WO2023074391A1 - Composition polymère, agent d'alignement de cristaux liquides, film de résine, film d'alignement de cristaux liquides, procédé de production d'élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

Composition polymère, agent d'alignement de cristaux liquides, film de résine, film d'alignement de cristaux liquides, procédé de production d'élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides Download PDF

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WO2023074391A1
WO2023074391A1 PCT/JP2022/038192 JP2022038192W WO2023074391A1 WO 2023074391 A1 WO2023074391 A1 WO 2023074391A1 JP 2022038192 W JP2022038192 W JP 2022038192W WO 2023074391 A1 WO2023074391 A1 WO 2023074391A1
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liquid crystal
group
organic group
formula
polymer composition
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PCT/JP2022/038192
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English (en)
Japanese (ja)
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崇 仲井
佳道 森本
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日産化学株式会社
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Priority to CN202280086162.4A priority Critical patent/CN118451142A/zh
Priority to JP2023556310A priority patent/JPWO2023074391A1/ja
Priority to KR1020247015938A priority patent/KR20240089719A/ko
Publication of WO2023074391A1 publication Critical patent/WO2023074391A1/fr

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    • 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
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy 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
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • 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
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Definitions

  • the present invention relates to a polymer composition, a liquid crystal alignment agent, a resin film, a liquid crystal alignment film, a method for manufacturing a liquid crystal display element, and a liquid crystal display element.
  • Liquid crystal display elements used in liquid crystal televisions, navigators, smartphones, etc. are usually provided with a liquid crystal alignment film for controlling the alignment state of liquid crystals.
  • a liquid crystal alignment film has a function of controlling the alignment of liquid crystal molecules in a certain direction in a liquid crystal display element.
  • a liquid crystal display element has a structure in which liquid crystal molecules forming a liquid crystal layer are sandwiched between liquid crystal alignment films formed on respective surfaces of a pair of substrates. There, the liquid crystal molecules are aligned in a certain direction by the liquid crystal alignment film and respond by applying a voltage to the electrodes provided between the substrate and the liquid crystal alignment film. As a result, the liquid crystal display element displays a desired image by utilizing the alignment change due to the response of the liquid crystal molecules.
  • liquid crystal alignment films have mainly been polyimide-based liquid crystal alignment films, which are obtained by applying a liquid crystal alignment agent whose main component is a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide to a glass substrate or the like and baking it. used.
  • a liquid crystal alignment agent whose main component is a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide
  • a liquid crystal display device is used, and lateral electric field methods such as an IPS (In Plane Switching) method and an FFS (Fringe Field Switching) method are being studied because of the demand for viewing angle characteristics (Patent Document 1).
  • IPS In Plane Switching
  • FFS Frringe Field Switching
  • Liquid crystal alignment films used in liquid crystal display elements of the IPS driving method and the FFS driving method require an alignment regulating force for suppressing afterimages (hereinafter also referred to as AC afterimages) generated by long-term AC driving.
  • AC afterimages an alignment regulating force for suppressing afterimages
  • high display quality is regarded as important, and specifications for display defects such as "afterimages" are becoming more and more severe.
  • pretilt angles that are lower than before are becoming more popular. has become required.
  • the present invention provides a polymer composition suitable for a liquid crystal alignment agent that provides a liquid crystal alignment film having excellent resistance to AC afterimage and a low pretilt angle, the liquid crystal alignment agent, the liquid crystal alignment film, and
  • An object of the present invention is to provide a liquid crystal display device having the liquid crystal alignment film.
  • a polymer composition characterized by containing the following components (A) and (B).
  • Component (A) At least one polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit represented by the following formula (a) and a polyimide which is an imidized product of the polyimide precursor.
  • X represents a tetravalent organic group.
  • Y represents a divalent organic group derived from a diamine.
  • Two R each independently represent a hydrogen atom or a monovalent organic group.
  • Two Z each independently represents a hydrogen atom or a monovalent organic group.
  • (X ar represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof.
  • Each of the two R independently represents a hydrogen atom or a monovalent organic group.
  • E is A divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol, wherein the organic diol contains a divalent organic group represented by the following formula (EG).)
  • EG divalent organic group represented by the following formula (EG).
  • n is an integer of 5 or more.
  • R represents a hydrogen atom or a methyl group.
  • the polymer composition suitable for the liquid-crystal aligning agent which can obtain the liquid-crystal aligning film which has excellent resistance to AC afterimage and has a low pretilt angle, this liquid-crystal aligning agent, this liquid-crystal aligning film, and this liquid crystal A liquid crystal display element having an alignment film can be obtained. Further, the liquid crystal display element has high display quality with few display defects.
  • halogen atoms include fluorine, chlorine, bromine and iodine atoms.
  • Boc represents a tert-butoxycarbonyl group.
  • the polymer composition of the present invention is a polyimide precursor having a repeating unit represented by the above formula (a) (hereinafter also referred to as a polyimide precursor (A)) and a polyimide that is an imidized product of the polyimide precursor It contains at least one polymer (A) selected from the group consisting of:
  • the polymer (A) may be of one type or two or more types.
  • Y represents a divalent organic group derived from diamine.
  • the divalent organic group derived from diamine includes, for example, a divalent organic group obtained by removing two amino groups from diamine. Examples of the diamine include the following diamines. The diamines may be used singly or in combination of two or more.
  • Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring.
  • the two Ars may be the same or different, and any hydrogen atom in the benzene ring, biphenyl structure, or naphthalene ring is a monovalent group.
  • p is an integer of 0 or 1.
  • the two or more m may be the same or different.
  • One or more hydrogen atoms on the benzene ring may be substituted with a monovalent group.
  • m and n are each independently 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-, - represents CH 2 O—, —CH 2 —OCO—, —COO—, or —OCO—, R 1 is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, or a fluorine atom having 1 to 10 carbon atoms; represents an alkoxy group containing, 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, when there are two m, n,
  • R is a hydrogen atom or -(CH 2 ) k -Boc (k is an integer of 0 to 3. In addition, k is 0, (CH 2 ) k represents a single bond.)
  • the monovalent group includes a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms.
  • diamine represented by the above formula (d o ) diamines represented by the following formulas (d o -1) to (d o -6), 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether are preferred.
  • any hydrogen atom in the benzene ring, biphenyl structure, or naphthalene ring may be replaced with a monovalent group.
  • the monovalent group include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, Examples include a fluoroalkenyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group, a nitro group and the like.
  • the diamine represented by the above formula (O) the following formulas (o-1) to (o-8), 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-diamino toluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(6-amino-2-naphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3-trifluoromethyl-4,4'-diamin
  • Y is a diamine represented by the formula (O), a diamine having an amide bond or a urea bond, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4, 4′-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, the formula (d o ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and the group “-N(D)-” (D is eliminated by heating to form a hydrogen atom represents a protecting group to be substituted, preferably a tert-butoxycarbonyl group), and is preferably a divalent organic group derived from a di
  • X represents a tetravalent organic group.
  • X preferably represents a tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof.
  • the tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof includes, for example, a tetravalent organic group obtained by removing four carboxy groups from the corresponding tetracarboxylic acid.
  • a tetravalent organic group derived from an acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof a tetravalent organic group derived from an alicyclic tetracarboxylic dianhydride or a derivative thereof
  • a tetravalent organic group derived from an organic group or an aromatic tetracarboxylic dianhydride or a derivative thereof can be mentioned.
  • the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure.
  • 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.
  • An 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. However, it is not necessary to consist only of an aromatic ring structure, and a part thereof may have a chain hydrocarbon structure or an alicyclic structure.
  • Examples of the tetracarboxylic dianhydride derivatives include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides.
  • the tetracarboxylic dianhydride or derivative thereof may be used singly or in combination of two or more.
  • acyclic aliphatic or alicyclic tetracarboxylic dianhydrides are selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure from the viewpoint of enhancing the liquid crystal orientation. It is preferably a tetracarboxylic dianhydride having at least one partial structure or a derivative thereof.
  • the above X is preferably a tetravalent organic group derived from a tetracarboxylic dianhydride represented by the following formula (t) or a derivative thereof.
  • X 1 is a structure selected from the following formulas (X1-1) to (X1-25). * represents a bond.
  • the tetracarboxylic dianhydride represented by the formula (t) in which X 1 is a formula (X1-1) to (X1-23) is an acyclic aliphatic or alicyclic tetracarboxylic dianhydride is an example of Further, tetracarboxylic dianhydrides represented by formula (t) in which X 1 is one of formulas (X1-24) to (X1-25) are examples of aromatic tetracarboxylic dianhydrides.
  • R 1 to R 21 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, It represents an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. * represents a bond.
  • R 1 to R 21 are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, from the viewpoint of enhancing liquid crystal orientation.
  • j and k are integers of 0 or 1
  • a 1 and A 2 are each independently a single bond, -O-, -CO-, -COO-, represents a phenylene group, a sulfonyl group, or an amide group.
  • a plurality of A 2 may be the same or different.
  • formula (X1-1) include the following formulas (1-1) to (1-6).
  • Formulas (1-1) and (1-2) are particularly preferred from the viewpoint of enhancing liquid crystal orientation. * has the same meaning as above.
  • the above X 1 is represented by the above formulas (X1-1) to (X1-10), (X1-18) to (X1-23), (X1-24) to (X1-25) , or (X1-26) to (X1-30) are preferred, the above formulas (X1-1), (X1-5), (X1-7) to (X1-10), (X1-21), (X1 -23), (X1-24) to (X1-25), or (X1-26) to (X1-30) are more preferable, and the above formulas (1-1), (1-2), (X1-5 ), (X1-7), (X1-9), or (X1-26) to (X1-30) are more preferred.
  • a monovalent hydrocarbon group having 1 to 20 carbon atoms As the monovalent organic group for R and Z in the above formula (a), a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the methylene group of the hydrocarbon group is -O-, -S-, -CO- , —COO—, —COS—, —NR 3 — (provided that R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms), —CO—NR 3 — (provided that R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.), -Si(R 3 ) 2 - (where R 3 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms).
  • a hydrocarbon group is a hydrocarbon group.
  • a monovalent group A substituted with —SO 2 —, etc., a monovalent hydrocarbon group, or at least one hydrogen atom bonded to a carbon atom of the monovalent group A is a halogen atom , hydroxy group, alkoxy group, nitro group, amino group, mercapto group, nitroso group, alkylsilyl group, alkoxysilyl group, silanol group, sulphino group, phosphino group, carboxy group, cyano group, sulfo group, acyl group, etc. a monovalent group having a heterocyclic ring.
  • Examples of monovalent organic groups for R and Z in the above formula (a) include, among others, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a tert-butoxy A carbonyl group or a 9-fluorenylmethoxycarbonyl group is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred.
  • R and Z are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
  • each of X, Y, R, and Z may be of one type or two or more types.
  • the content of the polymer (A) is preferably 70 to 99 parts by mass, more preferably 80 to 98 parts by mass, based on 100 parts by mass of the polymer composition.
  • the polymer (A) in the present invention is at least one polymer selected from the group consisting of a polyimide precursor having a repeating unit represented by the above formula (a) and a polyimide which is an imidized product of the polyimide precursor. be.
  • the polymer (A) may have a repeating unit represented by formula (a) and a terminal group.
  • terminal group refers to a group bonded to the terminals of the repeating units constituting the polymer (A).
  • Examples of terminal groups include amino groups, carboxy groups, acid anhydride groups, isocyanate groups, or derivatives thereof.
  • An amino group, a carboxyl group, an acid anhydride group, and an isocyanate group can be obtained by a normal condensation reaction, and the above derivatives can be obtained, for example, by blocking terminal groups with a terminal blocking agent, as described later. can be done.
  • the total of the repeating unit represented by formula (a) and its imidized structure is preferably 10 mol% or more, more preferably 20 mol% or more, of the total repeating units constituting the polymer (A).
  • the polymer (A) in the invention may further have a repeating unit represented by the following formula (U).
  • U 1 is a divalent organic group
  • U 1' is a divalent organic group derived from a diamine
  • C 1 and C 1' are each independently a hydrogen atom or a monovalent organic group. .
  • U1 is a divalent organic group.
  • Examples of U 1 include divalent organic groups derived from diisocyanates. The diisocyanate may be used alone or in combination of two or more.
  • examples of diisocyanates include aromatic diisocyanates and aliphatic diisocyanates.
  • aromatic diisocyanate means a diisocyanate having at least one aromatic group.
  • aliphatic diisocyanate means a diisocyanate having an aliphatic group and not having an aromatic group.
  • a divalent organic group derived from an aliphatic diisocyanate, which is an organic group having a number of 4 to 30, can be mentioned.
  • an aliphatic group includes both an acyclic aliphatic group and an alicyclic group.
  • U1 examples include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanates (eg, tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate), 1,4- Diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 4,4′-diisocyanatodiphenyl ether, 2,2′-bis(4-diisocyanate acid phenyl)propane, 4,4'-diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), 4,4'-diphenyl diisocyanate ether, 4,4'-diphenyl sulfone diisocyanate, 3,3'-dipheny
  • U 1' is a divalent organic group derived from diamine.
  • diamine examples include the diamines exemplified for the repeating unit (a) above, and preferred embodiments are the same as above.
  • Examples of the monovalent organic groups of C 1 and C 1′ in the formula (U) include the structures exemplified for R and Z in the repeating unit (a). From the viewpoint of obtaining the effects of the present invention, C 1 and C 1′ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
  • each of U 1 , U 1′ , C 1 , and C 1′ may be of one kind, or two or more kinds thereof.
  • the content of the repeating unit represented by the formula (U) is, from the viewpoint of obtaining the effect of the present invention, the above With respect to the total 100 mol% of the repeating unit (a), the imidized structure of the repeating unit (a) and the repeating unit represented by the above formula (U), 1 to 30 mol% is preferable, and 2 to 25 mol% is more preferred.
  • polyester (B) having a repeating unit represented by the above formula (b1) and having no repeating unit represented by the above formula (a) and its imidized structure. do. Polyester (B) may be used alone or in combination of two or more.
  • X ar in the above formula (b1) represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof.
  • 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. However, it is not necessary to consist only of an aromatic ring structure, and a part thereof may have a chain hydrocarbon structure or an alicyclic structure.
  • X ar in the above formula (b1) is preferably a tetravalent organic group derived from a tetracarboxylic dianhydride represented by the following formula (t) or a derivative thereof.
  • X 1 is a structure selected from the following formulas (X1-24) and (X1-25). * represents a bond.
  • j and k are integers of 0 or 1
  • a 1 and A 2 are each independently a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl group, or amido group; A plurality of A 2 may be the same or different.
  • E is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol
  • the organic diol is a divalent group represented by the above formula (EG).
  • the organic diol containing a divalent organic group represented by the above formula (EG) is not particularly limited as long as it contains the above formula (EG) in the molecule, but a diol having hydrogen atoms bonded to both ends of the above formula (EG) is more preferred.
  • the upper limit of n is preferably set so that the upper limit of the weight average molecular weight of the diol is 5,000 or less.
  • the upper limit of the molecular weight is set to 4,000 or less, and more preferably, the upper limit of the weight average molecular weight of the diol is set to 3,000 or less.
  • the upper limit of n is preferably 40, more preferably 30, and particularly preferably 20.
  • the lower limit of n is preferably 5, more preferably 6, from the viewpoint of enhancing liquid crystal orientation.
  • the diol containing a divalent organic group represented by the above formula (EG) includes pentaethylene glycol, hexaethylene glycol, trade names PEG-300, PEG-400, PEG- 600, PEG-1000, PEG-1500, PEG-2000, PEG-4000N, PEG-4000S, PEG-6000E, PEG-6000P, PEG-10000, PEG-13000, PEG-20000; product name PEG300 manufactured by Merck; PEG1000, PEG2000, PEG4000, PEG6000, PEG8000, PEG10000, PEG12000, PEG20000, PEG35000; product numbers P2139, P3265, P3515, 81210, 81240, 81260, 81285, 81310, 18 from SIGMA-ALDRICH 1986, 181994, 182001, 182028, 189456, 202304, 202312, 202320, 202339, 202398, 202421, 202436, 202444, 202452
  • PEG600, SINOPOL PEG1500, SINOPOL PEG4000 brand names PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#1540, PEG#4000, PEG#6000M manufactured by Lion Specialty Chemicals
  • Commercially available products such as Polyethylene Glycol 400 and Polyethylene Glycol 600 manufactured by Tokyo Kasei Kogyo Co., Ltd. can be mentioned.
  • Preferred specific examples of the diol having hydrogen atoms bonded to both ends of the above formula (EG) include pentaethylene glycol, hexaethylene glycol, Sanyo Chemical Industries Co., Ltd.
  • the above-mentioned polyethylene glycol and polypropylene glycol may be those obtained by subjecting ethylene oxide and propylene oxide to an anionic ring-opening polymerization reaction.
  • the polymerization reaction can be carried out using water, ethylene glycol, propylene glycol, etc.
  • the average molecular weight of the glycol exemplified in the diol containing a divalent organic group represented by (EG) above is the weight average molecular weight obtained based on polystyrene by gel permeation chromatography (GPC).
  • the content of the repeating unit represented by the above formula (b1) is preferably 10 mol% or more, more preferably 20 mol% or more, of the total repeating units constituting the polyester (B).
  • the upper limit is more preferably 90 mol % or less, and even more preferably 80 mol % or less.
  • Polyester (B) may further have a repeating unit represented by the following formula (b2). Polyester (B) may not have a repeating unit represented by the following formula (b2).
  • A1 is a divalent organic group derived from diisocyanate.
  • A2 is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol.
  • A1 is a divalent organic group derived from diisocyanate.
  • the diisocyanate may be used alone or in combination of two or more.
  • Examples of the diisocyanate include diisocyanate (DI EG ) having a divalent organic group represented by the above formula ( EG ), aromatic diisocyanate other than diisocyanate (DI EG ), and aliphatic diisocyanate.
  • DI EG diisocyanate having a divalent organic group represented by the above formula ( EG )
  • aromatic diisocyanate other than diisocyanate (DI EG ) aromatic diisocyanate other than diisocyanate
  • aliphatic diisocyanate means a diisocyanate having an aliphatic group and not having an aromatic group
  • Aliphatic diisocyanates can be mentioned.
  • an aliphatic group includes both an acyclic aliphatic group and an alicyclic group.
  • aromatic diisocyanates and aliphatic diisocyanates other than diisocyanate include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, toluene diisocyanates (e.g., 2,4-diisocyanate tolylene, 2 ,6-diisocyanate tolylene), 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 4,4′-diisocyanate Diphenyl ether, 2,2′-bis(4-phenyl diisocyanate)propane, 4,4′-diphenylmethane diisocyanate (4,
  • A2 is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxy groups from an organic diol.
  • the organic diols may be used singly or in combination of two or more.
  • Examples of the organic diol include a diol containing a divalent organic group represented by the above formula (EG); and a diol containing no divalent organic group represented by the above formula (EG).
  • Specific examples of diols not containing a divalent organic group represented by formula (EG) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, and 1,3-butanediol.
  • the polyester (B) in the present invention is a polyester that has a repeating unit represented by the above formula (b1) and does not have a repeating unit represented by the above formula (a) and its imidized structure.
  • the polyester (B) in the present invention may have the repeating units and terminal groups described above. The end groups are as described above.
  • the content of the repeating unit represented by the formula (b2) is 10 mol% of the total repeating units constituting the polyester (B).
  • the above is preferable, and 20 mol % or more is more preferable. Moreover, it is more preferably 90 mol % or less, and even more preferably 80 mol % or less.
  • the content of repeating units represented by the formula (b2) is the polyester (B) is preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 50 mol % or more of the entire repeating units constituting Moreover, the upper limit is more preferably 90 mol % or less, and even more preferably 80 mol % or less.
  • a 1 and A 2 may each be one type, or two or more types.
  • the content of the polyester (B) in the present invention is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, based on 100 parts by mass of the polymer composition.
  • polyimide precursor which is the polymer (A)
  • examples of the polyimide precursor, which is the polymer (A) include polyamic acids and polyamic acid esters.
  • a polyamic acid (a polyimide precursor having a repeating unit represented by the formula (a) in which R in the formula (a) is a hydrogen atom) can be produced by the following method. Specifically, the tetracarboxylic acid component containing the tetracarboxylic dianhydride or derivative thereof and the diamine component containing the diamine are mixed in the presence of an organic solvent at a temperature of preferably ⁇ 20 to 150° C., more preferably 0 to 50° C. °C, preferably 30 minutes to 24 hours, more preferably 1 to 12 hours (polycondensation).
  • U 1 is the same as U 1 in formula (U).
  • the organic solvent used in the above reaction 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.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D 3 represents an alkyl group having 1 to 4 carbon atoms.
  • 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 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.
  • the polyimide precursor is a polyamic acid ester (a polyimide precursor having a repeating unit represented by the formula (a) in which at least one of R in the formula (a) is a monovalent organic group), ( 1) a method of esterifying a polyamic acid obtained from a tetracarboxylic dianhydride and a diamine, (2) a method of reacting a tetracarboxylic acid diester dichloride and a diamine, and (3) a polycondensation of a tetracarboxylic acid diester and a diamine. It can be manufactured by a known method such as a method of causing
  • tetracarboxylic acid component containing a tetracarboxylic dianhydride or a derivative thereof, a diamine component, and optionally a diisocyanate compound are end-blocked using an appropriate end-blocking agent.
  • a stop-type polymer may be synthesized.
  • Terminal blockers include, for example, acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3- (3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride, etc.
  • di-tert-butyl dicarbonate dicarbonic acid diester compounds such as diallyl dicarbonate
  • acryloyl chloride methacryloyl chloride, chlorocarbonyl compounds such as 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-hexylamine , n-heptylamine, n-octylamine and other monoamine compounds
  • ethyl isocyanate phenyl isocyanate, naphthyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate and other unsaturated
  • the proportion of the end blocking agent used is preferably 20 mol parts or less, and preferably 10 mol parts or less, with respect to a total of 100 mol parts of the diamine component used and the organic diol component used as necessary. is more preferred.
  • the proportion of the terminal blocker used is preferably 0.01 mol part or more, more preferably 0.1 mol part or more, with respect to a total of 100 mol parts of the diamine component used.
  • Polyimide can also be obtained by ring-closing (imidizing) the polyimide precursor (A) of the polymer (A).
  • the imidization ratio as used herein means the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or derivatives thereof and carboxy groups (or derivatives thereof).
  • the imidization rate does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
  • Examples of methods for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, and catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.
  • the temperature when the polyimide precursor is thermally imidized in the solution is preferably 100 to 400° C., more preferably 120 to 250° C., and it is preferable to remove water generated by the imidization reaction from the system. .
  • Catalytic imidization of the polyimide precursor is carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, preferably -20 to 250°C, more preferably stirring at 0 to 180°C. can be done.
  • the amount of the basic catalyst is preferably 0.5 to 30 times the molar amount of the amic acid group, more preferably 2 to 20 times the molar amount, and the amount of the acid anhydride is preferably 1 to 50 times the molar amount of the amic acid group. It is preferably 3 to 30 molar times.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc.
  • pyridine is preferable because it has appropriate basicity for advancing the reaction.
  • the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride.
  • acetic anhydride is preferable because it facilitates purification after the reaction is completed.
  • the imidization rate by catalytic imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.
  • the reaction solution may be put into a solvent to precipitate.
  • Solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
  • the polymer precipitated by putting it into a solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure.
  • the impurities in the polymer can be reduced by redissolving the precipitated and recovered polymer in an organic solvent and repeating the operation of reprecipitating and recovering, for example, 2 to 10 times.
  • Solvents in this case include, for example, alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of solvents selected from these, because the purification efficiency is further improved.
  • the molecular weight of the polymer (A) used in the present invention is the weight measured by the GPC (Gel Permeation Chromatography) method when considering the strength of the liquid crystal alignment film obtained therefrom, the workability during film formation, and the coating property.
  • the average molecular weight is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 150,000.
  • the polyester (B) is, for example, a component (o) containing an organic diol having two hydroxy groups in the molecule, and a tetracarboxylic dianhydride having a tetravalent organic group represented by Xar in the molecule. or obtained by reacting with component (c) containing a derivative thereof.
  • the component (o) includes an organic diol (o) having a partial structure represented by the following formula (EG) in its molecule. (n is an integer of 5 or more. R represents a hydrogen atom or a methyl group.)
  • polyester (B) contains a repeating unit represented by the formula (b2)
  • a component (i) containing a compound containing two isocyanate groups in the molecule obtained by reacting
  • the (o) component, the (c) component, and the optionally used (i) component may each be of one type or two or more types.
  • organic diol (o) examples include organic diols exemplified by the repeating unit represented by the above formula (b1), and "H-EH” (E is synonymous with E in formula (b1). There is a diol compound represented by.
  • the monomer component for obtaining the polyester (B) contains the diol (o').
  • the reaction of the (o) component, the (c) component and the optionally used (i) component is usually carried out in an organic solvent.
  • the organic solvent used at that time is not particularly limited as long as it dissolves the produced polyester (B). Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methyl- ⁇ -caprolactam, dimethylsulfoxide, Tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoric acid triamide, ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve , ethyl cellosolv
  • polyester (B) may be used alone or in combination. Furthermore, even a solvent that does not dissolve the polyester (B) may be used by mixing with the above solvent. Moreover, since moisture in the organic solvent inhibits the polymerization reaction, it is preferable to use the organic solvent after dehydration and drying.
  • the blending amount of the (o) component and the (c) component is determined by the number of hydroxy groups and tetracarboxylic
  • the ratio (group (am)/hydroxy group) of the sum of the groups of the amic acid group or derivative thereof possessed by the acid dianhydride (hereinafter also referred to as group (am)) is preferably 0.8 or more and 1.2 or less. , more preferably 0.9 or more and 1.2 or less, more preferably 0.9 or more and 1.1 or less, in an organic solvent.
  • a method for synthesizing the polyester (B) obtained by reacting the (o) component, the (c) component and the (i) component is the ratio of the number of hydroxy groups to the total number of isocyanate groups and groups (am) ((isocyanate groups + groups (am))/hydroxy groups ) is preferably 0.8 or more and 1.2 or less, more preferably 0.9 or more and 1.2 or less, still more preferably 0.9 or more and 1.1 or less, obtained by reacting in an organic solvent. be done.
  • reaction with a diisocyanate compound or tetracarboxylic dianhydride or a derivative thereof may be performed after mixing two or more organic diols.
  • a diisocyanate compound or a tetracarboxylic dianhydride or a derivative thereof may be reacted separately.
  • the resulting terminal isocyanate compound or amic acid terminal or derivative thereof is further reacted with another organic diol compound, and This may be reacted with a diisocyanate compound or a tetracarboxylic dianhydride or derivative thereof.
  • a diisocyanate compound or a tetracarboxylic dianhydride or derivative thereof is further reacted with another organic diol compound, and This may be reacted with a diisocyanate compound or a tetracarboxylic dianhydride or derivative thereof.
  • the desired polyester (B) can be produced.
  • the reaction temperature of component (o) with component (c) and component (i) used as necessary is preferably 0 to 160°C, more preferably 10 to 150°C.
  • the reaction time can be appropriately selected depending on the reaction scale and reaction conditions employed.
  • the reaction may be carried out in the presence of a catalyst such as tertiary amines, alkali metals, alkaline earth metals, tin, zinc, titanium, cobalt or other metals or metalloid compounds.
  • the total concentration of components (o) and (i) in the reaction solution is preferably 1 to 50 mass %, more preferably 5 to 30 mass %.
  • the initial stage of the reaction may be carried out at a high concentration, and then the organic solvent may be added.
  • the molecular weight of the polyester (B) used in the present invention is the weight average measured by the GPC (Gel Permeation Chromatography) method when considering the strength of the liquid crystal alignment film obtained therefrom, workability during film formation and coating film properties.
  • the molecular weight is preferably 4,000 to 80,000, more preferably 6,000 to 60,000.
  • the polyester used in the present invention preferably has a viscosity at 25° C. of 10 to 5,000 mPa ⁇ s, more preferably 100 to 3,000 mPa ⁇ s.
  • the above viscosity is a preferable value when the solid content concentration in the polyester solution is in the range of 10 to 50% by mass.
  • the viscosity is within the above range from the viewpoint of suitably obtaining the effects of the present invention.
  • the above viscosity is a value measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample amount of 1.1 mL and a cone rotor TE-1 (1°34', R24) at a temperature of 25 ° C. is.
  • the polymer composition of the present invention may contain polymers other than the polymer (A) and other than the polyester (B).
  • polymers include polyesters other than polyester (B), polysiloxanes, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, and poly(styrene-maleic anhydride) copolymers.
  • poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, polymer selected from the group consisting of poly(meth)acrylate, etc. are mentioned.
  • poly(styrene-maleic anhydride) copolymers include SMA1000, 2000, 3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac Co., Ltd.), etc.
  • Poly(isobutylene-maleic anhydride) ) copolymers include Isoban-600 (manufactured by Kuraray Co., Ltd.)
  • specific examples of poly(vinyl ether-maleic anhydride) copolymers include GANTREZ AN-139 (methyl vinyl ether maleic anhydride resin , manufactured by ISP Japan).
  • Other polymers may be used singly or in combination of two or more.
  • the content of other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and more preferably 20 to 80 parts by mass with respect to the total 100 parts by mass of the polymer contained in the polymer composition. More preferred.
  • the polymer composition according to the present invention is preferably a liquid composition in which the polymer (A) and polyester (B) are dissolved or dispersed in an organic solvent.
  • the organic solvent contained in the polymer composition is not particularly limited as long as it uniformly dissolves the polymer components, but N,N-dimethylformamide, N,N-dimethylacetamide, N , N-dimethyllactamide, N,N-dimethylpropionamide, tetramethylurea, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, ⁇ -butyrolactone, ⁇ -valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropan
  • 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, particularly preferably 30 to 80% by mass, of the total solvent contained in the polymer composition.
  • the total content of the polymer (A) and the polyester (B) used in the present invention is preferably 1 to 100 parts by mass with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent, and 10 to 100 parts by mass.
  • the total content of the polymer (A) and the polyester (B) may be 90 parts by mass or less, or 80 parts by mass or less with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. good.
  • the organic solvent contained in the polymer composition is a solvent (also referred to as a poor solvent) that improves the coatability and surface smoothness of the coating film when the polymer composition is applied. It is preferred to use a mixed solvent. 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 polymer composition.
  • the type and content of the poor solvent are appropriately selected according to the coating apparatus, coating conditions, coating environment, and the like of the polymer composition.
  • Examples of poor solvents include diisopropyl ether, diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, -hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol mono Acetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl
  • 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 and ⁇ -butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2- pyrrolidone and propylene glycol diacetate, N,N-dimethyllactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N- Methy
  • the polymer composition of the present invention may additionally contain components other than the polymer component and the organic solvent (hereinafter also referred to as additive components).
  • additive components include, for example, crosslinkable compounds, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, dielectric constant and electrical resistance of resin films.
  • a compound for adjustment and the like can be mentioned.
  • the crosslinkable compound include a crosslinkable compound (c-1) having at least one substituent selected from an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group and an alkoxy group.
  • crosslinkable compound (c-2) having a polymerizable unsaturated group By containing the crosslinkable compound, it is possible to obtain a liquid crystal display element in which the occurrence of so-called flicker or the like, which occurs when the liquid crystal display element is irradiated with backlight immediately after the liquid crystal is driven, is reduced. You can also get the effect of being able to do it.
  • Preferred specific examples of the crosslinkable compounds (c-1) and (c-2) include the following compounds.
  • Examples of the epoxy group-containing compound (c-1) 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, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, Epicoat 828 (manufactured by Mitsubishi Chemical Corporation), etc.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin such as Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resin such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), etc. biphenyl skeleton-containing epoxy resins, EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.) and other phenol novolac-type epoxy resins, and EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.) and other (o, m, p-) cresol novolac-type epoxy resins.
  • isocyanurate compounds such as triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.), compounds described in paragraph [0037] of JP-A-10-338880, compounds described in WO2017/170483, etc.
  • the compound having an isocyanate group the diisocyanate compound described above;
  • the compound (c-1) having an oxetanyl group 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene (arone oxetane OXT-121 (XDO)), di[2-(3 -oxetanyl)butyl] ether (aron oxetane OXT-221 (DOX)), 1,4-bis[(3-ethyloxetane-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyl Oxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), paragraphs [0170] to [0175] of WO2011/132751 compounds having two or more oxet
  • the compound (c-1) having a hydroxy group and/or an alkoxy group N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide, 2,2-bis(4-hydroxy-3,5- dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1, 3,3,3-hexafluoropropane, WO 2015/072554, the compound described in paragraph [0058] of JP 2016-118753, the compound described in JP 2016-200798, WO2010 / 074269 compounds and the like;
  • the crosslinkable compound (c-2) having a polymerizable unsaturated group glycerin mono
  • the crosslinkable compounds (c-1) and (c-2) are, among others, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidyl aminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N , B-874N, B-882N, 1,3,5-tris(2-hydroxyethyl)isocyanurate, triglycidyl isocyanurate, N,N,N′,N′-tetrakis(2-hydroxyethyl)adipamide, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxymethylphenyl)prop
  • crosslinkable compounds examples include crosslinkable compounds, and are not limited to these.
  • the crosslinkable compound used in the polymer composition of the present invention may be of one type or a combination of two or more types.
  • the content of the crosslinkable compound in the polymer composition of the present invention is 0.1 to 150 parts by mass, or 0.1 to 100 parts by mass, or 1 to 50 parts by mass with respect to 100 parts by mass of all polymer components. part by mass.
  • Examples of compounds for adjusting the dielectric constant and electrical resistance of the resin film include monoamines having a nitrogen atom-containing aromatic heterocycle such as 3-picolylamine.
  • a monoamine having a nitrogen-containing aromatic heterocycle is used, it is preferably 0.1 to 30 parts by mass, more preferably 0.1 part by mass with respect to 100 parts by mass of the polymer component contained in the polymer composition. ⁇ 20 parts by mass.
  • Preferred specific examples of functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane.
  • Silane N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy silane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxysilane sidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane,
  • the solid content concentration in the polymer composition (ratio of the total mass of components other than the solvent of the polymer composition to the total mass of the polymer composition) is appropriately selected in consideration of viscosity, volatility, etc. , preferably in the range of 1 to 10 mass %. That is, the polymer composition is applied to the surface of the substrate as described later, and preferably heated to form a resin film.
  • a particularly preferred solid content concentration range varies depending on the method used to apply the polymer composition to the substrate.
  • the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass.
  • the printing method it is particularly preferable to set the solid content concentration in the range of 3 to 9% by mass, thereby setting the solution viscosity in the range of 12 to 50 mPa ⁇ s.
  • the ink jet method it is particularly preferable to set the solid content concentration in the range of 1 to 5% by mass, thereby setting the solution viscosity in the range of 3 to 15 mPa ⁇ s.
  • the temperature in preparing the polymer composition is preferably 10-50°C, more preferably 20-30°C.
  • the polymer composition described above can be applied, for example, onto a substrate and preferably subjected to heat treatment to volatilize the solvent component, thereby forming a resin film.
  • the polymer composition and resin film according to the present invention can be effectively applied to various technical applications, such as liquid crystal aligning agents, electronic circuit materials, semiconductor materials, electrical insulation materials, wire coating materials, lighting applications, and molding. It can be applied to various uses such as materials. Specifically, it can be applied to various resin films including display elements, semiconductor elements, actuators such as motors, various sensors such as piezoelectric sensors and pyroelectric sensors, and liquid crystal alignment films (liquid crystal alignment films for retardation films).
  • liquid crystal alignment films for scanning antennas and liquid crystal array antennas, or liquid crystal alignment films for transmission scattering type liquid crystal light control elements protective films (e.g. protective films for color filters), spacer films, interlayer insulating films, antireflection films, wiring coating films, antistatic films, electric motor insulating films (gate insulating films of flexible displays), and the like.
  • the polymer composition according to the present invention can be preferably applied as a liquid crystal aligning agent.
  • the liquid crystal aligning agent according to the present invention comprises the polymer composition according to the present invention. That is, the liquid crystal aligning agent which concerns on this invention contains the said polymer (A) and polyester (B) similarly to a polymer composition. Moreover, it is preferable to contain at least one of other polymers, organic solvents and additive components. For specific examples of the polymer (A), polyester (B), other polymers, organic solvents, and additive components, the blending ratio, solid content concentration, etc., the description of the polymer composition is applied. be able to.
  • a liquid crystal alignment film can be manufactured as a resin film by using the said polymer composition or the said liquid crystal aligning agent.
  • the liquid crystal display element which concerns on this invention comprises the liquid crystal aligning film formed using the said polymer composition or said liquid crystal aligning agent.
  • the operation mode of the liquid crystal display device according to the present invention is not particularly limited. It can be applied to various operation modes such as type (IPS type), FFS type, and optical compensation bend type (OCB type).
  • the liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (4), a method including steps (1) to (2) and (4), steps (1) to (3), and (4). -2) and (4-4), or by a method including steps (1) to (3), (4-3) and (4-4).
  • a process (1) is a process of apply
  • a specific example of step (1) is as follows.
  • the liquid crystal aligning agent of the present invention is applied to one surface of the substrate provided with the patterned transparent conductive film by an appropriate coating method such as a roll coater method, a spin coat method, a printing method, an inkjet method, or the like.
  • the substrate is not particularly limited as long as it is highly transparent, and in addition to a glass substrate and a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used.
  • the reflective liquid crystal display element if only one substrate is used, 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.
  • a substrate provided with electrodes made of a transparent conductive film or a metal film patterned in a comb shape and a counter substrate provided with no electrodes are used.
  • 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
  • a specific example of step (2) is as follows. After the liquid crystal aligning agent is applied onto the substrate in step (1), a heating means such as a hot plate, thermal circulation oven or IR (infrared) oven is used to evaporate the solvent or heat the polyamic acid or polyamic acid ester. Thermal imidization can be performed.
  • 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 reducing the solvent of the liquid crystal aligning agent can be, for example, 40 to 180°C. From the viewpoint of shortening the process, it may be carried out at 40 to 150°C.
  • the firing time is not particularly limited, but may be 1 to 10 minutes or 1 to 5 minutes.
  • a step of baking at a temperature range of 150 to 300° C. or 150 to 250° C. may be added after the above step.
  • the firing time is not particularly limited, but may be 5 to 40 minutes or 5 to 30 minutes.
  • the thickness of the film-like material after baking is preferably 5 to 300 nm, more preferably 10 to 200 nm, because if it is too thin, the reliability of the liquid crystal display element may be lowered.
  • Step (3) is a step of subjecting the film obtained in step (2) to orientation treatment. That is, in a horizontally aligned liquid crystal display element such as an IPS system or an FFS system, the coating film is subjected to an alignment ability imparting treatment. On the other hand, in a vertical alignment type liquid crystal display element such as VA mode or PSA mode, the formed coating film can be used as a liquid crystal alignment film as it is, but the coating film may be subjected to an alignment ability imparting treatment. Examples of the alignment treatment method for the liquid crystal alignment film include a rubbing treatment method and a photo-alignment treatment method.
  • the surface of the film-like material is irradiated with radiation polarized in a certain direction, and in some cases, heat treatment is performed to impart liquid crystal alignment (also referred to as liquid crystal alignment ability).
  • 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 while being heated 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 contact treatment using water or 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.
  • solvents may be used singly or in combination of two or more.
  • the temperature of the heat treatment for the above radiation-irradiated coating film is more preferably 50 to 300°C, more preferably 120 to 250°C.
  • the heat treatment time is preferably 1 to 30 minutes.
  • Step (4) Step of producing a liquid crystal cell> Two substrates on which liquid crystal alignment films are formed as described above are prepared, and liquid crystal is arranged between the two substrates facing each other. Specifically, the following two methods are mentioned. In the first method, first, two substrates are arranged to face each other with a gap (cell gap) interposed therebetween 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 liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used.
  • a liquid crystal composition with a positive dielectric anisotropy is also referred to as a positive liquid crystal
  • a liquid crystal composition with a negative dielectric anisotropy is also referred to as a negative liquid crystal.
  • 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.
  • Such additives include photopolymerizable monomers such as compounds having a polymerizable group (meth(a)acryloyl group, etc.); optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); Antioxidants; ultraviolet absorbers; dyes; antifoaming agents; polymerization initiators; 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.
  • the second method is a method called ODF (One Drop Fill) method.
  • ODF One Drop Fill
  • 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.
  • it is desirable to remove the flow orientation at the time of liquid crystal filling by heating to a temperature at which the liquid crystal composition used takes an isotropic phase and then slowly cooling to room temperature.
  • 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 sealant for example, an epoxy resin or the like containing aluminum oxide spheres as a curing agent and a spacer can be used.
  • Liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates.
  • a liquid crystal display element (PSA type liquid crystal display element) manufactured through a process of polymerizing a polymerizable compound by at least one of irradiating an active energy ray and heating while placing an object and applying a voltage between electrodes. It is preferably used.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group polymerized by at least one of active energy rays and heat is placed between the pair of substrates. It is also preferably used in a liquid crystal display element (SC-PVA mode type liquid crystal display element) manufactured through a process of arranging a liquid crystal alignment film containing a liquid crystal and applying a voltage between electrodes.
  • SC-PVA mode type liquid crystal display element manufactured through a process of arranging a liquid crystal alignment film containing a liquid crystal and applying a voltage between electrodes.
  • the polymerizable compound include polymerizable compounds having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule.
  • a method of manufacturing a liquid crystal display element may be employed in which a step of irradiating ultraviolet rays, which will be described later, is performed after performing the same as in (4) above. According to this method, a liquid crystal display device excellent in response speed can be obtained with a small amount of light irradiation, as in the case of manufacturing the PSA type liquid crystal display device.
  • the compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups in the molecule, and its content is 0.1 to 30 per 100 parts by mass of all polymer components. It is preferably parts by mass, more preferably 1 to 20 parts by mass.
  • the polymerizable group may be possessed by the polymer used for the liquid crystal aligning agent, and such a polymer includes, for example, a diamine component containing a diamine having the photopolymerizable group at its end, and used for the reaction.
  • a polymer includes, for example, a diamine component containing a diamine having the photopolymerizable group at its end, and used for the reaction. The polymer obtained is mentioned.
  • Step (4-4) Step of irradiating with ultraviolet rays>
  • the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (4-2) or (4-3) above.
  • the voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
  • As the light to be irradiated for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable.
  • a light source for irradiation light for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used.
  • the irradiation amount of light is preferably 1,000 to 200,000 J/m 2 , more preferably 1,000 to 100,000 J/m 2 .
  • a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell as necessary.
  • a polarizing plate to be attached to the outer surface of the liquid crystal cell, a polarizing film called "H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself.
  • a polarizing plate consisting of
  • the liquid crystal display device of the present invention can be effectively applied to various devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones, It can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.
  • the viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample amount of 1.1 mL, a cone rotor TE-1 (1 ° 34', R24), and a temperature of 25. Measured in °C.
  • Example 1 A 50 mL Erlenmeyer flask containing a stirrer was charged with the polyamic acid solution (PAA-1) (6.00 g) obtained in Synthesis Example 1 and the diluted solution of the polymer obtained in Synthesis Example 3 (Polymer-1) (0 .48 g), NMP (1.31 g), GBL (3.91 g), BCS (4.00 g), and NMP solution (additive solution) (0.30 g) containing 10% by mass of AD-1
  • the liquid crystal aligning agent (1) was obtained by adding and stirring at room temperature for 2 hours.
  • Liquid crystal aligning agents (2) to (12) were obtained in the same manner as in Example 1, except that the types and amounts of the polymer solution and solvent used were changed as shown in Table 2 below.
  • a liquid crystal cell having a configuration of a fringe field switching (FFS) mode liquid crystal display element was produced.
  • a substrate with electrodes was prepared.
  • a glass substrate having a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm was used as the substrate.
  • An ITO electrode having a solid pattern is formed on the substrate as a first layer to form a counter electrode, and a CVD (chemical vapor deposition) electrode is formed as a second layer on the first layer counter electrode.
  • a SiN (silicon nitride) film formed by the 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 formed by patterning an ITO film is arranged as a third layer, and two pixels of a first pixel and a second pixel are formed.
  • the size of each pixel was 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. Comparing the first region and the second region of each pixel, the forming directions of the electrode elements of the pixel electrodes constituting them were different. That is, when the direction connecting the bent portions of the plurality of electrode elements is taken as a reference, the electrode elements of the pixel electrode are formed so as to form an angle of 80° clockwise in the first region of the pixel, and the electrode elements of the pixel electrode are formed in the second region of the pixel. The electrode elements of the pixel electrode are formed so as to form an angle of 80° counterclockwise.
  • the directions of the rotational movement (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode in the plane of the substrate are mutually different. It was configured in the opposite direction.
  • an ITO film is formed on the surface and the back surface of the substrate with electrodes (first glass substrate) prepared above. It was applied to the surface of a glass substrate (second glass substrate) having columnar spacers with a height of 4 ⁇ m, by a spin coating method. Then, after drying on a hot plate at 80° C.
  • a negative type liquid crystal MLC-7026-100 (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 liquid crystal cell. After that, the obtained liquid crystal cell was heated at 120° C. for 1 hour and allowed to stand at 23° C. overnight before being used for evaluation.
  • This evaluation evaluates afterimages (also referred to as AC afterimages) caused by deterioration of the alignment performance of the liquid crystal alignment film during long-term AC driving.
  • an AC voltage of ⁇ 12 V was applied at a frequency of 60 Hz for 120 hours on a high-brightness backlight (luminous intensity: 20000 cd/m 2 ) having a surface temperature of 50°C.
  • the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left at room temperature for one day.
  • the liquid crystal cell is placed between two polarizing plates arranged so that the polarizing axes are orthogonal to each other, the backlight is turned on with no voltage applied, and the transmitted light of the first region of the first pixel is obtained.
  • the angle of rotation required when the arrangement angle of the liquid crystal cell is adjusted so that the intensity is minimized and then the liquid crystal cell is rotated so that the transmitted light intensity of the second region of the first pixel is minimized is defined as the angle ⁇ .
  • the first region and the second 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 rotation angle ⁇ of the liquid crystal cell. It can be said that the smaller the rotation angle ⁇ , the better the stability of the liquid crystal alignment.
  • each of the liquid crystal aligning agents obtained above was filtered through a filter having a pore size of 1.0 ⁇ m, and then applied to the electrode-attached substrate prepared above by a spin coating method. Then, after drying on a hot plate at 80° C. for 2 minutes, baking was performed in an infrared heating furnace at 230° C. for 20 minutes to form a coating film having a thickness of 100 nm to obtain a substrate with a liquid crystal alignment film.
  • a pretilt angle of 1.5 degrees or less was obtained by using the liquid crystal aligning agent of the example of the present invention. Moreover, normally, when a negative liquid crystal is used as a liquid crystal material, it is difficult to obtain good liquid crystal orientation, but by using the liquid crystal aligning agent of the example of the present invention, when a negative liquid crystal is used as a liquid crystal material, However, a liquid crystal display element having good liquid crystal orientation (that is, having excellent AC afterimage properties) was obtained.

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Abstract

La présente invention concerne une composition polymère qui est appropriée pour un agent d'alignement de cristaux liquides qui permet d'obtenir un film d'alignement de cristaux liquides qui a une excellente résistance à une image rémanente en CA et un faible angle de pré-inclinaison.　Cette composition polymère est caractérisée en ce qu'elle contient les composants (A) et (B) suivants. Composant (A) : au moins un polymère (A) qui est choisi dans le groupe constitué par un précurseur de polyimide comportant une unité de répétition représentée par la formule (a) et un polyimide qui est un produit imidisé du précurseur de polyimide. Composant (B) : un polyester (B) qui a une unité de répétition représentée par la formule (b1) mais ne possède pas l'unité de répétition représentée par la formule (a) et une structure imidisée de celle-ci. Formule (a) (La définition de chaque symbole est telle que décrite dans la description.) Formule (b1) (La définition de chaque symbole est telle que décrite dans la description.)
PCT/JP2022/038192 2021-10-28 2022-10-13 Composition polymère, agent d'alignement de cristaux liquides, film de résine, film d'alignement de cristaux liquides, procédé de production d'élément d'affichage à cristaux liquides et élément d'affichage à cristaux liquides WO2023074391A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07509510A (ja) * 1992-07-27 1995-10-19 ビーエーエスエフ　アクチェンゲゼルシャフト 重縮合物の使用方法および新規重縮合物
JP2001270936A (ja) * 2000-01-19 2001-10-02 Nippon Shokubai Co Ltd ポリエーテルポリエステルおよびその製造方法
JP2009235162A (ja) * 2008-03-26 2009-10-15 Toray Ind Inc 熱硬化性樹脂組成物
JP2012150503A (ja) * 2006-06-29 2012-08-09 Jnc Corp 液晶配向膜用組成物、液晶配向膜および液晶表示素子
WO2019082975A1 (fr) * 2017-10-26 2019-05-02 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
JP2020514803A (ja) * 2018-02-21 2020-05-21 エルジー・ケム・リミテッド 液晶配向剤組成物、これを用いた液晶配向膜の製造方法、およびこれを用いた液晶配向膜および液晶表示素子

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07509510A (ja) * 1992-07-27 1995-10-19 ビーエーエスエフ　アクチェンゲゼルシャフト 重縮合物の使用方法および新規重縮合物
JP2001270936A (ja) * 2000-01-19 2001-10-02 Nippon Shokubai Co Ltd ポリエーテルポリエステルおよびその製造方法
JP2012150503A (ja) * 2006-06-29 2012-08-09 Jnc Corp 液晶配向膜用組成物、液晶配向膜および液晶表示素子
JP2009235162A (ja) * 2008-03-26 2009-10-15 Toray Ind Inc 熱硬化性樹脂組成物
WO2019082975A1 (fr) * 2017-10-26 2019-05-02 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
JP2020514803A (ja) * 2018-02-21 2020-05-21 エルジー・ケム・リミテッド 液晶配向剤組成物、これを用いた液晶配向膜の製造方法、およびこれを用いた液晶配向膜および液晶表示素子

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