阅读说明：本技术 一种可水洗可拉伸的电子纸显示设备及其制备方法 (Washable stretchable electronic paper display equipment and preparation method thereof ) 是由 杨柏儒 邱志光 张高帆 钟敏 吴梓毅 秦宗 吴进 邓少芝 于 2021-10-21 设计创作，主要内容包括：本申请属于书写工具技术领域,尤其涉及一种可水洗可拉伸的电子纸显示设备及其制备方法。本申请的电子纸显示设备,包括凝胶电极层和微胶囊弹性体显示层,凝胶电极层固定设置在微胶囊弹性体显示层的表面；凝胶电极层的制备方法：凝胶单体、金属盐、碳纳米管、交联剂和引发剂混合,得到凝胶预制液；将凝胶预制液置于模具中,固化处理后得到凝胶电极层；微胶囊弹性体显示层的制备方法：将高分子材料与微胶囊混合,得到微胶囊弹性体溶液；将微胶囊弹性体溶液进行固化处理,将固化产物浸泡在溶剂中,洗涤和干燥,得到微胶囊弹性体显示层。本申请的电子纸显示设备,有效解决现有电子黑板/电子白板/书写屏等设备存在的结构复杂,不能水洗的缺陷。(The application belongs to the technical field of writing tools, and particularly relates to washable stretchable electronic paper display equipment and a preparation method thereof. The electronic paper display device comprises a gel electrode layer and a microcapsule elastomer display layer, wherein the gel electrode layer is fixedly arranged on the surface of the microcapsule elastomer display layer; the preparation method of the gel electrode layer comprises the following steps: mixing a gel monomer, a metal salt, a carbon nano tube, a cross-linking agent and an initiator to obtain a gel prefabricated liquid; placing the gel prefabricated liquid in a mold, and curing to obtain a gel electrode layer; the preparation method of the microcapsule elastomer display layer comprises the following steps: mixing a high polymer material with microcapsules to obtain a microcapsule elastomer solution; and (3) curing the microcapsule elastomer solution, soaking the cured product in a solvent, washing and drying to obtain the microcapsule elastomer display layer. The electronic paper display equipment effectively overcomes the defects that the existing electronic blackboard/electronic whiteboard/writing screen equipment is complex in structure and cannot be washed by water.)

1. The electronic paper display device is characterized by comprising a gel electrode layer and a microcapsule elastomer display layer, wherein the gel electrode layer is fixedly arranged on the surface of the microcapsule elastomer display layer;

the preparation method of the gel electrode layer comprises the following steps:

step 1, mixing a gel monomer, a metal salt, a carbon nano material, a cross-linking agent and an initiator to obtain a gel prefabricated liquid;

step 2, placing the gel prefabricated liquid in a mold, and curing to obtain a gel electrode layer;

the preparation method of the microcapsule elastomer display layer comprises the following steps:

step one, mixing a high polymer material with microcapsules to obtain a microcapsule elastomer solution;

and step two, curing the microcapsule elastomer solution, then soaking the cured product in a solvent, taking out the cured product, and washing and drying the cured product to obtain the microcapsule elastomer display layer.

2. The electronic paper display device according to claim 1, wherein in step 1, the gel monomer is selected from one or more of anionic unsaturated monomers and salts thereof, thiol group-containing unsaturated monomers, phenolic hydroxyl group-containing unsaturated monomers, amide group-containing unsaturated monomers, and amino group-containing unsaturated monomers.

3. The electronic paper display device of claim 2, wherein the anionic unsaturated monomer is selected from one or more of acrylamide, methacrylamide, anhydrous maleic acid, itaconic acid, cinnamic acid, vinyl sulfonic acid, propylene toluene sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, 2- (meth) acrylamide-2-methyl propane sulfonic acid, 2- (meth) acryloyl ethylamine sulfonic acid, 2- (meth) acryloyl propanol sulfonic acid, and 2-hydroxyethyl (meth) acryloyl phosphate;

the amido unsaturated monomer is selected from one or more of acrylamide, methacrylamide and N-ethyl (methyl) acrylamide;

the amino unsaturated monomer is selected from N, N-dimethylaminoethyl (meth) acrylate or/and N, N-dimethylaminopropyl (meth) acrylate.

4. The electronic paper display device of claim 1, wherein in step 1, the metal salt is selected from one or more of sodium salt, lithium salt, potassium salt, calcium salt, magnesium salt, and ammonium salt;

the carbon nano material is selected from one or more of single-walled carbon nano tube, multi-walled carbon nano tube, graphene, graphite and carbon nano sheet.

5. The electronic paper display device of claim 1, wherein in step 1, the cross-linking agent is selected from one or more of N, N-methylenebisacrylamide, polyethylene glycol, ethylene glycol, propylene glycol, glycerol, pentaerythritol, ethylenediamine, ethylene carbonate, propylene carbonate, N' -methylenebisdialkylphosphinyl (meth) acrylamide, (poly) ethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, (poly) ethylene glycol diglycidyl ether, and glycerol diglycidyl ether;

the initiator is selected from a photoinitiator or a thermal initiator; the photoinitiator is selected from one or more of benzoin derivatives, benzyl derivatives, acetophenone derivatives, benzophenone derivatives and azo compounds; the thermal initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl peroxide, butanone peroxide, amiobutyronitrile compounds, amitradine compounds, cycloamitradine compounds and amitramine compounds.

6. The electronic paper display device of claim 1, wherein in the step 1, the concentration of the gel monomer in the gel pre-forming liquid is 1-5 mol/L; the concentration of the metal salt is 1-5 mol/L; the mass percentage of the carbon nano material is 0.001-0.1 wt%; the mass percentage of the cross-linking agent is 0.01-0.1 wt%; the mass percentage of the initiator is 0.1-0.5 wt%.

7. The electronic paper display device of claim 1, wherein in step one, the polymer material is selected from one or more of PDMS, ecoflex, polyurethane, or SEBS; the mass ratio of the high polymer material to the microcapsule is (1-5) to (1-5).

8. The electronic paper display device of claim 1, wherein in step two, the solvent is selected from one or more of benzophenone, trimethylsilyl methacrylate, and propyl 3- (trimethoxysilyl) methacrylate.

9. The electronic paper display device of claim 1, further comprising a patterned gel electrode layer on which a preset pattern is provided;

the gel electrode layer, the microcapsule elastomer display layer and the patterned gel electrode layer are sequentially attached, combined and fixed, and display voltage is applied to the gel electrode layer and the patterned gel electrode layer, so that the display device with the preset pattern is obtained.

10. The method for manufacturing the electronic paper display device according to any one of claims 1 to 9, comprising the steps of:

arranging a gel electrode layer on the surface of the microcapsule elastomer display layer in situ, and carrying out curing treatment to obtain the electronic paper display device with the gel electrode layer and the microcapsule elastomer display layer fixedly connected with each other;

the preparation method of the gel electrode layer comprises the following steps:

step 1, mixing a gel monomer, a metal salt, a carbon nano material, a cross-linking agent and an initiator to obtain a gel prefabricated liquid;

step 2, placing the gel prefabricated liquid in a mold, and curing to obtain a gel electrode layer;

the preparation method of the microcapsule elastomer display layer comprises the following steps:

step one, mixing a high polymer material with microcapsules to obtain a microcapsule elastomer solution;

and step two, curing the microcapsule elastomer solution, soaking the cured product in a solvent, taking out, and washing and drying to obtain the microcapsule elastomer display layer.

Technical Field

The application belongs to the technical field of display equipment, and particularly relates to washable stretchable electronic paper display equipment and a preparation method thereof.

Background

Traditional electrophoretic patterns and pixel presets can only display fixed and limited information on a fixed screen, and cannot be changed after packaging. Therefore, a reflective display device with a rewritable function is widely used in education scenes. In order to implement the rewritable function, a conventional solution is to add a thin film transistor TFT array layer as a switch or a predetermined mode function layer to reinstall information.

Obviously, most of the existing devices such as the electronic blackboard/electronic whiteboard/writing screen need to additionally add a module in the screen body to realize pattern customization, and the module comprises a TFT array layer, a bluetooth module, a wireless reader-writer and the like, so that the existing writable display device has the defects of complex structure and incapability of being washed by water.

Disclosure of Invention

In view of this, the application provides a washable stretchable electronic paper display device and a preparation method thereof, which effectively solve the defects that the existing electronic blackboard/electronic whiteboard/writing screen and other devices are complex in structure and cannot be washed with water.

The application provides a washable electronic paper display device in a first aspect, which comprises a gel electrode layer and a microcapsule elastomer display layer, wherein the gel electrode layer is fixedly arranged on the surface of the microcapsule elastomer display layer;

the preparation method of the gel electrode layer comprises the following steps:

step 1, mixing a gel monomer, a metal salt, a carbon nano material, a cross-linking agent and an initiator to obtain a gel prefabricated liquid;

step 2, placing the gel prefabricated liquid in a mold, and curing to obtain a gel electrode layer;

the preparation method of the microcapsule elastomer display layer comprises the following steps:

step one, mixing a high polymer material with microcapsules to obtain a microcapsule elastomer solution;

and step two, curing the microcapsule elastomer solution, then soaking the cured product in a solvent, taking out the cured product, and washing and drying the cured product to obtain the microcapsule elastomer display layer.

Specifically, a specific pattern can be arranged in the mold according to actual needs, and the surface of the gel electrode layer is provided with the specific pattern after curing; the material of the mould is PET, PTFE or PMMA and other conventional materials.

Specifically, in the second step, the microcapsule elastomer solution may be subjected to a curing reaction in a mold, or a microcapsule elastomer display layer may be prepared by blade coating, and both of these two ways may control the thickness, shape and size of the microcapsule elastomer display layer.

In another embodiment, in step 1, the gel monomer is selected from one or more of anionic unsaturated monomers and salts thereof, thiol group-containing unsaturated monomers, phenolic hydroxyl group-containing unsaturated monomers, amido unsaturated monomers, and amino unsaturated monomers.

In another embodiment, the anionic unsaturated monomer is selected from one or more of acrylamide, methacrylamide, anhydrous maleic acid, itaconic acid, cinnamic acid, vinyl sulfonic acid, propylene toluene sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, 2- (meth) acryloyl ethylamine sulfonic acid, 2- (meth) acryloyl propanol sulfonic acid, and 2-hydroxyethyl (meth) acryloyl phosphate;

the amido unsaturated monomer is selected from one or more of acrylamide, methacrylamide and N-ethyl (methyl) acrylamide;

the amino unsaturated monomer is selected from N, N-dimethylaminoethyl (meth) acrylate or/and N, N-dimethylaminopropyl (meth) acrylate.

In another embodiment, in step 1, the metal salt is selected from one or more of sodium salt, lithium salt, potassium salt, calcium salt, magnesium salt and ammonium salt; the carbon nano material is selected from one or more of single-walled carbon nano tube, multi-walled carbon nano tube, graphene, graphite and carbon nano sheet.

In another embodiment, in step 1, the metal salt is selected from one or more of lithium chloride, potassium chloride, calcium chloride, sodium chloride and magnesium chloride.

In another embodiment, in step 1, the crosslinking agent is selected from one or more of N, N-methylenebisacrylamide, polyethylene glycol, ethylene glycol, propylene glycol, glycerol, pentaerythritol, ethylenediamine, carbonate ethylene, propylene carbonate, N' -methylenebisdialkylphosphinyl (meth) acrylamide, (poly) ethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, (poly) ethylene glycol diglycidyl ether, and glycerol diglycidyl ether;

the initiator is selected from a photoinitiator or a thermal initiator; the photoinitiator is selected from one or more of benzoin derivatives, benzyl derivatives, acetophenone derivatives, benzophenone derivatives and azo compounds; the thermal initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl peroxide, butanone peroxide, amiobutyronitrile compounds, amitradine compounds, cycloamitradine compounds and amitramine compounds.

In another embodiment, in the step 1, the concentration of the gel monomer in the gel pre-preparation liquid is 1-5 mol/L; the concentration of the metal salt is 1-5 mol/L; the mass percentage of the carbon nano material is 0.001-0.1 wt%; the mass percentage of the cross-linking agent is 0.01-0.1 wt%; the mass percentage of the initiator is 0.1-0.5 wt%.

Specifically, in step 2, the gel electrode layer can be prepared by using a conventional curing method, and the curing treatment is selected from thermal curing or/and photo-curing.

Specifically, in step 1, the carbon nanomaterial may be a carboxylated carbon nanomaterial, and may be a carboxylated single-walled carbon nanotube, a carboxylated multi-walled carbon nanotube, carboxylated graphene, carboxylated graphite, or a carboxylated carbon nanosheet; the carbon nanomaterial may also be a non-carboxylated carbon nanomaterial.

In another embodiment, in the first step, the polymer material is selected from one or more of PDMS, ecoflex, polyurethane, or SEBS.

In another embodiment, in the step one, the mass ratio of the polymer material to the microcapsule is (1-5): 1-5.

In another embodiment, in step two, the solvent is selected from one or more of benzophenone, trimethylsilyl methacrylate, and 3- (trimethoxysilyl) propyl methacrylate.

In particular, soaking the cured product in a solvent is a key to the in-situ adhesion of the microcapsule elastomer display layer when assembled with the gel electrode layer.

In another embodiment, the gel electrode layer fixedly disposed on the surface of the microcapsule elastomer display layer specifically includes: and arranging the gel electrode layer on the surface of the microcapsule elastomer display layer in situ in a light curing or heat curing mode, so that the gel electrode layer and the microcapsule elastomer display layer are fixedly connected with each other.

Specifically, in the second step, the microcapsule elastomer display layer can be prepared by using the conventional curing method, and the curing treatment is selected from thermal curing or/and light curing.

Specifically, in the second step, the microcapsule elastomer solution is cured and then immersed in a benzophenone solution (10 wt.% ethanol) at room temperature; the microcapsule/elastomer was then washed several times with ethanol and deionized water and then thoroughly dried with nitrogen to give a microcapsule elastomer display layer.

In another embodiment, the display device further comprises a patterned gel electrode layer, wherein a preset pattern is arranged on the patterned gel electrode layer;

the gel electrode layer, the microcapsule elastomer display layer and the patterned gel electrode layer are sequentially attached, combined and fixed, and after voltage is applied to the gel electrode layer and the patterned gel electrode layer, the display device displaying the preset pattern is obtained.

Specifically, the electronic paper display device of the present application may be provided with a three-layer structure, that is, a three-layer structure of a gel electrode layer, a microcapsule elastomer display layer, and a patterned gel electrode layer in sequence, wherein a display voltage (15V to 100V forward voltage or reverse voltage, application time is 1ms to 10min) is applied between the gel electrode layer and the patterned gel electrode layer, and a preset pattern on the patterned gel electrode layer is displayed on the electronic paper display device after the voltage is removed; when the preset pattern fades away, reapplying display voltage to the patterned gel electrode layer and the gel electrode layer, and after the voltage is removed, enabling the preset pattern to be displayed on the electronic paper display device again; when the preset pattern needs to be eliminated, a voltage which is opposite to the display voltage in polarity and is 15V-100V is applied to the patterned gel electrode layer and the gel electrode layer, and the preset pattern can be eliminated after the voltage is removed. Therefore, the electronic paper display device with the three-layer structure has the characteristics of displaying preset patterns for a long time (>40 days) after power failure, being washable, stretchable and deformable, and has wide application.

The second aspect of the application provides a preparation method of a washable stretchable electronic paper display device, which comprises the following steps:

arranging a gel electrode layer on the surface of the microcapsule elastomer display layer in situ, and carrying out curing treatment to obtain the electronic paper display device with the gel electrode layer and the microcapsule elastomer display layer fixedly connected with each other;

the preparation method of the gel electrode layer comprises the following steps:

step 1, mixing a gel monomer, a metal salt, a carbon nano material, a cross-linking agent and an initiator to obtain a gel prefabricated liquid;

step 2, placing the gel prefabricated liquid in a mold, and curing to obtain a gel electrode layer;

the preparation method of the microcapsule elastomer display layer comprises the following steps:

step one, mixing a high polymer material with microcapsules to obtain a microcapsule elastomer solution;

and step two, curing the microcapsule elastomer solution, soaking the cured product in a solvent, taking out, and washing and drying to obtain the microcapsule elastomer display layer.

Specifically, when the double-layer display device is used, a forward voltage or a reverse voltage of 15V-100V is applied to a pen point of the conductive pen, and writing can be performed on a microcapsule elastomer display layer of the double-layer display device; when the content of the double-layer display device needs to be erased, the voltage with the polarity opposite to that of writing and the voltage of 15V-100V is applied to the pen point of the conductive pen, so that the content on the device can be erased.

The application provides a washable electronic paper display device, which is a double-layer writable display device structure formed by mutually combining a gel electrode layer and a microcapsule elastomer display layer, wherein the gel electrode layer can be adhered to the surface of the microcapsule elastomer display layer in situ to form integration, the interface adhesion is very strong, and desorption slippage cannot occur, so that the washable electronic paper display device has good stretchability (> 80%); the integrated double-layer electronic paper display device structure has water washability, patterns on the electronic paper display device can be kept for a long time (>43 days), and the electronic paper display device still has the display capacity of the long-time pattern keeping capacity under water washing; the electronic paper display device that can write of this application user mode is simple, adopts the conductive pen that has different polarity voltages to write and clean on this display device, and is visible, and the electronic paper display device of this application need not complicated drive communication circuit realization pattern self-definition such as extra functional layer (like TFT array layer) or wireless, erasable, washable and the effect of tensile deformation, and the equipment structure of this application is very simple, has simplified the complex construction of current electronic blackboard/writing screen.

To sum up, the electronic paper display device of this application has can stretch, washable's characteristic, can bear the tensile up to 80% to still have bistable state and keep the pattern more than 40 days under the washing state, this has demonstrated that the display device of this application is significant to realizing wearable demonstration.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.

Fig. 1 is a flowchart of a method for manufacturing an electronic paper display device according to an embodiment of the present disclosure;

fig. 2 is a microscopic structure diagram of an electronic paper display device provided in an embodiment of the present application;

fig. 3 is a real object diagram of an electronic paper display device provided in an embodiment of the present application after writing;

fig. 4 is a diagram of an electronic paper display device soaked in water after being written according to an embodiment of the present application;

fig. 5 is a diagram of a real object of the electronic paper display device provided in the embodiment of the present application after being washed after being written;

fig. 6 is a diagram of a bent object after writing of the electronic paper display device according to the embodiment of the application;

fig. 7 is a real object diagram of the electronic paper display device curled after writing according to the embodiment of the present application;

fig. 8 is a diagram of an object distorted after writing by an electronic paper display device according to an embodiment of the present application;

fig. 9 is a drawing of an object after stretching after writing by the electronic paper display device according to the embodiment of the application.

Detailed Description

The application provides washable and stretchable electronic paper display equipment and a preparation method thereof, which are used for solving the technical defects that in the prior art, electronic blackboard/electronic whiteboard/writing screen equipment and the like are complex in structure and cannot be washed by water.

The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

The raw materials and reagents used in the following examples are commercially available or self-made.

Acrylamide (AAm), Ammonium Persulfate (APS), N-methylenebisacrylamide, (MBAA, a crosslinker for AAm), lithium chloride (LiCl), and Benzophenone (BP) of the following examples were purchased from Sigma-Aldrich.

Examples the following examples Polydimethylsiloxane (PDMS) elastomer (Sylgard 184) was purchased from Dow Corning Inc (Dow Corning Inc.) using PDMS as the AB component, where the a component was the PDMS base material and the B component was the corresponding curing agent.

The microcapsules of the following examples were purchased from Olympic electronics, Inc., Guangzhou, and were derived from conventional electrophoretic display technology, and have particles of different colors, and the microcapsules of the present example have black and white particles; the white particles and the black particles are mixed with each other in an original state; when a certain potential is applied, the white particles or the black particles move directionally under the specific potential.

The aqueous single-walled carbon nanotube dispersions of the following examples were purchased and carboxylated.

Example 1

The embodiment of the application relates to a double-layer electronic paper display device which can be stretched, washed, erased and written, in particular to a double-layer electronic blackboard (marked as a Bilayer structure SEPD), and the preparation method comprises the following steps:

referring to fig. 1, fig. 1 is a flowchart of a method for manufacturing an electronic paper display device according to an embodiment of the present application.

The preparation method of the gel electrode layer comprises the following steps:

1) synthesizing 2.17mol of AAm monomer powder, 2mol of LiCl solid salt and 16mL of carboxylated single-walled carbon nanotube aqueous dispersion (the carbon nanotubes account for 0.15 wt% of the aqueous dispersion) into hydrogel in deionized water, and then adding a crosslinking agent MBAA and an initiator APS related to the AAm powder, wherein the addition amount of the MBAA is 0.06 wt% (based on the gel preparation liquid), and the addition amount of the initiator APS is 0.16 wt% (based on the gel preparation liquid), so as to form the gel preparation liquid;

2) stirring the gel precast liquid for 30min, and degassing in a vacuum chamber for 10 min;

3) cutting PET by a laser cutting machine to obtain any shape;

4) pouring the gel prefabricated liquid into the patterned PET gaps, and curing by ultraviolet light (365nm) for ten minutes in a dark room;

5) and stripping the electrode on the solidified patterned hydrogel from the mold to obtain the gel electrode layer.

The preparation method of the microcapsule elastomer display layer comprises the following steps:

1) preparing a mixture of PDMS base material and microcapsule according to the weight ratio of 2:1 to obtain a microcapsule elastomer solution;

2) stirring the microcapsule elastomer solution for 30min at room temperature, and heating to evaporate the solvent at 120 ℃ for 1 hour;

3) adding a PDMS curing agent with the amount corresponding to the amount of the PDMS base material into the microcapsule elastomer solution obtained in the step 2, uniformly stirring, placing the mixture into a mold, and heating and curing the mixture for one hour at 70 ℃ to obtain microcapsules/elastomers;

4) the microcapsules/elastomers were immersed in benzophenone solution (10 wt.% ethanol) for 4 minutes at room temperature;

5) the microcapsule/elastomer was washed three times with ethanol and deionized water and then thoroughly dried with nitrogen to give a microcapsule elastomer display layer.

Assembling:

1) attaching and assembling the gel electrode layer with the pattern taken out of the mould and the microcapsule elastomer display layer in situ, and then carrying out curing treatment under the following curing conditions: ultraviolet lamp (wavelength 365nm, intensity 80mW cm)^-1) And irradiating the assembly for 15 minutes to obtain the electronic paper display device.

When microscopic examination is performed on the electronic paper display device in the embodiment of the present application, fig. 2 is a microscopic structural diagram of the electronic paper display device in the embodiment of the present application, and it can be seen from the diagram that a mixed film interface of the gel electrode layer and the microcapsule elastomer display layer shows a strong adhesive force.

Writing tests are carried out on the microcapsule elastomer display layer of the display device of the embodiment of the application by using a conductive pen, as shown in fig. 3, a forward voltage or a reverse voltage of 15V-100V is applied to a pen point of the conductive pen, so that writing can be carried out on the display device, and the potential of the conductive pen can drive black and white particles in the microcapsule to move, so that the black and white particles are displayed on the display device; when the content of the display device needs to be erased, the voltage with the polarity opposite to that of writing and the voltage of 15V-100V is applied to the pen point of the conductive pen, so that the content on the device can be erased. After the conductive pen is used for writing, the microcapsule elastomer display layer of the electrophoretic display in the display device of the application keeps bistable state, and the written pattern can be kept for a long time, and can be kept for more than 43 days. As a result of water washing, various deformation, and stretching treatments performed on the display device according to the embodiment of the present application, as shown in fig. 4 to 9, the display device according to the present application still has a display of a pattern retention capacity for a long time, and fig. 6 to 9 show excellent stretchability in various deformation modes.

Example 2

The invention can also manufacture three-layer washable, erasable and stretchable flexible electronic paper display equipment with preset patterns, and the specific preparation method is as follows:

the preparation method of the patterned gel electrode layer comprises the following steps:

1) synthesizing 2.17mol of AAm monomer powder and 2mol of LiCl solid salt into transparent hydrogel in deionized water, and then adding a crosslinking agent MBAA and an initiator APS related to the AAm powder, wherein the addition amount of the MBAA is 0.06 wt.% (based on the patterning gel prefabricated liquid), and the addition amount of the initiator APS is 0.16 wt.% (based on the patterning gel prefabricated liquid), so as to form the patterning gel prefabricated liquid;

2) stirring the patterned gel prefabricated liquid for 30min, and degassing in a vacuum chamber for 10 min;

3) cutting PET by a laser cutting machine to obtain any shape to obtain a patterned die;

4) pouring the patterned gel pre-solution into a patterned mold (patterned PET voids), and curing with ultraviolet light (365nm) for ten minutes in a dark room;

5) and stripping the cured patterned gel electrode layer from the mold to obtain the patterned gel electrode layer which is a transparent structure.

The preparation method of the gel electrode layer comprises the following steps:

1) synthesizing 2.17mol of AAm monomer powder, 2mol of LiCl solid salt and 16mL of carboxylated single-walled carbon nanotube aqueous dispersion (the carbon nanotubes account for 0.15 wt% of the aqueous dispersion) into hydrogel in deionized water, and then adding a crosslinking agent MBAA and an initiator APS related to the AAm powder, wherein the addition amount of the MBAA is 0.06 wt% (based on the gel preparation liquid), and the addition amount of the initiator APS is 0.16 wt% (based on the gel preparation liquid), so as to form the gel preparation liquid;

2) stirring the gel precast liquid for 30min, and degassing in a vacuum chamber for 10 min;

3) pouring the gel prefabricated liquid into a square polytetrafluoroethylene mold (without patterns), and curing by ultraviolet light (365nm) in a dark room for ten minutes;

4) and peeling the solidified non-pattern gel electrode layer from the mold to obtain the gel electrode layer.

The preparation method of the microcapsule elastomer display layer comprises the following steps:

1) preparing a mixture of PDMS base material and microcapsule according to the weight ratio of 2:1 to obtain a microcapsule elastomer solution;

2) stirring the microcapsule elastomer solution for 30min at room temperature, and heating to evaporate the solvent at 120 ℃ for 1 hour;

3) adding a PDMS curing agent with the amount corresponding to the amount of the PDMS base material into the microcapsule elastomer solution obtained in the step 2, uniformly stirring, placing the mixture into a mold, and heating and curing the mixture for one hour at 70 ℃ to obtain microcapsules/elastomers;

4) the microcapsules/elastomers were immersed in benzophenone solution (10 wt.% ethanol) for 4 minutes at room temperature;

5) the microcapsule/elastomer was washed three times with ethanol and deionized water and then thoroughly dried with nitrogen to give a microcapsule elastomer display layer.

Assembling:

1) sequentially attaching and combining the obtained patterned gel electrode layer, the microcapsule elastomer display layer and the gel electrode layer in situ, and then carrying out curing treatment under the following curing conditions: ultraviolet lamp (wavelength 365nm, intensity 80mW cm)^-1) Irradiation ofAnd assembling the materials for 15 minutes to obtain the three-layer electronic paper display device.

Applying a display voltage (15V-100V forward voltage or reverse voltage, the application time is 1 ms-10 min) on the patterned gel electrode layer and the gel electrode layer, and displaying a preset pattern on the patterned gel electrode layer on the electronic paper display device after removing the voltage; when the preset pattern fades away, reapplying display voltage to the patterned gel electrode layer and the gel electrode layer, and after the voltage is removed, enabling the preset pattern to be displayed on the electronic paper display device again; when the preset pattern needs to be eliminated, a voltage which is opposite to the display voltage in polarity and is 15V-100V is applied to the patterned gel electrode layer and the gel electrode layer, and the preset pattern can be eliminated after the voltage is removed.

The gel electrode layer added with the carbon nano material is not transparent, and the display effect is influenced, so that the gel electrode layer added with the carbon nano material is required to be arranged at the bottom, and the other patterned gel electrode layer without the carbon nano material is arranged at the top.

Compared with the electronic blackboard/electronic whiteboard/writing screen in the prior art, the double-layer display equipment has not only water washability, but also good stretchability, and can bear 80% of tensile strain.

The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.