CN101794043A - Liquid crystal membrane capable of being repeatedly processed and manufacturing method thereof - Google Patents
Liquid crystal membrane capable of being repeatedly processed and manufacturing method thereof Download PDFInfo
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- CN101794043A CN101794043A CN200910008572A CN200910008572A CN101794043A CN 101794043 A CN101794043 A CN 101794043A CN 200910008572 A CN200910008572 A CN 200910008572A CN 200910008572 A CN200910008572 A CN 200910008572A CN 101794043 A CN101794043 A CN 101794043A
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Abstract
The invention provides a liquid crystal membrane capable of being repeatedly processed, which comprises a first substrate, a first conductive layer and a liquid crystal layer, wherein the first conductive layer is arranged on the first substrate; the liquid crystal layer is arranged on the first conductive layer; and the liquid crystal layer contains microencapsulated liquid crystal particles dispersed in a thermoplastic macromolecule. The invention also provides a manufacturing method for the liquid crystal membrane.
Description
Technical field
The present invention relates to a kind of liquid crystal film, and particularly relates to a kind of electric tunable optical liquid crystal film that repeats to process.
Background technology
Electricity tunable optical glass (electrically switchable glass) claims intelligent glass (smart glass) again, belong to one of building decoration special glass, accompany liquid crystal film in the middle of it, utilize the characteristic of liquid crystal, by the size adjustment transmittance of automatically controlled change electric current, can realize that glass is from transparent to opaque conversion.Electric-controlled light-regulating glass now has been widely used in fields such as high-grade office, commerce, hospital, dwelling house, machine room, automobile and space flight, also can be used as the screen of projector.
The light modulation principle of electricity tunable optical glass is: under state of nature (not added electric field cuts off the power supply), the arrangement of its inner liquid crystal is random, makes incident light through liquid crystal layer scattering can take place, and is creamy white, and is promptly opaque.After adding electric field (energising), liquid crystal molecule becomes oriented and ordered arrangement from lack of alignment, and incident light can pass through liquid crystal layer, forms pellucidity.
The used liquid crystal film of known electric tunable optical glass is a kind of polymer-dispersed liquid crystal film (Polymerdispersed liquid crystal film; Therefore PDLC film), have light leakage phenomena when its distortion or pressurized, be not suitable for being applied to curved surface (for example glass for vehicle window), its reason may be to produce liquid crystal particle not of uniform size because liquid crystal discharged during monomer polymerization to cause.In addition, known light modulation liquid crystal film can't repeat applying/processing, and can't produce to become the continuous preparation technology of rolling (Roll-to-Roll process).
For addressing the above problem, be necessary to propose a kind of electric tunable optical liquid crystal film that repeats to process, it can become the continuous preparation technology's production of rolling, and can light leakage phenomena not arranged because of distortion or pressurized.
Summary of the invention
The object of the present invention is to provide a kind of electric tunable optical liquid crystal film that repeats to process, it can become the continuous preparation technology's production of rolling, and can light leakage phenomena not arranged because of distortion or pressurized.
The invention provides a kind of liquid crystal film that repeats to process, comprising: one first substrate; One first conductive layer is arranged on first substrate; And a liquid crystal layer is arranged on first conductive layer, and liquid crystal layer comprises the microencapsulation liquid crystal particle and is scattered in the thermal plastic high polymer.
The present invention provides a kind of manufacture method of the liquid crystal film that repeats to process in addition, comprises the following steps: mixing microcapsule liquid crystal particle and solid to form a liquid crystal coating, and wherein solid is a thermal plastic high polymer aqueous solution; Liquid crystal coating is coated a substrate that is covered with conductive layer; And, with the liquid crystal coating drying and forming-film of coating on this substrate.
The advantage of the liquid crystal film that repeats to process of the present invention is that it can not have light leakage phenomena because of distortion or pressurized, thereby make electric tunable optical liquid crystal film of the present invention can be applied to especially have on the object of curved surface, traditional electrical tunable optical liquid crystal film then can can't be done this type of application because of the distortion light leak; Another advantage of liquid crystal film of the present invention is that it has and can repeat stickiness/processability.
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, and conjunction with figs., be described in detail below:
Description of drawings
Fig. 1 shows the making flow process of the liquid crystal film of the embodiment of the invention;
Fig. 2 shows a kind of in order to the continuous preparation technology's equipment of the one-tenth rolling of making liquid crystal film of the present invention;
Fig. 3 is the diagrammatic cross-section of the liquid crystal film of one embodiment of the invention;
Fig. 4 is the diagrammatic cross-section of the liquid crystal film of another embodiment of the present invention;
Fig. 5～9 are the photoelectric property test result of the embodiment of the invention;
The penetrability of the electric tunable optical film sample that Figure 10 makes for the polyvinyl alcohol water solution that uses different ions content is to voltage relationship figure;
Wherein, primary clustering symbol description:
S100-S130～ process step 10,30,50～roller
15,25～ITO-PET film, 20～liquid crystal coating
35～electric tunable optical liquid crystal film 40～slot coated head
60～drying box, 80～heat posted is closed wheel
100,200～substrate 150,250～conductive layer
300～liquid crystal layer, 310～thermal plastic high polymer
320～microencapsulation liquid crystal particle 320a～liquid crystal molecule
320b～microcapsules outer wall 400～release film
Embodiment
The present invention uses the evenly mixed liquid crystal coating that makes of microencapsulation liquid crystal and thermoplastics type's macromolecule solid, can carry out large tracts of land generation rolling and be coated with preparation technology continuously, and the tunable optical liquid crystal film tool of made of the present invention can repeat stickiness/processability, and can or gently not press light leakage phenomena, have highly disguised because of distortion.
Below will cooperate Fig. 1 that the making flow process of the present invention's electricity tunable optical liquid crystal film is described.At first, the microencapsulation liquid crystal evenly mixes to form liquid crystal coating (step S100) with thermoplastics type's macromolecule solid.Known polymer dispersion type liquid crystal (Polymer dispersed liquid crystal; PDLC) be that liquid crystal directly is scattered in the polymer matrix, and the used microencapsulation liquid crystal (PDMLC of the present invention; Polymer dispersedmicroencapsulated liquid crystal) then be to comprise that also a microcapsules outer wall (capsule wall) coats liquid crystal material, makes liquid crystal be scattered in the polymer matrix in the mode of microencapsulation.Above-mentioned liquid crystal material for example is nematic phase (Nematic), cholesteric phase (Cholesteric), smectic phase (Smectic) or ferroelectricity (ferroelectric) liquid crystal, and the microcapsules outer wall is a macromolecular material, for example polyurethane (polyurethane), polyureas (polyurea), polyacrylic acid, epoxy resin, polyester etc.About the composition and the preparation method of microencapsulation liquid crystal can be with reference to U.S. Pat 6120701.About 1～6 μ m of the particle diameter of microencapsulation liquid crystal.It should be noted that carry out centrifugal treating by the dispersion liquid that will contain the microencapsulation liquid crystal and can filter out the close particle diameter of size, this is one of advantage of using in the microencapsulation liquid crystal.
Thermoplastics type's macromolecule solid used in the present invention is a thermal plastic high polymer aqueous solution, and its concentration is for example about 5～35%, preferable about 10～30% (percentage by weights).The thermal plastic high polymer solid includes, but is not limited to: polyvinyl alcohol (PVA) (PVA), polyurethane (PU), polyacrylic acid, polyvinylpyrrolidone (PVP), polyvinyl acetate (PVA) (PVAc) or aforesaid combination, and wherein preferable with polyvinyl alcohol (PVA) especially.In one embodiment, the weight average molecular weight of thermal plastic high polymer is about 27000～32000, average degree of polymerization about 550～650.One of feature of the present invention is to use the thermal plastic high polymer of low ion concentration as solid, and its ion concentration is preferable less than 100ppm, and is better for 1000ppm.The low ion concentration thermal plastic high polymer solid that uses can avoid causing leakage current, thereby improves the performance of electric tunable optical liquid crystal film.
In one embodiment, with microencapsulation liquid crystal and thermal plastic high polymer aqueous solution with 1: the 1-3 weight ratio is evenly mixed under room temperature, can prepare liquid crystal coating, the about 20-60% of its solid content, preferable about 30-50% (percentage by weight), the about 800-2000cps of viscosity under 25 ℃, preferable about 1000-1200cps.
Then, the liquid crystal coating that will contain microencapsulation liquid crystal and solid is coated on one and is covered with on the substrate of conductive layer, tin indium oxide-polyethylene terephthalate (ITO-PET) substrate (step S110) for example, and, form a liquid crystal layer with liquid crystal coating drying and forming-film (step S120).At last, the substrate that is covered with conductive layer with another sheet is fitted (step 130) again, can form electric tunable optical glass of the present invention.
Above-mentioned steps S110～S130 is preferably and is integrated in one one-tenth continuous preparation technology of rolling and carries out, to produce the liquid crystal film that large tracts of land becomes rolling.As shown in Figure 2, the ITO-PET film that will put in order volume with driving rolls 30 launches, the about 2-4 rice of for example available linear speed/minute the speed expansion.When ITO-PET film 15 during by roller 10, the liquid crystal coating 20 of step S110 gained is applied on the ITO-PET film via a slot coated head (slot die) 40, carry out drying and forming-film through a drying box 60 afterwards.Drying box 60 for example is the baking oven with multistage humidity province, and temperature range is preferable can be from 40 ℃ to 90 ℃.Close wheel 80 with for example about 90-110 ℃ and 25 applyings of another sheet ITO-PET film via heat posted again after the film forming, can generate electric tunable optical liquid crystal film 35 continuously, batch it at last and by take-up roller 50.It should be noted that device shown in Figure 2 only is into a kind of embodiment of the continuous preparation technology of rolling, but the present invention is not as limit.
See also Fig. 3, it shows the diagrammatic cross-section of the electric tunable optical liquid crystal film of the embodiment of the invention.As shown in FIG., electric tunable optical liquid crystal film of the present invention comprises that one first substrate 100, one first conductive layer 150 are arranged on first substrate 100 and a liquid crystal layer 300 is arranged on first conductive layer 150.Liquid crystal layer 300 comprises a plurality of microencapsulation liquid crystal particles 320 and is scattered in the thermal plastic high polymer 310, and wherein microencapsulation liquid crystal particle 320 is made of the microcapsules outer wall 320b and the liquid crystal molecule 320a of inside.Microencapsulation liquid crystal particle 320 is preferably 1: 2, better about 1: 1.5 with the weight ratio of thermal plastic high polymer 310 in the liquid crystal layer 300.On liquid crystal layer 300, also comprise one second conductive layer 250 and second substrate 200.First conductive layer 150 and second conductive layer 250 are as the orientation of electrode with control liquid crystal 320a.Under the situation of added electric field not, it is random that the liquid crystal molecule 320a of microencapsulation liquid crystal particle 320 inside arranges, and scattering takes place in liquid crystal layer 300 incident light, and is opaque.After adding electric field, liquid crystal molecule 320a becomes oriented and ordered arrangement from lack of alignment, and incident light can pass through fully, forms pellucidity.
In Fig. 3, first conductive layer 150 and second conductive layer 250 for example are tin indium oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide transparency conducting layers such as (AZO).First substrate 100 and second substrate 200 also can be other transparent polymer materials except PET, for example polycarbonate (PC), Polyethylene Naphthalate (PEN), polyimide (PI), polyethersulfone (PES) etc.In addition, if be applied in discontinuous preparation technology, also can use hard transparent base material, for example glass.The thickness of liquid crystal layer 300 is approximately from 10-20 μ m, and visual needed character is that high printing opacity (film) or height cover (thick film) and decide.By the viscosity of regulation and control liquid crystal coating, the width of slot coated head, the linear speed that base material moves, can arbitrarily control the thickness of liquid crystal layer.
One of advantage of electric tunable optical liquid crystal film of the present invention is can light leakage phenomena not arranged because of distortion or pressurized, its reason may be that employed microencapsulation liquid crystal can screen the distribution of particle size, and liquid crystal droplet can be fixed in be not subject to ambient pressure in the liquid crystal film and have and flow or metaboly.This characteristic makes electric tunable optical liquid crystal film of the present invention can be applied to have on the object of curved surface (for example glass for vehicle window or have the moulding glass of curved surface) especially, and traditional electrical tunable optical liquid crystal film then can can't be done this type of application because of the distortion light leak.
Another advantage of electric tunable optical liquid crystal film of the present invention is to have to repeat stickiness/processability.Because the used solid of the present invention is a thermal plastic high polymer, therefore second base material 200 (containing second conductive layer 250) on the liquid crystal layer 300 can repeat repeatedly to tear, fit and not influence its photoelectric property, has heavy industry, and tradition promptly can't be torn after using the electric tunable optical liquid crystal film of thermosetting solid (as epoxy resin) in a single day to fit with another base material, and is comparatively unfavorable for follow-up processing.
Fig. 4 shows the diagrammatic cross-section of the electric tunable optical liquid crystal film of another embodiment of the present invention.In this embodiment, be after liquid crystal layer 300 dryings, to use a release film 400 instead to fit in liquid crystal layer 300 surfaces, to replace second base material 200 and second conductive layer 250 among Fig. 3.The material of release film 400 for example is PET, polypropylene (PP), tygon (PE), Polyvinylchloride (PVC), silica resin (silicone) etc., and thickness can be from 10～100 μ m.Be replaced to release film by the ITO-PET film 25 with Fig. 2, the present invention can produce rolling and have the liquid crystal film of release film.This cuts into appropriate size after having the decision of size of the visual actual electrical tunable optical of product glass of release film again, can have the ITO-PET film of preliminary dimension or the electrically-conductive backing plate of other type (for example ITO-glass substrate) applying with another sheet after taking off release film, have adjustability on the processing procedure.
[synthesis example: microencapsulation liquid crystal particle]
(DH-032, worker grind institute's self-control with 40 gram liquid crystal with 2.5 gram polyurethane (Desmodur N-3200, Bayer Corp.); Δ n=0.19, Tc=89 ℃) evenly mix down in 60 ℃.10% polyvinyl alcohol water solutions that above-mentioned mixed solution added 200 grams stir, then under 50-55 ℃ with 3000rpm, carried out the particle that emulsification obtains particle diameter 1-10 μ m in 3 minutes.10% triethylene diamine (TriethyleneDiamine) that adds 25 grams afterwards reacted 10 hours down in 55 ℃ with 25 10% triethanolamines (Triethanolamine) that restrain.After reaction finishes, add 10% ammonium hydroxide of 20 grams, standing over night.At last the gained slurry is carried out centrifugally with the 5000rpm rotating speed, obtain the microencapsulation liquid crystal particle of size distribution 1-5 μ m.
[embodiment 1]
With the microencapsulation liquid crystal particle of synthesis example and 20% polyvinyl alcohol water solution according to 1: 1.5 (weight ratio) at room temperature ratio evenly mix, can make liquid crystal coating, the viscosity of coating is that 1000～1100cps (25 ℃), solid content are about 42%.The weight-average molecular weight of above-mentioned used polyvinyl alcohol (PVA) is 27000-32000, and the degree of polymerization is 550-650, and sodium ions content is lower than 60ppm.
With device shown in Figure 2, with PET-ITO film (being coated with fabric width is 1.1 meters) after the slot coated head is coated liquid crystal coating, enter five-part form baking oven (40～90 ℃ of temperature) drying, being about 4 meters/minute translational speeds with linear speed moves, it is film adhered with another sheet PET-ITO to close wheel through about 100 ℃ of heat posteds at last, generate electric tunable optical liquid crystal film continuously, THICKNESS CONTROL is 15 μ m.
[embodiment 2]
With embodiment 1, but wherein liquid crystal coating changes by the microencapsulation liquid crystal particle and at room temperature evenly mixes according to 1: 1.29: 0.21 (weight ratio) with 20% polyvinyl alcohol water solution, 20% polyurethane (PU) aqueous solution, and the viscosity of coating is that 800～900cps (25 ℃), solid content are about 42%.
[the photo analysis of electric tunable optical liquid crystal film]
The electric tunable optical liquid crystal film of embodiment 1,2 rolling cut after the electric tunable optical glass that glass gummed processing and preparing technology is produced, be of a size of wide 1.1 meters, long 3 meters.Measure its photoelectric property with perspectivity instrument (instrument of EDTM company), its result as shown in Figure 5, wherein the electric tunable optical liquid crystal film of embodiment 1 has the commercial goods Polyvision that high-transmittance (T%=65%@45V) has been better than Polytronix company
TM(T%=54%@45V).
[the photo analysis of the electric tunable optical liquid crystal film of different thickness]
Preparation technology according to embodiment 1, but control the spacing of different slit heads to base material, can be coated with out different wet-film thickness, carry out again can making the electric tunable optical liquid crystal film that build is 10 μ m and 17 μ m (this thickness does not comprise the thickness of PET-ITO base material) respectively behind the preparation technologies such as drying, applying, measure its penetrability.Result such as table 1 and shown in Figure 6: the penetrability poor (7%～66%) of thickness big (17 μ m), the power of promptly covering is good; The good transmittance (10%～70%) of thickness little (10 μ m), the power of promptly covering is poor.
Table 1
[can repeat processing/applying test]
The electric tunable optical film sample of measuring embodiment 1 do not tear and tears-and 3 times the penetrability of fitting is to voltage relationship figure, tear-fit experiment and measure its photo through laminator (binding temperature is 100 ℃) back for the sample that will tear, its result as shown in Figure 7, and is little with the photoelectric property difference of tearing-fitting sample after 3 times before not tearing.
[twisting light tight test]
Commercial goods Polyvision with the Polytronix company of long 21cm, wide 8cm
TMFold the hollow cylindrical that diameter is 6cm, measure the penetration of this film under different voltages, its result as shown in Figure 8, during as V=0, penetration is not 3% to the Polytronix commodity when twisting after measuring; Distortion back penetration promotes most 15%, differs 12%.
Similarly, the embodiment 1 electric tunable optical film sample of long 21cm, wide 8cm is folded the hollow cylindrical that diameter is 6cm, measures the penetration of this film under different voltages, its result as shown in Figure 9, when V=0, penetration is not 6% when twisting; Distortion back penetration promotes most 7%, only differs 1%, and confirming that electric tunable optical film of the present invention has when distortion not can light leak, can conform to still to possess highly concealed type on the bend glass.
[embodiment 3]
With embodiment 1, but wherein using ion concentration to be lower than 60ppm and ion concentration respectively is higher than two kind of 20% polyvinyl alcohol water solution of 3600ppm and is prepared into coating, and utilize scraper on the PET-ITO film, to be coated with, entered baking oven (80～90 ℃ of temperature) subsequently dry 7 minutes, it is film adhered to pass through about 100 ℃ of hot make-up machines and another sheet PET-ITO at last, promptly produce electric tunable optical liquid crystal film, THICKNESS CONTROL is 8 μ m and 15 μ m.
[the photo analysis of the electric tunable optical liquid crystal film that different ions content 20%PVA aqueous solution is made]
Measure embodiment 3 the low ion concentration of use (≤60ppm) and macroion content (〉=3600ppm) penetrability of the electric tunable optical film sample made of 20% polyvinyl alcohol water solution is to voltage relationship figure, its result as shown in figure 10, the penetrability that the electric tunable optical film (thickness is 8 μ m and 15 μ m) that uses low ion concentration 20% polyvinyl alcohol water solution to make is measured all is higher than the electric tunable optical film (thickness is 8 μ m and 15 μ m) that macroion content 20% polyvinyl alcohol water solution is made, when wherein using the thickness of the electric tunable optical film that macroion content 20% polyvinyl alcohol water solution makes to be higher than 15 μ m, both can burn out after the energising for several times and can't drive electric tunable optical film with voltage again.
Though the present invention with several preferred embodiments openly as above; right its is not in order to limit the present invention; any the technical staff in the technical field; without departing from the spirit and scope of the present invention; when can changing arbitrarily and retouching, so protection scope of the present invention is as the criterion when looking the accompanying Claim book person of defining.
Claims (23)
1. liquid crystal film that can repeat to process comprises:
One first substrate;
One first conductive layer is arranged on described first substrate; And
One liquid crystal layer is arranged on described first conductive layer, and described liquid crystal layer comprises the microencapsulation liquid crystal particle and is scattered in the thermal plastic high polymer.
2. the liquid crystal film that repeats to process according to claim 1, wherein said thermal plastic high polymer are polyvinyl alcohol (PVA), polyurethane, polyacrylic acid, polyvinylpyrrolidone, polyvinyl acetate (PVA) or aforesaid combination.
3. the liquid crystal film that repeats to process according to claim 1, the ion concentration of wherein said thermal plastic high polymer is less than 100ppm.
4. the liquid crystal film that repeats to process according to claim 1, the ion concentration of wherein said thermal plastic high polymer is less than 1000ppm.
5. the liquid crystal film that repeats to process according to claim 1, the weight average molecular weight 27000～32000 of wherein said thermal plastic high polymer.
6. the liquid crystal film that repeats to process according to claim 1, the average degree of polymerization 550～650 of wherein said thermal plastic high polymer.
7. the liquid crystal film that repeats to process according to claim 1, the thickness 10-20 μ m of wherein said liquid crystal layer.
8. the liquid crystal film that repeats to process according to claim 1 also comprises: one second conductive layer is arranged on the described liquid crystal layer, and one second substrate, is arranged on described second conductive layer.
9. the liquid crystal film that repeats to process according to claim 1 comprises that also a release film is arranged on the described liquid crystal layer.
10. the liquid crystal film that repeats to process according to claim 1, particle diameter 1～6 μ m of wherein said microencapsulation liquid crystal particle.
11. the liquid crystal film that repeats to process according to claim 1, wherein said first substrate is to be arranged on the curved surface.
12. the manufacture method of the liquid crystal film that can repeat to process comprises the following steps:
Mixing microcapsule liquid crystal particle and solid are to form a liquid crystal coating, and wherein said solid is a thermal plastic high polymer aqueous solution;
Described liquid crystal coating is coated a substrate that is covered with conductive layer; And
With the liquid crystal coating drying and forming-film of coating on the described substrate.
13. the manufacture method of the liquid crystal film that repeats to process according to claim 12, the concentration 5～35wt% of wherein said thermal plastic high polymer aqueous solution.
14. the manufacture method of the liquid crystal film that repeats to process according to claim 12, the concentration 10～30wt% of wherein said thermal plastic high polymer aqueous solution.
15. the manufacture method of the liquid crystal film that repeats to process according to claim 12, the solid content 20-60wt% of wherein said liquid crystal coating.
16. the manufacture method of the liquid crystal film that repeats to process according to claim 12, wherein said plastic macromolecule are polyvinyl alcohol (PVA), polyurethane, polyacrylic acid, polyvinylpyrrolidone, polyvinyl acetate (PVA) or aforesaid combination.
17. the manufacture method of the liquid crystal film that repeats to process according to claim 12, the ion concentration of wherein said thermal plastic high polymer is less than 1000ppm.
18. the manufacture method of the liquid crystal film that repeats to process according to claim 12, the ion concentration of wherein said thermal plastic high polymer is less than 100ppm.
19. the manufacture method of the liquid crystal film that repeats to process according to claim 12, wherein said liquid crystal coating is drying and forming-film under 40～90 ℃ temperature.
20. the manufacture method of the liquid crystal film that repeats to process according to claim 12 wherein also comprises behind drying and forming-film: fit with another substrate that is covered with conductive layer.
21. the manufacture method of the liquid crystal film that repeats to process according to claim 12 wherein also comprises behind drying and forming-film: fit with a release film.
22. according to the manufacture method of the described liquid crystal film that repeats to process of arbitrary claim in the claim 12～21, it is to carry out with one one-tenth continuous preparation technology of rolling.
23. the manufacture method of the liquid crystal film that repeats to process according to claim 22 also comprises: described liquid crystal film is conformed on the curved surface.
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| JP2019514047A (en) * | 2016-03-23 | 2019-05-30 | ガーディアン・グラス・エルエルシーＧｕａｒｄｉａｎ Ｇｌａｓｓ， Ｌｌｃ | Low haze switchable liquid crystal device for use in switchable windows or similar windows |
| US10921672B2 (en) | 2016-03-23 | 2021-02-16 | Guardian Glass, LLC | Low haze switchable window |
| CN111823677A (en) * | 2020-06-02 | 2020-10-27 | 中电科工程建设有限公司 | Brightness-adjustable lighting film |
| CN113183377A (en) * | 2021-05-14 | 2021-07-30 | 浙江凯信光电科技有限公司 | Liquid crystal high polymer coating transfer process based on optical lens or polarizing film |
| CN115407572A (en) * | 2022-11-01 | 2022-11-29 | 合肥精卓光电有限责任公司 | Light modulation valve and light modulation glass assembly |
| CN115407572B (en) * | 2022-11-01 | 2023-02-03 | 合肥精卓光电有限责任公司 | Light modulation valve and light modulation glass assembly |
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Application publication date: 20100804 |