NZ207420A - Nematic liquid crystal display - Google Patents

Description

* „ , , ar3-tJV Xi-'5-"65 Priority Dats(s): "" ' *1*"?) *3 Complete Specification Filed: ... ' ■TJ Class: 12 FEB 1988 Publication Date: I 304- P.O. Journal, No: toPATe»TQS:t-X£ T - ' " ~~ ~~ | -7 MAR 1984 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION ENCAPSULATED LIQUID CRYSTAL AND METHOD AND ENHANCED SCATTERING IN VOLTAGE SENSITIVE ENCAPSULATED LIQUID CRYSTAL Manchester R&D Partnership (an Ohio limited partnership) of 2731 Emerson Drive, Pepper Pike, Ohio 44124 U.S.A., which comprises - James Roeder Bell s Jr, (the only general partner), of 2731 Emerson Drive, Pepper Pike, Ohio 44124 U.S.A.; and James Roeder Bell, 111, Leslie Meriam Bell, and John Farmer Bell, also all of 2731 Emerson Drive, Pepper Pike, Ohio 44124 U.S.A. and James Lee Fergason of 23 Hawthorne Drive, Atherton, California 94025 U.S.A. (all limited partners). All of such partners are citizens of the United States of America, and Manchester R&D Partnership, the applicant is an Ohio limited partnership organized under the laws of the State of Ohio, U.S.A., do hereby declare the invention for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement: - 1 - Followed by la 207420 la TECHNICAL FIELD The present invention relates generally to the art of liquid crystals and more particularly, in one embodiment, to the scattering of light by liquid crystal material. Moreover, the invention relates to use of such scattering in a liquid crystal display apparatus to form a white or bright character and in optical shutter devices, e.g. to control brightness, to enhancing of the light output/contrast of a liquid crystal apparatus, especially of the type using encapsulated liquid crystal or liquid crystal material held in a containment medium, such as an emulsion, and to methods of making and using such liquid crystal apparatus.

The invention also relates, in another embodiment, to use of pleochroic dye in the liquid crystal for absorbing light incident thereon, and to corresponding methods of making and using same.

BACKGROUND Liquid crystal material currently is used in a wide variety of devices, including, for example, optical devices such as visual displays. A property of liquid crystals enabling use in visual displays is the ability to scatter and/or to absorb (especially when pleochroic dye is mixed with the liquid crystal) light when the liquid crystals are in a random alignment and the ability to transmit light when the liquid crystals are in an ordered alignment. 207 4 2 0 Frequently a visual display using liquid crystals displays dark characters on a gray or relatively light background. In various circumstances it would be desirable, though, using liquid crystal material to be able to display with facility relatively bright characters or other information, etc. on a relatively dark background. It would be desirable as well to improve the effective contrast between the character displayed and the background of the display itself.

An example of electrically responsive liquid crystal material and use thereof is found in U.S. Patent No. 3,322,485. Certain types of liquid crystal material are responsive to temperature, changing the optical characteristics, such as the random or ordered alignment of the liquid crystal material, in response to temperature of the liquid crystal material.

Currently there are three categories of liquid crystal materials, namely cholesteric, nematic and smectic. Various principles of the invention may be employed with various one or ones of the other known types of liquid crystal material or combinations thereof. The present invention preferably uses nematic liquid crystal material or a combination of nematic and some cholesteric type. More specifically, the liquid crystal material preferably is operationally nematic, i.e. it acts as nematic material and not as the other types. Operationally nematic means that in the absence of external fields, structural distortion of the liquid crystal is dominated by the orientation of the liquid crystal at its boundaries rather than by bulk effects, such as very strong twists as in cholesteric material, or layering as in smectic material. Thus, for example, chiral ingredients which induce a tendency to twist but cannot overcome the effects of boundary alignment still would be operationally nematic. Such material should have a positive dielectric anisotropy. Although various characteristics of the various liquid crystal materials are described in the prior art, one known characteristic is that of reversibility. Particularly, nematic liquid crystal material is known to be reversible, but cholesteric material ordinarily is not reversible.

Pleochroic dyes have been mixed with the liquid crystal material to form a solution therewith. The pleochroic dye generally aligns with the structure of the liquid crystal material. Therefore, such pleochroic dyes 20742 will tend to function optically in a manner similar to that of the liquid crystal material in response to a changing parameter, such as application or non-application of an electric field. Examples of the use of pleochroic dyes with liquid crystal material are described in U.S. Patents 3,499,702 and 3,551,026. One advantage to using pleochroic dye with the liquid crystal material is the eliminating of a need for a polarizer. However, in the nematic form a pleochroic device has relatively low contrast. In the past cholesteric material could be added to the nematic material together with the dye to improve contrast ratio. See for example the White et al article in Journal of Applied Physics, Vol. 45, No. 11, November 1974, at pages 4718-4723. However, although nematic material is reversible, depending on whether or not an electric field is applied across the same, cholesteric material ordinarily would not tend to its original zero field form when the electric field would be removed. Another disadvantage to use of pleochroic dye in solution with liquid crystal material is that the absorption of the dye is not zero in the field-on condition; rather, absorption in the field-on condition follows an ordering parameter, which relates to or is a function of the relative alignment of the dyes.

Usually liquid crystal material is anisotropic both optically (birefringence) and, for example in the case of nematic material, electrically. The optical anisotropy is manifest by the scattering of light when the liquid crystal material is in random alignment, and the transmission of light through the liquid crystal material when it is in ordered alignment. The electrical anisotropy may be a relationship between the dielectric constant or dielectric coefficient with respect to the alignment of the liquid crystal material.

In the past, devices using liquid crystals, such as visual display devices, have been relatively small. One reason is the fluidity of the liquid crystals, (the liquid crystal material may tend to flow creating areas of the display that have different thicknesses). As a result, the optical characteristics of the display may lack uniformity, have varying contrast characteristics at different portions of the display, etc.; the thickness variations in turn cause variations or gradations in optical properties of the liquid crystal 2074 2 0 device. Moreover, the varying thickness of the liquid crystal layer will cause corresponding variations in the electrical properties of the liquid crystal layer, such as capacitance and impedance, further reducing uniformity of a large size liquid crystal device. The varying electrical properties of the liquid crystal layer, then, also may cause a corresponding variation in the effective electric field applied across the liquid crystal material and/or in response to a constant electric field would respond differently at areas of the liquid crystal that are of different thicknesses.

To overcome such problems, the liquid crystal material should have an optimum uniform thickness. (As used herein the term "liquid crystal" material means the liquid crystals themselves and, depending on context, the pleochroic dye in solution therewith). There also should be an optimum spacing of the electrodes by which the electric field is applied to the liquid crystal material. To maintain such optimum thickness and spacing, rather close tolerances must be maintained. To maintain close tolerances, there is a limit as to the size of the device using such liquid crystals, for it is quite difficult to maintain close tolerances over large surface areas, for example.

Use of encapsulated liquid crystals disclosed in accordance with applicant's invention has enabled the satisfactory use of liquid crystals in relatively large size displays, such as billboards, etc., as is disclosed in such above applications; and another large (or small) scale use may be as an optical shutter to control passage of light from one area into another, say at a window or window-like area of a building. The present invention relates to .improvements in such encapsulated liquid crystals and to the utilization of the light scattering characteristic of the liquid crystal material as opposed, for example, to the light absorption (usually with pleochroic dye) characteristic thereof. The invention also relates to the use of such material and characteristics, for example, to obtain a relatively bright character or information displayed on a relatively dark or colored background in both small and large displays as an optical shutter, and so on. Such large displays and shutters may be about one square foot surface area or even larger. In accordance with the present invention the liquid crystal material most preferably is of the encapsulated type. 2074^0 -5- Followed by 5a As used herein with respect to the present invention, encapsulated liquid crystal material means liquid crystal material in a substantially closed containment medium, such as discrete capsules or cells, and preferably may be in the form of an emulsion of the liquid crystal material and the containment medium. Such emulsion should be a stable one. Various methods for making and using encapsulated liquid crystal material and apparatus associated therewith are disclosed below and in applicant's wo 83/01016 application, which is incorporated by reference.

One typical prior art display may include a support medium and liquid crystal material supported thereby. The display is relatively flat and is viewed from a viewing side from which a so-called front surface is viewed. The back surface of the support medium may have a light reflective coating tending to make the same appear relatively bright in comparison to relatively dark characters formed at areas where there is liquid crystal material. (Back, front, top, bottom, etc. are only for convenience; there is no constraint that in operation the viewing direction must be, for example, as shown from only the top, etc.). When the liquid crystal material is in ordered alignment incident light from the viewing direction passes through the liquid crystal material to the light reflective coating and also where there is no liquid crystal material passes directly to the light reflective coating; and no character is observed from the viewing direction. However, when the liquid crystal material is in random alignment, it will absorb some and scatter some incident light thereby to form a relatively dark character on a relatively light color background, for example of gray or other color depending on the type of light reflective coating. In this type of display it is undesirable for the liquid crystal material to scatter light because some of that scattered light will be directed back in the viewing direction thereby reducing the darkness or contrast of the character relative to the background of the display. Pleochroic dye often is added to the liquid crystal material to increase absorbence and, thus, contrast when the liquid crystal material is in random alignment.

BRIEF SUMMARY OF INVENTION Briefly, according to one aspect of the invention, liquid crystal apparatus is characterized in comprising plural volumes of— liquid crystal assembled in a containment medium for selectively pcjh^£rily ' f/ .-a\V IN Z ir7DEC 1987 y 2074^0 -5 a- scatterlng light or, In response to a prescribed field input applied to the volumes of liquid crystal assembled In the containment medium, transmitting light, said liquid crystal comprising operationally nematic liquid crystal having positive dielectric anisotropy and being operative to align with respect to the direction of such an applied field input and to undergo alignment, due to surface interaction, with respect to walls defining the volumes in said medium in the absence of such input, and the apparatus providing an optical response to such input by matching ordinary index of refraction of said liquid crystal with the index of refraction of the medium, and reflecting means for effecting total internal reflection of light scattered by said liquid crystal; according to another aspect the invention is characterized in comprising a method of displaying a bright character or other Information on a relatively dark background using liquid crystal contained in volumes formed in the containment medium, such liquid crystal being operationally nematic, having positive dielectric anisotropy, having an extraordinary Index of refraction that is different from the index of refraction of such containment medium and an ordinary index of refraction substantially matched to the index of refraction of such containment medium, comprising using surface Interaction with such containment medium distorting the natural structure of such liquid crystal to effect scattering of at least some light incident on such liquid crystal, reflecting at least some of such scattered light back to such volumes of liquid crystal for further scattering, transmitting to a viewing area at least some of the light scattered by such liquid crystal to form such character or other information, and selectively applying an electric field to such liquid crystal to align the same for transparency to form such relatively dark background; according to another aspect the encapsulated 207420 liquid crystal material is used in liquid crystal devices, such as relatively large size visual display devices and optical shutters; and according to further aspects there are provided methods for encapsulating liquid crystal material and for making a liquid crystal device using such encapsulated liquid crystal material.

In one embodiment of the invention broadly the liquid crystal scatters or absorbs light in the absence of a prescribed input, such as an electric field, and in the presence of such input scattering or absorption is reduced. Absorption is increased in the absence of such input by mixing pleochroic dye with the liquid crystal.

In another embodiment, which may include but preferably does not include pleochroic dye, succinctly stated, the invention relates to the isotropic scattering of light by liquid crystal material and to the use of such isotropically scattered light to yield a white or bright appearance, character, information, etc., especially relative to background, when a liquid crystal material is in a field-off or distorted alignment condition and a colored or dark appearance, e.g. the same as background, when a liquid crystal material is in field-on parallel or ordered alignment condition. Preferably the liquid crystal material is nearly completely isotropically scattering when in distorted alignment. Isotropic scattering means that when a beam of light enters the liquid crystal material there is virtually no -way to predict the exit angle of scattered light. Pleochroic dye preferably is not used in this embodiment because the dye would absorb light to reduce brightness when scattering and brightening would be intended.

As it is used herein with respect to the invention, the terms distorted alignment, random alignment and field-off condition mean essentially the same thing; namely, that the directional orientation of the liquid crystal molecules is distorted to an effectively curved configuration. Such distortion is effected, for example, by the wall of respective capsules. The particular distorted alignment of liquid crystal material in a given capsule usually always will be substantially the same in the absence of an electric field. On the other hand, as it is used herein with respect to the invention, parallel aligned, ordered alignment, and field-on condition means that the 20742 0 liquid crystal material in a capsule is generally aligned with respect to an externally applied electric field. Operationally nematic is defined above.

A capsule refers to a containment device or medium that confines a quantity of liquid crystal material, and "encapsulating medium" or "material" is that medium or material of which such capsules are formed. An "encapsulated liquid crystal" or "encapsulated liquid crystal material" means a quantity of liquid crystal material confined or contained in discrete volumes within the encapsulating medium, for example in a solid medium as individual capsules or dried stable emulsions.

Capsules according to this invention generally have an approximately spherical configuration (though this is not, per se, a requisite of the invention) having a diameter from about 0.3 to 100 microns, preferably 0.1 to 30 microns, especially 3 to 15 microns, for example 5 to 15 microns. In the context of this invention, encapsulation and like terms refer not only to the formation of such articles as are generally referred to as capsules, but also to the formation of stable emulsions or dispersions of the liquid crystal material in an agent (an encapsulating medium) which results in the formation of stable, preferably approximately uniformly sized, particles in a uniform surrounding medium. Techniques for encapsulation, generally referred to as microencapsulation because of the capsule size, as well known in the art (see, e.g., "Microcapsule Processing and Technology" by Asaji Kondo, published by Marcel Dekker, Inc.) and it will be possible for one skilled in the art, having regard to the disclosure herein, to determine suitable encapsulating agents and methods for liquid crystal materials.

A liquid crystal device is a device formed of liquid crystal material. In the present invention such devices are formed of encapsulated liquid crystals capable of providing a function of the type typically inuring to liquid crystal material; for example, such a liquid crystal device may be a visual display or an optical shutter that in response to application and removal of an electric field effects a selected attenuation of optical radiation, preferably including from far infrared through ultraviolet wavelengths.

One method of making encapsulated liquid crystals includes mixing together liquid crystal material and an encapsulating medium in 20742 0 which the liquid crystal material will not dissolve and permitting formation of discrete capsules containing the liquid crystal material.

A method of making a liquid crystal device including such encapsulated liquid crystal includes, for example applying such encapsulated liquid crystal material to a substrate. Moreover, such method may include providing means for applying an electric field to the liquid crystal material to affect a property thereof.

According to another feature of the invention an operationally nematic material in which is dissolved a pleochroic dye is placed in a generally spherical capsule. In the absence of an electric field, the capsule wall distorts the liquid crystal structure so it and the dye will tend to absorb light regardless of its polarization direction. When a suitable electric field is applied across such a capsule, for example across an axis thereof, the liquid crystal material will tend to align parallel to such field causing the absorption characteristic of such material to be reduced to one assumed when the liquid crystal material is in the planar configuration. To help assure that adequate electric field is applied across the liquid crystal material in the capsule, and not just across or through the encapsulating medium, and, in fact, with a minimum voltage drop across the wall thickness of the respective capsules, the encapsulating material preferably has a dielectric constant no less than the lower dielectric constant of the liquid crystal material, on the one hand, and a relatively large impedance, on the other hand. Ideally, the dielectric constant of the encapsulating medium should be close to the higher dielectric constant of the liquid crystal.

Contrast of a liquid crystal device employing encapsulated liquid crystals may be improved by selecting an encapsulating medium that has an index of refraction that is matched to the ordinary index of refraction of the liquid crystal material (i.e. the index of refraction parallel to the optical axis of the crystal. See, e.g. "Optics" by Borne & Wolf, or "Crystals and the Polarizing Microscope" by Hartshorne <5c Stewart. The encapsulating medium may be used not only to encapsulate liquid crystal material but also to adhere the capsules to a substrate for support thereon. Alternatively, a further binding medium may be used to hold the liquid crystal capsules 20742 0 relative to a substrate. In the latter case, though, preferably the additional binding medium has an index of refraction which is matched to that of the encapsulating medium for maintaining the improved contrast characteristic described above. Because the index of refraction of a material is generally strain-dependent, and strain may be induced in, e.g. the encapsulating medium, it may be necessary to consider this effect in matching the indices of refraction of the liquid crystal, encapsulating medium, and binding medium, if present. Further, if iridescence is to be avoided, it may be desirable to match the indices of refraction over a range of wavelengths to the extent possible, rather than at just one wavelength.

A feature of the spherical or otherwise curvilinear surfaced capsule which confines the liquid crystal material therein in accordance with the present invention is that the liquid crystal material tends to follow the curvature or otherwise to align itself generally parallel with the curved surfaces of such capsule. Accordingly, the liquid crystal structure tends to be forced or distorted to a specific form, being folded back on itself in a sense as it follows the capsule wall, so that the resulting optical characteristic of a given capsule containing liquid crystal material is such that substantially all light delivered thereto will be affected, for example, scattered (when no pleochroic dye is present) or absorbed (when pleochroic dye is present), when no electric field is applied, regardless of the polarization direction of the incident light. Even without dye this effect can cause scattering and thus opacity.

Another feature is the ability to control the effective thickness of the liquid crystal material contained in a capsule by controlling the internal diameter of such capsule. Such diameter control may be effected by a size fractionation separation process during the making of the encapsulated liquid crystals using any one of a variety of conventional or novel sorting techniques as well as by controlling the mixing process, the quantities of ingredients, and/or the nature of the ingredients provided during mixing. By controlling such thickness parameter to relatively close tolerances, then, the subsequent tolerance requirements when the final liquid crystal device is made using the encapsulated liquid crystals will not be as critical as was required in the past for non-encapsulated devices. 207420 However, a further and very significant feature of the present invention is that there appears to be no limitation on the size of a high quality liquid crystal device that can be made using the encapsulated liquid crystals in accordance with the present invention. More specifically, by providing for confinement of discrete quantities of liquid crystal material, for example, in the described capsules, the various problems encountered in the past that prevented the use of liquid crystal material in large size devices are overcome, for each individual capsule in effect can still operate as an independent liquid crystal device. Moreover, each capsule preferably has physical properties enabling it to be mounted in virtually any environment including one containing a plurality of further such liquid crystal capsules mounted to a substrate or otherwise supported for use in response to application and removal of some type of iexcitation source, such as, for example, an electric or magnetic field. This feature also enables placement of the liquid crystal material on only selected areas of the optical device, such as in large size displays (e.g. billboards), optical shutters, etc.

Important considerations in accordance with the invention, and the discovery of the inventor, are that an encapsulating medium having electrical properties matched in a prescribed way to the electrical properties of liquid crystal material encapsulated thereby and additionally preferably optically matched to optical properties of such liquid crystal material permits efficient and high quality functioning of the liquid crystal material in response to excitation or non-excitation by an external source; and that the interaction of the encapsulating medium with the liquid crystal material distorts the latter in a prescribed manner changing an operational mode of liquid crystal material. Regarding the latter, by forcing the liquid crystal structure to distort into generally parallel or conforming alignment with the capsule wall, the liquid crystals will absorb or block, rather than transmit, light when not subject to an electric field and will be functional with respect to all manners of incident light regardless of the direction of polarization, if any, of such incident light.

In accordance with one aspect of the present invention, a liquid crystal display can produce relatively bright or white characters, informa- 20742 0 -li- tion, etc., on a relatively dark background; the bright character is produced by liquid crystal material that is randomly aligned (preferably without pleochroic dye that would absorb and reduce scattering); the background is caused, for example, by liquid crystal material that is in ordered alignment and, thus, substantially optically transparent and/or by areas of the display where there is no liquid crystal material. When the liquid crystal material is in parallel or ordered alignment, only the relatively dark background, e.g., formed by an absorber, would appear. The foregoing is accomplished using relatively low power requirements, minimum liquid crystal material, and illumination either from the viewing side or direction or from the back or non-viewing side of the display. The principles of the invention also may be used in an optical shutter or light control device to control brightness, for example.

Briefly, the liquid crystal apparatus includes liquid crystal material for selectively primarily scattering or transmitting light in response to a prescribed input and a support medium for holding therein the liquid crystal material. In a preferred embodiment the liquid crystal material is of the encapsulated type that will cause substantially isotropic scattering of light incident thereon, including the scattering of some of such light back in the viewing direction toward, for example, the eye of an observer. More preferably, such liquid crystal is operationally nematic, has a positive dielectric anisotropy, and has an ordinary index of refraction that substantially matches that of the containment or encapsulating medium therefor.

In one embodiment, a large quantity of light that is isotropically scattered by the liquid crystal material is totally internally reflected by the support medium back to the liquid crystal material thereby illuminating the same and causing further isotropic scattering and brightening of the appearance of the liquid crystal material, for example to the eye of an observer. The internal reflectance characteristic of the support medium may be effected by the interface of such back surface with another medium, such as a solid, liquid, or gas, even including air, with the constraint that the index of refraction of the support medium is greater than the index of refraction of such other medium. The support medium may be comprised of 207 4 2 0 several components, including, for example, the containment/encapsulating material (or that with which the liquid crystal material is in emulsion), additional quantities of such encapsulating or other material, a mounting medium, such as a plastic-like film or glass, etc., all of which will be described in further detail below.

The back surface of the support medium may be optically transmissive so that light that reaches such surface in a direction substantially normal thereto will be transmitted. A light absorbing black or colored material beyond such back surface can help darken or color the apparent background on which the characters formed by liquid crystal material appear. Ordered alignment of the liquid crystal material will at least substantially eliminate the isotropic scattering so that substantially all the light passing through the liquid crystal material will also pass through the back surface of the support medium.

In an alternate embodiment, a tuned dielectric coating may be applied, e.g. by evaporation techniques, to the back surface of the support medium to effect selective constructive and destructive optical interference. The thickness of such tuned dielectric coating will be a function of lambda (^ ) divided by 2, lambda being the wavelength of light employed with the apparatus. Constructive interference will enhance the internal reflection, especially by reducing the solid angle within which light would not be totally internally reflected in the support medium; and, therefore, such interference will further brighten the appearance of the liquid crystal material characters.

Incident illumination for a liquid crystal display embodying the invention may be from the front or viewing side. Alternatively, incident illumination may be from the back side, preferably through a mask or director to direct light fully transmitted by the liquid crystal material out of the field or angle of view at the viewing side. However, light scattered by the liquid crystal material within the viewing angle would be seen.

Moreover, a cholosteric material may be added to the nematic liquid crystal material to expedite return of the latter to distorted alignment pattern following in general the configuration of the capsule or cell 207420 wall when the electric field is turned off, especially when the capsules are relatively large. Also, if desired, a viscosity controlling additive may be mixed with the liquid crystal. Further, an additive to the liquid crystal may be used to help force a preferred alignment of the liquid crystal structure in a capsule.

These and other embodiments of the invention will become apparent as the following description proceeds.

The following description and the annexed drawings set forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the invention may be employed.

BRIEF DESCRIPTION OF DRAWINGS In the annexed drawings: Fig. 1 is a schematic representation of a liquid crystal device in accordance with the present invention; Figs. 2 and 3 are enlarged schematic illustrations of a liquid crystal capsule in accordance with the present invention respectively under a no-field or field-off condition and under an applied electric field or field-on condition; Figs. 4 and 5 are schematic representations of a liquid crystal apparatus according to one embodiment of the invention, respectively in a no-field condition and in an applied electric field condition; Fig. 6 is a schematic representation of another embodiment of a liquid crystal apparatus in accordance with the present invention using an air gap to cause total internal reflection; Figs. 7 and 8 are schematic representations of another embodiment of liquid crystal apparatus in accordance with the present invention employing optical interference principles respectively under a no-field condition and under an applied electric field condition; Fig. 9 is an isometric view of a liquid crystal display apparatus in accordance with the present invention and which may be formed of any of the embodiments disclosed herein; 20742 0 Fig. 10 is a fragmentary schematic elevation view of another embodiment of liquid crystal apparatus using continuous layers of liquid crystal material and interrupted electrodes; Fig. 11 is a schematic isometric view, partly broken away, of the embodiment of Fig. 10; Fig. 12 is a schematic view of an approximately proportioned liquid crystal display according to the invention showing a more accurately representative size relationship of the support medium layers and encapsulated liquid crystal layer for the several embodiments herein; Fig. 13 is a schematic illustration of a nematic liquid crystal capsule with cholosteric material additive, which may be used with the several embodiments herein; Figs. 14 and 15 are schematic illustrations of still another embodiment of liquid crystal apparatus with a light control film director provided with incident illumination from the non-viewing side, respectively, in the field on and field off conditions; Fig. 16 is a schematic illustration similar to Figs. 14 and 15 but with the light control film director cemented to the support medium; Fig. 17 is a schematic illustration like Figs. 2 and 3 showing an alternate embodiment of encapsulated liquid crystal; and Fig. 18 is a schematic representation of a liquid crystal device in accordance with the invention employing pleochroic dye in the liquid crystal; Fig. 19 is an enlarged fragmentary view, partly broken away, of a portion of the liquid crystal display device of Fig. 9, but including pleochroic dye, for example, as in the embodiment illustrated in Fig. 18; and Fig. 20 is a schematic electric circuit diagram representation of a liquid crystal capsule according to the invention with an applied field.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to Figs. 1, 2 and 3, encapsulated liquid crystal material used in accordance with the present invention is illustrated. In Fig. 1 is a schematic representation of a liquid crystal apparatus 10 in accordance with the present invention. The apparatus 10 includes encapsulated liquid crystal 20742 0 material 11 represented by a single capsule in Figs. 1-3. Although the capsules illustrated in the drawings are shown in two dimensions and, therefore, planar form, it will be appreciated that the capsules are three dimensional, most preferably spherical. The capsule 11 is shown mounted in a preferably transparent support medium 12 having upper and lower portions 12a, 12b which may be integral with each other. The apparatus 10 also includes a pair of electrodes 13, 14 for applying an electric field across the liquid crystal material when a switch 15 is closed to energize the electrodes from a conventional voltage source 16.

A primary feature of the present invention is that such encapsulated liquid crystal material will isotropically scatter light impinging thereon when in a field-off random alignment condition; and in the field-on orderly aligned condition, such material will be substantially optically transparent.

The capsule 11 may be one of many capsules that are discretely formed or, more preferably, that are formed by mixing the liquid crystal material with a so-called encapsulating material or containment medium to form an emulsion, preferably a stable one. The emulsion may be applied to or sandwiched between the support media portions 12a, 12b, and electrodes 13, 14, as is illustrated. If desired, the support medium 12 and the so-called encapsulating material or containment medium may be the same material. As a further alternative, the upper and lower support medium portions 12a, 12b, or one of them, may be a plastic-like, glass, or like, preferably transparent, mounting material. In this latter case the electrodes 13, 14 may be applied to such mounting material and the encapsulated liquid crystal material/emulsion, including many capsules 11, for example, may be sandwiched between such mounting material 12a, 12b to form the apparatus 10, as will be described in further detail below.

A reflectance medium 18 forms an interface 19 with the lower support medium portion 12b to obtain the desired total internal reflection function. Due to the total internal reflection principle of operation, the liquid crystal material in the capsule 11 will be illuminated by incident light, for example represented by a light beam 17, and with light that it isotropi- £0742 cally scatters in the apparatus 10 so that from the viewing area 20 beyond the upper support medium portion 12a, the liquid crystal material 11 will appear white or relatively bright when under a no-field condition, e.g. the switch 15 is open. Although such isotropic scattering (and some absorption, especially with a pleochroic dye present in the encapsulated liquid crystal material) occurs in applicant's invention disclosed in the above co-pending application wo 83/01016 , the total internal reflection principle of the present invention enhances scattering and, thus, brightens the visual/optical appearance , of characters formed by the encapsulated liquid crystal material. A light absorbing layer 21 of black or colored material may be applied to the bottom or back surface of the reflectance medium 18 remote from the interface 19 to absorb light incident on the layer 21. applied to the lower support medium portion 12b, and the electrode 14 may be electrically conductive ink applied directly to the liquid crystal material or could be like the electrode 13. Other electrode material and mounting means therefor also may be used for either electrode. Examples include tin oxide and antimony doped tin oxide. Preferably the electrodes are relatively thin, for example, about 200 angstroms thick, and transparent so that they do not significantly affect the optics of the liquid crystal apparatus 10. contained within the confines or interior volume 31 of a capsule 32. Each capsule 32 may be a discrete one or alternatively the liquid crystal 30 may be contained in a stable emulsion of a containment medium or so-called encapsulating material 33 that tends to form a multitude of capsule-like environments for containing the liquid crystal material. For convenience of illustration, the capsules 32 are shown as discrete capsules in and preferably formed of the overall quantity of containment medium or encapsulating material 33. Preferably the capsule 32 is generally spherical, and the liquid crystal 30 is nematic or operationally nematic liquid crystal material having positive dielectric anisotropy. However, the principles of the invention would apply when the capsule 32 is of a shape other than spherical; such shape should provide the desired optical and electrical characteristics that The electrode 13 may be vacuum deposited indium tin oxide The encapsulated liquid crystal material 11 includes liquid crystal 207420 will satisfactorily coact with the optical characteristics of the liquid crystal material 30, e.g. index of refraction, and will permit an adequate portion of the electric field to occur across the liquid crystal 30 itself for effecting desired ordered or parallel alignment of the liquid crystal when it is desired to have a field-on condition. The shape also should tend to distort the liquid crystal material when in a field-off or random alignment condition. A particular advantage to the preferred spherical configuration of the capsule 32 is the distortion it effects on the liquid crystal 30 therein when in a field-off condition. This distortion is due, at least in part, to the relative sizes of the capsules and the pitch of the liquid crystal; they preferably are about the same or at least about the same order of magnitude. Moreover, nematic liquid crystal material has fluid-like properties that facilitate the conformance or the distortion thereof to the shape of the capsule wall in the absence of an electric field. On the other hand, in the presence of an electric field such nematic material will relatively easily change to ordered alignment with respect to such field.

Liquid crystal material of a type other than nematic or combinations of various types of liquid crystal material and/or other additives may be used with or substituted for the preferred nematic liquid crystal material as long as the encapsulated liquid crystal is operationally nematic. However, cholesteric and smectic liquid crystal material generally are bulk driven. It is more difficult to break up the bulk structure thereof for conformance to capsule wall shape and energy considerations in the capsule.

Turning to Figs. 2 and 3, a schematic representation of the single capsule 32 containing liquid crystal 30 is shown, respectively, in the field-off and field-on conditions. The capsules 32 have a generally smooth curved interior wall surface 50 defining the boundary for the volume 31. The actual dimensional parameters of the wall surface 50 and of the overall capsule 32 are related to the quantity of liquid crystal 30 contained therein and possibly to other characteristics of the individual liquid crystal material therein. Additionally, the capsule 32 applies a force to the liquid crystals 30 tending to pressurize or at least to maintain substantially constant the pressure within the volume 31. As a result of the foregoing, and due to the 207420 surfaee wetting nature of the liquid crystal, the liquid crystals which ordinarily in free form would tend to be parallel, although perhaps randomly distributed, are distorted to curve in a direction that generally is parallel to a relatively proximate portion of the interior wall surface 50. Due to such distortion the liquid crystals store elastic energy. For simplicity of illustration, a layer 51 of liquid crystal molecules whose directional orientation is represented by respective dashed lines 52 is shown in closest proximity to the interior wall surface 50. The directional orientation of the liquid crystal molecules 52 is distorted to curve in the direction that is parallel to a proximate area of the wall surface 50. The directional pattern of the liquid crystal molecules away from the boundary layer 52 within the capsule is represented by 53. The liquid crystal molecules are directionally represented in layers, but it will be appreciated that the molecules themselves are not confined to such layers. Thus, the organization in an individual capsule is predetermined by the organization of the structure 52 at the wall and is fixed unless acted on by outside forces, e.g. an electric field. On removal of the electric field the directional orientation would revert back to the original one, such as that shown in Fig. 2.

Nematic type material usually assumes a parallel configuration and usually is optical polarization direction sensitive. However, since the material 52 in the encapsulated liquid crystal 11 is distorted or forced to curved form in the full three dimensions of the capsule 32, such nematic liquid crystal material in such capsule takes on an improved characteristic of being insensitive to the direction of optical polarization of incident light. The inventor has discovered, moreover, that when the liquid crystal material 30 in the capsule 32 has pleochroic dye dissolved therein, such dye, which ordinarily also would be expected to have optical polarization sensitivity, no longer is polarization sensitive because the dye tends to follow the same kind of curvature orientation or distortion as that of the individual liquid crystal molecules 52.

The liquid crystal 30 in the capsule 32 has a discontinuity 55 in the generally spherical orientation thereof due to the inability of the liquid crystal to align uniformly in a manner compatible with parallel alignment 20742 with the wall 50 and a requirement for minimum elastic energy. Such discontinuity is in three dimensions and is useful to effect a distorting of the liquid crystal 30 further to decrease the possibility that the liquid crystal 30 would be sensitive to optical polarization direction of incident light. The discontinuity protrusion 55 would tend to cause scattering and absorption within the capsule, and the tangential or parallel alignment of the liquid crystal molecules with respect to portions of the interior wall surface 50 of the capsules both cause scattering and absorption within the capsule 32. When the electric field is applied, for example, as is shown in Fig. 3, the discontinuity will no longer exist so that such discontinuity will have a minimum effect on optical transmission when the encapsulated liquid crystal 11 is in a field-on or aligned condition.

Although the foregoing discussion has been in terms of a homogeneous orientation of the liquid crystal material (parallel to the capsule wall), such is not a requisite of the invention. All that is required is that the interaction between the wall and the liquid crystal produce an orientation in the liquid crystal near that wall that is generally uniform and piecewise continuous, so that the spatial average orientation of the liquid crystal material over the capsule volume is strongly curved and there is no substantial parallel direction of orientation of the liquid crystal structure in the absence of an electric field. It is this strongly curved orientation that results in the scattering and polarization insensitivity in the field-off condition, which is a feature of this invention.

In the field-on condition, or any other condition which results in the liquid crystal being in ordered or parallel alignment, as is shown in Fig. 3, the encapsulated liquid crystal 11 will transmit substantially all the light incident thereon and will tend not to be visible in the support medium 12. On the other hand, in the field-off condition when the liquid crystal is in distorted alignment, sometimes referred to herein as random alignment, for example as is shown in Fig. 2, some of the incident light will be absorbed, but also some of the incident light will tend to be scattered isotropically in the support medium 12. Using total internal reflection such isotropically scattered light can be redirected to the encapsulated liquid crystal 11 thus 207420 brightening the same tending to cause it to appear white to a viewer or viewing instrument.

The index of refraction of the encapsulating medium 32 and the ordinary index of refraction of the liquid crystal 30 should be matched as much as possible when in the field-on or liquid crystal orderly aligned condition to avoid optical distortion due to refraction of incident light passing therethrough. However, when the liquid crystal material is in distorted or random alignment, i.e. there is no field applied, there will be a difference in the indices of refraction at the boundary of the liquid crystal 30 and wall of capsule 32; the extraordinary index of refraction of the liquid crystal is greater than the index of refraction of the encapsulating medium. This causes refraction at that interface or boundary of the liquid crystal material and of the containment or encapsulating medium and, thus, further scattering. Light that is so further scattered will be internally reflected for further brightening in the liquid crystal appearance. Such occurrence of different indices of refraction is known or birefringence. Principles of birefringence are described in Optics by Sears and in Crystals And The Polarizing Microscope by Hartshorne and Stewart, the relevant disclosures of which are hereby incorporated by reference. Preferably the encapsulating or containment medium 32 and the support medium 12 have the same index of refraction to appear optically substantially as the same material, thus avoiding a further optical interface.

As long as the ordinary index of refraction of the liquid crystal material is closer to the index of refraction of the so-called encapsulating medium, than is the extraordinary index of refraction, a change in scattering will result when going from field-on to field-off conditions, and vice-versa. Maximum contrast results when the ordinary index of refraction matches the index of refraction of the medium. The closeness of the index matching will be dependent on the desired degree of contrast and transparency in the device, but the ordinary index of refraction of the crystal and the index of the medium will preferably differ by no more than 0.1, preferably 0.03, more preferably 0.01, especially 0.001. The tolerated difference will depend upon capsule size. 2074 2 0 Desirably the electric field E shown in Fig. 3 is applied to the liquid crystal 30 in the capsule 32 for the most part rather than being dissipated or dropped substantially in the encapsulating material. There should not be a substantial voltage drop across or through the material of which the wall 54 of the capsule 32 is formed; rather, the. voltage drop should occur across the liquid crystal 30 within the volume 31 of the capsule 32.

The electrical impedance of the encapsulating medium preferably should in effect be large enough relative to that of the liquid crystal in the encapsulated liquid crystal 11 that a short circuit will not occur exclusively through the wall 54, say from point A via only the wall to point B, bypassing the liquid crystal. Therefore, for example, the effective impedance to induced or displacement current flow through or via only the wall 54 from point A to point B should be greater than the impedance that would be encountered in a path from point A to point A' inside the interior wall surface 50, through the liquid crystal material 30 to point B' still within the volume 31, ultimately to point B again. This condition will assure that there will be a potential difference between point A and point B. Such potential difference should be large enough to produce an electric field across the liquid crystal material that will tend to align the same. It will be appreciated that due to geometrical considerations, namely the length through only the wall from point A to point B, for example, such condition still can be met even though the actual impedance of the wall material is lower than that of the liquid crystal material therein.

The dielectric constants (coefficients) of the material of which the encapsulating medium is formed and of which the liquid crystal is comprised, and the effective capacitance values of the capsule wall 54, particularly in a radial direction and of the liquid crystal across which the electric field E is imposed, all should be so related that the wall 54 of the capsule 32 does not substantially drop the magnitude of the applied electric field E. Ideally the capacitance dielectric constants (coefficients) of the entire layer 61 (Fig. 4) of encapsulated liquid crystal material should be substantially the same for the field-on condition. £07 The liquid crystal 30 will have a dielectric constant value that is anisotropic. It is preferable that the dielectric constant (coefficient) of the wall 54 be no lower than the dielectric constant (coefficient) of the anisotropic liquid crystal material 30 to help meet the above conditions for optimum operation. It is desirable to have a relatively high positive dielectric anisotropy in order to reduce the voltage requirements for the electric field E. The differential between the dielectric constant (coefficient) for the liquid crystal 30 when no electric field is applied, which should be rather small, and the dielectric constant (coefficient) for the liquid crystal when it is aligned upon application of an electric field, which should be relatively large, should be as large as possible. The dielectric constants (coefficients) relationships are discussed in the wo 83/01016 application, the entire disclosure of which is specifically incorporated by reference here. It should be noted, in particular, though, that the critical relationship of dielectric values and applied electric field should be such that the field applied across the liquid crystal material in the capsule(s) is adequate to cause alignment of the liquid crystal structure with respect to the field. The lower dielectric values of commonly used liquid crystals are, for example, from as low as about 3.5 to as high as about 8.

The capsules 32 may be of various sizes. The smaller the size, though, the higher the requirements will be for the electric field to effect alignment of the liquid crystal in the capsule. Preferably, though, the capsules should be of uniform size parameters so that the various characteristics, such as the optical and electrical characteristics, of an apparatus, such as a display, using the encapsulated liquid crystal will be substantially uniform. Moreover, the capsules 32 should be at least 1 micron in diameter so they appear as discrete capsules relative to an incident light beam; a smaller diameter would result in the light beam "seeing" the capsules as a continuous homogeneous layer and would not undergo the required isotropic scattering. Examples of capsule sizes, say from 1-30 microns diameter, and of liquid crystal material are in the above concurrently filed application and are hereby specifically incorporated by reference.

A preferred liquid crystal material in accordance with the best mode of the invention is that nematic material NM-8250, an ester soj^^g/y F* 20742 American Liquid Xtal Chemical Corp., Kent, Ohio, U.S.A. Other examples may be ester combinations, biphenyl and/or biphenyl combinations, and the like.

Several other types of liquid crystal material useful according to the invention include the following four examples, each being a recipe for the respective liquid crystal materials. The so-called 10% material has about 10% 4-cyano substituted materials; the 20% material has about 20% 4-cyano substituted materials, and so on.

% Material Pentylphenylmethoxy Benzoate Pentylphenylpentyloxy Benzoate Cyanophenylpentyl Benzoate Cyanophenylheptyl Benzoate Cyanophenylpentyloxy Benzoate Cyanophenylheptyloxy Benzoate Cyanophenyloctyloxy Benzoate Cyanophenylmethoxy Benzoate 20% Material Pentylphenylmethoxy Benzoate Pentylphenylpentyloxy Benzoate Cyanophenylpentyl Benzoate Cyanophenylheptyl Benzoate Cyanophenylpentyloxy Benzoate Cyanophenylheptyloxy Benzoate Cyanophenyloctyloxy Benzoate Cyanophenylmethoxy Benzoate 40% Material Pentylphenylmethoxy Benzoate P entylphenylpentyloxy Benzoate Cyanophenylpentyl Benzoate Cyanophenylheptyl Benzoate Cyanophenylpentyloxy Benzoate Cyanophenylheptyloxy Benzoate 54 grams 36 grams 2.6 grams 3.9 grams 1.2 grams 1.1 grams 9.94 grams 0.35 grams 48 grams 32 grams 5.17 grams 7.75 grams 2.35 grams 2.12 grams 1.88 grams 0.705 grams 36 grams 24 grams 10.35 grams 15.52 grams 4.7 grams 4.23 grams 207 4? Cyanophenyloctyloxy Benzoate 3.76 grams Cyanophenylmethoxy Benzoate 1.41 grams 40% MOD Pentylphenylmethoxy Benzoate 36 grams Pentylphenylpentyloxy Benzoate 24 grams Cyanophenylpentyl Benzoate 16 grams Cyanophenylheptyl Benzoate 24 grams The encapsulating medium forming respective capsules 32 should be of a type that is substantially completely unaffected by and does not affect the liquid crystal material. Various resins and/or polymers may be used as the encapsulating medium. A preferred encapsulating medium is polyvinyl alcohol (PVA), which has a good, relatively high, dielectric constant and an index of refraction that is relatively closely matched to that of the preferred liquid crystal material. An example of preferred PVA is an about 84% hydrolized, molecular weight of at least about 1,000, resin. Use of a PVA of Monsanto Company identified as Gelvatol 20/30 represents the best mode of the invention.

A method for making emulsified or encapsulated liquid crystals 11 may include mixing together the containment or encapsulating medium, the liquid crystal material, and perhaps a carrier medium, such as water. Mixing may occur in a variety of mixer devices, such as a blender, a colloid mill, which is most preferred, or the like. What occurs during such mixing is the formation of an emulsion of the ingredients, which subsequently can be dried eliminating the carrier medium, such as water, and satisfactorily curing the encapsulating medium, such as the PVA. Although the capsule 32 of each thusly made encapsulated liquid crystal 11 may not be a perfect sphere, each capsule will be substantially spherical in configuration because a sphere is the lowest free energy state of the individual droplets, globules or capsules of the emulsion, both when originally formed and after drying and/or curing.

The capsule size (diameter) preferably should be uniform in the emulsion for uniformity of operation with respect to effect on incident light and response to electric field. Exemplary capsule size range may be from 20742 0 about 0.3 to about 100 microns, preferably 0.3 to 30 microns, especially 3 to 15 microns, for example 5 to 15 microns.

Various techniques may be employed to form the support medium 12, which may be of the same or similar material as the encapsulating or containment medium. For example, the lower support medium 12b may be formed using a molding or casting process. The electrode 13 and liquid crystal material may be applied for support by that medium 12b. The electrode 14 may be applied, e.g. by printing. Thereafter, the upper support medium portion 12a may be poured or cast in place to complete enclosing the encapsulated liquid crystal material and the electrodes. Alternatively, the support medium portions 12a, 12b may be a substantially transparent plastic-like film or a plate of glass, as is described in Example 1, for example.

The reflectance medium 18, if a solid, for example, may be applied to the support medium portion 12b by a further casting or molding technique, and a lower coating 21 of black or colored light absorbing material may be applied to the back surface of the reflectance medium 18, i.e. the surface remote from the interface thereof with the lower support medium portion 12b. Alternatively, the reflectance medium may be an air or other fluid gap between the support medium portion 12b and the absorber 21, or a tuned dielectric layer may be applied by conventional evaporation technique directly to the bottom surface of the lower support medium portion 12b in place of the reflectance medium 18, as will be described further below.

The following are several examples of materials and methods for making liquid crystal display devices and operational characteristics thereof in accordance with the present invention.

Example 1 An example of the isotropically scattering material was produced by mixing about 2 grams of 8250 (an ester by American Liquid Xtal) nematic liquid crystal with about 4 grams of a 20% solution of Airco 405 polyvinyl alcohol (the other 80% of such solution was water). The material was mixed in a small homogenizer at low shear to form an emulsion. Using 20742 0 a doctor blade at about a 5 mil setting the emulsion was coated on an electrode of Intrex material already in position on a polyester film base of about 5 mils thickness. Such film was that known as Mylar. Another sheet of such film with such an electrode was placed on the encapsulated liquid crystal layer, thus sandwiching the latter between the respective electrodes and films. The individual encapsulated operationally nematic liquid crystal capsules or particles were about 4 to 5 microns in diameter and the total layer of encapsulated liquid crystal material was about 20 to 30 microns thick.

The device made according to Example 1 was tested. The resulting material scattered light in a zero electric field (hereinafter usually referred to as a zero field or field off condition) condition. In an applied field of 10 volts the scattering decreased and at 40 volts scattering stopped altogether.

Although a homogenizer was used, other types of mixers, blenders, etc., may be used to perform the desired mixing.

Example 2 An example of the isotropically scattering material was produced by mixing about 2 grams of 8250 nematic liquid crystal with about 4 grams of a 22% solution (78% water) of Gelvatol 20/30 (by Monsanto) polyvinyl alcohol. The material was mixed in a small homogenizer at low shear to form an emulsion. The emulsion was coated on Intrex film electrode and Mylar film polyester base, as in Example 1, with a doctor blade at a 5 mil setting and the sandwich was completed as in Example 1. The nematic capsules or particles were about 3 to 4 microns in diameter, and the encapsulated liquid crystal layer was about 25 microns thick.

The device made according to Example 2 was tested. The resulting material scattered light in a zero or field-off electric field condition. In an applied field of 10 volts the scattering decreased and at 40 volts scattering stopped altogether.

Example 3 An example of the isotropically scattering material was produced by mixing about 2 grams of E-63 (a biphenyl by British DrugHouse, a 207420 subsidiary of E. Merck of West Germany) nematic liquid crystal with about 4 grams of a 22% solution of Gelvatol 20/30 (by Monsanto) polyvinyl alcohol. The material was mixed in a small homogenizer at low shear to form an emulsion. The emulsion was coated on Intrex film electrode and Mylar film polyester base with a doctor blade at a 5 mil setting and the sandwich was completed as above. The thickness of the encapsulated liquid crystal layer was about 25 microns; the nematic capsules or particles were about 4 to 5 microns in diameter.

The device made according to Example 3 was tested. The resulting material scattered light in a zero field or field-off condition. In an applied field of 7 volts the scattering decreased and at 35 volts scattering stopped altogether.

Example 4 An example of the isotropically scattering material was produced by mixing about 2 grams of 8250 liquid crystal with about 4 grams of a 22% solution of Gelvatol 20/30 polyvinyl alcohol. The material was mixed in a small homogenizer at low shear to form an emulsion. The emulsion was coated on Intrex film electrode and Mylar polyester film base with a doctor blade at a 5 mil setting and the sandwich was completed as above. The thickness of the encapsulated liquid crystal layer was about 25 microns; the nematic capsules or particles were about 4 to 5 microns in diameter.

To improve the emulsion stability and coating uniformity 0.001% of GAF LO 630 non-ionic surfactant (detergent) was added before the mixing step. Improved performance instability of the emulsion and in coating of the emulsion onto the electrode/polyester film base were noted. The operational results were otherwise substantially similar to those described above with respect to Example 1.

Thus, it will be appreciated that in accordance with the invention a surfactant, preferably a non-ionic surfactant, a detergent, or the like may be mixed with the encapsulated liquid crystal material prior to depositing on the electrode coated film, as was just described above. 20742 0 -28-Example 5 The steps of Example 1 were followed using the same materials as in Example 1 except that 1/8 inch glass plate was substituted for the Mylar film. Operation was substantially the same as was described with respect to Example 1.

Example 6 A mixture was formed of 8250 nematic liquid crystal and a solution of 15% AN169 Gantrez in 85% water. Such Gantrez is poly(methyl vinyl ether/maleic anhydride), a polymaleic acid product, of GAF Corporation. The mixture was of 15% liquid crystal and 85% Gantrez as the containment medium. The mixture was homogenized at low shear to form an emulsion, which was applied to an electrode/support film as above; such support film was about 1.2 mils thick. After drying of the emulsion, the resulting liquid crystal emulsion responded to an electric field generally as above, scattering when in field-off condition, showing a threshold of about 7 volts to begin reducing scattering, and having a saturation level of substantially no scattering at about 45 volts.

Another example of an acid type containment medium useful in the invention is carbopole (carboxy polymethylene polymer by B. F. Goodrich Chemical Company), or polyacid.

Other types of support media 12 that may be used include polyester materials; and polycarbonate material, such as Kodel film. Tedlar film, which is very inert, also may be used if adequate adhesion of the electrode can be accomplished. Such media 12 preferably should be substantially optically transparent.

Several different polymer containment media that may be used are listed in Chart I below. The chart also indicates several characteristics of the respective polymers. 207420 CHARTI Temperature Molecular <5c Containment Medium Viscosity % Hydrolyzed Weight % Solutions /30 4-6 CPS 88.7 - 85.5 10,000 4% at 20°C Gelvatol, by Monsanto Company 40/20 2.4-3 CPS 77 - 72.9 3,000 4% at 20°C Gelvatol, by Monsanto Company 523, by 21-25 87 - 89 — 4% at 20°C Air Products And Chemicals, Inc. 72/60 55-60 99 -100 — 4% at 20°C Elvanol, by DuPont Co. 405 2-4 CPS 80 -82 — 4% at 20°C Poval, by Kurashiki Other Gelvatol PVA materials that may be used include those designated by Monsanto as 20-90; 9000; 20-60; 6000; 3000; and 40-10.

A preferred quantity ratio of liquid crystal material to containment medium is about one part by weight liquid crystal material to about three parts by weight of containment medium. Acceptable encapsulated liquid crystal emulsion operative according to the invention also may be achieved using a quantity ratio of about one part liquid crystal material to about two parts containment medium, e.g., Gelvatol PVA. Moreover, although a 1:1 ratio also will work, generally it will not function quite as well as material in the ratio range of from about 1:2 to about 1:3.

Turning now to Figs. 4 and 5, a portion 60 of a liquid crystal display device in accordance with the present invention is illustrated. The portion or device 60 is a completion of the liquid crystal apparatus 10 described above with reference to Fig. 1 in that plural encapsulated liquid crystals 11, indeed plural layers thereof, are contained in a support medium 12. The sizes, thicknesses, diameters, etc., of the several parts shown in 20742 Figs. 4 and 5 are not necessarily to scale; rather the sizes are such as is necessary to illustrate the several parts and their operation.

The electrodes 13, 14 are employed to apply a desired electric field to effect selective alignment of the liquid crystal material in the manner shown in Fig. 3, for example. Means other than electrodes may be employed to apply some type of input to the display device 60 for the purpose of effecting ordered or random alignment of the liquid crystal.

The encapsulated liquid crystals 11 are arranged in several layers 61 within the display portion 60. The layers 61 may be divided into several portions representing the various characters or portions of characters intended to be displayed by the display 60. For example, the longer lefthand portion 61L of the layers 61 shown in Fig. 4 may represent a section view through one part of a well known 7-segment display pattern, and the relatively short righthand portion 61R of the layers 61 shown in Fig. 4 may represent a part of another 7-segment character display. Various patterns of liquid crystal material may be employed in accordance with the present invention. A zone 62 of support medium 12 fills the area between the liquid crystal layer portions 61L, 61R. Subsequent reference to layers 61 will be in the collective, i.e. referring to layer 61 as including the several levels or layers comprising the same. As an example, the composite thickness of such layer 61 may be from about 0.3 mils to about 10 mils; uniform thickness is preferred for uniform response to electric field, scattering, etc.

Such an arrangement or pattern of encapsulated liquid crystal material layer portions 61L and 61R separated at zone 62 by support medium 12 or other material is facilitated, or even made possible due to the encapsulating or confining of the liquid crystal in discrete containment media, such as is formed by the preferred stable emulsion. Therefore, especially on a relatively large size device such as a display, billboard, optical shutter, etc., encapsulated liquid crystal material may be applied to the support medium 12 only where it is required to provide the selectable optical characteristics. Such patterning can reduce the amount of such material required for a particular application. Such patterning is further made possible due to the desired functional operation described in detail below. 207420 The display 60 may be used, for example, in an air environment, such air being represented by the reference numeral 63, and the air forms an interface 64 at the viewing side or from the viewing direction 20 with the support medium 12. The index of refraction N of the external medium 63 is different from the index of refraction N' of the encapsulating medium 12, the latter usually being larger than the former. As a result, a beam of light 65, which arrives generally from the viewing direction 20, passing through the interface 64 into the support medium 12 will be bent toward the normal, which is an imaginary line 66 perpendicular to that interface 64. That light beam 65a inside the support medium 12 will be closer to normal than the incident beam 65 satisfying the equation relationship N Sine -©-= N' Sine-©1, wherein-0-is the angle of the incident light beam 65 with respect to the normal and-©1 is the angle of the light beam 65a with respect to normal. Such mathematical relationship will apply at the interface 19, as follows: N' Sine -G1 = N" Sine To achieve the desired total internal reflection in accordance with the invention, the index of refraction N" of the reflectance medium 18 is smaller than the index of refraction N' of the support medium 12. Accordingly, if the light beam 65a, for example, were able to and did pass through the interface 19, it would be bent away from the normal at the interface 19 to the angle-©11 with respect to normal. Actually, since the light beam 65, 65a is not scattered off course by the liquid crystal material -in layers 61, i.e., because it passes through the zone 62, it will indeed likely exit through the interface 19.

In operation of a liquid crystal display 60 (Fig. 4) the operationally nematic liquid crystal 30 is in distorted or random alignment due to existence of a field-off condition. Incident light beam 70 enters the support medium 12 at the interface 64 and is bent as the light beam 70a that impinges as incident light on the layer 61 of encapsulated liquid crystal. The random or distorted encapsulated liquid crystal material will isotropically scatter the light incident thereon. Therefore, there are several possibilities of how such incident light beam 70a would tend to be scattered, as follows: A. One possibility is that the incident light beam 70a will be directed according to the dotted line 70b toward the interface 19. The angle 20742 at which the light beam 70b impinges on the interface 19 is within the illustrated solid angle oC (defined in the planar direction of the drawing of Fig. 4 by the dashed lines 71) of a so-called cone of illumination. Light falling within such solid angle ©< or cone of illumination is at too small an angle with respect to normal at the interface 19 to be totally internally reflected at that interface; therefore, the light beam 70b will pass through interface 19 while bending away from the normal to form the light beam 70c. Light beam 70c passes into the reflectance medium 18 and is absorbed by layer 21.

B. Another possibility is that the light beam 70a will be isotropically scattered in the direction of the light beam 70d outside the cone angle . Total internal reflection will occur at the interface 19 causing the light beam 70d to be reflected as light beam 70e back to the layer 61 of encapsulated liquid crystal material where it will be treated as another independently incident light beam thereto, just like the light beam 70a from which it was derived. Therefore, such light beam 70e will undergo isotropic scattering again as is described herein.

C. Still another possibility is that the incident light beam 70a, or that derived therefrom, such as the light beam 70e, will be isotropically scattered toward the interface 64 at an angle that is so close to normal at that interface 64 that the light beam will pass through the interface 64 into the "medium" 63, such as the air, to be viewed by an observer or observing instrument. The solid angle ' of a cone of illumination, like the cone angle c\ mentioned above, within which such scattered light beam 70e must fall to be emitted out through the interface 64 is represented by the single dot phantom lines 72. Light beam 70f represents such a light beam that is so emitted from the display 60. It is that light, e.g. the sum of such emitted light beams 70f, which exits at the interface 64 that causes the layer 61 of encapsulated liquid crystals 11 to give the appearance of a white or bright character as viewed from the viewing direction 20.

D. Still a further possibility is that the light beam 70a may be isotropically scattered in the direction of the light beam 70g. Light beam 70g is outside the solid cone angle ' and, therefore, will undergo total 207420 internal reflection at the interface 64, whereupon the reflected beam 7Oh will impinge back on the layer 61 as an effectively independent incident light beam, like the beam 70e mentioned above and having a similar effect.

The index of refraction of the electrodes 13,14 usually will be higher than that (those) of the containment medium and support medium and the containment and support media indices of refraction preferably are at least about the same. Therefore, the light passing from the containment medium into the electrode material will bend toward the normal, and that passing from the electrode into the support medium will bend away from the normal; the net effect of the electrode thus being nil or substantially negligible. Accordingly, the majority of total internal reflection will occur at the interfaces 19,64.

As viewed from the viewing direction 20, the zone 62 will appear dark or colored according to the composition of the absorbent layer 21. This is due to the fact that the light beam 65, 65a, 65b, representing the majority of light that passes through zone 62, will tend to pass through interface 64, support medium 12, the interface 19 and the reflectance medium 18, being bent toward or away from the normal, at respective interfaces as shown, ultimately being substantially absorbed by layer 21.

Briefly referring to Fig. 5, the field-on or ordered alignment condition and operation of the encapsulated liquid crystal layer 61 in the display device 60 are shown. The encapsulated liquid crystals 11 in the layer 61 of Fig. 5 are like those seen in Fig. 3. Therefore, like the light beam 65, 65a, 65b which passes through the zone 62 and is absorbed by the layer 21, the light beam 70, 70a, 70i will follow a similar path also being transmitted through the aligned and, thus, effectively transparent or non-scattering layer 61. At the interface 19, the light beam 70a will be bent away from the normal and subsequently light beam 7Oi will be absorbed by the layer 21. Accordingly, whatever visual appearance the light beam 65 would tend to cause with respect to an observer at the viewing location 20, so too will the light beam 70 cause the same effect when passing through the orderly aligned encapsulated liquid crystal material. Thus, when the display 60, and particularly the encapsulated liquid crystal material therein, is in the 2074 2 0 orderly aligned or field-on condition, the area at which the liquid crystal is located will have substantially the same appearance as that of the zone 62.

It is noted that if either the incident beam 65 or 70 were to enter the support medium 12 at the interface 64 at such a large angle with respect to the normal there, and, therefore, ultimately to impinge on the interface 19 at an angle greater than one falling within the so-called cone of light angle , such beam would be totally internally reflected at the interface 19. However, such reflected light probably would remain within the support medium 12 due to subsequent transmission through the layer of liquid crystal material 61 and subsequent total internal reflectance at the interface 64, etc.

In Fig. 6, the preferred reflectance medium 80 air is illustrated. In Fig. 6 primed reference numerals designate elements corresponding to those designated by the same unprimed reference numerals in Figs. 4 and 5. The display 60' has an interface 19' formed with air 80. To achieve absorbence of the light transmitted through the interface 19' and medium 80, a black or colored absorber 81 may be positioned at a location displaced from the interface 19'. The preferred absorber 81 is carbon black which may be mounted on a support surface positioned generally as is shown in Fig. 6. The preferred liquid crystal is NM-8250; the preferred containment medium is PVA; and the preferred support medium 12 is polyester. Moreover, it is preferred that the index of refraction of the support medium 12a, 12b and that of the containment medium for the liquid crystal be at least substantially the same; this helps to assure that the total internal reflection will occur primarily at the interfaces 19', 64' and not very much, if at all, at the interface between the containment medium and support medium; this minimizes optical distortion while maxi-mizing contrast. The display 60' functions substantially the same as the display 60 described above with reference to Figs. 4 and 5.

Referring, now, to Figs. 7 and 8, a modified liquid crystal display 90 includes a support medium 12 with a layer of encapsulated liquid crystal material 61, as above. However, at the interface 19 there is a tuned dielectric interference layer 91. The thickness of the dielectric layer 91, 20742 0 which is exaggerated in the drawings, preferably is an odd whole number function or multiple of lambda divided by two such as 3 7*/2, 5 7*/2, etc., wherein ft is the wavelength of the light in the support display 60. The tuned dielectric interference layer 91 may be applied to the back surface of the support medium 12 by conventional evaporation technique. Such dielectric layer may be comprised of barium oxide (BaO), lithium fluoride (LiF) or other material that provides the desired optical interference function. Preferably such layer has a smaller index of refraction than the medium 12 to obtain an interface 19 at which total internal reflection of light within cone angle will be internally reflected. A comprehensive description of optical interference is found in Optics by Born and Wolf, Fundamentals of Physics, 2nd Ed., 1981, Resnick and Halliday, pgs. 731-735, and in University Physics by Sears and Zemansky, the relevant disclosures of which are hereby incorporated by reference.

In the field-off/random liquid crystal alignment condition shown in Fig. 7 the display 90 will function substantially the same as the display 60 described above with respect to: (a) isotropic scattering of light by the encapsulated liquid crystal material layer 61; (b) the total internal reflection of that light falling outside the solid angle conec^ , this due to the interface 19 seen in Fig. 7, (or cK.' with respect to light isotropically scattered to the interface 64), and; (c) the transmitting of light, such as the light beam 70f, toward the viewing direction 20 to give the appearance of a white character on a relatively dark background.

By use of the tuned dielectric interference layer 91 and optical interference, in the field-off condition the illumination effected of the encapsulated liquid crystal layer 61 is further enhanced. Specifically, the effective cone of light angle cA becomes reduced to the angle (J) shown in Fig. 7. Generally, an incident light beam 92 impinging on the interface 64 will be deflected as the light beam 92a which then is incident on the layer 61. If the light beam 92a were isotropically scattered as beam 92b at an angle outside the original angle c*. , the total internal reflection operation described above with reference to the display 60 will occur. However, if the light beam 92a is isotropically scattered as light beam 92c at an angle 20742 0 falling within the cone of light but outside the cone of light (f, it will actually be reflected constructive optical interference will occur further to enhance the illumination of the encapsulated liquid crystal layer 61.

More particularly when the light beam 92c enters the tuned dielectric interference layer 91, at least a portion 9 2d actually will be reflected back toward the interface 19. At the interface 19, there will be constructive interference with another incident light beam 93 increasing the effective intensity of the internally reflected resultant light beam 94, which is directed back toward the encapsulated liquid crystal layer 61 enhancing the illumination thereof. The result of such constructive interference is that the display 90 yields more light beams scattered up to or reflected up to the layer 61 than in the display 60. However, there is a disadvantage in that the viewing angle at which the display 90 will function effectively is less than the viewing angle at which the display 60 will function effectively. Specifically, incident light entering the support medium 12 at an angle equal or less than the angle <=\ with respect to the interface 64, will tend to be totally reflected because the back or reflective surface of the tuned dielectric interference layer 91 will tend to act as a mirror so that some contrast will be lost in the display 90. The angled , if it exists at all, in connection with the display 60 would tend to be smaller than the angle of the display 90.

Light beams 95 and 96 (Eig. 7) that pass through the zone 62 of the display 90 and light beams 92L (Fig. 8) that pass through the orderly aligned (field-on) liquid crystal layer 61 and fall within the cone angle O will undergo destructive optical interference. Therefore, from the viewing area 20 the zone 62 and the area where there is ordered field-on liquid crystal will appear relatively dark, i.e. as a dark background relative to the white or brightly illuminated liquid crystal layer 61 portion that is field-off and scattering. If desired, an absorber (black or colored) may be used beyond the layer 91. Also, the color of background may be altered as a function of the thickness of the layer 91.

Turning now to Fig. 9, an example of a liquid crystal device 100 in accordance with the invention is shown in the form of a liquid crystal 207420 display device, which appears as a square cornered figure eight 101 within the substrate or support medium 12, which in this case preferably is a plastic material, such as Mylar, or may alternatively be another material, such as glass, for example. The shaded area appearing in Fig. 9 to form the square cornered figure eight is comprised of one or more layers 61 of encapsulated liquid crystals 11 arranged in one or more layers on and adhered to the substrate 12. An enlarged fragmentary section view of a portion of the figure eight 101 is illustrated in Fig. 4 as the display 60, 60' or 90 described above with reference to Figs. 4-8. Each of the seven segments of the figure eight 101 may be selectively energized or not so as to create various numeral characters. Energization here means the placing of the respective segments in a condition to appear bright relative to background. Therefore, energization means field-off or random alignment condition of, for example, segments 101a and 101b to display "1" while the other segments are in field-on, ordered alignment.

Figs. 10 and 11 illustrate, respectively in fragmentary section and fragmentary isometric-type views, an embodiment of the invention representing the preferred arrangement of the liquid crystal layer 61" and electrodes 13", 14" in the support medium 12". In Figs. 10 and 11, double primed reference numerals designate parts corresponding to those designated by unprimed reference numerals in Figs. 4 and 5, or primed reference numerals in Fig. 6. In particular, it is preferred according to the illustration of Figs. 10 and 11 that the display device 60"have the layer 61" and the electrode 13" substantially continuous over the entire or at least a relatively large portion of a display device. The electrode 13" may be connected, for example, to a source of electrical ground potential. The electrode 14" may be divided into a plurality of electrically isolated electrode portions, such as those represented at 14a, 14b, each of which may be selectively coupled to a source of electric potential to complete application of an electric field across that liquid crystal material which is between such energized electrode portion 14a or 14b and the other electrode 13". Therefore, for example, an electric field may be applied across the electrodes 14a, 13" causing the encapsulated liquid crystal material falling substantially directly there- 20742 0 between to be in ordered, field-on alignment and, thus, effectively optically transparent in the manner described above. At the same time, it may be that the electrode 14b is not connected to a source of electric potential so that the liquid crystal material between such electrode 14b and the electrode 13" will be in distorted or random alignment and, therefore, will appear relatively bright from the viewing direction 20". A small gap 120 between electrodes 14a, 14b provides electric isolation therebetween to permit the just-described separate energization or not thereof.

Briefly referring to Fig. 12, the preferred embodiment and best mode of the present invention is shown as the display 60'". In Fig. 12 the various portions designated by triple primed reference numerals correspond to those portions designated by similar reference numerals, as are described above. The display device 60'" is made generally in accordance with the numbered examples presented above. In particular, the lower support medium 12b"' is formed of Mylar film having an indium doped tin oxide Intrex electrode 13'" thereon; and the layer 61'" of encapsulated liquid crystal material was applied to the electrode coated surface, as is shown. Several electrode portions 14a'", 14b'", etc. with a respective gap 120'" therebetween, were applied either directly to the surface of the layer 61'" opposite the support medium 12b'" or to the support medium 12a'", and the latter was applied in the manner shown in Fig. 12 to complete a sandwich of the display device 60"'. Moreover, the reflectance medium 80'" was air, and a carbon black absorber 21'" mounted on a support shown in Fig. 12 was placed opposite such air gap 80'" from the support medium 12b'", as can be seen in the figure. Operation of the display device 60'" is according to the operation described above, for example, with reference to Figs. 4-6 and 10.

Referring to Fig. 13, an encapsulated liquid crystal 130 of the type described in Example 7 below is schematically shown. Such capsule 130 includes a spherical capsule wall 131 of containment material 132, operationally nematic liquid crystal material 133 inside the capsule, and a cholosteric chiral additive 134. The additive 134 is generally in solution with the nematic material 13, although the additive is shown in Fig. 13 at a central location because its function primarily is with respect to the liquid crystal 20742 0 material remote from the capsule wall, as is described further below. The capsule 130 is shown in field-off, distorted condition with the liquid crystal material distorted in the manner described above, for example, with reference to Fig. 2. The liquid crystal material most proximate the wall 131 tends to be forced to a shape curved like the inner boundary of that wall, and there is a discontinuity 135 analogous to the discontinuity 55 shown in Fig. 2.

Example 7 The steps of Example 1 were followed using the same materials and steps as in Example 1 except that 3% cholesterol oleate (chiral additive), a cholosteric material, was added prior to the mixing step, and then such mixing was carried out at very low shear. The resulting capsules were somewhat larger than those produced in Example 1. The encapsulated liquid crystal material was still operationally nematic.

In operation of the material formed in Example 7, it was found that the chiral additive improved (reduced) the response time of the operationally nematic encapsulated liquid crystal material, particularly in returning to the distorted alignment generally following the wall shape of the individual capsules, promptly after going from a field on to a field off condition. In such relatively large capsules, say about on the order of at least 8 microns total diameter, when going to the field off condition, it is the usual case that the liquid crystal material adjacent the capsule wall would return to the distorted alignment following the capsule wall shape or curvature faster than would the liquid crystal material closer to the center of the capsule; this disparity tends to slow the overall response time of the material. However, the chiral additive induces a tendency for the structure to twist. This influence on the nematic material is most noticeable remote from the capsule wall and, thus, speeds up the return of such relatively remote material to distorted alignment, preferably influenced by the shape of the capsule wall. Such chiral additive may be in the range of about 0.1% to about 8% of the liquid crystal material and a preferred range of about 2% to about 5%. The amount may vary depending on the additive and the liquid crystal and could even be outside the stated range as long as the capsule remains operationally nematic. 207420 It will be appreciated that the encapsulated liquid crystal 130 of Fig. 13 may be substituted in various embodiments of the invention described in this application in place of or in conjunction with the otherwise herein described encapsulated liquid crystal material. Operation would be generally along the lines described in Example 7.

Another additive also may be used to reduce and/or otherwise to control the viscosity of the liquid crystal during manufacturing of a device 60, for example. The reduced viscosity may have a positive effect on emulsion formation and/or on the process of applying the emulsion to an electrode covered support medium 12. An example of such an additive may be chloroform, which is water-soluble and leaves the emulsion on drying.

Example 8 An emulsion was prepared using about 15 grams of 22% (the rest was water) low viscosity, medium hydrolysis PVA; about 5 grams of 8250 liquid crystal (of American Liquid Xtal) containing about 3% (percentages are with respect to the weight of the liquid crystal) cholesterol oleate, about 0.1% of a 1% (the rest was water) solution of L.O. 630 surfactant, and 15% chloroform.

Such material was mixed at high shear for about 3 minutes. The capsules produced were about 1 to 2 microns in diameter. A layer of such encapsulated liquid crystal was applied to an electrode covered support medium using a doctor blade at a gap 5 setting. The material was dried and operated generally as the materials described above.

A modified liquid crystal display device 140 in accordance with the present invention is shown schematically in Figs. 14 and 15. In the device 140 the primary source of illumination is derived from a light source 141 at the so-called back or non-viewing side 142 of the display device. More specifically, the display device 140 includes a layer 61 of encapsulated liquid crystal between a pair of electrodes 13, 14 supported on upper and lower support media 12a, 12b generally in the manner disclosed above, for example with reference to Fig. 12. The reflectance medium 80 is an air gap, as was described in connection with the preferred embodiment above.

A light control film (LCF) sold by 3-M Company is shown at 143; the one preferrd is identified by product designation LCFS-ABRO-30°-OB- 20742 0 60°-CLEAR-GLOS-.030. The light control film 143 is a thin plastic sheet preferably of black substantially light absorbing material that has black micro-louvers 144 leading therethrough from the back surface 145 toward the front surface 146 thereof. Such film or like material may be used in connection with the various embodiments of the invention. Such film may in effect tend to collimate the light passing therethrough for impingement on the liquid crystal material.

The micro-louvers function like a Venetian blind to direct light from the source 141, for example light beams 150, 151, into and through the display device 140, and particularly through the support medium 12 and liquid crystal layer 61, at an angle that would generally be out of the viewing angle line of sight of an observer looking at the display device 140 from the viewing direction 20 - this when the liquid crystal is aligned or substantially optically transparent. Such field-on aligned condition is shown in Fig. 14 in which the light beams 150, 151 pass substantially through the display device 140 out of the line of view. Moreover, light, such as light beam 152, incident on the display device 140 from the viewing direction 20 will generally pass through the support medium 12 and aligned, field-on liquid crystal layer 61 for absorption by the black film 143, which functions as the absorber 21"1 in connection with Fig. 12, for example.

However, as is seen in Fig. 15, when the liquid crystal layer 61 is in the field-off condition, i.e. the liquid crystal is distorted or randomly aligned, the light beams 150, 151 from the source 141 are isotropically scattered by the layer of liquid crystal material 61 causing total internal reflection and brightened appearance of the liquid crystal material in the manner described above. Thus, for example, the beam 151 is shown being isotropically scattered as beam 151a, totally internally reflected as beam 151b, and being further isotropically scattered as beam 151c which is directed out through the interface 64 toward the viewing direction 20. The display device 140 of Figs. 14, 15 is particularly useful in situations where it is desirable to provide lighting from the back or non-viewing side. However, such display device also will function in the manner described above, for example with respect to the display device 60"' of Fig. 12, even without the 2 074 2 0 back light source 141 as long as adequate light is provided from the viewing direction 20. Therefore, the device 140 may be used in daylight, for example, being illuminated at one or both sides by ambient light with or without the light source 141, and at night or in other circumstances in which ambient lighting is inadequate for the desired brightness, for example, by using the illumination provided from the source 141.

A display device 160 in Fig. 16 is similar to the display device 140 except that the light control film 161 is cemented at 162 directly to, or is otherwise placed in abutment with the support medium material 12b. Total internal reflection would occur in the manner described above when the display device 160 is illuminated with light from the viewing direction 20 due primarily to the interface 64 of the support medium 12a with air. There also may be some total internal reflection at the interface 162. However, since the LCF film is directly applied to the support medium 12b, a relatively large quantity of the light reaching the interface 162 will be absorbed by the black film. Therefore, in the display device 160 it is particularly desirable to supply a back lighting source 141 to assure adequate illumination of the liquid crystal material in the layer 61 for achieving the desired bright character display function in accordance with the invention.

Briefly referring to Fig. 17, there is shown an alternate embodiment of encapsulated liquid crystal material 200, which may be substituted for the various other embodiments of the invention disclosed herein. The encapsulated liquid crystal material 200 includes operationally nematic liquid crystal material 201 in a capsule 202 having preferably a generally spherical wall 203. In Fig. 17 the material 200 is in field-off condition, and in that condition the structure 204 of the liquid crystal molecules is oriented to be normal or substantially normal to the wall 203 at the interface 205 therewith. Thus, at the interface 205 the structure 204 is generally oriented in a radial direction with respect to the geometry of the capsule 202. Moving closer toward the center of the capsule 202, the orientation of the structure 204 of at least some of the liquid crystal molecules will tend to curve in order to utilize, i.e. to fill, the volume of the capsule 202 with a substantially minimum free energy arrangement of the liquid crystal in the capsule, for example, as is seen in the drawing. 2074 2 Such alignment is believed to occur due to the addition of an additive to the liquid crystal material 201 which reacts with the support medium to form normally oriented steryl or alkyl groups at the inner capsule wall. More particularly, such additive may be a chrome steryl complex or Werner complex that reacts with PVA of the support medium (12) that forms the capsule wall 203 to form a relatively rigid crust or wall with a steryl group or moeity tending to protrude radially into the liquid crystal material itself. Such protrusion tends to effect the noted radial or normal alignment of the liquid crystal structure. Moreover, such alignment of the liquid crystal material still complies with the above strongly curved distortion of the liquid crystal structure in field-off condition because the directional derivatives taken at right angles to the general molecular direction are nonzero.

An example of such material 200 is presented below: EXAMPLE 9 To a 5 gm sample of 8250 nematic liquid crystal was added .005 gm of a 10% solution of Quilon M, a chrome steryl complex manufactured by DuPont, along with 3 gm of chloroform. The resulting material was homogenized at low shear with 15 gms of a 22% w/w solution of Gelvatol 20/30 PVA (the remaining 78% of such Gelvatol solution was water).

The result was an encapsulated liquid crystal in which the capsule wall reacted with the Quilon M to form an insoluble shell.

By observation with polarized light it was determined that the capsule wall aligned the liquid crystal in a radial direction.

A film was cast on a Mylar support medium already having an Intrex electrode thereon, as above, using a doctor blade with a gap setting of 5 mils. The resulting film had a thickness of 1 mil on drying. An auxiliary electrode was attached. The material began to align in the capsule at 10 volts and was fully aligned at 40 volts. Such alignment would be like that shown in Fig. 3 above.

The invention may be used in a variety of ways to effect display of data, characters, information, pictures, etc. on both small and large scale. According to the preferred embodiment and best mode of the 20742 -44- - invention, the liquid crystal material is placed in the support medium 12 at only those areas where characters, etc., are to be formed. In the alternative, the layer 61 may extend across the entire support medium 12, and only those areas where characters are to be displayed will have electrodes for controlling field-on/field-off with respect to the proximate portions of the liquid crystal layer 61. As an optical shutter, the invention may be used to adjust the effective and/or apparent brightness of light viewed at the viewing side. Various other designs also may be employed, as may be desired, utilizing the enhanced scattering effected by the total internal reflection and/or optical interference principles in accordance with the present invention. _ Turning now to Fig. 18, a liquid crystal device in accordance with the present invention is indicated at 310. The device 310 includes an encapsulated liquid crystal 311 which is supported by a mounting substrate 312 across which an electric field may be applied via electrodes 313, 314.

The electrode of 313 may be, for example, a quantity of vacuum deposited indium tin oxide applied to the substrate 312, and the electrode 314 may be, for example, electrically conductive ink. A protective layer or coating 315 may be applied over the electrode 314 for protective purposes but such layer .315 ordinarily would not be necessary for supporting or confining the encapsulated liquid crystal 311 or the electrode .314. Voltage may be applied to the electrodes 313, 314 from an AC or DC voltage source 316, selectively closable switch 317, and electrical leads 318, 319 in turn to apply an electric field across the encapsulated liquid crystal 311 when the switch 317 is closed.

The encapsulated liquid crystal 311 includes liquid crystal material 320 contained within the confines or interior volume 321 of a capsule 322. According to the preferred embodiment and the best mode of the present invention, the capsule 322 is generally spherical. However, the principles of the invention would apply when the capsule 322 is of a shape other than spherical. Such shape should provide the desired optical and electrical characteristics that will satisfactorily coexist with the optical characteristics of the liquid crystal 320, e.g. index of refraction, and will permit an 207420 adequate portion of the electric field to occur across the liquid crystal material 320 itself for effecting desired alignment of the liquid crystal structure when it is desired to have a field on condition. A particular advantage to the preferred spherical configuration of the capsule 322 will be described below with respect to the distortion it effects on the liquid crystal structure.

The mounting substrate 312 and the electrodes 313, 314 as well as the protective coating 315 may be optically transmissive so that the liquid crystal device 310 is capable of controlling transmission of light therethrough in response to whether or not an electric field is applied across the electrodes 313, 314 and, thus, across the encapsulated liquid crystal 311. Alternatively, the mounting substrate 312 may be optically reflective or may have thereon an optically reflective coating so that reflection by such reflective coating of incident light received through the protective coating 315 will be a function of whether or not there is an electric field applied across the encapsulated liquid crystal 311.

According to the preferred embodiment and best mode of the invention a plurality of encapsulated liquid crystals 311 would be applied to the mounting substrate 312 in a manner such that the encapsulated liquid crystals adhere to the mounting substrate 312 or to an interface material, such as the electrode 313, for support by the mounting substrate 312 and retention in a fixed position relative to the other encapsulated liquid crystals 311. Most preferably the encapsulating medium of which the capsule 322 is formed is also suitable for binding or otherwise adhering the capsule 322 to the substrate 312. Alternatively, a further binding medium (not shown) may be used to adhere the encapsulated liquid crystals 311 to the substrate 312. Since the capsules 322 are adhered to the substrate 312, and since each capsule 322 provides the needed confinement for the liquid crystal material 320, a second mounting substrate, such as the additional one typically required in the prior art liquid crystal devices, ordinarily would be unnecessary. However, for the purpose of providing protection from scarring, electrochemical deterioration, e.g. oxidation, or the like, of the electrode 314, a protective coating 315 may be provided on the side or 2074 2 0 surface of the liquid crystal device 310 opposite the mounting substrate 312, the latter providing the desired physical protection on its own side of the device 310.

Since the encapsulated liquid crystals 311 are relatively securely adhered to the substrate 312 and since there ordinarily would be no need for an additional substrate, as mentioned above, the electrode 314 may be applied directly to the encapsulated liquid crystals 321.

An enlarged fragmentary section view of a portion 332 of a liquid crystal display, for example, like the figure eight 101 and substrate 12 of Fig 9, is illustrated in Fig. 19. As is seen in Fig. 19^ on the surface of the substrate 12 (312 in Fig. 19), which may be approximately 10 .mils thick, is deposited a 200 angstrom thick electrode layer 333 of, for example, indium tin oxide or other suitable electrode material such as gold, aluminum, tin oxide, antimony tin oxide, etc. _ One or more layers 334 of plural encapsulated liquid crystals 311 are applied and adhered directly to the electrode layer 333. Such adherence according to the preferred embodiment and best mode is effected by the encapsulating medium that forms respective capsules 322, although, if desired, as was mentioned above, an additional adhering or binding material may be used for such adherence purposes. The thickness of the layer 334 may be, for example, approximately 0.3 to 10 mils, preferably 0.7 to 4 mils, more preferably 0.8 to 1.2 mils, especially 1 mil. Other thicknesses may also be used, depending inter alia on the ability to form a thin film and the electrical breakdown properties of the film. A further electrode layer 335 is deposited on the layer 334 either directly to the material of which the capsules 322 are formed or, alternatively, to the additional binding material used to bind the individual encapsulated liquid crystals 311 to each other and to the mounting substrate 312. The electrode layer 335 may be, for example, approximately 1/2 mil thick and may be formed, for example, of electrically conductive ink or of the materials mentioned above for layer 333. A protective coating layer 336 for the purposes described above with respect to the coating 15 in Fig. 18 also may be provided as is shown in Fig. 19.

A feature of the present invention utilizing the encapsulated liquid crystals 311 is that a versatile substrate 312 can be created to be 20742 0 capable of displaying virtually any desired display as a function of only the selective segments of conductive ink electrodes printed on the liquid crystal material. In this case, the entire surface 331 of the substrate 312 may be coated with electrode material 333, and even the entire surface of that electrode material may be coated substantially contiguously with layer 334 of encapsulated liquid crystals 311. Thereafter, a prescribed pattern of electrode segments of conductive ink 335 may be printed where desired on the layer 334. A single electrical lead may attach the surface 331 to a voltage source, and respective electrical leads may couple the respective conductive ink segments via respective controlled switches to such voltage source. Alternatively, the encapsulated liquid crystals 311 and/or the electrode material 333 may be applied to the surface 331 only at those areas where display segments are desired. The ability to apply encapsulated liquid crystal to only a desired area or plurality of areas such as the segments of a display by essentially conventional processes (such as e.g. silk-screening or other printing processes) is particularly attractive, when compared with the prior art, which has the problem of containing liquid crystals between flat plates.

The encapsulated liquid crystals in the layer 334 function to attenuate or not to attenuate light incident thereon in dependence on whether or not an electric field is applied thereacross. Preferably a pleochroic dye is present in solution in the liquid crystal material to provide substantial attenuation by absorption in the "field-off" condition but to be substantially transparent in the "field-on" condition. Such an electric field may be, for example, one produced as a result of the coupling of the electrode layer portions 333, 335 at an individual segment, such as segment 101a, of the liquid crystal device 10' to an electrical voltage source. The magnitude of the electric field required to switch the encapsulated liquid crystals 311 from a no field (deenergized) condition to a field-on (energized) condition may be a function of several parameters, including, for example, the diameter of the individual capsules and the thickness of the layer 334, which in turn may depend on the diameter of individual capsules 322 and the number of such capsules in the thickness direction of layer 334. 20742 0 Importantly, it will be appreciated that since the liquid crystal material 320 is confined in respective capsules 322 and since the individual encapsulated liquid crystals 311 are secured to the substrate 312, the size of the liquid crystal device 10' or any other liquid crystal device employing encapsulated liquid crystals in accordance with the present invention is virtually unlimited. Of course, at those areas where it is intended to effect a change in the optical properties of the encapsulated liquid crystals of such a device in response to a no field or field on condition, it would be necessary to have at such areas electrodes or other means for applying to such liquid crystals a suitable electric field.

The electrode layer 333 may be applied to the substrate 312 by evaporation, by vacuum deposition, by sputtering, by printing or by another conventional technique. Moreover, the layer 334 of encapsulated liquid crystals 311 may be applied, for example, by a web or gravure roller or by reverse roller printing techniques. The electrode layer 335 also may be applied by various printing, stenciling or other techniques. If desired, the electrode layer 333 may be prepared as a full coating of the substrate 312, such as Mylar, as described above, as part of the process in which the Mylar sheet material is manufactured, and the layer 334 also may be applied as part of such manufacturing process. - The inventor has discovered, moreover, that when the liquid crystal material 30 in the capsule 32 (Fig. 2) has pleochroic dye dissolved therein, such dye, which ordinarily also would be expected to have optical polarization sensitivity, no longer is polarization sensitive because the dye tends to follow the same kind of curvature orientation or distortion as that of the liquid crystal structure. It is noted here that in the capsule 32 the discontinuity 55 further distorts the liquid crystal structure which in turn further decreases the possibility that the liquid crystal material 30 would be sensitive to the optical polarization of the incident light. With the liquid crystal structure and pleochroic dye being distorted to fold in on itself generally in the manner illustrated in Fig. 5, for example, the encapsulated liquid crystal ordinarily will absorb or block light from being transmitted therethrough when no electric field is applied across the encapsulated liquid crystal and particularly across the liquid crystal material thereof. 20742 However, when an electric field is applied across the encapsulated liquid crystal in the manner illustrated in Fig. 3, the liquid crystal and any pleochroic dye in solution therewith will align in response to the electric field in the manner shown in such figure. Such alignment permits light to be transmitted through the encapsulated liquid crystal 11.

To optimize the contrast characteristics of a liquid crystal device, such as that shown at 10' in Fig. 9, comprised of encapsulated liquid crystals 11 with pleochroic dye therein, and more particularly, to avoid optical distortion, due to refraction of incident light passing from the encapsulating medium into the liquid crystal material and vice versa, the index of refraction of the encapsulating medium and that the ordinary index of refraction of the liquid crystal material should be matched so as to be as much as possible the same. The closeness of the index matching will be dependent on the desired degree of contrast and transparency in the device, but the ordinary index of refraction of the crystal and the index of the medium will preferably differ by no more than more preferably 0.01, especially 0.001. The tolerated difference will depend on capsule size and intended use of the device. The text "Optics" by Sears, published by Addison-Wesley, contains a thorough discussion of birefringence relevant to the foregoing, and the relevant portions of such text are incorporated herein by reference.

However, when no field is applied there will be a difference in indices of refraction at the boundary of the liquid crystal and capsule wall due to the extraordinary index of refraction of the liquid crystal being greater than the encapsulating medium. This causes refraction at that interface or boundary and thus further scattering and is a reason why encapsulated nematic liquid crystal material in accordance with the present invention, in particular, will function to prevent transmission of light even without the use of pleochroic dye; with such dye, though, substantial absorption of the scattered light will occur in the capsule.

Ordinarily the encapsulated liquid crystals 311 would be applied to the substrate 312 such that the individual encapsulated liquid crystals 311 are relatively randomly oriented and preferably several capsules thick to 20742 assure an adequate quantity of liquid crystal material to thereby provide the desired level of light blockage and/or transmission characteristics for, for example, a liquid crystal device 10' or the like.

In a liquid crystal device, such as that shown in 10' in Fig. 9, which is comprised of liquid crystal material 320 including pleochroic dye to form encapsulated liquid crystals 311 according to the invention (Fig. 18), it has been discovered that the degree of optical absorbency is at least about the same as that of relatively free (unencapsulated) liquid crystal material including pleochroic dye. It also has been discovered unexpectedly that when the electric field is applied in the manner illustrated in Fig. 3, for example, the clarity or lack of opaqueness of the encapsulated liquid crystal material 30 including pleochroic dye is at least about the same as that of the ordinary case in the prior art device 1 having dye in solution with relatively free liquid crystal material.

A schematic electric circuit diagram representing the circuit across which the electric field E of Fig. 3 is imposed is illustrated in Fig. 20. The electric field is derived from the voltage source 316 when the switch 317 is closed. A capacitor 370 represents the capacitance of the liquid crystal material 30,320 in the encapsulated liquid crystal 11, 311 when such electric field is applied in the manner illustrated in Fig. 3. The capacitor 371 represents the capacitance of the capsule wall 54 at an upper area (the direction conveniently referring to the drawing but having no other particular meaning). The capacitor 372 similarly represents the capacitance of the lower portion of the capsule exposed to the electric field E. The magnitudes of capacitance for each capacitor 370-372 will be a function of the dielectric constant (coefficient) of the material of which the respective capacitors are formed and of the spacing of the effective plates thereof. It is desirable that the voltage drop occurring across the respective capacitors 371, 372 will be less than the voltage drop across the capacitor 370; the result, then, is application of a maximum portion of the electric field E across the liquid crystal material 30 in the encapsulated liquid crystal 11, 311 for achieving optimized operation, i.e. alignment, of the liquid crystal structure thereof with a minimum total energy requirement of the voltage 207420 source 316. However, it is possible that the voltage drop in one or both capacitors 371, 372 will exceed the voltage drop across capacitor 370; this is operationally acceptable as long as the drop across the capacitor 370 (liquid crystal material) is great enough to produce an electric field that tends to align the liquid crystal material to and/or toward the field-on condition of Fig. 3, for example.

In connection with capacitor 371, for example, the dielectric material is that of which the wall 54 is formed relatively near the upper portion of the capsule 32,322. The effective plates of such capacitor 371 are the exterior and interior capsule wall surfaces and the same is true for the capacitor 372 at the lower portion of the capsule. By making the wall 54 as thin as possible, while still providing adequate strength for containment of the liquid crystal material, the magnitudes of capacitors 371, 372 can be maximized, especially in comparison to the rather thick or lengthy distance between the upper and lower portions of the liquid crystal material in the capsule which approximately or equivalently form the plates of the same number of the capacitor 370.

The liquid crystal material 320 will have a dielectric constant value that is anisotropic; therefore, such value also is referred to as dielectric coefficient. It is preferable that the dielectric constant of the wall 54 be no lower than the lower dielectric coefficient of the anisotropic liquid crystal material 20 to help meet the above conditions. Since a typical lower dielectric coefficient for liquid crystal material is about 6, this indicates that the dielectric constant of the encapsulating material is preferably at least about 6. Such value can vary widely depending on the liquid crystal material used, being, for example, as low as about 3.5 and as high as about 8 in the commonly used liquid crystals.

The encapsulated liquid crystal 311 has features such that since the liquid crystal structure is distorted and since the pleochroic dye similarly is distorted, absorbency or blockage of light transmission through the encapsulated liquid crystals will be highly effective when no electric field E is applied thereacross. On the other hand, due both to the efficient application of an electric field across the liquid crystal material 320 in the 2074 2 0 encapsulated liquid crystals 311 to align the liquid crystal molecules and the dye along therewith as well as the above described preferred index of refraction matching, i.e. of the encapsulating medium and of the liquid crystal material, so that incident light will not be refracted or bent at the interface between the capsule wall and the liquid crystal material 320 when an electric field is applied, the encapsulated liquid crystal 311 will have a good optically transmissive characteristic.

Since a plurality of encapsulated liquid crystals 11, 311 ordinarily is required to construct a final liquid crystal device, such as the device 10' of Fig. 9, and since those encapsulated liquid crystals are ordinarily present in several layers, it is desirable for the liquid crystal material to have a relatively high dielectric anisotropy in order to reduce the voltage requirements for the electric field E. More specifically, the differential between the dielectric coefficient for the liquid crystal material when no electric field is applied, which coefficient should be rather small, and the dielectric coefficient for the liquid crystal material when it is aligned upon application of an electric field, which coefficient should be relatively large, should be as large as possible consistent with the dielectric constant of the encapsulating medium.

As was noted above, the larger the capsule size, the smaller the electric field required to effect alignment of the liquid crystal molecules therein. However, the larger the sphere, the longer the response time. A person of ordinary skill in the art should have no difficulty, having regard to this disclosure, in determining a suitable or optimum capsule size for a given application.

The encapsulating medium forming capsules should be of a type that is substantially completely unaffected by and does not react with or otherwise chemically affect the liquid crystal material or the pleochroic dye. The dye should be soluble in the liquid crystal material and not subject to absorption by the encapsulating medium. Additionally, to achieve the desired relatively high impedance for the encapsulating medium, such medium should have a relatively high level of purity. Especially when the encapsulating medium is prepared as an aqueous dispersion or by ionic 20742 0 polymerization, etc., it is important that the level of ionic (conductive) impurities should be as low as possible.

Examples of pleochroic dyes that may suitably be used in the encapsulated liquid crystals 11 in accordance with the present invention are indophenol blue, Sudan black B, Sudan 3, and Sudan 2, and D-37, D-43 and D-85 by E. Merck identified above..._ .

EXAMPLE 10 .

A .45% Sudan black B pleochroic dye was dissolved in a liquid crystal which was composed of aromatic esters. Such combined material is commercially sold under the designation NMB250 by American Liquid Xtal Chemical Corp. of Kent, Ohio. Such material was mixed with a solution of 7% PVA, which had been purified to remove all salts. The solution also was made with ASTM-100 water. The resulting mixture was put into a colloid mill whose conegap setting was 4 mils, and the material was milled for four minutes to give a rather uniform particle suspension size. The result was a stable emulsion whose suspended particle size was approximately 3 microns. The emulsion was cast on a Mylar film which was precoatd with a 200 ohm per square layer of indium tin oxide electrode purchased from Sierracin. A doctor blade was used to cast the emulsion material on the Mylar film on the electrode coated side.

A 7 mil lay-down of the emulsion material was placed on such electrode and was allowed to dry to a total thickness of 0.8 mil. A second layer of such emulsion subsequently was laid on the first with a resulting aggregate layer of liquid crystal droplets in a polyvinyl alcohol matrix having a thickness of 1.6 mil. Preferably the encapsulated liquid crystals may be laid down in a single layer one or plural capsules thick.

The thusly formed liquid crystal device, including the layer of Mylar, electrode, and encapsulated liquid crystals was then tested by applying an electric field, whereupon the material changed from black to nearly clear-transparent. The material exhibited a very wide viewing angle, i.e. the angle at which light was transmitted, and the contrast ratio was 7:1 at 50 volts of applied electric field. The switching speed was about two milliseconds on and about 4 milliseconds off. 207420 -54-EXAMPLE 11 900 grams of 7% high viscosity fully hydrolysed polymer (SA-72 of American Liquid Xtal Chemical Corp.), 100 grams of 8250 nematic liquid crystal material also of American Liquid Xtal Chemical Corp., .45 grams of C26510 Sudan Black B, and .15 grams of C26100 Sudan HI (the latter two ingredients being pleochroic dyes), were used, he polymer was weighed out in a beaker. The liquid crystal was weighed out, was placed on a hot plate, and was heated slowly. The dye was weighed out on a balance and was added very slowly to the liquid crystal, being stirred until all the dye went into solution.

The liquid crystal and dye solution then was filtered through a standard Millipore filtering system using 8 m. filter paper. The filtered liquid crystal and dye solution was stirred into the polymer using a Teflon rod. Such mixture was encapsulated by placing the same in a colloid mill that was operated at medium shear for five minutes. The emulsion film was then pulled on a conductive polyester sheet.

In operation of such example, upon the application of a 10 volt electric field, the liquid crystal structure began to align, and at 40 volts reached saturation and maximum optical transmissivity.

EXAMPLE 12 The procedure of Example 11 was carried out using the same ingredients and steps except that a 5% high viscosity fully hydrolysed polymer, such as SA-72, was substituted for the 7% polymer of Example 2. Operational results were the same as in Example 2.

EXAMPLE 13 The process of Example 11 was carried out to make an emulsion using 4 grams of 20% medium viscosity, partly hydrolysed polymer (such as 405 identified in Table I above), 2 grams of 8250 nematic liquid crystal material halving 0.08% of D-37 magenta pleochroic dye (a proprietary pleochroic dye manufactured and/or sold by E. Merck of West Germany) in the solution with the liquid crystal.

A slide was taken using a Teflon rod, and upon inspection showed medium size capsules of about 3 to 4 microns in diameter. The material was 20742 filtered through a Millipore screen filter and another slide was taken; on inspection there was very little change in capsule size from the first-mentioned inspection.

The emulsion was pulled onto a conductive polyester support film as in Example 11 using a doctor blade set at a 5 mil gap. In operation, the encapsulated liquid crystal material began to align upon the application of an electric field of 10 volts and was at saturation or full on at from about 40 to 60 volts.

EXAMPLE 14 Using a glass rod cleaned and washed with deionized ASTM-100 water, 2 grams of 40% 8250 nematic liquid crystal material with 0.08% of D-37 pleochroic dye dissolved therein was stirred into 4 grams of- 405 desalted 20% by weight medium hydrolysis medium viscosity polymer very carefully for approximately 15 minutes. The material was then placed through a Millipore screen filter approximately 4 microns in size. A slide was taken after the bubbles had dissipated.

Thereafter, a film was pulled at a gap 5. mil setting on Intrex electrically conductive electrode film material that was placed on a polyester support of Mylar material. In operation it was evident that the liquid crystal material began aligning upon application of a 5 volt electric field. Contrast was good and the liquid crystal material was at full on or saturation upon the application of a 40 volt electric field.

EXAMPLE 15 This example used 8 grams of D-85 pleochroic dye dissolved in E-63 biphenyl liquid crystal. Such material is sold premixed by British Drug House, which is a subsidiary of E. Merck of West Germany. The example also used 16 grams of 20% PVA medium viscosity medium hydrolysis polymer as the encapsulating medium. The liquid crystal and pleochroic dye solution was mixed carefully by hand into the polymer at a slow rate. The combined material was then screened at a low shear. A slide was taken and on observation showed approximately 3 micron size capsules. A film of such emulsion was pulled onto an electrically conductive polyester sheet, as above, using a gap 5 mil setting. The film was on or began having liquid 207420 crystal structure align with the electric field at approximately 6 volts and was at saturation or full on at 24 volts.

EXAMPLE 16 A mixture was formed of 8250 nematic liquid crystal with 0.08% D-37 pleochroic dye in solution therewith and a solution of 15% AN169 Gantrez in 85% water. The mixture was of 15% liquid crystal and 85% Gantrez as the containment medium. The mixture was homogenized at low shear to form an emulsion, which was applied to an electrode/support film as above; such support film was about 1.2 mils thick. After drying of the emulsion, the resulting liquid crystal emulsion responded to an electric field generally as above, substantially absorbing or at least not substantially transmitting light when in field-off condition, showing a threshold of about 7 volts to begin transmitting, and having a saturation level of substantially maximum transmission at about 45 volts.

In accordance with the present invention the quantities of ingredients for making the encapsulated liquid crystals 11, for example in the manner described above, may be, as follows: The liquid crystal material - This material may be from about 5% to about 20% and preferably about 50% (and in some circumstances even greater depending on the nature of the encapsulating material) including the pleochroic dye, by 25% (when using Gelvatol as the encapsulating material) volume of the total solution delivered to the mixing apparatus, such as a colloid mill. The actual amount of liquid crystal material used should ordinarily exceed the volume quantity of encapsulating medium, e.g. PVA to optimize the capsule size.

The PVA - The quantity of PVA in the solution should be on the order of from about 5% to about 50%, and possibly even greater depending on the hydrolysis and molecular weight of the PVA, and preferably, as described above, about 22%. For example, if the PVA has too large a molecular weight, the resulting material will be like glass, especially if too much PVA is used in the solution. On the other hand, if the molecular weight is too low, use of too little PVA will result in too low a viscosity of the material, and the resulting emulsion will not hold up well, nor will the 20742 0 droplets of the emulsion solidify adequately to the desired spherical encapsulated liquid crystals.

Carrier medium - The remainder of the solution would be water or other, preferably volatile, carrier medium, as described above, with which the emulsion can be made and the material laid down appropriately on a substrate, electrode or the like.

It will be appreciated that since the uncured capsules or droplets of encapsulating medium and liquid crystal material are carried in a liquid, various conventional or other techniques may be employed to grade the capsules according to size so that the capsules can be reformed if of an undesirable size by feeding again through the mixing apparatus, for example, and so that the finally used capsules will be of a desired uniformity for the reasons expressed above.

Although the encapsulation technique has been described in detail with reference to emulsification, since the fact that the encapsulant material and binder are the same makes facile the production of liquid crystal devices; the preparation of discrete capsules of the liquid crystal material may on occasion be advantageous, and the use of such discrete capsules (with a binder) is within the contemplated scope of this invention.

Although the presently preferred invention operates in response to application and removal of an electric field, operation also may be effected by application and removal of a magnetic field.

STATEMENT OF INDUSTRIAL APPLICATION The invention may be used, inter alia, to produce a controlled optical display. 2074a! 0

Claims (42)

WHAT WE CLAIM IS:

1. Liquid crystal apparatus comprising plural volumes of liquid crystal assembled in a containment medium for selectively primarily scattering light or, in response to a prescribed field input applied to the volumes of liquid crystal assembled In the containment medium, transmitting light, said liquid crystal comprising operationally nematic liquid crystal having positive dielectric anisotropy and being operative to align with respect to the direction of such an applied field input and to undergo alignment, due to surface interaction, with respect to walls defining the volumes in said medium in the absence of such input, and the apparatus providing an optical response to such input by matching ordinary index of refraction of said liquid crystal with the index of refraction of the medium, and reflecting means for effecting total internal reflection of light scattered by said liquid crystal.

2. The apparatus of claim 1, wherein said liquid crystal and containment medium are cooperative in the absence of such an applied field input to effect substantially isotropic scattering of light.

3. The apparatus of eitner one of claims I or 2, said liquid crystal and containment medium comprising a layer of encapsulated liquid crystal, and said containment medium further comprising a support medium means for supporting said layer of encapsulated liquid crystal.

4. The apparatus of claim 3, further comprising a tuned dielectric interference layer on a surface of said support medium means for effecting optical constructive interference of at least some of the light In said support medium means incident on said interference layer or the interface thereof with said support medium means at an angle exceeding a predetermined cone angle and destructive interference of light incident at an angle within such cone angle.

5. The apparatus of any one of claims 1 to 4, said liquid crystal and containment medium comprising at least one layer of encapsulated operationally nematic liquid crystal, said liquid crystal having an ordinary index of refraction substantially matched to that of said 207420 -59- containment medium to maximize optical transmission In the presence of such an applied field input and to effect substantially Isotropic scattering in the absence of such an applied field input.

6. The apparatus of any one of claims 1 to 5, said containment medium having a viewing side and an opposite side, respective media at said viewing and opposite sides, and the Index of refraction of said containment medium being greater than the index of refraction of the medium at one of respectively such viewing and opposite sides, said reflecting means comprising an interface of such one of said sides with the medium thereat to effect total internal reflection of light in said containment medium incident on such interface at an angle exceeding a predetermined cone of light angle at which light would be transmitted through such interface.

7. The apparatus of claim 6, wherein said liquid crystal is operative in the absence of such an applied field input to scatter a substantial amount of light at an angle exceeding the total Internal reflection angle of said containment medium at such interface.

8. The apparatus of any one of claims 5 to 7, wherein the Index of refraction of said containment medium is greater than the indices of refraction of the media at both of said viewing and opposite sides, and said reflecting means comprises the interfaces of both said sides with such media to effect such total internal reflection.

9. The apparatus of any one of claims 1 to 8, wherein said liquid crystal has a natural structure, and said walls distort the natural structure of the liquid crystal to a distorted alignment in the absence of such an applied field input.

10. The apparatus of claim 9, further comprising additive means in said operationally nematic liquid crystal for expediting such distorting and return to distorted alignment upon the removal of such an applied field input.

11. The apparatus of claim 10, said additive means comprising a chiral additive.

12. The apparatus of any one of claims 9 to 11, wherein said walls form curved surfaces of the volumes containing quantities V |z-7 DEC 1987 J %c r , -J ^ -60- 2074^0 crystal, and said distorted alignment comprising alignment at least partly paralleling the curvature of such surfaces.

13. The apparatus of any one of claims 9 to 11, further comprising means for tending to force at least a portion of at least some of said liquid crystal Into substantially normal alignment with said walls.

14. The apparatus of claim 13, said means for tending to force comprising a chrome steryl complex, a chrome alkyl complex or a Werner complex that is reactive with said wall.

15. The apparatus of any one of claims 1 to 14, further comprising pleochroic dye in said liquid crystal.

16. The apparatus of claim 15, wherein said dye aligns with respect to the structure of said liquid crystal, whereby In the absence of such an applied field Input said dye effects substantial light absorption according to the color characteristics of the dye, and said liquid crystal responds to such an applied field input to align generally in parallel relation thereby to decrease the amount of light absorption by said dye.

17. The apparatus of any one of claims 1 to 16, further characterized in that the extraordinary index of refraction of said liquid crystal Is different from that of said containment medium to effect scattering of light in the absence of such an applied field input.

18. The apparatus of any one of claims 1 to 17, further comprising light director means for directing incident light into said containment medium and liquid crystal at one side thereof at a direction substantially out of the usual viewing line of sight of the apparatus.

19. The apparatus of claim 18, said reflecting means comprising a gap between said containment medium and said director means to cause a total internal reflection interface.

20. The apparatus of either one of claims 18 or 19, said director means comprising a light control film having light transmitting and light absorbing portions, said absorbing portion being positioned with respect to said Interface to absorb at least some light transmitted through said Interface.

21. The apparatus of any one of claims 1 to 20, further I -51- 2074<!U comprising optical absorbing means for absorbing light transmitted through one 3lde of said containment medium.

22. The apparatus of any one of claims 1 to 21, said reflecting means comprising means for reflecting light scattered by said liquid crystal back to said liquid crystal to display relatively bright characters or the like on a relatively dark background.

23. The apparatus of any one of claims 1 to 22, said liquid crystal being optically anisotropic, and wherein the difference between the ordinary Index of refraction of said liquid crystal and the index of refraction of said containment medium Is no more than 0.3.

24. The apparatus of any one of claims 1 to 23, further comprising substrate means for supporting a layer of said liquid crystal and containment medium, said layer being from 0.3 mil to 10 mils thick.

25. The apparatus of any one of claims 1 to 24, wherein such containment medium forms capsule-like volumes containing such liquid crystal, and wherein the diameter of such capsule-like volumes Is from 0.3 microns to 100 microns.

26. The apparatus of any one of claims 1 to 25, said liquid crystal being operative in said containment medium to affect optical transmission independently of polarization.

27. The apparatus of any one of claims 1 to 26, said liquid crystal being reversible.

28. The apparatus of any one of claims 1 to 27, said containment medium being selected from the group comprising resin, polymer, gelatin, Carbopole, Gantrez, polyvinyl alcohol, carboxy polymethylene polymer, and polymethyl vinyl ether/maletc anhydride.

29. The apparatus of any one of claims 1 to 28, further comprising means for applying an electric field to said liquid crystal to affect the alignment thereof and at least one of the absorbence and scattering of light thereby.

30. The apparatus of claim 29, said means for applying comprising electrode means for applying the electric field across said liquid crystal. -62- 207420

31. The apparatus of claim 30, further characterized in that plural volumes of liquid crystal in a containment medium cover a substantial portion of a support medium.

32. The apparatus of claim 31, further comprising plural electrode means for applying electric field to selected portions of said liquid crystal, said electrode means comprising plural electrodes positioned over relatively smaller areas of said support medium and liquid crystal than such substantial portion size of said liquid crystal covering said support medium.

33. The apparatus of claim 32, wherein one of said electrode means includes a sheet electrode covering a substantial surface of said containment medium.

34. The apparatus of any one of claims 30-33, said means for applying further comprising circuit means for providing electrical energy to said electrode means to create such electric field.

35. The apparatus of any one of claims 1 to 34, said liquid crystal having positive dielectric anisotropy.

36. The apparatus of claim 35, wherein the lower dielectric constant of said liquid crystal is between 3.5 and 8.

37. The apparatus of any one of claims 1 to 36, said liquid crystal and containment medium comprising an emulsion or a dispersion.

38. The apparatus of any one of claims 1 to 37, further comprising a light source for illuminating said liquid crystal.

39. An electro-optic display comprising the apparatus of any one of claims 1 to 38 substantially as described herein.

40. A billboard display comprising a liquid crystal apparatus of any one of claims 1 to 39 substantially as described herein.

41. A method of displaying a bright character or other Information on a relatively dark background using liquid crystal contained in volumes formed in the containment medium, such liquid crystal being operationally nematic, having positive dielectric anisotropy, having an extraordinary Index of refraction that is different from the index of refraction of such containment medium and an ordinary index of refraction substantially matched to the index of refraction of such containment -63- 2074^ medium, comprising using surface interaction with such containment medium distorting the natural structure of such liquid crystal to effect scattering of at least some light incident on such liquid crystal, reflecting at least some of such scattered light back to such volumes of liquid crystal for further scattering, transmitting to a viewing area at least some of the light scattered by such liquid crystal to form such character or other information, and selectively applying an electric field to such liquid crystal to align the same for transparency to form such relatively dark background. internally reflecting isotropically scattered light back to such liquid crystal to brighten the same. 43. The method of claim 41, further comprising absorbing at least some of the light transmitted by such liquid crystal.

42. The method of claim 41, said reflecting comprising totally MANCHESTER R&D PARTNERSHIP By their Attorney JAMES W PIPER