Summary of the invention
The object of the present invention is to provide a kind of flexible electronic control dimming medium and preparation method thereof, this flexible electronic control dimming medium of making through the method for making of this flexible electronic control dimming medium has advantages such as frivolous, flexible, flexible demonstration.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of flexible electronic control dimming medium; It is characterized in that: it comprises first base layer, second base layer; Between this first base layer and this second base layer, be provided with an accommodating layer, be concaved with a plurality of accommodating chamber on this accommodating layer, fill out in each this accommodating chamber and be provided with the light modulation thing; This light modulation thing is formed by smectic phase liquid crystal and additives mixed; This smectic phase liquid crystal is a category-A smectic phase liquid crystal organic compound, and this additive is provided with first conductive electrode layer at this first base layer towards a side of this accommodating layer for the compound of band conductive characteristic; Be provided with second conductive electrode layer at this second base layer towards a side of this accommodating layer, this first conductive electrode layer, second conductive electrode layer are used for being connected with a drives control device.
A kind of method for making of flexible electronic control dimming medium is characterized in that it comprises the steps:
Clean: first base layer and second base layer are cleaned up;
Electrode layer is established in plating: first conductive electrode layer is established in plating on this first base layer, and second conductive electrode layer is established in plating on this second base layer;
Coated polymer film: the thin polymer film that on this first conductive electrode layer, applies UV-curable;
Place mask plate: have the mask plate of setting pattern with one and place this thin polymer film one side or this first base layer, one side;
Cure polymer film: under design temperature; In one section setting-up time; Make this mask plate of UV-irradiation of setting light intensity; The corresponding part of open-work on this thin polymer film and this mask plate is cured, and the remainder of this thin polymer film maintains the original state, and solidifies the back that finishes and removes mask plate;
Clean the uncured polymer film portion: the polymer thin membrane portions of using the cleaning fluid flush away to maintain the original state formed accommodating chamber by the polymer thin membrane portions of flush away, thereby the accommodating layer making finishes;
Fill the light modulation thing: under preset temperature, with filling the light modulation thing that completely mixes in each accommodating chamber on this accommodating layer;
Fit: on this second conductive electrode layer, apply one deck adhesive glue, this second conductive electrode layer and this accommodating layer of having filled the light modulation thing are fitted tightly together, to form flexible electronic control dimming medium through this adhesive glue.
Advantage of the present invention is: the flexible electronic control dimming medium of the present invention according to the method for making of flexible electronic control dimming medium of the present invention is produced is flexible; Can carry out flexibility shows; Have the advantage that compact conformation, in light weight, thin thickness, demonstration contrast are high, can change display view angle, multistable, safety and environmental protection, power saving, long-term memory, can be widely used in fields such as building decoration and fitment, private control area, automotive electronics and broadcasting bulletin system.
Embodiment
Describe the present invention below in conjunction with accompanying drawing.
As shown in Figure 1; Flexible electronic control dimming medium of the present invention comprises first base layer 101, second base layer 102; Between this first base layer 101 and this second base layer 102, be provided with an accommodating layer 105; Be concaved with a plurality of accommodating chamber 1051 on this accommodating layer 105; Fill out in each this accommodating chamber 1051 and be provided with light modulation thing 106; Be provided with (plating is established) first conductive electrode layer 103 at this first base layer 101 towards a side of this accommodating layer 105, be provided with (plating is established) second conductive electrode layer 104 at this second base layer 102 towards a side of this accommodating layer 105, this first conductive electrode layer 103, second conductive electrode layer 104 is used for is connected with a drives control device (not shown).Medium of the present invention is a unit with accommodating chamber 1051, and the light modulation thing 106 in the accommodating chamber 1051 has formed a capacitance structure with these light modulation thing 106 corresponding first conductive electrode layers 103 and second conductive electrode layer 104.Aspect graph after Fig. 1 shows flexible electronic control dimming medium and is bent.
In reality was implemented, first base layer 101 and second base layer 102 can be plastic plate, preferably, can select for use flexible and have a flexible parent metal of better temperature tolerance, transmittance for PET material or other.The thickness of first base layer 101 and second base layer 102 is more than or equal to 0.01mm and smaller or equal to 10mm.Preferably, the thickness of this first base layer 101 and second base layer 102 can be made as 0.1mm.
In the reality, light modulation thing 106 forms (be referring to number of patent application 200710175959.9 Chinese invention patent application " a kind of electric-controlled light-regulating medium ") by smectic phase liquid crystal and additives mixed.This smectic phase liquid crystal is a category-A smectic phase liquid crystal organic compound, for example with silica-based compound, four cyano four octyl group biphenyl, tetraacethyl ester in last of the ten Heavenly stems four cyano biphenyl etc.Usually, in the time of between room temperature ± 50 ℃, the branch sub-cluster of smectic phase liquid crystal is the layered arrangement structure, demonstrates the starchiness of thickness.This additive is the compound of band conductive characteristic, and for example cetyltriethylammonium bromide etc. contains the compound of conductive ion.Consisting of of this light modulation thing 106: this smectic phase liquid crystal accounts for and mixes 90%~99.999% of general assembly (TW), and this additive accounts for and mixes 0.001%~10% of general assembly (TW).
In the reality, accommodating layer 105 is processed by the polymer monomer of UV-curable, and perhaps accommodating layer 105 is mixed by the polymer monomer of light trigger and UV-curable, and this light trigger accounts for and mixes 1%~10% of general assembly (TW).This polymer monomer can be any in epoxy resin, polyacrylate or the polymethacrylate.This polymer monomer can be cured under the irradiation of ultraviolet light.During actual curing; Mask plate through exposure usefulness comes this polymer monomer is cured; Thereby the pattern that is provided with of this mask plate determined the shape, structure, quantity of the accommodating layer 105 final accommodating chamber 1051 that form etc., and the precision of this accommodating layer 105 is controlled between several microns to tens millimeters.The thickness of this accommodating layer 105 is more than or equal to 0.01 μ m and smaller or equal to 10mm, and general thickness with accommodating layer 105 is decided to be 0.005-0.03mm and gets final product.
This first conductive electrode layer 103, second conductive electrode layer 104 are transparent, like ITO (tin indium oxide) etc., and can use auxiliary metal electrode as required, like aluminium, copper, silver etc.In the reality, this first conductive electrode layer 103 and second conductive electrode layer 104 can be the transparency electrode of whole piece.Perhaps; First conductive electrode layer 103 is made up of M strip line electrode that is arranged in parallel; Second conductive electrode layer 104 is made up of N strip row electrode that is arranged in parallel, and N row electrode of the M of first conductive electrode layer 103 column electrode and second conductive electrode layer 104 is perpendicular, and first conductive electrode layer 103 and second conductive electrode layer 104 form the pixel array of a M * N; This pixel array has M * N pixel; Correspondingly, accommodating layer 105 should be provided with M * N accommodating chamber 1051, this M * N pixel with fill out the corresponding one by one setting of M * N accommodating chamber 1051 that is provided with light modulation thing 106.
Flexible electronic control dimming medium of the present invention is produced through following method for making.As shown in Figure 2, this method for making comprises the steps:
Clean: first base layer 101 and second base layer 102 are cleaned up.
Electrode layer is established in plating: first conductive electrode layer 103 is established in plating on this first base layer 101, and second conductive electrode layer 104 (like Fig. 3 A) is established in plating on this second base layer 102.In actual the enforcement, if flexible electronic control dimming medium is applied in the production display screen, then after first, second conductive electrode layer 103,104 is established in plating; Also need be on this first base layer 101, first conductive electrode layer 103 that plating is established carries out photoetching, makes M strip line electrode that is arranged in parallel by lithography; And on this second base layer 102; Second conductive electrode layer 104 that plating is established carries out photoetching, makes N strip row electrode that is arranged in parallel by lithography, for the flexible electronic control dimming medium of having made; This M column electrode and this N row electrode should be perpendicular, and this M column electrode and this N row electrode have formed the pixel array of a M * N.
Coated polymer film: the thin polymer film 108 (getting final product UV cured polymer monomer) (like Fig. 3 B) that on this first conductive electrode layer 103, applies UV-curable.This coating step can adopt methods such as spin coating, spraying or silk-screen.
Place mask plate: have the mask plate 107 of setting pattern with one and place these thin polymer film 108 1 sides or this first base layer, 101 1 sides.Place in the mask plate step at this, if mask plate 107 is placed thin polymer film 108 1 sides, like Fig. 3 C-1; Then mask plate 107 can not contact with thin polymer film 108; 108 of mask plate 107 and thin polymer films are separated, and general, the distance that mask plate 107 and thin polymer film are 108 is greater than 5 μ m; Ultraviolet light can directly be radiated on the thin polymer film 108 via the open-work on the mask plate 107; Light utilization efficiency is higher, but because 108 of mask plate 107 and thin polymer films certain distance apart, thus mask plate 107 to put precision relatively poor.Certainly, can before placing the mask plate step, add a precuring thin polymer film step, at a certain temperature promptly; Within a certain period of time, make this thin polymer film 108 of UV-irradiation of certain light intensity, thus precuring thin polymer film 108; Reduce the flowability of thin polymer film 108, like this, in ensuing placement mask plate step; Mask plate 107 just can be close on the thin polymer film 108, has not only guaranteed efficiently light utilization efficiency but also has improved and put precision.If mask plate 107 is placed first base layer, 101 1 sides; Like Fig. 3 C-2; Then mask plate 107 can be close to first base layer 101, and it is higher that mask plate 107 is put precision like this, but because ultraviolet light need just can be radiated on the thin polymer film 108 via the open-work on the mask plate 107, first base layer 101 successively; Thereby light utilization efficiency is lower.In actual the enforcement, the pattern of this mask plate 107 (being the shape, position, quantity etc. of open-work) should be suitable with pattern to be shown, the corresponding non-display area of open-work part on the mask plate 107, the corresponding viewing areas of other parts on the mask plate 107.For example, make row-column electrode by lithography as if establishing in the electrode layer step in plating, then the open-work on the mask plate 107 partly should correspondingly be answered non-pixel zone, and other parts on the mask plate 107 are corresponding regional corresponding with pixel.
Cure polymer film: under design temperature; In one section setting-up time; Make this mask plate 107 of UV-irradiation of setting light intensity; The corresponding part of open-work on this thin polymer film 108 and this mask plate 107 (for example point out among Fig. 3 D 1081) is cured because of receiving the irradiation of wearing the ultraviolet light of ejaculation via open-work, the remainder of this thin polymer film 108 (for example point out among Fig. 3 D 1082) because of not with mask plate 107 on open-work relative, ultraviolet light can't shine on it; Thereby maintain the original state (like Fig. 3 D), solidify the back that finishes and remove mask plate 107.In actual the enforcement, in this cure polymer film step, the light application time of temperature, ultraviolet light, the irradiates light of ultraviolet light depend on the material and the thickness of thin polymer film 108 by force.Can know that in same light application time, same thin polymer film 108 is cured, temperature is high more in actual the enforcement, the irradiation light intensity of ultraviolet light is strong more, and curing rate is fast more; Under same temperature, same irradiation light intensity, thin polymer film 108 is thick more, and light application time required during curing is long more.Generally, Controllable Temperature is built in 0~100 ℃, and the irradiation light intensity of ultraviolet light can be controlled in 1W/cm
2~10000W/cm
2, the light application time of ultraviolet light can be between 1s~10h.
Clean the uncured polymer film portion: use the maintain the original state polymer thin membrane portions (for example point out among Fig. 3 D 1082) of (promptly uncured) of cleaning fluid flush away; Formed accommodating chamber 1051 (like Fig. 3 E) by the polymer thin membrane portions of flush away, thereby accommodating layer 105 making finish.This cleaning fluid can use isopropyl alcohol, acetone or high purity water etc.The key factor that forms and influence accommodating layer 105 has: temperature, ultraviolet light light application time and light intensity etc. when the proportioning proportion of the kind of polymer monomer, polymer monomer, curing.
Fill the light modulation thing: under preset temperature (being controlled between-50 degree to 150 degree), the light modulation thing 106 (like Fig. 3 F) that fillings in each accommodating chamber 1051 on this accommodating layer 105 are completely mixed.This filling light modulation thing step can adopt spraying, dip-coating, ODF or selectivity to apply methods such as (serigraphys).Wherein, spraying is to utilize flush coater that light modulation thing 106 is sprayed onto on accommodating layer 105 surfaces with vaporific form; Dip-coating is that the taking-up back dries, the uniform rete of the serious and difficult formation of this dip-coating method waste material in first base layer, the 101 immersion light modulation thing solution that formed accommodating layer 105 on it; ODF adopts drip, and light modulation thing 106 is accurately instiled in accommodating chamber 1051; Serigraphy is that light modulation thing 106 is evenly distributed on the equal liquid roller through doctor roll, thereby is imprinted on the APR version via equal liquid roller coat, and then is coated with and is imprinted on the accommodating layer 105.
Fit: on this second conductive electrode layer 104, apply one deck adhesive glue (not shown); Through this adhesive glue this second conductive electrode layer 104 and this accommodating layer 105 of having filled light modulation thing 106 are fitted tightly together, to form flexible electronic control dimming medium (like Fig. 3 G).In reality was implemented, first base layer 101 should be aimed at the position of second base layer 102, and adhesive glue can adopt UV glue (claiming no shadow glue, light-sensitive emulsion, ultraviolet cured adhesive again), and the thickness of UV glue should be controlled at smaller or equal to 1 μ m.This applying step can adopt the volume to volume technology to accomplish.In addition, this applying step also can adopt additive method to accomplish, for example; In accommodating chamber 1051, fill up on the accommodating layer 105 of light modulation thing 106, some eva films or PVB film are coated in the place except that accommodating chamber 1051, and second conductive electrode layer 104 is fitted on this eva film or the PVB film; Under vacuum; Simultaneously heating and pressurizing lets eva film or PVB film melts, the eva film of fusing or PVB film flow to spread all over the place beyond the accommodating chamber 1051, cooling cooling under vacuum then; Eva film or PVB film are solidified again, and the operation of at this moment fitting has just been accomplished.
When using medium of the present invention; Earlier this medium is bent to required form; Change the arrangement form of the smectic phase liquid crystal molecule in the light modulation thing 106 through being controlled at the driving pulse (being voltage signal) that applies on first, second conductive electrode layer 103,104 then; Thereby medium is switched between the different light rays state, make medium of the present invention demonstrate required pattern.
The transparency electrode that is whole piece with first, second conductive electrode layer 103,104 below is an example, and the light modulation principle (is that 200810102000.7 Chinese invention patent application " electric-controlled light-regulating medium " is understood but referenced patent application number is 200710175959.9 Chinese invention patent application " a kind of electric-controlled light-regulating medium " and number of patent application) of flexible electronic control dimming medium of the present invention is described.
Through drives control device output control voltage; On first, second conductive electrode layer 103,104, apply the driving pulse about 100v, 50Hz; When driving pulse action time the time less than 1 second; Smectic phase liquid crystal molecule in the light modulation thing 106 (being the potpourri in the application for a patent for invention of institute's reference) just twists, and forms out of order arrangement form.Because each of smectic phase liquid crystal molecule is to diversity (promptly because incident ray is different through the long optical axis of each liquid crystal, and the anaclasis angle of each liquid crystal is different, thereby the refractive index of each liquid crystal is different); Make the ray refraction of each smectic phase liquid crystal molecule of incident exist very big difference; Promptly in the light modulation thing 106 of this meagre thickness, optical index is producing violent variation, thereby strong scattering has taken place in accommodating chamber 1051 light; See from macroscopic view; The medium of the present invention of this moment is a kind of astigmatic effect, presents vaporific shading state, as acute-matte.
Through drives control device output control voltage, on first, second conductive electrode layer 103,104, apply the driving pulse about 100v, 1kHz, when driving pulse action time the time less than 1 second; Smectic phase liquid crystal molecule in the light modulation thing 106 just becomes regularly arranged form; At this moment, the long optical axis of smectic phase liquid crystal molecule is perpendicular to the plane of first, second conductive electrode layer 103,104, and the ray refraction of each smectic phase liquid crystal molecule of incident does not produce acute variation; Light can freely see through light modulation thing 106; Therefore, see that this moment, medium of the present invention demonstrated the bright state of full impregnated from macroscopic view.
After producing luminous effects such as scattering, full impregnated be bright for first, second conductive electrode layer 103,104 load driver pulses, medium of the present invention, just can remove voltage.The maintenance of this luminous effect does not need voltage to keep, promptly remove voltage after, the luminous effect that medium of the present invention produces in the time of still can keeping on-load voltage, and the voltage signal of effect is just in order to change the arrangement form of smectic phase liquid crystal molecule.In the present invention, this state that does not need electricity to drive and keep luminous effect is called " multistable " or " quasistatic ".And this " multistable " is because the additive in the light modulation thing 106 has adopted the compound of band conductive characteristic; When electric signal is applied to 103,104 last times of first, second conductive electrode layer; Ion in the compound of band conductive characteristic changes the generation to-and-fro movement according to electric potential difference; This motion can change the arrangement form of smectic phase liquid crystal molecule, and the smectic phase Liquid Crystal Molecules Alignment form after changing does not need the persistent movement of ion to keep, and is stable.
Certainly; The pulse that is applied to the driving pulse on first, second conductive electrode layer 103,104 through reasonable control is to number, frequency, voltage magnitude or action time; Can make the arrangement form of smectic phase liquid crystal molecule become the part distortion, with generation astigmatic effect in various degree, thereby on macroscopic view; Make medium of the present invention between bright two states of vaporific shading and full impregnated, produce multiple progressive state, like translucent etc. with different gray.
In addition, also can be mixed with dichroic dye in the light modulation thing 106, like flaxen azo group dichroic dye.Through mixing dichroic dye, can make the switching between the bright and coloured shading of media implementation full impregnated of the present invention.
Advantage of the present invention is following:
Flexible electronic control dimming medium of the present invention according to the method for making of flexible electronic control dimming medium of the present invention is produced is flexible; Can carry out flexibility shows; Have the advantage that compact conformation, in light weight, thin thickness, demonstration contrast are high, can change display view angle, multistable, safety and environmental protection, power saving, long-term memory, can be widely used in fields such as building decoration and fitment, private control area, automotive electronics and broadcasting bulletin system.
1, flexible electronic control dimming medium of the present invention is flexible, and the display image effect is fine under case of bending.Flexible electronic control dimming medium of the present invention can be used for making flexible electronic paper.If be mixed with dichroic dye in the medium of the present invention, then medium can demonstrate different colours.
2, in existing electric-controlled light-regulating medium (be referring to number of patent application 200810102000.7 Chinese invention patent application " electric-controlled light-regulating medium "); In order to support the thickness of two plastic film layers and control mixolimnion; The batching sphere or the spacer rod that need in the mixolimnion of two plastic sheeting interlayers, be mixed with certain density and have enough hardness; Can find that the thickness of mixolimnion is very sensitive to the homogeneity of batching sphere or spacer rod in actual the enforcement, and batching sphere or spacer rod cause damage to plastic film layers easily; The operation of therefore, sneaking into batching sphere or spacer rod needs accurate operation.But in flexible electronic control dimming medium of the present invention, accommodating layer directly supports base layer up and down, need not sneak into batching sphere or spacer rod in the light modulation thing, and therefore, medium of the present invention has been avoided above-mentioned defective well.In addition, accommodating layer has stabilization, and it can increase the crushing resistance of flexible electronic control dimming medium of the present invention.
3, method for making of the present invention can realize industrialization.If in the applying step of the method for making of flexible electronic control dimming medium of the present invention, adopt the volume to volume technology to accomplish, then the inventive method can realize industrialization better, and the throughput rate of flexible electronic control dimming medium is significantly increased.But produce to the flexible electronic control dimming medium rolling, then according to the corresponding size of demand intercepting (not restriction of size in theory).In industrialization was produced, the bad point in the rolling medium can effectively be avoided, and has improved the production qualification rate.
4, owing to be applied to two electric signal on the conductive electrode layer through control; The smectic phase liquid crystal molecule can demonstrate different arrangement form; Thereby medium of the present invention can switch between vaporific shading and the bright state of full impregnated, even between the multiple progressive state of different gray, switches.Switching time between the bright state of vaporific shading and full impregnated is very short, is generally several to dozens of milliseconds, if between the multiple progressive state of different gray, switch, then switch speed is faster.
5, because the conductive characteristic of additive, make remove electric signal after, the luminous effect that medium of the present invention produces in the time of still keeping on-load voltage has well " multistable " characteristic.And because this " multistable " characteristic, the required working current of medium of the present invention is little, only when changing the moment of smectic phase Liquid Crystal Molecules Alignment form, just need power up, and energy consumption is low.And because should " multistable " characteristic, medium of the present invention almost have electromagnetic radiation, and smectic phase liquid crystal material itself just do not have any toxic action, so medium health environment-friendly of the present invention.
The above is preferred embodiment of the present invention and the know-why used thereof; For a person skilled in the art; Under the situation that does not deviate from the spirit and scope of the present invention; Any based on conspicuous changes such as the equivalent transformation on the technical scheme of the present invention basis, simple replacements, all belong within the protection domain of the present invention.