WO2013099937A1 - Agent d'alignement de cristaux liquides, membrane d'alignement de cristaux liquides, élément d'écran à cristaux liquides, et procédé de fabrication d'élément d'écran à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, membrane d'alignement de cristaux liquides, élément d'écran à cristaux liquides, et procédé de fabrication d'élément d'écran à cristaux liquides Download PDF

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Publication number
WO2013099937A1
WO2013099937A1 PCT/JP2012/083638 JP2012083638W WO2013099937A1 WO 2013099937 A1 WO2013099937 A1 WO 2013099937A1 JP 2012083638 W JP2012083638 W JP 2012083638W WO 2013099937 A1 WO2013099937 A1 WO 2013099937A1
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liquid crystal
group
aligning agent
crystal aligning
component
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PCT/JP2012/083638
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English (en)
Japanese (ja)
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亮一 芦澤
洋一 山之内
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日産化学工業株式会社
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Priority to KR1020147020716A priority Critical patent/KR101986398B1/ko
Priority to JP2013551736A priority patent/JP6172463B2/ja
Priority to CN201280070648.5A priority patent/CN104136979B/zh
Publication of WO2013099937A1 publication Critical patent/WO2013099937A1/fr

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    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a liquid crystal display element that can be used in the manufacture of a liquid crystal display element of a vertical alignment method that is manufactured by irradiating ultraviolet rays with voltage applied to liquid crystal molecules. It relates to a manufacturing method.
  • a liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to a substrate are responded by an electric field also referred to as a vertical alignment (VA) method
  • an ultraviolet ray is applied while applying a voltage to the liquid crystal molecules in the manufacturing process.
  • VA vertical alignment
  • a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell.
  • a technique for increasing the response speed of liquid crystals is known (PSA (Polymer Sustained Alignment) type liquid crystal display).
  • PSA Polymer Sustained Alignment
  • the direction in which the liquid crystal molecules tilt in response to an electric field is controlled by protrusions provided on the substrate or slits provided on the display electrode, but a liquid crystal composition is added with a photopolymerizable compound.
  • the solubility of the polymerizable compound added to the liquid crystal is low, and there is a problem that when the addition amount is increased, it precipitates at a low temperature.
  • the addition amount of the polymerizable compound is reduced, a good alignment state cannot be obtained.
  • the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity (contamination) in the liquid crystal, there is a problem that the reliability of the liquid crystal display element is lowered.
  • the UV irradiation treatment necessary in the PSA mode is large, the components in the liquid crystal are decomposed and the reliability is lowered.
  • Non-Patent Document 2 the response speed of the liquid crystal display element is increased by adding the photopolymerizable compound to the liquid crystal alignment film instead of the liquid crystal composition (SC-PVA liquid crystal display) (for example, Non-Patent Document 2).
  • An object of the present invention is to solve the above-mentioned problems of the prior art, which can improve the response speed of a liquid crystal display element of a vertical alignment type, and further, the electrical characteristics of the obtained liquid crystal display element, particularly DC.
  • An object of the present invention is to provide a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a method for manufacturing a liquid crystal display element that can improve charge storage characteristics.
  • a polyimide precursor having a photoreactive side chain containing at least one selected from: and a polymer selected from a polyimide obtained by imidizing this polyimide precursor has a photoreactive side chain
  • the above-mentioned problems can be solved by mixing (blending) a polyimide selected from a diamine and a diamine having a predetermined structure as a raw material and a polyimide obtained by imidizing the polyimide precursor. The present invention was completed.
  • the liquid crystal aligning agent characterized by containing the following (A) component, (B) component, (C) component, and an organic solvent.
  • Component (A) a side chain that vertically aligns the liquid crystal, and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group And at least one polymer selected from polyimides obtained by imidizing this polyimide precursor.
  • Component (B) a polymerizable compound having a photopolymerizable or photocrosslinking group at one or more terminals.
  • Y 1 represents a secondary amine, tertiary amine, or a monovalent organic group having a heterocyclic structure
  • Y 2 represents a secondary amine, tertiary amine, or a divalent organic group having a heterocyclic structure. Represents an organic group.
  • R 11 is H or a methyl group.
  • R 12 is H or an alkyl group having 1 to 4 carbon atoms
  • Z 1 is a divalent alkyl group optionally having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms
  • Z 2 is a monovalent aromatic ring or heterocyclic ring optionally substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms.
  • a liquid crystal alignment film obtained by applying the liquid crystal aligning agent described in any one of 5.1 to 4 to a substrate and baking it.
  • a liquid crystal layer is provided by contacting a liquid crystal alignment film obtained by applying the liquid crystal alignment agent described in any one of 6.1 to 4 on a substrate and firing the substrate, and irradiating ultraviolet rays while applying a voltage to the liquid crystal layer.
  • a liquid crystal display element comprising a liquid crystal cell manufactured in the above manner.
  • a liquid crystal layer is provided by contacting the liquid crystal alignment agent described in any one of 1 to 4 with a liquid crystal alignment film obtained by applying and baking to a substrate, and ultraviolet light is applied to the liquid crystal layer while applying a voltage. And a liquid crystal cell.
  • the present invention it is possible to provide a vertical alignment type liquid crystal display element in which the response speed of the liquid crystal is high and the accumulation of direct current charges is small. And in this liquid crystal aligning agent, even if it is a case where the addition amount of a polymeric compound is small, a response speed can fully be improved.
  • the liquid crystal aligning agent of this invention is a liquid crystal aligning agent containing the said (A) component, (B) component, (C) component, and an organic solvent.
  • the liquid crystal alignment agent is a solution for forming a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction, in the present invention, in the vertical direction.
  • the liquid crystal aligning agent of the present invention is at least one selected from a side chain for vertically aligning liquid crystal and a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group as the component (A). And at least one polymer selected from polyimides obtained by imidizing this polyimide precursor. Examples of the polyimide precursor include polyamic acid (also referred to as polyamic acid), polyamic acid ester, and the like.
  • the side chain for vertically aligning the liquid crystal is not limited as long as the liquid crystal can be aligned vertically with respect to the substrate.
  • a long chain alkyl group, a ring structure or a branch in the middle of the long chain alkyl group may be used. Examples thereof include a group having a structure, a steroid group, and a group in which some or all of hydrogen atoms of these groups are replaced with fluorine atoms.
  • the side chain for vertically aligning the liquid crystal may be directly bonded to a polyimide precursor such as polyamic acid or the main chain of the polyimide, or may be bonded via an appropriate bonding group. Examples of the side chain for vertically aligning the liquid crystal include those represented by the following formula (a).
  • l, m and n each independently represents an integer of 0 or 1
  • R 3 represents an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—.
  • R 4 , R 5 and R 6 each independently represents a phenylene group or a cycloalkylene group
  • R 7 is a hydrogen atom
  • 2 to 24 represents an alkyl group or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a monovalent macrocyclic substituent comprising them.
  • R 3 in the above formula (a) is preferably —O—, —COO—, —CONH—, or an alkylene-ether group having 1 to 3 carbon atoms from the viewpoint of ease of synthesis.
  • R 4 , R 5 and R 6 in the formula (a) are l, m, n, R 4 and R 5 shown in Table 1 below from the viewpoint of ease of synthesis and ability to align liquid crystals vertically. And a combination of R 6 is preferred.
  • R 7 in the formula (a) is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably A hydrogen atom, an alkyl group having 2 to 12 carbon atoms, or a fluorine-containing alkyl group.
  • R 7 is preferably an alkyl group having 12 to 22 carbon atoms or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent Heterocycles and monovalent macrocyclic substituents composed of these are preferred, and alkyl groups having 12 to 20 carbon atoms or fluorine-containing alkyl groups are more preferred.
  • the amount of the side chain that vertically aligns the liquid crystal is not particularly limited as long as the liquid crystal alignment film can align the liquid crystal vertically.
  • the amount of side chains that vertically align the liquid crystal is possible within a range that does not impair the display characteristics of the element such as voltage holding ratio and accumulation of residual DC voltage. As few as possible is preferable.
  • the ability of a polymer having side chains for vertically aligning liquid crystals to align liquid crystals vertically varies depending on the structure of the side chains for vertically aligning liquid crystals, but in general, the side chains for vertically aligning liquid crystals. As the amount increases, the ability to align the liquid crystal vertically increases, and as the amount decreases, it decreases. Moreover, when it has a cyclic structure, compared with what does not have a cyclic structure, there exists a tendency for the capability to orientate a liquid crystal vertically.
  • the photoreactive side chain is a side chain having a functional group (hereinafter also referred to as a photoreactive group) that can react by irradiation with ultraviolet rays to form a covalent bond.
  • the photoreactive group is a side chain.
  • a methacryl group an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group.
  • At least one selected from a methacrylic group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group is used as the polymer composed of at least one of a polyimide precursor and a polyimide contained in the liquid crystal aligning agent.
  • the response speed can be remarkably improved by using a liquid crystal aligning agent together with the component (B) that is a polymerizable compound. .
  • the photoreactive side chain may be directly bonded to the polyimide precursor or the main chain of the polyimide, or may be bonded via an appropriate bonding group.
  • Examples of the photoreactive side chain include those represented by the following formula (b).
  • R 8 is a single bond or —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N Represents any one of (CH 3 ) —, —CON (CH 3 ) —, —N (CH 3 ) CO—, and R 9 is a single bond, or unsubstituted or substituted with a fluorine atom.
  • R 10 Is a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, Styryl a group and cinnamoyl group.
  • R 8 in the above formula (b) can be formed by an ordinary organic synthetic method, but from the viewpoint of ease of synthesis, —CH 2 —, —O—, —COO—, —NHCO —, —NH— and —CH 2 O— are preferred.
  • divalent carbocycle or divalent heterocycle carbocycle or heterocycle for replacing any —CH 2 — in R 9 include the following structures, but are not limited thereto. Is not to be done.
  • R 10 is preferably a methacryl group, an acryl group or a vinyl group from the viewpoint of photoreactivity.
  • the above formula (b) is more preferably a structure containing a group selected from the above formula (I).
  • the amount of the photoreactive side chain is preferably within a range in which the response speed of the liquid crystal can be increased by reacting with ultraviolet irradiation to form a covalent bond. In order to further increase the response speed of the liquid crystal As many as possible are preferable as long as other characteristics are not affected.
  • ⁇ Production method of component (A)> It has a side chain for vertically aligning such a liquid crystal and a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group.
  • the method for producing the component (A), which is at least one polymer selected from a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor, is not particularly limited.
  • a diamine having a side chain for vertically aligning a liquid crystal a tetracarboxylic dianhydride having a side chain for vertically aligning a liquid crystal, a methacryl group, an acrylic group, vinyl Group, allyl group, coumarin group, styryl group and cinnamoyl group
  • a dianhydride may be copolymerized.
  • a diamine having a side chain for vertically aligning the liquid crystal a long-chain alkyl group, a group having a ring structure or a branched structure in the middle of the long-chain alkyl group, a steroid group, a part of hydrogen atoms of these groups or
  • examples thereof include a diamine having a group in which all the fluorine atoms are replaced as a side chain, such as a diamine having a side chain represented by the above formula (a). More specifically, examples include diamines represented by the following formulas (2), (3), (4), and (5), but are not limited thereto.
  • a 10 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—.
  • a 11 represents a single bond or a phenylene group
  • a represents the same structure as a side chain for vertically aligning the liquid crystal represented by the above formula (a)
  • a ′ is represented by the above formula (a). (This represents a divalent group having a structure in which one element such as hydrogen is removed from the same structure as the side chain that vertically aligns the liquid crystal.)
  • a 14 is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
  • a 15 is a 1,4-cyclohexylene group or 1,4-phenylene.
  • a 16 is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A 15 )
  • a 17 is an oxygen atom or —COO— * (wherein , A bond with “*” is bonded to (CH 2 ) a 2 ), and a 1 is 0 or an integer of 1, a 2 is an integer of 2 to 10, 3 is 0 or an integer of 1.)
  • Binding positions of the two amino group (-NH 2) in equation (2) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • a 1 is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group.
  • a 2 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
  • 3 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
  • a 4 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, or —CH 2 —
  • a 5 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
  • a 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O—, or —NH—
  • a 7 represents fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy Group or hydroxyl group.
  • a 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
  • a 9 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .
  • diamine represented by the formula (3) include diamines represented by the following formulas [A-25] to [A-30], but are not limited thereto.
  • a 12 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—
  • a 13 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • diamine represented by the formula (4) examples include diamines represented by the following formulas [A-31] to [A-32], but are not limited thereto.
  • the above-mentioned diamines can be used alone or in combination of two or more depending on the properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.
  • the diamine having a side chain for vertically aligning the liquid crystal should be used in an amount of 5 to 50 mol% of the total diamine component used for the synthesis of the polyimide precursor (A) and the component (A) which is polyimide. More preferably, 10 to 40 mol% of the total diamine component is a diamine having a side chain for vertically aligning the liquid crystal, and particularly preferably 15 to 30 mol%.
  • the diamine having a side chain for vertically aligning the liquid crystal is used in an amount of 5 to 50 mol% of the polyimide precursor such as polyamic acid or the total diamine component used for the synthesis of the polyimide, the response speed is improved and the alignment of the liquid crystal is increased. Especially excellent in terms of immobilization ability.
  • diamine having a photoreactive side chain including at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group are represented by the above formula (b).
  • diamines having side chains More specifically, examples include diamines represented by the following general formula (6), but are not limited thereto.
  • the bonding position of the two amino groups (—NH 2 ) in Formula (6) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.
  • diamine having a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group include the following compounds: Although it is mentioned, it is not limited to this.
  • X is a single bond or a linking group selected from —O—, —COO—, —NHCO—, —NH—, Y is a single bond, or carbon that is unsubstituted or substituted by a fluorine atom. Represents an alkylene group of 1 to 20.
  • the diamine having a photoreactive side chain containing at least one selected from the methacryl group, acryl group, vinyl group, allyl group, coumarin group, styryl group and cinnamoyl group is a liquid crystal alignment property when used as a liquid crystal alignment film.
  • a photoreactive side chain containing at least one selected from the methacryl group, acryl group, vinyl group, allyl group, coumarin group, styryl group and cinnamoyl group is a liquid crystal alignment property when used as a liquid crystal alignment film.
  • the characteristics such as the pretilt angle, the voltage holding characteristic, the accumulated charge, the response speed of the liquid crystal when the liquid crystal display element is used, one kind or a mixture of two or more kinds can be used.
  • such a diamine having a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group is the component (A). It is preferable to use an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol% of the total diamine component used for the synthesis of the polyimide precursor such as polyamic acid and polyimide.
  • the polyimide precursor and polyimide such as polyamic acid as the component (A) have a diamine having a side chain for vertically aligning the liquid crystal or a photoreactive group as long as the effects of the present invention are not impaired.
  • Other diamines other than diamine can be used in combination as the diamine component of the raw material.
  • p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dicarboxy-4,
  • the above-mentioned other diamines can be used alone or in combination of two or more according to properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.
  • the tetracarboxylic dianhydride component that is reacted with the diamine component in the synthesis of the polyamic acid or the like that is the component (A) is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetra Carboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-
  • a raw material diamine also referred to as “diamine component”
  • a raw material tetracarboxylic dianhydride also referred to as “tetracarboxylic dianhydride component”
  • the synthesis method can be used.
  • a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent.
  • the reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
  • the organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid or the like dissolves. Furthermore, even if it is an organic solvent in which a polyamic acid etc. do not melt
  • organic solvent used in the reaction examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, e
  • the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent.
  • a method of adding by dispersing or dissolving in a solvent a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component.
  • the method of adding alternately etc. is mentioned, You may use any of these methods.
  • the diamine component or tetracarboxylic dianhydride component when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually.
  • the body may be mixed and reacted to form a high molecular weight body.
  • the temperature at the time of reacting the diamine component and the tetracarboxylic dianhydride component can be selected arbitrarily, and is, for example, in the range of ⁇ 20 ° C. to 150 ° C., preferably ⁇ 5 ° C. to 100 ° C.
  • the reaction can be carried out at any concentration.
  • the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass, based on the reaction solution.
  • the ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component can be selected according to the molecular weight of the polyamic acid or the like to be obtained. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced. If it shows a preferable range, it is 0.8 to 1.2.
  • the method for synthesizing the polyamic acid used in the present invention is not limited to the above-described method, and in the same manner as the general polyamic acid synthesis method, instead of the tetracarboxylic dianhydride, a tetracarboxylic acid having a corresponding structure is used.
  • the corresponding polyamic acid can also be obtained by reacting by a known method using a tetracarboxylic acid derivative such as acid or tetracarboxylic acid dihalide.
  • the polyimide precursor such as polyamic acid As a method of imidizing the polyimide precursor such as polyamic acid as described above to obtain a polyimide, thermal imidization in which a solution of the polyimide precursor such as polyamic acid is heated as it is, a catalyst is applied to the polyimide precursor solution such as polyamic acid.
  • the catalyst imidation to add is mentioned.
  • the imidation ratio from polyimide precursors, such as a polyamic acid, to a polyimide does not necessarily need to be 100%.
  • the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and is preferably carried out while removing water generated by the imidization reaction from the outside of the system.
  • the catalytic imidation of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 to 250 ° C., preferably 0 to 180 ° C.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
  • the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the reaction solution may be poured into a poor solvent and precipitated.
  • the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
  • the polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
  • the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
  • the liquid crystal aligning agent of this invention contains the polymeric compound which has the group which photopolymerizes or photocrosslinks in one or more terminal as (B) component. That is, the component (B), which is a polymerizable compound contained in the liquid crystal aligning agent of the present invention, is a compound having one or more terminals having groups that undergo photopolymerization or photocrosslinking.
  • the polymerizable compound having a photopolymerizable group is a compound having a functional group that causes polymerization upon irradiation with light.
  • the polymerizable compound having a photocrosslinkable group reacts with the polymer of the polymerizable compound and the polymer which is the component (A) or (C) by irradiation with light to crosslink with these. It is a compound having a functional group.
  • the polymerizable compound having a photocrosslinkable group also reacts with other polymerizable compounds having a photocrosslinkable group.
  • Such a polymerizable compound has a photoreactive property including a side chain for vertically aligning liquid crystal and at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group.
  • SC-PVA containing a polyimide precursor having a side chain and a component (A) which is at least one polymer selected from polyimides obtained by imidizing this polyimide precursor in a liquid crystal aligning agent.
  • Examples of the group that undergoes photopolymerization or photocrosslinking include monovalent groups represented by the above formula (II).
  • component (B) that is a polymerizable compound examples include a polymerizable compound having a photopolymerizable group at each of two ends as represented by the following formula (III), and a compound represented by the following formula (IV).
  • a polymerizable compound having a terminal having a photopolymerizable group and a terminal having a photocrosslinkable group, and a polymerizability having a photocrosslinkable group at each of two terminals represented by the following formula (V) Compounds.
  • R 12, Z 1 and Z 2 are the same as R 12, Z 1 and Z 2 in the formula (II)
  • Q 1 is a divalent organic group is there.
  • Q 1 has a ring structure such as a phenylene group (—C 6 H 4 —), a biphenylene group (—C 6 H 4 —C 6 H 4 —), a cyclohexylene group (—C 6 H 10 —), and the like. Preferably it is. This is because the interaction with the liquid crystal tends to increase.
  • V is a single bond or represented by —R 1 O—
  • R 1 is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably represented by —R 1 O— and R 1 is A linear or branched alkylene group having 2 to 6 carbon atoms
  • W represents a single bond or —OR 2 —
  • R 2 represents a linear or branched alkylene group having 1 to 10 carbon atoms, and preferably represents —OR 2 — and R 2 represents a linear or A branched alkylene group having 2 to 6 carbon atoms.
  • V and W may be the same or different, but if they are the same, synthesis is easy.
  • the polymerizable compound represented by the above formula is a compound having a specific structure having ⁇ -methylene- ⁇ -butyrolactone groups which are polymerizable groups at both ends, so that the polymer has a rigid structure to fix the alignment of liquid crystals.
  • a polyimide precursor and at least one polymer selected from polyimide obtained by imidizing this polyimide precursor are used.
  • the response speed can be greatly improved by using the liquid crystal display device of the vertical alignment system such as the SC-PVA liquid crystal display to be used.
  • the process of forming the liquid crystal alignment film includes a step of baking at a high temperature to completely remove the solvent.
  • a polymerizable group such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, or an epoxy group is added.
  • the compounds that are possessed have poor thermal stability and are difficult to withstand firing at high temperatures.
  • the polymerizable compound as described in the above formula having ⁇ -methylene- ⁇ -butyrolactone groups at both ends is sufficiently resistant to a high temperature, for example, a firing temperature of 200 ° C. or higher, because of its poor thermal polymerizability. Can do.
  • the photopolymerization or photocrosslinking group is a polymerizable compound having an acrylate group or a methacrylate group instead of an ⁇ -methylene- ⁇ -butyrolactone group
  • the acrylate group or methacrylate group is a spacer such as an oxyalkylene group.
  • the response speed is greatly improved, as in the case of the polymerizable compound having an ⁇ -methylene- ⁇ -butyrolactone group at both ends. be able to.
  • the polymerizable compound has a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group via a spacer such as an oxyalkylene group, the stability to heat is improved, or a high temperature, for example, 200 ° C. or higher. Can sufficiently withstand the firing temperature.
  • polymerizable compound represented by the formula (III) include polymerizable compounds of the following formula.
  • V represents a single bond or —R 1 O—
  • R 1 represents a linear or branched alkylene group having 1 to 10 carbon atoms, preferably represented by —R 1 O— and represented by R 1 Is a linear or branched alkylene group having 2 to 6 carbon atoms
  • W is a single bond or —OR 2 —
  • R 2 is a linear or branched alkylene group having 1 to 10 carbon atoms.
  • -OR 2 - synthesis and represented by R 2 .V and W is a linear or branched alkylene group having 2 to 6 carbon atoms may be the same or different structure but the same R 12 is H or an alkyl group having 1 to 4 carbon atoms.
  • the manufacturing method of (B) component which is such a polymeric compound is not specifically limited, For example, it can manufacture according to the synthesis example mentioned later.
  • the polymerizable compound represented by the following formula (1) can be synthesized by combining techniques in organic synthetic chemistry.
  • Taraga and the like represented by the following reaction formula can use 2- (bromomethyl) acrylic acid with SnCl 2 according to the method proposed by P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990). It can be synthesized by reacting (2- (bromomethyl) propenoic acid) with aldehyde or ketone.
  • Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas.
  • R ′ represents a monovalent organic group.
  • 2- (bromomethyl) acrylic acid is represented by the following reaction formula: K. Ramarajan, K. Kamalingam, DJO 'Donnell and KDBerlin, Organic Synthesis, vol.61, 56-59 (1983) It can be synthesized by the method proposed in.
  • the liquid crystal aligning agent of this invention has a photoreactive side chain containing at least 1 type selected from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group as (C) component.
  • a polyimide precursor obtained by a reaction of a diamine, at least one diamine selected from the above formulas (C-1) to (C-5) and a tetracarboxylic dianhydride, and imidizing the polyimide precursor; Contains a polymer selected from the resulting polyimide.
  • photoreactive side chain containing at least one selected from methacryl group, acryl group, vinyl group, allyl group, coumarin group, styryl group and cinnamoyl group are the above [component (A) ] Is the same as that described above.
  • diamine having a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group are the above [component (A) ] Is the same as that described above.
  • such a diamine having a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group is the component (C). It is preferable to use an amount of 10 mol% to 60 mol%, more preferably 10 mol% to 40 mol%, particularly preferably 20 mol% to the total diamine component used for the synthesis of polyimide precursor such as polyamic acid and polyimide. 30 mol%.
  • the polymer as component (C) is also made from at least one diamine selected from the above formulas (C-1) to (C-5). If at least one diamine selected from the above formulas (C-1) to (C-5) is also used as a raw material, the accumulated charge characteristics can be improved because these are diamines having a specific structure with high polarity. Examples of at least one diamine selected from the above formulas (C-1) to (C-5) include, but are not limited to, the following diamines.
  • At least one diamine selected from the above formulas (C-1) to (C-5) is 10 mol of the total diamine component used for the synthesis of the polyimide precursor such as polyamic acid and the polyimide as the component (C). It is preferable to use an amount of from 80 to 80 mol%.
  • a diamine having a side chain for vertically aligning the liquid crystal described in [Component (A)] or other diamine may be used as a raw material for the component (C).
  • a diamine having a side chain that vertically aligns the liquid crystal is also used as a raw material
  • a diamine having a side chain that vertically aligns the liquid crystal is synthesized from a polyimide precursor such as polyamic acid or a polyimide as component (C). It is preferable to use an amount of 10 mol% to 30 mol% of the total diamine component used in the above.
  • the tetracarboxylic dianhydride component to be reacted with the diamine component is the same as the tetracarboxylic dianhydride component described in [Component (A)] above.
  • the method for producing the component (C) includes a diamine having a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group; At least one diamine selected from the formulas (C-1) to (C-5), tetracarboxylic dianhydride, and, if necessary, a diamine having a side chain for vertically aligning liquid crystals, What is necessary is just to make another diamine etc. react and to obtain a polyimide precursor and a polyimide.
  • the production method is the same as that described in the above ⁇ Production method of component (A)> except that at least one diamine selected from the above formulas (C-1) to (C-5) is also used as a raw material.
  • the liquid crystal aligning agent of the present invention includes at least one selected from a side chain for vertically aligning liquid crystals and a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group.
  • Component (A) which is at least one polymer selected from a polyimide precursor having a photoreactive side chain, and a polyimide obtained by imidizing this polyimide precursor, and light at one or more terminals
  • Photoreactivity comprising (B) component which is a polymerizable compound having a group that undergoes polymerization or photocrosslinking, and at least one selected from methacryl, acryl, vinyl, allyl, coumarin, styryl, and cinnamoyl groups
  • the (C) component which is a polymer selected from the polyimide precursor obtained by reaction, and the polyimide obtained by imidating this polyimide precursor, and a solvent, and it is especially in the compounding ratio.
  • the content of the component (B) is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the component (A).
  • the content of the component (A) in the liquid crystal aligning agent of the present invention is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass. .
  • the content ratio of the component (A) and the component (C) is not particularly limited.
  • the liquid crystal aligning agent of this invention may contain other polymers other than (A) component and (C) component.
  • the content of the other polymer in all the polymer components is preferably 0.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass.
  • the molecular weight of the polymer of the liquid crystal aligning agent is determined based on GPC (Gel Permeation Chromatography) in consideration of the strength of the liquid crystal aligning film obtained by applying the liquid crystal aligning agent, workability at the time of forming the coating film, and uniformity of the coating film.
  • the weight average molecular weight measured by the above method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
  • the solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can dissolve or disperse the components (A), (B), and (C).
  • organic solvents as exemplified in the synthesis of the above polyamic acid and the like can be mentioned.
  • N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N, N-dimethylpropanamide are from the viewpoint of solubility.
  • two or more kinds of mixed solvents may be used.
  • Solvents that improve the uniformity and smoothness of the coating include, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol Thor, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert
  • the liquid crystal aligning agent may contain components other than those described above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.
  • Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.).
  • the ratio of use thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent. 1 part by mass.
  • compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds.
  • a phenol compound such as 2,2′-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol may be added.
  • the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent.
  • liquid crystal aligning agent is added with a dielectric or conductive material for changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, as long as the effects of the present invention are not impaired. May be.
  • the liquid crystal aligning agent of the present invention has a photoreactive property including a side chain for vertically aligning a liquid crystal and at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group.
  • the polymer has a photoreactive side chain containing at least one selected from a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can be used.
  • a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process.
  • an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal aligning agent is not particularly limited, and examples thereof include a screen printing method, an offset printing method, a flexographic printing method, an inkjet method, a dip method, a roll coater, a slit coater, and a spinner.
  • the firing temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and can be performed at any temperature of, for example, 100 to 350 ° C., preferably 120 ° C. to 300 ° C., more preferably 150 to 250 ° C.
  • This baking can be performed with a hot plate, a hot-air circulating furnace, an infrared furnace, or the like.
  • the thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 100 nm.
  • the liquid crystal display element of the present invention includes two substrates disposed to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent provided between the substrate and the liquid crystal layer. It is a vertical alignment type liquid crystal display element comprising a liquid crystal cell having the liquid crystal alignment film formed. Specifically, the liquid crystal aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal aligning film, and the two substrates are arranged so that the liquid crystal aligning films face each other.
  • Vertical alignment type liquid crystal display comprising a liquid crystal cell formed by sandwiching a liquid crystal layer composed of liquid crystal between two substrates and irradiating ultraviolet light while applying voltage to the liquid crystal alignment film and the liquid crystal layer It is an element.
  • the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is used to irradiate ultraviolet rays while applying voltage to the liquid crystal alignment film and the liquid crystal layer to polymerize the polymerizable compound, and the light possessed by the polymer.
  • the liquid crystal display element has a small accumulated charge.
  • the substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed.
  • a substrate on which a transparent electrode for driving liquid crystal As a specific example, the thing similar to the board
  • a substrate provided with a conventional electrode pattern or protrusion pattern may be used, but in the liquid crystal display element of the present invention, the liquid crystal aligning agent of the present invention is used as the liquid crystal aligning agent for forming the liquid crystal aligning film. It is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 ⁇ m is formed on one side substrate and no slit pattern or projection pattern is formed on the opposite substrate. The process can be simplified and high transmittance can be obtained.
  • a high-performance element such as a TFT type element
  • an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.
  • a substrate In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer may be used. Is possible. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.
  • the liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on this substrate and baking it, and the details are as described above.
  • the liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method, for example, a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Can be used.
  • a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal.
  • a liquid crystal cell can also be produced by a method in which the other substrate is bonded to the inside so as to be inside and sealed.
  • the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field between the electrodes installed on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer. And applying ultraviolet rays while maintaining this electric field.
  • the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.
  • the irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the smaller the irradiation amount of ultraviolet rays, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, and the irradiation time of ultraviolet rays can be reduced. This is preferable because the manufacturing efficiency is improved.
  • the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is memorized by this polymer.
  • the response speed of the obtained liquid crystal display element can be increased.
  • the photoreactive side chains of the (A) component and (C) component which are polymers, the (A) component and (C Since the photoreactive side chain of the component (B) and the component (B) which is a polymerizable compound react with each other the response speed of the obtained liquid crystal display device can be increased, and the accumulated charge characteristics are also improved.
  • the liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing a vertical alignment type liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also by rubbing treatment or photo-alignment treatment. It can also be suitably used for applications of the liquid crystal alignment film to be produced.
  • Diamine p-PDA p-phenylenediamine
  • m-PDA m-phenylenediamine
  • PCH 1,3-diamino-4- [4- (4-heptylcyclohexyl) phenoxy] benzene
  • DBA 3,5-diaminobenzoic acid
  • BEM -S 2- (methacryloyloxy) ethyl 3,5-diaminobenzoate represented by the following formula
  • DADPA N 1- (4-aminophenyl) benzene-1,4-diamine represented by the following formula
  • Polymerizable compound RM1 Polymerizable compound 5,5 ′-(4,4 ′-(biphenyl-4,4′-diylbis (oxy)) bis (butane-4,1-diyl) bis represented by the following formula (3-methylenedihydrofuran-2 (3H) -one)
  • the separated organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid.
  • the result of having measured the obtained white solid by NMR is shown below.
  • the obtained solid was dissolved in deuterated chloroform (CDCl 3 ) and measured at 300 MHz using a nuclear magnetic resonance apparatus (manufactured by Diol). From this result, it was confirmed that this white solid was an intermediate compound (RM1-A) represented by the following reaction formula. The yield was 92%.
  • RM2 polymerizable compound represented by the following formula 5,5 ′-(4,4 ′-(propane-2,2-diyl) bis (4,1-phenylene)) bis (oxy) bis (pentane-5 1-Diyl) bis (2-methacrylate)
  • RM2 was obtained according to the method described in JP-A-63-79853.
  • RM3 polymerizable compound represented by the following formula 5,5 ′-(4,4′-carbonylbis (4,1-phenylene) bis (oxy)) bis (pentane-5,1-diyl) bis (2- Methacrylate)
  • the molecular weight measurement conditions of a polymer are as follows.
  • Apparatus Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd.
  • Standard sample for preparing a calibration curve TSK standard polyethylene oxide (molecular weight of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight about 12,000, 4,000, 1,000).
  • the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. 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 appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
  • x is the proton peak integrated value derived from the NH group of the amic acid
  • y is the peak integrated value of the reference proton
  • ⁇ is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • NMP (24.0 g) was added to the obtained polyimide powder (A) (6.0 g) and dissolved by stirring at room temperature for 5 hours.
  • NMP (40.0g) and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent (A1) was obtained by stirring at room temperature for 5 hours.
  • liquid crystal aligning agent (A1) 60 mg (10 mass% with respect to solid content) of polymeric compound RM1 is added with respect to 10.0 g of said liquid crystal aligning agent (A1), and it stirs and dissolves at room temperature for 3 hours, and liquid crystal aligning agent (A2) ) was prepared.
  • liquid crystal aligning agent (A1) 60 mg (10 mass% with respect to solid content) of polymeric compound RM2 are added with respect to 10.0 g of said liquid crystal aligning agent (A1), and it stirs and dissolves at room temperature for 3 hours, and liquid crystal aligning agent (A3 ) was prepared.
  • liquid crystal aligning agent (A1) 60 mg (10 mass% with respect to solid content) of polymeric compound RM3 is added with respect to 10.0 g of said liquid crystal aligning agent (A1), and it stirs and dissolves at room temperature for 3 hours, and liquid crystal aligning agent (A4) ) was prepared.
  • NMP (24.0 g) was added to the obtained polyimide powder (B) (6.0 g), and dissolved by stirring at room temperature for 5 hours.
  • NMP (40.0g) and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent (B1) was obtained by stirring at room temperature for 5 hours.
  • liquid crystal aligning agent (B1) 60 mg (10 mass% with respect to solid content) of polymeric compound RM3 is added with respect to 10.0 g of said liquid crystal aligning agent (B1), and it stirs and dissolves at room temperature for 3 hours, liquid crystal aligning agent (B2 ) was prepared.
  • NMP (24.0 g) was added to the obtained polyimide powder (C) (6.0 g) and dissolved by stirring at room temperature for 5 hours.
  • NMP (40.0g) and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent (C1) was obtained by stirring at room temperature for 5 hours.
  • liquid crystal aligning agent (A1) and 7.0 g of liquid crystal aligning agent (C1) were mixed, and the liquid crystal aligning agent (C2) was obtained.
  • liquid crystal aligning agent (C2) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM3 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (C3).
  • NMP (24.0 g) was added to the obtained polyimide powder (D) (6.0 g) and dissolved by stirring at room temperature for 5 hours.
  • NMP (40.0g) and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent (D1) was obtained by stirring at room temperature for 5 hours.
  • liquid crystal aligning agent (A1) and 7.0 g of liquid crystal aligning agent (D1) were mixed, and the liquid crystal aligning agent (D2) was obtained.
  • liquid crystal aligning agent (D2) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM1 was added and dissolved by stirring for 3 hours at room temperature to prepare a liquid crystal aligning agent (D3).
  • liquid crystal aligning agent (D2) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM2 was added to the liquid crystal aligning agent (D2), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal aligning agent (D4).
  • liquid crystal aligning agent (D2) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM3 was added to the liquid crystal aligning agent (D2) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (D5).
  • NMP (24.0 g) was added to the obtained polyimide powder (E) (6.0 g) and dissolved by stirring at room temperature for 5 hours.
  • NMP (40.0g) and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent (E1) was obtained by stirring at room temperature for 5 hours.
  • liquid crystal aligning agent (A1) and 7.0 g of liquid crystal aligning agent (E1) were mixed, and the liquid crystal aligning agent (E2) was obtained.
  • liquid crystal aligning agent (E2) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM3 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (E3).
  • liquid crystal aligning agent (B1) and 7.0 g of liquid crystal aligning agent (E1) were mixed, and the liquid crystal aligning agent (E4) was obtained.
  • liquid crystal aligning agent (E4) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM3 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (E5).
  • NMP (24.0 g) was added to the obtained polyimide powder (F) (6.0 g) and dissolved by stirring at room temperature for 5 hours.
  • NMP (40.0g) and BCS (30.0g) were added to this solution, and the liquid crystal aligning agent (F1) was obtained by stirring at room temperature for 5 hours.
  • liquid crystal aligning agent (A1) and 7.0 g of liquid crystal aligning agent (F1) were mixed, and the liquid crystal aligning agent (F2) was obtained.
  • liquid crystal aligning agent (F2) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM3 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (F3).
  • liquid crystal aligning agent (B1) and 7.0 g of liquid crystal aligning agent (F1) were mixed, and the liquid crystal aligning agent (F4) was obtained.
  • liquid crystal aligning agent (F4) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM3 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (F5).
  • liquid crystal aligning agent (A1) and 7.0 g of liquid crystal aligning agent (G1) were mixed, and the liquid crystal aligning agent (G2) was obtained.
  • liquid crystal aligning agent (G2) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM3 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (G3).
  • liquid crystal aligning agent (A1) and 7.0 g of liquid crystal aligning agent (H1) were mixed, and the liquid crystal aligning agent (H2) was obtained.
  • liquid crystal aligning agent (H2) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM3 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (H3).
  • liquid crystal aligning agent (I2) 3.0 g of the liquid crystal aligning agent (A1) and 7.0 g of the liquid crystal aligning agent (I1) were mixed to obtain a liquid crystal aligning agent (I2).
  • liquid crystal aligning agent (I2) 60 mg of polymerizable compound RM3 (10% by mass with respect to the solid content) was added and stirred at room temperature for 3 hours to dissolve to prepare liquid crystal aligning agent (I3).
  • liquid crystal aligning agent (A1) and 7.0 g of liquid crystal aligning agent (J1) were mixed, and the liquid crystal aligning agent (J2) was obtained.
  • liquid crystal aligning agent (J2) 60 mg (10% by mass with respect to the solid content) of the polymerizable compound RM3 was added and dissolved by stirring for 3 hours at room temperature to prepare a liquid crystal aligning agent (J3).
  • Example 1 Using the liquid crystal aligning agent (D3) obtained in Synthesis Example 4, a liquid crystal cell was prepared according to the procedure shown below.
  • the liquid crystal aligning agent (D3) obtained in Synthesis Example 4 is spin coated on the ITO surface of the ITO electrode substrate on which the ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line / space of 5 ⁇ m is formed, and is 80 ° C. After drying for 90 seconds on this hot plate, baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
  • a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed thereon.
  • the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell.
  • a negative type liquid crystal (MLC-6608) was injected into this empty cell by a reduced pressure injection method, and a realignment treatment was performed at 120 ° C. for 1 hour to prepare a liquid crystal cell 1.
  • the response speed of the obtained liquid crystal cell 1 was measured by the following method. After that, in a state where a voltage of 20 Vp-p was applied to the liquid crystal cell 1, 20 J UV irradiation through a 365 nm band pass filter was applied from the outside of the liquid crystal cell 1. Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared. The results are shown in Table 2.
  • the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell.
  • a negative type liquid crystal (MLC-6608) was injected into this empty cell by a reduced pressure injection method, and a realignment treatment was performed at 120 ° C. for 1 hour to produce a liquid crystal cell.
  • the liquid crystal cell 2 was obtained by irradiating 20 J of UV through a 365 nm band pass filter from the outside of the liquid crystal cell.
  • the liquid crystal cell 1 created as described above was placed between a pair of polarizing plates in a measuring apparatus configured in the order of a backlight, a set of polarizing plates in a crossed Nicol state, and a light amount detector.
  • the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols.
  • a rectangular wave having a voltage of ⁇ 4 V and a frequency of 1 kHz is applied to the liquid crystal cell 1, and a change until the luminance observed by the light amount detector is saturated is captured by an oscilloscope, and the luminance when no voltage is applied A voltage of 0% and ⁇ 4 V was applied, the value of saturated luminance was taken as 100%, and the time taken for the luminance to change from 10% to 90% was taken as the response speed.
  • Example 2 The same operation as in Example 1 was performed except that the liquid crystal aligning agent (D4) was used instead of the liquid crystal aligning agent (D3), and the response speeds before and after UV irradiation were compared. Moreover, the residual DC voltage was measured.
  • the liquid crystal aligning agent (D4) was used instead of the liquid crystal aligning agent (D3), and the response speeds before and after UV irradiation were compared. Moreover, the residual DC voltage was measured.
  • Example 3 Except for using the liquid crystal aligning agent (D5) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed, and the response speed before and after UV irradiation was compared. Moreover, the residual DC voltage was measured.
  • Example 1 Comparative Example 1 Except for using the liquid crystal aligning agent (C3) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed, and the response speed before and after UV irradiation was compared. Moreover, the residual DC voltage was measured.
  • Example 2 Comparative Example 2 Except for using the liquid crystal aligning agent (E3) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed, and the response speeds before and after UV irradiation were compared. Moreover, the residual DC voltage was measured.
  • Example 4 Except for using the liquid crystal aligning agent (F3) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed, and the response speed before and after UV irradiation was compared. Moreover, the residual DC voltage was measured.
  • Example 3 Except for using the liquid crystal aligning agent (G3) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed to compare the response speed before and after UV irradiation. Moreover, the residual DC voltage was measured.
  • Example 4 Except for using the liquid crystal aligning agent (H3) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed to compare the response speed before and after UV irradiation. Moreover, the residual DC voltage was measured.
  • Example 5 Except for using the liquid crystal aligning agent (I3) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed to compare the response speed before and after UV irradiation. Moreover, the residual DC voltage was measured.
  • Example 6 Except for using the liquid crystal aligning agent (J3) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed, and the response speeds before and after UV irradiation were compared. Moreover, the residual DC voltage was measured.
  • Example 5 Comparative Example 5 Except for using the liquid crystal aligning agent (A2) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed, and the response speeds before and after UV irradiation were compared. Moreover, the residual DC voltage was measured.
  • Example 6 Comparative Example 6 Except for using the liquid crystal aligning agent (A3) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed to compare the response speed before and after UV irradiation. Moreover, the residual DC voltage was measured.
  • Example 7 Comparative Example 7 Except for using the liquid crystal aligning agent (A4) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed to compare the response speed before and after UV irradiation. Moreover, the residual DC voltage was measured.
  • Example 8 Except for using the liquid crystal aligning agent (B2) instead of the liquid crystal aligning agent (D3), the same operation as in Example 1 was performed to compare the response speed before and after UV irradiation. Moreover, the residual DC voltage was measured.

Abstract

La présente invention concerne un agent d'alignement de cristaux liquides comportant un constituant (A), un constituant (B), et un constituant (C) décrits en détail ci-dessous, ainsi qu'un solvant organique. Le constituant (A) est au moins un polymère choisi parmi les polymères suivants : un précurseur polyimide avec une chaîne latérale qui aligne un cristal liquide verticalement et une chaîne latérale photoréactive comportant au moins un groupe choisi parmi le groupe constitué d'un groupe méthacryle, d'un groupe acryle, d'un groupe vinyle, d'un groupe allyle, d'un groupe coumarine, d'un groupe styryle, et d'un groupe cinnamoyle, ; et un polyimide obtenu par imidisation de ce précurseur polyimide. Le constituant (B) est un composé polymérisable avec un groupe photo-polymérisé ou photo-réticulé sur au moins une extrémité terminale. Le constituant (C) est au moins un polymère choisi parmi les polymères suivants : un précurseur polyimide obtenu par la réaction d'un dianhydride tétracarboxylique avec une diamine ayant une chaîne latérale photoréactive comportant au moins un groupe parmi le groupe constitué d'un groupe méthacryle, d'un groupe acryle, d'un groupe vinyle, d'un groupe allyle, d'un groupe coumarine, d'un groupe styryle, et d'un groupe cinnamoyle, et au moins une diamine choisie parmi les formules (C-1) à (C5) représentées dans le dessin ; et un polyimide obtenu par imidisation de ce précurseur polyimide. (Dans les formules, Y1 représente une amine secondaire, une amine tertiaire, un groupe organique monovalent avec une structure hétérocyclique, tandis Y2 représente une amine secondaire, une amine tertiaire, un groupe organique divalent avec une structure hétérocyclique.)
PCT/JP2012/083638 2011-12-28 2012-12-26 Agent d'alignement de cristaux liquides, membrane d'alignement de cristaux liquides, élément d'écran à cristaux liquides, et procédé de fabrication d'élément d'écran à cristaux liquides WO2013099937A1 (fr)

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