WO2022234820A1 - 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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WO2022234820A1
WO2022234820A1 PCT/JP2022/019330 JP2022019330W WO2022234820A1 WO 2022234820 A1 WO2022234820 A1 WO 2022234820A1 JP 2022019330 W JP2022019330 W JP 2022019330W WO 2022234820 A1 WO2022234820 A1 WO 2022234820A1
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group
liquid crystal
bis
diamine
polymer
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PCT/JP2022/019330
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English (en)
Japanese (ja)
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翔一朗 中原
新平 新津
崇 仲井
友基 玉井
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日産化学株式会社
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Priority to CN202280033268.8A priority Critical patent/CN117280277A/zh
Priority to KR1020237040562A priority patent/KR20240004616A/ko
Priority to JP2023518681A priority patent/JPWO2022234820A1/ja
Publication of WO2022234820A1 publication Critical patent/WO2022234820A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element.
  • a liquid crystal display element is constructed by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes.
  • an organic film made of an organic material is used as a liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates. That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, is formed on the surfaces of the substrates that sandwich the liquid crystal and is in contact with the liquid crystal, and plays the role of orienting the liquid crystal in a certain direction between the substrates. Furthermore, the liquid crystal alignment film can control the pretilt angle of the liquid crystal.
  • a method of reducing the pretilt angle mainly by selecting a polyimide structure is known (see Patent Documents 1 and 2).
  • liquid crystal display elements In recent years, as the performance of liquid crystal display elements has improved, in addition to applications such as large-screen, high-definition liquid crystal televisions, it is also used in automotive applications such as car navigation systems, meter panels, surveillance cameras, and medical camera monitors. Liquid crystal display elements are used, and due to the demand for viewing angle characteristics, the IPS method and FFS method, which are excellent in viewing angle characteristics among driving methods for liquid crystal molecules, are being studied. (see Patent Document 3). In addition, in the IPS and FFS liquid crystal display elements, static electricity tends to accumulate in the liquid crystal cell, and the accumulated electric charge disturbs the liquid crystal alignment and affects the display as an afterimage. significantly lower.
  • Patent Document 4 discloses a liquid crystal aligning agent containing a polyamic acid or polyimide having a structural unit having an aromatic tetracarboxylic acid residue and a structural unit having an alicyclic tetracarboxylic acid residue. is proposed, and Patent Document 5 proposes a liquid crystal aligning agent containing a polyimide precursor having a diphenylamine skeleton.
  • an object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal display element with a low incidence of display defects (line burn-in) even when a negative liquid crystal is used as the liquid crystal material.
  • Another object of the present invention is to provide a liquid crystal aligning agent that provides a liquid crystal alignment film that has high stability in liquid crystal alignment and can reduce the generated charge in a short time while reducing the absolute value of the accumulated charge.
  • liquid crystal aligning agent having the following composition is optimal for achieving the above object, and completed the present invention.
  • a liquid crystal aligning agent comprising the following polymer (A), polymer (B) and crosslinkable compound (C).
  • R is the same as R in formula (d D ).
  • the polyimide precursor does not have an imide ring structure.
  • two Ars each independently represent a divalent benzene ring, a biphenyl structure, or a naphthalene ring, and any hydrogen atom on the ring may be replaced with a monovalent group.
  • L o is —O—(—Ar′—O—) n — (n is an integer of 0 to 3.
  • Ar′ represents a divalent benzene ring and a biphenyl structure, and any hydrogen atom on the ring is may be substituted with a monovalent group.
  • the plurality of Ar' may be the same or different.
  • -(CH 2 ) n - (n is an integer of 2 to 18 .)
  • Y D represents a divalent organic group having a group “—N(D)—” (D represents a protecting group that is eliminated by heating and replaced with a hydrogen atom) in the molecule.
  • R's each independently represent a hydrogen atom or a monovalent organic group.
  • Y B represents a divalent organic group that satisfies the following conditions (1) and (2).
  • R has the same definition as R in formula (d 0 ) above.
  • Condition (1) a heterocyclic ring containing a nitrogen atom and a secondary or tertiary amino group (provided that the group "-N(D')-"(D' is a protective group that is eliminated by heating and replaced with a hydrogen atom ) does not have a nitrogen atom-containing structure selected from the group consisting of excluding amino groups derived from ).
  • Condition (2) Does not have a side chain group with 6 or more carbon atoms. (a is an integer of 2 to 4, R a is an a-valent organic group, and the a bonding site with N is an aliphatic carbon atom.)
  • Boc represents a tert-butoxycarbonyl group.
  • Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
  • 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).
  • liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal display element with a low incidence of display defects (line burn-in) even when a negative liquid crystal is used as the liquid crystal material.
  • a liquid crystal alignment film can be obtained in which the stability of the liquid crystal alignment is high and the generated charge can be reduced in a short time while reducing the absolute value of the accumulated charge.
  • a liquid crystal alignment film in which abrasion of the film during alignment treatment is suppressed can be obtained, so a liquid crystal display device with excellent display quality can be obtained.
  • the liquid crystal aligning agent of the present invention is a polyimide precursor which is a reaction product of a diamine component containing a diamine represented by the above formula (d 0 ) and a diamine represented by the above formula (d D ) and a tetracarboxylic acid derivative component. It contains a polyimide polymer (A) obtained by imidizing a polyimide.
  • the high-temperature treatment required for thermal imidization becomes unnecessary.
  • the obtained liquid crystal alignment film has high stability of liquid crystal alignment, and a liquid crystal display element with a low incidence of display defects (line burn-in) can be obtained.
  • the polymer (A) is obtained by imidizing a polyimide precursor obtained from a tetracarboxylic acid derivative component containing a tetracarboxylic dianhydride and a diamine component containing a specific diamine.
  • the imidization rate of polyimide in the polymer (A) is preferably 10 to 100% from the viewpoint of reducing the occurrence rate of display defects.
  • the lower limit of the imidization rate is preferably 10%, more preferably 20%, still more preferably 50%, most preferably 70%, and the upper limit of the imidization rate is preferably 100%, more preferably 99%. 95% is even more preferred. Specific examples of materials used in the production of the polymer (A) and production methods are described in detail below.
  • the diamine component used in the production of the polymer (A), which is a polyimide contained in the liquid crystal aligning agent of the present invention, is a diamine represented by the following formula (d 0 ) and a diamine represented by the following formula (d D ) contains
  • the diamine represented by the following formula (d 0 ) and the diamine represented by the following formula (d D ) may be used singly or in combination of two or more. (The definition of each symbol in the formula is the same as above.)
  • the hydrogen atom on the benzene ring, biphenyl structure, or naphthalene ring of Ar′ contained in Ar and L o in the above formula (d 0 ) is, for example, a halogen atom, a carbon number of 1 to 10 (more preferably a carbon 1 to 5) alkyl group, alkenyl group having 2 to 10 carbon atoms (more preferably 2 to 5 carbon atoms), alkoxy group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms), 1 carbon atom to 10 (more preferably 1 to 5 carbon atoms) fluoroalkyl group, 2 to 10 carbon atoms (more preferably 2 to 5 carbon atoms) fluoroalkenyl group, 1 to 10 carbon atoms (more preferably 1 to 1 carbon atoms) 5) may be substituted with a fluoroalkoxy group, a hydroxy group, an alkyloxycarbonyl group having 1 to 10 carbon atoms (more preferably 1 to 5
  • the diamine represented by the above formula (d 0 ) includes 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and the following formulas (d 0 -1) to (d 0 - 10) compounds represented by 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8 -bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1 , 10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-
  • the diamine represented by the above formula (d D ) is preferably an aromatic diamine having one aromatic ring in the molecule, and any hydrogen on the aromatic ring
  • -NR-(R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms , a phenyl group, or the group “-D”)
  • the aromatic ring include a benzene ring, a naphthalene ring and an anthracene ring, preferably a benzene ring and a naphthalene ring, and more preferably a benzene ring.
  • Any hydrogen atom on the aromatic ring may be 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, or a fluorine atom containing 1 to 5 carbon atoms. may be replaced with a monovalent organic group in which a portion of the hydrogen atoms on the alkyl group having 1 to 5 carbon atoms is substituted with a hydroxy group.
  • D in the group "-N(D)-” represents a protective group that is detached by heating and replaced with a hydrogen atom, and is decomposed by heat and detached, and is converted to the group "-NH-".
  • the structure of D which is an organic group that can be eliminated by heat, includes a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a tertiary butoxycarbonyl group (tert-butoxycarbonyl group), and the like.
  • Typical examples include carbamate-based organic groups, but tertiary butoxy groups are preferred from the viewpoint of efficient thermal desorption, desorption at a relatively low temperature, and emission as a harmless gas when desorbed. Carbonyl groups are particularly preferred.
  • the diamine represented by the above formula (d D ) is preferably a diamine selected from the following formulas (d D -1) to (d D -7).
  • R represents a hydrogen atom or a tert-butoxycarbonyl group.
  • a preferable content of the diamine represented by the above formula (d 0 ) is preferably 50 to 95 mol %, preferably 50 to 90 mol %, based on the total diamine component used in the production of the polymer (A). Mole % is more preferred.
  • the preferred content of the diamine of formula (d D ) is 5 to 50 mol %, preferably 10 to 50 mol %, based on the total amount of the diamine component used in the production of the polymer (A). It is more preferable to have
  • the diamine component used in the production of the polymer (A) contained in the liquid crystal aligning agent of the present invention includes, in addition to the above diamines, various diamines (hereinafter referred to as other diamines 1 Also called.) can be used. Each of the other diamines 1 may be used alone or in combination of two or more.
  • diamines 1 include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine, 4-(2-(methylamino)ethyl)aniline, 4- (2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4
  • m and n are integers of 1 to 3 (provided that 1 ⁇ m + n ⁇ 4), j is an integer of 0 or 1,
  • X 1 is -(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH 3 )-, -NH-, -O-, -CH 2 O-, - represents CH 2 —OCO—, —COO—, or —OCO—
  • R 1 is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, a carbon number It represents an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms.
  • X 2 represents -O-, -CH 2 O-, -CH 2 -OCO-, -COO- or -OCO-.
  • R 2 represents a fluorine atom-containing alkyl group having 1 to 20 carbon atoms or an alkyl group having 3 to 20 carbon atoms.
  • the amount of the other diamines 1 is It is preferably 5 to 40 mol %, more preferably 10 to 40 mol %.
  • the total content of the diamines of the above formulas (d 0 ) and (d D ) is preferably 95 mol% or less with respect to the total diamine components used in the production of the polymer (A), It is preferably 90 mol % or less.
  • the tetracarboxylic acid derivative component used in the production of the polymer (A) of the present invention is not only tetracarboxylic dianhydride, but also its derivatives such as tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester, tetracarboxylic acid Dialkyl ester dihalides and the like can also be used.
  • the tetracarboxylic acid derivative component one type of tetracarboxylic dianhydride or derivative thereof may be used alone, or two or more types may be used in combination.
  • tetracarboxylic dianhydrides or derivatives thereof include acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, or these derivatives.
  • tetracarboxylic dianhydrides having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure, or these More preferably, it contains a derivative (hereinafter collectively referred to as a tetracarboxylic acid derivative having a specific partial structure), and at least one selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure.
  • a derivative hereinafter collectively referred to as a tetracarboxylic acid derivative having a specific partial structure
  • a tetracarboxylic dianhydride having a partial structure of or a derivative thereof is an aromatic tetracarboxylic dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an aromatic ring.
  • An acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not need to be composed only of a chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in part thereof.
  • 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.
  • the tetracarboxylic acid derivative component that can be used in the synthesis of the polymer (A) preferably includes the following tetracarboxylic dianhydrides or derivatives thereof (hereinafter collectively referred to as specific tetracarboxylic acid derivatives) ).
  • Acyclic aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3 ,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracar
  • More preferred examples of the above specific tetracarboxylic acid derivatives include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3 ,3
  • the usage ratio of the tetracarboxylic acid derivative having the specific partial structure or the specific tetracarboxylic acid derivative is preferably 10 mol% or more, more preferably 20 mol% or more, based on the total tetracarboxylic acid derivative components used. , more preferably 50 mol % or more.
  • the liquid crystal aligning agent of the present invention has "H-N(R)-YD'-N(R)-H" (YD ' is a group "-N(D ' )-"(D' is , represents a protective group that is eliminated by heating and replaced with a hydrogen atom.).
  • R has the same meaning as R in formula (d D ).
  • the polyimide precursor of the polymer (B) does not have an imide ring structure.
  • the diamine (d D'B ) By adding the diamine (d D'B ) to the diamine component used for producing the polymer (B), the polymer (B ) can be unevenly distributed. Therefore, the effect of improving the film strength possessed by the polymer (B) is increased, and the abrasion of the film during the alignment treatment is suppressed.
  • the diamine component used for producing the polymer (B) includes the diamine represented by the above formula (d B ).
  • the divalent organic group Y B contained in the diamine (d B ) satisfies the conditions (1) and (2) above.
  • the aspect of condition (1) the basicity of the polymer is lowered and the thermal imidization reaction of the polymer (B) is suppressed, so that it is possible to obtain a liquid crystal alignment film with high film strength.
  • the aspect of condition (2) the alignment control force of the liquid crystal is increased in the IPS system and the FFS system, and the alignment stability of the resulting liquid crystal alignment film can be enhanced.
  • a nitrogen atom selected from the group consisting of a heterocyclic ring containing a nitrogen atom and a secondary or tertiary amino group (excluding an amino group derived from the group "-N(D')-")
  • a diamine in which two groups "-NHR" (R has the same definition as R in the above formula (d B )) are bonded to a divalent organic group having a containing structure other A diamine having a specific nitrogen atom-containing structure exemplified for diamine 1 can be mentioned.
  • Examples of the diamine represented by the above formula (d B ) include an aromatic diamine (I) having one benzene ring; a diamine having two benzene rings and having two benzene rings linked by a single bond (II- a); an aromatic diamine in which two benzene rings are linked by a divalent group, wherein the divalent group is an oxygen atom or an organic group having 1 to 3 carbon atoms and is the same as the two benzene rings Aromatic diamines (II-b), which are bonded at the atoms of However, the aromatic diamine (I), the aromatic diamine (II-a) and the aromatic diamine (II-b) are diamines other than the above diamine (d D'B ), and the above conditions (1) and conditions (2) is satisfied.
  • diamine represented by the above formula (d B ) include the diamine represented by the formula (d M ) described later, and the diamine represented by the above formulas (d 0 -1) to (d 0 -10).
  • diamine (d D'B ) examples include the diamines exemplified for the diamine (d D ), including preferred embodiments.
  • the diamine (d D'B ) may be used alone or in combination of two or more.
  • specific examples of D' of the group "-N(D')-” include the structures exemplified for D of the above group "-N(D)-” including preferred embodiments.
  • a preferable content of the diamine of the above formula (d D'B ) is preferably 5 to 40 mol %, preferably 10 to 40 mol %, based on the total diamine component of the diamine component used in the production of the polymer (B). is more preferred.
  • the diamine component used for producing the polymer (B) preferably contains a diamine represented by the following formula (d M ).
  • (L M represents a single bond, —CH 2 —, —CO—, —O—, or —C(CH 3 ) 2 —.
  • L M ′ is a single bond or —(CH 2 ) m — (m is is an integer of 1 to 2.
  • Ar M represents a divalent benzene ring, any hydrogen atom on the ring may be replaced with a monovalent group.
  • a plurality of Ar M are present , the plurality of Ar 2 M may be the same or different, each of the plurality of R independently represents a hydrogen atom or a monovalent organic group, and n is an integer of 0 to 1.
  • a hydrogen atom on the benzene ring of Ar M is a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms.
  • a fluoroalkenyl group having 2 to 5 carbon atoms, a fluoroalkoxy group having 1 to 5 carbon atoms, a hydroxy group, an alkyloxycarbonyl group having 1 to 5 carbon atoms, a hydroxy group, a carboxy group, a cyano group, a nitro group, etc. may be
  • diamine represented by the above formula (d M ) include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m -phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 3-aminobenzylamine, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine , 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3 ,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dime
  • the diamine (d M ) may be used alone or in combination of two or more.
  • the preferred content of the diamine of the above formula (d M ) is preferably 60 to 95 mol%, preferably 60 to 90 mol%, of the total diamine component of the diamine component used in the production of the polymer (B). more preferred.
  • a diamine other than the diamine (d D'B ) and the diamine (d M ) (hereinafter also referred to as other diamine 2) may be used.
  • a specific example of the other diamine 2 is a diamine component for obtaining the above polymer (A), which satisfies the above conditions (1) and (2).
  • tetracarboxylic acid derivative component used in the production of the polymer (B) include the same compounds as those exemplified for the polymer (A), including preferred specific examples.
  • the tetracarboxylic acid derivative component used in the production of the polymer (B) is more preferably a tetracarboxylic acid derivative having the specific partial structure or a specific tetracarboxylic acid derivative, and the specific tetracarboxylic acid derivative Most preferably, the more preferred embodiment of is used.
  • the tetracarboxylic acid derivative having the specific partial structure or the specific tetracarboxylic acid derivative is contained in an amount of 10 mol% or more with respect to all the tetracarboxylic acid derivative components used in the production of the polymer (B). is preferred, more preferably 20 mol% or more, and even more preferably 50 mol% or more.
  • the tetracarboxylic acid derivative component used in the production of the polymer (B) is the aromatic Group tetracarboxylic dianhydrides or derivatives thereof are preferably contained, and among these, tetracarboxylic dianhydrides having a benzene ring structure or derivatives thereof are preferred. More preferred are the aromatic tetracarboxylic acid dianhydrides exemplified in the specific tetracarboxylic acid derivatives above, or derivatives thereof.
  • the tetracarboxylic acid derivative component used for producing the polymer (A) and the tetracarboxylic acid derivative component used for producing the polymer (B) may be the same or different.
  • the content ratio of the polymer (A) and the polymer (B) is from 10/90 in terms of the mass ratio of [polymer (A)]/[polymer (B)].
  • 90/10 is preferred, 20/80 to 90/10 is more preferred, and 20/80 to 80/20 is even more preferred.
  • a polyimide precursor such as polyamic acid or polyamic acid ester used for producing the polymer (A) and polymer (B) contained in the liquid crystal aligning agent of the present invention can be synthesized, for example, by the following method.
  • Synthesis of polyamic acid is carried out by reacting a diamine component containing the diamine and a tetracarboxylic acid derivative component containing the tetracarboxylic dianhydride or its derivative in an organic solvent.
  • the ratio of the tetracarboxylic dianhydride and the diamine used in the synthetic reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.5 to 2 per equivalent of the amino group of the diamine.
  • a ratio that provides equivalents is preferred, and a ratio that provides 0.8 to 1.2 equivalents is more preferred.
  • the reaction temperature in the polyamic acid synthesis reaction is preferably -20 to 150°C, more preferably 0 to 100°C.
  • the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.
  • the polyamic acid synthesis 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.
  • organic solvent examples include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone.
  • methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Solvents such as glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used.
  • Polyamic acid esters are produced by, for example, [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [III] a tetracarboxylic acid It can be obtained by a known method such as a method of reacting a diester dihalide and a diamine.
  • a polyimide can be obtained by ring-closing (imidizing) the polyimide precursor.
  • the method 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 usually 100 to 400° C., preferably 120 to 250° C., and the water generated by the imidization reaction is preferably removed 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.
  • Examples of basic catalysts include pyridine and triethylamine.
  • acid anhydrides include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride.
  • 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 polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyimide precursor and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. is.
  • 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.
  • a tetracarboxylic acid derivative component containing a tetracarboxylic acid dianhydride or a derivative thereof, and a diamine component containing the diamine, together with an appropriate terminal blocking agent end-blocking A stop-type polymer may be synthesized.
  • the end-blocking polymer has effects of improving the film hardness of the liquid crystal alignment film obtained by the coating film and improving the adhesion between the sealant and the alignment film.
  • the terminal of the polyimide precursor or polyimide in the present invention include an amino group, a carboxyl group, an acid anhydride group, or a group derived from a terminal blocking agent to be described later.
  • An amino group, a carboxyl group, and an acid anhydride group can be obtained by a normal condensation reaction, or can be obtained by terminal blocking using the following terminal blocking agents.
  • 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.
  • Acid anhydrides dicarbonic acid diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride and nicotinic acid chloride; aniline, 2-aminophenol, 3-aminophenol, 4 -aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n - monoamine compounds such as heptylamine and n-octylamine; ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or having unsaturated bonds such as 2-acryloyloxyethyl isocyanate and 2-methacryloy
  • the proportion of the end blocking agent used is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, per 100 mol parts in total of the diamine components used.
  • the liquid crystal aligning agent of the present invention contains a polymer (A), a polymer (B), and a crosslinkable compound (C) described below.
  • the liquid crystal aligning agent of the present invention may contain other polymers in addition to the polymer (A) and polymer (B).
  • Other polymer types include polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene or derivatives thereof, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like.
  • Other polymers may be used singly or in combination of two or more.
  • the content of the other polymer is preferably 30 parts by mass or less, more preferably 1 to 25 parts by mass, and further 1 to 20 parts by mass with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. preferable.
  • the liquid crystal alignment agent is used to produce the liquid crystal alignment film, and takes the form of a coating liquid from the viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is the form of the coating liquid containing an above-described polymer component and an organic solvent.
  • the organic solvent contained in the coating liquid is not particularly limited as long as the polymer component is uniformly dissolved.
  • Examples include N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethyllacto Amide, 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-dimethylpropanamide, N-(n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and ⁇ -butyrolactone are preferred.
  • the content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.
  • the organic solvent contained in the liquid crystal aligning agent is a mixture of the above solvents and a solvent (also referred to as a poor solvent) that improves the coatability and the surface smoothness of the coating film when applying the liquid crystal aligning agent.
  • a solvent also referred to as a poor solvent
  • the use of solvents is preferred. Specific examples of the poor solvent used in combination are shown below, but are not limited thereto.
  • the content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, particularly preferably 20 to 70% by mass, of the total solvent contained in the liquid crystal aligning agent.
  • the type and content of the poor solvent are appropriately selected according to the liquid crystal aligning agent coating device, coating conditions, coating environment, and the like.
  • poor solvents examples include diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, and diethylene glycol.
  • dimethyl ether diethylene glycol diethyl ether, 4-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 monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 1 -(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl
  • 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 liquid crystal aligning agent of the present invention contains the crosslinkable compound (C).
  • the crosslinking reaction with the epoxy crosslinking agent proceeds during baking, so that the thermal imidization reaction, that is, the thermal imidization reaction of the imide precursor contained in the polymer (B) component is suppressed. Therefore, the resulting liquid crystal alignment film has a reduced imidized structure, so that a liquid crystal alignment film capable of reducing the generated charge in a short time while reducing the absolute value of the accumulated charge can be obtained.
  • the content of the crosslinkable compound (C) in the liquid crystal aligning agent of the present invention is preferably 0.5 to 20 parts by mass, more preferably 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. is 1 to 15 parts by mass.
  • Specific examples of the crosslinkable compound (C) include N,N,N',N'-tetraglycidyl-1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,3-diamino Cyclohexane, N,N,N',N'-tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-2-methyl-4 -aminocyclohexyl)methane, bis(N,N-diglycidyl-3-methyl-4-aminocyclohe
  • the liquid crystal aligning agent of the present invention may additionally contain components (hereinafter also referred to as additive components) other than the polymers (A) and (B) and the crosslinkable compound (C).
  • 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, and the strength of the liquid crystal alignment film other than the crosslinkable compound (C).
  • other cross-linking compounds dielectric or conductive substances for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film, imidization accelerators, and the like.
  • a crosslinkable compound (C1) which is a compound having an oxiranyl group other than the crosslinkable compound (C); At least one crosslinkable compound selected from the group consisting of a crosslinkable compound (C2) which is a compound having at least one substituent selected from; and a crosslinkable compound (C3) which is a compound having a polymerizable unsaturated group compound.
  • crosslinkable compound (C1) examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether.
  • 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, jER828 Mitsubishi Chemical bisphenol A type epoxy resins such as JER807 (manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resins such as JER807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), YX6954BH30 (Mitsubishi Chemical Corporation) (manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), and (o, m, p-) cresol novolacs such as EOCN-
  • triglycidyl isocyanurates such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.), alicyclic epoxy resins such as Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.), N,N,N',N'-tetraglycidyl-1, 4-phenylenediamine, N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4.4'-diaminobiphenyl, 2,2-bis[4-(N,N-diglycidyl-4- aminophenoxy)phenyl]propane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, tetrakis(glycidyloxymethyl)methane, paragraph [0037] of JP-A-10-338880 and compounds described in International Publication No.
  • crosslinkable compounds (C2) and (C3) include compounds having two or more two or more oxetanyl groups described in paragraphs [0170] to [0175] of WO 2011/132751; AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B -870N, B-874N, compounds having a blocked isocyanate group such as B-882N (manufactured by Mitsui Chemicals, Inc.); 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl- 2-oxazoline), 2,2′-bis(5-methyl-2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, oxazolines such as Epocross (manufactured
  • crosslinkable compounds are examples of crosslinkable compounds, and are not limited to these. Examples thereof include components other than those described above disclosed on pages 53 [0105] to 55 [0116] of WO2015/060357. In addition, two or more types of crosslinkable compounds may be combined.
  • the content of the crosslinkable compounds (C1) to (C3) in the liquid crystal aligning agent of the present invention is 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. It is preferably 1 to 15 parts by mass, more preferably 1 to 15 parts by mass.
  • adhesion aid examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, vinyl trimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy
  • the solid content concentration in the liquid crystal aligning agent (ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but preferably It ranges from 0.5 to 15% by mass, more preferably from 1 to 10% by mass.
  • a particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when the spinner method is used, 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 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 can be used for a horizontal alignment type or vertical alignment type (VA type) liquid crystal alignment film. membrane.
  • VA type vertical alignment type
  • the liquid crystal display element of the present invention comprises the liquid crystal alignment film.
  • the liquid crystal display device of the present invention can be manufactured, for example, by a method including the following steps (1) to (3). (1) Step of applying a liquid crystal aligning agent onto a substrate On one surface of a substrate provided with a patterned transparent conductive film, the liquid crystal aligning agent of the present invention is applied, for example, by a roll coater method, a spin coat method, a printing method, or an inkjet method.
  • 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.
  • a plastic substrate such as an acrylic substrate or a polycarbonate substrate
  • 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.
  • preheating is preferably carried out first for the purpose of preventing dripping of the applied liquid crystal aligning agent.
  • the prebaking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C.
  • the pre-baking time is preferably 0.25-10 minutes, more preferably 0.5-5 minutes.
  • a heating (post-baking) step is further carried out.
  • the post-bake temperature is preferably 80-200°C, more preferably 120-180°C.
  • the post-bake time is preferably 5-200 minutes, more preferably 10-100 minutes.
  • the thickness of the film thus formed is preferably 5 to 300 nm, more preferably 10 to 200 nm.
  • the coating film formed in the above step (1) or (2) can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment.
  • Alignment imparting treatment includes rubbing treatment in which the coating film is rubbed in a fixed direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, cotton, etc., and photo-alignment treatment in which the coating film is irradiated with polarized or non-polarized radiation. processing and the like.
  • ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used as the radiation to irradiate the coating film.
  • the radiation When the radiation is polarized, it may be linearly polarized or partially polarized. Further, when the radiation used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When non-polarized radiation is applied, the direction of irradiation is oblique.
  • the following two methods are mentioned.
  • 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.
  • the peripheral portions of the two substrates are bonded together using a sealing agent, and the 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 opened. Seal.
  • 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.
  • 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 a curing agent and aluminum oxide spheres as spacers can be used.
  • the liquid crystal composition is not particularly limited, and may be a composition containing at least one liquid crystal compound (liquid crystal molecule) exhibiting a nematic phase (hereinafter also referred to as a nematic liquid crystal), or a liquid crystal exhibiting a smectic phase.
  • 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 structures or terphenyl structures linked by alkyl groups).
  • the liquid crystal composition may further contain an additive from the viewpoint of improving liquid crystal orientation.
  • additives include photopolymerizable monomers such as compounds having a polymerizable group; optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); antioxidants; UV absorbers; dyes; antifoaming agents; polymerization initiators; or polymerization inhibitors.
  • Positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081 manufactured by Merck.
  • negative liquid crystal include MLC-6608, MLC-6609, MLC-6610, MLC-7026 and MLC-7026-100 manufactured by Merck.
  • MLC-3023 manufactured by Merck & Co., Ltd. can be mentioned.
  • 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 for example, a polarizing film called "H film” in which iodine is absorbed while stretching orientation of polyvinyl alcohol is sandwiched between cellulose acetate protective films.
  • a polarizing plate made of the film itself can be mentioned.
  • the liquid crystal alignment film of the present invention can be applied to various uses other than the liquid crystal alignment film for the above uses. It can also be used for a liquid crystal alignment film for a transmission scattering type liquid crystal light control device. Furthermore, applications other than liquid crystal alignment films, such as protective films (e.g. protective films for color filters), spacer films, interlayer insulating films, antireflection films, wiring coating films, antistatic films, motor insulating films (flexible It can also be used for a gate insulating film of a display).
  • protective films e.g. protective films for color filters
  • spacer films e.g. protective films for color filters
  • interlayer insulating films e.g. antireflection films
  • wiring coating films e.g. antistatic films
  • motor insulating films flexible It can also be used for a gate insulating film of a display.
  • 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.
  • NMP N-methyl-2-pyrrolidone
  • GBL ⁇ -butyrolactone
  • BCS butyl cellosolve (ethylene glycol monobutyl ether)
  • ⁇ Measurement of imidization rate Put 20 mg of polyimide powder in an NMR sample tube (NMR sampling tube standard, ⁇ 5 (manufactured by Kusano Kagaku)), deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS (tetramethylsilane) mixture) (0 .53 mL) was added and sonicated until completely dissolved. This solution was subjected to proton NMR at 500 MHz using an NMR spectrometer (JNW-ECA500) (manufactured by JEOL Datum Co., Ltd.). For the imidization rate, a proton derived from a structure that does not change before and after imidization is determined as a reference proton.
  • JNW-ECA500 NMR spectrometer
  • Imidation rate (%) (1- ⁇ x/y) x 100
  • x is the proton peak integrated value derived from the NH group of the amic acid
  • y is the peak integrated value of the reference proton
  • ⁇ is one NH group proton of the amic acid in the case of polyamic acid (imidization rate is 0%). is the number ratio of reference protons to
  • A-1) was obtained.
  • 80.0 g of the polyamic acid solution (PAA-A-1) obtained above was placed in a 300 mL Erlenmeyer flask containing a stirrer, 70.0 g of NMP, 6.97 g of acetic anhydride, and 1 of pyridine. 80 g was added, stirred at room temperature for 30 minutes, and then reacted at 55° C. for 3 hours. This reaction solution was poured into 560 g of methanol, and the obtained precipitate was filtered off. After washing the precipitate with methanol, it was dried under reduced pressure at a temperature of 60° C.
  • polyimide powder The imidization rate of this polyimide was 75%. 9.00 g of this polyimide powder was taken into a 300 mL Erlenmeyer flask containing a stirrer, 36.0 g of NMP was added, and the solution was stirred at 50° C. for 20 hours to dissolve the solid content at a concentration of 20% by mass. A solution of polyimide (PI-A-1) was obtained. Table 1 shows the types and amounts of diamines and tetracarboxylic acid derivatives used in preparing the polyimide (PI-A-1) solution obtained in Synthesis Example 1, the presence or absence of E-1, and the imidization rate. show.
  • PAA-A-2 a polyamic acid solution
  • PAA-A-2 a polyamic acid solution
  • 100 g of the obtained polyamic acid solution was placed in a 200 mL Erlenmeyer flask equipped with a stirrer, 1.24 g (5.68 mmol) of E-1 was added, and the mixture was stirred at 40° C. for 15 hours.
  • a solution of polyamic acid (PAA-A-3) was obtained.
  • 100 g of the above (PAA-A-3) solution was placed in a 200 mL Erlenmeyer flask equipped with a stirrer, 66.7 g of NMP, 14.2 g of acetic anhydride, and 4.70 g of pyridine were added and stirred at room temperature for 30 minutes.
  • 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.
  • the substrate was a glass substrate with a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm.
  • An ITO electrode having a solid pattern is formed as the first layer on the substrate to constitute the counter electrode, and the second layer is formed on the first layer counter electrode by the CVD method.
  • a thin SiN (silicon nitride) film was formed.
  • the SiN film of the second layer has a film thickness of 500 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.
  • the pixel had a first region and a second region bounded by a line connecting bent portions of a plurality of electrode elements.
  • the formation directions of the electrode elements of the pixel electrodes that constitute them are 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. That is, in the first region and the second region of each pixel, 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.
  • liquid crystal aligning agents (1) to (9) were each filtered through a filter with a pore size of 1.0 ⁇ m, and then applied to the prepared substrate with electrodes by spin coating. After drying on a hot plate at 80° C. for 5 minutes, baking was performed in an IR oven at 150° C. for 20 minutes to obtain a polyimide film with a film thickness of 60 nm.
  • This polyimide film is subjected to rubbing alignment treatment with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 30 mm/sec, indentation length: 0.3 mm, rubbing direction: the above-mentioned plurality of pixel electrodes of the third layer).
  • ultrasonic waves were applied in pure water for 1 minute for cleaning, and water droplets were removed by air blow. Then, it dried at 80 degreeC for 15 minutes, and obtained the board
  • a glass substrate having columnar spacers with a height of 4 ⁇ m and having an ITO electrode formed on the back surface as a counter substrate was also treated in the same manner as described above to obtain a substrate with a liquid crystal alignment film subjected to alignment treatment. rice field.
  • a substrate with electrodes (a glass substrate with a size of 30 mm in width ⁇ 40 mm in length and a thickness of 1.1 mm, a glass A rectangular ITO electrode having a width of 10 mm, a length of 40 mm, and a thickness of 35 nm was formed on the substrate) by spin coating. After drying on a hot plate at 50° C. for 5 minutes, baking was performed in an IR oven at 150° C. for 20 minutes to form a coating film having a thickness of 60 nm to obtain a substrate with a liquid crystal alignment film.
  • This liquid crystal alignment film was subjected to rubbing alignment treatment with a rayon cloth (YA-20R manufactured by Yoshikawa Kako) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 30 mm / sec, indentation length: 0.3 mm).
  • the substrate was cleaned by irradiating ultrasonic waves for 1 minute inside, water droplets were removed by an air blow, and dried at 80° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.
  • a spacer of 4 ⁇ m was sprayed on the surface of one of the liquid crystal alignment films, and then a sealant (XN-1500T manufactured by Mitsui Chemicals, Inc.) was printed thereon.
  • heat treatment is performed at 150° C. for 60 minutes to harden the sealant to prepare an empty cell.
  • 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 a 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 to obtain a liquid crystal cell for voltage holding ratio measurement.
  • the liquid crystal cell was placed between two polarizing plates arranged so that the polarizing axes were perpendicular to each other, and the backlight was turned on with no voltage applied so that the brightness of the transmitted light was minimized.
  • the arrangement angle of the liquid crystal cell was adjusted. Then, the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel was the darkest to the angle at which the first region was the darkest was calculated as the angle ⁇ .
  • the angle ⁇ was similarly calculated by comparing the second region and the first region.
  • the stability of the liquid crystal alignment was defined as "good" when the angle ⁇ was less than 0.4°, and was defined as “poor” when the angle ⁇ was 0.4° or more. Table 4 shows the evaluation results.
  • a liquid crystal cell fabricated in the same manner as described above (Fabrication of FFS liquid crystal display element) was placed between two polarizing plates arranged so that their polarization axes were orthogonal to each other, and opposed to the pixel electrode.
  • the LED backlight is irradiated from below the two polarizing plates with the electrode shorted and at the same potential, and the brightness of the LED backlight transmitted light measured on the two polarizing plates is the minimum.
  • the angle of the liquid crystal cell was adjusted so that Next, a VT curve (voltage-transmittance curve) was measured while an AC voltage having a frequency of 60 Hz was applied to the liquid crystal cell, and the AC voltage at which the relative transmittance was 23% was calculated as the driving voltage.
  • the liquid crystal cell was driven by applying an AC voltage with a frequency of 60 Hz, which gave a relative transmittance of 23%, and at the same time, a DC voltage of 1 V was applied to drive the liquid crystal cell for 120 minutes. After that, the application of only the DC voltage was stopped, and the device was driven with only the AC voltage for another 15 minutes.
  • VT curve voltage-transmittance curve
  • the liquid crystal cell was driven for 60 minutes by applying an AC voltage with a frequency of 60 Hz at which the relative transmittance was 100%.
  • an AC voltage having a relative transmittance of 23% was applied, and an applied voltage capable of minimizing display flicker was measured while sweeping the DC voltage.
  • the absolute value of the applied voltage that can minimize this display flicker was defined as the amount of charge accumulation, and when this value exceeded 100 mV, it was defined as “bad", and when it was 100 mV or less, it was defined as "good”.
  • the afterimage evaluation according to the method described above was performed under temperature conditions in which the temperature of the liquid crystal cell was 40°C. Table 4 shows the evaluation results.
  • Liquid crystal aligning agents (1) to (9) were each applied to an ITO substrate by spin coating. After drying on a hot plate at 60° C. for 1 minute and 30 seconds, baking was performed in an IR oven at 150° C. for 20 minutes to form a coating film with a thickness of 100 nm. After that, the liquid crystal alignment film is rubbed twice with a rayon cloth (Yoshikawa Kako YA-20R) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, pushing length: 0.5 mm) twice. When the surface of the film was observed with a confocal laser microscope, the film surface was evaluated as "bad” if there were scratches, and as "good” if there were no scratches. Table 4 shows the evaluation results.
  • Table 4 below shows the evaluation results of the liquid crystal display elements using the liquid crystal aligning agents of Examples 1 to 4 and Comparative Examples 1 to 5 as described above.
  • the liquid crystal aligning agent of the present invention is useful for forming liquid crystal alignment films in a wide range of liquid crystal display devices such as IPS drive system and FFS drive system.

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Abstract

L'invention concerne un agent d'alignement de cristaux liquides grâce auquel un élément d'affichage à cristaux liquides ayant une faible incidence de défauts d'affichage (ligne de rodage-in) est obtenu même lorsqu'un cristal liquide de type négatif est utilisé en tant que matériau de cristaux liquides.　La présente invention concerne un agent d'alignement de cristaux liquides contenant un polymère (A), un polymère (B) et un composé réticulable (C).　Polymère (A) : L'invention concerne un polyimide obtenu par imidisation d'un précurseur de polyimide qui est un produit de réaction d'un composant dérivé d'acide tétracarboxylique et d'un composé diamine contenant une diamine représentée par la formule (d0) et une diamine représentée par la formule (dD).　Polymère (B) : L'invention concerne un précurseur de polyimide qui est un produit de réaction d'un composant dérivé tétracarboxylique et d'un composant diamine constitué d'une diamine (dD'B) représentée par "H-N(R)-YD'-N(R)-H" (YD' représentant un groupe organique divalent ayant "-N(D')-" dans sa molécule (où D' représente un groupe protecteur dissocié par chauffage et remplacé par un atome d'hydrogène), et R étant synonyme de R dans la formule (dD)) et une diamine représentée par la formule (dB) (à l'exclusion de la diamine (dD'B). Cependant, le précurseur de diamine ne possède pas de structure cyclique imide.　Composé réticulable (C) : L'invention concerne également un composé à base d'époxy représenté par la formule (En). (Dans la formule (d0) : les deux atomes Ar représentent chacun indépendamment un cycle benzène divalent, une structure biphényle, ou un cycle naphtalène, et tout atome d'hydrogène sur l'anneau peut être substitué par un groupe univalent ; et Lo représente -O-(-Ar'-O-)n- (n étant un nombre entier de 0 à 3, Ar' représentant un noyau benzénique divalent ou une structure biphényle, et tout atome d'hydrogène sur l'anneau pouvant être substitué par un groupe univalent), -(CH2)n- (n étant un nombre entier de 2 à 18), ou un groupe dans lequel au moins une partie des groupes -CH2- des –(CH2)n- sont substitués par -O-, -C(=O)-, or -O-C(=O)-. Dans la formule (dD), YD représente un groupe organique divalent ayant le groupe "-N(D)-" dans sa molécule (où D représente un groupe protecteur dissocié par chauffage et remplacé par un atome d'hydrogène). Dans les formules (d0) et (dD), la pluralité de R représentent chacun indépendamment un atome d'hydrogène ou un groupe organique univalent.) (YB représente un groupe organique divalent qui satisfait les conditions (1) et (2), et R est synonyme de R dans la formule (d0.)　Condition (1) : N'ayant pas de structure contenant un atome d'azote choisie dans le groupe constitué par les hétérocycles comprenant un atome d'azote et des groupes amino secondaires ou supérieurs (à l'exclusion des groupes amino dérivés du groupe "-N(D')-" (où D' représente un groupe protecteur dissocié par chauffage et remplacé par un atome d'hydrogène)).　Condition (2) : N'ayant pas de groupe à chaîne latérale en C6 ou plus dans la molécule de celui-ci. (Dans la formule (En), a est un nombre entier de 2 à 4, Ra est un groupe organique de valence a, et des sites de liaison avec N sont des atomes de carbone aliphatiques.)
PCT/JP2022/019330 2021-05-06 2022-04-28 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2022234820A1 (fr)

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WO2019065646A1 (fr) * 2017-09-26 2019-04-04 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage de cristaux liquides les mettant en oeuvre
WO2020158818A1 (fr) * 2019-01-30 2020-08-06 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides l'utilisant
WO2020175561A1 (fr) * 2019-02-27 2020-09-03 日産化学株式会社 Agent de traitement d'alignement de cristaux liquides, film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides

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US5731404A (en) 1995-11-01 1998-03-24 E. I. Du Pont De Nemours And Company Polyimide film from pyromellitic dianhydride and a bis(4-aminophenoxy) aromatic compound as an alignment layer for liquid crystal displays
JP3169062B2 (ja) 1996-07-11 2001-05-21 日産化学工業株式会社 液晶セル用配向処理剤
TW556029B (en) 2000-10-16 2003-10-01 Nissan Chemical Ind Ltd Aligning agent for liquid crystal for in-plane switching, liquid-crystal alignment film, and liquid-crystal display element
JPWO2014010402A1 (ja) 2012-07-11 2016-06-20 日産化学工業株式会社 ポリアミック酸エステルを含有する液晶配向剤、液晶配向膜、及び液晶表示素子
JP7298156B2 (ja) 2016-12-28 2023-06-27 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
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

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WO2019065646A1 (fr) * 2017-09-26 2019-04-04 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage de cristaux liquides les mettant en oeuvre
WO2020158818A1 (fr) * 2019-01-30 2020-08-06 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides l'utilisant
WO2020175561A1 (fr) * 2019-02-27 2020-09-03 日産化学株式会社 Agent de traitement d'alignement de cristaux liquides, film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides

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