamine having a photopolymerizable group at the terminal end such as methacrylic acid 2-(2,4-diaminophenoxy)ethyl or 2,4-diamino-N,N-diallylaniline; diamine having a radical polymerization initiator function such as 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone, 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl-3,5-diaminobenzoate; Diamines having an amide link such as 4,4'-diaminobenzanilide, diamines having a urea link such as 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,3-bis(4-aminophenethyl)urea;3,3'-Diaminodiphenyl ether, 3,4'-Diaminodiphenyl ether, 4,4'-Diaminodiphenyl ether, 1,4-Bis(4-aminophenoxy)benzene, 1,3-Bis(4-aminophenoxy)benzene, 2,2'-Bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-Bis(4-aminophenyl)hexafluoropropane, 2,2'-Bis(3-aminophenyl)hexafluoropropane, 2,2'-Bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-Bis(4-aminophenyl)propane, 2,2'-Bis(3-aminophenyl)propane, 2,2'-Bis(3-amino-4-methylphenyl)propane, 4,4'-Diaminobenzophenone, 1,4-Bis(4-aminophenyl)benzene, 1,3-Bis(4-aminophenyl)benzene, 1,4-Bis(4-aminobenzyl)benzene, 2,6-Diaminopyridine, 3,4-Diaminopyridine, 2,4-Diaminopyridine, 3,6-Diaminocarbazole, N-Methyl-3,6-Diaminocarbazole, 1,4-Bis-(4-aminophenyl)-Piperazine, 3,6-Diaminoacridine, N-Ethyl-3,6-Diaminocarbazole, N-Phenyl-3,6-Diaminocarbazole, N-(3-(1H-imidazole-1-yl)propyl-3,5-Diaminobenzamide, A diamine having at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocyclic ring, a secondary amino acid, and a tertiary amino group (hereinafter also referred to as a specific nitrogen atom-containing structure), represented by 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydride-4-methyl-2-oxazolyl]-benzeneamine, or a heterocyclic diamine such as a diamine represented by the following formulas (z-1) to (z-13), or a diamine having a diphenylamine structure such as 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-benzenediamine (provided that the nitrogen atom is removed by heating and hydrogen It does not have an amino group in the molecule to which a protecting group that is substituted by an atom is attached.2,4-Diaminophenol, 3,5-Diaminophenol, 3,5-Diaminobenzyl alcohol, 2,4-Diaminobenzyl alcohol, 4,6-Diaminoresorcinol, 4,4'-Diamino-3,3'-Dihydroxybiphenyl ; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, Diamines having a carboxyl group such as 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indene-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine; Diamines having a group “-N(D)-” (where D represents a protecting group that is detached by heating and substituted with a hydrogen atom, preferably a carbamate-based protecting group, and more preferably a tert-butoxycarbonyl group) of formulas (5-1) to (5-6) below; diamines having a steroid backbone such as cholestanyloxy-3,5-diaminobenzene, cholestenioxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyoxy)cholestan; diamines represented by formulas (V-1) to (V-2) below; diamines having a siloxane link such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane;Metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), diamines in which two amino groups are attached to a group represented by any of formulas (Y-1) to (Y-167) described in International Publication No. 2018 / 117239;

[0054] [Chemical Formula 5]

[0055]

[0056] [Chemical Formula 6]

[0057]

[0058] (Boc represents a tert-butoxycarbonyl group.)

[0059] [Chemical Formula 7]

[0060]

[0061] [Chemical Formula 8]

[0062]

[0063] [Chemical Formula 9]

[0064]

[0065] In the above equation (V-1), m and n are integers from 1 to 3, satisfying 1 ≤ m + n ≤ 4. j is an integer of 0 or 1. X 1 은, -(CH2) a - (a is an integer from 1 to 15), represents -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -CH2O-, -CH2-OCO-, -COO-, or -OCO-. R 1Silver represents a monovalent group such as a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxyalkyl group having 2 to 10 carbon atoms. In the above formula (V-2), X 2 represents -O-, -CH2O-, -CH2-OCO-, -COO-, or -OCO-. m, n, X 1 , R 1 If these two exist, each has the above definition independently.

[0066] When other diamines are used in addition to the above diamine (O), the amount of other diamine used is preferably 10 to 90 mol% and more preferably 20 to 80 mol% with respect to the total diamine components used.

[0067] The amount of the above other diamine used is preferably 10 to 90 mol% with respect to the total diamine component used in the manufacture of the polymer (P), and more preferably 20 to 80 mol%.

[0068] (Tetracarboxylic acid component)

[0069] When preparing the above polyamic acid (P'), the tetracarboxylic acid component reacted with the diamine component may be a tetracarboxylic acid dihydride, as well as a derivative of tetracarboxylic acid dihydride such as tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester dihalide.

[0070] The above tetracarboxylic acid dihydride or its derivative may include acyclic aliphatic tetracarboxylic acid dihydride, alicyclic tetracarboxylic acid dihydride, aromatic tetracarboxylic acid dihydride, or derivatives thereof. Among these, it is more preferable to contain a tetracarboxylic acid dihydride or its derivative having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. In particular, it is even more preferable to contain a tetracarboxylic acid dihydride or its derivative having at least one structure selected from the group consisting of a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0071] In addition, aromatic tetracarboxylic acid dihydrides are acid dihydrides obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to an aromatic ring.

[0072] A cyclic aliphatic tetracarboxylic acid dihydride is an acid dihydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not need to be composed solely of a chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in part.

[0073] A dihydrocitric acid alicyclic tetracarboxylic acid is an acid dihydrocitric acid obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to the alicyclic structure. However, none of these four carboxyl groups are bonded to an aromatic ring. In addition, it is not necessary for it to be composed solely of alicyclic structures, and it may have a chain hydrocarbon structure or an aromatic ring structure in part.

[0074] The tetracarboxylic acid component that can be used to manufacture the above polyamic acid (P') preferably contains the following tetracarboxylic acid dihydride or derivative thereof (in the present invention, these are collectively referred to as specific tetracarboxylic acid derivatives).

[0075] Acyclic aliphatic tetracarboxylic acid dihydrides such as 1,2,3,4-butanetetracarboxylic acid dihydride; 1,2,3,4-cyclobutanetetracarboxylic acid 2 anhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid 2 anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid 2 anhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic acid 2 anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid 2 anhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic acid 2 anhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic acid 2 anhydride, 1,2,3,4-cyclopentanetetracarboxylic acid 2 anhydride, 1,2,4,5-cyclohexanedetatecarboxylic acid dihydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid dihydride, 2,3,5-tricarboxycyclopentylacetic acid dihydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic acid dihydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, Bicyclo[2.2.2]octa-7-en 2,3,5,6-tetracarboxylic acid 2 anhydride, bicyclo[2.2.2]octa-2,3,5,6-tetracarboxylic acid 2 anhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]Octane-2:4,6:8-2 anhydride, etc., alicyclic tetracarboxylic acid dihydride; Pyromellitic acid 2 anhydride, 3,3',4,4'-benzophenone tetracarboxylic acid 2 anhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic acid 2 anhydride, 1,4,5,8-naphthalene tetracarboxylic acid 2 anhydride, 2,3,6,7-naphthalene tetracarboxylic acid 2 anhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid 2 anhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid 2 anhydride, 3,3',4,4'-biphenyl tetracarboxylic acid 2 anhydride, 2,2',3,3'-biphenyl tetracarboxylic acid 2 anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane 2 anhydride, Aromatic tetracarboxylic acid dihydrides such as ethylene glycol bis-anhydrotrimate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-oxydi(1,4-phenylene)bis(phthalic acid) dihydride, or 4,4'-methylenedi(1,4-phenylene)bis(phthalic acid) dihydride; and other tetracarboxylic acid dihydrides described in Japanese Patent Publication No. 2010-97188, etc.

[0076] Preferred examples of the specific tetracarboxylic acid derivatives mentioned above include 1,2,3,4-butanetetracarboxylic acid dihydride, 1,2,3,4-cyclobutanetetracarboxylic acid dihydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dihydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dihydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dihydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic acid dihydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic acid dihydride, and 1,2,3,4-cyclopentanetetracarboxylic acid 2 Anhydride, 1,2,4,5-cyclohexanedetatecarboxylic acid dihydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid dihydride, 2,3,5-tricarboxycyclopentylacetic acid dihydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8- dihydride, pyromellitic acid dihydride, 3,3',4,4'-benzophenone tetracarboxylic acid dihydride, 3,3',4,4'-biphenylsulfone tetracarboxylic acid dihydride, 1,4,5,8-naphthalene tetracarboxylic acid dihydride, 2,3,6,7-naphthalene tetracarboxylic acid dihydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dihydride, 3,3',4,4'-biphenyl tetracarboxylic acid dihydride, 2,2',3,3'-biphenyl tetracarboxylic acid dihydride, or derivatives thereof.

[0077] The usage ratio of the above-mentioned specific tetracarboxylic acid derivative is preferably 10 mol% or more with respect to the total tetracarboxylic acid component used, more preferably 20 mol% or more, and even more preferably 50 mol% or more.

[0078] (Liquid crystal alignment agent)

[0079] The liquid crystal orientation agent of the present invention is a liquid composition comprising, for example, a polymer (P) and other components used as needed, preferably dispersed or dissolved in a suitable solvent.

[0080] The total content of the polymer contained in the liquid crystal alignment agent of the present invention can be appropriately changed by setting the thickness of the film to be formed, but it is preferable to have 1 mass% or more in terms of forming a uniform and defect-free film, and 10 mass% or less in terms of storage stability of the solution. A particularly preferred total content of the polymer is 2 to 8 mass%.

[0081] The content of the polymer (P) used in the present invention is preferably 1 to 100 mass% with respect to the total polymer contained in the liquid crystal orientation agent, more preferably 10 to 100 mass%, and particularly preferably 20 to 100 mass%.

[0082] The liquid crystal alignment agent of the present invention may contain polymers other than polymer (P). Specific examples of other polymers include at least one polymer selected from the group consisting of a polyimide precursor obtained by using a diamine component that does not have the specific diamine in addition to the polymer (P) and a polyimide which is an imid of the polyimide precursor (also referred to as polymer (B) in the present invention), a polymer selected from the group consisting of polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, and poly(meth)acrylate.

[0083] Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley Corporation), GSM301 (manufactured by Gifu Shellac Co., Ltd.), and specific examples of poly(isobutylene-maleic anhydride) copolymers include Isobam-600 (manufactured by Kuraray Corporation). Specific examples of poly(vinyl ether-maleic anhydride) copolymers include Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Asiland Corporation).

[0084] Among them, polymer (B) is more preferable in that it reduces residual DC-derived residue.

[0085] The above other polymers may be used as a single type or in combination of two or more types. The content ratio of the other polymers 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, based on 100 parts by mass of the total polymers contained in the liquid crystal alignment agent.

[0086] (polymer (B))

[0087] Specific examples of the tetracarboxylic acid component used in the manufacture of the above polymer (B) include preferred embodiments and may be compounds identical to the compounds exemplified in polymer (P). The tetracarboxylic acid component used in the manufacture of the above polymer (B) is more preferably a tetracarboxylic acid dihydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring, or a derivative thereof, and the specific tetracarboxylic acid derivative is even more preferred, and it is most preferable to use a more preferred embodiment of the specific tetracarboxylic acid derivative.

[0088] In addition, the amount of the specific tetracarboxylic acid derivative used is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more with respect to the total tetracarboxylic acid component used in the manufacture of polymer (B).

[0089] As a diamine component for obtaining polymer (B), examples include the diamine exemplified in the polymer (P). Among these, a diamine having at least one group selected from the group consisting of urea bonds, amide bonds, carboxyl groups, and hydroxyl groups within the molecule, the formula (d AL -1) ∼ (d AL It is preferable to contain at least one diamine selected from the group consisting of a diamine represented by -10) and a diamine having a specific nitrogen atom-containing structure (in the present invention, these are also referred to as specific diamine (b). The diamine component may use one type of diamine alone or two or more types in combination.

[0090] When using the specific diamine (b) above, the amount used is preferably 10 mol% or more of the total diamine component used in the manufacture of the polymer (B), and more preferably 20 mol% or more. When using a diamine other than the specific diamine (b), the amount used is preferably 90 mol% or less of the total diamine component used in the manufacture of the polymer (B), and more preferably 80 mol% or less.

[0091] (Manufacture of polyamic acid)

[0092] The production of polyamic acid is carried out by reacting a diamine component and a tetracarboxylic acid component in an organic solvent. The ratio of the tetracarboxylic acid component and the diamine component used in the reaction for the production of polyamic acid is preferably such that the acid anhydride group of the tetracarboxylic acid component is 0.5 to 2 equivalents relative to 1 equivalent of the amino group of the diamine component, and more preferably 0.8 to 1.2 equivalents. As with conventional polycondensation reactions, the closer the equivalent of the acid anhydride group of the tetracarboxylic acid component is to 1 equivalent, the larger the molecular weight of the polyamic acid produced.

[0093] In the preparation of polyamic acid, the reaction temperature is preferably -20 to 150 ℃, and more preferably 0 to 100 ℃. In addition, the reaction time is preferably 0.1 to 24 hours, and more preferably 0.5 to 12 hours. The preparation of polyamic acid can be carried out at any concentration, but the concentration of polyamic acid is preferably 1 to 50 mass%, and more preferably 5 to 30 mass%. The initial reaction may be carried out at a high concentration, and then a solvent may be added.

[0094] Specific examples of the above organic solvents include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. In addition, when the solvent solubility of the polymer is high, solvents such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether may be used.

[0095] (Preparation of polyamic acid esters)

[0096] Polyamic acid esters can be obtained by known methods, such as, for example, [I] a method of reacting a polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, and [III] a method of reacting a tetracarboxylic acid diester dihalogenate with a diamine.

[0097] (Manufacture of polyimide)

[0098] Polyimide can be obtained by ring-closing (imidizing) a polyimide precursor, such as the polyamic acid or polyamic acid ester mentioned above. In addition, the imidization rate referred to in this specification is the ratio of the imide group to the total amount of the imide group and the carboxyl group (or its derivative) derived from the tetracarboxylic acid dihydride or its derivative. The imidization rate does not necessarily have to be 100% and can be adjusted arbitrarily depending on the use or purpose.

[0099] Methods for imidizing a polyimide precursor include thermal imidization, in which a solution of the polyimide precursor is heated as is, or catalytic imidization, in which a catalyst is added to a solution of the polyimide precursor.

[0100] When thermally imidizing a polyimide precursor in a solution, the temperature is preferably 100 to 400°C, more preferably 120 to 250°C, and it is preferable to perform the process while removing water generated by the imidization reaction from the system.

[0101] Catalytic imidization of a polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 mole times the amic acid group, preferably 2 to 20 mole times, and the amount of the acid anhydride is 1 to 50 mole times the amic acid group, preferably 3 to 30 mole times. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, or trioctylamine; among these, pyridine is preferred because it has basicity suitable for carrying out the reaction. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, or pyromellitic anhydride; among these, using acetic anhydride is preferred because it facilitates purification after the reaction is completed. The imidation rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0102] When recovering the polyimide precursor or polyimide produced from a reaction solution of a polyimide precursor or polyimide, the reaction solution can be precipitated by adding it to 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 adding it to a solvent can be recovered by filtration and then dried at room temperature or by heating under atmospheric or reduced pressure. Additionally, if the recovered polymer is redissolved in an organic solvent and the operation of redepositing and recovering is repeated 2 to 10 times, the impurities in the polymer can be reduced. Examples of solvents used at this time include alcohols, ketones, or hydrocarbons, and it is preferable to use three or more types of solvents selected from these, as this further increases the efficiency of purification.

[0103] In preparing the polyimide precursor or polyimide according to the present invention, a polymer with terminal encapsulation may be prepared by using a suitable terminal encapsulator together with a tetracarboxylic acid component containing tetracarboxylic acid dihydride or a derivative thereof, and a diamine component containing said diamine. The polymer with terminal encapsulation has the effect of improving the film hardness of the alignment film obtained by the coating film or improving the adhesion characteristics between the sealant and the alignment film.

[0104] Examples of the polyimide precursor or the end of the polyimide in the present invention include amino groups, carboxyl groups, acid anhydride groups, or groups derived from the end encapsulating agent described below. Amino groups, carboxyl groups, and acid anhydride groups can be obtained by a conventional condensation reaction or by encapsulating the end using the end encapsulating agent described below.

[0105] As terminal encapsulators, for example, acid anhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride; dicarbonate diester compounds such as di-tert-butyl bicarbonate and diallyl bicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinate chloride; Examples include 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, n-octylamine; isocyanates having unsaturated bonds such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, etc.

[0106] The usage ratio of the terminal encapsulant is preferably 0.01 to 20 moles per 100 moles of the total diamine components used, and more preferably 0.01 to 10 moles.

[0107] The weight-average molecular weight (Mw) of the polystyrene equivalent measured by gel permeation chromatography (GPC) of the polyimide precursor and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000, and even more preferably 10,000 to 50,000. In addition, the molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number-average molecular weight (Mn) of the polystyrene equivalent measured by GPC, is preferably 15 or less, and more preferably 10 or less. By being within this molecular weight range, good liquid crystal orientation of the liquid crystal display device can be secured.

[0108] The organic solvent contained in the liquid crystal orientation agent related to the present invention is not particularly limited as long as the polymer (P) or other polymers added as necessary are uniformly dissolved. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamid, N,N-dimethylpropionamide, tetramethylurea, N,N-diethylformamide, 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-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(t-butyl)-2-pyrrolidone, Examples include N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (collectively referred to as both solvents). Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, or γ-butyrolactone are preferred. The content of the both solvent is preferably 20 to 99 mass% of the total solvent contained in the liquid crystal orientation agent, more preferably 20 to 90 mass%, and particularly preferred is 30 to 80 mass%.

[0109] In addition, for the organic solvent contained in the liquid crystal alignment agent, it is preferable to use a mixed solvent in which a solvent (also called a non-solvent) that improves the applicability or surface smoothness of the coating film when applying the liquid crystal alignment agent is used in addition to the above solvent. Specific examples of non-solvents are described below, but are not limited thereto. The content of the non-solvent is preferably 1 to 80 mass% of the total solvent contained in the liquid crystal alignment agent, more preferably 10 to 80 mass%, and particularly preferably 20 to 70 mass%. The type and content of the non-solvent are appropriately selected according to the coating apparatus, coating conditions, coating environment, etc. of the liquid crystal alignment agent.

[0110] As co-solvents, for example, diisopropyl ether, diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, 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 monomethyl ether, Propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monopropyl ether, 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, cyclohexyl acetate, 4-methyl-2-pentyl acetate, 3-methyl methoxypropionate, 3-ethyl ethoxypropionate, 3-ethyl methoxypropionate, Examples include 3-propyl methoxypropionate, 3-butyl methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), etc.

[0111] Among these, diisobutylcarbinol, 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.

[0112] Preferred solvent combinations for both solvents and co-solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone and propylene glycol diacetate, N,N-dimethyllactoamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone and 3-ethyl ethoxypropionate and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and 3-ethyl ethoxypropionate and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 3-ethyl ethoxypropionate and diethylene glycol monopropyl ether, N-ethyl-2-pyrrolidone and 3-ethyl ethoxypropionate and diethylene glycol monopropyl ether, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate, N-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether, N,N-dimethyllactamide and ethylene glycol monobutyl ether, N,N-dimethyllactamide and propylene glycol diacetate, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and diethylene glycol monoethyl ether and Butyl cellosolve acetate, N-methyl-2-pyrrolidone and diethylene glycol monomethyl ether and butyl cellosolve acetate, N,N-dimethyllactamide 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 diisobutyl ketone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and Dipropylene glycol monomethyl ether,N-methyl-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 propylene glycol diacetate, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol dimethyl ether, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and Diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisobutylcarbinol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and propylene glycol diacetate, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and diisobutyl ketone, N-ethyl-2-pyrrolidone and γ-butyrolactone and Diisobutyl ketone, N-ethyl-2-pyrrolidone and N,N-dimethyllactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate, γ-butyrolactone and ethylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate and propylene glycol dimethyl ether, N-methyl-2-pyrrolidone and 4-methyl-2-pentyl acetate and ethylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and cyclohexyl acetate and 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and propylene glycol monomethyl ether, cyclopentanone and propylene glycol monomethyl ether,Examples include N-methyl-2-pyrrolidone, cyclohexanone, and propylene glycol monomethyl ether.

[0113] (Liquid crystal alignment agent)

[0114] The liquid crystal alignment agent of the present invention may contain, in addition to the polymer (P), the other polymer, and the organic solvent, other components (hereinafter also referred to as additive components). Examples of such additive components include, for instance, at least one crosslinkable compound selected from the group consisting of a crosslinkable compound having at least one substituent selected from oxiranyl groups, oxetanyl groups, block isocyanate groups, oxazoline groups, cyclocarbonate groups, hydroxyl groups, and alkoxy groups, and a crosslinkable compound 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 obtained liquid crystal alignment film.

[0115] Preferred specific examples of the above-mentioned crosslinking compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, bisphenol A type epoxy resin such as Epicoat 828 (manufactured by Mitsubishi Chemical), bisphenol F type epoxy resin such as Epicoat 807 (manufactured by Mitsubishi Chemical), hydrogenated bisphenol A type epoxy resin such as YX-8000 (manufactured by Mitsubishi Chemical), and YX6954BH30 (Mitsubishi Epoxy resins containing a biphenyl backbone such as (manufactured by Chemical Co., Ltd.), phenol novolak-type epoxy resins such as EPPN-201 (manufactured by Nippon Hwayakusho), (o,m,p-) cresol novolak-type epoxy resins such as EOCN-102S (manufactured by Nippon Hwayakusho), triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Co., Ltd.), alicyclic epoxy resins such as cellulose 2021P (manufactured by Daicel Chemical Industry Co., Ltd.), compounds containing a tertiary nitrogen atom represented by N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and compounds having two or more oxiranyl groups such as tetrakis(glycidyloxymethyl)methane; Compounds having two or more oxetanyl groups as described in paragraphs

[0170] to

[0175] of WO2011 / 132751; compounds having a block isocyanate group, such as Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Tosho Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemical Corporation);Compounds having an oxazoline group such as 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), 2,2'-bis(5-methyl-2-oxazoline), 1,2,4-tris(2-oxazolinyl-2)-benzene, epochose (manufactured by Nippon Catalytic Co.); compounds having a cyclocarbonate group as described in paragraphs

[0025] to

[0030] ,

[0032] of WO2011 / 155577; Compounds having hydroxyl or alkoxy groups, such as n,n,n',n'-tetrakis(2-hydroxyethyl)adipoamide, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxymethylphenyl)propane, and 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane; Examples of compounds include glycerin mono(meth)acrylate, glycerin di(meth)acrylate (mixture of 1,2-, 1,3-), glycerin tri(meth)acrylate, glycerol 1,3-diglycerolato di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate, and hexaethylene glycol mono(meth)acrylate.

[0116] The content of the above-mentioned crosslinkable compound is preferably 0.1 to 30 parts by mass per 100 parts by mass of the polymer component contained in the liquid crystal orientation agent, and more preferably 0.1 to 20 parts by mass.

[0117] Examples of compounds for adjusting the dielectric constant or electrical resistance include monoamines having a nitrogen atom-containing aromatic complex ring, such as 3-picolylamine. The content of the monoamine having a nitrogen atom-containing aromatic complex ring is preferably 0.1 to 30 parts by mass per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent, and more preferably 0.1 to 20 parts by mass.

[0118] Preferred embodiments of the above-mentioned 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, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, Examples include p-stylyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. The content of the functional silane compound is preferably 0.1 to 30 parts by mass per 100 parts by mass of the polymer component contained in the liquid crystal orientation agent, and more preferably 0.1 to 20 parts by mass.

[0119] The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected considering viscosity, volatility, etc., but is preferably 1 to 10 mass%.

[0120] The particularly preferred range of solid content concentration varies depending on the method used when applying the liquid crystal alignment agent to the substrate. For example, when using the spin coating method, it is particularly preferable that the solid content concentration be 1.5 to 4.5 mass%. When using the printing method, it is particularly preferable to set the solid content concentration to 3 to 9 mass%, thereby setting the solution viscosity to 12 to 50 mPa·s. When using the inkjet method, it is particularly preferable to set the solid content concentration to 1 to 5 mass%, thereby setting the solution viscosity to 3 to 15 mPa·s. The temperature at which the polymer composition is prepared is preferably 10 to 50°C, and more preferably 20 to 30°C.

[0121] (Liquid crystal alignment layer and liquid crystal display element)

[0122] A liquid crystal display element related to the present invention comprises a liquid crystal alignment layer formed using the liquid crystal alignment agent. The operating mode of the liquid crystal display element is not specifically limited and can be applied to various operating modes, such as, for example, TN type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type (IPS type, FFS type), optical compensation band type (OCB type), etc.

[0123] The liquid crystal display element of the present invention can be manufactured, for example, by a method including the following processes (1) to (4), a method including processes (1) to (2) and (4), a method including processes (1) to (3), (4-2) and (4-4), or a method including processes (1) to (3), (4-3) and (4-4).

[0124] <Process (1): Process of applying a liquid crystal alignment agent onto a substrate>

[0125] Process (1) is a process of applying a liquid crystal alignment agent onto a substrate. A specific example of process (1) is as follows.

[0126] A liquid crystal alignment agent is applied to one side of a substrate on which a patterned transparent conductive film is formed, using an appropriate coating method such as a roll coater, spin coater, printing, or inkjet method. Here, the material of the substrate is not particularly limited as long as it is a highly transparent substrate, and plastics such as acrylic and polycarbonate may be used in addition to glass and silicon nitride. Furthermore, in the case of a reflective liquid crystal display device, if only one side of the substrate is opaque, such as a silicon wafer, may be used, and in this case, a light-reflecting material such as aluminum may be used for the electrode. In addition, when manufacturing an IPS-type or FFS-type liquid crystal display device, a substrate on which an electrode consisting of a comb-patterned transparent conductive film or a metal film is formed, and a counter substrate on which no electrode is formed are used.

[0127] Methods for forming a film by applying a liquid crystal alignment agent to a substrate include screen printing, offset printing, flexographic printing, inkjet printing, or spraying. Among these, the coating and film formation method using inkjet printing can be preferably used.

[0128] <Process (2): Process of firing the coated liquid crystal alignment agent>

[0129] Process (2) is a process of forming a film by firing a liquid crystal orientation agent applied on a substrate. Specific examples of process (2) are as follows.

[0130] After applying the liquid crystal alignment agent onto the substrate in process (1), the solvent may be evaporated or the polyamic acid may be thermoimidized using a heating means such as a hot plate, a thermal circulation type oven, or an IR (infrared) type oven. The drying and firing processes after applying the liquid crystal alignment agent may be performed at any temperature and time, and may be performed multiple times. The temperature at which the liquid crystal alignment agent is fired may be, for example, 40 to 180°C. From the perspective of shortening the process, it may be performed at 40 to 150°C. The firing time is not particularly limited, but 1 to 10 minutes or 1 to 5 minutes may be used. When thermoimidizing the polyamic acid, a firing process may be added after the above process, for example, at 150 to 300°C or 150 to 250°C. Although the firing time is not specifically limited, a firing time of 5 to 40 minutes or 5 to 30 minutes can be used.

[0131] Since the film thickness of the film after firing may be 5 to 300 nm, and more preferably 10 to 200 nm, because if it is excessively thin, the reliability of the liquid crystal display device may be reduced.

[0132] <Process (3): Process of orientation treatment on the film obtained in Process (2)>

[0133] Process (3) is, in some cases, a process of aligning the film obtained in process (2). That is, in a horizontal alignment type liquid crystal display device such as the IPS method or FFS method, an alignment ability imparting treatment is performed on the film. On the other hand, in a vertical alignment type liquid crystal display device such as the VA method or PSA mode, the formed film can be used as a liquid crystal alignment film as is, but an alignment ability imparting treatment may be applied to the film. Methods for aligning the liquid crystal alignment film include rubbing treatment and photo-alignment treatment. As for the photo-alignment treatment method, a method of imparting liquid crystal alignment (also called liquid crystal alignment ability) can be used by irradiating the surface of the film with radiation polarized in a certain direction and, in some cases, preferably by performing a heat treatment at a temperature of 150 to 250°C. As radiation, ultraviolet or visible light having a wavelength of 100 to 800 nm can be used. Among these, it is preferably ultraviolet light having a wavelength of 100 to 400 nm, more preferably 200 to 400 nm.

[0134] The irradiation dose of the above radiation is preferably 1 to 10,000 mJ / cm², and among them, 100 to 5,000 mJ / cm² is more preferable. In addition, when irradiating with radiation, in order to improve liquid crystal alignment, the substrate having the above film may be irradiated while heating it at 50 to 250°C. The liquid crystal alignment film manufactured in this way can stably align liquid crystal molecules in a certain direction.

[0135] In addition, by the above method, the liquid crystal alignment layer irradiated with polarized radiation may be contact-treated using water or a solvent, or the liquid crystal alignment layer irradiated with radiation may be heat-treated.

[0136] The solvent used for the above contact treatment is not particularly limited as long as it is a solvent that dissolves the decomposition product generated from the film material by irradiation with radiation. 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, cyclohexyl acetate, etc. The solvent may be of one type or may be a combination of two or more types.

[0137] The temperature of the heat treatment for the coating film irradiated with the above-mentioned radiation is more preferably 50 to 300 ℃, and more preferably 120 to 250 ℃. The time of the heat treatment is preferably 1 to 30 minutes for each.

[0138] <Process (4): Process for manufacturing liquid crystal cells>

[0139] Two substrates having a liquid crystal alignment layer formed thereon are prepared as described above, and a liquid crystal composition is placed between the two opposing substrates. Specifically, the following two methods may be cited.

[0140] The first method first arranges two substrates facing each other with a gap (cell gap) between them so that each liquid crystal alignment film faces the other. Then, the periphery of the two substrates is bonded using a sealant, and a liquid crystal composition is injected and filled into the cell gap partitioned by the substrate surface and the sealant, and then the injection hole is sealed after contact with the film surface.

[0141] In addition, the second method is a technique called the ODF (One Drop Fill) method. For example, a UV-curable sealant is applied to a predetermined location on one of two substrates on which a liquid crystal alignment film is formed, and a liquid crystal composition is dropped onto several predetermined points on the surface of the liquid crystal alignment film. Then, the other substrate is laminated so that the liquid crystal alignment films face each other, and the liquid crystal composition is spread widely over the entire surface of the substrate and brought into contact with the film surface. Subsequently, the sealant is cured by irradiating ultraviolet light onto the entire surface of the substrate. In either method, it is additionally preferable to remove the flow alignment during liquid crystal filling by heating the liquid crystal composition used to a temperature at which it takes on an isotropic phase, and then slowly cooling it to room temperature.

[0142] In addition, when rubbing treatment is performed on the coating film, the two substrates are arranged facing each other so that the rubbing direction in each coating film is at a predetermined angle to each other, for example, orthogonal or antiparallel.

[0143] As a sealing agent, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer may be used. As for the liquid crystal composition, there are no particular limitations, and as a composition containing at least one liquid crystal compound (liquid crystal molecule), examples include a liquid crystal composition exhibiting a nematic phase (hereinafter also referred to as a nematic liquid crystal), a liquid crystal exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase, among which a nematic liquid crystal is preferred. In addition, various liquid crystal compositions having positive or negative dielectric anisotropy may be used. Furthermore, hereinafter, a liquid crystal composition having positive dielectric anisotropy is referred to as a positive liquid crystal, and a liquid crystal composition having negative dielectric anisotropy is referred to as a negative liquid crystal.

[0144] The above liquid crystal composition may contain a liquid crystal compound having a fluorine atom, a hydroxyl group, an amino group, a fluorine atom-containing group (e.g., a trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocyclic ring, a cycloalkane, a cycloalkene, a steroid backbone, a benzene ring, or a naphthalene ring, or may contain a compound having two or more rigid sites (methogen backbones) that exhibit liquid crystallization within the molecule (e.g., two rigid biphenyl structures, or a bimethogen compound in which a terphenyl structure is connected to an alkyl group).

[0145] In addition, the liquid crystal composition may further contain additives to improve liquid crystal orientation. Such additives may include photopolymerizable monomers such as compounds having polymerizable groups; optically active compounds (e.g., S-811 manufactured by Merck & Co., Ltd.); antioxidants; ultraviolet absorbers; pigments; antifoaming agents; polymerization initiators; or polymerization inhibitors.

[0146] Examples of positive liquid crystals include Merck's ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, or MLC-7081.

[0147] Examples of negative liquid crystals include Merck's MLC-6608, MLC-6609, MLC-6610, MLC-7026, or MLC-7026-100.

[0148] In addition, as a liquid crystal containing a compound having a polymerizable group, Merck's MLC-3023 can be cited.

[0149] The liquid crystal alignment agent of the present invention is preferably used in a liquid crystal display device (PSA type liquid crystal display device) manufactured by a process in which a liquid crystal composition containing a polymerizable compound that polymerizes by at least one of an active energy line and heat is disposed between a pair of substrates having a liquid crystal layer between them and a voltage is applied between the electrodes, and the polymerizable compound is polymerized by at least one of irradiation of an active energy line and heating.

[0150] In addition, the liquid crystal alignment agent of the present invention may have a liquid crystal layer between a pair of substrates equipped with electrodes, and may also be preferably used in a liquid crystal display device (SC-PVA mode type liquid crystal display device) manufactured by placing a liquid crystal alignment film containing a polymerizable group that polymerizes by at least one of an active energy line and heat between the pair of substrates and applying a voltage between the electrodes.

[0151] <Process (4-2): Case of PSA type liquid crystal display device>

[0152] Except for injecting or dropping a liquid crystal composition containing a polymerizable compound, the above (4) is carried out in the same manner. Examples of polymerizable compounds include polymerizable compounds having one or more polymerizable unsaturated groups in the molecule, such as acrylate groups or methacrylate groups.

[0153] <Process (4-3): Case of SC-PVA mode type liquid crystal display device>

[0154] After doing the same as in (4) above, a method of manufacturing a liquid crystal display device may be adopted by undergoing a process of irradiating ultraviolet light as described later. According to this method, a liquid crystal display device with excellent response speed can be obtained with a small amount of light irradiation, just as in the case of manufacturing a PSA type liquid crystal display device. The compound having a polymerizable group may be a compound having one or more of the polymerizable unsaturated groups in its molecule, and the content thereof is preferably 0.1 to 30 parts by mass per 100 parts by mass of all polymer components, and more preferably 1 to 20 parts by mass. In addition, the polymerizable group may have a polymer used as a liquid crystal alignment agent, and such a polymer may be, for example, a polymer obtained by using a diamine component containing a diamine having the photopolymerizable group at the terminal end in the reaction.

[0155] <Process (4-4): Ultraviolet Irradiation Process>

[0156] Light is irradiated onto a liquid crystal cell 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 direct current or alternating current. In addition, as the irradiating light, ultraviolet and visible light including light with a wavelength of 150 to 800 nm can be used, for example, but ultraviolet light including light with a wavelength of 300 to 400 nm is preferred. As a light source for the irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc., can be used. The amount of light irradiated is preferably 1,000 to 200,000 J / m², and more preferably 1,000 to 100,000 J / m².

[0157] In addition, a liquid crystal display device can be obtained by laminating a polarizer to the outer surface of a liquid crystal cell as needed. Examples of polarizers laminated to the outer surface of a liquid crystal cell include a polarizer in which a polarizing film called an "H film," which absorbs iodine while polyvinyl alcohol is stretched and oriented, is sandwiched between cellulose acetate protective films, or a polarizer consisting of the H film itself.

[0158] An IPS substrate, which is a comb electrode substrate used in an IPS mode, has a substrate, a plurality of linear electrodes formed on the substrate and arranged in a comb shape, and a liquid crystal alignment layer formed to cover the linear electrodes on the substrate.

[0159] In addition, the FFS substrate, which is a comb electrode substrate used in the FFS mode, comprises a substrate, a surface electrode formed on the substrate, an insulating film formed on the surface electrode, a plurality of linear electrodes formed on the insulating film and arranged in a comb shape, and a liquid crystal alignment film formed to cover the linear electrodes on the insulating film.

[0160] FIG. 1 is a schematic partial cross-sectional view showing an example of a transverse electric field liquid crystal display element of the present invention, and is an example of an IPS mode liquid crystal display element.

[0161] In the transverse electric field liquid crystal display element (1) exemplified in FIG. 1, a liquid crystal (3) is clamped between a comb electrode substrate (2) having a liquid crystal alignment layer (2c) and a counter substrate (4) having a liquid crystal alignment layer (4a). The comb electrode substrate (2) has a substrate (2a), a plurality of linear electrodes (2b) formed on the substrate (2a) and arranged in a comb shape, and a liquid crystal alignment layer (2c) formed to cover the linear electrodes (2b) on the substrate (2a). The counter substrate (4) has a substrate (4b) and a liquid crystal alignment layer (4a) formed on the substrate (4b). The liquid crystal alignment layer (2c) is, for example, a liquid crystal alignment layer of the present invention. The liquid crystal alignment layer (4c) is also likewise a liquid crystal alignment layer of the present invention.

[0162] In this horizontal electric field liquid crystal display element (1), when voltage is applied to the linear electrodes (2b), an electric field is generated between the linear electrodes (2b) as indicated by the electric field lines (L).

[0163] FIG. 2 is a schematic partial cross-sectional view showing another example of a transverse electric field liquid crystal display element of the present invention, and is an example of an FFS mode liquid crystal display element.

[0164] In the transverse electric field liquid crystal display element (1) exemplified in FIG. 2, a liquid crystal (3) is clamped between a comb electrode substrate (2) having a liquid crystal alignment layer (2h) and a counter substrate (4) having a liquid crystal alignment layer (4a). The comb electrode substrate (2) has a substrate (2d), a surface electrode (2e) formed on the substrate (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 shape, and a liquid crystal alignment layer (2h) formed to cover the linear electrodes (2g) on ​​the insulating film (2f). The counter substrate (4) has a substrate (4b) and a liquid crystal alignment layer (4a) formed on the substrate (4b). The liquid crystal alignment layer (2h) is, for example, the liquid crystal alignment layer of the present invention. The liquid crystal alignment layer (4a) is also the liquid crystal alignment layer of the present invention.

[0165] In this horizontal electric field liquid crystal display element (1), when voltage is applied to the surface electrode (2e) and the line electrode (2), an electric field is generated between the surface electrode (2e) and the line electrode (2g), as indicated by the electric field line (L).

[0166] Examples

[0167] The present invention will be explained in more detail below with reference to examples, but the present invention is not to be interpreted as being limited to these. The abbreviations of the compounds used and the methods for measuring each physical property are as follows.

[0168] (Organic solvent)

[0169] NMP: N-methyl-2-pyrrolidone, GBL: γ-butyrolactone,

[0170] BCS: Butyl cellosolve, BCA: Butyl cellosolve acetate

[0171] THF: Tetrahydrofuran, DMF: N,N-Dimethylformamide

[0172] (Acid 2 anhydrous)

[0173] [Chemical Formula 10]

[0174]

[0175] (Diamine)

[0176] [Chemical Formula 11]

[0177]

[0178] (Additives)

[0179] [Chemical Formula 12]

[0180]

[0181] <Measurement of Viscosity>

[0182] Measurements were taken using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample volume of 1.1 mL, and a cone rotor TE-1 (1°34', R24) at a temperature of 25 ℃.

[0183] <Measurement of Molecular Weight>

[0184] Mn and Mw were calculated by measuring with the following room temperature GPC (gel penetration chromatography) apparatus and as polyethylene glycol and polyethylene oxide equivalent values.

[0185] GPC apparatus: GPC-101 (manufactured by Showa Densha), Columns: GPC KD-803, GPC KD-805 (manufactured by Showa Densha) in series, Column temperature: 50 ℃, Eluent: N,N-dimethylformamide (as additives: lithium bromide monohydrate (LiBr·H2O) 30 mmol / L, crystalline anhydrous phosphoric acid (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L), Flow rate: 1.0 mL / min

[0186] Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weights; approx. 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Co.) and polyethylene glycol (molecular weights; approx. 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratory Co.).

[0187] [Synthesis of Monomers]

[0188] DA-1 to DA-3 are novel compounds not disclosed in literature, etc., and the products in the following monomer synthesis examples 1 to 3 are 1 Identification was performed by H-NMR analysis. The analysis conditions are as follows.

[0189] Device: BRUKER ADVANCE III-500 MHz

[0190] Measurement solvent: Deuterium dimethyl sulfoxide (DMSO-d6)

[0191] Reference substance: Tetramethylsilane (TMS) (δ 0.0 ppm for 1 H)

[0192] <Monomer Synthesis Example 1: Synthesis of DA-1>

[0193] [Chemical Formula 13]

[0194]

[0195] To 2-(4-nitrophenoxy)ethanol (30.0 g, 0.164 mol), THF (120 g) and pyridine (14.0 g, 0.177 mol) were added, and the mixture was stirred while cooling in an ice bath (0 ℃). To the resulting solution, adipic acid dichloride (17.0 g, 0.0929 mol) dissolved in THF (60 g) was added dropwise. After the dropwise addition was finished, the mixture was stirred at room temperature (25 ℃) for 20 minutes, and then stirred at 45 ℃ for 18 hours. After the reaction was finished, the mixture was cooled to room temperature (25 ℃), and water (540 g) was added to precipitate crystals. The crystals obtained by filtration were dried to obtain crude crystals (39 g). THF (300 g) was added to the crude crystals and heated and stirred at 70 ℃, and recrystallized by adding methanol (400 g) while cooling in an ice bath (0 ℃). This was filtered, and the obtained crystals were dried to obtain DA-1-1 (quantity: 34.0 g, 0.0713 mol, yield 88%).

[0196]

[0197] To the DA-1-1 (29.0 g, 0.0609 mol) obtained above, DMF (290 g) was added to purge the nitrogen, then carbon-supported palladium (5% Pd carbon powder (hydrated) Type K, manufactured by N·E·Kemkat Co.) (2.32 g) was added and purge the nitrogen again, and a hydrogen Tedler bag was installed and heated and stirred at 50°C for 18 hours. After the reaction was finished, the carbon-supported palladium was removed by passing it through a membrane filter, and water (1000 g) was added to the filtrate and stirred to precipitate crystals. This was filtered to obtain crude crystals (24 g). THF (92 g) was added to the crude crystals and heated and stirred at 50°C to wash the slurry, then cooled in an ice bath (0°C), filtered, and the obtained crystals were dried to obtain crystals (22 g). DMF (66 g) was added to the obtained crystals and heated and stirred at 50 ℃, then cooled in an ice bath (0 ℃), and then acetonitrile (88 g) was added to recrystallize. This was filtered, and the obtained crystals were dried to obtain DA-1 (quantity: 17.0 g, 0.0408 mol, yield 67%).

[0198]

[0199] <Monomer Synthesis Example 2: Synthesis of DA-2>

[0200] [Chemical Formula 14]

[0201]

[0202] DMF (210 g) and potassium carbonate (48.0 g, 0.347 mol) were added to 4'-hydroxy-4-nitrobiphenyl (30.0 g, 0.139 mol), and the mixture was heated and stirred at 80 °C for 30 minutes. To the resulting solution, 2-bromoethanol (26 g, 0.208 mol) dissolved in DMF (30 g) was added dropwise, and the mixture was heated and stirred at 80 °C for 18 hours. After the reaction was finished, the mixture was cooled to room temperature (25 °C), and water (480 g) was added to precipitate crystals. The mixture was filtered, and the obtained crystals were dried. Methanol was added to the filtrate, and the mixture was heated and stirred at 50 °C to wash the slurry. After cooling to room temperature (25 °C), the mixture was filtered. After concentrating the filtrate, tertiary crystals were extracted using the same procedure, and the obtained crystals were dried to obtain DA-2-1 (quantity: 31.0 g, 0.120 mol, yield 86%).

[0203]

[0204] To the DA-2-1 (26.0 g, 0.100 mol) obtained above, THF (230 g) and pyridine (8.20 g, 0.104 mol) were added, and the mixture was stirred while cooling in an ice bath (0 ℃). Adipic acid dichloride (9.9 g, 0.0541 mol) dissolved in THF (26 g) was added dropwise to this solution. After the dropwise addition was finished, the mixture was stirred at room temperature (25 ℃) for 5 hours, and then stirred at 45 ℃ for 1 hour. After the reaction was finished, the mixture was cooled to room temperature (25 ℃), and water (765 g) was added to precipitate crystals. This was filtered, and the obtained crystals were dried to obtain crude crystals (29 g). THF (290 g) was added to the crude crystals and heated and stirred at 60 ℃, then recrystallized by adding methanol (290 g) while cooling in an ice bath (0 ℃). This was filtered, and the obtained crystals were dried to obtain DA-2-2 (quantity: 24.0 g, 0.0382 mol, yield 76%).

[0205]

[0206] To the DA-2-2 (25.0 g, 0.0398 mol) obtained above, DMF (490 g) was added and nitrogen-substituted, then carbon-supported palladium (5% Pd carbon powder (hydrated) K type, manufactured by N·E·Kemkat Co.) (2.00 g) was added and nitrogen-substituted again, and a hydrogen Tedler bag was installed and stirred at room temperature (25 ℃) for 48 hours. After the reaction was finished, the carbon-supported palladium was removed by passing it through a membrane filter, and the filtrate was concentrated until crystals began to precipitate (residual amount of DMF: about 140 g). This was heated and stirred at 55 ℃ to completely dissolve it, cooled to room temperature (25 ℃), and acetonitrile (80 g) was added to precipitate crystals. This was filtered, and the obtained crystals were dried to obtain DA-2 (quantity: 20.0 g, 0.0352 mol, yield 88%).

[0207]

[0208] <Monomer Synthesis Example 3: Synthesis of DA-3>

[0209] [Chemical Formula 15]

[0210]

[0211] To 2-(4-nitrophenoxy)ethanol (35.7 g, 0.195 mol), THF (180 g) and pyridine (18.4 g, 0.232 mol) were added, and the mixture was stirred while cooling in an ice bath (0 ℃). Suberic acid dichloride (19.6 g, 0.0929 mol) dissolved in THF (60 g) was added dropwise to the resulting solution. After the dropwise addition was finished, the mixture was stirred at room temperature (25 ℃) for 20 minutes, and then stirred at 45 ℃ for 18 hours. After the reaction was finished, the mixture was cooled to room temperature (25 ℃), and water (400 g) was added to precipitate crystals. The crystals obtained by filtration were dried to obtain crude crystals (35 g). THF (180 g) was added to the crude crystals and heated and stirred at 70 ℃, and recrystallized by adding methanol (400 g) while cooling in an ice bath (0 ℃). This was filtered, and the obtained crystals were dried to obtain DA-3-1 (quantity: 30.9 g, 0.0613 mol, yield 66%).

[0212]

[0213] To the DA-3-1 (30.9 g, 0.0613 mol) obtained above, THF (770 g) was added to purge the nitrogen, and then carbon-supported palladium (5% Pd carbon powder (hydrated) Type K, manufactured by N·E·KemKat) (3.1 g) was added and purge the nitrogen again. A hydrogen Tedler bag was then installed, and the mixture was heated and stirred at 45°C for 24 hours. After the reaction was complete, the carbon-supported palladium was removed by passing it through a membrane filter, and the filtrate was concentrated. Then, while stirring, isopropyl alcohol (240 g) was added to precipitate crystals. This was filtered, and the obtained crystals were dried to obtain DA-3 (quantity: 24.9 g, 0.0560 mol, yield 91%).

[0214]

[0215] [Synthesis of Polymers]

[0216] <Synthesized Example 1>

[0217] DA-1 (2.29 g, 5.50 mmol) and NMP (16.8 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-1 (1.15 g, 5.27 mmol) and NMP (8.10 g) were added, and by stirring at 50 °C for 18 hours, a solution of polyamic acid (A-1) with a solid content concentration of 12 mass% (viscosity: 239 mPa·s) was obtained. The Mn of this polyamic acid was 10,094 and the Mw was 33,198.

[0218] <Synthesized Example 2>

[0219] DA-1 (2.54 g, 6.10 mmol) and NMP (18.6 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-2 (1.14 g, 5.81 mmol) and NMP (8.00 g) were added, and stirred at room temperature for 18 hours to obtain a solution of polyamic acid (A-2) with a solid content concentration of 12 mass% (viscosity: 241 mPa·s). The Mn of this polyamic acid was 12,332 and the Mw was 46,258.

[0220] <Synthesized Example 3>

[0221] DA-1 (3.12 g, 7.50 mmol) and NMP (22.9 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-3 (1.60 g, 7.14 mmol) and NMP (10.8 g) were added, and by stirring at 40 °C for 18 hours, a solution of polyamic acid (A-3) with a solid content concentration of 12 mass% (viscosity: 282 mPa·s) was obtained. The Mn of this polyamic acid was 10,704 and the Mw was 39,144.

[0222] <Synthesized Example 4>

[0223] DA-3 (2.58 g, 5.80 mmol) and NMP (23.2 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-3 (1.21 g, 5.40 mmol) and NMP (4.4 g) were added, and by stirring at 40 °C for 18 hours, a solution of polyamic acid (A-4) with a solid content concentration of 12 mass% (viscosity: 190 mPa·s) was obtained. The Mn of this polyamic acid was 10,832 and the Mw was 43,395.

[0224] <Synthesized Example 5>

[0225] DA-1 (2.27 g, 5.44 mmol), DA-6 (0.390 g, 1.36 mmol), and NMP (19.5 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-3 (1.45 g, 6.46 mmol) and NMP (10.1 g) were added, and by stirring at 40 °C for 18 hours, a solution of polyamic acid (A-5) with a solid content concentration of 12 mass% (viscosity: 327 mPa·s) was obtained. The Mn of this polyamic acid was 10,534, and the Mw was 37,647.

[0226] <Synthesized Example 6>

[0227] DA-1 (1.46 g, 3.50 mmol), DA-6 (1.00 g, 3.50 mmol), and NMP (18.0 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-3 (1.48 g, 6.58 mmol) and NMP (10.8 g) were added, and by stirring at 40 °C for 18 hours, a solution of polyamic acid (A-6) with a solid content concentration of 12 mass% (viscosity: 225 mPa·s) was obtained. The Mn of this polyamic acid was 10,400 and the Mw was 25,285.

[0228] <Synthesized Example 7>

[0229] DA-1 (0.73 g, 1.75 mmol), DA-6 (1.50 g, 5.24 mmol), and NMP (20.1 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-3 (1.47 g, 6.56 mmol) and NMP (6.9 g) were added, and by stirring at 40 °C for 18 hours, a solution of polyamic acid (A-7) with a solid content concentration of 12 mass% (viscosity: 236 mPa·s) was obtained. The Mn of this polyamic acid was 10,634 and the Mw was 31,097.

[0230] <Synthesized Example 8>

[0231] DA-3 (0.80 g, 1.80 mmol), DA-6 (1.55 g, 5.41 mmol), and NMP (21.1 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-3 (1.52 g, 6.78 mmol) and NMP (7.0 g) were added, and by stirring at 40 °C for 18 hours, a solution of polyamic acid (A-8) with a solid content concentration of 12 mass% (viscosity: 209 mPa·s) was obtained. The Mn of this polyamic acid was 9,900 and the Mw was 28,856.

[0232] <Synthesized Example 9>

[0233] DA-1 (1.67 g, 4.01 mmol), DA-4 (0.98 g, 4.01 mmol), and NMP (23.8 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-1 (1.63 g, 7.47 mmol) and NMP (7.6 g) were added, and by stirring at 50 °C for 18 hours, a solution of polyamic acid (A-9) with a solid content concentration of 12 mass% (viscosity: 300 mPa·s) was obtained. The Mn of this polyamic acid was 9,351 and the Mw was 31,020.

[0234] <Synthesized Example 10>

[0235] DA-2 (2.50 g, 4.40 mmol) and NMP (19.6 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-1 (0.873 g, 4.00 mmol) and NMP (5.10 g) were added, and by stirring at 50 °C for 18 hours, a solution of polyamic acid (A-10) with a solid content concentration of 12 mass% (viscosity: 231 mPa·s) was obtained. The Mn of this polyamic acid was 9,716 and the Mw was 25,390.

[0236] <Synthesized Example 11>

[0237] DA-2 (2.79 g, 4.90 mmol) and NMP (20.4 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-2 (0.88 g, 4.49 mmol) and NMP (6.35 g) were added, and stirred at room temperature for 18 hours to obtain a solution of polyamic acid (A-11) with a solid content concentration of 12 mass% (viscosity: 230 mPa·s). The Mn of this polyamic acid was 11,774 and the Mw was 32,286.

[0238] <Synthesized Example 12>

[0239] DA-6 (3.72 g, 13.0 mmol) and NMP (31.3 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. CA-2 (2.37 g, 12.1 mmol) and NMP (13.4 g) were added to the obtained diamine solution while stirring under water cooling, and stirred at room temperature for 18 hours to obtain a solution of polyamic acid (A-12) with a solid content concentration of 12 mass% (viscosity: 229 mPa·s). The Mn of this polyamic acid was 10,585 and the Mw was 27,581.

[0240] <Synthesized Example 13>

[0241] DA-7 (2.46 g, 6.40 mmol) and NMP (18.0 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-2 (1.23 g, 6.26 mmol) and NMP (8.40 g) were added, and by stirring at room temperature for 18 hours, a solution of polyamic acid (A-13) with a solid content concentration of 12 mass% (viscosity: 292 mPa·s) was obtained. The Mn of this polyamic acid was 16,511 and the Mw was 60,289.

[0242] <Synthesized Example 14>

[0243] DA-5 (2.07 g, 8.01 mmol) and NMP (18.6 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. CA-1 (1.65 g, 7.56 mmol) and NMP (14.8 g) were added to the obtained diamine solution while stirring under water cooling, and stirred at 50 °C for 18 hours to obtain a solution of polyamic acid (A-14) with a solid content concentration of 10 mass% (viscosity: 115 mPa·s). The Mn of this polyamic acid was 12,045 and the Mw was 27,326.

[0244] <Synthesized Example 15>

[0245] DA-6 (3.72 g, 13.0 mmol) and NMP (37.3 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-1 (2.64 g, 12.1 mmol) and NMP (9.30 g) were added, and by stirring at 50 °C for 18 hours, a solution of polyamic acid (A-15) with a solid content concentration of 12 mass% (viscosity: 278 mPa·s) was obtained. The Mn of this polyamic acid was 10,832 and the Mw was 43,395.

[0246] <Synthesized Example 16>

[0247] DA-7 (3.08 g, 8.00 mmol) and NMP (22.6 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-1 (1.61 g, 7.36 mmol) and NMP (11.8 g) were added, and by stirring at 50 °C for 18 hours, a solution of polyamic acid (A-16) with a solid content concentration of 12 mass% (viscosity: 256 mPa·s) was obtained. The Mn of this polyamic acid was 10,700 and the Mw was 37,763.

[0248] <Synthesized Example 17>

[0249] DA-6 (2.29 g, 8.00 mmol) and NMP (16.8 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-3 (1.69 g, 7.52 mmol) and NMP (12.4 g) were added, and by stirring at 40 °C for 18 hours, a solution of polyamic acid (A-17) with a solid content concentration of 12 mass% (viscosity: 240 mPa·s) was obtained. The Mn of this polyamic acid was 11,482 and the Mw was 38,490.

[0250] <Synthesized Example 18>

[0251] DA-7 (2.69 g, 7.00 mmol) and NMP (19.7 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-3 (1.54 g, 6.86 mmol) and NMP (10.1 g) were added, and by stirring at 40 °C for 18 hours, a solution of polyamic acid (A-18) with a solid content concentration of 12 mass% (viscosity: 283 mPa·s) was obtained. The Mn of this polyamic acid was 13,087 and the Mw was 45,255.

[0252] <Synthesized Example 19>

[0253] DA-8 (1.28 g, 6.42 mmol), DA-10 (0.32 g, 1.61 mmol), and NMP (14.3 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. CA-2 (1.49 g, 7.60 mmol) and NMP (13.3 g) were added to the obtained diamine solution while stirring under water cooling, and stirred at room temperature for 18 hours to obtain a solution of polyamic acid (A-19) with a solid content concentration of 10 mass% (viscosity: 125 mPa·s). The Mn of this polyamic acid was 11,120 and the Mw was 41,992.

[0254] <Synthesized Example 20>

[0255] DA-8 (2.99 g, 15.0 mmol), DA-9 (2.11 g, 5.01 mmol), DA-10 (0.99 g, 4.99 mmol), and NMP (44.6 g) were added to a 100 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. While stirring the obtained diamine solution under water cooling, CA-2 (4.51 g, 23.0 mmol) and NMP (15.4 g) were added, and by stirring at room temperature for 18 hours, a solution of polyamic acid (A-20) with a solid content concentration of 15 mass% (viscosity: 592 mPa·s) was obtained. The Mn of this polyamic acid was 12,080 and the Mw was 32,115.

[0256] <Synthesized Example 21>

[0257] DA-8 (5.42 g, 27.2 mmol), DA-10 (1.35 g, 6.80 mmol), and NMP (64.5 g) were added to a 100 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. CA-2 (1.53 g, 7.82 mmol) and NMP (10.2 g) were added to the obtained diamine solution while stirring under water cooling, and stirred at room temperature for 0.5 hours. Subsequently, CA-4 (6.38 g, 25.5 mmol) and NMP (8.50 g) were added to the solution while stirring under water cooling, and stirred at 50 °C for 18 hours to obtain a solution of polyamic acid (A-21) with a solid content concentration of 15 mass% (viscosity: 1,250 mPa·s). The Mn of this polyamic acid was 15,100, and the Mw was 54,900.

[0258] <Synthesized Example 22>

[0259] DA-4 (0.98 g, 4.00 mmol), DA-8 (0.78 g, 4.00 mmol), and NMP (10.1 g) were added to a 50 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. CA-4 (1.50 g, 6.00 mmol) and NMP (8.50 g) were added to the obtained diamine solution while stirring under water cooling, and stirred at 50 °C for 2 hours. Subsequently, CA-5 (0.49 g, 1.68 mmol) and NMP (2.80 g) were added to the solution while stirring under water cooling, and stirred at 50 °C for 18 hours to obtain a solution of polyamic acid (A-22) with a solid content concentration of 15 mass% (viscosity: 315 mPa·s). The Mn of this polyamic acid was 9,491, and the Mw was 26,134.

[0260] <Synthesized Example 23>

[0261] DA-4 (2.81 g, 11.5 mmol), DA-8 (2.29 g, 11.5 mmol), and NMP (45.9 g) were added to a 100 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. CA-4 (2.88 g, 11.5 mmol) and NMP (15.4 g) were added to the obtained diamine solution while stirring under water cooling, and stirred at 50 °C for 2 hours. Subsequently, CA-5 (2.86 g, 9.72 mmol) and NMP (2.8 g) were added to the solution while stirring under water cooling, and stirred at 50 °C for 18 hours to obtain a solution of polyamic acid (A-23) with a solid content concentration of 15 mass% (viscosity: 298 mPa·s). The Mn of this polyamic acid was 8,290, and the Mw was 22,181.

[0262] <Synthesized Example 24>

[0263] DA-4 (2.81 g, 11.5 mmol), DA-8 (2.29 g, 11.5 mmol), and NMP (45.9 g) were added to a 100 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. CA-6 (2.58 g, 11.5 mmol) and NMP (10.4 g) were added to the obtained diamine solution while stirring under water cooling, and stirred at room temperature for 2 hours. Subsequently, CA-5 (2.87 g, 9.72 mmol) and NMP (3.3 g) were added to the solution while stirring under water cooling, and stirred at 50 °C for 18 hours to obtain a solution of polyamic acid (A-24) with a solid content concentration of 15 mass% (viscosity: 300 mPa·s). The Mn of this polyamic acid was 9,018, and the Mw was 27,228.

[0264] <Synthesized Example 25>

[0265] DA-8 (4.14 g, 20.8 mmol), DA-10 (1.03 g, 5.19 mmol), and NMP (46.6 g) were added to a 100 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. CA-2 (2.20 g, 11.4 mmol) and NMP (7.50 g) were added to the obtained diamine solution while stirring under water cooling, and stirred at room temperature for 0.5 hours. Subsequently, CA-4 (3.25 g, 13.0 mmol) and NMP (6.20 g) were added to the solution while stirring under water cooling, and stirred at 50 °C for 18 hours to obtain a solution of polyamic acid (A-25) with a solid content concentration of 15 mass% (viscosity: 535 mPa·s). The Mn of this polyamic acid was 10,218, and the Mw was 29,128.

[0266] <Synthesized Example 26>

[0267] DA-8 (5.42 g, 27.2 mmol), DA-10 (1.35 g, 6.80 mmol), and NMP (64.5 g) were added to a 100 mL 4-neck flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. CA-2 (1.48 g, 7.55 mmol) and NMP (10.2 g) were added to the obtained diamine solution while stirring under water cooling, and stirred at room temperature for 0.5 hours. Subsequently, CA-4 (6.38 g, 25.5 mmol) and NMP (8.50 g) were added to the solution while stirring under water cooling, and stirred at 50 °C for 18 hours to obtain a solution of polyamic acid (A-26) with a solid content concentration of 15 mass% (viscosity: 530 mPa·s). The Mn of this polyamic acid was 9,982, and the Mw was 28,927.

[0268] The types and amounts of tetracarboxylic acid components and diamine components used in the above synthesis examples 1 to 26 are shown in Table 1.

[0269]

[0270] [Preparation of Liquid Crystal Orientation Agent]

[0271] <Example 1>

[0272] NMP (0.17 g), GBL (5.53 g), BCS (1.80 g), and BCA (0.60 g) were added to a solution (3.90 g) of polyamic acid (A-2) obtained in Synthesis Example 2, and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (AL-1) in which the mass ratio of polymer solids to each solvent (polymer solids : NMP : GBL : BCS : BCA) was 4 : 30 : 46 : 15 : 5.

[0273] <Examples 2–6, and Comparative Examples 1–6>

[0274] By carrying out the same procedure as in Example 1, except that the polyamic acid solution used was changed as shown in Table 2, liquid crystal alignment agents AL-2 to AL-6 of Examples 2 to 6 and liquid crystal alignment agents AL-C1 to AL-C6 of Comparative Examples 1 to 6 were obtained.

[0275] <Example 7>

[0276] A liquid crystal aligning agent (AL-7) was obtained by adding a solution (0.90 g) of polyamic acid (A-3) obtained in Synthesis Example 3, a solution (2.88 g) of polyamic acid (A-21) obtained in Synthesis Example 21, NMP (4.68 g), BCS (3.00 g), and AD-1 (1 mass% NMP solution, 0.54 g) to the solution (0.90 g) of polyamic acid (A-3) obtained in Synthesis Example 3, stirring at room temperature for 2 hours, so that the mass ratio of the polymer ((A-3) : (A-15)) is 20 : 80, the mass ratio of the polymer solids to each solvent (polymer solids : NMP : BCS) is 4.5 : 70.5 : 25, and the mixing ratio of AD-1 to 100 mass parts of the polymer is 1 mass part.

[0277] <Examples 8–18, and Comparative Examples 7–10>

[0278] By operating in the same manner as in Example 7, except that the type or amount of the polyamic acid solution, solvent, and additive used was changed as shown in Table 2, liquid crystal aligners AL-8 to AL-18 of Examples 8 to 18 and liquid crystal aligners AL-C7 to AL-C10 of Comparative Examples 7 to 10 were obtained.

[0279]

[0280] In Table 2, the numbers in parentheses represent the ratio (parts by mass) of each polymer and additive to 100 parts by mass of the total polymer components.

[0281] [Manufacturing of Liquid Crystal Cells]

[0282] <Manufacturing of FFS driving liquid crystal cells for negative liquid crystals>

[0283] A liquid crystal cell for a negative liquid crystal was manufactured having the configuration of an FFS mode liquid crystal display element.

[0284] First, a substrate for electrode formation was prepared. A glass substrate with dimensions of 30 mm × 35 mm and a thickness of 0.7 mm was used. On the substrate, an ITO electrode having a beta pattern constituting a counter electrode was formed as the first layer, and a SiN (silicon nitride) film was formed as the second layer by the CVD (chemical vapor deposition) method on the counter electrode of the first layer. The second layer SiN film used had a thickness of 300 nm and functioned as an interlayer insulating film. On the second layer SiN film, a comb-shaped pixel electrode formed by patterning an ITO film as the third layer was disposed, and two pixels, a first pixel and a second pixel, were formed. The size of each pixel was 10 mm in height and approximately 5 mm in width. At this time, the first layer counter electrode and the third layer pixel electrode were electrically insulated by the action of the second layer SiN film.

[0285] The pixel electrode of the third layer had a comb shape in which multiple electrode elements with a width of 3 μm, each having a central portion curved at an internal angle of 160°, were arranged parallel to each other at a distance of 6 μm, and one pixel had a first region and a second region bordered by a line connecting the curved portions of the multiple electrode elements.

[0286] When comparing the first and second regions of each pixel, the formation direction of the electrode elements of the pixel electrodes constituting them was different. That is, based on the line connecting the curved portions of the multiple pixel electrode elements, the electrode elements of the pixel electrodes in the first region of the pixel were formed to form an angle of 80° clockwise, and the electrode elements of the pixel electrodes in the second region of the pixel were formed to form an angle of 80° counterclockwise. In other words, in the first and second regions of each pixel, the direction of rotational movement (in-plane switching) of the liquid crystal induced by the application of voltage between the pixel electrode and the counter electrode within the substrate surface was configured to be opposite to each other.

[0287] Next, the liquid crystal alignment agent obtained above was filtered through a filter with a pore size of 1.0 μm and then applied to the surface of the prepared electrode forming substrate by spin coating. After drying for 2 minutes on a hot plate at 80°C, the film was fired for 20 minutes in an infrared furnace at 230°C to obtain a polyimide film with a thickness of 60 nm. This polyimide film was subjected to rubbing alignment treatment with a rayon cloth (HY-5318 manufactured by Hyperflex, Inc.) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm, rubbing direction: 180° relative to the line connecting the curved portions of the plurality of pixel electrode elements of the third layer pixel electrode), then cleaned by ultrasonic irradiation in pure water for 1 minute, and water droplets were removed by air blowing. Afterwards, the substrate was dried at 80°C for 10 minutes to obtain a liquid crystal alignment film attached substrate. As a counter substrate, a glass substrate having a columnar spacer with a height of 4 μm and an ITO electrode formed on its back surface was treated in the same manner as above to obtain a liquid crystal alignment film attached substrate with an alignment treatment. These two liquid crystal alignment film attached substrates were paired, and a sealant (XN-1500T manufactured by Mitsui Chemical Co., Ltd.) was printed on one substrate in a shape leaving a liquid crystal injection port, and the other substrate was attached with the liquid crystal alignment film surface facing each other and the rubbing direction being antiparallel. Afterwards, a heat treatment was performed at 150°C for 60 minutes to cure the sealant, thereby producing an empty cell with a cell gap of 4 μm. A negative liquid crystal MLC-7026-100 (manufactured by Merck) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell of the FFS method for negative liquid crystals. After that, the obtained liquid crystal cell was heated at 120°C for 1 hour, left at 23°C overnight, and then used for evaluation.

[0288] <Manufacturing of FFS driving liquid crystal cells for positive liquid crystals>

[0289] A liquid crystal cell for a positive liquid crystal was manufactured having the configuration of an FFS mode liquid crystal display element.

[0290] The substrate for forming the electrode was the same as the FFS driving liquid crystal cell for the negative liquid crystal above.

[0291] A positive liquid crystal cell using the FFS method for a negative liquid crystal was obtained by operating in the same manner as the manufacturing method for an FFS driving liquid crystal cell for a negative liquid crystal, except that the rubbing direction in the substrate for forming the electrode was changed to a 90° direction with respect to the line connecting the curved portions of the plurality of pixel electrode elements of the third layer pixel electrode, and the liquid crystal injected by the pressure injection method was changed to a positive type liquid crystal MLC-3019 (manufactured by Merck). After that, the obtained liquid crystal cell was heated at 120°C for 1 hour, left at 23°C overnight, and then used for evaluation.

[0292] <Manufacture of a Liquid Crystal Cell for Negative Liquid Crystals for Evaluation of Pretilt Angle and Voltage Retention Rate>

[0293] First, a substrate for forming electrodes was prepared. The substrate is a glass substrate with dimensions of 30 mm × 40 mm and a thickness of 0.7 mm. An ITO electrode with a film thickness of 35 nm is formed on the substrate, and the electrode was used in a stripe pattern with a spacing of 40 mm vertically and 10 mm horizontally.

[0294] Next, the liquid crystal alignment agent obtained above was filtered through a filter with a pore size of 1.0 μm and then applied to the prepared electrode forming substrate by the spin coating method. After drying on a hot plate at 80°C for 2 minutes, the substrate was fired in an infrared furnace at 230°C for 20 minutes to form a film with a thickness of 60 nm, thereby obtaining a liquid crystal alignment film attached substrate. This liquid crystal alignment film was subjected to rubbing alignment treatment with a rayon cloth (HY-5318 manufactured by Hyperflex, Inc.) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm), then ultrasonic irradiated in pure water for 1 minute and cleaned, after which water droplets were removed by an air blow, and then dried at 80°C for 10 minutes to obtain a liquid crystal alignment film attached substrate. Two substrates with liquid crystal alignment films attached were prepared. Spherical spacers with a particle size of 4 μm were scattered on the liquid crystal alignment film surface of one substrate, leaving a liquid crystal injection port, and a sealant (XN-1500T manufactured by Mitsui Chemical Co., Ltd.) was printed around it. The other substrate was then attached with the rubbing direction reversed and the film surfaces facing each other. Afterward, a heat treatment was performed at 150°C for 60 minutes, and the sealant was cured to produce an empty cell. A negative liquid crystal MLC-7026-100 (manufactured by Merck) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell. Subsequently, the obtained liquid crystal cell was heated at 120°C for 1 hour, left overnight at 23°C, and then used for each evaluation.

[0295] <Manufacture of a Liquid Crystal Cell for Positive Liquid Crystals for Evaluation of Pretilt Angle and Voltage Retention Rate>

[0296] The substrate for forming the electrode was the same as that used for the liquid crystal cell for negative liquid crystal used for evaluating the pretilt angle and voltage retention rate. A liquid crystal cell for positive liquid crystal was obtained by operating in the same manner as the method for manufacturing the liquid crystal cell for negative liquid crystal used for evaluating the pretilt angle and voltage retention rate, except that the liquid crystal injected by the reduced pressure injection method was changed to positive type liquid crystal MLC-3019 (manufactured by Merck). After that, the obtained liquid crystal cell was heated at 120°C for 1 hour, left at 23°C overnight, and then used for evaluation.

[0297] [Evaluation of Liquid Crystal Cell Characteristics]

[0298] The characteristics of the FFS driving liquid crystal cell manufactured above and the liquid crystal cell for evaluating the pretilt angle and voltage retention rate were evaluated as follows.

[0299] <Evaluation of Voltage Retention Rate After Backlight Endurance Test>

[0300] The liquid crystal cell for evaluating the voltage retention rate was left for 96 hours under irradiation by a high-brightness backlight (light source: LED, brightness: 30,000 cd / m²) with a surface temperature of 50°C. Subsequently, a voltage of 1 V at a temperature of 60°C was applied to the liquid crystal cell for 60 μsec, and the voltage after 167 msec was measured to calculate the voltage retention rate, indicating how well the voltage could be maintained. A higher voltage retention rate value indicates better performance. Specifically, when using a liquid crystal cell for negative liquid crystals, it was evaluated as "○" if the voltage retention rate was 54% or higher, and "×" if it was lower than 54%. When using a liquid crystal cell for positive liquid crystals, it was evaluated as "○" if the voltage retention rate was 85% or higher, and "×" if it was lower than 85%. In addition, it is known that if the voltage retention rate, which is one of the electrical characteristics of a liquid crystal display element, increases, line burn-in, which is one of the display defects of the liquid crystal display element, does not occur easily.

[0301] <Evaluation of Afterimage by Long-Term AC Driving>

[0302] Using the FFS driving liquid crystal cell manufactured above, an AC voltage of ±5.5 V at a frequency of 30 Hz was applied for 96 hours under irradiation with a high-brightness backlight (light source: LED, brightness: 30000 cd / m²). After that, the pixel electrode and the counter electrode of the FFS driving liquid crystal cell were short-circuited, and the cell was left at room temperature for one day.

[0303] After leaving it undisturbed, the FFS driving liquid crystal cell was installed between two polarizers arranged so that their polarization axes were orthogonal, and the backlight was turned on in a state where no voltage was applied. The arrangement angle of the FFS driving liquid crystal cell was then adjusted so that the brightness of the transmitted light was minimized. Then, the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel becomes darkest to the angle at which the first region of the first pixel becomes darkest was calculated as angle Δ. In the same way, the same angle Δ was calculated for the second pixel by comparing the second region and the first region.

[0304] When this angle Δ is 0.1° or less, it is defined as having excellent afterimage characteristics, i.e., “○”, and when it is greater than 0.1°, it is defined as “×” and an evaluation was performed.

[0305] <Evaluation of Field of View Characteristics>

[0306] The pretilt angle in the liquid crystal cell for evaluating the pretilt angle was measured using an AxoScan Müller Matrix Polarimator manufactured by Opto Matrix Inc. The viewing angle characteristic is better when the value of the pretilt angle is lower. Specifically, it was evaluated as “○” when the pretilt angle is 1.7° or less, and “×” when it is greater than 1.7°.

[0307] Table 3 shows the results of the voltage retention rate, afterimage evaluation, and viewing angle characteristics of the liquid crystal cells for negative liquid crystals using each liquid crystal alignment agent of Examples 1 to 15 and Comparative Examples 1 to 9.

[0308]

[0309] As shown in Table 3, the liquid crystal display device using the liquid crystal alignment film of Examples 1 to 15 obtained from a liquid crystal alignment agent using a diamine component containing specific diamines DA-1 to DA-3 had good voltage retention rate, afterimage characteristics, and viewing angle characteristics.

[0310] Table 4 shows the results of the voltage retention rate, afterimage evaluation, and viewing angle characteristics of a liquid crystal cell for a positive liquid crystal using each liquid crystal alignment agent of Examples 16 to 18 and Comparative Examples 9 and 10.

[0311]

[0312] As shown in Table 4, the liquid crystal display device using the liquid crystal alignment film of Examples 16 to 18, obtained from a liquid crystal alignment agent using a diamine component containing specific diamines DA-1 to DA-3, had good voltage retention rate, afterimage characteristics, and viewing angle characteristics.

[0313] Industrial applicability

[0314] The liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is widely used in liquid crystal display devices of various operating modes, for example, it may be used as a liquid crystal alignment film for a phase difference film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmission scattering type liquid crystal light-diffusing device.

[0315] The liquid crystal display element of the present invention can be effectively applied to devices having various functions, and, for example, can be used in liquid crystal televisions, watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, information displays, etc.

[0316] In addition, the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2021-067838 filed on April 13, 2021 are incorporated herein by reference and accepted as the disclosure of the specification of the present invention. Explanation of the symbols

[0317] 1 : Transverse electric field liquid crystal display element, 2 : Comb electrode substrate, 2a, 4b, 2d : Entry, 2b, 2g : linear electrode, 2c, 2h, 4a : Liquid crystal alignment layer, 2e : surface electrode, 2f : insulating film, 3 : LCD, 4 : Opposing substrate, L: Electric field lines

Claims

Claim 1 A liquid crystal orientation agent characterized by containing at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1). (In Equation (1), X1 represents a tetravalent organic group. Y1 is a divalent organic group represented by "-Ar1-OWO-Ar2-". Ar1 and Ar2 each independently represent either a divalent aromatic group of a divalent benzene ring or a biphenyl structure, and any hydrogen atom of the aromatic group may be substituted with a monovalent group. W is *-(CH2) m -LA-* ( L represents -OC(=O)- or -C(=O)-O-, and A is -(CH2) n - represents. m is an integer from 1 to 6. n is an integer from 1 to 16. If n is 2 or greater, any -CH2- constituting A may be substituted with -O-, -C(=O)-, -OC(=O)-, or -C(=O)-O-. Also, some of the hydrogen atoms in W may be substituted with halogen atoms, methyl groups, trifluoromethyl groups, or hydroxyl groups.) It is a divalent organic group having 4 to 20 carbon atoms represented by *. * indicates a bond loss. R and Z each independently represent a hydrogen atom or a monovalent organic group.) Claim 2 In claim 1, the polymer is of the following formula (D A A liquid crystal orientation agent, comprising at least one polymer (P) selected from the group consisting of a polyimide precursor obtained using a diamine component containing a diamine (O) represented by ) and a polyimide which is an imid of the polyimide precursor. (Ar1, Ar2, and W are as defined in Paragraph 1.) Claim 3 In Clause 2, the above formula (D A W in ) is, *-(CH2) p -OC(=O)-(CH2) q -*, *-(CH2) p -OC(=O)-(CH2) q -C(=O)-O-(CH2) r -*, or *-(CH2) p -C(=O)-O-(CH2) q -OC(=O)-(CH2) r -* and, p, q, r are each independently integers from 1 to 6, liquid crystal alignment agents. Claim 4 In claim 2, the diamine (O) is of the following formula (d A -1) ∼ (d A A liquid crystal aligning agent that is a diamine of any one selected from the group consisting of -5). (The above formula (d A -1) ∼ (d A -5) The hydrogen atoms on the benzene ring in this case may be replaced with monovalent substituents.) Claim 5 A liquid crystal orientation agent according to claim 2, wherein the polymer (P) is obtained by a polycondensation reaction of the diamine component and a tetracarboxylic acid component containing an acyclic aliphatic tetracarboxylic acid dihydride, an alicyclic tetracarboxylic acid dihydride, an aromatic tetracarboxylic acid dihydride, or a derivative thereof. Claim 6 A liquid crystal alignment agent according to claim 2, wherein the amount of the diamine (O) used is 5 mol% or more with respect to the diamine component. Claim 7 A liquid crystal orientation agent according to claim 2, further comprising at least one polymer (B) selected from the group consisting of a polyimide precursor obtained using a diamine component that does not contain the diamine (O) and a polyimide which is an imid of the polyimide precursor. Claim 8 A liquid crystal alignment agent according to claim 2, further comprising: at least one crosslinkable compound selected from the group consisting of a crosslinkable compound having at least one substituent selected from oxiranyl groups, oxetanyl groups, block isocyanate groups, oxazoline groups, cyclocarbonate groups, hydroxyl groups and alkoxy groups, and a crosslinkable compound 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 an additive component selected from a compound for adjusting the dielectric constant or electrical resistance of the obtained liquid crystal alignment film. Claim 9 A liquid crystal alignment film obtained from a liquid crystal alignment agent described in any one of claims 1 to 8. Claim 10 A liquid crystal display element having a liquid crystal alignment layer as described in claim 9. Claim 11 In claim 10, a liquid crystal display element that is a transverse electric field liquid crystal display element. Claim 12 A method for manufacturing a liquid crystal display element comprising the following processes (1) to (3): Process (1): A process of applying a liquid crystal alignment agent described in any one of claims 1 to 8 onto a substrate; Process (2): A process of firing the applied liquid crystal alignment agent to obtain a film; Process (3): A process of performing alignment treatment on the film obtained in Process (2). Claim 13 The following formula (d A -1) or expression (d A A diamine represented as -3). (The above formula (d A -1), (d A -3) The hydrogen atoms on the benzene ring in this case may be replaced with monovalent substituents.) Claim 14 A polymer obtained from a diamine component containing the diamine described in claim 13. Claim 15 A polyimide that is a polyimide precursor or an imidate thereof, obtained by a polycondensation reaction between a diamine component containing the diamine described in claim 13 and a tetracarboxylic acid component.

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