Liquid crystal aligning agent and liquid crystal display element

Abstract

A liquid crystal aligning agent containing: a polymer [alpha] obtained from a compound having a polymerizable group having a polymerizable unsaturated hydrocarbon group; a polymer [beta] that is at least one type selected from the group consisting of polyimides, polyamic acids, polyamic acid esters, polyamides, and polyureas; and a compound represented by formula (S1) as a solvent. # imgabs0 # (In formula (S1), Q1 and Q2 each independently represent an alkyl group having 1-4 carbon atoms, Q3 represents a linear, branched, or cyclic alkyl group having 1-8 carbon atoms, an alkoxyalkyl group having 2-8 carbon atoms, an alkylcarbonyl alkyl group having 4-8 carbon atoms, or a hydrogen atom, and the total number of carbon atoms in Q1, Q2, and Q3 is 4 or more.

Description

Technical Field

[0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal display element, and a method for producing the liquid crystal display element. Background Art

[0002] In recent years, liquid crystal display elements have been widely used in mobile phones, computers, and television displays. Liquid crystal display elements have the characteristics of being thin, lightweight, and low in power consumption, and are expected to be used in more areas such as VR (Virtual Reality) and ultra-high-definition displays in the future. Among the display modes of liquid crystal displays, various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment) have been proposed. In all display modes, a film (liquid crystal alignment film) that induces the liquid crystal to the desired orientation state is used.

[0003] In particular, in products with touch panels such as tablet PCs, smartphones, and smart TVs, the IPS method is preferred because the display is not easily disturbed even when touched. In recent years, in order to improve contrast and viewing angle characteristics, liquid crystal display elements using the FFS (Frindge Field Switching) method and liquid crystal orientation technology using the photo-orientation method have been applied.

[0004] However, compared with the IPS method, the FFS method has the problem of high manufacturing cost of the substrate and a unique display defect called Vcom offset. In addition, compared with the rubbing orientation method, the photo-orientation method has advantages in that it is easy to adapt to the expansion of the element and can greatly improve the display characteristics. On the other hand, there are technical problems in principle (if a photo-decomposable material is used, there is a display defect originating from the decomposed product, and if it is a photo-isomerized type, there is a burn-in caused by insufficient orientation force, etc.). In order to solve these technical problems, liquid crystal display element manufacturers and liquid crystal orientation film manufacturers are conducting various studies.

[0005] In recent years, it has been discovered that by forming a compatible interface between polymer and liquid crystal (a liquid-liquid crystal interface in a completely wetted state) at the contact interface between the liquid crystal and the substrate in a liquid crystal unit, a "zero-plane anchoring" state having no orientation restricting force in the in-plane direction can be formed, and a liquid crystal switching device having no switching threshold and orientation memory has been reported (see Patent Document 1).

[0006] A weak anchor IPS method using a weak anchor technology has been proposed, which can improve contrast and significantly reduce driving voltage compared to the conventional IPS method (see Patent Document 2).

[0007] The weak anchor IPS method is produced by using a liquid crystal alignment film having strong anchoring energy on one side of the substrate and using an organic thin film treated to have no anchoring energy on the other side of the substrate (having an electrode generating a lateral electric field).

[0008] In recent years, a weak anchor IPS method using a method of directly providing a thick polymer brush on a substrate has been proposed (see Patent Document 3).

[0009] In addition, as another method, a weak anchor IPS method is proposed, which uses a compound that can be free radical polymerized with a liquid crystal alignment film that can generate photo-free radicals, irradiates UV in the liquid crystal to cause a free radical reaction, and thus weakly anchors the liquid crystal (see Patent Document 4). This technology not only improves contrast and significantly reduces voltage drive by a method that can be mass-produced, but also achieves high-speed response and reduced screen burn-in.

[0010] The liquid crystal alignment film is a component of the liquid crystal display element, formed on the surface of the substrate that clamps the liquid crystal and is in contact with the liquid crystal, and plays the role of orienting the liquid crystal in a certain direction between the substrates. In addition, in addition to the role of orienting the liquid crystal in a certain direction such as a direction parallel to the substrate, the liquid crystal alignment film is sometimes required to control the pre-tilt angle of the liquid crystal. The ability of this liquid crystal alignment film to control the orientation of the liquid crystal (hereinafter referred to as the orientation control ability) is provided by performing an orientation treatment on the organic film constituting the liquid crystal alignment film.

[0011] As an orientation treatment method for a liquid crystal alignment film that is used to impart orientation control capability, a rubbing method has been known for a long time. Rubbing refers to an organic film such as polyvinyl alcohol, polyamide, polyimide on a substrate, and a method of rubbing (rubbing) its surface in a certain direction using a cloth such as cotton, nylon, polyester, etc., so that the liquid crystal is oriented in the direction of rubbing (rubbing direction). The rubbing method can easily achieve a relatively stable orientation state of liquid crystal, so it is used in the manufacturing process of an existing liquid crystal display element. In addition, as an organic film for a liquid crystal alignment film, an organic film of a polyimide system with excellent reliability, electrical properties, etc., such as heat resistance, is mainly selected.

[0012] However, the friction method of wiping the surface of the liquid crystal alignment film including polyimide etc. has the problem of generating dust or static electricity. In addition, due to the high precision of liquid crystal display elements in recent years or the unevenness caused by electrodes on the corresponding substrate or switch active elements for liquid crystal driving, it is impossible to wipe the surface of the liquid crystal alignment film evenly with a cloth, and sometimes it is impossible to achieve uniform liquid crystal orientation.

[0013] Therefore, as another alignment treatment method of a liquid crystal alignment film that does not require rubbing, a photo-alignment method is being actively studied.

[0014] The photo-alignment method includes various methods, and uses linearly polarized light or collimated light to form anisotropy in an organic film constituting a liquid crystal alignment film, and aligns liquid crystals according to the anisotropy.

[0015] As a main photo-alignment method, a decomposition-type photo-alignment method is known. In this method, for example, a polyimide film is irradiated with polarized ultraviolet light, and anisotropic decomposition is produced by utilizing the polarization direction dependence of ultraviolet absorption of the molecular structure. Then, the polyimide remaining without decomposition is used to align the liquid crystal (for example, refer to Patent Document 5).

[0016] In addition, as other photo-orientation methods, photo-crosslinking type and photo-isomerization type photo-orientation methods are also known. In the photo-crosslinking type photo-orientation method, for example, polyvinyl cinnamate is used, polarized ultraviolet light is irradiated, and a dimerization reaction (cross-linking reaction) occurs in the double bond part of the two side chains parallel to the polarized light. Then, the liquid crystal is oriented in a direction orthogonal to the polarization direction (for example, refer to non-patent document 1). In the photo-isomerization type photo-orientation method, when a side chain polymer having azobenzene in the side chain is used, polarized ultraviolet light is irradiated, and an isomerization reaction occurs in the azobenzene part of the side chain parallel to the polarized light, so that the liquid crystal is oriented in a direction orthogonal to the polarization direction (for example, refer to non-patent document 2).

[0017] As shown in the above examples, in the method for the orientation treatment of the liquid crystal alignment film using the light orientation method, there is no need for friction, and there is no need to worry about the generation of dust or static electricity. In addition, the substrate of the liquid crystal display element with a concave-convex surface can also be subjected to the orientation treatment, which becomes a method for the orientation treatment of the liquid crystal alignment film suitable for industrial production processes.

[0018] In the case of orienting the liquid crystal vertically relative to the substrate (referred to as the vertical orientation (VA) mode), a liquid crystal orientation film is used in which a hydrophobic group such as a long-chain alkyl group, a cyclic group or a combination of a cyclic group and an alkyl group (for example, see Patent Document 6), a steroid skeleton (for example, see Patent Document 7) is introduced into the side chain of the polyimide. In this case, when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, it is necessary to tilt the liquid crystal molecules from the substrate normal direction toward one direction in the substrate surface. As a method for this, for example, a method of providing a protrusion on a substrate, a method of providing a slit on a display electrode, a method of slightly tilting (pre-tilting) the liquid crystal molecules from the substrate normal direction toward one direction in the substrate surface by friction, and a method of pre-adding a photopolymerizable compound to a liquid crystal composition, used together with a vertical orientation film such as a polyimide, applying a voltage to the liquid crystal unit while irradiating ultraviolet light, thereby pre-tilting the liquid crystal (for example, see Patent Document 8), etc.

[0019] In recent years, as a method to replace the formation of protrusions or slits in the liquid crystal orientation control of the VA method and the PSA technology, a method (photo-orientation method) using anisotropic photochemical reactions based on polarized ultraviolet irradiation and the like has also been proposed. That is, it is known that by irradiating a photoreactive vertically oriented polyimide film with polarized ultraviolet light, an orientation restriction capability and pre-tilt angle performance are imparted, thereby enabling the tilt direction of the liquid crystal molecules when a voltage is applied to be uniformly controlled (see Patent Document 9). In this case, as with the existing orientation film, a polyimide-based liquid crystal orientation film having excellent durability and suitable for controlling the pre-tilt angle of the liquid crystal is used.

[0020] In the case of utilizing anisotropic photochemical reactions based on polarized ultraviolet irradiation, (meth) acrylic materials having photosensitive groups such as cinnamic acid and cinnamic acid esters in the side chains are often used (see Patent Document 10). In addition, from the viewpoints of reliability, tilt stability after long-term driving, and volume resistance value control, polymer blends with polyamic acid, soluble polyimide, etc. are used (see Patent Document 11).

[0021] Prior art literature

[0022] Patent Literature

[0023] Patent Document 1: Japanese Patent No. 2006-84536

[0024] Patent Document 2: Japanese Patent No. 4053530

[0025] Patent Document 3: Japanese Patent Application Publication No. 2013-231757

[0026] Patent Document 4: International Publication No. 2019 / 004433 Pamphlet

[0027] Patent Document 5: Japanese Patent No. 3893659

[0028] Patent Document 6: Japanese Patent Application Laid-Open No. 3-179323

[0029] Patent Document 7: Japanese Patent Application Laid-Open No. 4-281427

[0030] Patent Document 8: Japanese Patent No. 4504626

[0031] Patent Document 9: Japanese Patent No. 4995267

[0032] Patent Document 10: International Publication No. 2018 / 155675 Pamphlet

[0033] Patent Document 11: International Publication No. 2020 / 045549 Pamphlet

[0034] Non-patent literature

[0035] Non-patent document 1: M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992).

[0036] Non-patent document 2: K. Ichimura et al., Chem. Rev. 100, 1847 (2000). Summary of the invention

[0037] Technical problem to be solved by the invention

[0038] The inventors and others proposed a block copolymer or a polymer alloy thereof with polyamic acid, polyamic acid ester, and soluble polyimide as a material showing weak anchoring, and the block copolymer has a block segment that is incompatible with liquid crystal or becomes incompatible by heating and a block segment compatible with liquid crystal (with reference to Japanese patent application 2021-96448 and WO2022 / 260048). However, the block copolymer generally lacks solubility in NMP (N-methyl-2-pyrrolidone) and GBL (γ-butyrolactone) used in conventional liquid crystal alignment agents (reagents for forming liquid crystal alignment films), although solubility is shown, precipitation or gelation during storage becomes a technical problem, and when these solvents are used for coating, pinholes and unevenness are easily caused.

[0039] Furthermore, the block polymer segments compatible with liquid crystals in the block copolymers have no polarity due to their structure and have low viscosity. Therefore, the coating uniformity of the liquid crystal alignment film, especially the coating properties at the ends, is easily reduced, which may easily cause the ends of the liquid crystal alignment film to be non-linear or to be raised.

[0040] For these reasons, it is difficult to form a high-quality coating film using the flexographic printing method or inkjet coating method used in the liquid crystal alignment agent coating process. Therefore, the following problem arises: even if the weakly anchored IPS display element can obtain good characteristics, it is impossible to produce panels for televisions, smartphones, etc. through actual manufacturing processes.

[0041] The photo-alignment material using the photo-dimerization reaction of the cinnamic acid and cinnamic acid ester is mainly a polymer obtained by the polymerization of a polymerizable unsaturated hydrocarbon. Although the polymer obtained by the polymerization of a polymerizable unsaturated hydrocarbon also depends on the structure, it has poor compatibility with NMP and GBL used in conventional liquid crystal alignment agents (reagents for forming liquid crystal alignment films), the coating uniformity of the liquid crystal alignment film is deteriorated, and uneven film thickness is generated, which becomes a technical problem.

[0042] Furthermore, in order to ensure reliability, the polymer obtained by polymerization of polymerizable unsaturated hydrocarbons is often used in combination with polyamic acid or polyamic acid ester, or soluble polyimide. In particular, the polymer obtained by polymerization of polymerizable unsaturated hydrocarbons has a large difference in polarity or thermal expansion coefficient with polyamic acid or polyamic acid ester, or soluble polyimide, so the deterioration of the coating uniformity of the liquid crystal alignment film or the unevenness of the film thickness significantly manifests as a technical problem.

[0043] If such technical problems can be solved, it is believed that the yield during panel manufacturing will be optimized, which will also become a major cost advantage for panel manufacturers.

[0044] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a liquid crystal aligning agent capable of forming a coating film of higher quality than conventional methods, a liquid crystal display element using the same, and a method for producing a liquid crystal display element using the same.

[0045] Technical solutions for solving technical problems

[0046] The present inventors have conducted intensive studies to solve the above-mentioned technical problems, and as a result, have found that the above-mentioned technical problems can be solved, thereby completing the present invention having the following gist.

[0047] [1] A liquid crystal aligning agent comprising: a polymer α obtained from a compound having a polymerizable group having an unsaturated hydrocarbon group capable of being polymerized; a polymer β selected from at least one of polyimide, polyamic acid, polyamic acid ester, polyamide and polyurea; and a compound represented by the following formula (S1) as a solvent.

[0048] [Chemistry 1]

[0049]

[0050] (In formula (S1), Q 1 and Q 2 Each independently represents an alkyl group having 1 to 4 carbon atoms, Q 3 represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, an alkylcarbonylalkyl group having 4 to 8 carbon atoms, or a hydrogen atom, and Q 1 , Q 2 and Q 3 The total number of carbon atoms is 4 or more.)

[0051] [2] The liquid crystal aligning agent according to [1], wherein the polymerizable group is at least one selected from a (meth)acryloyloxy group, a (meth)acrylamide group, an allyl group, a styryl group, and a maleimide group.

[0052] [3] A liquid crystal alignment agent according to [1] or [2], wherein the compound represented by the formula (S1) is at least one selected from N,N-diethylacetamide, N,N-diethylformamide, N,N-dibutylformamide, N,N-dipropylacetamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 2-methoxy-N,N-diethylacetamide, 3-methoxy-N,N-diethylpropionamide, 4-oxo-N,N-diethylpentanamide and N,N-diethylcyclohexanecarboxamide.

[0053] [4] The liquid crystal aligning agent according to any one of [1] to [3], wherein the content of the compound represented by the formula (1) is 10 to 90% by mass relative to the total amount of the solvent component contained in the liquid crystal aligning agent.

[0054] [5] The liquid crystal aligning agent according to any one of [1] to [4], wherein a fired film obtained by applying and firing the liquid crystal aligning agent exhibits weak anchoring properties.

[0055] [6] The liquid crystal aligning agent according to any one of [1] to [5], which is a weak anchor liquid crystal aligning agent used for forming a liquid crystal aligning film of a liquid crystal cell having a liquid crystal and a liquid crystal aligning film,

[0056] The polymer α includes at least one selected from the group consisting of polymer A, polymer B, and polymer C described below.

[0057] Polymer A: a block copolymer having a block segment (A) which is compatible with the liquid crystal and a block segment (B) which is incompatible with the liquid crystal or becomes incompatible with the liquid crystal by firing.

[0058] Polymer B: a graft copolymer comprising a main polymer and a branch polymer bonded to the main polymer as a side chain of the main polymer, the branch polymer being compatible with the liquid crystal, and the main polymer being incompatible with the liquid crystal or becoming incompatible with the liquid crystal by firing.

[0059] Polymer C: a polymer having a polymer unit compatible with the liquid crystal and reacting with the polymer β by heating.

[0060] [7] The liquid crystal aligning agent according to [6], wherein the block segment (A) in the polymer A, the branched polymer in the polymer B, and the polymer unit compatible with the liquid crystal in the polymer C contain at least one selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5),

[0061] The block fragment (B) in the polymer A and the backbone polymer in the polymer B contain a compound represented by the following formula (6) as a constituent component.

[0062] [Chemistry 2]

[0063]

[0064] (In formula (2), M represents a polymerizable group having an unsaturated hydrocarbon group that can be polymerized, X represents a single bond, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond or a thioether bond, R1 represents an alkyl group having 1 to 20 carbon atoms into which a bonding group may be inserted, and n is an integer of 1 to 2. When n is 2, two Xs and two R1s may be the same or different.)

[0065] [Chemistry 3]

[0066]

[0067] (In formula (3), M represents a polymerizable group having an unsaturated hydrocarbon group capable of polymerization, S represents a single bond or a saturated hydrocarbon group having 1 to 6 carbon atoms into which a bonding group may be inserted, T represents an organic group represented by the following formula (3-T), and n is an integer of 1 to 2. When n is 2, the two Ts may be the same or different. Among them, when n is 2, S represents a saturated hydrocarbon group having 1 to 6 carbon atoms into which a bonding group may be inserted.)

[0068] [Chemistry 4]

[0069] *-X-Cy (3-T)

[0070] (In formula (3-T), * represents a bonding site. X is a bonding group selected from a single bond, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond, a thioether bond, -Si(R1)(R2)-(R1 and R2 each independently represent an alkyl group bonded to Si), -Si(R3)(R4)-O-(R3 and R4 each independently represent an alkyl group bonded to Si), and -N(R5)-(R5 represents a hydrogen atom or an alkyl group bonded to N), and Cy represents a non-aromatic cyclic group of 6 to 20 members.)

[0071] [Chemistry 5]

[0072]

[0073] (In formula (4), M represents a polymerizable group having an unsaturated hydrocarbon group that can be polymerized, R1 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms and having a linear or branched structure, and the three Xs each independently represent a hydrogen atom or the following formula (4-X). Among them, at least one of the three Xs represents formula (4-X).)

[0074] [Chemistry 6]

[0075]

[0076] (In formula (4-X), Y represents a single bond, -O-, -S- or -N(R)- (R represents a hydrogen atom bonded to N or an alkyl group having 1 to 4 carbon atoms.), and * represents a bonding site. R2, R3 and R4 each independently represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group which may have a substituent.)

[0077] [Chemistry 7]

[0078]

[0079] (In formula (5), M represents a polymerizable group having an unsaturated hydrocarbon group capable of polymerization, R1 to R3 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may be inserted with a bonding group, Ar represents an aromatic hydrocarbon group which may have a substituent, X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group which may have a substituent, and R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 may form a ring together. The total number of carbon atoms of R1X1, R2X2 and R3 is 1 or more.)

[0080] [Chemistry 8]

[0081]

[0082] (In formula (6), M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group, and n is an integer of 1 to 2. Z represents a group represented by the following formula (6-Z). When n is 2, the two Zs may be the same or different.)

[0083] [Chemistry 9]

[0084]

[0085] (In the formula (6-Z), L represents a group selected from a trialkoxysilyl group, an isocyanate group, a blocked isocyanate group, an epoxy group, an oxetane group, a vinyl group, an allyl group, an oxazoline group, an amino group, a protected amino group, an anilino group, a protected anilino group, a hydroxyl group, a protected hydroxyl group, a phenol group, a protected phenol group, a thiol group, a protected thiol group, a thiophenol group, a protected thiophenol group, an aldehyde group, a carboxyl group, a maleimide group, an N-hydroxysuccinimide ester group, an aromatic hydrocarbon group having 5 to 18 carbon atoms which may be inserted with a bonding group, an aromatic heterocyclic group having 5 to 18 carbon atoms which may be inserted with a bonding group, a cinnamic acid group, a cinnamic acid aromatic ester group, Functional groups selected from alkyl cinnamate, cinnamyl, phenyl benzoate, azophenyl, N-benzylideneanilide, stilbene and diphenylethynyl. J represents a single bond or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. K, when bonded to an aromatic hydrocarbon group, represents a linking group selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a carbamate bond and a thioether bond, and represents a single bond in all other cases. * represents a bonding site. m is an integer from 1 to 3. When m is 2 or 3, multiple K and L may be the same or different. In the case where J is a single bond, m is 1. )

[0086] [8] The liquid crystal aligning agent according to [7], wherein the branched polymer in the polymer B is derived from a macromonomer represented by the following formula (7).

[0087] [Chemistry 10]

[0088]

[0089] (In formula (7), P represents a polymerizable group having a polymerizable unsaturated hydrocarbon group, Q is a structure obtained by polymerizing a monomer containing at least one of the compounds represented by formulae (2) to (5), and n is an integer of 1 to 2. When n is 2, the two Qs may be the same or different.)

[0090] [9] The liquid crystal aligning agent according to [6], wherein the polymer C is a polymer represented by the following formula (8).

[0091] [Chemistry 11]

[0092]

[0093] In formula (8), A represents an n-valent organic group having a molecular weight of 500 or less and having a group that reacts with the polymer β by heating, selected from the following formulas (8-A-1) to (8-A-16).

[0094] Q is a divalent polymer unit that contains at least one compound selected from the compounds represented by the formulae (2) to (5) as a constituent component and is compatible with the liquid crystal.

[0095] R is a monovalent organic group selected from the following formulae (8-R-1) to (8-R-11) and having a molecular weight of 500 or less that does not react with the polymer β by heating.

[0096] n is an integer of 1 to 2. When n is 2, the two Qs and Rs may be the same or different.

[0097] [Chemistry 12]

[0098]

[0099] (In formulas (8-A-1) to (8-A-16), R1 and R2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, R3 and R4 each independently represent a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms, and X represents an oxygen atom or a sulfur atom. * represents a bonding site.)

[0100] [Chemistry 13]

[0101]

[0102] (In formulas (8-R-1) to (8-R-11), R1 and R2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and R3 and R4 each independently represent a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms. * represents a bonding site.)

[0103]

[10] The liquid crystal alignment agent according to any one of [1] to [4], which is a strong anchor liquid crystal alignment agent,

[0104] The fired film obtained by applying and firing the liquid crystal aligning agent expresses optical anisotropy by irradiation with polarized ultraviolet rays.

[0105]

[11] The liquid crystal alignment agent according to any one of [1] to [4] and

[10] , which is a strong anchor liquid crystal alignment agent,

[0106] The side chain structure of the mesogen constituting the polymer α includes at least one of the following formulae (10a) to (10q).

[0107] [Chemistry 14]

[0108]

[0109] (wherein n1 and n2 are each independently 0, 1, 2 or 3.

[0110] L is a single bond, an alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more -CH2- constituting the alkylene group having 1 to 12 carbon atoms is substituted by -O-, -S-, -C(=O)-O- or -OC(=O)-, and a part or all of the hydrogen atoms of the alkylene group and the divalent linking group may be replaced by halogen atoms.

[0111] T 1 It is a single bond or an alkylene group having 1 to 12 carbon atoms, and a part or all of the hydrogen atoms of the alkylene group may be substituted with halogen atoms.

[0112] A 1 , A 2 and D 1 Each is independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)-. 1 When A is a single bond, 2 Also a single bond.

[0113] Y 1 and Y 2 Each is independently a phenylene group or a naphthylene group, and a part or all of the hydrogen atoms of the phenylene group and the naphthylene group may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0114] P 1 , Q 1 and Q 2 Each independently represents a single bond, a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a part or all of the hydrogen atoms of the phenylene group and the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. 1 When the number is 2 or more, each Q 1 They can be the same or different; 2 When the number is 2 or more, each Q 2 They can be the same or different.

[0115] R is a hydrogen atom, a cyano group, a halogen atom, a carboxyl group, a linear or branched alkyl group having 1 to 40 carbon atoms, a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0116] X 1 , X 2 and X 3Each is independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. 1 When the number is 2 or more, each X 1 They can be the same or different; 2 When the number is 2 or more, each X 2 They can be the same or different.

[0117] Z 1a and Z 2a Each is independently a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, and a part or all of the hydrogen atoms of the alkyl group may be replaced by fluorine atoms.

[0118] Cou is a coumarin-6-yl group or a coumarin-7-yl group, and a part of the hydrogen atoms bonded thereto may be replaced by -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0119] E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.

[0120] G 1 and G 2 are each independently N or CH.

[0121] The dotted line is a bond.)

[0122] [Chemistry 15]

[0123]

[0124] [Chemistry 16]

[0125]

[0126] (In the formula, A 3 and A 4 Each is independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-C(=O)-. 4 When the number is 2 or more, each A 4 They can be the same or different.

[0127] R 1It is -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0128] R 2 It is a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group or a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a part or all of the hydrogen atoms in these groups may be replaced by -NO2, -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

[0129] R 3 It is a hydrogen atom, -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0130] E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.

[0131] L′ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more -CH2- constituting the alkylene group having 1 to 12 carbon atoms is substituted by -O-, -S-, -C(=O)-O- or -OC(=O)-, and a part or all of the hydrogen atoms of the alkylene group and the divalent linking group may be replaced by halogen atoms.

[0132] k1 to k5 are each independently an integer of 0 to 2, but the total of k1 to k5 is 2 or more.

[0133] k6 and k7 are each independently an integer of 0 to 2, but the total of k6 and k7 is 1 or more.

[0134] m1, m2 and m3 are each independently an integer of 1-3.

[0135] n is 0 or 1,

[0136] Z 1 and Z 2 Each is independently a single bond, -C(=O)-, -CH2-O- or -CF2-.

[0137] The dotted line is a bond.)

[0138] In addition, part or all of the hydrogen atoms of the benzene ring and the naphthalene ring in the formula may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.)

[0139]

[12] The liquid crystal aligning agent according to any one of [7] to [9], wherein M in the formula (2) is any of the following structures,

[0140] M in the formula (3) is any of the following structures,

[0141] M in the formula (4) is any of the following structures,

[0142] M in the formula (5) is any of the following structures.

[0143] [Chemistry 17]

[0144]

[0145] (In the formula, R1 and R2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and X, Y and Z each independently represent an oxygen atom or a sulfur atom. *, * 1 and* 2 Indicates the bonding site, * 1 and* 2 Any of them may be replaced by a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms.

[0146]

[13] The liquid crystal aligning agent according to any one of [6] to [9] and

[12] , wherein the polymer A to the polymer C are polymers obtained by living polymerization or chain transfer polymerization.

[0147]

[14] A liquid crystal display element comprising a liquid crystal alignment film formed using the liquid crystal alignment agent according to any one of [1] to

[13] .

[0148]

[15] The liquid crystal display element according to

[14] , which is a transverse electric field liquid crystal display element.

[0149]

[16] A method for producing a liquid crystal display element, comprising: applying and firing the liquid crystal alignment agent described in any one of [1] to

[13] .

[0150]

[17] The method for manufacturing a liquid crystal display element according to

[14] , wherein the liquid crystal display element is a lateral electric field liquid crystal display element.

[0151] Effects of the Invention

[0152] According to the present invention, compared with the prior art, the stability during storage, the coating property, and the uneven film thickness can be optimized, and the process load imposed on the manufacture of liquid crystal display elements can be reduced or the yield rate can be improved in actual industrialization. By using the materials and methods of the present invention, it is possible to provide materials and transverse electric field liquid crystal display elements and longitudinal electric field liquid crystal display elements that have excellent stability of the composition solution, greatly improved coating property using flexographic printing, and can stably exhibit excellent orientation characteristics compared with the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0153] Figure 1 This is a schematic cross-sectional view showing an example of a lateral electric field liquid crystal display element of the present invention.

[0154] Figure 2 This is a schematic cross-sectional view showing another example of the lateral electric field liquid crystal display element of the present invention. DETAILED DESCRIPTION

[0155] (Liquid Crystal Alignment Agent)

[0156] The liquid crystal aligning agent of this invention contains the compound represented by following formula (S1) as a solvent, and a polymer α, a polymer β.

[0157] The polymer α is a polymer obtained from a compound having a polymerizable group having a polymerizable unsaturated hydrocarbon group.

[0158] The polymer β is at least one polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyamide, and polyurea.

[0159] In addition, the compound represented by formula (S1) may be referred to as a "specific solvent".

[0160] [Chemistry 18]

[0161]

[0162] (In formula (S1), Q 1 and Q 2 Each independently represents an alkyl group having 1 to 4 carbon atoms, Q 3 represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, an alkylcarbonylalkyl group having 4 to 8 carbon atoms, or a hydrogen atom, and Q 1 , Q 2 and Q 3 The total number of carbon atoms is 4 or more.)

[0163] The technical problem of polymers obtained from compounds having polymerizable groups having polymerizable unsaturated hydrocarbon groups is that they lack solubility in NMP and GBL, which are conventionally used solvents. Although they are soluble, they precipitate or gel during storage, and when these solvents are used for coating, pinholes and unevenness are easily generated. Therefore, the coating uniformity of the liquid crystal alignment film obtained by coating the liquid crystal alignment agent, especially the coating properties of the end portion, is easily reduced, and the end portion of the liquid crystal alignment film is easily not straight or the end portion is raised.

[0164] The specific solvent is also characterized in that the viscosity of the solvent itself is high due to hydrogen bonds derived from amide bonds.

[0165] It is known that these technical problems can be solved by using a specific solvent in the liquid crystal aligning agent of the present invention, thereby increasing the viscosity and improving the storage stability, coating property and printability of the liquid crystal aligning agent. Furthermore, as a feature, less damage to the APR printing plate used in flexographic printing can be cited.

[0166] As Q in formula (S1) 1 and Q 2 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, etc. Among them, methyl and ethyl are preferred.

[0167] As Q in formula (S1) 3 Examples of the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and cyclohexyl. Among them, methyl and ethyl are preferred.

[0168] As Q in formula (S1) 3 Examples of the alkoxyalkyl group having 2 to 8 carbon atoms include C1 to C4 alkoxy C2 to C4 alkyl groups. Examples of the alkoxyalkyl group having 3 to 8 carbon atoms include 2-methoxyethyl, 2-butoxyethyl, 1-methoxymethyl, 2-methoxyethyl, and 3-methoxypropyl groups.

[0169] As Q in formula (S1) 3 Examples of the alkylcarbonylalkyl group having 4 to 8 carbon atoms include 4-oxopentyl, 3-oxopentyl, and 5-oxohexyl.

[0170] Preferred examples of the specific solvent include N,N-diethylacetamide, N,N-diethylformamide, N,N-dibutylformamide, N,N-dipropylacetamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 2-methoxy-N,N-diethylacetamide, 3-methoxy-N,N-diethylpropionamide, 4-oxo-N,N-diethylvaleramide, and N,N-diethylcyclohexanecarboxamide.

[0171] Although the introduction ratio of the specific solvent is not particularly limited, it is preferably 10 to 90 mass %, more preferably 30 to 80 mass % with respect to the total amount of the solvent component contained in the liquid crystal aligning agent.

[0172] Among the preferred specific solvents, when N,N-diethylacetamide, N,N-diethylformamide, N,N-dimethylpropionamide, and N,N-diethylpropionamide are used as the main solvent, the boiling point is slightly lower than that of conventional solvents, and the coating property may be deteriorated in printing and coating, which generates a waiting time from coating to drying. Therefore, among the specific solvents shown in (S1), it is preferred to use a specific high boiling point solvent with a higher boiling point in combination.

[0173] The specific high boiling point solvent is a solvent having a relatively high boiling point among the specific solvents represented by formula (S1), and refers to a solvent having a boiling point exceeding 200° C. Preferred examples of the specific high boiling point solvent include N,N-dibutylformamide, 4-oxo-N,N-diethylpentanamide, and N,N-diethylcyclohexanecarboxamide.

[0174] The boiling point here refers to the boiling point at 1 atmosphere pressure.

[0175] Although the introduction ratio of the specific high boiling point solvent is not particularly limited, it is preferably 5 to 50 mass %, more preferably 10 to 30 mass % with respect to the total amount of the solvent component contained in the liquid crystal aligning agent.

[0176] The polymerizable group is preferably at least one selected from the group consisting of a (meth)acryloyloxy group, a (meth)acrylamide group, an allyl group, a styryl group, and a maleimide group.

[0177] The liquid crystal alignment agent can be used for any of a weak anchor liquid crystal alignment agent and a strong anchor liquid crystal alignment agent.

[0178] It is preferable that the fired film obtained by applying and firing the liquid crystal aligning agent expresses weak anchoring property. Thereby, the liquid crystal aligning agent can be used as a weak anchor liquid crystal aligning agent.

[0179] It is preferable that the fired film obtained by applying and firing the liquid crystal aligning agent expresses optical anisotropy by irradiation with polarized ultraviolet light. Thereby, the liquid crystal aligning agent can be used as a strong anchor liquid crystal aligning agent.

[0180] In order to take into account the coating property, sealing adhesion or film strength of the oriented film, and good orientation characteristics, polymer α and polymer β are essential factors. In addition, the mixing ratio of polymer α and polymer β becomes an important factor. In order to properly take into account the characteristics, it is preferred to reduce the mass ratio of polymer α relative to polymer β. As a preferred introduction ratio (polymer α / polymer β), it is 0.1 / 99.9 to 50 / 50 (mass ratio), and more preferably 1.0 / 99.0 to 40 / 60 (mass ratio).

[0181] (Weak anchor)

[0182] In the present invention, the so-called "weak anchoring" means that there is a force that restricts the orientation of liquid crystal molecules in the azimuthal or polar directions relative to the substrate, but there is no anchoring strength (i.e., the interfacial elastic energy that maintains the position of the liquid crystal molecules or restores the liquid crystal molecules to their original state even if the orientation changes), or even if there is an anchoring strength, it is weaker than the intermolecular force between liquid crystals. In the weak anchoring of the present invention, it means that the azimuthal anchoring strength (A2) is less than 10 -5 [J / m 2 As described in Japanese Patent Publication No. 2013-231757, it is known that a polymer capable of forming a completely wet state with liquid crystal is provided at the interface of a substrate, and a polymer-liquid crystal mixed layer is formed by bringing it into contact with the liquid crystal, exhibiting a weak anchoring state.

[0183] (Weakly anchored oriented film)

[0184] In the present invention, the "weakly anchored alignment film" refers to a film that forms a weakly anchored state by contacting with liquid crystals, and is not limited to a solid film but also includes a liquid film covering a solid surface.

[0185] (Weakly anchored liquid crystal display element)

[0186] The weakly anchored orientation film and the strongly anchored orientation film defined above are coated on a substrate with electrodes respectively and bonded in pairs, thereby making it possible to produce a weakly anchored liquid crystal display element. In a weakly anchored liquid crystal display element, the azimuth anchoring strength of a liquid crystal orientation film is infinitely small, so a weak electric field or external field energy can be used to induce the orientation change of the liquid crystal, and usually the orientation change of the liquid crystal molecules in the non-moving area can also be caused. Therefore, especially in display elements using comb-tooth electrodes such as IPS and FFS, it is also possible to drive the liquid crystal molecules on the electrode with weak electric field strength. Therefore, compared with a liquid crystal display element in which both paired orientation films are composed of strongly anchored orientation films, it is possible to achieve high transmittance and low driving voltage.

[0187] The azimuthal anchoring strength is an index indicating the strength of the interfacial elastic energy between the liquid crystal molecules and the liquid crystal alignment film relative to the azimuthal direction. Methods for calculating the azimuthal anchoring strength include the torque balance method, the strong electric field method, the Geometry method (external field application method), and the Fredericks Transition method.

[0188] (Weak anchoring liquid crystal alignment agent)

[0189] The weak anchor liquid crystal aligning agent of one embodiment of the present invention is used for forming a liquid crystal aligning film of a liquid crystal cell including a liquid crystal and a liquid crystal aligning film.

[0190] The weak anchor liquid crystal alignment agent contains polymer α, polymer β and a specific solvent.

[0191] The polymer α preferably contains at least one selected from the group consisting of polymer A, polymer B, and polymer C.

[0192] In addition, in the specification, polymer α may be expressed as polymer (α), and polymer α and polymer (α) have the same meaning.

[0193] In the specification, polymer β may be expressed as polymer (β), and polymer β and polymer (β) have the same meaning.

[0194] In the specification, polymer A may be referred to as polymer (A), and polymer A and polymer (A) have the same meaning.

[0195] In the specification, polymer B may be expressed as polymer (B), and polymer B and polymer (B) have the same meaning.

[0196] In the specification, polymer C may be expressed as polymer (C), and polymer C and polymer (C) have the same meaning.

[0197] A preferred embodiment of the weakly anchored liquid crystal alignment agent of the present invention contains: a solid component of a block copolymer [polymer (A)] or a graft copolymer [polymer (B)] as described below, or [polymer (C)] that reacts with a polymer (β) by heating as a polymer α, and a specific solvent as a solvent for dissolving them.

[0198] The block copolymer and the graft copolymer are materials of the weak anchor film. The specific solvent used as the solvent shows very good solubility for the block copolymer or the graft copolymer and also shows good coating properties in spin coating or flexographic printing, so that a very high-quality weak anchor liquid crystal alignment film can be obtained.

[0199] Regarding the block copolymer and graft copolymer used in the present invention, the technical problem is that NMP and GBL, which are solvents used in the past, lack solubility. Although they show solubility, they precipitate or gel during storage. When these solvents are used for coating, pinholes and uneven generation are easily caused. Furthermore, the block segments dissolved in the liquid crystal possessed by the block copolymer and the graft copolymer are low in polarity and viscosity due to their structure. Therefore, the coating uniformity of the liquid crystal alignment film obtained by coating the liquid crystal alignment agent, especially the coating property of the end, is easily reduced, which easily causes the end of the liquid crystal alignment film to be not a straight line or the end thereof to be raised.

[0200] The specific solvent is also characterized in that the viscosity of the solvent itself is high due to hydrogen bonds derived from amide bonds.

[0201] It is known that these technical problems can be solved by using a specific solvent in the weak anchor liquid crystal aligning agent of the present invention, thereby increasing the viscosity and improving the storage stability, coating and printing properties of the liquid crystal aligning agent. Furthermore, as a feature, it can be mentioned that there is little damage to the APR printing plate used in flexographic printing.

[0202] (polymer α selected from polymer (A), polymer (B) and polymer (C))

[0203] The weak anchor liquid crystal alignment agent of the present invention is used for forming a liquid crystal alignment film of a liquid crystal cell having a liquid crystal and a liquid crystal alignment film.

[0204] The weak anchoring liquid crystal alignment agent of the present invention is characterized in that it contains: a polymer exhibiting weak anchoring properties, i.e., a polymer (α) containing at least one selected from polymer (A), polymer (B) and polymer (C), a polymer (β) not exhibiting weak anchoring properties, and the specific solvent.

[0205] Polymer (A): a block copolymer comprising a block segment (A) which is compatible with the liquid crystal and a block segment (B) which is incompatible with the liquid crystal or becomes incompatible with the liquid crystal by firing.

[0206] Polymer (B): a graft copolymer, wherein the graft copolymer has a main polymer and a branch polymer bonded to the main polymer as a side chain of the main polymer, the branch polymer is compatible with the liquid crystal, and the main polymer is incompatible with the liquid crystal or becomes incompatible with the liquid crystal by firing.

[0207] Polymer (C): a polymer having a polymer unit compatible with the liquid crystal and reacting with the polymer (β) by heating.

[0208] (Polymer A (block copolymer))

[0209] One embodiment of the “copolymer” in the present invention is a copolymer contained in a weak anchor liquid crystal aligning agent.

[0210] The block copolymer [polymer (A)] has a block segment (A) compatible with liquid crystal and a block segment (B) incompatible with liquid crystal or becoming incompatible with liquid crystal by firing. The block segment (A) includes a polymer that is compatible with liquid crystal even when the copolymer is fired.

[0211] The block segment (A) preferably contains at least one selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5) as a constituent component.

[0212] The block segment (B) preferably contains a compound represented by the following formula (6) as a constituent component.

[0213] The block copolymer may have three or more types of block segments.

[0214] The block copolymer is preferably a copolymer in which the main chain is not branched but extends in a linear chain.

[0215] In the present invention, by using a block segment compatible with a liquid crystal as a block segment of a block copolymer contained in one embodiment of a liquid crystal aligning agent, a weak anchor film can be produced more simply than in a conventional method.

[0216] The applicant has discovered that the compound represented by the following formula (2), the compound represented by the following formula (3), the compound represented by the following formula (4) and the compound represented by the following formula (5) are free radical polymerizable compounds contained in a liquid crystal composition that can produce a weakly anchored lateral electric field liquid crystal display element without generating a pretilt angle and stably, and that contribute to the occurrence of weak anchoring, and has filed applications (Japanese Patent Application No. 2020-134149, Japanese Patent Application No. 2020-163212, Japanese Patent Application No. 2021-041196, WO2022 / 030602, PCT / JP2021 / 35557 (WO / 2022 / 071286), WO2019 / 004433. The contents of these applications and public gazettes are hereby incorporated into this specification to the same extent as if all were explicitly stated.).

[0217] In addition, the applicant has discovered that a weakly anchored liquid crystal alignment agent comprising a polymer (A) can be used to manufacture a weakly anchored film more simply and stably than the existing method, and provides a lateral electric field liquid crystal display element, which can stably achieve low-voltage driving and high-speed response when the voltage is disconnected (OFF) without generating a pretilt angle even in a narrow unit gap, and can reduce screen burn-in, and can achieve both high backlight transmittance and low-voltage driving in a low-temperature environment, and has filed an application (Japanese Special Application No. 2021-96448 and PCT / JP2022 / 22993 (WO2022 / 260048). The contents of the application are hereby incorporated into this specification to the same extent as all explicit records.).

[0218] Block fragment (A) mainly plays a role of exhibiting weak anchoring properties.

[0219] [Chemistry 19]

[0220]

[0221] (In formula (2), M represents a polymerizable group having an unsaturated hydrocarbon group that can be polymerized, X represents a single bond, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond, or a thioether bond, R1 represents an alkyl group having 1 to 20 carbon atoms into which a bonding group may be inserted, and n is an integer of 1 to 2. When n is 2, two Xs and two R1s may be the same or different.)

[0222] Examples of the bonding group in the alkyl group having 1 to 20 carbon atoms into which the bonding group may be inserted include an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, a thioether bond, -Si(R 11 )(R 12 )-(R 11 and R 12 Each independently represents an alkyl group bonded to Si. ), -Si(R 13 )(R 14 )-O-(R 13 and R 14 Each independently represents an alkyl group bonded to Si. ), -N(R 15 )-(R 15 represents a hydrogen atom or an alkyl group bonded to N. ) as R 11 ~R 15 Examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms.

[0223] [Chemistry 20]

[0224]

[0225] (In formula (3), M represents a polymerizable group having an unsaturated hydrocarbon group capable of polymerization, S represents a single bond or a saturated hydrocarbon group having 1 to 6 carbon atoms into which a bonding group may be inserted, T represents an organic group represented by the following formula (3-T), and n is an integer of 1 to 2. When n is 2, the two Ts may be the same or different. Among them, when n is 2, S represents a saturated hydrocarbon group having 1 to 6 carbon atoms into which a bonding group may be inserted.)

[0226] [Chemistry 21]

[0227] *-X-Cy (3-T)

[0228] (In formula (3-T), * represents a bonding site. X is a bonding group selected from a single bond, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond, a thioether bond, -Si(R1)(R2)-(R1 and R2 each independently represent an alkyl group bonded to Si), -Si(R3)(R4)-O-(R3 and R4 each independently represent an alkyl group bonded to Si), and -N(R5)-(R5 represents a hydrogen atom or an alkyl group bonded to N), and Cy represents a non-aromatic cyclic group of 6 to 20 members.)

[0229] The saturated hydrocarbon group in S in formula (3) refers to an n+1-valent group formed by removing n+1 hydrogen atoms from a saturated hydrocarbon (n is the same integer as n in formula (3)). When n is 1, the saturated hydrocarbon group is an alkylene group.

[0230] In S in formula (3), the so-called saturated hydrocarbon group having 1 to 6 carbon atoms and having a bonding group inserted therein refers to an n+1-valent group having a bonding group inserted between carbon-carbons in a saturated hydrocarbon group having 2 to 6 carbon atoms, or an n+1-valent group having a bonding group inserted between a saturated hydrocarbon group having 1 to 6 carbon atoms and an atom (e.g., a carbon atom) bonded thereto.

[0231] Examples of the bonding group in S in formula (3) include a carbon-carbon unsaturated bond, an ether bond (-O-), an ester bond (-COO- or -OCO-), an amide bond (-CONH- or -NHCO-), etc. Examples of the carbon-carbon unsaturated bond include a carbon-carbon double bond, but the saturated hydrocarbon group having 1 to 6 carbon atoms in which the carbon-carbon double bond is inserted preferably has a carbon-carbon double bond inside and does not have a carbon-carbon double bond at its terminal.

[0232] When n is 1, examples of the alkylene group having 1 to 6 carbon atoms in which a bonding group may be inserted include an alkylene group having 1 to 6 carbon atoms and an oxyalkylene group having 1 to 6 carbon atoms.

[0233] The alkylene group having 1 to 6 carbon atoms may be a linear alkylene group, a branched alkylene group, or a cyclic alkylene group.

[0234] In X of the formula (3-T), R1 and R2 in -Si(R1)(R2)- are each independently an alkyl group bonded to Si, for example, an alkyl group having 1 to 6 carbon atoms.

[0235] In the X of the formula (3-T), R3 and R4 in -Si(R3)(R4)-O- are each independently an alkyl group bonded to Si, for example, an alkyl group having 1 to 6 carbon atoms.

[0236] In the formula (3-T), R5 of -N(R5)- in X is a hydrogen atom or an alkyl group bonded to N. The alkyl group is, for example, an alkyl group having 1 to 6 carbon atoms.

[0237] In formula (3-T), Cy is a 6- to 20-membered non-aromatic cyclic group, preferably an 8- to 18-membered non-aromatic cyclic group. It should be noted that Cy may be a 12- to 20-membered non-aromatic cyclic group. In formula (3-T), X is bonded to the atoms constituting the ring in Cy.

[0238] Examples of the atoms constituting the ring in the non-aromatic cyclic group include a carbon atom, an oxygen atom, a nitrogen atom, and a silicon atom.

[0239] The bond between atoms constituting the ring may be a single bond, a double bond, or a triple bond, and is preferably a single bond.

[0240] Examples of the ring in the non-aromatic cyclic group include cycloalkanes, cyclic ethers, cyclosiloxanes, etc. Examples of the cyclic ether include crown ethers. For example, in 12-crown-4, the atoms constituting the ring are carbon atoms and oxygen atoms, and the number of atoms is 12.

[0241] The ring may be a monocyclic ring or a polycyclic ring. Examples of the number of rings in a polycyclic ring include 2 to 4.

[0242] In a polycyclic ring, the bonding modes of the rings include the following three types, for example.

[0243] Sharing 1 atom: for example, spiro compounds

[0244] · Shared 2 atoms: For example, decalin, where two rings share 2 atoms

[0245] · Cross-linked structure: It is considered as a case where two rings share three or more atoms, such as norbornane

[0246] In the case of a polycyclic ring, the number of atoms constituting the ring is regarded as the number of ring members. For example, norbornane is a 7-membered ring.

[0247] A halogen atom or an alkyl group having 1 to 6 carbon atoms may be bonded to an atom constituting the ring in place of a hydrogen atom. Examples of the halogen atom include a fluorine atom and a chlorine atom.

[0248] [Chemistry 22]

[0249]

[0250] (In formula (4), M represents a polymerizable group having an unsaturated hydrocarbon group that can be polymerized, R1 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms and having a linear or branched structure, and the three Xs each independently represent a hydrogen atom or the following formula (4-X). Among them, at least one of the three Xs represents formula (4-X).)

[0251] [Chemistry 23]

[0252]

[0253] (In formula (4-X), Y represents a single bond, -O-, -S- or -N(R)- (R represents a hydrogen atom bonded to N or an alkyl group having 1 to 4 carbon atoms.), and * represents a bonding site. R2, R3 and R4 each independently represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group which may have a substituent.)

[0254] The aliphatic hydrocarbon group in R1 in formula (4) may have 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

[0255] The alkyl group having 1 to 6 carbon atoms in R2, R3 and R4 in formula (4-X) may be, for example, an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 4 carbon atoms. These alkyl groups may have a linear structure or a branched structure.

[0256] The aromatic hydrocarbon groups in R2, R3 and R4 in the formula (4-X) may be unsubstituted, or the hydrogen atoms may be replaced by substituents.

[0257] Examples of substituents of the aromatic hydrocarbon group which may have a substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and a haloalkoxy group having 1 to 4 carbon atoms. The halogenation in the haloalkyl group and the haloalkoxy group may be perhalogenation or partial halogenation. Examples of the halogen atom include a fluorine atom and a chlorine atom.

[0258] Examples of the aromatic hydrocarbon group which may have a substituent include a phenyl group and a naphthyl group.

[0259] The number of substituents in the aromatic hydrocarbon group is not particularly limited.

[0260] In formula (4), the number of formula (4-X) is one or more, and may be one, two, or three.

[0261] In formula (4), three Xs are independent of each other. Therefore, in formula (4), when there are two or more formulas (4-X), the two or more formulas (4-X) may have the same structure or different structures.

[0262] In formula (4-X), at least one of R2, R3 and R4 may be an aromatic hydrocarbon group which may have a substituent. Therefore, in formula (4-X), one of R2, R3 and R4 may be an aromatic hydrocarbon group which may have a substituent, two of R2, R3 and R4 may be aromatic hydrocarbon groups which may have a substituent, or three of R2, R3 and R4 may be aromatic hydrocarbon groups which may have a substituent.

[0263] [Chemistry 24]

[0264]

[0265] (In formula (5), M represents a polymerizable group having an unsaturated hydrocarbon group capable of polymerization, R1 to R3 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may be inserted with a bonding group, Ar represents an aromatic hydrocarbon group which may have a substituent, X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group which may have a substituent, and R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 may form a ring together. The total number of carbon atoms of R1X1, R2X2 and R3 is 1 or more.)

[0266] In R1 to R3 in formula (5), the so-called alkylene group having 1 to 6 carbon atoms and having a bonding group inserted therein refers to a divalent group having a bonding group inserted between carbon-carbons in the alkylene group having 1 to 6 carbon atoms, or a divalent group having a bonding group inserted between the alkylene group having 1 to 6 carbon atoms and the carbon atom to which it is bonded.

[0267] Examples of the bonding group include a carbon-carbon unsaturated bond, an ether bond (-O-), an ester bond (-COO- or -OCO-), an amide bond (-CONH- or -NHCO-), etc. Examples of the unsaturated bond include a carbon-carbon double bond, and the alkylene group having 1 to 6 carbon atoms inserted with the bonding group preferably has a carbon-carbon double bond inside and does not have a carbon-carbon double bond at its terminal.

[0268] Examples of the alkylene group having 1 to 6 carbon atoms into which a bonding group may be inserted include alkylene groups having 1 to 6 carbon atoms and oxyalkylene groups having 1 to 6 carbon atoms. The oxygen atom in the oxyalkylene group having 1 to 6 carbon atoms is bonded to the carbon atom bonded to M, R1, R2, and R3 in formula (5).

[0269] The alkylene group having 1 to 6 carbon atoms may be a linear alkylene group, a branched alkylene group, or a cyclic alkylene group.

[0270] Examples of the aromatic hydrocarbon group which may have a substituent in X1 and X2 in the formula (5) include a phenyl group, a naphthyl group, etc. which may have a substituent.

[0271] Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and a haloalkoxy group having 1 to 4 carbon atoms. The halogenation in the haloalkyl group and the haloalkoxy group may be perhalogenation or partial halogenation. Examples of the halogen atom include a fluorine atom and a chlorine atom.

[0272] Examples of R1 in formula (5) include a single bond and an alkylene group having 1 to 6 carbon atoms. More specifically, an alkylene group having 1 to 6 carbon atoms includes a linear alkylene group having 1 to 6 carbon atoms.

[0273] Examples of R2 in formula (5) include a single bond and an alkylene group having 1 to 6 carbon atoms. More specifically, an alkylene group having 1 to 6 carbon atoms includes a linear alkylene group having 1 to 6 carbon atoms.

[0274] Examples of R3 in formula (5) include a single bond and an alkylene group having 1 to 6 carbon atoms. More specifically, an alkylene group having 1 to 6 carbon atoms includes a linear alkylene group having 1 to 6 carbon atoms.

[0275] Examples of X1 in the formula (5) include a hydrogen atom and a phenyl group.

[0276] Examples of X2 in the formula (5) include a hydrogen atom and a phenyl group.

[0277] Examples of Ar in the formula (5) include a phenyl group and the like.

[0278] The total number of carbon atoms of R1X1, R2X2 and R3 in formula (5) is not particularly limited as long as it is 1 or more, and may be 2 or more.

[0279] The total number of carbon atoms of R1, R2, and R3 in formula (5) may be, for example, 18 or less, 15 or less, or 10 or less.

[0280] When X1 and X2 in formula (5) are hydrogen atoms, the total number of carbon atoms of R1, R2 and R3 is not particularly limited as long as it is 1 or more, and may be 2 or more.

[0281] In addition, when at least one of X1 and X2 in formula (5) is an aromatic hydrocarbon group which may have a substituent, the total number of carbon atoms of R1, R2 and R3 may be zero.

[0282] In formula (5), examples of the ring formed together with R1X1, R2X2 and the carbon atoms bonding to R1X1 and R2X2 include a hydrocarbon ring having 3 to 13 carbon atoms into which a bonding group may be inserted. The bonding group is as described above.

[0283] By using the structure of the above compound, it is easy to achieve high-speed response when the voltage is turned off (OFF), reduction of screen burn-in, high backlight transmittance in a low-temperature environment, and low-voltage driving.

[0284] Block fragment (A) can be a homopolymer of the above-mentioned compound, and a variety of compounds can also be used in combination. In the case of combination, it can be a random copolymerization or a block copolymerization. In the case of a combination of compound species compatible with liquid crystal, no matter how the combination method is, its ratio is not particularly limited. In the case of a combination with a compound species incompatible with liquid crystal described below, from the viewpoint of maintaining characteristics, the preferred combination ratio of the compound species incompatible with liquid crystal is 30 mol% or less, more preferably 20 mol% or less, but it is not limited. These combination methods, combined compound species, and combination ratios are preferably used within the range of being able to obtain target physical properties, display characteristics, electrical characteristics, etc.

[0285] The polymerizable unsaturated hydrocarbon group of the polymerizable compound used for forming the block segment (A) preferably has the following structure, but is not limited to these.

[0286]

[0287] (In the formula, R1 and R2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and X, Y and Z each independently represent an oxygen atom or a sulfur atom. *, * 1 and* 2 Indicates the bonding site, * 1 and* 2 Any of them may be replaced by a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms.

[0288] The polymerizable compound compatible with liquid crystal used for forming the block segment (A) in the polymer (A) preferably has the following structure, but is not limited to these.

[0289] [Chemistry 25]

[0290]

[0291] The block segment (A) swells in the liquid crystal mainly in a thin film state, and plays a role in forming a weak anchoring film. Depending on the molecular weight of the block segment (A), the physical properties of the weak anchoring film are greatly different, so the optimization of the molecular weight is not required, but the optimization of the molecular weight is important. From the viewpoint of forming a good weak anchoring film, the molecular weight of the preferred block segment (A) is 1000 to 100000, and more preferably 3000 to 50000. It should be noted that the molecular weight is the number average molecular weight (Mn) of polystyrene conversion obtained by gel permeation chromatography (GPC). In addition, the molecular weight distribution PDI (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) of polystyrene conversion obtained by GPC measurement to the number average molecular weight (Mn) is preferably 3.0 or less, and more preferably 2.0 or less.

[0292] The block segment (B) contributes to the stability of the weakly anchored liquid crystal alignment film in a thin film state.

[0293] The block segment (B) preferably has a side chain structure having at least one functional group selected from the group consisting of a trialkoxysilyl group, an isocyanate group, a blocked isocyanate group, an epoxy group, an oxetanyl group, a vinyl group, an allyl group, an oxazoline group, an amino group, a protected amino group, an anilino group, a protected anilino group, a hydroxyl group, a protected hydroxyl group, a phenol group, a protected phenol group, a thiol group, a protected thiol group, a thiophenol group, a protected thiophenol group, an aldehyde group, a carboxyl group, a maleimide group, an N-hydroxysuccinimide ester group, an aromatic hydrocarbon group having 5 to 18 carbon atoms which may be inserted with a bonding group, an aromatic heterocyclic group having 5 to 18 carbon atoms which may be inserted with a bonding group, a cinnamic acid group, a cinnamic acid aromatic ester group, a cinnamic acid alkyl ester group, a cinnamic acid phenyl ester group, an azophenyl group, an N-benzylideneanilino group, a stilbene group and a tolanyl group. Specific examples of the bonding group include the specific examples of the bonding group given in the description of formula (2) and the like.

[0294] In this case, the block fragment (B) contains, for example, a polymerizable compound having the above-mentioned functional group and a polymerizable group having a polymerizable unsaturated hydrocarbon group as a constituent component.

[0295] An example of the polymerizable compound used for forming the block segment (B) is represented by the following formula (6).

[0296] [Chemistry 26]

[0297]

[0298] (In formula (6), M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group, and n is an integer of 1 to 2. Z represents a group represented by the following formula (6-Z). When n is 2, the two Zs may be the same or different.)

[0299] [Chemistry 27]

[0300]

[0301] (In the formula (6-Z), L represents a group selected from a trialkoxysilyl group, an isocyanate group, a blocked isocyanate group, an epoxy group, an oxetane group, a vinyl group, an allyl group, an oxazoline group, an amino group, a protected amino group, an anilino group, a protected anilino group, a hydroxyl group, a protected hydroxyl group, a phenol group, a protected phenol group, a thiol group, a protected thiol group, a thiophenol group, a protected thiophenol group, an aldehyde group, a carboxyl group, a maleimide group, an N-hydroxysuccinimide ester group, an aromatic hydrocarbon group having 5 to 18 carbon atoms which may be inserted with a bonding group, an aromatic heterocyclic group having 5 to 18 carbon atoms which may be inserted with a bonding group, a cinnamic acid group, a cinnamic acid aromatic group Functional groups selected from aromatic ester groups, cinnamic acid alkyl ester groups, cinnamyl groups, benzoic acid phenyl ester groups, azophenyl groups, N-benzylideneanilide groups, stilbene groups and diphenylethynyl groups. J represents a single bond or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. K, when bonded to an aromatic hydrocarbon group, represents a connecting group selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a carbamate bond and a thioether bond, and represents a single bond in all other cases. * represents a bonding site. m is an integer of 1 to 3. When m is 2 or 3, multiple K and L may be the same or different. In the case where J is a single bond, m is 1. )

[0302] The block segment (B) has a side chain structure that is incompatible with liquid crystal or becomes incompatible with liquid crystal by firing. Examples of the compound species incompatible with liquid crystal used in the formation of the block segment (B) include highly polar compound species and compound species having a rigid structure, and examples of the compound species incompatible with liquid crystal by firing used in the formation of the block segment (B) include thermosetting compound species.

[0303] Examples of the polymerizable compound used for forming the block segment (B) include a compound having a polymerizable group having a polymerizable unsaturated hydrocarbon group and a highly polar structure.

[0304] The above-mentioned high polarity structure is preferably the following structure, but is not limited to these.

[0305] [Chemistry 28]

[0306]

[0307] (X and Y each independently represent an oxygen atom or a sulfur atom. R1 and R2 each independently represent a single bond or an alkylene group having 1 to 18 carbon atoms. R3 represents an alkyl group having 1 to 18 carbon atoms. One of A1, A2 and A3 represents N, and the remaining two represent CH. One of A4 and A5 represents N, and the remaining one represents CH. * represents a bonding site.)

[0308] Examples of the polymerizable compound used for forming the block segment (B) include a compound having a polymerizable group having a polymerizable unsaturated hydrocarbon group and a rigid structure.

[0309] The above-mentioned rigid structure is preferably the following structure, but is not limited to these.

[0310] [Chemistry 29]

[0311]

[0312] (X, Y and Z each independently represent an oxygen atom or a sulfur atom. R1 and R2 each independently represent a single bond or an alkylene group having 1 to 18 carbon atoms. R3 represents an alkyl group having 1 to 18 carbon atoms. * represents a bonding site, and n represents an integer of 1 to 5.)

[0313] Examples of the polymerizable compound used for forming the block segment (B) include a compound having a polymerizable group having a polymerizable unsaturated hydrocarbon group and a thermosetting structure.

[0314] The above-mentioned thermosetting structure is preferably the following structure, but is not limited to these.

[0315] [Chemistry 30]

[0316]

[0317] (X, Y and Z each independently represent an oxygen atom or a sulfur atom. R1, R2 and R3 each independently represent an alkyl group having 1 to 18 carbon atoms. R4 and R5 each independently represent a single bond or an alkylene group having 1 to 18 carbon atoms. * represents a bonding site.)

[0318] By using the structure of the above-mentioned compound in the block segment (B), the polymer A is less likely to be eluted into the liquid crystal due to the heat generated by driving the liquid crystal or lighting the backlight, and defects are less likely to occur.

[0319] Block fragment (B) can be a homopolymer of the above-mentioned compound, and a variety of compounds can also be used in combination. In the case of combination, it can be a random copolymerization or a block copolymerization. In the case of a combination of compound species that are incompatible with liquid crystal or become incompatible with liquid crystal by firing, no matter how the combination method is, its ratio is not particularly limited. In the case of a combination with the compound species that are compatible with liquid crystal, from the viewpoint of suppressing dissolution into liquid crystal, the preferred combination ratio of the compound species that are compatible with liquid crystal is 70 mol% or less, more preferably 50 mol% or less. However, as described above, block fragment (B) is only a block fragment that contributes to the stability of the film, and has no great relationship with the weak anchoring property, so as long as the stabilization of the film is supplemented, the compound species and the combination method of the combination are not particularly limited.

[0320] The polymerizable group having a polymerizable unsaturated hydrocarbon group of the polymerizable compound used for forming the block segment (B) preferably has the same structure as the polymerizable group having a polymerizable unsaturated hydrocarbon group described in the block segment (A).

[0321] The polymerizable compound in the polymer (A) that is incompatible with the liquid crystal forming the block segment (B) or becomes incompatible with the liquid crystal by firing preferably has the following structures. However, it is not limited to these.

[0322] [Chemistry 31]

[0323]

[0324] (In formulas (B-1) to (B-17), Me represents a methyl group and Et represents an ethyl group.)

[0325] The block segment (B) is mainly responsible for stabilization in the thin film state and has little to do with the physical properties of the weak anchor film. The stability of the film can be supplemented by the block segment (B), and the optimal molecular weight that can supplement the stability of the film varies depending on the type of compound used, so there is no particular limitation. In addition, depending on the type of compound used, advantages are shown in solvent selectivity and coating properties, so the type of compound constituting the block segment (B) and its molecular weight can be controlled according to the use and purpose.

[0326] Here, stabilization in a thin film state means that when the fired thin film comes into contact with liquid crystal, the block segment (B) is incompatible with the liquid crystal, and thus the block copolymer constituting the thin film does not dissolve into the liquid crystal.

[0327] One embodiment of the polymer (A) is characterized in that it is a copolymer having a block segment (A) compatible with liquid crystal and a block segment (B) incompatible with liquid crystal or becoming incompatible with liquid crystal by calcination, and the number of blocks is not limited, for example, it can be a composition having multiple block segments as (A)-(B)-(A), and the number and combination of the block segments are not particularly limited. In addition, the introduction of block segments that impart electrical properties can also be carried out. On the other hand, from the viewpoint of ease of synthesis, the number of block segments is preferably about 2 to 4, and from the viewpoint of film stability, the block segment at the end of the polymer is preferably a block segment (B).

[0328] As described above, the block segment (A) compatible with liquid crystal exhibits weak anchoring properties. The molecular weight of the block segment (A) has a large influence on the properties. Therefore, the molecular weight ratio of the block segment (A) to the block segment (B) is not limited.

[0329] The polymer (A) can be obtained, for example, by living polymerization. Living polymerization refers to a polymerization reaction that is not accompanied by side reactions such as chain transfer reactions and termination reactions in the polymerization reaction, and can obtain a polymer with a narrow molecular weight distribution and a highly controlled structure. For example, the following method can be cited: by introducing a stable covalent bond species called a dormant species into the polymerization active site, the deactivation of the active site is suppressed, so that side reactions such as chain transfer reactions and termination reactions do not occur. In living polymerization, living polymerization using free radicals in active species, living polymerization using cations, and living polymerization using anions can be cited. It is important to use them according to the structure and properties of the polymerizable compound used.

[0330] When obtaining a block copolymer as polymer (A), the polymerization method does not need to be particularly limited, but cationic polymerization and anionic polymerization mostly use alkali metals, metal complexes, and halogen compounds when generating active species. In liquid crystal displays, the mixing of metal residues, halogen compounds, etc. will become the main cause of screen burn-in and poor display, so it is preferred to use free radical polymerization that does not use metals or halogen compounds as much as possible. As active free radical polymerization, active free radical polymerization (NMP) using nitroxide free radicals as dormant species, atom transfer radical polymerization (ATRP) using metal complexes, reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) using sulfur compounds as dormant species, active free radical polymerization (TERP) using organic tellurium compounds, etc., reversible transfer catalytic polymerization (RTCP) using alkyl iodide compounds as dormant species and phosphorus compounds, alcohols, etc. as catalysts, etc., as preferred polymerization methods, active free radical polymerizations such as NMP, RTCP, and RAFT polymerization can be cited, and NMP or RAFT polymerization is particularly preferred.

[0331] When NMP is used, examples of the polymerization initiator used include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, 1,1′-bis(tert-butylperoxy)cyclohexane, hydrogen peroxide, and the like. The polymerization initiator is usually used in a ratio of 0.000001 to 0.1 mol parts, preferably 0.00001 to 0.01 mol parts, relative to 1 mol part of the monomer used. Examples of the nitroxide radical include compounds represented by the following formulas (N-1) to (N-12). The nitroxide radical is usually used in a ratio of 0.000001 to 0.1 mol parts, preferably 0.00001 to 0.01 mol parts, relative to 1 mol part of the monomer used. The reaction temperature in the above-mentioned polymerization is preferably 20 to 200° C., more preferably 40 to 150° C., and the reaction time is preferably 1 to 168 hours, more preferably 8 to 72 hours.

[0332] [Chemistry 32]

[0333]

[0334] When RTCP is used, in addition to low molecular weight dormant species that contribute to the development of activity, it is necessary to use an iodide catalyst or a hydride catalyst and a polymerization initiator for the purpose of promoting the reaction.

[0335] Examples of the polymerization initiator include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, 1,1′-bis(tert-butylperoxy)cyclohexane, hydrogen peroxide, etc. The polymerization initiator is usually used in an amount of 0.000001 to 0.1 parts by mole, preferably 0.00001 to 0.01 parts by mole, relative to 1 part by mole of the monomer used.

[0336] Examples of low molecular weight dormant species include compounds represented by the following formulae (Q-1) to (Q-3). The low molecular weight dormant species are usually used in an amount of 0.000001 to 0.1 mol part, preferably 0.00001 to 0.01 mol part, based on 1 mol part of the monomer used.

[0337] Examples of the iodide catalyst include compounds represented by the following formulae (P-1) to (P-4). The iodide catalyst is usually used in an amount of 0.000001 to 0.1 mol part, preferably 0.00001 to 0.01 mol part, based on 1 mol part of the monomer used.

[0338] Examples of the hydride catalyst include compounds represented by the following formulae (O-1) to (O-6). The hydride catalyst is used in an amount of 0.000001 to 0.1 mol part, preferably 0.00001 to 0.01 mol part, based on 1 mol part of the monomer used.

[0339] Usually, the reaction temperature in the above-mentioned polymerization is preferably 20 to 200° C., more preferably 40 to 150° C., and the reaction time is preferably 1 to 168 hours, more preferably 8 to 72 hours.

[0340] [Chemistry 33]

[0341]

[0342] [Chemistry 34]

[0343]

[0344] [Chemistry 35]

[0345]

[0346] When RAFT polymerization is used, examples of the polymerization initiator used include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, 1,1′-bis(tert-butylperoxy)cyclohexane, hydrogen peroxide, and the like. The polymerization initiator is usually used in a ratio of 0.000001 to 0.1 mol parts, preferably 0.00001 to 0.01 mol parts, relative to 1 mol part of the monomer used. As a chain transfer agent (RAFT agent), trithiocarbonate, dithiobenzoate, dithiocarbamate, and xanthate are preferred, and specific examples include compounds represented by the following formulas (R-1) to (R-24). The chain transfer agent is usually used in a ratio of 0.000001 to 0.1 mol parts, preferably 0.00001 to 0.01 mol parts, relative to 1 mol part of the monomer used. The reaction temperature in the above-mentioned polymerization is preferably 20 to 200° C., more preferably 40 to 150° C., and the reaction time is preferably 1 to 168 hours, more preferably 8 to 72 hours.

[0347] [Chemistry 36]

[0348]

[0349] The reason why active radicals are expressed in RAFT polymerization is that most of the active chains are in a dormant form, there are compounds that can reversibly inactivate growing radical species, and there is a rapid equilibrium between active chains and dormant chains.

[0350] By using RAFT polymerization, polymer terminal control, high-level molecular weight control, and molecular weight distribution control are possible.

[0351] In order to precisely synthesize functional polymers using RAFT polymerization, it is necessary to select an appropriate chain transfer agent in consideration of the reactivity of the monomers.

[0352] In RAFT polymerization, the polymer terminal can be controlled by thermally modifying or chemically modifying the RAFT terminal present at the growing terminal. In the case of thermal modification, the terminal can be modified to an unsaturated hydrocarbon group by heating at a temperature above the thermal decomposition temperature of the RAFT agent used. In addition, in the case of chemical modification, the terminal can be modified to a thiol bond accompanied by aminolysis by contact with primary amines, secondary amines, etc. Furthermore, by contacting with new monomers and free radical generators, new block segments can be provided at the terminal.

[0353] In RAFT polymerization, the molecular weight can be controlled by using the following formula (eq1): Specifically, the number average molecular weight (Mn) changes linearly with the ratio of the molar concentration of the monomer to the molar concentration of the chain transfer agent, and thus the molecular weight can be controlled.

[0354] [Number 1]

[0355]

[0356] (In the above formula (eq1), Mn (theor) represents the molecular weight of the polymer, [Monomer]0 represents the molar concentration of the monomer, [CTA]0 represents the molar concentration of the chain transfer agent, M monomer represents the molecular weight of the monomer, conv. represents the polymerization conversion rate, M CTA Indicates the molecular weight of the chain transfer agent. )

[0357] In addition, when the copolymer obtained by the above-mentioned polymerization is dissolved in a reaction solution, the said reaction solution may be provided for the preparation of a liquid crystal aligning agent directly, and the copolymer contained in a reaction solution may be separated and provided for the preparation of a liquid crystal aligning agent.

[0358] As the polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators (radical thermal polymerization initiators, radical photopolymerization initiators) and reversible addition-fragmentation chain transfer (RAFT) polymerization agents can be used.

[0359] The free radical thermal polymerization initiator is a compound that generates free radicals by heating to a decomposition temperature or higher. Examples of such free radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxide cyclohexane, etc.), alkyl peroxides (tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylcyclohexane, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (azobisisobutyronitrile, 2,2′-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.). The radical thermal polymerization initiator may be used alone or in combination of two or more.

[0360] The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-one, and 1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one. )-1-butanone, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 4,4′-bis(tert-butylperoxycarbonyl)benzophenone, 3,4,4′-tris(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4′-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3′,4′-dimethoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2′,4′-dimethoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2′-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, s-triazine, 1,3-bis(trichloromethyl)-5-(2′-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4′-methoxyphenyl)-s-triazine, 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5 ,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole, 2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4-dibromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3′-bis(methoxycarbonyl)-4,4′-bis(tert-butylperoxycarbonyl)benzophenone, 3,4′-bis(methoxycarbonyl)-4,3′-bis(tert-butylperoxycarbonyl)benzophenone, 4,4′-bis(methoxycarbonyl)-3,3′-bis(tert-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphth-2-yl-ethanone, 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1-(2-benzoyl)ethanone, etc. The free radical photopolymerization initiator may be used alone or in combination of two or more.

[0361] The organic solvent used in the synthesis of the polymer (A) may be any organic solvent that does not chemically react with the compound species constituting the copolymer and does not capture free radicals. For example, N,N-dimethylformamide, N,N-diethylformamide, N,N-dibutylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methyl-ε-caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethylphosphoramide, γ-Butyrolactone, isopropyl alcohol, methoxymethylpentyl alcohol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, di Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, cyclohexane, 2-ethyl-1-hexanol, benzene, xylene, toluene, ethylbenzene, isobutyl ketone, Propylbenzene, tert-butylbenzene, tetrahydrofuran, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, propyl pyruvate, butyl pyruvate, pentyl pyruvate, hexyl pyruvate, 2-ethylhexyl pyruvate, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, pentyl acetoacetate, hexyl acetoacetate, 2-ethylhexyl acetoacetate, methyl levulinate, ethyl levulinate, propyl levulinate, butyl levulinate, pentyl levulinate, hexyl levulinate, 2-ethylhexyl levulinate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl phthalate, dimethyl maleate, diethyl malonate, diethyl succinate, diethyl glutarate, diethyl adipate, diethyl phthalate, diethyl maleate, dipropyl malonate, dipropyl succinate, dipropyl glutarate, dipropyl adipate, dipropyl phthalate, dipropyl maleate, dibutyl malonate, dibutyl succinate, dibutyl glutarate, dibutyl adipate, dibutyl phthalate, dibutyl maleate, dipentyl malonate, dipentyl succinate, dipentyl glutarate, dipentyl adipate, dipentyl phthalate, dipentyl maleate, dihexyl malonate, dihexyl succinate, dihexyl glutarate, dihexyl adipate, dihexyl phthalate, dihexyl maleate, di-2-ethylhexyl malonate, 2-ethylhexyl succinate, 2-ethylhexyl glutarate, 2-ethylhexyl adipate, 2-ethylhexyl phthalate, 2-ethylhexyl maleate (hereinafter also referred to as "specific organic solvent". It should be noted that in the present specification, "specific solvent" and "specific organic solvent" refer to different groups.) and the like. These organic solvents can be used alone or in combination.

[0362] The radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, and the like can be used.

[0363] As the organic solvent used in the free radical polymerization reaction, there is no particular limitation as long as it is an organic solvent that dissolves the generated polymer. As a specific example thereof, the above-mentioned specific organic solvents can be cited. These organic solvents can be used alone or in combination of two or more.

[0364] Furthermore, even a solvent that does not dissolve the produced polymer may be used by mixing with the above-mentioned organic solvent as long as the produced polymer does not precipitate.

[0365] In addition, in radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, and therefore, it is preferable to use an organic solvent that is degassed as much as possible.

[0366] In addition, when the block copolymer obtained by the above polymerization is dissolved in the reaction solution, the reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or the block copolymer contained in the reaction solution may be separated and then used for the preparation of the liquid crystal aligning agent.

[0367] The polymerization temperature during free radical polymerization can be selected from any temperature of 30 to 150° C., preferably in the range of 50 to 100° C. The reaction can be carried out at any concentration. If the concentration is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, the monomer concentration is preferably 5 to 70% by mass, more preferably 10 to 50% by mass. In addition, an organic solvent may be added during the polymerization to apply a gradient to the polymerization concentration.

[0368] For the polymer generated by the reaction solution obtained by the above reaction, the reaction solution can be put into a poor solvent and precipitated and recovered, but the reprecipitation treatment is not necessary. As the poor solvent used in the precipitation, there can be mentioned: methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. The polymer put into the poor solvent and precipitated can be filtered and recovered, and then dried at room temperature or heated under normal pressure or reduced pressure. In addition, if the operation of redissolving the recovered polymer in an organic solvent and reprecipitating and recovering is repeated 2 to 10 times, the impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons, etc. can be mentioned. If more than 3 poor solvents selected from them are used, the efficiency of purification is further improved, so it is preferred.

[0369] (Polymer B (graft copolymer))

[0370] One embodiment of the "graft copolymer" in the present invention is a graft copolymer contained in a weak anchor liquid crystal aligning agent. The weak anchor liquid crystal aligning agent is used to form a film for aligning liquid crystals used in a liquid crystal display element, that is, a liquid crystal aligning film. In addition, the weak anchor liquid crystal aligning agent is used to form a liquid crystal aligning film of a liquid crystal cell having a liquid crystal and a liquid crystal aligning film.

[0371] The graft copolymer [polymer (B)] has a main body polymer and branch polymers bonded to the main body polymer as side chains of the main body polymer.

[0372] The branched polymers are compatible with liquid crystals.

[0373] The backbone polymer is incompatible with the liquid crystal or becomes incompatible with the liquid crystal by firing.

[0374] Graft copolymer is a general term for polymers with branched structures, and refers to a polymer having both a polymer corresponding to the "trunk" and a polymer corresponding to the "branch" bonded to the trunk as a side chain of the trunk. In one embodiment of the liquid crystal aligning agent of the present invention, a graft copolymer is used, but the graft copolymer of the present invention is characterized in that it has a branched polymer compatible with liquid crystals, and is incompatible with liquid crystals as a grafted copolymer or becomes incompatible with liquid crystals by firing. That is, the branched polymer compatible with liquid crystals swells due to compatibility with liquid crystals, thereby contributing to the formation of a weak anchoring state, and by being incompatible with liquid crystals as a grafted copolymer or becoming incompatible with liquid crystals by firing, the grafted copolymer is prevented from eluting into the liquid crystal, and by fixation with the substrate, crosslinking of polymers with each other, and crosslinking with the sealing component, a weakly anchored liquid crystal display element with excellent film hardness and sealing adhesion strength can be obtained.

[0375] The graft copolymer of the present invention is characterized in that it has a branch polymer that is compatible with liquid crystals and is incompatible with liquid crystals or becomes incompatible with liquid crystals by calcining. It should be noted that in order to make the graft copolymer incompatible with liquid crystals or make the graft copolymer incompatible with liquid crystals by calcining, the backbone polymer has a structure that is incompatible with liquid crystals or becomes incompatible with liquid crystals by calcining.

[0376] The graft copolymer of the present invention has a branch polymer compatible with liquid crystal and a main polymer incompatible with liquid crystal or made incompatible by heat, etc., which are preferably connected in a random arrangement by free radical polymerization, thereby achieving high sealing adhesion, solvent selectivity, and coating properties.

[0377] The applicant has discovered that a weakly anchored liquid crystal alignment agent comprising a polymer (B) is a weakly anchored liquid crystal alignment agent that can be easily manufactured and has good coating properties, has good adhesion to a sealant, can obtain a weakly anchored liquid crystal alignment agent that does not produce a pretilt angle and can simultaneously achieve low-voltage drive and high-speed response when the voltage is disconnected (OFF), and has filed an application (2021-156886 and WO2023 / 048278. The contents of the application are hereby incorporated into this specification to the same extent as all explicit records.).

[0378] The "branch polymer" in the graft copolymer of the present invention mainly plays a role in expressing weak anchoring characteristics.

[0379] The structure of the branched polymer compatible with liquid crystal is not particularly limited as long as it is a structure compatible with liquid crystal. For example, the branched polymer can be obtained by using a macromonomer represented by the following formula (7).

[0380] [Chemistry 37]

[0381]

[0382] (In formula (7), P represents a polymerizable group having a polymerizable unsaturated hydrocarbon group, Q is a structure obtained by polymerizing at least one monomer of the compounds represented by formulae (2) to (5), and n is an integer of 1 to 2. When n is 2, the two Qs may be the same or different.)

[0383] By using the structure of the above compound, it is easy to achieve high-speed response when the voltage is turned off (OFF), reduction of screen burn-in, high backlight transmittance in a low-temperature environment, and low-voltage driving.

[0384] The structure in which the terminal is removed in the branched polymer (for example, the structure of Q in formula (7)) can be, for example, a homopolymer structure using only one monomer represented by the above formulas (2) to (5), or a copolymer structure combining multiple monomers. When multiple monomers are combined with each other, it can be a random copolymerization or a block copolymerization. When the monomers represented by the above formulas (2) to (5) are combined with each other, regardless of the combination method, the ratio is not particularly limited. When combined with a compound species incompatible with liquid crystal as described below, from the viewpoint of maintaining the characteristics, the preferred combination ratio of the monomers incompatible with liquid crystal is 30 mol% or less, more preferably 20 mol% or less, but there is no limitation. These synthesis methods, combined monomers, and combination ratios are preferably used within the range that can obtain the target physical properties, display characteristics, electrical characteristics, etc.

[0385] The polymerizable group having a polymerizable unsaturated hydrocarbon group of the polymerizable compound used in the formation of the structure of P in the above formula (7) and Q can be selected from polymerizable groups having a polymerizable unsaturated hydrocarbon group that can be used in the polymerizable compound used in the formation of the block segment (A) or the block segment (B) in the above polymer A. However, it is not limited to these.

[0386] In polymer B, the branched polymer has a great relationship with the performance of weak anchoring characteristics. The physical properties of the weak anchoring film vary according to the molecular weight of the branched polymer, so the optimization of the molecular weight becomes important. From the viewpoint of forming a good weak anchoring film, the preferred number average molecular weight of the branched polymer is 1000 to 100000, more preferably 3000 to 50000, and the molecular weight distribution (PDI) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 3.0 or less, more preferably 2.0 or less. It should be noted that in the case where the grafted copolymer is synthesized by the grafting through method using a macromolecular monomer, the molecular weight described here is equivalent to the molecular weight of the macromolecular monomer.

[0387] The "backbone polymer" in the graft copolymer of the present invention mainly plays a role in stabilizing the weak anchoring liquid crystal alignment film in the thin film state.

[0388] The structure of the "backbone polymer" that is incompatible with liquid crystal or becomes incompatible with liquid crystal by firing is not particularly limited as long as it is a structure that dissolves in liquid crystal. For example, the backbone polymer can be obtained by using the compound represented by the above formula (6). In other words, the backbone polymer can include, for example, the compound represented by the above formula (6) as a constituent component.

[0389] By using the structure of the above-mentioned compound, the polymer B is less likely to be eluted into the liquid crystal due to the heat generated by driving the liquid crystal or lighting the backlight, and defects are less likely to occur.

[0390] The "backbone polymer" can be a homopolymer of the above-mentioned compound, or a plurality of compounds can be used in combination. In the case of a combination of compound species that are incompatible with liquid crystals or become incompatible with liquid crystals by firing, the ratio is not particularly limited regardless of the combination method. In the case of a combination with the compound species that are compatible with liquid crystals, from the viewpoint of suppressing dissolution into the liquid crystal, the preferred combination ratio of the compound species that are compatible with liquid crystals is 70 mol% or less, more preferably 50 mol% or less. However, the "backbone polymer" as shown above is only a unit that contributes to the stability of the film and has no great relationship with the weak anchoring property. Therefore, as long as the stabilization of the film is supplemented, the compound species and the combination method are not particularly limited.

[0391] The polymerizable group having a polymerizable unsaturated hydrocarbon group of the polymerizable compound used in forming the "backbone polymer" can be selected from the polymerizable groups having a polymerizable unsaturated hydrocarbon group that can be used in the polymerizable compound used in forming the block segment (A) or the block segment (B) in the above-mentioned polymer A. However, it is not limited to these.

[0392] The “backbone polymer” is mainly responsible for stabilization in the thin film state and has little to do with the physical properties of the weakly anchored membrane.

[0393] The stability of the film can be supplemented by the "trunk polymer", and the optimal molecular weight that can supplement the stability of the film varies depending on the type of compound used, so it is not particularly limited. On the other hand, in terms of the coating properties, sealing adhesion or film strength, and good weak anchoring properties of the weak anchoring oriented film, the introduction ratio of the "branch polymer" to the "trunk polymer" also becomes an important factor. For example, in terms of weak anchoring properties, the branch polymer plays an important role. If their introduction ratio becomes more, the strength of the film is impaired or thermal curing is hindered, so it is necessary to consider the appropriate introduction amount.

[0394] As shown above, the amount and molecular weight of the "backbone polymer" introduced have no effect (little effect) on the weak anchoring characteristics, so in terms of taking both of the above characteristics into consideration, the ratio of the number of molecules of the macromonomer represented by formula (7) used in the synthesis of the branch polymer to the number of molecules of the monomer represented by formula (6) used in the synthesis of the backbone polymer (introduction ratio) is preferably reduced. The preferred introduction ratio (macromonomer represented by formula (7) / monomer represented by formula (6)) is 0.1 / 99.9 to 50 / 50 (mol / mol), and more preferably 0.2 / 99.8 to 30 / 70 (mol / mol).

[0395] Taking into account the strength of the resulting coating film, workability during coating film formation, and uniformity of the coating film, the weight average molecular weight of the graft copolymer measured by GPC (Gel Permeation Chromatography) is preferably 2,000 to 5,000,000, and more preferably 5,000 to 2,000,000.

[0396] The macromonomer represented by formula (7) as a raw material for forming the branched polymer of the polymer B, i.e., the graft copolymer, can be obtained, for example, by a combination of living polymerization, chain transfer polymerization, and polymer terminal modification reaction. For example, as reported in the following reference, a chain transfer polymer having a carboxylic acid group at one terminal is synthesized by chain transfer polymerization of methyl methacrylate using thioglycolic acid as a chain transfer agent, and a macromonomer having a methacrylic acid group at one terminal can be synthesized by a high molecular weight reaction of the polymer with glycidyl methacrylate (Ito, K., Usami, N., Yamashita, Y.: Macromolecules, 13, 216 1980.).

[0397] In addition, it has been reported that a polymer having a radically polymerizable unsaturated bond at the terminal group can be obtained by continuous bulk polymerization at a high temperature of 200°C or higher (Toa Synthesis Research Annual Report TREND 2002, No. 5).

[0398] Main methods for synthesizing graft copolymers include the Grafting-to method (grafting method to the surface) of directly introducing a branch polymer into a main polymer, the Grafting-from method (grafting method from the surface) of polymerizing a monomer by a macromolecular initiator (a main polymer having a polymerization active point) to extend the branch polymer, and the Grafting-through method (grafting method through the surface) of polymerizing a macromolecular monomer (a polymer having a polymerizable functional group at a single end). Any method can be used, so the synthesis method is not limited.

[0399] The preparation method of the graft copolymer is not particularly limited, and a general method for industrial processing can be utilized. Specifically, the above-mentioned monomer can be used to prepare the graft copolymer by free radical polymerization, cationic polymerization or anionic polymerization. Among them, free radical polymerization is particularly preferred from the viewpoints of the ease of reaction control, the influence of halogen metal residues, etc.

[0400] As the polymerization initiator for free radical polymerization used in the synthesis of polymer (B), known compounds such as free radical polymerization initiators (free radical thermal polymerization initiators, free radical photopolymerization initiators), reversible addition-fragmentation chain transfer (RAFT) polymerization agents can be used, and can be selected from the free radical polymerization initiators that can be used in the synthesis of polymer A.

[0401] The organic solvent used in the synthesis of the polymer (B) may be any organic solvent that does not chemically react with the compound species constituting the copolymer and does not capture free radicals, and may be selected from organic solvents that can be used in the synthesis of the polymer A. The organic solvent may be used alone or in combination of two or more.

[0402] Furthermore, even a solvent that does not dissolve the produced polymer may be used by mixing with the above-mentioned organic solvent as long as the produced polymer does not precipitate.

[0403] In addition, in radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, and therefore, it is preferable to use an organic solvent that is degassed as much as possible.

[0404] When the graft copolymer obtained by the above polymerization is dissolved in the reaction solution, the reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or the graft copolymer contained in the reaction solution may be separated and then used for the preparation of the liquid crystal aligning agent.

[0405] The polymerization temperature during free radical polymerization can be selected from any temperature of 30 to 150° C., preferably in the range of 50 to 100° C. In addition, the reaction can be carried out at any concentration. If the concentration is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 40% by mass. The reaction can be carried out at a high concentration at the beginning, and then an organic solvent can be added.

[0406] In the above-mentioned free radical polymerization reaction, if the ratio of the free radical polymerization initiator is large relative to the monomer, the molecular weight of the obtained polymer becomes small, and if the ratio of the free radical polymerization initiator is small relative to the monomer, the molecular weight of the obtained polymer becomes large, so the ratio of the free radical initiator is preferably 0.1 to 10 mol% relative to the monomer to be polymerized. In addition, various monomer components, solvents, initiators, etc. can also be added during polymerization.

[0407] The polymer generated by the reaction solution obtained by the above reaction can be recovered by putting the reaction solution into a poor solvent and precipitating it, but the reprecipitation treatment is not necessary. As the poor solvent used in the precipitation, there can be mentioned: methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. The polymer put into the poor solvent and precipitated can be filtered and recovered, and then dried at room temperature or heated under normal pressure or reduced pressure. In addition, if the operation of redissolving the recovered polymer in an organic solvent and reprecipitating and recovering it is repeated 2 to 10 times, the impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons, etc. can be mentioned. If more than 3 poor solvents selected from them are used, the efficiency of purification is further improved, so it is preferred.

[0408] Polymer (C)

[0409] The polymer (C) has a polymer unit compatible with liquid crystal and reacts with the polymer (β) by heating.

[0410] The polymer (C) is characterized in that it is a polymer compatible with liquid crystal that can be synthesized by polymerizing a monomer compatible with liquid crystal (for example, living polymerization or chain transfer polymerization), and chemically reacts with the polymer (β) by heating, thereby becoming incompatible with liquid crystal.

[0411] The polymer (C) is used for weakly anchoring the liquid crystal aligning agent on the premise of being mixed with the polymer (β). The polymer (C) plays a role of expressing weak anchoring properties, and the polymer (β) plays a role of suppressing the elution of the polymer (C) into the liquid crystal.

[0412] In the process of coating and firing a polymer blend containing a polymer (C) and a polymer (β) mixed in an arbitrary ratio, the polymer (C) which is a polymer compatible with liquid crystals migrates to the surface layer and exhibits weak anchoring properties on the film surface. In addition, the polymer (C) and the polymer (β) are chemically bonded to compete with the surface layer migration of the polymer (C), thereby suppressing the dissolution of the polymer (C) into the liquid crystal.

[0413] It is known that the surface transferability is determined by the difference in thermal expansion coefficient and polarity of each polymer. The polymer (C) compatible with liquid crystal has a large thermal expansion coefficient and a low polarity. On the other hand, the polymer (β) has a small thermal expansion coefficient and a high polarity. Therefore, the polymer (C) is easy to transfer to the surface during the coating and firing process.

[0414] Polymer (β) preferably uses a polymer that reacts with the reactive groups contained in polymer (C) by heating, and has excellent coating properties, solvent selectivity, and adhesion to a film or substrate or a sealant. Thus, it is characterized in that it is possible to exhibit good and stable weak anchoring characteristics, good solvent selectivity, coating properties, and excellent adhesion to a film or a sealant or a substrate. Wherein, as long as polymer (C) is a polymer having a polymer unit compatible with liquid crystal and reacting with polymer (β), the polymerization method is not limited. In addition, as long as polymer (β) reacts with polymer (C) and can suppress polymer (C) from being eluted into a liquid crystal, the type of polymer and the polymerization method are not particularly limited.

[0415] The applicant has discovered that a weakly anchored liquid crystal alignment agent comprising a polymer such as polymer (C) (a polymer having a polymer unit compatible with liquid crystals and reacting with other polymers used in combination) is a weakly anchored liquid crystal alignment agent that can be easily manufactured and has good coating properties, and can provide a weakly anchored liquid crystal alignment film that has good adhesion to the seal, does not produce a pretilt angle, and can simultaneously achieve low-voltage drive and high-speed response when the voltage is disconnected (OFF), and has filed an application (Japanese Patent Application No. 2022-6921 and WO2023 / 140322. The contents of the application are hereby incorporated into this specification to the same extent as if all were explicitly stated.).

[0416] In the weak anchoring liquid crystal alignment agent comprising the polymer blend of the polymer (C) and the polymer (β) of the present invention, the polymer (C) mainly plays a role in expressing the weak anchoring property.

[0417] One embodiment of the polymer (C) is a polymer represented by the following formula (8).

[0418] [Chemistry 38]

[0419]

[0420] In formula (8), A represents an n-valent organic group having a molecular weight of 500 or less and having a group that reacts with the polymer β by heating, selected from the following formulas (8-A-1) to (8-A-16).

[0421] Q is a divalent polymer unit that contains as a constituent at least one selected from the compounds represented by the above formulae (2) to (5) and is compatible with liquid crystals.

[0422] R is a monovalent organic group selected from the following formulae (8-R-1) to (8-R-11) and having a molecular weight of 500 or less that does not react with the polymer β by heating.

[0423] n is an integer of 1 to 2. When n is 2, the two Qs and Rs may be the same or different.

[0424] [Chemistry 39]

[0425]

[0426] (In formulas (8-A-1) to (8-A-16), R1 and R2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, R3 and R4 each independently represent a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms, and X represents an oxygen atom or a sulfur atom. * represents a bonding site.)

[0427] [Chemistry 40]

[0428]

[0429] (In formulas (8-R-1) to (8-R-11), R1 and R2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and R3 and R4 each independently represent a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms. * represents a bonding site.)

[0430] The number of carbon atoms in the linear or branched alkyl group having 1 to 12 carbon atoms varies depending on the group, and may be, for example, 1 to 6 or 6 to 12.

[0431] The number of carbon atoms in the linear or branched alkylene group having 1 to 12 carbon atoms may be, for example, 1 to 6 or 1 to 3.

[0432] A in formula (8) is a group selected from the group consisting of formulae (8-A-1) to (8-A-16) described above, and is, for example, a partial structure of a RAFT agent in RAFT polymerization or a chain transfer agent in chain transfer polymerization described below.

[0433] For example, the -SC(=S)- group reacts with an amino group, a protected amino group, a hydroxyl group, a protected hydroxyl group, a thiol group, a protected thiol group, a carboxyl group, a protected carboxyl group, an isocyanate group, a protected isocyanate group, a maleimide group, a carboxylic anhydride group, a vinyl group, an allyl group, a styryl group, a (meth)acryloyl group, a (meth)acrylamide group, and the like.

[0434] The number of carbon atoms in the linear or branched alkyl group having 1 to 12 carbon atoms may be, for example, 1 to 6 or 1 to 3.

[0435] The number of carbon atoms in the linear or branched alkylene group having 1 to 12 carbon atoms may be, for example, 1 to 6 or 1 to 3.

[0436] R in formula (8) is a group selected from the above formulae (8-R-1) to (8-R-11), and is, for example, a partial structure of a RAFT agent in RAFT polymerization described below.

[0437] Q in the formula (8) is a divalent polymer unit compatible with liquid crystals and containing as a constituent at least one compound selected from the compounds represented by the formulae (2) to (5).

[0438] The monomer used in the synthesis of the polymer C may be a single component or a combination of a plurality of monomers. In addition, other radical polymerizable monomers described below may be used in combination.

[0439] The structure of Q in the polymer represented by formula (8) as an example of polymer (C) can be a homopolymer structure using only one compound (monomer) represented by the above formulas (2) to (5), or a copolymer structure combining multiple monomers. When multiple monomers are combined with each other, it can be a random copolymerization or a block copolymerization. When the monomers represented by the above formulas (2) to (5) are combined with each other, regardless of the combination method, the ratio is not particularly limited. When combined with a compound species incompatible with liquid crystal described below, from the viewpoint of maintaining the characteristics, the preferred combination ratio of the compound species incompatible with liquid crystal is 30 mol% or less, more preferably 20 mol% or less, but there is no limitation. These synthesis methods, combined monomers, and combination ratios are preferably used within the range that can obtain the target physical properties, display characteristics, electrical characteristics, etc.

[0440] Examples of compounds incompatible with liquid crystals include: compounds represented by formula (6); compounds having a polymerizable group and a highly polar structure, wherein the polymerizable group has the polymerizable unsaturated hydrocarbon group; compounds having a polymerizable group and a rigid structure, wherein the polymerizable group has the polymerizable unsaturated hydrocarbon group; and compounds having a polymerizable group and a thermosetting structure, wherein the polymerizable group has the polymerizable unsaturated hydrocarbon group.

[0441] One embodiment of a polymer blend comprising a polymer (C) and a polymer (β) is characterized in that it comprises a polymer (C) and a polymer (β), wherein the polymer (C) comprises a polymer obtained by polymerizing one or more monomers having a group that reacts with the polymer (β) by heating and is compatible with liquid crystals, and the polymer (β) reacts with the polymer (C) by heating to suppress the dissolution of the polymer (C) into the liquid crystal. Thus, high sealing adhesion, solvent selectivity, and coating properties can be obtained.

[0442] The temperature at which the group in the polymer (C) that reacts with the polymer (β) upon heating and the site in the polymer (β) that reacts with the n-valent organic group A in the polymer (C) upon heating react is not particularly limited, and may be, for example, 150° C. or above, or 200° C. or above.

[0443] In terms of the coating property, sealing adhesion or film strength, and good weak anchoring characteristics of the weak anchoring oriented film, it is preferred to use polymer (C) and polymer (β) in combination. In addition, the mixing ratio of polymer (C) and polymer (β) becomes an important factor. For example, in terms of weak anchoring characteristics, polymer (C) as a component showing weak anchoring properties plays an important role. If their introduction ratio becomes more, the strength of the film is impaired or thermal curing is hindered, so it is necessary to consider the appropriate introduction amount. On the other hand, the introduction amount and molecular weight of polymer (β) have no effect (little effect) on the weak anchoring characteristics, so in terms of the characteristics that are suitable for taking into account, it is preferred to reduce the mass ratio of polymer (C) relative to polymer (β). As a preferred introduction ratio (polymer C / polymer β), it is 0.1 / 99.9~50 / 50 (mass ratio), more preferably 1.0 / 99.0~40 / 60 (mass ratio).

[0444] The polymerizable group having a polymerizable unsaturated hydrocarbon group of the polymerizable compound used in forming Q in the above formula (8) can be selected from polymerizable groups having a polymerizable unsaturated hydrocarbon group that can be used in the polymerizable compound used in forming the block segment (A) or the block segment (B) in the above polymer A. However, it is not limited to these.

[0445] If the polymer (C) contacts the liquid crystal in a thin film state, a polymer-liquid crystal mixed layer is formed, showing weak anchoring properties. The thickness of the polymer-liquid crystal mixed layer formed according to the molecular weight of polymer C changes, and the weak anchoring property changes, so the optimization of the molecular weight becomes important. From the viewpoint of forming a good weak anchoring film, the preferred number average molecular weight of polymer C is 1000 to 100000, more preferably 3000 to 50000, and the molecular weight distribution (PDI) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 3.0 or less, more preferably 2.0 or less.

[0446] The polymer (C) is preferably obtained by living polymerization or chain transfer polymerization.

[0447] When obtaining polymer (C), the polymerization method does not need to be particularly limited. Cationic polymerization and anionic polymerization mostly use alkali metals, metal complexes, and halogen compounds when generating active species. In liquid crystal displays, the mixing of residues of metals, halogen compounds, etc. will become the main cause of screen burn-in and poor display. Therefore, it is preferred to use free radical polymerization that does not use metals or halogen compounds as much as possible. As active radical polymerization, active radical polymerization (NMP) using nitroxide radicals as dormant species, atom transfer radical polymerization (ATRP) using metal complexes, reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) using sulfur compounds as dormant species, active radical polymerization (TERP) using organic tellurium compounds, etc., using alkyl iodide compounds as dormant species, reversible transfer catalytic polymerization (RTCP) using phosphorus compounds, alcohols, etc. as catalysts, etc., as preferred polymerization methods, active radical polymerizations such as NMP, RTCP, and RAFT polymerization can be cited, and NMP or RAFT polymerization is particularly preferred. In addition, chain transfer polymerization is also preferably used.

[0448] When chain transfer polymerization is used, examples of the polymerization initiator used include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, 1,1′-bis(tert-butylperoxy)cyclohexane, hydrogen peroxide, and the like. The polymerization initiator is usually used in a ratio of 0.000001 to 0.1 mol parts, preferably 0.00001 to 0.01 mol parts, relative to 1 mol part of the monomer used. As the chain transfer agent, thiols are preferably used, and specific examples thereof include compounds represented by the following formulas (S-1) to (S-16). The chain transfer agent is usually used in a ratio of 0.000001 to 0.1 mol parts, preferably 0.00001 to 0.01 mol parts, relative to 1 mol part of the monomer used. The reaction temperature in the above-mentioned polymerization is preferably 20 to 200° C., more preferably 40 to 150° C., and the reaction time is preferably 1 to 168 hours, more preferably 8 to 72 hours.

[0449] [Chemistry 41]

[0450]

[0451] (In formulas (S-1) to (S-16), Me represents a methyl group and Et represents an ethyl group.)

[0452] By using chain transfer polymerization, polymer terminal control, molecular weight control, and molecular weight distribution control can be performed.

[0453] In chain transfer polymerization, polymers are obtained by competitive reactions of chain transfer and growth reactions. The molecular weight and molecular weight distribution of the polymer obtained by chain transfer polymerization are determined by the chain transfer constant (Cs) represented by the quotient of the chain transfer rate constant (kc) and the growth rate constant (kp). Generally, chain transfer polymerization can be a composition in which Cs is in the range of 1 to 60, and the monomer species and chain transfer agent species used, as well as their correct combination are important.

[0454] The chain transfer constant (Cs) greatly varies depending on the type of monomer or chain transfer agent used, and therefore needs to be appropriately selected.

[0455] As the polymerization initiator for free radical polymerization used in the synthesis of polymer (C), known compounds such as free radical polymerization initiators (free radical thermal polymerization initiators, free radical photopolymerization initiators), reversible addition-fragmentation chain transfer (RAFT) polymerization agents can be used, and can be selected from the free radical polymerization initiators that can be used in the synthesis of polymer A.

[0456] The organic solvent used in the synthesis of the polymer (C) may be any organic solvent that does not chemically react with the compound species constituting the copolymer and does not capture radicals, and can be selected from organic solvents that can be used in the synthesis of the polymer A.

[0457] The organic solvent used in the chain transfer polymerization reaction is not particularly limited as long as it is an organic solvent that dissolves the generated polymer. Specific examples thereof include the above-mentioned specific organic solvents, which may be used alone or in combination of two or more.

[0458] Furthermore, even a solvent that does not dissolve the produced polymer may be used by mixing with the above-mentioned organic solvent as long as the produced polymer does not precipitate.

[0459] In addition, in radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, and therefore, it is preferable to use an organic solvent that is degassed as much as possible.

[0460] In addition, when the polymer (C) obtained by the above polymerization is dissolved in the reaction solution, the reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or the polymer (C) contained in the reaction solution may be separated and then used for the preparation of the liquid crystal aligning agent.

[0461] The polymerization temperature during free radical polymerization can be selected from any temperature of 30 to 150° C., preferably in the range of 50 to 100° C. In addition, the reaction can be carried out at any concentration. If the concentration is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 40% by mass. The reaction can be carried out at a high concentration at the beginning, and then an organic solvent can be added.

[0462] In the above-mentioned free radical polymerization reaction, if the ratio of the free radical polymerization initiator is large relative to the monomer, the molecular weight of the obtained polymer becomes small, and if the ratio of the free radical polymerization initiator is small relative to the monomer, the molecular weight of the obtained polymer becomes large, so the ratio of the free radical initiator is preferably 0.1 to 10 mol% relative to the monomer to be polymerized. In addition, various monomer components, solvents, initiators, etc. can also be added during polymerization.

[0463] The polymer generated by the reaction solution obtained by the above reaction can be recovered by putting the reaction solution into a poor solvent and precipitating it, but the reprecipitation treatment is not necessary. As the poor solvent used in the precipitation, there can be mentioned: methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. The polymer put into the poor solvent and precipitated can be filtered and recovered, and then dried at room temperature or heated under normal pressure or reduced pressure. In addition, if the operation of redissolving the recovered polymer in an organic solvent and reprecipitating and recovering it is repeated 2 to 10 times, the impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons, etc. can be mentioned. If more than 3 poor solvents selected from them are used, the efficiency of purification is further improved, so it is preferred.

[0464] (Strong anchor)

[0465] In the present invention, "strong anchoring" means having the following anchoring strength: the liquid crystal molecules are oriented to be uniaxially oriented in the azimuthal or polar directions, and the orientation of the liquid crystal can be maintained even if energy is applied from the outside, or the liquid crystal molecules can be restored to their original positions even if the orientation changes. In the present invention, strong anchoring means that the azimuthal anchoring strength (A2) is greater than 10 -4 [J / m 2 ] situation.

[0466] (Strong anchoring oriented film)

[0467] In the present invention, "strongly anchored orientation film" refers to a film that forms a strong anchoring state by contacting with liquid crystals. It is a liquid crystal orientation film that can uniformly align liquid crystals in a uniaxial direction and has a sufficiently strong force to maintain the liquid crystals, i.e., the interface anchoring energy. The strongly anchored liquid crystal orientation agent used in the present invention includes two types: a strongly anchored liquid crystal orientation agent having an orientation restriction force that causes the liquid crystal to be uniaxially oriented in the horizontal direction and a strongly anchored liquid crystal orientation agent having an orientation restriction force that causes the liquid crystal to be uniaxially oriented in the azimuthal direction. The strongly anchored liquid crystal orientation film with horizontal orientation restriction force is obtained by rubbing or photo-orienting a cured film obtained by drying and firing after coating on a substrate. In addition, the strongly anchored liquid crystal orientation film with orientation restriction force in the azimuthal direction is obtained by photo-orienting a cured film obtained by drying and firing after coating on a substrate.

[0468] (Strong anchoring of liquid crystal display elements)

[0469] The two strongly anchored alignment films defined above are coated on the substrate with electrodes respectively and attached in pairs, thereby making it possible to produce a strongly anchored liquid crystal display element. The azimuth anchoring strength of the liquid crystal alignment film of the strongly anchored liquid crystal display element is large, so unlike the weakly anchored liquid crystal display element, it is impossible to change the orientation of the liquid crystal molecules directly above the electrode or directly above the strongly anchored liquid crystal alignment film, so it is impossible to achieve high transmittance and low driving voltage. On the other hand, there is no delay in response speed, which is a technical problem unique to weakly anchored liquid crystal display elements, and high-speed response can be achieved.

[0470] (a polymer (α) selected from polymers other than polymers (A), polymers (B) and polymers (C))

[0471] The strong anchor liquid crystal aligning agent of one embodiment of the present invention contains a polymer including at least one selected from the group consisting of compounds represented by the following formulae (10a) to (10q) as a constituent component.

[0472] (Polymer (α) as a component of a strong anchor liquid crystal aligning agent having horizontal alignment regulating force)

[0473] The strong anchoring liquid crystal alignment agent with horizontal orientation restriction of the present invention, for example, is a strong anchoring liquid crystal alignment agent of a polymer having a photoreactive site of a side chain that is photoreacted by ultraviolet rays, specifically, a side chain polymer that can show liquid crystal properties, or a mixed side chain polymer (hereinafter, also referred to as a side chain polymer) having a liquid crystal side chain polymer and a photosensitive side chain polymer. The coating obtained by the above polymer is also a film having a side chain polymer containing liquid crystal properties and photosensitivity. The coating is not subjected to friction treatment, and an orientation treatment is performed by polarized light irradiation. Then, after polarized light irradiation, a process of heating the side chain polymer film is performed to form a strong anchoring liquid crystal alignment film with horizontal orientation restriction. At this time, the tiny anisotropy exhibited by polarized light irradiation becomes a driving force, and the side chain polymer itself is effectively reoriented by self-organization. As a result, a highly efficient orientation treatment is achieved as a strongly anchored liquid crystal alignment film, and a strongly anchored liquid crystal alignment film endowed with high optical anisotropy can be obtained.

[0474] In the present invention, photoreactivity refers to the property of causing any one of (A-1) photocrosslinking (photodimerization) reaction, (A-2) photoisomerization and (A-3) photoFries rearrangement, or causing a plurality of reactions therein. The side chain polymer may preferably have a side chain that causes (A-1) photocrosslinking reaction and / or (A-2) photoisomerization reaction.

[0475] The side chain polymer is (i) a polymer that exhibits liquid crystallinity within a specified temperature range and has a photoreactive side chain. The side chain polymer (ii) can react with light in a wavelength range of 200 to 400 nm, preferably 240 to 400 nm, and exhibits liquid crystallinity within a temperature range of 50 to 300° C. The side chain polymer (iii) preferably has a photoreactive side chain that reacts with light in a wavelength range of 200 to 400 nm, preferably 240 to 400 nm, in particular polarized ultraviolet light. The side chain polymer (iv) exhibits liquid crystallinity within a temperature range of 50 to 300° C., and therefore preferably has a liquid crystal base group.

[0476] As shown above, the side chain polymer has a photoreactive side chain with photoreactivity. The structure of the side chain is not particularly limited, and preferably has a structure in which the reactions shown in (A-1), (A-2) and / or (A-3) above occur, and particularly preferably has a structure in which (A-1) photocrosslinking reaction and / or (A-2) photoisomerization reaction occur. It should be noted that the structure in which the photocrosslinking reaction (A-1) occurs is preferred from the aspect that the orientation of the side chain polymer can be stably maintained for a long time even if the structure after the reaction is exposed to external stress such as heat. In addition, the structure in which the photoisomerization reaction (A-2) occurs can be oriented under low exposure compared to photocrosslinking and photoFries rearrangement, and is preferred in terms of improving the production efficiency during the manufacture of a strongly anchored liquid crystal alignment film.

[0477] It is preferred that the side chain structure of the side chain polymer has a rigid mesogen component because the orientation of the liquid crystal is stable. Examples of the mesogen component include, but are not limited to, biphenyl, terphenyl, phenylcyclohexyl, and phenyl benzoate.

[0478] In the weak anchor liquid crystal alignment agent of the present invention comprising a polymer blend of a polymer (α) and a polymer (β) forming a strong anchor liquid crystal alignment agent having horizontal alignment restricting force, the polymer (α) mainly plays a role in highly uniaxially restricting the liquid crystal.

[0479] As the side chain having a photoreactive site that undergoes photoreaction by ultraviolet light contained in the polymer (α) (hereinafter also referred to as a side chain), a side chain represented by any one of the following formulae (10a) to (10f) is preferred. It should be noted that the number of benzene rings in one photosensitive side chain is preferably 3 or less from the viewpoint of solubility in a solvent.

[0480] [Chemistry 42]

[0481]

[0482] (wherein n1 and n2 are each independently 0, 1, 2 or 3.

[0483] L is a single bond, an alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more -CH2- constituting the alkylene group having 1 to 12 carbon atoms is substituted by -O-, -S-, -C(=O)-O- or -OC(=O)-, and a part or all of the hydrogen atoms of the alkylene group and the divalent linking group may be replaced by halogen atoms.

[0484] T 1 It is a single bond or an alkylene group having 1 to 12 carbon atoms, and a part or all of the hydrogen atoms of the alkylene group may be substituted with halogen atoms.

[0485] A1 , A 2 and D 1 Each is independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)-. 1 When A is a single bond, 2 Also a single bond.

[0486] Y 1 and Y 2 Each independently represents a phenylene group or a naphthylene group, and a part or all of the hydrogen atoms of the phenylene group and the naphthylene group may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0487] P 1 , Q 1 and Q 2 Each independently represents a single bond, a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a part or all of the hydrogen atoms of the phenylene group and the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. 1 When the number is 2 or more, each Q 1 They can be the same or different; 2 When the number is 2 or more, each Q 2 They can be the same or different.

[0488] R is a hydrogen atom, a cyano group, a halogen atom, a carboxyl group, a linear or branched alkyl group having 1 to 40 carbon atoms, a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0489] X 1 , X 2 and X 3 Each is independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. 1 When the number is 2 or more, each X 1 They can be the same or different; 2 When the number is 2 or more, each X 2 They can be the same or different.

[0490] Z 1a and Z 2aEach is independently a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, and a part or all of the hydrogen atoms of the alkyl group may be replaced by fluorine atoms.

[0491] Cou is a coumarin-6-yl group or a coumarin-7-yl group, and a part of the hydrogen atoms bonded thereto may be replaced by -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0492] E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.

[0493] G 1 and G 2 are each independently N or CH.

[0494] The dotted line is a bond.)

[0495] The alkylene group having 1 to 12 carbon atoms may be any of a linear, branched or cyclic group, and specific examples thereof include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl and decane-1,10-diyl.

[0496] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0497] The alkyl group having 1 to 5 carbon atoms may be linear or branched, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl.

[0498] Specific examples of the alkylcarbonyl group having 2 to 6 carbon atoms include methylcarbonyl (acetyl), ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, and n-pentylcarbonyl.

[0499] Specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and an n-pentoxy group.

[0500] Specific examples of the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms include a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, and a cyclooctanediyl group.

[0501] Specific examples of the cycloalkyl group having 3 to 7 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0502] The alkyl group having 1 to 3 carbon atoms may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, and an isopropyl group.

[0503] As the photosensitive side chain, a side chain represented by the following formula (10a-1), (10a-2), (10b-1), (10c-1), (10d-1), (10e-1) or (10f-1) is more preferable.

[0504] [Chemistry 43]

[0505]

[0506] (In the formula, L, A 1 , A 2 , Y 1 , Y 2 , P 1 , Q 1 , T 1 , R, X 1 , Z 1a , Z 2a , Cou, E, G 1 , G 2 , n1 and the dotted line are the same as above. 2 is a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a part or all of the hydrogen atoms of the phenylene group and the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0507] It should be noted that P in formula (10a-1) 2 is P from formula (10a) 1 Obtained by removing the single bond from

[0508] As the side chain represented by the formula (10a-1), a side chain represented by the following formula (10a-1-1) is preferred, and as the side chain represented by the formula (10a-2), a side chain represented by the formula (10a-2-1) is preferred.

[0509] [Chemistry 44]

[0510]

[0511] (Where L, R, and the dotted line are the same as above.)

[0512] As the side chain represented by the formula (10b-1), a side chain represented by the following formula (10b-1-1) is preferred.

[0513] [Chemistry 45]

[0514]

[0515] (In the formula, L, A 2 , Q 1 、T 1 , R and dotted line are the same as above. )

[0516] As the side chain represented by the formula (10c-1), a side chain represented by the following formula (10c-1-1), (10c-1-2) or (10c-1-3) is preferred.

[0517] [Chemistry 46]

[0518]

[0519] (Wherein, L, Cou and the dotted line are the same as above.)

[0520] As the side chain represented by the formula (10d-1), a side chain represented by the following formula (10d-1-1), (10d-1-2), (10d-1-3) or (10d-1-4) is preferred.

[0521] [Chemistry 47]

[0522]

[0523] (Where L, R, and the dotted line are the same as above.)

[0524] As the side chain represented by the formula (10e-1), a side chain represented by the following formula (10e-1-1) or (10e-1-2) is preferred.

[0525] [Chemistry 48]

[0526]

[0527] (Where L, R, and the dotted line are the same as above.)

[0528] As the side chain represented by the formula (10f-1), a side chain represented by the following formula (10f-1-1), (10f-1-2) or (10f-1-3) is preferred.

[0529] [Chemistry 49]

[0530]

[0531] (Where L, R, and the dotted line are the same as above.)

[0532] The side chain polymer used in the present invention has a photosensitive side chain bonded to the main chain, and can sense the best light selected from the wavelength of 200 to 400 nm, especially the light of 254 nm, 313 nm and 365 nm, to cause a crosslinking reaction, an isomerization reaction or a Fries rearrangement. The structure of the photosensitive side chain polymer is not particularly limited as long as it satisfies such characteristics, and the side chain structure preferably has a rigid liquid crystal unit component. When the above-mentioned side chain polymer is made into a single-layer phase difference film, a stable optical anisotropy can be obtained.

[0533] As a more specific example of the structure of a photosensitive side chain polymer, a structure having a main chain and a photosensitive side chain is preferred, wherein the main chain is composed of at least one free radical polymerizable group selected from (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and the like and siloxane.

[0534] In addition, the side chain polymer may also include a side chain that neither undergoes photodimerization nor photoisomerization (hereinafter, also referred to as a non-photosensitive side chain). As such a non-photosensitive side chain, a side chain represented by any one of the following formulae (10g) to (10q) is preferred, but is not limited thereto. It should be noted that in the following formulae, the dotted line is a bonding bond.

[0535] [Chemistry 50]

[0536]

[0537] [Chemistry 51]

[0538]

[0539] (In formula (10g) to (10q), A 3 and A 4 Each is independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-C(=O)-. 4 When the number is 2 or more, each A 4 They can be the same or different.

[0540] R 1 It is -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0541] R 2It is a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group or a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a part or all of the hydrogen atoms in these groups may be replaced by -NO2, -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

[0542] R 3 It is a hydrogen atom, -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0543] E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.

[0544] L′ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more -CH2- constituting the alkylene group having 1 to 12 carbon atoms is substituted by -O-, -S-, -C(=O)-O- or -OC(=O)-, and a part or all of the hydrogen atoms of the alkylene group and the divalent linking group may be replaced by halogen atoms.

[0545] k1 to k5 are each independently an integer of 0 to 2, but the total of k1 to k5 is 2 or more.

[0546] k6 and k7 are each independently an integer of 0 to 2, but the total of k6 and k7 is 1 or more.

[0547] m1, m2 and m3 are each independently an integer of 1-3.

[0548] n is 0 or 1.

[0549] Z 1 and Z 2 Each is independently a single bond, -C(=O)-, -CH2-O- or -CF2-.

[0550] The dotted lines are bonding bonds.

[0551] In addition, part or all of the hydrogen atoms of the benzene ring and the naphthalene ring in the formula may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.)

[0552] Specific examples of the monovalent nitrogen-containing heterocyclic group include pyrrolidinyl, piperidinyl, piperazinyl, pyrrolyl, pyridyl, etc. Specific examples of the monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms include cyclopentyl, cyclohexyl, etc. In addition, the alkyl group and alkoxy group include the same groups as those exemplified in the description of formulas (10a) to (10f).

[0553] The side chain type polymer used in the present invention can be obtained by polymerizing a monomer that provides a photosensitive side chain and, if necessary, a monomer that provides a non-photosensitive side chain.

[0554] Examples of the monomer that imparts a photosensitive side chain (hereinafter also referred to as monomer MA) include compounds represented by the following formula (M1-1), (M1-2), (M2), (M3), (M4), (M5) or (M6).

[0555] [Chemistry 52]

[0556]

[0557] (In the formula, A 1 , A 2 , D 1 , L, T 1 , Y 1 , Y 2 , P 1 , P 1′ , Q 1 , Q 2 , R, Z 1a , Z 2a ,Cou,E,X 1 , X 2 , G 1 , G 2 , n1 and n2 are the same as above.

[0558] PG represents a polymerizable group. )

[0559] The compound represented by the formula (M1-1) is preferably a compound represented by the following formula (M1-1-1), and the compound represented by the formula (M1-2) is preferably a compound represented by the following formula (M1-2-1).

[0560] [Chemistry 53]

[0561]

[0562] (In the formula, PG, L, Y 1 , Z 1a , Z 2a , P 2 and R are the same as above. )

[0563] The compound represented by the formula (M2) is preferably a compound represented by the following formula (M2-1).

[0564] [Chemistry 54]

[0565]

[0566] (In the formula, PG, A2 , L, T 1 , Y 1 , Z 1a , Z 2a , P 1 , Q 1 and R are the same as above. )

[0567] The compound represented by the formula (M3) is preferably a compound represented by the following formula (M3-1).

[0568] [Chemistry 55]

[0569]

[0570] (In the formula, PG, A 1 , L, X 1 , Q 1 , Cou and n1 are the same as above. )

[0571] The compound represented by the formula (M4) is preferably a compound represented by the following formula (M4-1).

[0572] [Chemistry 56]

[0573]

[0574] (In the formula, PG, A 1 , L, X 1 , Y 1 , Y 2 , Q 1 , E, R and n1 are the same as above. )

[0575] The compound represented by the formula (M5) is preferably a compound represented by the following formula (M5-1).

[0576] [Chemistry 57]

[0577]

[0578] (In the formula, PG, A 1 , L, X 1 , Y 1 , Y 2 , Q 1 , R and n1 are the same as above. )

[0579] The compound represented by the formula (M6) is preferably a compound represented by the following formula (M6-1).

[0580] [Chemistry 58]

[0581]

[0582] (In the formula, PG, A1 , L, X 1 , Y 1 , Y 2 , Q 1 , G 1 , G 2 , R and n1 are the same as above. )

[0583] The compound represented by the formula (M1-1) is preferably a compound represented by the following formula (M1-1-2), and the compound represented by the formula (M1-2) is preferably a compound represented by the following formula (M1-2-2).

[0584] [Chemistry 59]

[0585]

[0586] (In the formula, PG, L and R are the same as above.)

[0587] The compound represented by the formula (M2-1) is preferably a compound represented by the following formula (M2-2).

[0588] [Chemistry 60]

[0589]

[0590] (In the formula, PG, A 2 , L, T 1 , Q 1 and R are the same as above. )

[0591] The compound represented by the formula (M3-1) is preferably a compound represented by the following formula (M3-2), (M3-3) or (M3-4).

[0592] [Chemistry 61]

[0593]

[0594] (Wherein, PG, L and Cou are the same as above.)

[0595] The compound represented by the formula (M4-1) is preferably a compound represented by the following formula (M4-2), (M4-3), (M4-4) or (M4-5).

[0596] [Chemistry 62]

[0597]

[0598] (In the formula, PG, L and R are the same as above.)

[0599] The compound represented by the formula (M5-1) is preferably a compound represented by the following formula (M5-2) or (M5-3).

[0600] [Chemistry 63]

[0601]

[0602] (In the formula, PG, L and R are the same as above.)

[0603] The compound represented by the formula (M6-1) is preferably a compound represented by the following formula (M6-2), (M6-3) or (M6-4).

[0604] [Chemistry 64]

[0605]

[0606] (In the formula, PG, L and R are the same as above.)

[0607] Examples of the compound represented by formula (M1-1) include compounds represented by any of the following formulas (A-1-1-1) to (A-1-1-12). In the following formulas (A-1-1-1) to (A-1-1-12), PG is a polymerizable group, and s1 represents the number of methylene groups, which is an integer of 2 to 9. 11 is -H, -CH3, -OCH3, -C(CH3)3, -C(=O)-CH3 or -CN, R 12 It is -H, -CH3, -CN or -F.

[0608] [Chemistry 65]

[0609]

[0610] [Chemistry 66]

[0611]

[0612] [Chemistry 67]

[0613]

[0614] [Chemistry 68]

[0615]

[0616] Examples of the compound represented by formula (M1-2) include compounds represented by any one of the following formulae (A-1-2-1) to (A-1-2-4). In the following formulae, PG is a polymerizable group, and s1 is the same as described above.

[0617] [Chemistry 69]

[0618]

[0619] Specific examples of the compound represented by formula (M1-2) include 4-(6-methacryloyloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloyloxyhexyl-1-oxy)cinnamic acid, 4-(3-methacryloyloxypropyl-1-oxy)cinnamic acid, and 4-[4-(6-methacryloyloxyhexyl-1-oxy)benzoyloxy]cinnamic acid.

[0620] Examples of the compound represented by formula (M2) include compounds represented by any one of the following formulas (A-2-1) to (A-2-9). In the following formulas (A-2-1) to (A-2-9), PG is a polymerizable group, and s1 and s2 represent the number of methylene groups, each independently being an integer of 2 to 9. 21 It is -CH3, -OCH3, -C(CH3)3, -C(=O)-CH3, -CN or -F.

[0621] [Chemistry 70]

[0622]

[0623] [Chemistry 71]

[0624]

[0625] [Chemistry 72]

[0626]

[0627] Examples of the compound represented by formula (M3) include compounds represented by any one of the following formulae (A-3-1) to (A-3-5). In the following formulae, PG is a polymerizable group, and s1 is the same as described above.

[0628] [Chemistry 73]

[0629]

[0630] Examples of the compound represented by formula (M4) include compounds represented by any one of the following formulae (A-4-1) to (A-4-4). In the following formulae, PG is a polymerizable group, and s1 is the same as described above.

[0631] [Chemistry 74]

[0632]

[0633] Examples of the compound represented by formula (M5) include compounds represented by any one of the following formulae (A-5-1) to (A-5-3). In the following formulae, PG is a polymerizable group, and s1 is the same as described above.

[0634] [Chemistry 75]

[0635]

[0636] Examples of the compound represented by formula (M6) include compounds represented by any one of the following formulae (A-6-1) to (A-6-3). In the following formulae, PG is a polymerizable group, and s1 is the same as described above.

[0637] [Chemistry 76]

[0638]

[0639] Some of the monomers are commercially available, and some can be produced by the method described in, for example, International Publication No. 2015 / 002292.

[0640] As an example of the monomer that imparts a non-photosensitive side chain that undergoes neither photodimerization nor photoisomerization (hereinafter also referred to as monomer MB), there can be mentioned a monomer that can form a mesogen group in the side chain.

[0641] The liquid crystal unit group may be a group that forms a liquid crystal unit structure independently, such as biphenyl or phenyl benzoate, or a group that forms a liquid crystal unit structure by hydrogen bonding such as benzoic acid. The liquid crystal unit group having a side chain preferably has the following structure.

[0642] [Chemistry 77]

[0643]

[0644] As a specific example of the monomer MB, the following structure is preferred, wherein the structure has a polymerizable group derived from at least one of free radical polymerizable groups selected from hydrocarbons, (meth)acrylates, itaconates, fumarates, maleates, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane, and at least one of the structures of formulae (b1) to (b11). It is particularly preferred that the monomer MB has a polymerizable group derived from (meth)acrylate.

[0645] Preferred examples of the monomer MB include monomers represented by the following formulae (MB-1) to (MB-8). In the following formulae, PG is a polymerizable group, and p represents the number of methylene groups, which is an integer of 2 to 9.

[0646] [Chemistry 78]

[0647]

[0648] In addition, other monomers can be copolymerized within the range that does not impair the performance of photoreactivity and / or liquid crystal properties. Examples of the other monomers include monomers that are industrially available and capable of free radical polymerization. Specific examples of the other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.

[0649] Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

[0650] Specific examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracene methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate, and 8-ethyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate.

[0651] Specific examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracene methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate, and 8-ethyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate.

[0652] Specific examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, and the like.

[0653] Specific examples of the styrene compound include styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene, and the like.

[0654] Specific examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0655] The above configuration can provide a liquid crystal alignment film and a liquid crystal alignment agent, wherein the liquid crystal alignment film can obtain excellent liquid crystal orientation at any temperature by controlling the liquid crystal temperature of the polymer (α), has excellent display reliability, high voltage retention characteristics, and can reduce charge accumulation.

[0656] In the side chain polymer, the content of the photosensitive side chain and the non-photosensitive side chain is not particularly limited. The photosensitive side chain can be a homopolymer of 100 mol%, or two or more photosensitive side chains can be used. In the case of a copolymer of a photosensitive side chain and a non-photosensitive side chain, from the viewpoint of photoreactivity, the photosensitive side chain is preferably 5 to 99.9 mol%, more preferably 5 to 95 mol%, and from the viewpoint of photostability, it is further preferably 5 to 50 mol%. In addition, from the viewpoint of photoreactivity, the non-photosensitive side chain is preferably 95 mol% or less, more preferably 5 to 95 mol%, and from the viewpoint of photostability, it is further preferably 50 mol% or more. In the case of a copolymer, two or more photosensitive side chains and non-photosensitive side chains can also be used.

[0657] The side chain type polymer used in the present invention may contain other side chains. When the total content of the photosensitive side chain and the non-photosensitive side chain is less than 100 mol %, the content of the other side chains is the remainder.

[0658] PG in the monomers MA and MB is a polymerizable group, preferably a group represented by any one of the following formulas (PG1) to (PG9). Among them, from the viewpoint of easy control of the polymerization reaction and the stability of the polymer, an acryloyloxy group or a methacryloyloxy group represented by formula (PG1) is preferred. However, it is not limited to these.

[0659] [Chemistry 79]

[0660]

[0661] (Where R A are hydrogen atoms or methyl groups, and the dotted lines are bonds.)

[0662] Considering the strength of the obtained coating film, the workability during coating film formation, and the uniformity of the coating film, the weight average molecular weight (Mw) of the side chain polymer used in the present invention is preferably 2000 to 2000000, more preferably 2000 to 1000000, and further preferably 5000 to 200000. It should be noted that in the present invention, Mw is a polystyrene-converted measurement value based on the gel permeation chromatography (GPC) method.

[0663] The method for producing the side chain polymer is not particularly limited, and a general method for industrial processing can be used. Specifically, it can be produced by free radical polymerization, cationic polymerization or anionic polymerization of the vinyl group of monomer MA, monomer MB as required and other monomers. Among them, free radical polymerization is particularly preferred from the viewpoint of ease of reaction control.

[0664] As the polymerization initiator for free radical polymerization, known compounds such as free radical polymerization initiators (free radical thermal polymerization initiators, free radical photopolymerization initiators) and reversible addition-fragmentation chain transfer (RAFT) polymerization agents can be used, and can be selected from free radical polymerization initiators that can be used in the synthesis of the polymer A.

[0665] The radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, and the like can be used.

[0666] The organic solvent may be any organic solvent that does not chemically react with the compound species constituting the copolymer and does not capture radicals, and can be selected from organic solvents that can be used in the synthesis of the polymer A.

[0667] The organic solvent used in the chain transfer polymerization reaction is not particularly limited as long as it is an organic solvent that dissolves the generated polymer. Specific examples thereof include the above-mentioned specific organic solvents, which may be used alone or in combination of two or more.

[0668] Furthermore, even a solvent that does not dissolve the produced polymer may be used by mixing with the above-mentioned organic solvent as long as the produced polymer does not precipitate.

[0669] In addition, in radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, and therefore, it is preferable to use an organic solvent that is degassed as much as possible.

[0670] In addition, when the polymer (α) obtained by the above polymerization is dissolved in the reaction solution, the reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or the polymer (α) contained in the reaction solution may be separated and then used for the preparation of the liquid crystal aligning agent.

[0671] The polymerization temperature during free radical polymerization can be selected from any temperature of 30 to 150° C., preferably in the range of 50 to 100° C. In addition, the reaction can be carried out at any concentration. If the concentration is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 40% by mass. The reaction can be carried out at a high concentration at the beginning, and then an organic solvent can be added.

[0672] In the above-mentioned free radical polymerization reaction, if the ratio of the free radical polymerization initiator is large relative to the monomer, the molecular weight of the obtained polymer becomes small, and if the ratio of the free radical polymerization initiator is small relative to the monomer, the molecular weight of the obtained polymer becomes large, so the ratio of the free radical initiator is preferably 0.1 to 10 mol% relative to the monomer to be polymerized. In addition, various monomer components, solvents, initiators, etc. can also be added during polymerization.

[0673] The polymer generated by the reaction solution obtained by the above reaction can be recovered by putting the reaction solution into a poor solvent and precipitating it, but the reprecipitation treatment is not necessary. As the poor solvent used in the precipitation, there can be mentioned: methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. The polymer put into the poor solvent and precipitated can be filtered and recovered, and then dried at room temperature or heated under normal pressure or reduced pressure. In addition, if the operation of redissolving the recovered polymer in an organic solvent and reprecipitating and recovering it is repeated 2 to 10 times, the impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons, etc. can be mentioned. If more than 3 poor solvents selected from them are used, the efficiency of purification is further improved, so it is preferred.

[0674] (Polymer (α) as a component of a strong anchor liquid crystal aligning agent having an alignment regulating force in an azimuthal direction)

[0675] The strong anchoring liquid crystal alignment agent having an orientation-limiting force in the azimuthal direction of the present invention is a strong anchoring liquid crystal alignment agent comprising a polymer having a photoreactive site on the vertically oriented side chain that undergoes a photoreaction using ultraviolet rays. Specifically, it is a strong anchoring liquid crystal alignment agent comprising a side chain polymer having a photoreactive site that induces an axis-selective photoreaction by irradiating polarized ultraviolet rays and that restricts the orientation of liquid crystal molecules in the vertical direction.

[0676] The coating obtained by the above polymer is also a film of a side chain polymer including photosensitivity and vertical orientation. The coating is not subjected to rubbing treatment, and an orientation treatment is performed by polarized light irradiation. Polarized light irradiation can be irradiated from the normal direction of the coating, or from an angle inclined at any angle relative to the normal direction of the coating (oblique exposure), and a strong anchoring liquid crystal alignment film having an orientation restriction force in the azimuthal direction is formed by polarized light exposure. At this time, the axis-selective photoreaction corresponding to the polarized light direction and the irradiation angle of the polarized light exposure and the manifestation of anisotropy associated therewith become the driving force, which can more effectively restrict the orientation of the liquid crystal molecules to the azimuthal direction. It should be noted that the polymer (α) having an orientation restriction force in the azimuthal direction is different from the polymer (α) having a horizontal orientation restriction force, and is not based on the re-orientation of the heat treatment at the liquid crystal temperature of the polymer after polarized light exposure. Therefore, as long as there is no special reason, the heating treatment after polarized light exposure is not required, and liquid crystal properties are not required.

[0677] In the present invention, photoreactivity refers to the property of causing any one of (A-1) photocrosslinking (photodimerization) reaction, (A-2) photoisomerization and (A-3) photoFries rearrangement, or causing a plurality of reactions therein. The side chain polymer may preferably have a side chain that causes (A-1) photocrosslinking reaction and / or (A-2) photoisomerization reaction.

[0678] As shown above, the side chain polymer has a photoreactive side chain with photoreactivity. The structure of the side chain is not particularly limited, and preferably has a structure in which the reactions shown in (A-1), (A-2) and / or (A-3) above occur, and particularly preferably has a structure in which (A-1) photocrosslinking reaction and / or (A-2) photoisomerization reaction occur. It should be noted that the structure in which the photocrosslinking reaction (A-1) occurs is preferred from the viewpoint that the orientation of the side chain polymer can be stably maintained for a long time even if the structure after the reaction is exposed to external stress such as heat. In addition, the structure in which the photoisomerization reaction (A-2) occurs can be oriented under low exposure compared to photocrosslinking and photoFries rearrangement, and is preferred from the viewpoint of improving the production efficiency during the manufacture of a strongly anchored liquid crystal alignment film.

[0679] The structure of the side chain of the side chain type polymer has a hydrophobic alkyl side chain or cycloalkane at the end of the side chain not bonded to the main chain, which is preferred because the vertical orientation of the liquid crystal is stabilized. In addition, the main chain, the bonding site between the main chain and the side chain are rigid structures, which are preferred because the tilt angle is stabilized. Specifically, preferably phenyl, phenylmaleimide, etc., supplement the rigid group through π electron interaction. In addition, by making the site other than the vertical orientation side chain a thermal crosslinking group, the stabilization of the tilt angle can also be achieved.

[0680] In the weak anchor liquid crystal alignment agent of the present invention, which is a polymer blend of polymer (α) and polymer (β) and forms a strong anchor liquid crystal alignment agent having an alignment limiting force in the azimuthal direction, polymer (α) mainly plays a role in limiting the uniaxial alignment of the liquid crystal in the azimuthal direction.

[0681] As the vertically aligned side chain having a photoreactive site that undergoes a photoreaction by ultraviolet light (hereinafter also referred to as a photosensitive vertically aligned side chain), which is contained in the polymer (α), the side chains represented by the formulae (10a) to (10f) are preferred.

[0682] From the viewpoint of the degree of freedom in designing the vertical alignment side chain, the number of synthesis times, and the possibility of alignment treatment at low exposure, the photosensitive vertical alignment side chain is preferably a side chain represented by formula (10a) or formula (10b), and particularly preferably a side chain represented by the following formula (pa-1).

[0683] [Chemistry 80]

[0684]

[0685] In the formula, A represents a pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group, a thiophene-2,5-diyl group, a furan-2,5-diyl group, a 1,4- or 2,6-naphthylene group or a phenylene group, which is substituted by a group selected from a fluorine atom, a chlorine atom and a cyano group, or by an alkoxy group having 1 to 5 carbon atoms, or a linear or branched alkyl residue (which is substituted by one cyano group or one or more halogen atoms, as appropriate); R1 represents a single bond, an oxygen atom, -COO- or -OCO-; R2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group; R3 represents a single bond, an oxygen atom, -COO- or -OCO-; R4 represents a linear or branched alkyl group having 1 to 40 carbon atoms, or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group; D represents an oxygen atom, a sulfur atom or -NR d -(where R d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms); X and Y are each independently a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, and a part or all of the hydrogen atoms of the alkyl group may be replaced by fluorine atoms; a is an integer of 0 to 3; * represents a bonding position.

[0686] In the present invention, the site having a photosensitive vertically oriented side chain represented by the above formula (pa-1) in the molecule can be represented by the following formula (a-1), for example. In addition, the site can be a structure derived from a monomer represented by the following formula (a-1-m), but is not limited thereto. In the formula, Ia is a monovalent organic group represented by the following formula (pa-1).

[0687] [Chemistry 81]

[0688] -S a -I a (a-1)

[0689]

[0690] In the above formula (a-1) or (a-1-m), S a represents the spacer unit, S a The bonding group on the left side of arbitrarily bonds to the main chain of the polymer (α) via a spacer group.

[0691] S a For example, it can be represented by the structure of the following formula (Sp).

[0692] [Chemistry 82]

[0693] ----W1-A1-W2-A2-W3---- (Sp)

[0694] In formula (Sp),

[0695] The key on the left side of W1 indicates the same b Bonding,

[0696] The key on the right side of W3 represents the same b Bonding,

[0697] W1, W2 and W3 each independently represent a single bond, a divalent heterocycle, -(CH2) n -(wherein n represents 1 to 20), -OCH2-, -CH2O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF2O-, -OCF2-, -CF2CF2- or -C≡C-, and one or more non-adjacent CH2 groups in these substituents can be independently substituted by -O-, -CO-, -CO-O-, -O-CO-, -Si(CH3)2-O-Si(CH3)2-, -NR-, -NR-CO-, -CO-NR-, -NR-CO-O-, -OCO-NR-, -NR-CO-NR-, -CH=CH-, -C≡C- or -O-CO-O- (wherein R independently represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms).

[0698] A1 and A2 are each independently a group selected from a single bond, an alkylene group, a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group, and each group is unsubstituted or one or more hydrogen atoms may be replaced by a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group.

[0699] In formula (a-1-m), M aRepresents a polymerizable group. Examples of the polymerizable group include: (meth)acrylate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, (meth)acrylamide and free radical polymerizable groups of its derivatives, and siloxane. Preferably, it may be (meth)acrylate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, acrylamide.

[0700] r is an integer satisfying 1≤r≤3.

[0701] M b It is a group selected from a single bond, a (r+1)-valent heterocycle, a (r+1)-valent straight-chain or branched saturated hydrocarbon group having 1 to 10 carbon atoms, a (r+1)-valent aromatic group, and a (r+1)-valent alicyclic group, each of which is unsubstituted or one or more hydrogen atoms may be replaced by a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group.

[0702] As A1, A2 and M b The aromatic group in the formula (A) includes aromatic hydrocarbons having 6 to 18 carbon atoms such as benzene, biphenyl, and naphthalene. b The alicyclic group in the formula (A1, A2 and M) includes, for example, alicyclic hydrocarbons having 6 to 12 carbon atoms such as cyclohexane and bicyclohexane. b Examples of the heterocyclic ring in A1 and A2 include nitrogen-containing heterocyclic rings such as pyridine, piperidine, and piperazine. Examples of the alkyl group in A1 and A2 include linear or branched alkyl groups having 1 to 10 carbon atoms.

[0703] From the viewpoint of being able to show good vertical orientation control ability and stable pretilt angle, the group represented by the above (pa-1) is preferably the group represented by the following (pa-1-a). In addition, the structure of the part derived from the monomer represented by the following formula (pa-1-ma) can be cited, but it is not limited to this.

[0704] [Chemistry 83]

[0705]

[0706] In the formula (pa-1-a) or (pa-1-ma), M a 、M b , S a and r are the same as defined above.

[0707] In addition, Z is an oxygen atom or a sulfur atom.

[0708] X a and X b Each is independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms.

[0709] R1 to R4 have the same definitions as R1 to R4 in the above formula (pa-1).

[0710] R5 is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and is preferably a methyl group, a methoxy group or a fluorine atom.

[0711] a is an integer of 0-3, and b is an integer of 0-4.

[0712] In the formula (pa-1-a) or (pa-1-ma), S a The straight chain or branched alkylene group having 1 to 10 carbon atoms is preferably a straight chain or branched alkylene group having 1 to 8 carbon atoms, for example, preferably a methylene group, an ethylene group, a n-propylene group, a n-butylene group, a tert-butylene group, a n-pentylene group, a n-hexylene group, a n-heptylene group, or a n-octylene group.

[0713] As S a Examples of the divalent aromatic group include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, and 2,3,5,6-tetrafluoro-1,4-phenylene.

[0714] In the formula (pa-1-a) or (pa-1-ma), S a Examples of the divalent alicyclic group include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene.

[0715] As S a Examples of the divalent heterocyclic group include 1,4-pyridylene, 2,5-pyridylene, furan-1,4-diyl, piperazine-1,4-diyl and piperidine-1,4-diyl.

[0716] S a An alkylene group having 1 to 8 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is further preferred.

[0717] Examples of the divalent aromatic group for R2 include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, and naphthylene.

[0718] Examples of the divalent alicyclic group for R2 include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene.

[0719] Examples of the divalent heterocyclic group for R2 include 1,4-pyridylene, 2,5-pyridylene, furan-1,4-diyl, piperazine-1,4-diyl, piperidine-1,4-diyl and the like.

[0720] R2 is preferably 1,4-phenylene, trans-1,4-cyclohexylene, or trans-trans-1,4-bicyclohexylene.

[0721] Examples of the linear or branched alkyl group having 1 to 40 carbon atoms for R4 include linear or branched alkyl groups having 1 to 20 carbon atoms, and a part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-lauryl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl, and 2-(perfluorodecyl)ethyl.

[0722] Examples of R4, which is a monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group, include a cholesteryl group, a cholestanyl group, an adamantyl group, a group represented by the following formula (Alc-1) or (Alc-2) (wherein R7 is each a hydrogen atom, a fluorine atom or an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms may be substituted by a fluorine atom, and * indicates a bonding position), and the like.

[0723] [Chemistry 84]

[0724]

[0725] Examples of the monomer represented by the formula (pa-1-ma) include structures represented by the formulas (paa-1-ma1) to (paa-1-ma18), but are not limited thereto. In the formula, "E" represents the E form, and "t" represents that the cyclohexyl group is trans.

[0726] [Chemistry 85]

[0727]

[0728] [Chemistry 86]

[0729]

[0730] The polymer (α) constituting the strong anchor liquid crystal aligning agent having alignment regulating force in the azimuth direction of the present invention preferably copolymerizes a thermally crosslinkable group A and a thermally crosslinkable group B in addition to the above-mentioned photosensitive vertical alignment side chain in order to improve tilt stability and reliability.

[0731] The thermally crosslinkable group A and the thermally crosslinkable group B are each independently a group selected from a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, a group containing an epoxy portion, an oxetane group, a thiiranyl group, an isocyanate group and a blocked isocyanate group, and are selected in such a way that the thermally crosslinkable group A and the thermally crosslinkable group B undergo a crosslinking reaction by heat, wherein the thermally crosslinkable group A and the thermally crosslinkable group B may be the same as each other.

[0732] As such a combination of the heat-crosslinkable group A and the heat-crosslinkable group B, one is a carboxyl group and the other is an epoxy group, an oxetane group or a thiirane group; one is a hydroxyl group and the other is a blocked isocyanate group; one is a phenolic hydroxyl group and the other is an epoxy group, an oxetane group or a thiirane group; one is a carboxyl group and the other is a blocked isocyanate group; one is an amino group and the other is a blocked isocyanate group; both are N-alkoxymethylamides, etc. More preferred combinations are a carboxyl group and an epoxy group, a hydroxyl group and a blocked isocyanate group, etc.

[0733] When the thermally crosslinkable group A is introduced into the polymer (α), it is sufficient to copolymerize the monomer having the thermally crosslinkable group A. In addition, when the thermally crosslinkable group A and the thermally crosslinkable group B are introduced into the polymer (α), it is sufficient to copolymerize the monomer having the thermally crosslinkable group A and the monomer having the thermally crosslinkable group B.

[0734] Examples of the monomer having a thermally crosslinkable group include monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide;

[0735] Monomers having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, 2-(acryloyloxy)ethyl caprolactone, 2-(methacryloyloxy)ethyl caprolactone, poly(ethylene glycol)ethyl ether acrylate, poly(ethylene glycol)ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone;

[0736] Monomers having a phenolic hydroxyl group such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide and N-(hydroxyphenyl)maleimide;

[0737] Monomers having an amino group such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate;

[0738] (Meth)acrylamide compounds substituted with hydroxymethyl or alkoxymethyl, such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide;

[0739] Monomers having a group containing an epoxy moiety such as allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, 3-vinyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide;

[0740] 3-(Acryloyloxymethyl)oxetane, 3-(Acryloyloxymethyl)-2-methyloxetane, 3-(Acryloyloxymethyl)-3-ethyloxetane, 3-(Acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(Acryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(Acryloyloxymethyl)-2-phenyloxetane, 3-(Acryloyloxymethyl)-2,2-difluorooxetane, 3-(Acryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(Acryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-Acryloyloxyethyl)oxetane, 3-(2 Acrylic acid esters such as 3-(2-acryloxyethyl)-2-ethyloxetane, 3-(2-acryloxyethyl)-3-ethyloxetane, 3-(2-acryloxyethyl)-2-trifluoromethyloxetane, 3-(2-acryloxyethyl)-2-pentafluoroethyloxetane, 3-(2-acryloxyethyl)-2-phenyloxetane, 3-(2-acryloxyethyl)-2,2-difluorooxetane, 3-(2-acryloxyethyl)-2,2,4-trifluorooxetane, 3-(2-acryloxyethyl)-2,2,4,4-tetrafluorooxetane; 3-(methacryloxymethyl)oxetane, 3-(methyl)- 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-methacryloyloxyethyl)oxetane, 3-(2-methylacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluorooxetane Monomers having a group containing an oxetane moiety, such as 3-(2-methacryloyloxyethyl)-2-ethyloxetane, 3-(2-methacryloyloxyethyl)-3-ethyloxetane, 3-(2-methacryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methacryloyloxyethyl)-2-phenyloxetane, 3-(2-methacryloyloxyethyl)-2,2-difluorooxetane, 3-(2-methacryloyloxyethyl)-2,2,4-trifluorooxetane, and 3-(2-methacryloyloxyethyl)-2,2,4,4-tetrafluorooxetane;

[0741] 2,3-epithiopropyl acrylate or methacrylate, and monomers having a group containing a thiirane moiety, such as 2-, 3-, or 4-(β-epithiopropylthiomethyl)styrene, 2-, 3-, or 4-(β-epithiopropyloxymethyl)styrene, 2-, 3-, or 4-(β-epithiopropylthio)styrene, and 2-, 3-, or 4-(β-epithiopropyloxy)styrene;

[0742] Monomers having a blocked isocyanate group such as 2-(0-(1′-methylpropyleneamino)carboxyamino)ethyl acrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl acrylate, 2-(0-(1′-methylpropyleneamino)carboxyamino)ethyl methacrylate, and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate; etc. (Meth)acrylamide refers to both acrylamide and methacrylamide.

[0743] In addition, in the present invention, in addition to the monomer having a photosensitive vertically oriented side chain and the monomer having a thermally crosslinkable group A represented by the above formula (a-1-m), and the monomer having a thermally crosslinkable group B as required, other monomers copolymerizable with these monomers can also be used in combination.

[0744] Specific examples of such other monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds; acrylamide compounds such as N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, acrylamide, and monomers having a nitrogen-containing aromatic heterocyclic group and a polymerizable group.

[0745] Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracene methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecanyl acrylate, and 8-ethyl-8-tricyclodecanyl acrylate.

[0746] Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracene methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecanyl methacrylate, and 8-ethyl-8-tricyclodecanyl methacrylate.

[0747] Examples of the (meth)acrylamide compound include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide.

[0748] Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, and 3-vinyl-7-oxabicyclo[4.1.0]heptane.

[0749] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0750] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0751] The nitrogen-containing aromatic heterocycle in the monomer having a nitrogen-containing aromatic heterocyclic group and a polymerizable group may be a nitrogen-containing aromatic heterocycle containing at least one, preferably one to four, structures selected from the following formulas [Na] to [Nb] (wherein Z2 is a linear or branched alkyl group having 1 to 5 carbon atoms).

[0752] [Chemistry 87]

[0753]

[0754] In the formula, * represents the bonding site.

[0755] Specifically, oxazole ring, thiazole ring, pyridine ring, pyrimidine ring, quinoline ring, 1-pyrazoline ring, isoquinoline ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazine ring, phenanthroline ring, quinoxaline ring, benzothiazole ring, oxadiazole ring, acridine ring, etc. can be mentioned. In addition, the carbon atoms of these nitrogen-containing aromatic heterocyclic rings may have a substituent containing a heteroatom. Among them, for example, a pyridine ring can be mentioned.

[0756] Examples of the monomer having a nitrogen-containing aromatic heterocyclic group and a polymerizable group include 2-(2-pyridylcarbonyloxy)ethyl (meth)acrylate, 2-(3-pyridylcarbonyloxy)ethyl (meth)acrylate, and 2-(4-pyridylcarbonyloxy)ethyl (meth)acrylate.

[0757] The other monomers used in the present invention may be used alone or in combination of two or more.

[0758] The photosensitive vertical alignment side chain represented by the above formula (pa-1) forming the photosensitive side chain of the polymer (α) contained in the liquid crystal aligning agent of the present invention may be used alone or in combination of two or more.

[0759] The photosensitive vertical alignment side chain represented by the formula (pa-1) is preferably contained in a ratio of 5 to 95 mol %, 10 to 60 mol %, or 15 to 50 mol % based on all repeating units of the polymer.

[0760] The site having a thermally crosslinkable group in the polymer (α) of the present invention may be a thermally crosslinkable group A alone, or two or more sites including a thermally crosslinkable group A and a thermally crosslinkable group B may be used in combination.

[0761] The introduced amount of the site having a thermally crosslinkable group is preferably 5 to 95 mol%, 40 to 90 mol%, or 50 to 85 mol% of all repeating units of the polymer (α).

[0762] The content of the structure derived from the other monomer is preferably 0 to 40 mol%, 0 to 30 mol%, or 0 to 20 mol% of all repeating units of the polymer (α).

[0763] The polymer (α) contained in the strong anchor liquid crystal aligning agent of the present invention has high sensitivity to light, for example, and therefore can express the alignment control capability even in polarized ultraviolet irradiation with a low exposure dose.

[0764] In addition, the polymer (α) contains a heat-crosslinkable group A, and further contains a heat-crosslinkable group B in the component, so that even when the calcination time of the liquid crystal alignment agent is short, a crosslinking reaction containing the polymer (α) can be performed. Thus, when anisotropy is exhibited by photoreaction at the photo-alignment site, anisotropy is easily retained (stored) in the liquid crystal alignment film, thereby improving the liquid crystal orientation and exhibiting a pretilt angle of the liquid crystal.

[0765] In addition, a liquid crystal alignment film and a liquid crystal alignment agent can be provided which have good liquid crystal alignment, excellent pretilt angle expression capability, little change in pretilt angle even after long-term driving, excellent display reliability, high voltage holding characteristics, and can reduce charge accumulation.

[0766] Moreover, the liquid crystal aligning agent of this invention can aim at improvement of electric characteristics, such as improvement of voltage holding ratio and suppression of residual charge accumulation, by containing a polymer (β).

[0767] The polymer (α) constituting the strong anchor liquid crystal aligning agent having an orientation restricting force in the azimuthal direction of the present invention is obtained by copolymerizing a monomer having a photo-aligning group represented by the above formula (pa-1), a monomer having a thermally crosslinkable group A, and, if necessary, a monomer having a thermally crosslinkable group B. In addition, it can be copolymerized with the above other monomers.

[0768] The method for producing the polymer (α) is not particularly limited, and a general method for industrial processing can be used. Specifically, it can be produced by cationic polymerization, free radical polymerization, or anionic polymerization of the vinyl group of the monomer. Among them, free radical polymerization is particularly preferred from the viewpoints of ease of reaction control, etc.

[0769] As the polymerization initiator for free radical polymerization used in the synthesis of polymer (α), known compounds such as free radical polymerization initiators (free radical thermal polymerization initiators, free radical photopolymerization initiators), reversible addition-fragmentation chain transfer (RAFT) polymerization agents can be used, and can be selected from the free radical polymerization initiators that can be used in the synthesis of polymer A.

[0770] The organic solvent used in the synthesis of the polymer (α) may be any organic solvent that does not chemically react with the compound species constituting the copolymer and does not capture free radicals, and may be selected from organic solvents that can be used in the synthesis of the polymer A. The organic solvent may be used alone or in combination of two or more.

[0771] Furthermore, even a solvent that does not dissolve the produced polymer may be used by mixing with the above-mentioned organic solvent as long as the produced polymer does not precipitate.

[0772] In addition, in radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, and therefore, it is preferable to use an organic solvent that is degassed as much as possible.

[0773] When the graft copolymer obtained by the above polymerization is dissolved in the reaction solution, the reaction solution may be directly used for the preparation of the liquid crystal aligning agent, or the graft copolymer contained in the reaction solution may be separated and then used for the preparation of the liquid crystal aligning agent.

[0774] The polymerization temperature during free radical polymerization can be selected from any temperature of 30 to 150° C., preferably in the range of 50 to 100° C. In addition, the reaction can be carried out at any concentration. If the concentration is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 40% by mass. The reaction can be carried out at a high concentration at the beginning, and then an organic solvent can be added.

[0775] In the above-mentioned free radical polymerization reaction, if the ratio of the free radical polymerization initiator is large relative to the monomer, the molecular weight of the obtained polymer becomes small, and if the ratio of the free radical polymerization initiator is small relative to the monomer, the molecular weight of the obtained polymer becomes large, so the ratio of the free radical initiator is preferably 0.1 to 10 mol% relative to the monomer to be polymerized. In addition, various monomer components, solvents, initiators, etc. can also be added during polymerization.

[0776] The polymer generated by the reaction solution obtained by the above reaction can be recovered by putting the reaction solution into a poor solvent and precipitating it, but the reprecipitation treatment is not necessary. As the poor solvent used in the precipitation, there can be mentioned: methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. The polymer put into the poor solvent and precipitated can be filtered and recovered, and then dried at room temperature or heated under normal pressure or reduced pressure. In addition, if the operation of redissolving the recovered polymer in an organic solvent and reprecipitating and recovering it is repeated 2 to 10 times, the impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons, etc. can be mentioned. If more than 3 poor solvents selected from them are used, the efficiency of purification is further improved, so it is preferred.

[0777] The molecular weight of the polymer (α) constituting the strong anchor liquid crystal orientation agent having orientation limiting force in the azimuthal direction of the present invention is preferably 2000 to 1000000, and more preferably 5000 to 100000, when taking into account the strength of the obtained coating film, the operability during coating film formation, and the uniformity of the coating film, as measured by the GPC method.

[0778] (Polymer β (polymer that does not exhibit weak anchoring properties))

[0779] The polymer β is at least one polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyamide, and polyurea.

[0780] The polymer (β) is a polymer that does not exhibit weak anchoring properties, and plays a role in controlling the viscosity of a varnish (for example, a liquid crystal aligning agent) which is difficult to achieve with the polymer (α), optimizing the mechanical strength and sealing adhesion of the liquid crystal aligning film, and improving coating properties.

[0781] When the polymer (α) used together with the polymer (β) is a polymer (C) having a weak anchoring property, the polymer (β) plays a role in preventing the polymer (C) from eluting into the liquid crystal. Therefore, the polymer (β) reacts with the polymer (C) by heating, and therefore the polymer (β) needs to include a site that reacts with the polymer (C).

[0782] In order to react with the polymer (C) by heating, the polymer (β) is preferably a polymer containing at least one selected from an amino group, a protected amino group, a hydroxyl group, a protected hydroxyl group, a thiol group, a protected thiol group, a carboxyl group, a protected carboxyl group, an isocyanate group, a protected isocyanate group, a maleimide group, a carboxylic anhydride group, a vinyl group, an allyl group, a styryl group, a (meth)acrylic acid group and a (meth)acrylamide group as a site reactive with the polymer (C).

[0783] Here, the protecting group in the protective amino group, the protecting group in the protective hydroxyl group, the protecting group in the protective thiol group, the protecting group in the protective carboxyl group, and the protecting group in the protective isocyanate group refer to groups that are released by heating to generate an amino group, a hydroxyl group, a thiol group, a carboxyl group, and an isocyanate group, respectively.

[0784] Examples of the protecting group in the protected amino group include tert-butoxycarbonyl, benzyloxycarbonyl, 9-fluorenylmethoxycarbonyl, allyloxycarbonyl, phthaloyl, nitrobenzenesulfonyl, (2-trimethylsilyl)-ethanesulfonyl, 2,2,2-trichloroethoxycarbonyl and azido.

[0785] Examples of the protective group for protecting the hydroxyl group include a tetrahydropyranyl group, a methoxymethyl ether group, a trityl group, a tert-butyl group, a trialkylsilyl group, a tert-butoxycarbonyl group, a benzyl group, and an acetyl group.

[0786] Examples of the protecting group for protecting the thiol group include tert-butoxycarbonyl, benzyloxycarbonyl, 9-fluorenylmethoxycarbonyl, allyloxycarbonyl, phthaloyl, nitrobenzenesulfonyl, (2-trimethylsilyl)-ethanesulfonyl, 2,2,2-trichloroethoxycarbonyl and azido.

[0787] Examples of the protecting group for protecting the carboxyl group include methyl ester group, benzyl ester group, tert-butyl ester group and the like.

[0788] Examples of the protecting group for protecting the isocyanate group include a tert-butyl group, a dimethylpyrazolyl group, a methyl ethyl ketoxime group, and a lactam group.

[0789] The applicant has discovered that a weakly anchored liquid crystal alignment agent comprising a polymer such as polymer (C) (a polymer having a polymer unit compatible with liquid crystals and reacting with other polymers used in combination) is a weakly anchored liquid crystal alignment agent that can be easily manufactured and has good coating properties, and can provide a weakly anchored liquid crystal alignment film that has good adhesion to a sealant, does not produce a pretilt angle, and can simultaneously achieve low-voltage drive and high-speed response when the voltage is disconnected (OFF), and has filed an application (Japanese Patent Application No. 2022-6921 and WO2023 / 140322. The contents of the application are hereby incorporated into this specification to the same extent as if all were explicitly stated.).

[0790] The polymer (β) plays a role in controlling the viscosity of the varnish (for example, the liquid crystal aligning agent) which is difficult to achieve with the polymer (α), optimizing the mechanical strength and sealing adhesion of the liquid crystal aligning film, and improving the coating properties. Examples of polymers suitable for the polymer (β) include polyimide, polyamic acid, polyamic acid ester, polyamide and polyurea.

[0791] When polyamic acid, polyimide, or polyamic acid ester is used as polymer (β), there is a carboxyl group generated by the reaction of tetracarboxylic dianhydride and diamine, and there is a (anhydride) carboxylic acid or amino group at the terminal group of the polymer chain, so as long as the imidization rate is not 100%, all polyamic acids or polyimides are polymers (β) having carboxyl groups, for example, polymers that react with polymer (C) by heating. As polymer (β), for example, the following polymers containing diamine and tetracarboxylic dianhydride can be cited.

[0792] The following diamines can be mentioned as the diamine component used for the synthesis of polyamic acid and polyimide. Specifically, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dicarboxy-4,4′-diaminobiphenyl, 3,3 '-Difluoro-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyl diphenylamine, 3,3'-sulfonyl Diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4′-thiodiphenylamine, 3,3′-thiodiphenylamine, 4,4′-diaminodiphenylamine, 3,3′-diaminodiphenylamine, 3,4′-diaminodiphenylamine, 2,2′-diaminodiphenylamine, 2,3′-diaminodiphenylamine, N-methyl(4,4′-diaminodiphenyl)amine, N-methyl(3,3′-diaminodiphenyl)amine, N-methyl(3,4′-diaminodiphenyl)amine, N-methyl(2,2′-diaminodiphenyl)amine, N-methyl(2,3′-diaminodiphenyl)amine )amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4′-[1,4-phenylenebis(methylene)]diphenylamine, 4,4′-[1,3-phenylenebis(methylene)]diphenylamine, 3,4′-[1,4-phenylenebis(methylene)]diphenylamine, 3,4′-[1,3-phenylenebis(methylene)]diphenylamine, 3,3′-[1,4-phenylenebis(methylene)]diphenylamine, 3,3′-[1,3-phenylenebis(methylene)]diphenylamine 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N′-(1,4-phenylene)bis (4-aminobenzamide), N,N′-(1,3-phenylene)bis(4-aminobenzamide), N,N′-(1,4-phenylene)bis(3-aminobenzamide), N,N′-(1,3-phenylene)bis(3-aminobenzamide), N,N′-bis(4-aminophenyl)terephthalamide, N,N′-bis(3-aminophenyl)terephthalamide, N,N′-bis(4-aminophenyl)isophthalamide, N,N′-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4′-bis(4-aminophenoxy)diphenyl sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-amino-4-methylphenyl)propane, trans-1,4-bis(4-aminophenyl)cyclohexane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1, Aromatic diamines such as 9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane; bis(4-aminophenoxy) aliphatic diamines such as 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc.; 1,3-bis[2-( diamines having a urea structure such as [(p-aminophenyl)ethyl]urea, 1,3-bis[2-(p-aminophenyl)ethyl]-1-tert-butyloxycarbonylurea; diamines having a nitrogen-containing unsaturated heterocyclic structure such as N-p-aminophenyl-4-p-aminophenyl(tert-butyloxycarbonyl)aminomethylpiperidine; diamines having an N-Boc group (Boc represents tert-butyloxycarbonyl) such as N-tert-butyloxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine, etc.

[0793] The above-mentioned diamines can be used alone or in combination of two or more.

[0794] The tetracarboxylic dianhydride to be reacted with the diamine component is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3′,4,4′-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane alkane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3′,4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydiphthalic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclo butanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid, bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4.4.0]decane-2,4,7,9-tetracarboxylic acid, bicyclo[4.4.0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0. Dianhydrides of tetracarboxylic acids such as 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6.2.1.1.0<2,7>]dodecane-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2,3,5,6-tetracarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid.

[0795] Of course, the tetracarboxylic dianhydride can be used alone or in combination of two or more.

[0796] In the synthesis when the polymer is polyamic acid ester, the structure of the tetracarboxylic acid dialkyl ester to be reacted with the above-mentioned diamine component is not particularly limited, and specific examples thereof are given below.

[0797] Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, bicyclo[3.3.0] Octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3′,4,4′-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcyclooct-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0<2,5>]nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl ester, hexacyclo[6.6.0.1<2,7>.0<3,6>.1<9,14>.0<10,13>]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester, and the like.

[0798] Examples of the aromatic tetracarboxylic acid dialkyl esters include pyromellitic acid dialkyl esters, 3,3′,4,4′-biphenyltetracarboxylic acid dialkyl esters, 2,2′,3,3′-biphenyltetracarboxylic acid dialkyl esters, 2,3,3′,4′-biphenyltetracarboxylic acid dialkyl esters, 3,3′,4,4′-benzophenonetetracarboxylic acid dialkyl esters, 2,3,3′,4′-benzophenonetetracarboxylic acid dialkyl esters, bis(3,4-dicarboxyphenyl)ether dialkyl esters, bis(3,4-dicarboxyphenyl)sulfone dialkyl esters, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl esters, and 2,3,6,7-naphthalenetetracarboxylic acid dialkyl esters.

[0799] When the polymer (β) is a polyurea, an isocyanate group or an amino group is present at the terminal group of the polymer chain, so the entire polyurea is a polymer (β) having an isocyanate group or an amino group, which corresponds to a polymer reacted with the polymer (C) by heating, for example. Examples of such a polymer (β) include a polymer containing a diamine and a diisocyanate.

[0800] As a diamine, the diamine component used for synthesis|combination of the said polyamic acid and polyimide is mentioned, for example.

[0801] In the synthesis of polyurea, the diisocyanate to be reacted with the diamine component is not particularly limited, and can be used depending on availability, etc. The specific structure of the diisocyanate is shown below.

[0802] [Chemistry 88]

[0803]

[0804] In the formula, R2 and R3 represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0805] The aliphatic diisocyanates shown in formula (K-1) to (K-5) have poor reactivity, but have the advantage of improving solvent solubility, and the aromatic diisocyanates shown in formula (K-6) to (K-13) have the effect of being rich in reactivity and improving heat resistance, but can cite the disadvantage of reducing solvent solubility. In terms of versatility and characteristics, preferably formula (K-1), (K-7), (K-8), (K-9), (K-10), from the viewpoint of electrical characteristics, preferably formula (K-12), from the viewpoint of liquid crystal orientation, preferably formula (K-13). Diisocyanates can also be used in combination of two or more, preferably various applications according to the desired characteristics.

[0806] In addition, a part of diisocyanate may be replaced with the above-described tetracarboxylic dianhydride to use in the form of a copolymer of polyamic acid and polyurea, or in the form of a copolymer of polyimide and polyurea by chemical imidization.

[0807] When the polymer (β) is a polyamide, a carboxyl group or an amino group is present at the terminal group of the polymer chain, so that all the polyamides are polymers (β) having carboxyl groups or amino groups, and correspond to polymers that react with the polymer (C) by heating, for example. Examples of such polymers (β) include polymers containing dicarboxylic acids and diamines.

[0808] Examples of the dicarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and dicarboxylic acids containing a heterocyclic ring.

[0809] Examples of the aliphatic dicarboxylic acid include dicarboxylic acids such as malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, succinic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.

[0810] Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, Hexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-(2-norbornene)dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, camphoric acid, and the like.

[0811] Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4-anthraquinonedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4"-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenyl propane dicarboxylic acid, 4,4'-diphenyl hexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-bibenzyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-tolanethynyl dicarboxylic acid (4,4'-tolandicarboxylic dicarboxylic acids such as 4,4′-diphenylene diacetic acid, 4,4′-diphenylene dipropionic acid, 4-carboxycinnamic acid, p-phenylenedicarboxylic acid, 3,3′-[4,4′-(methylene di-p-phenylene)]dipropionic acid, 4,4′-[4,4′-(oxydi-p-phenylene)]dipropionic acid, 4,4′-[4,4′-(oxydi-p-phenylene)]dibutyric acid, (isopropylidene di-p-phenylenedioxy)dibutyric acid, and bis(p-carboxyphenyl)dimethylsilane.

[0812] Examples of the dicarboxylic acid containing a heterocyclic ring include 1,5-(9-oxofluorene)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid.

[0813] The dicarboxylic acids used may be substances having the structure of acid dihalides or acid anhydrides. In terms of maintaining the orientation of liquid crystal molecules, these dicarboxylic acids are particularly preferably dicarboxylic acids that can give polyamides with linear structures. Among them, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylethanedicarboxylic acid, 4,4′-diphenylpropanedicarboxylic acid, 4,4′-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis(phenyl)propanedicarboxylic acid, 4,4″-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid or their acid dihalides are preferably used. These compounds sometimes exist as isomers and may be mixtures containing them. In addition, two or more compounds may be used in combination. It should be noted that the dicarboxylic acids used in the present invention are not limited to the above-mentioned exemplified compounds.

[0814] When polyamic acid, polyamic acid ester, polyurea, and polyamide are obtained by reacting a diamine (also referred to as a "diamine component") as a raw material with a component selected from tetracarboxylic dianhydride (also referred to as a "tetracarboxylic dianhydride component"), a tetracarboxylic diester, a diisocyanate, and a dicarboxylic acid as a raw material, a known synthesis method can be used. Generally speaking, it is the following method: a diamine component is reacted with one or more components selected from tetracarboxylic dianhydride components, tetracarboxylic diesters, diisocyanates, and dicarboxylic acids in an organic solvent.

[0815] The polyamic acid can be synthesized by reacting a tetracarboxylic acid derivative component containing tetracarboxylic dianhydride with the diamine component in the presence of an organic solvent at -20 to 150°C, preferably 0 to 50°C (polycondensation reaction) for 30 minutes to 24 hours, preferably 1 to 12 hours.

[0816] Polyamic acid ester can be produced by known methods such as (1) a method of esterifying the above polyamic acid, (2) a method of reacting a tetracarboxylic acid derivative component containing a tetracarboxylic acid diester dichloride with the above diamine component, and (3) a method of polycondensing a tetracarboxylic acid derivative component containing a tetracarboxylic acid diester with diamine.

[0817] The polyimide can be synthesized by known methods such as (1) directly heating the solution of the polyamic acid or polyamic acid ester, (2) adding a catalyst (e.g., a basic catalyst such as pyridine, an acid anhydride such as acetic anhydride) to the solution of the polyamic acid or polyamic acid ester for catalytic imidization. It should be noted that the ring closure rate (also referred to as the imidization rate) of the functional group of the polyamic acid or polyamic acid ester of the polyimide of the present invention does not necessarily need to be 100%, and can be arbitrarily adjusted according to the use or purpose.

[0818] Polyurea can be synthesized by reacting the above-mentioned diisocyanate and the above-mentioned diamine component in the presence of an organic solvent at -20°C to 150°C, preferably 0 to 50°C (polycondensation reaction) for 30 minutes to 24 hours, preferably 1 to 12 hours.

[0819] The polyamide can be produced by a known method such as (1) a method of reacting a dicarboxylic acid dichloride derivative component with the above-mentioned diamine component, and (2) a method of polycondensing a dicarboxylic acid derivative component with a diamine.

[0820] As the organic solvent used in the synthesis of polymer (β), any organic solvent that does not chemically react with the compound species constituting the copolymer and does not capture free radicals can be selected from the organic solvents that can be used in the synthesis of the above-mentioned polymer (A). In addition, the organic solvent can be used alone or in combination of two or more.

[0821] The weight average molecular weight (Mw) of the polymer (β) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1000 to 500000, more preferably 2000 to 300000. In addition, the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the number average molecular weight (Mn) measured by GPC in terms of polystyrene is preferably 15 or less, more preferably 10 or less. By being in the above molecular weight range, excellent liquid crystal orientation can be exhibited, and excellent coating properties can be obtained regardless of the coating method.

[0822] (Other solvents)

[0823] The liquid crystal alignment agent of the present invention contains at least one specific solvent as a solvent component. As the organic solvent used in the liquid crystal alignment agent, other solvents other than the above-mentioned specific solvents can also be used. As the other solvents, for example: N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethylphosphoramide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol , ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, 2-ethyl-1,3-hexanediol, ethylene glycol, propylene glycol (1,2-propylene glycol), 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,5-hexanediol, 1,2-heptanediol, 1,3-heptanediol, 1,4-heptanediol, 1,5-heptanediol, 1,6-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,4-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,3-nonanediol, 1,5-nonanediol, 1,6-nonanediol, 1,9-nonanediol, 1,2-decanediol, 1,5-decanediol, 1,8-decanediol, 1,10-decanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, diethylene glycol, dipropylene glycol diol, dibutyl glycol, glycerol, 2-ethyl-1-hexanol, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, pentyl pyruvate, hexyl pyruvate, 2-ethylhexyl pyruvate, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, pentyl acetoacetate, hexyl acetoacetate, 2-ethylhexyl acetoacetate, methyl levulinate, ethyl levulinate, propyl levulinate, butyl levulinate, pentyl levulinate, hexyl levulinate, 2-ethylhexyl levulinate, propylene glycol, dimethyl ester, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl phthalate, dimethyl maleate, diethyl malonate, diethyl succinate, diethyl glutarate, diethyl adipate, diethyl phthalate, diethyl maleate, dipropyl malonate, dipropyl succinate, dipropyl glutarate, dipropyl adipate, dipropyl phthalate, dipropyl maleate, dibutyl malonate, dibutyl succinate, dibutyl glutarate, dibutyl adipate, dibutyl phthalate, dibutyl maleate, dibutyl malonate As long as they can be used as solvents, other solvents can be mentioned, such as amyl ester, diamyl succinate, diamyl glutarate, diamyl adipate, diamyl phthalate, diamyl maleate, dihexyl malonate, dihexyl succinate, dihexyl glutarate, dihexyl adipate, dihexyl phthalate, dihexyl maleate, di-2-ethylhexyl malonate, 2-ethylhexyl succinate, 2-ethylhexyl glutarate, 2-ethylhexyl adipate, 2-ethylhexyl phthalate, 2-ethylhexyl maleate, etc. These organic solvents can be used alone or in combination.

[0824] Although content of the organic solvent other than the specific solvent in the liquid crystal aligning agent is not particularly limited, it is preferably 10 to 90 mass % of the whole solvent contained in the liquid crystal aligning agent, and more preferably 20 to 70 mass %.

[0825] Furthermore, it is preferable to use a solvent that improves the uniformity and smoothness of the coating film in a mixture with an organic solvent having high solubility.

[0826] Examples of the solvent for improving the uniformity and smoothness of the coating film include isopropyl alcohol, methoxymethylpentyl alcohol, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether , dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isopentyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol , 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, 2-ethyl-1-hexanol, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, pentyl pyruvate, hexyl pyruvate, 2-ethylhexyl pyruvate, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, pentyl acetoacetate, hexyl acetoacetate, 2-ethylhexyl acetoacetate, methyl levulinate, ethyl levulinate, propyl levulinate, butyl levulinate, pentyl levulinate, hexyl levulinate, acetoacetate 2-ethylhexyl malonate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl phthalate, dimethyl maleate, diethyl malonate, diethyl succinate, diethyl glutarate, diethyl adipate, diethyl phthalate, diethyl maleate, dipropyl malonate, dipropyl succinate, dipropyl glutarate, dipropyl adipate, Dipropyl phthalate, dipropyl maleate, dibutyl malonate, dibutyl succinate, dibutyl glutarate, dibutyl adipate, dibutyl phthalate, dibutyl maleate, dipentyl malonate, dipentyl succinate, dipentyl glutarate, dipentyl adipate, dipentyl phthalate, dipentyl maleate, dihexyl malonate, dihexyl succinate, dihexyl glutarate,Dihexyl adipate, dihexyl phthalate, dihexyl maleate, di-2-ethylhexyl malonate, 2-ethylhexyl succinate, 2-ethylhexyl glutarate, 2-ethylhexyl adipate, 2-ethylhexyl phthalate, 2-ethylhexyl maleate, etc. These solvents can be mixed in multiple forms. When using these solvents, it is preferably 5 to 60% by mass of the total solvent contained in the liquid crystal aligning agent, and more preferably 10 to 40% by mass.

[0827] The liquid crystal aligning agent of the present invention may also contain ingredients other than those mentioned above. Examples thereof include: compounds that improve the uniformity of film thickness and surface smoothness when the composition contained in the liquid crystal aligning agent is applied, compounds that improve the adhesion between the composition contained in the liquid crystal aligning agent and the substrate, and compounds that further improve the film strength of the composition contained in the liquid crystal aligning agent.

[0828] As compounds for improving film thickness uniformity and surface smoothness, fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc. can be cited. More specifically, for example, EFTOP EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFAC F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by 3M Corporation), AsahiGuard AG710 (manufactured by AGC Corporation), SURFLONS-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimei Chemical Co., Ltd.), etc. can be cited.

[0829] When using these surfactants, the usage ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the polymer contained in the composition contained in the weak anchor liquid crystal aligning agent.

[0830] Specific examples of compounds that improve the adhesion between the composition contained in the liquid crystal alignment agent and the substrate include compounds containing functional silanes, compounds containing epoxy groups, etc. For example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, 3-ureidopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethyl Oxycarbonyl-3-aminopropyltriethoxysilane, N-(3-triethoxysilyl)propyltriethylenetetramine, N-(3-trimethoxysilyl)propyltriethylenetetramine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltriethoxysilane, Methoxysilane, N-benzyl-3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether Glycerol ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N′,N′-tetraglycidyl-m-phenylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, etc.

[0831] In addition, in order to further improve the film strength of the liquid crystal alignment film, phenol compounds such as 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane and tetrakis(methoxymethyl)bisphenol may be added. When these compounds are used, the total amount of the polymer contained in the weak anchor liquid crystal alignment agent is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass.

[0832] Furthermore, the composition contained in the liquid crystal aligning agent may contain a dielectric or conductive material for changing electrical properties such as the dielectric constant and conductivity of the weak anchor liquid crystal aligning film in addition to the above, within a range not impairing the effects of the present invention.

[0833] (Liquid crystal alignment film and liquid crystal display element)

[0834] The liquid crystal display element of the present invention is provided with a liquid crystal alignment film formed using the above-mentioned liquid crystal alignment agent. The working mode of the liquid crystal display element can be selected according to the type of polymer (α) used. For example, when the polymer (α) is a polymer that helps to show weak anchoring, namely polymer (A), polymer (B), polymer (C), or when the polymer (α) is a polymer that constitutes a strong anchoring liquid crystal alignment agent with an orientation limiting force in the horizontal direction, it is preferably an in-plane switching type (IPS type, FFS type) or an optical compensation bending type (OCB type). When the polymer (α) is a polymer that constitutes a liquid crystal alignment agent with an orientation limiting force in the azimuthal direction, the vertical alignment type (UV2A type) is preferred.

[0835] The liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (4).

[0836] <Step (1): Step of applying a liquid crystal aligning agent onto a substrate>

[0837] The step (1) is a step of applying a liquid crystal aligning agent on a substrate. Specific examples of the step (1) are shown below.

[0838] On one side of a substrate provided with a patterned transparent conductive film, a liquid crystal alignment agent is applied by an appropriate coating method such as a roller coating method, a spin coating method, a printing method, an inkjet method or a spray coating method. Here, as the material of the substrate, there is no particular limitation as long as it is a substrate with high transparency, and plastics such as acrylic acid and polycarbonate can be used together with glass and silicon nitride. In addition, in a reflective liquid crystal display element, if it is only a single-sided substrate, even opaque materials such as silicon wafers can be used, and the electrodes in this case can also use materials such as aluminum that reflect light. In addition, in the case of manufacturing an IPS type or FFS type liquid crystal display element, a substrate having an electrode patterned as a comb-shaped transparent conductive film or metal film and an opposing substrate without an electrode are used.

[0839] An IPS substrate, which is a comb-tooth electrode substrate used in an IPS type liquid crystal display element, has, for example, a substrate, a plurality of linear electrodes formed on the substrate and arranged in a comb-tooth shape, and a liquid crystal alignment film formed on the substrate so as to cover the linear electrodes.

[0840] It should be noted that the comb-tooth electrode substrate used in the FFS type liquid crystal display element, namely the FFS substrate, has, for example: a substrate, a surface electrode formed on the substrate, an insulating film formed on the surface electrode, a plurality of linear electrodes formed on the insulating film and arranged in a comb-tooth shape, and a liquid crystal orientation film formed in a manner covering the linear electrodes on the insulating film.

[0841] More preferred examples of methods for coating the liquid crystal alignment agent on a substrate and forming a film include: screen printing, offset printing, flexographic printing and other printing methods, spin coating, inkjet, spray coating, etc. Among them, flexographic printing, spin coating, or coating and film forming methods using inkjet can be preferably used.

[0842] The weakly anchored liquid crystal display element is produced using a first substrate or a second substrate having a weakly anchored alignment film formed using the weakly anchored liquid crystal alignment agent of the present invention, and a second substrate or a first substrate having a strongly anchored horizontal alignment film. It should be noted that in the present invention, the first substrate may be a substrate having a comb-tooth electrode, and the second substrate may be an opposing substrate. In addition, the second substrate may be a substrate having a comb-tooth electrode, and the first substrate may be an opposing substrate.

[0843] <Step (2): Step of calcining the applied liquid crystal aligning agent>

[0844] The step (2) is a step of baking the liquid crystal aligning agent applied on the substrate to form a film. A specific example of the step (2) is shown below.

[0845] After the liquid crystal alignment agent is applied to the substrate in step (1), the solvent can be evaporated or the thermal imidization of the polyamic acid can be performed by heating means such as a heating plate, a heat circulation oven or an IR (infrared) oven. The drying and firing steps after the application of the liquid crystal alignment agent can be performed at any temperature and time, and can be performed multiple times. The temperature for firing the liquid crystal alignment agent can be, for example, 40 to 180°C. From the perspective of shortening the process, it can be performed at 40 to 150°C. The firing time is not particularly limited, and 1 to 10 minutes or 1 to 5 minutes can be mentioned. In the case of thermal imidization of polyamic acid, after the above-mentioned step, a firing step such as 150 to 300°C or 150 to 250°C can be added. The firing time is not particularly limited, and 5 to 40 minutes or 5 to 30 minutes can be mentioned.

[0846] If the film thickness of the film-like material after firing is too thin, the reliability of the liquid crystal display element may decrease, so it is preferably 5 to 300 nm, and more preferably 10 to 200 nm.

[0847] <Step (3): Step of orienting the film obtained in step (2)>

[0848] Step (3) is a step of performing an orientation treatment on the film obtained in step (2) according to the circumstances. That is, in a horizontally oriented liquid crystal display element such as an IPS mode or an FFS mode, the coating film is treated to impart uniaxial orientation ability in the horizontal direction. In addition, regarding the weakly anchored liquid crystal orientation agent coated substrate in the weakly anchored liquid crystal display element, the fired coating film can be directly used as a liquid crystal orientation film, but the coating film can also be treated to impart orientation ability. On the other hand, in a vertically oriented liquid crystal display element such as a UV2A mode, the coating film is treated to impart uniaxial orientation ability in the azimuth direction. As an orientation treatment method for a liquid crystal orientation film, a rubbing orientation treatment method and a photo-orientation treatment method can be cited. As a photo-orientation treatment method, a method of irradiating the surface of the above-mentioned film-like object with radiation deflected in a certain direction, preferably performing a heat treatment at a temperature of 150 to 250° C. according to the circumstances, to impart liquid crystal orientation (also referred to as liquid crystal orientation ability) can be cited. As radiation, ultraviolet rays or visible light having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferred, and ultraviolet rays having a wavelength of 200 to 380 nm are more preferred.

[0849] The radiation dose is preferably 1 to 10000 mJ / cm 2 , among which 100 to 5000 mJ / cm 2 In addition, when irradiating with radiation, the irradiation may be performed while heating the substrate having the film-like material at 50° C. to 250° C. in order to improve the liquid crystal orientation. The liquid crystal alignment film produced in this way can stably align liquid crystal molecules in a certain direction.

[0850] Furthermore, the coating film irradiated with polarized radiation or subjected to rubbing orientation treatment by the above method may be subjected to contact treatment using water or a solvent. In addition, the film subjected to the above orientation treatment may be subjected to heat treatment without being subjected to contact treatment. Furthermore, the film subjected to the above contact treatment may be further subjected to heat treatment.

[0851] The solvent used in the contact treatment is not particularly limited as long as it is a solvent that dissolves decomposition products generated by the film-like material upon irradiation with radiation. Specific examples thereof include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, and the like.

[0852] The solvent may be used alone or in combination of two or more.

[0853] The temperature of the heat treatment of the coating film irradiated with radiation is more preferably 50 to 300° C., and further preferably 120 to 250° C. The time of the heat treatment is preferably 1 to 30 minutes.

[0854] <Step (4): Step of producing a liquid crystal cell>

[0855] Two substrates on which the liquid crystal alignment films are formed as described above are prepared, and liquid crystal is arranged between the two substrates arranged to face each other. Specifically, the following two methods are exemplified.

[0856] The first method is to firstly place two substrates opposite to each other with a gap (cell gap) between the liquid crystal alignment films, then use a sealant to bond the peripheries of the two substrates together, inject a liquid crystal composition into the substrate surface and the cell gap divided by the sealant to make contact with the film surface, and then seal the injection hole.

[0857] In addition, the second method is a method called ODF (One Drop Fill) method. A sealant such as a UV-curable sealant is applied at a predetermined position on one of the two substrates on which a liquid crystal alignment film is formed, and a liquid crystal composition is further dripped at a predetermined plurality of positions on the surface of the liquid crystal alignment film. Then, another substrate is bonded in a manner that the liquid crystal alignment film is opposite to each other, so that the liquid crystal composition is spread over the entire surface of the substrate and contacts the film surface. Next, ultraviolet light is irradiated on the entire surface of the substrate to cure the sealant. In the case of using any method, it is expected that the liquid crystal composition used will be further heated to a temperature at which it becomes an isotropic phase, and then slowly cooled to room temperature, thereby removing the flow orientation during liquid crystal filling.

[0858] When the coating film is subjected to a rubbing orientation treatment, the two substrates are disposed facing each other so that the rubbing directions of the coating films form a predetermined angle, for example, orthogonal or antiparallel.

[0859] As a sealant, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. As the above-mentioned liquid crystal composition, there is no particular limitation, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having a positive or negative dielectric anisotropy can be used. It should be noted that, hereinafter, a liquid crystal composition having a positive dielectric anisotropy is also referred to as a positive liquid crystal, and a liquid crystal composition having a negative dielectric anisotropy is also referred to as a negative liquid crystal.

[0860] The above-mentioned liquid crystal composition may contain liquid crystal compounds having fluorine atoms, hydroxyl groups, amino groups, fluorine-containing groups (for example, trifluoromethyl groups), cyano groups, alkyl groups, alkoxy groups, alkenyl groups, isothiocyanate groups, heterocyclic rings, cycloalkanes, cycloolefins, steroid skeletons, benzene rings, or naphthalene rings, and may also contain compounds having two or more rigid parts (liquid crystal unit skeletons) that exhibit liquid crystal properties in the molecule (for example, a bimesogen compound in which two rigid biphenyl structures or terphenyl structures are connected by an alkylene group).

[0861] Examples of the liquid crystal composition include a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, and a liquid crystal composition exhibiting a cholesteric phase. Among them, a liquid crystal composition exhibiting a nematic phase is preferred.

[0862] In addition, from the viewpoint of improving the orientation of the liquid crystal, the liquid crystal composition may further contain additives. Such additives include: photopolymerizable monomers such as compounds having polymerizable groups; optically active compounds (for example, S-811 manufactured by Merck Co., Ltd.); antioxidants; ultraviolet absorbers; pigments; defoamers; polymerization initiators; or polymerization inhibitors, etc.

[0863] As a positive liquid crystal, ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, or MLC-7081 manufactured by Merck is mentioned, for example.

[0864] As a negative liquid crystal, MLC-6608, MLC-6609, MLC-6610, or MLC-7026-100 manufactured by Merck is mentioned, for example.

[0865] The liquid crystal aligning film of the present invention is also preferably used for the following liquid crystal display elements.

[0866] A liquid crystal display element (PSA type liquid crystal display element) is manufactured by the following steps: a liquid crystal layer is provided between a pair of substrates having electrodes, a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat is arranged between the pair of substrates, a voltage is applied between the electrodes, and the polymerizable compound is polymerized by at least one of irradiation with active energy rays and heating.

[0867] Moreover, the liquid crystal aligning film of this invention is also preferably used for the following liquid crystal display element.

[0868] A liquid crystal display element (SC-PVA mode liquid crystal display element) is manufactured through the following steps: a liquid crystal layer is provided between a pair of substrates having electrodes, a liquid crystal orientation film containing polymerizable groups that are polymerized by at least one of active energy rays and heat is arranged between the pair of substrates, and a voltage is applied between the electrodes.

[0869] Furthermore, a polarizing plate is bonded to the outer surface of the liquid crystal cell as required, thereby obtaining a liquid crystal display element. Examples of the polarizing plate bonded to the outer surface of the liquid crystal cell include a polarizing plate formed by sandwiching a polarizing film called "H film" that absorbs iodine while stretching and orienting polyvinyl alcohol with a cellulose acetate protective film, or a polarizing plate containing the H film itself.

[0870] Figure 1 1 is a schematic cross-sectional view showing an example of a lateral electric field liquid crystal display element of the present invention, which is an example of an IPS mode liquid crystal display element.

[0871] exist Figure 1 In the illustrated transverse electric field liquid crystal display element 1, liquid crystal 3 is sandwiched between a comb-tooth electrode substrate 2 having a liquid crystal orientation film 2c and an opposing substrate 4 having a liquid crystal orientation film 4a. The comb-tooth electrode substrate 2 has: a substrate 2a, a plurality of linear electrodes 2b formed on the substrate 2a and arranged in a comb-tooth shape, and a liquid crystal orientation film 2c formed on the substrate 2a in a manner covering the linear electrodes 2b. The opposing substrate 4 has: a substrate 4b, and a weakly anchored liquid crystal orientation film or a strongly anchored horizontal orientation film (liquid crystal orientation film 4a) formed on the substrate 4b. The liquid crystal orientation film 2c is, for example, a weakly anchored orientation film or a strongly anchored horizontal orientation film of the present invention. The liquid crystal orientation films of the opposing substrates can be made by combining a strongly anchored orientation film and a weakly anchored liquid crystal orientation film.

[0872] In the lateral electric field liquid crystal display element 1 , when a voltage is applied to the linear electrodes 2 b , an electric field is generated between the linear electrodes 2 b as indicated by electric field lines L.

[0873] Figure 2 1 is a schematic cross-sectional view showing another example of the lateral electric field liquid crystal display element of the present invention, which is an example of an FFS-type liquid crystal display element.

[0874] exist Figure 2In the illustrated lateral electric field liquid crystal display element 1, liquid crystal 3 is sandwiched between a comb-tooth electrode substrate 2 having a liquid crystal alignment film 2h and an opposing substrate 4 having a liquid crystal alignment film 4a. The comb-tooth electrode substrate 2 has: a substrate 2d, a surface electrode 2e formed on the substrate 2d, an insulating film 2f formed on the surface electrode 2e, a plurality of linear electrodes 2g formed on the insulating film 2f and arranged in a comb-tooth shape, and a liquid crystal alignment film 2h formed on the insulating film 2f in a manner covering the linear electrodes 2g. The opposing substrate 4 has: a substrate 4b, and a liquid crystal alignment film 4a formed on the substrate 4b. The liquid crystal alignment film 4a and the above-described Figure 1 The liquid crystal alignment film 2h is the same as the liquid crystal alignment film 4a described above. Figure 1 The same as the liquid crystal alignment film 2c in.

[0875] In the lateral electric field liquid crystal display element 1 , when a voltage is applied to the surface electrode 2 e and the linear electrode 2 g , an electric field is generated between the surface electrode 2 e and the linear electrode 2 g as indicated by the electric field lines L.

[0876] Example

[0877] The present invention will be described in detail below with reference to Examples, but the present invention is not to be construed as being limited to these Examples. The abbreviations of the compounds and the methods for measuring the properties are as follows.

[0878] ((Component A) component compatible with liquid crystal)

[0879] [Chemistry 89]

[0880]

[0881] ((Component B) a component that is incompatible with liquid crystal or becomes incompatible by firing)

[0882] [Chemistry 90]

[0883]

[0884] Me represents a methyl group, and Et represents an ethyl group.

[0885] (Vertical oriented side chain)

[0886] [Chemistry 91]

[0887]

[0888] (RAFT Agent)

[0889] [Chemistry 92]

[0890]

[0891] (Removal of RAFT Agent)

[0892] [Chemistry 93]

[0893]

[0894] (Chain transfer agent)

[0895] [Chemistry 94]

[0896]

[0897] (Me represents methyl.)

[0898] (Polymerization initiator)

[0899] [Chemistry 95]

[0900]

[0901] VA-086 used was a product manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0902] (Diamine)

[0903] [Chemistry 96]

[0904]

[0905] (Boc represents tert-butyloxycarbonyl.)

[0906] (Tetracarboxylic dianhydride)

[0907] [Chemistry 97]

[0908]

[0909] (additive)

[0910] [Chemistry 98]

[0911]

[0912] (Solvent)

[0913] THF: Tetrahydrofuran

[0914] NMP: N-methyl-2-pyrrolidone

[0915] PGMEA: Propylene glycol monomethyl ether acetate

[0916] DEAc: N,N-diethylacetamide

[0917] DPAc: N,N-dipropylacetamide

[0918] 3MMP: 3-methoxy-N,N-dimethylpropionamide

[0919] DEPA: N,N-diethylpropionamide

[0920] DEF: Diethylformamide

[0921] 2MEA: 2-methoxy-N,N-diethylacetamide

[0922] 3MEP: 3-methoxy-N,N-diethylpropionamide

[0923] 4OEP: 4-Oxo-N,N-diethylpentanamide

[0924] ECHC: N,N-Diethylcyclohexanecarboxamide

[0925] DBF: N,N-dibutylformamide

[0926] DMAc: dimethylacetamide

[0927] DMF: dimethylformamide

[0928] PB: Propylene glycol monobutyl ether

[0929] BCS: Ethylene glycol monobutyl ether

[0930] BCAc: Ethylene glycol monobutyl ether acetate

[0931] Among the above solvents, DEAc, DPAc, 3MMP, DEPA, DEF, 2MEA, 3MEP, 4OEP, ECHC and DBF are specific solvents.

[0932] (Viscosity measurement)

[0933] The viscosity of the polyamic acid solution or the like was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) at a sample volume of 1.1 mL (milliliter), a conical rotor TE-1 (1°34′, R24), and a temperature of 25°C.

[0934] (Determination of Molecular Weight of Polymer α)

[0935] The molecular weight of the polymer (α) was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (CBM-20A) (manufactured by Shimadzu Corporation) and a column (Shodex (registered trademark) KF-804L and KF-803L connected in series) (manufactured by Showa Denko K.K.).

[0936] Column temperature: 40°C

[0937] Eluent: Tetrahydrofuran

[0938] Flow rate: 1.0mL / min

[0939] Standard sample for preparing calibration curve: Standard polystyrene (molecular weight: 197000, 55100, 12800, 3950, 1260) (manufactured by Tosoh Corporation)

[0940] (Determination of Molecular Weight of Polymer β)

[0941] The molecular weight of the polymer (β) was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200 (manufactured by Senshu Scientific Co., Ltd.) and a column (Shodex (registered trademark) KD-803 and KD-805 connected in series) (manufactured by Showa Denko K.K.).

[0942] Column temperature: 50°C

[0943] Eluent: DMF (as additives, lithium bromide monohydrate (LiBr·H2O) 30mmol / L, phosphoric acid·anhydrous crystals (orthophosphoric acid) 30mmol / L, THF 10ml / L),

[0944] Flow rate: 1.0mL / min

[0945] Standard samples for preparing the calibration curve: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight approximately 900,000, 150,000, 100,000, 30,000) and polyethylene glycol manufactured by Polymer Laboratories (molecular weight approximately 12,000, 4,000, 1,000)

[0946] <Synthesis of a polymer composed of one block segment>

[0947] (Synthesis Example 1-1)

[0948] A-1 (10.0 g, 70.3 mmol), R-3 (482 mg, 1.19 mmol) and AIBN (97.9 mg, 0.597 mmol) were measured in a 100 ml eggplant flask equipped with a stirrer and a nitrogen inlet tube, THF (10.6 g) was added, and after stirring at room temperature to dissolve, the system was replaced with nitrogen, and heated and stirred in an oil bath set at 60°C for 12 hours. After heating and stirring, methanol (50 g) was gently injected into the reaction solution while stirring to precipitate the solid, and stirred for 30 minutes. The precipitate was separated by filtration, and the slurry was washed with methanol (50 g) for a total of 2 times for 30 minutes, and the solid was vacuum dried at 50°C to obtain a polymer (p(A-1)). Number average molecular weight (Mn): 7500, weight average molecular weight (Mw): 8200.

[0949] (Synthesis Examples 1-2 to 1-31)

[0950] The same procedure as in Synthesis Example 1-1 is carried out except that the type of raw materials (monomers), type of initiator, type of controller, molar ratio of raw materials to controller [(controller / raw material)×100] and amount used are replaced with those shown in the following Table 1-1 or Table 1-2, thereby obtaining polymers (p(A-2) to (p(C-3 / B-6 / B-8)) shown in the following Tables 1-1 and 1-2.

[0951] [Table 1-1]

[0952]

[0953] [Table 1-2]

[0954]

[0955] <Synthesis of homopolymer using terminal group conversion>

[0956] (Synthesis example 1-32)

[0957] In a 50 ml eggplant-shaped flask equipped with a stirrer and a nitrogen inlet tube, p(A-2) (5.00 g, 0.562 mmol) obtained in Synthesis Example 1-2 was measured, THF (5.34 g) was added, and it was stirred at room temperature to dissolve. The system was substituted with nitrogen, AM-1 (338 mg, 5.62 mmol) was added, and it was stirred at room temperature for 6 hours. Confirm that the reaction solution has become transparent, and while stirring methanol (40 g), the reaction solution is gently injected to precipitate the solid, and stirred for 30 minutes. The precipitate was separated by filtration, and the slurry was washed with methanol (40 g) for a total of 2 times for 30 minutes, and the solid was vacuum dried at 50°C to obtain a homopolymer p(A-2)P. Number average molecular weight (Mn): 8800, weight average molecular weight (Mw): 9600.

[0958] <Synthesis of diblock polymer>

[0959] (Synthesis example 2-1)

[0960] In a 100 ml eggplant-shaped flask equipped with a stirrer and a nitrogen inlet tube, p(A-1) (3.15 g, 0.443 mmol), B-3 (6.90 g, 27.5 mmol) and AIBN (36.4 mg, 0.222 mmol) obtained in Synthesis Example 1-1 were weighed, THF (10.1 g) was added, and after stirring at room temperature to dissolve, the system was replaced with nitrogen, and heated and stirred in an oil bath set at 60°C for 12 hours. After heating and stirring, methanol (50 g) was gently injected into the reaction solution while stirring to precipitate the solid, and stirred for 30 minutes. The precipitate was separated by filtration, and the slurry was washed with methanol (50 g) for a total of 2 times for 30 minutes, and the solid was vacuum dried at 50°C to obtain a copolymer (BC-1). Number average molecular weight: 20500, weight average molecular weight: 22600.

[0961] (Synthesis Examples 2-2 to 2-38)

[0962] Polymers (BC-2) to (BC-38) shown in Tables 2-1 and 2-2 were obtained in the same manner as in Synthesis Example 2-1 except that the types of raw materials (monomers) used were changed to those shown in Table 2-1 or 2-2 below.

[0963] [Table 2-1]

[0964]

[0965] [Table 2-2]

[0966]

[0967] <Synthesis of triblock polymer>

[0968] (Synthesis example 3-1)

[0969] In a 100 ml eggplant flask equipped with a stirrer and a nitrogen inlet tube, BC-27 (5.23 g, 0.312 mmol), B-3 (4.90 g, 19.5 mmol) and AIBN (25.6 mg, 0.156 mmol) obtained in Synthesis Example 2-27 were weighed, THF (10.2 g) was added, and after stirring at room temperature to dissolve, the system was replaced with nitrogen, and heated and stirred in an oil bath set at 60°C for 12 hours. After heating and stirring, methanol (50 g) was gently injected into the reaction solution while stirring to precipitate the solid, and stirred for 30 minutes. The precipitate was separated by filtration, and the slurry was washed with methanol (50 g) for a total of 2 times for 30 minutes, and the solid was vacuum dried at 50°C to obtain a copolymer (BC-39). Number average molecular weight (Mn): 30800, weight average molecular weight (Mw): 40100.

[0970] (Synthesis Examples 3-2 to 3-6)

[0971] Polymers (BC-40) to (BC-44) shown in Table 3 below were obtained in the same manner as in Synthesis Example 3-1 except that the types of raw materials (monomers) and initiators used were changed to those shown in Table 3 below.

[0972] [Table 3]

[0973]

[0974] <Synthesis of macromonomer>

[0975] (Synthesis Example 4-1)

[0976] A-9 (10.00 g, 78.0 mmol), S-4 (0.216 g, 2.34 mmol) and AIBN (0.128 g, 0.780 mmol) were weighed in a 100 ml eggplant flask equipped with a stirrer and a nitrogen inlet tube, THF (10.3 g) was added, and after stirring at room temperature to dissolve, the system was replaced with nitrogen, and heated and stirred in an oil bath set at 60°C for 12 hours. After heating and stirring, cold methanol (30.0 g) was gently injected into the reaction solution while stirring to precipitate the solid, and stirred for 30 minutes. The precipitate was separated by filtration, and the slurry was washed with cold methanol (30.0 g) for a total of 2 times for 30 minutes, and the solid was vacuum dried at 50°C to obtain a prepolymer. Mn: 6000, Mw: 9900.

[0977] The prepolymer (10.0 g, 1.67 mmol), B-6 (0.829 g, 5.83 mmol), hydroquinone (8.1 mg), N,N-dimethyllaurylamine (2.0 mg) and xylene (20.0 g) synthesized by the above method were added to a 100 ml eggplant flask equipped with a stirrer and a nitrogen inlet tube, and stirred at room temperature to dissolve, and then heated and stirred in an oil bath set at 140°C for 6 hours. After heating and stirring, methanol (50.0 g) was gently injected into the reaction solution while stirring to precipitate the solid, and stirred for 30 minutes. The precipitate was separated by filtration, and the slurry was washed with methanol (50.0 g) for a total of 30 minutes twice, and the solid was vacuum dried at 50°C to obtain a macromonomer pM (A-9). Mn: 6100, Mw: 9900.

[0978] (Synthesis Examples 4-2 to 4-3)

[0979] The same procedure as in Synthesis Example 4-1 was carried out except that the type of raw material (component A) and the molar ratio of the raw material to the chain transfer agent (S-4) [(raw material / S-4)] were changed as shown in Table 4, thereby obtaining the macromonomers pM (A-2) and pM (A-8) shown in the following Table 4.

[0980] [Table 4]

[0981]

[0982] <Synthesis of Graft Copolymer>

[0983] (Synthesis Example 5-1)

[0984] In a 100 ml eggplant flask equipped with a stirrer and a nitrogen inlet tube, pM (A-9) (1.00 g, 0.167 mmol), B-1 (4.10 g, 16.5 mmol) and AIBN (82.1 mg, 0.500 mmol) were measured, THF (7.77 g) was added, and after stirring at room temperature to dissolve, the system was replaced with nitrogen, and heated and stirred in an oil bath set at 60°C for 12 hours. After heating and stirring, methanol (40 g) was gently injected into the reaction solution while stirring to precipitate the solid, and stirred for 30 minutes. The precipitate was separated by filtration, and the slurry was washed with methanol (40 g) for a total of 2 times for 30 minutes, and the solid was vacuum dried at 50°C to obtain a graft copolymer (GP-1). Number average molecular weight (Mn): 88700, weight average molecular weight (Mw): 172900.

[0985] (Synthesis Examples 5-2 to 5-16)

[0986] Graft copolymers (GP-2) to (GP-16) shown in Table 5 were obtained in the same manner as in Synthesis Example 5-1 except that the types, charge amounts and polymerization concentrations of the raw materials (monomers) used were changed to those shown in Table 5 below.

[0987] [Table 5]

[0988]

[0989] <Synthesis of polymer> (Synthesis Example 6)

[0990] In a 100 ml eggplant flask equipped with a stirrer and a nitrogen inlet tube, 2-((2-bromo-2-methylpropanoyl)oxy)ethyl methacrylate (5.00 g, 17.91 mmol), B-7 (0.078 g, 0.60 mmol), R-3 (0.72 g, 1.80 mmol) and AIBN (0.09 g, 0.54 mmol) were weighed, THF (10.2 g) was added, and after stirring at room temperature to dissolve, the system was replaced with nitrogen, and heated and stirred in an oil bath set at 60° C. for 12 hours. After heating and stirring, methanol (50.0 g) was gently injected into the reaction solution while stirring to precipitate a solid, and stirred for 30 minutes. The precipitate was collected by filtration, and slurry washing was performed again with methanol (50.0 g) twice for 30 minutes in total, and the solid was vacuum dried at 50° C. to obtain a prepolymer. Mn: 45,300, Mw: 68,000.

[0991] In a 50 ml eggplant flask equipped with a stirrer and a nitrogen inlet tube, the prepolymer synthesized by the above method (2.00 g, 0.03 mmol), B-1 (0.43 g, 1.76 mmol), A-2 (3.00 g, 17.62 mmol), ethyl 2-bromoisobutyrate (0.012 g, 0.06 mmol), CuBr (0.03 g, 0.19 mmol), N,N,N′,N″,N″-pentamethyldiethylenetriamine (0.043 g, 0.25 mmol) and anisole (7.5 g) were added, stirred at room temperature to dissolve, and then refrigerated degassed three times, and heated and stirred in an oil bath set at 90°C for 6 hours. After heating and stirring, methanol (50.0 g) was gently injected into the reaction solution while stirring to precipitate solids, and stirred for 30 minutes. The precipitate was separated by filtration, and the slurry was washed with methanol (50.0 g) twice for a total of 30 minutes, and the solid was vacuum dried at 50°C to obtain a bottle brush polymer (BBP-1). Mn: 203000, Mw: 384000.

[0992] <Synthesis of polyamic acid and polyimide>

[0993] (Synthesis Example 7-1)

[0994] DA-1 (0.433 g: 4.00 mmol), DA-2 (1.47 g: 6.00 mmol), DA-3 (1.92 g: 6.00 mmol) and DA-7 (1.37 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DEAc (68.6 g) was added, and after stirring to dissolve under a nitrogen atmosphere, TC-1 (4.17 g: 18.6 mmol) was added while maintaining at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-1) having a viscosity of about 370 mPa·s and a solid content concentration of 12% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 13,300 and a weight average molecular weight of 29,900.

[0995] (Synthesis Example 7-2)

[0996] In a 300 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, the polyamic acid solution (PAA-1) (40.0 g) obtained above was measured, DEAc (13.3 g) was added and stirred at room temperature for a while, and then acetic anhydride (3.14 g: 30.8 mmol) and pyridine (0.812 g, 10.3 mmol) were added, and stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then reacted at 50° C. for 3 hours under a nitrogen atmosphere. After the reaction was completed, the reaction solution was slowly injected into methanol (170 mL) cooled to below 10° C. while stirring to precipitate the solid, and stirred for 10 minutes. The precipitate was separated by filtration, and the slurry was washed with methanol (170 mL) for a total of 30 minutes twice, and the solid was vacuum dried at 80° C., thereby obtaining the target polyimide powder (SPI-1) (4.15 g, yield 86%). The imidization rate of the polyimide was 60%, and the number average molecular weight was 12,800 and the weight average molecular weight was 27,500.

[0997] (Synthesis Example 7-3)

[0998] DA-1 (0.649 g: 6.00 mmol), DA-2 (0.977 g: 4.00 mmol), DA-4 (1.55 g: 6.00 mmol) and DA-10 (1.59 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DEAc (65.9 g) was added, and after stirring to dissolve under a nitrogen atmosphere, TC-1 (4.21 g: 18.8 mmol) was added while being kept at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-2) having a viscosity of about 410 mPa·s and a solid content concentration of 12% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 13,000 and a weight average molecular weight of 26,700.

[0999] (Synthesis Example 7-4)

[1000] DA-1 (0.649 g: 6.00 mmol), DA-2 (2.44 g: 10.0 mmol) and DA-6 (1.17 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DEAc (34.3 g) was added, and after stirring to dissolve under a nitrogen atmosphere, TC-1 (4.30 g: 19.2 mmol) was added while maintaining at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-3) having a viscosity of about 780 mPa·s and a solid content concentration of 20% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 12,000 and a weight average molecular weight of 29,300.

[1001] (Synthesis Example 7-5)

[1002] DA-1 (0.649 g: 6.00 mmol), DA-2 (2.44 g: 10.0 mmol) and DA-8 (0.949 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DEAc (33.2 g) was added, and after stirring to dissolve under a nitrogen atmosphere, TC-1 (4.26 g: 19.0 mmol) was added while maintaining at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-4) having a viscosity of about 1180 mPa·s and a solid content concentration of 20% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 14200 and a weight average molecular weight of 33100.

[1003] (Synthesis Example 7-6)

[1004] DA-1 (0.649 g: 6.00 mmol), DA-2 (2.44 g: 10.0 mmol) and DA-9 (1.07 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DEAc (33.5 g) was added, and after stirring to dissolve under a nitrogen atmosphere, TC-1 (4.21 g: 18.8 mmol) was added while maintaining at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-5) having a viscosity of about 1030 mPa·s and a solid content concentration of 20% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 13500 and a weight average molecular weight of 32400.

[1005] (Synthesis Example 7-7)

[1006] In a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DA-5 (3.58 g: 12.0 mmol) and DA-11 (1.20 g: 8.00 mmol) were weighed, DEAc (48.0 g) was added, and after stirring to dissolve under a nitrogen atmosphere, TC-2 (3.69 g: 18.8 mmol) was added while maintaining at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-6) having a viscosity of about 730 mPa·s and a solid content concentration of 15% by mass. The molecular weight of the polyamic acid is a number average molecular weight of 12600 and a weight average molecular weight of 35200.

[1007] (Synthesis Example 7-8)

[1008] In a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DA-12 (0.793 g: 4.00 mmol) and DA-13 (3.19 g: 16.0 mmol) were weighed, DEAc (30.7 g) was added, and after stirring to dissolve under a nitrogen atmosphere, TC-2 (3.69 g: 18.8 mmol) was added while maintaining at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-7) having a viscosity of about 920 mPa·s and a solid content concentration of 15% by mass. The molecular weight of the polyamic acid is a number average molecular weight of 14,000 and a weight average molecular weight of 38,600.

[1009] (Synthesis Example 7-9)

[1010] DA-1 (0.433 g: 4.00 mmol), DA-2 (1.47 g: 6.00 mmol), DA-3 (1.92 g: 6.00 mmol) and DA-7 (1.37 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DEF (68.6 g) was added, and after stirring and dissolving under a nitrogen atmosphere, TC-1 (4.17 g: 18.6 mmol) was added while being kept at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-8) having a viscosity of about 340 mPa·s and a solid content concentration of 12% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 15100 and a weight average molecular weight of 32200.

[1011] (Synthesis Example 7-10)

[1012] DA-1 (0.433 g: 4.00 mmol), DA-2 (1.47 g: 6.00 mmol), DA-3 (1.92 g: 6.00 mmol) and DA-7 (1.37 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DPAc (68.6 g) was added, and after stirring and dissolving under a nitrogen atmosphere, TC-1 (4.17 g: 18.6 mmol) was added while being kept at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-9) having a viscosity of about 350 mPa·s and a solid content concentration of 12% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 14200 and a weight average molecular weight of 30400.

[1013] (Synthesis Example 7-11)

[1014] DA-1 (0.433 g: 4.00 mmol), DA-2 (1.47 g: 6.00 mmol), DA-3 (1.92 g: 6.00 mmol) and DA-7 (1.37 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, and DEPA (68.6 g) was added. After stirring and dissolving under a nitrogen atmosphere, TC-1 (4.17 g: 18.6 mmol) was added while being kept at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-10) having a viscosity of about 350 mPa·s and a solid content concentration of 12% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 13,900 and a weight average molecular weight of 30,700.

[1015] (Synthesis Example 7-12)

[1016] DA-1 (0.433 g: 4.00 mmol), DA-2 (1.47 g: 6.00 mmol), DA-3 (1.92 g: 6.00 mmol) and DA-7 (1.37 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, 3MMP (68.6 g) was added, and after stirring to dissolve under a nitrogen atmosphere, TC-1 (4.17 g: 18.6 mmol) was added while maintaining at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-11) having a viscosity of about 440 mPa·s and a solid content concentration of 12% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 12,800 and a weight average molecular weight of 29,900.

[1017] (Synthesis Example 7-13)

[1018] DA-1 (0.433 g: 4.00 mmol), DA-2 (1.47 g: 6.00 mmol), DA-3 (1.92 g: 6.00 mmol) and DA-7 (1.37 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DMAc (68.6 g) was added, and after stirring and dissolving under a nitrogen atmosphere, TC-1 (4.17 g: 18.6 mmol) was added while being kept at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-12) having a viscosity of about 390 mPa·s and a solid content concentration of 12% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 13100 and a weight average molecular weight of 30600.

[1019] (Synthesis Example 7-14)

[1020] DA-1 (0.433 g: 4.00 mmol), DA-2 (1.47 g: 6.00 mmol), DA-3 (1.92 g: 6.00 mmol) and DA-7 (1.37 g: 4.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, NMP (68.6 g) was added, and after stirring and dissolving under a nitrogen atmosphere, TC-1 (4.17 g: 18.6 mmol) was added while being kept at 10° C. or less in an ice bath, and reacted at room temperature under a nitrogen atmosphere for 18 hours to obtain a polyamic acid solution (PAA-13) having a viscosity of about 390 mPa·s and a solid content concentration of 12% by mass. The molecular weight of the polyamic acid was a number average molecular weight of 13700 and a weight average molecular weight of 31100.

[1021] (Synthesis Example 7-15)

[1022] In a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DA-14 (1.22 g: 8.00 mmol), DA-15 (1.45 g: 6.00 mmol) and DA-16 (2.28 g: 6.00 mmol) were weighed, DEAc (19.8 g) was added, and after stirring and dissolving under a nitrogen atmosphere, TC-3 (1.00 g: 4.00 mmol) was added, and the mixture was reacted at 60° C. for 1 hour. Next, the reaction solution was cooled to below 10° C. using an ice bath, TC-4 (0.872 g: 4.00 mmol) and DEAc (4.00 g) were added, and the mixture was reacted at room temperature for 1 hour. Furthermore, TC-2 (2.24 g: 11.4 mmol) and DEAc (12.4 g) were added, and the mixture was reacted at room temperature for 12 hours, thereby obtaining a polyamic acid solution (PAA-14) having a viscosity of about 720 mPa·s and a solid content concentration of 20% by mass. The molecular weight of the polyamic acid was 17,300 in number average molecular weight and 39,800 in weight average molecular weight.

[1023] (Synthesis Example 7-16)

[1024] In a 300 mL eggplant flask equipped with a stirrer and a nitrogen inlet tube, the polyamic acid solution (PAA-14) (20.0 g) obtained above was measured, NMP (20.0 g) was added and stirred at room temperature for a while, and then acetic anhydride (2.70 g: 26.5 mmol) and pyridine (1.05 g, 13.2 mmol) were added, and stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then reacted at 70° C. for 3 hours under a nitrogen atmosphere. After the reaction was completed, the reaction solution was slowly injected into methanol (130 mL) cooled to below 10° C. while stirring to precipitate a solid, and stirred for 10 minutes. The precipitate was separated by filtration, and the slurry was washed with methanol (130 mL) for a total of 30 minutes twice, and the solid was vacuum dried at 80° C., thereby obtaining the target polyimide powder (SPI-2) (4.15 g, yield 86%). The imidization rate of the polyimide was 75%, and the number average molecular weight was 16,700 and the weight average molecular weight was 40,200.

[1025] (Synthesis Example 7-17)

[1026] DA-14 (1.22 g: 8.00 mmol), DA-15 (1.45 g: 6.00 mmol) and DA-16 (2.28 g: 6.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DEF (19.8 g) was added, and after stirring and dissolving under a nitrogen atmosphere, TC-3 (1.00 g: 4.00 mmol) was added, and the mixture was reacted at 60° C. for 1 hour. Next, the reaction solution was cooled to 10° C. or less using an ice bath, TC-4 (0.872 g: 4.00 mmol) and DEF (4.00 g) were added, and the mixture was reacted at room temperature for 1 hour. Furthermore, TC-2 (2.24 g: 11.4 mmol) and DEF (12.4 g) were added, and the mixture was reacted at room temperature for 12 hours, thereby obtaining a polyamic acid solution (PAA-15) having a viscosity of about 700 mPa·s and a solid content concentration of 20% by mass. The molecular weight of the polyamic acid was 16,400 in number average molecular weight and 39,400 in weight average molecular weight.

[1027] (Synthesis Example 7-18)

[1028] DA-14 (1.22 g: 8.00 mmol), DA-15 (1.45 g: 6.00 mmol) and DA-16 (2.28 g: 6.00 mmol) were weighed in a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DPAc (19.8 g) was added, and after stirring and dissolving under a nitrogen atmosphere, TC-3 (1.00 g: 4.00 mmol) was added, and the mixture was reacted at 60° C. for 1 hour. Next, the reaction solution was cooled to 10° C. or less using an ice bath, TC-4 (0.872 g: 4.00 mmol) and DPAc (4.00 g) were added, and the mixture was reacted at room temperature for 1 hour. Furthermore, TC-2 (2.24 g: 11.4 mmol) and DPAc (12.4 g) were added, and the mixture was reacted at room temperature for 12 hours, thereby obtaining a polyamic acid solution (PAA-16) having a viscosity of about 690 mPa·s and a solid content concentration of 20% by mass. The molecular weight of the polyamic acid was 18,500 in number average molecular weight and 39,900 in weight average molecular weight.

[1029] (Synthesis Example 7-19)

[1030] In a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DA-14 (1.22 g: 8.00 mmol), DA-15 (1.45 g: 6.00 mmol) and DA-16 (2.28 g: 6.00 mmol) were weighed, DEPA (19.8 g) was added, and after stirring and dissolving under a nitrogen atmosphere, TC-3 (1.00 g: 4.00 mmol) was added, and the mixture was reacted at 60° C. for 1 hour. Next, the reaction solution was cooled to below 10° C. using an ice bath, TC-4 (0.872 g: 4.00 mmol) and DEPA (4.00 g) were added, and the mixture was reacted at room temperature for 1 hour. Furthermore, TC-2 (2.24 g: 11.4 mmol) and DEPA (12.4 g) were added, and the mixture was reacted at room temperature for 12 hours, thereby obtaining a polyamic acid solution (PAA-17) having a viscosity of about 710 mPa·s and a solid content concentration of 20% by mass. The molecular weight of the polyamic acid was 18,100 in number average molecular weight and 43,300 in weight average molecular weight.

[1031] (Synthesis Example 7-20)

[1032] In a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DA-14 (1.22 g: 8.00 mmol), DA-15 (1.45 g: 6.00 mmol) and DA-16 (2.28 g: 6.00 mmol) were weighed, 3MMP (19.8 g) was added, and after stirring and dissolving under a nitrogen atmosphere, TC-3 (1.00 g: 4.00 mmol) was added, and the mixture was reacted at 60° C. for 1 hour. Next, the reaction solution was cooled to below 10° C. using an ice bath, TC-4 (0.872 g: 4.00 mmol) and 3MMP (4.00 g) were added, and the mixture was reacted at room temperature for 1 hour. Furthermore, TC-2 (2.24 g: 11.4 mmol) and 3MMP (12.4 g) were added and reacted at room temperature for 12 hours to obtain a polyamic acid solution (PAA-18) having a viscosity of about 890 mPa·s and a solid content concentration of 20% by mass. The molecular weight of the polyamic acid was 17,900 in number average molecular weight and 39,100 in weight average molecular weight.

[1033] (Synthesis Example 7-21)

[1034] In a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DA-14 (1.22 g: 8.00 mmol), DA-15 (1.45 g: 6.00 mmol) and DA-16 (2.28 g: 6.00 mmol) were weighed, NMP (19.8 g) was added, and after stirring and dissolving under a nitrogen atmosphere, TC-3 (1.00 g: 4.00 mmol) was added, and the mixture was reacted at 60° C. for 1 hour. Next, the reaction solution was cooled to 10° C. or less using an ice bath, TC-4 (0.872 g: 4.00 mmol) and NMP (4.00 g) were added, and the mixture was reacted at room temperature for 1 hour. Furthermore, TC-2 (2.24 g: 11.4 mmol) and NMP (12.4 g) were added, and the mixture was reacted at room temperature for 12 hours, thereby obtaining a polyamic acid solution (PAA-19) having a viscosity of about 850 mPa·s and a solid content concentration of 20% by mass. The molecular weight of the polyamic acid was 18,300 in number average molecular weight and 40,100 in weight average molecular weight.

[1035] (Synthesis Example 7-22)

[1036] In a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DA-14 (1.22 g: 8.00 mmol), DA-15 (1.45 g: 6.00 mmol) and DA-16 (2.28 g: 6.00 mmol) were weighed, 2MEA (19.8 g) was added, and after stirring and dissolving under a ni...

Claims

1. A liquid crystal alignment agent, characterized in that: contain: A polymer α obtained from a compound having a polymerizable group having a polymerizable unsaturated hydrocarbon group; A polymer β, which is at least one selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyamide and polyurea; and A compound represented by the following formula (S1) as a solvent, In formula (S1), Q 1 and Q 2 Each independently represents an alkyl group having 1 to 4 carbon atoms, Q 3 represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, an alkylcarbonylalkyl group having 4 to 8 carbon atoms, or a hydrogen atom, and Q 1 , Q 2 and Q 3 The total number of carbon atoms is 4 or more.

2. The liquid crystal alignment agent according to claim 1, wherein The polymerizable group is at least one selected from the group consisting of a (meth)acryloyloxy group, a (meth)acrylamide group, an allyl group, a styryl group, and a maleimide group.

3. The liquid crystal alignment agent according to claim 1, wherein The compound represented by the formula (S1) is at least one selected from N,N-diethylacetamide, N,N-diethylformamide, N,N-dibutylformamide, N,N-dipropylacetamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 2-methoxy-N,N-diethylacetamide, 3-methoxy-N,N-diethylpropionamide, 4-oxo-N,N-diethylpentanamide and N,N-diethylcyclohexanecarboxamide.

4. The liquid crystal alignment agent according to claim 1, wherein Content of the compound represented by the said formula (1) is 10-90 mass % with respect to the whole amount of the solvent component contained in the said liquid crystal aligning agent.

5. The liquid crystal alignment agent according to claim 1, wherein The fired film obtained by applying and firing the liquid crystal aligning agent exhibits weak anchoring properties.

6. The liquid crystal alignment agent according to claim 1, which is a weak anchor liquid crystal alignment agent used in forming a liquid crystal alignment film of a liquid crystal cell having a liquid crystal and a liquid crystal alignment film, The polymer α contains at least one selected from the following polymer A, polymer B and polymer C, Polymer A: A block copolymer having a block segment (A) and a block segment (B), wherein: The block segment (A) is compatible with the liquid crystal, and the block segment (B) is incompatible with the liquid crystal, or becomes incompatible with the liquid crystal after sintering; Polymer B: a graft copolymer comprising a main polymer and a branch polymer bonded to the main polymer as a side chain of the main polymer, wherein the branch polymer is compatible with the liquid crystal, and the main polymer is incompatible with the liquid crystal or becomes incompatible with the liquid crystal by firing; Polymer C: a polymer having a polymer unit compatible with the liquid crystal and reacting with the polymer β by heating.

7. The liquid crystal alignment agent according to claim 6, wherein: The block segment (A) in the polymer A, the branched polymer in the polymer B, and the polymer unit compatible with the liquid crystal in the polymer C contain at least one selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5), The block fragment (B) in the polymer A and the backbone polymer in the polymer B contain a compound represented by the following formula (6) as a constituent component, In formula (2), M represents a polymerizable group having an unsaturated hydrocarbon group capable of polymerization, X represents a single bond, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond, or a thioether bond, R1 represents an alkyl group having 1 to 20 carbon atoms with or without a bonding group inserted therein, and n is an integer of 1 to 2; when n is 2, two Xs and two R1s are the same or different, In formula (3), M represents a polymerizable group having an unsaturated hydrocarbon group capable of polymerization, S represents a single bond, or a saturated hydrocarbon group having 1 to 6 carbon atoms with or without a bonding group inserted therein, T represents an organic group represented by the following formula (3-T), n is an integer of 1 to 2; when n is 2, the two Ts are the same or different, wherein when n is 2, S represents a saturated hydrocarbon group having 1 to 6 carbon atoms with or without a bonding group inserted therein, *-X-Cy (3-T) In formula (3-T), * represents a bonding site; X is a bonding group selected from a single bond, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond, a thioether bond, -Si(R1)(R2)-, -Si(R3)(R4)-O- and -N(R5)-, wherein R1 and R2 each independently represent an alkyl group bonded to Si, R3 and R4 each independently represent an alkyl group bonded to Si, and R5 represents a hydrogen atom or an alkyl group bonded to N; Cy represents a 6- to 20-membered non-aromatic cyclic group, In formula (4), M represents a polymerizable group having an unsaturated hydrocarbon group capable of polymerization, R1 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms and having a linear or branched structure, and three Xs each independently represent a hydrogen atom or the following formula (4-X), wherein at least one of the three Xs represents formula (4-X), In formula (4-X), Y represents a single bond, -O-, -S- or -N(R)-, wherein R represents a hydrogen atom bonded to N or an alkyl group having 1 to 4 carbon atoms; * represents a bonding site; R2, R3 and R4 each independently represent an alkyl group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group which may have a substituent, In formula (5), M represents a polymerizable group having an unsaturated hydrocarbon group capable of polymerization, R1 to R3 each independently represent a single bond, or an alkylene group having 1 to 6 carbon atoms with or without a bonding group inserted therein, Ar represents an aromatic hydrocarbon group with or without a substituent, X1 and X2 each independently represent a hydrogen atom, or an aromatic hydrocarbon group with or without a substituent, R1X1, R2X2, and the carbon atoms bonded to R1X1 and R2X2 may or may not form a ring, wherein the total number of carbon atoms of R1X1, R2X2, and R3 is 1 or more, In formula (6), M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group, n is an integer of 1 to 2; Z represents a group represented by the following formula (6-Z), and when n is 2, the two Zs are the same or different. In formula (6-Z), L represents a group selected from a trialkoxysilyl group, an isocyanate group, a blocked isocyanate group, an epoxy group, an oxetane group, a vinyl group, an allyl group, an oxazoline group, an amino group, a protected amino group, an anilino group, a protected anilino group, a hydroxyl group, a protected hydroxyl group, a phenol group, a protected phenol group, a thiol group, a protected thiol group, a thiophenol group, a protected thiophenol group, an aldehyde group, a carboxyl group, a maleimide group, an N-hydroxysuccinimide ester group, an aromatic hydrocarbon group having 5 to 18 carbon atoms with or without a bonding group, an aromatic heterocyclic group having 5 to 18 carbon atoms with or without a bonding group, and a cinnamic acid group. , a functional group selected from the group consisting of cinnamic acid aromatic ester group, cinnamic acid alkyl ester group, cinnamyl group, benzoic acid phenyl ester group, azophenyl group, N-benzylideneaniline group, stilbene group and diphenylethynyl group; J represents a single bond or an aliphatic hydrocarbon group having 1 to 6 carbon atoms; K, when bonded to an aromatic hydrocarbon group, represents a connecting group selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a carbamate bond and a thioether bond, and otherwise represents a single bond; * represents a bonding site; m is an integer from 1 to 3; when m is 2 or 3, multiple K and L are the same or different, and when J is a single bond, m is 1.

8. The liquid crystal alignment agent according to claim 7, wherein: The branched polymer in the polymer B is derived from a macromonomer represented by the following formula (7), In formula (7), P represents a polymerizable group having an unsaturated hydrocarbon group capable of polymerization, Q is a structure obtained by polymerizing a monomer comprising at least one of the compounds represented by formulae (2) to (5); n is an integer from 1 to 2; when n is 2, the two Qs are the same or different.

9. The liquid crystal alignment agent according to claim 7, wherein: The polymer C is a polymer represented by the following formula (8): In formula (8), A represents an n-valent organic group having a molecular weight of 500 or less and having a group that reacts with the polymer β by heating, selected from the following formulas (8-A-1) to (8-A-16), Q is a divalent polymer unit that contains at least one selected from the compounds represented by the formulae (2) to (5) as a constituent component and is compatible with the liquid crystal, R is a monovalent organic group selected from the following formulas (8-R-1) to (8-R-11), which does not react with the polymer β by heating and has a molecular weight of 500 or less, n is an integer of 1 to 2; when n is 2, the two Qs and Rs are the same or different, In formulas (8-A-1) to (8-A-16), R1 and R2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, R3 and R4 each independently represent a single bond or a linear or branched alkylene group having 1 to 12 carbon atoms, X represents an oxygen atom or a sulfur atom, and * represents a bonding site. In formulas (8-R-1) to (8-R-11), R1 and R2 each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms, R3 and R4 each independently represent a single bond or a straight-chain or branched alkylene group having 1 to 12 carbon atoms, and * represents a bonding site. 10 . The liquid crystal alignment agent according to claim 1 , which is a strong anchor liquid crystal alignment agent, and a fired film obtained by coating and firing the liquid crystal alignment agent exhibits optical anisotropy when irradiated with polarized ultraviolet light.

11. The liquid crystal alignment agent according to claim 1, which is a strong anchoring liquid crystal alignment agent, wherein the side chain structure of the liquid crystal unit constituting the polymer α comprises at least one of the following formulas (10a) to (10q), In formulas (10a) to (10f), n1 and n2 are each independently 0, 1, 2 or 3, L is a single bond, an alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more -CH2- constituting the alkylene group having 1 to 12 carbon atoms is replaced by -O-, -S-, -C(=O)-O-, or -OC(=O)-, and a part or all of the hydrogen atoms of the alkylene group and the divalent linking group are or are not replaced by halogen atoms; T 1 is a single bond or an alkylene group having 1 to 12 carbon atoms, wherein some or all of the hydrogen atoms of the alkylene group are replaced by halogen atoms or not; A 1 , A 2 and D 1 are each independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)-, wherein In T 1 When A is a single bond, 2 Also a single bond; Y 1 and Y 2 Each is independently a phenylene group or a naphthylene group, wherein a part or all of the hydrogen atoms of the phenylene group and the naphthylene group are replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; P 1 , Q 1 and Q 2 Each independently represents a single bond, a phenylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, wherein a part or all of the hydrogen atoms of the phenylene group and the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms are substituted with a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; in Q 1 When the number is 2 or more, each Q 1 Same or different from each other; in Q 2 When the number is 2 or more, each Q 2 the same as or different from one another; R is a hydrogen atom, a cyano group, a halogen atom, a carboxyl group, a linear or branched alkyl group having 1 to 40 carbon atoms, a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; X 1 , X 2 and X 3 Each of them is independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-, and in X 1 When the number is 2 or more, each X 1 Same or different from each other; in X 2 When the number is 2 or more, each X 2 the same as or different from one another; Z 1a and Z 2a Each is independently a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms, wherein some or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms; Cou is coumarin-6-yl or coumarin-7-yl, and a portion of hydrogen atoms bonded thereto is or is not replaced by -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-; G 1 and G 2 are each independently N or CH; The dotted line is the bond. In formula (10g) to (10q), A 3 and A 4 Each is independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-C(=O)-, in A 4 When the number is 2 or more, each A 4 the same as or different from one another; R 1 is -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; R 2 is phenyl, naphthyl, biphenyl, furyl, a monovalent nitrogen-containing heterocyclic group or a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, wherein a part or all of the hydrogen atoms of these groups are replaced by -NO2, -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; R 3 is a hydrogen atom, -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-; L′ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more -CH2- constituting the alkylene group having 1 to 12 carbon atoms is replaced by -O-, -S-, -C(=O)-O-, or -OC(=O)-, and a part or all of the hydrogen atoms of the alkylene group and the divalent linking group are or are not replaced by halogen atoms; k1 to k5 are each independently an integer of 0 to 2, but the total of k1 to k5 is 2 or more; k6 and k7 are each independently an integer of 0 to 2, but the total of k6 and k7 is 1 or more; m1, m2 and m3 are each independently an integer from 1 to 3; n is 0 or 1; Z 1 and Z 2 Each is independently a single bond, -C(=O)-, -CH2-O- or -CF2-; The dotted line is the bond. In addition, part or all of the hydrogen atoms on the benzene ring and naphthalene ring in formulas (10g) to (10q) may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

12. The liquid crystal aligning agent according to any one of claims 7 to 9, wherein M in the formula (2) is any of the following structures: M in the formula (3) is any of the following structures, M in the formula (4) is any of the following structures, M in the formula (5) is any of the following structures, In the formula, R1 and R2 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and X, Y and Z each independently represent an oxygen atom or a sulfur atom; *, * 1 and* 2 Indicates the bonding site, * 1 and* 2 Any one of them may be substituted by a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.

13. The liquid crystal alignment agent according to claim 6, wherein: The polymers A to C are polymers obtained by living polymerization or chain transfer polymerization.

14. A liquid crystal display element, characterized in that: A liquid crystal aligning film formed using the liquid crystal aligning agent according to claim 1 is provided.

15. The liquid crystal display element according to claim 14, wherein The liquid crystal display element is a transverse electric field liquid crystal display element.

16. A method for manufacturing a liquid crystal display element, characterized in that: The method comprises coating and firing the liquid crystal alignment agent according to claim 1.

17. The method for manufacturing a liquid crystal display element according to claim 16, wherein: The liquid crystal display element is a transverse electric field liquid crystal display element.

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