CN102654666A - Smectic phase liquid crystal dimming sheet and manufacturing method thereof - Google Patents
Smectic phase liquid crystal dimming sheet and manufacturing method thereof Download PDFInfo
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- CN102654666A CN102654666A CN2011100524554A CN201110052455A CN102654666A CN 102654666 A CN102654666 A CN 102654666A CN 2011100524554 A CN2011100524554 A CN 2011100524554A CN 201110052455 A CN201110052455 A CN 201110052455A CN 102654666 A CN102654666 A CN 102654666A
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Abstract
The invention discloses a smectic phase liquid crystal dimming sheet and a manufacturing method thereof. The dimming sheet comprises two body layers; a smectic phase liquid crystal dimming film layer is arranged between the two body layers; the smectic phase liquid crystal dimming film layer comprises two conductive electrode layers; a mixing layer is arranged between the two conductive electrode layers; the inner side face of each body layer is adhered to the outer side face of the corresponding conductive electrode layer through an adhesive layer; and a matrix layer can be arranged between each conductive electrode layer and the adhesive layer. The manufacturing method comprises the following steps of: cleaning and drying the matrix layer; manufacturing the conductive electrode layers; manufacturing the mixing layer; laying the adhesive layer and the body layers to obtain an initial laminated structure of the dimming sheet; and pressurizing, heating and cooling to obtain the dimming sheet. The dimming sheet provided by the invention has the characteristics of multiple steady states, is green, has low carbon, is healthy and environment-friendly, and can be widely applied to fields, such as architectural ornament and decoration, privacy control area and automotive electronics. The manufacturing method provided by the invention is simple and easy to control, has very low cost and is suitable for industrialization.
Description
Technical field
The present invention relates to a kind of light modulation structure and preparation method thereof, specifically, relate to smectic liquid crystal light modulation sheet of a kind of polymer architecture encapsulation type and preparation method thereof.
Background technology
At present, dimming glass market is fiery, and the kind of dimming glass is more and more, is widely used in fields such as vehicle glass, building decoration, outdoor curtain wall.Dimming glass is a kind of electrochromism dimming glass, and it controls the state of the functional material in polyester film or the interlayer through the safety low-voltage, and then reaches the purpose of variable color light modulation.The shade of this electrochromism dimming glass can be controlled through changing electric current, and then regulates sun lights and go into indoor intensity.When applying voltage for this electrochromism dimming glass, electrochromic material wherein is painted, and when removing voltage, this dimming glass is got back to vaporific lucifuge state, that is to say, this dimming glass needs impressed voltage always when keeping colored state.Can see that in practical application this dimming glass has lot of advantages.For example, when this dimming glass is in opaque state, can use, the entity curtain needn't be installed again, have antiultraviolet and sound insulation function, but the transmitance local dimming of the scalable sun has prompting or Presentation Function etc. as curtain.But, from practical application, also can find, though this dimming glass has above-mentioned plurality of advantages,, this dimming glass need be in electriferous state all the time, just necessary charged work, and do not have " multistable " characteristic.
For example, this dimming glass can use traditional nematic state (nematic) liquid crystal to be made, and still, what the nematic state liquid crystal used is polaroid, and transmittance is lower than 50%, generally is about 40%, so this dimming glass can not satisfy the bright demand of full impregnated.And the nematic state liquid crystal does not have " multistable " characteristic (" multistable " is meant the state that does not need driven and keep luminous effect, is also referred to as " quasistatic "), needs lasting electricity consumption, and certain energy consumption is arranged.
Again for example, a kind of electricity that is made into through liquid crystal polymer light regulating technology (PDLC) that occurs in the market causes dimming glass.This liquid crystal polymer light regulating technology mainly be with the nematic state liquid crystal with after Molecularly Imprinted Polymer mixes, through the arrangement attitude of control nematic state liquid crystal, make innerly to produce different refraction coefficients and demonstrate the macrostate conversion between printing opacity and the astigmatism.Specifically; This technology is: select an amount of nematic state liquid crystal to mix with a certain amount of molecule list compound, mixed potpourri is recorded in the crack of layer glass (glass has certain thickness), on the corresponding surface of layer glass, be coated with transparency electrode; Ultraviolet light through certain wavelength and intensity carries out treatment with irradiation; Make molecule list compound generation chemical change, agglomerated together and become Molecularly Imprinted Polymer, these Molecularly Imprinted Polymers are transparent.Because the nematic state liquid crystal molecule evenly mixes with Molecularly Imprinted Polymer; In the process that these Molecularly Imprinted Polymers form; It (is that Molecularly Imprinted Polymer becomes from fusion with the nematic state liquid crystal molecule and separates that the nematic state liquid crystal molecule is divided into one by one little blister space equably; Molecularly Imprinted Polymer has carried countless little liquid crystal bubbles like netted, and Molecularly Imprinted Polymer becomes carrier).Under no-voltage applies situation,, be a kind of mixed and disorderly relatively state generally, so scattering phenomenon is very obvious because the arrangement of nematic state liquid crystal molecule does not have very strong directivity.Under the situation that certain electric field applies, the nematic state liquid crystal molecule has just had the arrangement of directivity, and itself and large-area Molecularly Imprinted Polymer carrier have been eliminated the difference of refractive index, demonstrate clear state.This electricity of having used the liquid crystal polymer light regulating technology causes dimming glass and compares with the dimming glass of using traditional nematic state liquid crystal making, has better transparency, is applied to fields such as automobile light-modulating skylight at present more.But this liquid crystal polymer light regulating technology only has transparent and opaque two states, and neither " multistable ", it is the same with traditional nematic state liquid crystal, and pellucidity is kept in the power supply that needs to continue.
This shows, design that a kind of can freely to change the light modulation structure that light sees through state and have " multistable " characteristic be present urgent problem.
Summary of the invention
The object of the present invention is to provide a kind of smectic liquid crystal light modulation sheet and preparation method thereof, the light modulation sheet of producing through this method for making has " multistable " characteristic, can between the bright state of full impregnated, vaporific shading state, various gray state, switch.
To achieve these goals, the present invention has adopted following technical scheme:
A kind of smectic liquid crystal light modulation sheet is characterized in that: it comprises two body layer, is provided with smectic liquid crystal light modulation rete in the middle of these two body layer; This smectic liquid crystal light modulation rete comprises two conductive electrode layers; Two these conductive electrode layers are connected with the circuit external driving control device; Be provided with mixolimnion in the middle of these two conductive electrode layers, this mixolimnion comprises and is encapsulated in the potpourri of being made up of smectic liquid crystal, conducting objects and spacer in the polymer architecture; The medial surface of each this body layer is mutually bonding through an adhesive phase with the lateral surface of corresponding this conductive electrode layer respectively.
Also can be provided with base layer between said conductive electrode layer and the said adhesive phase.
A kind of method for making of smectic liquid crystal light modulation sheet, it is characterized in that: it comprises the steps:
The first step, cleaning, dried base layer;
In second step, on each base layer medial surface, make a conductive electrode layer, then cleaning, drying;
In the 3rd step, between two conductive electrode layers, make mixolimnion, thereby accomplish the making of smectic liquid crystal light modulation rete;
The 4th step; Cleaning, dry body layer; Lay an adhesive phase therein on the medial surface of a body layer; The smectic liquid crystal light modulation rete that the 4th step was made is placed on this adhesive phase, and a lateral surface of this smectic liquid crystal light modulation rete is contacted with this adhesive phase, and the conductive electrode layer in this smectic liquid crystal light modulation rete is connected with the circuit external driving control device; On another lateral surface of this smectic liquid crystal light modulation rete, lay an adhesive phase, a body layer then successively, thereby obtain light modulation sheet initiation layer stack structure;
The 5th step; Under the pressure of the temperature that is provided with, setting; This light modulation sheet initiation layer stack structure is pressurizeed, heats, make adhesive melts in the adhesive phase, slough bubble, this light modulation sheet initiation layer stack structure is bonded into integral body; Cool off under the vacuum condition in being in predetermined temperature range then, thereby obtain this smectic liquid crystal light modulation sheet.
Advantage of the present invention is:
Light modulation sheet of the present invention is a kind of polymer architecture encapsulation type light modulation sheet, and this light modulation sheet is different from traditional light modulating device (as: polymer dispersion, the nano particle-compound light modulating device of memory class polymkeric substance) by continuing to switch on and control.
The potpourri two of encapsulation can be immiscible between mutually in polymer architecture in the light modulation sheet of the present invention and the polymer architecture; Be do not contain in the polymer architecture not contain polymerizable molecular in smectic liquid crystal and the smectic liquid crystal, it is alternate miscible each other and influence the problem of quality to have solved on the market liquid crystal and polymerizable molecular in the polymer dispersion light modulating device two.
Light modulation sheet of the present invention uses smectic liquid crystal to realize dimming function; Realized " multistable " effect, the dimming state (vaporific shading state, the bright state of full impregnated or certain gray state) before outage back light modulation sheet of the present invention still can keep cutting off the power supply, dimming state need not switched on and kept; And traditional light modulating device can only return to original vaporific shading state after outage; Therefore, light modulation sheet of the present invention has very high practicality, energy-saving low-carbon.
Light modulation sheet of the present invention can be between vaporific shading state, the bright state of full impregnated, various gray state switches fast, and the transmittance when being in the bright state of full impregnated can reach more than 80%, and the astigmatism property when being in vaporific shading state is very stable, can reach the shading requirement.
Because designed adhesive phase in the light modulation sheet of the present invention, adhesive phase can play a very good protection, therefore, light modulation sheet of the present invention has withstand voltage anti-broken characteristics.If body layer adopts glass, cracked even glass damages, fragment also can be bonded on the adhesive phase, has avoided glass chip to drop and personnel's injury of causing.
Light modulation sheet of the present invention does not have any murder by poisoning, and health environment-friendly can be widely used in fields such as building decoration and fitment, private control area, automotive electronics.
Method for making of the present invention is simple and easy to control, and the light modulation sheet yield rate of producing is high, is suitable for industrialization, and cost is very low.
Description of drawings
Fig. 1 is that the structure of light modulation sheet first embodiment of the present invention is formed synoptic diagram;
Fig. 2 is that the structure of light modulation sheet second embodiment of the present invention is formed synoptic diagram;
Fig. 3 is the schematic perspective view (partial cut) of light modulation sheet second embodiment of the present invention;
Fig. 4 is the arrangement form synoptic diagram of smectic liquid crystal molecule under the low-frequency voltage effect;
Fig. 5 is the arrangement form synoptic diagram of smectic liquid crystal molecule under the HF voltage effect;
Fig. 6 is the method for making realization flow figure of light modulation sheet second embodiment of the present invention.
Embodiment
As shown in Figure 1, smectic liquid crystal light modulation sheet of the present invention comprises two body layer 200,300, is provided with smectic liquid crystal light modulation rete 100 in the middle of these two body layer 200,300; This smectic liquid crystal light modulation rete 100 comprises two conductive electrode layers 120,130; Two these conductive electrode layers 120,130 are connected with circuit external driving control device 700; Be provided with mixolimnion 110 in the middle of these two conductive electrode layers 120,130; This mixolimnion 110 comprise be encapsulated in the polymer architecture (constitute by polymerizable molecular under the microcosmic, state as follows), by smectic liquid crystal (microcosmic is down the smectic liquid crystal molecule, states as follows), (microcosmic is the conducting objects molecule down to conducting objects; State as follows) and the potpourri formed of spacer, two conductive electrode layers 120,130 and mixolimnion 110 have formed a capacitance structure; The medial surface of each this body layer 200,300 respectively with the lateral surface of corresponding this conductive electrode layer through adhesive phase mutually bonding (lateral surface of medial surface and conductive electrode layer 120 that is body layer 200 is mutually bonding through adhesive phase 400, and it is mutually bonding that the medial surface of body layer 300 and the lateral surface of conductive electrode layer 130 pass through adhesive phase 500).
As shown in Figure 2, also can be provided with base layer between the lateral surface of conductive electrode layer and the adhesive phase.That is to say; The lateral surface of each conductive electrode layer also can be provided with a base layer; The lateral surface of each this base layer is mutually bonding with the medial surface of corresponding body layer through an adhesive phase, thereby forms the different light modulation sheet of light modulation chip architecture a kind of and shown in Figure 1.Specifically; Like Fig. 2; The lateral surface of conductive electrode layer 120 is provided with a base layer 140, and the lateral surface of this base layer 140 is mutually bonding with the medial surface of corresponding body layer 200 through adhesive phase 400, and the lateral surface of conductive electrode layer 130 is provided with a base layer 150; The lateral surface of this base layer 150 is mutually bonding with the medial surface of corresponding body layer 300 through adhesive phase 500, and this polymer architecture plays effects bonding and two base layers 140,150 of support.
In actual design, the quantity of this smectic liquid crystal light modulation rete 100 is at least one.When the light modulation sheet has two or more smectic liquid crystal light modulation retes 100, be splicing construction between two or more these smectic liquid crystal light modulation retes 100, and whole light modulation sheet also can be realized the multi-disc splicing.
Body layer 200,300 can be made by transparent glass or organic transparent material, and the thickness range of this body layer is greater than 0cm and smaller or equal to 5cm.Wherein, glass can be simple glass, vehicle glass, external window of building glass, tempered glass or special glass etc., and organic transparent material can be organic resin hyaline layers such as PET, PMMA, acryl resin, transparent silica gel.Two body layer 200,300 can be processed for glass or process for organic transparent material simultaneously simultaneously, certainly, can a body layer be that glass is processed also, and another is processed for organic transparent material.
Bonding agent in the adhesive phase 400,500 may be selected to be PVB (Polyvinyl butyral polyvinyl butyral) or EVA (Ethylene-Vinyl AcetateCopolymers; The ethene-vinyl acetate co-polymer) hot melt adhesive; Also may be selected to be heat-curable glue or UV and solidify glue; This adhesive phase plays sticker adhesive effect (be solid state, behind over hot melting, can play the sticker adhesive effect) before hot melt.Wherein, the EVA flexibility of hot-melt adhesive is good, cohesive force is strong, safe, and PVB glue has good sound insulation property, can antiultraviolet, and safe.The thickness range of adhesive phase 400,500 is greater than 0cm and smaller or equal to 5cm.
This base layer 140,150 is the flexible transparent material; Can select polyethylene terephthalate (polyethylene terephthalate for use; PET) or polyimide (Polyimide; PI) or polyetherimide (Polyetherimide, PEI) or tygon (polyethylene, PE) or other are flexible and have a flexible parent metal of better temperature tolerance, transmittance, pulling strengrth, hot expansion and contraction.The thickness range of base layer is 0-10mm, is controlled between the 0.1-0.3mm preferable.When the thickness of two base layers is 0, promptly be light modulation sheet illustrated in fig. 1.
Conductive electrode layer the 120, the 130th is transparent; Its material can be ITO (tin indium oxide); Also can process for the organic material, inorganic material or the compound substance that possess the electrically conducting transparent performance by carbon nano tube-doped polymer molecule material etc., perhaps add on the basis of any in above-mentioned two kinds of materials metal such as cupric, silver, gold, carbon or nonmetal in any or appoint several kinds of conductive materials that constitute to process.The electrode shape of conductive electrode layer can be arbitrary shape, and the shape of each electrode can be identical or different.Normally; Conductive electrode layer is processed M strip shaped electric poles that is arranged in parallel, and another conductive electrode layer is processed N strip shaped electric poles that is arranged in parallel, and M electrode and N electrode be quadrature mutually; Thereby two conductive electrode layers form the pixel array of a M * N, are used for display pattern.
For mixolimnion 110; Polymer architecture can be got ready on the medial surface of conductive electrode layer (one or two) through direct printing or etching or nano impression or spraying by unimolecule body material or (thermoplasticity) polymerizable molecular material; Then heat curing or ultra-violet curing for have setting network, the isostructural polymerizable molecular material of point-like forms, this unimolecule body material is any in epoxy resin, polyacrylate or the polymethacrylate monomer.This polymer architecture is formed with accommodating chamber; This polymer architecture can be that spherical, little cylindric, thread, hemispherical, parallel strip, cube, rectangular parallelepiped, the intersection of rule is traditional thread binding, the mixed structure of network structure (like the hexagon cellular wall construction), square grid minor structure, irregular polygon structure or above-mentioned multiple structure etc.; This polymer architecture can be uniformly, and is also uneven.For example, polymer architecture 114 illustrated in fig. 3 is equally distributed hexagon cellular wall construction, forms the accommodating chamber 115 of hexagon cellular shape, and this accommodating chamber 115 is used for the potpourri that splendid attire is made up of smectic liquid crystal, conducting objects and spacer.Between this polymer architecture and smectic liquid crystal, conducting objects and the spacer can be miscible each other, disperse, be in contact with one another or at interval etc.Smectic liquid crystal is the category-A smectic liquid crystal, for example with in silica-based compound, four cyano four octyl group biphenyl or tetraacethyl ester in the last of the ten Heavenly stems four cyano biphenyl any or appoint several kinds mixing.Conducting objects in the nano particle, mineral compound, organic compound, CNT, Graphene, sodium carbonate, cetyltriethylammonium bromide of band conductive characteristic any or appoint several kinds mixing; The effect of conducting objects is the electric conductivity that increases mixolimnion; Under the voltage effect; Conducting objects is changed the arrangement form of smectic liquid crystal molecule by the driving and generating motion, thereby changes the photoelectric properties of smectic liquid crystal.Spacer is batching sphere or the spacer rod (spacer rod is seen 113 among Fig. 4 and Fig. 5) that polyester material or glass material are processed.
For mixolimnion 110, the consisting of of mixolimnion: smectic liquid crystal accounts for the 10%-99% that mixes general assembly (TW), and the polymerizable molecular material accounts for the 1%-90% that mixes general assembly (TW), and conducting objects accounts for the 0%-10% that mixes general assembly (TW), and spacer accounts for the 0%-20% that mixes general assembly (TW).
For example, smectic liquid crystal accounts for and mixes 99% of general assembly (TW), and the polymerizable molecular material accounts for and mixes 0.9% of general assembly (TW), and conducting objects accounts for mixes 0.02% of general assembly (TW), and spacer accounts for and mixes 0.08% of general assembly (TW).Again for example, smectic liquid crystal accounts for and mixes 10% of general assembly (TW), and the polymerizable molecular material accounts for and mixes 89.05% of general assembly (TW), and conducting objects accounts for mixes 0.05% of general assembly (TW), and spacer accounts for and mixes 0.9% of general assembly (TW).Again for example, smectic liquid crystal accounts for and mixes 89% of general assembly (TW), and the polymerizable molecular material accounts for and mixes 1% of general assembly (TW), and conducting objects accounts for mixes 1% of general assembly (TW), and spacer accounts for and mixes 9% of general assembly (TW).Again for example, smectic liquid crystal accounts for and mixes 9% of general assembly (TW), and the polymerizable molecular material accounts for and mixes 90% of general assembly (TW), and conducting objects accounts for mixes 0.1% of general assembly (TW), and spacer accounts for and mixes 0.9% of general assembly (TW).Again for example, smectic liquid crystal accounts for and mixes 45% of general assembly (TW), and the polymerizable molecular material accounts for and mixes 30% of general assembly (TW), and conducting objects accounts for mixes 10% of general assembly (TW), and spacer accounts for and mixes 15% of general assembly (TW).Again for example, smectic liquid crystal accounts for and mixes 89% of general assembly (TW), and the polymerizable molecular material accounts for and mixes 10.9% of general assembly (TW), and conducting objects accounts for mixes 0.01% of general assembly (TW), and spacer accounts for and mixes 0.09% of general assembly (TW).Again for example, smectic liquid crystal accounts for and mixes 63% of general assembly (TW), and the polymerizable molecular material accounts for and mixes 15% of general assembly (TW), and conducting objects accounts for mixes 2% of general assembly (TW), and spacer accounts for and mixes 20% of general assembly (TW).
For the light modulation sheet that base layer is arranged, polymer architecture has been bonding and has supported two base layers 140,150 effects.For the light modulation sheet that does not have base layer, this polymer architecture then has the effect that keeps smectic liquid crystal light modulation rete 100 structural forms.In mixolimnion 110; When the smectic liquid crystal molecule is regularly arranged; Because the optical refractive index of polymerizable molecular is very close with the optical refractive index of smectic liquid crystal molecule, so polymerizable molecular can not influence the transmittance of light, the optical properties of smectic liquid crystal molecule can not be affected; Promptly can not influence dimming capability (referring to transmittancy and astigmatic ability); When the irregular alignment of smectic liquid crystal molecule, light can transmission mix layer 110 be not to form because the optical refractive index on the molecular axis both direction of smectic liquid crystal molecule itself is different, and is irrelevant with polymerizable molecular.And " multistable " characteristic of light modulation sheet of the present invention is the attribute of smectic liquid crystal molecule, and is irrelevant with polymerizable molecular.But the polymerizable molecular material is many more, and the shared overall ratio of area that is used for light modulation is just more little, and dimming effect naturally will variation.Therefore, polymerizable molecular material proportion can not be too big.
Spacer is also just played a supporting role, and is used for controlling the thickness of mixolimnion 110, and therefore, the spacer proportion also need not be very big, is controlled at 0%-20% (not comprising 0%) and gets final product.The diameter of spacer promptly is the thickness of mixolimnion, and the quantity of spacer should suitably be confirmed with the selection of adopting ball or rod according to the mixolimnion thickness that reaches in advance.When the smectic liquid crystal molecule is regularly arranged; Because the optical refractive index of spacer is very close with the optical refractive index of smectic liquid crystal molecule; So spacer can not influence the transmittance of light; The optical properties of smectic liquid crystal molecule can not be affected, and spacer can not influence astigmatism property of the present invention and " multistable " characteristic yet.
Conducting objects mainly is the electric conductivity that increases mixolimnion 110; Conducting objects is changed the arrangement form of smectic liquid crystal molecule by the driving and generating motion under the voltage effect; So the consumption of conducting objects should be an amount of, be controlled at 0%-10% (not comprising 0%) and get final product, be difficult to drive greater than 10%.
And smectic liquid crystal plays the light modulation effect, and therefore, the consumption of smectic liquid crystal should be advisable at most.
In view of above-mentioned; In order to make dimming characteristic of the present invention reach preferable effect; The composition of mixolimnion 110 can be set at: smectic liquid crystal accounts for and mixes 84.94% of general assembly (TW); The polymerizable molecular material accounts for and mixes 15% of general assembly (TW), and conducting objects accounts for mixes 0.01% of general assembly (TW), and spacer accounts for and mixes 0.05% of general assembly (TW).Perhaps, smectic liquid crystal accounts for and mixes 80% of general assembly (TW), and the polymerizable molecular material accounts for and mixes 19% of general assembly (TW), and conducting objects accounts for mixes 0.1% of general assembly (TW), and spacer accounts for and mixes 0.9% of general assembly (TW).
The thickness of this mixolimnion 110 should be controlled at 5 microns～100 microns, and the THICKNESS CONTROL of this smectic liquid crystal light modulation rete 100 is at 5 microns～10000 microns.
In actual design; Mixolimnion 110 also can be mixed with dichroic dye; Preferably; Dichroic dye can account for and mix 5% of general assembly (TW), through an amount of dichroic dye is mixed into mixolimnion 110, can make light modulation sheet of the present invention realize the switching between bright, the coloured shading of full impregnated, the various coloured gray.
In addition, mixolimnion 110 also can be mixed with in two tropism's whitening agent, viscosity modifier, plasticity correctives, the foam-breaking agent any or appoint several kinds mixing.Two tropism's whitening agent have the effect that increases contrast.The viscosity of viscosity modifier scalable potpourri make potpourri be convenient to apply, and it has improved the driving effect of mixolimnion.The plasticity correctives is used to change the plasticity of light modulation sheet when high temperature, is convenient to fit.Foam-breaking agent is used to reduce the bubble of mixolimnion, boosts productivity.These adjuvants can account for the 0%-10% that mixes general assembly (TW) (other components according to the corresponding minimizing of original ratio some so that all components weight sum is 100%).
In actual design, also can on the lateral surface of two body layer 200,300, respectively post a protective seam 600, hurt sb.'s feelings to prevent the glass fragment that accident collision produces body layer.
In actual design, can attach a reflecting plate in a side of light modulation sheet of the present invention, like versicolor paper, plastics, fibre, woodwork or metallic article etc., can improve the contrast of displaying contents so effectively.
In actual design, the size of body layer and smectic liquid crystal light modulation rete 100 is restriction not, as long as smectic liquid crystal light modulation rete is not more than the size of body layer.If the very large-area light modulation sheet of structure then can splice a plurality of light modulation sheets and realize.
In actual use, if two body layer are selected the hard thicker glass of material for use, light modulation sheet then of the present invention can be as uses such as vehicle dormer window, external wall, glass curtain walls.If two body layer are selected organic transparent material for use, light modulation sheet then of the present invention has the flexible characteristic, can be widely used in various light modulation produce markets.
In practical application; Can light modulation sheet of the present invention be connected with skeleton on the application site such as automobile or construction wall; And be fixed through connection fittings, to the signal controlling of light modulation sheet of the present invention can be direct-connected through electric wire, remote control, acoustic control, temperature control, intelligence, image sensing, communication network control or light self-induction mode realize.
Be that the transparency electrode of whole piece is an example with conductive electrode layer 120,130 below, the principle of work of light modulation sheet of the present invention is described.
During use; Be applied to the voltage waveform (comprising voltage magnitude size, frequency, action time etc.) on the conductive electrode layer through reasonable control circuit driving control device 700; Make the smectic liquid crystal molecule in the mixolimnion 110 demonstrate different arrangement form; To reach the dimming effect of various light transmission rates; Light switches between transmission, scattering or even various progressive state, shows as light modulation sheet of the present invention on the macroscopic view and between the bright state of full impregnated, vaporific shading state, various gray state, switches.
As shown in Figure 4; Through drives control device 700 output control waveforms; The bidirectional pulse that applies 50v (a certain value gets final product between the 5v to 250v), 100Hz (a certain value gets final product between the 50Hz to 200Hz) on two conductive electrode layers 120,130 (only phase place is opposite for the bidirectional pulse that applies on two conductive electrode layers 120,130); When voltage action time the time less than 1 second; The smectic liquid crystal molecule 1 11 that is encapsulated in the polymer architecture (not shown among Fig. 4) twists under the drive of the conducting objects molecule 1 12 of motion, forms out of order arrangement form shown in Figure 4.Because each of smectic liquid crystal molecule 1 11 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 liquid crystal molecule 1 11 of incident exist very big difference; Promptly in the mixolimnion 110 of this meagre thickness, optical index is producing violent variation, thereby strong scattering has taken place light; See from macroscopic view; The light modulation sheet of the present invention of this moment is a kind of astigmatic effect, presents vaporific shading state, as acute-matte.The light modulation sheet of the present invention of this moment has a kind of diffuse effect, can reduce light pollution effectively, and can not increase indoor thermal effect.
As shown in Figure 5; Through drives control device 700 output control waveforms; The bidirectional pulse that applies 50v (a certain value gets final product between the 5v to 250v), 1000Hz (a certain value more than the 1000Hz gets final product) on two conductive electrode layers 120,130 (only phase place is opposite for the bidirectional pulse that applies on two conductive electrode layers 120,130); When voltage action time less than 1 second the time, the smectic liquid crystal molecule 1 11 that is encapsulated in the polymer architecture (not shown among Fig. 5) becomes regularly arranged form under effect of electric field, at this moment; The long optical axis of smectic liquid crystal molecule 1 11 is perpendicular to the conductive electrode layer plane; The ray refraction of each smectic liquid crystal molecule 1 11 of incident does not produce acute variation, and light can freely see through mixolimnion 110, and since the optical refractive index of polymerizable molecular and spacer rod 113 all the optical refractive index with smectic liquid crystal molecule 1 11 is very close; Polymerizable molecular and spacer rod 113 can not influence the transmittance of light; Therefore, see that this moment, light modulation sheet of the present invention demonstrated the bright state of full impregnated from macroscopic view.
Various gray states are the progressive states between bright state of full impregnated and the vaporific lucifuge state.Be applied to the control waveform on the conductive electrode layer through reasonable control; Can make the arrangement form of smectic liquid crystal molecule 1 11 become the part distortion; To produce astigmatic effect in various degree; That is, make light modulation sheet of the present invention between vaporific shading state and the bright state of full impregnated, produce the multiple progressive state of different gray, like translucent etc.
After producing luminous effects such as scattering or transmission for conductive electrode layer 120,130 on-load voltages, light modulation sheet 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 light modulation sheet 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 liquid crystal molecule 1 11.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 " characteristic is because the conducting objects in the mixolimnion 110 has conductive characteristic; When voltage signal is applied on two conductive electrode layers; Ion in the conducting objects just changes the generation to-and-fro movement according to electric potential difference; This motion can change the arrangement form of smectic liquid crystal molecule 1 11, and smectic liquid crystal molecule 1 11 arrangement form after changing do not need the persistent movement of ion to keep, and are stable." multistable " characteristic that this smectic liquid crystal and conducting objects produce and liquid crystal polymer light regulating technology produce, and to keep effect different, and the liquid crystal that has added Molecularly Imprinted Polymer in the liquid crystal polymer light regulating technology is to keep by surface force, intermolecular force and friction force in the number of polymers network.
As shown in Figure 6, the invention allows for a kind of method for making of making smectic liquid crystal light modulation sheet shown in Figure 2, this method for making comprises the steps:
The first step, cleaning, dried base layer 140,150.In reality was implemented, the cleaning process in this step can use the ultrasonic cleaning machine to clean, and base layer 140,150 cleans through the rinse bath that acetone, absolute ethyl alcohol, distilled water, deionized water, absolute ethyl alcohol tank liquor are housed successively.
In second step, making (for example sputter) conductive electrode layer (promptly on base layer 140 medial surfaces, make conductive electrode layer 120, on base layer 150 medial surfaces, make conductive electrode layer 130), cleaning, drying then on each base layer medial surface.In reality was implemented, the cleaning process in this step also can use the ultrasonic cleaning machine to clean, and the base layer that is coated with conductive electrode layer cleans through the rinse bath that acetone, absolute ethyl alcohol, distilled water, deionized water, absolute ethyl alcohol tank liquor are housed successively.In reality is implemented; Can carry out etching processing to conductive electrode layer 120,130 through dry method or wet etching method; Etch required electrode; Clean then, drying, this cleaning process can use the ultrasonic cleaning machine to clean, the base layer that has the etching electrode cleans through the rinse bath that tap water, distilled water, clean-out system, distilled water, deionized water, absolute ethyl alcohol tank liquor are housed successively.The electrode shape of conductive electrode layer etching and quantity can be set by actual requirement.Usually, two conductive electrode layers are etched electrode, the N electrode that is arranged in parallel that M is arranged in parallel respectively, so that M electrode and N electrode quadrature and form the array structure of M * N pixel mutually.
In the 3rd step, make mixolimnion 110 at two conductive electrode layers 120, between 130, thereby accomplish the making of smectic liquid crystal light modulation rete 100.
The 4th step; Cleaning, dry body layer 200,300; Lay an adhesive phase 400 therein on the medial surface of a body layer 200; The smectic liquid crystal light modulation rete 100 that the 4th step was made is placed on this adhesive phase 400, and a lateral surface of this smectic liquid crystal light modulation rete 100 is contacted with this adhesive phase 400, and the conductive electrode layer 120,130 in this smectic liquid crystal light modulation rete 100 is connected with circuit external driving control device 700; On another lateral surface of this smectic liquid crystal light modulation rete 100, lay an adhesive phase 500, a body layer 300 then successively, thereby obtain light modulation sheet initiation layer stack structure.In this step, carry out conductive electrode layer 120,130 when being connected with drives control device 700; The good electrode that is connected with drives control device 700 of cloth in the space that smectic liquid crystal light modulation rete 100 next doors are left makes all electrodes glitch-free drawing each other.
The 5th step; Under the pressure of the temperature that is provided with, setting, this light modulation sheet initiation layer stack structure is pressurizeed, heats, make adhesive melts in the adhesive phase 400,500, slough bubble; Fill all spaces in this light modulation sheet initiation layer stack structure full; Be bonded into integral body, cool off under the vacuum condition in being in predetermined temperature range then, thereby obtain this smectic liquid crystal light modulation sheet.In this step, the temperature of setting is controlled between 30-150 ℃, and the pressure of setting is controlled between the 1-105000Pa, and predetermined temperature range is 0-130 ℃.
Through after above-mentioned five steps, light modulation sheet of the present invention shown in Figure 2 has just completed.
In reality is implemented, there are two kinds of methods to realize above-mentioned the 3rd step.
A kind of method comprises the steps:
Step 1, will be under preset temperature by setting on the medial surface that mode that potpourri that proportion mixing smectic liquid crystal, polymerizable molecular material, conducting objects and spacer obtain gets ready through direct printing or etching or nano impression or spraying is coated in one of them or two conductive electrode layers.In reality, the preset temperature in this step is 0-150 ℃, and preferred temperature is 120 ℃, and in this temperature range, potpourri becomes starchiness, so that apply.Normally, room temperature-20 ℃ is during to+70 ℃, and the branch sub-cluster of smectic liquid crystal is the layered arrangement structure, demonstrates the starchiness of thickness.Coating procedure in this step can use coating machine.
Step 2, two base layers 140,150 of fitting make the potpourri that applies in the step 1 at two conductive electrode layers 120, between 130.Applying process in this step can adopt the volume to volume technology, can use equipment such as vacuum abutted machine or laminating machine to accomplish.The thickness of used applying glue of fitting should be controlled at smaller or equal to 1 μ m.
Step 3; In one section setting-up time in the design temperature scope; Potpourri in the ultraviolet irradiation step one of heating or use setting light intensity; Make the polymerizable molecular material be cured to form polymer architecture, and smectic liquid crystal, conducting objects and spacer be encapsulated in this polymer architecture (promptly being encapsulated in the accommodating chamber of this polymer architecture), thereby obtain smectic liquid crystal light modulation rete.In this step, the design temperature scope is 0～200 ℃, and setting-up time is controlled between 1s～10h, and the setting light intensity of ultraviolet light is controlled at 1W/cm
2～10000W/cm
2In actual the enforcement, the light application time of temperature, ultraviolet light, the irradiates light of ultraviolet light depend on the material and the thickness of polymerizable molecular material by force.Can know that in same light application time, same polymerizable molecular material 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, the polymerizable molecular material is thick more, and light application time required during curing is long more.
Second method comprises the steps:
Step 1 applies one deck therein and has the unimolecule body material of setting pattern on the medial surface of a conductive electrode layer 120.
Step 2; Will be under preset temperature be coated in by setting potpourri ink-jet that proportion mixings smectic liquid crystal, conducting objects and spacer obtain that (pattern on the unimolecule body material has formed concaveconvex structure in this each accommodating chamber with unimolecule body material formation of setting pattern; So; The bossing that sunk part is adjacent constitutes accommodating chamber, the accommodating chamber of the polymer architecture after this accommodating chamber promptly becomes).Preset temperature in this step is 0-150 ℃, and preferred temperature is 120 ℃, and in this temperature range, potpourri becomes starchiness, so that apply.Coating procedure in this step can use coating machine.
Step 3, two base layers 140,150 of fitting, this that makes that ink-jet in the step 2 is coated with potpourri have set pattern unimolecule body material at two conductive electrode layers 120, between 130, thereby obtain smectic liquid crystal light modulation rete initial configuration.Applying process in this step can adopt the volume to volume technology, can use equipment such as vacuum abutted machine or laminating machine to accomplish.The thickness of used applying glue of fitting should be controlled at smaller or equal to 1 μ m.
Step 4; In one section setting-up time in the design temperature scope; Make this smectic liquid crystal light modulation rete initial configuration of UV-irradiation of setting light intensity; This has unimolecule body material of setting pattern and is cured to form polymer architecture, and the potpourri that smectic liquid crystal, conducting objects and spacer are formed is encapsulated in this polymer architecture, thereby obtains smectic liquid crystal light modulation rete.In this step, the design temperature scope is 0～200 ℃, and setting-up time is controlled between 1s～10h, and the setting light intensity of ultraviolet light is controlled at 1W/cm
2～10000W/cm
2In actual the enforcement, the light application time of temperature, ultraviolet light, the irradiates light of ultraviolet light depend on coating by force this have the material and the thickness of the unimolecule body material of setting pattern.Can know in actual the enforcement that in same light application time, this same unimolecule body material with setting pattern that applies is cured, temperature is high more, the irradiation light intensity of ultraviolet light is strong more, and curing rate is fast more; Under same temperature, same irradiation light intensity, it is thick more that this of coating has a unimolecule body material of setting pattern, and light application time required during curing is long more.
Advantage of the present invention is:
Light modulation sheet of the present invention is a kind of polymer architecture encapsulation type light modulation sheet, and this light modulation sheet is different from traditional light modulating device (as: polymer dispersion, the nano particle-compound light modulating device of memory class polymkeric substance) by continuing to switch on and control.
The potpourri two of encapsulation can be immiscible between mutually in polymer architecture in the light modulation sheet of the present invention and the polymer architecture; Be do not contain in the polymer architecture not contain polymerizable molecular in smectic liquid crystal and the smectic liquid crystal, it is alternate miscible each other and influence the problem of quality to have solved on the market liquid crystal and polymerizable molecular in the polymer dispersion light modulating device two.
Light modulation sheet of the present invention uses smectic liquid crystal to realize dimming function; Realized " multistable " effect, the dimming state (vaporific shading state, the bright state of full impregnated or certain gray state) before outage back light modulation sheet of the present invention still can keep cutting off the power supply, dimming state need not switched on and kept; And traditional light modulating device can only return to original vaporific shading state after outage; Therefore, light modulation sheet of the present invention has very high practicality, energy-saving low-carbon.
Light modulation sheet of the present invention can be between vaporific shading state, the bright state of full impregnated, various gray state switches fast, and the transmittance when being in the bright state of full impregnated can reach more than 80%, and the astigmatism property when being in vaporific shading state is very stable, can reach the shading requirement.
Because designed adhesive phase in the light modulation sheet of the present invention, adhesive phase can play a very good protection, therefore, light modulation sheet of the present invention has withstand voltage anti-broken characteristics.If body layer adopts glass, cracked even glass damages, fragment also can be bonded on the adhesive phase, has avoided glass chip to drop and personnel's injury of causing.
Light modulation sheet of the present invention does not have any murder by poisoning, and health environment-friendly can be widely used in fields such as building decoration and fitment, private control area, automotive electronics.
Method for making of the present invention is simple and easy to control, and the light modulation sheet yield rate of producing is high, is suitable for industrialization, and cost is very low.
Above-mentioned 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.
Claims (10)
1. smectic liquid crystal light modulation sheet, it is characterized in that: it comprises two body layer, is provided with smectic liquid crystal light modulation rete in the middle of these two body layer; This smectic liquid crystal light modulation rete comprises two conductive electrode layers; Two these conductive electrode layers are connected with the circuit external driving control device; Be provided with mixolimnion in the middle of these two conductive electrode layers, this mixolimnion comprises and is encapsulated in the potpourri of being made up of smectic liquid crystal, conducting objects and spacer in the polymer architecture; The medial surface of each this body layer is mutually bonding through an adhesive phase with the lateral surface of corresponding this conductive electrode layer respectively.
2. smectic liquid crystal light modulation sheet as claimed in claim 1 is characterized in that:
Be provided with base layer between said conductive electrode layer and the said adhesive phase.
3. according to claim 1 or claim 2 smectic liquid crystal light modulation sheet is characterized in that:
Said polymer architecture is got ready on the medial surface of conductive electrode layer through direct printing or etching or nano impression or spraying by unimolecule body material or polymerizable molecular material; Heat curing or ultra-violet curing are that the polymerizable molecular material with setting structure forms, and this unimolecule body material is any in epoxy resin, polyacrylate or the polymethacrylate monomer;
Said smectic liquid crystal is the category-A smectic liquid crystal;
Said conducting objects in the nano particle, mineral compound, organic compound, CNT, Graphene, sodium carbonate, cetyltriethylammonium bromide of band conductive characteristic any or appoint several kinds mixing;
Said spacer is batching sphere or the spacer rod that polyester material or glass material are processed;
Consisting of of said mixolimnion: said smectic liquid crystal accounts for the 10%-99% that mixes general assembly (TW); Said polymerizable molecular material accounts for the 1%-90% that mixes general assembly (TW); Said conducting objects accounts for the 0%-10% that mixes general assembly (TW), and said spacer accounts for the 0%-20% that mixes general assembly (TW).
4. smectic liquid crystal light modulation sheet as claimed in claim 2 is characterized in that:
Said body layer selects for use transparent glass or organic transparent material to process; This transparent glass is any in simple glass, vehicle glass, external window of building glass, tempered glass or the special glass, and this organic transparent material is any in PET, PMMA, acryl resin or the transparent silica gel; Two said body layer are processed for glass simultaneously or are processed for organic transparent material simultaneously, perhaps, process another for glass and process for organic transparent material for one in two said body layer; The thickness range of said body layer is greater than 0cm and smaller or equal to 5cm;
Said adhesive phase is selected any in PVB, EVA hot melt adhesive, heat-curable glue or the UV curing glue for use; The thickness range of said adhesive phase is greater than 0cm and smaller or equal to 5cm;
Said base layer selects for use polyethylene terephthalate or polyimide or polyetherimide or tygon to process; The thickness range of said base layer is greater than 0mm and smaller or equal to 10mm;
Said conductive electrode layer selects for use ITO to process, and is perhaps processed by carbon nano tube-doped polymer molecule material, perhaps adds at the ITO material or on by the basis of carbon nano tube-doped polymer molecule material and is processed by metal or the nonmetal conductive material that constitutes; The electrode shape of said conductive electrode layer is any, and the shape of each electrode is identical or different.
5. smectic liquid crystal light modulation sheet as claimed in claim 3 is characterized in that:
Said smectic liquid crystal be with in silica-based compound, four cyano four octyl group biphenyl or tetraacethyl ester in the last of the ten Heavenly stems four cyano biphenyl any or appoint several kinds mixing.
6. smectic liquid crystal light modulation sheet as claimed in claim 3 is characterized in that:
Said polymer architecture is formed with accommodating chamber, and said polymer architecture is that spherical, little cylindric, thread, hemispherical, parallel strip, cube, rectangular parallelepiped, the intersection of rule is traditional thread binding, in the mixed structure of network structure, square grid minor structure, irregular polygon structure or above-mentioned multiple structure any; Said polymer architecture is even or inhomogeneous; Each other miscible or disperse or be in contact with one another or at interval between said polymer architecture and said smectic liquid crystal, conducting objects and the spacer.
7. according to claim 1 or claim 2 smectic liquid crystal light modulation sheet is characterized in that:
Said mixolimnion be mixed with in dichroic dye, two tropism's whitening agent, viscosity modifier, plasticity correctives or the foam-breaking agent any or appoint several kinds mixing.
8. the method for making of the described smectic liquid crystal light modulation of claim 2 sheet, it is characterized in that: it comprises the steps:
The first step, cleaning, dried base layer;
In second step, on each base layer medial surface, make a conductive electrode layer, then cleaning, drying;
In the 3rd step, between two conductive electrode layers, make mixolimnion, thereby accomplish the making of smectic liquid crystal light modulation rete;
The 4th step; Cleaning, dry body layer; Lay an adhesive phase therein on the medial surface of a body layer; The smectic liquid crystal light modulation rete that the 4th step was made is placed on this adhesive phase, and a lateral surface of this smectic liquid crystal light modulation rete is contacted with this adhesive phase, and the conductive electrode layer in this smectic liquid crystal light modulation rete is connected with the circuit external driving control device; On another lateral surface of this smectic liquid crystal light modulation rete, lay an adhesive phase, a body layer then successively, thereby obtain light modulation sheet initiation layer stack structure;
The 5th step; Under the pressure of the temperature that is provided with, setting; This light modulation sheet initiation layer stack structure is pressurizeed, heats, make adhesive melts in the adhesive phase, slough bubble, this light modulation sheet initiation layer stack structure is bonded into integral body; Cool off under the vacuum condition in being in predetermined temperature range then, thereby obtain this smectic liquid crystal light modulation sheet.
9. method for making as claimed in claim 8 is characterized in that:
Said the 3rd step specifically comprises:
Step 1, will be under preset temperature by setting on the medial surface that mode that potpourri that proportion mixing smectic liquid crystal, polymerizable molecular material, conducting objects and spacer obtain gets ready through direct printing or etching or nano impression or spraying is coated in one of them or two conductive electrode layers;
Step 2, two base layers of fitting make the potpourri that applies in the step 1 between two conductive electrode layers;
Step 3; In one section setting-up time in the design temperature scope; Potpourri in the ultraviolet irradiation step one of heating or use setting light intensity; Make the polymerizable molecular material be cured to form polymer architecture, and smectic liquid crystal, conducting objects and spacer be encapsulated in this polymer architecture, thereby obtain smectic liquid crystal light modulation rete.
10. method for making as claimed in claim 8 is characterized in that:
Said the 3rd step specifically comprises:
Step 1 applies the unimolecule body material with setting pattern therein on the medial surface of a conductive electrode layer;
Step 2, the potpourri ink-jet that will under preset temperature, obtain by setting proportion mixing smectic liquid crystal, conducting objects and spacer is coated in this each accommodating chamber with unimolecule body material formation of setting pattern;
Step 3, two base layers of fitting make ink-jet in the step 2 be coated with unimolecule body material that having of potpourri set pattern between two conductive electrode layers, thereby obtain smectic liquid crystal light modulation rete initial configuration;
Step 4; In one section setting-up time in the design temperature scope; Make this smectic liquid crystal light modulation rete initial configuration of UV-irradiation of setting light intensity; This has unimolecule body material of setting pattern and is cured to form polymer architecture, and the potpourri that smectic liquid crystal, conducting objects and spacer are formed is encapsulated in this polymer architecture, thereby obtains smectic liquid crystal light modulation rete.
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Application publication date: 20120905 |