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

Abstract

Provided is a liquid crystal alignment film which is applied to a low-temperature baking step and maintains a high voltage retention rate in a severe environment even when the amount of irradiated light in an alignment process performed by an optical alignment method is small. In addition, provided is a liquid crystal alignment film that exhibits good in-plane contrast uniformity.　This liquid crystal aligning agent contains at least one polymer (P) selected from the group consisting of: polyimide precursors each obtained by using a tetracarboxylic acid component including at least one selected from the group consisting of tetracarboxylic dianhydrides represented by formula (1) and derivatives thereof, and a diamine component including a diamine represented by formula (2-1) and a diamine represented by formula (2-2); and polyimides that are imides of the polyimide precursors. (In the formulae, the meaning of each symbol is as defined in the description.)

Description

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

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

[0002] Liquid crystal display devices are widely used as display units for personal computers, smartphones, mobile phones, televisions, etc. Liquid crystal display devices typically include a liquid crystal layer sandwiched between a display element substrate and a color filter substrate, pixel electrodes and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, and thin film transistors (TFTs) that switch electric signals supplied to the pixel electrodes. Known driving methods for liquid crystal molecules include vertical electric field methods such as the TN method and the VA method, and horizontal electric field methods such as the IPS (In Plane Switching) driving method and the FFS (Fringe Field Switching) driving method.

[0003] The most widely used liquid crystal alignment films in industry are produced by rubbing the surface of a film made of polyamic acid and / or imidized polyimide formed on an electrode substrate in one direction with a cloth such as cotton, nylon, or polyester. Rubbing is a simple, highly productive, and industrially useful method. As an alternative to rubbing, a photoalignment method is known, in which polarized radiation is irradiated to impart liquid crystal alignment ability. Proposed photoalignment methods include those utilizing photoisomerization reactions, photocrosslinking reactions, and photodecomposition reactions (see, for example, Non-Patent Document 1, Patent Documents 1, 2, and 3).

[0004] Japanese Patent Laid-Open No. 9-297313 Japanese Patent Laid-Open No. 2004-206091 WO2017 / 047596

[0005] "Functional Materials," November 1997, Vol. 17, No. 11, pp. 13-22

[0006] In recent years, CO ２To reduce emissions, so-called low-temperature baking, in which baking is performed at a low temperature during the manufacturing process of liquid crystal alignment films, has been considered. The baking process for producing polyimide-based liquid crystal alignment films requires particularly high temperatures compared to other processes for producing liquid crystal display elements. In addition to the environmental requirements mentioned above, the use of plastic substrates and the heat resistance required for color filters also necessitate the development of liquid crystal alignment agents capable of forming liquid crystal alignment films at baking temperatures of 200°C or less. Furthermore, with the prevalence of large-screen, high-resolution liquid crystal display elements and the increasing popularity of small display devices such as smartphones, tablet PCs, and car navigation systems, the demand for higher quality liquid crystal display elements is increasing more than ever before. For example, external stimuli such as light and heat can cause display defects such as image sticking (image sticking of sections and lines), unevenness, or smudges. To prevent these display defects, a liquid crystal alignment film with a high voltage holding ratio, which is a prerequisite for long-term reliability of so-called display quality, is required. Furthermore, when performing alignment treatment using a photoalignment method, the amount of light irradiation is a factor that affects energy costs and production speed, so it is preferable to perform alignment treatment with a low amount of light irradiation. However, the inventors' studies have revealed that when conventional liquid crystal alignment agents are applied to a low-temperature baking process and light irradiation is performed under conditions of low exposure, it becomes difficult to maintain a high voltage holding ratio in harsh environments where the liquid crystal is exposed to high temperatures and light irradiation for long periods of time. Furthermore, it has become clear that it is difficult to obtain a liquid crystal alignment film with good in-plane contrast uniformity, in which the variation (non-uniformity) of the twist angle of the liquid crystal within the liquid crystal alignment film is highly suppressed.

[0007] Therefore, in consideration of the above circumstances, the present invention aims to provide a liquid crystal alignment agent that can be applied to a low-temperature baking process and that can maintain a high voltage holding ratio in harsh environments even when the amount of light irradiation in alignment treatment by a photo-alignment method is low, and that can obtain a liquid crystal alignment film with good in-plane uniformity of contrast, as well as the liquid crystal alignment film, and a liquid crystal display element using the liquid crystal alignment film.

[0008] The present inventors have conducted extensive research and have found that the above problems can be solved by using a liquid crystal aligning agent containing a specific component, thereby completing the present invention.

[0009] Specifically, the present invention has the following aspects.

[0010] A liquid crystal aligning agent comprising at least one polymer (P) selected from the group consisting of a polyimide precursor obtained by using a tetracarboxylic acid component containing at least one selected from the group consisting of tetracarboxylic acid dianhydrides represented by the following formula (1) and derivatives thereof, and a diamine component containing a diamine represented by the following formula (2-1) and a diamine represented by the following formula (2-2), and a polyimide which is an imidized product of the polyimide precursor:

[0011]

[0012] (In formula (1), R １ ~R ４ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group; R １ ~R ４ At least one of the groups represented by the formula (2-1) is a group other than a hydrogen atom. Ｎ ) - * 1 (D Ｎ represents a thermally detachable group. *1 represents a bond bonded to a carbon atom other than the carbonyl carbon. Ｎ n21 and n22 each independently represent an integer of 1 or 2. n2 represents an integer of 2. In formula (2-1) and formula (2-2), the benzene ring is unsubstituted, or one or more hydrogen atoms on the benzene ring are substituted with a monovalent group. Z １ , Z ２are each independently a hydrogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkenyl group having 2 to 6 carbon atoms, or an optionally substituted aralkyl group having 7 to 13 carbon atoms. Throughout this specification, examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and * represents a bond. Boc represents a tert-butoxycarbonyl group. "tert-" can also be referred to as "t-". Fmoc represents a 9-fluorenylmethyloxycarbonyl group.

[0013] By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film that maintains a high voltage holding ratio even in a harsh environment, even when the low-temperature baking process is applied and the amount of light irradiation in the alignment treatment by the photoalignment method is small. Also, it is possible to obtain a liquid crystal alignment film with good in-plane uniformity of contrast.

[0014] <Polymer (P)> The liquid crystal aligning agent of the present invention contains at least one polymer (P) selected from the group consisting of a polyimide precursor obtained using a tetracarboxylic acid component containing at least one selected from the group consisting of tetracarboxylic acid dianhydrides represented by the above formula (1) and derivatives thereof (hereinafter also referred to as the "specific alicyclic tetracarboxylic acid component (p)"), a diamine component containing a diamine represented by the above formula (2-1) (hereinafter also referred to as the "specific diamine (1)"), or a diamine represented by the above formula (2-2) (hereinafter also referred to as the "specific diamine component") (hereinafter also referred to as the "specific diamine component"), and a polyimide which is an imidized product of the polyimide precursor. The polymer (P) may be one or more types. Here, the polyimide precursor is a polymer that can be obtained by imidizing polyamic acid, polyamic acid ester, or the like to obtain a polyimide.

[0015] (Tetracarboxylic Acid Component) The polyamic acid (P'), which is a polyimide precursor of the polymer (P), can be obtained, for example, by a polymerization reaction between the specific diamine component and the tetracarboxylic dianhydride represented by the formula (1). When producing the polymer (P), the tetracarboxylic acid component to be reacted with the diamine component may be not only a tetracarboxylic acid dianhydride, but also a derivative of a tetracarboxylic acid dianhydride such as a tetracarboxylic acid, a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester, or a tetracarboxylic acid dialkyl ester dihalide. １ ~R ４ Specific examples of the alkyl group having 1 to 6 carbon atoms in the above R include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. １ ~R ４ Specific examples of the alkenyl group having 2 to 6 carbon atoms in the above R include a vinyl group, a propenyl group, and a butenyl group, which may be linear or branched. １ ~R ４ Specific examples of the alkynyl group having 2 to 6 carbon atoms in the above R include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, and a 3-butynyl group. １ ~R ４ In the above formula, examples of the monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom include a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a pentafluoropropyl group, a trifluoromethoxy group, a 2,2,2-trifluoroethyl group, and a 2,2,2-trifluoroethoxy group. １ ~R ４ It is more preferable that at least two of R represent a group other than a hydrogen atom as defined above. １ and R ４ represents a group other than a hydrogen atom, and R ２ and R ３ It is more preferable that R represents a hydrogen atom. １ ~R ４are each independently a hydrogen atom or a methyl group, and R １ ~R ４ More preferably, at least one of R is a methyl group. １ ~R ４ It is more preferred that at least two of R are methyl groups. １ and R ４ is a methyl group, and R ２ and R ３ is a hydrogen atom. The proportion of the specific alicyclic tetracarboxylic acid component (p) used is preferably 10 mol% or more, more preferably 20 mol% or more, and most preferably 50 mol% or more, based on 1 mole of all tetracarboxylic acid components used in the polymer (P). The tetracarboxylic acid components used in the production of the polymer (P) may contain tetracarboxylic acid components other than the specific alicyclic tetracarboxylic acid component (p) (hereinafter also referred to as "other tetracarboxylic acid components"). When other tetracarboxylic acid components are used in addition to the specific alicyclic tetracarboxylic acid component (p), the content of the specific alicyclic tetracarboxylic acid component (p) is preferably 95 mol% or less, more preferably 90 mol% or less, based on 1 mole of all tetracarboxylic acid components used in the polymer (P). Furthermore, the content of the specific alicyclic tetracarboxylic acid component (p) is preferably 10 mol% or more, more preferably 20 mol% or more, based on 1 mole of all tetracarboxylic acid components used in the polymer (P). The content of the other tetracarboxylic acid component is more preferably 5 mol% to 90 mol%, even more preferably 10 to 80 mol%, and most preferably 10 to 50 mol%, relative to 1 mol of all tetracarboxylic acid components used in the polymer (P). Examples of the other tetracarboxylic acid component include acyclic aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides other than the tetracarboxylic acid dianhydride represented by formula (1), aromatic tetracarboxylic acid dianhydrides, and derivatives thereof. The acyclic aliphatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not have to be composed solely of a chain hydrocarbon structure, and may contain an alicyclic structure or an aromatic ring structure as part of the chain hydrocarbon structure.

[0016] The alicyclic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. Furthermore, it is not necessary for the structure to be composed solely of an alicyclic structure, and it may partially contain a chain hydrocarbon structure or an aromatic ring structure. The aromatic tetracarboxylic acid dianhydride is not particularly limited as long as it is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an aromatic ring. The acyclic aliphatic or alicyclic tetracarboxylic acid dianhydride or a derivative thereof is preferably a tetracarboxylic acid dianhydride or a derivative thereof having at least one partial structure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, from the viewpoint of improving liquid crystal alignment. The aromatic tetracarboxylic acid dianhydride or a derivative thereof is preferably a tetracarboxylic acid dianhydride or a derivative thereof having a benzene ring structure, from the viewpoint of improving liquid crystal alignment.

[0017] Specific examples of tetracarboxylic acid dianhydrides or derivatives thereof that can be used in the other tetracarboxylic acid components include the following: 1,2,3,4-butanetetracarboxylic acid dianhydride, or (Q) ２ -A (Q represents a monovalent succinic anhydride structure, and A represents -CH ２ -, an alkylene group having 2 to 18 carbon atoms, or -CH contained in the alkylene group ２represents a divalent organic group in which a portion of - is replaced by at least one group selected from the group consisting of a phenylene group, -O-, -NR- (R represents a hydrogen atom or a methyl group), -C(=O)-NR- (R represents a hydrogen atom or a methyl group), -C(=O)-O-, and -O-C(=O)-. ), acyclic aliphatic tetracarboxylic acid dianhydrides such as tetracarboxylic acid dianhydrides represented by the following formulas [CA-9] to [CA-10], [CA-14], [CA-21], and [CA-23] to [CA-25]; 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride, 3,3',4,4'-dicyclohexyl tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, alicyclic tetracarboxylic acid dianhydrides such as 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]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, or tetracarboxylic acid dianhydrides represented by the following formulas [CA-1], [CA-15], [CA-18], and [CA-22];Pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)-2,2-diphenylpropane dianhydride, ethylene glycol bicarbonate aromatic tetracarboxylic acid dianhydrides such as tetracarboxylic acid dianhydrides represented by the following formulae [CA-2] to [CA-8], [CA-11] to [CA-13], [CA-16] to [CA-17], and [CA-19] to [CA-20]; and other tetracarboxylic acid dianhydrides such as those described in JP-A-20-2000-97188.

[0018]

[0019]

[0020]

[0021] (Specific diamine (1)) The specific diamine (1) of the present invention is a diamine represented by the above formula (2-1). The specific diamine (1) may be used singly or in combination of two or more. One or more hydrogen atoms on the benzene ring bonded to the amino group in the above formula (2-1) may be substituted with a monovalent group, and examples of the monovalent group include a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkenyl group having 2 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, an alkyloxycarbonyl group having 2 to 3 carbon atoms, a cyano group, and a nitro group. Z in the above formula (2-1) １In the above formula (2-1), the "alkyl group having 1 to 6 carbon atoms" includes a monovalent group of a linear, branched, or cyclic aliphatic saturated hydrocarbon having 1 to 6 carbon atoms. Preferred examples include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, and a bicyclohexyl group. １ The "alkenyl group having 2 to 6 carbon atoms" in the above formula (2-1) includes a monovalent group of a linear, branched, or cyclic aliphatic unsaturated hydrocarbon having 2 to 6 carbon atoms and one or more carbon-carbon double bonds. Preferred specific examples include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, a cyclopropenyl group, a cyclopentenyl group, or a cyclohexenyl group. １ The "alkynyl group having 2 to 6 carbon atoms" in the formula (2-1) includes a monovalent group of a linear, branched, or cyclic aliphatic unsaturated hydrocarbon having 2 to 6 carbon atoms and one or more carbon-carbon triple bonds. Preferred specific examples include an ethynyl group, a 1-propynyl group, and a 2-propynyl group. １ Examples of the "aralkyl group having 7 to 13 carbon atoms" in Z include a benzyl group and a phenethyl group. １ Examples of the substituent that the alkyl group, alkenyl group, alkynyl group, or aralkyl group in the formula (I) may have include, but are not limited to, a halogen atom, a hydroxy group, a thiol group, a nitro group, an organoxy group, an organothio group, an organosilyl group, an acyl group, an ester group, a thioester group, a phosphate ester group, an amide group, and the like.

[0022] D Ｎ represents a thermally labile group, which is a protecting group that is replaced with a hydrogen atom by heat. ＮSpecific examples of the thermally detachable group in formula (2-1) include carbamate-based protecting groups, amide-based protecting groups, imide-based protecting groups, sulfonamide-based protecting groups, etc. Among these, carbamate-based protecting groups are preferred in terms of their high thermal detachability, and specific examples thereof include a Boc group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, a 1,1-dimethyl-2-cyanoethyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, and a 2-(trimethylsilyl)ethoxycarbonyl group. Among these, a Boc group is particularly preferred in terms of its excellent thermal detachability. In formula (2-1) above, L is a group selected from the group consisting of *1-N(D Ｎ ) - * 1 (D Ｎ represents a thermally detachable group. *1 represents a bond bonded to a carbon atom other than the carbonyl carbon. Ｎ )- is a divalent organic group having 2 to 6 carbon atoms, excluding the above-mentioned 1-N(D Ｎ *1 in *3-A is preferably bonded to two different carbon atoms of L, more preferably bonded to two different carbon atoms that form a chain structure, and more preferably bonded to two different carbon atoms that form an alkylene group. １１ -N(D Ｎ )-A １２ -L １ - is a divalent organic group represented by *4, １１ , A １２ each independently represents an alkylene group having 1 to 2 carbon atoms, and a hydrogen atom on a carbon atom of the alkylene group may be substituted with a halogen atom or a hydroxy group. １represents a single bond or -O-. *3 represents a bond bonded to an oxygen atom, and *4 represents a bond bonded to a benzene ring. More preferred specific examples of the diamine represented by formula (2-1) above include diamines represented by the following formulas (2-1-1) to (2-1-7).

[0023]

[0024] The content of the specific diamine (1) is preferably 5 mol % or more, more preferably 10 mol % or more, based on 1 mol of the diamine component used in the production of the polymer (P). When two or more specific diamines (1) are used in combination, the content of the specific diamine (1) refers to the total amount of the specific diamines (1).

[0025] (Specific diamine (2)) The specific diamine (2) of the present invention is a diamine represented by the above formula (2-2). The specific diamine (2) may be used singly or in combination of two or more. In particular, it is preferable to use a combination of two or more of the specific diamines (2) in order to obtain a liquid crystal alignment film with good in-plane uniformity of contrast. Z in the above formula (2-2) ２ Specific examples of Z in the above formula (2-1) １ More preferred specific examples of the diamine represented by formula (2-2) include 1,2-bis(4-aminophenoxy)ethane, 1,2-bis(4-amino-2-methylphenoxy)ethane, 1,2-bis(4-amino-3-methylphenoxy)ethane, 1,2-bis(4-amino-2-fluorophenoxy)ethane, 1,2-bis(4-amino-3-fluorophenoxy)ethane, and diamines represented by the following formulas (2-2-1) to (2-2-6).

[0026]

[0027] (In the above formula, n2 has the same definition as n2 in formula (2-2).) The content of the specific diamine (2) is preferably 5 mol % or more, and more preferably 10 mol % or more, per mole of the diamine component used in the production of the polymer (P). When two or more specific diamines (2) are used in combination, the content of the specific diamines (2) represents the total amount of the specific diamines (2).

[0028] (Other diamines) The diamine component used in the production of the polymer (P) may contain diamines other than the specific diamines (1) and (2) (hereinafter also referred to as "other diamines"). When other diamines are used in addition to the specific diamines (1) and (2), the total content of the specific diamines (1) and (2) in the diamine component is preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less, per mole of the diamine component used in the production of the polymer (P). Examples of other diamines are listed below, but are not limited to these. The other diamines may be used alone, in combination of two or more, or in combination of three or more.

[0029] Phenylenediamines such as p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, and 2,6-diaminotoluene; 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'- diaminobiphenyl compounds such as 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, and 2,3'-diaminobiphenyl;ＡＬ ) (excluding the specific diamine (2). Preferably, ＡＬ -1) to (d ＡＬ -9), 4,4'-diamino-3,3'-dimethyldiphenylmethane, 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, 1,2-bis(6-amino-2-naphthyloxy)ethane, 1,2-bis(6-amino-2-naphthyl)ethane, or 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine. ), diamines having a diphenyl ether structure such as 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, and 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, (D ＪＣ -14) (hereinafter, these are also collectively referred to as first diamines); diamines having a tetracarboxylic acid diimide structure such as N,N'-bis(4-aminophenyl)-cyclobutane-(1,2,3,4)-tetracarboxylic acid diimide, N,N'-bis(4-aminophenyl)-1,3-dimethylcyclobutane-(1,2,3,4)-tetracarboxylic acid diimide, and N,N'-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-cyclobutane-(1,2,3,4)-tetracarboxylic acid diimide; 4,4'-diaminoazobenzene, or (D ＪＣ -2) to (DＪＣ aromatic diamines having an azobenzene structure such as 4,4'-diaminostilbene, diaminotrans, or (D ＪＣ aromatic diamines having a tolan structure such as 4,4′-diaminochalcone, aromatic diamines having a chalcone structure such as 4,4′-diaminochalcone, 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, or (D ＪＣ -5), (D ＪＣ -7) to (D ＪＣ -9), (D ＪＣ -11), or (E)-4-aminophenyl 3-(4-aminophenyl)acrylate, (E)-4-amino-2-methylphenyl 3-(4-aminophenyl)acrylate, (E)-4-aminophenethyl 3-(4-aminophenyl)acrylate, (E,E)-bis-(4'-aminophenyl) 1,3-benzenediacrylate, (E,E)-bis-(4'-aminophenyl) 1,4-benzenediacrylate, or 4-aminophenyl Diamines having a photoalignment group, typified by aromatic diamines having a cinnamate structure, such as (2E)-3-(4-aminophenyl)-2-methyl-2-propenoate; diamines having a photopolymerizable group at the terminal, such as 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N,N-diallylaniline; diamines having a radical polymerization initiator function, such as 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone or 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl 3,5-diaminobenzoate; 4,4'-diaminobenzanilide, or (D ａｍ -1) to (D ａｍdiamines having an amide bond such as 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, and 1,3-bis(4-aminophenethyl)urea; diamines having a urea bond such as 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, and 2,2-bis(3-aminophenoxy)phenyl 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)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, or compounds represented by the following formula (D ＪＣ -4), (D ＪＣ -6), (D ＪＣ -10), (D ＪＣ -12) ~ (D ＪＣ-13) diamines represented by the formulae 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 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, and N-[3-(1H-imidazol-1-yl)propyl] heterocycle-containing diamines such as 3,5-diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-benzeneamine, or diamines represented by the following formulae (z-1) to (z-18), (z-20), (z-22) to (z-29), (z-31) to (z-37), and (z-39) to (z-41), or 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, diamines represented by the following formula (z-14), N,N'-bis(4-aminophenyl)-benzidine, and N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, Alternatively, diamines having a diphenylamine structure such as N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-benzenediamine, formula (z-19), formula (z-30), or formula (z-38), or diamines having at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group, and a tertiary amino group (hereinafter also referred to as a specific nitrogen atom-containing structure; however, the specific nitrogen atom-containing structure is a functional group other than the two amino groups involved in the polycondensation reaction), as typified by diamines represented by the following formula (z-21) (provided that the molecule does not have an amino group bonded to a protecting group that is cleaved by heating and replaced with a hydrogen atom):), 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, 1,2-bis(4-aminophenyl)ethane-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 diamines having a carboxy group such as 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine; diamines having a group "-N(D)-" (D represents a protecting group which is eliminated by heating and replaced with a hydrogen atom, preferably a carbamate protecting group, more preferably a tert-butoxycarbonyl group) such as those represented by the following formulas (5-1) to (5-17) (however, excluding specific diamine (1)).aromatic diamines typified by diamines having a fluorene skeleton such as 2,7-diaminofluorene or 9,9-bis(4-aminophenyl)fluorene; diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; acyclic aliphatic diamines typified by metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc.; alicyclic diamines typified by 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc., as well as diamines in which two amino groups are bonded to a group represented by any one of formulas (Y-1) to (Y-167) described in WO2018 / 117239.

[0030]

[0031] (Ar １ , and Ar １’ represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be unsubstituted or substituted with a monovalent group. １ and L １’ respectively represent a single bond, —O—, —C(═O)—, or —O—C(═O)—. A is —CH ２ -, an alkylene group having 2 to 12 carbon atoms, or a divalent organic group in which at least one of -O-, -C(=O)-O-, and -O-C(=O)- is inserted between the carbon-carbon bonds of the alkylene group. Any hydrogen atom possessed by A may be substituted with a halogen atom. However, -L １ -A-L １’ - is -O-(CH ２ ) ２ When Ar represents —O—, １ , and Ar １’At least one of the groups represents a naphthalene ring.) One or more hydrogen atoms on the benzene ring, biphenyl structure, or naphthalene ring may be substituted with a monovalent group, and examples of the monovalent group include a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkenyl group having 2 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, an alkyloxycarbonyl group having 2 to 3 carbon atoms, a cyano group, and a nitro group.

[0032]

[0033] (Formula (d ＡＬ In formula (d-2), the sum of l, m, and n is 1 to 12. ＡＬ In formula (d-5), the sum of m1, m2 and n is 1 to 12. ＡＬ In formula (d-7), the sum of m1, m2 and n is 3 to 12. ＡＬ In formula (d-8), the multiple m2s may be the same or different. ＡＬ -9) The sum of l, m, and n is 3 to 12.

[0034]

[0035]

[0036] (Formula (D ＪＣ In formula (14), k is an integer of 1 to 2. n1 and n2 are each independently an integer of 1 to 4. Any hydrogen atom on the benzene ring may be substituted with a methyl group, a methoxy group, or a halogen atom.

[0037]

[0038]

[0039]

[0040]

[0041]

[0042] (X in (z-11) １１-O-, -NH-, -C(=O)-NH-, -N(CH ３ )-(CH ２ ) ２ -O- or -O-(CH ２ ) ２ X in (z-12) represents —O—. １２ is -NH-, -N(CH ３ )-(CH ２ ) ２ -O- or -O-(CH ２ ) ２ Z in (z-13) represents —O—. １３ represents a hydrogen atom or a methyl group, and n represents an integer of 0 or 1. X in (z-15) １５ represents a methyl group or a phenyl group.

[0043]

[0044] (In formula (z-19), X １９ is -CH ２ -, -(CH ２ ) ３ represents -, -NH-.)

[0045]

[0046] (R in (z-27) represents a methyl group or a phenyl group. X in (z-30) ３０ is -N(CH ３ )- or -O-.

[0047]

[0048]

[0049] (In formula (z-39), X ３９ represents —C(═O)—, —O—, or —NH—. ３９ , R ３９’each independently represents a hydrogen atom or a methyl group.) Examples of the nitrogen atom-containing heterocycle that the diamine having the specific nitrogen atom-containing structure may have include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinoline, naphthyridine, quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, and hexamethyleneimine. Among these, pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole, and acridine are preferred.

[0050] From the viewpoint of enhancing liquid crystal alignment properties, the other diamine may be a diamine selected from the group consisting of the first diamine, a diamine having a tetracarboxylic diimide structure, a diamine having an amide bond, a diamine having a urea bond, and a diamine having a group "-N(D)-". The content of the other diamine is more preferably 5 to 85 mol%, even more preferably 10 to 80 mol%, and even more preferably 15 to 80 mol%, relative to 1 mol of the diamine component used in the production of polymer (P). Furthermore, when two or more other diamines are contained, the content of each diamine constituting each other diamine may be 30 mol% or less.

[0051] (Liquid Crystal Aligning Agent) The liquid crystal aligning agent of the present invention is a liquid composition obtained by dispersing or dissolving the polymer (P) and other components used as needed, preferably in a suitable solvent.

[0052] The liquid crystal aligning agent of the present invention may contain other polymers other than the polymer (P). Specific examples of other polymers include, in addition to the polymer (P), at least one polymer selected from the group consisting of a polyimide precursor obtained using a tetracarboxylic acid component that does not contain the specific alicyclic tetracarboxylic acid component (p) and a polyimide that is an imidized product of the polyimide precursor, at least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component that does not contain any of the specific diamines (1) to (2) and a polyimide that is an imidized product of the polyimide precursor (also referred to as polymer (B) in the present invention), 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 a polymer selected from the group consisting of poly(meth)acrylate.

[0053] Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley Corporation) and GSM301 (manufactured by Gifu Ceramics Manufacturing Co., Ltd.), and a specific example of poly(isobutylene-maleic anhydride) copolymers includes ISOBAN-600 (manufactured by Kuraray Co., Ltd.). A specific example of poly(vinyl ether-maleic anhydride) copolymers includes Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland Corporation).

[0054] Of the above other polymers, the polymer (B) is more preferred from the viewpoint of reducing afterimages resulting from residual DC.

[0055] The other polymers may be used singly or in combination of two or more. The content ratio of the other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and still more preferably 20 to 80 parts by mass, relative to 100 parts by mass of the total of the polymers contained in the liquid crystal aligning agent.

[0056] (Polymer (B)) Specific examples of the tetracarboxylic acid component used in the production of the polymer (B), including preferred specific examples, include the same compounds as those exemplified for the polymer (P), such as acyclic aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, aromatic tetracarboxylic acid dianhydrides, or derivatives thereof. The tetracarboxylic acid component used in the production of the polymer (B) more preferably contains a tetracarboxylic acid dianhydride 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 (hereinafter, these may be referred to as "specific tetracarboxylic acid component (B)").

[0057] The content of the specific tetracarboxylic acid component (B) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, based on 1 mol of all tetracarboxylic acid components used in the production of the polymer (B).

[0058] Examples of the diamine component for obtaining the polymer (B) include the diamines exemplified for the polymer (P) above, among which are the first diamine, a diamine having a urea bond, a diamine having an amide bond, 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, It is preferable to include at least one diamine selected from the group consisting of 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, the diamines having the specific nitrogen atom-containing structure, the diamines having a carboxy group, 4-(2-(methylamino)ethyl)aniline, and 4-(2-aminoethyl)aniline (hereinafter, these may be referred to as "specific diamine (b)"). As the diamine component, one diamine may be used alone, or two or more diamines may be used in combination.

[0059] When the specific diamine (b) is used, its content is preferably 10 mol% or more, more preferably 20 mol% or more, of the total diamine components used in the production of the polymer (B). When a diamine other than the specific diamine (b) is used, the content of the specific diamine (b) is preferably 90 mol% or less, more preferably 80 mol% or less, per mole of the total diamine components used in the production of the polymer (B). (Production of polyamic acid or derivative thereof) Polyamic acid or a derivative thereof is usually produced by reacting a diamine component with a tetracarboxylic acid component. Specifically, the method described in WO2015 / 012368 can be mentioned.

[0060] In producing the polyimide precursor or polyimide of the present invention, a terminal-capping polymer may be produced using a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride or a derivative thereof, a diamine component containing a diamine, and an appropriate terminal-capping agent. The terminal-capping polymer has the effect of improving the film hardness of the liquid crystal alignment film obtained by coating and improving the adhesion properties between the sealant and the liquid crystal alignment film.

[0061] Examples of the terminals of the polyimide precursor or polyimide in the present invention include an amino group, a carboxy group, an acid anhydride group, or a group derived from an end-capping agent described below. The amino group, carboxy group, and acid anhydride group can be obtained by a conventional condensation reaction or by blocking the terminals with the following end-capping agents.

[0062] Examples of the end-capping agent include acid anhydrides such as acetic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, and 4-ethynylphthalic anhydride; dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; and chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride. monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; and isocyanates having an unsaturated bond such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate.

[0063] The proportion of the end-capping agent used is preferably 0.01 to 20 parts by mole, and more preferably 0.01 to 10 parts by mole, per 100 parts by mole of the total of the diamine components used.

[0064] The polystyrene-equivalent weight average molecular weight (Mw) of the polyimide precursor and polyimide measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC, is preferably 15 or less, more preferably 10 or less. By having the molecular weight within this range, good liquid crystal alignment properties can be ensured in liquid crystal display elements.

[0065] The organic solvent contained in the liquid crystal aligning agent according to the present invention is not particularly limited as long as it can uniformly dissolve the polymer (P) and other polymers added as needed. Examples of the organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, 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, and the like. Examples of suitable solvents include N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone (collectively referred to as "good solvents"). Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.

[0066] Furthermore, the organic solvent contained in the liquid crystal aligning agent is preferably a mixed solvent containing, in addition to the above solvent, a solvent (also referred to as a poor solvent) that improves the coatability and surface smoothness of the coating film when the liquid crystal aligning agent is applied. Specific examples of poor solvents are listed below, but are not limited to these. The content of the poor solvent is preferably 1 to 80 mass %, more preferably 10 to 80 mass %, and particularly preferably 20 to 70 mass %, of the total solvent contained in the liquid crystal aligning agent. The type and content of the poor solvent are appropriately selected depending on the coater, coating conditions, coating environment, etc. of the liquid crystal aligning agent.

[0067] Examples of poor solvents include diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol ethanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, dipropylene 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, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), and the like.

[0068] Of these, diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferred.

[0069] Preferred solvent combinations of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, and N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether. Coal diacetate, N,N-dimethyl lactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone, ethyl 3-ethoxypropionate and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone, ethyl 3-ethoxypropionate and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ethyl 3-ethoxypropionate and diethylene glycol mono propyl ether, N-ethyl-2-pyrrolidone, ethyl 3-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-dimethyl lactamide and ethylene glycol monobutyl ether, N,N-dimethyl lactamide and propylene glycol diacetate, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether, N-ethyl-2 -pyrrolidone, diethylene glycol monoethyl ether, and butyl cellosolve acetate, N-methyl-2-pyrrolidone, diethylene glycol monomethyl ether, and butyl cellosolve acetate, N,N-dimethyl lactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, and 4-hydroxy-4-methyl-2-pentanone,N-ethyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and diisobutyl ketone, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and dipropylene glycol monomethyl ether Methyl-2-pentanone and propylene glycol diacetate, N-ethyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol dimethyl ether, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pi rolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisobutylcarbinol, N-methyl-2-pyrrolidone, γ-butyrolactone, and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol pyrene glycol monomethyl ether, N-ethyl-2-pyrrolidone, diethylene glycol diethyl ether, and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and propylene glycol diacetate, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and diisobutyl ketone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and diisobutyl ketone, N-ethyl-2-pyrrolidone, N,N-dimethyl lactamide, and diisobutyl ketone,Examples include N-methyl-2-pyrrolidone, ethylene glycol monobutyl ether, and ethylene glycol monobutyl ether acetate, γ-butyrolactone, ethylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, ethylene glycol monobutyl ether acetate, and propylene glycol dimethyl ether, N-methyl-2-pyrrolidone, 4-methyl-2-pentyl acetate, and ethylene glycol monobutyl ether, N-ethyl-2-pyrrolidone, cyclohexyl acetate, and 4-hydroxy-4-methyl-2-pentanone, cyclohexanone, and propylene glycol monomethyl ether, cyclopentanone, and propylene glycol monomethyl ether, and N-methyl-2-pyrrolidone, cyclohexanone, and propylene glycol monomethyl ether.

[0070] (Liquid Crystal Aligning Agent) The liquid crystal aligning agent of the present invention contains the polymer (P) and, if necessary, the other polymers and the organic solvent. The total content of the polymers contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the coating film to be formed, but is preferably 1% by mass or more from the viewpoint of forming a uniform, defect-free coating film, and is preferably 10% by mass or less from the viewpoint of storage stability of the solution. A particularly preferred total polymer content is 2 to 8% by mass.

[0071] The content of the polymer (P) used in the present invention is preferably 1 to 100 mass%, more preferably 10 to 100 mass%, particularly preferably 20 to 100 mass%, based on the total amount of polymers contained in the liquid crystal aligning agent.

[0072] The liquid crystal aligning 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 at least one crosslinking compound selected from the group consisting of a crosslinking compound having at least one substituent selected from an oxiranyl group, an oxetanyl group, a blocked isocyanate group, an oxazoline group, a cyclocarbonate group, a hydroxyalkyl group, and an alkoxy group, and a crosslinking 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 resulting liquid crystal alignment film.

[0073] Specific preferred examples of the crosslinkable 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, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl ether, bisphenol A type epoxy resins such as Epicoat 828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resins such as Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), biphenyl skeleton-containing epoxy resins such as YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), (o, m, p-) epoxy resins such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), azole novolac type epoxy resins, triglycidyl isocyanurates such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.), alicyclic epoxy resins such as Celloxide 2021P (manufactured by Daicel Corporation), compounds containing a tertiary nitrogen atom such as N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and oxiranyl such as tetrakis(glycidyloxymethyl)methane. compounds having two or more oxetanyl groups described in paragraphs

[0170] to

[0175] of WO 2011 / 132751; compounds having two or more oxetanyl groups; Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.);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)-benzene, and EPOCROS (manufactured by Nippon Shokubai Co., Ltd.); compounds having a cyclocarbonate group described in paragraphs

[0025] to

[0030] and

[0032] of WO2011 / 155577; N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydro compounds having a hydroxy group or an alkoxy group, such as (hydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane; and compounds represented by glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-,1,3-diglycerolate mixture), glycerin tris(meth)acrylate, glycerin 1,3-diglycerolate 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;

[0074] The content of the crosslinkable compound is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. Examples of the compound for adjusting the dielectric constant or electrical resistance include monoamines having a nitrogen-containing aromatic heterocycle, such as 3-picolylamine. The content of the monoamine having a nitrogen-containing aromatic heterocycle is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

[0075] Specific preferred examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. The content of the functional silane compound is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.

[0076] The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1 to 10 mass%.

[0077] The particularly preferred range of solid content varies depending on the method used to apply the liquid crystal aligning agent to the substrate. For example, when using a spin coating method, a solid content of 1.5 to 4.5 mass% is particularly preferred. When using a printing method, a solid content of 3 to 9 mass% is particularly preferred, thereby resulting in a solution viscosity of 12 to 50 mPa·s. When using an inkjet method, a solid content of 1 to 5 mass% is particularly preferred, thereby resulting in a solution viscosity of 3 to 15 mPa·s. The temperature when preparing the liquid crystal aligning agent is preferably 10 to 50°C, more preferably 20 to 30°C.

[0078] <Liquid Crystal Alignment Film / Liquid Crystal Display Element> A liquid crystal alignment film can be produced by using the liquid crystal aligning agent. The liquid crystal display element of the present invention includes the liquid crystal alignment film. The liquid crystal display element of the present invention can be applied to various operating modes, such as TN mode, STN (Super Twisted Nematic) mode, IPS mode, FFS mode, and optically compensated bend mode (OCB mode). The liquid crystal alignment film of the present invention is particularly suitable for liquid crystal display elements of horizontal alignment modes such as IPS mode or FFS mode. The liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (3), a method including steps (1) to (4), a method including steps (1) to (3), (3b), and (4), a method including steps (1) to (3), (3a), (3b), and (4), or a method including steps (1) to (2) and (4).

[0079] <Step (1): Step of applying a liquid crystal aligning agent to at least one of a first substrate and a second substrate> Step (1) is a step of applying the liquid crystal aligning agent of the present invention onto a substrate. Specific examples of step (1) are as follows.

[0080] The liquid crystal aligning agent of the present invention is applied to one side of a substrate having a patterned transparent conductive film by an appropriate application method, such as a roll coater method, a spin coat method, a printing method, or an inkjet method. The substrate is not particularly limited as long as it is highly transparent. In addition to glass substrates and silicon nitride substrates, plastic substrates such as acrylic substrates and polycarbonate substrates can also be used. In addition, in reflective liquid crystal display devices, an opaque material such as a silicon wafer can be used for only one substrate. In this case, a light-reflecting material such as aluminum can also be used for the electrode. Furthermore, when manufacturing an IPS or FFS liquid crystal display device, a substrate having an electrode made of a comb-shaped patterned transparent conductive film or metal film and an opposing substrate having no electrode are used. The transparent conductive film can be formed by a known method using, for example, indium tin oxide (ITO), indium zinc oxide (IZO), or a mixture thereof.

[0081] Examples of a method for applying the liquid crystal aligning agent to a substrate and forming a film include screen printing, offset printing, flexographic printing, an inkjet method, and a spray method. Among these, the application and film formation method by the inkjet method is preferably used.

[0082] <Step (2): Step of baking the applied liquid crystal aligning agent> Step (2) is a step of baking the liquid crystal aligning agent applied on the substrate to form a film. Specific examples of step (2) are as follows.

[0083] After applying the liquid crystal aligning agent to the substrate in step (1), the solvent can be evaporated or the polyamic acid or polyamic acid ester can be thermally imidized using a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven. The drying and baking steps after applying the liquid crystal aligning agent of the present invention can be performed at any temperature and for any time, and may be performed multiple times. The temperature in the baking step is preferably 30°C or higher and 200°C or lower. The temperature at which the solvent in the liquid crystal aligning agent is reduced can be, for example, 40 to 150°C. To shorten the process, the baking step may be performed at 40 to 120°C. The baking time is not particularly limited, but may be 1 to 10 minutes or 1 to 5 minutes. When thermally imidizing the polyamic acid or polyamic acid ester, a baking step at a temperature of 150°C or higher and 200°C or lower (hereinafter also referred to as the main baking step) may be added after the above step. The main firing step may be a step of firing at a temperature range of 160 to 200° C. or 160 to 190° C. The firing time is not particularly limited, but may be 5 to 40 minutes or 5 to 30 minutes. Note that the step (3b) may be carried out after the step (3) described below, without carrying out the main firing step.

[0084] If the film-like material after baking is too thin, the reliability of the liquid crystal display device may decrease, so the film thickness is preferably 5 to 300 nm, more preferably 10 to 200 nm.

[0085] <Step (3): Alignment Treatment of the Film Obtained in Step (2)> Step (3) is a step of, in some cases, aligning the film obtained in Step (2). That is, in the case of a horizontal alignment type liquid crystal display element such as an IPS type or an FFS type, the coating film is subjected to an alignment ability imparting treatment. Alignment treatment methods for liquid crystal alignment films include rubbing treatment and photo-alignment treatment, with photo-alignment treatment being more preferred. Photo-alignment treatment methods include irradiating the surface of the film with radiation (more preferably polarized radiation) to impart liquid crystal alignment properties (also referred to as liquid crystal alignment ability). As the radiation, ultraviolet light or visible light having a wavelength of 100 to 800 nm can be used. Of these, ultraviolet light having a wavelength of 100 to 400 nm is preferred, more preferably 200 to 400 nm. The rubbing treatment method includes rubbing the coating film in a specific direction with a roll wrapped around a cloth made of fibers such as nylon, rayon, or cotton.

[0086] In the photo-alignment treatment method, when the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, the radiation may be irradiated from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these. When irradiating with unpolarized radiation, the irradiation direction is preferably oblique.

[0087] The radiation dose is 1 to 10,000 mJ / cm ２ More preferably, 100 to 1,000 mJ / cm ２ is more preferably 100 to 500 mJ / cm ２ is most preferred.

[0088] When radiation is irradiated in the photo-alignment treatment, in order to improve the liquid crystal alignment, the substrate having the film-like material may be irradiated while being heated at, for example, 50 to 200° C. The liquid crystal alignment film prepared in this manner can stably align liquid crystal molecules in a certain direction.

[0089] The liquid crystal alignment film obtained by the above method may further be subjected to a step of contact treatment using a solvent (hereinafter also referred to as step (3a)). The solvent used in the contact treatment in step (3a) is not particularly limited as long as it is a solvent that dissolves the decomposition products generated from the film-like 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, and the like. Among these, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate are preferred from the viewpoints of versatility and solvent safety. Water, 1-methoxy-2-propanol, or ethyl lactate are more preferred. The solvent may be one type or a combination of two or more types. The liquid crystal alignment film used in the liquid crystal display element of the present invention may be prepared by carrying out the following step (3b) after the step (3). The step (3b) may be carried out on a film that has been subjected to the treatment in the step (3a) above, in addition to the film that has been subjected to the alignment treatment in the step (3).

[0090] <Step (3b): Step of Heat Treatment> The coating film irradiated with the radiation may be subjected to a heat treatment. The temperature for such heat treatment is preferably 50 to 200°C, more preferably 120 to 190°C, even more preferably 160 to 200°C, and still more preferably 160 to 190°C. The time for the heat treatment is preferably 1 to 30 minutes.

[0091] <Step (4): A step of disposing a liquid crystal layer between the first substrate and the second substrate so as to be adjacent to the alignment-treated film to prepare a liquid crystal cell> Step (4) is a step of disposing a liquid crystal layer between the first substrate and the second substrate so as to be adjacent to the alignment-treated film to prepare a liquid crystal cell. Note that the following describes an example in which a liquid crystal alignment film is formed on each of the first substrate and the second substrate. Specifically, the following two methods can be used.

[0092] In the first method, two substrates are placed opposite each other with a gap (cell gap) between them so that their liquid crystal alignment films face each other, and then the peripheries of the two substrates are bonded together using a sealant. A liquid crystal composition is injected into the substrate surfaces and the cell gap defined by the sealant so that it comes into contact with the film surface, and the injection hole is then sealed.

[0093] The second method is called the ODF (One Drop Fill) method. For example, a UV-curable resin composition (hereinafter also referred to as a sealant) is applied to a predetermined location on one of two substrates on which a liquid crystal alignment film has been formed, and a liquid crystal composition is then dropped onto several predetermined locations on the liquid crystal alignment film surface. The other substrate is then attached so that the liquid crystal alignment film faces the other substrate, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with UV light to cure the sealant. In either method, it is desirable to further heat the substrate to a temperature at which the liquid crystal composition is in an isotropic phase, and then slowly cool it to room temperature to remove flow alignment that occurs during liquid crystal filling.

[0094] When the coating films are subjected to rubbing treatment, the two substrates are placed opposite each other so that the rubbing directions of the coating films are at a predetermined angle, for example, perpendicular or anti-parallel to each other.

[0095] The sealing agent may be, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as spacers. The liquid crystal composition is not particularly limited, and any liquid crystal composition containing at least one liquid crystal compound (liquid crystal molecule) and having a positive or negative dielectric anisotropy may be used. Hereinafter, a liquid crystal composition having a positive dielectric anisotropy will be referred to as a positive liquid crystal, and a liquid crystal composition having a negative dielectric anisotropy will be referred to as a negative liquid crystal.

[0096] The liquid crystal composition may contain a liquid crystal compound having a fluorine atom, a hydroxy 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 heterocycle, a cycloalkane, a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring, or may contain a compound having two or more rigid moieties (mesogenic skeletons) that exhibit liquid crystallinity within the molecule (e.g., a bimesogenic compound in which two rigid biphenyl structures or terphenyl structures are linked by an alkylene group).

[0097] The liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase.

[0098] The liquid crystal composition may further contain an additive from the viewpoint of improving the liquid crystal alignment property, such as a photopolymerizable monomer having a polymerizable group, an optically active compound (e.g., S-811 manufactured by Merck Ltd.), an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerization initiator, or a polymerization inhibitor.

[0099] Examples of positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081 manufactured by Merck Co., Ltd.; and PA-1492 manufactured by DIC Corporation.

[0100] Examples of negative liquid crystals include MLC-6608, MLC-6609, MLC-6610, and MLC-7026-100 manufactured by Merck Co., Ltd.; and NA-1559 manufactured by DIC Corporation.

[0101] Furthermore, an example of a liquid crystal containing a compound having a polymerizable group is MLC-3023 manufactured by Merck.

[0102] A liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell as needed. Examples of the polarizing plate to be attached to the outer surface of the liquid crystal cell include a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine, sandwiched between cellulose acetate protective films, and a polarizing plate made of the H film itself.

[0103] The liquid crystal alignment film of the present invention can be used for various purposes other than the above-mentioned purposes, for example, as a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmission-scattering type liquid crystal dimming element. Furthermore, it can also be used for purposes other than liquid crystal alignment films, such as a protective film (e.g., a protective film for a color filter), a spacer film, an interlayer insulating film, an antireflection film, a wiring covering film, an antistatic film, and an insulating film for an electric motor (a gate insulating film for a flexible display).

[0104] The liquid crystal display element of the present invention can be effectively applied to various devices, and can be used in various display devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays.

[0105] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The abbreviations of the compounds used and the methods for measuring the physical properties are as follows:

[0106] (Organic solvent) NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve (tetracarboxylic dianhydride) CA-1 to CA-2: compounds represented by the following formulas (CA-1) to (CA-2)

[0107]

[0108] (Diamine) DA-1 to DA-9: Compounds represented by the following formulas (DA-1) to (DA-9), respectively

[0109]

[0110] (Additives) AD-1 to AD-3: Compounds represented by the following formulas (AD-1) to (AD-3), respectively

[0111] (End-capping agent) SA: succinic anhydride

[0112] <Measurement of Viscosity> Measurement was carried out at 25°C using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a cone rotor TE-1 (1°34', R24).

[0113] <Measurement of Molecular Weight> Measurement was carried out using the following room temperature GPC (gel permeation chromatography) apparatus under the following conditions, and Mn (number average molecular weight) and Mw (weight average molecular weight) were calculated as polyethylene glycol oxide equivalent values.

[0114] GPC apparatus: GPC-101 (manufactured by Resonac), Column: GPC KD-803 and GPC KD-805 (manufactured by Resonac) in series, Column temperature: 50°C, Eluent: N,N-dimethylformamide (additive: lithium bromide monohydrate (LiBr.H ２ o) at 30 mmol / L, anhydrous crystalline phosphoric acid (o-phosphoric acid) at 30 mmol / L, tetrahydrofuran (THF) at 10 mL / L), flow rate: 1.0 mL / min. Standard sample for creating a calibration curve: EasiVial PEG / PEO polyethylene glycol oxide PL2080-0201 (molecular weight: approximately 1,500, approximately 4,000, approximately 13,000, approximately 30,000, approximately 70,000, approximately 130,000, approximately 500,000, approximately 1,000,000, approximately 1,500,000) (manufactured by GL Sciences).

[0115] [Polymer Synthesis] <Synthesis Example 1> DA-1 (1.22 g, 4.99 mmol), DA-4 (1.94 g, 5.01 mmol), and NMP (23.2 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature (25°C) while supplying nitrogen. Thereafter, CA-1 (2.16 g, 9.64 mmol) and NMP (15.8 g) were added, and the mixture was stirred at 40°C for 24 hours to obtain a solution of polyamic acid (PAA-1) (viscosity: 457 mPa s). The Mn of this polyamic acid was 13,260 and the Mw was 41,938. Synthesis Example 2 DA-1 (1.22 g, 4.99 mmol), DA-5 (1.71 g, 5.01 mmol), and NMP (21.5 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25°C) while supplying nitrogen to dissolve the mixture. CA-1 (2.17 g, 9.68 mmol) and NMP (15.9 g) were then added, and the mixture was stirred at 40°C for 24 hours to obtain a solution of polyamic acid (PAA-2) with a solids concentration of 12% by mass (viscosity: 288 mPa s). The Mn of this polyamic acid was 12,613, and the Mw was 34,163.

[0116] Synthesis Example 3 DA-2 (1.60 g, 4.99 mmol), DA-4 (1.94 g, 5.01 mmol), and NMP (26.0 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25°C) while supplying nitrogen to dissolve the mixture. CA-1 (2.15 g, 9.59 mmol) and NMP (15.8 g) were then added, and the mixture was stirred at 40°C for 24 hours to obtain a solution of polyamic acid (PAA-3) with a solids concentration of 12% by mass (viscosity: 381 mPa s). The Mn of this polyamic acid was 13,063, and the Mw was 32,910. Synthesis Example 4 DA-2 (1.60 g, 4.99 mmol), DA-5 (1.71 g, 5.01 mmol), and NMP (24.3 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25°C) while introducing nitrogen to dissolve the mixture. CA-1 (2.16 g, 9.64 mmol) and NMP (15.9 g) were then added, and the mixture was stirred at 40°C for 24 hours to obtain a solution of polyamic acid (PAA-4) with a solids concentration of 12% by mass (viscosity: 359 mPa s). The Mn of this polyamic acid was 13,549, and the Mw was 34,102.

[0117] Synthesis Example 5: DA-1 (0.730 g, 2.99 mmol), DA-2 (0.960 g, 3.00 mmol), DA-3 (0.540 g, 1.98 mmol), DA-4 (0.780 g, 2.01 mmol) and NMP (22.1 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, CA-1 (2.15 g, 9.59 mmol) and NMP (15.7 g) were added, and the mixture was stirred at 40 ° C. for 24 hours to obtain a solution of polyamic acid (PAA-5) with a solids concentration of 12% by mass (viscosity: 394 mPa s). The Mn of this polyamic acid was 12,201 and the Mw was 29,527. Synthesis Example 6: DA-1 (0.730 g, 2.99 mmol), DA-2 (0.960 g, 3.00 mmol), DA-3 (0.540 g, 1.98 mmol), DA-5 (0.680 g, 1.99 mmol) and NMP (21.4 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, CA-1 (2.11 g, 9.41 mmol) and NMP (15.5 g) were added, and the mixture was stirred at 40 ° C. for 24 hours to obtain a solution of polyamic acid (PAA-6) with a solids concentration of 12% by mass (viscosity: 223 mPa s). The Mn of this polyamic acid was 9,166 and the Mw was 22,328.

[0118] Synthesis Example 7 DA-6 (0.540 g, 4.99 mmol), DA-4 (1.94 g, 5.01 mmol), and NMP (18.2 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, CA-1 (2.17 g, 9.68 mmol) and NMP (15.9 g) were added, and the mixture was stirred at 40 ° C. for 24 hours to obtain a solution of polyamic acid (PAA-7) with a solids concentration of 12% by mass (viscosity: 436 mPa s). The Mn of this polyamic acid was 15,608, and the Mw was 45,984. Synthesis Example 8 DA-6 (0.540 g, 4.99 mmol), DA-5 (1.71 g, 5.01 mmol), and NMP (16.5 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while introducing nitrogen to dissolve the mixture. Thereafter, CA-1 (2.19 g, 9.77 mmol) and NMP (16.1 g) were added, and the mixture was stirred at 40 ° C. for 24 hours to obtain a solution of polyamic acid (PAA-8) with a solids concentration of 12% by mass (viscosity: 545 mPa s). The Mn of this polyamic acid was 16,679, and the Mw was 52,802. Synthesis Example 9 DA-1 (0.733 g, 3.00 mmol), DA-2 (0.961 g, 3.00 mmol), DA-3 (0.545 g, 2.00 mmol), DA-4 (0.775 g, 2.00 mmol) and NMP (22.1 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, CA-1 (2.05 g, 9.15 mmol) and NMP (15.0 g) were added, and the mixture was stirred at 40 ° C. for 24 hours to obtain a solution of polyamic acid (PAA-9) with a solids concentration of 12% by mass (viscosity: 88 mPa s). The Mn of this polyamic acid was 7,380 and the Mw was 15,588. Synthesis Example 10 DA-1 (0.733 g, 3.00 mmol), DA-2 (0.961 g, 3.00 mmol), DA-3 (0.545 g, 2.00 mmol), DA-4 (0.775 g, 2.00 mmol), and NMP (22.1 g) were placed in a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25° C.) while supplying nitrogen.Thereafter, CA-1 (2.03 g, 9.05 mmol) and NMP (14.9 g) were added, and the mixture was stirred at 40°C for 24 hours to obtain a solution of polyamic acid (PAA-10) with a solids concentration of 12% by mass (viscosity: 79 mPa s). The polyamic acid had an Mn of 6,799 and an Mw of 14,300. The obtained polyamic acid solution (30.0 g) was weighed into a 50 mL Erlenmeyer flask containing a stirrer, and SA (0.149 g, 1.49 mmol) and NMP (1.10 g), which serve as end-capping agents, were added. The mixture was stirred at room temperature (25°C) for 24 hours to obtain a solution of end-capped polyamic acid (PAA-10M). Synthesis Example 11 DA-7 (1.59 g, 8.00 mmol), DA-8 (0.597 g, 2.00 mmol), and NMP (19.7 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature (25°C) while supplying nitrogen. Subsequently, CA-2 (1.76 g, 9.00 mmol) and NMP (15.9 g) were added, and the mixture was stirred at 40°C for 24 hours to obtain a solution of polyamic acid (PAA-11) with a solids concentration of 10% by mass (viscosity: 151 mPa s). The Mn of this polyamic acid was 12,112 and the Mw was 28,197. The obtained polyamic acid solution (30.0 g) was weighed out into a 50 mL Erlenmeyer flask containing a stirrer, and the end-capping agent SA (0.167 g, 1.67 mmol) and NMP (1.50 g) were added, followed by stirring at room temperature (25° C.) for 24 hours to obtain a solution of end-capped polyamic acid (PAA-11M). <Synthesis Example 12> DA-7 (1.49 g, 7.50 mmol), DA-8 (0.597 g, 2.00 mmol), DA-9 (0.121 g, 0.499 mmol), and NMP (19.9 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25° C.) while supplying nitrogen to dissolve the polyamic acid. Thereafter, CA-2 (1.80 g, 9.20 mmol) and NMP (16.2 g) were added and stirred at 40° C. for 24 hours to obtain a solution of polyamic acid (PAA-12) with a solids concentration of 10% by mass (viscosity: 134 mPa s). The polyamic acid had an Mn of 11,533 and an Mw of 26,208.

[0119] The specifications of the polyamic acid solutions obtained in the above synthesis examples are shown in Table 1. In Table 1, the numbers in parentheses for the tetracarboxylic acid component and diamine component represent the amount (parts by mole) of each tetracarboxylic acid component and each diamine component used relative to 100 parts by mole of the total amount of the diamine components used in each polymerization step.

[0120]

[0121] [Preparation of Liquid Crystal Alignment Agent] <Example 1> NMP (7.0 g), BCS (3.00 g), and AD-1 (0.084 g) were added to the solution (5.0 g) of polyamic acid (PAA-1) obtained in Synthesis Example 1 above, and the mixture was stirred at room temperature for 60 minutes to obtain liquid crystal alignment agent (AL-1). <Examples 2-3, Comparative Examples 1-5> Liquid crystal alignment agents (AL-2) to (AL-8) were obtained by carrying out the same procedure as in Example 1, except that the solution of polyamic acid used was replaced from (PAA-1) to (PAA-2) to (PAA-8). Example 4 To a solution (2.0 g) of the polyamic acid (PAA-9) obtained in Synthesis Example 9 above and a solution (3.6 g) of the polyamic acid (PAA-11M) obtained in Synthesis Example 11 above, NMP (3.94 g), a 2 mass % NMP solution of AD-3 (0.9 g), BCS (4.50 g), and AD-2 (0.06 g) were added, and the mixture was stirred at room temperature for 120 minutes to obtain a liquid crystal aligning agent (AL-9). Example 5 To a solution (2.0 g) of the polyamic acid (PAA-10M) obtained in Synthesis Example 10 above and a solution (3.6 g) of the polyamic acid (PAA-12) obtained in Synthesis Example 12 above, NMP (3.94 g), a 2 mass % NMP solution of AD-3 (0.9 g), BCS (4.50 g), and AD-2 (0.06 g) were added, and the mixture was stirred at room temperature for 120 minutes, thereby obtaining a liquid crystal aligning agent (AL-10). <Comparative Example 6> NMP (3.94 g), a 2 mass % NMP solution of AD-3 (0.9 g), BCS (4.50 g), and AD-2 (0.06 g) were added to a solution (2.0 g) of the polyamic acid (PAA-6) obtained in Synthesis Example 6 above and a solution (3.6 g) of the polyamic acid (PAA-11M) obtained in Synthesis Example 11 above, and the mixture was stirred at room temperature for 120 minutes to obtain a liquid crystal aligning agent (AL-11).

[0122] Table 2 shows the specifications of the liquid crystal aligning agents obtained in the above Examples and Comparative Examples.

[0123]

[0124] [Fabrication of Liquid Crystal Cell] First, a substrate with electrodes was prepared. The substrate was a glass substrate measuring 30 mm x 40 mm and 0.7 mm thick. ITO electrodes with a film thickness of 35 nm were formed on the substrate. The electrodes were in a stripe pattern spaced 40 mm vertically and 10 mm horizontally.

[0125] Next, each of the liquid crystal alignment agents (AL-1) to (AL-11) obtained above was filtered through a filter with a pore size of 1.0 μm, and then applied by spin coating to the electrode-attached substrate prepared above. The resulting mixture was then dried on a hot plate at 80°C for 1 minute and then baked in an infrared heating furnace at 180°C for 30 minutes to form a coating film with a thickness of 100 nm, resulting in a substrate with a liquid crystal alignment film. The coating surface was irradiated with polarized ultraviolet light via a 254 nm bandpass filter and a polarizer at the exposure dose listed in Table 3 (the optimal exposure dose for each liquid crystal alignment agent), and then baked in an infrared heating furnace at 180°C for 30 minutes to perform an alignment treatment, resulting in a substrate with a liquid crystal alignment film. Two substrates with this liquid crystal alignment film were prepared, and spherical spacers with a particle size of 4 μm were sprayed on the liquid crystal alignment film surface of one of the substrates. A sealant (Mitsui Chemicals, Inc., XN-1500T) was then printed around the periphery, leaving the liquid crystal injection port. Next, the other substrate with a liquid crystal alignment film was attached with the side on which the liquid crystal alignment film was formed facing inward, so that the alignment directions of the liquid crystal alignment films faced each other with an angle of 0°. This was then heated at 150°C for 60 minutes to harden the sealant, producing an empty cell. Negative liquid crystal NA-1559 (manufactured by DIC Corporation) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. The resulting liquid crystal cell was then heated at 120°C for 1 hour and left overnight at 23°C before being used for each evaluation.

[0126] [Evaluation of In-Plane Uniformity of Contrast] The variation in the twist angle of the liquid crystal cell was evaluated using an AxoStep manufactured by AXOMETRICS. The liquid crystal cell prepared as described above was placed on a measurement stage, and the distribution of circular retardance within the pixel plane was measured with no voltage applied, and 3σ, which is three times the standard deviation σ, was calculated. The smaller the 3σ value, the better the in-plane uniformity. As an evaluation standard, a 3σ value of less than 1.50 was rated as "good," and a 3σ value of 1.50 or greater was rated as "poor." The results are shown in Table 3.

[0127] [Evaluation of Backlight Resistance of Voltage Holding Ratio] A voltage of 1 V was applied to the liquid crystal cell at a temperature of 60°C for 60 μsec, and the voltage after 1667 msec was measured to calculate the voltage holding ratio, which is the initial voltage holding ratio. To measure the voltage holding ratio, a VHR-1 manufactured by Toyo Corporation was used.

[0128] Next, as a backlight resistance test, the liquid crystal cell was placed under a high-intensity backlight (light source: LED, brightness: 27000 cd / m) with a surface temperature of 50°C. ２ The liquid crystal cell was then left to stand under the same temperature for 120 hours. The voltage holding ratio of the liquid crystal cell was measured in the same manner as above. This was taken as the voltage holding ratio after the endurance test.

[0129] The backlight resistance of the voltage holding ratio was evaluated by defining a VHR change rate [%] (= 100 - 100 × (voltage holding ratio after resistance test) / (initial voltage holding ratio)) of less than 20% as "good" and a VHR change rate of 20% or more as "poor". The results are shown in Table 3. In Table 3 below, "-" in Comparative Example 4 and Comparative Example 6 indicates that the VHR change rate was not measured.

[0130]

[0131] As shown in Table 3, the liquid crystal alignment film obtained from the liquid crystal alignment agent using the diamine component having the specific diamine (1) and the specific diamine (2) had better liquid crystal alignment properties (in-plane uniformity of contrast) and reliability (backlight resistance of voltage holding ratio) than the liquid crystal alignment film obtained from the liquid crystal alignment agent using the diamine component not having at least one of the specific diamine (1) and the specific diamine (2).

[0132] By using the liquid crystal aligning agent of the present invention, a liquid crystal alignment film can be obtained that maintains a high voltage holding ratio even in harsh environments, even when applied to a low-temperature baking process and with a low light exposure dose during alignment treatment using a photoalignment method. Furthermore, a liquid crystal alignment film with good in-plane contrast uniformity can be obtained. Therefore, it is expected to be used in liquid crystal display elements that require high display quality, particularly liquid crystal display elements using IPS driving methods and FFS driving methods. Furthermore, these elements are also useful in liquid crystal displays for display purposes, dimming windows that control light transmission and blocking, optical shutters, etc.

[0133] The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2024-024110 filed on February 20, 2024 are hereby incorporated by reference as the disclosure of the present invention.

Claims

1. A liquid crystal aligning agent comprising at least one polymer (P) selected from the group consisting of a polyimide precursor obtained using a tetracarboxylic acid component containing at least one selected from the group consisting of tetracarboxylic acid dianhydrides represented by the following formula (1) and derivatives thereof, and a diamine component containing a diamine represented by the following formula (2-1) and a diamine represented by the following formula (2-2), and a polyimide which is an imidized product of the polyimide precursor. (In formula (1), R １ ~R ４ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group; R １ ~R ４ At least one of the groups represented by the formula (2-1) is a group other than a hydrogen atom. Ｎ ) - * 1 (D Ｎ represents a thermally detachable group. *1 represents a bond bonded to a carbon atom other than the carbonyl carbon. Ｎ n21 and n22 each independently represent an integer of 1 or 2. n2 represents an integer of 2. In formula (2-1) and formula (2-2), the benzene ring is unsubstituted, or one or more hydrogen atoms on the benzene ring are substituted with a monovalent group. Z １ , Z ２ are each independently a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms, each of which may have a substituent.

2. The liquid crystal aligning agent according to claim 1, wherein the contents of the diamine represented by the formula (2-1) and the diamine represented by the formula (2-2) are each 5 mol% or more relative to 1 mol of the diamine component used in the production of the polymer (P).

3. The liquid crystal aligning agent according to claim 1, wherein L in formula (2-1) is a divalent organic group having an alkylene group having 1 to 6 carbon atoms.

4. The liquid crystal aligning agent according to claim 1, wherein the diamine represented by formula (2-2) is 1,2-bis(4-aminophenoxy)ethane, 1,2-bis(4-amino-2-methylphenoxy)ethane, 1,2-bis(4-amino-3-methylphenoxy)ethane, 1,2-bis(4-amino-2-fluorophenoxy)ethane, 1,2-bis(4-amino-3-fluorophenoxy)ethane, or a diamine represented by the following formulas (2-2-1) to (2-2-6): (In the formula, n2 has the same definition as n2 in the formula (2-2).) 5. R in the formula (1) １ ~R ４ The liquid crystal aligning agent according to claim 1 , wherein at least two of the following represent groups other than hydrogen atoms in the definitions.

6. The liquid crystal aligning agent according to claim 1, wherein the content of the tetracarboxylic dianhydride represented by the formula (1) and its derivatives is 10 mol% or more relative to 1 mol of the tetracarboxylic acid component used in the production of the polymer (P).

7. The diamine component further comprises a phenylenediamine, a diaminobiphenyl compound, or a compound represented by the following formula (d ＡＬ ) (provided that the diamine represented by the formula (2-2) is excluded), diamines having a diphenyl ether structure, diamines having a tetracarboxylic acid diimide structure, diamines having an amide bond, diamines having a urea bond, and diamines having a group "-N(D)-" (provided that the diamine represented by the formula (2-1) is excluded). The liquid crystal aligning agent according to claim 1, containing at least one other diamine selected from the group consisting of (Ar １ , and Ar １’ represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be unsubstituted or substituted with a monovalent group. １ and L １’ respectively represent a single bond, —O—, —C(═O)—, or —O—C(═O)—. A is —CH ２ -, an alkylene group having 2 to 12 carbon atoms, or a divalent organic group in which at least one of -O-, -C(=O)-O-, and -O-C(=O)- is inserted between the carbon-carbon bonds of the alkylene group. Any hydrogen atom possessed by A may be substituted with a halogen atom. However, -L １ -A-L １’ - is -O-(CH ２ ) ２ When Ar represents —O—, １ , and Ar １’ At least one of represents a naphthalene ring.

8. The liquid crystal aligning agent according to claim 7, wherein the total content of the diamine represented by the formula (2-1) and the diamine represented by the formula (2-2) is 95 mol% or less relative to 1 mol of the diamine components used in the production of the polymer (P), and the content of the other diamines is 5 to 85 mol% relative to 1 mol of the diamine components used in the production of the polymer (P).

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

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

11. A method for manufacturing a liquid crystal display element, comprising the following steps (1) to (4): step (1): applying the liquid crystal alignment agent according to any one of claims 1 to 8 to at least one of a first substrate and a second substrate; step (2): baking the applied liquid crystal alignment agent to obtain a film; step (3): performing an alignment treatment on the film obtained in step (2); and step (4): arranging a liquid crystal layer between the first substrate and the second substrate so as to be adjacent to the alignment-treated film to prepare a liquid crystal cell.

12. The method for producing a liquid crystal display element according to claim 11, wherein the alignment treatment is a photo-alignment treatment.

13. The method for producing a liquid crystal display element according to claim 12, further comprising a step (3b) of carrying out a heat treatment between steps (3) and (4).

14. The method for producing a liquid crystal display element according to claim 13, wherein the temperature of the heat treatment in step (3b) is 50 to 200°C.

15. The method for producing a liquid crystal display element according to claim 14, wherein the liquid crystal display element is an IPS-type or FFS-type liquid crystal display element.

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