Color electrophoretic display
阅读说明：本技术 彩色电泳显示器 (Color electrophoretic display ) 是由 S·特尔佛 S·布尔 J·M·莫里森 L·M·斯洛米奇 D·D·米勒 O·V·巴里基那-泰 于 2015-09-10 设计创作，主要内容包括：一种电泳介质,包括流体、第一光散射粒子(1)(通常为白色)以及具有三种减法原色(通常为品红色、青色和黄色)的第二(2)、第三(3)和第四(4)粒子；这些彩色粒子(2-4)中的至少两种是非光散射的。第一(1)和第二(2)粒子带有聚合物涂层,以使得分离由第三(3)和第四(4)粒子形成的聚集体所需的电场大于分离由任意其他两种类型的粒子形成的聚集体所需的电场。还描述了用于驱动介质以产生白色、黑色、品红色、青色、黄色、红色、绿色和蓝色的方法。(An electrophoretic medium comprising a fluid, first light-scattering particles (1) (typically white) and second (2), third (3) and fourth (4) particles having three subtractive primary colors (typically magenta, cyan and yellow); at least two of the colored particles (2-4) are non-light scattering. The first (1) and second (2) particles are coated with a polymer such that the electric field required to separate the aggregates formed by the third (3) and fourth (4) particles is greater than the electric field required to separate the aggregates formed by any of the other two types of particles. Methods for driving the media to produce white, black, magenta, cyan, yellow, red, green, and blue colors are also described.)
1. A method of driving an electrophoretic display, the display comprising a layer of an electrophoretic medium disposed between first and second electrodes, the first electrode forming a viewing surface of the display and the electrophoretic medium comprising a plurality of first, second, third and fourth particles dispersed in a fluid, the display having a display device capable of applying + V between the first and second electrodes respectivelyH,+VL,0,-VLand-VHThe voltage regulator of (a), wherein:
+VH>+VL>0>-VL>–VH
the method comprises, in any order:
(a) driving the fourth particles by applying + V of a polarity between the electrodes towards the first electrodeHor-VHAlternately displaying at the viewing surface the color of the fourth particles and the color of the mixture of the fourth particles and the second particles, the series of first pulses being of opposite polarity to the first pulses but greater than the duration of the first pulsesLor-VLAlternating with the second pulse of (1); and
(b) driving the third particles by applying + V of a polarity between the electrodes towards the first electrodeHor-VHAlternately displaying at the viewing surface the color of the third particles and the color of the mixture of the third particles and the second particles, the series of third pulses being of opposite polarity to the third pulses but greater duration than the third pulsesLor-VLAlternates the fourth pulse of (2).
2. The method of claim 1, further comprising:
(c) driving the first particles by applying + V of a polarity between the electrodes towards the second electrodeLor-VLA series of fifth pulses that display substantially black at the viewing surface, the series of fifth pulses alternating with periods of substantially zero voltage difference between the electrodes; and
(d) driving the first particles by applying + V of a polarity between the electrodes towards the first electrodeLor-VLDisplaying the color of the first particles at the viewing surface, the series of sixth pulses alternating with periods of substantially zero voltage difference between the electrodes.
3. The method of claim 2, further comprising:
(e) driving the second particles by applying + V of a polarity between the electrodes towards the second electrodeLor-VLAlternately displaying at the viewing surface the color of the second particles or the color of a mixture of the third and fourth particles, the series of seventh pulses being of opposite polarity to the seventh pulses but greater than the length of the seventh pulsesLor-VLThe eighth pulse of (3) alternates.
4. The method of claim 1, further comprising:
(c) driving the second particles by applying + V of a polarity between the electrodes towards the second electrodeLor-VLAlternately displaying at the viewing surface the color of the second particles or the color of a mixture of the third and fourth particles, the series of seventh pulses being of opposite polarity to the seventh pulses but greater than the length of the seventh pulsesLor-VLThe eighth pulse of (3) alternates.
5. A method of driving an electrophoretic display, the display comprising a layer of an electrophoretic medium disposed between first and second electrodes, the first electrode forming a viewing surface of the display and the electrophoretic medium comprising a plurality of first, second, third and fourth particles dispersed in a fluid, the display having a display device capable of applying + V between the first and second electrodes respectivelyH0, and-VHThe voltage regulator of (a), wherein:
+VH>0>–VH
the method comprises, in any order:
(a) driving the fourth particles by applying + V of a polarity between the electrodes towards the second electrodeHor-VHAlternately displaying at the viewing surface the color of the fourth particles and the color of the mixture of the fourth particles and the second particles, the series of first pulses being of opposite polarity to the first pulses but greater duration than the first pulses+VHor-VHAlternating with the second pulse of (1); and
(b) driving the third particles by applying + V of a polarity between the electrodes towards the second electrodeHor-VHAlternately displaying at the viewing surface the color of the third particles and the color of the mixture of the third particles and the second particles, the series of third pulses being of opposite polarity to the third pulses but greater duration than the third pulsesHor-VHAlternates the fourth pulse of (2).
Technical Field
The present invention relates to a color electrophoretic display, and more particularly, to an electrophoretic display capable of representing more than two colors using a single layer of electrophoretic material including a plurality of color particles.
Background
The term color as used herein includes black and white. The white particles are typically of the light scattering type.
The term gray state is used herein in its conventional meaning in the imaging arts to refer to a state intermediate the two extreme optical states of a pixel, but does not necessarily imply a black-and-white transition between the two extreme states. For example, several patents and published applications by the incorporated of lngk, referenced below, describe electrophoretic displays in which the extreme states are white and dark blue, such that the intermediate gray state is effectively pale blue. In fact, as already mentioned, the change in optical state may not be a color change at all. The terms black and white may be used hereinafter to refer to the two extreme optical states of the display and should be understood to generally include extreme optical states not limited to black and white alone, such as the white and deep blue states mentioned above.
The terms bistable and bistability are used herein in their conventional sense in the art to refer to displays comprising display elements having first and second display states differing in at least one optical property such that, after any given element is driven to assume its first or second display state using an addressing pulse of finite duration, that state will last at least several times (e.g. at least 4 times) the minimum duration of the addressing pulse required to change the state of that display element after the addressing pulse has terminated. U.S. patent No.7,170,670 shows that some particle-based electrophoretic displays capable of displaying gray scale can be stabilized not only in their extreme black and white states, but also in their intermediate gray states, as can some other types of electro-optic displays. This type of display is properly referred to as multi-stable rather than bi-stable, but for convenience the term bi-stable may be used herein to cover both bi-stable and multi-stable displays.
The term impulse, as used herein in relation to driving an electrophoretic display, refers to the integral over time of the applied voltage during the period of time that the display is driven.
Particles that absorb, scatter or reflect light in a broad band or in a selected wavelength are referred to herein as colored or pigment particles. Various materials that absorb or reflect light, such as dyes or photonic crystals, in addition to pigments (which term is meant to be an insoluble color material in the strict sense), may also be used in the electrophoretic media and displays of the present invention.
Particle-based electrophoretic displays have been the subject of intensive development for many 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 may have the following properties compared to liquid crystal displays: good brightness and contrast, wide viewing angle, state bistability, and low power consumption. However, problems with the long-term image quality of these displays have prevented their widespread use. For example, the particles that make up electrophoretic displays tend to settle, resulting in insufficient lifetime of these displays.
As mentioned above, electrophoretic media require the presence of a fluid. In most prior art electrophoretic media, the fluid is a liquid, but the electrophoretic medium can be produced using a gaseous fluid; see, e.g., Kitamura, T.et al, electric filter movement for electronic Paper-like display, IDW Japan,2001, Paper HCS1-1, and Yamaguchi, Y.et al, inner display using insulating particles chargeless electric display, IDW Japan,2001, Paper AMD 4-4. See also U.S. patent nos. 7,321,459 and 7,236,291. Such gas-based electrophoretic media, when used in a direction that allows particle settling (e.g., in a sign in which the media is arranged in a vertical plane), appear to experience the same types of problems due to particle settling as liquid-based electrophoretic media. In fact, particle settling presents a more serious problem in gas-based electrophoretic media than in liquid-based electrophoretic media, since the viscosity of gaseous suspending fluids is lower compared to liquid suspending fluids, which allows faster settling of the electrophoretic particles.
A number of patents and applications assigned to or in the name of the Massachusetts Institute of Technology (MIT) and yingke corporation describe various techniques for use in packaging electrophoretic and other electro-optic media. Such encapsulated media comprise a plurality of small capsules, each capsule itself comprising an internal phase containing electrophoretically-mobile particles in a fluid medium, and a capsule wall surrounding the internal phase. Typically, the capsules themselves are held within a polymeric binder to form a coherent layer between the two electrodes. The techniques described in these patents and applications include:
(a) electrophoretic particles, fluids, and fluid additives; see, e.g., U.S. Pat. Nos. 7,002,728 and 7,679,814;
(b) capsule, adhesive and packaging process; see, e.g., U.S. patent nos. 6,922,276 and 7,411,719;
(c) films and sub-assemblies containing electro-optic material; see, e.g., U.S. Pat. Nos. 6,982,178 and 7,839,564;
(d) backsheets, adhesive layers, and other auxiliary layers and methods for use in displays; see, e.g., U.S. patent nos. 7,116,318 and 7,535,624;
(e) color formation and color adjustment; see, e.g., U.S. Pat. Nos. 6,017,584; 6,664,944, respectively; 6,864,875, respectively; 7,075,502, respectively; 7,167,155, respectively; 7,667,684, respectively; 7,791,789, respectively; 7,839,564, respectively; 7,956,841, respectively; 8,040,594, respectively; 8,054,526, respectively; 8,098,418, respectively; 8,213,076 and 8,363,299; and U.S. patent application publication No. 2004/0263947; 2007/0223079, respectively; 2008/0023332, respectively; 2008/0043318, respectively; 2008/0048970, respectively; 2009/0004442, respectively; 2009/0225398, respectively; 2010/0103502, respectively; 2010/0156780, respectively; 2011/0164307, respectively; 2011/0195629, respectively; 2011/0310461, respectively; 2012/0008188, respectively; 2012/0019898, respectively; 2012/0075687, respectively; 2012/0081779, respectively; 2012/0134009, respectively; 2012/0182597, respectively; 2012/0212462, respectively; 2012/0157269 and 2012/0326957;
(f) a method for driving a display; see, e.g., U.S. Pat. Nos. 5,930,026; 6,445,489, respectively; 6,504,524; 6,512,354, respectively; 6,531,997, respectively; 6,753,999, respectively; 6,825,970, respectively; 6,900,851, respectively; 6,995,550, respectively; 7,012,600; 7,023,420, respectively; 7,034,783, respectively; 7,116,466, respectively; 7,119,772; 7,193,625, respectively; 7,202,847, respectively; 7,259,744; 7,304,787, respectively; 7,312,794, respectively; 7,327,511, respectively; 7,453,445, respectively; 7,492,339, respectively; 7,528,822, respectively; 7,545,358, respectively; 7,583,251, respectively; 7,602,374, respectively; 7,612,760, respectively; 7,679,599, respectively; 7,688,297, respectively; 7,729,039, respectively; 7,733,311, respectively; 7,733,335, respectively; 7,787,169, respectively; 7,952,557, respectively; 7,956,841, respectively; 7,999,787, respectively; 8,077,141, respectively; 8,125,501, respectively; 8,139,050, respectively; 8,174,490, respectively; 8,289,250, respectively; 8,300,006, respectively; 8,305,341, respectively; 8,314,784, respectively; 8,384,658, respectively; 8,558,783 and 8,558,785; and U.S. patent application publication No. 2003/0102858; 2005/0122284, respectively; 2005/0253777, respectively; 2007/0091418, respectively; 2007/0103427, respectively; 2008/0024429, respectively; 2008/0024482, respectively; 2008/0136774, respectively; 2008/0291129, respectively; 2009/0174651, respectively; 2009/0179923, respectively; 2009/0195568, respectively; 2009/0322721, respectively; 2010/0220121, respectively; 2010/0265561, respectively; 2011/0193840, respectively; 2011/0193841, respectively; 2011/0199671, respectively; 2011/0285754 and 2013/0194250 (these patents and applications may be referred to hereinafter as MEDEOD (means for Driving Electro-optical Displays) applications);
(g) an application for a display; see, e.g., U.S. patent nos. 7,312,784 and 8,009,348; and
(h) non-electrophoretic displays, such as those described in U.S. patent nos. 6,241,921; 6,950,220, respectively; 7,420,549 and 8,319,759; and U.S. patent application publication No. 2012/0293858.
Many of the above patents and applications recognize that the walls surrounding discrete microcapsules in an encapsulated electrophoretic medium can be replaced by a continuous phase, thus creating a so-called polymer-dispersed electrophoretic display, wherein the electrophoretic medium comprises a plurality of discrete droplets of an electrophoretic fluid and a continuous phase of a polymeric material, and the discrete droplets of electrophoretic fluid within such a polymer-dispersed electrophoretic display can be considered capsules or microcapsules, even if there is no discrete capsule film associated with each individual droplet; see, for example, U.S. patent No.6,866,760. Thus, for the purposes of this application, such polymer-dispersed electrophoretic media are considered to be a subclass of encapsulated electrophoretic media.
A related type of electrophoretic display is the so-called microcell electrophoretic display. In microcell electrophoretic displays, the charged particles and fluid are not encapsulated within microcapsules, but rather are held within a plurality of cavities formed within a carrier medium (typically a polymer film). See, for example, U.S. patent nos. 6,672,921 and 6,788,449, both assigned to Sipix Imaging, inc.
Although electrophoretic media are typically opaque (because, for example, in many electrophoretic media, the particles substantially block the 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 display state is light-transmissive. See, e.g., U.S. patent nos. 5,872,552; 6,130,774, respectively; 6,144,361, respectively; 6,172,798; 6,271,823, respectively; 6,225,971, and 6,184,856. A dielectrophoretic display similar to an electrophoretic display but relying on a change in electric field strength may operate in a similar mode; see U.S. patent No.4,418,346. Other types of electro-optic displays can also operate in the shutter mode. Electro-optic media operating in shutter mode may be used in the multilayer structure of full color displays; in this configuration, at least one layer adjacent to the viewing surface of the display operates in a shutter mode to expose or hide a second layer further from the viewing surface.
Encapsulated electrophoretic displays are generally not plagued by the aggregation and settling failure modes of conventional electrophoretic devices and provide further benefits such as the ability to print or coat the display on a variety of flexible and rigid substrates. (use of the word "printing" is intended to include all forms of printing and coating including, but not limited to, premetered coating such as slot or slot die coating, slide or cascade coating, curtain coating, roll coating such as knife coating, forward and reverse roll coating, gravure coating, dip coating, spray coating, meniscus coating, spin coating, brush coating, air knife coating, 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.) thus, the resulting display can be flexible. In addition, because the display media can be printed (using a variety of methods), the display itself can be inexpensively manufactured.
The aforementioned U.S. patent No.6,982,178 describes a method of assembling solid state electro-optic displays, including encapsulated electrophoretic displays, that is well suited for mass production. Essentially, this patent describes a so-called Front Plane Laminate (FPL) comprising, in order, a light-transmissive electrically conductive layer, a layer of a solid electro-optic medium in electrical contact with the electrically conductive layer, a layer of adhesive, and a release sheet. Typically, the light-transmissive, electrically-conductive layer will be carried on a light-transmissive substrate, which is preferably flexible, in the sense that the substrate can be manually wound around a drum of, for example, 10 inches (254mm) in diameter without permanent deformation. The term optically transmissive is used in this patent and refers herein to a layer designated thereby that transmits sufficient light to enable a viewer looking through the layer to observe a change in the display state of the electro-optic medium, typically through the electrically conductive layer and the adjacent substrate (if present); where the electro-optic medium exhibits a change in reflectivity at non-visible wavelengths, the term optically transmissive should of course be understood to refer to transmission at the relevant non-visible wavelengths. The substrate is typically a polymeric film and typically has a thickness in the range of about 1 to about 25 mils (25-634 μm), preferably about 2 to about 10 mils (51-254 μm). The conductive layer is conveniently a thin metal layer or metal oxide layer, for example of aluminium or Indium Tin Oxide (ITO), or may be a conductive polymer. Poly (ethylene terephthalate) (PET) films coated with aluminum or ITO are commercially available, for example aluminized Mylar (Mylar is a registered trademark) from dupont, wilmington, tera, and such commercial materials may be well used for front plane laminates.
Assembly of an electro-optic display using such a front plane laminate may be achieved by: the release sheet is removed from the front plane laminate and the adhesive layer is contacted with the backplane under conditions effective to cause the adhesive layer to adhere to the backplane, thereby securing the adhesive layer, the layer of electro-optic medium, and the conductive layer to the backplane. This process is well suited for mass production, as the front plane laminate can be mass produced, typically using roll-to-roll coating techniques, and then cut into pieces of any size needed for a particular back sheet.
U.S. patent No.7,561,324 describes a so-called double release tab, which is essentially a simplified version of the front plane laminate of the aforementioned U.S. patent No.6,982,178. One form of dual release sheet comprises a layer of a solid electro-optic medium sandwiched between two adhesive layers, one or both of which are covered by a release sheet. Another form of dual release sheet comprises a layer of a solid electro-optic medium sandwiched between two release sheets. Both forms of the dual release film are used in a process substantially similar to that used to assemble an electro-optic display from the aforementioned front plane laminate but involving two separate laminations; typically, in a first lamination, the dual release sheet is laminated to the front electrode to form a front sub-assembly, and then in a second lamination, the front sub-assembly is laminated to the backplane to form the final display, although the order of the two laminations can be reversed as desired.
U.S. patent No.7,839,564 describes a so-called inverted front plane laminate which is a variation of the front plane laminate described in the aforementioned U.S. patent No.6,982,178. The 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 solid electro-optic medium layer, and a release sheet. The inverted front plane laminate is used to form an electro-optic display having a laminating adhesive layer between the electro-optic layer and a front electrode or front substrate, and a second typically thin adhesive layer may or may not be present between the electro-optic layer and the backplane. Such an electro-optic display may combine good resolution with good low temperature performance.
As mentioned above, the simplest prior art electrophoretic media display substantially only two colors. Such electrophoretic media use one type of electrophoretic particles having a first color in a colored fluid having a second, different color (in which case the first color is displayed when the particles are adjacent to 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 different first and second colors in a colorless fluid (in which case the first color is displayed when the first type of particles are adjacent to the viewing surface of the display and the second color is displayed when the second type of particles are adjacent to the viewing surface). Typically, the two colors are black and white. If a full color display is desired, a color filter array may be placed on the viewing side of a monochrome (black and white) display. Displays with color filter arrays rely on region sharing and color mixing 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 may be arranged in a one-dimensional (stripe) or two-dimensional (2 × 2) repeating pattern. Other choices of primary colors or more than three primary colors are also known in the art. Three (in the case of an RGB display) or four (in the case of an RGBW display) sub-pixels are chosen small enough so that at the desired viewing distance they visually blend together into a single pixel with a uniform color stimulus ("color blending"). An inherent drawback of area sharing is that the colorant is always present and the color can only be modulated by switching the corresponding pixel of the underlying monochrome display to white or black (turning the corresponding primary color on or off). For example, in an ideal RGBW display, each of the red, green, blue and white primaries occupy one quarter of the display area (one subpixel out of four), the white subpixel is as bright as the underlying monochrome display white, and each of the color subpixels is no brighter than one third of the monochrome display white. The luminance of the white color shown by the display as a whole cannot be greater than half the luminance of the white sub-pixel (the white area of the display is produced by displaying one white sub-pixel every four, plus each color sub-pixel in its colored form is equivalent to one third of the white sub-pixel, so that the combined three colored sub-pixels contribute no more than one white sub-pixel). In the case where the color pixel is switched to black, the luminance and saturation of the color are reduced by the region sharing. Region sharing is particularly problematic when mixing yellow because it is brighter than any other color of equal brightness, and saturated yellow is almost as bright as white. Switching the blue pixels (one quarter of the display area) to black makes the yellow too dark.
Multilayer stacked electrophoretic displays are known in the art; see, e.g., J.Heikenfeld, P.Drzaic, J-SYeo and T.Koch, Journal of the SID,19(2),2011, pp.129-156. In such a display, the ambient light passes through the image in each of the three subtractive primary colors, exactly like conventional color printing. Us patent No.6,727,873 describes a stacked electrophoretic display in which three layers of switchable cells are placed on a reflective background. Similar displays are known in which the colour particles are laterally displaced (see international application No. wo 2008/065605), or isolated into the micro-pits using a combination of vertical and lateral movements. In both cases, each layer is provided with an electrode for concentrating or dispersing the color particles on a pixel-by-pixel basis, so that each of the three layers requires a Thin Film Transistor (TFT) (two of the three layers of TFTs must be substantially transparent) and a light-transmissive counter electrode. This complex arrangement of electrodes is expensive to manufacture and in the current state of the art it is difficult to provide a sufficiently transparent plane of the pixel electrodes, especially when the white state of the display has to be observed through several layers of electrodes. Multi-layer displays also suffer from parallax problems because the thickness of the display stack approaches or exceeds the pixel size.
U.S. application publication nos. 2012/0008188 and 2012/0134009 describe a multicolor electrophoretic display having a single backplane that includes independently addressable pixel electrodes and a common light-transmissive front electrode. A plurality of electrophoretic layers are disposed between the back plate and the front electrode. The 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. However, there are disadvantages to the use of multiple electrophoretic layers located between a single set of address electrodes. The electric field experienced by the particles in a particular layer is lower than in the case of a single electrophoretic layer addressed with the same voltage. In addition, optical losses in the electrophoretic layer closest to the viewing surface (e.g., caused by light scattering or unwanted absorption) may affect the appearance of the image formed in the underlying electrophoretic layer.
Attempts have been made to provide full color electrophoretic displays using a single electrophoretic layer. For example, U.S. patent application publication No.2013/0208338 describes a color display that includes an electrophoretic fluid that includes one or both types of pigment particles dispersed in a transparent and colorless or colored solvent, the electrophoretic fluid being sandwiched between a common electrode and a plurality of drive electrodes. The drive electrode is held at a certain distance to expose the 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 having two contrasting colors. Both types of pigment particles are dispersed in a colored solvent or a solvent having uncharged or slightly charged colored particles dispersed therein. The method includes driving a display cell to display a color of a solvent or a color of uncharged or slightly charged color particles by applying a driving voltage, wherein the driving voltage is about 1 to about 20% of a full driving voltage. U.S. patent application publication nos. 2014/0092465 and 2014/0092466 describe electrophoretic fluids, and methods for driving electrophoretic displays. The fluid includes first, second and third types of pigment particles, all 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 have a charge level that is 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 a full-color display in the sense that the term "full-color display" is used hereinafter.
U.S. patent application publication No.2007/0031031 describes an image processing apparatus for processing image data to display an image on a display medium, where each pixel is capable of displaying white, black, and one other color. U.S. patent application publication nos. 2008/0151355; 2010/0188732 and 2011/0279885 describe color displays in which moving particles move through a porous structure. U.S. patent application publication Nos. 2008/0303779 and 2010/0020384 describe display media that include different colorsThe first, second and third particles of (1). The first and second particles may form an aggregate and the smaller third particles may move through pores left between the aggregated first and second particles. U.S. patent application publication No.2011/0134506 describes a display device including an electrophoretic display element including a plurality of types of particles encapsulated between a pair of substrates, at least one of the substrates being translucent and each of the respective plurality of types of particles being charged with the same polarity, differing in optical properties, and differing in migration speed and/or electric field threshold for movement, a translucent display-side electrode being provided on a substrate side on which the translucent substrate is provided, a first backside electrode being provided on a side of the other substrate, facing the display-side electrode, and a second backside electrode being provided on a side of the other substrate, facing the display-side electrode; and a voltage control section that controls voltages applied to the display-side electrode, the first back-side electrode, and the second back-side electrode so that a particle type having a fastest migration speed from the plurality of types of particles or a particle type having a lowest threshold from the plurality of types of particles is moved, sequentially through each of the different types of particles, to the first back-side electrode or to the second back-side electrode, and then the particles moved to the first back-side electrode are moved to the display-side electrode. U.S. patent application publication nos. 2011/0175939; 2011/0298835, respectively; 2012/0327504 and 2012/0139966 describe color displays that rely on the aggregation and threshold voltages of multiple particles. U.S. patent application publication No.2013/0222884 describes electrophoretic particles that include colored particles that include a polymer containing charged groups and a colorant; and a branched silicon-based polymer attached to the colored particles and comprising a reactive monomer and at least one monomer selected from a specific set of monomers as a co-polymerizable component. U.S. patent application publication No.2013/0222885 describes a dispersion for an electrophoretic display, comprising a dispersion medium, a population of colored electrophoretic particles dispersed in the dispersion medium and migrating in an electric field, a population of non-electrophoretic particles not migrating and having a color different from that of the population of electrophoretic particles, and a compound having a neutral polar group and a hydrophobic group, the compound being present in an amount based on the entire compositionThe dispersion is contained in the dispersion medium in a proportion of about 0.01 to about 1% by mass. U.S. patent application publication No.2013/0222886 describes a dispersion for a display comprising floating particles comprising: a core particle including a colorant and a hydrophilic resin; and covering a surface of each of the core particles and comprising a core particle having a particle size of 7.95 (J/cm)3)1/2Or a shell of a poor hydrophobic resin of greater solubility parameter. U.S. patent application publication nos. 2013/0222887 and 2013/0222888 describe electrophoretic particles having a specified chemical composition. Finally, U.S. patent application publication No.2014/0104675 describes particle dispersion including first and second color particles that move in response to an electric field, and a dispersion medium, the second color particles having a larger diameter than the first color particles and a charging characteristic identical to that of the first color particles, wherein a ratio (Cs/Cl) of a charge amount Cs of the first color particles to a charge amount Cl of the second color particles per unit area of the display is less than or equal to 5. Some of the aforementioned displays offer full color but at the cost of requiring long and cumbersome addressing methods.
U.S. patent application publication nos. 2012/0314273 and 2014/0002889 describe an electrophoretic device including a plurality of first and second electrophoretic particles contained in an insulating liquid, the first and second particles having different charging characteristics from each other; the device further comprises a porous layer, which is comprised in the insulating liquid and which is formed by the fibre structure. These patent applications are not full color displays in the sense that the term "full color display" is used hereinafter.
See also U.S. patent application publication No.2011/0134506 and the aforementioned application serial No. 14/277,107; the latter describes a full-color display using three different types of particles in a colored fluid, but the presence of the colored fluid limits the quality of the white state that can be achieved by the display.
In summary, the current state of the art is that full color displays typically involve compromises such as slow switching speeds (up to several seconds), high addressing voltages or compromises with respect to color quality.
The present invention seeks to provide a full colour display which uses only a single electrophoretic layer but is capable of displaying white, black, three subtractive primary colours (cyan, magenta and yellow) and three additive primary colours (red, green and blue) at each pixel of the display, and also provides a method of driving such an electrophoretic display.
Disclosure of Invention
Accordingly, the present invention provides an electrophoretic medium comprising:
(a) a fluid;
(b) a plurality of first particles and a plurality of second particles dispersed in the fluid, the first particles and the second particles having charges of opposite polarities, the first particles being light scattering particles, and the second particles having one of the subtractive primary colors; and
(c) a plurality of third particles and a plurality of fourth particles dispersed in the fluid, the third particles and the fourth particles having charges of opposite polarities, the third particles and the fourth particles each having a subtractive primary color different from each other and different from the second particles,
wherein the electric field required to separate the aggregates formed by the third and fourth particles is greater than the electric field required to separate the aggregates formed by any other two types of particles.
The present invention also provides an electrophoretic medium as described above, wherein the electric field required to separate the aggregates formed between the first and second particles is less than the electric field required to separate the aggregates formed between the third and fourth particles, the first and fourth particles, and the second and third particles.
In another embodiment, the present invention provides an electrophoretic medium comprising:
(a) a fluid;
(b) a plurality of first particles and a plurality of second particles dispersed in a fluid, the first particles and the second particles bearing charges of opposite polarity and each having a polymer coating such that the volume of polymer in a substantially unsolvated state (i.e., in a dry powder) is at least 20% of the total volume of the plurality of particles (i.e., including the core pigment and the polymer coating); the first particles are light scattering particles and the second particles have one of the subtractive primary colors;
(c) a plurality of third particles dispersed in the fluid, the third particles having a charge of the same polarity as the first particles, and having no or a polymeric coating, such that the volume of polymer in a substantially unsolvated state (i.e., in a dry powder) is no more than 15% of the total volume of the plurality of particles (i.e., including the core pigment and the polymeric coating); and having a subtractive primary color different from the second particles; and
(d) a plurality of fourth particles, the fourth particles bearing a charge of the same polarity as the second particles, and having no or a polymeric coating, such that the volume of polymer in a substantially unsolvated state (i.e., in a dry powder) is no more than 15% of the total volume of the plurality of particles (i.e., including the core pigment and the polymeric coating); and has a subtractive primary color different from the second and third particles.
Furthermore, the invention provides an electrophoretic medium in which at least two of the second, third and fourth particles are substantially non-scattering.
Furthermore, the invention provides an electrophoretic medium in which the first particles are white and the second, third and fourth particles are substantially non-scattering.
The present invention also provides an electrophoretic medium comprising four types of particles as described above dispersed in a fluid, wherein:
(a) the white particles and the fourth particles of the first or second particles each have a polymeric coating comprising at least about 60% by weight of an acrylate or methacrylate monomer, wherein the ester group comprises a hydrocarbon chain comprising at least about six carbon atoms; and
(b) the colored particles of the first or second particles have a physisorbed polymer coating comprising a polydimethylsiloxane-containing monomer.
In a preferred embodiment, the first and third particles are negatively charged and the second and fourth particles are positively charged.
In a preferred form of the electrophoretic medium of the invention, the first, second, third and fourth particles are white, cyan, yellow and magenta in color, respectively. The white and yellow particles are negatively charged, and the magenta and cyan particles are positively charged.
In another aspect, the present invention provides an electrophoretic medium comprising:
(a) a fluid;
(b) a plurality of first particles and a plurality of fourth particles dispersed in a fluid, the first particles and the fourth particles bearing charges of opposite polarity and each having a polymeric coating comprising at least about 60% by weight of an acrylate or methacrylate monomer, wherein the ester group comprises a hydrocarbon chain containing at least about six carbon atoms, one of the first particles and the fourth particles is a light-scattering particle, and the other of the first particles and the fourth particles is a substantially non-light-scattering particle having one of the subtractive primary colors;
(c) a plurality of second particles dispersed in the fluid, the second particles having a charge of the same polarity as the fourth particles, having a polymeric coating comprising at least about 60% by weight of a polydimethylsiloxane-containing monomer, and having a subtractive primary color different from the substantially non-light-scattering particles in the first particles and the fourth particles; and
(d) a plurality of third particles, charged with the same polarity as the first particles, are substantially non-light scattering and have a subtractive primary color different from the substantially non-light scattering particles of the first and fourth particles and different from the second particles.
In another aspect, the invention provides a method of driving an electrophoretic display of the invention, the display comprising a layer of an electrophoretic medium disposed between first and second electrodes, the first electrode forming a viewing surface of the display, the display having a display surface capable of applying + V between the first and second electrodes, respectivelyH,+VL,0,-VLand-VHA voltage regulating component of voltage difference, wherein:
+VH>+VL>0>-VL>–VH
the method comprises, in any order:
(a) by applying between the electrodes a + V of a polarity driving the fourth particles towards the first electrodeHor-VHIs alternately displayed at the viewing surfaceThe color of the fourth particles and the color of the mixture of the fourth and second particles, the series of first pulses being of opposite polarity to the first pulses but greater than + V of the duration of the first pulsesLor-VLAlternating with the second pulse of (1); and
(b) by applying between the electrodes a + V of a polarity driving the third particles towards the first electrodeHor-VHAlternately displaying at the viewing surface the color of the third particles and the color of the mixture of third and second particles, with + V having the opposite polarity to the third pulse but greater than the duration of the third pulseLor-VLAlternates the fourth pulse of (2).
The method may further comprise:
(c) by applying between the electrodes a + V of a polarity driving the first particles towards the second electrodeLor-VLA series of fifth pulses that display substantially black at the viewing surface, the series of fifth pulses alternating with periods of substantially zero voltage difference between the electrodes;
(d) by applying between the electrodes a + V of a polarity driving the first particles towards the first electrodeLor-VLDisplaying the color of the first particles at the viewing surface, the series of sixth pulses alternating with periods of substantially zero voltage difference between the electrodes.
Whether or not the method includes steps (c) and (d), the method may further include:
(e) by applying between the electrodes a + V of a polarity driving the second particles towards the second electrodeLor-VLAlternately displaying the color of the second particles or the color of the mixture of third and fourth particles at the viewing surface, with a series of seventh pulses of + V having opposite polarity to the seventh pulses but greater than the length of the seventh pulsesLor-VLThe eighth pulse of (3) alternates.
The invention also provides an alternative method of driving an electrophoretic display of the invention comprising a layer of an electrophoretic medium arranged between first and second electrodes, the first electrode being a transparent electrode, the electrophoretic medium being a transparent electrode, the second electrode being a transparent electrode, the electrophoretic medium being a transparent electrode, the first electrode being a transparent electrode, the second electrode being a transparent electrodeThe electrodes form a viewing surface of a display having a display surface capable of applying + V between the first and second electrodes, respectivelyH0, and-VHA voltage regulating component of voltage difference, wherein:
+VH>0>–VH
the method comprises, in any order:
(a) by applying between the electrodes a + V of a polarity driving the fourth particles towards the second electrodeHor-VHAlternately displaying at the viewing surface the color of the fourth particles and the color of the mixture of the fourth and second particles, the series of first pulses being of opposite polarity to the first pulses but greater than the duration of the first pulsesHor-VHAlternating with the second pulse of (1); and (b) driving the third particles towards the second electrode by applying + V between the electrodesHor-VHAlternately displaying at the viewing surface the color of the third particles and the color of the mixture of third and second particles, with + V having the opposite polarity to the third pulse but greater than the duration of the third pulseHor-VHAlternates the fourth pulse of (2).
This alternative method may optionally include any one or more of steps (c), (d) and (e) listed above.
The electrophoretic medium of the present invention may comprise any of the additives as used in prior art electrophoretic media as described, for example, in the above-mentioned yingke and MIT patents and applications. Thus, for example, the electrophoretic media of the present invention typically include 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 20000 and being substantially non-absorbing on the particles to improve the bistability of the display, as described in the aforementioned U.S. Pat. No.7,170,670.
As already mentioned, in a preferred embodiment, the invention entails the use of generally white light-scattering particles, and three substantially non-light-scattering particles. There is of course nothing like totally light scattering particles or totally non-light scattering particles, and the minimum degree of light scattering of the light scattering particles used in the electrophoresis of the present invention, and the maximum allowable degree of light scattering allowed in the substantially non-light scattering particles, may vary somewhat depending on factors such as the exact pigments used, their color, and the ability of the user or application to tolerate some deviation from the desired color. The scattering and absorption properties of pigments can be evaluated by measuring the diffuse reflectance against white and black backgrounds of samples of the pigment dispersed in a suitable matrix or liquid. The results from these measurements can be interpreted according to a number of models well known in the art, for example, the one-dimensional Kubelka-Munk process. In the present invention, it is preferred that the white pigment exhibits a diffuse reflectance of at least 5% measured on a black background at 550nm when the pigment is approximately isotropically distributed by 15% by volume in a layer having a thickness of 1 μm comprising the pigment and a liquid having a refractive index of less than 1.55. Under the same conditions, the yellow, magenta and cyan pigments preferably exhibit diffuse reflectance of less than 2.5% measured on a black background at 650, 550 and 450nm, respectively. (the wavelengths selected above for the measurement of yellow, magenta and cyan pigments correspond to the spectral regions of minimum absorption by these pigments.) color pigments meeting these criteria are referred to hereinafter as "non-scattering" or "substantially non-light-scattering".
Table 1 below shows the diffuse reflectance of preferred yellow, magenta, cyan and white pigments (Y1, M1, C1 and W1, described in more detail below) used in the electrophoretic media of the present invention, as well as their ratio of absorption and scattering coefficients according to the Kubelka-Munk analysis of these materials dispersed in a polyisobutylene matrix.
TABLE 1
The electrophoretic medium of the present invention may be in any of the forms discussed above. Thus, the electrophoretic medium may be unencapsulated, encapsulated in discrete capsules surrounded by capsule walls, or in the form of a polymer dispersion or microcell medium.
The invention extends to a front plane laminate, a double release sheet, an inverted front plane laminate or an electrophoretic display comprising an electrophoretic medium of the invention. The display of the present invention may be used in any application where prior art electro-optic displays are used. Thus, for example, the present displays may be used in electronic book readers, portable computers, tablets, cellular telephones, smart cards, signs, watches, shelf labels, and flash drives.
Drawings
Figure 1 of the accompanying drawings is a schematic cross-sectional view showing the position of individual particles in an electrophoretic medium of the invention when displaying black, white, three subtractive primary colors and three additive primary colors.
Fig. 2 schematically illustrates four types of pigment particles used in the present invention.
Fig. 3 shows in schematic form the relative strength of the interaction between pairs of particles of the present invention.
Figure 4 shows in schematic form the behaviour of a particle of the invention when subjected to an electric field of varying strength and duration.
Fig. 5A and 5B illustrate waveforms for driving the electrophoretic medium illustrated in fig. 1 to its black and white states, respectively.
Fig. 6A and 6B illustrate waveforms for driving the electrophoretic medium illustrated in fig. 1 to its magenta and blue states.
Fig. 6C and 6D show waveforms for driving the electrophoretic medium shown in fig. 1 to its yellow and green states.
Fig. 7A and 7B illustrate waveforms for driving the electrophoretic medium illustrated in fig. 1 to its red and cyan states, respectively.
Fig. 8-9 illustrate waveforms that may be used to drive the electrophoretic medium shown in fig. 1 to all of its color states in place of the waveforms shown in fig. 5A-5B, 6A-6D, and 7A-7B.
Fig. 10 is a diagram showing adsorption of the charge control agent of the present invention onto a specific particle.
Fig. 11 is a schematic cross section of an apparatus for observing the motion of particles of the present invention when subjected to an electric field in example 9 below.
Fig. 12 and 13 are images of the movement of the mixture of magenta and yellow particles of the present invention and the mixture of cyan and yellow particles of the present invention, respectively, when subjected to an electric field.
Fig. 14(a) is a photograph of an ITO coated glass slide immersed in a formulation containing cyan and white pigments and after a dc bias of 500V for 30 seconds.
FIG. 14(b) is a photograph of an ITO coated glass slide immersed in a formulation containing magenta and white pigments and after 30 seconds of DC bias at 500V.
FIG. 14(c) is a photograph of an ITO coated glass slide after immersion in a formulation containing magenta and yellow pigments and 30 seconds of 500V DC bias.
Fig. 15-18 are graphs showing the optical densities measured at 450nm, 550nm and 650nm when an electrophoretic medium of the invention and a similar medium lacking specific particles are switched.
Fig. 19-21 are graphs showing the average distance from the SNAP standard for all eight "primaries" as a function of the difference in zeta potential measured in the experiment described in example 14 below.
Detailed Description
As described above, the present invention provides an electrophoretic medium comprising one light-scattering particle (typically white) and three other particles providing three subtractive primary colors (note that in the co-pending application serial No. 62/048,591 filed on 9/10/2014 and the co-pending application serial No. 62/169,221 filed on 6/1/2015, the first, second, third, and fourth pigment types described above and below are referred to as first, third, fourth, and second pigment types, respectively).
The three particles providing the three subtractive primary colors may be substantially non-light scattering ("SNLS"). The use of SNLS particles allows for the mixing of colors and provides more color results than can be achieved with the same number of scattering particles. The aforementioned US2012/0327504 uses particles with subtractive primary colors, but requires two different voltage thresholds for independent addressing of the non-white particles (i.e. addressing the display with three positive and three negative voltages). These thresholds must be sufficiently separated to avoid cross talk and this separation requires the use of high addressing voltages for some colors. In addition, addressing the color particle with the highest threshold also moves all other color particles, and these other particles must then be switched to their desired positions with a lower voltage. This step-wise color addressing scheme produces undesirable color flicker and long transition times. The present invention does not require the use of such stepped waveforms and, as described below, addressing all colors can be accomplished with only two positive voltages and two negative voltages (i.e., only five different voltages are needed in the display, two positive voltages, two negative voltages and zero, but in certain embodiments, it is preferable that more different voltages be used to address the display, as described below).
As already mentioned, fig. 1 of the accompanying drawings is a schematic cross-sectional view showing the positions of individual particles in an electrophoretic medium of the invention when displaying black, white, three subtractive primary colors and three additive primary colors. In fig. 1, it is assumed that the viewing surface of the display is at the top (as shown), i.e. the user views the display from this direction, and light is incident from this direction. As already noted, in a preferred embodiment, only one of the four particles used in the electrophoretic medium of the present invention substantially scatters light, and in fig. 1, the particle is assumed to be a white pigment. Basically, the light scattering white particles form a white reflector against which any particles on the white particles are observed (as shown in fig. 1). Light entering the viewing surface of the display passes through the particles, reflects from the white particles, passes back through the particles and emerges from the display. Thus, the particles above the white particles can absorb various colors, and the color appearing to the user is the combination of the particles produced above the white particles. Any particles disposed below the white particles (from the user's point of view) are masked by the white particles and do not affect the displayed color. Since the second, third and fourth particles are substantially non-light scattering, their order or arrangement with respect to each other is unimportant, but for the reasons already stated their order or arrangement with respect to the white (light scattering) particles is critical.
More specifically, when cyan, magenta, and yellow particles are located below the white particles (position [ a ] in fig. 1), no particles are present above the white particles, and the pixel simply displays white. When a single particle is above a white particle, the color of the single particle is displayed, yellow, magenta and cyan in positions [ B ], [ D ] and [ F ], respectively, in fig. 1. When two types of particles are located on top of a white particle, the displayed color is a combination of the colors of the two types of particles; in fig. 1, at position [ C ], magenta and yellow particles show red, at position [ E ], cyan and magenta particles show blue, and at position [ G ], yellow and cyan particles show green. Finally, when all three color particles are located above the white particle (position [ H ] in fig. 1), all incident light is absorbed by the three subtractive primary particles and the pixel displays black.
It is possible that one subtractive primary color may be present by the light scattering particles, so that the display will comprise two types of light scattering particles, one of which is white and the other of which is colored. However, in this case the position of the light scattering colored particles with respect to the other colored particles covering the white particles will be important. For example, when appearing black (when all three colored particles are on white particles), the scattering colored particles cannot be on non-scattering colored particles (otherwise they will be partially or completely hidden behind the scattering particles, and the color appearing will be that of the scattering colored particles, not black).
If more than one type of colored particles scatter light, it will not be easy to appear black.
Fig. 1 shows an idealized situation in which the color is uncontaminated (i.e. the light scattering white particles completely mask any particles located behind the white particles). In practice, the masking with white particles may be imperfect so that there may be some small absorption of light by the particles that would ideally be completely masked. Such contamination typically reduces the luminance and chromaticity of the color being rendered. In the electrophoretic media of the present invention, this color contamination should be minimized to the extent that the color formed is commensurate with industry standards for color reduction. A particularly preferred criterion is SNAP (a criterion for newspaper advertisement production) which specifies values of L, a and b for each of the eight primary colors referred to above. (hereinafter, "primary color" will be used to refer to eight colors, black, white, three subtractive primary colors, and three additive primary colors, e.g.
As shown in fig. 1. )
Methods for electrophoretically arranging a plurality of differently colored particles in a "layer" as shown in fig. 1 have been described in the prior art. The simplest of these methods involves "racing" pigments with different electrophoretic mobilities; see, for example, U.S. patent No.8,040,594. This competition is more complex than initially understood, since the motion of the charged colour itself alters the electric field experienced locally within the electrophoretic fluid. For example, as positively charged particles move toward the cathode and negatively charged particles move toward the anode, their charge screens the electric field experienced by the charged particles midway between the two electrodes. It is conceivable that although the pigment competition is involved in the electrophoresis of the present invention, this is not the only phenomenon responsible for the arrangement of the particles shown in fig. 1.
A second phenomenon that can be used to control the motion of multiple particles is anisotropic aggregation between different pigment types; see, for example, the aforementioned US 2014/0092465. Such aggregation may be charge-involved (coulombic) or may occur due to, for example, hydrogen bonding or van der waals interactions. The strength of the interaction can be influenced by the choice of surface treatment of the pigment particles. For example, coulombic interaction may be impaired when the close proximity of oppositely charged particles is maximized by a steric barrier (typically a polymer grafted or absorbed to the surface of one or both particles). In the present invention, as described above, 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.
A third phenomenon that may be utilized to control the motion of multiple particles is voltage or current dependent mobility, as described in detail in the aforementioned application serial No. 14/277,107.
Fig. 2 shows a schematic cross-sectional representation of four pigment types (1-4) used in a preferred embodiment of the present invention. The polymer shell absorbed into the core pigment is indicated by black shading, while the core pigment itself is shown as unshaded. A wide variety of forms can be used for the core pigment: spherical, needle-shaped, or otherwise anisometric, aggregates of smaller particles (i.e., "grape clusters"), composite particles comprising small pigment particles or dyes dispersed in a binder, and the like, 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. For example, the polymer may be a block copolymer comprising insoluble and soluble portions. Some methods for attaching the polymeric shell to the core pigment are described in the examples below.
The first and second particle types in one embodiment of the present invention preferably have a stronger polymer shell than the third and fourth particle types. The light scattering white particles are of the first or second type (negatively or positively charged). In the following discussion it is assumed that the white particles carry a negative charge (i.e. are of type 1), but it will be clear to the skilled person that the general principles of the description will apply to a collection in which the white particles are positively charged particles.
In the present invention, the electric field required to separate aggregates formed of a mixture of the
In fig. 2, the core pigments including the particles are shown to have about the same size, and the electromotive potential of each particle (although not shown) is assumed to be about the same. The thickness of the polymeric shell surrounding each core pigment varied. As shown in fig. 2, the polymer shell is thicker for the particles of
To understand how the thickness of the polymer shell affects the electric field required to separate aggregates of oppositely charged particles, it may be helpful to consider the force balance between pairs of particles. In practice, aggregates may be composed of a large number of particles, and the situation will be more complex than for simple pairwise interactions. However, particle pair analysis does provide some guidance for understanding the present invention.
The force acting on one of a pair of particles in an electric field is given by:
wherein, FAppIs the force exerted on the particle by the applied electric field, FCIs the coulomb force, F, exerted on the particle by a second particle of opposite chargeVWIs an attractive van der Waals force exerted on one particle by a second particle, and FDDue to the attractive force exerted by the repulsive flocculation on the particle pairs due to the (optional) inclusion of the stabilizing polymer into the suspending solvent.
Force F exerted on the particle by the applied electric fieldAppGiven by:
where q is the charge of the particle, which is related to the electromotive potential (ζ) (approximately, at the huckel limit) as shown in equation (2), where a is the core pigment radius, s is the thickness of the polymer shell swollen by the solvent, and other symbols have their conventional meaning known in the art.
The magnitude of the force exerted on one particle by another particle due to coulomb interactions is approximately given by:
for
Note that F is applied to each particleAppForces act to separate particles, but the other three forces are attractive between particles. According to Newton's third law, F if it acts on a particleAppHigher than F acting on the otherAppForce (because the charge on one particle is higher than the charge on the other), the force acting to separate the pair is formed by two FAppThe weaker of the forces is given.
As can be seen from (2) and (3), the magnitude of the difference between the attracting and detaching coulomb terms is given by:
making (a + s) smaller or zeta larger makes the particles more difficult to separate if the particles have the same radius and zeta potential. Thus, in one embodiment of the present invention, it is preferred that the particles of
However, if the thickness of the polymer shell is increased, van der waals forces between particles may also be significantly altered. The polymer shell on the particle is swollen by the solvent and the surface of the core pigment that will interact via van der waals forces moves further away. For having a distance(s) from each other1+s2) Much larger radius (a)1,a2) The spherical core pigment of (a) is,
wherein A is the Hammerk constant. As the distance between the core pigments increases, the expression becomes more complex, but the effect remains the same: increase s1Or s2For reduction of grainsAttractive van der waals interactions between the daughter have a significant impact.
In this context, the basic principle behind the particle type shown in fig. 2 can be understood. The particles of
Table 2 below shows various properties of the particles used in the present invention. The methods of preparation of these particles are described in the examples below. The white particles W1 and W2 are particles of
TABLE 2
It can be seen that the amplitudes of the zeta potentials of the particles are similar to each other (at least within a factor of about 3): all lie in the range of about 25-70mV (absolute). The particle diameters quoted are measured in solution, with the polymer shell (if present) being swollen by the solvent. The particle size typically ranges from about 150nm to 1000 nm.
The extent of the polymeric shell is traditionally assessed by thermogravimetric analysis (TGA), which is a technique that: the temperature of the dried sample of particles is raised and the mass loss due to pyrolysis is measured as a function of temperature. Conditions can be found in which the polymer coating is lost but the core pigment remains (these conditions depend on the exact core pigment particles used). By using TGA, the proportion of mass of the particles that the polymer occupies can be measured, and this can be converted to volume fraction using the known density of the core pigment and the polymer attached to the core pigment.
As can be seen in table 2, the particles of
The particles of
In this analysis, it is assumed that the polymer shell uniformly encapsulates the entire surface of the core pigment. However, this is absolutely not guaranteed. (see, e.g., the aforementioned U.S. Pat. No.6,822,782, FIG. 6, and related descriptions at columns 16-17.) it is possible that the method of attachment of the polymer is more favorable to crystallizing one side of the core pigment than the other, and there may be partial areas of the core pigment with polymer coverage, and other areas with no or very little polymer coverage. Moreover, particularly when grafting techniques are used to attach the polymer to the pigment surface, the growth of the polymer may be incomplete, leaving large areas of the core pigment uncovered, even if the mass of grafted polymer is large.
One method that can be used to assess the coverage of the polymer is to measure the adsorption isotherm of relatively polar molecules onto the pigment surface. A method for performing this determination is described in the following example. A convenient polar molecule for use in this determination is a charge-regulating agent (CCA), which is an amphiphilic molecule comprising a polar head group and a non-polar tail group. Such molecules are known to form reverse micelles in non-polar solvents such as the suspending solvents used in the present invention. In the presence of pigment particles, polar head groups are known to adsorb to surfaces (typically polar) not protected by non-polar polymer chains. The extent of adsorption of the CCA onto the surface of the pigment is thus a measure of the area of the pigment that is not covered by the non-polar polymer and is therefore not accessible.
The last column in Table 2 shows a typical CCA per unit area (from Lu) for the particlesSolsperse19000 available from brizol Corporation). The extent of adsorption of the material onto particles of
Fig. 3 shows in schematic form the strength of the electric field required to separate the paired aggregates of the particle types of the present invention. The interaction between the particles of
Fig. 4 shows how these interactions can be exploited to implement all primary colors (subtraction, addition, black and white) as generally discussed with reference to fig. 1.
When addressed with a low electric field (fig. 4(a)), the
When addressed with a high electric field (fig. 4(B)), the
Starting from the state shown in fig. 4(B), a low voltage of opposite polarity moves the positively charged particles to the left and the negatively charged particles to the right. However, the positively charged particles 4 will encounter the negatively charged
As described above, preferably, the
The core pigment used in the white particles is typically a high refractive index metal oxide, as is well known in the art of electrophoretic displays. Examples of white pigments are described in the examples below.
As described above, the core pigment used to make the particles of types 2-4 provides three subtractive primary colors: cyan, magenta, and yellow.
Suitable yellow core pigments include c.i. pigment yellow 1,3,12,13,14,16,17,73,74,81,83,97,111,120,126,137,139,150,151,155,174,175,176,180,181,191,194,213, and 214. Preferred yellow core pigments include c.i. pigment yellow 139,155 and 180.
Suitable magenta core pigments include c.i.
Suitable cyan core pigments include c.i. pigment blue 15:1,15:2,15:3,15:4, and 79, and c.i. solvent blue 70.
The display device may be constructed using the electrophoretic fluid of the present invention in several ways known in the art. The electrophoretic fluid may be encapsulated in microcapsules or incorporated into a microcell structure that is sealed with a polymer layer as follows. The microcapsule or microcell layer may be coated or stamped onto a plastic substrate or film that carries a transparent coating of conductive material. The assembly may be laminated to a backplane carrying the pixel electrodes using a conductive adhesive.
A first embodiment of waveforms for implementing each of the particle layouts shown in fig. 1 will now be described with reference to fig. 5-7. This driving method is hereinafter referred to as "first driving scheme" of the present invention. In this discussion, it is assumed that the first particles are white and negatively charged, the second particles are cyan and positively charged, the third particles are yellow and negatively charged, and the fourth particles are magenta and positively charged. The skilled person will understand how, in case these assignments of particle colors are changed, the color transitions will change, as they may be provided as one of the first and second particles being white. Similarly, the polarity of the charge on all the particles can be reversed, and assuming that the polarity of the waveform used to drive the medium (see next paragraph) is similarly reversed, the electrophoretic medium will still function in the same manner.
In the discussion that follows, the waveform (voltage curve over time) applied to the pixel electrode of the backplane of the display of the present 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 potential difference between the back plate and the front electrode and the distance separating them. The display is typically viewed via its front electrode, so that it is the particles adjacent to the front electrode that control the colour displayed by the pixel, and the optical transitions involved are sometimes easier to understand, taking into account the potential of the front electrode relative to the backplane; this can be done simply by inverting the waveforms discussed below.
These waveforms require that each pixel of the display can be driven at five different addressing voltages, denoted as + Vhigh,+Vlow,0,-Vlowand-VhighShown as 30V,15V,0, -15V and-30V in fig. 5-7. In practice, it may be preferable to use a large number of addressing voltages. If only three voltages (i.e., + V) can be achievedhigh0, and-Vhigh) Then can be obtained by using the voltage VhighBut with pulse addressing of 1/n duty cycle to achieve the same with lower voltages(e.g., V)highN, where n is>A positive integer of 1) addresses the same result.
The waveform used in the present invention may include three phases: a DC-balancing phase, in which a DC-imbalance due to a previous waveform applied to the pixel is corrected, or in which a DC-imbalance to be induced in a subsequent color rendering transition is corrected (as known in the art); a "reset" phase in which the pixel returns to an initial configuration, the initial configuration being at least substantially the same regardless of the previous optical state of the pixel; and a "color rendering" stage as described below. The DC balancing and reset phases are optional and may be omitted according to the requirements of a particular application. The "reset" phase (if used) may be the same as the magenta rendering waveform described below, or may comprise driving the maximum possible positive and negative voltages continuously, or may be some other pulse pattern, as long as it returns the display to a state from which the subsequent color is reproducibly obtained.
Fig. 5A and 5B show in idealized form typical color rendering stages of waveforms for producing black and white states in a display of the present invention. The graphs in fig. 5A and 5B show the voltage applied to the backplane (pixel) electrodes of the display when the transparent common electrode on the top plane is grounded. The x-axis represents time measured in arbitrary units, while the y-axis is applied voltage (volts). Driving a display to a black (FIG. 5A) or white (FIG. 5B) state respectively with positive or negative impulse, preferably at a voltage Vlow) Because, as mentioned above, at VlowAt the corresponding field (or current), the magenta and yellow pigments are brought together. Thus, the white and cyan pigments move, while the magenta and yellow pigments remain stationary (or move at a much slower speed), and the display switches between a white state and a state corresponding to absorption with the cyan, magenta and yellow pigments (commonly referred to in the art as "synthetic black"). The length of the pulses driven to black and white can vary from about 10-1000 milliseconds, and the pulses can be separated by a rest (at zero applied volts) of length in the range of 10-1000 milliseconds. Although FIG. 5 shows a minutePulses of positive and negative voltages are shown separately to produce black and white, separated by "rest" periods providing zero voltage, but it is sometimes preferred that these "rest" periods include pulses of opposite polarity to the drive pulses but with lower impulses (i.e., with shorter duration or lower applied voltage, or both, than the primary drive pulse).
Fig. 6A-6D show typical color rendering stages for producing waveforms for magenta and blue (fig. 6A and 6B) and yellow and green (fig. 6C and 6D). In FIG. 6A, the waveform oscillates between positive and negative impulses, but the length of the positive impulse (t)p) Shorter than the length (t) of the negative impulsen) While at a positive shock applied voltage (V)p) Voltage (V) greater than negative impulsen). When:
Vptp＝Vntn
the waveform as a whole is "dc balanced". The time period of one cycle of positive and negative impulses may range from about 30-1000 milliseconds.
At the end of the positive impulse the display is in the blue state, and at the end of the negative impulse the display is in the magenta state. This is consistent with a change in optical density corresponding to movement of the cyan pigment, which is greater than the change corresponding to movement of the magenta or yellow pigment (relative to the white pigment). According to the assumptions presented above, it would be desirable if the interaction between the magenta pigment and the white pigment is stronger than the interaction between the cyan pigment and the white pigment. The relative mobility of the yellow and white pigments (both negatively charged) is much lower than the relative mobility of the cyan and white pigments (oppositely charged). Thus, in generating a preferred waveform for magenta or blue, a waveform consisting of V for at least one cycle is includedntnFollowing VptpIs preferred, wherein Vp>VnAnd tp<tn. When blue is required, the sequence is at VpEnd, and when magenta is required, the sequence is at VnAnd (6) ending.
FIG. 6B illustrates a method for producing magenta and blue using only three voltage levelsAlternative waveforms of states. In the alternative waveform, at least one cycle is composed of VntnFollowing VptpIs preferred, wherein Vp＝Vn＝VhighAnd t isn<tp. The sequence cannot be dc balanced. When blue is required, the sequence is at VpEnd, and when magenta is required, the sequence is at VnAnd (6) ending.
The waveforms shown in fig. 6C and 6D are the inverse of the waveforms shown in fig. 6A and 6B, respectively, and produce the corresponding complementary colors yellow and green. In a preferred waveform for producing yellow or green, as shown in FIG. 6C, a waveform consisting of V including at least one cycle is usedntnFollowing VptpOf the impulse of, wherein Vp<VnAnd t isp>tn. When green is desired, the sequence is at VpEnd, and when yellow is desired, the sequence is at VnAnd (6) ending.
Another preferred waveform for generating yellow or green using only three voltage levels is shown in fig. 6D. In this case, at least one cycle of V is usedntnFollowing VptpWherein V isp＝Vn＝VhighAnd t isn>tp. The sequence cannot be dc balanced. When green is desired, the sequence is at VpEnd, and when yellow is desired, the sequence is at VnAnd (6) ending.
Fig. 7A and 7B show the color rendering stages for rendering red and cyan waveforms on the display of the present invention. These waveforms also oscillate between positive and negative impulses, but they differ from the waveforms of fig. 6A-6D in that the time period of a one-cycle positive and negative impulse is typically longer, and the addressing voltage used can be (but need not be) lower. The red waveform of FIG. 7A includes a pulse (+ V) that produces blacklow) (similar to the waveform shown in FIG. 5A) and a subsequent shorter pulse of opposite polarity (-V)low) Which moves the cyan particles and changes black to red, the complementary color of cyan. The cyan waveform is the inverse of the red waveform, with the portion (-V) producing whitelow) And a subsequent short pulse (V)low) Which moves the cyan particles adjacent the viewing surface. As with the waveforms shown in fig. 6A-6D, cyan moves faster relative to white than magenta or yellow pigments. However, in contrast to the waveform of FIG. 6, the yellow pigment of the waveform of FIG. 7 remains on the same side of the white particles as the magenta particles.
The waveforms described above with reference to fig. 5-7 use a five-level drive scheme, i.e., a drive scheme in which, at any given time, the pixel electrode may be at either of two different positive voltages, two different negative voltages, or a zero voltage relative to a common front electrode. In the particular waveforms shown in fig. 5-7, the five levels are 0, ± 15V and ± 30V. However, in at least some cases, it has been found advantageous to use a seven-stage drive scheme, which uses seven different voltages: three positive, three negative, and zero. This seven-stage drive scheme may be referred to hereinafter as the "second drive scheme" of the present invention. The choice of the number of voltages used to address the display should take into account 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 arrangement required to provide this larger number of drive voltages to conventional device display drivers. The inventors have found that the use of seven different voltages provides a good compromise between the complexity of the display architecture and the color gamut.
The general principle used in generating the eight primary colors (white, black, cyan, magenta, yellow, red, green and blue) using this second drive scheme applied to a display of the invention, such as that shown in fig. 1, will now be described. As in fig. 5-7, it is assumed that the first pigment is white, the second pigment is cyan, the third pigment is yellow, and the fourth pigment is magenta. It will be clear to a person skilled in the art that if the assignment of the colour of the pigment is changed, the colour displayed by the display will change.
The maximum positive and negative voltages applied to the pixel electrode (denoted as ± Vmax in fig. 8) produce a color formed by the mixture of the second and fourth particles (cyan and magenta, to produce blue-see fig. 1E and 4B viewed from the right), or only the third particles (yellow-see fig. 1B and 4B viewed from the left-the white pigments scatter light and are located between the color pigments), respectively. These blue and yellow colors are not necessarily the best blue and yellow colors achievable by the display. The intermediate positive and negative voltages (denoted as ± Vmid in fig. 8) applied to the pixel electrodes produce black and white, respectively (but need not be the best black and white achievable by the display-see fig. 4A).
From these blue, yellow, black or white optical states, the other four primary colors can be obtained by moving only the second particles (in this case the cyan particles) relative to the first particles (in this case the white particles), using the lowest applied voltage (denoted as ± Vmin in fig. 8). Thus, shifting cyan out of blue (by applying-Vmin to the pixel electrode) produces magenta (see fig. 1E and 1D for blue and magenta, respectively); shifting cyan into yellow (by applying + Vmin to the pixel electrode) provides green (see fig. 1B and 1G for yellow and green, respectively); removing cyan from black (by applying-Vmin to the pixel electrode) produces magenta (see fig. 1H and 1C for black and red, respectively), and moving cyan into white (by applying + Vmin to the pixel electrode) provides cyan (see fig. 1A and 1F for white and cyan, respectively).
While these general principles are useful in constructing waveforms to produce particular colors in the displays of the present invention, in practice, the ideal behavior described above may not be observed, and modifications to the basic scheme are desirable.
A general waveform that implements the above-described modification of the basic principle is shown in fig. 8, in which the abscissa represents time (in arbitrary units) and the ordinate represents the voltage difference between the pixel electrode and the common front electrode. The magnitude of the three positive voltages used in the drive scheme shown in fig. 8 may be between about +3V and +30V, and the magnitude of the three negative voltages between about-3V and-30V. In an empirically preferred embodiment, the highest positive voltage + Vmax is +24V, the medium positive voltage + Vmid is 12V, and the lowest positive voltage + Vmin is 5V. In a similar manner, the negative voltages-Vmax, -Vmid and-Vmin are-24V, -12V and-9V in the preferred embodiment. It is not necessary that the magnitude of the voltage for any of the three voltage levels | + V | ═ V | -V |, but may be preferred in some circumstances.
There are four different stages in the general waveform shown in fig. 8. In the first phase ("a" in fig. 8), there are supply pulses at + Vmax and-Vmax (where "pulse" represents a unipolar square wave, i.e. a constant voltage applied for a predetermined time) for erasing a previous image presented on the display (i.e. "resetting" the display). The length (t) of these pulses1And t3) And length of rest (i.e., period of zero voltage therebetween) (t)2And t4) May be selected such that the overall waveform (i.e., the integral of the voltage over time over the overall waveform as shown in fig. 8) is dc balanced (i.e., the integral is substantially zero). Dc balancing can be achieved by adjusting the length of the pulses and pauses in phase a so that the net impulse provided in this phase is equal in magnitude and opposite in sign to the net impulse provided in the combination of phases B and C during which the display is switched to a particular desired color as described below.
The waveforms shown in fig. 8 are only for illustrating the structure of the general waveforms and are not intended to limit the scope of the present invention in any way. Thus, in fig. 8, a negative pulse is shown before a positive pulse in phase a, but this is not a requirement of the invention. The presence of only a single negative pulse and a single positive pulse in phase a is also not a requirement.
As noted above, the generic waveform is dc balanced in nature, and this may be preferred in certain embodiments of the invention. Alternatively, the pulses in phase a may provide dc balancing for a series of color transitions rather than for 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 previous applications cited in
In the second phase of the waveform (phase B in fig. 8), there are supply pulses using maximum and medium voltage amplitudes. In this stage, white, black, magenta, red and yellow are preferably presented in the manner previously described with reference to fig. 5-7. More generally, in this phase of the waveform, colors corresponding to type 1 particles (assuming that the white particles are negatively charged), combinations of
As described above (see FIG. 5B and related description), white color may be presented by a pulse or pulses at-Vmid. However, in some cases, the white color produced in this way may be contaminated with yellow pigment and appear as if it were pale yellow. To correct for this color contamination, some pulses of positive polarity need to be introduced. Thus, for example, white may be obtained by repetition of a single instance or multiple instances of a pulse sequence comprising a pulse having a length T1And pulses of amplitude + Vmax or + Vmid and subsequent length T2And a pulse of amplitude-Vmid, where T2>T1. The last pulse should be a negative pulse. In FIG. 8, the time t is shown5And then for time t6Four repeats of the sequence of-Vmid. During this pulse sequence, the appearance of the display oscillates between magenta (but typically not the ideal magenta) and white (i.e. the front of white is a state with lower L and higher a than the final white state). This is similar to the pulse sequence shown in fig. 6A, where oscillation between magenta and blue is 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.
As described above (see fig. 5A and related description), black can be obtained by a pulse or multiple pulses (separated by periods of zero voltage) presentation at + Vmid.
As described above (see FIGS. 6A and 6B and related description), magenta can be obtained by repetition of a single instance or multiple instances of a pulse train comprising a pulse train having a length T3And pulses of amplitude + Vmax or + Vmid and subsequent length T4And a pulse of amplitude-Vmid, where T4>T3. To produce magenta, the net impulse in this phase of the waveform should be more positive than the net impulse used to produce white. During the pulse train for generating magenta, the display will oscillate between a state of substantially blue and magenta. The front of the magenta is a state with a more negative and L lower than the final magenta state.
As described above (see FIG. 7A and associated description), red color may be achieved by repetition of a single instance or multiple instances of a pulse sequence comprising a pulse having a length T5And pulses of amplitude + Vmax or + Vmid and subsequent length T6And pulses of amplitude-Vmax or-Vmid. To produce red, the net impulse should be more positive than the net impulse used to produce white or yellow. Preferably, to produce red, the positive and negative voltages used are of substantially the same magnitude (both Vmax or both Vmid), the length of the positive pulse is longer than the length of the negative pulse, and the final pulse is a negative pulse. During the pulse sequence for generating red, the display will oscillate between a substantially black and red state. Red is preceded by a state with lower L, lower a and lower b than the final red state.
Yellow (see fig. 6C and 6D and associated description) may be obtained by repetition of a single instance or multiple instances of a pulse sequence comprising a pulse having a length T7And pulses of amplitude + Vmax or + Vmid and subsequent length T8And a pulse of amplitude-Vmax. The final pulse should be a negative pulse. Alternatively, as described above, yellow may be obtained by a single pulse or multiple pulses at-Vmax.
In the third phase of the waveform (phase C in fig. 8), there is a supply pulse of medium and minimum voltage amplitude in use. In this phase of the waveform, blue and cyan are produced after driving toward white in the second phase of the waveform, and green is produced after driving toward yellow in the second phase of the waveform. Thus, when the waveform transitions of the inventive display are observed, the blue and cyan are preceded by colors having b more positive than the final cyan or blue b value, and the green is preceded by a more yellow color, wherein L is higher, a and b are more positive than L, a and b of the final green. More generally, when the display of the present invention is rendering a color corresponding to colored ones of the first and second particles, the state is preceded by a substantially white state (i.e., having C less than about 5). When the display of the invention is presenting a color corresponding to the combination of the colored particles in the first and second particles and the particles of the third and fourth particles having an opposite charge to the particles, the display will first present a color of substantially the particles of the third and fourth particles having an opposite charge to the colored particles in the first and second particles.
Typically, cyan and green will be produced by a pulse sequence, wherein + Vmin must be used. This is because only at this minimum positive voltage, the cyan pigment can move relative to the white pigment independently of the magenta and yellow pigments. This movement of cyan pigments is required to assume either cyan starting from white or green starting from yellow.
Finally, in the fourth phase of the waveform (phase D in fig. 8), zero voltage is supplied.
Although the display of the present invention has been described as producing eight primary colors, in practice it is preferred that as many colors as possible be produced at the pixel level. The full color gray scale image may then be rendered by dithering between these colors using techniques well known to those skilled in the imaging arts. For example, the display may be configured to present eight additional colors in addition to the eight primary colors generated as described above. In one embodiment, 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 in a color space such as CIE L a b having substantially the same hue angle as the reference color but having a higher or lower L, respectively.
Typically, light colors are obtained in the same way as dark colors, but using waveforms with slightly different net impulses in phases B and C. Thus, for example, the light red, light green, and light blue waveforms have net impulses that are more negative than the corresponding red, green, and blue waveforms in phases B and C, while the dark cyan, dark magenta, and dark yellow waveforms have net impulses that are more positive than the corresponding cyan, magenta, and yellow waveforms in phases B and C. The variation of the net impulse can be achieved by varying the length of the pulses, the number of pulses or the amplitude of the pulses in phases B and C.
Grey is typically achieved by a sequence of pulses oscillating between a low or medium voltage.
It will be clear to those skilled in the art that in displays of the invention using Thin Film Transistor (TFT) array driving, the available time increment on the abscissa of fig. 8 is typically quantified by the frame rate of the display. Also, it is clear that the display is addressed by varying the potential of the pixel electrode relative to the front electrode, and this can be done by varying the potential of the pixel electrode or the front electrode or both. In the current state of the art, typically a matrix of pixel electrodes is present on the backplane, while the front electrode is common to all pixels. Thus, when the potential of the front electrode changes, the addressing of all pixels is affected. The basic structure of the waveform described above with reference to fig. 8 is the same regardless of whether a varying voltage is applied to the front electrode.
The general waveform shown in fig. 8 requires the drive electronics to provide up to seven different voltages to the data lines during an update of a selected row of the display. Although multi-level source drivers capable of delivering seven different voltages are available, many commercially available source drivers for electrophoretic displays only allow three different voltages (typically positive, zero and negative) to be delivered during a single frame. The term "frame" here refers to a single update of all rows in the display. The general waveform of fig. 8 can be modified to accommodate a three-level source driver architecture as long as the three voltages supplied to the panel (typically + V,0 and-V) can be changed from one frame to another. (i.e., so that, for example, in frame n, the voltage (+ Vmax,0, -Vmin) can be supplied, and in frame n +1, the voltage (+ Vmid,0, -Vmax) can be supplied).
Since a change in the voltage supplied to the source driver affects each pixel, the waveform needs to be modified accordingly so that the waveform used to generate each color must coincide with the supplied voltage. Fig. 9 shows a suitable modification to the general waveform of fig. 8. In phase A, no change is necessary, as only three voltages (+ Vmax,0, -Vmax) are required. The phases B are respectively defined as having a length L1And L2Sub-phases B1 and B2 instead, a specific set of three voltages is used during each sub-phase. In FIG. 9, in phase B1, the voltages (+ Vmax,0, -Vmax) are available, and in phase B2, the voltages + Vmid,0, -Vmid are available. As shown in FIG. 9, the waveform is in sub-phase B1 for time t5A pulse of + Vmax is required. Sub-phase B1 vs. time t5Long (e.g., to accommodate a waveform for another color, where longer than t may be needed5Pulse of) so as to be directed to the time L1–t5A zero voltage is supplied. Length t within sub-phase B15Pulse and length L of1–t5May be adjusted as desired (i.e., sub-phase B1 does not have to start at length t as shown)5Pulse of (d). By subdividing phases B and C into sub-phases, in which there is the option of one of three positive voltages, one of three negative voltages and zero, the same optical result can be achieved as would be obtained using a multi-level source driver, albeit at the expense of a longer waveform (to accommodate the necessary zero pulse).
When a top plane switch is used in conjunction with a three stage source driver, the same general principles apply as described above with reference to fig. 9. A top-plane switch may be preferred when the source driver is not able to supply voltages up to the preferred Vmax. Methods for driving electrophoretic displays using top-plane switches are well known in the art.
Typical waveforms for the second driving scheme according to the present invention are shown below in table 3, where the numbers in parentheses correspond to the number of frames driven with the indicated backplane voltage (relative to the top plane assumed to be at zero potential).
TABLE 3
In the reset phase pulses of maximum negative and positive voltages are provided to erase the previous state of the display. The number of frames at each voltage is shifted by an amount (shown as Δ for color x)x) Which compensates for the net impulse in the high/medium voltage and low/medium voltage phases of the rendered color. To achieve DC balance, ΔxIs chosen to be half the net impulse. It is not necessary that the reset phase be implemented exactly in the manner shown in the table; for example, when using a top-plane switch, a certain number of frames need to be assigned to negative and positive drives. In this case, it is preferable to provide the maximum number of high voltage pulses consistent with achieving DC balance (i.e., subtracting 2 Δ from the negative or positive frame as needed)x)。
In the high/medium voltage phase, a sequence of N repetitions of a pulse sequence suitable for each color is provided, as described above, where N may be 1-20. As shown, the sequence includes 14 frames, which are assigned a positive or negative voltage of magnitude Vmax or Vmid, or zero. The illustrated pulse sequence conforms to the discussion given above. It can be seen that the pulse sequences for rendering white, blue and cyan are the same in this phase of the waveform (since blue and cyan are achieved in this case starting from the white state, as described above). Also in this phase, the pulse sequence for rendering yellow and green is the same (since green is realized starting from the yellow state, as described above).
In the low/medium voltage phase, blue and cyan are obtained from white, and green is obtained from yellow.
Table 4 shows the results of driving a display fabricated using the coating laminated to a thin film transistor array backplane below prepared as described in example 11 part a. The waveform used is similar to that shown in table 3, where N is 18, and the display is addressed at 65 frames per second using the preferred voltages described above.
TABLE 4
Examples of the invention
Examples are now given, but by way of illustration only, to show details of preferred electrophoretic media of the present invention and processes for driving these preferred electrophoretic media. The particles used in these examples are as follows.
The white particles W1 are silanol-functionalized light-scattering pigments (titanium dioxide) to which polymeric materials including Lauryl Methacrylate (LMA) monomers are attached as described in U.S. patent No.7,002,728.
The white particles W2 were polymer coated titanium dioxide made substantially as described in example 1 of U.S. patent No.5,852,196, with a polymer coating comprising lauryl methacrylate and 2,2, 2-trifluoromethacrylate in an approximately 99:1 ratio.
Yellow particles Y1 were c.i. pigment yellow 180 used without a coating and dispersed by milling in the presence of Solsperse19000, as outlined in the aforementioned application No. 14/277,107 and below in example 1.
Yellow particles Y2 were c.i. pigment yellow 155 used without a coating and dispersed by milling in the presence of Solsperse19000, as outlined in the aforementioned application No. 14/277,107 and below in example 2.
Yellow particles Y3 were c.i. pigment yellow 139 used without a coating and dispersed by milling in the presence of Solsperse19000, as outlined in the aforementioned application No. 14/277,107 and below in example 3.
The yellow particles Y4 are c.i. pigment yellow 139 coated by a dispersion polymer including trifluoroethyl methacrylate, methyl methacrylate, and a monomer containing dimethylsiloxane in the manner described in example 4 below.
Magenta particles M1 were a positively charged magenta material (dimethylquinacridone, c.i. pigment red 122) coated using vinylbenzyl chloride and LMA as described in the aforementioned application No. 14/277,107 and below in example 5.
Magenta particles M2 are c.i. pigment red 122 coated by dispersion polymerization, methyl methacrylate, and a dimethyl siloxane-containing monomer in the manner described in example 6 below.
Cyan particles C1 are a copper phthalocyanine material (c.i. pigment blue 15:3) coated by a dispersion polymer including methyl methacrylate and a monomer containing dimethylsiloxane in the manner described in example 7 below.
Example 1: preparation of yellow pigment Y1
Yellow pigment Novoperm yellow P-HG (available from clariant, basel, switzerland), (26G) was combined with Isopar G (70G) and a solution of Solsperse19000 in Isopar G (available from lubol corporation, vicklov, ohio), and the mixture was dispersed by vigorously milling with glass beads for 1 hour to provide a yellow pigment dispersion.
Example 2: preparation of yellow pigment Y2
Yellow pigment Inkjet yellow 4GC (available from Clariant, Basel, Switzerland), (26G) was combined with Isopar G (70G) and Solsperse19000 solution (70G of a 20% w/w solution in Isopar G available from Lubok corporation, Wikeley, Ohio). The resulting mixture was dispersed by milling at 600RPM with 250mL of glass beads for 1 hour, followed by filtration through a 200 μm mesh screen to provide a yellow pigment dispersion.
Example 3: preparation of yellow pigment Y3
Yellow pigment Novoperm yellow P-M3R (available from Clariant, Basel, Switzerland), (28G) was combined with Isopar G (70G) and a solution of Solsperse19000 (available from Leboemon, Wikelov, Ohio, 70G of a 20% w/w solution in Isopar G). The resulting mixture was dispersed by milling at 600RPM with 250mL of glass beads for 1 hour, followed by filtration through a 200 μm mesh screen to provide a yellow pigment dispersion.
Example 4: preparation of yellow pigment Y4
A2 liter plastic bottle was charged with 64.0g of Novoperm yellow P M3R (Craine 118380), 12.6g of 2,2, 2-trifluoromethacrylate, 42.5g of methyl methacrylate, 100g of methacrylate-terminated poly (dimethylsiloxane) (Gelest MCR-M22, molecular weight 10000), 376g of Isopar E, 80g of a 20 wt% solution of Solsperse17000, and Zirconox beads (1.7-2.4 mm). The bottle was rolled for 24 hours before pouring into a 500mL reactor via a 200 μm mesh screen. The reactor was assembled using a nitrogen immersion tube, an overhead stirring impeller and an air condenser. The overhead air stirrer was set to 400rpm and the reaction mixture was purged with nitrogen at 65 ℃ for 30 minutes, after which the immersion tube was removed and the rotational flow nitrogen level was set. In a vial, 0.358g of 2, 2' -azobis (2-methylpropionitrile) (AIBN) was dissolved in ethyl acetate and added to the syringe. The vial was then rinsed with ethyl acetate and added to the same syringe. The resulting AIBN solution was injected into the reactor for more than 30 minutes, and the reaction mixture was heated for 16-24 hours. The reaction mixture was dispensed into a 1L centrifuge bottle and centrifuged. The supernatant was decanted and the remaining pigment was washed with Isopar E and centrifuged. This rinsing process was repeated two more times and after the final supernatant had been decanted off, the remaining pigment was dried in a vacuum oven at room temperature overnight.
The dried pigment was distributed to 25% by weight of the mixture with Isopar G using sonication and rolling, and the resulting dispersion was filtered through a 200 μm mesh screen and the percentage of solid material in the dispersion was measured.
Example 5: preparation of magenta pigment M1
Ink Jet magenta E02 (15 g from Claine) was dispersed in toluene (135 g). The dispersion was transferred to a 500mL round bottom flask and the headspace was degassed with nitrogen. The resulting reaction mixture was brought to 42C and at temperature equilibration, 4-vinylbenzyl chloride was added and the reaction mixture was allowed to stir at 42C under nitrogen overnight. The resulting product was allowed to cool to room temperature and centrifuged to isolate the functional pigment. The centrifuge cake was washed three times with toluene to give a functional magenta pigment (14.76 g).
The functional magenta pigment was treated with poly (lauryl methacrylate) as described in the above-mentioned U.S. Pat. No.7,002,728, and then combined with Isopar E to produce a magenta pigment dispersion, which was filtered through a 200 μm mesh membrane and its percent solids was determined to be 17.8%.
Example 6: preparation of magenta pigment M2
A1 liter plastic bottle was charged with 32.0g Ink Jet magenta E02 (Craine), 26.5g methyl methacrylate, 53g methacrylate-terminated poly (dimethylsiloxane) (Gelest MCR-M22, molecular weight 10000), 220g Isopar E, and Zirconox beads (1.7-2.4 mm). The bottle was rolled for 2 hours after which 250g of Isopar E was added to the pigment mixture. This was then poured into a 1L reactor via a 200 μm mesh screen. The reactor was assembled using a nitrogen immersion tube, an overhead stirring impeller and an air condenser. The overhead air stirrer was set to 400rpm and the reaction mixture was purged with nitrogen at 65 ℃ for 30 minutes, after which the immersion tube was removed and the rotational flow nitrogen level was set. In a vial, 0.6g of 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 resulting AIBN solution was injected into the reactor for more than 30 minutes, and the reaction mixture was heated for 16-24 hours. The reaction mixture was dispensed into a 1L centrifuge bottle and centrifuged. The supernatant was decanted and the remaining pigment was washed with Isopar E and centrifuged. This rinsing process was repeated two more times and after the final supernatant had been decanted off, the remaining pigment was dried in a vacuum oven at room temperature overnight.
The dried pigment was distributed to 25% by weight of the mixture with Isopar G using sonication and rolling, and the resulting dispersion was filtered through a 200 μm mesh screen and the percentage of solid material in the dispersion was measured.
Example 7: preparation of cyan pigment C1
A1 liter plastic bottle was charged with 32.0g Hostaperm blue B2G-EDS (Craine corporation 225226), 15g methyl methacrylate, 30g methacrylate-terminated poly (dimethylsiloxane) (Gelest MCR-M22, molecular weight 10000), 220g Isopar E, and Zirconox beads (1.7-2.4 mm). The bottle was rolled for 24 hours before pouring into a 500mL reactor via a 200 μm mesh screen. The reactor was assembled using a nitrogen immersion tube, an overhead stirring impeller and an air condenser. The overhead air stirrer was set to 400rpm and the reaction mixture was purged with nitrogen at 65 ℃ for one hour, after which the immersion tube was removed and the rotational flow nitrogen level was set. In a vial, 0.189g of 2, 2' -azobis (2-methylpropionitrile) (AIBN) was dissolved in ethyl acetate and added to the syringe. The vial was then rinsed with ethyl acetate and added to the same syringe. The resulting AIBN solution was injected into the reactor for more than 30 minutes, and the reaction mixture was heated for 16-24 hours. The reaction mixture was dispensed into a 1L centrifuge bottle and centrifuged. The supernatant was decanted and the remaining pigment was washed with Isopar E and centrifuged. This rinsing process was repeated three additional times and after the final supernatant had been decanted off, the remaining pigment was dried overnight in a vacuum oven at room temperature.
The dried pigment was distributed to 25% by weight of the mixture with Isopar G using sonication and rolling, and the resulting dispersion was filtered through a 200 μm mesh screen and the percentage of solid material in the dispersion was measured.
Example 8: measurement of adsorption isotherms of Solsperse19000 on particles of the invention
A20 gram sample at 10% w/w concentration in solvent (for white particles) or 5% w/w concentration in Isopar G solvent (for colored particles) was prepared containing Solsperse19000 at 10-20 concentrations varying from zero to about 0.5G/G of pigment. The sample was allowed to mix isostatically at room temperature for at least 24 hours, after which the particles were removed by centrifugation at 3500rpm for 1 hour (white pigment) or at 20000rpm for a coloured sample for 1 hour. The conductivity of the supernatant was measured and the concentration of the remaining Solsperse19000 was determined relative to the calibration curve.
The results obtained with cyan particles C1 and the base pigment (c.i. pigment blue 15:3, Hostaperm blue B2G-EDS available from clariant) are shown in fig. 10. It can be seen that the polymer shell reduced the amount of Solsperse19000 adsorbed onto the particles from about 100mg/g to about 15 mg/g. The adsorption of Solsperse19000 on the original cyan pigment observed in fig. 10 appears to decrease as more surfactant is added. This is an artifact of the measurement. In an ideal measurement, the amount adsorbed will be even. In the experiment, at very high surfactant levels, some tiny particles were produced, which may not be completely removed from the supernatant. Thus, the conductivity of the supernatant liquid is higher (due to the presence of the charged cyan particles) than in the case where the pigment is completely removed. Similar artifacts were not observed for the dispersion polymerized samples, suggesting that the pigment was completely engulfed in the polymer and that the primary particle size (and thus surface area) of the cyan core was not important for the experiments.
Example 9: visualization of particles of the invention moving in an electric field
Part A: preparation of electrophoretic fluids
Fluid (i): 0.91G of a 22% w/w dispersion of particle C1 as prepared in example 7 above in Isopar G containing 0.36% w/w of 4:1 mass ratio Solsperse 19000: Solsperse17000 combined with 1.33G of a 15% w/w dispersion of particle Y3 as prepared in example 3 above in Isopar G containing 0.36% w/w of 4:1 mass ratio Solsperse 19000: Solsperse17000 and 17.76G of Isopar G containing 0.36% w/w of 4:1 mass ratio Solsperse 19000: Solsperse 17000. The dispersion of particles C1 and Y3 was centrifuged beforehand at 20,000rpm for 45 minutes and diluted three more times with Isopar G containing 0.36% w/w of 4:1 mass ratio Solsperse 19000: Solsperse17000 to ensure that any soluble impurities were removed. After the fluid was prepared, it was dispersed for 90 minutes by sonication before use.
Fluid (ii): 1.33G of a 15% w/w dispersion of particle M1 as prepared in example 5 above in Isopar G containing 0.36% w/w of 4:1 mass ratio Solsperse 19000: Solsperse17000 combined with 1.33G of a 15% w/w dispersion of particle Y3 as prepared in example 3 above in Isopar G containing 0.36% w/w of 4:1 mass ratio Solsperse 19000: Solsperse17000 and 17.34G of Isopar G containing 0.36% w/w of 4:1 mass ratio Solsperse 19000: Solsperse 17000. The dispersion of particles M1 and Y3 was centrifuged beforehand at 20,000rpm for 45 minutes and diluted three more times with Isopar G containing 0.36% w/w of 4:1 mass ratio Solsperse 19000: Solsperse17000 to ensure that any soluble impurities were removed. After the fluid was prepared, it was dispersed for 90 minutes by sonication before use.
And part B: visualization of particle motion
Fluids (i) - (ii) were visualized using the apparatus shown in fig. 11. The thickness of the
Fluid is loaded into the capillary via a syringe, after which it is briefly waited for the flow to drop. Holding the other end of the capillary open helps relieve pressure when the syringe is released and accelerates cessation of flow.
The electrophoretic fluid is then subjected to an applied voltage as shown in fig. 12 and 13, and the moving image is taken with a
Fig. 12 shows the result of applying an electric field to the mixture of magenta pigment M1 and yellow pigment Y3 (fluid (i)). At even the highest voltages, the aggregates between these two particles are not separated, leaving only the reddish aggregates moving towards the cathode.
Fig. 13 shows the result of applying an electric field to the mixture of cyan pigment C1 and yellow pigment Y3 (fluid (ii)). At applied voltages of 1000V and higher, the two pigments are separated, with cyan traveling toward the cathode and yellow traveling toward the anode.
As is clear from fig. 12 and 13, the pigments M1 and Y3 of the present invention formed aggregates that remained intact when subjected to an electric field that separated the pigments C1 and Y3 of the present invention. Alternatively, the electric field strength required to separate the aggregates is specified in the order P3-P4> P3-P2 for particles of
Example 10: electrostatic separation of particles
Part A: preparation of electrophoretic fluids
Fluid (i): white particle dispersion (W1) (0.11G) prepared as described in example 12, part A below was combined with cyan particle dispersion (C1) (0.13G) prepared in example 7 above, Solsperse19000 (2% W/W solution in Isopar G60 mg), Solsperse17000 (2% W/W solution in Isopar G10 mg) and Isopar G (3.49G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition including a pigment in a mobile phase). The mixture was then diluted by combining the electrophoretic fluid (1.0G) with additional Isopar G (9.0G). The resulting mixture was thoroughly mixed overnight and sonicated for 90 minutes.
Fluid (ii): a white pigment dispersion (W1) (0.11G) prepared as described in example 12, part A below was combined with a magenta particle dispersion (M1) (0.13G) prepared as described in example 5 above, Solsperse19000 (2% W/W solution in Isopar G200 mg), Solsperse17000 (2% W/W solution in Isopar G50 mg) and Isopar G (3.17G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition including a pigment in a mobile phase). The mixture was then diluted by combining the electrophoretic fluid (1.0G) with additional Isopar G (9.0G). The resulting mixture was thoroughly mixed overnight and sonicated for 90 minutes.
Fluid (iii): the yellow particle dispersion (Y3) (0.32G) described in example 3 above was combined with the magenta particle dispersion (M1) (0.23G), Solsperse19000 (2% w/w solution in Isopar G of 260 mg), Solsperse17000 (2% w/w solution in Isopar G of 70 mg) and Isopar G (2.77G) as described in example 5 above. The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition including a pigment in a mobile phase). The mixture was then diluted by combining the electrophoretic fluid (1.0G) with additional Isopar G (9.0G). The resulting mixture was thoroughly mixed overnight and sonicated for 90 minutes.
And part B: testing of electrophoretic fluids
An ITO coated glass slide (approximately 25cm x 17.5mm) was immersed in a reservoir containing an electrophoretic fluid to a depth of approximately 20 mm. The gap between the glass plates was kept constant at a distance of 10mm, with the ITO-coated sides facing each other. The ITO-coated sides of the two plates were then electrically connected and a dc bias of 500V was applied for a total of 30 seconds.
The slide was then removed from the electrophoretic fluid and immediately rinsed with approximately 1mL Isopar E to remove any material not attached to the electrode surface. The slides are then examined to determine which particles have been attached to each slide. As can be seen in fig. 14(a), when fluid (i) was tested, the white and cyan particles were cleanly separated, the white particles were deposited on the anode, and the cyan particles were on the cathode. On the other hand, as seen in fig. 14(b), when the magenta/white fluid (ii) was tested, the two pigments were seen to be deposited together (this is particularly clear on the anode). Even more dramatic is the result of using fluid (iii), magenta/yellow: in this case, the magenta and yellow pigments are not separated and each is visible on both the anode and cathode. The conclusion of these experiments was that the electric field strength required to separate the aggregates was in the order of P1-P4> P1-P2 and P3-P4> P1-P2 for particles of
Example 11: reduced pigment set
Part A: preparation of yellow particle Dispersion (Y3)
The yellow pigment Novoperm yellow P-M3R (available from Clariant, Basel, Switzerland) (28G) was combined with Isopar G (116G) and a solution of Solsperse19000 (available from Leboemon, Wikelov, Ohio, 24G of a 20% w/w solution in Isopar G). The resulting mixture was dispersed by milling at 600RPM with 250mL of glass beads for 1 hour, followed by filtration through a 200 μm mesh screen to provide a yellow particle dispersion.
And part B: preparation of electrophoretic fluids
Fluid (i): a white particle dispersion (W1) (4.94G) prepared as described in example 12, part a below was combined with a magenta particle dispersion (M1) (0.92G) prepared as described in example 5 above, a yellow pigment dispersion (0.90G) as described above, Solsperse19000 (20% W/W solution in Isopar G of 0.23G), Solsperse17000 (20% W/W solution in Isopar G of 0.09G), Isopar G (2.42G), and poly (isobutylene) of molecular weight 850,000 (15% W/W solution in Isopar G of 0.49G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid.
Fluid (ii): a white particle dispersion (W1) (4.94G) prepared as described in example 12, part a below was combined with a cyan particle dispersion (C1) (0.61G of a 24.8% W/W dispersion), a yellow pigment dispersion (0.90G) as described above, Solsperse19000 (0.15G of a 20% W/W solution in Isopar G), Solsperse17000(0.07G of a 20% W/W solution in Isopar G), Isopar G (2.83G), and poly (isobutylene) of molecular weight 850,000 (15% W/W solution in Isopar G of 0.49G) prepared as described in example 7 above. The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid.
Fluid (iii): a white particle dispersion (W1) (4.94G) prepared as described in example 12, part a below was combined with a magenta particle dispersion (M1) (0.92G) prepared as described in example 5 above, a cyan particle dispersion (C1) (0.61G of 24.8% W/W dispersion) prepared as described in example 7 above, Solsperse19000 (20% W/W solution in Isopar G of 0.26G), Solsperse17000 (20% W/W solution in Isopar G of 0.06G), Isopar G (2.71G), and poly (isobutylene) of molecular weight 850,000 (15% W/W solution in Isopar G of 0.49G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid.
Fluid (iv): a white particle dispersion (W1) (34.59G of a 60% W/W dispersion) prepared as described in example 12, part a below was combined with a magenta dispersion (6.45G of a 16.5% W/W dispersion) prepared as described in example 5 above, a cyan dispersion (4.97G of a 24.8% W/W dispersion) prepared as described in example 7 above, a yellow pigment dispersion (6.29G of a 16.7% W/W dispersion) prepared as described in example 3 above, Solsperse17000 (0.66G of 20% W/W solution in Isopar G), Isopar G (13.7G), and poly (isobutylene) of molecular weight 850,000 (isobutylene) (3.35G of 15% W/W solution in Isopar G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid.
And part C: preparation of display device
The array of microcells imprinted on the polyethylene terephthalate film with the coating of transparent conductor (indium tin oxide, ITO) was filled with the electrophoretic fluid prepared as described in section B above. The microcells are hexagonal in shape, having a depth of 20 microns and a width of 130 microns measured from edge to edge. Excess electrophoretic fluid is removed from the microcells by a doctor blade and they are sealed with a composite polymer coating as described in U.S. provisional patent application No. 62/065575. The assembly was laminated to a glass backplane with ITO electrodes using a doped thermal glue having a thickness of 3 μm, substantially as described in U.S. patent No.7,012,735, to produce a display device.
And part D: electro-optical testing
The devices fabricated as described in section C were driven using the waveforms shown in table 5. The waveform includes four phases: (1) reset at low frequency at 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 FIG. 7 (B); and (4) zero volts. Each phase of the waveform using a square wave forms an alternation between the voltages V1 and V2 at the frequency shown, with the duty cycle shown (defined as the proportion of time in one cycle that the voltage V1 drives the display).
TABLE 5
Fig. 15-18 show the optical densities at 450nm (blue absorption), 550nm (green absorption), and 650nm (red absorption) obtained during the "cyan write" and "zero" phases of the waveforms shown in table 5. The raw optical density is converted to an "analytical density" by removing the absorption of the other pigments at the indicated wavelength, i.e. the optical density contributions of only the cyan pigment at 650nm, only the magenta pigment at 550nm, and only the yellow pigment at 450 nm. This is achieved as follows: a) the raw optical density is corrected by baseline subtraction due to optical losses in the device; b) the optical density at 650nm was not further corrected because only the cyan particles were significantly absorbing at this wavelength; c) optical density at 550nm by subtracting 0.5 OD (650)corrCorrected for, because the cyan particles have appreciable absorption of green light; and d) optical density at 450nm by subtracting 0.08 OD (650)corrAnd 0.29 OD (550)corrCorrected for because the cyan and magenta particles absorb some of the blue light. It is clear to the person skilled in the art that a more accurate correction can be made by taking into account all cross-absorption terms. After the correction is made, the optical density at 450nm is approximately proportional to the amount of yellow pigment on the observation side of the white pigment; the optical density at 550nm is approximately proportional to the amount of magenta pigment on the viewing side of the white pigment; and the optical density at 650nm is approximately proportional to the amount of cyan pigment on the viewing side of the white pigment.
Fig. 15 shows the optical density trace corresponding to a mixture of white, yellow and magenta particles (fluid (i)). No modulation from the white state is visually observable (at this low addressing voltage). This is consistent with the formation of nearly immobile aggregates formed by the yellow and magenta particles (i.e., the white pigment can move, but the (red) aggregates of the yellow and magenta particles cannot be displaced at this low addressing voltage).
Fig. 16 shows the optical density traces corresponding to a mixture of white, yellow and cyan particles (fluid (ii)). Much greater modulation of cyan (650nm, dynamic range of about 0.3 OD) and yellow (450nm, dynamic range of about 0.1 OD) is now seen (again at low addressing voltages). This is consistent with the formation of weaker aggregates between the yellow and cyan particles (as compared to aggregates formed between the yellow and magenta particles). The dynamic range of the cyan oscillation is much lower than when the yellow particles are not present (see fig. 17 below).
Fig. 17 shows the optical density trace corresponding to the mixture of white, magenta and cyan particles (fluid (iii)). Significant modulation of cyan (650nm, dynamic range of about 0.9 OD) and magenta (550nm, dynamic range of about 0.6 OD) is now seen (again at low addressing voltages). The increased optical density range of cyan versus that shown in fig. 16 is consistent with cyan and yellow forming aggregates that require a higher field to separate than cyan and white. Alternatively, it is stated that for particles of
Finally, fig. 18 shows the optical density traces corresponding to a mixture of white, yellow, magenta and cyan particles (fluid (iv)). There is now significant modulation of only cyan (650nm, dynamic range of about 0.9 OD) while magenta is suppressed (550nm, dynamic range of about 0.2 OD). The reduced optical density range for magenta versus that shown in fig. 17 is consistent with magenta and yellow forming aggregates that require a higher field to separate than cyan and yellow. The same results were obtained in examples 9 and 10, i.e. the electric field strength required to separate the aggregates was in the order P3-P4> P3-P2 for particles of
Example 12: comparison of electrophoretic compositions
Part A: preparation of a Dispersion of white particles
Titanium dioxide is silane treated as described in U.S. Pat. No.7,002,728, and the silane treated white pigment is polymerized with poly (lauryl methacrylate) to provide a coated white pigment. The dried pigment (1100G) was combined with Isopar G (733.33G) to produce the final white dispersion.
And part B: preparation of electrophoretic fluids
Fluid (i): the white pigment dispersion (4.95G) prepared in part A above was combined with a magenta dispersion (0.92G) prepared as described in example 5 above, a cyan dispersion (0.61G of a 24.8% w/w dispersion) prepared as described in example 7 above, a yellow pigment dispersion (0.90G) prepared as described in example 1 above, Solsperse17000 (0.09G of a 20% w/w solution in Isopar G), Isopar G (2.05G), and poly (isobutylene) of molecular weight 850,000 (0.48G of a 15% w/w solution in Isopar G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition including a pigment in a mobile phase) having a conductivity of 330 pS/cm.
Fluid (ii): the white pigment dispersion (3.46G) prepared in part A above was combined with a magenta dispersion (0.69G) prepared as described in example 5 above, a cyan dispersion (0.43G of a 24.9% w/w dispersion) prepared as described in example 7 above, a yellow pigment dispersion (0.63G) prepared as described in example 2 above, Solsperse17000(0.07G of a 20% w/w solution in Isopar G), Isopar G (1.38G), and poly (isobutylene) of molecular weight 850,000 (0.34G of a 15% w/w solution in Isopar G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition including a pigment in a mobile phase) having a conductivity of 200 pS/cm.
Fluid (iii): the white pigment dispersion (4.93G) prepared in part A above was combined with a magenta dispersion (0.85G) prepared as described in example 5 above, a cyan dispersion (23.6% w/w dispersion of 0.69G) prepared as described in example 7 above, a yellow pigment dispersion (0.90G) prepared as described in example 3 above, Solsperse17000 (20% w/w solution in Isopar G of 0.09G), Isopar G (2.05G), and poly (isobutylene) of molecular weight 850,000 (15% w/w solution in Isopar G of 0.48G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition including a pigment in a mobile phase) having a conductivity of 75 pS/cm.
Fluid (iv): the white pigment dispersion (4.95G) prepared in example 3, part C above was combined with the magenta dispersion (0.76G) prepared as described in part B of the same example, the cyan dispersion (0.66G of 22% w/w dispersion) prepared as described in examples 1 and 2 above, the yellow pigment dispersion (0.77G) prepared in example 4 above, Solsperse19000 (20% w/w solution in Isopar G0.38G), Solsperse17000 (20% w/w solution in Isopar G0.09G), Isopar G (1.92G), and poly (isobutylene) of molecular weight 850,000 (isobutylene) (15% w/w solution in Isopar G0.48G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition including a pigment in a mobile phase) having a conductivity of 134 pS/cm.
Fluid (v): a white pigment dispersion (4.92G of 59.8% w/w dispersion) prepared as described in U.S. Pat. No.7,002,728 was combined with a magenta dispersion (0.77G) prepared in example 5 above, a cyan dispersion (0.61G of 24.8% w/w dispersion) prepared as described in example 7 above, a yellow pigment dispersion (0.90G) prepared as described in example 3 above, Solsperse17000 (0.09G of 20% w/w solution in Isopar G), Isopar G (2.23G), and poly (isobutylene) of molecular weight 850,000 (15% w/w solution in Isopar G0.48G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition including a pigment in a mobile phase) having a conductivity of 54 pS/cm.
Fluid (vi): the white pigment dispersion (4.95G) prepared in part A above was combined with a magenta dispersion (1.43G of 24.6% w/w dispersion) prepared as described in example 6 above, a cyan dispersion (0.60G of 24.9% w/w dispersion) prepared as described in example 7 above, a yellow pigment dispersion (0.90G) prepared as described in example 3 above, Solsperse19000 (20% w/w solution in Isopar G0.15G), Solsperse17000 (20% w/w solution in Isopar G0.08G), Isopar G (1.42G), and poly (isobutylene) of molecular weight 850,000 (isobutylene) (15% w/w solution in Isopar G0.47G). The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition including a pigment in a mobile phase) having a conductivity of 100 pS/cm.
And part C: electro-optical testing
A parallel plate test cell was prepared comprising two horizontal 50x 55mm glass plates, each coated with a transparent conductive coating of Indium Tin Oxide (ITO), between which the electrophoretic medium to be tested was introduced. Silica spacer beads of nominal 20 μm diameter were included to maintain a constant gap between the glass plates. The electrophoretic fluid (95 μ L) prepared as described above was dispensed on the ITO coated side of the lower glass plate, and then the upper glass plate was placed on the fluid so that the ITO coated layer was in contact with the fluid. The ITO-coated sides of the upper and lower glass plates were then electrically connected.
The cells were driven using the waveforms summarized in table 6. The basic waveform is divided into six sections, each section being 20.5 seconds long. During each section, the square wave AC, which has a frequency of substantially 30Hz, is offset by the DC voltage shown in the table (each offset is not shown, but the sequence should be apparent from the table entry). The duty cycle (i.e., the proportion of time during which positive voltage is applied in one cycle of positive and negative voltage) of the square wave AC is varied as shown in the table. The entire test includes three repetitions of the basic waveform, each time with a different sequence of voltage offsets, shown as "high voltage offset", "medium voltage offset", and "low voltage offset". Thus, for example, the initial "high voltage offset" is-15V. The amplitude of the square wave AC is +/-30V for the "high voltage offset" sequence, +/-20V for the "medium voltage offset" sequence, and +/-10V for the "low voltage offset" sequence.
TABLE 6
The reflectance spectrum is acquired as the cell is electrically driven. These are used to calculate the CIE L, a and b values of the light reflected from the cell when the waveform is applied. For each spectral sample, the distance in space of L a b of the colors of the cells from each of the eight SNAP primaries is calculated in units of Δ E. For each electrophoretic fluid being measured, the minimum distance of the color displayed from the SNAP primary color is recorded; the smaller the distance, the closer the electrophoretic fluid performance is to the SNAP target.
The results of this evaluation for the six fluids tested are shown in table 7. As shown in table 2 above, particles Y1, Y2, Y3 and M1 had minimal or no polymer shell, while particles W1, W2, M2 and C1 had substantial polymer shells. The particle W1 has a lower electro-kinetic potential than the particle W2.
TABLE 7
In table 7, better results are obtained when the closest approach to the SNAP target is a smaller number (i.e., the distance to the target is shorter — ideally it would be zero). It can be seen that the best formulations are those where the particles of
Example 13: switching an electrophoretic device using a first drive scheme as described above
Part A: manufacture of display devicesPrepare for
The array of microcells imprinted on the polyethylene terephthalate film with the coating of transparent conductor (indium tin oxide, ITO) was filled with electrophoretic fluid (iii) prepared as described in example 10 above. The microcells are hexagonal in shape, having a depth of 20 microns and a width of 130 microns measured from edge to edge. Excess electrophoretic fluid was removed from the microcells by a doctor blade and they were sealed with a composite polymer coating as described in U.S. application serial No.62/065,575 filed on 10/17 2014. The assembly was laminated to a glass backplane with ITO electrodes using a doped thermal glue having a thickness of 3 μm, substantially as described in U.S. patent No.7,012,735, to produce a display device.
And part B: display device to electric drive of eight primary colors
The device fabricated as described in part a was driven using the waveforms shown in table 8. There are two sub-phases in the reset portion: 1) at high addressing voltages with a low frequency and 2) at the same voltage with a relatively high frequency. This stage is followed by a "color write" stage, followed by substantially the same rows as described above with reference to fig. 5-7. This phase of the waveform uses the form of a square waveform alternating between voltages V1 and V2 at the frequency shown, with a duty cycle (defined as the proportion of time in a cycle that the display is driven at voltage V1) shown. The columns starting with "end" have the term "V1" (i.e., omit the portion of the display that will be addressed at voltage "V2") when the final period of the square wave AC ends after being written with voltage "V1". In the absence of terms in columns that begin with an "end," the last period of the square wave AC is the same as the other periods.
TABLE 8
Table 9 shows the colors obtained after the test display was driven as described above. It can be seen that all eight primary colors are available; however, the quality of color reproduction is not as high as when the "second driving scheme" of the present invention is utilized (see table 4 above).
TABLE 9
Example 14: functionalized dispersion polymerization and silane treatment/polymerization ratio for
Part A: exemplary preparation of cyan particles comprising polydimethylsiloxane in a polymeric shell
A500 mL plastic bottle was charged with 32.0g Hostaperm blue B2G-EDS (Craiden, Inc. 225226), 12.5g methyl methacrylate, 25g methacrylate-terminated poly (dimethylsiloxane) (Gelest MCR-M22, molecular weight 10000), and Isopar E. The vial was shaken and the contents poured into a 500mL reactor and homogenized at 25C for 30 minutes. The homogenizer was removed and the reactor was reassembled with nitrogen immersion tube, overhead stirring impeller and air condenser. The overhead air stirrer was set to 400rpm and the reaction mixture was purged with nitrogen at 65 ℃ for one hour, after which the immersion tube was removed and the rotational flow nitrogen level was set. In a vial, 0.189g of 2, 2' -azobis (2-methylpropionitrile) (AIBN) was dissolved in ethyl acetate and added to the syringe. The vial was then rinsed with ethyl acetate and added to the same syringe. The resulting AIBN solution was injected into the reactor in a single addition and the reaction mixture was heated for 16-24 hours. The reaction mixture was then dispensed into a 1L centrifuge bottle and centrifuged. The supernatant was decanted and the remaining pigment was rinsed with Isopar E and centrifuged again. This rinsing process was repeated twice and after the final supernatant had been decanted off, the remaining pigment was dried overnight in a vacuum oven at room temperature.
The dried pigment was distributed to 30% by weight of the mixture with Isopar G using sonication and rolling, and the resulting dispersion was filtered through a 200 μm mesh screen and the percentage of solid material in the dispersion was measured.
And part B: exemplary preparation of Polymer coated cyan particles Using silane coupling/polymerization Process
A500 mL plastic bottle was charged with 45.0g of Heliogen blue D7110F (BASF corporation), concentrated aqueous ammonia solution, and water. The mixture was rolled to disperse the pigment and then milled using glass beads. In addition, 7.875g of N [3- (trimethoxysilyl) propyl ] -N' - (4-vinylbenzyl) ethylenediamine dihydrochloride (available from chemical technologies, USA), glacial acetic acid, and water were mixed in a glass jar and mixed by tumbling (or spinning) for 1 hour to form a hydrolyzed silane solution. The grinding of the cyan pigment was stopped and the hydrolyzed silane solution was added to the grinder. The pH was adjusted to about 9.4 using concentrated aqueous ammonium hydroxide solution. The milling was continued for a further 1 hour, after which the glass beads were removed by filtration and the resulting silane-functionalized pigment was isolated from the filtrate by centrifugation, dried at 70 ℃ for 16 hours, and then ground to a fine powder using a mortar and pestle.
Lauryl methacrylate (1 g per gram of dry pigment from the previous step) and toluene were added to the milled pigment and the mixture was subjected to multiple cycles of sonication and tumbling until completely dispersed. The resulting mixture was filtered through a 200 μm mesh screen into a round bottom flask equipped with a condenser and magnetic stirring, after which the flask was purged with nitrogen and the mixture was heated to 65 ℃. A solution of AIBN in ethyl acetate (0.428g) was then added dropwise and the mixture was heated at 65 ℃ for 17 hours, then cooled, and the pigment was collected by centrifugation. The raw pigment was redispersed to toluene by sonication and collected again by centrifugation (4500rpm,30 minutes) before drying at 70 ℃. The dried pigment was dispersed to 30% by weight of the mixture with Isopar G using sonication and rolling, followed by filtration through a 200 μm mesh screen and the percentage of solid material in the dispersion was measured.
Table 10 shows the properties of a series of pigments prepared according to the general methods listed above. In some cases, surfactants are added to aid in the dispersion of the core pigment particles prior to polymerization: this is shown in the table as a "dispersant" (PVP is polyvinylpyrrolidone; Solsperse 8000 is a surfactant available from lubol corporation of victoriv, ohio; OLOA 371 is a surfactant available from chevron orlon of belale, texas). A cross-linking agent is also added to the specific polymerization process: trimethylolpropane trimethacrylate (TMPTMA), as shown. The 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 schroeter pigment, cincinnati, ohio. The inorganic material that substantially scatters light has a surface that desirably has a functional group (for example, an oxygen atom bonded to a metal) that reacts with the silane coupling agent used in the above production method B.
And part C: preparation of electrophoretic fluids
The electrophoretic fluid was prepared using cyan particles C2-C15. Cyan pigments are added to the electrophoretic fluid composition in an amount in inverse proportion to their extinction coefficient. An exemplary preparation is given below.
The yellow pigment dispersion (0.64G) prepared in example 1 was combined with the magenta dispersion (0.85G) prepared in example 5, the white dispersion (4.93G) prepared in example 10 part A above, and a cyan dispersion (31.7% w/w dispersion of 0.47G of a pigment having an extinction coefficient of 2.24m2/G measured at 650 nm), Solsperse17000 (20% w/w solution in Isopar G of 0.06G), poly (isobutylene) of molecular weight 850,000, and additional Isopar G. The resulting mixture was mixed thoroughly overnight and sonicated for 90 minutes to produce an electrophoretic fluid (i.e., an electrophoretic composition including a pigment in a mobile phase) having a conductivity of about 30 pS/cm.
And part D: electro-optical testing
The electrophoretic fluid prepared in section C above was tested as described above in example 12, section C. Fig. 19-21 show the average distances from the SNAP standard for all eight primary colors of 14 different electrophoretic media, each containing different cyan particles, but comprising the same white, magenta, and yellow particles in the same mass ratio, as well as a charge-adjusting agent (mixture of Solsperse19000 and Solsperse17000 in a 4:1 ratio) and a polymeric stabilizer (polyisobutylene). As described above, the cyan particles are loaded in inverse proportion to their extinction coefficient. Three different types of cyan particles were used: a) materials functionalized by dispersion polymerization using methyl methacrylate, and methacrylate-terminated poly (dimethylsiloxane) monomers as described above in part a (particles C2-C9, shown by circles in fig. 19-21); b) organometallic materials functionalized by silane treatment and subsequent polymerization with lauryl methacrylate as described in part B above (particles C10-C13, shown by open squares in fig. 19-21); and C) inorganic materials functionalized by silane treatment and subsequent polymerization with lauryl methacrylate as described in part B above (particles C14-C15, shown by filled squares in FIGS. 19-21).
The abscissa of the graphs in fig. 19-21 is the difference in electromotive potential between the cyan pigment and the magenta pigment measured with Solsperse17000 as a charge regulator (the magenta pigment in all cases was particle M1 prepared as described in example 5 above). These zeta potentials are measured in Isopar E or Isopar G. Note that in the graphs in fig. 19-21, smaller values of distance from SNAP correspond to better color appearance.
As can be seen from fig. 19, when the organometallic core cyan pigment is coated by dispersion polymerization (method a, circles), the cyan hue performance is generally better than when the magenta pigment is coated by silane-treated/polylauryl methacrylate (method B, open squares). One rationale for this result is that the dispersion polymerization process provides a more effective steric barrier for the organometallic core cyan pigment (
Fig. 20 shows the same trend for the color magenta. According to the assumptions presented above, magenta is formed when the magenta pigment moves through the white pigment (in this case between the particles of
Fig. 21 shows that the polymer treatment of the cyan pigment makes little difference in rendering for yellow. This is not unexpected, as the strength of the interaction between the magenta and yellow pigments is believed to mediate the formation of yellow, as described above.
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