This invention relates to applications of electro-optic displays. More specifically, this invention relates to uses of electro-optic displays, especially but not exclusively, particle-based electrophoretic displays, in architectural, furnishing and similar applications.
The term “electro-optic”, as applied to a material or a display, is used herein in its conventional meaning in the imaging art to refer to a material having first and second display states differing in at least one optical property, the material being changed from its first to its second display state by application of an electric field to the material. Although the optical property is typically color perceptible to the human eye, it may be another optical property, such as optical transmission, reflectance, luminescence or, in the case of displays intended for machine reading, pseudo-color in the sense of a change in reflectance of electromagnetic wavelengths outside the visible range.
The term “gray state” is used herein in its conventional meaning in the imaging art to refer to a state intermediate two extreme optical states of a pixel, and does not necessarily imply a black-white transition between these two extreme states. For example, several of the E Ink patents and published applications referred to below describe electrophoretic displays in which the extreme states are white and deep blue, so that an intermediate “gray state” would actually be pale blue. Indeed, as already mentioned, the change in optical state may not be a color change at all. The terms “black” and “white” may be used hereinafter to refer to the two extreme optical states of a display, and should be understood as normally including extreme optical states which are not strictly black and white, for example the aforementioned white and dark blue states. The term “monochrome” may be used hereinafter to denote a drive scheme which only drives pixels to their two extreme optical states with no intervening gray states.
Some electro-optic materials are solid in the sense that the materials have solid external surfaces, although the materials may, and often do, have internal liquid- or gas-filled spaces. Such displays using solid electro-optic materials may hereinafter for convenience be referred to as “solid electro-optic displays”. Thus, the term “solid electro-optic displays” includes rotating bichromal member displays, encapsulated electrophoretic displays, microcell electrophoretic displays and encapsulated liquid crystal displays.
The terms “bistable” and “bistability” are used herein in their conventional meaning in the art to refer to displays comprising display elements having first and second display states differing in at least one optical property, and such that after any given element has been driven, by means of an addressing pulse of finite duration, to assume either its first or second display state, after the addressing pulse has terminated, that state will persist for at least several times, for example at least four times, the minimum duration of the addressing pulse required to change the state of the display element. It is shown in U.S. Pat. No. 7,170,670 that some particle-based electrophoretic displays capable of gray scale are stable not only in their extreme black and white states but also in their intermediate gray states, and the same is true of some other types of electro-optic displays. This type of display is properly called “multi-stable” rather than bistable, although for convenience the term “bistable” may be used herein to cover both bistable and multi-stable displays.
Several types of electro-optic displays are known. One type of electro-optic display is a rotating bichromal member type as described, for example, in U.S. Pat. Nos. 5,808,783; 5,777,782; 5,760,761; 6,054,071 6,055,091; 6,097,531; 6,128,124; 6,137,467; and 6,147,791 (although this type of display is often referred to as a “rotating bichromal ball” display, the term “rotating bichromal member” is preferred as more accurate since in some of the patents mentioned above the rotating members are not spherical). Such a display uses a large number of small bodies (typically spherical or cylindrical) which have two or more sections with differing optical characteristics, and an internal dipole. These bodies are suspended within liquid-filled vacuoles within a matrix, the vacuoles being filled with liquid so that the bodies are free to rotate. The appearance of the display is changed by applying an electric field thereto, thus rotating the bodies to various positions and varying which of the sections of the bodies is seen through a viewing surface. This type of electro-optic medium is typically bistable.
Another type of electro-optic display uses an electrochromic medium, for example an electrochromic medium in the form of a nanochromic film comprising an electrode formed at least in part from a semi-conducting metal oxide and a plurality of dye molecules capable of reversible color change attached to the electrode; see, for example O'Regan, B., et al., Nature 1991, 353, 737; and Wood, D., Information Display, 18(3), 24 (March 2002). See also Bach, U., et al., Adv. Mater., 2002, 14(11), 845. Nanochromic films of this type are also described, for example, in U.S. Pat. Nos. 6,301,038; 6,870,657; and 6,950,220. This type of medium is also typically bistable.
Another type of electro-optic display is an electro-wetting display developed by Philips and described in Hayes, R. A., et al., “Video-Speed Electronic Paper Based on Electrowetting”, Nature, 425, 383-385 (2003). It is shown in U.S. Pat. No. 7,420,549 that such electro-wetting displays can be made bistable.
One type of electro-optic display, which has been the subject of intense research and development for a number of years, is the particle-based electrophoretic display, in which a plurality of charged particles move through a fluid under the influence of an electric field. Electrophoretic displays can have attributes of good brightness and contrast, wide viewing angles, state bistability, and low power consumption when compared with liquid crystal displays. Nevertheless, problems with the long-term image quality of these displays have prevented their widespread usage. For example, particles that make up electrophoretic displays tend to settle, resulting in inadequate service-life for these displays.
As noted above, electrophoretic media require the presence of a fluid. In most prior art electrophoretic media, this fluid is a liquid, but electrophoretic media can be produced using gaseous fluids; see, for example, Kitamura, T., et al., “Electrical toner movement for electronic paper-like display”, IDW Japan, 2001, Paper HCS1-1, and Yamaguchi, Y, et al., “Toner display using insulative particles charged triboelectrically”, IDW Japan, 2001, Paper AMD4-4). See also U.S. Pat. Nos. 7,321,459 and 7,236,291. Such gas-based electrophoretic media appear to be susceptible to the same types of problems due to particle settling as liquid-based electrophoretic media, when the media are used in an orientation which permits such settling, for example in a sign where the medium is disposed in a vertical plane. Indeed, particle settling appears to be a more serious problem in gas-based electrophoretic media than in liquid-based ones, since the lower viscosity of gaseous suspending fluids as compared with liquid ones allows more rapid settling of the electrophoretic particles.
Numerous patents and applications assigned to or in the names of the Massachusetts Institute of Technology (MIT), E Ink Corporation, E Ink California, LLC. and related companies describe various technologies used in encapsulated and microcell electrophoretic and other electro-optic media. Encapsulated electrophoretic media comprise numerous small capsules, each of which itself comprises an internal phase containing electrophoretically-mobile particles in a fluid medium, and a capsule wall surrounding the internal phase. Typically, the capsules are themselves held within a polymeric binder to form a coherent layer positioned between two electrodes. In a microcell electrophoretic display, the charged particles and the fluid are not encapsulated within microcapsules but instead are retained within a plurality of cavities formed within a carrier medium, typically a polymeric film. The technologies described in these patents and applications include:
Many of the aforementioned patents and applications recognize that the walls surrounding the discrete microcapsules in an encapsulated electrophoretic medium could be replaced by a continuous phase, thus producing a so-called polymer-dispersed electrophoretic display, in which the electrophoretic medium comprises a plurality of discrete droplets of an electrophoretic fluid and a continuous phase of a polymeric material, and that the discrete droplets of electrophoretic fluid within such a polymer-dispersed electrophoretic display may be regarded as capsules or microcapsules even though no discrete capsule membrane is associated with each individual droplet; see for example, the aforementioned U.S. Pat. No. 6,866,760. Accordingly, for purposes of the present application, such polymer-dispersed electrophoretic media are regarded as sub-species of encapsulated electrophoretic media.
Although electrophoretic media are often opaque (since, for example, in many electrophoretic media, the particles substantially block transmission of visible light through the display) and operate in a reflective mode, many electrophoretic displays can be made to operate in a so-called “shutter mode” in which one display state is substantially opaque and one is light-transmissive. See, for example, U.S. Pat. Nos. 5,872,552; 6,130,774; 6,144,361; 6,172,798; 6,271,823; 6,225,971; and 6,184,856. Dielectrophoretic displays, which are similar to electrophoretic displays but rely upon variations in electric field strength, can operate in a similar mode; see U.S. Pat. No. 4,418,346. Other types of electro-optic displays may also be capable of operating in shutter mode. Electro-optic media operating in shutter mode may be useful in multi-layer structures for full color displays; in such structures, at least one layer adjacent the viewing surface of the display operates in shutter mode to expose or conceal a second layer more distant from the viewing surface.
An encapsulated electrophoretic display typically does not suffer from the clustering and settling failure mode of traditional electrophoretic devices and provides further advantages, such as the ability to print or coat the display on a wide variety of flexible and rigid substrates. (Use of the word “printing” is intended to include all forms of printing and coating, including, but without limitation: pre-metered coatings such as patch die coating, slot or extrusion coating, slide or cascade coating, curtain coating; roll coating such as knife over roll coating, forward and reverse roll coating; gravure coating; dip coating; spray coating; meniscus coating; spin coating; brush coating; air knife coating; silk screen printing processes; electrostatic printing processes; thermal printing processes; ink jet printing processes; electrophoretic deposition (See U.S. Pat. No. 7,339,715); and other similar techniques.) Thus, the resulting display can be flexible. Further, because the display medium can be printed (using a variety of methods), the display itself can be made inexpensively.
Other types of electro-optic materials may also be used in the present invention.
An electro-optic display normally comprises a layer of electro-optic material and at least two other layers disposed on opposed sides of the electro-optic material, one of these two layers being an electrode layer. In most such displays both the layers are electrode layers, and one or both of the electrode layers are patterned to define the pixels of the display. For example, one electrode layer may be patterned into elongate row electrodes and the other into elongate column electrodes running at right angles to the row electrodes, the pixels being defined by the intersections of the row and column electrodes. Alternatively, and more commonly, one electrode layer has the form of a single continuous electrode and the other electrode layer is patterned into a matrix of pixel electrodes, each of which defines one pixel of the display. In another type of electro-optic display, which is intended for use with a stylus, print head or similar movable electrode separate from the display, only one of the layers adjacent the electro-optic layer comprises an electrode, the layer on the opposed side of the electro-optic layer typically being a protective layer intended to prevent the movable electrode damaging the electro-optic layer.
The manufacture of a three-layer electro-optic display normally involves at least one lamination operation. For example, in several of the aforementioned MIT and E Ink patents and applications, there is described a process for manufacturing an encapsulated electrophoretic display in which an encapsulated electrophoretic medium comprising capsules in a binder is coated on to a flexible substrate comprising indium-tin-oxide (ITO) or a similar conductive coating (which acts as one electrode of the final display) on a plastic film, the capsules/binder coating being dried to form a coherent layer of the electrophoretic medium firmly adhered to the substrate. Separately, a backplane, containing an array of pixel electrodes and an appropriate arrangement of conductors to connect the pixel electrodes to drive circuitry, is prepared. To form the final display, the substrate having the capsule/binder layer thereon is laminated to the backplane using a lamination adhesive. (A very similar process can be used to prepare an electrophoretic display usable with a stylus or similar movable electrode by replacing the backplane with a simple protective layer, such as a plastic film, over which the stylus or other movable electrode can slide.) In one preferred form of such a process, the backplane is itself flexible and is prepared by printing the pixel electrodes and conductors on a plastic film or other flexible substrate. The obvious lamination technique for mass production of displays by this process is roll lamination using a lamination adhesive. Similar manufacturing techniques can be used with other types of electro-optic displays. For example, a microcell electrophoretic medium or a rotating bichromal member medium may be laminated to a backplane in substantially the same manner as an encapsulated electrophoretic medium.
As discussed in the aforementioned U.S. Pat. No. 6,982,178, (see column 3, lines 63 to column 5, line 46) many of the components used in solid electro-optic displays, and the methods used to manufacture such displays, are derived from technology used in liquid crystal displays (LCD's), which are of course also electro-optic displays, though using a liquid rather than a solid medium. For example, solid electro-optic displays may make use of an active matrix backplane comprising an array of transistors or diodes and a corresponding array of pixel electrodes, and a “continuous” front electrode (in the sense of an electrode which extends over multiple pixels and typically the whole display) on a transparent substrate, these components being essentially the same as in LCD's. However, the methods used for assembling LCD's cannot be used with solid electro-optic displays. LCD's are normally assembled by forming the backplane and front electrode on separate glass substrates, then adhesively securing these components together leaving a small aperture between them, placing the resultant assembly under vacuum, and immersing the assembly in a bath of the liquid crystal, so that the liquid crystal flows through the aperture between the backplane and the front electrode. Finally, with the liquid crystal in place, the aperture is sealed to provide the final display.
This LCD assembly process cannot readily be transferred to solid electro-optic displays. Because the electro-optic material is solid, it must be present between the backplane and the front electrode before these two integers are secured to each other. Furthermore, in contrast to a liquid crystal material, which is simply placed between the front electrode and the backplane without being attached to either, a solid electro-optic medium normally needs to be secured to both; in most cases the solid electro-optic medium is formed on the front electrode, since this is generally easier than forming the medium on the circuitry-containing backplane, and the front electrode/electro-optic medium combination is then laminated to the backplane, typically by covering the entire surface of the electro-optic medium with an adhesive and laminating under heat, pressure and possibly vacuum. Accordingly, most prior art methods for final lamination of solid electrophoretic displays are essentially batch methods in which (typically) the electro-optic medium, a lamination adhesive and a backplane are brought together immediately prior to final assembly, and it is desirable to provide methods better adapted for mass production.
Electro-optic displays are often costly; for example, the cost of the color LCD found in a portable computer is typically a substantial fraction of the entire cost of the computer. As the use of electro-optic displays spreads to devices, such as cellular telephones and personal digital assistants (PDA's), much less costly than portable computers, there is great pressure to reduce the costs of such displays. The ability to form layers of some solid electro-optic media by printing techniques on flexible substrates, as discussed above, opens up the possibility of reducing the cost of electro-optic components of displays by using mass production techniques such as roll-to-roll coating using commercial equipment used for the production of coated papers, polymeric films and similar media.
The aforementioned U.S. Pat. No. 6,982,178 describes a method of assembling a solid electro-optic display (including an encapsulated electrophoretic display) which is well adapted for mass production. Essentially, this patent describes a so-called “front plane laminate” (“FPL”) which comprises, in order, a light-transmissive electrically-conductive layer; a layer of a solid electro-optic medium in electrical contact with the electrically-conductive layer; an adhesive layer; and a release sheet. (The term “light-transmissive” is used in this patent and herein to mean that the layer thus designated transmits sufficient light to enable an observer, looking through that layer, to observe the change in display states of the electro-optic medium, which will normally be viewed through the electrically-conductive layer and adjacent substrate (if present); in cases where the electro-optic medium displays a change in reflectivity at non-visible wavelengths, the term “light-transmissive” should of course be interpreted to refer to transmission of the relevant non-visible wavelengths.) Typically, the light-transmissive electrically-conductive layer will be carried on a light-transmissive substrate, which is preferably flexible, in the sense that the substrate can be manually wrapped around a drum (say) 10 inches (254 mm) in diameter without permanent deformation. The term “light-transmissive” is used in this patent and herein to mean that the layer thus designated transmits sufficient light to enable an observer, looking through that layer, to observe the change in display states of the electro-optic medium, which will normally be viewed through the electrically-conductive layer and adjacent substrate (if present); in cases where the electro-optic medium displays a change in reflectivity at non-visible wavelengths, the term “light-transmissive”should of course be interpreted to refer to transmission of the relevant non-visible wavelengths. The substrate will typically be a polymeric film, and will normally have a thickness in the range of about 1 to about 25 mil (25 to 634 μm), preferably about 2 to about 10 mil (51 to 254 μm). The electrically-conductive layer is conveniently a thin metal or metal oxide layer of, for example, aluminum or ITO, or may be a conductive polymer. Poly(ethylene terephthalate) (PET) films coated with aluminum or ITO are available commercially, for example as “aluminized Mylar” (“Mylar” is a Registered Trade Mark) from E.I. du Pont de Nemours & Company, Wilmington DE, and such commercial materials may be used with good results in the front plane laminate.
Assembly of an electro-optic display using such a front plane laminate may be effected by removing the release sheet from the front plane laminate and contacting the adhesive layer with the backplane under conditions effective to cause the adhesive layer to adhere to the backplane, thereby securing the adhesive layer, layer of electro-optic medium and electrically-conductive layer to the backplane. This process is well-adapted to mass production since the front plane laminate may be mass produced, typically using roll-to-roll coating techniques, and then cut into pieces of any size needed for use with specific backplanes.
U.S. Pat. No. 7,561,324 describes a so-called “double release sheet” which is essentially a simplified version of the front plane laminate of the aforementioned U.S. Pat. No. 6,982,178. One form of the double release sheet comprises a layer of a solid electro-optic medium sandwiched between two adhesive layers, one or both of the adhesive layers being covered by a release sheet. Another form of the double release sheet comprises a layer of a solid electro-optic medium sandwiched between two release sheets. Both forms of the double release film are intended for use in a process generally similar to the process for assembling an electro-optic display from a front plane laminate already described, but involving two separate laminations; typically, in a first lamination the double release sheet is laminated to a front electrode to form a front sub-assembly, and then in a second lamination the front sub-assembly is laminated to a backplane to form the final display, although the order of these two laminations could be reversed if desired.
U.S. Pat. No. 7,839,564 describes a so-called “inverted front plane laminate”, which is a variant of the front plane laminate described in the aforementioned U.S. Pat. No. 6,982,178. This inverted front plane laminate comprises, in order, at least one of a light-transmissive protective layer and a light-transmissive electrically-conductive layer; an adhesive layer; a layer of a solid electro-optic medium; and a release sheet. This inverted front plane laminate is used to form an electro-optic display having a layer of lamination adhesive between the electro-optic layer and the front electrode or front substrate; a second, typically thin layer of adhesive may or may not be present between the electro-optic layer and a backplane. Such electro-optic displays can combine good resolution with good low temperature performance.
Electrophoretic and similar bistable electro-optic display media have until now been primarily used in electronic document readers (E-book readers), with some use in electronic storage media such as flash drives, portable computers, tablet computers, cellular telephones, smart cards, signs, watches, shelf labels, and variable transmission windows. However, the low power requirements, flexibility and light weight of electrophoretic and similar bistable electro-optic display media render them useful in numerous other applications, especially architectural and related applications.
The aforementioned US 2016/0259225 describes several application of electrophoretic displays in architectural application, especially color-changing tiles and other means of changing the color of room décor to alter the mood of a room. The aforementioned US 2016/0232835 describes driving method for electrophoretic displays which are particularly useful for large area displays, such as in furniture and architectural applications.
The term “architectural surface” is used herein to denote a surface of a building or similar structure, for example, a portable building, travel trailer or recreational vehicle, whether internal or external, although the inventions described below are likely to be used mainly on internal surfaces. The term “architectural surface” is also intended to include surfaces of architectural fixtures, and movable or permanent structures, such a room dividers, which act as temporary or permanent walls within buildings. Thus, the term “architectural surface” includes not only walls, ceilings and floors of buildings and similar structures, but surfaces of, for example, kitchen cabinets, appliances and islands, and the surfaces of doors, screens and room dividers.
As discussed in detail in the aforementioned US 2016/0259225, electro-optic displays, especially bistable electro-optic displays, open up novel possibilities for the treatment of architectural surfaces which allow for variation of the appearance of the surface, including patterning or displaying images on architectural surfaces; in effect, entire walls (or other similar surfaces, such as ceilings and room partitions or dividers) can become displays. Such “wall displays” may be useful in rooms used for multiple functions (such as hotel and similar function rooms) only a small proportion of which require large visual displays. In such cases, the cost of a large monitor may be difficult to justify and the appearance of the monitor when not is use (for the majority of the time the function room is used) may be objectionable. Similarly, the cost of a large, retractable projection screen and associated driving apparatus may be difficult to justify. Ideally, in such situations one would like have a large area of wall or similar surface which can be used to display images when required but which simply appears as a conventional wall surface when not in use for displaying images. The present invention seems to provide such a wall display.
Although present technology is capable of providing very large areas of electrophoretic and other display media, if necessary by joining parallel strips of such media, the major difficulty in providing large, high resolution displays is finding a way to drive the display. To a large extent, the complexity and cost of current display solutions have limited this type of application. To create a high resolution image on a large display area currently requires either an active matrix backplane or a passive matrix display, either of which requires complex electrical connections and a large number of drive signals; especially on an architectural scale, which could involve displays of 100 square feet (about 10 square meters) or more, the cost of any current active matrix or passive matrix display would be prohibitive for most applications. The present invention seeks to provide method of driving an architectural scale display in an economical manner.
Another aspect of the present invention relates to color adjustment on walls and similar architectural surfaces. It is notoriously difficult for most “laymen” (in this context, meaning those who are not skilled in color science) to select paints and other coloring materials (for example, floor, wall or ceiling tiles) to produce a desired effect in a room. Traditionally, retail stores provide small samples (“swatches”) of colors available in the paints they sell. Even if the swatches accurately represent the paint colors (and the differences between pigment-based paints and dye-based printing make exact matching difficult), viewing a small swatch in a large retail store under artificial illumination usually different from that used in homes, and surrounded by a palette of colors (for example, gray concrete floors, red or yellow metal racks and gray ceilings) bearing no resemblance to that typically present in a home, is likely to leave most layman choosing a paint color differing markedly from that they really want. Even if the customer takes a limited number of swatches home to evaluate them in situ, at least two major problems remain. Some colors may be perceived very differently depending upon whether they are illuminated with natural or artificial light, and the color perceived in natural light may vary considerable depending upon whether the natural light is the white light of noon or the more roseate light near dawn or dusk, and customers frequently fail to test the swatches under varying lighting conditions. Furthermore, because of the structure of the human eye, in which the color-perceiving cones are concentrated in the central area, with a preponderance of color-insensitive rods on the periphery, human color perception varies with the size of the color sample being viewed; there is a significant difference between so-called 2° color (in which the color sample subtends 2 degrees of arc as seen by the eye) and 10° color. In particular, pale (relatively unsaturated colors) tend to appear more saturated when large expanses of color are being viewed.
In an effort to reduce these problems, many paint stores now sell small samples of paint, enough to paint about one or two square feet of wall, so that customers can test various colors before making their final choice. However, buying and applying several paint samples involves significant expense and labor, and the appearance of a sample patch, which will typically be viewed against a background of the existing wall color, may still not accurately reflect the appearance of an entire wall of the same color; for example, a pale blue patch viewed against an existing yellow background may appear somewhat more saturated than the final pale blue wall, while a purple patch viewed against a red background will appear shifted towards blue. Furthermore, leaving several different patches of color on a wall may cause problems after later repainting, since the various colors may tend to show through the final color, leaving either a non-uniform final color or requiring an extra coat of paint to overcome the show through colors.
The result of all the aforementioned problems is that when it comes to selecting colors for indoor architectural features, most people find selecting the correct color to be a daunting task. Often, people have a particular hue or tone in mind but are disappointed by the appearance of their painting (or other color application, such as floor tiling), and their disappointment is increased by the fact repainting is the only corrective action available.
Furthermore, for reasons discussed in more detail in the aforementioned US 2016/0259225, it may be desirable to vary the color of architectural surfaces to allow for changes in the use of a room (for example, warm colors tend to more appropriate for friendly social gatherings, whereas cool colors may be more appropriate for study) or changes in lighting conditions, time of day or season of year, etc.
The present invention seeks to provide a treatment for architectural surfaces which reduces or overcomes the problems discussed above, and allows adjustment of the appearance of the surface without repainting.
In another aspect, this invention provides a method of forming an image on an architectural surface, the method comprising:
In this image-forming method, the photoconductive layer and the electro-optic layer may be arranged in either order between the two electrode layers. Typically, the photoconductive layer will be arranged between the electro-optic layer and the rear electrode because many photoconductive layers are either opaque or strongly colored, and hence would distort the color of the electro-optic layer as viewed by an observer seeing this layer through the front electrode. However, if the photoconductive layer used is substantially transparent, or colored in a manner which is not objectionable to the observer (for example, a yellow photoconductive layer in front of a black-white electro-optic layer might be used to provide a black-yellow display), the photoconductive layer may be disposed between the electro-optic layer and the front electrode (i.e., in front of the electro-optic layer). If the electro-optic layer strongly absorbs the radiation used for the imagewise exposure, it may be necessary to dispose the photoconductive layer in front of the electro-optic layer. Note that although the image produced will normally need to be visible to the human eye, there is no requirement that the radiation used for the imagewise exposure be visible; indeed, in some cases it may be convenient to use non-visible radiation (for example, near ultra-violet radiation) so as to allow for the formation of am image without any visible projection beam.
In one form of this method, the imagewise exposure is effected by projecting an image on to the architectural surface using a projector. Alternatively, particularly where the space in front of the architectural surface is limited, the imagewise exposure could be effected by passing a row of light emitters (for example, a strip of light emitting diodes) over the architectural surface; although this method is likely to be much slower than projecting the whole image at once, it may be acceptable in many architectural applications, where images may only be changed at lengthy intervals. If desired, the row of light emitters could be static along one edge of the display and a moving angled mirror could be used to direct light from the light emitters on to the display itself.
In the image forming method of the present invention, the stack provided on the architectural surface may include additional layers. In particular, the stack may include an additional adhesive layer between the front electrode layer and the electro-optic layer and/or between the electro-optic layer and the rear electrode layer. The film may also include a protective layer on the opposed side of the front electrode layer from the electro-optic layer. The film may also include any of the optional features of front plane laminates, inverted front plane laminates or double release films in the patents and applications discussed above.
In one aspect, this invention provides a film for application to an architectural surface, the film comprising, in order:
The light-transmissive colored front electrode layer may be a single layer of, for example, a dyed conductive polymer, such as a polythiophene. However, some common types of light-transmissive electrodes, for example sputtered metal oxides such as indium tin oxide, are not readily available in colored form, and in such cases it will generally be convenient to provide the light-transmissive colored front electrode layer as a double layer, with the conductive layer closer to the electro-optic layer and a separate colored layer on the opposed side of the conductive layer from the electro-optic layer.
There are two main variants of the film of the present invention. In the first variant, the electro-optic layer is a black-and-white film (i.e., one having black and white extreme states, and typically a number of gray states intermediate the black and white extreme states). This film variant allows one to alter the color tone of the architectural surface by modulating the reflectivity of the electro-optic layer behind the light-transmissive colored layer. In the second variant, the electro-optic layer is capable of displaying at least two different colors, so that one can alter the hue, and preferably also the tone, of the architectural surface by modulating the color (and preferably reflectivity) of the electro-optic layer.
The films of the present invention may have a variety of physical forms. When used on walls or similar vertical surfaces they may be in the form of long rolls which can be applied to the vertical surfaces in the same manner as conventional wallpaper. (In this case, provided that appropriate moisture barriers are provided to protect the electrode layers and the electro-optic layer, the adhesive layer may be of the water-activated type so that the film can be applied in the same manner as pre-pasted wallpaper.) Films intended to application to horizontal surfaces, such as countertops and ceilings, may also be in the form of rolls. Films intended for application to floors may be in the form of tiles, in which case it may be convenient to form the front and rear connecting means as edge connectors on each tile to make contact with adjacent tiles to allow multiple tiles to switch simultaneously.
The adhesive layer will typically be a pressure-sensitive adhesive, in which case the adhesive layer will normally need to be covered with a release sheet to prevent unwanted adhesion of the adhesive to other materials during transit, including other portions of the film if a long film is rolled during storage or transit. However, other types of adhesive may be used. For example, in some types of tiles intended for application to a relatively rough sub-floor, it may be desirable to a flowable heat-activated adhesive and expose the tiles to an appropriate temperature immediately prior to contacting them with the sub-floor. Also, as previously noted, water-activated adhesives may be used.
The front and rear connecting means (hereinafter “front and rear connectors”) may also have a variety of physical forms. In the case of films applied in the same manner as wallpaper, it will generally be convenient to supply operating voltages to the front and rear electrodes via two horizontal conductors running adjacent the upper and lower edges of the portion of the wall to which the film is to be applied. The front and rear connectors can then have the form of extensions of the front and rear electrode layers extending laterally beyond one or both lateral edges of the film and making electrical contact with horizontal conductors either directly or via conductive adhesives. Such front and rear connectors may be hidden behind adjacent pieces of film, and to prevent electrical short circuits it may be desirable to cover the exposed surfaces of the extensions with an insulating layer. Instead of providing an extension of the rear electrode layer, direct electrical contact may be effected between the rear electrode layer and an underlying conductor by, for example, doping a portion of the adhesive layer to render it sufficiently conductor (see U.S. Pat. No. 7,012,735 for dopants for increasing the conductivity of adhesives, removing a portion of the adhesive layer, and optionally replacing it with a conductive adhesive, or using a conductor with a rough surface and pressing the film on to the conductor until projections on the rough surface make contact with the rear electrode layer.
The film of the present invention may include additional layers. In particular, the film may include an additional adhesive layer between the front electrode layer and the electro-optic layer and/or between the electro-optic layer and the rear electrode layer. The film may also include a protective layer on the opposed side of the light-transmissive colored layer from the electro-optic layer (or the light-transmissive colored layer may also be configured to act as a protective layer to protect the remaining layers of the display from mechanical damage). The film may also include any of the optional features of front plane laminates, inverted front plane laminates or double release films in the patents and applications discussed above.
In another aspect, this invention provides a method of coating an architectural surface, the method comprising:
In another aspect this invention provides an architectural surface provided with spaced first and second conductors, and a plurality of pieces of a film of the present invention adhered to the architectural surface, with the front connecting means of each of the plurality of pieces electrically connected to the first conductor and the rear connecting means of each of the plurality of pieces electrically connected to the second conductor.
Some electro-optic layers used in the films of the present invention (and in the structures used in the image-forming method of the present invention), especially electrophoretic films, typically contain inflammable organic fluids, and may also contain polymeric films capable of ignition. Accordingly, at least some jurisdictions may require the exposed surfaces of the films or structures to be provided with an intumescent (fire-resistant) coating. Many conventional intumescent coatings are essentially opaque and thus unsuitable for use with films of the present invention. If a film of the present invention or an image-receiving surface used in the method of the present invention requires an intumescent coating, such a coating is preferably of the type described in the aforementioned copending provisional Application Ser. No. 62/703,156, the entire disclosure of which is incorporated herein by reference. These intumescent coatings comprise a layer of an intumescent material and at least one moisture barrier in contact with at least one surface of the layer of intumescent material, the intumescent material comprising an amine or amide containing compound. The intumescent material may be provided with first and second moisture barriers, with the intumescent material disposed between the first and second moisture barriers. The or each moisture barrier may comprise a protective film and a layer of adhesive. The protective film may comprise a material selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimides, cyclic olefin homopolymers or copolymers, and combinations thereof. The layer of adhesive may comprise an optically clear adhesive material. The moisture barrier may have has a water vapor transmission rate (WVTR) less than or equal to 0.01 g/m2/day at 60° C. and 100% relative humidity. The intumescent material may include a char-forming carbonaceous material, a dehydration catalyst, and a blowing agent. The char-forming carbonaceous material may be selected from the group consisting of polyols, polyamide-6, nanocomposites of polyamide-6 and clay, triazine derivatives, isocyanurate derivatives, ethanolamine-aminotriazine oligomers, and combinations thereof. The dehydration catalyst may be selected from the group consisting of ammonium polyphosphate, ammonium pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, chloroalkyl phosphates, chloroalkyl phosphonates, esters of organic phosphates or phosphonates, and combinations thereof. The blowing agent may be selected from the group consisting of melamine, triazine derivatives, and combinations thereof. The intumescent material may also comprise a binder resin, which may be selected from the group consisting of melamine formaldehyde, urea formaldehyde, polyacrylates, polyurethanes, polyvinyls, EVAs, PVAc, epoxides, silicates, and combinations thereof. The intumescent material may also comprise a plasticizer, which may be selected from the group consisting of glycerol and ethylene glycol. At least a portion of the layer of intumescent material will normally be located between the at least one moisture barrier and the layer of electro-optic material.
Specific embodiments of the present invention will now be described in more detail, though by way of illustration only, with reference to the accompanying drawings.
Part A: Image-Forming Method of the Present Invention
As already mentioned, in one aspect the present invention provides a method of forming an image on an architectural surface, the method comprising applying to the architectural surface, in order: a rear electrode layer; a light-transmissive front electrode layer; a photoconductive layer disposed between the front and rear electrode layers; and an electro-optic layer disposed between the front and rear electrode layers; applying a potential difference between the front and rear electrode layers; and imagewise exposing the front electrode layer to radiation effective to cause a change in the conductivity of the photoconductive layer, thereby causing an imagewise change in the optical state of the electro-optic layer.
The image-forming method of the present invention is designed to allow architectural sized (100 square foot, 10 square meter, or larger) high resolution images to be produced using unpatterned display media (i.e., with only two simple continuous electrodes, rather than a matrix of electrodes defining the pixels of the display) and no embedded electronic drivers. Essentially, the present invention solves this problem by inserting a layer of photoconductive material between the electrodes of an electro-optic display, thus forming a dual stimulus device, the stimuli being electric field and radiation, such that the display medium is addressed only when both stimuli are present.
When it is desired to produce a different image on the screen 200, the screen may be erased by removing the transparency 204 from the projector 202, thus allowing the entire area of the screen to be illuminated (and the entire photoconductive layer 110 thus rendered conductive), and applying between the electrode layers 104 and 112 a potential difference having a magnitude and polarity sufficient to drive the entire screen black. In practice, to avoid certain “memory” or “ghosting” effects common in certain electro-optic displays, it may be advisable to drive the entire screen from black to white and back again several times by reversing the polarity of the potential difference between the electrode layers 104 and 112.
It will be appreciated that the resolution of the image provided on the screen 200 is limited only by the resolution of the image provided by the projector 202, and any of the commercially known methods for the creation of high resolution projected images (for example, LCD projectors driven by computers) can be used. It is not essential to start image formation from a black screen; one could start from a white screen and drive the exposed areas to black (or to black and intermediate shades of gray), but note that in this case the final image would be a negative of the transparency 204.
The film shown in
The film used in the image-forming method of the present invention may be provided with a second adhesive layer and a release sheet on the opposed side of the rear electrode layer from the electro-optic layer to facilitate attachment of the film to an architectural surface, in the same manner as already described for the films of the present invention.
From the foregoing it will be seen that the image-forming method of the present invention allows high resolution addressing of large architectural displays using simple media with unpatterned electrodes. Also, using projected light to form the image makes the driving method simple and inexpensive.
Part B: Films for Varying Appearance of Architectural Surfaces
As already mentioned, in one aspect this invention provides a film for application to an architectural surface, the film comprising, in order: a light-transmissive colored layer; a light-transmissive front electrode layer; an electro-optic layer; a rear electrode layer; an adhesive layer; and a release sheet. This film is intended to be applied to an architectural surface by peeling the release sheet from the remaining layer of the film and contacting the adhesive layer (after any necessary activation, such as heating, if required) with the architectural surface, thereby securing the film (less the release sheet) to the architectural surface.
As will be apparent from the foregoing description, the film 300 may be produced by first producing a front plane laminate (FPL) as described in the aforementioned U.S. Pat. No. 6,982,178, starting from a film comprising the colored layer 304 and the front electrode layer 306. Separately, the lamination adhesive layer 312 is coated on to the release sheet, and the resultant adhesive layer/release sheet sub-assembly laminated to the rear electrode layer of the FPL to produce the final film. Such a process will leave an “extra” adhesive layer between the electro-optic layer 308 and the rear electrode layer 310 but such an extra adhesive layer is not objectionable provided it has the appropriate conductivity. Obviously, various other processes may be used to form the film 300. In particular, since the rear electrode layer 310 is planar, the electro-optic layer 308 could be coated on to the rear electrode 310, and thereafter a sub-assembly comprising the colored layer 304, front electrode layer 306 and a lamination adhesive layer could be laminated to the exposed electro-optic layer 308. Such a process will leave an “extra” adhesive layer between the electro-optic layer 308 and the front electrode layer 306 but such an extra adhesive layer is not objectionable provided it has the appropriate conductivity. This process has the advantage of avoiding subjecting the colored layer 304 to the elevated temperatures typically required to dry the electro-optic layer 308 when that layer is an encapsulated electrophoretic medium.
The colored layer 304 may be produced by applying a transmissive color overlay on to a receiver film. Alternatively, a transmissive color gel could be applied to the viewing surface of the front electrode layer shown in
Also mounted on the wall 400 are two strips 406, 408 of the film shown in
To allow for variations in the positions of the conductors 402, 404 (which need not be along the ends of the strips 406, 408 but can occupy intermediate positions) it may be desirable to provide the strip with multiple sets of connectors 410, 412 spaced from one another. Alternatively, the connectors 410, 412 can have a greater vertical dimension than illustrated in
In some cases, it may be advantageous to provide multiple sets of conductors 402, 404 on the wall, with corresponding multiple sets of connectors 410, 412. Such multiple sets of conductors and connectors can provide useful redundancy to enable the film to continue operating even if one contact fails. Multiple sets of conductors and connectors spaced from one another may also useful to produce interesting visual effects in the film in the manners described in US 2016/0232835 and US 2018/0136532.
However, the film 500 differs from the film 300 in that its electro-optic layer 508 is an encapsulated electrophoretic medium switchable between a white and a magenta state.
It will be apparent to those skilled in the art that numerous changes and modifications can be made in the specific embodiments of the invention described above without departing from the scope of the invention. Accordingly, the whole of the foregoing description is to be interpreted in an illustrative and not in a limitative sense.
With reference to
An electro-optic layer may also be embedded within the layer of adhesive material 16. The electro-optic layer may comprise a layer of electrophoretic media 22 having a layer of light-transmissive conductive material 18a, 18b applied to opposing sides of the layer of electrophoretic media 22. The layers of conductive material 18a, 18b serve as electrodes when connected to a power source (not shown) to apply an electric field across the thickness of the electrophoretic media 22 causing the electrophoretic media to switch optical states. An optional conductive adhesive layer 20a, 20b may be applied between the layers of conductive material 18a, 18b and the electrophoretic media 22.
This application is a continuation of copending application Ser. No. 16/224,896, filed Dec. 19, 2018 (published as U.S. Patent Application No. 2019/0187533), which claims benefit of Application Ser. No. 62/607,377, filed Dec. 19, 2017. This application is also related to U.S. Published Application Serial No. 2016/0259225 (now U.S. Pat. No. 10,175,550, issued Jan. 8, 2019) and 2016/0232835 (now U.S. Pat. No. 10,573,222, issued Feb. 25, 2020); U.S. Pat. Nos. 6,445,489; 6,704,133; 6,753,999 and 6,825,829; and provisional Application Ser. No. 62/703,156, filed Jul. 25, 2018 (now published as U.S. Patent Application No. 2020/0032081). The entire contents of these patents and applications and of all U.S. patents and published and copending applications mentioned below, are herein incorporated by reference.
Number | Name | Date | Kind |
---|---|---|---|
3932025 | Lakatos et al. | Jan 1976 | A |
4418346 | Batchelder | Nov 1983 | A |
4793691 | Enomoto | Dec 1988 | A |
5760761 | Sheridon | Jun 1998 | A |
5777782 | Sheridon | Jul 1998 | A |
5808783 | Crowley | Sep 1998 | A |
5872552 | Gordon, II et al. | Feb 1999 | A |
5930026 | Jacobson | Jul 1999 | A |
6017584 | Albert et al. | Jan 2000 | A |
6054071 | Mikkelsen, Jr. | Apr 2000 | A |
6055091 | Sheridon | Apr 2000 | A |
6097531 | Sheridon | Aug 2000 | A |
6118426 | Albert et al. | Sep 2000 | A |
6128124 | Silverman | Oct 2000 | A |
6130774 | Albert et al. | Oct 2000 | A |
6137467 | Sheridon et al. | Oct 2000 | A |
6144361 | Gordon, II et al. | Nov 2000 | A |
6147791 | Sheridon | Nov 2000 | A |
6172798 | Albert et al. | Jan 2001 | B1 |
6184856 | Gordon, II et al. | Feb 2001 | B1 |
6225971 | Gordon, II et al. | May 2001 | B1 |
6241921 | Jacobson et al. | Jun 2001 | B1 |
6271823 | Gordon, II et al. | Aug 2001 | B1 |
6301038 | Fitzmaurice et al. | Oct 2001 | B1 |
6445489 | Jacobson et al. | Sep 2002 | B1 |
6473072 | Comiskey et al. | Oct 2002 | B1 |
6504524 | Gates et al. | Jan 2003 | B1 |
6512354 | Jacobson et al. | Jan 2003 | B2 |
6531997 | Gates et al. | Mar 2003 | B1 |
6545797 | Chen et al. | Apr 2003 | B2 |
6664944 | Albert et al. | Dec 2003 | B1 |
6704133 | Gates et al. | Mar 2004 | B2 |
6710540 | Albert et al. | Mar 2004 | B1 |
6738050 | Comiskey et al. | May 2004 | B2 |
6753999 | Zehner et al. | Jun 2004 | B2 |
6784953 | Liang et al. | Aug 2004 | B2 |
6788452 | Liang et al. | Sep 2004 | B2 |
6825829 | Albert et al. | Nov 2004 | B1 |
6825970 | Goenaga et al. | Nov 2004 | B2 |
6864875 | Drzaic et al. | Mar 2005 | B2 |
6866760 | Paolini, Jr. et al. | Mar 2005 | B2 |
6870657 | Fitzmaurice et al. | Mar 2005 | B1 |
6900851 | Morrison et al. | May 2005 | B2 |
6914714 | Chen et al. | Jul 2005 | B2 |
6922276 | Zhang et al. | Jul 2005 | B2 |
6950220 | Abramson et al. | Sep 2005 | B2 |
6972893 | Chen et al. | Dec 2005 | B2 |
6982178 | LeCain et al. | Jan 2006 | B2 |
6995550 | Jacobson et al. | Feb 2006 | B2 |
7002728 | Pullen et al. | Feb 2006 | B2 |
7012600 | Zehner et al. | Mar 2006 | B2 |
7012735 | Honeyman | Mar 2006 | B2 |
7023420 | Comiskey et al. | Apr 2006 | B2 |
7030854 | Baucom et al. | Apr 2006 | B2 |
7034783 | Gates et al. | Apr 2006 | B2 |
7038656 | Liang et al. | May 2006 | B2 |
7038670 | Liang et al. | May 2006 | B2 |
7046228 | Liang et al. | May 2006 | B2 |
7052571 | Wang et al. | May 2006 | B2 |
7061166 | Kuniyasu | Jun 2006 | B2 |
7061662 | Chung et al. | Jun 2006 | B2 |
7072095 | Liang et al. | Jul 2006 | B2 |
7075502 | Drzaic et al. | Jul 2006 | B1 |
7112114 | Liang et al. | Sep 2006 | B2 |
7116318 | Amundson et al. | Oct 2006 | B2 |
7116466 | Whitesides et al. | Oct 2006 | B2 |
7119759 | Zehner et al. | Oct 2006 | B2 |
7119772 | Amundson et al. | Oct 2006 | B2 |
7144942 | Zang et al. | Dec 2006 | B2 |
7158282 | Liang et al. | Jan 2007 | B2 |
7167155 | Albert et al. | Jan 2007 | B1 |
7170670 | Webber | Jan 2007 | B2 |
7177066 | Chung et al. | Feb 2007 | B2 |
7193625 | Danner et al. | Mar 2007 | B2 |
7202847 | Gates | Apr 2007 | B2 |
7206119 | Honeyman et al. | Apr 2007 | B2 |
7236291 | Kaga et al. | Jun 2007 | B2 |
7236292 | LeCain | Jun 2007 | B2 |
7242514 | Chung et al. | Jul 2007 | B2 |
7259744 | Arango et al. | Aug 2007 | B2 |
7304787 | Whitesides et al. | Dec 2007 | B2 |
7312784 | Baucom et al. | Dec 2007 | B2 |
7312794 | Zehner et al. | Dec 2007 | B2 |
7321459 | Masuda | Jan 2008 | B2 |
7327511 | Whitesides et al. | Feb 2008 | B2 |
7339715 | Webber et al. | Mar 2008 | B2 |
7385751 | Chen et al. | Jun 2008 | B2 |
7408699 | Wang et al. | Aug 2008 | B2 |
7411719 | Paolini, Jr. et al. | Aug 2008 | B2 |
7420549 | Jacobson et al. | Sep 2008 | B2 |
7443571 | LeCain et al. | Oct 2008 | B2 |
7453445 | Amundson | Nov 2008 | B2 |
7492339 | Amundson | Feb 2009 | B2 |
7492505 | Liang et al. | Feb 2009 | B2 |
7513813 | Paolini, Jr. et al. | Apr 2009 | B2 |
7528822 | Amundson et al. | May 2009 | B2 |
7535624 | Amundson et al. | May 2009 | B2 |
7545358 | Gates et al. | Jun 2009 | B2 |
7561324 | Duthaler et al. | Jul 2009 | B2 |
7583251 | Arango et al. | Sep 2009 | B2 |
7602374 | Zehner et al. | Oct 2009 | B2 |
7612760 | Kawai | Nov 2009 | B2 |
7615325 | Liang et al. | Nov 2009 | B2 |
7636191 | Duthaler et al. | Dec 2009 | B2 |
7649666 | Isobe et al. | Jan 2010 | B2 |
7667684 | Jacobson et al. | Feb 2010 | B2 |
7679599 | Kawai | Mar 2010 | B2 |
7679813 | Liang et al. | Mar 2010 | B2 |
7679814 | Paolini, Jr. et al. | Mar 2010 | B2 |
7683606 | Kang et al. | Mar 2010 | B2 |
7684108 | Wang et al. | Mar 2010 | B2 |
7688297 | Zehner et al. | Mar 2010 | B2 |
7705824 | Baucom et al. | Apr 2010 | B2 |
7715088 | Liang et al. | May 2010 | B2 |
7728811 | Albert et al. | Jun 2010 | B2 |
7729039 | LeCain et al. | Jun 2010 | B2 |
7733311 | Amundson et al. | Jun 2010 | B2 |
7733335 | Zehner et al. | Jun 2010 | B2 |
7787169 | Abramson et al. | Aug 2010 | B2 |
7791782 | Paolini, Jr. et al. | Sep 2010 | B2 |
7791789 | Albert et al. | Sep 2010 | B2 |
7800813 | Wu et al. | Sep 2010 | B2 |
7821702 | Liang et al. | Oct 2010 | B2 |
7826129 | Wu et al. | Nov 2010 | B2 |
7839564 | Whitesides et al. | Nov 2010 | B2 |
7843621 | Danner et al. | Nov 2010 | B2 |
7843624 | Danner et al. | Nov 2010 | B2 |
7859742 | Chiu et al. | Dec 2010 | B1 |
7910175 | Webber | Mar 2011 | B2 |
7928659 | Mun et al. | Apr 2011 | B2 |
7952557 | Amundson | May 2011 | B2 |
7952790 | Honeyman et al. | May 2011 | B2 |
7956841 | Albert et al. | Jun 2011 | B2 |
7982479 | Wang et al. | Jul 2011 | B2 |
7982941 | Lin et al. | Jul 2011 | B2 |
7990600 | Sachs et al. | Aug 2011 | B2 |
7999787 | Amundson et al. | Aug 2011 | B2 |
8009348 | Zehner et al. | Aug 2011 | B2 |
8011592 | Wang | Sep 2011 | B2 |
3040594 | Paolini, Jr. et al. | Oct 2011 | A1 |
8034209 | Danner et al. | Oct 2011 | B2 |
8054526 | Bouchard | Nov 2011 | B2 |
8064962 | Wilcox et al. | Nov 2011 | B2 |
8068272 | LeCain et al. | Nov 2011 | B2 |
8077141 | Duthaler et al. | Dec 2011 | B2 |
8077381 | LeCain et al. | Dec 2011 | B2 |
8098418 | Paolini, Jr. et al. | Jan 2012 | B2 |
8125501 | Amundson et al. | Feb 2012 | B2 |
8220939 | Hiji et al. | Feb 2012 | B2 |
8139050 | Jacobson et al. | Mar 2012 | B2 |
8159636 | Sun et al. | Apr 2012 | B2 |
8162212 | Chung et al. | Apr 2012 | B2 |
8174490 | Whitesides et al. | May 2012 | B2 |
8177942 | Paolini, Jr. et al. | May 2012 | B2 |
8213076 | Albert et al. | Jul 2012 | B2 |
8243013 | Sprague et al. | Aug 2012 | B1 |
8274472 | Wang et al. | Sep 2012 | B1 |
8289250 | Zehner et al. | Oct 2012 | B2 |
8300006 | Zhou et al. | Oct 2012 | B2 |
8305341 | Arango et al. | Nov 2012 | B2 |
8314784 | Ohkami et al. | Nov 2012 | B2 |
8363299 | Paolini, Jr. et al. | Jan 2013 | B2 |
8373649 | Low et al. | Feb 2013 | B2 |
8384658 | Albert et al. | Feb 2013 | B2 |
8390301 | Danner et al. | Mar 2013 | B2 |
8422116 | Sprague et al. | Apr 2013 | B2 |
8441714 | Paolini, Jr. et al. | May 2013 | B2 |
8441716 | Paolini, Jr. et al. | May 2013 | B2 |
8456414 | Lin et al. | Jun 2013 | B2 |
8462102 | Wong et al. | Jun 2013 | B2 |
8466852 | Drzaic et al. | Jun 2013 | B2 |
8482835 | LeCain et al. | Jul 2013 | B2 |
8503063 | Sprague | Aug 2013 | B2 |
8514168 | Chung et al. | Aug 2013 | B2 |
8537105 | Chiu et al. | Sep 2013 | B2 |
8553012 | Baucom et al. | Oct 2013 | B2 |
8558783 | Wilcox et al. | Oct 2013 | B2 |
8558785 | Zehner et al. | Oct 2013 | B2 |
8558786 | Lin | Oct 2013 | B2 |
8558855 | Sprague et al. | Oct 2013 | B2 |
8576164 | Sprague et al. | Nov 2013 | B2 |
8576259 | Lin et al. | Nov 2013 | B2 |
8576470 | Paolini, Jr. et al. | Nov 2013 | B2 |
8576475 | Huang et al. | Nov 2013 | B2 |
8593396 | Amundson et al. | Nov 2013 | B2 |
8593721 | Albert et al. | Nov 2013 | B2 |
8605032 | Liu et al. | Dec 2013 | B2 |
8605354 | Zhang et al. | Dec 2013 | B2 |
8643595 | Chung et al. | Feb 2014 | B2 |
8649084 | Wang et al. | Feb 2014 | B2 |
8665206 | Lin et al. | Mar 2014 | B2 |
8670174 | Sprague et al. | Mar 2014 | B2 |
8681191 | Yang et al. | Mar 2014 | B2 |
8704756 | Lin | Apr 2014 | B2 |
8717664 | Wang et al. | May 2014 | B2 |
8730153 | Sprague et al. | May 2014 | B2 |
8786929 | LeCain et al. | Jul 2014 | B2 |
8786935 | Sprague | Jul 2014 | B2 |
8797634 | Paolini, Jr. et al. | Aug 2014 | B2 |
8810525 | Sprague | Aug 2014 | B2 |
8810899 | Sprague et al. | Aug 2014 | B2 |
8830553 | Patry et al. | Sep 2014 | B2 |
8830559 | Honeyman et al. | Sep 2014 | B2 |
8854721 | Danner et al. | Oct 2014 | B2 |
8873129 | Paolini, Jr. et al. | Oct 2014 | B2 |
8902153 | Bouchard et al. | Dec 2014 | B2 |
8902491 | Wang et al. | Dec 2014 | B2 |
8917439 | Wang et al. | Dec 2014 | B2 |
8928562 | Gates et al. | Jan 2015 | B2 |
8928641 | Chiu et al. | Jan 2015 | B2 |
8964282 | Wang et al. | Feb 2015 | B2 |
8973837 | Tsai et al. | Mar 2015 | B2 |
8976444 | Zhang et al. | Mar 2015 | B2 |
9013394 | Lin | Apr 2015 | B2 |
9013783 | Sprague | Apr 2015 | B2 |
9019197 | Lin | Apr 2015 | B2 |
9019198 | Lin et al. | Apr 2015 | B2 |
9019318 | Sprague et al. | Apr 2015 | B2 |
9075280 | Whitesides et al. | Jul 2015 | B2 |
9082352 | Cheng et al. | Jul 2015 | B2 |
9116412 | Lin | Aug 2015 | B2 |
9146439 | Zhang | Sep 2015 | B2 |
9164207 | Honeyman et al. | Oct 2015 | B2 |
9170467 | Whitesides et al. | Oct 2015 | B2 |
9170468 | Lin et al. | Oct 2015 | B2 |
9171508 | Sprague et al. | Oct 2015 | B2 |
9182646 | Paolini, Jr. et al. | Nov 2015 | B2 |
9188829 | Li et al. | Nov 2015 | B2 |
9195111 | Anseth et al. | Nov 2015 | B2 |
9197704 | Sun et al. | Nov 2015 | B2 |
9199441 | Danner | Dec 2015 | B2 |
9218773 | Sun et al. | Dec 2015 | B2 |
9224338 | Chan et al. | Dec 2015 | B2 |
9224342 | Lin | Dec 2015 | B2 |
9224344 | Chung et al. | Dec 2015 | B2 |
9230492 | Harrington et al. | Jan 2016 | B2 |
9238340 | Kayal et al. | Jan 2016 | B2 |
9251736 | Lin et al. | Feb 2016 | B2 |
9262973 | Wu et al. | Feb 2016 | B2 |
9268191 | Paolini, Jr. et al. | Feb 2016 | B2 |
9269311 | Amundson | Feb 2016 | B2 |
9279906 | Kang | Mar 2016 | B2 |
9285649 | Du et al. | Mar 2016 | B2 |
9293511 | Jacobson et al. | Mar 2016 | B2 |
9299294 | Lin et al. | Mar 2016 | B2 |
9341916 | Telfer et al. | May 2016 | B2 |
9360733 | Wang et al. | Jun 2016 | B2 |
9361836 | Telfer et al. | Jun 2016 | B1 |
9373289 | Sprague et al. | Jun 2016 | B2 |
9383623 | Lin et al. | Jul 2016 | B2 |
9390066 | Smith et al. | Jul 2016 | B2 |
9390661 | Chiu et al. | Jul 2016 | B2 |
9412314 | Amundson et al. | Aug 2016 | B2 |
9423666 | Wang et al. | Aug 2016 | B2 |
9459510 | Lin | Oct 2016 | B2 |
9460666 | Sprague et al. | Oct 2016 | B2 |
9491879 | Cheng et al. | Nov 2016 | B2 |
9495918 | Harrington et al. | Nov 2016 | B2 |
9501981 | Bilac et al. | Nov 2016 | B2 |
9513527 | Chan et al. | Dec 2016 | B2 |
9513743 | Sjodin et al. | Dec 2016 | B2 |
9514667 | Lin | Dec 2016 | B2 |
9541814 | Lin et al. | Jan 2017 | B2 |
9542895 | Gates et al. | Jan 2017 | B2 |
9554495 | Danner et al. | Jan 2017 | B2 |
9564088 | Wilcox et al. | Feb 2017 | B2 |
9612502 | Danner et al. | Apr 2017 | B2 |
9620048 | Sim et al. | Apr 2017 | B2 |
9620067 | Harrington et al. | Apr 2017 | B2 |
9627916 | Hsieh et al. | Apr 2017 | B2 |
9671668 | Chan et al. | Jun 2017 | B2 |
9672766 | Sjodin | Jun 2017 | B2 |
9691333 | Cheng et al. | Jun 2017 | B2 |
9697778 | Telfer et al. | Jul 2017 | B2 |
9721495 | Harrington et al. | Aug 2017 | B2 |
9733540 | LeCain et al. | Aug 2017 | B2 |
9740076 | Paolini, Jr. et al. | Aug 2017 | B2 |
9759980 | Du et al. | Sep 2017 | B2 |
9786233 | Hung | Oct 2017 | B2 |
9792861 | Chang et al. | Oct 2017 | B2 |
9792862 | Hung et al. | Oct 2017 | B2 |
9812073 | Lin et al. | Nov 2017 | B2 |
9966018 | Gates et al. | May 2018 | B2 |
10162242 | Wang et al. | Dec 2018 | B2 |
10175550 | Paolini, Jr. et al. | Jan 2019 | B2 |
10197883 | Paolini et al. | Feb 2019 | B2 |
10209556 | Rosenfeld et al. | Feb 2019 | B2 |
10229641 | Yang et al. | Mar 2019 | B2 |
10319313 | Harris et al. | Jun 2019 | B2 |
10339876 | Lin et al. | Jul 2019 | B2 |
10444553 | Laxton | Oct 2019 | B2 |
10514583 | Zhang | Dec 2019 | B2 |
10573222 | Paolini, Jr. et al. | Feb 2020 | B2 |
10672350 | Amundson et al. | Jun 2020 | B2 |
20020057250 | Michaelis | May 2002 | A1 |
20020090980 | Wilcox et al. | Jul 2002 | A1 |
20030076573 | Gates | Apr 2003 | A1 |
20030102858 | Jacobson et al. | Jun 2003 | A1 |
20040027327 | LeCain | Feb 2004 | A1 |
20040105036 | Danner et al. | Jun 2004 | A1 |
20040119681 | Albert et al. | Jun 2004 | A1 |
20040246562 | Chung et al. | Dec 2004 | A1 |
20050253777 | Zehner et al. | Nov 2005 | A1 |
20070091418 | Danner et al. | Apr 2007 | A1 |
20070103427 | Zhou et al. | May 2007 | A1 |
20070153361 | Danner | Jul 2007 | A1 |
20070176912 | Beames et al. | Aug 2007 | A1 |
20070237962 | Liang et al. | Oct 2007 | A1 |
20070285385 | Albert et al. | Dec 2007 | A1 |
20080024429 | Zehner | Jan 2008 | A1 |
20080024482 | Gates et al. | Jan 2008 | A1 |
20080043318 | Whitesides et al. | Feb 2008 | A1 |
20080048970 | Drzaic et al. | Feb 2008 | A1 |
20080136774 | Harris et al. | Jun 2008 | A1 |
20080303780 | Sprague et al. | Dec 2008 | A1 |
20090168067 | LeCain et al. | Jul 2009 | A1 |
20090174651 | Jacobson et al. | Jul 2009 | A1 |
20090225398 | Duthaler et al. | Sep 2009 | A1 |
20090322721 | Zehner et al. | Dec 2009 | A1 |
20100156780 | Jacobson et al. | Jun 2010 | A1 |
20100194733 | Lin et al. | Aug 2010 | A1 |
20100194789 | Lin et al. | Aug 2010 | A1 |
20100220121 | Zehner et al. | Sep 2010 | A1 |
20100265561 | Gates et al. | Oct 2010 | A1 |
20100302284 | Karaki | Dec 2010 | A1 |
20110043543 | Chen et al. | Feb 2011 | A1 |
20110063314 | Chiu et al. | Mar 2011 | A1 |
20110164301 | Paolini, Jr. et al. | Jul 2011 | A1 |
20110175875 | Lin et al. | Jul 2011 | A1 |
20110193840 | Amundson et al. | Aug 2011 | A1 |
20110193841 | Amundson et al. | Aug 2011 | A1 |
20110199671 | Amundson et al. | Aug 2011 | A1 |
20110221740 | Yang et al. | Sep 2011 | A1 |
20120001957 | Liu et al. | Jan 2012 | A1 |
20120098740 | Chiu et al. | Apr 2012 | A1 |
20120326957 | Drzaic et al. | Dec 2012 | A1 |
20130063333 | Arango et al. | Mar 2013 | A1 |
20130176288 | Hung et al. | Jul 2013 | A1 |
20130221112 | Lai et al. | Aug 2013 | A1 |
20130242378 | Paolini, Jr. et al. | Sep 2013 | A1 |
20130249782 | Wu et al. | Sep 2013 | A1 |
20130278995 | Drzaic et al. | Oct 2013 | A1 |
20140009817 | Wilcox et al. | Jan 2014 | A1 |
20140027044 | Kayal | Jan 2014 | A1 |
20140049808 | Yang | Feb 2014 | A1 |
20140055840 | Zang et al. | Feb 2014 | A1 |
20140078024 | Paolini, Jr. et al. | Mar 2014 | A1 |
20140078576 | Sprague | Mar 2014 | A1 |
20140204012 | Wu et al. | Jul 2014 | A1 |
20140206292 | Jung et al. | Jul 2014 | A1 |
20140240210 | Wu et al. | Aug 2014 | A1 |
20140253425 | Zalesky et al. | Sep 2014 | A1 |
20140293398 | Wang et al. | Oct 2014 | A1 |
20140362213 | Tseng | Dec 2014 | A1 |
20150005720 | Zang et al. | Jan 2015 | A1 |
20150118390 | Rosenfeld et al. | Apr 2015 | A1 |
20150262255 | Khajehnouri | Sep 2015 | A1 |
20150262551 | Zehner et al. | Sep 2015 | A1 |
20150268531 | Wang et al. | Sep 2015 | A1 |
20150301246 | Zang et al. | Oct 2015 | A1 |
20160012710 | Lu et al. | Jan 2016 | A1 |
20160048054 | Danner | Feb 2016 | A1 |
20160140910 | Amundson | May 2016 | A1 |
20160180777 | Lin et al. | Jun 2016 | A1 |
Number | Date | Country |
---|---|---|
102253502 | Nov 2011 | CN |
H1185064 | Mar 1999 | JP |
H1195691 | Apr 1999 | JP |
2002236471 | Aug 2002 | JP |
2003315847 | Nov 2003 | JP |
2005325677 | Nov 2005 | JP |
2007047446 | Feb 2007 | JP |
2000036560 | Jun 2000 | WO |
2004017135 | Feb 2004 | WO |
2017204328 | Nov 2017 | WO |
Number | Date | Country | |
---|---|---|---|
20220252954 A1 | Aug 2022 | US |
Number | Date | Country | |
---|---|---|---|
62607377 | Dec 2017 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 16224896 | Dec 2018 | US |
Child | 17727949 | US |