WO2021177080A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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WO2021177080A1
WO2021177080A1 PCT/JP2021/006672 JP2021006672W WO2021177080A1 WO 2021177080 A1 WO2021177080 A1 WO 2021177080A1 JP 2021006672 W JP2021006672 W JP 2021006672W WO 2021177080 A1 WO2021177080 A1 WO 2021177080A1
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liquid crystal
group
crystal alignment
formula
carbon atoms
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PCT/JP2021/006672
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English (en)
Japanese (ja)
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石川　和典
崇明 杉山
玲久 小西
一平 福田
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日産化学株式会社
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Priority to KR1020227025881A priority Critical patent/KR20220151604A/ko
Priority to JP2022505130A priority patent/JPWO2021177080A1/ja
Priority to CN202180018328.4A priority patent/CN115210637B/zh
Publication of WO2021177080A1 publication Critical patent/WO2021177080A1/fr

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    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.
  • liquid crystal displays have been widely used as display units for personal computers, smartphones, mobile phones, television receivers, and the like.
  • the 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 that apply an electric field to the liquid crystal layer, and an alignment film that controls the orientation of liquid crystal molecules in the liquid crystal layer. It includes a thin film transistor (TFT) that switches the electrical signal supplied to the pixel electrodes.
  • TFT thin film transistor
  • As the driving method of the liquid crystal molecule a longitudinal electric field method such as a TN method and a VA method, and a horizontal electric field method such as an IPS method and an FFS (fringe field switching) method are known.
  • liquid crystal alignment film in the industry is a film formed on an electrode substrate and made of polyamic acid and / or polyimide imidized thereof, with a cloth such as cotton, nylon, or polyester. It is manufactured by performing a so-called rubbing process of rubbing in one direction.
  • the rubbing process is a simple and highly productive industrially useful method.
  • the surface of the alignment film generated by the rubbing process is scratched, dusted, affected by mechanical force or static electricity, and in-plane of the alignment process.
  • problems such as non-uniformity of the above have been clarified.
  • Non-Patent Document 1 and Patent Document 1 As an orientation treatment method that replaces the rubbing treatment, a photo-alignment method that imparts a liquid crystal alignment ability by irradiating polarized radiation is known.
  • the photoalignment method 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 Non-Patent Document 1 and Patent Document 1).
  • the liquid crystal alignment film which is a constituent member of the liquid crystal display element, is a film for uniformly arranging liquid crystals, and the liquid crystal alignment is one of the important characteristics.
  • the liquid crystal alignment film obtained by the above photo-alignment method tends to have a lower liquid crystal alignment than the liquid crystal alignment film obtained by the conventional rubbing treatment, and the applicable range of the liquid crystal display device provided with the liquid crystal alignment film is wide. It was limited.
  • the twist angle slightly varies in the surface of the liquid crystal display element due to variations in manufacturing. Then, due to such in-plane variation, the brightness of the liquid crystal display element at the time of black display varies in the in-plane.
  • the present invention has been made in view of the above circumstances, and obtains a liquid crystal display element having high liquid crystal orientation, suppressing in-plane brightness variation during black display, and having improved contrast.
  • One of the purposes is to provide a liquid crystal alignment agent suitable for the photoalignment method.
  • a liquid crystal alignment agent containing a specific component As a result of diligent research, the present inventor has found that the above problems can be solved by using a liquid crystal alignment agent containing a specific component, and has completed the present invention. Specifically, the following is the gist.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and * represents a bond.
  • X represents a tetravalent organic group represented by the following formula (g)
  • Y represents an aromatic diamine satisfying the following conditions (1) and (2).
  • R 1 to R 4 are independently hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, and alkynyl group having 2 to 6 carbon atoms.
  • a part of -CH 2- contained in a monovalent organic group having 1 to 6 carbon atoms containing a group, an alkenyl group, an alkynyl group and a fluorine atom may be replaced with -O-).
  • Condition (1) Does not have a side chain group having 6 or more carbon atoms.
  • Condition (2) The two carbon-nitrogen bond axes derived from the amino group are not parallel to each other.
  • the present invention it is suitable for a liquid crystal display element having high liquid crystal orientation and excellent contrast in which the variation in brightness in the plane at the time of black display is suppressed, and a photoalignment method capable of obtaining the liquid crystal display element.
  • a liquid crystal alignment agent is provided.
  • the liquid crystal aligning agent of the present invention is an imidized polymer of a polyimide precursor containing a repeating unit (a0) represented by the above formula (0) and a repeating unit (a1) represented by the above formula (1).
  • the imidized polymer contains the polymer (A) having an imidization ratio of 80 to 95%.
  • X represents a tetravalent organic group represented by the following formula (g)
  • Y represents an aromatic diamine satisfying the following conditions (1) and (2).
  • R 1 to R 4 are independently hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, and alkynyl group having 2 to 6 carbon atoms.
  • a part of -CH 2- contained in a monovalent organic group having 1 to 6 carbon atoms containing a group, an alkenyl group, an alkynyl group and a fluorine atom may be replaced with -O-, and * is a bond.
  • Condition (1) Does not have a side chain group having 6 or more carbon atoms.
  • Condition (2) The two carbon-nitrogen bond axes derived from the amino group are not parallel to each other.
  • two carbon-nitrogen bond axes derived from an amino group are parallel to each other means that an aromatic diamine is used as a spherical / rod-shaped molecular structure model (for example, an HGS molecule manufactured by Maruzen Publishing Co., Ltd.).
  • structural model it means that the two carbon-nitrogen bond axes derived from the amino group can be arranged so as to be parallel to each other.
  • the above condition (2) "two carbon-nitrogen bond axes derived from an amino group are not parallel to each other” is derived from an amino group when the aromatic diamine is represented by a spherical / rod-shaped molecular structure model. This means that the two carbon-nitrogen bond axes cannot be arranged so that they are parallel to each other.
  • the molecular structure is optimized and the energy is minimized by the default MM2 force field setting, and the minimum (squared mean square root) is performed.
  • the RMS gradient is converged to 0.010, the case where the two carbon-nitrogen bond axes derived from the amino group are arranged so as to be parallel to each other is defined as "derived from the amino group" in the above condition (3).
  • alkyl group having 1 to 6 carbon atoms in R 1 to R 4 of the above formula (g) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group. , Tert-Butyl group, n-pentyl group and the like.
  • alkenyl group having 2 to 6 carbon atoms in R 1 to R 4 include a vinyl group, a propenyl group, a butynyl group and the like, and these may be linear or branched.
  • alkynyl group having 2 to 6 carbon atoms in R 1 to R 4 include an ethynyl group, a 1-propynyl group, a 2-propynyl group and the like.
  • halogen atom in R 1 to R 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom include a fluoromethyl group and a trifluoromethyl group.
  • a part of -CH 2- contained in the above-mentioned alkyl group, alkenyl group, alkynyl group and monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom may be replaced with -O-.
  • at least one of R 1 to R 4 represents a group other than the hydrogen atom in the above definition.
  • the tetravalent organic group represented by the above formula (g) is a tetravalent organic group represented by any of the following formulas (g-1) to (g-5) from the viewpoint of high photoreactivity. Is preferable, and a tetravalent organic group represented by the following formula (g-1) is more preferable. * Represents a bond.
  • Any hydrogen atom on the ring of Ar in the above formula (O) is a halogen 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, and a fluorine atom. It may be replaced with a monovalent organic group such as a monovalent organic group having 1 to 6 carbon atoms contained. Specific examples of these monovalent organic groups include the structures exemplified in R 1 to R 4 above.
  • Aromaatic diamine (d0) As the aromatic diamine (d0), an aromatic diamine having 4 to 40 carbon atoms is preferable from the viewpoint of efficiently obtaining the effects of the present invention. Specific examples include an aromatic diamine containing one aromatic ring in the molecule and two aromatic rings in the molecule, and the two aromatic rings are -CH 2- and -C (CH 3 ) 2-.
  • Examples thereof include group diamines and aromatic diamines having a heterocyclic structure.
  • the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.
  • some of the hydrogen atoms on the aromatic ring contain a hydroxy group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a carboxy group, a halogen atom, and a fluorine atom, and have 1 to 1 carbon atoms.
  • aromatic diamines represented by the following formulas (d0-1) to (d0-15), 1,3-bis (4-aminophenoxy) benzene, and bis [4- (4-aminophenoxy).
  • Phenyl] ether can be mentioned.
  • R is a monovalent with 1 to 5 carbon atoms containing a hydroxy group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a carboxy group, a halogen atom, and a fluorine atom.
  • R' represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R and R' may be the same or different from each other.
  • L is -CH 2- , -C (CH 3 ) 2- , -O-, -C.
  • L' represents a divalent organic group other than -NR- among the divalent organic groups defined in L above.
  • Q, Q', Q " Represents a heterocycle.
  • the respective bonds formed between the Q'and the benzene ring are not parallel to each other, and in the formulas (d0-10) and (d0-11), Q'and the nitrogen atom.
  • equation (d0-9) when n is 0, the respective bonds formed between Q "and the nitrogen atom are parallel to each other. If n is 1, the bonds formed between Q "and the nitrogen atom are not parallel to each other.
  • Equation (d0-13) Q and the adjacent nitrogen and carbon atoms The bonds formed between them are not parallel to each other.
  • each Q may be the same or different from each other.
  • n in the same formula is the same as each other.
  • heterocycles in the above Q, Q', Q' include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indol, benzoimidazole, purine, quinoline, isoquinolin, naphthylidine, quinoxalin, phthalazine, Examples thereof include triazine, carbazole, acrydin, piperidine, piperazine, pyrrolidine, hexamethyleneimine, oxazoline and the like.
  • Any hydrogen atom on the heterocycle has an alkyl group having 1 to 3 carbon atoms and 1 to 3 carbon atoms.
  • It may be substituted with at least one selected from the group consisting of an alkoxy group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms and a fluorine atom.
  • an alkoxy group a fluorine-containing alkyl group having 1 to 3 carbon atoms
  • a fluorine-containing alkoxy group having 1 to 3 carbon atoms and a fluorine atom examples are pyrrole, pyridine, pyrimidine, pyridazine, pyrazine, benzoimidazole, carbazole, piperidine, piperazine, oxazoline.
  • the respective bonds formed between the Q'and the benzene ring are not parallel to each other.
  • the bond positions of pyridine to be bonded to the benzene ring are the 2,4-position, the 2,6-position, and the 3,5-position, and "Q" and the nitrogen atom.
  • the respective bonds formed between and are not parallel to each other For example, in the case of pyridine, the bond position of pyridine that binds to the nitrogen atom is 2,4-position, 2,6-position or 3 , 5th place.
  • the bonds formed between the Q" and the nitrogen atom are parallel to each other, “saying, for example, that the bond position of pyridine that binds to the nitrogen atom is at the 2,5-position. Represents that. Further, “the bonds formed between Q and the adjacent nitrogen atom and carbon atom are not parallel to each other” means that, for example, pyridine is a bond of pyridine that is bonded to an adjacent nitrogen atom or carbon atom. Indicates that the position is 2,4-position, 2,6-position or 3,5-position.
  • aromatic diamine 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 2, 4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3'-diaminodiphenylmethane, 4,4' -Diaminodiphenylmethane, bis (4-aminophenoxy) methane, 1,5-bis (4-aminophenoxy) pentane, 1,3-bis (4-aminophenethyl) urea, 4,4'-diaminodiphenyl ether, 2,2 -Bis (3-aminophenyl) propane, 2,2-bis (4-
  • Y in the above formula (1) is 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,3'-diaminodiphenylmethane, 4,4'from the viewpoint of enhancing the liquid crystal orientation.
  • Aromaatic diamine (d1)) As the aromatic diamine (d1), an aromatic diamine having 4 to 40 carbon atoms is preferable from the viewpoint of efficiently obtaining the effects of the present invention. Further, it is preferable that the total number of carbon atoms and oxygen atoms in the main chain direction Q 2 has the above (d1) is an even number.
  • the preferable total number of carbon atoms and oxygen atoms in the main chain direction is 2n (n represents an integer of 1 to 9, preferably 1 to 8 and more preferably 1 to 6).
  • Specific examples of the aromatic diamine include an aromatic diamine in which two amino groups are bonded to the partial structure represented by the above formula (O).
  • Y 1 in the above formula (1) is preferably a divalent organic group derived from a diamine represented by the following formulas (d1-1) to (d1-14) from the viewpoint of enhancing the liquid crystal orientation.
  • the polymer (A) is an imidized polymer of a polyimide precursor having a repeating unit (a2) represented by the following formula (2), which is different from the repeating unit (a0) or (a1). May be good.
  • X 2 represents a tetravalent organic group
  • Y 2 represents a divalent organic group derived from an aromatic diamine having no side chain group having 6 or more carbon atoms
  • R and Z represent a divalent organic group. It is synonymous with R and Z in the above formula (0).
  • Y 2 is a divalent organic group defined by Y in the above formula (0) or the above formula (1). It represents a structure other than a divalent organic group defined by Y 1 in.
  • X 2 include a tetravalent organic group represented by the above formula (g) and a tetravalent organic group represented by any of the following formulas (X-1) to (X-25). , Tetravalent organic group derived from aromatic tetracarboxylic acid dianhydride and the like.
  • the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of a carboxy group bonded to an aromatic ring such as a benzene ring or a naphthalene ring.
  • an aromatic ring such as a benzene ring or a naphthalene ring.
  • Specific examples include tetravalent organic groups represented by any of the following formulas (Xa-1) to (Xa-2) and 4 represented by the following formulas (Xr-1) to (Xr-7). Tetravalent organic groups can be mentioned.
  • x and y are independently single bonds, ethers, carbonyls, esters, alkanediyl groups having 1 to 10 carbon atoms, 1,4-phenylene, and the like. It is a sulfonyl or amide group. J and k are integers of 0 or 1. * Represents a bond.
  • the tetravalent organic group represented by the above formula (Xa-1) or (Xa-2) may have a structure represented by any of the following formulas (Xa-3) to (Xa-19).
  • X 2 is represented by a tetravalent organic group represented by the above formula (g) or any of the above formulas (X-1) to (X-25). It is preferably a tetravalent organic group, and more preferably a tetravalent organic group represented by the above formula (g).
  • divalent organic group of Y 2 include the divalent organic group defined by Y in the above formula (0), the divalent organic group defined by Y 1 in the above formula (1), and p. -Phenylenediamine, 4,4'-diamino-2,2'-dimethylbiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3 , 3'-Difluoro-4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1, A group obtained by removing two amino groups from a amine such as 4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, and 4,4
  • Valuable organic groups 4- (2- (methylamino) ethyl) aniline, 4- (2-aminoethyl) aniline, 2,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic Acids, diamines having a diphenylamine skeleton such as the following formulas (Dp-5) to (Dp-6), and "-N (D)-(D is a carbamate type) such as the following formulas (5-5) to (5-9).
  • Boc represents a tert-butoxycarbonyl group.
  • Py independently represents a 2,5-pyridinylene group or a 2,5-pyrimidinylene group.
  • the polymer (A) is an imidized weight of a polyimide precursor having a repeating unit (a3) represented by the following formula (3), which is different from the repeating units (a0), (a1) and (a2). It may be coalesced.
  • X 3 represents a tetravalent organic group
  • Y 3 represents a divalent organic group other than the divalent organic group defined by Y 2 in the above formula (2)
  • R and Z represent the above formula ( It is synonymous with R and Z in 0).
  • X 3 is synonymous with a tetravalent organic group represented by the above formula (g)
  • Y 3 is a divalent organic group defined by Y in the above formula (0) or the above formula (1). It represents a structure other than a divalent organic group defined by Y 1 in.
  • X 3 include the structure exemplified by X 2 in the above formula (2), and from the viewpoint of preferably obtaining the effects of the present invention, a tetravalent organic represented by the above formula (g) is preferable. Is the basis.
  • divalent organic group Y 3, N-phenyl-3,6-diaminocarbazole, methacrylic acid 2- (2,4-di-aminophenoxy) ethyl, 2,4-diamino -N, N-diallyl Diamines having photopolymerizable groups such as aniline at the ends, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5- A diamine having a steroid skeleton such as cholestanyl diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, and 3,6-bis (4-aminobenzoyloxy) cholesterol, according to the following formula (V-1).
  • Examples thereof include a group obtained by removing two amino groups from a diamine such as an aliphatic diamine, and a group represented by any of the formulas (Y-1) to (Y-167) described in International Publication No. 2018/1172339. Effect from the viewpoint of obtaining suitably of the present invention, Y 3 is a group obtained by removing two amino groups from a diamine represented by the formula (5-10) - (5-13) are preferable.
  • X v1 to X v4 and X p1 to X p2 are independently ⁇ (CH 2 ) a ⁇ (a is an integer of 1 to 15).
  • X v5 represents -O-, -CH 2 O-, -CH 2 OCO-, -COO-, or -OCO-
  • Xa is single bond, -O-, -NH-, -O- (CH 2).
  • R v1 ⁇ R v4, R 1a ⁇ R 1b are each independently an alkyl group of 1 to 20 carbon atoms, a C1- Indicates 20 alkoxy groups or alkoxyalkyl groups having 2 to 20 carbon atoms.
  • Boc represents a tert-butoxycarbonyl group.
  • the total of the repeating unit (a0), the repeating unit (a1) and their imidized repeating units is 5 mol% or more with respect to all the repeating units. It is preferably present, and more preferably 10 mol% or more.
  • the polymer (A) preferably contains 1 to 40 mol% of the repeating unit (a1) and its imidized repeating unit with respect to all the repeating units in an amount of 1 to 35 mol%. It is more preferable to contain 1 to 30 mol%.
  • the polymer (A) preferably contains 1 to 95 mol% of the repeating unit (a2) and its imidized repeating unit with respect to all the repeating units, and 1 to 90 mol%. It is more preferably contained, and more preferably 5 to 90 mol% is contained.
  • the polymer (A) preferably contains 1 to 40 mol% of the repeating unit (a3) and its imidized repeating unit with respect to all the repeating units. It is more preferably contained, and further preferably 1 to 25 mol% is contained.
  • the imidized repeating unit of the polymer (A) is 95 mol% or less.
  • the polymer (A) contains a repeating unit (a0), a repeating unit (a1), and a repeating unit other than the imidized repeating unit thereof, the repeating unit (a0), the repeating unit (a1), and the like.
  • the total of the imidized repeating units of the above is preferably 95 mol% or less, more preferably 90 mol% or less.
  • the liquid crystal alignment agent of the present invention may contain at least one polymer (B) selected from the group consisting of a polyimide precursor and a polyimide having an imidization ratio of less than 80%. good.
  • examples of the polymer (B) include polymers having a repeating unit represented by the following formula (4).
  • X 4 is a tetravalent organic group and Y 4 is a divalent organic group.
  • Z is a carbon which may have a hydrogen atom and a substituent independently of each other.
  • tetravalent organic group in X 4 in the formula (4) tetravalent organic radical derived from tetravalent organic group derived from an aliphatic Tetokarubon dianhydride, alicyclic tetracarboxylic acid dianhydride or tetravalent organic radical derived from an aromatic tetracarboxylic acid dianhydride and the like, tetravalent organic groups exemplified above X 2 may be mentioned as specific examples.
  • X 4 is represented by any one tetravalent organic group represented by the above formula (g), the formula (X-1) ⁇ (X -25) A tetravalent organic group represented by the above formulas (Xa-1) to (Xa-2) or a tetravalent organic group represented by the above formulas (Xr-1) to (Xr-7).
  • Organic groups are preferable.
  • X 4 is 5 mol% of all repeating units contained repeating units is the specific tetravalent organic group in the polymer (B) It is preferably contained in an amount of 10 mol% or more, and more preferably contained in an amount of 10 mol% or more.
  • Examples of the divalent organic group in Y 4 of the above formula (4) include Y in the above formula (0) or the divalent organic group exemplified by Y 1 to Y 3 in the above formulas (1) to (3). Be done.
  • the polymer (B) is Y 4 is a nitrogen-containing heterocyclic ring, at least one nitrogen-containing structure selected from the secondary amino group and a group consisting of a tertiary amino group (hereinafter, Diamine having a nitrogen-containing structure), 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, carboxy group From a divalent organic group from which two amino groups have been removed from a diamine having a It is preferable that the polymer contains a repeating unit which is a divalent organic group (collectively referred to as “specific divalent organic group”) selected from the above
  • nitrogen-containing heterocycle examples include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indol, benzoimidazole, purine, quinoline, isoquinoline, naphthylidine, quinoxaline, phthalazine, triazine, carbazole, aclysine and piperidine.
  • the secondary amino group and the tertiary amino group that the diamine having a nitrogen-containing structure may have are represented by, for example, the following formula (n).
  • R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms
  • "*" represents a bond that binds to the hydrocarbon group.
  • the monovalent hydrocarbon group of R in the above formula (n) include an alkyl group such as a methyl group, an ethyl group and a propyl group; a cycloalkyl group such as a cyclohexyl group; and an aryl such as a phenyl group and a methylphenyl group. Group etc. can be mentioned.
  • R is preferably a hydrogen atom or a methyl group.
  • diamine having a nitrogen-containing structure examples include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, and N-methyl-3,6-.
  • diamine having a carboxy group examples include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid or 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid. Acid is mentioned.
  • Polymer (B) in terms afterimage from residual DC is small, it contains Y 4 is at least 1 mole% of the total repeating units contained repeating units is the specific bivalent organic group into the polymer (B) However, it may contain 5 mol% or more.
  • the content ratio of the polymer (A) and the polymer (B) is 10/90 to 90 in terms of the mass ratio of [polymer (A)] / [polymer (B)]. It may be / 10, 20/80 to 90/10, or 20/80 to 80/20.
  • the polyimide precursors polyamic acid ester and polyamic acid used in the present invention and the polyimide as an imidized polymer thereof can be synthesized by a known method as described in, for example, International Publication WO2013 / 157586.
  • the polymer (A) of the present invention can be obtained by imidizing the above-mentioned polyimide precursor.
  • the repeating unit of the polyimide precursor is ring-closed, but the ratio of the ring-closed repeating unit to all the repeating units of the polyimide precursor (also referred to as ring closure rate or imidization rate) is It is 80 to 95%, preferably 82 to 95%, and more preferably 85 to 95%.
  • the obtained liquid crystal alignment film has high liquid crystal alignment, so that the above-mentioned effect of the present invention can be obtained.
  • 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 solution is prepared at a concentration of 10 to 15% by mass, from the viewpoint of workability. , Not particularly limited.
  • the solution viscosity (mPa ⁇ s) of the polymer is a polymer having a concentration of 10 to 15% by mass prepared by using a good solvent of the polymer (for example, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C.
  • 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. ⁇ 300,000.
  • 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. Within such a molecular weight range, good orientation and stability of the liquid crystal display element can be ensured.
  • the liquid crystal alignment agent of the present invention contains a polymer (A) and, if necessary, a polymer (B).
  • the liquid crystal alignment agent of the present invention may contain other polymers in addition to the polymer (A) and the polymer (B).
  • examples of other types of polymers include polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene or derivatives thereof, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like.
  • the liquid crystal alignment agent is used for producing a liquid crystal alignment film, and takes the form of a coating liquid from the viewpoint of forming a uniform thin film.
  • the liquid crystal alignment agent of the present invention is also preferably a coating liquid containing the above-mentioned polymer component and an organic solvent.
  • the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, 1% by mass or more is preferable, and from the viewpoint of storage stability of the solution, 10% by mass or less is preferable. A particularly preferable concentration of the polymer is 2 to 8% by mass.
  • the organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component is uniformly dissolved.
  • Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl-2.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide or ⁇ -butyrolactone are preferable.
  • 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 amount of the solvent contained in the liquid crystal alignment agent. ..
  • the organic solvent contained in the liquid crystal alignment agent is a mixture of the above solvent and a solvent (also referred to as a poor solvent) that improves the coatability when the liquid crystal alignment agent is applied and the surface smoothness of the coating film.
  • a solvent also referred to as a poor solvent
  • the use of a solvent is preferred. Specific examples of the poor solvent used in combination are shown below, but the present invention is not limited thereto.
  • diisopropyl ether diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol)
  • ethylene glycol dimethyl ether ethylene glycol diethyl ether
  • ethylene glycol dibutyl ether 1,2-butoxyethane
  • diethylene glycol dimethyl ether diethylene glycol diethyl ether.
  • diisobutylcarbinol diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene.
  • Glycol monobutyl ether acetate or diisobutyl ketone is preferred.
  • the content of the poor solvent is preferably 1 to 80% by mass, more preferably 20 to 80% by mass, and particularly preferably 20 to 70% by mass of the total solvent contained in the liquid crystal alignment agent.
  • the type and content of the poor solvent are appropriately selected according to the coating apparatus for the liquid crystal alignment agent, coating conditions, coating environment, and the like.
  • 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, and N-methyl-2-.
  • the liquid crystal alignment agent of the present invention may additionally contain a component other than the polymer component and the organic solvent (hereinafter, also referred to as an additive component).
  • additive components include an adhesion aid for enhancing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealant, a compound for promoting imidization, and the strength of the liquid crystal alignment film.
  • examples thereof include a compound for enhancing the above (hereinafter, also referred to as a crosslinkable compound), a dielectric for adjusting the dielectric constant and the electric resistance of the liquid crystal alignment film, and a conductive substance.
  • an oxylanyl group from the viewpoint of exhibiting good resistance to AC afterimage and highly improving film strength, an oxylanyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, and a meldrum. It consists of a compound having at least one group selected from the group consisting of a group containing an acid structure, a cyclocarbonate group, and a group represented by the following formula (d), and a compound represented by the following formula (e). It may be at least one compound selected from the group (hereinafter, these are collectively referred to as compound (C)).
  • R 2 and R 3 are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms or "* -CH 2- OH", respectively, and * represents a bond.
  • A represents a (m + n) valent organic group having an aromatic ring
  • R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • m represents an integer of 1 to 6
  • n represents 0 to 0 to.
  • the hydrogen atom on the aromatic ring of A is a halogen 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, and a fluorine atom. It may be replaced with a monovalent organic group such as a monovalent organic group having 1 to 6 carbon atoms contained.
  • the compound having an oxylanyl group examples include the compound described in paragraph [0037] of JP-A-10-338880 and the compound having a triazine ring as a skeleton described in WO2017 / 170483. Examples thereof include compounds having two or more oxylanyl groups.
  • the compound having an oxetanyl group include the compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of International Publication No. 2011/132751.
  • the compound having a protected isocyanate group include the compounds having two or more protected isocyanate groups described in paragraphs [0046] to [0047] of Japanese Patent Application Laid-Open No. 2014-224978, International Publication No. 2015/141598.
  • Examples of the compound having three or more protected isocyanate groups described in paragraphs [0119] to [0120] of the above, and the compound represented by the following formulas (bi-1) to (bi-3) may be used. ..
  • Specific examples of the compound having a protected isothiocyanate group include compounds having two or more protected isothiocyanate groups described in Japanese Patent Application Laid-Open No. 2016-209488.
  • Specific examples of the compound having a group containing an oxazoline ring structure include compounds containing two or more oxazoline ring structures described in paragraph [0115] of Japanese Patent Application Laid-Open No. 2007-286597.
  • Specific examples of the compound having a group containing a Meldrum's acid structure include the compound having two or more Meldrum's acid structures described in International Publication No. WO2012 / 091088.
  • Specific examples of the compound having a cyclocarbonate group include the compounds described in WO2011 / 1555777.
  • Examples of the alkyl group having 1 to 3 carbon atoms of the groups R 2 and R 3 represented by the formula (d) include a methyl group, an ethyl group, a propyl group and an isopropyl group.
  • Examples of the (m + n) -valent organic group having an aromatic ring in A of the formula (e) include an aromatic hydrocarbon group having a carbon number of 6 to 30 (m + n) and an aromatic hydrocarbon group having a carbon number of 6 to 30. Examples thereof include (m + n) valent organic groups bonded directly or via a linking group, and (m + n) valent groups having an aromatic heterocycle. Examples of the aromatic hydrocarbon group include benzene and naphthalene.
  • aromatic heterocycle examples include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring, an indole ring, a quinoxaline ring, and an acridin ring. And so on.
  • linking group examples include -NR- (R is a hydrogen atom or a methyl group), an alkylene group having 1 to 10 carbon atoms, a group obtained by removing one hydrogen atom from the alkylene group, a divalent or trivalent cyclohexane ring, and the like. Can be mentioned. Any hydrogen atom of the alkylene group may be substituted with an organic group such as a fluorine atom or a trifluoromethyl group.
  • alkyl group having 1 to 5 carbon atoms in R of the formula (e) include specific examples of the alkyl group exemplified by R 1 to R 4 in the above formula (g). Specific examples include the compounds described in WO2010 / 074269, and the compounds represented by the following formulas (e-1) to (e-10).
  • the above compound is an example of a crosslinkable compound, and is not limited thereto.
  • components other than the above disclosed in International Publication No. 2015/060357 on pages 53 [0105] to 55 [0116] can be mentioned.
  • the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, and the crosslinking reaction proceeds. From the viewpoint of exhibiting good resistance to AC afterimages, the amount is more preferably 1 to 15 parts by mass.
  • adhesion aid examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N.
  • -Styryltrimethoxysilane 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxy Silane cups such as silane, tris- (trimethoxysilylpropyl) isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyandiapropyltriethoxysilane Ring agent can be mentioned.
  • silane coupling agent When a silane coupling agent is used, it should be 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent from the viewpoint of exhibiting good resistance to AC afterimages. It is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass.
  • Examples of the compound for promoting imidization include a basic site (eg: primary amino group, aliphatic heterocycle (eg, pyrrolidine skeleton), aromatic heterocycle (eg, imidazole ring, indole ring), or guanidino.
  • a basic site eg: primary amino group, aliphatic heterocycle (eg, pyrrolidine skeleton), aromatic heterocycle (eg, imidazole ring, indole ring), or guanidino.
  • Compounds having (such as groups) however, the above-mentioned crosslinkable compounds and adhesion aids are excluded
  • compounds in which the above-mentioned basic sites are generated at the time of firing are preferable. More preferably, it is a compound in which the above-mentioned basic site is generated at the time of firing, and specific examples thereof include compounds represented by the following formulas (B-1) to (B-17).
  • the content of the compound for promoting imidization is preferably 2 mol or less, more preferably 1 mol or less, still more preferably 0, based on 1 mol of the amic acid or the amic acid ester moiety of the polymer (A). 5.5 mol or less is good.
  • D represents an organic group desorbed by heating, and is preferably either a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. When there are a plurality of Ds, each D may be the same as or different from each other.
  • the method for producing a liquid crystal alignment film using the liquid crystal alignment agent of the present invention includes a step of applying the above liquid crystal alignment agent on a substrate (step (1)) and a step of heating the applied liquid crystal alignment agent to obtain a film (step).
  • Step (2)) the step of irradiating the film obtained in step (2) with polarized ultraviolet rays (step (3)), and if necessary, further, the film obtained in step (3) was subjected to 100 ° C.
  • the step (step (4)) of firing at a temperature higher than that of the step (2) is sequentially performed.
  • the substrate to which the liquid crystal alignment 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 or a polycarbonate substrate, or the like can also be used. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed, from the viewpoint of simplifying the process. Further, in the reflective liquid crystal display element, an opaque object such as a silicon wafer can be used if only one side of the substrate is used, and a material that reflects light such as aluminum can also be used for the electrode in this case.
  • the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, a method such as screen printing, offset printing, flexographic printing, or an inkjet method is generally used.
  • Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, a spray method, and the like, and these may be used depending on the intended purpose.
  • the step (2) is a step of heating the liquid crystal alignment agent applied on the substrate to form a film.
  • the liquid crystal aligning agent applied on the substrate in the step (1) is evaporated by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven, or is contained in a polymer. Thermal imidization of the amic acid or the amic acid ester of the above can be performed.
  • the heating step of the liquid crystal alignment agent applied on the substrate in the step (1) can be performed at any temperature and time, and may be performed a plurality of times.
  • the heating temperature can be, for example, 40 to 180 ° C., and from the viewpoint of shortening the process, it is preferably performed at 40 to 150 ° C., and more preferably 40 to 120 ° C.
  • the heating time is not particularly limited, and examples thereof include 1 to 10 minutes or 1 to 5 minutes.
  • a step of heating in a temperature range of, for example, 190 to 250 ° C. or 200 to 240 ° C. can be performed after the above step.
  • the heating time is not particularly limited, and examples thereof include a heating time of 5 to 40 minutes or 5 to 30 minutes.
  • the step (3) is a step of irradiating the film obtained in the step (2) with polarized ultraviolet rays.
  • the wavelength of ultraviolet rays is preferably 200 to 400 nm, and more preferably ultraviolet rays having a wavelength of 200 to 300 nm.
  • the substrate coated with the liquid crystal alignment film may be irradiated with ultraviolet rays while being heated at 50 to 250 ° C.
  • the irradiation amount of the radiation is preferably 1 ⁇ 10,000mJ / cm 2, more preferably 100 ⁇ 5,000mJ / cm 2.
  • the liquid crystal alignment film thus produced can stably orient the liquid crystal molecules in a certain direction.
  • the extinction ratio of linearly polarized ultraviolet rays is preferably 10: 1 or more, more preferably 20: 1 or more.
  • the step (4) is a step of firing the film obtained in the step (3) at 100 ° C. or higher and at a temperature higher than that of the step (2).
  • the firing temperature is not particularly limited as long as it is 100 ° C. or higher and higher than the firing temperature in step (2), but is preferably 150 to 300 ° C., more preferably 150 to 250 ° C., and further preferably 200 to 250 ° C. preferable.
  • the firing time is preferably 5 to 120 minutes, more preferably 5 to 60 minutes, and even more preferably 5 to 30 minutes. If the thickness of the liquid crystal alignment film after firing is too thin, the reliability of the liquid crystal display element may decrease. Therefore, the thickness is preferably 5 to 300 nm, more preferably 10 to 200 nm.
  • the obtained liquid crystal alignment film can be contact-treated with water or a solvent.
  • the solvent used for the contact treatment is not particularly limited as long as it is a solvent that dissolves the decomposition products generated from the liquid crystal alignment film by irradiation with ultraviolet rays. 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-.
  • Examples thereof include methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate and cyclohexyl acetate.
  • water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate is preferable, and water, 1-methoxy-2-propanol or ethyl lactate is more preferable from the viewpoint of versatility and solvent safety.
  • the solvent may be used alone or in combination of two or more.
  • Examples of the above-mentioned contact treatment that is, a method of treating a liquid crystal alignment film irradiated with polarized ultraviolet rays with water or a solvent, include a dipping treatment and a spray treatment (also referred to as a spray treatment).
  • the treatment time in these treatments is preferably 10 seconds to 1 hour from the viewpoint of efficiently dissolving the decomposition products generated from the liquid crystal alignment film by ultraviolet rays. Above all, it is preferable to carry out the immersion treatment for 1 to 30 minutes.
  • the solvent used during the contact treatment may be heated at room temperature, but is preferably 10 to 80 ° C, more preferably 20 to 50 ° C.
  • ultrasonic treatment or the like may be performed as necessary.
  • rinsing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone or to bake the liquid crystal alignment film.
  • a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone
  • the firing temperature is preferably 150 to 300 ° C, more preferably 180 to 250 ° C, and even more preferably 200 to 230 ° C.
  • the firing time is preferably 10 seconds to 30 minutes, more preferably 1 to 10 minutes.
  • the liquid crystal alignment film of the present invention is obtained from the above liquid crystal alignment agent.
  • the liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a transverse electric field type liquid crystal display element such as an IPS system or an FFS system, and is particularly useful as a liquid crystal alignment film for an FFS type liquid crystal display element.
  • the liquid crystal display element of the present invention includes the liquid crystal alignment film.
  • the liquid crystal display element is obtained by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention, then producing a liquid crystal cell by a known method, and using the liquid crystal cell.
  • a liquid crystal display element having a passive matrix structure will be described as an example.
  • a liquid crystal display element having an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
  • a transparent glass substrate is prepared, and a common electrode is provided on one substrate and a segment electrode is provided on the other substrate.
  • These electrodes can be, for example, ITO electrodes and are patterned so as to display a desired image.
  • an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode.
  • the insulating film can be, for example, a film of SiO 2- TiO 2 formed by the sol-gel method.
  • a liquid crystal alignment film is formed on each substrate, the other substrate is superposed on one substrate so that the liquid crystal alignment film surfaces face each other, and the periphery is bonded with a sealant.
  • a spacer is usually mixed in the sealant in order to control the substrate gap, and that the spacer for controlling the substrate gap is also sprayed on the in-plane portion where the sealant is not provided.
  • a part of the sealing agent is provided with an opening in which the liquid crystal can be filled from the outside.
  • the liquid crystal material is injected into the space surrounded by the two substrates and the sealant through the opening provided in the sealant, and then the opening is sealed with an adhesive.
  • a vacuum injection method may be used, or a method utilizing a capillary phenomenon in the atmosphere may be used.
  • the liquid crystal material either a positive type liquid crystal material or a negative type liquid crystal material may be used.
  • the 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 liquid crystal alignment film can be obtained in a smaller number of steps than in the conventional case by carrying out the step (3) after removing the organic solvent in the temperature range of 40 to 150 ° C.
  • the liquid crystal alignment agent of the present invention is particularly preferably used in a method for producing a liquid crystal alignment film, which comprises a step of removing an organic solvent in a temperature range of 40 to 150 ° C. in step (2) and then carrying out step (3). Can be done.
  • Boc represents a tert-butoxycarbonyl group.
  • Boc represents a tert-butoxycarbonyl group.
  • Fmoc represents a 9-fluorenylmethyloxycarbonyl group.
  • This reaction solution was put into 170 g of methanol, and the obtained precipitate was filtered off. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 80 ° C. to obtain a polyimide resin powder (imidization ratio: 86%). Further, 4.00 g of this polyimide resin powder was taken in a 500 mL Erlenmeyer flask containing a stirrer, 29.3 g of NMP was added, and the mixture was stirred and dissolved at 70 ° C. for 24 hours to dissolve the polyimide solution (PI-1). ) was obtained.
  • ⁇ Synthesis example 6> 2.69 g (9.0 mmol) of DA-6 and 7.17 g (36.0 mmol) of DA-11 were taken in a 200 mL four-necked flask with a stirrer and a nitrogen introduction tube, and the concentration of NMP was 12. It was added to a mass%, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, add 12.2 g (41.4 mmol) of CA-2, add NMP to a concentration of 12% by mass, and stir at 70 ° C. for 24 hours to prepare a solution of polyamic acid (41.4 mmol). PAA-1) was obtained.
  • the numerical values in parentheses in Table 1 represent the compounding ratio (molar portion) of each compound to 100 mol parts of the total amount of the tetracarboxylic acid derivative used in the synthesis for the tetracarboxylic acid component, and for the diamine component, The compounding ratio (molar part) of each compound with respect to 100 mol part of the total amount of diamine used for synthesis is shown.
  • the organic solvent the blending ratio (parts by mass) of each organic solvent with respect to 100 parts by mass of the total amount of the organic solvents used for preparing the polyimide solution is shown.
  • Examples 1 to 8> The same method as in Comparative Example 1 was carried out except that the polymer components used were changed as shown in Table 2 below, and liquid crystal alignment agents (1) to (8) were obtained, respectively.
  • Table 2 the values in parentheses indicate the mixing ratio (parts by mass) of each polymer component or additive with respect to 100 parts by mass of the total of the polymer components used in the preparation of the liquid crystal alignment agent for the polymer and the additive, respectively. show.
  • the organic solvent the blending ratio (parts by mass) of each organic solvent with respect to 100 parts by mass of the total amount of the organic solvents used for preparing the liquid crystal alignment agent is shown.
  • an FFS-driven liquid crystal cell was prepared by the procedure shown below, and its characteristics were evaluated.
  • the liquid crystal cell for the Fringe Field Switching (FFS) mode has a FOP (Finger on Plate) electrode layer formed on the surface thereof, which is composed of a surface-shaped common electrode, an insulating layer, and a comb-shaped pixel electrode.
  • FOP Fringe Field Switching
  • the glass substrate of No. 1 and the second glass substrate having a columnar spacer having a height of 3.5 ⁇ m on the front surface and an ITO film for preventing antistatic formation on the back surface were made into a set.
  • the above pixel electrode has a comb tooth shape in which a plurality of electrode elements having a width of 3 ⁇ m bent at an internal angle of 160 ° are arranged in parallel with an interval of 6 ⁇ m, and one pixel has a comb tooth shape. It has a first region and a second region with a line connecting the bent portions of the plurality of electrode elements as a boundary.
  • the liquid crystal alignment film formed on the first glass substrate is oriented so that the direction of equally dividing the internal angle of the pixel bending portion and the orientation direction of the liquid crystal are orthogonal to each other, and the liquid crystal alignment film formed on the second glass substrate is formed. The film is oriented so that the orientation direction of the liquid crystal on the first substrate and the orientation direction of the liquid crystal on the second substrate coincide with each other when the liquid crystal cell is produced.
  • a liquid crystal alignment agent filtered through a 1.0 ⁇ m filter was applied to the surface of each of the above sets of glass substrates by spin coating, and dried on a hot plate at 80 ° C. for 2 minutes. Then, the coating film surface is irradiated with ultraviolet rays having a wavelength of 254 nm, which is linearly polarized with an extinction ratio of 26: 1 via a polarizing plate, at 150 to 350 mJ / cm 2 , and then fired in a hot air circulation oven at 230 ° C. for 30 minutes to form a film. Two substrates with a liquid crystal alignment film having a thickness of 100 nm were obtained.
  • a sealant was printed on one of the above-mentioned set of substrates with a liquid crystal alignment film, the other substrate was bonded so that the liquid crystal alignment film surfaces faced each other, and the sealant was cured to prepare an empty cell.
  • a liquid crystal display (MLC-3019 manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature by a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. Then, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour (hereinafter, also referred to as “ISO treatment”), left overnight, and then used for each evaluation.
  • Table 3 shows the evaluation results of the liquid crystal display elements obtained by using the liquid crystal alignment agents (1) to (8) and (R1) obtained in Examples 1 to 8 and Comparative Example 1.
  • the liquid crystal alignment agent of the present invention is widely used for a liquid crystal display element of a longitudinal electric field system such as a TN system or a VA system, particularly a horizontal electric field system such as an IPS system or an FFS system.
  • a longitudinal electric field system such as a TN system or a VA system
  • a horizontal electric field system such as an IPS system or an FFS system.

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

Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui est approprié pour être utilisé dans des techniques de photo-alignement et permet d'obtenir un élément d'affichage à cristaux liquides qui présente des propriétés d'alignement de cristaux liquides supérieures et un contraste amélioré, dans lequel des variations dans le plan de la luminosité sont supprimées lors de l'affichage du noir.　L'invention concerne spécifiquement un agent d'alignement de cristaux liquides contenant un polymère (A) qui est un polymère imidisé d'un précurseur de polyimide comprenant une unité de répétition exprimée par la formule (0) et une unité de répétition exprimée par la formule (1), le degré d'imidisation du polymère imidisé étant de 80 à 95 %. (Dans la formule, X représente un groupe organique quadrivalent représenté par la formule (g), Y représente un groupe organique divalent dérivé d'une diamine aromatique qui satisfait la condition (1) et la condition (2), Y1 représente un groupe organique divalent dérivé d'une diamine aromatique (d1) qui satisfait la condition (1) et la condition (3), et R et Z représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle ayant de 1 à 6 atomes de carbone. Dans la formule (0) et la formule (1), les fractions de X peuvent être identiques ou différentes).
PCT/JP2021/006672 2020-03-06 2021-02-22 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2021177080A1 (fr)

Priority Applications (3)

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KR1020227025881A KR20220151604A (ko) 2020-03-06 2021-02-22 액정 배향제, 액정 배향막, 및 액정 표시 소자
JP2022505130A JPWO2021177080A1 (fr) 2020-03-06 2021-02-22
CN202180018328.4A CN115210637B (zh) 2020-03-06 2021-02-22 液晶取向剂、液晶取向膜以及液晶显示元件

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TW202146524A (zh) * 2020-06-10 2021-12-16 奇美實業股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件

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US20160122653A1 (en) * 2014-11-05 2016-05-05 Chi Mei Corporation Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2018030489A1 (fr) * 2016-08-10 2018-02-15 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'écran à cristaux liquides
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WO2015050135A1 (fr) 2013-10-01 2015-04-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides pour commutation dans le plan, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant

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WO2008062877A1 (fr) * 2006-11-24 2008-05-29 Nissan Chemical Industries, Ltd. Agent de traitement d'orientation de cristaux liquides et élément d'affichage à cristaux liquides produit en utilisant ledit agent
US20150353829A1 (en) * 2014-06-06 2015-12-10 Chi Mei Corporation Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
US20160122653A1 (en) * 2014-11-05 2016-05-05 Chi Mei Corporation Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2018030489A1 (fr) * 2016-08-10 2018-02-15 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'écran à cristaux liquides
WO2020040089A1 (fr) * 2018-08-20 2020-02-27 日産化学株式会社 Agent d'alignement de cristaux liquides et son procédé de production, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides

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CN114058384A (zh) * 2021-11-26 2022-02-18 深圳市道尔顿电子材料有限公司 一种聚酰亚胺光取向剂溶液及其制备方法和光取向膜、液晶盒

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JPWO2021177080A1 (fr) 2021-09-10
CN115210637B (zh) 2024-07-23
KR20220151604A (ko) 2022-11-15
CN115210637A (zh) 2022-10-18

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