WO2017146216A1 - 液晶表示素子 - Google Patents

液晶表示素子 Download PDF

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Publication number
WO2017146216A1
WO2017146216A1 PCT/JP2017/007148 JP2017007148W WO2017146216A1 WO 2017146216 A1 WO2017146216 A1 WO 2017146216A1 JP 2017007148 W JP2017007148 W JP 2017007148W WO 2017146216 A1 WO2017146216 A1 WO 2017146216A1
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Prior art keywords
liquid crystal
group
carbon atoms
formula
alkyl group
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PCT/JP2017/007148
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English (en)
French (fr)
Japanese (ja)
Inventor
保坂　和義
徳俊 三木
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日産化学工業株式会社
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Priority to JP2018501797A priority Critical patent/JP6406472B2/ja
Priority to CN201780013352.2A priority patent/CN108700766B/zh
Priority to KR1020187024247A priority patent/KR20180114070A/ko
Publication of WO2017146216A1 publication Critical patent/WO2017146216A1/ja

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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
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • 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 liquid crystal display element suitable as a reverse type element.
  • a TN (Twisted Nematic) mode As a liquid crystal display element, a TN (Twisted Nematic) mode has been put into practical use. In this mode, light is switched using the optical rotation characteristics of the liquid crystal, and it is usually necessary to use a polarizing plate. However, the use efficiency of light becomes low by using a polarizing plate. As a liquid crystal display element with high light utilization efficiency without using a polarizing plate, there is an element that switches between a liquid crystal transmission state (also referred to as a transparent state) and a scattering state. In general, those using polymer dispersed liquid crystal (PDLC) or polymer network liquid crystal (PNLC) are known.
  • PDLC polymer dispersed liquid crystal
  • PNLC polymer network liquid crystal
  • liquid crystal display elements a liquid crystal composition containing a polymerizable compound that is polymerized by ultraviolet rays is disposed between a pair of substrates provided with electrodes, and the liquid crystal composition is cured by irradiation with ultraviolet rays, whereby a liquid crystal layer, A cured product composite (for example, a polymer network) of the liquid crystal and the polymerizable compound is formed.
  • the transmission state and the scattering state of the liquid crystal are controlled by applying a voltage.
  • a liquid crystal display element (also referred to as a normal type element) that transmits light and is in a transmissive state.
  • the normal type element it is necessary to always apply a voltage in order to obtain a transmission state. Therefore, the power consumption is often used in applications that are often used in a transparent state, such as a window glass. Will become bigger.
  • the polymerizable compound in the liquid crystal composition has a role of forming a polymer network to obtain desired optical characteristics and a role of a curing agent for improving the adhesion between the liquid crystal layer and the liquid crystal alignment film.
  • a polymer network In order to improve the adhesion, it is necessary to make the polymer network denser. However, if the polymer network is made dense, the vertical alignment of the liquid crystal is inhibited, and the transparency and voltage when no voltage is applied in the reverse type device. The scattering characteristic at the time of application will be deteriorated. Therefore, the liquid crystal composition used for the reverse type element needs to improve the vertical alignment of the liquid crystal when the liquid crystal layer is formed.
  • the liquid crystal alignment film used for the reverse type element is a highly hydrophobic film for aligning the liquid crystal vertically, there is a problem that the adhesion between the liquid crystal layer and the liquid crystal alignment film is lowered. Therefore, a large amount of a polymerizable compound that functions as a curing agent must be introduced into the liquid crystal composition of the reverse type device. However, when a large amount of the polymerizable compound is introduced, the vertical alignment property of the liquid crystal is hindered, and there is a problem that the transparency when no voltage is applied and the scattering characteristics when a voltage is applied are greatly reduced.
  • the reverse type element may be used by sticking it to the window glass of an automobile or a building, so that the vertical alignment of the liquid crystal can be performed even in a harsh environment exposed to high temperature and high humidity for a long time. Therefore, it is necessary that the adhesion between the liquid crystal layer and the liquid crystal alignment film is high.
  • the present invention has a high vertical alignment property of the liquid crystal, good optical properties, that is, good transparency when no voltage is applied and good scattering property when a voltage is applied, and further the adhesion between the liquid crystal layer and the liquid crystal alignment film.
  • An object of the present invention is to provide a liquid crystal display element that can maintain these characteristics even in an environment that is high and exposed to high temperature and high humidity or light irradiation for a long time.
  • the present inventor has completed the present invention having the following gist.
  • the present invention has a liquid crystal layer made of a cured product by irradiation of ultraviolet rays with respect to a liquid crystal composition containing a liquid crystal and a polymerizable compound disposed between a pair of substrates provided with electrodes, and at least one of the substrates has a liquid crystal vertically
  • a liquid crystal display device comprising a liquid crystal alignment film that is aligned in the following manner, wherein the liquid crystal composition comprises a compound of the following formula [1-1a] and a compound of the following formula [2-1a],
  • the liquid crystal display element is a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent containing a polymer having a side chain structure represented by formula [4-1a] or formula [4-2a].
  • T 1 represents a structure selected from the following formulas [1-a] to [1-e].
  • T 2 represents a single bond or an alkylene group having 1 to 24 carbon atoms. 2 — is replaced by —O—, —CO—, —COO—, —OCO—, —CONH—, —NHCO—, —NH—, —CON (CH 3 ) —, —S— or —SO 2 —.
  • T 3 represents a cyclic group having a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group is An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.
  • T 4 is a single bond, —O—, —OCH 2 —, —CH 2 O—, —COO— or —OCO—, wherein T 5 represents a cyclic group having a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 to 3 carbon atoms alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, optionally .T 6 be substituted with a fluorine-containing alkoxy group or a fluorine atom having 1 to 3 carbon atoms 1 -C Represents an alkyl group having ⁇ 18, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group
  • S 2 represents a linear or branched alkylene group having 2 to 18 carbon atoms.
  • S 1 and any —CH 2 — in the alkylene group not adjacent to —N ⁇ C ⁇ O are —O—, —CO—, —COO—, —OCO—, —CONH—, —NHCO— or (It may be substituted with -NH-.
  • NS represents an integer of 1 to 4.)
  • S A and S c represent a single bond, —O—, —CH 2 O—, —COO—, —OCO—, —CONH—, —NHCO— or —NH—.
  • S B represents a hydrogen atom or a benzene ring.
  • (X 1 and X 3 each represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or —OCO—.
  • X 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15.)
  • X 4 represents a carbon having a benzene ring, a cyclohexane ring or a heterocyclic group having a heterocyclic ring, or a steroid skeleton.
  • X 5 represents a cyclic group having a benzene ring, a cyclohexane ring, or a heterocyclic ring, and any arbitrary group on these cyclic groups;
  • a hydrogen atom is an alkyl group having 1 to 3 carbon atoms, Alkoxy group 1-3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, good .
  • X 6 be substituted with a fluorine-containing alkoxy group or a fluorine atom having 1 to 3 carbon atoms alkyl group having 1 to 18 carbon atom
  • the transparency when no voltage is applied and the scattering characteristics when a voltage is applied are good. Furthermore, the adhesion between the liquid crystal layer and the liquid crystal alignment film is high, and high temperature and high humidity and light irradiation are applied for a long time. A liquid crystal display element capable of maintaining these characteristics even in an environment exposed to is obtained. Therefore, the element of the present invention is used as a reverse type element in a liquid crystal display for display purposes, a dimming window for controlling transmission and blocking of light, an optical shutter element, and the like.
  • the reason why the liquid crystal display element of the present invention has the above-mentioned excellent characteristics can be considered as follows.
  • the compound of the formula [1-1a] (also referred to as the specific compound (1)) contained in the liquid crystal composition used in the liquid crystal display device of the present invention has a rigid structure such as a benzene ring or a cyclohexane ring. Therefore, it is considered that the vertical alignment property of the liquid crystal is improved.
  • the compound of the formula [2-1a] also referred to as the specific compound (2) contained in the liquid crystal composition of the present invention undergoes a polymerization reaction due to the ultraviolet light of S 1 in the formula [2-1a].
  • the isocyanate group (—N ⁇ C ⁇ O) of the specific compound (2) is polymerized with the polymerizable compound in the liquid crystal composition by irradiation with ultraviolet rays.
  • the optical characteristics of the element particularly the improvement of transparency and the durability under harsh environments are increased.
  • the liquid crystal alignment film in the liquid crystal display element of the present invention is a polymer having a side chain structure (also referred to as a specific side chain structure) represented by the formula [4-1a] or [4-2a] (also referred to as a specific polymer). .) Is obtained from the liquid crystal aligning agent. Since the specific side chain structure shows a rigid structure, a liquid crystal display device using a liquid crystal alignment film having this side chain structure has a high and stable vertical alignment of liquid crystals. Therefore, in particular, in the case of the specific side chain structure of the formula [4-1a], an element that exhibits good optical characteristics can be obtained.
  • the liquid crystal composition of the present invention includes the specific compound (1) of the formula [1-1a] and the specific compound (2) of the formula [2-1a].
  • the liquid crystal nematic liquid crystal, smectic liquid crystal, or cholesteric liquid crystal can be used. Among these, those having negative dielectric anisotropy are preferable. From the viewpoint of low voltage driving and scattering characteristics, those having a large dielectric anisotropy and a large refractive index anisotropy are preferred.
  • two or more kinds of liquid crystals can be used according to the physical property values of the phase transition temperature, dielectric anisotropy and refractive index anisotropy.
  • liquid crystal display element As an active element such as a TFT (Thin Film Transistor), it is required that the liquid crystal has a high electric resistance and a high voltage holding ratio (also referred to as VHR). For this reason, it is preferable to use a fluorine-based or chlorine-based liquid crystal that has high electrical resistance and does not decrease VHR by active energy rays such as ultraviolet rays.
  • active energy rays such as ultraviolet rays.
  • the liquid crystal display element can be made into a guest-host type element by dissolving a dichroic dye in a liquid crystal composition.
  • a dichroic dye in this case, an element is obtained that is transparent when no voltage is applied and absorbs (scatters) when a voltage is applied.
  • the direction of the liquid crystal director changes by 90 degrees depending on the presence or absence of voltage application. Therefore, this liquid crystal display element can obtain a higher contrast than the conventional guest-host type element that switches between random alignment and vertical alignment by utilizing the difference in light absorption characteristics of the dichroic dye.
  • a guest-host type element in which a dichroic dye is dissolved is colored when the liquid crystal is aligned in the horizontal direction, and is opaque only in the scattering state. Therefore, as the voltage is applied, it is possible to obtain an element that switches from colorless and transparent when no voltage is applied to a colored opaque and colored transparent state.
  • the liquid crystal composition of the present invention contains a polymerizable compound in order to form a polymer network of the liquid crystal layer.
  • the polymer network may be a polymer network by introducing a polymerizable compound into a liquid crystal composition and causing a polymerization reaction by irradiation with ultraviolet rays during the production of a liquid crystal display element, or a polymerization compound may be preliminarily polymerized.
  • the polymer may be introduced into the liquid crystal composition. However, even when a polymer is used, it is necessary to have a site that undergoes a polymerization reaction upon irradiation with ultraviolet rays.
  • a polymerizable compound is added to the liquid crystal composition to prepare a liquid crystal display element. It is preferable to polymerize by ultraviolet irradiation to form a polymer network.
  • the polymerizable compound in the liquid crystal composition is not particularly limited as long as it dissolves in the liquid crystal, and may be a polymer containing an oligomer thereof, and when the polymerizable compound is dissolved in the liquid crystal, part or the whole of the liquid crystal composition. It is preferable that there is a temperature at which shows a liquid crystal phase. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, it is preferable that the liquid crystal display element is confirmed with the naked eye and the entire element has substantially uniform transparency and scattering characteristics.
  • the polymerizable compound is not particularly limited as long as it is a compound that is polymerized by ultraviolet rays, and the polymerization may proceed in any reaction form to form a polymer network. Specific reaction modes include radical polymerization, cationic polymerization, anionic polymerization, or polyaddition reaction.
  • radical polymerization is preferable as the reaction mode of the polymerizable compound from the viewpoint of the optical characteristics of the liquid crystal display element.
  • the following radical type polymerizable compounds or oligomers thereof can be used as the polymerizable compound.
  • a polymer obtained by polymerizing these polymerizable compounds can also be used.
  • Specific examples of the radical type polymerizable compound or oligomer thereof include the radical type polymerizable compounds described on pages 69 to 71 of International Publication No. 2015/146987.
  • the radical type polymerizable compound may be used alone or in combination of two or more depending on each characteristic.
  • the content of the polymer containing the polymerizable compound or the polymer oligomer thereof in the liquid crystal composition is based on 100 parts by mass of the liquid crystal in the liquid crystal composition in terms of adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film.
  • the amount is preferably 70 to 150 parts by mass, and more preferably 80 to 120 parts by mass.
  • a radical initiator (also referred to as a polymerization initiator) that generates radicals by ultraviolet rays is introduced into the liquid crystal composition for the purpose of promoting radical polymerization of the polymerizable compound. It is preferable. Specific examples include radical initiators described on pages 71 to 72 of International Publication No. 2015/146987.
  • the use ratio of the radical initiator is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition, from the viewpoint of adhesion between the liquid crystal layer of the liquid crystal display element and the liquid crystal alignment film. Preferably, it is 0.05 to 5 parts by mass.
  • the radical initiator can use 1 type (s) or 2 or more types according to each characteristic.
  • the specific compound (1) is a compound of the formula [1-1a], and in the formula [1-1a], T 1 , T 2 , T 3 , T 4 , T 5 , T 6 and nT are as defined above.
  • T 1 is preferably formula [1-b], formula [1-c] or formula [1-e], more preferably formula [1-b], from the viewpoint of addition reaction with the specific compound (2).
  • T 2 is preferably a single bond or an alkylene group having 1 to 12 carbon atoms, and any —CH 2 — in the alkylene group is —O—, —CO—, —COO—, —OCO—, —CONH—, — It may be substituted with NHCO—, —NH—, —CON (CH 3 ) —, —S— or —SO 2 —.
  • T 2 is more preferably a single bond or an alkylene group having 1 to 8 carbon atoms.
  • T 3 is preferably a benzene ring, a cyclohexane ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, more preferably a benzene ring or a cyclohexane ring, from the viewpoint of the optical characteristics of the device.
  • T 4 is preferably a single bond, —O—, —COO— or —OCO—, and more preferably a single bond.
  • T 5 is preferably a benzene ring or a cyclohexane ring from the viewpoint of the optical characteristics of the device.
  • T 6 is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, from the viewpoint of the optical characteristics of the device.
  • An alkyl group or an alkoxy group; nT is preferably from 0 to 3, more preferably 1 or 2.
  • T 7 represents the structure of the formula [1-b] or the formula [1-c].
  • T 8 represents a single bond or an alkylene group having 1 to 8 carbon atoms.
  • T 9 and T 10 each represent a benzene ring or a cyclohexane ring.
  • T 11 represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group.
  • mT represents an integer of 0-2.
  • Specific examples of the formula [1-2a] include compounds of the following formulas [1a-1] to [1a-24].
  • T a is .T b which represents single bond or an alkylene group having 1 to 8 carbon atoms is an alkyl group or an alkoxy group having 1 to 12 carbon atoms.
  • the use ratio of the specific compound (1) is preferably 1 to 40 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the liquid crystal in the liquid crystal composition, from the viewpoint of optical characteristics of the device. Most preferred is 1 to 20 parts by weight.
  • the specific compound (1) can use 1 type (s) or 2 or more types according to each characteristic.
  • the specific compound (2) is a compound of the formula [2-1a], and in the formula [2-1a], S 1 , S 2 and nS are as defined above.
  • S 1 is preferably formula [2-a], formula [2-b], formula [2-c] or formula [2-e] from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film. More preferred is the formula [2-a] or the formula [2-b].
  • S 2 is preferably a linear or branched alkylene group having 2 to 12 carbon atoms, and any —CH 2 — in the alkylene group not adjacent to S 1 and —N ⁇ C ⁇ O is —O—, It may be substituted with —CO—, —COO—, —OCO—, —CONH—, —NHCO— or —NH—. More preferably, S 2 is a linear or branched alkylene group having 2 to 8 carbon atoms. nS is preferably an integer of 2 to 4, and more preferably 2, from the adhesion between the liquid crystal layer and the liquid crystal alignment film.
  • the specific compound (2) is preferably a compound of the following formula [2-2a].
  • S 3 and S 5 represent formula [2-a] or formula [2-b], respectively.
  • S 4 represents a linear or branched alkylene group having 2 to 8 carbon atoms.
  • Specific examples of the formula [2-2a] include compounds of the following formulas [2a-1] to [2a-4].
  • N (NS1 and nS2 each represent an integer of 0 to 7, and nS1 + nS2 represents an integer of 1 to 7)
  • N (NS3 to nS5 each represents an integer of 0 to 6, and nS1 + nS2 + nS3 represents an integer of 1 to 6)
  • the use ratio of the specific compound (2) is preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition from the viewpoint of optical characteristics of the device. .
  • the specific compound (2) can use 1 type (s) or 2 or more types according to each characteristic.
  • the liquid crystal composition of the present invention preferably contains a compound represented by the following formula [3-1a] (also referred to as a specific compound (3)) in order to enhance the optical properties, particularly transparency, of the liquid crystal display element.
  • W 1 represents a structure selected from the following formulas [3-a] to [3-e].
  • W 2 represents a single bond or an alkylene group having 1 to 24 carbon atoms, and any —CH 2 — in the alkylene group is —O—, —CO—, —COO—, —OCO—, —CONH—, — It may be substituted with NHCO—, —NH—, —CON (CH 3 ) —, —S— or —SO 2 —.
  • W 3 represents a cyclic group having a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group has 1 to 3 may be substituted with an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group, or a fluorine atom.
  • W 4 represents at least one selected from the group consisting of a single bond, —CH 2 —, —O—, —OCH 2 —, —CH 2 O—, —COO—, and —OCO—.
  • W 5 represents a cyclic group having a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing group having 1 to 3 carbon atoms. It may be substituted with an alkoxy group or a fluorine atom.
  • W 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group, an alkoxy group, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms.
  • nW represents an integer of 0 to 4.
  • W A and W c represent a single bond, —O—, —CH 2 O—, —COO—, —OCO—, —CONH—, —NHCO— or —NH—.
  • W B represents a hydrogen atom or a benzene ring. Is shown.
  • W 1 is preferably the above formula [3-a], formula [3-b], formula [3-c] or formula [3-e]. More preferably, from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film, the formula [3-a], the formula [3-b] or the formula [3-c] is used.
  • W 2 is preferably a single bond or an alkylene group having 1 to 12 carbon atoms, and any —CH 2 — in the alkylene group is —O—, —CO—, —COO—, —OCO—, —CONH—, — It may be substituted with NHCO—, —NH—, —CON (CH 3 ) —, —S— or —SO 2 —.
  • W 2 is more preferably a single bond or an alkylene group having 1 to 8 carbon atoms.
  • W 3 is preferably a benzene ring, a cyclohexane ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, more preferably a benzene ring or a cyclohexane ring, from the viewpoint of the optical characteristics of the device.
  • W 4 is preferably a single bond, —CH 2 —, —O—, —COO— or —OCO—.
  • W 5 is preferably a benzene ring or a cyclohexane ring from the viewpoint of the optical characteristics of the device.
  • W 6 is preferably an alkyl group or alkoxy group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms, more preferably an alkyl group or alkoxy group having 1 to 12 carbon atoms, from the viewpoint of the optical characteristics of the device. It is.
  • nW is preferably an integer of 0 to 3, more preferably 0 to 2.
  • the specific compound (3) is preferably a compound of the following formulas [3a-1] to [3a-6] from the viewpoint of the optical properties of the device.
  • W a is an alkyl group having 1 to 18 carbon atoms or an alkoxy group, and is preferably an alkyl group having 1 to 12 carbon atoms.
  • W b is —O—, —COO— or —OCO—, and —O— is (P1 is an integer of 1 to 12, and preferably 1 to 8.
  • p2 is an integer of 1 to 3, preferably 1 or 2.
  • X c is —CH 2 —, —O—, —COO— or —OCO—, preferably —O—, —COO— or —OCO—.
  • X d is an alkyl group having 1 to 18 carbon atoms or alkoxy And is preferably an alkyl group having 1 to 12 carbon atoms,
  • X e is —O—, —COO— or —OCO—, preferably —O—,
  • p3 is an integer of 1 to 12, and 1 to 8 is preferable.
  • the specific compound (3) is most preferably a compound of the formula [3a-1] or the formula [3a-2] from the viewpoint of the optical properties of the device.
  • the use ratio of the specific compound (3) is preferably 1 to 40 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the liquid crystal in the liquid crystal composition, from the viewpoint of optical characteristics of the device. Most preferably, the amount is 1 to 20 parts by mass. Moreover, the specific compound (3) can use 1 type (s) or 2 or more types according to each characteristic.
  • the liquid crystal alignment film is obtained from a liquid crystal alignment treatment agent containing a polymer having a specific side chain structure represented by the formula [4-1a] or the formula [4-2a].
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and n are as defined above.
  • 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 preferred.
  • X 1 is more preferably 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 preferably a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or —COO—, from the viewpoint of ease of synthesis.
  • they are a single bond, — (CH 2 ) a — (a 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.
  • 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 alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms.
  • X 6 is more preferably an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and particularly preferably an alkyl group or an alkoxy group having 1 to 9 carbon atoms.
  • n is preferably an integer of 0 to 3, more preferably 0 to 2, from the viewpoint of availability of raw materials and ease of synthesis.
  • a preferable combination of X 1 to X 6 and n is a combination of (2-1) to (2-629) described in Tables 6 to 47 on pages 13 to 34 of International Publication No. WO2011 / 132751. It should be noted that Y1 to Y6 described in each table of the publication are to be read as X 1 to X 6 in the present invention.
  • the organic group having 12 to 25 carbon atoms having a steroid skeleton of (2-605) to (2-629) listed in each table of the above publications has 17 to 51 carbon atoms having a steroid skeleton in the present invention. It shall be read as an organic group.
  • Preferred combinations of X 1 to X 6 and n are (2-25) to (2-96), (2-145) to (2-168), (2-217) to (2-240), among others. , (2-268) to (2-315), (2-364) to (2-387), (2-436) to (2-483), or (2-603) to (2-615) Is 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 and X 8 are as defined above.
  • 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 specific side chain structure in the present invention is preferably the formula [4-1a] from the viewpoint that a high and stable liquid crystal vertical alignment can be obtained.
  • the specific polymer having a specific side chain structure is not particularly limited, but at least selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane.
  • One polymer is preferred. More preferably, it is a polyimide precursor, polyimide or polysiloxane.
  • a polyimide precursor or polyimide also collectively referred to as a polyimide polymer
  • they are a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component. Is preferred.
  • R 1 represents a tetravalent organic group.
  • R 2 represents a divalent organic group.
  • a 1 and A 2 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • a 3 and A 4 Each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, and n represents a positive integer.
  • the diamine component is a diamine having two primary or secondary amino groups in the molecule.
  • examples of the tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.
  • the polyimide polymer can be obtained relatively easily by using a tetracarboxylic dianhydride of the following formula [B] and a diamine of the following formula [C] as raw materials, the structure of the following formula [D]
  • a polyamic acid having an acid or a polyimide obtained by imidizing the polyamic acid is preferable.
  • the polymer of the formula [D] obtained above is added to the alkyl group having 1 to 8 carbon atoms of A 1 and A 2 of the formula [A] and A 3 of the formula [A] by a usual synthesis method.
  • an alkyl group having 1 to 5 carbon atoms or an acetyl group of A 4 can also be introduced.
  • a method for introducing the specific side chain structure into the polyimide polymer it is preferable to use a diamine having the specific side chain structure as a part of the raw material.
  • the diamine having a specific side chain structure is particularly preferably a diamine of the following formula [4a] (also referred to as a specific side chain diamine).
  • X represents the formula [4-1a] or the formula [4-2a].
  • the definitions and preferred combinations of X 1 , X 2 , X 3 , X 4 , X 5 , X 6 and n are as in the formula [4-1a]
  • the formula [4-1a] The definitions and preferred combinations of X 7 and X 8 in 4-2a] are as shown in the above formula [4-2a].
  • m is an integer of 1 to 4, particularly preferably 1.
  • a 4 in the formula [2-13] represents a linear or branched alkyl group having 3 to 18 carbon atoms.
  • R 3 in the formulas [2-4] to [2-6] represents at least one selected from the group consisting of —O—, —CH 2 O—, —COO—, and —OCO—.
  • preferred specific side chain type diamines are those represented by the formula [2-1] to the formula [2-6], the formula [2-9] to the formula [2-13] or the formula described in International Publication WO2013 / 125595. [2-22] to [2-31]. More preferred are diamines of the following formulas [4a-32] to [4a-41] from the viewpoint of the optical characteristics of the liquid crystal display element.
  • R 1 and R 2 each represents an alkyl group having 3 to 12 carbon atoms.
  • R 3 and R 4 each represent an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
  • Most preferred is a diamine of the above formula [4a-35] to formula [4a-37], formula [4a-40] or formula [4a-41] from the viewpoint of the optical properties of the device.
  • Specific examples of the specific side chain type diamine having the specific side chain structure of the formula [4-2a] include diamines of the formulas [DA1] to [DA11] described on page 23 of International Publication WO2013 / 125595. It is done.
  • a 1 in the formulas [DA1] to [DA5] represents an alkyl group having 8 to 18 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.
  • the use ratio of the specific side chain type diamine is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, based on the optical characteristics of the device and the adhesion between the liquid crystal layer and the liquid crystal alignment film. . Moreover, 1 type (s) or 2 or more types can be used for specific side chain type diamine according to each characteristic.
  • a diamine represented by the following formula [4b] (also referred to as a second diamine) is preferable.
  • X A represents a structure selected from the following formulas [4-1b] to [4-5b].
  • r is preferably an integer of 1 to 4, particularly 1.
  • a represents an integer of 0 to 4.
  • 0 or 1 is preferable in view of availability of raw materials and synthesis
  • b is preferably 0 to 4
  • 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.
  • X a and X b each represent a hydrocarbon group having 1 to 12 carbon atoms.
  • X c represents an alkyl group having 1 to 5 carbon atoms.
  • X d is a single bond, —O—, —NH—, —N (CH 3 ) —, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— or —OCO— is shown.
  • a single bond, —O—, —CH 2 O—, —CONH—, —CON (CH 3 ) — or —COO— is preferable. More preferred is a single bond, —O—, —CH 2 O— or —COO— from the viewpoint of ease of synthesis.
  • X e represents an alkylene group having 1 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms having a cyclic group consisting of a benzene ring, a cyclocyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is It may be substituted with an alkyl group, alkoxy group, fluorine-containing alkyl group, fluorine-containing alkoxy group or fluorine atom having 1 to 3 carbon atoms.
  • an organic group having 6 to 24 carbon atoms having a cyclic group composed of an alkylene group having 2 to 12 carbon atoms, a benzene ring or a cyclocyclohexane ring is preferable. More preferred is an alkylene group having 2 to 12 carbon atoms from the viewpoint of ease of synthesis and adhesion between the liquid crystal layer and the liquid crystal alignment film.
  • X f is a single bond, —O—, —NH—, —N (CH 3 ) —, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— or —OCO— is shown.
  • a single bond, —O—, —NHCO—, —N (CH 3 ) CO— or —OCO— is preferable.
  • More preferred is a single bond, —O—, —NHCO— or —OCO— from the viewpoint of ease of synthesis.
  • X g represents a structure selected from the following formulas [4-a] to [4-f]. In particular, from the viewpoint of ease of synthesis and adhesion between the liquid crystal layer and the liquid crystal alignment film, the formula [4-a], the formula [4-b], or the formula [4-e] is preferable.
  • X A represents a hydrogen atom or a benzene ring.
  • X B represents a single bond or a cyclic group consisting of a benzene ring, cyclohexane ring or heterocyclic ring.
  • X C represents an alkyl group having 1 to 18 carbon atoms, fluorine. A containing alkyl group, an alkoxy group or a fluorine-containing alkoxy group.
  • the second diamine include the second diamine and the diamines of the formulas [2-1] to [2-15] described in pages 20 to 22 of International Publication No. WO2015 / 199148.
  • a diamine of the formula [2-11], formula [2-12] or formula [2-15] is preferred.
  • 2,4-diaminophenol 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, and 3,5-diaminobenzoic acid from the viewpoint of solubility of the polyimide polymer in a solvent and optical characteristics.
  • the proportion of the second diamine to be used is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, based on the optical characteristics of the device and the adhesion between the liquid crystal layer and the liquid crystal alignment film.
  • the 2nd diamine can use 1 type (s) or 2 or more types according to each characteristic.
  • a diamine other than the diamines of the formulas [4a] and [4b] (also referred to as other diamines) can be used.
  • Specific examples include other diamine compounds described on pages 27 to 30 of International Publication No. WO2015 / 012368, and formulas [DA1] to [DA14] described on pages 30 to 32 of the publication. It is done. 1 type, or 2 or more types can be used for other diamines according to each characteristic.
  • Examples of the raw material tetracarboxylic acid component of the polyimide polymer include tetracarboxylic dianhydride represented by the following formula [5] and its derivatives: tetracarboxylic acid, tetracarboxylic dihalide, tetracarboxylic dialkyl ester, or tetracarboxylic acid. Dialkyl ester dihalides (also collectively referred to as specific tetracarboxylic acid components) are preferred.
  • Z represents a structure selected from the following formulas [5a] to [5l].
  • Z 1 to Z 4 are each a hydrogen atom, a methyl group, a chlorine atom or a benzene ring.
  • Z 5 and Z 6 are each a hydrogen atom or a methyl group.
  • Z is the formula [5a], the formula [5c], the formula [5d], the formula [5e], the formula [5f] from the viewpoint of ease of synthesis and polymerization reactivity.
  • Formula [5g], formula [5k] or formula [5l] is preferred. More preferably, they are the formula [5a], the formula [5e], the formula [5f], the formula [5g], the formula [5k], or the formula [5l]. From the viewpoint of the optical characteristics of the element, the formula [5a], formula [5e], Formula [5f], Formula [5g], or Formula [5l].
  • the use ratio of the specific tetracarboxylic acid component is preferably 1 mol% or more, more preferably 5 mol% or more, and particularly preferably 10 mol% or more with respect to the total tetracarboxylic acid component. Most preferably, it is 10 to 90 mol%.
  • tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used.
  • Specific examples of other tetracarboxylic acid components include other tetracarboxylic acid components described on pages 34 to 35 of International Publication No. WO2015 / 012368.
  • the specific tetracarboxylic acid component and other tetracarboxylic acid components can be used singly or in combination of two or more according to the respective characteristics.
  • the method for synthesizing the polyimide polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Specific examples include the methods described on pages 35 to 36 of International Publication No. WO2015 / 012368.
  • the reaction between the diamine component and the tetracarboxylic acid component is usually performed in a solvent containing the diamine component and the tetracarboxylic acid component.
  • the solvent used at that time is not particularly limited as long as the produced polyimide precursor is soluble.
  • the solvent examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl- Examples include imidazolidinone.
  • methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D1] to [D3] can be used.
  • D 1 and D 2 each represent an alkyl group having 1 to 3 carbon atoms.
  • D 3 represents an alkyl group having 1 to 4 carbon atoms.
  • Polyimide is a polyimide obtained by ring closure of a polyimide precursor.
  • the ring closure rate also referred to as imidization rate
  • the amic acid group does not need to be 100%, and the polyimide polymer solvent. From the standpoint of solubility, etc., 30 to 80% is preferable. More preferably, it is 40 to 70%.
  • the molecular weight of the polyimide polymer is 5,000 to 1 as the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained liquid crystal alignment film, workability during film formation, and coating properties. 1,000,000 is preferable, and 10,000 to 150,000 is more preferable.
  • polysiloxane obtained by polycondensation of alkoxysilane of the following formula [A1], or alkoxysilane of the following formula [A1], and the following formula [A2] and / or the following formula
  • Polysiloxanes obtained by polycondensation with alkoxysilane [A3] are preferred.
  • a 1 represents the above formula [4-1a] or [4-2a].
  • a 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • a 3 represents an alkyl group having 1 to 5 carbon atoms.
  • M represents an integer of 1 or 2.
  • n represents an integer of 0 to 2
  • p represents an integer of 0 to 3.
  • m + n + p is 4.
  • B 1 represents an organic group having 2 to 12 carbon atoms having at least one selected from the group consisting of vinyl group, epoxy group, amino group, mercapto group, isocyanate group, methacryl group, acrylic group, ureido group and cinnamoyl group.
  • B 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • B 3 represents an alkyl group having 1 to 5 carbon atoms
  • m represents an integer of 1 or 2
  • n represents an integer of 0 to 2.
  • P represents an integer of 0 to 3, where m + n + p is 4.
  • D 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • D 2 represents an alkyl group having 1 to 5 carbon atoms.
  • N represents an integer of 0 to 3.
  • a 2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • a 3 is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of polycondensation reactivity.
  • m is preferably 1 from the viewpoint of ease of synthesis.
  • n represents an integer of 0-2.
  • p is preferably an integer of 1 to 3, more preferably 2 or 3.
  • m + n + p is 4.
  • alkoxysilane of the formula [A1] include the alkoxysilanes of the formulas [2a-1] to [2a-32] described on pages 17 to 21 of International Publication WO2015 / 008846. Of these, formula [2a-9] to formula [2a-21], formula [2a-25] to formula [2a-28] or formula [2a-32] are preferred.
  • B 1 is preferably an organic group having a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group or a ureido group from the viewpoint of availability. More preferably, it is an organic group having a methacryl group, an acryl group or a ureido group.
  • B 2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • B 3 is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of polycondensation reactivity.
  • m is preferably an integer of 1 from the viewpoint of ease of synthesis.
  • n represents an integer of 0-2.
  • p is preferably an integer of 1 to 3, more preferably 2 or 3.
  • m + n + p is 4.
  • alkoxysilane of the formula [A2] include the alkoxysilane of the formula [2b] described on pages 21 to 24 of International Publication WO2015 / 008846.
  • D 1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • D 2 is preferably an alkyl group having 1 to 3 carbon atoms.
  • n represents an integer of 0 to 3.
  • alkoxysilane of the formula [A3] include the formula [2c] described on pages 24 to 25 of International Publication WO2015 / 008846.
  • examples of the alkoxysilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and the alkoxysilanes of the formulas [A1] to [A3].
  • the polysiloxane polymer is preferably a polysiloxane obtained by polycondensation of a plurality of types of alkoxysilanes from the viewpoint of polycondensation reactivity and solubility of the polysiloxane polymer in a solvent. That is, a polysiloxane obtained by polycondensation of two types of alkoxysilanes of the formula [A1] and formula [A2], and a polysiloxane obtained by polycondensation of two types of alkoxysilanes of the formulas [A1] and [A3]. It is preferable to use any one of siloxane and polysiloxane obtained by polycondensation of three types of alkoxysilanes of formula [A1], formula [A2] and formula [A3].
  • the proportion of the alkoxysilane of the formula [A1] is preferably 1 to 40 mol%, preferably 1 to 30 mol% in all alkoxysilanes. More preferred.
  • the proportion of the alkoxysilane of the formula [A2] used is preferably 1 to 70 mol% and more preferably 1 to 60 mol% in all alkoxysilanes.
  • the proportion of the alkoxysilane of the formula [A3] used is preferably 1 to 99 mol%, more preferably 1 to 80 mol%, based on the total alkoxysilane.
  • the method for polycondensing the polysiloxane polymer is not particularly limited. Specifically, the method described in pages 26 to 29 of International Publication No. WO2015 / 008846 can be mentioned.
  • a mixture in which a plurality of types of alkoxysilanes are mixed in advance is used. Even if it reacts using, it may react, adding several types of alkoxysilane sequentially.
  • the solution of the polysiloxane polymer obtained by the above method may be used as the specific polymer as it is, or if necessary, the solution of the polysiloxane polymer obtained by the above method may be used.
  • the polymer may be concentrated, diluted by adding a solvent, or substituted with another solvent to be used as a specific polymer.
  • the solvent used for dilution also referred to as an additive solvent
  • the additive solvent is not particularly limited as long as the polysiloxane polymer is uniformly dissolved, and one or more kinds can be arbitrarily selected.
  • the additive solvent examples include, in addition to the solvent used in the polycondensation reaction, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate.
  • ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
  • ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate.
  • the polysiloxane polymer and other polymers are used as the specific polymer, the polysiloxane polymer is subjected to a polycondensation reaction before mixing the other polymer with the polysiloxane polymer.
  • the generated alcohol is preferably distilled off at normal pressure or reduced pressure.
  • the liquid crystal aligning agent in this invention is a solution for forming a liquid crystal aligning film, and is a solution containing the specific polymer which has the said specific side chain structure, and a solvent.
  • the specific polymer having a specific side chain structure is not particularly limited, but is selected from the group consisting of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane.
  • the polymer is at least one polymer.
  • a polyimide precursor, polyimide or polysiloxane is preferable.
  • 1 type in these polymers, or 2 or more types can be used for a specific polymer.
  • All of the polymer components in the liquid crystal aligning agent may be specific polymers, or other polymers may be mixed.
  • the content of the other polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the specific polymer.
  • Examples of the other polymer include the above-mentioned polymers having no specific side chain structure of the above formula [4-1a] or [4-2a].
  • Content of the solvent in a liquid-crystal aligning agent can be suitably selected from a viewpoint of obtaining the coating method of a liquid-crystal aligning agent, and the target film thickness.
  • the content of the solvent in the liquid crystal aligning agent is preferably 50 to 99.9% by mass, more preferably 60 to 99% by mass, and particularly preferably. 65 to 99% by mass.
  • the solvent used for the liquid crystal aligning agent is not particularly limited as long as the solvent dissolves the specific polymer.
  • the specific polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility of the acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane in the solvent is low, A solvent (also referred to as “solvent A”) as shown in FIG.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone is preferably used. These may be used alone or in combination.
  • the specific polymer is an acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, cellulose, or polysiloxane
  • the specific polymer is a polyimide precursor, polyimide, polyamide, or polyester, and these specific polymers Can be used, a solvent as shown below (also referred to as solvent B) can be used.
  • the solvent B include the solvents B described on pages 58 to 60 of International Publication WO2014 / 171493.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, particularly the solvent A is used for the purpose of improving the coating property of the liquid crystal aligning agent. It is preferable to use ⁇ -butyrolactone together.
  • the solvent B is preferably 1 to 99% by mass, more preferably 10 to 99% by mass, and particularly preferably 20 to 95% by mass based on the total amount of the solvent contained in the liquid crystal aligning agent.
  • the liquid crystal aligning agent includes a compound having at least one selected from the group consisting of the following formulas [b-1] to [b-11] (specific compounds (A)) from the viewpoint of the optical characteristics of the liquid crystal display element. It is preferable to contain.
  • B a represents a hydrogen atom or a benzene ring.
  • B b to B d represent an alkyl group having 1 to 5 carbon atoms.
  • K 1 is 1 to 12 integer, from the viewpoint of the optical properties of the elements, 1-8 preferably .
  • k 2 is an integer of from 0 to 4, from the viewpoint of the optical properties of the element, preferably 1 or 2 .
  • K a is A single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— or —OCO— is particularly preferred.
  • K b represents an alkyl group, a fluorine-containing alkyl group, an alkoxy group or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.
  • an alkyl group or alkoxy group having 1 to 12 carbon atoms is preferable, and an alkyl group or alkoxy group having 1 to 8 carbon atoms is more preferable.
  • K 3 is an integer of 1 to 12, particularly 1 to 8 from the viewpoint of the optical characteristics of the element.
  • K c is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), Represents —O—, —CH 2 O—, —COO— or —OCO—, particularly preferably —COO— or —OCO— in view of availability of raw materials and ease of synthesis
  • K d is a single bond , —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— or —OCO—, in particular, from the viewpoint of availability and ease of synthesis, -O- or -COO- is preferable .
  • K e is an alkyl group, a fluorine-containing alkyl group, an alkoxy group or a fluorine-containing alkoxy group having 1 to 18 carbon
  • K 4 is an integer of 0 to 4, preferably 1 or 2 from the viewpoint of the optical characteristics of the liquid crystal display element.
  • K f is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group, an alkoxy group or a fluorine-containing alkoxy group. (In particular, an alkyl group or alkoxy group having 1 to 12 carbon atoms is preferable, and an alkyl group or alkoxy group having 1 to 8 carbon atoms is more preferable.)
  • K 5 is an integer of 1 to 12, preferably 1 to 8 from the viewpoint of the optical characteristics of the element.
  • K 6 is an integer of 0 to 4, and 1 or 2 is preferable from the viewpoint of the optical characteristics of the element.
  • K g is An alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group, an alkoxy group or a fluorine-containing alkoxy group, particularly preferably an alkyl group or alkoxy group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms; An alkyl group or an alkoxy group.
  • K h represents a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO—, or —OCO—. from the viewpoint of availability and ease of synthesis, -COO- or -OCO- are preferred .
  • K i represents an alkyl group, a fluorine-containing alkyl group, an alkoxy group or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. Naka However, it is an alkyl group or alkoxy group having 1 to 12 carbon atoms.
  • K 7 is an integer of 1 to 12, and is preferably 1 to 8 from the viewpoint of the optical characteristics of the element.
  • K j is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), ⁇ O—, —CH 2 O—, —COO— or —OCO— is preferred, and —COO— or —OCO— is preferred from the viewpoint of availability of raw materials and ease of synthesis, where K k is the number of carbon atoms.
  • 1 to 18 represents an alkyl group, a fluorine-containing alkyl group, an alkoxy group or a fluorine-containing alkoxy group, preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group, more preferably an alkyl group having 1 to 8 carbon atoms. Group or alkoxy group.
  • the formula [b-1a], the formula [b-2a], the formula [b-7a], the formula [b-8a], the formula [b-10a], the formula [b-11a], the formula [b- 13a], formula [b-14a], formula [b-16a] or formula [b-17a] is more preferred.
  • the use ratio of the specific compound (A) in the liquid crystal aligning agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 100 parts by mass of the specific polymer from the viewpoint of optical characteristics of the device. Is 20 parts by mass, and particularly preferably 1 to 10 parts by mass.
  • a specific compound (A) can be used 1 type, or 2 or more types according to each characteristic.
  • the liquid crystal aligning agent includes a compound having an epoxy group, an isocyanate group, an oxetane group, or a cyclocarbonate group, or a group consisting of a hydroxy group, a hydroxyalkyl group, and a lower alkoxyalkyl group in order to increase the strength of the liquid crystal alignment film. It is preferable to contain a compound having at least one kind of group selected (collectively also referred to as a specific crosslinkable compound). In that case, it is necessary to have two or more of these groups in the compound. Specific examples of the crosslinkable compound having an epoxy group or an isocyanate group include those described on pages 63 to 64 of International Publication No. WO2014 / 171493.
  • crosslinkable compound having an oxetane group examples include formulas [4a] to [4k] described on pages 58 to 59 of International Publication No. WO2011 / 132751.
  • Specific examples of the crosslinkable compound having a cyclocarbonate group include Formulas [5-1] to [5-42] described on pages 76 to 82 of International Publication WO2012 / 014898.
  • Specific examples of the crosslinkable compound having at least one group selected from the group consisting of a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group include melamine derivatives described on pages 65 to 66 of International Publication No. 2014/171493.
  • benzoguanamine derivatives and formulas [6-1] to [6-48] described on pages 62 to 66 of International Publication No. WO2011 / 132751 may be mentioned.
  • the content of the specific crosslinkable compound in the liquid crystal aligning agent is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of all polymer components. In order for the crosslinking reaction to proceed and to exhibit the desired effect, the amount is more preferably 0.1 to 50 parts by weight, and most preferably 1 to 30 parts by weight based on 100 parts by weight of the total polymer components.
  • the liquid crystal alignment treatment agent preferably contains at least one generator (also referred to as a specific generator) selected from the group consisting of a photo radical generator, a photo acid generator and a photo base generator.
  • the specific generator includes specific generators described on pages 54 to 56 of International Publication No. 2014/171493.
  • a photo radical generator is preferable from the viewpoint of adhesion between the liquid crystal layer and the liquid crystal alignment film.
  • the liquid crystal aligning agent is a compound having at least one structure selected from the group consisting of the following formulas [e-1] to [e-8] for the purpose of enhancing the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film. It is preferable to contain (also referred to as a specific adhesion compound).
  • E 1 represents a hydrogen atom or a benzene ring.
  • E 2 represents a cyclic group consisting of a benzene ring, a cyclohexane ring or a heterocyclic ring.
  • E 3 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group, an alkoxy group. Group or fluorine-containing alkoxy group.
  • Specific examples of the specific adhesion compound include the formula [6] described on pages 43 to 46 of International Publication No. WO2015 / 012368. Furthermore, the adhesive compounds described on pages 61 to 63 of International Publication No. WO2014 / 171493 can be mentioned.
  • the content of the specific adhesion compound in the liquid crystal aligning agent is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components. 100 parts by mass is more preferable, and 1 to 50 parts by mass is most preferable.
  • the specific adhesion compound may be used alone or in combination of two or more depending on each property.
  • the formula [M1] to the formula shown in pages 69 to 73 of International Publication No. WO2011 / 132751 A nitrogen-containing heterocyclic amine compound of [M156] can be added.
  • This amine compound may be added directly to the liquid crystal aligning agent, but it is preferably added after a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent.
  • the solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer.
  • the liquid crystal aligning agent can be added with a compound that improves the coating film thickness uniformity and surface smoothness. Furthermore, compounds that improve the adhesion between the liquid crystal alignment film and the substrate and the surface smoothness can be added.
  • the compound for this purpose include a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and the like. Specific examples include those described on page 67 of International Publication No. WO2014 / 171493. Further, the use ratio is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total polymer components contained in the liquid crystal aligning agent.
  • the compound that improves the adhesion between the liquid crystal alignment film and the substrate include compounds described on pages 67 to 69 of International Publication No. WO2014 / 171493. Further, the use ratio is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total polymer components contained in the liquid crystal aligning agent.
  • a liquid crystal alignment treatment agent may be added with a dielectric or conductive material for the purpose of changing electrical characteristics such as dielectric constant or conductivity of the liquid crystal alignment film.
  • the substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate.
  • a plastic substrate such as an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate, and a film thereof. Can be used.
  • a plastic substrate or a film is preferable.
  • a substrate on which an ITO (Indium Tin Oxide) electrode, an IZO (Indium Zinc Oxide) electrode, an IGZO (Indium Gallium Zinc Oxide) electrode, an organic conductive film, etc. are formed. Is preferred.
  • a substrate on which a metal such as a silicon wafer or aluminum or a dielectric multilayer film is formed can be used as long as the substrate is only on one side.
  • liquid crystal alignment film for vertically aligning liquid crystal molecules.
  • This liquid crystal alignment film can be obtained by applying a liquid crystal alignment treatment agent on a substrate and baking it, followed by alignment treatment by rubbing treatment or light irradiation.
  • a liquid crystal alignment treatment agent on a substrate and baking it, followed by alignment treatment by rubbing treatment or light irradiation.
  • the liquid crystal alignment film in the present invention it can be used as a liquid crystal alignment film without these alignment treatments.
  • the application method of the liquid crystal aligning agent is not particularly limited, but industrially includes screen printing, offset printing, flexographic printing, ink jet method, dipping method, roll coater method, slit coater method, spinner method, spray method, etc. Depending on the type of substrate and the film thickness of the liquid crystal alignment film, it can be selected as appropriate.
  • the liquid crystal alignment treatment agent After the liquid crystal alignment treatment agent is applied on the substrate, it is heated to 30 to 300 ° C., preferably depending on the type of the substrate and the solvent used, by a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven.
  • the liquid crystal alignment film can be obtained by evaporating the solvent at 30 to 250 ° C.
  • the treatment is preferably performed at 30 to 150 ° C. If the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption, and if it is too thin, the reliability of the device may be lowered. Therefore, the thickness is preferably 5 to 500 nm, more preferably 10 to 300 nm. Particularly preferably, the thickness is 10 to 250 nm.
  • a spacer for controlling the electrode gap (gap) of the liquid crystal display element may be incorporated.
  • the injection method of a liquid crystal composition is not specifically limited, For example, the following method is mentioned. That is, when a glass substrate is used as a substrate, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a sealant is applied to four pieces of one side of the substrate except for a part, and then the surface of the liquid crystal alignment film is An empty cell is produced by bonding the other substrate to the inside.
  • a method of obtaining a liquid crystal composition injection cell by injecting the liquid crystal composition under reduced pressure from a place where the sealant is not applied can be mentioned.
  • a plastic substrate or a film is used as a substrate, a pair of substrates having a liquid crystal alignment film is prepared, and a liquid crystal composition is formed on one substrate by an ODF (One Drop Filling) method or an inkjet method. Is dropped, and then the other substrate is bonded to obtain a liquid crystal composition injection cell.
  • ODF One Drop Filling
  • the adhesion between the liquid crystal layer and the liquid crystal alignment film is high, it is not necessary to apply the sealing agent to the four pieces of the substrate.
  • the gap of the liquid crystal display element can be controlled by the above-described spacer or the like.
  • Examples of the method include a method of introducing a spacer having a target size into the liquid crystal composition, a method using a substrate having a column spacer of a target size, and the like.
  • the gap can be controlled without introducing a spacer.
  • the size of the gap of the liquid crystal display element is preferably 1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, and particularly preferably 2 to 30 ⁇ m. If the gap is too small, the contrast of the device is lowered, and if it is too large, the drive voltage of the device is increased.
  • the liquid crystal display element of the present invention can be obtained by curing the liquid crystal composition in a state where a part or the whole of the liquid crystal composition exhibits liquid crystallinity to form a cured product composite of the liquid crystal and the polymerizable compound.
  • the liquid crystal composition is cured by irradiating the liquid crystal composition injection cell with ultraviolet rays.
  • the light source of the ultraviolet irradiation device used at that time include a metal halide lamp and a high-pressure mercury lamp.
  • the wavelength of ultraviolet light is preferably 250 to 400 nm. Of these, 310 to 370 nm is preferable.
  • heat treatment may be performed after irradiation with ultraviolet rays.
  • the temperature at that time is preferably 40 to 120 ° C., more preferably 40 to 80 ° C.
  • E1 alkoxysilane monomer represented by the following formula [E1], E2: octadecyltriethoxysilane, E3: 3-methacryloxypropyltrimethoxysilane, E4: 3-ureidopropyltriethoxysilane, E5: tetraethoxysilane
  • NMP N-methyl-2-pyrrolidone
  • ⁇ -BL ⁇ -butyrolactone
  • BCS ethylene glycol monobutyl ether
  • PB propylene glycol monobutyl ether
  • PGME propylene glycol monomethyl ether
  • ECS ethylene glycol monoethyl ether
  • EC diethylene glycol Monoethyl ether
  • the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid that appear in the vicinity of 9.5 ppm to 10.0 ppm. It calculated
  • Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100 (X is the accumulated proton peak value derived from NH group of amic acid, y is the accumulated peak value of reference proton, ⁇ is the reference proton for one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) The number ratio.
  • This reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered off. This deposit was wash
  • the imidation ratio of this polyimide was 58%, Mn was 17,200, and Mw was 47,500.
  • ⁇ Synthesis Example 11> Prepare a solution of alkoxysilane monomer by mixing EC (29.2 g), E1 (4.10 g) and E5 (38.8 g) in a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube. did. To this solution, a solution prepared by mixing EC (14.6 g), water (10.8 g), and oxalic acid (0.50 g) as a catalyst was added dropwise at 25 ° C. over 30 minutes. The mixture was further stirred at 25 ° C. for 30 minutes.
  • ⁇ Synthesis Example 19 ⁇ -BL (1.70 g) and PGME (55.0 g) were added to the polyamic acid solution (4) (10.0 g) obtained in Synthesis Example 4, and the mixture was stirred at 25 ° C. for 2 hours. Then, Q1 (0.14g) and K1 (0.14g) were added, and it stirred at 25 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (7).
  • compositions of the liquid crystal alignment treatment agents in Synthesis Examples 13 to 27 are summarized in Tables 3 and 4. All of these liquid crystal alignment treatment agents were confirmed to be uniform solutions with no abnormalities such as turbidity and precipitation.
  • Tables 3 and 4 the numerical values in parentheses for the specific compound (A), the specific crosslinkable compound, the specific generator, and the specific adhesive compound added to the liquid crystal alignment treatment agent are the specific polymers. Content (mass part) with respect to 100 mass parts is shown. In addition, “-” in the table indicates that it is not used.
  • ⁇ Liquid crystal composition (3) Mix L1 (3.24 g), R1 (1.20 g), R2 (1.20 g), P1 (0.012 g), T1 (0.202 g), S1 (0.202 g) and W1 (0.202 g) And it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal composition (3).
  • ⁇ Liquid crystal composition (6) > L1 (2.84 g), R1 (1.20 g), R2 (1.20 g), P1 (0.012 g) and T1 (0.202 g) were mixed and stirred at 25 ° C. for 6 hours to obtain a liquid crystal composition (6) was obtained.
  • ⁇ Liquid crystal composition (7) > L1 (2.84 g), R1 (1.20 g), R2 (1.20 g), P1 (0.012 g) and S1 (0.202 g) were mixed and stirred at 25 ° C. for 6 hours to obtain a liquid crystal composition (7) was obtained.
  • the liquid crystal aligning agent obtained in the synthesis example was subjected to pressure filtration with a membrane filter having a pore diameter of 1 ⁇ m.
  • the obtained solution was spin-coated on an ITO surface of a glass substrate with an ITO electrode (length: 100 mm, width: 100 mm, thickness: 0.7 mm) washed with pure water and IPA (isopropyl alcohol), and placed on a hot plate. Then, heat treatment was performed at 100 ° C. for 5 minutes and in a heat circulation clean oven at 210 ° C. for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm.
  • Two ITO substrates with the obtained liquid crystal alignment film were prepared, and a spacer having a particle diameter of 6 ⁇ m was applied to the liquid crystal alignment film surface of one of the substrates. Thereafter, the liquid crystal composition is dropped onto the surface of the liquid crystal alignment film coated with the spacer on the substrate by ODF (One Drop Filling) method, and then bonded so that the liquid crystal alignment film interface of the other substrate faces.
  • ODF One Drop Filling
  • the liquid crystal display element before this treatment was cut with a wavelength of 350 nm or less using a metal halide lamp with an illuminance of 20 mW / cm 2 and irradiated with ultraviolet rays for an irradiation time of 30 seconds. At that time, the temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled to 25 ° C. Thereby, a liquid crystal display element (reverse type element) (glass substrate) was obtained. The liquid crystal orientation was evaluated using this liquid crystal display element. The liquid crystal alignment was confirmed by observing the device with a polarizing microscope (Nikon Corporation, ECLIPSE E600WPOL) to determine whether the liquid crystal was aligned vertically. As a result, in the liquid crystal display elements of Examples and Comparative Examples 2 to 4, the liquid crystal was vertically aligned. However, in the liquid crystal display element of Comparative Example 1, the liquid crystal was not vertically aligned.
  • the liquid crystal aligning agent obtained in the synthesis example was subjected to pressure filtration with a membrane filter having a pore diameter of 1 ⁇ m.
  • the obtained solution was coated with a bar coater on the ITO surface of a PET (polyethylene terephthalate) substrate (length: 150 mm, width: 150 mm, thickness: 0.2 mm) washed with pure water and thermally circulated.
  • a heat treatment was performed at 120 ° C. for 2 minutes in a mold clean oven to obtain an ITO substrate with a liquid crystal alignment film having a thickness of 100 nm.
  • liquid crystal display element Two ITO substrates with the obtained liquid crystal alignment film were prepared, and a 6 ⁇ m spacer was applied to the liquid crystal alignment film surface of one of the substrates. Thereafter, the liquid crystal composition is dropped onto the liquid crystal alignment film surface coated with the spacer of the substrate by the ODF method, and then bonded so that the liquid crystal alignment film interface of the other substrate faces. A liquid crystal display element was obtained.
  • the liquid crystal display element before this treatment was cut at a wavelength of 350 nm or less using a metal halide lamp with an illuminance of 20 mW / cm 2 and irradiated with ultraviolet rays for an irradiation time of 30 seconds. At that time, the temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was controlled to 25 ° C. Thereby, a liquid crystal display element (reverse type element) (plastic substrate) was obtained. The liquid crystal orientation was evaluated using this liquid crystal display element. The liquid crystal alignment was confirmed by observing the device with a polarizing microscope (Nikon Corporation, ECLIPSE E600WPOL) to determine whether the liquid crystal was aligned vertically. As a result, in the liquid crystal display element of the example, the liquid crystal was vertically aligned.
  • the transmittance after being stored in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 90% RH for 36 hours was also evaluated.
  • the lower the rate of decrease in the transmittance after storage in the constant temperature and humidity chamber with respect to the transmittance (initial value) immediately after the production of the liquid crystal display element the better the evaluation.
  • the transmittance was also evaluated.
  • the evaluation method is the same conditions as described above. Furthermore, as a stability test for the light irradiation of the liquid crystal display element, the transmittance after irradiation with ultraviolet rays of 5 J / cm 2 in terms of 365 nm using a tabletop UV curing device (HCT3B28HEX-1 manufactured by Senlite Co., Ltd.) Evaluation was also performed. Specifically, the lower the transmittance reduction rate after ultraviolet irradiation with respect to the transmittance (initial value) immediately after manufacturing the liquid crystal display element, the better the evaluation.
  • Evaluation of the scattering characteristic at the time of voltage application was performed by applying 30V to a liquid crystal display element (a glass substrate and a plastic substrate) by alternating current drive, and visually observing the alignment state of a liquid crystal.
  • the liquid crystal display element that was clouded that is, the one that obtained the scattering characteristics was considered excellent in this evaluation (good display in the table).
  • the alignment state of the liquid crystal after being stored in a constant temperature and humidity chamber at a temperature of 80 ° C. and a humidity of 90% RH for 36 hours was also confirmed.
  • the liquid crystal display element that was clouded, that is, the one that obtained the scattering characteristics was considered excellent in this evaluation (good display in the table).
  • Tables 8 to 10 collectively show the adhesion results (adhesion) between the liquid crystal layer and the liquid crystal alignment film after storage in a constant temperature and humidity chamber (constant temperature and humidity) and after irradiation with ultraviolet rays (ultraviolet rays).
  • Examples 1 to 17 and Comparative Examples 1 to 7 As shown in Tables 5 to 10 below, using any one of the liquid crystal aligning agents (1) to (15) and any one of the liquid crystal compositions (1) to (7), the optical characteristics ( (Transparency and scattering characteristics) and adhesion between the liquid crystal layer and the liquid crystal alignment film were evaluated.
  • Examples 1 to 3, 11, 13, and 16 and Comparative Examples 1 to 4 a liquid crystal display element was prepared on a glass substrate and evaluated, and Examples 4 to 10, 12, 14, 15, 17 In Comparative Examples 5 to 7, a liquid crystal display element was produced with a plastic substrate and evaluated. The results of these evaluations are summarized in Tables 5 to 10.
  • * 1 Evaluation was not possible because the liquid crystal was not vertically aligned.
  • * 2 A very small amount of bubbles was observed in the device.
  • * 3 A small amount of bubbles was observed in the element (more than * 2).
  • * 4 Bubbles were observed in the element (more than * 3).
  • * 5 Many bubbles were observed in the element (more than * 4).
  • the liquid crystal display elements of the examples have better optical characteristics than the comparative examples, that is, the liquid crystal display elements with good liquid crystal orientation after storage in a high-temperature bath and transparency when no voltage is applied. became. Furthermore, the adhesion between the liquid crystal layer and the vertical liquid crystal alignment film was also high. In particular, these characteristics were good even when a plastic substrate was used as the substrate of the liquid crystal display element. In addition, the liquid crystal display elements of the examples have better optical characteristics than the comparative examples, that is, transparency at the initial stage, after storage in a constant temperature and humidity chamber, and after application of ultraviolet light, when no voltage is applied, and the liquid crystal layer The adhesion of the liquid crystal alignment film was also high. In particular, when a plastic substrate was used as the substrate of the liquid crystal display element, these characteristics were good.
  • the examples containing the specific compounds (1) and (2) in the liquid crystal composition were compared with the comparative example in which they were not introduced or the comparative example in which only one of them was introduced.
  • the optical characteristics under the conditions and the adhesion between the liquid crystal and the liquid crystal alignment film increased.
  • the liquid crystal was not aligned vertically. Specifically, it is Comparative Example 1.
  • the optical properties, particularly the transparency increased. Specifically, it is a comparison between Examples 7 and 8 under the same conditions.
  • the diamine having the specific side chain structure of the formula [4-1a] is used in the specific side chain structure in the specific polymer of the liquid crystal aligning agent, the diamine having the formula [4-2a] is used.
  • the optical properties, particularly transparency increased. Furthermore, even after storing in a constant temperature and humidity chamber for a long time, which was conducted as an emphasis test, the result was highly transparent.
  • the adhesion between the liquid crystal layer and the liquid crystal alignment film was particularly high under severe conditions. Specifically, this is a comparison between Examples 1 and 3.
  • the specific compound (A) was contained in the liquid crystal aligning agent, the optical properties, particularly the transparency became high. Specifically, it is a comparison between Examples 4 and 5 under the same conditions.
  • the specific crosslinkable compound was introduced into the liquid crystal aligning agent, the adhesion between the liquid crystal layer and the liquid crystal aligning film was increased particularly under severe conditions. Specifically, this is a comparison between Examples 4 and 6.
  • the liquid crystal display element of the present invention is suitably used for elements used in transportation equipment such as automobiles, railways, and aircraft, specifically, optical shutter elements used for light control windows and room mirrors.
  • this element has higher light-intake efficiency at night than conventional reverse-type elements, and can further enhance the effect of preventing glare from outside light. Comfort can be improved and reliability is increased.
  • this element can also be used for the light guide plate of display devices such as LCD (Liquid Crystal Display) and OLED (Organic Light-emitting Diode), and the back plate of these displays.
  • display devices such as LCD (Liquid Crystal Display) and OLED (Organic Light-emitting Diode)
  • the back plate of these displays for example, when the screen is displayed on the transparent display by combining the transparent display and the present element, in order to suppress the entry of light from the rear surface with the present element Can be used.
  • the present element is in a scattering state where a voltage is applied when performing screen display on a transparent display, and the screen display can be made clear. After the screen display is completed, the device is in a transparent state where no voltage is applied.

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CN112041739A (zh) * 2018-04-27 2020-12-04 日产化学株式会社 液晶调光元件
JPWO2019208765A1 (ja) * 2018-04-27 2021-05-20 日産化学株式会社 液晶調光素子
JP7355007B2 (ja) 2018-04-27 2023-10-03 日産化学株式会社 ゲストホスト型液晶調光素子用の液晶配向剤
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JP2020016710A (ja) * 2018-07-23 2020-01-30 Jsr株式会社 液晶素子及びその製造方法、表示装置、並びに液晶組成物

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