U.S. patent application number 11/017181 was filed with the patent office on 2006-06-22 for reflective display based on liquid crystal materials.
This patent application is currently assigned to Eastman Kodak Company. Invention is credited to Krishnan Chari, John C. Kowalczyk, Charles M. JR. Rankin.
Application Number | 20060134564 11/017181 |
Document ID | / |
Family ID | 36121307 |
Filed Date | 2006-06-22 |
United States Patent
Application |
20060134564 |
Kind Code |
A1 |
Chari; Krishnan ; et
al. |
June 22, 2006 |
Reflective display based on liquid crystal materials
Abstract
The present invention relates to a high contrast reflective
display comprising at least one substrate, at least one
electrically conductive layer and at least one close-packed,
ordered monolayer of domains of electrically modulated material in
a fixed, preferably crosslinked, polymer matrix and a method of
making the same.
Inventors: |
Chari; Krishnan; (Fairport,
NY) ; Kowalczyk; John C.; (Rochester, NY) ;
Rankin; Charles M. JR.; (Penfield, NY) |
Correspondence
Address: |
Paul A. Leipold;Patent Legal Staff
Eastman Kodak Company
343 State Street
Rochester
NY
14650-2201
US
|
Assignee: |
Eastman Kodak Company
|
Family ID: |
36121307 |
Appl. No.: |
11/017181 |
Filed: |
December 20, 2004 |
Current U.S.
Class: |
430/330 |
Current CPC
Class: |
C09K 2323/02 20200801;
C09K 2323/00 20200801; G02F 1/133305 20130101; G02F 2202/38
20130101; G02F 1/1334 20130101; G02F 1/13345 20210101; G02F 1/13718
20130101 |
Class at
Publication: |
430/330 |
International
Class: |
G03F 7/00 20060101
G03F007/00 |
Claims
1. A high contrast reflective display comprising at least one
substrate, at least one electrically conductive layer and at least
one electronically modulated imaging layer, wherein said
electronically modulated imaging layer comprises a close-packed,
ordered monolayer of domains of electrically modulated material in
a fixed polymer matrix.
2. The high contrast reflective display of claim 1 wherein said
substrate is flexible.
3. The high contrast reflective display of claim 1 wherein said
substrate is transparent.
4. The high contrast reflective display of claim 3 further
comprising a second substrate.
5. The high contrast reflective display of claim 1 wherein said
electrically conductive layer a surface conductivity of less than
10.sup.4 ohms/sq.
6. The high contrast reflective display of claim 1 wherein said
electrically conductive conductive layer comprises ITO.
7. The display of claim 1 wherein said electrically conductive
layer comprises polythiophene.
8. The high contrast reflective display of claim 1 further
comprising at least a second electrically conductive layer, wherein
said at least one close-packed, ordered monolayer of electrically
modulated material in a crosslinked polymer matrix is between said
at least one electrically conductive layer and said second
conductive layer.
9. The high contrast reflective display of claim 1 wherein at least
one electrically conductive layer is patterned.
10. The high contrast reflective display of claim 1 further
comprising a means for applying electrical field across said at
least one close-packed, ordered monolayer of electrically modulated
material in a fixed polymer matrix.
11. The high contrast reflective display of claim 1 wherein said
electrically modulating material is a liquid crystalline
material.
12. The high contrast reflective display of claim 1 wherein said
electrically modulated material comprises a bistable liquid
crystalline material.
13. The high contrast reflective display of claim 12 wherein said
bistable liquid crystalline material comprises a chiral nematic
liquid crystal layer.
14. The high contrast reflective display of claim 1 wherein said at
least one close-packed, ordered monolayer of electrically modulated
material is a hexagonally closest packed monolayer of light
modulating material.
15. The high contrast reflective display of claim 1 wherein said at
least one close-packed, ordered monolayer of electrically modulated
material has a repeat pattern or periodicity with a repeat distance
of the order of the wavelength of visible light.
16. The high contrast reflective display of claim 1 wherein said
fixed polymer matrix is a crosslinked polymer matrix.
17. The high contrast reflective display of claim 1 wherein said
fixed polymer matrix is not rigid prior to drying.
18. The high contrast reflective display of claim 1 wherein said
fixed polymer matrix is in a random configuration if the coating is
dried at a temperature that is above the sol-gel transition
temperature.
19. The high contrast reflective display of claim 1 wherein said
fixed polymer matrix prior to crosslinking has a sol-gel transition
temperature or thermal gelation temperature or chill set
temperature below 23.degree. C.
20. The high contrast reflective display of claim 1 wherein said
fixed polymer matrix prior to crosslinking has a sol-gel transition
temperature or thermal gelation temperature or chill set
temperature below 10.degree. C.
21. The high contrast reflective display of claim 1 wherein said
electrically modulated material to said fixed polymer matrix ratio
is from 6:1 to 0.5:1
22. The high contrast reflective display of claim 1 wherein said
electrically modulated material to said fixed polymer matrix ratio
is 3:1.
23. The high contrast reflective display of claim 1 wherein said
fixed polymer matrix comprises gelatin.
24. The high contrast reflective display of claim 23 wherein said
gelatin is in a random coil configuration if the coating is dried
at a temperature that is above the sol-gel transition temperature
of gelatin.
25. The high contrast reflective display of claim 23 wherein said
gelatin is fish gelatin.
26. The high contrast reflective display of claim 25 wherein said
fish gelatin is deep water fish gelatin.
27. The high contrast reflective display of claim 23 wherein said
gelatin has lower imino acid content than bovine gelatin.
28. The high contrast reflective display of claim 1 wherein said
fixed polymer matrix further comprises a hardening agent.
29. The high contrast reflective display of claim 1 further
comprising a protective layer.
30. The high contrast reflective display of claim 29 wherein said
protective layer comprises gelatin.
31. The high contrast reflective display of claim 30 wherein said
gelatin contains molecules in a helix configuration.
32. The high contrast reflective display of claim 1 wherein said
electrically modulated imaging layer further comprises
polyvinylalcohol (PVA).
33. The high contrast reflective display of claim 1 wherein said at
least one electronically modulated imaging layer has a RMS surface
roughness of less than 1.5 microns
34. The high contrast reflective display of claim 1 comprising a
stack of at least two of said high contrast reflective displays,
wherein a stack comprises at least one substrate, at least one
electrically conductive layer and at least one close-packed,
ordered monolayer of domains of electrically modulated material in
a fixed polymer matrix.
35. A method of making a high contrast reflective display
comprising: providing a substrate; applying a conductive layer;
applying at least one layer of domains of electrically modulated
material in a polymer matrix; drying the at least one applied layer
of said domains of electrically modulated material in a polymer
matrix at a temperature above the chill set temperature or sol-gel
transition temperature of said polymer matrix to permit
self-assembly of said domains of electrically modulated material
into a close-packed monolayer of said domains of electrically
modulated material; and fixing said polymer matrix to preserve said
close-packed monolayer of domains of electrically modulated
material.
36. The method of claim 35 further comprising: applying a second
aqueous layer containing gelatin; chill setting said second aqueous
layer containing gelatin; and drying said second aqueous layer.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a high contrast
displays.
BACKGROUND OF THE INVENTION
[0002] There is significant interest in low cost flexible
electronic displays. Typically, such displays comprise a light
modulating component embedded in a binder (most commonly polymer)
matrix that is coated over a conductive plastic support. Broadly
speaking, a light modulating component is a material that changes
its optical properties such as its ability to reflect or transmit
light in response to an electric field. The light modulating
component may be a liquid crystalline material such as a nematic
liquid crystal, a chiral nematic or cholesteric liquid crystal or a
ferroelectric liquid crystal. The light modulating material may
also be a water insoluble liquid containing particles that undergo
electrophoresis or motion such as rotation or translation in
response to an electric field. Displays comprising a liquid
crystalline material in a polymer matrix are referred to as polymer
dispersed liquid crystal (PDLC) displays.
[0003] There are two main methods for fabricating PDLC devices:
emulsion methods and phase separation methods. Emulsion methods
have been described in U.S. Pat. Nos. 4,435,047 and 5,363,482. The
liquid crystal is mixed with an aqueous solution containing
polymer. The liquid crystal is insoluble in the continuous phase
and an oil-in-water emulsion is formed when the composition is
passed through a suitable shearing device, such as a homogenizer.
The emulsion is coated on a conductive surface and the water
allowed to evaporate. A second conductive surface may then be
placed on top of the emulsion or imaging layer by lamination,
vacuum deposition, or screen printing to form a device. While the
emulsion methods are straightforward to implement, droplet size
distributions tend to be broad resulting in a loss in performance.
For cholesteric liquid crystal devices, also referred to herein as
CLC devices, this typically means reduced contrast and brightness.
Phase separation methods were introduced in an effort to overcome
this difficulty.
[0004] Phase separation methods have been outlined in U.S. Pat. No.
4,688,900 and in Drzaic, P. S. in Liquid Crystal Dispersions, pgs.
30-51, published by World Scientific, Singapore (1995). The liquid
crystal and polymer, or precursor to the polymer, are dissolved in
a common organic solvent. The composition is then coated on a
conductive surface and induced to phase separate by application of
ultraviolet (UV) radiation or by the application of heat or by
evaporation of the solvent, resulting in droplets of liquid crystal
in a solid polymer matrix. A device may then be constructed
utilizing this composition. Although phase separation methods
produce dispersed droplets having more uniform size distributions,
there are numerous problems with this approach. For example, the
long term photostability of photopolymerized systems is a concern
due to the presence of photoinitiators that produce reactive free
radicals. Photoinitiators not consumed by the polymerization
process can continue to produce free radicals that can degrade the
polymer and liquid crystals over time. Furthermore, it is also
known that UV radiation is harmful to liquid crystals.
Specifically, exposure to UV radiation can lead to decomposition of
the chiral dopant in a cholesteric liquid crystal mixture,
resulting in a change in the reflected color. The use of organic
solvents may also be objectionable in certain manufacturing
environments.
[0005] U.S. Pat. No. 6,423,368 and U.S. Pat No. 6,704,073 propose
to overcome the problems associated with the prior art methods
through the use of droplets of the liquid crystal material prepared
using a limited coalescence process. In this process, the
droplet-water interface is stabilized by particulate species, such
as colloidal silica. Surface stabilization by particulate species
such as colloidal silica is particularly preferred as it can give
narrow size distribution and the size of the droplets can be
controlled by the concentration of the particulate species
employed. The materials prepared via this process are also referred
to as Pickering Emulsions and are described more fully by
Whitesides and Ross (J. Colloid Interface Sci. 169, 48 (1995)). The
uniform droplets may be combined with a suitable binder and coated
on a conductive surface to prepare a device. The process provides
improvement in brightness and contrast over prior art processes. It
also overcomes some of the problems associated with photoinitators
and UV radiation. However, there is still much room for
improvement, particularly in terms of the switching voltage or the
voltage needed to change the orientation of the liquid crystal from
one state to another. The latter has a significant effect on the
overall cost of the display. A low switching voltage is extremely
desirable for low cost displays.
[0006] The device described by U.S. Pat. No. 6,423,368 and U.S. Pat
No. 6,704,073 suffers from drawbacks because of the structure of
the coated layer. Undesirably, there may be more than a monolayer
of droplets between the two electrodes. Furthermore, the process of
coating a heated emulsion of the liquid crystal in a gelatin binder
onto a substrate with a conductive layer and subsequently lowering
the temperature of the coating to change the state of the coated
layer from a free flowing liquid to a gel state (referred to as a
sol-gel transition) prior to drying the coating results in an
extremely uneven distribution of droplets of liquid crystal. At the
microscopic scale there are regions of the coating containing
overlapping droplets and other regions with no droplets at all
between the electrodes. The uneven distribution of droplets results
in a decrease in contrast and an increase in switching voltage.
[0007] U.S. Pat. No. 6,271,898 and U.S. Pat. No. 5,835,174 also
describe compositions suitable for flexible display applications
that employ very uniform sized droplets of liquid crystal in a
polymer binder. However, no attempt is made to control the
thickness or the distribution of droplets in the coated layer
resulting in less than optimum performance.
[0008] U.S. patent application Ser. No. 10/718,900 shows that the
maximum contrast in a bistable chiral nematic liquid crystal
display prepared by the limited coalescence method is obtained when
the uniform liquid crystal domains or droplets are coated as
substantially a monolayer on the first conductive support. The
bistable states in these chiral nematic liquid crystal displays are
the planar reflecting state and the weakly scattering focal conic
state. Back-scattering of light from the weakly scattering focal
conic state increases drastically when there is more than a
monolayer of droplets between the conductive surfaces. While the
method provides displays with an improvement in brightness and
contrast, it still falls short of optimum performance because the
gelatin binder is made to undergo a sol-gel transition prior to
drying of the coating resulting in an uneven structure.
[0009] Rudhardt et al. (Applied Physics Letters vol. 82, page 2610,
2003) describe a method of fabricating a light modulating device
wherein a composition containing very uniform droplets of liquid
crystal in an aqueous solution of polymer binder is spread on an
indium tin oxide (ITO) coated glass surface and the water allowed
to evaporate. The droplets of liquid crystal spontaneously
self-assemble into a hexagonal close-packed (HCP) monolayer. A
second ITO coated glass surface is placed over the coated layer of
droplets as the top electrode to complete construction of the
device. A uniform monolayer thickness is achieved for the coated
layer and the close-packed distribution of droplets is also
extremely well defined. Both features result in a low switching
voltage. However, there are numerous problems with this approach.
Firstly, the uniform droplets of liquid crystal are prepared by
extrusion through a thin capillary into a flowing fluid. When a
droplet at the tip of the capillary grows to reach critical size,
viscous drag exceeds surface tension and breakoff occurs, producing
highly monodisperse emulsions. Clearly, this method of creating one
droplet at a time is not suitable for large scale manufacture.
Secondly, the method by which the second (top) electrode is applied
may be suitable for construction of small scale displays on rigid
substrates such as glass but is not viable for large area low cost
displays on flexible substrates.
[0010] US 2003/0137717A1 and US 2004/0217929A1 indicate that a
close-packed monolayer of droplets of the light modulating
component may be desirable for obtaining high brightness and
contrast in a polymer dispersed electrophoretic display. However
the method of making droplets described in these applications is a
standard emulsification process that does not result in emulsions
having a narrow size distribution that is desirable for obtaining
close-packed monolayers by spontaneous self-assembly. The preferred
method of preparing droplets in US 2003/0137717A1 and US
2004/0217929A1 also involves encapsulation resulting in droplets or
capsules in the size range of 20 to 200 microns with wall thickness
of 0.2 to 10 microns. The relatively large droplet size and wall
thickness result in high switching voltages. The latter is
particularly a problem for bistable CLC devices. Encapsulation is
clearly not desirable but these applications do not teach how a
second conducting layer is to be applied on top of the coated layer
of droplets in the absence of encapsulation. In the absence of
encapsulation, droplets of the light modulating component may
directly come in contact with the organic solvent in the screen
printed conducting ink leading to contamination or poisoning of the
light modulating component. This is particularly a concern if the
light modulating component is a liquid crystal material.
[0011] To overcome the difficulties of US 2003/0137717A1 and US
2004/0217929A1, US 2004/0226820A1 teaches that a close-packed
monolayer of droplets may be obtained by using electro-deposition
followed by washing after the droplets have been spread on a
suitable surface using a coating knife or coating head such as a
slot die coating head. However, the additional steps of
electro-deposition and washing are cumbersome and not suitable for
manufacturing on a large scale. Even with these additional steps, a
close-packed monolayer of uniform thickness is not achieved. The
root mean square (RMS) surface roughness is about 6 microns because
of non-uniform droplets or capsules. This is a very high value of
surface roughness that would result in irregular or incomplete
curing if a UV curable screen printed conducive ink is used as the
second electrode. The irregular curing will result in increased
switching voltages. Furthermore, a surface roughness of this
magnitude will also result in significant non-uniformity of
switching voltage across the area of the display since the
switching voltage is directly related to the thickness of the
coated layer.
[0012] US 2003/0137717A1, US 2004/0217929A1 and US 2004/0226820A1
also teach using polymer latex as the preferred binder. The use of
polymer latex materials is not desirable for a number of reasons.
Many commercial latex materials contain high boiling organic
co-solvents that render them unsuitable for use in PDLC films due
to the poisoning effect the solvents have on the liquid crystal or
other light modulating component. This is particularly true if the
droplets are not encapsulated as is desirable from the point of
view of reduced switching voltage. Latex polymers also have an
affinity for the liquid crystal or other light modulating component
leading to dissolution of the light modulating component into the
polymer matrix. Furthermore, if the latex is not fully transparent,
it can lead to a loss of contrast. Other binders suggested in US
2004/0217929A1 such as acrylics or polyvinylalcohol are difficult
to fix or cross-link if used alone. Fixing or cross-linking is
desired in order to preserve the close-packed monolayer structure
when other layers are spread over it.
[0013] For these reasons, an alternative approach is clearly
needed.
PROBLEM TO BE SOLVED
[0014] There remains a need for a reduced cost, display having
excellent brightness, high contrast, and low switching voltage.
SUMMARY OF THE INVENTION
[0015] The present invention relates to a high contrast reflective
display comprising at least one substrate, at least one
electrically conductive layer and at least one close-packed,
ordered monolayer of domains of electrically modulated material in
a fixed polymer matrix and a method of making the same.
ADVANTAGEOUS EFFECT OF THE INVENTION
[0016] The present invention includes several advantages, not all
of which are incorporated in a single embodiment. A display
according to the present invention would be low cost and require
low switching voltage. In the case of a cholesteric or chiral
nematic liquid crystal display, the resulting display is expected
to have reflectance closer to the theoretical limit of 50% and
higher contrast.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 represents the diffraction pattern caused by
Fraunhofer diffraction of light indicating a close-packed ordered
monolayer of chiral nematic liquid crystal (CLC) droplets (or
droplets of the light modulating material) in the coating of the
invention.
[0018] FIG. 2 represents the diffraction pattern by Fraunhofer
diffraction of light indicating a very disordered coating of the
CLC droplets, according to the prior art.
[0019] FIG. 3 illustrates the electro-optic response of a display
device based on one embodiment of the method of the invention.
[0020] FIG. 4 illustrates the electro-optic response of a display
device based on the method of the prior art.
[0021] FIG. 5 illustrates the electro-optic response of a display
device based on a second embodiment of the method of the
invention.
[0022] FIG. 6 illustrates a display based on one embodiment of the
invention.
[0023] FIG. 7 illustrates a display based on a second embodiment of
the invention.
[0024] FIG. 8 illustrates a typical response of a bistable
cholesteric or chiral nematic liquid crystal material to voltage
pulses.
[0025] FIG. 9 illustrates the uniformity of the surface of the
coated layer of the light modulating component prepared according
to the method of the invention.
[0026] FIG. 10 illustrates fixing the architecture of the coated
layer of the light modulating component of uniform thickness
according to the method of the invention.
[0027] FIG. 11 illustrates the electro-optic response of a display
device using polymer latex as binder in the imaging layer.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The present invention relates to a high contrast reflective
display comprising at least one substrate, at least one
electrically conductive layer and at least one close-packed,
ordered monolayer of domains of electrically modulated material in
a fixed, preferably crosslinked, polymer matrix and a method of
making the same. In the preferred embodiment, the electrically
modulated material is a chiral nematic liquid crystal incorporated
in a polymer matrix. Chiral nematic liquid crystalline materials
may be used to create electronic displays that are both bistable
and viewable under ambient lighting. Furthermore, the liquid
crystalline materials may be dispersed as micron sized droplets in
an aqueous medium, mixed with a suitable binder material and coated
on a flexible conductive support to create potentially low cost
displays. The operation of these displays is dependent on the
contrast between the planar reflecting state and the weakly
scattering focal conic state. In order to derive the maximum
contrast from these displays, it is desired that the chiral nematic
liquid crystal domains or droplets are spread on a conductive
support as a close-packed ordered monolayer. It is possible to
prepare such an ordered monolayer by first applying an aqueous
dispersion of chiral nematic liquid crystal domains to the
substrate in the presence of a suitable binder, allowing the
domains or droplets to self-assemble into a close-packed ordered
monolayer, preferably a hexagonal close-packed (HCP) monolayer and
then allowing the binder material to set, become fixed or crosslink
to preserve the close-packed ordered monolayer structure so that
other aqueous layers can be spread above the imaging layer without
affecting the close-packed structure.
[0029] In general, the light modulating imaging layer contains
electrically modulated material domains dispersed in a binder. For
purposes of the present invention domains are defined to be
synonymous with micelles and/or droplets. The electrically
modulated material may be electrochromic material, rotatable
microencapsulated microspheres, liquid crystal materials,
cholesteric/chiral nematic liquid crystal materials, polymer
dispersed liquid crystals (PDLC), polymer stabilized liquid
crystals, surface stabilized liquid crystals, smectic liquid
crystals, ferroelectric material, electroluminescent material or
any other of a very large number of light modulating imaging
materials known in the prior art. The domains of the electrically
modulated imaging layer include droplets having uniform domain
size, with few, if any, parasitic domains, which are domains with
random or uncontrolled sizes and which have undesirable
electro-optical properties, within the dried coatings, as described
in previous patent art.
[0030] The display includes a suitable electrically modulated
material disposed on a suitable support structure, such as on or
between one or more electrodes. The term "electrically modulated
material" as used herein is intended to include any suitable
nonvolatile material. Suitable materials for the electrically
modulated material are described in U.S. patent application Ser.
No. 09/393,553 and U.S. Provisional Patent Application Ser. No.
60/099,888, the contents of both applications are herein
incorporated by reference.
[0031] The electrically modulated material may also be an
arrangement of particles or microscopic containers or
microcapsules. Each microcapsule contains an electrophoretic
composition of a fluid, such as a dielectric or emulsion fluid, and
a suspension of colored or charged particles or colloidal material.
According to one practice, the particles visually contrast with the
dielectric fluid. According to another example, the electrically
modulated material may include rotatable balls that can rotate to
expose a different colored surface area, and which can migrate
between a forward viewing position and/or a rear nonviewing
position, such as gyricon. Specifically, gyricon is a material
comprised of twisting rotating elements contained in liquid filled
spherical cavities and embedded in an elastomer medium. The
rotating elements may be made to exhibit changes in optical
properties by the imposition of an external electric field. Upon
application of an electric field of a given polarity, one segment
of a rotating element rotates toward, and is visible by an observer
of the display. Application of an electric field of opposite
polarity, causes the element to rotate and expose a second,
different segment to the observer. A gyricon display maintains a
given configuration until an electric field is actively applied to
the display assembly. Gyricon materials are disclosed in U.S. Pat.
No. 6,147,791, U.S. Pat. No. 4,126,854 and U.S. Pat. No. 6,055,091,
the contents of which are herein incorporated by reference.
[0032] According to one practice, the microcapsules may be filled
with electrically charged white particles in a black or colored
dye. Examples of electrically modulated material suitable for use
with the present invention are set forth in International Patent
Application Publication Number WO 98/41899, International Patent
Application Publication Number WO 98/19208, International Patent
Application Publication Number WO 98/03896, and International
Patent Application Publication Number WO 98/41898, the contents of
which are herein incorporated by reference.
[0033] The electrically modulated material may also include
material disclosed in U.S. Pat. No. 6,025,896, the contents of
which are incorporated herein by reference. This material comprises
charged particles in a liquid dispersion medium encapsulated in a
large number of microcapsules. The charged particles can have
different types of color and charge polarity. For example white
positively charged particles can be employed along with black
negatively charged particles. The described microcapsules are
disposed between a pair of electrodes, such that a desired image is
formed and displayed by the material by varying the dispersion
state of the charged particles. The dispersion state of the charged
particles is varied through a controlled electric field applied to
the electrically modulated material.
[0034] Further, the electrically modulated material may include a
thermochromic material. A thermochromic material is capable of
changing its state alternately between transparent and opaque upon
the application of heat. In this manner, a thermochromic imaging
material develops images through the application of heat at
specific pixel locations in order to form an image. The
thermochromic imaging material retains a particular image until
heat is again applied to the material. Since the rewritable
material is transparent, UV fluorescent printings, designs and
patterns underneath can be seen through.
[0035] The electrically modulated material may also include surface
stabilized ferrroelectric liquid crystals (SSFLC). Surface
stabilized ferroelectric liquid crystals confining ferroelectric
liquid crystal material between closely spaced glass plates to
suppress the natural helix configuration of the crystals. The cells
switch rapidly between two optically distinct, stable states simply
by alternating the sign of an applied electric field.
[0036] Magnetic particles suspended in an emulsion comprise an
additional imaging material suitable for use with the present
invention. Application of a magnetic force alters pixels formed
with the magnetic particles in order to create, update or change
human and/or machine readable indicia. Those skilled in the art
will recognize that a variety of bistable nonvolatile imaging
materials are available and may be implemented in the present
invention.
[0037] The electrically modulated material may also be configured
as a single color, such as black, white or clear, and may be
fluorescent, iridescent, bioluminescent, incandescent, ultraviolet,
infrared, or may include a wavelength specific radiation absorbing
or emitting material. There may be multiple layers of electrically
modulated material. Different layers or regions of the electrically
modulated material may have different properties or colors.
Moreover, the characteristics of the various layers may be
different from each other. For example, one layer can be used to
view or display information in the visible light range, while a
second layer responds to or emits ultraviolet light. The nonvisible
layers may alternatively be constructed of nonelectrically
modulated material based materials that have the previously listed
radiation absorbing or emitting characteristics. The electrically
modulated material employed in connection with the present
invention preferably has the characteristic that it does not
require power to maintain display of indicia.
[0038] The most preferred electrically modulated material is a
light modulating material, such as a liquid crystalline material.
The liquid crystalline material can be one of many different liquid
crystal phases such as; nematic (N), chiral nematic (N*), or
smectic, depending upon the arrangement of the molecules in the
mesophase. Chiral nematic liquid crystal (N*LC) displays are
preferably reflective, that is, no backlight is needed, and can
function without the use of polarizing films or a color filter.
[0039] Chiral nematic liquid crystal refers to the type of liquid
crystal having finer pitch than that of twisted nematic and super
twisted nematic used in commonly encountered liquid crystal
devices. Chiral nematic liquid crystals are so named because such
liquid crystal formulations are commonly obtained by adding chiral
agents to host nematic liquid crystals. Chiral nematic liquid
crystals may be used to produce bistable or multi-stable displays.
These devices have significantly reduced power consumption due to
their nonvolatile "memory" characteristic. Since such displays do
not require a continuous driving circuit to maintain an image, they
consume significantly reduced power. Chiral nematic displays are
bistable in the absence of a field, the two stable textures are the
reflective planar texture and the weakly scattering focal conic
texture. In the planar texture, the helical axes of the chiral
nematic liquid crystal molecules are substantially perpendicular to
the substrate upon which the liquid crystal is disposed. In the
focal conic state the helical axes of the liquid crystal molecules
are generally randomly oriented. Adjusting the concentration of
chiral dopants in the chiral nematic material modulates the pitch
length of the mesophase and, thus, the wavelength of radiation
reflected. Chiral nematic materials that reflect infrared radiation
and ultraviolet have been used for purposes of scientific study.
Commercial displays are most often fabricated from chiral nematic
materials that reflect visible light. Some known LCD devices
include chemically etched, transparent, conductive layers overlying
a glass substrate as described in U.S. Pat. No. 5,667,853,
incorporated herein by reference. Suitable chiral nematic liquid
crystal compositions preferably have a positive dielectric
anisotropy and include chiral material in an amount effective to
form focal conic and twisted planar textures. Chiral nematic liquid
crystal materials are preferred because of their excellent
reflective characteristics, bistability and gray scale memory.
[0040] Modern chiral nematic liquid crystal materials usually
include at least one nematic host combined with a chiral dopant. In
general, the nematic liquid crystal phase is composed of one or
more mesogenic components combined to provide useful composite
properties. The nematic component of the chiral nematic liquid
crystal mixture may be comprised of any suitable nematic liquid
crystal mixture or composition having appropriate liquid crystal
characteristics. Nematic liquid crystals suitable for use in the
present invention are preferably composed of compounds of low
molecular weight selected from nematic or nematogenic substances,
for example from the known classes of the azoxybenzenes,
benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl
benzoates, phenyl or cyclohexyl esters of cyclohexanecarboxylic
acid, phenyl or cyclohexyl esters of cyclohexylbenzoic acid, phenyl
or cyclohexyl esters of cyclohexylcyclohexanecarboxylic acid,
cyclohexylphenyl esters of benzoic acid, of cyclohexanecarboxyiic
acid and of cyclohexylcyclohexanecarboxylic acid, phenyl
cyclohexanes, cyclohexyibiphenyls, phenyl cyclohexylcyclohexanes,
cyclohexylcyclohexanes, cyclohexylcyclohexenes,
cyclohexylcyclohexylcyclohexenes, 1,4-bis-cyclohexylbenzenes,
4,4-bis-cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines,
phenyl- or cyclohexylpyridines, phenyl- or cyclohexylpyridazines,
phenyl- or cyclohexyidioxanes, phenyl- or cyclohexyl-1,3-dithianes,
1,2-diphenylethanes, 1,2-dicyclohexylethanes,
1-phenyl-2-cyclohexylethanes,
1-cyclohexyl-2-(4-phenylcyclohexyl)ethanes,
1-cyclohexyl-2',2-biphenylethanes,
1-phenyl-2-cyclohexylphenylethanes, optionally halogenated
stilbenes, benzyl phenyl ethers, tolanes, substituted cinnamic
acids and esters, and further classes of nematic or nematogenic
substances. The 1,4-phenylene groups in these compounds may also be
laterally mono- or difluorinated. The liquid crystalline material
of this preferred embodiment is based on the achiral compounds of
this type. The most important compounds, that are possible as
components of these liquid crystalline materials, can be
characterized by the following formula R'--X--Y-Z-R'' wherein X and
Z, which may be identical or different, are in each case,
independently from one another, a bivalent radical from the group
formed by -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -Pyr-,
-Dio-, --B-Phe- and --B-Cyc-, wherein Phe is unsubstituted or
fluorine-substituted 1,4-phenylene, Cyc is trans-1,4-cyclohexylene
or 1,4-cyclohexenylene, Pyr is pyrimidine-2,5-diyl or
pyridine-2,5-diyl, Dio is 1,3-dioxane-2,5-diyl, and B is
2-(trans-1,4-cyclohexyl)ethyl, pyrimidine-2,5-diyl,
pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl. Y in these compounds is
selected from the following bivalent groups --CH.dbd.CH--,
--C.ident.C--, --N.dbd.N(O)--, --CH.dbd.CY'--, --CH.dbd.N(O)--,
--CH2-CH2-, --CO--O--, --CH2-O--, --CO--S--, --CH2-S--,
--COO-Phe-COO-- or a single bond, with Y' being halogen, preferably
chlorine, or --CN, R' and R'' are, in each case, independently of
one another, alkyl, alkenyl, alkoxy, alkenyloxy, alkanoyloxy,
alkoxycarbonyl or alkoxycarbonyloxy with 1 to 18, preferably 1 to
12 C atoms, or alternatively one of R' and R'' is --F, --CF3,
--OCF3, --Cl, --NCS or --CN. In most of these compounds R' and R'
are, in each case, independently of each another, alkyl, alkenyl or
alkoxy with different chain length, wherein the sum of C atoms in
nematic media generally is between 2 and 9, preferably between 2
and 7. The nematic liquid crystal phases typically consist of 2 to
20, preferably 2 to 15 components. The above list of materials is
not intended to be exhaustive or limiting. The lists disclose a
variety of representative materials suitable for use or mixtures,
which comprise the active element in light modulating liquid
crystal compositions. Chiral nematic liquid crystal materials and
cells, as well as polymer stabilized chiral nematic liquid crystals
and cells, are well known in the art and described in, for example,
U.S. patent application Ser. No. 07/969,093, Ser. No. 08/057,662,
Yang et al., Appl. Phys. Lett. 60(25) pp 3102-04 (1992), Yang et
al., J. Appl. Phys. 76(2) pp 1331 (1994), published International
Patent Application No. PCT/US92/09367, and published International
Patent Application No. PCT/US92/03504, all of which are
incorporated herein by reference.
[0041] Suitable commercial nematic liquid crystals include, for
example, E7, E44, E48, E31, E80, BL087, BL101, ZLI-3308, ZLI-3273,
ZLI-5048-000, ZLI-5049-100, ZLI-5100-100, ZLI-5800-000,
MLC-6041-100.TL202, TL203, TL204 and TL205 manufactured by E. Merck
(Darmstadt, Germany). Although nematic liquid crystals having
positive dielectric anisotropy, and especially cyanobiphenyls, are
preferred, virtually any nematic liquid crystal known in the art,
including those having negative dielectric anisotropy should be
suitable for use in the invention. Other nematic materials may also
be suitable for use in the present invention as would be
appreciated by those skilled in the art.
[0042] The chiral dopant added to the nematic mixture to induce the
helical twisting of the mesophase, thereby allowing reflection of
visible light, can be of any useful structural class. The choice of
dopant depends upon several characteristics including among others
its chemical compatibility with the nematic host, helical twisting
power, temperature sensitivity, and light fastness. Many chiral
dopant classes are known in the art: for example, G. Gottarelli and
G. Spada, Mol. Cryst. Liq. Crys., 123, 377 (1985), G. Spada and G.
Proni, Enantiomer, 3, 301 (1998) and references therein. Typical
well known dopant classes include 1,1-binaphthol derivatives,
isosorbide and similar isomannide esters as disclosed in U.S. Pat.
No. 6,217,792, TADDOL derivatives as disclosed in U.S. Pat. No.
6,099,751, and the pending spiroindanes esters as disclosed in U.S.
patent application Ser. No. 10/651,692 by T. Welter et al., filed
Aug. 29, 2003, titled "Chiral Compounds And Compositions Containing
The Same," hereby incorporated by reference.
[0043] The pitch length of the liquid crystal materials may be
adjusted based upon the following equation (1):
.lamda..sub.nm=n.sub.avp.sub.0 where .lamda..sub.max is the peak
reflection wavelength, that is, the wavelength at which reflectance
is a maximum, n.sub.av is the average index of refraction of the
liquid crystal material, and p.sub.0 is the natural pitch length of
the chiral nematic helix. Definitions of chiral nematic helix and
pitch length and methods of its measurement, are known to those
skilled in the art such as can be found in the book, Blinov, L. M.,
Electro-optical and Magneto-Optical Properties of Liquid Crystals,
John Wiley & Sons Ltd. 1983. The pitch length is modified by
adjusting the concentration of the chiral material in the liquid
crystal material. For most concentrations of chiral dopants, the
pitch length induced by the dopant is inversely proportional to the
concentration of the dopant. The proportionality constant is given
by the following equation (2): p.sub.0=1/(HTP.c) where c is the
concentration of the chiral dopant and HTP is the proportionality
constant.
[0044] For some applications, it is desired to have liquid crystal
mixtures that exhibit a strong helical twist and thereby a short
pitch length. For example in liquid crystalline mixtures that are
used in selectively reflecting chiral nematic displays, the pitch
has to be selected such that the maximum of the wavelength
reflected by the chiral nematic helix is in the range of visible
light. Other possible applications are polymer films with a chiral
liquid crystalline phase for optical elements, such as chiral
nematic broadband polarizers, filter arrays, or chiral liquid
crystalline retardation films. Among these are active and passive
optical elements or color filters and liquid crystal displays, for
example STN, TN, AMD-TN, temperature compensation, polymer free or
polymer stabilized chiral nematic texture (PFCT, PSCT) displays.
Possible display industry applications include ultralight,
flexible, and inexpensive displays for notebook and desktop
computers, instrument panels, video game machines, videophones,
mobile phones, hand held PCs, PDAs, e-books, camcorders, satellite
navigation systems, store and supermarket pricing systems, highway
signs, informational displays, smart cards, toys, and other
electronic devices.
[0045] The liquid crystalline droplets or domains are typically
dispersed in a continuous binder. In one embodiment, a chiral
nematic liquid crystal composition may be dispersed in a continuous
polymeric matrix. Such materials are referred to as "polymer
dispersed liquid crystal" materials or "PDLC" materials. Suitable
hydrophilic binders include both naturally occurring substances
such as proteins, protein derivatives, cellulose derivatives (for
example cellulose esters), gelatins and gelatin derivatives,
polysaccaharides, casein, and the like, and synthetic water
permeable colloids such as poly(vinyl lactams), acrylamide
polymers, latex, poly(vinyl alcohol) and its derivatives,
hydrolyzed polyvinyl acetates, polymers of alkyl and sulfoalkyl
acrylates and methacrylates, polyamides, polyvinyl pyridine,
acrylic acid polymers, maleic anhydride copolymers, polyalkylene
oxide, methacrylamide copolymers, polyvinyl oxazolidinones, maleic
acid copolymers, vinyl amine copolymers, methacrylic acid
copolymers, acryloyloxyalkyl acrylate and methacrylates, vinyl
imidazole copolymers, vinyl sulfide copolymers, and homopolymer or
copolymers containing styrene sulfonic acid. Gelatin is
preferred.
[0046] Gelatin is derived from a material called collagen. Collagen
has a high content of glycine and of the imino acids proline and
hydroxyproline. It has a triple helix structure made up of three
parallel chains. When collagen in water is heated above a certain
temperature, it will denature to form gelatin. Concentrated gelatin
solutions form rigid gels when cooled. This phenomenon is known as
sol-gel transition or thermal gelation and is the result of
secondary bonding, such as hydrogen bonding, between gelatin
molecules in solution. It should be noted that this property is not
limited to gelatin; for example, aqueous solutions of agar, a
polysaccharide from seaweed, will also form rigid gels upon
cooling. Partial renaturation of gelatin also occurs upon cooling.
The latter refers to the formation of triple helix collagen-like
structures. The structures do not form if gelatin is not chill set
prior to drying. In other words, molecules of gelatin remain in a
random coil configuration if the coating is dried at a temperature
that is above the sol-gel transition temperature. The presence of
helix structures may be detected by x-ray diffraction. Chill set
gelatin containing molecules in a helix configuration has
relatively low solubility in cold water and organic solvents
compared to the random coil gelatin. This property enables chill
set gelatin to be an effective barrier between the organic solvent
in printed conductive inks and the light modulating material.
[0047] Useful "gelatins," as that term is used generically herein,
include alkali treated gelatin (cattle bone or hide gelatin), acid
treated gelatin (pigskin gelatin), fish skin gelatin and gelatin
derivatives such as acetylated gelatin, and phthalated gelatin. Any
type of gelatin may be used, provided the gelatin has sufficient
molecular weight to allow the crosslinker to crosslink or the
fixative to fix or set. Fish gelatins have lower imino acid content
compared to mammalian gelatins. The sol-gel transition temperature
or thermal gelation temperature or chill set temperature is lower
if the imino acid content is smaller. For example, the chill set
temperature of gelatins derived from deep water fish such as cod,
haddock or pollock is significantly lower than that of cattle
gelatin. Aqueous solutions of these gelatins remain fluid until
about 10.degree. C. whereas solutions of cattle gelatin will gel at
room temperature. Other hydrophilic colloids that can be utilized
alone or in combination with gelatin include dextran, gum arabic,
zein, casein, pectin, collagen derivatives, collodion, agar-agar,
arrowroot, albumin, and the like. Still other useful hydrophilic
colloids are water soluble polyvinyl compounds such as polyvinyl
alcohol, polyacrylamide, poly(vinylpyrrolidone), and the like.
Useful liquid crystal to gelatin ratios should be between 6:1 and
0.5:1 liquid crystal to gelatin, preferably 3:1.
[0048] Other organic binders such as polyvinyl alcohol (PVA) or
polyethylene oxide (PEO) can be used as minor components of the
binder in addition to gelatin. Such compounds are preferably
machine coatable on equipment associated with photographic
films.
[0049] It is desirable that the binder has a low ionic content. The
presence of ions in such a binder hinders the development of an
electrical field across the dispersed liquid crystal material.
Additionally, ions in the binder can migrate in the presence of an
electrical field, chemically damaging the light modulating layer.
The coating thickness, size of the liquid crystal domains, and
concentration of the domains of liquid crystal materials are
designed for optimum optical properties. Heretofore, the dispersion
of liquid crystals is performed using shear mills or other
mechanical separating means to form domains of liquid crystal
within light modulating layer.
[0050] A conventional surfactant can be added to the emulsion to
improve coating of the layer. Surfactants can be of conventional
design, and are provided at a concentration that corresponds to the
critical micelle concentration (CMC) of the solution. A preferred
surfactant is Aerosol OT, commercially available from Cytec
Industries, Inc.
[0051] In a preferred embodiment, the liquid crystal and gelatin
emulsion are coated and dried to optimize the optical properties of
the light modulating layer. In one embodiment, the layer is coated
to provide a final coating containing a substantial monolayer of
N*LC domains. The term "substantial monolayer" is defined by the
Applicants to mean that, in a direction perpendicular to the plane
of the display, there is no more than a single layer of domains
sandwiched between the electrodes over 90% of the area of the
display (or the imaging layer).
[0052] The amount of material needed for a monolayer can be
determined by calculation based on individual domain size.
Furthermore, improved viewing angle and broadband features may be
obtained by appropriate choice of differently doped domains based
on the geometry of the coated droplet and the Bragg reflection
condition.
[0053] The addition of a bacteriostat prevents gelatin degradation
during emulsion storage and during material operation. The gelatin
concentration in the emulsion when coated is preferably between
about 2 and 20 weight percent based on the weight of the emulsion.
In the final emulsion, the liquid crystal material may be dispersed
at 15% concentration in a 5% gelatin aqueous solution.
[0054] A crosslinking agent or hardener may be used to preserve the
architecture of the close-packed monolayer of coated droplets after
it has been formed by self-assembly. Other methods of fixing the
architecture of the close-packed monolayer of domains may also be
used, although crosslinking is preferred. The effects of the
crosslinker may be characterized based on the reaction of certain
amino acid residues in gelatin. For example, the amount of
histadine is typically reduced from about 4 residues per 1000 to
less than 2.5 residues per 1000 upon cross-linking. Also the amount
of hydroxylysine is reduced from about 6.9 residues per 1000 to
less than 5.1 residues per 1000. Many conventional hardeners are
known to crosslink gelatin. Gelatin crosslinking agents (i.e., the
hardener) are included in an amount of at least about 0.01 wt. %
and preferably from about 0.1 to about 10 wt. % based on the weight
of the solid dried gelatin material used (by dried gelatin it is
meant substantially dry gelatin at ambient conditions as for
example obtained from Eastman Gel Co., as compared to swollen
gelatin), and more preferably in the amount of from about 1 to
about 5 percent by weight. More than one gelatin crosslinking agent
can be used if desired. Suitable hardeners may include inorganic,
organic hardeners, such as aldehyde hardeners and olefinic
hardeners. Inorganic hardeners include compounds such as aluminum
salts, especially the sulfate, potassium and ammonium alums,
ammonium zirconium carbonate, chromium salts such as chromium
sulfate and chromium alum, and salts of titanium dioxide, and
zirconium dioxide. Representative organic hardeners or gelatin
crosslinking agents may include aldehyde and related compounds,
pyridiniums, olefins, carbodiimides, and epoxides. Thus, suitable
aldehyde hardeners include formaldehyde and compounds that contain
two or more aldehyde functional groups such as glyoxal,
gluteraldehyde and the like. Other preferred hardeners include
compounds that contain blocked aldehyde functional groups such as
aldehydes of the type
tetrahydro-4-hydroxy-5-methyl-2(1H)-pyrimidinone polymers (Sequa
SUNREZ.RTM. 700), polymers of the type having a glyoxal polyol
reaction product consisting of 1 anhydroglucose unit: 2 glyoxal
units (SEQUAREZ.RTM. 755 obtained from Sequa Chemicals, Inc.),
DME-Melamine non-formaldehyde resins such as Sequa CPD3046-76
obtained from Sequa Chemicals Inc., and 2,3-dihydroxy-1,4-dioxane
(DHD). Thus, hardeners that contain active olefinic functional
groups include, for example, bis-(vinylsulfonyl)-methane (BVSM),
bis-(vinylsulfonyl-methyl) ether (BVSME),
1,3,5-triacryloylhexahydro-s-triazine, and the like. In the context
of the present invention, active olefinic compounds are defined as
compounds having two or more olefinic bonds, especially
unsubstituted vinyl groups, activated by adjacent electron
withdrawing groups (The Theory of the Photographic Process, 4th
Edition, T. H. James, 1977, Macmillan Publishing Co., page 82).
Other examples of hardening agents can be found in standard
references such as The Theory of the Photographic Process, T. H.
James, Macmillan Publishing Co., Inc. (New York 1977) or in
Research Disclosure, September 1996, Vol. 389, Part IIB (Hardeners)
or in Research Disclosure, September 1994, Vol. 365, Item 36544,
Part IIB (Hardeners). Research Disclosure is published by Kenneth
Mason Publications, Ltd., Dudley House, 12 North St., Emsworth,
Hampshire P010 7DQ, England. Olefinic hardeners are most preferred,
as disclosed in U.S. Pat. Nos. 3,689,274, 2,994,611, 3,642,486,
3,490,911, 3,635,718, 3,640,720, 2,992,109, 3,232,763, and
3,360,372.
[0055] Among hardeners of the active olefin type, a preferred class
of hardeners particularly are compounds comprising two or more
vinyl sulfonyl groups. These compounds are hereinafter referred to
as "vinyl sulfones". Compounds of this type are described in
numerous patents including, for example, U.S. Pat. Nos. 3,490,911,
3,642,486, 3,841,872 and 4,171,976. Vinyl sulfone hardeners are
believed to be effective as hardeners as a result of their ability
to crosslink polymers making up the colloid.
[0056] The liquid crystalline droplets or domains may be formed by
any method, known to those of skill in the art, which will allow
control of the domain size. For example, Doane et al. (Applied
Physics Letters, 48, 269 (1986)) disclose a PDLC comprising
approximately 0.4 .mu.m droplets of nematic liquid crystal 5CB in a
polymer binder. A phase separation method is used for preparing the
PDLC. A solution containing monomer and liquid crystal is filled in
a display cell and the material is then polymerized. Upon
polymerization the liquid crystal becomes immiscible and nucleates
to form droplets. West et al. (Applied Physics Letters 63, 1471
(1993)) disclose a PDLC comprising a chiral nematic mixture in a
polymer binder. Once again a phase separation method is used for
preparing the PDLC. The liquid crystal material and polymer (a
hydroxy functionalized polymethylmethacrylate) along with a
crosslinker for the polymer are dissolved in a common organic
solvent toluene and coated on an indium tin oxide (ITO) substrate.
A dispersion of the liquid crystal material in the polymer binder
is formed upon evaporation of toluene at high temperature. The
phase separation methods of Doane et al. and West et al. require
the use of organic solvents that may be objectionable in certain
manufacturing environments.
[0057] In a preferred embodiment, a method referred to as "limited
coalescence" is used to form uniformly sized emulsions of liquid
crystalline material. For example, the liquid crystal material can
be homogenized in the presence of finely divided silica, a
coalescence limiting material, such as LUDOX.RTM. from DuPont
Corporation. A promoter material can be added to the aqueous bath
to drive the colloidal particles to the liquid-liquid interface. In
a preferred embodiment, a copolymer of adipic acid and
2-(methylamino)ethanol can be used as the promoting agent in the
water bath. The liquid crystal material can be dispersed using
ultrasound to create liquid crystal domains below 1 micron in size.
When the ultrasound energy is removed, the liquid crystal material
coalesces into domains of uniform size. The limited coalescence
process is described more fully by Whitesides and Ross (J. Colloid
Interface Sci. 169, 48 (1995)), by Giermanska-Kahn, Schmitt, Binks
and Leal-Calderon (Langmuir, 18, 2515 (2002)), and U.S. Pat. No.
6,556,262, all incorporated herein by reference.
[0058] The distribution of droplet sizes is such that the
coefficient of variation (cv) defined as the standard deviation of
the distribution divided by the arithmetic mean is less than 0.25,
preferably less than 0.2 and most preferably less than 0.15. The
limited coalescent materials can be coated using a photographic
emulsion coating machine onto sheets of polyester having an ITO
coating with a sheet conductivity of 300 ohms per square. The
coating can be dried to provide a polymerically dispersed
cholesteric coating. By using limited coalescence, there are few,
if any, parasitic smaller domains (having undesirable
electro-optical properties) within the dried coatings.
[0059] The size ranges of domains in the dried coating are varied
as the mixture dries and the domains flatten. In one embodiment,
the resulting domains are flattened by the drying process and have
on average a thickness substantially less than their length. The
flattening of the domains can be achieved by proper formulation and
sufficiently rapid drying of the coating.
[0060] Preferably, the domains are flattened spheres and have on
average a thickness substantially less than their length,
preferably at least 50% less. More preferably, the domains on
average have a thickness (depth) to length ratio of 1:2 to 1:6. The
flattening of the domains can be achieved by proper formulation and
sufficiently rapid drying of the coating. The domains preferably
have an average diameter of 2 to 30 microns. The imaging layer
preferably has a thickness of 10 to 150 microns when first coated
and 2 to 20 microns when dried. Most preferably the imaging layer
or light modulating layer has a thickness between 2 to 6 microns,
particularly if the light modulating material is a chiral nematic
liquid crystal.
[0061] The flattened domains of liquid crystal material can be
defined as having a major axis and a minor axis. In a preferred
embodiment of a display or display sheet, the major axis is larger
in size than the cell (or imaging layer) thickness for a majority
of the domains. Such a dimensional relationship is shown in U.S.
Pat. No. 6,061,107, hereby incorporated by reference in its
entirety.
[0062] In U.S. Pat. No. 3,600,060, incorporated herein by
reference, the domains of the dried light modulating material had
particle size varying in diameter by a ratio of 10:1. This creates
large domains and smaller parasitic domains. Parasitic domains have
reduced characteristics when compared with optimized larger
domains. The reduced characteristics include reduced brightness and
if the parasitic domains are small enough diminished bistability of
the cholesteric liquid crystal.
[0063] The dispersed domains have an average diameter of 2 to 30
microns, preferably 5 to 15 microns. The domains are dispersed in
an aqueous suspension. The size ranges for the dried coating are
varied as the mixture dries and the domains flatten.
[0064] By varying the amount of silica and copolymer relative to
the liquid crystalline material, uniform domain size emulsions of
the desired average diameter (by microscopy), can be produced. This
process produces domains of a selected average diameter.
[0065] The resulting domains are flattened by the drying process
and have on average a thickness substantially less than their
length, preferably at least 50% less. More preferably, the domains
on average have a thickness (depth) to length ratio of 1:2 to
1:10.
[0066] For optimal performance one requires a monolayer of coated
droplets having a close-packed structure of uniform thickness.
Calculations by Yang and Mi (J. Phys. D: Appl. Phys. Vol. 33, page
672, 2000) have shown that for a chiral nematic liquid crystalline
material of a given handedness, maximum reflectance is obtained if
the thickness of the chiral nematic liquid crystal material between
the electrodes is about ten times the pitch of the chiral nematic
helix. For a green reflecting chiral nematic liquid crystal
material with .lamda..sub.max of 550 nm and n.sub.av of 1.6 the
pitch is 344 nm. Therefore, maximum reflectance is obtained for a
3.4 .mu.m thick layer of this material. For chiral nematic liquid
crystal materials that reflect in the red and near infrared
portions of the spectrum, the pitch and therefore the thickness of
the coated layer needed for maximum reflectance will be somewhat
higher but even in these cases a thickness of about 5 .mu.m is
sufficient, if the refractive index is close to 1.6. In other
words, increasing the thickness of the layer beyond this does not
provide an increase in reflectance.
[0067] It is also well documented that the switching voltage
increases linearly with thickness. Since it is desirable to have
the lowest possible switching voltage, a uniform thickness of about
5 .mu.m is most preferred for the coated layer of droplets,
provided the droplets have a close-packed structure. Under certain
conditions, monodisperse droplets of the light modulating material
will spontaneously self-assemble on a surface into a hexagonal
close-packed (HCP) structure. The process has been described in
detail by Denkov et al. (Nature, vol. 361, p. 26, 1993). When an
aqueous suspension of droplets is spread on a surface, the droplets
initially assume a random, disordered or uncorrelated distribution.
However, as a function of drying, when the level of water reaches
the top of the droplets, there is a strong attractive force known
as the capillary force that drives the droplets into a close-packed
ordered or correlated structure. The attractive energy of the
capillary force is much greater than the thermal energy. However,
it is important that lateral movement of droplets is not impeded by
a strong attraction to the surface or by an increase in viscosity
of the medium in which they are suspended. The latter would happen
if the binder is gelatin and the coated layer of droplets is chill
set prior to drying.
[0068] The formation of a close-packed structure in two dimensions,
starting from a random distribution of droplets, is sometimes
referred to as two-dimensional crystallization and should have a
monodisperse population of droplets or a population of droplets
having low polydispersity (Kumacheva et al. Physical Review Letters
vol. 91, page 1283010-1, 2003). A population of droplets of light
modulating material having sufficiently low polydispersity to
create a close-packed structure may be achieved by the limited
coalescence process. The close-packed structure is readily
observable under an optical microscope. Furthermore, the
close-packed structure has a repeat pattern or periodicity wherein
the repeat distance is of the order of the wavelength of visible
light. A coating having such a pattern exhibits Fraunhofer
diffraction when placed before a source of visible light such as a
visible light laser. The phenomenon of Fraunhofer diffraction is
described more fully by Lisensky et al. Journal of Chemical
Education, vol. 68, February 1991.
[0069] For perfectly monodisperse droplets (cv less than 0.1), a
hexagonal close-packed (HCP) structure is obtained. The diffraction
pattern for such a structure is in the form of spots. If there is a
minor level of polydispersity (cv between 0.1 and 0.2), the
diffraction pattern of the close-packed structure is in the form of
a single ring or a set of concentric rings.
[0070] The close-packed monolayer structure of coated droplets may
be preserved by fixing or crosslinking the binder. This allows a
second aqueous layer to be coated above the layer containing the
light modulating material without disturbing the close-packed
organization. In a preferred embodiment, the second layer functions
as a protective overcoat for the light modulating material.
[0071] A preferred embodiment of the display device shown in FIG. 6
comprises a clear flexible support 101 with a clear conducting
layer 102. The imaging layer or light modulating layer (layer 1)
contains a close-packed monolayer of droplets of the light
modulating material 104 along with crosslinked binder 103 in a
random coil configuration. A protective overcoat 105 is composed of
polymer in a helix configuration. The second electrode 106
comprises screen printed carbon conductive ink.
[0072] A second preferred embodiment of the display device, shown
in FIG. 7, comprises a clear flexible support 101 with a clear
conducting layer 102. The imaging layer or light modulating layer
(layer 1) contains a close-packed monolayer of droplets of the
light modulating material 104 along with crosslinked binder 103 in
a random coil configuration. A protective overcoat 107 is composed
of polymer in a helix configuration and dispersed carbon black for
improved contrast. The second electrode 108 comprises screen
printed silver conductive ink.
[0073] In addition to binder and hardener, liquid crystal layers
may also contain a small amount of light absorbing colorant,
preferably an absorber dye. It is preferred that an absorbing dye
is used to selectively absorb back scattered light from the focal
conic state at the lowest wavelengths in the visible part of the
spectrum. Further, the colorant selectively absorbs similarly
scattered light from the planar state, while only minimally
absorbing the main body of reflected light. The colorants may
include both dyes and pigments. The colorant may absorb light
components, which may cause turbidity of color in the color display
performed by selective reflection of the liquid crystal or may
cause lowering of a transparency in the transparent state of the
liquid crystal, and therefore can improve the display quality. Two
or more of the components in the liquid crystal display may contain
a coloring agent. For example, both the polymer and the liquid
crystal may contain the coloring agent. Preferably, a colorant is
selected, which absorbs rays in a range of shorter wavelengths than
the selective reflection wavelength of the liquid crystal.
[0074] Any amount of colorant may be used, provided that addition
of the colorant does not remarkably impair the switching
characteristics of the liquid crystal material for display. In
addition, if the polymeric binder is formed by polymerization, the
addition does not inhibit the polymerization. An exemplary amount
of colorant is from at least 0.1 weight % to 5 weight % of the
liquid crystal material.
[0075] In a preferred embodiment, the colorants, preferably
absorber dyes, are incorporated directly in the chiral nematic
liquid crystal materials. Any colorants that are miscible with the
cholesteric liquid crystal materials are useful for this purpose.
Most preferred are colorants that are readily soluble in toluene.
By readily soluble is meant a solubility greater than 1 gram per
liter, more preferably greater than 10 grams per liter and most
preferably greater than 100 grams per liter. Toluene soluble dyes
most compatible with the cholesteric liquid crystal materials are
anthraquinone dyes such as Sandoplast Blue 2B from Clariant
Corporation, phthalocyanine dyes such as Savinyl Blue GLS from
Clariant Corporation or Neozapon Blue 807 from BASF Corporation,
methine dyes such as Sandoplast Yellow 3G from Clariant Corporation
or metal complex dyes such as Neozapon Yellow 157, Neozapon Orange
251, Neozapon Green 975, Neozapon Blue 807 or Neozapon Red 365 from
BASF Corporation. Other colorants are Neopen Blue 808, Neopen
Yellow 075, Sudan Orange 220 or Sudan Blue 670 from BASF
Corporation. Other types of colorants may include various kinds of
dyestuff such as dyestuff for resin coloring and dichromatic
dyestuff for liquid crystal display. The dyestuff for resin
coloring may be SPR RED 1 (manufactured by Mitsui Toatsu Senryo
Co., Ltd.). The dichromatic dyestuff for liquid crystal is
specifically SI-424 or M-483 (both manufactured by Mitsui Toatsu
Senryo Co., Ltd.).
[0076] Another aspect of the present invention relates to a display
sheet comprising a substrate, an electrically conductive layer
formed over the substrate, and a liquid crystal containing imaging
layer comprising a chiral nematic material formed by the above
described methods disposed over the electrically conductive
layer.
[0077] As used herein, the phrase a "liquid crystal display" (LCD)
is a type of flat panel display used in various electronic devices.
At a minimum, a LCD comprises a substrate, at least one conductive
layer and a liquid crystal layer. LCDs may also comprise two sheets
of polarizing material with a liquid crystal solution between the
polarizing sheets. The sheets of polarizing material may comprise a
substrate of glass or transparent plastic. The LCD may also include
functional layers. In one embodiment of a LCD, a transparent,
multilayer flexible support is coated with a first conductive
layer, which may be patterned, onto which is coated the light
modulating liquid crystal layer. A second conductive layer is
applied and overcoated with a dielectric layer to which dielectric
conductive row contacts are attached, including via holes that
permit interconnection between conductive layers and the dielectric
conductive row contacts. An optional nanopigmented functional layer
may be applied between the liquid crystal layer and the second
conductive layer.
[0078] The liquid crystal (LC) is used as an optical switch. The
substrates are usually manufactured with transparent, conductive
electrodes, in which electrical "driving" signals are coupled. The
driving signals induce an electric field which can cause a phase
change or state change in the liquid crystal material, thus
exhibiting different light reflecting characteristics according to
its phase and/or state.
[0079] Cholesteric liquid crystals are bistable at zero field and
drive schemes may be designed based on their response to voltage
pulses. A typical response of a bistable cholesteric or chiral
nematic liquid crystal material to voltage pulses is shown in FIG.
8. The horizontal axis represents the amplitude of the addressing
voltage pulse and the vertical axis represents the reflectance
measured after the liquid crystal relaxes to the stable state
following application of the voltage pulse. The solid line is the
response, when the material is initially in the planar state or
texture, and the dashed line is the response, when the material is
initially in the focal conic texture. In the conventional drive
scheme for bistable cholesteric displays, the displays are
addressed row by row. With reference to FIG. 8, if the row voltage
VR is set at VR=(V3+V4)/2, then the column voltage VC has to be
within the range V4-VR<VC<V1 for all columns in order to
derive maximum contrast without cross-talk in a matrix or
multiplexed display. By without cross-talk, it is meant that the
portion of the image that has already been written on a multi-row
display device will not be altered when a new row is selected and
addressed. From the above relationships, it follows that for
maximum contrast without cross-talk, (V4-V3)/2<V1. If we define
a quantity Vqm=2V1/(V4-V3), it is clearly desirable that Vqm is
greater than or at least equal to 1.
[0080] The displays may employ any suitable driving schemes and
electronics known to those skilled in the art, including the
following, all of which are incorporated herein by reference in
their entireties: Doane, J. W., Yang, D. K., Front--lit Flat Panel
Display from Polymer Stabilized Cholesteric Textures, Japan Display
92, Hiroshima October 1992; Yang, D. K. and Doane, J. W.,
Cholesteric Liquid Crystal/Polymer Gel Dispersion: Reflective
Display Application, SID Technical Paper Digest, Vol XXIII, May
1992, p. 759, et sea.; U.S. patent application Ser. No. 08/390,068,
filed Feb. 17, 1995, entitled "Dynamic Drive Method and Apparatus
for a Bistable Liquid Crystal Display" and U.S. Pat. No.
5,453,863.
[0081] A typical display in its simplest form comprises a sheet
supporting a conventional polymer dispersed electrically modulated
material. The sheet includes a substrate. Substrate can be made of
a polymeric material, such as Kodak Estar film base formed of
polyester plastic, and have a thickness of between 20 and 200
microns. For example, substrate can be a 80 micron thick sheet of
transparent polyester. Other polymers, such as transparent
polycarbonate, can also be used. Alternatively, substrate can be
thin, transparent glass.
[0082] A first conductor is formed over substrate. First conductor
can be a transparent, electrically conductive layer of tin-oxide or
indium-tin-oxide (ITO), with ITO being the preferred material.
Typically, first conductor is sputtered onto the substrate to a
resistance of less than 250 ohms per square. Alternatively, first
conductor can be an opaque electrical conductor formed of metal
such as copper, aluminum or nickel. If first conductor is an opaque
metal, the metal can be a metal oxide to create a light absorbing
first conductor. A second conductor may be applied to the surface
of light modulating imaging layer. Second conductor should have
sufficient conductivity to carry a field across light modulating
imaging layer. Second conductor can be formed in a vacuum
environment using materials such as aluminum, tin, silver,
platinum, carbon, tungsten, molybdenum, or indium.
[0083] In a preferred embodiment of the invention, the display
device or display sheet has simply a single imaging layer of liquid
crystal material along a line perpendicular to the face of the
display, preferably a single layer coated on a flexible substrate.
Such as structure, as compared to vertically stacked imaging layers
each between opposing substrates, is especially advantageous for
monochrome shelf labels and the like. Structures having stacked
imaging layers, however, are optional for providing additional
advantages in some case.
[0084] In a typical matrix-addressable light emitting display
device, numerous light emitting devices are formed on a single
substrate and arranged in groups in a regular grid pattern.
Activation may be by rows and columns, or in an active matrix with
individual cathode and anode paths. OLEDs are often manufactured by
first depositing a transparent electrode on the substrate, and
patterning the same into electrode portions. The organic layer(s)
is then deposited over the transparent electrode. A metallic
electrode can be formed over the electrode layers. For example, in
U.S. Pat. No. 5,703,436 to Forrest et al., incorporated herein by
reference, transparent indium tin oxide (ITO) is used as the Hole
injecting electrode, and a Mg----Ag-ITO electrode layer is used for
electron injection.
[0085] The flexible plastic substrate can be any flexible
self-supporting plastic film that supports the thin conductive
metallic film. "Plastic" means a high polymer, usually made from
polymeric synthetic resins, which may be combined with other
ingredients, such as curatives, fillers, reinforcing agents,
colorants, and plasticizers. Plastic includes thermoplastic
materials and thermosetting materials.
[0086] The flexible plastic film must have sufficient thickness and
mechanical integrity so as to be self-supporting, yet should not be
so thick as to be rigid. Typically, the flexible plastic substrate
is the thickest layer of the composite film in thickness.
Consequently, the substrate determines to a large extent the
mechanical and thermal stability of the fully structured composite
film.
[0087] Another significant characteristic of the flexible plastic
substrate material is its glass transition temperature (Tg). Tg is
defined as the glass transition temperature at which plastic
material will change from the glassy state to the rubbery state. It
may comprise a range before the material may actually flow.
Suitable materials for the flexible plastic substrate include
thermoplastics of a relatively low glass transition temperature,
for example up to 150.degree. C., as well as materials of a higher
glass transition temperature, for example, above 150.degree. C. The
choice of material for the flexible plastic substrate would depend
on factors such as manufacturing process conditions, such as
deposition temperature, and annealing temperature, as well as post
manufacturing conditions such as in a process line of a displays
manufacturer. Certain of the plastic substrates discussed below can
withstand higher processing temperatures of up to at least about
200.degree. C., some up to 300-350.degree. C., without damage.
[0088] Typically, the flexible plastic substrate is polyethylene
terephthalate (PET), polyethylene naphthalate (PEN),
polyethersulfone (PES), polycarbonate (PC), polysulfone, a phenolic
resin, an epoxy resin, polyester, polyimide, polyetherester,
polyetheramide, cellulose acetate, aliphatic polyurethanes,
polyacrylonitrile, polytetrafluoroethylenes, polyvinylidene
fluorides, poly(methyl (x-methacrylates), an aliphatic or cyclic
polyolefin, polyarylate (PAR), polyetherimide (PEI),
polyethersulphone (PES), polyimide (PI), Teflon
poly(perfluoro-alboxy) fluoropolymer (PFA), poly(ether ether
ketone) (PEEK), poly(ether ketone) (PEK), poly(ethylene
tetrafluoroethylene) fluoropolymer (PETFE), and poly(methyl
methacrylate) and various acrylate/methacrylate copolymers (PMMA).
Aliphatic polyolefins may include high density polyethylene (HDPE),
low density polyethylene (LDPE), and polypropylene, including
oriented polypropylene (OPP). Cyclic polyolefins may include
poly(bis(cyclopentadiene)). A preferred flexible plastic substrate
is a cyclic polyolefin or a polyester. Various cyclic polyolefins
are suitable for the flexible plastic substrate. Examples include
Arton.RTM. made by Japan Synthetic Rubber Co., Tokyo, Japan, Zeanor
T made by Zeon Chemicals L.P., Tokyo Japan, and Topas.RTM. made by
Celanese A. G., Kronberg Germany. Arton is a
poly(bis(cyclopentadiene)) condensate that is a film of a polymer.
Alternatively, the flexible plastic substrate can be a polyester. A
preferred polyester is an aromatic polyester such as Arylite.
Although various examples of plastic substrates are set forth
above, it should be appreciated that the substrate can also be
formed from other materials such as glass and quartz.
[0089] The flexible plastic substrate can be reinforced with a hard
coating. Typically, the hard coating is an acrylic coating. Such a
hard coating typically has a thickness of from 1 to 15 microns,
preferably from 2 to 4 microns and can be provided by free radical
polymerization, initiated either thermally or by ultraviolet
radiation, of an appropriate polymerizable material. Depending on
the substrate, different hard coatings can be used. When the
substrate is polyester or Arton, a particularly preferred hard
coating is the coating known as "Lintec". Lintec contains UV cured
polyester acrylate and colloidal silica. When deposited on Arton,
it has a surface composition of 35 atom % C, 45 atom % 0, and 20
atom % Si, excluding hydrogen. Another particularly preferred hard
coating is the acrylic coating sold under the trademark "Terrapin"
by Tekra Corporation, New Berlin, Wis.
[0090] The LCD contains at least one conductive layer, which
typically is comprised of a primary metal oxide. This conductive
layer may comprise other metal oxides such as indium oxide,
titanium dioxide, cadmium oxide, gallium indium oxide, niobium
pentoxide and tin dioxide. See, Int. Publ. No. WO 99/36261 by
Polaroid Corporation. In addition to the primary oxide such as ITO,
the at least one conductive layer can also comprise a secondary
metal oxide such as an oxide of cerium, titanium, zirconium,
hafnium and/or tantalum. See, U.S. Pat. No. 5,667,853 to Fukuyoshi
et al. (Toppan Printing Co.) Other transparent conductive oxides
include, but are not limited to ZnO.sub.2, Zn.sub.2SnO.sub.4,
Cd.sub.2SnO.sub.4, Zn.sub.2In.sub.2O.sub.5, MgIn.sub.2O.sub.4,
Ga.sub.2O.sub.3--In.sub.20.sub.3, or TaO.sub.3. The conductive
layer may be formed, for example, by a low temperature sputtering
technique or by a direct current sputtering technique, such as DC
sputtering or RF-DC sputtering, depending upon the material or
materials of the underlying layer. The conductive layer may be a
transparent, electrically conductive layer of tin oxide or indium
tin oxide (ITO), or polythiophene (PDOT). Typically, the conductive
layer is sputtered onto the substrate to a resistance of less than
250 ohms per square. Alternatively, conductive layer may be an
opaque electrical conductor formed of metal such as copper,
aluminum or nickel. If the conductive layer is an opaque metal, the
metal can be a metal oxide to create a light absorbing conductive
layer.
[0091] The material is coated over patterned ITO first conductors
to provide a polymer dispersed cholesteric coating having a dried
thickness of less than 50 microns, preferably less than 25 microns,
more preferably less than 15 microns, most preferably less than
about 10 microns.
[0092] Indium tin oxide (ITO) is the preferred conductive material,
as it is a cost effective conductor with good environmental
stability, up to 90% transmission, and down to 20 ohms per square
resistivity. An exemplary preferred ITO layer has a % T greater
than or equal to 80% in the visible region of light, that is, from
greater than 400 nm to 700 nm, so that the film will be useful for
display applications. In a preferred embodiment, the conductive
layer comprises a layer of low temperature ITO, which is
polycrystalline. The ITO layer is preferably 10-120 nm in
thickness, or 50-100 nm thick to achieve a resistivity of 20-60
ohms/square on plastic. An exemplary preferred ITO layer is 60-80
nm thick.
[0093] The conductive layer is preferably patterned. The conductive
layer is preferably patterned into a plurality of electrodes. The
patterned electrodes may be used to form a LCD device. In another
embodiment, two conductive substrates are positioned facing each
other and cholesteric liquid crystals are positioned there between
to form a device. The patterned ITO conductive layer may have a
variety of dimensions. Exemplary dimensions may include line widths
of 10 microns, distances between lines, that is, electrode widths,
of 200 microns, depth of cut, that is, thickness of ITO conductor,
of 100 nanometers. ITO thicknesses on the order of 60, 70, and
greater than 100 nanometers are also possible.
[0094] The display may also contain a second conductive layer
applied to the surface of the light modulating layer. The second
conductive layer desirably has sufficient conductivity to carry a
field across the light modulating layer. The second conductive
layer may be formed in a vacuum environment using materials such as
aluminum, tin, silver, platinum, carbon, tungsten, molybdenum, or
indium. Oxides of these metals can be used to darken patternable
conductive layers. The metal material can be excited by energy from
resistance heating, cathodic arc, electron beam, sputtering or
magnetron excitation. The second conductive layer may comprise
coatings of tin oxide or indium tin oxide, resulting in the layer
being transparent. Alternatively, second conductive layer may be
printed conductive ink.
[0095] For higher conductivities, the second conductive layer may
comprise a silver based layer which contains silver only or silver
containing a different element such as aluminum (Al), copper (Cu),
nickel (Ni), cadmium (Cd), gold (Au), zinc (Zn), magnesium (Mg),
tin (Sn), indium (In), tantalum (Ta), titanium (Ti), zirconium
(Zr), cerium (Ce), silicon (Si), lead (Pb) or palladium (Pd). In a
preferred embodiment, the conductive layer comprises at least one
of gold, silver and a gold/silver alloy, for example, a layer of
silver coated on one or both sides with a thinner layer of gold.
See, Int. Publ. No. WO 99/36261 by Polaroid Corporation. In another
embodiment, the conductive layer may comprise a layer of silver
alloy, for example, a layer of silver coated on one or both sides
with a layer of indium cerium oxide (InCeO). See U.S. Pat. No.
5,667,853, incorporated herein in by reference.
[0096] The second conductive layer may be patterned irradiating the
multilayered conductor/substrate structure with ultraviolet
radiation so that portions of the conductive layer are ablated
therefrom. It is also known to employ an infrared (IR) fiber laser
for patterning a metallic conductive layer overlying a plastic
film, directly ablating the conductive layer by scanning a pattern
over the conductor/film structure. See: Int. Publ. No. WO 99/36261
and "42.2: A New Conductor Structure for Plastic LCD Applications
Utilizing `All Dry` Digital Laser Patterning," 1998 SID
International Symposium Digest of Technical Papers, Anaheim,
Calif., May 17-22, 1998, no. VOL. 29, May 17, 1998, pages
1099-1101, both incorporated herein by reference.
[0097] In a preferred embodiment, second conductors are printed
conductive ink such as ELECTRODAG 423SS screen printable electrical
conductive material from Acheson Corporation. Such printed
materials are finely divided graphite particles in a thermoplastic
resin. The second conductors are formed using printed inks to
reduce display cost. The use of a flexible support for substrate
layer, laser etched first conductors, machine coating polymer
dispersed cholesteric layer, and printing second conductors permit
the fabrication of very low cost memory displays. Small displays
formed using these methods can be used as electronically rewritable
transaction cards for inexpensive, limited rewrite
applications.
[0098] A light absorbing second conductor may be positioned on the
side opposing the incident light. In the fully evolved focal conic
state the cholesteric liquid crystal is transparent, passing
incident light, which is absorbed by second conductor to provide a
black image. Progressive evolution to the focal conic state causes
a viewer to see an initial bright reflected light that transitions
to black as the cholesteric material changes from planar state to a
fully evolved focal conic state. The transition to the light
transmitting state is progressive, and varying the low voltage time
permits variable levels of reflection. These variable levels can be
mapped out to corresponding gray levels, and when the field is
removed, light modulating layer maintains a given optical state
indefinitely. The states are more fully discussed in U.S. Pat. No.
5,437,811.
[0099] In addition to a second conductive layer, other means may be
used to produce a field capable of switching the state of the
liquid crystal layer as described in, for example, U.S. Pat Appl.
Nos. 20010008582 A1, 20030227441 A1, 20010006389 A1, and U.S. Pat.
Nos. 6,424,387, 6,269,225, and 6,104,448, all incorporated herein
by reference.
[0100] The LCD may also comprise at least one "functional layer"
between the conductive layer and the substrate. The functional
layer may comprise a protective layer or a barrier layer. The
protective layer useful in the practice of the invention can be
applied in any of a number of well known techniques, such as dip
coating, rod coating, blade coating, air knife coating, gravure
coating and reverse roll coating, extrusion coating, slide coating,
curtain coating, and the like. The liquid crystal particles and the
binder are preferably mixed together in a liquid medium to form a
coating composition. The liquid medium may be a medium such as
water or other aqueous solutions in which the hydrophilic colloid
are dispersed with or without the presence of surfactants. A
preferred barrier layer may acts as a gas barrier or a moisture
barrier and may comprise SiOx, AlOx or ITO. The protective layer,
for example, an acrylic hard coat, functions to prevent laser light
from penetrating to functional layers between the protective layer
and the substrate, thereby protecting both the barrier layer and
the substrate. The functional layer may also serve as an adhesion
promoter of the conductive layer to the substrate.
[0101] In another embodiment, the polymeric support may further
comprise an antistatic layer to manage unwanted charge build up on
the sheet or web during roll conveyance or sheet finishing. In
another embodiment of this invention, the antistatic layer has a
surface resistivity of between 10.sup.5 to 10.sup.12 ohms. Above
10.sup.12, the antistatic layer typically does not provide
sufficient conduction of charge to prevent charge accumulation to
the point of preventing fog in photographic systems or from
unwanted point switching in liquid crystal displays. While layers
greater than 10.sup.5 will prevent charge buildup, most antistatic
materials are inherently not that conductive and in those materials
that are more conductive than 10.sup.5, there is usually some color
associated with them that will reduce the overall transmission
properties of the display. The antistatic layer is separate from
the highly conductive layer of ITO and provides the best static
control when it is on the opposite side of the web substrate from
that of the ITO layer. This may include the web substrate
itself.
[0102] Another type of functional layer may be a color contrast
layer. Color contrast layers may be radiation reflective layers or
radiation absorbing layers. In some cases, the rearmost substrate
of each display may preferably be painted black. The color contrast
layer may also be other colors. In another embodiment, the dark
layer comprises milled nonconductive pigments. The materials are
milled below 1 micron to form "nanopigments". In a preferred
embodiment, the dark layer absorbs all wavelengths of light across
the visible light spectrum, that is from 400 nanometers to 700
nanometers wavelength. The dark layer may also contain a set or
multiple pigment dispersions. Suitable pigments used in the color
contrast layer may be any colored materials, which are practically
insoluble in the medium in which they are incorporated. Suitable
pigments include those described in Industrial Organic Pigments:
Production, Properties, Applications by W. Herbst and K. Hunger,
1993, Wiley Publishers. These include, but are not limited to, Azo
Pigments such as monoazo yellow and orange, diazo, naphthol,
naphthol reds, azo lakes, benzimidazolone, diazo condensation,
metal complex, isoindolinone and isoindolinic, polycyclic pigments
such as phthalocyanine, quinacridone, perylene, perinone,
diketopyrrolo-pyrrole, and thioindigo, and anthriquinone pigments
such as anthrapyrimidine.
[0103] The functional layer may also comprise a dielectric
material. A dielectric layer, for purposes of the present
invention, is a layer that is not conductive or blocks the flow of
electricity. This dielectric material may include a UV curable,
thermoplastic, screen printable material, such as Electrodag 25208
dielectric coating from Acheson Corporation. The dielectric
material forms a dielectric layer. This layer may include openings
to define image areas, which are coincident with the openings.
Since the image is viewed through a transparent substrate, the
indicia are mirror imaged. The dielectric material may form an
adhesive layer to subsequently bond a second electrode to the light
modulating layer.
[0104] The liquid crystal containing composition of the invention
can be applied by any of a number of well known techniques, such as
dip coating, rod coating, blade coating, air knife coating, slide
(or bead) coating, curtain coating, and the like.
[0105] After coating, the layer is generally dried by simple
evaporation, which may be accelerated by known techniques such as
convection heating. Known coating and drying methods are described
in further detail in Research Disclosure No. 308119, Published
December 1989, pages 1007 to 1008. The coating is maintained above
the chill set temperature or sol-gel transition temperature of
gelatin during drying of the imaging layer or light modulating
layer to permit self-assembly of the droplets into a close-packed
monolayer.
[0106] A coated sheet can be formed using inexpensive, efficient
layering methods. A single large volume of sheet material can be
coated and formed into various types of smaller sheets for use in
display devices such as transaction cards, shelf labels, large
format signage, and the like. Displays in the form of sheets in
accordance with the present invention are inexpensive, simple, and
fabricated using low cost processes.
[0107] In the preferred embodiment, the imaging layer or light
modulating layer is first applied and maintained above the chill
set temperature or sol-gel transition temperature of gelatin. After
drying, the binder in this layer is allowed to crosslink to
preserve the close-packed monolayer distribution of coated
droplets. A second aqueous layer containing gelatin is then
applied. The coating is chill set prior to drying of the second
layer in order to allow the gelatin molecules in the second layer
to adopt a helix structure In a preferred commercial embodiment,
the substrate to be coated is in the form of a moving web. After
completing the manufacture of a coated liquid crystal sheet
material between spaced electrodes, the sheet material can be cut
into a plurality of smaller, individual areas for use in various
display or other applications.
[0108] A close-packed monolayer of uniform thickness may provide
enhanced performance with respect to surface roughness. In
conventional liquid crystal coatings containing non-uniform
droplets or capsules, the root mean square (RMS) surface roughness
has been measured at about 6 microns. This is a very high value of
surface roughness that would result in irregular or incomplete
curing if a UV curable screen printed conducive ink is used as the
second electrode. The irregular curing will result in increased
switching voltages. Furthermore, a surface roughness of this
magnitude will also result in significant non-uniformity of
switching voltage across the area of the display since the
switching voltage is directly related to the thickness of the
coated layer. The self-assembled droplets or domains in the present
close-packed monolayer demonstrates a RMS surface roughness of less
than 1.5 microns, more preferably less than 1.0 microns and most
preferably less than 0.5 microns.
[0109] The following examples are provided to illustrate the
invention.
EXAMPLE 1
[0110] This example illustrates the close-packed ordered monolayer
structure obtained according to the invention compared to the
random structure of a control coating.
[0111] Chiral nematic liquid crystal (CLC) compositions with center
wavelengths of reflection (CWR) at 540 nm and 590 nm were prepared
by adding the appropriate amount of a high twist chiral dopant to
the nematic host mixture BL087 obtained from Merck, Darmstadt,
Germany. The CLC composition with CWR at 590 nm also contained 0.2%
weight/weight (w/w) of the blue absorbing dye Neopen Yellow 057
from BASF Corporation.
Method I (Invention)
[0112] A dispersion of the CLC composition with CWR at 590 nm was
prepared as follows. To 241 grams of distilled water was added 3.6
grams of Ludox TM colloidal silica suspension and 7.4 grams of a
10% w/w aqueous solution of a copolymer of methylaminoethanol and
adipic acid. To this was added 108 grams of the CLC composition.
The mixture was stirred using a Silverson mixer at 5000 rpm. It was
then passed through a microfluidizer at 3000 psi. Finally, the
resulting dispersion was passed through a 23 .mu.m filter. The
droplet size distribution in the dispersion was measured using a
Coulter Counter. It was found that the mean size was 9.7 microns
with a coefficient of variation (cv) of 0.14.
[0113] The above dispersion was mixed with an aqueous solution of
fish skin gelatin from Norland Products Inc. having a
weight-average molecular weight of 83,800 and a polydispersity of
3.4, an aqueous solution of polyvinylalcohol (PVA)(type GL-05 from
Nippon Gohsei Limited), a solution of Aerosol OT in water and a
solution of bis(vinylsulfonyl)methane in water to give a coating
composition containing 15% w/w CLC material, 4.5% fish skin
gelatin, 0.5% PVA, 0.07% Aerosol OT coating aid and 0.1%
bis(vinylsulfonyl)methane crosslinker. The composition was spread
over a plastic support with a thin layer of indium tin oxide (ITO)
at 37.67 cm.sup.3/m.sup.2 to give a dry uniform coverage of about
5400 mg/m.sup.2 of CLC material. The PVA prevented agglomeration of
the liquid crystal domains during self-assembly and helped minimize
defects in the coating. The plastic support (Dupont ST504) with a
sputter coated ITO conductive layer (300 ohm/sq resistivity) was
obtained from Bekaert. The thickness of the ITO layer is
approximately 240 Angstroms. During the operation, the plastic
support was placed over a coating block that was maintained at room
temperature (23.degree. C.) and the coating composition was also
delivered or applied at the same temperature. The resulting coating
was then dried under ambient conditions (23.degree. C.). The fish
gelatin does not chill set at room temperature and, thus, had not
chill set at the onset of drying.
[0114] A sample of the dried coating was positioned facing a
helium-neon laser (Spectra Physics model 155A). A screen was placed
behind the sample. The distance from the source of laser light to
the sample was 20.6 cm and the distance from the sample to the
screen was 10.5 cm. As shown in FIG. 1, the invention coating
showed diffraction rings on the screen caused by Fraunhofer
diffraction of light indicating an ordered close-packed monolayer
of CLC droplets in the coating.
Method 2 (Control)
[0115] A dispersion of the CLC composition with CWR at 540 nm was
prepared as follows. To 172.1 grams of distilled water was added
2.6 grams of Ludox TM colloidal silica suspension and 5.3 grams of
a 10% w/w aqueous solution of a copolymer of methylaminoethanol and
adipic acid. To this was added 77.2 grams of the CLC composition.
The mixture was stirred using a Silverson mixer at 5000 rpm. It was
then passed through a microfluidizer at 3000 psi. Finally, the
resulting dispersion was passed through a 23 .mu.m filter. The
droplet size distribution in the dispersion was measured using a
Coulter Counter. It was found that the mean size was 9.4 microns
with a coefficient of variation (cv) of 0.14.
[0116] The above dispersion was mixed with an aqueous solution of
conventional Type IV cattle gelatin having a weight-average
molecular weight of 229,000 and a polydispersity of 5.4, a solution
of Alkanol XC in water and a solution bis(vinylsulfonyl)methane in
water to give a coating composition containing 8% w/w CLC material,
5% gelatin, 1% Alkanol XC coating aid and 0.05%
bis(vinylsulfonyl)methane crosslinker. The composition was then
spread over a plastic support with a thin layer of indium tin oxide
(ITO) to give a uniform coverage of about 5400 mg/m.sup.2. The
plastic support (Dupont ST504) with a sputter coated ITO conductive
layer (300 ohm/sq resistivity) was obtained from Bekaert.. The
thickness of the ITO layer is approximately 240 Angstroms. During
the operation, the coating block was maintained at a temperature
close to room temperature (23.degree. C.) and the coating
composition was delivered or applied at a temperature of 45.degree.
C. The resulting coating was then dried under ambient conditions
(23.degree. C.). It should be noted that conventional gelatin will
chill set at this temperature prior to the onset of drying since
the sol-gel transition temperature of conventional gelatin is above
room temperature.
[0117] A sample of this coating was inspected using the same laser
light source under the same conditions as before. As shown in FIG.
2, in this case the diffraction pattern is distinctly different,
indicative of a very disordered or random coating of the CLC
droplets.
EXAMPLE 2
[0118] This example illustrates the improved electro-optical
properties of a device fabricated according to the invention
compared to a control device.
Method I (Invention)
[0119] A dispersion of CLC material was prepared in a manner
similar to Method I of Example 1.
[0120] The dispersion was mixed with an aqueous solution of Type IV
cattle gelatin having a weight-average molecular weight of 117,000
and a polydispersity of 3.7, an aqueous solution of
polyvinylalcohol (PVA)(type GL-05 from Nippon Gohsei Limited), a
solution of Aerosol OT in water and a solution
bis(vinylsulfonyl)methane in water to give a coating composition
containing 15% w/w CLC material, 4.5% gelatin, 0.5% PVA, 0.07%
Aerosol OT and 0.1% bis(vinylsulfonyl)methane. The composition was
spread over a plastic support with a thin layer of indium tin oxide
(ITO) to give a uniform coverage of about 5400 mg/M.sup.2 of CLC
material. The coated layer was referred to as layer 1. During the
operation, the plastic support was placed over a coating block that
was maintained at a temperature of 45.degree. C. and the coating
composition was also delivered or applied at the same
temperature.
[0121] The resulting coating was then dried at 45.degree. C. The
coating was kept aside for 48 hours to allow the crosslinking of
gelatin to go to completion. Analysis of a portion of the coating
by laser light as in Example 1 showed rings due to Fraunhofer
diffraction of light. Analysis of a second portion of the coating
by x-ray diffraction showed a complete absence of triple helix
structure in gelatin. In other words, the gelatin molecules in
layer 1 were in a random coil configuration. The coating was then
placed on a coating block that was maintained at 23.degree. C. A 4%
w/w solution of Type IV cattle gelatin was then coated over layer 1
at a uniform wet coverage of about 28 cm.sup.3/m.sup.2. This second
layer was referred to as layer 2. The coating was then dried at
room temperature (23.degree. C.).
[0122] Analysis of a portion of the coating by x-ray diffraction
now showed a peak at low angle associated with the triple helix
structure of gelatin indicating that at least some of the gelatin
molecules in layer 2 were in the triple helix configuration.
Analysis by laser light showed that the close-packed structure had
been preserved even after the second layer had been applied. A
carbon-based conductive ink (Electrodag 423SS from Acheson
Corporation) was then screen printed on top of layer 2 to complete
the construction of the display device.
[0123] The electro-optic response of the device is shown in FIG. 3.
The horizontal axis is the amplitude of the addressing voltage
pulse and the vertical axis is the reflectance of the CLC material
measured at 0 volts about 2 seconds after application of the
addressing pulse. The reflectance was measured using an X-rite 938
spectrodensitometer. The addressing pulse was a square wave with
frequency of 250 Hz and duration of 100 milliseconds. The open
circles represent the response when the material was initially in
the planar texture and the filled circles represent the response
when the material was initially in the focal conic state. A voltage
pulse higher than 70 volts (V4) switched the display into the
reflecting state and a voltage pulse between 44 and 54 volts (V2
and V3 respectively) switched the display into the weakly
scattering or dark state. Voltages less than V1 (8 volts) did not
influence the state of the display. In this case the quantity Vqm,
defined as 2V1/(V4-V3), was equal to 1. For a multi-row and column
matrix display using conventional drive it is important that Vqm is
greater than or equal to 1 to ensure maximum contrast without
cross-talk.
Method 2 (Control)
[0124] A dispersion of CLC material and coating composition were
prepared in a manner similar to Method 2 of Example 1. The
composition was coated as described under Method 2 of Example 1. A
carbon-based conductive ink (Electrodag 423SS from Acheson
Corporation) was then screen printed on top of the coating to
create the display device. The electro-optic response of the device
is shown in FIG. 4. In this case, a voltage pulse higher than 130
volts (V4) switched the display into the reflecting (bright) state
and a voltage pulse between 44 and 64 volts (V2 and V3
respectively) switched the display into the weakly scattering or
dark state. The contrast ratio defined as the reflectance of the
bright state divided by that of the dark state was 15.8. Voltages
less than 14 volts (V1) did not influence the state of the display.
Based on these parameters Vqm was only 0.42.
[0125] It is clear that the voltage needed to switch the display
into the reflecting state was significantly greater than that of
the invention device. Furthermore, the contrast of a multiplexed
display based on this method may be greatly inferior compared to
the method of the invention because of the relatively low value of
Vqm.
EXAMPLE 3 (Invention)
[0126] A dispersion of CLC material and coating composition were
prepared as described under Method 1 of Example 1. The composition
was spread over a plastic support (Dupont ST504) with a thin layer
of ITO (approximately 240 Angstroms in thickness and 300 ohm/sq
resistivity) at 37.7 cm.sup.3/m.sup.2 to give a uniform dry
coverage of about 5400 mg/m.sup.2 for the CLC material. During the
operation, the plastic support was placed over a coating block that
was maintained at 45 C and the coating composition was delivered at
23 C. The resulting coating of the imaging layer was dried at 45 C.
All of these temperatures were above the sol-gel transition
temperature of the binder.
[0127] The coating of the imaging layer was kept aside for 48 h to
allow the cross-linking of gelatin to go to completion. The coating
was then placed on a coating block that was maintained at 30 C. A
composition containing 4% Type IV cattle gelatin, 1.4% carbon black
and 0.1% Aerosol OT in distilled water was then spread over it
using a coating knife with 0.008 cm gap to constitute the
protective overcoat. The coating was dried at 30 C. For this top
layer or protective overcoat, the temperature of the coating block
and the drying temperature were both below the sol-gel transition
temperature of the binder. A silver-based conducting ink was then
screen printed over the dried protective layer to complete
construction of the display device. The electro-optic response of
this device is shown in FIG. 5. A voltage pulse higher than 72
volts (V4) switched the display into the reflecting state and a
voltage pulse between 32 and 44 volts (V2 and V3 respectively)
switched the display into the weakly scattering or dark state. The
contrast ratio was 33.1.
[0128] It is clear that the voltages needed to switch the display
into the bright state and the dark state were considerably lower
than those for the control.
[0129] Furthermore, the contrast ratio was significantly higher
indicating a much improved display at low voltage.
EXAMPLE 4 (Invention)
[0130] This example illustrates the uniformity of thickness of the
imaging layer using the method of the invention. It is preferred
that the RMS surface roughness is less than 1.5 microns, it is more
preferred that the RMS surface roughness is less than 1.0 microns
and it is most preferred that the RMS surface roughness is less
than 0.5 microns.(reasons for the uniformity of thickness are in
the prior art section).
[0131] A dispersion of CLC material and coating composition were
prepared as described under Method 1 of Example 1. The composition
was spread over a plastic support (Dupont ST504) with a thin layer
of ITO (approximately 240 Angstroms in thickness and 300 ohm/sq
resistivity) at 37.7 cm.sup.3/m.sup.2 to give a uniform dry
coverage of about 5400 mg/m.sup.2 for the CLC material. During the
operation, the plastic support was placed over a coating block that
was maintained at 45 C and the coating composition was delivered at
23 C. The resulting coating of the imaging layer was dried at 45 C.
All of these temperatures were above the sol-gel transition
temperature of the binder.
[0132] The coating of the imaging layer was kept aside for 48 hours
to allow the crosslinking of gelatin to go to completion. The
surface roughness profile was then obtained using a Zeiss LSM 510
laser scanning microscope from Carl Zeiss Microimaging Inc., One
Zeiss Drive, Thornwood N.Y. 10594. FIG. 9 shows a micrograph of the
coating of the imaging layer along with the surface roughness
profile. The roughness profile shows the variation in thickness as
a function of distance along a line drawn across the surface of the
coating. From such a profile it is possible to calculate the root
mean square (RMS) surface roughness (see for example Wyko NT8000
Set Up and Operation Guide June 2003 version 3.01 Veeco Industries
Inc. 2650 East Elvira Road, Tuscon Ariz. 85706). For this coating
the RMS surface roughness was about 0.4 microns.
[0133] The coating was then immersed in acetone to remove the
liquid crystal material. After removal of the liquid crystal
material, the coating was once again examined using the laser
confocal microscope. The corresponding micrograph is shown in FIG.
10. The coating now shows well-defined cavities in areas that were
originally occupied by droplets of the liquid crystal. Note that
the crosslinked binder resisted dissolution. In other words,
cross-linking the binder allowed the close-packed structure to be
fixed or locked into place. The attached profile shows that the
imaging layer had a uniform thickness of about 5 microns.
EXAMPLE 5 (Control)
[0134] This example illustrates the effect of using a polymer latex
as the binder material in the imaging layer instead of gelatin.
[0135] A CLC composition with CWR at 450 nm was prepared by adding
the appropriate amount of a high twist chiral dopant to the nematic
host mixture BL087 obtained from Merck, Darmstadt, Germany.
[0136] A dispersion of the CLC composition with CWR at 450 nm was
prepared as follows. To 166 grams of distilled water was added 2.6
grams of Ludox TM colloidal silica suspension and 5.1 grams of a
10% w/w aqueous solution of a copolymer of methylaminoethanol and
adipic acid. To this was added 74.6 grams of the CLC composition.
The mixture was stirred using a Silverson mixer at 5000 rpm. It was
then passed through a microfluidizer at 3000 psi. Finally, the
resulting dispersion was passed through a 23 .mu.m filter. The
droplet size distribution in the dispersion was measured using a
Coulter Counter. It was found that the mean size was 9.4 microns
with a coefficient of variation (cv) of 0.14.
[0137] The above dispersion was mixed with an aqueous suspension of
polyurethane polymer latex NeoRez R-967 from NeoResins, Wilmington
Mass., USA and a solution of coating aid Olin 10 G in water to give
a coating composition containing 15% w/w CLC material, 5.0% polymer
latex and 0.1% Olin 10 G. The composition was spread over a plastic
support with a thin layer of indium tin oxide (ITO) using a coating
knife with 0.008 cm gap. The plastic support (Dupont ST504) with a
sputter coated ITO conductive layer (300 ohm/sq resistivity) was
obtained from Bekaert. The thickness of the ITO layer is
approximately 240 Angstroms. During the operation, the plastic
support was placed over a coating block that was maintained at room
temperature (23.degree. C.) and the coating composition was also
delivered or applied at the same temperature. The resulting coating
was then dried under ambient conditions (23.degree. C.). The
coating was then placed on a coating block that was maintained at
23 C. A composition containing 4% Type IV cattle gelatin and 0.1%
Aerosol OT in distilled water was then spread over it using a
coating knife with 0.008 cm gap to constitute the protective
overcoat. The coating was dried at 23 C. For this top layer or
protective overcoat, the temperature of the coating block and the
drying temperature were both below the sol-gel transition
temperature of the binder. A carbon-based conductive ink
(Electrodag 423SS from Acheson Corporation) was then screen printed
over the protective overcoat to complete the construction of the
display device.
[0138] The electro-optic response of the device is shown in FIG.
11. The horizontal axis is the amplitude of the addressing voltage
pulse and the vertical axis is the reflectance of the CLC material
measured at 0 volts about 2 seconds after application of the
addressing pulse. The reflectance was measured using an X-rite 938
spectrodensitometer. The addressing pulse was a square wave with
frequency of 250 Hz and duration of 100 milliseconds. The open
circles represent the response when the material was initially in
the planar texture and the filled circles represent the response
when the material was initially in the focal conic state. A voltage
pulse higher than 138 volts (V4) switched the display into the
reflecting state and a voltage pulse between 64 and 86 volts (V2
and V3 respectively) switched the display into the weakly
scattering or dark state. Voltages less than V1 (12 volts) did not
influence the state of the display. In this case the quantity Vqm,
defined as 2V1/(V4-V3), was equal to 0.46. Once again it is clear
that the voltage needed to switch the display into the reflecting
state was significantly greater than that of the invention device.
Furthermore, the contrast of a multiplexed display based on this
method may be greatly inferior compared to the method of the
invention because of the relatively low value of Vqm.
[0139] The invention has been described in detail with particular
reference to certain preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
* * * * *