This application is related to copending application Ser. No. 10/708,121, filed Feb. 2, 2004 (Publication No. 2004/0252360), which is a continuation-in-part of application Ser. No. 10/064,389, filed Jul. 9, 2002 (Publication No. 2003/0025855, now U.S. Pat. No. 6,831,769), which claims benefit of Application Ser. No. 60/304,117, filed Jul. 9, 2001. The aforementioned application Ser. No. 10/708,121 claims benefit of Application Ser. No. 60/319,934, filed Feb. 11, 2003 and Application Ser. No. 60/319,973, filed Feb. 26, 2003.
This application is also related to copending application Ser. No. 10/605,024, filed Sep. 2, 2003 (Publication No. 2004/0155857), which claims benefit of Application Ser. No. 60/319,516, filed Sep. 3, 2002.
This application is also related to copending application Ser. No. 10/907,065, filed Mar. 18, 2005 (Publication No. 2005/0146774), which is a divisional of application Ser. No. 10/249,957, filed May 22, 2003 (now U.S. Pat. No. 6,982,178), which claims benefit of Application Ser. No. 60/319,300, filed Jun. 10, 2002, and Application Ser. No. 60/320,186, filed May 12, 2003.
This application is also related to the following applications and patents: (a) application Ser. No. 10/329,023 (Publication No. 2003/0112491), filed Dec. 24, 2002, now U.S. Pat. 7,109,968; (b) U.S. Pat. No. 6,727,881, issued on application Ser. No. 09/140,846, filed Aug. 27, 1998, of which the aforementioned application Ser. No. 10/329,023 is a continuation; (c) U.S. Pat. No. 6,124,851, issued on application Ser. No. 08/504,896, filed Jul. 20, 1995, of which the aforementioned application Ser. No. 09/140,846 is a continuation-in-part; (d) application Ser. No. 08/983,404, filed Mar. 26, 1999, of which the aforementioned application Ser. No. 09/140,846 is a continuation-in-part; (e) International Application No. PCT/US96/12000 (Publication No. WO 97/04398), of which the aforementioned application Ser. No. 08/983,404 is the United States national phase; (f) U.S. Pat. No. 6,120,588, issued on application Ser. No. 08/935,800, filed Sep. 23, 1997, of which the aforementioned application Ser. No. 09/140,846 is a continuation-in-part; (g) Provisional Applications Ser. Nos. 60/057,118; 60/057,122; 60/057,133; 60/057,163; 60/057,716; 60/057,798; 60/057,799; 60/059,358; 60/059,543; 60/065,529; 60/065,605; 60/065,630; 60/066,115; 60/066,147; 60/066,245; 60/066,246; 60/066,334; 60/066,418; 60/070,935; 60/070,939; 60/070,940; 60/071,371; 60/072,390; 60/074,454; 60/076,955; 60/076,956; 60/076,957; 60/076,959; 60/076,978; 60/078,363; 60/081,362; 60/081,374; 60/083,252; 60/085,096; 60/090,222; 60/090,223; 60/090,232; 60/092,046; 60/092,050; 60/092,742; and 60/093,689; from all of which the aforementioned application Ser. No. 09/140,846 claims priority; (h) U.S. Pat. No. 6,657,772; (i) Application Ser. No. 60/304,015, filed Jul. 9, 2001, from which the aforementioned application Ser. No. 10/064,279 claims priority; (j) application Ser. No. 10/249,957, filed May 23, 2003 (now U.S. Pat. No. 6,982,178); and (k) U.S. Pat. No. 6,312,304.
The entire contents of all the aforementioned patents and applications, and of all United States Patents, published applications and copending applications mentioned below are herein incorporated by reference.
This invention relates to electro-optic displays and to materials, especially binders, for use therein. This invention relates in part to binders with electrical and other properties which render them especially suitable for use in electro-optic displays. The invention also provides polyurethanes which may also be useful in applications other than electro-optic displays. This invention also relates to certain articles of manufacture useful in the production of electro-optic displays.
Electro-optic displays comprise a layer of electro-optic material, a term which is used herein in its conventional meaning in the art to refer to a material having first and second display states differing in at least one optical property, the material being changed from its first to its second display state by application of an electric field to the material. The optical property is typically color perceptible to the human eye, but may be another optical property, such as optical transmission, reflectance, luminescence or, in the case of displays intended for machine reading, pseudo-color in the sense of a change in reflectance of electromagnetic wavelengths outside the visible range.
The electro-optic displays of the present invention typically contain an electro-optic material which is a solid in the sense that the electro-optic material has solid external surfaces, although the material may, and often does, have internal liquid- or gas-filled spaces, and to methods for assembling displays using such an electro-optic material. Such displays using solid electro-optic materials may hereinafter for convenience be referred to as “solid electro-optic displays”. Thus, the term “solid electro-optic displays” includes rotating bichromal member displays (see below), encapsulated electrophoretic displays, microcell electrophoretic displays and encapsulated liquid crystal displays.
The terms “bistable” and “bistability” are used herein in their conventional meaning in the art to refer to displays comprising display elements having first and second display states differing in at least one optical property, and such that after any given element has been driven, by means of an addressing pulse of finite duration, to assume either its first or second display state, after the addressing pulse has terminated, that state will persist for at least several times, for example at least four times, the minimum duration of the addressing pulse required to change the state of the display element. It is shown in published U.S. patent application Ser. No. 2002/0180687 that some particle-based electrophoretic displays capable of gray scale are stable not only in their extreme black and white states but also in their intermediate gray states, and the same is true of some other types of electro-optic displays. This type of display is properly called “multi-stable” rather than bistable, although for convenience the term “bistable” may be used herein to cover both bistable and multi-stable displays.
Several types of electro-optic displays are known. One type of electro-optic display is a rotating bichromal member type as described, for example, in U.S. Pat. Nos. 5,808,783; 5,777,782; 5,760,761; 6,054,071 6,055,091; 6,097,531; 6,128,124; 6,137,467; and 6,147,791 (although this type of display is often referred to as a “rotating bichromal ball” display, the term “rotating bichromal member” is preferred as more accurate since in some of the patents mentioned above the rotating members are not spherical). Such a display uses a large number of small bodies (typically spherical or cylindrical) which have two or more sections with differing optical characteristics, and an internal dipole. These bodies are suspended within liquid-filled vacuoles within a matrix, the vacuoles being filled with liquid so that the bodies are free to rotate. The appearance of the display is changed to applying an electric field thereto, thus rotating the bodies to various positions and varying which of the sections of the bodies is seen through a viewing surface. This type of electro-optic medium is typically bistable.
Another type of electro-optic display uses an electrochromic medium, for example an electrochromic medium in the form of a nanochromic film comprising an electrode formed at least in part from a semi-conducting metal oxide and a plurality of dye molecules capable of reversible color change attached to the electrode; see, for example O'Regan, B., et al., Nature 1991, 353, 737; and Wood, D., Information Display, 18(3), 24 (March 2002). See also Bach, U., et al., Adv. Mater., 2002, 14(11), 845. Nanochromic films of this type are also described, for example, in U.S. Pat. Nos. 6,301,038; 6,870.657; and 6,950,220. This type of medium is also typically bistable.
Another type of electro-optic display is an electro-wetting display developed by Philips and described in an article in the Sep. 25, 2003 issue of the Journal “Nature” and entitled “Performing Pixels: Moving Images on Electronic Paper”, Hayes, R. A., et al., “Video-Speed Electronic Paper Based on Electrowetting”, Nature, 425, 383-385 (2003). It is shown in copending application Ser. No. 10/711,802, filed Oct. 6, 2004 (Publication No. 2005/0151709), that such electro-wetting displays can be made bistable.
Another type of electro-optic display, which has been the subject of intense research and development for a number of years, is the particle-based electrophoretic display, in which a plurality of charged particles move through a fluid under the influence of an electric field. Electrophoretic displays can have attributes of good brightness and contrast, wide viewing angles, state bistability, and low power consumption when compared with liquid crystal displays. Nevertheless, problems with the long-term image quality of these displays have prevented their widespread usage. For example, particles that make up electrophoretic displays tend to settle, resulting in inadequate service-life for these displays.
As noted above, electrophoretic media require the presence of a fluid. In most prior art electrophoretic media, this fluid is a liquid, but electrophoretic media can be produced using gaseous fluids; see, for example, Kitamura, T., et al., “Electrical toner movement for electronic paper-like display”, IDW Japan, 2001, Paper HCS1-1, and Yamaguchi, Y., et al., “Toner display using insulative particles charged triboelectrically”, IDW Japan, 2001, Paper AMD4-4). See also U.S. Patent Publication No. 2005/0001810; European Patent Applications 1,462,847; 1,482,354; 1,484,635; 1,500,971; 1,501,194; 1,536,271; 1,542,067; 1,577,702; 1,577,703; and 1,598,694; and International Applications WO 2004/090626; WO 2004/079442; and WO 2004/001498. Such gas-based electrophoretic media appear to be susceptible to the same types of problems due to particle settling as liquid-based electrophoretic media, when the media are used in an orientation which permits such settling, for example in a sign where the medium is disposed in a vertical plane. Indeed, particle settling appears to be a more serious problem in gas-based electrophoretic media than in liquid-based ones, since the lower viscosity of gaseous suspending fluids as compared with liquid ones allows more rapid settling of the electrophoretic particles.
Numerous patents and applications assigned to or in the names of the Massachusetts Institute of Technology (MIT) and E Ink Corporation have recently been published describing encapsulated electrophoretic media. Such encapsulated media comprise numerous small capsules, each of which itself comprises an internal phase containing electrophoretically-mobile particles suspended in a liquid suspending medium, and a capsule wall surrounding the internal phase. Typically, the capsules are themselves held within a polymeric binder to form a coherent layer positioned between two electrodes. Encapsulated media of this type are described, for example, in U.S. Pat. Nos. 5,930,026; 5,961,804; 6,017,584; 6,067,185; 6,118,426; 6,120,588; 6,120,839; 6,124,851; 6,130,773; 6,130,774; 6,172,798; 6,177,921; 6,232,950; 6,249,271; 6,252,564; 6,262,706; 6,262,833; 6,300,932; 6,312,304; 6,312,971; 6,323,989; 6,327,072; 6,376,828; 6,377,387; 6,392,785; 6,392,786; 6,413,790; 6,422,687; 6,445,374; 6,445,489; 6,459,418; 6,473,072; 6,480,182; 6,498,114; 6,504,524; 6,506,438; 6,512,354; 6,515,649; 6,518,949; 6,521,489; 6,531,997; 6,535,197; 6,538,801; 6,545,291; 6,580,545; 6,639,578; 6,652,075; 6,657,772; 6,664,944; 6,680,725; 6,683,333; 6,704,133; 6,710,540; 6,721,083; 6,724,519; 6,727,881; 6,738,050; 6,750,473; 6,753,999; 6,816,147; 6,819,471; 6,822,782; 6,825,068; 6,825,829; 6,825,970; 6,831,769; 6,839,158; 6,842,167; 6,842,279; 6,842,657; 6,864,875; 6,865,010; 6,866,760; 6,870,661; 6,900,851; 6,922,276; 6,950,200; 6,958,848; 6,967,640; 6,982,178; 6,987,603; 6,995,550; 7,002,728; 7,012,600; 7,012,735; 7,023,430; 7,030,412; 7,030,854; 7,034,783; 7,038,655; 7,061,663; 7,071,913; 7,075,502; 7,075,703; 7,079,305; 7,106,296; 7,109,968; 7,110,163 and 7,110,164; and U.S. Patent Applications Publication Nos. 2002/0060321; 2002/0090980; 2002/0113770; 2002/0180687; 2003/0011560; 2003/0102858; 2003/0151702; 2003/0222315; 2004/0014265; 2004/0075634; 2004/0094422; 2004/0105036; 2004/0112750; 2004/0119681; 2004/0136048; 2004/0155857; 2004/0180476; 2004/0190114; 2004/0196215; 2004/0226820; 2004/0239614; 2004/0257635; 2004/0263947; 2005/0000813; 2005/0001812; 2005/0007336; 2005/0012980; 2005/0017944; 2005/0018273; 2005/0024353; 2005/0062714; 2005/0067656; 2005/0078099; 2005/0099672; 2005/0122284; 2005/0122306; 2005/0122563; 2005/0122564; 2005/0122565; 2005/0134554; 2005/0146774; 2005/0151709; 2005/0152018; 2005/0152022; 2005/0156340; 2005/0168799; 2005/0179642; 2005/0190137; 2005/0212747; 2005/0213191; 2005/0219184; 2005/0253777; 2005/0270261; 2005/0280626; 2006/0007527; 2006/0023296; 2006/0024437; and 2006/0038772; and International Applications Publication Nos. WO 00/38000; WO 00/36560; WO 00/67110; and WO 01/07961; and European Patents Nos. 1,099,207 B1; and 1,145,072 B1.
Many of the aforementioned patents and applications recognize that the walls surrounding the discrete microcapsules in an encapsulated electrophoretic medium could be replaced by a continuous phase, thus producing a so-called “polymer-dispersed electrophoretic display” in which the electrophoretic medium comprises a plurality of discrete droplets of an electrophoretic fluid and a continuous phase of a polymeric material, and that the discrete droplets of electrophoretic fluid within such a polymer-dispersed electrophoretic display may be regarded as capsules or microcapsules even though no discrete capsule membrane is associated with each individual droplet; see for example, the aforementioned U.S. Pat. No. 6,866,760. Accordingly, for purposes of the present application, such polymer-dispersed electrophoretic media are regarded as sub-species of encapsulated electrophoretic media. Furthermore, the continuous phase of such a polymer-dispersed electrophoretic medium may be regarded as a binder since it surrounds and encapsulates the individual droplets in the same manner that a binder surrounds the individual capsules in a conventional encapsulated electrophoretic display.
A related type of electrophoretic display is a so-called “microcell electrophoretic display”. In a microcell electrophoretic display, the charged particles and the fluid are not encapsulated within microcapsules but instead are retained within a plurality of cavities formed within a carrier medium, typically a polymeric film. The material as the carrier medium may be regarded as the binder of the microcell display in as much as it forms a continuous phase which surrounds and encapsulates discrete droplets of an internal phase (electrophoretic particles and surrounding fluid) in a manner exactly analogous to the continuous phase or binder of a polymer-dispersed electrophoretic medium. Microcell displays are described for example, in International Application Publication No. WO 02/01281, and published US Application No. 2002/0075556, both assigned to Sipix Imaging, Inc. Hereinafter, the term “microcavity electrophoretic display” may be used to cover both encapsulated and microcell electrophoretic displays.
An encapsulated electrophoretic display typically does not suffer from the clustering and settling failure mode of traditional electrophoretic devices and provides further advantages, such as the ability to print or coat the display on a wide variety of flexible and rigid substrates. (Use of the word “printing” is intended to include all forms of printing and coating, including, but without limitation: premetered coatings such as patch die coating, slot or extrusion coating, slide or cascade coating, curtain coating; roll coating such as knife over roll coating, forward and reverse roll coating; gravure coating; dip coating; spray coating; meniscus coating; spin coating; brush coating; air knife coating; silk screen printing processes; electrostatic printing processes; thermal printing processes; inkjet printing processes; and other similar techniques.) Thus, the resulting display can be flexible. Further, because the display medium can be printed (using a variety of methods), the display itself can be made inexpensively.
Although electrophoretic media are often opaque (since, for example, in many electrophoretic media, the particles substantially block transmission of visible light through the display) and operate in a reflective mode, many electrophoretic displays can be made to operate in a so-called “shutter mode” in which one display state is substantially opaque and one is light-transmissive. See, for example, the aforementioned U.S. Pat. Nos. 6,130,774 and 6,172,798, and U.S. Pat. Nos. 5,872,552; 6,144,361; 6,271,823; 6,225,971; and 6,184,856. Dielectrophoretic displays, which are similar to electrophoretic displays but rely upon variations in electric field strength, can operate in a similar mode; see U.S. Pat. No. 4,418,346.
Other types of electro-optic materials, for example, polymer-dispersed liquid crystal, may also be used in some of the displays of the present invention.
In considering the choice of materials for use in an electro-optic display, attention must be paid to the process by which the display is to be assembled. Most prior art methods for final production of electrophoretic displays are essentially batch methods in which the electro-optic medium, a lamination adhesive and the backplane are only brought together immediately prior to final assembly, and it is desirable to provide methods better adapted for mass production. The aforementioned U.S. Pat. No. 6,982,178 describes a method of assembling a solid electro-optic display (including a particle-based electrophoretic display) which is well adapted for mass production. Essentially, this patent describes a so-called “front plane laminate” (“FPL”) which comprises, in order, a light-transmissive electrically-conductive layer; a layer of a solid electro-optic medium in electrical contact with the electrically-conductive layer; an adhesive layer; and a release sheet. Typically, the light-transmissive electrically-conductive layer will be carried on a light-transmissive substrate, which is preferably flexible, in the sense that the substrate can be manually wrapped around a drum (say) 10 inches (254 mm) in diameter without permanent deformation. The term “light-transmissive” is used in this patent and herein to mean that the layer thus designated transmits sufficient light to enable an observer, looking through that layer, to observe the change in display states of the electro-optic medium, which will be normally be viewed through the electrically-conductive layer and adjacent substrate (if present). The substrate will be typically be a polymeric film, and will normally have a thickness in the range of about 1 to about 25 mil (25 to 634 μm), preferably about 2 to about 10 mil (51 to 254 μm). The electrically-conductive layer is conveniently a thin metal oxide layer of, for example, aluminum or indium tin oxide (ITO), or may be a conductive polymer. Polyethylene terephthalate (PET) films coated with aluminum or ITO are available commercially, for example as “aluminized Mylar” (“Mylar” is a Registered Trade Mark) from E. I. du Pont de Nemours & Company, Wilmington Del., and such commercial materials may be used with good results in the front plane laminate.
Assembly of an electro-optic display using such a front plane laminate may be effected by removing the release sheet from the front plane laminate and contacting the adhesive layer with the backplane under conditions effective to cause the adhesive layer to adhere to the backplane, thereby securing the adhesive layer, layer of electro-optic medium and electrically-conductive layer to the backplane. This process is well-adapted to mass production since the front plane laminate may be mass produced, typically using roll-to-roll coating techniques, and then cut into pieces of any size needed for use with specific backplanes.
The aforementioned U.S. Pat. No. 6,982,178 also describes a method for testing the electro-optic medium in a front plane laminate prior to incorporation of the front plane laminate into a display. In this testing method, the release sheet is provided with an electrically conductive layer, and a voltage sufficient to change the optical state of the electro-optic medium is applied between this electrically conductive layer and the electrically conductive layer on the opposed side of the electro-optic medium. Observation of the electro-optic medium will then reveal any faults in the medium, thus avoiding laminating faulty electro-optic medium into a display, with the resultant cost of scrapping the entire display, not merely the faulty front plane laminate.
The aforementioned U.S. Pat. No. 6,982,178 also describes a second method for testing the electro-optic medium in a front plane laminate by placing an electrostatic charge on the release sheet, thus forming an image on the electro-optic medium. This image is then observed in the same way as before to detect any faults in the electro-optic medium.
The aforementioned 2004/0155857 describes a so-called “double release film” which is essentially a simplified version of the front plane laminate previously described. One form of the double release sheet comprises a layer of a solid electro-optic medium sandwiched between two adhesive layers, one or both of the adhesive layers being covered by a release sheet. Another form of the double release sheet comprises a layer of a solid electro-optic medium sandwiched between two release sheets. Both forms of the double release film are intended for use in a process generally similar to the process for assembling an electro-optic display from a front plane laminate already described, but involving two separate laminations; typically, in a first lamination the double release sheet is laminated to a front electrode to form a front sub-assembly, and then in a second lamination the front sub-assembly is laminated to a backplane to form the final display.
The aforementioned U.S. Pat. No. 7,110,164 describes a process for assembling an electro-optic display in which a layer of an electro-optic medium is coated on a first release sheet, a layer of lamination adhesive is coated on a second release sheet, and the two resulting structures are laminated together to form a structure comprising, in order, the first release sheet, the electro-optic layer, the adhesive layer and the second release sheet.
In view of the advantages of the assembly method using a front plane laminate described in the aforementioned U.S. Pat. No. 6,982,178, it is desirable that materials intended for use in an electro-optic display be capable of being incorporated into such a front plane laminate. It is also desirable that such materials be capable of being incorporated into a double release film as previously described, and in the aforementioned structure described in U.S. Pat. No. 7,110,164.
As already indicated, when an electro-optic display is produced using a front plane laminate or double release film, a layer of lamination adhesive is normally present between the electrodes in the final display. (More than one layer of adhesive may be present between the electrodes; see for example copending Application Ser. No. 60/596,743, filed Oct. 18, 2005, which describes a form of double release film referred to as an “inverted front plane laminate”.) As discussed in the aforementioned U.S. Pat. No. 6,831,769, the electrical properties of the lamination adhesive can have a substantial effect on the electro-optic properties of the display. However, the lamination adhesive is not necessarily the only polymeric component present between the electrodes in an electro-optic display. As described in, for example, the aforementioned U.S. Pat. No. 6,839,158, in an encapsulated electrophoretic display the electro-optic layer normally comprises, in addition to the capsules themselves, a polymeric binder which, upon drying or curing, serves to form the capsules into a mechanically coherent layer especially when, as this patent teaches is desirable, the capsules are present in the form of a monolayer of capsules. The binder is also present between the electrodes in the final display and hence also affects the electro-optic properties of the display. Indeed, to the extent that the binder lies closer to the capsules of an encapsulated electrophoretic display than does the lamination adhesive (which is typically separated from the internal phase by some thickness of binder), the binder may have a greater effect on the electro-optic properties of a display than the lamination adhesive. Similarly the continuous matrix of a rotating bichromal member medium, the continuous phase of a polymer-dispersed electrophoretic display and the wall material used in a microcell display (all of which essentially correspond to the binder of an encapsulated electrophoretic display, and all of which will hereinafter be considered binders) can have major effects on the electro-optic properties of the display. The present invention relates to binders with improved electrical and mechanical properties for use in electro-optic displays, and to displays, front plane laminates, inverted front plane laminates and double release films incorporating such binders.
Accordingly, this invention provides a first polyurethane, this first polyurethane being formed from an isocyanate and a polyester diol having a molecular weight less than about 2000, or a polyester diol containing two polyester diol segments connecting by a steric hindrance group, each of the polyester diol segments having a molecular weight less than about 2000.
The term “steric hindrance group” is used herein to denote any group capable of connecting two polyester diol segments together and having sufficient bulk to provide steric hindrance to the crystallization of the segments. The steric hindrance group may comprise, for example, a quaternary carbon atom; a specific useful group being a —C(CH3)2— grouping.
This first polyurethane of the present invention may be formed from a polycaprolactone diol having a molecular weight less than about 1500. When the polycaprolactone diol comprises two polycaprolactone segments connected by a steric hindrance group, each of the segments may have a molecular weight not greater than about 1500. The polyurethane may be in the form of an aqueous latex.
This invention also provides a second polyurethane of the present invention, this second polyurethane being formed from an isocyanate and a polyester diol, the polyurethane not crystallizing between about −10° C. and about 70° C. when coated as a thin film. The term “thin film” is used herein to denote a film having a thickness of the order of about 20 μm.
The second polyurethane may be in the form of an aqueous latex.
This invention extends to an electro-optic display comprising a layer of a solid electro-optic material, and at least one electrode arranged to apply an electric field to the layer of electro-optic material, the layer of electro-optic material comprising a binder, wherein the binder comprises a first or second polyurethane of the present invention.
This invention also provides an electronic book reader, portable computer, tablet computer, cellular telephone, smart card, sign, watch, shelf label or flash drive comprising a display of the present invention.
This invention also extends to an article of manufacture (a front plane laminate) comprising in order: a light-transmissive electrically-conductive layer; a layer of a solid electro-optic medium comprising a binder and in electrical contact with the electrically-conductive layer; an adhesive layer; and a release sheet, wherein the binder comprises a first or second polyurethane of the present invention.
This invention also extends to an article of manufacture (a double release film) comprising a layer of a solid electro-optic medium comprising a binder and having first and second surfaces on opposed sides thereof; a first adhesive layer on the first surface of the layer of electro-optic medium; a release sheet disposed on the opposed side of the first adhesive layer from the layer of electro-optic medium; and a second adhesive layer on the second surface of the layer of electro-optic medium, wherein the binder comprises a first or second polyurethane of the present invention.
This invention also extends to an article of manufacture (an inverted front plane laminate) comprising, in order: at least one of a light-transmissive protective layer and a light-transmissive electrically-conductive layer; an adhesive layer; a layer of a solid electro-optic medium comprising a binder; and a release sheet, wherein the binder comprises a first or second polyurethane of the present invention.
This invention also extends to an article of manufacture (a double release film) comprising:
Finally, this invention also extends to an article of manufacture comprising:
The manner in which the binders of the present invention can be used in the production of an electro-optic display will now be described, though by way of illustration only, with reference to
The front plane laminate (generally designated 100) shown in
The substrate 110 is typically a transparent plastic film, such as a 7 mil (177 μm) poly(ethylene terephthalate) (PET) sheet. The lower surface (in
The electro-optic layer 130 may be deposited on the conductive layer 120, typically by slot coating, the two layers being in electrical contact. The electro-optic layer 130 shown in
The FPL 100 is desirably prepared by coating the lamination adhesive 180, in liquid form, conveniently by slot coating, on to release sheet 190, drying (or otherwise curing) the adhesive to form a solid layer and then laminating the adhesive and release sheet to the electro-optic layer 130, which has previously been coated on to the substrate 110 bearing the conductive layer 120; this lamination may conveniently be effected using hot roll lamination. (Alternatively, but less desirably, the lamination adhesive may be applied over the electro-optic layer 130 and there dried or otherwise cured before being covered with the release sheet 190.) The release sheet 190 is conveniently a 7 mil (177 μm) film; depending upon the nature of the electro-optic medium used, it may be desirable to coat this film with a release agent, for example a silicone. As illustrated in
For further details regarding front plane laminates and processes for the preparation and use thereof, the reader is respectfully directed to the aforementioned U.S. Pat. No. 6,982,178.
A double release sheet (generally designated 300) of the present invention is shown in
The sheet 300 may be formed by first coating the release sheet 310 with a layer of adhesive, which is then dried or cured to form the first adhesive layer 308. Next, a mixture of the capsules 304 and binder 306 is printed or otherwise deposited on the first adhesive layer 308, and then the mixture is dried or cured to form a coherent layer 302. Finally, a layer of adhesive is deposited over the layer 302, dried or cured to form the second adhesive layer 312, and covered by the second release sheet 314.
It will be apparent to those skilled in coating technology that this sequence of operations used to form the sheet 300 is well adapted for continuous production and that, by careful choice of materials and process conditions, it may be possible to carry out the entire sequence of operations in a single pass through conventional roll-to-roll coating apparatus.
To assemble a display using a double release film such as the film 300, one release sheet (typically that on to which the electro-optic material was coated) is peeled away, and the remaining layers of the double release film are attached to a front substrate using, for example a thermal, radiation, or chemically based lamination process. Typically, the front substrate will include a conductive layer which will form the front electrode of the final display. The front substrate may include additional layers, such as an ultra-violet filter or a protective layer intended to protect the conductive layer from mechanical damage. Thereafter, the other release sheet is peeled away, thereby exposing the second adhesive layer, which is used to attach the electro-optic material coating assembly to a backplane. Again, a thermal, radiation, or chemically based lamination process may be used. It will be appreciated that the order of the two laminations described is essentially arbitrary and could be reversed, although it practice it is almost always more convenient to laminate the double release film to the front substrate first, and thereafter to laminate the resulting front subassembly to the backplane.
For further details regarding double release films and processes for the preparation and use thereof, the reader is respectfully directed to the aforementioned 2004/0155857.
The displays of the present invention may be used in any application in which prior art electro-optic displays have been used. Thus, for example, the present displays may be used in electronic book readers, portable computers, tablet computers, cellular telephones, smart cards, signs, watches, shelf labels and flash drives.
As already mentioned, the present invention relates to “custom” polyurethanes having properties which render them especially useful as binders in encapsulated electrophoretic and other types of electro-optic displays. The general reasons why polyurethanes are preferred as binders in electro-optic displays have already been summarized above; of the commercially available polyurethanes, NeoRez R 9314 and R 9621 are especially useful, a preferred blend comprising 75 weight per cent of the former and 25 weight per cent of the latter.
However, although this 75/25 blend provides good overall display performance, there are some drawbacks associated with its use. Firstly, due to the presence of a higher weight fraction of polyester segments in R 9314, this material undergoes a melting/crystallization transition around 40° C. The polymer crystallization results in changes in electrical properties of the material, which affect the display performance over time. Secondly, the use of a polymer blend is generally undesirable because the polymers in the blend could potentially undergo a macrophase separation, resulting in a heterogeneous material. Thirdly, use in electro-optic displays is a very minor use of commercial polyurethanes, so that the manufacturers of such materials may change them to improve their performance in larger scale uses in a manner which compromises their effectiveness as binders in electro-optic displays. Thus, there is a need for a single component “custom” polyurethane of known composition having properties optimized for use as a binder in electro-optic displays.
The present invention controls the length of the polyester segment in a polyurethane. It is known that the crystalline transition in polyurethanes such as R 9314 is due to the long polyester segments present between the urethane linkages on the polymer backbone. By reducing the length of the polyester segments (below a partial molecular weight of about 2000) between the urethane groups, the polyester segments are rendered incapable of chain folding crystallization, thus eliminating the crystallization of the polymer as a whole. To synthesize such a polymer, one uses a polyester diol with a relatively short chain length. The diol may be polycaprolactone diol having a molecular weight not greater than about 1500.
Two different types of polyester diols may be used in the present process. The first type is typified by the following Formula I:
where m+n<13.
This first type of polyester diol contains two polyester segments (polycaprolactone segments in Formula I) linked by a group which does not provide any hindrance to crystallization of the polyester segments. The molecular weight of this type of polyester diol should not exceed about 2000.
The second type of polyester diol is typified by the following Formula II:
where m<13 and n<13.
This second type of polyester diol contains two polyester segments (polycaprolactone segments in Formula II) linked by a steric hindrance group which is sufficiently bulky and thus provides sufficient steric hindrance to hinder the crystallization of the polyester segments. In this type of polyester diol, the two polyester segments are in effect isolated from each other by the steric hindrance group and each segment can have a molecular weight up to about 2000.
The following Examples are given, though by way of illustration only, to show details of preferred polyurethanes of the present invention.
A polyurethane prepolymer was synthesized under a nitrogen atmosphere in a jacketed 500 mL glass reactor equipped with a mechanical stirrer, a thermometer, and a nitrogen inlet. 4,4′-Methylenebis(cyclohexyl isocyanate) (20.99 g, Bayer Desmodur W), polycaprolactone diol (31.25 g, Aldrich, average Mn ca. 1250), and dibutyltin dilaurate (0.04 g, Aldrich) were charged into the reactor and the mixture was heated at 80° C. for 2 hours. Thereafter, a solution of 2,2-bis(hydroxymethyl)propionic acid (3.35 g, Aldrich) in 1-methyl-2-pyrrolidinone (10 g, Aldrich) was added into the reactor and the reaction allowed to proceed at 80° C. for another hour to give an isocyanate-terminated prepolymer. The reactor temperature was then lowered to 60° C. for 30 minutes, and triethylamine (2.4 g, Aldrich) was added to neutralize the carboxylic acid. The reactor temperature was then further lowered to 30° C. and de-ionized water (105 g) was added to convert the prepolymer to a water-borne dispersion. Chain extension was carried out immediately after the dispersing step with hexamethylenediamine (3.5 g, Aldrich) dissolved in a small amount of de-ionized water over 1 hour at 30° C. Finally, the dispersion was heated at 60° C. for one hour to ensure that all the residual isocyanate groups had reacted.
A polyurethane prepolymer was synthesized under a nitrogen atmosphere in a jacketed glass reactor equipped with a mechanical stirrer, a thermometer, and a nitrogen inlet. 4.4′-Methylenebis(cyclohexyl isocyanate (18.3 g) is added to the reactor, followed by 1-methyl-2-pyrrolidone (27 g), polycaprolactone (2000 molecular weight, 49.3 g), and 2,2-bis(hydroxymethyl)propionic acid (3.4 g). The reactor was heated to 95° C. for 4 hours and then cooled to 70° C. to form an isocyanate-terminated prepolymer. Triethylamine (2.0 g) was added slowly to the prepolymer and the resultant mixture mixed for 30 minutes. Water (84 g) was added to a second reactor equipped with a mechanical stirrer and a thermocouple. Prepolymer (80 g) was then slowly transferred from the first reactor to the second reactor with stirring. Hexamethylenediamine (2.7 g of a 70% solution) was added to the second reactor for chain extension, and the resultant dispersion was heated to 80° C. for 1 hour to complete the reaction.
The polyurethanes prepared in Examples 1 and 2 above were subjected to differential scanning calorimetry. To provide a control, the aforementioned 75:25 R 9314/R 9621 blend (designated simply “Blend” in
From
Tests were conducted to determine whether the polyurethane of Example 2 had better storage stability than that of the aforementioned R 9314/R 9621 blend. For this purpose, a dried film of each binder was laminated between two ITO-coated polyester poly(ethylene terephthalate) films, the ITO layers of course being in direct contact with the polyurethane. To ensure that all samples had the same thermal history, they were heated in an oven at 70° C. for a few hours and then equilibrated at 25° C. and 50 per cent relative humidity for five days. The time zero in the test described below was taken at the end of this period of storage.
The samples were then stored at 25° C. and 50 per cent relative humidity for six weeks, and the resistance of the binder layer was measured at intervals. The results obtained are shown in
The results in
It will be apparent to those skilled in the art that numerous changes and modifications can be made in the specific embodiments of the present invention described above without departing from the scope of the invention. In particular, although the invention has been described above mainly in connection with encapsulated electrophoretic media having discrete capsules, similar advantages can be achieved by the use of the binders of the present invention in the other types of electro-optic displays previously discussed. Accordingly, the whole of the foregoing description is to be construed in an illustrative and not in a limitative sense.
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