JP4460149B2 - Electrophoretic displays and materials - Google Patents

Description

[0001]
The present invention relates to electrophoretic displays, in particular, encapsulated electrophoretic displays, and materials useful for making such displays.
[0002]
(Background of the Invention)
Electrophoretic displays have been the subject of intense research and development for many years. Electrophoretic displays have attributes of superior brightness and contrast, wide viewing angle, state bistability, and low power consumption when compared to liquid crystal displays. Nevertheless, the long-term image quality problems of these displays have hindered their widespread use to date.
[0003]
Recent inventions of encapsulated electrophoretic displays solve many of these problems and provide additional advantages over liquid crystal displays. Some additional advantages are the ability to print or coat the display material on a variety of flexible or rigid substrates. The problems of clustering and sedimentation that have plagued prior art electrophoretic displays and have resulted in poor display lifetimes are now solved.
[0004]
The purpose of the present disclosure is to describe electrophoretic displays, particularly encapsulated electrophoretic displays, the classification of materials that should be useful in constructing these displays, and some specific materials It is.
[0005]
(Summary of the Invention)
The successful construction of an encapsulated electrophoretic display requires the proper interaction of several different types of materials and processes. Materials such as polymer binders, capsule membranes, and electrophoretic particles and fluids must all be chemically compatible. The capsule membrane may engage electrophoretic particles with useful surface interactions and may serve as an inert physical boundary between the fluid and the binder. The polymer binder may be cured as an adhesive between the capsule membrane and the electrode surface.
[0006]
In some cases, a separate encapsulation step of the process is not necessary. To form what may be referred to as a “polymer dispersed electrophoretic display”, the electrophoretic fluid may be directly dispersed or emulsified in the binder (or a precursor of the binder material). In such displays, the individual electrophoretic phases can be referred to as capsules or microcapsules even in the absence of a capsule membrane. Such polymer dispersed electrophoretic displays are considered a subset of encapsulated electrophoretic displays.
[0007]
In an encapsulated electrophoretic display, a binder material surrounds the capsule and separates the two bordering electrodes. The binder material must be compatible with the capsule and the bordering electrode and must have properties that allow easy printing or coating. The binder material may also have barrier properties against water, oxygen, ultraviolet light, electrophoretic fluid, and other materials. In addition, the binder material may include surfactants and crosslinkers that may aid in coating or durability. The polymer dispersed electrophoretic display may be an emulsion or a phase separation type.
[0008]
The present invention provides electrophoretic displays, in particular encapsulated electrophoretic displays, and materials used in such displays. The capsule may be spherical or non-spherical. In an electrophoretic display, application of an electric field causes at least some of the particles to move or rotate. The electric field may be an alternating electric field or a direct electric field. The electric field can be created by at least one electrode pair disposed adjacent to the binder material comprising the particles. The particles may be, for example, absorbing pigments, scattering pigments, or luminescent particles. The particles may be composed of any combination of dyes, pigments, polymers.
[0009]
Such a display may also include, for example, one type of particle that retroreflects or substantially retroreflects light and another type that absorbs light. By applying an electric field, the particles of the encapsulated display can be oriented so that the capsules retroreflect or substantially retroreflect light. By applying another electric field, the particles can be oriented such that the capsule does not absorb or retroreflect light. The display may also include a retro-reflective substrate, where when one type of particles is oriented in a particular pattern, light passes through the capsule to the substrate and the substrate reflects the light. When the second type of particles are oriented in a particular pattern, the capsule absorbs light or otherwise does not retro-reflect. Types of retroreflective or reflective materials that can be used in constructing a retroreflective or reflective substrate, respectively, include glass spheres and diffractive reflective layers.
[0010]
Another type of display has particles of different colors. Such a display has at least two, preferably at least three, different particle types, each type of particle having a different electrophoretic mobility. Different electrophoretic mobilities provide particles with electrophoretic mobilities that do not substantially overlap so that, when a different electric field is applied, different subsets of colored particles are visible on the surface of the capsule.
[0011]
Another type of display includes luminescent particles and a visible light blocking medium that may include light absorbing particles or dyes. When a different electric field is applied, the particles can selectively or uniformly luminescence on the front surface (the bright pixels are visible to the eye) or the back surface (the fluid absorbs radiation) of the capsule. When different electric fields are applied, either the luminescent particles or the light blocking particles can rise to the capsule surface, thereby giving the capsule a bright or dark appearance, respectively.
[0012]
In another type of electrophoretic display, the particles themselves may be encapsulated pigments, dyes, pigment dispersions, dye solutions, and any combination thereof. These particles are dispersed in a suspending fluid and then encapsulated in a capsule in a binder. The particles may be dispersed within the suspending fluid, and each particle may include a plurality of solid particles, a dye, or both. The suspending fluid may be a single fluid or a mixture of two or more fluids. In one embodiment, the particles may have a diameter between about 10 nm and about 5 μm, and the capsules may have a diameter between about 5 μm and about 200 μm. In another embodiment, the particles may have a flexible outer surface and may be a polymer layer surrounding a dye or dye solution.
[0013]
The advantage of this system is that it is known to produce improved particles with better control of absorbance, optical properties, charge, mobility, shape, size, density, surface chemistry, stability, and processability. Emulsification or encapsulation techniques can be used. The number of all polar dyes and / or particles and liquids that can be used to obtain a high control level of the optical properties of this system is enormous. To obtain properties that are difficult to achieve with pigments, it is possible to create particles that are capsules containing dyes and / or particles. The present invention relates to these encapsulated electrophoretic displays and materials such as dyes, pigments, binders and the like that may be useful in constructing these displays.
[0014]
An encapsulated electrophoretic display may include two or more different types of particles. Such a display may include, for example, a display that includes a plurality of anisotropic particles and a plurality of second particles in a suspending fluid. Application of the first electric field can cause the anisotropic particles to be in a specific orientation and provide optical properties. Next, application of the second electric field can cause the plurality of second particles to move in parallel, thereby disturbing the orientation of the anisotropic particles and disturbing the optical characteristics. Alternatively, the orientation of the anisotropic particles may allow easier translation of the plurality of second particles. The particles may have a refractive index that substantially matches the refractive index of the suspending fluid.
[0015]
Finally, the encapsulated display can include an electroosmotic display. Such a display may include a capsule that includes a fluid of matched refractive index that moves within the capsule to create a homogeneous capsule upon application of an electric field. The capsule may also include a porous inner material, such as alkyl cellulose, that swells as the fluid of matched refractive index within the capsule moves. The electroosmotic display may also include two or more immiscible fluids that move within the capsule to create different optical properties when an electric field is applied. Optical effects can occur as a result of planar index mismatch or non-planar index mismatch.
[0016]
The materials used to make the electrophoretic display relate to, but are not limited to, the types of materials such as particles, dyes, suspending fluids and binders used to make the display. In one embodiment, the types of particles that can be used to make a suspended particle display include scattering pigments, absorbing pigments, and luminescent particles. Such particles may be transparent. Suitable particles include titania, which can be coated in one or two layers with a metal oxide such as aluminum oxide or silicon oxide. Such particles may also be retroreflective and have a reflective coating. Such particles may be configured as corner cubes. The luminescent particles can include, for example, zinc sulfide particles. The zinc sulfide particles may also be encapsulated with an insulating coating to reduce conductivity. The light blocking or absorbing particles can include, for example, dyes or pigments.
[0017]
The suspending (ie, electrophoresis) fluid may be a highly resistant fluid. The suspending fluid may be a single fluid or a mixture of two or more fluids. The suspending fluid, whether a single fluid or a mixture of fluids, can have a density that substantially matches the density of the particles in the capsule. The suspending fluid may be a halogenated hydrocarbon such as tetrachloroethylene. The halogenated hydrocarbon may also be a low molecular weight polymer. One such low molecular weight polymer is poly (chlorotrifluoroethylene). The degree of polymerization of the polymer may be from about 2 to about 10.
[0018]
The types of dyes used in electrophoretic displays are well known in the art. These dyes may be soluble in the suspending fluid. These dyes may also be part of the polymer chain. The dye can be polymerized by thermal diffusion, photochemical diffusion and chemical diffusion processes. A single dye may be used or a mixture of dyes may be used.
[0019]
Furthermore, the capsule may be formed in the binder or later dispersed in the binder. Materials used as binders include water-soluble polymers, water-dispersed polymers, oil-soluble polymers, thermosetting polymers, thermoplastic polymers, and uv or radiation curable polymers.
[0020]
The present invention is further understood in light of the following drawings, description, and appended claims.
[0021]
(Detailed description of the invention)
In the figures, the same reference numerals represent corresponding parts.
[0022]
The present invention relates to improved encapsulated electrophoretic displays and materials useful for constructing these displays. In general, an encapsulated electrophoretic display includes one or more particle species that absorb or scatter light. One example is a system in which the capsule contains one or more species of electrophoretically moving particles dispersed in a dyed suspending fluid. In another embodiment, the capsule includes two separate particle types suspended in a clear suspending fluid, one particle type absorbing light (black) and the other particle type scattering light. This is a white system. There are other extensions (more than two particle types, with or without dyes, etc.). The particles are usually solid pigments, dyed particles, or pigment / polymer composites.
[0023]
The electrophoretic display of the present invention is described below. These displays are preferably microencapsulated electrophoretic displays. Materials that may be useful for such displays are also described below.
[0024]
I. Electrophoresis display
The object of the present invention is a very flexible reflection that can be easily manufactured and consumes little power (or in the case of a bi-stable display, not at all) and can therefore be incorporated into various applications. Type display. The invention features a printable display that includes an encapsulated electrophoretic display medium. The resulting display is flexible. Since the display medium can be printed, the display itself can be manufactured at low cost.
[0025]
An encapsulated electrophoretic display can be configured such that the optical state of the display is stable for some time. If the display has two states that are stable in this manner, the display is said to be bistable. A display is said to be multistable if more than two states of the display are stable. For the purposes of the present invention, the term bistable is used to indicate a display in which any optical state remains fixed once the addressing voltage is removed. The definition of the bistable state depends on the application of the display. A slowly decaying optical state can be effectively bistable if the optical state does not change substantially over the required view time. For example, on a display that is updated every few minutes, a display image that is stable for hours or days is effectively bistable for its application. In the present invention, the term bistable also refers to a display having an optical state that lasts long enough to be effectively bistable for the application in question. Alternatively, it is possible to construct an encapsulated electrophoretic display where the image decays quickly once the addressing voltage to the display is removed (ie, the display is not bistable or multistable). As described below, in some applications it is advantageous to use a non-bistable encapsulated electrophoretic display. Whether the encapsulated electrophoretic display is bistable and the bistability of the encapsulated electrophoretic display should be controlled by appropriate chemical modification of the electrophoretic particles, suspending fluid, capsule, and binder material. Can do.
[0026]
Encapsulated electrophoretic displays can take many forms. The display may include capsules dispersed in a binder. The capsule may be any size or shape. The capsule may be spherical, for example, and may have a diameter in the millimeter or micron range, but is preferably 10 microns to a few hundred microns. As described below, the capsule may be formed by an encapsulation technique. The particles may be encapsulated in a capsule. The particles may be two or more different particle types. The particles may be colored, luminescent, light-absorbing or transparent, for example. The particles can include, for example, neat pigments, dyed (rake) pigments, or pigment / polymer composites. The display may further include a suspending fluid in which the particles are dispersed.
[0027]
In electrophoretic displays, particles can be oriented or translated by applying an electric field to the capsule. The electric field may include an alternating electric field or a direct electric field. The electric field may be provided by at least one electrode pair disposed adjacent to the display including the capsule.
[0028]
Throughout the specification, reference will be made to the term printed or printed. The term print used throughout the specification refers to pre-weighed coatings such as patch die coating, slot or extrusion coating, slide or cascade coating, and curtain coating; knife over roll coating, forward or reverse roll coating Gravure coating; Dip coating; Spray coating; Meniscus coating; Spin coating; Brush coating; Air knife coating; Silk screen printing process; Electrostatic printing process; Thermal printing process; It is intended to include all forms of prints and coatings. “Print element” refers to an element formed using any of the above techniques.
[0029]
FIG. 1 shows an electrophoretic display of the present invention. The binder 11 includes at least one capsule 13 that is filled with a plurality of particles 15 and a dyed suspending fluid 17. In one embodiment, particles 15 are titania particles. When a suitable polarity DC electric field is applied to the capsule 13, the particles 15 move to the viewing surface of the display and scatter light. When the applied electric field is reversed, the particles 15 move to the rear surface of the display. At this time, the view surface of the display looks dark.
[0030]
FIG. 2 shows an electrophoretic display of the present invention. The display includes an anisotropic particle 10 and a second set 12 of particles within a capsule 14. The capsule has electrodes 16 and 16 'disposed adjacent to the capsule. The electrodes are connected to a voltage source 18. The voltage source 18 may provide an alternating current (AC) field or a direct current (DC) field to the capsule 14. In this display, an AC electric field orients the anisotropic particles 10 to allow light to pass through the capsule. Brownian motion usually recovers particles slowly to an isotropic state. However, in this display, a second set 12 of transparent particles of matching refractive index is used to provide internal turbulence and to disturb the orientation of anisotropic particles. By applying a DC electric field that is switched at a much lower frequency, the second set of particles translates and disturbs any oriented anisotropic particles. This causes the display to reset to its scattering state much more quickly. When the orientation of anisotropic particles is disturbed, the display cell appears dark. This mechanism works in an encapsulated liquid cell, a polymer dispersed liquid cell, or a normal liquid cell.
[0031]
In another embodiment of the present invention, an electrophoretic display using a retroreflective surface is described. This implementation need not be encapsulated and can be implemented in the form of a standard electrophoretic display. 3 and 4 show such a display.
[0032]
In FIG. 3, the capsule 20 is filled with suspending fluid and particles 22. The suspending fluid may be a highly resistant fluid. When the particles are attracted towards the electrode 24 by the application of an electric field, the particles occupy a small portion of the viewable area of the display. This exposes the transparent electrode 26 and allows light to be reflected from the surface 28. This surface may consist of a glass sphere, for example a diffractive reflection layer such as a holographic reflector, any other known retroreflective surface, or any other surface that contrasts with particles. . At this time, the capsule looks like the substrate 28 at first glance.
[0033]
FIG. 4 shows the second state of the capsule. The particles 22 contained in the capsule 20 move toward the electrode 26 by application of an electric field. Thus, these particles cover the surface 28, and when the capsule is viewed from above, the capsule appears to have the properties of a particle.
[0034]
FIG. 5 shows another embodiment of the present invention. In this embodiment, the reflective display can be selectively retroreflective by manipulating charged particles to block the retroreflective light path or create a retroreflective surface. In the present embodiment, the capsule 30 includes retroreflective particles 32 and black particles 34. Retroreflective particles can include, for example, retroreflective corner cubes or hemispherical reflectively coated particles. When an appropriate voltage is applied between the electrodes 36 and 36 ', the black particles 34 can move to the viewing surface of the display and create a dark state. If the retroreflective particles can move to the top surface of the display by applying different electric fields, these retroreflective particles create a retroreflective surface, resulting in a bright state.
[0035]
In another embodiment, a display is described that can be selectively retroreflective. In general, this display works by manipulating charged particles to block the retroreflective path or create a retroreflective surface. The particles move within the capsule (eg, electrophoretically). 6A-6C show the contemplated configuration.
[0036]
The capsules are arranged in a two-dimensional or three-dimensional corner cube type structure that can be created by embossing or other means. In two situations, as shown in FIGS. 6A and 6B, particles 38 allow light 40 to pass and be reflected by corner cube 42. However, as shown in FIG. 6C, in the third state, the particles 38 prevent most of the incident light 40 from being retro-reflected by the corner cube 42.
[0037]
In another embodiment shown in FIG. 7, a single capsule serves as a retroreflector in much the same way as a glass bead. Only light that enters the incident side 44 with a vertical displacement away from the center by a distance greater than the critical distance y strikes the total internal reflection (TIR) side 46 at an angle large enough to be totally internally reflected. This light strikes near the center on the TIR side. Therefore, on the incident side 44, the retroreflection effect occurs in a direction away from the central axis. However, on the TIR side 46, most retro-reflection effects occur at the center in the vertical direction.
[0038]
Therefore, an electronically addressable retroreflective display in which the retroreflective state and the non-retroreflective state are as shown in FIGS. 8A and 8B can be configured. In FIG. 8A, the particles 43 are shown towards the front of the capsule 45. This configuration allows light to enter and exit from the TIR side of the capsule. In FIG. 8B, the particles 43 are shown towards the bottom of the capsule 45. In this configuration, the particles block the light path and thereby prevent light from being reflected from the TIR side of the capsule.
[0039]
That is, any configuration that can rearrange particles within a capsule or capsule cavity in a binder, with or without an external physical reflector, to switch from a retroreflective state to a non-retroreflective state. Intended.
[0040]
In another embodiment of the invention, a multi-color encapsulated electrophoretic display is contemplated. In this embodiment, a display that may include capsules is filled with at least one suspending fluid and at least two, preferably three particle types. These particles are different colors and have electrophoretic mobilities that do not substantially overlap. As used herein, the phrase “substantially non-overlapping electrophoretic mobilities” means that less than 25%, preferably less than 5%, of differently colored particles have the same or similar electrophoretic mobilities. means. As an example, in a system with two particle types, less than 25% of the particles of one species have the same or similar electrophoretic mobility as the particles of the other species. Finally, in another embodiment, one of the colors may be represented by a dye dispersed in the suspending fluid.
[0041]
Examples of multi-color encapsulated electrophoretic displays may include magenta particles having an average zeta potential of 100 mV, cyan particles having an average zeta potential of 60 mV, and yellow particles having an average zeta potential of 20 mV. When addressing this display to the magenta state, applying an electric field in one direction pulls all particles to the back of the cell. The electric field is then reversed for a time just sufficient for the magenta particles to move to the top surface of the display cell. Cyan and yellow particles also move in this reversal field, but these particles do not move as fast as magenta particles and are therefore obscured by magenta particles.
[0042]
When addressing the display to the cyan state, applying an electric field in one direction pulls all particles to the back of the cell. The electric field is then reversed for just enough time for the magenta and cyan particles to move to the top surface of the display cell. Then, when the electric field is reversed again, the magenta particles moving faster than the cyan particles expose the cyan particles at the top of the display.
[0043]
Finally, when achieving a yellow display, all particles are drawn to the front of the display. Then, when the electric field is reversed, yellow particles lagging behind the magenta and cyan particles are exposed at the front of the display.
[0044]
A display using field effect luminescence is also an embodiment of the present invention. Examples of field effect luminescent embodiments of the present invention require an AC voltage of about 300-400 Hz. However, this high frequency does not cause any net displacement of the luminescent particles. Luminescent particles are generally conductive. Thus, encapsulation in a polymer or other dielectric material is useful to reduce conductivity.
[0045]
9 and 10 show the white state and dark state of the display cell 48 of this embodiment, respectively. The luminescent particles 50 may be, for example, zinc sulfide particles that emit light when excited by an AC electric field. The AC field may be superimposed on the DC field used to address the particles or dyes, or may be superimposed after the DC field. The second particle species 52 in the fluid blocks light emitted from the particles when the display is addressed to a dark state.
[0046]
When a DC electric field is applied by the two electrodes 53, the luminescent particles 50 move to the view plane of the display 48 and are excited to emit light, resulting in a bright state. When an electric field of opposite polarity is applied, the luminescent particles 50 move to the back side of the display 48, and the light blocking particles 52 cause the light emitted from the luminescent particles 50 to exit from the viewing surface of the display. As a result, a dark state is obtained. The luminescent particles may be photoluminescent or electroluminescent. The photoluminescent particles may be excited by continuous ultraviolet light, otherwise they may be excited by radiation from the front of the display, or the illumination source may be behind the display. In the latter case, the dye or second particle species allows ultraviolet radiation to pass through the display.
[0047]
In another embodiment of the invention, the electrophoretic display comprises a capsule in a binder, the capsule comprises a plurality of particles, which are themselves encapsulated pigments, dyes, dispersions, or dyes. It is a solution. In this embodiment, for example, pigment is encapsulated to form particles in the range of tens of nanometers to several micrometers, and then these particles are dispersed and encapsulated. Examples are scattering pigments, absorbing pigments or luminescent particles. These particles are then used as electrophoretic particles. Furthermore, in this embodiment of the invention, it is possible to encapsulate the dye solution and use it as electrophoretic particles.
[0048]
Furthermore, in this embodiment it is possible not only to encapsulate fluid dyes or particles, but also to encapsulate fluid dyes and solid particles. These particles have the optical or electrical properties of the particles themselves, and these properties can supplement the properties of the dye.
[0049]
These encapsulated particles can be useful for both encapsulated and non-encapsulated electrophoretic displays. The average particle diameter ranges from about 10 nm to about 5 μm. These capsules must be small enough to move within larger capsules, and typically have a diameter size in the range of about 5 μm to about 400 μm.
[0050]
In another embodiment of the invention, an encapsulated electroosmotic display is described. In this embodiment, the porous or gelled internal phase of the capsule is a fluid of matched refractive index (ie, the difference between the refractive index of the fluid and the refractive index of the internal phase is preferably within 0.5). It swells (ie, fills) and is expelled by movement caused by electroosmosis. When the pores of the material are filled with fluid, the capsule serves as a homogeneous optical material, thereby transmitting or reflecting light primarily according to the bulk properties of the medium. However, when the holes are emptied by the moving fluid, there is a large amount of optical index mismatch and light scattering is greatly increased.
[0051]
The porous internal phase of the capsule may comprise a cellulosic material such as alkylcellulose. Examples of alkylcellulose include, but are not limited to, methylcellulose, methylhydroxyethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, and sodium carboxymethylcellulose.
[0052]
In other embodiments of the present invention, the capsule of the electrophoretic display preferably has a non-spherical shape. Due to the absorption or scattering by the encapsulant and the absorption or scattering of the binder, there is some light loss associated with the encapsulated electrophoretic display compared to the non-encapsulated display. Many of these losses arise from spherical cavities. Accordingly, it would be advantageous to provide a non-spherical microcapsule, specifically a densely packed array of non-spherical cavities. It is desirable that the top of the microcapsule has a flat surface that is coplanar with the view electrode and the vertical or near vertical wall. The capsule may be, for example, a slightly flattened sphere, an essentially cylindrical, very flattened sphere, or a polyhedral polyhedron.
[0053]
A display having a non-spherical capsule may include a binder having a non-spherical cavity containing oil. The cavities containing these oils may be elastomer capsules. In a preferred embodiment, the aspect ratio of these cavities (ie, the ratio of width to height) is preferably greater than about 1.2. The aspect ratio is more preferably greater than about 1.5, and in particularly preferred embodiments, the aspect ratio is greater than about 1.75. In a preferred embodiment, a display having non-spherical capsules has a binder volume fraction (ie, a fraction of the total volume) between about 0 and about 0.9. More preferably, the volume fraction is between about 0.05 and about 0.2.
[0054]
This type of display has both a rear surface and a view surface. In the preferred embodiment, the view plane is substantially planar. As used herein, the expression “substantially planar” means a curvature of less than about 2.0 m (ie, the reciprocal of the radius of curvature). In particularly preferred embodiments, both the rear surface and the view surface are substantially planar. Further, such display embodiments preferably have greater than about 80% optically active portion (ie, the percentage of total surface area that can change optical properties), more preferably about 90%. % Of optically active moieties.
[0055]
Non-spherical microcapsules may be formed during the encapsulation phase, for example by using a non-uniform shear field or compression pressure. Such non-spherical capsules may also be formed during display processing when the binder is dry or hardened. In such a system, as the binder shrinks, the binder brings the capsules closer together and pulls the capsules downward toward the substrate on which the capsules are coated. For example, aqueous evaporative binders such as aqueous acrylic, urethane, or poly (vinyl alcohol) tend to exhibit such shrinkage properties. Any other evaporative binder, emulsion, or solution is also suitable. The solvent need not be water, and may be an organic liquid or a combination of liquids.
[0056]
Such non-spherical capsules can be formed by applying a force to the membrane when the membrane is dry or cured, thereby permanently deforming the capsule. Such force may be applied by a roller pair, a vacuum lamination press, a mechanical press, or any other suitable means. Such non-spherical capsules may also be formed by stretching a cured film to one or both of the planar axes of the film. After completion of the curing process, the capsule can protrude above the surface of the cured film, resulting in a lens effect that enhances the optical properties of the capsule. Finally, the capsule may also consist of a material that softens in the binder, which allows for a flattened capsule when the capsule and binder are placed to cure the binder.
[0057]
In another embodiment, the polymer dispersed electrophoretic display is configured in a manner similar to the polymer dispersed liquid crystal display. As the binder dries or hardens, the encapsulated phase is drawn into the non-spherical cavity.
[0058]
The electrophoretic display is configured as either an encapsulated electrophoretic display or a polymer-dispersed electrophoretic display (similar to a polymer-dispersed liquid crystal display), and the capsule or droplet is flattened, the binder shrinks Or non-spherical by mechanical force. In each case, the capsule must be deformable, otherwise the capsule may rupture. In the case of polymer dispersed electrophoretic displays, the encapsulated phase changes shape as the polymer shrinks. Furthermore, the encapsulated phase may be deformed asymmetrically by stretching the substrate. Another technique that can be used is to first dry the binder so that a hard skin is formed on it. The remainder of the binder can then be dried slowly without worrying about the top surface breaking or being too uneven.
[0059]
The electrode adjacent to the electrophoretic display may comprise a conductive polymer such as, for example, polyaniline. These materials may be soluble, allowing these materials to be coated, for example by web coating.
[0060]
Means for addressing an encapsulated electrophoretic display (or other display) are also described. Referring to FIG. 11, electrodes 66 and 66 'are on one side of the display. These electrodes may be part of a head (“stylus”) that is scanned over the display. There may be more, less than one capsule, or just one capsule per electrode pair. Applying a DC electric field to the pixel moves the particles to one side and exposes the underlying substrate 68 (eg, mirror, retro-reflective coating, diffuse reflective coating, etc.). Under the influence of the AC electric field, the particles 70 can be distributed throughout the space and cause the appearance of predominantly dark pixels. The electrode itself may be transparent or opaque.
[0061]
A similar structure is described with reference to FIGS. 12A and 12B. However, the electrodes 72 and 72 'are different in size (eg, a factor greater than 2). By changing the electric field polarity, the particles move and mask any of the electrodes. In one case (FIG. 12A), the particles cover a small area and the pixels are primarily reflective. In the other case (FIG. 12B), the particles 74 'cover a large area and the pixels are primarily absorptive. The material may be reversed. For example, the particles may be reflective and the backing material may be absorbent. There may be a mask covering one of the electrode locations on the material.
[0062]
This display addressing method involves writing using an electrostatic head that is permanently attached to the fixture or held by hand. This method may also be applied to encapsulated magnetophoretic materials. This method may also be applied to polymer stabilized liquid crystal technology and may be applied to any type of bistable liquid crystal material, for example nematic on a photoalignment layer. This method may also be applied to suspended particle displays.
[0063]
Referring again to both FIG. 11 and FIG. 12, in either embodiment, the back electrode is not reflective but may be provided as a transmissive, translucent, or otherwise transparent backing material. Good. In these embodiments, as described above, the DC field can cause dark (absorbent) particles to cover one electrode and the pixel is primarily transmissive. These embodiments allow the display to be used to be a “shutter” of light. For example, a display including the described capsule can be addressed so that all pixels present in the display are primarily transparent. In this case, the display serves as a window or transparent device. Alternatively, the display is partially transmissive when a portion of the capsule is addressed. If all capsules are addressed using an AC electric field, the display is either opaque or reflective.
[0064]
II. Materials used for electrophoretic displays
Useful materials for constructing the above encapsulated electrophoretic display are described below. Many of these materials are known to those skilled in the art of making conventional electrophoretic displays or to those skilled in microencapsulation. These material and process combinations, together with other necessary components found in encapsulated electrophoretic displays, constitute the invention described below.
[0065]
A.particle
As mentioned above, the choice of particles used in electrophoretic displays is very flexible. For purposes of the present invention, a particle is any component that is charged or can acquire a charge (ie, has or can acquire electrophoretic mobility), and in some cases, This mobility may be zero or close to zero (ie, the particles do not move). The particles may be neat pigments, dyed (rake) pigments, or pigment / polymer composites, and may be any other component that can be charged or acquire a charge. Typical considerations for electrophoretic particles are the optical properties, electrical properties, and surface chemistry of the particles. The particles may be organic or inorganic compounds, and the particles may absorb light or scatter light. The particles used in the present invention can further include scattering pigments, absorbing pigments, and luminescent particles. The particles may be retroreflective, such as corner cubes, and may be electroluminescent or photoluminescent, such as zinc sulfide particles that emit light when excited by an AC electric field. Finally, the particles may be surface treated to improve interaction with the charging agent or charge, or to improve dispersibility.
[0066]
The preferred particle used in the electrophoretic display of the present invention is titania. The titania particles may be coated with a metal oxide, such as aluminum oxide or silicon oxide. The titania particles can have one, two or more layers of metal oxide coating. For example, the titania particles used in the electrophoretic display of the present invention may have an aluminum oxide coating and a silicon oxide coating. These coatings may be applied to the particles in any order.
[0067]
The electrophoretic particles are typically pigments, polymers, lake pigments, or some combination of the above. The neat pigment may be any pigment, and in the case of light colored particles, for example, a pigment such as rutile (titania), anatase (titania), barium sulfate, kaolin, or zinc oxide is useful. Some typical particles have a high refractive index, a high scattering coefficient, and a low absorption coefficient. Some particles are absorbent, such as colored pigments or carbon black used in paints and inks. The pigment must also be insoluble in the suspending fluid. Yellow pigments such as diarylide yellow, hansa yellow, and benzidine yellow have also found use in similar displays. Any other reflective material may be used for the light colored particles, including non-pigment materials such as metal particles.
[0068]
Useful neat pigments include, but are not limited to: PbCr_FourCyan Blue GT 55-3295 (American Cyanamid Company, Wayne, NJ), Cibacron Black BG (Ciba Company, Inc., Newport, DE), Cibacron Turquoise Blue G (Ciba), Cibaron Black BGL (Cb), Cb Orasol Black BRG (Ciba), Orasol Black RBL (Ciba), Acetamine Black, CBS (EI du Pont de Nemours and Company, Inc., Wilmington, DE), Crocein Scarlet N Ex (du Pont) (27290), Fiber Black VF (duPont) (30235), Luxor Fast Black L (duPont) (Solv. Black 17) Nilosin base no. 424 (duPont) (50415 B), Oil Black BG (duPont) (Solv. Black 16), Rotary Black RM (duPont), Sebron Brilliant Red 3 B (duPont); Basic Black DSC (Dye Specialties, Inc.) , Hectorene Black (Dye Specialties, Inc.), Azosol Brilliant Blue B (GAF, Dystuff and Chemical Division, Wayne, NJ) (Solv. Blue 9), Azosol Brilliant Green BA (GAF) (Solv. Green 2) Azosol Fast Brilliant Red B (GAF), Azosol Fast Orange RA Conc. (GAF) (Solv. Orange 20), Azosol Fast Yellow GRA Conc. (GAF) (13900 A), basic black KMPA (GAF), benzofix black CW-CF (GAF) (35435), ceritazole BNFV Ex soluble CF (GAF) (Disp. Black 9), seriton fast blue AF Ex Conc (GAF) (Disp. Blue 9), Cyper Black IA (GAF) (Basic Black 3), Diamine Black CAP Ex Conc (GAF) (30235), Diamond Black EAN Hi Conc. CF (GAF) (15710), Diamond Black PBBA Ex (GAF) (16505); Direct Deep Black EA Ex CF (GAF) (30235), Hansa Yellow G (GAF) (11680); Indanthrene Black BBK powder (GAF ) (59850), Indian Carbon CLGS Conc. CF (GAF) (53295), Kachigen Deep Black NND Hi Conc. CF (GAF) (15711), Rapidogen Black 3 G (GAF) (Azoic Black 4); Sulfocyanine Black BA-CF (GAF) (26370), Zambezi Black VD Ex Conc. (GAF) (30015); Lubanoc Red CP-1495 (The Sherwin-Williams Company, Cleveland, OH) (15630); Jet Black 11 (Columbian Carbon Company, Atlanta, GA) (carbon black having a particle size of about 25 μm) Agglomerates), Statex B-12 (Columbian Carbon Co.) (furnace black with an average particle size of 33 μm), and chrome green.
[0069]
The particles can also include lake pigments or dye pigments. Lake pigments are particles with dyes deposited or dyed. Lakes are metal salts of anionic dyes that dissolve easily. These are azo, triphenylmethane or anthraquinone structured dyes containing one or more sulfonic acid or carboxylic acid groups. These are usually deposited on the substrate by calcium, barium or aluminum salts. Typical examples are Peacock Blue Lake (CI Pigment Blue 24) and Persian Orange (CI Acid Orange 7 Lake), Black M Toner (GAF) (a mixture of black dye and carbon black deposited on the lake).
[0070]
The dark particles of the dyeing type may be composed of any light absorbing material such as carbon black or an inorganic black material. The dark material may also be selectively absorbent. For example, dark green pigments can be used. Black particles may also be formed by dyeing latex with metal oxide, such latex copolymers are butadiene, styrene, isoprene, methacrylic acid, methyl methacrylate, acrylonitrile, vinyl chloride, acrylic acid, sodium styrene. It consists of any one of sulfonate, vinyl acetate, chlorostyrene, dimethylaminopropyl methacrylamide, isocyanoethyl methacrylate, and N- (isobutoxymethacrylamide), optionally diacrylate, triacrylate, dimethyl acrylate, and trimethacrylate, etc. Of conjugated diene compounds. Black particles may also be formed by dispersion polymerization techniques.
[0071]
In systems comprising pigments and polymers, the pigments and polymers may form multiple domains within the electrophoretic particles and may be aggregates of smaller pigment / polymer combination particles. Alternatively, the central pigment core may be surrounded by a polymer shell. The pigment, polymer, or both may include a dye. The optical purpose of the particles can be light scattering, light absorption, or both. Useful sizes can range from 1 nm to about 100 μm as long as the particles are smaller than the bounding capsule. The density of the electrophoretic particles can substantially match the density of the suspended (ie, electrophoretic) fluid. As used herein, if the density difference between the suspending fluid and the particles is between about 0 g / ml and about 2 g / ml, the suspending fluid has a density that “substantially matches” the density of the particles. Then it is prescribed. This difference is preferably between about 0 g / ml and about 0.5 g / ml.
[0072]
Useful polymers for the particles include, but are not limited to: Polystyrene, polyethylene, polypropylene, phenol resin, Du Pont Elvax resin (ethylene-vinyl acetate copolymer), polyester, polyacrylate, polymethacrylate, ethylene acrylic acid or methacrylic acid copolymer (Nucrel resin-DuPont, Primacor resin-Dow Chemical), acrylic Copolymers and terpolymers (Elvacite resin, DuPont), and PMMA. Useful materials for homopolymer / pigment phase separation at high shear melt include, but are not limited to: Polyethylene, polypropylene, polymethyl methacrylate, polyisobutyl methacrylate, polystyrene, polybutadiene, polyisoprene, polyisobutylene, polylauryl methacrylate, polystearyl methacrylate, polyisobornyl methacrylate, poly-t-butyl methacrylate, polyethyl methacrylate, polymethyl acrylate , Polyethyl acrylate, polyacrylonitrile, and two or more copolymers of the above materials. Some useful pigment / polymer composites available commercially include, but are not limited to: Process Magenta PM 1776 (Magruder Color Company, Inc., Elizabeth, NJ), Methyl Violet PMA VM6223 (Magruder Color Company, Inc., Elizabeth, NJ), and Naphthol FGR RF6257 (Maglur, Ezrbeth, MJ) .
[0073]
The pigment-polymer composite is formed by a physical process (eg, attrition or ball milling), a chemical process (eg, microencapsulation or dispersion polymerization), or any other process known in the particle manufacturing art. obtain. From the examples below it can be seen that processes and materials for both particle production and particle charging are generally obtained from the field of liquid toner or immersion phenomena. These examples do not limit the invention. Thus, any of the known processes from liquid phenomena are particularly relevant, but not only.
[0074]
Although new useful electrophoretic particles can still be discovered, many particles already known to those skilled in the art of electrophoretic displays and liquid toners may also prove useful. In general, the polymer requirements for liquid toners and encapsulated electrophoretic inks are that the pigment or dye must be easily incorporated into it either by physical, chemical or physicochemical processes, and colloidal stability The same, in that it can help and include a charging location, or a material that includes a charging location can be incorporated. One common requirement from the liquid toner industry, which is not shared by encapsulated electrophoretic ink, is that the toner must be able to “fix” the image, ie after toner particle deposition. It must be able to melt and produce a uniform film.
[0075]
Typical particle manufacturing techniques are derived from liquid toners and other fields and include ball milling, attrition, jet milling, and the like. The process is described for the case of colored polymer particles. In such cases, the pigment is usually incorporated into the polymer in some type of high shear mechanism such as a screw extruder. The composite material is then ground (wet or dry) to a starting size of about 10 μm. Then, for example, ISOPAR^?(Exxon, Houston, TX) in a carrier liquid, optionally with any charge control agent (s) and under high shear until the final particle size and / or size distribution is achieved Grind for a few hours.
[0076]
Another particle manufacturing technique available from the liquid toner field is to add polymer, pigment and suspending fluid to the media mill. The mill is heated to the temperature at which the polymer substantially swells with the solvent upon startup. This temperature is typically around 100 ° C. In this state, the pigment is easily encapsulated in the swollen polymer. After a suitable time, typically several hours, the mill is gradually cooled back to ambient temperature with stirring. A sufficiently small particle size, typically a number? ? ? Milling can be continued for some time to achieve diameters from to several microns. At this time, a charging agent may be added. Optionally, additional suspending fluid may be added.
[0077]
Chemical processes such as dispersion polymerization, mini or microemulsion polymerization, suspension polymerization precipitation, phase separation, solvent evaporation, in situ polymerization, seed emulsion polymerization, or any of the general categories of microencapsulation The process can be used. A typical process of this type is a phase separation process in which dissolved polymer material is deposited from solution onto the dispersed pigment surface by solvent dilution, evaporation, or thermal changes. Other processes include chemical means for dyeing polymer latex, for example using metal oxides or dyes.
[0078]
B.Suspended fluid
The suspending fluid containing the particles can be selected based on properties such as density, refractive index, and solubility. Suitable suspending fluids have low dielectric constant (about 2), high volume resistivity (about 10 ^ 15 ohm-cm), low viscosity (less than 5 cst), low toxicity and environmental impact, low water solubility (less than 10 ppm), It has a high specific gravity (greater than 1.5), a high boiling point (greater than 90 ° C.), and a low refractive index (less than 1.2).
[0079]
The choice of suspending fluid may be based on consideration of chemical inertness, density matching with the electrophoretic particles, or chemical compatibility with the electrophoretic particles and the boundary capsule. If it is desired to move the fluid, the viscosity of the fluid must be low. The refractive index of the suspending fluid may also substantially match the refractive index of the particles. As used herein, if the refractive index difference between the suspending fluid and the particles is between about zero and about 0.3, preferably between about 0.05 and about 0.2, the suspending fluid Is said to be “substantially coincident” with the refractive index of the particles.
[0080]
Further, the fluid may be selected to be a poor solvent for some polymers. This is advantageous when used for the production of microparticles. This is because antisolvents increase the range of polymeric materials useful for producing polymer and pigment particles. Organic solvents such as halogenated organic solvents, saturated linear or branched hydrocarbons, silicone oils, and low molecular weight halogen-containing polymers are some useful suspending fluids. The suspending fluid may comprise a single fluid. However, this fluid is often a blend of more than one fluid to adjust its chemical and physical properties. In addition, the fluid may include a surface modifier to modify the surface energy or charge of the electrophoretic particles or the capsules that serve as the boundary. Reactants or solvents (eg, oil soluble monomers) for the microencapsulation process may also be included in the suspending fluid. A charge control agent may also be added to the suspending fluid.
[0081]
Useful organic solvents include, for example, epoxides such as decane epoxide and dodecane epoxide, such as cyclohexyl vinyl ether and vinyl ethers such as Decave ™ (International Flavors & Fragrances, Inc., New York, NY), and toluene and naphthalene, for example. Aromatic hydrocarbons include, but are not limited to: Useful halogenated organic solvents include, but are not limited to, tetrafluorodibromoethylene, tetrachloroethylene, trifluorochloroethylene, 1,2,4-trichlorobenzene, carbon tetrachloride. These materials have a high density. Useful hydrocarbons include dodecane, tetradecane, Isopar ™ series (Exxon, Houston, TX), Norpar ™ (a series of normal paraffin liquids), Shell-Sol ™ (Shell, Houston, TX) , And Sol-Trol ™ (Shell) aliphatic hydrocarbons, naphtha, and other petroleum-based solvents, but are not limited to these. These materials usually have a low density. Useful examples of silicone oils include, but are not limited to, octamethylcyclosiloxane and higher molecular weight cyclic siloxanes, poly (methylphenylsiloxane), hexamethyldisiloxane, and polydimethylsiloxane. These materials usually have a low density. Useful low molecular weight halogen-containing polymers include poly (chlorotrifluoroethylene) polymer (Halogenated hydrocarbon Inc., River Edge, NJ), Galden ™ (perfluoroether of Ausimont, Morristown, NJ), or Dupont ( Such as, but not limited to, Krytox ™ from Wilmington, DE). In a preferred embodiment, the suspending fluid is a poly (chlorotrifluoroethylene) polymer. In particularly preferred embodiments, the polymer has a degree of polymerization of about 2 to about 10. Many of the above materials are available in a range of viscosities, densities, and boiling points.
[0082]
The fluid must be able to be made into small droplets before the capsule is formed. The process of forming small droplets includes flow-through jets, membranes, nozzles or orifices, and shear-based emulsification mechanisms. The formation of small droplets may be assisted by an electric or sound field. For emulsion type encapsulation, surfactants and polymers may be used to help stabilize and emulsify the droplets. A preferred surfactant for use in the display of the present invention is sodium dodecyl sulfate.
[0083]
In some displays, it may be advantageous for the suspending fluid to contain a light absorbing dye. This dye must be soluble in the fluid but is generally insoluble in the other components of the capsule. The choice of dye material is very flexible. The dye may be a pure compound or a blend of dyes to achieve a specific color such as black. These dyes may be fluorescent. In this case, a display is created whose fluorescent properties depend on the location of the particles. The dye may be photoactive, in which case it changes to another color or becomes colorless upon irradiation with either visible or ultraviolet light, providing another means for obtaining an optical response. . The dye may also be polymerizable, in which case it forms a solid absorbent polymer within the bounding shell.
[0084]
There are many dyes that can be selected for use in encapsulated electrophoretic displays. Important properties here include light fastness, suspension solubility, color, and cost. These dyes are generally from the class of azo, anthraquinone, and triphenylmethane dyes and can be chemically modified to increase solubility in the oil phase and reduce adsorption by the fluid surface. .
[0085]
Many dyes already known to those skilled in the electrophoretic display art will prove useful. Useful azo dyes include, but are not limited to, oil red dyes and the Sudan Red and Sudan Black dye series. Useful anthraquinone dyes include, but are not limited to, oil blue dyes and the macrolex blue dye series. Useful triphenylmethane dyes include, but are not limited to, Michler hydrol, malachite green, crystal violet, and auramine O.
[0086]
C.Charge control agent and particle stabilizer
Charge control agents are used to provide superior electrophoretic mobility to the electrophoretic particles. The stabilizer prevents the electrophoretic particles from aggregating and prevents the electrophoretic particles from irreversibly depositing on the capsule wall. Either component can be composed of materials over a wide range of molecular weights (low molecular weight, oligomers or polymers) and can be pure or a mixture. Specifically, suitable charge control agents are generally adapted from the liquid toner field. The charge control agent used to modify and / or stabilize the particle surface charge is applied as is generally known in the field of liquid toners, electrophoretic displays, non-aqueous paint dispersions, and engine oil additives. The In all of these areas, charged species may be added to the non-aqueous medium to increase electrophoretic mobility or increase electrostatic stabilization. These materials can also improve steric stabilization. Different charging theories are assumed, such as selective ion adsorption, proton transfer, and contact charging.
[0087]
Any charge control agent or charge directing agent may be used. These components typically consist of low molecular weight surfactants, polymeric agents, or blends of one or more components that stabilize the sign and / or magnitude of the charge on the electrophoretic particles or It plays the role of denaturing by other methods. The charging properties of the pigment itself may be explained by taking into account the acidic or basic surface properties of the pigment, or the charging site may occur on the surface of the carrier resin (if any) Or a combination of these two. Additional pigment properties that may be relevant are particle size distribution, chemical composition, and light fastness. The charge control agent used to modify and / or stabilize the particle surface charge is applied as is generally known in the field of liquid toners, electrophoretic displays, non-aqueous paint dispersions, and engine oil additives. The In all of these areas, charged species may be added to the non-aqueous medium to increase electrophoretic mobility or increase electrostatic stabilization. These materials can also improve steric stabilization. Different charging theories are assumed, such as selective ion adsorption, proton transfer, and contact charging.
[0088]
Charge adjuvants may also be added. These materials increase the effectiveness of the charge control agent or charge directing agent. The charge auxiliary agent may be a polyhydroxy compound or an amino alcohol compound. These compounds are preferably soluble in the suspending fluid by an amount of at least 2% by weight. Examples of polyhydroxy compounds containing at least two hydroxyl groups include ethylene glycol, 2,4,7,9-tetramethyl-decyne-4,7-diol, poly (propylene glycol), pentaethylene glycol, triethylene Propylene glycol, triethylene glycol, glycerol, pentaerythritol, glycerol-tri-12 hydroxy stearate, propylene glycerol monohydroxy stearate, and ethylene glycol monohydroxy stearate are not limited to these. Examples of amino alcohol compounds containing at least one alcohol function and one amine function in the same molecule include triisopropanolamine, triethanolamine, ethanolamine, 3-amino-1 propanol, o-aminophenol, 5- Examples include, but are not limited to, amino-1-pentanol and tetra (2-hydroxyethyl) ethylene-diamine. The charge adjuvant is preferably present in the suspending fluid in an amount of about 1 mg / g to about 100 mg / g, more preferably about 50 mg / g to about 200 mg / g of particle mass.
[0089]
The surface of the particles may also be chemically modified, for example, to aid dispersion, improve surface charge, and improve dispersion stability. Surface modifiers include organosiloxanes, organohalogen silanes, and other functional silane coupling agents (Dow Corning ™ Z-6070, Z-6124, and 3 additives, Midland, MI); organotitanates And zirconates (Tyzor ™ TOT, TBT, and TE series, Dupont, Wilmington, DE); long chain (C12-C50) alkyl and alkylbenzene sulfonic acids, fatty amines or diamines, and their salts or quaternary derivatives As well as amphiphilic polymers that can be covalently bonded to the particle surface.
[0090]
In general, it is believed that charging results in an acid-base reaction between some portion present in the continuous phase and the particle surface. Thus, useful materials are materials that can participate in such reactions or any other charging reaction known in the art.
[0091]
Different classes of useful charge control agents include organic sulfates or sulfonates, metal soaps, block or comb copolymers, organic amides, organic zwitterions, and organic phosphates and phosphonates. These classifications do not limit the invention. Useful organic sulfates and sulfonates include bis (2-ethylhexyl) sodium sulfosuccinate, calcium dodecylbenzene sulfonate, calcium petroleum sulfonate, neutral or basic barium dinonylnaphthalene sulfonate, neutral or basic calcium disulfate. Nonyl naphthalene sulfonate, dodecyl benzene sulfonic acid sodium salt, and ammonium lauryl sulfate include, but are not limited to. Useful metal soaps include basic or neutral barium petronate; calcium petronate; Co, Ca, Cu, Mn, Ni, Zn and Fe salts of naphthenic acid; Ba, Al, Zn, Cu, Pb of stearic acid And Fe salts; aluminum tristearate, aluminum octylate, lithium heptanoate, iron stearate, iron distearate, barium stearate, chromium stearate, magnesium octylate, calcium stearate, iron naphthenate, zinc naphthenate, etc. And divalent and trivalent metal carboxylates; but not limited to: heptanoic acid Mn and Zn; and octylic acid Ba, Al, Co, Mn and Zn. Useful block or comb polymers include (A) a polymer of 2- (N, N) dimethylaminoethyl methacrylate quaternized with methyl-p-toluenesulfonate and (B) poly-2-ethylhexyl methacrylate. An AB diblock copolymer and a comb graft copolymer having an oil-soluble tail of poly (12-hydroxystearic acid), having a molecular weight of about 1800, and depending on an oil-soluble anchor group of poly (methyl methacrylate-methacrylic acid); However, it is not limited to these. Useful organic amides include, but are not limited to, polyisobutylene succinimides such as OLOA 1200, and N-vinyl pyrrolidone polymers. Useful organic zwitterions include, but are not limited to lecithin. Useful organophosphates and phosphonates include, but are not limited to, phosphated mono- and diglyceride sodium salts with saturated or unsaturated acid substituents.
[0092]
A particle dispersion stabilizer may be added to prevent flocculation or adhesion of particles to the capsule wall. Non-aqueous surfactants may be used in typical high resistance liquids used as suspending fluids in electrophoretic displays. These surfactants include, but are not limited to, glycol ethers, acetylene glycols, alkanoamides, sorbitol derivatives, alkyl amines, quaternary amines, imidazolines, dialkyl oxides, and sulfosuccinates.
[0093]
D.Encapsulated
Encapsulation has a long and rich history, and many processes and polymers have been found to be useful in producing capsules. The encapsulation of the internal phase can be accomplished in a number of different ways. A number of suitable procedures for microencapsulation are described in Microencapsulation, Processes and Applications (edited by IE Vandegaer), Plenum Press, New York, NY (1974), and Gutcho, Microcaptures and MirculeNuculeTens. Park Ridge, N .; J. et al. (1976). In this specification, both of the above documents are incorporated by reference. The process falls into several general categories: physical processes such as interfacial polymerization, in situ polymerization, coextrusion and other phase separation processes, in-liquid curing, and simple / complex coacervation categories. All of these categories can be applied to the present invention.
[0094]
It should be appreciated that many materials and processes are useful for making the displays of the present invention. Useful materials for the simple coacervation process include, but are not limited to, gelatin, polyvinyl alcohol, polyvinyl acetate, and cellulose derivatives such as carboxymethylcellulose. Useful materials for complex coacervation processes include gelatin, acacia, carrageenan, carboxymethylcellulose, hydrolyzed styrene anhydride copolymer, agar, alginate, casein, albumin, methyl vinyl ether comalane anhydride, and phthalate Acid cellulose, but is not limited thereto. Useful materials for the phase separation process include, but are not limited to, polystyrene, PMMA, polyethyl methacrylate, polybutyl methacrylate, ethyl cellulose, polyvinyl pyridine, and polyacrylonitrile. Useful materials for in situ polymerization processes include polyhydroxyamides having aldehydes, melamines, or ureas and formaldehyde; water-soluble oligomers of melamines or urea and formaldehyde condensates; and, for example, styrene, MMA, and acrylonitrile, Vinyl monomers such as, but not limited to. Finally, useful materials for the interfacial polymerization process include, but are not limited to, diacyl chlorides such as sebacoyl, adipoyl, and di- or polyamines or alcohols, and isocyanates. Useful emulsion polymerized materials can include, but are not limited to, styrene, vinyl acetate, acrylic acid, butyl acrylate, t-butyl acrylate, methyl methacrylate, and butyl methacrylate.
[0095]
The resulting capsules can be dispersed in a curable carrier, resulting in an ink that can be printed or coated onto any shape or curved large surface using conventional printing and coating techniques.
[0096]
In the context of the present invention, those skilled in the art will select the encapsulation procedure and wall material based on the desired capsule properties. These properties include: capsule radius distribution; electrical, mechanical, diffusion and optical properties of the capsule wall; and chemical compatibility with the internal phase of the capsule.
[0097]
The capsule wall generally has a high electrical resistivity. Although it is possible to use walls with a relatively low resistivity, this can limit performance if a relatively high addressing voltage is required. A complete description of the relevant electrical properties of the capsule wall is described in US Pat. No. 4,605,284, which is hereby incorporated by reference in its entirety. The capsule wall must also be mechanically strong (but mechanical strength is not critical when the finished capsule powder is dispersed and coated in a curable polymer binder) ). The capsule wall should generally not be porous. However, if it is desirable to use an encapsulation procedure that produces porous capsules, these capsules may be overcoated in a post-processing step (ie, second encapsulation). Furthermore, when the capsule is dispersed in a curable binder, the binder serves to close the pores. The capsule wall must be optically transparent. However, the wall material may be selected to match the refractive index of the internal phase of the capsule (ie, the suspending fluid) or the binder in which the capsule is dispersed. For some applications (eg, insertion between two fixed electrodes), a monodisperse capsule radius is desirable.
[0098]
A very suitable encapsulation technique for the present invention is described in US Pat. No. 4,087,376, the entire disclosure of which is incorporated herein by reference. This procedure involves the polymerization of urea and formaldehyde in the aqueous phase of an oil / water emulsion in the presence of a negatively charged carboxyl-substituted linear hydrocarbon polyelectrolyte material. The resulting capsule wall is a urea / formaldehyde copolymer that encloses and separates the internal phase. The capsule is transparent, mechanically strong and has excellent resistance properties.
[0099]
A related art of in situ polymerization uses an oil / water emulsion formed by dispersing an electrophoretic composition (ie, a dielectric liquid containing a suspension of pigment particles) in an aqueous environment. The monomer polymerizes to form a polymer with a higher affinity for the internal phase than for the aqueous phase, thereby condensing around the emulsified oily droplets. One particularly useful in situ polymerization process condenses urea and formaldehyde in the presence of poly (acrylic acid) (see, eg, US Pat. No. 4,001,140). In another useful process described in US Pat. No. 4,273,672, any of a variety of crosslinkers carried in an aqueous solution is deposited around very small oil droplets. Such crosslinkers include aldehydes, particularly formaldehyde, glyoxal, or glutaraldehyde; alum; zirconium salts; and polyisocyanates. In this specification, the entire disclosures of the aforementioned US Pat. Nos. 4,001,140 and 4,273,672 are incorporated by reference.
[0100]
The coacervation approach also uses an oil / water emulsion. One or more colloids are made droplets (ie agglomerated) from the aqueous phase and deposited as a shell around the oily droplets by controlling the temperature, pH and / or relative concentration, thereby microcapsules To produce. Suitable materials for coacervation include gelatin and acacia. See, for example, US Pat. No. 2,800,457. In this specification, the entire disclosure of the above patent is incorporated by reference.
[0101]
The interfacial polymerization approach relies on the presence of oil soluble monomers in the electrophoretic composition. This oil-soluble monomer is present again as an emulsion in the aqueous phase. Monomers in the minute hydrophobic droplets react with the monomers introduced into the aqueous phase, polymerize at the interface between the droplets and the surrounding aqueous medium, and form a shell around the droplets. The resulting wall is relatively thin and may be permeable, but this process does not require the high temperature properties of some other processes, thus providing greater flexibility with respect to the choice of dielectric liquid. give.
[0102]
FIG. 13A shows an exemplary apparatus and environment for performing emulsion-based encapsulation. The oil / water emulsion is prepared in a container 76 comprising a device 78 for monitoring the temperature and a device 80 for controlling the temperature. A pH monitor 82 may also be included. Impeller 84 may be used to maintain agitation throughout the encapsulation process and in combination with an emulsifier to control the size of emulsion droplets 86 resulting in a finished capsule. The aqueous continuous phase 88 may include, for example, a prepolymer or various system modifiers.
[0103]
FIG. 13B shows an oil droplet 90 comprising a substantially transparent suspending fluid 92 in which white microparticles 94 and black particles 96 are dispersed. Preferably, the particles 94 and 96 have a density that substantially matches the density of the suspending fluid 92. The liquid phase may also contain several threshold / bistable modifiers, charge control agents, and / or hydrophobic monomers to effect interfacial polymerization.
[0104]
FIG. 13C shows a similar oil drop 98 containing a suspending fluid 100 dyed in dark color containing a dispersion of white particles 94 and a suitable charge control agent.
[0105]
Coating aids may be used to improve the uniformity and quality of the coated or printed electrophoretic ink material. A wetting agent is typically added to adjust the interfacial tension at the coating / substrate interface and to adjust the liquid / air surface tension. Wetting agents include, but are not limited to, anionic and cationic surfactants and nonionic species such as silicone or fluoropolymer based materials. Dispersants may be used to modify the interfacial tension between the capsule and the binder to provide control of flocculation and particle settling.
[0106]
A surface tension modifier may be added to adjust the air / ink interface tension. In such applications, polysiloxanes are typically used to improve surface leveling and minimize other defects in the coating. Surface tension modifiers include, for example, DuPont (Wilmington, DE) Zonyl ™ series, 3M (St. Paul, MN) Fluorod ™ series, and Autochem (Glen Rock, NJ) fluoroalkyl series, Fluorinated surfactants such as; siloxanes such as Silwet ™ from Union Carbide (Danbury, CT); and polyethoxy and polypropoxy alcohols, but are not limited to these. Antifoaming agents such as silicone and silicone-free polymeric materials may be added to enhance air movement from within the ink to the surface and to facilitate the bursting of bubbles on the coating surface. Other useful defoamers include: glyceryl esters; polyhydric alcohols; formulated defoamers such as alkylbenzenes, natural fats, fatty acids, and metal soap oils; and silicones made from combinations of dimethylsiloxane polymers and silica Examples include, but are not limited to, a defoaming agent. Stabilizers such as uv absorbers and antioxidants may also be added to improve the life of the ink.
[0107]
Other additives for controlling properties such as coating viscosity and foaming may also be used in the coating fluid. It can be seen that stabilizers (uv absorbers, antioxidants) and other additives are useful in practical materials.
[0108]
E.Binder material
The binder is used as a non-conductive adhesive medium that supports and protects the capsule and bonds the electrode material to the capsule dispersion. Many forms and chemical types of binders are available. Among these binders are water soluble polymers, aqueous polymers, oil soluble polymers, thermosetting and thermoplastic polymers, and radiation curable polymers.
[0109]
Among the water-soluble polymers are various polysaccharides, polyvinyl alcohol, N-methylpyrrolidone, N-vinylpyrrolidone, various Carbowax ™ species (Union Carbide, Danbury, CT), and poly-2-hydroxyethyl acrylate There is.
[0110]
Water-dispersed or aqueous systems are generally latex compositions, and typical latex compositions are Neorez ™ and Neocry ™ resins (Zeneca Resins, Wilmington, Mass.), Acrysol ™ (Rohm and Haas, Philadelphia, PA), Bayhydrol ™ (Bayer, Pittsburg, PA), and Cytec Industries (West Patterson, NJ) HP lines. These latex compositions are generally polyurethane latexes, and may be formulated with one or more of acrylic, polyester, polycarbonate, or silicone, each latex having a glass transition temperature, "tack" degree, softness, Provides a cured resin in a specific set of properties defined by transparency, flexibility, water permeability and solvent resistance, elongation and tensile strength, thermoplastic flow, and solids level. Some aqueous systems can be mixed with reactive monomers and catalyzed to form more complex resins. Some can be further cross-linked by the use of a cross-linking agent such as aziridine which reacts with the carboxyl group.
[0111]
Typical applications of aqueous resins and aqueous capsules are shown below. Centrifugate large volumes of particles at low speed to separate excess water. After a given centrifugation process, for example after 10 minutes at 60 × G, the capsule is seen at the bottom of the centrifuge tube and the water part is seen at the top. Carefully remove water (by decantation or pipette). Measure the mass of the remaining capsules and add a mass of resin to be between one-eighth and one-tenth of the capsule weight. The mixture is gently mixed with a vibration mixer for about 30 minutes. After about 30 minutes, the mixture is ready for coating on a suitable substrate.
[0112]
An example of a thermosetting system is the Epoxy genus. The viscosities of these binary systems can vary widely, and the reactivity of the pair determines the “pot life” of the mixture. If the pot life is long enough to allow the coating operation, the capsules can be coated in a regular array in the coating process before the resin cures and cures.
[0113]
Thermoplastic polymers are melted at high temperatures. The thermoplastic polymer is often a polyester. A typical application of this type of product is hot melt glue. The dispersion of heat resistant capsules may be coated with such a medium. The solidification process begins during cooling, and the final hardness, transparency and flexibility are affected by polymer branching and molecular weight.
[0114]
Oil-soluble or solvent-soluble polymers are often similar in composition to aqueous systems. However, water itself is clearly an exception. The tolerances in making solvent systems are very large and are limited only by the choice of solvent and the solubility of the polymer. Of considerable importance in solvent-based systems is the viability of the capsule itself, and nothing can be done to reduce the integrity of the capsule with a solution.
[0115]
Radiation curable resins are generally found in solvent-based systems. The capsules may be dispersed in such media and coated, and then the resin may be cured by timed exposure to a threshold level of long or short wavelength ultraviolet radiation. As in all cases of curing the polymer resin, the final properties depend on the monomer, oligomer, crosslinker branching and molecular weight.
[0116]
However, many “water-reducing” monomers and oligomers are on the market. In the strict sense, these monomers and oligomers are not water soluble, but water is an acceptable diluent at low concentrations and can be relatively easily dispersed in the mixture. Under these circumstances, water is used to reduce the viscosity (from the first thousands to hundreds of thousands centipoise). Water-based capsules, such as capsules made from protein or polysaccharide materials, can be dispersed in such media and coated, provided that the viscosity can be sufficiently low. Curing of such systems is generally by ultraviolet radiation.
[0117]
III. Example
Example 1
The following procedure illustrates the gelatin / acacia microencapsulation used in the electrophoretic display of the present invention.
[0118]
APreparation of oil (internal) phase
In a 1 L flask, 0.5 g of oil blue N (Aldrich, Milwaukee, Wis.), 0.5 g of Sudan Red 7B (Aldrich), 417.25 g of halogenated hydrocarbon oil 0.8 (Halogenated hydrocarbon Products Corp., River). Edge, NJ), and 73.67 g of Isopar-G ™ (Exxon, Houston, TX). The mixture is stirred at 60 ° C. for 6 hours and then cooled to room temperature. Place 50.13 g of the resulting solution into a 50 mL polypropylene centrifuge tube and add 1.8 g of titanium dioxide (TiO 2).₂) (DuPont, Wilminfron, DE), 0.78 g of a 10% solution of OLOA 1200 (Chevron, Somerset, NJ) in halogenated hydrocarbon oil 0.8, and 0.15 g of Span 85 (Aldrich). The mixture is then sonicated in an Aquasonic Model 75D sonicator (VWR, Westchester, PA) for 5 minutes at 30 ° C. and power 9.
[0119]
B.Preparation of aqueous phase
10.0 g Acacia (Aldrich) is dissolved in 100.0 g water with stirring for 30 minutes at room temperature. The resulting mixture is decanted into two 50 mL polypropylene centrifuge tubes and centrifuged at about 2000 rpm for 10 minutes to remove insoluble material. 66 g of the purified solution is then decanted into a 500 mL unbaffled jacketed reactor and the solution is then heated to 40 ° C. A 6 blade (vertical geometry) saddle stirrer is then placed directly under the surface of the liquid. While stirring the solution at 200 rpm, 6 g of gelatin (300 bloom, type A, Aldrich) is carefully added over about 20 seconds to avoid clumping. The agitation is then reduced to 50 rpm to reduce foaming. The resulting solution is then stirred for 30 minutes.
[0120]
C.Encapsulated
While stirring at 200 rpm, the oil phase prepared as described above is slowly poured into the aqueous phase prepared as described above for about 15 seconds. The resulting oil / water emulsion is emulsified for 20 minutes. To this emulsion is slowly added 200 g of water preheated to 40 ° C. over a period of about 20 seconds. The pH is then lowered to 4.4 over 5 minutes using a 10% acetic acid solution (Aldrich acetic acid). The pH is monitored using a pH meter previously calibrated with pH 7.0 and pH 4.0 buffers. Stir for 40 minutes. Then 150 g of water preheated to 40 ° C. is added and the reactor contents are then cooled to 10 ° C. When the solution temperature reaches 10 ° C., 3.0 mL of 37% formalin solution (Aldrich) is added and the solution is stirred for another 60 minutes. The pH is raised to 10.0 by adding 20 g sodium carboxymethylcellulose (NaCMC) followed by 20 wt% sodium hydroxide (NaOH) solution. The thermostat bath is then set to 40 ° C. and allowed to stir for another 70 minutes. Allow the slurry to cool to room temperature with stirring overnight. At this time, the resulting capsule slurry is ready for sieving.
[0121]
D.Display formation
Two procedures for preparing an electrophoretic display from the capsule slurry are described below.
[0122]
1. Procedure using urethane binder
The resulting capsule slurry from above is mixed with an aqueous urethane binder NeoRez R-9320 (Zeneca Resins, Wilmington, Mass.) In a ratio of 1 part binder to 10 parts capsule. The resulting mixture is then coated on a 0.7 mm thick sheet of polyester film sputtered with indium-tin-oxide using a doctor blade. The blade gap of the doctor blade is controlled to 0.18 mm so as to place a single capsule layer. The coated membrane is then dried with hot air (60 ° C.) for 30 minutes. After drying, in a Chemrollments (Fairfield, OH) hot roll laminate, the dried film was applied to a backplane containing a 3 mm thick polyester sheet screen printed with thick film silver and dielectric ink at 60 psi and 15 psi pressure. Laminate at high temperature. An anisotropic tape is used to bond the backplane to the membrane. The conductive area forms the addressable area of the resulting display.
[0123]
2. Procedure using urethane / polyvinyl alcohol binder
The resulting capsule slurry from the above was prepared by combining an aqueous binder comprising a mixture of NeoRez R-966 (Zeneca Resins) and Airvol 203 (polyvinyl alcohol, Airvol Industries, Allentown, Pa.) With a 20% solution of Airvol 203 solution. Mix in a ratio of 1 part NeoRez R-966 to 5 parts capsules. The resulting mixture is then coated on a 0.7 mm thick sheet of polyester film sputtered with indium-tin-oxide using a doctor blade. The blade gap of the doctor blade is controlled to 0.18 mm so as to place a single capsule layer. The coated membrane is then dried with hot air (60 ° C.) for 30 minutes. After drying, the thick film silver ink is printed directly on the back of the dry film and cured at 60 ° C. The conductive area forms the addressable area of the display.
[0124]
Example 2
The following are examples of the preparation of microcapsules by in situ polymerization.
[0125]
In a 500 mL unbaffled jacketed reactor, mix 50 mL of a 10 wt% aqueous solution of ethylene komalein anhydride (Aldrich), 100 mL of water, 0.5 g of resorcinol (Aldrich), and 5.0 g of urea (Aldrich). The mixture is stirred at 200 rpm and the pH is adjusted to 3.5 over 1 minute using a 25 wt% NaOH solution. The pH is monitored using a pH meter previously calibrated with pH 7.0 and pH 4.0 buffers. To this is slowly added an oil phase prepared as described in Example 1 above, and stirring is accelerated to 450 rpm to reduce the average particle size to less than 200 μm. Then 12.5 g of a 37 wt% aqueous formaldehyde solution is added and the temperature is raised to 55 ° C. The solution is heated at 55 ° C. for 2 hours.
[0126]
Example 3
The following are examples of microcapsule preparation by interfacial polymerization.
[0127]
To 44 g of the oil phase prepared as described in Example 1 above, 1.0 g of sebacoyl chloride (Aldrich) is added. 3 ml of this mixture is then dispersed in 200 mL of water with stirring at 300 rpm at room temperature. Next, 2.5 mL of a 10 wt% aqueous solution of 1,6-diaminohexane is added to the dispersion. After about 1 hour, capsules are formed.
[0128]
Thus, encapsulated electrophoretic displays and materials useful for constructing encapsulated electrophoretic displays are described. Other aspects and advantages of the invention will be apparent in view of the above description. Accordingly, the scope of the invention is limited only by the appended claims.
[Brief description of the drawings]
FIG. 1 is a schematic view of encapsulated light scattering particles.
FIG. 2 shows a capsule containing particles in a suspending fluid with an electrode pair disposed adjacent to the capsule.
FIG. 3 is a view of a capsule containing light-absorbing particles in a suspending fluid with a reflective or retroreflective substrate disposed on the bottom of the capsule. The state is shown where the particles move towards one of the electrode pairs so that light can pass through the capsule and be reflected by the substrate.
FIG. 4 shows the capsule of FIG. 3 which prevents particles from moving to allow light to reach the substrate, thereby preventing light from being reflected by the substrate.
FIG. 5 shows a capsule comprising light absorbing particles and retroreflective particles.
FIG. 6A shows a capsule containing a reflective corner cube on the bottom and particles. In this figure, the particles are arranged so that light can pass through the capsule and be reflected by the corner cube.
FIG. 6B shows a capsule containing a reflective corner cube on the bottom and particles. In this figure, the particles are arranged so that light can pass through the capsule and be reflected by the corner cube.
FIG. 6C shows a microcapsule including a reflective corner cube on the bottom and particles. In this figure, the particles are arranged so that light cannot pass through the capsule and cannot be reflected by the corner cube.
FIG. 7 shows how a capsule can reflect light.
8A shows the capsule of FIG. 7 where particles contained within the capsule are arranged to allow light to enter and be reflected by the capsule.
FIG. 8B shows the capsule of FIG. 7 where the particles contained within the capsule are arranged to prevent light incident on the capsule from being reflected.
FIG. 9 shows a capsule comprising luminescent particles and light absorbing particles. In this figure, luminescent particles are placed toward the top surface of the capsule, thereby providing light.
FIG. 10 shows the capsule of FIG. 9 with light absorbing particles positioned toward the top surface of the capsule, thereby preventing light from exiting the capsule.
FIG. 11 shows a capsule placed adjacent to a reflective substrate and two electrodes, with the particles within the capsule aligned to allow light to pass through the capsule and be reflected by the substrate. Is done.
FIG. 12A shows two capsules in a binder placed adjacent to a reflective substrate and two electrodes, particles within the capsule being reflected by the substrate through the capsule Aligned to allow for.
FIG. 12B shows a capsule placed adjacent to a reflective substrate and two electrodes, so that particles within the capsule prevent light from passing through the capsule and from being reflected by the substrate. Aligned.
FIG. 13A is a diagram of an apparatus for performing emulsion-based encapsulation.
FIG. 13B is a diagram of oil droplets of a suspending fluid in which white and black particles are dispersed.
FIG. 13C is a dark fluid dyed suspension fluid oil droplet with dispersed white microparticles and charge control agent.

Claims (16)

An encapsulated electrophoretic display having a view surface and a rear surface,
The display
A polymer matrix;
A plurality of elastomer capsules disposed within the polymer matrix;
Including
The plurality of elastomer capsules are:
Capsule wall,
A cavity inside the capsule wall, containing a fluid;
Including
Each capsule includes a viewing surface that is substantially planar and a plurality of sidewalls extending away from the viewing surface, the cavity having a polyhedral shape having a plurality of surfaces. Wherein the fluid is oil in the cavity, a display according to claim 1. It said height aspect ratio of the width to the cavity is greater than 1.2, display according to any one of claims 1 or claim 2. It said aspect ratio is greater than 1.5, display of claim 3. It said aspect ratio is greater than 1.75, display of claim 4. The display according to any one of claims 1 to 5, wherein the volume fraction of the polymer matrix is greater than 0.0 and less than or equal to 0.9. The volume fraction is between 0.05 and 0.2, display of claim 6. The display according to any one of claims 1 to 7 , wherein the rear surface is substantially flat. The optically active portion of the view surface is greater than 80%, display according to any one of claims 1 to 8. The optically active portion is greater than 90%, display of claim 9. A process for making an encapsulated electrophoretic display,
(A) curing the binder, wherein the binder comprises a plurality of elastomer capsules disposed in the binder, the plurality of elastomer capsules comprising a capsule wall and an inner side of the capsule wall And a cavity containing a fluid in
(B) By applying a mechanical force to the binder, the binder has a non-spherical shape having a substantially planar view surface and a plurality of side walls extending away from the view surface. Forming each capsule, the cavity having a polyhedral shape having a plurality of faces, and
Manufacturing method including. Occurs wherein step (a) and (b) at the same time, process of claim 11. The manufacturing method according to claim 11 , wherein the mechanical force is applied by at least one of a roller, a vacuum lamination press, and a mechanical press. Wherein the mechanical force, said binder is stretched A process according to any one of claims 11-13. A process for making an encapsulated electrophoretic display,
The method includes curing a binder, the binder having a plurality of elastomer capsules disposed in the binder, the plurality of elastomer capsules including a capsule wall and an inner side of the capsule wall. And a cavity containing fluid, including a step,
The binder is an evaporative binder that deforms as the binder cures, whereby the plurality of capsules are substantially planar and a plurality of sidewalls extending away from the view plane. A method of forming a non-spherical shape having a shape of a polyhedron having a plurality of faces. The evaporative binder is an acrylic, urethane or poly (vinyl alcohol) binder A process according to claim 15.

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