CN109961877A - Plasma spraying formula graphene transparent conductive film substrate preprocess method - Google Patents
Plasma spraying formula graphene transparent conductive film substrate preprocess method Download PDFInfo
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- CN109961877A CN109961877A CN201711408298.XA CN201711408298A CN109961877A CN 109961877 A CN109961877 A CN 109961877A CN 201711408298 A CN201711408298 A CN 201711408298A CN 109961877 A CN109961877 A CN 109961877A
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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
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
The invention discloses a kind of plasma spraying formula graphene transparent conductive film substrate preprocess methods, which is characterized in that using processing gas such as hydrogen, oxygen, nitrogen or helium, handling by ac magnetic field makes its plasma and be ejected into substrate surface;To carry out the modified pretreatment in surface, clean the surface and reduction surface tension to film substrate, and in Surface Creation polar group.Also disclose a kind of roll-to-roll continuous preparation method of graphene transparent conductive film using above-mentioned preprocess method.The advantages that present invention utilizes the surface preparations that room temperature plasma spraying principle realizes transparent film substrate, have implementation simply, easy to operate, are conducive to control, and pretreating effect is good high-efficient, can be improved the adhesion effect of film substrate follow-up function layer.
Description
Technical field
The invention belongs to graphene transparent conductive film preparation fields, and in particular to saturating to a kind of plasma spraying formula graphene
Bright conduction film base material preprocess method.
Background technique
Graphene is that a kind of ideal photon and photoelectron material, graphene transparent conductive film can be widely applied to hand
The fields such as machine, tablet computer and touch panel device are a kind of very widely used electronics industry basic materials.
Existing conventional transparent graphene conductive film preparation method, usually CVD method need first to grow shape on copper foil
At graphene film, one layer of organic glass protective layer is then smeared again, and then corrosion, which is fallen, is transferred to film for graphene film after copper foil
Then substrate surface removes organic glass protective layer again.This preparation method, there are process conditions harshnesses;Operating procedure is complicated;
In the presence of can not overcome inherence, inherent shortcoming, leading to yield rate, at high cost, low efficiency cannot achieve continuous production lower than 40%;
And the defects of product only has lower conduction/light transmission ratio, i.e., quality factor are low, and electric conductivity is poor.
Number of patent application 201510481379.7 was once disclosed a kind of preparation method of graphene film, was soaked using ultrasonic wave
Graphene oxide solution is applied in PET film, is carbonized, is graphitized and obtains stone by bubble stirring graphene oxide, impurity screening
Black alkene film.But this mode still has complex process, and carbonization and graphitization step are difficult to control accurately, and lead to product matter
Measure poor defect.This preparation method can not obtain the graphene transparent conductive film of available PET carrying, but by PET
Film is carbonized together with graphene, then is graphitized.The graphene film being prepared, light transmittance are extremely low or even completely impermeable
Light, poorly conductive, it is impossible to be used in transparent conductive film.It is generally used as heat conducting film.
It is other that there are also rotary coatings, dipping absorption, LB method (Langmuir-Blodgett), self-assembly method (SA;Self-
Assembly) etc..In these methods, first two is only suitable for making in laboratory.LB method and self-assembly method can obtain comparing having
The multi-layer ultrathin membrane of sequence.Self-assembly method is simple and easy to do, without special device, usually takes water as a solvent, and has with molecular level control
The advantages of depositing process processed and membrane structure.It can use successive sedimentation heterogeneity, prepare two dimension or even three-dimensional ratio between film layer
More orderly structure realizes the functions such as the light, electricity, magnetic of film, therefore in recent years by attention.But both methods is used to practical system
Producing transparent conductive film film, microprocess is extremely complex, is not suitable for volume production.
Side so far still without relatively simple, efficient, inexpensive large-scale production graphene transparent conductive film
Method.
The CN201410847076.8 that the present inventor once applied is disclosed a kind of metal nanometer line-graphene gantry knot
The manufacturing method of structure composite material, but there is no announce specific roll-to-roll graphene transparent conductive film continuous producing method.
Still lack one kind so far, technique requires low, high-efficient, at low cost, easy to control, high-quality, suitable extensive
The graphene transparent conductive film preparation method of production.The significant problem urgently to be resolved as those skilled in the art.
To solve the above-mentioned problems, applicant considers to devise a kind of roll-to-roll graphene transparent conductive film continuously side of preparation
Method, in this method, including the following steps being successively carried out continuously: the modified pretreatment in surface a, is carried out to transparent film substrate,
Clean the surface and reduction surface tension;B, film substrate surface is continuously coated with multi-functional priming coat, it is made to further decrease surface
Tension increases the binding force with graphene conductive material layer;C, at least one layer of grapheme material layer, grapheme material layer are coated
Including at least several small flake graphite alkene, and the metal nanometer line grown thereon;D, coating is made to spread over multi-functional bottom
Numerous mutual overlapped points welding is whole between the metal nanometer line on grapheme material on coating, and fixed between each layer
It is integrated.
But wherein, how a step is specifically realized, can implement simply, easy to operate, is conducive to control, improves pre-
Treatment effect improves the adhesion effect of film substrate follow-up function layer, becomes those skilled in the art and needs further to consider solution
Certainly the problem of.
Summary of the invention
In view of the above shortcomings of the prior art, it is utilized the technical problems to be solved by the present invention are: how to provide one kind
Room temperature plasma spraying principle, and implement simply, it is easy to operate, it is conducive to control, pretreating effect is good high-efficient, can be improved thin
The plasma spraying formula graphene transparent conductive film substrate preprocess method of the adhesion effect of film base material follow-up function layer.
Vocabulary of terms involved in the application is as follows: quality factor: the ratio between electrically conducting transparent membrane conductivity and light transmittance σdc/
σopt.Transparent conductive film is in addition to excellent electric conductivity, it is also necessary to the ratio between excellent conductivity, light transmission (σdc/σopt )。σdc
Determine the surface resistance of transparent conductive film, σoptDetermine the light transmission rate of transparent conductive film.Quality factor can describe electrically conducting transparent very well
The photoelectric properties of film.
In order to solve the above technical problems, technical scheme is as follows:
A kind of plasma spraying formula graphene transparent conductive film substrate preprocess method, which is characterized in that using hydrogen, oxygen,
The processing gas such as nitrogen or helium, handling by ac magnetic field makes its plasma and is ejected into substrate surface;To thin
Film base material (being specifically as follows the film substrates such as PET, PEN, PMMA, PC film or PI film) carries out the modified pretreatment in surface, cleaning
Surface and reduction surface tension, and in Surface Creation polar group.
In this way, passing through bombardment of the lotus energy particle to film substrate surface in plasma: or by free radical, ion with it is thin
Film base material surface molecular reaction production volatile small molecule removes material surface weak boundary: to cause surface microscopic topographic to become
Change --- roughing in surface: and along with chain break, formation of free radical etc..Plasma and film substrate material surface are mutual
Effect, makes film substrate surface active, grafting or cross-linking reaction: introducing active group on the surface of the material, or passes through these activity
Group is introduced compared with long-chain branch compound: or one layer of corsslinking molecular is formed on the surface of the material.Oxygen is exponentially introduced thin transparent membrane material
Expect surface, foring a large amount of oxygen-containing polar group makes film substrate surface be easy to the functional groups with coating.Generate polymerization
Object free radical promotes fiber sheath to generate the reactions such as etching, exchange, grafting and copolymerization.Further, since material is in treatment process
In, molecule, atom and ion in plasma penetrate into material surface, and the atom of material surface escapes into plasma.This
A technical process can achieve the unapproachable chemically and physically modified effect of conventional method.
Which mainly causes the variation of material surface chemical characteristic, and Macroscopic physical pattern varying less or can be ignored not
Meter, corona treatment are only related to from material surface to the tens of angstroms of ranges to the 1000 Izods right side, base inside transparent thin-film material
Matter does not change.Material body characteristic is not influenced.Therefore the surface for being particularly suitable for the organic materials such as polymer is modified.It is this
Processing mode belongs to nonequilibrium plasma processing mode.
As optimization, this method can specifically be realized using gas plasma ejection processing device, the gas plasma
Ejection processing device includes horizontally disposed substrate, and substrate is located above one section of horizontal route of film substrate, and base lower surface is perpendicular
It is directly fixedly installed the ion injection torch array being made of injection torch jet pipe downwards, sprays torch jet pipe and is made for insulating materials, spray
Torch jet pipe upper end connection gas source is penetrated, diametrically opposite both ends in torch jet pipe circumferential lateral surface is sprayed and is further fixedly arranged on pairs of electricity
Pole is additionally provided with the controller being connected with electrode.
In this way, gas source provides processing gas and air pressure, spray processing gas downwards from injection torch jet pipe, while by control
Device coordination electrode processed generates ac magnetic field, so that generating glow discharge phenomenon, Huo Zhe electricity inside the gas spray pipe between electrode
Hold couple microwave discharge phenomenon or inductive coupling microwave discharge phenomenon, so that after processing gas is ionized at a lower temperature
It sprays, under the premise of which does not influence film substrate itself acute variation, realizes the modification to film substrate surface.Tool
Have that structure is simple, processing efficiently, can be realized non-equilibrium plasma processing, and degree of ionization is high;Gas has higher activation degree.
The plasma with higher energy is obtained and maintained at lower temperatures, thermally sensitive transparent organic film material is more suitable for
The advantages that material.
Further, the injection torch jet pipe is arranged in multiple rows of on substrate for uniform but dislocation.In this way, Heterogeneous Permutation
Ion sprays torch array, can preferably improve treatment effect.
The electrode sections are arc-shaped and fitting is fixed on outside injection torch jet pipe.In this way, can be preferably conducive to electric field
It is formed and is conducive to improve electric field action effect.
Further, two pairs of electrodes are provided on the injection torch jet pipe, two pairs of electrodes are vertically intervally arranged, and each pair of
Electrode connecting line direction is arranged vertically.
In this way, can better ensure that can pass through electric field through all gas in overspray torch jet pipe, and obtain more
Add uniform electric field treatment effect.
The invention also discloses a kind of roll-to-roll continuous preparation methods of graphene transparent conductive film, it is characterized in that, including
The following steps being successively carried out continuously: it a, is pre-processed using plasma spraying formula graphene transparent conductive film substrate as described above
Method, which is realized, carries out the modified pretreatment in surface, clean the surface and reduction surface tension to transparent film substrate;B, film substrate
Surface is continuously coated with multi-functional priming coat, it is made to further decrease surface tension, the combination of increase and graphene conductive material layer
Power;C, it is coated at least one layer of grapheme material layer, grapheme material layer includes at least several small flake graphite alkene, Yi Jiqi
The metal nanometer line of upper growth;D, make coating spread over the metal nanometer line on grapheme material on multi-functional priming coat it
Between numerous mutual overlapped points welding be whole, and be fixed as one between each layer;It further include step e after Step d, in above-mentioned step
Suddenly treated, and film substrate surface is continuously coated with anti-reflection optical match layer;Further include step f overlay film after step e, that is, is being arranged
The film substrate upper and lower surface of good anti-reflection optical match layer fits over setting layer protecting film.Above-mentioned roll-to-roll graphene is transparent
The continuous preparation method of conductive film have it is easy to operate, it is low in cost, be conducive to control, the advantages that high production efficiency, good product quality.
Therefore present invention utilizes the surface preparation that room temperature plasma spraying principle realizes transparent film substrate, has and implement
Simply, easy to operate, it is conducive to control, pretreating effect is good high-efficient, can be improved the attachment effect of film substrate follow-up function layer
The advantages that fruit.
Detailed description of the invention
Fig. 1 is the gas plasma used when a kind of continuous preparation method specific implementation of roll-to-roll graphene transparent conductive film
The structural principle simplified schematic diagram of ejection processing device.
Fig. 2 is the sided corona treatment dress used when a kind of continuous preparation method specific implementation of roll-to-roll graphene transparent conductive film
The structural principle simplified schematic diagram set.
Fig. 3 is at the surface oxidation used when a kind of continuous preparation method specific implementation of roll-to-roll graphene transparent conductive film
Manage the structural principle simplified schematic diagram of device.
Fig. 4 is that the dimple roller that uses when a kind of continuous preparation method specific implementation of roll-to-roll graphene transparent conductive film is poor
The structural principle simplified schematic diagram of fast apparatus for coating overlook direction.
Fig. 5 is that the quantitative feeding used when a kind of continuous preparation method specific implementation of roll-to-roll graphene transparent conductive film turns
Move the structural principle simplified schematic diagram of apparatus for coating.
Fig. 6 is the blade coating dress used when a kind of continuous preparation method specific implementation of roll-to-roll graphene transparent conductive film
The structural principle simplified schematic diagram set.
Fig. 7 is the slit coating used when a kind of continuous preparation method specific implementation of roll-to-roll graphene transparent conductive film
The structural principle simplified schematic diagram of device.
Fig. 8 is the light pulse welding used when a kind of continuous preparation method specific implementation of roll-to-roll graphene transparent conductive film
The structural principle simplified schematic diagram of device.
Fig. 9 is the gas at normal temperature etc. used when a kind of continuous preparation method specific implementation of roll-to-roll graphene transparent conductive film
The structural principle simplified schematic diagram of ion injection fusion splicing devices.
Figure 10 is the roller hot pressing used when a kind of continuous preparation method specific implementation of roll-to-roll graphene transparent conductive film
The structural principle simplified schematic diagram of device.
Specific embodiment
Below with reference to the specific embodiment and attached drawing of a kind of roll-to-roll continuous preparation method of graphene transparent conductive film,
The present invention is described in further details.
A kind of continuous preparation method of roll-to-roll graphene transparent conductive film, it is characterized in that, including what is be successively carried out continuously
Following steps: a, to transparent film substrate (being specifically as follows the film substrates such as PET, PEN, PMMA, PC film or PI film) into
The modified pretreatment in row surface, clean the surface and reduction surface tension, and in Surface Creation polar group;B, film substrate surface connects
The continuous multi-functional priming coat of coating, makes it further decrease surface tension, increases the binding force with graphene conductive material layer, increase
Its polar group number simultaneously adjusts refractive index;C, it is coated at least one layer of grapheme material layer, grapheme material layer includes at least
Several small flake graphite alkene (the flake graphite alkene that may generally be several to dozens of micron square area sizes), and thereon
The metal nanometer line of growth;D, coating is spread between the metal nanometer line on the grapheme material on multi-functional priming coat
Numerous mutual overlapped points welding is whole, and is fixed as one between each layer.
When it is implemented, can also include step e after Step d, in above-mentioned steps, treated that film substrate surface is continuous
It is coated with anti-reflection optical match layer.Anti-reflection optical match layer is used to remove surface spikes and Wei Keng after grapheme material layer welding,
So that product surface is smooth, light transmittance is improved, and adjust refractive index and make increased each layer refractive index and substrate refractive index close
Unanimously.
When it is implemented, can also include step f overlay film after step e, that is, setting the transparent of anti-reflection optical match layer
Film upper and lower surface fits over setting layer protecting film.Play the protective effect to product.
When it is implemented, a step, can realize substrate table by the way of room temperature plasma spraying torch ARRAY PROCESSING
Face pretreatment.The plasma spraying processing is, using processing gas such as hydrogen, oxygen, nitrogen or helium, by alternating current
Magnetic field processing makes its plasma and is ejected into substrate surface.Film substrate surface is banged by lotus energy particle in plasma
It hits: or production volatile small molecule is reacted with film substrate surface molecular for material surface weak boundary by free radical, ion
Removal: to cause surface microscopic topographic to change --- roughing in surface: and along with chain break, formation of free radical etc..Deng from
Daughter and film substrate material surface interactions, make film substrate surface active, grafting or cross-linking reaction: drawing on the surface of the material
Enter active group, or is introduced by these active groups compared with long-chain branch compound: or one layer of corsslinking molecular is formed on the surface of the material.
Oxygen is exponentially introduced transparent thin-film material surface, and foring a large amount of oxygen-containing polar group makes film substrate surface be easy to and apply
The functional groups of material.Free polymer readical is generated, fiber sheath is promoted to generate the reactions such as etching, exchange, grafting and copolymerization.This
Outside, during processing due to material, the molecule in plasma, atom and ion penetrate into material surface, material surface
Atom escapes into plasma.This technical process can achieve the unapproachable chemically and physically modified effect of conventional method.
The step mainly causes the variation of material surface chemical characteristic, and Macroscopic physical pattern varying less or can be ignored not
Meter, corona treatment are only related to from material surface to the tens of angstroms of ranges to the 1000 Izods right side, base inside transparent thin-film material
Matter does not change.Material body characteristic is not influenced.Therefore the surface for being particularly suitable for the organic materials such as polymer is modified.
This processing mode belongs to nonequilibrium plasma processing mode.When it is implemented, gas shown in FIG. 1 can be used
Body plasma spraying processing unit realizes that the gas plasma ejection processing device includes horizontally disposed substrate 1, substrate 1
Above 2 one sections of horizontal routes of film substrate, base lower surface is fixedly installed straight down to be made of injection torch jet pipe 3
Ion sprays torch array, sprays torch jet pipe 3 and is made for insulating materials, and injection 3 upper end of torch jet pipe connects gas source 4, sprays torch jet pipe 3
Diametrically opposite both ends are further fixedly arranged on pairs of electrode 5 in circumferential lateral surface, are additionally provided with the controller being connected with electrode 5
6。
In this way, gas source provides processing gas and air pressure, spray processing gas downwards from injection torch jet pipe, while by control
Device coordination electrode processed generates ac magnetic field, so that generating glow discharge phenomenon, Huo Zhe electricity inside the gas spray pipe between electrode
Hold couple microwave discharge phenomenon or inductive coupling microwave discharge phenomenon, so that after processing gas is ionized at a lower temperature
It sprays, under the premise of which does not influence film substrate itself acute variation, realizes the modification to film substrate surface.Tool
Have that structure is simple, processing efficiently, can be realized non-equilibrium plasma processing, and degree of ionization is high;Gas has higher activation degree.
The plasma with higher energy is obtained and maintained at lower temperatures, thermally sensitive transparent organic film material is more suitable for
The advantages that material.
In above-mentioned gas plasma spraying processing unit, better choice is that the injection torch jet pipe 3 is uniformly but to misplace
Arrangement on substrate 1 multiple rows of.In this way, the ion of Heterogeneous Permutation sprays torch array, treatment effect can be preferably improved.More preferably
, 5 section of electrode is fixed on outside injection torch jet pipe in minor arc shape and fitting.In this way, can be preferably conducive to electric field
It is formed and is conducive to improve electric field action effect.Further, two pairs of electrodes, two pairs of electrodes are provided on the injection torch jet pipe 3
It is vertically intervally arranged, and each pair of electrode connecting line direction is arranged vertically.In this way, can better ensure that through in overspray torch jet pipe
All gas can pass through electric field, and obtain more uniform electric field treatment effect.
In a step, it can also realize that substrate surface pre-processes by the way of high-voltage corona processing;At the high-voltage corona
Reason, even if film substrate passes through the electric field of a high-frequency high voltage, so that plastic film substrate surface generates corona discharge and shows
As, and low temperature plasma is generated, generate the frosting on plastic film substrate surfaceRadical reactionAnd send out polymer
Raw crosslinking, substrate surface is roughening and to increase its rightPolar solventWetability, these gas ions by shock by electricity and penetrate by
Its molecular structure of the surface breakdown of body is printed, and then processed surface molecular is aoxidized and polarized, ion electric shock erosion surface, with
It causes to increase the adhesive ability to subsequent layers.
The mode of above-mentioned high-voltage corona processing specifically can be using corona treatment plant shown in Fig. 2 realization, including one
The shell 7 of rectangle, housing cavity constitute processing workspace, and workspace side is provided with substrate import, and the other side is provided with substrate
It exports, the housing cavity between substrate inlet and outlet forms the space for being advanced through and generating electric field for film substrate 2, shell
Intracavitary be horizontally disposed with has corona cathode transfer roller 8 in body 7, and corona cathode transfer roller 8 is arranged along perpendicular to 2 direction of travel of film substrate,
It is metal material inside corona cathode transfer roller 8 and constitutes electric field cathode, corona cathode transfer roller 8 is arranged at intervals in the vertical direction
The controller 10 that electric field anode 9, electric field anode and electric field cathode are respectively set to hull outside with one is connected.In this way, transfer roller
It electric field and generates under control of the controller while for driving plastic film substrate to advance as being formed between cathode and anode
Corona discharge, breakdown air generate the surface treatment that low-temperature plasma realizes plastic film substrate.
In above-mentioned corona treatment plant, better choice is that electric field anode 9 includes several along plastic film substrate advance side
To spaced several metal electrode boards, metal electrode board is for the point for generating electric field that discharges close to transfer roller one side edge
Sharp shape and be parallel to corona cathode transfer roller 8 setting.In this way, a cathode corresponds to the parallel sharp plate-shaped anode of multiple groups, Ke Yigeng
The discharge spark of multiple groups parallel interval is generated well, treatment effect can be caused unbalanced to avoid single positive corona discharge mode
Defect, improve treatment effect.Further, corona cathode transfer roller and corresponding electric field anode are along substrate direction of travel interval
Be arranged two groups and for generating two electric fields, the respective corona cathode transfer roller of two electric fields is horizontally disposed and corresponding electric field sun
Pole is located at two sides up and down.Sided corona treatment can be carried out to film substrate upper and lower surface simultaneously in this way and be not necessarily to extra intermediate calender rolls
Adjustment direction, and it is conducive to tensioning.
In a step, it can also be that surface oxidation treatment method realizes the surface preparation of film substrate, make film substrate surface
It carries out oxidation reaction and increases polar group number.Specifically there are flame method, acid processing etc..Surface oxidation treatment can increase polymer
The polarity on surface is so as to improve the wellability to water, adhesive strength and printing.Flame method can increase surface oxidation effect
The polarity of bright film surface, so as to improve the wellability to water, cementability and can coating.In air by gas flame
Transparent membrane surface is managed, so that its surface oxidation is generated carbon-oxygen bond, makes it easy in conjunction with coating.
Above-mentioned surface oxidation treatment method can be using surface oxidation treatment device shown in Fig. 3 realization, the surface oxidation
Processing unit, including a flame spray head substrate 11, flame spray head substrate 11 are arranged in parallel in 2 one sections of horizontal segment roads of film substrate
Above diameter, 11 lower surface of flame spray head substrate is provided with the flame spray head being arranged in rows along film substrate width direction straight down
12, flame spray head 12 is connected with gas source 13 by tracheae, and flow control switch valve 14 is provided on the tracheae.In this way, can be with
The distance that flame spray head jets out flames is controlled by adjusting flow control switch valve, it can be just to film substrate surface reality
The Baking out being now able to bear in range, make its generate oxidation reaction, generate a large amount of polar group, make its it is subsequent be easy to and
Coating combines.Have many advantages, such as that structure is simple, handles convenient and efficient efficient.
In above-mentioned surface oxidation treatment device, better choice is that the flame spray head 12 is along film substrate direction of advance
It is spaced apart to be multiple rows of, and every row's flame spray head shifts to install.In this way, can better ensure that uniform to film substrate surface
Toast oxidation effectiveness.Further, the gas source 13 is hydrogen source gas, in this way, the reactive material that burning generates is water, it will not be right
Film substrate performance impacts.Further, between flame spray head 12 and film substrate 2 and positioned at film substrate approaching side position
It sets and is additionally provided with atomizer 12a, atomizer 12a front end emission direction is consistent with 2 direction of advance of film substrate, atomizer
The rear end 12a is connected by conveyance conduit and a container 15, and oxidizing acid solution is provided in container, is also set up in conveyance conduit
There are booster pump 16 and control valve 17.In this way, it is molten to spray oxidizing acid from atomizer by booster pump and control valve control
Liquid, oxidizing acid solution, then the thrust through flame spray head make it drop into film substrate surface, then under the action of flame, fastly
Speed generates oxidation reaction, generates a large amount of polar group, improves polar group number, and it is subsequent and apply to greatly improve film substrate
The combination effect of material.
In b step, the multi-functional priming coat, it include total content is 0.2% ~ 5% to receive that material, which can be effective component,
Rice Zinc oxide particles, titanium dioxide nanoparticle, nanometer silicon dioxide particle, one or more of nano zircite particle and
Total content is continuously applied to thin for the multi-functional bottom coating (solvent is preferably water) that 3% ~ 20% water-based acrylic resin is constituted
The surface of film base material, drying form.
First material is dissolved in polar solvent (water preferably can be used in polar solvent) when preparation, is obtained after mixing more
Function bottom coating by the way of coating, is applied to the surface of film substrate again, then (baking can be used using drying
Case drying) after obtain multi-functional priming coat.Using the multi-functional priming coat of the ingredient, water soluble acrylic acid is conducive to follow-up function layer
Bonding, can provide more polar group numbers, preferably reduction film substrate surface tension, apply rear technique water paint
It covers and easily spreads out homogenization conductive coating;Make conductive layer and basement membrane reaches high bond strength, (such as in conjunction with hot pressing below
Technique realizes embedded physical bond);The thin-film refractive index of nano particle adjustment simultaneously makes it exactly match the transparent of subsequent coated
The refractive index of conductive film layer.It is unlikely to show because of the refractive index difference with bottom after can also making transparent conductive film layer etched pattern
Shadow;The multi-functional priming coat that i.e. b step obtains has both the function for the shadow that disappears.
In b step, the multi-functional priming coat can be prepared with the mode that dimple roller differential is coated with.The method can be with
It is to be coated with using contact, i.e., using micro-textured roller as coating metering roll, line number has very wide range.Micro-textured roller
It is mounted in precision bearing seat, is directly driven by a motor rotation, direction and the film of rotation are walked to expect contrary.Coating is to cut
Coating is applied to film surface by the mode cut.Contact coating means do not have back pressure rubber rollers, eliminates since counter-pressure cylinder adds
Press some potential unfavorable factors generated.
The method, which can also be, to be set side by side using an applicator roll and a coating back flow roll and is respectively driven by motor
Differential speed rotation moves ahead and passes through so that film substrate is driven by coating back flow roll so that applicator roll speed is greater than coating back flow roll
Between applicator roll and coating back flow roll, so that the coating for being provided in be coated with roller surface is extruded to by differential by coating back flow roll
Film substrate surface.Have coating weight accurate in this way, change coating weight is easy, and adjustment coated face is easy, and transfer coated quality is high,
The advantages that simple and reliable, repetition stability is fine, easy to control, high-efficient.
Specifically, the dimple roller differential coating can be real using dimple roller differential apparatus for coating shown in Fig. 4
Existing, the dimple roller differential apparatus for coating includes an applicator roll 18 being set side by side and a coating back flow roll 19, applicator roll
18 are respectively sequentially connected with a power motor with coating back flow roll 19 and can lean on power motor drive differential synchronous rotary, coating
18 velocity of rotation of roller is greater than coating back flow roll;Film substrate is by applicator roll 18 and coats between back flow roll 19, so that the film passed through
Substrate is coated back flow roll tensioning and is bonded with applicator roll 18;19 surface of applicator roll is provided with width along the length direction and is
The micro-recesses 20 of 0.015mm-0.5mm are additionally provided with the coating feeding device to connect with micro-recesses 20.In this way, can be more
The synchronous coating control of differential is realized well, and structure is simple, it is easy to implement.
In above-mentioned dimple roller differential apparatus for coating, better choice is that the coating back flow roll 18 is shorter in length than applicator roll
Length and consistent with the micro-recesses length on applicator roll.Realize that the full surface of film substrate applies in this way, can better ensure that
Cloth.Further, the coating feeding device, including being located at the coating chamber inside applicator roll 18, the setting of 20 bottom of micro-recesses
There are through-hole 21 and coating chamber to communicate, the shaft of applicator roll one end is hollow charging shaft 22 and is connected to coating chamber that charging turns
Axis outer end is connected by rotating seal 23 with feed pipe, and the feed pipe other end passes through feed pump 24 and a container for paint
25 are connected.By feed pump stock and certain pressure can be provided in this way, so that the coating in applicator roll is under pressure
It from being penetrated in through-hole into miniature pit, and is applied on film substrate by differential in turn, has structure simple, feeding is convenient
The advantages that quick controllable.Further, the through-hole 21 is evenly arranged along micro-recesses length direction.Facilitate micro-recesses in this way
The interior coating penetrated is more uniform, improves coating homogeneity.Further, the micro-recesses 20 on the applicator roll 18 are
The helicla flute of spiral shape setting preferably improves in such manner, it is possible to improve the area of micro-recesses and film substrate contact and smears effect
Fruit.Further, it is additionally provided with pulp-collecting box 26 below the applicator roll and coating back flow roll, the pulp-collecting box 26 is located at container for paint
It is connected above 25 and by recovery channel 27 with container for paint 25.It can recycle to form circulation coating by self weight splicing in this way,
Coating utilization efficiency is improved, site environment health is kept, and is conducive to realize cleaning.
In b step, the multi-functional priming coat can also be realized by the way of quantitative feeding transfer coated.Adopt
It is fed with a metering roller, is then coated on film substrate using a transferring roller transfer.This mode, has
The advantages that structure is simple, easy to control, is readily able to accurately control coating layer thickness, and the material of coating is uniformly dispersed.
The mode of quantitative feeding transfer coated can specifically use quantitative feeding transfer coated device shown in fig. 5 to realize,
The quantitative feeding transfer coated device, including a metering roller 28,28 surface of metering roller is continuously and equably
Distribution setting is there are many preset miniature pit of volume, miniature pit diameter range 0.002mm-5mm, further includes and quantitative feeding
The connected feed mechanism of roller 28,28 side of metering roller is affixed side by side is provided with a transferring roller 29, and transferring roller 29 is backwards
Metering roller side is affixed side by side is provided with a coating back flow roll 30, and film substrate 2 is by transferring roller 29 and coating back flow roll 30
Between, so that the film substrate 2 passed through is coated back flow roll tensioning and is bonded with transferring roller, the metering roller 28, transferring roller
29 are arranged with the coating linkage of back flow roll 30.In this way, using the device, in use, first quantitative feeding will be arrived on coating by feed mechanism
Then roller surface quantitatively shifts and is coated to transferring roller by transferring roller and coat on the film substrate between back flow roll, therefore has
Have that structure is simple, easy to control, the advantages of can be realized accurate quantification coating control.
Above-mentioned to synchronize in accurate apparatus for coating, better choice is that the feed mechanism includes being set to metering roller
Upper magazine 31 is closed away from one of the reversed side of transferring roller, on magazine side is corresponded to metering roller in closing and is provided with and is used for
With the coating opening of quantitative feeding roller surface fitting, it is coated with to be respectively arranged on opening upper and lower seamed edge and is axially cut with metering roller
The scraper 32 of line at an angle.Using such feed mechanism, the coating is set in the upper magazine 31 of closing, and quantitative
It is coated to quantitative feeding roller surface by being coated with opening when feed roller rotates, then using the blade and feed of adjustment scraper 32
The distance controlling paint thickness of roller 28 can be realized accurate quantification feed.And have many advantages, such as that structure is simple, it is conducive to control.Into
One step, 31 both ends of magazine are connected with downwards cartridge holder 33 in the closing, and upper 33 lower end of cartridge holder is hingedly mounted on
In rack.It is safeguarded in this way, can be convenient and overturn the upper magazine of opening closing by rotary loading box support.Further, institute
It states and gear is installed in metering roller 28, transferring roller 29 and the coating respective shaft of back flow roll 30 and is intermeshed, by any tooth
Wheel is connected with a motor (gear is not shown in the figure with motor) realizes linkage transmission.In this way, having structure simple, and realize
Synchronous interaction transmission control.Further, 29 both ends of transferring roller, which are installed downwards, is connected with telescoping mechanism 34, telescoping mechanism 34
Fixing end is fixed on the rack, and the telescopic end of telescoping mechanism 34 is connected up in transfer roll end, the tooth at the transferring roller both ends
It takes turns position to be higher than metering roller and coat the gear position at back flow roll both ends, be resetted downwards so that transferring roller drives by telescoping mechanism
When, transferring roller both ends gear can be dropped downward into and be engaged between feed roller and the gear for coating back flow roll both ends.In this way, setting
Telescoping mechanism, can facilitate and be jacked up upwards by transferring roller is whole, in favor of realizing the work such as cleaning and maintenance speed regulation;Simultaneously should
Unique texture enables to the lifting of transferring roller not influence the engaged transmission again of three gears, therefore very easy to use quick.
Further, it is additionally provided with a pulp-collecting box 35 below the metering roller 28, transferring roller 29 and coating back flow roll 30, it is described fixed
The projection of amount feed roller and transferring roller straight down drops into 35 range of pulp-collecting box.In this way, can be returned by pulp-collecting box splicing
It receives and utilizes, improve coating utilization efficiency, guarantee job site environment health.
In b step, the setting of the multi-functional priming coat can also be realized by the way of blade coating.I.e. first according to
By feeding roller by coating be coated on film substrate surface after, then using scraper scrape obtain required thickness multi-functional priming coat.
This mode can make it preferably control the functional layer thickness of acquisition by the position for adjusting control scraper.
Specifically, the mode of the blade coating, can be realized, the scraper using knife coating apparatus shown in fig. 6
Apparatus for coating, including horizontal alignment are affixed one feeding roller 36 of setting and a feeding back flow roll 37, feeding roller 36 and feed mechanism
It is connected and realizes coating feeding, also face is disposed with a horizontally disposed scraper 38 above feeding roller 36, on feeding back flow roll 37
Founder has to a scraper back flow roll 39, the setting of scraper back flow roll described in 38 blade face of scraper, 2 motion path of film substrate is disposed with
There is the route segment moved straight up and by feeding roller 36 and feeding back flow roll 37 and 38 blade of scraper and scraper back flow roll
Between 39.In this way, being first passed through between feeding roller and feeding back flow roll when film substrate 2 moves straight up, and realized by feeding roller
Feeding scrapes the dope layer of required thickness by scraper then when by scraper.By the way of vertically scraping, Ke Yigeng
The coating for scraping required thickness of coating layer well, and conveniently scraping falls downwards and is deposited in film substrate surface, guarantees to enter
The paint thickness on the film substrate surface of doctor position is enough, and pit defect is not present in the dope layer scraped;And extra coating
It can fall to downwards on feeding roller and recycle.
In above-mentioned knife coating apparatus, better choice is that 36 surface of feeding roller is continuous and is evenly distributed setting
There are many preset miniature pit of volume, miniature pit diameter range 0.05mm-5mm.In this way, convenient preferably by miniature recessed
Hole accumulation coating is to be better achieved the coating to film substrate.Further, the feed mechanism, including one be set to
Expect a coating material cartridge 40 on the outside of roller, feeding roller is corresponded on 40 side of coating material cartridge and is provided with painting for being bonded with feeding roller surface
Cloth opening is coated with the scraper being respectively arranged on opening upper and lower seamed edge with feeding roller axial direction tangent line at an angle.Using such
Feed mechanism, the coating are set in coating material cartridge, and are coated to feeding roller surface by being coated with opening in the rotation of feeding roller,
Then control paint thickness is scraped using scraper, can be realized accurate quantification feed.And have structure simple, it is conducive to control etc.
Advantage.Further, coating material cartridge mounting bracket 41, coating material cartridge mounting bracket are connected with to outer lower side on the coating material cartridge 40
41 lower ends are hingedly mounted in rack.It is carried out in this way, can be convenient and open coating material cartridge by rotation coating material cartridge mounting bracket overturning
Feeding.Further, it is additionally provided with recycling box 42 below the feeding roller, the coating conveniently fallen down realizes recycling, and is conducive to protect
Hold site environment health.
In b step, the setting of the multi-functional priming coat can also be using slot die coating (slot die)
Mode is realized.Coating is set in a coating material cartridge body, setting corresponds to the narrow of film substrate width together on coating box body
Then coating is squeezed out by control pressure and is applied to film substrate surface by seam.This mode realizes control by control pressure
System can be realized pre-measured coating, and for coating wet thickness up to 1um, even more thin achievable single layer and the double-deck coating, speed are reachable
300 ms/min, have and be suitble to roll-to-roll (roll to roll) continuous coating process, the control precision of coating thickness is high, has
Implement simple, easy to control advantage.
The mode of above-mentioned slot die coating, can specifically be realized using narrow slit type coating apparatus shown in Fig. 7, described
Narrow slit type coating apparatus, including a coating box body 43,43 lower end of coating box body are vertically provided with a coated panel 44, coated panel
One of coating slit, the width side of one section of horizontal segment in coating 2 material path of slit face film base are offered in 44 downwards
To setting, it is provided with a slot coated back flow roll 45 below coating slit face film substrate, slot coated back flow roll 45 will be thin
Film base material 2 is supported and is connected at coating slit exit, and 43 bore seal of coating box body is arranged and is loaded with coating, is applied
Body upper end is provided with and communicated with tracheae 46 upwards and is connected to pneumatic supply, and pneumatic control valve 47 is provided on tracheae.In this way, by
Pressure control valve regulation air inflow, and then adjusting coating tray interior pressure, so that coating always can be with stable pressure quilt
It is forced on film substrate, guarantees the uniformity of coating.
In the narrow slit type coating apparatus, better choice is that the 44 lower end side shape of coated panel is half downwards
Circle, coating are opened in semicircle lower end medium position with slit.It is scratched this way it is possible to avoid generating, guarantees the stabilization of coating
Property.Further, pressure sensor 49, institute are additionally provided between the 45 both ends shaft of slot coated back flow roll and mounting bracket 48
Pressure sensor 49 is stated to be connected with pneumatic control valve 47.In this way, can be by suffered by pressure sensor detection slot coated back flow roll
Pressure size, feedback control pneumatic control valve, guarantee that coating is extruded with the pressure of stable equilibrium, guarantee the equal of coating
Weighing apparatus is stablized.Further, the coating box body 43 is located above film substrate along the side of film substrate direction of advance and also sets up
There is the even roller 50 of pressure, press and be additionally provided with the even back flow roll 51 of pressure below even roller 50, film substrate 2 is located in even 50 He of roller of pressure
It presses between even back flow roll 51, even roller 50 and a connection of pressure mechanism 52 set up is pressed to be mounted on the rack.In this way, can make
It is coated with slit squeeze out coating, be extruded in roller even through over-voltage uniformly, better ensure that coating reliability and
Even property.Improve coating quality.Further, it presses even 50 surface of roller to be provided with one layer of non-sticking lining 53, avoids due to bonding and shadow
Ring coating quality.Using which, pre-measured coating easy to accomplish;Coating wet thickness is even more thin up to 1um;It can be achieved single
Layer and it is multi-layer coated
In step c, the grapheme material layer is continuously coated with, grapheme material coating by grapheme material coating
Principle active component includes the graphene that growth thereon is parallel to the metal nanometer line of graphene planes, further includes (a small amount of) make
For the resin of bonding agent.Specifically stone can be prepared disclosed in granted patent CN201410847076.8 using the present inventor
The composite material and preparation method of black alkene portal structure.I.e. principle active component includes metal nanometer line and metal nanoparticle
And the graphene microchip of the size of square micron magnitude, mention it can preferably after subsequent welding is in portal structure
High conduction performance.The mode that grapheme material layer is arranged in step c can be consistent with the mode that multi-functional priming coat is arranged, i.e., will
After material is dissolved in polar solvent, it is coated on multi-functional priming coat, therefore is not described here in detail by the way of coating.
In Step d, the welding of grapheme material layer is realized, can use the side of high frequency program control pulse xenon lamp light pulse welding
Formula is realized.Controlled with high-frequency impulse (preferably 50HZ frequencies above) to the grapheme material layer on film substrate by xenon lamp
It is irradiated, presses in conjunction with pressure roll, so that existing again after metal nanometer line and metal nanoparticle sorption enhanced illumination thermal energy
Pressure acts on lower welding and grapheme material layer is fixed as one.The mode of this light pulse welding has and implements simple, control
The advantages that system is convenient, reliable in quality.It is non-using silver nano material when especially suitable nano wire and nano particle are silver-colored material
Linear character is easy sorption enhanced thermal property under high power pulse illumination, realizes the welding of grapheme material layer.
Specifically, the mode of the light pulse welding can be realized using the light pulse fusion splicing devices of structure shown in Fig. 8,
The light pulse fusion splicing devices include two xenon lamp devices being connected with high-frequency impulse control module, before and after two xenon lamp devices between
Every the top for being juxtaposed on the 2 one section of horizontal segment in path of film substrate, two downward face film bases of xenon lamp device direction of illumination
Material is arranged, and a welding pressure roller 54, welding 54 lower section of pressure roller are provided with above the film substrate between two xenon lamp devices
Be correspondingly arranged on a welding back flow roll 55, welding pressure roller 54 and welding back flow roll 55 by 2 sandwiched of film substrate in the inner.This
Sample, film substrate first pass through an xenon lamp device, under the high-frequency impulse illumination of xenon lamp, so that metal nanometer line and metal nano
Particle sorption enhanced illumination thermal energy completes preliminary welding, then again by the pressure of welding pressure roller, allows the material to molten
Be pressed further by based on contact it is closely knit be integrated to obtain required layer structure, then again pass by the irradiation of xenon lamp device
Ensure each fusion point position reliability of completing that overlapped, avoids fusion point caused by squeezing from disconnecting, guarantee that graphene material is made
The electric conductivity of the bed of material is met the requirements.Therefore device has structure simple, easy to control, welding excellent effect, obtained graphene
The advantages that material layer electric conductivity is excellent.
In above-mentioned light pulse fusion splicing devices, better choice is that the xenon lamp device includes an entirety in downwardly open
Tubaeform shell 56, uniform intervals are provided with multiple rows of xenon lamp 57 in shell 56, and every row's xenon lamp 57 is along film substrate width side
To setting and mutual dislocation is arranged.In this way, the uniformity of illumination can be better ensured that, guarantee that grapheme material absorbs heat
Equilibrium, the grapheme material layer various loci electric conductivity guaranteed are consistent.Further, the welding 54 top of pressure roller
It is connected by pressure mechanism 58 with rack.Welding can be controlled by pressure mechanism 58 in this way to be pressed with pressure roller, guarantee its pressure
Big minor adjustment is moderate, improves and grapheme material layer quality is made.
In Step d, the welding of grapheme material layer is realized, it can be real by the way of room temperature plasma self limiting welding
It is existing.
The room temperature plasma is from limit introduced details, using the processing gas such as hydrogen, oxygen, nitrogen or helium, warp
Crossing ac magnetic field processing makes its plasma and is ejected into grapheme material layer surface.Pass through lotus energy particle pair in plasma
The bombardment of grapheme material layer surface, provides energy so that the metal nanometer line grown on graphene in grapheme material layer and
The metal nanometer line metal infall grown on adjoining graphite alkene due to coating generation sandwiched therebetween interval, by argon-arc plasma field
Excitation and polarization, form part " hot spot " at the interval, make the intersection of metal nanometer line that nanoscale welding occur.It realizes
Welding causes electric conductivity to sharply increase.This mode is easy to operate, and welding is reliable and stable, and treatment temperature is lower, to film base
The influence of material and grapheme material is smaller, will not cause the modification of film substrate.
This processing mode belongs to nonequilibrium plasma processing mode.Gas at normal temperature shown in Fig. 9 can specifically be used
Plasma spraying fusion splicing devices realize that the gas at normal temperature plasma spraying fusion splicing devices include horizontally disposed mounting plate 59,
Mounting plate 59 is located above 2 one sections of horizontal routes of film substrate, and 59 lower surface of mounting plate is fixedly installed tubulose straight down
Gas nozzle 60, gas nozzle 60 are made for insulating materials, 60 upper end of gas nozzle connection gas source vessel 61, outside gas nozzle 60
Diametrically opposite both ends are further fixedly arranged on positive electrode and negative electrode 62 on all sides, are additionally provided with and positive electrode and negative electrode
62 connected controllers 63.
In this way, gas source vessel provides processing gas and air pressure, sprays processing gas downwards from gas nozzle, rely on simultaneously
Controller controls positive electrode and negative electrode generates ac magnetic field, so that producing inside the gas nozzle between positive electrode and negative electrode
Glow discharge phenomenon perhaps capacitive coupling microwave discharge phenomenon or inductive coupling microwave discharge phenomenon are given birth to, so that processing gas
It sprays after being ionized at a lower temperature, under the premise of which does not influence film substrate itself acute variation, realizes to film
The introduced details of the grapheme material layer of substrate surface.Simple with structure, processing efficiently, can be realized at nonequilibrium ionization
Reason, degree of ionization are high;Gas has higher activation degree.Obtain and maintain at lower temperatures the plasma with higher energy
Body, the advantages that being more suitable for thermally sensitive transparent organic film material.
In above-mentioned gas at normal temperature plasma spraying fusion splicing devices, better choice is, the gas nozzle 60 be uniformly but
Dislocation is arranged in multiple rows of on mounting plate 59.In this way, multiple rows of gas nozzle of Heterogeneous Permutation, can preferably improve processing effect
Fruit.The positive electrode and negative electrode section are fixed on outside gas nozzle in minor arc shape and fitting.In this way, can preferably be conducive to electricity
Formation and be conducive to improve electric field action effect.Further, two pairs of positive electrodes and yin are provided on the gas nozzle 60
Electrode, two pairs of electrodes are vertically intervally arranged, and each pair of positive electrode and negative electrode line direction are arranged vertically.In this way, can be more
Guaranteeing well can be by electric field by all gas in gas nozzle, and obtains more uniform electric field treatment effect.
In Step d, heat welded can also be realized by the way of roller hot pressing, i.e., after being heated to roller, so that
Film substrate passes through between roller and the pressure roller for being affixed setting, heats by roller to film substrate and presses again by pressure roller, leads to
The mode for crossing high temperature hot pressing makes metal nanometer line and metal nanoparticle dissolving cured with grapheme material and consolidation, obtains
To the grapheme material layer of parameter and performance stable and uniform.This mode can be conducive to improve welding effect in favor of flow line production
Fruit improves electric conductivity, can preferably make each layer be pressed closely knit, improve physical parameter consistency.
The roller heat pressing type welding process can specifically be realized, the rolling using roller hot-press arrangement shown in Fig. 10
Cylinder hot-press arrangement including roller 64 and pressure roller 65 and is the roller heating mechanism of roller heating, and the pressure roller 65 is set side by side
In roller side, 65 both ends of pressure roller are arranged on the telescopic end of a telescoping mechanism 66, and the fixing end of telescoping mechanism 66 is fixed on
In rack, 64 direction of telescopic direction slidable of the telescoping mechanism 66 is arranged.Using this device, have structure simple,
It can be realized flow line production, facilitate the advantages that adjusting pressure.
In the roller hot-press arrangement, better implementation scheme is that the roller heating mechanism includes the rolling of metal material
Cylinder inner core further includes the heating coil 67 outside roller side, and the heating coil 67 is for generating magnetic field and in roller
Induced current is generated in the roller inner core for making it internal when rotation realizes heating.In this way, the rotation using roller itself generates heat
Can, have structure simple, is conducive to setting, convenient the advantages that degree of heat is controlled by heating coil current.Further, described
Telescoping mechanism 66 can be cylinder, simple in structure and low in cost, and be conducive to be set and controlled.
In step e, the anti-reflection optical match layer is continuously coated with by anti-reflection optical match coated coating, including with
Under type: a, the one or more using following resins: tetrafluoroethene and the unformed amorphous of perfluorinated alkyl vinyl ether copolymer
Property resin (the unformed amorphous resin AF of such as Du Pont, AF1600/AF2400, SPC-1410), perfluoroethylene-propylene (FEP), with
And nano granular of zinc oxide, the titanium dioxide nanoparticle, nanometer silicon dioxide particle, nano oxygen of b, total content for 0.2% ~ 5%
Change one or more of zirconium particle, is formulated as anti-reflection optical match coated coating with fluoride solvent and is coated with;
Or with a, modified aliphatic urethane acrylate, 200,000 vinyl polysiloxanes of relative molecular weight, relative molecular weight 5
Thousand ~ 6,000 sulfydryl polysiloxanes and the acrylic acid silicon-fluorine polymer object of relative molecular weight 50,000 ~ 60,000 it is one or more;B, always contain
Nano granular of zinc oxide, titanium dioxide nanoparticle, nanometer silicon dioxide particle and the nano zircite particle that amount is 0.2% ~ 5%
One or more of;C, photoinitiator and light stabilizer;Anti-reflection optical match layer is obtained after the coated UV solidification of three kinds of materials;
Or with a, water soluble acrylic resin, b, the nano granular of zinc oxide that total content is 0.2% ~ 5%, nano silica
One or more of grain, titanium dioxide nanoparticle, nano zircite particle;It is coated dry that two kinds of materials are mixed into water paint
It is dry to obtain anti-reflection optical match layer.
In such manner, it is possible to preferably improve graphene film surface property consistency, it can preferably adjust reduction and obtain stone
The refractive index of black alkene film, and reduce reflection and increase light transmittance, improve graphene film performance.
In step e, the set-up mode of the anti-reflection optical match layer can be consistent with multi-functional priming coat set-up mode,
It is not described here in detail.
The method of the present invention, f step, i.e. overlay film step, i.e., after anti-reflection optical match layer is set, then in the upper of film substrate
Lower surface respectively covers bonding layer protecting film.Convenient product obtained is formal before use, providing protection to graphene film.Tool
When body is implemented, overlay film step is realized by the way of the extruding of a pair of of pressure roller.
The present invention implements the quality factor σ that industrial graphene transparent conductive film has superelevationdc /σopt, common is super
1000 are crossed, more preferably reaches 1200 ~ 1500, it is optimal up to 1800.In contrast, commonly lack the quality factor σ of layer graphenedc/
σoptAbout 550 or so.The quality factor σ of ITOdc/σoptAbout in 300-350 or so, the polycrystalline graphite of CVD method preparation
The quality factor σ of alkenedc/σoptOnly about 100 ~ 180 or so.
Claims (8)
1. a kind of plasma spraying formula graphene transparent conductive film substrate preprocess method, which is characterized in that use hydrogen, oxygen
The processing gas such as gas, nitrogen or helium, handling by ac magnetic field makes its plasma and is ejected into substrate surface;With right
Film substrate carries out the modified pretreatment in surface, clean the surface and reduction surface tension, and in Surface Creation polar group.
2. plasma spraying formula graphene transparent conductive film substrate preprocess method as described in claim 1, which is characterized in that
Realize that the gas plasma ejection processing device includes horizontally disposed substrate using gas plasma ejection processing device,
Substrate is located above one section of horizontal route of film substrate, and base lower surface is fixedly installed straight down to be made of injection torch jet pipe
Ion spray torch array, spray torch jet pipe for insulating materials be made, injection torch jet pipe upper end connect gas source, spray torch jet pipe outside
Diametrically opposite both ends are further fixedly arranged on pairs of electrode on all sides, are additionally provided with the controller being connected with electrode.
3. plasma spraying formula graphene transparent conductive film substrate preprocess method as claimed in claim 2, which is characterized in that
The injection torch jet pipe is arranged in multiple rows of on substrate for uniform but dislocation.
4. plasma spraying formula graphene transparent conductive film substrate preprocess method as claimed in claim 2, which is characterized in that
Two pairs of electrodes are provided on the injection torch jet pipe, two pairs of electrodes are vertically intervally arranged, and each pair of electrode connecting line direction is vertical
Arrangement.
5. a kind of continuous preparation method of roll-to-roll graphene transparent conductive film, which is characterized in that including be successively carried out continuously with
Lower step: it a, is realized using plasma spraying formula graphene transparent conductive film substrate preprocess method described in claim 3 or 4
The modified pretreatment in surface, clean the surface and reduction surface tension are carried out to transparent film substrate;B, film substrate surface is continuous
It is coated with multi-functional priming coat, it is made to further decrease surface tension, increases the binding force with graphene conductive material layer;C, it applies again
Cloth at least one layer grapheme material layer, grapheme material layer include at least several small flake graphite alkene, and grow thereon
Metal nanometer line;D, spread over coating numerous between the metal nanometer line on the grapheme material on multi-functional priming coat
Mutual overlapped points welding is whole, and is fixed as one between each layer;It further include step e after Step d, after above-mentioned steps processing
Film substrate surface be continuously coated with anti-reflection optical match layer;Further include step f overlay film after step e, that is, is setting anti-reflection light
The film substrate upper and lower surface for learning matching layer fits over setting layer protecting film.
6. the roll-to-roll continuous preparation method of graphene transparent conductive film as claimed in claim 5, which is characterized in that in b step,
The multi-functional priming coat, be by include total content be 0.2% ~ 5% nano granular of zinc oxide, titanium dioxide nanoparticle, receive
One or more of rice silica dioxide granule, nano zircite particle and total content are 3% ~ 20% water-based acrylic resin composition
Multi-functional bottom coating be continuously applied to the surface of film substrate, drying forms.
7. the roll-to-roll continuous preparation method of graphene transparent conductive film as claimed in claim 5, which is characterized in that in step c,
The grapheme material layer is continuously coated with by grapheme material coating, grapheme material coating principle active component packet
The graphene that growth thereon is parallel to the metal nanometer line of graphene planes is included, further includes the resin as bonding agent.
8. the roll-to-roll continuous preparation method of graphene transparent conductive film as claimed in claim 5, which is characterized in that in step e,
The anti-reflection optical match layer, is continuously coated with, including following manner by anti-reflection optical match coated coating: a, using following
The one or more of resin: tetrafluoroethene and the unformed amorphous resin of perfluorinated alkyl vinyl ether copolymer, perfluoroethylene third
Alkene and b, it the nano granular of zinc oxide that total content is 0.2% ~ 5%, titanium dioxide nanoparticle, nanometer silicon dioxide particle, receives
One or more of rice zirconia particles are formulated as anti-reflection optical match coated coating with fluoride solvent and are coated with;
Or with a, modified aliphatic urethane acrylate, the vinyl polysiloxane of relative molecular weight 200,000, relative molecular weight 5
Thousand ~ 6,000 sulfydryl polysiloxanes and the acrylic acid silicon-fluorine polymer object of relative molecular weight 50,000 ~ 60,000 it is one or more;B, always contain
Nano granular of zinc oxide, titanium dioxide nanoparticle, nanometer silicon dioxide particle and the nano zircite particle that amount is 0.2% ~ 5%
One or more of;C, photoinitiator and light stabilizer;Anti-reflection optical match layer is obtained after the coated UV solidification of three kinds of materials;
Or with a, water soluble acrylic resin, b, the nano granular of zinc oxide that total content is 0.2% ~ 5%, nano-titanium dioxide nanometer
One or more of particle, nanometer silicon dioxide particle, nano zircite nano particle;Two kinds of materials are mixed into water paint warp
Coating is dried to obtain anti-reflection optical match layer.
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CN114472522A (en) * | 2022-01-26 | 2022-05-13 | 重庆墨希科技有限公司 | Method and device for preparing high-conductivity graphene metal composite material with assistance of plasma |
CN117531647A (en) * | 2024-01-10 | 2024-02-09 | 靖江瑞泰电子材料有限公司 | Surface treating agent device is scribbled in SMD upper cover area |
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CN1906235A (en) * | 2004-10-06 | 2007-01-31 | 日东电工株式会社 | Hard coating film, antireflective hard coating film, optical element and image display device |
CN104934108A (en) * | 2014-12-31 | 2015-09-23 | 重庆元石石墨烯技术开发有限责任公司 | Metallic nanowire-graphene bridge structural composite material and preparation method thereof |
CN105761774A (en) * | 2014-12-19 | 2016-07-13 | 北京生美鸿业科技有限公司 | Novel electrode material applicable to intelligent liquid crystal dimming film and preparation method thereof |
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CN1906235A (en) * | 2004-10-06 | 2007-01-31 | 日东电工株式会社 | Hard coating film, antireflective hard coating film, optical element and image display device |
CN105761774A (en) * | 2014-12-19 | 2016-07-13 | 北京生美鸿业科技有限公司 | Novel electrode material applicable to intelligent liquid crystal dimming film and preparation method thereof |
CN104934108A (en) * | 2014-12-31 | 2015-09-23 | 重庆元石石墨烯技术开发有限责任公司 | Metallic nanowire-graphene bridge structural composite material and preparation method thereof |
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CN117531647A (en) * | 2024-01-10 | 2024-02-09 | 靖江瑞泰电子材料有限公司 | Surface treating agent device is scribbled in SMD upper cover area |
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