Multicolor liquid crystal writing device
11143898 · 2021-10-12
Assignee
Inventors
Cpc classification
G02F1/133365
PHYSICS
G02F1/13718
PHYSICS
G02F1/1334
PHYSICS
G02F1/133617
PHYSICS
International classification
G02F1/1337
PHYSICS
Abstract
Described are multicolor liquid crystal writing devices that exhibit high brightness and contrast and methods for manufacturing multicolor liquid crystal writing devices that exhibit high brightness and contrast. The liquid crystals used in the devices and methods described are photosensitized using UV light to modify a reflective character of the liquid crystals and different amounts, intensities, wavelengths, or exposure durations of UV light provide for different reflective colors.
Claims
1. A liquid crystal device comprising: a first conductive layer; a second conductive layer; and; a liquid crystal film between the first conductive layer and the second conductive layer, the liquid crystal film comprising a liquid crystal layer including cholesteric liquid crystals, the cholesteric liquid crystals comprising nematic liquid crystals and a photosensitive chiral dopant, the liquid crystal layer including a first region and a second region, the first region and the second region correspond to transversely separated areas across the liquid crystal layer, wherein: the first region corresponds to a first ultraviolet (UV) light exposure region, the second region corresponds to a second UV light exposure region, the first UV light exposure region and the second UV light exposure region correspond to regions of different UV light exposure across the liquid crystal film, the liquid crystals in the first region are photosensitized by UV exposure, based on the first UV light exposure region, to have a first pitch, and the liquid crystals in the second region are photosensitized by UV exposure, based on the second UV light exposure region, to have a second pitch that is different from the first pitch.
2. The liquid crystal device of claim 1, wherein a first concentration ratio of different isomers of the photosensitive chiral dopant in the first region is different from a second concentration ratio of different isomers of the photosensitive chiral dopant in the second region.
3. The liquid crystal device of claim 2, wherein the photosensitive chiral dopant comprises a chiral azobenzene dopant, wherein the first concentration ratio and the second concentration ratio correspond to concentration ratios of cis-isomers to trans-isomers of the chiral azobenzene dopant.
4. The liquid crystal device of claim 1, wherein: UV light intensities differ between the first UV light exposure region and the second UV light exposure region; or UV light wavelengths differ between the first UV light exposure region and the second UV light exposure region; or UV light exposure durations differ between the first UV light exposure region and the second UV light exposure region.
5. The liquid crystal device of claim 1, wherein cholesteric liquid crystals in the first region of the liquid crystal layer exhibit a reflective state of a first color, wherein cholesteric liquid crystals in the second region of the liquid crystal layer exhibit a reflective state of a second color, wherein the second color and the first color are different.
6. The liquid crystal device of claim 1, the liquid crystal film further comprising one or more polymer layers, wherein the one or more polymer layers are formed by the UV exposure, to polymerize uncured polymer to form cured polymer.
7. The liquid crystal device of claim 1, the liquid crystal film further comprising a cross-linked polymer network, wherein the cross-linked polymer network is formed from multifunctional monomers subject to the UV exposure.
8. The liquid crystal device of claim 1, the liquid crystal film further comprising another chiral dopant different from the photosensitive chiral dopant.
9. The liquid crystal device of claim 1, wherein the cholesteric liquid crystals in the liquid crystal layer exhibit a reflective state and a scattering state, wherein the reflective state is stable in the absence of an electric field applied between the first conductive layer and the second conductive layer, and wherein the scattering state is stable in the absence of an electric field applied between the first conductive layer and the second conductive layer.
10. The liquid crystal device of claim 1, wherein the cholesteric liquid crystals in a light scattering state in the liquid crystal layer change to a light reflective state in response to applied mechanical pressure.
11. The liquid crystal device of claim 1, wherein the cholesteric liquid crystals in a light reflective state in the liquid crystal layer change to a light scattering state in response to an electric field applied between the first conductive layer and the second conductive layer.
12. The liquid crystal device of claim 1, further comprising: a passivation film between the first conductive layer and the liquid crystal layer or between the second conductive layer and the liquid crystal layer; or a first passivation film between the first conductive layer and the liquid crystal layer and a second passivation film between the second conductive layer and the liquid crystal layer.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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(11) The figures depict embodiments of the present disclosure for purposes of illustration only. One skilled in the art will readily recognize from the following description that alternative embodiments of the structures and methods illustrated may be employed without departing from the principles, or benefits touted, of this disclosure.
(12) In the appended figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a dash and a second label that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the second reference label.
DETAILED DESCRIPTION
(13) In the following description, for the purposes of explanation, specific details are set forth in order to provide a thorough understanding of certain inventive embodiments. However, it will be apparent that various embodiments may be practiced without these specific details. The figures and description are not intended to be restrictive.
(14) Described herein are liquid crystal displays and writing devices that exhibit high brightness and contrast and methods for manufacturing liquid crystal displays and writing devices that exhibit high brightness and contrast. The liquid crystal displays and writing devices optionally include first and second conductive layers and a liquid crystal film between the conductive layers. The liquid crystal film can include liquid crystal layers and polymer layers, constructed such that the liquid crystal film exhibits a bistable configuration, where different states of liquid crystals (e.g., a focal conic state and a planar state) within the film are stable in the absence of an applied electric field. Further details regarding bistable liquid crystal writing devices may be found in U.S. patent application Ser. No. 15/237,568, filed on Aug. 15, 2016, now U.S. Pat. No. 10,228,599, issued on Mar. 12, 2019, which is hereby incorporated by reference in its entirety.
(15) Each of the different stable states can possess different optical characteristics. For example, the focal conic state may exhibit a light scattering characteristic and the planar state may exhibit a light reflecting characteristic. When placed over a background, the focal conic state may have an appearance similar to a background behind the liquid crystal film. The planar state, however, may reflect light of a particular color (i.e., wavelength or wavelength range), and have an appearance of a bright color, for example. By applying a force or pressure to the liquid crystal displays and writing devices, the liquid crystal film can transition from the focal conic state to the planar state. Since the planar state is stable, a reflective appearance may be maintained where the pressure or force was applied, allowing for a user to write or draw on the liquid crystal display or writing device. Further, by applying a potential between the conductive layers, the liquid crystals can be exposed to an electric field and have their orientation actively adjusted (e.g., to a perpendicular state), which may be transparent or may scatter light, similar to the focal conic state. After the potential is removed, the liquid crystals can relax back to the stable focal conic state.
(16) A cholesteric liquid crystal can be formed from liquid crystal materials possessing inherent chirality, like cholesterols, or by mixing chiral molecules (dopants) into nematic liquid crystals. The chirality of the cholesteric liquid crystals makes the liquid crystal molecules align with one another at a certain angle that yields a helical microstructure. The pitch length of a cholesteric liquid crystal helix is defined as the unit length for a complete rotation. The central wavelength of the reflection of a cholesteric liquid crystal is given by:
(17)
where n.sub.e is the extraordinary refractive index, n.sub.o is the ordinary refractive index, and P is the pitch. In the case of a cholesteric liquid crystal formed by doping chiral dopant into a nematic liquid crystal, P is controlled by the helical twist power (HTP) of the chiral dopant, which is a function of the concentration of the chiral dopant.
(18) In contrast to other liquid crystal displays and writing devices, the liquid crystal displays and writing devices (liquid crystal devices) described herein can exhibit multiple different reflective colors. By placing cholesteric liquid crystals having different pitch lengths across different areas of the liquid crystal film or in different regions of the liquid crystal film, the reflective color may vary as a function of position in the liquid crystal devices. The technique advantageously applied herein for achieving different pitch lengths includes using a cholesteric liquid crystals comprising nematic liquid crystals and a photosensitive chiral dopant and exposing the photosensitive chiral dopant to ultraviolet light to adjust the pitch length of the cholesteric liquid crystals.
(19) Example photosensitive chiral dopants include, but are not limited to, chiral azobenzene dopants, which may have a general molecular structure of:
(20) ##STR00002##
where R.sup.1 and R.sup.2 are independently the same or different side groups. In some examples, at least one of R.sup.1 or R.sup.2 includes a stereocenter, which can provide chirality. Azobenzene compounds, like the chiral azobenzene dopants used herein, can exist in two isomeric forms, a cis configuration and a trans configuration. Conversion between the two configurations can be mediated by exposure to light, such as UV light. In the cis configuration, the benzene rings are on the same side of the double bond, while in the trans configuration, the benzene rings are on opposite sides of the double bond:
(21) ##STR00003##
The different isomers may modify the HTP differently, so by adjusting the relative concentrations of the different isomeric forms of the photosensitive chiral dopant, the HTP and pitch length can be controlled. By exposing the photosensitive chiral dopant to a particular amount, intensity, wavelength, or duration of ultraviolet light, the pitch length of cholesteric liquid crystals in different regions of the liquid crystal devices can be controlled, allowing the liquid crystals different regions to exhibit different reflective colors. In some cases, multiple different liquid crystals with different pitch lengths may be used in the same region to achieve a particular reflective color combination configuration, such as a combination of a blue reflective color and a green reflective color.
(22) Liquid crystal devices described here may optionally employ liquid crystal films formulated with chiral azobenzene dopants, chiral dopants, oligomers, monomers, and photoinitiators. The liquid crystal films may be cured using an ultraviolet (UV) curing process, which may polymerize the prepolymer components (oligomers, monomers, and/or photoinitiators) and isomerize portions of the chiral azobenzene dopants. As more of the chiral azobenzene dopants are photoisomerized from the trans-isomer to the cis-isomer, the reflection wavelength of the cholesteric liquid crystals may red-shift. By curing different areas of the liquid crystal film with different amounts, intensities, or wavelengths, or durations of UV light, the different areas can undergo different red-shift amounts and thus the different areas can exhibit different colors upon application of pressure or force.
(23) Liquid Crystal Writing Devices
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(25) Liquid crystal device 100 may also comprise other layers, including one or more substrate layers 120 and 125 and, optionally, passivation layers 130 and 135. Substrate layers 120 and 125 may optionally comprise multiple layers. Example substrates may include polymer films, such as polyethylene terephthalate (PET), polyimide (PI), polypropylene (PP), or the like, glass, quartz, or any other suitable substrate material. Optionally, substrate 120 and/or 125 may be transparent. Optionally, substrate 125 may be non-transparent and may exhibit a background color (e.g., a dark color to mimic a background of a blackboard). Use of a dark background color may be advantageous to provide for high contrast with reflective liquid crystal states. Passivation layers 125 and 130 may be inert, nonreactive, and/or insulating layers, and may serve to limit contact between liquid crystal film 105 and first conductive layer 110 and second conductive layer 115, so as to avoid unnecessary or unwanted chemical reactions between the first and second conductive layers 110 and 115 and components of liquid crystal film 105, such as polymer components or liquid crystal components. Use of a passivation layer may be particularly desirable when first conductive layer 110 and/or second conductive layer 115 comprises a conductive polymer. Example materials for passivation layers 125 and 130 include, but are not limited to, polymer materials (e.g., PET, PI) and dielectric materials, like silicon dioxide or silicon nitride. Passivation layers 125 and 130 may also serve to encapsulate the liquid crystal film 105.
(26) As shown in
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(30) Multicolor Liquid Crystal Writing Devices
(31) Mark 255 is shown in
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(33) Any desirable number of reflective colors and arrangement of areas are contemplated according to the present disclosure. In
(34) Use of vertically arranged horizontal stripes or horizontally arranged vertical stripes may be advantageous for manufacturing multicolor liquid crystal writing devices, as striped configurations may be easily achieved using roll-to-roll processing methods, as described below. Other geometrical or arbitrary areas for different reflective colors may be used, however.
(35) For example, stripes of other orientations may be used.
(36) In one additional example, areas of arbitrary shape may be used.
(37) Methods of Manufacturing Liquid Crystal Writing Devices
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(39) At block 805, the liquid crystal film is subjected to an ultraviolet (UV) curing process by exposing the liquid crystal film to UV light. The UV curing process may perform several functions, including photosensitizing the liquid crystals to control and/or set a pitch length in the liquid crystals, which allows tuning a reflective wavelength of the liquid crystals, and polymerizing the uncured polymer. The UV curing process may advantageously use multiple UV light exposure regions, which may allow different regions or areas of the liquid crystal film to be subjected to different intensities, wavelengths, and/or durations of UV light exposure. In this way, the photosensitive chiral dopants in the different regions can be subjected to different amounts, intensities, or wavelengths of UV light, allowing for varied control over the concentration of different isomeric orientations of the photosensitive chiral dopant. As noted above, the relative concentrations of different isomeric orientations of the photosensitive chiral dopant can impact the helical twist power and pitch of a cholesteric liquid crystal, which directly impacts the reflective wavelength of a reflecting configuration (e.g., state or orientation) of a cholesteric liquid crystal.
(40) At block 815, a first conductive layer is placed above the liquid crystal film. Optionally, a first passivation layer is also placed above the liquid crystal film, at block 820, such as between the liquid crystal film and the first conductive layer. At block 825, a second conductive layer is placed below the liquid crystal film. Optionally, a second passivation layer is also placed below the liquid crystal film, at block 830, such as between the liquid crystal film and the second conductive layer.
(41) At block 835, a UV protection film may be optionally provided above the liquid crystal film. Use of a UV protection film may be advantageous for limiting the cholesteric liquid crystals to exposure to additional UV light, which could modify the relative concentration of different isomeric orientations of a photosensitive chiral dopant and change the reflective wavelength of the liquid crystal.
(42) At block 840, a substrate is placed below the liquid crystal film, such as below the liquid crystal film, optional second passivation layer, and second conductive layer. The substrate may advantageously exhibit a dark or black color, to provide a contrast with the reflective color of cholesteric liquid crystals in the liquid crystal film when in a reflective configuration or orientation. In some cases, the substrate may be transparent, which may allow for the liquid crystal device to be used as a transparent writing or display device.
(43) It will be appreciated that the order of operations shown in
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(45) As shown, roller 910 may be in contact with another roller which is immersed in a source of a liquid crystal mixture for roll-to-roll application of the liquid crystal mixture onto substrate 905. Such a configuration is merely intended to be illustrative and is not intended to be limiting. For example, roller 910 may itself optionally be immersed in the source of liquid crystal mixture. Other specific roll coating techniques may be used to apply the liquid crystal mixture to substrate 905, such as use of gravure coaters, reverse coaters, slot die coaters, lip coaters, knife coaters, blade roll coaters, blade coaters, chamber doctor coaters, bar coaters, air knife (air doctor) coaters, or the like. Optionally, a roll-to-roll application process for applying the liquid crystal mixture to the substrate 905 may not be used and another application process may be used instead. For example, a spray coating process may be used, a spin coating process may be used, an inkjet printing process may be used, a screen printing process may be used. Roll-to-roll processing techniques may be advantageous as such a process may allow for quick and efficient formation of large areas of liquid crystal devices.
(46) After the liquid crystal mixture is applied to substrate 905, it is subjected to UV light exposure from a UV light source 925 as part of a UV curing process, where the UV light can polymerize uncured polymer present in the liquid crystal mixture and photosensitize cholesteric liquid crystals present in the liquid crystal mixture. The UV light generated by UV light source 925 can have a spatial variation, which may be useful for photosensitizing the cholesteric liquid crystals in different areas according to different UV exposures, intensities, or wavelengths.
(47) After the UV curing process, the substrate 905 and liquid crystal film 920 may be passed adjacent to or between additional rollers 930 and 935, such as to apply another substrate 940 over liquid crystal film 920 and generate liquid crystal device 945. Substrate 940 may optionally include multiple layers, and may include, for example, a carrier or base layer (e.g., itself a substrate), a conductive layer, a passivation layer, a UV protection film, or the like. Liquid crystal device 945 may be subjected to additional processing steps following attachment of substrate 940.
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(49) The intensities, wavelengths, and/or exposure durations of UV light may differ between first UV light region and second UV light region and allow areas 1050 and 1055 of liquid crystal film 1005 to exhibit different optical properties, such as different reflective wavelengths of the cholesteric liquid crystals when in a reflective configuration or orientation. The resultant liquid crystal device may be similar to liquid crystal device 400 depicted in
(50) In some embodiments, the liquid crystal film 1005 is not moving and may be processed according to a batch process, such as to achieve the liquid crystal device 600 depicted in
(51) The invention may be further understood by the following non-limiting examples.
Example 1
(52) A liquid crystal film was prepared and had the following components, indicated in weight percent:
(53) HCCH company positive liquid crystal SL-79 (HCCH), about 53.5%;
(54) Chiral dopant S811, about 10.2%;
(55) ##STR00004##
about 4.1%;
(56) ##STR00005##
about 11.3%;
Norland NOA65, about 5.3%;
Pentaerythritol triacrylate, about 4.6%;
Shenzhen Guangxinyi Company UV 8003, about 7.8%;
1,10-Bis(acrylyloy)decane, about 2.2%;
IRGACURE 651, about 1.0%.
(57) Three different areas of the liquid crystal film were cured using different UV exposure conditions. Area 1: 365 nm, 3 mW/cm.sup.2 for about 120 seconds. Area 2: 365 nm, 3 mW/cm.sup.2 for about 150 seconds. Area 3: 365 nm, 3 mW/cm.sup.2 for about 170 seconds. The resultant cured liquid crystal film exhibited the following reflective colors when subjected to a pressure or force to modify the alignment of the liquid crystals. Area 1: blue color. Area 2: green color. Area 3: red color.
Example 2
(58) A liquid crystal film was prepared and had the following components, indicated in weight percent:
(59) HCCH company positive liquid crystal SL-79 (HCCH), about 50.5%;
(60) Chiral dopant 5811, about 9.5%;
(61) ##STR00006##
about 4.1%;
(62) ##STR00007##
about 15.3%;
Ethoxylated glycerine triacrylate, about 1.8%;
Trimethylolpropane triacrylate, about 2.3%;
Ethoxylated trimethylolpropane triacrylate, about 1.7%;
1,9-Bis(acryloyloxy)nonane, about 1.6%;
Isodecyl methacrylate, about 2.1%;
Shenzhen Guangxinyi Company UV 9001, about 10.1%;
IRGACURE 651, about 1.2%.
(63) Three different areas of the liquid crystal film were cured using different UV exposure conditions. Area 1: 365 nm, 3 mW/cm.sup.2 for about 120 seconds. Area 2: 365 nm, 5 mW/cm.sup.2 for about 120 seconds. Area 3: 365 nm, 7 mW/cm.sup.2 for about 120 seconds. The resultant cured liquid crystal film exhibited the following reflective colors when subjected to a pressure or force to modify the alignment of the liquid crystals. Area 1: blue color. Area 2: green color. Area 3: red color.
Example 3
(64) A liquid crystal film was prepared and had the following components, indicated in weight percent:
(65) HCCH company positive liquid crystal SL-83 (HCCH), about 57.1%;
(66) ##STR00008##
about 23.1%;
Pentaerythritol triacrylate, about 1.5%;
Trimethylolpropane trimethacrylate, about 2.3;
Shenzhen Guangxinyi Company UV 9003, about 5.1%;
Shenzhen Guangxinyi Company UV 8116, about 5.6%;
Shenzhen Guangxinyi Company UV 8006, about 4.2%;
IRGACURE 651, about 1.1%.
(67) Three different areas of the liquid crystal film were cured using different UV exposure conditions. Area 1: 365 nm, 5 mW/cm.sup.2 for about 120 seconds. Area 2: 355 nm, 5 mW/cm.sup.2 for about 130 seconds. Area 3: 345 nm, 5 mW/cm.sup.2 for about 140 seconds. The resultant cured liquid crystal film exhibited the following reflective colors when subjected to a pressure or force to modify the alignment of the liquid crystals. Area 1: blue color. Area 2: green color. Area 3: red color.
(68) When a group of substituents is disclosed herein, it is understood that all individual members of those groups and all subgroups and classes that can be formed using the substituents are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. As used herein, “and/or” means that one, all, or any combination of items in a list separated by “and/or” are included in the list; for example “1, 2 and/or 3” is equivalent to “‘1’ or ‘2’ or ‘3’ or ‘1 and 2’ or ‘1 and 3’ or ‘2 and 3’ or ‘1, 2 and 3’”.
(69) Spatial descriptions, such as “above,” “below,” “up,” “left,” “right,” “down,” “top,” “bottom,” “vertical,” “horizontal,” “side,” “higher,” “lower,” “upper,” “over,” “under,” and so forth are indicated with respect to the orientation shown in the figures unless otherwise specified and are not intended to be limiting. It should be understood that the spatial description used herein are for purposes of illustration only and that practical implementations of the structures described herein can be spatially arranged in any orientation or manner.
(70) The foregoing description of the embodiments of the disclosure has been presented for the purpose of illustration; it is not intended to be exhaustive or to limit the disclosure to the precise forms disclosed. Persons skilled in the relevant art can appreciate that many modifications and variations are possible in light of the above disclosure.
(71) Some portions of this description describe the embodiments of the disclosure in terms of algorithms and symbolic representations of operations on information. These algorithmic descriptions and representations are commonly used by those skilled in the data processing arts to convey the substance of their work effectively to others skilled in the art. These operations, while described functionally, computationally, or logically, are understood to be implemented by computer programs or equivalent electrical circuits, microcode, or the like. Furthermore, it has also proven convenient at times, to refer to these arrangements of operations as modules, without loss of generality. The described operations and their associated modules may be embodied in software, firmware, and/or hardware.
(72) Steps, operations, or processes described may be performed or implemented with one or more hardware or software modules, alone or in combination with other devices. In some embodiments, a software module is implemented with a computer program product comprising a computer-readable medium containing computer program code, which can be executed by a computer processor for performing any or all of the steps, operations, or processes described.
(73) Embodiments of the disclosure may also relate to an apparatus for performing the operations described. The apparatus may be specially constructed for the required purposes, and/or it may comprise a general-purpose computing device selectively activated or reconfigured by a computer program stored in the computer. Such a computer program may be stored in a non-transitory, tangible computer readable storage medium, or any type of media suitable for storing electronic instructions, which may be coupled to a computer system bus. Furthermore, any computing systems referred to in the specification may include a single processor or may be architectures employing multiple processor designs for increased computing capability.
(74) Embodiments of the disclosure may also relate to a product that is produced by a computing process described herein. Such a product may comprise information resulting from a computing process, where the information is stored on a non-transitory, tangible computer readable storage medium and may include any embodiment of a computer program product or other data combination described herein.
(75) The language used in the specification has been principally selected for readability and instructional purposes, and it may not have been selected to delineate or circumscribe the inventive subject matter. It is therefore intended that the scope of the disclosure be limited not by this detailed description, but rather by any claims that issue on an application based hereon. Accordingly, the disclosure of the embodiments is intended to be illustrative, but not limiting, of the scope of the disclosure, which is set forth in the following claims.