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

Abstract

The purpose of the present application is to provide a polyimide-based liquid crystal alignment film having excellent adhesion (close adhesion) between a sealant and a substrate, a liquid crystal alignment agent capable of obtaining the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film. A diamine having a structure represented by the following formula (1), a polymer obtained therefrom, and a liquid crystal alignment agent containing the polymer. In formula (1), T 1 and T 2 Each independently represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -N(CH3)-, -CON(CH3)-, and -N(CH3)CO-, W represents a single bond or a divalent organic group, and Q represents a substituent represented by formula (2). The two Qs present in the molecule are the same or different. In formula (2), X represents a single bond, -O-, -COO-, -OCO-, and -S-, and R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A is a protecting group which is replaced by a hydrogen atom by heat, and n is an integer of 1 to 6.

Description

Technical Field

[0001] The present invention relates to a polymer having a protective group which is replaced by a hydrogen atom by heat, a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element using the same, and a novel diamine used therein. Background Art

[0002] As liquid crystal display elements, various driving methods have been developed with different electrode structures, physical properties of liquid crystal molecules used, manufacturing processes, etc. For example, there are known liquid crystal display elements such as TN (twisted nematic) type, STN (super-twisted nematic) type, VA (vertical alignment) type, MVA (multi-domain vertical alignment) type, IPS (in-plane switching) type, FFS (fringe field switching) type, PSA (polymer-sustained alignment) type, etc.

[0003] These liquid crystal display elements include a liquid crystal alignment film to orient liquid crystal molecules. From the perspective of excellent properties such as heat resistance, mechanical strength, and affinity with liquid crystals, the material of the liquid crystal alignment film generally uses a film containing a polymer such as polyamic acid, polyimide, and polysiloxane.

[0004] With the high precision of liquid crystal display elements, in order to suppress the contrast reduction of liquid crystal display elements and reduce the residual image phenomenon, for liquid crystal alignment films, in addition to showing excellent liquid crystal orientation and stable pretilt angle, high voltage holding rate, suppression of residual image caused by AC drive, less residual charge when DC voltage is applied, and / or rapid relaxation of residual charge accumulated by DC voltage are becoming increasingly important. In order to respond to the above requirements, various schemes have been proposed for polyimide-based liquid crystal alignment films (see patent documents 1 to 5).

[0005] Prior art literature:

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 9-316200

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 10-104633

[0009] Patent Document 3: Japanese Patent Application Laid-Open No. 8-76128

[0010] Patent Document 4: Japanese Patent Application Laid-Open No. 9-138414

[0011] Patent Document 5: Japanese Patent Application Laid-Open No. 11-38415 Summary of the invention

[0012] Problem that the invention aims to solve

[0013] In recent liquid crystal display elements, in order to expand the effective pixel area, it is required to further reduce the so-called frame area where the peripheral outer edge of the substrate does not form pixels. With the narrow frame of the panel, the sealant used when bonding two substrates to make a liquid crystal display element is applied to the polyimide liquid crystal alignment film, but since there is no polar group on the polyimide, the sealant and the surface of the liquid crystal alignment film cannot form a covalent bond, and there is a problem that the bonding between the substrates becomes insufficient. Therefore, it becomes a subject to improve the adhesion (closeness) between the polyimide liquid crystal alignment film and the sealant and substrate.

[0014] Solutions for solving problems

[0015] The present inventors have conducted intensive studies to solve the above problems and have found that various properties can be improved simultaneously by introducing a specific structure into a polymer contained in a liquid crystal aligning agent, thereby completing the present invention. The present invention is based on the above findings and has the following gist.

[0016] 1. A liquid crystal aligning agent comprising a polymer obtained from a diamine represented by the following general formula (1) and an organic solvent.

[0017]

[0018] (In formula (1), T 1 and T 2 Each independently represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-, and W represents a single bond or a divalent organic group (wherein T 1 or T 2 When W is a single bond, Q represents a substituent represented by the following formula (2). The two Qs present in the molecule may be the same or different.

[0019]

[0020] (In formula (2), X is any of a single bond, -O-, -COO-, -OCO-, and -S-, and R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A is a protecting group that is replaced by a hydrogen atom by heat, and n is an integer of 1 to 6.

[0021] Effects of the Invention

[0022] According to the liquid crystal aligning agent of this invention, the liquid crystal display element which is excellent in the adhesiveness (adhesion) between a polyimide-type liquid crystal aligning film, a sealant, and a board|substrate, and the liquid crystal aligning film which provides this element can be obtained.

[0023] According to the liquid crystal aligning agent of the present invention, a liquid crystal aligning film having excellent adhesion to a sealant can be obtained. By using the liquid crystal aligning film, an excellent, impact-resistant liquid crystal display element can be obtained for the adhesion of substrates to each other. The mechanism for improving the adhesion to the sealant may not be clear, and it can be considered that the group with the NA structure is in the prescribed position of the benzene ring, so that the intramolecular cyclization is suppressed when the NA group of the A group from the diamine is replaced by a hydrogen atom. It is believed that as a result, the amino group generated by heating the protective group leaving is exposed on the surface of the liquid crystal aligning film, and due to the interaction between the functional group in the group and the sealant, the adhesion of the liquid crystal aligning film and the sealant is improved. DETAILED DESCRIPTION

[0024] The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent containing a polymer (hereinafter also referred to as a specific polymer) obtained from a diamine having a structure (hereinafter also referred to as a specific structure) represented by the above formula (1). Each condition will be described in detail below.

[0025] <Diamine having a specific structure>

[0026] In the above formula (1), T 1 、T 2 , W, and Q have the same meanings as described above.

[0027] In the above formula (1), T 1 and T 2 Preferably, each independently represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, and -N(CH3)-, and W is preferably a single bond or a hydrocarbon group containing a linear, branched, or cyclic structure. The number of carbon atoms in the hydrocarbon group is preferably 1 to 20, and a part of the hydrocarbon group may be substituted with -O-, -COO-, or -OCO-. Specific examples of preferred cyclic structures include phenylene and cyclohexylene.

[0028] In the above formula (2), X is preferably any of a single bond, -O-, -COO- and -OCO-, and R 1 A is preferably a tert-butoxycarbonyl group, and n is preferably an integer of 1-6.

[0029] Specific examples of the diamine of the above formula (1) include diamines represented by the following DA-1 to DA-4, but are not limited thereto. In the formula, Boc represents a tert-butoxycarbonyl group.

[0030]

[0031] <Polymer>

[0032] The polymer of the present invention is a polymer obtained using the above diamine. As specific examples, polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide, etc. can be cited. From the viewpoint of use as a liquid crystal aligning agent, it is more preferably selected from at least one of a polyimide precursor having a structural unit represented by the following formula (3) and a polyimide as its imide product.

[0033]

[0034] Among them, X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y 1 is a divalent organic group derived from a diamine having a structure represented by the above formula (1), R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 2 It is preferably a hydrogen atom, a methyl group or an ethyl group. 2 The same as or different from each other.

[0035] <Tetracarboxylic dianhydride>

[0036] X1 is a tetravalent organic group from a tetracarboxylic acid derivative, and its structure is not particularly limited. In addition, X1 in the polyimide precursor can be appropriately selected according to the degree of required characteristics such as the solubility of the polymer in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal orientation when the liquid crystal aligning film is made, the voltage holding rate, and the accumulated charge, and can be one or more in the same polymer.

[0037] When showing specific examples of X1, the structures of formulae (X-1) to (X-46) disclosed in Items 13 and 14 of International Publication No. 2015 / 119168 may be cited.

[0038] Preferred structures of X1 are shown below, but the present invention is not limited thereto.

[0039]

[0040] Among the above structures, (A-1) and (A-2) are particularly preferred from the viewpoint of photo-orientation, (A-4) is particularly preferred from the viewpoint of further improving the relaxation rate of accumulated charges, and (A-15) to (A-17) are particularly preferred from the viewpoint of further improving the liquid crystal orientation and the relaxation rate of accumulated charges.

[0041] <Polymer (other structural units)>

[0042] The polyimide precursor having the structural unit represented by formula (3) may further have at least one selected from the structural unit represented by the following formula (4) and imidized structures thereof within a range not impairing the effects of the present invention.

[0043]

[0044] In formula (4), X2 is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y2 is a divalent organic group derived from a diamine that does not contain the structure of formula (1) in the main chain direction, R5 has the same definition as R2 in the above formula (3), and R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In addition, at least one of the two R6s is preferably a hydrogen atom. The two R5s and R6s are respectively the same or different from each other.

[0045] As a specific example of X2, including preferred examples, the same structure as the example illustrated by X1 of formula (3) can be cited. In addition, Y2 in the polyimide precursor is a divalent organic group from a diamine having a structure not containing formula (1) in the main chain direction, and its structure is not particularly limited. In addition, Y2 can be appropriately selected according to the degree of required characteristics such as the solubility of the polymer in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal orientation when the liquid crystal aligning film is made, the voltage retention rate, the accumulated charge, etc., and can be one in the same polymer, or can be mixed with more than two.

[0046] Specific examples of Y2 include the structure of formula (2) disclosed in item 4 of International Publication No. 2015 / 119168 and the structures of formulas (Y-1) to (Y-97) and (Y-101) to (Y-118) disclosed in items 8 to 12; the divalent organic group obtained by removing two amino groups from formula (2) disclosed in item 6 of International Publication No. 2013 / 008906; the divalent organic group disclosed in item 8 of International Publication No. 2015 / 122413 The divalent organic group formed by removing two amino groups from the disclosed formula (1); the structure of the formula (3) disclosed in item 8 of International Publication Gazette 2015 / 060360; the divalent organic group formed by removing two amino groups from the formula (1) recorded in item 8 of Japanese Patent Publication 2012-173514; the divalent organic group formed by removing two amino groups from the formulas (A) to (F) disclosed in item 9 of International Publication Gazette 2010-050523, etc.

[0047] Preferred structures of Y2 are shown below, but the present invention is not limited thereto.

[0048]

[0049]

[0050] Among the above structures, from the viewpoint of further improving the film hardness, (B-28), (B-29) and the like are particularly preferred, from the viewpoint of further improving the liquid crystal orientation, (B-1) to (B-3) and the like are particularly preferred, from the viewpoint of further improving the relaxation rate of the accumulated charge, (B-14) to (B-18) and (B-27) and the like are particularly preferred, and from the viewpoint of further improving the voltage holding rate, (B-26) and the like are preferred.

[0051] In addition, in (B-28) to (B-30), there are two n which are the same or different from each other.

[0052] <Diamine having a specific side chain structure)>

[0053] In addition, as Y 2 It is also preferable to use a diamine having a specific side chain structure. The diamine having a specific side chain structure is represented by the following formulas [1] and [2], for example.

[0054]

[0055] In the above formula [2], X represents a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -COO-, -(CH2) m -, -SO2- or a divalent organic group consisting of any combination thereof. Among them, X is preferably a single bond, -O-, -NH-, -O-(CH2) m -O-. Examples of "any combination thereof" include -O-(CH2) m -O-, -OC(CH3)2-, -CO-(CH2) m -、-NH-(CH2) m -、-SO2-(CH2) m -、-CONH-(CH2) m -、-CONH-(CH2) m -NHCO-, -COO-(CH2) m -OCO-, etc., but not limited to these. m is an integer of 1-8.

[0056] In the above formulas [1] and [2], Y each independently represents at least one selected from the side chain structures represented by formulas [S1] to [S3]. In the above formula [2], two Ys may be the same or different. The details of the side chain structures represented by formulas [S1] to [S3] are described below.

[0057] In the above formula [2], the position of Y relative to X may be the meta position or the ortho position, and is preferably the ortho position. That is, the above formula [2] is preferably the following formula [2'].

[0058]

[0059] In the above formula [2], the positions of the two amino groups (-NH2) can be any positions on the benzene ring, preferably the positions shown in the following formulas [2]-a1 to [2]-a3, and more preferably the following formula [2]-a1. In the following formula, X is the same as in the above formula [2]. It should be noted that the following formulas [2]-a1 to [2]-a3 are used to illustrate the positions of the two amino groups, and the description of Y shown in the above formula [2] is omitted.

[0060]

[0061] Therefore, based on the above formulas [2'] and [2]-a1 to [1]-a3, the above formula [2] is preferably any structure selected from the following formulas [2]-a1-1 to [2]-a3-2, and more preferably a structure represented by the following formula [2]-a1-1. In the following formulas, X and Y are the same as in the case of formula [2].

[0062]

[0063] The di-side chain diamines represented by the above formula [2] may be used alone or in combination of two or more. Depending on the properties required for the liquid crystal alignment film or liquid crystal display element, one or more may be used alone or in combination of two or more. When two or more are used in combination, the ratio thereof may be appropriately adjusted.

[0064] In the above formulae [1] and [2], Y represents a specific side chain structure selected from the group represented by the following formulae [S1] to [S3]. The specific side chain structure will be described below in the order of formulae [S1] to [S3].

[0065] Examples of the specific side chain structure include diamines having a specific side chain structure represented by the following formula [S1].

[0066]

[0067] In the above formula [S1], X 1 and X 2Each independently represents a single bond, -(CH2) a -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -COO-, -OCO- or -((CH2) a1 -A1) m1 -. In this case, a plurality of a1s are each independently an integer of 1 to 15, a plurality of A1s are each independently an oxygen atom or -COO-, and m1 is 1 to 2.

[0068] Among them, from the perspective of raw material availability and ease of synthesis, X 1 and X 2 Each is independently preferably a single bond, -(CH2) a -(a is an integer of 1 to 15), -O-, -CH2O- or -COO-. More preferably, X 1 and X 2 Each is independently a single bond, -(CH2) a -(a is an integer from 1 to 10), -O-, -CH2O- or -COO-.

[0069] In the above formula [S1], G 1 and G 2 Each independently represents a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. m and n are each independently an integer of 0 to 3, and the total of m and n is 1 to 4.

[0070] X 1 , X 2 , G 1 and G 2 When there are multiple X 1 , X 2 , G 1 and G 2 are the same as or different from each other.

[0071] In the above formula [S1], R 1 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms, forming R 1 Any hydrogen in the group may be substituted with fluorine. Examples of divalent aromatic groups having 6 to 12 carbon atoms include phenylene, biphenylene, and naphthylene. Examples of divalent alicyclic groups having 3 to 8 carbon atoms include cyclopropylene and cyclohexylene.

[0072] Therefore, as preferred specific examples of the above formula [S1], the following formulas [S1-x1] to [S1-x7] can be listed, but are not limited to these.

[0073]

[0074] In the above formulas [S1-x1] to [S1-x7], R 1 The same as in the above formula [S1]. p Represents -(CH2) a -(a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2O-, -COO- or -OCO-. A1 represents an oxygen atom or -COO-* (a is a bond with "*" and (CH2) a2 A2 represents an oxygen atom or *-COO- (the bond with "*" is connected to (CH2) a2 a1 is an integer of 0 or 1, and a2 is an integer of 2 to 10. Cy, that is, a group described as "Cy" in a cyclohexane ring represents a 1,4-cyclohexylene group or a 1,4-phenylene group.

[0075] In addition, as an example of the specific side chain structure, there is a specific side chain structure represented by the following formula [S2].

[0076] -X 3 -R 2 [S2]

[0077] In the above formula [S2], X 3 represents a single bond, -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2O-, -COO- or -OCO-. From the viewpoint of liquid crystal orientation, X 3 Preferably, it is -CONH-, -NHCO-, -O-, -CH2O-, -COO- or -OCO-. 2 represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, forming R 2 Any hydrogen in R may be substituted with fluorine. 2 An alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms is preferred.

[0078] Furthermore, as an example of the specific side chain structure, there is a specific side chain structure represented by the following formula [S3].

[0079] -X 4 -R 3 [S3]

[0080] In the above formula [S3], X 4R represents -CONH-, -NHCO-, -O-, -COO- or -OCO-. 3 The steroid skeleton here has a structure having a steroid skeleton. The steroid skeleton has a skeleton represented by the following formula (st) in which three six-membered rings are bonded to one five-membered ring.

[0081]

[0082] As an example of the above formula [S3], the following formula [S3-x] can be cited, but it is not limited to this.

[0083]

[0084] In the above formula [S3-x], X represents the above formula [X1] or [X2]. In addition, Col represents a group selected from the group consisting of the above formulas [Col1] to [Col3], and G represents a group selected from the group consisting of the above formulas [G1] to [G4]. * represents a site bonded to another group.

[0085] Examples of preferred combinations of X, Col and G in the above formula [S3-x] include a combination of formula [X1], formula [Col1] and [G2], a combination of formula [X1], formula [Col2] and [G2], a combination of formula [X2], formula [Col1] and [G2], a combination of formula [X2], formula [Col2] and [G2], and a combination of formula [X1], formula [Col3] and [G1].

[0086] In addition, as specific structures of the above formula [S3], there can be listed the structure obtained by removing the hydroxyl group from the steroid compound described in paragraph

[0024] of Japanese Patent Application Laid-Open No. 4-281427, the structure obtained by removing the acyl chloride group from the steroid compound described in paragraph

[0030] of the same publication, the structure obtained by removing the amino group from the steroid compound described in paragraph

[0038] of the same publication, the structure obtained by removing the halogen group from the steroid compound described in paragraph

[0042] of the same publication, and the structures described in paragraphs

[0018] to

[0022] of Japanese Patent Application Laid-Open No. 8-146421.

[0087] These diamines having specific side chain structures represented by formulas [S1] to [S3] can be used alone or in combination of two or more. Depending on the properties required for the liquid crystal alignment film or liquid crystal display element, one or more diamines can be used alone or in combination of two or more diamines. In addition, when two or more diamines are used in combination, their ratio can be appropriately adjusted.

[0088] Examples of the diamine having a side chain structure selected from the group represented by the above formulas [S1] to [S3] include diamines having structures of the following formulas [1-S1] to [1-S3] and [2-S1] to [1-S3], respectively.

[0089]

[0090] In the above formulas [1-S1] and [2-S1], X 1 , X 2 , G 1 , G 2 , R 1 , m and n are the same as those in the above formula [S1]. In the above formula [1-S2], X 3 and R 2 The same as in the above formula [S2]. In the above formula [1-S3], X 4 and R 3 The same as in the above formula [S3]. In the above formulas [1-S1] and [2-S1] to [2-S3], X 1 , X 2 , G 1 , G 2 , X 3 , R 2 , X 4 , R 3 When there are multiple X, m and n, 1 , X 2 , G 1 , G 2 , X 3 , R 2 , X 4 , R 3 , m and n are respectively the same as or different from each other.

[0091] Among them, as the diamine represented by the above formulas [1-S1] to [1-S3], for example, specific structures shown below can be mentioned, but it is not limited thereto.

[0092]

[0093] Examples of the diamines represented by the formulas [2-S1] to [2-S3] include specific structures as shown below, but are not limited thereto.

[0094]

[0095] <Other diamines: diamines having photoreactive side chains>

[0096] In addition, as Y 2It is also preferable to use a diamine having a photoreactive side chain. When the diamine component contains a diamine having a photoreactive side chain, a photoreactive side chain can be introduced into a specific polymer or another polymer.

[0097] Examples of the diamine having a photoreactive side chain include diamines represented by the following formula [VIII] or [IX], but are not limited thereto.

[0098]

[0099] In the above formulas [VIII] and [IX], the positions of the two amino groups (-NH2) can be any positions on the benzene ring, for example, the 2,3, 2,4, 2,5, 2,6, 3,4 or 3,5 positions on the benzene ring can be cited relative to the connecting group of the side chain. From the aspect of reactivity when synthesizing polyamic acid, the 2,4, 2,5 or 3,5 positions are preferred. If the ease of synthesizing diamine is also considered, the 2,4 or 3,5 positions are more preferred.

[0100] In the above formula [VIII], R 8 R represents a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)- or -N(CH3)CO-. 8 Particularly preferred is a single bond, -O-, -COO-, -NHCO- or -CONH-.

[0101] In the above formula [VIII], R 9 represents a single bond or an alkylene group having 1 to 20 carbon atoms which is optionally substituted by a fluorine atom. The -CH2- of the alkylene group here may be optionally replaced by -CF2- or -CH=CH-, and may be optionally replaced by any of the following groups when they are not adjacent to each other: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, or a divalent carbocyclic or heterocyclic ring.

[0102] Among the above, the divalent carbocyclic ring or heterocyclic ring can specifically be a structure selected from the following formula (1a), but is not limited thereto.

[0103]

[0104] In the above formula [VIII], R 9 It can be formed by a common organic synthesis method, and from the viewpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferred.

[0105] In the above formula [VIII], R 10represents a photoreactive group selected from the group consisting of the following formula (1b). 10 Preferred is a methacryloyl group, an acryloyl group or a vinyl group.

[0106]

[0107] In the above formula [IX], Y1 represents -CH2-, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH- or -CO-. Y2 represents an alkylene group having 1 to 30 carbon atoms or a divalent carbocyclic ring or heterocyclic ring. One or more hydrogen atoms in the alkylene group, divalent carbocyclic ring or heterocyclic ring may be substituted with a fluorine atom or an organic group. When the following groups are not adjacent to each other, the -CH2- of Y2 may be substituted with these groups: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. It should be noted that the above-mentioned organic group includes, for example, a substituent selected from the group consisting of an alkyl group containing a halogen atom, an alkoxy group containing a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 1 to 10 carbon atoms; and a heteroatom-containing group in which the carbon-carbon bond of any methylene group of the above-mentioned alkyl group containing a halogen atom, an alkoxy group containing a halogen atom, an alkyl group, an alkoxy group, and an alkenyl group is interrupted by an oxygen atom.

[0108] In the above formula [IX], Y3 represents -CH2-, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO- or a single bond. Y4 represents a cinnamoyl group. Y5 represents a single bond, an alkylene group having 1 to 30 carbon atoms, or a divalent carbocyclic ring or heterocyclic ring. One or more hydrogen atoms in the alkylene group, divalent carbocyclic ring or heterocyclic ring may be substituted with a fluorine atom or an organic group. When the following groups are not adjacent to each other, -CH2- in Y5 may be substituted with these groups: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. Y6 represents a photopolymerizable group such as an acryloyl group or a methacryloyl group. It should be noted that the above-mentioned organic group includes, for example, a substituent selected from the group consisting of an alkyl group containing a halogen atom, an alkoxy group containing a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 1 to 10 carbon atoms; and a heteroatom-containing group in which the carbon-carbon bond of any methylene group of the above-mentioned alkyl group containing a halogen atom, an alkoxy group containing a halogen atom, an alkyl group, an alkoxy group, and an alkenyl group is interrupted by an oxygen atom.

[0109] Specific examples of the diamine having a photoreactive side chain represented by the above formula [VIII] or [IX] include diamines selected from the following formula (1c), but are not limited thereto.

[0110]

[0111] In the above formula (1c), X 9 and X 10 Each independently represents a single bond, -O-, -COO-, -NHCO- or -NH-. Y represents an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom.

[0112] The diamine having a photoreactive side chain also includes the diamine of the following formula [VII]. The diamine of formula [VII] contains a site having a radical generating structure in the side chain. The radical generating structure decomposes by ultraviolet irradiation to generate radicals.

[0113]

[0114] In the above formula [VII], Ar represents at least one aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, and the hydrogen atoms of the aromatic hydrocarbon group are optionally substituted by halogen atoms. Ar bonded to the carbonyl group interferes with the absorption wavelength of ultraviolet rays, and therefore, in the case of long wavelength, a structure with a long conjugated length such as naphthylene and biphenylene is preferred. On the other hand, if Ar becomes a structure such as naphthylene and biphenylene, the solubility sometimes deteriorates, and in this case, the difficulty of synthesis becomes higher. If the wavelength of ultraviolet rays is in the range of 250nm to 380nm, even phenyl can obtain sufficient characteristics, and therefore, Ar is most preferably phenyl.

[0115] In the above Ar, the aromatic hydrocarbon group may have a substituent other than a halogen atom. Examples of the substituent here are preferably electron-donating organic groups such as an alkyl group, a hydroxyl group, an alkoxy group, and an amino group.

[0116] In the above formula [VII], R1 and R2 each independently represent an alkyl group, alkoxy group, benzyl group or phenethyl group having 1 to 10 carbon atoms. In the case of an alkyl group or an alkoxy group, R1 and R2 may form a ring.

[0117] In addition, in the above formula [VII], T1 and T2 each independently represent a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)- or a connecting group of -N(CH3)CO-.

[0118] In formula [VII], S represents a single bond, or an unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms. -CH2- or -CF2- in the alkylene group may be optionally replaced by -CH=CH-, and may be optionally replaced by any of the following groups when they are not adjacent to each other: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, or a divalent heterocyclic ring.

[0119] In the formula [VII], Q represents a structure selected from the following formula (1d).

[0120]

[0121] In the above formula (1d), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R3 represents -CH2-, -NR-, -O- or -S-. Two Rs may be the same or different.

[0122] In the above formula [VII], Q is preferably an electron-donating organic group, preferably a hydroxyl group, an alkoxy group, an amino group, etc., which are also listed in the above examples of Ar. When Q is an amino derivative, when a polyamic acid as a polyimide precursor is polymerized, undesirable situations such as the generated carboxylic acid group and the amino group forming a salt may occur, and therefore, a hydroxyl group or an alkoxy group is more preferably used.

[0123] In the above formula [VII], the positions of the two amino groups (-NH2) may be any of o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine, and are preferably m-phenylenediamine or p-phenylenediamine from the viewpoint of reactivity with an acid dianhydride.

[0124] Therefore, as a preferred specific example of the above formula [VII], the following formula can be cited from the viewpoints of ease of synthesis, high versatility, properties, etc. In the following formula, n is an integer of 2 to 8.

[0125]

[0126] The diamines having photoreactive side chains represented by the above formula [VII], [VIII] or [IX] may be used alone or in combination of two or more. Depending on the liquid crystal orientation, pretilt angle, voltage holding characteristics, accumulated charge and other characteristics when the liquid crystal alignment film is formed, the liquid crystal response speed when the liquid crystal display element is formed, etc., one or more diamines may be used alone or in combination of two or more. In addition, when two or more diamines are used in combination, the ratio thereof may be appropriately adjusted.

[0127] When the polyimide precursor having a structural unit represented by formula (3) also has a structural unit represented by formula (4), the structural unit represented by formula (3) is preferably 10 mol% or more, more preferably 15 mol% or more, and particularly preferably 20 mol% or more, relative to the total of formula (3) and formula (4).

[0128] The molecular weight of the polyimide precursor used in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and further preferably 10,000 to 100,000 in terms of weight average molecular weight.

[0129] Examples of polyimides having a divalent group represented by formula (1) in the main chain include polyimides obtained by ring-closing the above-mentioned polyimide precursors. The ring-closure ratio (also referred to as imidization ratio) of the amic acid group in the polyimide is not necessarily 100% and can be arbitrarily adjusted according to the application and purpose.

[0130] Examples of a method for imidating a polyimide precursor include thermal imidization in which a solution of a polyimide precursor is directly heated, and catalytic imidization in which a catalyst is added to a solution of a polyimide precursor.

[0131] The liquid crystal aligning agent of the present invention is a composition containing the above-mentioned specific polymer and an organic solvent, and may contain two or more specific polymers of different structures. In addition, as long as the effects described in the present invention are exerted, the liquid crystal aligning agent of the present invention may also contain polymers other than the specific polymer (hereinafter also referred to as the second polymer), various additives.

[0132] When the liquid crystal aligning agent of the present invention contains the second polymer, it is preferable that the ratio of the specific polymer to all polymer components is 5 mass % or more, and as one example thereof, 5 to 95 mass % can be mentioned.

[0133] Examples of the second polymer include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene or derivatives thereof, poly(styrene-phenylmaleimide) derivatives, and poly(meth)acrylate.

[0134] In particular, it is preferable to use a polyamic acid obtained from a tetracarboxylic dianhydride component and a diamine component (hereinafter, also referred to as a second polyamic acid) as the second polymer.

[0135] Examples of the tetracarboxylic dianhydride component for obtaining the second polyamic acid include compounds represented by the following formula (11): The acid dianhydride component may be composed of one compound or two or more compounds.

[0136]

[0137] In the formula (11), A is a tetravalent organic group, preferably a tetravalent organic group having 4 to 30 carbon atoms.

[0138] Specific examples and preferred examples of A include the same structures as those exemplified for X1 in formula (3).

[0139] The diamine component for obtaining the second polyamic acid can be appropriately determined depending on the purpose, and for example, a diamine represented by the following formula (12) can be used.

[0140]

[0141] (Y9 represents a divalent organic group. A9 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and they may be the same or different. From the viewpoint of liquid crystal orientation, A9 is preferably a hydrogen atom or a methyl group.)

[0142] The structure of Y9 of the formula (12) which is preferred when used as a diamine component for obtaining the second polyamic acid is shown below, but the present invention is not limited thereto.

[0143]

[0144] For the purpose of improving electrical properties and relaxing properties, Y9 is preferably a divalent organic group having a tertiary nitrogen atom, or a divalent organic group having -NH-CO-NH- in the molecule. As a specific example of formula (12) when Y9 is a divalent organic group having a tertiary nitrogen atom, it is a diamine having a pyrrole structure described in International Publication WO2017 / 126627, preferably a diamine having a structure represented by the following formula (pr),

[0145]

[0146] (R 1 represents a hydrogen atom, hydrogen, a fluorine atom, an amino group, a hydroxyl group, a methyl group, and R 2 Each independently is a single bond or a group "*1-R 3 -Ph-*2”, R 3 represents a single bond, selected from -O-, -COO-, -OCO-, -(CH2) l -、-O(CH2) m O-, -CONH- and -NHCO- are divalent organic groups (l and m represent integers of 1 to 5), *1 represents the site bonded to the benzene ring in formula (pr), and *2 represents the site bonded to the amino group in formula (pr). Ph represents a phenylene group. n represents 1 to 3. R 1 and R 2 When there are two or more, two or more R 1and R 2 The diamine having a pyrrole structure described in International Publication WO2018 / 062197 is preferably a diamine having a structure represented by the following formula (pn),

[0147]

[0148] (R 1 and R 2 Each independently represents a hydrogen atom or a methyl group, R 3 Indicates a single bond or group "*1-R 4 -Ph-*2”, R 4 represents a single bond, selected from -O-, -COO-, -OCO-, -(CH2) l -、-O(CH2) m O-, -CONH- and -NHCO- are divalent organic groups (l and m represent integers of 1 to 5), *1 represents the site bonded to the benzene ring in the formula (pn), and *2 represents the site bonded to the amino group in the formula (pn). Ph represents a phenylene group. n represents 1 to 3. There are two or more R 1 , R 2 and R 3 When more than 2 R 1 , R 2 and R 3 They are the same as or different from each other. ); a diamine having a carbazole structure described in International Publication WO2018 / 110354, preferably a diamine having a structure represented by the following formula (cz).

[0149]

[0150] (R 1 represents a hydrogen atom or a methyl group, R 2 represents a methyl group. ); a diamine having a nitrogen-containing heterocyclic ring as described in paragraphs

[0173] to

[0188] of International Publication WO2015 / 046374, a diamine having a nitrogen-containing structure as described in paragraph

[0050] of Japanese Patent Application Laid-Open No. 2016-218149, a diamine represented by the following formula (BP),

[0151]

[0152] (X is a biphenyl ring or a fluorene ring, Y is a group selected from a benzene ring, a biphenyl ring or -phenylene-Z-phenylene-, and Z is a divalent group represented by -O-, -NH-, -CH2-, -SO2-, -C(CH3)2- or -C(CF3)2-. A and B are each independently a hydrogen atom or a methyl group.), 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)piperazine, 4,4'-[4,4'-propane-1,3-diylbis(piperidin-1,4-diyl)]diphenylamine, 2,4-diamino-6-isopropylamino Propoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2 -ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl)aniline, 4,4'-diphenylmethylamine, 4,4'-diphenylamine, 3,6-diaminocarbazole, 9-methyl-3,6-diaminocarbazole, 9-ethyl-3,6-diaminocarbazole, diamines represented by the following formulas (w1) to (w2), and the like.

[0153]

[0154] (Sp represents phenylene, pyrrolidine, piperidine, piperazine, a divalent chain hydrocarbon group having 2 to 20 carbon atoms, or a group in which -CH2- of the divalent chain hydrocarbon group is replaced by a group selected from -O-, -CO-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS-, -NR- (R represents a methyl group), pyrrolidine, piperidine and piperazine.)

[0155] Specific examples of the above formula (12) when Y9 in the formula (12) is a divalent organic group having -NH-CO-NH- in the molecule include diamines in which A1 in the above formula (4) is -NH-CO-NH- or a group in which at least one -CH2- of a chain hydrocarbon group having 2 to 20 carbon atoms is replaced by -NH-CO-NH-, or a group in which at least one -CH2- of a chain hydrocarbon group having 2 to 20 carbon atoms is replaced by -NH-CO-NH- and at least one of the other -CH2- is replaced by a group selected from -O-, -CO-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS- and -NR- (R represents a methyl group). Specific examples of more preferred diamines include diamines represented by the following formulas (U-1) to (U-9).

[0156]

[0157] Preferred specific examples of the diamines represented by the above formulae (w1) to (w2) include diamines represented by the following formulae (n3-1) to (n3-7) and diamines represented by the following formulae (n4-1) to (n4-6).

[0158]

[0159] In order to improve printability, diamine compounds having a carboxyl group (-COOH group) or a hydroxyl group (-OH group) may also be used. Specifically, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid may be mentioned. Among them, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferred. In addition, diamine compounds represented by the following formulas [3b-1] to [3b-4] and diamine compounds whose amino groups are secondary amino groups may also be used.

[0160]

[0161] (In formula [3b-1], Q 1represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-, m1 and m2 each independently represent an integer of 0 to 4 and m1+m2 represents an integer of 1 to 4, in formula [3b-2], m3 and m4 each independently represent an integer of 1 to 5, in formula [3b-3], Q 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms, m5 represents an integer of 1 to 5, and in the formula [3b-4], Q 3 and Q 4 Each independently represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-, and m6 represents an integer from 1 to 4.)

[0162] As the diamine component for obtaining the second polyamic acid, diamines used in specific polymers and known diamines can be used in addition to the above, but the present invention is not limited thereto. The diamine component for obtaining the second polyamic acid may be one diamine or a combination of two or more diamines.

[0163] <Production methods of polyamic acid, polyamic acid ester, and polyimide>

[0164] The polyamic acid ester, the polyamic acid, and the polyimide which are the polyimide precursors used in the present invention can be synthesized by a known method described in, for example, International Publication WO2013 / 157586.

[0165] <Liquid crystal alignment agent>

[0166] The liquid crystal aligning agent of the present invention contains a specific polymer. The liquid crystal aligning agent of the present invention can contain other polymers on the basis of the specific polymer and the second polymer used as desired. As the types of other polymers, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetals, polystyrene or its derivatives, poly (styrene-phenyl maleimide) derivatives, poly (meth) acrylates, etc. can be listed.

[0167] The liquid crystal alignment agent is used to make a liquid crystal alignment film, and from the viewpoint of forming a uniform film, a coating liquid is used. For the liquid crystal alignment agent of the present invention, it is preferably a coating liquid containing a polymer component containing a specific polymer and an organic solvent. At this time, the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed according to the setting of the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, it is preferably more than 1% by mass, and from the viewpoint of the storage stability of the solution, it is preferably less than 10% by mass. The concentration of the polymer is particularly preferably 2 to 8% by mass.

[0168] The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as it is a solvent in which the polymer component can be uniformly dissolved. If specific examples are given, they can be listed as: N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide (also collectively referred to as "good solvents"). Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide or γ-butyrolactone are preferably used. The good solvent in the liquid crystal aligning agent of the present invention is preferably 20 to 99% by mass of the whole solvent contained in the liquid crystal aligning agent, more preferably 20 to 90% by mass, particularly preferably 30 to 80% by mass.

[0169] In addition, the organic solvent contained in the liquid crystal aligning agent is preferably a mixed solvent of a solvent (also called a poor solvent) that improves the coating property and surface smoothness of the coating film when the liquid crystal aligning agent is applied on the basis of the above-mentioned solvent. Specific examples of the organic solvent used in combination are listed below, but are not limited to these examples.

[0170] Examples thereof include diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-( 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isopentyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), and the like.

[0171] Among them, diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and diisobutyl ketone are preferably used.

[0172] Preferred solvent combinations of the good solvent and the poor solvent include: N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-methyl- 2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, etc. These poor solvents are preferably 1 to 80% by mass of the total solvent contained in the liquid crystal aligning agent, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. The type and content of such solvents are appropriately selected according to the coating device, coating conditions, coating environment, etc. of the liquid crystal aligning agent.

[0173] The liquid crystal aligning agent of the present invention may also contain additional components other than the polymer component and the organic solvent. Such additional components include: a bonding aid for improving the adhesion between the liquid crystal aligning film and the substrate, the adhesion between the liquid crystal aligning film and the sealing material, a compound for improving the strength of the liquid crystal aligning film (hereinafter also referred to as a cross-linking compound), a dielectric for adjusting the dielectric constant and resistance of the liquid crystal aligning film, a conductive material, etc.

[0174] As the above-mentioned cross-linking compound, from the viewpoint of less generation of AC afterimage and high improvement effect of film strength, it is preferred to use a compound having at least one group selected from the group consisting of an oxiranyl group, an oxetane group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum acid structure, a cyclic carbonate group and a group represented by the following formula (d), or a compound selected from the compounds represented by the following formula (e) (hereinafter, they are also collectively referred to as compound (C)).

[0175]

[0176] (In formula (d), R2 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH2-OH". * represents a connecting bond. In formula (e), A represents an organic group having an (m+n) valence of an aromatic ring, R and R' represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 to 6, and n represents an integer of 0 to 4. Any hydrogen atom of the above aromatic ring may be optionally replaced by a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, or a fluoroalkoxy group having 1 to 10 carbon atoms.)

[0177] Specific examples of compounds having an oxirane group include compounds described in paragraph

[0037] of Japanese Patent Application Laid-Open No. 10-338880, compounds having a triazine ring in the skeleton described in International Publication No. WO2017 / 170483, and compounds having two or more oxirane groups. Among them, compounds containing nitrogen atoms such as N,N,N',N',-tetraglycidyl-m-xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-p-phenylenediamine, and compounds represented by the following formulas (r-1) to (r-3) are particularly preferred.

[0178]

[0179] Specific examples of the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in paragraphs

[0170] to

[0175] of International Publication No. 2011 / 132751.

[0180] Specific examples of compounds having protected isocyanate groups include compounds having two or more protected isocyanate groups described in paragraphs

[0046] to

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

[0119] to

[0120] of International Publication No. 2015 / 141598. Among these, compounds represented by the following formulas (bi-1) to (bi-3) are preferred.

[0181]

[0182] Specific examples of the compound having a protected isothiocyanate group include compounds having two or more protected isothiocyanate groups described in JP-A-2016-200798.

[0183] Specific examples of the compound having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures described in paragraph

[0115] of JP-A-2007-286597.

[0184] Specific examples of the compound having a group containing a Michaelis acid structure include compounds having two or more Michaelis acid structures described in International Publication No. WO2012 / 091088.

[0185] Specific examples of the compound having a cyclic carbonate group include compounds described in International Publication No. WO2011 / 155577.

[0186] Examples of the C1-3 alkyl group represented by R2 and R3 in the group represented by the above formula (d) include the groups exemplified in the above formulas (l) and (n).

[0187] Specific examples of compounds having a group represented by the above formula (d) include, for example, compounds having two or more groups represented by the above formula (d) described in paragraph

[0058] of International Publication WO2015 / 072554 and Japanese Patent Application Publication No. 2016-118753, compounds described in Japanese Patent Application Publication No. 2016-200798, etc. Among these, compounds represented by the following formulas (hd-1) to (hd-8) are preferred.

[0188]

[0189] Examples of the (m+n)-valent organic group having an aromatic ring in A of the above formula (e) include: an (m+n)-valent aromatic hydrocarbon group having 5 to 30 carbon atoms, an (m+n)-valent organic group to which an aromatic hydrocarbon group having 5 to 30 carbon atoms is directly or via a linking group, and an (m+n)-valent group having an aromatic heterocyclic ring. Examples of the above aromatic hydrocarbon group include benzene and naphthalene. Examples of the aromatic heterocyclic ring include: a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a pyridazine ring, a pyrazine ring, a phenylimidazole ring, a benzimidazole ring, an indole ring, a quinoxaline ring, an acridine ring, and the like. Examples of the above linking group include: an alkylene group having 1 to 10 carbon atoms, a group formed by removing one hydrogen atom from the above alkylene group, a divalent or trivalent cyclohexane ring, and the like. It should be noted that any hydrogen atom of the above alkylene group may be substituted by an organic group such as a fluorine atom or a trifluoromethyl group. Specific examples include compounds described in International Publication No. WO2010 / 074269. Preferred specific examples include the following formulas (e-1) to (e-10).

[0190]

[0191] The above compound is an example of a crosslinking compound, but is not limited thereto. For example, components other than the above disclosed on pages 53

[0105] to 55

[0116] of International Publication No. 2015 / 060357 can be cited. In addition, the crosslinking compound contained in the liquid crystal aligning agent of the present invention may be one kind or a combination of two or more kinds.

[0192] The content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, and is more preferably 1 to 15 parts by mass from the viewpoint of allowing the crosslinking reaction to proceed, expressing the target effect, and reducing the occurrence of AC image sticking.

[0193] 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-aminopropyltrimethoxysilane, and N-ethoxy Carbonyl-3-aminopropyl triethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N-trimethoxysilylpropyl triethylenetriamine, 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-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl triethoxysilane Alkane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Silane coupling agents such as oxypropyl triethoxysilane, p-phenylvinyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, and 3-isocyanate propyl triethoxysilane. When using these silane coupling agents, from the viewpoint of less generation of AC afterimage, the amount is preferably 0.1 to 30 parts by mass, and 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.

[0194] <Liquid crystal alignment film and liquid crystal display element>

[0195] A liquid crystal alignment film can be manufactured by using the above-mentioned liquid crystal alignment agent. In addition, the liquid crystal display element of the present invention has a liquid crystal alignment film formed using the above-mentioned liquid crystal alignment agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited, for example, it can be applied to various operation modes such as TN (Twisted Nematic) type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type (IPS type), FFS (Fringe Field Switching) type, optical compensation bending type (OCB type), etc.

[0196] The liquid crystal display element of the present invention can be produced, for example, by a process including the following steps (1-1) to (1-3). In step (1-1), the substrate used varies depending on the desired operation mode. Steps (1-2) and (1-3) are common to each operation mode.

[0197] [Step (1-1): Formation of coating film]

[0198] First, the liquid crystal aligning agent of the present invention is applied on a substrate, and then the applied surface is heated to form a coating film on the substrate.

[0199] (1-1A)

[0200] For example, in the case of manufacturing a TN type, STN type or VA type liquid crystal display element, first, two substrates with patterned transparent conductive films are used as a pair, and the prepared liquid crystal alignment agent is preferably applied to each transparent conductive film forming surface thereof by offset printing, spin coating, roller coating or inkjet printing. As a substrate, a transparent substrate formed of glass such as float glass and soda glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As a transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG Company, USA) formed of tin oxide (SnO2), an ITO film formed of indium oxide-tin oxide (In2O3-SnO2), etc. can be used. In order to obtain a patterned transparent conductive film, for example, the following methods can be used: a method of forming a pattern by photoetching after forming a transparent conductive film without a pattern; a method of using a mask having a desired pattern when forming a transparent conductive film; etc. When applying the liquid crystal alignment agent, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a pretreatment may be performed by applying a functional silane compound, a functional titanium compound, etc. on the surface of the substrate where the coating film is to be formed.

[0201] After the liquid crystal alignment agent is applied, it is preferred to perform preliminary heating (pre-baking) for the purpose of preventing the applied liquid crystal alignment agent from sagging. The pre-baking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C. The pre-baking time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Afterwards, the solvent is completely removed, and a calcination (post-baking) process is performed as needed to thermally imidize the amide acid structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80 to 300°C, and more preferably 120 to 250°C. The post-baking time is preferably 5 to 200 minutes, and more preferably 10 to 100 minutes. The film thickness of the film formed in this way is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μm.

[0202] (1-1B)

[0203] In the case of manufacturing an IPS type or FFS type liquid crystal display element, the liquid crystal alignment agent is applied to the electrode forming surface of the substrate provided with an electrode patterned into a comb-shaped transparent conductive film or metal film and one side of the opposing substrate without an electrode, and then each coated surface is heated to form a coating film. The material of the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the formed coating film are the same as those described above (1-1A). As a metal film, for example, a film formed of a metal such as chromium can be used.

[0204] In any of the above (1-1A) and (1-1B), a liquid crystal alignment film or a coating film of a liquid crystal alignment film is formed by removing an organic solvent after applying a liquid crystal alignment agent to a substrate. In this case, the coating film may be further heated after formation, thereby performing a dehydration ring-closure reaction of the polyamic acid, polyamic acid ester and polyimide contained in the liquid crystal alignment agent of the present invention to form a coating film that has been further imidized.

[0205] [Step (1-2): Orientation-imparting treatment]

[0206] In the case of manufacturing TN type, STN type, IPS type or FFS type liquid crystal display elements, the coating formed in the above step (1-1) is subjected to a treatment of imparting liquid crystal orientation ability. Thus, the coating is endowed with the orientation ability of the liquid crystal molecules to form a liquid crystal orientation film. As an orientation ability imparting treatment, for example: a friction treatment in which a roll formed of a cloth made of fibers such as nylon, rayon, and cotton is wound and rubbed along a certain direction on the coating; a light orientation treatment in which the coating is irradiated with polarized or non-polarized radiation, etc. On the other hand, in the case of manufacturing a VA type liquid crystal display element, the coating formed in the above step (1-1) can be used directly as a liquid crystal orientation film, or the coating can be subjected to an orientation ability imparting treatment.

[0207] In the case where the coating film is given liquid crystal orientation ability by photo-orientation treatment, as the radiation irradiated to the coating film, for example, ultraviolet rays and visible light containing wavelengths of 150 to 800 nm can be used. In the case where the radiation is polarized, it can be linearly polarized or partially polarized. In addition, in the case where the radiation used is linearly polarized or partially polarized, the irradiation can be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of them. In the case of irradiating non-polarized radiation, the irradiation direction is set to an oblique direction.

[0208] As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used. Ultraviolet rays in a preferred wavelength range can be obtained by combining a light source with, for example, a filter, a diffraction grating, etc. The irradiation amount of the radiation is preferably 10 to 5,000 mJ / cm 2 , more preferably 30 to 2,000 mJ / cm 2 .

[0209] In order to improve the reactivity, the coating film may be irradiated with light while being heated. The temperature during heating is usually 30 to 250°C, preferably 40 to 200°C, and more preferably 50 to 150°C.

[0210] In addition, when ultraviolet rays containing light with a wavelength of 150 to 800 nm are used, the light irradiation film obtained in the above process can be used directly as a liquid crystal alignment film, or the light irradiation film can be calcined, cleaned with water or an organic solvent, or a combination thereof. The calcination temperature at this time is preferably 80 to 300°C, more preferably 80 to 250°C. The calcination time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. It should be noted that the calcination can be performed once or more than twice. The photo-alignment treatment here is equivalent to the photo-irradiation treatment in a state where it is not in contact with the liquid crystal layer.

[0211] The organic solvent used for the above-mentioned cleaning is not particularly limited. Specific examples thereof 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 or cyclohexyl acetate.

[0212] It should be noted that the liquid crystal alignment film after the friction treatment can also be further treated as follows so that each area of ​​the liquid crystal alignment film has different liquid crystal alignment capabilities, and the treatment is: by irradiating a portion of the liquid crystal alignment film with ultraviolet rays, the pretilt angle of a portion of the liquid crystal alignment film is changed; on the basis of forming an anti-etching film on the surface of a portion of the liquid crystal alignment film, the friction treatment is performed in a direction different from the previous friction treatment, and then the anti-etching film is removed. In this case, the viewing field characteristics of the obtained liquid crystal display element can be improved. The liquid crystal alignment film suitable for VA type liquid crystal display elements can also be preferably used in PSA (Polymer sustained alignment) type liquid crystal display elements.

[0213] [Step (1-3): Construction of Liquid Crystal Cell]

[0214] (1-3A)

[0215] Prepare two substrates with liquid crystal alignment films formed as described above, and configure liquid crystal between the two substrates arranged opposite to each other, thereby manufacturing a liquid crystal unit. When manufacturing a liquid crystal unit, for example, the following two methods can be listed. The first method is a method known in the past. First, two substrates are arranged opposite to each other with a gap (cell gap) between them in a manner that each liquid crystal alignment film is opposite to each other, and the peripheral portions of the two substrates are bonded together using a sealant. After the liquid crystal is injected into the cell gap divided by the substrate surface and the sealant, the injection hole is sealed, thereby manufacturing a liquid crystal unit. The second method is a method called ODF (One Drop Fill: liquid crystal dripping) method. A sealant such as a UV-curable sealant is applied to a specified position on one of the two substrates formed with a liquid crystal alignment film, and after further dripping liquid crystal to a specified number of positions on the surface of the liquid crystal alignment film, another substrate is bonded in a manner that the liquid crystal alignment film is opposite to each other, and the liquid crystal is pushed to the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal unit. In the case of using any method, it is desirable to further heat the liquid crystal cell manufactured as described above to a temperature at which the liquid crystal used becomes isotropic and then gradually cool it to room temperature to remove the flow alignment during liquid crystal filling.

[0216] As the sealant, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used.

[0217] As liquid crystal, nematic liquid crystal and smectic liquid crystal can be listed, wherein nematic liquid crystal is preferred, for example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenylcyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, etc. can be used. In addition, cholesteric phase liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate can also be added to these liquid crystals; chiral agents sold under the trade names "C-15", "CB-15" (Merck Company); strong dielectric liquid crystals such as decyloxybenzylidene amino-2-methylbutyl cinnamate are used. In addition, anisotropic dyes can be added to the liquid crystal. The term "dye" refers to a substance that can absorb light in at least a part or the entire range or deform it in a concentrated manner in the visible light region, such as 400nm or 700nm wavelength range, and the term "anisotropic dye" refers to a substance that can perform anisotropic absorption of light in at least a part or the entire range of the above-mentioned visible light region. By using dyes such as those described above, the color sense of the liquid crystal unit can be adjusted. The type of anisotropic dye is not particularly limited, for example, black dye or color dye can be used. The ratio of anisotropic dye to liquid crystal can be appropriately selected within the range that does not damage the target physical properties of the present invention. For example, relative to 100 parts by mass of liquid crystal compounds, anisotropic dye can be included in a ratio of 0.01 parts by mass to 5 parts by mass, and the above ratio can be changed within an appropriate range as needed.

[0218] (1-3B)

[0219] When a PSA type liquid crystal display element is produced, a liquid crystal cell is constructed in the same manner as in (1-3A) above except that a photopolymerizable compound such as the following formula (w-1) to (w-5) is injected or dropped together with the liquid crystal.

[0220]

[0221] Then, the liquid crystal unit is irradiated with light while a voltage is applied between the conductive films of a pair of substrates. The voltage applied here can be set to, for example, a direct current or alternating current of 5 to 50 V. In addition, as the irradiated light, for example, ultraviolet rays and visible rays containing wavelengths of 150 to 800 nm can be used, preferably ultraviolet rays containing wavelengths of 300 to 400 nm. As the light source of the irradiated light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used. It should be noted that the ultraviolet rays in the above-mentioned preferred wavelength range can be obtained by combining a light source with, for example, a filter, a diffraction grating, etc. The irradiation amount of light is preferably 100 mJ / cm 2 Above and less than 30,000mJ / cm 2 , more preferably 100 to 20,000 mJ / cm 2 .

[0222] (1-3C)

[0223] When a coating film is formed on a substrate using a liquid crystal alignment agent containing a compound (polymer or additive) having a photopolymerizable group, the following method can also be used: a liquid crystal unit is constructed in the same manner as in (1-3A) above, and then a liquid crystal display element is manufactured by irradiating the liquid crystal unit with light while applying a voltage between the conductive films of a pair of substrates. According to this method, the advantages of the PSA mode can be achieved with a small amount of light irradiation. The light irradiation of the liquid crystal unit can be carried out in a state where the liquid crystal is driven by applying a voltage, or it can be carried out in a state where a low voltage is applied to the extent that the liquid crystal is not driven. The applied voltage can be set to, for example, a direct current or alternating current of 0.1 to 30 V. Regarding the conditions of the irradiated light, the description of (1-3B) above can be applied. The light irradiation treatment here is equivalent to the treatment of light irradiation in a state of contact with the liquid crystal layer.

[0224] Then, a polarizing plate is attached to the outer surface of the liquid crystal cell, thereby obtaining the liquid crystal display element of the present invention. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include: a polarizing plate formed by sandwiching a polarizing film called "H film" formed by stretching and absorbing iodine while polyvinyl alcohol is oriented with a cellulose acetate protective film; or a polarizing plate composed of the H film itself.

[0225] The liquid crystal display element of the present invention can be effectively used in various devices, for example, it can be used in various display devices such as watches, portable game consoles, word processors, notebook computers, car navigation systems, cameras, PDAs, digital cameras, mobile phones, smart phones, various monitors, LCD televisions, and information displays.

[0226] Example

[0227] The present invention is further specifically described by the following examples. However, the present invention is not limited to these examples. The abbreviations of the following compounds and the determination methods of various properties are as follows.

[0228] (Acid dianhydride)

[0229] DC-1 to DC-3: compounds represented by the following formula (DC-1) to (DC-3), respectively

[0230] (Diamine)

[0231] DA-1 to DA-10: compounds represented by the following formulas (DA-1) to (DA-10), respectively

[0232] (Solvent)

[0233] NMP: N-methyl-2-pyrrolidone

[0234] BCS: Butyl Cellosolve

[0235]

[0236] (Boc represents tert-butoxycarbonyl.)

[0237] The following methods for measuring the various properties and methods for preparing measurement samples used for the measurements are as described below.

[0238] <Viscosity measurement>

[0239] The viscosity of the polyamic acid solution or the like was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) at a sample volume of 1.1 mL (milliliter), a conical rotor TE-1 (1°34', R24), and a temperature of 25°C.

[0240] <Determination of molecular weight>

[0241] The molecular weights of the polyimide precursor, polyimide, and the like were measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.) and columns (KD-803 and KD-805) (manufactured by Showa Denko K.K.).

[0242] Column temperature: 50°C

[0243] Eluent: N,N-dimethylformamide (as additives, lithium bromide monohydrate (LiBr·H2O) at 30 mmol / L (liter), anhydrous phosphoric acid (orthophosphoric acid) at 30 mmol / L, tetrahydrofuran (THF) at 10 ml / L)

[0244] Flow rate: 1.0ml / min

[0245] Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories).

[0246] <Measurement of Imidization Ratio>

[0247] Add 20 mg of polyimide powder into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, (manufactured by Kusano Scientific Co., Ltd.)), deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixed product) (0.53 mL) was added, and ultrasonic waves were applied to completely dissolve it. The solution was measured with a 500 MHz proton NMR using an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL DATUM). Regarding the imidization rate, the proton from the structure that does not change before and after the imidization is determined as the reference proton, and the peak cumulative value of the proton from the NH group of the amic acid appearing near 9.5 to 10.0 ppm is used to calculate it by the following formula.

[0248] Imidization rate (%) = (1-α·x / y) × 100

[0249] In the above formula, x is the peak cumulative value of protons derived from the NH group of the amic acid, y is the peak cumulative value of the reference proton, and α is the ratio of the reference proton to the number of protons per NH group of the amic acid in the case of polyamic acid (imidation ratio 0%).

[0250] DA-1 to DA-4 are novel compounds not disclosed in literature and the like, and their synthesis methods are described in detail below.

[0251] The products described in the following Synthesis Examples 1 to 4 were used 1 The identification was carried out by H-NMR analysis (analysis conditions are as follows).

[0252] Device: BRUKER ADVANCE III-500MHz

[0253] Determination solvent: DMSO-d6

[0254] Reference material: Tetramethylsilane (TMS) (δ0.0ppm for 1 H)

[0255] (Synthesis Example 1: Synthesis of DA-1)

[0256] DA-1 was synthesized by the following steps.

[0257]

[0258] <Synthesis of compound [1]>

[0259] Chloroform (720 g), thionyl chloride (117 g, 0.986 mol) and pyridine (1 mL) were added to (4,4'-dinitro-[1,1'-biphenyl]-2,2'-diyl)dimethanol (120 g, 0.394 mol), and the mixture was stirred at 50°C for 19 hours. After the reaction was completed, water (720 g) was added to the reaction solution for separation and washing, and chloroform (720 g) was added for separation and extraction. The obtained organic phase was concentrated, and the crystals were slurry-washed with hexane (20.0 g) and filtered. The obtained crystals were dried to obtain compound [1] (yield: 115 g, 0.337 mol, yield 85%).

[0260] 1 H-NMR (500MHz) in DMSO-d6: 8.59 (d, J=3.0Hz, 2H), 8.36-8.32 (m, 2H), 7.63 (m, 2H), 4.69 (d, J=15.0Hz, 2H), 4.48 (d, J=14.5Hz, 2H).

[0261] <Synthesis of Compound [2]>

[0262] N,N-dimethylformamide (460 g) and potassium phthalimide (131 g, 0.708 mol) were added to compound [1] (115 g, 0.337 mol), and the mixture was stirred at 25° C. for 19 hours. After the reaction, ethyl acetate (960 g) and water (960 g) were added, and white crystals were precipitated. The crystals were filtered out and washed with water (600 g), and the obtained crystals were dried to obtain compound [2] (yield: 125 g, 0.222 mol, yield 66%).

[0263] 1 H-NMR (500MHz) in DMSO-d6: 8.26 (d, J=2.5Hz, 2H), 8.17-8.14 (m, 2H), 7.85-7.80 (m, 8H), 7.56 (d, J=10.5Hz, 2H), 4.74-4.62 (m, 4H).

[0264] <Synthesis of compound [3]>

[0265] Tetrahydrofuran (595 g) and hydrazine monohydrate (79%) (174 g, 4.29 mol) were added to compound [2] (119 g, 0.212 mol), and the mixture was stirred at 65°C for about 3 days. After the reaction was completed, white crystals gradually precipitated out of the system, so they were removed by filtration, and the filtrate was concentrated and dried to obtain a crude product of compound [3] (yield: 65.6 g). The obtained compound was used directly in the next step.

[0266] 1 H-NMR (500MHz) in DMSO-d6: 8.55 (d, J=2.4Hz, 2H), 8.18-8.15 (m, 2H), 7.41 (d, J=8.4Hz, 2H), 3.50-3.38 (m, 4H), 3.26 (br, 4H).

[0267] <Synthesis of compound [4]>

[0268] Methanol (300 g) was added to the crude product of compound [3] (50.0 g, 0.165 mol), and the mixture was stirred while cooling in an ice bath. Di-tert-butyl dicarbonate (74.0 g, 0.339 mol) diluted with methanol (50.0 g) was added dropwise while paying attention to heat release. After the addition was completed, the mixture was stirred at 25°C for 3 hours. Since white crystals gradually precipitated out of the system, the residue was washed with methanol (150 g) while filtering, and the obtained crystals were dried to obtain compound [4] (yield: 65.7 g, 0.131 mol, yield 79%).

[0269] 1 H-NMR (500MHz) in DMSO-d6: 8.27 (s, 2H), 8.22 (d, J=10.0Hz, 2H), 7.47-7.37 (m, 4H), 3.95-3.76 (m, 4H), 1.36 (s, 18H).

[0270] <Synthesis of DA-1>

[0271] Tetrahydrofuran (300 g) and methanol (60.0 g) were added to compound [4] (50.0 g, 0.0995 mol), and the atmosphere was purged with nitrogen. Then, 5% palladium carbon (water-containing product) (4.00 g) was added and the atmosphere was purged with nitrogen. A hydrogen gas collection bag (Tedlar Bag) was connected and the mixture was stirred at 25° C. for 24 hours. After the reaction was completed, the palladium carbon was removed by passing through a membrane filter, and the filtrate was concentrated and dried to obtain DA-1 (yield: 42.9 g, 0.0969 mol, yield 97%).

[0272] 1H-NMR (500MHz) in DMSO-d6: 6.95 (t, J=5.0Hz, 2H), 6.66 (d, J=10.0Hz, 2H), 6.56 (s, 2H), 6.44 (m, 2H), 4.97 (s, 4H), 3.82-3.74 (m, 8H), 1.38 (s, 18H).

[0273] (Synthesis Example 2: Synthesis of DA-2)

[0274] DA-2 was synthesized by the following steps.

[0275]

[0276] <Synthesis of compound [5]>

[0277] 2-Chloroethylamine hydrochloride (51.9 g, 0.447 mol) and triethylamine (49.6 g, 0.490 mol) were added to methanol (204 g), and stirred under nitrogen atmosphere and ice cooling. Di-tert-butyl dicarbonate (117 g, 0.536 mol) dissolved in methanol (102 g) was added dropwise while paying attention to heat generation, and stirred at 25°C for 15 hours when heat generation stopped. After the reaction was completed, 4-dimethylaminopyridine (0.543 g, 4.44 mmol) was added, and the mixture was stirred at 60°C for 1 hour to react the excess di-tert-butyl dicarbonate with methanol, and the reaction solution was concentrated. Ethyl acetate (300 g) was added to the concentrated crude product, and the mixture was washed with pure water (300 g × 3 times) by separation. The organic phase was concentrated under reduced pressure and dried to obtain a crude product of compound [5] (yield: 77.8 g). The obtained compound was used in the next step as it is.

[0278] <Synthesis of compound [6]>

[0279] 2-Amino-5-nitrophenol (54.8 g, 0.356 mol), potassium carbonate (61.8 g, 0.447 mol), and potassium iodide (5.90 g, 0.0355 mol) were added to N,N-dimethylacetamide (210 g), and the temperature was raised to 100°C. A crude product (77.8 g) of compound [5] dissolved in N,N-dimethylacetamide (70.0 g) was added dropwise, and the mixture was stirred at 100°C for 21 hours. Ethyl acetate (280 g) and pure water (280 g) were added to the reaction solution, and the precipitated crystals were separated by filtration to obtain a crude product of compound [6]. The filtrate was concentrated, and ethyl acetate (90.0 g) and methanol (340 g) were added and stirred. After the crystals precipitated, the mixture was filtered, and the obtained crystals were washed with methanol (140 g) to obtain a crude product of compound [6]. The crude products obtained in the above two operations were combined, crystallized with ethyl acetate (480 g) and toluene (480 g), and filtered. The obtained crystals were dried to obtain compound [6] (yield: 63.3 g, 0.213 mol).

[0280] 1 H-NMR(500MHz)in DMSO-d6: 7.74 (dd, 1H, J=8.8Hz, 2.4Hz), 7.53 (d, 1H, J=2.4Hz), 6.64 (d, 1H, J=8.8Hz), 7 .20(t, 1H, J=6.0Hz), 4.00-3.97(m, 2H), 6.54(br, 2H), 3.39-3.34(m, 2H), 1.93(s, 9H).

[0281] <Synthesis of Compound [7]>

[0282] Tetrahydrofuran (90.0 g) and pyridine (4.28 g, 0.0541 mol) were added to compound [6] (15.0 g, 0.0505 mol), and the mixture was stirred while being cooled to 5°C in an ice bath. Adipoyl chloride (4.50 g, 0.0246 mol) diluted with tetrahydrofuran (15.0 g) was added dropwise, and the mixture was stirred at 25°C for 19 hours after the addition was completed. After the reaction was completed, water (105 g) was added to the reaction solution, and methanol (315 g) was added and stirred for 40 minutes to precipitate crystals. The crystals were filtered and dried to obtain compound [7] (yield: 15.6 g, 0.0221 mol, yield 90%).

[0283] 1H-NMR(500MHz)in DMSO-d6: 9.23 (s, 2H), 8.49 (d, J=9.0Hz, 2H), 7.90-7.87 (m, 2H), 7.77 (s, 2H), 7.23 (t, J=5.5Hz, 2H), 4.14(br, 4H), 3.40(br, 4H), 2.59(br, 4H), 1.70(br, 4H), 1.42(s, 18H).

[0284] <Synthesis of DA-2>

[0285] N,N-dimethylformamide (465 g) was added to compound [7] (15.5 g, 0.0220 mol), and after nitrogen substitution, 5% palladium carbon (water-containing) (1.24 g) was added and nitrogen substitution was performed. A hydrogen gas collection bag was connected and stirred at 50°C for 5 days. After the reaction was completed, the palladium carbon was removed by passing it through a membrane filter, and ethyl acetate (930 g) was added to the filtrate, and the mixture was separated and washed three times with water (800 g). The organic phase was concentrated and dried to obtain DA-2 (yield: 9.41 g, 0.0146 mol, yield 66%).

[0286] 1 H-NMR(500MHz)in DMSO-d6: 8.54 (s, 2H), 7.46 (d, J=8.5Hz, 2H), 7.05 (t, J=5.5Hz, 2H), 6.20 (d, J=2.0Hz, 2H), 6.09-6.07 (m, 2H), 4.90 (s, 4H), 3.83 (t, J=5.5Hz, 4H), 3.30 (br, 4H), 2.33 (br, 4H), 1.62 (br, 4H), 1.42 (s, 18H).

[0287] (Synthesis Example 3: Synthesis of DA-3)

[0288] DA-3 was synthesized by the following steps.

[0289]

[0290] <Synthesis of compound [8]>

[0291] Tetrahydrofuran (90.0 g) and pyridine (4.28 g, 0.0541 mol) were added to compound [6] (15.0 g, 0.0505 mol), and the mixture was stirred while being cooled to 5°C in an ice bath. Terephthaloyl chloride (5.00 g, 0.0246 mol) diluted with tetrahydrofuran (15.0 g) was added dropwise, and after completion of the addition, the mixture was stirred at 25°C for 20 hours. After completion of the reaction, water (105 g) was added to the reaction solution, and methanol (315 g) was added, and the mixture was stirred for 40 minutes to precipitate crystals. The crystals were filtered and dried to obtain compound [8] (yield: 14.4 g, 0.0198 mol, yield 81%).

[0292] 1 H-NMR(500MHz)in DMSO-d6: 9.80 (s, 2H), 8.49 (d, J=9.0Hz, 2H), 8.17 (s, 4H), 7.98-7.96 (m, 2H), 7.87 (d, J =2.0Hz, 2H), 7.21(t, J=5.5Hz, 2H), 4.24-4.22(m, 4H), 3.47-3.46(m, 4H), 1.27(s, 18H).

[0293] <Synthesis of DA-3>

[0294] N,N-dimethylformamide (489 g) was added to compound [8] (14.3 g, 0.0203 mol), and after nitrogen substitution, 5% palladium carbon (water-containing) (1.14 g) was added and nitrogen substitution was performed. A hydrogen collection bag was connected and stirred at 50°C for about 5 days. After the reaction was completed, the palladium carbon was removed by passing it through a membrane filter, and ethyl acetate (978 g) was added to the filtrate, and the filtrate was washed with water (800 g) three times. The organic phase was concentrated and dried to obtain DA-3 crude crystals. It was crystallized with ethyl acetate and hexane and filtered, and the obtained crystals were dried to obtain DA-3 (yield: 10.0 g, 0.0151 mol, yield 74%).

[0295] 1 H-NMR(500MHz)in DMSO-d6: 9.30 (s, 2H), 8.05 (s, 4H), 7.44 (d, J = 8.5Hz, 2H), 7.01 (t, J = 5.5Hz, 2H), 6.29 (d, J = 1.5Hz, 2 H), 6.18-6.16 (m, 2H), 5.06 (s, 4H), 3.91 (t, J=5.0Hz, 4H), 3.33 (br, 4H), 1.62 (br, 4H), 1.42 (s, 18H).

[0296] (Synthesis Example 4: Synthesis of DA-4)

[0297] DA-4 was synthesized by the following steps.

[0298]

[0299] <Synthesis of compound [9]>

[0300] N,N-dimethylacetamide (150 g) and potassium carbonate (67.0 g, 0.485 mol) were added to ethylene glycol (13.7 g, 0.221 mol), and the mixture was heated and stirred at an internal temperature of 100°C. 2-Fluoro-5-nitrobenzonitrile (76.0 g, 0.458 mol) dissolved in N,N-dimethylacetamide (300 g) was added dropwise through a dropping funnel over 50 minutes, and the mixture was heated and stirred for 6 hours from the end of the addition. After the reaction was completed, the reaction solution was cooled and then poured into stirred water (2250 g) to perform water crystallization. The mixed solution was filtered, tetrahydrofuran (100 g) was added to the obtained wet crystals, and stirred, and a concentrated hydrochloric acid / methanol = 1 / 1 mixed solvent (100 g) was added and filtered. The filtered crystals were dried to obtain compound [9] (yield: 54.6 g, 0.700 mol, yield 70%).

[0301] <Synthesis of compound

[10] >

[0302] Tetrahydrofuran (305 g) was added to compound [9] (30.5 g, 0.0861 mol) and replaced with nitrogen. Borane-tetrahydrofuran complex (287 mL, 0.9 mol / L solution: 0.258 mol) was added dropwise at 25°C. After the addition was completed, the mixture was heated under reflux at 65°C for 17 hours. After the reaction was completed, methanol was added to quench the remaining borane, and a 1 / 1 mixed solvent of concentrated hydrochloric acid / methanol (400 g) was added, followed by stirring at 25°C for 14 hours. The mixture was filtered out using a Buchner funnel, washed with tetrahydrofuran and dried to obtain compound

[10] (yield: 19.3 g, 0.0443 mol, yield 51%).

[0303] <Synthesis of compound

[11] >

[0304] Methanol (77.2 g) and triethylamine (10.3 g, 0.0976 mol) were added to compound

[10] (19.3 g, 0.0443 mol), and the mixture was stirred under nitrogen atmosphere and ice-cooling. Di-tert-butyl dicarbonate (21.3 g, 0.0976 mol) dissolved in methanol (19.3 g) was added dropwise, and the mixture was stirred at 45°C for 15 hours. After the reaction was completed, the reaction solution was introduced into water (96.5 g) for crystallization. Furthermore, methanol (128 g) was added and filtered to obtain yellow crystals with a greasy feel. The mixture was washed with tetrahydrofuran / methanol to remove the greasy feel, and filtered to obtain yellow crystals (11A). The filtrate was concentrated, and washed with tetrahydrofuran / methanol in the same manner to obtain yellow crystals (11B). The obtained crystals (11A, 11B) were dried to obtain compound

[11] (yield: 17.1 g, 0.0304 mol, yield 69%).

[0305] 1 H-NMR(500MHz)in DMSO-d6: 8.23-8.18 (m, 2H), 8.02 (d, J=1.0Hz, 2H), 7.39 (br, 2H), 7.31 (d, J=9.0Hz, 2H), 4.61 (s, 4H), 4.12 (d, J=6.0Hz, 4H), 1.41 (s, 18H).

[0306] <Synthesis of DA-4>

[0307] Compound

[12] (27.0 g, 0.0480 mol) was added with tetrahydrofuran (459 g) and methanol (27 g), and the atmosphere was purged with nitrogen. Then, 5% palladium carbon (water-containing product) (2.16 g) was added and the atmosphere was purged with nitrogen. A hydrogen collection bag was connected and the mixture was stirred at 25° C. for 3 days. Since the reaction did not proceed completely, the palladium carbon was removed by passing through a membrane filter, and then 5% palladium carbon (water-containing product) (2.16 g) was added again and the atmosphere was purged with nitrogen. A hydrogen collection bag was connected and the mixture was stirred at 45° C. for 2 days to complete the reaction. After the reaction was completed, the palladium carbon was removed by passing through a membrane filter, and the filtrate was concentrated. The crude product was purified by column chromatography (ethyl acetate / hexane=2 / 1 (volume ratio)) to obtain DA-4 (yield: 13.7 g, 0.0273 mol, yield 57%).

[0308] 1 H-NMR(500MHz)in DMSO-d6: 6.93 (t, J=5.5Hz, 2H), 6.71 (d, J=8.5Hz, 2H), 6.44 (s, 2H), 6.41-6 .39 (m, 2H), 4.63 (s, 4H), 4.11 (s, 4H), 4.06 (d, J=6.0Hz, 4H), 1.34 (s, 18H).

[0309] "Synthesis of Polyamic Acid"

[0310] (Synthesis Example 5)

[0311] 1.62 g (2.2 mmol) of a 60 wt% NMP solution of DA-1, 1.43 g (13.2 mmol) of DA-7, and 2.51 g (6.6 mmol) of DA-8 were weighed into a 50 mL four-necked flask equipped with a stirrer, and 19.7 g of NMP was added and stirred to dissolve. 2.75 g (11.0 mmol) of DC-1 was added while stirring the diamine solution, and 11.0 g of NMP was added, and the mixture was stirred at 60° C. for 3 hours. Subsequently, 1.94 g (9.89 mmol) of DC-2 was added while stirring the solution, and 7.06 g of NMP was added, and the mixture was stirred at 40° C. for 15 hours to obtain a polyamic acid solution (A-1, viscosity: 721 mPa·s, number average molecular weight: 10,143).

[0312] (Synthesis Examples 6 to 9)

[0313] The polyamic acid solutions (A-2) to (A-5) shown in Table 1 were obtained in the same manner as in Synthesis Example 5 except that the diamine component and the acid dianhydride component were changed as shown in the table below. The viscosity and molecular weight of the obtained polyamic acid are shown in Table 1 below.

[0314]

Table 1

[0315] [Table 1]

[0316]

[0317] "Synthesis of Soluble Polyimide"

[0318] (Synthesis Example 10)

[0319] After adding NMP to the polyamic acid solution (A-1) (25g) obtained in Synthesis Example 5 and diluting it to 6.5% by mass, acetic anhydride (5.76g) and pyridine (1.79g) as imidization catalysts were added, and the mixture was reacted at 50°C for 3 hours. The reaction solution was put into methanol (300mL), and the obtained precipitate was filtered out. The precipitate was washed with methanol, and dried under reduced pressure at 100°C to obtain polyimide powder (A-1-PI). The imidization rate of the polyimide was 52%. NMP (21.6g) was added to the polyimide powder (A-1-PI) (2.4g) obtained above, and it was dissolved by stirring at 80°C for 20 hours to obtain a soluble polyimide (A-1-PI) solution.

[0320] (Synthesis Examples 11 to 14)

[0321] Soluble polyimide solutions (A-2-PI) to (A-5-PI) shown in Table 2 were obtained in the same manner as in Synthesis Example 10 except that the polyamic acid solution was changed as shown in Table 2 below. The imidization ratios of the obtained soluble polyimides are shown in Table 2 below.

[0322]

Table 2

[0323] [Table 2]

[0324]

[0325] "Preparation of Liquid Crystal Alignment Agents"

[0326] (Example 1)

[0327] NMP (6.0 g) and BCS (8.0 g) were added to the polyamic acid (A-1) solution (6.0 g) obtained in Synthesis Example 5, and the mixture was stirred at room temperature for 10 hours to obtain a liquid crystal aligning agent (PAA-1) containing 6% by mass of polyamic acid (A-1), 54% by mass of NMP, and 40% by mass of BCS.

[0328] (Example 2)

[0329] BCS (16.0 g) was added to the soluble polyimide (A-1-PI) solution (24.0 g) obtained in Synthesis Example 10, and the mixture was stirred at room temperature for 10 hours to obtain a liquid crystal alignment agent (SPI-1) containing 6% by mass of soluble polyimide (A-1-PI), 54% by mass of NMP, and 40% by mass of BCS.

[0330] (Examples 3 to 6 and Comparative Examples 1 to 4)

[0331] Liquid crystal aligning agents (PAA-2) to (PAA-5) and (SPI-2) to (SPI-5) were obtained in the same manner as in Example 1 or 2, except that the polyamic acid solution or the soluble polyimide solution was changed as shown in the following Table 3.

[0332]

Table 3

[0333] [Table 3]

[0334]

[0335] "Preparation of samples for seal tightness evaluation"

[0336] The liquid crystal alignment agent prepared in the above-mentioned Examples 1 to 6 and Comparative Examples 1 to 4 was spin-coated on a rectangular glass substrate with a transparent electrode of 30 mm in length × 40 mm in width × 1.1 mm in thickness, dried on a hot plate at 70°C for 90 seconds, and then fired in a hot air circulation oven at 230°C for 20 minutes to form a liquid crystal alignment film with a film thickness of 100 nm.

[0337] Prepare two substrates obtained in this way, apply a 4μm microbead spacer on the liquid crystal alignment film surface of one substrate, and then apply a sealant (723K1 manufactured by Kyoritsu Chemical Industry Co., Ltd.). Next, bond the liquid crystal alignment film surfaces of these substrates to each other and the overlapping width of the substrates to be 1cm. At this time, adjust the amount of sealant added so that the diameter of the sealant after bonding is 3mm. After fixing the two bonded substrates with a clamp, irradiate them with a wavelength of 365nm converted to 4J / cm 2 The film was cured by ultraviolet light at 120° C. for 1 hour to prepare a sample for evaluating adhesion.

[0338] "Determination of seal tightness"

[0339] The evaluation of adhesion is carried out using a desktop precision universal testing machine (AGS-X 500N) (manufactured by Shimadzu Corporation). After the end portions of the upper and lower substrates of the obtained evaluation sample are fixed, the upper portion of the central portion of the substrate is squeezed to measure the strength (N) during peeling. Then, the pressure (N) is standardized with the value obtained by the diameter (mm) of the measured sealant to implement the evaluation of sealing adhesion (N / mm). The results are shown in Table 4.

[0340] As a result, the sealing adhesion of Examples 1 to 6 obtained from diamines DA-1, DA-2, and DA-3 having two Boc amino groups was greater than that of Comparative Examples 1 to 2 obtained from diamine DA-6 having one Boc amino group. In addition, the sealing adhesion of Examples 1 to 6 was higher than that of Comparative Examples 3 to 4 in which the Boc amino groups contained in the compositions were unified with those of Examples 1 to 6 at an equal mol %.

[0341]

Table 4

[0342] [Table 4]

[0343]

[0344] "Synthesis of Polyamic Acid"

[0345] (Synthesis Examples 15 to 17)

[0346] Using the diamine components and the acid dianhydride components shown in Table 5 below, all the diamine components were dissolved in NMP, the acid dianhydride component was added thereto, and the mixture was stirred at 40° C. for 15 hours to obtain polyamic acid solutions (A-6) to (A-8).

[0347] The numerical values ​​in parentheses in Table 5 indicate the mixing ratio (mol parts) of each compound relative to 100 mol parts of the total amount of diamines used in the synthesis in the case of diamine components, and indicate the mixing ratio (mol parts) of each compound relative to 100 mol parts of the total amount of acid dianhydrides used in the synthesis in the case of acid dianhydride components. In the case of organic solvents, the mixing ratio (mass parts) of each organic solvent relative to 100 parts by mass of the total amount of organic solvents contained in the prepared solution is indicated.

[0348]

Table 5

[0349] [Table 5]

[0350]

[0351] "Preparation of Liquid Crystal Alignment Agents"

[0352] (Example 7 and Comparative Examples 5-6)

[0353] Liquid crystal aligning agents (PAA-6) to (PAA-8) were obtained in the same manner as in Example 1, except that the polyamic acid solution was changed as shown in Table 6 below.

[0354]

Table 6

[0355] [Table 6]

[0356]

[0357] "Preparation of samples for seal tightness evaluation"

[0358] The liquid crystal aligning agent obtained in Example 7 and Comparative Examples 5-6 was filtered with a filter having a pore size of 1.0 μm and then spin-coated on a rectangular ITO substrate of 30 mm in length × 40 mm in width × 1.1 mm in thickness. After drying on a hot plate at 80°C for 2 minutes, it was calcined in a hot air circulation oven at 230°C for 30 minutes to form a coating film with a thickness of 100 nm. The coating surface was subjected to a light irradiation of 200 mJ / cm 2 The substrate was irradiated with ultraviolet light having a wavelength of 254 nm and linearly polarized with an extinction ratio of 26:1. The substrate was heated on a hot plate at 230°C for 30 minutes to obtain a substrate with a liquid crystal alignment film.

[0359] After applying a 4μm microbead spacer on the surface of the liquid crystal alignment film of the substrate thus obtained, a sealant (XN-1500T manufactured by Kyoritsu Chemical Industry) is dripped at a position 5mm away from the short side of the substrate. At this time, the amount of sealant dripped is adjusted so that the diameter of the sealant after bonding is 3mm. Next, an ITO substrate of the same size as above is prepared without coating the liquid crystal alignment agent, and the overlapping width of the substrate is 1cm. After fixing the two laminated substrates with a clamp, heat cure at 150°C for 1 hour to prepare a sample for adhesion evaluation.

[0360] "Determination of seal tightness"

[0361] The seal adhesion (N / mm) was evaluated by the same method as above. The results are shown in Table 7.

[0362] The results showed that Example 7 obtained from diamine DA-4 having two Boc amino groups had greater seal adhesion than Comparative Example 6 obtained from diamine DA-6 having one Boc amino group. In addition, Example 7 obtained from diamine DA-4 having a substituent having a Boc amino group at the meta position of the amino group had greater seal adhesion than Comparative Example 5 obtained from diamine DA-5 having a substituent having a Boc amino group at the ortho position of the amino group substituted with a substituent having a Boc amino group.

[0363]

Table 7

[0364] [Table 7]

[0365]

[0366] From the above results, it can be seen that in the adhesion evaluation, the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the diamine compound DA-1, DA-2, DA-3 or DA-4 shows higher adhesion than the liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent of the diamine compound DA-5 or DA-6. Specifically, it is shown by the comparison of Examples 1 to 6 and Comparative Examples 1 to 4 shown in Table 4 and the comparison of Example 7 and Comparative Examples 5 to 6 in Table 7.

[0367] As described above, the use of the diamine represented by the formula (1) of the present application can improve the seal adhesion.

[0368] Industrial Applicability

[0369] The liquid crystal display element using the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can be suitably used in liquid crystal display elements. In addition, these elements are also useful in liquid crystal displays for display purposes, and further in dimming windows and optical shutters for controlling the transmission and shielding of light.

[0370] It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2020-23546 filed on February 14, 2020 are incorporated herein by reference and are incorporated as a disclosure of the specification of the present invention.

Claims

1. A liquid crystal aligning agent comprising a polymer obtained from a diamine represented by the following general formula (1) and an organic solvent, In formula (1), T 1 and T 2 Each independently represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, and -N(CH3)-, W represents a single bond or a hydrocarbon group having a linear, branched, or cyclic structure, wherein, T 1 or T 2 When it is a single bond, W is a single bond, Q represents a substituent represented by the following formula (2), and two Qs present in the molecule are the same or different from each other, In formula (2), X is any of a single bond, -O-, -COO- and -OCO-, and R 1 is a hydrogen atom, A is a tert-butoxycarbonyl group, n is an integer of 1 to 6, and the diamine is any of the following DA-1 to DA-4, 2. The liquid crystal alignment agent according to claim 1, wherein The polymer is at least one polymer selected from the group consisting of a polyimide precursor which is a polycondensate of the diamine represented by the formula (1) and tetracarboxylic dianhydride, and a polyimide which is an imide product thereof.

3. The liquid crystal alignment agent according to claim 2, wherein: The polyimide precursor has a structural unit represented by the following formula (3): Among them, X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y 1 is a divalent organic group derived from a diamine having a structure represented by the above formula (1), R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and there are 2 R 2 The same as or different from each other.

4. The liquid crystal alignment agent according to claim 3, wherein: In the formula (3), X 1 is at least one selected from the group consisting of the following structures (A-1) to (A-21), 5. The liquid crystal alignment agent according to claim 3, wherein: The polyimide precursor further has a structural unit represented by the following formula (4): In formula (4), X2 is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y2 is a divalent organic group derived from a diamine that does not contain the structure of formula (1) in the main chain direction, R5 has the same definition as R2 in formula (3), R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and two R5 and R6 are respectively the same or different from each other.

6. The liquid crystal alignment agent according to claim 4, wherein: The polymer which has the structural unit represented by the said formula (3) is contained in 10 mol% or more with respect to all the polymers contained in a liquid crystal aligning agent. 7 . A liquid crystal alignment film obtained from the liquid crystal alignment agent according to claim 1 . A liquid crystal display element comprising the liquid crystal aligning film according to claim 7 .

9. A polymer obtained from a diamine, wherein the diamine is any one of DA-1 to DA-4 below, in, The polymer is at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (3) and a polyimide which is an imide product thereof, Among them, X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y 1 is a divalent organic group derived from the diamine, R 2 It is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

10. The polymer according to claim 9, wherein In the formula (3), X 1 The structure is at least one selected from the following structures, 11. The polymer according to claim 9 or 10, wherein The content of the structural unit represented by the formula (3) is 10 mol% or more based on the total structural units of the polymer.

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