Color electrophoretic layers containing microcapsules with non-ionic polymer walls.

Abstract

To provide a color electrophoretic layer including microcapsules with nonionic polymeric walls.SOLUTION: A capsule comprises a capsule wall and an electrophoretic fluid encapsulated by the capsule wall. The capsule wall comprises a cross-linked nonionic, water-soluble or water-dispersible polymer. The electrophoretic fluid comprises a suspending fluid, first pigment particles, second pigment particles, and third pigment particles. In some embodiments, the electrophoretic fluid includes a fourth electrophoretic particle. The first, second and third particles are electrically charged, suspended in the suspending fluid, and capable of moving through the suspending fluid upon application of an electric field to the capsule.SELECTED DRAWING: Figure 4

Description

[Background technology]

[0001] (Related Applications) This application claims priority to U.S. Provisional Patent Application No. 62 / 952,534, filed December 23, 2019. All references, patents, and patent applications disclosed herein are incorporated by reference in their entirety.

[0002] Conventional electrophoretic displays based on microencapsulated pigments, such as those found in most electronic readers, use coacervates of gelatin and acacia to form the microcapsule walls. For black and white displays, this material has been shown to provide excellent performance, and such capsules are relatively easy to manufacture. More complex three- and four-color electrophoretic systems have been developed in which the pigments are encapsulated in microcells rather than microcapsules. (Methods for forming, filling, and sealing such microcells are described in numerous patents and patent applications held by E Ink Corporation.) However, for large area display applications, it may be preferable to have the option of microcapsule architecture, since the maximum size of the embossed microcell area may, in some embodiments, be limited by the diameter of the embossing drum.

[0003] It would be useful to have a device with microcapsules containing three or more pigments, such that the same electrophoretic fluid would produce optical states similar to those obtained in a microcell compartment or liquid test cell (e.g., test pixel) with only minor adjustments to the addressing waveform required, which is typically not possible using gelatin / acacia capsule walls.

[0004] In this regard, there is a long and rich history of encapsulation, and many processes and polymers have been proposed as materials for electrophoretic capsules.For example, US Published Patent Application No. 2006 / 0245038 proposes many possible substances, including gelatin, polyvinyl alcohol, polyvinyl acetate, and cellulose derivatives, as materials for manufacturing capsule walls via coacervation process.However, no guidance is provided regarding the possible influence of capsule wall materials on the function of encapsulated electrophoretic fluid. Summary of the Invention [Means for solving the problem]

[0005] In a first aspect, a capsule for electrophoretic media is provided. The capsule comprises a capsule wall and an electrophoretic fluid encapsulated by the capsule wall. Specifically, the capsule comprises a capsule wall comprising a water-soluble (or water-dispersible) and cross-linked non-ionic polymer, while the electrophoretic fluid comprises a suspending solvent, a first pigment particle, a second pigment particle, and a third pigment particle, the first, second, and third particles being differently colored, electrically charged, suspended in the suspending fluid, and capable of moving through the suspending fluid in response to application of an electric field to the capsule. In some embodiments, the non-ionic polymer is a polyol. In some embodiments, the polyol is polyvinyl alcohol. In some embodiments, the capsule wall comprises a hardened coacervation layer formed from a non-ionic polymer and a polyvinyl lactam, which is optionally polyvinylpyrrolidone. In some embodiments, the capsule wall is optionally cross-linked by reaction with a dialdehyde, which is glutaraldehyde. In some embodiments, the suspension medium comprises a hydrocarbon, such as a mixture of hydrocarbons, such as ISOPAR® E, available from Sigma-Aldrich. In some embodiments, one or more of the pigment particles are reflective. In some embodiments, one or more of the pigment particles are absorptive. In some embodiments, the electrophoretic fluid further comprises a fourth pigment particle. In some embodiments, the electrophoretic fluid comprises a white pigment, a yellow pigment, a magenta pigment, and a cyan pigment. In some embodiments, the electrophoretic fluid comprises a white pigment, a black pigment, a yellow pigment, and a red pigment. In some embodiments, the electrophoretic fluid comprises a black pigment, a red pigment, a yellow pigment, and a blue pigment. In some embodiments. The capsules of the present invention may further comprise a binder contained within the electrophoretic medium and surrounding the capsules. In some embodiments, the capsules have an average diameter of 15 μm to 50 μm, with less than one third of the capsules (by number) being smaller than 15 μm or larger than 50 μm.Such an electrophoretic medium may then be incorporated into an electrophoretic display, which includes at least one electrode disposed adjacent to the electrophoretic medium and arranged to apply an electric field to the electrophoretic medium. The electrophoretic display may be rectangular in shape and have a diagonal measurement of more than 30 cm, for example more than 50 cm. The electrophoretic display may additionally include a second electrode or electrode layer, which may include an array of pixel electrodes controlled with thin film transistors. In some embodiments, one or more of the electrodes may be light-transmitting.

[0006] In a second aspect, a method for producing the capsules of the present invention is provided. The method includes providing a polymer solution comprising a non-ionic, water-soluble, or water-dispersible starting polymer in an aqueous solvent; providing an electrophoretic fluid comprising a suspending solvent and pigment particles; mixing the polymer solution and the electrophoretic fluid to create a reaction mixture; heating the reaction mixture to a temperature above a lower critical solution temperature of the polymer solution, thereby forming an oil-in-water emulsion comprising the electrophoretic fluid; adding a crosslinker to the oil-in-water emulsion, thereby forming a hardening mixture; and heating the hardening mixture to form a capsule that encapsulates the electrophoretic medium. In some embodiments, the polymer solution comprises polyvinyl alcohol. In some embodiments, the polymer solution comprises a copolymer of vinyl acetate. In some embodiments, the method further includes adding a second non-ionic, water-soluble, or water-dispersible starting polymer to the polymer solution. In some embodiments, the second non-ionic polymer is polyvinylpyrrolidone. In some embodiments, the crosslinker is glutaraldehyde. In some embodiments, the method additionally includes the step of adding a coacervation inducer to the polymer solution. In some embodiments, the coacervation inducer is a water-soluble (or water-dispersible) salt. In some embodiments, the salt is a sulfate salt, such as sodium sulfate. The present invention provides, for example, the following: (Item 1) A capsule comprising a capsule wall and an electrophoretic fluid encapsulated by the capsule wall, the capsule wall comprises a water-soluble or water-dispersible, crosslinked, non-ionic polymer; The electrophoretic fluid comprises a suspending solvent, first pigment particles, second pigment particles, and third pigment particles, the first, second, and third particles being differently colored and electrically charged, suspended in the suspending fluid, and capable of moving through the suspending fluid in response to application of an electric field to the capsule. (Item 2) 2. The capsule according to claim 1, wherein the non-ionic polymer is a polyol. (Item 3) 3. The capsule according to claim 2, wherein the polyol is polyvinyl alcohol. (Item 4) 2. The capsule of claim 1, wherein the capsule wall comprises a hardened coacervation layer formed from the non-ionic polymer and polyvinyl lactam. (Item 5) 5. The capsule according to item 4, wherein the polyvinyl lactam is polyvinylpyrrolidone. (Item 6) 2. The capsule according to claim 1, wherein the capsule wall is crosslinked by reaction with a dialdehyde. (Item 7) 7. The capsule according to claim 6, wherein the dialdehyde is glutaraldehyde. (Item 8) 2. The capsule of claim 1, wherein the suspending solvent comprises a hydrocarbon. (Item 9) Item 1, the capsule of item 1, wherein the electrophoretic fluid further comprises fourth pigment particles. (Item 10) Item 1. An electrophoretic medium comprising a plurality of capsules according to item 1 and a binder surrounding the capsules. (Item 11) 11. An electrophoretic display comprising a layer of an electrophoretic medium according to item 10 and at least one electrode disposed adjacent to the electrophoretic medium and arranged to apply an electric field to the electrophoretic medium. (Item 12) 11. An electrophoretic medium according to item 10, comprising capsules having an average diameter of 15 μm to 50 μm, wherein less than one third (by number) of said capsules are smaller than 15 μm or larger than 50 μm. (Item 13) 13. An electrophoretic display comprising a layer of the electrophoretic medium of item 12 and at least one electrode disposed adjacent to the electrophoretic medium and arranged to apply an electric field to the electrophoretic medium. (Item 14) 1. A method for producing a capsule that encapsulates an electrophoretic medium, the method comprising: providing a polymer solution comprising a non-ionic, water-soluble, or water-dispersible starting polymer in an aqueous solvent; Providing an electrophoretic fluid comprising a suspending solvent and pigment particles; mixing the polymer solution and the electrophoretic fluid to form a reaction mixture; heating the reaction mixture to a temperature above a lower critical solution temperature of the polymer solution, thereby forming an oil-in-water emulsion containing the electrophoretic fluid; adding a crosslinker to said oil-in-water emulsion, thereby forming a cured mixture; heating the cured mixture to form capsules encapsulating the electrophoretic medium; A method comprising: (Item 15) Item 15. The method of item 14, wherein the polymer solution comprises polyvinyl alcohol. (Item 16) Item 15. The method of item 14, wherein the polymer solution comprises a copolymer of vinyl acetate. (Item 17) 15. The method of claim 14, further comprising adding a second non-ionic, water-soluble, or water-dispersible starting polymer to the polymer solution. (Item 18) 18. The method of claim 17, wherein the second non-ionic polymer is polyvinylpyrrolidone. (Item 19) 15. The method of claim 14, wherein the cross-linking agent is glutaraldehyde. (Item 20) 15. The method of claim 14, further comprising adding a coacervation inducer to the polymer solution. (Item 21) 21. The method of claim 20, wherein the coacervation inducer is a water-soluble or water-dispersible salt. [Brief description of the drawings]

[0007] [Figure 1] Figure 1A is a schematic representation of a typical encapsulated electrophoretic display. Figure 1B is a schematic representation of an exemplary encapsulated electrophoretic display that includes three different types of charged pigment particles.

[0008] [Diagram 2] FIG. 2 is a schematic representation of a thin film transistor (TFT) array for controlling the pixel electrodes and associated scan (gate) and data (source) drivers.

[0009] [Diagram 3] FIG. 3 is a schematic flow chart illustrating an exemplary method for encapsulating an electrophoretic fluid.

[0010] [Figure 4] Figure 4A shows the size distribution of droplet intermediates in an exemplary process for producing microcapsules according to the present application, and Figure 4B shows the size distribution of microcapsules produced from the droplets of Figure 4A.

[0011] [Diagram 5]Figure 5A shows a photomicrograph of a dried coating made with the capsules of Figure 4B dispersed in a polyurethane binder and incorporated into a test pixel, and Figure 5B shows a scanning electron micrograph (SEM) cross-section of the coating of Figure 5A.

[0012] [Figure 6A] Figure 6A illustrates an example waveform for driving an electrophoretic display including an encapsulated electrophoretic medium to achieve a red display state, Figure 6B illustrates a waveform for driving the encapsulated electrophoretic medium to achieve a white display state, and Figure 6C illustrates a waveform for driving the encapsulated electrophoretic medium to achieve a black display state. [Figure 6B] Figure 6A illustrates an example waveform for driving an electrophoretic display including an encapsulated electrophoretic medium to achieve a red display state, Figure 6B illustrates a waveform for driving the encapsulated electrophoretic medium to achieve a white display state, and Figure 6C illustrates a waveform for driving the encapsulated electrophoretic medium to achieve a black display state. [Figure 6C] Figure 6A illustrates an example waveform for driving an electrophoretic display including an encapsulated electrophoretic medium to achieve a red display state, Figure 6B illustrates a waveform for driving the encapsulated electrophoretic medium to achieve a white display state, and Figure 6C illustrates a waveform for driving the encapsulated electrophoretic medium to achieve a black display state.

[0013] [Figure 7] FIG. 7 shows the size distribution of non-ionic polymer microcapsules after sieving using various sieve sizes and a comparison with state-of-the-art gelatin capsules.

[0014] [Figure 8]Figure 8A shows a micrograph of a dried coating made with non-ionic polymer microcapsules sieved at 15 μm and incorporated into a test pixel, and Figure 8B shows a scanning electron micrograph (SEM) cross-section of the coating of Figure 8A. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Detailed Description In a first aspect, the present invention relates to a novel electro-optical medium based on electrophoretic fluids encapsulated in microcapsules, based on non-ionic polymers. Such non-ionic polymer capsules are in contrast to conventional polymer capsules with ionic groups, such as those present in gelatin and acacia capsules. The capsules disclosed herein are typically formed from coacervates of non-ionic polymers encapsulating an internal phase comprising a mixture of a non-polar solvent and more than two types of charged pigment particles. Surprisingly, it has been found that the microcapsules, when addressed with the same waveform, provide nearly identical (or better) electro-optical performance compared to test cells or microcells incorporating the same fluid. In other words, the encapsulation process does not introduce any abrupt changes in the mechanics of pigment motion induced by the electrical addressing of the display. Such "drop in" capability means that the encapsulated medium of the present invention can be used with existing infrastructures such as backplanes and drivers.

[0016] Without being bound to any particular theory, it appears that non-ionic microcapsule walls may be less likely to interfere with the charge balance that must be maintained within the electrophoretic fluid, especially when complex results are expected, such as in the case of multicolor displays. Thus, electro-optic media can be coated over large surfaces and layered with electrodes and / or other layers to create a variety of electro-optic devices, including sunlight-readable displays and smart windows.

[0017] An electrophoretic display typically comprises a layer of electrophoretic material and at least two other layers disposed on opposite sides of the electrophoretic material, one of these two layers being an electrode layer. In most such displays, both layers are electrode layers, and one or both of the electrode layers are patterned to define pixels of the display. For example, one electrode layer may be patterned into elongated row electrodes and the other into elongated column electrodes extending at right angles to the row electrodes, the pixels being defined by the intersections of the columns and the 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 electrophoretic display, where the display is intended for use with a separate stylus, printhead, or similar movable electrode, only one of the layers adjacent to the electrophoretic layer comprises an electrode; the layer opposite the electrophoretic layer is typically a protective layer intended to prevent the movable electrode from damaging the electrophoretic layer.

[0018] A conventional microcapsule-based electrophoretic display (EPID) is shown in FIG. 1A. The display 100 typically comprises a layer of electrophoretic material 130 and at least two other layers 110 and 120 disposed on the opposite side of the electrophoretic material 130, at least one of these two layers being an electrode layer, for example as depicted by layer 110 in FIG. 1A. The front electrode 110 may represent the viewing side of the display 100, in which the front electrode 110 may be a transparent conductor such as indium tin oxide (ITO) (coated on a transparent substrate such as polyethylene terephthalate (PET)). Other flexible conductive materials such as conductive polymers or polymers with conductive additives may also be used for the front electrode. Such an EPID also includes a backplane 150, comprising a plurality of drive electrodes 153 and a substrate layer 157, as illustrated in FIG. 1A. The layer of electrophoretic material 130 may contain microcapsules 133 dispersed in a polymer binder 139 to hold the electrophoretic pigment white particles 135, black particles 137, and solvent. Typically, the pigment particles 137 and 135 are controlled (displaced) using an electric field produced between the front electrode 110 and the pixel electrodes 153. In many conventional EPIDs, an electric driving waveform is transmitted to the pixel electrodes 153 via conductive traces (not shown) that are coupled to thin film transistors (TFTs), allowing the pixel electrodes to be addressed in a row-column addressing scheme. In some embodiments, the front electrode 110 is simply grounded and the image is driven by providing positive and negative potentials to the pixel electrodes 153, which are individually addressable. In other embodiments, potentials may also be applied to the front electrode 110 to provide a larger variation in the field that may be provided between the front electrode and the pixel electrodes 153. In some embodiments, third (red particles) 132 may be included in the electrophoretic display, as shown in FIG. 1B.

[0019] In many embodiments, the TFT array forms an active matrix for image driving, as shown in FIG. 2. For example, each pixel electrode (153 in FIG. 1A) is coupled to a thin film transistor 210 that is patterned into an array, connected to an elongated row electrode 220 and an elongated column electrode 230, and extending perpendicular to the row electrode 220. In some embodiments, the pixels comprise transistors fabricated from metal oxides. In some embodiments, the pixels comprise transistors formed from doped polymers. In some embodiments, one electrode layer has the form of a single sustaining electrode, and the other electrode layer is patterned into a matrix of pixel electrodes, each of which defines one pixel of the display. As shown in FIG. 2, a data (source) driver 250 is connected to the column electrode 230 and provides a source voltage to all the TFTs in the column to be addressed. A scan (gate) driver 240 is connected to the row electrode 220 to provide a bias voltage that can open (or close) the gate of each TFT along the row. Of course, the locations of the data and source drivers are arbitrary and they can be swapped from the positions shown in Figure 2. The gate scan rate is typically about 60-100 Hz, however faster or slower scans may be appropriate in some cases.

[0020] Typically, taking the gate source voltage positive allows the source voltage to be shorted to the drain. Taking the gate negative with respect to the source drops the drain source current, effectively letting the drain float. Because the scan drivers act in a sequential manner, there is typically some measurable delay in update time between the top row electrode and the bottom row electrode. It is understood that the assignment of "row" and "column" electrodes is somewhat arbitrary, and TFT arrays can be fabricated with the roles of row and column electrodes swapped. In some embodiments, the TFT array is substantially flexible, however, individual components such as individual pixel transistors or driver circuits may not be flexible. Flexible traces for supplying voltages to individual pixels may be formed from flexible materials such as conductive polymers or polymers doped with conductive materials such as metal particles, nanoparticles, nanowires, nanotubes, graphite, and graphene. In some embodiments, the TFTs can be fabricated from organic thin film transistors.

[0021] Although conventional EPID media are described as "black and white", they are typically driven to multiple different states between black and white to achieve various tones or "grayscales". In addition, a given pixel may be driven between a first grayscale state and a second grayscale state (including the white and black endpoints) by driving the pixel through a transition from an initial gray level to a final gray level (which may or may not be different from the initial gray level). The term "waveform" will be used to indicate the overall voltage versus time curve used to effect a transition from a specific initial gray level to a specific final gray level. Typically, such a waveform will comprise multiple waveform elements. These elements are essentially rectangular (i.e., a given element comprises the application of a constant voltage for a period of time). An element may be referred to as a "pulse" or a "drive pulse".

[0022] The term "gray state" is used herein in its conventional sense in the imaging arts to refer to a state intermediate the two extreme optical states of a pixel, and does not necessarily imply a black-white transition between these two extreme states. For example, it is known to use electro-optic displays as variable transmittance windows, where the extreme states are substantially transparent and essentially opaque, such that an intermediate "gray state" may be partially transmissive, but in fact may not be a gray color. In fact, if the particles used are light scattering, a partially transmissive "gray state" may in fact be colored white. The term "monochrome" may hereinafter be used to refer to a drive scheme that drives a pixel only to its two extreme optical states, with no intervening gray states.

[0023] The terms "bistable" and "bi-stable" are used herein in their conventional sense in the art to refer to a display with display elements having first and second display states differing in at least one optical property, where a given element is driven with an addressing pulse of finite duration to assume either the first or second display state, and where the state remains after the addressing pulse is terminated for at least several times, e.g., at least four times, the minimum duration of the addressing pulse required to change the state of the display element. In U.S. Pat. No. 7,170,670, it is shown 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 for some other types of electro-optic displays. This type of display is properly called "multistable" rather than bistable, but for convenience the term "bistable" may be used herein to cover both bistable and multistable displays.

[0024] Numerous patents and applications assigned to or in the name of Massachusetts Institute of Technology (MIT) and E Ink Corporation describe various techniques used in encapsulated electrophoretic and other electro-optic media. Such encapsulated media include a number of small capsules, each of which itself comprises an internal phase that contains electrophoretically mobile particles in a fluid medium, and a capsule wall that surrounds the internal phase. Some of the materials and techniques described in the patents and applications listed below are relevant to the fabrication of the variable transmittance devices described herein, including: (a) Electrophoretic particles, fluids, and fluid additives (e.g., [ka] reference) (b) Capsules, binders, and encapsulation processes (e.g., [ka] reference) (c) Films and subassemblies containing electro-optical materials (see, e.g., 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, e.g., U.S. Pat. Nos. 7,116,318 and 7,535,624) (e) Color formation and color control (see, e.g., U.S. Pat. Nos. 7,075,502 and 7,839,564) (f) Methods for driving displays (see, e.g., U.S. Pat. Nos. 7,012,600 and 7,453,445) (g) Display Applications (see, e.g., U.S. Pat. Nos. 7,312,784 and 8,009,348) (h) Non-electrophoretic displays (see, e.g., U.S. Pat. Nos. 6,241,921, 6,950,220, 7,420,549, and 8,319,759, and U.S. Patent Application Publication No. 2012 / 0293858)

[0025] Electrophoretic Fluid

[0026] The internal phase of the electro-optic medium comprises electrically charged pigment particles dispersed in a suspending solvent. In an exemplary embodiment, the solvent in which the three types of pigment particles are dispersed is clear and colorless and may be either one or a combination of two or more liquids. It preferably has a low viscosity and dielectric constant in the range of about 2 to about 30, preferably about 2 to about 15, for high particle mobility. Examples of suitable dielectric solvents include hydrocarbons such as ISOPAR® (Sigma-Aldrich), decahydronaphthalene (DECALIN), 5-ethylidene-2-norbornene, fatty oils, paraffin oils, silicone fluids, aromatic hydrocarbons such as toluene, xylene, phenylxylylethane, dodecylbenzene, and alkylnaphthalenes, halogenated solvents such as perfluorodecalin, perfluorotoluene, perfluoroxylene, dichlorobenzotrifluoride, 3,4,5-trichlorobenzotrifluoride, chloropentafluoroethane, dichlorononane, pentachlorobenzene, and perfluorinated solvents such as FC-43, FC-70, and FC-5060 (3M Company, St. Paul, MN), low molecular weight halogen-containing polymers such as poly(perfluoropropylene oxide) (TCI America, Portland, OR), poly(chlorotrifluoroethylene)s such as halocarbon oils (Halocarbon Product Corp., River Edge, (Ausimont USA, Thorofare, NJ), perfluoropolyalkyl ethers such as Galden (Ausimont USA, Thorofare, NJ) or Krytox oils, and greases K-Fluid series (DuPont, Wilmington, DE), polydimethylsiloxane-based silicone oils such as DC-200 (Dow Corning, Midland, MI).

[0027] The refractive index of the inner layer is modified by the addition of an index matching agent, such as Cargille® index matching fluid available from Cargille-Sacher Laboratories Inc. (Cedar Grove, NJ).

[0028] Color Pigment Particles

[0029] The charged pigment particles may be of various colors and compositions. In addition, the charged pigment particles may be functionalized with a surface polymer to improve state stability. Such pigments are described in U.S. Patent Publication No. 9,921,451, which is incorporated by reference in its entirety. As anticipated above, the electrophoretic fluid forming the internal phase of the microcapsules includes three or more types of charged pigment particles dispersed in a suspending solvent. For ease of illustration, the three types of pigment particles may be referred to as white particles, black particles, and color particles. This configuration is illustrated in FIG. 1B, where red particles 132 are present in addition to conventional white particles 135 and black particles 137. However, it is understood that the scope of the present invention broadly encompasses pigment particles of any color, so long as the three types of pigment particles have visually contrasting colors. For example, the electrophoretic fluid may include a particle set of reflective white particles and cyan, yellow, and magenta absorbing particles. Alternatively, the electrophoretic fluid may include a particle set of absorbing black particles and red, yellow, and blue reflective particles.

[0030] For example, if the charged particles are white, they may be formed from inorganic pigments such as TiO2, ZrO2, ZnO, Al2O3, Sb2O3, BaSO4, PbSO4 or equivalent. They may also be polymer particles or composite particles engineered to have the desired refractive index, with a high refractive index (>1.5), of a certain size (>100 nm), and white color. For black charged particles, they may be formed from CI pigment black 26 or 28 or equivalent (e.g., manganese ferrite black spinel or copper chromite black spinel) or carbon black. The third type of pigment particles may be red, green, blue, magenta, cyan, or yellow, etc. Pigments for this type of particle may include, but are not limited to, CI pigments PR254, PR122, PR149, PG36, PG58, PG7, PB28, PB15:3, PY138, PY150, PY155, or PY20. They are commonly used organic pigments described in the Dye Factor Handbooks "New Pigment Application Technology" (CMC Publishing Co, Ltd, 1986) and "Printing Ink Technology" (CMC Publishing Co, Ltd, 1984). Specific examples include Clariant Hostaperm Red D3G 70-EDS, Hostaperm Pink E-EDS, PV fast Red D3G, Hostaperm Red D3G70, Hostaperm Blue B2G-EDS, Hostaperm Yellow H4G-EDS, Hostaperm Green GNX, BASF Irgazine Red L3630, Cinquasia Red L 4100 HD, and Irgazin Red L3 660 HD; Sun Chemical phthalocyanine blue, phthalocyanine green, diarylide yellow, or diarylide AAOT yellow.

[0031] The percentage of the three types of pigment particles in the electrophoretic fluid may vary. For example, the black particles may occupy about 0.1% to 10%, preferably 0.5% to 5%, of the volume of the electrophoretic fluid, the white particles may occupy about 1% to 50%, preferably 5% to 15%, of the volume of the fluid, and the color particles may occupy 2% to 20%, preferably 4% to 10%, of the volume of the fluid. Other particulate matter may be present in the fluid, included as additives to improve the performance of the display device, such as switching speed, imaging bistability, and reliability.

[0032] In an exemplary embodiment, two of the three types of pigment particles carry opposite charge polarities, and the third type of pigment particles is slightly charged. The term "slightly charged" is defined as a third type that carries only a fraction of the charge carried by the more highly charged first two types of particles. For example, if the black particles are positively charged and the white particles are negatively charged, the color pigment particles are slightly charged. In other words, the charge carried by the black and white particles is much stronger than the charge carried by the color particles. In an exemplary embodiment, the color pigment particles carry less than 75%, less than 50%, less than 40%, or less than 30% of the charge carried by the more highly charged white and black particles. Typically, the amount of charge of the "slightly charged" particles is one-half to one-third that of the more highly charged particles. In addition, the third type of particles that carry a slight charge have a charge polarity that is the same as that carried by either one of the other two types of more strongly charged particles.

[0033] The surface of the charged particle may be modified by known techniques based on the charge polarity and charge level of the particle required, as described in US Patent Nos. 6,822,782, 7,002,728, 9,366,935, and 9,372,380 and US Publication No. 2014-0011913. The particle may exhibit an inherent charge, or may be explicitly charged using an electric field control agent, or may acquire a charge when suspended in a solvent. Suitable electric field control agents are well known in the art. They may be polymeric or non-polymeric, or ionic or non-ionic in nature. Examples of electric field control agents may include, but are not limited to, Solsperse 17000 (active polymeric dispersant), Solsperse 9000 (active polymeric dispersant), OLOA11000 (succinimide ashless dispersant), Unithox 750 (ethoxylate), Span 85 (sorbitan trioleate), Petronate L (sodium sulfonate), Alcolec LV30 (soy lecithin), Petrostep B100 (petroleum sulfonate) or B70 (barium sulfate), Aerosol OT, polyisobutylene derivatives or poly(ethylene-co-butylene) derivatives, and the like. In addition to the suspending solvent and charged pigment particles, the internal phase may include stabilizers, surfactants, and electric field control agents. The stabilizing materials may be adsorbed onto the charged pigment particles when dispersed in the solvent. The stabilizing material keeps the particles separated from one another when the particles are in their dispersed state such that the variable permeability medium is substantially impermeable.

[0034] As known in the art, dispersing charged particles (typically carbon black, as explained above) in solvents with low dielectric constants may be aided by the use of surfactants. Such surfactants typically include a polar "head group" and a non-polar "tail group" that is compatible with or soluble in the solvent. In the present invention, the non-polar tail group is preferably a saturated or unsaturated hydrocarbon moiety or another group that is soluble in a hydrocarbon solvent, such as, for example, poly(dialkylsiloxane). The polar group may be any polar organic functionality, including ionic materials such as ammonium, sulfonate or phosphonate, or acidic or basic groups. In particular, preferred head groups are carboxylic acid or carboxylate groups. Stabilizing agents suitable for use with the present invention include polyisobutylene and polystyrene. In some embodiments, dispersing agents such as polyisobutenyl succinimide and / or sorbitan trioleate and / or 2-hexadecanoic acid are added.

[0035] The three types of pigment particles may have variable sizes. In one embodiment, one of the three types of pigment particles is larger than the other two types. It should be noted that of the three types of pigment particles, the one type of particles that is slightly charged preferably has a larger size. For example, both the black and white particles are relatively small, and their sizes (tested through dynamic light scattering) may range from about 50 nm to about 800 nm, more preferably from about 200 nm to about 700 nm, and in this exemplary embodiment, the slightly charged color particles are preferably about 2 to about 50 times, more preferably about 2 to about 10 times larger than the black and white particles.

[0036] The term "threshold voltage" in the context of the present invention is defined as the maximum bias voltage that can be applied to a group of pigment particles without causing the pigment particles to appear on the viewing side of the display device. The term "viewing side" refers to the side of the display device where the image is seen by the viewer. In one aspect of the present application, at least one of the three types of pigment particles may demonstrate a threshold voltage under a triangular voltage driving test. The threshold voltage is either an inherent property of the charged pigment particles or an additive induced property. In the former case, a threshold is generated and relies on certain attractive forces between the particles or between the particles and a certain substrate surface. The threshold may also be generated through the interaction of two types of oppositely charged particles. In the latter case referred to above, a threshold material may be added that induces or enhances the threshold property of the electrophoretic fluid to achieve the threshold voltage. The threshold material may be any material that is soluble or dispersible in the solvent of the electrophoretic fluid and that carries or induces a charge opposite to that of the charged pigment particles. The threshold material may be sensitive or insensitive to changes in the applied voltage. The term "threshold material" may broadly include dyes or pigments, electrolytes or polyelectrolytes, polymers, oligomers, surfactants, charge control agents, and the like. Additional information related to threshold materials may be found in U.S. Patent No. 8,115,729.

[0037] Encapsulant

[0038] In one aspect of the invention, the non-ionic capsule wall is made from one or more starting homopolymers or copolymers that are water-soluble or water-dispersible in pH-neutral aqueous solutions and are non-ionic. In one embodiment, the starting polymer is essentially uncharged in an aqueous solution having a pH in the range of about 2-12. In other non-exclusive embodiments, the starting polymer is essentially uncharged in an aqueous solution having a pH in the range of about 3-11, 4-10, 5-9, or 6-8. Optionally, or alternatively, the starting polymer is essentially uncharged at the operating conditions of the electrophoretic medium in which the capsule is incorporated. In a preferred embodiment, at least one of the non-ionic wall polymers is characterized by three or more functional groups capable of forming covalent bonds with a crosslinker to strengthen the capsule wall. Exemplary functional groups include alcoholic hydroxyl (-OH) moieties attached to saturated carbons that are either part of the polymer chain or connected thereto via a crosslinking moiety.

[0039] It should be understood that the starting polymer may in some cases contain a small number of electrically charged functional groups, provided that the number of charges does not substantially deteriorate the performance of the capsule. For example, the starting polymer may be a polyol containing carboxylic or amino moieties that are ionized at the pH of the electrophoretic medium, but the number of ionic functional groups is too small to adversely affect the properties of non-ionic capsules, for example, in the manner seen with gelatin / acacia capsules. In some cases, the starting polymer may contain functional groups that are charged at a certain pH range, but once incorporated into the capsule wall, produce neutral moieties, emphasizing the neutrality of this feature in the final product. Exemplary functional groups of this type include carboxylic acids that are incorporated into ester moieties and amino groups that become part of amide or carbamate moieties in the final product capsule wall.

[0040] As used herein, unless otherwise stated, the term "polymer" includes molecules consisting of at least 50 repeating subunits, such as, for example, polyvinyl lactams, e.g., polyvinylpyrrolidone (PVP), hydrophilic polyethers, e.g., polyethylene glycol (PEG), polyethylene oxide-polypropylene oxide (PEO-PPO), polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO), vinylpyrrolidone vinyl acetate copolymers, polysaccharides, and water-soluble polysiloxanes.

[0041] Exemplary polyhydroxyl polymers, also known as polyols, can also be represented by the formula (CHCHOH): n These include those having 1,2- and / or 1,3-diol structures, such as polyvinyl alcohol (PVOH) having n alcohol groups, where n can be hundreds or even thousands, depending on the molecular weight of the PVOH. In cases where the PVOH is prepared by hydrolysis of the corresponding homopolymer polyvinyl acetate, the PVOH may contain less than 50% of polyvinyl acetate units, in particular less than 20% of polyvinyl acetate units. In some embodiments, the polyvinyl alcohol may also contain a small proportion, for example up to 20%, or alternatively up to 10%, or up to 5% of copolymer units of ethylene, propylene, acrylamide, methacrylamide, dimethacrylamide, hydroxyethyl methacrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, vinylpyrrolidone, hydroxyethyl acrylate, allyl alcohol, styrene, or similar comonomers typically used. It is also possible to use, for example, hydrolyzed ethylene-vinyl acetate (EVA), or copolymers of hydrolyzed or partially hydrolyzed vinyl acetate, available as vinyl chloride-vinyl acetate, N-vinylpyrrolidone-vinyl acetate, and maleic anhydride-vinyl acetate.Polysaccharides provide another class of preferred polyols, such as ethyl cellulose, hydroxypropyl methylcellulose, guar gum, dextrins, starches, and other related materials, such as those well known in the art.

[0042] Preferably, the average molecular weight of the starting polymer is at least about 10,000 daltons. Upper limits on the average molecular weight can be up to 25,000, 50,000, or 75,000 daltons, although upper limits of 100,000 daltons or higher are also envisioned.

[0043] Crosslinkers include molecules with two or more reactive carbonyl groups, such as saturated dialdehydes of 2 to 6 carbons, that are capable of reacting with the hydroxyl groups of the polyol-initiated polymer and forming covalent bonds. The reaction between the alcohol groups of the polyol and the carbonyl moieties of the dialdehyde forms crosslinks that strengthen the structure of the microcapsules. Other possible crosslinkers include organotitanates or zirconates, and borates. It is also possible to stabilize the polymer by heating and cooling steps that may induce physical crosslinks, for example, by means of entanglement or hydrogen bonding. Configurations in which the starting polymer features reactive groups other than hydroxyl are also envisioned, provided the crosslinker includes moieties capable of reacting with such groups to form covalent bonds.

[0044] Encapsulating the electrophoretic fluid

[0045] In a further aspect, a method is provided for encapsulating an electrophoretic fluid by depositing one or more non-ionic, water-soluble, or water-dispersible starting polymers onto emulsified droplets of the electrophoretic fluid using a process of coacervation, also called phase separation. Coacervation involves the separation of the liquid phase of the coating material from the polymer solution and the wrapping of the phase as a coacervated layer around the suspended core droplet. Coacervation can be brought about when the surface energy of the core droplet and the coating material are adjusted by varying some parameters of the system, such as, for example, temperature, pH, or composition. The coacervated layer is then hardened by means of heat, crosslinking, and / or solvent removal techniques, resulting in the product microcapsules as the hardened coacervated layer transforms into a solidified capsule wall.

[0046] FIG. 3 illustrates a representative embodiment of the method. An aqueous solution of one or more water-dispersible starting polymers is prepared (30) and then mixed with an electrophoretic fluid (32), and the resulting mixture is heated to a temperature above the lower critical solution temperature (LCST) (34). The polymers coacervate, resulting in emulsified droplets. The process may be controlled by adding a coacervation inducer, such as a salt, to the polymer solution. The effectiveness of various salts in controlling the LCST is explained by the Hofmeister series of experiments, as is well known in the art. A crosslinker is then added (36), and the resulting mixture is allowed to react until the coacervated phase hardens to form the capsule wall.

[0047] In one embodiment, curing occurs in the absence of heating, and the curing mixture is left to react at or below the temperature at which it is formed. In another embodiment, the curing mixture is heated to a higher temperature (38), either directly or in increments in a stepwise manner, and then curing is allowed to complete at the higher temperature upon which heating is discontinued and the mixture is cooled (39), either spontaneously or by active heat removal.

[0048] It has been found that better results are obtained when curing is performed in the presence of heat. Without being bound to any particular theory, one possible explanation is that in the absence of heat, the coacervated polymer on the outer layer of the capsule precursor is susceptible to redissolution in aqueous media at a higher rate than the crosslinking reaction. The capsules produced are then separated by size by sieving or other size exclusion sorting methods. Capsules larger than about 120 μm are difficult to use because they tend to break from shear forces during processing. In addition, capsules larger than 100 μm are visible to the naked eye, and therefore their presence can be perceived as ripples in the variable transmittance film.

[0049] After size sorting, the capsules are mixed with a binder to create a slurry for coating, for example, using slot coating, knife coating, spin coating, etc. Alternatively, the capsules may be suspended and sprayed as described in U.S. Pat. No. 9,835,925, which is incorporated herein by reference in its entirety. In certain embodiments of the present application, the binder comprises a polymer, for example, a water-soluble polymer such as latex, including polyvinyl alcohol, which may be cationically modified, or a polyurethane material, for example. As anticipated above, the capsules of the present application surprisingly perform well when assessed using waveforms having the same structure as those used to drive the same electrophoretic fluid in a test cell or microcell.

[0050] Below are representative examples illustrating aspects of the present invention. EXAMPLES

[0051] Example 1 Example 1 - Preparing polyvinyl alcohol microcapsules A solution of polyvinylpyrrolidone (112.0 g of a 20% solution, 1.3 MDa average molecular weight) and polyvinyl alcohol (74.7 g of a 10% solution, Mowiol 23-88, available from Kuraray, Japan) was mixed and stirred for 1 hour at 4° C., then a solution of sodium sulfate (88.36 g of a 16.7% aqueous solution) was added to bring the cloud point temperature to 25° C. The solution was stirred at 4° C. until the precipitate was dissolved, and accordingly, a three-pigment electrophoretic fluid (120 g of a fluid similar to that described in the aforementioned U.S. Patent No. 8,717,664, incorporated herein by reference in its entirety) containing white, black, and red particles was added subsurface, after which the temperature was increased to 9° C., and the solution was stirred at 400 rpm for 9 minutes to form droplets.

[0052] Thirty grams of a mixture comprising 15.15 g of a 50 wt. % aqueous solution of glutaraldehyde, 1.52 g of 10% acetic acid, 0.27 g of 0.9% hydrogen chloride, and 13.36 g of water was then added at a temperature of 9° C. The resulting mixture was held at 9° C. for 50 minutes, after which the temperature was increased to 15° C. After holding at this temperature for 1 hour, the mixture was heated to 60° C. and held at this temperature for 135 minutes, then cooled to 25° C. The capsules were collected after 30 minutes and stored in a refrigerator at 5° C. for one week before being purified by centrifugation. The force required to rupture an individual capsule, normalized to the capsule diameter, was about 48 N / m. Figures 4A and 4B show the droplets and capsule size distribution of the material produced according to the above procedure. Figure 4A shows the droplets prior to capsule wall formation and gelatin control using the present invention. FIG. 4B shows the present invention at the end of the capsule wall formation reaction and after size selection by sieving.

[0053] Microcapsule Coating

[0054] Following preparation and isolation of the microcapsules, they were incorporated into a coating slurry with 60 mg of cationically modified polyvinyl alcohol polymer CM-318 (Kuraray, Japan) in aqueous solution. The slurry had a concentration of 21 g / m 2 The microcapsules were coated onto a 4 mm thick poly(ethylene terephthalate) (PET) substrate with a transparent conductive coating of indium tin oxide (ITO) to yield a coating with a specific weight of 1. The resulting coating of microcapsules was then incorporated into pixels with a carbon backplane.

[0055] Figure 5A shows a micrograph of the microcapsule coating, while Figure 5B shows a cross-section of the coating. As can be seen in Figure 5A, there are some voids within the microcapsule coating, but it is notable that the coating is essentially a monolayer. The cross-section shows that the dried microcapsules 500 have flattened sides and form a uniform layer approximately 15 micrometers thick. For ease of visualization, two capsules within the capsule layer are bounded with a white polygon.

[0056] Test pixels formed as described above were switched using conventional waveforms as illustrated in Figures 6A-6C. The same electrophoretic fluid containing black, white, and red particles was also incorporated into microcells and gelatin / acacia capsules, and the resulting products were formed into pixels and switched using the same conventional waveforms used for the microcapsules above.

[0057] The performance of the test pixels is measured using the CIELAB (also known as CIE L * a * b * The results were quantified according to the RGB (also known as RGB) color space and reported below in Table 1. [Table 1]

[0058] It can be seen that the microcell and polyvinyl alcohol capsules achieve good white, black, and red states and can produce the same colors when addressed using the conventional voltage sequence of U.S. Patent No. 8,717,664. However, the gelatin / acacia capsules, in this case, have a * >31, it is not possible to achieve either a neutral black state or a red state. It is readily apparent that the behavior of identical electrophoretic fluids is very different when they are contained within gelatin / acacia microcapsules, and the correct color cannot be obtained. This was unexpected, since gelatin / acacia microcapsules have been shown to provide excellent performance for black and white displays, and were expected to perform similarly to more complex electrophoretic fluids.

[0059] Without wishing to be bound by any particular theory, it is known that in gelatin / acacia, the amount of microcapsule wall charge is a function of pH. In the coating slurry, the pH is typically adjusted to alkaline to ensure that the carboxylate groups in the capsule wall are ionized. When these groups are charged (as they are at high pH), the capsules have a reduced tendency to stick together, while at low pH, intracapsule sticking can cause the viscosity of the slurry to be too high for efficient coating. However, when the electrophoretic fluid contains more than two pigments, it may not be desirable to increase the pH of the coating solution, as the materials added to achieve this may interfere with the final performance of the electrophoretic display. In some cases, it may be possible to restore satisfactory performance and recover the desired optical state in the gelatin / acacia microcapsules by adjusting the addressing waveform, but typically substantial chemical adjustments are required to the electrophoretic fluid itself. It would be preferable to have a coating slurry that is less sensitive to pH.

[0060] Furthermore, capsules with charged walls also stick to the substrate onto which they are coated and therefore lose the ability to rearrange efficiently to form a monolayer coating. Although manufacturing processes can be controlled to produce uniform coatings with capsules having charged walls, typically monolayer coatings are much more easily produced using capsules without wall charges.

[0061] It is also noteworthy that forming polyvinyl alcohol microcapsules requires much less time than the conventional processes used to form gelatin / acacia capsules: a 120 g batch of electrophoretic fluid was encapsulated into polyvinyl alcohol-based capsules in roughly 4 hours, whereas the standard gelatin / acacia process typically takes more than 13 hours.

[0062] Example 2 Example 2 - Improved capsule size discrimination Additional microcapsules with full color (CMYW) electrophoretic fluids were formed using the same non-ionic polymer formulation as in Example 1 above. The electrophoretic fluids were prepared from the following ingredients: a dispersion containing a white pigment (71.41 g of a 55.71 wt% dispersion of polymer-coated TiO2 as described in U.S. Pat. No. 8,582,196), a dispersion containing a magenta pigment (15.21 g of a 24.99 wt% dispersion of CI Pigment Red 122 coated with vinylbenzyl chloride and lauryl methacrylate (LMA) as described in U.S. Pat. No. 9,697,778), a dispersion containing a cyan pigment (14.23 g of a 25.43 wt% dispersion of methyl methacrylate (MMA) and dimethylsiloxane coated with methyl methacrylate (MMA) and dimethylsiloxane), and a dispersion containing a white pigment (71.41 g of a 55.71 wt% dispersion of polymer-coated TiO2 as described in U.S. Pat. No. 8,582,196), a dispersion containing a magenta pigment (15.21 g of a 24.99 wt% dispersion of CI Pigment Red 122 coated with vinylbenzyl chloride and lauryl methacrylate (LMA) as described in U.S. Pat. No. 9,697,778), a dispersion containing a cyan pigment (14.23 g of a 25.43 wt% dispersion of methyl methacrylate (MMA) and dimethylsiloxane coated with methyl methacrylate (MMA) and dimethylsiloxane). A dispersion containing a yellow pigment (CI Pigment Blue 15:3, coated with methyl methacrylate (MMA), 2,2,2-trifluoroethyl methacrylate (TFEM), and monomethacryloxypropyl terminated polydimethylsiloxane, 13.64 g of a 35.62 wt % dispersion of CI Pigment Yellow 155), CCA111 (3.04 g of a 75 wt % solution), and poly(isobutylene) of greater than 500,000 average molecular weight (3.67 g of a 9.94 wt % solution of PIB in ISOPAR® E), was prepared by combining and mixing overnight and equilibrating with additional ISOPAR® E.

[0063] A solution of polyvinylpyrrolidone (74.07 g of a 15% solution, 1.3 MDa molecular weight) and polyvinyl alcohol (55.55 g of a 10% solution, Mowiol 23-88, available from Kuraray, Otemachi, Chiyoda, Tokyo, Japan) with 152.38 g of water was mixed and stirred at 5° C. for 1 hour, then a solution of sodium sulfate was added (88.36 g of a 16.7% aqueous solution). The resulting mixture has a cloud point temperature of ≦10° C. The solution was stirred at 5° C. until the precipitate was dissolved, and accordingly, 120 g of electrophoretic fluid described above was added subsurface, and the solution was stirred at 600 rpm for 66 minutes to form droplets.

[0064] At that point, 30 g of a mixture comprising 15.15 g of 50% aqueous glutaraldehyde, 1.52 g of 10% acetic acid, 0.27 g of 0.9% hydrogen chloride, and 13.36 g of water was added at 5° C. and the pH was adjusted to 2.6 with 0.239 g of hydrogen chloride (37%). The temperature was then increased to 52° C. and held for 75 minutes before cooling down to 25° C. The capsules formed were collected and washed by sieving methods. The force required to rupture an individual capsule, normalized to the capsule diameter, was approximately 335.1 N / m.

[0065] The capsules produced were washed and separated by size by sieving. In many cases, the fraction passing through the sieve contained broken capsules and crosslinked blobs of polymer that did not actually encapsulate the electrophoretic internal phase (charged pigment particles distributed in a hydrocarbon solvent). Different sieves with various opening sizes (25 μm, 20 μm, 15 μm) were used to collect the different capsule fragments and the capsule size distribution was measured (see FIG. 7). For comparison, a standard gelatin acacia microcapsule formulation was also prepared using the above CMYW electrophoretic fluid and sieved at 20 μm. The SVD average sizes for the distributions shown in FIG. 7 were 35 μm for the gelatin control, 31 μm for the PVOH capsules sieved at 25 μm, 26 μm for the PVOH capsules sieved at 20 μm, and 24 μm for the PVOH capsules sieved at 15 μm. In addition, the total time for encapsulation and separation is significantly reduced from the standard gelatin-acacia procedure. For example, 120 g of electrophoretic fluid is encapsulated in polyvinyl alcohol in about 3.5 hours, whereas the gelatin / acacia process may typically require more than 13 hours. A comparison of capsule size distribution for PvOH capsules made as above and sieved at 15 μm versus standard gelatin acacia microcapsules sieved at 20 μm is shown in Table 2. [Table 2]

[0066] Further analysis of the mass balances of the various processes showed that the PVOH encapsulation process increased the yield of encapsulated electrophoretic medium compared to the standard gelatin encapsulation method, which resulted in little pigment being wasted as it was not encapsulated during the process.

[0067] Following preparation and isolation of the microcapsules, they were incorporated into a coating slurry with 60 mg of modified polyvinyl alcohol polymer CM318 in aqueous solution. The slurry had a concentration of 21 g / m 2The resulting coating of microcapsules was incorporated into a test pixel with a carbon backplane using the methods described in detail in U.S. Pat. No. 6,982,178, which is incorporated herein by reference in its entirety. The quality of the coating obtained with 15 μm sieved PvOH capsules can be seen in FIGS. 8A and 8B. Furthermore, comparing FIGS. 8A and 8B with FIGS. 5A and 5B, it is readily apparent that the sieving process results in a smaller, more uniform capsule distribution, resulting in a very thin (12 μm) and regular monolayer of capsules (see FIG. 8B). In the cross-sectional view, an exemplary white oval is drawn on the capsule layer to illustrate the approximate size of the capsules within the capsule layer (FIG. 8B). Importantly, because the resulting capsules are smaller than standard gelatin capsules, the charged pigment particles can move back and forth across the viewing surface at higher speeds when driven with a standard voltage drive, thereby improving the refresh experience for the viewer.

[0068] Test pixels similar to those shown in Figures 8A and 8B were driven using conventional waveforms for a four-particle full-color electrophoretic medium, as described, for example, in U.S. Patent No. 9,921,451, which is incorporated by reference in its entirety. The PvOH capsules exhibited a slightly larger color gamut when compared to the gelatin-acacia control. [Table 3]

[0069] The various test pixels were additionally evaluated for switching speed. The PvOH capsules exhibited a slightly higher color gamut than their gelatin-acacia counterparts at both 18 and 42 frames when driven with the alternating primary color test pattern, corresponding to approximately 500 and 210 ms switching times, respectively. The higher color gamut at the same frame rate indicates a faster switching speed for the PvOH capsules compared to the gelatin-acacia. The smaller PVOH fragments exhibited a higher color gamut at 18 frames, meaning that the switching speed of the smaller size capsules could potentially be faster than the control. [Table 4]

[0070] 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, and therefore, the whole of the foregoing description is to be interpreted in an illustrative rather than a limiting sense.

Claims

1. A capsule comprising a capsule wall and an electrophoretic fluid encapsulated by the capsule wall, the capsule wall comprises a hardened coacervation layer formed from a non-ionic polyol and polyvinylpyrrolidone, the non-ionic polyol being water-soluble or water-dispersible and crosslinked; The electrophoretic fluid includes a suspending solvent, an ionic charge control agent, first pigment particles, second pigment particles, and third pigment particles, the first pigment particles, the second pigment particles, and the third pigment particles being differently colored and electrically charged, suspended in the suspending solvent, and capable of moving through the suspending solvent upon application of an electric field to the capsule.

2. The capsule of claim 1, wherein the capsule wall is crosslinked by reaction with a dialdehyde.

3. The capsule described in claim 2, wherein the dialdehyde is glutaraldehyde.

4. The capsule of claim 1, wherein the suspension solvent comprises a hydrocarbon.

5. The capsule of claim 1, wherein the electrophoretic fluid further comprises a fourth pigment particle.

6. An electrophoretic medium comprising a plurality of capsules as described in claim 1 and a binder surrounding the plurality of capsules.

7. An electrophoretic display comprising a layer of an electrophoretic medium as described in claim 6 and at least one electrode, the at least one electrode being positioned adjacent to the electrophoretic medium and arranged to apply an electric field to the electrophoretic medium.

8. The electrophoretic medium of claim 6, comprising capsules having an average diameter of 15 μm to 50 μm, and less than one-third of the capsules (by number) are smaller than 15 μm or larger than 50 μm.

9. An electrophoretic display comprising a layer of an electrophoretic medium as described in claim 8 and at least one electrode, the at least one electrode being positioned adjacent to the electrophoretic medium and arranged to apply an electric field to the electrophoretic medium.

10. A method for producing a capsule encapsulating an electrophoretic medium, the method comprising: providing a polymer solution, the polymer solution comprising a water-soluble or water-dispersible non-ionic polyol and a water-soluble or water-dispersible polyvinylpyrrolidone in an aqueous solvent; providing an electrophoretic fluid, the electrophoretic fluid comprising a suspending solvent, an ionic charge control agent, and pigment particles; mixing the polymer solution with the electrophoretic fluid to form a reaction mixture; heating the reaction mixture to a temperature above a lower critical solution temperature of the polymer solution, thereby forming an oil-in-water emulsion containing the electrophoretic fluid; adding a crosslinker to the oil-in-water emulsion, thereby forming a cured mixture; heating the curing mixture to form capsules encapsulating the electrophoretic medium; A method comprising:

11. The method of claim 10, wherein the polymer solution comprises a copolymer of vinyl acetate.

12. The method of claim 10, wherein the crosslinking agent is glutaraldehyde.

13. The method of claim 10, further comprising adding a coacervation inducer to the polymer solution, the coacervation inducer being a water-soluble or water-dispersible salt.

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