WO2016125870A1 - Agent d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et procédé de fabrication d'élément d'affichage à cristaux liquides - Google Patents

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

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WO2016125870A1
WO2016125870A1 PCT/JP2016/053413 JP2016053413W WO2016125870A1 WO 2016125870 A1 WO2016125870 A1 WO 2016125870A1 JP 2016053413 W JP2016053413 W JP 2016053413W WO 2016125870 A1 WO2016125870 A1 WO 2016125870A1
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liquid crystal
component
group
display element
polyimide
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PCT/JP2016/053413
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English (en)
Japanese (ja)
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暁子 若林
耕平 後藤
章吾 檜森
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日産化学工業株式会社
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Priority to CN201680008962.9A priority Critical patent/CN107209423B9/zh
Priority to KR1020177023922A priority patent/KR102502321B1/ko
Priority to KR1020237005293A priority patent/KR102607979B1/ko
Priority to JP2016573424A priority patent/JP6662306B2/ja
Publication of WO2016125870A1 publication Critical patent/WO2016125870A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133703—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by introducing organic surfactant additives into the liquid crystal material
    • 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 display element, and a method for manufacturing a liquid crystal display element that can be used for manufacturing a vertical alignment type liquid crystal display element manufactured by irradiating liquid crystal molecules with ultraviolet rays.
  • a voltage is applied to the liquid crystal molecules during the manufacturing process.
  • Some include a step of irradiating with ultraviolet rays.
  • 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 PSA (Polymer sustained Alignment) element (see Patent Document 1 and Non-Patent Document 1) is known which has a high response speed of liquid crystal.
  • the tilting direction of the liquid crystal molecules in response to the electric field is controlled by a protrusion provided on the substrate, a slit provided in the display electrode, or the like.
  • the response speed of the liquid crystal display element is faster than the method of controlling the tilt direction of the liquid crystal molecules only by the protrusions and slits.
  • the deterioration of the residual DC characteristics causes burn-in that leads to the deterioration of the display characteristics (afterimage) of the liquid crystal display element.
  • Conventional methods for improving residual DC are known to promote charge transfer by electrostatic interaction such as salt formation or hydrogen bonding between a carboxy group and a nitrogen-containing aromatic heterocycle.
  • Patent Documents 10 to 12 there are few knowledges on how to improve the residual DC when using alkenyl liquid crystals.
  • An object of the present invention is to improve the response speed of a vertical alignment type liquid crystal display device, and further to use a liquid crystal composition containing an electrical property and a residual DC property of the obtained liquid crystal display device, particularly an alkenyl liquid crystal.
  • the present invention provides 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 residual DC characteristics.
  • a liquid crystal aligning agent applied to a conductive film of a pair of substrates having a conductive film and heated to form a coating film on a liquid crystal cell disposed opposite to the coating film so that the coating film faces the liquid crystal layer.
  • a liquid crystal aligning agent for a liquid crystal display element formed by irradiation and containing the following component (A), component (B), and an organic solvent.
  • Component (B) a polyimide precursor which is a reaction product of a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride selected from the following formulas (1) and (1 ′) and a diamine component, and the polyimide At least one polymer selected from the group consisting of polyimides that are imidized precursors.
  • the component (B) may be the same polymer as the component (A) when it has a side chain for vertically aligning the liquid crystal. (Wherein j and k are each independently 0 or 1, and x and y are each independently a single bond, carbonyl, ester, phenylene, sulfonyl or amide group.) 2.
  • the side chain for vertically aligning the liquid crystal in the component (A) is represented by the following formula (a): 4.
  • R 1 represents an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—, —CONH.
  • R 2 , R 3 and R 4 each independently represents a phenylene group, a fluorine-containing phenylene group or a cycloalkylene group
  • R 5 is a hydrogen atom
  • a liquid crystal display device comprising the liquid crystal alignment film as described in 5 above. 7).
  • the liquid crystal aligning agent containing the following (A) component, (B) component, and an organic solvent is apply
  • a method for manufacturing a liquid crystal display element comprising a third step of irradiating light.
  • Component (A) at least one polymer selected from the group consisting of a polyimide precursor having a side chain for vertically aligning liquid crystal and polyimide which is an imidized product of this polyimide precursor.
  • Component (B) a polyimide which is a reaction product of a tetracarboxylic dianhydride component containing at least one tetracarboxylic dianhydride selected from the group consisting of the following formulas (1) and (1 ′) and a diamine At least one polymer selected from the group consisting of a precursor and a polyimide which is an imidized product of this polyimide precursor.
  • the component (B) may be the same polymer as the component (A) when it has a side chain for vertically aligning the liquid crystal. (Wherein j, k, x and y are as described above.) 8).
  • the liquid crystal layer is a liquid crystal layer containing a liquid crystalline compound having an alkenyl liquid crystal.
  • the ultraviolet irradiation amount is 1 to 50 J / cm 2 .
  • 10. 10 The method for producing a liquid crystal display element according to any one of 7 to 9, wherein the liquid crystal display element is a vertical alignment type display element.
  • the liquid crystal aligning agent used for the manufacturing method of this invention is a liquid crystal aligning agent for vertical alignment type liquid crystal display elements containing the said (A) component, (B) component, and an organic solvent.
  • the component (B) may be the same polymer as the component (A).
  • the liquid crystal alignment agent is a solution for producing a liquid crystal alignment film
  • 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 comprises, as component (A), at least one heavy selected from the group consisting of a polyimide precursor having a side chain for vertically aligning liquid crystals and a polyimide that is an imidized product of this polyimide precursor. Contains coalescence.
  • 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 group having a ring structure or a branched structure in the middle of a long-chain alkyl group, a steroid group, a group in which some or all of hydrogen atoms of these groups are replaced with fluorine atoms, and the like can be mentioned.
  • the side chain that vertically aligns the liquid crystal may be directly bonded to the main chain of polyamic acid or polyimide, or may be bonded through 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 1 represents an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—, —CONH—, or an alkylene-ether group having 1 to 3 carbon atoms
  • R 2 , R 3 , and R 4 each independently represent a phenylene group, a fluorine-containing phenylene group, or a cycloalkylene group.
  • R 5 is a hydrogen atom, an alkyl group having 2 to 24 carbon atoms, a fluorine-containing alkyl group having 2 to 24 carbon atoms, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a combination thereof. Represents a monovalent macrocyclic substituent.
  • R 1 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 2 , R 3 and R 4 in formula (a) are l, m, n, R 2 and R shown in Table 1 below from the viewpoint of ease of synthesis and ability to align liquid crystals vertically. A combination of 3 and R 4 is preferred.
  • R 5 in formula (a) is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms, or a fluorine-containing alkyl group having 2 to 14 carbon atoms. And more preferably a hydrogen atom, an alkyl group having 2 to 12 carbon atoms, or a fluorine-containing alkyl group having 2 to 12 carbon atoms.
  • R 5 is preferably an alkyl group having 12 to 22 carbon atoms, a fluorine-containing alkyl group having 12 to 22 carbon atoms, a monovalent aromatic ring, a monovalent fatty acid.
  • the content of the side chain for vertically aligning the liquid crystal is not particularly limited as long as the liquid crystal alignment film can vertically align the liquid crystal.
  • the content of the side chain that vertically aligns the liquid crystal within the range in which the vertical alignment can be maintained is possible. As few as possible is preferable.
  • the ability of a polymer having a side chain that vertically aligns the liquid crystal to vertically align the liquid crystal varies depending on the structure of the side chain that vertically aligns the liquid crystal. Generally, as the content of the side chain that vertically aligns the liquid crystal increases, the ability to align the liquid crystal vertically increases, and decreases as the content decreases. In addition, side chains having a cyclic structure tend to have a higher ability to orient liquid crystal vertically than side chains having no cyclic structure.
  • a component (A) which is at least one polymer selected from the group consisting of a polyimide precursor having a side chain for vertically aligning such a liquid crystal and a polyimide obtained by imidizing this polyimide precursor is produced.
  • the method is not particularly limited.
  • a diamine having a side chain for vertically aligning liquid crystals may be copolymerized with the tetracarboxylic dianhydride.
  • Examples of the diamine having a side chain for vertically aligning the liquid crystal include 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, and part or all of hydrogen atoms of these groups
  • a diamine having a side chain with a group in which is substituted with a fluorine atom for example, a diamine having a side chain represented by the above formula (a). More specifically, for example, diamines represented by the following formulas (2), (3), (4) and (5) can be exemplified, but the invention is 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 hydrogen atom or the like is removed from the same structure as the side chain for vertically aligning 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 a 1,4-phenylene group.
  • 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— * (where “*” Is a bond with (CH 2 ) a 2 ).
  • a 1 is 0 or an integer of 1
  • a 2 is an integer of 2 to 10
  • a 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 having 2 to 24 carbon atoms.
  • 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 having 1 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.
  • 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) examples 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 It indicates -NH-, a 13 represents an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms of 1 to 22 carbon atoms.
  • diamine represented by the formula (4) examples include diamines represented by the following formulas [A-31] to [A-32], but are not limited thereto.
  • [A-1], [A-2], [A-3], [A-4], [A-5], from the viewpoint of the ability to align the liquid crystal vertically and the response speed of the liquid crystal Diamines of [A-25], [A-26], [A-27], [A-28], [A-29], or [A-30] are preferred.
  • the above diamines can be used alone or in combination of two or more depending on the liquid crystal alignment properties, pretilt angle, voltage holding characteristics, accumulated charge and the like when the liquid crystal alignment film is formed.
  • Such a diamine having a side chain for vertically aligning the liquid crystal is preferably used in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the component (A) which is a polyamic acid, more preferably 10 to It is 40 mol%, particularly preferably 15 to 30 mol%.
  • the amount of the diamine having a side chain for vertically aligning the liquid crystal is 5 to 50 mol% of the diamine component used for the synthesis of the polyamic acid, it is particularly excellent in terms of the ability to fix the vertical alignment.
  • diamines other than the diamine which has the side chain which orients the said liquid crystal vertically can be used together as a diamine component for polyamic acid.
  • diamines 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, and decomposed by ultraviolet irradiation And a diamine having a site where a radical is generated in the side chain.
  • examples of the diamine having a photoreactive side chain include, but are not limited to, the diamine represented by the following general formula (6).
  • R 6 is a single bond, —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, or —N (CH 3 ) CO—
  • R 7 is a single bond, unsubstituted or substituted with a fluorine atom and having 1 to 20 carbon atoms
  • R 7 is a single bond, unsubstituted or substituted with a fluorine atom and having 1 to 20 carbon atoms
  • R 7 is a single bond, unsubstituted or substituted with a fluorine atom and having 1 to 20 carbon atoms
  • R 7 is a single bond, unsubstituted or substituted with a fluorine atom and having 1 to 20 carbon atoms
  • —CH 2 — in the alkylene group may be optionally replaced by
  • 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 group including at least one selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group are as follows. Examples include, but are not limited to, compounds.
  • J 1 is a single bond, a bonding group selected from —O—, —COO—, —NHCO—, or —NH—
  • J 2 is a single bond, or is unsubstituted or substituted by a fluorine atom.
  • Examples of the diamine having a side chain that is decomposed by irradiation with ultraviolet rays and generating a radical include the diamine represented by the following general formula (7), but are not limited thereto.
  • Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, which may be substituted with an organic group, and a hydrogen atom may be replaced with a halogen atom.
  • R 9 And R 10 are each independently an alkyl group or alkoxy group having 1 to 10 carbon atoms
  • T 1 and T 2 are each independently a single bond, —O—, —S—, —COO—, — OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, or —N (CH 3 ) CO—
  • the bonding position of the two amino groups (—NH 2 ) in the above formula (7) 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. In view of easiness of synthesis, high versatility, characteristics and the like, the structure represented by the following formula is most preferable, but is not limited thereto. (In the formula, n is an integer of 2 to 8.)
  • 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 formed.
  • the tetracarboxylic dianhydride to be reacted with the diamine component in the synthesis of polyamic acid 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′-biphenyl Tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-di Carboxyphenyl) methan
  • 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 dissolves. Furthermore, even if it is an organic solvent in which a polyamic acid does not melt
  • organic solvent 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, ethyl
  • 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 to 150 ° C., preferably ⁇ 5 to 100 ° C.
  • the reaction can be performed at an arbitrary 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 with respect to 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 to be obtained. Similar to the normal polycondensation reaction, the molecular weight of the polyamic acid produced increases as the molar ratio approaches 1.0. A preferred range 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, like the general polyamic acid synthesis method, instead of the tetracarboxylic dianhydride, a tetra-structure 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 carboxylic acid or tetracarboxylic acid dihalide.
  • Examples of the method for imidizing the polyamic acid to obtain a polyimide include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
  • the imidation ratio from polyamic acid to polyimide is preferably 30% or more, more preferably 50 to 99%, since the voltage holding ratio can be increased.
  • 70% or less is preferable from the viewpoint of whitening characteristics, that is, from the viewpoint of suppressing the precipitation of the polymer in the varnish. In consideration of both characteristics, 50 to 80% is more preferable.
  • the temperature is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferably performed while removing water generated by the imidation reaction from 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 the amidic acid group
  • the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amido group. 30 mole times.
  • 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, etc. 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, reaction time, and the like.
  • the reaction solution may be poured into a poor solvent and precipitated.
  • the poor solvent used for precipitation generation 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 at normal temperature or under 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 the present invention comprises, as component (B), a tetracarboxylic dianhydride component containing at least one tetracarboxylic dianhydride selected from the group consisting of the above formulas (1) and (1 ′), It contains at least one polymer selected from the group consisting of a polyimide precursor obtained by reaction with diamine and a polyimide obtained by imidizing this polyimide precursor.
  • the light irradiation causes a gap between the liquid crystal and the liquid crystal alignment film.
  • the residual DC characteristics can be improved by the interaction that appears to occur.
  • the tetracarboxylic dianhydride selected from the above formulas (1) and (1 ′) include, but are not limited to, the following compounds.
  • At least one tetracarboxylic dianhydride selected from the group consisting of the above formulas (1-1) to (1-5) is a tetracarboxylic dianhydride component used for the synthesis of the component (B) which is a polyamic acid. It is preferable to use an amount of 10 to 100% of the above. More preferably, 10 to 60% is used. More preferably, since the voltage holding ratio can be increased, at least one tetracarboxylic dianhydride selected from the group consisting of formula (1-1), formula (1-3), and formula (1-5) is used.
  • the total amount of the tetracarboxylic dianhydride components used for the synthesis of the component (B) is preferably 10 to 40 mol%, more preferably 20 to 40 mol%.
  • tetracarboxylic dianhydrides described in the component (A) may be used as a raw material for the component (B).
  • the tetracarboxylic dianhydride having an aliphatic group or an alicyclic group is used in an amount of 0 to 90 mol% of the tetracarboxylic dianhydride component used for the synthesis of the component (B) that is a polyamic acid. It is preferable.
  • the polymer as the component (B) may be made from at least one diamine selected from the group consisting of the following formulas (B-1) to (B-5) as a raw material.
  • Y 1 represents a monovalent organic group having a secondary amine, tertiary amine, or heterocyclic structure
  • Y 2 is a divalent organic having a secondary amine, tertiary amine, or heterocyclic structure. Represents a group.
  • At least one diamine having a specific structure with high polarity selected from the above formulas (B-1) to (B-5) is used, or a diamine having a carboxy group and a nitrogen-containing aromatic heterocyclic ring.
  • charge transfer is promoted by electrostatic interactions such as salt formation and hydrogen bonding, so that the residual DC characteristics can be improved.
  • Examples of at least one diamine selected from the group consisting of the formulas (B-1) to (B-5) include, but are not limited to, the following diamines.
  • the polymer which is the component (B) is obtained by using the diamine having a side chain for vertically aligning the liquid crystal used in the component (A) or the other diamine described in the section of the component (A). Also good.
  • At least one diamine selected from the group consisting of the above formulas (B-1) to (B-5) is used in an amount of 10 to 80 mol% of the diamine component used for the synthesis of the component (B) which is a polyamic acid. It is preferably used, and more preferably 20 to 70 mol%. More preferably, since the voltage holding ratio can be increased, the diamine exemplified above is selected from the group consisting of 3,5-diaminobenzoic acid and 3,5-diamino-N- (pyridin-3-ylmethyl) benzamide. At least one diamine component is preferably used in an amount of 20 to 70 mol% of the total diamine components used for the synthesis of component (B).
  • At least one tetracarboxylic dianhydride selected from the group consisting of the above formulas (1) and (1 ′), and, if necessary, other tetracarboxylic acids A tetracarboxylic dianhydride component containing a dianhydride can be reacted with a diamine component to obtain a polyimide precursor or a polyimide.
  • the method for producing the component (B) is based on the above-mentioned “component (A)” except that at least one tetracarboxylic dianhydride selected from the group consisting of the above formulas (1) and (1 ′) is used as a raw material. It is the same as “Manufacturing method”.
  • the liquid crystal aligning agent of the present invention is at least one polymer selected from the group consisting of a polyimide precursor having a side chain for vertically aligning liquid crystals and a polyimide which is an imidized product of this polyimide precursor.
  • the total content of the component (A) and the component (B) in the liquid crystal aligning agent of the present invention is not particularly limited, but is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably Is 3 to 10% by mass.
  • the content ratio of the component (A) and the component (B) is not particularly limited.
  • the component (B) may have the same polymer as the component (A) by having a side chain for vertically aligning the liquid crystal.
  • the liquid crystal aligning agent of this invention may contain other polymers other than (A) component and (B) component.
  • the content of the other polymer in all the components of the polymer is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass.
  • the molecular weight of the polymer of the liquid crystal aligning agent is GPC (Gel Permeation Chromatography) in consideration of the strength of the liquid crystal aligning film obtained by applying the liquid crystal aligning agent, workability when forming the coating film, uniformity of the coating film, etc. ),
  • the weight average molecular weight measured by the method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
  • the organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can dissolve or disperse components such as the component (A) and the component (B).
  • combination of said polyamic acid can be mentioned.
  • N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like are soluble.
  • N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferable, but 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, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, prop
  • the liquid crystal aligning agent may contain components other than those described above. Examples include a compound that improves the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, a compound that improves the adhesion between the liquid crystal aligning film and the substrate, and the film strength of the liquid crystal aligning film is further improved. Compound etc. are mentioned.
  • 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 is added. Also good. When these compounds are used, 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 the purpose of changing the electrical properties such as the dielectric constant or 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 is at least one polymer selected from the group consisting of a polyimide precursor having side chains for vertically aligning liquid crystals and a polyimide obtained by imidizing this polyimide precursor (A ) Component and a polyimide precursor obtained by reaction with a tetracarboxylic dianhydride component containing at least one tetracarboxylic dianhydride selected from the group consisting of the above formulas (1) and (1 ′), and Since the component (B) which is at least 1 type of polymer chosen from the group which consists of a polyimide obtained by imidating this polyimide precursor is contained, a residual DC characteristic can be made favorable.
  • the substrate is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
  • 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 only one substrate is used. In this case, a material that reflects light such as aluminum can be used as the electrode.
  • 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 baking 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 to 300 ° C., more preferably 150-250 ° 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 is formed of two substrates disposed so as 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.
  • the liquid crystal display element of a vertical alignment system comprising a liquid crystal cell having a liquid crystal alignment film formed.
  • the liquid crystal alignment agent of the present invention is applied onto two substrates and baked to form a liquid crystal alignment film, and the two substrates are arranged so that the liquid crystal alignment films face each other.
  • This is a vertical alignment type liquid crystal display element comprising a liquid crystal cell produced by sandwiching a liquid crystal layer composed of liquid crystal between the two substrates and irradiating with ultraviolet rays.
  • the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention by using the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention and irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet rays, an interaction occurs between the liquid crystal and the liquid crystal alignment film of the present invention.
  • the liquid crystal display element has a small liquid crystal residual DC and is unlikely to cause image sticking.
  • 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 is formed.
  • substrate described with the said liquid crystal aligning film can be mentioned.
  • the liquid crystal display element of the present invention may use a substrate provided with a conventional electrode pattern or protrusion pattern, but by having a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention, Operation is possible even if a substrate with a structure in which 1 to 10 ⁇ m line / slit electrode pattern is formed on one side substrate and no slit pattern or projection pattern is formed on the opposite substrate, and the process at the time of device fabrication is 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 transmissive liquid crystal display element the above-described substrate is generally used.
  • an opaque substrate such as a silicon wafer can be used if only one substrate is used. is there. 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.
  • nematic liquid crystal having negative dielectric anisotropy can be used as the liquid crystal composition used in the liquid crystal display element of the present invention.
  • dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, and terphenyl liquid crystal can be used.
  • an alkenyl liquid crystal in combination A conventionally well-known thing can be used as such an alkenyl type liquid crystal.
  • a compound represented by the following formula can be exemplified, but the present invention is not limited thereto.
  • the liquid crystal composition constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited as long as it is a liquid crystal material used in a vertical alignment method.
  • MLC-6608, MLC-6609, etc. which are liquid crystal compositions having negative dielectric anisotropy, manufactured by Merck & Co., Inc. can be used.
  • MLC-3022, MLC-3023 (including photopolymerizable compound (RM)) manufactured by Merck Co., Ltd. which are liquid crystal compositions containing alkenyl liquid crystals and having negative dielectric anisotropy, 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, spacers such as beads are dispersed on the liquid crystal alignment film on one substrate, and an adhesive is applied around the substrate, and then a liquid crystal alignment film is formed. There is a method in which the other side is bonded so that the surface on the inner side becomes the inner side, and liquid crystal is injected under reduced pressure for sealing.
  • a liquid crystal cell can also be manufactured by a method in which the other substrate is bonded and sealed with the other surface facing inward.
  • the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • the step of manufacturing the liquid crystal cell by irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet rays may be performed at any time after the liquid crystal is sealed.
  • the irradiation amount of ultraviolet rays is, for example, 1 to 60 J / cm 2 , preferably 40 J / cm 2 or less, and the smaller the irradiation amount of ultraviolet rays, the lower the reliability caused by the destruction of the members constituting the liquid crystal display element.
  • the wavelength of the ultraviolet rays used is preferably 300 to 500 nm, more preferably 300 to 400 nm.
  • the irradiation of the liquid crystal alignment film and the liquid crystal layer with ultraviolet rays may be performed while applying a voltage and maintaining the electric field.
  • the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.
  • 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 a rubbing process or a photo-alignment process. It can also be suitably used for producing a liquid crystal alignment film to be formed.
  • NMP N-methyl-2-pyrrolidone.
  • BCS Butyl cellosolve.
  • ⁇ Polyimide molecular weight measurement> Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. Column: Column manufactured by Shodex (KD-803, KD-805), Column temperature: 50 ° C.
  • N N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) at 10 ml / L), Flow rate: 1.0 ml / min, Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight about 9,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation and polyethylene glycol (molecular weight about 12,000, molecular weight manufactured by Polymer Laboratories) 4,000 and 1,000).
  • 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 NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). It is the number ratio of the reference proton to one proton.
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
  • NMP (18.0 g) was added to the obtained polyimide powder A (2.0 g), and dissolved by stirring at 70 ° C. for 12 hours.
  • BCS (13.3g) was added to this solution, and liquid crystal aligning agent A1 was obtained by stirring at room temperature for 2 hours.
  • a liquid crystal aligning agent U1 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder B (2.0 g) was used instead of the polyimide powder A. Then, BODA (3.75 g, 15 mmol), DA-3 (1.90 g, 4.99 mmol), m-PDA (2.16 g, 20.0 mmol), were dissolved in NMP (29.7 g), and 60 After reacting at 4 ° C. for 4 hours, PMDA (2.10 g, 9.63 mmol) and NMP (9.92 g) were added and reacted at 40 ° C.
  • a liquid crystal aligning agent L1 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder C (2.0 g) was used instead of the polyimide powder A.
  • the liquid crystal aligning agent U1 thus obtained was mixed as a first component with 5.0 g, and the liquid crystal aligning agent L1 as a second component was mixed with 5.0 g to obtain a liquid crystal aligning agent A2.
  • a liquid crystal aligning agent U2 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder D (2.0 g) was used instead of the polyimide powder A.
  • BODA 123 g, 491 mmol
  • DBA 127 g, 837 mmol
  • DA-1 60.7 g, 148 mmol
  • polyimide powder E The imidation ratio of this polyimide was 73%, the number average molecular weight was 13000 and the weight average molecular weight was 39000.
  • a liquid crystal aligning agent L2 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder E (2.0 g) was used instead of the polyimide powder A.
  • the obtained liquid crystal aligning agent U2 was mixed with 5.0 g as the first component, and 5.0 g was mixed with the liquid crystal aligning agent L2 as the second component to obtain a liquid crystal aligning agent A3.
  • a liquid crystal aligning agent U3 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder F (2.0 g) was used instead of the polyimide powder A.
  • BODA (3.15 g, 12.6 mmol)
  • DA-3 (2.40 g, 6.31 mmol)
  • DBA (1.28 g, 8.40 mmol)
  • 3AMPDA (1.25 g, 6.31 mmol)
  • NMP 30.4 g
  • PMDA (1.79 g, 8.19 mmol
  • NMP (10.14 g) were added and reacted at room temperature for 4 hours to obtain a polyamic acid solution.
  • a liquid crystal aligning agent L3 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder G (2.0 g) was used instead of the polyimide powder A.
  • the obtained liquid crystal aligning agent U3 was mixed as a first component with 5.0 g, and the liquid crystal aligning agent L3 as a second component was mixed with 5.0 g to obtain a liquid crystal aligning agent A4.
  • a liquid crystal aligning agent L4 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder H (2.0 g) was used instead of the polyimide powder A.
  • the liquid crystal aligning agent U1 obtained in Synthesis Example 2 was mixed as a first component with 5.0 g, and the liquid crystal aligning agent L4 as a second component was mixed with 5.0 g to obtain a liquid crystal aligning agent A5.
  • a liquid crystal aligning agent L5 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder J (2.0 g) was used instead of the polyimide powder A.
  • Synthesis Example 3 5.0 g of the obtained liquid crystal aligning agent U2 as a first component and 5.0 g of the liquid crystal aligning agent L5 as a second component were mixed to obtain a liquid crystal aligning agent A8.
  • a liquid crystal aligning agent L6 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder L (2.0 g) was used instead of the polyimide powder A.
  • Synthesis Example 3 5.0 g of liquid crystal aligning agent U2 obtained as a first component and 5.0 g of liquid crystal aligning agent L6 as a second component were mixed to obtain liquid crystal aligning agent A9.
  • a liquid crystal aligning agent U4 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder M (2.0 g) was used instead of the polyimide powder A.
  • BODA (1.20 g, 4.80 mmol
  • DBA (1.46 g, 9.59 mmol
  • 3AMPDA (1.74 g, 7.18 mmol
  • DA-3 (2.74 g, 7.20 mmol) were then added to NMP.
  • (28.58 g) was dissolved and reacted at 60 ° C. for 2 hours.
  • PMDA (1.05 g, 4.81 mmol
  • NMP (4.19 g) were added and reacted at room temperature for 4 hours.
  • CBDA (2.78 g, 14.18 mmol) and NMP ( 11.1 g) was added and reacted at room temperature for 4 hours to obtain a polyamic acid solution.
  • NMP NMP
  • acetic anhydride 8.90 g
  • pyridine 2.76 g
  • This reaction solution was poured into methanol (472 g), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder N.
  • a liquid crystal aligning agent L7 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder N (2.0 g) was used instead of the polyimide powder A. 3.0 g of the obtained liquid crystal aligning agent U4 as a first component and 7.0 g of the liquid crystal aligning agent L7 as a second component were mixed to obtain a liquid crystal aligning agent A10.
  • a liquid crystal aligning agent L8 was obtained in the same manner as in Synthesis Example 1 except that the obtained polyimide powder O (2.0 g) was used instead of the polyimide powder A.
  • the liquid crystal aligning agent U4 obtained in Synthesis Example 10 was mixed as a first component with 3.0 g, and the liquid crystal aligning agent L8 as a second component was mixed with 7.0 g to obtain a liquid crystal aligning agent A11.
  • NMP (18.0 g) was added to the obtained polyimide powder P (2.0 g), and the mixture was dissolved by stirring at 70 ° C. for 12 hours.
  • BCS (13.3g) was added to this solution, and it stirred at room temperature for 2 hours, and obtained liquid crystal aligning agent A12.
  • Example A Using the liquid crystal aligning agent A1 obtained in Synthesis Example 1, a liquid crystal cell was prepared according to the procedure shown below.
  • the liquid crystal aligning agent A1 obtained in Synthesis Example 1 is spin-coated on the ITO surface of the ITO electrode substrate on which an 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 the hot plate, baking was performed in a hot air circulation oven at 200 ° C. for 20 minutes to form a liquid crystal alignment film having a thickness of 100 nm.
  • liquid crystal aligning agent A1 is spin-coated on the ITO surface on which no electrode pattern is formed, dried on an 80 ° C. hot plate for 90 seconds, and then baked in a 200 ° C. hot air circulation oven for 20 minutes.
  • a 100 nm liquid crystal alignment film was formed.
  • the sealing compound solvent type thermosetting type epoxy resin
  • 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.
  • Liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.), which is a liquid crystal composition containing no alkenyl-based liquid crystal, was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell.
  • the obtained liquid crystal cell was annealed (realignment treatment) for 30 minutes in a circulation oven at 110 ° C. Thereafter, the liquid crystal cell was irradiated with light under the following conditions, and the voltage holding ratio and residual DC were measured under the following conditions. For comparison, the voltage holding ratio and residual DC were also measured under the same conditions for a liquid crystal cell that was not irradiated with light.
  • UV Light irradiation
  • UV was passed through a 365 nm bandpass filter and irradiated with 6 J / cm 2 (the lamp used was a USHIO Super High Pressure Mercury Lamp LL, ORC UV Light Measure Model UV-M03A (attachment: UV The illuminance was measured at ⁇ 35).
  • the obtained liquid crystal cell was measured by applying a voltage of 1 V for 60 ⁇ s at a temperature of 60 ° C. using a VHR-1A manufactured by Toyo Technica Co., Ltd., and measuring a voltage holding ratio after 1667 ms. .
  • Example B Comparative Example A, Reference Example A
  • a liquid crystal cell irradiated with light was manufactured by performing the same operation as in Example A, and the voltage holding ratio and residual DC were measured. .
  • Example 1 A light-irradiated liquid crystal cell was produced in the same manner as in Example A except that MLC-3022 (trade name of Merck), which is a liquid crystal composition containing an alkenyl liquid crystal, was used instead of MLC-6608. The voltage holding ratio and residual DC were measured.
  • MLC-3022 trade name of Merck
  • Examples 2 to 4, 8 to 14 Except for using the liquid crystal aligning agent described in Table 3 instead of the liquid crystal aligning agent A1, a liquid crystal cell irradiated with light was manufactured by performing the same operation as in Example 1, and the voltage holding ratio and the residual DC were measured. .
  • Example 5 Instead of MLC-6608, MLC-3023 (trade name of Merck), which is a liquid crystal composition containing an alkenyl liquid crystal and RM (photopolymerizable compound), is used, and liquid crystal aligning agent A2 is used instead of liquid crystal aligning agent A1. Further, instead of light irradiation, a liquid crystal cell irradiated with light was manufactured by performing the same operation as in Example A except that the PSA treatment was performed under the following conditions, and the voltage holding ratio and residual DC were measured.
  • UV processing With a DC voltage of 15 V applied, UV was applied from the outside of the liquid crystal cell through a 325 nm high-pass filter at 10 J / cm 2 (the lamp used was a USHIO Super High Pressure Mercury Lamp LL, ORC UV Light Measure Illuminance was measured with Model UV-M03A (attachment: UV-35). Thereafter, UV (UV lamp: FLR40SUV32 / A-1) was irradiated for 30 minutes using a UV-FL irradiation apparatus manufactured by Toshiba Lighting & Technology Co., Ltd. in a state where no voltage was applied.
  • Example 15 to 19 A PSA-treated liquid crystal cell was produced by performing the same operation as in Example 5 except that the liquid crystal aligning agent described in Table 4 was used instead of the liquid crystal aligning agent A2, and the voltage holding ratio and residual DC were measured. .
  • Example 6 Example A except that MLC-3022 (trade name of Merck), which is a liquid crystal composition containing an alkenyl liquid crystal, was used instead of MLC-6608, and liquid crystal aligning agent A2 was used instead of liquid crystal aligning agent A1.
  • MLC-3022 trade name of Merck
  • liquid crystal aligning agent A2 was used instead of liquid crystal aligning agent A1.
  • a liquid crystal cell irradiated with light was manufactured in the same manner, and the liquid crystal cell was annealed for 3 hours in a circulation oven at 150 ° C., and then the voltage holding ratio and residual DC were measured.
  • Example 7 Example A except that MLC-3022 (trade name of Merck), which is a liquid crystal composition containing an alkenyl liquid crystal, was used instead of MLC-6608, and liquid crystal aligning agent A2 was used instead of liquid crystal aligning agent A1.
  • a liquid crystal cell irradiated with light was manufactured by performing the same operation, and the liquid crystal cell was annealed for 3 hours in a circulation oven at 150 ° C., and further irradiated with light under the same conditions. Retention and residual DC were measured.
  • Table 2 shows the results of using MLC-6608, which is a conventional liquid crystal not containing an alkenyl liquid crystal, as Examples A and B, Comparative Example A, and Reference Example A.
  • MLC-6608 which is a conventional liquid crystal not containing an alkenyl liquid crystal
  • Comparative Example A and Reference Example A that do not use a polymer having a structural unit derived from PMDA
  • the accumulation of residual DC is suppressed in Reference Example A using a highly polar diamine, which is a conventional technique for reducing residual DC.
  • Example A and Example B using the polymer having a structural unit derived from PMDA there is a difference in the degree depending on the introduction amount of the structural unit derived from PMDA, but the residual DC is smaller than that in Comparative Example A. It is reduced, and further reduction is seen by light irradiation.
  • MLC-6608 which is a liquid crystal composition that does not contain an alkenyl-based liquid crystal
  • the alignment film can also be reduced by light irradiation.
  • Table 3 shows the results using MLC-3022 which is a liquid crystal composition containing an alkenyl liquid crystal. Compared with Table 2, it can be seen that the overall voltage holding ratio is reduced.
  • Comparative Example 1 and Comparative Example 2 also in Comparative Example 2 using the liquid crystal aligning agent A6 that was effective in residual DC with MLC-6608, the accumulated amount of residual DC was large regardless of the presence or absence of light irradiation.
  • Example 11, Example 12, Example 13, and Example 14 the residual DC in the unirradiated light was large as in Comparative Example 2, but was greatly reduced by performing the light irradiation.
  • Table 4 shows the results using MLC-3023, which is a liquid crystal composition containing alkenyl liquid crystal and RM. Similar to Table 3, the voltage holding ratio is low compared to Table 2, but Comparative Examples 3 and 4 have a large amount of residual DC accumulated regardless of the presence or absence of the PSA treatment. However, in Examples 5 and 15 to 19 using polymers having structural units derived from PMDA, CA-1 or CA-2, residual DC was greatly reduced by performing the PSA treatment. Thus, when a liquid crystal composition containing an alkenyl-based liquid crystal is used, the conventional residual DC reduction method is not effective, and a polymer having a structural unit derived from PMDA, CA-1 or CA-2 is used. By using the liquid crystal alignment film including the residual DC, the residual DC is reduced by performing the PSA process.
  • Example 5 Similar to the examples shown in Table 3 and Table 4, the polymer having PMDA-derived structural units was used, and factors that can reduce the accumulation of residual DC by light irradiation were examined (Table 5).
  • Example 5 when light irradiation was performed using liquid crystal aligning agent A2 containing the polymer which has a structural unit derived from PMDA, residual DC has decreased compared with non-irradiation. Furthermore, when annealing was performed at 150 ° C. for 3 hours after light irradiation, accumulation of residual DC was confirmed to be the same as the result of non-light irradiation (Example 6).
  • the tetracarboxylic dianhydride for example, the formula (1) and the formula (1 ′)
  • PMDA structural unit derived from
  • the liquid crystal display element obtained by the present invention is useful as a vertical alignment type liquid crystal display element such as a PSA liquid crystal display or an SC-PVA liquid crystal display.
  • a vertical alignment type liquid crystal display element such as a PSA liquid crystal display or an SC-PVA liquid crystal display.

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Abstract

L'invention concerne un agent d'alignement de cristaux liquides ayant de bonnes caractéristiques de courant continu résiduel, un film orienté à cristaux liquides, un élément d'affichage à cristaux liquides, et un procédé de fabrication d'un élément d'affichage à cristaux liquides. L'agent d'alignement de cristaux liquides est destiné à être utilisé dans un élément d'affichage à cristaux liquides obtenu par photo-irradiation d'une cellule à cristaux liquides dans laquelle une paire de substrats, ayant des films conducteurs qui sont revêtus d'un agent d'alignement de cristaux liquides et chauffés pour former un film de revêtement, sont agencés en opposition avec les films de revêtement faisant face à une couche de cristaux liquide intermédiaire. L'agent d'alignement de cristaux liquides contient le constituant (A), le constituant (B) et un solvant organique suivants. Constituant (A) : au moins un polymère choisi dans le groupe constitué de précurseurs de polyimide ayant des chaînes latérales pour amener les cristaux liquides à s'orienter verticalement, et des polyimides qui sont des imides de ces précurseurs de polyimide. Constituant (B) : au moins un polymère choisi dans le groupe constitué de précurseurs de polyimide qui sont des produits de réaction d'un constituant de diamine et d'un constituant de dianhydride tétracarboxylique qui contient un dianhydride tétracarboxylique choisi parmi les équations (1) et (1') suivantes, et des polyimides qui sont des imides de ces précurseurs de polyimide. Lorsque le constituant (B) a des chaînes latérales pour amener les cristaux liquides à s'orienter verticalement, le constituant peut être un polymère identique à celui du constituant (A). (j et k sont 0 ou 1, et x et y sont des liaisons simples, des groupes carbonyle, ou analogues.)
PCT/JP2016/053413 2015-02-06 2016-02-04 Agent d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et procédé de fabrication d'élément d'affichage à cristaux liquides WO2016125870A1 (fr)

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KR1020177023922A KR102502321B1 (ko) 2015-02-06 2016-02-04 액정 배향제, 액정 표시 소자 및 액정 표시 소자의 제조 방법
KR1020237005293A KR102607979B1 (ko) 2015-02-06 2016-02-04 액정 배향제, 액정 표시 소자 및 액정 표시 소자의 제조 방법
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KR20190055196A (ko) * 2016-09-29 2019-05-22 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
JPWO2018062439A1 (ja) * 2016-09-29 2019-07-11 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
JPWO2018062440A1 (ja) * 2016-09-29 2019-07-18 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
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KR102465496B1 (ko) * 2016-09-29 2022-11-09 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막, 및 액정 표시 소자
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