WO2018097155A1 - Procédé de fabrication d'élément d'affichage à cristaux liquides, substrat pour élément d'affichage à cristaux liquides et ensemble d'éléments d'affichage à cristaux liquides - Google Patents

Procédé de fabrication d'élément d'affichage à cristaux liquides, substrat pour élément d'affichage à cristaux liquides et ensemble d'éléments d'affichage à cristaux liquides Download PDF

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WO2018097155A1
WO2018097155A1 PCT/JP2017/041921 JP2017041921W WO2018097155A1 WO 2018097155 A1 WO2018097155 A1 WO 2018097155A1 JP 2017041921 W JP2017041921 W JP 2017041921W WO 2018097155 A1 WO2018097155 A1 WO 2018097155A1
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liquid crystal
group
carbon atoms
display element
crystal display
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PCT/JP2017/041921
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English (en)
Japanese (ja)
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亮一 芦澤
徳俊 三木
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日産化学工業株式会社
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Priority to CN201780084134.8A priority Critical patent/CN110192148B/zh
Priority to KR1020197017683A priority patent/KR102609041B1/ko
Priority to JP2018552604A priority patent/JP7227557B2/ja
Publication of WO2018097155A1 publication Critical patent/WO2018097155A1/fr

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    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a method for manufacturing a liquid crystal display element, a substrate for a liquid crystal display element, and a liquid crystal display element assembly, and in particular, a vertical alignment type liquid crystal display produced by irradiating ultraviolet rays with voltage applied to liquid crystal molecules.
  • the present invention relates to an element manufacturing method, a liquid crystal display element substrate, and a liquid crystal display element assembly.
  • a liquid crystal display element of a method in which liquid crystal molecules aligned perpendicular to the substrate respond by an electric field also referred to as a vertical alignment (VA) method
  • VA vertical alignment
  • a photopolymerizable compound is previously added to the liquid crystal composition, and a polyimide-based vertical alignment film is used, and ultraviolet rays are applied while applying a voltage to the liquid crystal cell. Therefore, a technique for increasing the response speed of liquid crystal (PSA (Polymer Sustained Alignment) type element, for example, see Patent Document 1 and Non-Patent Document 1) is known.
  • PSA Polymer Sustained Alignment
  • the direction in which the liquid crystal molecules incline in response to an electric field is usually controlled by protrusions provided on the substrate or slits provided on the display electrode, but photopolymerization is performed in the liquid crystal composition.
  • photopolymerization is performed in the liquid crystal composition.
  • the first alignment film is formed on the first substrate using the first alignment liquid containing the first alignment agent
  • the second alignment film is formed on the second substrate using the second alignment liquid containing the second alignment agent.
  • light irradiation is performed while applying an electric field with a liquid crystal layer sandwiched between these substrates, and the first pretilt angle is expressed in the liquid crystal molecules adjacent to the first alignment film, while adjacent to the second alignment film.
  • a method of manufacturing a liquid crystal display element that causes a liquid crystal molecule to exhibit a second pretilt angle has been proposed (see Patent Document 3).
  • JP 2003-307720 A WO2015 / 033921 Republic of Korea 10-2016-0002599
  • Patent Document 3 it is necessary to use two kinds of liquid crystal aligning agents, and there is a problem that a large capital investment is required due to an increase in the number of processes and an increase in production lines.
  • An object of the present invention is to provide a method for producing a liquid crystal display element capable of producing a liquid crystal display element having liquid crystal layers having different alignment states on both sides more easily without involving the above-mentioned problems, and this production method. It is an object to provide a substrate for a liquid crystal display element and a liquid crystal display element assembly using the above.
  • the present inventors have used a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation, and before providing a liquid crystal layer, liquid crystal on at least one side in advance. Irradiate light to the alignment film and invalidate at least part of the radical generation structure of the radical generation structure of the liquid crystal alignment film on one side, or perform light irradiation so that the amount of light irradiation differs for both radicals.
  • the inventors have found that a liquid crystal layer having different alignment states can be formed on both sides of the liquid crystal layer by making the generation ability different, and the present invention has been completed.
  • the present invention has the following gist.
  • a liquid crystal alignment film forming step of forming a liquid crystal alignment film with a liquid crystal aligning agent having the same composition containing a polymer having a radical generating structure that generates radicals by light irradiation on each of the surfaces of the pair of substrates; and the pair of substrates A liquid crystal alignment film light irradiating step in which at least one of the liquid crystal is irradiated with light to change the amount of light applied to the liquid crystal alignment films in different states, and then a liquid crystal layer containing a liquid crystal compound is formed between the pair of substrates And a liquid crystal layer forming step.
  • a substrate for forming a liquid crystal display element comprising a liquid crystal alignment film, wherein the liquid crystal alignment film is formed of a liquid crystal alignment agent containing a polymer having a radical generating structure that generates radicals upon light irradiation.
  • a substrate for forming a liquid crystal display element wherein a radical is generated from at least a part of the radical generating structure by light irradiation.
  • a liquid crystal display element assembly comprising a liquid crystal display element forming substrate having a pair of liquid crystal alignment films and a liquid crystal layer provided between the pair of liquid crystal display element substrates,
  • the liquid crystal alignment film of the formation substrate for a liquid crystal display element is formed of a liquid crystal aligning agent having the same composition containing a polymer having a radical generating structure that generates radicals upon light irradiation, and at least one is irradiated with light.
  • the liquid crystal display element assembly is characterized in that the light irradiation amounts of the two differ from each other.
  • a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation is used, and at least one liquid crystal alignment film is irradiated in advance before providing a liquid crystal layer.
  • a liquid crystal layer having different alignment states on both sides of the liquid crystal layer can be formed, and a liquid crystal display element having a liquid crystal layer having different alignment states on both sides can be more easily manufactured.
  • a method, a liquid crystal display element substrate and a liquid crystal display element assembly used in the manufacturing method can be provided.
  • liquid crystal aligning agent suitable for a vertical alignment type liquid crystal display element, particularly a PSA type liquid crystal display element, which has a high response speed.
  • the method for producing a liquid crystal display element according to the present invention includes forming a liquid crystal alignment film on each of the surfaces of a pair of substrates with a liquid crystal alignment agent containing a polymer having a radical generating structure that generates radicals upon light irradiation. Between the forming step, the liquid crystal alignment film light irradiating step in which at least one of the pair of substrates is irradiated with light and the amount of light irradiation to the liquid crystal alignment film is different, and then between the pair of substrates, And a liquid crystal layer forming step of forming a liquid crystal layer containing a liquid crystal compound.
  • liquid crystal alignment film forming step of the present invention a substrate on which a liquid crystal alignment film formed with a liquid crystal alignment agent having the same composition is prepared.
  • the liquid crystal aligning agent used here is a liquid crystal aligning agent containing a polymer having a radical generating structure that generates radicals by light irradiation. Details of the liquid crystal aligning agent will be described later.
  • a liquid crystal alignment film light irradiation step in which at least one of the pair of substrates is irradiated with light so that the amount of light irradiation to the liquid crystal alignment films is different.
  • the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least part of the radical generating ability of the radical generating structure of the liquid crystal alignment film on one side, or both Irradiation is performed so that the amount of light irradiation is different so that the radical generating ability on both sides is different.
  • the light irradiation is to invalidate at least a part of the radical generation structure of the provided liquid crystal alignment film, that is, to generate radicals at this point and not to generate radicals thereafter.
  • the light irradiation may be performed with light having a wavelength necessary to deactivate the radical generating structure.
  • the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least a part of the radical generating structure, thereby invalidating the radical generating ability.
  • one is a liquid crystal alignment film having no radical generation ability
  • the other is a liquid crystal alignment film having radical generation ability
  • one is a liquid crystal alignment film having low radical generation ability
  • the other is a liquid crystal alignment film having high radical generation ability.
  • the liquid crystal alignment films of the substrates on both sides are irradiated with light, but the amount of light irradiation is different on both sides, and the amount of radical generation structure to be invalidated is different on both sides.
  • one is a liquid crystal alignment film having a low radical generation capability and the other is a liquid crystal alignment film having a high radical generation capability so that the radical generation capability on both sides is different.
  • a liquid crystal layer forming step of forming a liquid crystal layer containing a polymerizable compound between the pair of substrates is included. Accordingly, since the liquid crystal layer is formed by being sandwiched between a pair of liquid crystal alignment films having different radical generation capabilities, it is possible to form an asymmetric liquid crystal layer having different pretilt angles on both sides.
  • the polymer having a radical generating structure used in the present invention has a site where a radical is generated by light irradiation, for example, ultraviolet irradiation, as a side chain.
  • a radical is generated by light irradiation, for example, ultraviolet irradiation
  • Examples of the specific polymer include a polymer having a side chain structure represented by the following formula (I) as a radical generating structure in which radicals are generated by ultraviolet irradiation.
  • Ar represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, in which an organic group may be substituted, and a hydrogen atom may be substituted with a halogen atom.
  • R 1 and R 2 are each independently an alkyl group or alkoxy group having 1 to 10 carbon atoms
  • T1 and T2 are each independently a single bond or —O—, —COO—, —OCO—, — NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, —N (CH 3 ) CO—
  • the alkylene group —CH 2 — or —CF 2 — may be optionally replaced with —CH ⁇ CH—, and when any of the following groups is not adjacent to each
  • R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 3 represents —CH 2 —, —NR—, —O—, or —S—).
  • Ar to which carbonyl is bonded is involved in the absorption wavelength of ultraviolet rays. Therefore, when the wavelength is increased, a structure having a long conjugate length such as naphthylene or biphenylene is preferable.
  • Ar may be substituted with a substituent, and the substituent is preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, and an amino group.
  • R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group, or a phenethyl group. In the case of an alkyl group or an alkoxy group, R 1 and R 2 are May be formed.
  • Q is preferably an electron donating organic group, and the above group is preferable.
  • Q is an amino derivative
  • the side chain structure of the formula (I) can be handled as a raw material. It is preferable from the viewpoint of easy synthesis of the polymer.
  • the site where radicals are generated by ultraviolet irradiation in the above formula (I) is preferably as follows.
  • (b) or (c) is preferable from the viewpoint of the reliability of the obtained liquid crystal display element.
  • —T 1 —ST 2 — serves as a linking group that connects diaminobenzene and a site that generates a radical upon irradiation with ultraviolet rays.
  • 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—.
  • S is a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom (provided that —CH 2 — or —CF 2 — of the alkylene group is optionally substituted with —CH ⁇ CH—). If any of the following groups are not adjacent to each other, these groups may be substituted; —O—, —COO—, —OCO—, —NHCO—, —CONH—, — NH—, a divalent carbocyclic ring or a heterocyclic ring. In particular, T 2 is most preferably —O— in terms of synthesis difficulty.
  • S is preferably an alkylene group having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, from the viewpoint of synthesis difficulty or solubility.
  • examples of the specific polymer used in the present invention include a polymer having a side chain structure represented by the following formula (II).
  • a point means a bond to the main chain of the polymer
  • n is an integer selected from 1 to 12
  • X is a single bond, —O—, —COO—, —OCO—, — NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, or —N (CH 3 ) CO— is represented.
  • Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms having at least one unsaturated bond which is necessarily bonded to the carbonyl carbon of the imide group, and a part of the carbon atoms constituting the cyclic hydrocarbon is heterogeneous. It may be replaced by an atom.
  • Such a specific polymer has an organic group represented by the above formula (II) in the side chain. It is considered that this organic group is excited by ultraviolet irradiation to generate a radical, or has a function of chain-transferring a radical generated by another organic group, and functions as a radical generating structure.
  • the structure having the function of chain-transferring this radical is also included in the radical generating structure of the present invention.
  • Cy that is, a cyclic hydrocarbon group having at least one unsaturated bond
  • a structure in which the bonds are directly connected is preferable.
  • the greater the number of unsaturated bonds the higher the absorbance in the ultraviolet region and the longer the absorption wavelength, which is preferable when performing long wavelength exposure.
  • an aromatic hydrocarbon group having 6 to 14 carbon atoms, a heterocyclic compound, and the like are more preferable.
  • a cyclic hydrocarbon group containing no hetero atom is preferable.
  • the two points of Cy each represent a bond to imidocarbonyl carbon.
  • the number of carbon atoms forming the ring structure increases, the structure becomes more rigid and the solubility in the solvent becomes poor. Therefore, from the viewpoint of monomer synthesis and the ease of handling of the monomer, the number of carbon atoms is relatively high. Fewer cyclic hydrocarbon groups are preferred, and particularly preferred are cyclohexene, benzene, naphthalene, biphenylene and the like. More preferred is the following structure.
  • the hydrogen atom of the cyclic hydrocarbon group directly connected to the imide ring may be replaced with a fluorine atom or the like, or an organic group may be substituted.
  • the organic group to be substituted is not particularly limited, but introduction of an organic group having a strong electron donating property or electron accepting property is preferable because an effect of increasing the absorption wavelength is expected.
  • a nitro group or an amino group may trap a generated radical
  • a monovalent organic group having a molecular weight of 14 to 100 is preferable, for example, an organic group such as a hydroxy group or a hydroxyl group, An alkoxyl group or an alkyl group having a relatively small molecular weight can be mentioned, but since the introduced substituent may trap the generated radical, it is necessary to pay attention to the selection of the substituent. For the above reasons, it is most preferably unsubstituted.
  • —X—C n (H 2 ) n — represents a connecting site with a polymer chain.
  • the linking site is not particularly limited. A bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) —, or — N (CH 3 ) CO— and the like can be mentioned.
  • the alkylene linked to X is preferably an alkylene having 1 to 12 carbon atoms, and the alkylene may have an unsaturated bond, a branched chain, or a cyclic structure, and the hydrogen atom in the alkylene is replaced with fluorine. It may be done. From the viewpoint of reagent availability and synthesis, X is —O— as the most easily synthesized structure, and alkylene is a straight-chain alkylene having 1 to 6 carbon atoms.
  • the means for introducing the side chain into the polymer is not particularly limited. Examples thereof include a method of obtaining a polymer by polymerization using a monomer having a side chain structure represented by the above formula (II), a method of introducing by polymer modification, and the like. Preferably, it is a method of introducing into a polymer using a monomer having an organic group represented by the above formula (I).
  • the radical generating structure of the present invention is not limited to those described above, and any other side chain structure having a radical generating structure other than the described side chain structure can be preferably used.
  • a polymer containing a radical generating structure containing a reactive mesogen structure (see Patent Document 3, claim 1, etc.) in the side chain can be used.
  • the specific polymer contained in the liquid crystal aligning agent used in the present invention contains a liquid crystal in addition to the side chain having a radical generating structure represented by the above formula (I) or (II) (hereinafter also referred to as a specific side chain). It is preferred to have side chains that are oriented vertically.
  • the side chain for vertically aligning the liquid crystal is represented by the following formula [III-1] or [III-2]. In addition, you may mix
  • X 1 is a single bond, - (CH 2) a - (a is an integer of 1 ⁇ 15), - O - , - CH 2 O -, - COO- or -OCO- .
  • X 2 representing a is Represents a single bond or (CH 2 ) b — (b is an integer of 1 to 15.)
  • X 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), Represents —O—, —CH 2 O—, —COO—, or —OCO—, wherein X 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring;
  • the hydrogen atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon
  • X 4 is selected from an organic group having a carbon number of 17 to 51 having a steroid skeleton That may be a divalent organic group .
  • X 5 represents a divalent cyclic group selected from benzene ring, cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, C 1 - 3 may be substituted with an alkyl group of 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
  • X 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
  • X 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O, from the viewpoint of availability of raw materials and ease of synthesis.
  • — Or —COO— is preferable, and more preferable is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • X 2 is preferably a single bond or (CH 2 ) b — (b is an integer of 1 to 10).
  • X 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, or —COO—, among these, from the viewpoint of ease of synthesis. And more preferably a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O— or —COO—.
  • X 4 is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton from the viewpoint of ease of synthesis.
  • X 5 is preferably a benzene ring or a cyclohexane ring.
  • n is preferably 0 to 3 and more preferably 0 to 2 in view of availability of raw materials and ease of synthesis.
  • X 6 is preferably an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
  • the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention has 12 to 20 carbon atoms having a steroid skeleton.
  • An organic group having 12 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.
  • (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-268) to (2-315) , (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) are preferred.
  • Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).
  • X 7 represents a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— or —OCO—.
  • X 8 represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. Among them, X 7 is preferably a single bond, —O—, —CH 2 O—, —CONH—, —CON (CH 3 ) — or —COO—, and more preferably a single bond, —O—, — CONH- or -COO-.
  • X 8 is preferably an alkyl group having 8 to 18 carbon atoms.
  • the side chain for vertically aligning the liquid crystal it is preferable to use a structure represented by the formula [III-1] from the viewpoint that a high and stable vertical alignment of the liquid crystal can be obtained.
  • 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 specific polymer contained in the liquid crystal aligning agent of the present invention has, for example, a photoreactive side chain in addition to the side chain having a radical generating structure represented by the above formula (I) or (II). May be.
  • the photoreactive side chain has a functional group (hereinafter also referred to as a photoreactive group) that can react by irradiation with light such as ultraviolet rays (UV) to form a covalent bond.
  • UV ultraviolet rays
  • the photoreactive side chain may be directly bonded to the main chain of the polymer, or may be bonded via a linking group.
  • the photoreactive side chain is represented, for example, by the following formula [IV].
  • R 8 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— is represented.
  • R 9 represents a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and —CH 2 — in the alkylene group is optionally substituted with —CF 2 — or —CH ⁇ CH—.
  • R 10 represents a photoreactive group selected from the following formulae.
  • R 8 is preferably a single bond, —O—, —COO—, —NHCO—, or —CONH—.
  • R 9 can be formed by a common organic synthetic method, but from the viewpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferable.
  • Y 1 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, or —CO—.
  • Y 2 is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms or organic It may be substituted with a group.
  • Y 2 when the following groups are not adjacent to each other, —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
  • Y 3 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond.
  • Y 4 represents a cinnamoyl group.
  • Y 5 is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms Alternatively, it may be substituted with an organic group.
  • —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
  • Y 6 represents a photopolymerizable group which is an acrylic group or a methacryl group.
  • R 10 is preferably a methacryl group, an acryl group or a vinyl group from the viewpoint of photoreactivity.
  • the abundance of the photoreactive side chain is preferably within a range where the response speed of the liquid crystal can be increased by reacting with ultraviolet irradiation to form a covalent bond.
  • the polymer having a radical generating structure used in the present invention is not particularly limited, but a polyimide-based, poly (meth) acrylate-based, polysiloxane-based polymer, or the like can be preferably used.
  • a polyimide-based, poly (meth) acrylate-based, polysiloxane-based polymer, or the like can be preferably used.
  • other polymers can be synthesized using known techniques (radical polymerization, sol-gel method, etc.).
  • the method for producing a polyimide precursor having a specific side chain and a polyimide obtained by imidizing the polyimide precursor is not particularly limited.
  • Examples include a method of polymerizing a compound, a method of polymerizing a tetracarboxylic dianhydride and a diamine, and then modifying a compound containing a specific side chain into a polymer by some kind of reaction.
  • a method of polymerizing a diamine compound containing a specific side chain and tetracarboxylic dianhydride or tetracarboxylic diester is preferable.
  • the method similar to the above-mentioned is mentioned also about the method of manufacturing the polyimide precursor which has the side chain which orientates a liquid crystal vertically in addition to a specific side chain, and the polyimide which imidated this polyimide precursor.
  • the preferable method is also preferably a method of polymerizing a diamine compound containing a side chain for vertically aligning a liquid crystal and a tetracarboxylic dianhydride or a tetracarboxylic acid diester.
  • a polyimide having a radical generating structure in the side chain can be prepared by using one or more of diamines such as the following specific diamines 1 to 3, for example.
  • the diamine (hereinafter also referred to as a specific diamine) used in the production of the above-mentioned polymer forming the liquid crystal aligning agent of the present invention has, as a side chain, a site having a radical generating structure that is decomposed by ultraviolet irradiation to generate radicals. And represented by the following formula (1).
  • the diaminobenzene in the formula (1) may have any structure of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine. However, in terms of reactivity with acid dianhydride, m-phenylenediamine, or p-Phenylenediamine is preferred.
  • n is an integer of 2 to 8.
  • the specific diamine 1 is a dinitro compound through each step, a mononitro compound having an amino group with a protective group that can be removed in the reduction process, or a diamine, and is synthesized by a reduction reaction that is usually used. It can be obtained by converting a group into an amino group or deprotecting a protecting group.
  • n is an integer of 2 to 8.
  • the base to be used is not particularly limited, inorganic bases such as potassium carbonate, sodium carbonate and cesium carbonate, and organic bases such as pyridine, dimethylaminopyridine, trimethylamine, triethylamine and tributylamine are preferable.
  • the method for reducing the dinitro compound, which is a diamine precursor is not particularly limited. Usually, palladium carbon, platinum oxide, Raney nickel, platinum carbon, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran. There is a method in which reduction is carried out with hydrogen gas, hydrazine, hydrogen chloride or the like in a solvent such as dioxane or alcohol. You may use an autoclave etc. as needed.
  • an unsaturated bond site is included in the structure, if palladium carbon or platinum carbon is used, the unsaturated bond site may be reduced and become a saturated bond. Reduction conditions using a transition metal such as tin chloride, poisoned palladium carbon or platinum carbon, platinum carbon doped with iron or the like as a catalyst are preferable.
  • the diamine of the present invention can be obtained by deprotecting the diaminobenzene derivative protected with a benzyl group or the like in the same reduction step.
  • the specific diamine 1 is preferably 10 to 80 mol%, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol% of the diamine component used for the synthesis of the polyamic acid.
  • the specific diamine 2 of the present invention can be represented by a diamine having an organic group represented by the formula (II) as a side chain, that is, the following formula (VI).
  • Sp is an alkylene group having 1 to 12 carbon atoms, and the alkylene group may have an unsaturated bond, a branched chain, or a cyclic structure.
  • X represents a single bond or a linking group.
  • Cy represents a cyclic hydrocarbon group having 5 to 14 carbon atoms having at least one unsaturated bond which is necessarily bonded to the carbonyl carbon of the imide group, and a part of the carbon atoms constituting the cyclic hydrocarbon is heterogeneous. It may be replaced by an atom.
  • the diaminobenzene in the formula (VI) may have a structure of any of o-phenylenediamine, m-phenylenediamine, or p-phenylenediamine. However, in terms of reactivity with acid dianhydride, m-phenylenediamine, Or p-phenylenediamine is preferred.
  • a preferred structure of the formula (VI) is a diamine represented by the following formula (X),
  • n is an integer from 1 to 6)
  • the structure represented by the following formula (XI) is most preferable from the viewpoints of ease of synthesis, high versatility, characteristics, and the like.
  • the specific diamine 2 is a dinitro compound through each step, a mononitro compound having an amino group with a protective group that can be removed in the reduction process, or a diamine, and is synthesized by a reduction reaction usually used. It can be obtained by converting a group into an amino group or deprotecting a protecting group.
  • a method of obtaining a diamine precursor by reacting an alcohol, alkylamine, alkyl halide or the like having a target imide structure with dinitrobenzene, or by reacting an alkylamine having dinitrobenzene already introduced with an acid anhydride examples thereof include a Mitsunobu reaction between an alcohol already introduced with dinitrobenzene and an N unsubstituted imide, and a method of condensing an alkyl halide already introduced with dinitrobenzene and an N unsubstituted imide in the presence of a base or a metal catalyst.
  • the method for reducing the dinitro compound, which is a diamine precursor is not particularly limited. Usually, palladium carbon, platinum oxide, Raney nickel, platinum carbon, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran. There is a method in which reduction is carried out with hydrogen gas, hydrazine, hydrogen chloride or the like in a solvent such as dioxane or alcohol. You may use an autoclave etc. as needed.
  • an unsaturated bond site is included in the structure, if palladium carbon or platinum carbon is used, the unsaturated bond site may be reduced and become a saturated bond. Reduction conditions using a transition metal such as tin chloride, poisoned palladium carbon or platinum carbon, platinum carbon doped with iron or the like as a catalyst are preferable.
  • the diamine of the present invention can be obtained by deprotecting the diaminobenzene derivative protected with a benzyl group or the like in the same reduction step.
  • the specific diamine 3 of the present invention is represented by the following formula (11).
  • the specific diamine 3 has a photoreactive structure in which radicals are generated by ultraviolet irradiation in a single molecular structure and a structure in which liquid crystals are aligned vertically. That is, the photoreactive structure is a 4-chromanone structure bonded to the phenylenediamine skeleton via X 11 , and the structure for vertically aligning the liquid crystal is bonded to 4-chromanone —X 2 —X 3 -X 4 structure.
  • each definition of X 11 , X 12 , X 13 and X 14 is as described above.
  • X 11 is preferably —O— or —CH 2 O— from the viewpoint of ease of synthesis.
  • X 12 and X 13 are preferably cyclohexane rings from the viewpoint of high vertical alignment.
  • X 14 is preferably an alkyl group having 3 to 7 carbon atoms from the viewpoint of availability of raw materials.
  • Preferred examples of the specific diamine 3 include the following.
  • the method for reducing the dinitro compound is not particularly limited, and usually palladium-carbon, platinum-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-alumina, platinum carbon sulfide, etc. are used as catalysts. , Ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohol-based solvents, hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride, and the like.
  • the method for synthesizing the dinitro compound represented by the general formula (12) is not particularly limited and can be synthesized by any method. Specific examples thereof include those shown in the following scheme (13). It can be synthesized by the method.
  • X 15 is any one of chlorine, bromine, iodine, fluorine, —OH, —COOH, —COOCl, — (CH 2 ) a OH (a is an integer of 1 to 15).
  • X 12 to X 14 in the phenol compound B are the same as those in the formula 1.
  • the compound shown here is an example and is not specifically limited.
  • the specific diamine is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 60 mol%, particularly preferably 30 mol% to 50 mol% of the diamine component used for the synthesis of the polyamic acid. is there.
  • X represents the structure of the above formula [III-1] or [III-2], and n represents an integer of 1 to 4.
  • R 8 , R 9 and R 10 are as defined above.
  • Y 1 to Y 6 are as described above.
  • Specific examples of the specific side chain diamine include structures represented by the following formulas [2a-1] to [2a-31].
  • R 1 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or —CH 2 OCO—
  • R 2 represents a linear or branched alkyl group having 1 to 22 carbon atoms, A linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched, fluorine-containing alkyl group or fluorine-containing alkoxyl group having 1 to 22 carbon atoms.
  • R 3 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 — or —CH 2 —
  • R 4 is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkyl group. Group or fluorine-containing alkoxyl group.
  • R 5 is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O —
  • R 6 represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.
  • R 7 is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • R 8 is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • a 4 is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A 3 is a 1,4-cyclohexylene group or a 1,4-phenylene group.
  • a 2 is an oxygen atom or COO- * (where a bond with “*” is bonded to A 3 ), and A 1 is an oxygen atom or COO— * (where “*” is a bond)
  • the hand binds to (CH 2 ) a 2 ).
  • a 1 is an integer of 0 or 1
  • a 2 is an integer of 2 to 10
  • a 3 is an integer of 0 or 1.
  • examples of the diamine having the specific side chain structure represented by the formula [III-2] include diamines represented by the following formulas [2b-1] to [2b-10].
  • a 1 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
  • a 1 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or —NH.
  • a 2 represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.
  • the above 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 is preferably used in an amount of 5 to 70 mol% of the diamine component used for the synthesis of the polyamic acid, more preferably 20 mol% to 60 mol% of the diamine component, Particularly preferred is 20 to 50 mol%.
  • a diamine having a specific side chain structure As a method for introducing a side chain having photoreactivity into a polyimide polymer, it is preferable to use a diamine having a specific side chain structure as a part of the diamine component.
  • the diamine having a photoreactive side chain is a diamine having a side chain represented by Formula [VIII] or Formula [IX].
  • the bonding positions of the two amino groups (—NH 2 ) in Formula [VIII] and Formula [IX] are 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 examples include, but are not limited to, the following.
  • X 9 and X 10 are each independently a single bond, —O—, —COO—, —NHCO—, or —NH—, a linking group, and Y is a carbon atom which may be substituted with a fluorine atom. Represents an alkylene group of ⁇ 20.
  • examples of the diamine having a photoreactive side chain include a diamine having a group causing a photodimerization reaction and a group causing a photopolymerization reaction represented by the following formula in the side chain.
  • Y 1 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, or —CO—.
  • Y 2 is an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms or organic It may be substituted with a group.
  • Y 2 when the following groups are not adjacent to each other, —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
  • Y 3 represents —CH 2 —, —O—, —CONH—, —NHCO—, —COO—, —OCO—, —NH—, —CO—, or a single bond.
  • Y 4 represents a cinnamoyl group.
  • Y 5 is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocycle or a heterocycle, and one or more hydrogen atoms of the alkylene group, divalent carbocycle or heterocycle are fluorine atoms Alternatively, it may be substituted with an organic group.
  • —CH 2 — may be substituted with these groups; —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
  • Y 6 represents a photopolymerizable group which is an acrylic group or a methacryl group.
  • the diamine having a photoreactive side chain depends on the liquid crystal alignment property when it is used as a liquid crystal alignment film, the pretilt angle, the voltage holding property, the characteristics such as accumulated charge, the response speed of the liquid crystal when it is used as a liquid crystal display device, etc. 1 type or 2 types or more can be mixed and used.
  • the diamine having a photoreactive side chain is preferably used in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably 30 to 50 mol% of the diamine component used for the synthesis of the polyamic acid. It is.
  • the liquid crystal aligning agent of the present invention comprises, as component (A), a polyimide precursor having a side chain for vertically aligning liquid crystals and a side chain having a radical generating structure represented by the above formula (I), and this Contains at least one polymer selected from polyimides obtained by imidizing a polyimide precursor and at least one diamine selected from the following formulas (B-1) to (B-5) as component (B)
  • 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.
  • tetracarboxylic dianhydride selected from the above formulas (3) and (4) When at least one tetracarboxylic dianhydride selected from the above formulas (3) and (4) is used as a raw material, it may cause an interaction between [liquid crystal-alignment film] by light irradiation, or may improve accumulated charge characteristics. be able to.
  • the tetracarboxylic dianhydride represented by the formula selected from the formulas (3) and (4) include, but are not limited to, the following compounds.
  • At least one tetracarboxylic dianhydride selected from the above formulas (1-1) to (1-4) 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.
  • a tetracarboxylic dianhydride other than the above formulas (1-1) to (1-4) may be used as a raw material for the component (B) as long as the effects of the present invention are not impaired.
  • Specific examples include, but are not limited to, the tetracarboxylic dianhydrides described in the component (A).
  • tetracarboxylic dianhydride having an aliphatic group or an alicyclic group is also used as a raw material
  • 0 to 90% of the tetracarboxylic dianhydride component used for the synthesis of the component (B), which is a polyamic acid Is preferably used.
  • the diamine component to be reacted is not particularly limited, and specific examples thereof Examples of the diamine include the diamines mentioned in the component (A), but at least one diamine selected from the above formulas (B-1) to (B-5) is preferably used from the viewpoint of accumulated charge characteristics.
  • the polymer as the component (B) includes a polyimide precursor obtained using a diamine component containing at least one diamine selected from the following formulas (B-1) to (B-5) as a raw material,
  • the polymer selected from the polyimide obtained by imidating a polyimide precursor may be sufficient.
  • 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.
  • a diamine having a specific structure with a high polarity selected from the above formulas (B-1) to (B-5) is used, or a diamine having a carboxyl group and a diamine having a nitrogen-containing aromatic heterocyclic ring.
  • charge transfer is promoted by electrostatic interactions such as salt formation and hydrogen bonding, so that accumulated charge characteristics can be improved.
  • Examples of at least one diamine selected from the formulas (B-1) to (B-5) include, but are not limited to, the following diamines.
  • Alicyclic diamines such as diamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3 -Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Examples thereof include aliphatic diamines such as diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.
  • 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 component to be reacted with the diamine component 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-dicarboxy) Phen
  • the liquid crystal aligning agent of the present invention may contain a polymerizable compound having a photopolymerizable or photocrosslinkable group at two or more terminals as required.
  • a polymerizable compound is a compound having two or more terminals having a group that undergoes 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 compound having a photocrosslinking group is at least one selected from a polymer of a polymerizable compound, a polyimide precursor, and a polyimide obtained by imidizing the polyimide precursor by irradiating light. It is a compound having a functional group capable of reacting with the polymer and crosslinking with these polymers.
  • a compound having a photocrosslinkable group also reacts with a compound having a photocrosslinkable group.
  • the liquid crystal aligning agent of the present invention containing the polymerizable compound in a vertical alignment type liquid crystal display element such as an SC-PVA type liquid crystal display By using the liquid crystal aligning agent of the present invention containing the polymerizable compound in a vertical alignment type liquid crystal display element such as an SC-PVA type liquid crystal display, the side chain and the photoreactive property for aligning the liquid crystal vertically are used. Compared to the case of using a polymer having a side chain and this polymerizable compound alone, the response speed can be remarkably improved, and the response speed can be sufficiently improved even with a small amount of the polymerizable compound added. Can do.
  • Examples of the group that undergoes photopolymerization or photocrosslinking include monovalent groups represented by the following formula (X).
  • R 12 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Z 1 is a divalent group optionally substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms.
  • Z 2 represents 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.
  • the polymerizable compound examples include a compound having a photopolymerizable group at each of two terminals represented by the following formula (XI), a terminal having a photopolymerizable group represented by the following formula (XII), and light.
  • Examples thereof include a compound having a terminal having a cross-linking group and a compound having a photo-crosslinking group at each of two terminals represented by the following formula (XIII).
  • R 12, Z 1 and Z 2 are the same as R 12, Z 1 and Z 2 in the formula (X), 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.
  • polymerizable compound represented by the formula [XI] examples include a polymerizable compound represented by the following formula (4).
  • V and W are each represented by a single bond or —R 1 O—, and R 1 is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably — R 1 is represented by R 1 O—, and R 1 is a linear or branched alkylene group having 2 to 6 carbon atoms.
  • V and W may be the same or different, but synthesis is easy when they are the same.
  • 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 polymerizable compound having a structure bonded to a phenylene group via a can significantly improve the response speed particularly like the polymerizable compound having ⁇ -methylene- ⁇ -butyrolactone groups at both ends. .
  • a polymerizable compound having a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group through a spacer such as an oxyalkylene group has improved heat stability, and a high temperature, for example, a firing temperature of 200 ° C. or higher. Can withstand enough.
  • ⁇ Synthesis of polyamic acid> In obtaining a polyamic acid by a reaction between a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. In general, a diamine component and a tetracarboxylic dianhydride component are reacted in an organic solvent. The reaction of the diamine component and tetracarbonic dianhydride 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 is soluble. Furthermore, even if it is an organic solvent in which a polyamic acid does not melt
  • organic solvent used in the above reaction examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, and N-ethyl-2.
  • -Pyrrolidone 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, 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 cellosolve, Tilcerosolve acetate, butylcellosolve acetate, ethylcellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol
  • the method of reacting a diamine component and a tetracarboxylic dianhydride component in an organic solvent is to stir a solution in which the diamine component is dispersed or dissolved in the organic solvent, and the tetracarboxylic dianhydride component as it is or an organic solvent.
  • Dispersing or dissolving in a solution adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent, alternating tetracarboxylic dianhydride component and diamine component Any of the methods of adding to In addition, when the diamine component or tetracarboxylic dianhydride component is 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 which the diamine component and the tetracarboxylic dianhydride component are reacted is, for example, in the range of ⁇ 20 ° C. to 150 ° C., preferably ⁇ 5 ° C. to 100 ° C.
  • the total concentration of the diamine component and the tetracarboxylic dianhydride component is preferably 1 to 50% by mass, and more 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 usual polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced, and 0.8 to 1.2 if it shows a preferred range.
  • 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.
  • 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 not necessarily 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 polyamic acid ester is a reaction of a tetracarboxylic acid diester dichloride with a diamine similar to the synthesis of the polyamic acid, a suitable condensing agent with a diamine similar to the synthesis of the tetracarboxylic acid diester and the polyamic acid, It can be produced by reacting in the presence of a base or the like. It can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxylic acid in the amic acid using a polymer reaction. Specifically, for example, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C.
  • a polyamic acid ester By reacting for ⁇ 4 hours, a polyamic acid ester can be synthesized.
  • the polyimide can also be obtained by heating the polyamic acid ester at a high temperature to promote dealcoholization and ring closure.
  • 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 operation of re-dissolving the recovered polymer in an organic solvent and repeating the reprecipitation recovery 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 agent of the present invention contains at least one specific polymer having a radical generating structure in the side chain, and the content of the specific polymer is preferably 0.5 to 20% by mass, more preferably 0.5 to 15%. % By mass, particularly preferably 1 to 10% by mass.
  • the liquid crystal aligning agent of the present invention may contain a polymer other than the above polymer.
  • the content of such other polymer in all the components of the polymer is preferably 0.5 to 80% by mass, more preferably 20 to 50% 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, and uniformity of the coating film. )
  • 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 solvent contained in the liquid crystal aligning agent is not particularly limited.
  • combination of said polyamic acid can be mentioned.
  • N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and 3-methoxy-N, N-dimethylpropanamide are soluble.
  • two or more kinds of mixed solvents may be used.
  • a solvent that improves the uniformity and smoothness of the coating film mixed with a solvent in which the components of the liquid crystal aligning agent are highly soluble examples include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, 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-butyl ether, dipropylene glycol,
  • 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 (Asahi Glass Co., Ltd.) and the like.
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent. .
  • 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.
  • These compounds are 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.
  • liquid crystal aligning agent By applying this liquid crystal aligning agent on a substrate and baking it, a liquid crystal alignment film for vertically aligning liquid crystals can be formed.
  • the response speed of the liquid crystal display element using the liquid crystal aligning film obtained can be made quick.
  • the polymerizable compound that has two or more terminal groups that are photopolymerized or photocrosslinked, which may be contained in the liquid crystal aligning agent of the present invention is not contained in the liquid crystal aligning agent, or the liquid crystal aligning agent.
  • the photoreaction becomes highly sensitive even in the so-called PSA mode, and a tilt angle can be imparted even with a small amount of ultraviolet irradiation.
  • a cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate and then drying and baking as necessary can be used as a liquid crystal aligning film as it is.
  • the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or a voltage is applied to the liquid crystal display element after filling the liquid crystal as a PSA alignment film It is also possible to irradiate with UV. In particular, it is useful to use as an alignment film for PSA.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate.
  • Glass plate polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone ,
  • Plastic substrates such as trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose 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 printing methods such as screen printing, offset printing, flexographic printing, ink jet method, spray method, roll coating method, dip, roll coater, slit coater, and spinner. From the standpoint of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention.
  • the coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film.
  • the drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. It is preferable.
  • the drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes.
  • the baking temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, and is, for example, 100 to 350 ° C, preferably 120 to 300 ° C, and more preferably 150 ° C to 250 ° C.
  • the firing time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, and more preferably 20 minutes to 90 minutes. Heating can be performed by a generally known method such as 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 20 to 200 nm.
  • a liquid crystal alignment film forming step for forming a liquid crystal alignment film as described above is performed on each of the surfaces of a pair of substrates.
  • a liquid crystal alignment film light irradiation step is performed in which at least one of the pair of substrates is irradiated with light so that the amount of light irradiation to the liquid crystal alignment films is different.
  • the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least part of the radical generating ability of the radical generating structure of the liquid crystal alignment film on one side, or both Irradiation is performed so that the amount of light irradiation is different so that the radical generating ability on both sides is different.
  • the liquid crystal alignment film of the substrate used on one side is irradiated with light to invalidate at least a part of the radical generating structure, thereby invalidating the radical generating ability.
  • one is a liquid crystal alignment film having no radical generation ability
  • the other is a liquid crystal alignment film having radical generation ability
  • one is a liquid crystal alignment film having low radical generation ability
  • the other is a liquid crystal alignment film having high radical generation ability.
  • the liquid crystal alignment films of the substrates on both sides are irradiated with light, but the amount of light irradiation is different on both sides, and the amount of radical generation structure to be invalidated is different on both sides.
  • one is a liquid crystal alignment film having a low radical generation capability and the other is a liquid crystal alignment film having a high radical generation capability so that the radical generation capability on both sides is different.
  • the liquid crystal alignment film using the liquid crystal aligning agent of the same composition of the present invention has a predetermined liquid crystal alignment ability based on the functions of various side chains of the polymer described above.
  • the amount of radicals generated by the ultraviolet rays during the PSA process differs for each substrate. Therefore, the reaction rate of the polymerizable compound is different at each substrate interface, and the liquid crystal alignment ability is also different.
  • a wavelength of about 250 nm to 600 nm can be used, and the wavelength is preferably adjusted appropriately for the radical generating structure.
  • the structure shown in the formula (I) since the structure shown in the formula (I) often has absorption up to about 250 nm to 420 nm, it is preferable to irradiate ultraviolet rays of 250 nm to 420 nm in accordance with the absorption wavelength. Although it is necessary to match the desired light irradiation amount with a desired panel characteristic, it is preferable to change the light irradiation suitably because long-time light irradiation leads to an increase in tact time in the element manufacturing process. Generally, it is considered that the radical generating structure can be deactivated more efficiently by performing light irradiation in accordance with the maximum absorption wavelength of the radical generating structure.
  • the suitable light irradiation amount is preferably 500 mJ / cm 2 to 100 J / cm 2 , more preferably 1 J / cm 2 to 70 J. / Cm 2 , more preferably 1 J / cm 2 to 40 J / cm 2 .
  • the portion close to the surface of the liquid crystal layer is adjacent. Since the alignment state is formed based on the liquid crystal alignment ability of the liquid crystal alignment film, the alignment states on both surfaces are different. Specifically, when the side chain is vertically aligned, an asymmetric liquid crystal layer having different pretilt angles on both sides can be realized.
  • the liquid crystal display device manufacturing method of the present invention includes a liquid crystal layer forming step of forming a liquid crystal layer containing a liquid crystal compound between the pair of substrates. Accordingly, since the liquid crystal layer is formed by being sandwiched between a pair of liquid crystal alignment films having different radical generation capabilities, it is possible to form an asymmetric liquid crystal layer having different pretilt angles on both sides.
  • Liquid crystal display device substrate> When a liquid crystal alignment film is formed using a liquid crystal aligning agent containing a specific polymer having a radical generating structure, the radical generating structure is used to generate radicals by light irradiation when forming the liquid crystal layer. Is normal.
  • the liquid crystal alignment film of the substrate used on at least one side is irradiated with light to invalidate at least a part of the radical generating structure before providing the liquid crystal layer, thereby invalidating the radical generating ability.
  • a substrate in which at least a part of the radical generating structure is invalidated is the substrate for a liquid crystal display element of the present invention.
  • the liquid crystal display element assembly of the present invention uses the liquid crystal display element substrate of the present invention described above and a substrate in which a liquid crystal alignment film is formed using a liquid crystal aligning agent having the same composition, and a liquid crystal material that forms a liquid crystal layer therebetween. Is sandwiched between them. Moreover, it is a liquid crystal display element substrate according to the present invention, wherein a pair of substrates with different light irradiation amounts irradiated in advance is used, and a liquid crystal material to be a liquid crystal layer is sandwiched therebetween.
  • the liquid crystal display element manufactured by the method for manufacturing a liquid crystal display element of the present invention can produce a liquid crystal cell by a known method using the above-described substrate for a liquid crystal display element of the present invention, and thereby a pair of radical generating ability is different. Since the liquid crystal layer is formed between the liquid crystal alignment films, an asymmetric liquid crystal layer having different pretilt angles on both sides can be obtained.
  • the liquid crystal display element include 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.
  • a vertical alignment type liquid crystal display device comprising a liquid crystal cell having the above-described liquid crystal alignment film.
  • the liquid crystal alignment agent of the present invention is applied to two substrates and baked to form a liquid crystal alignment film, and at least one of the radical generating structures is invalidated by irradiating light to at least one of the substrates.
  • Two substrates are arranged so that liquid crystal alignment films having different radical generating capabilities of the radical generating structure face each other, and a liquid crystal layer composed of liquid crystals is sandwiched between the two substrates, that is, the liquid crystal alignment film
  • a liquid crystal layer is provided in contact with each other, and is produced by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.
  • 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 photoreactive property of the polymer.
  • the alignment of the liquid crystal is more efficiently fixed, and the liquid crystal display device is remarkably excellent in response speed.
  • 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.
  • the liquid crystal aligning agent of the present invention since the liquid crystal aligning agent of the present invention is used, a line of 1 to 10 ⁇ m, for example, is formed on one side substrate. / Slit electrode pattern is formed, and it is possible to operate even in the structure where slit pattern or projection pattern is not formed on the counter substrate.
  • the liquid crystal display element of this structure can simplify the process at the time of manufacture and has 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 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 such as MLC-6608 or MLC-6609 manufactured by Merck & Co., Inc. Liquid crystal can be used.
  • a liquid crystal containing a polymerizable compound represented by the following formula can be used.
  • a known method can be used as a method of sandwiching the liquid crystal layer between two substrates. 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 each other so as to be inside, and sealing is performed.
  • the thickness of the spacer 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 / cm 2 , preferably 40 J / cm 2 or less, and the smaller the ultraviolet irradiation amount, the lowering of reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed.
  • the production efficiency is improved by reducing the ultraviolet irradiation time, which is preferable.
  • the polymerizable compound when ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is stored by this polymer.
  • the response speed of the obtained liquid crystal display element can be increased.
  • a polyimide precursor having a side chain for vertically aligning liquid crystal and a photoreactive side chain when irradiated with ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, and the polyimide precursor as an imide Since the photoreactive side chains of at least one polymer selected from the polyimide obtained by the reaction or the photoreactive side chains of the polymer react with the polymerizable compound, the liquid crystal display element obtained The response speed can be increased.
  • Diamine compounds represented by the following formulas DA-4 to DA-7.
  • the molecular weight measurement conditions of polyimide are as follows. Apparatus: Room-temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. Column: Columns manufactured by Shodex (KD-803, KD-805) Column temperature: 50 ° C.
  • GPC Room-temperature gel permeation chromatography
  • 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 (44.0 g) was added to the obtained polyimide powder (A) (6.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
  • 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (A1) was obtained by stirring at room temperature for 5 hours.
  • NMP (44.0 g) was added to the obtained polyimide powder (B) (6.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
  • 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (B1) was obtained by stirring at room temperature for 5 hours.
  • NMP (44.0 g) was added to the obtained polyimide powder (C) (6.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
  • 3AMP (1 mass% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (C1) was obtained by stirring at room temperature for 5 hours.
  • NMP (44.0 g) was added to the obtained polyimide powder (D) (6.0 g), and dissolved by stirring at 70 ° C. for 20 hours. NMP (10.0g) and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (D1) was obtained by stirring at room temperature for 5 hours.
  • NMP (44.0 g) was added to the obtained polyimide powder (E) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 10 hours.
  • 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (E1) was obtained by stirring at room temperature for 5 hours.
  • NMP (44.0 g) was added to the obtained polyimide powder (F) (6.0 g), and dissolved by stirring at 70 ° C. for 20 hours.
  • 3AMP (1 wt% NMP solution) 6.0g, NMP (4.0g), and BCS (40.0g) were added to this solution, and the liquid crystal aligning agent (F1) was obtained by stirring at room temperature for 5 hours.
  • Table 1 shows the compositions of the liquid crystal alignment agents A1, B1, and C1.
  • Table 2 shows the compositions of the liquid crystal alignment agents D1, E1, F1, and G1.
  • Example 1 Using the liquid crystal aligning agent (A2) obtained in Synthesis Example 4, a liquid crystal cell was prepared according to the procedure shown below.
  • the liquid crystal aligning agent (A2) obtained in Synthesis Example 4 was 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 was formed, After drying for 90 seconds on the hot plate, baking was performed in a hot air circulation oven at 230 ° C. for 30 minutes to form a liquid crystal alignment film (A2-1) having a film thickness of 100 nm.
  • a liquid crystal alignment film (A2-2) having a thickness of 100 nm was formed.
  • each of the liquid crystal alignment films (A2-1, A2-2) is irradiated with 10 J / cm 2 of UV of a high-pressure mercury lamp with a wavelength of 325 nm or less cut to deactivate the radical generating structure existing in the alignment film.
  • Pre-UV For the measurement of the irradiation amount, a UV-35 light receiver was connected to UV-M03A manufactured by ORC.
  • a sealant (a thermosetting sealant XN-1500T manufactured by Mitsui Chemicals) 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-3023 (trade name, manufactured by Merck & Co., Inc.) containing a polymerizable compound for PSA was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell.
  • UV of a high pressure mercury lamp passed through a 365 nm band-pass filter was irradiated from the outside of the liquid crystal cell at 10 J / cm 2 (1st-UV). Thereafter, irradiation with a fluorescent UV lamp (FLR40SUV32 / A-1) for 30 minutes without applying a voltage to the liquid crystal cell (2nd-UV) to deactivate unreacted polymerizable compounds present in the liquid crystal cell. It was.
  • a liquid crystal cell was arranged between a pair of polarizing plates in a measuring device 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 ⁇ 7 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the 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 is obtained.
  • a voltage of 0% and ⁇ 7 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.
  • a liquid crystal cell having an asymmetric pretilt angle was prepared in the same procedure as described above except that the liquid crystal alignment film (A2-1) was not irradiated with Pre-UV, and the response speed was measured. The results are shown in Table 3.
  • Examples 2 to 3 A liquid crystal cell was produced in the same manner as in Example 1 except that 20-40 J / cm 2 was irradiated instead of 10 J / cm 2 irradiated as Pre-UV in Example 1, and the pretilt angle of the liquid crystal cell was Was measured.
  • Example 4 The same operation as in Example 1 was performed except that 1 J / cm 2 of UV from a high-pressure mercury lamp passed through a band-pass filter with a wavelength of 313 nm was irradiated instead of 10 J / cm 2 irradiated as Pre-UV in Example 1. A liquid crystal cell was prepared, and the pretilt angle of the liquid crystal cell was measured.
  • Examples 5 to 8 A liquid crystal cell was prepared in the same manner as in Examples 1 to 4 except that the alignment agent used was changed from the liquid crystal alignment agent (A2) to the liquid crystal alignment agent (B2), and the pretilt angle of the liquid crystal cell was measured. Went.
  • An alignment film (B2-1) applied to 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 is formed on the ITO film on which the electrode pattern is not formed.
  • the alignment film applied on the surface was designated as (B2-2).
  • Example 1 A liquid crystal cell was produced in the same manner as in Example 1 except that Pre-UV was not irradiated in Example 1, and the pretilt angle of the liquid crystal cell was measured.
  • Example 2 A liquid crystal cell was prepared in the same manner as in Example 5 except that Pre-UV was not irradiated in Example 5, and the pretilt angle of the liquid crystal cell was measured.
  • Example 9 to 12 A liquid crystal cell was produced in the same manner as in Examples 1 to 4 except that the liquid crystal aligning agent (A2) was changed to the liquid crystal aligning agent (D2), and the pretilt angle of the liquid crystal cell was measured.
  • An alignment film (D2-1) applied 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 is formed on the ITO film on which the electrode pattern is not formed.
  • the alignment film applied to the surface was designated as (D2-2).
  • Example 13 to 16 A liquid crystal cell was produced in the same manner as in Examples 1 to 4 except that the liquid crystal aligning agent (A2) was changed to the liquid crystal aligning agent (E2), and the pretilt angle of the liquid crystal cell was measured.
  • An alignment film (E2-1) applied 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 is formed on the ITO film on which the electrode pattern is not formed.
  • the alignment film applied to the surface was designated as (E2-2).
  • Example 3 A liquid crystal cell was prepared in the same manner as in Example 9 except that Pre-UV was not irradiated in Example 9, and the pretilt angle of the liquid crystal cell was measured.
  • Example 4 A liquid crystal cell was prepared in the same manner as in Example 13 except that Pre-UV was not irradiated in Example 13, and the pretilt angle of the liquid crystal cell was measured.
  • the substrate is irradiated with Pre-UV to deactivate the radical generating structure in the alignment film, and the pretilt angle is less likely to be exhibited during the PSA treatment (1st-UV). It was confirmed that it would be too late.
  • Pre-UV irradiation since Pre-UV irradiation is not performed, a radical generating structure remains in the alignment film, and a sufficient pretilt can be obtained even when a wavelength of 365 nm with relatively weak energy is used during PSA treatment (1st-UV). It can be seen that the angle and response speed can be obtained.
  • the pretilt angle on the side irradiated with Pre-UV should be the pretilt angle described in the examples in Table 3 and Table 5, but the Pre-UV It is considered that the pretilt angle described in the comparative examples in Table 3 and Table 5 is the non-irradiated side (ITO electrode pattern side in this example).
  • a liquid crystal display element having an asymmetric pretilt angle can be obtained using one type of liquid crystal aligning agent without impairing the response speed required for the liquid crystal display element. It becomes possible to create.

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Abstract

La présente invention comprend : une étape de formation du film d'alignement de cristaux liquides pour former, sur chaque surface d'une paire de substrats, un film d'alignement de cristaux liquides avec des agents d'alignement de cristaux liquides ayant la même composition et contenant des polymères qui ont une structure de génération de radicaux pour générer des radicaux par irradiation de lumière; une étape d'irradiation de lumière de film d'alignement de cristaux liquides pour irradier de la lumière sur au moins l'une des paires de substrats pour produire un état dans lequel les quantités de lumière irradiée sur les films d'alignement de cristaux liquides diffèrent; puis une étape de formation de couche de cristaux liquides pour former une couche de cristaux liquides comprenant un composé de cristaux liquides entre la paire de substrats.
PCT/JP2017/041921 2016-11-22 2017-11-22 Procédé de fabrication d'élément d'affichage à cristaux liquides, substrat pour élément d'affichage à cristaux liquides et ensemble d'éléments d'affichage à cristaux liquides WO2018097155A1 (fr)

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KR1020197017683A KR102609041B1 (ko) 2016-11-22 2017-11-22 액정 표시 소자의 제조 방법 그리고 액정 표시 소자용 기판 및 액정 표시 소자 조립체
JP2018552604A JP7227557B2 (ja) 2016-11-22 2017-11-22 液晶表示素子の製造方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019013339A1 (fr) * 2017-07-14 2019-01-17 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides mettant en œuvre celui-ci
WO2019244821A1 (fr) * 2018-06-18 2019-12-26 日産化学株式会社 Procédé de production d'un film d'ancrage azimutal nul, et élément d'affichage à cristaux liquides
WO2021125327A1 (fr) * 2019-12-18 2021-06-24 日産化学株式会社 Procédé de fabrication d'un élément d'affichage à cristaux liquides à motif

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014038431A1 (fr) * 2012-09-05 2014-03-13 シャープ株式会社 Polymère pour films d'alignement et dispositif d'affichage à cristaux liquides
WO2016140288A1 (fr) * 2015-03-04 2016-09-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2016140328A1 (fr) * 2015-03-04 2016-09-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2016140302A1 (fr) * 2015-03-04 2016-09-09 日産化学工業株式会社 Précurseur de polyimide, et agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides comprenant un précurseur

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5841491B2 (ja) * 1976-04-07 1983-09-12 株式会社東芝 液晶素子
JP4175826B2 (ja) 2002-04-16 2008-11-05 シャープ株式会社 液晶表示装置
CN102197109B (zh) * 2008-10-29 2014-05-14 默克专利股份有限公司 液晶显示器
KR101734600B1 (ko) * 2009-11-09 2017-05-11 제이엔씨 주식회사 액정 표시 소자, 액정 조성물 및 배향제 그리고 액정 표시 소자의 제조방법
KR101725997B1 (ko) 2010-03-16 2017-04-12 한양대학교 산학협력단 중합된 메조겐을 함유하는 배향 조절막을 구비하는 액정 표시 장치 및 그 제조 방법
JP5552894B2 (ja) * 2010-05-14 2014-07-16 Ｊｓｒ株式会社 液晶配向剤および液晶表示素子
JP5927859B2 (ja) * 2011-01-11 2016-06-01 Jsr株式会社 液晶表示素子の製造方法
KR20120105722A (ko) * 2011-03-16 2012-09-26 삼성디스플레이 주식회사 액정 표시 장치 및 그 제조 방법
CN103562785B (zh) * 2011-03-31 2016-02-10 日产化学工业株式会社 液晶取向剂、液晶取向膜、液晶显示元件及液晶显示元件的制造方法以及聚合性化合物
CN103619803B (zh) * 2011-05-31 2016-01-20 Dic株式会社 肉桂酸衍生物及其聚合物、以及由其固化物构成的液晶取向层
KR101988082B1 (ko) * 2012-10-18 2019-06-11 닛산 가가쿠 가부시키가이샤 조성물, 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
JP6301954B2 (ja) * 2012-12-21 2018-03-28 ロリク アーゲーＲｏｌｉｃ Ａｇ 平面光配向のための方法
WO2014142168A1 (fr) * 2013-03-12 2014-09-18 日産化学工業株式会社 Agent d'alignement de cristaux liquides contenant un composé réticulable ayant un groupe photoréactif
JP6311343B2 (ja) * 2013-05-09 2018-04-18 Jsr株式会社 液晶配向剤、液晶配向膜、液晶表示素子、液晶配向膜の製造方法、位相差フィルム及び位相差フィルムの製造方法
KR102069822B1 (ko) * 2013-07-24 2020-01-28 삼성디스플레이 주식회사 액정 표시 장치 및 그 제조 방법
JP6561833B2 (ja) 2013-09-03 2019-08-21 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
KR102376844B1 (ko) 2014-06-30 2022-03-23 삼성디스플레이 주식회사 곡면형 표시 장치 및 이의 제조방법
KR20170075834A (ko) * 2015-12-23 2017-07-04 삼성디스플레이 주식회사 액정표시장치 및 이의 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014038431A1 (fr) * 2012-09-05 2014-03-13 シャープ株式会社 Polymère pour films d'alignement et dispositif d'affichage à cristaux liquides
WO2016140288A1 (fr) * 2015-03-04 2016-09-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2016140328A1 (fr) * 2015-03-04 2016-09-09 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
WO2016140302A1 (fr) * 2015-03-04 2016-09-09 日産化学工業株式会社 Précurseur de polyimide, et agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides comprenant un précurseur

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019013339A1 (fr) * 2017-07-14 2019-01-17 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et élément d'affichage à cristaux liquides mettant en œuvre celui-ci
KR20200027967A (ko) * 2017-07-14 2020-03-13 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 그것을 사용한 액정 표시 소자
KR102572922B1 (ko) 2017-07-14 2023-08-30 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 그것을 사용한 액정 표시 소자
WO2019244821A1 (fr) * 2018-06-18 2019-12-26 日産化学株式会社 Procédé de production d'un film d'ancrage azimutal nul, et élément d'affichage à cristaux liquides
JPWO2019244821A1 (ja) * 2018-06-18 2021-07-26 日産化学株式会社 ゼロ面アンカリング膜の製造方法及び液晶表示素子
JP7367674B2 (ja) 2018-06-18 2023-10-24 日産化学株式会社 ゼロ面アンカリング膜の製造方法及び液晶表示素子
WO2021125327A1 (fr) * 2019-12-18 2021-06-24 日産化学株式会社 Procédé de fabrication d'un élément d'affichage à cristaux liquides à motif

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CN110192148A (zh) 2019-08-30
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