WO2014084309A1 - 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
WO2014084309A1
WO2014084309A1 PCT/JP2013/082053 JP2013082053W WO2014084309A1 WO 2014084309 A1 WO2014084309 A1 WO 2014084309A1 JP 2013082053 W JP2013082053 W JP 2013082053W WO 2014084309 A1 WO2014084309 A1 WO 2014084309A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
carbon atoms
formula
group
alkyl group
Prior art date
Application number
PCT/JP2013/082053
Other languages
English (en)
Japanese (ja)
Inventor
雅章 片山
徳俊 三木
幸司 巴
奈穂 菊池
保坂　和義
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 KR1020197028318A priority Critical patent/KR20190112215A/ko
Priority to KR1020177006142A priority patent/KR20170029022A/ko
Priority to CN201380071507.XA priority patent/CN104956259B/zh
Priority to JP2014549891A priority patent/JP6331028B2/ja
Publication of WO2014084309A1 publication Critical patent/WO2014084309A1/fr

Links

Images

Classifications

    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • 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
    • G02F1/133715—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films by first depositing a monomer
    • 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
    • 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.
  • liquid crystal display elements have become widely used in large-screen liquid crystal televisions and high-definition mobile applications (display parts of digital cameras and mobile phones).
  • the unevenness of the step of the substrate is getting larger.
  • the liquid crystal alignment film is uniformly coated on a large substrate or a step from the viewpoint of display characteristics.
  • a liquid crystal alignment treatment agent also called coating solution
  • polyamic acid or solvent-soluble polyimide also called resin
  • resin which is a polyimide precursor
  • the solvent of the coating solution includes N-methyl-2-pyrrolidone, ⁇ -butyrolactone, and the like that are excellent in the solubility of the resin (also referred to as a good solvent), and the uniformity of the liquid crystal alignment film.
  • butyl cellosolve which is a solvent having low resin solubility (also referred to as a poor solvent), or the like is mixed (see, for example, Patent Document 1).
  • a liquid crystal alignment treatment agent using a polyamic acid or a solvent-soluble polyimide obtained by using a diamine compound having a side chain tends to lower the coating film uniformity of the liquid crystal alignment film.
  • uniform coating properties i.e., when repelling or pinholes occur
  • that portion becomes a display defect. Therefore, it is necessary to increase the amount of introduction of a poor solvent having high wettability of the coating solution to the substrate.
  • a poor solvent is inferior in the ability to dissolve a polyamic acid or a polyimide, there exists a problem that resin precipitation will occur when it mixes in large quantities.
  • liquid crystal display elements have been used for mobile applications such as smartphones and tablet computers.
  • a sealant used for bonding the substrates of the liquid crystal display elements is present at a position close to the end of the liquid crystal alignment film. Therefore, when the coating property of the end portion of the liquid crystal alignment film is deteriorated, that is, when the end portion of the liquid crystal alignment film is not a straight line, or the end portion is raised, between the substrates of the sealing agent. The adhesive effect is lowered, and the reliability of the liquid crystal display element is lowered.
  • Another object of the present invention is to provide a liquid crystal display element having the above-described liquid crystal alignment film.
  • an object of the present invention is to provide a liquid crystal alignment treatment agent that can provide the above-described liquid crystal alignment film.
  • the present invention has the following gist.
  • Liquid crystal aligning agent containing the following (A) component and (B) component.
  • (A) Component Propylene glycol monobutyl ether.
  • Y 1 represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
  • Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15)
  • Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15) ), —O—, —CH 2 O—, —COO— or —OCO—
  • Y 4 is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a carbon number of 12 to 25
  • an 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, or an alkyl group having 1 to 3 carbon
  • Y 5 represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, 3 alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms may be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms, n is an integer of 0 ⁇ 4, Y 6 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
  • Y 1 represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
  • Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15)
  • Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15) ), —O—, —CH 2 O—, —COO— or —OCO—
  • Y 4 is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a carbon number of 12 to 25
  • an 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, or an alkyl group having 1 to 3 carbon
  • Y 5 represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, atoms 1 alkoxyl group-3, fluorine-containing alkyl group having 1 to 3 carbon atoms may be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms, n is an integer of 0 - 4, 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 or a fluorine-containing alkoxyl group having 1 to 18 carbon
  • X represents a substituent having a structure selected from Formula [2a], Formula [2b], Formula [2c] or Formula [2d] below, and m represents an integer of 1 to 4) .
  • a represents an integer of 0 to 4
  • b represents an integer of 0 to 4
  • X 1 and X 2 are each independently carbon.
  • X 3 represents an alkyl group having 1 to 5 carbon atoms).
  • the tetracarboxylic acid component in the polymer of the component (B) contains a compound represented by the following formula [3], according to any one of (1) to (3) above Liquid crystal aligning agent.
  • Z 1 is a group having a structure selected from the following formulas [3a] to [3j]).
  • Z 2 to Z 5 represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
  • Z 6 and Z 7 are A hydrogen atom or a methyl group, which may be the same or different.
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D 3 represents an alkyl group having 1 to 4 carbon atoms
  • Polymerizability comprising a liquid crystal layer between a pair of substrates provided with electrodes, and polymerized by at least one of active energy rays and heat between at least one of the pair of substrates and the liquid crystal layer.
  • a liquid crystal composition containing a compound is used, and the liquid crystal display device is manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.
  • the liquid crystal aligning film as described in 9).
  • a liquid crystal display element comprising the liquid crystal alignment film according to (11).
  • a liquid crystal display device comprising the liquid crystal alignment film according to (13).
  • liquid crystal aligning agent containing a solvent having a specific structure of the present invention and a polymer having a side chain of a specific structure
  • the wet spreading property of the coating solution to the substrate is high, and uniform coating properties can be obtained.
  • the liquid crystal aligning film which is excellent in these characteristics can be provided.
  • the liquid crystal display element which has said liquid crystal aligning film, and the liquid-crystal aligning agent which can provide said liquid crystal aligning film can be provided.
  • the present invention relates to a liquid crystal alignment treatment agent containing the following components (A) and (B), a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.
  • Component (A) propylene glycol monobutyl ether (also referred to as a specific solvent).
  • Y 1 represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
  • Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15)
  • Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15) ), —O—, —CH 2 O—, —COO— or —OCO—
  • Y 4 is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a carbon number of 12 to 25
  • an 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, or an alkyl group having 1 to 3 carbon
  • Y 5 represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, 3 alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms may be substituted with a fluorine-containing alkoxyl group or a fluorine atom having 1 to 3 carbon atoms, n is an integer of 0 ⁇ 4, Y 6 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
  • the specific solvent of the present invention can be used as a poor solvent used for enhancing the coating properties of the liquid crystal alignment film. Since the specific solvent of the present invention has higher wettability of the coating solution to the substrate than ethylene glycol monobutyl ether (also referred to as butyl cellosolve or BCS) which is usually used as a poor solvent, It is possible to obtain a liquid crystal alignment film excellent in coating properties in which holes are not easily generated. Furthermore, since the wet spreading property of the coating solution is increased, the linearity of the end portion of the liquid crystal alignment film is increased, and the bulge of the end portion can be suppressed.
  • ethylene glycol monobutyl ether also referred to as butyl cellosolve or BCS
  • the component (B) of the present invention is at least one polymer selected from a polyimide precursor or polyimide. Especially, when using the composition of this invention for a liquid crystal aligning film as a liquid crystal aligning agent, it is preferable to use the specific polymer which has the specific side chain structure shown by said Formula [1].
  • the specific side chain structure of the present invention has 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 in the side chain portion.
  • These benzene rings, cyclohexyl rings, heterocyclic rings, or divalent organic groups having 12 to 25 carbon atoms and having a steroid skeleton exhibit a rigid structure as compared with conventional long-chain alkyl groups.
  • the stability of the side chain site to heat and ultraviolet light is improved, and a liquid crystal alignment film having a stable pretilt angle against heat and light can be obtained.
  • the liquid crystal aligning agent containing the specific solvent and specific polymer of the present invention can form a liquid crystal alignment film having excellent coating properties. Moreover, the liquid crystal aligning agent containing the specific solvent and specific polymer of the present invention becomes a liquid crystal alignment film whose pretilt angle does not change even when exposed to high temperature and light irradiation for a long time. Further, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having excellent display characteristics can be provided.
  • the specific solvent of the present invention is propylene glycol monobutyl ether.
  • the specific solvent of the present invention is preferably 5 to 70% by mass of the whole organic solvent contained in the liquid crystal aligning agent in order to enhance the effect of increasing the wet spreading property of the coating solution to the substrate described above.
  • 10 to 70% by mass is preferable. More preferred is 10 to 60% by mass.
  • the specific polymer which is the component (B) of the present invention is a polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.
  • the polyimide precursor has a structure represented by the following formula [A].
  • R 1 is a tetravalent organic group
  • R 2 is a divalent organic group having a carboxyl group
  • a 1 and A 2 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • Each of A 3 and A 4 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group, and may be the same or different
  • n is Indicates a positive integer).
  • the diamine component is a diamine compound having two primary or secondary amino groups in the molecule
  • the tetracarboxylic acid component is a tetracarboxylic acid compound, tetracarboxylic dianhydride, dicarboxylic acid dihalide compound,
  • a dicarboxylic acid dialkyl ester compound or a dialkyl ester dihalide compound may be mentioned.
  • R 1 and R 2 are as defined in formula [A]).
  • the polymer of the formula [D] obtained above is added to the alkyl group having 1 to 8 carbon atoms of A 1 and A 2 represented by the formula [A] and the formula [A] by a usual synthesis method. It is also possible to introduce an alkyl group having 1 to 5 carbon atoms or an acetyl group of A 3 and A 4 shown.
  • the specific polymer of the present invention comprises at least one heavy selected from a polyimide precursor or a polyimide obtained by reacting a diamine component having a specific side chain structure represented by the following formula [1] with a tetracarboxylic acid component. It is a coalescence.
  • Y 1 represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. .
  • a single bond — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO -Is preferred.
  • More preferred is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15).
  • a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
  • Y 3 represents a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. .
  • a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O— or —COO— is preferable from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • Y 4 is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • Y 4 may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms and having a steroid skeleton. Among these, from the viewpoint of ease of synthesis, a benzene ring, a cyclohexane ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton is preferable.
  • Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • a benzene ring or a cyclohexane ring is preferable.
  • n represents an integer of 0 to 4.
  • 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.
  • 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, 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. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
  • a diamine compound having a specific side chain structure is preferably used as a part of the raw material.
  • a diamine compound represented by the following formula [1a] also referred to as a specific side chain diamine compound.
  • Y 1 represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. .
  • a single bond — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO -Is preferred.
  • More preferred is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15).
  • a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
  • Y 3 represents a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—. .
  • a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O— or —COO— is preferable from the viewpoint of ease of synthesis. More preferred is a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • Y 4 is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • Y 4 may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms and having a steroid skeleton. Among these, from the viewpoint of ease of synthesis, a benzene ring, a cyclohexane ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton is preferable.
  • Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • a benzene ring or a cyclohexane ring is preferable.
  • n represents an integer of 0 to 4.
  • 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.
  • 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, 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. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
  • Preferable combinations of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and n in the formula [1a] include items 13 to 34 of International Publication No. WO2011 / 132751 (published on October 27, 2011). Examples thereof include the same combinations as (2-1) to (2-629) listed in Tables 6 to 47 in the section. In each table of the International Publication, Y 1 to Y 6 in the present invention are shown as Y 1 to Y 6 , but Y 1 to Y 6 are read as Y 1 to Y 6 .
  • (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) are preferred.
  • Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240) or (2-603) to (2- 606).
  • m is an integer of 1 to 4. Preferably, it is an integer of 1.
  • the structure is represented by the following formula [1a-1] to [1a-31].
  • R 1 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or —CH 2 OCO—
  • R 2 represents C1-22 linear or branched alkyl group, C1-22 linear or branched alkoxyl group, C1-22 linear or branched fluorine-containing alkyl group or fluorine-containing alkoxyl Group).
  • R 3 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 — or —CH 2 —, wherein R 4 is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, carbon number 1 to 22 linear or branched fluorine-containing alkyl groups or fluorine-containing alkoxyl groups).
  • R 5 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O— or —NH—, wherein R 6 is fluorine, cyano, trifluoromethane, nitro, azo, formyl, acetyl, acetoxy Or a hydroxyl group).
  • R 7 is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is Trans isomer).
  • R 8 is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is Trans isomer).
  • a 4 is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
  • a 3 is a 1,4-cyclohexylene group or A 2 -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.
  • Said specific side chain type diamine compound according to the characteristics such as solubility in a solvent when used as a specific polymer of the present invention, liquid crystal alignment when used as a liquid crystal alignment film, voltage holding ratio and accumulated charge, One type or a mixture of two or more types can also be used.
  • diamine component for producing the specific polymer that is the component (B) of the present invention it is also preferable to use a diamine compound represented by the following formula [2].
  • X represents a substituent having a structure selected from the following formula [2a], formula [2b], formula [2c] or formula [2d].
  • m represents an integer of 1 to 4.
  • a represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis
  • b represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis
  • X 1 and X 2 each independently represent a hydrocarbon group having 1 to 12 carbon atoms.
  • X 3 represents an alkyl group having 1 to 5 carbon atoms.
  • examples of the diamine compound represented by the formula [2] include 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5- In addition to diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, the following formula [ Examples thereof include diamine compounds having structures represented by 2-1] to [2-6].
  • 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid 2, Preference is given to 5-diaminobenzoic acid, 3,5-diaminobenzoic acid, diamine compounds of the formula [2-1], formula [2-2] or formula [2-3].
  • the diamine compound represented by the formula [2] has characteristics such as solubility and coating properties of the specific polymer of the present invention in a solvent, liquid crystal alignment property, voltage holding ratio, and accumulated charge when a liquid crystal alignment film is formed. Depending on the situation, one kind or a mixture of two or more kinds can be used.
  • diamine component for producing the specific polymer which is the component (B) of the present invention a diamine compound other than the diamine compounds represented by the formulas [1a] and [2] (also referred to as other diamine compounds) is used as the diamine component.
  • diamine component for producing the specific polymer which is the component (B) of the present invention
  • a diamine compound other than the diamine compounds represented by the formulas [1a] and [2] also referred to as other diamine compounds
  • Can be used as Specific examples of other diamine compounds are shown below, but are not limited to these examples.
  • examples of other diamine compounds include those having an alkyl group, a fluorine-containing alkyl group or a heterocyclic ring in the diamine side chain.
  • diamine compounds represented by the following formulas [DA1] to [DA13] can be exemplified.
  • a 1 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).
  • a 1 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or —NH—
  • a 2 represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms).
  • p represents an integer of 1 to 10).
  • diamine compounds represented by the following formulas [DA12] to [DA13] can also be used as other diamine compounds.
  • n represents an integer of 1 to 5
  • diamine compounds represented by the following formulas [DA18] to [DA21] can also be used.
  • a 1 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —O —, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON (CH 3 ) — Or —N (CH 3 ) CO—, each of m 1 and m 2 represents an integer of 0 to 4, and m 1 + m 2 represents an integer of 1 to 4, and in the formula [DA19], m 3 and m 4 each represent an integer of 1 to 5, and in formula [DA20], A 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms, m 5 represents an integer of 1 to 5, [DA21] in, A 3 is
  • a 1 represents —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ).
  • a 3 is a hydrocarbon group, A 3 is a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO— or —O (CH 2 ) m — (m is an integer of 1 to 5), A 4 is a nitrogen-containing aromatic heterocycle, and n is 1 to 4 is an integer).
  • diamine compounds represented by the following formula [DA23] and formula [DA24] can also be used as other diamine compounds.
  • the above-mentioned other diamine compounds may be one or two kinds depending on the solubility of the specific polymer of the present invention in a solvent and the properties of liquid crystal orientation, voltage holding ratio, accumulated charge, etc.
  • the above can also be mixed and used.
  • tetracarboxylic acid component As the tetracarboxylic acid component for producing the specific polymer which is the component (B) of the present invention, a tetracarboxylic dianhydride represented by the following formula [3] or a tetracarboxylic acid which is a tetracarboxylic acid derivative thereof It is preferable to use a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound (all are collectively referred to as a specific tetracarboxylic acid component).
  • Z 1 is a group having a structure selected from the following formulas [3a] to [3j].
  • Z 2 to Z 5 represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
  • Z 6 and Z 7 represent a hydrogen atom or a methyl group, and may be the same or different.
  • Z 1 is represented by the formula [3a], from the viewpoint of ease of synthesis and polymerization reactivity when producing a polymer.
  • a structure represented by Formula [3c], Formula [3d], Formula [3e], Formula [3f], or Formula [3g] is preferable. More preferred is a structure represented by formula [3a], formula [3e], formula [3f] or formula [3g], and particularly preferred is formula [3e], formula [3f] or formula [3g]. It is.
  • the specific tetracarboxylic acid component of the present invention is preferably 1 mol% or more of the total tetracarboxylic acid component. More preferred is 5 mol% or more, and particularly preferred is 10 mol% or more.
  • the usage-amount is made into 20 mol% or more of the whole tetracarboxylic acid component, and it is desired An effect is obtained. Preferably, it is 30 mol% or more.
  • all of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure of the formula [3e], the formula [3f], or the formula [3g].
  • tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used as long as the effects of the present invention are not impaired.
  • tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds, or dialkyl ester dihalide compounds.
  • tetracarboxylic acid components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalene.
  • Tetracarboxylic acid 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro 2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5- Pyridine
  • the specific tetracarboxylic acid component and other tetracarboxylic acid components depend on the solubility of the specific polymer of the present invention in a solvent and the characteristics of liquid crystal alignment, voltage holding ratio, accumulated charge, etc. when used as a liquid crystal alignment film. In addition, one type or a mixture of two or more types can be used.
  • the method for synthesizing the specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid.
  • a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine compound, dehydration polycondensation reaction of tetracarboxylic acid and primary or secondary diamine compound Or a polycarboxylic acid dihalide and a primary or secondary diamine compound are polycondensed to obtain a polyamic acid.
  • a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine compound, a dicarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and a primary a method of polycondensation with a secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.
  • polyimide In order to obtain polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
  • the reaction between the diamine component and the tetracarboxylic acid component is usually carried out with the diamine component and the tetracarboxylic acid component in an organic solvent.
  • the organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the organic solvent used for reaction below is given, it is not limited to these examples.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and solvents represented by the following formulas [D-1] to [D-3].
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • D 3 represents an alkyl group having 1 to 4 carbon atoms
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is dispersed or dissolved in the organic solvent as it is.
  • a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent a method of alternately adding a diamine component and a tetracarboxylic acid component, etc. Any of these methods may be used.
  • the polymerization temperature 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 is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, 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 to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the 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 ring closure of the polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%. It can be arbitrarily adjusted according to the purpose.
  • Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalytic 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, and trioctylamine. Among them, pyridine is preferable because it has a basicity appropriate for advancing 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 solvent and precipitated.
  • 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 in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating.
  • the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.
  • the molecular weight of the specific polymer of the present invention is 5 in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained therefrom, workability during film formation, and coating properties. It is preferably from 1,000 to 1,000,000, more preferably from 10,000 to 150,000.
  • the liquid crystal aligning agent of this invention is a coating solution for forming a liquid crystal aligning film, and is a coating solution containing a specific solvent and a specific polymer.
  • All of the polymer components in the liquid crystal aligning agent of the present invention may be the specific polymer of the present invention, or other polymers may be mixed.
  • the content of the other polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass, of the specific polymer of the present invention.
  • examples of other polymers include a diamine compound represented by the formula [1a], a diamine compound represented by the formula [2], and a polyimide polymer that does not use a specific tetracarboxylic acid component.
  • a polymer other than the polyimide polymer specifically, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or polysiloxane may be used.
  • the organic solvent in the liquid crystal alignment treatment agent of the present invention preferably has an organic solvent content of 70 to 99.9% by mass from the viewpoint of forming a uniform liquid crystal alignment film by coating. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.
  • 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 (also referred to as a good solvent) that dissolves the specific polymer.
  • an organic solvent also referred to as a good solvent
  • a good solvent is given to the following, it is not limited to these examples.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and ⁇ -butyrolactone are preferably used.
  • the solubility of the specific polymer in the solvent is high, it is preferable to use the solvents represented by the formulas [D-1] to [D-3] (also referred to as component (D) above).
  • the good solvent in the liquid crystal aligning agent of the present invention is preferably 10 to 80% by mass of the total solvent contained in the liquid crystal aligning agent. Of these, 20 to 70% by mass is preferable. More preferred is 30 to 60% by mass.
  • a specific solvent propylene glycol monobutyl ether as a component is contained.
  • the specific solvent is preferably 5 to 70% by mass of the whole organic solvent contained in the liquid crystal aligning agent. Among these, 10 to 70% by mass is preferable. More preferred is 10 to 60% by mass.
  • a poor solvent other than the specific solvent also referred to as other poor solvent
  • the liquid crystal aligning agent of the present invention can be used in combination with the liquid crystal aligning agent of the present invention as long as the effects of the present invention are not impaired.
  • Specific examples of other poor solvents are listed below, but are 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- Ethane All, 1,2-propanediol, 1,3-propan
  • 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monobutyl ether (also referred to as component (E) above) or the above-mentioned formulas [D-1] to [[ D-3] is preferably used.
  • These other poor solvents are preferably 1 to 60% by mass of the whole organic solvent contained in the liquid crystal aligning agent. Among these, 1 to 50% by mass is preferable. More preferred is 5 to 40% by mass.
  • the liquid crystal aligning agent of the present invention comprises a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, unless the effects of the present invention are impaired.
  • a crosslinkable compound having at least one substituent selected from the group, or a crosslinkable compound having a polymerizable unsaturated bond can also be introduced. 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, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl , Triglycidyl-p-
  • the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].
  • n represents an integer of 1 to 3).
  • n represents an integer of 1 to 3
  • n represents an integer of 1 to 3
  • n represents 1 to 100 Indicates an integer
  • n represents an integer of 1 to 10).
  • the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].
  • n represents an integer of 1 to 10
  • n represents an integer of 1 to 10
  • n represents an integer of 1 to 100, and in the formula [5-37], n represents an integer of 1 to 10).
  • polysiloxanes having at least one structure represented by the following formulas [5-38] to [5-40] can also be mentioned.
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represents a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, An alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, at least one of which represents a structure represented by the formula [5].
  • n an integer of 1 to 10
  • Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
  • a melamine resin, a urea resin, a guanamine resin, and a glycoluril such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
  • 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 or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per
  • 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.
  • Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.
  • crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol.
  • Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane or glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl
  • E 1 represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring; 2 represents a group selected from the following formula [7a] or [7b], and n represents an integer of 1 to 4.
  • crosslinkable compound used for the liquid-crystal aligning agent of this invention may be 1 type, and may be combined 2 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 all polymer components.
  • the amount is more preferably 0.1 to 100 parts by weight, and most preferably 1 to 50 parts by weight, based on 100 parts by weight of all polymer components.
  • liquid crystal alignment treatment agent of the present invention a compound that improves the uniformity of the film thickness and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used as long as the effects of the present invention are not impaired. Furthermore, a compound that improves the adhesion between the liquid crystal alignment film and the substrate can also be used.
  • Examples of the compound that further improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.). 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 all the polymer components contained in the liquid crystal aligning agent. It is.
  • 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 weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of all polymer components contained in the liquid crystal aligning agent. 20 parts by mass. 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 storage stability of the liquid crystal aligning agent may be deteriorated.
  • a dielectric or conductive material for changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film may be added.
  • the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment or light irradiation. In the case of vertical alignment, etc., it can be used as a liquid crystal alignment film without alignment treatment.
  • the substrate used at this time is not particularly limited as long as it is a highly transparent substrate.
  • a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed.
  • 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 for applying the liquid crystal aligning agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, an inkjet method, or the like is generally used.
  • Examples of other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and 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 preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal aligning agent, by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven.
  • the liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 30 to 250 ° C. If the thickness of the liquid crystal alignment 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. Is 10 to 100 nm.
  • the fired liquid crystal alignment 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 alignment treatment agent of the present invention by the above-described method and then preparing a liquid crystal cell by a known method.
  • a method for manufacturing a liquid crystal cell 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 place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of bonding the substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are dispersed, and the like.
  • the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and active energy rays and heat between at least one of the pair of substrates and the liquid crystal layer.
  • a liquid crystal produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while arranging a liquid crystal composition containing a polymerizable compound polymerized by at least one and applying a voltage between electrodes It is also preferably used for display elements.
  • ultraviolet rays are suitable as the active energy ray.
  • 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.
  • the above liquid crystal display element controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method.
  • a PSA method a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound.
  • the pretilt of the 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.
  • the PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.
  • a liquid crystal cell is prepared 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, and a polymerizable compound is produced by at least one of irradiation with ultraviolet rays and heating.
  • the orientation of the liquid crystal molecules can be controlled by polymerizing.
  • a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed.
  • the substrate is bonded and sealed.
  • a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed.
  • 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 part 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 polymerizable compound After producing the liquid crystal cell, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.
  • the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board
  • ultraviolet rays are suitable as the active energy ray.
  • the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.
  • liquid crystal aligning agent of the present invention contains a specific compound having a double bond site that reacts by irradiation with heat or ultraviolet rays, the alignment of liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. .
  • liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
  • Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which the substrate is attached and sealed after the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed.
  • the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
  • 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.
  • B1 3,5-Diaminobenzoic acid (diamine compound represented by the following formula [B1])
  • B2 Diamine compound represented by the following formula [B2]
  • C1 p-phenylenediamine (diamine compound represented by the following formula [C1])
  • C2 4,4′-diaminodiphenylamine (diamine compound represented by the following formula [C2])
  • C3 1,3-diamino-4-octadecyloxybenzene (diamine compound represented by the following formula [C3])
  • D1 1,2,3,4-cyclobutanetetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [D1])
  • D2 Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [D2])
  • D3 Tetracarboxylic dianhydride represented by the following formula [D3]
  • D4 Tetracarboxylic dianhydride represented by the following formula [D4]
  • PB Propylene glycol monobutyl ether (organic solvent as component (C) of the present invention)
  • NMP N-methyl-2-pyrrolidone
  • NEP N-ethyl-2-pyrrolidone
  • ⁇ -BL ⁇ -butyrolactone
  • PGME Propylene glycol monomethyl ether
  • PCS Ethylene glycol monopropyl ether
  • DEEE Diethylene glycol monoethyl ether (organic solvent which is component (E) of the present invention)
  • BCS Ethylene glycol monobutyl ether
  • the molecular weights of the polyimide precursor and the polyimide in the synthesis example are determined using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and a column (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as follows.
  • the imidation ratio of polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, ⁇ 5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and 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).
  • the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid that appear in the vicinity of 9.5 ppm 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.
  • This reaction solution was put into methanol (700 ml), and the resulting precipitate was separated by filtration. This deposit was wash
  • the imidation ratio of this polyimide was 55%, the number average molecular weight was 17,900, and the weight average molecular weight was 40,100.
  • This reaction solution was put into methanol (700 ml), and the resulting precipitate was separated by filtration. This deposit was wash
  • the imidation ratio of this polyimide was 50%, the number average molecular weight was 16,100, and the weight average molecular weight was 37,900.
  • Tables 2 to 4 show the liquid crystal aligning agents of the present invention.
  • liquid crystal alignment treatment agents obtained in the examples and comparative examples of the present invention, “Evaluation of printability of liquid crystal alignment treatment agents”, “Evaluation of ink jet coatability of liquid crystal alignment treatment agents”, “Preparation of liquid crystal cell and “Evaluation of liquid crystal alignment (normal cell)”, “Evaluation of pretilt angle (normal cell)” and “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)” were performed.
  • the conditions are as follows.
  • the pinhole of the liquid crystal alignment film was evaluated by visually observing the liquid crystal alignment film under a sodium lamp. Specifically, the number of pinholes confirmed on the liquid crystal alignment film was counted, and the smaller the number of pinholes, the better the evaluation.
  • Evaluation of the linearity of the edge part of a liquid crystal aligning film was performed by observing the liquid crystal aligning film of a right end part with respect to a printing direction with an optical microscope. Specifically, the difference between (1) and (2) in FIG. 1 of the liquid crystal alignment film image obtained by observing at an optical microscope magnification of 25, that is, the length of A in FIG. did. At that time, images of all liquid crystal alignment films were obtained at the same magnification. The shorter the length of A, the better the linearity of the end of the liquid crystal alignment film. Evaluation of the bulge of the edge part of a liquid crystal aligning film was performed by observing the liquid crystal aligning film of a right end part with respect to a printing direction by an optical microscope. Specifically, the length of B in FIG.
  • Tables 5 to 7 show the number of pinholes, the length of A, and the length of B of the liquid crystal alignment films obtained in Examples and Comparative Examples.
  • Liquid crystal aligning agent (6) obtained in Example 6 of the present invention Liquid crystal aligning agent (12) obtained in Example 12, Liquid crystal aligning agent (20) obtained in Example 20, and Example The liquid crystal aligning agent (21) obtained in No. 21 was subjected to pressure filtration with a membrane filter having a pore diameter of 1 ⁇ m, and ink jet coatability was evaluated.
  • As the ink jet coater HIS-200 (manufactured by Hitachi Plant Technology) was used.
  • Tables 5 and 6 show the number of pinholes in the liquid crystal alignment film obtained in the examples.
  • the surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.
  • Two obtained ITO substrates with a liquid crystal alignment film were prepared, combined with a 6 ⁇ m spacer sandwiched with the liquid crystal alignment film surface inside, and a sealant (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was printed.
  • the sealing agent was cured by heat treatment at 120 ° C. for 90 minutes in a heat-circulating clean oven to produce an empty cell.
  • Liquid crystal was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).
  • nematic liquid crystal MLC-6608
  • Liquid crystal alignment was evaluated using the liquid crystal cell obtained above. The liquid crystal alignment was confirmed by observing the liquid crystal cell with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to check for the presence of alignment defects. Specifically, those in which no alignment defect was observed were considered excellent in this evaluation (shown as good in Tables 8 to 10).
  • Tables 8 to 10 show the liquid crystal orientation results obtained in the examples and comparative examples.
  • the pretilt angle was evaluated using the liquid crystal cell obtained in “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)”.
  • the pretilt angle was measured after the liquid crystal injection, after heat treatment at 95 ° C. for 5 minutes, and after heat treatment at 120 ° C. for 5 hours. Furthermore, after the liquid crystal was injected, the liquid crystal cell after heat treatment at 95 ° C. for 5 minutes was measured after irradiation with ultraviolet rays of 10 J / cm 2 in terms of 365 nm. The smaller the change in the pretilt angle after the heat treatment at 120 ° C.
  • the pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Furthermore, ultraviolet irradiation was performed using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlite).
  • Tables 8 to 10 show the results of the pretilt angles obtained in the examples and comparative examples.
  • This solution was washed with pure water and IPA at the center with a 10 ⁇ 10 mm ITO electrode substrate with a pattern spacing of 20 ⁇ m (vertical 40 mm ⁇ width 30 mm, thickness 0.7 mm) and at the center with a 10 ⁇ 40 mm ITO electrode substrate
  • Spin coating was performed on the ITO surface (length 40 mm ⁇ width 30 mm, thickness 0.7 mm), and heat treatment was performed on a hot plate at 100 ° C. for 5 minutes to obtain a polyimide coating film having a thickness of 100 nm.
  • After the coated surface was washed with pure water, it was heat-treated at 100 ° C. for 15 minutes in a heat circulation type clean oven to obtain a substrate with a liquid crystal alignment film.
  • This substrate with a liquid crystal alignment film was combined with a 6 ⁇ m spacer sandwiched with the liquid crystal alignment film surface inside, and the periphery was adhered with a sealant to produce an empty cell.
  • a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) was added to the empty cell by a reduced pressure injection method, and a polymerizable compound (1) represented by the following formula was added to 100% by mass of the nematic liquid crystal (MLC-6608). Liquid crystal mixed with 0.3% by mass of the polymerizable compound (1) was injected, and the injection port was sealed to obtain a liquid crystal cell.
  • the response speed of the liquid crystal cell after the ultraviolet irradiation was higher than that of the liquid crystal cell before the ultraviolet irradiation, so that it was confirmed that the alignment direction of the liquid crystal was controlled. Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.
  • ECLIPSE E600WPOL polarizing microscope
  • NEP (18.9 g) and PB (14.4 g) were added to the polyamic acid solution (1) (10.5 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 1, and the mixture was heated to 25 ° C. And stirred for 3 hours to obtain a liquid crystal aligning agent (1).
  • This liquid crystal aligning agent (1) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • “evaluation of printability of liquid crystal aligning agent”, “preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)” and “pretilt "Evaluation of corner (normal cell)” was performed.
  • Example 2 NMP (16.0 g) and PB (15.7 g) are added to the polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 2, and the mixture is heated to 25 ° C. And stirred for 3 hours to obtain a liquid crystal aligning agent (2).
  • This liquid crystal aligning agent (2) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • Example 3 NMP (14.0 g), PB (11.8 g) and BCS (5.90 g) were added to the polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 2. ) And stirred at 25 ° C. for 3 hours to obtain a liquid crystal aligning agent (3).
  • This liquid crystal aligning agent (3) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • NMP (17.6 g) was added to the polyimide powder (3) (2.50 g) obtained by the synthesis method of Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (21.5 g) was added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (4).
  • This liquid crystal aligning agent (4) was confirmed to be a uniform solution without any abnormalities such as turbidity and generation of precipitates.
  • NMP (8.00 g) and NEP (12.0 g) were added to the polyimide powder (3) (2.55 g) obtained by the synthesis method of Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. .
  • PB (16.0 g) and BCS (4.00 g) were added, and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (5).
  • This liquid crystal aligning agent (5) was confirmed to be a uniform solution with no abnormalities such as turbidity and precipitation.
  • NMP (8.56 g) and NEP (12.8 g) were added to the polyimide powder (3) (1.55 g) obtained by the synthesis method of Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. .
  • PB (17.1 g) and BCS (4.30 g) were added, and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (6).
  • This liquid crystal aligning agent (6) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • “evaluation of ink jet coatability of liquid crystal aligning agent” was performed under the above-described conditions.
  • NMP (19.6 g) was added to the polyimide powder (4) (2.50 g) obtained by the synthesis method of Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (3.90 g), PCS (7.80 g) and BCS (7.80 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (7).
  • This liquid crystal aligning agent (7) was confirmed to be a uniform solution with no abnormalities such as turbidity and precipitation.
  • ⁇ -BL (18.0 g) was added to the polyimide powder (5) (2.56 g) obtained by the synthesis method of Synthesis Example 5 and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (16.0g) and PGME (6.00g) were added to this solution, and it stirred at 40 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (8).
  • This liquid crystal aligning agent (8) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • NEP (22.0 g) was added to the polyimide powder (6) (2.55 g) obtained by the synthesis method of Synthesis Example 6 and dissolved by stirring at 70 ° C. for 24 hours.
  • PB 8.00 g
  • BCS (10.0 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (9).
  • This liquid crystal aligning agent (9) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • Example 10 NMP (6.00 g) and NEP (12.0 g) were added to the polyimide powder (7) (2.55 g) obtained by the synthesis method of Synthesis Example 7 and dissolved by stirring at 70 ° C. for 24 hours. . To this solution were added PB (16.0 g) and DEEE (6.00 g), and the mixture was stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (10). This liquid crystal aligning agent (10) was confirmed to be a uniform solution with no abnormalities such as turbidity and precipitation.
  • NEP (19.6 g) was added to the polyimide powder (7) (2.50 g) obtained by the synthesis method of Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (19.6 g) was added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (11).
  • This liquid crystal aligning agent (11) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • NEP (20.7 g) was added to the polyimide powder (7) (1.50 g) obtained by the synthesis method of Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (20.7 g) was added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (12).
  • This liquid crystal aligning agent (12) was confirmed to be a uniform solution without any abnormalities such as turbidity and generation of precipitates.
  • “evaluation of ink jet coatability of liquid crystal aligning agent” was performed under the above-described conditions.
  • NMP (20.0 g) was added to the polyimide powder (8) (2.55 g) obtained by the synthesis method of Synthesis Example 8, and the mixture was dissolved by stirring at 70 ° C. for 24 hours.
  • PB (8.00 g), PCS (8.00 g) and BCS (4.00 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (13).
  • This liquid crystal aligning agent (13) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • ⁇ -BL (20.1 g) was added to the polyimide powder (8) (2.57 g) obtained by the synthesis method of Synthesis Example 8, and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (16.1 g) and DEEE (4.00 g) were added, and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (14).
  • This liquid crystal aligning agent (14) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • Example 15 NMP (5.94 g) and NEP (15.9 g) were added to the polyimide powder (9) (2.53 g) obtained by the synthesis method of Synthesis Example 9 and dissolved by stirring at 70 ° C. for 24 hours. . To this solution, PB (17.8 g) was added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (15). This liquid crystal aligning agent (15) was confirmed to be a uniform solution with no abnormalities such as turbidity and precipitation.
  • NMP (20.0 g) was added to the polyimide powder (10) (2.55 g) obtained by the synthesis method of Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours.
  • PB 12.0 g
  • PCS 8.00 g
  • This liquid crystal aligning agent (16) was confirmed to be a uniform solution with no abnormalities such as turbidity and precipitation.
  • Example 17 > NMP (11.1 g), NEP (6.92 g) and PB (13.7 g) were added to the polyamic acid solution (11) (10.0 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 11. ) And stirred at 25 ° C. for 3 hours to obtain a liquid crystal aligning agent (17).
  • This liquid crystal aligning agent (17) was confirmed to be a uniform solution with no abnormalities such as turbidity and precipitation.
  • Example 18 NMP (16.0 g), PB (5.90 g) and BCS (9.80 g) were added to a polyamic acid solution (11) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 11. ) And stirred at 25 ° C. for 3 hours to obtain a liquid crystal aligning agent (18).
  • This liquid crystal aligning agent (18) showed no abnormality such as turbidity and generation of precipitates, and was confirmed to be a uniform solution.
  • NEP (22.1 g) was added to the polyimide powder (12) (2.56 g) obtained by the synthesis method of Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (4.00 g) and BCS (14.0 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (19).
  • This liquid crystal aligning agent (19) showed no abnormality such as turbidity and generation of precipitates, and was confirmed to be a uniform solution.
  • NEP (19.2 g) was added to the polyimide powder (12) (1.55 g) obtained by the synthesis method of Synthesis Example 12 and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (12.8g) and BCS (10.7g) were added to this solution, and it stirred at 40 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (20).
  • This liquid crystal aligning agent (20) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • “evaluation of ink jet coatability of liquid crystal aligning agent” was performed under the above-described conditions.
  • ⁇ -BL (22.7 g) was added to the polyimide powder (12) (1.50 g) obtained by the synthesis method of Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (14.5 g) and PGME (4.10 g) were added and stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (21).
  • This liquid crystal aligning agent (21) was confirmed to be a uniform solution with no abnormalities such as turbidity and generation of precipitates.
  • “evaluation of ink jet coatability of liquid crystal aligning agent” was performed under the above-described conditions.
  • NEP (21.5 g) was added to the polyimide powder (13) (2.50 g) obtained by the synthesis method of Synthesis Example 13, and dissolved by stirring at 70 ° C. for 24 hours.
  • PB (11.8g) and BCS (5.90g) were added to this solution, and it stirred at 40 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (22).
  • This liquid crystal aligning agent (22) was confirmed to be a uniform solution without any abnormalities such as turbidity and generation of precipitates.
  • * 3 Indicates the proportion of the polymer in the composition (liquid crystal aligning agent).
  • * 4 Indicates the proportion of the polymer in the composition (liquid crystal aligning agent).
  • the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example of the present invention does not generate pinholes compared to the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example. Uniform coating properties were exhibited. Furthermore, the linearity of the edge part of a liquid crystal aligning film was high, and the result that the swelling of the edge part of a liquid crystal aligning film was also small was obtained. In particular, even with a liquid crystal alignment agent using a polyamic acid or a solvent-soluble polyimide obtained by using the diamine compound having a specific side chain structure of the present invention, the above-described results with high effects were obtained.
  • the specific solvent is included in the comparison between the example including the specific solvent of the present invention and the comparative example not including the specific solvent.
  • the comparative example without many alignment defects associated with pinholes were observed. Specifically, this is a comparison between Example 2 and Comparative Example 1, and a comparison between Example 4 and Comparative Example 2 and Comparative Example 3.
  • a liquid crystal containing no specific side chain structure is compared with the liquid crystal alignment treatment agent containing the specific side chain structure of the present invention and the liquid crystal alignment treatment agent not containing the specific side chain structure.
  • the alignment treatment agent had a low pretilt angle stability, that is, a large change with respect to heating and ultraviolet rays was obtained. Specifically, it is a comparison between Example 2 and Comparative Example 4 and a comparison between Example 4 and Comparative Example 4.
  • the liquid crystal aligning agent of these comparative examples does not contain a specific solvent, many pinholes are generated in the liquid crystal alignment film, the linearity of the end of the liquid crystal alignment film is low, and the end of the liquid crystal alignment film is raised. was a big result. Furthermore, in the evaluation of the liquid crystal alignment of the liquid crystal cell, many alignment defects associated with pinholes were observed.
  • the liquid crystal alignment treatment agent of the present invention exhibits a uniform coating property that does not cause pinholes, and further has a liquid crystal alignment film that has a high linearity at the end of the liquid crystal alignment film and a small bulge at the end of the liquid crystal alignment film. Obtainable.
  • the liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film that does not cause alignment defects associated with pinholes.
  • similar results can be obtained even with a liquid crystal alignment treatment agent using a polyamic acid or a solvent-soluble polyimide obtained by using a diamine compound having a side chain.
  • the liquid crystal display element having the liquid crystal alignment film obtained from 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, etc. It is useful for a device, a TFT liquid crystal device, particularly a vertical alignment type liquid crystal display device.
  • the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful for a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element. That is, a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and containing a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates, A liquid crystal display element manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes, and further comprising a liquid crystal layer between a pair of substrates provided with electrodes, A liquid crystal produced by placing a liquid crystal alignment film containing a polymerizable group that polymerizes at least one of active energy rays and heat between substrates and polymerizing the polymerizable group while applying a voltage between the electrodes. It is also useful for display elements.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (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 contenant le composant (A) et le composant (B) décrits ci-dessous. Composant (A): un propylène glycol monobutyl éther. Composant (B): au moins un polymère choisi parmi des polyimides et des précurseurs de polyimides, obtenus en faisant réagir un composant de diamine présentant une structure représentée par la formule [1] est un composant d'acide tétracarboxylique. (Dans la formule [1], Y1 représente une liaison simple ou similaire; Y2 représente une liaison simple ou -(CH2)b- (b représentant un entier de 1 à 15); Y3 représentant une liaison simple ou similaire; Y4 représentant un groupe cyclique divalent; Y5 représentant un groupe cyclique divalent; n représentant un entier de 0 à 4; et Y6 représentant un groupe alkyle comprenant 1 à 18 atomes de carbone, ou un groupe similaire.)
PCT/JP2013/082053 2012-11-29 2013-11-28 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides WO2014084309A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020197028318A KR20190112215A (ko) 2012-11-29 2013-11-28 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR1020177006142A KR20170029022A (ko) 2012-11-29 2013-11-28 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
CN201380071507.XA CN104956259B (zh) 2012-11-29 2013-11-28 液晶取向处理剂、液晶取向膜及液晶显示元件
JP2014549891A JP6331028B2 (ja) 2012-11-29 2013-11-28 液晶配向処理剤、液晶配向膜および液晶表示素子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012261432 2012-11-29
JP2012-261432 2012-11-29

Publications (1)

Publication Number Publication Date
WO2014084309A1 true WO2014084309A1 (fr) 2014-06-05

Family

ID=50827940

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/082053 WO2014084309A1 (fr) 2012-11-29 2013-11-28 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 (1) JP6331028B2 (fr)
KR (3) KR20190112215A (fr)
CN (1) CN104956259B (fr)
TW (1) TWI635135B (fr)
WO (1) WO2014084309A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016173544A (ja) * 2015-03-18 2016-09-29 Jsr株式会社 液晶表示素子及びその製造方法、並びに液晶配向剤
WO2016158942A1 (fr) * 2015-03-30 2016-10-06 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
JP2017037129A (ja) * 2015-08-07 2017-02-16 住友ベークライト株式会社 感光性樹脂組成物の製造方法
KR20170023153A (ko) * 2014-06-25 2017-03-02 닛산 가가쿠 고교 가부시키 가이샤 액정 표시 소자
KR20190129111A (ko) 2017-03-31 2019-11-19 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3422092B1 (fr) * 2016-02-26 2020-10-14 Nissan Chemical Corporation Dispositif d'affichage à cristaux liquides
TWI767035B (zh) * 2017-07-28 2022-06-11 日商日產化學股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63151928A (ja) * 1986-12-16 1988-06-24 Matsushita Electric Ind Co Ltd 有機膜印刷装置
JPH0618899A (ja) * 1992-07-01 1994-01-28 Fuji Photo Film Co Ltd 液晶表示素子
EP0639629A1 (fr) * 1993-08-19 1995-02-22 Nissan Chemical Industries Ltd. Vernis de polyimide
JPH07109438A (ja) * 1993-08-19 1995-04-25 Nissan Chem Ind Ltd ポリイミドワニス
CN1710467A (zh) * 2004-06-18 2005-12-21 Jsr株式会社 垂直液晶定向剂以及垂直液晶显示元件
JP2006030961A (ja) * 2004-06-18 2006-02-02 Jsr Corp 垂直液晶配向剤、および垂直液晶表示素子
WO2006070819A1 (fr) * 2004-12-28 2006-07-06 Nissan Chemical Industries, Ltd. Materiau avec alignement de cristaux liquides pour alignement vertical, pellicule avec alignement de cristaux liquides et element d’affichage a cristaux liquides utilisant ceux-ci
WO2006126555A1 (fr) * 2005-05-25 2006-11-30 Nissan Chemical Industries, Ltd. Agent d’alignement pour cristaux liquides et dispositif d’affichage à cristaux liquides l’utilisant
WO2008117759A1 (fr) * 2007-03-23 2008-10-02 Nissan Chemical Industries, Ltd. Composé de diamine, acide polyamique, polyimide et agent d'alignement à cristaux liquides
WO2012008464A1 (fr) * 2010-07-13 2012-01-19 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
WO2012133826A1 (fr) * 2011-03-31 2012-10-04 日産化学工業株式会社 Agent d'alignement de cristaux liquides et film d'alignement de cristaux liquides utilisant ledit agent

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0237324A (ja) 1988-07-27 1990-02-07 Sanyo Electric Co Ltd ポリイミド配向膜の製造方法

Patent Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63151928A (ja) * 1986-12-16 1988-06-24 Matsushita Electric Ind Co Ltd 有機膜印刷装置
JPH0618899A (ja) * 1992-07-01 1994-01-28 Fuji Photo Film Co Ltd 液晶表示素子
EP0639629A1 (fr) * 1993-08-19 1995-02-22 Nissan Chemical Industries Ltd. Vernis de polyimide
CN1101654A (zh) * 1993-08-19 1995-04-19 日产化学工业株式会社 聚酰亚胺漆
JPH07109438A (ja) * 1993-08-19 1995-04-25 Nissan Chem Ind Ltd ポリイミドワニス
US5916632A (en) * 1993-08-19 1999-06-29 Nissan Chemical Industries Ltd. Polyimide varnish
DE69424482T2 (de) * 1993-08-19 2000-09-14 Nissan Chemical Industries, Ltd. Polyimid-Lack verwendbar als Flüssigkristallorientierungsschicht
KR100330385B1 (ko) * 1993-08-19 2003-08-14 닛산 가가쿠 고교 가부시키 가이샤 폴리이미드와니스
CN1710467A (zh) * 2004-06-18 2005-12-21 Jsr株式会社 垂直液晶定向剂以及垂直液晶显示元件
JP2006030961A (ja) * 2004-06-18 2006-02-02 Jsr Corp 垂直液晶配向剤、および垂直液晶表示素子
KR20060045968A (ko) * 2004-06-18 2006-05-17 제이에스알 가부시끼가이샤 수직 액정 배향제 및 수직 액정 표시 소자
TWI359858B (en) * 2004-06-18 2012-03-11 Jsr Corp Vertical liquid crystal alignment agent and vertic
WO2006070819A1 (fr) * 2004-12-28 2006-07-06 Nissan Chemical Industries, Ltd. Materiau avec alignement de cristaux liquides pour alignement vertical, pellicule avec alignement de cristaux liquides et element d’affichage a cristaux liquides utilisant ceux-ci
JP5109371B2 (ja) * 2004-12-28 2012-12-26 日産化学工業株式会社 垂直配向用液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子
KR20070087564A (ko) * 2004-12-28 2007-08-28 닛산 가가쿠 고교 가부시키 가이샤 수직 배향용 액정 배향제, 액정 배향막 및 그것을 이용한액정 표시 소자
CN101057178A (zh) * 2004-12-28 2007-10-17 日产化学工业株式会社 垂直定向用液晶定向剂、液晶定向膜及使用了该液晶定向膜的液晶显示元件
TWI375096B (fr) * 2004-12-28 2012-10-21 Nissan Chemical Ind Ltd
CN101176032A (zh) * 2005-05-25 2008-05-07 日产化学工业株式会社 液晶取向处理剂及使用该处理剂的液晶显示元件
KR20080016816A (ko) * 2005-05-25 2008-02-22 닛산 가가쿠 고교 가부시키 가이샤 액정 배향 처리제 및 그것을 이용한 액정 표시 소자
WO2006126555A1 (fr) * 2005-05-25 2006-11-30 Nissan Chemical Industries, Ltd. Agent d’alignement pour cristaux liquides et dispositif d’affichage à cristaux liquides l’utilisant
TWI407211B (zh) * 2005-05-25 2013-09-01 Nissan Chemical Ind Ltd A liquid crystal alignment agent and a liquid crystal display device using the liquid crystal display device
JP5151478B2 (ja) * 2005-05-25 2013-02-27 日産化学工業株式会社 液晶配向処理剤及びそれを用いた液晶表示素子
JP5273035B2 (ja) * 2007-03-23 2013-08-28 日産化学工業株式会社 液晶配向処理剤
KR20090123898A (ko) * 2007-03-23 2009-12-02 닛산 가가쿠 고교 가부시키 가이샤 디아민 화합물, 폴리아믹산, 폴리이미드 및 액정 배향 처리제
CN101641323A (zh) * 2007-03-23 2010-02-03 日产化学工业株式会社 二胺化合物、聚酰胺酸、聚酰亚胺及液晶定向处理剂
WO2008117759A1 (fr) * 2007-03-23 2008-10-02 Nissan Chemical Industries, Ltd. Composé de diamine, acide polyamique, polyimide et agent d'alignement à cristaux liquides
TW200906768A (en) * 2007-03-23 2009-02-16 Nissan Chemical Ind Ltd Diamine compound, polyamic acid, polyimide and liquid crystal aligning agent
WO2012008464A1 (fr) * 2010-07-13 2012-01-19 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
TW201217433A (en) * 2010-07-13 2012-05-01 Nissan Chemical Ind Ltd Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN103097949A (zh) * 2010-07-13 2013-05-08 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
WO2012133826A1 (fr) * 2011-03-31 2012-10-04 日産化学工業株式会社 Agent d'alignement de cristaux liquides et film d'alignement de cristaux liquides utilisant ledit agent
TW201307478A (zh) * 2011-03-31 2013-02-16 Nissan Chemical Ind Ltd 液晶配向劑，及使用其之液晶配向膜
CN103562784A (zh) * 2011-03-31 2014-02-05 日产化学工业株式会社 液晶取向剂及使用该液晶取向剂的液晶取向膜

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10386681B2 (en) 2014-06-25 2019-08-20 Nissan Chemical Industries, Ltd. Liquid crystal display element
KR101944638B1 (ko) * 2014-06-25 2019-01-31 닛산 가가쿠 가부시키가이샤 액정 표시 소자
KR20170023153A (ko) * 2014-06-25 2017-03-02 닛산 가가쿠 고교 가부시키 가이샤 액정 표시 소자
US20170199434A1 (en) * 2014-06-25 2017-07-13 Nissan Chemical Industries, Ltd. Liquid crystal display element
JP2016173544A (ja) * 2015-03-18 2016-09-29 Jsr株式会社 液晶表示素子及びその製造方法、並びに液晶配向剤
CN105988252A (zh) * 2015-03-18 2016-10-05 Jsr株式会社 液晶显示组件及其制造方法、以及液晶取向剂
KR20170131548A (ko) * 2015-03-30 2017-11-29 닛산 가가쿠 고교 가부시키 가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
CN107615147A (zh) * 2015-03-30 2018-01-19 日产化学工业株式会社 液晶取向剂、液晶取向膜和液晶表示元件
JPWO2016158942A1 (ja) * 2015-03-30 2018-01-25 日産化学工業株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
WO2016158942A1 (fr) * 2015-03-30 2016-10-06 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
KR102591734B1 (ko) * 2015-03-30 2023-10-19 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
JP2017037129A (ja) * 2015-08-07 2017-02-16 住友ベークライト株式会社 感光性樹脂組成物の製造方法
KR20190129111A (ko) 2017-03-31 2019-11-19 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자

Also Published As

Publication number Publication date
KR20190112215A (ko) 2019-10-02
CN104956259B (zh) 2019-04-16
TWI635135B (zh) 2018-09-11
KR20170029022A (ko) 2017-03-14
JP6331028B2 (ja) 2018-05-30
JPWO2014084309A1 (ja) 2017-01-05
KR20150087401A (ko) 2015-07-29
TW201434971A (zh) 2014-09-16
CN104956259A (zh) 2015-09-30

Similar Documents

Publication Publication Date Title
JP6414145B2 (ja) 液晶配向処理剤、液晶配向膜及び液晶表示素子
JP2020056034A (ja) 組成物、液晶配向処理剤、液晶配向膜及び液晶表示素子
JP6368955B2 (ja) 液晶配向処理剤、液晶配向膜および液晶表示素子
JP6331028B2 (ja) 液晶配向処理剤、液晶配向膜および液晶表示素子
JP5930239B2 (ja) 組成物、液晶配向処理剤、液晶配向膜および液晶表示素子
JP6299977B2 (ja) 液晶配向処理剤、液晶配向膜および液晶表示素子
WO2015046374A1 (fr) Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides l'utilisant
WO2014189128A1 (fr) Agent de traitement pour orientation de cristaux liquides, film d'orientation de cristaux liquides et dispositif d'affichage à cristaux liquides
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
WO2015053394A1 (fr) Composition, agent de traitement pour l'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
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
WO2015046373A1 (fr) Agent d'alignement de cristaux liquides et élément d'affichage à cristaux liquides utilisant cet agent d'alignement
JP6102752B2 (ja) 液晶配向処理剤、液晶配向膜及び液晶表示素子
JP5930238B2 (ja) 組成物、液晶配向処理剤、液晶配向膜および液晶表示素子
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
JP6683955B2 (ja) 液晶配向処理剤、液晶配向膜及び液晶表示素子

Legal Events

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

Ref document number: 13857865

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014549891

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20157016561

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 13857865

Country of ref document: EP

Kind code of ref document: A1