CN111161906A - Low-resistance transparent conductive film and preparation method thereof - Google Patents
Low-resistance transparent conductive film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a conductive material, in particular to a low-resistance transparent conductive film and a preparation method thereof. The low-resistance transparent conductive film comprises a substrate, a conductive layer and a protective layer, wherein the conductive layer and the protective layer are alternately arranged; the conducting layer is at least two layers, the protective layer is at least two layers, and one conducting layer is arranged on the surface of the base material. The low-resistance transparent conductive film provided by the invention forms a parallel circuit by a conductive layer containing one or more of nano silver, graphene, carbon nano tubes or conductive polymers and a protective layer containing a compound with a conjugated structure, a charge transfer complex, a composite conductive polymer material and the like, thereby greatly reducing the resistance value of the conductive film.
Description
Technical Field
The invention relates to a conductive material, in particular to a low-resistance transparent conductive film and a preparation method thereof.
Background
The transparent conductive film (transparent conductive film for short) is a conductive material which can conduct electricity and has high light transmittance in a visible light range, and has wide application in the fields of touch screens, flat panel displays, solar cells, light emitting diodes and the like.
As a representative of nano materials, a transparent conductive thin film of a nano silver wire (hereinafter, abbreviated as AgNW) has attracted attention of researchers in recent years due to its excellent characteristics in electrical, optical and mechanical properties. The transparent conductive film prepared by the AgNW has the advantages of high visible light transmittance, low surface resistance, smooth and flat surface, good flexibility and the like, and is lower in price compared with the ITO film widely used at present.
In the prior art, the production method for coating the nano silver wire on the substrate such as transparent glass to form the transparent conductive film generally comprises the following steps: firstly, preparing a nano silver wire coating liquid, generally, uniformly stirring the nano silver wire in glue, then adding or not adding an auxiliary agent (a mixture containing a dispersing agent, a curing agent and a solvent), then coating the prepared nano silver wire coating liquid on the surface of a transparent substrate to form a nano silver wire conductive coating, and finally baking and curing to obtain the nano silver wire conductive coating. The main component of the glue is one or more high molecular organic matters, the high molecular organic matters can generally reduce the transmittance and the conductivity of the nano silver wire conductive layer, and when the transmittance is about 85%, the sheet resistance value of the nano silver wire conductive film can only reach about 30 omega/sq. In order to reduce the surface resistance of the AgNW transparent conductive film, the surface resistance is generally achieved by increasing the thickness of the AgNW layer, which inevitably sacrifices the light transmittance (i.e., visible light transmittance) of the conductive film, increases the haze of the conductive film, and thus reduces the overall effect of the conductive film.
Disclosure of Invention
The invention aims to overcome the defects and provides a low-resistance transparent conductive film and a preparation method thereof.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the low-resistance transparent conductive film comprises a substrate, wherein the low-resistance transparent conductive film further comprises conductive layers and protective layers, and the conductive layers and the protective layers are alternately arranged; the conducting layer is at least two layers, the protective layer is at least two layers, and one conducting layer is arranged on the surface of the base material.
Furthermore, the resistance of the conductive layer arranged on the surface of the substrate is smaller than that of other protective layers.
Further, in the above-mentioned case,
the conductive layer contains a conductive component; preferably, the conductive component is one or more of nano silver, graphene, a carbon nanotube or a conductive polymer;
the protective layer contains resin or conductive material; preferably, the resin contains a compound with a conjugated structure and a charge transfer complex, and the conductive material is a composite conductive polymer material, indium tin oxide or an inorganic semiconductor material.
Further, in the above-mentioned case,
the conjugated structure is one or more of pyrrole, thiophene, aniline and derivatives thereof, oligomeric pyrrole, oligomeric thiophene, oligomeric aniline or copolymers among the pyrrole, thiophene, aniline and oligomeric pyrrole;
the charge transfer complex is a charge transfer complex formed by TMB, TCNQ or both;
the composite conductive polymer material is formed by adding conductive filler or fibers into a polymer material, wherein the conductive filler is one or more of conductive carbon powder, conductive zinc oxide, conductive ITO (indium tin oxide) and antistatic ATO (antimony tin oxide);
the inorganic semiconductor material is selenium, germanium, monocrystalline silicon or a compound formed by a third main group element and a fifth main group element.
Furthermore, the sheet resistance of the low-resistance transparent conductive film is 0.1-80 omega/sq, the transmittance is 50-92%, and the haze is 0.6-20%.
Further, the substrate is a copolymer or a mixture or a laminated object of one or more materials of glass, polycarbonate, polyacrylate, polyimide, polyolefin and polyester, or a film obtained by functional coating treatment;
preferably, the polyolefin is polyethylene and the polyester is polyethylene terephthalate.
Furthermore, the thickness of the base material is 1-200 μm, the thickness of the conductive layer is 10-500nm, and the thickness of the protective layer is 10-500 nm.
The invention also provides a preparation method of the low-resistance transparent conductive film, wherein the preparation method comprises the following steps:
s1, preparing a conductive layer coating liquid;
s2, preparing a protective layer coating liquid;
s3, coating the conductive layer coating liquid on the surface of the base material, and drying or curing after coating to obtain a conductive layer;
s4, coating the protective layer coating liquid on the surface of the conductive layer, and drying or curing after coating to obtain a protective layer;
s5, repeating the steps S3 and S4 to obtain the low-resistance transparent conductive film.
Further, the composition of the conductive layer coating liquid is as follows:
further, the monomer is a water-soluble or alcohol-soluble organic small molecular compound; preferably a water-soluble or alcohol-soluble organic small molecule compound having a relative molecular mass of less than 500; more preferably at least one of polyethylene glycol diacrylate, butyl acrylate, glyceryl acrylate, pentaerythritol tripropionate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, N-vinylpyrrolidone or acryloylmorpholine.
The resin is water-soluble or alcohol-soluble resin; at least one of aliphatic urethane acrylate oligomer, epoxy acrylate oligomer, or polyester (meth) acrylate is preferable.
Specifically, the aliphatic polyurethane acrylate oligomer can be Sadoma CN9006NS or Changxing chemical DR-U026, etc.; the epoxy acrylate oligomer can be chemical 6210G of Changxing, and the like; the polyester (methyl) acrylate can be M-7100 synthesized in east Asia and the like.
In the invention, the auxiliary agent can be one or more selected from wetting dispersant, defoaming agent and film-forming auxiliary agent.
In the present invention, the wetting dispersant is mainly used for reducing the surface tension of the inkForce, improving the leveling property of the ink; such as bike DISPERBYK-199, DISPERBYK-2015, DISPERBYK-2012, BYK3410, DISPERBYK-180; TEGOERBYK-1802tps, 740, 750, 755, A,
Wet 280, Wet KL 245, Dispers 650; in particular, the wetting dispersant may also participate in the photocuring reaction, thereby giving the printed article a transparent appearance. Specifically, the wetting dispersant may be one or more of a silicone acrylate and a modified polysiloxane-based polymer capable of radiation crosslinking. The organic silicon acrylate capable of being subjected to radiation crosslinking can be TEGO RAD 2010, 2011, 2100, 2200N, 2250 and the like of Digao company, and can participate in a photocuring reaction and perform a crosslinking reaction, so that phenomena such as fogging of a printed product can be inhibited; the modified polysiloxane polymer may be BYK-333, BYK-371, BYK-377 from Bick, Tego wet 270 from Digao, Tego Glide 450 from Digao, and the like. The defoaming agent is mainly used for eliminating bubbles generated in the filtering and printing processes and avoiding the generated bubbles from influencing the printing fluency; the defoamer can be a silicone-free polymer, such as digao silicone-free defoamers TEGO Airex 920, TEGO Airex 921, and the like.
The film-forming assistant is used for preventing the ink composition from depositing, so that the stability of the ink composition in the storage process is ensured; the type of the film-forming aid is not particularly limited as long as the aforementioned requirements are satisfied. The film-forming auxiliary agent is starch, arabic gum, pectin, agar, gelatin, alginate jelly, carrageenan, dextrin, etc., general gelatin, soluble starch, polysaccharide derivative, etc.; the synthetic product comprises at least one of carboxymethyl cellulose, propylene glycol alginate, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, casein, sodium polyacrylate, polyoxyethylene, and polyvinylpyrrolidone.
In the present invention, the initiator used may be an aqueous initiator or an alcohol-soluble initiator.
Specifically, the aqueous initiator may be an aryl ketone, including at least one of a benzophenone derivative, a thioxanthone derivative, an alkyl aryl ketone derivative, or a benzil derivative. The aqueous initiator can also be at least one of a photoinitiator 2959, Dow AMP-95, IRGACURE 819 or IRGACURE 500.
The alcohol-soluble initiator can be at least one of 2-hydroxy-2-methyl-phenyl acetone-1 (photoinitiator 1173), TPO or BDK.
The solvent is one or more of water, ethanol or isopropanol.
Further, the composition of the protective layer coating liquid is as follows:
in the present invention, when preparing the conductive layer coating liquid or the protective layer coating liquid, it is only necessary to stir and mix the conductive layer coating liquid or the protective layer coating liquid uniformly according to the composition and the ratio of each coating liquid.
In the invention, the conductive component is one or more of nano silver, graphene, carbon nano tubes or conductive polymers; the resin contains a compound with a conjugated structure and a charge transfer complex, and the conductive material is a composite conductive high polymer material, indium tin oxide or an inorganic semiconductor material.
Further, the conjugated structure is one or more of pyrrole, thiophene, aniline and derivatives thereof, oligomeric pyrrole, oligomeric thiophene, oligomeric aniline or copolymers between the pyrrole, the oligomeric thiophene and the oligomeric aniline; the charge transfer complex is a charge transfer complex formed by TMB, TCNQ or both; the composite conductive polymer material is formed by adding conductive filler or fibers into a polymer material, wherein the conductive filler is one or more of conductive carbon powder, conductive zinc oxide, conductive ITO (indium tin oxide) and antistatic ATO (antimony tin oxide); the inorganic semiconductor material is selenium, germanium, monocrystalline silicon or a compound formed by a third main group element and a fifth main group element.
Further, the resin is polyethylene, polyvinyl chloride, epoxy resin, polyurethane, polyacrylate, polymethyl methacrylate, fluoropolymer, polyamide, polyimide, polysiloxane, polycarbonate, polysulfone, polyvinyl alcohol, polyester, acrylonitrile-butadiene-phenylpropene copolymer or a blend thereof.
The functional material is at least one of an ultraviolet absorbent, an antioxidant or a high-refraction high-hardness additive, specifically, the ultraviolet absorbent is one or a combination of more of salicylates, benzophenones, benzotriazoles, substituted acrylonitrile, triazines and hindered amines, the antioxidant is a free radical scavenging antioxidant such as N-phenyl- α -naphthylamine, alkyl phenothiazine and the like, the metal deactivation antioxidant such as one or a combination of more of benzotriazole derivatives and mercaptobenzothiazole derivatives, and the high-refraction high-hardness additive is silicon micropowder, talcum powder, argil, mica, silicon dioxide, fly ash, silicate and other minerals, glass fibers, carbon fibers, whiskers and the like.
In the invention, the initiator used in the protective layer can also be a water-insoluble initiator, including benzoin and derivatives (benzoin, benzoin dimethyl ether, etc.); benzils (diphenylethanone, etc.); alkylphenones (diethoxyacetophenone and the like); acylphosphine oxides (aroylphosphine oxide, bisbenzoylphenylphosphine oxide, etc.); benzophenones (benzophenone, etc.).
The auxiliary agent is the same as above.
The solvent is one or more of acetone, butanone, methyl ethyl ketone, ethyl acetate, toluene, xylene, heavy aromatic hydrocarbon and butyl acetate.
In the invention, the curing is photo-curing or thermal curing.
Compared with the prior art, the invention has the following advantages:
the low-resistance transparent conductive film provided by the invention forms a parallel circuit by a conductive layer containing one or more of nano silver, graphene, carbon nano tubes or conductive polymers and a protective layer containing a compound with a conjugated structure, a charge transfer complex, a composite conductive polymer material and the like, thereby greatly reducing the resistance value of the conductive film.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic structural diagram of a five-layer low-resistance transparent conductive film according to the present invention;
FIG. 2 is a schematic structural view of a seven-layer low-resistance transparent conductive film according to the present invention;
wherein, in the figure:
1-substrate, 2-conductive layer, 3-protective layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A low-resistance transparent conductive film comprises a substrate 1, a conductive layer 2 and a protective layer 3, wherein the conductive layer 2 and the protective layer 3 are alternately arranged; the conductive layer 2 has at least two layers, and the protective layer 3 has at least two layers, for example, the conductive layer 2 and the protective layer 3 may have two layers or three layers; one of the conductive layers 2 is disposed on the surface of the substrate 1.
As shown in fig. 1, a five-layer low-resistance transparent conductive film is provided, which specifically comprises: a low-resistance transparent conductive film comprises a substrate 1, a conductive layer 2 and a protective layer 3, wherein the conductive layer 2 and the protective layer 3 are alternately arranged, the conductive layer 2 and the protective layer 3 are respectively two layers, and one layer of the conductive layer 2 is arranged on the surface of the substrate 1.
As shown in fig. 2, a low-resistance transparent conductive film with a seven-layer structure is provided, which specifically comprises: a low-resistance transparent conductive film comprises a substrate 1, a conductive layer 2 and a protective layer 3, wherein the conductive layer 2 and the protective layer 3 are alternately arranged, the conductive layer 2 and the protective layer 3 are three layers, and one layer of the conductive layer 2 is arranged on the surface of the substrate 1.
The conducting layer 2 contains one or more of nano silver, graphene, carbon nano tubes or conducting polymers, and the thickness is 10-500 nm; the protective layer 3 contains resin or conductive material, specifically, the resin contains a compound with a conjugated structure and a charge transfer complex, and the conductive material is a composite conductive polymer material, indium tin oxide or an inorganic semiconductor material. The thickness of the conductive layer is 10-500 nm.
The conjugated structure is one or more of pyrrole, thiophene, aniline and derivatives thereof, oligomeric pyrrole, oligomeric thiophene, oligomeric aniline or copolymers among the pyrrole, thiophene, aniline and oligomeric pyrrole;
the charge transfer complex is a charge transfer complex formed by TMB, TCNQ or both;
the composite conductive polymer material is formed by adding conductive filler or fibers into a polymer material, wherein the conductive filler is one or more of conductive carbon powder, conductive zinc oxide, conductive ITO (indium tin oxide) and antistatic ATO (antimony tin oxide);
the inorganic semiconductor material is selenium, germanium, monocrystalline silicon or a compound formed by a third main group element and a fifth main group element.
The thickness of the substrate is 1-200 μm, and the substrate is a copolymer, a mixture or a laminated product of one or more materials of glass, polycarbonate, polyacrylate, polyimide, polyolefin and polyester, or a film obtained by functional coating treatment; preferably, the polyolefin is polyethylene and the polyester is polyethylene terephthalate.
The sheet resistance of the low-resistance transparent conductive film is 0.1-80 omega/sq, the transmittance is 50-92%, and the haze is 0.6-20%.
The preparation method of the low-resistance transparent conductive film comprises the following steps:
s1, preparing a conductive layer coating liquid;
s2, preparing a protective layer coating liquid;
s3, coating the conductive layer coating liquid on the surface of the base material, and drying or curing after coating to obtain a conductive layer;
s4, coating the protective layer coating liquid on the surface of the conductive layer, and drying or curing after coating to obtain a protective layer;
s5, repeating the steps S3 and S4 to obtain the low-resistance transparent conductive film.
Example 1
In the present embodiment, a low resistance transparent conductive film is provided, as shown in fig. 1, which includes a substrate 1, two conductive layers 2 and two protective layers 3, wherein each conductive layer 2 and each protective layer 3 are alternately disposed, and one conductive layer 2 is disposed on a surface of the substrate 1. The base material is a polyethylene terephthalate film with the thickness of 125 mu m; the conductive layer 2 contains nano silver; the protective layer 3 contains a compound with a conductive group oligothiophene. The square resistance of the low-resistance transparent conductive film is 2 omega/sq, the transmittance is 66 percent, and the haze is 10 percent.
The step of preparing the low-resistance transparent conductive film specifically comprises the following steps:
s1, preparing a conductive layer coating liquid: 0.5% of nano-silver wire, 0.01% of wetting dispersant (DISPERBYK-2012), 0.0001% of trimethylolpropane triacrylate, 1% of photoinitiator 1173 of trimethylolpropane triacrylate and the balance of water, and stirring for 30min to obtain the nano-silver wire coating liquid. Wherein 1kg of the nano silver wire coating liquid contains 5g of nano silver wires; the diameter of the nano silver wire is less than or equal to 25 nanometers, and the length of the nano silver wire is 5-25 micrometers;
s2, preparation of protective layer coating liquid: cleviosTMF100T coating, 0.003 percent of N-phenyl- α -naphthylamine, 0.01 percent of photoinitiator 2959, 0.01 percent of auxiliary agent (Greatech GT8003 from Gudi), and the balance of water/isopropanol (1:1) are stirred for 30min to obtain a protective layer coating solution, wherein 1kg of the protective layer coating solution contains 10g of PEDOT/PSS conductive polymer.
S3, coating of a conductive layer coating liquid: conveying the PET substrate by a conveyor belt of a coating device, uniformly coating the conductive layer coating liquid prepared in the step S1 on the surface of the PET substrate by a coating head above the conveyor belt, drying at 120 ℃ for 2min after coating to obtain a nano silver wire conductive layer, wherein the thickness of the conductive layer coating liquid coated on the surface of the PET substrate is about 40 mu m;
s4, coating protective layer coating liquid: conveying the PET substrate with the nano silver wire conductive layer to coating equipment again, uniformly coating the protective layer coating liquid prepared in the step S2 on the surface of the nano silver wire conductive layer through a coating head above a conveying belt, drying at 120 ℃ for 2min after coating, and thus obtaining the conductive film with a layer of nano silver wire, wherein the thickness of the protective layer coating liquid coated on the surface of the nano silver wire conductive layer is about 20 microns; the measured surface resistance is 6ohm/sq, the transmittance is 89 percent, and the haze is 5.6 percent;
s5, repeating the steps S3 and S4 to obtain a low-resistance transparent conductive film with two layers of nano silver wire conductive layers and two layers of oligothiophene protective layers; the surface resistance was measured to be 2ohm/sq, transmittance 66%, haze 10%.
Example 2
In the present embodiment, a low resistance transparent conductive film is provided, as shown in fig. 1, which includes a substrate 1, two conductive layers 2 and two protective layers 3, wherein each conductive layer 2 and each protective layer 3 are alternately disposed, and one conductive layer 2 is disposed on a surface of the substrate 1. The base material is a polyethylene terephthalate film with the thickness of 125 mu m; the conductive layer 2 contains nano silver; the protective layer 3 contains a protective layer with antistatic ATO solution ATO-050 of Shanghai Zhengnzhen nanometer technology Limited. The sheet resistance of the low-resistance transparent conductive film is 13 omega/sq, the transmittance is 85 percent, and the haze is 3.1 percent.
The step of preparing the low-resistance transparent conductive film specifically comprises the following steps:
s1, preparing a conductive layer coating liquid: 0.15% of nano-silver wire, 0.003% of wetting dispersant (DISPERBYK-2012), CN9006NS0.1% of sartomera, 5% of initiator TPO (by mass of sartomera CN9006 NS) and the balance of water/ethanol (1:1), and stirring for 30min to obtain a nano-silver wire coating liquid; wherein 1kg of the nano silver wire coating liquid contains 1.5g of nano silver wires; the diameter of the nano silver wire is less than or equal to 25 nanometers, and the length of the nano silver wire is 5-25 micrometers;
s2, preparation of protective layer coating liquid: 0.1% of ATO-050 coating, 10% of carbon fiber, 1% of initiator aroylphosphine oxide, 0.01% of auxiliary agent (TEGO Airex 921) and the balance solvent ethyl acetate, and stirring for 30min to obtain a protective layer coating liquid; wherein 1kg of the protective layer coating liquid contained 1g of ATO conductive material.
S3, coating of a conductive layer coating liquid: conveying the PET substrate by a conveyor belt of a coating device, uniformly coating the conductive layer coating liquid prepared in the step S1 on the surface of the PET substrate by a coating head above the conveyor belt, drying at 120 ℃ for 2min after coating to obtain a nano silver wire conductive layer, wherein the thickness of the conductive layer coating liquid coated on the surface of the PET substrate is about 20 mu m;
s4, coating protective layer coating liquid: conveying the PET substrate with the nano silver wire conductive layer to coating equipment again, uniformly coating the protective layer coating liquid prepared in the step S2 on the surface of the nano silver wire conductive layer through a coating head above a conveying belt, drying at 120 ℃ for 2min after coating, and thus obtaining the conductive film with a layer of nano silver wire, wherein the thickness of the protective layer coating liquid coated on the surface of the nano silver wire conductive layer is about 20 microns; the measured surface resistance was 21ohm/sq, transmittance was 88%, haze was 2.6%;
s5, repeating the steps S3 and S4 to obtain a low-resistance transparent conductive film with two layers of nano silver wire conductive layers and two layers of ATO protective layers; the surface resistance was measured to be 13ohm/sq, transmittance 85%, haze 3.1%.
Example 3
The present embodiment provides a low-resistance transparent conductive film, as shown in fig. 2, including a substrate 1, three conductive layers 2 and three protective layers 3, wherein each conductive layer 2 and each protective layer 3 are alternately disposed, and one conductive layer 2 is disposed on the surface of the substrate 1. The substrate is a polycarbonate film and has the thickness of 200 mu m; the conductive layer 2 contains graphene; the protective layer 3 contains ITO. The square resistance of the low-resistance transparent conductive film is 21 omega/sq, the transmittance is 82%, and the haze is 2.1%.
The step of preparing the low-resistance transparent conductive film specifically comprises the following steps:
s1, preparing a conductive layer coating liquid: 0.1% of graphene, 0.01% of wetting dispersant (DISPERBYK-2012), 0.5% of Yangxing chemical 6210G, 3% of initiator BDK in the mass of the Yangxing chemical 6210G and the balance of water, and stirring for 30min to obtain the conductive layer coating liquid.
S2, preparation of protective layer coating liquid: ITO 1%, 0.01% glass fiber, 0.001% initiator diethoxyacetophenone, 0.01% auxiliary agent (polyvinylpyrrolidone), and the balance of butanone, and stirring for 30min to obtain the protective layer coating liquid.
S3, coating of a conductive layer coating liquid: conveying the polycarbonate substrate by a conveying belt of a coating device, uniformly coating the conductive layer coating liquid prepared in the step S1 on the surface of the polycarbonate substrate by a coating head above the conveying belt, drying for 2min at 120 ℃ after coating to obtain a conductive layer, wherein the thickness of the conductive layer coating liquid coated on the surface of the polycarbonate substrate is about 20 mu m;
s4, coating protective layer coating liquid: conveying the polycarbonate substrate with the nano silver wire conductive layer to coating equipment again, uniformly coating the protective layer coating liquid prepared in the step S2 on the surface of the graphene conductive layer through a coating head above a conveying belt, and performing UV (ultraviolet) curing for 1min after coating to obtain the graphene conductive film with one layer, wherein the thickness of the protective layer coating liquid coated on the surface of the graphene conductive layer is about 20 microns; the measured surface resistance was 36ohm/sq, transmittance was 89%, haze was 1.6%;
s5, repeating the steps S3 and S4 twice to obtain a low-resistance transparent conductive film with three graphene conductive layers and three ITO protective layers; the surface resistance was measured to be 21ohm/sq, transmittance 85%, haze 2.2%.
Comparative example 1
This comparative example provides a low-resistance transparent conductive film having the same structure as that of example 1, as shown in fig. 1, including a substrate 1, two conductive layers 2 and two protective layers 3, each conductive layer 2 being alternately disposed with each protective layer 3, wherein one conductive layer 2 is provided on the surface of the substrate 1. The base material is a polyethylene terephthalate film with the thickness of 125 mu m; the conductive layer 2 contains nano silver; the protective layer 3 contains a urethane resin protective layer. The sheet resistance of the low-resistance transparent conductive film is 21 omega/sq, the transmittance is 85 percent, and the haze is 3.1 percent.
The step of preparing the low-resistance transparent conductive film specifically comprises the following steps:
s1, preparing a conductive layer coating liquid: 0.5% of nano-silver wire, 0.01% of wetting dispersant (DISPERBYK-2012), 0.0001% of trimethylolpropane triacrylate, 1% of photoinitiator 1173 of trimethylolpropane triacrylate and the balance of water, and stirring for 30min to obtain the nano-silver wire coating liquid. Wherein 1kg of the nano silver wire coating liquid contains 5g of nano silver wires; the diameter of the nano silver wire is less than or equal to 25 nanometers, and the length of the nano silver wire is 5-25 micrometers;
s2, preparation of protective layer coating liquid: 1% of polyurethane resin coating resin, 0.01% of an auxiliary agent (GreatechGT 8003 of Gudi corporation), 0.01% of a binder (cationic epoxy compound photocuring resin) and the balance of a solvent xylene, and stirring for 30min to obtain a protective layer coating liquid;
s3, coating of a conductive layer coating liquid: conveying the PET substrate by a conveyor belt of a coating device, uniformly coating the conductive layer coating liquid prepared in the step S1 on the surface of the PET substrate by a coating head above the conveyor belt, drying at 120 ℃ for 2min after coating to obtain a nano silver wire conductive layer, wherein the thickness of the conductive layer coating liquid coated on the surface of the PET substrate is about 20 mu m;
s4, coating protective layer coating liquid: conveying the PET substrate with the nano silver wire conductive layer to coating equipment again, uniformly coating the protective layer coating liquid prepared in the step S2 on the surface of the nano silver wire conductive layer through a coating head above a conveying belt, drying at 120 ℃ for 2min after coating, and thus obtaining the conductive film with a layer of nano silver wire, wherein the thickness of the protective layer coating liquid coated on the surface of the nano silver wire conductive layer is about 20 microns; the measured surface resistance is 23ohm/sq, the transmittance is 89 percent, and the haze is 2.6 percent;
s5, repeating the steps S3 and S4 to obtain a low-resistance transparent conductive film with two layers of nano silver wire conductive layers and two layers of ATO protective layers; the surface resistance was measured to be 21ohm/sq, transmittance 85%, haze 3.1%.
It can be seen from comparing example 1 and comparative example 1 that the conductive film provided by the present invention has lower surface resistance, higher transmittance and lower haze. Therefore, the method can remarkably reduce the surface resistance of the conductive film by changing the components of the protective layer coating liquid, and meanwhile, the transmittance of the conductive film is not sacrificed, and the haze of the conductive film is not increased.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The low-resistance transparent conductive film comprises a substrate (1), and is characterized by further comprising conductive layers (2) and protective layers (3), wherein the conductive layers (2) and the protective layers (3) are alternately arranged; the conductive layer (2) is at least two layers, the protective layer (3) is at least two layers, and one conductive layer (2) is arranged on the surface of the base material (1).
2. The transparent conductive film according to claim 1, wherein the conductive layer (2) provided on the surface of the substrate (1) has a resistance lower than that of the protective layer (3).
3. The transparent conductive film with low resistance according to claim 2,
the conductive layer (2) contains a conductive component; preferably, the conductive component is one or more of nano silver, graphene, a carbon nanotube or a conductive polymer;
the protective layer (3) contains resin or conductive material; preferably, the resin contains a compound with a conjugated structure and a charge transfer complex, and the conductive material is a composite conductive polymer material, indium tin oxide or an inorganic semiconductor material.
4. The transparent conductive film with low resistance according to claim 3,
the conjugated structure is one or more of pyrrole, thiophene, aniline and derivatives thereof, oligomeric pyrrole, oligomeric thiophene, oligomeric aniline or copolymers among the pyrrole, thiophene, aniline and oligomeric pyrrole;
the charge transfer complex is a charge transfer complex formed by TMB, TCNQ or both;
the composite conductive polymer material is formed by adding conductive filler or fibers into a polymer material, wherein the conductive filler is one or more of conductive carbon powder, conductive zinc oxide, conductive ITO (indium tin oxide) and antistatic ATO (antimony tin oxide);
the inorganic semiconductor material is selenium, germanium, monocrystalline silicon or a compound formed by a third main group element and a fifth main group element.
5. The transparent conductive film with low resistance according to any one of claims 1 to 4, wherein the transparent conductive film with low resistance has a sheet resistance of 0.1 to 80 Ω/sq, a transmittance of 50 to 92% and a haze of 0.6 to 20%.
6. The transparent conductive film with low resistance according to claim 5, wherein the substrate is a copolymer or a mixture or a laminate of one or more of glass, polycarbonate, polyacrylate, polyimide, polyolefin and polyester, or a film obtained by a functional coating treatment;
preferably, the polyolefin is polyethylene and the polyester is polyethylene terephthalate.
7. The transparent conductive film with low resistance according to claim 6, wherein the thickness of the substrate is 10 to 200 μm, the thickness of the conductive layer (2) is 10 to 500nm, and the thickness of the protective layer (3) is 10 to 500 nm.
8. A method for preparing a low-resistance transparent conductive film according to any one of claims 1 to 7, comprising the steps of:
s1, preparing a conductive layer coating liquid;
s2, preparing a protective layer coating liquid;
s3, coating the conductive layer coating liquid on the surface of the base material, and drying or curing after coating to obtain a conductive layer;
s4, coating the protective layer coating liquid on the surface of the conductive layer, and drying or curing after coating to obtain a protective layer;
s5, repeating the steps S3 and S4 to obtain the low-resistance transparent conductive film.
9. The production method according to claim 8, wherein in step S1, the composition of the conductive layer coating liquid is as follows:
10. the production method according to claim 8 or 9, wherein in step S2, the composition of the protective layer coating liquid is as follows:
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114694877A (en) * | 2020-12-28 | 2022-07-01 | 乐凯华光印刷科技有限公司 | Nano-silver wire composite transparent conductive film |
| CN115491137A (en) * | 2022-08-22 | 2022-12-20 | 苏州华苏塑料有限公司 | Portable transparent electric-conduction heat-conduction protective film and preparation method thereof |
-
2020
- 2020-01-19 CN CN202010059248.0A patent/CN111161906A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114694877A (en) * | 2020-12-28 | 2022-07-01 | 乐凯华光印刷科技有限公司 | Nano-silver wire composite transparent conductive film |
| CN115491137A (en) * | 2022-08-22 | 2022-12-20 | 苏州华苏塑料有限公司 | Portable transparent electric-conduction heat-conduction protective film and preparation method thereof |
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