WO1992012219A1 - Dispositif a cristaux liquides disperses dans un polymere, presentant une matrice polymerisable aux ultraviolets et une transmission optique variable, et procede de preparation de ce dispositif - Google Patents

Dispositif a cristaux liquides disperses dans un polymere, presentant une matrice polymerisable aux ultraviolets et une transmission optique variable, et procede de preparation de ce dispositif Download PDF

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Publication number
WO1992012219A1
WO1992012219A1 PCT/US1992/000173 US9200173W WO9212219A1 WO 1992012219 A1 WO1992012219 A1 WO 1992012219A1 US 9200173 W US9200173 W US 9200173W WO 9212219 A1 WO9212219 A1 WO 9212219A1
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Prior art keywords
liquid crystal
ultraviolet radiation
matrix
pdlc
crystal material
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PCT/US1992/000173
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English (en)
Inventor
Stephen A. Miller
William A. Huffman
Laurence R. Gilbert
George F. Vesley
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Minnesota Mining And Manufacturing Company
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Publication date
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to BR9205462A priority Critical patent/BR9205462A/pt
Priority to JP4504497A priority patent/JPH06504387A/ja
Priority to KR1019930702045A priority patent/KR930703416A/ko
Publication of WO1992012219A1 publication Critical patent/WO1992012219A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—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
    • G02F2203/00—Function characteristic
    • G02F2203/30—Gray scale

Definitions

  • This invention relates to a polymer-dispersed liquid crystal device (hereinafter referred to as a "PDLC device") and, more particularly, to a PDLC device which is based on an ultraviolet polymerizable matrix.
  • Devices according to the invention display a selectively adjustable, variable transmission of specular light as a function of applied voltage.
  • This invention also relates to a method for preparing PDLC devices generally.
  • PDLC devices generally comprise droplets of a biaxially birefringent, nematic liquid crystal material dispersed in a transparent polymeric matrix.
  • PDLC devices are of interest because they can be electrically controlled or switched between relatively translucent (i.e. light scattering) and relatively transparent (i.e. light transmitting) states. This occurs because the liquid crystal droplets exhibit birefringence. As a result, the droplets strongly scatter light when they are randomly oriented in the matrix and the PDLC devices appear translucent. However, upon the application of either an electric field or a magnetic field, the droplets become aligned along the direction of the electric/magnetic field vector and more directly transmit light. Alternatively, the droplets can be thermally stressed to induce alignment.
  • the devices appear transparent.
  • PDLC devices switch from a state in which they appear translucent to a state in which they appear transparent.
  • the devices revert to a translucent state.
  • PDLC devices are sometimes described as being switchable between opaque and transparent states. Strictly interpreted, the description of PDLC devices in the "field-off" state as "opaque" is not correct.
  • opaque and translucent have apparently been used synonymously and there seems to be no significant misunderstanding regarding the functional appearance of the devices. More accurately, PDLC devices in the field-off, nonaligned state transmit light, but the light is dispersed to the extent that images viewed through the devices appear cloudy or diffuse. That is, the PDLC devices are translucent. Truly "opaque” devices do not transmit light.
  • PDLC devices have found use as light valves, filters and shutters.
  • the devices have also been used in information display arrangements where it is desirable to have a sharp, rapidly achieved contrast between the translucent and transparent states for addressing purposes such as is required for multiplexing.
  • sharp it is meant that the devices experience a substantial change in the percentage of light incident upon the device which can be specularly transmitted therethrough for a correspondingly small change in the amount of applied voltage. That is, a small change in the voltage (e.g., a change of less than 10 volts) applied to the device causes the device to switch between the transparent and translucent conditions.
  • rapid it is meant that the time required for the device to switch between the transparent and translucent states is very short (on the order of milliseconds) . It is an objective of most presently known
  • PDLC devices to exist in only one of two extreme states (either translucent-off or transparent-on) . These devices do not provide a uniform, variable optical transmission or variable grey scale. Furthermore, these PDLC devices cannot be varied and selectively adjusted from, at one extreme, a translucent off-state (corresponding to about 0% relative transmission) to, at another extreme, a transparent on-state (corresponding to about 100% relative transmission) with an infinite number of intermediate, preferably uniform, specular light transmission levels in between. This inability to provide an infinite number of intermediate light transmission levels is believed to be due, in part, to the objective that the devices switch sharply
  • the devices tend to exist only in these extreme states.
  • Variable grey scale PDLC devices would be useful in numerous applications. If provided in the form of thin, flexible sheets, the devices could be applied to motor vehicle sunroofs cr side windows so that occupants of the motor vehicle could adjust the PDLC device to regulate the amount of specular light passed therethrough. Similarly, the devices could be applied to architectural windows, sloped glazings, skylights, interior glass partitions and the like to provide glare and/or privacy control for occupants of the building.
  • PDLC devices and methods for preparing them have been described both in the scientific and patent literature.
  • a device which suggests a variable grey scale is disclosed in U.S. Patent No. 4,749,261 to McLaughlin et al. and assigned to Taliq Corporation.
  • This patent discloses a shatterproof liquid crystal panel which comprises a pair of transparent boundary surfaces formed of glass or plastic with nematic curvilinearly aligned phase (“NCAP") liquid crystal material disposed therebetween.
  • the NCAP liquid crystal material comprises plural volumes of an optically transparent liquid crystal formed in an optically transparent containment medium such as a polyvinyl alcohol or a latex.
  • the volumes of liquid crystal material may be separate from one another, may be interconnected to one or more volumes, or may include both separate and interconnected volumes.
  • the liquid crystal material may be prepared as an emulsion of liquid crystal and containment medium, the emulsion being subsequently dried (i.e., cured).
  • the liquid crystal material may comprise a plurality of individually formed capsules of liquid crystal in a containment medium.
  • the panel further includes a pair of electrodes and a variable element which can adjust the magnitude of an electric field applied to the liquid crystal material. P.eportedly, by varying the magnitude of the electric field applied across the liquid crystal material, the extent to which light is transmitted through the panel may be varied.
  • the NCAP liquid crystal materials of the McLaughlin et al. patent are made by an emulsion or encapsulation technique which is described more fully in U.S. Patent No. 4,435,047 to Fergason.
  • Emulsion or encapsulation typically involves emulsifying a liquid crystal material with an aqueous phase containing the encapsulating medium, spreading the emulsion onto a substrate, and allowing the aqueous phase to evaporate.
  • Such systems are sensitive to moisture degradation and demand the use of relatively thick, spacer-separated substrates which can be easily coated.
  • FIG. 4 describes a liquid crystal display device which includes a substrate having a thickness of about 10 mils,
  • PDLC devices such as those disclosed herein involve polymerization-induced phase separation, a technique which offers certain advantages over the emulsion or encapsulation process.
  • Polymerization-induced phase separation is a solvent-free approach which results in the formation of structures which are less moisture- sensitive.
  • polymerization-induced phase separation allows for the production of higher molecular weight matrices which have enhanced structural properties so as to impart certain desired characteristics to the matrix.
  • phase separation liquid crystal microdroplets spontaneously form in a polymer matrix upon the separation of the liquid crystal and matrix phases.
  • Phase separation is induced by causing the uncured matrix material to polymerize.
  • a polymerization induced-phase separation in which the uncured matrix material polymerizes upon exposure to ultraviolet (UV) radiation is particularly desirable because these systems are easily handled, do not require two-part formulations (as do epoxy-based systems) , and because the phase separation kinetics can be readily controlled by adjusting the' process parameters.
  • UV ultraviolet
  • U.S. Patent No. 3,935,337 to Taylor More recently, U.S. Patent No. 4,728,547 to Vaz et al. disclosed an optically responsive film comprising liquid crystals dispersed in an UV-curable polymer matrix. Liquid crystal/matrix material was applied between a pair of 20 micron ( ⁇ ) silica microsphere-separated glass plates and then exposed to UV radiation. UV-curable polymer matrices include those based on thiol-ene chemistry.
  • FIG. 1 of the Vaz et al. patent suggests that within the polymer matrix, a uniform distribution of equally sized liquid crystal microdroplets is desirable.
  • the liquid crystal microdroplets should be about 0.1 to 10 ⁇ , preferably 0.5 to l ⁇ in diameter.
  • High intensity UV radiation was used to cure the liquid crystal/matrix system (6 seconds of exposure 3 to 4 inches from a 300 Watt/inch mercury discharge lamp) .
  • the film may be used for information displays, light shutters and the like, applications for which a variable grey scale would be undesirable.
  • U.S. Patent No. 4,834,509 to Gunjima et al. discloses an optical device in which liquid crystal material is uniformly dispersed in a vinyl group- containing matrix that may be polymerized with UV energy.
  • the liquid crystal/matrix blend is disposed between a pair of electrode-bearing substrates.
  • mechanical spacers e.g., glass, plastic or ceramic particles
  • the devices are useful as large area displays, light controllers and light shutters, applications for which a variable grey scale would be undesirable.
  • U.S. Patent No. 4,688,900 to Doane et al. and assigned to Kent State University discloses a light modulating material comprising liquid crystal droplets dispersed in an epoxy or a polyurethane matrix.
  • the light modulating material is disposed intermediate a pair of substrates.
  • the matrix is cured in a phase separation process either thermally, upon exposure to UV light energy, or with a chemical promoter.
  • Relatively thick structures in which the boundary layers (substrates) are separated by spacers and in which equally sized spherical liquid crystal droplets are uniformly dispersed in the matrix are provided.
  • Thermally-cured epoxy-based polymer matrices are also disclosed in U.S. Patent Nos. 4,673,255 and 4,685,771, each to West et al. and each assigned to Kent State University. None of the aforementioned patents assigned to Kent State University is known to exhibit a uniform, selectively adjustable, variable grey scale but rather are useful in information displays, light shutters, and the like.
  • U.S. Patent No. 4,944,576 to Lacker et al. discloses a PDLC device in which microdroplets of a liquid crystal material are dispersed within a photopolymerizable matrix material.
  • the liquid crystal/matrix blend was applied between a pair of spacer-separated, electrode-coated substrates and cured with UV radiation.
  • An electric field, a magnetic field or a mechanical stress is applied during photopolymerization to partially align the liquid crystal microdroplets.
  • the PDLC device performs similarly to known devices but with lower threshold and operating voltages. Lower threshold and operating voltages are typically associated with a sharp transition between the translucent and transparent states which is supported by the failure of FIG. 4 (graphical plots of % transmission v. 100 Hz Signal, rms volts (i.e., voltage)) to describe a variable grey scale PLDC device.
  • U.S. Patent No. 4,938,568 to Margerum et al. discloses various PDLC devices comprising microdroplets of a liquid crystal material dispersed in a photopolymerizable matrix and applied between a pair of electrode-coated, spacer-separated substrates.
  • Marger ⁇ et al. can create a variation in the size of the liquid crystal microdroplets.
  • several different types of PDLC films may be obtained by spatially varying the conditions of polymerization over the film so that the sizes of the liquid crystal droplets are also spatially varied.
  • the exposure intensity is spatially varied by exposing the film through a mask which has a spatial variation in transmissivity.
  • the mask may be at least partially transmissive over its entire area, thereby enabling substantially the entire film to polymerize at about the same time, but at spatially varying polymerization rates corresponding to the spatial variation in mask transmissivity.
  • polymerization may take place in a two-step process by an exposure with the mask in one step, and an exposure without the mask at a different exposure intensity in another step. This technique is based on the observation by Margerum et al. that liquid crystal droplet size may be reduced by increasing the intensity of the UV radiation.
  • FIG. 3 illustrates alternating bands of "large” and “small” liquid crystal droplets which repeat from one edge of the PDLC film to the opposite edge.
  • FIG. 5 schematically illustrates a variation in liquid crystal droplet size through a PDLC film from one major planar surface to the other.
  • the resulting PDLC devices have reduced operating voltages relative to those previously known.
  • a reduction in operating voltage is typically associated with a sharp transition between the transparent on-state and the translucent off-state. Consequently, this patent does not disclose a PDLC device which exhibits a variable grey scale.
  • U.S. Patent No. 4,411,495 to Beni et al discloses a refractive index switchable display cell, the opacity of which may be ' varied by changing the amplitude of an electric field applied across the device.
  • the cell comprises a preformed, commercial porous filter imbibed with a liquid crystal material.
  • the preformed filter serves as a spacer and the device is described as "providing a gray scale."
  • Interest in PDLC devices has spawned a multitude of technical and academic articles.
  • a PDLC device employing a poly(methyl methacrylate) matrix may have a switching voltage of about 200 volts (V)
  • an identical device reportedly having the same droplet size and shape but using an epoxy matrix may have a switching voltage of 20 V.
  • Liquid Crystal Films SPIE, Vol. 1080, Liquid Crystal Chemistry. Physics and Applications (1989) , pp. 53-61 by A. M. Lackner et al. teaches the formation of PDLC devices comprising liquid crystal droplets dispersed in an UV-curable thiol-ene matrix, the liquid crystal/matrix system being applied between a pair of spacer-separated, electrode-coated substrates. Liquid crystal droplet size was reduced by increasing the intensity of the UV radiation. At an intensity of approximately 13 milliwatts/sq. cm (mW/cm 2 ) , a droplet diameter of about 1.0 ⁇ was achieved. The PDLC devices are not reported as exhibiting a variable grey scale.
  • a Light Control Film Composed of Liquid Crystal Droplets Dispersed in an UV-Curable Polymer Liquid Crystal. 1987, Vol. 146, pp. 1-15 by N. A. Vaz et al. discloses a PDLC device comprising submicron size liquid crystal droplets uniformly dispersed in an UV-curable matrix. The photomicrograph of FIG. 1 appears to show liquid crystal droplets of substantially equal size. The liquid crystal/ uncured matrix material is disposed between a pair of spacer-separated, electrode-coated substrates and cured by exposure to UV radiation of 85 mW/cm 2 intensity (50% uncertainty) . PDLC film thickness was typically 27 to 30 ⁇ .
  • the devices are useful for displays and light shutters but do not otherwise exhibit a variable grey scale.
  • the discussion on pages 6 and 7 of the article suggests that the performance of the device illustrated in FIG. 2 has not been optimized and that it would be desirable to have a sharper transition (i.e., the transition between the translucent off-state and the transparent on-state should occur over a smaller voltage range) .
  • UV-polymerizable matrix is advantageous.
  • PDLC devices which make use of such techniques do not exhibit a variable grey scale. Consequently, there is a need for a PDLC device which exhibits a variable grey scale and which employs an UV-polymerizable matrix.
  • the matrix material is typically cured (polymerized) by exposing the uncured matrix material to relatively high intensity UV radiation sources, for example, medium or high pressure mercury or mercury/ enon lamps.
  • relatively high intensity UV radiation sources for example, medium or high pressure mercury or mercury/ enon lamps.
  • Such radiation sources can become quite hot during operation, necessitating the use of elaborate and expensive cooling and temperature control systems.
  • Such radiation sources have also been associated with certain maintenance problems. Accordingly, it would be desirable if PDLC devices could be produced in a method which utilizes relatively low intensity UV radiation to cure the uncured polymer matrix material.
  • the invention relates to a polymer-dispersed liquid crystal device which comprises a multiplicity of droplets of a birefringent, functionally nematic liquid crystal material dispersed in a matrix which comprises the reaction product of ultraviolet radiation polymerizable materials.
  • the device specularly transmits incident light as a function of the magnitude of an electric field applied across the device and has a delta V (" ⁇ V") greater than or equal to 15 volts (V) .
  • ⁇ V may be calculated according to the following equations:
  • V 80+0 is a first applied voltage corresponding to a first percentage of the total incident light transmitted by the device as specular light
  • V 20+0 is a second applied voltage corresponding to a second percentage of the total incident light transmitted by the device as specular light.
  • the "first percentage of the total incident light transmitted by the device as specular light” ( ⁇ %T 80+0 ) is equal to the sum of (a) the percentage of the total incident light transmitted by the device as specular light at 0 applied volts (%T 0 ) and (b) 80% of the difference between (i) the percentage of the total incident light transmitted by the device as specular light at 100 applied volts (%T 100 ) and (ii) %T 0 .
  • the “second percentage of the total incident light transmitted by the device as specular light” ( ⁇ %T 20+0 ) is equal to the sum of (a) %T 0 and (b) 20% of the difference between %T 100 and %T 0 .
  • ⁇ V is at least 20 V, more preferably in the range of 20 to 30 V.
  • devices formed according to the invention exhibit a selectively adjustable and, preferably, unifor TM grey scale.
  • Liquid crystal materials useful in forming the droplets include birefringent materials having at least one nematic mesophase, for example, birefringent chiral nematic and birefringent nematic type, although any liquid crystal material which is suitably birefringent may be used.
  • a liquid crystal material is suitably birefringent if the difference between the ordinary and extraordinary indices of refraction (i.e., the optical anisotropy) is in the range of about 0.01 to O.5..
  • Polymeric matrices in which the liquid crystal droplets may be dispersed preferably comprise reaction products of materials such as monomers, oligomers or reactive polymers which may be polymerized by photoinitiation.
  • Suitable polymer matrix materials include monofunctional and/or multifunctional (meth)acrylates; allyl or
  • (meth)aerylated oligomers of polyurethanes, polyesters, polyols, polybutadienes, or epoxies; and thiol-enes are also known. Formation of a device according to the invention is typically carried out in a polymerization-induced phase separation process.
  • the liquid crystal material and the uncured polymer matrix material are preferably combined in a ratio of 40:60 to 60:40 (parts by weight) respectively.
  • the liquid crystal/polymer matrix exists as a film which preferably has a thickness in the range 5 to 25 microns ( ⁇ ) , more preferably 10 to 25 ⁇ , and most preferably 15 to 21 ⁇ , so as to ensure that the device can be fully switched at an applied voltage of 120 V or less.
  • the device may further comprise a pair of electrodes (at least one of which is partially transparent) adjacent to the device, the electrodes being connected to a variable power supply.
  • the electrodes may be provided in the form of an at least partially transparent metal or metal alloy (e.g. tin, gold, silver, indium oxide, indium tin oxide as well as other transition metals or transition metal oxides) that can be coated onto a substrate such as glass or a plastic.
  • Devices according to the invention are useful in conjunction with, for example, motor vehicle sunroofs or architectural windows.
  • the vehicle or building occupants may selectively adjust the amount of specular light transmitted through the device so as to satisfy their particular desires, such as reducing the amount of glare.
  • the invention also relates to a process for preparing a PDLC material.
  • the process includes the steps of:
  • the radiation source is a fluorescent lamp. It may also bs useful to control the temperature of the solution prior to and during polymerization to prevent premature temperature- induced phase separation of the liquid crystal and radiation polymerizable materials.
  • the UV radiation exposure may be carried out in two stages such that the liquid crystal material at least partially phase separates from the ultraviolet radiation polymerizable material in the first stage and formation of the PDLC material is completed in the second stage as the matrix fully cures.
  • the intensity of the UV radiation in the second stage may be greater than that used in the first stage.
  • the resulting PDLC material has a microstructure which permits a device formed therewith to have a ⁇ V of greater than or equal to 15 V.
  • a filler such as finely divided silica may enhance the formation of a PDLC material.
  • FIG. 1 is a schematic view, partially in cross-section, of a PDLC device according to the invention
  • FIG. 2 is a graphical plot of % transmission v. applied voltage for a PDLC device according to the invention and for a presently known
  • FIG. 3 is a schematic drawing illustrating a method for producing PDLC devices according to the invention.
  • FIG- 4 is a photomicrograph (enlarged
  • FIG. 5 is a photomicrograph (enlarged 250OX) of a PDLC device formed according to the invention.
  • This invention relates to both a polymer dispersed liquid crystal (“PDLC”) device which displays a variable grey scale and to a method for making PDLC devices in general.
  • PDLC polymer dispersed liquid crystal
  • variable grey scale it is meant that the amount of specular light which is passed or transmitted through the device can be selectively and, preferably, uniformly adjusted to satisfy the demands of particular users.
  • a translucent off-state corresponding to about 0% relative light transmission
  • a transparent on-state corresponding to about 100% relative light transmission
  • a user of the device can selectively adjust the same so that it transmits any desired amount of specular light.
  • the degree of light scattering through the device may be adjusted by varying the magnitude of an electric field applied across the device.
  • the device 10 comprises a PDLC film 12 having a multiplicity of liquid crystal droplets 14 dispersed in a polymeric matrix 16.
  • Liquid crystal materials useful in forming the droplets 14 are functionally nematic and suitably birefringent. Typically they have at least one nematic mesophase and display positive dielectric anisotropy and/or positive diamagnetic anisotropy in the polymer matrix 16.
  • functionally nematic it is meant that the liquid crystal material is conventionally considered to be “nematic” (e.g., birefringent nematic type, birefringent chiral nematic type, as well as mixtures thereof) or, if not considered “nematic” in the conventional sense, has the capacity to function as a nematic material (e.g., cholesteric types and mixtures thereof) .
  • liquid crystal material is "suitably birefringent” may be determined with reference to its optical anisotropy ( ⁇ n) .
  • Liquid crystal materials useful in. the invention are biaxially birefringent and have essentially rod- shaped molecules. The major axis of a liquid crystal molecule is regarded as its optic axis.
  • a body of liquid crystal molecules in the nematic mesophase displays an ordinary index of refraction (n 0 ) perpendicular to the optic axes of the molecules and an extraordinary index of refraction (n e ) parallel to the optic axes.
  • n e and n 0 the optical anisotropy or ⁇ n
  • ⁇ n the optical anisotropy
  • ⁇ n the optical anisotropy
  • ⁇ n the optical anisotropy
  • ⁇ n the optical anisotropy
  • ⁇ n the optical anisotropy
  • ⁇ n the optical anisotropy
  • ⁇ n the optical anisotropy
  • n 0 should be closely matched to the index of refraction of the polymer matrix material (e.g., + 0.02, preferably, +0.002) so as to enhance the transparency of the PDLC device in the on-state.
  • the polymer matrix material should be optically isotropic so as to minimize undesirable birefringence effects of the liquid crystal material.
  • liquid crystal materials useful in the invention include LICRISTAL E7, BL006, BL009, ML1005, ML1008, 17151, 17153,
  • Polymeric matrix materials 16 in which the liquid crystal droplets may be dispersed preferably comprise reaction products of materials such as monomers, oligomers or reactive polymers which may be polymerized by photoinitiation.
  • materials such as monomers, oligomers or reactive polymers which may be polymerized by photoinitiation.
  • photoinitiation systems involving different chemistries are known and may be used in the invention to cure the uncured matrix material.
  • Suitable techniques for providing polymer matrix 16 include radical polymerization of monofunctional and/or multifunctional alkyl acrylates and methacrylates.
  • Useful monofunctional aerylate monomers include, for example, unsaturated aerylate esters of non-tertiary alkyl alcohols, the molecules of which have from l to about 14 carbon atoms. Included within this class of monomers are, for example, isocctyl acrylat ⁇ , " isononyl acrylat ⁇ , 2-ethyl-hexyl aerylate, decyl aerylate, dodecyl acrylate, n-butyl acrylate, and hexyl acrylate.
  • the alkyl acrylate monomers may be used to form homopolymers, copolymers or- higher order polymers for the polymer matrix material or they may be copolymerized with polar monomers.
  • the polar copolymerizable monomers may be selected from monomers such as acrylic acid, itaconic acid, hydroxyalkyl acrylates, cyanoalkyl acrylates, acrylamides or substituted acrylamides, N-vinyl pyrrolidone, N-vinyl caprolactam, acrylonitrile, vinyl chloride or diallyl phthalate.
  • Non-polar monomers such as isobornyl acrylate, dicyclopentadiene acrylate, etc. are also suitable for use in the invention.
  • Multifunctional acrylates include 1,6 hexanadioldiacrylate, trimethylpropane triacrylate, propylene glycol dimethacrylate etc. can be used as major components of the matrix or alternatively may be incorporated at lower levels (e.g. 0.05 to 2 parts by weight of the total monomer content) to function as crosslinkers.
  • Suitable aerylated polybutadiene is SARTOMER CD 5000 (commercially available from Sartomer Co.).
  • a useful acrylated polyester is SARTOMER 609 (from Sartomer Co.) and a suitable acrylated polyurethane is SARTOMER 9610 (Sartomer Co.) .
  • Blends of the reactive oligomers and the alkyl ester monomers described above may be used.
  • Blends may be useful in adjusting certain properties such as the refractive index of the polymer matrix material, the solubility of the liquid crystal material in the polymer matrix material, or the viscosity of the liquid crystal/polymer matrix system.
  • the ratio of oligomer to monomer will depend on the physical properties of the oligomer and may vary from neat monomer to neat oligomer.
  • the mixture At the temperature at which the mixture is to be applied to a substrate (if a substrate ' is employed) (typically a temperature in the range from about 60° to 120°F (about 16° to 49°C)), the mixture should have a viscosity which renders it coatable and the liquid crystal material should remain soluble therein.
  • the polymer matrix material may also contain a photoinitiator to aid in polymerization of the monomers.
  • Photoinitiators that are useful for polymerizing the acrylate monomer include the benzoin ethers, substituted benzoin ethers such as benzoin methyl ether or benzoin isopropyl ether, substituted acetophenones such as 2,2-diethoxy-acetophenone, and 2,2-dimethoxy-2-phenyl-acetophenone, substituted alpha-ketols such as 2-methyl-2-hydroxypropiophenone, aromatic sulphonyl chlorides such as 2-naphthalene sulphonyl chloride, and photoactive oximes such as 1-phenyl-l,l-propanedione-2-(O-ethoxycarbonyl) oxime.
  • the amount of photoinitator is from about 0.01 part to about 10 parts, per 100 parts monomer weight.
  • radical polymerization initiating systems which may be used include 3,4-bistrichloro- methyl-6-substituted-s-triazines, and benzophenone with an amine, for example, benzophenone and p-(N,N-diethylamino) ethyl benzor-ate.
  • Reactants useful for the polymeric matrix material also include UV polymerizable systems based on thiol-ene chemistry.
  • An. example of such a system is based on the reaction products of triallyl isocyanurate and/or other suitable mono-, di- and triallyl ethers or esters, and one or more suitable polythiol oligomers selected from the group consisting of Z[OCO(CH 2 ) n SH] m , wherein
  • UV polymerizable systems based on thiol-ene chemistry comprise, in major part, monofunctional or multifunctional allyl compounds containing an hydroxyl group reacted with a mono- or multifunctional isoeyanate, which reaction product is subsequently reacted with one or more suitable polythiol oligomers having the structure described above.
  • This UV polymerizable system may include other allyl functional monomers.
  • the system may optionally include as a third material, a mono-, di-, or triallyl compound which reacts with the polythiol.
  • the polymer matrix material may also comprise a blend of monofunptional (meth)acrylates, and/or multifunctional (meth)acrylates, and the polythiol oligomers described above.
  • the proportions of the various allyl and/or (meth)acrylate compounds noted above in the several different systems and the polythiol are selected so as to produce a relatively high molecular weight polymer.
  • the stoichiometric ratio of allyl and/or (meth)acrylate compound to polythiol is in the range of about 1.5 to 2.5, more preferably, about 2.
  • Examples of useful polymer matrices based on thiol-ene chemistry include NOA 65 and NOA 68 (each commercially available from Norland Products, Inc. New Brunswick, New Jersey) which include photoinitiators.
  • the liquid crystal material may also be dispersed in a polymer matrix formed by the polymerization of a functional epoxy monomer or oligomer, and a polyol.
  • a functional epoxy monomer or oligomer and a polyol.
  • These systems can be photoinitiated by diaryl iodiu or triaryl sulfonium salts such as triphenyl sulfonium hexafluoroantimonate.
  • photoactive organometallic compounds known to catalyze epoxy polymerization may be used, such as those disclosed in European patent publication no. 109,851.
  • a suitable epoxy resin mixture is, for example, a blend of EPON 828 (commercially available from Shell Chemical Co.) and trimethylene glycol, in a ratio of about 4:1 parts by weight and about 0.5 part (based on total epoxy content) of an UV energy activated curative such as FC-508 (commercially available from Minnesota Mining and Manufacturing Co.).
  • Various other monomers may be incorporated into the polymer materials described hereinabove to usefully adjust the physical characteristics thereof.
  • other monomers may be included to adjust the refractive index of the polymer matrix material relative to the refractive index of the liquid crystal material.
  • the polymer matrix material should be selected such that the liquid crystal material is soluble in the photopolymerizable mixture, although an application of heat may be necessary to achieve this. Upon polymerization of the mixture, the liquid crystal material should become insoluble in the polymer matrix and form droplets.
  • Formation of a PDLC film according to the invention is typically carried out in a phase separation process.
  • Polymerization induced-phase separation has been found to be useful when the uncured polymer matrix material is miscible with a low molecular weight liquid crystal material.
  • Liquid crystal droplets form when the solubility of the liquid crystal material in the polymer matrix material decreases as a result of an increase in the molecular weight of the matrix material which occurs when the matrix material polymerizes to form a continuous phase. As the solubility of the liquid crystal material decreases, it phase separates from the polymer matrix material and forms droplets. The droplets increase in size until the polymer matrix material locks in the final droplet morphology.
  • the liquid crystal droplets should be present in a range of sizes (diameters) extending from about 0.1 to about 10 microns ( ⁇ ) , preferably about 0.8 to 5 ⁇ , and more preferably about 1 to 3 ⁇ .
  • the polymerization is carried out in the presence of the liquid crystal material thereby enabling tailoring of the polymer matrix material in terms of molecular weight, crosslink density, liquid crystal compatibility, and adhesion.
  • Premature phase separation refers to an unwanted, thermally-induced phase separation that occurs before the "desired” phase separation (which results from a decrease in the solubility of the liquid crystal material as explained above) .
  • Premature phase separation can be reduced by heating the liquid crystal and uncured polymer matrix materials to form a homogeneous solution and further by continuing to apply heat prior to and during curing. With the appropriate selection of the liquid crystal and polymer matrix materials, it is believed that control of premature phase separation by temperature regulation results in the production of PDLC devices having larger numbers of smaller diameter liquid crystal droplets than is otherwise achievable.
  • Phase separation of the liquid crystal material upon polymerization of the uncured polymer matrix material to form a dispersion of droplets in the matrix material may be enhanced by the addition of a filler such as finely divided silica having a B.E.T. surface area of at least 10 m 2 /g (preferably 50 to 400 m 2 /g) to the polymerizable matrix material prior to the addition of the liquid crystal material.
  • a filler such as finely divided silica having a B.E.T. surface area of at least 10 m 2 /g (preferably 50 to 400 m 2 /g)
  • Fumed or precipitated silica of either the hydrophobic or hydrophilic type may be used. It is believed thar tha presence of the silica changes the solubility of the liquid crystal material in the uncured polymer matrix material thereby desirably altering the dynamics of phase separation.
  • the amount of silica will vary depending on the particular liquid crystal and polymer matrix materials. Generally about 0.1 to 5 (preferably 0.5 to 2) weight percent silica, based on the weight of the polymer matrix material is effective.
  • An example of a commercially available hydrophobic fumed silica which is useful in the invention is AEROSIL R 972 (available from Degussa Corp.).
  • An example of a commercially available hydrophilic fumed silica is
  • CAB-O-SIL M-5 (available from Cabot Corp., Cab-O-Sil Division, Tuscola, II.).
  • the liquid crystal material and the polymer matrix material are provided in approximately equal parts by weight although the parts by weight ratio of the liquid crystal material to the polymer matrix material can vary from 40:60 to 60:40. If the liquid crystal material comprises less than about 40 parts by weight or more than about 60 parts by weight, then one or more of the following may be materially adversely, affected: switching performance, adhesion, environmental stability and cost.
  • the PDLC film 12 may be provided in free-standing form, in many applications it will be desirable to provide a sandwichlike construction in which the PDLC film 12 is interposed between a pair of first and second substrates 18 and 20, respectively. It will be understood that the device 10 may be provided with only a single substrate if, for example, the device is to be applied to a motor vehicle sunroof or an architectural window in which case the sunroof or the window have a function analogous to that of the second substrate.
  • At least one of the substrates 18 and 20 is at least partially transparent to allow incident visible light to pass therethrough.
  • One of the substrates (preferably the one on which light first impinges) may be modified to have selective light transmission characteristics, for example, to selectively transmit light of a wavelength corresponding to a certain color of the visible spectrum, ultraviolet light or infrared light.
  • Materials suitable for the substrates 18 and 20 include glass (which may be tempered) and plastics such as polyester (or a copolyester) , polyethersulfone, polyimide, polyethylene terephthalate, polyethylene naphthalate, poly(methyl methacrylate) , and polycarbonate.
  • the substrates may be treated so as to enhance their abrasion and scratch resistance.
  • the substrates are typically about 25 to 50 ⁇ thick for flexible, durable constructions, although they may range in thickness from 1 ⁇ to greater than 250 ⁇ . If glass is employed for at least one of the substrates, a thickness in excess of 250 ⁇ may be useful.
  • the device 10 may further comprise first and second electrodes 22 and 24, respectively, which are positioned intermediate the substrates 18 and 20 and the PDLC film 12.
  • the electrodes 22 and 24 are connected to, respectively, first and second leads 26 and 28 (for example, a conductive adhesive tape or the like) which, in turn, are electrically connected to a variable power supply 30, preferably of the alternating current type.
  • the frequency of the alternating field should be in the range of 40 to 100 hertz.
  • the field should alternate sufficiently rapidly so that a human observer of the device cannot perceive flickering.
  • the optic axes of the liquid crystal droplets become aligned. If the refractive indices of the liquid crystal material and the polymer matrix material have been closely matched, the film 12 will switch between the translucent off-state and the transparent on-state.
  • the electrodes 22 and 24 may be formed of various materials including chromium, indium oxide, tin oxide, stainless steel, indium tin oxide, gold, silver, copper, aluminum, titanium, cadmium stanate, other transition metal oxides, and mixtures and alloys thereof. With the use of certain electrode materials (e.g. silver) it may be desirable to environmentally protect the same with a thin. passivating dielectric layer. The use of such a protective layer may enhance the ability of the electrode to resist thermal, chemical, moisture and/or ultraviolet-induced degradation. An example of such a protective layer is A1 2 0 3 .
  • the electrodes must be capable of receiving an electrical input from the leads 26 and 28 and transmitting the same so as to apply an electric field across the film 12.
  • the electrodes 22 and 24 are positioned adjacent to opposite sides or surfaces of the film 12 and extend over, across and parallel to the same.
  • At least one of the electrodes 22 and 24 preferably comprises a conductive coating that is at least partially transparent to visible light, although electrodes which provide preferential light transmission characteristics, such as color tint or ultraviolet or infrared filter, may be used.
  • the electrodes 22 and 24 need not be equally transparent.
  • At least one of the electrodes should provide a visible light transmission of at least 1%, preferably at least 10%, and more preferably at least 50%.
  • the electrode coating should have a conductivity greater than 0.001 mhos per square.
  • the electrode material may be coated or otherwise applied to the first and second substrates 18 and 20.
  • Maximum light transmission through the device is determined by selection of material used for the electrode and the thickness of the coating. Typically, maximum light transmission ranges from about 30% to about 80%.
  • a user of the device 10 manipulates and selectively adjusts the variable power supply 30 to vary the magnitude of the electric field applied across the film 12 until the device 10 transmits the desired amount of specular light, the amount which is desired being dependent on the particular situation.
  • the thickness of the PDLC film 12 influences at least in part its optical characteristics.
  • the film has a thickness in the range of about 5 to 25 ⁇ , more preferably in the range of about 10 to 25 ⁇ , and most preferably in the range of about 15 to 21 ⁇ . If the film thickness exceeds about 25 ⁇ , the initial voltage at which the device 10 begins to switch may be too high for effective use in relatively low voltage environments (for example, an automobile) or the device may require increased amounts of power to switch between the translucent off-state and the transparent on-state.
  • the maximum voltage required to fully switch the film should be less than 120 volts (V) , preferably less than 100 V, and most preferably between about 40. to 60 V. (All voltages referenced herein are reported as root mean square (RMS) values.)
  • the device 10 may appear transparent even in the off-state (i.e., without any voltage being applied) .
  • Devices in which the PDLC film thickness is about 5 to 10 ⁇ may also be useful in constructions where one of the electrodes is fully reflective and the PDLC film functions as an anti- reflection layer that can be transitioned between the translucent and transparent states at a relatively low applied voltage.
  • An example of such a device is a membrane switch bearing a reflective pad in a contrasting color relative to the switch background and in which the pad repeatedly cycles between the translucent and transparent states when touched so as to change visibility in low light environments.
  • the desired thickness of the PDLC film is also related to the difference between the ordinary (n 0 ) and extraordinary (n e ) indices of refraction of the liquid crystal material. If the difference is in the range of about 0.22 to about 0.26, a PDLC film thickness in the range of 15 to 21 ⁇ is preferred. If the index of refraction difference is less than 0.22, then the film may need to have a thickness greater than 21 ⁇ . Alternatively, if the index of refraction difference is greater than 0.26. then the film may be comprised of a thickness less than 15 ⁇ . (The relationships between the index of refraction and the PDLC film thickness assume a constant droplet structure.)
  • Whether a particular device exhibits a variable grey scale within the scope of the invention may be determined with reference to a graphical plot of the percentage of total light incident on the device which is transmitted unscattered therethrough (i.e., specular light) (referred to herein at times as “% transmission” or “%T”) as a function of the voltage which is applied across the PDLC film. More particularly, whether a device exhibits a variable grey scale m be determined with reference to the voltage differential required to change the transmissivity of the device from a first value to a second value.
  • Whether a PDLC device exhibits a variable grey scale is determined as follows:
  • the % transmission of the device is measured at 0 applied volts (referred to herein at times as “%T 0 ”) and 100 applied volts (referred to herein at times as M %T 100 ”) .
  • the % transmission at 100 V was selected for measurement since, for many devices, a graphical plot of %T vs. applied voltage shows a slope of about 0 at that portion of the plot. For those devices in which the %T has not reached a plateau (i.e., the slope is not zero), 100 V provides a convenient reference point.
  • the difference between %T 100 and %T 0 is calculated, this difference sometimes being referred herein to as " ⁇ %T” or "the total change in % transmission" (“the total change in %T”) .
  • ⁇ %T 80 M and ⁇ T% 20 are then calculated.
  • the %T at 0 applied volts (%T 0 ) is then added to each of ⁇ %T 80 and ⁇ %T 20 , the two sums sometimes being referred to herein as, respectively, “ ⁇ %T 80+0 " and " ⁇ %T 20+0 .”
  • ⁇ i ⁇ e applied voltages corresponding to ⁇ %T 80+0 and ⁇ %T 20+0 are then determined, these values sometime being referred to herein as, respectively, V 80+0 and V 0+0 .
  • the voltage differential between V 80+0 and V 20+ o (referred to herein at times as ⁇ V) is then calculated.
  • a variable grey scale is found when ⁇ V is greater than or equal to 15 V, more preferably greater than or equal to 20 V, and most preferably in the range of 20 to 30 V. Device performance may be negatively materially affected if ⁇ V is greater than about 60 V.
  • FIG. 2 a graphical plot of %T as a function of applied voltage, the performance of a PDLC device according to the invention is shown as the curve labeled with the reference letter A.
  • This particular device has a %T 0 of about 3% (i.e., a 3% transmission at 0 applied volts corresponding to the translucent off-state) and a %T 100 of about 97% (i.e, a 97% transmission at 100 applied volts corresponding to the transparent on-state) .
  • the ⁇ %T (%T 100 -%T 0 ) of the "curve A" device is about 94% (i.e., 97% - 3%).
  • the applied voltage corresponding to ⁇ %T 80+0 i.e, 78.2%
  • the applied voltage corresponding to ⁇ %T 20+0 i.e, 21.8%
  • the difference between the two applied voltages i.e, ⁇ V) is 22 V (44 V - 22 V) .
  • the performance of a presently known device is also illustrated in FIG. 2 as the curve labeled with the reference letter B.
  • the data used to prepare curves A and B in FIG. 2 were normalized so that the performance of the two devices could be fairly compared on the same graph. Data normalization is a frequently used analytical technique and is well understood by those skilled in the art. In order to simplify the calculations necessary to derive ⁇ V, it is preferred that the data be normalized to yield a maximum transmission (i.e, a %T of 100%) at 100 V. In the preparation of FIG. 2, however, the data were normalized to yield a maximum transmission at 120 V.
  • the presently known device is manufactured by and commercially available from Ajinomoto Co., Inc., Tokyo Japan. Using the same method of calculation as described above, the ⁇ V of the Ajinomoto device is about 8. volts. A ⁇ V of less than 15 V is desired in applications where sharp switching (such as for display arrangements or multiplexing) is important. In these devices, it is desirable to minimize both ⁇ V and the threshold voltage (i.e, the minimum applied voltage at which the device begins to switch between the translucent and transparent states) .
  • the power needed to operate the device is reduced because it begins to switch at a lower voltage and because it switches more sharply (i.e., it switches over a smaller voltage range or ⁇ V) .
  • the cost of the drive circuitry is also a major factor in the overall performance of the display device.
  • a saturation voltage i.e., the voltage required to achieve a maximum % transmission
  • a saturation voltage of 15 V or less is preferred. Such considerations are important where it is desirable to have sequential addressing of certain areas (e.g., pixels in a display device).
  • variable grey scale devices In addition to a voltage differential of at least 15 V, variable grey scale devices preferably exhibit a uniform appearance as the voltage is varied between the threshold voltage (corresponding to the translucent off-state) and the maximum voltage (corresponding ro the transparent on-state) . That is, the relative translucent/transparent appearance should be substantially uniform across the entire PDLC device.
  • a PDLC device according to the invention will display a uniform appearance if it has a ⁇ V of at least 15 V. In those PDLC devices which are presently known and which do not display a variable grey scale, the transition between the translucent and transparent states is uneven and non-uniform. These devices tend to have a blotchy appearance while transitioning.
  • the ability to achieve a variable grey scale device having a uniform appearance during transition is also related to the structure of the liquid crystal droplets. That is, a range or variation in the size or diameter of the liquid crystal droplets positively contributes to the provision of a PDLC device which uniformly transitions between the translucent and transparent conditions.
  • Other characteristics of PDLC devices are also related to the attainment of a device which has a uniform translucent/transparent appearance.
  • the PLDC device comprising liquid crystal droplets dispersed in a polymer matrix material should be of substantially equal thickness. While this condition is necessary to achieving a uniform appearance, it is not sufficient.
  • FIG. 3 there is shown a schematic illustration of one method for producing PDLC devices according to the invention.
  • the first and second substrates 18 and 20 are formed of the same material although it will be understood that the substrates may be different.
  • a large (e.g., 60 inch (152 cm) width) roll 32 of a suitable, flexible substrate material is provided and has applied thereto an at least partially transparent conductive electrode to provide a roll 34 of electrode-coated substrate.
  • the conductive electrode may be any of the materials described hereinabove and may be applied to the substrate roll 32 by chemical vapor deposition, vacuum metalization, sputter coating or other similar techniques as are well known in the industry, the application step being identified generally by the reference numeral 36.
  • Separate rolls 34 of electrode-coated substrate are mounted on upper and lower rotatable spindles 38 and 40. In production, the separate rolls 34 correspond to, respectively, the first and second substrates 18 and 20.
  • the first and second substrates 18 and 20 with the first and second electrodes 22 and 24 having been applied thereto as described above are supplied to upper and lower nip rollers 42 and 44 of a precision, two roll nip coater to bring the electrode-coated surfaces of the substrates into facing relationship.
  • Nip rollers 42 and 44 may be heated, if necessary, to prevent premature phase separation of the liquid crystal and polymer matrix materials.
  • a pump 46 feeds liquid crystal/uncured polymer matrix material blend from a reservoir 48 to the nip rollers 42 and 44 by way of conduit 50. The gap between the nip rollers 42 and 44 is adjusted so as to provide the desired PDLC film thickness. After exiting from the nip rollers, the temperature of the sandwichlike construction comprising the first and second substrates with the liquid crystal/unpolymerized matrix material therebetween is maintained (to prevent premature temperature-induced phase separation) until it is passed between two opposed banks 52 and 54 of fluorescent, low intensity UV lamps in order to polymerize the matrix material.
  • UV lamp bulbs with different spectral responses are commercially available and may be used.
  • the polymerization chemistry of matrix material and the absorption characteristics of the photoinitiator may influence bulb section.
  • the PDLC device 10 may be collected in a rolled form 56 for ease of handling.
  • the method described above for manufacturing PDLC devices employs relatively low intensity UV radiation sources having a continuous emission spectrum, where a major portion of the energy output of the source preferably falls within at least a part of the wavelength range of 280 to 450 nanometers (nm) .
  • An example of such an ultraviolet radiation source is a fluorescent lamp. Fluorescent lamps are generally understood to have two kinds of spectral power emission. One kind is a continuous spectrum provided by the fluorescent phosphor. The second kind comprises narrow bands of energy emitted by the mercury component of the lamp. Thus, a fluorescent lamp. Fluorescent lamps are generally understood to have two kinds of spectral power emission. One kind is a continuous spectrum provided by the fluorescent phosphor. The second kind comprises narrow bands of energy emitted by the mercury component of the lamp. Thus, a
  • continuous emission spectrum is distinguished from the narrow band cr line spectra afforded by other radiation sources such as high pressure mercury discharge lamps.
  • radiation sources such as high pressure mercury discharge lamps.
  • Known PDLC production techniques utilize relatively high intensity UV radiation sources such as mercury or mercury/xenon discharge lamps.
  • Preferred low intensity fluorescent lamps have an emission spectrum in the range of 280 to 450 nanometers (nm) .
  • the emission spectrum of the UV radiation source is preferably selected so as to match the. absorption spectrum of the photoinitiator, thereby maximizing absorption of the UV radiation by the photoinitiator and accelerating the curing reaction (i.e., polymerization of the uncured matrix material) .
  • Each of fluorescent lamp banks 52 and 54 may comprise a single low intensity fluorescent lamp or a plurality thereof arranged sequentially. Although an arrangement involving a pair of opposed fluorescent lamp banks (such as illustrated in FIG. 3) is preferred, the lamps may be oriented to irradiate only one side of the substrate and liquid crystal/uncured polymer matrix material sandwich construction.
  • the average radiation intensity of each of the fluorescent lamp banks is in the range of about 0.25 to 10 mW/cm 2 (more preferably in the range of about 0.5 to 5 mW/cm 2 ) .
  • the total radiation received by the sandwich construction be in the range of about 100 to 1500 mJ/cm 2 (50 to 750 mJ/cm 2 per side) .
  • the particular radiation intensity and total energy exposure requirements will vary depending on the liquid crystal, initiator and polymer matrix materials.
  • the polymerizable material which provides the polymer matrix sufficiently gels to "lock in” the final liquid crystal droplet morphology. It is believed that once the uncured matrix material has received about 30 mJ/cm 2 of UV radiation per side (for example a 30 second exposure to radiation having an intensity of about 1 mW/cm 2 per side) , the polymer matrix material will have sufficiently gelled or set to allow for the use of higher intensity UV radiation.
  • a "two stage low intensity” UV radiation approach may be used in which a "first stage” having a radiation intensity of less than or about 3 mW/cm 2 is followed by a “second stage” having a radiation intensity of less than about 10 mW/cm 2 but greater than that used in the "first stage," both sides of the construction typically being exposed in each stage.
  • the rate of polymerization or curing of the matrix material may be accelerated by exposing one side of the partially cured (i.e., partially phase separated) system to "high intensity" UV radiation, for example, radiation having an average intensity of about 20 to 200 mW/cm 2 (total energy exposure in the "high intensity” stage of about 200 to 1500 mJ/cm 2 ) .
  • high intensity UV radiation for example, radiation having an average intensity of about 20 to 200 mW/cm 2 (total energy exposure in the "high intensity” stage of about 200 to 1500 mJ/cm 2 ) .
  • the actual radiation intensity and exposure requirements will vary with the liquid crystal and polymer matrix materials.
  • the use of low intensity UV radiation sources, as opposed to higher intensity UV sources, offers several advantages.
  • low intensity fluorescent lamps (unlike the presently used high intensity, medium or high pressure mercury and mercury/xenon radiation sources) operate at lower temperatures thereby reducing or eliminating the need for elaborate and expensive cooling systems. Infrared heating of the sample is minimal; elaborate light filters are not needed to control cure parameters. Also, low intensity fluorescent lamps can be immediately restarted following a production shut-down (unlike the mercury and mercury/xenon sources) . As noted hereinabove, it may be desirable in certain applications to provide a PDLC device comprising a film which is bonded to only one substrate or comprising a free-standing film.
  • the process described above is employed except that the substrate supplied from the lower spindle 40 to the lower nip roller 44 is a 25 ⁇ polyester film which has not had electrode material applied thereto. Once the uncured polymeric matrix material has been polymerized upon exposure to UV radiation, the untreated polyester film is peeled away. In the case of a free-standing PDLC film, neither substrate in the above described process is provided with electrode material. After the matrix material has polymerized upon exposure to UV radiation, both substrates are removed.
  • the device may be applied to a surface such as a motor vehicle sunroof, a motor vehicle side window, or an architectural window with, for example, a suitable adhesive.
  • the adhesive is optically transparent.
  • a user of the variable grey scale PDLC device 10 can selectively adjust the amount of specular light transmitted therethrough.
  • the device 10 can be adjusted to have 0% relative transmission, 100% relative transmission, or an infinite number of intermediate specular light transmission levels.
  • the device preferably has a uniform, even appearance.
  • a PDLC device was formed as described below. Equal parts by weight of LICRISTAL E7 liquid crystal material and N0A65 polymer matrix material were combined with heating and stirring until the liquid crystal material completely dissolved. The liquid crystal/uncured polymer matrix material blend was poured between a pair of 25 ⁇ thick polyester films which previously had been coated with a silver electrode material on one surface of each film. The two films were held with their electrode-coated surfaces in facing relationship by the nip rollers of a precision two roll nip coater. The gap between the nip rollers was set to provide a liquid crystal material/uncured polymer matrix material film thickness of 15 to 18 ⁇ .
  • the uncured polymer matrix material was polymerized by positioning the sandwichlike construction comprising the two electrode-coated substrates and the liquid crystal material/unpolymerized matrix material between a pair of opposed banks of fluorescent black light phosphor lighting elements, each bank being positioned to illuminate one of the polyester films. Lighting elements having a spectral distribution between 300 to 400 nm and a maximum output a 351 nm were employed.
  • the lighting elements were adjusted so as to provide an average intensity of 1 to 2 mW/cm 2 through each electrode-coated polyester film (i.e., per side) .
  • Each side of the sandwichlike construction received a total energy exposure of 100 millijoules/sq. cm (mJ/cm 2 ) .
  • the construction as a whole was exposed to a total energy of 200 mJ/cm 2 .
  • the level of incident radiation was determined with an EIT low intensity UVIMAP radiometer or UVIRAD radiometer each having a spectral response in the range of 300 to 400 nm and a maximum response at 358 nm.
  • Electrically conductive adhesive tape was secured to a portion of each electrode-coated substrate that had not had liquid crystal/uncured matrix material applied thereto. Each tape was then connected to an alternating current (AC) power supply having a variable voltage output.
  • AC alternating current
  • a series of PDLC devices was prepared as described above in the general preparation except that the particular liquid crystal material employed was varied as shown below in Table 1.
  • the average intensity of the UV radiation was 1.1 mW/cm 2 per side.
  • the average intensity of the UV radiation was 2 mW/cm 2 per side and the total energy to which the entire structure was exposed was 300 mJ/cm 2 (150 mJ/cm 2 per side) .
  • the average intensity was 2 mW/cm 2 per side and the total energy was 200 mJ/cm 2 (100 mJ/cm 2 per side) .
  • each PDLC device was evaluated by measuring the applied voltage necessary to provide various levels of specular light transmission through the device and graphically plotting the data to provide a %T v. applied voltage curve as described above.
  • the curve labeled with the reference letter A in FIG. 2 is based on an evaluation of the PDLC device of example 2.
  • specular transmission (%T) for a particular applied voltage was measured with a Perkin-Elmer LAMBDA 9 spectrophotometer having an integrating sphere. Measurements were made at a wavelength of 550 nm. The acceptance angle of the optical system was between 3° and 4°. PDLC samples were switched with a VARIAC variable AC power supply operating at a frequency of 60 hz.
  • Table 1 reports values for ⁇ V, as described more fully hereinabove.
  • liquid crystal materials are identi ied by their commercial trade designation. All liquid crystal materials are commercially available from EM Industries, Hawthorne, NY.
  • Table 1 shows that a wide variety of liquid crystal materials may be employed in PDLC devices according to the invention.
  • the switching curve for each example had a ⁇ V of at least 21 V and exhibited a uniform visual appearance upon transitioning between the translucent off-state and the transparent on-state.
  • FIG. 4 a photomicrograph (enlarged 3000X) of the PDLC device of example 2, the liquid crystal droplets range in size from about 0.1 ⁇ to about 3 ⁇ .
  • the range of droplet sizes allows, at least in part, for the PDLC device to gradually, smoothly and uniformly transition from the translucent off-state, through an infinite number of intermediate states, to the transparent on-state.
  • Droplets of different size require different applied voltages in order to switch. Some of the droplets exhibit a nonuniform shape.
  • FIG. 4 also shows that liquid crystal droplets clustered near opposed, major planar surfaces of the PDLC film tend to be smaller in size than droplets clustered in a zone intermediate areas adjacent to the major planar surfaces.
  • Example 11 A PDLC device was.prepared as described above in the general preparation except that the liquid crystal material was BL009, the polymer matrix material was N0A68, the UV radiation average intensity was 2 mW/cm 2 per side, and the total energy to which the construction was exposed was 300 mJ/cm 2 (150 mJ/cm 2 per side) .
  • The. optical performance of the device was evaluated as described above. In a graph of %T v. applied voltage, the device of example 11 had a ⁇ V of 30 V and displayed a uniform visual appearance upon transitioning between the translucent off-state and the transparent on-state.
  • a series of PDLC devices was prepared as described above in the general preparation to observe the effect of varying the thickness of the substrates.
  • Substrate thickness and the liquid crystal material were varied as shown below in Table 2.
  • the UV radiation average intensity was 1.92 mW/cm 2 per side and the total energy was 191 mJ/cm 2 (95.5-mJ/cm 2 per side).
  • the UV radiation average intensity was 1.1 mW/cm 2 per side and the total energy exposure was 100 mJ/cm 2 (50 mJ/cm 2 per side) .
  • liquid crystal materials are identified by their commercial trade designation. All liquid crystal materials are commercially available from EM Industries, Hawthorne, NY.
  • the PDLC device had a ⁇ V greater than 20 V and exhibited a uniform visual appearance upon transitioning between the translucent o -state and the transparent on-state.
  • the grey scale performance of a PDLC device was not materially affected by varying the substrate thickness.
  • Examples 15-17 A series of PDLC devices was prepared as described above in the general preparation with the exception that the liquid crystal material was BL009. The average intensity of the UV radiation was 1.1 mW/cm 2 per side and the total energy exposure was 100 mJ/cm 2 (50 mJ/cm 2 per side) . The proportions of liquid crystal material and polymer matrix material were varied as shown below in Table 3. The liquid crystal material and polymer matrix material amounts are reported in parts by weight.
  • Each example had a ⁇ V of at least 15 V and exhibited a uniform visual appearance upon transitioning between the translucent off-state and the transparent on-state. Increasing the proportion of liquid crystal material decreased the percentage of specular light transmitted through the device in the off-state and reduced the maximum %T. Examples 18-19
  • a series of PDLC devices was prepared as described above in the general preparation except that the liquid crystal material was BL009, the parts by weight ratio of liquid crystal material to polymer matrix material was 60:40, and the thickness of the liquid crystal material/polymer matrix PDLC film was varied as shown below in Table 4.
  • the average intensity of the UV radiation was 1.1 mW/cm 2 per side and the total energy exposure was 100 mJ/cm 2 (50 mJ/cm 2 per side) .
  • Each device had a ⁇ V of at least 15 V and exhibited a uniform visual appearance upon transitioning between the translucent off-state and the transparent on-state. It was observed that thinner films had an increased %T at 0 applied volts (corresponding to the off-state condition) than did thicker films.
  • a PDLC device was prepared as described above in the general preparation except that the electrode material was indium tin oxide on a 178 ⁇ thick polyester film.
  • the average intensity of the UV radiation was 1.1 mW/cm 2 per side and the total energy exposure was 100 mJ/cm 2 (50 mJ/cm 2 per side) .
  • the device had a ⁇ V of 37 V and demonstrated a uniform visual appearance upon transitioning between the translucent off-state and the transparent on-state. Changing the electrode material did not materially adversely affect the performance of the device.
  • Examples 21-22 a PDLC device was prepared as described above in the general preparation except that the LICRISTAL E7 liquid crystal material was supplemented with 0.1% (by weight of the LICRISTAL E7) of CB15, a cholesteric liquid crystal material comprising a cyanobiphenyl mixture having a 2- methylbutyl alkyl group and commercially available from EM Industries.
  • the average intensity of the UV radiation was 1.1 mW/cm 2 per side.
  • the total energy exposure was 100 mJ/cm 2 (50.mJ/cm 2 per side).
  • Example 22 paralleled example 21 except that the LICRISTAL E7 was replaced by BL009.
  • the electrodes of examples 21 and 22 included a thin, protective, passivating dielectric layer. Each device had a ⁇ V of 23 V and demonstrated a uniform visual appearance upon transitioning between the translucent off-state and the transparent on-state.
  • Examples 23 to 27 below illustrate the benefit of reducing or preventing premature, thermally-induced phase separation by heating the nip rollers and/or regulating the air temperature in the zone preceding and into the- zone containing the low intensity fluorescent lamps.
  • the particular air and nip roll temperatures are a function of the liquid crystal and polymer matrix materials. In each example, the temperatures were selected to allow for the creation of well-formed liquid crystal droplets.
  • the thickness of each substrate in examples 23 to 27 was about 50 ⁇ .
  • the electrodes in each of examples 23 to 27 included a thin, protective, passivating dielectric layer of A1 2 0 3 .
  • a PDLC device was prepared according to the general preparation except that the liquid crystal material was 17723 (BL036) and the thickness of the PLDC film was about 20 ⁇ . Furthermore, the nip rollers were maintained at about 85°F (29°C) and the air temperature in the zone preceding and into the zone containing the fluorescent lamps was maintained at about 90 ⁇ F (32°C).
  • Each side of the sandwich construction comprising the pair of electrode-coated substrates and the liquid crystal material/uncured polymer matrix material was first exposed to UV radiation of 1 mW/cm 2 average intensity for about 10 seconds followed by a subsequent average intensity exposure of 2 mW/cm2 for 2 minutes for a total subsequent energy exposure of 480 mJ/cm 2 (240 mJ/cm 2 per side) .
  • the resulting PDLC device included a multiplicity of liquid crystal droplets having sizes ranging from about 0.6 to about 2.2 ⁇ dispersed in the cured polymer matrix. The device exhibited a ⁇ V of 35 V and a uniform visual appearance upon transitioning between the translucent off-state and the transparent on-state.
  • a 20 ⁇ thick PDLC device was prepared according to example 23 except that the temperature of the nip rollers was about 92°F (33°C), the air temperature in the zone preceding and into the zone containing the fluorescent light banks was about 92°F (33°C), the initial average UV radiation intensity was 0.5 mW/cm 2 per side (30 mJ/cm 2 total energy exposure, 15 mJ/cm 2 per side) , and the subsequent UV radiation exposure was provided by a 200 Watt/inch high intensity mercury lamp with an average intensity of 24 mW/cm 2 .
  • the liquid crystal droplets in the resulting PDLC device ranged in size from 1.1 to 3.2 ⁇ .
  • the device exhibited a ⁇ V of 26 V and a uniform visual appearance upon transitioning between the translucent off-state and the transparent on-state.
  • a 20 ⁇ thick PDLC device was prepared according to example 23 except that the polymer matrix material was blended with 0.5 % by weight (based on the weight of the polymer matrix) of AEROSIL R 972 hydrophobic fumed silica using a high speed air mixer. The liquid crystal material was then added and thoroughly mixed to provide a uniform dispersion. The temperature of the nip rollers was about 93°F (34°C) and the air temperature in the zone preceding and into the zone, containing the fluorescent light banks was about 92°F (33°C) .
  • the sandwich construction was cured for eight minutes under a low intensity UV radiation source that provided an average intensity of 0.54 mW/cm 2 per side and a total energy exposure of 518 mJ/cm 2 (259 mJ/cm 2 per side) .
  • the liquid crystal droplets in the resulting PDLC device ranged in size from 0.8 to 2.7 ⁇ .
  • the PDLC device displayed a ⁇ V of 35 V and a uniform visual appearance upon transitioning between the translucent off-state and the transparent on- state.
  • Example 26 A 20 ⁇ thick PDLC device was prepared according to the procedure of example 23 except that the liquid crystal material was BL009.
  • the temperature of the nip rollers was about 110°F (43°C) and the air temperature in the zone preceding and into the zone containing the fluorescent lamps was about 120°F (49 ⁇ C) .
  • Higher temperatures were required to prevent the premature temperature-induced phase separation of the BL009 liquid crystal material as compared to the BL036 liquid crystal material.
  • the subsequent UV radiation exposure provided an intensity of 2.4 mW/cm 2 per side and a total energy of 288 mJ/cm 2 per side.
  • a photomicrograph (enlarged 250OX) of the PDLC device of example 26 the resulting liquid crystal droplets were well formed and ranged in size from 0.7 to 2 ⁇ .
  • the PDLC device demonstrated a ⁇ V of 33 V and a uniform, visual appearance upon transitioning between the translucent off-state and the transparent on- state.
  • a PDLC device was prepared according to the procedure of example 23 except that the liquid crystal material was LICRISTAL E7 and the thickness of the PDLC film was about 15 ⁇ .
  • the temperature of the nip rollers was about 67 ⁇ F (19°C) and the air temperature in the zone preceding and into the zone containing the fluorescent lamp banks was about 70°F (21°C) .
  • the liquid crystal droplets ranged in size from 0.5 to 1.6 ⁇ .
  • the resulting PDLC device had a ⁇ V of 20 V and exhibited a uniform visual appearance upon transitioning between the translucent off-state and the transparent on-state.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • Dispersion Chemistry (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
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  • Liquid Crystal Substances (AREA)

Abstract

L'invention se rapporte à un dispositif à cristaux liquides dispersés dans un polymère, qui comprend une multitude de gouttelettes d'une matière à cristaux liquides fonctionnellement nématique et biréfringent, cette matière étant dispersée dans une matrice contenant le produit de réaction de matières polymérisables par exposition à un rayonnement ultraviolet. Un tel dispositif transmet de façon spéculaire la lumière incidente en fonction de l'amplitude d'un champ électrique appliqué en travers du dispositif. La différence entre une première tension appliquée, correspondant à un premier pourcentage de la lumière incidente totale transmise par le dispositif comme lumière spéculaire, et une seconde tension appliquée, correspondant à un second pourcentage de la lumière incidente totale transmise par le dispositif en tant que lumière spéculaire, est supérieure ou égale à 15 volts. Grâce à la présente invention, on peut obtenir un dispositif à cristaux liquides dispersés dans un polymère qui affiche une échelle de gris variable présentant une transmission optique uniforme. Un procédé permettant de fabriquer un tel dispositif à cristaux liquides dispersés dans un polymère est également décrit.
PCT/US1992/000173 1991-01-11 1992-01-10 Dispositif a cristaux liquides disperses dans un polymere, presentant une matrice polymerisable aux ultraviolets et une transmission optique variable, et procede de preparation de ce dispositif WO1992012219A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BR9205462A BR9205462A (pt) 1991-01-11 1992-01-10 Dispositivo de cristal liquido disperso em polimero,e,processo para a preparacao de um dispositivo de cristal liquido disperso em um polimero
JP4504497A JPH06504387A (ja) 1991-01-11 1992-01-10 紫外線重合性マトリックス及び可変性の光透過率を有する高分子分散型液晶素子及びその調製方法
KR1019930702045A KR930703416A (ko) 1991-01-11 1992-01-10 자외선 중합가능 매트릭스 및 가변 광학적 투과를 갖는 중합체 분산 액체 결정 디바이스 및 그 제조방법

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US64003491A 1991-01-11 1991-01-11
US640,034 1991-01-11

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WO (1) WO1992012219A1 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0619360A1 (fr) * 1993-04-06 1994-10-12 Thomson-Csf Matériau électrooptique à base de cristal liquide dispersé dans un polymère, procédé d'élaboration par modification chimique de l'interface et dispositif à base de ce matériau
WO1994026841A1 (fr) * 1993-05-06 1994-11-24 Raychem Corporation Procede de production d'une matiere a base de cristaux liquides
WO1995027017A1 (fr) * 1994-03-31 1995-10-12 Raychem Corporation Telomeres amphiphiles
WO1995029966A1 (fr) * 1994-04-29 1995-11-09 Minnesota Mining And Manufacturing Company Modulateur de lumiere comprenant une matrice preparee a partir de reactants allyle
FR2721316A1 (fr) * 1994-06-21 1995-12-22 Thomson Csf Procédé d'obtention de matériaux composites à base de polymère réticulé et de molécules fluides, comprenant une étape de séchage en phase supercritique.
US5516455A (en) * 1993-05-03 1996-05-14 Loctite Corporation Polymer dispersed liquid crystals in radiation curable electron-rich alkene-thiol polymer mixtures
US5593615A (en) * 1994-04-29 1997-01-14 Minnesota Mining And Manufacturing Company Light modulating device having a matrix prepared from acid reactants
EP0772074A1 (fr) * 1995-11-01 1997-05-07 E.I. Du Pont De Nemours And Company Films de polyimide à partir de déanhydride d'acide pyromellitique et de composés aromatiques bis-(4-aminophénoxy) pour des couches d'alignement de dispositifs d'affichage à cristal liquide
US5695594A (en) * 1996-01-05 1997-12-09 Raychem Corporation Method of making a liquid crystal light valve
WO2000026973A1 (fr) * 1998-11-02 2000-05-11 Presstek, Inc. Oxydes conducteurs transparents pour ecran plat en plastique
EP1116771A2 (fr) * 2000-01-06 2001-07-18 Eastman Kodak Company Méthode de fabrication de matériaux ayant des domaines limités de coalescence uniforme
WO2004016560A2 (fr) * 2002-08-17 2004-02-26 3M Innovative Properties Company Film electroconducteur flexible
US6929864B2 (en) 2002-08-17 2005-08-16 3M Innovative Properties Company Extensible, visible light-transmissive and infrared-reflective film and methods of making and using the film
US7215473B2 (en) 2002-08-17 2007-05-08 3M Innovative Properties Company Enhanced heat mirror films
WO2008075001A3 (fr) * 2006-12-16 2008-10-02 Pelikon Ltd Dispositifs d'affichage électroluminescents
TWI502055B (zh) * 2012-07-12 2015-10-01 液晶組成物、液晶顯示面板及其製造方法
US9822454B2 (en) 2006-12-28 2017-11-21 3M Innovative Properties Company Nucleation layer for thin film metal layer formation
WO2021073992A1 (fr) 2019-10-15 2021-04-22 Covestro Intellectual Property Gmbh & Co. Kg Vitrage à intensité réglable électriquement
CN113939765A (zh) * 2019-06-28 2022-01-14 凸版印刷株式会社 调光片及调光装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140053740A (ko) 2012-10-26 2014-05-08 삼성디스플레이 주식회사 표시 장치 및 이의 구동 방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0205261A2 (fr) * 1985-06-10 1986-12-17 General Motors Corporation Gouttelettes de cristal liquide dispersées dans des films minces de polymères réticulables aux U.V.
EP0238164A1 (fr) * 1986-01-17 1987-09-23 Raychem Corporation Panneau à cristaux liquides
EP0272585A2 (fr) * 1986-12-23 1988-06-29 Asahi Glass Company Ltd. Dispositif optique à cristaux liquides et procédé de fabrication.
WO1989006371A2 (fr) * 1987-12-30 1989-07-13 Hughes Aircraft Company Materiau a cristaux liquides disperses dans un polymere d'acrylate et dispositifs realises a partir de ce materiau
US4938568A (en) * 1988-01-05 1990-07-03 Hughes Aircraft Company Polymer dispersed liquid crystal film devices, and method of forming the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0205261A2 (fr) * 1985-06-10 1986-12-17 General Motors Corporation Gouttelettes de cristal liquide dispersées dans des films minces de polymères réticulables aux U.V.
EP0238164A1 (fr) * 1986-01-17 1987-09-23 Raychem Corporation Panneau à cristaux liquides
EP0272585A2 (fr) * 1986-12-23 1988-06-29 Asahi Glass Company Ltd. Dispositif optique à cristaux liquides et procédé de fabrication.
WO1989006371A2 (fr) * 1987-12-30 1989-07-13 Hughes Aircraft Company Materiau a cristaux liquides disperses dans un polymere d'acrylate et dispositifs realises a partir de ce materiau
US4938568A (en) * 1988-01-05 1990-07-03 Hughes Aircraft Company Polymer dispersed liquid crystal film devices, and method of forming the same

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2703690A1 (fr) * 1993-04-06 1994-10-14 Thomson Csf Matériau électrooptique à base de cristal liquide dispersé dans un polymère, procédé d'élaboration par modification chimique de l'interface et dispositif à base de ce matériau.
EP0619360A1 (fr) * 1993-04-06 1994-10-12 Thomson-Csf Matériau électrooptique à base de cristal liquide dispersé dans un polymère, procédé d'élaboration par modification chimique de l'interface et dispositif à base de ce matériau
US5525381A (en) * 1993-04-06 1996-06-11 Thomson-Csf Electro-optical material based on polymer-dispersed liquid crystal, method for the preparation thereof by chemical modification of the interface and device based on this material
US5516455A (en) * 1993-05-03 1996-05-14 Loctite Corporation Polymer dispersed liquid crystals in radiation curable electron-rich alkene-thiol polymer mixtures
WO1994026841A1 (fr) * 1993-05-06 1994-11-24 Raychem Corporation Procede de production d'une matiere a base de cristaux liquides
WO1995027017A1 (fr) * 1994-03-31 1995-10-12 Raychem Corporation Telomeres amphiphiles
WO1995029966A1 (fr) * 1994-04-29 1995-11-09 Minnesota Mining And Manufacturing Company Modulateur de lumiere comprenant une matrice preparee a partir de reactants allyle
US5593615A (en) * 1994-04-29 1997-01-14 Minnesota Mining And Manufacturing Company Light modulating device having a matrix prepared from acid reactants
US5641426A (en) * 1994-04-29 1997-06-24 Minnesota Mining And Manufacturing Company Light modulating device having a vinyl ether-based matrix
EP0688851A1 (fr) * 1994-06-21 1995-12-27 Thomson-Csf Procédé d'obtention de matériaux composites à base de polymère réticulé et de molécules fluides, comprenant une étape de séchage en phase supercritique
FR2721316A1 (fr) * 1994-06-21 1995-12-22 Thomson Csf Procédé d'obtention de matériaux composites à base de polymère réticulé et de molécules fluides, comprenant une étape de séchage en phase supercritique.
US5605727A (en) * 1994-06-21 1997-02-25 Thomson-Csf Method for obtaining composite materials based on cross-linked polymer and fluid molecules, comprising a step of drying in supercritical phase
EP0772074A1 (fr) * 1995-11-01 1997-05-07 E.I. Du Pont De Nemours And Company Films de polyimide à partir de déanhydride d'acide pyromellitique et de composés aromatiques bis-(4-aminophénoxy) pour des couches d'alignement de dispositifs d'affichage à cristal liquide
US5731404A (en) * 1995-11-01 1998-03-24 E. I. Du Pont De Nemours And Company Polyimide film from pyromellitic dianhydride and a bis(4-aminophenoxy) aromatic compound as an alignment layer for liquid crystal displays
US5856432A (en) * 1995-11-01 1999-01-05 E. I. Dupont De Nemours And Company Polyimide film from pyromellitic dianhydride and a bis (4-aminophenoxy) aromatic compound as an alignment layer for liquid crystal displays
US5695594A (en) * 1996-01-05 1997-12-09 Raychem Corporation Method of making a liquid crystal light valve
WO2000026973A1 (fr) * 1998-11-02 2000-05-11 Presstek, Inc. Oxydes conducteurs transparents pour ecran plat en plastique
EP1116771A2 (fr) * 2000-01-06 2001-07-18 Eastman Kodak Company Méthode de fabrication de matériaux ayant des domaines limités de coalescence uniforme
EP1116771A3 (fr) * 2000-01-06 2001-09-26 Eastman Kodak Company Méthode de fabrication de matériaux ayant des domaines limités de coalescence uniforme
US7215473B2 (en) 2002-08-17 2007-05-08 3M Innovative Properties Company Enhanced heat mirror films
WO2004016560A3 (fr) * 2002-08-17 2004-04-08 3M Innovative Properties Co Film electroconducteur flexible
US6929864B2 (en) 2002-08-17 2005-08-16 3M Innovative Properties Company Extensible, visible light-transmissive and infrared-reflective film and methods of making and using the film
US6933051B2 (en) 2002-08-17 2005-08-23 3M Innovative Properties Company Flexible electrically conductive film
WO2004016560A2 (fr) * 2002-08-17 2004-02-26 3M Innovative Properties Company Film electroconducteur flexible
CN1675059B (zh) * 2002-08-17 2010-06-16 3M创新有限公司 包括多个可见光透射层的挠性导电薄膜
WO2008075001A3 (fr) * 2006-12-16 2008-10-02 Pelikon Ltd Dispositifs d'affichage électroluminescents
US8854575B2 (en) 2006-12-16 2014-10-07 Mflex Uk Limited Electroluminescent displays
US9822454B2 (en) 2006-12-28 2017-11-21 3M Innovative Properties Company Nucleation layer for thin film metal layer formation
TWI502055B (zh) * 2012-07-12 2015-10-01 液晶組成物、液晶顯示面板及其製造方法
CN113939765A (zh) * 2019-06-28 2022-01-14 凸版印刷株式会社 调光片及调光装置
CN113939765B (zh) * 2019-06-28 2023-12-12 凸版印刷株式会社 调光片及调光装置
WO2021073992A1 (fr) 2019-10-15 2021-04-22 Covestro Intellectual Property Gmbh & Co. Kg Vitrage à intensité réglable électriquement

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AU1243092A (en) 1992-08-17
EP0566683A1 (fr) 1993-10-27
KR930703416A (ko) 1993-11-30
CA2096826A1 (fr) 1992-07-12
JPH06504387A (ja) 1994-05-19

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