Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, method for producing liquid crystal element, and compound

Abstract

The present invention provides a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, a method for manufacturing a liquid crystal element, and a compound. A liquid crystal alignment agent comprises a polymer component and a compound [A], wherein the compound [A] is at least one selected from the group consisting of a compound represented by formula (1) and a compound represented by formula (2). In formula (1), Y 1 and Y 2 is a hydrogen atom or a monovalent organic group. 1 An organic group having a valence of (c+d) that satisfies (i), (ii), or (iii). (i) A group having a valence of (c+d) with 1 to 8 carbon atoms, wherein at least one methylene group of a saturated chain hydrocarbon group is substituted with -O. (ii) A saturated hydrocarbon group having a valence of (c+d) with 11 or more carbon atoms. (iii) -S, -SO2, or -CO. In formula (2), Y 3 and Y 4 At least one of the groups is a monovalent group represented by any one of formulas (Y-1) to (Y-6).

Description

Technical Field

[0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, a method for manufacturing a liquid crystal element, and a compound. Background Art

[0002] Liquid crystal elements include a liquid crystal alignment film that aligns liquid crystal molecules in a liquid crystal layer in a specific direction. Typically, a liquid crystal alignment film is formed by applying a liquid crystal alignment agent, made by dissolving a polymer component in an organic solvent, to a substrate surface, preferably by heating the substrate.

[0003] In recent years, large-screen, high-definition LCD televisions have become mainstream, and the widespread use of small display terminals such as smartphones and tablet personal computers (tablet PCs) has further increased the demand for higher-quality liquid crystal elements. Therefore, various liquid crystal alignment agents have been proposed to improve the performance of liquid crystal alignment films and enhance the various characteristics of liquid crystal elements (see, for example, Patent Document 1). Patent Document 1 discloses a liquid crystal alignment agent containing a polyimide or a polyimide precursor and a compound having a structure in which a hydroxymethyl group is bonded to an aromatic ring.

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1] International Publication No. 2010 / 074269 Summary of the Invention

[0007] [Problems to be solved by the invention]

[0008] Liquid crystal elements are not only used in display terminals such as personal computers as in the past, but can also be used for a variety of applications both indoors and outdoors, such as liquid crystal televisions, car navigation systems, mobile phones, smart phones, information displays, phase difference films, dimming films, etc. In addition, with the expansion of the use of applications, it is envisaged that liquid crystal elements will be used in more severe environments than before. For example, liquid crystal elements are sometimes exposed to backlight for a long time due to long-term continuous driving, or are used in high temperature and high humidity environments. In addition, since liquid crystal elements are used in harsh environments, the liquid crystal alignment film is easily peeled off from the substrate. On the other hand, when the liquid crystal alignment film peels off from the substrate, there is concern that the display quality of the liquid crystal element will decline.

[0009] This invention was made in view of the said problem, and its main object is to provide the liquid crystal aligning agent which can improve the adhesiveness of a film with respect to a substrate.

[0010] [Technical means to solve the problem]

[0011] According to the present invention, the following means can be provided.

[0012] [1] A liquid crystal alignment agent comprising a polymer component and a compound [A], wherein the compound [A] is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).

[0013] [Chemistry 1]

[0014]

[0015] (In formula (1), Y 1 and Y 2 are independently a hydrogen atom or a monovalent organic group. 1 and X 2 Each independently represents a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. a1 and a2 each independently represent an integer from 1 to 3. b1 and b2 each independently represent an integer from 0 to 3. 1≦a1+b1≦5 and 1≦a2+b2≦5 are satisfied. Z 1 It is an organic group having a valence of (c+d) that satisfies the following (i), (ii) or (iii).

[0016] (i) a group having 1 to 8 carbon atoms and a valence of (c+d) in which at least one methylene group of a saturated chain hydrocarbon group is substituted by -O-; a group having 1 to 8 carbon atoms and a valence of (c+d) in which at least one hydrogen atom of a saturated chain hydrocarbon group is substituted by a fluorine atom and at least one methylene group of the saturated chain hydrocarbon group is substituted by -O-; or a group having 2 to 8 carbon atoms and a valence of (c+d) in which at least one hydrogen atom of a saturated chain hydrocarbon group is substituted by a carboxyl group.

[0017] (ii) a (c+d)-valent saturated hydrocarbon group having 11 or more carbon atoms, or a (c+d)-valent aromatic hydrocarbon group having 7 or more carbon atoms.

[0018] (iii) -S-, -SO2- or -CO-.

[0019] c and d are each independently an integer of 1 to 3. In the case of (iii), c+d=2. 1 、Y 2 、X 1 and X 2 When there are multiple identical symbols in the formula, the bases of the identical symbols may be the same or different.)

[0020] [Chemistry 2]

[0021]

[0022] (In formula (2), Y 3 and Y4 are independently a hydrogen atom or a monovalent organic group. 3 and Y 4 At least one of X is a monovalent group represented by any one of the following formulas (Y-1) to (Y-6). 3 and X 4 Each of a3 and a4 is independently an integer of 1 to 3. Each of b3 and b4 is independently an integer of 0 to 3. 1≦a3+b3≦5 and 1≦a4+b4≦5 are satisfied. 2 is an organic group with a valence of (e+f). e and f are each independently an integer of 1 to 3. 3 、Y 4 、X 3 and X 4 When there are multiple identical symbols in the formula, the bases of the identical symbols may be the same or different.)

[0023] [Chemistry 3]

[0024]

[0025] (In formula (Y-1) to formula (Y-6), R a and R b Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. "*" represents a bond.

[0026] [2] A liquid crystal alignment film formed using the liquid crystal alignment agent according to [1].

[0027] [3] A liquid crystal element comprising the liquid crystal alignment film according to [2].

[0028] [4] A method for manufacturing a liquid crystal element, comprising: a step of applying the liquid crystal alignment agent of [1] onto each of the conductive films of a pair of substrates having a conductive film to form a coating film; a step of arranging the pair of substrates coated with the liquid crystal alignment agent so that the coating films face each other with a liquid crystal layer sandwiched therebetween to construct a liquid crystal unit; and a step of irradiating the liquid crystal unit with light while applying a voltage between the conductive films.

[0029] [5] A compound represented by the following formula (1):

[0030] [Chemistry 4]

[0031]

[0032] (In formula (1), Y 1 and Y 2 are independently a hydrogen atom or a monovalent organic group. 1 and X2 Each independently represents a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. a1 and a2 each independently represent an integer from 1 to 3. b1 and b2 each independently represent an integer from 0 to 3. 1≦a1+b1≦5 and 1≦a2+b2≦5 are satisfied. Z 1 A (c+d)-valent group having 2 to 8 carbon atoms in a saturated chain hydrocarbon group in which at least one hydrogen atom is replaced by a carboxyl group, or a (c+d)-valent group having 1 to 8 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom and at least one methylene group of the saturated chain hydrocarbon group is replaced by -O-. c and d are each independently an integer of 1 to 3. 1 、Y 2 、X 1 and X 2 When there are multiple identical symbols in the formula, the bases of the identical symbols may be the same or different.)

[0033] [6] A compound represented by the following formula (2).

[0034] [Chemistry 5]

[0035]

[0036] (In formula (2), Y 3 and Y 4 are independently a hydrogen atom or a monovalent organic group. 3 and Y 4 At least one of X is a monovalent group represented by any one of the following formulas (Y-3) to (Y-5). 3 and X 4 Each of a3 and a4 is independently an integer of 1 to 3. Each of b3 and b4 is independently an integer of 0 to 3. 1≦a3+b3≦5 and 1≦a4+b4≦5 are satisfied. 2 is an organic group with a valence of (e+f). e and f are each independently an integer of 1 to 3. 3 、Y 4 、X 3 and X 4 When there are multiple identical symbols in the formula, the bases of the identical symbols may be the same or different.)

[0037] [Chemistry 6]

[0038]

[0039] (In formula (Y-3) to formula (Y-5), R a and R bEach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. "*" represents a bond.

[0040] [Effects of the Invention]

[0041] According to the liquid crystal aligning agent of this invention, by containing a polymer component and compound [A] together, a liquid crystal aligning film excellent in adhesiveness with respect to a board|substrate can be formed. DETAILED DESCRIPTION

[0042] Liquid Crystal Alignment Agents>>

[0043] The liquid crystal alignment agent disclosed herein contains a polymer component and at least one compound [A] selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2). The following describes the components contained in the liquid crystal alignment agent and other components optionally blended as needed.

[0044] In addition, in this specification, the so-called "hydrocarbon group" means a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The so-called "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed only of a chain structure. Among them, it can be saturated or unsaturated. The so-called "alicyclic hydrocarbon group" refers to a hydrocarbon group that only contains an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. Among them, it is not necessary to be composed only of an alicyclic hydrocarbon structure, and a hydrocarbon group having a chain structure in a part thereof is also included. The so-called "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. Among them, it is not necessary to be composed only of an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be included in a part thereof.

[0045] <Polymer composition>

[0046] The polymer component contained in the liquid crystal alignment agent is cross-linked as long as it is cross-linked by compound [A], and its main skeleton is not particularly limited. As polymer component, for example, polyamic acid, polyamic acid ester, polyimide, polyamine, polyenamine (Polyenamine), polyorganosiloxane, polyester, polyamide, polyamide-imide, polystyrene, polybenzoxazole precursor, polybenzoxazole, cellulose derivative, polyacetal, polymaleimide, styrene-maleimide copolymer or poly (methyl) acrylate are main skeletons and have the polymer of the functional group reacting (cross-linking reaction) with compound [A]. In addition, (methyl) acrylate refers to acrylate and methacrylate. So-called polyenamine is a polymer with a carbon-carbon double bond on the ortho position of the amino group of polyamine, for example, polyenamino ketone, polyenamino ester, polyenamino nitrile, polyenamino sulfonyl etc. can be listed.

[0047] As the polymer component, from the perspective of improving the liquid crystal orientation and voltage holding characteristics of the liquid crystal element, preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, a polymer having a partial structure derived from a monomer having a polymerizable unsaturated bond, and polyorganosiloxane is preferred. From the perspective of improving the liquid crystal orientation and voltage holding characteristics and providing a high degree of freedom in the selection of monomers, the liquid crystal aligning agent of the present disclosure is particularly preferably one comprising, as the polymer component, at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide (hereinafter also referred to as "polymer (PA)").

[0048] In terms of enhancing the effect of improving the adhesion of the film by using the compound [A], the liquid crystal aligning agent of the present disclosure is preferably: at least a part of the polymer (PA) contained in the liquid crystal aligning agent contains a structural unit derived from a diamine having a diamine selected from the group consisting of "* 4 -NR 11 R 12 ”, “* 4 -NR 13 -* 5 ”, “* 4 -NR 14 -CO-NR 15 -* 5 ”, “* 4 -NR 16 -CO-* 5 ",and"* 4 -COOR 17 ”(Among them, R 11 is a hydrogen atom or a monovalent organic group. 12 is a protecting group. 13 ~R 17 are independently a hydrogen atom or a protecting group. 4 "and"* 5 " represents a bond to a carbon atom constituting a carbon-carbon bond.) is at least one group (hereinafter also referred to as "specific group A"). By using a polymer containing a structural unit having such a specific group A, the reaction with the polymer components caused by the compound [A] can be promoted, and the adhesion between the liquid crystal alignment film and the substrate can be further improved, which is preferred in this respect.

[0049] Here, in the specific group A, R 11 The monovalent organic group represented is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms or a protecting group.

[0050] The protecting group possessed by the specific group A is preferably a monovalent organic group (thermal detachable group) that is detached by heat. As a specific example of the protecting group of the amino group, for example, there can be mentioned: a carbamate protecting group, an amide protecting group, an imide protecting group, a sulfonamide protecting group, etc. Among the groups, a carbamate protecting group is preferred, and as a specific example thereof, for example, there can be mentioned: a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, a 1,1-dimethyl-2-cyanoethyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a 2-(trimethylsilyl)ethoxycarbonyl group, etc. With respect to the high detachability caused by heat, and the fact that the compound of the group detached by heating during film formation can be discharged to the outside of the film as a gas, among the groups, a tert-butoxycarbonyl group (Boc (t-Butyloxy carbonyl) group) is particularly preferred.

[0051] As a protecting group for carboxyl (R 17 ), and examples thereof include a tert-butyl group, an acetal ester structure of a carboxylic acid, and a ketal ester structure of a carboxylic acid.

[0052] Furthermore, the specific group A can be introduced into any of the main chain and the side chain of the polymer. 4 -NR 13 -* 5 " is preferably a part of the main chain of the polymer. Here, the so-called "main chain" of the polymer refers to the longest "trunk" part in the atomic chain of the polymer. "Side chain" refers to the part branching from the "trunk" of the polymer.

[0053] Specific examples of the specific group A include the following groups.

[0054] [Chemistry 7]

[0055]

[0056] (In the formula, "*" represents a bond to a carbon atom constituting a carbon-carbon bond.)

[0057] In a polymer (PA) containing a structural unit derived from a monomer having a specific group A, the content of the structural unit derived from the monomer having the specific group A relative to all monomer units in the polymer is preferably 2 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. Furthermore, the content of the structural unit derived from the monomer having the specific group A relative to all monomer units in the polymer is preferably 45 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less. The specific group A contained in the polymer (PA) may be one or more.

[0058] The polymer component contained in the liquid crystal alignment agent of the present invention preferably has a base (hereinafter also referred to as an "orientation group") that can impart a pretilt angle to the liquid crystal molecules in the liquid crystal layer when the liquid crystal alignment film is arranged adjacent to the liquid crystal layer. The orientation group mentioned here refers to a base that can impart liquid crystal orientation ability without light irradiation relative to the organic film formed by the liquid crystal alignment agent. Specific examples of orientation groups include: alkyl groups with 4 to 20 carbon atoms, alkoxy groups with 4 to 20 carbon atoms, fluoroalkyl groups with 4 to 20 carbon atoms, fluoroalkoxy groups with 4 to 20 carbon atoms, groups with a mesogenic structure having two or more rings (preferably at least one ring selected from the group consisting of cyclohexane rings, benzene rings and naphthalene rings) bonded directly or via a divalent linking group (for example, an oxygen atom, -CO- or -COO-), and groups having a steroid skeleton.

[0059] The polymer component preferably contains a polymer having a partial structure represented by the following formula (3) as a polymer having an aligning group.

[0060] *-L 1 -R 1 -R 2 -R 3 -R 4 …(3)

[0061] (In formula (3), L 1 Single bond, -O-, -CO-, -COO-* 1 、-OCO-* 1 、-NR 25 -、-NR 25 -CO-* 1 、-CO-NR 25 -* 1 , an alkanediyl group having 1 to 6 carbon atoms, a divalent group in which a hydrogen atom of an alkanediyl group having 2 to 6 carbon atoms is substituted with a hydroxyl group, -OR 26 -* 1 , or -R 26 -O-* 1 (Among them, R 25 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. 26 It is an alkanediyl group having 1 to 3 carbon atoms. 1 "Indicates that the 1 R 1 and R 3 R is independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted cycloalkylene group. 2 is a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted cycloalkylene group, or -R 27 -B 1 -R 28 -(where R27 and R 28 are independently substituted or unsubstituted phenylene or cycloalkylene; B 1 Single bond, -O-, -COO-* 2 、-OCO-* 2 、-OCH2-* 2 、-CH2O-* 2 , or an alkanediyl group having 1 to 3 carbon atoms; "* 2 " indicates that the 28 ). R 4 Represents a hydrogen atom, a fluorine atom, a cyano group, or CH3COO-* 3 (“* 3 " indicates that the 3 ), an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a fluoroalkoxy group having 1 to 18 carbon atoms, a hydrocarbon group having 17 to 51 carbon atoms with a steroid skeleton, or a monovalent group in which a hydrogen atom possessed by an alkyl group or a fluoroalkyl group having 1 to 18 carbon atoms is substituted with a cyano group. 1 、R 2 and R 3 All single bonds, or R 1 、R 2 and R 3 When the total number of substituted or unsubstituted phenylene groups and cycloalkylene groups is one, R 4 It is an alkyl group having 4 to 18 carbon atoms, a fluoroalkyl group having 4 to 18 carbon atoms, an alkoxy group having 4 to 18 carbon atoms, a fluoroalkoxy group having 4 to 18 carbon atoms, or a hydrocarbon group having 17 to 51 carbon atoms and having a steroid skeleton. "*" indicates a bond.

[0062] In the formula (3), L 1 The alkanediyl represented by is preferably linear. 25 Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, and an alkyl group having 1 to 3 carbon atoms is preferred.

[0063] About R 4 , an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a fluoroalkoxy group having 1 to 18 carbon atoms, or a monovalent group in which a hydrogen atom possessed by an alkyl group or a fluoroalkyl group having 1 to 18 carbon atoms is substituted with a cyano group is preferably a straight-chain group. These groups preferably have 2 to 18 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 4 to 18 carbon atoms. As R 4 Examples of the hydrocarbon group having 17 to 51 carbon atoms and a steroid skeleton include cholesteryl, cholesterenyl, and lanostanyl.

[0064] In the alignment group, from the viewpoint of obtaining a liquid crystal element showing good liquid crystal alignment, R 1 、R 2 and R 3 Preferably, the 1 、R 2 and R 3 The total number of at least one of substituted or unsubstituted phenylene groups and substituted or unsubstituted cycloalkylene groups is two or more, and more preferably 2 to 4.

[0065] Specific examples of the aligning group include groups represented by the following formulae (3-1) to (3-10).

[0066] [Chemistry 8]

[0067]

[0068] (In formula (3-1) to formula (3-10), R 20 X is a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a fluoroalkoxy group having 1 to 20 carbon atoms. 21 is -O-, -COO-, or an alkylene group having 1 to 3 carbon atoms. "*" represents a bond.

[0069] The liquid crystal alignment agent disclosed herein preferably contains at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide as a polymer having an alignment group. In the polymer, the content of the structural unit having the alignment group is preferably 1 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more relative to the total amount of the monomer units possessed by the polymer. In addition, the content of the structural unit having the alignment group is preferably 40 mol% or less, more preferably 35 mol% or less, and further preferably 30 mol% or less relative to the total amount of the monomer units possessed by the polymer. In addition, the alignment group contained in the polymer component may be only one type or may be two or more types.

[0070] Next, preferred examples of the polymer contained in the liquid crystal aligning agent of the present disclosure are described.

[0071] (Polyamic acid)

[0072] Polyamic acid can be obtained by reacting tetracarboxylic dianhydride with a diamine compound.

[0073] Tetracarboxylic dianhydride

[0074] Examples of the tetracarboxylic dianhydride used in the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride and the like.

[0075] Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, Furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, etc.; Aromatic tetracarboxylic dianhydrides include, for example, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, ethylene glycol bis(trimellitic)anhydride, 4,4'-carbonyldiphthalic anhydride, etc. In addition, tetracarboxylic dianhydrides described in Japanese Patent Application Laid-Open No. 2010-97188 can also be used. As tetracarboxylic dianhydrides, one type can be used alone or two or more types can be used in combination.

[0076] In order to obtain a liquid crystal alignment film exhibiting good voltage holding characteristics, the tetracarboxylic dianhydride used in the synthesis of the polyamic acid preferably contains at least one selected from the group consisting of aliphatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides, and more preferably contains alicyclic tetracarboxylic dianhydride. The amount of alicyclic tetracarboxylic dianhydride used relative to the total amount of tetracarboxylic dianhydride used in the synthesis of the polyamic acid is preferably 20 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more.

[0077] Diamine compounds

[0078] As the diamine compound used in the synthesis of polyamic acid, known diamine compounds can be used. Examples of the diamine compound include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. The diamine compound used in the synthesis of polyamic acid preferably contains a diamine having a specific group A, as it has high reactivity with compound [A] caused by heating and can further promote crosslinking.

[0079] Specific examples of the diamine having a specific group A include compounds represented by the following formula (d-1-1) to formula (d-1-28).

[0080] [Chemistry 9]

[0081]

[0082] [Chemistry 10]

[0083]

[0084] [Chemistry 11]

[0085]

[0086] [Chemistry 12]

[0087]

[0088] (Wherein, Boc represents tert-butoxycarbonyl.)

[0089] When synthesizing a polymer (PA) containing structural units derived from a monomer having a specific group A, the amount of the diamine having the specific group A used is preferably 4 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, relative to the total amount of diamines used in the synthesis of the polymer. Furthermore, the amount of the diamine having the specific group A used is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 60 mol% or less, relative to the total amount of diamines used in the synthesis of the polymer. When synthesizing the polymer (PA), the diamine having the specific group A may be used alone or in combination of two or more.

[0090] In the case of forming a liquid crystal alignment film of a vertical alignment type and a polymer stabilized alignment type (PSA) type liquid crystal element, when synthesizing a polymer (PA), it is preferred to use a diamine having a specific group A and a diamine having an alignment group. The diamine having an alignment group is preferably a diamine having a partial structure represented by the formula (3). Specific examples of diamines having an alignment group include: dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzene. Cholesteryl aminobenzoate, cholesteryl 3,5-diaminobenzoate, lanosteryl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 5ξ-cholestane-3-yl 3,5-diaminobenzoate, the following formula (E-1):

[0091] [Chemistry 13]

[0092]

[0093] (In formula (E-1), X I and X II are independently a single bond, -O-, *-COO- or *-OCO- (wherein "*" represents I The bond of R I is an alkanediyl group having 1 to 3 carbon atoms, R II is a single bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1. However, a and b cannot be 0 at the same time. ) and the like.

[0094] When synthesizing a polymer having an aligning group as the polymer (PA), the amount of the diamine having an aligning group used is preferably 2 mol% or more, more preferably 6 mol% or more, and even more preferably 10 mol% or more, relative to the total amount of diamines used in the synthesis of the polymer. Furthermore, the amount of the diamine having an aligning group used is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, relative to the total amount of diamines used in the synthesis of the polymer. When synthesizing the polymer (PA), the diamine having an aligning group may be used alone or in combination of two or more.

[0095] Examples of the diamine compound used in the synthesis of polyamic acid include, in addition to the above, m-xylylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like; examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and the like;

[0096] Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, 1,2-bis(4-aminophenoxy)ethane, 1,6-bis(4-aminophenoxy)hexane, bis[2-(4-aminophenyl)ethyl]adipic acid, 2,6-diaminopyridine, 1,4-bis-(4-aminophenyl)-piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)benzene] Examples of the present invention include 1,4-bis(4-aminophenyl)piperazine, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylenediisopropylidene)dianiline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[4,4'-propane-1,3-diylbis(piperidin-1,4-diyl)]diphenylamine, 4,4'-diaminobenzanilide, 4,4'-diaminostilbene, and 1,4-bis(4-aminophenyl)piperazine. Examples of diaminoorganosiloxanes include 1,3-bis(3-aminopropyl)tetramethyldisiloxane. In addition, diamines described in Japanese Patent Application Laid-Open No. 2010-97188 can also be used.

[0097] When synthesizing polyamic acid, the amount of other diamines used is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less relative to the total amount of diamines used in the synthesis. When synthesizing a polymer, the other diamines may be used alone or in combination of two or more.

[0098] Synthesis of polyamic acid

[0099] Polyamic acid can be obtained by reacting the tetracarboxylic dianhydride and diamine compound as described above with a molecular weight modifier as needed. The ratio of the tetracarboxylic dianhydride and diamine compound used in the synthesis reaction of polyamic acid is preferably a ratio in which the anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents relative to 1 equivalent of the amino group of the diamine compound. As molecular weight modifiers, for example, acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, and n-butylamine; monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate, etc. The ratio of the molecular weight modifier used is preferably 20 parts by mass or less relative to a total of 100 parts by mass of the tetracarboxylic dianhydride and diamine compound used.

[0100] The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours.

[0101] Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. A particularly preferred organic solvent is preferably one or more selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphoric triamide, m-cresol, xylenol, and halogenated phenols, or a mixture of one or more of these with other organic solvents (e.g., butyl cellosolve, diethylene glycol diethyl ether, etc.). The amount (a) of the organic solvent used is preferably such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1% to 50% by mass relative to the total amount (a+b) of the reaction solution.

[0102] In this manner, a reaction solution in which polyamic acid is dissolved can be obtained. The reaction solution can be used directly for preparing a liquid crystal alignment agent, or the polyamic acid contained in the reaction solution can be separated and then used for preparing a liquid crystal alignment agent.

[0103] (Polyamic acid ester)

[0104] Polyamic acid ester can be obtained, for example, by the following methods: [I] a method of reacting the polyamic acid obtained by the synthesis reaction with an esterifying agent; [II] a method of reacting a tetracarboxylic acid diester with a diamine compound; [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine compound. The polyamic acid ester contained in the liquid crystal alignment agent may have only an amic acid ester structure, or may be a partial ester in which an amic acid structure and an amic acid ester structure coexist. In addition, the reaction solution formed by dissolving the polyamic acid ester can be directly used for the preparation of the liquid crystal alignment agent, or the polyamic acid ester contained in the reaction solution can be separated and then used for the preparation of the liquid crystal alignment agent.

[0105] (Polyimide)

[0106] Polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid synthesized as described above and imidizing it. Polyimide can be a complete imide formed by dehydrating and ring-closing all the amic acid structures possessed by the polyamic acid as its precursor, or it can be a partial imide formed by dehydrating and ring-closing only a part of the amic acid structure and coexisting amic acid structure and imide ring structure. The polyimide used in the reaction is preferably an imidization rate of 20% to 99%, more preferably 30% to 90%. The imidization rate is expressed as a percentage relative to the total number of amic acid structures and the number of imide ring structures of the polyimide. Here, a part of the imide ring can also be an isoimide ring.

[0107] The dehydration ring-closure of polyamic acid is preferably carried out by the following method: dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closure catalyst to the solution and heating as needed. In the method, as a dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride, etc. can be used. The amount of the dehydrating agent used is preferably set to 0.01 mol to 20 mol relative to 1 mol of the amic acid structure of the polyamic acid. As a dehydration ring-closure catalyst, for example, a tertiary amine such as pyridine, collidine, dimethylpyridine, triethylamine, etc. can be used. The amount of the dehydration ring-closure catalyst used is preferably set to 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent used. As the organic solvent used in the dehydration ring-closure reaction, the organic solvents exemplified as those used in the synthesis of polyamic acid can be cited. The reaction temperature of the dehydration ring-closure reaction is preferably 0°C to 180°C. The reaction time is preferably 1.0 hour to 120 hours. The reaction solution containing the polyimide obtained in this way may be used for preparation of a liquid crystal aligning agent as it is, or may be used for preparation of a liquid crystal aligning agent after isolating the polyimide. Polyimide can also be obtained by imidation of polyamic acid ester.

[0108] When using a photo-alignment method to impart liquid crystal alignment capability to an organic film formed using a liquid crystal alignment agent, it is preferred that at least a portion of the polymer components be a polymer having a photo-alignment group. A photo-alignment group is a functional group capable of imparting anisotropy to the film through a photoreaction such as photoisomerization, photodimerization, photoFries rearrangement, or photodecomposition induced by light irradiation.

[0109] Specific examples of the photo-alignment group include: an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a cinnamic acid structure-containing group containing cinnamic acid or a derivative thereof (cinnamic acid structure) as a basic skeleton, a chalcone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a cyclobutane-containing structure containing cyclobutane or a derivative thereof as a basic skeleton, a styrene-containing group having styrene or a derivative thereof as a basic skeleton, a phenyl benzoate-containing group containing phenyl benzoate or a derivative thereof as a basic skeleton, and the like. Among the above-mentioned groups, the photo-aligning group is preferably at least one selected from the group consisting of a group containing azobenzene, a group containing a cinnamic acid structure, a group containing chalcone, a group containing stilbene, a group containing a cyclobutane structure, and a group containing phenyl benzoate. In terms of high sensitivity to light and ease of introduction into a polymer, a group containing a cinnamic acid structure or a group containing a cyclobutane structure is preferred.

[0110] The polymer having a photo-alignment group can be obtained, for example, by the following methods: (1) a method of obtaining it by polymerization using a monomer having a photo-alignment group; (2) a method of synthesizing a polymer having an epoxy group in a side chain and reacting the epoxy group-containing polymer obtained by the synthesis with a carboxylic acid having a photo-alignment group. The content ratio of the photo-alignment group in the polymer can be appropriately set according to the type of the photo-alignment group in order to impart the desired liquid crystal orientation ability to the coating film. For example, in the case of a group containing a cinnamic acid structure, the content ratio of the photo-alignment group is preferably set to 5 mol% or more, more preferably 10 mol% to 60 mol% relative to the total structural units of the polymer having the photo-alignment group. In the case where the photo-alignment group is a structure containing cyclobutane, the content ratio of the photo-alignment group is preferably set to 50 mol% or more, more preferably 80 mol% or more relative to the total structural units of the polymer having the photo-alignment group. In addition, as a polymer having a photo-alignment group, one type can be used alone, or two or more types can be used in combination.

[0111] The polymer components contained in the liquid crystal alignment agent may be a single type or multiple types. For example, the liquid crystal alignment agent may contain a first polymer and a second polymer having a higher polarity than the first polymer. In this case, the second polymer having a higher polarity tends to be present in the lower layer, while the first polymer tends to be present in the upper layer, thereby enabling phase separation, which is preferred in this respect. Preferred forms of the polymer components of the liquid crystal alignment agent include the following (I) to (III).

[0112] (I) The first polymer and the second polymer are in the form of polymers selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide.

[0113] (II) One of the first polymer and the second polymer is a polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, and the other is in the form of polyorganosiloxane.

[0114] (III) One of the first polymer and the second polymer is at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide, and the other is a polymer having a structural unit derived from a monomer having a polymerizable unsaturated bond (hereinafter also referred to as "polymer (Pm)").

[0115] (Polysiloxane)

[0116] The polyorganosiloxane contained in the liquid crystal alignment agent can be obtained by, for example, hydrolyzing / condensing a hydrolyzable silane compound. Examples of the hydrolyzable silane compound include: alkoxysilane compounds such as tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldiethoxysilane; nitrogen / sulfur-containing alkoxysilane compounds such as 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, and N-(3-cyclohexylamino)propyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-aminopropyltrimethoxysilane. Examples of the hydrolyzable silane compounds include epoxy-containing silane compounds such as 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; unsaturated bond-containing alkoxysilane compounds such as 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, vinyltriethoxysilane, and p-phenyleneditrimethoxysilane; and trimethoxysilylpropylsuccinic anhydride. Hydrolyzable silane compounds may be used alone or in combination of two or more. Furthermore, the term "(meth)acryloyloxy" encompasses both "acryloyloxy" and "methacryloyloxy."

[0117] The hydrolysis / condensation reaction is carried out by reacting one or more of the silane compounds described above with water, preferably in the presence of a suitable catalyst and an organic solvent. When the reaction is carried out, the proportion of water used is preferably 1 to 30 moles relative to 1 mole of the silane compound (total amount). As the catalyst used, for example, there can be mentioned: acid, alkali metal compound, organic base, titanium compound, zirconium compound, etc. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and should be appropriately set. For example, relative to the total amount of the silane compound, it is preferably 0.01 times mole to 3 times mole. As the organic solvent used, for example, hydrocarbons, ketones, esters, ethers, alcohols, etc. can be mentioned. Among the organic solvents, it is preferred to use a water-insoluble or poorly water-soluble organic solvent. Relative to a total of 100 parts by mass of the silane compound used in the reaction, the proportion of the organic solvent used is preferably 10 parts by mass to 10,000 parts by mass.

[0118] The hydrolysis / condensation reaction is preferably carried out by heating in an oil bath, for example. In this case, the heating temperature is preferably set to 130°C or less, and the heating time is preferably set to 0.5 to 12 hours. After the reaction is completed, the organic solvent layer separated from the reaction solution is optionally dried using a desiccant to remove the solvent, thereby obtaining the target polyorganosiloxane. The synthesis method of the polyorganosiloxane is not limited to the hydrolysis / condensation reaction described above; for example, it can be carried out by reacting a hydrolyzable silane compound in the presence of oxalic acid and an alcohol.

[0119] When the polyorganosiloxane is set as a polymer having a functional group such as an orientation group or a photo-orientation group, the synthesis method thereof is not particularly limited. For example, the following method can be cited: at least a part of the raw material uses an epoxy-containing silane compound to synthesize a polyorganosiloxane having an epoxy group in the side chain (hereinafter also referred to as "epoxy-containing polyorganosiloxane"), and then the epoxy-containing polyorganosiloxane is reacted with a carboxylic acid having a functional group. The method is simple and is preferred in terms of increasing the introduction rate of the functional group. In addition, a polyorganosiloxane having a functional group in the side chain can also be synthesized by reacting a hydrolyzable silane compound having a functional group in the monomer. For the polyorganosiloxane, the weight average molecular weight (Mw) of the polystyrene conversion measured by gel permeation chromatography (GPC) is preferably in the range of 100 to 50,000, and more preferably in the range of 200 to 10,000.

[0120] (Polymer (Pm))

[0121] Examples of monomers having a polymerizable unsaturated bond used in the synthesis of the polymer (Pm) include compounds having a (meth)acryloyl group, a vinyl group, a vinylphenyl group, a maleimide group, etc. Furthermore, as the polymer (Pm), from the perspectives of easy introduction of functional groups and good liquid crystal orientation, at least one selected from the group consisting of poly(meth)acrylates, maleimide-based polymers, and styrene-maleimide-based copolymers can be preferably used.

[0122] Specific examples of the monomer having a polymerizable unsaturated bond include: unsaturated carboxylic acids such as (meth)acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, and vinylbenzoic acid; unsaturated carboxylic acid esters such as alkyl (meth)acrylates (for example, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.), cycloalkyl (meth)acrylates, benzyl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 4-hydroxybutyl glycidyl acrylate; unsaturated polycarboxylic acid anhydrides such as maleic anhydride; and (meth)acrylic compounds.

[0123] Aromatic vinyl compounds such as styrene, methylstyrene, divinylbenzene, and 4-(glycidyloxymethyl)styrene; conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene;

[0124] Maleimide compounds such as N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, 4-(2,5-dioxo-3-pyrrolidin-1-yl)benzoic acid, N-(4-glycidyloxyphenyl)maleimide, N-glycidyloxymaleimide, 3-maleimidobenzoic acid, 3-maleimidopropionic acid, 3-(2,5-dioxo-3-pyrrolidin-1-yl)benzoic acid, and methyl 4-(2,5-dioxo-3-pyrrolidin-1-yl)benzoate. In addition, when the polymer (Pm) is a polymer having a functional group, a compound having a functional group can also be used as a monomer having a polymerizable unsaturated bond. In addition, the monomer having a polymerizable unsaturated bond can be used alone or in combination of two or more.

[0125] The polymer (Pm) can be obtained, for example, by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator. As the polymerization initiator used, for example, preferably azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). The proportion of the polymerization initiator used is preferably set to 0.01 to 30 parts by mass relative to 100 parts by mass of all monomers used in the reaction. The polymerization reaction is preferably carried out in an organic solvent. As the organic solvent used in the reaction, for example, alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, etc. are listed, preferably diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, etc. The reaction temperature is preferably set to 30°C to 120°C, and the reaction time is preferably set to 1 hour to 36 hours. The amount of the organic solvent used (a) is preferably such that the total amount (b) of the monomers used in the reaction is 0.1% to 60% by mass relative to the total amount (a+b) of the reaction solution. The weight average molecular weight (Mw) of the polymer (Pm) in terms of polystyrene as measured by GPC is preferably 250 to 500,000, more preferably 500 to 100,000.

[0126] In the embodiments (II) and (III), the total content of polyamic acid, polyamic acid ester, and polyimide is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass to 98% by mass relative to the total amount of the polymer components contained in the liquid crystal alignment agent, from the perspective of obtaining a liquid crystal element with sufficiently high liquid crystal orientation and voltage holding characteristics. In the case of imparting liquid crystal orientation ability to an organic film formed using a liquid crystal alignment agent by a photo-alignment method, it is preferable to use at least one polymer selected from the group consisting of polyorganosiloxane, poly(meth)acrylate, or styrene-maleimide copolymer as a polymer having a photo-alignment group, thereby obtaining an alignment film with better liquid crystal orientation.

[0127] Regarding the content ratio of the polymer component in the liquid crystal alignment agent, from the viewpoint of sufficiently improving the film strength, it is preferably set to 50 mass % or more, more preferably to 60 mass % or more, and even more preferably to 70 mass % or more, relative to the total mass of the solid components contained in the liquid crystal alignment agent (the total mass of the components of the liquid crystal alignment agent other than the solvent).

[0128] <Compound [A]>

[0129] The compound [A] is at least one selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2).

[0130] [Chemistry 14]

[0131]

[0132] (In formula (1), Y 1 and Y 2 are independently a hydrogen atom or a monovalent organic group. 1 and X 2 Each independently represents a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. a1 and a2 each independently represent an integer from 1 to 3. b1 and b2 each independently represent an integer from 0 to 3. 1≦a1+b1≦5 and 1≦a2+b2≦5 are satisfied. Z 1 It is an organic group having a valence of (c+d) that satisfies the following (i), (ii) or (iii).

[0133] (i) a group having 1 to 8 carbon atoms and a valence of (c+d) in which at least one methylene group of a saturated chain hydrocarbon group is substituted by -O-; a group having 1 to 8 carbon atoms and a valence of (c+d) in which at least one hydrogen atom of a saturated chain hydrocarbon group is substituted by a fluorine atom and at least one methylene group of the saturated chain hydrocarbon group is substituted by -O-; or a group having 2 to 8 carbon atoms and a valence of (c+d) in which at least one hydrogen atom of a saturated chain hydrocarbon group is substituted by a carboxyl group.

[0134] (ii) a (c+d)-valent saturated hydrocarbon group having 11 or more carbon atoms, or a (c+d)-valent aromatic hydrocarbon group having 7 or more carbon atoms.

[0135] (iii) -S-, -SO2- or -CO-.

[0136] c and d are each independently an integer of 1 to 3. In the case of (iii), c+d=2. 1 、Y 2 、X 1 and X 2 When there are multiple identical symbols in the formula, the bases of the identical symbols are the same or different.)

[0137] [Chemistry 15]

[0138]

[0139] (In formula (2), Y 3 and Y 4 are independently a hydrogen atom or a monovalent organic group. 3 and Y 4 At least one of X is a monovalent group represented by any one of the following formulas (Y-1) to (Y-6). 3 and X 4Each of a3 and a4 is independently an integer of 1 to 3. Each of b3 and b4 is independently an integer of 0 to 3. 1≦a3+b3≦5 and 1≦a4+b4≦5 are satisfied. 2 is an organic group with a valence of (e+f). e and f are each independently an integer of 1 to 3. 3 、Y 4 、X 3 and X 4 When there are multiple identical symbols in the formula, the bases of the identical symbols are the same or different.)

[0140] [Chemistry 16]

[0141]

[0142] (In formula (Y-1) to formula (Y-6), R a and R b Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. "*" represents a bond.

[0143] (Compound represented by the above formula (1))

[0144] In the formula (1), Y 1 and Y 2 The monovalent organic group represented by may be a monovalent hydrocarbon group having 1 to 20 carbon atoms, or at least one of the methylene groups of the hydrocarbon group may be replaced by -O-, -S-, -CO-, -COO-, or -NR b -、-CONR b - etc. substituted monovalent group (R b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms), a monovalent heterocyclic group, etc. 1 、Y 2 In the case of a monovalent hydrocarbon group, the monovalent hydrocarbon group is preferably an alkyl group having 1 to 7 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and more preferably an alkyl group having 1 to 7 carbon atoms.

[0145] Y 1 and Y 2 The monovalent organic group represented by is preferably a group that is removed by heating during film formation. 1 and Y 2In the case of a group that is thermally detachable, preferred specific examples include: ether-based protecting groups such as alkyl groups having 1 to 7 carbon atoms, benzyl, and p-methoxybenzyl; acetal-based protecting groups such as methoxymethyl, ethoxyethyl, and 2-tetrahydropyranyl; acyl-based protecting groups such as acetyl and benzoyl; allyl-based protecting groups such as allyl and methallyl; and silyl-ether-based protecting groups such as trimethylsilyl, triethylsilyl, and tert-butyldimethylsilyl. From the perspective of achieving both ease of thermal detachment and storage stability, among these groups, ether-based protecting groups, acetal-based protecting groups, and acetyl groups are preferred, and alkyl groups having 1 to 7 carbon atoms, 2-tetrahydropyranyl, methoxymethyl, 1-ethoxyethyl, and acetyl groups are more preferred.

[0146] From the viewpoint of improving the adhesion between the liquid crystal alignment film and the substrate and the storage stability of the liquid crystal aligning agent, Y 1 and Y 2 Preferred are hydrogen atoms, ether-based protecting groups, acetal-based protecting groups or acetyl groups among the above, and more preferred are hydrogen atoms, C1-7 alkyl groups, acetyl groups, 2-tetrahydropyranyl groups, methoxymethyl groups or 1-ethoxyethyl groups.

[0147] X 1 and X 2 Preferred are hydroxyl groups, alkyl groups having 1 to 3 carbon atoms, and alkoxy groups having 1 to 3 carbon atoms.

[0148] From the viewpoint of sufficiently obtaining the effect of improving the adhesion between the liquid crystal aligning film and the substrate, a1 and a2 are each preferably 2 or 3. a1+b1 and a2+b2 are each preferably 2 or more, more preferably 2-4.

[0149] Regarding c and d, c+d is preferably 2 to 6, more preferably 2 to 4, from the viewpoint of achieving a sufficient improvement effect on adhesion to the substrate and a balance between storage stability.

[0150] In Z 1 When (i) is satisfied, Z 1 It is (Z1), (Z2) or (Z3) below.

[0151] (Z1) A (c+d)-valent group having 1 to 8 carbon atoms, in which at least one methylene group of a saturated chain hydrocarbon group is substituted with -O-.

[0152] (Z2) A (c+d)-valent group having 1 to 8 carbon atoms, in which at least one hydrogen atom of a saturated chain hydrocarbon group is substituted with a fluorine atom and at least one methylene group of the saturated chain hydrocarbon group is substituted with -O-.

[0153] (Z3) A saturated chain hydrocarbon group having a valence of (c+d) and 2 to 8 carbon atoms, in which at least one hydrogen atom is replaced by a carboxyl group.

[0154] In the group (Z1), the saturated chain hydrocarbon group may be linear or branched. When the saturated chain hydrocarbon group is linear, when a pair of substrates are bonded together via a sealant after forming a liquid crystal alignment film, narrowing the width of the sealant (seal width) can improve the adhesion between the alignment film and the substrate (hereinafter also referred to as "narrow adhesion"), which is preferred in this respect. In addition, when the saturated chain hydrocarbon group is linear, c+d is preferably 2.

[0155] In the group (Z1), the position of the oxygen atom in the saturated chain hydrocarbon group is not particularly limited. The oxygen atom may be present between carbon-carbon bonds of the saturated chain hydrocarbon group, may be present at the end of the saturated chain hydrocarbon group (i.e., the portion bonded to the benzene ring in formula (1)), or may be present at both carbon-carbon bonds and ends. In the above, the group (Z1) is preferably bonded to the saturated chain hydrocarbon group via Z by an oxygen atom. 1 The group of at least one benzene ring connected is more preferably a group bonded to the Z 1 And the base of all the benzene rings connected.

[0156] The number of oxygen atoms contained in the group (Z1) is preferably two or more, more preferably 2 to 6, from the viewpoint of further improving narrow width adhesion.

[0157] The group (Z2) is a group in which at least one hydrogen atom bonded to a carbon atom in the group (Z1) is substituted with a fluorine atom. In the group (Z2), the saturated chain hydrocarbon group is preferably a straight chain group for the same reasons as for the group (Z1). The description of the specific examples and preferred examples of the position of the oxygen atom in the group (Z2) refers to the description of the group (Z1).

[0158] In the group (Z3), the saturated chain hydrocarbon group may be straight-chain or branched. In addition, the position and number of the carboxyl group in the saturated chain hydrocarbon group are not particularly limited. In terms of obtaining a liquid crystal alignment film with higher narrow-width adhesion, the carboxyl group is preferably bonded to a saturated chain hydrocarbon portion connecting two or more benzene rings in formula (1) via an alkanediyl group. In this case, the degree of freedom of the carboxyl group's activity is increased, which can improve self-crosslinking properties, and is therefore preferred in this regard.

[0159] From the viewpoint of achieving both narrow-width adhesion and storage stability, the number of carboxyl groups possessed by the group (Z3) is preferably 1 to 6, more preferably 1 to 3.

[0160] In Z 1 When (i) is satisfied, preferred specific examples of the compound represented by the formula (1) include a compound represented by the following formula (1-z-1) and a compound represented by the following formula (1-z-2).

[0161] [Chemistry 17]

[0162]

[0163] (In formula (1-z-1), R 5 Y is an alkanediyl group having 1 to 8 carbon atoms, a fluoroalkanediyl group having 1 to 8 carbon atoms, or a divalent group having 2 to 8 carbon atoms containing -O- between carbon-carbon bonds of an alkanediyl group. 1 、Y 2 、X 1 、X 2 , a1, a2, b1 and b2 have the same meanings as in the formula (1).

[0164] [Chemistry 18]

[0165]

[0166] (In formula (1-z-2), R 8 is a single bond or a (c+1)-valent saturated chain hydrocarbon group. 9 is a single bond or a (d+1)-valent saturated chain hydrocarbon group. 10 is a saturated chain hydrocarbon group with a valence of (g+2). 11 is an alkanediyl group. 8 、R 9 、R 10 and R 11 The total number of carbon atoms in Y is 2 to 8. g is an integer of 1 to 3. 1 、Y 2 、X 1 、X 2 , a1, a2, b1, b2, c and d have the same meanings as in the formula (1).

[0167] In the formula (1-z-1), R 5 Preferably "*-O-(CH2) h -O-*", "*-O-(CF2) h -O-*" or "*-O-(R 6 -O) i -*" represented by the group (wherein, R 6 is an alkanediyl group having 2 to 4 carbon atoms. h is an integer of 1 to 8. i is an integer of 1 to 4. ).

[0168] In the above formula (1-z-2), c and d are each preferably 1 or 2, more preferably 1, from the viewpoint of exhibiting adhesion to the substrate and storage stability in a well-balanced manner.

[0169] g is preferably 1 or 2.

[0170] By making the liquid crystal aligning agent contain Z in the formula (1) 1The compound satisfying (i) can form a liquid crystal alignment film with good adhesion to the substrate. In particular, in a touch screen type liquid crystal element, in order to ensure a wide movable area as much as possible and to achieve miniaturization of the display panel, the sealing width is narrowed in order to achieve a narrow frame of the liquid crystal element. In this case, a liquid crystal alignment film with excellent adhesion (i.e., narrow width adhesion) between the alignment film and the substrate can also be formed, which is preferred in this respect. That is, according to Z in the formula (1), 1 The compound satisfying (i) can obtain a liquid crystal alignment film having excellent adhesion to the substrate and being suitable for narrowing the frame of the liquid crystal element. In addition, by using the compound as a cross-linking agent, when a liquid crystal alignment agent containing the cross-linking agent is prepared, a liquid crystal element showing a high voltage holding rate can also be obtained. In terms of high compatibility with polymer components and good coating properties and liquid crystal orientation, Z 1 Among the groups (Z1) to (Z3), the group (Z1) or the group (Z3) is preferred.

[0171] In Z 1 When (ii) is satisfied, Z 1 It is (Z4) or (Z5) below.

[0172] (Z4) a (c+d)-valent saturated hydrocarbon group having 11 or more carbon atoms.

[0173] (Z5) a (c+d)-valent aromatic hydrocarbon group having 7 or more carbon atoms.

[0174] In Z 1 When Z is a basis (Z4), 1 (ie, a saturated hydrocarbon group) preferably has an alicyclic structure. In this case, preferred specific examples of the compound represented by the formula (1) include compounds represented by the following formula (1-z-3).

[0175] [Chemistry 19]

[0176]

[0177] (In formula (1-z-3), R 12 is a (c+1)-valent saturated chain hydrocarbon group or alicyclic group. 13 is a (d+1)-valent saturated chain hydrocarbon group or alicyclic group. 14 and R 15 R are independently a single bond or an alkanediyl group. 16 is an alkanediyl group or a divalent group having an alicyclic structure. 12 、R 13 、R 14 、R 15 and R 16 The total number of carbon atoms is 11 or more. 12、R 13 and R 16 At least one of them has an alicyclic structure. 1 、Y 2 、X 1 、X 2 , a1, a2, b1, b2, c and d have the same meanings as in the formula (1).

[0178] In the formula (1-z-3), R 12 and R 13 The alicyclic group represented is a group obtained by removing (c+1) or (d+1) hydrogen atoms from the ring portion of an alicyclic hydrocarbon ring. In terms of forming a liquid crystal alignment film with high tolerance to high temperature and high humidity, the alicyclic hydrocarbon ring preferably has 4 or more ring members, more preferably 5 or more ring members, and further preferably has 5 to 12 ring members. From the perspective of achieving a well-balanced combination of easy access to the compound, adhesion to the substrate, and tolerance to high temperature and high humidity, the alicyclic structure possessed by the group (Z4) is particularly preferably a cyclopentane ring, a cyclohexane ring, or a cycloheptane ring.

[0179] In terms of the high temperature and humidity tolerance improvement effect, R 12 and R 13 It is preferred that at least one of them is an alicyclic group, and it is more preferred that both of them are alicyclic groups.

[0180] R 14 and R 15 The alkanediyl group represented by R may be linear or branched. 14 and R 15 It is preferably a single bond or an alkanediyl group having 1 to 5 carbon atoms, and more preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms.

[0181] R 16 The alkanediyl represented by R may be linear or branched. 16 In the case of an alkanediyl group, the number of carbon atoms is preferably 1 to 10, and more preferably 1 to 5. 12 and R 13 When at least one of R is an alicyclic group, 16 Preferably it is an alkanediyl group. 16 In the case of a divalent group having an alicyclic structure, R 16 , for example, a group represented by the following formula (r-1) can be mentioned.

[0182] [Chemistry 20]

[0183]

[0184] (In formula (r-1), R 17 is an alkanediyl group. 18is a single bond or an alkanediyl group. 19 is a monovalent alicyclic group. “*” represents a bond.

[0185] In formula (r-1), R 17 The carbon number is preferably 1 to 3. 18 It is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms. 19 A substituted or unsubstituted cyclohexylene group is preferred. Examples of the substituent include a methyl group, an ethyl group, and a fluorine atom.

[0186] From the viewpoint of further improving the high-temperature and high-humidity tolerance, c and d are each preferably 2 or 3, more preferably 2.

[0187] From the viewpoint of improving coating properties and suppressing uneven orientation, R 12 、R 13 、R 14 、R 15 and R 16 The total number of carbon atoms is preferably 40 or less, more preferably 30 or less.

[0188] In Z 1 In the case of the base (Z5), as Z 1 Examples of the aromatic ring possessed by the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. 1 In the case of group (Z5), preferred specific examples of the compound represented by the above formula (1) include compounds represented by the following formula (1-z-4).

[0189] [Chemistry 21]

[0190]

[0191] (In formula (1-z-4), R 20 is a single bond or a (c+1)-valent saturated chain hydrocarbon group. 21 is a single bond or a (d+1)-valent saturated chain hydrocarbon group. 22 Is a divalent group with an aromatic ring structure. 20 、R 21 and R 22 The total number of carbon atoms in Y is 7 or more. 1 、Y 2 、X 1 、X 2 , a1, a2, b1, b2, c and d have the same meanings as in the formula (1). 20 In the case of a single bond, c is 1. 21 When it is a single bond, d is 1.)

[0192] In the formula (1-z-4), R 22 Preferred is a group represented by the following formula (r-2-1) or a group represented by the following formula (r-2-2).

[0193] [Chemistry 22]

[0194]

[0195] (In formula (r-2-1), R 23 is an alkanediyl group. 24 is a single bond or an alkanediyl group. 25 is a monovalent aromatic ring group. In formula (r-2-2), R b is a substituent. t is an integer from 0 to 4. “*” represents a bond.

[0196] In formula (r-2-1), R 23 It can be straight chain or branched. 23 The number of carbon atoms in R is preferably 1 to 3. 24 It is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms. 25 Preferably, it is a substituted or unsubstituted phenyl group or naphthyl group. Examples of the substituent include a methyl group, an ethyl group, and a fluorine atom.

[0197] In formula (r-2-2), as R b Examples of the substituents represented by include a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and an acetyl group. t is preferably 0 to 2.

[0198] c and d are preferably 1 or 2, more preferably 1, respectively.

[0199] From the viewpoint of improving coating properties and suppressing uneven orientation, R 20 、R 21 and R 22 The total number of carbon atoms is preferably 40 or less, more preferably 30 or less.

[0200] By making the liquid crystal aligning agent contain Z in the formula (1) 1 The compound satisfying (ii) can form a liquid crystal alignment film having good adhesion to the substrate. 1 The structure has high hydrophobicity. By including such compound [A] in the liquid crystal alignment agent, it is not easy to cause performance degradation even when exposed to a high temperature and high humidity environment, and a liquid crystal alignment film with excellent high temperature and high humidity tolerance can be formed. In this respect, it is preferred. That is, according to Z in the formula (1), 1The compound satisfying (ii) can obtain a liquid crystal alignment film having not only excellent adhesion to the substrate but also excellent high temperature and high humidity tolerance. In addition, by using the compound as a cross-linking agent, when a liquid crystal alignment agent containing the cross-linking agent is prepared, a liquid crystal cell showing a high voltage holding ratio can also be obtained, which is preferred in this respect.

[0201] In Z 1 When (iii) is satisfied, Z 1 In this case, the compound represented by the formula (1) can be represented by the following formula (1-z-5).

[0202] [Chemistry 23]

[0203]

[0204] (In formula (1-z-5), Z 3 Is -S-, -SO2- or -CO-. 1 、Y 2 、X 1 、X 2 , a1, a2, b1 and b2 have the same meanings as in the above formula (1).

[0205] In terms of forming a liquid crystal alignment film having excellent adhesion to the substrate even when the temperature during film formation is set to a high temperature (for example, 200° C. or higher), Z in formula (1-z-5) is 3 It is preferably -S- or -SO2-, more preferably -SO2-.

[0206] By making the liquid crystal aligning agent contain Z in the formula (1) 1 The compound satisfying (iii) can form a liquid crystal alignment film having good adhesion to the substrate. 1 In the case where the compound [A] showing an electron-withdrawing structure is introduced, even when the temperature during film formation (post-baking temperature) is set to a high temperature, the liquid crystal alignment film is not easily peeled off from the substrate, thereby forming a liquid crystal alignment film with excellent adhesion to the substrate, which is preferable in this respect. Considering that the post-baking temperature is increased in the manufacturing step to shorten the film formation step, according to Z in the formula (1), 1 The compound satisfying (iii) is not prone to film peeling even when the post-bake temperature is increased, has a wide process suitability range, and can suppress the decline in manufacturing yield, which is preferred in this respect. In addition, by using the compound as a cross-linking agent, when a liquid crystal alignment agent containing the cross-linking agent is prepared, a liquid crystal cell showing a high voltage holding ratio can also be obtained, which is preferred in this respect.

[0207] As a specific example of the compound represented by the above formula (1), Z 1 Examples of the compound satisfying (i) include compounds represented by the following formulae (1-1-1) to (1-1-13); Z 1 Examples of the compound satisfying condition (ii) include compounds represented by the following formulae (1-2-1) to (1-2-12); Z 1 Examples of the compound satisfying condition (iii) include compounds represented by the following formulae (1-3-1) to (1-3-9). The compound represented by formula (1) may be used alone or in combination of two or more.

[0208] [Chemistry 24]

[0209]

[0210] [Chemistry 25]

[0211]

[0212] [Chemistry 26]

[0213]

[0214] [Chemistry 27]

[0215]

[0216] [Chemistry 28]

[0217]

[0218] (Compound represented by the formula (2))

[0219] In the formula (2), as Y 3 and Y 4 The monovalent organic group represented by may be a monovalent hydrocarbon group having 1 to 20 carbon atoms, at least one of the methylene groups of the hydrocarbon group is substituted by -O-, -S-, -CO-, -COO-, -NR b -、-CONR b -substituted monovalent group (R b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms), a monovalent heterocyclic group, etc. 3 、Y 4 In the case of a monovalent hydrocarbon group, the monovalent hydrocarbon group is preferably an alkyl group having 1 to 7 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 4 to 7 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and still more preferably an alkyl group having 4 to 7 carbon atoms.

[0220] Y 3 and Y 4 The monovalent organic group represented by is preferably a group that is removed by heating during film formation. 3 and Y 4 In the case of a group that is detached by heat, preferred specific examples include: ether-based protecting groups such as alkyl groups having 1 to 7 carbon atoms, benzyl groups, and p-methoxybenzyl groups; acetal-based protecting groups such as methoxymethyl groups, ethoxyethyl groups, and 2-tetrahydropyranyl groups; acyl-based protecting groups such as acetyl groups and benzoyl groups; allyl-based protecting groups such as allyl groups and methallyl groups; and silyl-ether-based protecting groups such as trimethylsilyl groups, triethylsilyl groups, and tert-butyldimethylsilyl groups. In addition, (meth)acryloyl groups may also be used as Y. 3 and Y 4 The monovalent organic group represented by is introduced into the compound represented by the formula (2). From the viewpoint of ease of thermal removal, among the above groups, an ether-based protecting group, an acetal-based protecting group, or an acetyl group is preferred, and an alkyl group having 1 to 7 carbon atoms, a 2-tetrahydropyranyl group, a methoxymethyl group, a 1-ethoxyethyl group, or an acetyl group is more preferred.

[0221] In the compound represented by formula (2), Y in formula (2) 3 and Y 4 At least one of them is a group represented by any one of the formulas (Y-1) to (Y-6). By including such a compound in the liquid crystal alignment agent, the adhesion of the liquid crystal alignment film to the substrate can be improved, and when the liquid crystal alignment film is peeled off from the substrate in the manufacturing step of the liquid crystal element and the substrate is reused (reprocessed), the liquid crystal alignment film can be easily peeled off from the substrate (the reprocessability can be improved), which is preferred in this respect. In addition, by using the compound represented by the formula (2) as a cross-linking agent, when a liquid crystal alignment agent containing a cross-linking agent is prepared, a liquid crystal element showing a high voltage holding rate can also be obtained, which is preferred in this respect. From the viewpoint of achieving both adhesion and reprocessability of the liquid crystal alignment film to the substrate, Y 3 and Y 4 It is preferably a group represented by any one of the formulae (Y-2) to (Y-6) among the formulae (Y-1) to (Y-6), and in terms of obtaining a liquid crystal element with good liquid crystal orientation and voltage retention, it is more preferably a group represented by any one of the formulae (Y-2) and (Y-4) to (Y-6), and is particularly preferably an alkyl group having 4 to 7 carbon atoms, a 2-tetrahydropyranyl group, a methoxymethyl group, a 1-ethoxyethyl group or an acetyl group.

[0222] Y in the formula (2) 3 and Y 4In terms of obtaining a liquid crystal alignment film having good adhesion to the substrate, the total number of the groups represented by any one of the formulas (Y-1) to (Y-6) is preferably two or more. In terms of obtaining a liquid crystal alignment film having good adhesion to the substrate and reworkability in a well-balanced manner, Y in the formula (2) is particularly preferably 3 and Y 4 All of them are groups represented by any one of the formulae (Y-1) to (Y-6). In addition, the compound represented by the formula (2) may have only one group represented by the formulae (Y-1) to (Y-6), or may have two or more groups.

[0223] X 3 and X 4 Preferred are hydroxyl groups, alkyl groups having 1 to 3 carbon atoms, and alkoxy groups having 1 to 3 carbon atoms.

[0224] As Z 2 , which include: a chain hydrocarbon group with a (e+f) valence of 1 to 12 carbon atoms, an alicyclic hydrocarbon group with a (e+f) valence of 3 to 12 carbon atoms, an aromatic hydrocarbon group with a (e+f) valence of 6 to 12 carbon atoms, etc. 2 It is preferably a (e+f)-valent linear or branched chain hydrocarbon group having 1 to 12 carbon atoms, and more preferably a (e+f)-valent linear or branched saturated chain hydrocarbon group having 1 to 10 carbon atoms.

[0225] From the viewpoint of sufficiently obtaining the effect of improving the adhesion between the liquid crystal aligning film and the substrate, a3 and a4 are each preferably 2 or 3. a3+b3 and a4+b4 are each preferably 2 or more, more preferably 2-4.

[0226] Regarding e and f, e+f is preferably 2 to 6, more preferably 2 to 4, from the viewpoint of sufficiently obtaining the effect of improving the adhesion to the substrate and from the viewpoint of a balance with storage stability.

[0227] By including the compound represented by the formula (2) as a crosslinking agent in the liquid crystal aligning agent, a liquid crystal aligning film having good adhesion to the substrate can be formed. 3 、Y 4 The introduction of the specific groups represented by the above formula (Y-1) to formula (Y-6) is preferred from the viewpoint of forming a liquid crystal aligning film having excellent reworkability.

[0228] Specific examples of the compound represented by formula (2) include compounds represented by the following formulas (2-1-1) to (2-1-10), etc. The compound represented by formula (2) may be used alone or in combination of two or more.

[0229] [Chemistry 29]

[0230]

[0231] [Chemistry 30]

[0232]

[0233] About the content of compound [A] in the liquid crystal aligning agent, with respect to the aspect of the improvement effect of the adhesion to the substrate that can be fully improved, relative to the total amount 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, it is preferably set to more than 0.5 parts by mass, more preferably set to more than 1 part by mass, and then preferably set to more than 2 parts by mass. In addition, about the content of compound [A], with respect to the viewpoint of suppressing the performance degradation caused by excessive addition and the viewpoint of making storage stability good, relative to the total amount 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, it is preferably set to less than 40 parts by mass, more preferably set to less than 30 parts by mass, and then preferably set to less than 20 parts by mass. In addition, as compound [A], one can be used alone, or two or more can be used in combination.

[0234] <Other ingredients>

[0235] The liquid crystal alignment agent of the present disclosure may also contain other compounds other than the polymer component and compound [A] as needed. As a specific example thereof, epoxy compounds (for example, N, N, N', N'-tetraglycidyl-m-phenylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-aminomethylcyclohexane, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, etc.), functional silane compounds (for example, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, etc.), antioxidants, metal chelate compounds, curing accelerators, surfactants, fillers, dispersants, photosensitizers, etc. In addition, the content of other compounds can be appropriately selected according to each compound within the scope of the effect of the present disclosure. When using a compound different from the compound [A] as a crosslinking agent in combination, content of the different compound is preferably 5 mass % or less, more preferably 1 mass % or less relative to the total amount of the compound [A] contained in the liquid crystal aligning agent.

[0236] (Solvent)

[0237] The liquid crystal alignment agent disclosed herein is prepared in the form of a liquid composition, wherein the polymer component, compound [A], and optionally other components are dissolved in a solvent. The solvent is preferably an organic solvent, for example, an aprotic polar solvent, a phenolic solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like.

[0238] Specific examples of the organic solvent used include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, cyclohexanone, 3-methoxy-1-butanol, etc. These can be used alone or in combination of two or more.

[0239] The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1% by mass to 10% by mass. If the solid content concentration is 1% by mass or more, the film thickness of the coating can be fully ensured, and there is a tendency to obtain a good liquid crystal alignment film. In addition, if the solid content concentration is 10% by mass or less, the film thickness of the coating will not become excessively large. In addition, the viscosity of the liquid crystal alignment agent can be appropriately increased, and there is a tendency to make the coating property good.

[0240] Liquid crystal alignment film and liquid crystal element

[0241] The liquid crystal alignment film of the present invention is formed by a liquid crystal alignment agent prepared as described above. In addition, the liquid crystal element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operating mode of the liquid crystal in the liquid crystal element is not particularly limited, and can be applied to various modes such as twisted nematic (TN) type, super twisted nematic (STN) type, vertical alignment (VA) type (including vertical alignment-multi-domain vertical alignment (VA-MVA) type, vertical alignment-patterned vertical alignment (VA-PVA) type, etc.), in-plane switching (IPS) type, fringe field switching (FFS) type, optically compensated bend (OCB) type, polymer stabilized alignment (PSA) type, etc. The liquid crystal element can be manufactured, for example, by a method including the following steps 1 to 3. In step 1, the substrate used varies depending on the desired operating mode. Steps 2 and 3 are common to all operating modes.

[0242] <Step 1: Coating film formation>

[0243] First, a liquid crystal alignment agent is applied to a substrate, and the applied surface is preferably heated to form a coating film on the substrate. As a substrate, for example, a transparent substrate comprising the following materials can be used: glass such as float glass and soda glass; resins such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly(alicyclic olefin). As a transparent conductive film provided on one surface of the substrate, a NESA film (a registered trademark of PPG, USA) comprising tin oxide (SnO2) and an indium tin oxide (In2O3-SnO2) (Indium Tin Oxide, ITO) film can be used. In the case of manufacturing a TN type, STN type or VA type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, in the case of manufacturing an IPS type or FFS type liquid crystal element, a substrate provided with electrodes patterned into a comb shape and an opposing substrate on which no electrodes are provided are used. The liquid crystal aligning agent is applied to the substrate on the electrode formation surface, preferably by offset printing, flexographic printing, spin coating, roll coater or inkjet printing.

[0244] After applying the liquid crystal alignment agent, it is preferred to perform preheating (prebaking) for the purpose of preventing dripping of the applied liquid crystal alignment agent. The prebaking temperature is preferably 30°C to 200°C, and the prebaking time is preferably 0.25 minutes to 10 minutes. Then, a calcination (post-baking) step is performed for the purpose of completely removing the solvent. The calcination temperature (post-baking temperature) at this time is preferably 80°C to 250°C, more preferably 80°C to 200°C. The post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film thus formed is preferably 0.001 μm to 1 μm.

[0245] <Step 2: Orientation treatment>

[0246] In the case of manufacturing a TN type, STN type, IPS type or FFS type liquid crystal cell, a process (orientation treatment) of imparting liquid crystal orientation capability to the coating film formed in the step 1 is implemented. Thus, the orientation capability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. As an orientation treatment, the following treatment can be used: a friction treatment in which a roller wound with a cloth containing fibers such as nylon, rayon, and cotton is rubbed in a certain direction against the coating film formed on the substrate, or a light orientation treatment in which the coating film formed on the substrate is irradiated with light to impart liquid crystal orientation capability to the coating film. On the other hand, in the case of manufacturing a vertically aligned (VA) type liquid crystal cell, the coating film formed in the step 1 can be used directly as a liquid crystal alignment film, but in order to further improve the liquid crystal orientation capability, the coating film can also be subjected to an orientation treatment. A liquid crystal alignment film preferred for a vertically aligned liquid crystal cell can also be preferably used for a PSA type liquid crystal cell.

[0247] In the photo-alignment treatment, light irradiation can be carried out by the following methods, etc.: a method of irradiating the coating after the post-baking step, a method of irradiating the coating after the pre-baking step and before the post-baking step, and a method of irradiating the coating during the coating heating process in at least any one of the pre-baking step and the post-baking step. As radiation irradiated to the coating, for example, ultraviolet rays and visible light containing light with a wavelength of 150nm to 800nm can be used. Preferably, ultraviolet rays containing light with a wavelength of 200nm to 400nm are used. When the radiation is polarized, it can be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, irradiation can be carried out in a direction perpendicular to the substrate surface, in an oblique direction, or in a combination of these directions. The irradiation direction in the case of non-polarized radiation is set to an oblique direction.

[0248] Examples of the light source include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, and excimer lasers. The radiation dose to the substrate surface is preferably 400 J / m 2 ~50,000J / m 2 , more preferably 1,000 J / m 2 ~20,000J / m 2 After the light irradiation for imparting alignment ability, the substrate surface may be cleaned using water, an organic solvent (e.g., methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.) or a mixture thereof, or the substrate may be heated.

[0249] <Step 3: Liquid Crystal Cell Construction>

[0250] Prepare two substrates with liquid crystal alignment films formed as described above, and manufacture a liquid crystal cell by configuring a liquid crystal adjacent to the liquid crystal alignment film between the two substrates. When manufacturing a liquid crystal cell, for example, the following methods can be cited: two substrates are arranged opposite to each other with a gap in a manner that the liquid crystal alignment films face each other, the peripheral portions of the two substrates are bonded together using a sealant, and a method of injecting a filling liquid crystal into the cell gap surrounded by the substrate surface and the sealant and sealing the injection hole, a method of utilizing a liquid crystal droplet (One Drop Fill, ODF) method, etc. As a sealant, for example, an epoxy resin containing a hardener and aluminum oxide balls as a spacer can be used. As liquid crystals, nematic liquid crystals and disc-shaped liquid crystals can be cited, among which nematic liquid crystals are preferred. In the PSA mode, after constructing the liquid crystal cell, the liquid crystal cell is subjected to light irradiation treatment while a voltage is applied between the conductive films possessed by a pair of substrates.

[0251] In the case of manufacturing a PSA type liquid crystal element, the liquid crystal element can be manufactured by a method including the following three steps.

[0252] A step of applying the liquid crystal aligning agent of the present disclosure onto the conductive film of each of a pair of substrates having a conductive film to form a coating film.

[0253] A step of constructing a liquid crystal cell by arranging a pair of substrates coated with a liquid crystal aligning agent so that the coated films face each other with a liquid crystal layer interposed therebetween.

[0254] A step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films.

[0255] Specifically, first, a liquid crystal and a photopolymerizable monomer are injected or dropped between a pair of substrates having a conductive film. A liquid crystal cell is constructed in the same manner as in Steps 1 to 3 above, except for this aspect. Conventionally known compounds can be used as photopolymerizable monomers. Polyfunctional (meth)acrylic monomers are preferred.

[0256] 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 5V to 50V. As the irradiated light, for example, ultraviolet rays and visible light containing wavelengths of 150nm to 800nm can be used. Among the light, ultraviolet rays containing wavelengths of 300nm to 400nm are preferred. 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. As the irradiation amount of light, 1,000J / m 2 ~200,000J / m 2 , more preferably 1,000 J / m 2 ~100,000J / m 2 .

[0257] For each mode of liquid crystal cell, a polarizing plate is then attached to the outer surface of the liquid crystal cell as needed to produce a liquid crystal element. Examples of polarizing plates include those made by sandwiching a polarizing film called "H film" made by stretching and aligning polyvinyl alcohol while allowing it to absorb iodine, between a cellulose acetate protective film, or a polarizing plate consisting solely of the H film.

[0258] The liquid crystal element disclosed herein can be effectively applied to various applications. Specifically, it can be applied to various display devices such as watches, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (PDAs), digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays, as well as to light-adjusting films and retardation films.

[0259] [Example]

[0260] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

[0261] In the following examples, the solution viscosity, weight average molecular weight (Mw), number average molecular weight (Mn), and imidization ratio of the polymer were measured by the following methods.

[0262] <Polymer Solution Viscosity>

[0263] The solution viscosity of the polymer was measured at 25°C using an E-type viscometer.

[0264] <Weight average molecular weight and number average molecular weight>

[0265] Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. Molecular weight distribution (Mw / Mn) was calculated based on the obtained Mw and Mn.

[0266] Device: Showa Denko's "GPC-101"

[0267] GPC columns: Combination of "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804" manufactured by Shimadzu GLC Co., Ltd.

[0268] Mobile phase: tetrahydrofuran (THF)

[0269] Column temperature: 40°C

[0270] Flow rate: 1.0 mL / min

[0271] Sample concentration: 1.0 mass%

[0272] Sample injection volume: 100 μL

[0273] Detector: Differential refractometer

[0274] Standard material: monodisperse polystyrene

[0275] <Imidization ratio of polyimide>

[0276] The polyimide solution was poured into pure water, the obtained precipitate was fully dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl sulfoxide. The hydrogen nuclear magnetic resonance (H-NMR) was performed at room temperature using tetramethylsilane as a reference substance. 1 H-NuclearMagnetic Resonance, 1 H-NMR) determination. 1 The imidization ratio [%] was determined from the H-NMR spectrum using the following formula (1).

[0277] Imidization rate [%] = (1-(β 1 / (β 2 ×α)))×100…(1)

[0278] (In formula (1), β 1 is the peak area of the proton origin of the NH group appearing near the chemical shift of 10 ppm, β 2is the peak area of other proton sources, and α is the ratio of the number of other protons to one proton of the NH group in the polymer precursor (polyamic acid).

[0279] The abbreviations of the compounds used in the following examples are shown below. In addition, for convenience, the "compound represented by formula (X)" may be simply referred to as "compound (X)".

[0280] Monomer and side chain carboxylic acid

[0281] [Chemistry 31]

[0282]

[0283] [Chemistry 32]

[0284]

[0285] [Chemistry 33]

[0286]

[0287] [Chemistry 34]

[0288]

[0289] [Chemistry 35]

[0290]

[0291] Compound [A]

[0292] [Chemistry 36]

[0293]

[0294] [Chemistry 37]

[0295]

[0296] [Chemistry 38]

[0297]

[0298] <Polymer Synthesis>

[0299] 1. Synthesis of polyimide

[0300] [Synthesis example 1]

[0301] 70 parts by mole of 2,3,5-tricarboxycyclopentylacetic dianhydride and 30 parts by mole of pyromellitic dianhydride as tetracarboxylic dianhydride, 30 parts by mole of cholesteryloxy-2,4-diaminobenzene as a diamine, 40 parts by mole of compound (D-4), and 30 parts by mole of 3,5-diaminobenzoic acid were dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at 40°C for 24 hours to obtain a solution containing 20% by mass of polyamic acid. Subsequently, NMP was added to the obtained polyamic acid solution, and 3.00 molar equivalents of pyridine and acetic anhydride were added to the carboxyl groups of the polyamic acid, respectively, and a dehydration ring-closure reaction was carried out at 80°C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with fresh γ-butyrolactone and further concentrated to obtain a solution containing 20% by mass of a polyimide with an imidization ratio of 63% (referred to as "Polymer (P-1)"). A small aliquot of this solution was added with NMP to prepare a 10% by mass solution. The solution viscosity was measured to be 37 mPa·s.

[0302] [Synthesis Example 2, Synthesis Example 9 to Synthesis Example 16]

[0303] Polymerization was carried out in the same manner as in Synthesis Example 1 except that the types and amounts of tetracarboxylic dianhydride and diamine used in the polymerization were changed as shown in Table 1, thereby obtaining solutions containing polymer (P-2) and polymers (P-9) to (P-16) each of which is polyimide.

[0304] 2. Synthesis of polyamic acid

[0305] [Synthesis example 3]

[0306] 70 parts by mole of 2,3,5-tricarboxycyclopentylacetic dianhydride and 30 parts by mole of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, and 30 parts by mole of cholesteryloxy-2,4-diaminobenzene, 40 parts by mole of 3,5-diamino-N,N-bis(pyridin-3-ylmethyl)benzamide, and 30 parts by mole of 3,5-diaminobenzoic acid as diamines were dissolved in NMP and reacted at 40°C for 24 hours to obtain a solution containing 20% by mass of polyamic acid (hereinafter referred to as "polymer (P-3)"). A small amount of this solution was aliquoted and added to NMP to prepare a solution having a concentration of 10% by mass. The solution viscosity was measured to be 42 mPa·s.

[0307] [Synthesis Example 4 to Synthesis Example 8, Synthesis Example 17]

[0308] Polymerization was carried out in the same manner as in Synthesis Example 3 except that the types and amounts of tetracarboxylic dianhydride and diamine used in the polymerization were changed as shown in Table 1, thereby obtaining solutions containing polymers (P-4) to (P-8) and (P-17) as polyamic acids. In Table 1, the numerical values for anhydrides represent the ratio (parts by mole) of each compound relative to 100 parts by mole of the total amount of tetracarboxylic dianhydride used in the synthesis. The numerical values for diamines represent the ratio (parts by mole) of each compound relative to 100 parts by mole of the total amount of diamines used in the synthesis.

[0309] [Table 1]

[0310]

[0311] 3. Synthesis of polyorganosiloxane

[0312] [Synthesis Example 18]

[0313] A 1000ml three-necked flask was charged with 90.0g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 500g of methyl isobutyl ketone, and 10.0g of triethylamine and mixed at room temperature. Subsequently, 100g of deionized water was added dropwise from a dropping funnel over 30 minutes, mixed under reflux, and reacted at 80°C for 6 hours. After the reaction was completed, the organic layer was removed and washed with a 0.2% by mass aqueous solution of ammonium nitrate until the washed water became neutral. The solvent and water were then distilled off under reduced pressure. An appropriate amount of methyl isobutyl ketone was added to obtain a 50% by mass solution of a polymer (ESSQ-1) of a polyorganosiloxane having epoxy groups.

[0314] In a 500 ml three-necked flask, 6.28 g of compound (C-1) (20 mol% relative to the amount of epoxy groups in polymer (ESSQ-1)), 3.44 g of compound (C-3) (10 mol% relative to the amount of epoxy groups in polymer (ESSQ-1)), 2.00 g of tetrabutylammonium bromide, 80 g of a solution containing polymer (ESSQ-1), and 239 g of methyl isobutyl ketone were added and stirred at 90°C for 18 hours. After cooling to room temperature, separation and washing with distilled water were repeated 10 times. The organic layer was then recovered, concentrated using a rotary evaporator and diluted with NMP twice, and then adjusted with NMP to a solids concentration of 10% by mass to obtain an NMP solution of polymer (PS-1).

[0315] [Synthesis Example 19]

[0316] An NMP solution containing 10% by mass of a polymer (PS-2) as a polyorganosiloxane was obtained in the same manner as in Synthesis Example 18, except that the type and amount of the side chain carboxylic acid used in the reaction were changed as described in Table 2. In Table 2, the numerical values of the side chain carboxylic acid represent the ratio (side chain modification ratio, mol %) to the amount of epoxy groups in the polymer (ESSQ-1).

[0317] [Table 2]

[0318]

[0319] 4. Synthesis of Styrene-Maleimide Polymers

[0320] [Synthesis Example 20]

[0321] Under nitrogen, a 100 mL two-necked flask was charged with 10 mol parts of compound (M-1) and 10 mol parts of compound (M-4) as polymerization monomers, 35 mol parts of methacrylic acid, and 45 mol parts of glycidyl methacrylate, 2 mol parts of 2,2'-azobis(2,4-dimethylvaleronitrile) as a free radical polymerization initiator, and 50 ml of tetrahydrofuran as a solvent. Polymerization was carried out at 70°C for 5 hours. After reprecipitation in methanol, the precipitate was filtered and vacuum-dried at room temperature for 8 hours to obtain the target polymer (PM-1). The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 30,000, and the molecular weight distribution (Mw / Mn) was 2.

[0322] [Synthesis Example 21, Synthesis Example 22]

[0323] Polymers (PM-2) and (PM-3) as styrene-maleimide copolymers were obtained in the same manner as in Synthesis Example 20, except that the types and amounts of the polymerizable monomers used in the reaction were changed as shown in Table 3. In Table 3, the numerical values for the monomers represent the proportion (parts by mole) of each compound relative to 100 parts by mole of the total amount of the monomers used in the synthesis.

[0324] [Table 3]

[0325]

[0326] 5. Preparation and evaluation of liquid crystal alignment agents (1)

[0327] [Example 1: PSA-type liquid crystal display element]

[0328] (1) Preparation of liquid crystal alignment agent (AL-1)

[0329] To the solution containing 100 parts by mass of the polymer (P-1) obtained in Synthesis Example 1, 5 parts by mass of the compound (Ad-1) and NMP and butyl cellosolve (BC) as solvents were added to prepare a solution having a solvent composition of NMP / BC = 50 / 50 (mass ratio) and a solids concentration of 4.0% by mass. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent (AL-1).

[0330] (2) Evaluation of reprocessability

[0331] On a transparent conductive film including an ITO film provided on one surface of a glass substrate having a thickness of 1 mm, a liquid crystal alignment agent (AL-1) was applied using a spinner, and pre-baked at 100 ° C for 90 seconds using a hot plate to form a coating having a film thickness of about 0.10 μm. The operation was repeated to form two substrates with coatings. Then, the two obtained substrates were stored in a dark room at 25 ° C under a nitrogen environment. 12 hours and 48 hours after the start of storage, one substrate was taken out respectively, and after being immersed in a beaker of NMP adjusted to 40 ° C for 2 minutes, it was washed several times with ultrapure water, and water droplets on the surface were removed by blowing. The substrate was observed using an optical microscope to investigate whether the coating had residue, thereby evaluating the ease of peeling (reprocessing) of the liquid crystal alignment film from the substrate. In the evaluation, if no coating film residue was observed after NMP immersion even on a substrate removed 48 hours after the start of storage, the reworkability was rated "good (○)". If coating film residue was observed on the substrate after 48 hours but not on the substrate after 12 hours, the reworkability was rated "acceptable (△)". If no coating film residue was observed on the substrate after 12 hours, the reworkability was rated "poor (×)". The results showed that the reworkability was "good (○)" in the above examples.

[0332] (3) Evaluation of film adhesion

[0333] The liquid crystal alignment agent (AL-1) prepared above was applied to a glass substrate using a spinner, and pre-baked for 2 minutes using a hot plate at 80°C, and then heated for 30 minutes in an oven at 230°C with nitrogen substituted in the box (post-baking), thereby forming a coating with an average film thickness of 0.10 μm. The same operation was repeated to prepare two glass substrates with coatings formed thereon. On the coating of one glass substrate with a coating, an ODF sealant (manufactured by Sekisui Chemical Co., Ltd., S-WB42) was applied in a manner to a width of 1 mm, and the coating of another glass substrate was bonded in a manner that the coating was in contact with the ODF sealant. Then, a metal halide lamp was used to irradiate 30,000 J / m 2After being exposed to light (converted to 365 nm), the film was heated in an oven at 120°C for 1 hour. Then, the adhesion strength was measured using a tensile compression tester (model: SDWS-0201-100SL) from Imada Manufacturing Co., Ltd. to evaluate the adhesion of the film to the substrate. During the evaluation, the adhesion strength was set to 175 N / cm 2 The above cases are rated as "good (○)", and the pressure is set to 150 N / cm 2 More than but less than 175N / cm 2 If the load is less than 150 N / cm, set it as "OK (△)". 2 The case of was rated as "poor (×)". As a result, in the above example, the adhesion force was 192 N / cm 2 , thus the adhesion was evaluated as "good (○)".

[0334] (4) Preparation of liquid crystal composition

[0335] To 10 g of nematic liquid crystal (MLC-6608, manufactured by Merck), 5% by mass of a liquid crystal compound represented by the following formula (L1-1) and 0.3% by mass of a photopolymerizable compound represented by the following formula (L2-1) were added and mixed to obtain a liquid crystal composition LC1.

[0336] [Chemistry 39]

[0337]

[0338] (5) Manufacturing of PSA-type liquid crystal display elements

[0339] The liquid crystal alignment agent (AL-1) prepared above was applied to each electrode surface of two glass substrates each having a conductive film including an ITO electrode patterned into a slit shape using a liquid crystal alignment film printer (manufactured by Japan Photographic Printing Co., Ltd.), heated on a hot plate at 80°C (pre-baked) for 2 minutes to remove the solvent, and then heated on a hot plate at 230°C (post-baked) for 10 minutes to form a coating having an average film thickness of 0.06 μm. The coating was ultrasonically cleaned in ultrapure water for 1 minute and then dried in a clean oven at 100°C for 10 minutes to obtain a pair (two sheets) of substrates having a liquid crystal alignment film. In addition, the pattern of the electrode used is the same type of pattern as the electrode pattern in the PSA mode.

[0340] Then, an epoxy resin adhesive containing alumina balls with a diameter of 5.5 μm was applied to the outer edge of the surface of one of the pair of substrates having the liquid crystal alignment film, and then the surfaces of the liquid crystal alignment films were overlapped and pressed together to cure the adhesive. Then, the liquid crystal composition LC1 prepared above was filled between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port was sealed with an acrylic light-curing adhesive, thereby manufacturing a liquid crystal unit. Then, an alternating current of 10 V at a frequency of 60 Hz was applied between the conductive films of the liquid crystal unit and, while the liquid crystal was being driven, an ultraviolet irradiation device using a metal halide lamp as a light source was used at a radiation intensity of 100,000 J / m 2 The ultraviolet rays were irradiated at an irradiation dose of 100 nm. The irradiation dose was measured using a light meter with a wavelength of 365 nm. Polarizing plates were then attached to the outer surfaces of the substrate so that their polarization directions were perpendicular to each other and formed a 45° angle with the optical axis of the ultraviolet rays from the liquid crystal alignment film projected onto the substrate surface. This produced a PSA-type liquid crystal display element.

[0341] (6) Evaluation of liquid crystal orientation

[0342] The PSA-type liquid crystal display element manufactured above was observed using an optical microscope to evaluate the presence or absence of abnormal domains in the change of brightness and darkness when a voltage of 5 V was turned on and off (applied and released). The liquid crystal orientation was evaluated by assigning "A" to the case where there were no abnormal domains, "B" to the case where there were some abnormal domains, and "C" to the case where there were abnormal domains throughout. The result was "A" for the liquid crystal orientation in the above-mentioned example.

[0343] (7) Evaluation of voltage holding ratio (VHR)

[0344] For the PSA type liquid crystal display element manufactured as described above, after applying a voltage of 5V with an application time of 60 microseconds and a span of 167 milliseconds, the voltage holding rate was measured 167 milliseconds after the application was released. The measuring device was VHR-1 manufactured by TOYO Technica (Co., Ltd.). At this time, if the voltage holding rate is 98% or more, it is set to "S", if it is 95% or more and less than 98%, it is set to "A", if it is 80% or more and less than 95%, it is set to "B", if it is 50% or more and less than 80%, it is set to "C", and if it is less than 50%, it is set to "D". As a result, in the embodiment, the voltage holding rate was evaluated as "A".

[0345] [Example 2, Example 3, Example 5]

[0346] Liquid crystal alignment agents were prepared using the same solvent composition and solid content concentration as in Example 1, except that the formulation composition was changed to that shown in Table 4. Furthermore, using each liquid crystal alignment agent, reworkability and film adhesion were evaluated in the same manner as in Example 1. Furthermore, PSA-type liquid crystal display elements were manufactured and evaluated for liquid crystal orientation and voltage holding ratio. The results of these evaluations are shown in Table 4. In Table 4, "-" indicates that the compound was not used.

[0347] [Comparative Example 1]

[0348] A liquid crystal alignment agent (AR-1) was prepared using the same polymer, solvent composition, and solid content concentration as in Example 1, except that compound (Ad-1) was not added. Furthermore, using the prepared liquid crystal alignment agent, reworkability and film adhesion were evaluated in the same manner as in Example 1. Furthermore, a PSA-type liquid crystal display element was manufactured and evaluated for liquid crystal orientation and voltage holding ratio. The results of these evaluations are shown in Table 4.

[0349] [Example 4: Photovertical Liquid Crystal Display Element]

[0350] (1) Preparation of Liquid Crystal Alignment Agent, and Evaluation of Reworkability and Film Adhesion

[0351] A liquid crystal aligning agent (AL-4) was prepared using the same solvent composition and solid content concentration as in Example 1, except that the formulation composition was changed to that shown in Table 4. Furthermore, using the liquid crystal aligning agent (AL-4), reworkability and film adhesion were evaluated in the same manner as in Example 1. The results of these evaluations are shown in Table 4.

[0352] (2) Manufacturing of vertical liquid crystal display elements

[0353] The liquid crystal alignment agent (AL-4) prepared above was applied to the transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a spinner, and pre-baked for 1 minute using a hot plate at 80°C. Then, in an oven purged with nitrogen, the inside of the box was heated at 230°C for 1 hour to form a coating film with a thickness of 0.1 μm. Subsequently, a Hg-Xe lamp and a Glan-Taylor prism were used to irradiate the surface of the coating film with 1,000 J / m2 of polarized ultraviolet light containing a bright line of 313 nm from a direction inclined at 40° from the normal line of the substrate. 2 The same operation is repeated to prepare a pair (two sheets) of substrates having liquid crystal alignment films.

[0354] On the periphery of the surface of the liquid crystal alignment film of one of the substrates in the substrate, an epoxy resin adhesive with a diameter of 3.5 μm is applied by screen printing. Then, the liquid crystal alignment film surfaces of a pair of substrates are faced to each other, and the optical axis of the ultraviolet light of each substrate is pressed in an antiparallel manner in the projection direction of the substrate surface. The adhesive is thermally cured at 150 ° C for 1 hour. Then, after filling the gap between the substrates with a negative liquid crystal (Merck (Merck), MLC-6608) from the liquid crystal injection port, the liquid crystal injection port is sealed with an epoxy adhesive. Furthermore, in order to remove the flow orientation during liquid crystal injection, it is heated at 130 ° C and then slowly cooled to room temperature. Then, on both sides of the outer side of the substrate, the polarizing plates are attached in a manner such that the polarization directions of the polarizing plates are orthogonal to each other and the optical axis of the ultraviolet light of the liquid crystal alignment film is at a 45 ° angle to the projection direction of the substrate surface, thereby manufacturing a light vertical liquid crystal display element.

[0355] (3) Evaluation of liquid crystal orientation

[0356] The liquid crystal orientation of the optical vertical liquid crystal display element produced above was evaluated in the same manner as in Example 1. As a result, the liquid crystal orientation was "A" in the above example.

[0357] (4) Evaluation of voltage holding ratio (VHR)

[0358] The voltage holding ratio of the optical vertical liquid crystal display element manufactured above was evaluated in the same manner as in Example 1. As a result, the voltage holding ratio was evaluated as "A" in the above example.

[0359] [Reference Example 1A, Reference Example 2A]

[0360] Liquid crystal alignment agents (AR-2) and (AR-3) were prepared using the same solvent composition and solid content concentration as in Example 1, except that compound (Ad-12) or compound (Ad-14) was used as an additive instead of compound [A] and the formulation composition was changed to that shown in Table 4. Furthermore, using each liquid crystal alignment agent, reworkability and film adhesion were evaluated in the same manner as in Example 1. Furthermore, PSA-type liquid crystal display devices were manufactured and evaluated for liquid crystal orientation and voltage holding ratio. The results of these evaluations are shown in Table 4.

[0361] [Table 4]

[0362]

[0363] As shown in Table 4, Examples 1 to 5 containing Compound (Ad-1), Compound (Ad-2), or Compound (Ad-3) exhibited improved film adhesion and reworkability compared to Comparative Example 1, which did not contain a crosslinking agent. Furthermore, Examples 1 to 5 also achieved a good rating of "A" for liquid crystal orientation and voltage holding ratio.

[0364] Furthermore, in Reference Examples 1A and 2A, which used other crosslinking agents (Ad-12) and (Ad-14) instead of Compound [A], the films exhibited good adhesion but poor reworkability. Furthermore, Reference Examples 1A and 2A also exhibited inferior voltage holding ratios compared to Examples 1 to 5.

[0365] 6. Preparation and evaluation of liquid crystal alignment agents (2)

[0366] [Example 6: PSA-type liquid crystal display element]

[0367] (1) Preparation of liquid crystal alignment agent (AL-6)

[0368] To the solution containing 100 parts by mass of the polymer (P-1) obtained in Synthesis Example 1, 5 parts by mass of the compound (Ad-4) and NMP and butyl cellosolve (BC) as solvents were added to prepare a solution having a solvent composition of NMP / BC = 50 / 50 (mass ratio) and a solids concentration of 4.0% by mass. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent (AL-6).

[0369] (2) Evaluation of film adhesion

[0370] The liquid crystal aligning agent (AL-6) prepared above was used to perform evaluation in the same manner as in "(3) Evaluation of film adhesion" of Example 1. As a result, in the above example, the adhesion strength was 189 N / cm 2 , thus the adhesion was evaluated as "good (○)".

[0371] (3) Evaluation of film adhesion after high-temperature baking

[0372] The liquid crystal alignment agent (AL-6) prepared in (1) above was applied to a glass substrate using a spinner, and pre-baked for 2 minutes using a hot plate at 80°C, and then heated for 30 minutes in a 300°C oven with nitrogen substituted in the box (post-baking), thereby forming a coating with an average film thickness of 0.10 μm. The same operation was repeated to prepare two glass substrates with coatings. On the coating of one glass substrate with a coating, an ODF sealant (S-WB42 manufactured by Sekisui Chemical) was applied in a manner that the width became 1 mm, and the coating of another glass substrate was bonded in a manner that the coating was in contact with the ODF sealant. Then, a metal halide lamp was used to irradiate 30,000 J / m 2 After being exposed to light (converted to 365 nm), the film was heated in an oven at 120°C for 1 hour. Then, the adhesion strength was measured using a tensile compression tester (model: SDWS-0201-100SL) from Imada Manufacturing Co., Ltd. to evaluate the adhesion of the film to the substrate. During the evaluation, the adhesion strength was set to 175 N / cm 2 The above cases are rated as "particularly good (◎)", and the 2 More than but less than 175N / cm 2 The case is set as "good (○)", and the 2 More than but less than 160N / cm 2 If the load is less than 150 N / cm, set it as "OK (△)". 2 The case of was rated as "poor (×)". As a result, in the above-mentioned embodiment, the adhesion force was 190 N / cm 2 , thus being evaluated as "particularly good (◎)" in terms of adhesion.

[0373] (4) Manufacturing of PSA-type liquid crystal display elements

[0374] A PSA-type liquid crystal display element was produced in the same manner as in Example 1 except that the liquid crystal aligning agent (AL-6) was used, and the liquid crystal orientation and voltage holding ratio were evaluated. The results were as follows: the liquid crystal orientation was evaluated as "A" and the voltage holding ratio was evaluated as "S" in the above example.

[0375] [Example 7, Example 8, Example 10, Example 11 and Comparative Example 2, Comparative Example 3]

[0376] Liquid crystal alignment agents were prepared using the same solvent composition and solid content concentration as in Example 6, except that the formulation composition was changed to that shown in Table 5. Furthermore, using each liquid crystal alignment agent, film adhesion was evaluated in the same manner as in Example 6, and PSA-type liquid crystal display elements were manufactured and evaluated for liquid crystal orientation and voltage holding ratio. The results of these evaluations are shown in Table 5. In Table 5, "-" indicates that the compound was not used.

[0377] [Example 9: Photovertical Liquid Crystal Display Element]

[0378] The formulation composition was changed to that shown in Table 5. A liquid crystal alignment agent (AL-9) was prepared using the same solvent composition and solid content concentration as in Example 6, except for this aspect. Furthermore, the film adhesion evaluation was performed using the liquid crystal alignment agent (AL-9) in the same manner as in Example 6. Furthermore, a photo-vertical liquid crystal display element was manufactured using the liquid crystal alignment agent (AL-9) in the same manner as in Example 4, and the liquid crystal orientation and voltage holding ratio were evaluated. As a result, the liquid crystal orientation and voltage holding ratio were evaluated as "A" in the aforementioned example.

[0379] [Table 5]

[0380]

[0381] As shown in Table 5, Examples 6 to 11 containing Compound (Ad-4) exhibited improved film adhesion and film adhesion after high-temperature baking compared to Comparative Example 2, which did not contain a crosslinking agent. Furthermore, Examples 6 to 11 also exhibited good liquid crystal orientation and voltage holding ratio, rated "S" or "A."

[0382] In contrast, in Comparative Example 3, which used another crosslinking agent (Ad-12) instead of Compound (Ad-4), while the film adhesion was good at a post-bake temperature of 230°C, the film adhesion was poor when the post-bake temperature was increased to 300°C. Furthermore, Comparative Example 3 also exhibited inferior voltage holding ratios compared to Examples 6 to 11.

[0383] 7. Preparation and evaluation of liquid crystal alignment agents (3)

[0384] [Example 12: PSA-type liquid crystal display element]

[0385] (1) Preparation of liquid crystal alignment agent (AL-12)

[0386] To the solution containing 100 parts by mass of the polymer (P-1) obtained in Synthesis Example 1, 5 parts by mass of the compound (Ad-5) and NMP and butyl cellosolve (BC) as solvents were added to prepare a solution having a solvent composition of NMP / BC = 50 / 50 (mass ratio) and a solids concentration of 4.0% by mass. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent (AL-12).

[0387] (2) Evaluation of film adhesion

[0388] The liquid crystal aligning agent (AL-12) prepared above was used to evaluate the film adhesion in the same manner as in "(3) Evaluation of film adhesion" of Example 1. As a result, the adhesion strength was 191 N / cm in the above example. 2 , thus the adhesion was evaluated as "good (○)".

[0389] (3) Manufacturing and evaluation of PSA-type liquid crystal display elements

[0390] A PSA-type liquid crystal display element was produced in the same manner as in Example 1 except that the liquid crystal aligning agent (AL-12) was used, and the liquid crystal orientation and voltage holding ratio were evaluated. The results were as follows: the liquid crystal orientation was evaluated as "A" and the voltage holding ratio was evaluated as "S" in the above example.

[0391] (4) Evaluation of high temperature and high humidity tolerance

[0392] After a PSA-type liquid crystal display element manufactured using a post-bake temperature of 230°C was stored in an oven set at 60°C and 90% humidity for 300 hours, the voltage holding ratio was measured in the same manner as above. The value was set as VHR2, and the voltage holding ratio measured before storage under high temperature and high humidity conditions of 60°C and 90% humidity was set as VHR1. The reduction in voltage holding ratio ΔVHR was calculated by subtracting VHR1 from VHR2, and the high temperature and high humidity tolerance was evaluated using ΔVHR. When ΔVHR was less than 5%, it was rated as "particularly good (◎)", when it was 5% or more and less than 10%, it was rated as "good (○)", when it was 10% or more and less than 20%, it was rated as "acceptable (△)", and when it was 20% or more, it was rated as "poor (×)". The result was "particularly good (◎)" in the above example.

[0393] [Example 13, Example 14, Example 16, Example 17]

[0394] Liquid crystal alignment agents were prepared using the same solvent composition and solid content concentration as in Example 12, except that the formulation composition was changed to that shown in Table 6. Furthermore, using each liquid crystal alignment agent, film adhesion was evaluated in the same manner as in Example 12, and PSA-type liquid crystal display elements were manufactured and evaluated for liquid crystal orientation, voltage holding ratio, and high-temperature and high-humidity tolerance. The results of these evaluations are shown in Table 6. In Table 6, "-" indicates that the compound was not used.

[0395] [Comparative Example 4]

[0396] A liquid crystal aligning agent (AR-6) was prepared using the same solvent composition and solid content concentration as in Example 12, except that polymer (P-1) was replaced with polymer (P-15) and compound (Ad-5) was not added. Furthermore, using the prepared liquid crystal aligning agent, film adhesion was evaluated in the same manner as in Example 12, and a PSA-type liquid crystal display element was manufactured and evaluated for liquid crystal orientation, voltage holding ratio, and high temperature and high humidity tolerance. The results of these evaluations are shown in Table 6.

[0397] [Example 15: Photovertical Liquid Crystal Display Element]

[0398] The formulation composition was changed as shown in Table 6. Except for this aspect, a liquid crystal alignment agent (AL-15) was prepared with the same solvent composition and solid content concentration as in Example 12. In addition, the liquid crystal alignment agent (AL-15) was used to evaluate the adhesion of the film in the same manner as in Example 12. Furthermore, a light vertical liquid crystal display element was manufactured in the same manner as in Example 4 using the liquid crystal alignment agent (AL-15), and the liquid crystal orientation, voltage holding ratio, and high temperature and high humidity tolerance were evaluated. As a result, in the embodiment, the liquid crystal orientation was evaluated as "A" and the voltage holding ratio was evaluated as "S". In addition, the evaluation of high temperature and high humidity tolerance was "◎".

[0399] [Example 18: FFS Type Liquid Crystal Display Element]

[0400] (1) Preparation of Liquid Crystal Alignment Agent and Evaluation of Film Adhesion

[0401] A liquid crystal aligning agent (AL-18) was prepared using the same solvent composition and solid content concentration as in Example 12, except that the formulation composition was changed to that shown in Table 6. Furthermore, using the liquid crystal aligning agent (AL-18), the film adhesion was evaluated in the same manner as in Example 12. The results of the evaluation are shown in Table 6.

[0402] (2) Manufacturing of FFS-type liquid crystal display elements

[0403] On each surface of a glass substrate having a flat electrode, an insulating layer and a comb-shaped electrode stacked on one side and an opposite glass substrate having no electrode, a spinner is used to apply the liquid crystal alignment agent (AL-18) prepared above, and pre-baking is performed on a heating plate at 80°C for 1 minute. Then, in an oven in which nitrogen is substituted, heating is performed at 230°C for 1 hour to form a coating having a film thickness of 0.1 μm. For the coating, a friction machine having a roller wound with nylon cloth is used to perform friction treatment at a roller speed of 1000 rpm, a platform moving speed of 2.5 cm / second, and a hair pressing length of 0.4 mm. Then, ultrasonic cleaning is performed in ultrapure water for 1 minute, followed by drying in a clean oven at 100°C for 10 minutes to obtain a substrate having a liquid crystal alignment film. The series of operations are repeated to form a pair (two sheets) of substrates having a liquid crystal alignment film.

[0404] An epoxy resin adhesive containing 3.5 μm diameter alumina spheres was screen-printed around the periphery of the surface of one of the substrates having the liquid crystal alignment film. The substrates were then overlapped and pressed together with their respective liquid crystal alignment film surfaces facing each other, and the adhesive was cured. Subsequently, nematic liquid crystal (MLC-6221, manufactured by Merck) was injected into the space between the pair of substrates through a liquid crystal injection port. The liquid crystal injection port was then sealed with an acrylic light-curing adhesive, and polarizing plates were attached to both outer surfaces of the substrates to produce an FFS liquid crystal display device.

[0405] (3) Evaluation of liquid crystal orientation, voltage retention, and high temperature and high humidity tolerance

[0406] The FFS liquid crystal display element manufactured in (2) was evaluated for liquid crystal orientation, voltage holding ratio, and high temperature and humidity tolerance in the same manner as in Example 12. The results were as follows: the liquid crystal orientation was evaluated as "A" and the voltage holding ratio was evaluated as "S" in the above example. Furthermore, the high temperature and humidity tolerance was evaluated as "◎."

[0407] [Reference Example 1B, Reference Example 2B]

[0408] As an additive, compound (Ad-12) or compound (Ad-13) was used instead of compound [A], and the formulation composition was changed to that shown in Table 6. Liquid crystal alignment agents (AR-7) and (AR-8) were prepared using the same solvent composition and solid content concentration as in Example 12. Furthermore, using each liquid crystal alignment agent, the film adhesion was evaluated in the same manner as in Example 12, and PSA-type liquid crystal display devices were manufactured and evaluated for liquid crystal orientation, voltage holding ratio, and high temperature and high humidity tolerance. The results of these evaluations are shown in Table 6.

[0409] [Table 6]

[0410]

[0411] As shown in Table 6, Examples 12 to 16 containing Compound (Ad-5) or Compound (Ad-7) exhibited excellent film adhesion and high-temperature and high-humidity resistance compared to Comparative Example 4, which did not contain a crosslinking agent. Furthermore, Examples 12 to 16 also achieved good ratings of "S" or "A" for liquid crystal orientation and voltage holding ratio.

[0412] Furthermore, in Reference Examples 1B and 2B, which used other crosslinking agents (Ad-12) or (Ad-13) instead of Compounds (Ad-5) and (Ad-7), while the film adhesion was good, the high-temperature and high-humidity tolerance of the liquid crystal element was poor. Furthermore, Reference Examples 1B and 2B also exhibited inferior voltage holding ratios compared to Examples 12 to 16.

[0413] 8. Preparation and evaluation of liquid crystal alignment agents (4)

[0414] [Example 19: PSA Type Liquid Crystal Display Element]

[0415] (1) Preparation of liquid crystal alignment agent (AL-19)

[0416] To the solution containing 100 parts by mass of the polymer (P-1) obtained in Synthesis Example 1, 5 parts by mass of the compound (Ad-6) and NMP and butyl cellosolve (BC) as solvents were added to prepare a solution having a solvent composition of NMP / BC = 50 / 50 (mass ratio) and a solids concentration of 4.0% by mass. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent (AL-19).

[0417] (2) Evaluation of film adhesion (seal width 1 mm)

[0418] The liquid crystal aligning agent (AL-19) prepared above was used to perform evaluation in the same manner as in "(3) Evaluation of film adhesion" of Example 1. As a result, in the above-mentioned example, the adhesion strength was 189 N / cm 2 , thus the adhesion was evaluated as "good (○)".

[0419] (3) Evaluation of film adhesion (seal width 0.5 mm)

[0420] In the "(3) Evaluation of Adhesion of Film" of Example 1, the liquid crystal aligning agent (AL-19) prepared above was used and the seal width was changed from 1 mm to 0.5 mm. The adhesion of the film was evaluated in the same manner as in Example 1 (3). During the evaluation, the adhesion force was set to 175 N / cm 2The above cases are rated as "particularly good (◎)", and the 2 More than but less than 175N / cm 2 The case is set as "good (○)", and the 2 More than but less than 160N / cm 2 If the load is less than 150 N / cm, set it as "OK (△)". 2 The case of was rated as "poor (×)". As a result, in the above-mentioned embodiment, the adhesion force was 185 N / cm 2 , thus being evaluated as "particularly good (◎)" in terms of adhesion.

[0421] (4) Manufacturing of PSA-type liquid crystal display elements

[0422] A PSA-type liquid crystal display element was produced in the same manner as in Example 1 except that the liquid crystal aligning agent (AL-19) was used, and the liquid crystal orientation and voltage holding ratio were evaluated. The results were as follows: the liquid crystal orientation was evaluated as "A" and the voltage holding ratio was evaluated as "S" in the above example.

[0423] [Example 20, Example 21, Examples 23 to 25, Example 27, and Comparative Examples 5 to 8]

[0424] Liquid crystal alignment agents were prepared using the same solvent composition and solid content concentration as in Example 17, except that the formulation composition was changed to that shown in Table 7. Furthermore, using each liquid crystal alignment agent, film adhesion was evaluated in the same manner as in Example 19, and PSA-type liquid crystal display elements were manufactured and evaluated for liquid crystal orientation and voltage holding ratio. The results of these evaluations are shown in Table 7. In Table 7, "-" indicates that the compound was not used.

[0425] [Example 22: Photovertical Liquid Crystal Display Element]

[0426] The formulation composition was changed to that shown in Table 7. Except for this, a liquid crystal alignment agent (AL-22) was prepared with the same solvent composition and solid content concentration as in Example 19. In addition, the liquid crystal alignment agent (AL-22) was used to evaluate the adhesion of the film in the same manner as in Example 9. Furthermore, a photo-vertical liquid crystal display element was manufactured in the same manner as in Example 5 using the liquid crystal alignment agent (AL-22), and the liquid crystal orientation and voltage holding ratio were evaluated. The liquid crystal orientation of the liquid crystal display element was evaluated as "good", and the voltage holding ratio was evaluated as "good".

[0427] [Example 26: FFS Type Liquid Crystal Display Element]

[0428] (1) Preparation of liquid crystal alignment agent and evaluation of film adhesion

[0429] A liquid crystal aligning agent (AL-26) was prepared using the same solvent composition and solid content concentration as in Example 19, except that the formulation composition was changed to that shown in Table 7. Furthermore, the liquid crystal aligning agent (AL-26) was used to evaluate the adhesion of the film in the same manner as in Example 19. As a result, in the above-described example, the adhesion of the film was evaluated as "good (○)" when the seal width was set to 1 mm, and as "particularly good (◎)" when the seal width was set to 0.5 mm.

[0430] (2) Evaluation of liquid crystal orientation

[0431] An FFS liquid crystal display element was produced using the liquid crystal aligning agent (AL-26) in the same manner as in Example 18, and the liquid crystal orientation was evaluated in the same manner as in Example 1. As a result, the liquid crystal orientation was "A" in the above example.

[0432] (3) Evaluation of voltage holding ratio (VHR)

[0433] An FFS liquid crystal display element was produced using the liquid crystal aligning agent (AL-26) in the same manner as in Example 18, and the voltage holding ratio was evaluated in the same manner as in Example 1. As a result, the voltage holding ratio was evaluated as "S" in the above example.

[0434] [Table 7]

[0435]

[0436] As shown in Table 7, Examples 19 to 27 containing Compounds (Ad-6) and (Ad-8) to (Ad-10) exhibited good film adhesion even when the seal width was narrowed to 0.5 mm, compared to Comparative Example 5, which did not contain a crosslinking agent. Furthermore, Examples 19 to 27 also achieved good ratings of "S" or "A" for liquid crystal orientation and voltage holding ratio.

[0437] In contrast, in Comparative Examples 6 to 8, which used other crosslinking agents (Ad-12), (A-13), or (Ad-14) instead of Compound (Ad-6) and Compounds (Ad-8) to (Ad-10), the film adhesion was insufficient when the seal width was narrowed, resulting in poor evaluations. Furthermore, Comparative Examples 6 to 8 also performed poorly in terms of voltage holding ratio compared to Examples 19 to 27.

Claims

1. A liquid crystal alignment agent comprising a polymer component and a compound [A], wherein the compound [A] is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). In formula (1), Y 1 and Y 2 Each of X is independently a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a 2-tetrahydropyranyl group, a methoxymethyl group, a 1-ethoxyethyl group, or an acetyl group; 1 and X 2 are each independently a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; a1 and a2 are each independently an integer of 1 to 3; b1 and b2 are each independently an integer of 0 to 3; wherein, Satisfy 1≦a1+b1≦5 and 1≦a2+b2≦5; Z 1 is an organic group having a valence of (c+d) that satisfies the following (i), (ii) or (iii); (i) a group having 1 to 8 carbon atoms and a valence of (c+d) in which at least one methylene group of a saturated chain hydrocarbon group is substituted with -O-; a group having 1 to 8 carbon atoms and a valence of (c+d) in which at least one hydrogen atom of a saturated chain hydrocarbon group is substituted with a fluorine atom and at least one methylene group of the saturated chain hydrocarbon group is substituted with -O-; or a group having 2 to 8 carbon atoms and a valence of (c+d) in which at least one hydrogen atom of a saturated chain hydrocarbon group is substituted with a carboxyl group; (ii) a (c+d)-valent saturated hydrocarbon group having 11 or more and 40 or less carbon atoms, or a (c+d)-valent aromatic hydrocarbon group having 7 or more and 40 or less carbon atoms, wherein in the Z 1 In the case of the (c+d)-valent aromatic hydrocarbon group having 7 or more and 40 or less carbon atoms, the compound represented by the formula (1) is a compound represented by the following formula (1-z-4): In formula (1-z-4), R 20 is a single bond or a (c+1)-valent saturated chain hydrocarbon group; R 21 is a single bond or a (d+1)-valent saturated chain hydrocarbon group; R 22 is a group represented by the following formula (r-2-1) or a group represented by the following formula (r-2-2); wherein, R 20 、R 21 and R 22 The total number of carbon atoms in Y is 7 or more and 40 or less; 1 、Y 2 、X 1 、X 2 , a1, a2, b1, b2, c and d have the same meanings as those in formula (1); in R 20 In the case of a single bond, c is 1; in the case of R 21 In the case of a single bond, d is 1, In formula (r-2-1), R 23 is an alkanediyl group having 1 to 3 carbon atoms, R 24 is a single bond or an alkanediyl group having 1 to 3 carbon atoms, R 25 is a substituted or unsubstituted phenyl or naphthyl group; In formula (r-2-2), R b is a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or an acetyl group, t is an integer from 0 to 4, and "*" represents a bond; (iii) -S- or -SO2-; c and d are each independently an integer of 1 to 3; wherein, in the case of (iii), c+d=2; for Y 1 、Y 2 、X 1 and X 2 , when there are multiple identical symbols in the formula, the bases of the identical symbols are the same or different from each other, In formula (2), Y 3 and Y 4 are independently a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a 2-tetrahydropyranyl group, a methoxymethyl group, a 1-ethoxyethyl group or an acetyl group; wherein Y in formula (2) 3 and Y 4 At least one of them is a monovalent group represented by any one of the following formulas (Y-1) to (Y-6); 3 and X 4 are each independently a hydroxyl group or an alkyl group having 1 to 3 carbon atoms; a3 and a4 are each independently an integer of 1 to 3; b3 and b4 are each independently an integer of 1 to 3; wherein 1≦a3+b3≦5 and 1≦a4+b4≦5 are satisfied; Z 2 is an organic group with a valence of (e+f); e and f are each independently an integer of 1 to 3; for Y 3 、Y 4 、X 3 and X 4 , when there are multiple identical symbols in the formula, the bases of the identical symbols are the same or different from each other, In formula (Y-1) to formula (Y-6), R a and R b Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; * represents a bond.

2. The liquid crystal aligning agent according to claim 1, wherein The polymer component includes at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, a polymer having a partial structure derived from a monomer having a polymerizable unsaturated bond, and polyorganosiloxane.

3. The liquid crystal aligning agent according to claim 1 or 2, wherein The polymer component includes a polymer having a partial structure represented by the following formula (3), *-L 1 -R 1 -R 2 -R 3 -R 4 …(3) In formula (3), L 1 Single bond, -O-, -CO-, -COO-* 1 、-OCO-* 1 、-NR 25 -、-NR 25 -CO-* 1 、-CO-NR 25 -* 1 , an alkanediyl group having 1 to 6 carbon atoms, a divalent group in which a hydrogen atom of an alkanediyl group having 2 to 6 carbon atoms is substituted with a hydroxyl group, -OR 26 -* 1 , or -R 26 -O-* 1 , where R 25 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms; R 26 An alkanediyl group having 1 to 3 carbon atoms; * 1 Represents R 1 The bond of R 1 and R 3 are each independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted cycloalkylene group; R 2 is a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted cycloalkylene group, or -R 27 -B 1 -R 28 -, where R 27 and R 28 are independently substituted or unsubstituted phenylene or cycloalkylene; B 1 Single bond, -O-, -COO-* 2 、-OCO-* 2 、-OCH2-* 2 、-CH2O-* 2 , or an alkanediyl group having 1 to 3 carbon atoms;* 2 Represents R 28 The bond of R 4 Represents a hydrogen atom, a fluorine atom, a cyano group, or CH3COO-* 3 , an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a fluoroalkoxy group having 1 to 18 carbon atoms, a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton, or a monovalent group in which a hydrogen atom possessed by an alkyl group or a fluoroalkyl group having 1 to 18 carbon atoms is substituted with a cyano group, wherein * 3 Represents R 3 The bond of R 1 、R 2 and R 3 All single bonds, or R 1 、R 2 and R 3 When the total number of substituted or unsubstituted phenylene groups and cycloalkylene groups is one, R 4 It is an alkyl group having 4 to 18 carbon atoms, a fluoroalkyl group having 4 to 18 carbon atoms, an alkoxy group having 4 to 18 carbon atoms, a fluoroalkoxy group having 4 to 18 carbon atoms, or a hydrocarbon group having 17 to 51 carbon atoms and having a steroid skeleton; * represents a bond.

4. The liquid crystal aligning agent according to claim 1 or 2, wherein The polymer component comprises the following polymer: the polymer is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and has a structural unit derived from a diamine, wherein the diamine has a structure selected from the group consisting of 4 -NR 11 R 12 、* 4 -NR 13 -* 5 、* 4 -NR 14 -CO-NR 15 -* 5 、* 4 -NR 16 -CO-* 5 ,and* 4 -COOR 17 At least one partial structure in the group consisting of, wherein R 11 is a hydrogen atom or a monovalent hydrocarbon group with 1 to 10 carbon atoms or a protecting group; R 12 is a protecting group; R 13 ~R 17 are independently a hydrogen atom or a protecting group; * 4 and* 5 It represents a bond to a carbon atom constituting a carbon-carbon bond. 5 . A liquid crystal alignment film formed using the liquid crystal alignment agent according to claim 1 . A liquid crystal element comprising the liquid crystal alignment film according to claim 5 .

7. A method for manufacturing a liquid crystal element, comprising: A step of applying the liquid crystal alignment agent according to any one of claims 1 to 4 onto the conductive film of each of a pair of substrates having a conductive film to form a coating film; a step of arranging a pair of substrates coated with the liquid crystal alignment agent so that the coating films face each other with the liquid crystal layer sandwiched therebetween, thereby constructing a liquid crystal cell; as well as and irradiating the liquid crystal cell with light while applying a voltage across the conductive films.

Images