Patent Grant
11754903
Electro-optic assemblies useful in the production of electro-optic displays, and to materials for use in such assemblies are disclosed. More specifically, binder compositions having controlled volume resistivity, and electro-optic assemblies incorporating such materials, are disclosed.
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.
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.
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. The technologies described in these patents and applications include:
(a) Electrophoretic particles, fluids and fluid additives; see for example U.S. Pat. Nos. 5,961,804; 6,017,584; 6,120,588; 6,120,839; 6,262,706; 6,262,833; 6,300,932; 6,323,989; 6,377,387; 6,515,649; 6,538,801; 6,580,545; 6,652,075; 6,693,620; 6,721,083; 6,727,881; 6,822,782; 6,831,771; 6,870,661; 6,927,892; 6,956,690; 6,958,849; 7,002,728; 7,038,655; 7,052,766; 7,110,162; 7,113,323; 7,141,688; 7,142,351; 7,170,670; 7,180,649; 7,226,550; 7,230,750; 7,230,751; 7,236,290; 7,247,379; 7,277,218; 7,286,279; 7,312,916; 7,375,875; 7,382,514; 7,390,901; 7,411,720; 7,473,782; 7,532,388; 7,532,389; 7,572,394; 7,576,904; 7,580,180; 7,679,814; 7,746,544; 7,767,112; 7,848,006; 7,903,319; 7,951,938; 8,018,640; 8,115,729; 8,199,395; 8,257,614; 8,270,064; 8,305,341; 8,361,620; 8,363,306; 8,390,918; 8,582,196; 8,593,718; 8,654,436; 8,902,491; 8,961,831; 9,052,564; 9,114,663; 9,158,174; 9,341,915; 9,348,193; 9,361,836; 9,366,935; 9,372,380; 9,382,427; and 9,423,666; and U.S. Patent Applications Publication Nos. 2003/0048522; 2003/0151029; 2003/0164480; 2003/0169227; 2003/0197916; 2004/0030125; 2005/0012980; 2005/0136347; 2006/0132896; 2006/0281924; 2007/0268567; 2009/0009852; 2009/0206499; 2009/0225398; 2010/0148385; 2011/0217639; 2012/0049125; 2012/0112131; 2013/0161565; 2013/0193385; 2013/0244149; 2014/0011913; 2014/0078024; 2014/0078573; 2014/0078576; 2014/0078857; 2014/0104674; 2014/0231728; 2014/0339481; 2014/0347718; 2015/0015932; 2015/0177589; 2015/0177590; 2015/0185509; 2015/0218384; 2015/0241754; 2015/0248045; 2015/0301425; 2015/0378236; 2016/0139483; and 2016/0170106;
(b) Capsules, binders and encapsulation processes; see for example U.S. Pat. Nos. 5,930,026; 6,067,185; 6,130,774; 6,172,798; 6,249,271; 6,327,072; 6,392,785; 6,392,786; 6,459,418; 6,839,158; 6,866,760; 6,922,276; 6,958,848; 6,987,603; 7,061,663; 7,071,913; 7,079,305; 7,109,968; 7,110,164; 7,184,197; 7,202,991; 7,242,513; 7,304,634; 7,339,715; 7,391,555; 7,411,719; 7,477,444; 7,561,324; 7,848,007; 7,910,175; 7,952,790; 7,955,532; 8,035,886; 8,129,655; 8,446,664; and 9,005,494; and U.S. Patent Applications Publication Nos. 2005/0156340; 2007/0091417; 2008/0130092; 2009/0122389; and 2011/0286081;
(c) Films and sub-assemblies containing electro-optic materials; see for example U.S. Pat. Nos. 6,982,178 and 7,839,564;
(d) Backplanes, adhesive layers and other auxiliary layers and methods used in displays; see for example U.S. Pat. Nos. 7,116,318 and 7,535,624;
(e) Color formation and color adjustment; see for example U.S. Pat. Nos. 7,075,502 and 7,839,564;
(f) Methods for driving displays; see for example U.S. Pat. Nos. 7,012,600 and 7,453,445;
(g) Applications of displays; see for example U.S. Pat. Nos. 7,312,784 and 8,009,348; and
(h) Non-electrophoretic displays, as described in U.S. Pat. No. 6,241,921 and U.S. Patent Application Publication No. 2015/0277160; and applications of encapsulation and microcell technology other than displays; see for example U.S. Patent Application Publications Nos. 2015/0005720 and 2016/0012710.
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 media may also be used in the displays of the present invention.
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 encapsulated and 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, 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.
Electro-optic displays manufactured using lamination procedures normally have a layer of lamination adhesive between the electro-optic layer itself and the backplane, and the presence of this lamination adhesive layer affects the electro-optic characteristics of the displays. In particular, the electrical conductivity of the lamination adhesive layer affects both the low temperature performance and the resolution of the display. The low temperature performance of the display can (it has been found empirically) be improved by increasing the conductivity of the lamination adhesive layer, for example by doping the adhesive and/or binder with an inorganic or organic salt, such as potassium acetate, tetrabutylammonium chloride, tetrabutylammonium hexafluorophosphate, or other materials as described in the aforementioned U.S. Pat. Nos. 7,012,735 and 7,173,752. However, increasing the conductivity of the lamination adhesive tends to increase pixel blooming (a phenomenon whereby the area of the electro-optic layer which changes optical state in response to change of voltage at a pixel electrode is larger than the pixel electrode itself), and this blooming tends to reduce the resolution of the display.
To prevent blooming without negatively impacting temperature performance, dopants have been incorporated into the binder system of the electro-optic media, rather than the lamination adhesive. For example, colored encapsulated electrophoretic media, particularly multicolored capsules with four pigments, highly conductive binders have demonstrated improved performance in electro-optic states, color gamut, and temperature performance, as well as blooming. Achieving sufficiently high conductivities in the binder to obtain these results, however, is difficult with small molecule additives like tetrabutylammonium hexafluorophosphate. High concentrations of the dopants are required, and these high levels of concentration will significantly alter the mechanical properties of the binder, often leading to lamination and coating difficulties, or poor adhesion. Furthermore, the small molecule dopants may diffuse out of the binder and into the lamination adhesive.
Thus, there is a need for improved binder compositions for electro-optic displays and assemblies.
One aspect of the present invention is an electro-optic medium comprising an encapsulated material and a binder, the encapsulated material being configured to switch optical states upon application of an electric field, and the binder comprising a polymer having a plurality of side chains, wherein at least a portion of the side chains comprise an ionic moiety.
These and other aspects of the present invention will be apparent in view of the following description.
The drawing Figures depict one or more implementations in accord with the present concepts, by way of example only, not by way of limitations. In the figures, like reference numerals refer to the same or similar elements.
Generally, the various embodiments of the present invention provide an electro-optic medium comprising an encapsulated material configured to switch optical states upon the application of an electric field and a binder that comprises a polymer having a plurality of side chains, wherein at least a portion of the side chains comprise an ionic moiety. As used herein throughout the specification and the claims, “polymer” includes both homo-polymers and copolymers. The polymer is preferably a polyion having a high molecular weight (about 100,000 g/mol up to 1,000,000 g/mol), more preferably a polycation, most preferably a polycation comprising quaternized amines. The polymers are preferably good film-forming polymers. When mixed into the binder and applied as a layer, the resulting film preferably exhibits consistent mechanical properties over the entire area of the film and is chemically compatible with the other materials within the display stack when incorporated into a display, such that phase separation is minimized or eliminated.
The conductivity of the polymer in the binder may be controlled by varying the molecular weight of the polymer or the number of ionic side chains along the polymeric backbone of the polymer. Blends of polymers may also be used in the binder compositions according to the various embodiments of the present invention. The polymers with ionic side chains preferably exhibits a faint color, e.g. a pale yellow, but are more preferably colorless. The films containing the polymers preferably exhibit substantially uniform conductivity over the area of the film, and preferably maintain this property over time to improve the lifetime operation of the display.
As previously noted, the binder compositions made according to the various embodiments of the present invention may be included in various types of encapsulated electro-optic materials, such as rotating bichromal members, electrowetting materials, or electrophoretic media. The binder included in the various embodiments of the present invention are particularly well suited for encapsulated electrophoretic media comprising a plurality of electrically charged particles and a fluid, the charged particles being movable upon application of the electric field. The plurality of electrically charged particles may comprise at least two differently colored particles, such as red, green, blue, cyan, magenta, yellow, Hack, and white.
The one or more polymers containing ionic side chains that may be included in the binder compositions according to the various embodiments of the present invention are preferably highly conductive. The one or more polymers may have a conductivity of about 10−10 to 10−1 S/cm, preferably about 10−9 to about 10−2 S/cm, more preferably about 10−8 to about 10−4 S/cm, and most preferably a conductivity of about 10−7 to 10−6 S/cm.
The ionic functionality of the polymer may be covalently bonded to the polymeric backbone of the polymer. The ionic functionality present in the side chains may be provided by anionic moieties, cationic moieties, zwitterionic moieties, and combinations thereof. When the functionality of the side chains is anionic, it is preferred that functionality is provided by moieties that are not pH sensitive, such as sulfonic or phosphonic acid groups. Of the total number of side chains bonded to the polymeric backbone, the ionic side chains may constitute with increasing preference in the order given, at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, and 40%, and not more than, with increasing preference in the order given, 100%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, and 45%. As previously noted, the conductivity of the polymers may be controlled, not only by the number of ionic side chains, but also by the molecular weight of the polymers. The ionic polymers included in the various embodiments of the present invention may have a number average molecular weight, with increasing preference in the order give, of at least 20,000; 50,000; 100,000; 150,000; 200,000; 250,000; 300,000; 350,000; and 400,000 g/mol, and not more than, with increasing preference in the order given, 1,000,000; 950,000; 900,000; 850,000; 800,000; 750,000; 700,000; 650,000; 600,000; 550,000; and 500,000 g/mol.
The molecular weight of the polymer, as well as its glass transition temperature (Tg), may be selected depending on the desired mechanical properties of the final film containing the polymer, as well as the desired physical properties of the materials during processing, such as lamination, when fabricating a display.
The ionic polymers may be straight or branched polymers, e.g. comb polymers, brush polymers, dendritic polymers, star-shaped polymers, etc. The polymeric backbone may be derived from one or more polymers including, but not limited to, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyacrylates, polymethacrylates, polyurethanes, polysaccharides, polyolefins, polyethers, polyesters, polypeptides, proteins, and combinations thereof. In order to provide the polymeric backbone of the one or more polymers with ionic side chains, the one or more polymers may be functionalized by reacting the one or more polymers with one or more or more compounds including, but not limited to, sulfonic acids, phosphonic acids, quarternary amines, pyridines, imidazoles, carboxylic acids, salts of the aforementioned compounds, and combinations thereof.
In addition to the polyions, the binder composition may further comprise one or more polymers and/or oligomers that are not functionalized with an ionic side chain, such as water-soluble polymers, water-borne polymers, oil-soluble polymers, thermoset (e.g. epoxies) and thermoplastic polymers (e.g. polyesters), and radiation-cured polymers. Optional additives may include additives, such as small molecule coating aids or thickeners to modify the viscosity of the binder.
Among the water-soluble polymers are the various polysaccharides, the polyvinyl alcohols, N-methylpyrrolidone, N-vinylpyrrolidone, the various Carbowax® species (Union Carbide, Danbury, Conn.), and poly-2-hydroxyethylacrylate.
The water-dispersed or water-borne systems are generally latex compositions, typified by the Neorez® and Neocryl® resins (Zeneca Resins, Wilmington, Mass.), Acrysol® (Dow, Philadelphia, Pa.), Bayhydrol® (Bayer, Pittsburgh, Pa.), and the Cytec Industries (West Paterson, N.J.) HP line. These are generally lattices of polyurethanes, occasionally compounded with one or more of the acrylics, polyesters, polycarbonates or silicones, each lending the final cured resin in a specific set of properties defined by glass transition temperature, degree of “tack,” softness, clarity, flexibility, water permeability and solvent resistance, elongation modulus and tensile strength, thermoplastic flow, and solids level. Some water-borne systems can be mixed with reactive monomers and catalyzed to form more complex resins. Some can be further cross-linked by the use of a crosslinking reagent, such as an aziridine, for example, which reacts with carboxyl groups.
The electro-optic media according to the various embodiments of the present invention comprise a blend of the aforementioned binder and encapsulated material. The internal phase of the electro-optic medium preferably includes charged pigment particles in a suspending fluid. The fluids may be of low dielectric constant (preferably less than 10 and desirably less than 3). Especially preferred solvents include aliphatic hydrocarbons such as heptane, octane, and petroleum distillates such as Isopar (Exxon Mobil) or Isane® (Total); terpenes such as limonene, e.g., 1-limonene; and aromatic hydrocarbons such as toluene. A particularly preferred solvent is limonene, since it combines a low dielectric constant (2.3) with a relatively high refractive index (1.47). The index of refraction of the internal phase may be modified with the addition of index matching agents such as Cargille® index matching fluids available from Cargille-Sacher Laboratories Inc. (Cedar Grove, N.J.). In encapsulated media of the present invention, it is preferred that the refractive index of the dispersion of particles match as closely as possible that of the encapsulating material.
Charged pigment particles may be of a variety of colors and compositions. Additionally, the charged pigment particles may be functionalized with surface polymers to improve state stability. Such pigments are described in U.S. Patent Publication No. 2016/0085132, which is incorporated by reference in its entirety. For example, if the charged particles are of a white color, they may be formed from an inorganic pigment such as TiO2, ZrO2, ZnO, Al2O3, Sb2O3, BaSO4, PbSO4 or the like. They may also be polymer particles with a high refractive index (>1.5) and of a certain size (>100 nm) to exhibit a white color, or composite particles engineered to have a desired index of refraction. Black charged particles, they may be formed from CI pigment black 26 or 28 or the like (e.g., manganese ferrite black spinel or copper chromite black spinel) or carbon black. Other colors (non-white and non-black) may be formed from organic pigments such as CI pigment PR 254, PR122, PR149, PG36, PG58, PG7, PB28, PB15:3, PY83, PY138, PY150, PY155 or PY20. Other examples include Clariant Hostaperm Red D3G 70-EDS, Hostaperm Pink E-EDS, PV fast red D3G, Hostaperm red D3G 70, Hostaperm Blue B2G-EDS, Hostaperm Yellow H4G-EDS, Novoperm Yellow HR-70-EDS, Hostaperm Green GNX, BASF Irgazine red L 3630, Cinquasia Red L 4100 HD, and Irgazin Red L 3660 HD; Sun Chemical phthalocyanine blue, phthalocyanine green, diarylide yellow or diarylide AAOT yellow. Color particles can also be formed from inorganic pigments, such as CI pigment blue 28, CI pigment green 50, CI pigment yellow 227, and the like. The surface of the charged particles may be modified by known techniques based on the charge polarity and charge level of the particles required, as described in U.S. Pat. Nos. 6,822,782, 7,002,728, 9,366,935, and 9,372,380 as well as US Publication No. 2014-0011913, the contents of all of which are incorporated herein by reference in their entirety.
The particles may exhibit a native charge, or may be charged explicitly using a charge control agent, or may acquire a charge when suspended in a solvent or solvent mixture. Suitable charge control agents are well known in the art; they may be polymeric or non-polymeric in nature or may be ionic or non-ionic. Examples of charge control agent may include, but are not limited to, Solsperse 17000 (active polymeric dispersant), Solsperse 9000 (active polymeric dispersant), OLOA 11000 (succinimide ashless dispersant), Unithox 750 (ethoxylates), Span 85 (sorbitan trioleate), Petronate L (sodium sulfonate), Alcolec LV30 (soy Petrostep 8100 (petroleum sulfonate) or 1370 (barium sulfonate), Aerosol OT, polyisobutylene derivatives or polyethylene co-butylene) derivatives, and the like. In addition to the suspending fluid and charged pigment particles, internal phases may include stabilizers, surfactants and charge control agents. A stabilizing material may be adsorbed on the charged pigment particles when they are dispersed in the solvent. This stabilizing material keeps the particles separated from one another so that the variable transmission medium is substantially non-transmissive when the particles are in their dispersed state. As is known in the art, dispersing charged particles (typically a carbon black, as described above) in a solvent of low dielectric constant may be assisted by the use of a surfactant. Such a surfactant typically comprises a polar “head group” and a non-polar “tail group” that is compatible with or soluble in the solvent. In the present invention, it is preferred that the non-polar tail group be a saturated or unsaturated hydrocarbon moiety, or another group that is soluble in hydrocarbon solvents, such as for example a poly(dialkylsiloxane). The polar group may be any polar organic functionality, including ionic materials such as ammonium, sulfonate or phosphonate salts, or acidic or basic groups. Particularly preferred head groups are carboxylic acid or carboxylate groups. Stabilizers suitable for use with the invention include polyisobutylene and polystyrene. In some embodiments, dispersants, such as polyisobutylene succinimide and/or sorbitan trioleate, and/or 2-hexyldecanoic acid are added.
The gelatin-based capsule walls used in the variable transmission devices have been described in many of the E Ink and MIT patents and applications mentioned above. The gelatin is available from various commercial suppliers, such as Sigma Aldrich or Gelitia USA. It can be obtained in a variety of grades and purity depending upon the needs of the application. Gelatin primarily comprises collagen that has been collected from animal products (cow, pig, poultry, fish) and hydrolyzed. It comprises a mixture of peptides and proteins. In many of the embodiments described herein the gelatin is combined with acacia (gum arabic), which is derived from the hardened sap of the acacia tree. Acacia is a complex mixture of glycoproteins and polysaccharides, and it is often used as a stabilizer in food stuffs. Aqueous solutions of acacia and gelatin can be coacervated with a non-polar internal phase, as described below, to produce clear and flexible capsules containing internal phase.
Capsules incorporating gelatin/acacia may be prepared as follows; see, for example U.S. Pat. No. 7,170,670, incorporated by reference in its entirety. In this process, an aqueous mixture of gelatin and acacia is emulsified with a hydrocarbon internal phase (or other water-immiscible phase) to encapsulate the internal phase. The mixture is heated and the pH lowered to form a gelatin/acacia coacervate, thereby forming capsules. The temperature of the resultant mixture is then lowered and an aqueous solution of glutaraldehyde (an agent for cross-linking the capsule walls) is added. The resultant mixture is then warmed and stirred vigorously. A finishing step (holding the capsule mixture at 50 C for about one hour) is used to deactivate remaining glutaraldehyde, thereby assuring that the capsules will separate during sieving. The process yields capsules in the range of 20-100 μM and often incorporates over 50 percent of the starting materials into useable capsules. The capsules produced are then separated by size by sieving or other size exclusion sorting. After size sorting, the capsules are mixed with the binder to create a slurry for coating, e.g., using slot coating, knife coating, spin coating, etc. The weight ratio of capsule to binder in the electro-optic medium may be 4:1 to 50:1, more preferably 10:1 to 30:1, and most preferably about 15:1.
The electro-optic media made according to the various embodiments of the present invention may be incorporated into electro-optic displays and assemblies. 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.
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. 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 Del., 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
Aqueous capsule slurries comprising gelatin; acacia microcapsules having a mean size of approximate 40 μm containing a dispersion of white and three different colored pigments (cyan, magenta, and yellow) in a nonpolar solvent were mixed into four different binders; A) a polyvinyl alcohol) with cationic side chains, B) a low molecular weight polyvinylpyrrolidone with cationic side chains, C) a high molecular weight polyvinylpyrrolidone with cationic side chains, and D) a polyurethane dispersion control. Each binder was mixed at a ratio of 1 part by weight binder to 15 parts by weight of capsules. The polyurethane binder was also mixed with thickeners, a small molecule ionic dopant, and coating aids. The resultant mixtures were bar coated on to a 125 μm thick indium-tin oxide coated polyester film. The coated film was dried to produce an electrophoretic medium approximately 21 μm thick (18-25 g/m2 depending on density) containing essentially a single layer of capsules. Each dried film was laminated with a polyurethane adhesive doped with conductive salts, which was subsequently laminated to a screen-printed backplane assembly approximately 2 inches square to create an electrophoretic display test module. The module was driven using a waveform summarized in Table 1. The basic waveform is divided into six sections, each 20.5 seconds long. During each section a square-wave AC fundamental with 30 Hz frequency is offset by a DC voltage as shown in the table (not every offset is shown, but the sequence should be obvious from the table entries). The duty cycle of the square wave AC (i.e., the proportion of the time of one cycle of positive and negative voltages during which the positive voltage is applied) is varied as shown in the table. The whole test consists of three repetitions of the basic waveform, each time with a different voltage offset sequence, shown as “High V offset”, “Mid V offset” and “Low V offset”. Thus, for example, the initial “High V offset” is −15V. The magnitude of the square wave AC is +/−30V for the “High V offset” sequence, +/−20V for the “Mid V offset” sequence, and “+/−10V for the “Low V offset” sequence.
As the display was electrically driven, various optical states were generated and reflection spectra were acquired. These were used to calculate CIE L*, a* and b* values for the light reflected from the display as the waveform was applied. For each spectral sample, a distance in L*a*b* space of the color of the display from each of the eight SNAP (Specifications for Newsprint Advertising Production) color standard primaries was calculated in units of ΔE*. For each electrophoretic display tested, the minimum distances of the colors displayed from the SNAP primaries were recorded. The primary colors were red, green, blue, yellow, cyan, magenta, white and black (R, G, B, Y, C, M, W, and K). The lower the distance, the closer is the performance of the electrophoretic display to the SNAP target, indicating better color saturation of the optical state of the display. The primary colors of the inventive displays were significantly closer to the SNAP color value compared to those of the control electrophoretic display. The results are summarized in Table.
Color gamut results: In addition to primary color measurements provided in Table 2, the full volume color gamut from all measured points was determined for each electrophoretic display. Larger volume color gamut indicates an electrophoretic device of higher color capability. The results of this assessment are provided in
Evaluations of electrophoretic displays comprising the control and inventive electrophoretic media at different temperatures (0° C., 25° C., and 50° C.) were also performed. They showed that the display that comprise inventive electrophoretic media with binder comprising polymers with cationic side chains provide improved color performance, that is, more saturated primary colors and larger volume color gamut, compared to the display that comprises the control electrophoretic medium with polyurethane dispersion including small molecule dopants.
Blooming results: Blooming evaluations were made using a Mikrotron K/W Camera at 50× magnification at 25° C. and 35° C., switched from both a K (black) and W (white) background, using an EVK3 with a TPC 28V controller, and 1000 ms pulses at 65 Hz. The samples were switched to checkerboard patterns from the previous state and the optical shift was normalized to the dynamic range. The electrophoretic display comprising (a) the inventive electrophoretic medium with a polyvinyl alcohol) having cationic side chains polymer binder (Binder A), and (b) an adhesive layer having an ionic dopant (tetrabutylammonium hexafluorophosphate) at a concentration of 180 ppm, exhibited very little blooming at both temperatures.
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. All of the aforementioned issued patents and pending patent applications are incorporated herein by reference in their entireties.
This application claims the benefit of and priority to U.S. Provisional Patent Application having Ser. No. 62/768,572, filed on Nov. 16, 2018, the contents of which are incorporated by reference herein in their entireties.
| Number | Name | Date | Kind |
|---|---|---|---|
| 4418346 | Batchelder | Nov 1983 | 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 et al. | Jul 1999 | A |
| 5961804 | Jacobson et al. | Oct 1999 | A |
| 6017584 | Albert et al. | Jan 2000 | A |
| 6054071 | Mikkelsen, Jr. | Apr 2000 | A |
| 6055091 | Sheridon et al. | Apr 2000 | A |
| 6067185 | Albert et al. | May 2000 | A |
| 6097531 | Sheridon | Aug 2000 | A |
| 6120588 | Jacobson | Sep 2000 | A |
| 6120839 | Comiskey 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 |
| 6249271 | Albert et al. | Jun 2001 | B1 |
| 6262706 | Albert et al. | Jul 2001 | B1 |
| 6262833 | Loxley et al. | Jul 2001 | B1 |
| 6271823 | Gordon, II et al. | Aug 2001 | B1 |
| 6300932 | Albert | Oct 2001 | B1 |
| 6301038 | Fitzmaurice et al. | Oct 2001 | B1 |
| 6323989 | Jacobson et al. | Nov 2001 | B1 |
| 6327072 | Comiskey et al. | Dec 2001 | B1 |
| 6377387 | Duthaler et al. | Apr 2002 | B1 |
| 6392785 | Albert et al. | May 2002 | B1 |
| 6392786 | Albert et al. | May 2002 | B1 |
| 6459418 | Comiskey et al. | Oct 2002 | B1 |
| 6515649 | Albert et al. | Feb 2003 | B1 |
| 6538801 | Jacobson et al. | Mar 2003 | B2 |
| 6580545 | Morrison et al. | Jun 2003 | B2 |
| 6652075 | Jacobson | Nov 2003 | B2 |
| 6693620 | Herb et al. | Feb 2004 | B1 |
| 6721083 | Jacobson et al. | Apr 2004 | B2 |
| 6727881 | Albert et al. | Apr 2004 | B1 |
| 6822782 | Honeyman et al. | Nov 2004 | B2 |
| 6831771 | Ho et al. | Dec 2004 | B2 |
| 6839158 | Albert et al. | Jan 2005 | B2 |
| 6866760 | Paolini Jr. et al. | Mar 2005 | B2 |
| 6870657 | Fitzmaurice et al. | Mar 2005 | B1 |
| 6870661 | Pullen et al. | Mar 2005 | B2 |
| 6914713 | Chung et al. | Jul 2005 | B2 |
| 6922276 | Zhang et al. | Jul 2005 | B2 |
| 6927892 | Ho et al. | Aug 2005 | B2 |
| 6950220 | Abramson et al. | Sep 2005 | B2 |
| 6956690 | Yu et al. | Oct 2005 | B2 |
| 6958848 | Cao et al. | Oct 2005 | B2 |
| 6958849 | Chen et al. | Oct 2005 | B2 |
| 6982178 | LeCain et al. | Jan 2006 | B2 |
| 6987603 | Paolini, Jr. et al. | Jan 2006 | B2 |
| 7002728 | Pullen et al. | Feb 2006 | B2 |
| 7012600 | Zehner et al. | Mar 2006 | B2 |
| 7012735 | Honeyman et al. | Mar 2006 | B2 |
| 7038655 | Herb et al. | May 2006 | B2 |
| 7052766 | Zang et al. | May 2006 | B2 |
| 7061663 | Cao et al. | Jun 2006 | B2 |
| 7071913 | Albert et al. | Jul 2006 | B2 |
| 7075502 | Drzaic et al. | Jul 2006 | B1 |
| 7079305 | Paolini, Jr. et al. | Jul 2006 | B2 |
| 7109968 | Albert et al. | Sep 2006 | B2 |
| 7110162 | Wu et al. | Sep 2006 | B2 |
| 7110164 | Paolini, Jr. et al. | Sep 2006 | B2 |
| 7113323 | Ho et al. | Sep 2006 | B2 |
| 7116318 | Amundson et al. | Oct 2006 | B2 |
| 7141688 | Feng et al. | Nov 2006 | B2 |
| 7142351 | Chung et al. | Nov 2006 | B2 |
| 7170670 | Webber | Jan 2007 | B2 |
| 7173752 | Doshi et al. | Feb 2007 | B2 |
| 7180649 | Morrison et al. | Feb 2007 | B2 |
| 7184197 | Liang et al. | Feb 2007 | B2 |
| 7202991 | Zhang et al. | Apr 2007 | B2 |
| 7226550 | Hou et al. | Jun 2007 | B2 |
| 7230750 | Whitesides et al. | Jun 2007 | B2 |
| 7230751 | Whitesides et al. | Jun 2007 | B2 |
| 7236290 | Zhang et al. | Jun 2007 | B1 |
| 7236291 | Kaga et al. | Jun 2007 | B2 |
| 7242513 | Albert et al. | Jul 2007 | B2 |
| 7247379 | Pullen et al. | Jul 2007 | B2 |
| 7277218 | Hwang et al. | Oct 2007 | B2 |
| 7286279 | Yu et al. | Oct 2007 | B2 |
| 7304634 | Albert et al. | Dec 2007 | B2 |
| 7312784 | Baucom et al. | Dec 2007 | B2 |
| 7312916 | Pullen et al. | Dec 2007 | B2 |
| 7321459 | Masuda et al. | Jan 2008 | B2 |
| 7339715 | Webber et al. | Mar 2008 | B2 |
| 7375875 | Whitesides et al. | May 2008 | B2 |
| 7382514 | Hsu et al. | Jun 2008 | B2 |
| 7390901 | Yang et al. | Jun 2008 | B2 |
| 7391555 | Albert et al. | Jun 2008 | B2 |
| 7411719 | Paolini, Jr. et al. | Aug 2008 | B2 |
| 7411720 | Honeyman et al. | Aug 2008 | B2 |
| 7420549 | Jacobson et al. | Sep 2008 | B2 |
| 7453445 | Amundson | Nov 2008 | B2 |
| 7473782 | Yang et al. | Jan 2009 | B2 |
| 7477444 | Cao et al. | Jan 2009 | B2 |
| 7532388 | Whitesides et al. | May 2009 | B2 |
| 7532389 | Li et al. | May 2009 | B2 |
| 7535624 | Amundson et al. | May 2009 | B2 |
| 7561324 | Duthaler et al. | Jul 2009 | B2 |
| 7572394 | Gu et al. | Aug 2009 | B2 |
| 7576904 | Chung et al. | Aug 2009 | B2 |
| 7580180 | Ho et al. | Aug 2009 | B2 |
| 7679814 | Paolini, Jr. et al. | Mar 2010 | B2 |
| 7746544 | Comiskey et al. | Jun 2010 | B2 |
| 7767112 | Hou et al. | Aug 2010 | B2 |
| 7839564 | Whitesides et al. | Nov 2010 | B2 |
| 7848006 | Wilcox et al. | Dec 2010 | B2 |
| 7848007 | Paolini, Jr. et al. | Dec 2010 | B2 |
| 7903319 | Honeyman et al. | Mar 2011 | B2 |
| 7910175 | Webber | Mar 2011 | B2 |
| 7951938 | Yang et al. | May 2011 | B2 |
| 7952790 | Honeyman et al. | May 2011 | B2 |
| 7955532 | Liang et al. | Jun 2011 | B2 |
| 8009348 | Zehner et al. | Aug 2011 | B2 |
| 8018640 | Whitesides et al. | Sep 2011 | B2 |
| 8035886 | Jacobson | Oct 2011 | B2 |
| 8115729 | Danner et al. | Feb 2012 | B2 |
| 8129655 | Jacobson et al. | Mar 2012 | B2 |
| 8199395 | Whitesides et al. | Jun 2012 | B2 |
| 8257614 | Gu et al. | Sep 2012 | B2 |
| 8270064 | Feick et al. | Sep 2012 | B2 |
| 8305341 | Arango et al. | Nov 2012 | B2 |
| 8361620 | Zang et al. | Jan 2013 | B2 |
| 8363306 | Du et al. | Jan 2013 | B2 |
| 8390918 | Wilcox et al. | Mar 2013 | B2 |
| 8446664 | Chen et al. | May 2013 | B2 |
| 8582196 | Walls et al. | Nov 2013 | B2 |
| 8593718 | Comiskey et al. | Nov 2013 | B2 |
| 8654436 | Feick | Feb 2014 | B1 |
| 8902491 | Wang et al. | Dec 2014 | B2 |
| 8961831 | Du et al. | Feb 2015 | B2 |
| 9005494 | Valianatos et al. | Apr 2015 | B2 |
| 9052564 | Sprague et al. | Jun 2015 | B2 |
| 9114663 | Ho et al. | Aug 2015 | B2 |
| 9158174 | Walls et al. | Oct 2015 | B2 |
| 9341915 | Yang et al. | May 2016 | B2 |
| 9348193 | Hiji et al. | May 2016 | B2 |
| 9361836 | Telfer et al. | Jun 2016 | B1 |
| 9366935 | Du et al. | Jun 2016 | B2 |
| 9372380 | Du et al. | Jun 2016 | B2 |
| 9382427 | Du et al. | Jul 2016 | B2 |
| 9423666 | Wang et al. | Aug 2016 | B2 |
| 9428649 | Li et al. | Aug 2016 | B2 |
| 9557623 | Wang et al. | Jan 2017 | B2 |
| 9664978 | Arango et al. | May 2017 | B2 |
| 9670367 | Li et al. | Jun 2017 | B2 |
| 9688859 | Yezek et al. | Jun 2017 | B2 |
| 9726957 | Telfer et al. | Aug 2017 | B2 |
| 9778537 | Wang et al. | Oct 2017 | B2 |
| 9835926 | Sprague et al. | Dec 2017 | B2 |
| 9921451 | Telfer et al. | Mar 2018 | B2 |
| 10444553 | Laxton | Oct 2019 | B2 |
| 10444590 | Duthaler et al. | Oct 2019 | B2 |
| 20030048522 | Liang et al. | Mar 2003 | A1 |
| 20030151029 | Hsu et al. | Aug 2003 | A1 |
| 20030164480 | Wu et al. | Sep 2003 | A1 |
| 20040030125 | Li et al. | Feb 2004 | A1 |
| 20050012980 | Wilcox et al. | Jan 2005 | A1 |
| 20050105159 | Paolini | May 2005 | A1 |
| 20050156340 | Valianatos et al. | Jul 2005 | A1 |
| 20070091417 | Cao et al. | Apr 2007 | A1 |
| 20080130092 | Whitesides et al. | Jun 2008 | A1 |
| 20090009852 | Honeyman et al. | Jan 2009 | A1 |
| 20090096355 | Ohuchi | Apr 2009 | A1 |
| 20090122389 | Whitesides | May 2009 | A1 |
| 20090206499 | Whitesides | Aug 2009 | A1 |
| 20090225398 | Duthaler et al. | Sep 2009 | A1 |
| 20090244693 | Nishio | Oct 2009 | A1 |
| 20100148385 | Balko et al. | Jun 2010 | A1 |
| 20110217639 | Sprague | Sep 2011 | A1 |
| 20110286081 | Jacobson | Nov 2011 | A1 |
| 20120049125 | Du et al. | Mar 2012 | A1 |
| 20130161565 | Laxton | Jun 2013 | A1 |
| 20130193385 | Li et al. | Aug 2013 | A1 |
| 20130244149 | Wang et al. | Sep 2013 | A1 |
| 20140011913 | Du et al. | Jan 2014 | A1 |
| 20140078024 | Paolini, Jr. et al. | Mar 2014 | A1 |
| 20140078573 | Comiskey et al. | Mar 2014 | A1 |
| 20140078576 | Sprague | Mar 2014 | A1 |
| 20140078857 | Nelson et al. | Mar 2014 | A1 |
| 20140104674 | Ting et al. | Apr 2014 | A1 |
| 20140231728 | Du et al. | Aug 2014 | A1 |
| 20150005720 | Zang | Jan 2015 | A1 |
| 20150177590 | Laxton | Jun 2015 | A1 |
| 20150185509 | Wang et al. | Jul 2015 | A1 |
| 20150241754 | Du et al. | Aug 2015 | A1 |
| 20150301425 | Du et al. | Oct 2015 | A1 |
| 20160012710 | Lu et al. | Jan 2016 | A1 |
| 20160170106 | Wang et al. | Jun 2016 | A1 |
| 20160366909 | Geremia | Dec 2016 | A1 |
| 20170088758 | Bzowej et al. | Mar 2017 | A1 |
| Entry |
|---|
| Wood, D., “An Electrochromic Renaissance?” Information Display, 18(3), (Mar. 24, 2002) Mar. 1, 2002. |
| O'Regan, B. et al., “A Low Cost, High-efficiency Solar Cell Based on Dye-sensitized colloidal TiO2 Films”, Nature, vol. 353, pp. 737-740 (Oct. 24, 1991). |
| Bach, Udo. et al., “Nanomaterials-Based Electrochromics for Paper-Quality Displays”, Adv. Mater, vol. 14, No. 11, pp. 845-848, (Jun. 5, 2002). |
| Hayes, R.A. et al., “Video-Speed Electronic Paper Based on Electrowetting”, Nature, vol. 425, No. 25, pp. 383-385 (Sep. 2003). |
| Kitamura, T. et al., “Electrical toner movement for electronic paper-like display”, Asia Display/IDW '01, pp. 1517-1520, Paper HCS1-1 (2001). |
| Yamaguchi, Y. et al., “Toner display using insulative particles charged triboelectrically”, Asia Display/IDW '01, pp. 1729-1730, Paper AMD4-4 (2001). |
| Number | Date | Country | |
|---|---|---|---|
| 62768572 | Nov 2018 | US |
