Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
  • G02F1/166—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
  • G02F1/167—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect by electrophoresis
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0004—Coated particulate pigments or dyes
  • C09B67/0008—Coated particulate pigments or dyes with organic coatings
  • C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
  • G02F1/1685—Operation of cells; Circuit arrangements affecting the entire cell
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
  • G09G3/00—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes
  • G09G3/20—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters
  • G09G3/2003—Display of colours
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
  • G09G3/00—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes
  • G09G3/20—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters
  • G09G3/34—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source
  • G09G3/3433—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source using light modulating elements actuated by an electric field and being other than liquid crystal devices and electrochromic devices
  • G09G3/344—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source using light modulating elements actuated by an electric field and being other than liquid crystal devices and electrochromic devices based on particles moving in a fluid or in a gas, e.g. electrophoretic devices
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
  • G02F1/1675—Constructional details
  • G02F2001/1678—Constructional details characterised by the composition or particle type
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
  • G02F2201/12—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode
  • G02F2201/121—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode common or background
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
  • G02F2201/12—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode
  • G02F2201/123—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode pixel
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F2203/00—Function characteristic
  • G02F2203/34—Colour display without the use of colour mosaic filters
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
  • G09G2300/00—Aspects of the constitution of display devices
  • G09G2300/04—Structural and physical details of display devices
  • G09G2300/0439—Pixel structures
  • G09G2300/0452—Details of colour pixel setup, e.g. pixel composed of a red, a blue and two green components
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
  • G09G2310/00—Command of the display device
  • G09G2310/06—Details of flat display driving waveforms
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
  • G09G2310/00—Command of the display device
  • G09G2310/06—Details of flat display driving waveforms
  • G09G2310/061—Details of flat display driving waveforms for resetting or blanking
  • G09G2310/063—Waveforms for resetting the whole screen at once
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
  • G09G2310/00—Command of the display device
  • G09G2310/06—Details of flat display driving waveforms
  • G09G2310/068—Application of pulses of alternating polarity prior to the drive pulse in electrophoretic displays
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
  • G09G2320/00—Control of display operating conditions
  • G09G2320/02—Improving the quality of display appearance
  • G09G2320/0247—Flicker reduction other than flicker reduction circuits used for single beam cathode-ray tubes
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
  • G09G2320/00—Control of display operating conditions
  • G09G2320/02—Improving the quality of display appearance
  • G09G2320/0252—Improving the response speed

Definitions

• This invention relates to colored electrophoretic displays, and more specifically to electrophoretic displays capable of rendering more than two colors using a single layer of electrophoretic material comprising a plurality of colored particles.
• color as used herein includes black and white. White particles are often of the light scattering type.
• gray state is used herein in its conventional meaning in the imaging art to refer to a state intermediate two extreme optical states of a pixel, and does not necessarily imply a black-white transition between these two extreme states.
• E Ink patents and published applications referred to below describe electrophoretic displays in which the extreme states are white and deep blue, so that an intermediate gray state would actually be pale blue. Indeed, as already mentioned, the change in optical state may not be a color change at all.
• black and white may be used hereinafter to refer to the two extreme optical states of a display, and should be understood as normally including extreme optical states which are not strictly black and white, for example the aforementioned white and dark blue states.
• 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. Patent 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.
• bistable 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.
• impulse when used to refer to driving an electrophoretic display, is used herein to refer to the integral of the applied voltage with respect to time during the period in which the display is driven.
• a particle that absorbs, scatters, or reflects light, either in a broad band or at selected wavelengths, is referred to herein as a colored or pigment particle.
• Electrophoretic displays have been the subject of intense research and development for a number of years. In such displays, a plurality of charged particles (sometimes referred to as pigment 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.
• electrophoretic media require the presence of a fluid.
• 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 HCSl-1, and Yamaguchi, Y., et al, Toner display using insulative particles charged triboelectrically, IDW Japan, 2001, Paper AMD4-4). See also U.S. Patents 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.
• 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.
• a related type of electrophoretic display is a so-called microcell electrophoretic display.
• the charged particles and the fluid are not encapsulated within microcapsules but instead are retained within a plurality of cavities formed within a carrier medium, typically a polymeric film.
• a carrier medium typically a polymeric film.
• 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. Patents 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. Patent No. 4,418,346.
• Electro-optic media operating in shutter mode can be used 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. Patent No. 7,339,715); and other similar techniques.)
• 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
• 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 ⁇ ), preferably about 2 to about 10 mil (51 to 254 ⁇ ).
• the electrically-conductive layer is conveniently a thin metal or metal oxide layer of, for example, aluminum or indium tin oxide (ITO), or may be a conductive polymer.
• ITO indium tin oxide
• PET Poly(ethylene terephthalate) films coated with aluminum or ITO are available commercially, for example as aluminized Mylar (Mylar is a Registered Trade Mark) from E.I. du Pont de Nemours & Company, Wilmington DE, and such commercial materials may be used with good results in the front plane laminate.
• Assembly of an electro-optic display using such a front plane laminate may be effected by removing the release sheet from the front plane laminate and contacting the adhesive layer with the backplane under conditions effective to cause the adhesive layer to adhere to the backplane, thereby securing the adhesive layer, layer of electro-optic medium and electrically-conductive layer to the backplane.
• This process is well-adapted to mass production since the front plane laminate may be mass produced, typically using roll-to-roll coating techniques, and then cut into pieces of any size needed for use with specific backplanes.
• U.S. Patent 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. Patent 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 subassembly is laminated to a backplane to form the final display, although the order of these two laminations could be reversed if desired.
• U. S. Patent 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. Patent No. 6,982, 178.
• This inverted front plane laminate comprises, in order, at least one of a light- transmissive protective layer and a light-transmissive electrically-conductive layer; an adhesive layer; a layer of a solid electro-optic medium; and a release sheet.
• This inverted front plane laminate is used to form an electro-optic display having a layer of lamination adhesive between the electro-optic layer and the front electrode or front substrate; a second, typically thin layer of adhesive may or may not be present between the electro-optic layer and a backplane.
• Such electro-optic displays can combine good resolution with good low temperature performance.
• electrophoretic media essentially display only two colors.
• Such electrophoretic media either use a single type of electrophoretic particle having a first color in a colored fluid having a second, different color (in which case, the first color is displayed when the particles lie adjacent the viewing surface of the display and the second color is displayed when the particles are spaced from the viewing surface), or first and second types of electrophoretic particles having differing first and second colors in an uncolored fluid (in which case, the first color is displayed when the first type of particles lie adjacent the viewing surface of the display and the second color is displayed when the second type of particles lie adjacent the viewing surface).
• the two colors are black and white.
• a color filter array may be deposited over the viewing surface of the monochrome (black and white) display. Displays with color filter arrays rely on area sharing and color blending to create color stimuli. The available display area is shared between three or four primary colors such as red/green/blue (RGB) or red/green/blue/white (RGBW), and the filters can be arranged in one-dimensional (stripe) or two-dimensional (2x2) repeat patterns. Other choices of primary colors or more than three primaries are also known in the art.
• the three (in the case of RGB displays) or four (in the case of RGBW displays) sub-pixels are chosen small enough so that at the intended viewing distance they visually blend together to a single pixel with a uniform color stimulus ('color blending').
• the inherent disadvantage of area sharing is that the colorants are always present, and colors can only be modulated by switching the corresponding pixels of the underlying monochrome display to white or black (switching the corresponding primary colors on or off).
• each of the red, green, blue and white primaries occupy one fourth of the display area (one sub-pixel out of four), with the white sub-pixel being as bright as the underlying monochrome display white, and each of the colored sub-pixels being no lighter than one third of the monochrome display white.
• the brightness of the white color shown by the display as a whole cannot be more than one half of the brightness of the white sub-pixel (white areas of the display are produced by displaying the one white sub-pixel out of each four, plus each colored sub-pixel in its colored form being equivalent to one third of a white sub-pixel, so the three colored sub-pixels combined contribute no more than the one white sub-pixel).
• the brightness and saturation of colors is lowered by area-sharing with color pixels switched to black.
• Area sharing is especially problematic when mixing yellow because it is lighter than any other color of equal brightness, and saturated yellow is almost as bright as white. Switching the blue pixels (one fourth of the display area) to black makes the yellow too dark.
• Multilayer, stacked electrophoretic displays are known in the art; see, for example, J. Heikenfeld, P. Drzaic, J-S Yeo and T. Koch, Journal of the SID, 19(2), 2011, pp. 129-156. In such displays, ambient light passes through images in each of the three subtractive primary colors, in precise analogy with conventional color printing.
• U.S. Patent No. 6,727,873 describes a stacked electrophoretic display in which three layers of switchable cells are placed over a reflective background. Similar displays are known in which colored particles are moved laterally (see International Application No. WO 2008/065605) or, using a combination of vertical and lateral motion, sequestered into micropits.
• each layer is provided with electrodes that serve to concentrate or disperse the colored particles on a pixel-by -pixel basis, so that each of the three layers requires a layer of thin- film transistors (TFT's) (two of the three layers of TFT's must be substantially transparent) and a light- transmissive counter-electrode.
• TFT's thin- film transistors
• Such a complex arrangement of electrodes is costly to manufacture, and in the present state of the art it is difficult to provide an adequately transparent plane of pixel electrodes, especially as the white state of the display must be viewed through several layers of electrodes.
• Multi-layer displays also suffer from parallax problems as the thickness of the display stack approaches or exceeds the pixel size.
• U.S. Applications Publication Nos. 2012/0008188 and 2012/0134009 describe multicolor electrophoretic displays having a single back plane comprising independently addressable pixel electrodes and a common, light-transmissive front electrode. Between the back plane and the front electrode is disposed a plurality of electrophoretic layers. Displays described in these applications are capable of rendering any of the primary colors (red, green, blue, cyan, magenta, yellow, white and black) at any pixel location.
• optical losses in an electrophoretic layer closest to the viewing surface may affect the appearance of images formed in underlying electrophoretic layers.
• U.S. Patent Application Publication No. 2013/0208338 describes a color display comprising an electrophoretic fluid which comprises one or two types of pigment particles dispersed in a clear and colorless or colored solvent, the electrophoretic fluid being sandwiched between a common electrode and a plurality of driving electrodes. The driving electrodes are kept at a certain distance in order to expose a background layer.
• U.S. Patent Application Publication No. 2014/0177031 describes a method for driving a display cell filled with an electrophoretic fluid comprising two types of charged particles carrying opposite charge polarities and of two contrast colors.
• the two types of pigment particles are dispersed in a colored solvent or in a solvent with non-charged or slightly charged colored particles dispersed therein.
• the method comprises driving the display cell to display the color of the solvent or the color of the non-charged or slightly charged colored particles by applying a driving voltage which is about 1 to about 20% of the full driving voltage.
• a driving voltage which is about 1 to about 20% of the full driving voltage.
• U.S. Patent Application Publication No. 2014/0092465 and 2014/0092466 describe an electrophoretic fluid, and a method for driving an electrophoretic display.
• the fluid comprises first, second and third types of pigment particles, all of which are dispersed in a solvent or solvent mixture.
• the first and second types of pigment particles carry opposite charge polarities, and the third type of pigment particles has a charge level being less than about 50% of the charge level of the first or second type.
• the three types of pigment particles have different levels of threshold voltage, or different levels of mobility, or both. None of these patent applications disclose full color display in the sense in which that term is used below.
• U.S. Patent Application Publication No. 2007/0031031 describes an image processing device for processing image data in order to display an image on a display medium in which each pixel is capable of displaying white, black and one other color.
• U.S. Patent Applications Publication Nos. 2008/0151355; 2010/0188732; and 201 1/0279885 describe a color display in which mobile particles move through a porous structure.
• U.S. Patent Applications Publication Nos. 2008/0303779 and 2010/0020384 describe a display medium comprising first, second and third particles of differing colors. The first and second particles can form aggregates, and the smaller third particles can move through apertures left between the aggregated first and second particles.
• 201 1/0134506 describes a display device including an electrophoretic display element including plural types of particles enclosed between a pair of substrates, at least one of the substrates being translucent and each of the respective plural types of particles being charged with the same polarity, differing in optical properties, and differing in either in migration speed and/or electric field threshold value for moving, a translucent display-side electrode provided at the substrate side where the translucent substrate is disposed, a first back-side electrode provided at the side of the other substrate, facing the display-side electrode, and a second back-side electrode provided at the side of the other substrate, facing the display-side electrode; and a voltage control section that controls the voltages applied to the display-side electrode, the first back-side electrode, and the second back-side electrode, such that the types of particles having the fastest migration speed from the plural types of particles, or the types of particles having the lowest threshold value from the plural types of particles, are moved, in sequence by each of the different types of particles, to the first back-side electrode or to the second back-side electrode, and then the
• U.S. Patent Applications Publication Nos. 2011/0175939; 2011/0298835; 2012/0327504; and 2012/0139966 describe color displays which rely upon aggregation of multiple particles and threshold voltages.
• U.S. Patent Application Publication No. 2013/0222884 describes an electrophoretic particle, which contains a colored particle containing a charged group-containing polymer and a coloring agent, and a branched silicone-based polymer being attached to the colored particle and containing, as copolymerization components, a reactive monomer and at least one monomer selected from a specific group of monomers.
• 2013/0222885 describes a dispersion liquid for an electrophoretic display containing a dispersion medium, a colored electrophoretic particle group dispersed in the dispersion medium and migrates in an electric field, a non-electrophoretic particle group which does not migrate and has a color different from that of the electrophoretic particle group, and a compound having a neutral polar group and a hydrophobic group, which is contained in the dispersion medium in a ratio of about 0.01 to about 1 mass % based on the entire dispersion liquid.
• 2013/0222886 describes a dispersion liquid for a display including floating particles containing: core particles including a colorant and a hydrophilic resin; and a shell covering a surface of each of the core particles and containing a hydrophobic resin with a difference in a solubility parameter of 7.95 (J/cm 3 ) 1/2 or more.
• U.S. Patent Applications Publication Nos. 2013/0222887 and 2013/0222888 describe an electrophoretic particle having specified chemical compositions.
• 2014/0104675 describes a particle dispersion including first and second colored particles that move in response to an electric field, and a dispersion medium, the second colored particles having a larger diameter than the first colored particles and the same charging characteristic as a charging characteristic of the first color particles, and in which the ratio (Cs/Cl) of the charge amount Cs of the first colored particles to the charge amount CI of the second colored particles per unit area of the display is less than or equal to 5.
• U.S. Patent Applications Publication Nos. 2012/0314273 and 2014/0002889 describe an electrophoresis device including a plurality of first and second electrophoretic particles included in an insulating liquid, the first and second particles having different charging characteristics that are different from each other; the device further comprising a porous layer included in the insulating liquid and formed of a fibrous structure.
• the present invention seeks to provide a full color display using only a single electrophoretic layer but capable of white, black, the three subtractive primary colors (cyan, magenta and yellow) and the three additive primary colors (red, green and blue) at every pixel of the display, and a method of driving such an electrophoretic display.
• this invention provides an electrophoretic medium comprising:
• This invention also provides an electrophoretic medium as described above in which the electric field required to separate aggregates formed between the first and second particles is less than that required to separate aggregates formed between the third and the fourth particles, the first and fourth particles, and the second and third particles.
• this invention provides an electrophoretic medium comprising:
• a plurality of fourth particles bearing charges of the same polarity as the second particles having either no polymer coating or a polymer coating such that the volume of the polymer in the essentially unsolvated state (i.e., in the dried powder) is not more than 15% of the total volume of the plurality of particles (i.e., including the core pigment and the polymer coating); and having a subtractive primary color different from those of the second and third particles.
• this invention provides such an electrophoretic medium in which at least two of the second, third and fourth particles are substantially non-scattering.
• this invention provides such an electrophoretic medium in which the first particle is white and the second, third and fourth particles are substantially non- scattering.
• This invention also provides an electrophoretic medium comprising four types of particle as described above dispersed in a fluid, wherein:
• the white particles of the first or second particles and the fourth particles each have a polymer coating comprising at least about 60 per cent by weight of an acrylate or methacrylate ester monomer wherein the ester group comprises a hydrocarbon chain comprising at least about six carbon atoms;
• the colored particles of the first or second particles have a physisorbed polymer coating comprising a polydimethylsiloxane-containing monomer.
• first and third particles are negatively charged and the second and fourth particles are positively charged.
• the first, second, third and fourth particles are respectively white, cyan, yellow and magenta in color.
• the white and yellow particles are negatively charged and the magenta and cyan particles are positively charged.
• this invention provides an electrophoretic medium comprising:
• this invention provides a method of driving an electrophoretic display of the invention, the display comprising a layer of the electrophoretic medium disposed between first and second electrodes, with the first electrode forming the viewing surface of the display, the display having voltage control means capable of applying voltage differences of +VH, +VL, 0, -VL and -VH between the first and second electrodes respectively, where:
• This method may further comprise:
• the method may further comprise:
• the present invention also provides an alternate method of driving an electrophoretic display of the present invention, the display comprising a layer of the electrophoretic medium disposed between first and second electrodes, with the first electrode forming the viewing surface of the display, the display having voltage control means capable of applying voltage differences of +VH, 0, and -VH between the first and second electrodes respectively, where:
• the electrophoretic media of the present invention may contain any of the additives used in prior art electrophoretic media as described for example in the E Ink and MIT patents and applications mentioned above.
• the electrophoretic medium of the present invention will typically comprise at least one charge control agent to control the charge on the various particles, and the fluid may have dissolved or dispersed therein a polymer having a number average molecular weight in excess of about 20,000 and being essentially non-absorbing on the particles to improves the bistability of the display, as described in the aforementioned U.S. Patent No. 7, 170,670.
• the present invention requires the use of a light-scattering particle, typically white, and three substantially non-light- scattering particles.
• a completely light-scattering particle or a completely non-light-scattering particle and the minimum degree of light scattering of the light-scattering particle, and the maximum tolerable degree of light scattering tolerable in the substantially non-light-scattering particles, used in the electrophoretic of the present invention may vary somewhat depending upon factors such as the exact pigments used, their colors and the ability of the user or application to tolerate some deviation from ideal desired colors.
• the scattering and absorption characteristics of a pigment may be assessed by measurement of the diffuse reflectance of a sample of the pigment dispersed in an appropriate matrix or liquid against white and dark backgrounds. Results from such measurements can be interpreted according to a number of models that are well-known in the art, for example, the one-dimensional Kubelka-Munk treatment.
• the white pigment exhibit a diffuse reflectance at 550 nm, measured over a black background, of at least 5% when the pigment is approximately isotropically distributed at 15% by volume in a layer of thickness 1 ⁇ comprising the pigment and a liquid of refractive index less than 1.55.
• the yellow, magenta and cyan pigments preferably exhibit diffuse reflectances at 650, 650 and 450 nm, respectively, measured over a black background, of less than 2.5% under the same conditions.
• the wavelengths chosen above for measurement of the yellow, magenta and cyan pigments correspond to spectral regions of minimal absorption by these pigments.
• Colored pigments meeting these criteria are hereinafter referred to as “non-scattering" or “substantially non-light-scattering”.
• Table 1 below shows the diffuse reflectance of preferred yellow, magenta, cyan and white pigments useful in electrophoretic media of the present invention (Yl, Ml, CI and Wl, described in more detail below), together with the ratio of their absorption and scattering coefficients according to the Kubelka-Munk analysis of these materials as dispersed in a poly(isobutylene) matrix.
• the electrophoretic medium of the present invention may be in any of the forms discussed above.
• the electrophoretic medium may be unencapsulated, encapsulated in discrete capsules surrounded by capsule walls, or in the form of a polymer-dispersed or microcell medium.
• This invention extends to a front plane laminate, double release sheet, inverted front plane laminate or electrophoretic display comprising an electrophoretic medium of the present invention.
• the displays of the present invention may be used in any application in which prior art electro-optic displays have been used.
• the present displays may be used in electronic book readers, portable computers, tablet computers, cellular telephones, smart cards, signs, watches, shelf labels and flash drives.
• Figure 1 of the accompanying drawings is a schematic cross-section showing the positions of the various particles in an electrophoretic medium of the present invention when displaying black, white, the three subtractive primary and the three additive primary colors.
• Figure 2 shows in schematic form the four types of pigment particle used in the present invention
• Figure 3 shows in schematic form the relative strengths of interactions between pairs of particles of the present invention
• Figure 4 shows in schematic form behavior of particles of the present invention when subjected to electric fields of varying strength and duration;
• Figures 5A and 5B show waveforms used to drive the electrophoretic medium shown in Figure 1 to its black and white states respectively.
• Figures 6A and 6B show waveforms used to drive the electrophoretic medium shown in Figure 1 to its magenta and blue states.
• Figures 6C and 6D show waveforms used to drive the electrophoretic medium shown in Figure 1 to its yellow and green states.
• Figures 7A and 7B show waveforms used to drive the electrophoretic medium shown in Figure 1 to its red and cyan states respectively.
• Figures 8-9 illustrate waveforms which may be used in place of those shown in Figures 5A-5B, 6A-6D and 7A-7B to drive the electrophoretic medium shown in Figure 1 to all its color states.
• Figures 10 is a graph illustrating the adsorption of a charge control agent on to certain particles of the invention.
• Figure 11 is a schematic cross-section through an apparatus used in Example 9 below to view the motion of particles of the invention when subjected to an electric field.
• Figures 12 and 13 are images of the motion of mixtures of magenta and yellow particles of the invention, and cyan and yellow particles of the invention, respectively, when subjected to an electric field.
• Figure 14(a) is a photograph of ITO coated glass slides after being submerged in a formulation containing cyan and white pigments and DC biased for 30 seconds at 500 V.
• Figure 14(b) is a photograph of ITO coated glass slides after being submerged in a formulation containing magenta and white pigments and DC biased for 30 seconds at 500 V.
• Figure 14(c) is a photograph of ITO coated glass slides after being submerged in a formulation containing magenta and yellow pigments and DC biased for 30 seconds at 500 V.
• Figures 15-18 are graphs showing the optical densities measured at 450 nm, 550 nm, and 650 nm as an electrophoretic medium of the present invention and similar media lacking certain particles are switched.
• Figures 19-21 are graphs showing the average distance from the SNAP standard for all eight "primary colors" as a function of differences in zeta potential, as measured in experiments described in Example 14 below.
• the present invention provides an electrophoretic medium which comprises one light-scattering particle (typically white) and three other particles providing the three subtractive primary colors.
• one light-scattering particle typically white
• three other particles providing the three subtractive primary colors.
• the three particles providing the three subtractive primary colors may be substantially non-light-scattering ("SNLS").
• SNLS particles allows mixing of colors and provides for more color outcomes than can be achieved with the same number of scattering particles.
• the aforementioned US 2012/0327504 uses particles having subtractive primary colors, but requires two different voltage thresholds for independent addressing of the non-white particles (i.e., the display is addressed with three positive and three negative voltages). These thresholds must be sufficiently separated for avoidance of cross-talk, and this separation necessitates the use of high addressing voltages for some colors.
• addressing the colored particle with the highest threshold also moves all the other colored particles, and these other particles must subsequently be switched to their desired positions at lower voltages.
• Such a step-wise color-addressing scheme produces flashing of unwanted colors and a long transition time.
• the present invention does not require the use of a such a stepwise waveform and addressing to all colors can, as described below, be achieved with only two positive and two negative voltages (i.e., only five different voltages, two positive, two negative and zero are required in a display, although as described below in certain embodiments it may be preferred to use more different voltages to address the display).
• Figure 1 of the accompanying drawings is a schematic cross-section showing the positions of the various particles in an electrophoretic medium of the present invention when displaying black, white, the three subtractive primary and the three additive primary colors.
• the viewing surface of the display is at the top (as illustrated), i.e., a user views the display from this direction, and light is incident from this direction.
• this particle is assumed to be the white pigment.
• this light-scattering white particle forms a white reflector against which any particles above the white particles (as illustrated in Figure 1) are viewed.
• the particles above the white particles may absorb various colors and the color appearing to the user is that resulting from the combination of particles above the white particles. Any particles disposed below (behind from the user's point of view) the white particles are masked by the white particles and do not affect the color displayed. Because the second, third and fourth particles are substantially non-light-scattering, their order or arrangement relative to each other is unimportant, but for reasons already stated, their order or arrangement with respect to the white (light-scattering) particles is critical.
• one subtractive primary color could be rendered by a particle that scatters light, so that the display would comprise two types of light-scattering particle, one of which would be white and another colored.
• the position of the light-scattering colored particle with respect to the other colored particles overlying the white particle would be important. For example, in rendering the color black (when all three colored particles lie over the white particles) the scattering colored particle cannot lie over the non-scattering colored particles (otherwise they will be partially or completely hidden behind the scattering particle and the color rendered will be that of the scattering colored particle, not black).
• Figure 1 shows an idealized situation in which the colors are uncontaminated (i.e., the light-scattering white particles completely mask any particles lying behind the white particles).
• the masking by the white particles may be imperfect so that there may be some small absorption of light by a particle that ideally would be completely masked.
• Such contamination typically reduces both the lightness and the chroma of the color being rendered.
• color contamination should be minimized to the point that the colors formed are commensurate with an industry standard for color rendition.
• a particularly favored standard is SNAP (the standard for newspaper advertising production), which specifies L*, a* and b* values for each of the eight primary colors referred to above. (Hereinafter, "primary colors" will be used to refer to the eight colors, black, white, the three subtractive primaries and the three additive primaries as shown in Figure 1.)
• a second phenomenon that may be employed to control the motion of a plurality of particles is hetero-aggregation between different pigment types; see, for example, the aforementioned US 2014/0092465.
• Such aggregation may be charge-mediated (Coulombic) or may arise as a result of, for example, hydrogen bonding or Van der Waals interactions.
• the strength of the interaction may be influenced by choice of surface treatment of the pigment particles. For example, Coulombic interactions may be weakened when the closest distance of approach of oppositely-charged particles is maximized by a steric barrier (typically a polymer grafted or adsorbed to the surface of one or both particles).
• a steric barrier typically a polymer grafted or adsorbed to the surface of one or both particles.
• such polymeric barriers are used on the first, and second types of particles and may or may not be used on the third and fourth types of particles.
• Figure 2 shows schematic cross-sectional representations of the four pigment types (1-4) used in preferred embodiments of the invention.
• the polymer shell adsorbed to the core pigment is indicated by the dark shading, while the core pigment itself is shown as unshaded.
• a wide variety of forms may be used for the core pigment: spherical, acicular or otherwise anisometric, aggregates of smaller particles (i.e., "grape clusters"), composite particles comprising small pigment particles or dyes dispersed in a binder, and so on as is well known in the art.
• the polymer shell may be a covalently-bonded polymer made by grafting processes or chemisorption as is well known in the art, or may be physisorbed onto the particle surface.
• the polymer may be a block copolymer comprising insoluble and soluble segments.
• First and second particle types in one embodiment of the invention preferably have a more substantial polymer shell than third and fourth particle types.
• the light-scattering white particle is of the first or second type (either negatively or positively charged).
• the white particle bears a negative charge (i.e., is of Type 1), but it will be clear to those skilled in the art that the general principles described will apply to a set of particles in which the white particles are positively charged.
• the electric field required to separate an aggregate formed from mixtures of particles of types 3 and 4 in the suspending solvent containing a charge control agent is greater than that required to separate aggregates formed from any other combination of two types of particle.
• the electric field required to separate aggregates formed between the first and second types of particle is, on the other hand, less than that required to separate aggregates formed between the first and fourth particles or the second and third particles (and of course less than that required to separate the third and fourth particles).
• FA PP is the force exerted on the particle by the applied electric field
• Fc is the Coulombic force exerted on the particle by the second particle of opposite charge
• Fvw is the attractive Van der Waals force exerted on one particle by the second particle
• FD is the attractive force exerted by depletion flocculation on the particle pair as a result of (optional) inclusion of a stabilizing polymer into the suspending solvent.
• the Van der Waals forces between the particles may also change substantially if the thickness of the polymer shell increases.
• the polymer shell on the particles is swollen by the solvent and moves the surfaces of the core pigments that interact through Van der Waals forces further apart.
• si+S2 the distance between them
• TGA thermal gravimetric analysis
• particles of types 1 and 2 (Wl, W2, M2, CI) have volume fractions of polymer of at least about 25%, corresponding to dried polymer shell thicknesses, for typical particle sizes, of at least 25 nm. In the suspending solvent, the polymer shell will extend further than this as it takes up the solvent.
• Particles of types 3 and 4 either have no polymer shell at all, or a polymer shell that has a volume fraction not exceeding about 15%, corresponding to dried polymer shell thicknesses, for typical particle sizes, of 0 - 10 nm.
• a convenient polar molecule for use in this determination is a charge control agent (CCA), which is an amphiphilic molecule comprising a polar head group and a non-polar tail group.
• CCA charge control agent
• Such molecules are known to form reverse micelles in non-polar solvents such as the suspending solvents used in the present invention.
• the polar head groups are known to adsorb onto surfaces (that are typically polar) that are not protected by non-polar polymeric chains. The degree of adsorption of the CCA onto the pigment surface is thus a measure of the area of the pigment surface that is not covered by the non-polar polymer and therefore inaccessible.
• Figure 3 shows in schematic form the strengths of the electric fields required to separate pairwise aggregates of the particle types of the invention.
• the interaction between particles of types 3 and 4 is stronger than that between particles of types 2 and 3.
• the interaction between particles of types 2 and 3 is about equal to that between particles of types 1 and 4 and stronger than that between particles of types 1 and 2. All interactions between pairs of particles of the same sign of charge as weak as or weaker than the interaction between particles of types 1 and 2.
• Figure 4 shows how these interactions may be exploited to make all the primary colors (subtractive, additive, black and white), as was discussed generally with reference to Figure 1.
• particle 1 is white
• particle 2 is cyan
• particle 3 is yellow
• particle 4 is magenta.
• the core pigment used in the white particle is typically a metal oxide of high refractive index as is well known in the art of electrophoretic displays. Examples of white pigments are described in the Examples below.
• Suitable yellow core pigments include C.I. Pigment Yellows 1, 3, 12, 13, 14, 16,
• Preferred yellow core pigments include C.I. Pigment Yellows 139, 155 and
• Suitable magenta core pigments include C.I. Pigment Reds 12, 14, 48:2, 48:3, 48:4, 57: 1, 112, 122, 146, 147, 176, 184, 185, 209, 257 and 262, and C.I. Pigment Violets 19 and 32.
• One preferred magenta core pigment is C.I. Pigment Red 122.
• Suitable cyan core pigments include C.I. Pigment Blues 15: 1, 15:2, 15:3, 15:4 and 79, and C.I. Solvent Blue 70.
• a display device may be constructed using an electrophoretic fluid of the invention in several ways that are known in the prior art.
• the electrophoretic fluid may be encapsulated in microcapsules or incorporated into microcell structures that are thereafter sealed with a polymeric layer.
• the microcapsule or microcell layers may be coated or embossed onto a plastic substrate or film bearing a transparent coating of an electrically conductive material. This assembly may be laminated to a backplane bearing pixel electrodes using an electrically conductive adhesive.
• the polarities of the charges on all the particles can be inverted and the electrophoretic medium will still function in the same manner provided that the polarity of the waveforms (see next paragraph) used to drive the medium is similarly inverted.
• the waveform (voltage against time curve) applied to the pixel electrode of the backplane of a display of the invention is described and plotted, while the front electrode is assumed to be grounded (i.e., at zero potential).
• the electric field experienced by the electrophoretic medium is of course determined by the difference in potential between the backplane and the front electrode and the distance separating them.
• the display is typically viewed through its front electrode, so that it is the particles adjacent the front electrode which control the color displayed by the pixel, and if it is sometimes easier to understand the optical transitions involved if the potential of the front electrode relative to the backplane is considered; this can be done simply by inverting the waveforms discussed below.
• each pixel of the display can be driven at five different addressing voltages, designated +Vhi g h, +Viow, 0, -Viow and -Vhigh, illustrated as 30V, 15V, 0, - 15V and -30V in Figures 5-7.
• addressing voltages designated +Vhi g h, +Viow, 0, -Viow and -Vhigh, illustrated as 30V, 15V, 0, - 15V and -30V in Figures 5-7.
• +Vhi g h, 0, and -Vhigh it may be possible to achieve the same result as addressing at a lower voltage (say, Vhi g h/n where n is a positive integer > 1) by addressing with pulses of voltage Vhigh but with a duty cycle of 1/n.
• [Para 114]Waveforms used in the present invention may comprise three phases: a DC- balancing phase, in which a DC imbalance due to previous waveforms applied to the pixel is corrected, or in which the DC imbalance to be incurred in the subsequent color rendering transition is corrected (as is known in the art), a "reset” phase, in which the pixel is returned to a starting configuration that is at least approximately the same regardless of the previous optical state of the pixel, and a "color rendering” phase as described below.
• the DC- balancing and reset phases are optional and may be omitted, depending upon the demands of the particular application.
• the "reset" phase may be the same as the magenta color rendering waveform described below, or may involve driving the maximum possible positive and negative voltages in succession, or may be some other pulse pattern, provided that it returns the display to a state from which the subsequent colors may reproducibly be obtained.
• Figures 5A and 5B show, in idealized form, typical color rendering phases of waveforms used to produce the black and white states in displays of the present invention.
• the graphs in Figures 5A and 5B show the voltage applied to the backplane (pixel) electrodes of the display while the transparent, common electrode on the top plane is grounded.
• the x- axis represents time, measured in arbitrary units, while the y-axis is the applied voltage in Volts.
• Driving the display to black ( Figure 5A) or white ( Figure 5B) states is effected by a sequence of positive or negative impulses, respectively, preferably at voltage Viow because, as noted above, at the fields (or currents) corresponding to Viow the magenta and yellow pigments are aggregated together.
• the white and cyan pigments move while the magenta and yellow pigments remain stationary (or move with a much lower velocity) and the display switches between a white state and a state corresponding to absorption by cyan, magenta and yellow pigments (often referred to in the art as a "composite black").
• the length of the pulses to drive to black and white may vary from about 10-1000 milliseconds, and the pulses may be separated by rests (at zero applied volts) of lengths in the range of 10-1000 milliseconds.
• Figure 5 shows pulses of positive and negative voltages, respectively, to produce black and white, these pulses being separated by "rests" where zero voltage is supplied, it is sometimes preferred that these "rest” periods comprise pulses of the opposite polarity to the drive pulses, but having lower impulse (i.e., having a shorter duration or a lower applied voltage than the principal drive pulses, or both).
• Figures 6A-6D show typical color rendering phases of waveforms used to produce the colors magenta and blue ( Figures 6A and 6B) and yellow and green ( Figures 6C and 6D).
• the waveform oscillates between positive and negative impulses, but the length of the positive impulse (t P ) is shorter than that of the negative impulse (t n ), while the voltage applied in the positive impulse (V P ) is greater than that of the negative impulse (V n ).
• the period of one cycle of positive and negative impulses may range from about 30-1000 milliseconds.
• a sequence of impulses comprising at least one cycle of V P t P followed by Vntn is preferred, where V P > V n and t P ⁇ t n .
• V P > V n and t P ⁇ t n .
• Figure 6B shows an alternative waveform for the production of magenta and blue states using only three voltage levels.
• This sequence cannot be DC- balanced. When the color blue is required, the sequence ends on V P whereas when the color magenta is required the sequence ends on Vn.
• Figures 7A and 7B show color rendering phases of waveforms used to render the colors red and cyan on a display of the present invention. These waveforms also oscillate between positive and negative impulses, but they differ from the waveforms of Figures 6A- 6D in that the period of one cycle of positive and negative impulses is typically longer and the addressing voltages used may be (but are not necessarily) lower.
• the red waveform of Figure 7A consists of a pulse (+Viow) that produces black (similar to the waveform shown in Figure 5A) followed by a shorter pulse (-Viow) of opposite polarity, which removes the cyan particles and changes black to red, the complementary color to cyan.
• the cyan waveform is the inverse of the red one, having a section that produces white (-Viow) followed by a short pulse (Viow) that moves the cyan particles adjacent the viewing surface.
• the cyan moves faster relative to white than either the magenta or yellow pigments.
• the yellow pigment in the Figure 7 waveforms remains on the same side of the white particles as the magenta particles.
• the waveforms described above with reference to Figures 5-7 use a five level drive scheme, i.e., a drive scheme in which at any given time a pixel electrode may be at any one of two different positive voltages, two different negative voltages, or zero volts relative to a common front electrode.
• the five levels are 0, ⁇ 15V and ⁇ 30V. It has, however, in at least some cases been found to be advantageous to use a seven level drive scheme, which uses seven different voltages: three positive, three negative, and zero.
• This seven level drive scheme may hereinafter be referred to as the "second drive scheme" of the present invention.
• the choice of the number of voltages used to address the display should take account of the limitations of the electronics used to drive the display. In general, a larger number of drive voltages will provide greater flexibility in addressing different colors, but complicates the arrangements necessary to provide this larger number of drive voltages to conventional device display drivers. The present inventors have found that use of seven different voltages provides a good compromise between complexity of the display architecture and color gamut.
• FIG. 8 A generic waveform embodying modifications of the basic principles described above is illustrated in Figure 8, in which the abscissa represents time (in arbitrary units) and the ordinate represents the voltage difference between a pixel electrode and the common front electrode.
• the magnitudes of the three positive voltages used in the drive scheme illustrated in Figure 8 may lie between about +3V and +30V, and of the three negative voltages between about -3V and -30V.
• the highest positive voltage, +Vmax is +24 V
• the medium positive voltage, +Vmid is 12V
• the lowest positive voltage, +Vmin is 5V.
• negative voltages -Vmax, -Vmid and -Vmin are; in a preferred embodiment -24V, -12V and -9V. It is not necessary that the magnitudes of the voltages
• pulses there are supplied pulses (wherein “pulse” signifies a monopole square wave, i.e., the application of a constant voltage for a predetermined time) at +Vmax and -Vmax that serve to erase the previous image rendered on the display (i.e., to "reset” the display).
• the lengths of these pulses (ti and t3) and of the rests (i.e., periods of zero voltage between them (t2 and t4) may be chosen so that the entire waveform (i.e., the integral of voltage with respect to time over the whole waveform as illustrated in Figure 8) is DC balanced (i.e., the integral is substantially zero).
• DC balance can be achieved by adjusting the lengths of the pulses and rests in phase A so that the net impulse supplied in this phase is equal in magnitude and opposite in sign to the net impulse supplied in the combination of phases B and C, during which phases, as described below, the display is switched to a particular desired color.
• the generic waveform is intrinsically DC balanced, and this may be preferred in certain embodiments of the invention.
• the pulses in phase A may provide DC balance to a series of color transitions rather than to a single transition, in a manner similar to that provided in certain black and white displays of the prior art; see for example U.S. Patent No. 7,453,445 and the earlier applications referred to in column 1 of this patent.
• phase B in Figure 8 there are supplied pulses that use the maximum and medium voltage amplitudes.
• the colors white, black, magenta, red and yellow are preferably rendered in the manner previously described with reference to Figures 5-7. More generally, in this phase of the waveform the colors corresponding to particles of type 1 (assuming that the white particles are negatively charged), the combination of particles of types 2, 3, and 4 (black), particles of type 4 (magenta), the combination of particles of types 3 and 4 (red) and particles of type 3 (yellow), are formed.
• white may be rendered by a pulse or a plurality of pulses at -Vmid.
• the white color produced in this way may be contaminated by the yellow pigment and appear pale yellow.
• white may be obtained by a single instance or a repetition of instances of a sequence of pulses comprising a pulse with length Ti and amplitude +Vmax or +Vmid followed by a pulse with length T2 and amplitude -Vmid, where T 2 > Ti.
• the final pulse should be a negative pulse.
• Figure 8 there are shown four repetitions of a sequence of +Vmax for time is followed by -Vmid for time te.
• the appearance of the display oscillates between a magenta color (although typically not an ideal magenta color) and white (i.e., the color white will be preceded by a state of lower L* and higher a* than the final white state).
• a magenta color although typically not an ideal magenta color
• white i.e., the color white will be preceded by a state of lower L* and higher a* than the final white state.
• This is similar to the pulse sequence shown in Fig. 6A, in which an oscillation between magenta and blue was observed.
• the difference here is that the net impulse of the pulse sequence is more negative than the pulse sequence shown in Fig. 6A, and thus the oscillation is biased towards the negatively charged white pigment.
• black may be obtained by a rendered by a pulse or a plurality of pulses (separated by periods of zero voltage) at +Vmid.
• magenta may be obtained by a single instance or a repetition of instances of a sequence of pulses comprising a pulse with length T3 and amplitude +Vmax or +Vmid, followed by a pulse with length T 4 and amplitude -Vmid, where T 4 > T3.
• the net impulse in this phase of the waveform should be more positive than the net impulse used to produce white.
• the display will oscillate between states that are essentially blue and magenta.
• the color magenta will be preceded by a state of more negative a* and lower L* than the final magenta state.
• red may be obtained by a single instance or a repetition of instances of a sequence of pulses comprising a pulse with length T5 and amplitude +Vmax or +Vmid, followed by a pulse with length T6 and amplitude -Vmax or -Vmid.
• the net impulse should be more positive than the net impulse used to produce white or yellow.
• the positive and negative voltages used are substantially of the same magnitude (either both Vmax or both Vmid)
• the length of the positive pulse is longer than the length of the negative pulse
• the final pulse is a negative pulse.
• the display will oscillate between states that are essentially black and red. The color red will be preceded by a state of lower L*, lower a*, and lower b* than the final red state.
• [Para 136]Yellow may be obtained by a single instance or a repetition of instances of a sequence of pulses comprising a pulse with length T7 and amplitude +Vmax or +Vmid, followed by a pulse with length Ts and amplitude -Vmax.
• the final pulse should be a negative pulse.
• the color yellow may be obtained by a single pulse or a plurality of pulses at -Vmax.
• phase C in Figure 8 there are supplied pulses that use the medium and minimum voltage amplitudes.
• the colors blue and cyan are produced following a drive towards white in the second phase of the waveform, and the color green is produced following a drive towards yellow in the second phase of the waveform.
• the colors blue and cyan will be preceded by a color in which b* is more positive than the b* value of the eventual cyan or blue color
• the color green will be preceded by a more yellow color in which L* is higher and a* and b* are more positive than L*, a* and b* of the eventual green color.
• a display of the present invention is rendering the color corresponding to the colored one of the first and second particles, that state will be preceded by a state that is essentially white (i.e., having C* less than about 5).
• a display of the present invention When a display of the present invention is rendering the color corresponding to the combination of the colored one of the first and second particles and the particle of the third and fourth particles that has the opposite charge to this particle, the display will first render essentially the color of the particle of the third and fourth particles that has the opposite charge to the colored one of the first and second particles.
• cyan and green will be produced by a pulse sequence in which +Vmin must be used. This is because it is only at this minimum positive voltage that the cyan pigment can be moved independently of the magenta and yellow pigments relative to the white pigment. Such a motion of the cyan pigment is necessary to render cyan starting from white or green starting from yellow.
• the display of the invention has been described as producing the eight primary colors, in practice, it is preferred that as many colors as possible be produced at the pixel level. A full color gray scale image may then be rendered by dithering between these colors, using techniques well known to those skilled in imaging technology.
• the display may be configured to render an additional eight colors.
• these additional colors are: light red, light green, light blue, dark cyan, dark magenta, dark yellow, and two levels of gray between black and white.
• the terms "light” and “dark” as used in this context refer to colors having substantially the same hue angle in a color space such as CIE L*a*b* as the reference color but a higher or lower L*, respectively.
• Gray colors are typically achieved by a sequence of pulses oscillating between low or mid voltages.
• Fig. 9 shows an appropriate modification to the generic waveform of Figure 8.
• phase A no change is necessary, since only three voltages (+Vmax, 0, -Vmax) are needed.
• Phase B is replaced by subphases Bl and B2 are defined, of lengths Li and L 2 , respectively, during each of which a particular set of three voltages are used.
• phase B l voltages +Vmax, 0, -Vmax) are available, while in phase B2 voltages +Vmid, 0 , -Vmid are available.
• the waveform requires a pulse of +Vmax for time is in subphase B l .
• Subphase B l is longer than time is (for example, to accommodate a waveform for another color in which a pulse longer than is might be needed), so a zero voltage is supplied for a time Li - ts.
• the location of the pulse of length is and the zero pulse or pulses of length Li - ts within subphase B l may be adjusted as required (i.e., subphase B l does not necessarily begin with the pulse of length ts as illustrated).
• top plane switching When top plane switching is used in combination with a three-level source driver, the same general principles apply as described above with reference to Fig. 9. Top plane switching may be preferred when the source drivers cannot supply a voltage as high as the preferred Vmax. Methods for driving electrophoretic displays using top plane switching are well known in the art.
• N can be 1-20.
• this sequence comprises 14 frames that are allocated positive or negative voltages of magnitude Vmax or Vmid, or zero.
• the pulse sequences shown are in accord with the discussion given above. It can be seen that in this phase of the waveform the pulse sequences to render the colors white, blue and cyan are the same (since blue and cyan are achieved in this case starting from a white state, as described above). Likewise, in this phase the pulse sequences to render yellow and green are the same (since green is achieved starting from a yellow state, as described above).
• Table 4 shows the results from driving a display made using a coating prepared as described in Example 11 , Part A, below laminated to a thin-film transistor array backplane.
• White particle Wl is a silanol-functionalized light-scattering pigment (titanium dioxide) to which a polymeric material comprising lauryl methacrylate (LMA) monomers has been attached as described in U.S. Patent No. 7,002,728.
• White particle W2 is a polymer-coated titania produced substantially as described in Example 1 of United States Patent No. 5,852, 196, with a polymer coating comprising an approximately 99: 1 ratio of lauryl methacrylate and 2,2,2-trifluoroethyl methacrylate.
• [Para 158]Yellow particle Yl is C.I. Pigment Yellow 180, used without coating and dispersed by attrition in the presence of Solsperse 19000, as described generally in the aforementioned Application Serial No. 14/277, 107 and in Example 1, below.
• [Para 159]Yellow particle Y2 is C.I. Pigment Yellow 155 used without coating and dispersed by attrition in the presence of Solsperse 19000, as described generally in the aforementioned Application Serial No. 14/277, 107 and in Example 2, below.
• [Para 160]Yellow particle Y3 is C.I. Pigment Yellow 139, used without coating and dispersed by attrition in the presence of Solsperse 19000, as described generally in the aforementioned Application Serial No. 14/277, 107 and in Example 3, below.
• Yellow particle Y4 is C.I. Pigment Yellow 139, which is coated by dispersion polymerization, incorporating trifluoroethyl methacrylate, methyl methacrylate and dimethylsiloxane-containing monomers in a manner described in Example 4 below.
• Magenta particle Ml is a positively-charged magenta material (dimethylquinacridone, C.I. Pigment Red 122) coated using vinylbenzyl chloride and LMA as described in the aforementioned Application Serial No. 14/277,107 and in Example 5, below.
• Magenta particle M2 is a C.I. Pigment Red 122 which is coated by dispersion polymerization, methyl methacrylate and dimethylsiloxane-containing monomers in a manner described in Example 6 below.
• Cyan particle CI is a copper phthalocyanine material (C.I. Pigment Blue 15:3) which is coated by dispersion polymerization, incorporating methyl methacrylate and dimethylsiloxane-containing monomers in a manner described in Example 7 below.
• the reactor was assembled with a nitrogen immersion tube, overhead stirring impeller and an air condenser.
• the overhead air stirrer was set to 400 rpm and the reaction mixture was purged with nitrogen for 30 min at 65 °C, after which the immersion tube was removed and the rotometer nitrogen level set.
• 0.358 g 2,2'-azobis(2- methylpropionitrile) (AIBN) was dissolved in ethyl acetate and added to a syringe.
• the vial was then rinsed with ethyl acetate and added to the same syringe.
• the resultant AIBN solution was injected into the reactor over 30 min and the reaction mixture was heated for 16- 24 hours.
• the reaction mixture was dispensed into a 1 L centrifuge bottle and centrifuged. The supernatant was decanted, and the remaining pigment was washed with Isopar E and centrifuged. This washing process was repeated two additional times, and after the final supernatant was decanted, the remaining pigment was dried in a vacuum oven at room temperature overnight.
• Ink Jet Magenta E 02 (available from Clariant Corporation, 15 g) was dispersed in toluene (135 g). The dispersion was transferred to a 500 mL round bottom flask and the headspace was degassed with nitrogen. The resultant reaction mixture was brought to 42 C and, upon temperature equilibration, 4-vinylbenzylchloride was added and the reaction mixture was allowed to stir at 42 C under nitrogen overnight. The resulting product was allowed to cool to room temperature and centrifuged to isolate the functionalized pigment. The centrifuge cake was washed three times with toluene to give the functionalized magenta pigment (14.76 g).
• the overhead air stirrer was set to 400 rpm and the reaction mixture was purged with nitrogen for 30 min at 65 °C, after which the immersion tube was removed and the rotometer nitrogen level set.
• AIBN 2,2'-azobis(2-methylpropionitrile)
• the vial was then rinsed with ethyl acetate and added to the same syringe.
• the resultant AIBN solution was injected into the reactor over 30 min and the reaction mixture was heated for 16-24 hours.
• the reaction mixture was dispensed into a 1 L centrifuge bottle and centrifuged.
• the supernatant was decanted, and the remaining pigment was washed with Isopar E and centrifuged. This washing process was repeated two additional times, and after the final supernatant was decanted, the remaining pigment was dried in a vacuum oven at room temperature overnight.
• the overhead air stirrer was set to 400 rpm and the reaction mixture was purged with nitrogen for one hour at 65 °C, after which the immersion tube was removed and the rotometer nitrogen level set.
• AIBN 2,2'-azobis(2-methylpropionitrile)
• the vial was then rinsed with ethyl acetate and added to the same syringe.
• the resultant AIBN solution was injected into the reactor over 30 min and the reaction mixture was heated for 16-24 hours.
• the reaction mixture was dispensed into a 1 L centrifuge bottle and centrifuged.
• the supernatant was decanted, and the remaining pigment was washed with Isopar E and centrifuged. This washing process was repeated three additional times, and after the final supernatant was decanted, the remaining pigment was dried in a vacuum oven at room temperature overnight.
• the dispersions of particles CI and Y3 had previously been centrifuged at 20,000 rpm for 45 minutes and rediluted with Isopar G containing 0.36 % w/w of a 4: 1 mass ratio of Solsperse 19000: Solsperse 17000 three times to ensure that any soluble impurities had been removed. After the fluid had been prepared it was dispersed by sonication for 90 minutes before use.
• Figure 12 shows the result of applying an electric field to the mixture of magenta pigment Ml and yellow pigment Y3 (fluid (i)). At even the highest voltage the aggregate between these two pigments is not separated, remaining as reddish conglomerates that migrate towards the cathode.
• Figure 13 shows the result of applying an electric field to the mixture of cyan pigment CI and yellow pigment Y3 (fluid (ii)). At applied voltages of 1000 V and higher the two pigments are separated, the cyan traveling towards the cathode and the yellow towards the anode.
• the devices produced as described in Part C was driven using a waveform as shown in Table 5.
• the waveform comprised four phases: (1) a reset with a low frequency at a high addressing voltage; (2) writing to the white state using a method similar to that described above with reference to Table 3; (3) writing to the cyan state using a method similar to that described above with reference to Figure 7(B); and (4) zero Volts.
• Each phase of the waveform used a square-wave form alternating between voltages VI and V2 at the frequency shown, with a duty cycle (defined as the proportion of the time of one cycle at which the display was driven at voltage VI) as indicated.
• Figures 15-18 show the optical densities at 450 nm (blue light absorption), 550 nm (green light absorption) and 650 nm (red light absorption) obtained during the "cyan writing" and "zero" phases of the waveform shown in Table 5.
• the raw optical densities were converted to "analytical densities", i.e., the optical density contributions of only the cyan pigment at 650 nm, only the magenta pigment at 550 nm, and only the yellow pigment at 450 nm, by removal of the absorptions of the other pigments at the indicated wavelengths.
• the optical density at 450 nm was approximately proportional to the amount of yellow pigment on the viewing side of the white pigment; the optical density at 550 nm was approximately proportional to the amount of magenta pigment on the viewing side of the white pigment; and the optical density at 650 nm was approximately proportional to the amount of cyan pigment on the viewing side of the white pigment.
• Figure 15 shows the optical density traces corresponding to a mixture of the white, yellow and magenta particles (fluid (i)). There is seen (at this low addressing voltage) virtually no modulation from the white state. This is consistent with the formation of an almost immobile aggregate formed by the yellow and magenta particles (i.e., the white pigment may move but at this low addressing voltage cannot displace the (red) aggregate of the yellow and magenta particles.
• Figure 16 shows the optical density traces corresponding to a mixture of the white, yellow and cyan particles (fluid (ii)). There is now seen (again at the low addressing voltage) considerably greater modulation of cyan (650 nm, dynamic range approximately 0.3 OD) and yellow (450 nm, dynamic range approximately 0.1 OD). This is consistent with the formation of a weaker aggregate between the yellow and cyan particles than was formed between the yellow and magenta particles. The dynamic range of cyan oscillation is much lower than when the yellow particle is not present (cf. Figure 17, below).
• Figure 17 shows the optical density traces corresponding to a mixture of the white, magenta and cyan particles (fluid (iii)).
• cyan 650 nm, dynamic range approximately 0.9 OD
• magenta 550 nm, dynamic range approximately 0.6 OD
• the increased optical density range in cyan versus that shown in Figure 16 is consistent with cyan and yellow forming an aggregate that requires a higher field to separate than cyan and white.
• the electric field strength required to separate aggregates appears to be in the order P2-P3 > P2- Pl for particles of types 1, 2 and 3.
• Figure 18 shows the optical density traces corresponding to a mixture of the white, yellow, magenta and cyan particles (fluid (iv)).
• cyan 650 nm, dynamic range approximately 0.9 OD
• magenta has been suppressed
• 550 nm, dynamic range approximately 0.2 OD 550 nm, dynamic range approximately 0.2 OD.
• the reduced optical density range in magenta versus that shown in Figure 17 is consistent with magenta and yellow forming an aggregate that requires a higher field to separate than cyan and yellow.
• [Para 225]Titanium dioxide was silane-treated as described in U.S. Patent No. 7,002,728, and the silane-treated white pigment was polymerized with poly(lauryl methacrylate) to afford the coated white pigment.
• the dry pigment (1100 g) was combined with Isopar G (733.33 g) to give the final white dispersion.
• a parallel-plate test cell was prepared consisting of two horizontal 50 x 55 mm glass plates each coated with a transparent, conductive coating of indium tin oxide (ITO) between which was introduced the electrophoretic medium to be tested. Silica spacer beads of nominally 20 ⁇ diameter were incorporated to maintain a constant gap between the glass plates.
• the electrophoretic fluid prepared as described above (95 ⁇ ) was dispensed onto the ITO-coated face of the lower glass plate and then the upper glass plate was placed over the fluid so that the ITO coating was in contact with the fluid. Electrical connections were then made to the ITO-coated sides of both the top and bottom glass plates.
• Fluid v also performs worse than the control: in this fluid the white pigment (type 1 particle) has a higher zeta potential than in fluids i, ii, and iii, and thus would be expected to interact more strongly with the cyan pigment (type 2 particle), which is not preferred in the invention.
• Table 9 shows the colors that were obtained after the test display was driven as described above. It can be seen that all eight primary colors were obtainable; however, the quality of the color rendition was not as high as when the "second drive scheme" of the invention was employed (see Table 4 above).
• the overhead air stirrer was set to 400 rpm and the reaction mixture was purged with nitrogen for one hour at 65°C, after which the immersion tube was removed and the rotometer nitrogen level set.
• AIBN 2,2'-azobis(2-methylpropionitrile)
• the vial was then rinsed with ethyl acetate and added to the same syringe.
• the resultant AIBN solution was injected into the reactor in a single addition and the reaction mixture heated for 16-24 hours.
• the reaction mixture was then dispensed into a 1 L centrifuge bottle and centrifuged.
• the supernatant was decanted, and the remaining pigment was washed with Isopar E and again centrifuged. This washing procedure was repeated twice, and after the final supernatant was decanted, the remaining pigment was dried in a vacuum oven at room temperature overnight.
• the dried pigment was dispersed to a 30 per cent by weight mixture with Isopar G using sonication and rolling and the resulting dispersion was filtered through 200 ⁇ mesh and the percentage of solid material in the dispersion measured.
• the attrition of the cyan pigment was halted and the hydrolyzed silane solution was added into the attritor.
• the pH was adjusted to about 9.4 with concentrated aqueous ammonium hydroxide solution.
• Attrition was then continued for a further 1 hour, after which the glass beads were removed by filtration and the resultant silane-functionalized pigment was isolated from the filtrate by centrifugation, dried at 70°C for 16 hours, and then ground with a mortar and pestle to a fine powder.
• the crude pigment was redispersed with sonication into toluene and again collected by centrifugation (4500 rpm, 30 min), then dried at 70°C.
• the dried pigment was dispersed to a 30 per cent by weight mixture with Isopar G using sonication and rolling, then filtered through 200 ⁇ mesh and the percentage of solid material in the dispersion measured.
• [Para 256]Table 10 shows the properties of a series of pigments prepared according to the general methods outlined above.
• a surfactant was added to aid in the dispersion of the core pigment particles prior to polymerization: this is indicated as the "dispersion aid" in the Table (PVP is poly(vinylpyrollidone); Solsperse 8000 is a surfactant available from Lubrizol Corporation, Wickliffe, OH; OLOA 371 is a surfactant available from Chevron Oronite, Bellaire, TX).
• TMPTMA trimethylolpropane trimethacrylate
• Core pigments Pigment Blue 15:3 and Pigment Blue 15:4 are copper phthalocyanine materials (i.e., organometallic compounds).
• the core pigments shown as EX1456 and BL0424 are inorganic materials available from The Shepherd Color Company, Cincinnati, OH.
• Electrophoretic fluids were prepared with cyan particles C2 - CI 5.
• the cyan pigments were added in to electrophoretic fluid compositions in amounts that were in inverse proportion to their extinction coefficients.
• An exemplary preparation is given below.
• Example 1 The yellow pigment dispersion prepared in Example 1 (0.64 g) was combined with the magenta dispersion prepared in Example 5 (0.85 g), the white dispersion prepared in Example 10, Part A above (4.93 g), and the cyan dispersion (0.47 g of a 31.7% w/w dispersion for a pigment of extinction coefficient 2.24 m2/g as measured at 650 nm), Solsperse 17000 (0.06 g of a 20% w/w solution in Isopar G), poly(isobutylene) of molecular weight 850,000 and additional Isopar G. The resultant mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition comprising a pigment in a mobile phase) having a conductivity of approximately 30 pS/cm.
• an electrophoretic fluid i.e., an electrophoretic composition comprising a pigment in a mobile phase having a conductivity of approximately 30 pS/
• cyan particle Three different types of cyan particle were used: a) materials functionalized by dispersion polymerization using methyl methacrylate and monomethacrylate terminated poly(dimethylsiloxane) monomers as described in Part A above (particles C2-C9, shown by open circles in Figures 19-21); b) organometallic materials functionalized as described in Part B above by silane treatment followed by polymerization with lauryl methacrylate (particles C10-C13, shown by open squares in Figures 19-21); and c) inorganic materials functionalized as described in Part B above by silane treatment followed by polymerization with lauryl methacrylate (particles C14-C15, shown by filled squares in Figures 19-21) .
• the inorganic cyan particles (filled squares) have much higher zeta potential and give good color results, possibly because the silane treatment, as noted above, is more efficient when applied to an inorganic than to an organic surface.
• the inorganic core pigment scatters light substantially, and the black state obtained from these formulations (L* 34 and 36, respectively, for C14 and C15) was much poorer than the black state obtained from the better organometallic pigments (for example L* 28 and 27, respectively, for C3 and C4).
• Figure 20 shows the same trend for the color magenta.
• the magenta color is formed when the magenta pigment moves more slowly through the white pigment (due to heteroaggregation, in this case between particles of types 1 and 4) than the cyan pigment (which, being a particle of type 2, has only a weak heteroaggregation with particles of type 1).
• the silane treatment does not provide as effective a steric polymer shell as the dispersion polymerization process for the organometallic core cyan pigment, such that the discrimination between magenta and cyan pigments is less evident.

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