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WO2020085450A1 - Agent d'alignment de cristaux liquides, film d'alignment de cristaux liquides et élément d'affichage à cristaux liquides - Google Patents

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

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Publication number
WO2020085450A1
WO2020085450A1 PCT/JP2019/041769 JP2019041769W WO2020085450A1 WO 2020085450 A1 WO2020085450 A1 WO 2020085450A1 JP 2019041769 W JP2019041769 W JP 2019041769W WO 2020085450 A1 WO2020085450 A1 WO 2020085450A1
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Prior art keywords
group
liquid crystal
formula
polymer
carbon atoms
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PCT/JP2019/041769
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English (en)
Japanese (ja)
Inventor
直史 長谷川
尚宏 野田
永井　健太郎
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to CN201980070307.XA priority Critical patent/CN112888996B/zh
Priority to JP2020552602A priority patent/JP7375766B2/ja
Priority to KR1020217013120A priority patent/KR102845022B1/ko
Publication of WO2020085450A1 publication Critical patent/WO2020085450A1/fr
Anticipated expiration legal-status Critical
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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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device.
  • Liquid crystal display elements are widely used in TVs, large monitors, personal computers, mobile phones, smartphones, etc. In recent years, liquid crystal display elements have been increasingly used under high temperature and high humidity, such as car navigation systems and meters installed in vehicles, and display parts of industrial equipment and measuring equipment installed outdoors.
  • the vertical alignment type liquid crystal display element has been widely used in recent years because of its wide viewing angle, fast response speed and large contrast.
  • a photopolymerizable compound is added to the liquid crystal composition in advance and used together with a liquid crystal alignment film such as a polyimide system, and the film is irradiated with ultraviolet rays while applying a voltage to the liquid crystal cell to tilt the film at a tilt angle.
  • a liquid crystal alignment film such as a polyimide system
  • a composition for a liquid crystal display device for forming at least one of a liquid crystal layer and a liquid crystal alignment layer of a liquid crystal display device which has a chain transfer function. It has been proposed to include a compound having a structure capable of expressing (see Patent Document 2).
  • a sulfide compound disclosed as a compound having a structure capable of exhibiting a chain transfer function to be contained in a composition for a liquid crystal display device has a strong odor and has a problem in handling, so that it is industrially mass-produced. There was a problem that it could not be manufactured.
  • Benzyl isopropenyl ether which is a vinyl ether disclosed as a compound having a structure capable of expressing a chain transfer function, is a low molecular weight component and an unreacted component remains in the liquid crystal alignment film, and It may cause display failure.
  • the response speed of vertical alignment type liquid crystal display elements has been required to be further increased, and the photopolymerizable compound reacts efficiently and the ability to impart a tilt angle. Is required.
  • a liquid crystal aligning agent comprising a polymer having a side chain represented by the following formula (1) and a side chain represented by the following formula (2).
  • R 1c and R 2c each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • Y c represents a single bond or —CO—.
  • Ar 1 represents a phenylene group or a naphthylene group.
  • T 1c and T 2c are each independently a single bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, Represents —N (CH 3 ) —, —CON (CH 3 ) —, or —N (CH 3 ) CO—, wherein A c represents a single bond or a C 1-20 optionally substituted by a fluorine atom.
  • (Q represents a group selected from the following formulas (q-1) to (q-4)
  • R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 3 represents —CH 2 —, —NR—, Represents —O— or —S—, and * represents a bond to an adjacent carbon atom.
  • R 1r and R 2r each independently represent an alkyl group or an alkoxy group having 1 to 10 carbon atoms, Represents a benzyl group or a phenethyl group
  • Ar 2 represents a divalent aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, which may be substituted with an organic group
  • a hydrogen atom is a halogen atom.
  • T 1r and T 2r are each independently a single bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O. -, -N (CH 3 )-, -CON (CH 3 )-, Or -N (CH 3) .
  • a representative of CO- r is a single bond, an alkylene group having a fluorine atom is 1 carbon atoms which may be ⁇ 20 substituted with a divalent aromatic ring group having 6 to 12 carbon atoms
  • a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention has a wide viewing angle, a fast response speed, and a large contrast.
  • the liquid crystal aligning agent of the present invention includes a side chain represented by the following formula (1) (hereinafter, also referred to as specific side chain 1) and a side chain represented by the following formula (2) (hereinafter, specific side chain 2). Also referred to as a).
  • R 1c , R 2c , Y c , Ar 1 , T 1c , T 2c , A c and n in the above formula (1) are as described above.
  • R 1c and R 2c each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 1c and R 2c each independently have 1 to 10 carbon atoms. It preferably represents an alkyl group.
  • alkyl group having 1 to 10 carbon atoms examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl. , T-octyl, nonyl, isononyl, decyl or isodecyl are preferred.
  • Ar 1 is preferably a phenylene group or a biphenylene group.
  • T 1c and T 2c are preferably each independently a single bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, or —CH 2 O—.
  • a c is a single bond, an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, a divalent aromatic ring group having 6 to 12 carbon atoms, or a divalent aliphatic group having 3 to 8 carbon atoms. Cyclic groups are preferred. Further, n is preferably 1 to 2.
  • Preferred structures of —Ar 1 — (Y c —CHR 1c R 2c ) n in formula (1) include the following (ch-1) to (ch-6). (R 1c and R 2c have the same meaning as in the above formula (1).)
  • R 1r, R 2r, Ar 2 , T 1r, T 2r, A r are as above.
  • Ar 2 is preferably a phenylene group or a biphenylene group from the viewpoint of high photoreactivity.
  • T 1r and T 2r are preferably each independently a single bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH— or —CH 2 O—.
  • a r is a single bond, an alkylene group having fluorine atom and 1 carbon atoms which may be substituted with 20, divalent cycloaliphatic divalent aromatic ring group, or a C 3-8 having 6 to 12 carbon atoms Cyclic groups are preferred.
  • the R 1c and R 2c of the above formula (1), the R 1r of the above formula (2), and the alkyl group having 1 to 10 carbon atoms which constitutes R 2r may be linear or branched. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl.
  • the C 1 to C 20 alkylene group constituting A c of the above formula (1) and A r of the above formula (2) may be a straight chain, a branched chain or a cyclic chain.
  • Specific examples include methylene group, ethylene group, n-propylene group, isopropylene group, cyclopropylene group, 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, 1,1-dimethyl-n-propylene group.
  • Examples of the aromatic ring group having 6 to 12 carbon atoms which constitutes A c of the above formula (1) and A r of the above formula (2) include a benzene ring, a biphenylene ring, and a naphthalene ring.
  • Examples of the alicyclic group having 3 to 8 carbon atoms which composes A c in the above formula (1) and A r in the above formula (2) include a cyclopentane ring and a cyclohexane ring.
  • Preferred structures of —Ar 2 —CO—CR 1r R 2r Q in formula (1) include formulas (ra-1) to (ra-6). Among them, (ra-2) or (ra-3) is preferable from the viewpoint of reliability of the obtained liquid crystal display element.
  • the polymer contained in the liquid crystal aligning agent of the present invention is, in addition to the specific side chain 1 and the specific side chain 2, a side chain represented by the following formula (3) (hereinafter also referred to as a specific side chain 3). ) May be included.
  • R 1 is — (CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CON (CH 3 ) —, —NH—, —O—, —CH 2 O-, -CH 2 OCO-, -COO-, -OCO-, or-(CH 2 ) a1- A 1- (CH 2 ) a 2 -A 2- represents A 1 is an oxygen atom or -COO.
  • R 2 , R 3 and R 4 each independently represent a phenylene group, a fluorine-containing phenylene group or a cycloalkylene group.
  • R 5 is a linear alkyl group having 2 to 24 carbon atoms, a fluorine-containing alkyl group having 2 to 24 carbon atoms, an alkoxy group having 2 to 24 carbon atoms, an alkoxyalkyl group having 2 to 24 carbon atoms, or a steroid skeleton. Represents a structure having.
  • R 5 is a linear alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group having 2 to 24 carbon atoms, 1 + m + n ⁇ 1 is satisfied, and when R 5 is a structure having a steroid skeleton, 1, m and n represent 0, R 1 is — (CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CON (CH 3 ) —, —NH—, It represents -O-, -CH 2 O-, -CH 2 OCO-, -COO-, or -OCO-.
  • Specific examples of the structure having a steroid skeleton include a structure having a skeleton represented by the following formula (st).
  • Preferred structures of the specific side chain 3 include the following formulas (S1-x1) to (S1-x7) and formula (S3-x).
  • R 1 represents a linear alkyl group having 2 to 24 carbon atoms, an alkoxy group having 2 to 24 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms.
  • X p is — (CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CON (CH 3 ) —, —NH—, —O—, —CH 2 Represents O-, -CH 2 OCO-, -COO-, or -OCO-.
  • a 1 is an oxygen atom or —COO- * (however, a bond marked with * bonds with (CH 2 ) a2 ),
  • a 2 is an oxygen atom or * —COO— (however, a bond marked with *)
  • a hand is bonded to (CH 2 ) a2 ),
  • a 1 and a 3 are each independently an integer of 0 or 1
  • a 2 is an integer of 1 to 10 and Cy is 1,4- Represents a cyclohexylene group or a 1,4-phenylene group.
  • X represents the formula (X1) or (X2).
  • Col represents at least one selected from the group consisting of the above formulas (Col1) to (Col4).
  • G represents the above formula (G1) or (G2). * Represents a position to be bonded to another group.
  • More preferable structures of the formula (S3-x) include the following formulas (S3-1) to (S3-6).
  • the specific polymer contained in the liquid crystal aligning agent of the present invention may be a polymer containing a unit having a specific side chain 1 and a unit having a specific side chain 2 (hereinafter, also referred to as a specific copolymer) or may be a specific polymer. It may be a mixture (hereinafter, also referred to as a polymer blend) containing a polymer having a side chain 1 and a polymer having a specific side chain 2.
  • the specific copolymer may have a unit having a specific side chain 3 in addition to a unit having a specific side chain 1 and a unit having a specific side chain 2.
  • the polymer blend has a polymer having a specific side chain 1 and a polymer having a specific side chain 2 and contains a unit having a specific side chain 3 in any of the polymers, or has a specific side chain. It may be a mixture containing a polymer having 1, a polymer having a specific side chain 2 and a polymer having a specific side chain 3.
  • the specific copolymer may be a diamine having a specific side chain 1 and a polymer having a specific side chain 2, but a group consisting of polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, and poly (meth) acrylate. It is preferably a polymer having a skeleton selected from Among them, it is a polyimide formed by a polycondensation reaction of a diamine component containing a diamine having a specific side chain 1 and a diamine having a specific side chain 2, and / or an imidized polyamic acid. Is preferred.
  • the content ratio of the unit having the specific side chain 1 to the unit having the specific side chain 2 in the specific copolymer is preferably 5/95 to 95 / in terms of molar ratio (specific side chain 1 / specific side chain 2). 5, more preferably 10/90 to 90/10.
  • the specific copolymer contains a unit having a specific side chain 3
  • the content ratio thereof is a molar ratio (specific side chain 3 / specific side chain 3 / unit of the unit having the specific side chain 1 and the unit having the specific side chain 2).
  • (Specific side chain 1 + specific side chain 2)) is preferably 10/90 to 90/10, more preferably 10/90 to 80/20.
  • the polymer blend is a polymer composed of a polyamic acid formed by a polycondensation reaction of a diamine component containing a diamine having a specific side chain 1 and a tetracarboxylic acid component, and / or a polyimide obtained by imidizing the polyamic acid. And a mixture of a diamine component containing a diamine having a specific side chain 2, a polyamic acid formed by a polycondensation reaction with a tetracarboxylic acid component, and / or a polymer composed of a polyimide imidized with the polyamic acid. Is preferred.
  • the content ratio of the polymer having the specific side chain 1 and the polymer having the specific side chain 2 in the polymer blend is a weight ratio (polymer having the specific side chain 1 / polymer having the specific side chain 2). It is preferably 10/90 to 90/10, more preferably 20/80 to 80/20. By setting such a ratio within the above range, the light irradiation amount at the time of imparting the tilt is reduced.
  • the specific polymer of the present invention is, as a preferable diamine having a specific side chain 1 used as a part of the raw material for obtaining the specific copolymer or the polymer blend, represented by the following formula (d-1) ).
  • formula (d-1) the meanings of R 1c , R 2c , Y c , Ar 1 , T 1c , T 2c , A c , and n are as defined in the above formula (1) and their preferred ones. It is the same including. It is particularly preferable that R 1c and R 2c are both methyl from the viewpoint of availability of raw materials.
  • Preferred specific examples of the diamine represented by the formula (d-1) include the following formulas (1-a) to (1-j).
  • a preferable diamine having a specific side chain 2 used as a part of the raw material thereof is represented by the following formula (d-2).
  • the diamine represented by In the above formula (d-2), R 1r , R 2r, Y r, meaning of Ar 2, T 1r, T 2r, and A r is included as in the formula (2), and their preferred Is the same.
  • Preferred specific examples of the diamine represented by the formula (d-2) include the following formulas (2-a) to (2-d).
  • the specific polymer of the present invention further has a side chain represented by the following formula (3) in addition to the side chain represented by the formula (1) and the side chain represented by the formula (2).
  • the diamine component is represented by the following formula (d-3) in addition to the diamine represented by the formula (d-1) and the diamine represented by the formula (d-2). Diamines are used.
  • l, m, n, and R 1 to R 5 are the same as those in the above formula (3) including preferable ones.
  • z represents an integer of 1 to 2
  • Y 3 represents a structure represented by the following formulas (Ar 3-1 ) to (Ar 3-2 ).
  • a 3a represents a divalent organic group having a single bond or an aromatic group.
  • a 3b represents a trivalent group having an aromatic group.
  • * 1 represents a bonding position to -R 1- (R 2 ) l- (R 3 ) m- (R 4 ) nR 5
  • * 2 represents a bonding position to -NH 2 .
  • Examples of the divalent organic group having an aromatic group for A 3a include a structure represented by the following formula (R1).
  • X 1 is a single bond, —O—, —C (CH 3 ) 2 —, —NH—, —CO—, —NHCO—, —COO—, — (CH 2 ) m —, —SO 2 -, --O-(CH 2 ) m --O--, --OC (CH 3 ) 2- , --CO-(CH 2 ) m- , --NH-(CH 2 ) m- , --SO 2- ( CH 2 ) m ⁇ , —CONH— (CH 2 ) m —, —CONH— (CH 2 ) m —NHCO—, —COO— (CH 2 ) m —OCO— and the like can be mentioned.
  • Q 1 examples include groups in which two hydrogen atoms have been removed from an aromatic hydrocarbon having 6 to 20 carbon atoms such as a benzene ring and a naphthyl ring.
  • m is an integer of 1 to 8.
  • * 2 represents a bonding position to —NH 2
  • * 3 represents a bonding position to a benzene ring.
  • Examples of the trivalent organic group having an aromatic group in A3b include a structure represented by the following formula (R2).
  • X 2 has the same meaning as X 1 in formula (R1)
  • Q 2 is a group obtained by removing three hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms such as a benzene ring and a naphthyl ring.
  • * 1 represents a bonding position to -R 1- (R 2 ) l- (R 3 ) m- (R 4 ) n -R 5
  • * 2 represents a bonding position to -NH 2 .
  • 3 represents the bonding position to the benzene ring.
  • diamine represented by the above formula (d-3) include diamines represented by the following formulas (V-1) to (V-13).
  • X v1 to X v4 and X p1 to X p8 are each independently-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, It represents —CON (CH 3 ) —, —NH—, —O—, —CH 2 O—, —CH 2 OCO—, —COO—, or —OCO—.
  • X V6 to X V7 and X s1 to X s4 each independently represent —O—, —COO— or —OCO—.
  • X a to X f represent a single bond, —O—, —NH—, or —O— (CH 2 ) m —O—.
  • R v1 to R v4 and R 1a to R 1h each independently represent a linear alkyl group having 2 to 24 carbon atoms, an alkoxy group having 2 to 24 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms.
  • m represents an integer of 1 to 8.
  • the diamine component for obtaining the specific polymer is represented by the diamine represented by the formula (d-1), the diamine represented by the formula (d-2), and the diamine represented by the formula (d-3).
  • diamine other diamine (hereinafter, also referred to as other diamine) may be used in combination.
  • diamine described in paragraph [0169] of International Publication WO2015 / 046374, the diamine having a carboxyl group or a hydroxyl group described in paragraphs [0171] to [0172], and described in paragraphs [0173] to [0188].
  • a diamine having a nitrogen-containing heterocycle a diamine having a nitrogen-containing structure described in paragraph [0050] of JP-A-2016-218149, a diamine having a pyrrole structure described in International Publication WO2017 / 126627, preferably the following formula: Diamine having a structure represented by (pr) (R 1 represents a hydrogen atom, a hydrogen, fluorine atom, cyano group, hydroxy group, a methyl group, R 2 each independently represents a single bond, or * 1-R 3 -Ph- * 2 , R 3 Is a single bond, a divalent organic group selected from -O-, -COO-, -OCO-,-(CH 2 ) l-, -O (CH 2 ) m O-, -CONH-, and -NHCO- (1 and m are integers from 1 to 5), * 1 represents a position to be bonded to the benzene ring in the formula (pr), and * 2 is
  • Ph represents a phenylene group, n represents 1 to 3
  • Diamine having a pyrrole structure described in International Publication WO2018 / 062197 preferably diamine having a structure represented by the following formula (pn):
  • R 1 and R 2 each represent a hydrogen atom or a methyl group, R 3 independently represents a single bond or * 1-R 4 -Ph- * 2, R 4 represents a single bond, —O—, —COO.
  • a diamine having a thiophene or furan structure described in International Publication WO2018 / 092759 preferably a diamine having a structure represented by the following formula (sf):
  • Y 1 represents a sulfur atom or an oxygen atom
  • R 2 independently represents a single bond or * 1-R 5 —Ph- * 2
  • R 5 represents a single bond, —O—, —COO—
  • * 1 represents a position bonded to the benzene ring in the formula (pn)
  • * 2 represents a position bonded to the amino group in the formula (pn)
  • Ph represents a phenylene group
  • n represents 1 Represents ⁇ 3.
  • the functional group capable of forming a covalent bond upon irradiation with light also referred to as a photoreactive group
  • a photoreactive group for the purpose of increasing the response speed of a liquid crystal when used as a diamine containing an organosiloxane and a liquid crystal display device.
  • diamine having a benzophenone skeleton examples include 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone and 4,4′-bis [4- (4-amino- ⁇ , ⁇ -Dimethylbenzyl) phenoxy] benzophenone, diamines represented by the following formulas (z-1) to (z-4), and the like can be given.
  • examples of the above-mentioned other diamines include those having a structure of the following formula (11).
  • A is a single bond or a divalent organic group
  • R 1 , R 2 and R 3 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • A is a single bond or a divalent organic group.
  • the structure of the divalent organic group is represented by, for example, the following formula (12).
  • B is a divalent linking group
  • R 5 and R 6 are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
  • R 5 and R 6 are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
  • R 7 , R 8 , R 9 , R 10 and R 11 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • the monovalent hydrocarbon group is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group or a decyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group.
  • bicycloalkyl group such as bicyclohexyl group
  • alkenyl group such as vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, hexenyl group
  • aryl group such as phenyl group, xylyl group, biphenyl group, naphthyl group
  • An aralkyl group such as a benzyl group, a phenylethyl group and a phenylcyclohexyl group.
  • some or all of the hydrogen atoms of these monovalent hydrocarbon groups are halogen atoms, hydroxyl groups, thiol groups, carboxyl groups, thioester groups, amide groups, alkyl groups, cycloalkyl groups, bicycloalkyl groups, alkenyl groups. It may be substituted with an aryl group, an aralkyl group or the like.
  • R 7 , R 8 , R 9 , R 10 , and R 11 have a bulky structure such as an aromatic ring or an alicyclic structure, the solubility of the polymer may be reduced, and therefore, methyl group, ethyl group, or ethyl group may be used.
  • a group, an alkyl group such as a propyl group and a butyl group, or a hydrogen atom is preferable, and a hydrogen atom is more preferable.
  • R 1 , R 2 and R 3 in the formula (11) are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
  • the monovalent organic group include a monovalent hydrocarbon group, a hydroxyl group, a thiol group, an ester group, a carboxyl group, a thioester group, an amide group, an organooxy group, an organosilyl group, an organothio group and an acyl group.
  • a monovalent hydrocarbon group is preferable from the viewpoint of high resistance to high temperature and high humidity.
  • the monovalent hydrocarbon group examples include the examples of the above monovalent hydrocarbon groups, and some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be the same as those described above for R 7 and R 8.
  • substitutable groups exemplified by R 9 , R 9 and R 10 they may be substituted with groups such as a pyrrole group, an imidazole group and a pyrazole group.
  • R 1 and R 2 are preferably an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or a hydrogen atom, and more preferably a hydrogen atom.
  • R 3 is preferably an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or a hydrogen atom, and more preferably a hydrogen atom.
  • N1, n2, n3, n4, n5 and n6 each independently represent an integer of 1 to 10.
  • the diamine having the structure represented by the above formula (11) is preferably a diamine represented by the following formula (M1) from the viewpoint of high resistance to high temperature and high humidity of the liquid crystal alignment film.
  • Z 1 is a substituent having a structure represented by the above formula (11), and n is an integer of 1 to 4.
  • Y 1 is a (n + 2) -valent organic group having 5 to 40 carbon atoms.
  • the (n + 2) -valent organic group having 5 to 40 carbon atoms in Y 1 is, for example, a hydrocarbon group such as a chain hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, or a hydrocarbon group in the hydrocarbon group.
  • Groups having a functional group such as, for example, a (n + 2) -valent heterocycle, and the like.
  • each of these groups may have a substituent such as a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group or the like.
  • a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom
  • the (n + 2) -valent chain hydrocarbon group is a group obtained by removing (n + 1) hydrogen atoms from the monovalent alkyl group for R 7 , R 8 , R 9 , R 10 and R 11 . And a group obtained by removing (n + 1) hydrogen atoms from the monovalent alkenyl group.
  • the (n + 2) -valent alicyclic hydrocarbon group is a group obtained by removing (n + 1) hydrogen atoms from the monovalent cycloalkyl group in R 7 , R 8 , R 9 , R 10 and R 11 . Examples thereof include a group obtained by removing (n + 1) hydrogen atoms from the monovalent bicycloalkyl group.
  • the (n + 2) -valent aromatic hydrocarbon group is a group obtained by removing (n + 1) hydrogen atoms from the monovalent aryl group in R 7 , R 8 , R 9 , R 10 and R 11 , and 1 above. Examples thereof include a group obtained by removing (n + 1) hydrogen atoms from a valent aralkyl group.
  • divalent heterocycle a divalent pyrrole ring, a divalent thiophene ring, a divalent furan ring, a 5-membered heterocycle such as a pyrrolidinylene group, a piperidinylene group, a piperazinylene group, a pyridinylene group, a pyridazinylene group, Examples include 6-membered heterocycles such as pyrimidinylene groups.
  • the steroid skeleton has a skeleton represented by the following formula (st) in which three 6-membered rings and one 5-membered ring are bonded.
  • Y 1 is preferably an aromatic ring-containing (n + 2) -valent organic group having 5 to 40 carbon atoms, specifically, having 5 to 40 carbon atoms.
  • a divalent heterocycle, a group having a functional group such as a divalent group having a steroid skeleton introduced therein, or an (n + 2) -valent group having an aromatic heterocycle is preferable.
  • the aromatic heterocycle is preferably a nitrogen-containing aromatic heterocycle having a nitrogen atom in the ring portion.
  • Specific examples thereof include a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring and a triazine ring, and a pyridine ring, a pyrimidine ring or a triazine ring is more preferable.
  • Y 1 is preferably an (n + 2) -valent aromatic hydrocarbon group having 5 to 40 carbon atoms, which has a structure represented by the following formula (Ar 1 ). It is preferably a group having a (n + 2) valence of 5 to 40.
  • a 1 represents a single bond or a divalent organic group having an aromatic ring.
  • formula (M1) More preferable specific examples of the formula (M1) include the following formulas (M1-1) to (M1-13).
  • Z 1 is a structure represented by the above formula (11), c is an integer of 1 to 4, d and e are integers of 1 to 2, and n is an integer of 2 to 6.
  • the diamine having the structure represented by the formula (11) is at least one selected from the group consisting of diamines represented by the following formulas (M-1) to (M-6). Is preferred.
  • N1, n2, n3, n4, n5 and n6 each independently represent an integer of 1 to 10.
  • Examples of the above-mentioned other diamines also include diamines having a structure represented by the following formula (21).
  • R 1 represents hydrogen or a monovalent organic group
  • * represents a site bonded to another group.
  • Examples of the diamine having the oxazoline skeleton represented by the above formula (21) include diamines selected from the group represented by the following formulas (21-1) to (21-3).
  • R 1 is the same as in formula (21) above.
  • R 2 is a single bond, —O—, —COO—, —OCO—, — (CH 2 ) 1 —, —O (CH 2 ) 1 O—, —CONR 11 —, —NR 11 CO— and —NR 11
  • W 1 is a structure selected from the following group (3-1)
  • W 2 is selected from the following group (3-2)
  • W 3 represents a structure selected from the following group (3-3)
  • W 4 represents a structure selected from the following group (3-4).
  • R 11 represents hydrogen or a monovalent organic group
  • l represents an integer of 1 to 12
  • a represents an integer of 0 or 1.
  • * 1 represents a site that binds to an amino group in formulas (21-1) to (21-3), and * 2 represents a site that binds to an oxazoline ring.
  • * 1 represents a site that binds to an amino group in formulas (21-1) to (21-3)
  • * 3 represents a site that binds to R 2 .
  • * 3 represents a site that binds to R 2 .
  • * 2 represents a site that binds to the oxazoline ring.
  • X represents a substituent, hydrogen atom; halogen atom; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group; halogenated alkyl group having 1 to 6 carbon atoms such as trifluoromethyl group; dimethyl methoxy group, an alkoxy group having 1 to 6 carbon atoms such as an ethoxy group; a substituted amino group such as an amino group represents an amide group such as NHCOCH 3 or NHCOCH 2 CH 3, NHCOOtBu.
  • tBu represents a tertiary butyl group.
  • R 1 is the same as that in the above formula (21), and a hydrogen atom, a methyl group (Me) or an ethyl group (Et) is particularly preferable.
  • R 11 is the same as that in the above formula (21), and a hydrogen atom, a Me group or an Et group is particularly preferable.
  • n represents an integer of 1 to 6
  • m represents an integer of 1 to 12.
  • the above-mentioned other diamines may be used in one kind or in two kinds depending on the solubility of the specific polymer in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal aligning property in the case of a liquid crystal aligning film, the voltage holding ratio, the accumulated charge and the like. It is also possible to use a mixture of more than one type.
  • tetracarboxylic acid component for obtaining the specific polymer of the present invention it is preferable to use tetracarboxylic dianhydrides represented by the following formulas [4] to [6].
  • tetracarboxylic acid dianhydrides represented by the formulas [4] to [6] not only the tetracarboxylic acid dianhydrides represented by the formulas [4] to [6], but also tetracarboxylic acid derivatives thereof, such as tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl Ester dihalides can also be used.
  • Z 1 represents at least one structure selected from the following [4a] to [4k].
  • j and k are each independently an integer of 0 or 1.
  • x and y are each independently a single bond, carbonyl, ester, phenylene, sulfonyl or amide group.
  • Z 1 to Z 4 represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, and may be the same or different.
  • Specific preferred examples of the formula [4a] include the structures [4a-1] and [4a-2] below.
  • Z 5 and Z 6 represent a hydrogen atom or a methyl group, and may be the same or different.
  • Z in the formula [4] from the viewpoint of easiness of synthesis and easiness of polymerization reactivity when producing a polymer, formula [4a], formula [4c] to formula [4g] or formula [4k] ]
  • the tetracarboxylic dianhydride and the tetracarboxylic acid derivative thereof having a structure represented by the following are preferred. More preferred are those having a structure represented by Formula [4a] or Formula [4e] to Formula [4g].
  • tetracarboxylic acid dianhydrides having the structure represented by [4a], formula [4e] or formula [4f], and tetracarboxylic acid derivatives thereof. More preferred specific examples include tetracarboxylic acid dianhydrides having the structures represented by [4a-1], formula [4a-2], formula [4e], and formula [4f], and tetracarboxylic acid derivatives thereof. .
  • the tetracarboxylic acid component represented by the formula [4] is preferably 1 to 100 mol% in 100 mol% of all the tetracarboxylic acid components used. Among them, 5 to 95 mol% is preferable, and 20 to 80 mol% is more preferable.
  • the tetracarboxylic acid component may be selected from one type depending on the solubility of the specific polymer in the solvent, the coating property of the liquid crystal aligning agent, the liquid crystal aligning property of the liquid crystal aligning film, the voltage holding ratio, the accumulated charge and the like. Alternatively, two or more kinds may be mixed and used.
  • the tetracarboxylic acid component other than the specific tetracarboxylic acid component may be used in the polyimide polymer of the specific polymer.
  • examples of the other tetracarboxylic acid component include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester and tetracarboxylic acid dialkyl ester dihalide shown below.
  • 1,2,5,6-naphthalene tetracarboxylic acid 1,4,5,8-naphthalene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid
  • Bis (3,4-dicarboxyphenyl) methane 2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) ) Diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,4,9,10-perylenetetracarboxylic acid or 1,3- Examples thereof include diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.
  • the polyimide precursor which is the specific polymer in the present invention, is obtained by reacting a diamine component and a tetracarboxylic acid component.
  • a method of polycondensing a tetracarboxylic dianhydride and a primary or secondary diamine to obtain a polyamic acid a dehydration polycondensation reaction of a tetracarboxylic acid and a primary or secondary diamine
  • a method for obtaining a polyamic acid or a method for obtaining a polyamic acid by polycondensing a tetracarboxylic acid dihalide and a primary or secondary diamine is used.
  • the specific polymer can be obtained by reacting the above-mentioned tetracarboxylic acid component and diamine component together with a molecular weight modifier, if necessary.
  • a molecular weight modifier examples include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamines such as aniline, cyclohexylamine and n-butylamine, monoisocyanates such as phenyl isocyanate and naphthyl isocyanate.
  • the proportion of the molecular weight modifier used is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the total of the tetracarboxylic acid component and the diamine component used.
  • a method of polycondensing a tetracarboxylic acid in which a carboxylic acid group is dialkyl esterified with a primary or secondary diamine, and a tetracarboxylic acid dihalide in which a carboxylic acid group is dialkyl esterified A method of polycondensing a secondary or secondary diamine or a method of converting a carboxyl group of a polyamic acid into an ester is used.
  • the reaction between the diamine component and the tetracarboxylic acid component is usually carried out in the solvent of the diamine component and the tetracarboxylic acid component.
  • the solvent used at that time is not particularly limited as long as it can dissolve the generated polyimide precursor. Specific examples of the solvent used in the reaction are shown below, but the solvent is not limited to these examples. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-2-imidazolidinone Is mentioned.
  • methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formulas [D-1] to [D-3] is used.
  • the indicated solvents can be used.
  • D 1 represents an alkylene group having 1 to 3 carbon atoms
  • D 2 represents an alkylene group having 1 to 3 carbon atoms
  • D-3 represents an alkylene group having 1 to 4 carbon atoms.
  • solvents may be used alone or in combination. Further, even a solvent that does not dissolve the polyimide precursor may be used as a mixture with the solvent as long as the generated polyimide precursor does not precipitate. Further, since water in the solvent inhibits the polymerization reaction and causes hydrolysis of the generated polyimide precursor, it is preferable to use dehydrated and dried solvent.
  • the reaction can be performed at any concentration, but if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and the concentration is high. If too much, the viscosity of the reaction solution becomes too high, and it becomes difficult to uniformly stir. Therefore, the amount is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the reaction can be performed at a high concentration in the initial stage, and then a solvent can be added.
  • the ratio of the total number of moles of the diamine component and the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyimide precursor produced.
  • the polyimide of the present invention is a polyimide obtained by ring-closing the above-mentioned polyimide precursor, and in this polyimide, the ring-closing rate of the amic acid group (also referred to as imidization rate) does not necessarily have to be 100%, and the application and It can be arbitrarily adjusted according to the purpose.
  • a method of ring-closing the polyamic acid or the polyamic acid alkyl ester which is the polyimide precursor is used.
  • 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 is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to remove water generated by the imidization reaction outside the system.
  • Catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring the mixture at -20 ° C to 250 ° C, preferably 0 ° C to 180 ° C. it can.
  • the amount of basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, of the amic acid group, and the amount of acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times, of the amic acid groups. Double.
  • Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferable because purification after the reaction is easy.
  • the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.
  • the reaction solution may be poured into a solvent to cause precipitation.
  • the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
  • the polymer precipitated by pouring it into a solvent can be collected by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
  • the operation of re-dissolving the polymer recovered by precipitation and re-precipitating and recovering it in a solvent is repeated 2 to 10 times, impurities in the polymer can be reduced.
  • the solvent in this case include 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 weight average molecular weight (Mw) in terms of polyethylene oxide measured by gel permeation chromatography (GPC) of the polyimide precursor and the polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300, It is 000. Further, the molecular weight distribution (Mw / Mn) represented by the ratio of Mw and the number average molecular weight (Mn) in terms of polyethylene oxide measured by GPC is preferably 15 or less, more preferably 10 or less. Within such a molecular weight range, good alignment of the liquid crystal display device can be ensured.
  • the liquid crystal alignment agent of the present invention is a coating solution for forming a liquid crystal alignment film, and is a coating solution for forming a liquid crystal alignment film containing a specific polymer and a solvent.
  • a specific polymer any polyimide-based polymer such as polyamic acid, polyamic acid alkyl ester and polyimide may be used.
  • All the polymers in the liquid crystal aligning agent of the present invention may be all specific polymers or may be mixed with other polymers. Examples of the other polymer include a polyimide-based polymer having no specific side chain 1, specific side chain 2, and specific side chain 3.
  • a cellulose-based polymer an acrylic polymer, a methacrylic polymer, polystyrene, a polyamide or a polysiloxane may be used.
  • the content of the other polymer other than that is preferably 5 to 90 parts by mass, and 10 to 60 parts by mass with respect to 100 parts by mass of the polymer obtained by combining the specific polymer and the other polymer. Is more preferable.
  • the content of the solvent in the liquid crystal aligning agent of the present invention is preferably 70 to 99.9% by mass. This content can be appropriately changed depending on the coating method of the liquid crystal aligning agent and the target film thickness of the liquid crystal aligning film.
  • the solvent used for the liquid crystal aligning agent of the present invention is not particularly limited as long as it is a solvent that dissolves the polymer (also referred to as a good solvent). Specific examples of the good solvent are shown below, but the invention is not limited to these examples.
  • N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, dimethylsulfoxide, ⁇ -butyrolactone, ⁇ -valero Lactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy- 4-methyl-2-pentanone and the like can be mentioned.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, 1,3-dimethyl-2-imidazolidinone, 3- Methoxy-N, N-dimethylpropanamide or 3-butoxy-N, N-dimethylpropanamide is preferred.
  • the solubility of the polymer in the solvent is high, it is preferable to use the solvents represented by the above formulas [D-1] to [D-3].
  • the good solvent in the liquid crystal aligning agent of the present invention is preferably 5 to 99 mass% of the whole solvent contained in the liquid crystal aligning agent. Above all, 10 to 90 mass% is preferable.
  • a solvent also referred to as a poor solvent
  • a solvent that improves the coating property and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied
  • Specific examples of the poor solvent are shown below, but the invention is not limited to these examples.
  • ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol , 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etanji 1,2-propanediol, 1,3-propan
  • 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl -2-Pentanone, propylene glycol diacetate, dipropylene glycol monomethyl ether or propylene carbonate are preferred.
  • the amount of these poor solvents is preferably 1 to 95% by mass based on the whole solvent contained in the liquid crystal aligning agent. Above all, 10 to 90 mass% is preferable.
  • a compound that improves the film thickness uniformity and the surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied can be used.
  • the compound that improves the film thickness uniformity and the surface smoothness of the liquid crystal alignment film include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant.
  • Ftop EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafac F171, F173, R-30 (above manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (above) , Manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (all manufactured by Asahi Glass Co., Ltd.).
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent.
  • the liquid crystal aligning agent of the present invention is described in paragraphs [0194] to [0200] of International Publication WO2011 / 132751 as a compound that promotes charge transfer in a liquid crystal alignment film to accelerate charge loss of the device. It is also possible to add a nitrogen-containing heterocyclic amine represented by the formulas [M1] to [M156], more preferably a nitrogen-containing heterocyclic amine represented by the following formulas (B-1) to (B-40). it can.
  • This amine may be added directly to the liquid crystal aligning agent, but it is preferable to add it after forming a solution having a concentration of 0.1 to 10%, preferably 1 to 7% with a suitable solvent.
  • the solvent is not particularly limited as long as it is a solvent that dissolves the above-mentioned polyimide polymer.
  • the liquid crystal aligning agent of the present invention includes a crosslinkable compound that is a compound that crosslinks a specific polymer, adhesion for increasing the adhesion between the liquid crystal alignment film and the substrate, and the adhesion between the liquid crystal alignment film and the sealing material.
  • a crosslinkable compound that is a compound that crosslinks a specific polymer, adhesion for increasing the adhesion between the liquid crystal alignment film and the substrate, and the adhesion between the liquid crystal alignment film and the sealing material.
  • Auxiliary agents may be added.
  • the crosslinkable compound has a crosslinkable compound having at least one substituent selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a blocked isocyanate group, a hydroxyl group and an alkoxyl group, and a polymerizable unsaturated group. It is preferable to introduce at least one compound selected from the group consisting of crosslinkable compounds. In addition, it is preferable that two or more of these substituents and polymerizable unsaturated bonds are contained in the crosslinkable compound from the viewpoint of enhancing crosslinkability.
  • crosslinkable compound examples include compounds having an epoxy group or an isocyanate group described in paragraphs [0169] to [0190] of International Publication No. 2011/1327751, a compound having an oxetane group, a hydroxyl group, an alkoxyl group or a lower group.
  • Preferred specific examples of the crosslinkable compound include compounds represented by the following formulas (CL-1) to (CL-11).
  • the content of the crosslinkable compound is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent, and from the viewpoint of enhancing the orientation of the liquid crystal, it is more preferable.
  • the amount is preferably 0.1 to 50 parts by mass, more preferably 1 to 50 parts by mass.
  • adhesion aid examples include functional silane compounds.
  • the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. is there. If it is less than 0.1 parts by mass, the effect of improving the adhesiveness cannot be expected, and if it is more than 30 parts by mass, the orientation of the liquid crystal may be deteriorated.
  • the liquid crystal aligning agent of the present invention includes a poor solvent, a crosslinkable compound, an adhesion aid, a compound that improves the film thickness uniformity and surface smoothness of a resin coating or a liquid crystal alignment film, and a compound that promotes charge loss.
  • a dielectric material or a conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film may be added.
  • the liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film after being applied on a substrate and baked, and then subjected to an alignment treatment such as rubbing treatment or light irradiation. Further, in the case of vertical alignment application, it can be used as a liquid crystal alignment film without alignment treatment.
  • the liquid crystal alignment film of the present invention can be used for a horizontal alignment type or a vertical alignment type (VA system, PSA mode, SC-PVA mode, etc.) liquid crystal alignment film, and among them, PSA mode, SC-PVA mode, etc. It is a liquid crystal alignment film suitable for a vertical alignment type liquid crystal display element, and can control pretilt with a small light irradiation amount.
  • the substrate used in this case is not particularly limited as long as it is a highly transparent substrate, and a glass substrate as well as a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. From the viewpoint of simplifying the process, it is preferable to use a substrate on which an ITO electrode for driving liquid crystal is formed. Further, in the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.
  • the method of applying the liquid crystal aligning agent is not particularly limited, but industrially, a method such as screen printing, offset printing, flexo printing, or inkjet method is generally used. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method or a spray method, and these may be used depending on the purpose.
  • the liquid crystal aligning agent After applying the liquid crystal aligning agent on the substrate, it is heated at 30 to 300 ° C., preferably 30 ° C., depending on the solvent used for the liquid crystal aligning agent, by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) type oven.
  • the solvent can be evaporated at a temperature of up to 250 ° C. to form a liquid crystal alignment film. If the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display device, and if it is too thin, the reliability of the liquid crystal display device may be deteriorated. Is 10 to 100 nm.
  • the liquid crystal display device of the present invention is a liquid crystal display device in which a substrate with a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the above-mentioned method, and then a liquid crystal cell is produced by a known method.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and contains a polymerizable compound which is polymerized by at least one of active energy rays and heat between the pair of substrates.
  • a liquid crystal display element manufactured by a step of polymerizing a polymerizable compound by arranging a liquid crystal composition and applying a voltage between electrodes and at least one of irradiation with an active energy ray and heating.
  • ultraviolet rays are suitable as the active energy rays.
  • the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm.
  • the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, the ultraviolet ray and the heating may be performed at the same time.
  • the above liquid crystal display element controls the pretilt of liquid crystal molecules by the PSA (Polymer Sustained Alignment) method.
  • a small amount of a photopolymerizable compound for example, a photopolymerizable monomer is mixed in a liquid crystal material, a liquid crystal cell is assembled, and then a predetermined voltage is applied to the liquid crystal layer, and the photopolymerizable compound is irradiated with ultraviolet rays. Etc., and the pre-tilt of liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. Further, since the PSA method does not require rubbing treatment, it is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control pretilt by rubbing treatment.
  • the liquid crystal display device of the present invention after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment agent of the present invention by the method described above, to prepare a liquid crystal cell, the polymerizable compound by at least one of irradiation and heating of ultraviolet rays.
  • the alignment of liquid crystal molecules can be controlled by polymerizing.
  • To give an example of PSA liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, disperse spacers on the liquid crystal alignment film of one of the substrates, and place the liquid crystal alignment film surface inside. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure for sealing, or the liquid crystal is dropped on the surface of the liquid crystal alignment film on which the spacers are scattered, and then the substrates are bonded for sealing. Can be mentioned.
  • a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed with the liquid crystal.
  • the polymerizable compound include compounds having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule.
  • the polymerizable compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the liquid crystal component.
  • the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and the orientation of the liquid crystal cannot be controlled. Seizure characteristics are deteriorated.
  • heat or ultraviolet rays are irradiated while applying a voltage of AC or DC to the liquid crystal cell to polymerize the polymerizable compound. Thereby, the alignment of the liquid crystal molecules can be controlled.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferable to use it for a liquid crystal display device manufactured by a process of arranging a liquid crystal alignment film containing the above and applying a voltage between the electrodes, that is, the SC-PVA mode.
  • ultraviolet rays are suitable as the active energy rays.
  • the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm.
  • the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, the ultraviolet ray and the heating may be performed at the same time.
  • a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, or a polymer containing a polymerizable group is mentioned.
  • Specific examples of the polymer having a polymerizable group are not particularly limited as long as it is a polymer having the photoreactive group, and examples thereof include a polymer obtained by using the diamine having the photoreactive group. .
  • a pair of substrates on which the liquid crystal alignment film of the present invention is formed is prepared, spacers are scattered on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is formed.
  • the other substrate is bonded so that it is on the inside, and the liquid crystal is injected under reduced pressure to seal it, or the liquid crystal is dropped on the surface of the liquid crystal alignment film on which spacers are scattered, and then the substrates are bonded and sealed. And the like.
  • the orientation of the liquid crystal molecules can be controlled by applying heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
  • Example 5 Using the liquid crystal aligning agent (A1) obtained in Example 1, a liquid crystal cell was prepared by the procedure shown below.
  • the liquid crystal aligning agent (A1) obtained in Example 1 was spin-coated on the ITO surface of an ITO electrode substrate having an ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m. After drying for 90 seconds on a hot plate at °C, it was baked for 15 minutes in a hot air circulating oven at 230 °C, to form a liquid crystal alignment film having a film thickness of 100 nm.
  • liquid crystal aligning agent (A1) was spin-coated on the ITO surface on which no electrode pattern was formed, dried for 90 seconds on a hot plate at 80 ° C., and then baked for 15 minutes in a hot air circulation oven at 230 ° C. A liquid crystal alignment film having a film thickness of 100 nm was formed.
  • a sealant (solvent-type thermosetting epoxy resin) was printed on the spacer. Then, the surface of the other substrate on which the liquid crystal alignment film was formed was placed inside, and after bonding with the previous substrate, the sealant was cured to prepare an empty cell.
  • Liquid crystal MLC-3023 (trade name (polymerizable compound-containing liquid crystal) manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell.
  • Example 5 (Examples 6 to 12, Comparative Examples 3 to 6)
  • the liquid crystal aligning agent shown in Table 1 obtained in Examples 1 to 4 or Comparative Example 1 or 2 was used, and UV irradiation was performed as follows.
  • a liquid crystal cell was prepared in the same manner as in Example 5 except that the pretilt angle was measured for the liquid crystal cell after UV irradiation in the same manner as in Example 5.
  • the UV irradiation was 20 J / cm 2 in Examples 6, 8, 10, and 12 and Comparative Examples 4 and 6, as shown in Table 1.
  • the measurement results of the pretilt angle are summarized in the table.
  • Examples 5 to 8 are smaller than Comparative Examples 3 to 4 and Examples 9 to 12 are smaller in tilt angle of the liquid crystal cell than Comparative Examples 5 to 6. Therefore, it was confirmed that the tilt imparting ability is improved by using the liquid crystal display element of the present invention.
  • a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention has a wide viewing angle, a high response speed, and a large contrast, and thus is suitable for a large-screen high-definition television, a large monitor, and the like. Can be used.
  • the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2018-202179 filed on October 26, 2018 are cited herein and incorporated as a disclosure of the specification of the present invention. It is a thing.

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Abstract

La présente invention concerne un agent d'alignement de cristaux liquides qui est capable de former un film d'alignement de cristaux liquides qui permet la réalisation d'un élément d'affichage à cristaux liquides ayant un grand angle de vision, une vitesse de réponse rapide et un contraste élevé. L'invention concerne également un agent d'alignement de cristaux liquides qui est caractérisé en ce qu'il contient un polymère qui a une chaîne latérale représentée par la formule (1) et une chaîne latérale représentée par la formule (2). (Dans la formule (1), chacun de R1c et R2c représente un atome d'hydrogène ou un groupe alkyle ayant de 1 à 10 atomes de carbone ; Yc représente une liaison simple ou -CO- ; Ar1 représente un groupe phénylène, un groupe naphtylène ou un groupe biphénylène ; chacun de T1c et T2c représente une liaison simple, -O-, -COO- ou similaire ; Ac représente une liaison simple, un groupe alkylène ayant de 1 à 20 atomes de carbone ou similaire ; n représente un nombre de 1 à 4 ; et * représente une main de liaison.) (Dans la formule (2), Q représente un groupe représenté par l'une des formules (q-1)-(q-4) ou similaire ; chacun de R1r et R2r représente un groupe alkyle ayant de 1 à 10 atomes de carbone, un groupe alcoxy ou similaire ; Ar2 représente un groupe hydrocarboné aromatique divalent ; chacun de T1r et T2r représente une liaison simple, -O -, -COO- ou similaire ; Ar représente une liaison simple, un groupe alkylène ayant de 1 à 20 atomes de carbone ou similaire ; et * représente une main de liaison.)
PCT/JP2019/041769 2018-10-26 2019-10-24 Agent d'alignment de cristaux liquides, film d'alignment de cristaux liquides et élément d'affichage à cristaux liquides Ceased WO2020085450A1 (fr)

Priority Applications (3)

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CN201980070307.XA CN112888996B (zh) 2018-10-26 2019-10-24 液晶取向剂、液晶取向膜及液晶表示元件
JP2020552602A JP7375766B2 (ja) 2018-10-26 2019-10-24 液晶配向剤、液晶配向膜、及び液晶表示素子
KR1020217013120A KR102845022B1 (ko) 2018-10-26 2019-10-24 액정 배향제, 액정 배향막, 및 액정 표시 소자

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JP2018202179 2018-10-26

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011132751A1 (fr) * 2010-04-22 2011-10-27 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
JP2014206720A (ja) * 2013-03-19 2014-10-30 Jsr株式会社 液晶配向剤、液晶配向膜、液晶表示素子、重合体及び化合物
WO2016140288A1 (fr) * 2015-03-04 2016-09-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6369014B2 (ja) 2013-02-25 2018-08-08 Jsr株式会社 液晶表示素子用組成物、並びに液晶表示素子及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011132751A1 (fr) * 2010-04-22 2011-10-27 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
JP2014206720A (ja) * 2013-03-19 2014-10-30 Jsr株式会社 液晶配向剤、液晶配向膜、液晶表示素子、重合体及び化合物
WO2016140288A1 (fr) * 2015-03-04 2016-09-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides

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CN112888996B (zh) 2024-11-08
KR20210082462A (ko) 2021-07-05
TW202104435A (zh) 2021-02-01
KR102845022B1 (ko) 2025-08-11
TWI830796B (zh) 2024-02-01
JP7375766B2 (ja) 2023-11-08
CN112888996A (zh) 2021-06-01
JPWO2020085450A1 (ja) 2021-09-16

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