Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
  • C09K19/56—Aligning agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
  • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1092—Polysuccinimides
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

• the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal aligning film.
• Liquid crystal display elements are now widely used as display devices that are thin and light.
• a liquid crystal alignment film is used to control the alignment state of the liquid crystal.
• liquid crystal display elements have become widely used in large-screen liquid crystal televisions and high-definition mobile applications (display parts of digital cameras and mobile phones).
• the unevenness of the step of the substrate is getting larger. Even in such a situation, it is required that the liquid crystal alignment film be uniformly formed on a large substrate or a step from the viewpoint of display characteristics.
• the liquid crystal alignment film is required to have high functions for controlling the alignment state of the liquid crystal (also referred to as liquid crystal alignment) and also for electrical characteristics such as reliability and image sticking characteristics in the liquid crystal display element.
• a polyimide polymer of polyamic acid or soluble polyimide is generally used as the liquid crystal alignment film (see, for example, Patent Document 1).
• the polyimide-based polymer used in the conventional liquid crystal alignment film is not necessarily sufficiently soluble in the solvent, and when the liquid crystal aligning agent is applied on the substrate, the polymer component is not present on the substrate. It may precipitate (also called whitening). This phenomenon called whitening has become a serious problem as the line for producing the liquid crystal alignment film becomes larger. This is considered to occur when the liquid crystal aligning agent contains moisture in the atmosphere and the solubility of the polymer is lowered.
• An object of the present invention is to provide a liquid crystal aligning agent excellent in whitening resistance and coating film uniformity, and a liquid crystal alignment film excellent in liquid crystal alignment.
• another object is to provide a liquid crystal display element having such a liquid crystal alignment film.
• the present inventor has found that a liquid crystal aligning agent containing a polymer having a specific structure is extremely effective for achieving the above object, and has completed the present invention. That is, the present invention has the following gist. (1) It has a partial structure represented by the following formula [U] and has at least one side chain structure selected from a structure represented by the following formulas [S1] and [S2] and a structure having a steroid skeleton. A liquid crystal aligning agent containing at least one polymer selected from a polyimide precursor and polyimide.
• Y 1 is a single bond, —O—, —S—, —COO— or —OCO—
• K 1 and K 2 each independently represent a —CH 2 — group or a —CHR 1a — group ( R 1a represents an —OH group or a monovalent organic group.)
• R 1a represents an —OH group or a monovalent organic group.
• Any one of K 1 and K 2 may be replaced by a —C (O) group
• R 3 and R 4 are each independently , An alkylene group having 1 to 7 carbon atoms, and * represents a site bonded to another group.
• X 1 and X 2 are independently a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CON (CH 3 ) —, —NH -, - O -, - COO -, - OCO-, or ((CH 2) a1 -A 1 ) m1 - ( each independently plurality of a1 represents an integer of 1 to 15, a plurality of a 1 each Independently represents an oxygen atom or COO—, and m 1 represents 1 to 2, and G 1 and G 2 independently represent a bivalent aromatic group having 6 to 12 carbon atoms or 3 carbon atoms.
• a divalent alicyclic group selected from divalent alicyclic groups of 8 to 8, wherein any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, Substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
• R 1 is alkyl of 1 to 20 carbon atoms, from 1 to 20 carbon atoms alkoxy, or carbon atoms 2-20 alkoxyalkyl, any hydrogen in these groups may be replaced by fluorine.
• X 3 represents a single bond, —CONH—, —NHCO—, —CON (CH 3 ) —, —NH—, —O—, —CH 2 O—, —COO— or OCO—, and R 2 represents carbon An alkyl having 1 to 20 carbon atoms or an alkoxyalkyl having 2 to 20 carbon atoms, and any hydrogen in these groups may be replaced by fluorine.
• the liquid crystal aligning agent of the present invention is excellent in whitening resistance and coating film uniformity, can obtain a liquid crystal aligning film excellent in liquid crystal aligning property, and has a liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention. Is excellent in display quality and can be suitably used for various display devices.
• the liquid crystal aligning agent of the present invention has a partial structure represented by the formula [U] (also referred to as a specific partial structure), and at least one selected from the formulas [S1], [S2] and a steroid skeleton.
• a polymer (also referred to as a specific polymer) having a side chain structure (also referred to as a specific side chain structure) is contained.
• the meanings of Y 1 , Y 2 , K 1 , K 2 , R 3 , R 4 , and * in the formula [U] are as described above.
• the monovalent organic group constituting R 1a when K 1 and K 2 are —CHR 1a — group includes a hydrocarbon group; a hydroxyl group, a carboxyl group, a hydroxyl group, a thiol group, or a carboxyl group.
• the hydrocarbon group herein may be any of a straight chain, a branched chain or a cyclic chain, and may be a saturated hydrocarbon or an unsaturated hydrocarbon.
• some of the hydrogen atoms of the hydrocarbon group may be replaced by carboxyl groups, hydroxyl groups, thiol groups, silicon atoms, halogen atoms, etc., and are linked by a linking group such as an ether bond, an ester bond, or an amide bond. It may be.
• the alkylene group having 1 to 7 carbon atoms constituting R 3 and R 4 may be any of linear, branched or cyclic. Specifically, methylene group, ethylene group, n-propylene group, isopropylene group, cyclopropylene group, 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, 1,1-dimethyl-n-propylene group 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1-ethyl-n-propylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1- Methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group,
• Y 1 and Y 2 in the formula [U] are preferably —O—, —COO—, or —OCO— from the viewpoint of polymer supply.
• K 1 and K 2 are each a —CH 2 — group, —CH (OH) — group, —CO— group, —CH (CH 3 ) — group, —CH (O—Boc) — group. preferable. “Boc” refers to a tert-butoxycarbonyl group.
• R 3 and R 4 are preferably a methylene group, an ethylene group, or an n-propylene group.
• Preferred examples of the partial structure represented by the above formula [U] include the following formula [U-Ar].
• the specific polymer further has at least one specific side chain structure selected from the group consisting of the following formulas [S1] and [S2] and a steroid skeleton.
• the meanings of X 1 , X 2 , G 1 , G 2 , R 1 , m and n in the formula [S1] are as described above.
• X 1 and X 2 are each a single bond, — (CH 2 ) a — (a is 1 to 15), —O—, from the viewpoint of availability of raw materials and ease of synthesis.
• —CH 2 O— or COO— is preferred. More preferably, it is a single bond, — (CH 2 ) a — (wherein a is 1 to 10), —O—, —CH 2 O—, or COO—.
• Examples of the divalent aromatic group having 6 to 12 carbon atoms in G 1 and G 2 include phenylene, biphenylene, naphthalene and the like.
• Examples of the divalent alicyclic group having 3 to 8 carbon atoms include cyclopropylene and cyclohexylene.
• G 1 and G 2 are preferably phenylene, biphenylene, naphthalene, cyclopropylene, or cyclohexylene.
• R 1 is more preferably an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
• formula [S1] include the following formulas [S1-x1] to [S1-x7].
• R 1 is an alkyl group having 1 to 20 carbon atoms
• X p is — (CH 2 ) a — (a is an integer of 1 to 15).
• a 1 is —O— or —COO— * (where a bond marked with “*” binds to (CH 2 ) a2 ), and A 2 is —O— or * —COO— (where a "*" is a bond marked with (CH 2) binds to a2)
• a 1, a 3 are each independently 0 or 1
• a 2 is 2 ⁇ 10, Cy Is a 1,4-cyclohexylene group or a 1,4-phenylene group.
• X 3 and R 2 in the formula [S2] are as described above.
• X 3 is preferably —CONH—, —NHCO—, —O—, —CH 2 O—, —COO— or OCO— from the viewpoint of liquid crystal alignment.
• R 2 is preferably alkyl having 3 to 20 carbons or alkoxyalkyl having 2 to 20 carbons from the viewpoint of liquid crystal orientation.
• the structure having a steroid skeleton can be represented by the following formula [S3].
• X 4 represents —CONH—, —NHCO—, —O—, —COO— or OCO—
• R 3 represents a structure having the steroid skeleton.
• a preferred specific example of the formula [S3] is the following formula [S3-x]. In the formula, * indicates a bonding position.
• the structure having a steroid skeleton include a structure obtained by removing a hydroxy group from a steroid compound described in paragraph [0024] of Japanese Patent Application Laid-Open No. 4-281427, and an acid chloride group removed from a steroid compound described in paragraph [0030].
• the structure described in [0022] can be given.
• the specific polymer in the present invention is at least one polymer selected from a polyimide precursor and a polyimide (also collectively referred to as a polyimide polymer).
• a polyimide precursor also collectively referred to as a polyimide polymer.
• the polyimide which is a polyimide precursor obtained by making a diamine component and a tetracarboxylic-acid component react, or its imidation thing is preferable.
• the polyimide precursor is represented by the following formula [A].
• R 1 is a tetravalent organic group
• R 2 is a divalent organic group
• a 1 and A 2 are each independently a hydrogen atom or an alkylene group having 1 to 5 carbon atoms
• a 3 and A 4 are each independently a hydrogen atom, an alkylene group having 1 to 5 carbon atoms or an acetyl group
• n is a positive integer.
• the diamine component include diamines having two primary or secondary amino groups in the molecule.
• tetracarboxylic acid component examples include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide.
• a diamine having two primary or secondary amino groups in the molecule a tetracarboxylic acid or a tetracarboxylic acid It can be obtained by reacting with an anhydride.
• a polyamic acid alkyl ester in which A 1 and A 2 in the formula [A] are an alkylene group having 1 to 5 carbon atoms the diamine, a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester, or a tetracarboxylic acid It can be obtained by reacting with a dialkyl ester dihalide.
• an alkylene group having 1 to 5 carbon atoms of A 1 and A 2 represented by the formula [A] can be introduced into the polyamic acid obtained by the above method.
• the specific polymer at least one side selected from a structural unit having a partial structure of the formula [U], a structure of the formulas [S1] and [S2], and a structure having a steroid skeleton.
• a polymer containing a structural unit having a chain structure hereinafter also referred to as a copolymer
• a polymer containing a structural unit having a partial structure of the formula [U] the formulas [S1], [S2]
• a mixture hereinafter also referred to as polymer blend
• the method for introducing the partial structure of the formula [U] into the polymer is not particularly limited, but a diamine having the structure of the formula [U], specifically, a diamine represented by the following formula [U-1] is used. It is preferable to use a part of the raw material.
• Y A represents an organic group having the structure of Formula [U]
• a 1 and A 2 each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. Show. More specifically, a diamine represented by the following formula [Ua] is preferable.
• Y 1 and Y 2 are each independently a single bond, —O—, —S—, —COO— or —OCO—.
• K 1 and K 2 each independently represent a —CH 2 — group or —CHR 1a — group (R 1a represents an —OH group or a monovalent organic group), where K 1 and K Either one of 2 may be replaced by a —C (O) group.
• R 3 and R 4 are each independently an alkylene group having 1 to 7 carbon atoms. Any hydrogen atom of the benzene ring may be substituted with a monovalent organic group.
• a 1 and A 2 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
• amine [Ua] include the following formulas [U-1a] to [U-6a].
• a 1 to A 2 each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, and the Boc group represents tert-butoxycarbonyl. Indicates a group.
• diamine [Ua] More preferred specific examples of the diamine [Ua] include the following formulas [UM-1] to [UM-13].
• the method for introducing at least one side chain structure selected from the structures of the formulas [S1] and [S2] and a structure having a steroid skeleton into the polymer is not particularly limited, but the formulas [S1] and [S2 It is preferable to use a diamine having a side chain structure selected from a structure having a steroid skeleton as a part of the raw material.
• a diamine represented by the following formula [S1-a] is preferably used as a part of the raw material.
• B is the formula [S1], [S2] or [S3], and A 1 and A 2 are each independently a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.
• a hydrogen atom or an alkylene group having 1 or 2 carbon atoms is preferable.
• m is 1 to 4, and 1 is particularly preferable from the viewpoint of easy synthesis.
• Preferred examples of the formulas [S1] to [S3] are as described above.
• the amount of the diamine represented by the formula [Ua] and the diamine represented by the formula [S1-a] in obtaining the copolymer is the total diamine component, respectively.
• the total amount of the diamine represented by the formula [Ua] and the diamine represented by the formula [S1-a] is preferably 5 to 100 mol% in 100 mol% of all diamine components. ⁇ 100 mol% is preferred, and 20 ⁇ 100 mol% is particularly preferred.
• the amount of the diamine represented by the formula [Ua] is whitening resistance in 100 mol% of the diamine component used in the polymer containing the residue of the formula [Ua] as a constituent unit. Is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more. Further, the amount of the diamine of the formula [S1-a] used is that the liquid crystal orientation is improved in 100 mol% of the diamine component used in the polymer containing the residue of the formula [S1-a] as a structural unit. 1 mol% or more is preferable, 2 mol% or more is more preferable, and 5 mol% or more is still more preferable. A particularly preferred specific example is 20 mol% or more.
• the diamine of the formula [Ua] and the diamine of the formula [S1-a] are the solubility of the specific polymer in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal alignment property when the liquid crystal alignment film is used, the voltage holding ratio. Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds may be used.
• a diamine other than the diamine of the formula [Ua] and the diamine of the formula [S1-a] (also referred to as other diamine) can be used.
• a diamine having a nitrogen-containing heterocyclic ring a diamine having a nitrogen-containing structure described in paragraph [0050] of JP-A-2016-218149, 1,3-bis (3-aminopropyl) -1,1,3,3 -Increase the response speed of liquid crystals when using organosiloxane-containing diamines such as tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1,3,3-tetramethyldisiloxane, and liquid crystal display devices.
• Functional group capable of forming a covalent bond I can be exemplified diamines having.
• More preferred specific examples include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4 ′.
• diamines of the present invention are soluble in the solvent of the polymer of the present invention, coating properties of the liquid crystal aligning agent, liquid crystal alignment properties when used as a liquid crystal alignment film, voltage holding ratio, accumulated charge, etc.
• One type or a mixture of two or more types can also be used.
• the amount of the diamine of the formula [Ua] is 100 mol% of the diamine component used in the polymer containing the residue of the formula [Ua] as a constituent unit. 20 to 100 mol% can be mentioned.
• tetracarboxylic acid component for producing the polymer of the present invention that is, the polyimide polymer
• a tetracarboxylic dianhydride represented by the following formula [4] it is preferable to use a tetracarboxylic dianhydride represented by the following formula [4].
• the tetracarboxylic dianhydride represented by the formula [4] but also the tetracarboxylic acid derivative tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dihalide It can also be used.
• Z represents at least one structure selected from the following [4a] to [4k].
• Z 1 to Z 4 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, and may be the same or different.
• Preferable specific examples of Z 1 to Z 4 include the following structures [4a-1] and [4a-2].
• Z 5 and Z 6 represent a hydrogen atom or a methyl group, and may be the same or different.
• Z in the formula [4] from the viewpoint of easy synthesis and ease of polymerization reactivity when producing a polymer, the formula [4a], the formula [4c] to the formula [4g] or the formula [4k] ]
• the tetracarboxylic dianhydride of the structure shown by these and its tetracarboxylic acid derivative are preferable. More preferable is the structure represented by the formula [4a] or the formula [4e] to the formula [4g].
• tetracarboxylic dianhydrides and their tetracarboxylic acid derivatives having the structure represented by [4a], formula [4e] or formula [4f]. More preferable specific examples include tetracarboxylic dianhydrides having the structures represented by [4a-1], formula [4a-2], formula [4e], and formula [4f] and their tetracarboxylic acid derivatives. .
• the tetracarboxylic acid component represented by the formula [4] in the polymer of the present invention is preferably 1 to 100 mol% in 100 mol% of all tetracarboxylic acid components. Among these, 5 to 95 mol% is preferable. More preferred is 20 to 80 mol%.
• the tetracarboxylic acid component of the present invention has properties such as solubility of the polymer of the present invention in a solvent, coating properties of a liquid crystal aligning agent, liquid crystal alignment properties, voltage holding ratio, and accumulated charge when used as a liquid crystal alignment film. Depending on the situation, one kind or a mixture of two or more kinds may be used.
• tetracarboxylic acid components other than the specific tetracarboxylic acid component can also be used in the polyimide polymer of the polymer of the present invention.
• examples of other tetracarboxylic acid components include the following tetracarboxylic acids, tetracarboxylic dianhydrides, tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides.
• tetracarboxylic acid components include 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic 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 ′ -Benzophenone tetracarboxylic 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, bis (3,4-dicarboxyphenyl) dimethylsilane
• the other tetracarboxylic acid components of the present invention are properties such as solubility of the polymer of the present invention in a solvent, coating properties of a liquid crystal aligning agent, liquid crystal alignment properties, voltage holding ratio, accumulated charge, etc. Depending on the situation, one kind or a mixture of two or more kinds may be used.
• the method for producing a polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydrides and derivatives of the tetracarboxylic acid is reacted with a diamine component consisting of one or more diamines. And a method of obtaining a polyamic acid.
• tetracarboxylic dianhydride and primary or secondary diamine are polycondensed to obtain polyamic acid
• tetracarboxylic acid and primary or secondary diamine are subjected to dehydration polycondensation reaction.
• a method of obtaining a polyamic acid or a method of polycondensing a tetracarboxylic acid dihalide and a primary or secondary diamine to obtain a polyamic acid is used.
• the polymer can be obtained by reacting the tetracarboxylic acid component and the diamine component as described above together with a molecular weight modifier as necessary.
• the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamines such as aniline, cyclohexylamine and n-butylamine, and monoisocyanates such as phenyl isocyanate and naphthyl isocyanate. Can do.
• the use ratio of the molecular weight modifier is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, with respect to 100 parts by mass in total of the tetracarboxylic acid component and the diamine component to be used.
• a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine, a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and 1 A method of polycondensation with a secondary or secondary diamine or a method of converting a carboxyl group of a polyamic acid into an ester is used.
• polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
• the reaction between the diamine component and the tetracarboxylic acid component is usually carried out in a solvent with the diamine component and the tetracarboxylic acid component.
• the solvent used at that time is not particularly limited as long as the produced polyimide precursor is soluble. Although the specific example of the solvent used for reaction below is given, it is not limited to these examples.
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-2-imidazolidinone Is mentioned.
• the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3]
• the indicated solvents can be used.
• D 1 represents an alkylene group having 1 to 3 carbon atoms
• D 2 represents an alkylene group having 1 to 3 carbon atoms
• D-3 represents an alkylene group having 1 to 4 carbon atoms.
• solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced
• the reaction can be performed at an arbitrary concentration. However, if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and the concentration is high. If it is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
• the initial reaction can be carried out at a high concentration, and then a solvent can be added.
• the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
• the polyimide of the present invention is a polyimide obtained by ring closure of the polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%. It can be arbitrarily adjusted according to the purpose. Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalyst imidization in which a catalyst is added to the polyimide precursor solution.
• the temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
• the catalytic imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 ° C to 250 ° C, preferably 0 ° C to 180 ° C. it can.
• the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
• Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
• Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
• the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
• the reaction solution may be poured into a solvent and precipitated.
• the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
• the polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating.
• the polymer collected by precipitation is redissolved in a solvent and then re-precipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
• the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.
• the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the polyimide precursor and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. It is.
• the molecular weight distribution (Mw / Mn) represented by the ratio between Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.
• the liquid crystal aligning agent of this invention is a coating solution for forming a liquid crystal aligning film (it is also called a resin film), and is a coating solution for forming the liquid crystal aligning film containing a specific polymer and a solvent.
• a specific polymer any polyimide polymer such as polyamic acid, polyamic acid alkyl ester, and polyimide may be used. All of the polymers in the liquid crystal aligning agent of the present invention may be specific polymers, or other polymers may be mixed. Other polymers include polyimide having no side chain structure selected from the partial structure represented by the formula [U], the structure represented by the formulas [S1] to [S2], and the structure having a steroid skeleton.
• a cellulose polymer an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or polysiloxane may be used.
• the content of the other polymer is preferably 5 to 90 parts by mass, preferably 10 to 60 parts by mass with respect to 100 parts by mass of the polymer including the specific polymer and the other polymer. Is more preferable.
• the content of the solvent in the liquid crystal aligning agent of the present invention is preferably 70 to 99.9% by mass. This content can be appropriately changed depending on the application method of the liquid crystal aligning agent and the film thickness of the target liquid crystal alignment film.
• the solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if it is a solvent (it is also called a good solvent) which dissolves a polymer. Although the specific example of a good solvent is given to the following, it is not limited to these examples.
• N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, ⁇ -valero Lactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy- 4-methyl-2-pentanone and the like can be mentioned.
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, 1,3-dimethyl-2-imidazolidinone, 3- Methoxy-N, N-dimethylpropanamide or 3-butoxy-N, N-dimethylpropanamide is preferred.
• the solubility of the polymer in the solvent is high, it is preferable to use the solvents represented by the formulas [D-1] to [D-3].
• the good solvent in the liquid crystal aligning agent of the present invention is preferably 5 to 99% by mass of the whole solvent contained in the liquid crystal aligning agent. Among these, 10 to 90% by mass is preferable.
• the liquid crystal aligning agent of this invention can use the solvent (it is also called a poor solvent) which improves the coating property and surface smoothness of a liquid crystal aligning film at the time of apply
• a poor solvent is given to the following, it is not limited to these examples.
• ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etanji 1,2-propanediol, 1,3-propaned
• 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl -2-Pentanone, propylene glycol diacetate, dipropylene glycol monomethyl ether or propylene carbonate are preferred.
• These poor solvents are preferably 1 to 95% by mass of the whole solvent contained in the liquid crystal aligning agent. Among these, 10 to 90% by mass is preferable.
• the liquid crystal aligning agent of the present invention has a crosslinkable property having at least one substituent selected from a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group.
• a compound or a crosslinkable compound having a polymerizable unsaturated bond may be contained. It is preferable to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.
• Examples of the crosslinkable compound having an epoxy group or an isocyanate group include compounds described in paragraph [0087] of International Publication No. WO2015 / 008846.
• crosslinkable compound having a cyclocarbonate group examples include the crosslinkability represented by the formulas [5-1] to [5-42] described on pages 76 to 82 of International Publication WO2012 / 014898.
• Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include compounds described in paragraphs [0090] to [0092] of International Publication No. WO2015 / 008846.
• crosslinkable compound having a polymerizable unsaturated bond examples include the compounds described in paragraph [0186] of International Publication No. WO2011 / 132751.
• a compound represented by the formula [5] described in paragraph [0188] of International Publication No. WO2011 / 132751 can also be used.
• the said compound is an example of a crosslinkable compound, It is not limited to these.
• the crosslinkable compound used for the liquid crystal aligning agent of this invention may be one type, and may combine two or more types.
• the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components.
• the amount is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components. More preferred is 1 to 50 parts by mass.
• the liquid crystal aligning agent of this invention can use the compound which improves the uniformity of the film thickness of a liquid crystal aligning film at the time of apply
• the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
• F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).
• the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. is there.
• the liquid crystal aligning agent of the present invention includes compounds represented on pages 69 to 73 of International Publication No. WO2011 / 132751 as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge release of the device. Nitrogen-containing heterocyclic amines represented by [M1] to formula [M156] can also be added.
• the amine may be added directly to the liquid crystal aligning agent, but it is preferable to add the amine after making a solution with a suitable solvent at a concentration of 0.1 to 10%, preferably 1 to 7%.
• the solvent is not particularly limited as long as it is a solvent that dissolves the polyimide polymer described above.
• the liquid crystal aligning agent of the present invention includes a liquid crystal in addition to the above poor solvent, crosslinkable compound, resin film or compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film, and a compound that promotes charge removal.
• a dielectric material or conductive material for changing the electrical properties such as the dielectric constant and conductivity of the alignment film may be added.
• the liquid crystal aligning agent of this invention can be used as a liquid crystal aligning film by apply
• it can be used as a liquid crystal alignment film without alignment treatment.
• the substrate used at this time is not particularly limited as long as it is a highly transparent substrate.
• a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed.
• an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.
• the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, a method performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like is common.
• Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, or a spray method, and these may be used depending on the purpose.
• the heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven is used, depending on the solvent used for the liquid crystal aligning agent, 30 to 300 ° C., preferably 30
• the liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of ⁇ 250 ° C. If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm.
• the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then producing a liquid crystal cell by a known method.
• the liquid crystal aligning agent of this invention has a liquid crystal layer between a pair of board
• a liquid crystal display element produced by a step of polymerizing a polymerizable compound by disposing a liquid crystal composition and applying a voltage between electrodes while at least one of irradiation with active energy rays and heating.
• ultraviolet rays are suitable as the active energy ray.
• the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm.
• the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C.
• the above liquid crystal display element controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method.
• a PSA method a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound.
• the pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer.
• the PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.
• a liquid crystal cell is prepared, and a polymerizable compound is applied by at least one of ultraviolet irradiation and heating. Polymerization can control the orientation of liquid crystal molecules.
• a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure and sealed, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed and then the substrate is bonded and sealed. Can be mentioned.
• a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed.
• the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule.
• the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component.
• the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases and the liquid crystal display element.
• the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.
• the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferable to use it for a liquid crystal display element manufactured through a process of disposing a liquid crystal alignment film containing and applying a voltage between electrodes, that is, an SC-PVA mode.
• ultraviolet rays are suitable as the active energy ray.
• the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C.
• a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent or a polymer containing a polymerizable group examples include methods using components.
• Specific examples of the polymer containing a polymerizable group are not particularly limited as long as the polymer has the photoreactive group, and a polymer obtained by using the diamine having the photoreactive group can be exemplified. .
• a pair of substrates on which the liquid crystal alignment film of the present invention is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is prepared.
• the other substrate is bonded so that the inner side is inside, the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
• the method of performing etc. is mentioned.
• the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
• the liquid crystal aligning agent of the present invention can provide a liquid crystal aligning film that can exhibit a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time.
• a liquid crystal alignment film that suppresses a decrease in the voltage holding ratio and quickly relaxes the residual charges accumulated by a DC voltage is obtained. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability and is suitable for a large-screen high-definition liquid crystal television, a small and medium-sized car navigation system, a smartphone, and the like. Can be used.
• the molecular weight of the polyimide precursor and polyimide is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and a column (KD-803, KD-805) (manufactured by Shodex). It measured as follows.
• the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid that appear in the vicinity of 9.5 ppm to 10.0 ppm. It calculated
• Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
• x is a proton peak integrated value derived from NH group of amic acid
• y is a peak integrated value of reference proton
• ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
• NEP was added to the polyamic acid solution (1) (30.0 g) obtained in Synthesis Example 1 and diluted to 6%, and then acetic anhydride (3.42 g) and pyridine (2.65 g) were added as imidization catalysts. And reacted at 60 ° C. for 2 hours.
• This reaction solution was put into methanol (1946 ml), and the resulting precipitate was separated by filtration. This deposit was wash
• Table 1 shows the polyimide polymers obtained in the above synthesis examples.
• * 1 represents polyamic acid.
• Example 1 NEP (0.55 g), GBL (0.55 g) and PB (1.40 g) are added to the polyamic acid solution (1) (3.50 g) obtained in Synthesis Example 1, and the mixture is stirred at 25 ° C. for 6 hours. Thus, a liquid crystal aligning agent (1) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
• Example 2 NMP (0.05 g), BCS (1.05 g) and DME (1.05 g) were added to the polyamic acid solution (2) (3.50 g) obtained in Synthesis Example 2, and the mixture was stirred at 25 ° C. for 6 hours. Thus, a liquid crystal aligning agent (2) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
• Example 3 CHN (22.5 g), ⁇ -VL (11.6 g), and PGME (22.5 g) were added to the polyimide powder (3) (1.75 g) obtained in Synthesis Example 3, and the mixture was stirred at 50 ° C. for 6 hours. did. Further, K1 (0.17 g) was added, and the mixture was stirred at 25 ° C. for 4 hours to obtain a liquid crystal aligning agent (3).
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
• Example 4 NMP (2.70 g) was added to the polyimide powder (4) (0.30 g) obtained in Synthesis Example 4, and the mixture was stirred at 50 ° C. for 6 hours. Further, 7.00 g of the polyamic acid solution (5) obtained in Synthesis Example 5 was added, PC (6.58 g), NEP (6.50 g) and NMP (10.25 g) were added, and the mixture was stirred at 25 ° C. for 4 hours. Thus, a liquid crystal aligning agent (4) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
• a liquid crystal aligning agent (R1) was obtained in the same manner as in Example 1 except that the polyamic acid solution (R-1) obtained in Comparative Synthesis Example 1 was used.
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
• * 1, * 2, and * 3 represent the following meanings.
• * 1 The mass part of the crosslinkable compound with respect to 100 mass parts of all the polymers is shown.
• * 2 Indicates parts by mass of each solvent relative to 100 parts by mass of all solvents.
• * 3 Indicates the ratio of all the polymers in the liquid crystal aligning agent.
• the liquid crystal aligning agents (1) to (4) were subjected to pressure filtration with a membrane filter having a pore diameter of 1 ⁇ m, and the inkjet coating property was evaluated.
• As the ink jet coater HIS-200 (manufactured by Hitachi Plant Technology) was used. Coating is performed on an ITO (indium tin oxide) deposition substrate cleaned with pure water and isopropyl alcohol (IPA), the nozzle pitch is 0.423 mm, the scan pitch is 0.5 mm, the coating speed is 40 mm / second, and the coating is performed. The time from to the temporary drying was 60 seconds, and the temporary drying was performed on a hot plate at 70 ° C. for 5 minutes.
• the coating properties of the obtained substrate with a liquid crystal alignment film were confirmed. Specifically, the coating film was visually observed under a sodium lamp to confirm the presence or absence of pinholes. As a result, in any of the liquid crystal alignment films obtained in any of the examples, no pinhole was found on the coating film, and a liquid crystal alignment film having excellent coating properties was obtained.
• the liquid crystal aligning agent (1) or (3) obtained in the examples was filtered under pressure with a membrane filter having a pore diameter of 1 ⁇ m to produce a liquid crystal cell (normal cell).
• the liquid crystal aligning agent was spin-coated on the ITO surface of a 40 ⁇ 30 mm ITO electrode substrate (length 40 mm ⁇ width 30 mm, thickness 0.7 mm) washed with pure water and IPA, on a hot plate A heat treatment was performed at 100 ° C. for 5 minutes and at 230 ° C. for 30 minutes in a thermal circulation clean oven to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm.
• the liquid crystal aligning agent (2) or (4) obtained by the Example produced the board
• the coated surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm. .
• Two ITO substrates with the obtained liquid crystal alignment film were prepared, combined with a liquid crystal alignment film surface inside and sandwiched by a spacer having a pore diameter of 6 ⁇ m, and the periphery was adhered with a sealant to prepare an empty cell.
• a liquid crystal cell ordinary cell
• liquid crystal MLC-6608, manufactured by Merck Japan
• any liquid crystal cell it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystals were uniformly aligned.
• the polymerizable compound (1) represented by the following formula was used except that a liquid crystal obtained by mixing 0.3 part by mass of the polymerizable compound (1) with respect to 100 parts by mass of the nematic liquid crystal (MLC-6608) was used as described above.
• a liquid crystal cell was prepared in the same procedure as in “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”.
• the polymer of the present invention showed higher solubility when mixed with water than the polymer obtained from the comparative synthesis example.
• the liquid crystal aligning agent from Table 3 showed higher whitening resistance than the liquid crystal aligning agent of the comparative example.
• Example 5 As shown in Table 5, a liquid crystal aligning agent was obtained in the same manner as in Example 4 except that the polyamic acid solution (6) obtained in Synthesis Example 6 or the polyimide powder (7) obtained in Synthesis Example 7 was used. (5) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation. When the PSA cell was prepared using the liquid crystal aligning agent (5), the liquid crystal was uniformly aligned.
• the liquid crystal aligning agent of the present invention can be suitably used for, for example, a large-screen, high-definition liquid crystal television, a small-to-medium-sized car navigation system, a smartphone, and the like, and is a TN element, STN element, TFT liquid crystal element, particularly a vertical alignment type. Useful for liquid crystal display elements. Furthermore, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful for a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element.

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