WO2017217430A1 - Élément à cristaux liquides, composition de cristaux liquides, et écran, affichage et fenêtre utilisant l'élément à cristaux liquides - Google Patents

Élément à cristaux liquides, composition de cristaux liquides, et écran, affichage et fenêtre utilisant l'élément à cristaux liquides Download PDF

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WO2017217430A1
WO2017217430A1 PCT/JP2017/021873 JP2017021873W WO2017217430A1 WO 2017217430 A1 WO2017217430 A1 WO 2017217430A1 JP 2017021873 W JP2017021873 W JP 2017021873W WO 2017217430 A1 WO2017217430 A1 WO 2017217430A1
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liquid crystal
group
voltage
substituent
crystal element
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Japanese (ja)
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紀行 木田
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三菱ケミカル株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • 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
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • 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
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • 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
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • 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
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • 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
    • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering

Definitions

  • the present invention relates to a liquid crystal element and a liquid crystal composition capable of switching between a light transmission state and a light scattering state without using a polarizing plate, and a screen, a display, and a window using the liquid crystal element.
  • a transmission-scattering type liquid crystal element using a difference between the refractive index between a polymer and a liquid crystal or a liquid crystal domain by combining a liquid crystal and a transparent polymer resin does not require a polarizing plate. It is attracting attention because of its high visible light utilization efficiency.
  • transmission-scattering type liquid crystal elements polymer-stabilized liquid crystals (PSLC: Polymer-Stabilized Liquid Crystals) and polymer-dispersed liquid crystals (PDLC: Polymer Dispersed Liquid Crystals) are widely known.
  • PSLC Polymer-stabilized liquid crystals
  • PDLC Polymer-dispersed liquid crystals
  • a minute amount of polymer of about 5% by weight is connected as a network network in a continuously spreading liquid crystal phase.
  • the latter has a structure in which liquid crystal phase droplets are dispersed in a polymer film (Non-Patent Document 1).
  • liquid crystal elements have been put into practical use as dimming shutters for the purpose of protecting design and privacy in vehicles such as trains, automobiles, windows, doors, partitions, etc. of buildings such as business buildings and hospitals. It is also used as a display device for displaying characters and figures. In such a device, since the use time in the transparent state is generally overwhelmingly long, from the viewpoint of power saving, it is transparent when no voltage is applied, and operates in a reverse mode electro-optic effect that operates in a scattering state when a voltage is applied. It is desirable to have
  • a liquid crystal composition to which a polymerizable monomer is added is photocured while maintaining a transparent state such as homogeneous, planar, homeotropic, etc. And a method of forming a polymer resin composite is known.
  • PSCT Polymer Stabilized Cholesteric Texture
  • ⁇ a chiral nematic liquid crystal having a positive dielectric anisotropy
  • PDLC a dielectric constant
  • Liquid crystals having negative anisotropy are known.
  • the latter has problems such as a large temperature dependency of light transmittance, a large viewing angle dependency, or an expensive liquid crystal.
  • the former has the advantages that the temperature dependence of the light transmittance is small and the viewing angle dependence of the light transmittance is small, and that the response speed of the element is fast, and is promising.
  • Patent Documents 1 to 3 disclose transmission-scattering liquid crystal elements that exhibit high transparency when transparent, high scattering when shielded, and high-speed response by applying a specific polymerizable monomer.
  • PSLC and PDLC have a problem in which the appearance and uniformity of the liquid crystal element is impaired if composition separation such as precipitation of solid components occurs when the liquid crystal composition is stored for a long time or a liquid crystal element is manufactured. Therefore, a polymerizable monomer having high solubility in the host liquid crystal is selected.
  • PSA Polymer Sustained Alignment
  • a liquid crystal composition to which a very small amount of polymerizable monomer of 1% by weight or less is added is photocured in a liquid crystal element to form a polymer film on the alignment film surface, thereby stabilizing the liquid crystal alignment. It is known that a high-speed response and high electrical reliability of a liquid crystal element can be obtained by using this technique.
  • Patent Document 4 discloses a liquid crystal element that exhibits a high-speed response by applying a specific polymerizable monomer.
  • Patent Document 5 discloses a liquid crystal element that exhibits a high-speed response and high electrical reliability by applying a specific polymerizable monomer having high host liquid crystal solubility.
  • Patent Document 6 discloses a novel PDLC material that can be operated by either light scattering under electric field off conditions, transparent under electric field on conditions, or light scattering under electric field on conditions and transparent under electric field off conditions.
  • Patent Document 7 includes a liquid crystalline ester compound containing two or more F atoms, a nematic liquid crystal containing a liquid crystalline tolan compound, and the like, so that a low driving voltage can be achieved when used in a liquid crystal display element.
  • a liquid crystal composition is disclosed.
  • the liquid crystal composition As the liquid crystal composition, application of a polymerizable monomer having high host liquid crystal solubility is required. Further, the transmission-scattering type liquid crystal element is required to have characteristics such as high transparency when transparent (transmitting), high scattering when shielded (scattering), high-speed response, and high electrical reliability. Conventionally, a method for individually improving these characteristics has been shown, but a method for satisfying all of these properties in a balanced manner has not been shown.
  • the transparency (transmission) of the transmission-scattering type liquid crystal element may be a light transmission (transparency) state when at least one of DC and AC voltages is not applied (when the power is OFF). At least one of them may be in a light transmissive (transparent) state when applied (when the power is turned on), or at least one of a direct current and an alternating voltage only when switching from a light scattering (light shielding) state to a light transmissive (transparent) state. May be in a light transmissive (transparent) state.
  • the light scattering (light shielding) of the transmission-scattering type liquid crystal element may be a light scattering (light shielding) state when at least one of a direct current and an alternating voltage is applied (when the power is turned on). At least one of these may be in a light scattering (light-shielding) state when no mark is applied (when the power is off), and only when switching from the light transmission (transparent) state to the light scattering (light-shielding) state, A light scattering (light-shielding) state may be applied by applying at least one.
  • Patent Documents 4 and 5 are optimized for the PSA technology, cannot be switched to the scattering mode, and require a member such as a polarizing plate to be used as a display. There was a problem that got worse. If these are applied to a transmission-scattering type liquid crystal device, the high solubility of the polymerizable monomer in the host liquid crystal, the high transparency of the liquid crystal device when transparent, the high scattering property when shielded from light, the high-speed response and the high electrical reliability. Either or both were insufficient.
  • Patent Document 6 Although it is excellent in high transparency at the time of transparency, high scattering property at the time of light shielding, high-speed response, etc., according to the study of the present inventor, application to a window of a building and a window of a vehicle, It has been found that there is a problem with the light resistance required when irradiating projector light or backlight as a display device. That is, it has been found that the performance of the light adjusting device is deteriorated when exposed to ultraviolet rays or visible light for a long time. The same applies to the technique described in Japanese Patent Application Laid-Open No. 2016-110148 issued on June 20, 2016.
  • Patent Document 7 Although it is excellent in the high scattering property at the time of light shielding, the transparency at the time of transparency is poor, and the contrast at power ON / OFF is insufficient. I understood.
  • the present invention has been made in view of the above problems, and provides a high-performance liquid crystal element that satisfies the following required characteristics (1) and (2), and a liquid crystal composition capable of obtaining the liquid crystal element. Is an issue. It is another object of the present invention to provide a screen, a display, and a window having the liquid crystal element.
  • (2) Excellent light resistance Specifically, the performance of the light control device is maintained even after the light resistance test is performed.
  • the present inventor has obtained a specific chiral nematic liquid crystal component and a liquid crystal composition using a polymerizable monomer, and a specific chiral nematic liquid crystal component and a polymer resin phase in the liquid crystal light control layer.
  • the present inventors have found that the above-mentioned problems can be solved by using a liquid crystal element containing a composite containing. That is, the gist of the present invention is as follows.
  • Liquid crystal dimming comprising at least one transparent substrate, having a pair of substrates with electrodes arranged opposite to each other, and a composite containing a chiral nematic liquid crystal phase and a polymer resin phase between the substrates
  • the phase contains at least one compound represented by the following formula (2), (3), or (4), and the total amount of these compounds is 15% by weight or more based on the total amount of the chiral nematic liquid crystal component.
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent
  • X 1 and X 4 are Each independently represents a divalent group which may have a substituent
  • X 2 and X 3 each independently represent a divalent group which may have a direct bond or a substituent
  • a 1 to A 3 each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent.
  • An aliphatic hydrocarbon ring group or a divalent condensed ring group which may be any one of an aromatic hydrocarbon ring, an aromatic heterocycle and an aliphatic hydrocarbon ring; or it is constituted by one or more, a 1 ⁇ at least one aromatic optionally substituted hydrocarbon group and location of the a 3
  • m 1 and m 4 are each independently, 0 or an integer of 6 or less
  • m 2 and m 3 are each Independently, it represents an integer of 0 or more and 4 or less.
  • S 1 ⁇ S 4 are each independently a hydrogen atom, substituted one or more carbon atoms, which may, of 10 or less alkyl group or a substituted Represents an alkoxyl group having 1 to 10 carbon atoms that may have a group
  • Y 1 to Y 6 each independently represent any of a hydrogen atom, a fluorine atom, and a cyano group
  • Y 1 to Y Any one of 3 is a fluorine atom
  • any one of Y 4 to Y 6 is a fluorine atom
  • B 1 to B 5 may each independently have a substituent
  • C 1 to C 3 each independently represents a direct bond or any of the following groups (6a) to (6d)
  • n 1 to n 3 are Each independently represents 0 or 1; ]
  • the distance (d) between the pair of substrates with electrodes arranged opposite to each other is 2 ⁇ m or more and 100 ⁇ m or less, and the relationship between the chiral pitch length (p) of the chiral nematic liquid crystal and d is: The liquid crystal element according to any one of [1] to [3], wherein d / p ⁇ 1.
  • the haze when applying at least one of a DC voltage and an AC voltage is 70% or more.
  • the liquid crystal element In the temperature range of ⁇ 10 ° C. or higher, the liquid crystal element has a visible light transmittance of 100% when no voltage is applied, and a visible light transmittance of 0% when at least one of a DC voltage and an AC voltage is applied.
  • the visible light transmittance when no voltage is applied is when at least one of a DC voltage and an AC voltage is applied.
  • the haze when no voltage is applied is 70% or more, and at least one of a DC voltage and an AC voltage
  • the liquid crystal element according to any one of [1] to [7] and [11], wherein the haze upon application is 15% or less.
  • the liquid crystal element In a temperature range of ⁇ 10 ° C. or higher, the liquid crystal element has a visible light transmittance of 100% when at least one of a DC voltage and an AC voltage is applied, and a visible light transmittance of 0% when no voltage is applied.
  • R 3 ′ and R 4 ′ each independently represent an unsaturated acyl group
  • X 1 ′ and X 4 ′ each independently have a substituent 2 X 2 ′ and X 3 ′ each independently represents a divalent group that may have a direct bond or a substituent
  • a 1 ′ to A 3 ′ each independently A divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, an aliphatic hydrocarbon ring group which may have a substituent Or a divalent fused ring group, which is composed of any one or more of an aromatic hydrocarbon ring, an aromatic heterocycle and an aliphatic hydrocarbon ring
  • a 1 At least one of ' to A 3' is an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent
  • m 1 ′ and m 4 ′ each independently represent an integer of 0 or more and 6 or less
  • S 1 to S 4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent.
  • Y 1 to Y 6 each independently represent any of a hydrogen atom, a fluorine atom, and a cyano group
  • Y 1 to Y Any one of 3 is a fluorine atom
  • any one of Y 4 to Y 6 is a fluorine atom
  • B 1 to B 5 may each independently have a substituent
  • C 1 to C 3 each independently represents a direct bond or any of the following groups (6a) to (6d)
  • n 1 to n 3 are Each independently represents 0 or 1; ]
  • a chiral nematic liquid crystal composition containing a polymerizable monomer and a chiral nematic liquid crystal component having a positive dielectric anisotropy, including a polymerizable monomer represented by the following formula (8): ), (3), or (4).
  • a liquid crystal composition comprising at least one compound represented by (4), wherein the total amount of these compounds is 15% by weight or more based on the chiral nematic liquid crystal component.
  • R 3 ′′ and R 4 ′′ each independently represents an unsaturated acyl group, and X 1 ′′ and X 4 ′′ each independently have a substituent.
  • X 2 ′′ and X 3 ′′ each independently represents a divalent group which may have a direct bond or a substituent, and
  • a 1 ′′ to A 1 3 ′′ each independently has a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent.
  • S 1 to S 4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent.
  • Y 1 to Y 6 each independently represent any of a hydrogen atom, a fluorine atom, and a cyano group
  • Y 1 to Y Any one of 3 is a fluorine atom
  • any one of Y 4 to Y 6 is a fluorine atom
  • B 1 to B 5 may each independently have a substituent
  • C 1 to C 3 each independently represents a direct bond or any of the following groups (6a) to (6d)
  • n 1 to n 3 are Each independently represents 0 or 1; ]
  • a liquid crystal device satisfying the following required characteristics (1) and (2), a liquid crystal composition capable of obtaining the liquid crystal device, and a screen, display and window having the liquid crystal device.
  • the (1) Excellent performance as a light control element. Specifically, the haze is low when transparent, the haze is high when scattered, and the response time is short.
  • (2) Excellent light resistance. Specifically, the performance of the light control device is maintained even after the light resistance test is performed.
  • the liquid crystal device of the present invention has excellent performance as a light control device and excellent light resistance, and can sufficiently maintain the original excellent light control device performance even after performing a light resistance test.
  • the liquid crystal element and the liquid crystal composition of the present invention are useful for screens, displays, windows and the like because of the above characteristics.
  • it can be used as a visual field blocking element in a building window, a partition, or the like.
  • It can also be used as a display for notice boards, show windows, computer terminals, projections, and the like.
  • the liquid crystal element of the present invention can be switched between a transparent state and a light shielding state (transmission-scattering type). Switching between the transparent state and the light-shielding state is achieved by that the liquid crystal element has at least one transparent substrate and has a pair of substrates with electrodes arranged opposite to each other, and a chiral nematic liquid crystal phase and a polymer resin between the substrates. This can be realized by electrically driving a liquid crystal light control layer including a composite including a phase. As the liquid crystal light control layer, a composite of a transmission-scattering chiral nematic liquid crystal phase and a polymer resin phase, which can be switched between a transparent state and a light shielding state by electric drive, can be used.
  • the structure represented by the formula (1) has the following performance.
  • a network-like network structure is formed at the interface between the liquid crystal phase and the polymer resin phase, and in the network structure, the polymer has rigidity capable of maintaining a fine structure of about 10 nm to 100 nm.
  • the interface area between the polymer resin phase and the chiral nematic liquid crystal phase is large.
  • the orientation of the polymer is high.
  • the interaction between the ⁇ electrons of the polymer and the ⁇ electrons of the chiral nematic liquid crystal is large.
  • the orientation of the chiral nematic liquid crystal is controlled, while scattering at the interface between the chiral nematic liquid crystal phase and the polymer resin phase is sufficiently reduced, and haze is reduced.
  • the domain size is 100 nm ⁇ suitable for visible light scattering in the focal conic structure of the chiral nematic liquid crystal polydomain (the spiral axis of the chiral nematic liquid crystal is in a different direction for each domain). Since it can distribute in the range of 10 micrometers, haze becomes high.
  • the liquid crystal element of the present invention can significantly improve the light resistance by including a predetermined amount or more of a specific liquid crystal compound represented by the following formulas (2) to (4) in the chiral nematic liquid crystal component.
  • the light control device performance can be maintained even after the light resistance test.
  • the liquid crystal light control layer, the alignment film, the sealing material, and the like may be deteriorated to generate ionic impurities. It is considered that when this impurity stays in the liquid crystal light control layer, an abnormality of the internal electric field occurs and the performance of the light control element deteriorates. That is, by using the liquid crystal compounds represented by the following formulas (2) to (4), the amount of ionic impurities generated by light absorption is reduced, and the uptake of the generated ionic impurities is reduced. The internal electric field abnormality in the liquid crystal light control layer can be suppressed.
  • Such a liquid crystal compound having a high light resistance generally has a small refractive index anisotropy ( ⁇ n), and thus exhibits a trade-off in which a high haze cannot be produced at the time of light shielding, but is represented by the formulas (2) to (4).
  • ⁇ n refractive index anisotropy
  • the liquid crystal element of the present invention is a liquid crystal light control layer comprising at least one transparent substrate, a pair of substrates with electrodes arranged opposite to each other, and a composite containing a chiral nematic liquid crystal phase and a polymer resin phase between the substrates Is sandwiched between them.
  • the polymer resin phase contains a structure represented by the following formula (1) in the polymer, the dielectric anisotropy of the chiral nematic liquid crystal phase is positive, and the chiral nematic liquid crystal phase has the formula (
  • the liquid crystal compounds represented by 2) to (4) are not particularly limited as long as they contain a predetermined value or more, but typical configurations will be described below.
  • the material for the substrate examples include colorless and transparent, colored and transparent materials such as inorganic transparent materials such as glass and quartz, metals, metal oxides, semiconductors, ceramics, plastic plates, and plastic films.
  • the electrode is formed on the substrate by, for example, a thin film of a metal oxide, metal, semiconductor, organic conductive material or the like on the entire surface or part of the substrate by a known coating method, a printing method, a vapor deposition method such as sputtering, or the like. The Alternatively, it may be partially etched after forming a conductive thin film.
  • an ITO (mixture of indium oxide and tin oxide) electrode on a transparent polymer film such as PET is deposited by sputtering or printing. It is desirable to use an electrode substrate formed using Note that wiring for connecting the electrodes or connecting the electrodes and the outside may be provided on the substrate.
  • a segment driving electrode substrate, a matrix driving electrode substrate, an active matrix driving electrode substrate, or the like may be used.
  • the electrode surface provided on the substrate is a protective film or alignment film made of an organic compound such as polyimide, polyamide, silicon, and cyanide, an inorganic compound such as SiO 2 , TiO 2 , and ZrO 2 , or a mixture thereof.
  • the substrate may be aligned so that the liquid crystal is aligned with respect to the substrate surface.
  • any alignment treatment can be used as long as the liquid crystal composition in contact has a planar structure. It doesn't matter.
  • the two substrates may be homogeneously aligned, or may be a so-called hybrid in which one is homogeneously aligned and the other is homeotropic aligned.
  • the electrode surface may be directly rubbed, or a normal alignment film such as polyimide used for TN liquid crystal, STN liquid crystal or the like may be used.
  • a so-called photo-alignment method can be used in which the organic thin film on the substrate is irradiated with light having anisotropy such as linearly polarized light to give the film anisotropy.
  • the alignment treatment of the substrate is not necessarily required if the alignment of the unpolymerized liquid crystal composition can be controlled with respect to the substrate surface. That is, before the liquid crystal composition of the present invention to be described later is photopolymerized, the liquid crystal composition can be aligned to take a planar structure by a method such as flowing the liquid crystal composition or applying a shear stress. it can.
  • the opposing substrate may have an adhesive layer including a resin body that adheres and supports the substrate as appropriate at the peripheral portion.
  • the end face of the liquid crystal element or the injection port of the liquid crystal composition in the present invention is a tape such as an adhesive tape, a thermocompression bonding tape, a thermosetting tape, and / or a thermosetting resin, a photocurable resin, a moisture curable resin Curable resins such as room temperature curable adhesives, anaerobic adhesives, epoxy adhesives, silicone adhesives, fluororesin adhesives, polyester adhesives, vinyl chloride adhesives, and thermoplastic resins
  • a tape such as an adhesive tape, a thermocompression bonding tape, a thermosetting tape, and / or a thermosetting resin
  • a photocurable resin such as room temperature curable adhesives, anaerobic adhesives, epoxy adhesives, silicone adhesives, fluororesin adhesives, polyester adhesives, vinyl chloride adhesives, and thermoplastic resins
  • this sealing may provide an effect of preventing deterioration of the liquid crystal element.
  • the end face may be entirely covered, or a curable resin or thermoplastic resin may be poured from the end face into the liquid crystal element to be solidified. It may be covered.
  • a spacer such as spherical or cylindrical glass, plastic, ceramic, or plastic film may be present between the substrates arranged opposite to each other.
  • the spacer may be present as a component of the liquid crystal composition of the present invention so that it may be present in the liquid crystal light control layer between the substrates.
  • the spacer is dispersed on the substrate during the assembly of the liquid crystal element or mixed with an adhesive. Or may be present in the adhesive layer.
  • liquid crystal light control layer included in the liquid crystal element of the present invention preferably includes a composite including a chiral nematic liquid crystal phase and a polymer resin phase.
  • a polymer-stabilized liquid crystal in which a polymer network derived from the polymerizable monomer is formed in a continuous liquid crystal phase
  • a polymer-dispersed liquid crystal the liquid crystal phase is a polymer resin
  • the liquid crystal light control layer of the present invention can switch between a light transmission state and a light scattering state by a DC voltage, an AC voltage, a pulse voltage, or a combination thereof having an effective value equal to or greater than a threshold value.
  • the liquid crystal light control layer may be driven in a reverse mode in which a light transmission state is applied when no voltage is applied and a light scattering state is applied when a voltage is applied, or a light transmission state is applied when a voltage is applied. It may be driven in the normal mode. Alternatively, a memory mode drive in which voltage is applied only when switching between the light transmission state and the light scattering state may be used.
  • the liquid crystal composition of the present invention can be applied to any liquid crystal element in the reverse mode, normal mode, and memory mode.
  • a method for manufacturing a reverse mode liquid crystal device for example, a method using PSLC is disclosed in Japanese National Publication No. 06-507505.
  • a method of manufacturing a normal mode liquid crystal element is disclosed in, for example, a method using PSLC in Japanese National Patent Publication No. 06-507505, Japanese Unexamined Patent Publication No. 07-043690, Japanese Unexamined Patent Publication No. 2007-57671, etc.
  • a method using PDLC is disclosed.
  • a method for producing a memory mode liquid crystal element using the liquid crystal composition of the present invention for example, a method using PSLC is disclosed in Japanese Patent Publication No. 7-507083.
  • the liquid crystal spiral axis When used in the reverse mode as the liquid crystal light control layer, when no voltage is applied to the liquid crystal element, the liquid crystal spiral axis becomes a planar phase in which almost all the liquid crystal spiral axes are perpendicular to the substrate, and a light transmission state is obtained.
  • the liquid crystal helical axis with positive dielectric anisotropy undergoes a phase transition to a focal conic phase facing a random direction, and the light scattering state become. By switching between these two phases, the haze of the liquid crystal element can be controlled.
  • the liquid crystal spiral axis of the liquid crystal phase dispersed in the polymer resin phase is random due to strong binding by the polymer resin phase. It becomes a focal conic phase facing the direction, and becomes a light scattering state.
  • the major axis of the liquid crystal molecules having a positive dielectric anisotropy becomes a homeotropic phase in a direction perpendicular to the substrate, and the light transmission state Become.
  • the liquid crystal light control layer of the present invention includes a chiral nematic liquid crystal phase containing a specific liquid crystal compound and a polymer resin phase having a specific molecular structure
  • the element system such as PSLC and PDLC.
  • the liquid crystal light control layer of the present invention is more preferably PSLC or PDLC.
  • PSLC is characterized in that the polymer resin phase has a network-like polymer network structure, and the ratio of the polymer resin phase to the total of the liquid crystal phase and the polymer resin phase is 10% by weight or less.
  • the liquid crystal phase is continuously connected in the optical layer.
  • PSLC has the advantage that the elastic interaction at the interface between the liquid crystal phase and the polymer resin phase is large, and the response speed of falling of the liquid crystal element is faster than other systems. In addition, transparency when no voltage is applied to the liquid crystal element and scattering intensity when a voltage is applied can be sufficiently increased.
  • the characteristic of PDLC is that the liquid crystal phase is dispersed in droplets in the polymer resin phase, and the ratio of the polymer resin phase to the total of the liquid crystal phase and the polymer resin phase is about 5% by weight or more. . Since PDLC has a role as a binder in the polymer resin phase, PDLC has advantages such as excellent element strength such as adhesion and impact resistance and flexibility.
  • the ratio of the chiral nematic liquid crystal phase and the polymer resin phase in the liquid crystal light control layer of the present invention is not particularly limited as long as the effects of the present invention are not impaired.
  • the polymer resin phase is preferably 10% by weight or less, and more preferably 7% by weight or less, based on the total of the chiral nematic liquid crystal phase and the polymer resin phase. Moreover, it is preferable that it is 0.1 weight% or more, and it is still more preferable that it is 1 weight% or more.
  • the ratio of the polymer resin phase to the total of the chiral nematic liquid crystal phase and the polymer resin phase is 0.1% by weight or more, the polymer resin phase becomes mechanically tough and tends to be excellent in repeated durability of the liquid crystal element.
  • liquid crystal molecules can receive sufficient interface interaction, the contrast and response speed of transmission scattering of the liquid crystal element may be improved.
  • the ratio of the polymer resin phase to the total of the chiral nematic liquid crystal phase and the polymer resin phase is 10% by weight or less, an increase in driving voltage is suppressed, and the transparency of the liquid crystal element tends to increase. .
  • the liquid crystal light control layer of the present invention may contain other components in addition to the chiral nematic liquid crystal phase and the polymer resin phase.
  • a pigment may be included. Specifically, it can be used in a state where a dichroic dye is added and dissolved in the liquid crystal.
  • the intrinsic absorption wavelength based on the molecular orientation of the dye that is, the absorption, transmission, and scattering characteristics of light of a specific wavelength according to the dichroic ratio are electrically It can be used as a dimming / optical element member that can be controlled to a high degree.
  • a pigment it is possible to strongly absorb only a component of a specific wavelength or to enhance scattering, and it is possible to complement wavelength anisotropy. This makes it possible to design a desired color rendering effect according to the application destination of the element.
  • polymer resin phase of the present invention contains a structure represented by the following formula (1).
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent
  • X 1 and X 4 each independently represent a divalent group which may have a substituent
  • X 2 and X 3 each independently represent a divalent group which may have a direct bond or a substituent
  • a 1 to A 3 each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent.
  • An aliphatic hydrocarbon ring group or a divalent condensed ring group which may be any one of an aromatic hydrocarbon ring, an aromatic heterocycle and an aliphatic hydrocarbon ring;
  • at least one of A 1 to A 3 is an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent.
  • Including at least one of m 1 and m 4 each independently represent an integer of 0 or more and 6 or less, and m 2 and m 3 each independently represent an integer of 0 or more and 4 or less.
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • the alkyl group having 1 to 6 carbon atoms may be linear or branched.
  • R 1 and R 2 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. preferable.
  • the substituent that the alkyl group having 1 to 6 carbon atoms may have is not particularly limited, and examples thereof include a halogen atom and a cyano group from the viewpoint of solubility in liquid crystals.
  • X 1 and X 4 each independently represent a divalent group that may have a substituent, and X 2 and X 3 each independently have a direct bond or a substituent.
  • the divalent group of X 2 and X 3 is not particularly limited, and examples thereof include an ether bond, an ester bond, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic heterocyclic group, and the like. Among these, from the viewpoint of high solubility in the liquid crystal, an aliphatic hydrocarbon group such as a linear, branched or cyclic alkylene group or an ether bond is preferable.
  • the divalent group of X 1 and X 4 is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an aromatic heterocyclic group. Among these, from the viewpoint of high solubility in liquid crystals, an aliphatic hydrocarbon group, particularly a linear, branched or cyclic alkylene group is preferable.
  • the combination of X 1 , X 2 , X 3 and X 4 is not particularly limited, and may be the same, partially or completely different, but is preferably the same from the viewpoint of ease of production.
  • Examples of the substituent that X 1 , X 2 , X 3, and X 4 may have include an alkyl group, an alkoxy group, a hydroxy group, and a carboxyl group. Among these, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms are preferable from the viewpoint of solubility in liquid crystals.
  • Examples of the aliphatic hydrocarbon group for X 1 , X 2 , X 3 and X 4 include a linear, branched or cyclic divalent aliphatic hydrocarbon group.
  • a linear, branched or cyclic divalent aliphatic hydrocarbon group For example, methylene, ethylene, propylene, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, 1,2-cyclopentanediyl, 1,3-cyclopentanediyl, 1,4-cyclo Pentanediyl group, 1,1-cyclohexanediyl group, 1,2-cyclohexanediyl group, 1,3-cyclohexanediyl group, 1,4-cyclohexanediyl group, 1,1-cycloheptanediyl group, 1,2-cyclohexane Heptanediyl group, 1,3-cycloheptanedi
  • the divalent aliphatic hydrocarbon group preferably has 4 or more carbon atoms, more preferably 5 or more. Moreover, 8 or less is preferable and 7 or less is still more preferable. When the carbon number is within this range, the orientation with the liquid crystal tends not to be hindered.
  • the aromatic hydrocarbon groups for X 1 , X 2 , X 3 and X 4 are not particularly limited as long as the effects of the present invention are not impaired.
  • the divalent aromatic hydrocarbon group is a divalent group obtained by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon ring or a condensed ring formed by condensing 2 to 4 aromatic hydrocarbon rings.
  • the carbon number of the divalent aromatic hydrocarbon group is preferably 6 or more, while the carbon number is preferably 30 or less, more preferably 26 or less, and even more preferably 18 or less. When the carbon number is within this range, the reactivity during polymerization tends to be improved.
  • divalent aromatic hydrocarbon group examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, And groups obtained by removing two hydrogen atoms from a fluorene ring or the like.
  • a group obtained by removing two hydrogen atoms from a benzene ring or naphthalene ring that is, a phenylene group or a naphthalene group is preferable from the viewpoint of improving solubility in liquid crystals.
  • the aromatic heterocyclic group for X 1 , X 2 , X 3 and X 4 is not particularly limited as long as the effects of the present invention are not impaired.
  • the divalent aromatic heterocyclic group is a divalent group obtained by removing two hydrogen atoms from a monocyclic aromatic heterocyclic ring or a condensed ring formed by condensing 2 to 4 aromatic heterocyclic rings.
  • the number of atoms (membership) constituting the aromatic heterocyclic ring of the divalent aromatic heterocyclic group is preferably 5 or more.
  • the number of atoms constituting the aromatic heterocycle is preferably 30 or less, more preferably 26 or less, and particularly preferably 18 or less. When the number of atoms constituting the aromatic heterocycle is within this range, the reactivity during polymerization tends to be improved.
  • divalent aromatic heterocyclic group examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring.
  • a group obtained by removing two hydrogen atoms from a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, or an oxadiazole ring is preferable from the viewpoint of solubility in liquid crystals.
  • a 1 to A 3 each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. And may represent an aliphatic hydrocarbon ring group (cyclic aliphatic hydrocarbon group) or a divalent condensed ring group.
  • the divalent fused ring group is composed of one or more of an aromatic hydrocarbon ring, an aromatic heterocycle and an aliphatic hydrocarbon ring.
  • Examples of the divalent aromatic hydrocarbon group which may have a substituent of A 1 to A 3 and the divalent aromatic heterocyclic group which may have a substituent include X 1 , X 2 , those exemplified in the description of X 3 and X 4 can be mentioned, is the same preferable groups.
  • the divalent aliphatic hydrocarbon ring group of A 1 to A 3 is not particularly limited as long as the effects of the present invention are not impaired.
  • carbon number of a bivalent aliphatic hydrocarbon ring group 5 or more are still more preferable.
  • 8 or less is preferable and 7 or less is still more preferable. It is preferable for the carbon number to be in this range because it is difficult for the alignment with the liquid crystal to be inhibited.
  • a divalent fused ring group composed of any one or more of A 1 to A 3 aromatic hydrocarbon rings, aromatic heterocycles and aliphatic hydrocarbon rings (hereinafter simply referred to as “fused ring group”).
  • fused ring group composed of any one or more of A 1 to A 3 aromatic hydrocarbon rings, aromatic heterocycles and aliphatic hydrocarbon rings
  • the combination of the rings constituting the condensed ring is not particularly limited, but preferably an aliphatic hydrocarbon ring. It is formed by condensing 2 to 4 rings containing one or more, and specific examples thereof include those exemplified as a divalent condensed ring group containing an aliphatic hydrocarbon ring described later.
  • Examples of the substituent that the aromatic hydrocarbon group, aromatic heterocyclic group, aliphatic hydrocarbon ring group, and condensed ring group of A 1 to A 3 may have include an alkyl group, an alkoxy group, a hydroxy group, and a carboxyl group. Groups and the like. Among these, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is preferable from the viewpoint of solubility in liquid crystals.
  • At least an aliphatic hydrocarbon ring is included in the structural portion represented by the following (hereinafter sometimes referred to as “specific position A”), and by including an aliphatic hydrocarbon ring at the specific position A, the ultraviolet or visible light absorption of the polymerizable compound is suppressed, the generation of decomposition products is reduced, and the electrical reliability of the liquid crystal element is improved.
  • a mixture in which a plurality of liquid crystalline substances are mixed absorbs ultraviolet light to cause some molecules to undergo a photoreaction and generate ionic impurities.
  • the polymerizable compound not all molecules contribute to the polymerization reaction when absorbing ultraviolet light, and some molecules generate ionic impurities as a side reaction. Therefore, an exposure process in which a liquid crystal composition containing a liquid crystal and a polymerizable compound is sandwiched between two electrode substrates and the polymerizable compound is polymerized by exposure to ultraviolet light generates the ionic impurities, and the liquid crystal element has an electrical property. It causes a decrease in reliability.
  • the specific position A which is a position where the ⁇ electron conjugation is reduced or divided, is aliphatic. Presumed to be due to the inclusion of the hydrocarbon ring, which efficiently traps the active radicals generated by the mixture of liquid crystals and polymerizable compounds by absorbing ultraviolet light and efficiently converts them into a polymerization reaction. Is done.
  • the ionic impurities in the liquid crystal phase are deposited at the interface between the liquid crystal phase and the polymer resin phase and / or the alignment film due to repeated power ON / OFF switching for the liquid crystal element and continuous driving for a long time. This is one of the causes of the “burn-in” phenomenon.
  • the haze at the time of transparency increases and the transparency deteriorates.
  • the ionic impurities generated in the liquid crystal phase can be reduced, so that the burn-in can be suppressed and the transparency at the time of light shielding is increased.
  • the liquid crystal element can be made excellent in colorless transparency. Furthermore, since the ionic impurities in the liquid crystal phase can be reduced, it is advantageous for electric driving of the liquid crystal element, and it is highly effective when the liquid crystal element is turned on in the reverse mode or when the liquid crystal element is turned off in the normal mode. It also has excellent scattering properties and fast response.
  • the specific position A includes an aliphatic hydrocarbon ring as long as at least one aliphatic hydrocarbon ring is included in the specific position A.
  • at least one of A 1 to A 3 may be an aliphatic hydrocarbon ring group, or may be in a form in which an aliphatic hydrocarbon ring group and another group are connected by a direct bond.
  • the condensed ring group may contain an aliphatic hydrocarbon ring.
  • the specific position A is the above-mentioned “divalent aliphatic hydrocarbon ring group”, the following “divalent aliphatic hydrocarbon” Examples thereof include a “linking group between a cyclic group and another cyclic group” or “a divalent condensed cyclic group containing an aliphatic hydrocarbon ring”.
  • a divalent linking group of an aliphatic hydrocarbon ring group and another cyclic group (A divalent linking group of an aliphatic hydrocarbon ring group and another cyclic group)
  • the group in which the aliphatic hydrocarbon ring group and another cyclic group are linked by a direct bond is not particularly limited as long as it does not impair the effects of the present invention, but includes the following groups.
  • the divalent condensed ring group in which the aliphatic hydrocarbon ring group is condensed with another ring is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include the following groups.
  • the number of carbons at the specific position A is preferably 6 or more, and more preferably 12 or more. Moreover, 50 or less is preferable and 30 or less is still more preferable. When the carbon number is within this range, the reactivity during polymerization during the formation of the liquid crystal element is improved, and the electrical reliability of the liquid crystal element tends to be improved.
  • (M 1 and m 4 ) m 1 and m 4 each independently represent an integer of 0 or more and 6 or less.
  • 0, 1 or 2 is preferable from the viewpoint of improving the solubility in the liquid crystal, and in particular, m 1 and m 4 are preferably 0 because the reactivity during polymerization tends to be improved.
  • m 2 and m 3 each independently represents an integer of 0 or more and 4 or less.
  • m 2 and m 3 are preferably 0, 1 or 2 from the viewpoint of improving the solubility in liquid crystal.
  • R 1 , R 2 , X 1 , X 2 , X 3 , X 4 , A 1 , A 2 , A 3 , m 1 , m 2 , m 3 and m 4 is not particularly limited, but X 2 and A
  • X 2 is a direct bond, an ether bond, an ester bond, a straight chain or branched alkylene group having 2 to 6 carbon atoms
  • a 2 has the following structure: It is preferable in terms of both high solubility in water and light control element performance. The same applies to the combination of X 3 and A 3 .
  • the polymer resin phase of the present invention includes a polymer resin obtained by polymerizing a polymerizable monomer to be described later, as long as the effect of the present invention is not impaired other than the structure represented by the formula (1).
  • Other components and structures may be included.
  • the polymer resin phase of the present invention includes a structure other than the structure represented by the formula (1), the structure represented by the formula (1) included in the polymer resin phase of the present invention and other structures
  • the ratio is not particularly limited as long as the effect of the present invention is not impaired, but the structure represented by the formula (1) is preferably 30% by weight or more, more preferably 50% by weight or more, and most preferably. 80% by weight or more.
  • the ratio of the structure represented by the formula (1) in the polymer resin phase of the present invention is in an appropriate range, liquid crystal element production in a short time, high contrast, short response time, etc. tend to be sufficiently obtained. It is in.
  • the upper limit of the content of the structure represented by the formula (1) in the polymer resin phase of the present invention is 100% by weight.
  • Specific examples of the structure other than the structure represented by the formula (1) that may be contained in the polymer resin phase of the present invention include, for example, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, butyl ethyl Acrylate, butoxyethyl acrylate, 2-cyanoethyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-hydroxypropyl acrylate, 2-ethoxyethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, dicyclopentanyl Acrylate, dicyclopentenyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, isoamyl acrylate, isobornyl acrylate, isodecyl acrylate, laur Acrylate, morpholine acrylate,
  • Polyfunctional acrylate compounds diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, dicyclopentanyl dimethacrylate, glycerol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl Recall dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate, urethane methacrylate oligomer, 2,2,3,3,4,4-hexafluoro-1,5-pentadiol dimeth
  • the polymer resin of the polymer resin phase of the present invention is a copolymer
  • any of an alternating copolymer, a block copolymer, a random copolymer, and a graft copolymer may be used.
  • the chiral nematic liquid crystal phase (hereinafter sometimes referred to as “the chiral nematic liquid crystal phase of the present invention” or “the liquid crystal phase of the present invention”) contained in the liquid crystal light control layer of the liquid crystal element of the present invention is anisotropic in dielectric constant. And at least one compound represented by the following formula (2), (3), or (4) is 15% by weight or more in total with respect to the total amount of the chiral nematic liquid crystal component To do.
  • S 1 to S 4 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted alkyl group having 1 to 10 carbon atoms.
  • B 1 to B 5 each independently represents any of the following groups (5a) to (5h) which may have a substituent:
  • C 1 to C 3 each independently represents a direct bond or any of the following groups (6a) to (6d):
  • n 1 to n 3 each independently represents 0 or 1.
  • the chiral nematic liquid crystal used in the liquid crystal phase of the present invention and the liquid crystal composition described below has a positive dielectric anisotropy. Since the dielectric anisotropy of the chiral nematic liquid crystal phase of the present invention is positive, the liquid crystal element of the present invention can be used as a reverse-mode, normal-mode, and memory-mode transmission-scattering type device.
  • the value of the dielectric anisotropy ( ⁇ ) of the chiral nematic liquid crystal is not particularly limited as long as it is positive, but is preferably 5 or more, and more preferably 8 or more for reducing the driving voltage of the liquid crystal element.
  • a polymerization initiator described later it is polymerizable that each molecule constituting the chiral nematic liquid crystal does not have absorption at a wavelength overlapping the absorption wavelength of the polymerization initiator. This is preferable from the viewpoint of shortening the polymerization time of the monomer.
  • the liquid crystal itself may be an aggregate of liquid crystalline compounds exhibiting a cholesteric phase, or a chiral nematic liquid crystal may be obtained by adding a chiral agent to the nematic liquid crystal. From the viewpoint of designing the liquid crystal composition, it is preferable to add a chiral agent to the nematic liquid crystal according to the purpose and control the chiral pitch length (p) and the liquid crystal-isotropic phase transition temperature (T ni ).
  • the relationship d / p between the chiral pitch length (p) of the chiral nematic liquid crystal and the distance (d) between the pair of substrates with electrodes arranged opposite to each other is 1 or more. It is preferable. More preferably, it is 2 or more, and particularly preferably 4 or more. Moreover, it is preferable that it is 20 or less, and it is especially preferable that it is 12 or less.
  • the driving voltage is within the above range from the viewpoint of achieving both light shielding characteristics and energy saving and safety.
  • the p of the chiral nematic liquid crystal is preferably 0.3 ⁇ m or more, and more preferably 0.8 ⁇ m or more. On the other hand, it is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less.
  • p is not less than the above lower limit value, the driving voltage of the liquid crystal element tends to be kept low, and when it is not more than the above upper limit value, the contrast tends to be high.
  • the concentration of the chiral agent may be determined by calculating backward from the required value of p.
  • p ⁇ n n is the refractive index of chiral nematic liquid crystal
  • the finally obtained liquid crystal element is colored when no voltage is applied, and is out of the visible light range.
  • p since it becomes colorless and transparent when no voltage is applied, p may be selected according to the purpose.
  • the distance (d) between the pair of substrates with electrodes disposed opposite to each other in the liquid crystal element of the present invention needs to be not less than p of the chiral nematic liquid crystal to be used, preferably 2 ⁇ m or more, and more preferably 3 ⁇ m or more. It is preferably 5 ⁇ m or more. Moreover, 100 micrometers or less are preferable and 20 micrometers or less are still more preferable.
  • the light transmittance of the liquid crystal element decreases with increasing d, and the response time of the display element may become longer.
  • d is too small, the light shielding characteristics during driving are reduced, and in the case of a large-area liquid crystal element, the liquid crystal element may be short-circuited.
  • the liquid crystal-isotropic phase transition temperature (T ni ) of the chiral nematic liquid crystal is preferably 50 ° C. or higher, and more preferably 70 ° C. or higher, since the upper temperature limit at which the liquid crystal element can operate is determined by T ni of the chiral nematic liquid crystal. 80 ° C. or higher is particularly preferable. On the other hand, since viscosity tends to increase as T ni increases, it is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
  • the dielectric anisotropy value ( ⁇ ), the liquid crystal-isotropic phase transition temperature (T ni ), and the chiral pitch length (p) of the chiral nematic liquid crystal are measured according to the methods described in Examples below. . ⁇ can also be calculated by an additive rule from the dielectric anisotropy of each constituent molecule contained in the liquid crystal composition or the liquid crystal phase.
  • the refractive index anisotropy ( ⁇ n) of the chiral nematic liquid crystal is preferably 0.10 or more, and more preferably 0.15 or more, from the viewpoint of enhancing scattering during light shielding.
  • ⁇ n of the chiral nematic liquid crystal is preferably 0.35 or less, and more preferably 0.30 or less. Within the above range, the chiral nematic liquid crystal tends to be chemically stable and light resistance is improved.
  • This refractive index anisotropy ( ⁇ n) can be measured by a critical angle method, a minimum deviation method, a V block method, or the like.
  • S 1 is a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted alkyl group having 1 to 10 carbon atoms.
  • examples of the substituent that S 1 may have include an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an amino group, a carboxy group, A cyano group etc. are mentioned.
  • it is an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxyl group having 1 or more and 4 or less carbon atoms, or a fluorine atom, but each of ⁇ n, ⁇ , and T ni is set to a high value, and further the solubility of the polymerizable monomer from the viewpoint of a favorable, S 1 is more preferably no substituent.
  • Y 1 to Y 3 are each independently any one of a hydrogen atom, a fluorine atom and a cyano group. Any one of Y 1 to Y 3 is a fluorine atom. Further, among the Y 1 ⁇ Y 3, that the number of hydrogen atoms is 0 or 1, and large values of ⁇ n and [Delta] [epsilon], more preferred from the viewpoint of light resistance and good. In particular, the number of cyano groups is preferably 0 or 1 from the viewpoint of increasing the value of ⁇ n, increasing the value of ⁇ , and obtaining good light resistance.
  • S 2 is a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted alkyl group having 1 to 10 carbon atoms.
  • An alkoxyl group; S 2 is particularly preferably an alkyl group having 2 or more and 8 or less carbon atoms, or an alkoxyl group having 2 or more and 8 or less carbon atoms, and particularly a linear alkyl group having 2 or more and 6 or less carbon atoms. preferable.
  • each of ⁇ n, ⁇ , and T ni tends to have a high value, and the solubility of the polymerizable monomer tends to be good.
  • examples of the substituent that S 2 may have include an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an amino group, a carboxy group, A cyano group etc. are mentioned.
  • 1 or more carbon atoms, alkyl group of 4 or less, having 1 or more carbon atoms is a 4 or less alkoxyl group or a fluorine atom, [Delta] n, a high value of each of ⁇ and T ni, further solubility of the polymerizable monomers From the viewpoint of improving the quality of S 2, it is more preferable that S 2 has no substituent.
  • Y 4 to Y 6 are each independently any one of a hydrogen atom, a fluorine atom and a cyano group, and any one of Y 4 to Y 6 is a fluorine atom. is there. Further, among the Y 4 ⁇ Y 6, that the number of hydrogen atoms is 0 or 1, and large values of ⁇ n and [Delta] [epsilon], more preferred from the viewpoint of light resistance and good. In particular, the number of cyano groups is preferably 0 or 1 from the viewpoint of increasing the values of ⁇ n and ⁇ and further improving light resistance.
  • B 1 is any one of (5a), (5b), (5g), and (5h) among the groups (5a) to (5h).
  • any of (5b), (5g) and (5h) is preferable from the viewpoint of the liquid crystal temperature range.
  • the substituent that B 1 may have include an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an amino group, a carboxy group, and a cyano group.
  • Etc Preferably, it is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a fluorine atom. From the viewpoint of making ⁇ n and ⁇ high and improving light resistance, B 1 Is more preferable not to have a substituent.
  • B 2 is any one of the groups (5a) to (5h) described above (5a), (5b), (5c), (5d), (5e), and (5f). Is preferable from the viewpoint of making each of ⁇ n, ⁇ , and T ni high and further improving light resistance, and is particularly any one of (5c), (5d), (5e), and (5f). Is preferred.
  • B 3 is preferably (5a) or (5b) among any of the groups (5a) to (5h), and particularly (5a) is represented by ⁇ n, ⁇ and T ni .
  • Each is preferable from the viewpoint of setting a high value and obtaining good light resistance.
  • the substituent that B 3 may have include an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an amino group, a carboxy group, and a cyano group.
  • it is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a fluorine atom.
  • ⁇ n and ⁇ are set to high values, and from the viewpoint of high light resistance.
  • B 3 preferably has no substituent.
  • n 1 is 0 or 1, but preferably n 1 is 0.
  • C 1 to C 3 each independently represents a direct bond or any one of the groups (6a) to (6d). From the viewpoint of improving light resistance, the above (6c) is preferable. ) Or (6d).
  • S 3 and S 4 may each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent.
  • S 3 is particularly preferably an alkyl group having 2 to 8 carbon atoms, an alkoxyl group having 2 to 8 carbon atoms, and more preferably a linear alkyl group having 2 to 6 carbon atoms. .
  • each of ⁇ n, ⁇ and T ni has a large value, and the solubility of the polymerizable monomer tends to be improved.
  • substituent which may be possessed by S 3 1 or more carbon atoms, alkyl group of 4 or less, 1 or more carbon atoms, 4 or less alkoxyl group, halogen atom, hydroxy group, amino group, carboxy group, A cyano group etc. are mentioned.
  • it is an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxyl group having 1 or more and 4 or less carbon atoms, or a fluorine atom, but each of ⁇ n, ⁇ , and T ni is set to a high value, and further the solubility of the polymerizable monomer
  • S 3 does not have a substituent.
  • S 4 is particularly preferably an alkyl group having 2 or more and 8 or less carbon atoms or an alkoxy group having 2 or more and 8 or less carbon atoms, and a linear alkyl group having 2 or more and 6 or less carbon atoms or 2 or more, 6 or less carbon atoms.
  • the following alkoxy groups are more preferable. These groups are preferable from the viewpoint of increasing the values of ⁇ n, ⁇ , and T ni and, further, the solubility of the polymerizable monomer.
  • examples of the substituent that S 4 may have include an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an amino group, a carboxy group, A cyano group etc. are mentioned.
  • it is an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxyl group having 1 or more and 4 or less carbon atoms, or a fluorine atom, but each of ⁇ n, ⁇ , and T ni is set to a high value, and further the solubility of the polymerizable monomer
  • S 4 does not have a substituent.
  • B 4 is preferably (5a) or (5b) among the groups (5a) to (5h), and particularly preferably (5b) is the liquid crystal temperature. It is preferable from the viewpoint of the range.
  • the substituent that B 4 may have include an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an amino group, a carboxy group, and a cyano group.
  • it is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a fluorine atom, but B 4 is substituted from the viewpoint of high ⁇ n, high ⁇ , and high light resistance. It is preferable to have no group.
  • B 5 is preferably (5a) or (5b) among the groups (5a) to (5h), and particularly preferably (5b) from the viewpoint of the liquid crystal temperature range.
  • substituents that B 5 may have include an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an amino group, a carboxy group, and a cyano group.
  • Etc Preferably, it is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a fluorine atom. From the viewpoint of making ⁇ n and ⁇ high and improving light resistance, It is more preferable that B 5 does not have a substituent.
  • n 2 and n 3 are 0 or 1, but preferably n 2 and n 3 are 0.
  • the liquid crystal phase of the present invention may contain only one of the compounds represented by the above formulas (2), (3) and (4) or may contain two or more. Also good. When it contains two or more compounds, it may contain one or more compounds represented by formula (2) and one or more compounds represented by formula (3). It may well contain one or more of the compounds represented by formula (2) and one or more of the compounds represented by formula (4). 1 type or 2 types or more of a compound and 1 type or 2 or more types of a compound represented by Formula (4) may be included, and 1 type or 2 of a compound represented by Formula (2) One or more of the compounds represented by Formula (3) and one or more of the compounds represented by Formula (4) and one or more of the compounds represented by Formula (4) may be included. From the viewpoint of increasing ⁇ n and improving light resistance, one or more compounds represented by formula (2), one or more compounds represented by formula (3), and formula (4) It is preferable that 1 or more types of the compound represented by these are included.
  • the liquid crystal phase of the present invention may contain a liquid crystal component other than the compounds represented by the above formulas (2) to (4).
  • the nematic liquid crystal as the other liquid crystal component may be any known one, and there is no particular limitation on the molecular skeleton, substituent, and molecular weight of the constituent molecules, and it may be a synthetic product or a commercial product. It is preferable that the dielectric anisotropy of the nematic liquid crystal is positive and large in order to make the dielectric anisotropy of the chiral nematic liquid crystal phase of the liquid crystal element and the chiral nematic liquid crystal of the liquid crystal composition positive.
  • each molecule constituting the constituent molecule does not have absorption at a wavelength overlapping the absorption wavelength of the initiator.
  • various additives may be included as long as the optical and electrical characteristics of the dichroic dye and the liquid crystal element are not disturbed.
  • the liquid crystal compound refers to a compound that takes a liquid crystal state at 25 ° C. and 1 atm.
  • the liquid crystal state means a state in which the translational symmetry is lost in the aggregate of compounds but the alignment regularity is maintained. Generally, it means a state having fluidity and anisotropy.
  • the definition of liquid crystal is described in detail in “Liquid Crystal Handbook” Maruzen Co., Ltd. (2000), pages 1 to 7.
  • liquid crystal compounds may be used alone or in combination of any two or more at any ratio.
  • cholesteric liquid crystal and nematic liquid crystal those having low viscosity and high dielectric anisotropy are preferable in terms of high-speed response and manufacturability of the liquid crystal element.
  • the chiral agent may be any compound as long as it exhibits optical activity, may be a synthetic product or a commercial product, may itself exhibit liquid crystallinity, and further has a polymerizable functional group. May be. Further, dextrorotatory or levorotatory may be used, and a dextrorotatory chiral agent and a levorotatory chiral agent may be used in combination. However, the chiral agent used in the present invention excludes compounds corresponding to the formulas (2) to (4).
  • the chiral agent those having a large dielectric anisotropy per se and a low viscosity are preferable from the viewpoint of driving voltage reduction and response speed of the liquid crystal element, and the chiral agent is an index of the force for twisting the liquid crystal.
  • Examples of commercially available chiral agents include CB15 (trade name, manufactured by Merck), C15 (trade name, manufactured by Merck), S-811 (trade name, manufactured by Merck), R-811 (trade name, manufactured by Merck), S-1011 (trade name, manufactured by Merck), R-1011 (trade name, manufactured by Merck), and the like.
  • the liquid crystal phase of the present invention contains a total of the compounds represented by the above formula (2), (3) or (4), and contains 15% by weight or more based on the total amount of chiral nematic liquid crystal components.
  • the effect of this invention cannot be acquired as content of the compound represented by Formula (2), (3) or (4) is less than the said minimum.
  • the total ratio of the compounds represented by the formula (2), (3) or (4) to the total amount of the chiral nematic liquid crystal component is 18 wt. % Or more, more preferably 20% by weight or more, still more preferably 40% by weight or more, and particularly preferably 60% by weight or more.
  • the upper limit of the content ratio is usually 90% by weight or less in order to ensure the content of the chiral agent and the like.
  • the liquid crystal phase of the present invention comprises two or more compounds represented by the above formula (2), (3) or (4), particularly a compound represented by the formula (2), (3) or (4). It is preferable from the viewpoint of achieving both high ⁇ n and high light resistance.
  • the compound represented by the formula (2) is represented by 10 to 80% by weight and the formula (3) with respect to the total of the compounds represented by the formula (2), (3) or (4). From the viewpoint of the liquid crystal temperature range and the solubility of the polymerizable monomer, it is preferable to contain 10 to 80% by weight of the compound and 10 to 80% by weight of the compound represented by the formula (4).
  • the liquid crystal phase of the present invention contains a liquid crystal compound other than the compound represented by formula (2), (3) or (4), the value of ⁇ n is improved, the value of ⁇ is improved, the liquid crystal temperature range is increased. Effects such as expansion and improved solubility of the polymerizable monomer can be obtained. Since the effect of the present invention by using the compound represented by the formula (2), (3) or (4) tends to be sufficiently obtained, the content of the other liquid crystal compound is chiral nematic liquid crystal. It is preferable that it is 50 weight% or less with respect to the total amount of a component.
  • the chiral agent is preferably used in an amount of about 1 to 50% by weight based on the total amount of chiral nematic liquid crystal components.
  • the chiral nematic liquid crystal component is a liquid component contained in the liquid crystal light control layer of the liquid crystal element, and is usually a compound represented by the formula (2), (3) or (4) and necessary. This corresponds to the total of other liquid crystal compounds and chiral agents used accordingly.
  • the liquid crystal composition of the present invention is a chiral nematic liquid crystal composition having a positive dielectric anisotropy containing a polymerizable monomer and a chiral nematic liquid crystal component, and having a polymerizable property represented by the following formula (7): Containing at least one of the compounds represented by the formula (2), (3), or (4), including a monomer, in a total amount of 15% by weight or more based on the total amount of the chiral nematic liquid crystal component.
  • These compounds are preferably contained in a total amount of 18% by weight or more, more preferably 20% by weight or more, still more preferably 40% by weight or more, based on the total amount of liquid crystal components in the liquid crystal composition. It is particularly preferable to contain at least% by weight.
  • the polymerizable monomer represented by the following formula (7) is preferably contained in an amount of 0.5% by weight or more, more preferably 0.8% by weight or more, and more preferably 1% by weight or more based on the liquid crystal composition. Is more preferable, on the other hand, it is preferable to contain 10 wt% or less, and more preferably 8 wt% or less. It exists in the tendency for the performance and light resistance as a light control element to improve more because it is the said range.
  • R 3 ′ and R 4 ′ each independently represents an unsaturated acyl group
  • X 1 ′ and X 4 ′ each independently represent a divalent group which may have a substituent
  • X 2 ′ and X 3 ′ each independently represent a divalent group which may have a direct bond or a substituent
  • a 1 ′ to A 3 ′ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent.
  • a cyclic group, m 1 ′ and m 4 ′ each independently represent an integer of 0 or more and 6 or less, and m 2 ′ and m 3 ′ each independently represent an integer of 0 or more and 4 or less.
  • R 3 ′ and R 4 ′ each independently represents an unsaturated acyl group.
  • the type and number of unsaturated bonds that the unsaturated acyl group has are not particularly limited.
  • carbon number is not specifically limited, 3 or more are preferable, 10 or less are preferable and 5 or less are still more preferable. When the carbon number is within this range, the reactivity during polymerization tends to be improved.
  • the unsaturated acyl group for R 3 ′ and R 4 ′ include an acryloyl group, a propioyl group, a methacryloyl group, a crotonoyl group, and a cinnamoyl group.
  • an acryloyl group or a methacryloyl group is preferable from the viewpoint of improving the reactivity during polymerization.
  • X 1 ′ , X 2 ′ , X 3 ′ and X 4 ′ examples include those exemplified as X 1 , X 2 , X 3 and X 4 in the formula (1), and preferred examples are also the same. is there.
  • a 1 ′ to A 3 ′ examples include those exemplified as A 1 to A 3 in the formula (1), and preferred examples are also the same.
  • a composite of a liquid crystal phase and a polymer resin phase is designed to enhance the elastic interaction at the interface between the liquid crystal phase and the polymer resin phase in the liquid crystal light control layer by an intermolecular ⁇ - ⁇ interaction.
  • a polymerizable monomer having a molecular structure in which a ⁇ -electron system is distributed throughout the molecule was used.
  • such a polymerizable monomer may cause a problem that the polymerizable monomers are stacked by ⁇ - ⁇ interaction in the liquid crystal composition and the solubility in the liquid crystal is lowered.
  • the polymerizable property in which an aromatic hydrocarbon ring is introduced at a position where the area of ⁇ - ⁇ stacking between the polymerizable monomers is reduced is preferable to use a monomer because the solubility in liquid crystal can be improved.
  • a polymerizable monomer having an aromatic hydrocarbon ring introduced at a position to reduce the area of ⁇ - ⁇ stacking is used, it has an effect on high transparency when transparent, high scattering when shielding light, and high-speed response. Thus, a liquid crystal element excellent in these performances can be obtained.
  • the polymerizable monomer represented by the formula (7) is a group having a plurality of benzene rings such as a phenyl group or a naphthyl group, which a polymerizable monomer generally used as a liquid crystal composition has,
  • One benzene ring is a cycloalkyl group such as a cyclohexyl group.
  • the liquid crystal composition of the present invention may contain only one type of polymerizable monomer represented by the above formula (7) as the polymerizable monomer, or may contain two or more types. Moreover, other polymerizable monomers may be included together with the polymerizable monomer represented by Formula (7). Specifically, other polymerizable monomers having one or more ethylenically unsaturated double bonds, such as (meth) acrylic or vinyl, and one ethylenically unsaturated double bond It may be copolymerized with the polymerizable monomer represented by the above formula (7) by a polymerization reaction.
  • an aliphatic hydrocarbon ring is contained in the structural portion represented by
  • ⁇ Other polymerizable monomers examples include, for example, a monofunctional (meth) acrylic monomer, a bifunctional (meth) acrylic monomer, and a trifunctional monomer described in JP-A-9-90328.
  • Polymerizable monomers such as the above polyfunctional (meth) acrylic monomers, polymerizable oligomers such as (meth) acrylic oligomers, and the like can be used.
  • a vinyl monomer is mentioned as another polymerizable monomer which the liquid-crystal composition of this invention may contain.
  • the vinyl monomer examples include styrene, chlorostyrene, ⁇ -methylstyrene, divinylbenzene and the like.
  • the liquid crystal composition of the present invention may contain only one kind of these other polymerizable monomers, or may contain two or more kinds.
  • the polymer resin of the polymer resin phase of the present invention is a copolymer
  • any of an alternating copolymer, a block copolymer, a random copolymer, and a graft copolymer may be used.
  • the chiral nematic liquid crystal component contained in the liquid crystal composition of the present invention is synonymous with the chiral nematic liquid crystal component described in the description of the chiral nematic liquid crystal phase of the liquid crystal element of the present invention, and specific examples, preferred ranges, and the like are also synonymous.
  • the liquid crystal composition of the present invention preferably contains a polymerization initiator.
  • the polymerization initiator is not particularly limited, by selecting and adjusting the polymerization reactivity with the polymerizable monomer, chemical structure, molecular weight, initiator efficiency, etc., the peak area ratio of the polymer resin phase is set to a specific range, The effects of the present invention can be obtained.
  • Polymerization initiators include radical polymerization initiators that undergo intramolecular cleavage due to various physical factors such as light and heat, or generate hydrogen by extracting hydrogen from other molecules, but without applying heat.
  • a radical photopolymerization initiator that can be polymerized at a temperature equal to or lower than the phase transition temperature of the liquid crystal is preferable in that the thermal effect on the liquid crystal is small.
  • the radical photopolymerization initiator is not particularly limited in molecular structure, but it is preferable to select a compound that can be dissolved in the chiral nematic liquid crystal that is the host liquid crystal. Further, since the molecules constituting the liquid crystal composition of the present invention typically have ultraviolet light absorption of a wavelength of 350 nm or less, a radical photopolymerization initiator itself can be selected to be radicalized by light of a wavelength of 350 nm or more. preferable.
  • radical photopolymerization initiators examples include acylphosphine oxides, alkylphenones, titanocenes, polyhalogen compounds, alkyl boron salts of cyanine dyes, and triarylbiimidazoles. Among them, acylphosphine oxides, alkylphenones The radical photopolymerization initiator is preferably an acylphosphine oxide radical photopolymerization initiator from the viewpoint of polymerization efficiency.
  • acylphosphine oxide radical photopolymerization initiator examples include known monoacylphosphine oxide derivatives, bisacylphosphine oxide derivatives, trisacylphosphine oxide derivatives, and the like.
  • examples of commercially available products include monoacylphosphine derivatives such as Lucirin TPO (trade name, manufactured by BASF) and IRGACURE 819 (trade name, manufactured by BASF).
  • the content of the polymerizable monomer represented by the formula (7) in the liquid crystal composition of the present invention is preferably 0.5% by weight or more and 10% by weight or less. More preferably, it is 7 weight% or less, Especially preferably, it is 6.5 weight% or less. Further, it is more preferably 0.7% by weight or more, particularly preferably 1% by weight or more.
  • the content of the polymerizable monomer represented by the formula (7) is not less than the above lower limit, the haze at the time of light shielding is increased, the response time is shortened, and by being not more than the above upper limit, the haze at the time of transparency is low. At the same time, the drive voltage can be kept within the practical range.
  • the ratio of the polymerizable monomer represented by the formula (7) and the other polymerizable monomer impairs the effect of the present invention.
  • the amount of the polymerizable monomer represented by the formula (7) in the total polymerizable monomer is preferably 30% by weight or more, more preferably 50% by weight or more, and most preferably 80%. % By weight or more.
  • the ratio of the polymerizable monomer represented by the formula (7) is within an appropriate range, a liquid crystal device can be produced in a short time, and high-speed response, high transparency, high scattering, low coloration, high coloration can be achieved. There is a tendency to obtain a liquid crystal element excellent in durability and deterioration with time.
  • the upper limit of the polymerizable monomer represented by the formula (7) in all the polymerizable monomers is 100% by weight.
  • the total ratio of the polymerizable monomers to the liquid crystal composition is usually 0.7% by weight or more, preferably 1.2% by weight or more. % By weight or less, preferably 7% by weight or less.
  • this ratio is in an appropriate range, the durability against repeated use of the liquid crystal element tends not to decrease, and the haze at the time of transparency does not increase excessively, and the haze at the time of opaqueness does not tend to decrease.
  • the content ratio of the liquid crystal component in the liquid crystal composition is usually 90% by weight or more, preferably 91% by weight or more in the liquid crystal composition, and usually 99% by weight or less, preferably 98% by weight or less. is there. By being in this range, the balance of the transparency and optical response characteristics of the liquid crystal element tends to be obtained.
  • the content of the compound represented by the formula (2), (3) or (4) and the content of the chiral agent in the liquid crystal component are the same as the content in the liquid crystal phase of the present invention described above.
  • the content of the polymerization initiator in the liquid crystal composition is usually 0.01% by weight or more, preferably 0.05% by weight or more in the liquid crystal composition. On the other hand, it is usually 5% by weight or less, preferably 1% by weight or less. Within this range, the polymerization proceeds sufficiently, and the durability against repeated use of the liquid crystal element obtained from the liquid crystal composition and the haze at the time of transparency tend to be good.
  • the liquid crystal composition of the present invention may contain a light stabilizer, an antioxidant, a thickener, a polymerization inhibitor, a photosensitizer, an adhesive, an antifoaming agent, a surfactant and the like.
  • the method for producing the liquid crystal composition of the present invention is not particularly limited, but the liquid crystal composition can be produced by mixing the component compounds of the liquid crystal composition with a known stirrer or shaker. Heating may be performed during mixing. In the case of heating, the heating temperature is not particularly limited as long as the component compound does not cause a thermal reaction.
  • the liquid crystal composition of the present invention is designed to show cholesteric phase at room temperature (25 ° C.), the liquid crystal - isotropic phase transition temperature (T ni) is preferably at least 40 ° C., or higher still 60 ° C. are preferred, in particular 80 C. or higher is preferable. If T ni of the liquid crystal composition of the present invention is less than the above lower limit, there is a concern that the liquid crystal structure may be destroyed due to a temperature rise derived from a light source or reaction heat during polymerization. On the other hand, since viscosity tends to increase as T ni increases, it is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
  • the chiral pitch length (p) of the liquid crystal composition of the present invention is preferably 0.3 ⁇ m or more, and more preferably 0.8 ⁇ m or more. On the other hand, it is preferably 3 ⁇ m or less, and more preferably 2 ⁇ m or less.
  • p is not less than the above lower limit value, the driving voltage of the obtained liquid crystal element tends to be kept low, and when it is not more than the above upper limit value, the contrast tends to be high.
  • liquid crystal composition of the present invention is a liquid crystal composition containing a polymerizable monomer, a chiral nematic liquid crystal component having a positive dielectric anisotropy, and comprising a polymerizable monomer represented by the following formula (8): Including at least one compound represented by the following formula (2), (3), or (4), wherein the total amount of these compounds is 15% by weight or more based on the chiral nematic liquid crystal component It is.
  • R 3 ′′ and R 4 ′′ each independently represents an unsaturated acyl group
  • X 1 ′′ and X 4 ′′ each independently have a substituent.
  • represents may also be a divalent group
  • X 2 '' and X 3 '' each independently represent a direct bond or an optionally substituted divalent radical
  • a 1 '' ⁇ a 3 '' Each independently represents a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent.
  • a 1 ′′ to A 3 ′′ is an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • Ah , M 1 '' and m 4 '' are each independently, 0 or an integer of 6 or less
  • m 2 '' and m 3 '' are each independently, represent 0 or more, an integer of 4 or less .
  • R 3 ′′ and R 4 ′′ are, include those exemplified as R 3 'and R 4' in each of the formulas (7), preferable ones are also same.
  • an aliphatic hydrocarbon ring is contained in the structural portion represented by
  • polymerizable monomer represented by the formula (8) are the same as the polymerizable monomer represented by the formula (7). The invention is not limited to these unless it exceeds the gist.
  • the polymerizable monomer represented by the formula (8) is preferably contained in the liquid crystal composition in an amount of 0.5% by weight or more, more preferably 0.8% by weight or more, and further preferably 1% by weight or more. On the other hand, it is preferably 10% by weight or less, more preferably 8% by weight or less. By being in these ranges, light resistance and dimming element performance tend to be compatible.
  • the liquid crystal composition of the present invention may contain other monomers in addition to the polymerizable monomer represented by the formula (8). Specific examples, contents, preferred ranges, and the like of other monomers are the same as those described in the liquid crystal composition containing the formula (7). Further, the liquid crystal composition of the present invention may be in a liquid crystal state or a liquid state at room temperature of 25 ° C.
  • the chiral nematic liquid crystal component contained in the liquid crystal composition of the present invention is a liquid component contained in the liquid crystal light control layer of the liquid crystal element, and is usually a compound represented by the formula (2), (3) or (4) This corresponds to the sum of the other liquid crystal compounds used as necessary and the chiral agent.
  • the chiral nematic liquid crystal component has a positive dielectric anisotropy. Since the dielectric anisotropy of the chiral nematic liquid crystal component is positive, a liquid crystal element using the liquid crystal composition can be used as a transmission-scattering type element in a reverse mode, a normal mode, and a memory mode.
  • the value of the dielectric anisotropy ( ⁇ ) of the chiral nematic liquid crystal component is not particularly limited as long as it is positive, but is preferably 5 or more, and more preferably 8 or more for reducing the driving voltage of the liquid crystal element. .
  • the polymerization time of the polymerizable monomer is shortened because the individual molecules constituting the chiral nematic liquid crystal component do not have absorption at a wavelength that overlaps the absorption wavelength of the polymerization initiator. This is preferable.
  • the method for measuring physical properties such as ⁇ of the chiral nematic liquid crystal component in the liquid crystal composition of the present invention is not particularly limited.
  • the temperature of the liquid crystal composition is cooled to T ni or less, the liquid crystal composition is phase-shifted into a chiral nematic liquid crystal having a positive dielectric anisotropy, and at that temperature, the dielectric anisotropy and chiral pitch of the liquid crystal composition are changed.
  • the compound represented by the formula (2), (3) or (4) has the same meaning as that of the compound used for the liquid crystal composition containing the formula (7), and the preferred range and the like are also the same.
  • the compound represented by the formula (2), (3) or (4) is contained in a total of 15% by weight or more, preferably 18% by weight or more based on the chiral nematic liquid crystal component in the liquid crystal composition. It is more preferably 20% by weight or more, further preferably 40% by weight or more, and particularly preferably 60% by weight or more.
  • the upper limit of the content ratio is usually 90% by weight or less in order to ensure the content of the chiral agent and the like. It exists in the tendency for the performance and light resistance as a light control element to improve more because it is the said range.
  • the content ratio of the liquid crystal component in the liquid crystal composition is usually 90% by weight or more, preferably 91% by weight or more in the liquid crystal composition, and usually 99% by weight or less, preferably 98% by weight or less. is there. By being in this range, the balance of the transparency and optical response characteristics of the liquid crystal element tends to be obtained.
  • the content of the compound represented by the formula (2), (3) or (4) and the content of the chiral agent in the liquid crystal component are the same as the content in the liquid crystal phase of the present invention described above.
  • the chiral agent may be any compound as long as it exhibits optical activity, may be a synthetic product or a commercial product, may itself exhibit liquid crystallinity, and further has a polymerizable functional group. May be. Further, dextrorotatory or levorotatory may be used, and a dextrorotatory chiral agent and a levorotatory chiral agent may be used in combination.
  • the chiral agent used in the present invention excludes compounds corresponding to the formulas (2) to (4). Specifically, it is synonymous with the chiral agent shown in the liquid crystal composition containing the formula (7), and the preferred range and the like are also synonymous.
  • the liquid crystal composition of the present invention has a dielectric anisotropy of 0 or more.
  • the liquid crystal element of the present invention can be used as a transmission-scattering type element in reverse mode, normal mode and memory mode.
  • the value of dielectric anisotropy ( ⁇ ) of the chiral nematic liquid crystal composition is not particularly limited as long as it is 0 or more, but is preferably positive, more preferably 5 or more, and 8 or more. It is preferable for reducing the driving voltage of the liquid crystal element.
  • the polymerization time of the polymerizable monomer is determined so that the individual molecules constituting the nematic liquid crystal do not have absorption at a wavelength overlapping the absorption wavelength of the polymerization initiator. This is preferable in terms of shortening.
  • the liquid crystal composition of the present invention is a polymerization initiator, a light stabilizer, an antioxidant, a thickener, a polymerization inhibitor, a photosensitizer, an adhesive, and an antifoaming agent as long as the effects of the present invention are not significantly impaired. Further, it may contain a surfactant or the like. These are respectively synonymous with what was mentioned by the liquid crystal composition containing the said Formula (7), and a specific example, a preferable range, etc. are also synonymous.
  • the liquid crystal composition of the present invention is used as a liquid crystal material by allowing a layer containing the cured product to exist between a pair of substrates disposed opposite to each other as described above.
  • the method for forming the liquid crystal light control layer of the liquid crystal element of the present invention is not particularly limited.
  • the peripheral part of a pair of substrates with electrodes arranged opposite to each other with a spacer is formed as a sealing cell by forming an adhesive layer with a photo-curable adhesive or the like, and normal pressure is applied to one or more adhesive layers provided in advance.
  • a method of forming the film by polymerization and curing with radiation such as ultraviolet light, visible light, and electron beam.
  • a substrate with electrodes supplied continuously is sandwiched between two rubber rolls, and the liquid crystal composition of the present invention containing or dispersing a spacer is sandwiched between them, and then photocured continuously.
  • the liquid crystal composition of the present invention containing or dispersing a spacer is sandwiched between them, and then photocured continuously.
  • the liquid crystal composition is flowed before the uncured liquid crystal composition is photocured, or a liquid crystal composition is subjected to shear stress. It is necessary to orient the composition to assume a planar structure.
  • the liquid crystal composition can have a planar structure by injecting the liquid crystal composition of the present invention into a sealed cell that has not been subjected to alignment treatment.
  • the method for polymerizing the polymerizable monomer in the liquid crystal composition of the present invention is preferably photopolymerization.
  • the light source for photopolymerization may be any light source that has a spectrum at the absorption wavelength of the radical photopolymerization initiator used, and typically any light source that can irradiate light having a wavelength of 220 nm to 450 nm.
  • Examples include high pressure mercury lamps, ultra high pressure mercury lamps, halogen lamps, metal halide lamps, UV-LEDs, blue LEDs, white LEDs, and the like.
  • a heat ray cut filter, an ultraviolet ray cut filter, a visible light cut filter, or the like may be used in combination.
  • the light may be irradiated to at least one surface from the transparent substrate of the liquid crystal element, and when both substrates holding the liquid crystal composition are transparent, both surfaces may be irradiated with light.
  • Light irradiation may be performed at one time or may be performed by dividing into several times.
  • PSCOF Phase Separated Composite Organic Film
  • irradiance of the light irradiated to the liquid crystal composition between the substrates is usually 0.01 mW / cm 2 or more, preferably 1 mW / cm 2 or more, more preferably 10 mW / cm 2 or more, particularly preferably Is 30 mW / cm 2 or more. If the irradiance is too small, the polymerization does not proceed sufficiently. Moreover, what is necessary is just to give the integrated irradiation amount of 2 J / cm ⁇ 2 > or more normally to photopolymerization of a liquid crystal composition, Preferably it is 3 J / cm ⁇ 2 > or more.
  • the light irradiation time may be determined in accordance with the irradiance of the light source. From the viewpoint of improving productivity, the light irradiation is usually completed within 200 seconds, preferably within 60 seconds, while the light irradiation is performed for 10 seconds or more. preferable. If the light irradiation time is too short, the repetition durability of the liquid crystal element may be inferior.
  • the temperature at which the liquid crystal composition is polymerized is usually preferably 0 ° C. or higher and 40 ° C. or lower.
  • the temperature is at least the above lower limit, the polymerization reaction tends to proceed.
  • the temperature is not more than the above upper limit, an increase in the temperature of the device due to the heat accumulated with the polymerization reaction can be suppressed, and the polymerization can be performed at a temperature below the phase transition temperature of the liquid crystal. Accordingly, the liquid crystal alignment is not locally disturbed, and the optical characteristics and driving durability of the liquid crystal element are hardly affected.
  • the chiral nematic liquid crystal is dispersed or formed into a continuous layer in a thin film-like transparent polymer, but the continuous layer shows the best contrast. Is formed.
  • the liquid crystal element of the present invention can be used as a transmission-scattering type element in reverse mode, normal mode, and memory mode.
  • the liquid crystal element of the present invention can be switched from a transparent state to a scattering state (opaque state) by applying a voltage or returning from a voltage application state to a voltage non-application state. . Therefore, there is a region where the visible light transmittance when a voltage is applied is lower than the visible light transmittance when no voltage is applied.
  • the liquid crystal device of the present invention when used in the normal mode, switching from the transparent state to the scattering state (opaque state) by applying no voltage or returning from the voltage non-application state to the voltage application state. can do. Therefore, there is a region where the visible light transmittance when no voltage is applied is lower than the visible light transmittance when a voltage is applied.
  • the liquid crystal element of the present invention performs optical modulation by switching light scattering, display can be performed without using a polarizing plate. Therefore, the liquid crystal element of the present invention can have a transmittance exceeding 50% and has high light utilization efficiency.
  • the voltage here refers to at least one of alternating current and direct current.
  • a screen using a liquid crystal element capable of switching between a transparent state and a light-shielding state is used as a transparent body, and an image projected by a projector or the like is imaged when the screen is in a transparent state.
  • a see-through display is possible.
  • the projector or the like projects an image on a part or the whole of the screen, and when the screen is in a transparent state, the projector or the like
  • the screen and the image projector are synchronized so that the image is not projected.
  • the liquid crystal element is required to have high responsiveness, high contrast, and a specific haze value, and the liquid crystal element of the present invention can be suitably used.
  • a voltage sufficient to cause the chiral nematic liquid crystal phase to transition from the planar state to the focal conic state may be applied between the electrodes.
  • a voltage sufficient to cause the chiral nematic liquid crystal phase to transition from the planar state to the focal conic state may be applied between the electrodes.
  • the applied waveform is not particularly limited, such as direct current, alternating current, pulse, or a composite wave thereof.
  • a DC voltage preferably 0.5 msec or more
  • an AC voltage it may be a sine wave, a rectangular wave, a triangular wave, or a composite wave thereof, preferably 0.5 msec or more at a frequency of 100 kHz or less
  • switching can be performed by applying a pulse width of 0.5 msec or more.
  • the driving voltage of the liquid crystal element is typically 60 V or less, preferably 30 V or less for a DC voltage, typically 120 Vp-p or less, preferably 90 Vp-p or less for an AC voltage, and a maximum value of 60 V or less for a pulse voltage.
  • the maximum value is 30V or less.
  • the upper limit of the operating temperature of the liquid crystal element of the present invention is T ni of the chiral nematic liquid crystal phase.
  • the operating temperature range is preferably ⁇ 10 ° C. or higher, more preferably 0. It is above °C. Moreover, it is preferably 60 ° C. or lower, and more preferably 40 ° C. or lower.
  • the haze of the liquid crystal element of the present invention is preferably 15% or less when no voltage is applied (when the power is turned off), and is 70 when at least one of a DC voltage and an AC voltage is applied (when the power is turned on). % Or more is preferable. In particular, it is preferably 10% or less when the power is turned off and 90% or more when the power is turned on.
  • the haze exceeds 15% in a room or under a fluorescent lamp, the cloudiness is conspicuous.
  • the haze is less than 70%, a silhouette on the other side of the liquid crystal element tends to be seen.
  • the normal mode it is preferably 15% or less when at least one of a DC voltage and an AC voltage is applied (when the power is turned on), and preferably 70% or more when no voltage is applied (when the power is turned off). . In particular, it is preferably 10% or less when the power is turned on and 90% or more when the power is turned off.
  • the haze exceeds 15% in a room or under a fluorescent lamp, the cloudiness is conspicuous.
  • the haze is less than 70%, a silhouette on the other side of the liquid crystal element tends to be seen.
  • the parallel light transmittance of the liquid crystal element of the present invention is 75% or more when the power is turned off, preferably 15% or less when the power is turned on, and 80% or more when the power is turned off. It is particularly preferred that it is sometimes 10% or less. If it is less than 75% indoors or under a fluorescent lamp, it is dim, and if it exceeds 15%, an object in front tends to be seen.
  • the normal mode it is preferably 75% or more when the power is on, 15% or less when the power is off, 80% or more when the power is on, and particularly preferably 10% or less when the power is off. If it is less than 75% indoors or under a fluorescent lamp, it is dim, and if it exceeds 15%, an object in front tends to be seen.
  • the haze of the liquid crystal element and the parallel light transmittance are measured according to JIS K7136 (2000).
  • the response time described in this specification refers to the visible light transmission when the liquid crystal element is saturated by decreasing the transmittance of visible light (380 to 800 nm) when no voltage is applied to 100% and by applying a voltage.
  • the rate is normalized to 0%, the time until the visible light transmittance reaches 10% when applying a test waveform (rectangular wave of 100 Hz in this embodiment) (rising response time), the test waveform It is defined as the time until the visible light transmittance reaches 90% when no voltage is applied (falling response time).
  • the visible light transmittance when the liquid crystal element is applied with at least one of a DC voltage and an AC voltage is normalized to 100%, and the visible light transmittance is reduced to 0% when it is saturated by applying no voltage.
  • the test waveform 100 Hz rectangular wave in this embodiment
  • the time until the visible light transmittance reaches 90% (rising response time)
  • the visible when the test waveform is not applied It is defined as the time until the light transmittance reaches 10% (falling response time).
  • the method for measuring the response time is measured by the method described in the examples.
  • the response time of the liquid crystal element of the present invention is preferably 8 msec or less, more preferably 5 msec or less, and more preferably 3 msec or less, in the temperature range of ⁇ 10 ° C. or higher. Particularly preferred.
  • the rise response time and the fall response time are the same.
  • the liquid crystal element of the present invention can be used for screens, displays, windows and the like.
  • the liquid crystal composition of the present invention can be used for a liquid crystal element and the like.
  • it can be used as a display panel or projection panel such as a liquid crystal element for blocking the visual field of buildings windows, partitions, show windows, etc., or by switching the display electrically with high-speed response. Can do.
  • Projection systems include front projection and rear projection, and are not particularly limited.
  • a rear projection system disclosed in Japanese Patent Laid-Open No. 6-82748 or International Publication No. 2009/150579, and a projection using coherent light as a light source disclosed in Japanese Patent Laid-Open No. 2010-217291. Name the system.
  • T ni Liquid Crystal-Isotropic Phase Transition Temperature (T ni ) of Liquid Crystal Composition
  • T ni Liquid Crystal-Isotropic Phase Transition Temperature (T ni ) of Chiral Nematic Liquid Crystal Phase>
  • the phase transition due to the temperature rise of the liquid crystal element was obtained by observing with a polarizing microscope (ECLIPSE LV100N POL manufactured by Nikon) and a hot stage (FP82 manufactured by METTLER).
  • ⁇ ⁇ 1 ⁇ 2 .
  • ⁇ 1 is the dielectric constant in the major axis direction of the liquid crystal molecules
  • ⁇ 2 is the dielectric constant in the uniaxial direction of the liquid crystal molecules.
  • D represents the thickness of the liquid crystal phase.
  • S represents the overlapping portion of the electrodes of the two electrode substrates. It represents the area of).
  • ⁇ of the chiral nematic liquid crystal phase of the liquid crystal element was obtained by an addition rule of dielectric anisotropy of the liquid crystal component.
  • a chiral nematic liquid crystal or a liquid crystal composition is injected into an empty cell having a gap of 12 ⁇ m composed of a transparent glass substrate with an electrode layer that has been subjected to a homogeneous alignment treatment, and a selective reflection wavelength ⁇ measured by a spectrophotometer (SolidSpec-3700 manufactured by Shimadzu Corporation).
  • p ⁇ / n (where n represents the refractive index of the chiral nematic liquid crystal or liquid crystal composition).
  • ⁇ Measurement method of haze of liquid crystal element The haze of the liquid crystal element was measured according to JIS K7136 at room temperature (25 ° C.) with a haze meter NDH5000SP (manufactured by Nippon Denshoku). For driving the liquid crystal, a rectangular wave of 100 Hz was applied, and the measurement voltage was 80 Vp-p.
  • ⁇ Measurement method of response time of liquid crystal element The response time of the liquid crystal element was measured at a room temperature of 25 ° C. For driving the liquid crystal, a rectangular wave of 100 Hz was applied, and the measurement voltage was 80 Vp-p. A halogen lamp was used as the light source and a photodiode was used as the detector. The rise response time and the fall response time when a test waveform was applied while light was vertically incident on the liquid crystal element were measured, and the sum of these was evaluated as the response time.
  • ⁇ Light resistance test method of liquid crystal element The light resistance test of the liquid crystal element was performed using a xenon weather meter (Ci4000 manufactured by Atlas). The test was conducted at a black panel temperature of 35 ° C., humidity of 50% RH, no rain, irradiance of 680 W / m 2 , and 40 hours. A UV cut filter (SC-39 manufactured by Fuji Film Co., Ltd.) was attached to the sample.
  • L1-I had an OFF haze of 3.4%, an ON (80 Vp-p applied) haze of 98.1%, and a response time (80 Vp-p applied) of 5.0 msec.
  • L1-I after light resistance test is 4.1% haze when OFF, 98.0% when ON (80 Vp-p applied), and response time (80 Vp-p applied) is 5.0 msec. Maintained good performance.
  • L2-I had an OFF haze of 3.1%, an ON (80 Vp-p applied) haze of 98.0%, and a response time (80 Vp-p applied) of 4.7 msec.
  • L2-I after the light resistance test has a haze of 3.5% when OFF, a haze of 97.4% when ON (80 Vp-p applied), and a response time (80 Vp-p applied) of 4.5 msec. Maintained good performance.
  • L3-I had a haze of 2.0% when OFF, a haze of 97.1% when ON (80 Vp-p applied), and a response time (80 Vp-p applied) of 5.8 msec.
  • L3-I after the light resistance test has a haze of 2.7% when OFF, a haze of 97.0% when ON (80 Vp-p applied), and a response time (80 Vp-p applied) of 5.7 msec. Maintained good performance.
  • L4-I had a haze of 2.9% when OFF, 95.9% of haze when ON (80 Vp-p applied), and a response time (80 Vp-p applied) of 5.3 msec.
  • L4-I after light resistance test is 3.1% haze when OFF, 93.7% haze when ON (80 Vp-p applied), and response time (80 Vp-p applied) is 5.4 msec. Maintained good performance.
  • L5-I haze at OFF was 2.4%
  • haze at ON (80 Vp-p applied) was 95.5%
  • response time (80 Vp-p applied) was 5.6 msec.
  • L5-I after the light resistance test has a haze of 2.8% when OFF, a haze of 95.4% when ON (80 Vp-p applied), and a response time (80 Vp-p applied) of 5.7 msec. Maintained good performance.
  • L6-I had an off haze of 3.1%, an on (80 Vp-p applied) haze of 93.5%, and a response time (80 Vp-p applied) of 5.0 msec.
  • L6-I after the light resistance test has a haze of 3.3% when OFF, a haze of 92.2% when ON (80 Vp-p applied), and a response time (80 Vp-p applied) of 4.9 msec. Maintained good performance.
  • L7-I liquid crystal element
  • L7-I In L7-I, the haze at OFF was 89.0%, the haze at ON (100 Vp-p applied) was 16.3%, and the response time (100 Vp-p applied) was 12.4 msec.
  • L7-I after the light resistance test has a haze of 89.2% when OFF, 18.1% when ON (applied 100Vp-p), and a response time (applied 100Vp-p) of 11.3msec. Maintained good performance.
  • L8-I haze at OFF was 89.0%, haze at ON (100 Vp-p applied) was 15.8%, and response time (100 Vp-p applied) was 16.9 msec.
  • L8-I after the light resistance test has a haze of 96.8% when OFF, a haze of 16.5% when ON (100 Vp-p applied), and a response time (100 Vp-p applied) of 15.2 msec. Maintained good performance.
  • L9-I had a haze of 2.4% when OFF, a haze of 97.6% when ON (80 Vp-p applied), and a response time (80 Vp-p applied) of 4.8 msec.
  • L9-I after the light resistance test has 3.1% haze when OFF, 88.9% haze when ON (80 Vp-p applied), and response time (80 Vp-p applied) is 5.0 msec. The scattering performance at the time of ON was lowered.
  • a chiral nematic liquid crystal composition L10 shown in Table-10A was prepared.
  • L10 contains a total of 11.5% by weight of the compounds represented by formulas (2) to (4) with respect to the total liquid crystal components.
  • This L10 was processed in the same manner as in Example 1 to obtain a liquid crystal element L10-I.
  • L10-I had a haze of 2.0% when OFF, a haze of 97.9% when ON (80 Vp-p applied), and a response time (4.6 Vp-p applied) of 4.6 msec.
  • L10-I after the light resistance test has a haze of 2.7% when OFF, a haze of 83.5% when ON (applied 80Vp-p), and a response time (applied 80Vp-p) of 4.3msec. The scattering performance at the time of ON was lowered.
  • a chiral nematic liquid crystal composition L11 shown in Table-11A was prepared.
  • L11 contains a total of 11.5% by weight of the compounds represented by formulas (2) to (4) with respect to the total liquid crystal components.
  • This L11 was processed by the same method as in Example 1 to obtain a liquid crystal element L11-I.
  • L11-I has a haze of 9.7% when turned off, a haze of 97.9% when turned on (applied 80Vp-p), and a response time (applied 80Vp-p) of 11.2msec.
  • the light control performance was inferior due to the high response time.
  • L11-I after the light resistance test has a haze of 10.1% when OFF, a haze of 93.2% when ON (80 Vp-p applied), and a response time (80 Vp-p applied) of 10.5 msec.
  • the dimming performance was inferior because the haze was high when transparent and the response time was long.
  • a chiral nematic liquid crystal composition L12 shown in Table-12A was prepared.
  • L12 does not contain the compounds represented by formulas (2) to (4).
  • This L12 was processed by the same method as in Example 1 to obtain a liquid crystal element L12-I.
  • L12-I haze at OFF was 3.2%
  • haze at ON (80 Vp-p applied) was 96.8%
  • response time (80 Vp-p applied) was 4.8 msec.
  • L12-I after the light resistance test has an OFF haze of 3.4%
  • a response time (80 Vp-p applied) of 5.1 msec.
  • the scattering performance at the time of ON was lowered.
  • the liquid crystal element of the present invention obtained by using the liquid crystal composition of the present invention has a low haze when transparent, on the other hand, a high haze when scattering, and a short response time. It can be seen that the optical device has excellent performance as an optical element, and can maintain the performance sufficiently even after the light resistance test, and has excellent light resistance.

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Abstract

La présente invention concerne un élément à cristaux liquides qui comporte : une paire de substrats opposés qui sont chacun pourvus d'une électrode, au moins un desdits substrats étant un substrat transparent; et une couche de commande de lumière à cristaux liquides interposée entre les substrats et contenant un complexe qui comprend une phase cristalline liquide nématique chirale et une phase de résine polymère, la phase de résine polymère comprenant une structure spécifique, la phase de cristaux liquides nématiques chiraux ayant une anisotropie diélectrique positive, la phase de cristaux liquides nématiques chiraux contenant au moins un type parmi des composés spécifiques, et la quantité totale desdits composés en utilisation représente 15 % en poids ou plus par rapport à la quantité totale du composant cristal liquide nématique chiral.
PCT/JP2017/021873 2016-06-14 2017-06-13 Élément à cristaux liquides, composition de cristaux liquides, et écran, affichage et fenêtre utilisant l'élément à cristaux liquides WO2017217430A1 (fr)

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CN108676565A (zh) * 2018-03-19 2018-10-19 北京八亿时空液晶科技股份有限公司 一种液晶材料及其应用
WO2019220299A1 (fr) * 2018-05-18 2019-11-21 株式会社半導体エネルギー研究所 Élément à cristaux liquides, panneau d'affichage et dispositif d'affichage
JP2019200414A (ja) * 2018-05-15 2019-11-21 凸版印刷株式会社 調光装置
WO2020115936A1 (fr) * 2018-12-06 2020-06-11 Dic株式会社 Composition de cristaux liquides et élément d'affichage à cristaux liquides
JP2021139946A (ja) * 2020-03-02 2021-09-16 凸版印刷株式会社 調光装置、および、調光シートの駆動方法
JP2021139945A (ja) * 2020-03-02 2021-09-16 凸版印刷株式会社 調光装置、および、調光シートの駆動方法
CN113589575A (zh) * 2021-08-13 2021-11-02 河北工业大学 一种聚合物蜂网液晶显示器制造方法

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JP2013534640A (ja) * 2010-05-19 2013-09-05 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 液晶媒体を含む光学的スイッチ素子

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JP2013534640A (ja) * 2010-05-19 2013-09-05 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング 液晶媒体を含む光学的スイッチ素子
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108676565A (zh) * 2018-03-19 2018-10-19 北京八亿时空液晶科技股份有限公司 一种液晶材料及其应用
JP2019200414A (ja) * 2018-05-15 2019-11-21 凸版印刷株式会社 調光装置
JP7293733B2 (ja) 2018-05-15 2023-06-20 凸版印刷株式会社 調光装置
WO2019220299A1 (fr) * 2018-05-18 2019-11-21 株式会社半導体エネルギー研究所 Élément à cristaux liquides, panneau d'affichage et dispositif d'affichage
WO2020115936A1 (fr) * 2018-12-06 2020-06-11 Dic株式会社 Composition de cristaux liquides et élément d'affichage à cristaux liquides
JPWO2020116555A1 (ja) * 2018-12-06 2021-02-15 Dic株式会社 液晶組成物及び液晶表示素子
JP2021139946A (ja) * 2020-03-02 2021-09-16 凸版印刷株式会社 調光装置、および、調光シートの駆動方法
JP2021139945A (ja) * 2020-03-02 2021-09-16 凸版印刷株式会社 調光装置、および、調光シートの駆動方法
CN113589575A (zh) * 2021-08-13 2021-11-02 河北工业大学 一种聚合物蜂网液晶显示器制造方法

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