WO2011132751A1 - 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

Info

Publication number
WO2011132751A1
WO2011132751A1 PCT/JP2011/059867 JP2011059867W WO2011132751A1 WO 2011132751 A1 WO2011132751 A1 WO 2011132751A1 JP 2011059867 W JP2011059867 W JP 2011059867W WO 2011132751 A1 WO2011132751 A1 WO 2011132751A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
group
carbon atoms
fluorine
integer
Prior art date
Application number
PCT/JP2011/059867
Other languages
English (en)
Japanese (ja)
Inventor
徳俊 三木
耕平 後藤
雅章 片山
幸司 園山
和義 保坂
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to CN201180030910.9A priority Critical patent/CN102947753B/zh
Priority to JP2012511706A priority patent/JP5713009B2/ja
Priority to KR1020127030217A priority patent/KR101775181B1/ko
Publication of WO2011132751A1 publication Critical patent/WO2011132751A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation

Definitions

  • the present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.
  • a polyimide film is used as a liquid crystal alignment film used in a liquid crystal display element.
  • This polyimide film is formed by using a solution of a polyamic acid, which is a precursor of polyimide, or a solution of a solvent-soluble polyimide as a substrate. The method of apply
  • coating and baking is taken.
  • This polyamic acid or solvent-soluble polyimide is generally synthesized by reacting a tetracarboxylic acid derivative such as tetracarboxylic dianhydride with a diamine.
  • pretilt angle control of the liquid crystal in which the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained at an arbitrary value. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film.
  • the method using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle in accordance with the proportion of the diamine used, so that the desired pretilt angle is obtained. This is relatively easy and is useful as a means for increasing the pretilt angle.
  • Examples of the side chain structure of the diamine that increases the pretilt angle of the liquid crystal include a long-chain alkyl group or a fluoroalkyl group (for example, see Patent Document 1), a cyclic group or a combination of a cyclic group and an alkyl group (for example, see Patent Document 2), A steroid skeleton (see, for example, Patent Document 3) is known.
  • JP-A-2-282726 Japanese Patent Laid-Open No. 3-179323 JP-A-4-281427
  • MVA Multi-domain Vertical Alignment
  • TN Transmission Nematic
  • the liquid crystal injection speed is lowered, so that the production efficiency at the time of manufacturing the liquid crystal display element is deteriorated, and when the ODF (One Drop Drop Filling) method is used.
  • ODF One Drop Drop Filling
  • the present invention has been made in view of the above circumstances, and improves the liquid crystal wettability on the liquid crystal alignment film, has high production efficiency at the time of manufacturing a liquid crystal display element, and does not cause poor display of alignment unevenness. It is providing a processing agent, a liquid crystal aligning film, and a liquid crystal display element.
  • the present inventors have achieved the above object by a polyimide precursor having a specific side chain structure and a liquid crystal aligning agent containing polyimide obtained by dehydrating and ring-closing the polyimide precursor. Therefore, the present invention has been found to be extremely effective, and the present invention has been completed.
  • the present invention has the following gist.
  • Liquid crystal alignment treatment comprising a diamine compound represented by the following formula [1] and a polymer obtained by reacting a diamine component containing the diamine compound represented by the following formula [2] with tetracarboxylic dianhydride. Agent.
  • X 1 is a divalent organic group selected from —NHCO—, —N (CH 3 ) CO—, —CONH—, —CON (CH 3 ) —, and X 2 is a single bond.
  • a benzene ring or a cyclohexyl ring is a divalent organic group selected from a benzene ring or a cyclohexyl ring
  • X 4 is a cyclohexyl ring
  • X 5 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or 1 carbon atom. From 18 to 18 fluorine-containing alkoxyl groups, and n is an integer from 1 to 4.
  • Y 1 represents —O—, —CH 2 O—, — (CH 2 ) a — (a is an integer of 1 to 10), —COO—, —OCO—, or Y 2 is a divalent organic group selected from a bond
  • Y 2 is a single bond or a divalent organic group selected from — (CH 2 ) b — (b is an integer of 1 to 10)
  • Y 3 Is a divalent organic group selected from a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or —OCO—.
  • Y 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, on the cyclic group
  • Arbitrary hydrogen atoms include an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, The fluorine-containing alkoxyl group having 1 to 3 carbon atoms, may be substituted with one selected from a fluorine atom
  • Y 5 represents a divalent cyclic group selected from cyclohexyl ring, a benzene ring or a heterocyclic cyclohexane
  • any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon
  • Z 1 is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms).
  • Z 2 to Z 5 are groups selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, which may be the same or different, and in the formula [3g] Z 6 and Z 7 are a hydrogen atom or a methyl group, and each may be the same or different.
  • liquid crystal aligning agent a crosslinkable compound having at least one substituent selected from the group consisting of epoxy group, oxetane group, isocyanate group and cyclocarbonate group, hydroxyl group, hydroxyalkyl group, alkoxyl group and lower alkoxyalkyl
  • liquid crystal alignment treatment according to any one of (1) to (4), having a crosslinkable compound having at least one substituent selected from the group consisting of groups, or a crosslinkable compound having a polymerizable unsaturated bond Agent.
  • liquid crystal aligning agent according to any one of (1) to (5), wherein the polymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and ring-closing polyamic acid.
  • liquid crystal aligning agent according to any one of (1) to (6), wherein the liquid crystal aligning agent contains 5 to 60% by mass of a poor solvent.
  • a liquid crystal alignment film used for a liquid crystal display element which is a polymer obtained by polymerizing the polymerizable compound while applying a voltage to the liquid crystal layer, and is obtained by a method of controlling the alignment direction of the liquid crystal during driving.
  • a liquid crystal display element comprising the liquid crystal alignment film according to (10), wherein the polymerization is performed while applying a voltage to the liquid crystal layer using a liquid crystal material in which a liquid crystal is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation.
  • a liquid crystal display element obtained by polymerizing an organic compound and obtained by a method of controlling the alignment direction of liquid crystal during driving.
  • liquid crystal aligning agent of the present invention By using the liquid crystal aligning agent of the present invention, there is provided a liquid crystal display element having high liquid crystal wettability on the liquid crystal alignment film, high production efficiency at the time of producing the liquid crystal display element, and no display defects of alignment unevenness. be able to.
  • the present invention includes a diamine component including a diamine compound represented by the following formula [1] (also referred to as a specific diamine compound) and a diamine compound represented by the following formula [2] (also referred to as a specific side chain diamine compound);
  • a liquid crystal aligning agent containing a polymer obtained by reacting with tetracarboxylic dianhydride, a liquid crystal aligning film obtained using the liquid crystal aligning agent, and a liquid crystal display device having the liquid crystal aligning film is there.
  • X 1 is a divalent organic group selected from —NHCO—, —N (CH 3 ) CO—, —CONH—, —CON (CH 3 ) —, and X 2 is a single bond.
  • a benzene ring or a cyclohexyl ring is a divalent organic group selected from a benzene ring or a cyclohexyl ring
  • X 4 is a cyclohexyl ring
  • X 5 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or 1 carbon atom. From 18 to 18 fluorine-containing alkoxyl groups, and n is an integer from 1 to 4.
  • Y 1 is —O—, —CH 2 O—, — (CH 2 ) a — (a is an integer of 1 to 10), —COO—, —OCO—, or a single bond
  • Y 2 is a single bond or a divalent organic group selected from — (CH 2 ) b — (b is an integer of 1 to 10)
  • Y 3 is A divalent organic group selected from a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or —OCO—.
  • Y 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton.
  • the hydrogen atom is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, Fluorine-containing alkoxyl group having 1 to 3 carbon atoms, may be substituted with one selected from a fluorine atom
  • Y 5 represents a divalent cyclic group selected from cyclohexyl ring, a benzene ring or a heterocyclic cyclohexane
  • Arbitrary hydrogen atoms on these cyclic groups are alkyl groups having 1 to 3 carbon atoms, alkoxyl groups having 1 to 3 carbon atoms, fluorine-containing alkyl groups having 1 to 3 carbon atoms, or fluorine containing 1 to 3 carbon atoms
  • n is an integer of 0 to 4
  • Y 6 is an alkyl group
  • the liquid crystal alignment film obtained from the liquid crystal aligning agent using the specific diamine compound of the present invention and the specific side chain type diamine compound even when a large amount of diamine components having side chains are used in order to obtain a high pretilt angle, The liquid crystal wettability on the liquid crystal alignment film is increased.
  • the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention it is possible to provide a liquid crystal display element that has high production efficiency at the time of manufacturing the liquid crystal display element and that does not cause poor display of alignment unevenness. .
  • the specific diamine compound of the present invention is a diamine compound represented by the following formula [1].
  • X 1 is a divalent organic group selected from —NHCO—, —N (CH 3 ) CO—, —CONH—, —CON (CH 3 ) —, and in particular, —NHCO— , -CONH- is preferable. More preferred is —NHCO—.
  • X 2 is a divalent organic group selected from a single bond, a benzene ring, or a cyclohexyl ring, that is, a phenylene group or a cyclohexylene group. Among them, a single bond or benzene A ring is preferred.
  • X 3 is a divalent organic group selected from a benzene ring or a cyclohexyl ring.
  • X 4 is a divalent organic group selected from a benzene ring or a cyclohexyl ring.
  • X 5 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
  • an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
  • n is an integer of 1 to 4, and an integer of 1 or 2 is particularly preferable.
  • Preferred combinations of X 1 , X 2 , X 3 , X 4 and n in the formula [1] are as shown in 1-1 to 1-64 shown in Tables 1 to 5.
  • the specific side chain diamine compound of the present invention is a diamine compound represented by the following formula [2].
  • Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or —OCO—. It is a divalent organic group selected.
  • a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, or —COO— is preferable because the side chain structure can be easily synthesized.
  • it is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O—, or —COO—.
  • Y 2 is a single bond or a divalent organic group selected from — (CH 2 ) b — (b is an integer of 1 to 15). Among these, a single bond or — (CH 2 ) b — (b is an integer of 1 to 0) is preferable.
  • Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO—, or —OCO—. It is a divalent organic group selected.
  • a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or —OCO— is preferable because they are easy to synthesize.
  • they are a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or —OCO—.
  • Y 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton
  • Arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms
  • an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexyl ring or a steroid skeleton is preferable.
  • Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl having 1 to 3 carbon atoms.
  • a benzene ring or a cyclohexyl ring is preferable.
  • Y 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, or It is a hydrogen atom.
  • an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
  • it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
  • n is an integer of 0 to 4. Preferably, it is an integer of 0-2.
  • Preferred combinations of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , and n in Formula [2] are as shown in Tables 2-1 to 2-629 shown in Tables 6 to 47.
  • c is an integer from 1 to 10.
  • c is an integer from 1 to 10.
  • c is an integer from 1 to 10.
  • a is an integer from 1 to 10.
  • a is an integer from 1 to 10.
  • a is an integer from 1 to 10.
  • a is an integer from 1 to 10.
  • a is an integer from 1 to 10.
  • a and c are each independently an integer of 1 to 10.
  • m is an integer of 1 to 4. Preferably, it is an integer of 1 to 2.
  • the structure is represented by the following formula [2-1] to formula [2-32].
  • R 1 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, —CH 2 OCO—
  • R 2 Is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).
  • R 3 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, Or —CH 2 —, wherein R 4 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group).
  • R 5 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 — or —O—, wherein R 6 is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.
  • R 7 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer, respectively. is there).
  • R 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer, respectively. is there).
  • a 4 represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
  • a 3 represents a 1,4-cyclohexylene group or 1, 4 -Phenylene group
  • a 2 is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A 3 )
  • a 1 is an oxygen atom or —COO— * (However, the bond marked with “*” binds to (CH 2 ) a 2.
  • a 1 is an integer of 0 or 1
  • a 2 is an integer of 2 to 10.
  • a 3 is an integer of 0 or 1).
  • a diamine having an alkyl group or a fluorine-containing alkyl group in the diamine side chain can be used.
  • diamines represented by the following formulas [DA1] to [DA12] can be exemplified.
  • a 1 is 1 or more carbon atoms 22 an alkyl group, or a fluorine-containing alkyl group).
  • a 2 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—.
  • a 3 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).
  • p is an integer of 1 to 10).
  • the above-mentioned other diamine compounds may be used alone or in combination of two or more depending on the properties such as liquid crystal orientation, voltage holding ratio, and accumulated charge when the liquid crystal alignment film is used.
  • tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) represented by the following formula [3] as a part of the raw material.
  • Z 1 is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.
  • Z 1 is a tetravalent group represented by, for example, the following formulas [3a] to [3j].
  • Z 2 to Z 5 are groups selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, which may be the same or different, and in the formula [3g], Z 6 and Z 7 are a hydrogen atom or a methyl group, and may be the same or different.
  • Z 1 particularly preferred structure of Z 1 is represented by formula [3a], formula [3c], formula [3d], formula [3e], formula [3f], or from the viewpoint of polymerization reactivity and ease of synthesis.
  • Formula [3g] particularly preferred structure of Z 1 is represented by formula [3a], formula [3c], formula [3d], formula [3e], formula [3f], or from the viewpoint of polymerization reactivity and ease of synthesis.
  • the above-mentioned other tetracarboxylic dianhydrides can be used alone or in combination of two or more depending on the properties such as liquid crystal alignment properties, voltage holding ratio, accumulated charge, etc. when the liquid crystal alignment film is formed.
  • the polymer used in the present invention includes a specific diamine compound represented by the above formula [1] and a diamine component containing a specific side chain diamine compound represented by the above formula [2] and a tetracarboxylic acid diester.
  • the method for synthesizing the polymer of the present invention is not particularly limited, but a method of reacting a diamine component with tetracarboxylic dianhydride, as in a general polyimide precursor (for example, polyamic acid) or polyimide synthesis method. Can be used. At that time, tetracarboxylic acid derivatives such as tetracarboxylic acid or tetracarboxylic acid dihalide can also be used.
  • the liquid crystal alignment film obtained by using the polymer of the present invention increases the wettability of the liquid crystal on the liquid crystal alignment film as the content ratio of the specific diamine compound in the diamine component increases. It is possible to provide a liquid crystal display element that is high and does not cause poor display of uneven alignment. In addition, the pretilt angle of the liquid crystal can be increased as the content of the specific side chain diamine compound increases.
  • the content of the specific side chain diamine compound in the diamine component is preferably 0.01 to 99 mol with respect to 1 mol of the specific diamine compound. More preferably, it is 0.1 to 50 mol, still more preferably 0.5 to 20 mol, and most preferably 0.5 to 10 mol.
  • a specific tetracarboxylic dianhydride represented by the above formula [3] as the tetracarboxylic dianhydride.
  • 1 mol% or more of tetracarboxylic dianhydrides are specific tetracarboxylic dianhydrides.
  • 5 mol% or more of the tetracarboxylic dianhydride is a specific tetracarboxylic dianhydride, and more preferably 10 mol% or more.
  • specific tetracarboxylic dianhydride may be sufficient as 100 mol% of tetracarboxylic dianhydride.
  • the polyimide precursor of the present invention by a reaction between a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used.
  • the diamine component and tetracarboxylic dianhydride are reacted in an organic solvent.
  • the reaction between the diamine component and tetracarboxylic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
  • the organic solvent used for the reaction between the diamine component and tetracarboxylic dianhydride is not particularly limited as long as the generated polyimide precursor is soluble. Specific examples are given below.
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent.
  • a method of adding by dispersing or dissolving a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component. Any of these methods may be used.
  • the diamine component or tetracarboxylic dianhydride when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed and reacted to form a high molecular weight product.
  • the polymerization temperature at that time can be selected from -20 ° C. to 150 ° C., but is preferably in the range of ⁇ 5 ° C. to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight copolymer, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. Since it becomes difficult, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the ratio of the total number of moles of the diamine component and the total number of moles of tetracarboxylic dianhydride is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
  • the polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the polyamic acid which is the polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.
  • the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, and catalyst imidization in which a catalyst is added to the polyimide precursor solution.
  • the temperature is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
  • the catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
  • 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 with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the reaction solution may be poured into a poor solvent and precipitated.
  • the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
  • the polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
  • the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
  • the molecular weight of the polyimide precursor or polyimide contained in the liquid crystal aligning agent of the present invention is determined by considering the strength of the coating film obtained therefrom, the workability at the time of coating film formation, and the uniformity of the coating film.
  • the weight average molecular weight measured by Gel Permeation Chromatography is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • the liquid crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution which the resin component for forming a resin film melt
  • the resin component includes the above-described polymer of the present invention, that is, the diamine component including the specific diamine compound represented by the formula [1] and the specific side chain diamine compound represented by the formula [2].
  • the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
  • all of the resin components may be the polymer of the present invention, and other polymers may be mixed with the polymer of the present invention.
  • the content of the polymer other than the polymer of the present invention in the resin component is 0.5 to 15% by mass, preferably 1 to 10% by mass.
  • Examples of such another polymer include a polyimide precursor or a polyimide that does not use a specific diamine compound and a specific side chain diamine compound as a raw material.
  • a crosslinkable compound that is a compound that crosslinks a polymer for the purpose of obtaining a liquid crystal alignment film whose voltage holding ratio does not decrease even under heat or ultraviolet irradiation, specifically, At least one selected from the group consisting of a crosslinkable compound having at least one substituent selected from an epoxy group, an isocyanate group, an oxetane group, and a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, an alkoxyl group, and a lower alkoxyalkyl group. It is preferable to introduce a crosslinkable compound having a seed substituent or a crosslinkable compound having a polymerizable unsaturated bond. In addition, it is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.
  • crosslinkable compound having an epoxy group or an isocyanate group examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, and tetraglycidyl.
  • the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].
  • crosslinkable compounds represented by the following formulas [4a] to [4k].
  • Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxyl group, and a lower alkoxyalkyl group include, for example, an amino resin having a hydroxyl group, an alkoxyl group, or a lower alkoxyalkyl group, such as a melamine resin. And urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, and ethylene urea-formaldehyde resin.
  • the lower alkoxyalkyl group is, for example, an alkoxyalkyl group having 1 to 4 carbon atoms.
  • crosslinkable compound for example, a melamine derivative, a benzoguanamine derivative or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group or both can be used.
  • the melamine derivative and benzoguanamine derivative may exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.
  • Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
  • Eight-substituted MW-30 (from Sanwa Chemical Co., Ltd.), methoxymethylated melamines such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 and the like Methoxymethylated etoxy Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzogu
  • benzene or phenolic compounds having a hydroxyl group or an alkoxyl group examples include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis (sec -Butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.
  • crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meta ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (me ) Acrylate, neopentyl glycol di (meth) acrylate,
  • a 1 is an n-valent group selected from a cyclohexyl ring, a bicyclohexyl ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, or a phenanthrene ring
  • a 2 is a group selected from the following formula [5a] or [5b]
  • n is an integer of 1 to 4.
  • crosslinkable compound contained in the liquid crystal aligning agent of this invention may be one type, and may be combined two or more types.
  • the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymer of the present invention made of a polyimide precursor or polyimide.
  • the amount is more preferably 0.1 to 100 parts by weight, particularly 1 to 50 parts by weight, so that the crosslinking reaction proceeds and the desired effect is exhibited and the orientation of the liquid crystal is not lowered.
  • Nitrogen-containing heterocyclic amine compounds represented by the following formulas [M1] to [M156] are used as compounds that promote charge transfer in the liquid crystal alignment film and promote charge release of a liquid crystal cell using the liquid crystal alignment film. It is preferable to add.
  • the nitrogen-containing heterocyclic amine compound may be added directly to the polymer solution, but it is made into a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass with an appropriate solvent. It is preferable to add after adding.
  • the solvent is not particularly limited as long as it is an organic solvent that dissolves the above-described resin component.
  • the organic solvent used in the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent that dissolves the above-described resin component. Examples thereof include N-methyl-2-pyrrolidone and butyl cellosolve.
  • the liquid crystal aligning agent of the present invention preferably contains a poor solvent.
  • the poor solvent refers to a solvent that improves film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied. Specific examples of the poor solvent include the following.
  • solvents may be used alone or in combination.
  • the above poor solvent it is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and further preferably 20 to 60% by mass of the total solvent contained in the liquid crystal aligning agent. %.
  • the liquid crystal aligning agent of the present invention may contain components other than those described above. Examples thereof include a solvent compound that improves film thickness uniformity and surface smoothness, and a compound that improves the adhesion between the liquid crystal alignment film and the substrate.
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
  • F-top EF301, EF303, EF352 manufactured by Tochem Products
  • MegaFuck F171, F173, R-30 manufactured by Dainippon Ink
  • Florard FC430, FC431 manufactured by Sumitomo 3M
  • Asahi Guard AG710 Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass) and the like.
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
  • Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing 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 the resin component contained in the liquid crystal aligning agent. It is. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • the liquid crystal alignment treatment agent of the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. May be added.
  • the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
  • an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
  • Calcination after applying the liquid crystal aligning agent on the substrate can form a coating film by evaporating the solvent at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate. If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
  • liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
  • Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like.
  • the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the liquid-crystal aligning agent of this invention has the high wettability of the liquid crystal on a liquid-crystal aligning film, it can inject
  • the liquid crystal alignment treatment agent of the present invention is a liquid crystal layer using a liquid crystal display element in which alignment unevenness easily occurs during liquid crystal injection, that is, a liquid crystal material in which a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed with liquid crystal. It is also useful for a liquid crystal display device obtained by a method of controlling the alignment direction of liquid crystal during driving with a polymer obtained by polymerizing a polymerizable compound while applying a voltage to the substrate.
  • liquid crystal display element After obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, a liquid crystal cell is prepared, and a polymerizable compound is polymerized by irradiation with heat or ultraviolet rays.
  • the liquid crystal display element has a controlled orientation.
  • liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
  • Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like.
  • the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the liquid crystal used in this case is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation.
  • the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule.
  • the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component.
  • the polymerizable compound When the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases, and the liquid crystal display The burn-in characteristic of the element is deteriorated.
  • the orientation of the liquid crystal can be controlled by polymerizing the polymerizable compound by irradiating the liquid crystal cell with heat or ultraviolet rays while applying an AC or DC voltage.
  • the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
  • PCH7DAB 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene
  • PBCH5DAB 1,3-diamino-4- ⁇ 4- [trans-4- (trans-4 -N-pentylcyclohexyl) cyclohexyl] phenoxy ⁇ benzene
  • m-PBCH5DABz 1,3-diamino-5- ⁇ 4- [4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxymethyl ⁇ benzene
  • ColDAB -1 Specific side chain diamine compound represented by the following formula
  • Crosslinkable compound (1) YH-434L (manufactured by Tohto Kasei) (epoxy-based crosslinkable compound)
  • Crosslinkable compound (2) OXT-221 (manufactured by Toa Gosei) (oxetane-based crosslinkable compound)
  • Crosslinkable compound (3) crosslinkable compound represented by the following formula (hydroxylated phenol-based crosslinkable compound)
  • the molecular weight of polyimide in the synthesis example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and columns (KD-803, KD-805) (manufactured by Shodex). Measured.
  • GPC gel permeation chromatography
  • the imidation ratio of polyimide in the synthesis example was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 (Kusano Kagaku)) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) Then, it was completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum).
  • JNW-ECA500 deuterated dimethyl sulfoxide
  • the imidation rate is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears near 9.5 to 10.0 ppm. It calculated
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • x is a proton peak integrated value derived from NH group of amic acid
  • y is a peak integrated value of reference proton
  • ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
  • Table 48 shows the polyamic acid and polyimide of the present invention.
  • a liquid crystal alignment treatment agent is spin-coated on the ITO surface of a substrate with 3 ⁇ 4 cm ITO electrodes, and is heated on a hot plate at 80 ° C. for 5 minutes, and then heated at 220 ° C. for 30 minutes in a heat-circulating clean oven. A substrate with a 100 nm thick polyimide liquid crystal alignment film was obtained.
  • Example 1 The polyamic acid solution (1) (10.5 g), NMP (8.50 g), and BCS (24.6 g) having a resin solid content concentration of 24.9% by mass obtained in Synthesis Example 1 were added at 25 ° C. By mixing for a time, a liquid crystal aligning agent (1) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 2 The polyimide powder (2) (2.52 g), NMP (22.3 g), and BCS (19.7 g) obtained in Synthesis Example 2 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal aligning agent (2 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 3 The polyimide powder (3) (2.50 g), NMP (24.0 g), and BCS (17.6 g) obtained in Synthesis Example 3 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (3 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 4 The polyimide powder (4) (2.51 g), NMP (26.1 g), and BCS (15.7 g) obtained in Synthesis Example 4 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (4 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 5 The polyimide powder (5) (2.50 g), NMP (29.9 g), and BCS (11.8 g) obtained in Synthesis Example 5 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (5 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 6 The polyamic acid solution (6) (11.0 g), NMP (11.1 g), and BCS (23.7 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 6 were obtained at 25 ° C. By mixing for a time, a liquid crystal aligning agent (6) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 7 The polyimide powder (7) (2.51 g), NMP (30.0 g), and BCS (11.8 g) obtained in Synthesis Example 7 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (7 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 8 The polyimide powder (8) (2.50 g), NMP (26.0 g), and BCS (15.7 g) obtained in Synthesis Example 8 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (8 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 9 The polyimide powder (9) (2.50 g), NMP (31.9 g), and BCS (9.80 g) obtained in Synthesis Example 9 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (9 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 10 The polyimide powder (10) (2.53 g), NMP (30.3 g), and BCS (11.9 g) obtained in Synthesis Example 10 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (10 ) This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 11 The polyimide powder (2) (2.50 g), NMP (22.1 g), BCS (19.6 g), and crosslinkable compound (1) (0.25 g) obtained in Synthesis Example 2 were added at 25 ° C.
  • the liquid crystal aligning agent (11) was obtained by mixing for 12 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 12 The polyimide powder (3) (2.50 g), NMP (24.0 g), BCS (17.6 g), and crosslinkable compound (2) (0.50 g) obtained in Synthesis Example 3 were added at 25 ° C.
  • the liquid crystal aligning agent (12) was obtained by mixing for 12 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • Example 13 The polyimide powder (3) (2.51 g), NMP (24.1 g), BCS (17.7 g), and the crosslinkable compound (3) (0.25 g) obtained in Synthesis Example 3 were added at 25 ° C. It mixed for 12 hours and obtained the liquid-crystal aligning agent (13). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
  • the liquid crystal wettability on the liquid crystal alignment film is high while the pretilt angle of the liquid crystal is high.
  • Comparative Example 1 Comparative Example 2, and Comparative Example 5 using only the specific side chain type diamine compound, the pretilt angle of the liquid crystal is high, but the liquid crystal wettability on the liquid crystal alignment film is low. Further, Comparative Example 3 using a side chain diamine compound other than the specific diamine compound and the specific side chain diamine compound similarly has a high pretilt angle of the liquid crystal, but low wettability of the liquid crystal on the liquid crystal alignment film. As a result. In addition, in Comparative Example 4 using only the specific diamine compound, the liquid crystal wettability on the liquid crystal alignment film was high, but the pretilt angle of the liquid crystal was low.
  • the liquid crystal alignment treatment agent of the present invention can obtain a liquid crystal alignment film having high liquid crystal wettability on the liquid crystal alignment film.
  • a liquid crystal alignment film having high liquid crystal wettability even when a large amount of a diamine component having a side chain is used to obtain a high pretilt angle, the effect can be obtained. Therefore, by using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal display element that has high production efficiency at the time of manufacturing the liquid crystal display element and does not cause poor display of alignment unevenness.
  • the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is a liquid crystal display element in which alignment unevenness easily occurs during liquid crystal injection, that is, a liquid crystal mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation.
  • This is a polymer obtained by polymerizing a liquid crystal layer while applying a voltage to the liquid crystal layer, and is also useful for a liquid crystal display device obtained by a method for controlling the alignment direction of liquid crystal during driving.

Landscapes

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

Abstract

L'invention concerne un agent d'alignement de cristaux liquides qui contient un polymère obtenu par réaction entre un dianhydride d'acide tétracarboxylique et un composant de diamine contenant les composés de diamine de la formule 1 et de la formule 2. Dans la formule 1, X1 représente un groupe organique divalent choisi parmi -NHCO-, -N(CH3)CO-, -CONH- et -CON(CH3)- ; X2 représente un groupe organique divalent choisi parmi une simple liaison, un noyau benzénique et un noyau cyclohexyle ; X3 et X4 représentent des groupes organiques divalents choisis parmi un noyau benzénique et un noyau cyclohexyle ; X5 est choisi parmi un groupe alkyle en C1-18, un groupe alkyle en C1-18 contenant du fluor, un groupe alcoxy en C1-18 et un groupe alcoxy en C1-18 contenant du fluor ; et n est un entier valant de 1 à 4. Dans la formule 2, Y1 représente un groupe organique divalent choisi parmi une simple liaison, -(CH2)a (a étant un entier valant de 1 à 10), -O-, -CH2O-, -COO- et -OCO- ; Y2 représente un groupe organique divalent choisi parmi une simple liaison et -(CH2)b (b étant un entier valant de 1 à 10) ; Y3 représente un groupe organique divalent choisi parmi une simple liaison, -(CH2)c (c étant un entier valant de 1 à 10), -O-, -CH2O-, -COO- et -OCO- ; Y4 représente un groupe cyclique divalent choisi parmi un noyau benzénique, un noyau cyclohexyle et un hétérocycle, ou bien un groupe organique divalent en C12-25 ayant un squelette de stéroïde, tout atome d'hydrogène donné des groupes cycliques susmentionnés pouvant être remplacé par un groupe choisi parmi un groupe alkyle en C1-3, un groupe alcoxy en C1-3, un groupe alkyle en C1-3 contenant du fluor, un groupe alcoxy en C1-3 contenant du fluor, et un atome de fluor ; Y5 représente un groupe cyclique divalent choisi parmi un noyau benzénique, un noyau cyclohexyle et un hétérocycle, tout atome d'hydrogène donné de ces groupes cycliques pouvant être remplacé par un groupe choisi parmi un groupe alkyle en C1-3, un groupe alcoxy en C1-3, un groupe alkyle en C1-3 contenant du fluor, un groupe alcoxy en C1-3 contenant du fluor, et un atome de fluor ; n est un entier valant de 0 à 4 ; Y6 est un groupe alkyle en C1-18, un groupe alkyle en C1-18 contenant du fluor, un groupe alcoxy en C1-18, un groupe alcoxy en C1-18 contenant du fluor, ou un atome d'hydrogène ; et m est un entier valant de 1 à 4.
PCT/JP2011/059867 2010-04-22 2011-04-21 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides WO2011132751A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201180030910.9A CN102947753B (zh) 2010-04-22 2011-04-21 液晶取向处理剂、液晶取向膜及液晶显示元件
JP2012511706A JP5713009B2 (ja) 2010-04-22 2011-04-21 液晶配向処理剤、液晶配向膜及び液晶表示素子
KR1020127030217A KR101775181B1 (ko) 2010-04-22 2011-04-21 액정 배향 처리제, 액정 배향막 및 액정 표시 소자

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2010-099170 2010-04-22
JP2010099170 2010-04-22
JP2010-105674 2010-04-30
JP2010105674 2010-04-30

Publications (1)

Publication Number Publication Date
WO2011132751A1 true WO2011132751A1 (fr) 2011-10-27

Family

ID=44834267

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/JP2011/059868 WO2011132752A1 (fr) 2010-04-22 2011-04-21 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
PCT/JP2011/059867 WO2011132751A1 (fr) 2010-04-22 2011-04-21 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/059868 WO2011132752A1 (fr) 2010-04-22 2011-04-21 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides

Country Status (5)

Country Link
JP (2) JP5713009B2 (fr)
KR (2) KR101775181B1 (fr)
CN (2) CN102947753B (fr)
TW (2) TWI447146B (fr)
WO (2) WO2011132752A1 (fr)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013105523A1 (fr) * 2012-01-12 2013-07-18 和光純薬工業株式会社 Agent d'alignement de cristaux liquides
WO2013115387A1 (fr) * 2012-02-03 2013-08-08 日産化学工業株式会社 Agent d'alignement des cristaux liquides, film d'alignement des cristaux liquides et élément d'affichage à cristaux liquides
WO2013125595A1 (fr) * 2012-02-22 2013-08-29 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
CN103364996A (zh) * 2012-03-30 2013-10-23 索尼公司 液晶显示装置及其制造方法
KR20140084278A (ko) * 2011-11-01 2014-07-04 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR20140114749A (ko) * 2013-03-19 2014-09-29 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막, 액정 표시 소자, 중합체 및 화합물
CN104737069A (zh) * 2012-08-30 2015-06-24 日产化学工业株式会社 液晶取向处理剂及使用该液晶取向处理剂的液晶显示元件
KR20150100494A (ko) * 2014-02-25 2015-09-02 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
KR20150119199A (ko) * 2013-02-13 2015-10-23 닛산 가가쿠 고교 가부시키 가이샤 액정 배향막의 제조 방법, 액정 배향막, 액정 표시 소자 및 액정 배향제
WO2016204178A1 (fr) * 2015-06-16 2016-12-22 三菱化学株式会社 Film d'alignement, et composition pour films d'alignement
WO2017038627A1 (fr) * 2015-08-28 2017-03-09 日産化学工業株式会社 Nouveau composé de diamine possédant une capacité de génération de radicaux et une capacité de génération de bases, et nouveau polymère imide utilisant ledit nouveau composé de diamine comme matériau de départ
EP3163367A4 (fr) * 2014-06-25 2018-01-24 Nissan Chemical Industries, Ltd. Élément d'affichage à cristaux liquides
KR20190031570A (ko) * 2016-08-03 2019-03-26 닛산 가가쿠 가부시키가이샤 곡면 형상을 갖는 액정 패널을 구비하는 액정 표시 소자 및 그것을 위한 액정 배향제
WO2019244939A1 (fr) * 2018-06-19 2019-12-26 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 l'utilisant, et procédé de production dudit élément d'affichage à cristaux liquides, et composé diamine
WO2020085450A1 (fr) * 2018-10-26 2020-04-30 日産化学株式会社 Agent d'alignment de cristaux liquides, film d'alignment de cristaux liquides et élément d'affichage à cristaux liquides
WO2021065933A1 (fr) 2019-10-02 2021-04-08 日産化学株式会社 Élément de commande de lumière à cristaux liquides
JP2022140484A (ja) * 2016-02-15 2022-09-26 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
WO2023157876A1 (fr) 2022-02-17 2023-08-24 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

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102072871B1 (ko) * 2012-04-18 2020-02-03 닛산 가가쿠 가부시키가이샤 광 배향법용의 액정 배향제, 액정 배향막 및 액정 표시 소자
CN105164580B (zh) * 2013-03-01 2019-04-19 日产化学工业株式会社 液晶表示元件、液晶取向膜和液晶取向处理剂
WO2014157235A1 (fr) * 2013-03-26 2014-10-02 日産化学工業株式会社 Élément d'affichage à cristaux liquides, film d'alignement de cristaux liquides, et agent de traitement d'alignement à cristaux liquides
TWI490253B (zh) * 2013-07-12 2015-07-01 Daxin Materials Corp 液晶配向劑、液晶配向膜以及液晶顯示元件
TWI477479B (zh) * 2013-07-18 2015-03-21 Daxin Materials Corp 二胺苯化合物、聚合物、配向膜用組成物、配向膜以及液晶顯示元件
WO2015012368A1 (fr) * 2013-07-25 2015-01-29 日産化学工業株式会社 Élément d'affichage à cristaux liquides, agent d'alignement de cristaux liquides, et film d'alignement de cristaux liquides
CN105637410B (zh) * 2013-08-14 2019-08-02 日产化学工业株式会社 液晶表示元件
KR102069288B1 (ko) * 2013-08-28 2020-01-23 삼성디스플레이 주식회사 액정 배향제 및 액정 표시 장치
TWI487731B (zh) * 2013-09-04 2015-06-11 Daxin Materials Corp 液晶配向劑、液晶配向膜及液晶顯示元件
CN106462011B (zh) * 2014-03-27 2021-11-12 日产化学工业株式会社 液晶表示元件、液晶取向膜和液晶取向处理剂
EP3159737B1 (fr) * 2014-06-17 2021-05-26 Nissan Chemical Corporation Élément d'affichage à cristaux liquides, film d'alignement de cristaux liquides et agent de traitement d'alignement de cristaux liquides
JP6418317B2 (ja) * 2015-03-02 2018-11-07 日産化学株式会社 液晶表示素子
TWI602811B (zh) * 2016-10-04 2017-10-21 達興材料股份有限公司 二胺化合物、聚合物、絕緣膜與電子裝置
TWI679217B (zh) * 2018-03-02 2019-12-11 達興材料股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件
JP2022067054A (ja) * 2020-10-19 2022-05-02 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子及び液晶素子の製造方法
JPWO2023013622A1 (fr) * 2021-08-06 2023-02-09

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008010528A1 (fr) * 2006-07-18 2008-01-24 Nissan Chemical Industries, Ltd. agent d'orientation de cristaux liquides, film orienté de cristaux liquides et élément d'affichage à cristaux liquides L'utilisant
WO2009148100A1 (fr) * 2008-06-04 2009-12-10 日産化学工業株式会社 Agent d’alignement de cristaux liquides et élément d’affichage à cristaux liquides l’utilisant
WO2010047316A1 (fr) * 2008-10-22 2010-04-29 日産化学工業株式会社 Agent d'alignement de cristaux liquides et élément à cristaux liquides utilisant ledit agent

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100205963B1 (ko) * 1997-05-29 1999-07-01 이서봉 액정 배향막용 신규 가용성 폴리이미드 수지
US6194039B1 (en) * 1999-10-22 2001-02-27 Elsicon, Inc. Materials for inducing alignment in liquid crystals and liquid crystal displays
JP4600616B2 (ja) * 2000-07-07 2010-12-15 Ｊｓｒ株式会社 液晶配向剤および液晶表示素子
US7113241B2 (en) * 2001-08-31 2006-09-26 Sharp Kabushiki Kaisha Liquid crystal display and method of manufacturing the same
JP4013052B2 (ja) * 2002-09-25 2007-11-28 日産化学工業株式会社 液晶配向処理剤および液晶表示素子
JP4122516B2 (ja) 2003-11-12 2008-07-23 Ｊｓｒ株式会社 液晶配向膜およびその製造法
CN1762978B (zh) * 2004-10-05 2010-12-15 Jsr株式会社 新型二胺化合物、聚合物以及液晶取向剂
TWI406838B (zh) * 2006-08-04 2013-09-01 Jnc Corp 二胺、液晶配向劑、液晶配向膜和液晶顯示裝置
JP2008176304A (ja) 2006-12-22 2008-07-31 Jsr Corp 液晶配向剤、液晶配向膜、液晶表示素子および光学部材
JP5071659B2 (ja) * 2007-02-22 2012-11-14 Ｊｓｒ株式会社 液晶配向剤および液晶表示素子
KR101492656B1 (ko) 2007-03-23 2015-02-12 닛산 가가쿠 고교 가부시키 가이샤 디아민 화합물, 폴리아믹산, 폴리이미드 및 액정 배향 처리제
JP5067570B2 (ja) * 2007-08-01 2012-11-07 Ｊｓｒ株式会社 液晶配向剤、液晶配向膜および液晶表示素子
KR101589322B1 (ko) * 2008-01-25 2016-01-27 닛산 가가쿠 고교 가부시키 가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
TWI460209B (zh) * 2008-05-09 2014-11-11 Chi Mei Corp Liquid crystal aligning agent and method for producing liquid crystal alignment film
WO2010035719A1 (fr) 2008-09-24 2010-04-01 日産化学工業株式会社 Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008010528A1 (fr) * 2006-07-18 2008-01-24 Nissan Chemical Industries, Ltd. agent d'orientation de cristaux liquides, film orienté de cristaux liquides et élément d'affichage à cristaux liquides L'utilisant
WO2009148100A1 (fr) * 2008-06-04 2009-12-10 日産化学工業株式会社 Agent d’alignement de cristaux liquides et élément d’affichage à cristaux liquides l’utilisant
WO2010047316A1 (fr) * 2008-10-22 2010-04-29 日産化学工業株式会社 Agent d'alignement de cristaux liquides et élément à cristaux liquides utilisant ledit agent

Cited By (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101938923B1 (ko) * 2011-11-01 2019-04-10 닛산 가가쿠 가부시키가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
JP2017226647A (ja) * 2011-11-01 2017-12-28 日産化学工業株式会社 新規なジアミン化合物、ポリイミド前駆体及びポリイミド
KR20140084278A (ko) * 2011-11-01 2014-07-04 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
JPWO2013065755A1 (ja) * 2011-11-01 2015-04-02 日産化学工業株式会社 液晶配向処理剤、液晶配向膜及び液晶表示素子
WO2013105523A1 (fr) * 2012-01-12 2013-07-18 和光純薬工業株式会社 Agent d'alignement de cristaux liquides
JPWO2013105523A1 (ja) * 2012-01-12 2015-05-11 和光純薬工業株式会社 液晶配向剤
WO2013115387A1 (fr) * 2012-02-03 2013-08-08 日産化学工業株式会社 Agent d'alignement des cristaux liquides, film d'alignement des cristaux liquides et élément d'affichage à cristaux liquides
CN104246591B (zh) * 2012-02-03 2017-08-08 日产化学工业株式会社 液晶取向处理剂、液晶取向膜及液晶显示元件
KR20140120353A (ko) * 2012-02-03 2014-10-13 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
TWI575022B (zh) * 2012-02-03 2017-03-21 Nissan Chemical Ind Ltd Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
KR102012060B1 (ko) 2012-02-03 2019-10-14 닛산 가가쿠 가부시키가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
JPWO2013115387A1 (ja) * 2012-02-03 2015-05-11 日産化学工業株式会社 液晶配向処理剤、液晶配向膜及び液晶表示素子
KR102035366B1 (ko) * 2012-02-22 2019-10-22 닛산 가가쿠 가부시키가이샤 조성물, 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
JP2020056034A (ja) * 2012-02-22 2020-04-09 日産化学株式会社 組成物、液晶配向処理剤、液晶配向膜及び液晶表示素子
JPWO2013125595A1 (ja) * 2012-02-22 2015-07-30 日産化学工業株式会社 組成物、液晶配向処理剤、液晶配向膜及び液晶表示素子
JP2018083943A (ja) * 2012-02-22 2018-05-31 日産化学工業株式会社 組成物、液晶配向処理剤、液晶配向膜及び液晶表示素子
TWI568796B (zh) * 2012-02-22 2017-02-01 Nissan Chemical Ind Ltd A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device
KR20140129217A (ko) * 2012-02-22 2014-11-06 닛산 가가쿠 고교 가부시키 가이샤 조성물, 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
CN104136542A (zh) * 2012-02-22 2014-11-05 日产化学工业株式会社 组合物、液晶取向处理剂、液晶取向膜及液晶显示元件
WO2013125595A1 (fr) * 2012-02-22 2013-08-29 日産化学工業株式会社 Composition, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides
CN103364996A (zh) * 2012-03-30 2013-10-23 索尼公司 液晶显示装置及其制造方法
CN104737069B (zh) * 2012-08-30 2018-08-10 日产化学工业株式会社 液晶取向处理剂及使用该液晶取向处理剂的液晶显示元件
CN104737069A (zh) * 2012-08-30 2015-06-24 日产化学工业株式会社 液晶取向处理剂及使用该液晶取向处理剂的液晶显示元件
CN105122128A (zh) * 2013-02-13 2015-12-02 日产化学工业株式会社 液晶取向膜的制造方法、液晶取向膜、液晶表示元件和液晶取向剂
CN105122128B (zh) * 2013-02-13 2017-11-28 日产化学工业株式会社 液晶取向膜的制造方法、液晶取向膜、液晶表示元件和液晶取向剂
KR102172134B1 (ko) 2013-02-13 2020-10-30 닛산 가가쿠 가부시키가이샤 액정 배향막의 제조 방법, 액정 배향막, 액정 표시 소자 및 액정 배향제
KR20150119199A (ko) * 2013-02-13 2015-10-23 닛산 가가쿠 고교 가부시키 가이샤 액정 배향막의 제조 방법, 액정 배향막, 액정 표시 소자 및 액정 배향제
KR102078613B1 (ko) 2013-03-19 2020-02-18 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막, 액정 표시 소자, 중합체 및 화합물
KR20140114749A (ko) * 2013-03-19 2014-09-29 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막, 액정 표시 소자, 중합체 및 화합물
JP2018205763A (ja) * 2014-02-25 2018-12-27 Jsr株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
KR102193532B1 (ko) * 2014-02-25 2020-12-21 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
KR20150100494A (ko) * 2014-02-25 2015-09-02 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
JP2016042177A (ja) * 2014-02-25 2016-03-31 Jsr株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
EP3163367A4 (fr) * 2014-06-25 2018-01-24 Nissan Chemical Industries, Ltd. Élément d'affichage à cristaux liquides
US10386681B2 (en) * 2014-06-25 2019-08-20 Nissan Chemical Industries, Ltd. Liquid crystal display element
JPWO2016204178A1 (ja) * 2015-06-16 2018-04-12 三菱ケミカル株式会社 配向膜及び配向膜用組成物
WO2016204178A1 (fr) * 2015-06-16 2016-12-22 三菱化学株式会社 Film d'alignement, et composition pour films d'alignement
JPWO2017038627A1 (ja) * 2015-08-28 2018-07-12 日産化学工業株式会社 ラジカル発生能及び塩基発生能を有する新規なジアミン化合物及びそれを原料とする新規なイミド系重合体
WO2017038627A1 (fr) * 2015-08-28 2017-03-09 日産化学工業株式会社 Nouveau composé de diamine possédant une capacité de génération de radicaux et une capacité de génération de bases, et nouveau polymère imide utilisant ledit nouveau composé de diamine comme matériau de départ
JP2022140484A (ja) * 2016-02-15 2022-09-26 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
JP7351382B2 (ja) 2016-02-15 2023-09-27 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
KR102438830B1 (ko) 2016-08-03 2022-08-31 닛산 가가쿠 가부시키가이샤 곡면 형상을 갖는 액정 패널을 구비하는 액정 표시 소자 및 그것을 위한 액정 배향제
JPWO2018025872A1 (ja) * 2016-08-03 2019-06-20 日産化学株式会社 曲面形状を有する液晶パネルを備える液晶表示素子及びそのための液晶配向剤
KR20190031570A (ko) * 2016-08-03 2019-03-26 닛산 가가쿠 가부시키가이샤 곡면 형상을 갖는 액정 패널을 구비하는 액정 표시 소자 및 그것을 위한 액정 배향제
JPWO2019244939A1 (ja) * 2018-06-19 2021-07-15 日産化学株式会社 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子並びに該液晶表示素子の製造方法、ジアミン化合物
WO2019244939A1 (fr) * 2018-06-19 2019-12-26 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 l'utilisant, et procédé de production dudit élément d'affichage à cristaux liquides, et composé diamine
JP7401853B2 (ja) 2018-06-19 2023-12-20 日産化学株式会社 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子並びに該液晶表示素子の製造方法
WO2020085450A1 (fr) * 2018-10-26 2020-04-30 日産化学株式会社 Agent d'alignment de cristaux liquides, film d'alignment de cristaux liquides et élément d'affichage à cristaux liquides
JPWO2020085450A1 (ja) * 2018-10-26 2021-09-16 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
JP7375766B2 (ja) 2018-10-26 2023-11-08 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
WO2021065933A1 (fr) 2019-10-02 2021-04-08 日産化学株式会社 Élément de commande de lumière à cristaux liquides
WO2023157876A1 (fr) 2022-02-17 2023-08-24 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

Also Published As

Publication number Publication date
TWI447146B (zh) 2014-08-01
KR20130091651A (ko) 2013-08-19
JP5936000B2 (ja) 2016-06-15
TW201209077A (en) 2012-03-01
JPWO2011132752A1 (ja) 2013-07-18
CN102947753B (zh) 2015-09-02
CN102947752B (zh) 2015-10-07
TWI486380B (zh) 2015-06-01
WO2011132752A1 (fr) 2011-10-27
JPWO2011132751A1 (ja) 2013-07-18
KR101775181B1 (ko) 2017-09-05
TW201209076A (en) 2012-03-01
CN102947752A (zh) 2013-02-27
KR20130091652A (ko) 2013-08-19
CN102947753A (zh) 2013-02-27
KR101775182B1 (ko) 2017-09-05
JP5713009B2 (ja) 2015-05-07

Similar Documents

Publication Publication Date Title
JP5713009B2 (ja) 液晶配向処理剤、液晶配向膜及び液晶表示素子
JP5904121B2 (ja) 液晶配向処理剤、液晶配向膜及び液晶表示素子
WO2013035803A1 (fr) Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JP6368955B2 (ja) 液晶配向処理剤、液晶配向膜および液晶表示素子
JP5900337B2 (ja) 液晶配向処理剤、液晶配向膜及び液晶表示素子
JP5998931B2 (ja) 液晶配向処理剤、液晶配向膜、及び液晶表示素子
JP6331028B2 (ja) 液晶配向処理剤、液晶配向膜および液晶表示素子
JP6065074B2 (ja) ジアミン化合物、ポリイミド前駆体及びポリイミド
JP6465159B2 (ja) 新規なジアミン化合物、ポリイミド前駆体及びポリイミド
JP5874646B2 (ja) 液晶配向処理剤、液晶配向膜および液晶表示素子
JP6052171B2 (ja) 組成物、液晶配向処理剤、液晶配向膜及び液晶表示素子
JP6079627B2 (ja) 組成物、液晶配向処理剤、液晶配向膜及び液晶表示素子
WO2013115387A1 (fr) Agent d'alignement des cristaux liquides, film d'alignement des cristaux liquides et élément d'affichage à cristaux liquides
JP6003882B2 (ja) 組成物、液晶配向処理剤、液晶配向膜、及び液晶表示素子
WO2014126102A1 (fr) Procédé de production pour film d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides et agent d'alignement de cristaux liquides
JP6264577B2 (ja) 液晶配向処理剤、液晶配向膜および液晶表示素子

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180030910.9

Country of ref document: CN

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

Ref document number: 11772083

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012511706

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20127030217

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 11772083

Country of ref document: EP

Kind code of ref document: A1