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

Abstract

Provided is a liquid crystal alignment film exhibiting excellent in-plane uniformity of a liquid crystal alignment regulating force even when a liquid crystal alignment agent has been dried at a low temperature.　The liquid crystal alignment agent is characterized by containing polymer (A) and polymer (B).　Polymer (A): A polyamic acid containing a structural unit (a-1Ta) represented by formula (1Ta) and a structural unit (a-1Da) represented by formula (1Da).　Polymer (B): A polyamic acid containing a structural unit (b-1Tb) represented by formula (1Tb) and a structural unit (b-1Db) represented by formula (1Db), with at least some of the terminals including a non-amino group, and the non-amino group being a functional group represented by formula (E). [Formula 1] (The definitions of the symbols are as described in the specification.) [Formula 2] (The definitions of the symbols are as described in the specification.) [Formula 3] (The definitions of the symbols are as described in the specification.) [Formula 4] [Formula 5] (The definitions of the symbols are as described in the specification.)

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 have traditionally been widely used as display units for personal computers, smartphones, mobile phones, television receivers, etc. Liquid crystal display devices include, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, pixel electrodes and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the 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 methods for driving liquid crystal molecules include vertical electric field methods such as the TN (Twisted Nematic) method and the VA (Vertical Alignment) method, and horizontal electric field methods such as the IPS (In-Plane Switching) method and the FFS (Fringe Field Switching) method.

[0003] Currently, the most widely used industrial liquid crystal alignment films are produced by performing an alignment treatment on the surface of a film made of a polymer, typically polyamic acid and / or imidized polyimide, formed on an electrode substrate. In recent years, as liquid crystal display elements have become higher in performance, resolution, and size, photo-alignment methods have been investigated, in which liquid crystal alignment ability is imparted by irradiating polarized radiation. Proposed photo-alignment methods include those utilizing photoisomerization reactions, photo-crosslinking reactions, and photodecomposition reactions (see, for example, Non-Patent Document 1 and Patent Document 1).

[0004] Japanese Patent Application Publication No. 9-297313

[0005] "Liquid Crystal Photo-Alignment Film" Kidowaki, Ichimura, Functional Materials, November 1997, Vol. 17, No. 11, pp. 13-22

[0006] Generally, a liquid crystal alignment film is formed by applying a liquid crystal alignment agent, which is a polyamic acid or polyimide dissolved in an organic solvent, to a substrate, followed by pre-drying and baking. Pre-drying is typically performed at a drying temperature of 80°C or higher. However, with the recent trend toward larger liquid crystal display devices and lower costs, pre-drying of liquid crystal alignment agents has become more common. However, conventional liquid crystal alignment agents can easily cause variations (non-uniformity) in the twist angle of the liquid crystal within the liquid crystal alignment film when dried at low temperatures. Therefore, a liquid crystal alignment agent capable of producing a liquid crystal alignment film with reduced variations in the twist angle of the liquid crystal even when dried at low temperatures has been desired.

[0007] In view of the above, an object of the present invention is to provide a liquid crystal alignment agent that can produce a liquid crystal alignment film having excellent in-plane uniformity of liquid crystal alignment control force even when the liquid crystal alignment agent is dried at low temperatures, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element.

[0008] As a result of intensive research into achieving the above-mentioned object, the present inventors have found that using a liquid crystal aligning agent containing a first polyamic acid having a structural unit derived from a specific tetracarboxylic acid derivative and a structural unit derived from a diamine, and a second polyamic acid having a specific non-amino terminal structure and having a structural unit derived from the specific tetracarboxylic acid derivative and a structural unit derived from a diamine, is extremely effective in achieving the above-mentioned object, and have completed the present invention.

[0009] The present invention includes the following aspects.

[0010] A liquid crystal aligning agent comprising the following polymer (A) and polymer (B):

[0011] Polymer (A): A polyamic acid (A) having a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine, wherein the structural unit derived from the tetracarboxylic acid derivative is a structural unit represented by the following formula (1T ａ As a diamine-derived structural unit, a structural unit (a-1Ta) represented by the following formula (1D ａ The polyamic acid as described above, which contains a structural unit (a-1Da) represented by the formula (a-1Da).

[0012] Polymer (B): A polyamic acid (B) having a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine, wherein the structural unit derived from the tetracarboxylic acid derivative is a structural unit represented by the following formula (1T ｂ As a diamine-derived structural unit, a structural unit (b-1Tb) represented by the following formula (1D ｂ ), wherein at least a portion of the terminals of the polyamic acid (B) contain a non-amino group, and the non-amino group is a functional group represented by the following structural formula (E):

[0013]

[0014] (Formula (1T ａ ) Medium X ａ represents a tetravalent organic group represented by the following formula (X-1): ａ ) in Y ａ represents a divalent organic group derived from a diamine. Each Z independently represents a hydrogen atom or a monovalent organic group.

[0015]

[0016] (In formula (X-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, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, or a phenyl group; R １ ~R ４ At least one of represents a group other than a hydrogen atom as defined above. * represents a bond.)

[0017]

[0018] (Formula (1T ｂ ) Medium X ｂ is a tetravalent organic group represented by the following formula (X-2), or a tetravalent organic group having an alicyclic structure with five or more members (T ５ａ ) is represented by the formula (1D ｂ ) in Y ｂrepresents a divalent organic group derived from a diamine. Z represents a group represented by the formula (1D ａ ) is synonymous with Z in

[0019]

[0020]

[0021] (In formula (E), Q is a monovalent organic group selected from the following groups (e1) to (e2). * represents a bond.) (e1) An acyclic hydrocarbon group having 1 to 6 carbon atoms. (e2) A monovalent organic group having 2 to 30 carbon atoms and having 1 or 2 carboxy groups (however, the monovalent organic group does not include an acid anhydride group).

[0022] According to the present invention, it is possible to provide a liquid crystal alignment agent that can obtain a liquid crystal alignment film having excellent in-plane uniformity of liquid crystal alignment restraining force even when the liquid crystal alignment agent is dried at low temperatures, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element.

[0023] 1 is a schematic cross-sectional view showing an example of an IPS mode in-plane switching liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention, and FIG. 2 is a schematic cross-sectional view showing an example of an FFS mode in-plane switching liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.

[0024] Hereinafter, a liquid crystal alignment agent containing a specific polymer component, a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film will be described in detail. However, the explanation of the constituent elements described below is an example of one embodiment of the present invention, and the present invention is not limited to these contents.

[0025] In the following description, examples of a "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Furthermore, "tert-", which means tertiary, is also represented by "t-". "Boc" represents a tert-butoxycarbonyl group, and "*" represents a bond. (Terminal Amino Group) The liquid crystal aligning agent of the present invention contains the above polymer (A) and polymer (B). At least a portion of the terminals of the polyamic acid (B) in the polymer (B) contain a non-amino group, and the non-amino group is a functional group represented by the above structural formula (E). That is, preferably, at least a portion of the terminal amino groups of the polyamic acid (B) are modified to have the non-amino group.

[0026] The proportion of terminal amino groups in the polyamic acid (B) is preferably 60% or less based on all the terminals of the polyamic acid (B).

[0027] The "abundance rate of terminal amino groups" referred to here is, for example, in the case of polyamic acid (B), the proportion of terminal amino groups expressed as a percentage based on all terminals of polyamic acid (B).

[0028] The phrase "based on all terminals of the polyamic acid (B)" means that the total number of amino terminals and non-amino terminals of the polyamic acid (B) is 100%, and includes the case where any terminal is 0%.

[0029] The abundance of terminal amino groups is １ It can be estimated from the change in peak intensity of the terminal amino group using H-NMR. The abundance of terminal amino groups in the polyamic acid (B) used in the present invention is more preferably 30% or less, even more preferably 10% or less, and particularly preferably 1% or less. The abundance of terminal amino groups in the polyamic acid (B) used in the present invention may also be 0%. That is, all of the terminals of the polyamic acid (B) used in the present invention may contain the non-amino group.

[0030] The non-amino group is a functional group represented by the above structural formula (E). The functional group represented by the above structural formula (E) is preferably bonded to a nitrogen atom of the diamine residue.

[0031] Preferred examples of (e1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a vinyl group, an allyl group, and a methallyl group.

[0032] Preferred specific examples of the compound that gives the above (e1) include residues derived from acyclic acid anhydrides such as acetic anhydride, acrylic anhydride, methacrylic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, isovaleric anhydride, hexanoic anhydride, and heptanoic anhydride.

[0033] Preferred examples of (e2) include monovalent organic groups having a residue derived from a dicarboxylic acid anhydride and having one or two carboxy groups.

[0034] Specific examples of dicarboxylic acid anhydrides that give the above (e2) include compounds (e2-1) that do not have an alkoxysilane structure and compounds (e2-2) that have an alkoxysilane structure.

[0035] Specific examples of compound (e2-1) include aromatic or aliphatic cyclic dicarboxylic acid anhydrides such as phthalic anhydride, 3-hydroxyphthalic anhydride, 4-ethynylphthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, allylsuccinic anhydride, (β-methallyl)succinic anhydride, itaconic anhydride, exo-7-oxanorbornene-2,3-dicarboxylic anhydride, trimellitic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 4-ethynylphthalic anhydride, cyclohexene-1,2-dicarboxylic anhydride, 2,2′-biphenyldicarboxylic anhydride, diglycolic anhydride, 3,3-dimethylglutaric anhydride, and 2,3-naphthalenedicarboxylic anhydride.

[0036] The aliphatic ring in the aliphatic cyclic dicarboxylic acid anhydride may be a saturated aliphatic ring or an unsaturated aliphatic ring.

[0037] Specific examples of compound (e2-2) include 4-(3-trimethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-triethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-trimethoxysilylpropyl)phthalic anhydride, 4-(3-triethoxysilylpropyl)phthalic anhydride; (C1-6)alkoxydimethylsilyl(C2-8)alkyl succinic anhydrides such as 2-(methoxydimethylsilyl)ethyl succinic anhydride, 3-(dimethylmethoxysilyl)propyl succinic anhydride, and 3-(dimethylethoxysilyl)propyl succinic anhydride; di(C1-6)alkoxymethylsilyl such as 2-(dimethoxymethylsilyl)ethyl succinic anhydride. tri(C1-6)alkoxysilyl(C2-8)alkyl succinic anhydrides such as 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, [3-(trimethoxysilyl)propyl]succinic anhydride, or [3-(triethoxysilyl)propyl]succinic anhydride; 4-(3-dimethylmethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-dimethylethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-dimethylmethoxysilylpropyl)phthalic anhydride, or 4-(3-dimethylethoxysilylpropyl)phthalic anhydride.

[0038] <Polyamic Acid (A)> (Structural Unit Derived from Tetracarboxylic Acid Derivative Contained in Polyamic Acid (A)) The polyamic acid (A) in the polymer (A) of the present invention contains, as a structural unit derived from a tetracarboxylic acid derivative, a structural unit represented by the above formula (1T ａ The polymer (A) may be composed of one or more types of structural units (a-1Ta), and the structural units (a-1Ta) may be composed of one or more types of structural units. ａ ) X ａ represents a tetravalent organic group represented by the above formula (X-1).

[0039] R in the above formula (X-1) １ ~R ４Specific examples of the alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 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 t-butyl group, and an n-pentyl group. １ ~R ４ Specific examples of the alkenyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, in the above R include a vinyl group, a propenyl group, and a butynyl group, which may be linear or branched. １ ~R ４ Specific examples of the alkynyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, in the above formula include an ethynyl group, a 1-propynyl group, and a 2-propynyl group.

[0040] The above R １ ~R ４ In the formula (I), examples of the monovalent organic group containing 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, that contains a fluorine atom include a fluoromethyl group, a trifluoromethyl group, a trifluoromethoxy group, a 2,2,2-trifluoroethyl group, a 2,2,2-trifluoroethoxy group, a pentafluoroethyl group, and a pentafluoropropyl group.

[0041] The above formula (X-1) is preferably one selected from the group consisting of the following formulae (x1-1) to (x1-5).

[0042]

[0043] From the viewpoint of suitably obtaining the effects of the present invention, the structural unit (a-1Ta) contained in the polyamic acid (A) of the present invention is preferably 60 mol % or more, and more preferably 70 mol % or more, relative to 1 mol of all structural units derived from tetracarboxylic acid derivatives contained in the polyamic acid (A).

[0044] The polyamic acid (A) of the present invention contains, as a structural unit derived from a tetracarboxylic acid derivative, a compound represented by the following formula (2T ａ The structural unit (2-1Ta) may be of one type or of two or more types.

[0045]

[0046] (X in the formula ａ represents a tetravalent organic group derived from a tetracarboxylic dianhydride other than the tetravalent organic group represented by the above formula (X-1). ａ ) in ２ａ Specific examples of the tetravalent organic group include a tetravalent organic group having an alicyclic structure with five or more members (T ５ａ ), or a tetravalent organic group obtained by removing two acid anhydride groups from the following tetracarboxylic acid dianhydrides (hereinafter, these may be collectively referred to as "other tetracarboxylic acid dianhydrides").

[0047] acyclic aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride or tetracarboxylic acid dianhydrides represented by the following formulae (AL-1) to (AL-7); alicyclic tetracarboxylic acid dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (provided that the tetravalent organic group (T ５ａ ) excluding tetracarboxylic dianhydrides having the following structure: 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'-perfluoroisopropylidenedi(phthalic anhydride), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride Aromatic tetracarboxylic acid dianhydrides such as hydrates, 4,4'-bis(3,4-dicarboxyphenoxy)-2,2-diphenylpropane dianhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-oxydi(1,4-phenylene)bis(phthalic)dianhydride, or 4,4'-methylenedi(1,4-phenylene)bis(phthalic)dianhydride; and also tetracarboxylic acid dianhydrides described in JP 2010-97188 A.

[0048]

[0049] More preferred examples of the other tetracarboxylic acid dianhydrides include 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, and 2,2',3,3'-biphenyltetracarboxylic acid dianhydride.

[0050] The tetravalent organic group (T ５ａ ) is preferably a tetravalent organic group having a 5- to 8-membered alicyclic structure, and more preferably a tetravalent organic group having a 5- to 7-membered alicyclic structure. Note that, when the alicyclic structure to which the acid anhydride group is bonded is a polycyclic structure, the alicyclic structure having 5 or more members means that each of the rings contained in the polycyclic structure has 5 or more atoms constituting the ring. Furthermore, the alicyclic structure may be bonded to at least one of the two acid anhydride groups, and may have a chain hydrocarbon structure or an aromatic ring structure in addition to the alicyclic structure.

[0051] Tetravalent organic group (T ５ａ ) is preferably a compound represented by the following formula (X ５ａ -1) to (X ５ａ -18). ５ａ ) is, from the viewpoint of suitably obtaining the effects of the present invention, (X ５ａ -1) to (X ５ａ -4) is more preferable.

[0052]

[0053] The polyamic acid (A) has the formula (2T ａ The proportion of the structural units represented by the formula (I) is preferably 40 mol % or less, more preferably 30 mol % or less, based on 1 mol of all structural units derived from tetracarboxylic acid derivatives contained in the polyamic acid (A).

[0054] The details of the diamine-derived structural unit contained in the polyamic acid (A) will be described later. <Polyamic Acid (B)> (Tetracarboxylic Acid Derivative-Derived Structural Unit Contained in the Polyamic Acid (B)) The liquid crystal aligning agent of the present invention is a polyamic acid (B) having, together with the polyamic acid (A), a tetracarboxylic acid derivative-derived structural unit and a diamine-derived structural unit, and the tetracarboxylic acid derivative-derived structural unit is a polyamic acid (B) having, as the tetracarboxylic acid derivative-derived structural unit, a structural unit represented by the above formula (1T ｂ The polyamic acid contains the above-mentioned polyamic acid containing a structural unit (b-1Tb) represented by the formula (b-1Tb).

[0055] The polyamic acid (B) may be composed of one type or two or more types. Furthermore, each of the structural units constituting the polyamic acid (B) may be composed of one type or two or more types.

[0056] The above formula (1T ｂ ) X ｂ The tetravalent organic group that gives the formula (T) is a tetravalent organic group obtained by removing two anhydride groups from 1,2,3,4-cyclobutanetetracarboxylic dianhydride, or the above tetravalent organic group (T ５ａ ) and a tetravalent organic group obtained by removing two anhydride groups from a tetracarboxylic dianhydride having the formula (I).

[0057] In order to suitably obtain the effects of the present invention, the polyamic acid (B) preferably contains the structural unit (b-1Tb) in an amount of more than 40 mol %, and more preferably 50 mol % or more, relative to 1 mol of all structural units derived from tetracarboxylic acid derivatives contained in the polyamic acid (B).

[0058] The polyamic acid (B) of the present invention contains, as a structural unit derived from a tetracarboxylic acid derivative, a compound represented by the following formula (2T ｂ ) may have a structural unit (b-2Tb) represented by the formula (b-2Tb).

[0059]

[0060] (X in the formula ２ｂ is X ｂ represents a tetravalent organic group other than the above formula (2T ｂ ) in ２ｂSpecific examples of the tetravalent organic group include a tetravalent organic group obtained by removing two anhydride groups from an acyclic aliphatic tetracarboxylic dianhydride, a tetravalent organic group obtained by removing two anhydride groups from an alicyclic tetracarboxylic dianhydride (provided that the tetravalent organic group represented by the above formula (X-2) and the above tetravalent organic group (T ５ａ ), and a tetravalent organic group obtained by removing two anhydride groups (—C(═O)—O—C(═O)—) from an aromatic tetracarboxylic dianhydride.

[0061] Here, 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 only of a chain hydrocarbon structure, and it may also have an alicyclic structure or an aromatic ring structure as part of it.

[0062] Alicyclic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. Furthermore, they do not necessarily have to be composed solely of an alicyclic structure, and may partially contain a chain hydrocarbon structure or an aromatic ring structure. Aromatic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an aromatic ring.

[0063] In order to preferably obtain the effects of the present invention, the above X ２ｂ The tetravalent organic group derived from an aromatic tetracarboxylic dianhydride in X is preferably a tetracarboxylic dianhydride having a benzene ring. ｂ The tetravalent organic group derived from the aromatic tetracarboxylic dianhydride in the formula (2T ａ ) in ２ａ In order to obtain the effects of the present invention, the above-mentioned X is a tetravalent organic group obtained by removing two anhydride groups from the aromatic tetracarboxylic dianhydride exemplified above. ２ｂThe tetravalent organic group in the formula (I) is preferably a tetravalent organic group obtained by removing two anhydride groups from a tetracarboxylic acid dianhydride having at least one partial structure selected from the group consisting of a substituted cyclobutane ring structure and a cyclobutene ring structure, or a tetravalent organic group obtained by removing two anhydride groups from an acyclic aliphatic tetracarboxylic acid dianhydride exemplified above as the other tetracarboxylic acid dianhydrides.

[0064] More preferred X ２ｂ is a tetravalent organic group represented by the above formula (X-1), or a tetravalent organic group obtained by removing two anhydride groups from the acyclic aliphatic tetracarboxylic acid dianhydrides exemplified above as the other tetracarboxylic acid dianhydrides.

[0065] In order to suitably obtain the effects of the present invention, the polyamic acid (B) preferably has a content of the structural unit (b-2Tb) of less than 60 mol %, and more preferably 50 mol % or less, relative to 1 mol of all structural units derived from tetracarboxylic acid derivatives contained in the polyamic acid (B).

[0066] Specific examples of the diamine-derived structural unit contained in the polyamic acid (B) include specific examples of the diamine-derived structural unit contained in the polyamic acid (A) described below. (Diamine-derived structural unit contained in the polyamic acid (A) and the polyamic acid (B)) The polyamic acid (A) in the polymer (A) of the present invention contains, as the diamine-derived structural unit, a structural unit represented by the above formula (1D ａ The structural unit (a-1Da) is represented by the structural unit (a-1D ａ ) may be one type or two or more types.

[0067] The above formula (1D ａ In the above formula, the monovalent organic group represented by Z is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a methylene group of the hydrocarbon group may be substituted with -O-, -S-, -CO-, -COO-, -COS-, -NR ３ --CO-NR ３ -, -Si(R ３ ) ２ - (However, R ３ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. ３ When there are multiple R ３may be the same or different, —SO ２ - or the like; a monovalent group in which at least one hydrogen atom bonded to a carbon atom of the above-mentioned monovalent hydrocarbon group or the above-mentioned monovalent group A is substituted with a halogen atom, a hydroxy group, an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxysilyl group, a silanol group, a sulfino group, a phosphino group, a carboxy group, a cyano group, a sulfo group, an acyl group or the like; and a monovalent group having a heterocycle.

[0068] The above formula (1D ａ In the above formula (I), the monovalent organic group for Z is preferably 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 a t-butoxycarbonyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0069] The above formula (1D ａ In order to preferably obtain the effects of the present invention, two Z's in the formula (I) are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

[0070] The polyamic acid (B) in the polymer (B) of the present invention contains, as a diamine-derived structural unit, a structural unit represented by the above formula (1D ｂ The structural unit (b-1Db) may be of one type or of two or more types. ｂ The monovalent organic group of Z in the formula (1D ａ ) is synonymous with Z.

[0071] Preferred structural units of the structural unit (a-1Da) include diamine (0) "H-N(Z)-Ar １ -L １ -A-L １’ -Ar １’ -N(Z)-H"-derived structural unit (1D-1), or a structural unit (1D-2) derived from a diamine other than the diamine (0) (hereinafter also referred to as "other diamine").

[0072] Here, Ar １ , Ar １’each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring. １ , Ar １’ Any hydrogen atom on the ring may be substituted with a monovalent group. A represents a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms.

[0073] L １ , L １’ each independently represents a single bond, -O-, -S-, -C(=O)-, -O-C(=O)-, -C(=O)-NR- (R represents a hydrogen atom or a monovalent organic group), or -NR-C(=O)- (R represents a hydrogen atom or a monovalent organic group). (Diamine (0)) L of the above diamine (0) １ , L １’ Examples of the monovalent organic group for R in -C(=O)-NR- or -NR-C(=O)- include alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms, alkenyl groups having 2 to 3 carbon atoms, acyl groups having 2 to 3 carbon atoms, alkylsilyl groups having 1 to 3 carbon atoms, alkoxysilyl groups having 1 to 3 carbon atoms, and monovalent organic groups in which at least a portion of the hydrogen atoms in these groups have been substituted with at least either halogen atoms or hydroxy groups.

[0074] Ar of the diamine (0) １ and Ar １’ Examples of the monovalent group that is a substituent for any hydrogen atom on the ring include monovalent groups such as a halogen atom; an alkyl group having 1 to 3 carbon atoms; an alkyl group having 1 to 3 carbon atoms in which at least a portion of the hydrogen atoms is substituted with a halogen atom or a hydroxy group; an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms in which at least a portion of the hydrogen atoms is substituted with at least one of the above halogen atoms and a hydroxy group; an alkenyl group having 2 to 3 carbon atoms; an acyl group having 2 to 3 carbon atoms; an alkylsilyl group having 1 to 3 carbon atoms; an alkoxysilyl group having 1 to 3 carbon atoms; a hydroxy group, and a nitrile group.

[0075] Ar of the diamine (0) １ and Ar １’Specific examples of the alkyl group include 1,4-phenylene, 1,3-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 2-butyl-1,4-phenylene, 2-isopropyl-1,4-phenylene, 2-t-butyl-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-ethoxy-1,4-phenylene, 2-propoxy-1,4-phenylene, 2-butoxy-1,4-phenylene, and 2-fluoro-1,4 a benzene ring which may have a substituent such as 4,4'-biphenylylene, 2-methyl-4,4'-biphenylylene, 2-ethyl-4,4'-biphenylylene, 2-propyl-4,4'-biphenylylene, 2-butyl-4,4'-biphenylylene, 2- t-butyl-4,4'-biphenylylene, 2-methoxy-4,4'-biphenylylene, 2-ethoxy-4,4'-biphenylylene, 2-fluoro-4,4'-biphenylylene, 3-methyl-4,4'-biphenylylene, 3-ethyl-4,4'-biphenylylene, 3-propyl-4,4'-biphenylylene, 3-butyl-4,4'-biphenylylene, 3-t-butyl-4,4'-biphenylylene, 3-methoxy-4,4'-biphenylylene, 3-ethoxy-4,4'-biphenylylene biphenyl structures which may have a substituent such as phenylylene, 3-fluoro-4,4'-biphenylylene, 2,2'-dimethyl-4,4'-biphenylylene, 3,3'-dimethyl-4,4'-biphenylylene, 3,3'-biphenylylene, 5-methyl-3,3'-biphenylylene, and 5,5'-dimethyl-3,3'-biphenylylene; and naphthalene rings which may have a substituent such as 1,5-naphthylene, 2,6-naphthylene, and 1-methyl-2,6-naphthylene.

[0076] A in the diamine (0) is a divalent organic group having 1 to 10 carbon atoms and an alkylene structure. When the alkylene structure has three or more carbon-carbon bonds, any carbon-carbon bond constituting the alkylene structure may be replaced with a carbon-carbon double bond. A is preferably an alkylene group (q0) having 1 to 10 carbon atoms; a divalent organic group (q1) obtained by inserting —O—, —C(═O)—, —NH—, —O—C(═O)—, or —C(═O)—O— between the carbon-carbon bonds of the alkylene group; or a divalent organic group (q2) having at least one —NR—C(═O)—NR— (wherein R represents a hydrogen atom or a monovalent organic group) between the carbon-carbon bonds of the alkylene group.

[0077] Here, the monovalent organic group of R in the above-mentioned —NR—C(═O)—NR— is L of the above-mentioned diamine (0). １ and L １’ Examples of the structure include the structures exemplified for R in —C(═O)—NR—, which represents:

[0078] Preferred specific examples of (q0), (q1) and (q2) are as follows:

[0079] *-(CH ２ ) ｎ - *, * - (CH ２ ) ｎ１ -O-(CH ２ ) ｎ２ -*, *-(CH ２ ) ｍ１ -OC(=O)-(CH ２ ) ｎ’ -C(=O)-O-(CH ２ ) ｍ２ -*, *-(CH ２ ) ｍ１ -C(=O)-O-(CH ２ ) ｎ’ -OC(=O)-(CH ２ ) ｍ２ - *, * - (CH ２ ) ｎ１ -NR-C(=O)-NR-(CH ２ ) ｎ２ *In the above chemical formula, R represents a hydrogen atom or a monovalent organic group. The monovalent organic group is L of the above diamine (0).１ and L １’ Examples of the structure include the structures exemplified for R in —C(═O)—NR—, which represents the following: Two Rs may be the same or different.

[0080] n is an integer of 1 to 10, more preferably an integer of 2 to 10, and even more preferably an integer of 2 to 6.

[0081] m1 and m2 each independently represent an integer of 0 to 4; n' represents an integer of 1 to 6; the sum of m1, m2 and n' is 1 to 8.

[0082] *-(CH ２ ) ｎ１ -O-(CH ２ ) ｎ２ -In *, n1 and n2 are each independently an integer of 1 to 6, and the sum of n1 and n2 is 2 to 10.

[0083] *-(CH ２ ) ｎ１ -NR-C(=O)-NR-(CH ２ ) ｎ２ -In *, n1 and n2 are each independently an integer of 1 to 6, and the sum of n1 and n2 is 2 to 9.

[0084] *-L １ -A-L １’ From the viewpoint of suitably obtaining the effects of the present invention, the following embodiments are preferred for -*. In the formulae below, the definitions of m1, m2, n, n', n1, and n2 are the same as in the formulae above. Furthermore, in the formulae below, R represents a hydrogen atom or a monovalent organic group. When two Rs are present, they each independently have the above definition. As the monovalent organic group, the group represented by the formula (H １ ) L １ and L １’ Examples of the structure include the structures exemplified for R in —C(═O)—NR—, which represents:

[0085] *-(CH ２ ) ｎ -*, -O-(CH ２ ) ｎ -O-*, *-O-(CH ２ ) ｎ１ -O-(CH ２ ) ｎ２-O-*, *-C(=O)-(CH ２ ) ｎ -C(=O)-*, *-C(=O)-NR-(CH ２ ) ｎ -O-*, *-OC(=O)-(CH ２ ) ｎ -O-*, *-OC(=O)-(CH ２ ) ｎ -OC(=O)-*, *-OC(=O)-(CH ２ ) ｎ -C(=O)-O-*, *-(CH ２ ) ｍ１ -OC(=O)-(CH ２ ) ｎ’ -C(=O)-O-(CH ２ ) ｍ２ -* *-S-(CH ２ ) ｎ -S-*, *-C(=O)-NR-(CH ２ ) ｎ -NR-C(=O)-*, *-C(=O)-O-(CH ２ ) ｎ -OC(=O)-*, *-(CH ２ ) ｍ１ -C(=O)-O-(CH ２ ) ｎ’ -OC(=O)-(CH ２ ) ｍ２ -* *-O-(CH ２ ) ｎ -*, *-S-(CH ２ ) ｎ -*, *-NR-C(=O)-(CH ２ ) ｎ -C(=O)-NR-* *-(CH ２ ) ｎ１ -NR-C(=O)-NR-(CH ２ ) ｎ２ -* Furthermore, from the viewpoint of preferably obtaining the effects of the present invention, *-(CH ２ ) ｎ -*, *-O-(CH ２ ) ｎ -O-*, *-O-(CH ２ ) ｎ - * is preferred.

[0086] The polyamic acid (A) contains, as a diamine-derived structural unit, Y ａ is a divalent organic group having three or more benzene rings, ａ ) may contain at least one structural unit represented by the formula (I).

[0087] Here, the benzene ring in the "divalent organic group having three or more benzene rings" also includes benzene rings constituting a fused ring. When counting the number of benzene rings in the diamine (0), a naphthalene ring is counted as having two benzene rings, an anthracene ring is counted as having three benzene rings, and a biphenyl structure is counted as having two benzene rings.

[0088] In the polyamic acid (A), Ar １ and Ar １’ In terms of suitably achieving the effects of the present invention, a combination of the above-mentioned optionally substituted benzene ring and the above-mentioned optionally substituted benzene ring is preferred.

[0089] In order to suitably obtain the effects of the present invention, the structural unit (1D-1) preferably has a divalent organic group represented by any one of the following formulae (h1-1) to (h1-14).

[0090] In formulae (h1-1) to (h1-14), the bonding positions of the benzene ring are preferably the 1st and 4th positions, and the bonding positions of the naphthalene ring are preferably the 2nd and 6th positions.

[0091] In formula (h1-4), —CH ２ The total number of -'s is 10 or less.

[0092] In formulae (h1-7), (h1-8), and (h1-14), —CH ２ The total number of - is 8 or less, and two m's may be the same or different.

[0093] In addition, the hydrogen atoms on the benzene rings of the following formulae (h1-1) to (h1-14) may be substituted with a methyl group, a methoxy group, or a fluorine atom.

[0094]

[0095] In one embodiment, the polyamic acid (A) preferably contains the structural unit (1D-1) in an amount of 5 to 95 mol %, more preferably 10 to 95 mol %, and even more preferably 20 to 80 mol %, relative to 1 mol of all structural units derived from diamines contained in the polyamic acid (A).

[0096] Examples of other diamines in the structural unit (1D-2) derived from other diamines include the following.

[0097] p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 1,4-diamino-2,5-methoxybenzene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine, semi-aromatic diamines having a secondary amino group and a primary amino group (preferably 4-(2-( 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy- 4,4'-diaminobiphenyl, 3-trifluoromethyl-4,4'-diaminobiphenyl, 2-trifluoromethyl-4,4'-diaminobiphenyl, 3-fluoro-4,4'-diaminobiphenyl, 2-fluoro-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl) specific diamines such as methyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,7-diaminonaphthalene (hereinafter, these will also be collectively referred to as "specific diamine (1)").); 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; 4,4'-diamino azobenzene, diaminotolan, 4,4-diaminochalcone, or [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, or [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop diamines having a photoalignment group, such as aromatic diamines having a cinnamate structure, typified by 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N,N-diallylaniline; diamines having a photopolymerizable group at the terminal, such as 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone and 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl-3,5-diaminobenzoate; diamines having an amide bond, such as 4,4'-diaminobenzanilide; diamines having a urea bond, such as 1,3-bis(4-aminophenyl)urea; H. ２ New York Ｄ -NH ２ (Y Ｄrepresents a divalent organic group having -N(D)- (D represents a protecting group which is eliminated by heating and replaced with a hydrogen atom) in the molecule; diamines having a thermally eliminable group such as 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane ethane, 4,4'-diaminodiphenylmethane, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 2,2'-bis[4-(4-aminophenoxy) phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 4, 4'-Diaminobenzophenone, 1,4-bis(4-aminobenzyl)benzene; 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, N-(3-(1H-imidazol-1-yl)propyl-3,5-Diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-benzenamine, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-2-oxazolyl]-benzenamine, 1,4-bis(p-aminobenzyl)piperazine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, 4-(4-aminophenoxycarbonyl)-1-(4-amino phenyl)piperidine, 2,5-bis(4-aminophenyl)pyrrole, 4,4'-(1-methyl-1H-pyrrole-2,5-diyl)bis[benzenamine], 1,4-bis-(4-aminophenyl)-piperazine, 2-N-(4-aminophenyl)pyridine-2,5-diamine, 2-N-(5-aminopyridin-2-yl)pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-6-aminobenzimidazole heterocycle-containing diamines such as 5-(1H-benzimidazol-2-yl)benzene-1,3-diamine, or diamines represented by the following formulae (z-1) to (z-5), or 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1 diamines having at least one nitrogen atom-containing structure selected from the group consisting of a heterocycle containing a nitrogen atom, and a secondary or tertiary amino group (excluding amino groups derived from -N(D)- (D represents a protecting group which is eliminated by heating and replaced with a hydrogen atom); hereinafter, this may also be referred to as a "specific nitrogen atom-containing structure". However, the specific nitrogen atom-containing structure is an atomic group other than the two amino groups which participate in the polycondensation reaction), typified by diamines having a diphenylamine structure such as 2,4-benzenediamine; 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamino-3,3'-dihydroxybiphenyl; 2,4-diaminobenzoic acid, 2,5-Diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diamino diamines having a carboxy group such as 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylether-3,3'-dicarboxylic acid; 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; cholestanyloxy-3,5-diaminobenzene, ... diamines having a steroid skeleton such as stenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestanyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane; diamines represented by the following formulae (V-1) and (V-2); diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane: diamines such as acyclic aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4'-methylenebis(cyclohexylamine); and 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.

[0098]

[0099]

[0100] (In formula (V-1), m and n are integers of 0 to 3 (provided that 1≦m+n≦4 is satisfied), j is an integer of 0 or 1, and X １ is -(CH ２ ) ａ -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ３ )-, -NH-, -O-, -CH ２ O-, -CH ２ represents —OCO—, —COO—, or —OCO—. １ represents a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms. ２ is -O-, -CH ２ O-, -CH ２ In formulae (z-2), (V-1), and (V-2), m, n, and X represent —OCO—, —COO—, or —OCO—. １ , R １ When two of these groups are present, each independently has the definition defined above.) D in -N(D)- of the diamine having the thermally detachable group described above is preferably a carbamate-based organic group typified by a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a Boc group, etc. The Boc group is particularly preferred from the viewpoints that it is efficiently detached by heat, detaches at a relatively low temperature, and is discharged as a harmless gas upon detachment.

[0101] Preferable examples of the diamines having a thermally detachable group exemplified as the other diamines include those represented by the following formula (d Ｄａ -1) to (d Ｄａ -8) is preferred.

[0102]

[0103] (Formula (d Ｄａ −2), (d Ｄａ -6), (d ＤａIn formula (1D-7), R represents a hydrogen atom or a Boc group.) In one embodiment, when the polyamic acid (A) used in the present invention has the structural unit (1D-2), it more preferably contains a structural unit derived from the specific diamine (1), from the viewpoint of suitably achieving the effects of the present invention.

[0104] The content of the structural units derived from the specific diamine (1) is preferably 5 to 95 mol %, more preferably 5 to 90 mol %, and even more preferably 20 to 80 mol %, based on 1 mol of all structural units derived from diamines contained in the polyamic acid (A).

[0105] In order to enhance the two-phase separation between the two polymers, the polyamic acid (A) may contain, as the structural unit (1D-2), a structural unit derived from a diamine having a thermally detachable group. The structural unit derived from a diamine having a thermally detachable group preferably accounts for 5 to 40 mol %, more preferably 5 to 35 mol %, and even more preferably 5 to 30 mol %, based on 1 mol of all structural units derived from diamines contained in the polyamic acid (A).

[0106] Furthermore, in order to suitably obtain the effects of the present invention, the polyamic acid (A) preferably has as the structural unit (1D-2) a structural unit derived from a diamine other than the diamine having the thermally detachable group, and the other diamine does not have a side chain group having 3 or more carbon atoms.

[0107] Here, examples of diamines that do not have a side chain group having 3 or more carbon atoms include diamines that have the above-mentioned photoalignable group but do not have a side chain group having 3 or more carbon atoms, diamines that have the above-mentioned specific nitrogen atom-containing structure but do not have a side chain group having 3 or more carbon atoms, and diamines represented by the above formula (V-1) that do not have a side chain group having 3 or more carbon atoms.

[0108] The polyamic acid (A) and / or the polyamic acid (B) are selected from the group consisting of the above-mentioned Y and the polyamic acid (B) in view of the small afterimage caused by the residual DC. ａ , and / or Y ｂis preferably a divalent organic group obtained by removing two amino groups from a diamine having a urea bond (for example, a diamine (0) in which A is a divalent organic group (q2), or a diamine having a urea bond exemplified in the above-mentioned other diamines), a diamine having an amide bond, a diamine having the above-mentioned specific nitrogen atom-containing structure, a diamine having a carboxy group, or a diamine selected from the group consisting of 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, p-phenylenediamine, and m-phenylenediamine (these are also collectively referred to as "specific divalent organic group (b)").

[0109] The polyamic acid (A) and / or the polyamic acid (B) are selected from the group consisting of the above-mentioned Y and the polyamic acid (B) in view of the small afterimage caused by the residual DC. ａ , and / or Y ｂ is the specific divalent organic group (b) of the formula (1D ｂ ) may be contained in an amount of 5 mol % or more, preferably 10 mol %, and more preferably 20 mol % or more relative to 1 mol of all structural units derived from diamines contained in the polyamic acid (A) and / or the polyamic acid (B).

[0110] Furthermore, from the viewpoint of suitably achieving the effects of the present invention, it is preferable that the polyamic acid (A) and / or polyamic acid (B) be a structural unit (b-1Db) derived from a diamine other than the diamine having the thermally detachable group, and that the other diamine is a structural unit derived from a diamine having no side chain group having 3 or more carbon atoms.

[0111] The above formula (1D ｂ As the monovalent organic group of Z in the above formula (1D ａ ) and Z in the above formula (I) are examples of the structures shown above.

[0112] One embodiment of the liquid crystal aligning agent of the present invention includes, but is not limited to, the following embodiment (BL).

[0113] Aspect (BL): An aspect in which the polyamic acid (A) contains the structural unit (1D-1) in an amount of 5 to 95 mol % relative to 1 mol of all diamine-derived structural units contained in the polyamic acid (A), and the polyamic acid (B) contains the specific divalent organic group (b) in an amount of 10 mol % or more relative to 1 mol of all diamine-derived structural units contained in the polyamic acid (B).

[0114] In the liquid crystal aligning agent of the present invention, from the viewpoint of the effects of the present invention, particularly, of reducing afterimages caused by residual DC, the content ratio of the polyamic acid (A) to the polyamic acid (B) may be 10 / 90 to 90 / 10, 20 / 80 to 90 / 10, or 20 / 80 to 80 / 20, in terms of the mass ratio of [polyamic acid (A) / polyamic acid (B)].

[0115] <Production of Polyamic Acid> The polyamic acid contained in the liquid crystal aligning agent of the present invention can be produced, for example, by the following method.

[0116] A polymer having an amic acid structure (polyamic acid) can be obtained by reacting a tetracarboxylic dianhydride component, a diamine component, and an amino terminal modifier, which is added as needed. ａ When the diamine component has a structure represented by the formula -N(Z)-Y ａ The structure of -N(Z)- (Y ａ , Z is defined as above.) is used, and as the tetracarboxylic acid derivative component, a diamine having X ａ (X ａ The definitions of are the same as above.) is used.

[0117] The ratio of the tetracarboxylic dianhydride to the diamine used in producing the polyamic acid is preferably 0.5 to 2 equivalents, more preferably 0.8 to 1.2 equivalents, of the acid anhydride groups of the tetracarboxylic dianhydride per equivalent of the amino groups of the diamine. As in a typical polycondensation reaction, the closer the equivalent of the acid anhydride groups of the tetracarboxylic dianhydride is to 1 equivalent, the higher the molecular weight of the resulting polyamic acid.

[0118] The reaction temperature in the production of the polyamic acid is preferably −20 to 150° C., more preferably 0 to 100° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

[0119] The polyamic acid can be produced at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration in the early stages, and then a solvent can be added.

[0120] At least some of the terminals of the polyamic acid (B) contain the non-amino group. At least some of the terminals of the polyamic acid (A) may contain the non-amino group. The non-amino group can be formed, for example, by using an amino terminal modifier.

[0121] Preferred specific examples of the amino terminal modifier include the above-mentioned acyclic acid anhydrides, compound (e2-1), and compound (e2-2).

[0122] The polyamic acid (A) and / or polyamic acid (B) can be obtained, for example, by the following production method (a), production method (b), or a method using both of them.

[0123] Production method (a): A method of polymerizing (polycondensing) a tetracarboxylic dianhydride component, a diamine component, and an amino terminal modifier added as needed in an organic solvent.

[0124] Production method (b): A method in which a tetracarboxylic dianhydride component and a diamine component are reacted in an organic solvent to obtain a polymer solution containing a polyamic acid having unmodified amino terminals, and then an amino terminal modifier is added to the polymer solution to react the terminals of the polymer.

[0125] In the above-mentioned production method (b), in order to obtain a polyamic acid having an amino terminal, the ratio of the diamine to the tetracarboxylic dianhydride used in the production of the polyamic acid is sufficient as long as the ratio of the diamine to the tetracarboxylic dianhydride is equal to or greater than the ratio of the tetracarboxylic dianhydride, and the amount of the acid anhydride group of the tetracarboxylic dianhydride is preferably 0.5 to 1.0 equivalents, more preferably 0.8 to 1.0 equivalents, per equivalent of the amino group of the diamine.

[0126] The proportion of the amino terminal modifier used is preferably 40 parts by mol or less, and more preferably 30 parts by mol or less, per 100 parts by mol of the total of the diamine components used.

[0127] The proportion of the amino terminal modifier used is preferably 0.1 part by mol or more, and more preferably 0.2 part by mol or more, per 100 parts by mol of the total of the diamine components used.

[0128] The temperature when reacting the polyamic acid with the amino terminal modifier may be the same as the reaction temperature in the production of the polyamic acid, or the reaction may be carried out while heating. The heating temperature is preferably 30 to 80°C, more preferably 30 to 60°C. The reaction time is preferably 0.1 to 24 hours, more preferably 1 to 24 hours.

[0129] Specific examples of organic solvents used in the production of the polyamic acid include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. Furthermore, when the polyamic acid to be produced has high solvent solubility, solvents such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether can be used.

[0130] <Solution Viscosity and Molecular Weight of Polyamic Acid> From the viewpoint of workability, the polyamic acid used in the present invention preferably has a solution viscosity of, for example, 10 to 1,000 mPa·s when the polyamic acid is prepared into a solution having a concentration of 10 to 15% by mass. The solution viscosity (mPa·s) of the polymer is a value measured at 25°C using an E-type rotational viscometer for a polymer solution having a concentration of 10 to 15% by mass prepared using a good solvent for the polymer (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0131] The polyamic acid preferably has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of 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 number average molecular weight (Mn) in terms of polystyrene measured by GPC, is preferably 15 or less, more preferably 10 or less. Having the molecular weight in this range ensures good alignment and stability of the liquid crystal display element.

[0132] The liquid crystal aligning agent of the present invention may contain a polymer other than the polymer (A) and the polymer (B). Specific examples of the other polymer include at least one polymer (Q) selected from the group consisting of polyimide precursors other than the polymer (A) and the polymer (B) and polyimides that are imidized products of the polyimide precursors, 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. 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.), a specific example of poly(isobutylene-maleic anhydride) copolymers includes ISOBAN-600 (manufactured by Kuraray Co., Ltd.), and a specific example of poly(vinyl ether-maleic anhydride) copolymers includes Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland Corporation).

[0133] The other polymers may be used singly or in combination of two or more. The content ratio of the other polymers is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, based on 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

[0134] In this specification, the polymer component is a general term for the polymer (A), the polymer (B), and other polymers contained in the liquid crystal aligning agent. When the polymers contained in the liquid crystal aligning agent are only the polymer (A) and the polymer (B), the polymer component refers to the polymer (A) and the polymer (B).

[0135] <Liquid crystal aligning agent> The liquid crystal aligning agent of the present invention is used for producing a liquid crystal alignment film, and is in the form of a coating liquid from the viewpoint of forming a uniform thin film. The liquid crystal aligning agent of the present invention is also preferably a coating liquid containing the above-mentioned polymer component and a solvent.

[0136] The content (concentration) of the polymer component contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the setting of the thickness of the coating film to be formed, but from the viewpoint of forming a uniform and defect-free coating film, it is preferably 1 mass % or more relative to the total amount of the liquid crystal aligning agent, and from the viewpoint of storage stability of the solution, it is preferably 10 mass % or less.

[0137] From the viewpoint of suitably obtaining the effects of the present disclosure, the total content ratio of polymer (A) and polymer (B) in the liquid crystal aligning agent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 50 parts by mass or more, relative to 100 parts by mass of the total of the polymers contained in the liquid crystal aligning agent. When the liquid crystal aligning agent contains other polymers, the content ratio of polymer (A) and polymer (B) is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, relative to 100 parts by mass of the polymer components contained in the liquid crystal aligning agent.

[0138] The solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can uniformly dissolve the polymer component. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. , N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-(3-methoxypropyl)-2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-(4-methoxybutyl)-2-pyrrolidone, 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.

[0139] In addition, the solvent contained in the liquid crystal aligning agent is preferably a mixed solvent containing, in addition to the above solvent, a solvent (hereinafter also referred to as a "poor solvent") that improves the coatability when applying the liquid crystal aligning agent and the surface smoothness of the coating film. Specific examples of the poor solvent to be used in combination are listed below, but are not limited to these.

[0140] For example, diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol Examples of the lactic acid bacteria include propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, and diisobutyl ketone (2,6-dimethyl-4-heptanone). 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 coating device, coating conditions, coating environment, etc. of the liquid crystal aligning agent.

[0141] 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.

[0142] 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-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, and N-methyl-2-pyrrolidone and γ- butyrolactone, propylene glycol monobutyl ether, and diisobutyl ketone; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisopropyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisobutyl carbinol; N-methyl-2-pyrrolidone, γ-butyrolactone, and dipropylene glycol dimethyl ether; and N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether.

[0143] The liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the solvent (hereinafter also referred to as "additive components"). Examples of such additive components include a compound for increasing the strength of the liquid crystal alignment film (hereinafter also referred to as "crosslinkable compound"), an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate or between the liquid crystal alignment film and the sealant, a dielectric or conductive substance for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film, or an imidization accelerator for promoting imidization.

[0144] Examples of the crosslinkable compound include at least one crosslinkable compound selected from the group consisting of a crosslinkable compound (c-1) having at least one substituent selected from an epoxy group, an oxetanyl group, an oxazoline structure, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group, and an alkoxy group, and a crosslinkable compound (c-2) having a polymerizable unsaturated group.

[0145] Specific preferred examples of the crosslinkable compounds (c-1) and (c-2) include the following compounds: Examples of compounds having an epoxy group 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-2,4-hexanediol, bisphenol A epoxy resins such as Epicoat 828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F epoxy resins such as Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), and hydrogenated bisphenols such as YX-8000 (manufactured by Mitsubishi Chemical Corporation). phenol A type epoxy resins, 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-) cresol novolac type epoxy resins such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), compounds in which a tertiary nitrogen atom is bonded to an aromatic carbon atom such as tetrakis(glycidyloxymethyl)methane, N,N,N',N'-tetraglycidyl-1,4-phenylenediamine, N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4.4'-diaminobiphenyl, 2,2-bis[4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane;N,N,N',N'-tetraglycidyl-1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,3-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-2-methyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl) ) cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)benzene, 1,4-bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, 1,3,5-tris(N,N-diglycidylaminomethyl)benzene and other compounds in which a tertiary nitrogen atom is bonded to an aliphatic carbon atom; isocyanurate compounds such as triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.); compounds described in paragraph

[0037] of JP-A-10-338880 and compounds described in WO2017 / 170483; Examples of compounds having an oxetanyl group include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (Aron Oxetane OXT-121 (XDO)), bis[2-(3-oxetanyl)butyl]ether (Aron Oxetane OXT-221 (DOX)), 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), and compounds having two or more oxetanyl groups described in paragraphs

[0170] to

[0175] of WO2011 / 132751;

[0146] Examples of compounds having an oxazoline structure include compounds such as 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), and 2,2'-(m-phenylene)bis(2-oxazoline), polymers and oligomers having an oxazoline group such as EPOCROS (trade name, manufactured by Nippon Shokubai Co., Ltd.), and compounds described in paragraph

[0115] of Japanese Patent Application Laid-Open No. 2007-286597; Examples of compounds having a cyclocarbonate group include N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N',-di[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine, and the compounds described in paragraphs

[0025] to

[0030] and

[0032] of WO2011 / 155577; Examples of compounds having a blocked isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, and Millionate MS-50 (all manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals, Inc.), compounds having two or more blocked isocyanate groups described in paragraphs

[0046] to

[0047] of Japanese Patent Application Laid-Open No. 2014-224978, and compounds having three or more blocked isocyanate groups described in paragraphs

[0119] to

[0120] of WO2015 / 141598; Examples of compounds having a hydroxy group and / or an alkoxy group include 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-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane, compounds described in WO2015 / 072554 and paragraph

[0058] of JP2016-118753A, compounds described in JP2016-200798A, and compounds described in WO2010 / 074269A;Examples of crosslinkable compounds having a polymerizable unsaturated group include glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-, 1,3-mixture), glycerin tris(meth)acrylate, glycerol 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;

[0147] The above compounds are examples of crosslinkable compounds, and are not limited thereto. For example, components other than those described above are disclosed on pages 53

[0105] to 55

[0116] of WO2015 / 060357. Two or more types of crosslinkable compounds may be combined.

[0148] When a crosslinkable compound is used, the content of the crosslinkable compound in the liquid crystal aligning agent is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

[0149] Examples of the adhesion aid 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, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-3-triethoxysilylpropyltriethylenetetramine, N-3-trimethoxysilylpropyltriethylenetetramine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Examples of silane coupling agents include silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0150] When an adhesion aid is used, the content of the adhesion aid in the liquid crystal aligning agent 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.

[0151] Examples of the dielectric or conductive material include monoamines having a nitrogen-containing aromatic heterocycle, such as 3-picolylamine.

[0152] When a dielectric or conductive substance is used, the content of the dielectric or conductive substance in the liquid crystal aligning agent 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. (Liquid Crystal Alignment Film) The liquid crystal alignment film of the present invention is formed using the liquid crystal aligning agent of the present invention.

[0153] The method for producing a liquid crystal alignment film of the present invention comprises, for example, applying the above-mentioned liquid crystal aligning agent to a substrate, baking the applied liquid crystal aligning agent, and irradiating the resulting film with polarized radiation.

[0154] A preferred embodiment of the method for producing a liquid crystal alignment film of the present invention includes, for example, a method for producing a liquid crystal alignment film, which includes a step of applying the above-mentioned liquid crystal alignment agent to a substrate (step (1)), a step of baking the applied liquid crystal alignment agent (step (2)), and, in some cases, a step of performing an alignment treatment on the film obtained in step (2) (step (3)).

[0155] <Step (1)> The substrate onto which the liquid crystal aligning agent used in the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and glass substrates, silicon nitride substrates, acrylic substrates, polycarbonate substrates, and other plastic substrates can also be used. In this case, using a substrate on which an ITO (Indium Tin Oxide) electrode for driving the liquid crystal is formed is preferable from the viewpoint of simplifying the process. Furthermore, in a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used for only one substrate, and in this case, a light-reflecting material such as aluminum can also be used for the electrode. Furthermore, when manufacturing an IPS drive system or FFS drive system liquid crystal display element, a substrate provided with an electrode made of a comb-shaped patterned transparent conductive film or metal film and an opposing substrate without an electrode are used.

[0156] Examples of a method for applying the liquid crystal alignment agent to a substrate and forming a film include screen printing, offset printing, flexographic printing, an inkjet method, and a spray method. Among these, the application and film formation method by the inkjet method is preferably used.

[0157] An IPS substrate, which is a comb-tooth electrode substrate used in the IPS system (mode), has a base material, a plurality of linear electrodes formed on the base material and arranged in a comb-tooth pattern, and a liquid crystal alignment film formed on the base material so as to cover the linear electrodes.

[0158] The FFS substrate, which is a comb-tooth electrode substrate used in the FFS method (mode), has a base material, a surface electrode formed on the base material, an insulating film formed on the surface electrode, a plurality of linear electrodes formed on the insulating film and arranged in a comb-tooth shape, and a liquid crystal alignment film formed on the insulating film so as to cover the linear electrodes.

[0159] FIG. 1 is a schematic cross-sectional view showing an example of an IPS mode in-plane switching liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.

[0160] In the IPS LCD element 1 illustrated in Fig. 1, liquid crystal 3 is sandwiched between a comb-shaped electrode substrate 2 having a liquid crystal alignment film 2c and a counter substrate 4 having a liquid crystal alignment film 4a. The comb-shaped electrode substrate 2 has a base material 2a, a plurality of linear electrodes 2b formed on the base material 2a and arranged in a comb-like pattern, and a liquid crystal alignment film 2c formed on the base material 2a so as to cover the linear electrodes 2b. The counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2c is a liquid crystal alignment film of the present invention. The liquid crystal alignment film 4c is also a liquid crystal alignment film of the present invention.

[0161] In the IPS LCD element 1 shown in FIG. 1, when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as indicated by electric force lines L.

[0162] FIG. 2 is a schematic cross-sectional view showing an example of an FFS mode in-plane switching liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.

[0163] In the IPS LCD element 1 illustrated in Figure 2, liquid crystal 3 is sandwiched between a comb-shaped electrode substrate 2 having a liquid crystal alignment film 2h and a counter substrate 4 having a liquid crystal alignment film 4a. The comb-shaped electrode substrate 2 has a base material 2d, a surface electrode 2e formed on the base material 2d, an insulating film 2f formed on the surface electrode 2e, a plurality of linear electrodes 2g formed on the insulating film 2f and arranged in a comb-like pattern, and a liquid crystal alignment film 2h formed on the insulating film 2f so as to cover the linear electrodes 2g. The counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2h is a liquid crystal alignment film of the present invention. The liquid crystal alignment film 4a is also a liquid crystal alignment film of the present invention.

[0164] In the IPS LCD element 1 shown in FIG. 2, when a voltage is applied to the surface electrodes 2e and the linear electrodes 2g, an electric field is generated between the surface electrodes 2e and the linear electrodes 2g as indicated by electric force lines L.

[0165] <Step (2)> Step (2) is a step of baking the liquid crystal aligning agent applied to the substrate to form a film. After applying the liquid crystal aligning agent to the substrate, the solvent can be evaporated or the amic acid or amic acid ester in the polymer can be thermally imidized using a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven. The drying and baking steps after applying the liquid crystal aligning agent of the present invention can be performed at any temperature and for any time, and may be performed multiple times. The temperature for evaporating the solvent in the liquid crystal aligning agent can be, for example, 40 to 180°C as the heating means temperature, but may also be 40 to 150°C from the perspective of shortening the process. The baking time is not particularly limited, but is, for example, 1 to 10 minutes, preferably 1 to 5 minutes. When a step of thermally imidizing the amic acid in the polymer is performed in addition to the step of evaporating the solvent, a further baking step can be performed after the solvent evaporation step at a heating means temperature of, for example, 150 to 300°C, preferably 150 to 250°C. The baking time in the thermal imidization step is not particularly limited, but is, for example, 5 to 40 minutes, and preferably 5 to 30 minutes.

[0166] If the film-like material after baking is too thin, the reliability of the liquid crystal display element may decrease, so the thickness is preferably 5 to 300 nm, and more preferably 10 to 200 nm. <Step (3)> Step (3) is a step of performing an alignment treatment on the film obtained in step (2). Alignment treatment methods for liquid crystal alignment films include rubbing treatment and photo-alignment treatment, with photo-alignment treatment being preferred. Examples of photo-alignment treatment methods include irradiating the surface of the film-like material with polarized radiation in a certain direction, and optionally performing a heat treatment 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, and more preferably 200 to 400 nm.

[0167] The radiation dose is 1 to 10,000 mJ / cm ２ is preferred, and 100 to 5,000 mJ / cm ２ is more preferred.

[0168] Examples of light sources that can be used for the irradiation light include low-pressure mercury lamps, high-pressure mercury lamps, deep UV lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury-xenon lamps, excimer lasers (e.g., KrF excimer lasers), fluorescent lamps, LED lamps, halogen lamps (e.g., sodium lamps), and microwave-excited electrodeless lamps.

[0169] Furthermore, when polarized light is used as the irradiation light, the higher the extinction ratio of the polarized light, the higher the anisotropy that can be imparted. For example, in the case of ultraviolet light, the extinction ratio of polarized ultraviolet light is more preferably 10:1 or more, and even more preferably 20:1 or more.

[0170] In addition, when irradiating with radiation, in order to improve the liquid crystal alignment, the substrate having the film-like material may be irradiated while being heated at 50 to 250° C. The liquid crystal alignment film thus produced can stably align liquid crystal molecules in a certain direction.

[0171] Furthermore, the liquid crystal alignment film irradiated with polarized radiation by the above method can be contacted with a solvent or the liquid crystal alignment film irradiated with radiation can be heat-treated.

[0172] The solvent used in the contact treatment is not particularly limited, as long as it dissolves the decomposition products generated from the film-like material by irradiation 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, and cyclohexyl acetate. Among these, water, 2-propanol, 1-methoxy-2-propanol, and ethyl lactate are preferred from the viewpoints of versatility and solvent safety. Water, 1-methoxy-2-propanol, and ethyl lactate are more preferred. The solvent may be one type or a combination of two or more types.

[0173] Examples of the contact treatment include immersion treatment and spray treatment (also referred to as spray treatment). The treatment time in these treatments is preferably 10 seconds to 1 hour from the viewpoint of efficiently dissolving the decomposition products generated from the film-like material by irradiation with radiation. In particular, immersion treatment for 1 minute to 30 minutes is more preferable. The solvent used in the contact treatment may be at room temperature or heated, preferably 10 to 80°C, and more preferably 20 to 50°C. In addition, ultrasonic treatment or the like may be performed as necessary from the viewpoint of the solubility of the decomposition products.

[0174] After the contact treatment, it is preferable to perform rinsing (also called "rinsing") with a low-boiling solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone, and then calcination. In this case, either rinsing or calcination may be performed, or both may be performed. The calcination temperature is preferably 150 to 300°C, more preferably 180 to 250°C, and even more preferably 200 to 230°C. The calcination time is preferably 10 seconds to 30 minutes, and more preferably 1 minute to 10 minutes.

[0175] The heat treatment of the coating film irradiated with the radiation is preferably carried out at 50 to 300° C. for 1 to 30 minutes, more preferably at 120 to 250° C. for 1 to 30 minutes.

[0176] (Liquid Crystal Display Element) The liquid crystal display element of the present invention has the liquid crystal alignment film of the present invention.

[0177] The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a liquid crystal display element of a horizontal electric field type such as an IPS type or an FFS type, from the viewpoint of obtaining high liquid crystal alignment properties, and is particularly useful as a liquid crystal alignment film for a liquid crystal display element of an FFS type.

[0178] A liquid crystal display element can be produced by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention, preparing a liquid crystal cell by a known method, and arranging liquid crystals in the liquid crystal cell. Specifically, the following two methods can be mentioned.

[0179] 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.

[0180] The second method is called the ODF (One Drop Fill) method. For example, a UV-curable sealant is applied to a predetermined location on one of two substrates on which a liquid crystal alignment film 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.

[0181] In either the first method or the second method, it is further desirable to heat the liquid crystal composition used to a temperature at which it assumes an isotropic phase, and then slowly cool it to room temperature to remove flow alignment that occurs during liquid crystal filling.

[0182] When the coating films are subjected to a rubbing treatment, the two substrates are arranged to face each other so that the rubbing directions of the coating films are at a predetermined angle, for example, perpendicular or antiparallel. Similarly, when a photo-alignment treatment is performed, the substrates are arranged to face each other so that the alignment directions are at a predetermined angle, for example, perpendicular or antiparallel.

[0183] The sealing agent may be, for example, an epoxy resin containing a hardener and aluminum oxide spheres as spacers. The liquid crystal may be a nematic liquid crystal or a smectic liquid crystal, with a nematic liquid crystal being preferred.

[0184] The liquid crystal composition is not particularly limited, and is a composition containing at least one liquid crystal compound (liquid crystal molecule), and either a liquid crystal composition having a positive dielectric anisotropy (also called a positive liquid crystal composition or positive liquid crystal) or a liquid crystal composition having a negative dielectric anisotropy (also called a negative liquid crystal composition or negative liquid crystal) may be used, but negative liquid crystal materials are preferred.

[0185] 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 crystal properties within the molecule (e.g., a bimesogenic compound in which two rigid biphenyl structures or terphenyl structures are connected by an alkyl group). 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.

[0186] In order to improve the alignment properties of the liquid crystal, the liquid crystal composition may further contain additives, such as photopolymerizable monomers having a polymerizable group as described below, optically active compounds (e.g., S-811 manufactured by Merck), antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, or polymerization inhibitors.

[0187] Examples of the positive liquid crystal include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081 manufactured by Merck.

[0188] Examples of negative liquid crystals include MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, and MLC-7029 manufactured by Merck.

[0189] In the PSA mode, MLC-3023 manufactured by Merck is an example of a liquid crystal containing a compound having a polymerizable group.

[0190] Next, polarizing plates are installed. Specifically, a pair of polarizing plates are attached to the surfaces of the two substrates opposite the liquid crystal layer. Examples of polarizing plates include a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine, sandwiched between cellulose acetate protective films, and a polarizing plate made of the H film itself.

[0191] 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 properties are as follows: (Organic solvents) NMP: N-methyl-2-pyrrolidone BCS: Ethylene glycol monobutyl ether (Tetracarboxylic acid dianhydrides) CA-1 to CA-3: Compounds represented by the following formulas (CA-1) to (CA-3), respectively

[0192]

[0193] (Diamine) DA-1 to DA-9: Compounds represented by the following formulas (DA-1) to (DA-9), respectively

[0194]

[0195] (Amino terminal modifiers) AD-1 to AD-15: Compounds represented by the following formulas (AD-1) to (AD-15), respectively.

[0196]

[0197] (Additives) CL-1 to CL-6: Compounds represented by the following formulas (CL-1) to (CL-6), respectively

[0198] <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).

[0199] <Measurement of Molecular Weight> Measurement was carried out using the following room temperature GPC (gel permeation chromatography) device, and Mn (number average molecular weight) and Mw (weight average molecular weight) were calculated as values ​​converted into polyethylene glycol and polyethylene oxide.

[0200] GPC apparatus: GPC-101 (manufactured by Resonac (formerly Showa Denko) Co., Ltd.), Column: GPC KD-803 and GPC KD-805 (manufactured by Resonac (formerly Showa Denko) Co., Ltd.) in series, Column temperature: 50°C, Eluent: N,N-dimethylformamide (with lithium bromide monohydrate (LiBr.H) as an additive). ２o-Phosphoric acid (o-Phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L), Flow rate: 1.0 mL / min. Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, about 150,000, about 100,000, and about 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, about 4,000, and about 1,000) (manufactured by Polymer Laboratory Co., Ltd.).

[0201] [Polymer Synthesis] <Synthesis Example 1> DA-1 (0.65 g, 6.0 mmol), DA-3 (2.20 g, 9.0 mmol), DA-4 (2.88 g, 9.0 mmol), DA-5 (2.39 g, 6.0 mmol), and NMP (59.56 g) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature while supplying nitrogen to dissolve. Thereafter, CA-1 (6.19 g, 27.6 mmol) and NMP (45.37 g) were added under ice cooling, and the mixture was stirred at 40 ° C. for 12 hours to obtain a polyamic acid solution PAA-1 (viscosity: 83 mPa s, Mn: 5689, Mw: 12606) having a solids concentration of 12% by mass. Synthesis Example 2 Into a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, DA-1 (0.49 g, 4.5 mmol), DA-2 (0.55 g, 4.5 mmol), DA-3 (2.20 g, 9.0 mmol), DA-6 (1.63 g, 6.0 mmol), DA-5 (2.39 g, 6.0 mmol), and NMP (53.24 g) were added, and the mixture was stirred at room temperature while supplying nitrogen to dissolve. Thereafter, under ice cooling, CA-1 (6.19 g, 27.6 mmol) and NMP (45.37 g) were added, and the mixture was stirred at 40 ° C. for 12 hours to obtain a polyamic acid solution PAA-2 (viscosity: 85 mPa s, Mn: 6674, Mw: 14665) having a solids concentration of 12% by mass. Synthesis Example 3 DA-7 (4.78 g, 24.0 mmol), DA-8 (1.79 g, 6.0 mmol), and NMP (59.15 g) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature while supplying nitrogen to dissolve. Thereafter, CA-2 (5.30 g, 27.0 mmol) and NMP (47.65 g) were added under ice cooling, and the mixture was stirred at room temperature (25° C.) for 12 hours to obtain a polyamic acid solution PAA-3 (viscosity: 122 mPa s, Mn: 8774, Mw: 23336) having a solids concentration of 10% by mass. Synthesis Example 4 DA-7 (4.78 g, 24.0 mmol), DA-1 (0.65 g, 6.0 mmol), and NMP (48.88 g) were placed in a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature while supplying nitrogen to dissolve the mixture.Thereafter, CA-2 (5.59 g, 28.5 mmol) and NMP (50.30 g) were added under ice cooling, and the mixture was stirred at room temperature (25° C.) for 12 hours to obtain a polyamic acid solution PAA-4 (viscosity: 228 mPa s, Mn: 16496, Mw: 37449) having a solid content concentration of 10 mass %.

[0202] <Synthesis Example 5> DA-1 (2.59 g, 24.0 mmol), DA-9 (0.65 g, 6.0 mmol), and NMP (29.20 g) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature while feeding nitrogen. Thereafter, under ice cooling, CA-3 (1.89 g, 7.6 mmol) and NMP (25.93 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 2 hours. Thereafter, after cooling to 15 ° C., CA-2 (4.12 g, 21.0 mmol) and NMP (12.70 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 12 hours to obtain a polyamic acid solution PAA-5 (viscosity: 325 mPa s, Mn: 12675, Mw: 31125) having a solids concentration of 12% by mass. <Synthesis Example 14> DA-7 (4.78 g, 24.0 mmol), DA-8 (1.79 g, 6.0 mmol), and NMP (59.15 g) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature while feeding nitrogen to dissolve. Thereafter, under ice cooling, CA-3 (3.75 g, 15.0 mmol) and NMP (24.62 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 2 hours. Thereafter, after cooling to 15 ° C., CA-2 (2.74 g, 14.0 mmol) and NMP (12.01 g) were added, and the mixture was stirred at 50 ° C. for 12 hours to obtain a polyamic acid solution PAA-6 (viscosity: 456 mPa s, Mn: 20228, Mw: 52631) having a solids concentration of 12% by mass. [Synthesis of Polymer Having Non-Amino Terminal Structure] <Synthesis Example 6> AD-1 (0.05 g, 0.5 mmol) and NMP (0.45 g) were added to 20 g of the above polyamic acid solution (PAA-3), and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-1). <Synthesis Example 7> AD-1 (0.10 g, 1.0 mmol) and NMP (0.90 g) were added to 20 g of the above polyamic acid solution (PAA-3), and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-2). <Synthesis Example 8> AD-1 (0.15 g, 1.5 mmol) and NMP (1.35 g) were added to 20 g of the above polyamic acid solution (PAA-3), and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-3).Synthesis Example 9: To 20 g of the polyamic acid solution (PAA-3), AD-2 (0.16 g, 1.0 mmol) and NMP (1.4 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-4). Synthesis Example 10: To 20 g of the polyamic acid solution (PAA-3), AD-3 (0.15 g, 1.0 mmol) and NMP (1.35 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-5).

[0203] Synthesis Example 11: To 20 g of the polyamic acid solution (PAA-3), AD-4 (0.10 g, 1.0 mmol) and NMP (0.90 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-6). Synthesis Example 12: To 20 g of the polyamic acid solution (PAA-4), AD-1 (0.06 g, 0.6 mmol) and NMP (0.54 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-4-1). Synthesis Example 13: To 20 g of the polyamic acid solution (PAA-5), AD-1 (0.08 g, 0.8 mmol) and NMP (0.59 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-5-1). Synthesis Example 15: To 20 g of the polyamic acid solution (PAA-6), AD-1 (0.04 g, 0.4 mmol) and NMP (0.29 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-6-1). Synthesis Example 16: To 20 g of the polyamic acid solution (PAA-3), AD-5 (0.10 g, 1.0 mmol) and NMP (0.90 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-7). Synthesis Example 17: To 20 g of the polyamic acid solution (PAA-3), AD-6 (0.10 g, 1.0 mmol) and NMP (0.90 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-8). Synthesis Example 18: To 20 g of the polyamic acid solution (PAA-3), AD-7 (0.23 g, 1.0 mmol) and NMP (2.07 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-9). Synthesis Example 19: To 20 g of the polyamic acid solution (PAA-3), AD-8 (0.12 g, 1.0 mmol) and NMP (1.08 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-10).Synthesis Example 20: To 20 g of the polyamic acid solution (PAA-3), AD-9 (0.17 g, 1.0 mmol) and NMP (1.53 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-11). Synthesis Example 21: To 20 g of the polyamic acid solution (PAA-3), AD-10 (0.14 g, 1.0 mmol) and NMP (1.26 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-12). Synthesis Example 22: To 20 g of the polyamic acid solution (PAA-3), AD-11 (0.16 g, 1.0 mmol) and NMP (1.44 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-13). Synthesis Example 23: To 20 g of the polyamic acid solution (PAA-3), AD-12 (0.20 g, 1.0 mmol) and NMP (1.80 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-14). Synthesis Example 24: To 20 g of the polyamic acid solution (PAA-3), AD-13 (0.17 g, 1.0 mmol) and NMP (1.53 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-15). Synthesis Example 25: To 20 g of the polyamic acid solution (PAA-3), AD-14 (0.17 g, 1.0 mmol) and NMP (1.53 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-16). Synthesis Example 26 To 20 g of the above polyamic acid solution (PAA-3), AD-15 (0.31 g, 1.0 mmol) and NMP (2.79 g) were added, and the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid having a non-amino terminal structure (PAA-3-17).

[0204] The specifications of the polyamic acids obtained in the above synthesis examples are shown in Table 1.

[0205]

[0206] [Preparation of Liquid Crystal Alignment Agent] Comparative Example 1 Using the polyamic acid solution PAA-1 and the polyamic acid solution PAA-3, the polyamic acid solution PAA-1 (3.3 g) and the polyamic acid solution PAA-3 (6.0 g) were mixed so that the mass ratio of the two types of polymers was 40: 60. To this mixture, NMP (3.6 g), BCS (6.0 g), an NMP solution containing 10 wt% of CL-1 (0.1 g), and an NMP solution containing 1 wt% of CL-6 (1.0 g) were added with stirring, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal alignment agent (AL-R1) having a mass ratio of polymer solids to each solvent (polymer solids:NMP:BCS) of 5:65:30. <Comparative Examples 2 to 7, Examples 1 to 23> By carrying out the same operation as in Comparative Example 1 above with the mixing amounts shown in Table 2, liquid crystal aligning agents (AL-R2) to (AL-R7) and (AL-1) to (AL-23) were obtained, each having a polymer solid content to each solvent mass ratio (polymer solid content:NMP:BCS) of 5:65:30. <Example 24> Using the polyamic acid solution PAA-2 and the polyamic acid solution PAA-3-2, the polyamic acid solution PAA-2 (3.3 g) and the polyamic acid solution PAA-3-2 (6.0 g) were mixed so that the mass ratio of the two types of polymers became 40:60. To this mixture, NMP (3.6 g), BCS (6.0 g), an NMP solution (0.1 g) containing 10 wt% of CL-2, and an NMP solution (1.0 g) containing 1 wt% of CL-6 were added with stirring, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (AL-24) having a polymer solid content to each solvent mass ratio (polymer solid content:NMP:BCS) of 5:65:30. Example 25 Using the above polyamic acid solution PAA-2 and the above polyamic acid solution PAA-3-2, the polyamic acid solution PAA-2 (3.3 g) and the polyamic acid solution PAA-3-2 (6.0 g) were mixed so that the mass ratio of the two types of polymers became 40:60. To this mixture, NMP (3.6 g), BCS (6.0 g), an NMP solution containing 10 wt % of CL-3 (0.1 g), and an NMP solution containing 1 wt % of CL-6 (1.0 g) were added with stirring, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (AL-25) having a mass ratio of polymer solids to each solvent (polymer solids:NMP:BCS) of 5:65:30.Example 26 Using the polyamic acid solution PAA-2 and the polyamic acid solution PAA-3-2, the polyamic acid solution PAA-2 (3.3 g) and the polyamic acid solution PAA-3-2 (6.0 g) were mixed so that the mass ratio of the two polymers was 40: 60. To this mixture, NMP (3.6 g), BCS (6.0 g), an NMP solution containing 10 wt% of CL-4 (0.1 g), and an NMP solution containing 1 wt% of CL-6 (1.0 g) were added with stirring, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (AL-26) having a mass ratio of polymer solids to each solvent (polymer solids: NMP: BCS) of 5: 65: 30. Example 27 Using the polyamic acid solution PAA-2 and the polyamic acid solution PAA-3-2, the polyamic acid solution PAA-2 (3.3 g) and the polyamic acid solution PAA-3-2 (6.0 g) were mixed so that the mass ratio of the two polymers was 40: 60. To this mixture, NMP (3.6 g), BCS (6.0 g), an NMP solution containing 10 wt% of CL-5 (0.1 g), and an NMP solution containing 1 wt% of CL-6 (1.0 g) were added with stirring, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (AL-27) having a mass ratio of polymer solids to each solvent (polymer solids: NMP: BCS) of 5: 65: 30.

[0207]

[0208] [Preparation of FFS Drive Liquid Crystal Cell] <Comparative Examples 1 to 7, Examples 1 to 27> Liquid crystal cells having the structure of an FFS mode liquid crystal display element were prepared.

[0209] First, a substrate with electrodes was prepared. The substrate was a rectangular glass substrate measuring 30 mm x 35 mm and 0.7 mm thick. A solid-patterned ITO electrode constituting a common electrode was formed on the substrate as the first layer. A SiN (silicon nitride) film formed by CVD (chemical vapor deposition) was formed on the first common electrode as the second layer. The second SiN film had a thickness of 300 nm, which served as an interlayer insulating film. A comb-shaped pixel electrode formed by patterning an ITO film as the third layer was placed on the second SiN film. Two pixels, a first pixel and a second pixel, were formed, each measuring 10 mm long and 5 mm wide. This electrode-equipped substrate had a structure in which the first common electrode and the third pixel electrode were insulated by the second SiN film.

[0210] The pixel electrode of the third layer had a comb-like shape with the central portion bent at an interior angle of 160° and multiple electrode lines, each 3 μm wide, arranged parallel to each other at intervals of 6 μm. One pixel was formed by multiple electrode lines and had a first region and a second region separated by a line connecting the bent portions.

[0211] Next, the liquid crystal alignment agents (AL-R1) to (AL-R7), (AL-1) to (AL-27) obtained in the above Comparative Examples 1 to 7 and Examples 1 to 27 were filtered through a filter with a pore size of 1.0 μm, and then applied by spin coating to the above electrode-attached substrate (hereinafter referred to as the "electrode substrate") and a glass substrate (hereinafter referred to as the "counter substrate") having a 4 μm high columnar spacer with an ITO film formed on the back surface. After drying for 2 minutes on a hot plate at 50 ° C, it was baked for 30 minutes in an IR oven at 230 ° C to form a coating film with a thickness of 100 nm. 400 mJ / cm of 254 nm polarized ultraviolet light was applied to the coating surface through a 240 nm low-cut filter and a polarizer. ２The substrate was then irradiated with UV light and baked for 30 minutes in an IR oven at 230°C to obtain a substrate with a liquid crystal alignment film. The liquid crystal alignment film formed on the electrode substrate was oriented so that the direction dividing the interior angles of the pixel bends was perpendicular to the alignment direction of the liquid crystal. The liquid crystal alignment film formed on the counter substrate was oriented so that the alignment direction of the liquid crystal on the electrode substrate coincided with the alignment direction of the liquid crystal on the counter substrate when the liquid crystal cell was fabricated. The two substrates were combined into a pair, and a sealant (Mitsui Chemicals, Inc., XN-1500T) was printed on one substrate using a dispenser. Another substrate was then attached to the pair, facing each other with the alignment directions of the liquid crystal alignment films aligned at 0°. The bonded substrates were then pressure-bonded and heated in a circulating hot air oven at 150°C for 60 minutes to harden the sealant, producing an empty cell. Positive liquid crystal MLC-3019 (manufactured by Merck) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell. The obtained FFS drive liquid crystal cell was then heated at 120°C for 1 hour and left at 23°C overnight before being used for evaluation.

[0212] [Evaluation of in-plane uniformity of liquid crystal alignment restraining force] When the FFS drive liquid crystal cells obtained using the liquid crystal alignment agents (AL-1) to (AL-27) of Examples 1 to 27 were visually observed, it was confirmed that there was no disturbance in the liquid crystal alignment and that the liquid crystal was aligned uniformly in the plane.

[0213] Furthermore, using an AxoStep manufactured by AXOMETRICS, the twist angle variation of the FFS-driven liquid crystal cells obtained in the above Comparative Examples 1 to 7 and Examples 1 to 27 was evaluated. The liquid crystal cells prepared above were 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. The results are shown in Table 3.

[0214]

[0215] As shown in Table 3, compared to the liquid crystal alignment agents (AL-R1) to (AL-R3) using polyamic acids (PAA-3) to (PAA-5) that do not have a non-amino terminal structure in the second component, the liquid crystal alignment agents (AL-1) to (AL-8), (AL-12) to (AL-22) using polyamic acids (PAA-3-1) to (PAA-3-17), (PAA-4-1), and (PAA-5-1) that have a non-amino terminal structure, had better in-plane uniformity of the liquid crystal alignment restraint force. In addition, compared to the liquid crystal alignment agents (AL-R4) to (AL-R7) using polyamic acids (PAA-3) to (PAA-6) that do not have a non-amino terminal structure as the second component, the liquid crystal alignment agents (AL-9) to (AL-11), (AL-23) to (AL-27) using polyamic acids (PAA-3-2), (PAA-4-1), (PAA-5-1), and (PAA-6-1) that have a non-amino terminal structure, had better in-plane uniformity of the liquid crystal alignment restraint force.

[0216] By using the liquid crystal aligning agent of the present invention, a liquid crystal alignment film with high in-plane uniformity of the liquid crystal alignment restraining force can be obtained even when dried at low temperatures. Therefore, it is possible to obtain a liquid crystal display element with high display quality while reducing energy consumption in the manufacturing process of the liquid crystal display element. These elements are useful in liquid crystal displays for display purposes, light control windows that control the transmission and blocking of light, optical shutters, etc. The liquid crystal display element of the present invention can be effectively applied to devices with various functions, such as liquid crystal televisions, clocks, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, and information displays.

[0217] The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2024-024113 filed on February 20, 2024 are hereby incorporated by reference as the disclosure of the present invention.

[0218] 1: In-plane switching liquid crystal display element, 2: comb-tooth electrode substrate, 2a: substrate, 2b: linear electrode, 2c: liquid crystal alignment film, 2d: substrate, 2e: plane electrode, 2f: insulating film, 2g: linear electrode, 2h: liquid crystal alignment film, 3: liquid crystal, 4: opposing substrate, 4a: liquid crystal alignment film, 4b: substrate, L: electric field line

Claims

1. A liquid crystal aligning agent characterized by containing the following polymer (A) and polymer (B): Polymer (A): A polyamic acid (A) having a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine, wherein the structural unit derived from the tetracarboxylic acid derivative is a structural unit represented by the following formula (1T ａ As a diamine-derived structural unit, a structural unit (a-1Ta) represented by the following formula (1D ａ The polyamic acid as described above, which contains a structural unit (a-1Da) represented by the formula (a-1Da). Polymer (B): A polyamic acid (B) having a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine, wherein the structural unit derived from the tetracarboxylic acid derivative is a structural unit represented by the following formula (1T ｂ As a diamine-derived structural unit, a structural unit (b-1Tb) represented by the following formula (1D ｂ ), wherein at least a portion of the terminals of the polyamic acid (B) contain a non-amino group, and the non-amino group is a functional group represented by the following structural formula (E): (Formula (1T ａ ) Medium X ａ represents a tetravalent organic group represented by the following formula (X-1): ａ ) in Y ａ represents a divalent organic group derived from a diamine. Each Z independently represents a hydrogen atom or a monovalent organic group. (In formula (X-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, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, or a phenyl group; R １ ~R ４ At least one of represents a group other than a hydrogen atom as defined above. * represents a bond.) (Formula (1T ｂ ) Medium X ｂ is a tetravalent organic group represented by the following formula (X-2), or a tetravalent organic group having an alicyclic structure with five or more members (T ５ａ ) is represented by the formula (1D ｂ ) in Y ｂ represents a divalent organic group derived from a diamine. Z represents a group represented by the formula (1D ａ ) is synonymous with Z in (In formula (E), Q is a monovalent organic group selected from the following groups (e1) to (e2). * represents a bond.) (e1) An acyclic hydrocarbon group having 1 to 6 carbon atoms. (e2) A monovalent organic group having 2 to 30 carbon atoms and having 1 or 2 carboxy groups (however, the monovalent organic group does not include an acid anhydride group).

2. The liquid crystal aligning agent according to claim 1, wherein (e1) is a residue derived from an acyclic acid anhydride.

3. The liquid crystal aligning agent according to claim 1, wherein (e2) has a residue derived from a dicarboxylic acid anhydride and is a monovalent organic group having one or two carboxy groups (however, the monovalent organic group does not include an acid anhydride group), and the dicarboxylic acid anhydride is selected from a compound (e2-1) not having an alkoxysilane structure or a compound (e2-2) having an alkoxysilane structure.

4. The liquid crystal aligning agent according to claim 3, wherein the compound (e2-1) is an aromatic or aliphatic cyclic dicarboxylic acid anhydride.

5. The compound (e2-2) is 4-(3-trimethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-triethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-trimethoxysilylpropyl)phthalic anhydride, 4-(3-triethoxysilylpropyl)phthalic anhydride, (C1-6)alkoxydimethylsilyl(C2-8)alkylsuccinic anhydride; di(C1-6)alkoxymethylsilyl(C2-8) ) alkyl succinic anhydride; tri(C1-6)alkoxysilyl(C2-8) alkyl succinic anhydride; 4-(3-dimethylmethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-dimethylethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-dimethylmethoxysilylpropyl)phthalic anhydride or 4-(3-dimethylethoxysilylpropyl)phthalic anhydride, the liquid crystal aligning agent according to claim 3, selected from.

6. The liquid crystal aligning agent according to claim 1, wherein the formula (X-1) is selected from the group consisting of the following formulas (x1-1) to (x1-5): (* represents a bond.) 7. The structural unit (a-1Da) is a diamine (0) "H-N(Z)-Ar １ -L １ -A-L １’ -Ar １’ The liquid crystal aligning agent according to claim 1 or 2, wherein the structural unit (1D-1) is derived from "-N(Z)-H" or the structural unit (1D-2) is derived from a diamine other than the diamine (0). １ , Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring. １ , Ar １’ Any hydrogen atom on the ring may be substituted with a monovalent group. A represents a divalent organic group having an alkylene structure and 1 to 10 carbon atoms. Z represents a group represented by the formula (1D ａ ) has the same meaning as Z in L. １ , L １’ each independently represents a single bond, —O—, —S—, —C(═O)—, —O—C(═O)—, —C(═O)—NR— (R represents a hydrogen atom or a monovalent organic group), or —NR—C(═O)— (R represents a hydrogen atom or a monovalent organic group).

8. In the structural unit (a-1Da), Ar １ and Ar １’ The liquid crystal aligning agent according to claim 7 , wherein is a combination of an optionally substituted benzene ring and an optionally substituted benzene ring.

9. The diamine other than the diamine (0) in the structural unit (1D-2) is p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 1,4-diamino-2,5-methoxybenzene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine, semi-aromatic diamines having a secondary amino group and a primary amino group, 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3-trifluoromethyl-4,4 '-diaminobiphenyl, 2-trifluoromethyl-4,4'-diaminobiphenyl, 3-fluoro-4,4'-diaminobiphenyl, 2-fluoro-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-di The liquid crystal aligning agent according to claim 7, which is selected from the group consisting of aminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,7-diaminonaphthalene.

10. A method for producing a liquid crystal alignment film, comprising applying the liquid crystal aligning agent according to any one of claims 1 to 9 to a substrate, baking the applied film, and irradiating the resulting film with polarized radiation.

11. The method for producing a liquid crystal alignment film according to claim 10, wherein the baking temperature is 150 to 250°C.

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

13. A liquid crystal display device comprising the liquid crystal alignment film according to claim 12.

14. The liquid crystal display element according to claim 13, which is of an IPS drive system or an FFS drive system.

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