CN106297964A - A kind of compound transparent electricity conductive film and preparation method thereof - Google Patents
A kind of compound transparent electricity conductive film and preparation method thereof Download PDFInfo
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- CN106297964A CN106297964A CN201610643280.7A CN201610643280A CN106297964A CN 106297964 A CN106297964 A CN 106297964A CN 201610643280 A CN201610643280 A CN 201610643280A CN 106297964 A CN106297964 A CN 106297964A
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H—ELECTRICITY
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
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Abstract
The present invention relates to a kind of compound transparent electricity conductive film and preparation method thereof, the step of its preparation method is as follows: S1, at metal substrate surface catalytic growth monocrystalline sublayer graphene film, obtains structure I；S2, the graphene membrane surface in structure I coats nano silver wire and dries, it is thus achieved that composite construction II；S3, even spread liquid photocurable material in flexible and transparent substrate, obtain composite construction III；S4, is directed at pressing by the liquid photocurable coating in composite construction III with the nano silver wire coating in composite construction II, obtains composite construction IV；S5, carries out irradiation to composite construction IV, makes liquid photocurable coating be changed into solid-state, obtains composite construction V；S6, by electrochemical process stripping means, separates the metal substrate in composite construction V, obtains composite conducting fexible film.The method is simple and reliable, is suitable for large-scale production, prepared compound transparent electricity conductive film, excellent electric conductivity, and transmitance is high, dependable performance.
Description
Technical field
The present invention relates to transparent conductive film preparation field, in detail, relate to a kind of composite conductive thin film and preparation side thereof
Method.
Background technology
Transparent conductive material is the important component part of a lot of electronic device, such as touch screen, display, Electronic Paper, the sun
Energy battery etc..Along with the progress of science and technology, utilizing flexible and transparent conductive material to manufacture electronic product rollable, folding becomes new
Development trend.
In transparent conductive material field, traditional tin indium oxide (ITO), it is faced with asking of corresponding tcrude ore day by day exhaustion
Topic；Meanwhile, there will be brittle fracture and broken, that sheet resistance raises problem during the conductive film bending that prepared by tin indium oxide.
It is difficult in adapt to the growth requirement of flexible electronic devices.
In recent years, research worker have developed nano silver wire and CVD transparent graphene conductive film in order to substitute ITO, and
Make remarkable progress.But, nano silver wire has problems: 1. the silver wire being exposed to surface is the most oxidized, and surface electricity occurs
The problem that resistance raises；2. conductive network, fine pattern, open circuit；3. follow current, overlapped points fuses.The problem of Graphene is: change
Large-area graphene transparent conductive film prepared by vapour deposition (CVD) technology is polycrystalline structure, high impedance crystal boundary between domain
Cause graphene film product sheet resistance higher.At present, generally use chemical doping technique, improve the electric conductivity of thin film, reduction side
Resistance.But adulterant mostly is little molecule, through the operations such as washing, high-temperature process, dopant molecule generation series of physical
Learn change and lose, cause sheet resistance persistently to rise.Therefore individually nano silver wire or CVD grapheme conductive film are applied to
Bright conductive material field face huge challenge.
For solving nano silver wire and the problems referred to above of CVD Graphene further, can be the most compound by both, on the one hand, silver
Nano wire is combined with Graphene, and effect is obvious, and compound sheet resistance is decreased obviously；On the other hand, the Graphene on surface has been possible not only to
Effect protection silver wire, stops oxidation, it is also possible to improve the uniformity of conductive film surface current.At present, open report is mostly
The method that nano silver wire is compound with graphene oxide (GO).GO is with native graphite as raw material, peels off preparation by chemical oxidation
, remain a small amount of oxidizing species, nano silver wire can be produced slowly etching；Additionally, GO poorly conductive, both are combined
Based on nano silver wire conduction, too much GO can reduce composite conductive on the contrary, reduces light transmittance simultaneously；And reduction-oxidation graphite
The method of alkene, or inefficient, or toxicity is bigger.Nano silver wire is compound with CVD graphene film also to be had been reported, but deposits
Need to solve, such as in problems, it is impossible to the compound preparation of large area mass, CVD Graphene transfer defect is many, silver nanoparticle
Line-CVD Graphene contact impedance is high.
Summary of the invention
The problem compound with CVD Graphene for solving nano silver wire, the present invention is compound with liquid photocurable material for both
Medium, is optimized nano silver wire dispersion and combination process simultaneously, it is achieved that nano silver wire and Graphene large area are criticized
Quantifying compound preparation, it is ensured that CVD Graphene transfer integrity, reduce contact impedance between the two simultaneously, composite conducting performance is excellent.
The technical problem to be solved is: by composite conductive thin film, its nano silver wire comprising bottom and table
The Graphene of layer, prepares nano silver wire and (CVD technology growth) graphene composite conductive layer by coating process, and passes through
Liquid photocurable material (LLC, Liquid Light-curing Coating) is fitted, is solidified, transfer techniques realizes nano silver wire
Transparent base is transferred to graphene composite conductive layer, so that the Graphene of preparation and nano silver wire compound transparent electricity conductive film
Low square resistance and high permeability uniform, controllable, there is water-fast, the heat stability of improvement simultaneously.
The technical scheme is that the preparation method of a kind of compound transparent electricity conductive film,
This preparation method step includes:
S1, uses chemical gaseous phase depositing process at metal substrate surface catalytic growth monocrystalline sublayer graphene film, obtains stone
The structure I of ink alkene film-metal substrate；
S2, the graphenic surface in structure I coats nano silver wire dispersion liquid and dries, it is thus achieved that nano silver wire-graphene film-
The composite construction II of metal substrate；
S3, even spread liquid photocurable material in flexible and transparent substrate, obtain liquid photocurable coating-flexible and transparent
The composite construction III of substrate；
S4, is directed at pressure by the liquid photocurable coating in composite construction III with the nano silver wire coating in composite construction II
Close, obtain the composite construction IV of flexible and transparent substrate-liquid photocurable coating-silver nanowire layer-graphene film-metal substrate；
S5, carries out irradiation to composite construction IV, makes liquid photocurable coating be changed into solid-state, obtain flexible and transparent substrate-
The composite construction V of solid-state light solidifying coating-nano silver wire-graphene film-metal substrate；
S6, by electrochemical process stripping means, separates the metal substrate in composite construction V, obtains having flexible and transparent
The composite conducting fexible film of substrate-solid-state light solidifying coating-nano silver wire-graphene film.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described nano silver wire dispersion liquid is aqueous liquid dispersion, and wherein adds nanoscale emulsion.
Further, described nanoscale emulsion is the water-based emulsion of polyester-type aliphatic polyurethane resin, and resin concentration is
0.01～100mg/mL.
Further, in described step S3, described liquid photocurable material is the one in radically curing system material, can
Solidifying in the range of the light wave of 275～400nm, viscosity is 50-1000cps, it is preferred that range of viscosities is 50～200cps.
Further, described liquid photocurable material organic solvent diluting becomes coating fluid, and solvent for use is ethanol, isopropyl
In alcohol, ethyl lactate at least one.
Further, in described step S4, the laminate pressure of described alignment pressing is 2～2.5Mpa.
On the basis of technique scheme, the present invention further comprises a kind of compound transparent electricity conductive film:
Graphene film (1) that this conductive film includes setting gradually, silver nanowire layer (2), solid-state light solidifying coating (3),
Flexible and transparent basal layer (4)；
Described graphene film (1) is formed in metal substrate surface catalytic growth monocrystalline sublayer；
Described silver nanowire layer (2) is at graphene film (1) surface-coated nano silver wire dispersion liquid and dries formation；
Described solid-state light solidifying coating (3) is by the upper even spread liquid photocurable material of flexible and transparent basal layer (4)
Formed.
Further, described nano silver wire dispersion liquid is aqueous liquid dispersion, and this nano silver wire dispersion liquid also comprises nanoscale breast
Liquid.
Further, described nanoscale emulsion is the water-based emulsion of polyester-type aliphatic polyurethane resin, and resin concentration is
0.01～100mg/mL.
Further, described liquid photocurable material is the one in radically curing system material, can 275～
Solidifying in the range of the light wave of 400nm, viscosity is 50-1000cps, and preferred range of viscosities is 50～200cps.
Further, the sheet resistivity resistance number of described compound transparent electricity conductive film is 5～200 sheet resistances.
Further, the transmitance of described compound transparent electricity conductive film is 85～92%.
The invention has the beneficial effects as follows: can be with control realization low square resistance with high with the compound of graphene film by nano silver wire
Transmitance；There is water-resistant stability and the heat-resistant stability of improvement of excellence simultaneously；Additionally Graphene and nano silver wire composite guide
The transfer integrity of electric layer is realized with solidification crosslinking by the infiltration of LLC；And sheet resistance uniformity and reproducibility, laid by painting
The standby nano silver wire coating weight that is precisely controlled realizes, it is ensured that the stability of bulk article；Top layer graphene film conductive layer, improves thin film
Surface chemistry inertia, effectively stops silver wire oxidation, improves surface current and is uniformly distributed.
Accompanying drawing explanation
The structure chart layer of composite transparent conductive film prepared by Fig. 1 position present invention；
Fig. 2 is the schematic flow sheet of composite transparent conductive film prepared by the present invention；
In accompanying drawing, the list of parts representated by each label is as follows:
1, graphene film, 2, silver nanowire layer, 3, solid-state light solidifying coating, 4, flexible and transparent basal layer
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with accompanying drawing, example is served only for explaining the present invention, and
Non-for limiting the scope of the present invention.
As it is shown in figure 1, prepare the schematic flow sheet of composite transparent conductive film for the present invention, its as shown in Figures 2 and 3 transparent
Conducting membrane structure and exterior view detailed description following steps:
S1, uses chemical gaseous phase depositing process at metal substrate surface catalytic growth monocrystalline sublayer graphene film, obtains stone
The structure I of ink alkene film-metal substrate；
S2, the graphenic surface in structure I coats nano silver wire dispersion liquid and dries, it is thus achieved that nano silver wire-graphene film-
The composite construction II of metal substrate；
S3, even spread liquid photocurable material in flexible and transparent substrate, obtain liquid photocurable coating-flexible and transparent
The composite construction III of substrate；
S4, is directed at pressure by the liquid photocurable coating in composite construction III with the nano silver wire coating in composite construction II
Close, obtain the composite construction IV of flexible and transparent substrate-liquid photocurable coating-silver nanowire layer-graphene film-metal substrate；
S5, carries out irradiation to composite construction IV, makes liquid photocurable coating be changed into solid-state, obtain flexible and transparent substrate-
The composite construction V of solid-state light solidifying coating-nano silver wire-graphene film-metal substrate；
S6, by electrochemical process stripping means, separates the metal substrate in composite construction V, obtains having flexible and transparent
The composite conducting fexible film of substrate-solid-state light solidifying coating-nano silver wire-graphene film.
The present invention provides the transparent conductive film of the graphene film including prepared by base material, nano silver wire coating and CVD.
Wherein, as long as above-mentioned base material clear flexible material is just not particularly limited, especially, it is preferred that optical grade is gathered right
PET (PET, Polyethylene Terephthalate), polymethyl methacrylate (PMMA, Poly
Methyl Methacrylate), polyether sulfone (PES, Poly Ether Sulfone), Merlon (PC, Poly
Carbonate), the one in polyimides (PI, Poly Imide).
The nano silver wire coating fluid of the present invention is made up of nano silver wire aqueous dispersions and nano-scale water emulsion and auxiliary agent.
The preferred aqueous dispersion of nano silver wire of the present invention, on the one hand, experiment find, water-dispersible nano silver wire and other
The composite effect of conductive material is substantially better than alcohol dispersion；On the other hand, using aqueous dispersion, " three wastes " are less, more ring
Protect, be more beneficial for large-scale production.
Preferably, a length of 10～100 μm of the above-mentioned nano-silver thread included by the compound transparent electricity conductive film of the present invention,
Draw ratio is 500～2000:1.Preferably, diameter 25～30nm, length 20～30 μm.
The nano silver wire concentration of the above-mentioned coating fluid included by the compound transparent electricity conductive film of the present invention is 0.1～10mg/
ML, coating thickness is 5～200 μm.It is furthermore preferred that nano silver wire concentration is 0.5mg/mL, coating thickness is close according to required silver wire
Depending on degree.
Water-based emulsion component in nano silver wire coating fluid, is effectively improved the nano silver wire conductive layer after film forming and Graphene
The ply adhesion of film and compactness；Emulsifying agent and levelling agent, reduce the surface tension of coating fluid, improve uniform levelability.
The preferred waterborne polyurethane resin of nano-scale water emulsion of the present invention, water polyacrylic acid resin, water-base epoxy
The macromolecule emulsions such as acrylate, waterborne organic silicon resin.Preferably, described nano-scale water emulsion be polyurethane and
Emulsion prepared by polyacrylate, nano-scale water emulsion can also is that following: the breast of polyether-type, polyester-type or polycarbonate type
Liquid, aliphatic, alicyclic or aromatic series, the emulsion of polyurethane acrylate resin；Poly-(methyl) acrylic acid methyl ester., poly-(methyl)
Butyl acrylate, poly-(methyl) 2-(Acryloyloxy)ethanol and the multiple mixing of acrylate monomer (randomly, block, grafting) polymer
The emulsion of resin etc..Preferably, aqueous polyurethane emulsion, molecule contains the carbamate structures of a large amount of strong hydrogen bondings, can be bright
The each ply adhesion of aobvious raising.
Preferably, the water-based emulsion of polyester-type aliphatic polyurethane resin, resin concentration is 0.01～100mg/mL.Preferably
, water-base resin concentration is 0.1mg/mL.
The emulsifying agent main component of the present invention is hydrophilic macromolecule, it is preferred that TritonX, cellulose, Polyethylene Glycol etc.,
It is effectively improved the coating fluid levelling uniformity at substrate surface.
The graphene film of the present invention is grown on the metallic substrate surface such as copper, nickel, platinum, cobalt by CVD technology.Preferably, copper
Matter substrate.Preferably, the graphene film of lattice dimensions 5～100 μm, the monolayer accounting of Graphene is 90～96%.
The method of silver coating nanowire dispersion on the metal base of graphene film is had to include spin-coating method, blade coating in growth
The multiple method such as method, spraying process.Wherein, spin-coating method is unfavorable for that scale produces continuously；Knife coating easy damaged base material and conduction are coated with
Layer surface.Preferably spraying process, and two traditional fluid spraying processes, not only effective rate of utilization is low, and consumption of raw materials cost is high；And it is silver-colored
Nanowire dispersion, easily piles up at nozzle mouth and reunites, affect coating homogeneity, and meanwhile, the outlet air pressure of two fluid sprayings is relatively big,
Easily the metal substrate surface such as the thinnest copper after taking off fire are produced impact failure.Preferably, ultrasonic spraying.
Ultrasonic spraying, higher to coating fluid effective rate of utilization, effectively reduce coating consumption and post processing cost；Outlet pressure
Being adjustable to will not be to producing impact at the bottom of thin metal matrix；Coating homogeneity is more easy to control, produces more stable continuously.
In order to ensure coating homogeneity, use the mode repeatedly sprayed.
The graphene film of the present invention is grown on the metallic substrate surface such as copper, nickel, platinum, cobalt by CVD technology, it is preferred that copper
Matter substrate；Preferably, the graphene film of lattice dimensions 5～100 μm.By LLC pressing, solidify, transfer to transparent flexible base material
Surface.
The transfer light solidifying coating of the present invention is not limited to any type LLC, but must assure that its optical clear
Property, film transmission rate will not be reduced after coating, i.e. optical thin film photo-curing material (Light-curing Coating of
Optical film).Preferably, the radical UV curing system of curing rate esters of acrylic acid faster.Preferably, main body tree
Fat is the urethane acrylate resinoid of the carbamate structures on strand containing a large amount of strong hydrogen bondings, has higher gluing
Power and toughness.
The LLC of the present invention can be by organic solvent diluting, including various common solvents.As long as solubilized LLC, it is not limited to alcohol
Class, ketone or esters solvent.Preferably, the dissolubility such as ethanol, isopropanol, ethyl lactate is good, low toxicity, low abnormal smells from the patient, lower boiling
Polar solvent.
Organic solvent diluting LLC is to certain viscosity so that it is can be spread evenly across substrate surface by coating apparatus.Dry
After, pressing is covered on nano silver wire and the metallic substrates of graphene composite conductive layer.LLC can be diluted to relatively low glutinous by solvent
Degree, it is ensured that silver nanowire layer and graphene film are infiltrated fully.Meanwhile, by the modulation of LLC content Yu wet-film thickness, can be by
LLC build controls to nanoscale.Preferably, the solid content of LLC is 1～100mg/mL.
The method being coated with LLC solution on flexible and transparent base material includes the multiple methods such as spin-coating method, knife coating, spraying process.
Preferably, it is adaptable to the nick coating method being difficult to scratch of film product continuous prodution.
The growth being coated with silver nanowire layer of the present invention has the metal base of graphene film and is coated with the transparent of LLC
The equipment of flexible parent metal laminating, is not limited to the press equipments such as any type of rolling, lamination.Preferably, pressing contact surface is thick
Rugosity is less than 1 μm, and partial operation environment reaches the equipment of 100 grades of purification standards.Preferably, pressing pressure be 0.1～
20MPa.It is furthermore preferred that pressing pressure is 2～2.5MPa.
LLC is in bonding processes, it is possible to complete wetting silver nanowire layer and graphene film.After ultraviolet light polymerization, film layer energy
Enough firm constraint nano silver wires and Graphene, it is ensured that in stripping process, transfer is completely.Meanwhile, pressing working procedure, suitable pressing
Power, can be effectively improved between nano silver wire and with contact density between Graphene, improve electric conductivity further.
After fully solidifying, cooling down, remove metal base, but be not limited to the side of any removable metal base
Method.Preferably, electrochemical stripping method, laminating base material is totally submerged in alkaline aqueous solution, metal base is connected with negative pole, logical
Electricity, is electrolysed water in metallic substrate surface, produces bubble, and bubbling peels off Graphene；Realize Graphene and transferred to by LLC transparent soft
Property base material, thus prepare Graphene and nano silver wire composite conductive thin film.
Preferably, the alkali of the present invention is technical grade sodium hydroxide, it is preferred that the concentration of sodium hydrate aqueous solution be 0.5～
5mol/L。
Hereinafter, by specific embodiment as it is shown in figure 1, compound transparent electricity conductive film of the present invention and preparation method thereof is entered
Row explanation
Embodiment 1
(1) preparation of nano silver wire coating fluid
With diameter 25～30nm, the nano silver wire aqueous liquid dispersion of length 20～30 μm is main material, and admittedly contains with silver wire
On the basis of amount, it is separately added into the emulsifying agent (pluronic polymer as water-soluble in triton x-100, cellulose etc.) and 1/5 of 1/5
Water-base resin (such as Holland's aqueous polyurethane emulsion such as this tal fibre PU-704, PU-653), and be diluted to silver wire with deionized water
Concentration is 0.5mg/mL, and preparation can be used for the coating fluid of spraying；
(2) preparation of LLC coating fluid
By the LLC proportioning in proportion of preparation, and with ethanol dilution to certain solid content, prepare the LLC solution that can be coated with；
(3) coating silver nanowire layer
Nano silver wire coating fluid step (1) prepared is by the way of spraying, and being spread evenly across growth has graphene layer
Metallic substrate surface (i.e. structure I)；Dry some minutes in 110 DEG C, except volatile matters such as water, obtain composite construction II；
(4) coating LLC
UV diluent prepared by step (2) is coated optical grade PET base material surface；In some points of 80 DEG C of hot-air seasonings
Clock, removes volatile solvent, and film forming, obtains composite construction III；
(5) transparent flexible base material is pasted
By the liquid photocurable coating of composite construction III prepared by step (4), in the composite construction II prepared with step (3)
Nano silver wire coating alignment, under the pressure of 2MPa rolling laminating, obtain composite construction IV；If solidifying under ultraviolet exposure machine
Dry minute, obtain composite construction V；
(6) stripping metal base material
After sufficiently cool, the composite construction V step (5) prepared, immersing concentration is 2mol/L sodium hydrate aqueous solution
In, metal base is connected with negative pole, and makes positive pole immerse in aqueous alkali, form successive loops.Energising, treats that metallic substrate surface goes out
After existing bubble, slowly peel off, make metal base separate with PET base material.Now, under the constraint of the LC film of solid-state, Graphene with
Nano silver wire is transferred in PET base material, and nano silver wire is in close contact with Graphene, and nano silver wire is positioned at bottom, aoxidizes stone
Ink alkene is positioned at top layer, obtains Graphene and nano silver wire compound transparent electricity conductive film；
The complex method of graphene film prepared by nano silver wire conductive layer provided in the present embodiment and CVD is only
Being schematic, other any complex methods that can form described silver nanowire layer and graphene layer all replace described method, example
As the modes such as available blade coating, spin coating, dip-coating replace ultrasonic spraying, form nano silver wire conductive layer；Available spraying, spin coating, dip-coating
Replace nick to be coated with etc. mode, form the LLC layer of liquid.
The graphene composite conductive that embodiment 1～12 provides the nano silver wire transferring in PET base material and CVD to prepare is thin
Film, in addition to the condition described in table 1, concrete operating process is identical with preparation example 1.
The experiment condition of table 1 1～10
Performance test
Nano silver wire and graphene composite conductive thin film to experiment condition 1～12 preparation carry out performance test, survey respectively
Examination:
1. surface resistivity: use the sheet resistance of four probe method test compound conductive film；
2. water resistance: under room temperature, is totally submerged the composite conductive thin film of graphene film-nano silver wire-PET base material
In ionized water, after reaching soak time, sample is taken out, dries up, test its electric conductivity by four probe method；
3. resistance to elevated temperatures: the composite conductive thin film of graphene film-nano silver wire-PET base material is put into the baking oven of 150 DEG C
In, (meet the electronic product of some backend application process requirements in the fabrication process, as PET base material is added after heating 2h
Hot shrinking processes), take out sample, after cooling, with its electric conductivity of four probe tests；
4. transmitance: with ultraviolet-visible spectrophotometer (the general TU-1900 of general analysis) test sample wavelength be 290～
The transmitance of 780nm scope (not deducting optical grade PET base material).
Experiment condition 1～12 the performance test results is as shown in table 2:
Table 2 1～12 experiment condition the performance test results
By experiment condition 1～12 it can be seen that along with the increase of the raising of nano silver wire layer thickness, i.e. wet-film thickness, lead
Electrically improve, and transmitance declines.But between the electric conductivity of composite conductive thin film and nano silver wire layer thickness, it is not linear
Relation.Along with the raising of silver wire thickness, compound sheet resistance downward trend slows down, i.e. along with the raising of electric conductivity, and the contribution of Graphene
It is gradually lowered；Meanwhile, the raising to electric conductivity that rises of silver wire unit intensity the most gradually weakens.
Before and after the immersion of each print, sheet resistance all almost without change, shows composite conductive thin film resistance to water pole prepared by this technique
Good.
Along with the LLC concentration of liquid and the transfer of the raising of coating thickness, nano silver wire and Graphene are more complete.But high temperature
In Heating Experiment, initial conduction performance is the poorest, and sheet resistance is the highest, i.e. silver wire density is the lowest；Meanwhile, the sample that the LC film of solid-state is the thickest
Product, after heating, sheet resistance rises the most obvious.Main cause is, the LC film of solid-state is in long-term thermal histories, and macromolecule thaws, aggravation
Molecular motion, release solidification process in produce internal stress, glued membrane expand, not only pull open the spacing of nano silver wire, between silver wire
Non-conductive section increase；At the same time it also is possible to burst graphene layer, thus causing electric conductivity to decline, sheet resistance substantially rises.Cause
And, the build of liquid LLC to control in certain scope.
In this manual, the schematic representation of above-mentioned term is necessarily directed to identical embodiment or example.
And, the specific features of description, structure, material or feature can with in one or more embodiments in office or example with suitably
Mode combines.Additionally, in the case of the most conflicting, those skilled in the art can be by the difference described in this specification
The feature of embodiment or example and different embodiment or example is combined and combines.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is example
Property, it is impossible to being interpreted as limitation of the present invention, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, revises, replaces and modification.
Claims (13)
1. the preparation method of a compound transparent electricity conductive film, it is characterised in that this preparation method comprises the steps:
S1, uses chemical gaseous phase depositing process at metal substrate surface catalytic growth monocrystalline sublayer graphene film, obtains Graphene
The structure I of film-metal substrate；
S2, the graphenic surface in structure I coats nano silver wire dispersion liquid and dries, it is thus achieved that nano silver wire-graphene film-metal
The composite construction II of substrate；
S3, even spread liquid photocurable material in flexible and transparent substrate, obtain liquid photocurable coating-flexible and transparent substrate
Composite construction III；
S4, is directed at pressing by the liquid photocurable coating in composite construction III with the nano silver wire coating in composite construction II,
Composite construction IV to flexible and transparent substrate-liquid photocurable coating-silver nanowire layer-graphene film-metal substrate；
S5, carries out irradiation to composite construction IV, makes liquid photocurable coating be changed into solid-state, obtains flexible and transparent substrate-solid-state
The composite construction V of light solidifying coating-nano silver wire-graphene film-metal substrate；
S6, by electrochemical process stripping means, separates the metal substrate in composite construction V, obtains having flexible and transparent base
The composite conducting fexible film of the end-solid-state light solidifying coating-nano silver wire-graphene film.
The preparation method of compound transparent electricity conductive film the most according to claim 1, it is characterised in that in described step S1,
The monolayer accounting of described graphene film is 90-96%, graphene film monocrystalline a size of 5-100 μm.
The preparation method of compound transparent electricity conductive film the most according to claim 1 and 2, it is characterised in that described step S2
In, described nano silver wire dispersion liquid is aqueous liquid dispersion, and wherein adds nanoscale emulsion.
The preparation method of compound transparent electricity conductive film the most according to claim 3, it is characterised in that described nanoscale breast
Liquid is the water-based emulsion of polyester-type aliphatic polyurethane resin, and resin concentration is 0.01-100mg/mL.
The preparation method of compound transparent electricity conductive film the most according to claim 1, it is characterised in that in described step S3,
Described liquid photocurable material belongs to the one in radically curing system material, can consolidate in the range of the light wave of 275-400nm
Changing, range of viscosities is 50-200cps.
The preparation method of compound transparent electricity conductive film the most according to claim 1, it is characterised in that in described step S3,
Described liquid photocurable material organic solvent diluting becomes coating fluid, solvent for use be in ethanol, isopropanol, ethyl lactate extremely
Few one.
The preparation method of compound transparent electricity conductive film the most according to claim 1, it is characterised in that in described step S4,
The laminate pressure of described alignment pressing is 2-2.5Mpa.
8. a compound transparent electricity conductive film, it is characterised in that this conductive film includes graphene film (1), the silver set gradually
Nano wire layer (2), solid-state light solidifying coating (3), flexible and transparent basal layer (4)；
Described graphene film (1) is formed in metal substrate surface catalytic growth monocrystalline sublayer；
Described silver nanowire layer (2) is at graphene film (1) surface-coated nano silver wire dispersion liquid and dries formation；
Described solid-state light solidifying coating (3) is to be formed by the upper even spread liquid photocurable material of flexible and transparent basal layer (4)
's.
Compound transparent electricity conductive film the most according to claim 8, it is characterised in that described nano silver wire dispersion liquid is aqueous
Dispersion liquid, this nano silver wire dispersion liquid also comprises nanoscale emulsion.
Compound transparent electricity conductive film the most according to claim 9, it is characterised in that described nanoscale emulsion is polyester
The water-based emulsion of type aliphatic polyurethane resin, resin concentration is 0.01-100mg/mL.
11. compound transparent electricity conductive films according to claim 8, it is characterised in that described liquid photocurable material belongs to
One in radically curing system material, can solidify in the range of the light wave of 275-400nm, and range of viscosities is 50-
200cps。
12. compound transparent electricity conductive films according to claim 8, it is characterised in that described compound transparent electricity conductive film
Sheet resistivity resistance number be 5-200 sheet resistance.
13. compound transparent electricity conductive films according to claim 8, it is characterised in that described compound transparent electricity conductive film
Transmitance be 85-92%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106128563A (en) * | 2016-08-15 | 2016-11-16 | 东莞市纳利光学材料有限公司 | A kind of conductive and heat-conductive film and preparation method thereof |
| CN110176433A (en) * | 2019-04-30 | 2019-08-27 | 杭州电子科技大学 | A kind of flexibility base compound substrate and preparation method thereof |
| TWI674302B (en) * | 2017-03-07 | 2019-10-11 | 日商同和電子科技有限公司 | Method for manufacturing silver nanowire ink and silver nanowire ink and transparent conductive coating film |
| CN114188091A (en) * | 2021-11-28 | 2022-03-15 | 北京大华博科智能科技有限公司 | Patterned transparent circuit and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120436A (en) * | 1982-12-27 | 1984-07-12 | Seikosha Co Ltd | Manufacture of anisotropically conductive rubber sheet |
| CN104464955A (en) * | 2014-11-28 | 2015-03-25 | 中国科学院金属研究所 | Method for manufacturing large-area high-performance graphene composite transparent conductive films on large scale |
| CN105786242A (en) * | 2016-02-02 | 2016-07-20 | 广州聚达光电有限公司 | Flexible touch panel sensing film and preparation method thereof |
| US20160225482A1 (en) * | 2015-01-30 | 2016-08-04 | Xerox Corporation | Composition comprising silver nanowires |
-
2016
- 2016-08-08 CN CN201610643280.7A patent/CN106297964A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120436A (en) * | 1982-12-27 | 1984-07-12 | Seikosha Co Ltd | Manufacture of anisotropically conductive rubber sheet |
| CN104464955A (en) * | 2014-11-28 | 2015-03-25 | 中国科学院金属研究所 | Method for manufacturing large-area high-performance graphene composite transparent conductive films on large scale |
| US20160225482A1 (en) * | 2015-01-30 | 2016-08-04 | Xerox Corporation | Composition comprising silver nanowires |
| CN105786242A (en) * | 2016-02-02 | 2016-07-20 | 广州聚达光电有限公司 | Flexible touch panel sensing film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 罗祥林: "《功能高分子材料》", 28 February 2010 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106128563A (en) * | 2016-08-15 | 2016-11-16 | 东莞市纳利光学材料有限公司 | A kind of conductive and heat-conductive film and preparation method thereof |
| TWI674302B (en) * | 2017-03-07 | 2019-10-11 | 日商同和電子科技有限公司 | Method for manufacturing silver nanowire ink and silver nanowire ink and transparent conductive coating film |
| CN110176433A (en) * | 2019-04-30 | 2019-08-27 | 杭州电子科技大学 | A kind of flexibility base compound substrate and preparation method thereof |
| CN110176433B (en) * | 2019-04-30 | 2020-12-18 | 杭州电子科技大学 | Flexible base composite substrate and preparation method thereof |
| CN114188091A (en) * | 2021-11-28 | 2022-03-15 | 北京大华博科智能科技有限公司 | Patterned transparent circuit and preparation method and application thereof |
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