CN100351677C - Liquid crystal display device containing nano polymer network and its manufacturing method - Google Patents
Liquid crystal display device containing nano polymer network and its manufacturing method Download PDFInfo
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- CN100351677C CN100351677C CNB2004100216267A CN200410021626A CN100351677C CN 100351677 C CN100351677 C CN 100351677C CN B2004100216267 A CNB2004100216267 A CN B2004100216267A CN 200410021626 A CN200410021626 A CN 200410021626A CN 100351677 C CN100351677 C CN 100351677C
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Abstract
The present invention discloses a liquid crystal display structure which contains a nanometer polymer network, and a manufacturing method thereof. The present invention is composed of a liquid crystal box, cholesteryl liquid crystal, polymer films and the polymer network in the liquid crystal, wherein the inner surface of the liquid crystal box has transparent conductive films; the cholesteryl liquid crystal is filled into the liquid crystal box; the polymer films which are covered on the transparent conductive films are manufactured by the phase disengagement method. The display has two steady states of a colorless transparent state and a white reflection state in zero electric field. When a black screen is arranged behind the display, patterns with black text on white or white text on black can be displayed. The display has the characteristics of simple manufacture technology, bright indicating background color, high contrast degree, etc.
Description
Technical field
The invention belongs to the flat pannel display field in the photoelectron technology, it is particularly related to the compound that utilizes polymkeric substance and the liquid crystal structure as the display of display medium manufacturing.
Background technology
Display by the compound manufacturing of liquid crystal and polymkeric substance mainly contains " polymer dispersed liquid crystal " (PDLC:PolymerDispersed Liquid Crystal), " polymer network liquid crystal " (PNLC:Polymer Network Liquid Crystal).The structure and the manufacture method of above-mentioned liquid crystal and compound that polymkeric substance is formed are delivered on the document of many home and overseas, and be all known by the people.
The architectural feature of PDLC is the liquid crystal droplet that polymkeric substance wraps up, and the size of droplet is generally less than 10 microns.Under the no external electric field situation, the sensing of the director of liquid crystal is at random in the different droplets, thereby compound presents the strong scattering process to light, the scattering state that compound is creamy white.If the electric field intensity that applies is stronger, be enough to make when liquid crystal director is all parallel with electric field in all droplets, because of the ordinary refraction index of liquid crystal consistent with refractive index polymer, so compound presents transparent characteristic.
The architectural feature of PNLC is to have polymer network in the liquid crystal, and the mesh size of network is generally in micron dimension, and the radial dimension of network is below 1 micron.Principle of work and the PDLC of PNLC are similar.When no electric field exists, liquid crystal is owing to the existence of polymer network, and being oriented to of the inner liquid crystal director of each grid is definite, and the sensing of director is different in the heterogeneous networks, thereby different grids in liquid crystal be oriented to different at random, the scattering state that compound is creamy white.If the electric field intensity that applies is stronger, be enough to make when liquid crystal director is all parallel with electric field in the all-network, because of the ordinary refraction index of liquid crystal consistent with refractive index polymer, so compound presents transparent characteristic.
As the liquid crystal in PDLC and the PNLC, common have a following several types: 1. nematic crystal; 2. chiral liquid crystal and cholesteryl liquid crystal.Can add the composition of nematic crystal and non-liquid-crystal compounds in chiral liquid crystal and the cholesteryl liquid crystal, mode as a kind of molecules align, after adding the composition of nematic crystal and a small amount of (below 20%) non-liquid-crystal compounds, they remain chiral liquid crystal or cholesteryl liquid crystal.Because chiral liquid crystal or cholesteryl liquid crystal be not difference in purposes of the present invention, below defer to the custom of industry, chiral liquid crystal or cholesteryl liquid crystal all are called cholesteryl liquid crystal.
It is display medium that common cholesteric liquid crystal display adopts cholesteryl liquid crystal, and its pitch is a fixed value.If select lower potential pulse, extra electric field places burnt taper attitude with liquid crystal, and then display is transparent.As long as place the backboard of black at the back of display, seem to be exactly black from the front.Usually selecting black is the color of the character of display.On the contrary, if select the higher voltage pulse, then extra electric field places flat state with liquid crystal, light enters this refractive index and is in the medium that the cycle changes Bragg reflection can take place, the light wave identical with the optics pitch of liquid crystal just is reflected back, from the front, display demonstrates the color consistent with this optical wavelength.Owing to have only the light of single wavelength to be reflected, so display presents solid color, such as shown in green.Usually selecting green is the background color of display.No matter cholesteric liquid crystal display is to bore attitude in the plane attitude or Jiao, all is steady state (SS) when not having external electric field, so, be called the null field bistable display again with the display of cholesteryl liquid crystal manufacturing.This kind display does not just need external electric field to keep the state of demonstration after information writes, and power consumption economizes especially.
The desired display screen of e-book is a cholesteric liquid crystal display.The structure of this display screen is the structure that is full of cholesteryl liquid crystal in the liquid crystal cell.This structure can realize the mutual conversion of cholesteryl liquid crystal from plane attitude (screw axis and surperficial quadrature) to burnt awl attitude (screw axis is parallel with the surface) under suitable external electric field, just do not need external electric field to keep the state of demonstration after information writes, so very power saving.Usually, No. 5 batteries of two joints can use under normal reading about 3 months, compared with the e-book of the LCD of using STN can only use 5 hours, use the e-book of TFT LCD can only use to come in 3 hours, its advantage is very significant.
Yet the books that people were accustomed to reading should be white gravoply, with black engraved characters, rather than the surplus of the green end, and at the problems referred to above, people are actively improving the performance of this display, make it to obtain the beneath effect that shows surplus of the white back of the body.
Chinese patent 92103952.2 discloses and has a kind ofly had ITO (tin indium oxide with two, a kind of nesa coating) folder one deck contains the cholesteryl liquid crystal of polymer network between the glass, because of existing polymer network, it make the pitch of cholesteryl liquid crystal be subjected to perturbation in this LCD, pitch difference at the cholesteryl liquid crystal of the diverse location of each display, the wavelength of Bragg reflection is also different, thus broadening the wavelength coverage of reflectance spectrum of LCD.Because being the monomer of terminal groups as central bridged bond, with the acrylate, this patent employing biphenyl and phenylester realize polymer network by polymerization, this monomer and ITO do not have affinity, so on ITO, can not form film, can only in the body of cholesteryl liquid crystal, form polymer network.The such structure polymer network of manufacturing (body of cholesteryl liquid crystal in) though can the catoptrical spectral range of broadening, limited to the range of adjustment of cholesteryl liquid crystal pitch owing to polymer network, spectral range is wide inadequately.
Further, in order to reduce the conversion voltage of plane attitude and burnt awl attitude, United States Patent (USP) 6,133, liquid crystal cell is made after also having deposited the smooth polyimide of one deck again in the surface of also having introduced two electrodes that constitute liquid crystal cell for No. 975, in liquid crystal cell, pour into liquid crystal then, make the scheme of polymer network.But smooth and liquid crystal had stronger grappling effect because of the polyimide film surfacing, so the catoptrical frequency spectrum of broadening is not had help, can only increase the width of ferroelectric hysteresis loop in the electro-optical characteristic.
Included list of references describes in the cholesteryl liquid crystal method, principle and the effect of adding polymer network in detail in the above-mentioned data, and following explanation supposition those of ordinary skill in the art has read and understood fully background information that patent that foregoing, this patent quote and these patents quote and the pertinent literature of having published before present patent application day.
Chinese patent 00812435.3 discloses a kind ofly makes the method for thin polymer film with phase disengagement method on glass substrate, the surface smoothing of film is to realize that liquid crystal is at surface orientation.But in liquid crystal, can not produce polymer network.
Summary of the invention
The purpose of this invention is to provide a kind of LCD that contains the nanometer polymer network and preparation method thereof, adopt the LCD that contains the nanometer polymer network of method preparation of the present invention, make light realize that in whole visible spectrum frequency range uniform Bragg reflection realizes showing on the white background characteristics of the effect of surplus thereby have.
Term definition:
1. nanometer polymer network: the polymer network of the radial dimension of network skeleton below 500 nanometers, hereinafter to be referred as polymer network.
2. polymer film and polymer network: in order to explain the effect of polymer film and polymer network, in this instructions the polymkeric substance in the liquid crystal cell is divided into polymer film and polymer network two parts, wherein radial dimension is polymer film at 0.5 micron with the top calculation, 0.5 micron is a polymer network with the lower part calculation, this does not also mean that the interface is arranged between them.
3. grappling, orientation, calibration, aligning: 4 speech synonyms, the same meaning is described in different book informations, i.e. physical or chemical treatment of carrying out at solid surface, thus the surface of solid has that the liquid crystal molecule of making is parallel to definitely or definitely perpendicular to or favour the surface definitely and arrange.
4. be separated: the homogeneous phase potpourri of liquid crystal material and polymerisable monomer (liquid crystal phase or isotropy liquid phase) is under the effect of heat or light, and polymerisable monomer generation polymerization becomes the process that solid or gel are separated out.
5. plane attitude: the screw axis of the cholesteryl liquid crystal in the liquid crystal cell is towards consistent and perpendicular to the state on liquid crystal cell surface.
A kind of LCD that contains the nanometer polymer network provided by the invention, it comprises: inside surface is coated with the liquid crystal cell of transparent conductive film, liquid crystal cell inside surface (being the transparent conductive film surface), cholesteryl liquid crystal, the size of the optics pitch of described cholesteryl liquid crystal is in visible wavelength range, it is characterized in that it also comprises: polymer film 1 that forms in the phase separation and polymer network 2, described polymer film 1 is covered in the liquid crystal cell inside surface, described polymer network 2 is arranged in cholesteryl liquid crystal, and described polymer film 1 and described polymer network 2 are as a whole.
In addition, above-mentioned polymer film 1 and polymer network 2 are made of acrylic ester compound (as the Ethylene glycol dimethacrylate) polymerization that does not contain benzene nucleus in the molecular structure, or are made of the multipolymer of the two or more acrylic ester monomers that do not contain benzene nucleus.These monomers do not contain phenyl group, and its polymkeric substance and liquid crystal acting force are less, and with ITO reasonable affinity are arranged.In addition, if adopt the common polymerization of two or more acrylic ester monomers to obtain above-mentioned polymer film 1 and polymer network 2, the chemical constitution that then has a kind of monomer at least is the structure with plural propenyl, as the polymkeric substance that is formed by Ethylene glycol dimethacrylate and methyl methacrylate copolymer.
Also have, the diameter of above-mentioned polymer network 2 skeletons is preferably between 20 nanometer to 100 nanometers below 500 nanometers, so that liquid crystal is had stronger grappling effect.
Liquid crystal cell is the structure of being put in opposite directions, being sealed with frame adhesive on every side by the transparency electrode 4 of last transparency carrier 5 and following transparency carrier 6, and its structure and manufacturing process have been that liquid crystal is known in the industry for a long time.Liquid crystal cell of the presently claimed invention is: go up transparency carrier 5 and following transparency carrier 6 and all be with the transparent conductive film pattern, both distances are preferably between 6 microns to 12 microns, the electrode of transparent conductive film is drawn outside the liquid crystal cell sealed frame, so that external circuit drives.
The principle Analysis that contains the LCD of nanometer polymer network of the present invention:
We find that in experiment the plane catoptrical wavelength of attitude cholesteric liquid crystal display is relevant with the direction of watching, along with viewing angle is spent to 60 degree changes the green variation from Chinese red to orchid continuously of the color of plane attitude cholesteric liquid crystal display from 0.This just points out us: except preparation polymer network in liquid crystal, if again at the method deposition one layer of polymeric film of liquid crystal cell inside surface to be separated, eliminate of grappling or the orientation effect of liquid crystal cell inside surface to liquid crystal, and allowing polymer network come the grappling liquid crystal molecule, the screw axis of cholesteryl liquid crystal is just only relevant with polymer network in different positions like this.Because of polymer network at random towards, so the screw axis that is anchored to the cholesteryl liquid crystal on the polymer network is just not necessarily perpendicular to the surface of liquid crystal cell.Like this, forceful electric power is pressed after the pulse, and cholesteryl liquid crystal does not just have the plane attitude, can only get the state that approaches the plane attitude, below this state is called " ideal plane attitude ".From microcosmic, display is the helical axis directions difference of cholesteryl liquid crystal everywhere, all departs from the direction perpendicular to the liquid crystal cell surface, so the wavelength of the Bragg reflection optical of these positions is also just different; On macroscopic view, the color of demonstration is the mixing of multi-wavelength's light, so the reflected light frequency spectrum has obtained broadening.In fact, adopt the present invention program can realize the reflection of white light.Similarly, it is " pseudo-burnt awl attitude " that light current is pressed postimpulse burnt taper attitude, experiment showed, that pseudo-burnt awl attitude bores attitude with Jiao and compare, and display effect does not have evident difference.
Because the present invention requires polymer film not to liquid crystal aligning, be exactly key of the present invention so select the proper method of suitable polymkeric substance and selection preparation polymkeric substance.On the principle, the present invention is based on the result of study of following two aspects:
On the one hand, people such as Wu Baogang infer according to the relation of the size of droplet among the PDLC and threshold voltage, suitable monomer material in polymerization and in the phase separation interface of formed solid-liquid crystal less to the grappling effect of liquid crystal.Based on this, derived the relation of the ovality of the threshold voltage of PDLC and liquid crystal droplet, this relation is to be admitted by academia and to widely apply (Baogang WU, et., al.:Response time and voltages for PDLC light shutters, Liquid Crystals, 1989, Vol.5, No.5, pp1453-1469).This formula shows, if droplet is spherical, then threshold voltage is 0.This has just more deepened such notion, and the interface of formed solid-liquid crystal did not have a grappling effect substantially to liquid crystal during promptly suitable polymerisable monomer was separated by polymerization.Therefore, the present invention adopts phase separation to prepare polymer film.
On the other hand, according to the report of document, be separated the preparation polymer network to liquid crystal but have tangible orientation effect (Wang Qingbing etc. control liquid crystal molecular orientation with polymer network, Jilin University's natural science journal, 1996 04 phases, pp51-54).
The present invention is exactly the application of above-mentioned two aspect results of study.
Because the polymer film of phase separation preparation has covered the transparency electrode of liquid crystal cell inside surface, so it is all nonsensical to carry out any processing that influences liquid crystal aligning in advance at the liquid crystal cell inside surface.
Essence of the present invention is: made the not polymer film 1 of orientation effect with phase disengagement method on two electrode surfaces of the LCD that contains the nanometer polymer network, the polymer network 2 of manufacturing in this polymer film 1 and the cholesteryl liquid crystal forms one.The LCD that contains the nanometer polymer network is leaned on the orientation stabilization of polymer network to liquid crystal under zero electric field, ideal plane attitude and two stable show states of pseudo-burnt awl attitude are arranged, and the color of its demonstration is switched between water white transparency attitude and white reflection attitude.If when a blank screen is put in the behind of the LCD that contains the nanometer polymer network, just can show literal, figure, the image of white gravoply, with black engraved characters or black matrix wrongly written or mispronounced character.
The structure of liquid crystal cell and manufacture method have been behaved known.Usually, it comprises at least: two Zhang Pings row is placed, inside surface is coated with the transparent substrate 5,6 of transparent conductive film (transparent conductive film can be carved into any plane figure), for example glass substrate; The resin that plays sealing and adhesive effect around the substrate.Because of the polymer film in the structure of the present invention has covered the inside surface of liquid crystal cell, so all nonsensical to any processing in advance of glass substrate surface.Based on this, the present invention does not require glass substrate surface is handled.In order to pour into liquid crystal, in two transparent substrates 5,6 of bonding, rise all around sealing and adhesive effect resin to reserve at least one perfusing hole, wait and use resin-sealed this perfusing hole again after liquid crystal irritated.Common two transparent substrates are separated by 3 to 20 microns.Parallel in order to guarantee between the substrate 5,6, between two substrates, place some introns usually in addition, it is spherical that introns are generally, and its diameter is consistent with spacing between the substrate.Obviously, for convenience, yield rate and the other reasons of making, can also in said structure, add other elements.
A kind of preparation method who contains the LCD of nanometer polymer network provided by the invention is characterized in that adopting following steps:
Through after the above step, just can obtain the LCD that contains the nanometer polymer network of the present invention.
The preparation method's of the LCD that contains the nanometer polymer network provided by the invention principle of work:
Because of Ethylene glycol dimethacrylate better with the affinity of ITO than the affinity of liquid crystal and ITO, ITO and liquid crystal interface cause free free radical easily under ultraviolet light, so being separated that ultraviolet light causes at first occurs on the ITO of glass substrate, the liquid crystal cell inside surface the ITO layer at first be deposited the not polymer film of orientation effect of one deck.Increase with polymerization time, polymerization process is extended in liquid crystal, Ethylene glycol dimethacrylate in the liquid crystal or Ethylene glycol dimethacrylate and other potpourris that contains the compound of propenyl also begin polymerization, and polymer film extends to form polymer network to liquid crystal inside.So on the transparent conductive film surface, just the polymer film of the inside surface of liquid crystal cell will form an integral body with the polymer network in the cholesteryl liquid crystal.Compare with method disclosed on the document, that only in cholesteryl liquid crystal, make polymer network, the compound that contains propenyl that the present invention needs is more, this is because except the polymer network in liquid crystal need consume the propenyl compounds, and the polymer film that covers at the liquid crystal cell inside surface also will consume a lot of propenyl compounds.
The invention has the advantages that: compare for No. 92103952 with Chinese patent application, on the one hand, except having utilized the adjusting of polymer network to cholesteryl liquid crystal pitch, catoptrical spectral range is obtained beyond the increase, also added the character of the random orientation of screw axis under the orientation effect of liquid crystal cell interpolymer network of cholesteryl liquid crystal, made light in whole visible spectrum frequency range, realize uniform Bragg reflection; On the other hand, the inside surface of liquid crystal cell all need not to handle before and after envelope box and perfusion liquid crystal, has simplified preparation process; The defective of liquid crystal cell inside surface is leaned on the polymer film of light initiation polymerization institute deposit subsequently and is covered.
Description of drawings
Fig. 1 is a structural representation of the present invention
Wherein 1 is polymer film, and 2 is polymer network, and 3 is cholesteryl liquid crystal, and 4 is transparency electrode, and 5 and 6 are respectively transparency carrier and following transparency carrier;
Fig. 2 is the synoptic diagram of polymer network of the present invention to the orientation effect of liquid crystal
Wherein 1 is polymer film, and 2 is polymer network, and 3 is cholesteryl liquid crystal, and 4 is transparency electrode, and 5 and 6 are respectively transparency carrier and following transparency carrier;
Fig. 3 is the principle schematic of broadening Bragg reflection spectrum of the present invention
Wherein 1 is polymer film, 2 is polymer network, 3 is cholesteryl liquid crystal, 4 is transparency electrode, 5 and 6 are respectively transparency carrier and following transparency carrier, and 7 is incident light, and 8 is reflected light, a represents represented position incident light and cholesteryl liquid crystal screw axis approaching parallel, and b represents represented position incident light and cholesteryl liquid crystal screw axis near vertical;
Fig. 4 removes last transparency carrier 5 for structure of the present invention, again liquid crystal is removed the later on left polymer film and the scanning electron microscope microphoto of network
Wherein 1 is polymer film, and 2 is polymer network;
Fig. 5 removes the later on left polymer film and the stereoscan photograph of network xsect to liquid crystal for structure of the present invention
Wherein 1 is polymer film, and 2 is polymer network, and 6 are following transparency carrier.
The contrast accompanying drawing is introduced the present invention in detail below.
As shown in Figure 1, the transparency electrode 4 of last transparency carrier 5 and following transparency carrier 6 is put in opposite directions, seal into liquid crystal cell by known manufacture method, cholesteryl liquid crystal 3 fills in wherein, polymer network 2 to all the winds extends among cholesteryl liquid crystal 3, be connected above-mentioned two transparency carriers 5,6 on transparency electrode 4 on polymer film 1 on become as a whole.
Shown in accompanying drawing 2 dotted line left-hand components, after the high voltage pulse, the screw axis 3a of cholesteryl liquid crystal 3 tends to perpendicular to last transparency carrier 5 or following transparency carrier 6.But because the existence of polymer network 2, cholesteryl liquid crystal 3 is along the polymer network 2 approximate one section network orientation that is parallel to the direction of transparency carrier 5 or following transparency carrier 6, so the screw axis 3a of cholesteryl liquid crystal 3 is approximately perpendicular to the direction of last transparency carrier 5 or following transparency carrier 6.Because the sensing of screw axis 3a is different everywhere, all in all, this is not the plane attitude, but a kind of ideal plane attitude.
Shown in accompanying drawing 2 dotted line right-hand components, after the low voltage pulse, the screw axis 3a of cholesteryl liquid crystal 3 tends to be parallel to transparency carrier 5 or following transparency carrier 6.But because the existence of polymer network 2, cholesteryl liquid crystal 3 is along the one section network orientation of polymer network 2 approximately perpendicular to the direction of last transparency carrier 5 or following transparency carrier 6, so the approximate direction that is parallel to transparency carrier 5 or following transparency carrier 6 of the screw axis 3a of cholesteryl liquid crystal 3.Because the sensing of screw axis 3a is different everywhere, all in all, this is not burnt awl attitude, but a kind of pseudo-burnt awl attitude.
As shown in Figure 3, incident light 7 enters cholesteryl liquid crystal 3 by last transparency carrier 5, transparency electrode 4, polymer film 1, Bragg reflection takes place in cholesteryl liquid crystal 3: near on the local a of transparency carrier 5, because of liquid crystal is anchored on the polymer network, its screw axis is parallel with incident light 7, so it is longer that the wavelength of Bragg reflection takes place; If the regulating action of 2 pairs of these place's liquid crystal pitch of polymer network wherein makes the pitch of liquid crystal long, then the wavelength of Bragg reflection is just longer.And near on the local b of transparency carrier 5, because of liquid crystal is anchored on another polymer network, the angle of its screw axis and 7 one-tenth bigger of incident lights, the wavelength of Bragg reflection is shorter; If the regulating action of 2 pairs of pitch of polymer network wherein makes the pitch ratio of this place's liquid crystal shorter, then the wavelength of Bragg reflection is just shorter.Minimal wave length in the reflected light and long wavelength in the reflected light have been represented in the formed reflected light 8 of this two places Bragg reflection.
Actual conditions are: the screw axis of liquid crystal is anchored on the sensing polymer network at random, with the direction on transparent substrate 5 or 6 surfaces also be at random.Simultaneously, polymer network may allow pitch increase to the influence of the pitch of liquid crystal, also may allow pitch reduce, and its effect is again at random.The result of above-mentioned factor stack is exactly the light wave that has comprised various wavelength in the reflected light, thereby realizes the reflection of white light.
Provided the present invention by the embodiment manufactured samples as accompanying drawing 4, then the last transparent substrate 5 of sample has been peeled off, removes, again the liquid crystal in the sample soaked, removes solvent and the later left polymer film 1 of liquid crystal and the scanning electron microscope microphoto (seeing main photo) of polymer network 2 with solvent (normal hexane) with technique known (cooled with liquid nitrogen method).Polymer film 1 is dry to be shunk because of solvent evaporates makes, and can see that polymer film 1 splits on the photo, can see polymer network 2 from the seam that splits.Photo demonstrates between polymer film 1 and the polymer network 2 as a whole, and polymer network 2 is aggregated thing film 1 and covers.The small photo in accompanying drawing 4 upper right corner is the amplification of polymer network 2 parts.
Provided the present invention by the embodiment manufactured samples as accompanying drawing 5, then sample is done a crosscut with technique known (needing cooled with liquid nitrogen), again the polymer film 1 left after solvent (normal hexane) immersion of the liquid crystal in the sample, removing solvent and the liquid crystal and the stereoscan photograph of polymer network 2 structures.It is an integral body fully that photo demonstrates between polymer film 1 and the polymer network 2.
Embodiment
Embodiment 1:
At the trade mark is the CB15 (E.Merck) that adds general assembly (TW) 39% among the YM8 (Yantai Wan Run Fine Chemical Co., Ltd), and such mixed liquid crystal is a cholesteryl liquid crystal, and its optics pitch is about 580 nanometers, corresponding to orange-yellow light wavelength in the visible light.The Ethylene glycol dimethacrylate that adds general assembly (TW) 5% to 15% then for example adds 10% Ethylene glycol dimethacrylate.Preferably add 2～5% benzophenone as light trigger.Said mixture stirred evenly obtain liquid crystal-monomer mixture.Get two glass clean, that have ITO (tin indium oxide) electrically conducting transparent membrane material, technology system liquid crystal cell (need not be coated with alignment agent, also not do other any processing on nesa coating routinely.), control enclosure is thick about 10 microns, by technique known the electrode on the lower glass plate is drawn.Above-mentioned liquid crystal-monomer mixture is charged into liquid crystal cell by known method.The liquid crystal cell that will be filled with liquid crystal-monomer mixture then places 2mW/cm
2Peak wavelength is that the ultraviolet light of 460nm exposed 0.5 hour down.Because of Ethylene glycol dimethacrylate better with the affinity of ITO than the affinity of liquid crystal and ITO, ITO and liquid crystal interface cause free free radical easily under ultraviolet light, so being separated that ultraviolet light causes at first occurs near the glass substrate, makes the ITO layer on the glass substrate be deposited the one layer of polymeric film.Passing in time, polymerization is extended in liquid crystal.When the Ethylene glycol dimethacrylate in the liquid crystal also began polymerization, the branch that extends in liquid crystal from the polymer film just had been deep into liquid crystal inside, formed the polymer network of liquid crystal inside.Like this, cover the polymer film on transparent conductive film surface and just become as a whole with polymer network in the cholesteryl liquid crystal.
Embodiment 2:
At the trade mark is the CB15 (E.Merck) that adds general assembly (TW) 39% among the YM8 (Yantai Wan Run Fine Chemical Co., Ltd), and such mixed liquid crystal is a cholesteryl liquid crystal, and its optics pitch is about 520 nanometers, corresponding to the wavelength of green light in the visible light.Add the Ethylene glycol dimethacrylate of general assembly (TW) (y-x) %, the propenyl compounds of x% then, methyl methacrylate for example, wherein the span of y is 5 to 15, the x span is (0～0.8) y.For example 6% Ethylene glycol dimethacrylate, 6% butyl methacrylate.Preferably add 2～5% benzophenone again as light trigger.Said mixture stirred evenly obtain liquid crystal-monomer mixture.Get two glass clean, that have ITO (tin indium oxide) electrically conducting transparent membrane material, technology system liquid crystal cell (need not be coated with alignment agent, also not do other any processing on nesa coating routinely.), control enclosure is thick about 10 microns, draws by the electrode that known scheme will go up on the lower glass plate.Above-mentioned liquid crystal-monomer mixture is charged into liquid crystal cell by known method.The liquid crystal cell that will be filled with liquid crystal-monomer mixture then places 2mW/cm
2Peak wavelength is that the ultraviolet light of 460nm exposed 1 hour down.Because of the potpourri of Ethylene glycol dimethacrylate better with the affinity of ITO than the affinity of liquid crystal and ITO, glass and liquid crystal interface be caused free free radical under ultraviolet light, so being separated that ultraviolet light causes at first occurs near the glass substrate, make on the ITO layer on the glass substrate the not polymer film of orientation effect of deposit one deck.Passing in time, polymerization is extended in liquid crystal.When the Ethylene glycol dimethacrylate in the liquid crystal also began polymerization, the branch that extends in liquid crystal from the polymer film just had been deep into liquid crystal inside, formed the polymer network of liquid crystal inside.Like this, cover the polymer film on transparent conductive film surface and just become as a whole with polymer network in the cholesteryl liquid crystal.
According to here the narration method, those of ordinary skill in the art just can produce the LCD of structure of the present invention.
Claims (4)
1, a kind of LCD that contains the nanometer polymer network, it comprises: inside surface is coated with liquid crystal cell, the cholesteryl liquid crystal of transparent conductive film, and the size of the optics pitch of described cholesteryl liquid crystal is characterized in that it also comprises in visible wavelength range:
Polymer film that forms in the phase separation (1) and polymer network (2), described polymer film (1) is covered in the transparent conductive film surface, described polymer network (2) is arranged in cholesteryl liquid crystal, and described polymer film (1) is as a whole with described polymer network (2).
2, a kind of LCD that contains the nanometer polymer network according to claim 1 is characterized in that described polymer film
(1) and polymer network (2) adopt the acrylic ester compound polymerization that does not contain benzene nucleus in the molecular structure to constitute, the described acrylic ester compound that does not contain benzene nucleus is an Ethylene glycol dimethacrylate.
3, a kind of LCD that contains the nanometer polymer network according to claim 1 is characterized in that described polymer film
(1) and polymer network (2) adopt the multipolymer of the two or more acrylic ester monomers do not contain benzene nucleus to constitute, the multipolymer of described two or more acrylic ester monomers is polymkeric substance that Ethylene glycol dimethacrylate and methyl methacrylate copolymer form.
4, a kind of LCD that contains the nanometer polymer network according to claim 1, the diameter that it is characterized in that described polymer network (2) skeleton is below 500 nanometers.
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| JP6808916B2 (en) * | 2015-08-11 | 2021-01-06 | Dic株式会社 | Liquid crystal display element |
| CN105974675B (en) * | 2016-07-13 | 2019-02-19 | 深圳市华星光电技术有限公司 | Flexible display panels and preparation method thereof |
| CN106200186B (en) * | 2016-09-07 | 2020-06-09 | 深圳市宝立创科技有限公司 | Liquid crystal handwriting device and manufacturing method thereof |
| CN106980216A (en) * | 2017-04-20 | 2017-07-25 | 深圳市屏柔科技有限公司 | A kind of hand-written LCDs and preparation method thereof |
| CN111736377B (en) * | 2020-06-17 | 2022-04-26 | 深圳市华星光电半导体显示技术有限公司 | Liquid crystal layer, preparation method thereof and liquid crystal display device |
| CN112946966B (en) * | 2021-02-03 | 2023-03-14 | 电子科技大学 | Large-angle liquid crystal optical phased array scanning assembly |
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| CN1054208C (en) * | 1991-05-02 | 2000-07-05 | 肯特州大学 | Liquid crystalline light modulating device and material |
| US6133975A (en) * | 1996-05-10 | 2000-10-17 | Kent State University | Bistable liquid crystal display device using polymer stabilization |
| CN1399729A (en) * | 1999-09-03 | 2003-02-26 | 肯特州大学 | Fabrication of aligned liquid crystal cell/film by simultaneous alignment and phase separation |
| US6597422B1 (en) * | 1998-12-15 | 2003-07-22 | Rolic Ag | Orientation layer for a liquid crystal material |
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- 2004-01-08 CN CNB2004100216267A patent/CN100351677C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054208C (en) * | 1991-05-02 | 2000-07-05 | 肯特州大学 | Liquid crystalline light modulating device and material |
| US6133975A (en) * | 1996-05-10 | 2000-10-17 | Kent State University | Bistable liquid crystal display device using polymer stabilization |
| US6597422B1 (en) * | 1998-12-15 | 2003-07-22 | Rolic Ag | Orientation layer for a liquid crystal material |
| CN1399729A (en) * | 1999-09-03 | 2003-02-26 | 肯特州大学 | Fabrication of aligned liquid crystal cell/film by simultaneous alignment and phase separation |
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| 液晶中形成的聚合物网络织构及形貌的研究 王庆兵等.液晶与显示，第14卷第2期 1999 * |
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| 用聚合物网络控制液晶分子取向 王庆兵等.吉林大学自然科学学报，第4期 1996 * |
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| CN1641416A (en) | 2005-07-20 |
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