CN108962503A - A kind of preparation method and its application of ultrastability epoxy packages silver nanowires flexible transparent electrode - Google Patents
A kind of preparation method and its application of ultrastability epoxy packages silver nanowires flexible transparent electrode Download PDFInfo
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- CN108962503A CN108962503A CN201810856124.8A CN201810856124A CN108962503A CN 108962503 A CN108962503 A CN 108962503A CN 201810856124 A CN201810856124 A CN 201810856124A CN 108962503 A CN108962503 A CN 108962503A
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- silver nanowires
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0013—Apparatus or processes specially adapted for manufacturing conductors or cables for embedding wires in plastic layers
Abstract
The present invention relates to a kind of preparation method and applications of ultrastability epoxy packages silver nanowires flexible transparent electrode.The preparation method comprises the following steps: on silver nanowires dispersion to flexible parent metal, will form certain thickness dispersion liquid liquid film, then dries；Using plasma surface etching method or heating, the contact of silver nanowires is promoted；It compounds epoxy monomer and curing agent to obtain mixed liquor, using spraying or blade coating mode, mixed liquor after compounding is covered into the silver nanowires surface after corona treatment or heat treatment, is heating and curing to get ultrastability epoxy packages silver nanowires flexible transparent electrode film is arrived.The flexible transparent electrode membrane material that the present invention is prepared all has very excellent performance in terms of thermo-oxidative stability, bending resistance, rub resistance, scratch resistance, caking property, solvent resistance and resistant to sulfur aggressivity.
Description
Technical field
The invention belongs to flexible transparent conductive film fields, and in particular to a kind of ultrastability epoxy packages silver nanowires
The preparation method and applications of flexible transparent electrode.
Background technique
Transparent electrode material is with a wide range of applications in many fields, for example, transparent electrode may be used as plate electricity
The cathode material of the touch-screen display of brain and mobile phone, or it is applied to solar battery.Commercial transparent electrode is main at present
It is prepared by tin indium oxide (ITO).
The defect of ITO is: first, the content of indium is limited in the earth's crust；Second, ITO are very crisp, are not suitable for being applied to flexible dress
It sets.Therefore, the substitute of numerous ITO is come into being.The ITO substitute of mainstream has at present: metal grill, graphene, carbon nanometer
Pipe, silver nanowires.Wherein, silver nanowires has the advantage that 1) silver wire has very high draw ratio；2) silver wire is relatively easy
Synthesis；3) what silver wire can be easy carries out coating operation in flexible parent metal；4) silver wire can pass through pressure, light, heat, plasma etc.
Means are welded.
The preparation field in transparent electrode of exposed silver nanowires has very important defect.Silver nanowires is for soft
Property substrate adhesiveness it is excessively poor, lack wearability, and be very easy to be oxidized.Therefore these of silver nanowires how to be promoted
Performance.It is most important for the application of silver wire transparent electrode material.
For these performance boosts of silver nanowires, has more documents and materials report at present.For example, using graphene
To silver nanowires surface coating (such as document Nano Lett.2015,15,4206-4213；Carbon2014,69,437-443；
Nanoscale 2013,5,7750-7755；RSC Adv.2016,6,67389-67395), or sol-gel method is utilized, by nothing
Machine oxide is deposited on silver wire surface, improves oxidation resistent susceptibility (such as the document: Journal of Materials of silver nanowires
Chemistry C 2014,2,3914-3920；ACS Appl.Mater.Interfaces 2015,7,24601-24607)；Also
Silver nanowires can be encapsulated in polyurethane (Materials&Design 2017,129,180-185), photoresist (ACS
Appl.Mater.Interfaces2015,7,23297-23304), epoxy resin (RSC Adv.2015,5,27657-
27664), poly-dopamine (Nanoscale 2014,6,4812-4818), polysiloxanes (Adv.Mater.2012,24,5117-
5122), polyvinyl alcohol (Adv.Mater.2010,22,4484-4488), polycarbonate (Nanotechnology 2013,24,
Etc. 275603) in polymer materials.
However, drawback of the prior art is that: 1) graphene and can not based on the inorganic oxide of " sol-gel method "
Excellent wearability and adhesiveness are provided；2) thickness of polymer material generally reaches several microns, much larger than silver nanowires
Diameter (about 20~150nm), silver wire is then fully embedded in polymeric substrate, at this time, it may be necessary to polymeric layer is removed, or
By polymeric layer etching edge, conductive network could be formed.
It is of the existing technology in order to overcome the problems, such as, on the basis of guaranteeing wearability and adhesiveness, CN105702381A
Report a kind of method using epoxy resin and polyurethane aqueous emulsions encapsulation silver nanowires.This method is first by silver nanoparticle wire bonding
It is connected into continuous conduction network, is then encapsulated using resin solidification.However, relative to single silver nanowires, the silver of weldedization
Nanometer network can not be moved effectively in epoxy resin and polyurethane base material, so having led in the patent, fluoropolymer resin
What cannot centainly be applied is too thick, if resinous coat is too thick, silver nanoparticle network will be all covered, so that silver wire networks forfeit is led
Electrically.Also, to avoid excessive polymer covering silver nano line surface so that electric conductivity reduces, used in water-based emulsion
Concentration is relatively low, although ensure that the electric conductivity of electrode film in this way, the polymer emulsion of this low concentration is for wearability, glutinous
Attached property and antioxidative promotion are limited.Therefore, how under the premise of guaranteeing silver nanowires electric conductivity, the raising of amplitude peak
These performances of transparent electrode film, it is extremely important for this field.
Summary of the invention
In order to further enhance the wearability, adhesion and inoxidizability of transparent electrode film, the deficiencies in the prior art are solved,
The primary purpose of the present invention is that providing a kind of preparation method of ultrastability epoxy packages silver nanowires flexible transparent electrode.
Present invention utilizes the surfaces of silver wire single during epoxy resin thermosetting from principle of displacement, using pure epoxy resin as base
Material encapsulates silver nanowires and prepares silver nanowires transparent electrode thin film, and preparation method is simple to operation.
The ultrastability epoxy packages as made from above-mentioned preparation method that another object of the present invention is to provide one kind silver
Nano wire flexible transparent electrode material, has the advantages that high-wearing feature, high-adhesiveness, high chemical stability.
A further object of the present invention is to provide above-mentioned ultrastability epoxy packages silver nanowires flexible transparent electrodes
Using.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of ultrastability epoxy packages silver nanowires flexible transparent electrode, comprising the following steps:
(1) coating of silver nanowires
By on certain density silver nanowires dispersion to flexible parent metal, certain thickness dispersion liquid liquid film is formed,
Then it dries；
(2) the contact splicing of silver nanowires
The contact that silver nanowires is promoted using plasma surface etching method or heating, i.e., to the dispersion liquid after drying
Liquid film carries out corona treatment or heat treatment, obtains the silver nanowires after corona treatment or heat treatment；
(3) encapsulation of silver nanowires
Epoxy monomer and curing agent are compounded to obtain mixed liquor, total constitution of epoxy monomer and curing agent in the mixed liquor
Amount concentration is 5~60mg/mL；The mixed liquor after compounding is covered by step (2) treated silver nanowires surface again；?
Under vacuum or air atmosphere, it is heating and curing to get ultrastability epoxy packages silver nanowires flexible transparent electrode film is arrived, wherein
Epoxy resin layer thickness after solidification are 0.4~2.0 μm.
In heat curing process of the invention, epoxy resin is semi liquid state, single during resin solidification is solid
Silver nanowires is slowly bent, and is migrated to epoxy resin surface, and epoxy resin surface is partly exposed to, and forms conductive film.
Preferably, the concentration of step (1) the silver nanowires dispersion liquid is 0.5~5.0mg/mL.
Preferably, step (1) flexible parent metal is polyethylene terephthalate thin film (PET), Kapton
(PI) or one of polycarbonate membrane (PC).
Preferably, in step (1) using spraying or in the way of scratching by certain density silver nanowires dispersion to soft
Property substrate on formed dispersion liquid liquid film, the dispersion liquid film thickness be 10~40 μm；The drying is in air atmosphere and room
The lower drying of temperature.
Preferably, specific step is as follows for step (2) the plasma surface etching method: utilizing air plasma, will do
Dispersion liquid liquid film after dry is surface-treated；The air plasma processing time is 30~600 seconds, and operation voltage is
200~1500V, power are 5~15W, and vacuum degree is 300~1000mTorr；Specific step is as follows for step (2) described heating:
By the dispersion liquid liquid film after drying under vacuum or air atmosphere, in 80~150 DEG C of 10~40min of baking.
It allows silver nanowires surface that can contact with each other in the present invention, rather than welds together.Silver nanowires itself is due to system
Standby problem, surface usually contain some polymer stabilizers, and polymer stabilizer electric conductivity is very poor, so needing in step (2)
These polymer stabilizers are removed.Remove polymer stabilizer after, between silver nanowires and silver nanowires can substance connect
Touching, electric conductivity will be promoted significantly.Certainly this contact is closer, and electric conductivity promotion is more obvious.In above-mentioned technological parameter model
It encloses and carries out corona treatment or heat the electric conductivity that can guarantee the film finally prepared to greatest extent, if exceeding these
The electric conductivity of range, film can reduce, or even become non-conductive.
Preferably, epoxy monomer described in step (3) is bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, neighbour
Cresol novolac epoxy resins, o-phthalic acid diglycidyl ester, four glycidyl group -4,4,-diaminodiphenylmethane, 3,4- ring
The mixture of one or more of oxygen cyclohexyl methyl -3,4- epoxycyclohexylcarboxylate.
Preferably, curing agent described in step (3) is isophorone diamine, tetrabydrophthalic anhydride, polyamide, polyethers
The mixture of one or more of amine, triethanolamine, piperazine, aniline-formaldehyde resin.
Preferably, step (3) mixed liquor, in epoxy monomer in epoxy-functional and curing agent reactive hydrogen molar ratio
Example is 1.0:0.6~1.0:1.1.If reactive hydrogen is very little, the crosslinking of epoxy-functional can not be effectively realized, can seriously reduce and lead
Every mechanical performance of electrolemma.It is usually stronger using volatility such as ethyl alcohol, butanone, methanol, isopropanols in step (3)
Solvent carries out compounding mixed liquor.
Preferably, step (3) temperature being heating and curing is room temperature to 150 DEG C, and the time is 2~120h.
Preferably, the mixed liquor after compounding is covered by plasma using spraying or scratching mode in step (3)
The silver nanowires surface of processing or heat treatment.
Ultrastability epoxy packages silver nanowires flexible transparent electrode made from the above method can be applied to Flexible Displays,
The fields such as solar battery, touch control component.
Compared with prior art, the present invention has the following advantages and beneficial effects:
The present invention is first by silver nanowires dispersion to flexible parent metal surface, then passes through plasma or heat treatment
The contacting with each other property of silver wire is improved, heat cure encapsulation finally is carried out to silver nanowires using epoxy resin.In encapsulation process,
In the epoxy substrate of melting, therefore single silver nanowires meeting Spontaneous migration, ensure that Thin film conductive to epoxy coating surface
While property, preferred epoxy coating thickness makes the physical chemistry of film stably obtain significant increase.The present invention is prepared into
The flexible transparent electrode membrane material arrived, in thermo-oxidative stability, bending resistance, rub resistance, scratch resistance, caking property, solvent resistant
Property and resistant to sulfur aggressivity in terms of, all have very excellent performance.
Detailed description of the invention
Fig. 1 is a kind of preparation method schematic diagram of the silver nanowires flexible transparent electrode of hypervelocity stability of the present invention.
Fig. 2 is the silver nanowires flexible transparent electrode Scanning Electron microscope photo that embodiment 2 is prepared.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) coating of silver nanowires
Using spraying method, concentration on the silver nanowires dispersion to PET of 0.5mg/ml, is formed into 40 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 30 seconds, behaviour
Making voltage is 1500V, power 15W, vacuum degree 300mTorr.
(3) encapsulation of silver nanowires
Bisphenol A diglycidyl ether and polyamide are compounded to obtain mixed liquor, in mixed liquor bisphenol A diglycidyl ether and
The overall quality concentration of polyamide is 5mg/mL, and the molar ratio of epoxy-functional and reactive hydrogen is 1:0.6；Recycle spraying side
Mixed liquor is covered the silver nanowires surface after step (2) corona treatment by formula.Under vacuum, room temperature is solid
Change 120h, obtains sample 1.The epoxy coating of the sample is with a thickness of 2 μm.
Embodiment 2
(1) coating of silver nanowires
Using spraying method, concentration on the silver nanowires dispersion to PI of 0.5mg/ml, is formed into 40 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 200 seconds, behaviour
Making voltage is 700V, power 7W, vacuum degree 600mTorr.
(3) encapsulation of silver nanowires
Bisphenol A diglycidyl ether and isophorone diamine are compounded to obtain mixed liquor, bisphenol-A two shrinks sweet in mixed liquor
The overall quality concentration of oily ether and isophorone diamine is 10mg/ml, and the molar ratio of epoxy-functional and reactive hydrogen is 1:
0.6；Spraying method is recycled, mixed liquor is covered into the silver nanowires surface after step (2) corona treatment.True
Under empty atmosphere, 110 DEG C of 4h that are heating and curing obtain sample 2.The epoxy coating of the sample is with a thickness of 1.8 μm.
Embodiment 3
(1) coating of silver nanowires
Using spraying method, concentration on the silver nanowires dispersion to PC of 0.5mg/ml, is formed into 40 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 600 seconds, behaviour
Making voltage is 300V, power 5W, vacuum degree 1000mTorr.
(3) encapsulation of silver nanowires
Bisphenol F diglycidyl ether and polyetheramine are compounded to obtain mixed liquor, in mixed liquor Bisphenol F diglycidyl ether and
The overall quality concentration of polyetheramine is 20mg/ml, and the molar ratio of epoxy-functional and reactive hydrogen is 1:0.7；Recycle spraying
Mixed liquor is covered the silver wire surface after step (2) corona treatment by mode.Under vacuum, 60 DEG C of heating
Solidify 48h, obtains sample 3.The epoxy coating of the sample is with a thickness of 1.5 μm.
Embodiment 4
(1) coating of silver nanowires
Using spraying method, concentration on the silver nanowires dispersion to PET of 5.0mg/ml, is formed into 10 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
The silver nanowires film coated and drying finishes is toasted under air atmosphere, baking temperature is 80 DEG C, is dried
The roasting time is 40min.
(3) encapsulation of silver nanowires
Bisphenol F diglycidyl ether and isophorone diamine are compounded to obtain mixed liquor, Bisphenol F two is shunk sweet in mixed liquor
The overall quality concentration of oily ether and isophorone diamine is 30mg/ml, and the molar ratio of epoxy-functional and reactive hydrogen is 1:
0.7；Spraying method is recycled, mixed liquor is covered into the silver nanowires surface after step (2) heat treatment.In vacuum atmosphere
Under enclosing, room temperature curing for 24 hours, obtains sample 4.The epoxy coating of the sample is with a thickness of 1. μm.
Embodiment 5
(1) coating of silver nanowires
Using spraying method, concentration on the silver nanowires dispersion to PI of 5.0mg/ml, is formed into 10 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 500 seconds, behaviour
Making voltage is 1300V, power 13W, vacuum degree 900mTorr.
(3) encapsulation of silver nanowires
O-cresol formaldehyde epoxy resin and triethanolamine are compounded to obtain mixed liquor, in mixed liquor o-cresol formaldehyde epoxy resin and
The overall quality concentration of triethanolamine is 40mg/ml, and the molar ratio of epoxy-functional and reactive hydrogen is 1:0.8；Recycle spray
Mixed liquor is covered the silver nanowires surface after step (2) corona treatment by painting mode.Under vacuum, 80
DEG C be heating and curing 4h, obtains sample 5.The epoxy coating of the sample is with a thickness of 1.0 μm.
Embodiment 6
(1) coating of silver nanowires
Using spraying method, concentration on the silver nanowires dispersion to PC of 5.0mg/ml, is formed into 10 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 600 seconds, behaviour
Making voltage is 300V, power 5W, vacuum degree 1000mTorr.
(3) encapsulation of silver nanowires
O-cresol formaldehyde epoxy resin and triethanolamine/piperazine (mass ratio of triethanolamine and piperazine is 1:1) are compounded
To mixed liquor, o-cresol formaldehyde epoxy resin and triethanolamine/piperazine overall quality concentration are 50mg/ml, epoxy in mixed liquor
The molar ratio of functional group and reactive hydrogen is 1:0.8；Recycle spraying method, by mixed liquor cover by step (2) etc. from
Daughter treated silver nanowires surface.Under vacuum, 60 DEG C are heating and curing for 24 hours, obtain sample 6.The epoxy of the sample
Coating layer thickness is 0.7 μm.
Embodiment 7
(1) coating of silver nanowires
Using spraying method, concentration on the silver nanowires dispersion to PET of 3.0mg/ml, is formed into 25 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
The silver nanowires film coated and drying finishes is toasted under air atmosphere, baking temperature is 100 DEG C, is dried
The roasting time is 30min.
(3) encapsulation of silver nanowires
O-phthalic acid diglycidyl ester and piperazine are compounded to obtain mixed liquor, phthalic acid two shrinks in mixed liquor
The overall quality concentration of glyceride and piperazine is 60mg/ml, and the molar ratio of epoxy-functional and reactive hydrogen is 1:0.8；It is sharp again
With spraying method, mixed liquor is covered into the silver nanowires surface after step (2) corona treatment.In vacuum
Under, 60 DEG C of 72h that are heating and curing obtain sample 7.The epoxy coating of the sample is with a thickness of 0.4 μm.
Embodiment 8
(1) coating of silver nanowires
Using spraying method, concentration on the silver nanowires dispersion to PI of 3.0mg/ml, is formed into 25 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 300 seconds, behaviour
Making voltage is 800V, power 8W, vacuum degree 700mTorr.
(3) encapsulation of silver nanowires
By o-phthalic acid diglycidyl ester and isophorone diamine/polyetheramine (isophorone diamine/polyetheramine quality
Than obtaining mixed liquor for 1:2) compounding, o-phthalic acid diglycidyl ester and isophorone diamine/polyetheramine in mixed liquor
Overall quality concentration is 40mg/ml, and the molar ratio of epoxy-functional and reactive hydrogen is 1:0.9；Spraying method is recycled, will be mixed
It closes liquid and covers the silver wire Nanosurface after step (2) corona treatment.Under vacuum, 80 DEG C are heating and curing
6h obtains sample 8.The epoxy coating of the sample is with a thickness of 1.0 μm.
Embodiment 9
(1) coating of silver nanowires
Using spraying method, concentration on the silver nanowires dispersion to PC of 3.0mg/ml, is formed into 25 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Baking temperature is 120 DEG C, baking time 20min.
(3) encapsulation of silver nanowires
By four glycidyl group -4,4,-diaminodiphenylmethane and aniline-formaldehyde resin compound to obtain mixed liquor, mixed liquor
The overall quality concentration of middle four glycidyl group -4,4,-diaminodiphenylmethane and aniline-formaldehyde resin is 60mg/ml, epoxy
The molar ratio of functional group and reactive hydrogen is 1:0.9；Spraying method is recycled, mixed liquor is covered and is heated by step (2)
Treated silver nanowires surface.Under vacuum, 120 DEG C of 16h that are heating and curing obtain sample 9.The epoxy coating of the sample
With a thickness of 0.4 μm.
Embodiment 10
(1) coating of silver nanowires
In the way of blade coating, on the silver nanowires dispersion to PET for being 4.0mg/ml by concentration, 15 μ m-thicks are formed
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 100 seconds, behaviour
Making voltage is 500V, power 6W, vacuum degree 400mTorr.
(3) encapsulation of silver nanowires
By four glycidyl group -4,4,-diaminodiphenylmethane and piperazine compound to obtain mixed liquor, and four shrink in mixed liquor
The overall quality concentration of glyceryl -4,4,-diaminodiphenylmethane and piperazine is 50mg/ml, epoxy-functional and reactive hydrogen
Molar ratio is 1:0.9；Blade coating mode is recycled, mixed liquor is covered into the Yin Na after step (2) corona treatment
Nanowire surface.Under air atmosphere, 120 DEG C are heating and curing for 24 hours, obtain sample 10.The epoxy coating of the sample is with a thickness of 0.7 μ
m。
Embodiment 11
(1) coating of silver nanowires
In the way of blade coating, on the silver nanowires dispersion to PI for being 4.0mg/ml by concentration, 15 μ m-thicks are formed
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 200 seconds, behaviour
Making voltage is 700V, power 7W, vacuum degree 600mTorr.
(3) encapsulation of silver nanowires
3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexylcarboxylate and aniline-formaldehyde resin are compounded and mixed
Liquid, the overall quality of 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexylcarboxylate and aniline-formaldehyde resin is dense in mixed liquor
Spending is 30mg/ml, and the molar ratio of epoxy-functional and reactive hydrogen is 1:0.9；Blade coating mode is recycled, mixed liquor is covered
Silver nanowires surface after step (2) corona treatment.Under air atmosphere, 100 DEG C of 48h that are heating and curing obtain sample
Product 11.The epoxy coating of the sample is with a thickness of 1.2 μm.
Embodiment 12
(1) coating of silver nanowires
In the way of blade coating, on the silver nanowires dispersion to PC for being 4.0mg/ml by concentration, 15 μ m-thicks are formed
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 100 seconds, behaviour
Making voltage is 500V, power 6W, vacuum degree 400mTorr.
(3) encapsulation of silver nanowires
It compounds 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexylcarboxylate and triethanolamine to obtain mixed liquor, mix
Closing the overall quality concentration of 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexylcarboxylate and triethanolamine in liquid is 20mg/
The molar ratio of ml, epoxy-functional and reactive hydrogen is 1:0.9；Blade coating mode is recycled, mixed liquor is covered by step
(2) the silver nanowires surface after corona treatment.Under air atmosphere, 120 DEG C of 2h that are heating and curing obtain sample 12.The sample
The epoxy coating of product is with a thickness of 1.5 μm.
Embodiment 13
(1) coating of silver nanowires
In the way of blade coating, on the silver nanowires dispersion to PET for being 1.5mg/ml by concentration, 30 μ m-thicks are formed
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
The silver nanowires film coated and drying finishes is toasted under vacuum, baking temperature is 150 DEG C, is dried
The roasting time is 10in.
(3) encapsulation of silver nanowires
By bisphenol A diglycidyl ether/four glycidyl group -4,4,-diaminodiphenylmethane (the two mass ratio is 2:1)
It compounds to obtain mixed liquor, bisphenol A diglycidyl ether/four glycidyl group -4,4 in mixed liquor,-diamino hexichol with polyetheramine
The overall quality concentration of methane and polyetheramine is 10mg/ml, and the molar ratio of epoxy-functional and reactive hydrogen is 1:1.0；It is sharp again
With blade coating mode, mixed liquor will be compounded and cover the silver nanowires surface after step (2) heat treatment.In air atmosphere
Under, 120 DEG C of 12h that are heating and curing obtain sample 13.The epoxy coating of the sample is with a thickness of 1.8 μm.
Embodiment 14
(1) coating of silver nanowires
In the way of blade coating, on the silver nanowires dispersion to PI for being 1.5mg/ml by concentration, 30 μ m-thicks are formed
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 30 seconds, behaviour
Making voltage is 1500V, power 15W, vacuum degree 300mTorr.
(3) encapsulation of silver nanowires
By Bisphenol F diglycidyl ether/3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexylcarboxylate's (the two quality
Than obtaining mixed liquor for 1:1) and polyamide/piperazine (the two mass ratio is 3:1) compounding, Bisphenol F 2-glycidyl in mixed liquor
Ether/3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexylcarboxylate and polyamide/piperazine overall quality concentration are 5mg/
The molar ratio of ml, epoxy-functional and reactive hydrogen is 1:1.0；Blade coating mode is recycled, mixed liquor is covered by step
(2) the silver nanowires surface after corona treatment.Under air atmosphere, 100 DEG C of 48h that are heating and curing obtain sample 14.The sample
The epoxy coating of product is with a thickness of 2 μm.
Embodiment 15
(1) coating of silver nanowires
In the way of blade coating, on the silver nanowires dispersion to PC for being 1.5mg/ml by concentration, 30 μ m-thicks are formed
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 300 seconds, behaviour
Making voltage is 800V, power 8W, vacuum degree 700mTorr.
(3) encapsulation of silver nanowires
By o-cresol formaldehyde epoxy resin/o-phthalic acid diglycidyl ester (the two mass ratio is 1:2) and tetrahydro neighbour's benzene
Dicarboxylic acid anhydride compounds to obtain mixed liquor, o-cresol formaldehyde epoxy resin/o-phthalic acid diglycidyl ester and tetrahydro in mixed liquor
The overall quality concentration of phthalic anhydride is 30mg/ml, and the molar ratio of epoxy-functional and reactive hydrogen is 1:1.0；It is sharp again
With blade coating mode, mixed liquor is covered into the silver nanowires surface after step (2) corona treatment.In air atmosphere
Under, 100 DEG C of 120h that are heating and curing obtain sample 15.The epoxy coating of the sample is with a thickness of 1.2 μm.
Embodiment 16
(1) coating of silver nanowires
In the way of blade coating, on the silver nanowires dispersion to PET for being 1.0mg/ml by concentration, 35 μ m-thicks are formed
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
The silver nanowires film coated and drying finishes is toasted under vacuum, baking temperature is 130 DEG C, is dried
The roasting time is 25min.
(3) encapsulation of silver nanowires
By bisphenol A diglycidyl ether/o-cresol formaldehyde epoxy resin (the two mass ratio is 2:1) and tetrahydrophthalic acid
Acid anhydride compounds to obtain mixed liquor, bisphenol A diglycidyl ether/o-cresol formaldehyde epoxy resin and tetrabydrophthalic anhydride in mixed liquor
Overall quality concentration be 60mg/ml, the molar ratio of epoxy-functional and reactive hydrogen is 1:1.1；Blade coating mode is recycled, it will
Mixed liquor covers the silver nanowires surface after step (2) heat treatment.Under air atmosphere, 120 DEG C are heating and curing
72h obtains sample 16.The epoxy coating of the sample is with a thickness of 0.4 μm.
Embodiment 17
(1) coating of silver nanowires
In the way of blade coating, on the silver nanowires dispersion to PI for being 1.0mg/ml by concentration, 35 μ m-thicks are formed
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 400 seconds, behaviour
Making voltage is 1000V, power 10W, vacuum degree 800mTorr.
(3) encapsulation of silver nanowires
By Bisphenol F diglycidyl ether/o-phthalic acid diglycidyl ester (the two mass ratio be 1:1) and polyamide/
Triethanolamine (the two mass ratio is 4:1) compounding obtains mixed liquor, Bisphenol F diglycidyl ether/phthalic acid in mixed liquor
2-glycidyl ester and polyamide/triethanolamine overall quality concentration are 10mg/ml, mole of epoxy-functional and reactive hydrogen
Ratio is 1:1.1；Blade coating mode is recycled, mixed liquor is covered into the silver nanowires after step (2) corona treatment
Surface.Under air atmosphere, 100 DEG C of 12h that are heating and curing obtain sample 17.The epoxy coating of the sample is with a thickness of 1.8 μm.
Embodiment 18
(1) coating of silver nanowires
In the way of blade coating, on the silver nanowires dispersion to PC for being 1.0mg/ml by concentration, 35 μ m-thicks are formed
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
(2) the splicing contact of silver nanowires
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 500 seconds, behaviour
Making voltage is 1300V, power 13W, vacuum degree 900mTorr.
(3) encapsulation of silver nanowires
By four glycidyl group -4,4,-diaminodiphenylmethane/3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexyl
Carboxylate (the two mass ratio is 1:1) and polyamide compound to obtain mixed liquor, four glycidyl group -4,4 in mixed liquor,-diamino
The overall quality concentration of base diphenyl-methane/3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexylcarboxylate and polyamide is
The molar ratio of 20mg/ml, epoxy-functional and reactive hydrogen is 1:1.1；Recycle blade coating mode, by mixed liquor cover by
Silver nanowires surface after step (2) corona treatment.Under air atmosphere, 60 DEG C of 3h that are heating and curing obtain sample 18.It should
The epoxy coating of sample is with a thickness of 1.5 μm.
Comparative example
To confirm the advance of the present invention compared with the prior art, spy carries out following two comparative examples.
Comparative example 1
Using spraying method, concentration on the silver nanowires dispersion to PET of 0.5mg/ml, is formed into 40 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 30 seconds, behaviour
Making voltage is 1500V, power 15W, vacuum degree 300mTorr.Obtain contrast sample 1.
Electric conductivity and light transmittance test are directly carried out to the electrode film of above-mentioned steps preparation.
Note: in the comparative example, transparent electrode film does not carry out epoxy resin encapsulation.
Comparative example 2
Using spraying method, concentration on the silver nanowires dispersion to PET of 0.5mg/ml, is formed into 40 μ m-thicks
Dispersion liquid liquid film, then dry in air atmosphere and at room temperature.
Air plasma processing is carried out to the silver nanowires film coated and drying finishes, the processing time is 30 seconds, behaviour
Making voltage is 1500V, power 15W, vacuum degree 300mTorr.
Electric conductivity and light transmittance test are directly carried out to the electrode film of above-mentioned steps preparation.
Bisphenol F diglycidyl ether and polyamide are compounded to obtain mixed liquor, in mixed liquor Bisphenol F diglycidyl ether and
The overall quality concentration of polyamide is 5mg/ml, and the molar ratio of epoxy-functional and reactive hydrogen is 1:1.1；Recycle spraying side
Mixed liquor is covered the silver nanowires surface after step (2) corona treatment by formula.In vacuum and room temperature
Under, solidify 120h, obtains contrast sample 2.The epoxy coating of the sample is with a thickness of 0.1 μm.
Note: in the comparative example, epoxy coating with a thickness of 0.1 μm, be lower than preferred thickness (0.4 of the present invention
~2.0 μm)
According to following test method to sample test performance prepared by above-described embodiment 1-18 and comparative example 1-2,
It the results are shown in Table 1 and table 2.
1. sheet resistance (Rs)
Film surface resistance is measured using four-point probe measurment instrument, every film is at least tested 10 times, is averaged.Probe is straight
500 μm of diameter, probe spacing 0.5mm, test 10 μ A of electric current
2. light transmittance (T%)
Utilize ultraviolet-uisible spectrophotometer testing film transparency, permeability of the testing film for 550nm visible light.
Before test, take uncoated PET, PI or PC as reference.
3. thermo-oxidative stability
Film is placed in Muffle furnace, under air atmosphere, in 200 DEG C of baking 60min, takes out test surfaces resistance and thoroughly
Light rate.
4. bending resistance
It is the semi-circular of 1cm by film bends to diameter, repeated flex 500 times, test surfaces resistance and light transmittance.
5. rub resistance
By the tight cotton of Thin film conductive face paste, apply certain pressure, guarantee pressure is 17kPa, drags the distance of 10cm, is repeated
500 times, test surfaces resistance and light transmittance.
6. scratch resistance
The pencil of different hardness is fixed on 501 pencil hardness testers, push to test instrument transverse shifting on film,
Pencil point is observed for the scraping effect of coating, until recording pencil hardness at this time when coating is not scraped off just.
7. adhesiveness
It willAdhesive tape is bonded in transparent electrode conductive surface with the pressure pressing of 10N, then quickly tears off, weight
It is 1000 times multiple, test surfaces resistance and light transmittance.
8. solvent resistance
By transparent electrode thin film be placed in ethanol solution in, be standing and soaking 48h, dried after taking-up, test surfaces resistance and thoroughly
Light rate.
9. resistant to sulfur aggressivity
Transparent electrode thin film is placed in and is impregnated 30min by the ethanol solution (concentration 0.2mg/ml) for preparing sulphur, is tested thin
Film surface resistance and light transmittance.
1 properties of sample of table
2 properties of sample of table
By embodiment as can be seen that the silver nanowires flexible transparent electrode film by epoxy resin encapsulation has ideal
Electric conductivity, sheet resistance value is fully able to meet application demand between 18.8~24.3 Ω/.
After 200 DEG C of heated oxides are calcined, the film surface resistance value of epoxy packages has almost no change, un-encapsulated
Electrode film then become non-conductive.After 500 bendings, the film surface resistance value of epoxy packages does not occur obviously to change
Become, un-encapsulated electrode film sheet resistance value then improves 50%.After 500 rub resistances are tested, epoxy packages
Film surface resistance value it is only a small amount of promoted, un-encapsulated electrode film then becomes non-conductive.Stick survey by 1000 times
After examination, the film surface resistance of epoxy resin encapsulation is almost unchanged, and un-encapsulated electrode film then becomes non-conductive；Scratch resistance
Wiping test proves, the film surface hardness of epoxy resin encapsulation is 2B, and un-encapsulated electrode film hardness is lower than 6B；By
After ethyl alcohol impregnates within 48 hours, the film surface resistance of epoxy resin encapsulation is almost unchanged, and un-encapsulated electrode film then becomes
It obtains non-conductive；After 30min sulphur corrosion, still conductive, the un-encapsulated electrode of the film surface of epoxy resin encapsulation
Film then becomes non-conductive.
It is above-mentioned analysis shows, epoxy resin, which encapsulates, is capable of the physics and chemistry of significant increase silver nanowires transparent electrode thin film
Stability has reliable application value.
It is found by comparative experiments: physics and change of the thickness of epoxy coating for silver nanowires transparent electrode thin film
The influence for learning stability is very big.After epoxy coating thickness is lower than preferred thickness of the invention, although silver nanowires is physico
Stability, which still has, significantly to be promoted, but its surface rub resistance, adhesiveness, scratch resistance, solvent resistant, resistant to sulfur aggressivity, phase
It is still defective for thicker epoxy coating.It tests obtained related data and shows relatively thin epoxy coating
Thickness is unable to satisfy existing application demand after above-mentioned test.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of ultrastability epoxy packages silver nanowires flexible transparent electrode, which is characterized in that including with
Lower step:
(1) by silver nanowires dispersion to flexible parent metal, dispersion liquid liquid film is formed, is then dried；
(2) corona treatment or heat treatment are carried out to the dispersion liquid liquid film of step (1) after dry；
(3) epoxy monomer and curing agent are compounded to obtain mixed liquor, total constitution of epoxy monomer and curing agent in the mixed liquor
Amount concentration is 5~60mg/mL；The mixed liquor after compounding is covered after step (2) corona treatment or heat treatment again
Silver nanowires surface；Under vacuum or air atmosphere, it is heating and curing to get soft to ultrastability epoxy packages silver nanowires
Property transparent electrode film, wherein epoxy resin layer after solidifying with a thickness of 0.4~2.0 μm.
2. a kind of preparation side of ultrastability epoxy packages silver nanowires flexible transparent electrode according to claim 1
Method, which is characterized in that corona treatment described in step (2) are as follows: air plasma is utilized, by the dispersion liquid after drying
Film is surface-treated；The air plasma processing time is 30~600 seconds, and operation voltage is 200~1500V, power
For 5~15W, vacuum degree is 300~1000mTorr；
Step (2) described heat treatment are as follows: by the dispersion liquid liquid film after drying under vacuum or air atmosphere, dried at 80~150 DEG C
Roasting 10~40min.
3. a kind of preparation side of ultrastability epoxy packages silver nanowires flexible transparent electrode according to claim 1
Method, which is characterized in that step (3) described mixed liquor, in epoxy monomer in epoxy-functional and curing agent reactive hydrogen molar ratio
For 1.0:0.6~1.0:1.1.
4. a kind of preparation side of ultrastability epoxy packages silver nanowires flexible transparent electrode according to claim 1
Method, which is characterized in that epoxy monomer described in step (3) is bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, adjacent first
Novolac epoxy resin, o-phthalic acid diglycidyl ester, four glycidyl group -4,4,-diaminodiphenylmethane, 3,4- epoxy
The mixture of one or more of cyclohexyl methyl -3,4- epoxycyclohexylcarboxylate.
5. a kind of preparation side of ultrastability epoxy packages silver nanowires flexible transparent electrode according to claim 1
Method, which is characterized in that curing agent described in step (3) is isophorone diamine, tetrabydrophthalic anhydride, polyamide, polyethers
The mixture of one or more of amine, triethanolamine, piperazine, aniline-formaldehyde resin.
6. a kind of ultrastability epoxy packages silver nanowires flexible transparent electrode according to any one of claims 1 to 5
Preparation method, which is characterized in that step (3) temperature that is heating and curing is room temperature to 150 DEG C, and the time is 2~120h；Using
Spraying or blade coating mode, cover silver nanowires surface for the mixed liquor after compounding.
7. a kind of ultrastability epoxy packages silver nanowires flexible transparent electrode according to any one of claims 1 to 5
Preparation method, which is characterized in that the concentration of step (1) the silver nanowires dispersion liquid be 0.5~5.0mg/mL；
Step (1) flexible parent metal is in polyethylene terephthalate thin film, Kapton or polycarbonate membrane
One kind.
8. a kind of ultrastability epoxy packages silver nanowires flexible transparent electrode according to any one of claims 1 to 5
Preparation method, which is characterized in that by silver nanowires dispersion to flexibility base in the way of spraying or blade coating in step (1)
Dispersion liquid liquid film is formed on material, the dispersion liquid film thickness is 10~40 μm；The drying is in air atmosphere and at room temperature
It is dry.
9. a kind of ultrastability epoxy packages silver nanowires flexible transparent electrode, which is characterized in that it is by claim 1 to 8
A kind of preparation method of described in any item ultrastability epoxy packages silver nanowires flexible transparent electrodes is made.
10. a kind of application of ultrastability epoxy packages silver nanowires flexible transparent electrode as claimed in claim 9, feature
It is, which is applied to Flexible Displays, solar battery or touch-control
Member arts.
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| CN114544050A (en) * | 2022-02-28 | 2022-05-27 | 佛山科学技术学院 | Flexible tension sensor based on oriented conductive nanofibers and preparation method and application thereof |
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|---|---|---|---|---|
| CN101292362A (en) * | 2005-08-12 | 2008-10-22 | 凯博瑞奥斯技术公司 | Nanowires-based transparent conductors |
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| CN101292362A (en) * | 2005-08-12 | 2008-10-22 | 凯博瑞奥斯技术公司 | Nanowires-based transparent conductors |
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Application publication date: 20181207 |