CN106873279A - A kind of electrochromic film and preparation method thereof - Google Patents
A kind of electrochromic film and preparation method thereof Download PDFInfo
- Publication number
- CN106873279A CN106873279A CN201710186039.0A CN201710186039A CN106873279A CN 106873279 A CN106873279 A CN 106873279A CN 201710186039 A CN201710186039 A CN 201710186039A CN 106873279 A CN106873279 A CN 106873279A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- polymerisable monomer
- coating
- ultraviolet light
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13718—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on a change of the texture state of a cholesteric liquid crystal
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13762—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering containing luminescent or electroluminescent additives
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Liquid Crystal (AREA)
Abstract
The invention discloses a kind of electrochromic film and preparation method thereof, the electrochromic film is made up of multilayer materials, and every layer of composite includes macromolecule network, liquid crystal molecule and dyestuff；The liquid crystal molecule is dispersed in inside the macromolecule network；The dyestuff being dispersed between the macromolecule network and the liquid crystal molecule in dyestuff, and different composite material layer has absorption to the visible ray of different-waveband.The present invention makes the driving voltage of liquid crystal molecule between layers different by adjusting the structure of macromolecule network in every layer of composite, prepared electrochromic film can be presented different colors when different voltages are applied, it is high with stability, change Color tunable, it is various the advantages of.
Description
Technical field
The invention belongs to feature liquid crystal material prepare and applied technical field, more particularly to a kind of electrochomeric films and
Its preparation method.
Background technology
Electrochromism refers to material when electric field is applied, the property that absorption or reflectance spectrum to visible ray change,
Material with electrochromic property is referred to as electrochromic material.
By the development of more than ten years, electrochromic material is widely used, whether military project or in daily life
In work, all important roles of performer.In military field, one of discoloration art in modern battlefield is exactly using reversible color material
Material, makes that the color of protected target surface change colour as the color of background is different and residing background blendes together integrally, so as to reach
To the stealthy purpose of vision.If for example, the surface of the barracks of army, covers one layer of electrochomeric films material, it is possible to root
According to any its color of change is needed, the color same with surrounding environment is made it have.
Electrochromic material, also tool has been widely used in daily life, can be used for building, automobile and flies
The fields such as the door and window of machine.People can as needed change the color of door and window, adjust the transmitance of door glass, reach energy-conservation mesh
's；Can also be used as the controllable optical thin-film material such as liquid crystal display width visual angle effect film and HDR light transmission rates regulation and control film.
At present both at home and abroad in the research of electrochromic material, its study hotspot is concentrated mainly on following a few class materials：
(1) inorganic, metal oxide, this kind of material mainly using transition metal oxide under certain condition its metal from
There is transformation and the change of color occur in the valence state of son.Wherein, most representational material is WO3, tungsten ion therein is in height
It is in colourless during valence state, and is in blueness in lower valency.But this kind of material is difficult to the transformation of multiple color, and electric color rings
It is more long between seasonable, while after a long time use, can make because of accumulation of the ionic charge counterion in electrochromic device
Electric color performance degradation.
(2) organic electrochromic material, such as polypyrrole, polythiophene, polyaniline.This kind of material mainly using its valence band and
The energy difference of conduction band is changed colour, therefore its color limited by electroconductive molecule electron energy band and cannot realize multiple color
Switching.And this kind of material is equally difficult to the preparation of filming, large area.
In a word, electrochromic material has been widely used in military project and civil area tool.But existing electrochromic material,
Have the shortcomings that short life and change color can not arbitrarily set.These shortcomings greatly constrain off-color material in China's national defense
Build and the effect played in economic construction.
The content of the invention
The shortcomings of in order to solve existing electrochromic material short life and change color arbitrarily to set, the present invention is carried
A kind of novel electrochromic thin-film material that can arbitrarily regulate and control with good stability and change color and its preparation side are supplied
Method.
A kind of electrochromic film that the present invention is provided, is made up of multilayer materials, and every layer of composite includes macromolecule
Network, liquid crystal molecule and dyestuff；The liquid crystal molecule is dispersed in inside the macromolecule network；The macromolecule network and described
The dyestuff being dispersed between liquid crystal molecule in dyestuff, and different composite material layer has absorption to the visible ray of different-waveband.
Above-mentioned electrochromic film, prepares liquid crystal material in every layer of raw material of composite, polymerisable monomer and (aggregates into high score
Sub-network), the proportioning of dyestuff be：
Liquid crystal material：10.0~90.0 weight portions；
Polymerisable monomer：10.0~80.0 weight portions；
Dyestuff：0.01~20.0 weight portion.
Preferably selected as one of above-mentioned technical proposal, the polymerisable monomer can be all polymerizable by non-liquid crystal
Monomer composition, or collectively constituted by liquid crystal liquid crystal property polymerisable monomer and non-liquid crystal polymerisable monomer.
Preferably selected as one of above-mentioned technical proposal, the composition according to the polymerisable monomer is different, film
The selection of preparation method and liquid crystal material is also different.If polymerisable monomer is polymerizable by liquid crystal liquid crystal property polymerisable monomer and non-liquid crystal
Monomer is collectively constituted, then every layer of composite need to need to select courage in solidification using the preparation method of step-by-step polymerization, liquid crystal material
Steroid phase liquid crystal material；If polymerisable monomer is all made up of non-liquid crystal polymerisable monomer, every layer of composite is in solidification
Can direct step completion polymerization, liquid crystal material selection nematic phase or liquid crystal material of cholesteric phase.That is, the composite wood
One or more layers the macromolecule network in material is gathered jointly by liquid crystal liquid crystal property polymerisable monomer and non-liquid crystal polymerisable monomer
When conjunction is formed, corresponding liquid crystal material is liquid crystal material of cholesteric phase；One or more layers the high score in the composite
When sub-network is polymerized by non-liquid crystal polymerisable monomer, corresponding liquid crystal material is Nematic phase liquid crystal material and/or cholesteric
Phase liquid crystal material
Described step-by-step polymerization and ultraviolet light step-by-step polymerization mentioned below refer to by every layer of composite can
Polymerized monomer realizes polymerization by controllable mode, and it is included under ultraviolet light-initiated pre-polymerization and ultraviolet light and electric field collective effect
Power-up polymerization, the pre-polymerization is so that in system 10%~90% non-liquid crystal polymerisable monomer and 0.1%~90%
Liquid crystal liquid crystal property polymerisable monomer realizes polymerization, so as to be formed with certain viscosity and with mesh-structured preliminary high score subnet
Network, has substantially vertical orientated macromolecule by being formed polymerization in mesh under the collective effect of ultraviolet light and electric field again afterwards
Network.According to purposes (such as the requirement of rigidity and flexible and product performance), the degree of polymerization of pre-polymerization can be controlled realize for
The control of step-by-step polymerization.The mode of control can select to extend or shorten the time of ultraviolet lighting, such as select the illumination of pre-polymerization
Time, in order to obtain the product with different pre-polymerization degree, the pre-polymerization ultraviolet lighting time that can be selected could within 10-600s
Being 10-30s, 30-60s, 60-120s, 100-200s, 200-400s, 400-600s.When controlling the ultraviolet lighting of pre-polymerization
Between can obtain non-liquid crystal polymerisable monomer extent of polymerization (monomer reaction ratio) for 10-20%, 20-30%, 30-50%,
50-60%, 60-70%, 70-90% and liquid crystal liquid crystal property polymerisable monomer extent of polymerization (monomer reaction ratio) are 0.1-10%,
The prepolymer product of 10-20%, 20-40%, 40-60%, 60-70%, 70-90%.Control has been used in embodiments of the invention
The mode of ultraviolet lighting time processed controls step-by-step polymerization, but those skilled in the art it is to be understood that other can control to gather
The method of conjunction progress can also be applied to implementation of the invention.
Preferably selected as one of above-mentioned technical proposal, the driving voltage of liquid crystal molecule in every layer of composite
It is different.
Preferably selected as one of above-mentioned technical proposal, the driving voltage of liquid crystal molecule in every layer of composite
Can be adjusted by controlling the mesh size of macromolecule network.
Preferably selected as one of above-mentioned technical proposal, the mesh chi of macromolecule network in every layer of composite
Very little size is 1 μm~100 μm.The mesh aperture of the network can be by controlling polymerisable monomer in every layer of composite raw material
Content, polymerization process in ultraviolet ray intensity, the content of light trigger etc. be adjusted.If polymerisable monomer is by liquid crystal liquid crystal property
Polymerisable monomer and non-liquid crystal polymerisable monomer are constituted, then can also form vertical orientated inside the mesh of macromolecule network
Network, based on general knowledge after aperture is controlled, the vertical orientated macromolecule network prepared according to the inventive method
Also can be changed.For described mesh size, different value ranges, such as 1-10,10-20,20-40,40- can be selected
60,60-80,80-100 micron, mesh diameter is limited by, corresponding vertical orientated macromolecule network size also can be corresponding
It is changed into smaller size.
Preferably selected as one of above-mentioned technical proposal, the liquid crystal material may be selected Nematic phase liquid crystal material or by
The liquid crystal material of cholesteric phase of Nematic phase liquid crystal material and chipal compounds composition.
Described Nematic phase liquid crystal material may be selected but be not limited to following some markets liquid crystal material on sale, such as immortality Hua Qing
SLC-1717, SLC-7011, TEB30A of liquid crystal material Co., Ltd etc., the E7 of Merck KGaA liquid crystal material company, E44,
E48, ZLI-1275 etc..Those skilled in the art can also obtain corresponding Nematic phase liquid crystal material by voluntarily mixture
Described chipal compounds include but are not limited to one or more in following molecule, such as cholesteryl nonanoate,
The such as CB15, C15, S811, R811, S1011, R1011
Preferably selected as one of above-mentioned technical proposal, the dyestuff in each layer is to the visible of different-waveband
Light has absorption.
Preferably selected as one of above-mentioned technical proposal, the polymerisable monomer is ultraviolet light polymerisable monomer, can
All it is made up of non-liquid crystal ultraviolet light polymerisable monomer, or by non-liquid crystal ultraviolet light polymerisable monomer and liquid crystal liquid crystal property ultraviolet light
Polymerisable monomer is collectively constituted.Wherein non-liquid crystal ultraviolet light polymerisable monomer may be selected but be not limited only to it is following in one kind or
It is several, such as unsaturated polyester (UP), epoxy acrylate, urethane acrylate, polyester acrylate, epoxy acrylate, polyenoid
Thiol, polyether acrylate, water-and acrylate, vinyl ethers etc..
Liquid crystal liquid crystal property ultraviolet light polymerisable monomer also may be selected but be not limited to one or more in following molecule, such as：
Wherein, m, n are 4~8 integer, and x, y are 1 or 2, and E, Q each stand alone as acrylate-based, or epoxide group, or
Urethane acrylate base, or sulfydryl.Molecule is listed below for reference, it is not limited to these materials：
Above-mentioned light trigger may be selected benzophenone, benzoin dimethylether (UV 651), chloro thioxanthone (ITX), 2,
4- diethyl thioxanthones (DETX), isopropyl thioxanthone (ITX), 2- hydroxyl -2,2- methyl isophthalic acids-phenylacetone (UV1173)
Deng, but it is not limited only to these materials.
The present invention also provides the preparation method of foregoing electrochromic film, if polymerisable monomer is all by non-liquid crystal ultraviolet light
Polymerisable monomer is constituted, including：
(1) by liquid crystal material (LC) and polymerisable monomer, initiator, dyestuff R1Blending, obtains the homogeneous coating T of mixing1；
(2) coating apparatus are utilized by T1It is coated with uniformly on conductive film, and is controlled by controlling the conditions such as coating speed
The thickness of coating, forms coating L1；
(3) ultraviolet light coating L is utilized under conditions of inert gas shielding1For a period of time, photochromic layer Y is obtained1；
(4) by liquid crystal material (LC), polymerisable monomer, dyestuff R2, initiator mixing to be obtaining uniform coating T2；Utilize
Coating apparatus are by T2In photochromic layer Y1Upper coating is uniform, forms coating L2；Then using ultraviolet under conditions of inert gas shielding
Light irradiation coating L2For a period of time, photochromic layer Y is obtained2；
(5) repeat the above steps, until obtaining coating Ln, n is natural number；
(6) another piece of conductive film is layered on coating LnOn, electric field is applied by conductive film, while continuation is entered to film
Row ultraviolet light, makes the remaining polymerisable monomer polymerization in conductive film inside complete, obtains electrochomeric films.
In above-mentioned preparation method, the dyestuff R of different coatingnIt is different, the visible ray to different-waveband has suction respectively
Receive.
In step (1) and (4), the parts by weight of liquid crystal material, polymerisable monomer, initiator and dyestuff are：10~90 weights
Measure the liquid crystal material of part, the polymerisable monomer of 10~80 weight portions, the initiator of 0.1~5 weight portion and 0.01~20 weight portion
Dyestuff.
The present invention also provides another preparation method of foregoing electrochromic film, if polymerisable monomer is by liquid crystal liquid crystal property ultraviolet light
Polymerisable monomer and non-liquid crystal ultraviolet light polymerisable monomer are collectively constituted, including：
(1) by liquid crystal material (LC) and polymerisable monomer, initiator, dyestuff R1Blending, obtains the homogeneous coating T of mixing1；
(2) coating apparatus are utilized by T1It is coated with uniformly on conductive film, and is controlled by controlling the conditions such as coating speed
The thickness of coating, forms coating L1；
(3) ultraviolet light coating L is utilized under conditions of inert gas shielding1, make coating L1Middle non-liquid crystal is polymerizable
There is incomplete polymerisation in the liquid crystal liquid crystal property polymerisable monomer of monomer sum, obtain pre- poly layer Y1；
(4) by liquid crystal material (LC), polymerisable monomer, dyestuff R2, initiator mixing to be obtaining uniform coating T2；Utilize
Coating apparatus are by T2In pre- poly layer Y1Upper coating is uniform, forms coating L2；Then using ultraviolet under conditions of inert gas shielding
Light irradiation coating L2, make coating L2It is anti-to there is not exclusively polymerization in the liquid crystal liquid crystal property polymerisable monomer of middle non-liquid crystal polymerisable monomer sum
Should, obtain pre- poly layer Y2；
(5) repeat the above steps, until obtaining pre- poly layer Yn, n is natural number；
(6) another piece of conductive film is layered on pre- poly layer YnOn, electric field is applied by conductive film, while continuing to film
Ultraviolet light is carried out, makes the remaining polymerisable monomer polymerization in film inside complete, obtain electrochomeric films.
In above-mentioned preparation method, the dyestuff R of different coatingnIt is different, the visible ray to different-waveband has suction respectively
Receive.
In step (1) and (4), the proportioning of liquid crystal material, polymerisable monomer, initiator and dyestuff is：10~90 weight portions
Liquid crystal material, the polymerisable monomer of 10~80 weight portions, the dye of the initiator of 0.1~5 weight portion and 0.01~20 weight portion
Material.
Structure by adjusting macromolecule network in every layer of composite of the invention, makes the drive of liquid crystal molecule between layers
Dynamic voltage is different, and prepared electrochromic film can be presented different colors when different voltages are applied, high with stability,
Change Color tunable, it is various the advantages of.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the macromolecule network of prepared blue coating cross sections in embodiment 1；
Fig. 2 is the stereoscan photograph of the macromolecule network of prepared yellow coating cross sections in embodiment 1；
Fig. 3 is reflectance spectrum of the prepared film in embodiment 1 respectively in the case where 0V, 30V and 75V voltage is applied；
Fig. 4 is the stereoscan photograph of the macromolecule network in prepared red coatings section in embodiment 2；
Fig. 5 is the stereoscan photograph of the macromolecule network of prepared yellow coating cross sections in embodiment 2；
Fig. 6 is reflectance spectrum of the prepared film in embodiment 2 respectively in the case where 0V, 63V and 92V voltage is applied.
Specific embodiment
Embodiments of the invention are the following is, it is only used as explanation of the invention and not limits.
Reacted in 25 DEG C of environment of room temperature in examples below.Used polymerisable monomer in embodiment 1,2
Title and structural formula it is listed below：
Wherein, HMPA (Hydroxypropyl methacrylate) structure is
LMA (Lauryl methacrylate) structure is
PEDGA600 (Polyethylene glycol diacrylate) structure is
Bis-EMA15 (Bisphenol a ethoxylate dimethacrylate) structure is
C6M(2-methyl-1,4-phenylene-bis(4-((6-acryloyloxy)hexyl)oxy)benzoate)
Structure is
Initiator 651 (2,2-dimethoxy-1,2-diphenylethan-1-one) structure for being used is
The ratio (weight ratio) of each component is shown in Table 1 and table 2. respectively in used polymerisable monomer in embodiment 1,2
The proportioning of the polymerized monomer each component used in the embodiment 1 of table 1.
| Title | Ratio (wt%) |
| HPMA | 45.6 |
| LMA | 30.4 |
| Bis-EMA15 | 16.4 |
| PEGDA600 | 7.6 |
The proportioning of the polymerized monomer each component used in the embodiment 2 of table 2.
| Title | Ratio (wt%) |
| HPMA | 45.6 |
| LMA | 30.4 |
| Bis-EMA15 | 11.4 |
| PEGDA600 | 7.6 |
| C6M | 5.0 |
Embodiment 1
The liquid crystal material selected in the present embodiment is Nematic phase liquid crystal material (N-LC), and entitled SLC-1717 buys certainly
Shijiazhuang Cheng Zhiyonghua liquid crystal materials Co., Ltd.Those skilled in the art also the associated liquid crystal of commercially available other companies or from
Row mixture is obtained.The dyestuff selected in the present embodiment is blue and weld, and buying from Yuyao City chaste tree sea chemical color has
Limit company, those skilled in the art also the dyestuff of commercially available other companies or voluntarily synthesizes, and can be applied to the present invention thin
The preparation of film.
Step one：
Mixture mixture M1。M1In selected liquid crystal, polymerisable monomer, initiator, the title of dyestuff and its with such as table
Listed by 3.Each component in table 2 is carried out into mixture according to proportioning, and is stirred at room temperature to form isotropic liquid, mixing is equal
It is even.Mixture gross mass is 15g.
Mixture M in the embodiment 1 of table 3.1The proportioning of each material for being used
| Title | Ratio (wt%) |
| N-LC | 55.2 |
| Polymerisable monomer | 43.5 |
| Initiator | 0.5 |
| Blue dyes | 0.8 |
Step 2：
Using coating apparatus by M1It is coated in and a piece of is coated with the plastic sheeting of tin indium oxide (ITO) electrically conducting transparent that (ITO leads
Electric layer is upward), form one layer of uniform blueness coating.
Step 3：
Under conditions of nitrogen protection, the coating in step 2 is irradiated using the ultraviolet light of 365nm, ultraviolet light intensity
It is 8mw/cm2, light application time is 600s, forms the photochromic layer Y doped with blue dyes1。
Step 4：
Mixture mixture M2。M2In selected liquid crystal, polymerisable monomer, initiator, the title of dyestuff, with the such as institute of table 3
Row.Each component in table 4 is carried out into mixture according to proportioning, and is stirred at room temperature to form isotropic liquid, be well mixed.It is mixed
Compound gross mass is 15g.
Mixture M in the embodiment 1 of table 4.2The proportioning of each material for being used
| Title | Ratio (wt%) |
| N-LC | 66.0 |
| Polymerisable monomer | 32.7 |
| Initiator | 0.5 |
| Weld | 0.8 |
Step 5：
Using coating apparatus by M2It is coated in photochromic layer Y1On, form one layer of uniform yellow coating.
Step 6：
The plastic sheeting of ITO conductive layer (conductive layer is inside) is coated with by another to be covered on the yellow coating of step 5.
Step 7：
By this film at room temperature by wavelength for the ultraviolet light of 365nm is irradiated, ultraviolet light intensity is 0.5mw/cm2, light
It is 600s according to the time, that is, obtains the electrochomeric films of embodiment 1.
By the photochromic layer Y in step 3115 days are immersed in cyclohexane solvent to wash away liquid crystal molecule, are seen with ESEM
The pattern of the macromolecule network of blue coating cross sections is examined, as shown in Figure 1.
The electrochromic film that will be finally given is soaked in cyclohexane solvent 15 days to wash away liquid crystal molecule, uses ESEM
The pattern of the macromolecule network of yellow coating cross sections is observed, as shown in Figure 2.
Using reflectance spectrum of the ultraviolet-uisible spectrophotometer testing film in the case where 30V voltages and 75V voltages is applied, such as scheme
Shown in 3.
Embodiment 2
The liquid crystal material selected in the present embodiment is liquid crystal material of cholesteric phase (N*-LC), is by used in example 1
Nematic phase liquid crystal material SLC-1717 and the mixture of chiral compound S 811 form (SLC-1717 of 90 weight portions and 10 weight portions
S811 mixes).Those skilled in the art also the associated liquid crystal of commercially available other companies or voluntarily mixture be obtained.In the present embodiment
The dyestuff of selection is red and weld, is bought from Yuyao City Jing Hai chemical colors Co., Ltd, those skilled in the art
Member also the dyestuff of commercially available other companies or voluntarily synthesizes, and can be applied to the preparation of film of the present invention.
Step one：
Mixture mixture H1。H1In selected liquid crystal, polymerisable monomer, initiator, the title of dyestuff and its with such as table
Listed by 5.Each component in table 5 is carried out into mixture according to proportioning, and is stirred at room temperature to form isotropic liquid, mixing is equal
It is even.Mixture gross mass is 15g.
Mixture H in the embodiment 2 of table 5.1The proportioning of each material for being used
| Title | Ratio (wt%) |
| N*-LC | 57.0 |
| Polymerisable monomer | 41.7 |
| Initiator | 0.5 |
| Orchil | 0.8 |
Step 2：
Using coating apparatus by H1It is coated in and a piece of is coated with (ITO on the plastic sheeting of tin indium oxide (ITO) transparency conducting layer
Conductive layer is upward), form one layer of uniform red coatings.
Step 3：
Under conditions of nitrogen protection, the coating in step 2 is irradiated using the ultraviolet light of 365nm, ultraviolet light intensity
It is 6.0mw/cm2, light application time is 90s, forms the photochromic layer Y doped with orchil1。
Step 4：
Mixture mixture H2。H2In selected liquid crystal, polymerisable monomer, initiator, the title of dyestuff and its with such as table
Listed by 6.Each component in table 6 is carried out into mixture according to proportioning, and is stirred at room temperature to form isotropic liquid, mixing is equal
It is even.Mixture gross mass is 15g.
Mixture H in the embodiment 2 of table 6.2The proportioning of each material for being used
| Title | Ratio (wt%) |
| N*-LC | 70.2 |
| Polymerisable monomer | 28.5 |
| Initiator | 0.5 |
| Weld | 0.8 |
Step 5：
Using coating apparatus by H2It is coated in photochromic layer Y1On, form one layer of uniform blueness coating.
Step 6：
The plastic sheeting of ITO conductive layer (conductive layer is inside) is coated with by another to be covered on the blue coating of step 5.
Step 7：
By this film at room temperature by wavelength for the ultraviolet light of 365nm is irradiated, ultraviolet light intensity is 0.5mw/cm2, light
It is 90s according to the time, film is then made into Top electrode, applies 50.0Hz, 170v voltages, and continue with the ultraviolet light of 365nm
Irradiated, ultraviolet light intensity is 1.5mw/cm2, exposure time is 10min, that is, obtain the electrochomeric films of embodiment 2.
By the photochromic layer Y in step 3115 days are immersed in cyclohexane solvent to wash away liquid crystal molecule, are seen with ESEM
The pattern of the macromolecule network in red coatings section is examined, as shown in Figure 4.
The electrochromic film that will be finally given is soaked in cyclohexane solvent 15 days to wash away liquid crystal molecule, uses ESEM
The pattern of the macromolecule network of yellow coating cross sections is observed, as shown in Figure 5.
Applying 63V and applying the reflectance spectrum under 92V voltages using ultraviolet-uisible spectrophotometer testing film, such as scheming
Shown in 6.
It should be noted last that, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted.Although ginseng
The present invention is described in detail according to embodiment, it will be apparent to an ordinarily skilled person in the art that to technical side of the invention
Case is modified or equivalent, and without departure from the spirit and scope of technical solution of the present invention, it all should cover in the present invention
Right in the middle of.
Claims (10)
1. a kind of electrochromic film, it is characterised in that the electrochromic film is made up of multilayer materials, every layer of composite
Including macromolecule network, liquid crystal molecule and dyestuff；The liquid crystal molecule is dispersed in inside the macromolecule network；The macromolecule
Visible ray tool of the dyestuff in dyestuff, and different composite material layer to different-waveband is dispersed between network and the liquid crystal molecule
There is absorption.
2. electrochromic film according to claim 1, it is characterised in that prepare liquid crystal material in every layer of raw material of composite
Material, polymerisable monomer, the proportioning of dyestuff are：
Liquid crystal material：10.0~90.0 weight portions；
Polymerisable monomer：10.0~80.0 weight portions；
Dyestuff：0.01~20.0 weight portion.
3. electrochromic film according to claim 2, it is characterised in that the polymerisable monomer all can by non-liquid crystal
Polymerized monomer is constituted, or is collectively constituted by liquid crystal liquid crystal property polymerisable monomer and non-liquid crystal polymerisable monomer.
4. electrochromic film according to claim 3, it is characterised in that one or more layers the institute in the composite
State macromolecule network to be polymerized jointly by liquid crystal liquid crystal property polymerisable monomer and non-liquid crystal polymerisable monomer, corresponding liquid crystal molecule
It is liquid crystal material of cholesteric phase；Or, one or more layers the macromolecule network in the composite can by non-liquid crystal
Polymerized monomer is polymerized, and corresponding liquid crystal molecule is Nematic phase liquid crystal material and/or liquid crystal material of cholesteric phase.
5. electrochromic film according to claim 4, it is characterised in that the non-liquid crystal polymerisable monomer is non-liquid crystal
Property ultraviolet light polymerisable monomer, selected from one or more in following material：Unsaturated polyester (UP), epoxy acrylate, polyurethane
Acrylate, polyester acrylate, epoxy acrylate, polyenoid thiol, polyether acrylate, water-and acrylate and second
Alkenyl ethers；The liquid crystal liquid crystal property polymerisable monomer is liquid crystal liquid crystal property ultraviolet light polymerisable monomer, selected from the one kind in following material or
It is various：
Wherein, m, n are 4~8 integer, and x, y are 1 or 2, and E, Q each stand alone as acrylate-based, epoxide group, polyurethane third
Olefin(e) acid ester group or sulfydryl.
6. electrochromic film according to claim 1, it is characterised in that the drive of liquid crystal molecule in every layer of composite
Dynamic voltage is different.
7. electrochromic film according to claim 1, it is characterised in that the mesh of macromolecule network in every layer of composite
Size is 1 μm~100 μm.
8. a kind of method for preparing any electrochromic film of claim 1~7, comprises the following steps：
1) by liquid crystal material, polymerisable monomer, dyestuff R1With initiator mixing, uniform coating T is obtained1, wherein described polymerizable
Monomer is non-liquid crystal ultraviolet light polymerisable monomer；
2) by coating T1Uniform, formation coating L is coated with conductive film1；
3) ultraviolet light coating L is utilized under conditions of inert gas shielding1For a period of time, photochromic layer Y is obtained1；
4) by liquid crystal material, polymerisable monomer, dyestuff R2With initiator mixing, uniform coating T is obtained2, wherein described polymerizable
Monomer is non-liquid crystal ultraviolet light polymerisable monomer；By coating T2In photochromic layer Y1Upper coating is uniform, forms coating L2；Then exist
Ultraviolet light coating L is utilized under conditions of inert gas shielding2For a period of time, photochromic layer Y is obtained2；
5) repeat the above steps, until obtaining applying Ln, wherein n is natural number；
6) another piece of conductive film is layered on coating LnOn, electric field is applied by conductive film, while carrying out ultraviolet lighting to film
Penetrate, the remaining polymerisable monomer polymerization in film inside is complete, obtains electrochomeric films.
9. a kind of preparation method for preparing any electrochromic film of claim 1~7, comprises the following steps：
1) by liquid crystal material, polymerisable monomer, dyestuff R1With initiator mixing, uniform coating T is obtained1, wherein described polymerizable
Monomer is collectively constituted by liquid crystal liquid crystal property ultraviolet light polymerisable monomer and non-liquid crystal ultraviolet light polymerisable monomer；
2) by T1Uniform, formation coating L is coated with conductive film1；
3) ultraviolet light coating L is utilized under conditions of inert gas shielding1, make coating L1Middle non-liquid crystal ultraviolet light can gather
There is incomplete polymerisation in the liquid crystal liquid crystal property ultraviolet light polymerisable monomer for closing monomer sum, obtain pre- poly layer Y1；
4) by liquid crystal material, polymerisable monomer, dyestuff R2With initiator mixing, uniform coating T is obtained2, wherein described polymerizable
Monomer is collectively constituted by liquid crystal liquid crystal property ultraviolet light polymerisable monomer and non-liquid crystal ultraviolet light polymerisable monomer；By coating T2In pre-polymerization
Layer Y1Upper coating is uniform, forms coating L2；Ultraviolet light coating L is then utilized under conditions of inert gas shielding2, make painting
Layer L2There is incomplete polymerisation in the liquid crystal liquid crystal property ultraviolet light polymerisable monomer of middle non-liquid crystal ultraviolet light polymerisable monomer sum, obtain
To pre- poly layer Y2；
5) repeat the above steps, until obtaining pre- poly layer Yn, wherein n is natural number；
6) another piece of conductive film is layered on pre- poly layer YnOn, electric field is applied by conductive film, while continuation carries out purple to film
Outer light irradiation, makes the remaining polymerisable monomer polymerization in conductive film inside complete, obtains electrochomeric films.
10. method according to claim 8 or claim 9, it is characterised in that the non-liquid crystal ultraviolet light polymerisable monomer is selected from
One or more in following material：Unsaturated polyester (UP), epoxy acrylate, urethane acrylate, polyester acrylate, ring
Oxypropylene acid esters, polyenoid thiol, polyether acrylate, water-and acrylate and vinyl ethers；
The liquid crystal liquid crystal property ultraviolet light polymerisable monomer is selected from one or more in following material：
Wherein, m, n are 4~8 integer, and x, y are 1 or 2, and E, Q each stand alone as acrylate-based, epoxide group, polyurethane third
Olefin(e) acid ester group or sulfydryl；
The liquid crystal material is Nematic phase liquid crystal material and/or liquid crystal material of cholesteric phase；
The initiator is selected from one or more in following material：Benzophenone, benzoin dimethylether, chloro thioxanthone,
2,4- diethyl thioxanthones, isopropyl thioxanthone and 2- hydroxyl -2,2- methyl isophthalic acids-phenylacetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710186039.0A CN106873279A (en) | 2017-03-24 | 2017-03-24 | A kind of electrochromic film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710186039.0A CN106873279A (en) | 2017-03-24 | 2017-03-24 | A kind of electrochromic film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106873279A true CN106873279A (en) | 2017-06-20 |
Family
ID=59173530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710186039.0A Pending CN106873279A (en) | 2017-03-24 | 2017-03-24 | A kind of electrochromic film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106873279A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110596961A (en) * | 2019-10-17 | 2019-12-20 | 北京大学 | Electric control light adjusting film and preparation method thereof |
| CN111948864A (en) * | 2020-08-21 | 2020-11-17 | 中国人民解放军96901部队25分队 | Chiral property-adjustable electrochromic device and preparation method thereof |
| CN112649996A (en) * | 2020-12-14 | 2021-04-13 | 北京科技大学 | Method for preparing broadband reflection cholesteric liquid crystal film by ink-jet printing |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202372728U (en) * | 2011-12-16 | 2012-08-08 | 京东方科技集团股份有限公司 | Color polymer dispersed liquid crystal (PDLC) display device |
| CN104130769A (en) * | 2014-08-01 | 2014-11-05 | 北京大学 | Electrochromatic functional material and electrochromatic device |
| CN104360526A (en) * | 2014-11-17 | 2015-02-18 | 张家港康得新光电材料有限公司 | Electric control dimming film |
| CN106405916A (en) * | 2016-12-16 | 2017-02-15 | 北京大学 | Reverse type electric-control liquid-crystal light adjusting film and preparation method thereof |
| CN106526945A (en) * | 2016-12-16 | 2017-03-22 | 北京大学 | Liquid crystal light adjusting film with temperature control and electric control functions and preparation method thereof |
-
2017
- 2017-03-24 CN CN201710186039.0A patent/CN106873279A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202372728U (en) * | 2011-12-16 | 2012-08-08 | 京东方科技集团股份有限公司 | Color polymer dispersed liquid crystal (PDLC) display device |
| CN104130769A (en) * | 2014-08-01 | 2014-11-05 | 北京大学 | Electrochromatic functional material and electrochromatic device |
| CN104360526A (en) * | 2014-11-17 | 2015-02-18 | 张家港康得新光电材料有限公司 | Electric control dimming film |
| CN106405916A (en) * | 2016-12-16 | 2017-02-15 | 北京大学 | Reverse type electric-control liquid-crystal light adjusting film and preparation method thereof |
| CN106526945A (en) * | 2016-12-16 | 2017-03-22 | 北京大学 | Liquid crystal light adjusting film with temperature control and electric control functions and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110596961A (en) * | 2019-10-17 | 2019-12-20 | 北京大学 | Electric control light adjusting film and preparation method thereof |
| CN111948864A (en) * | 2020-08-21 | 2020-11-17 | 中国人民解放军96901部队25分队 | Chiral property-adjustable electrochromic device and preparation method thereof |
| CN111948864B (en) * | 2020-08-21 | 2023-05-16 | 中国人民解放军96901部队25分队 | Electrochromic device with adjustable chiral property and preparation method thereof |
| CN112649996A (en) * | 2020-12-14 | 2021-04-13 | 北京科技大学 | Method for preparing broadband reflection cholesteric liquid crystal film by ink-jet printing |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106773234B (en) | A kind of temperature control light modulation film and preparation method thereof with shielding near infrared light function | |
| CN106405916B (en) | A kind of flexibility transreflective liquid crystal light modulation film and preparation method thereof | |
| CN106526945B (en) | A kind of liquid crystal light modulation film and preparation method thereof having both temperature control and electric control function | |
| CN101679865B (en) | Pre-polymer formulations for liquid crystal displays | |
| CN106699960B (en) | A kind of temperature control light modulation film and its step-by-step polymerization preparation method | |
| CN106896541A (en) | A kind of thermochromic thin film and preparation method thereof | |
| Shen et al. | Electrically switchable light transmittance of epoxy-mercaptan polymer/nematic liquid crystal composites with controllable microstructures | |
| CN106886102A (en) | A kind of trans electrically-controlled liquid crystal light modulation film and preparation method thereof | |
| CN106873279A (en) | A kind of electrochromic film and preparation method thereof | |
| CN106932992A (en) | The flexible electro-chromic device and preparation method of a kind of regulation and control near infrared light | |
| CN107015382A (en) | A kind of thin-film material for having electroluminescent and thermochromic function concurrently and preparation method thereof | |
| CN108363255B (en) | A kind of electrochromism membrane material and its electrochromism membrane module of preparation | |
| CN108957825B (en) | Trans-electric control dimming film capable of adjusting near-infrared light transmittance and preparation method thereof | |
| CN106324883B (en) | The method that ultraviolet-heating step-by-step polymerization prepares cholesteric liquid crystal function film | |
| CN106483730A (en) | A kind of have controllable liquid crystal film of total reflection function and preparation method thereof | |
| CN106324884A (en) | Preparation method for reverse polymer dispersed liquid crystal thin film | |
| CN109752879A (en) | A kind of electric-controlled light-regulating film of maskable near infrared light and preparation method thereof | |
| CN109752893B (en) | Temperature control light adjusting film for sectionally regulating and controlling visible light and near infrared light transmissivity and preparation method thereof | |
| DE19623147A1 (en) | Twist liq. crystal displays used for e.g. computer or work processor screens | |
| CN108663828A (en) | A kind of electric-controlled light-regulating film and preparation method thereof | |
| CN106366235A (en) | Color polymer dispersed liquid crystal material preparation method | |
| CN110007499A (en) | A kind of Multifunctional liquid crystal light modulation film with multiple response, transmission element and preparation method thereof | |
| US11905417B2 (en) | Anthraquinone compound, liquid crystal composition for dimming including said compound, and dimming element | |
| CN107015394A (en) | Trans electric-controlled light-regulating film with shielding near infrared light function and preparation method thereof | |
| CN103074074A (en) | Light-modulatable composition and formation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170620 |