WO2021202606A1 - Structure à paroi polymère améliorée et ses procédés de fabrication - Google Patents

Structure à paroi polymère améliorée et ses procédés de fabrication Download PDF

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Publication number
WO2021202606A1
WO2021202606A1 PCT/US2021/024995 US2021024995W WO2021202606A1 WO 2021202606 A1 WO2021202606 A1 WO 2021202606A1 US 2021024995 W US2021024995 W US 2021024995W WO 2021202606 A1 WO2021202606 A1 WO 2021202606A1
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WIPO (PCT)
Prior art keywords
light modulating
polymer
acrylate
substrate
modulating device
Prior art date
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PCT/US2021/024995
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English (en)
Inventor
Piotr Popov
Robb Bagge
Neil Cramer
Original Assignee
Nitto Denko Corporation
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Application filed by Nitto Denko Corporation filed Critical Nitto Denko Corporation
Priority to JP2022559507A priority Critical patent/JP2023519964A/ja
Priority to KR1020227033714A priority patent/KR20220160592A/ko
Priority to CN202180025838.4A priority patent/CN115380241A/zh
Publication of WO2021202606A1 publication Critical patent/WO2021202606A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133377—Cells with plural compartments or having plurality of liquid crystal microcells partitioned by walls, e.g. one microcell per pixel
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
    • 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
    • G02F1/13775—Polymer-stabilized liquid crystal layers
    • 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
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/13—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used used in the technical field of thermotropic switches
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars

Definitions

  • the present disclosure relates to light modulating devices having improved polymer walls construction.
  • Liquid crystals or other kinds of functional liquid phase materials may be used for light modulation in response to various external stimuli, such as thermal stimulus, UV light stimulus, electric field stimulus, magnetic field stimulus and so on.
  • various external stimuli such as thermal stimulus, UV light stimulus, electric field stimulus, magnetic field stimulus and so on.
  • the vertical dimension parallel to the vector of gravitational acceleration
  • gravitational effects on a liquid crystal layer may dominate the capillary effect, depending on capillary cell gap width, surface tension, contact angle, etc.
  • window devices may be exposed to broad range of environmental conditions, such as broad range of temperatures. Light modulating liquid compositions may experience significant thermal expansion at elevated temperature and due to gravity may accumulate at the bottom and cause undesired "gravity mura" defects or even damage the device.
  • PDLC Polymer dispersed liquid crystal
  • PDLC devices have poor optical performance and such devices require relatively high driving voltage.
  • other approaches for compartmentalized liquid crystal layers have been described.
  • these approaches may not satisfy the optical clarity requirements for display and/or smart window applications.
  • these may not be utilizable in roll-to-roll fabrication processes necessary for high speed manufacturing requirements.
  • the polymer walls, ribs, or connectors may not have sufficient adhesion to the electrically conducting materials or substrates.
  • a light modulating device may address any or all of the shortcomings mentioned above having a high quality polymer wall structure formed in a controlled process and/or compatible with high throughput manufacturing requirements.
  • Such a device may have better transparency in one of its states, improved viewing angles and low power consumption (for example, capable of battery powering).
  • the light modulating devices described herein may be useful in methods for controlling the amount of light and/or heat passing through a window.
  • the light modulating devices described herein may further be useful in efforts to provide privacy, reduce heat from ambient sunlight, and control harmful effects of ultraviolet light.
  • the current disclosure describes an improved polymer wall structure, useful in light modulating devices.
  • the improved polymer wall structure, the light modulating device incorporating the same, and the methods of making the same may be in accordance with any of the embodiments as described herein.
  • Some embodiments include a light modulating device comprising: a first transparent electrically conductive substrate; a second transparent electrically conductive substrate; silane couplers covalently bonded to the first transparent electrically conductive substrate and the second transparent electrically conductive substrate, wherein the silane couplers comprise a reactive monomer methacrylate unit, wherein at least some of the reactive monomer methacrylate units of the silane couplers are covalently bonded to, or entangled with, an acrylate polymer in a light modulating layer; wherein the light modulating layer comprises a liquid crystal compound and the acrylate polymer, and is positioned between the first transparent electrically conductive substrate and the second transparent electrically conductive substrate; and wherein the acrylate polymer is part of a polymer wall system connecting the first substrate and the second substrate.
  • Some embodiments include a polymer wall construct, polymer wall system and/or construct for connecting plural substrates.
  • the system may comprise a first substrate, such as a hydroxy activated substrate; a silane coupler bonded to the hydroxy activated substrate, the silane coupler comprising a silane group and a (meth)acrylate group, the silane coupler covalently bonded to the hydroxy activated substrate; and at least a first reactive monomer unit or its resulting polymer chains, at least some first reactive polymer units entangled or covalently bonded to the silane coupler.
  • the polymer wall construct may further comprise a second silane coupler entangled or covalently bonded to first reactive monomer unit or its resulting polymer chains; and a second hydroxy activated substrate, the second silane coupler covalently bonded to the second hydroxy activated substrate.
  • the silane coupler may be methacryloxypropyltrimethoxysilane.
  • the reactive monomer may be a monofunctional monomer.
  • the entangled or covalently bonded polymer construct may comprise a linear polymer chain.
  • the silane coupled polymer structure may comprise a crosslinked and/or branched polymer chains.
  • the polymer structures may not be covalently bonded to silane couplers but linked to them via chain entanglements.
  • the reactive monomer may be a mixture of a monofunctional monomer and a multi-functional monomer.
  • the reactive monomer may be selected from acrylic acid, a vinyl-pyrrolidinone, acryloyl morpholine, 2-phenoxyethyl acrylate, an alkoxyalkylacrylate, an alkylaryl acrylate, and a heteroarylacrylate.
  • the multi-functional monomer may be selected from hexane-1, 6-dithiol (HDT), ethylene glycol diacrylate (EGDA), hexane- 1,6- diyl diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tricyclodecane dimethanol diacrylate (TCDDA), hydroxy pivalic acid neoentyl glycol diacrylate (HPNDA), tris[2-(acryloyloxy)ethyl] isocyanurate (TATATO), or pentaerythritol tetrakis(3-mercaptopropionate) (PETMP).
  • HDT hexane-1, 6-dithiol
  • EGDA ethylene glycol diacrylate
  • HDDA hexane- 1,6- diyl diacrylate
  • DPGDA dipropylene glycol diacrylate
  • TCDDA tricyclodecane dimethanol diacrylate
  • HPNDA hydroxy pivalic acid
  • a light modulating device may comprise a first transparent hydroxy activated electrically conductive element; a second transparent hydroxy activated electrically conductive element; a light modulating layer, said light modulating layer comprising a plurality of polymer walls bonded respectively to and between the first transparent hydroxy activated electrically conductive element and the second transparent hydroxy activated electrically conductive element, the polymer walls may comprise a silane coupler bonded to the first and second hydroxy activated conductive element; and reactive monomer consisting of acrylate or methacrylate units from this point referenced as (meth)acrylate units, and at least some reactive monomer (meth)acrylate units coupled to the respective silane coupler.
  • the reactive monomer (meth)acrylate units may comprise a monofunctional or multi-functional (meth)acrylate unit.
  • the reactive monomer (meth)acrylate units are a mixture of 2-Phenoxyethyl acrylate (PEA) and tricyclodecane dimethanol diacrylate (TCDDA).
  • the reactive monomer (meth)acrylate units are a mixture of PEA and AA (acrylic acid).
  • Some embodiments include a method for attaching a first substrate to a second substrate comprising providing a first hydroxylated substrate; activating the first substrate to introduce hydroxy groups to the first substrate; bonding a silane (meth)acrylate coupler to the hydroxy activated first substrate; and bonding at least one monofunctional monomer to the silane coupler.
  • the method for attaching a first substrate to a second substrate, wherein providing a first hydroxylated substrate may comprise providing a first substrate and activating the first substrate.
  • the method for activating the first substrate may comprise applying ozone plasma treatment and/or piranha surface treatment to the first substrate.
  • the piranha solution treatment includes: applying a solution of sulfuric acid and hydrogen peroxide to hydroxylate the substrate surface; rinsing the hydroxylated substrate surfaces with water; rinsing the substrates subsequently with acetone and drying said substrates under a stream of pressurized air or nitrogen gas.
  • FIG. 1 Is a schematic representation of the adhesion mechanism of polymer wall constructs to the substrate.
  • FIG. 2 Is a schematic representation of two opposing substrates linked together by a polymer wall and silane coupling at the interfaces.
  • FIG. 3 Is a schematic cross section of a light modulating device incorporating the polymer wall structure described herein.
  • FIG. 4 Demonstrates the results of peel strength test of the sample that included the PEA reactive monomer without liquid crystals.
  • the test was designed to demonstrate that the peel strength reaches a high value due to silane coupling of the polymerized PEA to the substrates.
  • the width of the sample was 1 inch.
  • FIG. 5 Is an image taken with a polarizing microscope to demonstrate PEA- based polymer walls 51 for compartmentalization of liquid crystals 52.
  • FIG. 6 Demonstrates the results of peel strength test of the sample that included the non-crosslinked PEA-based polymer walls. The test shows that peel strength value decreases dramatically due to the presence of LC. The width of the sample was 1 inch.
  • FIG. 7 Is an image taken with a polarizing microscope to demonstrate PEA with AA (acrylic acid) additive based polymer walls 71 for compartmentalization of liquid crystals 72.
  • FIG. 8 Demonstrates the results of peel strength test of the sample that included the PEA with AA based polymer walls. The test shows that peel strength value improves due to AA. The width of the sample was 1 inch.
  • FIG. 9 Is an image taken with a polarizing microscope to demonstrate PEA- based polymer walls crosslinked with TCDDA 91 for compartmentalization of liquid crystals 92.
  • FIG. 10 Demonstrates the results of peel strength test of the sample that included the TCDDA crosslinked PEA-based polymer walls. The test shows that peel strength value improves due to crosslinking. The width of the sample was 1 inch.
  • a polymer wall structure which may be used in light modulating devices useful in window type applications for energy efficiency and privacy, are disclosed.
  • the light modulating devices described herein may be switched between an opaque light scattering state to a transparent state by the application of an electromagnetic field.
  • transparent as used herein, meant that the structures do not absorb a significant amount of visible light radiation or reflect a significant amount of visible light radiation, rather, it is transparent to visible light radiation.
  • polymer matrix is a term of art, as used herein refers to a viscous composition or mixture of at least one polymer (or reactive monomer), at least one liquid crystal compound, and a photo-initiator.
  • the matrix may contain solvents, crosslinkers and other polymerizable monomers.
  • monofunctional is a term of art, as used herein, refers to compounds with one radically polymerizable groups.
  • multi-functional is a term of art, as used herein, refers to compounds, e.g., (meth)acrylates, with two ("difunctional”) or more (“polyfunctional”), preferably 2 to 4, radically polymerizable groups.
  • linear polymer refers to a macromolecule made of monomeric units arranged in a straight and / or unbranched line.
  • crosslinked polymer refers to a macromolecule that has covalent bonds between the polymer molecules.
  • the liquid crystal composition may comprise a photoinitiator
  • the statement “the liquid crystal composition may comprise a photoinitiator” should be interpreted as, for example, “In some embodiments, the liquid crystal composition comprises a photoinitiator,” or “In some embodiments, the liquid crystal composition does not comprise a photoinitiator,” or “In some embodiments, the liquid crystal composition will comprise a photoinitiator/' or “In some embodiments, the liquid crystal composition will not comprise a photoinitiator/' etc.
  • a polymer wall construct such as construct 10
  • a substrate such as substrate 12
  • the substrate comprises pendent functional oxygen groups 14, e.g., formed by reaction with hydroxyl or hydroxy groups, extending therefrom.
  • silane coupling groups such as silane groups 16
  • a polymer 22, such as poly (meth)acrylate unit fragments may be entangled with, or coupled with, at least one silane group 16.
  • the functional groups in polymer 22, such as -CO2- are omitted from FIG. 1 for simplicity in viewing.
  • the polymer construct may comprise a linear polymer chain.
  • the silane coupled polymer structure may comprise crosslinked and/or branched polymer chains.
  • a polymer wall construct such as construct 20, comprises a first substrate and a second substrate.
  • the polymer wall construct may comprise a first hydroxy activated substrate, such as substrate 12A, having pendent functional oxygen group 14A, silane couplers, such as silane couplers 16A, covalently bound to the pendant hydroxy group 14A of the hydroxy activated substrate 12A.
  • the silane coupler 16A may further comprise a reactive monomer coupling end, wherein the reactive monomer is entangled with, or coupled with, a reactive monomer of the second substrate.
  • polymer 22 may be coupled to silane- hydroxy coupling end of the first silane coupler 16A.
  • the second silane coupler 16B may comprise a reactive monomer coupled with or entangled with the polymeric 22 made out of reactive monomer precursors, wherein the silane coupler 16B may have a coupling end coupled or entangled to the second hydroxy activated substrate 12B, e.g., by condensation with a pendant hydroxy or hydroxyl group 14B.
  • a light modulating device such as device 30, comprises: a first transparent electrically conductive element, such as element 32; a second transparent electrically conductive element 34; and a light modulating layer 33 disposed therebetween.
  • the transparent electrically conductive elements 32 and 34
  • the light modulating device may comprise a liquid crystal compound (not shown).
  • a plurality of polymer wall constructs may be positioned between, and bonded to, the first and second transparent electrically conductive elements as described above, e.g., with a pendantfunctional group, e.g., the silane groups coupled to hydroxyl groups of the conductive elements (see FIG. 2).
  • the electrically conductive elements may comprise substrates 42A and 42B and transparent electrically conductive layers 44A and 44B, respectively.
  • the substrates (42A and 42B) may be non-conductive materials.
  • the width of the polymer wall of construct 38 may have a dimension L.
  • the polymer wall construct 38 defines the dimension of the compartment S.
  • a cell gap, defined as G may space apart the first and second transparent electrically conductive elements.
  • Electrical leads, 46A and 46B may be attached to the electrically conductive layers 44A and 44B, respectively.
  • the polymer wall constructs 38 may define cavities 40 therebetween.
  • a light modulating composition 48 e.g., a mixture of a polymer matrix and liquid crystal composition, may be disposed within the defined cavities 40.
  • An external voltage source (not shown) may be connected to electrical leads, such as 46A and 46B, to switch the light modulating device from an opaque state to a transparent state.
  • the voltage source may be an AC voltage source.
  • the voltage source may be an AC-DC inverter and a battery.
  • the voltage source may be a DC battery, such as thin cell.
  • a polymer wall system may comprise two transparent substrates, wherein the system may comprise a first hydroxy activated substrate.
  • the system may comprise a first and a second or, e.g., a pair of opposing transparent substrates.
  • the transparent substrates may comprise a first transparent electrically conductive substrate and a second transparent electrically conductive substrate.
  • the substrates may comprise non-conductive material. The substrate is not particularly limiting, and one skilled in the art of light shutters would be able to determine an appropriate material for the substantially transparent substrates. Some non-limiting examples include glass and polymer films.
  • Typical polymer films include films made of polyolefin, polyester, polyethylene terephthalate, polyvinyl chloride, polyvinyl fluoride, polyvinylidene difluoride, polyvinyl butyral, polyacrylate, polycarbonate, polyurethane, etc., and/or combinations thereof.
  • the substrates may comprise a first transparent electrode and a second (opposing) transparent electrode.
  • the transparent electrodes may comprise an indium tin oxide (ITO), a fluorine doped tin oxide (FTO), a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), a silver oxide, a zinc oxide, or other transparent conductive polymer film coating.
  • the opposing substrates may have an inside facing conductive surface and an outward/distal facing exterior surface.
  • the non-conductive substrate may comprise a non-conductive material and/or may be disposed upon the outward/distal facing exterior surface.
  • the non-conducting materials may be selected from AI 2 O 3 , SiO x , and other transparent dielectrics, to prevent or reduce potential electrical shorting when bending the device.
  • Chemical vacuum deposition, chemical vapor deposition, evaporation, sputtering or other suitable coating techniques may be used for applying electrodes on substrate.
  • the transparent element may comprise a first substrate, e.g., a first transparent electrode, and a second substrate, e.g., a second transparent electrode.
  • the transparent element may be activated.
  • the transparent element may be activated in orderto facilitate covalent bonding between a silane coupler and the transparent element.
  • the activated transparent element comprises a surface hydroxyl group.
  • the surface hydroxyl group may be reacted with a silane coupler and/or a silyl group disposed therein, to introduce a covalent bond between the activated substrate and the silane coupler.
  • the surface functional group of the activated transparent element may be a hydroxy or hydroxyl group. In some embodiments, the surface functional group of the activated transparent element may be a hydrolyzed epoxide group.
  • the transparent element may comprise polymer wall constructs bonded to, and between, the first and second substrates, wherein the polymer wall constructs define plural reservoirs within the walls of the constructs. In some embodiments, the polymer wall constructs may comprise at least a first and/or second acrylate monomer units and/or subunit. In some embodiments, the transparent element may comprise a liquid crystal composition disposed within the plural reservoirs.
  • the first conductive substrate and/or the second conductive substrate may comprise an electron conduction layer, wherein the layer is in physical communication with the base of the substrate.
  • the base of the substate may be a non-conductive material.
  • the electron conduction layer is placed in direct physical communication with the base, such as a layer on top of the base.
  • the electron conduction layer may be impregnated directly into the base (e.g., ITO glass) or sandwiched in between two bases to form a single conductive substrate.
  • the base of the substrate may comprise a non-conductive material.
  • non-conductive material may comprise any suitable material, such as a suitable polymer, glass, polycarbonate, or combinations thereof.
  • the substrate polymer may comprise polyvinyl alcohol (PVA), polycarbonate (PC), acrylics including but not limited to poly(methyl methacrylate) (PMMA), polystyrene, allyl diglycol carbonate (e.g. CR-39), polyesters, polyetherimide (PEI) (e.g. Ultem ® ), cycloolefin polymers (e.g.
  • the electron conduction layer may comprise a transparent conductive oxide, conductive polymer, metal grids, carbon nanotubes (CNT), graphene, or a combination thereof.
  • the transparent conductive oxide may comprise a metal oxide.
  • the metal oxide may comprise iridium tin oxide (IrTO), indium tin oxide (ITO), fluorine doped tin oxide (FTO), doped zinc oxide, or combinations thereof.
  • the metal oxide may comprise indium tin oxide incorporated onto the base, e.g. ITO glass, ITO PET, or ITO PEN.
  • the polymer wall construct may comprise a silane coupler for covalent coupling to the hydroxy activated substrate.
  • the silane coupler may comprise a silane group (e.g. a trialkoxysilane, such as trimethoxysilane) and an acrylic group, such as a (meth)acrylate group, an acrylate group, etc.
  • the silane group may be covalently bonded to the hydroxy activated substrate, and may include an alkylene spacer (e.g. -C n H2 n -, wherein n is, for example, 0, 1, 2, 3, 4, 5, etc,) between the acrylate group and the silane group.
  • the silane coupler may be 3-(trimethoxysilyl)propyl methacrylate (Silane A174, [3- (methacryloyloxy)propyl]trimethoxysilane ) (CAS 2530-85-0, Millipore Sigma, St. Louis, MO, USA), as shown below.
  • the coupler above has a (meth)acrylate group, a trimethoxysilane group, and a -C H - or -(CH ) - alkylene spacer.
  • the method for growing the polymer walls comprises placing a photomask, having defined apertures therein, upon one of the substrates, wherein the apertures have a defined width and a defined spacing between them; applying photocuring radiation through the photomask apertures upon the polymer precursor composition for a period of time and intensity to cure the reactive monomers and form a plurality of polymer walls, at least some of the plurality of polymer walls extending between the substrates and defining a plurality of compartments therein; and removing the photomask.
  • the polymer walls may be a produce of reacting a reactive monomer.
  • the polymer wall composition is selected to prepare a polymerwall conversion (curing/solidifying) within a desired conversion/curing time.
  • the polymer wall which is a reaction product of a selected reactive monomer may have about 80% conversion in less than 7 minutes, less than 8 minutes, or less than 10 minutes, when exposed to 0.5 mW/cm 2 .
  • the reactive monomer may effect or provide for coupling or linkage between the activated hydroxy substrate and a silane coupler-activated transparent electron conducting layer.
  • the reactive monomer units may be (meth)acrylate units.
  • the reactive monomer may comprise a monofunctional monomer. In some embodiments, the reactive monofunctional monomer unit may comprise an epoxide functional group. In some embodiments, the reactive monomer may comprise a mono(meth)acrylate monomer.
  • the acrylate polymer may be a product of reacting any suitable monomer, or combination of monomers, such as acryloyl morpholine, phenoxy[alkyl] acrylate, acrylic acid, ethyl acrylate, 2-ethylhexyl acrylate [EHA], hydroxyethyl methacrylate, butyl acrylate, vinyl-pyrrolidinone or combinations thereof. It is believed that these reactive monomers are suitable because they have relatively small molecular weight and are expected to diffuse more quickly through liquid crystal formulations to form the polymerwalls atthe desired locations.
  • the monofunctional monomer may be selected from acrylic acid, a vinyl-pyrrolidinone, acryloyl morpholine, phenoxy acrylate, an alkoxyalkylacrylate, an alkylaryl acrylate, and a heteroarylacrylate.
  • Suitable first reactive monomers are described in Table 1 below.
  • the acrylate polymer may be a product of reacting a monofunctional monomer unit and a multi-functional monomer unit.
  • the multi-functional unit may comprise at least two functional groups, e.g., at least two epoxide groups.
  • the multi-functional monomeric unit may be partially polymerized with the multi-functional monomeric unit to provide crosslinking within the polymer walls.
  • the multi-functional monomeric unit e.g., a cross-linking monomer, may comprise a difunctional or multi-functional monomer, e.g., di(meth)acrylate, tri(meth)acrylate or multi(meth)acrylate monomer.
  • the second reactive monomer may comprise (HDT), tricyclodecanedimethanol diacrylate (TCDDA), 1,6-hexanediol diacrylate (HDDA), hydroxyl pivalic acid neopentyl glycol diacrylate (M210), trimethylolpropane triacrylate (TMPTA), ethylene glycol diacrylate (EDDA), diethylene glycol diacrylate (DEGDA), diethylene glycol dimethacrylate (DEGDMA), triethylene glycol diacrylate (TEGDA), diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylol propane, diallyl ether, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerithritol tetracrylate, pentaerythol pentacrylate, dipentaerythrytol hydroxy pentacrylate] or combinations thereof.
  • the multi-functional monomer unit may be selected from hexane-1, 6- dithiol (HDT), ethylene glycol diacrylate (EGDA), hexane-1, 6-diyl diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tricyclodecane dimethanol diacrylate (TCDDA), hydroxy pivalic acid neopentyl glycol diacrylate (HPNDA), tris[2-(acryloyloxy)ethyl] isocyanurate (TATATO), and / or pentaerythritol tetrakis(3-mercaptopropionate) (PETMP).
  • Suitable additive monomers are described in Tables 2, 3 and 4 below:
  • the ratio of monofunctional monomer unitsto multi-functional units may be about 20 wt%, about 25 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt% monofunctional units to about 80 wt%, about 70 wt%, about 60 wt%, about 50 wt%, about 40 wt%, about 30 wt%, about 25 wt%, or about 20 wt% multi-functional units and/or any combination of values set forth herein, e.g., 25.0 wt%-75.0 wt%, monofunctional monomeric units to 75.0 wt% to 25 wt% multi-functional monomeric units.
  • the polymerized polymer mixture of the monofunctional and multi functional monomers may provide increased resistance to tensile forces and contributes to the attainment of the level of separation resistance between opposite ends of the aforementioned polymer walls.
  • the tensile strength between the polymer wall attached substrates may be on the order of 0.3 to 1.0 N/cm, e.g., about 0.5 N/cm.
  • the polymer walls may be a product of reacting a mixture containing a phenoxyalkyl acrylate, such as a phenoxyethyl acrylate (e.g. 2-phenoxy acrylate).
  • a phenoxyalkyl acrylate such as a phenoxyethyl acrylate (e.g. 2-phenoxy acrylate).
  • the reaction mixture containing phenoxyalkyl acrylate e.g. 2-phenoxy acrylate
  • the combination of the phenoxyalkyl acrylate (e.g. 2-phenoxy acrylate) and the additive (e.g. acrylic acid or tricyclodecane dimethanol diacrylate), and their reaction products (such as polymerization reaction products), are about 90-99% or about 95-99% of the weight of the light modulating layer
  • a light modulating device may comprise a light modulating layer.
  • the light modulating layer may comprise monomer subunits as described above, a liquid crystal compound, a polymerization inhibitor compound, and/or a UV blocker compound.
  • the polymer wall construct may be used in liquid crystal smart antenna elements; flexible beam steering light diffusers for smart indoor illumination; and/or flexible films for smart goggles and helmet visors.
  • the polymer wall construct may comprise a regular repeating geometric pattern.
  • dimension S (as shown in FIG. 3) may be the side dimension of the pattern, e.g., a square, which are liquid crystal rich, in which liquid crystals may freely flow. It is believed that the size of the repeating pattern may reduce the liquid crystal from excessive flows within the cell gap.
  • the value of S may be chosen between a minimum value - no smaller than cell gap size of the device (for example 10 pm) to ensure that optical properties of polymer network device are not hindered.
  • the distance between opposite walls of a repeating geometric pattern or cell for example, the distance between opposite walls through the center of the repeating geometric pattern, e.g.
  • the repeating geometric pattern may have an area of about 100-4,000,000 pm 2 , about 100-2,500 pm 2 , about 2,500-10,000 pm 2 , about 10,000- 50,000 pm 2 , about 50,000-100,000 pm 2 , about 100,000-250,000, about 250,000-500,000 pm 2 , about 500,000-1,000,000 pm 2 , or about 1,000,000-2,000,000.
  • the polymer walls may have a thickness of about 5-100 pm, about 5-20 pm, about 20-40 pm, about 40-60 pm, about 60-80 pm, or about 80-100 pm.
  • the light modulating layer may further contain spacer beads, such as plastic (e.g. polystyrene) or glass spacer beads, having a diameter of about 1-30 pm, about 5-15 pm, or about 10 pm. These may be helpful in maintaining the desired thickness of the light modulating layer before and during photocuring.
  • spacer beads such as plastic (e.g. polystyrene) or glass spacer beads, having a diameter of about 1-30 pm, about 5-15 pm, or about 10 pm.
  • the light modulating layer may comprise phenothiazine, or may be prepared by reacting a mixture containing phenothiazine, in an amount that is about 0.1-4%, about 0.5-2%, or about 1% of the weight of the light modulating layer or a precursor mixture to the light modulating layer.
  • Electrical lead wires and/or a power source may be attached to the electrodes.
  • An external voltage source may be connected to the electrical leads to switch the light shutter from an opaque focal conic state to a transparent state.
  • the external voltage source may also be used to pulse an electrical field to help maintain the optically transparent state by recharging the light shutter.
  • the voltage source may be an AC voltage source.
  • the voltage source may be an AC-DC inverter and a battery.
  • the voltage source may be a DC battery, such as thin cell.
  • the light modulating layer may comprise a liquid crystal and polymer composite.
  • the light modulating layer may comprise a liquid crystal composition and a light modulating layer polymer, where the liquid crystal composition may be dispersed in the polymer.
  • the liquid crystal composition polymer may comprise polymer precursors and initiators, which may be polymerized in situ.
  • the polymer precursors may comprise monomers, oligomers, or any combination thereof, before polymerization.
  • the polymer may be a photopolymer.
  • the photopolymer may comprise polymer precursors and a photoinitiator.
  • the polymer may be a thermoplastic polymer.
  • the thermoplastic polymer may comprise polymer precursors and a thermal initiator.
  • the photopolymer may comprise a UV-curable polymer ora visual light- based photopolymer.
  • the polymer may comprise a combination of a thermoplastic polymer and a photo/UV-curable polymer.
  • the ratio of liquid crystal compound to polymer may be between about 25:1 to about 1:1. In some embodiments, the ratio of liquid crystal compound to polymer may be between about 15:1 to about 3:1. In some embodiments, the ratio of liquid crystal compound to polymer may be between about 10:1 to about 8:1, or about 9:1.
  • the liquid crystal composition may comprise a photoinitiatior, e.g. in an amount of about 0.05-2%, about 0.05-1%, about 1-2%, or about 0.4-0.6% by weight.
  • the photoinitiator may comprise a UV irradiation photoinitiator.
  • the photoinitiator may also comprise a co-initiator.
  • the photoinitiator may comprise an a-alkoxydeoxybenzoin, a,a- dialkyloxydeoxybenzoin, a,a-dialkoxyacetophenone, a,a-hydroxyalkylphenone, O-acyl a- oximinoketone, dibenzoyl disulphide, S-phenyl thiobenzoate, acylphosphine oxide, dibenzoylmethane, phenylazo-4-diphenylsulphone, 4-morpholino-a- dialkylaminoacetophenone and combinations thereof.
  • the photoinitiator may comprise 2,4,6-trimethylbenzoyl)phosphine oxide (e.g.
  • Irgacure ® 184 Irgacure ® 369, Irgacure ® 500, Igracure ® 651, Igracure ® 907, Irgacure ® 1117, Irgacure ® 1700, 4,4'-bis(N,N-dimethylamino)benzophenone (Michlers ketone), (1-hydroxycyclohexyl) phenyl ketone, 2,2-diethoxyacetophenone (DEAP), benzoin, benzyl, benzophenone, or combinations thereof.
  • Irgacure ® 184 Irgacure ® 369, Irgacure ® 500, Igracure ® 651, Igracure ® 907, Irgacure ® 1117, Irgacure ® 1700, 4,4'-bis(N,N-dimethylamino)benzophenone (Michlers ketone), (1-hydroxy
  • the photoinitiator may comprise a blue-green and/or red sensitive photoinitiator.
  • the blue-green and/or red photoinitiator may comprise Irgacure ® 784, dye rose bengal ester, rose bengal sodium salt, campharphinone, methylene blue and the like.
  • co-initiators may comprise N- phenylglycine, triethylamine and combinations thereof. It is believed that the co-initiators may help to control the curing rate of the original pre-polymer, such that material properties may be manipulated.
  • the photoinitiator may comprise an ionic photoinitiator.
  • the ionic photoinitiator may comprise a benzophenone, camphorquinone, fluorenone, xanthone, thioxanthone, benzyls, a- ketocoumarin, anthraquinone, terephthalophenone, and combinations thereof.
  • the photoinitiator may comprise Igracure ® 907.
  • the light modulating layer may comprise a light modulating polymer matrix.
  • the polymer matrix may comprise at least one liquid crystal compound.
  • the at least one liquid crystal compound may comprise a nematic liquid crystal material.
  • the at least one liquid crystal compound may comprise a positive dielectric liquid crystal compound.
  • the at least one liquid crystal compound may comprise a dual frequency liquid crystal compound.
  • the at least one liquid crystal compound and the chiral dopant may form cholesteric liquid crystals.
  • concentration of the at least one liquid crystal compound may be calculated by subtracting the total amount of chiral dopant(s), reactive mesogen(s), and the UV photo-initiator(s) from 100.
  • the wt% of the at least one liquid crystal compound may be in the range of about 50 wt% to about 99 wt% of the total weight of the polymer matrix, or about 50-55 wt%, about 55-60 wt%, about 60-65 wt%, about 65-70 wt%, about 70-75 wt%, about 75-80 wt%, about 80-85 wt%, about 85-90 wt%, about 90-95 wt%, about 95-99 wt%, about 52 wt%, about 53, about 54 wt%, about 71 wt%, about 72 wt% about 73 wt% ⁇ about 74 wt%, about 82 wt%, about 83 wt%, about 84 wt% about 85, about 86 wt%, about 87 wt%, about 88 wt%, or any value in a range bounded by any of these these ranges.
  • Some embodiments include a method for attaching a first substrate to a second substrate.
  • the method may comprise providing a first hydroxy activated substrate.
  • the hydroxy groups may be formed on the first substrate by ozone plasma treatment or piranha solution treatment. Using either of these activation methods may lead to an ITO surface that is very hydrophilic, which indicates the successful surface enrichment with -OH (hydroxy) groups.
  • the method may comprise, bonding a silane acrylate to the hydroxy activated first substrate. In some embodiments, the method may comprise covalently bonding at least one reactive monomer to the silane coupler. In some embodiments the at least one reactive monomer may be a monofunctional (meth)acrylate monomer. In some embodiments, the reactive monofunctional (meth)acrylate monomer may comprise a linear alkyl segment. In some embodiments, the reactive monomer may be a mixture of a reactive monofunctional monomer and a reactive multi-functional monomer. In some embodiments, the reactive multi-functional monomer may crosslink the reactive monofunctional monomer.
  • Embodiment 1 A polymer wall system connecting plural substrates, the system comprising: a first hydroxy activated substrate; a silane coupler bonded to the hydroxy activated substrate, the silane coupler comprising a silane-hydroxy coupling end and a (meth)acrylate coupling end, the silane- hydroxy coupling end covalently bonded to the hydroxy activated substrate; and at least some reactive polymer (meth)acrylate chain covalently bonded to the silane coupler (meth)acrylate coupling end.
  • Embodiment 2 The polymer wall system of embodiment 1, further comprising: a second silane coupler coupled or entangled to first reactive monofunctional monomer unit; and a second hydroxy activated substrate, the second silane coupler comprising a silane- hydroxy coupling end and a (meth)acrylate coupling end, the silane-hydroxy coupling end coupled to the second hydroxy activated substrate.
  • Embodiment 3 The polymer wall system of embodiments 1 or 2, wherein the silane coupler is methacryloxypropyltrimethoxysilane.
  • Embodiment 4 The polymer wall system of embodiments 1 or 2, wherein the reactive monomer is a monofunctional monomer.
  • Embodiment 5 The polymer wall system of embodiments 1 or 2 wherein its structure comprises linear chains by polymerizing the reactive monomers.
  • Embodiment 6 Monomer formulation is a mixture of a monofunctional monomer and a multi-functional monomer.
  • Embodiment 7 The polymer wall system of embodiments 1 or 2, wherein the reactive monomer is selected from acrylic acid, a vinyl-pyrrolidinone, acryloyl morpholine, phenoxy acrylate, an alkoxyalkylacrylate, an alkylaryl acrylate, and a heteroarylacrylate.
  • the reactive monomer is selected from acrylic acid, a vinyl-pyrrolidinone, acryloyl morpholine, phenoxy acrylate, an alkoxyalkylacrylate, an alkylaryl acrylate, and a heteroarylacrylate.
  • Embodiment 8 The polymer wall system of embodiments 1 or 2, wherein the multi-functional monomer is selected from HDT, EGDA, HDD, DPGDA, TCDDA, HPNDA, TATATO, or PETMP.
  • Embodiment 9 A light modulating device comprising: a first transparent hydroxy activated electrically conductive element; a second transparent hydroxy activated electrically conductive element; a light modulating layer, said light modulating layer comprising a plurality of polymer walls bonded respectively to and between the first transparent hydroxy activated electrically conductive element and the second transparent hydroxy activated electrically conductive element, the polymer walls comprising a silane coupler bonded to the first and second hydroxy activated conductive element; and reactive monomer acrylate units, at least some reactive monomer acrylate units coupled or their polymerized chains entangled with the respective silane coupler.
  • Embodiment 10 The light modulating device of embodiment 9, wherein the reactive monomer acrylate units comprise a monofunctional or multi-functional acrylate unit.
  • Embodiment 11 The light modulating device of embodiment 10, wherein the reactive monomer acrylate units are a mixture of PEA and acrylic acid.
  • Embodiment 12 The light modulating device of embodiment 10, wherein the reactive monomer acrylate units are a mixture of PEA and TCDDA.
  • Embodiment 13 A method for attaching a first substrate to a second substrate, the method comprising: providing a first substrate; activating the first substrate to introduce hydroxy groups to the first substrate; bonding a silane acrylate coupler to the hydroxy activated first substrate; and bonding at least one monofunctional monomer to the silane coupler.
  • Embodiment 14 The method of embodiment 13, wherein the introducing hydroxy groups to the first substrate is selected from ozone plasma treatment, or piranha solution treatment.
  • Embodiment 15 The method of embodiment 13, wherein the piranha solution treatment includes, applying a solution of sulfuric acid and hydrogen peroxide to hydroxylate the substrate surface; rinsing the hydroxylated substrate surfaces with water; rinsing the water rinsed surfaces with acetone; and drying the rinsed hydroxylated substrate surfaces.
  • ITO indium tin oxide
  • the above cleaned ITO substrate was subjected to ozone plasma treatment (UV-1 model UV-Plasma cleaner, (SAMCO, Santa Clara, CA, USA) oxygen flow rate of 0.5 liters/min for 5 min to activate the substrate surface, e.g., increase the surface hydroxy functionalization.
  • UV-1 model UV-Plasma cleaner SAMCO, Santa Clara, CA, USA
  • a piranha etching solution was made by slowly adding 30.0 mL of hydrogen peroxide (3% solution, Kroger Co., Cincinnati, OH, USA) to 30.0 mL of concentrated (95%-98%) sulfuric acid (H2SO4) Millipore Sigma-Aldrich, St. Louis, MO, USA (1:3 ratio of H202:H2S04), carefully stirred and allowed to cool to room temperature.
  • H2SO4 concentrated (95%-98%) sulfuric acid
  • Millipore Sigma-Aldrich Millipore Sigma-Aldrich, St. Louis, MO, USA (1:3 ratio of H202:H2S04
  • a similar sized transparent electrode element (3.0 inches by 1 inches) was submerged within the above described piranha etching solution for less than or equal to 30 seconds, e.g., about 20 seconds.
  • the treated transparent electrode element was rinsed with distilled water and then rinsed with acetone.
  • the treated substrates were then dried under a stream of pressurized air.
  • the activated substrates of the Examples above were soaked in a toluene solution containing 1.5 vol% catalyst such as triethylamine and 0.5 vol% of silane coupler, e.g., methacryloxypropyltrimethoxysilane (Gelest product code: SIM6487.4, CAS: 2530-85-0) for about 45 minutes.
  • the substrates were then rinsed in pure toluene and then the substrates were placed under 25 mmHg vacuum for about 30 minutes to completely evaporate residual solvent.
  • Ex-5 was prepared from a mixture of
  • nematic liquid crystal material QYPDLC-8 Qingdao QY Liquid Crystal Co. Ltd.
  • PEA 2-phenoxyethyl acrylate
  • Ex-1 a test sample was prepared and showed that polymerized PEA has extremely poor adhesion to the non-functionalized substrates. The peel strength was around 0 N/cm, whether or not a photomask was used.
  • Ex-2 a test sample was prepared to demonstrate the effectiveness of silane coupling of the PEA-based polymer to the substrates. Due to silane coupler functionalization of the substrates the peel strength of the PEA-based sample increased significantly to a value of about 2.4 N/cm (FIG. 4).
  • a test sample was prepared including the compartmentalized liquid crystals.
  • a photomask with square pattern having 30 pm wide lines and 200 pm spacings between the said lines has been placed over the sample during UV polymerization of the PEA.
  • the PEA has polymerized to produce polymer walls (51) and liquid crystal-rich compartments (52) has formed between them as shown in FIG. 5. Due to the presence of liquid crystals, the peel strength in this example dropped down significantly to about 0.16 N/cm (FIG. 6).
  • a test sample was prepared. A photomask with square pattern having 30 pm wide lines and 200 pm spacings between the said lines has been placed over the sample during UV polymerization of the PEA with AA.
  • PET-ITO flexible substrate (Elecrysta C100-02RJC5B, Nitto Denko, Osaka, JP) were rinsed with acetone and blow-dried with compressed air.
  • the second substrate was placed on top of the droplet in contact with its conducting layer surface, a roller was then applied to spread the formulation between the substrates.
  • both substrates of the light modulating device with polymer walls were electrically connected by soldering wires to the ITO terminals such that each conductive substrate is in electrical communication with a voltage source, where the communication is such that when the voltage is applied an electric field is generated across the device.
  • the voltage provides the necessary electric field across the device to enable the reorientation of the liquid crystal molecules. Peel strength measurement
  • Peel strength was measured by a tensile force tester using the protocol as described in ASTM D1876 "T-peel test” or also known as “180 degrees peel test” at a rate of 30 cm/min.

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Abstract

L'invention concerne un dispositif de modulation de lumière compartimenté par des parois polymères ayant une adhérence améliorée à des substrats transparents électriquement conducteurs et une cohésion améliorée à l'intérieur desdites parois.
PCT/US2021/024995 2020-03-30 2021-03-30 Structure à paroi polymère améliorée et ses procédés de fabrication WO2021202606A1 (fr)

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JP2022559507A JP2023519964A (ja) 2020-03-30 2021-03-30 改良ポリマー壁構造及びその作製方法
KR1020227033714A KR20220160592A (ko) 2020-03-30 2021-03-30 개선된 폴리머 벽 구조물 및 이를 제조하는 방법
CN202180025838.4A CN115380241A (zh) 2020-03-30 2021-03-30 改善的聚合物壁式结构及其制造方法

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Citations (4)

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Publication number Priority date Publication date Assignee Title
US20060227262A1 (en) * 2003-08-06 2006-10-12 Roel Penterman Liquid-filled composite with supporting memembers covalenty bonded to the substrates
US20100302476A1 (en) * 2007-11-28 2010-12-02 Nippon Sheet Glass Company, Limited Liquid crystal light control device and method for producing the same
US20160154259A1 (en) * 2014-12-02 2016-06-02 Lg Display Co., Ltd. Light controlling apparatus and method of fabricating the same
US20170307915A1 (en) * 2014-09-30 2017-10-26 Seiko Electric Co., Ltd. Light control device and method for manufacturing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060227262A1 (en) * 2003-08-06 2006-10-12 Roel Penterman Liquid-filled composite with supporting memembers covalenty bonded to the substrates
US20100302476A1 (en) * 2007-11-28 2010-12-02 Nippon Sheet Glass Company, Limited Liquid crystal light control device and method for producing the same
US20170307915A1 (en) * 2014-09-30 2017-10-26 Seiko Electric Co., Ltd. Light control device and method for manufacturing the same
US20160154259A1 (en) * 2014-12-02 2016-06-02 Lg Display Co., Ltd. Light controlling apparatus and method of fabricating the same

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