CN109961904A - Blade coating formula graphene transparent conductive film substrate functional layer setting method - Google Patents

Abstract

The invention discloses a kind of blade coating formula graphene transparent conductive film substrate functional layer setting methods, which is characterized in that after coating is first coated on film substrate surface by feeding roller, then the multi-functional priming coat for obtaining required thickness is scraped using scraper.It also discloses and uses a kind of roll-to-roll continuous preparation method of graphene transparent conductive film that the above method realizes each functional layer coating.Present invention utilizes the coating process that blade coating principle realizes each functional layer of transparent film substrate, have the advantages that implementation is simple, easy to operate, conducive to control, coating weight is accurate, and coating efficiency is high, and stability is good.

Description

Blade coating formula graphene transparent conductive film substrate functional layer setting method

Technical field

The invention belongs to graphene transparent conductive film preparation fields, and in particular to transparent to a kind of blade coating formula graphene Conductive film base material functional layer setting 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 deposition 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；E, in above-mentioned steps, treated that film substrate surface is continuously coated with anti-reflection optical match layer.

Wherein, the multi-functional priming coat, the functional layers such as grapheme material layer and anti-reflection optical match layer setting when, It is to consider to realize by the way of coating.But when these functional layers are arranged, what kind of mode coating is specifically realized using, It can implement simply, it is easy to operate, it is conducive to control, improves Painting effect, and improve obtained functional layer performance；As this field Technical staff needs further to consider the problems of to solve.

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 Blade coating principle, and implement simply, it is easy to operate, it is conducive to control, coating weight is accurate, and coating efficiency is high, and stability is good to scrape Cutter painting cloth graphene transparent conductive film substrate functional layer setting method.

Vocabulary of terms involved in the application is as follows: quality factor: the ratio between electrically conducting transparent membrane conductivity and light transmittance σ_dc/ σ_opt.Transparent conductive film is in addition to excellent electric conductivity, it is also necessary to the ratio between excellent conductivity, light transmission (σ_dc/σ_opt )。σ_dc Determine the surface resistance of transparent conductive film, σ_optDetermine the light transmission rate of transparent conductive film.Quality factor describe transparent conductive film very well Photoelectric properties.

In order to solve the above technical problems, technical scheme is as follows:

A kind of blade coating formula graphene transparent conductive film substrate functional layer setting method, which is characterized in that first rely on feeding roller After coating is coated on film substrate surface, then the multi-functional priming coat for obtaining required thickness is scraped using scraper.

This mode can make it preferably control the functional layer thickness of acquisition by the position for adjusting control scraper.

As optimization, this method can specifically be realized using knife coating apparatus below, the knife coating apparatus, packet Include that horizontal alignment is affixed a feeding roller of setting and a feeding back flow roll, feeding roller are connected with feed mechanism and realize on coating Material, feeding roller top also face are disposed with a horizontally disposed scraper, and face is disposed with a doctor back above feeding back flow roll Roller, the setting of scraper back flow roll described in scraper edge face, film substrate motion path have a route segment moved straight up And by between feeding roller and feeding back flow roll and scraper edge and scraper back flow roll.

In this way, being first passed through between feeding roller and feeding back flow roll when film substrate 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.

Further, the feeding roller surface is continuous and is evenly distributed the preset miniature pit of volume there are many settings, Miniature pit diameter range 0.05mm-5mm.In this way, convenient preferably by miniature pit accumulation coating to be better achieved pair The coating of film substrate.

Further, the feed mechanism, a coating material cartridge being set on the outside of feeding roller including one, coating material cartridge side Upper corresponding feeding roller is provided with the opening of the coating for being bonded with feeding roller surface, is respectively arranged on coating opening upper and lower seamed edge With the scraper of feeding roller axial direction tangent line at an angle.Using such feed mechanism, the coating is set in coating material cartridge, and It is coated to feeding roller surface by being coated with opening in the rotation of feeding roller, then scrapes control paint thickness, energy using scraper Enough realize accurate quantification feed.And have many advantages, such as that structure is simple, it is conducive to control.

Further, coating material cartridge mounting bracket, coating material cartridge mounting bracket are connected with to outer lower side on the coating material cartridge Lower end is 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 Material.

Further, it is additionally provided with recycling box below the feeding roller, the coating conveniently fallen down realizes recycling, and is conducive to protect Hold site environment health.

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: the modified pretreatment in surface, clean the surface and reduction table a, are carried out to transparent film substrate Face tension；B, film substrate surface is continuously coated with multi-functional priming coat, it is made to further decrease surface tension, increase and graphene The binding force of conductive material layer；C, it is coated at least one layer of grapheme material layer, grapheme material layer includes at least several small Flake graphite alkene, and the metal nanometer line grown thereon；D, coating is made to spread over the graphene material on multi-functional priming coat Numerous mutual overlapped points welding is whole between metal nanometer line on material, and is fixed as one between each layer；After Step d also Including step e, in above-mentioned steps, treated that film substrate surface is continuously coated with anti-reflection optical match layer；Further include after step e Step f overlay film fits over setting layer protecting film in the film substrate upper and lower surface for setting anti-reflection optical match layer；Its In, it is all made of when multi-functional priming coat and grapheme material layer and anti-reflection optical match layer are set and scrapes cutter painting as described above Cloth graphene transparent conductive film substrate functional layer setting method realizes coating.Above-mentioned roll-to-roll graphene transparent conductive film is continuous Preparation method 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 coating process that blade coating principle realizes each functional layer of transparent film substrate, has and implement Simply, the advantages that easy to operate, conducive to control, coating weight is accurate, coating efficiency height, stability is good.

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, it is thick then to scrape control coating using scraper 32 Degree can be realized accurate quantification feed.And have many advantages, such as that structure is simple, it is conducive to control.Further, magazine in the closing 31 both ends are connected with downwards cartridge holder 33, and upper 33 lower end of cartridge holder is hingedly mounted in rack.In this way, can be convenient logical The upper magazine of rotary loading box support overturning opening closing is crossed to be safeguarded.Further, the metering roller 28, transferring roller 29 It is driven with being equipped with gear in the coating respective shaft of back flow roll 30 and being intermeshed realization linkage, any gear and a motor (gear is not shown in the figure with motor) transmission is connected.In this way, having structure simple, and realize synchronous interaction transmission control.Into One step, 29 both ends of transferring roller, which are installed downwards, is connected with telescoping mechanism 34, and 34 fixing end of telescoping mechanism is fixed on the rack, The telescopic end of telescoping mechanism 34 is connected up in transfer roll end, and the gear position at the transferring roller both ends is higher than metering roller With the gear position at coating back flow roll both ends, when so that transferring roller driving reset downwards by telescoping mechanism, transferring roller both ends gear energy It enough drops downward into and is engaged between feed roller and the gear for coating back flow roll both ends.In this way, the telescoping mechanism of setting, can facilitate By the whole jack-up upwards of transferring roller, in favor of realizing the work such as cleaning and maintenance speed regulation；The unique texture enables to turn simultaneously The lifting for moving roller does not influence the engaged transmission again of three gears, therefore very easy to use quick.Further, the quantitative confession A pulp-collecting box 35 is additionally provided with below material roller 28, transferring roller 29 and coating back flow roll 30, the metering roller and transferring roller are perpendicular Straight downward projection drops into 35 range of pulp-collecting box.In this way, can be recycled by pulp-collecting box splicing, improves coating and utilize Efficiency guarantees 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 is from limit plasma 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 nanometer silicon dioxide particle, titanium dioxide nanoparticle, 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, 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, nanometer silicon dioxide particle, titanium dioxide nanoparticle 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 superelevation_dc /σ_opt, 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 graphene_dc/ σ_optAbout 550 or so.The quality factor σ of ITO_dc/σ_optAbout in 300-350 or so, the polycrystalline graphite of CVD method preparation The quality factor σ of alkene_dc/σ_optOnly about 100 ~ 180 or so.

Claims (10)

1. a kind of blade coating formula graphene transparent conductive film substrate functional layer setting method, which is characterized in that first rely on feeding After coating is coated on film substrate surface by roller, then the multi-functional priming coat for obtaining required thickness is scraped using scraper.

2. blade coating formula graphene transparent conductive film substrate functional layer setting method as described in claim 1, feature exist In using knife coating apparatus below realization, the knife coating apparatus is affixed a feeding of setting including horizontal alignment Roller and a feeding back flow roll, feeding roller are connected with feed mechanism and realize coating feeding, and also face is disposed with one above feeding roller Horizontally disposed scraper, feeding back flow roll top face is disposed with a scraper back flow roll, scraper back flow roll described in scraper edge face Setting, film substrate motion path have a route segment moved straight up and pass through feeding roller and feeding back flow roll and scrape Between knife blade and scraper back flow roll.

3. blade coating formula graphene transparent conductive film substrate functional layer setting method as claimed in claim 2, feature exist In the feeding roller surface is continuous and is evenly distributed the preset miniature pit of volume there are many settings, miniature pit diameter model Enclose 0.05mm-5mm.

4. blade coating formula graphene transparent conductive film substrate functional layer setting method as claimed in claim 2, feature exist In, the feed mechanism, a coating material cartridge being set on the outside of feeding roller including one corresponds to feeding roller on coating material cartridge side and sets It is equipped with the coating opening for being bonded with feeding roller surface, is respectively arranged on coating opening upper and lower seamed edge and is axially cut with feeding roller The scraper of line at an angle.

5. blade coating formula graphene transparent conductive film substrate functional layer setting method as claimed in claim 4, feature exist In being connected with coating material cartridge mounting bracket to outer lower side on the coating material cartridge, coating material cartridge mounting bracket lower end is hingedly mounted on In rack.

6. blade coating formula graphene transparent conductive film substrate functional layer setting method as claimed in claim 2, feature exist In the feeding roller lower section is additionally provided with recycling box.

7. 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: the modified pretreatment in surface, clean the surface and reduction surface tension a, are carried out 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；Wherein, multi-functional primary coat is set It is all made of when layer and grapheme material layer and anti-reflection optical match layer and scrapes cutter painting as described in claim 3 or 4 or 5 or 6 Cloth graphene transparent conductive film substrate functional layer setting method realizes coating.

8. the roll-to-roll continuous preparation method of graphene transparent conductive film as claimed in claim 7, 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.

9. the roll-to-roll continuous preparation method of graphene transparent conductive film as claimed in claim 7, 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.

10. the roll-to-roll continuous preparation method of graphene transparent conductive film as claimed in claim 7, which is characterized in that step e In, the anti-reflection optical match layer is continuously coated with, including following manner: a, use by anti-reflection optical match coated coating The one or more of following resins: tetrafluoroethene and the unformed amorphous resin of perfluorinated alkyl vinyl ether copolymer, poly- perfluor Second propylene and b, the nano granular of zinc oxide that total content is 0.2% ~ 5%, nanometer silicon dioxide particle, nano-titanium dioxide One or more of grain, nano zircite particle are formulated as anti-reflection optical match coated coating with fluoride solvent and are 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, nanometer silicon dioxide particle, titanium dioxide nanoparticle 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.