CN102621617B - Production method for nano-doped electric field controlled liquid crystal round polaroid - Google Patents
Production method for nano-doped electric field controlled liquid crystal round polaroid Download PDFInfo
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- CN102621617B CN102621617B CN201210050394.2A CN201210050394A CN102621617B CN 102621617 B CN102621617 B CN 102621617B CN 201210050394 A CN201210050394 A CN 201210050394A CN 102621617 B CN102621617 B CN 102621617B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 41
- 230000005684 electric field Effects 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002086 nanomaterial Substances 0.000 claims abstract description 13
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 17
- 210000002858 crystal cell Anatomy 0.000 claims description 10
- 239000004988 Nematic liquid crystal Substances 0.000 claims description 6
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 claims description 6
- -1 dimethyl butyrate alcohol derivatives Chemical class 0.000 claims description 5
- 239000002322 conducting polymer Substances 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 230000001939 inductive effect Effects 0.000 claims description 4
- 239000002071 nanotube Substances 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical class OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 claims description 2
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical class C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 claims description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 2
- 230000003098 cholesteric effect Effects 0.000 claims description 2
- 150000001841 cholesterols Chemical class 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002127 nanobelt Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000011521 glass Substances 0.000 abstract description 5
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- 238000001228 spectrum Methods 0.000 description 3
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
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Abstract
The invention provides a production method for an electric field controlled wide wave reflection liquid crystal round polaroid, which belongs to the technical field of functional material liquid crystal display. By enabling one-dimensional nano materials and cholesteric liquid crystal to be mixed and poured into a liquid crystal box or a thin membrane, the method exerts different electric fields to control reflection wave width. The method has the advantages of being simple in composition and process, reflection wave width of the polaroid can be controlled through electric fields according to actual needs, and reversible control also can be achieved. The method can be applied to functional thin membranes and devices such as intelligent glass, electronic paper, liquid crystal display light incremental membranes and the like.
Description
Technical field
The invention belongs to functional material technical field of liquid crystal display, provide a kind of can electric field the manufacture method of liquid crystal circular polarizing disk of regulation and control wide wave reflection, use nano particle cholesteric liquid crystal compound system to realize the manufacture of the liquid crystal circular polarizing disk of wide wave reflection.
Background technology
Because polaroid has unique optical characteristics, thereby have a wide range of applications in display device, transportation industries, national defence and Cutting-edge science technology.At present conventional polaroid be mainly absorption-type polaroid, although this class polaroid is cheap, there are many shortcoming and defect, for example light loss is large, working environment is limited, the absorption bands of finished product is fixing can not be adjusted etc.And can electric field the reflective polarizer of regulation and control because its excellent performance has broad application prospects, as the light brightness enhancement film of liquid crystal display, intelligent glass, shielded film, energy-saving reflecting coating, electronic paper etc.
As everyone knows, cholesteric liquid crystal is because its special helical structure makes its optical property that possesses many uniquenesses, as circular dichroism, selective reflecting, optical activity etc.And the selective reflecting important optical property that is one of them.For cholesteric liquid crystal, along its screw axis, liquid crystal molecule points to vows that the length of the corresponding screw axis of rotating 360 degrees becomes pitch, represents with P.The selective reflecting of cholesteryl liquid crystal is followed bragg's formula: λ=λ
0=n * P, reflection bandwidth: Δ λ=P * Δ n, here, n=(n
0+ n
e)/2, Δ n=n
e-n
0, wherein, n
eand n
0respectively extraordinary ray and the ordinary refraction index of liquid crystal.In reflection wavestrip, the part of the circularly polarized light identical with cholesteric liquid crystal screw axis rotation direction reflection in incident light, remaining part transmission.In visible region, because the greatest birefringence Δ n of cholesteric liquid crystal is approximately 0.3, so reflection bandwidth on be limited to 100nm.Wide for significantly increasing reflection wave, main method is in system, to form pitch gradient or pitch uneven distribution.The people (CN97191106.1) such as nineteen ninety-five Holland scientist D.J.Broer use photopolymerisable composite system, and (monomer that comprises photopolymerization chirality is cholesterol acrylate, photopolymerization nematic phase acrylate, uv absorption pigments etc.), (radiation intensity is less than 0.05mW/cm to utilize very weak ultraviolet ray
2) irradiate, prepare macromolecule network/uv absorption pigment compound substance and realized pitch gradient distribution wide wave reflection.Principle is that the interpolation of uv absorption pigment has caused ultraviolet ray intensity gradient, and adding weak ultraviolet light chiral monomer has sufficient time diffusion, thereby forms pitch gradient, to obtain the selective reflecting polaroid to whole visible light wave range.Because the degree that monomer spreads in liquid crystal is relevant with UV radiation intensity, therefore the formed bandwidth of this method is very responsive to ultraviolet irradiation intensity, therefore in manufacture process, to use monochromatic light sensor to detect polaroid, once reach required bandwidth, will improve at once ultraviolet irradiation intensity.Its equipment is more complicated, more difficult control.System has also been used uv absorption pigment in addition, has increased manufacturing cost.
Summary of the invention
The object of the invention is to provide a kind of manufacture method that can realize the liquid crystal circular polarizing disk of wide wave reflection, by better simply technique, manufacture a kind of liquid crystal circular polarizing disk that can realize wide wave reflection, and the reflection wave of this polaroid is wide can be regulated and controled by the electric field applying according to actual needs, and do not need ultraviolet polymerization.
A preparation method for the electric field controllable liquid crystal circular polarizing disk of mixed nanometer, its concrete manufacturing process is:
1, mixed liquid crystal: mixed by a kind of cholesteric liquid crystal and a kind of monodimension nanometer material, cholesteric liquid crystal is to be that negative negativity nematic liquid crystal and chipal compounds mixes by specific inductive capacity.The content 1.0-35.0wt% of chipal compounds, the content 60.0-98.8wt% of negative liquid crystal, the content 0.2-5.0wt% of nano material.
2, the above-mentioned material mixing is injected to 10um-100um liquid crystal cell or the film that process through planar orientation on surface, liquid crystal is in cholesteric phase planar texture state; At this moment on the substrate of liquid crystal cell or film, add 0V-190V, 10Hz-100KHz AC field, regulates different voltage, frequency, waveform can obtain the wide different liquid crystal circular polarizing disk of selective reflecting ripple.
Described planar orientation is processed and is adopted rubbing manipulation, Vacuum Coating method or chemical method;
Described nematic liquid crystal, its specific inductive capacity, for negative, is planar orientation at high-frequency alternating current after the match;
Described chipal compounds is Binaphthol analog derivative, cholesterol analog derivative, chirality Zhong Xin alcohol derivatives, styrene glycol analog derivative, with 2,2 ' substituted biphenyl is the compound, dimethyl butyrate alcohol derivatives at photolytic activity center or containing the compound of diformazan butyl;
Described monodimension nanometer material is that diameter is 30nm-500nm, the inorganic nano material that length is 0.5um-10.0um or conducting polymer nano material, and nano material is nanotube, nanometer rods, nano wire or nanobelt; Inorganic nano material is bismuth sulfide, copper sulfide, cadmium sulfide, zinc sulphide or zinc paste; Conducting polymer nano material is polyaniline, polypyrrole or polythiophene;
Of the present invention except above-mentioned several compositions: negativity nematic liquid crystal, chipal compounds, outside monodimension nanometer material, also can be according to selected composition, technique and actual needs, determine whether carry out planar orientation processing, and whether add other components such as light, thermal polymerization monomer, initiating agent, catalyzer.
Advantage or good effect
Can realize the reflective liquid crystal circular polarizing disk of wide wave reflection, and the reflection wave of this polaroid is wide can be according to actual needs, the electric field applying by adjustment is controlled, and can realize reversible regulation and control.Therefore also can be applied on some function films and device, as intelligent glass, electronic paper, liquid crystal display light increment film etc.In addition, this method composition and technique are simple, thereby simplify process equipment, effectively reduce production cost.
Accompanying drawing explanation
Fig. 1 is the transmitted light spectrogram of example 1 of the present invention under varying strength electric field.
Fig. 2 is the transmitted light spectrogram of example 2 of the present invention under varying strength electric field.
Fig. 3 is the transmitted light spectrogram of the invention process sample 3 under different frequency electric field.
Fig. 4 is during example 1 of the present invention and sample 2 power up before powering up and removes the transmittance graph after electricity.
Embodiment
Below with following example explanation the present invention.The present invention is not only defined in these several embodiment.
The preparation of liquid crystal cell: with the polyvinyl alcohol water solution of 2.0wt%, the method by spin coating is coated on the conducting surface of ito glass, 80 ℃ of bakings 30 minutes, then use flannelette along a direction friction orientation.Two glass sheet conducting surfaces that have been orientated are relative, and place along frictional direction antiparallel, with the separation pad that thickness is 20.0 ± 1.0um, control the thickness of liquid crystal cell, use glue pasting together of boundaries, make parallel-oriented liquid crystal cell.
(1) implement the material mixture ratio SLC10V513-200/ chipal compounds D1/ bismuth sulfide nano pipe=93.0/5.0/2.0 (wt%) of sample 1
(2) implement the material mixture ratio of sample 2
SLC10V513-200/S811/ polyaniline nanotube=83.0/15.0/2.0 (wt%)
(3) implement the material mixture ratio of sample 3
SLC10V513-200/R1011/ bismuth sulfide nano-rod=91.0/8.0/1.0 (wt%)
Sample 3 is selected negative liquid crystal SLC10V513-200, chipal compounds R1011, diameter is that 50nm-150nm length is the bismuth sulfide nano-rod of 1um-3um, by said ratio, sample mix is even, in the liquid crystal cell that utilizes capillary action to pour into prepare, apply dextrorotation AC field, voltage 150V, conversion frequency is from 100Hz to 1000Hz, and under test different frequency, sample sees through spectrum.Figure 3 shows that sample 3 is not powered up and apply respectively the transmittance graph under 200Hz, 400Hz, 600Hz, 800Hz, 1000Hz electric field, the visible reduction reflection wave along with electric field frequency is wide to broaden gradually.
The instrument that test is used is ultraviolet-visible-near infrared spectrometer (Jasco V-570).In test process, except sample being applied to its transmissivity of different electrical field tests, the transmissivity after sample power-off is also tested.Fig. 4 applies 1.0KHz square-wave electric field to sample 1 and sample 2, before powering up (0V) respectively, in powering up (190V) and remove electricity after the transmittance graph of (E OFF).Can find out, sample substantially can recover and original wave band and the wide consistent transmissivity of ripple after removing electric field, repeatedly adds and removes electric field, can realize reversible regulation and control.
Table 1
(1) negative liquid crystal (the brilliant company limited of immortal magnificent clear liquid)
Claims (1)
1. a preparation method for the electric field controllable liquid crystal circular polarizing disk of mixed nanometer, is characterized in that: concrete manufacturing process is:
A. mixed liquid crystal: mixed by a kind of cholesteric liquid crystal and a kind of monodimension nanometer material, cholesteric liquid crystal is to be that negative negativity nematic liquid crystal and chipal compounds mixes by specific inductive capacity; The content 1.0-35.0wt% of chipal compounds, the content 60.0-98.8wt% of negativity nematic liquid crystal, the content 0.2-5.0wt% of nano material;
B. the above-mentioned material mixing is injected to 10 um-100 um liquid crystal cell or the films that process through planar orientation on surface, liquid crystal is in cholesteric phase planar texture state; At this moment on the substrate of liquid crystal cell or film, add 0 V-190 V, 10 Hz-100 KHz AC field, regulate different voltage, frequency, waveform can obtain the wide different liquid crystal circular polarizing disk of selective reflecting ripple; Wherein, described planar orientation is processed and is adopted rubbing manipulation, Vacuum Coating method or chemical method; Described nematic liquid crystal, its specific inductive capacity, for negative, is planar orientation at high-frequency alternating current after the match; Described chipal compounds is Binaphthol analog derivative, cholesterol analog derivative, chirality Zhong Xin alcohol derivatives, styrene glycol analog derivative, with 2,2 ' substituted biphenyl is the compound, dimethyl butyrate alcohol derivatives at photolytic activity center or containing the compound of diformazan butyl; Described monodimension nanometer material is that diameter is 30 nm-500 nm, and length is inorganic nano material or the conducting polymer nano material of 0.5 um-10.0 um, and nano material is nanotube, nanometer rods, nano wire or nanobelt; Inorganic nano material is bismuth sulfide, copper sulfide, cadmium sulfide, zinc sulphide or zinc paste; Conducting polymer nano material is polyaniline, polypyrrole or polythiophene.
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| JP2017097217A (en) * | 2015-11-26 | 2017-06-01 | 大日本印刷株式会社 | Optical film and image display device |
| JP7055146B2 (en) * | 2017-11-08 | 2022-04-15 | 富士フイルム株式会社 | Optical laminated film and organic electroluminescence display device |
| CN108508668B (en) * | 2018-03-26 | 2020-09-25 | 北京科技大学 | Titanium dioxide nanorod array film/cholesteric liquid crystal composite wide wave reflecting film |
| CN109100889A (en) * | 2018-10-17 | 2018-12-28 | 东南大学 | The high degree of polarization LCD nanometer rods backlight of integrated form |
| CN111308762B (en) * | 2020-04-01 | 2021-05-07 | 深圳市华星光电半导体显示技术有限公司 | A display panel and electronic device |
| CN112592724B (en) * | 2020-11-22 | 2022-03-18 | 北京科技大学 | A method for preparing broadband reflective film material by nano-zinc oxide film diffusion method |
| CN112433404B (en) * | 2020-11-22 | 2021-08-27 | 北京科技大学 | Method for preparing wide wave reflection cholesteric liquid crystal film by photo-thermal response technology |
| CN116360143A (en) * | 2023-06-01 | 2023-06-30 | 合肥精卓光电有限责任公司 | Composite polymorphic light modulation device and preparation method thereof |
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| CN1776483A (en) * | 2005-11-25 | 2006-05-24 | 北京科技大学 | A method of manufacturing a liquid crystal polarizer capable of broad-wave reflection |
| CN101373233A (en) * | 2008-10-21 | 2009-02-25 | 北京科技大学 | A preparation method of circular polarizer with controllable electric field of selective reflection width |
| CN101477221A (en) * | 2009-01-12 | 2009-07-08 | 北京科技大学 | Production method for thin-film materials with electric-controlled wide wave reflection characteristics |
| CN101710192A (en) * | 2009-12-23 | 2010-05-19 | 北京科技大学 | Preparation method of liquid crystal polarizing film with characteristic of ultra-wide wave reflection |
| CN102649907A (en) * | 2011-05-06 | 2012-08-29 | 京东方科技集团股份有限公司 | Magnetic-control liquid crystal material, preparation method of liquid crystal display device and display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1776483A (en) * | 2005-11-25 | 2006-05-24 | 北京科技大学 | A method of manufacturing a liquid crystal polarizer capable of broad-wave reflection |
| CN101373233A (en) * | 2008-10-21 | 2009-02-25 | 北京科技大学 | A preparation method of circular polarizer with controllable electric field of selective reflection width |
| CN101477221A (en) * | 2009-01-12 | 2009-07-08 | 北京科技大学 | Production method for thin-film materials with electric-controlled wide wave reflection characteristics |
| CN101710192A (en) * | 2009-12-23 | 2010-05-19 | 北京科技大学 | Preparation method of liquid crystal polarizing film with characteristic of ultra-wide wave reflection |
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