CN1111289C - High reflecting rate polymer dispersing liquid crystal light valve displaying device - Google Patents
High reflecting rate polymer dispersing liquid crystal light valve displaying device Download PDFInfo
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- CN1111289C CN1111289C CN 96116056 CN96116056A CN1111289C CN 1111289 C CN1111289 C CN 1111289C CN 96116056 CN96116056 CN 96116056 CN 96116056 A CN96116056 A CN 96116056A CN 1111289 C CN1111289 C CN 1111289C
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- liquid crystal
- light valve
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Abstract
The present invention relates to a high reflecting rate polymer dispersing liquid crystal light valve displaying device which belongs to a liquid crystal light valve film used for displaying electronic messages. The device has a basic structure having a polymer used as a winding phase and liquid crystal as a dispersing phase, and the basic structure is clamped between two transparent conductive films; the liquid crystal is mixed with chiral cholester liquid crystal from normal nematic liquid crystal and enveloped in the polymer in the form of drops to form a two-phase system. The device has the advantages that the dispersing liquid crystal of an original polymer adds the function of directional reflection on the basis of the functions of penetrating or scattering light rays under the action of an electric field. The device can be used for integrating an electric control light penetrating curtain and information storage and display.
Description
The present invention relates to a kind of polymers dispersed liquid crystal light valve display device of new construction.Original Polymer Dispersed Liquid Crystal can see through light or scattering under electric field action, and the present invention has increased the orienting reflex function again, and belong to the electronic information demonstration and use the liquid crystal light valve film, be a kind of high reflecting rate polymer dispersing liquid crystal light valve displaying device specifically.
The history of the device that polymkeric substance and liquid crystal droplet dispersion form existing three more than ten years is mixed for the thermic look by Qiu Jier (Churchill) people of etc.ing with polyvinyl alcohol (PVA) water-soluble polymers and cholesteric liquid crystal in early days and becomes and show or the field causes look change demonstration.Because the limitation of cholesteric liquid crystal can only drive with electron beam at that time, and display mode only is change in color, conducting and the shutoff that can't be satisfied with to light.The eighties has been invented with polyvinyl alcohol water solution and eurymeric nematic liquid crystal by Cathy Ferguson (Fergason) and has been made liquid crystal microballoon dispersed system, through coating, oven dry, operation such as compound is produced with scattering or is absorbed as the light valve display of mechanism, (the Kent State Univcrsity of U.S. Kent State University afterwards, Ohio USA) invented polymer monomer or given polymers and the eurymeric nematic liquid crystal is mixed into the dissolving homogeneous phase earlier, through be coated with compound after again through the heating, methods such as ultraviolet ray irradiation or electron beam irradiation make liquid crystal progressively be separated into the droplet dispersed system in polymer polymerizing a part amount increase process, and are named as Polymer Dispersed Liquid Crystal (Polymer Dispersed LiquidCrystal-PDLC) light valve display.Its scattering mechanism meets the following conditions:
1) liquid crystal is to ordinary refraction index n
oEqual the optical index n of polymkeric substance
p: n
o=n
p
2) liquid crystal is to the extraordinary ray refractive index n
eOptical index n much larger than polymkeric substance
p: n
e" n
p
Because the polymers dispersed liquid crystal light valve display to the scattering strength of visible light be proportional to optical index residual quantity _ Δ n square: Δ n
2=(n
e-n
p)
2=(n
e-n
o)
2Optical index residual quantity Δ n has characterized the optical anisotropy of liquid crystal molecule.Owing to be subjected to the restriction of chemical constitution.Δ n value maximum is no more than 0.28.(the Δ n of paper is 0.5～1.0) thereby its shortcoming are that the object of pressing close to is lacked screening ability or opacifying strength, and dispersion effect is not as paper.Owing to lack the front-reflection function, limited the range of application of this light valve greatly simultaneously.Even can use two secondary color dyestuffs to increase its contrast, show occasion but what adopt because of its is mechanism of absorption, also can't be used for white.
The object of the invention is to overcome shortcoming of the prior art, a kind of high reflecting rate polymer dispersing liquid crystal light valve displaying device is proposed, make it original Polymer Dispersed Liquid Crystal (PDLC) can under the electric field action light seen through or the function basis of scattering on increase the orienting reflex function and strengthen scattering function.
The object of the invention is realized by following technical scheme: this high reflecting rate polymer dispersing liquid crystal light valve displaying device, basic structure with " polymkeric substance as external phase, liquid crystal as disperse phase ", and the quilt folder spreads between the two-layer transparent conductive film, it is characterized in that liquid crystal is to be mixed with cholesteric liquid crystal by the eurymeric nematic liquid crystal, is formed binary system with the droplet form by envelope in polymkeric substance.In liquid crystal droplet, liquid crystal molecule forms the helical arrangement with intrinsic pitch and chirality.Can not have only a kind of droplet of mixed liquid crystal in polymkeric substance and mixing in the phase system layer of liquid crystal, but have under the pitch of two kinds of liquid crystal molecule helical arrangement with the microballoon dispersion, and then their are evenly mixed to disperse to enter mix the phase system layer.
Transparent conductive film among the present invention, its substrate can be mylars, and transparent ITO-tin indium oxide coating is arranged on the surface within it.Because the present invention has used the potpourri of eurymeric nematic liquid crystal and chirality cholesteric liquid crystal, in its droplet, liquid crystal molecule forms has the helical arrangement of intrinsic pitch and chirality, and is different from that original technology only has a kind of nematic liquid crystal and relies on the molecular force balance and form the state of the mixed and disorderly first preface of liquid crystal molecule in its droplet.The present invention original technology can only see through light or the basis of scattering on increased the orienting reflex function.
Eurymeric nematic liquid crystal among the present invention is meant a kind of in all eurymeric nematic liquid crystals, can be alkyl (alkoxy) biphenyl nitrile liquid crystal series, and chemical structural formula is
R
1(C=2～7) are straight-chain paraffin; Or alkyl (alkoxy) terphenyl nitrile liquid crystal series, chemical structural formula is
Be straight-chain paraffin; Or alkyl (alkoxy) miaow pyridine benzene nitrile liquid crystal series, chemical structural formula is
-CN.R
3(c=3～7) are straight-chain paraffin; Or alkyl (alkoxy) cyclopentyl benzene nitrile liquid crystal series, chemical structural formula is
Be straight-chain paraffin.Chiral liquid crystal among the present invention is meant a kind of in all chiral liquid crystal or the cholesteric liquid crystal, can be CB-15, and its structure is
CN, for moral is enclosed the product of E.MERK company, or R-1011, its structural formula is C
5H
Product for German E.MERK company; Or all kinds of cholesterol esterses and chlorine compare thing.
Polymkeric substance among the present invention is meant all thermoset resin monomers and gives polymers, or hot-melt resin monomer and pre-polymer, or ultraviolet ray and electron beam can be consolidated the type monomer and give polymers, or water soluble resin, epoxy resin is arranged usually, polyacrylic resin, urethane resin, polyvinyl alcohol resin, polyvinyl acetal-based resin has increased kind greatly on the polymeric material kind that is suitable for.
Eurymeric nematic liquid crystal and chirality cholesteric liquid crystal diameter of droplets between 2～10 microns, 4 microns of average out to.And exchange device liquid crystal droplet diameter is between 0.6～2 micron, and 1 micron of average out to is to obtain the maximum scattering to visible light.Liquid-drop diameter of the present invention had both satisfied Prague (Bragy) conditioned reflex, made cut-in voltage lower again.In general, the liquid crystal droplet diameter is big more, and Bragg reflection is strong more, in the liquid crystal droplet
Between scattering process also strong more; Diameter of droplets is more little, and Bragg reflection is weak more, and the scattering process of liquid crystal ball and polymer interface is big more.Generally, suitably determine the size of microballoon according to the specific requirement of using.
The shape of liquid crystal droplet should make it flat for well as far as possible, and its ovality should be as far as possible little, and the ellipticity scope is best with 0.3～0.6.Because the droplet near circular that ellipticity is bigger is unfavorable for producing Bragg reflection, and ellipticity hour, is convenient to produce the high reflectance Bragg effect.Be easy to realize ellipticity required for the present invention from technology, for example can control the volumetric shrinkage of polymkeric substance, the evaporation rate of control solvent, control composite pressure etc.
Employed several polymer raw material is according to identical or composite near identical mass ratio in the 1O% scope; Employed several liquid crystal raw material is composite according to following mass ratio: at the eurymeric nematic liquid crystal of each color of light wavelength to the ratio of cholesteric liquid crystal be 10: 10 to 15: 5 with, the ratio of the quality of employed two kinds of hardening agent C apcure 3-800 and C apcure 40 is 97: 3 to 99: 1.The ratio of the quality of its potpourri when mixing again with liquid crystal compound is (1～1.4): 10.The employed degree of polymerization is that the percent concentration of 1750 polyvinyl alcohol water solution is 6%-10%, and its quality is 10: 3 to 10: 5 with the ratio of liquid crystal compound quality.
The manufacture technology of this liquid crystal light valve display device is more complicated meticulousr than the manufacture technology of original general polymer dispersed liquid crystal light valve, also has technical breakthrough simultaneously.Original common process is with polymer monomer or gives polymers and liquid crystal is mixed into the dissolving homogeneous phase, makes liquid crystal progressively be separated into the droplet dispersed system after compound again in the polymer polymerizing process with physical method through coating.And the present invention has had new technological breakthrough on this basis: the one, and give in the process of curing liquid crystal droplet at polymkeric substance and realize being separated, and at the inner liquid crystal molecule aggregate that forms of droplet
The 2nd, do not rely on the polymer polymerizing process, but the potpourri of liquid crystal and aqueous solutions of polymers is obtained liquid crystal microballoon dispersion liquid with the physical method of high-speed stirred; The 3rd, do not adopt conventional compound coating process, but will dissimilar dispersion liquids according to primary coat with push up the sequencing that is coated with, compound again after the coating.
Advantage of the present invention be with original Polymer Dispersed Liquid Crystal (PDLC) can under the electric field action light seen through or the function basis of scattering on increased the orienting reflex function.This invention can be used for automatically controlled printing opacity curtain, but usable reflection infrared ray, also can be used as the electronics screen, be used for the contrast that display can improve conducting state and close off-state, particularly improved the optics contrast under the dark background, can carry out multichannel drives, improve actuating speed, thereby the perfect greatly practicality of Polymer Dispersed Liquid Crystal technology, when it when combining, just might be realized contemporary state-of-the-art development target one collection information storage and flexible readable electronic newspaper or the e-book that are shown in one with multistable liquid product display techniques (MLCD).
Description of drawings:
Fig. 1 is a kind of high reflecting rate polymer dispersing liquid crystal light valve displaying device structural drawing, and its liquid crystal droplet with helical arrangement molecule presents the selection reflex to incident ray.
Fig. 2 also is a kind of high rate polymers dispersed liquid crystal light valve display device structure figure that penetrates, the effect that the microballoon dispersion state that the pitch that its two kinds of liquid crystal molecules are arranged in the shape of a spiral is different has binary complementary color mixed structure reflected white-light.
Fig. 3, Fig. 4 represent the liquid crystal droplet of different ovalitys, among Fig. 3, and ovality ε=1, Fig. 4 is ovality ε=0.5.
Fig. 5 represents the transmittance and the impressed voltage relation of common PDLC device.
Fig. 6 represents it is transmittance of the present invention and impressed voltage relation.
Two kinds of high reflecting rate polymer dispersing liquid crystal light valve displaying devices of proposed by the invention this, has polymkeric substance (3) as external phase, liquid crystal droplet (4) is as disperse phase, and spread between the two-layer film substrate (1) that has transparent conductive film coating (2) by folder.This liquid crystal droplet is to be mixed with cholesteric liquid crystal by the eurymeric nematic liquid crystal, with droplet morphology by envelope in polymkeric substance (3), form binary system.
Among Fig. 1, the left side is the added electric field state, right-hand part is an added electric field state not, when added electric field not, the potpourri of the cholesteric liquid crystal of liquid crystal droplet and eurymeric nematic liquid crystal has the selection reflex according to the pitch and the chirality of its intrinsic to incident ray A, and reflected light B is arranged: the one, and chirality is selected, and liquid crystal reflects back the incident light A component identical with self hand of spiral, the 2nd, wavelength is selected, and the incident light that liquid crystal only will satisfy following relationship produces Prague (Bragg) reflection:
Δλ＝Δn.ρ
Δ λ shows that reflecting light claims scope, and Δ n is the optical anisotropy of liquid crystal, and ρ is the pitch of Liquid Crystal Molecules Alignment.The centre wavelength of reflection is
λ=n. ρ, n represents the average light refractive index.
Can be according to different application scenarios, λ may be selected to be infrared region, visible region etc.
Do the time spent at first extra electric field, another optical effect is scattering process, and scattered light is C
oIt can be divided into two kinds again: a kind of is the interface scattering of liquid crystal droplet and polymkeric substance inclusion complex, and this situation that acts on common PDLC device is identical, and its scattering strength is
Sc
1∝〔(n
e+n
o/2)-n
p〕
2。
Another kind of then be the chiral liquid crystal molecular aggregate of liquid crystal droplet inside
Between scattering.
Be the cybotactates with chiral liquid crystal molecule of identical optical axis, its maximum scattering intensity is Sc
1∝ (n
e-n
o)
2
This scattering is prevalent in the chiral liquid crystal system after the external disturbance.By Sc
1With Sc
2Two kinds of scattering mechanisms that expression formula reflected and the Bragg reflection that formula Δ λ=△ n. ρ provides mechanism have comprehensively promptly constituted " shutoff " effect under the no electric field action.The scattering mechanism contrast single with the PDLC of routine, it is obviously strengthened the shutoff effect of light.
Having under the extra electric field effect, the chirality helical structure of liquid crystal droplet inside is straightened, and the derotation is a nematic phase. and all molecules are orientated with outer field direction, and this state is identical with common PDLC effect, n
o=nP
1Device is clear state.
Fig. 2 represents the structure of reflected white-light. according to the requirement of reflection wavelength. cut open respectively fully at wavelength X
1, λ
2Two kinds of liquid crystal microballoon dispersions (4-a) and (4-b), then it is mixed.Blending ratio meets waiting of international CIE standard chromatic graph can point or D
65Color temperature point, λ
1, λ
2Also should satisfy the requirement of complementary color each other.For example: λ
1Be red wavelength, λ
2Be the blue look wavelength of green grass or young crops.When above-mentioned night brilliant droplet dispersion liquid evenly coat ITO indium tin oxide conductive film and drying after, add a cover compound another layer conductive film, promptly obtained device of the present invention.Wherein (3-a) is polymeric over coat, (3-b) is copolymer bottom coating.There is following show state in this device:
1, added electric field not, i.e. E=O zone, device is a white.
2, increase electric field, i.e. E＞Eth zone, device is clear state.
In Fig. 1, Fig. 2, A represents incident light, and B represents reflected light, and C represents scattered light, and D represents emergent light.
Embodiment 1
With epoxy resin Epon 828, ELR 4221, ELR 4299 with each ratio of 1/3 composite evenly after, take by weighing 10 grams and be placed in the stirrer, this is a kind of polymkeric substance; Get liquid crystal RO-TN-4040.7 gram, liquid crystal CB-15-0.3 gram, also add its mixed potpourri in the stirrer, together stir with the polymer ring epoxy resins, the spy mixes after limpid, adds 98: 2 potpourri, 1 gram of hardening agent Capcure 3-800 and Capcure 40 again, add again 20 microns of 0.005 gram between separated material, push composite coating machine after stirring, quilt is pressed from both sides spreads on two surface resistivity 80 Ω
Tin indium oxide (ITO) transparent conductive film in, the heating furnace of putting into 45 ℃ then gives curing 4 hours, treat liquid crystal with 4 microns droplets of mean diameter be separated finish after, put into 75 ℃ of heating furnaces again and carry out back curing 8 hours, just obtain high reflecting rate polymer dispersing liquid crystal light valve displaying device, can reflect visible light.
Embodiment 2
Get aqueous solution 9 gram of polyvinyl alcohol (PVA) (degree of polymerization is 1750) of 7% concentration and potpourri 4.5 grams that are modulated to red liquid crystal RO-TN-404 and liquid crystal CB15 and together put into the high speed agitator stirring, obtain the liquid crystal microballoon dispersion liquid of 8 microns of mean diameters, as primary coat solution.Get aqueous solution 9 grams of the polyvinyl alcohol (PVA) of 7% concentration again, and the potpourri 4.5 that is modulated into the green liquid crystal RO-TN-404 of orchid and liquid crystal R1011, CB15 restrains, together put into high speed agitator and stir the liquid crystal microballoon dispersion liquid that obtains 8 microns of mean diameters, as the top applying soln.
With the coating weight of 10 microns of primary coat solution butt thickness, coat surface resistivity 80 Ω with the recessed roller coat of accurate miniature city machine
Mylar on, treat undercoat oven dry after, to be coated with butt thickness be 10 microns top applying soln on the top again, after the drying, compound another layer conductive polyester film.Promptly obtain high reflecting rate polymer dispersing liquid crystal light valve displaying device.
Under no electric field action, this high reflecting rate polymer dispersing liquid crystal light valve displaying device is the reflecting body film of white; Under the electric field driven, be transparent body film outside.
Claims (6)
1, a kind of polymers dispersed liquid crystal light valve display device, has polymkeric substance as external phase, liquid crystal is as the basic structure of disperse phase, and the quilt folder spreads between the two-layer transparent conductive film, its special liquid crystal that is seized with terror is to be mixed with the chirality cholesteric liquid crystal by the eurymeric nematic liquid crystal, in polymkeric substance, formed binary system with the droplet form by envelope, liquid crystal droplet is a flat pattern, its ellipticity scope is 0.3-0.6, in mixing in the phase system layer of polymkeric substance and liquid crystal, arrange one or both liquid crystal droplets, liquid crystal molecule forms the helical arrangement with intrinsic pitch and chirality, the pitch difference of two kinds of liquid crystal droplets in the liquid crystal droplet.
2, according to the described polymers dispersed liquid crystal light valve display device of claim 1, it is characterized in that the eurymeric nematic liquid crystal is meant a kind of in all eurymeric nematic liquid crystals, be alkyl biphenyl eyeball liquid crystal series, or alkyl terphenyl eyeball liquid crystal series, or alkyl miaow pyridine benzene eyeball liquid crystal series, or alkyl cyclopentyl benzene eyeball liquid crystal series.
3, according to the described polymers dispersed liquid crystal light valve display device of claim 1, it is characterized in that the chirality cholesteric liquid crystal is meant a kind of in all chirality cholesteric liquid crystals, be CB-15, or R-1011, or various cholesterol esters and chloride.
4, according to the described polymers dispersed liquid crystal light valve display device of claim 1, its special polymkeric substance that is seized with terror is meant all thermoset resin monomers and gives polymers, or hot-melt resin monomer and give polymers, or ultraviolet ray and electron beam can consolidate the type monomer and give polymers, or water soluble resin: include epoxy resin, polyacrylic resin, polyurethane resin, polyvinyl alcohol resin, polyvinyl acetal-based resin.
5, according to the described polymers dispersed liquid crystal light valve display device of claim 1, it is characterized in that employed several polymer raw material is according to identical or composite near identical mass ratio in 10% scope, employed several liquid crystal raw material is composite according to following mass ratio: is between 10: 10 to 15: 5 at the eurymeric nematic liquid crystal of each color of light wavelength to the ratio of cholesteric liquid crystal, the ratio of the quality of employed two kinds of hardening agent Capcure 3-800 and Capcure 40 is 97: 3 to 99: 1, the ratio of the quality of its potpourri when mixing again with liquid crystal compound is (1-1.4): 10, the employed degree of polymerization is that the percent concentration of 1750 polyvinyl alcohol water solution is 6%-10%, and its quality is 10: 3 to 10: 5 with the ratio of liquid crystal compound quality.
6, according to the described polymers dispersed liquid crystal light valve display device of claim 1, it is characterized in that eurymeric nematic liquid crystal and chiral liquid crystal diameter of droplets are between the 2-10 micron, 4 microns of average out to, promptly satisfy Bragg's condition of reflection, and, compare with the display device with other diameter of droplets, cut-in voltage is lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96116056 CN1111289C (en) | 1996-11-04 | 1996-11-04 | High reflecting rate polymer dispersing liquid crystal light valve displaying device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96116056 CN1111289C (en) | 1996-11-04 | 1996-11-04 | High reflecting rate polymer dispersing liquid crystal light valve displaying device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1181568A CN1181568A (en) | 1998-05-13 |
| CN1111289C true CN1111289C (en) | 2003-06-11 |
Family
ID=5123245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96116056 Expired - Fee Related CN1111289C (en) | 1996-11-04 | 1996-11-04 | High reflecting rate polymer dispersing liquid crystal light valve displaying device |
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| Country | Link |
|---|---|
| CN (1) | CN1111289C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071031A (en) * | 2010-12-24 | 2011-05-25 | 北京科技大学 | Method for preparing epoxy-based polymer dispersed liquid crystal film material |
| CN102654687B (en) * | 2012-02-29 | 2015-06-03 | 京东方科技集团股份有限公司 | Transparent display device |
| US9429787B2 (en) | 2012-02-29 | 2016-08-30 | Boe Technology Group Co., Ltd. | Transparent display unit |
| KR102205991B1 (en) * | 2013-04-18 | 2021-01-21 | 메르크 파텐트 게엠베하 | Layer or article comprising cholesteric polymer particles |
| ES2861386T3 (en) * | 2015-03-18 | 2021-10-06 | Gauzy Ltd | Electrically switchable solar absorbent and reflective film and glazing |
| CN104656338B (en) * | 2015-03-20 | 2017-09-29 | 京东方科技集团股份有限公司 | The preparation method of grating, display device and grating |
| CN110616018B (en) * | 2019-10-14 | 2021-06-29 | 智谱纳米科技(上海)有限公司 | Spectrum selective reflection liquid crystal film and preparation method thereof |
| CN111117409A (en) * | 2019-12-31 | 2020-05-08 | 苏州艾科迪新材料科技有限公司 | Colorful polymer coating and preparation method thereof |
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1996
- 1996-11-04 CN CN 96116056 patent/CN1111289C/en not_active Expired - Fee Related
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