WO2023068085A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et composé - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et composé Download PDF

Info

Publication number
WO2023068085A1
WO2023068085A1 PCT/JP2022/037650 JP2022037650W WO2023068085A1 WO 2023068085 A1 WO2023068085 A1 WO 2023068085A1 JP 2022037650 W JP2022037650 W JP 2022037650W WO 2023068085 A1 WO2023068085 A1 WO 2023068085A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
liquid crystal
carbon atoms
aligning agent
formula
Prior art date
Application number
PCT/JP2022/037650
Other languages
English (en)
Japanese (ja)
Inventor
玲久 小西
達也 結城
Original Assignee
日産化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to KR1020247015937A priority Critical patent/KR20240090440A/ko
Priority to JP2023554499A priority patent/JPWO2023068085A1/ja
Priority to CN202280080758.3A priority patent/CN118355319A/zh
Publication of WO2023068085A1 publication Critical patent/WO2023068085A1/fr

Links

Classifications

    • 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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to liquid crystal aligning agents, liquid crystal aligning films, liquid crystal display elements, and compounds that can be used therefor.
  • a liquid crystal display device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer, an alignment film for controlling the orientation of liquid crystal molecules in the liquid crystal layer, A thin film transistor (TFT) or the like is provided for switching an electric signal supplied to the pixel electrode.
  • TFT thin film transistor
  • Driving methods for liquid crystal molecules include vertical electric field methods such as the TN (Twisted Nematic) method and VA (Vertical Alignment) method, and horizontal electric field methods such as the IPS (In-Plane Switching) method and the FFS (Fringe Field Switching) method.
  • TN Transmission Nematic
  • VA Very Alignment
  • IPS In-Plane Switching
  • FFS Frringe Field Switching
  • the liquid crystal alignment film that is most widely used industrially is formed on an electrode substrate, and the surface of a film made of a polymer typified by polyamic acid and/or polyimide imidized thereof is coated with cotton, nylon, or the like. It is produced by rubbing in one direction with a cloth such as polyester.
  • the rubbing treatment is a simple, highly productive and industrially useful method.
  • a photo-alignment method that imparts liquid crystal alignment ability by irradiating polarized radiation is known as an alignment treatment method that replaces the rubbing treatment. ing.
  • Non-Patent Document 1 a method using a photoisomerization reaction, a method using a photocrosslinking reaction, a method using a photodecomposition reaction, and the like have been proposed (see, for example, Non-Patent Document 1 and Patent Document 1).
  • a panel vibration test is sometimes performed as a reliability test of liquid crystal display elements for mobile applications such as smartphones and in-vehicle applications such as car navigation systems. In this vibration test, it is required that defects such as bright spots do not occur.
  • a method of increasing the mechanical strength of the liquid crystal alignment film can be considered.
  • a method for improving the mechanical strength of the liquid crystal alignment film, particularly the film strength there is a method of adding a cross-linking agent to the liquid crystal alignment agent.
  • the stability of liquid crystal alignment is also important. If the alignment stability is low, the liquid crystal will not return to its initial state after being driven for a long period of time, causing a decrease in contrast and burn-in (hereinafter referred to as AC afterimage).
  • a liquid crystal aligning agent containing a specific polyimide component and a specific hydroxyalkylamide compound has been proposed (see, for example, Patent Document 2).
  • Patent Document 2 a liquid crystal aligning agent containing a specific polyimide component and a specific hydroxyalkylamide compound.
  • the liquid crystal alignment film used there needs to be more reliable than ever. It is desired to maintain good properties even after prolonged exposure under.
  • a liquid crystal aligning agent containing a specific polyimide-based polymer and a compound has been proposed as a means for solving display defects caused by the AC afterimage and voltage holding ratio (see, for example, Patent Document 3).
  • liquid crystal aligning agent that can satisfy all of these requirements at a high level is desired. Furthermore, when the liquid crystal aligning agent is stored at room temperature for a long time, the components contained in the liquid crystal aligning agent are insolubilized and precipitated, or gelation occurs and becomes unusable, so it is necessary to store it frozen. can occur. Therefore, a liquid crystal aligning agent excellent in storage stability during frozen storage, in which components contained in the liquid crystal aligning agent do not precipitate during frozen storage, is also desired.
  • a liquid crystal aligning agent containing the following (A) component and a compound (B) represented by the following formula (1).
  • (A) component a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative component containing at least one compound selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof and a diamine component;
  • W is *1-NH(Boc), *1-N(Boc) 2 , and “*1-N(Boc)-*1” (*1 is an aliphatic carbon atom.
  • R and R' are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a group "*-C(R 2 ) 2 -C(R 1 ) 2 -OH" (* represents a bond.
  • R 1 and R 2 each independently represent a hydrogen atom or 1 having 1 to 6 carbon atoms and at least one of R and R' is the group "*-C(R 2 ) 2 -C(R 1 ) 2 - OH”.
  • the liquid crystal aligning agent which can obtain the liquid crystal aligning film which has high film
  • the compound (B) has an imidization-promoting structure and a cross-linking site in the same molecule, it cross-links during baking to reduce sublimation and easily improve orientation. In addition, since compound (B) has a group having a protected amino site with high solubility, storage stability during frozen storage is improved.
  • halogen atom includes fluorine atom, chlorine atom, bromine atom, iodine atom and the like.
  • Boc represents a tert-butoxycarbonyl group, and "*" represents a binding position.
  • the liquid crystal aligning agent of this invention contains the said (A) component.
  • the polymer component means a component composed of a polymer, and may be composed of one type of polymer, or may be composed of a plurality of types of polymers.
  • the polymer (A) may be of one type or two or more types.
  • the polymer (A) contained in the component (A) is a tetracarboxylic acid derivative component containing at least one compound selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof, and a diamine component undergoing a polymerization reaction.
  • polyimide polymer (A)) selected from the group consisting of a polyimide precursor obtained by A polyimide precursor in the polyimide polymer (A) is obtained by polymerizing a tetracarboxylic acid derivative component and a diamine component.
  • the tetracarboxylic acid derivative component includes at least one compound selected from the group consisting of tetracarboxylic dianhydrides and derivatives thereof (hereinafter collectively referred to as tetracarboxylic dianhydride-based compounds).
  • examples of the polyimide precursor include polyamic acid and polyamic acid ester.
  • tetracarboxylic dianhydride derivatives examples include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides.
  • the polyimide polymer (A) is a polyamic acid
  • the polyimide polymer (A) is, for example, a tetracarboxylic acid derivative component containing tetracarboxylic dianhydride and a diamine component polymerized (polycondensation ) is obtained by the reaction.
  • the polyimide in the polyimide polymer (A) is obtained by imidizing the polyamic acid.
  • the polyimide-based polymer (A) is a polyamic acid ester, it can be obtained by the method described later, and a polyimide is obtained by imidating the polyamic acid ester.
  • tetracarboxylic dianhydride-based compound examples include aromatic tetracarboxylic dianhydrides, acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and derivatives thereof. be done.
  • the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an aromatic ring.
  • An acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not need to be composed only of a chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in part thereof.
  • the aromatic tetracarboxylic dianhydride or derivative thereof has at least one partial structure selected from the group consisting of a benzene ring structure, a naphthalene ring structure, and an aromatic heterocyclic structure from the viewpoint of enhancing liquid crystal orientation.
  • a tetracarboxylic dianhydride or a derivative thereof is preferred.
  • An alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to the aromatic ring. Moreover, it is not necessary to consist only of an alicyclic structure, and a part thereof may have a chain hydrocarbon structure or an aromatic ring structure.
  • acyclic aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride, or a derivative thereof has a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure from the viewpoint of enhancing liquid crystal orientation.
  • a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of or a derivative thereof is preferable.
  • aromatic tetracarboxylic dianhydride acyclic aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride is, among others, a tetracarboxylic dianhydride represented by the following formula (2) is preferred.
  • X represents a structure selected from the group consisting of the following formulas (x-1) to (x-17) and the following formulas (xr-1) to (xr-2).)
  • R 1 to R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a an alkynyl group, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, or represents a phenyl group, wherein R 5 and R 6 each independently represents a hydrogen atom or a methyl group, and in formulas (xr-1) to (xr-2), j and k is an integer of 0 or 1, and A 1 and A 2 each independently represent a single bond, —O—, —CO—, —COO—, a phenylene group, a sulfonyl group, or an amide
  • Preferred specific examples of the tetracarboxylic dianhydride represented by the above formula (2) include X being the above formulas (x-1) to (x-8), (x-10) to (x-11) , and (xr-1) to (xr-2).
  • the above formula (x-1) is preferably selected from the group consisting of the following formulas (x1-1) to (x1-6).
  • the amount of the tetracarboxylic dianhydride or derivative thereof represented by the above formula (2) when producing the polyimide polymer (A) is 1 mol of the total tetracarboxylic acid derivative component to be reacted with the diamine component. On the other hand, 5 mol% or more is preferable, 10 mol% or more is more preferable, and 20 mol% or more is still more preferable.
  • the diamine component used for producing the polyimide precursor is not particularly limited, a diamine component containing a diamine represented by the following formula (3) is preferable.
  • Ar 1 and Ar 1′ each independently represent a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more A hydrogen atom may be substituted with a monovalent group
  • Ar 1 and Ar 1' in the formula (3) each independently represent a benzene ring, a biphenyl structure, or a naphthalene ring.
  • One or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group, and the monovalent group includes a halogen atom, an alkyl having 1 to 3 carbon atoms, group, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkenyl group having 2 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, An alkyloxycarbonyl group having 2 to 3 carbon atoms, a cyano group, a nitro group and the like can be mentioned.
  • the bonding position between the amino group and L 1 or L 1′ with respect to the benzene ring is more preferably 1,4-position or 1,3-position, 1,4-position is more preferred.
  • the bonding positions of the amino group and L 1 or L 1′ with respect to the biphenyl structure are preferably 4,4′-positions or 3,3′-positions, more preferably 4,4′-positions.
  • the bonding positions of the amino group and L 1 or L 1′ with respect to the naphthalene ring are preferably 1,5-positions or 2,6-positions, more preferably 2,6-positions.
  • Preferred specific examples of Ar 1 and Ar 1' include a benzene ring, a biphenyl structure and a naphthalene ring.
  • a preferred specific example of A is a linear alkylene group having 2 to 6 carbon atoms.
  • n is an integer of 1-12, more preferably an integer of 2-12, and even more preferably an integer of 2-6.
  • the sum of m1, m2 and n' is an integer of 3-12, preferably an integer of 6-12.
  • Each of m1 and m2 is preferably an integer of 1 to 4, more preferably an integer of 2 to 4.
  • n′ is preferably an integer of 1-6, more preferably an integer of 2-6, and even more preferably an integer of 2-4.
  • the ratio of the diamine represented by formula (3) is preferably 1 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more, relative to 1 mol of the diamine component. preferable.
  • the polyimide polymer (A) may contain diamines other than the diamines described above. Examples of other diamines are listed below, but the present invention is not limited to these. In addition to the diamine represented by the above formula (3), when other diamines are used in combination, the amount of the diamine represented by the formula (3) to the diamine component is preferably 90 mol% or less, and 80 mol%. The following are more preferred. Examples of other diamines are listed below, but the present invention is not limited to these. The other diamines may be used singly or in combination of two or more.
  • p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 1, 4-diamino-2,5-dimethoxybenzene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine, secondary amino group and primary
  • a semi-aromatic diamine having an amino group preferably 4-(2-(methylamino)ethyl)aniline) (here, the semi-aromatic diamine refers to and the other amino group refers to a diamine not bound to an aromatic ring.), 4-(2-aminoethyl)aniline, 2-(6-amino-2-naphthyl)ethylamine, 2,2
  • At least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary or tertiary amino group, typified by a diamine having a diphenylamine structure of -N(D)- (D represents a protective group that is eliminated by heating and replaced with a hydrogen atom. ) except amino groups derived from );
  • m and n are each an integer of 0 to 3 (provided that 1 ⁇ m + n ⁇ 4), j is an integer of 0 or 1, and X 1 is - (CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CO—N(CH 3 )—, —NH—, —O—, —CH 2 O— , —CH 2 —OCO—, —COO—, or —OCO—, wherein R 1 is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, represents an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms, wherein X 2 is -O- or -
  • D in -N(D)- of the other diamines described above is a carbamate-based protective group represented by a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, Boc, and the like.
  • Boc is particularly preferred from the viewpoint that it is efficiently desorbed by heat, is desorbed at a relatively low temperature, and is discharged as a harmless gas when desorbed.
  • diamines having thermally-leaving groups include diamines selected from the following formulas (d-1) to (d-7).
  • R represents a hydrogen atom or Boc.
  • the diamine having the thermally-leaving group is used as the diamine component used in the production of the polyimide precursor, from the viewpoint of suitably obtaining the effect of the present invention, it is preferably 5 to 40 mol per 1 mol of the diamine component. %, more preferably 5 to 35 mol %, even more preferably 5 to 30 mol %.
  • the polymer (A) is a polyimide precursor obtained using a diamine component containing a diamine having the nitrogen atom-containing structure from the viewpoint of reducing residual DC-derived afterimages or improving electrical properties, and the polyimide precursor It may contain at least one polymer selected from the group consisting of imidized products of polyimide (hereinafter also referred to as polyimide-based polymer (Q)).
  • the tetracarboxylic acid derivative component for obtaining the polyimide-based polymer (Q) include a tetracarboxylic acid derivative component containing the above-described tetracarboxylic dianhydride-based compound.
  • the tetracarboxylic dianhydride-based compound for obtaining the polyimide polymer (Q) is preferably a tetracarboxylic dianhydride represented by the above formula (2) or a derivative thereof.
  • the amount of the tetracarboxylic dianhydride or derivative thereof represented by the above formula (2) is preferably 10 mol% or more, preferably 20 mol%, based on 1 mol of the total tetracarboxylic acid derivative component to be reacted with the diamine component. The above is more preferable.
  • the amount of the diamine having the nitrogen atom-containing structure is 5 to 100 mol with respect to the total amount of the diamine component for obtaining the polymer (Q). %, more preferably 10 to 95 mol %, even more preferably 20 to 80 mol %.
  • a diamine component for obtaining the polyimide polymer (Q) a diamine other than the diamine having a nitrogen atom-containing structure may be further contained.
  • the amount of diamine (c) used is preferably 1 to 95 mol%, more preferably 5 to 90 mol%, and further 20 to 80 mol%, based on the total amount of the diamine component for obtaining the polymer (Q). preferable.
  • the (A) component contained in the liquid crystal aligning agent of the present invention is the polyimide polymer (Q) and a polyimide precursor obtained using a diamine component that does not contain a diamine having a nitrogen atom-containing structure and the polyimide It may be a mixture with at least one polymer selected from the group consisting of imidized precursors (hereinafter also referred to as polyimide polymer (H)).
  • the diamine represented by the above formula (3) p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 1,4-diamino-2,5-dimethoxybenzene, 2,5-diaminotoluene, 2,6-diamino toluene, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine, semi-aromatic diamines having secondary and primary amino groups (preferably 4-(2-(methylamino)ethyl) aniline.) (Here, a semi-aromatic diamine refers to a diamine in which one amino group is bonded to an aromatic ring and the other amino group is not bonded to an aromatic ring.), 4-aminobenzylamine, 2-(4-aminophenyl
  • the content ratio of the polyimide polymer (Q) and the polyimide polymer (H) is the mass ratio of [polyimide polymer (Q)]/[polyimide polymer (H)], and is 10/90 to 90/ It is preferably 10, more preferably 20/80 to 80/20, even more preferably 30/70 to 70/30.
  • (A) component contained in the liquid crystal aligning agent of this invention may contain other polymers other than a polymer (A).
  • other polymers include polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic acid). anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, and polymers selected from the group consisting of poly(meth)acrylates.
  • poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac Manufacturing Co., Ltd.) and the like.
  • Anhydride) copolymers include Isoban-600 (manufactured by Kuraray Co., Ltd.), and specific examples of poly(vinyl ether-maleic anhydride) copolymers include Gantrez AN-139 (methyl vinyl ether anhydride). maleic acid resin, manufactured by Ashland).
  • Other polymers may be used singly or in combination of two or more.
  • the content of the other polymer is more preferably 0.1 to 90 parts by mass, still more preferably 1 to 90 parts by mass, per 100 parts by mass of component (A) contained in the liquid crystal aligning agent.
  • Polyamic acid which is one of polyimide precursors, can be produced by the following method. Specifically, a tetracarboxylic acid derivative component containing a tetracarboxylic dianhydride and the diamine component are mixed in the presence of an organic solvent at a temperature of preferably -20 to 150°C, more preferably 0 to 50°C. It can be synthesized by reacting (polycondensation reaction) for 30 minutes to 24 hours, more preferably 1 hour to 12 hours.
  • organic solvent used in the above reaction examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone can be mentioned.
  • methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or propylene glycol monomethyl ether ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used. These may be used in combination of two or more.
  • the reaction can be carried out at any concentration, preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial stage of the reaction can be carried out at a high concentration, and then the 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 derivative component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer this molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced.
  • the polyamic acid obtained in the above reaction can be recovered by precipitating the polyamic acid by injecting the reaction solution into a poor solvent while stirring well. Further, a purified polyamic acid powder can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating. Poor solvents include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.
  • a polyamic acid ester which is one of the polyimide precursors, can be obtained by (1) a method of esterifying the polyamic acid, (2) a method of reacting a tetracarboxylic acid derivative component containing a tetracarboxylic acid diester dichloride with a diamine component, ( 3) It can be produced by a known method such as a method of polycondensing a tetracarboxylic acid derivative component including a tetracarboxylic acid diester with a diamine.
  • the above-mentioned polyamic acid and polyamic acid ester may be a terminal-modified polymer obtained by using an appropriate terminal blocking agent together with the tetracarboxylic acid derivative component and the diamine component as described above when producing them.
  • Terminal blockers include, for example, acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, and trimellitic anhydride.
  • Acid monoanhydrides such as anhydrides; dicarbonic acid diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride and nicotinic acid chloride; aniline, 2-aminophenol, 3 -aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n - monoamine compounds such as hexylamine,
  • the proportion of the terminal blocking agent used is preferably 40 mol parts or less, more preferably 30 mol parts or less, with respect to a total of 100 mol parts of the diamine component used. Moreover, the proportion of the terminal blocker used is preferably 0.01 mol or more, more preferably 0.1 mol or more, with respect to a total of 100 mol parts of the diamine component used.
  • the polyimide used in the present invention can be produced by imidizing the above polyimide precursor by a known method.
  • the ring closure rate (also referred to as imidization rate) of the functional groups of the polyamic acid or polyamic acid ester does not necessarily need to be 100%, and can be arbitrarily adjusted according to the application and purpose.
  • the imidization rate of the polyimide in the polymer (A) of the present invention may be, for example, 20 to 100%, 50 to 99%, or 70 to 99% from the viewpoint of reducing the occurrence rate of display defects.
  • thermal imidization is performed by heating the solution of the polyamic acid or polyamic acid ester as it is, or a catalyst (eg, catalyzed imidization by adding a basic catalyst such as pyridine, an acid anhydride such as acetic anhydride).
  • a catalyst eg, catalyzed imidization by adding a basic catalyst such as pyridine, an acid anhydride such as acetic anhydride.
  • the polyamic acid, polyamic acid ester and polyimide used in the present invention preferably have a solution viscosity of, for example, 10 to 1000 mPa s when the concentration is 10 to 15% by mass, from the viewpoint of workability. , is not particularly limited.
  • the solution viscosity (mPa s) of the polymer is a polymer having a concentration of 10 to 15 mass% prepared using a good solvent for the polymer (eg, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25° C. for a solution using an E-type rotational viscometer.
  • the polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyamic acid, polyamic acid ester and polyimide is preferably 1,000 to 500,000, more preferably 2,000. ⁇ 500,000.
  • the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. With such a molecular weight range, it is possible to ensure good liquid crystal orientation of the liquid crystal display element.
  • the liquid crystal aligning agent of the present invention contains the compound (B) represented by the above formula (1).
  • One type of compound (B) may be used, or two or more types may be used.
  • the compound (B) itself is also an object of the present invention independently of the liquid crystal aligning agent of the present invention.
  • R and R' are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a carbon number 1 to 6 alkoxy groups or groups “*—C(R 2 ) 2 —C(R 1 ) 2 —OH” (* represents a bond.
  • R 1 and R 2 are each independently a hydrogen atom or a carbon represents a monovalent organic group of numbers 1 to 6), wherein at least one of R and R′ is the group “*—C(R 2 ) 2 —C(R 1 ) 2 -OH”. From the viewpoint of suitably obtaining the effects of the present invention, R and R' preferably represent the group "*-C(R 2 ) 2 -C(R 1 ) 2 -OH”.
  • alkyl groups having 1 to 6 carbon atoms in R and R' in the above formula (1) include methyl group and ethyl group; examples of alkenyl groups having 2 to 6 carbon atoms include vinyl group and propenyl group; Examples of alkynyl groups having 2 to 6 numbers include ethynyl group and propynyl group; examples of alkoxy groups having 1 to 6 carbon atoms include methoxymethyl group and methoxyethyl group.
  • the monovalent organic group having 1 to 6 carbon atoms for R 1 and R 2 in the above group "*-C(R 2 ) 2 -C(R 1 ) 2 -OH" is an alkyl group having 1 to 6 carbon atoms. , alkenyl groups having 2 to 6 carbon atoms, and alkynyl groups having 2 to 6 carbon atoms. Some or all of the hydrogen atoms in the alkyl group, alkenyl group, and alkynyl group may be substituted with a substituent. A halogen atom, a cyano group, a nitro group, a hydroxy group, etc. are mentioned as said substituent.
  • R 1 and R 2 are preferably hydrogen atoms or methyl groups.
  • W in the above formula (1) is *1-NH(Boc), *1-N(Boc) 2 , and “*1-N(Boc)-*1” (*1 is a bond to an aliphatic carbon atom. represents an organic group having a group having a protected amino moiety (ap) selected from the group consisting of (a) and having 1 to 30 carbon atoms excluding a Boc group.
  • W is, specifically, "W-COOH" (W is synonymous with W in formula (1).
  • W also referred to as carboxylic acid (W).) Remove the carboxy group from the carboxylic acid represented by groups. From the viewpoint of suitably obtaining the effects of the present invention, W in the above formula (1) more preferably has a group having a protected amino moiety in which the amino group constituting the nitrogen atom-containing heterocyclic ring described later is protected.
  • the compound represented by the above formula (1) is more preferably a compound represented by the following formula (b).
  • R and R' are synonymous with R and R' in formula (1), and R" represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group for R′′ in the above formula (b) includes a monovalent organic group having 1 to 29 carbon atoms, and the organic group is a monovalent hydrocarbon group having 1 to 29 carbon atoms ( a monovalent acyclic chain hydrocarbon group having 1 to 29 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 29 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 29 carbon atoms), At least one methylene group in the hydrocarbon group is -O-, -S-, -CO-, -COO-, -COS-, -NR 1 -, -CONR 1 - (R 1 is a hydrogen atom or carbon number
  • a monovalent organic group (u) substituted with a divalent functional group such as a hydrocarbon group of 1 to 6), or at least one hydrogen atom of the above hydrocarbon group or organic group (u) is a halogen atom , an amino group (excluding a nitrogen atom-containing heterocyclic ring),
  • the aromatic hydrocarbon group may be composed only of an aromatic hydrocarbon group (e.g., benzene ring, etc.), part of which contains at least one of an acyclic chain structure and the alicyclic structure. Further, the alicyclic hydrocarbon group may be composed only of an alicyclic structure (for example, a cyclohexane ring, etc.), part of which contains an acyclic chain structure. good too.
  • the monovalent organic group for R′′ in the above formula (b) is more preferably a monovalent organic group having a nitrogen atom-containing heterocyclic ring or a derivative thereof, from the viewpoint of suitably obtaining the effects of the present invention. Preferred nitrogen atom-containing Heterocycles are as described below.
  • the carboxylic acid (W) is a carboxylic acid represented by HOOC-C(R")(-NHBoc) (R" is synonymous with R" in formula (b)) from the viewpoint of raw material availability. Acids or derivatives thereof are preferred.
  • the compound (B) is, for example, a carboxylic acid (W) or a derivative thereof (active ester compound, acid halide, etc.) and "HN (R) (R')" (R, R' are (synonymous with R and R').
  • the carboxylic acid (W) contains *1-NH(Boc), *1-N(Boc) 2 and “*1-N(Boc)-*1)” (*1 is an aliphatic carbon A group having a protected amino site (ap) selected from the group consisting of a bond that binds to an atom.
  • the carboxylic acid (W) protects the amino groups possessed by the carboxy group-containing polyamine (pA) having two or more amino groups, represented by, for example, a carboxy group-containing monoamine (mA) or a carboxy group-containing diamine. obtained by As for the protection of amino groups, some of the amino groups possessed by the amine may be protected, or all of the amino groups may be protected.
  • monoamines include aliphatic monoamines such as glycine, alanine, methionine, isoleucine, norleucine, phenylalanine, or proline.
  • polyamines include aliphatic polyamines such as arginine, lysine, ornithine, or histidine.
  • the carboxylic acid (W), monoamine (mA), and polyamine (pA) preferably have a nitrogen atom-containing heterocyclic ring or a derivative thereof, among others, from the viewpoint of suitably obtaining the effects of the present invention.
  • Specific examples of the nitrogen atom-containing heterocyclic ring include aziridine, azetidine, pyrrole, imidazole, imidazolidine, pyrrolidine, piperidine, piperazine, morpholine, pyrazole, indole, benzimidazole, or carbazole.
  • specific examples of derivatives of the nitrogen atom-containing heterocyclic ring include compounds in which any hydrogen atom of the nitrogen atom-containing heterocyclic ring is substituted with the following substituents.
  • substituents examples include linear or branched alkyl groups having 1 to 4 carbon atoms, linear or branched alkoxy groups having 1 to 4 carbon atoms, hydroxy groups, halogen atoms, nitro group, cyano group, trifluoromethyl group, —NR 7 R 8 or —CONR 7 R 8 group, wherein R 7 and R 8 each independently represent a hydrogen atom, linear or branched It represents a chain alkyl group having 1 to 4 carbon atoms.
  • the carboxylic acid (W) preferably has a group having a protected amino moiety, in which the amino group constituting the nitrogen atom-containing heterocyclic ring is protected.
  • the group having a protected amino site in which the amino group constituting the nitrogen atom-containing heterocyclic ring is protected include a group having a protected amino site in which the secondary amino group constituting imidazole is protected, and piperidine. and a group having a protected amino site in which at least one of the secondary amino groups constituting piperazine is protected.
  • the compound represented by the above formula (1) is more preferably a compound represented by any one of the following formulas (b-1) to (b-4).
  • the content of the compound (B) contained in the liquid crystal aligning agent of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of component (A). parts, more preferably 1 to 10 parts by mass.
  • the liquid crystal aligning agent of this invention is used in order to produce a liquid crystal aligning film, and takes the form of a coating liquid from a viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of the present invention, it is preferable that the liquid crystal aligning agent is a coating liquid containing the above-described polymer component and a solvent.
  • the content (concentration) of the polymer component contained in the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of the coating film to be formed. 1 mass % or more is preferable with respect to the whole quantity of a point and a liquid crystal aligning agent, and 10 mass % or less is preferable from the point of the storage stability of a solution.
  • the content of the polymer (A) in the liquid crystal aligning agent is preferably 10 parts by mass or more with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. Yes, more preferably 20 parts by mass or more, and still more preferably 50 parts by mass or more.
  • the content of the polymer (A) when the liquid crystal aligning agent contains another polymer is as described above.
  • the solvent contained in the liquid crystal aligning agent is not particularly limited as long as it uniformly dissolves the polymer component.
  • Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide and ⁇ -butyrolactone.
  • ⁇ -valerolactone 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl )-2-pyrrolidone, N-(3-methoxypropyl)-2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-(4-methoxybutyl)-2-pyrrolidone, N-cyclohexyl-2 -pyrrolidone (these are collectively referred to as "
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and ⁇ -butyrolactone are preferred.
  • the content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.
  • the solvent contained in the liquid crystal aligning agent is a mixed solvent in which a solvent (also referred to as a poor solvent) that improves the coatability and the surface smoothness of the coating film when applying the liquid crystal aligning agent is used in addition to the above solvent. is preferred. Specific examples of the poor solvent used in combination are shown below, but are not limited thereto.
  • the content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, particularly preferably 20 to 70% by mass, of the total solvent contained in the liquid crystal aligning agent.
  • the type and content of the poor solvent are appropriately selected according to the liquid crystal aligning agent coating device, coating conditions, coating environment, and the like.
  • diisobutyl carbinol propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate or diisobutyl ketone are preferred.
  • Preferred solvent combinations of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone and ethylene glycol monobutyl ether, N-methyl-2- Pyrrolidone, ⁇ -butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N
  • the liquid crystal aligning agent of the present invention may additionally contain components (hereinafter also referred to as additive components) other than the polymer component and the solvent.
  • additive components include compounds for increasing the strength of the liquid crystal alignment film (hereinafter also referred to as cross-linking compounds), adhesion between the liquid crystal alignment film and the substrate, and adhesion between the liquid crystal alignment film and the sealing agent. Adhesion aids for increasing the dielectric constant and electrical resistance of the liquid crystal alignment film, dielectrics and conductive substances.
  • crosslinkable compound examples include a crosslinkable compound (c-1) having at least one substituent selected from an epoxy group, an oxetanyl group, an oxazoline structure, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group and an alkoxy group.
  • crosslinkable compound (c-1) and (c-2) include the following compounds.
  • epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane.
  • Polymers and oligomers having an oxazoline group such as compounds described in paragraph [0115] of Japanese Patent Application Laid-Open No. 2007-286597;
  • compounds having a cyclocarbonate group N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N' ,-Di[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine and paragraphs [0025] to [0030] and [0032] of WO2011/155577 compounds of;
  • Examples of compounds having a blocked isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B
  • crosslinkable compounds are examples of crosslinkable compounds, and are not limited to these.
  • components other than those described above disclosed on pages 53 [0105] to 55 [0116] of WO2015/060357 may be used.
  • the content of the crosslinkable compound in the liquid crystal aligning agent is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. , more preferably 1 to 15 parts by mass.
  • adhesion aid examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N -ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-3-triethoxysilylpropyltriethylenetetramine, N-3-trimethoxysilylpropylprop
  • the content of the adhesion aid in the liquid crystal aligning agent is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer component contained in the liquid crystal aligning agent, and more It is preferably 0.1 to 20 parts by mass.
  • dielectric or conductive substances include monoamines having nitrogen-containing aromatic heterocycles such as 3-picolylamine.
  • the content of the dielectric or conductive substance in the liquid crystal aligning agent is 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. is preferred, and more preferably 0.1 to 20 parts by mass.
  • the liquid crystal aligning film of the present invention is formed using the liquid crystal aligning agent of the present invention.
  • the method for producing a liquid crystal alignment film of the present invention includes, for example, applying the above liquid crystal alignment agent to a substrate, baking the substrate, and irradiating the resulting film with polarized radiation.
  • a preferred embodiment of the method for producing a liquid crystal alignment film of the present invention includes, for example, the step of applying the liquid crystal alignment agent to the substrate (step (1)), and the step of baking the applied liquid crystal alignment agent (step (2)). and a method for producing a liquid crystal alignment film, which optionally includes a step (step (3)) of subjecting the film obtained in step (2) to orientation treatment.
  • the substrate to which the liquid crystal aligning agent used in the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can also be used. In that case, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for driving the liquid crystal is formed, in terms of process simplification.
  • an opaque material such as a silicon wafer can be used, and in this case, a light-reflecting material such as aluminum can be used for the electrodes.
  • Screen printing, offset printing, flexographic printing, inkjet method, spray method, etc. can be used as methods for applying the liquid crystal aligning agent to the substrate and forming a film.
  • the coating method and the film-forming method by the inkjet method can be preferably used.
  • a process (2) is a process of baking the liquid crystal aligning agent apply
  • the solvent is evaporated by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven, or the thermal imide of the amic acid or amic acid ester in the polymer. It is possible to change
  • the drying and baking steps after applying the liquid crystal aligning agent of the present invention can be performed at any desired temperature and time, and may be performed multiple times.
  • the temperature for evaporating the solvent of the liquid crystal aligning agent can be, for example, 40 to 180° C.
  • the temperature of the heating means may be 40 to 150° C. from the viewpoint of shortening the process.
  • the firing time is not particularly limited, it is, for example, 1 to 10 minutes, preferably 1 to 5 minutes.
  • the temperature of the heating means is, for example, 150 to 300. C., preferably in the temperature range of 150-250.degree.
  • the baking time in the thermal imidization step is not particularly limited, but is, for example, 5 to 40 minutes, preferably 5 to 30 minutes.
  • Step (3) is a step of subjecting the film obtained in step (2) to orientation treatment. That is, in a vertical alignment type liquid crystal display element such as a VA system or a PSA system (Polymer Sustained Alignment), the formed coating film can be used as it is as a liquid crystal alignment film, but the coating film is subjected to an alignment ability imparting treatment. may be applied.
  • a rubbing treatment method may be used, but a photo-alignment treatment method is preferable.
  • Examples of the photo-alignment treatment include a method in which the surface of the film is irradiated with radiation polarized in a certain direction and optionally subjected to heat treatment to impart liquid crystal alignment (also referred to as liquid crystal alignment ability).
  • radiation ultraviolet light 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, more preferably 200 to 400 nm are preferred.
  • the radiation dose is preferably 1 to 10,000 mJ/cm 2 , more preferably 100 to 5,000 mJ/cm 2 .
  • the substrate having the film-like material may be irradiated with heating at 50 to 250° C. in order to improve liquid crystal orientation.
  • the liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a fixed direction.
  • the liquid crystal alignment film irradiated with polarized radiation can be subjected to a contact treatment using a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.
  • the solvent used in the contact treatment is not particularly limited as long as it dissolves the decomposed product produced from the film-like material by irradiation with radiation.
  • Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like.
  • water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate are preferable from the viewpoint of versatility and solvent safety. More preferred are water, 1-methoxy-2-propanol or ethyl lactate.
  • Solvents may be used singly or in combination of two or more.
  • the above contact treatment includes immersion treatment and spray treatment (also called spray treatment).
  • the treatment time in these treatments is preferably 10 seconds to 1 hour from the viewpoint of efficiently dissolving the decomposition products produced from the film-like material by irradiation with radiation. Among them, it is more preferable to perform the immersion treatment for 1 minute to 30 minutes.
  • the solvent used in the contact treatment may be at room temperature or heated, but is preferably 10 to 80°C, more preferably 20 to 50°C.
  • ultrasonic treatment or the like may be performed as necessary.
  • rinsing also called rinsing
  • a low-boiling solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone
  • baking either one of rinsing and baking may be performed, or both may be performed.
  • the firing temperature is preferably 150 to 300°C, more preferably 180 to 250°C, and still more preferably 200 to 230°C.
  • the firing time is preferably 10 seconds to 30 minutes, more preferably 1 minute to 10 minutes.
  • the heat treatment of the radiation-irradiated coating film is preferably carried out at 50 to 300° C. for 1 to 30 minutes, more preferably at 120 to 250° C. for 1 to 30 minutes.
  • the liquid crystal display element of the present invention has the liquid crystal alignment film of the present invention.
  • the liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a horizontal electric field type liquid crystal display element such as an IPS type or an FFS type liquid crystal display element from the viewpoint of obtaining high liquid crystal orientation, and is particularly suitable for an FFS type liquid crystal display element. It is useful as a liquid crystal alignment film.
  • the liquid crystal display element is produced by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention, producing a liquid crystal cell by a known method, and arranging the liquid crystal in the liquid crystal cell. can be done. Specifically, the following two methods are mentioned.
  • the first method first, two substrates are arranged facing each other with a gap (cell gap) between them so that the respective liquid crystal alignment films face each other. Next, the peripheries of the two substrates are bonded together using a sealing agent, and a liquid crystal composition is injected and filled into the cell gap defined by the substrate surface and the sealing agent to contact the film surface, and then the injection hole is sealed. stop.
  • the second method is a technique called the ODF (One Drop Fill) method.
  • a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, an ultraviolet light-curing sealant, and a liquid crystal composition is applied to several predetermined places on the surface of the liquid crystal alignment film. drip.
  • the other substrate is attached so that the liquid crystal alignment films face each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface.
  • the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant.
  • the liquid crystal composition used is further heated to a temperature at which it assumes an isotropic phase, and then slowly cooled to room temperature, so that the flow orientation at the time of filling the liquid crystal should be removed.
  • the coating film is subjected to the rubbing treatment, the two substrates are arranged opposite to each other so that the rubbing directions of the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.
  • the alignment directions are arranged to face each other at a predetermined angle, for example, perpendicular or antiparallel.
  • Liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.
  • the liquid crystal composition is not particularly limited, and is a composition containing at least one liquid crystal compound (liquid crystal molecule) and having a positive dielectric anisotropy (positive liquid crystal composition, also referred to as positive liquid crystal). ) or a liquid crystal composition having a negative dielectric anisotropy (also referred to as a negative liquid crystal composition or a negative liquid crystal) may be used, but a negative liquid crystal composition is preferred.
  • the above liquid crystal composition contains a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocyclic ring, a cycloalkane,
  • a liquid crystal compound having a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring may be included, and a compound having two or more rigid sites (mesogenic skeleton) exhibiting liquid crystallinity in the molecule (for example, two rigid biphenyl structure, or a bimesogenic compound in which a terphenyl structure is linked by an alkyl group).
  • the liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase.
  • the liquid crystal composition may further contain an additive from the viewpoint of improving liquid crystal orientation.
  • additives include photopolymerizable monomers such as compounds having a polymerizable group described below; optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); antioxidants; UV absorbers; dyes; antifoaming agents; polymerization initiators; or polymerization inhibitors.
  • Positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019 and MLC-7081 manufactured by Merck.
  • MLC-3023 manufactured by Merck Co., Ltd. can be used as a liquid crystal containing a compound having a polymerizable group.
  • a polarizing plate is installed. Specifically, a pair of polarizing plates are attached to the surfaces of the two substrates opposite to the liquid crystal layer.
  • the polarizing plate examples include a polarizing plate in which a polarizing film called "H film” in which iodine is absorbed while stretching orientation of polyvinyl alcohol is sandwiched between cellulose acetate protective films, or a polarizing plate composed of the H film itself. .
  • NMP N-methyl-2-pyrrolidone
  • BCS butyl cellosolve (ethylene glycol monobutyl ether)
  • THF tetrahydrofuran
  • GBL ⁇ -butyrolactone
  • AD-1 (Monomer Synthesis Example 1 Synthesis of AD-1) AD-1 was synthesized according to the scheme below. ⁇ Synthesis of AD-1-1> In a flask, N,N'-di(tert-butoxycarbonyl)-L-histidine (1.86 g, 5.23 mmol, manufactured by Merck) and THF (18.6 g) were added and dissolved, and EDC (0. 812 g, 5.23 mmol) was added and stirred at room temperature (25° C.) for 30 minutes.
  • AD-1-1 (7.40 g, 14.8 mmol) and dichloromethane (52 g) were added and dissolved in the flask. Furthermore, triethylamine (TEA, 2.99 g, 29.6 mmol) was added, and a solution obtained by dissolving bis[2-(trimethylsiloxy)ethyl]amine (4.06 g, 16.3 mmol) in dichloromethane (22 g) was placed in the flask. and stirred at room temperature (25° C.) for 18 hours to react. Bis[2-(trimethylsiloxy)ethyl]amine was synthesized with reference to the method described in WO2009/046536.
  • a liquid crystal aligning agent (AL-2) was obtained by performing the same operation as in Example 1, except that AD-1 was not added.
  • Example 3 Perform the same operation as in Example 1, except that AD-2 (0.071 g, 0.15 mmol) and AD-3 (0.048 g, 0.15 mmol) are added instead of AD-1. Thus, a liquid crystal aligning agent (AL-4) was obtained.
  • the liquid crystal aligning agents AL-1 to AL-4 obtained in Example 1 and Comparative Examples 1 to 3 were each applied to an ITO substrate by spin coating. After drying the applied liquid crystal aligning agent on a hot plate at 80° C. for 2 minutes, it was baked in an IR oven at 230° C. for 30 minutes to form a coating film having a thickness of 100 nm. The surface of this coating film was irradiated with 300 mJ/cm 2 of linearly polarized ultraviolet light having a wavelength of 254 nm and an extinction ratio of 26:1 through a polarizing plate for orientation treatment, and then baked in an IR oven at 230° C. for 30 minutes. A substrate with a liquid crystal alignment film was obtained.
  • the liquid crystal alignment film was rubbed with a rayon cloth (manufactured by Yoshikawa Kako, YA-20R) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm/sec, pushing length: 0.5 mm).
  • the haze value (turbidity) of the film was evaluated using a haze meter (manufactured by Suga Test Instruments Co., Ltd., HZ-V3). It can be said that the smaller the haze value, the less the film is scraped, that is, the higher the film hardness.
  • the evaluation criteria the case where the haze value was 0.30 or less was evaluated as "good", and the case where the haze value was greater than 0.30 was evaluated as "poor”.
  • a liquid crystal cell having the structure of an FFS mode liquid crystal display element was produced.
  • a substrate with electrodes was prepared.
  • a glass substrate having a rectangular shape of 30 mm ⁇ 50 mm and a thickness of 0.7 mm was used as the substrate.
  • an ITO electrode thinness: 50 nm, electrode width: 20 mm long, 10 mm wide
  • a SiN (silicon nitride) film formed by a CVD (chemical vapor deposition) method was formed.
  • the SiN film of the second layer has a film thickness of 300 nm and functions as an interlayer insulating film.
  • a comb-shaped pixel electrode (thickness: 50 nm) formed by patterning an ITO film is arranged as the third layer, and the first pixel and the second pixel are arranged. Two pixels were formed, and the size of each pixel was about 10 mm long and about 5 mm wide.
  • the counter electrode of the first layer and the pixel electrode of the third layer were electrically insulated by the action of the SiN film of the second layer.
  • the pixel electrode of the third layer has a comb shape in which a plurality of electrode elements each having a width of 3 ⁇ m and having a central portion bent at an internal angle of 160° are arranged in parallel with an interval of 6 ⁇ m.
  • Each pixel had a first region and a second region bounded by a line connecting bent portions of a plurality of electrode elements.
  • the coating film surface was irradiated with 300 mJ/cm 2 of linearly polarized ultraviolet light having a wavelength of 254 nm and an extinction ratio of 26:1 through a polarizing plate for orientation treatment.
  • a substrate with an alignment film was obtained.
  • the liquid crystal alignment film formed on the substrate with the electrode is aligned so that the direction of equally dividing the interior angle of the bent portion of the pixel is orthogonal to the alignment direction of the liquid crystal, and the liquid crystal alignment film is formed on the second glass substrate.
  • alignment treatment was performed so that the alignment direction of the liquid crystal on the first glass substrate and the alignment direction of the liquid crystal on the second glass substrate were the same when the liquid crystal cell was produced.
  • the above two substrates are set as a set, and a sealant (XN-1500T manufactured by Mitsui Chemicals, Inc.) is printed around the liquid crystal injection port, and another substrate is placed so that the alignment direction facing the liquid crystal alignment film surface is 0. °. After that, a heat treatment was performed at 150° C. for 60 minutes to cure the sealant to prepare an empty cell. Liquid crystal MLC-3019 (manufactured by Merck & Co.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. After that, the obtained liquid crystal cell was heated at 110° C. for 1 hour and allowed to stand overnight before being used for evaluation.
  • a sealant XN-1500T manufactured by Mitsui Chemicals, Inc.
  • the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the first pixel is darkest to the angle at which the first region of the first pixel is darkest is calculated as the angle ⁇ .
  • the second region and the first region were compared to calculate a similar angle ⁇ .
  • the average value of the angle ⁇ between the first pixel and the second pixel was calculated as the angle ⁇ of the liquid crystal cell.
  • the angle ⁇ of the liquid crystal cell obtained above was defined as “ ⁇ ” when it was less than 0.05°, and was defined as “X” when it was 0.05° or more.
  • VHR of 95% or more was defined as " ⁇ "
  • a VHR of 90% or more and less than 95% was defined as " ⁇ ”
  • a VHR of less than 90% was defined as "X”.
  • Table 2 below shows the results of evaluation of afterimage, evaluation of voltage holding ratio, and evaluation of hardness of liquid crystal alignment films in Example 1 and Comparative Examples 1 to 3 by long-term AC driving.
  • Example 2 A 10% NMP solution of AD-1 (1.20 g) was added to a 50 mL Erlenmeyer flask containing a stir bar, and NMP (2.80 g), GBL (3.00 g) and BCS (3.00 g) were added, The mixture was stirred overnight with a magnetic stirrer to obtain a cross-linking agent solution (Sol-1).
  • the obtained liquid crystal cell can be provided with good afterimage resistance and voltage holding ratio. It was found that the obtained liquid crystal alignment film can provide a higher film hardness and can form a liquid crystal alignment agent excellent in low-temperature storage stability.
  • the liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention can be suitably used for various liquid crystal display elements represented by IPS drive system and FFS drive system liquid crystal display elements. These display elements are not limited to liquid crystal displays intended for display, and are also useful in light control windows and optical shutters for controlling the transmission and blocking of light.
  • IPS drive system and FFS drive system liquid crystal display elements These display elements are not limited to liquid crystal displays intended for display, and are also useful in light control windows and optical shutters for controlling the transmission and blocking of light.
  • the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2021-170565 filed on October 18, 2021 are cited here and incorporated as disclosure of the specification of the present invention. is.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention fournit un agent d'alignement de cristaux liquides permettant d'obtenir un d'obtenir un film d'alignement de cristaux liquides de résistance élevée, présentant une inhibition d'image rémanente CA, et de taux de maintien de tension élevé, y compris après exposition pendant une longue durée à des températures élevées. L'invention fournit également un film d'alignement de cristaux liquides obtenu à partir de cet agent d'alignement de cristaux liquides, et un élément d'affichage à cristaux liquides mettant en œuvre ce film d'alignement de cristaux liquide. L'agent d'alignement de cristaux liquides de l'invention comprend un composant (A), et un composé (B) représenté par la formule (1). Le composant (A) consiste en un composant polymère qui comprend un polymère (A) choisi dans un groupe constitué : d'un précurseur de polyimide obtenu par réaction de polymérisation d'une part d'un composant dérivé d'acide tétracarboxylique contenant au moins un composé choisi dans un groupe constitué d'un dianhydride d'acide tétracarboxylique et d'un dérivé de celui-ci, et d'autre part d'un composant diamine ; et d'un polyimide consistant en un produit d'imidisation de ce précurseur de polyimide. (La définition de chaque symbole est telle que décrite dans la description.)
PCT/JP2022/037650 2021-10-18 2022-10-07 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et composé WO2023068085A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020247015937A KR20240090440A (ko) 2021-10-18 2022-10-07 액정 배향제, 액정 배향막, 액정 표시 소자, 및 화합물
JP2023554499A JPWO2023068085A1 (fr) 2021-10-18 2022-10-07
CN202280080758.3A CN118355319A (zh) 2021-10-18 2022-10-07 液晶取向剂、液晶取向膜、液晶显示元件以及化合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-170565 2021-10-18
JP2021170565 2021-10-18

Publications (1)

Publication Number Publication Date
WO2023068085A1 true WO2023068085A1 (fr) 2023-04-27

Family

ID=86058183

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/037650 WO2023068085A1 (fr) 2021-10-18 2022-10-07 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et composé

Country Status (5)

Country Link
JP (1) JPWO2023068085A1 (fr)
KR (1) KR20240090440A (fr)
CN (1) CN118355319A (fr)
TW (1) TW202328291A (fr)
WO (1) WO2023068085A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011149071A1 (fr) * 2010-05-28 2011-12-01 日産化学工業株式会社 Agent d'alignement de cristaux liquides qui comprend un composé contenant un groupe clivable thermiquement, et film d'alignement de cristaux liquides
WO2017119461A1 (fr) * 2016-01-07 2017-07-13 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant
WO2020184628A1 (fr) * 2019-03-12 2020-09-17 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant
WO2021006182A1 (fr) * 2019-07-08 2021-01-14 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3893659B2 (ja) 1996-03-05 2007-03-14 日産化学工業株式会社 液晶配向処理方法
KR102420194B1 (ko) 2014-10-20 2022-07-12 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 그것을 사용한 액정 표시 소자
KR102483499B1 (ko) 2016-11-18 2022-12-30 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011149071A1 (fr) * 2010-05-28 2011-12-01 日産化学工業株式会社 Agent d'alignement de cristaux liquides qui comprend un composé contenant un groupe clivable thermiquement, et film d'alignement de cristaux liquides
WO2017119461A1 (fr) * 2016-01-07 2017-07-13 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant
WO2020184628A1 (fr) * 2019-03-12 2020-09-17 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant
WO2021006182A1 (fr) * 2019-07-08 2021-01-14 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant

Also Published As

Publication number Publication date
CN118355319A (zh) 2024-07-16
JPWO2023068085A1 (fr) 2023-04-27
KR20240090440A (ko) 2024-06-21
TW202328291A (zh) 2023-07-16

Similar Documents

Publication Publication Date Title
WO2022176680A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2023286733A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de production d'un élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides
WO2022270287A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2022234820A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2023068085A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et composé
WO2023286735A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, procédé de production d'élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides
WO2023032753A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2023068084A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, composé, et polymère
WO2022220199A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2024142964A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2022190896A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2024219400A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2023157876A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2024162336A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2023074390A1 (fr) Agent d'alignement de cristaux liquides, film aligné de cristaux liquides, élément d'affichage à cristaux liquides et composé
WO2023008203A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, composé et polymère
WO2024166693A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, composé et polymère
WO2023074570A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
WO2022250007A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, diamine et polymère
WO2023074392A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2023013622A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2024204521A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides et leurs procédés de fabrication
TW202436598A (zh) 液晶配向劑、液晶配向膜及液晶顯示元件
WO2023032784A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
TW202436601A (zh) 液晶配向劑、液晶配向膜及液晶顯示元件

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22883389

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023554499

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20247015937

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22883389

Country of ref document: EP

Kind code of ref document: A1